Plant Design Project Final 2

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PLANT DESIGN PROJECT (SKKK 4824)

2016/2017 SEM 2
PRODUCTION OF 15, 000 MTA DIMETHYL CARBONATE
SUPERVISOR:
Assoc. Prof. Dr. Zainura Zainon Noor
DESIGN TEAM MEMBERS:
AQILA BINTI ALIAS A13KK0016

MOH YEE KHIM A13KK0050
NIA DAMIYATHI ABDUL HAWI A13KK0087
RAVINDRAN A/L PERIMAL A13KK0126
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EXECUTIVE SUMMARY
Dimethyl carbonate was initially produced by the reaction of methanol and

phosgene but the extreme toxicity of phosgene prompted new sustainable and benign
manufacturing processes. Considering the economic potential for each process, their
sustainability prospects and product yield, the transesterification of propylene carbonate
with methanol has been chosen to complement the design of a plant capable in
producing 15,000 MTA of dimethyl carbonate in Malaysia. Dimethyl carbonate has seen
its potential application in the solvent, pharmaceutical, plastic, fuel and paint industries
at the global stage. The key drivers of dimethyl carbonate production lies on the
polycarbonate and paint demands in which by 2023, 53.2% of the total volume of
dimethyl carbonate produced is expected to be taken up by the polycarbonate industry.
Gebeng, Pahang is chosen as our plant site because its development is based on
petrochemical and chemical industry. The industrial land is located nearby Gebeng
bypass which eases traffic flow from the industrial land to Kuantan Port, links Kuala
Lumpur and Kuantan directly via East Coast Highway. Gebeng has been selected as our
plant location due to the lowest land price ranging from RM 15.00 – 30.00 / ft 2. The
future expansion and project enlargement is made possible with enough land for project
continuation. Furthermore, the abundance of raw material in the same city will also
reduce the cost of transportation of the raw material as well as the availability of good
transportation and port facilities.
The operation of the proposed plant is 340 days annually and 24 hours daily in
which the remaining amount of operation time will be reserved for plant maintenance
and repair of unit operations down time. With the presence of CeCu catalyst, the
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conversion rate of propylene carbonate to dimethyl carbonate is approximately 65%.

Manual calculations is done to provide a detailed overview for process synthesis using
Microsoft Excel 2010 worksheet whereas the process simulation is executed with Aspen
PLUS simulator. The percentage errors of deviation for both material and energy
balances in terms of manual calculations and simulation are less than the 15% limit.
Thus, it is deemed feasible for the proposed plant to produce 15,000 MTA of dimethyl
carbonate.
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TABLE OF CONTENT
CHAPTER TITLE PAGE
TABLE OF CONTENTS iii

LIST OF TABLES vi
LIST OF FIGURES vii
1.0 LITERATURE REVIEW & PROJECT

CONCEPTION
1.1 Chemical Product Background 1
1.1.1 Physical and Chemical Properties of Dimethyl 3
Carbonate
1.1.2 Applications of Dimethyl Carbonate
1.1.3 Safety Measures and Toxicity
1.1.4 Storage and Handling
1.2 Market Survey 5
1.2.1 Market Demand of Dimethyl Carbonate
1.2.2 Global Outlook
1.2.3 Asia Pacific Outlook
1.2.4 Malaysia Outlook
1.2.5 Market Price of Dimethyl Carbonate
1.2.6 Availability of Raw Materials
1.3 Site Selection 5
1.3.1 Suggested Locations
1.3.2 Factors of Selection and Comparisons between
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Locations
1.3.3 Matrix for Site Selection
1.4 Process Selection
1.4.1 Direct Synthesis from Carbon Dioxide and
Methanol
1.4.2 Transesterification of methanol and propylene
carbonate using CeCu
1.4.3 Oxidative Carbonylation of Methanol
2.0 PROCESS CREATION AND SYNTHESIS

2.1 Process Synthesis 6
2.1.1 Step 1: Eliminate Difference in Molecular 8
Type
2.1.2 Step 2: Distribution of Chemicals 10
2.1.3 Step 3: Eliminate Differences in Composition
2.1.4 Step 4: Elimination of Differences in
Temperature, Pressure and Phase
2.1.5 Step 5: Task Integration
2.2 Process Description
3.0 MANUAL MATERIAL AND ENERGY BALANCE

CALCULATIONS
3.1 Introduction 27
3.2 Manual Material Balance Calculation 31
3.3 Material Balance Based on Equipment 31
3.4 Manual Energy Balance Calculation 32
4.0 PRELIMINARY SIMULATION OF MATERIAL

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AND ENERGY BALANCE

4.1 Introduction
4.2 Aspen PLUS Simulation
4.3 Absolute Relative Deviation
4.4 Comparison between Manual Calculations and
Simulation Results
4.4.1 Material Balance
4.4.2 Energy Balance
5.0 INNOVATION POTENTIAL

5.1 Comparison between Patented and New Process
Flow
Design
6.0 PROCESS HEAT INTEGRATION

6.1 Introduction
6.2 Pinch Technology Analysis
6.3 Data Extraction
6.4 Program Table Algorithm
6.5 Heat Exchanger Network
7.0 PROCESS OPTIMIZATION

7.1 Introduction
7.2.1 Scope of Optimization Problems
7.2 Optimization on Distillation Column (DC-101)
7.3 Comparison between Conditions Before & After
Optimization
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8.0 EQUIPMENT SIZING AND COSTING

8.1 Introduction
8.2 Reactors
8.3 Separation Columns
8.4 Compressor
8.5 Expander
8.6 Pumps
8.7 Heat Exchangers
8.8 Heaters
8.9 Mixers
9.0 MECHANICAL DESIGN

9.1 Introduction
9.2 General Mechanical Design Procedures
9.3 Summary of Mechanical Design of Equipment DC-
100
10.0 WASTE TREATMENT

10.1 Introduction
10.2 Waste Management Hierarchy
10.3 Waste Minimization and Pollution Prevention
10.4 Air Quality Standard Information
10.5 Methodology
10.5.1 Waste Sources Identification
11.0 PROCESS CONTROL AND INSTRUMENTATION

11.1 Introduction
11.2 Objectives of Process Control
11.3 Controller Configurations
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11.4 Piping and Instrumentation Diagram (PID)

Elements
11.5 Individual Unit Control System
11.5.1 Control System for Reactors (SR-1 and SR-2)
11.5.2 Control System for Distillation Column 1
(DC-
100)
11.5.3 Control System for Distillation Column 2
(DC-
101)
11.5.4 Control System for High Pressure Column
(HPC-100)
11.5.5 Control System for Low Pressure Column
(LPC-100)
11.5.6 Control System for Pressure-Reducing Valve
1 (VLV-100)
1 (VLV-100)
2 (VLV-101)
3 (VLV-102)
11.5.9 Control System for Heater 1 (H-100)
11.5.11 Control System for Pump 1 (P-100)
12.0 PROCESS SAFETY

12.1 Introduction
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12.2 General Safety Guidelines

12.3 Worker Safety
12.4 Safety in Pipeline Layout
12.5 General Safety in Dimethyl Carbonate Production
Plant
12.6 Plant Layout
12.7 Hazard and Operability Studies (HAZOP)
Introduction
12.8 HAZOP Study Execution
12.8.1 Reactor
12.8.2 Distillation Column
12.8.3 Pump
12.8.4 Valve
12.8.5 Compressor
12.8.6 Flash Column
12.8.7 Heat Exchanger
12.8.8 Mixer
12.9 Fault Tree Analysis
12.9.1 Fault and Probability Data
12.9.2 Minimal Cut Set
12.9.3 Analysis
12.9.4 Reactors (SR-1 & SR-2)
12.9.5 Flash Column (LPC-100)
12.9.6 Distillation Column (DC-100, DC-101 &
HPC-100)
12.9.7 Pump (P-100, P-101 & P-102)
12.9.8 Pressure-Reducing Valves (VLV-100, VLV-
101 & VLV-102)
12.9.9 Heaters (H-100 & H-101)
12.9.10 Summary
12.10 Plant Startup and Shutdown
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12.10.1 Introduction
12.10.2 Plant Startup
12.10.3 Plant Shutdown
13.0 PROFITABILTIY ANALYSIS

12.1 Introduction
12.3 Worker Safety
12.5 General Safety in Dimethyl Carbonate Production
Plant
12.6 Plant Layout
12.7 Hazard and Operability Studies (HAZOP)
Introduction

14.0 CONCLUSION
APPENDICES
Appendix A: Material Safety Data Sheet (MSDS)
Appendix B: Raw Material Supplier
Appendix C: Physical and Chemical Properties
Appendix D: Manually Developed Design and Stream
Summary Table
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Appendix E: Simulation Design and Stream Summary

Table
REFERENCES
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LIST OF FIGURES
FIGURE NO. TITLE PAGE

1.1 Global Consumption of Dimethyl Carbonate 10
According to End-Use
1.2 Global Dimethyl Carbonate Market Value (USD 11
Billion)
1.3 U.S Dimethyl Carbonate Market Size by Application 12
from 2013-2024 (USD Million)
1.4 Global Dimethyl Carbonate Market by Region 2015- 14
2023
1.5 Total Value of Imports by Countries in India 15
1.6 Malaysia Plastic Compounding Market by Product, 16
2014-2025 (USD Million)
1.7 Global Methanol Supply and Demand 18
1.8 Global Methanol Demand Based on Applications 19
2.1 Flow Diagram of Chemical Distribution in the 50
System 51
2.2 Flow Diagram of Chemical Distribution in the
System with Recycled Stream 53
2.3 Flowsheet of 1st Alternative Separation Process of
Dimethyl Carbonate 54
2.4 Flowsheet of 2nd Alternative Separation Process of
Dimethyl Carbonate
2.5 Flow Diagram of Difference Elimination in 45
Temperature, Pressure and Phase Change Operations
for First Alternative
2.6 Flow Diagram of Difference Elimination in 47
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Temperature, Pressure and Phase Change Operations

for Second Alternative 44
2.7 Flow Diagram of Task Integration for First
2.8 Alternative
Flow Diagram of Task Integration for Second
Alternative
6.1 Heat Cascade Diagram
6.2 Grid Diagram of Heat Exchanger
6.3 Heat Integrated PFD of DMC Production Plant
7.1 Capital-Energy-Trade-Off for DC-101
9.1 Horizontal Cylindrical Vessel on Saddle Supports
9.2 Typical Skirt Support Designs
9.3 Bracket Supports
9.4 Mechanical Design Drawing of Distillation Column 1
(DC-100)
10.2 Waste Minimization Techniques
11.1 Process Control Loop of Reactors (SR-1 & SR-2)
11.2 Process Control Loop of Distillation Column 1 (DC-
100)
11.3 Process Control Loop of Distillation Column 2 (DC-
101)
11.4 Process Control Loop of High Pressure Column
(HPC-100)
11.5 Process Control Loop of Low Pressure Column
(LPC-100)
11.6 Process Control Loop of Pressure-Reducing Valve 1
(VLV-100)
(VLV-101)
(VLV-102)
11.9 Process Control Loop of Heater 1 (H-100)
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11.10 Process Control Loop of Heater 2 (H-101)

11.11 Process Control Loop of Pump 1 (P-100)
11.14 Process & Instrumentation Diagram (PID) for DMC
Production Plant
12.1 Plant Layout
12.2 Summary of Procedures of A HAZOP Study
12.3 Fault Tree Analysis for Reactors (SR-1 & SR-2)
12.4 Fault Tree Analysis for Flash Column (LPC-100)
12.5 Fault Tree Analysis for Distillation Column (DC-100,
DC-101 & DC-102)
12.6 Fault Tree Analysis for Pumps (P-100, P-101 & P-
102)
12.7 Fault Tree Analysis for Valves (VLV-100, VLV-101
& VLV-102)
12.8 Fault Tree Analysis for Heaters (H-100 & H-101)
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LIST OF TABLES
TABLE NO. TITLE PAGE

1.1 Annual Production Capacity of DMC in Asia Pacific 13
in 2016
1.2 Top Suppliers of DMC in India 15
1.3 Average Market Price of Dimethyl Carbonate, 2013- 17
2017
1.4 Summarized Description of Considered Site 21
Locations
1.5 Land Prices and Availability of Suggested Locations 22
1.6 Industrial Electricity Tariff (Applicable throughout 25
Malaysia)
1.7 Water Tariff Rates in Pahang 26
1.8 Water Tariff Rates in Johor 26
1.9 Water Tariff Rates in Penang 27
1.10 Logistics of Suggested Locations 28
1.11 Raw Materials Potential Suppliers of Suggested 29
Locations
1.12 Matrix for site selection 31
1.13 Market Prices of Chemicals for Reaction 1 35
2.1 Chemicals Involved in Reactions 43
2.2 Gross Profit for Production of Dimethyl Carbonate 46
(Based on Chemical Prices in Table 2.1)
2.3 Matrix for Process Selection 47
2.4 Boiling and Melting Points of Chemicals at 1 atm 54
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2.5 Comparison between Alternative 1 (Figure 2.3) and 57

Alternative 2 (Figure 2.4)
2.6 Description of Selected Unit Operations 77
3.1 Important Values of Components Involved
3.2 Heat of Formation at 298.15 K and 1 atm
3.3 Standard Heat Capacity at 298.15 K and 1 atm
3.4 Standard Heat of Vaporization
4.1 Percentage Errors of Material Balance for Each
Stream
4.2 Percentage Errors of Energy Balance for Each Stream
5.1 Modification to New Process Design
6.1 Stream Data Table
6.2 Shifted Temperature Data Table (ΔTmin=10oC)
7.1 Extracted Data for Optimization
7.2 Comparison Before and After Optimization for
Distillation Column (DC-101)
8.1 Plug Flow Reactor (SR-1) Equipment Specification
Sheet
8.2 Packed Bed Reactor (SR-2) Equipment Specification
Sheet
8.3 Distillation Column 1 (DC-100) Equipment
Specification Sheet
8.4 Distillation Column 2 (DC-101) Equipment
Specification Sheet
8.5 High Pressure Column (HPC-100) Equipment
Specification Sheet
8.6 Low Pressure Column (LPC-100) Equipment
Specification Sheet
8.7 Compressor (C-100) Equipment Specification Sheet
8.8 Expander (C-101) Equipment Specification Sheet
8.9 Pump 1 (P-100) Equipment Specification Sheet
8.10 Pump (P-101) Equipment Specification Sheet
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8.11 Pump (P-102) Equipment Specification Sheet

8.12 Heat Exchangers Equipment Specification Sheet
8.13 Heaters Equipment Specification Sheet
8.14 Mixer 1 (MIX-100) Equipment Specification Sheet
8.15 Mixer 2 (MIX-101) Equipment Specification Sheet
9.1 Minimum Practical Wall Thickness
9.2 Maximum Allowable Joint Efficiency
9.3 Specification Design Sheet of Distillation Column 1
(DC-100)
10.1 Description of Waste Management Hierarchy
10.2 Description of Waste Minimization and Waste
Treatment
10.3 ‘Criteria’ Pollutants under National Ambient Air
Quality Standards
11.1 Basic Symbols in Piping and Instrumentation
Diagram (P&ID)
11.2 General Functions of Control Elements
11.3 Control Loops for Reactors (SR-1 and SR-2)
11.4 Control Loops for Distillation Column 1 (DC-100)
11.5 Control Loops for Distillation Column 2 (DC-101)
11.6 Control Loops for High Pressure Column (HPC-100)
11.7 Control Loops for Low Pressure Column (LPC-100)
11.8 Control Loops for Pressure-Reducing Valve 1 (VLV-
100)
101)
102)
11.11 Control Loops for Heater 1 (H-100)
11.12 Control Loops for Heater 2 (H-101)
11.13 Control Loops for Pump 1 (P-100)
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12.1 Effect Assessment of Aquatic Organisms

12.2 Environmental Fate of Dimethyl Carbonate
12.3 Toxicity Assessment
12.4 Parameters Associated with Line or Vessels of
12.5 Process
12.6 Guide Words for HAZOP Analysis
12.7 Failure Risk Data of Instruments
Summarized Failure Risk Analysis of Studied
Equipment
CHAPTER 1
LITERATURE REVIEW & PROJECT CONCEPTION
1.1 Chemical Product Background
Dimethyl carbonate (DMC) is an organic compound with the formula

OC(OCH3)2. At room temperature, it is a colorless and transparent liquid with a pungent
odor with a relative density (D204) of 1.0694, a melting point of 4°C, boiling point of
90.3°C, the flash point being 21.7°C (opening) and being 16.7°C (closed ) and the
refractive index being 1.3687. It is also flammable and non-toxic and is miscible with
almost all organic solvents in any proportion with alcohols, ketones and esters. It is
slightly soluble in water and classified as a carbonate ester that is similar to a carbonic
acid in which both hydrogen are replaced by methyl groups. Different names have been
closely related to DMC which include methyl carbonate, carbonic acid and dimethyl
ester.
Dimethyl carbonate was originally made by the reaction of two moles of

methanol with one mole of phosgene. However, due to phosgene’s extreme toxicity, it is
now manufactured by the transesterification of propylene carbonate and methanol or the
copper-catalyzed reaction of methanol, oxygen and carbon monoxide. In recent years,
various methods of production has been discovered and applied in the industrial scale
such as the transesterification of ethylene carbonate with methanol, urea methanolysis,
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oxidative carbonylation of methanol or even direct synthesis from carbon dioxide and
methanol. Some has been very well incorporated and commercialized into major
companies venturing into this field of production especially in Asia Pacific namely
China and Japan.
Dimethyl carbonate is increasingly used as a methylating agent in place of

hazardous, waste-generating compounds such as dimethyl sulfate and methyl halides.
This compound has also found use recently as a solvent that is exempted from the
restrictions placed on most volatile organic compounds (VOCs) in the United States of
America. Other than that, dimethyl carbonate is often considered to be a green reagent.
Dimethyl carbonate (DMC) is an environmentally benign substitute for dimethyl
sulphate and methyl halides since it is a well-known non-toxic reagent as compared to
other carboxylating or alkylating agents (phosgene and methyl halides, respectively).
Besides, DMC does not produce inorganic salts. In fact, the leaving group, methyl
carbonate, decomposes giving as by products only methanol and CO2.
1.1.1 Physical and Chemical Properties of Dimethyl Carbonate
The physical and chemical properties of dimethyl carbonate and relevant raw
materials required in its production are shown in Appendix C.
1.1.2 Applications of Dimethyl Carbonate
1.1.2.1 Organic solvent
Dimethyl carbonate (DMC) is a relatively new chemical on the market. Although

it has been known for longer times, only until recently the use was limited to several
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major usages. DMC is mainly used as an organic solvent in synthesis of other

compounds and as a monomer of polycarbonates in which 51% of the world production
is used for this purpose (Coker, A., 2012). However, only till a few years ago the
potential usages were not seen. DMC could be used as a basis for organic paints due to
its low boiling point (90˚C) and ability to dissolve a wide range of compounds. DMC
represents a viable alternative to acetate esters and ketones in most applications, from
paints to adhesives, taking advantage of its good solvency power. It should also be
reminded that DMC is the file leader of many derived carbonic esters, available by
transesterification reactions, whose properties can be tailored according to the target
applications, like in the field of lubricating oils. DMC, as a non-aqueous electrolyte
component, is finding increasing application in the field of lithium rechargeable batteries
too as an electrolyte.
1.1.2.2 Traditional substitute of toxic materials
Dialkyl carbonates can be handled safely without the special precautions due to
their moderate toxicity in comparison with the conventional carbonylating (i.e.
phosgene) and alkylating agents (i.e. alkyl halides and dimethyl sulphate) which are
some of the toxic materials. Besides, the formation of inorganic salts as byproducts and
the related disposal problems are avoided. The third advantage of dialkyl carbonates is
their appreciable selectivity following the hard–soft acid–base (HSAB) principle. With
changes in reaction temperature, the nucleophilic substitution on DMC follows two
different mechanisms therefore, low temperatures allow carboxymethylation reaction,
whereas high temperatures give methylation derivatives. It can also be used for synthesis
of diphenyl carbonate, isocyanate and allyl diglycol carbonate ester as well as for the
synthesis of various kinds of carbamate pesticides such as carbaryl. It can also be
utilised as an intermediate of organic synthesis such as anisole, dimethoxybenzene,
alkylated aryl amines, symmetrical diamine urea and methyl carbazate. In the
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pharmaceutical industry, it can be used for making amino oxazolidinone, ciprofloxacin,

β- keto acid ester class pharmaceutical intermediates.
1.1.2.3 Paints, inks and coatings
Dimethyl carbonate (DMC) finds use as a solvent in paints, inks and coatings.
This is because DMC has an ultra-low MIR value, which is a chemical's ability to form
atmospheric ozone. The lower the MIR value, the less ozone generated and safer it is.
Dimethyl Carbonate is also a medium evaporating polar solvent with a low toxicity and
methanol like odor. Besides the environmental friendly characteristics, it offers a low
vapor pressure, suitable liquid temperature range and unique solubility property essential
for paints, inks and coatings. DMC is a viable alternative to acetate esters and ketones in
most applications, from paints to adhesives, taking advantage of its good solvency
power. DMC also acts as an intermediate in the synthesis of polymers, pesticides,
antioxidants and high performance resins.
1.1.2.4 Polycarbonate production
The potential demand for DMC could be much higher. Its main use as an
intermediate in polycarbonate production currently accounts for just over half of its
consumption. Polycarbonate is a type of plastics known for their optical transparency,
impact resistance, and high dielectric strength. For example, polycarbonates are found
in DVD and Blu-ray discs, safety goggles, eyeglass lenses, bullet-resistant windows,
electrical insulators, aircraft and missile components. This abundance and variety of
applications generates substantial demand for DMC and makes production a viable
investment.
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1.1.2.5 Pharmaceutical and intermediate chemical
In the pharmaceutical sector, DMC is mainly used as methylating agent in the

synthesis of anti-infective drugs, analgesic – anti pyretic drugs, vitamins and central
nervous system drugs. DMC is also used as a methylating reagent in the production of
variety of substrates including thiols, thiophenols, aromatic amines, arylacetonitriles,
arylacetoesters, aroxyacetonitriles, aroxyacetoesters, alkylarylsulfones,
benzylarylsulfones, and lactones. DMC has good reactivity and low toxicity. It is an
important environmental friendly intermediate for organic synthesis. DMC is good
solvent with comparatively less toxicity. It can replace halogenated solvents such as
chlorobenzene. Methylation with DMC is very selective. The mono methylation of
phenylacetonitrile, O-methylation of phenol and N-methylation of aniline are such
examples.
1.1.2.6 Fuel additives
There is future potential demand as a possible fuel additive. DMCs possible use
as a gasoline blending component has been under consideration for some years, due to
its very high oxygen content (53 weight percent), good blending octane and freedom
from phase separation, low toxicity and rapid biodegradability. The high oxygen content
of DMC makes it a candidate to replace MTBE as an oxygenated fuel additive. Usually
10% of MTBE (methyl tertbutyl ether) is added while only 3.3% DMC is needed. The
oxygen content of a DMC molecule is 53% whereas the oxygen content of MTBE
molecule is 17%. Automotive emission tests at Amoco showed that at the same weight
percent oxygen in the fuel, DMC reduced total hydrocarbon, carbon monoxide and
formaldehyde more than did MTBE. The use of dimethyl carbonate as a gasoline
blending component in major regions such as North America and China is uncertain. In
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the United States, while MTBE is largely phased out, ethanol remains the major gasoline
blending agent. In China, MTBE still appears to be the gasoline addictive of choice.
1.1.3 Safety Measures and Toxicity
Dimethyl carbonate can be hazardous in case of skin contact (irritant), of eye

contact (irritant) but slightly hazardous in case of skin contact (permeator), of ingestion
and of inhalation. Inhalation of high vapor concentrations of dimethyl carbonate instead
may cause symptoms like headache, dizziness, tiredness, nausea and vomiting. This also
result in acute potential health effects such skin irritation since it can be absorbed
through the skin as well as eye irritation. When inhaled or ingested, it may cause
respiratory tract irritation that can lead to central nervous system depression or breathing
difficulties and irritation of the digestive tract respectively. Repeated or prolonged
exposure to the dimethyl carbonate can produce target organs damage. However, the
toxicological properties of dimethyl carbonate have not been fully investigated.
Dimethyl carbonate is also flammable and when heated, explosion of containers

holding it may explode. Vapors released may even form explosive mixtures with air and
travel to sources of ignition and flash back. On the other hand, decomposition by heating
might lead to the emission of acrid smoke and irritating fumes. It can be incompatible
with certain materials namely oxidizing agents, strong acids and strong bases. Violent
reaction or ignition is expected upon contact with potassium tert-butoxide.
1.1.4 Storage and Handling
The conditions for safe storage of dimethyl carbonate include any

incompatibilities and keeping the container tightly closed in a dry and well-ventilated
place. Any containers which are opened must be carefully resealed and kept upright to
prevent leakage. Dimethyl carbonate reacts with acids to liberate heat along with
methanol and carbon dioxide. Strong oxidizing acids may cause a vigorous reaction that
7
is sufficiently exothermic to ignite the reaction products. Heat is also generated by the
interaction with caustic solutions. Flammable hydrogen is generated by mixing with
alkali metals and hydrides.
Dimethyl carbonate should be kept away from ignition sources by incorporating
explosion-proof equipment. Ignition sources include heat, sparks, open flames or even
hot surfaces whereas explosion-proof equipment can involve electrical, ventilating and
lighting equipment. Besides, measures should be taken as well for prevention in the
build-up of electrostatic charges. This can be done by using only non-sparking tools and
ground or bond containers and receiving equipment.
Inhalation of vapor or mist of dimethyl carbonate can be avoided by personal

protective equipment. The eye or face protection includes face shield and safety glasses
that are tested and approved under appropriate government standards. Gloves can
provide protection to the skin and should use proper glove removal technique to avoid
skin contact with dimethyl carbonate. Impervious clothing or flame retardant antistatic
protective clothing are required as well according to the concentration and amount of the
dangerous substance at the specific workplace. As risk assessment shows air-purifying
respirators are appropriate and needed, a full-face respirator with multipurpose
combination (US) or type ABEK (EN 14387) respirator cartridges can be used as a
backup to engineering controls. If the respirator is the sole means of protection, use a
full-face supplied air respirator.
1.2 Market Survey
1.2.1 Market Demand of Dimethyl Carbonate
The two key drivers of dimethyl carbonate production are two of its largest
applications in the industries of polycarbonates and paints and coatings. The
polycarbonate is the tough material having few grades that are optically transparent. This
8
material is widely used in the engineering and various applications. It offers properties
such as extrusion and injection molding technique to develop products with various
shapes and size, excellent heat and UV resistance, and thermo-formation.
Polycarbonates are currently in very high demand from the rapidly growing end-user
industries of automotive and electronics. Both industries are currently in full swing and
are expected to continue growing in the near future. As a result, the higher demand for
polycarbonates becomes a driver for the manufacture of dimethyl carbonate. Similarly,
the paints and coatings industry is being boosted by the construction industry,
consequently upping the demand for dimethyl carbonate. Increasing demand from food
and beverage packaging and the medical packaging application is also expected to boost
the growth of the polycarbonate market during the years to come. The welcoming
demand of polycarbonate will be good news to the production of dimethyl carbonate
over the years.
The demand of dimethyl carbonate goes hand in hand with the success of
polycarbonate industry. According to reports on “Polycarbonate Market for Electronics,
Packaging, Construction, Automotive, Optical Media and Other Applications: Global
Industry Perspective, Comprehensive Analysis and Forecast, 2014 – 2020”, the global
demand for polycarbonate was valued at USD 13.50 billion in 2014, and is expected to
reach USD 18.50 billion in 2020, growing at a CAGR of 5.8% between 2015 and 2020.
The needs of dimethyl carbonate as the starting material towards polycarbonate
production is proven crucially important in many years to come.
The rising polycarbonate industry in electronics sector can be another great

platform for dimethyl carbonate to enhance production capacity in the future.
Polycarbonate helps to reduce the weight of vehicle which increases the fuel efficiency
and reduces impact on environment. In 2014, the electronics was the dominant
application segment in terms of total revenue generated and it accounted around 25%
shares of the market. Heavy consumption of polycarbonate in the automotive industry is
expected to be a major factor driving the market growth worldwide.
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The potential application of dimethyl carbonate as a gasoline additive in the

energy sector, on the other hand, will provide growth opportunities by 2024. By 2023,
53.2% of the total volume of dimethyl carbonate produced is expected to be taken up by
the polycarbonate industry. Dimethyl carbonate is an important constituent in the
manufacture of polycarbonates, as it is used to produce diphenyl carbonate, one of the
core chemicals in the condensation polymerization process that produces
polycarbonates. The applications of polycarbonates are diverse and include appliances,
lighting devices, medical devices, optical media, electronics, and automobiles. Most of
these industries, especially the automotive and electronics industries, are showing a
positive growth rate. Therefore, their demand for polycarbonates is expected to drive the
production of dimethyl carbonate.
Depending on the application, different grades of dimethyl carbonate are

required. The dimethyl carbonate weight percent ranges from industrial grade (>99.0
weight percent) to pharmaceutical grade (>99.5 weight percent) to battery grade (>99.9
weight percent). The figure below estimates the global consumption of dimethyl
carbonate according to end-use. Solvent use includes the use of dimethyl carbonate as an
elctrolyte in lithium ion batteries.
Figure 1.1: Global Consumption of Dimethyl Carbonate According to End-Use

(Source: CHEMSYSTEMS PERP PROGRAM Dimethyl Carbonate 2012S12 Report)
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1.2.2 Global Outlook
Dimethyl carbonate market size was valued over USD 410 million in 2015 and is
forecast to experience gains exceeding 5% CAGR by 2024. By the end of 2016, this
market revenue should be reaching US$440 million. The global market for dimethyl
carbonate is expected to progress at a CAGR of 6.6% between 2015 and 2023 in terms
of revenue. By the end of 2023, the market is expected to be valued at US$690.1
million. In terms of volume, dimethyl carbonate global production is expected to weigh
in at 599 kilo tons.
The global polycarbonate industry was valued at over USD 14 billion in 2015
and is projected to reach USD 22 billion by 2024, at over 5% CAGR. The industry will
expand at a rapid pace, particularly in Asia Pacific due to robust growth in the regional
automotive and electronics sectors. Emerging economies in Asia Pacific are expected to
be major markets for electronics due to modernization, such as increasing smartphone
customer base, along with increasing consumer disposable income. This is expected to
boost electrical components demand. This will consequently boost industry growth.
11
Figure 1.2: Global Dimethyl Carbonate Market Value (USD Billion)

(Source: Global Dimethyl Carbonate (DMC) Market Research Report 2016)
Additionally, global automotive production, including personal and commercial
vehicles, was roughly around 90 million units in 2015. Polycarbonate exhibits superior
light transmission, creep modulus, dimensional stability, heat resistance and electrical
insulation, which makes the product desirable to find application in automotive parts.
Escalating paint and coatings industry is another factor propelling the dimethyl
carbonate market size over the forecast timeframe, and was valued at over USD 110
billion in 2015, estimated to reach USD 165 billion by 2024.
In Europe, dimethyl carbonate was recognized as a non-toxic chemical in 1992,

after which it steadily started to replace chloromethane, phosgene, and methyl
chloroformate in several end-use industries. A majority of the demand for dimethyl
carbonate in Europe is expected to continue originating from Germany and France.
The key players involved with the production of dimethyl carbonate include
Dongying City Longxing Chemical Co., Ltd., Shandong Shida Shenghua Chemical
Group Co., Ltd., Alfa Aesar, EMD Millipore Corporation, HaiKe Chemical Group,
Akzo Nobel N.V., UBE Industries Limited, Tangshan Chaoyang Chemical Co., Ltd.,
and BASF SE.
12
Figure 1.3: U.S Dimethyl Carbonate Market Size by Application from 2013-2024 (USD
Million)
Source: Dimethyl Carbonate Market Size by Application Industry Analysis Report,
Regional Outlook, Growth Potential, Price Trends, Competitive Market Share &
Forecast, 2016 – 2024
1.2.3 Asia Pacific Outlook
Dimethyl carbonate includes ester exchange synthesis method and oxidative

carbonylation process on the base of technology, which represent 67% and 25% of
global dimethyl carbonate market. Polycarbonate and medicine are the main application
of dimethyl carbonate product and Asia is the largest dimethyl carbonate market on
production and consumption. Global dimethyl carbonate market is projected to reach $
1.99 billion by 2018 with a GAGR of 16.4% from 2014 and Asia will have a big
dynamic momentum on the market growth.
Table 1.1: Annual Production Capacity of DMC in Asia Pacific in 2016

COMPANY COUNTRY CAPACITY (MTA)
Ube Industries Japan 100,000
Tongling Jintai Chemical China 100,000
Industrial Co. Ltd.
Chaoyang Chemical Group China 85,000
Enichem Synthesis Italy 50,000
13
Qingdao Jumpover China 50,000

Trading Co., Ltd.
Dongying Hi-tech Spring China 45,000
Chemical Industry Co. Ltd.
Jiangsu GranPure Trading China 45,000
Co., Ltd.
Shandong Wells Chemical China 30,000
Industry Co. Ltd.
Kowa Company, Ltd. Japan 20,000
Shandong Depu Chemical China 10,000
Industry Science and
Technology Co. Ltd.
By the end of 2023, the Asia Pacific demand for dimethyl carbonate is expected
to be at 49.26% of the market. Europe comes in at second place in terms of demand
followed by North America in third. Asia Pacific, particularly led by China, India,
Indonesia, dominated the global dimethyl carbonate market size in 2015. In addition, the
region is forecast to experience highest gains mainly owing to robust growth in the
electronics, automotive and paints & coatings on account of increasing consumer
disposable income. Furthermore, upgrading customer preferences towards colorful and
high quality paints will complement industry growth by 2024.
China is a massive contributor to the Asia Pacific demand for dimethyl

carbonate. Together with Japan, the two regions are expected to take up more than three
quarters of the total dimethyl carbonate volume in Asia Pacific by 2023. In fact, China is
considered to be a top producer and consumer of dimethyl carbonate in the world
currently, as the players in this country also export large quantities of dimethyl
carbonate to emerging economies. As shown in Figure 1.4 below, Asia Pacific is
14
expected to dominate the global dimethyl carbonate market by almost 50% of the total
supply with a compounded annual growth rate of 6.6%.
Figure 1.4: Global Dimethyl Carbonate Market by Region 2015-2023

(Source: Transparency Market Research Analysis, 2016)
The total value and volume of imports in India, based on the source from Zauba
Technologies and Data Services Pvt Ltd, are USD 19,407,021 and 13,467.508 MTA
respectively in 2016 which shows the great demand in India in years to come. The top
suppliers of dimethyl carbonate in India as shown in Table and Figure proves that the
DMC market demand in Asia Pacific is dominated mainly by China and Japan.
Table 1.2: Top Suppliers of DMC in India (Zauba Technologies and Data Services,
2016)
TOP SUPPLIERS (COUNTRY) TOTAL VALUE OF IMPORT (USD)
China 18,621,017
Japan 783,712
15
United Kingdom 1,717
Figure 1.5: Total Value of Imports by Countries in India

(Source: Zauba Technologies and Data Services, 2016)
1.2.4 Malaysia Outlook
The dimethyl carbonate industry prospects in Malaysia progresses at a relatively

slow rate as there is hardly substantial data discovered that may indicate the
development of this industry on local grounds. This could possibly due to the lack of
necessary technologies or research available towards the production capabilities of
dimethyl carbonate. However, based on the wide applications of dimethyl carbonate,
there is promising potential for its development in Malaysia as this industry can be
channeled towards the needs of existing industries locally such as the polycarbonate
industry.
16
Figure 1.6: Malaysia Plastic Compounding Market by Product, 2014-2025 (USD

Million)
Source: Malaysia Plastic Compounding Market Analysis By Product, By End-Use, and
Segment Forecasts, 2014 – 2025
Polycarbonates are one of the most commonly developed plastics in Malaysia.

