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1.

0 Introduction

Acetone is the simplest ketone and one of the most abundant volatile organic compounds in the
atmosphere, with typical mixing ratios ranging from a few hundred parts per trillion to several
parts per billion or more [1]. Formulation and production of other chemicals can account for up to
75 percent of all uses of acetone. Acetone is a volatile organic compound that is considered to have
low toxicity, though improper use of it can cause serious problems. There are several uses for
acetone, including in chemicals, solvents and nail polish remover. The most common use of
acetone is to formulate other chemicals [1]. Beyond chemicals and solvents, other uses for acetone
exist in the production of cosmetics and household and personal care products. Acetone is
classified as a low-toxicity volatile organic compound. It easily evaporates in the air, dissolves in
water and is highly flammable. Chemical manufacturers can produce acetone, although it also can
be found in the environment as a naturally occurring substance. However, by the late 1950s, routes
to produce solvents from petroleum were made cost-competitive with fermentation [4]. In addition,
the major feedstock at the time was molasses, which spiked in price because of animal feed
demand. Acetone is typically produced in commercial quantities as a by-product during the
formation of phenol. However, acetone manufactured thus generally contains small amounts of
the reactant benzene and the desired product phenol. In the past, these impurities were deemed to
be within allowable limits [2]. However, recent downward revisions of these limits by the US Food
and Drug Administration has made alternative processes (which do not involve benzene) more
attractive.
1.1 Definition of acetone

Acetone is a colorless liquid with a distinctive taste and ‘fruity’ odor.

- Formula: CH3COCH3

- Molecular Weight: 58.079 g/mol.

- Chemical structure:

Acetone is the simplest and most important of the ketones. It is a colorless, mobile flammable
liquid with a mildly pungent and somewhat aromatic odor [3]. It is miscible in all proportions with
water and with organic solvents such as diethyl ether, methanol, ethyl alcohol, and esters. It is used
as solvent for cellulose acetate and nitro cellulose , as a carrier for acetylene , and as a raw material
for the chemical synthesis of a wide range of products , e.g. ketone bis-phenol ,di-acetone alcohol,
mesityl oxide, methyl isobutyl Ketone, hexylene glycol (2-methyl-2, 4-pentanediol), and
isophorone.

1.1.1 Historical Background


Until World War I, acetone was manufactured by the dry distillation of calcium acetate, which
was obtained by neutralizing pyroligneous acid (wood distillate) with lime and evaporating to
dryness. When World War I began, new methods of manufacture were explored [3]. Calcium
acetate could be made from acetic acid which had been produced by fermentation of alcohol
or from acetylene. However, this method could not compete with the fermentation process
developed by Weizmann and Hamlyn for the conversion of carbohydrate (cornstarch or
molasses) to acetone and butyl and ethyl alcohol by use of a special bacillus. Publicker
Industries, Commercial Solvents, and National Distillers, at one time, had combined bio-
fermentation process acetone capacity of 22,700 metric tons per year [4].
This method, in turn, became non-competitive in the late 1950s and early 1960s owing to the
economics of scale of the cumene hydro-peroxide-to-phenol and the isopropyl alcohol
dehydrogenation processes. Production of acetone by dehydrogenation of isopropyl alcohol
began in the early 1920s.
It remained the dominant production method through the sixties, in 1976, 60% of United States
acetone capacity was based on cumene hydro-peroxide. In 1974, about 65% of the acetone
produced was via the cumene hydro-peroxide process.
The process for direct oxidation of propylene to acetone was developed in the early to
middle1960s by Waker Chemie. However, this technology is not known to be in use in the
United States. In the middle 1960s, virtually all United States acetone was produced from
propylene. The two important routes in the United States to acetone are cumene hydroperoxide
cleavage and dehydrogenation of isopropyl alcohol. An undefined minor portion of the acetone
from isopropyl alcohol is produced by catalytic oxidation.

1.1.2 Acetone properties


It is colourless, 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 [5]. Acetone is used as a solvent for cellulose acetate and
nitrocellulose, as a such ketone, hexylene glycol(2-methyl-2,4-pentanediol), and isophorone
carrier for acetylene and as raw material for the chemical synthesis of a wide range of products
as ketene, methyl methacrylate, bisphenol A, diacetone alcohol, mesityl oxide, methyl isobutyl.
1.1.3 Physical properties
Properties of acetone as a function of Temperature
Temperature Viscosity Specific Vapour pressure Surface tension
°C mPa.s gravity Kpa Dyn/cm
t/20°C
0 0.4 0.807 9.3 26.2
20 0.32 0.783 24.7 28.7
40 0.27 0.759 54.5 21.2
60 - - 112 18.7
80 - - 226.6 16.2
100 - - 386.5 -

Table 1: Physical properties of acetone

Physical properties

Property Value
Formula C3H6O
Melting point, °C -94.6
Appearance Colorless liquid
Density, g/cm1 0.791
Molar mass, g/mol 58.08
Flash point -20°C
Viscosity, at 10° C, mPa.s 0.36
Boiling point at 1atm, ° C 56.1
Specific heat of liquid,J/g.k 2.6
Heat of vaporization, kJ/mol 29.1
Electrical conductivity at 25° C, S/cm 5.5*10-8
Specific heat of vapor, J/mol.k 92.1
Heat of combustion of liquid, kJ/mol 1787
Heat of formation of gas at 25° C, kJ/mol -216.5
Heat of formation of liquid at 25° C, kJ/mol -248
Entropy of liquid at 298.15k, J/k 200.1
Acidity 19.2
Basicity -5.2
Table2: Physical Properties of acetone

1.1.4 Chemical Properties


Acetone has closed-cup flash point of -18° C and an autoignition temperature of 538° C.
The explosive limits of acetone-air mixtures lie between 2.15 and 13.o vol % acetone in
air at 25 ° C Acetone shows the typical reactions of saturated aliphatic ketones. It forms
crystalline compounds with alkali bisulfites; e.g. with sodium bisulphate, the compound
(CH3)2C(OH)SO3Na is obtained [6]. Reducing agents converts convert acetone to
isopropyl alcohol and pinacol. Propane is the product of the Clemmensen reduction:

Isopropyl amine is produced by reductive ammonolysis of acetone:

Acetone undergoes much condensation reaction. For example, condensation with amines
will yield Schiff bases. Orthoformic esters condense with acetone to form acetals. With
hydrogen sulfide, acetone reacts to form thioketone; with mercaptans, it yields thioketals.
In the presence of an amine, or ammonia, various esters condense readily with acetone. In
the presence of sodium alkoxides and sodium amide, β-diketones are formed. It is also
possible to produce β-diketones by reaction of acetone with carboxylic anhydrides in the
presence of boron trifluoride [7]. Acetone is stable to many of the usual oxidants, such as
Fehlingʼs solution, silver nitrate, cold nitric acid, and neutral potassium permanganate, but
it can be oxidized with some of the stronger oxidants such as alkaline potassium
permanganate, chromic acid, hot nitric acid. Acetone can also be oxidized by an alkali
metal hypohalite or by halogen in the presence of a base, to a halo-form and alkali metal
acetate.
1.1.5 Uses of acetone

Figure1: Uses of acetone


Roughly 75% of the acetone delivered is utilized to manufacture different synthetic
compounds though 12% of it acts as a dissolvable thus as a solvent [7].
 As a solvent:
Acetone is a realized dissolvable in dissolving plastics and engineered
filaments incorporating those utilized in jugs produced using polystyrene and
a few sorts of polypropylene.in a few paints and disappears it is utilized as an
unpredictable part. In spite of the fact that itself it is an unpredictable and
combustible compound, it is utilized in the capacity and transportation of
acetylene which can't be securely pressurized as an unadulterated compound.
As a degreaser and cleaner Acetone can be utilized to break up dangerous
compound spills [8].
 Medical employments
Acetone is utilized in the therapeutic business for various purposes.it is utilized
by dermatologists for medicinal purposes to strip off dry skin.
 As a concoction moderate
As expressed before acetone is utilized in the manufacture of different
synthetic concoctions. A model is given in the creation of dissolvable
subsidiaries which currently account for roughly 33% of the absolute
utilization of acetone. Methyl metracrylate is a genuine model. It is delivered
by reacting cyanide with acetone to shape acetone cyanohydrin. Acetone
cyanohydrin is reacted with concentrated sulphuric acid to deliver methacrylate
sulfate. To get methyl metracrylate the methalcrylate sulfate is reacted with
methanol [9].
 Laboratory
Due its unpredictability and minimal effort acetone is utilized in the washing
of research facility product, for example, measuring utencils and test tubes.
Acetone is utilized in flouriscent imaging this is driven by its properties of
having a high fume pressure. It is additionally beneficial for gas blending
estimations in with Planar Laser Induced Flourecence considering the direct
connection between the fluorescence force, acetone fixation, and laser control
in an isobaric and isothermal condition [9].
 Domestic and different employments
Acetone is an essential added substance in cleaning operators, for example, nail
clean remover. It very well may be blended in with Automatic Transmission
Fluid to make a liquid that is more infiltrating and can relax rusted or stuck
jolts [8].
1.1.6 Analysis and storage
Acetone can be determined by treating with hydroxylamine hydrochloride and titrating the
liberated hydrochloric acid. The iodine (hypoiodate) is the basis of another useful method
of analysis. The excess iodine is titrated, and the amount which has reacted with the acetone
is thus determined by difference. In current industrial practice, gas chromatography is also
widely used, especially for quality control purposes [10]. The chief impurity in acetone is
usually few tenths of one percent of water. Acetone contains no oxidizable impurities, and
the color of a few drops of permanganate is retained for several hours. Other test methods
were covered in the previous section [10]. Since acetone, as commercially produced today,
is virtually a pure product, common practice is to store the product in steel tanks. Acetone
is also transported in steel drums, tank trucks, and rail cars.
1.2 MARKETS AND COMPETITION ANTICIPATED
The expanding industrialization in creating nations has prompted the expansion use of
acetone or has prompted acetone markets development. Acetone (propanone), is a natural
compound utilized as a solvent (about 35% of worldwide utilization of the item) in different
businesses, for example, development, car and hardware. Acetone is for the most part utilized
in the creation of Methyl Methacrylate (MMA) 25 percent of worldwide utilization and
Bisphenol-A (BPA) [11]. A global key acetone market research forecasted acetone demand
for the period 2014-2024 as shown by the graph below.

