Acetone 1

Acetone
Stylianos Sifniades, Allied Signal Inc., Morristown, New Jersey 07962, United States

Alan B. Levy, Allied Signal Inc., Morristown, New Jersey 07962, United States

1. Introduction . . . . . . . . . . . . . . . . 1 8. Uses . . . . . . . . . . . . . . . . . . . . . 10
2. Physical Properties . . . . . . . . . . . 1 8.1. Methyl Methacrylate . . . . . . . . . . 10
3. Chemical Properties . . . . . . . . . . . 2 8.2. Bisphenol A . . . . . . . . . . . . . . . . 11
4. Production . . . . . . . . . . . . . . . . . 3 8.3. Aldol Chemicals . . . . . . . . . . . . . 11
4.1. Cumene Oxidation (Hock Process) . 3 8.4. Solvent Uses . . . . . . . . . . . . . . . . 11
4.2. Dehydrogenation of 2-Propanol . . . 6 9. Economic Aspects . . . . . . . . . . . . 12
4.3. Propene Oxidation . . . . . . . . . . . . 7
10. Toxicology and Occupational Health 13
4.4. Oxidation of 2-Propanol . . . . . . . . 8
11. Derivatives . . . . . . . . . . . . . . . . . 13
4.5. Oxidation of p-Diisopropyl Benzene 8
4.6. Fermentation of Biomass . . . . . . . 8 11.1. Acetone Cyanohydrin . . . . . . . . . . 13
5. Environmental Protection . . . . . . . 8 11.2. Diacetone Alcohol . . . . . . . . . . . . 15
6. Quality Specifications and Analysis . 9 11.3. Miscellaneous Derivatives . . . . . . . 16
7. Storage and Transportation . . . . . . 10 12. References . . . . . . . . . . . . . . . . . 16

1. Introduction 2. Physical Properties

Acetone, 2-propanone, dimethyl ketone, Acetone has the following physical proper-
CH3 COCH3 , [67-64-1], is the first and most ties: M r 58.081; bp at 101.3 kPa, 56.2 ◦ C;
important member of the homologous series of mp − 94.7 ◦ C; relative density, d 04 0.81378,
aliphatic ketones. It is a colorless, mobile liquid d 15 20
4 0.79705, d 4 0.7908; relative vapor den-
widely used as a solvent for various polymers. sity (air = 1) 2.0025; refractive index n20 D
Its largest application, however, is as an inter- 1.35868; critical temperature 235.0 ◦ C, crit-
mediate in the synthesis of methyl methacrylate, ical pressure 4.6 MPa (46 bar), critical den-
bisphenol A, diacetone alcohol, and other prod- sity 0.278 g/cm3 ; cubic expansion coeffi-
ucts. cient (18 ◦ C) 1.43 × 10−3 K−1 ; compressibil-
Acetone was first manufactured by the dry ity coefficient (18 ◦ C) 1.286 × 10−6 kPa−1
distillation of calcium acetate [62-54-4]. Cal- (1.286×10−4 bar−1 ).
cium acetate was originally a product of wood Viscosity in mPa · s: 1.53 (− 80 ◦ C), 0.71
distillation, and later was obtained by fermenta- (− 40 ◦ C), 0.40 (0 ◦ C), 0.32 (20 ◦ C), 0.27
tion of ethanol. Carbohydrate fermentation di- (40 ◦ C). Surface tension in mN · m−1 : 38.1
rectly to acetone and butyl and ethyl alcohols (− 91.09 ◦ C), 23.9 (15 ◦ C), 23.3 (20 ◦ C), 23.0
displaced these processes in the 1920s. The car- (24.8 ◦ C), 22.0 (30 ◦ C), 21.6 (42 ◦ C).
bohydrate route, in turn, was replaced in the Thermal properties: Specific heat capacity,
1950s and 1960s by the 2-propanol dehydro- cp (20 ◦ C) 2.135 kJ kg−1 K−1 ; heat of fusion
genation process and by the oxidation of cumene (− 95 ◦ C) 98.47 kJ kg−1 ; heat of vaporization
to phenol [108-95-2] plus acetone. Together with (30 ◦ C) 545.2 kJ kg−1 , (0 ◦ C) 588.2 kJ kg−1 ;
direct propene oxidation, these methods account molar entropy 0.2001 kJ mol−1 K−1 ; heat of
for over 95 % of the acetone produced world- combustion 1804 kJ mol−1 ; heat of formation
wide. (20 ◦ C) 235.3 kJ/mol; thermal conductivity of
the liquid 1.976 W m−1 K−1 .
Vapor Pressure in kPa: 24 (20 ◦ C), 37.3
(30 ◦ C), 56.0 (40 ◦ C), 82.8 (50 ◦ C), 114.8

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a01 079
2 Acetone

(60 ◦ C), 214.8 (80 ◦ C), 372.8 (100 ◦ C), 929.6 3. Chemical Properties
(140 ◦ C).
Electrical properties: Electric conductivity Pure acetone is essentially inert to air oxidation
(20 ◦ C) 5.5 × 10−8 Ω −1 cm−1 ; dipole moment and to diffuse sunlight under ambient conditions.
(20 ◦ C) 2.69 Debye; dielectric constant of Its chemical stability diminishes significantly in
the liquid 21.58 (0 ◦ C), 22.64 (10 ◦ C), 20.70 the presence of water. Acetone may react vio-
(25 ◦ C), 19.38 (40 ◦ C); dielectric constant of the lently and sometimes explosively, especially in
vapor 1.0235 (24.8 ◦ C), 1.0277 (29.8 ◦ C). a confined vessel [5]. For example it is partic-
At ambient temperature acetone is a clear, ularly sensitive to oxidizing agents, such as ni-
colorless liquid with a characteristic odor. It is trosyl chloride [6] [2696-92-6], chromium tri-
miscible in all proportions with water and po- oxide [7] [1333-82-0], and hydrogen peroxide
lar organic solvents, such as the lower molecu- [8] [7722-84-1], or organic peroxides [9]. Mix-
lar mass alcohols, carboxylic acids, and ethers. tures of acetone with chloroform [67-66-3] may
It is miscible in limited proportions with non- react violently in the presence of alkali [10]. Re-
polar solvents, such as hydrocarbons. Some action even may be initiated by surface alkali on
azeotropic mixtures are shown in Tables 1 and 2 new glassware [11]. Acetone has a flash point
[3], [4]. of −17 ◦ C (closed cup). Flammability limits in
air are: lower 2.13 vol %, upper 13 vol %; au-
Table 1. Acetone binary azeotropes ∗ toignition temperature 465 ◦ C. The flammabil-
ity of acetone can be reduced by mixing it with
Second component Acetone, wt % bp (101.3 kPa), less flammable and/or less volatile solvents [12].
◦
C
Fires have been started during recovery of ace-
Carbon tetrachloride 88.5 56.08 tone from air by adsorption on activated carbon
2-Butylchloride 80 55.75
Hexane 53.5 49.7 when air flow was too low to effectively remove
Methyl acetate 49 55.65 the heat generated by surface oxidation [13].
Diethylamine 38 51.55 Acetone undergoes typical carbonyl reac-
Carbon disulfide 33 39.25
tert-Butylchloride 25 49.2 tions with particular ease. Acid- or base-
Isoprene 20 30.5 catalyzed self-condensation produces the dimers
n-Propylchloride 15 45.8
Methanol 14 55.59 diacetone alcohol and mesityl oxide and the cy-
clic trimer isophorone.
∗ Source and further examples [3]. Under strongly basic conditions hydrogen
cyanide adds to acetone to form 2-cyano-
Table 2. Acetone ternary azeotropes ∗ 2-propanol (acetone cyanohydrin), an impor-
Components (A is acetone) Composition, bp (101.3 kPa),
tant intermediate in the manufacture of methyl
wt % ◦
C methacrylate and other methacrylate esters (Sec-
tion 8.1).
B water 0.81 38.04
C carbon disulfide 75.21 In liquid ammonia solution acetone con-
B water 0.4 32.5 denses with acetylene [74-86-2] in the presence
C isoprene 92.0
B chloroform 46.7 57.5
of catalytic amounts of alkali metals to form 2-
C methanol 23.4 methyl-3-butyn-2-ol [115-19-5], an intermedi-
B chloroform 70.2 55.0 ate in the synthesis of isoprene [14] [563-46-2].
C ethanol 6.8
B methanol 16 51.1 Catalytic hydrogenation of acetone yields 2-
C cyclohexane 40.5 propanol [67-63-0]. Pyrolysis produces methane
B methyl acetate 5.6 49.7
C hexane 43.3
[74-82-8] and ketene [463-51-4], a powerful
acetylating agent. A more economical source of
∗ Source and further examples [4]. ketene, however, is the pyrolysis of acetic acid,
which produces ketene and water.
Acetone dissolves many synthetic Reductive ammonolysis of acetone yields
resins, e.g., nitrocellulose, acetylcellulose, isopropylamine [75-31-0]. Condensation with
poly(acrylate esters), and alkyd resins. It also 2 mol phenol in the presence of an acidic catalyst
dissolves most natural resins, fats, and oils. yields bisphenol A (Section 8.2), an important
 Acetone 3

