Executive Summary

The purpose of having this mini project is to expose students with technologies related to the
downstream processing of oil and gas, i.e focusing on petrochemical plants. The product that we
will focus on is Acetone ((CH₃)₂CO). The production of acetone is vital as acetone pose to have
many uses to the society and industries. In this report we will be considering the production of
acetone via many technologies and compare on the issues regarding each technology
represented. The technical, chemical reaction, economic and environmental aspect of these
technology will be compared based on their process variables. A future prospect on the
technology used to produce acetone will also be discussed in this report.
Introduction

Acetone is the organic compound with the formula (CH3)2CO, a colorless, mobile,
flammable liquid, the simplest example of the ketones. Acetone is miscible with water and serves
as an important solvent in its own right, typically as the solvent of choice for cleaning purposes in
the laboratory. About 6.7 million tons were produced worldwide in 2010, mainly for use as a
solvent and production of methyl methacrylate and bisphenol A. Familiar household uses of
acetone are as the active ingredient in nail polish remover and as paint thinner. It is a common
building block in organic chemistry.

Acetone is naturally produced and disposed of in the human body because of normal
metabolic processes. It is normally present in blood and urine. Diabetic people produce it in larger
amounts. Reproductive toxicity tests show that it has low potential to cause reproductive problems.
In fact, the body naturally increases the level of acetone in pregnant women, nursing mothers and
children because their higher energy requirements lead to higher levels of acetone production.
Ketogenic diets that increase acetone in the body are used to reduce epileptic attacks in infants and
children who suffer from recalcitrant refractory epilepsy. Acetone (dimethyl ketone, 2-propane,
CH3COCH3) formulation weight 58,079 is the simplest and the most important of the ketones. It
is a colorless, mobile, flammable liquid with a mildly pungent and somewhat aromatic odor. It is
miscible in all proportions with water and with organic solvents such as ether, methanol, ethyl
alcohol, and esters.
Acetone is used as a solvent for cellulose acetate and nitrocellulose, as a carrier for
acetylene and as a raw material for the chemical synthesis of a wide range of products such as
ketene, Methyl methacrylate, bisphenol A, diacetone alcohol mesityl oxide, methyl isobutyl
ketone, Hexylene glycol (2-methyl-2, 4-pentanediol), and isophorone.
 Acetone is produced in various ways which includes;

The Cumene Hydro peroxide Process for Phenol and Acetone

Isopropyl Alcohol Dehydrogenation

Direct Oxidation of Hydrocarbons to a Number of Oxygenated Products

The Diisopropylbenzene Process for Hydroquinone (or Resorcinol) and Acetone

The p-Cymene Hydro peroxide Process for p Cresol and Acetone

Acetone as a By-Product of the Propylene Oxide Process Used by Oxirane

Catalytic Oxidation of Isopropyl Alcohol

Physical and Chemical Properties:

Appearance: - Liquid. Clear.

Molecular wt.: - 58.079
Color: - Colorless.
Density/specific gravity (g/ml): - 0.79 Temperature (°C): 20
Melting Point -94.60C
Boiling Point 56.130C (at 760 mm Hg)
Vapor Pressure: - 24 .7 KP at Temperature (°C):
20Evaporation Rate: - .6
Volatile by vol. (%): - 10
Solubility description: - Miscible with water.
Solubility Value (g/100g H 2O20°C): - 100
Auto Ignition Temp. (°C): - 540
Flammability limit (lower) (%): - 2.1
Flammability limit (upper) (%): - 13.0
Stability and Reactivity:

Stability: - Stable under normal conditions of use.

Conditions to avoid: - Avoid contact with: Strong oxidizing agents. Avoid

Contact with acids. Avoid heat, flames and other

. Sources of ignition

Materials to avoid: - Potassium sulphate, sodium hydroxide, Sulphur acid,

Nitric acid, hydrogen peroxide, chloroform, activated

Carbon, Bromine.

Hazardous Decomp.Product - Thermal decomposition or burning may release oxides

Of carbon and other hazardous gases or vapors

Uses:

About a third of the world's acetone is used as a solvent, and a quarter is consumed as a precursor
to methyl methacrylate.