Figure2: Global acetone market volume

The global acetone market was valued at USD 5.75 billion in 2016 and is likely to witness growth
over the forecast period. The major consumers of MMA are the United States, China, Japan,
Germany, and Singapore.

The major players in the global acetone market are


 INEOS Phenol company,
 Mitsui chemicals,
 U.S Chemicals,
 DOW chemicals,
 Shell,
 Minda,
 Formosa chemicals and
 Sunoco

INEOS phenol is the largest world producer of acetone producing 1.2million tons of acetone
annually. Its global manufacturing capacity is almost double as compared to their competitors.

The regions in which acetone demand is high are as follows


 North America: U.S
 Europe: Russia and Germany
 Asia Pacific: China and India
 Central and South America: Brazil

In the Asia Pacific region, China is to dominate. China’s MMA supply is expected to increase in
2019, due to an increase in upcoming plant capacities. Wanhua Chemical had already introduced
its 50 000metric ton per year MMA plant, in 2018. Additionally, Heilongjiang Zhongmen Longxin
Chemical and Jiangsu Sailboat may be expanding their capacities at their respective MMA plant
locations, in 2019.

However, a close look on the U.S acetone markets particularly its acetone production capacities
and other foreign producers supplying the U.S during period 2016 -2018 brought up the following
computation. According to the U.S. Department of Commerce (“Commerce”) and the U.S.
International Trade Commission (“USITC” or “Commission”), U.S. purchasers of acetone are
firms that produce methyl methacrylate (“MMA”), bisphenol A (“BPA”), and other downstream
chemical products, and chemical distributors. Leading purchasers include MMA producers. The
major U.S. MMA producers are Dow, Evonik, and Lucite [12]. The leading U.S. producers of
acetone are

 AdvanSix,
 Altivia,
 Goodyear,
 INEOS,
 Olin and
 Shell

The leading foreign producers of acetone for United States are


 Belgium,
 Korea,
 Saudi Arabia,
 Singapore,
 Sasol of South Africa and
 Spain.
THE UNITED STATES MARKET CHARACTERISTICS AND DISTRIBUTION
It has been reported that there were significant changes in the product mix or marketing for acetone
since January 1, 2016. U.S. Producers’ capacity increased from 2016 to 2017, by 7.9 percent, and
then decreased from 2017 to 2018, by 12.2 percent. All in all, U.S. production was relatively stable
from 2016 to 2018, declining by 1.1 percent. Shell’s shutdown of one of its acetone/phenol lines
in Deer Park, Texas in 2018 February instead of the planned January 2018 resulted in oversupply
of acetone in the Gulf region. [1] The shutdown was driven by a desire to balance the phenol
market and resulted in reduced acetone supply by 147,700 short tons annually. From 2016 to 2018,
foreign producers (Subject imports) reported that capacity declined in South Africa but did not
change in Singapore and Spain, increased in Korea and Belgium and in Saudi Arabia.
Non-subject imports accounted for 3 percent of total U.S. imports in 2018. The largest source of
nonsubject imports during 2016-18 was Taiwan, which accounted for most of nonsubject imports
in 2016 and 2017, but a small share in 2018. Finland and Italy were the largest sources of
nonsubject imports in 2018 [13].

Apparent U.S. consumption of acetone totaled approximately 1.3 million short tons ($1.0 billion)
in 2018.U.S. producers’ U.S. shipments of acetone totaled 1.0 million short tons ($871 million) in
2018 and accounted for 80.9 percent of apparent U.S. consumption by quantity and 82.0 percent
by value. U.S. imports from subject sources totaled 247 million short tons ($182 million) in 2018
and 18.5 percent of apparent U.S. consumption by quantity and 17.4 percent by value. U.S. imports
from non-subject sources totaled 8.1 million short tons ($6 million) in 2018 and accounted for 0.6
percent of apparent U.S. consumption by quantity and 0.6 percent by Value. The U.S. demand for
acetone grew by about 7 percent from 2016 to 2018.

U.S. producers reported selling acetone to all U.S. regions that is Midwest, Southeast, Central
Southwest, Pacific Coast, Mountains, and Other regions. For U.S. producers, 39.5 percent of sales
were within 100 miles of their production facility, 41.5 percent were between 101 and 1,000 miles,
and 19.0 percent were over 1,000 miles. Importers sold 40.6 percent within 100 miles of their U.S.
point of shipment, 53.0 percent between 101 and 1,000 miles, and 6.3 percent over 1,000 miles.

U.S PRODUCTION CAPACITY AND UTILIZATION

2016 2017 2018


TOTAL CAPACITY (Short 1,383,994 1,493,188 1,310,652
tons)
TOTAL PRODUCTION (short 1,168,219 1,195,613 1,154,964
ton)
AVERAGEbCAPACITY 84.41 80.07 88.12
UTILIZATION (%)

Table3 : united states production capacity


Figure4: united states production capacity
U.S IMPORT VOLUMES & PRICES (2016-2018)

Figure5: import volumes


APPARENT U.S CONSUMPTION
YEAR 2016 2017 2018
ITEM DESCRIPTION Quantity Value Quantity Value Quantity Value
(short ($1000) (short ($1000) (short ($1000)
tons) tons) tons)
U.S. producers' U.S. 1,080,430 613,303 1,061,774 841,609 1,085,547 871,113
shipments
U.S. imports (Belgium, 110,047 59,700 175,822 128,266 255,735 188,943
Korea, S.Africa, Spain,
Singapore )
Apparent U.S. consumption 1,190,477 673,003 1,237,596 969,875 1,341,282 1,060,056
Table 5: acetone consumption

BUSINESS CYCLES
Acetone market was subject to business cycles with seasonality in the U.S. markets. The demand
for acetone used for MMA for coatings is highest in the spring and summer, and that acetone
demand tends to be lowest in the fourth quarter of the year. [2]Respondents stated that the acetone
industry typically has 5- to 7-year cycles, depending on crude oil prices, propylene demand, phenol
supply and demand, and acetone supply and demand.
Others report that March/April and October/November are peak demand seasons whilst other
importers reported that seasonal demand is related to housing starts and year-end inventory control
SUBSTITUTE PRODUCTS
Methyl ethyl ketone (“MEK”) and ethyl acetate can be used as substitutes for acetone as a solvent
in paints and coatings. MMA can also be produced using production methods that do not use
acetone, including ethylene-based production. There is currently no ethylene-based production of
MMA in the United States, but there is such production in Asia and the Middle East.

THE INDUSTRY IN BELGIUM


INEOS Europe AG (“INEOS Europe”) is believed to be the only producer of acetone in Belgium.
(3) According to GTA, the leading export markets for acetone from Belgium are Germany,
accounting for 38.3 percent of its acetone exports and the United Kingdom accounting for 17.9
percent. In 2018, the United States accounted for 9.4 percent of acetone from Belgium, which
represented its fourth largest export market.

Table6 Source: Official exports statistics under HS subheading 2914.11 as reported by EuroStat
in the Global Trade Atlas database, accessed March 15, 2019.

THE INDUSTRY IN KOREA


Kumho P&B Chemicals, Inc. and LG Chem, Ltd. are the producers of acetone in Korea. According
to GTA, the leading export markets for acetone from Korea are China accounting for 44.1 percent,
the United States accounting for 28.9 percent, and Japan accounting for 10.9 percent in 2018.
Table7 Source: Official exports statistics under HS subheading 2914.11 as reported by Korea
Customs and Trade Development Institution in the Global Trade Atlas database accessed March
15, 2019.

THE INDUSTRY IN SAUDI ARABIA


Rabigh Refining & Petrochemical Co. and Saudi Kayan Petrochemical Company are major
acetone producers in Saudi Arabia. According to GTA, the leading export markets for acetone
from Saudi Arabia are China which accounted for 36.6 percent of its 2018 acetone exports, United
Kingdom which accounted for 26.0, and Turkey which accounted for 22.3 percent.
Table8 Source: Exports statistics under HS subheading 2914.11 as reported by UN Comtrade in
the Global Trade Atlas database, accessed March 15, 2019.
THE INDUSTRY IN SINGAPORE
Mitsui Phenols Singapore Pte Ltd is believed to be the only producer of acetone in Singapore.
According to GTA, the leading export markets for acetone from Singapore in 2018 were Thailand
which accounted for 25.1 percent of Singapore’s acetone export, Indonesia, which accounted for
14.0 percent, and Germany, which accounted for 11.1 percent.