monomer used in the manufacture of polycar- Fermentation of cornstarch and molasses to

bonate resins. acetone and 1-butanol was important in the past.
Perchlorination yields hexachloroacetone It is believed to be practiced today to a limited
[116-16-5], which is cleaved into chloro- extent in several countries.
form [67-66-3] and sodium trichloroacetate
[650-51-1] upon treatment with sodium hydrox-
ide. 4.1. Cumene Oxidation (Hock Process)
(Fig. 1)

Propene [115-07-1] is added to benzene

4. Production [71-43-2] to form cumene [98-82-8], which is
then oxidized by air to cumene hydroperoxide
Approximately 83 % of the acetone produced (1), and cleaved in the presence of an acid cat-
worldwide is manufactured from cumene as a alyst. Phenol [108-95-2] and acetone produced
coproduct with phenol. In the United States and in the process are recovered by distillation.
Western Europe dehydrogenation of 2-propanol
is also important, whereas in Japan catalytic ox-
idation of propene is used as a second process.
Cumene, 2-propanol, and propene together as
starting materials account for over 95 % of the
acetone produced worldwide. Because propene
is used in the manufacture of both cumene and
2-propanol, propene is the ultimate raw material
for the production of acetone. The alkylation of benzene by propene pro-
Small amounts of acetone are made by oxida- ceeds under typical Friedel – Crafts conditions.
tion of p-diisopropyl benzene and of p-cymene. In 1996, a number of processes using zeolite cat-
Coproducts from these reactions are hydro- alysts came on-stream. The cumene produced is
quinone and p-cresol, respectively. Acetone is purified by chemical means and refined by dis-
also produced by propene oxidation and as a tillation to 99.9 % minimum purity. Oxidation-
byproduct of acetic acid manufacture. grade cumene must meet strict quality standards.

Figure 1. Cumene phenol – acetone process (Allied)

a) Oxidizers; b) Flash column; c) Carbon adsorber; d) Alkaline extraction and wash; e) Cumene hydroperoxide decomposer;
f) Dicumyl peroxide decomposer; g) Ion exchange; h) Crude acetone column; i) Acetone-refining column; j) Cumene column;
k) α-Methylstyrene column; l) Phenol column; m) Phenol residue topping column
AMS = α-methylstyrene
4 Acetone
Table 3. Specifications for oxidation-grade cumene (zeolite process) [15]

Property ASTM test Specification

Appearance Clear, colorless liquid

Color, Pt – Co scale D1209-79 15 max.
d 15.5
15.5 D891-59 0.864 – 0.867
Acid wash color, W scale D848-62 2 max.
Sulfur compounds D853-47 Free from H2 S and SO2
Copper corrosion D849-47 No iridescence, gray or black
Distillation range D950-56 1.0 ◦ C max.
Cumene content 99.93 % min.
Phenolics content 5 ppm max.
Cumene hydroperoxide content 200 ppm max.
Sulfur content 0.1 ppm max.

The newer zeolite-based processes have led to For these reasons, most plants operate between
slightly tighter specifications (Table 3) [15]. 25 and 40 wt % in the last oxidation reactor.
A minor but significant byproduct of the oxi-
Cumene Oxidation. The oxidation of dation is dicumyl peroxide [80-43-3]. This arises
cumene is a free-radical chain reaction [16]. during the termination of the chain reaction.
The chain initiator is cumene hydroperoxide, Dicumyl peroxide also contributes to chain ini-
the main product of the reaction. The rate of tiation [17], but to a much lesser degree than
oxygen consumption can be approximated by cumene hydroperoxide. Other minor byproducts
the following expression: are formaldehyde and formic acid, which are

produced along with acetophenone by methyl
−dcO2 2ki cROOH group degradation.
= kp · cRH
dt kt The oxygen needed for cumene oxidation is
supplied by air. Use of pure oxygen has been sug-
cRH and cROOH are the concentrations of gested [18] but is disfavored by both economic
cumene and cumene hydroperoxide, respec- and safety considerations [19]. At low initiation
tively; k i , k p , and k t are the rate constants for rates, the rate of the reaction is essentially inde-
chain initiation, propagation, and termination. pendent of the oxygen concentration at a partial
The expression shows that the rate of oxi- pressure of oxygen over 33 kPa (0.33 bar) [20].
dation is zero in the absence of cumene hydro- A detailed study of the rate of oxygen uptake
peroxide. This is not exactly true, because the in a bubble column as a function of temperature
expression is only an approximation; but the and partial oxygen pressure has been made [21].
oxidation of cumene does require long induc- The study served as a basis for a mathematical
tion periods when starting with pure cumene. model of the oxidation [22], [23].
Consequently, the industrial oxidation always is Two cumene oxidation processes are used
carried out in a series of continuous reactors; in the United States, which with minor vari-
the concentration of cumene hydroperoxide is ations are practiced also in the rest of the
at least 8 wt % in the first reactor. Because the world [19], [22]. One process was developed by
sum of cRH and cROOH remains roughly con- Hercules and licensed by Kellogg (previously
stant during the reaction, the rate of reaction BP/Hercules) and GE/Lummus [24]. The other
cannot increase indefinitely as cROOH increases. process was developed by Allied and licensed
The maximum rate is achieved at approximately by Allied/UOP [25–28].
35 wt % cumene hydroperoxide. In both processes several reactors are em-
Besides cumene hydroperoxide, both di- ployed in series. Fresh and recycled cumene are
methylphenylmethanol and acetophenone are fed to the first reactor, which may operate at
also formed as byproducts during this oxida- 8 – 12 wt % cumene hydroperoxide. The con-
tion. These arise from a secondary chain reac- centration increases by 4 – 8 wt % in each suc-
tion that proceeds in parallel with the main chain. cessive reactor; the last reactor may operate at
Byproduct formation is accelerated as the con- 25 – 40 wt % cumene hydroperoxide. Fresh air
centration of cumene hydroperoxide increases.
 Acetone 5

