(HTS) High Temperature Shift Catalyst (VSG-F101) - Comprehensiev OverviewGerard B. Hawkins
The document discusses improvements in high temperature shift catalysts. It describes the characteristics and operational issues of traditional HTS catalysts and how the new VULCAN Series VSG-F101 catalyst has addressed these issues through modifications to its microstructure and composition. The VSG-F101 has shown improved activity, strength, and resistance to thermal and mechanical stresses during plant upsets compared to previous catalysts.
This document discusses primary reforming processes for producing hydrogen and ammonia. It describes a simplified steam reforming process that involves steam reforming, water-gas shift reaction, hydrogen purification, and ammonia synthesis. Steam reforming converts hydrocarbon feeds to hydrogen, carbon monoxide, carbon dioxide, and water using steam and a catalyst inside heated tubes. There are various options for reforming sections, including pre-reformers, secondary reformers, and gas-heated reformers. Tubular steam reformers are commonly used and can be top fired, side fired, or use a terraced wall design depending on the process designer and plant capacity.
This document discusses secondary reforming in ammonia and hydrogen/syngas production. It explains that ammonia plants commonly use a secondary reformer fired with air, as the nitrogen from air is useful for ammonia synthesis. However, hydrogen/syngas plants less commonly use secondary reforming because nitrogen cannot be tolerated in the process and an air separation unit may not be available or affordable to provide oxygen. The document outlines the key components of secondary reformers - the burner design, mixing volume, and catalyst - which must all be optimized to improve performance.
Common poisons include
Sulfur
Chlorides and other halides
Metals including arsenic, vanadium, mercury, alkali metals (including potassium)
Phosphates
Organo-metalics
Hydrogen Plant Flowsheet - Effects of Low Steam RatioGerard B. Hawkins
Effect of Low Steam Ratio on the Steam Reformer
Effect of Low Steam Ratio on H T Shift & PSA
Effect of Low Steam Ratio on Gross Efficiency
Effect of Low Steam Ratio on Net Efficiency
Alternative schemes for improving heat recovery
The Benefits and Disadvantages of Potash in Steam ReformingGerard B. Hawkins
Why do we include potash ?
What are the benefits ?
What are the disadvantages ?
Catalyst Deactivation
Carbon Deposition : Thermodynamics & Kinetics
Carbon formation margin
Reaction chemistry (Tube inlet)
Hydrocarbons undergo cracking reactions on hot surfaces at the tube inlet
Products of catalytic cracking reactions can form polymeric carbon
The document discusses various technologies for producing hydrogen and synthesis gas, including steam reforming, partial oxidation, coal gasification, and water electrolysis. It provides an overview of the main industrial processes used for ammonia synthesis gas production, noting that about 85% is based on steam reforming of natural gas or other light hydrocarbons. Various hydrogen and syngas production processes are also compared in terms of energy consumption, investment cost, and production cost.
Catalyst Catastrophes in Syngas Production - II
Contents
Review of incidents by reactor
Primary reforming
Secondary reforming
HTS
LTS
Methanator
Reactor loading
Support media
Some general comments on alternative actions when a plant gets into abnormal operation
This document discusses ammonia (NH3) formation over steam reforming catalysts. It provides rules of thumb for NH3 formation in primary and secondary reformers, noting it is kinetically limited and does not reach equilibrium. NH3 formation is influenced by nitrogen concentration, hydrogen concentration, temperature, catalyst activity, residence time, and pressure. The document also presents theoretical rate equations and discusses how process conditions like steam:carbon ratio affect NH3 production. Graphs demonstrate the effect of temperature and pressure on NH3 production.
Equilibrium Effects
- Methane Steam
- Water Gas Shift
Relationship of Kp to Temperature
Relationship of WGS Kp to Temperature
Effect of Temperature on Methane Slip
Approach to Equilibrium
Reaction Path and Equilibrium
Effect of Pressure Increase
Operating Parameters
- Pressure
- Temperature
- Feed Rate
- Steam to Carbon
Effect of Exit Temperature Spread
Useful Tools
Calculating ATM
Catalyst Catastrophes in Syngas Production - I
The Hazards
Review incidents by reactor
Purification….
Through the various unit operations to
Ammonia synthesis
Nickel Carbonyl
Pre-reduced catalysts
Discharging catalysts
Conclusion
The document discusses different types of reformers used in ammonia plants, including pre-reformers, primary reformers, and secondary reformers. It provides details on the process, internals, catalysts, and operating conditions of each reformer type. Primary reformers are described as duplex reforming furnaces containing nickel catalyst-loaded tubes that are fired by natural gas burners to drive the endothermic reforming reactions. Key variables that impact the reforming reactions such as temperature, pressure, steam-to-carbon ratio, and catalyst activity are also summarized.
(LTS) Low Temperature Shift Catalyst - Comprehensive OverviewGerard B. Hawkins
The document discusses low temperature shift catalysts used in hydrogen production plants. It describes the purpose of low temperature shift catalysts in further converting carbon monoxide to carbon dioxide to improve hydrogen yield and remove impurities. It then covers the chemistry, typical operating conditions, factors influencing catalyst activity like temperature profile and poisons, and byproduct formation issues. The document promotes the VSG-C111/112 series as superior catalysts, highlighting their resistance to poisons like sulfur and chloride, low methanol byproduct formation, high activity, and strength properties.
This document summarizes different processes for removing carbon dioxide from ammonia plant streams. It discusses why CO2 removal is important, and describes common processes like MEA and MDEA absorption. The Benfield process uses hot potassium carbonate solution promoted by diethanolamine to physically absorb CO2. Issues with the Benfield process include foaming, corrosion, and vanadation problems. Retrofitting with a new amine promoter called LRS 10 can improve CO2 removal efficiency and reduce energy costs for the Benfield process.