The plastic compounding market size in Malaysia was valued at USD 580.1 million in
2015 and is anticipated to grow at a CAGR of 6.6% over the forecast period. Growing
acceptance of lightweight, energy-efficient vehicles to combat depleting fossil fuel
resources has led to high industry growth in recent years. Malaysia is also one of the
largest exporters of plastic products, among the ASEAN countries, with major exports
destination being Europe, China Singapore, Japan and Thailand. The exports of these
end-user products of plastics is increasing, which is further increasing the demand for
plastics in the country.
At present, dimethyl carbonate may not significantly produced at local grounds

but its global and Asia market demand has improved over the years and it has the
potential to be an ever-growing industry in the future. Therefore, the construction of a
dimethyl carbonate plant will bring benefits to the manufacturing industry in Malaysia
17
since the economic potential of our country can be increased following the exports of
dimethyl carbonate based on their growing future demand. It will be a great investment
in the long run if this dimethyl carbonate manufacturing plant is made successful.
1.2.5 Market Price of Dimethyl Carbonate
The average market prices of dimethyl carbonate in 2017 and the previous four
years are tabulated in Table 1.1 below in which they are sourced from available
information in ICIS Chemical Business and Platts Global Petrochemical Index and
Zauba Technologies and Data Services.
Table 1.3: Average Market Price of Dimethyl Carbonate, 2013-2017

Average Market Price
Year
(US Dollar / Metric ton)
2013 1150
2014 2145
2015 989
2016 1230
2017 1250
1.2.6 Availability of Raw Materials
1.2.6.1 Future Prospects of Methanol Industry
The methanol industry in Malaysia accounts for only around three percent of the
overall production in the Asia-Pacific region. Its demand is expected to increase in the
18
coming years quite significantly due to a healthy demand from the formaldehyde-based
resin and automobile fuel sector. The growth in demand for methanol in Malaysia is
expected to be at the rate of five percent during the forecast period, and the majority of
domestic demand would be fulfilled by imports. This correlates well with the global
demand and supply as shown in Figure 1.5 that is expected to experience steady growth
in years to come as the average increase in total capacity of plants worldwide is fuelled
by the higher operating rate required.
Figure 1.7: Global Methanol Supply and Demand (Source: IHS 2013)
Malaysia’s methanol demand was mainly driven by the formaldehyde sector.

MTBE and acetic acid were the two other major methanol end-use markets. Methanol is
a basic building block in a large number of chemically complex materials such as
plastics. It can be recovered from these materials by chemically destructive processes
which decompose complex inorganic molecules into their simple components. However,
as shown in Figure 1.6, various industrial applications can be created and practiced
currently in which their demand have a positive outlook in the future when industrial
capacity is expected to increase.
19
Figure 1.8: Global Methanol Demand Based on Applications (Source: IHS 2013)
When methanol is used to process bio-waste material into biodiesel, it produces a

hydrocarbon fuel with properties similar to diesel fuel. Conversion can be accomplished
on scales that range from 30-gallon capacity trash-can-sized batches, to continuous
processes operated intermittently, to continuously operated plants with capacities
ranging from 4 million to 100 million gallons per year. Typically, people using methanol
to produce biodiesel in small-scale batch applications are not trained chemists. Operators
are likely unaware of the hazards and regulatory compliance necessary to manufacture
fuel safely and legally. These individuals may not be trained or experienced in handling
concentrated hazardous chemicals such as lye (sodium/potassium hydroxide, Na/KOH)
and methanol. Operators of intermittently operated continuous processes will likely be
familiar with precautions and laws that accompany production of biodiesel, but they may
or may not have the proper equipment and procedures and training necessary for self-
protection and efficient chemical handling.
20
The methanol market in Malaysia is highly consolidated, with only one player,
PETRONAS. The company accounted for 100% of the installed capacity in the region
during 2011. The domestic demand was fulfilled by in-house production and the
majority of in-house production was exported to Japan and China.
1.3 Site Selection
1.3.1 Suggested Locations
The location of a new plant is crucial towards the sustainability and production
capacity of the manufacture of a particular chemical product or any industrial-grade
materials. Judging on a long-term basis, a chemical plant has to be strategically and
safely located to prevent untoward incidents to the public and environment as well as to
accommodate the competitive and economical perspective of market opportunities.
These major concerns are guided by various factors that are to be taken into
consideration which include the tax incentives, land price and availability, utility tariff,
logistics, labour, availability of raw materials and market supply.
For the construction of our new dimethyl carbonate manufacturing plant, three
major industrial locations have been considered that is mainly focused in Peninsular
Malaysia due to better market prospects and industrial development. The locations
include as the following:
a) Tanjung Langsat Industrial Estate, Pasir Gudang, Johor

b) Gebeng Industrial Area (Phase IV), Pahang
c) Batu Kawan, Free Industrial Zone, Penang
21
Table 1.4: Summarized Description of Considered Site Locations

Batu Kawan, Free
Locations / Tanjung Langsat Gebeng (Phase IV)
Industrial Zone,
Characteristics (Johor) (Pahang)
Penang
Distance from 42 km from Johor 40 km from Kuantan 44 km from
nearest town Bahru and 45 km Georgetown
from Singapore
Power supply Tenaga Nasional Tenaga Nasional Tenaga Nasional
Berhad Berhad Berhad
Water supply Syarikat Air Johor Semambu Water Perbadanan Bekalan
(SAJ) Sungai Treatment Plant Air Pulau Pinang
Layang (PBAPP)
Type of Heavy and medium Heavy industry and Heavy and medium
industry industry petrochemical industry
1.3.2 Factors of Selection and Comparisons between Locations
1.3.2.1 Land price and availability
The suitable and conducive land for the construction of a sustainable and
functional dimethyl carbonate manufacturing plant should be widely available at
selected locations. This also refers to the hectares of land or area accessible to our
plant’s needs. Our 15,000 MTA-production capacity chemical plant will require
approximately 10 acres of land that will also provide space for auxiliary and additional
buildings and facilities such as warehouse, cafeteria, cooling water and others. The land
price is defined in terms of RM per square feet and it should be sufficiently low to
reduce expenses.
22
Table 1.5: Land Prices and Availability of Suggested Locations

Batu Kawan, Free
Industrial Zone,
Penang
Area available 597.14 1528.50 782.43
(hectares)
Average land 34.00 – 45.00 15.00 – 30.00 38.00-80.00
price (RM/ft2)
Developer  Perbadanan Perbadanan Penang
Tempatan Pasir Kemajuan Negeri Development
Gudang (PBTPG) Pahang (PKNP) Corporation
 Johor
Corporation
(JCORP)
1.3.2.2 Tax incentives
i) Gebeng, Pahang
The major tax incentives for companies that invest in the manufacturing sector
are the Pioneer Status or Investment Tax Allowance. Eligibility for Pioneer Status or
Investment Tax Allowance is based on certain priorities, including the levels of value-
added, technology used and industrial linkages.
 A company granted Pioneer Status gain a benefit of a partial exemption from

payment of income tax. It pays tax on 30% of its statutory income *, with the
23
exemption period commencing from its Production Day (defined as the day its
production level reaches 30% of capacity).
 A company granted Investment Tax Allowance (ITA) gets an allowance of 60%
on qualifying capital expenditure (factory, plant, machinery and other equipment
used for the approved project) incurred within five years from the date the first
qualifying capital expenditure is made.
 Companies can offset this allowance against 70% of statutory income for each
year of assessment. Any unutilized allowances can be carried forward to
subsequent years until fully utilized. The remaining 30% of the statutory income
will be taxed at the prevailing company tax.
 Pioneer Status with income tax exemption of 100% of statutory income for a
period of 5 years; or Investment Tax Allowance of 100% on the qualifying
capital expenditure incurred within a period of 5 years. The allowance can be
offset against 100% of statutory income for each year of assessment.
 Stamp duty exemption for all clusters promoted by East Coast Economic Region
Development Council (ECERDC) on transfer or lease of land or building.
 Withholding Tax Exemption (WTE) on royalty and technical fees
ii) Tanjung Langsat, Johor
Incentives provided by the government include the Promotions of Investment

Act 1986, Income Tax Act 1967, Customs Act 1967, Sales Act 1972 and Excise Act
1976. As for industrial area in Johor state which is designated from TPM Technopark
Sdn. Bhd., the incentives includes:
Pioneer status (PS) with income tax exemption of 100% of statutory income for a
period of 10 years. Unabsorbed capital allowances and accumulated losses incurred
during the pioneer period can be carried forward and deducted from the post pioneer
income of the company Businesses are entitled to 10 years exemption from corporate
24
tax. Investment Tax allowance (ITA) of 100% of qualifying capital expenditure incurred
within a period of 5 years. The allowance can be used to offset against 100% of statutory
income in each year of assessment. Unutilized allowances can be carried forward until
fully absorbed.
Tariff related incentives such as full exemption from import duty on raw materials and
components; exemption of import duty and sales tax on machinery and equipment;
drawback of excise duty, sales tax and import duty paid. Dividends paid from the
exempt income are exempted from tax in the hands of its shareholder. Incentives for
export, R&D and manpower training
iii) Batu Kawan, Penang
Incentives provided for the Free Industrial Zone in Penang include:
Pioneer Status referring to income tax exemption of 70% or 100% on the statutory
income for five years. Investment Tax referring to investment tax allowance of 60% or
100% on the qualifying capital expenditure for five years. The allowance can be utilized
to offset against statutory income. Reinvestment Allowance referring to reinvestment
allowance of 50% for 15 years on the qualifying capital expenditure. The allowance can
be offset against 70% or 100% of the statutory income. Accelerated Capital Allowance
referring to an accelerated capital allowance consisting of an initial allowance of 40%
and an annual allowance of 20% is available for the three years after the reinvestment
allowance period
1.3.2.3 Electricity tariff
Table 1.6: Industrial Electricity Tariff (Applicable throughout Malaysia)

25
Tariff Category Unit Rates (1st

January 2017)
Tariff Ds – Low Voltage Industrial Tariff
For all kWh sen/kWh 43.60
The Minimum Monthly Charge is RM 7.20
Tariff E1 – Medium Voltage General
Industrial Tariff RM/kW 28.50
For each kilowatt of maximum demand per month sen/kWh 33.70
For all kWh RM 600.00
The Minimum Monthly Charge is
Tariff E2 – Medium Voltage Pea/Off-Peak
Industrial Tariff
For each kilowatt of maximum demand per month
during the peak period RM/kW 34.30
For all kWh during the peak period sen/kWh 35.00
For all kWh during the off-peak period sen/kWh 19.90
Tariff E3 – High Voltage Peak/Off-Peak
Industrial Tariff
For each kilowatt of maximum demand per month RM/kW 30.20
during the peak period
For all kWh during the peak period sen/kWh 32.90
For all kWh during the off-peak period sen/kWh 18.30
1.3.2.4 Water tariff
i) Gebeng, Pahang
26
Table 1.7: Water Tariff Rates in Pahang

Type of Charge Rates
(Non-Domestic Supplies)
INDUSTRIAL
Consumption:
Band 1 0 – 227 m3 @ RM0.92/m3
Band 2 >227 m3 @ RM0.84/m3
Minimum charge RM30.00 (Use in the Approved Industrial
Zones)
ii) Tanjung Langsat, Johor
Table 1.8: Water Tariff Rates in Johor

INDUSTRIAL/COMMERCIAL/
TRADING Non-Domestic
Industrial/Commercial
Consumption: 0 – 35 m3 @ RM2.80/m3
Band 1 >35 m3 @ RM3.30/m3
Band 2 RM30.00
Minimum charge
iii) Batu Kawan, Penang
Table 1.9: Water Tariff Rates in Penang

27
INDUSTRIAL
Consumption:
Band 1 0 - 20 m3 @ RM 0.85/m3
Band 2 20 - 40 m3 @ RM 1.05/m3
Band 3 40 - 200 m3 @ RM 1.30/m3
Band 4 >200 m3 @ RM 1.45/m3
Minimum charge RM30.00 (Use in the Approved Industrial
Zones)
1.3.2.5 Logistics
Meeting customer demand and providing superior service is one of the most
important benefits of good logistics management. Logistics management is also
important for creating visibility into a company’s supply chain. Proper logistics
management drives increased revenue. Improved customer service can bring a good
reputation to a company’s brand and generate more business, and supply chain visibility
creates opportunity for major cost savings in operations. Logistics management will give
a company control over inbound freight, keep inventory at optimal levels, organize the
reverse flow of goods, and utilize freight moves on the proper transportation modes
where all of which can cut costs significantly.
Table 1.10: Logistics of Suggested Locations

Batu Kawan, Free
Industrial Zone,
Penang
Port facilities Pasir Gudang Port Kuantan Port (25 km Penang Port (5 km
(48 km from city) from city) from city)
Land Main road to Main road to Kuala Bayan Lepas is
transportation Singapore and North- Lumpur, Johor Bahru conveniently
28
South Highway and Singapore connected to

(PLUS) mainland
Peninsular
Malaysia via the
Second Penang
Bridge, which
links Batu Maung
on Penang Island
with Batu Kawan
in Seberang Perai
Distances 450 m from Dry 5 km from Kuantan 6 km to Penang
Cargo Jetty that port International
import and export 33 km from Sultan Airport
goods Ahmad Shah Airport 7 km to the nearest
60 km from Senai Approximately 8.2 highway
International Airport km to the nearest 24 km to Penang
20 km from the highway Port
nearest North-South
Highway interchange
1.3.2.6 Labour
Labour includes both physical and mental work undertaken for some monetary
reward. In this way, workers working in factories are included in labour. Land and
capital are considered as the passive factors of production, because they alone cannot
start the production process. Production from land and capital starts only when a man
makes efforts. Production begins with the active participation of man. Therefore, labour
is an active factor of production. Production can be started only with the help of labour.
It means labour is the beginning of production.
29
In all three suggested locations, local labour of adequate skills can be scouted
and trained to operate the plant. Available labour can be found from polytechnics,
universities and human resources and technical skills developer around the local states.
1.3.2.7 Raw materials
Raw materials can be explained as substance or material used in the

manufacturing or primary production of goods and are often altered for use in various
processes prior to being used in the manufacturing process. It is important to have a
plant at an area where the availability of raw materials is wide and easily accessible.
Besides, the production capacity of the raw materials available should be significantly
sufficient to accommodate the dimethyl carbonate production itself. This also includes
the selling price of the raw materials as well based on different manufacturers or
suppliers.
Table 1.11: Raw Materials Potential Suppliers of Suggested Locations

Batu Kawan, Free
Industrial Zone,
Penang
Raw material 1) KLH Chemicals 1) BASF 1) City-Chemical
supplier Sdn Bhd PETRONAS Industry Berhad
Cap: 5 kMTA Chemicals Sdn Cap: 8 kMTA
2) Netforce Chemical Bhd
Sdn Bhd Cap: 20 kMTA
Cap: 3 kMTA
1.3.2.8 Market supply
It is best that the dimethyl carbonate plant is strategically located at an industrial

area with positive marketing prospects and widely accessible to industrial demands.
30
Foreign markets will be an additional incentive to the market supply of dimethyl

carbonate especially in South East Asia. The suggested locations have commendable
access to foreign and local market distribution, however, Tanjung Langsat, Johor and
Batu Kawan, Penang have more well-renowned accessibility and foundation to extensive
market distribution that is still comparable to that of Gebeng, Pahang.
31
1.3.3 Matrix for Site Selection
Table 1.12: Matrix for site selection

Site 1 Site 2 Site 3
Criteria Weightage
Tanjung Langsat, Johor Gebeng, Pahang Batu Kawan, Penang
Availability of 597.14 hectares 1528.50 hectares 782.43 hectares

0.25
land 1 3 2
RM 34.00 – 45.00 / ft2 RM 15.00 – 30.00 / ft2 RM 38.00-80.00 / ft2
Land price 0.20
2 3 1
450 m from Dry Cargo
Jetty that import and export 5 km from Kuantan port 24 km to Penang Port
Marketing area 0.20
goods
3 2 1
1) KLH Chemicals 1) BASF PETRONAS 1) City-Chemical
Sdn Bhd Chemicals Sdn Bhd Industry Berhad
Cap: 5 kMTA Cap: 20 kMTA Cap: 8 kMTA
Raw material
0.15 2) Netforce Chemical
supply
Sdn Bhd
Cap: 3 kMTA
1 3 2
Logistics 0.10 450 m from Dry Cargo 5 km from Kuantan port 6 km to Penang
32
Jetty that import and export 33 km from Sultan Ahmad International Airport
goods Shah Airport 7 km to the nearest
60 km from Senai Approximately 8.2 km to the highway
International Airport nearest highway 24 km to Penang Port
20 km from the nearest
North-South Highway
interchange
1 2 3
Water tariff :
Water tariff : Water tariff :
0 - 20 m3 @ RM 0.85/m3
0 – 35 m3 @ RM2.80/m3 0 – 227 m3 @ RM0.92/m3
20 - 40 m3 @ RM 1.05/m3
Utility tariff 0.10 >35 m @ RM3.30/m
3 3
>227 m @ RM0.84/m
3 3
40 - 200 m3 @ RM 1.30/m3
>200 m3 @ RM 1.45/m3
1 3 2
Total 1.00 1.60 2.70 1.70
Remark: Rating from 1-3, 1 is the worst while 3 is the best.
33
Based on overall score obtained from the matrix, it is best to choose Gebeng,
Pahang as our Plant Site. Gebeng industrial land focusing on industry that based on
petrochemical and chemical. The industrial land is located nearby Gebeng bypass which
eases traffic flow from the industrial land to Kuantan Port, links Kuala Lumpur and
Kuantan directly via East Coast Highway. A few criteria that we considered while
making judgment for site selection. We put availability of suitable land as the most
importance criteria, followed by land price and marketing area, then raw material
supply, and lastly, the logistics and utility tariff. Gebeng has been selected as our plant
location due to the lowest land price ranging from RM 15.00 – 30.00 / ft 2 compare to
Tanjung Langsat and Batu Kawan. The future expansion and project enlargement made
possible with enough land for the project continuation. Furthermore, the abundant of raw
material in the same city will also reduce the cost of transportation of the raw material as
well as the availability of good transportation and port facilities. As a conclusion,
building a dimethyl carbonate-producing plant in Gebeng will definitely give us huge
advantages.
1.4 Process Selection
This section will describe three types of commercial processes of dimethyl

carbonate production that had been utilized in current manufacturing industry.
Subsection 1.4.1 until 1.4.3 shows the top three process route for the production of
dimethyl carbonate.
1.4.1 Direct synthesis from carbon dioxide and methanol
The direct synthesis of dimethyl carbonate by reaction between carbon dioxide

and methanol. Differing from other synthetic routes, the carbonyl group is derived from
CO2 directly without any other intermediates, which is non-toxic, non-corrosive, non-
34
flammable and abundant. Notably, this route, yielding water as the sole by-product, has
the same atom economy as oxidative carbonylation. Furthermore, the utilization of CO 2
avoids the risk of explosion caused by the co-existence of oxygen and carbon monoxide.
From the above, it is considered as an attractive and sustainable route for dialkyl
carbonates synthesis based on green chemistry principles.
Reaction route (stoichiometric feed CO2 + 2CH3OH → (CH3O)2CO + H2O

[kmol])
Raw materials CH3OH & CO2
Supply chain CH3OH from natural gas
CO2 separated from flue gas by absorption
(MEA)
Catalyst CHT-HMS
Energy Consumption (MJ/DMC 1152.8
produced)
By-products and co-products H2O & unreacted CH3OH
Economic potential RM 2.65/kg (CH3O)2CO
Conversion of CH3OH 8.3%
Waste and emissions Methylformate, unreacted CO2
Health and safety issues Methylformate
Extremely flammable
Harmful if swallowed or inhaled
Causes serious eye irritation
May cause respiratory irritation
Advantages Large availability of raw materials
Single step reaction
Renewable feedstock
Disadvantages Highest energy consumption
Low conversion of DMC
Low yield of DMC
35
Methylformate as a waste
1.4.1.1 Chemical Price
The market prices of the chemicals that are used in this process route are listed in
Table 1.13.
Table 1.13: Market Prices of Chemicals for Reaction 1

Chemical Price (USD/kg) Price (RM/kg)
Carbon Dioxide 0.58 2.59
Dimethyl Carbonate 1.25 5.56
Methanol 0.52 2.31
Water - -
*Currency rate: USD 1 = RM4.44
1.4.1.2 Economic Potential
The economic potential for this process is calculated as below

Overall CO2 + 2CH3OH (CH3O)2CO + H2O
Kgmol 1 2 1 1
MW 44.01 32.04 90.08 18.01
kg 44.01 64.08 90.08 18.01
kg/kg 0.4886 0.7114 1.0000 0.2000
RM/kg 2.59 2.31 5.56 -
Gross profit = (5.56 x 1) – [(2.59 x 0.4886) + (2.31 x 0.7114)]

= RM 2.65/kg (CH3O)2CO
36
1.4.2 Transesterification of methanol and propylene carbonate using CeCu as a

catalyst
Transesterification of methanol and propylene carbonate consists of two set of

reactions. The first reaction is the synthesis of propylene carbonate using propylene
oxide and carbon dioxide. The second reaction is the reaction of propylene carbonate
and two mole of methanol to produce propylene glycol; and dimethyl carbonate. This
route is particularly attractive for being CO 2-based. Generally speaking, carbon dioxide
can be considered as an environmentally friendly and widely available feedstock,
available as a waste emission of industrial processes. Chemical utilization of CO 2 for
DMC manufacture would be a means to turn this waste into a non-waste, allowing us to
view CO2 as a useful resource. The reaction path is shown below:
Reaction route (stoichiometric feed C3H6O + CO2 → C4H6O3

[kmol]) C4H6O3 + 2CH3OH → (CH3O)2CO +
C3H8O2
Raw materials CH3OH, CO2, & C3H6O3
Intermediate: C4H6O3
O2 from air (distillation)
Propylene oxide from H2O2 and propene
Catalyst First step: ion exchange resin D201
Second step: CeCu catalyst
Energy Consumption (MJ/DMC -746.3
produced)
By-products and co-products Propylene glycol, unreacted CH3OH, &
propylene carbonate
Conversion of C4H6O3 100%
37
Conversion of CH3OH 65%

Waste and emissions No waste
Health and safety issues Propylene oxide
extremely flammable
is harmful if swallowed, inhaled, or came
in contact with skin
may cause respiratory irritation
may cause genetic defects and cancer
Advantages CO2 is a feedstock in first step
Valuable by-product
Disadvantages Low yield of DMC
Low conversion of DMC
Two steps reaction
Propylene oxide use is an inherent risk
Table 1.14.

Carbon Dioxide 0.58 2.59
Methanol 0.52 2.31
Propylene Carbonate - -
Propylene Glycol 1.43 6.34
Propylene Oxide 1.20 5.33
38
Water - -
The economic potential for this process is calculated as below:
Overall C3H6O + CO2 + 2CH3OH (CH3O)2CO + C3H8O

Kgmol 1 1 2 1 1
MW 58.08 44.01 32.04 90.08 76.09
kg 58.08 44.01 64.08 90.08 76.09
kg/kg 0.6447 0.4886 0.7114 1.0000 0.8447
RM/kg 5.33 2.59 2.31 5.56 6.34
Gross profit = [(5.56 x 1) + (6.34 x 0.8447)] – [(5.33 x 0.6447) + (2.59 x 0.4886) +

(2.31 x 0.7114)]
1.4.3 Oxidative carbonylation of methanol (ENiChem)
The direct oxidative carbonylation of methanol to dimethyl carbonate uses

carbon monoxide, oxygen and methanol as raw materials. It is the most favorable route
in respect of thermodynamics and the operating conditions are relatively moderate.
Additionally, the formation of water as the only co-product is considered a green benefit
of the oxidative carbonylation method compared with the phosgenation approach. More
importantly, the raw materials and carbon monoxide can be derived from coal, natural
gas, shale gas and biomass.
39
Reaction route (stoichiometric feed 2CH3OH + 1/2O2 + CO → (CH3O)2CO +

[kmol]) H2O
Raw materials CH3OH, O2 & CO
O2 from air (distillation) CO from
natural gas
Catalyst CuCl2
Energy Consumption (MJ/DMC 131.5
produced)
By-products and co-products Unreacted CH3OH, O2,CO, & H2O
Conversion of CH3OH 16.49%
Waste and emissions No waste
Health and safety issues Carbon monoxide
Flammable
Toxic for human
CO and O2 must be fed at a carefully
controlled rate to avoid the risk of
explosion
Advantages One step reaction
High yield of DMC
High conversion of DMC
No waste
Disadvantages High feedstock and process cost
Use of CO as a feedstock is a inherent risk

40
Table 1.15.

Carbon Monoxide 0.60 2.66
Methanol 0.52 2.31
Oxygen - -
Water - -
The economic potential for this process is calculated as below:
Overall 2CH3O + 1/2O2 + CO (CH3O)2CO + H2O

H
Kgmol 2 1/2 1 1 1
MW 32.04 16.00 28.01 90.08 18.01
kg 64.08 8.00 28.01 90.08 18.01
kg/kg 0.7114 0.088 0.310 1.0000 0.2000
9 9
RM/kg 2.31 - 2.66 5.56 -
Gross profit = (5.56 x 1) – [(2.66 x 0.3109) + (2.31 x 0.7114)]

41
CHAPTER 2
PROCESS CREATION AND SYNTHESIS
2.1 Process Synthesis
Process synthesis is t h e s t e p in design w h e r e t h e chemical e n g i n e e r selects

the
component p a r t s a n d how t o interconnect them t o c r e a t e his flowsheet.
Process synthesis is the step in design where the design team selects the
component parts and how to interconnect them to create the flowsheet for the
production of dimethyl carbonate (DMC). Furthermore, it involves identification of
the processing route to produce the desired product, investigation of chemical
reactions needed, selection and design of the operations involved in the processing
route, as well as calculations of utility requirements, the calculations of waste and
emissions to the surroundings and many more. In this chapter, all the five key steps
of process synthesis were analyzed and determined by the design team accordingly.
2.1.1 Step 1: Eliminate Difference in Molecular Type
Table 2.1 shows the data from the chemistry laboratory focusing on several
reaction paths for manufacturer of DMC from several sources. Most of the reactions
paths of producing DMC are well known due to DMC have been commodity
chemicals for many years. Therefore, the design team proposed to carry out process
synthesis for newer substance as the data emerging from the research.
42
Table 2.1: Chemicals Involved in Reactions

Chemical Molecular Chemical Cost(RM/kg)
Weight Formula
(kg/kmol)
Carbon Dioxide 44.01 CO2 2.59
Carbon monoxide 28.01 CO 2.66
Dimethyl 90.08 C3H6O3 5.56
Carbonate
Methanol 32.04 CH3OH 2.31
Oxygen 16.00 O2 -
Propylene 102.09 C4H6O3 -
carbonate
Propylene glycol 76.09 C3H8O2 6.34
Propylene oxide 58.08 C3H6O 5.33
Water 18.01 H2O -
The challenge is to guide the chemists away from those reaction paths that
lead to processes that are costly to build and operate, and to arrive at designs that are
economical and environmentally friendly. Furthermore, another supercritical
challenge is to arrive at designs as fast as possible, to be able to capture the market
before another company develops a competitive process or chemical. Therefore, the
principal reaction pathways of DMC production as follows:
1) Direct Synthesis of Carbon Dioxide and Methanol
CO2 + 2CH3OH → (CH3O)2CO + H2O
Direct synthesis of DMC, is a dual-purpose green reagent and solvent, from

carbon dioxide (CO2) and methanol (CH3OH) is one of the promising routes.
43
This one step reaction path is considered as an environmental friendly

reaction, as the carbonyl group is derived from CO 2 directly without any other
intermediates, which is non-toxic, non-corrosive, non-flammable and
abundant. This direct reaction route results in high atom-efficiency. Notably,
this route yielding water as the sole by-product. This reaction is an
equilibrium-limited reaction and only a very small amount of DMC could be
produced (Dou 2010). Furthermore, the process involves a slightly lower
conversion of raw material (methanol), which is only 8.3% and the yield of
DMC is only 6%.
2) Transesterification of methanol and propylene carbonate
C3H6O + CO2 → C4H6O3

C4H6O3 + 2CH3OH → (CH3O)2CO + C3H8O2
Transesterification of propylene carbonate with methanol is an attractive

route for the production of DMC. Carbon dioxide is effectively utilize in the
production of DMC through cycloaddition of CO2 to epoxides to form cyclic
carbonates which gives 100% atom efficiency (Assabumrungrat 2014). This
route has many distinct advantages such as: first, it is free from corrosion to
equipment; second, there is no waste formation; and third, it has higher
conversion (Kumar et al., 2016). It provides a good conversion of propylene
carbonate as well as yield of DMC, which are 65.4% and 71.9% respectively
by using CeCu catalyst at optimum reaction condition (Kumar et al., 2016).
For this reaction, propylene glycol which is a valuable chemical is obtained as
a by-product.
3) Oxidative carbonylation of methanol (ENiChem)
2CH3OH + 1/2O2 + CO → (CH3O)2CO + H2O

44
The one-step liquid- phase methanol oxidative carbonylation process,

developed by Enichem, is by far the most popular phosgene-free route for the
industrial production of DMC. The yield of DMC reported 60-70% by using
CuCl2 as a catalyst and the conversion of methanol is about 16.49%
accordingly. However, this process produces severe equipment corrosion and
catalyst deactivation because CuCl2 has been used as the active catalysts (Pei
et al., 2016). Apart from that, CuCl2 is sparingly soluble in methanol and as a
result the substrate cannot react with the catalyst effectively to form an active
intermediate (Mketo 2010). However, the formation of water as the only co-
product is considered a green benefit of the oxidative carbonylation method.
More importantly, the raw materials and carbon monoxide can be derived
from coal, natural gas, shale gas and biomass.
By the information given before, the design team would reject reaction path 1
(Direct Synthesis of Carbon Dioxide and Methanol) due to the low conversion of
methanol and low yield of DMC. Therefore, this leaves the other reaction paths (2
and 3) as potentially attractive to be selected on the basis of chemical prices. For this
case, the gross profit of the reaction is taken as a basis for choosing the best reaction
path. Table 2.2 shows the gross profit for all three reaction path mention early.
Table 2.2: Gross Profit for Production of Dimethyl Carbonate (Based on Chemical
Prices in Table 2.1)
Reaction Overall Reaction Gross Profit
Path (RM/kg of DMC)
1 CO2 + 2CH3OH → (CH3O)2CO + H2O 2.65
2 C3H6O + CO2 → C4H6O3 4.57
C4H6O3 + 2CH3OH → (CH3O)2CO + C3H8O2
3 2CH3OH + 1/2O2 + CO → (CH3O)2CO + H2O 3.09
Reaction path 2 and 3 which have highest gross profit will proceed to the next
step of screening that considers the several key selection criteria involving mainly on
conversion and operating conditions. The reactions involved are transesterification of
methanol and propylene carbonate using CeCu catalyst and oxidative carbonylation
45
of methanol by using CuCl2 catalyst. However, for clarification and impartiality

purposes, Reaction 1 involving the direct synthesis of CO 2 and methanol will still be
considered for the following screening step.
The ratings code of 1, 2 and 3 will represent the level of ratings with 1 being
the lowest while 3 being the highest. These codes will be multiplied with the
weightage and the point of every characteristic will be summed up. The highest
points collected will be selected for the next procedure which focuses on the
subsequent steps. The matrix for the process selection is shown in Table 2.3.
46
Table 2.3: Matrix for Process Selection

Reaction 2
Reaction 1
Transesterification of methanol Reaction 3
Criteria Weightage Direct synthesis of CO2 &
& propylene carbonate using Oxidative carbonylation of methanol
methanol
ionic liquid as catalyst
RM 2.65/kg (CH3O)2CO RM 4.57/kg (CH3O)2CO RM 3.09/kg (CH3O)2CO

Gross profit 0.20
1 3 2
Yield of DMC is about 6% Yield of DMC is about 72% Yield of DMC may reach 60-70% with
Yield/ CuCl2
conversion/ 0.20 Conversion about 8.3% Conversion about 65% Conversion about 16.49%
selectivity Selectivity is about 91% Selectivity is about 95% Selectivity is 97%
1 3 2
Development of manufacturing
Process condition is well- using CeCu catalyst shows
Process condition is applied in most of
determined but is less applied promising results with
Process stability 0.15 the industry
in most of the industry developed transesterification
process
1 2 3
Side reactions/ 0.15 Water and unreacted Propylene glycol, unreacted Water, unreacted methanol, oxygen and
47
methanol methanol, propylene carbonate carbon monoxide

by-products
3 1 2
Carbon monoxide replaces carbon

Only carbon dioxide and Similar to Reaction 1 added
dioxide as raw material together with
Cost of feed 0.10 methanol are required with propylene carbonate
methanol and oxygen (air)
3 1 2
Methylformate and CO and O2 may cause explosion if not

Environmental No waste is produced
0.10 unreacted CO2 controlled properly, no waste is produced
effects & safety
2 3 1
50°C 150°C 120°C

Temperature 0.05
3 1 2
148 atm 19.7 atm 26.6 atm

Pressure 0.05
1 3 2
Total 1.00 1.70 2.25 2.05
Remark: Rating from 1-3, 1 is the worst while 3 is the best.
48
According to the total marks obtained from the matrix, Reaction 2 is highly
preferred. Although most chemical plants of the industry uses the oxidative
carbonylation of methanol process in the production of dimethyl carbonate, however,
the transesterification of propylene carbonate has seen its application tremendously
promising in recent years and more research proves influential towards better
productivity. Reaction 2 has the best potential toward production and in terms of
sustainability of the industry, although there is still much research needed to improve
the yield and conversion and thus, reduce the amounts of wastes. In this case, the use
of the cerium-cupric, CeCu catalyst would be further add to sustainability positively.
Besides, the conversion of the raw material and the DMC yield is improved
significantly compared to the other considered reactions. Despite the complex by-
products produced by Reacion 2, the fact that propylene glycol can be sold outweigh
the handling of the by-product itself which further enhances the gross profit of this
reaction. In fact, Reaction 2 does not cause potential explosion as compared to that of
Reaction 3 in which the combination of carbon monoxide and oxygen are possible
ignition sources. The operating temperature for all three reactions are not too
extremely high but Reaction 2 boasts the lowest operating pressure which proves
vital in having a safe operation. In short, Reaction 2 is better than Reaction 1 and 3 in
most of the top aspects especially in terms of the gross profit and dimethyl carbonate
yield.
49
2.1.2 Step 2: Distribution of Chemicals
In this step, the possible sources and sinks are matched accordingly so that,
the total mass flow into a rector equals the total mass flow out. The plant is proposed
to produce 15,000 MTA of 99% purity of DMC. The mixing operation is introduced
to eliminate the differences in flow rates when a sink is supplied by two or more
sources. In other cases, a single source is divided among several sinks. The
propylene oxide and carbon dioxide are matched with their sinks into the propylene
carbonate synthesis reactor. It is assumed that propylene oxide and carbon dioxide
enter the reactor in the stoichiometric ratio of 1:1.097 as in reaction 2. This is
because it is not practical to design the reactor for complete conversion of limiting
reactant (Propylene Oxide); instead, the reactor effluent emerges with some of the
limiting reactant still present and is then usually subjected to a separation process to
remove the unrecovered reactant from the product. However, for this case the
unreacted carbon dioxide does not undergoes separation process because it does not
affect the next reaction due to its inert property. The experimental data indicates
100% conversion of propylene oxide at the reactor condition 250°C and 19.74 atm.
From the Figure 2.1, it can be clearly seen that the flow rates of 1185.11 kg/hr
propylene oxide and 985.28 kg/hr of carbon dioxide produce 2083.65 kg/hr of
propylene carbonate and 87.13 kg/hr of carbon dioxide respectively.
Figure 2.1: Flow Diagram of Chemical Distribution in the System

50
Figure 2.2: Flow Diagram of Chemical Distribution in the System with Recycled
Stream
Next, the propylene carbonate source from the reactor is sent to its sink in the
transesterification operation, which operates at 150°C and 1 atm. Only 65% of
propylene oxide is converted to dimethyl carbonate with a by-product of propylene
glycol. To satisfy the overall material balance, 2083.65 kg/hr of propylene carbonate
must produce 1838.24 kg/hr of dimethyl carbonate and 1552.76 kg/hr of propylene
glycol. The additional propylene carbonate and methanol needed are computed by
mass balance to equal 704.16 kg/hr and 1121.97 kg/hr respectively. Since, the
reaction converts 65% of propylene carbonate and methanol into dimethyl carbonate,
the unconverted reactants can be recycled back to the reactor. Therefore, the recycle
stream is introduced and the mass balance is calculated using the following formula.
From that, the total mass flow rate into and out of the reactor as well as the recycle
stream can be calculated based on the assumptions listed below:
1. Basis of production is 15,000 metric tons of dimethyl carbonate per year.