is pumped in parallel to each reactor and vented The cleavage proceeds through an ionic
at the top after removal of organic vapors. mechanism and releases approximately 252 kJ/
In the Hercules process, the oxidation of mol of cumene hydroperoxide decomposed [30].
cumene is carried out at approximately 620 kPa The reaction rate accelerates rapidly with in-
(6 bar)/90 – 120 ◦ C, in the presence of a sodium creasing temperature. Consequently, decompo-
carbonate buffer [29]. Under these conditions sition of cumene hydroperoxide commonly is
the residence time in the oxidizer train is carried out in a continuously stirred reactor in
4 – 8 h and the hydroperoxide molar selectivity which the steady-state concentration of cumene
90 – 94 %. The spent air is first passed through hydroperoxide is maintained at a low level. The
water cooled and refrigerated condensers in se- heat released by the reaction can be used to esti-
ries to remove organic vapors, and is finally mate the concentration of hydroperoxide present
vented. The condensate is returned to the oxi- in the reactor at any time [33].
dizers after treatment [29]. The molar selectivity of the cleavage to phe-
In the Allied/UOP process (Fig. 1) the oxida- nol and acetone is higher than 99.5 % at tempera-
tion is carried out at atmospheric pressure. No tures below 70 ◦ C, but it decreases at higher tem-
buffer or promoter is added, but great care is peratures as increasing amounts of dimethylphe-
taken to wash all streams recycled to the oxi- nylmethanol and acetophenone (in addition to
dizer with alkali and water [27]. Temperature those present in the cumene oxidate) are formed
is maintained at 80 – 100 ◦ C. Residence time in (Table 4) [28].
the oxidizer train is 10 – 20 h and hydroperox-
Table 4. Formation of byproducts during cumene hydroperoxide
ide molar selectivity is 92 – 96 %. Spent air is decomposition ∗
vented after organic vapors are removed by con-
Temp. ◦ C Molar ratio (byproducts/phenol)×100
densation followed by activated carbon adsorp-
tion. The recovered materials are washed with DMPM equivalents∗∗ Acetophenone
aqueous sodium hydroxide and water, then re- 70 0.36 0.06
turned to the oxidizers. 90 0.61 0.06
The oxidation of cumene generates approx- 110 1.24 0.15
122 2.19 0.25
imately 116 kJ of heat per mole of cumene ox- 146 5.04 0.69
idized [30]. Part of this heat is carried to the
∗ Pure cumene hydroperoxide added to
condensers by organic vapors (this part is larger phenol – acetone – cumene solution containing initially 0.5 wt %
in the Allied/UOP process because of the lower water and 100 ppm sulfuric acid; data from [28].
operating pressure). The rest is removed by heat ∗∗ Sum of dimethylphenylmethanol, α-methylstyrene, and their
condensation products.
exchangers.
In both processes cumene hydroperoxide is
Acetone produced during the cleavage of
concentrated to over 80 wt % by evaporation of
cumene hydroperoxide can react further. Oxi-
excess cumene. In the Hercules process the oxi-
dation by cumene hydroperoxide forms hydrox-
date is washed with water prior to distillation in
yacetone [34] to the extent of 0.2 – 0.5 % of
order to remove the buffer added during oxida-
acetone present. Self-condensation catalyzed by
tion.
acid results in diacetone alcohol and mesityl ox-
Cumene Hydroperoxide Cleavage. ide. Conversion of acetone to these condensates
Cumene hydroperoxide [80-15-9] is cleaved is normally below 0.1 % but may increase upon
to phenol and acetone in the presence of cat- protracted exposure to strong acid. For example,
alytic amounts of a strong acid. The acid most when the cumene hydroperoxide cleavage was
commonly used is sulfuric acid. Sulfur dioxide carried out with refluxing acetone using a sul-
is used as catalyst in the Allied/UOP process. fonic acid resin as catalyst, approximately 1.7 %
Several patents claim the use of solid acids as of acetone was transformed to diacetone alcohol
catalysts for the decomposition [31]. Strongly and mesityl oxide [32].
acidic resins have been used to that effect in Under the conditions of the cumene hydro-
the Soviet Union [32]. However, all commercial peroxide cleavage, dimethylphenylmethanol is
units use strong mineral acids or SO2 , which dehydrated to α-methylstyrene (2) and also
generates sulfuric acid in situ, as catalysts. forms undesirable condensates.
6 Acetone

In the Allied/UOP process the cleavage mix-

ture is treated with an ion-exchange resin to
remove the acid catalyst and then is distilled.
Acetone is removed first in a crude acetone
column and purified by distillation with steam
Compound (2) may be either hydrogenated [35] in an acetone-refining column. Cumene, α-
to cumene and recycled, or recovered and sold. methylstyrene, and phenol are recovered by se-
In the Hercules process, the cumene hydro- quential distillation of the bottoms from the
peroxide decomposition is carried out in a crude acetone column. Cumene is recycled to
constant-flow, stirred tank reactor in the pres- the oxidizers after it has been washed with al-
ence of sulfuric acid or another strong mineral kali, and α-methylstyrene is marketed.
acid [19], [28]. The acid is added to the re-
actor as an acetone solution. The reactor tem-
perature is maintained below 95 ◦ C by reflux- 4.2. Dehydrogenation of 2-Propanol
ing approximately 2.8 kg acetone per kilogram
cumene hydroperoxide. The ratio of the quantity The hydration of propene [115-07-1] gives 2-
of reflux to the quantitiy of hydroperoxide fed is propanol [67-63-0], which is then dehydro-
used as a monitor of the cleavage reaction [19]. genated to acetone. In the United States a C3
In the Allied/UOP process the cumene hydro- stream containing 40 – 60 % propene is used for
peroxide cleavage is carried out at 60 – 80◦ C in the manufacture of 2-propanol (4).
a pressurized, constant-flow, back-mixed reac-
tor. Temperature is controlled by means of heat
exchangers in the loop. The catalyst is either
sulfuric acid or sulfur dioxide. Up to 5 wt %
cumene hydroperoxide remains unreacted. Un-
der these conditions, dimethylphenylmethanol The dehydrogenation of (4) is endothermic
combines with cumene hydroperoxide to form by 66.6 kJ/mol at 327 ◦ C. The equilibrium con-
dicumyl peroxide (3) [ 80-43-3], which upon stant, K p (bar), obeys the following equation
subsequent heating to 110 – 140 ◦ C in a short- [37]:
residence-time plug-flow reactor is cleaved into
log K p = − 2764/T + 1.516 log T + 1.765
phenol, acetone, and α-methylstyrene.
The main side reaction is the dehydration of
2-propanol to propene. Other competing reac-
tions are the self-condensation of acetone to di-
acetone alcohol, which leads to further conden-
sation products.
A large number of catalysts for 2-propanol
dehydrogenation have been studied, includ-
This sequence suppresses the formation of con- ing copper, zinc, and lead metals, as well as
densates by approximately 50 %. Variants of metal oxides, e.g., zinc oxide, copper oxide,
this two-stage process have been patented [36]. chromium-activated copper oxide, manganese
oxide, and magnesium oxide. Inert supports,
Product Separation. In the Hercules pro- such as pumice, may be used.
cess the cleavage mixture is neutralized with Highly active catalysts are the precious met-
base and then fed to a separation column. The als platinum and ruthenium [39] or 0.25 % plat-
overheads from this column contain acetone, inum on sodium-activated alumina [40]. These
α-methylstyrene, and cumene; acetone is re- catalysts are particularly effective for the dehy-
covered by distillation, and α-methylstyrene drogenation of aqueous 2-propanol, which is ob-
is hydrogenated without prior separation from tained by hydration of propene.
cumene. This cumene stream is then recycled to All catalysts gradually lose activity because
the oxidizers. Phenol from the bottoms of the of a buildup of carbon deposits, so the operat-
separation column is recovered by distillation. ing temperature is increased as the catalyst ages.
 Acetone 7