Table9 Source: Official exports statistics under HS subheading 2914.11 as reported by


International Enterprise Singapore in the Global Trade Atlas database, accessed March 15, 2019.

THE INDUSTRY IN SOUTH AFRICA

Sasol South Africa Limited (“Sasol”) is believed to be the only producer of acetone in South
Africa. According to GTA, the leading export markets for acetone from South Africa include
Belgium, which accounted for 41.7 percent of acetone exports from South Africa in 2018,
United States, which accounted for 34.4 percent, and Singapore, which accounted 10.5 percent.
Table10 Source: Official exports statistics under HS subheading 2914.11 as reported by
International Enterprise South Africa in the Global Trade Atlas database, accessed March 15,
2019.

THE INDUSTRY IN SPAIN


One foreign producer is Cepsa Quimica S.A. According to GTA, the leading export markets for
acetone from Spain include Netherlands, which accounted for 62.1 percent of acetone exports from
Spain, France, which accounted for 15.0 percent, and German, which accounted for 8.7 percent.
Table11 Source: Official imports statistics of imports from Spain under HS subheading 2914.11
as reported by various national statistical authorities in the Global Trade Atlas database, accessed
March 15, 2019.
1.3 RAW MATERIALS SUPPLY AND AVAILABILITY

Supply and Demand

Isopropanol is a colorless, flammable liquid available in finished-product concentrations anywhere


from 60% to 99% and is suitable for various uses in household products, processing industries,
cosmetic and pharmaceutical product manufacturers [14]. Uses include as a solvent for cleaning
electronics, as 'rubbing alcohol', stencil cleaning applications, cleaning of assemblies, Isopropanol
is often also used as a rinsing media when cleaning with a solvent for hybrid or ceramic
applications prior to bonding.

Based on grade, the global isopropyl alcohol demand is categorized into:

 Industrial grade
 Pharmaceutical grade
 Cosmetic grade
 Electronic grade
Based on application, the global isopropyl alcohol demand is categorized into:

 Process solvent
 Cleaning agents
 Coating solvent
 Intermediates
 Others

Based on end-use industries, the global isopropyl alcohol demand is categorized into:

 Cosmetic & Personal care


 Pharmaceutical
 Food & Beverage Industry
 Paints & Coatings
 Chemical
 Others
North America, Eastern Europe, and the Asia Pacific are the major consumers of isopropyl alcohol
in the global market. Increasing disposable income coupled with rising awareness about personal
care products are two main factors which have led to an increase in the consumption, and
ultimately the production, of isopropyl alcohol in these regions [13]. Though there is a high local
demand for Isopropanol manufactured in these regions, a large portion of the product is available
for export to other (developing) regions such as Southern Africa. Brazil is one of major producers
of cosmetic and personal care products, and as such the Latin America region is also expected to
witness significant growth opportunities for the isopropyl alcohol market and production.

Some of the major companies/manufacturers in the global isopropyl alcohol market are:

 BASF SE

 Royal Dutch Shell Plc.

 Exxon Mobil Corporation

 The Dow Chemical Company

 Clariant

 Mitsui Chemicals, Inc.

 LG Chem Ltd.

 LCY GROUP

 Zibo Nuoao Chemical Co.,Ltd.

 Perrigo Company plc

 Ami Chemicals

Isopropanol production is mostly based on demand at any given time, with notable fluctuations in
overall availability based on economic, political, geographical environmental and/or social
occurrences and trends. For example, increasing urbanization as well as pollution has led to the
emergence of many health hazards as well as skin diseases [15]. This is expected to lead to an
increase in the use of cosmetic, personal care products and cleaning agents worldwide. To meet
the increasing demand, chemical companies are working on developing new chemicals as raw
material ingredients or as finished products, such as isopropanol and acetone, required by the
cosmetic and personal care industry [16]. This will lead to an increase in the availability of
isopropyl alcohol which is used as a solvent during the manufacturing process of various chemical
products. Another example is the drop-in isopropanol availability for export from the United States
amid the US-China trade war in which sentiment became bearish and demand dwindled, causing
some exporters and importers to delay shipping material [16]. In Europe, weakening Eurozone
indicators in the early stages of the decade led to European producers having reducing capacity
with cases such as LyondellBasell shutting its 110,000 tonne/year Berre, France plant towards the
end of 2009. However, the French producer Novapex started a new 40,000 tonne/year plant at
Roussillon, France in January 2010 and recovery was expected to be weak in 2010 with
improvement not until the second half of the year.

Handling during Transportation, and Storage effects on Availability.

Due to properties described in the data sheets such as flammability and low toxicity, as well as
common water content values, facilities for handling isopropanol should conform to set
regulations. It can be stored safely for extensive durations of time if done in a suitable manner,
however this is not a norm and it is preferred on-site amounts coinciding with the amounts to be
sold or processed. As storage space for flammable liquids is generally limited, most manufacturers
order Isopropanol as needed and minimize storage quantity [17]. This translates to limited
amounts of imported isopropanol being present in each area, but with the readily available option
of importing required amounts when the need arises, from major manufacturers mostly based
overseas [12].

The manufacturer or reseller provide an analysis or datasheet which will include the manufacture
date. There is no definitive standard for the shelf life of isopropyl alcohol. However, packaging
and storage conditions are the most important factor in shelf life, especially during transportation
where regulation of conditions is particularly harder [18]. Because most isopropyl alcohol contains
water content, it’s important that the container is always properly resealed when stored or not in
use. When exposed to air, the alcohol evaporates faster than the water content. As the alcohol
evaporates, water content remains, thus skewing the actual alcohol to water volume. Metal
containers may be used for transportation and storage [19]. These are available in sizes as small as
5 gallons. Some rusting may be expected to occur in long term storage, due to the moisture present.
Although suspended rust particles can be removed using filters, a preferred method is to use an
alternate material of construction, such as a lined steel tank or a tank made of stainless steel or
aluminium. The metal containers prevent degradation caused by light, plastic leech, or spills/drips
caused by punctures or container damage. Under ideal storage conditions, the shelf life of IPA is
roughly three years from the manufacture date [20].

Assuming adequate storage conditions over the lifetime of the product, Isopropanol is generally a
stable chemical. Ultimately taking precautionary measures in the transportation and storage of
isopropanol will enable importing (transporting) and storage of larger volumes of the chemical,
increasing the availability within the region.

Copper

Typically, the availability of minerals is based on the concept of reserves and resources. Copper is
naturally present in the Earth’s crust, at a concentration of about 67 parts per million. According
to the United States Geological Survey (USGS), copper reserves amount to 690 million tonnes
(Mt). According to this Survey conducted in 2013, since 1950, reports have regularly shown that
there have always been, on average, 40 years of copper reserves and over 200 years of resources
available. The USGS assessed undiscovered copper in two deposit types that account for about
80% of the world’s copper supply [21]. Porphyry copper deposits account for about 60% of the
world’s copper. In porphyry copper deposits, copper ore minerals are disseminated in igneous
intrusions. Sediment-hosted stratabound copper deposits, in which copper is concentrated in layers
in sedimentary rocks, account for about 20% of the world’s identified copper.

Copper is most commonly present in the earth’s crust as copper-iron-sulfide and copper sulfide
minerals, e.g. chalcopyrite (CuFeS2), bornite (CusFeS2) and chalcocite (Cu2S). The concentration
of these minerals in an ore body is low [22]. Typical copper ores contain from 0.5% Cu (open pit
mines) to 1 or 2% Cu (underground mines). Pure copper metal is produced from these ores by
concentration, smelting and refining.

While most mines operate with copper concentrations of between 0.2 and 0.8 %, some of the
richest ore bodies, located in central to southern Africa, can contain 5–6% copper. There are over
70 known deposits in Zimbabwe that have produced copper either as a primary or secondary
product including Makonde, Kadoma, Mutare, Chirumanzu, Chegutu, Kwekwe, Shurugwi,
Beitbridge, Gokwe, Bindura, Chipinge, Bikita, Insiza, Makonde, Harare, Bulawayo, Shamva,
Chiredzi, Nkayi, Mudzi, Chegutu, Bindura, Kwekwe, Hurungwe, Bubi, Makonde, Bikita, Gwanda
and Masvingo.

Figure: map of copper in Zimbabwe

The main producing area has been the Magondi Basin in an area stretching for over 150km. Similar
copper deposits are found in the south eastern part of the country in the Umkondo Basin. Several
copper prospects also occur in hydrothermal deposits in Archaean Greenstone Belts and in granite
e.g. Inyathi, Copper duke [23]. Primary copper production slowed down following closure of
Mhangura, and it is now being produced as a by-product of other minerals e.g. Gold, Nickel. In
addition, recycling, innovation and mining exploration continue to contribute to the long-term
availability of copper. Metallic copper occurs occasionally in nature and for this reason, it was
known to man about 7000 B.C. Its early uses were in jewelry, utensils, tools and weapons, which
has led to a high level of scrap accumulation over the years. Scrap copper and copper alloys
become a major source for Copper when process-able. Recycle of copper and copper-alloy scrap
used objects i.e. old scrap, accounts for 10-1 5% of pre-manufacture copper production. Recycle
of manufacturing wastes i.e. new scrap, accounts for another 25 or 35%. This copper is recovered
by simple melting of high-purity scrap and smelting/refining of impure scrap.