Most modern ammonia processes are based on steam-reforming of natural gas or naphtha.
The 3 main technology suppliers are Uhde (Uhde/JM Partnership), Topsoe & KBR.
The process steps are very similar in all cases.
Other suppliers are Linde (LAC) & Ammonia Casale.
This document discusses operating pre-reformers at high temperatures and the associated benefits and drawbacks. It notes that while higher temperatures allow for better thermal efficiency and feedstock flexibility in reformers, they can also cause hydrothermal sintering of catalysts over time from high heat and steam. The document provides guidelines for startup, reduction, and operation of pre-reformer catalysts to maximize performance while mitigating sintering risks.
1. The document discusses gas burner technology and design for application, covering topics such as combustion reactions and products, emissions, heat transfer effects, design considerations, CFD and FEM analysis, testing, and noise.
2. Key aspects of burner design include the burner body/flame diffuser, distributor, and front flange, which impact modulation, emissions, and noise behavior. Design is customized based on the application and gases used.
3. Testing evaluates performance with reference and limit gases to ensure stability, emissions, and modulation over a range of gas qualities. CFD and FEM are used to analyze flame shape, temperatures, stresses, and failure prediction.
Introduction and Theoretical Aspects
Catalyst Reduction and Start-up
Normal Operation and Troubleshooting
Shutdown and Catalyst Discharge
Nickel Carbonyl Hazard
Enhancing the Kinetcs of Mill Scale Reduction: An Eco-Friendly Approach (Part 2)chin2014
This document summarizes a research paper on enhancing the kinetics of mill scale reduction using hydrogen gas as an eco-friendly approach. The document includes:
1. An introduction to mill scale, its composition, and issues with current techniques for treating it.
2. A literature review summarizing previous research on reducing iron oxide using hydrogen and production of sponge iron powder from mill scale.
3. The objectives of experimentally studying the reduction kinetics using hydrogen gas at different temperatures and times to efficiently produce iron powder.
1) Methanation is the final stage of synthesis gas purification to reduce carbon oxides like CO and CO2 to trace levels using a nickel-based catalyst.
2) Typical methanation reactions are highly exothermic and occur between 270-290°C with carbon oxide inlet levels of 0.1-1.0% and carbon oxide slip less than 5 ppm.
3) Normal methanator operation involves monitoring inlet/outlet temperatures and carbon oxide levels to detect any issues like catalyst aging or poisoning that could impact the removal of carbon oxides to the required levels.
Ammonia production from natural gas, haldor topsoe processGaurav Soni
The document provides information about the various sections of an ammonia plant, including the desulfurization, reforming, shift, CO2 removal, methanation, and ammonia synthesis sections. It details the processes that occur in each section, including catalysts used and operating parameters. The goal is to produce 99.73% pure ammonia from natural gas feedstock using a high-pressure synthesis process.
ammonia National Fertilizer Limited BathindaDngL611667
This document provides information on the various sections of an ammonia plant, including the desulfurization, reforming, shift, CO2 removal, methanation, and ammonia synthesis sections. It details the processes that occur in each section, including catalysts used and operating parameters. The goal is to produce 99.73% pure ammonia from natural gas and recycled byproducts using a high-pressure catalytic process across six main sections.
This document provides an overview of Fischer-Tropsch synthesis technology for producing synthetic fuels and chemicals from natural gas and other resources. It discusses the key steps which include gasification of resources to produce syngas, reforming of natural gas to syngas, water-gas shift reaction, and the Fischer-Tropsch synthesis over catalysts to produce liquid fuels and waxes. It also summarizes different catalyst types including iron and cobalt catalysts used in the Fischer-Tropsch process and compares various reactor configurations for the synthesis.
01 21-2015 basic deaerator science revealed final Desareador de oxigeno.lorenzo Monasca
The document provides an overview of basic deaerator science. It discusses how deaerators work to remove dissolved oxygen and carbon dioxide from boiler feedwater, which reduces corrosion and protects boilers. It covers the hydrologic cycle, types of deaerators including spray, tray, and packed column designs, component selection and sizing, and the benefits of using a deaerator. Key points are that deaeration heats, agitates, and releases gases to improve water quality and boiler protection.
The document provides information about an ammonia production plant, including:
1. The plant produces 910 tons of ammonia per day using natural gas, steam, and air as raw materials in a process involving desulphurization, gas preparation through reforming, shift conversion, gas purification, and ammonia synthesis.
2. Key equipment includes primary and secondary reforming furnaces, waste heat boilers, shift converters, a CO2 removal system, and storage tanks.
3. The process starts with desulphurization of natural gas, followed by steam reforming to produce hydrogen, shift conversion to remove carbon monoxide, and gas purification including CO2 removal to produce a hydrogen-rich
The document provides guidelines for safely starting up and reducing steam reforming catalyst. It discusses warm-up procedures to avoid condensation, reducing the catalyst with hydrogen or hydrocarbons, and gradually introducing feedstock. It also summarizes a case study where overfiring during start-up led to tube failures due to much higher than normal temperatures as a result of deviations from proper procedures.