The catalyst is regenerated periodically by burn- mixture of acetone (92 % selectivity) and propi-
ing out the deposits. A good catalyst lasts for onaldehyde (2 – 4 % selectivity) is produced.
several months.
In a typical process, the azeotropic mixture
of water and 2-propanol (87.8 wt % 2-propanol)
is evaporated (sometimes using steam as carrier)
and fed to a catalyst bed in a reactor specially
designed for effective heat transfer. Hydrogen,
produced downstream, may be mixed with the The process is analogous to the oxidation of
feed to prevent catalyst fouling. The reactor con- ethylene to acetaldehyde by the Wacker process.
sists of a multitude of 2.5-mm steel tubes heated The catalyst solution typically contains 0.045 M
by oil, high-pressure steam, hot gases, or molten palladium(II) chloride, 1.8 M copper(II) chlo-
salts. The reaction produces hydrogen (> 99 % ride, and acetic acid [45]. The reaction usually
purity) as a valuable byproduct. This is separated is carried out in two alternating stages. In the
by condensing all other components. Acetone is first stage, air is used to oxidize the metal ions
separated by distillation. The process is illus- to the +2 oxidation state. In the second, air is
trated in Figure 2. Typical operating conditions removed and propene added. Palladium(II) ox-
are shown in Table 5. idizes propene, and the resulting palladium(I)
is reoxidized by the pool of copper(II). Reac-
tion conditions are 1 – 1.4 MPa (10 – 14 bar) and
110 – 120 ◦ C. Propene conversion is higher than
4.3. Propene Oxidation [43], [44] 99 %.
Besides propionaldehyde, chlorinated car-
Direct oxidation of propene (Wacker – Hoechst bonyl compounds and carbon dioxide also are
process) currently is practiced only in Japan. A

Table 5. Gas-phase dehydrogenation of 2-propanol

Company Catalyst Temperature, Pressure, Conversion, Selectivity, Yield, Reference

◦
C kPa % % %

Standard Oil ZnO/ZnO2 400 201 – 304 98.2 90.2 88.6 [38]
Knapsack-Griesheim CuO/Cr2 O3 /Na2 O pumice 300 89.5 99.0 88.6 [39]
Toyo-Rayon CuO/NaF/SiO2 300 93.4 100 93.4 [40]
Engelhard Industries 5 % Pt/C 310 92.4 [41]
Usines de Melle CuO/Cr2 O3 /SiO2 220 151 75 98.2 73.7 [42]

Figure 2. Acetone production via 2-propanol dehydrogenation

a) Reactor; b) Heating loop; c) Refrigeration; d) Distillation columns
8 Acetone

formed. Acetone and the byproducts are re- Tire & Rubber Company use this process in
moved from the catalyst solution by flash evap- the United States. Annual US capacity is es-
oration with steam and separated by fractional timated to be 18 – 20 t/a. Sumitomo Chemical
distillation. Propionaldehyde (bp 49 ◦ C) distills Company and Mitsui Petrochemical Industries
in one column and acetone (bp 56 ◦ C) distills in of Japan use a similar process to produce p-
the other. cresol from cymene. Their annual capacity of
acetone byproduct is 48 000 t.

4.4. Oxidation of 2-Propanol [46]

4.6. Fermentation of Biomass
In the absence of catalysts 2-propanol reacts
with oxygen via a free-radical reaction to form The fermentation of cornmeal or molasses by
acetone and hydrogen peroxide. various members of the Clostridium genus
yields a mixture of 1-butanol, acetone, and
ethanol in 2 % overall concentration. The prod-
ucts are recovered by steam distillation and then
Until the mid-1980s the Shell process used fractionated.
hydrogen peroxide for the manufacture of glyc- The process was started during World War II
erol from propene. The theoretical yield of ace- to provide acetone needed for the manufacture
tone based on glycerol produced is 1.26 kg/kg. of cordite. The last operating plant in the United
Acetone yields of about 90 % of theoretical were States (Publicker Industries) closed in 1977.
obtained. The mixture of butanol, acetone and ethanol
produced has been considered for use as a gaso-
line substitute in France [48]. Research aimed
at increasing the concentration of useful prod-
4.5. Oxidation of p-Diisopropyl Benzene ucts obtained in the process was carried out in
the United States in the early 1980s [49]. The
Acetone is coproduced with hydroquinone
future of the fermentation process is tied to the
[123-31-9] from p-diisopropylbenzene
availability of petrochemical feedstocks. High
[100-18-5] in a process analogous to the phe-
oil prices during the oil crises of the mid to
nol – acetone production from cumene.
late 1970s led to renewed interest in the pro-
cess. Given the low oil prices of the 1990s and
the ready availability of feedstocks at reasonable
prices, it does not appear that these processes can
compete under current conditions.

In the Goodyear process [47] p-diisopropyl- 5. Environmental Protection

benzene is oxidized by oxygen in the pres-
ence of caustic. The p-diisopropylbenzene di- Because approximately 70 % of acetone is pro-
hydroperoxide (5) [3159-98-6] formed is crys- duced from cumene, a close examination of this
tallized and washed with benzene. It is then dis- process is warranted. Potential pollution sources
solved in acetone and cleaved to hydroquinone in a phenol – acetone plant are emissions to the
and acetone in the presence of sulfuric acid. atmosphere and liquid discharge. Atmospheric
Next the acid is neutralized with ammonia and emissions from the phenol – acetone process in
the ammonium sulfate formed is filtered. Ace- the late 1970s have been estimated [29]. How-
tone is recovered by distillation from the re- ever over the past 20 years, and particularly in
action mixture. Some of this acetone is recy- the 1990s with the renewal of the Clean Air Act,
cled to the cleavage section while the rest passes these emissions have been reduced significantly.
through a finishing column for purification to at Aqueous streams containing significant
least 99.5 %. Eastman Chemical and Goodyear amounts of organic substances arise from the
 Acetone 9

