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Article No : a04_475

2-Butanone
DETLEF HOELL, Sasol Solvents Germany GmbH, Moers, Germany
THOMAS MENSING, Sasol Solvents Germany GmbH, Moers, Germany
RAFAEL ROGGENBUCK, Sasol Solvents Germany GmbH, Moers, Germany
MICHAEL SAKUTH, Sasol Solvents Germany GmbH, Moers, Germany
EGBERT SPERLICH, Sasol Solvents Germany GmbH, Moers, Germany
THOMAS URBAN, Sasol Solvents Germany GmbH, Moers, Germany
WILHELM NEIER, Deutsche Texaco AG, Moers, Germany
GUENTER STREHLKE, Deutsche Texaco AG, Moers, Germany

1. Introduction. . . . . . . . . . . . . . . . . . . . . . 431 8.1. Occupational Exposure . . . . . . . . . .... 439


2. Physical Properties . . . . . . . . . . . . . . . . 432 8.2. Toxicokinetics and Metabolism . . . .... 440
3. Chemical Properties . . . . . . . . . . . . . . . 432 8.2.1. Absorption . . . . . . . . . . . . . . . . . . . .... 440
4. Production . . . . . . . . . . . . . . . . . . . . . . . 434 8.2.1.1. Oral Exposure . . . . . . . . . . . . . . . . . .... 440
4.1. Catalytic Dehydrogenation of sec-Butyl 8.2.1.2. Inhalation Exposure. . . . . . . . . . . . . .... 440
Alcohol (SBA) in the Gaseous Phase . . . . . 434 8.2.1.3. Dermal Exposure. . . . . . . . . . . . . . . .... 440
4.2. MEK as a Byproduct of the Fischer- 8.2.2. Distribution . . . . . . . . . . . . . . . . . . . .... 440
Tropsch Coal-to-Liquid Process. . . . . . . 436 8.2.3. Metabolism . . . . . . . . . . . . . . . . . . . .... 440
4.3. Liquid-Phase Oxidation of n-Butane . . . 436 8.2.4. Elimination and Excretion . . . . . . . . .... 440
4.4. Oxidation of sec-Butylbenzene According 8.2.5. Mechanism of Action . . . . . . . . . . . .... 441
to the Hock Phenol Synthesis. . . . . . . . . 437 8.2.6. Toxic Effects. . . . . . . . . . . . . . . . . . .... 441
4.5. Direct Oxidation of n-Butenes (Hoechst- 8.2.6.1. Oral Exposure . . . . . . . . . . . . . . . . . .... 441
Wacker Process) . . . . . . . . . . . . . . . . . . 437 8.2.6.2. Inhalation Exposure. . . . . . . . . . . . . .... 441
5. Quality, Storage, Transportation . . . . . . 438 8.2.6.3. Occupational Health . . . . . . . . . . . . .... 442
6. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439 8.2.6.4. Regulations . . . . . . . . . . . . . . . . . . . .... 442
7. Economic Aspects . . . . . . . . . . . . . . . . . 439 References . . . . . . . . . . . . . . . . . . . .... 442
8. Toxicology and Occupational Health . . . 439

1. Introduction Maruzen (JP), Oxiteno (BR), Petro Brazi (RO),


Sasol (RSA, Germany), Shell (NL), SK Corp
2-Butanone [78-93-3], methyl ethyl ketone, Ulsan (KOR), Tasco Chemical (Taiwan); Tonen
MEK, is the second link in the homologous series (JP) [8]. Interest in MEK as a solvent for paints
of aliphatic ketones and, next to acetone, the most and adhesives has been growing since the 1980s.
important commercially produced ketone. 2-Bu- In general, MEK is considered to be in competi-
tanone is produced primarily by dehydrogenation tion to ethyl acetate, especially as a low-boiling
of 2-butanol, analogous to the production of solvent. It has broad application as a solvent for
acetone by dehydrogenation of gaseous isopro- nitrocellulose, cellulose acetate butyrate, ethyl
pyl alcohol on copper, zinc, or bronze catalysts at cellulose, acrylic resins, vinyl acetates, and vinyl
400 550  C. At 80 95 % 2-butanol conver- chloride vinyl acetate copolymer (based on
sion, MEK selectivity is > 95 %. Butenes (dehy- synthetic surface-coating preparation). It is fa-
dration) and higher ketones (auto condensation) vored as a lacquer solvent because of its low
are byproducts. In 2005, about 1  106 t of MEK viscosity, high solids concentration, and wide
were produced worldwide. diluents tolerance.
2-Butanone is produced by Arkema (F), Ce- The withdrawal of MEK from the HAP
lanese (US), Exxon (GB, US), Idemitsu (JP), (hazardous air pollutant) list in 2005 was impor-