Solvent use:

Acetone is a good solvent for most plastics and synthetic fibers including those used in laboratory
bottles made of polystyrene, polycarbonate and some types of polypropylene. It is ideal for
thinning fiberglass resin, cleaning fiberglass tools and dissolving two-part epoxies and superglue
before hardening. It is used as a volatile component of some paints and varnishes. As a heavy-duty
degreaser, it is useful in the preparation of metal prior to painting; it also thins polyester resins,
vinyl and adhesives. It is also useful for high reliability soldering applications to remove solder
rosin after soldering is complete. This helps to prevent the Rusty bolt effect from occurring due to
dirty solder contacts.
Storage of acetylene:

Although flammable itself, acetone is also used extensively as a solvent for the safe transporting
and storing of acetylene, which cannot be safely pressurized as a pure compound. Vessels
containing a porous material are first filled with acetone followed by acetylene, which dissolves
into the acetone. One litter of acetone can dissolve around 250 litters of acetylene.

Methyl methacrylate:

This application begins with the initial conversion of acetone to acetone cyanohydrins:

(CH3)2CO + HCN → (CH3)2C (OH) CN

In a subsequent step, the nitrile is hydrolyzed to the unsaturated amide, which is esterified:

(CH3)2C (OH) CN + CH3OH → CH2= (CH3) CCO2CH3 + NH3

The third major use of acetone (about 20%) entails its condensation with phenol to give bisphenol
A

(CH3)2CO + 2 C6H5OH → (CH3)2C (C6H4OH) 2 + H2O

Bisphenol A is a component of many polymers such as polycarbonates, polyurethanes, and epoxy

resins.

Medical and cosmetic uses:

Acetone is used in a variety of general medical and cosmetic applications and is also listed as a
component in food additives and food packaging.

Acetone is commonly used in chemical peeling. Common agents used today for chemical peels
are salicylic acid, glycolic acid, 30% salicylic acid in ethanol, and trichloroacetic acid (TCA). Prior
to chemexfoliation, the skin should be cleaned properly, and excess fat removed. This process is
known as defatting. Acetone, Septisol, or a combination of these agents is commonly used in this
process.

Laboratory uses: -

In the laboratory, acetone is used as a polar aprotic solvent in a variety of organic reactions, such
as SN2 reactions. The use of acetone solvent is also critical for the Jones oxidation. It is a common
solvent for rinsing laboratory glassware because of its low cost and volatility. H\however, it does
not form an azeotrope with water (see azeotrope (data)). Despite its common use as a supposed
drying agent, it is not effective except by bulk displacement and dilution. Acetone can be cooled
with dry ice to −78 °C without freezing; acetone/dry ice baths are commonly used to conduct
reactions at low temperatures. Acetone is fluorescent under ultraviolet light, and its vapor may
be used as a fluorescent tracer in fluid flow experiments.

Domestic and other niche uses:

Acetone is often the primary component in cleaning agents such as nail polish remover. Ethyl
acetate, another organic solvent, is sometimes used as well. Acetone is a component of superglue
remover and it easily removes residues from glass and porcelain.

It can be used as an artistic agent; when rubbed on the back of a laser print or photocopy placed
face-down on another surface and burnished firmly, the toner of the image transfers to the
destination surface. Make-up artists use acetone to remove skin adhesive from the netting of wigs
and moustaches by immersing the item in an acetone bath, then removing the softener glue residue
with a stiff brush.

Figure 1 shows the nomenclature of acetone

Figure 2 shows the example of acetone and some of its usages

Market Demand:
The country's requirement for acetone is totally met through import. Data obtained from the
Ethiopian Customs Authority regarding the import of acetone for the period covering 1997 - 2011
is given in a graph below.