various wash operations and sumps at the plant. Section 313) list in June of 1995. Acetone is not
Insoluble material is recovered by decantation. regulated as a known or suspected carcinogen,
Phenol and acetone (0.5 – 3 wt % each) are the and the National Toxicology Program (NTP) has
most abundant organic compounds remaining in recommended against testing for carcinogenic-
the water after decantation. There are also mi- ity because of its low toxicity and absence of any
nor quantities (0.001 – 0.1 wt %) of cumene, α- evidence supporting the carcinogenic potential
methylstyrene, dimethylphenylmethanol, ace- of acetone.
tophenone, formaldehyde, formic acid, and var- Acetone is listed as a “U” waste under the Re-
ious condensates. Of these compounds, phe- source Conservation and Recovery Act (RCRA)
nol, formaldehyde, and formic acid are listed as based on its ignitability. “U” wastes are commer-
hazardous substances in the U.S. Federal Wa- cial chemicals that must be treated as hazardous
ter Pollution Control Act [50], but only phenol wastes when discarded. Because of its RCRA
is present in sufficient quantities to require re- listing it is included in the list of hazardous sub-
moval. Phenol is removed from the aqueous so- stances in the Superfund statute (Comprehen-
lution by solvent extraction, steam stripping, or sive Environmental Response, Compensation,
adsorption on carbon or resins [51] and subse- and Liability Act).
quently is recovered. The recovered phenol is
valuable enough to pay for the capital and op-
erating expenses of phenol abatement. Residual
phenol in the water (10 – 500 ppm) is destroyed
6. Quality Specifications and
by biological degradation. Analysis
The federal regulatory status of acetone has
Acetone is produced industrially in relatively
changed. Acetone was granted VOC-exempt sta-
high purity, the main impurity being water.
tus by EPA on June 16, 1995 [53]. As of August,
Table 6 summarizes the quality requirements
1997, forty-four states had promulgated similar
for commercial 99.5 % acetone. Methods for
state rules. In states that have not yet promul-
preparing very high purity acetone from the
gated state exemptions, acetone may technically
commercial material are given in reference [54].
still be regulated as a VOC. Acetone is not listed
Gas chromatography is the most widely used
as a hazardous air pollutant (HAP) under section
method for the quantitative analysis of acetone.
112(b) of the Clean Air Act (CAA), or as an
For example, good separation of acetone from
extremely hazardous substance under EPCRA
other low-boiling organic compounds can be ob-
Section 302. Acetone is also not listed as a pri-
tained on a 30 m × 0.32 mm Carbowax capillary
ority pollutant under the Clean Water Act. It has
column. Extensive data on packed column sepa-
been approved under the CAA as a substitute
rations are compiled in [55]. Infrared (carbonyl
for ozone-depleting substances. Acetone was re-
absorption, 1711 cm−1 ) and 1 H NMR (singlet
moved from the Federal Emergency Planning
at ca. 1.05 ppm) spectroscopy may be used for
and Community Right-to-Know Act (EPCRA
both qualitative and quantitative analysis.

Table 6. Standard specifications for acetone, ASTM D329-90

Property ASTM test Specification

Relative density D268

20/20 ◦ C 0.7910 – 0.7930
25/25 ◦ C 0.7865 – 0.7885
Color D1209 ≤ 5 on platinum-cobalt scale
Distillation range D1078 1.0 ◦ C, including 56.1 ◦ C
Nonvolatile matter D1353 ≤ 5 mg/100 mL
Odor D1296 characteristic, nonresidual
Water D1364 ≤0.5 wt % ∗
Acidity (as acetic acid) D1613 ≤0.002 wt %
Water miscibility D1722 passes test
Alkalinity (as ammonia) D1614 ≤0.001 wt %
Permanganate time D1363 ≥30 min at 25 ◦ C

∗ This water limit ensures that the material is miscible without turbidity with 19 volumes of 99 % heptane at 20 ◦ C (ASTM D1476).
10 Acetone
Table 7. Estimated 1995 US acetone consumption by area of
7. Storage and Transportation application [59]

Use Acetone used, 103 t

Acetone has a low flash point; therefore, all ship-
ping and storage containers must carry a red, di- Acetone 500
amond shaped “flammable liquid” label. Strict cyanohydrin/methacrylates
Bisphenol A 203
precautions should be taken to guard against fire Aldol chemicals 140 (total)
hazards whenever acetone is handled. All wiring Methyl isobutyl carbinol 35
Methyl isobutyl ketone 76
should be installed as described in Article 500 of Others 22
the U.S. National Electrical Code or correspond- Solvent use 191
ing regulations in other countries. Explosion- Other uses 90
Total 1124
proof motors, switches, etc., should be used. Ac-
cumulation of static electricity should be pre-
vented by grounding and humidity control. Use
of spark-resistant tools is recommended. Small 8.1. Methyl Methacrylate
fires may be controlled by use of carbon dioxide
or dry chemical extinguishers. “Alcohol”-type Acetone is condensed with hydrogen cyanide to
foam should be used on larger fires; water spray form acetone cyanohydrin (6) (see Section 11.1),
will reduce the intensity of the flame. which is next hydrolyzed with sulfuric acid to
Contact of acetone with oxidants should be methacrylamide sulfate (7).
avoided because it may lead to explosion [5]. Further reaction with methanol yields methyl
Contamination with chlorinating agents may methacrylate (8) [80-62-6]. Approximately
lead to the formation of toxic chloroketones. 0.70 kg of acetone is required per kilogram of
Prolonged exposure to direct sunlight may result methyl methacrylate produced.
in the formation of carbon monoxide. Packaging
requirements for acetone are described in para-
graph 49 CFR 173.242 (bulk), Bulk Packaging
with Packaging for Certain Medium Hazard Liq-
uids and Solids, Including Solids with Dual Haz-
ards [56]. Transportation of acetone is covered in
paragraph 49 CFR 172.101, Table of Hazardous
Materials, of the Department of Transport Reg-
ulations [57]. The international transportation
codes are IMDG Code D 3102; UN no. 1090; Higher methacrylate esters may be produced
CFR 49, 172.101; RID (ADR, ADNR): Class 3, either by transesterification of methyl methacry-
IATA: flammable liquid. The quantity of acetone late or by esterification of methacrylic acid (9)
in one package may not exceed 5 L in plastic, [79-39-0]; the latter is made by hydrolysis of
metal or aluminum, 1 L in glass, or 0.5 L in a methacrylamide sulfate:
glass ampoule in a passenger aircraft. The quan-
tity of acetone in one package may not exceed
60 L in a cargo plane.

At the end of 1995 there were 22 plants man-

8. Uses ufacturing MMA in the United States, West-
ern Europe, and Japan. Five basic process
The main uses of acetone are as a chemical in- routes have been commercialized: The ace-
termediate and as a solvent. The estimated 1995 tone cyanohydrin route; two-stage oxidation of
acetone consumption by area of application in isobutylene to methacrylic acid followed by es-
the USA is shown in Table 7 [59]. terification; two-stage oxidation of tert-butyl al-
cohol to methacrylic acid followed by esteri-
fication; hydroformylation of ethylene to pro-
pionaldehyde, condensation with formaldehyde
 Acetone 11

to methacrolein, oxidation, and esterification

(BASF); and ammoxidation of tert-butyl alco-
hol to methacrylonitrile, which is hydrolyzed
to methacrylamide sulfate and then esterified
to MMA (Asahi). One new route has been an-
nounced by Mitsubishi Gas Chemicals, which
is a recycle version of the acetone cyanohydrin
route. A 41 × 103 t/a plant to make MMA and
MAA started up in 1997. Worldwide production
of MMA in 1996 was about 1682 × 103 t [60].