 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


DOI: 10.1002/14356007.a04_475.pub2
432 2-Butanone Vol. 6

tant to maintain the market position for MEK in Table 2. Binary azeotropic mixtures of MEK [12]
the US. bp of bp of MEK content
Moreover, MEK can be used as an activator component, azeotrope, of azeotrope,
 
for oxidative reactions, as a selective extractive Component C C wt %
agent, as a special solvent for dewaxing mineral Water 100.0 73.4 88.7
oil fractions, and as a chemical intermediate. Benzene 80.2 78.4 44.3
n-Hexane 68.9 64.3 29.5
n-Heptane 98.4 77.0 71.3
Cyclohexane 80.8 71.8 44.1
2. Physical Properties Methanol 64.7 63.9 32.8
Ethanol 78.3 74.0 60.9
MEK is a colorless, low-viscosity, flammable Isopropyl alcohol 82.4 77.5 70.4
liquid with a characteristic ketone-like odor sim- tert-Butyl alcohol 82.5 78.7 69.0

ilar to that of acetone. With a bp of 79.6  C and


Ethyl acetate 77.1 77.0 18.0
Methyl propionate 79.8 79.0 60.0
an Mr of 72.1 it is classified as a low-boiling, fast Di-isopropyl ether 68.3 66.8 16.2
evaporating solvent. MEK is only partially mis- Di-n-propyl ether 90.1 78.3 74.6
cible with water, whereas it is completely misci-
ble with most organic solvents. Physical proper-
ties of MEK are provided in Table 1. MEK does not form a binary azeotropie with
MEK forms binary and ternary azeotropic toluene, m-xylene, n-butanol, isobutanol, 2-
mixtures in combination with water and several butanol, 4-methyl-2-pentanol, allyl alcohol,
organic compounds. Examples of binary and methyl acetate, isopropyl acetate, n-butyl ace-
ternary azeotropes are given in Table 2 and 3. tate, isobutyl acetate, formic acid, and acetic
acid.
Table 1. Physical Properties of MEK [911]

Property Value 3. Chemical Properties


Mr 72.107
mp,  C 86.7 Under normal conditions and in the absence of
bp,  C 79.6
Liquid density at 25  C, g/cm3 0.7995
atmospheric oxygen, MEK is stable. Care must
Critical temperature,  C 262.45 be taken after prolonged storage because perox-
Critical pressure, MPa 4.15 ides may form in the presence of oxygen [14, 15].
Critical density, r, g/cm3 0.270
Vapor pressure at 25  C, kPa 12.71 Table 3. Ternary azeotropic mixtures of MEK [13]
Refractive index at 25  C, n25
D 1.3764
Liquid viscosity at 25  C, mPa  s 0.395 bp of bp of Composition
Liquid heat capacity at 25 C, J g1 K1

2.200
component, azeotrope, of azeotrope,
Heat of vaporization at 79.6  C, kJ/mol 31.55  
Component C C wt %
Heat of fusion, J/mol 7456
Surface tension at 20  C, mN/m 24.6 MEK 79.6 17.5
Thermal conductivity, W m1 K1 Benzene 80.2 68.9 73.6
at 0  C 0.150 Water 100.0 8.9
20  C 0.145 MEK 79.6 27.1
50  C 0.137 n-Hexane 68.9 56 68.1
Solubility at 20  C Water 100.0 4.8
MEK in water, wt % 27.5 MEK 79.6 35
water in MEK, wt % 12.5 Cyclohexane 80.8 63.6 60
Flash point (DIN 51755),  C 1 Water 100.0 5
Flash point closed cup,  C 6,1 MEK 79.6 75
Flammability limits in air Ethanol 78.3 73.2 14
lower, vol % 1.8 Water 100.0 11
upper, vol % 11.5 MEK 79.6 88
Ignition temperature,  C 505 Isopropyl alcohol 82.4 73.4 1
Electric conductivity at 20  C, W1 cm1 5  108 Water 100.0 11
Dipole moment, Debye 3.18 MEK 79.6 16.7
Dielectric constant of the liquid at 20  C 15.45 Isopropyl alcohol 82.4 68.9 23.3
Evaporation number (ether1) 2.6 Cyclohexane 80.8 60.0
Vol. 6 2-Butanone 433