The market demand for Acetone for the past years

QUANTITY(Mt.Tons)
180
160
Quantity (metric tonnes)

140
120
100
2011, 91.8
80
60
40
20
0
1996 1998 2000 2002 2004 2006 2008 2010 2012
Year
Projected Demand -: Acetone is used as a solvent in the production of paint, varnish, lacquer,
cellulose acetate, potassium iodide and permanganate. It is also used to clean dry parts of precision
equipment’s, delustering for cellulose acetate fibre and specification testing of vulcanized rubber
products. This clearly indicates that demand for acetone is directly related with the development
of the industrial sector. Taking this in consideration, annual average growth of 7% is applied to
forecast the future demand. The forecasted demand up to the year 2017 is given in Table 3.2. 55-
6 import figures were much higher than the imports in the following years. In 1998, the import
figure was about 90.6 tonnes while in the following years, i.e., 1999 and 2000 the import figure
dropped to 52.7 tonnes and 24.7 tonnes respectively. Similarly, import figure in the year 2001 was
about 154 tones while in the following four consecutive years, i.e., from 2002 - 2005 import ranges
from only 34 tonnes to about 58 tonnes. This probably indicates that the high imports in some
years were used as buffer stocks for the following years. Hence, some portions of the imports were
distributed among the subsequent years in which recorded import figures were found to be
comparatively low. By looking to the above argument, the present effective demand is estimated
using the following methodology.
The average import figures in the recent past six years, i.e., 2001- 2006 is taken as an effective
demand for the year 2007 since the product is directly related with the growth of the
manufacturing sector, an annual average growth rate of 7% (which is recorded by the industrial
sector in the past) is applied to arrive at the current (year 2007) demand.

The project demand of Acetone Supply

160
140 2017, 137.7
Quantity (metric tonnes)

120
100
80
60
40
20
0
2011 2012 2013 2014 2015 2016 2017 2018
Years

QUANTITY(Mt.Tons)
Technologies Chemical Reaction Representation

As mentioned above, there are several methods to the production of acetone which includes:
(a) Oxidation of Isopropyl benzene
(b) Oxidation of Butanol
(c) Co product of Glycerine- H2O2 process
(d) Oxidation of Isopropyl Benzene (Cumene)
(e) Catalytic Dehydrogenation of Isopropanol

(a) Acetone by oxidation of Propylene: A process for acetone production by 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 overall reaction is as follows

C3H6+1/2O2 CH3COCH3

(b) Oxidation of Butanol:

Catalytic oxidation of n butane using either cobalt or manganese acetate produces acetic
acid at 75-80% yield. By products of commercial value are obtained in variable amounts.
In the Celanese process the oxidation reaction is performed at a temperature range 150-
2250C and pressure of approx 505 atm.

CH3CH2CH2CH3 + O2 CH3COOH + CH3COCH3

(c) Co product of Glycerine- H2O2 process:

When Glycerine is produced from propylene via acrolein then acetone is produced as a
by-product.

CH3CH═CH2 + H2O CH3CHOHCH3 + O2 CH3COCH3 + H2O2

(d) Oxidation of Isopropyl Benzene (Cumene): Cumene is synthesised from propylene and
benzene, followed by oxidation for the formation of hydro peroxide and splitting the same
into acetone and phenol. The crude products are then fractionated to get pure acetone and
phenol.

(e) Dehydrogenation of Isopropanol: Acetone is produced from catalytic dehydrogenation

of isopropanol. The catalyst used in this process is ZNO. The crude product obtained from
this process is fractioned and pure product is obtained.

(CH3)2CHOH (CH3)3CO + H2
Technology Comparison
From the technologies represented, there are three process which is used worldwide to
produce acetone. Some of it it’s main process is to produce acetone, and some produces acetone
as by-products. From the technologies represented, the three best process that can be taken into
considerations are the cumene process, dehydrogenation process and catalytic oxidation process.
The table below compromises the technical, economic and environmental overview of these
procedures to produce acetone industrially.

Cumene Hydroperoxide method

Process

Cumene hydroperoxide is produced at approximately 130℃ via the oxidation of cumene

with air in the presence of aqueous sodium carbonate as a catalyst (Lewis, 1993; CEH, 1998).
Cumene hydroperoxide is collected on activated charcoal, desorbed with trichlorofluoromethane,
and analyzed by gas chromatography/mass spectrometry (GC/MS) (Cocheo et al., 1983). It is a
captive intermediate in the production of acetone and phenol (Lewis, 1993). This invention relates
to a method for the decomposition of organic hydroperoxides, and more particularly this invention
relates to a method for producing phenol and acetone by decomposition of cumene hydroperoxide
over a modified montmorillonite acidic clay catalyst. The montmorillonite acidic clay 5 is
modified with a heteropoly acid or titanium, zirconium or aluminum. The invention is particularly
advantageous in that the decomposition takes place at mild temperatures and phenol/acetone is
generated in at least as high as 99% mole yield. The catalyst is very attractive in that by-products
are produced in a much smaller percentage than with standard acid catalysis.