8.2. Bisphenol A (→ Phenol Derivatives)

Bisphenol A (10), 4,4 -isopropylidenediphenol
[80-05-7] is manufactured by condensation of
2 mol phenol with 1 mol acetone in the presence
of an acid catalyst:
Approximately 1.25 kg of acetone is used per
kilogram of methylisobutyl ketone produced.
The US 1996 production of ca. 100 × 103 t
of MIBK consumed ca 75 × 103 t of acetone.
The US manufacturers are: Eastman (Kingsport,
Tennessee), Shell (Deer Park, Texas), and Union
Approximately 0.28 kg of acetone is required Carbide (Institute, West Virginia) [62]. Methyl
per kilogram of bisphenol A. In the 1990s, isobutyl ketone is used as a solvent for nitro-
bisphenol A has had the fastest growing de- cellulose lacquers, vinyl polymers, and acrylic
mand of the phenol derivatives. Four US. com- resins [62].
panies produce bisphenol A: Shell (Deer Park, Diacetone alcohol, mesityl oxide, and
Texas), General Electric (Mount Vernon, In- isophorone are used mainly as solvents. Their
diana), Dow (Freeport, Texas), and Aristech use has diminished in the USA because of their
(Haverill, Ohio). Estimated worldwide usage in status as photochemically reactive solvents un-
1995 was 1600 × 103 t [61]. der Rule 66 of Los Angeles County [52]. The
primary use of 4-methyl-2-pentanol is for ore
flotation, and 2-methyl-2,4-pentanediol is used
8.3. Aldol Chemicals (see Section 11.2, in hydraulic fluids and printing inks.
also → Ketones)

These chemicals are produced by conden-

sation of acetone. Two moles of acetone 8.4. Solvent Uses
form 1 mol of diacetone alcohol, 4-hydroxy-
4-methyl-2-pentanone (11) [123-42-2]. Sub- Acetone is used as a solvent for paints, varnishes,
sequent dehydration yields mesityl oxide, 4- and lacquers. It is also used as a wash solvent
methyl-3-penten-2-one (12) [141-79-7]. Hy- for these materials and as a spinning solvent in
drogenation of (11) yields 2-methyl-2,4- the manufacture of cellulose acetate. A small
pentanediol (13) [107-41-5]. By hydrogena- amount of acetone is used as a solvent for acety-
tion of (12) methyl isobutyl ketone (14) lene. Approximately 191 × 103 t of acetone was
[108-10-1] is available; further hydrogenation consumed in direct solvent applications. The
produces 4-methyl-2-pentanol (15) [108-11-2]. major solvent market for acetone is in paints and
Three moles of acetone are condensed to 1 mol coatings. Consumption of acetone in these appli-
of isophorone, 3,5,5-trimethyl-2-cyclohexen-1- cations increased by 9 × 103 t in 1995 because
one (16) [78-59-1]. of its delisting as a VOC.
12 Acetone

The pharmaceutical industry is also a large nol. Consequently, phenol demand determines
consumer of acetone for the manufacture of to a large extent the availability of acetone. For-
pharmaceuticals, vitamins, and cosmetics. In tunately acetone serves to some extent the same
1995 acetone consumption in pharmaceutical markets as phenol does. These are mainly the
and cosmetic applications was (36 – 43) × 103 t. automotive and housing markets. As a result,
The removal of acetone from the VOC list when economic conditions place a demand on
has made it more attractive as a solvent, particu- phenol, acetone demand also increases. How-
larly for replacing other chemicals on the VOC ever, an unusually steep demand for phenol may
list. Following the EPA’s August 1995 action, render acetone an overabundant byproduct [63].
eight states automatically delisted acetone as a Because the single largest use of acetone is as
volatile organic compound. As of August, 1997, an intermediate in the manufacture of methacry-
forty-four states had promulgated similar state lates, alternate routes to methacrylates, such as
rules. the oxidation of C4 hydrocarbons, are a poten-
tial threat to acetone. When C4 hydrocarbon
stocks are in demand for the manufacture of
9. Economic Aspects gasoline additives, they are not likely to be used
for acrylate manufacture. However, production
The United States acetone capacity by manu- of methacrylate by oxidation of C4 hydrocar-
facturer and production process can be found in bons started in Japan in 1982 [65].
[63]. World capacity data are given in Table 8 Dehydrogenation of 2-propanol accounted
[59]. The United States acetone production for for approximately 80 % of US acetone pro-
the last two decades is summarized in Table 9 duced in 1960. As the cumene-based process
[59]. Worldwide production in 1994 was: USA expanded, the 2-propanol contribution shrank to
1281 × 103 t/a; Western Europe 1200 × 103 t/a; 52 % in 1970, 27 % in 1980, and 6 % in 1994. If
Asia 746 × 103 t/a. acetone supply does outstrip demand, it is likely
that production based on 2-propanol will be fur-
Table 8. World acetone capacity, 1995 [59], [64]
ther curtailed.
Location Capacity, 103 t Phenol manufacturing processes that do not
coproduce acetone have been developed partly
United States 1281
Mexico 22.3
because of fears that there will be a sup-
Western Europe 1200 ply/demand imbalance between phenol and ace-
Japan 475 tone. DSM and its licensees produce phenol by
Other Asia 271.4
Others 592 the air oxidation of toluene via benzaldehyde
World total 3842 and benzoic acid. Subsequently, benzoic acid is
decomposed to phenol with a copper catalyst.
Table 9. United States acetone production, 103 t [59] This route provides phenol, benzaldehyde, and
benzoic acid. Mitsui Petrochemical has devel-
Year From From Other Total oped a recycle scheme for converting the ace-
2-propanol cumene
tone byproduct from the cumene hydroperoxide
1970 379 329 26 734 rearrangement back to propylene for feed to the
1975 312 433 745
1980 250 693 943 front end of the cumene process. Solutia (for-
1985 41 768 3 812 merly Monsanto) and the Boreskov Institute of
1990 70 972 17 1059 Catalysis have developed a catalyst capable of
1994 73 1110 20 1203
oxidizing benzene in high yield with nitrous ox-
ide to give directly phenol. The key to this pro-
In 1995 the phenol process accounted for cess is the inexpensive nitrous oxide available as
83 % of all acetone made and 9 % was derived a byproduct from the manufacture of adipic acid.
from 2-propanol; only 8 % was produced by all Asahi Chemical has patented a process in which
other processes (66 × 103 t/a from propene ox- benzene is partly hydrogenated to cyclohexene.
idation in Japan). The cyclohexene is hydrolyzed to cyclohexanol
The economics of acetone are unusual. The or oxidized to cyclohexanone; dehydrogenation
bulk of acetone is made as a coproduct with phe- then gives phenol [66].
 Acetone 13