In actual dollars, the selling price of copper has moved upwards. In constant dollars, however, the
price has fallen precipitously [24]. At the start of 21st century, it was near a 50-year low. The low
price is caused by an excess of supply over demand. It is difficult for producers but beneficial to
users.

In the wacker process the major raw materials used is propylene and palladium (II) chloride
catalyst. Below is a brief account of the mentioned raw materials:

PROPYLENE

Propylene or propene is an important building block for many chemicals It has quite several uses
which other than acetone production includes, production of cumene, propanol, phenol, propanone
and butanol [25].

World 94 million tonnes


Asia Pacific 27 million tonnes
Europe 15 million tonnes
US 13 million tonnes
Middle east 7.5 million tonnes
Table 12: Shows the annual production of propylene in the world (2005)
These overwhelming values of propylene have been manufactured using two processes for many
years, steam cracking and catalytic cracking method. Industrially propylene can be obtained into
three different grades, these are:

1) Polymer grade with a minimum purity of 99.5%

2) Chemical grade with a minimum purity of 93-94%

3) Refinery grade with a purity of around 70% with a minimum of 60%

The major industries competing with the Acetone Manufacturing industry for raw material

Propylene are polypropylene, acrylonitrile, oxo chemicals, and acrylic acid

In Zimbabwe there is no propylene producing industry hence the nearest source of the raw material
is South Africa. Sasol and Safripol are the major suppliers of acetone South Africa produces 650
000 tonnes of the raw materal,520 000 by Sasol and 150 000 by Safripol.

Internationally, major producers are Chevron Phillips Chemical, Dow Chemical, Equist Chemical,
ExxonMobil, Huntsman, LGChem, Mitsubishi Chemical, Mitsui Chemicals.

PALLADIUM CHLORIDE

It is also known as palladium dichloride. It is manufactured by the reaction of chlorine with


palladium metal at high temperatures. The major players of palladium markets include Synthon,
Chimet and India Platinum among others.

Cost of Raw Material

Propylene Polymer grade: $0.926/kg


Chemical Grade: $0.881/Kg
Palladium (II) chloride $17 637/KG
In the fermentation/ maturation process, the major raw materials for the process is the sugars or
molasses being fermented and the bacteria that suppresses the production of butanol and other
fermentation products.

Sugars/ molasses

In the current Zimbabwe economic and agricultural situation there is no enough molasses to
support the already running industry since the current molasses is used for animal feed stock due
to the drought in the region while the rest is used in some other processes such that 75%of the
companies that uses molasses as their main raw material ended up importing from Mozambique
and Zambia since there is much there that can as well sustain them. It could be possible to set up
an agricultural scheme so as to meet the demands of the fed required for the production of acetone
via fermentation hence its becomes a requisite to import the molasses for the acetone production
while in the long run there could be a plant expansion by having the agricultural section where
molasses is will be produced.

Bacteria

For an effective initiation of the plant a favorable start up the biocatalyst had to be imported and
the supplier is told the specifications as per desired by the company. Hence the availability of the
culture depends on the source where it is to be supplied from and hence that’s the limitation mainly
is due to the importation of the bio catalyst.
1.4 TECHNOLOGIES FOR THE PRODUCTION OF ACETONE
Acetone can be produced industrially by several methods or processes all leads to the final
product acetone. The process is a multistage that can be utilized for a small industrial
production of acetone in the presence of sodium hyroxide as the source of the hydroxyl ions

1.4.1 Hydrolysis of gem dichlorides


Introduction
For the hydrolysis of 2.2dirchloropane, the reaction is done in an alkaline where the OH-
attacks the partially carbon giving leading to the formation of 2 Chrolo Propane-2-ol there
is further nucleophilic substitution on the remaining chlorine nucleophile attached to form
a propane-2,2-diol on which water is removed from the di-ol to form acetone which is the
desired product as shown below

The dihalide gem is produced when the alkane which are readily available reacted with the
halogen for example chlorine in the presence of ultraviolet light [26]. A free radical
substitution reaction occurs and thus the 2,2 dichloropropane is produced.
Preparation of Alkyl Halides

Free Radical
Halogenation Usually this method gives mixtures of mono-, di-, tri- etc halogenated
compounds, which is considered an inefficient method for the synthesis of a desired
compound. Consider propane: Sometimes if there can be control over the selectivity
of halogenation this is a useful route [27].
Halogenation from alkene
The addition reaction is taken or happens in few steps where by the first step there
Is formation of the halide contained at the two carbon atoms from the double bond
then with the addition of a base to produce a triple bond on the akyne then finally
the halogens ae presented on the same carbon to form a gem dihalide [25].

Process flow diagram of acetone production

R-CH=CH2+X2 R-CHX-CH2X
R-CHX-CH2X+ base R-CCH(alkyne-tripple bond in CCH group)
R-CCH+ 2HX [R-CX=CH2 + HX R-CX2-CH3

Advantages

Cheap method to produce acetone


High purity of acetone produced

Disadvantages

It is a small-scale process still done at a laboratory process and it’s still an experiment from
understanding of organic chemistry reactions.
It is not an authentic method to produce commercial acetone

Conclusion
This method of producing acetone has proven to be having high yields and conversion though
its practicality is still verge and is not yet a proved but nothing but just an appreciation of
organic chemistry hence its still a process under study to be an world-wide method considered
at an industrial level [28].

1.4.2 Oxidation of isopropyl alcohol

Introduction

Isopropyl alcohol is a secondary alcohol that can be oxidized to produce a


corresponding ketone thus a method which is described by a few stages below such that
the product of higher value is produced as the above used had clearly state these in
detail [29].

Procedure
1. Introduce 25g IPA and 100cc water into the reaction flask.
2. Transfer to addition funnel a cooled solution of 45g of sodium dichromate
3. 75cc water and 40cc concentrated Sulfuric acid
4. Heat to boiling point and remove flame
5. Add chromic acid solution until boiling resumes spontaneously
6. Maintain gentle boiling by adding chromic acid until half of the oxidant is used
7. Distill the acetone by applying a small flame not exceeding 60⁰C.

If temperature is exceeded, collect the distillate in separate flask and redistill.


This procedure is still to be evaluated and scaled up for an industrial beneficiation of
the method for acetone production.

Advantages

High yield (75-80% or more)


High purity product (over 99%)

Disadvantages

Cold oxidation leaves some IPA unoxidized


Over oxidation can hardly be avoided especially towards the end when the
mixture contains more acetone and little alcohol ie continuation of oxidation to
acetic acid and carbon dioxide occurs.Invalid source specified.

Catalysts activities on the reaction kinetics

Picolinic Acid Catalysis of the Chromic Acid Oxidation of Isopropyl Alcohol


This is a specifically catalyzed oxidation of an organic substrate by chromic acid. Picolinic
acid has a very high rate accelerating effect on the reaction between chromic acid and IPA
producing acetone. The catalysis is highly specific and related to the proximity of the
Nitrogen atom and carboxylic group.

At constant acidity, the reaction is first order in chromium (VI), isopropyl alcohol, and in
picolinic acid. It is also first order in isopropyl alcohol throughout the entire range of
acidities

The acidity dependence is second order in hydrogen ions at low acidities and approaches a
zero-order acidity dependency at high acid concentrations

The reaction mechanism is as shown below


The mechanism above leads to the rate law below

This is derived from equations 2 to 6 below


We believe that the reason for the catalytic activity of Picolinic acid depends on its ability
to stabilize intermediate chromium valence states, probably chromium (IV), through
complex formation.

Catalytic oxidation of IPA to acetone on divided cupric oxides.

Acetone is produced by mild oxidation of IPA on copper oxide catalysts. It’s produced on
the cuprous and the cupric oxide sites. It is believed that acetone is strongly adsorbed on
cupric oxide at the beginning of the experiment and then at the end IPA reduces the solid
and acetone is weakly adsorbed on the cuprous oxide nuclei. The reducing power of the
air-alcohol mixture towards solids depends on the composition of the gas. Nitrogen is
observed to be used as a carrier gas and reduces the solid at temperatures around 120⁰C.

The actual catalyst is active cupric oxide resulting from oxidation of the cuprous oxide
nuclei. An associated side reduction of the solid occurs.

According to Mars and Van Krevelen mechanism,

Alcohol + oxidized catalyst Acetone + reduced catalyst

Reduced catalyst + oxygen Oxidized catalyst.


The reoxidation of the catalyst proceed more slowly than the formation of the active
catalyst surface.

For constant temperature of 200⁰C, the influences of pressures of the reactants was studied
and the reaction scheme and thus kinetic equation is in agreement with Mars and Krevelen
Invalid source specified.which states that the kinetic equation is

1 1 1
= +
VAC PAl Kred Kox PO2 n

Advantages

At low temperatures, the catalyst show good selectivity towards acetone


production.Invalid source specified.

Disadvantages

Associated carbonation of the solids


The alcohol may be oxidized to carbon dioxide and water

1.4.3 Fermentation process

Introduction

Acetone-butanol-ethanol (ABE) maturation of sugar utilizing Clostridium


Acetoutylicum to the solvents acetone, butanol and ethanol was first worked on
during the First World War in 1912 when the need of acetone use rose as an
utilization of cordite (a smokeless weapons powder). It turned into the second
biggest maturation procedure to be done at modern level, with ethanol creation
being first in the aging procedures. Anyway after the War, interest for acetone bit
by bit diminished and furthermore the molasses which was utilized as crude
material in the maturation procedure was the primary feedstock by the 1950s
affecting a sharp increment in the obtaining costs. These variables affected the
reduction in enthusiasm for ABE aging.