DEBOTTLENECKING METALLURGICAL AND SULPHUR-BURNING SULPHURIC ACID PLANTS: CAPA...COBRAS
This document discusses concepts for debottlenecking and increasing capacity in sulfuric acid plants. It outlines strategies to unplug arteries by reducing pressure drops through improvements to catalysts, heat exchangers, packing, and mist eliminators. Performance can be enhanced by increasing SO2 gas strength, utilizing furnace bypasses, and adjusting blower locations. Emissions can be reduced through catalyst and tower design improvements as well as gas bypassing and tail gas scrubbing. The document provides examples of projects that have used these strategies to increase acid production and reduce operating costs at various sulfuric acid plants.
This document discusses various techniques for hydrogen production including treatment of gas mixtures, decomposition of hydrocarbons, and decomposition of water. It provides details on steam reforming, partial oxidation processes, and electrolysis of water. Steam reforming involves a catalytic reaction of methane and steam at high temperatures and pressures to produce hydrogen and carbon monoxide. Partial oxidation processes use oxygen and steam in an exothermic reaction to partially oxidize hydrocarbons into hydrogen, carbon monoxide, and carbon dioxide. Electrolysis and thermochemical cycles can also be used to decompose water into hydrogen and oxygen through electrical or thermal means.
This document describes an ammonia plant with three urea plants. It summarizes the key details of each plant including their commissioning dates, capacities, and revamp history. It then provides details on the ammonia and urea production processes, including descriptions of the main units involved at each stage of production from natural gas feedstock to the final urea product. Process diagrams and pictures are included to illustrate the key components and flow of materials through the plant.
Post-combustion CO2 capture and its effects on power plantsHamid Abroshan
This slide is a presentation of a conference paper discussing the post-combustion Carbon Dioxide capture from steam power plants. The main question in this paper was to choose the best location in flue gas path, where flue gas will be extracted and sent to absorption tower.
High level introduction
Mainstream syngas = steam reforming processes
Ammonia; methanol; hydrogen/HyCO
Town gas
Steam reforming; low pressure cyclic
Direct reduction iron (DRI)
HYL type processes; Midrex type processes
Presentation given by Richard T. J. Porter from ETII, University of Leeds, on "CO2QUEST Typical Impurities in Captured CO2 Streams" at the EC FP7 Projects: Leading the way in CCS implementation event, London, 14-15 April 2014
Vacuum carburizing provides advantages over traditional gas carburizing methods, including faster carbon transfer without surface oxidation, improved case depth uniformity, and integration into manufacturing processes with little consumption of carburizing gas and no need for furnace atmospheres. Vacuum carburizing allows for higher carburizing temperatures and shorter treatment times compared to gas carburizing. Parts treated with vacuum carburizing have cleaner surfaces without intergranular oxidation, more consistent case depths and carbon profiles, less distortion and variation, and potential operational cost advantages.
This workshop presentation provides regulators, consultants, and field applicators with an understanding of the operational processes behind thermal conductive heating (TCH) utilizing a gas powered system known commercially as Gas Thermal Remediation (GTR). A brief review of the various thermal options available today is presented to highlight the key differentiating operational factors. Additionally, benefits from heat generation, such as increased rates of naturally occurring processes (including hydrolysis, increased bio-availability, different forms of bio-degradation at various temperature regimes), and the primary contaminant removal mechanisms for thermal conductive heating are reviewed through three published literature references and case study review. The course examines various site conditions, identifies the remediation challenges leading to a thermal solution, and evaluates the results.
Similar to Theory and Practice of Steam Reforming (20)
Pressure Relief Systems Vol 2
Causes of Relief Situations
This Volume 2 is a guide to the qualitative identification of common causes of overpressure in process equipment. It cannot be exhaustive; the process engineer and relief systems team should look for any credible situation in addition to those given in this Part which could lead to a need for pressure relief (a relief situation).
This document provides guidelines for engineering design of pressure relief systems. It discusses key principles such as identifying potential overpressure and underpressure causes, sizing relief systems to prevent hazards, and safely disposing of relieved materials. The guidelines cover statutory requirements, recommended design procedures, and documentation standards. The overall goal is to preserve equipment integrity and prevent failure from over or under pressure during all process phases.
GAS DISPERSION - A Definitive Guide to Accidental Releases of Heavy GasesGerard B. Hawkins
GAS DISPERSION - A Definitive Guide to Accidental Releases of Heavy Gases
This Process Safety Guide has been written with the aim of assisting process engineers, hazard analysts and environmental advisers in carrying out gas dispersion calculations. The Guide aims to provide assistance by:
• Improving awareness of the range of dispersion models available within GBHE, and providing guidance in choosing the most appropriate model for a particular application.
• Providing guidance to ensure that source terms and other model inputs are correctly specified, and the models are used within their range of applicability.
• Providing guidance to deal with particular topics in gas dispersion such as dense gas dispersion, complex terrain, and modeling the chemistry of oxides of nitrogen.
• Providing general background on air quality and dispersion modeling issues such as meteorology and air quality standards.
• Providing example calculations for real practical problems.
SCOPE
The gas dispersion guide contains the following Parts:
1 Fundamentals of meteorology.
2 Overview of air quality standards.
3 Comparison between different air quality models.
4 Designing a stack.
5 Dense gas dispersion.
6 Calculation of source terms.
7 Building wake effects.
8 Overview of the chemistry of the oxides of nitrogen.
9 Overview of the ADMS complex terrain module.
10 Overview of the ADMS deposition module.
11 ADMS examples.
12 Modeling odorous releases.
13 Bibliography of useful gas dispersion books and reports.
14 Glossary of gas dispersion modeling terms.
Appendix A : Modeling Wind Generation of Particulates.