10. Toxicology and Occupational Minimum lethal concentration in air (LC50 )

Health was 50.1 g/m3 (21 100 ppm) for rats exposed to
acetone vapor for 8 h and 44 g/m3 (18 500 ppm)
Acetone is one of the least toxic industrial sol- for mice exposed for 4 h Human exposure to ace-
vents [67]. However, exposure to vapor at high tone has been studied [72–77]. Eye and nasal ir-
concentration should be avoided because it can ritation were observed at 1.2 g/m3 . Other effects
produce temporary narcosis and cause slight eye are similar to those of ethanol, but the anesthetic
irritation. Repeated skin contact with the liquid potency is greater. Prolonged or repeated skin
defats the skin and may cause dermatitis. The contact may defat the skin and can produce der-
liquid is also irritating to the eyes and may cause matitis. Direct contact of acetone with the eyes
moderate corneal injury. can produce corneal injury. Acetone is a solvent
The ACGIH [68] has adopted a time- of comparatively low acute and chronic toxic-
weighted average threshold limit value (TLV- ity. However it does not have sufficient warn-
TWA) of 750 ppm, 1.78 g/m3 , and a short- ing properties to prevent repeated exposures to
term exposure limit (TLV-STEL) of 1000 ppm, vapors, which may have adverse effects. There
2.375 g/m3 , for acetone. OSHA regulations [69] have been no reports that prolonged inhalation
set a limit of 2.4 g/m3 . However, the ACGIH of low vapor concentrations result in any serious
has issued a notice of intended change to lower chronic effects in humans.
the TLV to 500 ppm (1.19 g/m3 ), and the STEL Cases of acetone poisoning are rare [67]. In
to 750 ppm (1.78 g/m3 ) [70]. Exposure lim- one case, a solvent mixture containing 90 % ace-
its (TLV-TWA) adopted by the main industrial tone and 9 % pentane was used to set a cast for
countries are shown in Table 10 [71]. The odor a broken leg on a 10-year-old boy [78]. The boy
threshold of acetone is 48 mg/m3 provided de- became ill and collapsed 12 h later. After the cast
sensitization has not occurred. Animal studies was removed the boy became comatose but re-
have shown acetone to be relatively nontoxic covered completely in 4 days. In another case, a
[67], [71]. 42-year-old man ingested 200 mL of acetone and
became comatose for 12 h [79]. Subsequently,
Table 10. Time-weighted average threshold limits for acetone [71] hyperglycemia was diagnosed and attributed to
Country Limit, mg/m3 acetone ingestion.
Acetone does not cause neurotoxicity, an oc-
Australia 1780 cupational disorder caused by exposure to some
Belgium 1780
Germany 2400 higher aliphatic ketones and related compounds
Italy 1000 [80]. Acetone vapor is absorbed with 75 % ef-
Japan 470
Netherlands 1780 ficiency by the lungs [76]. The half-life for the
Former Soviet Union 475 elimination of acetone by expired air is approxi-
United States 1780 mately 5 h. The metabolism of acetone may pro-
ceed through 1,2-propanediol [67], [81], [82].
LD50 (oral, mouse) 4 – 8 g/kg [67]
LD50 (oral, rabbit) 5.3 g/kg [67]
LD50 (intraperitoneal, mouse) 1.3 g/kg [67] 11. Derivatives
LD50 (dermal, rabbit) 20 g/kg [71]
Nonteratogenic at 39 or 78 mg per chicken egg
[67] 11.1. Acetone Cyanohydrin
Nonmutagenic in the Salmonella/microsome
(Ames) test [67] Acetone cyanohydrin, 2-hydroxy-2-methylpro-
Nononcogenic on skin of mice, three times a panenitrile, CH3 C(OH)(CN)CH3 [75-86-5] is
week for 1 year [67] an important chemical intermediate for the man-
Moderate corneal injury on rabbit eye [67] ufacture of methacrylates (→ Methacrylic Acid
Environmental toxicity: LC50 (rainbow trout, and Derivatives). Small amounts of acetone
96 h) 5540 mg/L; LC50 (bluegill sunfish, 96 h) cyanohydrin are used in insecticide manufac-
8300 mg/L. ture.
14 Acetone

Physical Properties. Acetone cyanohydrin exchange resins. A schematic flowsheet of the

is a colorless liquid. The pure compound is prac- Rohm & Haas [89] process is shown in Fig-
tically odorless but usually has an odor of bitter ure 3. Acetone and liquid hydrogen cyanide are
almonds because of traces of hydrogen cyanide. fed continuously to a cooled reactor along with
It is very soluble in water and polar solvents and an alkaline catalyst. The catalyst is next neutral-
sparingly soluble in hydrocarbons. ized with sulfuric acid and the resulting salt is
M r 85.11, mp −19 ◦ C, relative density d 254 removed by filtration. The crude product is then
0.9267, relative vapor density (air = 1) 2.96, re- distilled in a two-stage process. The overheads
fractive index n25 ◦
D 1.3980, flash point 73 C. from the first column consist mainly of acetone
and hydrogen cyanide, which are recycled to the
Vapor pressure
reactor. The second column removes water over-
p, kPa 5.3 3.1 1.3 1.2 head and leaves 98 % pure acetone cyanohydrin
t, ◦ C 95 82 74 72 at the bottom. Nitto Chemical claims a two-
column distillation system that delivers acetone
cyanohydrin of 99.1 % purity [90]. The man-
Chemical Properties. Acetone cyanohydrin ufacture of acetone cyanohydrin produces no
exhibits the combined characteristics of a ni- byproducts other than small amounts of sul-
trile and an alcohol. Under neutral and par- fate salts formed during catalyst neutralization.
ticularly under alkaline conditions it decom- However, the conversion of acetone cyanohy-
poses to acetone and hydrogen cyanide. The drin to methacrylate in the classical process
decomposition is inhibited by the addition of produces a large amount of ammonium sulfate
small amounts of sulfuric or phosphoric acid; byproduct, which is usually pyrolyzed to sul-
consequently, technical-grade material is stabi- furic acid. An alternative process developed by
lized by addition of 0.01 wt % of either acid. Mitsubishi Gas Chemical recycles the HCN via
Reaction with concentrated sulfuric acid con- formamide. In this process HCN is not directly
verts acetone cyanohydrin to methacrylamide consumed and no ammonium sulfate is formed.
sulfate; subsequent neutralization with ammo-
nia yields methacrylamide [79-39-0]; alcoholy- Uses. By far the largest use of acetone
sis yields methacrylate esters; alternatively, hy- cyanohydrin is as an intermediate in the
drolysis gives methacrylic acid [79-41-4].The synthesis of methyl methacrylate [80-62-6],
yield of methacrylic acid is improved if 3 – 10 % methacrylic acid, and higher methacrylate es-
oleum is used instead of 100 % sulfuric acid in ters. A small amount is converted to methacry-
the reaction with acetone cyanohydrin [83]. lamide. The estimated amount of acetone used in
the manufacture of methacrylate esters in 1995
Production. Acetone cyanohydrin is manu- in the United States was 500 × 103 t (Table 7).
factured by the base-catalyzed condensation of Based on this estimate, the quantity of acetone
acetone with hydrogen cyanide according to the cyanohydrin produced as an intermediate was
following mechanism [84]: approximately 714 × 103 t.
Certain esters of acetone cyanohydrin, such
as 2-chloroethyl-α-cyanoisopropylsulfite [91]
and α-cyanoisopropyl-2,6-dichlorobenzoate
[92] have strong fungicidal, herbicidal, and
insecticidal properties. Nitrilurethanes made
from acetone cyanohydrin and substituted
phenylisocyanates are intermediates for 4-
The reaction is reversible but formation of the iminooxazolidin-2-ones, which are plant growth
cyanohydrin is quite favorable; the equilibrium inhibitors [93].
constant is 28 L/mol at 20 – 25 ◦ C [85]. The
reaction usually is carried out in the liquid Transportation and Toxicology. Most ace-
phase. Representative catalysts used industrially tone cyanohydrin is consumed on site for the
are sodium hydroxide [86], potassium hydrox- manufacture of methacrylates. Because of its
ide [87], potassium carbonate [88], and anion- high toxicity, acetone cyanohydrin is classified
 Acetone 15