As of now, the developing interest for inexhaustible transportation powers to


alleviate ozone depleting substance outflows is being empowered by both the
advancement of new advances (S, et al., 2008) and the improvement of once
industrially settled procedures. (Whiten, 2012) This has prompted an enthusiasm
for ABE aging and concentrates in progress of the procedure are being explored.

Process Description

Substrate pretreatment

The raw material, molasses, is first prepared to give out a concentration of fermentable
sugars of 5 – 7.5% per wt/vol. This is achieved by cooking and sterilizing the molasses at
a temperature of 107 to 120ºC for 15 to 60 min.

Fermentation Process

At an industrial scale, the production takes place in a batch process with use of 50 000 to
200 000 gallons capacitated fermenters. These fermenters are filled to 90% capacity under
a blanket of carbon dioxide, and this sterile carbon dioxide is periodically bubbled to
facilitate mixing after inoculation stage.

Before addition of the feed to the fermenters, the feed mixture, comprising of water,
molasses and broth, is first pasteurized after being mixed in a mixing tank.

The broth, according to Invalid source specified., which the bacteria will operate in may
consists of the following components; (NH4 )2 SO4, KH2 PO4 , NaCl, Yeast Extract,
Asparagine, Water, etc. This process is termed as pre-fermentation. After pasteurization of
the feed, it is then added to the fermenters which will run the fermentation process for 24
hours before it is drained, washed, stripped of oxygen and re-filled with the feed.Invalid
source specified.. The products from the fermentation vessel include acetone, butanol,
ethanol and unreacted molasses and broth, while the bacteria cells are reused 2 times before
they are replaced with new cells. The non-condensable gases include hydrogen and carbon
dioxide which proceed to gas purification sections.

Purification

The purification process includes the extraction of acetone, butanol and ethanol from the
extraction unit, the distillation/stripping section and the gas purification section as it is
shown in the block diagram in figure 1 below;

Figure: Block Diagram of ABE Industrial Fermentation Process

Fermentation Efficiency

Fermentations utilizing molasses as a substrate were run at a lower temperature (29 to 35°C), with
31 to 32°C being optimum for many strains. Solvent yields based on the fermentable sugars were
usually around 29 to 33%, and cell metabolism is inhibited when the concentration of solvents
reached 18 to 22 g/liter, although in practice lower concentrations are often obtained.Invalid
source specified.. Solvent ratios for the current industrial process lie at 6:3:1 (butanol-acetone-
ethanol). The conversion of the molasses lie at 50% to carbon dioxide & hydrogen while 33.39%
is converted to the solvents.

Advantages

Various substrates can be substituted for the fermentation process, this also opens the
potential to improvement and better technologies with better substrates used.
With the rising prices for mineral oil, it has now the economical and technological potential
to replace petro-chemistry to produce fuels from renewable resources. Invalid source
specified.
Promotes recycling as the substrate uses food-waste products
Promotes green / renewable energy decreasing the carbon footprint and avoiding toxic
chemicals as far as possible.

Disadvantages

Butanol is highly toxic to biological systems at quite low concentrations, which means that
the level of solvents obtainable in the final fermentation broth were only of the order of 2%
maximum. The recovery of these low concentrations of solvents by distillation is expensive
because of the large amount of energy required. Invalid source specified.
Due to intrinsic limitations suffered by the fermentation process, the yields of the process
are quite low.
Production ratios of solvents favour the formation of butanol more than the formation of
acetone which is the main/desired product.
Fermentation process is complex and requires maintaining sterile conditions to avoid
contamination due to phage infections which will further affect the yield of products.
The fermentation process produces large volumes of effluent, which require a large focus
on specific processes for handling, treatment, and processing.
Large amounts of energy needed for production through batch processes as compared to
continuous processes.
1.4.4 Ozonolysis of alkenes
Introduction
Ozonolysis is an organic reaction where the unsaturated bonds of alkene compounds are
cleaved with ozone, which is a reactive allotrope of oxygen. The terms ozonolysis, or
“oxidative cleavage” originated in the 1800’s with its inventor, Christian Friedrich
Schönbein. The reaction also is attributed to Carl Dietrich Harries, thus it is sometimes
termed “Harries ozonolysis”.

The process allows for carbon-carbon double or triple bonds to be replaced by double
bonds with oxygen. Double bonded Alkenes form organic compounds in which the carbon–
carbon bond has been replaced by a carbonyl group. The outcome of the reaction depends
on the type of multiple bond being oxidized and the work-up conditions. On an industrial
scale, azelaic acid and pelargonic acids are produced from ozonolysis. Ozonolysis also
occurs naturally and would break down repeated units used in rubber and other polymers.
At Laboratory scale, Alkenes can be oxidized with ozone to form alcohols, aldehydes or
ketones, or carboxylic acids.

Procedure
In a typical lab procedure, ozone is bubbled through a solution of the alkene in methanol
at −78 °C until the solution takes on a characteristic blue color, which is due to unreacted
ozone. This indicates complete consumption of the alkene. Alternatively, various other
chemicals can be used as indicators of this endpoint by detecting the presence of ozone. If
ozonolysis is performed by bubbling a stream of ozone-enriched oxygen through the
reaction mixture, the gas that bubbles out can be directed through a potassium iodide
solution. When the solution has stopped absorbing ozone, the ozone in the bubbles oxidizes
the iodide to iodine, which can easily be observed by its violet color. For closer control of
the reaction itself, an indicator such as Sudan Red III can be added to the reaction mixture.
Ozone reacts with this indicator more slowly than with the intended ozonolysis target. The
ozonolysis of the indicator, which causes a noticeable color change, only occurs once the
desired target has been consumed. The presence of unreacted ozone in solution (seeing its
blue color) or in the bubbles (via iodide detection) only indicates when all alkenes have
reacted.

After completing the initial step, a reagent is then added to convert the intermediate
(usually ozonide) to a carbonyl derivative. Reductive work-up conditions are used for
ketone production, where use of triphenylphosphine, thiourea, zinc dust, or dimethyl
sulfide produces aldehydes or ketones while the use of sodium borohydride produces
alcohols as a ketone intermediate. Dichloromethane is often used to facilitate timely
cleavage of the ozonide where azelaic acid and pelargonic acids are produced from
ozonolysis of oleic acid on an industrial scale.

Ketones (particularly acetone) can be formed through reductive workup with use of (O3)
ozone, in the presence of a reducing agent such as dimethyl sulphide or zinc & acetic acid.
After the reduction takes place the reducing agent will attach to the remaining third oxygen
from O3 that is not seen in our final product. Because of this, along with our carbonyl
products we will also find dimethyl sulfoxide or ZnO being produced.

Ozonolysis Reaction and Mechanism


The products of ozonolysis will vary depending on two things:

1. The R groups that are attached to the alkene:


a. Ends of alkenes with –R groups on both sides = Ketones
b. Ends of alkenes with 1 –H = Aldehydes
c. Ends of alkenes with 2 –Hs (yielding single carbon fragments) = Formaldehyde.

2. Use of “reductive workup” with reducing agents mentioned above, or use of “oxidative
workup” with reagents such as hydrogen peroxide.

When the reductive workup reaction takes place, intermediates obtained are the
molozonide and the ozonide compunds.
Molozonide Intermediate
The first intermediate product in the ketone production mechanism is a molozonide
molecule, formed from electrophilic addition of ozone to the Carbon-Carbon
double bond. It is a cyclic structure containing 3 oxygen atoms connected in a row,
also referred to as a 1,2,3-trioxolane. This will be your unstable intermediate which
will further undergo a rearrangement to form a carbonyl and a carbonyl oxide
molecule. An ozonide is more stable than the molozonide, however it still exhibits
a fair amount of instability.

Step 1

Ozonide Intermediate

The second intermediate in the second step of the reaction is the ozonide compound which
is then further reduced to carbonyl products. This results in the breaking of bonds replacing
it by a Carbon-Oxygen double bond instead. The carbonyl and the carbonyl oxide
rearranges itself and reforms to create the stable ozonide intermediate. A reductive workup
could then be performed to convert the ozonide molecule into the desired carbonyl
products.

Criegee Intermediate

Rudolf Criegee proposed the mechanism therefore the ‘Criegee zwitterion’ or ‘Criegee
intermediate’ refer to an intermediate that appears between the molozonide and the
ozonide.

Step 2
Overall reaction

1.4.5 From alkane nitriles

1.4.6 Decomposition of Isopropyl alcohol

Introduction

Isopropyl alcohol may be decomposed at controlled, elevated temperatures to Acetone


and Hydrogen products in a catalyzed reaction to produce high acetone yields (+90%)
in the following reaction:
C3H8O = C3H6O + H2

The catalyst used may be homogenous for example water, or heterogeneous for example
manganese (II) oxide or chalcopyrite at a specified range of temperatures. The
decomposition reaction may occur simultaneously with other reactions such as
dehydrogenation. Selectivity towards the decomposition reaction depends on the chosen
catalyst and reaction conditions such as temperature and pressure. Ultimately these factors
also determine the by products produced, for example when manganese oxide is used
mesityl oxide and heavier ketones are to be produced at certain temperature value and
partial pressures, and the overall percentage purity of the desired product.