APPENDIX B TABLE OF PROPERTY VALUES FOR SPECIFIC CHEMICALS
101 Things That Can Go Wrong on a Primary Reformer - Best Practices GuideGerard B. Hawkins
This document discusses common problems that can occur in primary reformers and associated equipment. It identifies issues that can lead to plant shutdowns or efficiency losses, grouping them under catalysts, tubes, furnace boxes, burners, flue gas ducts, headers, and refractories. Some examples discussed include carbon formation, tube overheating, flame impingement, leaks in air preheaters, combustion air maldistribution, and damage to coffins. The document provides an overview of these issues to improve plant reliability over its lifespan.
El impacto en el rendimiento del catalizador por envenenamiento y ensuciamien...Gerard B. Hawkins
El documento describe los procesos de refinería y catalizadores, así como los efectos del envenenamiento y ensuciamiento en el rendimiento de los catalizadores. El envenenamiento reduce la actividad de los catalizadores al bloquear los sitios activos o modificar la química de la superficie, lo que afecta la actividad y selectividad. Los niveles bajos de contaminantes tienen un mayor impacto en catalizadores con menor área de superficie. El envenenamiento también puede causar cambios estructurales en el catalizador y permitir
Theory of Carbon Formation in Steam Reforming
Contents
1 Introduction
2 Underpinning Theory
2.1 Conceptualization
2.2 Reforming Reactions
2.3 Carbon Formation Chemistry
2.3.1 Natural Gas
2.3.2 Carbon Formation for Naphtha Feeds
2.3.3 Carbon Gasification
2.4 Heat Transfer
3 Causes
3.1 Effects of Carbon Formation
3.2 Types of Carbon
4 What are the Effects of Carbon Formation?
4.1 Why does Carbon Formation Get Worse?
4.1.1 So what is the Next Step?
4.2 Consequences of Carbon Formation
4.3 Why does Carbon Form where it does?
4.3.1 Effect on Process Gas Temperature
4.4 Why does Carbon Formation Propagate Down the Tube?
4.4.1 Effect on Radiation on the Fluegas Side
4.5 Why does Carbon Formation propagate Up the Tube?
5 How do we Prevent Carbon Formation
5.1 The Role of Potash
5.2 Inclusion of Pre-reformer
5.3 Primary Reformer Catalyst Parameters
5.3.1 Activity
5.3.2 Heat Transfer
5.3.3 Increased Steam to Carbon Ratio
6 Steam Out
6.1 Why does increasing the Steam to Carbon Ratio Not Work?
6.2 Why does reducing the Feed Rate not help?
6.3 Fundamental Principles of Steam Outs
TABLES
1 Heat Transfer Coefficients in a Typical Reformer
2 Typical Catalyst Loading Options
FIGURES
1 Hot Bands
2 Conceptual Pellet
3 Naphtha Carbon Formation
4 Heat Transfer within an Reformer
5 Types of Carbon Formation
6 Effect of Carbon on Nickel Crystallites
7 Absorption of Heat
8 Comparison of "Base Case" v Carbon Forming Tube
9 Carbon Formation Vicious Circle
10 Temperature Profiles
11 Carbon Pinch Point
12 Carbon Formation
13 Effect on Process Gas Temperature
14 How does Carbon Propagate into an Unaffected Zone?
15 Movement of the Carbon Forming Region
16 Effect of Hot Bands on Radiative Heat Transfer
17 Effect of Potash on Carbon Formation
18 Application of a Pre-reformer
19 Effect of Activity on Carbon Formation
Adiabatic Reactor Analysis for Methanol Synthesis Plant Note Book Series: P...Gerard B. Hawkins
The document discusses adiabatic reactor analysis for methanol synthesis from syngas. It provides the reaction kinetics and calculates conversion, temperature, and reactor volume needed at different conversions. Energy and mass balances are used to derive relationships between conversion, temperature and reaction rate. Data is generated to plot conversion versus volumetric flow rate for reactor sizing. The plot indicates a continuous stirred tank reactor (CSTR) could achieve 85% conversion before switching to a plug flow reactor (PFR) for higher conversion with less volume.
STEAMING PROCEDURE FOR VULCAN STEAM REFORMING CATALYSTSGerard B. Hawkins
The document discusses procedures for steaming Vulcan steam reforming catalysts to recover from sulfur poisoning and carbon formation incidents. It describes maintaining steam flow at 30-40% of design levels and an outlet temperature above 780°C. Gas samples should be taken hourly to monitor CO2, CH4, H2S and SO2. Steaming is complete when CO2 levels stabilize over 2-3 samples after increasing the temperature. The process typically takes 12-24 hours to complete and closely monitors pressure drop and tube conditions. After steaming, the catalyst requires reduction before restarting hydrocarbon feed.