2. Production hours are restricted 340 days per year and running 24 hours
every day. The rest of the days are used for breakdowns and monthly
maintenance.
3. Reaction takes place in the propylene carbonate synthesis reactor and
transesterification reactor unit without side reaction.
4. The system is in steady state.
5. No leakage in pipes and vessel in the system.
51
6. No reaction occurs in expander, mixer or heat exchanger. Therefore, the

total input of any substance is assumed equal to the total output of the
substance.
Production rate of dimethyl carbonate
15,000 metric ton 1000 kg 1 year 24 operation hours

× × ×
1 year 1 metric ton 340 operation days 1 operation day
¿ 1,838.24 kg /hr
Recycle propylene carbonate stream
1−x
× Stoichiometric feed of propylene carbonate
x
1−0.65 kg
× 2083.65 of propylene carbonate
0.65 hr
¿ 1121.97 kg /hr
Recycle methanol stream
1−x
× Stoichiometric feed of methanol
x
1−0.65 kg
× 1307.72 of methanol
0.65 hr
=704.16 kg/hr
52
2.1.3 Step 3: Eliminate Differences in Composition
The separation processes to obtain high purity of dimethyl carbonate consists

of two possible alternatives as shown in Figure 2.3 and Figure 2.4. The major
products from the transesterification of methanol with propylene carbonate include
dimethyl carbonate and propylene glycol with excess and unreacted methanol and
propylene carbonate. The raw materials as well as the consequent chemicals
produced are required to go through a series of separation units to achieve a high-
purity dimethyl carbonate. The mixture of chemicals at the beginning of the reactions
can be separated according to the boiling points of the chemicals used as tabulated in
Table 2.4
Figure 2.3: Flowsheet of 1st Alternative Separation Process of Dimethyl Carbonate

53
Figure 2.4: Flowsheet of 2nd Alternative Separation Process of Dimethyl Carbonate
Table 2.4: Boiling and Melting Points of Chemicals at 1 atm

Chemicals Melting Point (°C) Boiling Point (°C)
Propylene Glycol -60.0 187.6
Propylene Oxide -112.13 34.23
Propylene Carbonate -48.8 242.0
Carbon Dioxide -56.6 -78.5
Methanol -97.8 64.7
The transesterification of methanol with propylene carbonate begins with the

production of propylene carbonate at the first reactor. This initial reaction involves
carbon dioxide and propylene oxide as the raw materials and occurs at 100°C and
138 atm with complete conversion to produce propylene carbonate as the subsequent
raw material for the second reaction later on.
54
The second reactor operates at 150°C and 1 atm which involve the main
reaction to produce dimethyl carbonate (DMC). Propylene carbonate produced from
the previous reaction is used together with methanol to undergo transesterification
process towards DMC production with a conversion rate of 65% for both raw
materials.
Apart from the production of the propylene glycol by-product, there will also
be unreacted methanol and propylene carbonate present in the outlet stream of the
second reactor. The separations of these chemicals are based on their respective
boiling points. Up to this point of process flow, both alternatives possess similar
route of reaction. The following separation description is based on the respective
alternative.
2.1.3.1 Alternative 1 Separation Process Description
The distillation column (Column 1) is used to separate methanol (CH 3OH),

propylene carbonate (C4H6O3) and propylene glycol (C3H8O2) from the desired DMC
product. As methanol forms an azeotropic mixture with DMC and their boiling
points are significantly apart from that of C4H6O3 and C3H8O2, both methanol and
DMC are separated according to the heuristics which state the most difficult
separation is done lastly and are directed to the azeotropic distillation column
(Column 2).
The azeotropic distillation column (Column 2) separates the desired DMC

product from methanol to achieve a higher purity level of DMC up to 99%. The
separated methanol can be recycled to the mixer prior to Reactor 2 to compensate its
reaction with recycled propylene carbonate as the raw materials to produce dimethyl
carbonate (DMC).
The other distillation column (Column 3) will result in the separation of

propylene carbonate (C4H6O3) and propylene glycol (C3H8O2) in which the former
55
can be recycled back to the mixer before Reactor 2 whereas the latter can be sold in
the market that can further improve the profit of this process.
2.1.3.2 Alternative 2 Separation Process Description
As compared to Alternative 1, the first distillation column (Column 1) is used

to separate methanol (CH3OH) from the desired DMC product, propylene carbonate
(C4H6O3) and propylene glycol (C3H8O2). This is due to the fact that methanol has the
lowest boiling point which renders it as the most volatile among the rest. According
to the heuristics, the component that has the highest volatility should be removed
first. The separated methanol can be recycled back to the reactor through the mixer
preceding it.
The bottoms product from the first distillation column will be directed to the
second distillation column (Column 2) which separates the desired DMC product
from propylene carbonate (C4H6O3) and propylene glycol (C3H8O2) to achieve a
higher purity level of DMC up to 99%. Dimethyl carbonate has the second lowest
boiling point and based on the direct sequence choice, DMC is valid as the next
component to be separated because its greater volatility as compared to propylene
carbonate and propylene glycol. The gaseous DMC will be condensed accordingly to
obtain its liquid state.
The final distillation column (Column 3) will result in the separation of

propylene carbonate (C4H6O3) and propylene glycol (C3H8O2), coming from the
bottoms product of the second distillation column. The former can be recycled back
to the mixer before Reactor 2 whereas the latter can be sold in the market that can
further improve the profit of this process. Similarly, their separation is based on the
comparison of their relative volatility.
2.1.3.3 Selection of Desired Alternative

56
A comparison is made between the two alternatives provided that considers

the compliance of related heuristics as shown in Table 2.5 below.
Table 2.5: Comparison between Alternative 1 (Figure 2.3) and Alternative 2 (Figure
2.4)
SIMILARITIES
Both utilize two reactors

Similar operating temperature and pressure before the first separation
Similar recycle streams with a mixer in between two reactors
DIFFERENCES
ALTERNATIVE 1 ALTERNATIVE 2
Separation follows a part of the direct Separation follows the direct sequence:
sequence:
DMC-Methanol / Propylene carbonate- DMC / Methanol / Propylene
Propylene glycol carbonate / Propylene glycol
Follow Heuristic 2 Follows Heuristic 2
Azeotropic mixture of DMC-Methanol Azeotropic mixture of DMC-Methanol
is separated first from PC and PG. The is not separated first from PC and PG
most difficult separation is done the instead, methanol is separated first.
last.
Follows Heuristic 4 Violates Heuristic 4
The desired DMC product which The desired DMC product which
requires the highest purity is separated requires the highest purity is not
at the end of the sequence. separated at the end of the sequence
instead, at the second component
separation.

DMC-Methanol azeotropic mixture has Methanol is removed first which is
the greatest molar percentage among the followed by DMC, PC and PG.
components and is removed first of the
sequence to decrease the size and cost
of the following distillation column and
57
piping system.
Follows Heuristic 3
Violates Heuristic 3
Separation favors near equimolar Separation does not favor near
amounts of distillate and bottoms equimolar amounts of distillate and
bottoms
As a conclusion, Alternative 1 is selected as the better choice of separation

process due to its overwhelming compliance to the heuristics as compared to
Alternative 2.
58
2.1.4 Step 4: Elimination of Differences in Temperature, Pressure and Phase
Figure 2.5 and 2.6 shows the temperature, pressure and phase changes for the process flow diagrams shown above. The elaborations of
the specific changes are done as below.
Figure 2.5: Flow Diagram of Difference Elimination in Temperature, Pressure and Phase Change Operations for First Alternative
59
Figure 2.6: Flow Diagram of Difference Elimination in Temperature, Pressure and Phase Change Operations for Second Alternative
60
a) CO2 and Propylene Oxide Inlet Streams to CSTR
Gas CO2 Gas CO2 Gas CO2

-78°C, 1 atm 179°C, 19.7 atm 250°C, 19.7 atm
Pressure Temp.
change change
Liquid C3H6O Liquid C3H6O
15°C, 1 atm Pressure Liquid C3H6O Temp. 250°C, 19.7 atm
change change
18°C, 19.7 atm
The first reaction
involves the production of propylene carbonate as the raw material for dimethyl
carbonate production subsequently. Propylene carbonate can be produced by the
reaction between carbon dioxide and propylene oxide in a CSTR. Both gaseous
carbon dioxide and liquid propylene oxide will undergo pressure changes at first
followed by a temperature change to complement the required optimum conditions in
the production of propylene carbonate. The pressure changes from atmospheric level
at 1 atm to 19.7 atm which is the operating pressure needed in the CSTR and is
followed by a change in temperature at their natural state to 250°C as the operating
temperature.
b) Effluent from CSTR
Gas C4H6O3 Liquid C4H6O3 Liquid C4H6O3

250°C, 19.7 atm Pressure 150°C, 1 atm Temp. 196°C, 1 atm
change change
The effluent from the CSTR contains liquid propylene carbonate at 250°C
and 19.7 atm from the complete conversion of the reaction between carbon dioxide
and propylene oxide. For proper handling and safety purposes, pressure change is
done from 19.7 atm to 1 atm which is then followed by a consequent temperature
61
change to 150°C. These conditions are in accordance with the required operating
conditions for the next main reaction involving the production of dimethyl carbonate.
c) Effluent from PBR
Liquid mixture Liquid mixture

150°C, 1 atm Pressure 150°C, 2 atm
change
In packed bed reactor (PBR), the main reaction towards the production of
dimethyl carbonate from methanol and propylene carbonate occurs at 150°C and 1
atm as required in the presence of CeCu catalyst. Its effluent consists of unreacted
methanol and propylene carbonate; by-product propylene glycol and dimethyl
carbonate itself. The effluent will undergo an increase in pressure from 1 atm to 2
atm before entering the distillation column at 2 atm. The increased pressure is
selected on the basis of relative volatility of the components so that the azeotropic
mixture of DMC-methanol can be separated easily and effectively.
d) Distillate Products from Distillation Column 1
Liquid DMC & Liquid DMC & Liquid DMC &

methanol methanol methanol
93°C, 2 atm Pressure 94°C, 10 atm 150°C, 10 atm
Temp.
change
change
The distillate product
consisting of dimethyl carbonate and methanol from the first distillation column is
the stream discussed. Based on their respective boiling points and relative volatility,
the azeotropic nature of dimethyl carbonate-methanol mixture requires specific
separation system and in this case, the pressure swing distillation is used. However, it
is originally at 93°C and 2 atm from the distillation column so a pressure and
temperature change operation is required to complement the operating conditions of
the following pressure swing distillation columns.
62
e) Bottoms Product from Distillation Column 1
Liquid PC & PG Liquid PC & PG

222°C, 2 atm Pressure 198°C, 1 atm
change
The first distillation column produces a bottoms product consisting of

propylene carbonate (PC) and propylene glycol (PG) at 222°C and 2 atm. To
complement the operating conditions of the second distillation column, a pressure
change operation is needed from 2 atm to 1 atm.
f) Methanol Inlet to PBR
Liquid methanol Liquid methanol

25°C, 1 atm Temp. 150°C, 1 atm
change
Methanol is one of the raw materials needed to produce dimethyl carbonate

and this occurs in PBR. The methanol inlet is heated from room temperature to the
required operating temperature of the PBR at 150°C. Before being heated, the
methanol feed stream combines beforehand with the recycle methanol stream from
the pressure-swing distillation column.
g) Dimethyl Carbonate Bottoms Product from High Pressure Column
Liquid DMC Liquid DMC Liquid DMC

183°C, 10 atm 90°C, 1 atm 25°C, 1 atm
63
Pressure Temp.
change change
The bottoms product from the pressure-swing distillation column or the

segmented high pressure column consists mainly of dimethyl carbonate at liquid
state. There is a need to change its pressure and temperature to enable it to be
handled and stored in a conducive and convenient form which refers to the reference
atmospheric pressure and temperature at 25°C and 1 atm.
h) Propylene Glycol Distillate Product from Distillation Column 2
Liquid PG Liquid PG
188°C, 1 atm Temp. 25°C, 1 atm
change
The top product from the second distillation column involved in the
separation of propylene carbonate and propylene glycol consists mainly of propylene
glycol at 188°C and 1 atm. Propylene glycol can be sold to existing market as
another source of profit. Hence, it is better to convert the propylene glycol into the
liquid state which can be handled easily and conveniently. Pressure and temperature
change operations might be involved to achieve the desired outcome.
i) Methanol Distillate Product from High Pressure Column

137°C, 10 atm 64°C, 1 atm
Pressure
change
The top product from the high pressure column, a segment of the pressure
swing distillation column, involved in the separation of the azeotropic mixture of
dimethyl carbonate and methanol consists mainly of methanol at 137°C and 10 atm.
64
Methanol can be recycled back prior to the methanol inlet to PBR for the production
of dimethyl carbonate. Hence, it is required to purify further the distillate product
from the high pressure column to complement this need. Pressure and temperature
change operations might be involved to achieve the operating conditions of the
following low pressure column.
j) Propylene Carbonate Recycle Stream
Liquid propylene Liquid propylene

carbonate Temperature carbonate
241°C, 1 atm change 196 °C, 1 atm
The bottom product of DC-101 which is liquid propylene carbonate is

discharge at 241°C and 1 atm. The stream later recycles back to a feed stream of
propylene carbonate. The feed stream is at 196 °C and 1 atm. Therefore, temperature
change is required in order to recycle back the propylene carbonate.
k) Methanol Recycle Stream

62°C, 1 atm Temperature 30 °C, 1 atm
change
The top product from low pressure column which is liquid methanol is
discharge at 62°C and 1 atm. The liquid methanol is recycling back to the feed
stream. However the liquid methanol produced need to be cool down to 30°C in
order to meet the conditions of feed methanol.
2.1.5 Step 5:Task Integration

65
In Step 5 of Task Integration step, all the reaction and process will be
substitute with appropriate and suitable unit processes. The possible flow diagrams
of this step is show figure 2.7 and figure 2.8 respectively based on flow diagram in
step 4. Basically, both flow diagram is almost the same and only differ in term of
their separation part in order to get the desired product (dimethyl carbonate). Based
on the figures above, figure 2.7 has been selected for the production of Dimethyl
Carbonate. This is because process flow diagram in figure 2.7 is roughly more
economical than figure 2.8 as the number of unit operation involved in that process is
less. Moreover, the separation part in the first alternative is highly preferable as it
follow the heuristics rules which are very helpful to determine the optimum final
design. Table 2.6 shows the summary and description of every unit operations used
in the production of dimethyl carbonate based on the chosen alternative flow diagram
(Figure 2.7).
66
Figure 2.7: Flow Diagram of Task Integration for First Alternative

67
Figure 2.8: Flow Diagram of Task Integration for Second Alternative

68
Table 2.6: Description of Selected Unit Operations

Unit Operations Description
Compressor & Expander Function:
(C-100, C-101)  To compress the feed stream in order
for pressure change occur
C-100: Compress the gas feed of carbon

dioxide at 1 atm to 19.7 atm
Operating Temperature: 179oC
Operating Pressure: 19.7 atm
C-101: Compress the product stream from

the PFR of 19.7 atm to 1 atm
Operating Temperature: 196 oC
Operating Pressure: 1 atm
Cooler Function:
(E100,E-101, E-102)  To decrease the temperature
E-100: Decrease temperature of DMC

product stream from 90 oC to 25 oC
E-101: Decrease temperature of C3H8O2

product stream from 188 oC to 25 oC

product stream of mixer-100 from
196 oC to 150 oC
E-103: Decrease temperature of CH3OH

product OF HPC from 137 oC to 50 oC
69

product of DC-101 from 241 oC to
196 oC
Distillation Column Function:

(D-100, D-101)  To separate multiple component in
order to get high purity of desired
product
D-100:
Top Product: CH3OH, DMC
Bottom Product: C3H8O2, C4H6O3
D-101:
Top Product: C3H8O2
Bottom Product: C4H6O3
Heater Function:
(H-100, H-101, H-102, H-103)  To increase the temperature
H-100: Increase temperature of CO2 feed

stream from 179 oC to 250 oC
H-101: Increase temperature of C3H6O feed

stream from 18 oC to 250 oC
H-102: Increase temperature of the mixture

of CH3OH and DMC stream from 94
o
C to 150 oC
70

H-103: Increase temperature of CH3OH

mixture stream from 30 oC to 150 oC
Pressurized Column Function:

(HPC-100,LPC-100)  To separate methanol (CH3OH) and
dimethyl carbonate (DMC)
HPC:
LPC:
Mixer Function:
(M-100, M-101)  To mixer the feed stream and recycle
stream
M-100: Mix the C4H6O3 feed with C4H6O3

recycle
M-101: Mix the CH3OH feed with CH3OH

recycle
Operating Temperature:30oC
Pump Function:
(P-100, P-101, P-102)  To increase the pressure
P-100: Increase pressure of C3H6O feed from

71
1 atm to 19.7 atm

Phase: Liquid
P-101: Increase pressure of product stream

of second reactor from 1 atm to 2
atm
Phase: Liquid
P-102: Increase pressure of mixture stream

of CH3OH and DMC from 2 atm to
10 atm
Phase: Liquid
Reactor Function:
(SR-1, SR-2)  Place for desired reaction to occur
SR-1: Place for reaction between carbon

dioxide and propylene oxide occur in
order to produce propylene carbonate
Conversion of propylene oxide: 100%
SR-2: Place for transesterification of

methanol and polylene carbonate to
occur
Overall Conversion: 65%
Catalyst: CeCu
Valve Function:
(V-100, V-101, V-102)  To decrease the pressure
72
V-100: Decrease the pressure of bottom

product from first distillation
column to 1 atm
V-101: Decrease the pressure of top product

stream from HPC to 1 atm
V-102: Decrease the pressure of bottom

product stream from HPC to 1 atm
2.2 Process Description
A CO2 stream (Stream 1) and a C3H6O stream (Stream 4) which consist of their
pure gaseous and liquid form respectively is directed to temperature and pressure change
unit operations in the form of compressor, pump and heaters where all the feed streams
are converted to vapor phase prior entering the first reactor. These streams (Stream 1 and
Stream 4) are then fed into a plug flow reactor (SR-1) where both components are
reacted and converted to form propylene carbonate as one of the main raw materials for
the DMC production. The reaction conversion is 100 % and there is no particular side
reaction with other by-products.
Stream 7 as the outlet stream of the PFR channels the C4H6O3 to an expander (C-
101) for pressure reduction operation from 19.7 to 1 atm which cause a consequent
phase change from vapor to liquid in Stream 8. This is followed by a mixer (MIX-100)
that combines Stream 8 with the recycle C4H6O3 stream (Stream 29). The resulting
73
Stream 9 is directed to a cooler (E-102) with regards of the required operating

temperature and pressure of the CSTR at 150°C and 1 atm. On the other hand, fresh
CH3OH feed (Stream 24) is mixed with recycle CH3OH stream (Stream 23) before
entering the CSTR to undergo the main reaction namely, transesterification with C4H6O3
to produce DMC. The reaction conversion is 65% with 72% yield and C3H8O2 is the only
by-product produced. The recycle CH3OH stream (Stream 23) consists of almost 100%
CH3OH with extremely minor traces of C4H6O3 and C3H8O2.
The reactor outlet (Stream 11) is then fed into a pump to increase the pressure
from 1 to 2 atm where it is then fed into a distillation column (DC-100). It is meant to
separate the azeotropic DMC-CH3OH mixture (Stream 13) from C4H6O3 and C3H8O2.
The bottoms product of DC-100 (Stream 16) is further separated at the distillation
column (DC-101) at 1 atm to Stream 28 and Stream 29 which consists of a major portion
of C3H8O2 and C4H6O3 respectively. The distillate C3H8O2 product from DC-101 (Stream
28) is then fed to a cooler to reduce the temperature from 187.69°C to 25°C and it can be
sold at 99.98% purity. Stream 29 consists of 99.9% C4H6O3 with very minor traces of
C3H8O2 which can be recycled back to the PBR for DMC production.
As for the distillate products from DC-100 (Stream 13), DMC is separated from
CH3OH using pressure-swing distillation consisting of a High-Pressure Column (HPC-
100) and a Low-Pressure Column (LPC-100). Stream 13 is first fed to a pump and heater
to satisfy the required operating HPC conditions at 10 atm. Pressure swing distillation is
deemed to be a simpler and more economical method of azeotropic separation which
involves the use of two columns at different pressures.
In the High-Pressure Column (HPC-100), almost 99% of the DMC molar flow
rate is collected in the bottoms product of HPC-100 (Stream 19) at 99% purity before
subsequent pressure and temperature reduction operation. The distillate product (Stream
17) from HPC-100 is temperature- and pressure-adjusted to 50°C and 1 atm respectively
according to the operating conditions of the following Low-Pressure Column (LPC-
74
100). LPC-100 aims to recover as much CH3OH as possible for the purpose of recycling
back to the PBR through Stream 23. It also prevent build-up of inerts such as CO2 or
DMC in the PBR if left uncontrolled.
75
CHAPTER 3
MANUAL MATERIAL AND ENERGY BALANCE CALCULATIONS
3.1 Introduction
A detailed material and energy balance are crucial compartments in a plant

design project due to their relation to both equipment sizing and economic evaluation
throughout the stages of designing later on. There are various ways or methods of
manual calculation and computer programming software or even process simulators that
can assist the complex calculations in an easier and more effective way.
This plant design project will involve the manual calculations of the material and
energy balance within the process based on simple and quick methods in Systematic
Methods of Chemical Process Design (Biegler et al., 1997) and other several methods in
Transport Processes and Unit Operations (Geankoplis, C.J., 1993). The manual
calculations will be shown briefly in the following sub-chapters based on equipment and
the process simulation is executed using Aspen Plus simulator.
76
3.2 Manual Material Balance Calculation
Material balances are the some of the basic parts of a process design. Mass and
matter cannot be created nor destroyed, as stated by the law of conservation of mass.
This statements tells us that mass and matter could only enter and exit a system, be it in
the same form or another form. Additional mass could not be created in the system nor
be reduced within the system unless mass enters or leaves the system respectively. The
general equation of the law of mass conservation is shown for a particular component:
Input + Generation = Output + Consumption + Accumulation
For a steady-state process, the accumulation term will be neglected whereas in

the absence of a chemical reaction, the equation will be reduced to:
Input = Output
This dimethyl carbonate production plant does not involve any mass destruction
or generation as described. It involves purely the mass inlet that is equal to the mass
outlet. All material balance calculations will be based on the mass basis for evaluation
purposes.
Antoine Equation constants can be used to determine the partial pressure of each
pure component especially with those which are related to the vapor phase in the system.
The equation is as follows:
B
ln P° = A –
T ( K ) +C
77
Table 3.1: Important Values of Components Involved

Componen Formula Mol. Tbp Ant A Ant B Ant C
t Weight (°C)
(kg/kmol)
Propylene
C3H6O 58.08 34.2 7.01443 1086.369 228.594
oxide
Carbon
CO2 44.01 -78.5 7.58828 861.82 271.883
dioxide
Propylene
C4H6O3 102.09 242.0 9.6179 4097.7 184.78
carbonate
Methanol CH3OH 32.04 64.7 8.08097 1583.271 239.7
Dimethyl
(CH3O)2CO 90.08 90.5 Based on vapor pressure table
carbonate
Propylene
C3H8O2 76.09 188.2 9.18762 2651.27 232.783
glycol
3.3 Material Balance Based on Equipment
3.3.1. Centrifugal Compressor (C-100)
Component Inlet Outlet

S34 S2
78
kmol/hr kg/hr kmol/hr kg/hr

CO2 22.3826 985.0588 22.3826 985.0588
Total 22.3826 985.0588 22.3826 985.0588
3.3.2 Heater (H-100)

S2 S3
CO2 22.3826 985.0588 22.3826 985.0588
Total 22.3826 985.0588 22.3826 985.0588
79
3.3.3 Centrifugal Pump (P-100)

S4 S5
C3H6O 20.4100 1185.4128 20.4100 1185.4128
Total 20.4100 1185.4128 20.4100 1185.4128
3.2.4 Heater (H-101)

S5 S6
C3H6O 20.4100 1185.4128 20.4100 1185.4128
Total 20.4100 1185.4128 20.4100 1185.4128
80
3.3.5 Plug Flow Reactor (SR-1)
Reaction Conversion (%)

C3H6O + CO2 → C4H6O3 100
(with ion exchange resin D201 catalyst) (1:1.096 molar ratio C3H6O: CO2)

S3 S6 S7
kmol/hr kg/hr kmol/hr kg/hr kmol/hr kg/hr
CO2 22.3826 985.058 - - 1.9726 86.8147
8
C3H6O - - 20.4100 1185.412 - -
8
C4H6O3 - - - - 20.4100 2083.6569
Total 22.3826 985.058 20.4100 1185.412 22.3826 2170.4716
8 8
81
3.3.6 Gas Expander (C-101)

S7 S8
CO2 1.9726 86.8147 1.9726 86.8147
C4H6O3 20.4100 2083.6569 20.4100 2083.6569
Total 22.3826 2170.4716 22.3826 2170.4716
3.3.7 Mixer (MIX-100)

82
S8 S32 S9
CO2 1.9726 86.8147 - - 1.9726 86.8147
C4H6O3 20.4100 2083.656 10.9900 1121.969 31.4000 3205.6266
9 7
Total 22.3826 2170.471 10.9900 1121.969 33.3726 3292.4413
6 7
3.3.8 Cooler (E-102)

S9 S10
CO2 1.9726 86.8147 1.9726 86.8147
C4H6O3 31.4000 3205.6266 31.4000 3205.6266
Total 33.3726 3292.4413 33.3726 3292.4413
83
3.3.9 Mixer (MIX-101)

S24 S33 S25
CH3OH 40.8312 1308.2316 21.9735 704.0309 62.8047 2012.2625
DMC - - 0.0021 0.1892 0.0021 0.1892
Total 40.8312 1308.2316 21.9756 704.2201 62.8068 2012.4517
3.3.10 Heater (H-103)

84

S25 S26
CH3OH 62.8047 2012.2625 62.8047 2012.2625
DMC 0.0021 0.1892 0.0021 0.1892
Total 62.8068 2012.4517 62.8068 2012.4517
3.3.11 Packed Bed Reactor (SR-2)
Reaction Conversion (%)

C4H6O3 + 2CH3OH → (CH3O)2CO + C3H8O2 65
(with CeCu catalyst)
85

S10 S26 S11
CO2 1.9726 86.8147 - - 1.9726 86.8147
CH3OH - - 62.8047 2012.262 21.9820 704.2403
5
C4H6O3 31.4000 3205.626 - - 10.9900 1121.9691
6
DMC - - 0.0021 0.1892 20.4121 1838.7220
C3H8O2 - - - - 20.4100 1552.9969
Total 33.3726 3292.441 62.8068 2012.451 75.7667 5304.8930
3 7
Streams S10/26 S11
Total mole 96.1794 75.7667
Total mass 5304.8930 5304.8930

86

S11 S12
CO2 1.9726 86.8147 1.9726 86.8147
CH3OH 21.9820 704.2403 21.9820 704.2403
C4H6O3 10.9900 1121.9691 10.9900 1121.9691
DMC 20.4121 1838.7220 20.4121 1838.7220
C3H8O2 20.4100 1552.9969 20.4100 1552.9969
Total 75.7667 5304.8930 75.7667 5304.8930
3.3.13 Distillation Column 1 (D-100)
Component Formula Mol. Weight Tbp

(kg/kmol) (°C)
Carbon dioxide CO2 44.01 -78.5
Methanol CH3OH 32.04 64.7
Dimethyl carbonate (CH3O)2CO 90.08 90.5
Propylene glycol C3H8O2 76.09 188.2
Propylene carbonate C4H6O3 102.09 242.0
87
Component Formula Vapor Pressure

(mmHg)
Carbon dioxide CO2 540.4350
Methanol CH3OH 264.8488
Dimethyl carbonate (CH3O)2CO 1819.5742
Propylene glycol C3H8O2 141.4450
Propylene carbonate C4H6O3 12.5233
Component Formula Relative Volatility

Component Formula Split Fraction (ξk)


S12 S13 S16
CO2 1.9726 86.8147 1.9726 86.8147 - -
CH3OH 21.9820 704.2403 21.9753 704.0887 0.0047 0.1506
C4H6O3 10.9900 1121.969 0.0000 0.0000 10.9900 1121.9691
88
1
DMC 20.4121 1838.722 20.4100 1838.538 0.0021 0.1839
0 1
C3H8O2 20.4100 1552.996 0.0020 0.1522 20.4080 1552.8447
9
Total 75.7667 5304.893 44.3599 2629.593 31.4068 2675.2993
0 7
Streams S12 S13/16
Total mole 75.7667 75.7667
Total mass 5304.8930 5304.8930

S13 S14
CO2 1.9726 86.8147 1.9726 86.8147
CH3OH 21.9753 704.0887 21.9753 704.0887
DMC 20.4100 1838.5381 20.4100 1838.5381
89
C3H8O2 0.0020 0.1522 0.0020 0.1522

Total 44.3599 2629.5937 44.3599 2629.5937
3.3.15 Heater (H-102)

S14 S15
CO2 1.9726 86.8147 1.9726 86.8147
CH3OH 21.9753 704.0887 21.9753 704.0887
DMC 20.4100 1838.5381 20.4100 1838.5381
C3H8O2 0.0020 0.1522 0.0020 0.1522
90
Total 44.3599 2629.5937 44.3599 2629.5937
3.3.16 Pressure-Swing Distillation (High Pressure) Column (HPC-100)

Propylene carbonate C4H6O3 0
91

S15 S17 S19
CO2 1.9726 86.8147 1.9726 86.8147 - -
CH3OH 21.9753 704.0887 21.9735 704.0309 0.0018 0.0577
DMC 20.4100 1838.5381 0.0021 0.1892 20.4079 1838.3489
C3H8O2 0.0020 0.1522 - - 0.0020 0.1522
Total 44.3599 2629.5937 23.9482 791.0348 20.4117 1838.5589
Streams S15 S17/19
Total mole 44.3599 44.3599
Total mass 2629.5937 2629.5937
3.3.17 Cooler (E-103)

S17 S18
CO2 1.9726 86.8147 1.9726 86.8147
CH3OH 21.9735 704.0309 21.9735 704.0309
DMC 0.0021 0.1892 0.0021 0.1892
Total 23.9482 791.0348 23.9482 791.0348
92
3.3.18 Pressure Reducing Valve (VLV-102)

S19 S20
CH3OH 0.0018 0.0577 0.0018 0.0577
DMC 20.4079 1838.3489 20.4079 1838.3489
C3H8O2 0.0020 0.1522 0.0020 0.1522
Total 20.4117 1838.5589 20.4117 1838.5589
93
3.3.19 Cooler (E-100)

S20 S21
CH3OH 0.0018 0.0577 0.0018 0.0577
DMC 20.4079 1838.3489 20.4079 1838.3489
C3H8O2 0.0020 0.1522 0.0020 0.1522
Total 20.4117 1838.5589 20.4117 1838.5589

S18 S31
94
CO2 1.9726 86.8147 1.9726 86.8147

CH3OH 21.9735 704.0309 21.9735 704.0309
DMC 0.0021 0.1892 0.0021 0.1892
Total 23.9482 791.0348 23.9482 791.0348
3.3.21 Pressure-Swing Distillation (Low Pressure) Column (LPC-100)

Propylene carbonate C4H6O3 0

S31 S23 S22
95

CO2 1.9726 86.8147 - - 1.9726 86.8147
CH3OH 21.9735 704.030 21.9735 704.030 - -
9 9
DMC 0.0021 0.1892 0.0021 0.1892 - -
Total 23.9482 791.034 21.9756 704.220 1.9726 86.8147
8 1
Streams S18 S22/23
Total mole 21.9756 21.9756
Total mass 791.0348 791.0348

S16 S27
CH3OH 0.0047 0.1506 0.0047 0.1506
C4H6O3 10.9900 1121.9691 10.9900 1121.9691
DMC 0.0021 0.1839 0.0021 0.1839
C3H8O2 20.4080 1552.8447 20.4080 1552.8447
96
Total 31.4068 2675.2993 31.4068 2675.2993
3.3.23 Distillation Column 2 (DC-101)
Component Formula Mol. Weight Tbp

(kg/kmol) (°C)
Methanol CH3OH 32.04 64.7
Dimethyl carbonate (CH3O)2CO 90.08 90.5
Propylene glycol C3H8O2 76.09 188.2
Propylene carbonate C4H6O3 102.09 242.0
97
Component Formula Vapor Pressure

(mmHg)
Component Formula Relative Volatility



S27 S28 S29
CH3OH 0.0047 0.1506 0.0046 0.1474 0.0001 0.0032
C4H6O3 10.9900 1121.969 0.0011 0.1123 10.9889 1121.8568
1
DMC 0.0021 0.1839 0.0021 0.1839 - -
C3H8O2 20.4080 1552.844 20.4058 1552.677 0.0002 0.1674
98
7 3
Total 31.4068 2675.299 20.4136 1553.120 10.9932 1122.2684
3 9
Streams S27 S28/29
Total mole 31.4068 31.4068
Total mass 2675.2293 2675.2293
3.3.24 Cooler (E-101)

S28 S30
CH3OH 0.0046 0.1474 0.0046 0.1474
C4H6O3 0.0011 0.1123 0.0011 0.1123
DMC 0.0021 0.1839 0.0021 0.1839
C3H8O2 20.4058 1552.6773 20.4058 1552.6773
Total 20.4136 1553.1209 20.4136 1553.1209
99
3.3.25 Cooler (E-104)

S29 S32
CH3OH 0.0001 0.0032 0.0001 0.0032
C4H6O3 10.9889 1121.8568 10.9889 1121.8568
DMC - - - -
C3H8O2 0.0002 0.1674 0.0002 0.1674
Total 10.9932 1122.2684 10.9932 1122.2684
3.3.26 Cooler (E-105)

100

S23 S33
CH3OH 21.9735 704.0309 21.9735 704.0309
DMC 0.0021 0.1892 0.0021 0.1892
Total 21.9756 704.2201 21.9756 704.2201
3.3.27 Mixer (MIX-102)

