Acetone (CH3COCH3)

Acetone (propanone) is a colorless, volatile, flammable liquid. In the body, extremely

small amounts are found in normal urine, but larger quantities occur in the urine and
blood of people with diabetes, sometimes imparting a fruity odor to the urine and
breath. Acetone is one of the ketone bodies, and is used as a solvent in many
pharmaceutical and commercial preparations. Acetone is an organic compound with the
formula (CH3)2CO. In medicine, dermatologists use acetone with alcohol for skin
treatments for acne. In cosmetics, acetone is a primary component of nail polish
remover.

Chemical compound
Alternative titles: 2-propanone; dimethyl ketone; propanone
acetone (CH3COCH3), also called 2-propanone or dimethyl

ketone, organic solvent of industrial and chemical significance, the simplest and most

important of the aliphatic (fat-derived) ketones. Pure acetone is a colourless, somewhat

aromatic, flammable, mobile liquid that boils at 56.2 C (133 F).
Acetone is capable of dissolving many fats and resins as well as cellulose ethers,
cellulose acetate, nitrocellulose, and other cellulose esters. Because of the latter quality,
acetone is used extensively in the manufacture of artificial fibres (such as some rayons)
and explosives. It is used as a chemical intermediate in pharmaceuticals.

Preparation
In 2010, the worldwide production capacity for acetone was estimated at 6.7 million
tonnes per year. With 1.56 million tonnes per year, the United States had the highest
production capacity,[26] followed by Taiwan and mainland China. The largest producer
of acetone is INEOS Phenol, owning 17% of the world's capacity, with also significant
capacity (78%) by Mitsui, Sunoco and Shell in 2010. INEOS Phenol also owns the
world's largest production site (420,000 tonnes/annum) in Beveren (Belgium). Spot
price of acetone in summer 2011 was 11001250 USD/tonne in the United States.

Current method
Acetone is produced directly or indirectly from propylene. Approximately 83% of
acetone is produced via the cumene process; as a result, acetone production is tied to
phenol production. In the cumene process, benzene is alkylated with propylene to
produce cumene, which is oxidized by air to produce phenol and acetone:

Other processes involve the direct oxidation of propylene (Wacker-Hoechst

process), or the hydration of propylene to give 2-propanol, which is oxidized to
acetone.

Older methods
Previously, acetone was produced by the dry distillation of acetates, for
example calcium acetate in ketonic decarboxylation.
Ca(CH3COO)2 CaO(s) + CO2(g) + (CH3)2CO (v)
Before that, during World War I acetone was produced using acetone-butanolethanol fermentation with Clostridium acetobutylicum bacteria, which was
developed by Chaim Weizmann (later the first president of Israel) in order to
help the British war effort in the preparation of Cordite. This acetone-butanolethanol fermentation was eventually abandoned when newer methods with better
yields were found.

Acetic acid (CH3COOH)

Chemical compound
Alternative titles: ethanoic acid; glacial acetic acid

acetic acid (CH3COOH), also called ethanoic acid, the most important of
the carboxylic acids. A dilute (approximately 5 percent by volume) solution of
acetic acid produced by fermentation and oxidation of naturalcarbohydrates is
called vinegar; a salt, ester, or acylal of acetic acid is called acetate. Industrially,
acetic acid is used in the preparation of metal acetates, used in some printing
processes; vinyl acetate, employed in the production of plastics; cellulose acetate,
used in making photographic films and textiles; and volatile organic esters (such
as ethyl and butyl acetates), widely used as solvents for resins, paints.

Preparation:
Acetic acid is produced industrially both synthetically and by bacterial fermentation.
About 75% of acetic acid made for use in the chemical industry is made by
the carbonylation of methanol, explained below. Alternative methods account for the
rest. The biological route accounts for only about 10% of world production, but it

remains important for the production of vinegar, as many food purity laws stipulate that
vinegar used in foods must be of biological origin. As of 20032005, total worldwide
production of virgin acetic acid was estimated at 5 Mt/a (million tonnes per year),
approximately half of which was then produced in the United
States. European production stood at approximately 1 Mt/a and was declining, and
0.7 Mt/a were produced in Japan. Another 1.5 Mt were recycled each year, bringing the
total world market to 6.5 Mt/a. Since then the global production has increased to 10.7
Mt/a (in 2010), and further, however, slowing increase in production is predicted. The
two biggest producers of virgin acetic acid are Celaneseand BP Chemicals. Other major
producers include Millennium Chemicals, Sterling Chemicals, Samsung, Eastman,
andSvensk Etanolkemi.
Methanol carbonylation
Most acetic acid is produced by methanol carbonylation. In this process, methanol
and carbon monoxide react to produce acetic acid according to the equation:

The process involves iodomethane as an intermediate, and occurs in three steps.

