Chapter 1 3
Chapter 1 3
Chapter 1 3
INTRODUCTION
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1.1 Background of the Study
Acetone is the simplest ketone and one of the most abundant volatile organic compounds
(VOCs) in the atmosphere, with typical mixing ratios ranging from a few hundred parts per
trillion (pptv) to several parts per billion (ppbv) or more. It is a volatile organic compound
(VOC) that is considered to have low toxicity, though improper use of it can cause serious
problems. There are a number of uses for acetone, including in chemicals, solvents and nail
polish remover. The most common use of acetone is to formulate other chemicals. Beyond
chemicals and solvents, other uses for acetone exist in the production of cosmetics and
household and personal care products.
In the production of acetone different methods are presented. The cumene process is the
most common worldwide, but as a byproduct, benzene (carcinogen) is lowering the purity of
acetone and increasing production costs by separation. The oxidation of polypropylene has a low
conversion of acetone. In the dehydrogenation of IPA, high purity acetone is obtained, the IPA
can be used in aqueous solution, and the conversion of acetone is high and has no substances,
which are significantly hazardous to health.
1.2 Problem
1.2.1 Acetone
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1.2.2 Isopropyl Alcohol
The catalytic dehydrogenation of isopropyl alcohol has been studied as a means to utilize
waste heat via an endothermic chemical reaction, which produces acetone and hydrogen. The
system absorbs low temperature waste heat (roughly 80oC) at the generation site and stores it as
chemical substances with minimal energy loss. When needed, the products of the chemical
reaction may be recombined to give high quality heat (150-200 oC) at the user site, via the
exothermic reverse reaction. Thus, the exothermic hydrogenation of acetone produces the initial
reactant, isopropyl alcohol, thereby completing the cycle. According to thermodynamic
constraints, low temperature heat must be rejected from the system, which is accomplished
during the separation of isopropyl alcohol and acetone.
There are many methods to synthesize acetone. One of the most efficient methods is the
dehydrogenation of isopropyl alcohol, which is the proposed method in this project. Another
method to synthesize acetone is called the cumene process, in which benzene (C 6H6) reacts with
propylene (C3H6) to form cumene (C9H12). After reaction, cumene is oxidized to form acetone
(CH3)2CO with phenol (C6H6O), as is clarified in the equations below (Hudson, 2015; Coulson et
al., 1999b).
C 6 H 6 +C 3 H 6 → C9 H 12
C 9 H 12 +O2 →(CH ¿¿ 3)2 CO+ C6 H 6 O ¿
The cumene process method is quite expensive, since it requires the raw materials and
extra separation equipment to separate acetone from many different materials (Moore &
Parker,2007; Coulson et al., 1999b). Another method for the production of acetone is by the
direct oxidation of propylene using air. In this process the catalysis consists of a solution of
copper chloride containing small quantities of palladium chloride. The reaction takes place under
a moderate pressure and at 100°C. It is exothermic by 61 kcal/mole of acetone produced. The
overall reaction is as follows:
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2 CH 3 −CH =CH 2 +O2 →2 CH 3 −CO−CH 3
Propylene Oxygen Acetone
But then this process also suffers from high capital costs and corrosion problems. Therefore,
this study will focus on the more economic method of dehydrogenation of isopropyl alcohol
over the cumene and oxidation process method (Icis, 2019).
1.3 Opportunity
From a recent research conducted with regards to the global acetone market growth, it is
predicted to increase at a compound annual growth rate (CAGR) of around 2% per year,
beginning on year 2017 to 2023.
One of the industry that greatly affects the consumption of acetone is the paints and
coatings market which is projected to grow from US$160.54 billion in 2017 to US$209.36
billion by 2022, at a CAGR of 5.45 percent. Thus, an acetone production plant can be expected
to be profitable since acetone is one of the most common solvent utilized in the production of
paint.
Due to the continuous development of automotive and electronics sectors in Asia, there
has been a solid rise for acetone in terms of regional development. India, in particular has been
experiencing a positive demand in MMA from the aforementioned industries, resulting to an
increased acetone demand in the Indian market of around 4.2% from 2005-06 to 2016-17. With
this information in mind, establishing an acetone production plant in the Philippines can be a
solution in providing cheaper acetone for India.