Figure 3. Rohm and Haas acetone cyanohydrin process [89]

a) Reactor; b) Cooling; c) Filter press; d) Concentrator; e) Concentrator; f) Condenser; g) Vacuum jet; h) Pump for acetone
and HCN recycle

as a poison B and all shipping containers must 18.84 kJ kg−1 K−1 , thermal expansion coeffi-
carry a “poison inhalation hazard” label [57]. cient (20 ◦ C) 0.00099 K−1 , viscosity at 20 ◦ C
Transport aboard a passenger-carrying or cargo 2.9 mPa · s, surface tension (20 ◦ C) 31.0 mN/m,
aircraft is forbidden [58]. Acetone cyanohydrin dielectric constant (25 ◦ C) 18.2, heat of com-
has the following toxicologic properties [94]: bustion 3544.5 kJ/mol, flash point 58 ◦ C, lower
LD50 (oral, rat) 18.6 mg/kg; LD50 (oral, rab- explosion limit in air 2.6 vol % , auto ignition
bit) 14 mg/kg; LD50 (dermal, rabbit) 17 mg/kg; temperature 624 ◦ C.
LD50 (dermal, guinea pig) 150 mg/kg; aquatic
Vapor pressure
toxicity rating (TLm96) 10 to 1 ppm. Threshold
limit values have been established as cyanide: p, kPa 101.3 1.7 0.108
t, ◦ C
TLV-STEL, 4.7 ppm ceiling limit (5 mg/m3 ) 168.1 61.7 20.0

[68].
Azeotropic mixture with water: bp 98.8 ◦ C/
101.3 kPa, 12.7 wt % diacetone alcohol.
11.2. Diacetone Alcohol
Chemical Properties. Diacetone alcohol
Diacetone alcohol, 4-hydroxy-4-methyl-2- dehydrates readily in the presence of acids
pentanone [123-42-2] to form mesityl oxide. Catalytic hydrogena-
tion [95] yields hexylene glycol. In the pres-
ence of bases, diacetone alcohol reverts to
acetone. The reaction is first order in di-
acetone alcohol and first order in base. The
dissociation is accompanied by volume in-
is a dimer of acetone that is used as a solvent crease; consequently, the reaction is inhibited
and as an intermediate for the manufacture of by pressure [96]. The second-order rate con-
mesityl oxide, methyl isobutyl ketone, and hexy- stant is 7.33×10−4 L mol−1 s−1 at 101.3 kPa
lene glycol. and decreases to 2.38×10−4 L mol−1 s−1 at
4.05×105 kPa. In neutral aqueous solution, dis-
Physical Properties. Diacetone alcohol is a sociation to acetone is very slow at room tem-
colorless liquid of mild odor. It is miscible with perature; it reaches approximately 0.1 % in 1
water and polar solvents and is an excellent sol- year.
vent for cellulose acetate and various oils and Diacetone alcohol may be acylated by acetic
resins. M r 116.16, mp − 47 ◦ C, relative den- anhydride under mild conditions to form diace-
sity, d 20 20
4 0.9387, refractive index nD 1.4235, tone alcohol acetate [1637-25-8], 4-methyl-4-
heat of vaporization at the boiling point at 101.3 acetyloxy-2-pentanone, which is claimed as an
kPa 357.1 kJ/kg, specific heat capacity (20 ◦ C) octane-improving gasoline additive [97]. Con-
16 Acetone

densation with urea in the presence of sulfuric not exempt from restrictions under Rule 66 and
acid yields diacetone-monourea, 3,4-dihydro- related federal regulations [52]. Therefore, US
4,4,6-trimethyl-2(1H)-pyrimidone [4628-47-1] sales have declined more than 50 % since 1978,
[98], [99]. reaching 10 000 t/a for the past several years and
are expected to remain flat. A large portion of di-
acetone alcohol is used as an intermediate for the
manufacture of mesityl oxide, methyl isobutyl
ketone, and hexylene glycol.

The compound is claimed to improve the egg- Transportation and Toxicology. Diacetone
laying capacity of hens [98]. alcohol has a flash point of 58 ◦ C, and all trans-
port containers must carry a “flammable liq-
Production. Diacetone alcohol is manufac- uid” label. Threshold limit values (TLV) for
tured by self-condensation of acetone in the diacetone alcohol vapor at the workplace are:
presence of a basic catalyst. The reaction is 50 ppm, 240 mg/m3 (TLV-TWA) [69]; MAK is
exothermic by 14.65 kJ/mol and is easily re- 50 mL/m3 , 240 mg/m3 . These limits also apply
versible. The equilibrium concentration of di- to the other major industrial countries [71]. The
acetone alcohol is 23.1 wt % at 0 ◦ C and de- toxicologic properties of diacetone alcohol are
creases with increasing temperature [100]. Ki- as follows [107]: LD50 (oral, rat) 4 g/kg; LD50
netic considerations dictate, however, a higher (intraperitoneal, mouse) 933 mg/kg; LD50 (der-
temperature for the manufacture of diacetone mal, rabbit) 13.5 g/kg; aquatic toxicity rating
alcohol. An optimum temperature range is (TLm96) 1000 – 100 ppm.
10 – 20 ◦ C.
The self-condensation of acetone is carried
out in continuous-flow reactors containing a 11.3. Miscellaneous Derivatives
solid alkaline catalyst, such as barium hydrox-
ide or calcium hydroxide [101], [102]. Anion- Acetone is used in the production of methyl amyl
exchange resins have been investigated [103], ketone (MAK, 2-heptanone). MAK is produced
[104], but are not believed to be used commer- by the condensation of n-butyraldehyde and ace-
cially. Catalyst performance deteriorates with tone. In 1995, US consumption of acetone for
time, but may last up to 1 year. A patent [105] MAK was approximately 12 × 103 t, producing
describes how addition of small amounts of ca. 17.5 × 103 t of MAK. Eastman Chemical
methanol, ethanol, or 2-propanol to the reaction is the sole US producer. Acetone is also used
mixture retards catalyst deterioration. The selec- to produce methyl isoamyl ketone (MIAK) by
tivity for diacetone alcohol is 90 – 95 %. Mesityl condensation of acetone with isobutyraldehyde.
oxide and higher condensates, such as triacetone Eastman Chemical is the sole US producer of
alcohol, are the main products. The acetone so- MIAK, which is primarily used in lacquers and
lution of the crude product is neutralized, e.g., surface coatings. Other minor uses of acetone in-
with phosphoric acid [106], prior to concentra- clude the manufacture of DuPont triazine herbi-
tion under reduced pressure. The recovered ace- cide Bladex [(3.5 – 3.6) × 103 t/a]; Ethoxyquin,
tone is recycled to the condensation reactor and a Monsanto antioxidant (2.7 × 103 t/a), as a raw
the acidity adjusted by subsequent addition of material in the production of hexafluoroacetone,
a base, such as triethylamine. After such treat- methylbutynol, and pseudoionone; and as an
ment, diacetone alcohol of 99.68 % purity was auxiliary blowing agent for the production of
obtained by vacuum distillation [106]. flexible polyurethane foam.

Uses. Diacetone alcohol is an excellent sol-

vent for many natural and synthetic resins. It is
12. References
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 Acetone 17

2. Ullmann, 4. Aufl., 7 : 25. 29. J. L. Delaney, T. W. Hughes: Source

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Acetonedicarboxylic Acid → Oxocarboxylic Acids

Acetonitrile → Nitriles
Acetophenone → Ketones
Acetylacetone → Ketones
Acetyl Chloride → Acetic Acid
Acetylcholine → Neuropharmacology