S1 S22 S34
CO2 20.4100 898.2441 1.9726 86.8147 22.3826 985.0588
CH3OH - - 0.0047 0.1505 0.0047 0.1505
Total 28.0351 898.2441 1.9773 86.9652 30.0124 985.2093
101
3.4 Manual Energy Balance Calculation
In accordance to the conservation of energy, the first law of thermodynamics can

be written as shown below:
Energy out = Energy in + Generation – Consumption – Accumulation
At the steady-state condition, the first law of thermodynamics for an open system
is deduced as shown below:
Energy out = Energy in
3.4.1 Assumptions in Energy Balance Evaluation
Similar to the assumptions made for the material balances, ideal properties are
also assumed in the evaluation for the energy balances. The detailed assumptions used to
calculate the energy flow rate of each streams are listed below:
i) The kinetic and potential energies for these streams are neglected and
only enthalpy changes are considered in the calculations.
ii) All processes in the equipment are at steady-state conditions.
iii) Pressure (Po) and temperature (To) are taken at 1 atm and 298.15 K
respectively for the standard reference state or datum for enthalpy where
∆H=0.
iv) For preliminary calculations, there is no ∆H of mixing or pressure effect
on ∆H.
v) No other heat outlet or inlet from the surrounding, each unit operation
and pipe in the system is assumed perfectly insulated.
102
3.4.2 Enthalpy (∆H)
The reference state for the components are at liquid state with 298.15 K and 1
atm. The general formula of specific enthalpy for gas and liquid mixtures are:
Enthalpy for vapour phase streams:
∆Hv (T,y) = ∑
k
y k(∆ H o + C o (T) dT + ∆ H k )
f ,k ∫ p, k vap
Enthalpy for liquid phase streams:
∆HL (T,y) = ∑
k
y k(∆ H o + C o (T) dT )
f ,k ∫ p, k
where
∆ H of ,k = heat of formation for component k at standard reference state, J/mol
∫ C op , k(T) = temperature dependent heat capacities for component k, J/mol.K

y k = molar flowrate for component k, kmol/hr
Table 3.2: Heat of Formation (∆ H of ,k ) at 298.15 K and 1 atm

Component Formula Heat of Formation (∆ H of ,k ,
kJ/mol)
-117.1 (g)
Propylene oxide C3H6O
-120.81 (l)
Carbon dioxide CO2 -412.90 (l)
103
-393.50 (g)
Propylene carbonate C4H6O3 -613.80
Methanol CH3OH -238.60
Dimethyl carbonate (CH3O)2CO -607.27
Propylene glycol C3H8O2 -501.00
3.4.3 Heat Capacity
The reference state for the components are at liquid state with 298.15 K and 1
atm except for carbon dioxide which is at vapour state at the specified conditions. The
general formula of specific capacities for gas and liquid mixtures are:
Heat capacity for vapour and liquid phase streams:
∫ C op , k(T) dT = Ak (T-To) + ( Bk )(T2-To2) + (C ) (T3-To3)
Where A, B, C : constants for component k at standard reference state,

kJ/mol
T : stream temperature, °C
To : reference temperature, °C
Table 3.3: Standard heat capacity (∫ C p , k(T)) at 298.15 K and 1 atm

o
Component Heat Capacity (∆Cp,k, kJ/mol)

Propylene oxide 0.0722
Carbon dioxide 0.8440
Propylene carbonate 0.1674
Methanol 0.0811
104
Dimethyl carbonate 0.2190

Propylene glycol 0.1899
3.4.4 Heat of Vaporization (∆Hvap)
The estimation of heat of vaporization at different liquid state is determined

using the Watson’s correlation. The detailed equation for heat of vaporization is:
k k 0.38
T c −T 2
∆Hvap,k (T2) = ∆Hvap,k (Tb) x k k
T c −T b
Where T kc : critical temperature

k
Tb : atmospheric boiling point for component k
To evaluate or determine the standard heat of vaporization at the boiling point

temperature, Trouton’s rule is applied. For the components which are polar and has low
molecular weight, the equation is as follows:
∆Hvap,k (Tb) = 0.109 x T kb
Table 3.4: Standard heat of vaporization (∆Hvap,k (Tb))

Component Heat of Vaporization (∆Hvap,k, kJ/mol)
Propylene oxide 27.89
Carbon dioxide 16.70
Propylene carbonate 57.80
Methanol 35.27
Dimethyl carbonate 38.36
Propylene glycol 71.20
105
3.4.5 Energy Balance Based on Equipment
Pipeline
References : CO2 (g, 25°C, 1 atm)

ṅin Ĥin ṅout Ĥout
Substance (kmol/ (kJ/mol) (kmol/ (kJ/mol)
h) h)
CO2 (g) 22.3827 Ĥ1 22.3827 Ĥ2
For Stream 1,
Carbon dioxide (g, 25 °C, 1 atm) → Carbon dioxide (g, -78 °C, 1 atm)
6 kJ
Ḣ 1=−8.89× 10
h
For Stream 22,
Carbon dioxide (g, 25 °C, 1 atm) → Carbon dioxide (g, 52°C, 1 atm)
kJ
Ḣ 22=−0.772 ×106
h
For Stream 34,
Carbon dioxide (g, 25 °C, 1 atm) → Carbon dioxide (g, -65°C, 1 atm)
6 kJ
Ḣ 34=−8.88× 10
h
106
C-100

h) h)
CO2 (g) 22.3827 Ĥ1 22.3827 Ĥ2
For Stream 34,

Carbon dioxide (g, 25 °C, 1 atm) → Carbon dioxide (g, -65 °C, 1 atm)
6 kJ
Ḣ 1=−8.88 ×10
h
For Stream 2,
Carbon dioxide (g, 25 °C, 1 atm) → Carbon dioxide (g, 179.06 °C, 1 atm)
→ Carbon dioxide (g, 179.06 °C, 19.7 atm)
kJ
Ḣ 2=−8.67× 106
h
H-100
107

h) h)
CO2 (g) 22.3827 Ĥ2 22.3827 Ĥ3
For Stream 3,
Carbon dioxide (g, 25 °C, 1 atm) → Carbon dioxide (g, 250 °C, 1 atm)
→ Carbon dioxide (g, 250 °C, 19.7 atm)
kJ
Ḣ 3=−8.60× 106
h
P-100
References : C3H6O (l, 25°C, 1 atm)

h) h)
108
C3H6O (l) 20.41 Ĥ4 20.41 Ĥ5
For Stream 4,
C3H6O (l, 25 °C, 1 atm) → C3H6O (l, 15 °C, 1 atm)
6 kJ
Ḣ 4 =−2.49 ×10
h
For Stream 5,
C3H6O (l, 25 °C, 1 atm) → C3H6O (l, 18.49 °C, 1 atm) → C3H6O (l, 18.49 °C, 19.7 atm)
kJ
Ḣ 5=−2.48× 106
h
H-101
References : C3H6O (l, 25°C, 1 atm)

h) h)
C3H6O (l) 20.41 Ĥ5 - -
C3H6O (g) - - 20.41 Ĥ6
For Stream 6,
C3H6O (l, 25 °C, 1 atm) → C3H6O (l, 34.2 °C, 1 atm) → C3H6O (g, 34.2 °C, 1 atm)
→ C3H6O (g, 250 °C, 1 atm) → C3H6O (g, 250 °C, 19.7 atm)
6 kJ
Ḣ 6=−1.69× 10
h
109
SR-1
References : C3H6O (l, 25°C, 1 atm), CO2 (g, 25°C, 1

atm), C4H6O3 (l, 25°C, 1 atm)
h) h)
C3H6O (g) 20.41 Ĥ6 - -
CO2 (g) 22.3827 Ĥ3 1.9726 Ĥ7a
C4H6O3 (g) - - 20.41 Ĥ7b
For Stream 7,
Carbon dioxide (g, 25 °C, 1 atm) → Carbon dioxide (g, 250 °C, 1 atm)
110
→ Carbon dioxide (g, 250 °C, 19.7 atm)

7 kJ
Ḣ 7=−1.13× 10
h
C-101
References : CO2 (g, 25°C, 1 atm), C4H6O3 (l, 25°C, 1 atm)

Substance (kmol/ (kJ/mol) (kmol/h) (kJ/mol)
h)
C4H6O3 (g) 20.41 Ĥ7b 20.41 Ĥ8b
CO2 (g) 1.9726 Ĥ7a 1.9726 Ĥ8a
For Stream 8,
Carbon dioxide (g, 25 °C, 1 atm) → Carbon dioxide (g, 196.5°C, 1 atm)
7 kJ
Ḣ 8=−1.27× 10
h
MIX-100
111
References : CO2 (g, 25°C, 1 atm), C4H6O3 (l, 25°C, 1 atm),

CH3OH (l, 25°C, 1 atm), C3H8O2 (l, 25°C, 1 atm)
Inlet Outlet
Substance ṅin Ĥin ṅin Ĥin ṅout Ĥout
(kmol/h) (kJ/mol) (kmol/ (kJ/mol) (kmol/h) (kJ/mol)
h)
C4H6O3 (l) 20.41 Ĥ8b 10.99 Ĥ32a 31.4 Ĥ9b
CO2 (g) 1.9726 Ĥ8a - - 1.9726 Ĥ9a
CH3OH (l) - - 0.0001 Ĥ32b - -
C3H8O2 (l) - - 0.0022 Ĥ32c - -
For Stream 9,
Carbon dioxide (g, 25 °C, 1 atm) → Carbon dioxide (g, 355.9°C, 1 atm)
7 kJ
Ḣ 9=−1.78× 10
h
For Stream 32,
C4H6O3 (l, 25°C, 1 atm) →C4H6O3 (l, 196.5°C, 1 atm)
6 kJ
Ḣ 32=−6.38 ×10
h
112
E-102
References : C4H6O3 (l, 25°C, 1 atm), CO2 (g, 25°C, 1 atm)

Substance (kmol/h) (kJ/ (kmol/h) (kJ/mol)
mol)
C4H6O3 (l) 31.40 Ĥ9b 31.40 Ĥ10b
CO2 (g) 1.9726 Ĥ9a 1.9726 Ĥ10a
For Stream 10,

Carbon dioxide (g, 25 °C, 1 atm) → Carbon dioxide (g, 150°C, 1 atm)
7 kJ 6 kJ 7 kJ
Ḣ 10=−1.85 ×10 −0.767 ×10 Ḣ =−1.93 ×10
h h 10 h
SR-2
113
References : C4H6O3 (l, 25°C, 1 atm), CH3OH (l, 25°C, 1 atm),

(CH3O)2CO (l, 150°C, 1 atm), C3H8O2 (l, 25°C, 1 atm),
CO2 (g, 25°C, 1 atm)
Substance (kmol/h) (kJ/mol) (kmol/h) (kJ/mol)
C4H6O3 (l) 31.40 Ĥ10b 10.99 Ĥ11a
CO2 (g) 1.9726 Ĥ10a 1.9726 Ĥ11e
CH3OH (l) 62.80 Ĥ26 21.98 Ĥ11b
(CH3O)2CO (l) - - 20.41 Ĥ11c = 0
C3H8O2 (l) - - 20.41 Ĥ11d
For Stream 26,

CH3OH (l, 25°C, 1 atm) → CH3OH (l, 150°C, 1 atm)
7 kJ
Ḣ 26=−1.43 ×10
h
For Stream 11,

C4H6O3 (l, 25°C, 1 atm) → C4H6O3 (l, 150°C, 1 atm)
7 kJ
Ḣ 11=−3.47 ×10
h
P-101
114

(CH3O)2CO (l, 150°C, 1 atm), C3H8O2 (l, 25°C, 1 atm),
CO2 (g, 25°C, 1 atm)
C4H6O3 (l) 10.99 Ĥ11a 10.99 Ĥ12a
CH3OH (l) 21.98 Ĥ11b 21.98 Ĥ12b
(CH3O)2CO (l) 20.41 Ĥ11c = 0 20.41 Ĥ12c
C3H8O2 (l) 20.41 Ĥ11d 20.41 Ĥ12d
CO2 (g) 1.9726 Ĥ11e 1.9726 Ĥ12e
For Stream 12,

C4H6O3 (l, 25°C, 1 atm) → C4H6O3 (l, 150°C, 1 atm) → C4H6O3 (l, 150°C, 2 atm)
7 kJ
Ḣ 12=−3.47 ×10
h
MIX-101
115
References : CH3OH (l, 25°C, 1 atm)

Inlet Outlet
Substance ṅin Ĥin ṅin Ĥin ṅout Ĥout
(kmol/h) (kJ/mol) (kmol/ (kJ/mol) (kmol/h) (kJ/mol)
h)
CH3OH (l) 21.969 Ĥ33 40.8312 Ĥ24 62.80 Ĥ25
For Stream 24,

6 kJ
Ḣ 24=−9.73 ×10
h
For Stream 25,
CH3OH (l, 25°C, 1 atm) → CH3OH (l, 41.82°C, 1 atm)
kJ
Ḣ 25=−1.49 ×107
h
For Stream 33,
kJ
Ḣ 33=−5.23 ×10 6
h
H-103
116
References : CH3OH (l, 25°C, 1 atm)

h) h)
CH3OH (l) 62.80 Ĥ25 62.80 Ĥ26
For Stream 25,

CH3OH (l, 25°C, 1 atm) → CH3OH (l, 41.82°C, 1 atm)
kJ
Ḣ 25=−1.49 ×107
h
For Stream 26,
kJ
Ḣ 26=−1.43 ×10 7
h
DC-100
References : C4H6O3 (l, 25°C, 1 atm), CH3OH (l, 25°C, 1 atm), (CH3O)2CO (l,
150°C, 1 atm), C3H8O2 (l, 25°C, 1 atm), CO2 (g, 25°C, 1 atm)
117
ṅin Ĥin ṅout Ĥout ṅout Ĥout

Substance (kmol/h) (kJ/mol) (kmol/h) (kJ/mol) (kmol/h) (kJ/mol)
C4H6O3 (l) 10.99 Ĥ12a - - 10.99 Ĥ16a
CH3OH (l) 21.98 Ĥ12b 21.9753 Ĥ13a 0.0047 Ĥ16c
(CH3O)2CO 20.41 Ĥ12c 20.4079 Ĥ13b 0.0021 Ĥ16d

(l)
C3H8O2 (l) 20.41 Ĥ12d 0.0020 Ĥ13c 20.4080 Ĥ16b
CO2 (g) 1.9726 Ĥ12e 1.9726 Ĥ13d - -
For Stream 12,

C4H6O3 (l, 25°C, 1 atm) → C4H6O3 (l, 150°C, 1 atm) → C4H6O3 (l, 150°C, 2 atm)
7 kJ
Ḣ 12=−3.47 ×10
h
For Stream 13,
CH3OH (l, 25°C, 1 atm) → CH3OH (l, 93.52°C, 1 atm) → CH3OH (l, 93.52°C, 2 atm)
7 kJ
Ḣ 13=−1.85 ×10
h
For Stream 16,

C4H6O3 (l, 25°C, 1 atm) → C4H6O3 (l, 222.06°C, 1 atm) → C4H6O3 (l, 222.06°C, 2 atm)
7 kJ
Ḣ 16=−1.61 ×10
h
P-102
118
References : CH3OH (l, 25°C, 1 atm), (CH3O)2CO (l, 150°C, 1 atm),

C3H8O2 (l, 25°C, 1 atm), CO2 (g, 25°C, 1 atm)
CH3OH (l) 21.9753 Ĥ13a 21.9753 Ĥ14a
(CH3O)2CO (l) 20.4079 Ĥ13b 20.4079 Ĥ14b
C3H8O2 (l) 0.0020 Ĥ13c 0.0020 Ĥ14c
CO2 (g) 1.9726 Ĥ13d 1.9726 Ĥ14d
For Stream 13,

7 kJ
Ḣ 13=−1.85 ×10
h
For Stream 14,
7 kJ
Ḣ 14=−1.85× 10
h
H-102
119

C3H8O2 (l, 25°C, 1 atm), CO2 (g, 25°C, 1 atm)
CH3OH (l) 21.9753 Ĥ14a 21.9753 Ĥ15a
(CH3O)2CO (l) 20.4079 Ĥ14b 20.4079 Ĥ15b
C3H8O2 (l) 0.0020 Ĥ14c 0.0020 Ĥ15c
CO2 (g) 1.9726 Ĥ14d 1.9726 Ĥ15d
For Stream 14,

7 kJ
Ḣ 14=−1.85× 10
h
For Stream 15,
CH3OH (l, 25°C, 1 atm) → CH3OH (l, 150°C, 1 atm) → CH3OH (l, 150°C, 10 atm)
kJ
Ḣ 15=−1.82 ×107
h
HPC-100
120
References : CH3OH (l, 25°C, 1 atm), (CH3O)2CO (l, 150°C, 1 atm), C3H8O2 (l,
25°C, 1 atm), CO2 (g, 25°C, 1 atm)
ṅin Ĥin ṅout Ĥout ṅout ṅout
Substance (kmol/h) (kJ/mol) (kmol/h) (kJ/mol) (kmol/h) (kmol/h)
CH3OH (l) 21.9753 Ĥ15a 21.9735 Ĥ17a 0.0018 Ĥ19b
(CH3O)2CO 20.4079 Ĥ15b 0.0021 Ĥ17b 20.4058 Ĥ19a

(l)
C3H8O2 (l) 0.0020 Ĥ15c - - 0.0020 Ĥ19c
CO2 (g) 1.9726 Ĥ15d 1.9726 Ĥ17c - -
For Stream 15,

7 kJ
Ḣ 15=−1.82 ×10
h
For Stream 17,
CH3OH (l, 25°C, 1 atm) → CH3OH (l, 137.33°C, 1 atm) → CH3OH (l, 137.33°C, 10
atm)
kJ
Ḣ 17=−5.80 ×10 6
h
For Stream 19,
121
(CH3O)2CO (l, 150°C, 1 atm) → (CH3O)2CO (l, 183.94°C, 1 atm)

→ (CH3O)2CO (l, 183.94°C, 10 atm)
7 kJ
Ḣ 19=−1.22 ×10
h
E-103

CO2 (g, 25°C, 1 atm)
ṅin Ĥin ṅout ṅout
Substance (kmol/h) (kJ/mol) (kmol/h) (kmol/h)
CH3OH (l) 21.9735 Ĥ17a 21.9735 Ĥ18a
(CH3O)2CO (l) 0.0021 Ĥ17b 0.0021 Ĥ18b
CO2 (g) 1.9726 Ĥ17c 1.9726 Ĥ18c
For Stream 17,

CH3OH (l, 25°C, 1 atm) → CH3OH (l, 137.33°C, 1 atm) → CH3OH (l, 137.33°C, 10
atm)
6 kJ
Ḣ 17=−5.80 ×10
h
For Stream 18,
122
6 kJ
Ḣ 18=−5.97 × 10
h
VLV-101

CO2 (g, 25°C, 1 atm)
CH3OH (l) 21.9735 Ĥ18a 21.9735 Ĥ31a
(CH3O)2CO (l) 0.0021 Ĥ18b 0.0021 Ĥ31b
CO2 (g) 1.9726 Ĥ18c 1.9726 Ĥ31c
For Stream 18,

kJ
Ḣ 18=−5.97 × 106
h
For Stream 31,
kJ
Ḣ 31=−5.97 ×10 6
h
123
VLV-102

C3H8O2 (l, 25°C, 1 atm)
CH3OH (l) 0.0018 Ĥ19b 0.0018 Ĥ20c
(CH3O)2CO (l) 20.4058 Ĥ19a 20.4058 Ĥ20a
C3H8O2 (l) 0.0020 Ĥ19c 0.0020 Ĥ20b
For Stream 19,

→ (CH3O)2CO (l, 183.94°C, 10 atm)
7 kJ
Ḣ 19=−1.22 ×10
h
For Stream 20,
7 kJ
Ḣ 20=−1.27 × 10
h
VLV-100
124

(CH3O)2CO (l, 150°C, 1 atm), C3H8O2 (l, 25°C, 1 atm)
C4H6O3 (l) 10.99 Ĥ16a 10.99 Ĥ27a
CH3OH (l) 0.0047 Ĥ16c 0.0047 Ĥ27c
(CH3O)2CO (l) 0.0021 Ĥ16d 0.0021 Ĥ27d
C3H8O2 (l) 20.4080 Ĥ16b 20.4080 Ĥ27b
For Stream 16,

C4H6O3 (l, 25°C, 1 atm) → C4H6O3 (l, 222.06°C, 1 atm) → C4H6O3 (l, 222.06°C, 2 atm)
7 kJ
Ḣ 16=−1.61 ×10
h
For Stream 27,
C4H6O3 (l, 25°C, 1 atm) → C4H6O3 (l, 198.75°C, 1 atm)
7 kJ
Ḣ 27=−1.63 ×10
h
LPC-100
125
References : CH3OH (l, 25°C, 1 atm), (CH3O)2CO (l, 150°C, 1 atm), CO2 (g, 25°C,
1 atm)
CH3OH (l) 21.9735 Ĥ31a 0.0047 Ĥ22a 21.9688 Ĥ23
(CH3O)2CO 0.0021 Ĥ31b 0.0021 Ĥ22b - -

(l)
CO2 (g) 1.9726 Ĥ31c 1.9726 Ĥ22c - -
For Stream 31,

kJ
Ḣ 31=−5.97 ×10 6
h
For Stream 22,
6 kJ
Ḣ 22=−0.772 ×10
h
For Stream 23,
6 kJ
Ḣ 23=−5.18 ×10
h
E-100
126

C3H8O2 (l, 25°C, 1 atm)
CH3OH (l) 0.0018 Ĥ20c 0.0018 Ĥ21c
(CH3O)2CO (l) 20.4058 Ĥ20a 20.4058 Ĥ21a
C3H8O2 (l) 0.0020 Ĥ20b 0.0020 Ĥ21b
For Stream 20,

7 kJ
Ḣ 20=−1.27 × 10
h
For Stream 21,
(CH3O)2CO (l, 150°C, 1 atm) → (CH3O)2CO (l, 25°C, 1 atm)
7 kJ
Ḣ 21=−1.30 ×10
h
DC-101
127
References : C4H6O3 (l, 25°C, 1 atm), CH3OH (l, 25°C, 1 atm), (CH3O)2CO (l,
150°C, 1 atm), C3H8O2 (l, 25°C, 1 atm)
C4H6O3 (l) 10.99 Ĥ27a 0.0011 Ĥ28a 10.9889 Ĥ29a
CH3OH (l) 0.0047 Ĥ27c 0.0046 Ĥ28c 0.0001 Ĥ29c
(CH3O)2CO 0.0021 Ĥ27d 0.0021 Ĥ28d - -

(l)
C3H8O2 (l) 20.4080 Ĥ27b 20.4058 Ĥ28b 0.0022 Ĥ29b
For Stream 27,

7 kJ
Ḣ 27=−1.63 ×10
h
For Stream 28,
kJ
Ḣ 28=−9.91×10 6
h
For Stream 29,
6 kJ
Ḣ 29=−6.44 × 10
h
E-101
128

(CH3O)2CO (l, 150°C, 1 atm), C3H8O2 (l, 25°C, 1 atm)
C4H6O3 (l) 0.0011 Ĥ28a 0.0011 Ĥ30a
CH3OH (l) 0.0046 Ĥ28c 0.0046 Ĥ30c
(CH3O)2CO (l) 0.0021 Ĥ28d 0.0021 Ĥ30d
C3H8O2 (l) 20.4058 Ĥ28b 20.4058 Ĥ30b
For Stream 28,

kJ
Ḣ 28=−9.91×10 6
h
For Stream 30,

C4H6O3 (l, 25°C, 1 atm) → C4H6O3 (l, 25°C, 1 atm)
7 kJ
Ḣ 30=−1.02 ×10
h
129
CHAPTER 4
PRELIMINARY SIMULATION OF MATERIAL AND ENERGY BALANCE
4.1 Introduction
The process simulation of this chemical plant design is executed using a software
called ASPEN PLUS to precede the calculations. Appendix E shows the stream
summary table based on manual calculations whereas Appendix F illustrates the overall
process flow diagram and stream summary table obtained from process simulation.
The software used for the simulation, modelling and optimization of all flow
sheets was Aspen PLUS, a process simulator software that is used to create or simulate
models and optimize flow sheets. A model created in PLUS environment also features
the possibility to have sub models inside a top level model. To simulate a flow sheet, the
process is run while PLUS calculates the degrees of freedom and solves the
multivariable system. PLUS features as well the possibility to use initialization
procedures instead of assigning initial conditions on the models. Although it is really
handy, it may be time consuming especially in the column models which are really
sensitive to initial guesses.
130
4.2 Aspen PLUS Simulation
A computer based process simulator is a useful tool for designers and plant
operators in a number of ways. The ability to imagine and simulate the operations of
one’s own plant is a very crucial capability. A computer generated simulator could
provide information vital for the users to substitute data that are not readily available
from the control instrumentation and literature. Simulations of the plant could also be
used to cross check the actual performance comparing to the simulated work load and
efficiency. Thus, errors and mistakes such as faulty instruments and instrument could be
readily identified and rectified.
For the current project, the simulator program used is called Aspen PLUS. The
simulation carried out for this project is to compare the results of manual calculations
and the simulated values to provide assurance that the assumptions and calculations
made were correct and as close as possible to actual plant operations.
4.3 Absolute Relative Deviation (ARD)
After obtaining all the necessary information and values for each stream, the
manually-calculated values were compared with the simulated values to verify the
validity of the manual calculations and justify the assumptions made. ARD or
percentage error is calculated based on the equation shown below. The calculations for
error is the same for both mass balance and energy balance as well as equipment duties.
Simulation calculated value−Manually calculated value

ARD or Error (%) = x 100
Simulation calculated value
131
4.4 Comparison between Manual Calculations and Simulation Results
The summary of the comparison between manual calculations and simulation

results of each stream is shown from Table 4.1 until Table 4.3.
4.4.1 Material Balance
As shown in Table 4.1, most of the streams have low percentage errors which are
less than the limit set at 15%. As a whole, the process is still deemed acceptable since
most streams register percentage errors within the limit set.
Table 4.1: Percentage Errors of Material Balance for Each Stream

Mass Flow Rate (kg/hr)
Stream Error (%)
Manual Simulation
1 898.25 898.24 0.001
2 985.06 985.28 0.022
3 985.06 985.28 0.022
4 1185.41 1185.41 0.000
5 1185.41 1185.41 0.000
6 1185.41 1185.41 0.000
7 2170.47 2170.69 0.010
8 2170.47 2170.69 0.010
9 3292.44 3292.64 0.006
10 3292.44 3292.64 0.006
11 5304.89 5304.20 0.013
12 5304.89 5304.20 0.013
13 2629.59 2630.09 0.019
14 2629.59 2630.09 0.019
15 2629.59 2630.09 0.019
132
16 2675.30 2675.11 0.007

17 791.03 791.65 0.078
18 791.03 791.65 0.078
19 1838.56 1838.26 0.016
20 1838.56 1838.26 0.016
21 1838.56 1838.26 0.016
22 86.81 87.04 0.264
23 704.22 704.60 0.054
24 1308.23 1308.00 0.017
25 2012.45 2012.60 0.007
26 2012.45 2012.60 0.007
27 2675.30 2675.11 0.007
28 1553.12 1553.16 0.003
29 1122.27 1121.94 0.029
30 1553.12 1553.16 0.003
31 791.03 791.65 0.078
32 1122.27 1121.94 0.029
33 704.22 704.60 0.054
34 985.06 985.28 0.022
As shown in Table 4.2, most of the streams have commendable low percentage
errors which are still lesser than the limit set at 15%. Among the largest errors obtained
was found in Stream 6 at 14.996% with justifications of this error provided. As a whole,
the process is still deemed acceptable since most streams register percentage errors
within the limit set.
133
Table 4.2: Percentage Errors of Energy Balance for Each Stream

Heat Flow Rate (kJ/hr)
Stream Error (%)
Manual Simulation
1 -8.89E+06 -8.10E+06 0.113
2 -8.67E+06 -8.65E+06 0.115
3 -8.60E+06 -8.59E+06 0.116
4 -2.49E+06 -2.50E+06 0.400
5 -2.48E+06 -2.49E+06 0.402
6 -1.69E+06 -1.47E+06 14.966
7 -1.13E+07 -1.20E+07 5.755
8 -1.27E+07 -1.22E+07 4.199
9 -1.78E+07 -1.89E+07 5.835
10 -1.93E+07 -2.02E+07 4.654
11 -3.47E+07 -3.39E+07 2.511
12 -3.47E+07 -3.39E+07 2.511
13 -1.85E+07 -1.85E+07 0.062
14 -1.85E+07 -1.85E+07 0.101
15 -1.82E+07 -1.72E+07 5.752
16 -1.61E+07 -1.57E+07 2.543
17 -5.80E+06 -5.95E+06 2.537
18 -5.97E+06 -5.96E+06 0.212
19 -1.22E+07 -1.18E+07 3.905
20 -1.27E+07 -1.18E+07 7.810
21 -1.30E+07 -1.24E+07 4.604
22 -7.72E+05 -7.76E+05 0.227
23 -5.18E+06 -5.16E+06 0.485
24 -9.73E+06 -9.71E+06 0.206
25 -1.49E+07 -1.49E+07 0.260
26 -1.43E+07 -1.40E+07 2.289
27 -1.63E+07 -1.57E+07 3.369
28 -9.91E+06 -9.26E+06 7.019
134
29 -6.44E+06 -6.61E+06 2.572

30 -1.02E+07 -9.97E+06 2.608
31 -5.97E+06 -5.96E+06 0.212
32 -6.38E+06 -6.71E+06 4.918
33 -5.23E+06 -5.23E+06 0.000
34 -8.88E+06 -8.87E+06 0.001
4.4.2.1 Justifications
1) Stream 6 which recorded the largest percentage difference in terms of energy

balance at 14.966% is rather close with the 15% limit set, however, this is
probably due to the difference in the reference conditions and kinetic model used
in the ASPEN simulation software as compared to those being used in our
manual calculations.
135
CHAPTER 5
INNOVATION POTENTIAL
5.1 Comparison between Patented and New Process Flow Design
The process flow diagram for the production of dimethyl carbonate has been
developed based on the reference of previous research studies and existing patented
designs. The patented design and new process flow design that has been developed are
shown in the Appendix E. There were some significant changes or modifications made
that would improve the production rate and efficiency of the dimethyl carbonate. The
summarized modifications and their respective effects is concluded in Table 5.1.
Table 5.1: Modification to New Process Design

Modifications Patented Design New Process Design
Vapor-phase The feed streams of CO2 and The feed streams of CO2 and
reactants in Plug propylene oxide, excluding the propylene oxide, excluding
Flow Reactor methanol stream, are in liquid the methanol stream, are in
(PFR) phase. CO2 is fed in the form of vapor phase. Lower pressure
supercritical fluid which required (~20 atm) due to
requires extremely high existing natural CO2 gas.
pressure (~140 atm) to do so. Vapor-phase reactants
promote better reaction
136
velocitye.
Purification system Crude CO2 and propylene Pure CO2 and propylene oxide
for reactants is oxide are fed into the Plug are bought by distributors and
absent Flow Reactor (PFR). Possible manufacturers. Purification
purification systems for the systems are not required to
reactants are required for this avoid purchasing additional
operation. equipment for the purification
of the reactants. High purity
of CO2 and propylene oxide
are necessary for the reaction.
Recycling of There is no methanol recycle Methanol recovered from
methanol recovered operation executed which leads Low Pressure Column is large
to a large amount of waste and enough to be sufficiently
methanol wastage as well as recycled back prior entering
eventual high cost of purchase the Packed Bed Reactor
of methanol. (PBR). This can eliminate
problems posed when
methanol recycle operation is
not executed.
Pressure-swing Extractive distillation is used Pressure-swing distillation
distillation which requires an additional consists of two separate
technique is used to solvent. The solvent requires columns namely High
deal with DMC- further another separation Pressure Column and Low
methanol operation to recycle it for Pressure Column. It is used
azeotropic mixture wastage reduction purposes. when the azeotropic
Water is usually selected as the temperature and composition
solvent but it will eventually are sensitive to the operating
form another azeotropic pressure. DMC-methanol
mixture with methanol. This mixture falls in this category.
also means a far more costly It may cause high energy cost
solvent such as aniline is but it is an environmental-
137
needed. Extractive distillation friendly process and does not

is only energy-efficient when a require additional separating
suitable solvent can be found agents. Azeotropic mixture is
but it also creates dealt by merely the change in
environmental concerns. operating pressure when
extractive distillation might
require additional separation
column if the solvent forms
another azeotropic mixture
with another reactant.
CeCu catalyst is Ion-exchange resin is used. It Apart from encouraging better
used in the can only be used in a few reaction rate from 16% to
transesterification cycles and requires continuous 72% DMC yield, CeCu
reaction between maintenance every now and catalyst can be regenerated
propylene then. easily and is deemed to be last
carbonate and longer than the application of
methanol to ion exchange resin. It can be
produce DMC dried at 120°C for 12 hours
and reactivated at 500°C for 4
hours.
138
CHAPTER 6
PROCESS HEAT INTEGRATION
6.1 Introduction
Energy usage is one of the driving forces of the chemical industry, where heating
and cooling of material flow is needed to achieve the optimal conditions for the
production of certain waste or the decomposition of unneeded waste. However, most
energy consumption first seen in designs are usually wasteful, as energy circulation does
not occur in the original design. Therefore, it is crucial to conduct energy recovery
within the compounds of the production plant.
As stated before, it is important that energy could be recovered without the

addition of external utilities, such as the need for heating steam or cooling water. For
this purpose, the technique of energy integration has been long applied in the chemical
industry, which matches hot streams and cold streams in a plant to establish a heat
exchanger network and achieve the objective stated previously. Before proceeding to the
design for internal heat exchanger network, the first process flow design and its original
heat exchangers have to be determined, along with its intended energy duties, to provide
139
comparison with the utility consumption after the integration. Through this, energy
utilities could be optimised with the reduction of external utilities and the operating cost
of obtaining the utilities.
With the necessary information obtained, Pinch Technology could be used to

determine the pinch temperature point, minimum heating and cooling requirements of
the plant. Pinch point refers to the where the hot streams and the cold streams are the
most constrained and the minimum temperature difference set between the two streams
could be evident. This will be followed by the maximum recovery design, which is the
heat exchanger network placed in both above the Pinch and below the Pinch regions.
Finally, with the heat exchanger network in place, a new process flow could be created
which helps in reducing the utilities consumption.
6.2 Pinch Technology Analysis
Pinch Technology Analysis is to be applied for the heat integration of the

production plant. Out of the various methods to conduct Pinch Analysis, the Problem
Algorithm Table method was chosen to provide the analysis. The steps of how to
conduct the Problem Algorithm Table method is as shown.
Steps:
1. Extract data, such as ΔT and average heat capacity, Cp from the
simulator.
2. TS and TT are shifted according to the ΔTmin, which in most cases are
10°C. The shifted temperatures are set up in intervals and similar values
are removed.
a. For hot streams, TS & TT are shifted by deducting ½ ΔTmin.
b. For cold streams, TS & TT are shifted by adding ½ ΔTmin.
140
3. Problem Algorithm Table is used to determine heat change as basis for

heat table cascade.
4. Heat table cascade is used to determine the minimum heating
requirement, QSteam, minimum cooling requirement, and the pinch
point, TPinch, which will be shown in the next section.
5. The pairing of streams are done using maximum energy recovery (MER)
method. There are several rules of thumb to conducting this method:
a. For region above Pinch, heat exchange could only occur if CpC >
CpH.
b. For region below Pinch, heat exchange could only occur if CpH >
CpC..
6. Utility consumption and area of heat exchange is calculated accordingly.
7. Comparison between before and after the heat integration is done to
determine the MER efficiency.
6.3 Data Extraction
To calculate the energy recovery of the process, the crucial part is data extraction
where the backbone of the process energy stream dissected. The plant consists of ten
heat exchangers, E-100, E-101, E-102, E-103, E-104, H-100, H-101 H-102 and H-103
and consists of two type of stream, hot and cold. Hot streams possess surplus energy
which needs to be stripped from it while cold stream is deficit in term of energy. Thus,
pinch analysis is able to calculate the energy recovered from those streams.
Table 6.1: Stream Data Table

Type Equipment Stream Stream T in T out Q FCp
in out (°C) (°C) (kW) (kW/°C)
C1 H-100 2 3 200.8 250.0 14 0.28
C2 H-101 5 6 18.5 250.0 283 1.22
141
C3 H-102 14 15 10.8 150.0 353 2.54