Calculation of an Ammonia Plant Energy Consumption: Gerard B. Hawkins
Calculation of an Ammonia Plant Energy Consumption:
Case Study: #06023300
Plant Note Book Series: PNBS-0602
CONTENTS
0 SCOPE
1 CALCULATION OF NATURAL GAS PROCESS FEED CONSUMPTION
2 CALCULATION OF NATURAL GAS PROCESS FUEL CONSUMPTION
3 CALCULATION OF NATURAL GAS CONSUMPTION FOR PILOT BURNERS OF FLARES
4 CALCULATION OF DEMIN. WATER FROM DEMIN. UNIT
5 CALCULATION OF DEMIN. WATER TO PACKAGE BOILERS
6 CALCULATION OF MP STEAM EXPORT
7 CALCULATION OF LP STEAM IMPORT
8 DETERMINATION OF ELECTRIC POWER CONSUMPTION
9 DETERMINATION OF THE TOTAL ENERGY CONSUMPTION OF THE AMMONIA PLANT ISBL
10 ADJUSTMENT OF ELECTRIC POWER CONSUMPTION FOR TEST RUN CONDITIONS
11 CALCULATION OF AMMONIA SHARE IN MP STEAM CONSUMPTION IN UTILITIES
12 CALCULATION OF AMMONIA SHARE IN ELECTRIC POWER CONSUMPTION IN UTILITIES
13 DETERMINATION OF THE TOTAL ENERGY CONSUMPTION OF THE AMMONIA PLANT OSBL
14 DETERMINATION OF THE TOTAL ENERGY CONSUMPTION OF THE AMMONIA PLANT
Ammonia Plant Technology
Pre-Commissioning Best Practices
GBHE-APT-0102
PICKLING & PASSIVATION
CONTENTS
1 PURPOSE OF THE WORK
2 CHEMICAL CONCEPT
3 TECHNICAL CONCEPT
4 WASTES & SAFETY CONCEPT
5 TARGET RESULTS
6 THE GENERAL CLEANING SEQUENCE MANAGEMENT
6.6.1 Pre-cleaning or “Physical Cleaning
6.6.2 Pre-rinsing
6.6.3 Chemical Cleaning
6.6.4 Critical Factors in Cleaning Success
6.6.5 Rinsing
6.6.6 Inspection and Re-Cleaning, if Necessary
7 Systems to be treated by Pickling/Passivation
Ammonia Plant Technology
Pre-Commissioning Best Practices
Piping and Vessels Flushing and Cleaning Procedure
CONTENTS
1 Scope
2 Aim/purpose
3 Responsibilities
4 Procedure
4.1 Main cleaning methods
4.1.1 Mechanical cleaning
4.1.2 Cleaning with air
4.1.3 Cleaning with steam (for steam networks only)
4.1.4 Cleaning with water
4.2 Choice of the cleaning method
4.3 Cleaning preparation
4.4 Protection of the devices included in the network
4.5 Protection of devices in the vicinity of the network
4.6 Water flushing procedure
4.6.1 Specific problems of water flushing
4.6.2 Preparation for water flushing
4.6.3 Performing a water flush
4.6.4 Cleanliness criteria
4.7 Air blowing procedure
4.7.1 Specific problems of air blowing
4.7.2 Preparation for air blowing
4.7.3 Performing air blowing
4.7.4 Cleanliness checks
4.8 Steam blowing procedure
4.8.1 Specific problems of steam blowing
4.8.2 Preparation for steam blowing
4.8.3 Performing steam blowing
4.8.4 Cleanliness checks
4.9 Chemical cleaning procedure
4.9.1 Specific problems of cleaning with a chemical solution
4.9.2 Preparation for chemical cleaning
4.9.3 Performing a chemical cleaning
4.9.4 Cleanliness criteria
4.10 Re-assembly - general guideline
4.11 Preservation of flushed piping
DESIGN OF VENT GAS COLLECTION AND DESTRUCTION SYSTEMS Gerard B. Hawkins
DESIGN OF VENT GAS COLLECTION AND DESTRUCTION SYSTEMS
CONTENTS
1 INTRODUCTION
1.1 Purpose
1.2 Scope of this Guide
1.3 Use of the Guide
2 ENVIRONMENTAL ISSUES
2.1 Principal Concerns
2.2 Mechanisms for Ozone Formation
2.3 Photochemical Ozone Creation Potential
2.4 Health and Environmental Effects
2.5 Air Quality Standards for Ground Level Concentrations of Ozone, Targets for Reduction of VOC Discharges and Statutory Discharge Limits
3 VENTS REDUCTION PHILOSOPHY
3.1 Reduction at Source
3.2 End-of-pipe Treatment
4 METHODOLOGY FOR COLLECTION & ASSESSMENT OF PROCESS FLOW DATA
4.1 General
4.2 Identification of Vent Sources
4.3 Characterization of Vents
4.4 Quantification of Process Vent Flows
4.5 Component Flammability Data Collection
4.6 Identification of Operating Scenarios
4.7 Quantification of Flammability Characteristics for Combined Vents
4.8 Identification, Quantification and Assessment of Possibility of Air Ingress Routes
4.9 Tabulation of Data
4.10 Hazard Study and Risk Assessment
4.11 Note on Aqueous / Organic Wastes
4.12 Complexity of Systems
4.13 Summary
5 SAFE DESIGN OF VENT COLLECTION HEADER SYSTEMS
5.1 General
5.2 Process Design of Vent Headers
5.3 Liquid in Vent Headers
5.4 Materials of Construction
5.5 Static Electricity Hazard
5.6 Diversion Systems
5.7 Snuffing Systems