Figure: IPA decomposition

Decomposition under Water Catalysis


The decomposition reaction using water as a catalyst is the most widely used at industrial
level and is the route to be used as the basis of the IPA decomposition description. Main
components or equipment involved in this process are the reactor, separation units (flash
and distillation columns) and heat exchangers. A PFR reactor may be used as it is capable
of efficient heat transfer, continuous production at high temperatures, with a high
conversion per unit volume. Isopropyl alcohol and water as a catalyst are fed into the
reactor at a temeperature of 298 K (25°C) and pressure of 101.325 kPa (1 bar). In these
conditions, the reaction is endothermic with 90% of isopropyl alcohol decomposing to
acetone and hydrogen. Heat is supplied from hot water to the reactor, where heat exchanger
tubes carry water at temperatures as high as 700K to the reactor. The hot water is supplied
from a fired heater. Shell and tube heat exchangers are used due to their high efficiency of
heat transfer because the amount of heat distributes over the number of tubes, which makes
the heat transfer occur more quickly
Process Description
Figure: Production of acetone from IPA decomposition process flow

The stream leaving the reactor containing the desired products is cooled from its high temperature
by a heat exchanger unit. This is done to prepare the stream to be fed into the distillation column
and to avoid all components evaporating in the column. Water is used in the heat exchanger to
cool the stream, from about 400K to 278K. In the distillation column, hydrogen, with the lowest
boiling point, is the first component that leaves the mixture upon evaporation. A boiler is required
to warm the mixture. H2 along with a small amount of acetone, isopropyl alcohol, and water
evaporates to the top of the distillation column in a vapor phase. The mixture must be liquidized
in order to separate the small amount of acetone. A condenser is placed at the top of the column to
cool the vapour mixture as reflux. The small amount of acetone accompanies H2 out of the
condenser to the refrigeration unit. Refrigeration cools the H2 into a liquid phase to efficiently
store it, and then the acetone is liquidized, separated and combined in mixture with the boiler
components.

The mixture from this stream is then heated to about 350K, for the purposes of reaching the boiling
point of the second component to be separated i.e. acetone. Once again hot water is employed in
the heating of the stream. The mixture then enters the second distillation column, where Acetone
is evaporated with a small amount of isopropyl alcohol by use of another boiler at the bottom of
the column. The mixture is again condensed at the top of the column where isopropyl alcohol is
separated from the acetone and returns to the distillation column as reflux material. Acetone is
converted from a gas to liquid phase due to the difficulty of storing acetone as a gas. Water and
isopropyl alcohol leave the column from the bottom.

The stream from the second column is heated through a heat exchanger, before the mixture enters
the third distillation column. Isopropyl alcohol is separated from water after the operation
temperature reaches the boiling point of isopropyl alcohol. The resulting vapour contains a small
amount of water. The mixture is cooled at which point isopropyl alcohol is separated from the rest
of the water. A refrigerator turns the isopropyl alcohol from a vapour phase to a liquid phase and
it is recycled to the reactor.

There are three waste streams resulting from this process. First, the hydrogen is separated from the
first distillation column. This waste product may be processed into other products such as fuel and
ammonia, or distributed to other hydrogen processing plants. Second, isopropyl alcohol is
separated from the third distillation column, which may be recycled from this column back to the
reactor. Finally, the water component is separated from the third distillation column, which could
be used as catalyst for the reactor. The water may be recycled back to the reactor, used as the heat
transfer medium, or used in hydrogen scrubbing. Advantages and disadvantages associated with
the decomposition process are described in the table below:

Advantages

Catalysts used are widely available locally and hence ultimately cheap
Product purity is high above 95%
Catalyst flexibility since it could be homogenous or heterogenous

Disadvantages

The process is associated with many process units, making it complex ad hence costly
Recycling water the third distillation column will be expensive
Many operations requiring a large amount of energy.

1.4.7 Oxidation of propylene

Introduction
Acetone is produced by further extension of the Wacker process which was used to
produce acetaldehyde by the oxidation of ethylene in the presence of a palladium (II)
chloride catalyst. From the Wacker process Acetone is formed by the direct oxidation
of propylene. The transformed reaction comprises the formation of a complex with
propylene in the presence of palladium chloride and in the hydrochloric acid medium.

INDUSTRIAL MANUFACTURE

Propylene is vaporised and heated to 115oC.it is introduced at the base of the oxidation
reactor to which the catalyst is added. The catalyst solution is preheated to the same
temperature and operates at 1.2 x 106 Pa absolute. The exit streams leave at a
temperature of 120oC and are flashed at 0.5 x 106 Pa absolute, to allow for the
separation of reactants and the products of the reaction medium in gaseous form.
The regeneration of the catalyst is kept in liquid phase. The operation conditions of the
latter process are at 110oC and 1.2 x 106 Pa absolute in the presence of precompressed
air. Off gases are separated from the catalyst system by flashing at 0.15x 106 Pa
absolute.

Acetone stripped in the gas phase is recovered by water scrubbing in an absorption


column operating at atmospheric pressure and 50oc along with other organic
compounds. These are recycled with the catalyst solution.

The acetone produced is distilled to separate the light ends with heavy ends separation
to remove products such as water and acetic acid which are heavyInvalid source
specified..
ADVANTAGES

Reactions are one-step, produce crude product (mixed with catalyst solution) directly from
starting material.
Yields are high-92 to 94% for acetone,
Energy consumption is relatively low—about 18 kwh. per 100 lb. of ketone.
Feed can be a mixture of olefins and saturated hydrocarbons.

DISADVANTAGES

Production of acetone from propylene oxidation process is that propylene required for the
process should be 99 % pure
Many by products are formed which lead to the questioning of the acetone yield
Acidic catalyst solutions are corrosive
Chlorinated by products are formed which lead to the need of a cleaning process that is
rather expensive
Process is not done worldwide, so far it is only practised in japan
Catayst is expensive
Because acid is used there are high corrosion problems

1.4.8 Dehydrogenation of Isoproyl alcohol

Introduction

Isopropyl alcohol (IPA) in vapor phase can be dehydrogenized to acetone of high purity
(>95%) and hydrogen in the presence of a catalyst by an endothermic reaction
represented below

Catalyst
CH3 − CHOH − CH3 (v) → CH3 − CO − CH3 (v) + H2 (g) ∆H = +62.9KJ/mol

Reaction Kinetics

The reaction kinetics for this reaction is first order with respect to the concentration of
alcohol and can be estimated from the following Arrhenius equation:

−Ea
−rIPA = K o exp [ ]C
RT IPA

With

Ea = 72.38 MJ/Kmol and

K o = 3.51 × 105 m3 gas/m3 bulk catalyst.

The catalysts that can be applied are

Copper (natural chalcopyrite) Invalid source specified.


Carbon-supported copper
Silver
Platinum
Palladium metal
Modified cobalt
Co-Ni/MgO catalysts Invalid source specified.
Sulfides of transition metals of the groups IV, V, and VI
Zinc oxide-Zirconium oxide combinations
Combinations of chromium oxide and copper
Combinations of copper and silicon
CuO–NiO Nano composites Invalid source specified.
Carbon-supported Pt and Cu–Pt catalysts Invalid source specified.

Catalyst selection

Cu is highly selective for alcohol dehydrogenation but suffers from low activity and a
propensity to sinter; thus, the addition of a second metal may not only increase
dehydrogenation activity and catalyst lifetime and still maintain high selectivity, but also
facilitate reduction of the Cu precursor to metallic Cu.

Copper chromite systems have been in use but replacement with more environmentally
benign copper catalysts, such as carbon-supported Cu, is of current interest because of the
prohibition of chromite disposal in landfills by the Environmental Protection Agency.

Experimental work on IPA dehydrogenation using Carbon supported Pt and carbon


supported Cu-Pt catalysts by R.M Rioux and M.A Vennice reviewed that at 448 K and 14
Torr IPA, for an activated carbon heat treated at 1223 K as the support, the turnover
frequency (TOF) on the Pt catalyst was 0.11 s−1, the TOF on the Cu catalyst was 0.020
s−1. Invalid source specified. Turn over frequency of the catalyst is defined as the amount
of reactant converted into product by the catalyst in the unit time. Carbon-supported Pt
catalysts are much more active for IPA dehydrogenation than their Cu counterparts, and on
a TOF basis, Pt is 5 times more active than Cu. Pt is known to be more active for
hydrogenation/dehydrogenation reactions than CuInvalid source specified., although Cu
has better selectivity in dehydrogenation reactions Invalid source specified.Invalid
source specified.

The apparent activation energy for acetone production from IPA on Pt/C was 6.8 kcal
mol−1, compared with 21 kcal mol−1 for the monometallic Cu/C catalysts. Apparent
activation energies for the Cu–Pt/C catalysts (7–9 kcal mol−1) were comparable to those
of Pt/C at lower temperatures and decreased further to ∼ 3 kcal mol−1 above 443 K.Invalid
source specified.

However the cost of platinum is high as compared to copper. Copper is abundant and has good
selectivity in dehydrogenation reactions and has high catalyst lifetime. We thus choose the carbon
supported Cu catalyst for this reaction.

Reaction conditions

Temperature (325-350⁰C)
Pressure in the reactor

Associated reactions

At temperatures below 325⁰C the IPA undergoes a condensation reaction resulting in the
production of Di-isopropyl ether and water instead of our desired Acetone.