C4 H-103 25 26 30.0 150.0 264 2.20
H1 E-100 20 21 183.9 25.0 167 1.05
H2 E-101 28 30 187.7 25.0 197 1.21
H3 E-102 9 10 196.0 150.0 234 5.09
H4 E-103 17 18 137.0 50.0 45 0.52
H5 E-104 29 32 241.8 196.0 30 0.66
H6 E-105 23 33 62.0 30.0 19 0.59
Composite curve is one of the good methods to set energy targets. Nevertheless,
it is inconvenient because to integrate energy for a plant, one has to base on a graphical
illustration. This inevitably will cause errors in read values because of parallax errors
making exact reading difficult to achieve. To solve this, a more systematic approach is
proposed here. This is known as the Problem Table Algorithm, which has been briefly
touched upon in the earlier part of this chapter. For this plant, ΔTmin is chosen to be
10°C, not through economic analysis but according to practical constraints. It is assumed
that shell-and-tube heat exchangers are used in this plant and therefore, the suggested
ΔTmin is 10°C (Seider, 2004).
Steps taken to perform Problem Table Algorithm analysis are listed in

chronological order as follows:-
a) Process streams are selected from Process Flow Diagram (PFD) of the
proposed plant. Selection is based on the presence of heat exchanger units
along the stream.
b) Determine hot streams and cold streams. Hot streams are streams that
need to be cooled down. Cold streams are just the opposite.
142
c) Fix ΔTmin.
d) Obtain values of flow rate (F), specific heat capacity (CP) and stream
temperature (T) from simulation results.
e) Evaluate FCP and ΔH.
f) Evaluate shifted temperature, TS for Tsupply and Ttarget.
• For hot streams, Ts,supply = Tsupply - ΔTmin/2
Ts,target = Ttarget - ΔTmin/2
• For cold streams, Ts,supply = Tsupply + ΔTmin/2
Ts,target = Ttarget + ΔTmin/2
g) List shifted temperature from top to bottom in an increasing manner.
Remove duplicates if any.
h) Evaluate ΔTint for every interval.
i) Sketch hot and cold streams with an arrowed straight line going from their
respective Tsupply to Ttarget. This way, cold streams will have straight lines
with an arrow pointing upward whereas hot streams will have arrow pointing
downward.
j) Evaluate ΣFCP,Hot – ΣFCP,Cold for every shifted temperature interval.
k) Evaluate ΔH by multiplying results from step (j) with their respective
temperature intervals. Negative values mean deficit of heat whereas positive
values mean surplus of heat.
l) Draw a heat cascade table and insert all evaluated ΔH values from top to
bottom into the table. Cascade the heat from higher to lower TS.
m) Draw another similar table and add the largest negative heat flow to the top
of the heat cascade table and cascade the heat all the way down the table.
n) Determine the pinch point. Pinch point occurs at the interval where the heat
flow is zero.
o) Determine the minimum heating, QH,min and cooling, QC,min
requirements. QH,min is the value of the largest negative heat flow added to
the top of the table. QC,min is the resultant value of heat flow at the bottom
table after cascading of heat flow.
Table 6.2: Shifted Temperature Data Table (ΔTmin=10oC)

143
Actual Shifted
Type HEX Tin Tout T′in T′out FCP ∆T Q
(oC) (oC) (oC) (oC) (kW/oC) (oC) (kW)
C1 H-100 200.8 250.0 205.8 255 0.28 71 14
C2 H-101 18.5 250.0 23.5 255 1.22 232 283
C3 H-102 10.8 150.0 15.8 155 2.54 56 353
C4 H-103 30.0 150.0 35 155 2.20 120 264
H1 E-100 183.9 25.0 178.9 20 1.05 46 167
H2 E-101 187.7 25.0 182.7 20 1.21 163 197
H3 E-102 196.0 150.0 191 145 5.09 45 234
H4 E-103 137.0 50.0 132 45 0.52 65 45
H5 E-104 241.8 196.0 236.8 191 0.66 87 30
H6 E-105 62.0 30.0 57 25 0.59 32 19
144
Table 6.3: Program Table Algorithm (PTA)
T (oC) ∆TInterval(°C) FCPnet(kW/oC)

246 H3
1 0.3704
245
45 -0.8493
201 H1
8 7.8383
193 H2
46 8.3325
174 C1
C1
19 8.6063
155
10 -0.4517
145
3 -3.3286
142 H5
H5
47 -2.7858
95 H4
H4
6 -1.5038
89 C3
22 -0.0158
67 H6
H6
12 0.4183
55
20 -0.1245
35
5 -0.5586
30
5 -2.3348
C4
145
146
Figure 6.1: Heat Cascade Diagram
Figure 6.1 clearly shows the process-to-process heat exchange where the pinch
analysis could minimize the heating and cooling utility.
147
The minimum heating requirement, QH min = 219.438 kW

The minimum cooling requirement, QC min = 0 kW
6.5 Heat Exchanger Network
The design for the heat exchanger network is started at the pinch point. There are
several rules that must be considered during the design. As mentioned before,
assumption has been made that no individual exchanger should have a temperature
difference smaller than ΔTmin. Besides, in order to achieve the energy target, set by the
composite curves, there must be no heat transfer across the pinch either by process-to-
process heat transfer or inappropriate use of utilities. To comply with this rules, the
process should be divided at the pinch, where the design is done based on the above and
below pinch.
6.5.1 Above and Below Pinch Design
For the above pinch design, the following rules must be fulfilled:
i. The temperature differences of the hot and cold streams must be greater or equal
to ΔTmin. (≥10°C).
ii. Above the pinch, only heater (eg. steam, heating oil) can be used up to QH,min.
ii. Only can pair stream where the cold stream CpC is greater or equal to hot stream
CpH (CpC ≥ CpH)
iii. Check that the temperature profile of stream matching is not crossing.
For the below pinch design, the following rules must be fulfilled:
i. The temperature differences of the cold and hot streams must be greater or equal
to ΔTmin (≥10°C).
148
ii. Below the pinch, only cooler (eg. cooling water, refrigerant) can be used up to
QC,min.
iii. Only can pair stream where the cold stream CpC is smaller or equal to hot stream
CpH (CpC ≤ CpH)
iv. Check that the temperature profile of stream matching is not crossing
196
H1 2 150
188
H2 3 25
241
H3 8 5 196
90
H4 1 25
137
H5 4 50
62
H6 7 6 30
179
250 8 7 C1
18
250 H 5 C2
219.44 kW
94
150 1 C3
30
150 6 4 3 2 C4
Figure 6.2: Grid Diagram of Heat Exchanger
Heat Exchanger 1 (H4-C3)

Q = 83.33 kW

Q = 27.78 kW
149

Q = 80.55 kW

Q = 47.22 kW

Q = 0.01 kW

Q = 11.11 kW

Q = 2.78 kW

Q = 16.66 kW
Initial heating and cooling requirement before heat integration:
Heating=( (25−13) ×0.9459 ) + ( (89−25)× 2.3348 ) + ((145−89)× 3.8228 ) + ( (174−145)×0.9459 )+ ((245−
Heating=488.89 kW
Cooling=( (246−201)×0.3704 ) + ((201−193)× 0.6039 ) + ((193−155)× 1.0981 )+ ((155−142)×0.4942 ) +
Cooling=269.45 kW
Heat recovered:
Heating=488.89 kW−219.44 kW
150
Heating=269.45 kW
Cooling=269.45 kW −0 kW
Cooling=269.45 kW
Percentage saving for heating and cooling utilities:
269.45
Heating= × 100 %
488.88
Heating=55 %
269.45
Cooling= ×100 %
269.45
Cooling=100 %
151
Figure 6.3: Heat Integrated PFD of DMC Production Plant

152
CHAPTER 7
PROCESS OPTIMIZATION
7.1 Introduction
Process synthesis is t h e s t e p in design w h e r e t h e chemical e n g i n e e r selects t h e

component p a r t s a n d how t o interconnect them t o c r e a t e his flowsheet.
Any kind of process that systematically comes up with solutions that are better
than the previews solution is known as a process optimisation Optimization can be used
in different tasks such as new system design, the synthesis of a new processing network,
and the retrofit design and operational improvements in heat exchanger, reactor, and
separation networks. This kind of process performs searches in a large search space,
hitting small, low probability targets Thus, optimisation used in chemical engineering to
find the best available option for a problem (Klemes, 2011).
7.2.1 Scope of Optimisation Problems
An objective function provides a scalar quantitative performance measure that

needs to be minimized or maximized. This can be the system’s cost, yield, and profit
(Biegler,2010). The objective function can be formulated in terms of a single variable or
a combination of dependent and decision variables. The value of the objective function
153
can be changed by manipulating the decision variables. There are two types of system
properties that determine this function:
a) Parameters
A set of characteristics that do not differ with respect to the choice to be made.
b) Variables
A set of characteristics that are allowed to differ (Klemes, 2011). Some of the
variables are specified by the decision maker or are manipulated by the
optimization tools; these are referred to as specifications or decision variables
(Klemes, 2011). The remaining variables are termed dependent variables, and
their values are determined by the specifications and the system’s internal
relationships
Behavior of a system is described by predictive model. The behavior of system

translates into a set of equations and inequalities that we term constraints. These
constraints contain a feasible region that defines limits of performance for the system
(Biegler 2010). Variables that appear in the predictive model must be adjusted to satisfy
the constraints. This can usually be accomplished with multiple instances of variable
values, leading to a feasible region that is determined by a subspace of these variables.
In many engineering problems, this subspace can be characterized by a set of decision
variables that can be interpreted as degrees of freedom in the process (Biegler 2010).
7.2 Optimization on Distillation Column (DC-101)
For this plant, the optimization process was conducted on distillation column,
DC-101. The objective function is to minimize the total cost emerge during operating
the equipment while, increase the profit of selling the product. Reflux ratio and number
of stages of the distillation column were set as the variable. The constraints is to achieve
154
at least 99% of propylene carbonate recovery. Other variables such as feed condition,
feed stage, operating pressure and temperature were at constant value to act as a
parameter.
First, Underwood shortcut method is used to calculate minimum reflux ratio, R m

by using constant average α values and assumes constant flows in both sections of
tower. For given value of q (for this case q assumed to be 1) and feed composition, θ is
determined (θ is between αHK and αLK). Then, the θ is substitute in the second equation in
order to determine Rm value. This method provides a reasonably accurate value. The two
equations to be solved in order to determine the minimum reflux ratio are as follows.
α x
∑ αi−θi , f =1−q
i
α x
∑ αi −θ
i ,d
=Rm +1
i
Next, the minimum number of stages, Nm is obtained by using Fenske equation

as stated below. The xLD is the mole fraction of light key in distillate, xLB is mole fraction
in bottoms. The average value of αL of the light key is calculated from α LD at the top
temperature (dew point) of the tower and αLB at the bottom temperature:
N m=
[(
log ⁡
xL , D D
xH , D D )( xH , B B
x L, B B )]
log [ α L ,av ]
α L ,av = √α LD α LB
155
By obtaining the minimum number of stages, Nm and minimum reflux ratio, Rm

the empirical relationship of Gilliand can be used to determine the number of stages at
desired reflux ratio. Parameter X and Y represented in the equations below:
N −N m R−Rm
Y= ,X=
N +1 R +1
Y =1−e
[( 1+54.4 X
11 +117.2 X )( XX−1 )]
0.5
From the equation listed above, it can be noticed that the number of stages
required will be dependent on the reflux ratio. Table 7.1 shows the extracted data to for
the graph of optimization.
156
Table 7.1: Extracted Data for Optimization

Number of Reflux Ratio, Annualized Total Total Cost ($)
Stages, N R Capital Cost Operating
($) Cost ($)
30 0.2537 34064.54085 162733.9398 196798.4806
29 0.2538 33637.48556 162740.9418 196378.4274
28 0.2538 33203.51279 162750.739 195954.2518
27 0.2539 32762.17416 162761.5039 195523.6781
26 0.2540 32312.98821 162773.3529 195086.3411
25 0.2541 31855.4409 162786.4613 194641.9022
24 0.2543 31388.98321 162801.0449 194190.0281
23 0.2544 30913.02839 162817.3717 193730.4001
22 0.2546 30426.94894 162835.7790 193262.7279
21 0.2547 29930.07325 162856.6968 192786.7700
20 0.2549 29422.77072 162880.6818 192303.4526
19 0.2552 28791.97204 162908.4681 191700.4401
18 0.2554 28155.32624 162941.0424 191096.3687
17 0.2558 27512.49276 162979.7631 190492.2559
16 0.2562 26863.09509 163026.5510 189889.6461
15 0.2567 26206.71498 163084.2110 189290.9259
14 0.2573 25542.87942 163160.8745 188703.7539
13 0.2581 24871.07122 163257.4324 188128.5036
12 0.2592 24190.68906 163388.2400 187578.9291
11 0.2608 23501.04439 163575.3006 187076.3450
10 0.2635 22801.28741 163889.9249 186691.2123
157
9 0.2681 22090.42122 164432.9383 186523.3596

8 0.2788 21366.78491 165704.5998 187071.3847
7 0.3108 20627.1340 169488.1066 190115.2406
6 0.3809 19869.3353 177788.0159 197657.3512
5 0.5094 19094.28024 192987.6619 212081.9422
4 0.7808 18309.06645 225108.4530 243417.5195
3 1.6938 17596.58486 333149.3899 350745.9748
Before discussing the economic trade-offs, it is important to be aware of the fact

that the three mentioned important operating parameters R (reflux ratio), N (number of
stages or trays) and P (pressure) are part of a technical relation in the sense that there are
a large number of combinations of R, N and P that will provide the desired separation
effect. For a given column pressure (P), a reduced reflux ratio (R) can be compensated
for by increasing the number of trays (N) and vice versa. Increase in number of stages
will result in larger column height and thus increased investment cost. Meanwhile, the
increase in reflux ratio will lead to increase in reboiler and condenser duties (Q R and QC)
that will result in increased operating cost (energy) and increased investment cost due to
increased heat transfer areas in the heat exchangers. The reduction in reflux ratio to
achieve the same separation effect. This means reduced reboiler and condenser duties
which in turn result in reduced operating cost (energy) and reduced investment cost due
to a reduced need for heat transfer surface in the heat exchangers. This will result in a
capital-energy trade – off of the distillation column. Figure 7.1 below shows the capital-
energy trade-off for DC-101.
158
Cost vs Number of Stages

400000
350000
300000
Annualized Cost, $
250000
200000
150000
100000
50000
0
1 6 11 16 21 26 31
Number of Trays,N
Annualized Capital Cost Total Operating Cost Total Cost (USD/year)
Figure 7.1: Capital-Energy-Trade-Off for DC-101
From the Figure 7.1, the capital cost decreases initially and increases afterwards.
Meanwhile, the total operation cost increases linearly as number of stages decrease. The
optimum condition of DC-101 is where the lowest total annualized cost achieved at
$186,523.3596 with optimum reflux ratio of 0.2681 and optimum number of stages of 9.
7.3 Comparison between Conditions Before & After Optimization
The purpose of optimization is to produce a positive change towards the process

of the whole production plant, be it from the aspect of efficiency or expenses of the
operating plant. In order to show that, the work done for optimization was not wasted,
comparison is done in terms of saving or increased in terms of cost and efficiency of
the plant respectively.
159
Table 7.2: Comparison Before and After Optimization for Distillation Column (DC-
101)
Before Optimization After Optimization
Annualized Capital 27532.1375 22090.4212
Cost ($)
Operating Cost ($) 281272.3545 164432.9383
Total Cost ($) 308804.4920 186,523.3596
Total Saved ($) 122281.1324
Percentage Saved 60.40%
The results shown are quite significant, with a cost saving of about 60.40%, a
large amount of about $122281.1324 is conserved for other purposes of the plant, which
shows the capability of what optimization could improve for the plant.
160
CHAPTER 8
EQUIPMENT SIZING AND COSTING
8.1 Introduction
Equipment sizing is the one of the important parts in the plant design project
especially when analyzing the feasibility and profitability of the plant. This is because it
involves the calculation of the equipment design as well as their respective cost which
includes the type of constructing material, length of vessel, diameter of pipelines and
some even the inner diameter. After implementing heat integration, there are 25
equipment that are involved in the dimethyl carbonate production plant. This include
major equipment such as reactors, distillation columns, flash columns, heat exchangers,
pumps and relief valves. In this section, the summary of the sizing and costing of each
equipment is outlined.
8.2 Reactors
Reactor is the heart of the chemical plant where the reactions take place to
convert the raw materials to desired products. There are a few main parameters needed
to be considered in order to design the reactor. The first parameter is the type of reactor.
161
In this chemical plant, the reactors used are Plug Flow Reactor (PFR) and Packed Bed
Reactor (PBR).
8.2.1 Plug Flow Reactor (SR-1)
The plug flow reactor involves the reaction between carbon dioxide and
propylene oxide in gaseous forms to produce propylene carbonate as one of the raw
materials needed for the production of dimethyl carbonate later on.
Main reaction:
CO2 + C3H6O  C4H6O3

Carbon dioxide Propylene oxide Propylene carbonate
Conversion: 96%
Assumptions made: - Steady state condition
- Exothermic reaction
162
Table 8.1: Plug Flow Reactor (SR-1) Equipment Specification Sheet

Equipment Specification Sheet
Item No : SR-1
Identification : Plug Flow Reactor
Function : To produce propylene carbonate from propylene oxide and carbon dioxide
Technical Specification Design Sizing
Design Type Vertical Diameter (m) 1.1549
Material of Construction Carbon steel Height (m) 4.6196
Volume (m3) 4.8399
Operating Condition
Temperature (°C) 250
Pressure (atm) 19.7
Equipment cost estimation : RM 1,142,264.57
8.2.2 Packed Bed Reactor (SR-2)
The packed bed reactor involves the transesterification reaction between

methanol and propylene carbonate to produce dimethyl carbonate as the desired
chemical product and propylene glycol as the by-product that can be sold in the market
as well.
Main reaction:
CH3OH + C4H6O3  C4H6O3 + C3H8O2

Methanol Propylene carbonate Propylene carbonate Propylene glycol
Conversion: 65%
Assumptions made: - Steady state condition
163
- Exothermic reaction
Table 8.2: Packed Bed Reactor (SR-2) Equipment Specification Sheet
Item No : SR-2
Identification : Packed Bed Reactor
Function : To produce dimethyl carbonate and propylene glycol (by-product) from
transesterification reaction between propylene carbonate and methanol
Design Type Vertical Diameter (m) 1.5556
Material of Construction Carbon steel Height (m) 6.2224
Volume (m3) 11.8254
Operating Condition
Pressure (atm) 1
8.3 Separation Columns
The separation columns used in this chemical plant include ordinary distillation
columns and a flash column aimed to facilitate desired separation of the components to
obtain a highly pure final dimethyl carbonate product.
8.3.1.1 Distillation Column 1 (DC-100)

164
Table 8.3: Distillation Column 1 (DC-100) Equipment Specification Sheet

Item No : DC-100
Identification : Distillation column 1
Function : To separate azeotropic DMC-methanol mixture from propylene glycol and
propylene carbonate
Design Type Vertical Inside Diameter 1.0713 m
Material of Stainless steel 304 Wall thickness to 0.0027 m
Construction withstand internal
pressure
Material of Mineral wool, 60 Wall thickness to 0.0041 m
insulation mm withstand wind
load, earthquakes
Height 8.8392 m Outside diameter 1.1303 m
Weight 1631.2070 kg Corrosion 0.0064 m
allowance
Column type Tray column Tray spacing 0.5080 m
Tray type Sieve
Operating Condition
Top temperature 9.41°C No. of tray 25
Bottom 222.07°C Feed tray 11
temperature
Top pressure 2 atm Feed condition Liquid
Bottom pressure 2 atm Liquid flow rate 5305.13 kg/h
165
8.3.1.2 Distillation Column 2 (DC-101)
Table 8.4: Distillation Column 2 (DC-101) Equipment Specification Sheet

Item No : DC-101
Identification : Distillation column 2
Function : To separate propylene glycol from propylene carbonate
pressure
load, earthquakes
allowance
Tray type Sieve
Operating Condition
temperature
Equipment cost estimation : RM2,513,757.02
166
8.3.1.3 High Pressure Column (HPC-100)
Table 8.5: High Pressure Column (HPC-100) Equipment Specification Sheet

Item No : HPC-100
Identification : High Pressure Column
Function : To separate DMC from azeotropic DMC-methanol mixture
pressure
load, earthquakes
allowance
Tray type Sieve
Operating Condition
temperature
167
8.3.2 Flash Column
8.3.2.1 Low Pressure Column (LPC-100)
Table 8.6: Low Pressure Column (LPC-100) Equipment Specification Sheet

Item No : LPC-100
Identification : Low Pressure Column
Function : To separate methanol from trace compounds for recycling
Material of Carbon steel Wall thickness to 0.0035 m
pressure
Material of - Wall thickness to 0.0018 m
insulation withstand wind
load, earthquakes
allowance
Operating Condition
Temperature 50°C Feed flow rate 791.53 kg/h
Pressure 1 atm Liquid flow rate 704.44 kg/h
Vapor flow rate 87.09 kg/h
168
8.4 Compressor
Table 8.7: Compressor (C-100) Equipment Specification Sheet

Item No : C-100
Identification : Screw Compressor
Function : To compress the gas feed of carbon dioxide at 1 atm to 19.7 atm
Expander Specification
Material of construction Stainless Steel Power 80.192 hp
Consumption
Molar gas flowrate 22387.74 Work Capacity 57.738 hp
mol/hr
Operating Condition
Pressure (atm) 19.7
Equipment cost estimation : RM 279,182.88
8.5 Expander
Table 8.8: Expander (C-101) Equipment Specification Sheet

Item No : C-101
Identification : Expander
Function : To compress the product stream from the PFR of 19.7 atm to 1 atm
Expander Specification
Material of construction Carbon Steel Power 104.569 hp
Consumption
Theoretical brake 2603.093 kg/h Heat Duty 74.506 hp
horsepower, PT
Operating Condition
169

Pressure (atm) 1
8.6 Pumps
8.6.1 Pump 1 (P-100)
Table 8.9: Pump 1 (P-100) Equipment Specification Sheet

Item No : P-100
Identification : Centrifugal Pump
Function : To increase pressure of C3H6O feed from 1 atm to 19.7 atm
Pump Specification Electric Motor Specifications
Material of construction Cast Steel Power 2.074 hp
Consumption
Flowrate 1185.410 kg/h
Operating Condition
Pressure (atm) 19.7
Equipment cost estimation : RM 53, 715.79
170
8.6.2 Pump 2 (P-101)
Table 8.10: Pump (P-101) Equipment Specification Sheet

Item No : P-101
Function : To increase pressure of product stream of second reactor from 1 atm to 2
atm
Material of construction Cast Iron Power 0.505 hp
Consumption
Operating Condition
Pressure (atm) 2
8.6.3 Pump 3 (P-102)
Table 8.11: Pump (P-102) Equipment Specification Sheet

Item No : P-102
Function : To increase pressure of C3H6O feed from 1 atm to 19.7 atm
Material of construction Cast Steel Power 1.756 hp
Consumption
Operating Condition
171
Pressure (atm) 19.7
8.7 Heat Exchangers
There are a wide variety of heat exchangers is available for heating, cooling,
condensing, and vaporizing process streams, particularly liquids and gases. The heat
exchangers used in this chemical plant include nine double-pipe heat exchangers and a
shell-and-tube heat exchanger aimed to transfer heat between the streams in the
production of dimethyl carbonate. For heat exchange surface areas of less than 200 ft 2,
double-pipe heat exchangers are selected over shell-and-tube heat exchangers.
Table 8.12: Heat Exchangers Equipment Specification Sheet

Heat Purchase cost
Item No. Type Area (m2)
Exchanger (RM)
1 HEX-100 Double-pipe 1.80 17,610.38
2 HEX-101 Double-pipe 1.24 16,603.82
3 HEX-102 Double-pipe 12.14 23,987.01
4 HEX-103 Shell-and-tube 19.79 122,075.19
5 HEX-104 Double-pipe 2.30 18,313.23
6 HEX-105 Double-pipe 3.47 19,562.75
7 HEX-106 Double-pipe 6.56 21,662.63
8 HEX-107 Double-pipe 10.32 23,289.60
9 HEX-108 Double-pipe 0.87 15,675.36
10 HEX-109 Double-pipe 3.21 19,311.11
Total purchase cost RM 298,091.08
172
8.8 Heaters
Table 8.13: Heaters Equipment Specification Sheet

Purchase cost
Heater Item No. Area (m2)
(RM)
1 H-100 0.66 14,994.20
2 H-101 9.08 22,821.04
Total Purchase Cost RM 37,815.24
8.9 Mixers
8.9.1 Mixer 1 (MIX-100)
Table 8.14: Mixer 1 (MIX-100) Equipment Specification Sheet

Item No : MIX-100
Identification : Mixer 1
Function : To mix propylene carbonate-filled streams from the plug flow reactor
(Stream 8) and
the propylene carbonate recycle stream from DC-101 (Stream 32)
respectively
Parameter Unit Value
Agitator speed, N rpm 1750
Volume, V m3 0.6472
Tank diameter, D m 0.5906
Tank height, H m 2.3624
Agitator diameter, Di m 0.1969
Blast pitch, P m 0.3544
Power consumption Hp 7.0972
173
Costing
Equipment Cost (RM)
Propeller 19,661.94
Pressure vessel 21,578.40
TOTAL COST 41,240.34
8.10.2 Mixer 2 (MIX-101)
Table 8.15: Mixer 2 (MIX-101) Equipment Specification Sheet

Item No : MIX-101
Identification : Mixer 2
Function : To mix pure methanol feed inlet (Stream 24) with methanol recycle stream
(Stream
33) from LPC-100
Parameter Unit Value
Agitator speed, N rpm 1750
Volume, V m3 0.4262
Tank diameter, D m 0.5138
Tank height, H m 2.0553
Agitator diameter, Di m 0.1713
Blast pitch, P m 0.3083
Power consumption Hp 3.2829
Costing
Equipment Cost (RM)
Propeller 17,246.66
Pressure vessel 17,649.19
TOTAL COST 34,895.85
174
175
CHAPTER 9
MECHANICAL DESIGN
9.1 Introduction
This chapter focuses on the mechanical engineering design of process vessels

in the production of dimethyl carbonate. The detailed mechanical designs were not
performed because mechanical engineers are the more appropriate and qualified
engineers to bear the responsibilities for that task. The design procedure was based on
British Standard BS 5500 for pressure vessels which covers vessel fabricated in
stainless and alloy steels as well as aluminium. The design was incorporated with
safety factors to ensure conservativeness in the calculations and follows the minimum
requirements dictated by the code. Besides, the appropriate materials of construction
were chosen for each equipment to withstand the operating conditions of the proposed
production plant as compared to designated operating conditions.
The design will be focused on the distillation column specifically at DC-100

which refers to the separation column for the azeotropic mixture of DMC-methanol from
other components. The following section will discuss the general design procedures. In
addition, the overall drawing depicting the mechanical design of the process vessel and
its corresponding equipment specification sheet is also presented.
176
The detailed sample calculations for the mechanical design of DC-100 are
provided in the Appendix. The mechanical design calculations are conducted based on
Chemical Engineering Volume 6, Systematic Methods of Chemical Process Design and
A Guide to Chemical Engineering Process Design and Economics.
9.2 General Mechanical Design Procedures
There are several major parameters that requires consideration when the
mechanical engineering design of a pressure vessel or a separation column is involved.
The parameters discussed are as the following.
9.2.1 Design Pressure
A vessel must be designed to withstand the maximum pressure to which it is

likely to be subjected in operation. For vessels under internal pressure, the design
pressure is normally taken as the pressure at which the relief device is set. This will
normally be 5 to 10 per cent above the normal working pressure, to avoid spurious
operation during minor process upsets. When deciding the design pressure, the
hydrostatic pressure in the base of the column should be added to the operating pressure,
if significant.
Vessels subjected to external pressure should be designed to resist the maximum

differential pressure that is likely to occur in service. Vessels likely to be subjected to
vacuum should be designed for a full negative pressure of 1 bar, unless fitted with an
effective, and reliable, vacuum breaker.
177
The pressure vessel in the production of dimethyl carbonate is subjected to

internal pressure since the vessel pressure is higher than ambient pressure. The design
pressure was taken as 10 percent of the operating pressure to avoid damage during
operation minor process offset.
9.2.2 Design Temperature
The strength of metals decreases with increasing temperature so the maximum

allowable design stress will depend on the material temperature. The design temperature
at which the design stress is evaluated should be taken as the maximum working
temperature of the material, with due allowance for any uncertainty involved in
predicting vessel wall temperatures.
9.2.3 Materials of Construction
Pressure vessels are constructed from plain carbon steels, low and high alloy
steels, other alloys, clad plate, and reinforced plastics. Selection of a suitable material
must take into account the suitability of the material for fabrication (particularly
welding) as well as the compatibility of the material with the process environment. The
pressure vessel design codes and standards include lists of acceptable materials; in
accordance with the appropriate material standards.
Thus, the process vessels that are in contact with corrosive materials or operating
at high temperature will be fabricated. In this plant, most equipment will use stainless
steel 304 instead of the higher cost of stainless steel 316 despite its better resistance to
corrosion especially for more saline or chloride-exposed environments. It is because the
stainless steel 304 is still deemed sufficient for the corrosive components existing in the
178
process streams of dimethyl carbonate production. All the other process vessels shall use
carbon steel as the material of construction.
9.2.4 Design Stress (Nominal Design Strength)
For design purposes, it is necessary to decide a value for the maximum

allowable stress (nominal design strength) that can be accepted in the material of
construction. This is determined by applying a suitable “design stress factor” (factor of
safety) to the maximum stress that the material could be expected to withstand without
failure under standard test conditions. The design stress factor allows for any
uncertainty in the design methods, the loading, the quality of the materials, and the
workmanship. For materials not subjected to high temperatures, the design stress is
based on the yield stress (or proof stress) or the tensile strength (ultimate tensile stress)
of the material at the design temperature. The values were obtained from the tabulated
data from the literature study.
9.2.5 Corrosion Allowance
The “corrosion allowance” is the additional thickness of metal added to allow for
material lost by corrosion and erosion, or scaling. The allowance to be used should be
agreed between the customer and manufacturer. Corrosion is a complex phenomenon
and it is not possible to give specific rules for the estimation of the corrosion allowance
required for all circumstances. The allowance should be based on experience with the
material of construction under similar service conditions to those for the proposed
design.
For carbon and low-alloy steels, where severe corrosion is not expected, a
minimum allowance of 2.0 mm should be used; where more severe conditions are
179
anticipated, this should be increased to 4.0 mm. Most design codes and standards specify
a minimum allowance of 1.0 mm.
Corrosion allowable of 4 mm was added to the maximum wall thickness of each

equipment which is the minimum allowable limit. The dimethyl carbonate production
plant has contacts with corrosive materials and the corrosion allowable was made for
conservatism and as a safety factor to allow for material cost by erosion.
9.2.6 Design Weight of Loads
A structure must be designed to resist gross plastic deformation and collapse

under all the conditions of loading. The loads to which a process vessel will be subject in
service are listed below. They can be classified as major loads that must always be
considered in vessel design, and subsidiary loads. Formal stress analysis to determine
the effect of the subsidiary loads is only required in the codes and standards where it is
not possible to demonstrate the adequacy of the proposed design by other means; such as
by comparison with the known behavior of existing vessels.
They are seven major sources of dead weight loads:
 Vessel shell
 Vessel fitting (man-way, nozzles)
 Internal fitting, plate (plus the fluid on the plates), heating and cooling coils
 External fitting, ladders, platforms, piping
 Auxiliary equipment which is not self-supported, condenser, agitators
 Insulation
 Weight of liquid to fill vessel (the vessel will be filled for hydraulic
pressure test and may fill with process liquid due to offset (miss-
operating).
180
9.2.7` Wall Thickness
There will be a minimum wall thickness required to ensure that any vessel is
sufficiently rigid to withstand its own weight, and any incidental loads. As a general
guide the wall thickness of any vessel should not be less than the values given below;
the values include a corrosion allowance of 2 mm. The maximum wall thickness will
include vessels internal pressure and design pressure.
Table 9.1: Minimum Practical Wall Thickness

Vessel Diameter (m) Minimum thickness (mm)
1 5
1 to 2 7
2 to 2.5 9
2.5 to 3.0 10
3.0 to 3.5 12
9.2.8 Design of Domed Head
The end of cylindrical vessels is closed by head of various shapes such as flat
plates, hemispherical heads, ellipsoidal or torispherical heads. The choices of the
closure for the vessels in the dimethyl carbonate production plant were based on the
operating pressure.
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9.2.9 Analysis of Stresses
Analysis of stresses were performed to determine pressure, dead weight and

bending stress and check to ensure that it is below the maximum allowable design stress.
9.2.10 Welded Joint Efficiency
The strength of a welded joint will depend on the type of joint and the quality of
the welding. The soundness of welds is checked by visual inspection and by non-
destructive testing (radiography). The possible lower strength of a welded joint
compared with the virgin plate is usually allowed for in design by multiplying the
allowable design stress for the material by a “welded joint factor” J. The value of the
joint factor used in design will depend on the type of joint and amount of radiography
required by the design code. Typical values are shown in Table 9.2. Taking the factor as
1.0 implies that the joint is equally as strong as the virgin plate; this is achieved by
radiographing the complete weld length, and cutting out and remaking any defects. The
use of lower joint factors in design, though saving costs on radiography, will result in a
thicker, heavier, vessel, and the designer must balance any cost savings on inspection
and fabrication against the increased cost of materials.
Table 9.2: Maximum Allowable Joint Efficiency

Degree of radiography
Type of Joint
100% Spot None
Double-welded butt
1.00 0.85 0.70
or equivalent
Single-weld butt
joint with bonding 0.90 0.80 0.65
strips
9.2.11 Vessel Support Design

182
The method used to support a vessel will depend on the size, shape, and weight
of the vessel; the design temperature and pressure; the vessel location and arrangement;
and the internal and external fittings and attachments. Horizontal vessels are usually
mounted on two saddle supports; Figure 9.1. Skirt supports are used for tall, vertical
columns; Figure 9.2. Brackets, or lugs, are used for all types of vessel; Figure 9.3. The
supports must be designed to carry the weight of the vessel and contents, and any
superimposed loads, such as wind loads. Supports will impose localized loads on the
vessel wall, and the design must be checked to ensure that the resulting stress
concentrations are below the maximum allowable design stress. Supports should be
designed to allow easy access to the vessel and fittings for inspection and maintenance.
Figure 9.1: Horizontal Cylindrical Vessel on Saddle Supports

183
Figure 9.2: Typical Skirt-Support Designs (a) Straight Skirt (b) Conical Skirt
Figure 9.3: Bracket Supports (a) Supported on Legs (b) Supported from Steel-Work
184
9.3 Summary of Mechanical Design of Equipment DC-100
The overall drawing shows the mechanical design of engineering that indicates
the important dimension of the equipment. Also, the equipment specification data sheet
was prepared for the equipment along with its estimated cost in the dimethyl carbonate
production plant. It must be emphasized that the estimated cost of the equipment was
based on the results of economic analysis and fixed capital cost which is presented in the
Chapter 9. The detailed sample calculations for this mechanical design are shown in the
Appendix.
Figure 9.4: Mechanical Design Drawing of Distillation Column 1 (DC-100)
Table 9.3: Specification Design Sheet of Distillation Column 1 (DC-100)