A catalyst, metal carbonyl, is needed for the carbonylation (step 2).
1. CH3OH + HI CH3I + H2O
2. CH3I + CO CH3COI
3. CH3COI + H2O CH3COOH + HI
Two related processes for the carbonylation of methanol: the rhodiumcatalyzed Monsanto process, and the iridium-catalyzed Cativa process. The latter
process is greener and more efficient and has largely supplanted the former process,
often in the same production plants. Catalytic amounts of water are used in both
processes, but the Cativa process requires less, so the water-gas shift reaction is
suppressed, and fewer byproducts are formed.
By altering the process conditions, acetic anhydride may also be produced on the same
plant using the rhodium catalysts.
Acetaldehyde oxidation
Prior to the commercialization of the Monsanto process, most acetic acid was produced
by oxidation of acetaldehyde. This remains the second-most-important manufacturing
method, although it is usually uncompetitive with the carbonylation of methanol.

The acetaldehyde may be produced via oxidation of butane or light naphtha, or by

hydration of ethylene. When butane or lightnaphtha is heated with air in the presence of
various metal ions, including those of manganese, cobalt,
and chromium, peroxidesform and then decompose to produce acetic acid according to
the chemical equation:
2 C4H10 + 5 O2 4 CH3COOH + 2 H2O
The typical reaction is conducted at temperatures and pressures designed to be as hot as
possible while still keeping the butane a liquid. Typical reaction conditions are 150 C
(302 F) and 55 atm. Side-products may also form, includingbutanone, ethyl
acetate, formic acid, and propionic acid. These side-products are also commercially
valuable, and the reaction conditions may be altered to produce more of them where
needed. However, the separation of acetic acid from these by-products adds to the cost
of the process.
Under similar conditions and using similar catalysts as are used for butane oxidation,
the oxygen in air to produce acetic acid can oxidize acetaldehyde.
2 CH3CHO + O2 2 CH3COOH
Using modern catalysts, this reaction can have an acetic acid yield greater than 95%.
The major side-products are ethyl acetate, formic acid, and formaldehyde, all of which
have lower boiling points than acetic acid and are readily separated bydistillation.
Ethylene oxidation
Acetaldehyde may be prepared from ethylene via the Wacker process, and then
oxidized as above. In more recent times, chemical company Showa Denko, which
opened an ethylene oxidation plant in ita, Japan, in 1997, commercialized a cheaper
single-stage conversion of ethylene to acetic acid. The process is catalyzed by
a palladium metal catalyst supported on a heteropoly acid such as tungstosilicic acid. It
is thought to be competitive with methanol carbonylation for smaller plants (100
250 kt/a), depending on the local price of ethylene. The approach will be based on
utilizing a novel selective photocatalytic oxidation technology for the selective
oxidation of ethylene and ethane to acetic acid. Unlike traditional oxidation catalysts,
the selective oxidation process will use UV light to produce acetic acid at ambient
temperatures and pressure.

Oxidative fermentation
For most of human history, acetic acid bacteria of the genus Acetobacter have made
acetic acid, in the form of vinegar. Given sufficient oxygen, these bacteria can produce
vinegar from a variety of alcoholic foodstuffs. Commonly used feeds include apple
cider, wine, and fermented grain, malt, rice, or potato mashes. The overall chemical
reaction facilitated by these bacteria is:
C2H5OH + O2 CH3COOH + H2O
A dilute alcohol solution inoculated with Acetobacter and kept in a warm, airy place
will become vinegar over the course of a few months. Industrial vinegar-making
methods accelerate this process by improving the supply of oxygen to the bacteria.
The first batches of vinegar produced by fermentation probably followed errors in
the winemaking process. If must is fermented at too high a temperature, acetobacter
will overwhelm the yeast naturally occurring on the grapes. As the demand for vinegar
for culinary, medical, and sanitary purposes increased, vintners quickly learned to use
other organic materials to produce vinegar in the hot summer months before the grapes
were ripe and ready for processing into wine. This method was slow, however, and not
always successful, as the vintners did not understand the process.
One of the first modern commercial processes was the "fast method" or "German
method", first practised in Germany in 1823. In this process, fermentation takes place in
a tower packed with wood shavings or charcoal. The alcohol-containing feed is trickled
into the top of the tower, and fresh air supplied from the bottom by either natural or
forced convection. The improved air supply in this process cut the time to prepare
vinegar from months to weeks.
Nowadays, most vinegar is made in submerged tank culture, first described in 1949 by
Otto Hromatka and Heinrich Ebner. In this method, alcohol is fermented to vinegar in a
continuously stirred tank, and oxygen is supplied by bubbling air through the solution.
Using modern applications of this method, vinegar of 15% acetic acid can be prepared
in only 24 hours in batch process, even 20% in 60-hour fed-batch process.[38]
Anaerobic fermentation
Species of anaerobic bacteria, including members of the
genus Clostridium or Acetobacterium can convert sugars to acetic acid directly, without
using ethanol as an intermediate. The overall chemical reaction conducted by these
bacteria may be represented as:

C6H12O6 3 CH3COOH
These acetogenic bacteria produce acetic acid from one-carbon compounds, including
methanol, carbon monoxide, or a mixture of carbon dioxide and hydrogen:
2 CO2 + 4 H2 CH3COOH + 2 H2O
This ability of Clostridium to utilize sugars directly, or to produce acetic acid from less
costly inputs, means that these bacteria could potentially produce acetic acid more
efficiently than ethanol-oxidizers like Acetobacter. However, Clostridium bacteria are
less acid-tolerant than Acetobacter. Even the most acid-tolerantClostridium strains can
produce vinegar of only a few per cent acetic acid, compared to Acetobacter strains that
can produce vinegar of up to 20% acetic acid. At present, it remains more cost-effective
to produce vinegar using Acetobacter than to produce it using Clostridium and then
concentrate it. As a result, although acetogenic bacteria have been known since 1940,
their industrial use remains confined to a few niche applications.

Acetaldehyde (CH3CHO)
Chemical compound
Alternative title: ethanal
acetaldehyde (CH3CHO), also called ethanal, an aldehyde used as a starting material
in the synthesis of 1-butanol (n-butyl alcohol), ethyl acetate, perfumes, flavourings,
anilinedyes, plastics, synthetic rubber, and other chemical compounds. It has been
manufactured by the hydration of acetylene and by the oxidation of ethanol (ethyl
alcohol). Today the dominant process for the manufacture of acetaldehyde is
the Wacker process, developed between 1957 and 1959, which catalyzes the oxidation
of ethylene to acetaldehyde. The catalyst is a two-component system consisting of
palladium chloride, PdCl2, and copper chloride, CuCl2.

Pure acetaldehyde is a colourless.

Preparation:
In 2003, global production was about 1 million tonnes. Before 1962, ethanol and
acetylene were the major sources of acetaldehyde. Since then, ethylene is the dominant
feedstock.

The main production method is the oxidation of ethylene via the Wacker process. The
process involves oxidation of ethylene using a homogeneous palladium/copper system:
2 CH2=CH2 + O2 2 CH3CHO
In the 1970s, the world capacity of this process, the Wacker-Hoechst direct oxidation,
increased to over 2 million tonnes/year.
When smaller quantities are required, it can also be prepared by the partial oxidation of
ethanol, in an exothermic reaction. This process typically is conducted over a silver
catalyst at about 500650 C.
CH3CH2OH + 1/2 O2 CH3CHO + H2O
This method is one of the oldest routes for the industrial of preparation of acetaldehyde.
Acetaldehyde can also be produced by the hydration of acetylene, catalyzed
by mercury salts. The reaction produces ethenol, which tautomerizes to acetaldehyde.
This industrial route was dominant prior to the Wacker process. One drawback of this
process is the formation of polymerization and condensation products of acetaldehyde.
Furthermore, the production of acetylene is costly and environmentally problematic.
The wet oxidation process was used before the Wacker process was commercially
established. Iron(III) sulfate is added to reoxidize the mercury metal to the mercury(II)
salt to maintain required concentration of catalyst and, thus, avoiding direct handling of
mercury. Acetylene reacts at 9095 C and the acetaldehyde formed is separated from
water and mercury and cooled to 2530 C. Iron(II) sulfate is formed in the reaction
and is oxidized in a separate reactor with 30% nitric acid at 95 C. Pure acetaldehyde is
obtained by fractional distillation of the aqueous solution at about 200 kPa.
Other methods
Traditionally but no longer viable economically, acetaldehyde was produced by the
partial dehydrogenation of ethanol:
CH3CH2OH CH3CHO + H2
In this endothermic process, ethanol vapor is passed at 260290 C over a copper-based
catalyst. The process was once attractive because of the value of the hydrogen
coproduct.
The hydroformylation of methanol with catalysts like cobalt, nickel, or iron salts also
produces acetaldehyde. This process is of no industrial importance. Similarly
noncompetitive, acetaldehyde arises from synthesis gas with modest selectivity.