It is known that cumene can be oxidized to cumene hydroperoxide and that cumene
hydroperoxide can be decomposed by various means to provide phenol and acetone. The use of
clays in catalysis is known.

The present invention provides a method to produce phenol and acetone by the
decomposition of cumene hydroperoxide in the presence of a catalyst comprising a
montmorillonite acidic clay which has been modified by a heterophony acid, or by titanium,
zirconium or aluminum, at a temperature of 20° to 150°C and a pressure of 0.1 to 7 MPa. Examples
demonstrate the effectiveness of, for example, tungstophosphoric acid on montmorillonite acidic
clays and zirconium and titanium modified montmorillonite silica-alumina clays.

Advantages of Cumene Hydroperoxide Disadvantages of Cumene Hydroperoxide

Catalytic Oxidation
Process

Fresh and recycled toluene first enter the oxidation reactor. The oxidation reactor is a gas-
liquid reactor in which air is sparged through a column of liquid (toluene). To reduce side reactions,
toluene is used as a limiting reactant. The catalyst is fed to the reactor along with the toluene
stream. After reaction, several products are formed including undesired impurities such as
benzaldehyde, benzyl alcohol, benzyl benzoate, CO and CO2. The reactor is facilitated with vent
after cooling and partial condensation of the air mixed hydrocarbon vapor stream. The liquid
product from the reactor then enters a distillation column which separates toluene from the other
organics. The organics then enters a hot water wash unit where hot water extracts benzoic acid.
All other impurities don't dissolve in water and leave the wash unit as heavy ends. The benzoic
acid rich hot water stream is sent to a crystallizer where benzoic acid crystals are formed. The
benzoic acid crystals are once again washed with water to obtain benzoic acid crystals. The benzoic
acid crystals are then melted and fed to the second oxidation reactor. The second oxidation reactor
is fed with air and cupric benzoate catalyst.

Steam is also added to the reactor to enhance the temperature of the reactants quickly. Once
again gas liquid reaction is facilitated. Cooling is facilitated by using a jacket or cooling tubes.
From the reactor two phases are obtained namely vapor and liquid. The vapor and liquid both
consist of phenol and therefore, both are subjected to series of separation steps to extract phenol
and enrich the same. The vapor enters a fractionating tower which separates the unreacted benzoic
acid from other compounds. The top product is obtained after partial condensation followed by
phase separation. The phase separator produces three streams namely the vent stream (that consists
of N2, CO and CO2), the aqueous water + phenol stream and the organic crude phenol stream. The
crude phenol stream is partially sent as a reflux to the fractionators and withdrawn as a product as
well. The bottom product from the second oxidation reactor consists of organic compounds and is
sent to water wash. After water wash, heavy compounds such as tar are removed, and phenol is
dissolved in water. This water + phenol mixture is mixed with the water + phenol mixture obtained
from the fractionators separating benzoic acid.
 The crude phenol is fed to a fractionator to obtain purified phenol as bottom product and
phenol + water mixture as a top product. The top product here is an azeotrope. The phenol + water
coming from three different sources can enter a distillation column that generates water waste as
a top product and a crude phenol stream as a bottom product.

Advantages of Catalytic Oxidation of Disadvantages of Catalytic Oxidation of

Propylene Propylene
Dehydrogenation of Isopropyl Alcohol (ISA)
Process

The base case study deals with the production of acetone from isopropyl alcohol by the
dehydrogenation reaction in the gas phase of the isopropyl alcohol in the presence of the
catalyst, then undergoes cooling, condensation and purification (separation of impurities
from the product - IPA, water) To obtain acetone with high purity (99.9%).

- MIXING: The concentration of IPA in the feed is different from that recirculated from the top of
the IPA distillation column, which contains small quantities of the product (acetone) that could not
be separated in the acetone distillation column. For this reason, it is necessary to mix these two
streams before entering the vaporizer, to homogenize the properties of the mixture. The resulting
mixture of IPA, water and a depreciable amount of acetone requires to be vaporized, since the
catalytic dehydrogenation reaction is carried out in the gas phase to improve the contact between
the catalyst and the reactant mixture.