Equipment Specification Design Sheet
Identification Azeotropic Mixture Separation
Item No DC-100
Function To separate azeotropic DMC-methanol
mixture from propylene glycol and
propylene carbonate
Specifications
Design orientation Vertical
Column type Sieve
Number of plates 15
Operating Conditions Weight of Load
Temperature (°C) Vessel (kN)
Operating pressure (atm) Plate (kN)
Design pressure (atm) Total weight (kN)
Design stress (N/mm2)
Material of construction
Average wall thickness
185
(in)
Wind loading (kN/m)
Bending moment (MNm)
Head and Closure Design Analysis of Stress
Type Horizontal pressure
stress (N/mm2)
Thickness (mm) Longitudinal pressure
stress (N/mm2)
Dead weight stress
(N/mm2)
Bending stress (N/mm2)
Longitudinal stress
(N/mm2)
Upwind
Downwind
Elastic stability
(N/mm2)
Skirt Support Design
Total weight loading (kN)
Bending moment at skirt base (kNm)
Bending stress (N/mm2)
Maximum resultant stress (N/mm2)
Tensile strength
Compressive strength
Skirt thickness (mm)
Cost per equipment
186
CHAPTER 10
Waste Treatment
10.1 Introduction
This chapter will deal with wastes generated from the production of dimethyl
carbonate. Raw materials that were used in the production will undergo a series of
processing steps and generate several by-products as well as the desired product in
which unwanted products can be sold to generate additional income or utilized in other
environmental-friendly ways. Since it is impossible to achieve a complete (100%)
conversion rate of the raw materials into valuable products, the generation of residual
waste is inevitable and alternatives are introduced to reduce the detrimental effects
caused by these residual waste towards the environment and society.
In Malaysia, the Department of Environment (DOE) is responsible to ensure that

a waste treatment is present in all chemical plants prior to the treatment of the waste to
an acceptable form or level before discharge. The pollution of the environment and
imbalance of the natural ecosystem such as aquatic ecosystem can be caused by the
direct discharge of untreated waste materials. Besides, there is also the economic
187
considerations whereby the treated waste can be recovered for production purposes or
sold as another useful by-product. With that, there are two approaches identified to deal
with the waste generated by any form of industry namely waste minimization and end-
of-pipe treatment.
Waste minimization involves the elimination or reduction of the harmful and

persistent waste generated from the source of the reaction between raw materials or the
excess unreacted materials from the similar reaction. It also involves redesigning
products or changing societal patterns, concerning consumption and production of waste
generation, to prevent the creation of waste. The most environmentally resourceful,
economically efficient and cost effective way to manage waste is to not have to address
the problem in the first place. Waste minimization should be seen as a primary focus for
most waste management strategies as it can contribute to the reduction in capital cost
and operation time.
The end-of-pipe treatment, on the other hand, involves the transformation of the
waste generated into another form of useful or less harmful materials or components by
physical, chemical and biological methods or the combination of several methods. This
ensures the safe discharge of the transformed waste that will not cause extreme
detrimental effects to the environment. Hazardous waste materials, despite the treatment
made, can be directed to established waste treatment facilities or organizations such as
the waste management center of Kualiti Alam at Port Dickson, Negeri Sembilan.
The effective waste management system is illustrated by the waste management

hierarchy. The top priority option in waste management decisions aspect lies on
pollution prevention or source reduction. The waste management is led by source
reduction which is followed by recycling. Source reduction refers to the preferably direct
188
in-situ waste reduction due to the fact that generation or accumulation of the waste
materials will still occur in a recycle loop. Waste treatment should only be considered
before the final preferable disposal option is considered when these two preferred
options are no longer possible.
Figure 10.1 below shows the hierarchy of waste management in the order from
the most preferred options to the least preferred ones.
Figure 10.1: Waste Management Hierarchy
Table 10.1: Description of Waste Management Hierarchy

Terms Description
Prevention Prevention of waste production at the
plant at first
Minimization Minimize waste generation
Reuse Reuse of waste stream as an ingredient in
a productive process or recovery of a
reusable component
Recycling Recycling of waste
Energy recovery The use of physical, chemical, biological
189
or thermal technologies to reduce the

volume, toxicity and/or mobility of waste
Disposal The placement of waste into landfill or
the underground injection of waste
10.3 Waste Minimization and Pollution Prevention
Waste minimization and treatment in terms of reuse or recycling are considered

as the top priorities option in effluent handling. The best solution in dealing with
effluents is to avoid the waste production at the first place or in other words, waste
production is minimized. This can help to reduce waste treatment and raw materials
purchasing cost at the same time. However, if it is inconvenient or difficult to reduce the
extent of waste generation at the reaction point of view, the waste can either be treated in
a more sustainable approach or reused for a beneficial purpose. The significance of both
waste minimization and waste treatment are explored as shown in Table 10.2 below.
Table 10.2: Description of Waste Minimization and Waste Treatment

Term Description
Waste minimization The reduction of waste to a feasible extent, of any solid or
hazardous waste prior to any treatment, storage or
disposal
Waste treatment The dealing of waste by means of certain techniques to
achieve a reduction in volume, toxicity and/or mobility of
waste after the waste has been generated and prior to
disposal
190
10.3.1 Objectives of Waste Minimization and Waste Treatment
The waste minimization and waste treatment plant is entitled to achieve the
following objectives as stated below when dealing with waste generation.
a) Reduce waste treatment and disposal cost, raw material purchasing cost and
other operating costs such as utility costs.
b) Meet state and national waste minimization and treatment policy goals.
c) Reduce potential environmental liabilities.
d) Protect public health and workers’health.
The summary of waste minimization and pollution prevention is presented in Figure

10.2 below.
Figure 10.2: Waste Minimization Techniques

191
10.4 Air Quality Standard Information
Ambient air quality standard is a national target for an acceptable concentration

specific pollutant in air. Under the Clean Air Act, EPA develops two standards pollutant
of concern.
1) A primary standard to protect public health. The Clean Air Act mandated
primary standards to be based entirely on health-related information, without
considering the cost of attaining the standard.
2) A second standard to protect public welfare. Public welfare includes soils, water,
crops, vegetation, buildings, property, animals, wildlife, weather visibility,
transportation and other economic values as well as personal being.
The Clean Air Act, which was last amended in 1990, requires EPA to set
National Ambient Air Quality Standards for pollutants considered harmful to public
health and the environment.
The EPA Office of Air Quality Planning and Standards (OAQPS) has set
National Ambient Air Quality Standards for six principal pollutants, which are called
“criteria” pollutants. They are listed as in Table 10.5 as shown below.
Table 10.3: ‘Criteria’ Pollutants under National Ambient Air Quality Standards
Pollutant Primary / Averaging Level Form
Secondary Time
Carbon monoxide Primary 8 hours 9 ppm Not to be
(CO) 1 hour 35 ppm exceeded more
than once per
year
Lead (Pb) Primary and Rolling 3 0.15 Not to be
192
secondary month µg/m3 exceeded

average
Nitrogen dioxide Primary 1 hour 100 ppb 98th percentile of
(NO2) 1-hour daily
maximum
concentrations,
averaged over 3
years
Primary and 1 year 53 ppb Annual mean
secondary
Ozone (O3) Primary and 8 hours 0.070 ppm Annual fourth-
secondary highest daily
maximum 8-
hour
concentration,
averaged over 3
years
Particle PM2.5 Primary 1 year 12.0 Annual mean,
Pollution µg/m3 averaged over 3
(PM) years
Secondary 1 year 15.0 Annual mean,
µg/m3 averaged over 3
years
Primary and 24 hours 35 µg/m3 98th percentile,
secondary averaged over 3
years
PM10 Primary and 24 hours 150 µg/m3 Not to be
secondary exceeded more
than once per
year on average
over 3 years
193
Sulfur dioxide (SO2) Primary 1 hour 75 ppb 99th percentile of

1-hour daily
maximum
concentrations,
averaged over 3
years
Secondary 3 hours 0.5 ppm Not to be
exceeded more
than once per
year
10.5 Methodology
This chapter deals with the methodology of the evaluation work of waste
minimization in dimethyl carbonate production plant. They include:
1) Waste Sources Definition

2) Waste Sources Description
3) Air Quality Standard information
4) Selection of Treatment Methods / Alternatives
5) Waste Treatment Plant Design / Alternatives
10.4.1 Waste Sources Identification
In the production of dimethyl carbonate, there is no waste generated. There is

only one stream that is meant as a waste stream, namely Stream 22 which consists
mainly of carbon dioxide but it is then recycled back to the feed inlet to the plug flow
reactor (SR-1) for further reaction to produce propylene carbonate for dimethyl
194
carbonate production. Thus, there is no imperative need of a wastewater treatment

plant for this dimethyl carbonate production plant.
195
CHAPTER 11
PROCESS CONTROL AND INSTRUMENTATION
11.1 Introduction
The importance of a proper design of control system in a chemical plant is partly

relevant in enabling a better and convenient handling and monitoring of the process flow
without the need of a large number of operators to do so which may prove to be rather
costly. With that, a proper design of a control system on the process will allow the plant
to somehow operate automatically and continuously which will also rectify errors upon
detection whereby the requirement of human actions and decisions is involved before
further implications and problems are allowed to happen.
As a matter of fact, the design of a control system will involve a large number of
theoretical and practical considerations such as the quality of the control response,
stability of the operating plant, the reliability of the control system, the range of control
and ease of start-up, shut down and change over, the ease of operation and the cost of
control system.
196
11.2 Objectives of Process Control
There are several reasons behind the provision of automated process control in a
chemical plant, be it from safety, production, operating or economic perspectives. In
other words, it could be seen as constraints or conditions in which the process control
will operate within the boundaries of the stated constraints or conditions. The
requirements that are involved and considered in relation to process control will be
discussed in the following section.
11.2.1 Safety
For a typical chemical process, the primary requirement is the safe operation for
the well-being of people in the plant and conservation of economic resources of the
process in terms of safety measures allocation. Therefore, it would be best that the
operating conditions including pressure, temperature, concentration of certain
components and other parameters are ensured within the safety limits in order to reduce
the risk of any serious, life-threatening accidents or incidents such as explosions.
11.2.2 Product Specifications
A plant should achieve the desired production rate and product quality during the
initial design of the plant. The process control design in this plant will complement the
plant to effectively and efficiently produce 15,000 MTA of dimethyl carbonate from the
transesterification of methanol and propylene carbonate. Besides the production rate, the
purity of dimethyl carbonate should be taken into consideration too whereby a specific
standard should be achieved.
197
11.2.3 Operating Constraints
Operating constraints usually refers to the equipment’s capability to function and

perform with the appropriate measures. For example, certain levels in vessels and
columns should not exceed the operating limit as it would flood the equipment and cause
overflow and backflow, compromising the safety and efficiency of the equipment. The
process control loops are set up to assist the conditions to remain in the suitable range of
said equipment.
11.2.4 Economic Considerations
Process control is also created to reduce the excessive utilization of raw materials
or utilities while maintaining the product quality at specified levels. With that, the plant
will be able to conserve economic resources and at the same time, still reaping the
profits at higher margins. Also, other constraints are also satisfied through the
establishment of process control systems.
11.3 Controller Configurations
In process control design, there are several controller configurations that can be
considered to be implemented according to the needs of the plant itself. The most
common controller strategy is the feedback control which is followed by feed forward
control. Some other type of controller strategies discussed includes cascade control and
ratio control.
198
11.3.1 Feedback Control
Feedback control is the most common control configurations in the process

industry. It is due to the simple need of minimal knowledge about the process to be
controlled. In feedback control, the control will detect offsets in the measured
parameters and corrective actions are enabled through manipulating variables that will
affect the measured parameters. Despite that, it has its own disadvantages. For instance,
it does not execute the corrective actions until after a deviation in the controlled variable
occurs, thereby making perfect control effectiveness impossible to achieve. It does not
provide predictive control action to compensate for the effects of known or measurable
disturbances.
11.3.2 Feed forward Control
Unlike feedback control, feed forward control configuration usually measures

disturbances instead of the controlled variables and corrective actions are enabled before
offsets could occur in the controlled variables. This would result in better quality
products output constantly but disadvantages are also present for feed forward control
system. For example, in order to have an effective use of the control configuration,
sufficient knowledge has to be known by the user in order to estimate changes in the
manipulated variable made by the disturbances and manipulated variables.
11.3.3 Ratio Control
Ratio control is a distinguished type of feed forward control that has a

widespread application in the process industries. Its objective is to maintain the ratio of
two process variables at a specified value and the variables mentioned are usually flow
199
rates. Ratio control could be used to specify relative amounts of components in blending
operations, maintain a stoichiometric ratio of reactants to a reactor, keeping a specified
reflux ratio for a distillation column and holding the fuel-air ratio to a furnace at the
optimum value.
11.3.4 Cascade Control
Cascade control is an alternative approach which can significantly improve the

dynamic response to disturbances. Another set of secondary measurement point and
secondary feedback controller is added to the original set. The secondary measurement
point is located so that it recognizes the upset condition sooner than the controlled
variable. It is widely used in the application when disturbances are associated with the
manipulated variable or when the final control element exhibits nonlinear behavior.
11.4 Piping and Instrumentation Diagram (PID) Elements
The piping and instrumentation diagram provides a graphical representation of

control configurations required for the process. It illustrates the measurement devices,
controllers as well as actuators of the control loop. The standard measurement is
developed based on the International Society of Automation in developing the plant’s
P&ID using specific symbols known as legends to help point out the actual instruments
needed. The legends of the diagram are shown in Table 10.1 with their respective
descriptions.
200
Table 11.1: Basic Symbols in Piping and Instrumentation Diagram (P&ID)

Hardware Element Symbol Description
Indicator TIC Temperature Indicator Controller
PIC Pressure Indicator Controller
FIC Flow Indicator Controller
LIC Level Indicator Controller
Controller TC Temperature Controller
PC Pressure Controller
FC Flow Controller
CC Composition Controller
Transmitter TT Temperature Transmitter
PT Pressure Transmitter
LT Level Transmitter
FT Flow Transmitter
Alarm TA Temperature Alarm
PA Pressure Alarm
LA Level Alarm
Valve Controller Diaphragm Valve
Pneumatic Transmission Line

Transmission Line
Electric Transmission Line
Table 11.2: General Functions of Control Elements

Pressure Control Instruments
Instrument Function
PI Detects the pressure change in the equipment
PC Makes the decision what action should be done. Decision is
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sent to final control element (valve) to do an action.

PAH Detects high pressure in equipment. When pressure exceeds
the pressure limit, it sends a signal to the PC.
PAL Detects low pressure in the equipment. When pressure is
lower than the pressure limit, it sends a signal to the PC.
PRA Monitors the pressure of the system
Temperature Control Elements
TI Detects the temperature change in the equipment
TC Makes the decision about the temperature. Decision is sent to
the final control element (valve) to do an action
TAH Detects high temperature in equipment. When temperature
exceeds temperature limit, it send a signal to TC.
TAL Detects low temperature in equipment. When temperature is
lower than temperature limit, it sends a signal to TC.
Flow Control Elements
FI Detects the flow in the streamline to the major equipment.
This element will detect the flow change in the streamline.
FC Makes a decision on what action should be taken.
FRA To monitor the flow rate of the stream
Liquid Level Control Element
LI Detects the liquid level change
LC Makes a decision what action should be taken
LAH Detects higher liquid level change
LAL Detects lower liquid level change
Composition Control Element
CI Detects the composition change
CRA To monitor the concentration of distillate component
CC Makes a decision what action should be taken
* The installation of PIA, TIA and LIA will make the signal (pressure, temperature and
level) more sensitive to be detected.
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11.5 Individual Unit Control System
11.5.1 Control System for Reactors (SR-1 and SR-2)
It is important for reactors to have control systems of their own because they are the most crucial parts in a chemical plant in
the production of the desired component. The stability of the reactor needs to be maintained in a way that is able to sustain the
productivity of the plant as well as the safety of all those that are involved in the plant operation.
Table 11.3: Control Loops for Reactors (SR-1 and SR-2)

Reactors (SR-1 and SR-2)
To control the temperature of the reactors (SR-1 and SR-2) at
Control Objective 1 :
250°C and 150°C respectively
Controlled Measured Manipulated Control
Disturbances Justifications
variables variables variables configuration
Temperature of  Temperature of Amount of heating Temperature of Cascade Temperature is
reactor reactor steam entering the reactor influent maintained to
 Temperature of jacket assure that there is
steam entering no runaway
jacket reaction and the
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reaction rate is
maintained
To maintain the pressure of the reactors (SR-1 and SR-2) at 19.7
atm and 1 atm respectively
Pressure of reactor  Pressure of Amount of mass Flow rate inlet to Feedback The pressure should
reactor flow leaving the reactor be controlled to
reactor prevent accidents
such as explosions
as well as to
maintain the
reaction rate
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(a)
205
(b)
Figure 11.1: Process Control Loop of Reactors (a) SR-1, (b) SR-2
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11.5.2 Control System for Distillation Column 1 (DC-100)
The distillation column serves to separate the desired product from the other by-products or undesired materials. The
distillation column, however, is quite sensitive to changes in operating conditions such as temperature, pressure and others. Therefore,
it is important that a process control system is present to prevent off-sets in the operating conditions of the separation unit.
Table 11.4: Control Loops for Distillation Column 1 (DC-100)

Distillation Column 1 (DC-100)
Control Objective 1 : To control the level in the distillation column
Level in distillation Level in distillation Flow of stream at Inlet feed Feedback The level should be
column column bottoms maintained to avoid
overflow in the
column and to
ensure the safety of
the workers
exposed
Control Objective 2 : To control the pressure of the distillation column

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Pressure of Pressure of Flow of gas stream Temperature of gas Feedback The pressure should
distillation column distillation column leaving at top of stream leaving at be maintained to
column top of column prevent pressure
build-up and to
ensure that the
separation
efficiency is high
Control Objective 3 : To control the level of the condenser tank
Level of condenser Level of condenser Flow of cooling Temperature of Feedback The level of the
tank tank water entering cooling water condenser is
condenser maintained to avoid
the occurrence of
overflow in the tank
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Figure 11.2: Process Control Loop of Distillation Column 1 (DC-100)

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11.5.3 Control System for Distillation Column 2 (DC-101)
Table 11.5: Control Loops for Distillation Column 2 (DC-101)

Distillation Column 2 (DC-101)
overflow in the
column and to
the workers
exposed

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build-up and to
ensure that the
separation
efficiency is high
the occurrence of
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Figure 11.3: Process Control Loop of Distillation Column 2 (DC-101)

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11.5.4 Control System for High Pressure Column (HPC-100)
Table 11.6: Control Loops for High Pressure Column (HPC-100)

High Pressure Column (HPC-100)
overflow in the
column and to
the workers
exposed

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build-up and to
ensure that the
separation
efficiency is high
the occurrence of
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Figure 11.4: Process Control Loop of High Pressure Column (HPC-100)
11.5.5 Control System for Low Pressure Column (LPC-100)

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The low pressure column in this plant will function almost similarly to a flash column which also operates on the basis of
pressure and temperature change. Therefore, it is important that these conditional parameters are kept in check in order to obtain
products of high purity and quality. In order to achieve this, process control design is important for the flash column to be fully
functional and efficient.
Table 11.7: Control Loops for Low Pressure Column (LPC-100)

Low Pressure Column (LPC-100)
Control Objective 1 : To control the level in the flash column
Level in column Level in column Flow of Stream 23 Inlet flow of Stream Feedback The level should be
31 maintained to avoid
overflow in the
column and to ensure
the safety of the
workers exposed
Control Objective 2 : To control the pressure of the distillation column at 1 atm

Controlled Measured Manipulated Disturbances Control Justifications
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Pressure of column Pressure of column Flow of Stream 22 Amount of gas Feedback The pressure should
composition in be maintained to
Stream 31 prevent pressure
build-up and to
ensure that the
separation efficiency
is high
Control Objective 3 : To control the temperature of the column at 25°C
Temperature of  Temperature of Amount of cooling Temperature of Cascade Temperature of the
column vessel water entering heat influent to heat vessel should be
 Temperature of exchanger … exchanger … maintained to produce
cooling water separation of highest
efficiency between
methanol and other
undesired
components
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Figure 11.5: Process Control Loop of Low Pressure Column (LPC-100)

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11.5.6 Control System for Pressure-Reducing Valve 1 (VLV-100)
The pressure-reducing valves in this chemical plant aim mainly to create a reduction in pressure for liquid-phase streams in
order to complement the operating pressures required for individual unit operations and to achieve suitable product condition for
proper storage. This explains the need for a process control system to ensure the pressure reduction operation functions as desired
without compromising the feasibility of the process and the safety of the personnel involved directly with it.
Table 11.8: Control Loops for Pressure-Reducing Valve 1 (VLV-100)

Pressure-Reducing Valve 1 (VLV-100)
Control Objective 1 : To control the pressure of Stream 27 inlet to DC-101
Pressure of Stream Pressure of Stream Flow rate of liquid Flow rate of Stream Feedback The pressure should
27 inlet to DC-101 27 inlet to DC-101 in Stream 16 27 inlet to DC-101 be maintained to
prevent pressure
build-up
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Figure 11.6: Process Control Loop of Pressure-Reducing Valve 1 (VLV-100)

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Control Objective 1 : To control the pressure of Stream 31 inlet to LPC-100
31 inlet to LPC-100 31 inlet to LPC-100 in Stream 18 31 inlet to LPC-100 be maintained to
prevent pressure
build-up
221

222

To control the pressure of Stream 20 inlet for final DMC product
storage and handling
20 20 in Stream 19 20 be maintained to
prevent pressure
build-up and for the
purpose of proper
storage and
handling of DMC
223

224
Table 11.11: Control Loops for Heater 1 (H-100)

Heater 1 (H-100)
Control Objective 1 : To control the temperature of Stream 21 at 25°C
Temperature of Temperature of Amount of heating Temperature of Feedback Temperature of
Stream 3 Stream 3 liquid entering Stream 2 Stream 3 is to be
heater H-100 maintained to
provide best
conversion for the
reaction in SR-1
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Figure 11.9: Process Control Loop of Heater 1 (H-100)

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Table 11.12: Control Loops for Heater 2 (H-101)

Heater 2 (H-101)
Control Objective 1 : To control the temperature of Stream 10 at 150°C
Temperature of Temperature of Amount of heating Temperature of Feedback Temperature of
Stream 6 Stream 6 liquid entering Stream 5 Stream 10 is to be
heater H-101 maintained to
provide best
conversion for the
reaction in SR-1
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Figure 11.10: Process Control Loop of Heater 2 (H-101)

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Table 11.13: Control Loops for Pump 1 (P-100)

Pump 1 (P-100)
Control Objective 1 : To control the outlet flow of pump
Flow rate of Stream Flow rate of Stream Flow rate of Stream Inlet flow of Stream Cascade The flow rate should
5 5 4 4 be maintained to
avoid overpressure in
the pump
Control Objective 2 : To control the pressure of the pump
Pressure of pump Pressure of pump Flow of Stream 4 Inlet flow of Stream Cascade The pressure should
4 be maintained to
prevent pressure
build-up and maintain
safety
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Figure 11.11: Process Control Loop of Pump 1 (P-100)

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Pump 2 (P-101)
the pump
11 be maintained to
prevent pressure
safety
231

232

Pump 3 (P-102)
the pump
13 be maintained to
prevent pressure
safety
233

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Figure 11.14: Process & Instrumentation Diagram (P&ID) for DMC Production Plant
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CHAPTER 12
PROCESS SAFETY
12.1 Introduction
Safety, hazard and risks are some of the issues or terms that are closely related to
a chemical process safety. Safety or loss prevention is the prevention of accidents by
using appropriate technologies or procedural methods to identify the hazards created by
a chemical plant and to eliminate them before an accident occurs. Hazard, on the other
hand, is defined as any possible unpredictable factors that have the potential to cause an
accident whereas risk is related to the extent of probability of a particular hazard that
will result in an accident.
Therefore, due to the emergence of the knowledge and awareness of these danger
signs, many significant advanced technologies and progressive methods have been
created and implemented in chemical process safety ever since. Safety is important in
the development of scientific disciplines nowadays which include many highly technical
and complex theories and practices. The chemical industry has traditionally devoted
considerable attention to safety, beginning with the research and development of new
processes through plant design and construction. In a chemical plant, the main hazards
usually involve toxic and corrosive chemicals, explosions, fires and accidents which is
rather common as well among other industrial activities. The Health and Safety at Work
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Act 1974 provided a new legal administrative framework to promote, simulate and
encourage even higher standards of health and safety at work.
There are several safety aspects that needs to be considered in chemical

production plants such as chemical storage and handling, chemical transportation, plant
location and safety precautions for the workers’ well-being. In order to build a new
chemical plant, the plant must be sufficiently far apart from any housing area. Besides,
the plant layout has to be considered as well which refers to the location of the
equipment in the plant. Any chemicals used in the plant have to be labeled as dangerous
and it is a good measure in getting familiar with the chemical’s characteristics and
hazards prior to usage. The individual safety aspects are considered as described in the
following.
12.2.1 Storage and Handling of Chemicals
The proper storage and handling of hazardous chemicals is important because

their presence itself pose significant risk in huge amount if not monitored or handled
appropriately since various chemicals are also occasionally used for other processes such
as water treatment, cleaning, waste treatment and others. The precautionary measure that
can be undertaken is to ensure that the storage tank farm should not be situated adjacent
to any urban development areas to eliminate any possibility of events such as Vapor
Cloud Explosion (VPE), fireball or toxic cloud that could drift over the population
nearby. This also refers to the need of a buffer zone planned around and within the plant.
Safe storage also begins with an up-to-date inventory of hazardous chemicals

that can be used to apprise personnel of the dangers in a laboratory, shop, or work area.
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An accurate inventory is also necessary if emergency responders are to respond

effectively to a fire or chemical release in the area. All hazardous chemicals must also be
clearly labeled for the benefit of current users, emergency personnel, and future users.
Unknown chemicals can be expensive to dispose of therefore, all labels are ensured to be
legible and in good condition. Otherwise, damaged or missing labels have to be repaired
or replaced as soon as possible.
Besides, chemical materials must be segregated and stored according to their

chemical family or hazard classification unless they are compatible. Accidental contact
between incompatible chemicals can result in a fire, an explosion, the formation of
highly toxic and/or flammable substances, or other potentially harmful reactions.
12.2.2 Transportation of Chemicals
Most accidental releases of dangerous liquids or vapor in chemical processing

plants occurred at road and rail tanker loading and unloading stations. This involves the
consideration of the different hazards created which concentrate and interact at these
points. The hazards include:
 Vehicle hazards – collisions, error in parking position, unauthorized starting and

damage to and poor maintenance of vehicles
 Hazards of temporary hose and solid pipe connections
 Hazards of ignition both from vehicle engines and from electricity
 Hazards of overfilling and errors in sequence of valve opening and closing
Loading and offloading should only be allowed at carefully selected sites where
necessary facilities are installed. It should be within but near the perimeter fence, in
paved, leveled or concreted areas. The bay must be clearly marked and provided with
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light roofs and upper side coverings to protect against sun and driving rain, but without
end wall for easy through-transit of vehicles and good natural ventilation. Only vehicles
approved for the liquid in question may be used (King, R., 1990).
Some of the checklist when dealing with the transport of hazardous chemicals at
further distances include:
 Avoid transporting with food, water or other reactive chemicals

 Follow the separation and segregation rules for transporting mixed classes of
hazardous chemical
 Secure hazardous chemicals on the vehicle so they cannot move or fall
 Keep a record of the chemicals being carried
 Separate foodstuffs from chemicals
 Make sure the required signs and equipment for the vehicle are well-prepared
 Make sure the driver of the vehicle has the correct licence and is trained in
emergency procedures
12.2.3 Plant Layout and Location
A chemical plant has to be located sufficiently far from any housing areas in
order to minimize the probability of harming the public during any explosion, fire or
toxic release events which may cause catastrophic effects to the affected surrounding. A
good plant layout includes little or minimum possible movement of chemical materials
during the operations and one that involves unidirectional flow of the materials during
operations without involving any back tracking. There has to be maximum visibility,
minimum handling and maximum accessibility to the chemicals that can ensure proper
security with maximum flexibility.
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Chemical process layout is related to the relative position of the equipment or

facility of the process. Here, efficiency means economic efficiency, operability and
flexibility, availability for future expansion, safety and reliability, and/or environmental
friendliness. In many cases, economic efficiency is the main objective, but considering
the other elements, especially safety, is important for the sustainability of the process.
12.2.4 Process Utilities
A chemical plant should be designed in a way so that the sudden failure of one or
more utility supplies do not prove disastrous or undermine the feasibility and hence, the
safety of the process. The routing of service supplies should be as secure as possible.
The position of underground supplies should be clearly marked on drawings and, where
possible, by ground posts. Underground supplies must be adequately protected from
heavy vehicles. The different utility supplies are described as follows:
12.2.4.1 Electricity
The use of flameproof and intrinsically safe electrical equipment and conduit is
to reduce the risk of flammable gases, vapors and dusts. A ‘hazardous zone drawing’ is
made when all sources of leaks of flammable materials have been identified. This will
show the categories of electrical equipment that are allowed in each zone.
The loss of electrical power is exceptionally detrimental to the process if it

causes materials to solidify in a process or pipeline, air-cooled and refrigerated heat
exchangers to cease functioning and cooling water and process pumps to fail. Reliable
back-up systems, which are ultimately reliant on local battery power packs, are
important to deal with the problems caused. In order to prevent electrical shock, the
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equipment must be properly grounded with entire wiring and electrical component
should comply with the standards of the local authority. Besides, there is a necessity to
have regular check and maintenance on all equipment to prevent future accidents.
12.2.4.2 Steam
Steam pipework, expansion bends and supports must be designed to high

standards to resist the stresses caused by high velocities. Careful thought must be given
to the collection and disposal of steam condensate from reboiler, steam heaters and traps.
The system should be designed to prevent the escape of steam near the plant which
causes local fog, condensation on nearby surfaces, corrosion and accidents.
12.2.4.3 Cooling Water
Problems found in cooling water include corrosion, scaling, growth of mollusks

and the presence of solid objects, which block heat exchanger tubes, small valves and
lines. This requires expert study to kill algae and mollusks; and to control pH, scaling,
precipitation and corrosion. Another problem of circulating cooling water systems is the
day-to-night temperature fluctuations, which cause process disturbances. In situations
where cooling water failure is significant, stand-by pumps provided with an alternative
power source are often installed.
12.2.4.4 Process Air

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Failure of the compressor usually results in an automatic emergency plant

shutdown, but the consequences are seldom disastrous. Air entering air-separation plants
requires special treatment to remove traces of hydrocarbons and other impurities to
prevent plant explosions.
12.2.4.5 Refrigerant
Many of the refrigerants formerly in common use are flammable (e.g. propylene)
and toxic (e.g. ammonia). Refrigeration plants using refrigerants other than water should
be designed so that the refrigerant is always under a positive pressure when the plant is
running.
12.2.5 Flammability
Flammability simply means the ease with which a material burns in air (or
occasionally in some other stated gas such as O2). It applies to gases, liquids and solids.
In most process industries, it is of the highest concerns regarding the flammability of
gases, liquids and their vapors and of dispersed dusts and liquid droplets in which all are
referring to as fuels. The result of ignition can be a fire or explosion or sometimes both.
Accidental fires and explosions of flammable air mixtures often follow the
escape of combustible materials, which may result from an uncontrolled reaction or an
explosion within the process or storage plant. The constructional materials used in the
process industries are mostly of low flammability, although the plant and structure used
often require fire protection. Flammable gases and vapors of flammable liquids are in
many ways more dangerous than the liquids themselves. This is because they are
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invisible, cannot easily be contained and may travel considerable distance before they
reach an ignition source and ignite.
12.2.5.1 Parameters of Flammability
There is no single parameter by which the flammability of different materials can

be compared to all the needs that are to be considered. The flash point is an important
parameter for liquids with relatively low boiling point. The following lists include
properties which, while affecting flammability to some degree, are mainly important for
containing and fighting fires:
 Flammability limit (for gases and vapor)

 Flash-point (for liquid and low-melting solids)
 Auto ignition temperature (mainly for gases and vapor)
 Burning velocity (mainly for gases and vapor)
 Heat of combustion (for all materials)
 Oxygen requirements for complete combustion
 Specific gravity relative to:
- Air, for gases and vapor
- Water, for liquid
 Solubility in water (mainly for liquid)
 Melting point and softening point for solids
 Viscosity (mainly for liquids and low melting solids)
 Carbon/ H2 ratio (mainly for hydrocarbons)
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12.2.6 Explosion
Explosion in the vapor spaces of fixed roof storage tanks have seen its constant
number of events in recent years. The combustion reaction occurs in premixed medium
and is expanded by "flame propagation" through the premixed medium. The flame
propagation phenomenon is mainly governed by the combustion reaction rate, and the
propagation speed is relatively fast. The reason for the large number of explosion is that
explosive mixtures are present in the vapor space of many storage tanks. It is almost to
be certain that a source of ignition will never turn up, particularly if the liquid in the tank
has a low conductivity so that static charges can accumulate on the liquid. For this
reason, many companies insist that fixed roof storage tanks containing hydrocarbons
above their flash points must be blanketed with nitrogen. Other companies insist that
such hydrocarbons are stored only in floating roof tanks.
In confined explosions, depending on the degree of venting, the early time-blast

phenomena will be similar to a free air spherical or hemispherical burst. However,
gaseous products will remain trapped in the closed space and the shock wave will be
reflected from the boundaries of the compartment until the energy of the explosion is
dissipated into heat. Reflected waves will propagate and interact with other surfaces
generating more reflected waves. After a peak overpressure the high pressure and
temperature gases will expand throughout the space in a more lengthy process. This is
known as the gas pressure phase, where pressure will decay to ambient pressure as the
gases cool down or leakages occur (Salvado et al., 2017).
12.2.7 Leaks
Leakage of process materials is one of the major hazards faced by most process
industries. Most of the materials handled will not burn or explode unless mixed with air
in certain proportions. To prevent fires and explosions, the fuel must be kept in the plant
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and the air out of the plant. The latter is relatively easier because most plants operate at
atmospheric pressure. Nitrogen (N2) is widely used to keep air out of low-pressure
equipment such as storage tanks, stacks, centrifuges and equipment which is de-
pressurized for maintenance.
The main problem in preventing fires and explosions is thus preventing the
process material from leaking out of the plant to maintain plant integrity. Similarly, if
toxic or corrosive materials are handled, they are hazardous only when they leak. Many
leaks have been discussed under other headings, including leaks which occurred during
maintenance, as the result of human error, or as the result of overfilling storage tanks.
Other leaks have occurred as the result of pipe or vessel failures.
12.2.8 Environmental Issues
Methanol can enter the body either through the respiratory system, skin or the
digestive tract, and toxicity effects on the body are similar regardless of the pathway.
While certain risks, particularly those associated with skin contact or accidental
ingestion, are easily mitigated by use of proper fuel handling procedures and controls,
the risks associated with exposure to evaporative or tailpipe emissions from methanol
vehicles are far more complex and less well understood. Inhalation exposure risk
scenarios vary in concentration levels and duration: methanol concentrations in confined
or poorly-ventilated areas such as personal garages can be fairly high, but the time of
exposure may be fairly short.
Apart from these direct risks, this paper also discusses the indirect risks of
methanol use, including exhaust emissions of air toxics such as formaldehyde and life-
cycle emissions of climate-changing “greenhouse” gases. There is also the indirect
health risk of greenhouse gas emissions resulting from methanol fuel production.
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However, the potential public health and/or welfare impact of greenhouse gas emissions
poses a significant global challenge and widespread use of either coal or natural gas for
methanol fuel production could exacerbate an already critical situation. Traditional
methods of producing methanol from coal release approximately twice the equivalent
CO2 emissions per unit energy as conventional petroleum, unless measures are taken to
reduce or displace the carbon emissions. These broader consequences of methanol fuel
use must be measured relative to the considerable human health challenges posed by the
continued use of petroleum-based fuels (Brusstar et al., n.d.).
12.3 Worker Safety
A few basic safety rules that must be observed by workers when dealing directly
and indirectly with a chemical process in a plant involve the following:
 No smoking or eating
 No drinking of alcoholic liquor
 No drinking, except from water fountains
 Safety instructions and danger signs must be observed
 Wear all personal protective equipment provided and replace damaged
items immediately
 Do not enter processing areas other than your own place of work
 Do not temper with faulty equipment or electrical fitting; report such faults
to supervisors
 Get immediate medical attention for injuries, however minor they appear
 Report all accidents to super visors
 Do not lose temper, or indulge in ‘horse-play’
 Know the location of fire alarms, extinguishers and escape routes
 When in doubt; ask supervisors
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Personal protective clothing and/or equipment (PPC/E) are needed against

particular hazards of the working environment. PPC/H should be selected to meet the
following general requirements:
 Adequate protection against the specific hazard(s) to which the worker

will be exposed
 Minimum weight and discomfort compatible with efficient protection
 Flexible but effective attachment to the body
 Weight carried by a part of the body which is able to support it
 No restrictions on those body movements and sensory perceptions which
are essential to the job
 Durability
 Clothing should be attractive
 Accessibility of parts which should be maintainable on the premises
 No additional hazards introduced by the PPC/Es even when they are
misused
 Compliance with relevant standards
12.3.1 Body Protection
The environmental conditions and surroundings in which its operatives are

conducted should be taken into proper consideration. Chemical protective clothing has
been divided into three groups namely, light, medium and heavy duty. Light duty
chemical protective clothing generally consists of uncoated cotton or synthetic
fabrics with water-resistant finish in the form of overalls, laboratory coats and smocks.
It is used by workers who are at slight risk from relatively harmless chemicals.
Medium duty chemical protective clothing consists of an apron of one of