Explosions may occur because of instantaneous lyzed aldolization) the a-position of the carbonyl
decomposition of peroxides. group is first occupied [20, 21].
2-Butanone is unsaponifiable and heat- and
light-resistant. It decomposes only after pro-
longed UV exposure (yielding ethane, methane,
carbon monoxide, ethylene, and diacetyl) [16].
Diacetyl [431-03-8] is formed by oxidation
Thus, the base-catalyzed aldolization with
with air in the presence of special catalysts [17].
less than stoichiometric amounts of formalde-
Methyl ethyl ketone peroxide [19393-67-0], a
hyde yields 2-methyl butane-1-ol-3-one [20] and
polymerization catalyst, is formed by oxidation
exhaustive hydroxymethylation, with reduction
with a 30 % solution of hydrogen peroxide [18].
of the carbonyl group (crossed Cannizzaro reac-
Nitric acid and other strong oxidants oxidize
tion), produces desoxyanhydroeneaheptite [22].
MEK to a mixture of formic and propionic
acids [18].
2-Butanol [78-92-2] is obtained by catalytic
reduction with hydrogen [18]. It can also be
formed by electrolytic reduction in sodium ace-
tate solution or by reduction with ammonium
amalgam or lithium aluminum hydride. 3,4-Di-
methyl-3,4-hexanediol is obtained by electrolyt-
ic reduction in an acidic medium or by reduction When MEK is reacted with primary and sec-
with magnesium amalgam [18]. ondary alcohols, higher ketones are obtained.
Methyl ethyl ketone forms addition products Reaction with sec-butyl alcohol gives ethyl amyl
with hydrogen cyanide as well as with sodium ketone [106-68-3] [23].
and potassium hydrogen sulfites. In an alkaline Methyl ethyl ketone reacts with polyoxy com-
medium, MEK condenses with aldehydes to pounds or epoxides to form cyclic products.
form higher unsaturated ketones. Condensation Amyl nitrite [110-46-3] attacks the CH2 group
with formaldehyde to form methyl isopropenyl in a-position to the carbonyl group and yields the
ketone [563-80-4], an intermediate for further monooxime of diacetyl.
syntheses, is of particular interest. During base-
catalyzed autocondensation in the liquid
phase and during gase-phase condensation on
alkalinized copper catalysts, the carbonyl group
reacts with the methyl group, whereas during
acid-catalyzed condensation the methylene The keto group reacts with amino groups
group in a-position to the carbonyl group is with elimination of water. In combination with
attacked [19]. hydroxylamine [7803-49-8], methyl ethyl ketox-
ime, an antiskinning agent, is formed.
Condensation of MEK with aliphatic esters
and anhydrides gives b-diketones.
Phenols react with MEK to form oxypheny-
lene compounds. In combination with phenol,
2,2-hydroxyphenyl butane is obtained, a homo-
log of hydroxyphenyl propane (Bisphenol A [80-
05-7]), an important material for the production
of synthetic resins.
Methyl ethyl ketone and citral [5392-40-5] Methyl ethyl ketone can be halogenated in the
condense to form methylpseudoionone that can a-position. Methyl ethyl ketone reacts with
be cyclized to methylionone, a compound used Grignard compounds to form tertiary alcohols.
for producing synthetic violet perfume. With acetylene in the presence of sodium am-
During condensation with low-molecular al- ide 3-methyl-1-pentyn-3-ol [77-75-8] is formed.
dehydes (during base-catalyzed and acid-cata- N-Methyl-formyl-aminobutane is obtained from
434 2-Butanone Vol. 6