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North East Asia, on the other hand, has been known to be the largest global acetone
market, which accounted for about 40% of the total in volume terms. This can prove to be
beneficial for the construction of Acetone production plant in the Philippines seeing as it gives
them a possibility for a potential trade with the globally largest consumer of acetone.
There are many methods to synthesize acetone. Early processes for the manufacture of
acetone were based on the thermal decomposition of calcium acetate or the carbohydrate
fermentation of corn starch or molasses. The ready availability of propylene in the 1960s led to
routes based on the cumene peroxidation, this converts two relatively cheap starting materials,
benzene and propylene, into two more valuable ones, phenol and acetone. However, major
disadvantage from this process is that some amount of reactant benzene is present along with
desired product which is toxic; propylene oxidation, wherein acetone can be produced by the
direct oxidation of propylene using air. In this process the catalysis consists of a solution of
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copper chloride containing small quantities of palladium chloride but then this process requires
propylene that should be 99% pure; and dehydrogenation of isopropyl alcohol in which an
aqueous solution of isopropyl alcohol is fed into the reactor, where the stream is vaporized and
reacted over a solid catalyst. The primary advantage of this process is that the acetone produced
is free from trace aromatic compounds, particularly benzene. For this reason, acetone produced
from IPA is favored by different industries.
More often after the separation process through a distilling column, the output will
contain an IPA (Isopropyl alcohol) – water azeotrope that will be recycle and will be an
advantage to have a higher purity of product, less separation process needed, and a decrease in
the cost of utilities. An energy saving of 35% for hot utilities and 37% for cold utilities can be
obtained. High temperature of reactor must be maintained to get a high conversion of acetone.
Due to the listed disadvantages, it can be seen that the most efficient method to produce acetone
will be the dehydrogenation of isopropyl alcohol.
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1.6 Scope and Limitations
The study focuses on the production of acetone by dehydrogenation of isopropyl alcohol
and engineering and economic feasibility of an acetone production plant. The study will be
conducted within the Philippines and will be performed using isopropyl alcohol as the source
material.
The isopropyl that will be used will contain 12% water and the operating temperature will
be limited to 380oC. The dehydrogenation will be carried out in a tubular reactor. The
temperature in this reactor will be limit within the range of 420 o-550oC in order to have a
conversion will be at the range of 75%-95%.
The study is limited to the available information accessed through local government
portals and available researches, journals, and studies as of the development of this report.
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CHAPTER 2
PRELIMINARY STUDIES
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2.1 Product Specifications and Market
2.1.1 Acetone
Acetone is a solvent commonly used applications such as, liquid printing inks, nail polish
removers, lacquer thinners, lacquers, in the filling of acetylene cylinders, bituminous paints,
polyester resins, PVC cloth manufacture, explosives and adhesives. It is used as a raw material
for the manufacture of di acetone alcohol, hexylene glycol, methyl iso-butyl ketone and fine
chemicals. Acetone is used in the refining of petroleum products as well and the manufacture of
grease.
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PROPERTY Euro 4-PH TEST METHODS
Acetone market value is predicted to increase at a CAGR of 5% from 2016 to 2026, this
proves to be a positive long-term outlook on its demand. Additionally, it is expected that by the
end of 2026, the global acetone market value of US$ 7.3 Billion and approximately 6.1 million
tons in terms of market consumption (Future Market Insights, 2016).
Asia Pacific is currently hailed as the largest acetone consumer and is expected to hold
true until the end of forecast period as a result of growth increase of upcoming economies for
automotive and electronics industries. Due to the development of automotive segment, India,
China, Malaysia, and Indonesia are all predicted to have the highest rate of growth in the acetone
market in this region.