6 SAFE DESIGN OF THERMAL OXIDISERS
6.1 Introduction
6.2 Design Basis
6.3 Types of High Temperature Thermal Oxidizer
6.4 Refractories
6.5 Flue Gas Treatment
6.6 Control and Safety Systems
6.7 Project Program
6.8 Commissioning
6.9 Operational and Maintenance Management
APPENDICES
A GLOSSARY
B FLAMMABILITY
C EXAMPLE PROFORMA
D REFERENCES
DOCUMENTS REFERRED TO IN THIS PROCESS GUIDE
TABLE
1 PHOTOCHEMICAL OZONE CREATION POTENTIAL REFERENCED
TO ETHYLENE AS UNITY
FIGURES
1 SCHEMATIC OF TYPICAL VENT COLLECTION AND THERMAL OXIDIZER SYSTEM
2 TYPICAL KNOCK-OUT POT WITH LUTED DRAIN
3 SCHEMATIC OF DIVERSION SYSTEM
4 CONVENTIONAL VERTICAL THERMAL OXIDIZER
5 CONVENTIONAL OXIDIZER WITH INTEGRAL WATER SPARGER
6 THERMAL OXIDIZER WITH STAGED AIR INJECTION
7 DOWN-FIRED UNIT WITH WATER BATH QUENCH
8 FLAMELESS THERMAL OXIDATION UNIT
9 THERMAL OXIDIZER WITH REGENERATIVE HEAT RECOVERY
10 TYPICAL PROJECT PROGRAM
11 TYPICAL FLAMMABILITY DIAGRAM
12 EFFECT OF DILUTION WITH AIR
13 EFFECT OF DILUTION WITH AIR ON 100 Rm³ OF FLAMMABLE GAS
PRACTICAL GUIDE ON THE SELECTION OF PROCESS TECHNOLOGY FOR THE TREATMENT OF A...Gerard B. Hawkins
PRACTICAL GUIDE ON THE SELECTION OF PROCESS TECHNOLOGY FOR THE TREATMENT OF AQUEOUS ORGANIC EFFLUENT STREAMS
CONTENTS
0 INTRODUCTION/PURPOSE
1 SCOPE
2 FIELD OF APPLICATION
3 DEFINITIONS
3.1 IPU
3.2 AOS
3.3 BODs
3.4 COD
3.5 TOC
3.6 Toxicity
3.7 Refractory Organics/Hard COD
3.8 Heavy Metals
3.9 EA
3.10 Biological Treatment Terms
3.11 BATNEEC
3.12 BPEO
3.13 EQS/LV
3.14 IPC
3.15 VOC
3.16 F/M Ratio
3.17 MLSS
3.18 MLVSS
4 DESIGN/ECONOMIC GUIDELINES
5 EUROPEAN LEGISLATION
5.1 General
5.2 Integrated Pollution Control (IPC)
5.3 Best Available Techniques Not Entailing Excessive Costs (BATNEEC)
5.4 Best Practicable Environmental Option (BPEO)
5.5 Environmental Quality Standards(EQS)
6 IPU EXIT CONCENTRATION
7 SITE/LOCAL REQUIREMENTS
8 PROCESS SELECTION PROCEDURE
8.1 Waste Minimization Techniques (WMT)
8.2 AOS Stream Definition
8.3 Technical Check List
8.4 Preliminary Selection of Suitable Technologies
8.5 Process Sequences
8.6 Economic Evaluation
8.7 Process Selection
APPENDICES
A DIRECTIVE 76/464/EEC - LIST 1
B DIRECTIVE 76/464/EEC - LIST 2
C THE EUROPEAN COMMISSION PRIORITY CANDIDATE LIST
D THE UK RED LIST
E CURRENT VALUES FOR EUROPEAN COMMUNITY ENVIRONMENTAL QUALITY STANDARDS AND CORRESPONDING LIMIT VALUES
F ESTABLISHED TECHNOLOGIES
G EMERGING TECHNOLOGY
H PROPRIETARY/LESS COMMON TECHNOLOGIES
J COMPARATIVE COST DATA
PRACTICAL GUIDE ON THE REDUCTION OF DISCHARGES TO ATMOSPHERE OF VOLATILE ORGA...Gerard B. Hawkins
PRACTICAL GUIDE ON THE REDUCTION OF DISCHARGES TO ATMOSPHERE OF VOLATILE ORGANIC COMPOUNDS (VOCs)
FOREWORD
CONTENTS
1 INTRODUCTION
2 THE NEED FOR VOC CONTROL
3 CONTROL AT SOURCE
3.1 Choice or Solvent
3.2 Venting Arrangements
3.3 Nitrogen Blanketing
3.4 Pump Versus Pneumatic Transfer
3.5 Batch Charging
3.6 Reduction of Volumetric Flow
3.7 Stock Tank Design
4 DISCHARGE MEASUREMENT
4.1 By Inference or Calculation
4.2 Flow Monitoring Equipment
4.3 Analytical Instruments
4.4 Vent Emissions Database
5 ABATEMENT TECHNOLOGY
5.1 Available Options
5.2 Selection of Preferred Option
5.3 Condensation
5.4 Adsorption
5.5 Absorption
5.6 Thermal Incineration
5.7 Catalytic Oxidation
5.8 Biological Filtration
5.9 Combinations of Process technologies
5.10 Processes Under Development
6 GLOSSARY OF TERMS
7 REFERENCES
Appendix 1. Photochemical Ozone Creation Potentials
Appendix 2. Examples of Adsorption Preliminary Calculations
Appendix 3. Example of Thermal Incineration Heat and Mass Balance
Appendix 4. Cost Correlations
Getting the Most Out of Your Refinery Hydrogen PlantGerard B. Hawkins
Getting the Most Out of Your Refinery Hydrogen Plant
Contents
Summary
1 Introduction
2 "On-purpose" Hydrogen Production
3 Operational Aspects
4 Uprating Options on the Steam Reformer
4.1 Steam Reforming Catalysts and Tube Metallurgy
4.2 Oxygen-blown Secondary Reformer
4.3 Pre-reforming
4.4 Post-reforming
5 Downstream Units
6 Summary of Uprating Options
7 Conclusions
EMERGENCY ISOLATION OF CHEMICAL PLANTS
CONTENTS
1 Introduction
2 When should Emergency Isolation Valves be Installed