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several impervious and resistant materials such as natural or synthetic rubber, PVC-
coated fabrics or leather. These are useful for workers exposed to quite a wide range of
chemicals, oils and hydrocarbons.
Heavy duty chemical-resistant clothing is based mainly on PVC or PVC-coated

fabrics in the form of boiler suits, long surgical coats, bib and brace overalls, leggings
and three-quarter-length suits. Contaminated chemical-resistant clothing should always
be washed or hosed down before the wearer removes it and proper provision must be
made for storing, inspecting and maintaining it.
12.3.2 Hand Protection
Harmful substances often enter the body through the skin of the hands,
particularly through cuts and abrasion. Several types of gloves, gauntlets and mittens in
a variety of materials are available to protect the hands from corrosive chemicals and
other harmful substances, as well as abrasion, cuts, extremes of temperature and high
voltages.
PVC gloves are available in various types such as smooth-surfaced gloves

which protects the skin against contact with acids, alkalis, chemicals, solvents, oils and
fats. Gloves with a matt surface coating provide better grip and abrasion resistance
whereas cotton linings increase comfort and absorb sweat. Besides, leather gloves can
protect the worker’s hand from rough surfaces and special insulated gloves can provide
protection from hot objects. On the other hand, cut-resistant gloves prevent cuts from
knives or sharp edges. The effects of excessive vibration from hand-tools and
machinery can be reduced with anti-vibration gloves whereas blood and germs
protection is enabled with disposable gloves.
Gloves must also be used when the worker’s hands are clean apart from regular
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cleaning of any fabric and leather gloves. It must be ensured that the gloves have the
right size and length for the particular job and must be replaced if cuts, tears, holes or
defects are present.
12.3.3 Head Protection
The main risks of head injury in the workplaces include when there is a
possibility that a worker may be struck on his head by a falling or flying object or when
a worker may strike his head against a protruded object or may be struck by a swinging
object. The safety helmet selected should satisfy certain performance requirements
including shock absorption, resistance to penetration; and be adjustable to fit and make
comfortable to the user. Certainly, the safety helmet can never be effective unless it is
properly worn for the purpose.
Special headwear is provided for industrial workers to protect against particular

hazards. Safety helmets are also provided to protect against impact of falling objects,
exposure to abnormal heat, chemical splashes, contact with high-voltage sources and
risk of sideways crushing. Safety helmet also contains long hair and prevents its
entanglement with machinery; protects the wearer from rain and extremes temperature;
and also shades the eyes.
Other safety head wears include welders’ helmets to which visors or face shields
are attached, acoustic helmets for those exposed to high noise levels, bump caps and
scalp protectors for protection against bruising in confined places, shot-blasting helmets
and air-stream helmets. The use of safety helmet, like other personal protective
equipment, is always regarded as the last resort for accident prevention. In principle,
reducing or controlling the risks of injury at source should be considered first.
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12.3.4 Foot Protection
Safety shoes are required where the potential for serious injury to the foot may
result from an employee's daily job duties. Foot injuries may occur in areas where there
are rolling or falling objects, objects piercing the sole, or where feet are exposed to
electrical hazards.
Most safety foot wears are designed to protect the toes from impact or crushing
from falling objects. Other hazards against which safety footwear is available include
penetration trough the mid-sole and upper, oil and chemical penetration, slipping, heat
and metal turnings. Antistatic rubber footwear has sufficiently high electrical resistance
to protect against electrocution hazards while allowing electrostatic charges to dissipate
harmlessly.
12.3.5 Eye Protection
The majority of impact injuries result from flying or falling objects, or sparks
striking the eye. Most of these objects are smaller than a pin head and can cause serious
injury such as punctures, abrasions, and contusions. While working in a hazardous area
where the worker is exposed to flying objects, fragments, and particles, primary
protective devices such as safety spectacles with side shields or goggles must be worn.
Secondary protective devices such as face shields are required in conjunction with
primary protective devices during severe exposure to impact hazards.
The main forms of protection are safety spectacles, safety goggles and shields.
Safety spectacles have toughened glass or plastic lenses in various tints, with plastic or
metal frames and may have ventilated side shields for protection against low-energy
droplets and particles. Safety goggles which enclose the eyes completely, with or
250
without ventilation, and which are kept position by an elastic headband, provide more
complete protection than spectacles but are less comfortable to wear. Conditions where
goggles should be considered include work in dusty atmospheres, work in injurious
chemicals (in fine sprays or mists form), work with toxic and irritating gases; and work
where impact from large particles are possible.
12.3.6 Respiratory Protection
Respiratory Protective Equipment (RPEs) are of two main types; respirators and
breathing apparatus. Respirators depend on the oxygen in the air surrounding the
wearer for respiration and provide means for removing the hazardous contaminants
from the air before it is breathed. They may not be used in oxygen-deficient
atmospheres or in ones that present an immediate danger to life.
Breathing apparatus provides an independent supply of air or oxygen for the

wearer and does not depend for oxygen on the surrounding atmosphere. It can be used
for a wider range of hazards. There are five main types of breathing apparatus include:
1. Self-contained closed circuit which the exhaled air is passed through a chemical
which replaces its carbon dioxide with oxygen.
2. Self-contained open-circuit which supplies air on demand (through a lung-

governed valve) or at constant flow (through a pressure reducer and flow
controller) to a full-face mask with an exhalation valve. For professional use, a
limited supply of compressed air is contained in a cylinder attached to the
wearer’s body.
3. Compressed air-line which is similar to open-circuit apparatus with a small-

diameter air hose from a safe compressed air source replacing the compressed
251
air cylinder, routinely used in industry for tasks such as cleaning and paint
spraying.
4. Fresh air hose in which air suitable for respiration is drawn from an adjacent
uncontaminated area through a larger-diameter hose by the breathing of the
wearer, with or without a blower.
5. Escape breathing apparatus, a simple form of self-contained breathing

apparatus for short-duration use which is usually of open-circuit type, with its
own small compressed air cylinder.
Pipelines throughout the ECE region transport large volumes of hazardous

substances, such as crude oil, its derivatives and natural gas. If pipelines are
constructed, monitored, operated and maintained as required by international and
national legislation and according to national and international industry standards and
good practices, they can be safe and environmentally sound. However, they can also
represent a serious risk to human health and the environment. External interference,
corrosion and poor maintenance are the most common causes of pipeline accidents.
Safety considerations in deciding pipeline layout are considered in this section.

Pipe layout in a building should be kept to the shortest possible and most of the
pipeline must be kept preferably outdoors. Pipelines could be laid above or
underground. Underground layout is preferred only when chances of leakage are
negligible. Above ground pipes must be guarded against vibrations, thermal expansion,
shocks and sagging due to own load.
In straight pipe, only compressive stresses exits, due to which it will bend to
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form an arc of a circle to accommodate the expansion. Since this is not desirable, by
providing expansion loop in the pipeline, the change in length due to thermal expansion
is contained within the loop. In addition to this, at high temperature, creep phenomena
set in which slowly relaxes the stresses developed.
12.5 General Safety in Dimethyl Carbonate Production Plant
12.5.1 Handling of Dimethyl Carbonate
The flammability and explosion risks of dimethyl carbonate are widely

recognized and well documented. Liquid or vapor dimethyl carbonate in high
concentrations can potentially result in certain safety and health risks to workers. The
safety hazards, industrial health risks, and exposure limits for ethylene may be updated
or modified through studies and regulatory changes.
Standards frequently vary from country to country. OSHA regulations require

all ethylene manufacturers to provide customers with the latest Material Safety Data
Sheets (MSDS) for dimethyl carbonate. The MSDS also can be used to notify users of
applicable regulations. Users should disseminate such information in accordance with
the OSHA regulations to give warning of possible hazards to all appropriate persons. In
general terms, these documents contain physical data on the product, information for
safety and emergency situations, recommended procedures for immediate medical
treatment, identification of fire and explosion hazards, current hazard information, and
current occupational health, exposure, and protection guidelines.
The regulations require that the MSDS be updated to reflect significant new
information in these areas. It should be referred to the supplier's MSDS for dimethyl
253
carbonate for more detailed information regarding safety, health, and/or toxicity data.
The supplier's MSDS can be contacted for specific recommendations on handling
dimethyl carbonate under regular operations and in emergencies. Supervisory and
operating staff must have access to the MSDS and receive training on hazardous
chemicals in their work area.
12.5.2 Environmental Fate and Toxicity
Dimethyl carbonate is partitioned into air and water with negligible amounts in
soil, sediment and biota. In the aqueous environment it is considered to be readily
biodegradable. Its low partition coefficient suggests that dimethyl carbonate has low
bioaccumulation potential. The following information indicates that dimethyl carbonate
is not environmentally hazardous.
Table 12.1: Effect Assessment of Aquatic Organisms

Effect Assessment Result
Aquatic Toxicity Fish, daphnia, algae and plant studies indicate that
the environmental toxicity of dimethyl carbonate is
low
Table 12.2: Environmental Fate of Dimethyl Carbonate

Fate and Behavior Result
Biodegradation Dimethyl carbonate is readily biodegradable in
water. Biodegradability in soil and sediment is not
relevant.
Bioaccumulation potential Based on the low partition coefficient, it is
concluded that the bioaccumulation potential of
dimethyl carbonate is very low and does not need
254
to be studied further.
PBT/vPvB conclusion Dimethyl carbonate is neither PBT nor vPvB based
on biodegradation and bioaccumulation results and
no hazard to aquatic species.
It could be expected that dimethyl carbonate is likely to be absorbed into the

body by the dermal route of exposure and, based on its moderate vapour pressure of 7.57
KPa at 25°C and its boiling point of 90°C, it could also be expected that absorption
through inhalation might be likely. However, according to the toxicity studies, there was
no indication of inhalatory or dermal absorption, metabolism, excretion or distribution.
The acute rat oral, dermal and inhalation studies, together with the repeat dose inhalation
study and the one generation reproductive toxicity study indicated no resultant adverse
toxicity. Similarly, there was no evidence of significant skin or eye irritation or
sensitization potential.
Table 12.3: Toxicity Assessment

Effect Assessment Result
Acute Toxicity (oral/dermal/inhalation) Dimethyl carbonate is of low acute
toxicity via oral, skin and inhalation
routes of exposure.
Irritation/Corrosivity Dimethyl carbonate is not irritating to the
(skin/eye/respiratory tract) skin or to the eyes. Corrosivity was not
tested on the basis of the absence of
irritation properties.
Sensitization (skin/respiratory tract) Based on the available data, dimethyl
carbonate is not considered to have skin
or respiratory sensitization properties.
Repeated Dose Exposure Test results with oral exposure indicate
that there is no marked repeated dose
toxicity. Repeated dose toxicity via the
255
inhalation and dermal exposure route

have not been tested.
Mutagenicity All available test data indicates that
Dimethyl carbonate does not cause
mutagenic effects.
Carcinogenicity No carcinogenicity data is available.
Reproductive Toxicity All available data suggest that dimethyl
carbonate has no adverse fertility or
reproductive effects.
12.5.3 Disposal Consideration
Care must be taken in the handling and disposal of laboratory-sized and larger
samples of ethylene. Laboratory and sample storage facilities should be appropriate for
the associated risks. Test and handling procedures should be clear and the laboratory
and operating personnel well trained. Methods for in-plant disposal of samples include
venting to a control device such as a flare or controlled incineration at a remote site
with remote control of the ignition source to help protect personnel and property.
The disposal in large quantities requires the help of a competent specialist is

recommended. There are several chemical disposal companies specializing in the
transportation and disposal of hazardous materials. These companies have the proper
and suitable equipment and trained personnel to handle the disposal activities in a safe
and environmental-friendly manner.
256
12.5.4 Exposure Limits
The exposure limit of dimethyl carbonate to the workers is calculated based

on 8-hours Time Weighted Average (TWA). The formula is shown as below:
E = (Ca Ta+CbTb+...Cn Tn) ÷ 8
Where,
E is the equivalent exposure for the working shift
C is the concentration during any period of time T where the concentration
remains constant
T is the duration in hours of the exposure at the concentration C
12.5.5 Storage of Dimethyl Carbonate
The conditions for safe storage of dimethyl carbonate include any

incompatibilities and keeping the container tightly closed in a dry and well-ventilated
place. Any containers which are opened must be carefully resealed and kept upright to
prevent leakage. Dimethyl carbonate reacts with acids to liberate heat along with
methanol and carbon dioxide. Strong oxidizing acids may cause a vigorous reaction that
is sufficiently exothermic to ignite the reaction products. Heat is also generated by the
interaction with caustic solutions. Flammable hydrogen is generated by mixing with
alkali metals and hydrides.
Dimethyl carbonate should be kept away from ignition sources by incorporating

explosion-proof equipment. Ignition sources include heat, sparks, open flames or even
hot surfaces whereas explosion-proof equipment can involve electrical, ventilating and
lighting equipment. Besides, measures should be taken as well for prevention in the
257
build-up of electrostatic charges. This can be done by using only non-sparking tools and
ground or bond containers and receiving equipment.
There are two basic types of vessels that can be used to store dimethyl
carbonate namely, pressurized or cylindrical (bullet tanks) and flat bottom storage
tanks. The most common way to store liquid dimethyl carbonate is in flat bottom
insulated tanks at atmospheric pressure. For smaller capacities, liquid dimethyl
carbonate can be stored in pressurized vessels (cylinders or spheres). They are
generally constructed to ASME Boiler & Pressure Vessel Code Section VIII.
12.6 Plant Layout
Site layout for a plant consists of the process units involved which is located in
the main plant and other auxiliary buildings. The layout, which refers to each
department, must be arranged in order to give maximum work productivity, efficiency and
minimum operational costs. The layout of plant must consider three main factors
namely, comfort, ability and safety; economical flow of material and the area utilized to
build the plant.
The auxiliary building and services required on the site in additional to the main
process units are as follows:
 Office (administration)
 Utilities such as boiler, power generation, cooling water
 Storage for raw material and product
 Storage for maintenance and operating supply
 Waste treatment plant
 Laboratory
258
 Maintenance workshop
 Canteen and prayer room
Figure 12.1: Plant Layout
According to Figure 12.1 above, the utilities building is located near the process
section to give the most economical flow of supplies such as steam to the process units
and is important in reducing heat losses by steam. In the plant layout above, it also
shows the location of offices and other facilities in the plant. This plant layout is
developed to ensure the safety for the workers and all the assets in the plant.
12.7 Hazard and Operability Studies (HAZOP) Introduction
The hazard and operability studies or HAZOP for short is a formal procedure
used to identify hazards present in a chemical process plant. The usage of HAZOP
helps in the identification of all the possible errors and problems which could arise
from the operations and processes. It is considered systematic, effective,
comprehensive, and flexible and is well accepted by the chemical and petrochemical
industries. Typically, HAZOP is intended to be a formal safety audit and review of an
operating plant or a modification of the plant to ensure that the probabilities of major
accidents could be eliminated and the consequences could be reduced to acceptable
levels as compared to before the modification. Although this maybe the case, HAZOP
could be applied during the design stage as to enable any modifications to be
incorporated into the final design before construction of the plant.
Hazard identification is the action of observing unsafe conditions and unsafe

acts that could potentially cause accidents. This phase could be done through various
mediums, such as conducting walk- through surveys, audits, check-list and inspections
259
around the plants compound. For the case of HAZOP, it is done through the
experiences of engineers and their understanding of the processes, to determine
possible hazards that could arise due to deviation from suitable conditions of the
processes. The conclusion of the studies will suggest suitable routes to eliminate the
possible errors that could occur through the addition of proper instruments or safety
procedures.
12.7.1 Objectives of HAZOP Analysis
The objectives of a HAZOP analysis involve the following:
 To critically examine the inadequacies in systems by considering it as a fully

integrated dynamic unit, rather than the ‘ad hoc’ design approach.
 To coordinate the various discipline involved in the project and provide a means
for an overall systematic analysis of the system.
 To identify hazards or deficiencies and potential operational problems which
may lead to hazards such as fire, explosion, toxic exposure or reduced
productivity.
 To identify and prevent hazards in chemical plants that are growing in
complexity while traditional standards are no longer adequate to keep errors in
check.
12.7.2 Advantages and Disadvantages of HAZOP Analysis
Advantages
 Provide comprehensive identification of hazards from operational upsets,

260
operational procedures and equipment failures.

 Results in fewer commissioning and operational problems.
 Induces less down time for chemical processing plants.
 Producing better informed staff and plant personnel, greater confidence by staff
during operational hours.
 Used as evidence of comprehensive thoroughness in safety review and analysis,
earning trust and confidence of insurers, investors and inspectors.
Disadvantages
 It is quite tedious to apply, especially on larger and complex plants.

 Requires a team of experts to provide judgement based on experience and
understanding of the processes involved.
 Requires considerable amounts of time to complete.
 Could only identify hazards without taking risk into consideration.
12.7.3 HAZOP Study Procedures
There are a set of procedures and specific terms that are to be used and obeyed
when conducting the HAZOP studies. The specific terms mentioned are guide words,
which are used to describe possible deviations of certain parameters involved from the
ideal process condition, and thereby shows a more standardized way of mentioning
parameter changes and acknowledge the consequences of the deviations accordingly.
Procedures:
1. Obtain detailed information on the processes of the plant, such as PFD,

equipment specs, material of construction, MSDS, mass and energy balance,
261
simulation data and etc.

2. From the PFD, each equipment is identified and divided into units, such as
reactor unit and distillation column unit, and the HAZOP study is done for each
of the units identified.
3. Study nodes for each unit are identified. Examples of study node are heating
coil and tank of reactor, smaller operation units of the larger units identified in
Step 2.
4. Provide brief description of the function of the study node.
5. Relate process parameters to the study nodes
6. Apply guide words to the process parameters selected for the node. Guide
words are shown in Table 12.2.
7. For each deviation, determine possible causes and note any already available
protective systems, if any.
8. Evaluate possible consequences of the deviations
9. Recommend possible action or solutions to eliminate the deviations.
10. Repeat Steps 2-9 for each units, their respective study nodes as well as their
respective parameters associated.
Table 12.4: Parameters Associated with Line or Vessels of Process

Parameters Process Lines Process Vessels
Flow  -
Level - 
Temperature  
Pressure  
Concentration  
pH  
Viscosity  
State  
Agitation - 
Volume - 
262
Reaction - 
Sample - 
Table 12.5: Guide Words for HAZOP Analysis

Guide Words Meaning Comment
No, Not, None Complete negation No part of the design intention is
of the intention achieved, but nothing else happens.
More, Higher, Quantitative Applies to quantities such as flow
Greater Increase rate and temperature and to
activities such as heating and
reaction.
Less, Lower Quantitative Applies to quantities such as flow
Decrease rate and temperature and to
activities such as heating and
reaction.
As Well As Qualitative All design and operating intentions
Increase are achieved along with some
additional activity such as
contamination of process streams.
Part Of Qualitative Only some of the design
Decrease intentions are achieved,
some are not
Reverse Logical Opposite Most applicable to activities such
of as flow or chemical reaction. Also
applicable to substances, for
example poison instead of
antidote
Other than Complete No part of the original intention is
Substitution achieved, original intention is
replaced by something else.
Sooner Than Too early or in Applied to process steps or actions
wrong order
Later Than Too late or in Applied to process steps or actions
wrong order
Where Else In additional Applies to process locations, or
locations locations in operating procedures.
263
Figure 12.2: Summary of Procedures of A HAZOP Study
12.8 HAZOP Study Execution
In this dimethyl carbonate production plant, HAZOP studies are done on several
unit operations of the plant design which includes two units of reactors, one unit of flash
column, four units of distillation columns, heat exchangers; heaters, three units of
pumps, three units of pressure-reducing valves, a compressor and a gas expander. The
264
HAZOP studies will only be done once for similar units and are displayed in the
following section.
265
12.8.1 Reactor
UNIT OF OPERATION Reactor SR-1
IDEAL CONDITIONS Temperature (oC) 250 Pressure (atm) 19.7
FUNCTION OF UNIT To house the production of propylene carbonate from the reaction between carbon
dioxide and propylene oxide
FUNCTION OF STUDY Vessel – To provide area for the reaction occur
NODES
Heating jacket – To provide heating to maintain temperature at desire conditions
Study Node Reactor Vessel

PARAMETERS ACTION REQUIRED
GUIDE POSSIBLE CAUSES POSSIBLE
WORDS CONSEQUENCES
Flow No 1. Blockage in pipe 1. No reaction occur 1. Schedule regular
2. The vessel is clogged 2. Decrease the cleaning the pipes
from the inside production of 2. Regular checking and
3. Feed pipe or supply propylene maintenance vessel
pipe rupture carbonate until no and pipe
4. Control valve fail to production 3. Install level control
open alarm
266
5. Pump is close 4. Install bypass piping

to the reactor
5. Install automated
pump
Flow High 1. Control valve failure 1. Runaway reaction 1. Install high level
2. Increase pumping 2. Overload reaction control alarm
capacity in vessel 2. Install automated
3. Controller fails and 3. Pressure build up pump
valve fully open might occur 3. Install automated
valve
Low 1. Control valve failure 1. Lower the 1. Install low level
2. Controller fails and production rate control alarm
valve fully closed 2. Install automated
3. Pump failure valve
4. Pipe leakage 3. Maintenance pump
4. Regular checking and
maintenance piping
system
Reverse 1. Pressure in reactor is 1. Damage the 1. Install a one way flow
higher than inlet flow pipelines and valve
267
preceding
equipment
Temperature High 1. Feed or supply 1. Runaway reaction 1. Install high
temperature is too can cause pressure temperature alarm
high build up, might 2. Install temperature
result in explosion controller
Low 1. Feed temperature is 1. Cause low yield of 1. Install low
too low production temperature alarm
temperature controller
3. Install heating jacket
using steam as a
medium
Pressure High 1. Outlet pipe blocked 1. Cause reverse flow 1. Regular cleaning of
2. Temperature in vessel 2. Runaway reaction reactor piping system
too high 2. Install relief valve
3. Install high pressure
alarm
Low 1. Reactor leakage 1. Low reaction yield 1. Install low pressure
obtain alarm
268
2. Regular checking the

reactor condition
Reaction Low 1. Low temperature 1. Low productivity 1. Install low
2. Low pressure rate temperature alarm
3. Low feed 2. *same as above 2. Install low pressure
3. *same as above alarm
3. Install low flow alarm
Study Node Heating Jacket
WORDS CONSEQUENCES
Flow No 1. Unavailability of 1. Low temperature at 1. Look for several
heating steam reactor vessel supplier of heating
2. Heating steam pipe resulting in lower steam
clogged production yields 2. Regular checking and
maintenance vessel
and pipe
Flow High 1. Valve failure 1. Overheating of 1. Install high level
2. Controller fails and reactor vessel, control alarm
valve fully open result in runaway 2. Install automated
reaction valve
269
Low 1. Heating steam pipe 1. Low temperature 1. Install low level

leaked or partially in reactor control alarm
clogged 2. Low yield of 2. Regular checking the
product controller
Temperature High 1. Heating steam enter 1. Overheating of 1. Install high
at high temperature reactor vessel, temperature alarm
result in runaway
reaction
Low 1. Heating steam enter 1. Lower temperature 1. Install low
at low temperature at reactor vessel temperature alarm
cause low reaction
yield
Pressure High 1. Heating steam enter 1. Can damage the 1. Install safety relief
at high pressure reactor and heating valve
jacket
Low 1. Heating steam enter 1. Insufficient heating 1. Install low pressure
at lower pressure due to superheated alarm at heating steam
steam pipe
270
UNIT OF OPERATION Reactor SR-2
IDEAL CONDITIONS Temperature (oC) 150 Pressure (atm) 11
FUNCTION OF UNIT To house the transesterification reaction of methanol and propylene carbonate to
produce DMC
FUNCTION OF STUDY Vessel – To provide area for the reaction occur
NODES
Heating jacket – To provide heating to maintain temperature at desire conditions
Study Node Reactor Vessel

WORDS CONSEQUENCES
Flow No 1. Blockage in pipe 1. No reaction occur 1. Schedule regular
2. The vessel is clogged 2. Decrease the cleaning the pipes
from the inside production of 2. Regular checking and
3. Feed pipe or supply propylene maintenance vessel
pipe rupture carbonate until no and pipe
4. Control valve fail to production 3. Install level control
open alarm
5. Pump is close 4. Install bypass piping
to the reactor
271
pump
Flow High 1. Control valve failure 1. Runaway reaction 1. Install high level
2. Increase pumping 2. Overload reaction control alarm
capacity in vessel 2. Install automated
3. Controller fails and 3. Pressure build up pump
valve fully open might occur 3. Install automated
valve
Low 1. Control valve failure 1. Lower the 1. Install low level
2. Controller fails and production rate control alarm
valve fully closed 2. Install automated
3. Pump failure valve
4. Pipe leakage 3. Maintenance pump
4. Regular checking and
maintenance piping
system
Reverse 1. Pressure in reactor is 1. Damage the 1. Install a one way
higher than inlet flow pipelines and flow valve
preceding
equipment
272
Temperature High 1. Feed or supply 1. Runaway reaction 1. Install high

temperature is too can cause pressure temperature alarm
high build up, might 2. Install temperature
result in explosion controller
Low 1. Feed temperature is 1. Cause low yield of 1. Install low
too low production temperature alarm
temperature
controller
3. Install heating jacket
using steam as a
medium
Pressure High 1. Outlet pipe blocked 1. Cause reverse 1. Regular cleaning of
2. Temperature in flow reactor piping system
vessel too high 2. Runaway reaction 2. Install relief valve
3. Install high pressure
alarm
Low 1. Reactor leakage 1. Low reaction yield 1. Install low pressure
obtain alarm
2. Regular checking the
273
reactor condition
Reaction Low 1. Low temperature 1. Low productivity 1. Install low
2. Low pressure rate temperature alarm
3. Low feed 2. *same as above 2. Install low pressure
3. *same as above alarm
3. Install low flow
alarm
Study Node Heating Jacket
WORDS CONSEQUENCES
Flow No 1. Unavailability of 1. Low temperature 1. Look for several
heating steam at reactor vessel supplier of heating
2. Heating steam pipe resulting in lower steam
clogged production yields 2. Regular checking and
maintenance vessel
and pipe
Flow High 1. Valve failure 1. Overheating of 1. Install high level
2. Controller fails and reactor vessel, control alarm
valve fully open result in runaway 2. Install automated
reaction valve
274
Low 1. Heating steam pipe 1. Low temperature 1. Install low level

leaked or partially in reactor control alarm
clogged 2. Low yield of 2. Regular checking the
product controller
Temperature High 1. Heating steam enter 1. Overheating of 1. Install high
at high temperature reactor vessel, temperature alarm
result in runaway
reaction
Low 1. Heating steam enter 1. Lower temperature 1. Install low
at low temperature at reactor vessel temperature alarm
cause low reaction
yield
Pressure High 1. Heating steam enter 1. Can damage the 1. Install safety relief
at high pressure reactor and heating valve
jacket
Low 1. Heating steam enter 1. Insufficient 1. Install low pressure
at lower pressure heating due to alarm at heating
superheated steam steam pipe
275
UNIT OF Distillation Column, DC-100

OPERATION
IDEAL FEED TEMP (oC) 150 PRESSURE (ATM) 2
CONDITIONS
TOP COLUMN TEMP (oC) 93 REBOILER TEMP 222
(oC)
FUNCTION OF To separate multiple component in order to get high purity of desired product by means of
UNIT relative volatility and vapour-liquid equilibrium (VLE)
FUNCTION OF Reboiler – A type of heat exchanger typical used to provide heat to the bottom of
STUDY NODES
distillation column
Study Node Reboiler

PARAMETERS ACTION
REQUIRED
WORDS CONSEQUENCES
Flow No 1. Blockage in pipe 1. Column dry out 1. Install low level
2. Control valve shut 2. Possible dangerous alarm
down 2. Regular checking
276
3. Valves Fail concentration maintenance

4. Tube leakage and 3. No operation procedure and
blocking schedule
5. Pump failure 3. Install bypass
4. Emergency plant
shut down
Flow Low 1. Blockage in pipe 1. Column dry out 1. Install low level
2. Control valve shut 2. Changes in product alarm
down quality 2. Install automated
3. Valves fail pump
4. Tube leakage and 3. Install automated
blocking valve
5. Pump failure 4. Regular checking
maintenance
procedure and
schedule
5. Emergency plant
shut down
High 1. Control valve is fully 1. Flooding in the 1. Install high level
opened
column control alarm
2. Increase pumping
277
capacity 2. Changes in product 2. Check

3. Control valves failure quality maintenance
3. Temperature procedure and
decrease schedule
4. Rise in bottom 3. Install double
control valve
4. Regular checking
and maintenance
pumping system
Reverse 1. Too high pressure 1. No operation 1. Install check
inside the column 2. Pressure build up valve
2. Pump failure inside the column or
at the reboiler
Temperature High 1. High temperature of 1. Product quality 1. Install high
the feed stream becomes temperature
2. Steam flow inlet into significantly low alarm at the
reboiler increase 2. Low purity of column
3. Faulty instrumentation separation obtain 2. Control the
and control 3. Can cause flooding steam flow into
4. Heater control failure inside the column reboiler
278
5. Coolant at condenser 4. Cause pressure 3. Control the

fail to operate well changes inside the temperature of
column feed stream
4. Check the
instrumentation
conditions
Low 1. Low temperature of 1. Product quality 1. Install low
2. Loss of heating (steam significantly low alarm
leaking) 2. Low purity of 2. Install automated
3. Reducing pressure separation obtain temperature
4. Faulty instrumentation 3. Can cause flooding controller
and control inside the column 3. Control the
5. Depressurization of 4. Cause pressure steam flow into
liquefied gas changes inside the reboiler
column
Reflux More 1. Control valve fail to 1. Increase reflux ratio 1. Install level
operate well 2. Increase the duty at controller inside
2. Pumping failure the condenser and reflux drum
reboiler 2. Install alarm
279
level for rising of

drum level
Less 2. Control valve fail to 2. Reduce reflux ratio 3. Install level
operates well 3. Reduce the purity or controller inside
3. Pumping failure quality of the reflux drum
product 4. Install alarm
level for lower
level inside the
drum
Level Low 1. Blockage inside the 1. Pressure build up 1. Preventive
inlet feed stream inside the column maintenance
2. Rupture at the outflow 2. Error in separation 2. Install level
valve which disturb the controller and
3. Pump fail to operate VLE of the system alarm
well 3. Reduce the product
quality
High 1. Leakage of valve 1. Flooding inside the 1. Preventive
which causes column maintenance
overflow inside the 2. Error in separation 2. Install level
column which disturb the controller and
280
2. Instrument for level VLE of the system alarm

indicator is fail to 3. Reduce the product
operate quality
3. Blockage at the
bottom stream
Pressure Low 1. Generation of vacuum 1. Low separation 1. Install low
conditions obtain pressure alarm
2. Undetected leakage 2. Flooding inside the 2. Regular
3. Low gas release column maintenance the
4. Changes in piping system of
viscosity/density of column
compound
High 1. Steam heating enter at 1. Can damage the 1. Install high
high pressure column pressure alarm
2. Flooding occur
UNIT OF Distillation Column, DC-101

OPERATION
IDEAL FEED TEMP (oC) 198 PRESSURE (atm) 1
CONDITIONS
281
TOP COLUMN TEMP (oC) 188 REBOILER TEMP 241

(oC)
FUNCTION OF To separate multiple component in order to get high purity of desired product by means of
UNIT relative volatility and vapour-liquid equilibrium (VLE)
FUNCTION OF Reboiler – A type of heat exchanger typical used to provide heat to the bottom of
STUDY NODES
distillation column
Study Node Reboiler

PARAMETERS ACTION
REQUIRED
WORDS CONSEQUENCES
Flow No 1. Blockage in pipe 1. Column dry out 1. Install low
2. Control valve shut 2. Possible dangerous level alarm
down concentration 2. Regular
3. Valves Fail 3. No operation checking
4. Tube leakage and maintenance
blocking procedure and
5. Pump failure schedule
3. Install bypass
4. Emergency plant
shut down
282
Flow Low 1. Blockage in pipe 1. Column dry out 1. Install low level
2. Control valve shut 2. Changes in product alarm
down quality 2. Install automated
3. Valves fail pump
4. Tube leakage and 3. Install automated
blocking valve
5. Pump failure 4. Regular
checking
maintenance
procedure and
schedule
5. Emergency plant
shut down
High 1. Control valve is fully 1. Flooding in the 1. Install high level
opened
column control alarm
2. Increase pumping
2. Changes in product 2. Check
capacity
quality maintenance
3. Control valves failure
3. Temperature procedure and
decrease schedule
4. Rise in bottom 3. Install double
283
control valve
4. Regular
checking and
maintenance
pumping system
Reverse 1. Too high pressure 1. No operation 1. Install check
inside the column 2. Pressure build up valve
2. Pump failure inside the column or
at the reboiler
Temperature High 1. High temperature of 1. Product quality 1. Install high
2. Steam flow inlet into significantly low alarm at the
reboiler increase 2. Low purity of column
3. Faulty separation obtain 2. Control the
instrumentation and 3. Can cause flooding steam flow into
control inside the column reboiler
4. Heater control failure 4. Cause pressure 3. Control the
5. Coolant at condenser changes inside the temperature of
fail to operate well column feed stream
4. Check the
284
instrumentation
conditions
Low 1. Low temperature of 1. Product quality 1. Install low
2. Loss of heating significantly low alarm
(steam leaking) 2. Low purity of 2. Install automated
3. Reducing pressure separation obtain temperature
4. Faulty 3. Can cause flooding controller
instrumentation and inside the column 3. Control the
control 4. Cause pressure steam flow into
5. Depressurization of changes inside the reboiler
liquefied gas column
Reflux More 1. Control valve fail to 1. Increase reflux ratio 1. Install level
operate well 2. Increase the duty at controller inside
2. Pumping failure the condenser and reflux drum
reboiler 2. Install alarm
level for rising
of drum level
Less 4. Control valve fail to 1. Reduce reflux ratio 1. Install level
operates well 2. Reduce the purity or controller inside
285
5. Pumping failure quality of the reflux drum

product 2. Install alarm
level for lower
level inside the
drum
Level Low 1. Blockage inside the 4. Pressure build up 1. Preventive
inlet feed stream inside the column maintenance
2. Rupture at the outflow 5. Error in separation 2. Install level
valve which disturb the controller and
3. Pump fail to operate VLE of the system alarm
well 6. Reduce the product
quality
High 1. Leakage of valve 1. Flooding inside the 1. Preventive
which causes column maintenance
overflow inside the 2. Error in separation 2. Install level
column which disturb the controller and
2. Instrument for level VLE of the system alarm
indicator is fail to 3. Reduce the product
operate quality
3. Blockage at the
286
bottom stream
Pressure Low 1. Generation of vacuum 1. Low separation 1. Install low
conditions obtain pressure alarm
2. Undetected leakage 2. Flooding inside the 2. Regular
3. Low gas release column maintenance the
4. Changes in piping system of
viscosity/density of column
compound
High 1. Steam heating enter at 1. Can damage the 1. Install high
high pressure column pressure alarm
2. Flooding occur
12.8.3 Pump
UNIT OF Centrifugal Pump, P-100