- REACTOR: To carry out the reaction it is necessary to bring the feed mixture into contact with
the catalyst, to supply the heat of reaction because it is endothermic, to feed the reactants and to
withdraw the products in such a way as to favor the kinetics and selectivity. All these operations
must be carried out in a reactor that allows the reactants to be converted into desired products.

- CONDENSER AND COOLING: The reactor outlet current is at high temperatures, for this
reason it is necessary to cool this stream, to condense the IPA, acetone and water vapors to improve
the separation of the liquid and gaseous phases in the Flash tab. The reactor output stream is made
up acetone, water, isopropyl alcohol and hydrogen. To separate the desired product from the other
components it is necessary to carry out several separation operations.
Advantages of Dehydrogenation of ISA Disadvantages of Dehydrogenation of ISA
 In the production of Acetone different methods are presented, of which three are
outstanding: Cumene process, oxidation process of polypropylene and the process of
dehydrogenation of Isopropyl alcohol. Catalytic dehydrogenation of isopropanol can be chosen as
a synthetic route when high-purity acetone is required, such as in biomedical applications. In this
process 88% of isopropanol is recycled so this process is cost effective and gives approx. 99%
pure product. The comparison of these techniques is displayed in the table below.

Technical Economical Environmental

Catalytic  The cumene process is  Economically, the  Many of these acid

Cumene technically very hard cumene process catalysts require
Process to scale industrially. requires the use of substantial expenditure
 Difficulties in expensive metals such for production of
achieving >99.9% as Titanium as active phenol and acetone,
purity phenol required sites on the K-10 clay there are disposal
by today's market to ensure proper problems with spent
place due to process. acids or their salts.
entrainment or  In addition, by-  Production of benzene
breakthrough of said products such as 2- as intermediate which
acids. phenyl-2-propanol are is carcinogenic and
produced along with might endanger the live
the product and must of workers handling
somehow be removed this.
and processed.
Catalytic  High purity Acetone is  The integration and  In the dehydrogenation
Dehydrogenation obtained (98%-99%) process are well of IPA, high purity
Process known by process Acetone is obtained,
engineers, therefore and the conversion of
there is no need for acetone is high and has
extra professional no by-products, which
manpower. are significantly
hazardous to health
Catalytic  Low conversion of  A high concentration  If oxygen dissolved in
Oxidation acetone which is lower of HCl aqueous excess is discharged
Process than 99% solution is used and into the gas phase, it is
 Since oxygen molecule hence choice of mixed with propylene
is not directly reacted expensive corrosion to have a possibility of
with propylene, but a resistant material is troubles such as
complicated oxidation- required. explosion
reduction system is
utilized.
Future Alternative
Production of acetone and butanol by fermentation

Figure 3: Schematic representation of microbial chemical production from renewable

resources. A renewable resource is converted into a substrate stream, which can be
microbially converted into a base chemical. The chemical must be purified before it can be
upgraded to more advanced products.

The acetone–butanol (ABE) fermentation is a process in which bacteria of the species

Clostridium acetobutylicum convert the carbohydrate in a dilute, liquid medium into a

mixture of solvents: acetone, butanol and ethanol in an approximate final ratio of 3:6:1.

After fermentation, the solvents are present in the medium at a level of 2–3%, representing

an overall yield of around 30% based on the carbohydrate, and are separated

and concentrated by fractional distillation. During fermentation, which generally takes

about 48 h, large volumes of gas are also evolved comprising a mixture of 60% carbon

dioxide and 40% hydrogen by volume.

100 years after the first industrial exploitation of the Clostridial acetone-butanol

fermentation this process is still of high interest, commercially as well as scientifically. It still

poses many questions, holds a lot of secrets, and many aspects have yet to be understood.
Future generations of scientists will have enough to do to understand and optimize the

underlying metabolic processes. At the same time, it is one of the oldest and best studied

microbial chemical production processes, so we can a learn a lot from its development. The

centennial year is a good point to stop for a moment, look at this development and think

about what it must teach us for many other endeavors. This is of special relevance now, as

our societies strive to free ourselves from our dependence on petroleum.

Conclusion

References