3 Emergency Isolation Valves and Associated Equipment
3.1 Installations on existing plant
3.2 Actuators
3.3 Power to close or power to open
3.4 The need for testing
3.5 Hand operated Emergency Valves
3.6 The need to stop pumps in an emergency
3.7 Location of Operating Buttons
3.8 Use of control valves for Isolation
4 Detection of Leaks and Fires
5 Precautions during Maintenance
6 Training Operators to use Emergency Isolation Valves
7 Emergency Isolation when no remotely operated valve is available
References
Glossary
Appendix I Some Fires or Serious Escapes of Flammable Gases or Liquids that could have been controlled by Emergency Isolation Valves
Appendix II Some typical Installations
Amine Gas Treating Unit - Best Practices - Troubleshooting Guide Gerard B. Hawkins
Amine Gas Treating Unit Best Practices - Troubleshooting Guide for H2S/CO2 Amine Systems
Contents
Process Capabilities for gas treating process
Typical Amine Treating
Typical Amine System Improvements
Primary Equipment Overview
Inlet Gas Knockout
Absorber
Three Phase Flash Tank
Lean/Rich Heat Exchanger
Regenerator
Filtration
Amine Reclaimer
Operating Difficulties Overview
Foaming
Failure to Meet Gas Specification
Solvent Losses
Corrosion
Typical Amine System Improvements
Degradation of Amines and Alkanolamines during Sour Gas Treating
APPENDIX
Best Practices - Troubleshooting Guide
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3. Steam Reforming of Methane
CH4 + H2O CO + 3H2 (Steam Reforming))
CO + H2O CO2 + H2 (water Gas Shift)
• Overall strongly endothermic
• Need to get large amounts of heat in
– narrow-bore steam reformer tubes
4. Steam Reforming of Heavier
Hydrocarbons
CnHm + nH2O nCO + (n+m/2)H2
Still endothermic
Easier than methane
More prone to carbon formation
5. Contents
Steam reforming reactions
Steam reforming catalysts
• catalyst activity
• catalyst development and testing
• importance of gas and htc
Equilibrium considerations
Carbon formation
Poisoning
Steam reformer modelling
Pre - and post reforming
6. Steam Reforming Catalyst
Steam reforming can be done without
catalyst, but needs very high temperatures
• partial oxidation
Modern steam reforming catalyst use
nickel on a ceramic support
• with or without promoters and stabilisers
• precious metals offer alternatives to Ni
Supports must be strong; inert; thermally
and chemically stable
Catalysts lower the temperature at which
steam reforming occurs at a high rate
7. Steam Reforming Catalyst Activity
Reaction highly endothermic
• may be limited by process of getting
heat in to reactant sites
Process may also be limited by diffusion
8. Activity Testing
Define some measure of reaction
• exit methane
Measure for a range of catalysts under
fixed conditions
• flow, temperature pressure, catalyst
10. Diffusion Processes
Molecular diffusion, Dm
• determined by rate at which molecules collide
with each other
• depends on pressure
• independent of pore radius
Knudsen diffusion, Dk
• determined by the rate at which molecules
collide with pore walls
• depends on pore radius
11. Check for Knudsen Diffusion
Mean free path of molecules must be greater
than pore radius for Knudsen diffusion to
dominate
• at 700oC (1290oF), mean free path is 100 Angstrom
Typical pore radius for steam reforming
catalyst is 150 - 1000 Angstrom
• Not Knudsen regime
12. Steam Reforming Catalyst Activity
Intrinsic activity (chemical reaction only)
Extrinsic activity (includes heat and mass
transfer effects)
Steam reforming dominated by extrinsic
effects
Influence of pressure significant
21. Steam Reformer Tubes
Need to get a lot of heat in
• narrow bore tubes
High temperatures and pressures
• tubes in creep region
• tubes will fail by rupture
• tube life very sensitive to temperature
23. Top Fired Reformer
Distance Down Tube m (ft)
TubeWallTemperature
DegC(DegF)
0 1 2 3 4 5 6 7 8 9 10 11 12
BASE CASE
BASE CASE WITH TWICE
SURFACE AREA
BASE CASE WITH TWICE
HEAT TRANSFER
840
800
760
720
(1544)
(1472)
(1400)
(6) (12) (18) (24) (30) (36)
Effect of Catalyst Design Variables on
Tube Wall Temperature
24. Tube Wall
Bulk Process
Gas Temp.