OPERATION
IDEAL TEMPERATURE(OC) 18 PRESSURE (atm) 19.7
CONDITIONS
FUNCTION OF To increase pressure of C3H6O feed from 1 atm to 19.7 atm before enter the reactor vessel
287
UNIT
WORDS CONSEQUENCES
Flow No 1. Pipe or pump 1. Pipe clog 1. Regular maintenance
rupture 2. No pumping fluid and checking the
2. Large leaking in occur piping and pumping
pipelines system
3. Blockage in pipe 2. Install flow detector
Low 1. Valve not fully 1. Compound 1. Install automated
open released valve
2. Pump failure 2. Reduce production 2. Install flow controller
rate 3. Regular maintenance
3. Cavitation occur the pump
inside pump
4. Defective pump
High 1. Increased 1. Increased suction 1. Install automated

pumping capacity pressure valve
2. Control valve trim 2. Increase fluid 2. Install flow controller
changed
288
3. Reduced delivery density 3. Regular maintenance

head 3. Can cause damage the pump
to pump
Reverse 1. Pump failure 1. No pumping can be 1. Install flow indicator
2. Pump reversed done and negative flow
3. Two-way flow 2. Pipe clog alarm
Pressure High 1. Relief valve 1. Vessel over 1. Install high pressure
malfunction pressure alarm
2. Priming occur 2. Can cause damage 2. Schedule regular
inside pump to pump, might maintenance of relief
3. Positive result in explosion valve
displacement
pump
Low 1. Relief valve fail to 1. Compound 1. Install pressure low
open released to alarm
2. Blockage of atmosphere 2. Update procedure to
blanket gas 2. Cavitation and handle relief valve fail
regulating valve priming occur open
3. Undetected
leakage
289

OPERATION
IDEAL TEMPERATURE(OC) 150 PRESSURE (atm) 2
CONDITIONS
FUNCTION OF To increase pressure of product stream of second reactor from 1 atm to 2 atm
UNIT
WORDS CONSEQUENCES
pipelines system
open released valve
3. Cavitation occur
290
inside pump the pump

4. Defective pump

changed density 3. Regular maintenance
3. Reduced delivery 3. Can cause damage the pump
head to pump
Reverse 1. Pump failure 1. No pumping can 1. Install flow indicator
2. Pump reversed be done and negative flow
displacement
pump
Low 1. Relief valve fail 1. Compound 1. Install pressure low
291
to open released to alarm

blanket gas 2. Cavitation and handle relief valve
regulating valve priming occur fail open
3. Undetected
leakage

OPERATION
CONDITIONS
FUNCTION OF To increase pressure of mixture stream of CH3OH and DMC from 2 atm to 10 atm
UNIT
WORDS CONSEQUENCES
pipelines system
292

open released valve
3. Cavitation occur the pump
inside pump
4. Defective pump

changed density 3. Regular maintenance
3. Reduced delivery 3. Can cause damage the pump
head to pump
Reverse 1. Pump failure 1. No pumping can be 1. Install flow indicator
2. Pump reversed done and negative flow
293

displacement
pump
Low 1. Relief valve fail to 1. Compound 1. Install pressure low
open released to alarm
blanket gas 2. Cavitation and handle relief valve fail
regulating valve priming occur open
3. Undetected
leakage
294
12.8.4 Valve
UNIT OF Pressure Reducing Valve , VLV-100

OPERATION
CONDITIONS
FUNCTION OF To decrease the pressure of bottom product from first distillation column to 1 atm
UNIT
WORDS CONSEQUENCES
Pressure High 1. Valve malfunction 1. Can cause damage 1. Install high pressure
2. Valve isolated to valve alarm
2. Reverse flow of 2. Schedule regular
liquid occur maintenance of valve
Low 1. Valve fail to open 1. Compound released 1. Install pressure low
2. Blockage of to atmosphere alarm
blanket gas 2. Gas dissolving in 2. Update procedure to
regulating valve liquid handle valve fail open
3. Undetected
leakage in
295
pipelines
Flow Less 1. Pipe blockage 1. Temperature of 1. Install low level alarm
2. Fouling of valve process fluid 2. Cleaning the pipelines
3. Valve not fully increase
open
More 1. Control faults 1. Increase pressure 1. Install high level alarm
2. Valve failure inside valve 2. Install automated valve
2. Valve maybe controller
damage

OPERATION
IDEAL TEMPERATURE(oC) 50 PRESSURE (atm) 1
CONDITIONS
FUNCTION OF To decrease the pressure of top product stream from HPC to 1 atm
UNIT
GUIDE POSSIBLE POSSIBLE
WORDS CAUSES CONSEQUENCES
Pressure High 1. Valve 1. Can cause damage 1. Install high pressure
296
malfunction to valve alarm

2. Valve isolated 2. Reverse flow of 2. Schedule regular
Low 1. Valve fail to open 1. Compound 1. Install pressure low
2. Blockage of released to alarm
blanket gas atmosphere 2. Update procedure to
regulating valve 2. Gas dissolving in handle valve fail
3. Undetected liquid open
leakage in
pipelines
Flow Less 1. Pipe blockage 1. Temperature of 1. Install low level
2. Fouling of valve process fluid alarm
3. Valve not fully increase 2. Cleaning the
open pipelines
More 1. Control faults 1. Increase pressure 1. Install high level
2. Valve failure inside valve alarm
2. Valve maybe 2. Install automated
damage valve controller

297
OPERATION
IDEAL TEMPERATURE(oC) 90 PRESSURE (atm) 1
CONDITIONS
FUNCTION OF To decrease the pressure of bottom product stream from HPC to 1 atm
UNIT
WORDS CONSEQUENCES
Pressure High 1. Valve malfunction 1. Can cause damage 1. Install high pressure
2. Valve isolated to valve alarm
2. Reverse flow of 2. Schedule regular
Low 1. Valve fail to open 1. Compound released 1. Install pressure low
2. Blockage of to atmosphere alarm
blanket gas 2. Gas dissolving in 2. Update procedure to
regulating valve liquid handle valve fail open
3. Undetected
leakage in
pipelines
Flow Less 1. Pipe blockage 1. Temperature of 1. Install low level alarm
process fluid
298
2. Fouling of valve increase 2. Cleaning the pipelines

3. Valve not fully
open
More 1. Control faults 1. Increase pressure 1. Install high level alarm
2. Valve failure inside valve 2. Install automated valve
2. Valve maybe controller
damage
12.8.5 Compressor
UNIT OF Screw Compressor, C-100

OPERATION
IDEAL TEMPERATURE(OC) 179 PRESSURE (atm) 19.7
CONDITIONS
FUNCTION OF To compress the gas feed of carbon dioxide at 1 atm to 19.7 atm
UNIT
FUNCTION OF Suction valve - the component where air flow is controlled
STUDY NODES
STUDY NODES SUCTION VALVE
299

WORDS CONSEQUENCES
Pressure Less 1. Valve partly or 1. Business loss 1. Install gas detection
completely closed 2. Damage system
2. Human error compressor 2. Water monitors
3. Strainer is choked 3. Rise in temperature, 3. Training worker
4. Leakage or cause fire &
puncture in explosion
pipeline
5. Breaking of gasket
6. Low suction
7. Engine fails
More 1. Valve completely 1. Discharge valve 1. Install high pressure
or partially closed will blow alarm
2. Gas trapping when 2. Decrease the 2. Regular checking and
shut down suction pressure cleaning
3. Install controller for
suction valve
300
Temperature High 1. Insufficient 1. Increase 1. Install high

cooling temperature inside temperature alarm
2. Suction pressure compressor 2. Water monitor
low 2. Can cause damage 3. Monitor the discharge
to compressor gas temperature
12.8.6 Flash Column
UNIT OF Low Pressure (Flash) Column, LPC-101

OPERATION
CONDITIONS
FUNCTION OF To separate methanol (CH3OH) and dimethyl carbonate (DMC) to get high purity of product
UNIT
FUNCTION OF Vessel – To house the flash separation process
STUDY NODES
WORDS CONSEQUENCES
301
Pressure High 1. High column 1. Result in lower 1. Install safety relief

temperature concentration of valve
2. Feed mixture product obtained 2. Install high pressure
enters at higher 2. Possible explosion alarm
pressure
Low 1. Low column 1. Result in lower 1. Install low pressure
temperature concentration of alarm
2. Feed mixture product obtain
enters at lower
pressure
Temperature High 1. Feed mixture 1. Builds up pressure, 1. Install high temperature
entering the vessel lead to possible alarm
is high explosion
temperature
Low 1. Feed mixture 1. Result in less 1. Install low temperature
entering the vessel separation between alarm
is low temperature desired product and
by-product
Level High 1. Outlet stream 1. Overflow in the 1. Schedule regular
clogged
flash column cleaning sessions
2. Control valve
302
failure 2. Install high level alarm
12.8.7 Heat Exchanger
UNIT OF Heat Exchanger

OPERATION
FUNCTION OF To exchange the heat energy between hot stream and cold stream
UNIT
FUNCTION OF Shell – to provide area of exchange heat in hot stream
STUDY NODES
Tube – to provide area of exchange heat in cold stream
STUDY NODES Tube and Shell

WORDS CONSEQUENCES
Flow No 1. Pipe broken 1. Not achieve a desire 1. Install a filter at the
2. Pump and valve temperature cool stream
malfunction 2. Effect further 2. Install flow indicator
303
3. Pipe plugging process 3. Install temperature

3. Temperature and indicator and high
pressure increase temperature alarm
High 1. Valve fail to open 1. Not achieve a desire 1. Install an orifice plate
2. The pump cannot temperature 2. Install a flow meter
be control 2. Effect further 3. Install high flow alarm
3. The hot fluid pipe process 4. Schedule regular
raptures 3. Temperature and maintenance of valves
4. Amount of the pressure increase
component in cool
stream increases
Flow Low 1. Control valve 1. Not achieve a desire 1. Install a low flow
malfunction temperature alarm
2. The cool stream 2. Effect further 2. Schedule regular
flow pipe is process maintenance of valve
plugged 3. Temperature and
pressure increase
Reverse 1. Cool stream pump 1. Difficult to control 1. Install one way flow
not functioning the temperature valve at the coolant
2. Higher pressure in flowing out flowing in pipe
304
flow out 2. Cooling is not 2. Ensure the pump is

effective for always in good
equipment condition and
functional
Temperature High 1. Heat exchanger is 1. Pressure will 1. Install high
not functioning increase temperature alarm at
2. Temperature of the 2. Explosion will the out flow hot fluid
hot fluid is too high occur stream
3. Valve failure 3. Failure of other 2. Repair the damage
equipment part of heat exchanger
Low 1. Control system not 1. Temperature 1. Install low
functioning increases with that temperature alarm
2. No temperature condition 2. Schedule regular
change at the 2. Failure of other cleaning of valves and
coolant flow stream equipment pipes
3. Condensation
occurs at the tube
of the heat
exchanger
305
12.8.8 Mixer
UNIT OF Mixer, MIX-100

OPERATION
CONDITIONS
FUNCTION OF To mixer the feed stream and recycle stream
UNIT
WORDS CONSEQUENCES
Flow No 1. Flow control valve 1. Mixing process 1. Install flow controller
failure cannot be done valve
2. Pipe blockage 2. Decrease the rate of 2. Install flow indicator
3. Equipment failure mixing 3. Repair and cleaning
3. Loss of feed to the pipe
mixer
Low 1. Flow control valve 1. Low flow rate of 1. Install flow controller
failure component in valve
306
2. Pipe blockage mixer 2. Install flow indicator

3. Fouling of vessel 2. Rate of mixing 3. Repair and cleaning
drop the pipe
More 1. Pressure 1. Rate of mixing 1. Install flow indicator
differential is too increase 2. Consider alternatives
high 2. Reaction build up trip system
2. Failure of control 3. Poor product 3. Install high level
3. Increase pump quality alarm
capacity 4. Deviation in
pressure
Temperature High 1. Temperature 1. High mixer 1. Install high
controller failure temperature temperature alarm
2. Valve failed or into temperature
blocked controller to control
temperature control
valve

OPERATION
CONDITIONS
307

UNIT
WORDS CONSEQUENCES
2. Pipe blockage 2. Decrease the rate 2. Install flow indicator
3. Equipment failure of mixing 3. Repair and cleaning
mixer
drop the pipe
308

pressure
controller failure temperature temperature alarm
2. Valve failed or into temperature
blocked controller to control
temperature control
valve

OPERATION
IDEAL TEMPERATURE(OC) -65 PRESSURE (atm) 1
CONDITIONS
UNIT
WORDS CONSEQUENCES
309

2. Pipe blockage 2. Decrease the rate of 2. Install flow indicator
3. Equipment failure mixing 3. Repair and cleaning
mixer
drop the pipe
pressure
controller failure temperature temperature alarm into
2. Valve failed or temperature controller
310
blocked to control temperature

control valve
311
12.9 Fault Tree Analysis
Fault tree analysis is an effect and cause diagram that uses standard symbols
developed in the defense industry and is used heavily in safety engineering. It is a
structured approach for analyzing the root causes of a failure in the equipment which
are not yet fully understood. In fault tree analysis, overall undesired system failures
could be broken down further to component failure modes and operator actions for
better comprehension of the failure. Although there are other methods to assess the
failure of systems, experts feel that fault tree analysis is better suited to understand
layers and relationships of causes of equipment failures.
12.9.1 Fault and Probability Data
As compared to HAZOP analysis, fault tree analysis focuses more on

quantitative analysis. To be more specific, it is to determine the probability of the plant
to face failure and damage during its operational lifetime. For this purpose, it is crucial
to obtain accurate data concerning the faulty aspect of equipment and instrument which
maintains and supports the operations and well-being of the plant. In norm practices,
the fault data is obtained through experience and thorough inspection of the equipment
and instrument used around a plant, and in most cases are plant specific. Although this
may be the case, a generalised data was taken in order to assess the failure risk of
equipment around the plant. The probability of instrument failure is calculated through
Equation 11.1 and is related an operational period of 1 year (Crowl & Louvar 2001).
The data are shown in Table 12.4.
P = 1 - e−µt ….. (Eq. 12.1)
Where,
312
P is the probability of failure of instrument

µ is the failure rate of instrument in faults/year
t is the time period of operation assessed for the instrument
Table 12.6: Failure Risk Data of Instruments

Instruments µ (Faults/year) P (Probability)
Controller 0.290 0.2517
Control valve 0.028 0.0276
Flow switch 1.120 0.6737
Indicator lamp 0.044 0.0430
Pressure switch 0.140 0.1306
Temperature switch 0.220 0.1975
Pressure relief valve 0.022 0.0218
Level switch 0.220 0.1975
Electric motor 0.511 0.4001
Reference: Crowl & Louvar 2001, Mannan 2004
12.9.2 Minimal Cut Set
The fault tree development consists of multiple levels of basic events and sub-
events linked together by OR and AND gates. The minimal cut set analysis is present to
rearrange the fault tree developed so that basic events that appear in different parts of the
fault tree is not double counted in the quantitative analysis. The results of the minimal
cut set analysis is a new fault tree, logically equivalent to the original, consisting of an
OR gate beneath the top event, whose inputs are the minimal cut sets. Each minimal cut
set is an AND gate containing a set of basic inputs. A software could be used to generate
the minimal cut set using the Boolean Algebra.
313
12.9.3 Analysis
The analysis will be done on several equipment utilized by the designed plant.
The equipment chosen for the analysis include the reactor, pump, flash column and
distillation column. The equipment stated here will represent their respective major
equipment categories of the plant.
314
12.9.4 Reactors (SR-1 & SR-2)
Figure 12.3: Fault Tree Analysis for Reactors (SR-1 & SR-2)
315
Overpressure of reactor
P (D, OR) = P(1)+P(2) = 1- [(1-0.1306) x (1-0.0430)]
= 0.1679 (probability of pressure alarm failing)
P(E, OR) = P(3) + P(4) + P(5) = 1-[(1-0.1306) x (1-0.2517) x (1-0.0276)]
= 0.3674 (probability of pressure control system failing)
P(B, AND) = P(D) × P(E)×P(6) = 0.1679 × 0.3674 × 0.0218
= 0.013 (probability of overpressure)
Overheating of reactor
P(F, OR) = P(7) + P(8) = 1-[(1-0.1975) x (1-0.0430)]
= 0.2320 (probability of temperature alarm failing)
P(G, OR) = P(9) + P(10) + P(11) = 1-[(1-0.1975) x (1-0.2517) x (1-0.0276)
= 0.4161 (probability of temperature control system failing)
P(C, AND) = P(F) × P(G) = 0.2320 × 0.4161
= 0.0965 (probability of overheating)
Failure of reactor
P(A, OR) = P(B) + P(C) = 1-[(1-0.013)-(1-0.0965)]
= 0.1082
316
12.9.5 Flash Column (LPC-100)
Figure 12.4: Fault Tree Analysis for Flash Column (LPC-100)

317
Overpressure of flash column

P (D, OR) = P(1)+P(2) = 1- [(1-0.1306) x (1-0.0430)]
P(E, OR) = P(3) + P(4) + P(5) = 1-[(1-0.1306) x (1-0.2517) x (1-0.0276)]
P(B, AND) = P(D) × P(E)×P(6) = 0.1679 × 0.3674 × 0.0218
Overheating of flash column

P(F, OR) = P(7) + P(8) = 1-[(1-0.1975) x (1-0.0430)]
P(G, OR) = P(9) + P(10) + P(11) = 1-[(1-0.1975) x (1-0.2517) x (1-0.0276)
P(C, AND) = P(F) × P(G) = 0.2320 × 0.4161
Failure of flash column

P(A, OR) = P(B) + P(C) = 1-[(1-0.013)-(1-0.0965)]
= 0.1082
318
12.9.6 Distillation Column (DC-100, DC-101 & HPC-100)
Figure 12.5: Fault Tree Analysis for Distillation Column (DC-100, DC-101 & HPC-100)
319
Overpressure of distillation column

P (D, OR) = P(1)+P(2) = 1- [(1-0.1306) x (1-0.0430)]
P(E, OR) = P(3) + P(4) + P(5) = 1-[(1-0.1306) x (1-0.2517) x (1-0.0276)]
P(B, AND) = P(D) × P(E)×P(6) = 0.1679 × 0.3674 × 0.0218
Overheating of distillation column

P(F, OR) = P(7) + P(8) = 1-[(1-0.1975) x (1-0.0430)]
P(G, OR) = P(9) + P(10) + P(11) = 1-[(1-0.1975) x (1-0.2517) x (1-0.0276)
P(C, AND) = P(F) × P(G) = 0.2320 × 0.4161
Failure of distillation column

P(A, OR) = P(B) + P(C) = 1-[(1-0.013)-(1-0.0965)]
= 0.1082
320
12.9.7 Pump (P-100, P-101 & P-102)
Figure 12.6: Fault Tree Analysis for Pumps (P-100, P-101 & P-102)
321
Overpressure of pump
P(C,OR) = P(1) + P(2) = 1-[(1-0.1306) x (1-0.0430)]
= 0.1679 (probability of alarm failure)
P(B,AND) = P(C) × P(3) = 0.1679 × 0.0218
Failure of pump
P(A, OR) = P(B) + P(4) = 1-[(1-0.0037) x (1-0.4001)]
= 0.4023
322
12.9.8 Pressure-Reducing Valves (VLV-100, VLV-101 & VLV-102)
Figure 12.7: Fault Tree Analysis for Valves (VLV-100, VLV-101 & VLV-102)
323
Overpressure of valve
P (D, OR) = P(1)+P(2) = 1- [(1-0.1306) x (1-0.0430)]
P(E, OR) = P(3) + P(4) + P(5) = 1-[(1-0.1306) x (1-0.2517) x (1-0.0276)]
P(B, AND) = P(D) × P(E)×P(6) = 0.1679 × 0.3674 × 0.0218
Overflow in valve
P(F, OR) = P(7) + P(8) = 1-[(1-0.6737) x (1-0.0430)]
= 0.6877 (probability of flow alarm failing)
P(G, OR) = P(9) + P(10) + P(11) = 1-[(1-0.6737) x (1-0.2517) x (1-0.0276)
= 0.7626 (probability of flow control system failing)
P(C, AND) = P(F) × P(G) = 0.6877 × 0.7626
= 0.5244 (probability of overflow)
Failure of valve
P(A, OR) = P(B) + P(C) = 1-[(1-0.013)-(1-0.5244)]
= 0.5306
324
12.9.9 Heaters (H-100 & H-101)
Figure 12.8: Fault Tree Analysis for Heaters (H-100 & H-101)
325
Overpressure of heater
P (D, OR) = P(1)+P(2) = 1- [(1-0.1306) x (1-0.0430)]
P(E, OR) = P(3) + P(4) + P(5) = 1-[(1-0.1306) x (1-0.2517) x (1-0.0276)]
P(B, AND) = P(D) × P(E)×P(6) = 0.1679 × 0.3674 × 0.0218
High temperature of heating medium

P(F, OR) = P(7) + P(8) = 1-[(1-0.1975) x (1-0.0430)]
P(G, OR) = P(9) + P(10) + P(11) = 1-[(1-0.1975) x (1-0.2517) x (1-0.0276)
P(C, AND) = P(F) × P(G) = 0.2320 × 0.4161
Failure of heater
P(A, OR) = P(B) + P(C) = 1-[(1-0.013)-(1-0.0965)]
= 0.1082
12.9.10 Summary
Table 12.7: Summarized Failure Risk Analysis of Studied Equipment

Probability of
Equipment Faults/year MTBF
Failure
Reactor 0.1082 0.1145 8.7336
Distillation Column 0.1082 0.1145 8.7336
Flash Column 0.1082 0.1145 8.7336
Pump 0.4023 0.5147 1.9429
326
Valves 0.5306 0.7563 1.3222

Heater 0.1082 0.1145 8.7336
The probability of failure for each equipment studied are shown in Table 11.4
above. The same probability of failure of 0.1082 was found for the reactors, distillation
columns, flash column and heaters. This results in the possible 0.1145 faults per year
and the minimum time before a fault (MTBF) happens will be about 9 years. In fact,
the pump is of greater importance as the parts of the motor could easily be damaged, be
it the electric motor or the pump section. Therefore, it has a higher probability to face
failure during the operation of the plant, resulting in about 0.5147 faults per year and
minimum time before the fault happens is about 2 years. This goes the same for
pressure-reducing valves which face even more significant effect from possible damage
due to their 0.7563 faults per year rate which is the highest among the rest. Besides, it
is expected for the valves to be replaced after about 1.5 years before they are
permanently disabled.
In conclusion, it would be best for the operators to place much-needed attention

to the pumps and valves to ensure that there is no significant damage that will affect the
plant’s operation and the safety of the personnel. There should be constant monitoring
of the equipment and it has to be ensured that all the instruments associated with each
equipment are functioning well.
A plant start-up involves a point in the project in which process fluids and
conditions are established with an intent of making products. It is also defined as the
327
transitional phase between plant construction completion and commercial operations,

including all of the activities that bridge these two phases. Critical steps within the
startup phase include system turnover, check-out of systems, commissioning of
systems, introduction of feedstock, and performance testing.
On the other hand, a plant shutdown can be defined as a scheduled down period
for a plant for scheduled maintenance for an extended period of time. Shutdowns
provide unique opportunities to a maintenance department not normally available
during standard operation or even during short shutdown periods. It is essential to
conduct a plant maintenance shutdown to keep the facility running smoothly despite it
can be timely and causes loss in production but the benefits of scheduled maintenance
of the machinery can help to prevent future failures and decreases downtime.
The startup and shutdown of a plant must be handled safely and easily, yet
flexible enough to be carried out in several ways. The operating limits of the plant must
not be exceeded and dangerous mixtures must not be formed. It is occasionally
necessary to introduce additional equipment, sampling point, instrumentation and lines
and identify their uses on the engineering line diagram. There are several important
aspects that needs to be taken into consideration during the startup and shutdown of the
plant.
The following shows the pre-startup procedures that should be implemented in a

plant startup process.
1) Before the man-ways covers are installed on the towers or vessels, a final
inspection should be made of the interiors of each tower and vessels for
328
cleanliness and conformance to the design specification.

2) Check all the items in the “turnaround Worklist” whether they have been
completed and all the equipment and the associated lines have correctly
reassembled.
3) If any heat exchangers were opened during the turnaround for inspection,
cleaning and mechanical work, they must be hydrostatically tested after they
have been assembled.
4) Check all the instruments control loops that the alarm circuits are functioning
correctly.
5) Check all the level gauge glasses for cleanliness.
6) Make sure that all the control valves operable.
7) Check all the orifice plates have been installed properly.
8) Check the pumps for operability.
9) Check all the utilities, power steam and cooling water. Check all the steam traps
are functioning.
10) Make sure that all the safety valves are tested, installed and the block valve are
sealed in their respective operating position.
11) Check all onsite fire protection equipment such as extinguishers, water hoses,
nozzles and steam hoses are in place and ready for immediate use.
12) Check all the drains are unplugged and all the water drained from equipment.
13) Make sure all the flanges and man heads have good gasket and are made up tight.
14) The safety valve header, the blow down line and the flare system are successfully
commissioned.
15) All the blinds are required for tightness testing and air freeing equipment are
available, removed or installed.
16) Make all the steam tracing is operable.
17) The supply of chemicals are adequate and at band.
18) Air freeing and tightness testing.
19) Gas blanketing.
20) Catalyst should be activated and sufficiently warm reaction to commence when
the flow of reactants is started.
329
The following shows the pre-shutdown procedures that should be implemented

in a plant shutdown process.
1) The ‘Turn-around Work list’ is to be prepared to include all items for repair,
cleaning, inspection and modification.
2) The detailed plan of the shutdown and turnaround for the day to day and
probably hour by hour schedule of the sequence of the events are to be prepared.
3) Before shutting down, the following should be checked:
 The firefighting equipment are to be correctly located.
 The personal protective equipment are to be available for immediate use.
All items that are required for the shutdown of the unit operations should be
made available. These items include blinds, hoses for steaming out circuits and
equipment, hoses for draining circuit equipment of liquid, connections for connecting
those hoses.
12.10.4 Plant Emergency Shutdown
The emergency shutdown of the plant is mostly due to the following:
1. Losses of utility supply such as cooling water, electricity, steam and others.
2. Mechanical failure of equipment prevents normal operation or result in a
serious fire or leak.
3. An emergency response plan should be prepared for the safety of the
employees and public. The two steps should be taken during the event of an
330
emergency. Firstly, determine the extent of the emergency condition.

Secondly, decide on how to cope with emergency.
4.
331
CHAPTER 14
CONCLUSION
The proposed dimethyl carbonate (DMC) production plant will operate

towards the annual production capacity of about 100,000 metric tons (MT) of
dimethyl carbonate. The main reaction route that will be utilized is the
transesterification of propylene carbonate with methanol which has the major
advantage of the absence of any significant waste produced as a move towards
sustainability and environmental-friendly approach. Besides, this chemical route also
produces a marketable by-product in the form of propylene glycol which can be sold
at RM6.34 per kg. With the current market price of dimethyl carbonate at about
RM5.50 per kg and combined with the selling of propylene glycol as well, the margin
for profit will be rather high despite one of the raw materials, propylene oxide, being
more costly. There will be an estimated profit of about RM 2.63/kg of dimethyl
carbonate produced.
Due to the need for methanol resources as the more essential raw material and
land availability purposes, the planned location of the plant will be at Gebeng, Pahang
because this industrial land focuses mainly on industry that is based on petrochemical
332
and chemical industry which can serve as a great marketing prospect. Although raw
material availability is the primary concern, other factors were also taken into account
such as land prices, utilities provision, marketing potential and others. Since the Gebeng
area is close the Gebeng bypass which is strategically located near to the Kuantan Port
that links Kuala Lumpur and Kuantan directly via East Coast Highway, it would not be a
problem in terms of transportation access. Besides, Gebeng also possesses some of the
cheapest land prices in the nation and the abundance of raw materials is present as well.
The innovation potential in this process and plant design is the application of
CeCu catalyst which could potentially replace most commercially available catalysts in
the industry that is used to produce dimethyl carbonate. The catalyst used in most
previous research and process is the ion-exchange resin. Although ion-exchange resin
is commercially available, it can only be used in a few cycles and requires continuous
maintenance gradually. Therefore, CeCu catalyst is a promising development in this
aspect despite it is still currently new within lab-scale production. However, it still
shows great potential as it could provide about 72% conversion of methanol and
propylene carbonate as compared to the original rate at 16%. Another innovation
incorporated in this design is the application of pressure-swing distillation in dealing
with the separation of azeotropic DMC-methanol mixture in contrary with extractive
distillation. This is because the former is more environmental-friendly and avoid the
use of an additional separating agents with only changes being made to the operating
pressure.
The operation of this plant will run for 24 hours a day, 7 days a week and about
340 days a year (8200 hours), allowing about 20 days or more for plant shut down for
maintenance and equipment check. The resulting flow for each component is viewed on
an hour basis. The consumption of carbon dioxide and propylene oxide is about 1 ton
and 1.2 tons per hour respectively (feeds into reactor), dimethyl carbonate production
about 2 tons per hour and propylene glycol at about 1.5 tons per hour. Due to the use of
the CeCu catalyst, the conditions can be lowered to about 150°C, as compared to other
catalysts, which may result in greater reaction temperature of about 500-600°C. The
333
reaction pressure at 1 atm is sufficient enough to provide a pressurized condition for the
transesterification of propylene carbonate and methanol.
Manual calculations were conducted for both mass and energy balances with
basis from chemical engineering principles. Assumptions were also made while
required data was obtained from literature study and research, thereby rendering the
calculations to be rather accurate. The HYSYS simulation program was also used to
simulate the planned process and this provided a basis of comparison for the manual
calculations and the assumptions made for the calculations. As a result, the difference
between the manual and simulated results were all below 15%, with the highest
difference at about 14%. This low percentage difference proved that the calculations
were quite close to that of actual conditions and therefore, the design could proceed
without making any major alterations.
As for optimization, one of the distillation columns (DC-101) was analyzed

using the GAMS optimization program. Emphasis was put on the dimensions of the
reactor, which could hold the catalyst and possess proper heating area for the reactor to
maintain the temperature at 250°C. The approach towards optimization will be the
comparison of the results before and after the optimization execution in which a total of
about 70% could be saved in terms of column cost, which amounts to RM5 millions of
savings in terms of capital costs. Other than that, manual calculations were made to
ascertain proper feed stage for the distillation column as well as the operating
temperature of the flash column to obtain the highest purity of distillate.
Process control served to provide a well-automated plant which could sustain

itself with minimal human intervention. Based on the safety aspects of the plant,
various criteria were taken into consideration in planning for a proper plant startup,
shutdown, material management and handling and so on to ensure the safety of
personnel around the plant. The Hazard and Operability Study (HAZOP) analysis was
also done for the plant that aims to plan precautionary steps for unprecedented
334
situations involving the failure of control systems. These control systems could be
made fully automated to alert personnel to the possible risk of any system failures. In
addition, the fault tree analysis was also conducted on major equipment of the plant to
foresee the possible risk of facing equipment failure and with that, operators can be
notified beforehand regarding to equipment which are more susceptible to failure.
The economic analysis for the plant involved the estimation of the payback
period as well as the rate of return. With the MARR set at 20%, an internal rate of
return (IRR) or Discounted Cash Flow Rate of Return (DCFRR) of 65.67% is quite
favourable as it yields high returns for the plant. With EMIP at 2.15 years, the
investment in the plant will be secure about .2.15 years, when the investment capital
mostly be gathered after that period of time. The breakeven point at 41 thousand tons of
dimethyl carbonate production per year justified the plant to operate at a capacity of
15,000 metric tons per year. Lastly, the short payback period would also peak investors
interest in the plant, as within 6 years of the plant design being conceive, the plant
could regain all of its capital spending and begin to profit afterwards.
In conclusion, the setup of this dimethyl carbonate production plant will be a

rewarding opportunity due to its good profitability and sustainable credibility despite its
currently underdeveloped industry on local grounds. Nevertheless, dimethyl carbonate
has found many applications in the market now especially in the production of
polycarbonate. Its influence on the global market is relatively extensive with Japan and
China as some of the major leading manufacturers of dimethyl carbonate. Besides, the
potential for sustainable and environmental-friendly plant designs has also gain much-
needed attention due to the current worldwide outlook on environmental issues. Thus, it
is deemed feasible for make this plant to produce 15,000 MTA of dimethyl carbonate a
reality because it has the potential to be an ever-growing industry in the future.

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i

PLANT DESIGN PROJECT (SKKK 4824)

PRODUCTION OF 15, 000 MTA DIMETHYL CARBONATE

Assoc. Prof. Dr. Zainura Zainon Noor

DESIGN TEAM MEMBERS:

AQILA BINTI ALIAS A13KK0016

Dimethyl carbonate was initially produced by the reaction of methanol and

conversion rate of propylene carbonate to dimethyl carbonate is approximately 65%.

CHAPTER TITLE PAGE

TABLE OF CONTENTS iii

1.0 LITERATURE REVIEW & PROJECT

2.0 PROCESS CREATION AND SYNTHESIS

3.0 MANUAL MATERIAL AND ENERGY BALANCE

4.0 PRELIMINARY SIMULATION OF MATERIAL

AND ENERGY BALANCE

5.0 INNOVATION POTENTIAL

6.0 PROCESS HEAT INTEGRATION

7.0 PROCESS OPTIMIZATION

8.0 EQUIPMENT SIZING AND COSTING

9.0 MECHANICAL DESIGN

10.0 WASTE TREATMENT

11.0 PROCESS CONTROL AND INSTRUMENTATION

11.4 Piping and Instrumentation Diagram (PID)

12.0 PROCESS SAFETY

12.2 General Safety Guidelines

13.0 PROFITABILTIY ANALYSIS

12.10 Plant Startup and Shutdown

Appendix E: Simulation Design and Stream Summary

FIGURE NO. TITLE PAGE

Temperature, Pressure and Phase Change Operations

11.10 Process Control Loop of Heater 2 (H-101)

TABLE NO. TITLE PAGE

2.5 Comparison between Alternative 1 (Figure 2.3) and 57

8.11 Pump (P-102) Equipment Specification Sheet

12.1 Effect Assessment of Aquatic Organisms

LITERATURE REVIEW & PROJECT CONCEPTION

1.1 Chemical Product Background

Dimethyl carbonate (DMC) is an organic compound with the formula

Dimethyl carbonate was originally made by the reaction of two moles of

Dimethyl carbonate is increasingly used as a methylating agent in place of

1.1.1 Physical and Chemical Properties of Dimethyl Carbonate

1.1.2 Applications of Dimethyl Carbonate

1.1.2.1 Organic solvent

Dimethyl carbonate (DMC) is a relatively new chemical on the market. Although

major usages. DMC is mainly used as an organic solvent in synthesis of other

1.1.2.2 Traditional substitute of toxic materials

pharmaceutical industry, it can be used for making amino oxazolidinone, ciprofloxacin,

1.1.2.3 Paints, inks and coatings

1.1.2.4 Polycarbonate production

1.1.2.5 Pharmaceutical and intermediate chemical

In the pharmaceutical sector, DMC is mainly used as methylating agent in the

1.1.2.6 Fuel additives

1.1.3 Safety Measures and Toxicity

Dimethyl carbonate can be hazardous in case of skin contact (irritant), of eye

Dimethyl carbonate is also flammable and when heated, explosion of containers

1.1.4 Storage and Handling

The conditions for safe storage of dimethyl carbonate include any

Inhalation of vapor or mist of dimethyl carbonate can be avoided by personal

1.2 Market Survey

1.2.1 Market Demand of Dimethyl Carbonate