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Approximately 96% of global acetone production is a phenol production by-product. This
trend in phenol production, therefore, is also applicable to acetone. The solvent sector consists of
34% of global demand, the largest of all applications. Continuous positive growth is to be
expected through 2022, with Methyl methacrylate (MMA) as one of the largest end use for
acetone, closely behind solvent production, and Bisophenol A (BPA) as third. However, by the
end of year 2023, BPA sector is predicted to surpass that of MMA (HIS Markit, 2018)
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Acetone market growth is predicted to stabilize at a CAGR of 0.0% from 2013-
2023.With the acetone market in the Philippines having 4,000 tons produced in the year 2013,
100% have gone to production of solvents, which was considered to have the largest share of
acetone consumption in that same year, and the only sector to not experience decrease in
production. Currently, no Philippine production of acetone is expected in the medium term and
the market is predicted to have an unbalanced supply and demand, showing mixed dynamics
within the forecast period (Williams and Marshall strategy, 2019).
2.2.1.1 Specifications
The main raw material for the production of acetone is isopropyl alcohol (IPA). The
isopropyl alcohol will be sourced with specifications from a foreign chemical supplier, since
there is no local IPA producer. The table below shows typical specifications for isopropyl
alcohol.
Property Value
Appearance Clear and free from suspended matter
Purity, % m/m >99.9%
Acidity, % m/m 0.001% max
Water, % m/m <0.01
Density, g/cm3 0.786 max
Benzene content 1 max
Refractive index 1378 max
Non-volatile matter 0.001 max
According to the isopropyl alcohol market report, the Asia-Pacific region dominated the
global market share in 2018. This can be attributed to the flourishing personal care and cosmetics
industry in the region which has eased the growth of IPA as is it used in the production of skin
lotions, nail paints, shampoos, etc. residential and commercial construction activities are also
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increasing in countries, such as Vietnam, Indonesia, and Philippines. Asia is followed by North
America, Europe, and South America.
For the location of the plant, the source of raw material was considered. The propose
plant will be in Batangas, Batangas Province and is near Batanagas port and pier. The primary
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source of the isopropyl alcohol will be in China. Since isopropyl alcohol will be imported from
China, it is advantageous if the plant location is near ports.
The location is also near Calumpang River, which is reasonable given that the waste from
the plant won’t be that heavy in COD and BOD content
The proposed acetone plant aims to produce at least 21 million liters. With a projected
amount of considerable isopropyl alcohol, the production capacity is based on the expected IPA
supply at the desired location. An annual 26 million liters of isopropyl alcohol feed is expected
annually to sustain the projected demand.
Because acetone is forecasted to be required throughout the year, the plant will be
operated continuously.
The fresh feed IPA solution is combined with a small IPA solution recycle stream,
vaporized, and fed to a vapor-phase reactor which is heated by molten salt at a high temperature.
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Reactor effluent is cooled and fed to a separator. The gas containing hydrogen and acetone from
the separator is fed to a stripper in which a water stream is used to recover acetone. The liquid
streams from the stripper and separator are fed to the acetone column, which produces a high
purity acetone out the top, and the reflux removes the small amount of dissolved hydrogen. The
IPA column produces a high purity water at the bottom and IPA-water azeotrope which is
recycled back to the vessel.
The researchers of the study made full utilization of the software ASPEN HYSYS V11
available at the Chemical Engineering Department in Adamson University. Specific designs an
adjustment was confirmed through concepts based on fundamental chemical engineering
knowledge. The thermodynamic fluid package used for this purpose is Peng-Robinson.
The reactor was designed and simulated in HYSYS as a fixed bed plug flow reactor.
The reactor occurs in vapor phase at a temperature of 350C and a pressure of 1.8-2 bars
in the presence of catalyst.
kJ
CH 3−CHOH −CH 3 (v ) Catalyst CH 3−CO−CH 3 ( v ) + H 2 ( g) H =+62.9
→ mol
At a temperature lower than 325C, the following reaction is more expected to occur, and
ether (di-isopropyl ether) is obtained as the product instead of acetone.
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So, the suitable temperature conditions for the reaction is between 325C to 350C.
In the distilling column T-203, IPA and water are separated. The inlet temperature is
105°C. The outlet temperature of the top and the bottom product are both 111.50°C. The top
product containing IPA is recycled to the feed drum V-201. It is assumed that the concentration
of stream 14 and stream 1 are the same. The bottom product of T-203 is pure water and is
discarded. The top product of T-203 can be recycled to the scrubber T-201 if a cooler is used.
Due to the high temperature of the top product it can't be recycled to T-201.