2CH3 − CHOH − CH3 (v) → (CH3 )2 CH − O − CH(CH3 )2 (aq) + H2 O(l)

At temperatures above 350⁰C, a dehydration reaction is expected to be significant with production


of propylene gas and water instead of our desired Acetone.
CH3 − CHOH − CH3 (v) → CH2 = CH − CH3 (v) + H2 O(v)

Process description

An aqueous solution of IPA is mixed with IPA recycle stream and water in the feed drum thus
ensuring a homogenous mixture is obtained. This mixture is fed to a vaporizer to vaporize the
reactants thereby ensuring maximum contact is achieved between the catalyst and reactants in
downstream process in the gas phase reactor.

The resulting mixture is fed to the reactor into which heat is supplied and contact is ensured
between reactant mixture and catalyst. The product stream from the reactor contains acetone, H2
gas, may also contain Di-isopropyl ether, Propene gas and water.

It is send to a cooler and then a condenser in order to cool this stream and condense IPA, Acetone
and water to improve the separation between the gaseous phase and liquid phase in the Flash
drum/tank. We are using flash separation to separate hydrogen ie flashing it out since it has low
solubility though some hydrogen is dissolved in the liquid. Unfortunately, along with hydrogen
some amount of acetone and isopropyl alcohol is also flashed out. In order to recover these, a
scrubber unit (Absorber) is used in which water is used for scrubbing.

The bottoms from flash unit and absorber are fed to the acetone distillation column. This stream
contains acetone, IPA, water and some dissolved hydrogen. Manipulation of the differences in
volatilities of these compounds allows us to obtain the desired acetone. The bottoms from the
acetone distillation column consist of IPA, Water and insignificant acetone and are sent to the IPA
distillation column.

The IPA distillation column has a top stream consisting mainly of IPA and some negligible
acetone. This stream is recycled to the feed drum. The bottoms from the IPA distillation consist of
mainly water product and 0.1% IPA. This stream if cooled, it can be recycled to the
scrubber.Invalid source specified.

Advantages

 High purity product


 High conversion rates
 Acetone is primary product and unassociated with any dangerous chemical
 Simple separation processes required

Disadvantages

 The raw material (IPA) is toxic, it affects the nervous and respiratory system.
 Raw material highly flammable.

Block diagram
Comparison between the processes and selection of process
Due to several processes that can be done to produce acetone, analysis is therefore a requisite to
select a process to produce acetone. The Kepner Tregoe method is done to select the process. Easy
way to evaluate the technologies according to certain factors that has influency either directly or
indirectly linked to the final product and environmental impacts. These factors had been listed
below and the code given to it for the K-T analysis:

Technology code

Alkane nitrile 1.1


Gem halides 1.2

Ozonolysis 1.3

Oxidation of IPA 1.4

Propylene oxidation 1.5

Dehydrogen of IPA 1.6

IPA Decomposition 1.7

ABE Fermantation 1.8

Chacteristic Factor

1. Yield
2. Environmental aspects
3. Raw material availability
4. Complexicity
5. Purity
6. Durability
7. Capital costs
8. Operation cost
9. Maintanance costs

1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8

1 1 2 3 2 3 3 3 1
2 1 2 1 1 1 3 2 3

3 1 1 1 3 3 3 3 2

4 1 1 1 2 1 2 2 1

5 3 3 2 3 2 3 3 1

6 1 1 2 2 2 2 2 3

7 2 2 2 2 1 2 1 3

8 2 2 1 2 1 2 1 2

9 2 2 3 2 1 2 1 2

Total 14 16 16 19 15 22 18 18

 Major disadvantage of the production of acetone from cumene process is that some
amount of reactant benzene is present along with desired product which is toxic.
 The disadvantage of production of acetone from propylene oxidation process is that
propylene required for the process should be 99 % pure.

From the above table and analysis of the processes, the process of choice due to the use of
acetone to be produced the dehydrogenation of isopropyl method is the selected process

1.5 PRELIMINARY ECONOMIC EVALUATION OF CHOSEN PROCESS

Introduction
The preliminary economic evaluation of the project was done based on step wise method to
estimate the capital cost of the proposed plant.The proposed plant is to produce 50 000tonnes of
acetone /year

Assumptions

1. Plant availability is assumed to be 92.6 % translating to 8000hours/year.

Capital Investment for the acetone plant

STEP COUNTING METHOD

Step counting estimating methods provide a way of making a quick, order of magnitude, estimate
of the capital cost of a proposed project. The technique is based on the premise that the capital cost
is determined by a number of significant processing steps in the overall process.

Since the total tonnage of the proposed plant is less than 60 000 tonnes,we use the following
formula.

𝑸
C=150 000N( 𝑺 )0.3

where:

N=number of functioning units(5)

C=capital cost in pounds sterling

S= reactor conversion(96.7%)

Q=plant capacity/tonne/year(50 000)

C=150 000x5(50 000)0.3


𝑆0.967
=1,459,170

Inflation Adjustment of capital cost estimate

Cost indices were used to relate the past cost of the existing plant to its present cost according to
the relation:

𝑪𝒐𝒔𝒕 𝒊𝒏𝒅𝒆𝒙 𝒊𝒏 𝒚𝒆𝒂𝒓 𝑩


𝑪𝒐𝒔𝒕 𝒊𝒏 𝒚𝒆𝒂𝒓 𝑩 = 𝑪𝒐𝒔𝒕 𝒊𝒏 𝒚𝒆𝒂𝒓 𝑨 (𝑪𝒐𝒔𝒕 𝒊𝒏𝒅𝒆𝒙 𝒊𝒏 𝒚𝒆𝒂𝒓 𝑨) (2)

Using the following indices 2019 – 603.1

2015 – 573.1

603.1
𝐶𝑜𝑠𝑡 𝑖𝑛 2019 = 19459170 ( )
573.1

= $20477797.43

Fixed cost Estimation

An estimate of the fixed capital cost was calculated using the formula:

𝑪𝒕 = 𝑪𝒇 + 𝑪𝒘 (3)

Where Ct is the total capital investment cost of the proposed plant,

Cf is the fixed capital cost and Cw is the working capital cost.


Coulson and Richardson Volume 6 estimates the working capital cost to be 15% of the fixed capital
cost.

Therefore: 𝑪𝒘 = 𝟎. 𝟏𝟓𝑪𝒇 (4)

Substituting equation (4) into equation (3)

Ct = Cf + 0.15Cf

𝐶𝑡
𝐶𝑓 =
1.15

$19459170
𝑪𝒇 =
1.15

= $16921017.39

Production cost estimates

Table 1.17: Manufacturing costs

Item
Cost USD

Maintenance costs 5% of Cf $846050.87


Operating labor 6% of Cf $1015261.043
Laboratory 20% of operating labour $203052.21
Supervision 20% of operating labour $203052.21
Plant overheads 50% of operating labour $507630.52
Capital cost 10% of Cf $1692101.74
Insurance 1% of Cf $169210.17
Taxes 2% of Cf $338420.35
Royalties 1% of Cf $169210.17
Total $5143989.29

Variable Costs

Raw Material costs

Assumptions

1. 1 tonne of acetone requires 1.034 tonnes of isopropyl alcohol

2. Iso propyl alcohol purity of 99.9%

3. Conversion based on IPA= 96.7%

4. Yield of acetone based on IPA= 99.7%

Basis 1 tonne of acetone

Amount of isopropyl alcohol required per tonne of acetone = 1000/(0.967 x 0.99)

= 957.33kg

Total amount of IPA required per year = 50 000 x (957.33/1000)

= 47,866.5tonnes/year
Raw material costs

Isopropyl alcohol= USD $1250/tonne

Table 1.18: Cost of raw materials

COST OF RAW MATERIALS

$/tonne £/tonne Annual Cost

IPA 1250 966.30. 48,315,000

Utilities cost (7% of Cf) = £1184471.22

Total direct production costs = Manufacturing costs+ Raw material costs+ Utilities cost

=£ 5143989.29+ £43,315,000 + £1184471.22

= £49643460

Sales expenses (20% of Total direct costs) = 0.2 x $49643460

= £9,928,692

Total Expenses = Total direct production costs + Sales expenses

= £59,572,152

Sales revenue
Table 1.19: Sales revenue

Price(£/tonne)
Product Annual Revenue $

Acetone 1376.01 68,800,500

Hydrogen 77.30 3,865,000

Total Sales Revenue 72,665,500

Annual profit = Total sales revenue – Total expenses

= £72,665,500- £59,572,152

= £13,093,348

Annual Depreciation = 10% of Cf

= $1692102.