715oC (1319oF)
1200oC (2192oF)
830oC (1526oF)
775oC (1427oF)
Fluegas
Outside tube wall temperature
Inside tube wall temperature
Gas film
Temperature Profile
Top-fired reformer, 40% down
25. TemperatureDegC(DegF)
Tube Wall Temperature Limit
Poor stability
Good stability
Days on Line
0 1,000500100 200 300 400 600 700 800 900
925
(1697)
900
(1652)
875
(1607)
850
(1562)
Effect of Catalyst Stability on
Tube wall Temperature
31. Effect of Pressure
• Exit methane proportional to pressure squared
• lower exit methane at lower pressures
• overall plant economics dictate higher
pressures, typically 20 bar (300 psi)
CH4 + H2O CO + 3H2
F[CO ] F[H2]3 Kms Pt2
F[CH4] =
F[H2O]
32. Effect of Steam- to- Carbon Ratio
• Exit methane inversely proportional to steam
• lower methane requires more steam
• actual value depends on overall plant design
• s/c ratio typically 5-6 on older plants
• s/c ratio typically 3 on newer plants
CH4 + H2O CO + 3H2
F[CO ] F[H2]3 Kms Pt2
F[CH4] =
F[H2O]
33. • Exit methane proportional to Kms
• Kms approx inversely proportional to temperature
• lower methane requires higher temperatures
• limited by tube metallurgy
Effect of Temperature
CH4 + H2O CO + 3H2
F[CO ] F[H2]3 Kms Pt2
F[CH4] =
F[H2O]
35. Feedstock Refinery Off
Gas
Methane Butane Naphtha
C/H Ratio CH6 CH4 CH2.5 CH2.2
Exit Gas
CH4
CO
CO2
H2
6.67
8.14
4.45
80.74
5.35
12.18
9.12
73.35
4.29
14.17
12.36
69.16
4.01
14.73
13.77
67.49
All at exit temperature 850 Deg C (1562 Deg F)
Exit pressure 30 atas (435 psi)
Steam/carbon ratio 3.5
Effect of Feedstock
37. Approach to equilibrium
The system is not actually at equilibrium,
but close to it
A measure of catalyst performance is the
Approach to Equilibrium, ATEms
• ATEms = 0 when at equilibrium
• the bigger ATEms, the further from
equilibrium
38. Temperature oC (oF)
770 780 790 800 810 820
2
4
6
8
10
12
Methaneslip(%)
(1418) (1454)(1436) (1472) (1490)
Exit CH4
Approach to Equilibrium
(1508)
ATE
Equilibrium
Temp Gas Temp
39. 0 0.2 0.4 0.6 0.8 1
200
(392)
400
(752)
600
(1112)
800
(1472)
Fraction down tube
TemperatureoC(oF)
Gas Temp Eq'm Temp
Approach to equilibrium
40. Contents
Steam reforming reactions
Steam reforming catalysts
Equilibrium considerations
Carbon formation
• formation and removal reactions
• role of alkali
• range of catalysts
Poisoning
Steam reformer modelling
Pre-and post-reforming
43. Carbon Formation
CH4 C + 2H2 (Thermal Cracking)
CO + H2 C + H2O (CO Reduction)
2CO C + CO2 (CO disproportionation
“Boudouard”)
44. Carbon Formation
Direction of reaction determined by
process gas conditions
Generally, CO reduction and Boudouard
are carbon removing
Generally, cracking restricted to top half
of reformer
49. 800
100
10
1.0
0.1
0.6
0.5
0.4
0.3
550 600 650 700 750
Increasing
Potash
Content
1100 1200 1300 1400
(°F)
Carbon Formation - Effect of Alkali
Carbon Formation
Zone
Temperature (°C)
pH2
2
pCH4
No Carbon
Formation
50. Role of Alkali
Reduces likelihood that carbon will be
formed
Enables carbon to be removed readily
Incorporation into support must be done
correctly
• Release rate not too fast/slow
• Effect on activity
53. Feedstock Natural Gas
Reforming
Non-
alkalised
Associated
Gas Ref
Lightly
alkalised
Dual Feedstock
Reforming
Moderately
alkalised
Naphtha
Reforming
Heavily
alkalised
Non-alkalised Low alkali Moderate alkali High alkali
Naphtha 3.0-3.5
Light Naphtha 6.0-8.0 3.0-4.0 2.5-3.0
Butane 4.0-5.0 2.5-3.5 2.0-3.0
Propane, LPG 3.0-4.0 2.5-3.0 2.0-2.5
Refinery Gas 6.0-10.0 3.0-4.0 2.0-3.0 2.0-2.5
Associated
Gas 5.0-7.0 2.0-3.0 2.0-2.5
Natural Gas 2.5-4.0 1.5-2.0 1.0-2.0
Pre-reformed
Gas 2.0-3.0 1.0-2.0 1.0-2.0
Typical Steam Ratios for Catalyst/
Feedstock Combinations
54. Alternatives to Alkali
• Precious metals can also be used instead
of Ni as the catalyst
– Significant higher activity and hydrogenation
activity yields lower carbon formation rates
– Platinum, Ruthenium …etc
– Effective “ultra”-purification essential
• Lanthanum used in addition to Ni
– Helps also with the removal of carbon
• Magnesium/Ni
– Also suppresses carbon formation rates
– However, magnesium not stable with steam
56. Sulfur Poisoning
Most common poison
Severe levels (.5ppm) can lead to rapid
catalyst deactivation
“Normal” levels (20-30ppbv) leads to very
slow deactivation
Sulfur equilibrium depends on
temperature
58. Sulfur Poisoning
Complex; some disagreement in literature,
particularly at low levels
Low level Sulfur will lead to increased twt
with time
Other deactivation mechanisms also
operate
59. Sulfur Poisoning - Precious Metals
Reforming
• Precious metals require ultra-low poison
levels
– Typically <5 ppbv
– Use specialised purifcation absorbent
downstream of ZnO
• Typical S slip 1-2 ppbv
60. Catalyst Sintering
Initial rapid sintering
Slower subsequent sintering
Temperature dependent
Both Ni crystallites and support sinter
71. Pre-reforming
Low temperature adiabatic steam
reforming
Wide range of feedstocks
Requires highly active, high nickel
catalyst
Exo/endothermic, depending on feedstock
Converts all heavy hydrocarbons to
methane
72. Temperature
475 deg C
(890 deg F)
410 deg C
(770 deg F)
0 10050
NG Pre-reformer
Temperature Profile
Percentage Down Bed
73. 450 Deg C
(842 Deg F)
500 Deg C
(932 Deg
F)
Percentage Down Bed
Temperature
Naphtha Pre-reforming temperature
Profile
75. Post-reforming
Heat exchange type of steam reformer
Uses steam reformer exit gas as heating
medium for fresh feed
Compact design
• small footprint
Uses conventional catalyst
No extra fuel firing needed
• no increase in Nox emissions
Typically allows 25 % increase in rate