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The bottom product will enter another column to recover the acetone and to recycle the
remaining solution of IPA.
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CHAPTER 3
THE PROCESS
An azeotropic mixture of isopropyl alcohol (IPA) and water (88 wt% IPA) is fed into V-
201, where it is mixed with the recycled unreacted IPA/water mixture, Stream 14. Feed stream is
at room temperature (25°C) and at a pressure of 1.01 bar. The recycle stream is at a temperature
of 83°C and at a pressure of 1.20 bar. The mixture is then pumped to raise its pressure. The
temperature and pressure of the stream leaving the pump are 32°C and 2.30 bar. The mixture is
then sent to E-201 to change the stream’s phase into vapor. The temperature at the entrance of
the unit is the temperature leaving the pump, which is 32°C, and the leaving temperature is
234°C at a pressure of 2.16 bar. The reaction that takes place inside the R-201 is endothermic.
For this reason, the R-201 has to be heated. Heat is provided using a circulating stream of molten
salt, Stream 4. The molten salt is circulated through H-201, where it is heated above 350°C, and
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this heated molten salt is used to provide the heat to the reaction during the process. Acetone and
hydrogen gas are produced and water and isopropyl alcohol are discharged at 350°C and 1.91
bar. The reactor effluent, which contains hydrogen, water, acetone, and unreacted IPA, is cooled
in E-202 and E-203 prior entering the V-202. The entrance temperature of E-202 is 350°C, and
the leaving temperature is 45°C, which is the entrance temperature for the E-203. The mixture
leaves E-203 at 20°C and 1.63 bar. V-202 is operating isothermally, which means the
temperature is constant at 20°C. In V-202, the hydrogen is flashed out from the mixture of
isopropyl alcohol, water, and acetone. Along with hydrogen, some amount of isopropyl alcohol
and acetone is also flashed out. To recover these, a stripper unit is used. Water entering T-201 is
at a temperature of 20°C. The temperature of the leaving stream, which contains acetone, water,
and isopropyl alcohol, is found to be 27°C and 1.63 bar. The bottom products of the T-201 and
V-202 are mixed together before entering T-202, which is used to separate the acetone from the
mixture. It operates at 61°C. The top product is composed of 99wt% acetone. From the bottom
product, isopropyl alcohol, water, and a very little amount of 0.1% acetone is obtained. In T-203,
isopropyl alcohol and water are separated. The top product is recycled to the V-201, which is
assumed to have the same concentration with the feed stream. The bottom product is pure water
and is thrown away as waste water.
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3.1.3 R-201 IPA Reactor
The reaction that takes place inside the reactor is endothermic. For this reason, the reactor
has to be heated. Heat is provided using a circulating stream of molten salt, Stream 4. The molten
salt is circulated through the small-scale furnace where it is heated above 350°C, and this heated
molten salt is used to provide the heat to the reaction during the process. Acetone and hydrogen
gas are produced and water and isopropyl alcohol are discharged at 350°C and 1.91 bar.
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3.1.8 T-203 Isopropyl Alcohol Column
In the IPA column, isopropyl alcohol and water are separated. The top product is recycled
to the surge vessel, which is assumed to have the same concentration with the feed stream. The
bottom product is pure water and is thrown away as waste water.
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H319 Causes serious eye irritation
H336 May cause drowsiness or dizziness
Precautionary Statements
P303+P361+P353 IF ON SKIN (or hair): Remove/Take off
immediately all contaminated clothing. Rinse skin
with water/shower.
P304+P340 IF INHALED: Remove person to fresh air and
keep comfortable for breathing.
P305+P351+P338 IF IN EYES: Rinse cautiously with water for
several minutes. Remove contact lenses, if
present and easy to do. Continue rinsing
NFPA HMIS
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Precautionary Statements
P271+P403 Use and store only outdoors or in a well-ventilated
place
CGA-PG05 Use a back-flow preventive device in the piping
CGA-PG02 Protect from sunlight when ambient temperature
exceeds 52°C (125°F)
NFPA
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P303+P361+P353 IF ON SKIN (or hair): Remove/Take off immediately all
contaminated clothing. Rinse skin with water/shower.
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CHAPTER 4
LIST AND SUMMARIES
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