Fixed capital investment


Payback period =
Annual profit + annual depreciation

𝐏𝐚𝐲𝐛𝐚𝐜𝐤 𝐩𝐞𝐫𝐢𝐨𝐝 = 1.14 years

The acetone manufacturing plant seems to be an economically attractive project based on the
preliminary economic analysis carried out. The project is e xpected to have a payback period of
1.14 years which makes it quite desirable.
1
Rate of return =
Payback period

= 0.87

1.5 SITE SURVEY AND SITE LOCATION

 LOCAL COMMUNITY CONSIDERATIONS


The proposed plant must fit in and be satisfactory to the nearby network. Full thought must
be given to the protected area of the plant, so it doesn't force a significant hazard to the
network. Sometimes further advancement of a site might be confined by the legislature
because of general supposition, ecological contamination issues, or concern with respect
to the danger of a significant mishap in an exceptionally industrialized territory. On another
site, the nearby network must have the option to give enough offices to the plant work
force: schools, banks, lodging, and recreational and social offices. The nearby network
should likewise be counseled about plant water utilization and release and the impact of
the plant on neighborhood traffic. A few networks invite new plant development as a
wellspring of new openings and monetary success. More affluent networks commonly do
less to energize the structure of new assembling plants and now and again may effectively
debilitate substance plant development.
 Environmental impact and effluent disposal
Several methods for predicting and evaluating the impact of a development project on man
and the environment. In the present stage, it is important to give precision on some
characteristics of each environmental consequence to establish a classification. Each
consequence likely to occur must be defined by four parameters:
 The magnitude, based on a scale decided at the beginning; three degrees of
magnitude for each repercussion will be assessed: major, minor, negligible.
 The period of occurrence, particularly for impact occurring only during the
construction phase or those likely to occur after a long period.
 The reversibility. This notion can be absolute (e.g. disappearance of a threatened
species), or economic (e.g. enormous cost of amending soils lost through erosion).
 The type: direct (primary) or indirect (secondary). A direct impact is a direct
destruction of an element of the environment (e.g. a forest is cut down to build the
plant), an indirect impact is a knock-on effect (e.g. an animal disappears because
its habitat was lost during project implementation).

After the evaluation of these parameters together with the environmental


management agency and the ability to meet their environmental aspects and
standards hence the proceedings are considered for the plant installation and
construction commences.

 AVAILABILITY OF LABOUR

For a successful and uninterrupted working operation of a plant, availability of adequate


supply of labour with reasonable wages is very essential. Labour will be needed for the
plant construction and its day to day operation. Skilled and unskilled labour is needed. For
the Acetone plant skilled labour will be brought in from different areas which includes
places away the site. It is also necessary that there be an adequate supply of unskilled labour
locally and labour that will be suitable for training to operate the plant. In Zimbabwe both
personnel are available in most areas.

 POLITICAL AND STRATEGIC CONSIDERATIONS

This is one of the most important aspects to be considered. Zimbabwe has been battling
with the problem of rural-urban migration since independence in 1980 and has been trying
to rectify the problem by creating employment in rural areas. Setting the plant in a rural
area will help to alleviate this problem. Also there are areas in Zimbabwe that are not
suitable for agriculture and the government has been trying to set up other economic
activities in such areas so as to improve the livelihoods of the local people. There is a lot
of pressure on urban infrastructure because of expanding industry and growing populations
and hence the need to decentralize industry and encourage development of other regions.
Capital grants, tax concessions, and other inducements are often given by governments to
direct new investment to preferred locations, such as areas of high unemployment. The
availability of such grants can be the overriding consideration in site selection. In a
globalised economy, there may be an advantage to be gained by locating the plant within
an area with preferential tariff agreements. Availability of government regional
development grants or tax incentives, subsidies, etc. development or discharge emissions
were put into consideration during the selection of a suitable site for plant location.

 Availability of suitable land

Proposed plant land should be spacious to accommodate all process units for the
production. The land should ideally be flat, well drained and have suitable load-bearing
characteristics. The land should be located away from residential and business areas as the
products, acetone and hydrogen may have negative health effects when in contact with
them. The price for acquiring the land should also be considered, deserted or highly
unoccupied land may be cheaper to purchase as compared to areas with a lot of activity
already in place. However since the materials handled (isopropyl alcohol and acetone) are
highly toxic chemicals, land chosen should not be too far off from hospitals (town areas)
where the affected can be quickly and professionally attended to.

 Availability of utilities

The acetone production technology to be used requires water, coal, isopropyl alcohol as
the input materials. Hence in the selection of site, it is important to consider the proximity
of a river or dam which will be used as a water source for the plant. The site should be
close to a coal mine or in the railway network which will ease the transportation of the coal
in bulk quantities. The availability of the major raw material should also be taken into
consideration and the site is to be located close to the suppliers to indirectly cut on
production costs by minimizing the distance and decreasing transportation costs.
 Transportation Considerations.

Ideally, any chemical plant must be located near at least two major transportation forms.
Since freight charges of raw materials and finished goods enter into the cost of production,
transportation facilities are becoming the governing factor in economic location of the
plant. Depending upon the volume of the raw materials and finished products, a suitable
method of transportation like rail, road, water transportation and air transport is selected
and accordingly plant location is decided. Important consideration should be that the cost
of transportation should remain small in comparison to the total cost of production.

 Chemical Transportation Considerations

In the case of a land locked country such as Zimbabwe, the most readily available modes
would be road and rail. Transportation by road is common for local distribution from
central warehouses, while transportation by rail is more widespread for long distance
transport of bulk chemicals. The raw materials and end products require to have
uninterrupted receipt and dispatch facilities through good road connections, proper linking
with ports and railheads. Raw materials and products may be imported and exported by
road from neighboring countries such as South Africa and Botswana. Locally, raw
materials and products may also be transported by road and rail, preferably over short
distances to save on transportation costs. Cost of distribution is an important item in the
overhead expenses, so it will be advantageous to be near the centre of demand for finished
products. As such the plant should be located near a ready market or near a sustainable
transportation route.

 Personnel Transportation Considerations

Besides transportation of chemical goods, site selection also depends on the availability of
transport routes for workers and professionals. Day to day workers need a well-functioning
transportation system and/or route to be able to report to work every business day on time.
Professionals such as equipment and product specialists may occasionally be requested on
site and as such a reliable transport route is of great importance.
Rail transport is a means of conveyance of passengers and goods by way of wheeled
vehicles running on rail track, known as a railway or railroad. Railed vehicles move with
much less friction than rubber tires on paved roads, making trains more energy efficient.
Regional and commuter trains feed cities from suburbs and surrounding areas, while intra-
urban transport is performed by high-capacity tramways and rapid transits, often making
up the backbone of a city's public transport.
Motorcars offer high flexibility, but are deemed with high energy and area use, and the
main source of noise and air pollution in cities. Buses allow for more efficient travel at the
cost of reduced flexibility. Road transport by truck is often the initial and final stage of
freight transport.

 The Hazards of Chemical Transportation

The transportation of hazardous goods poses significant financial risks and threats to
people and the environment in the form of explosions, fires, toxic leaks, radioactive spills,
and the inhalation of corrosive substances. Such threats make safe chemical transportation
and ultimately, the choice of a good transportation system, an issue of paramount
importance. The production of acetone is associated with the following type of chemicals
that require on-site and off-site transportation:
Explosives
Gases
Flammable liquids
Toxic substances

The main raw material and product in the plant are both classified as flammable liquids.

The more common form of chemical transportation occurs when moving chemicals
between buildings on the same site. Chemical transport of dangerous substances externally
arguably presents a bigger risk of larger scale incidents than on-site chemical transport
because the quantities of chemicals transported externally are often much larger. Key on-
site practices in relation to transportation include:

Ensure you appropriately segregate mixed classes of hazardous substances to avoid


the risk of a reaction while they are in transport.
Always classify chemicals according to their hazards as designated by the UN so
you can select appropriate packaging for all goods being transported.
Only approved portable tanks and containers may be used to store and transport
class 3 flammable liquids. Portable tanks must include provisions for emergency
vents that can be used to decrease internal pressure under fire exposure conditions.
Only hire competent and registered carriers to transport hazardous substances for
both domestic and international transport.

Site selection

Mutare

Mutare is 'Zimbabwe's Gateway to the Sea'. It is the fourth biggest city in Zimbabwe, and
the managerial focus of Manicaland territory. It lies around 8 km from the fringe with Mozambique
and is only 290 kilometers from the Mozambican port of Beira. The city is served by phenomenal
rail and street frameworks and is associated by rail with the port of Beira in Mozambique. Mutare
is Zimbabwe's nearest city to the ocean (Indian Ocean) making it a decent vital area for the vehicle
cost delicate import and fare acetone production business.

With a populace of roughly 200,000, Mutare is the business focal point of a rich rural
movement as it is arranged in the core of Zimbabwe's timber developing territories. Mutare
now has great stockpile of water following the $170 million Pungwe project that was
executed to guarantee an adequate and enduring inventory of water to the city for its
residential and industrial needs.

Mutare is additionally part of the Beira Corridor. The Beira passage is basically a 100 km
wide channel for big business advancement and development of merchandise from the
inside of Southern Africa locale to the port of Beira at the Indian Ocean. The Beira corrido,
a universal advancement including Zimbabwe, Mozambique, Zambia, Malawi and South
Africa is supported by private segment and non-legislative loaning associations. This is a
task that was set up to advance productive transportation over the outskirts. Street and rail
connects to the ocean are in phenomenal fix and the port itself has been modernized for
safe stockpiling and treatment of merchandise.

As far as venture motivations, Mutare offers potential financial specialists one of a kind
points of Interest over different focuses. Speculation motivating forces are intended to
make it less expensive for financial specialists to fire up their undertakings.

References

[1] D. S. Safar, in p37,85,93.

[2] U. i. t. commission, "Acetone from Belgium, Korea, Saudi," in Publication 4884 , washington D.C,
2019 April.

[3] "https://ihsmarkit.com/products/acetone-chemical-economics-handbook.html;," august 2018.


[Online]. [Accessed 9 march 2019].

[4] Duhe, in conference transcript, 2019.

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