MEK plus N-methylformamide. The Reformatz- mentioned that the oxidative dehydrogenation of
ky reaction produces the b-oxyester from sec-butyl alcohol to produce MEK plus stochio-
monobromine-substituted esters [23]. metric amounts of water is also discussed in the
literature [32].
The direct oxidation of n-butenes (Hoechst-
4. Production Wacker process, Maruzen process, [33, 34]) has
not been generally accepted, because of unde-
Today MEK is mainly produced by dehydroge- sired byproduct formation.
nation of 2-butanol (sec-butyl alcohol, SBA), The oxidation of n-butenes with ethylbenzene
i.e., approximately 92% of all production capaci- hydroperoxide to form butylene oxides and sub-
ties worldwide use this process technique (2006). sequent hydration and formation of ketones
SBA itself can easily be produced by hydra- seems not to be attractive anymore because of
tion of n-butenes (from petrochemically pro- its technical difficulties in operational realiza-
duced C4-raffinates) in a two-step process (cata- tion. Styrene, n-butanol, and MEK are obtained
lyst used is liquid sulfuric acid), or in a single- as coupled products [35].
step process by direct addition of water on a
stabilized acidic ion exchange resin, which is
used as a catalyst [24]. 4.1. Catalytic Dehydrogenation of
The remaining 8% of MEK is produced by sec-Butyl Alcohol (SBA) in the Gaseous
fatal production via FischerTropsch [25] or by a Phase
process, in which liquid n-butane is oxidized
catalytically to produce acetic acid and MEK as The catalytic dehydrogenation of sec-butyl alco-
byproduct [26]. hol (SBA) is an endothermic reaction (DHR
Following a closure of its MEK production 51 kJ/mol). The equilibrium constant Kp for
plant in the U.S., Shell Chemicals announced in SBA to MEK can be calculated by the following
2005 [27] the building of a 300400  103 t/a equation [36]:
world-scale plant for phenol production using the
Shells phenol acetone MEK (SPAM) technolo- log KP 2:790  T 1 1:51 log T1:865
gy. SPAM technology uses benzene, propene, T reaction temperature
and n-butenes as feedstock components to pro-
duce phenol and MEK with acetone as byproduct The MEK concentration in the reaction mixture
via the traditional process pathways, i.e., the increases with temperature and levels out at
intermediates cumene and sec-butylbenzene are approx. 350  C (assuming that no consecutive
oxidized according to Hocks phenol synthesis reactions follow) [37].
route, which gives phenol and the named ketones Copper [38], zinc [39], or bronze [40] are
after acid-catalyzed splitting. typical catalysts for the gas-phase dehydroge-
A 300400  103 t/a SPAM phenol plant, nation. Compared to copper as catalyst, zinc or
which is planned in the Far East by Shell Che- bronze usually require higher dehydrogenation
micals, would co-produce 130140  103 t/a temperatures (400 C). Usually, zinc oxide
MEK. shows a lower selectivity because of a dehy-
The first attempts using this production route dration side-reaction of SBA to n-butenes.
were not economically viable because of long Platinum on alumina [41], copper or chromium
reaction times combined with low product yields [42, 43] as well as copper, and zinc on alumina
[28]. After some improvements, i.e., mixing of [41] are recommended as dehydrogenation cat-
cumene with sec-butylbenzene, the reaction alysts for SBA, which contains significant
times could be reduced to a major extent, which amount of water. Commercially used catalysts
led to a higher product selectivity [29]. are reactivated by oxidation with air after 36
The auto-oxidation of liquid sec-butyl alco- months of usage. Reactivation is necessary if
hol, which gives MEK and hydrogen peroxide the alcohol conversion rate is reduced over
[30], and the catalytic oxidative hydration of time-on-stream by contamination of the cata-
gaseous n-butenes [31] are no longer economical lytical active sides with water, deposits of
process pathways. In this context, it should be butene oligomers and di-sec-butyl-ether [44],
Vol. 6 2-Butanone 435

which are removed by use of higher tempera- occurs on a copper catalyst. The endothermic
tures and oxidation. reaction heat of 51 kJ/mol is supplied by a heat
Typically, the commercial catalysts show a transfer oil system. The gaseous product stream
total lifetime of more than several years. leaves the reactor and, after cooling to ambient
Deutsche Texaco developed a process tech- temperature, it is split into a liquid crude MEK
nology for MEK production based on dehydro- phase and a gaseous hydrogen phase. The hydro-
genation of anhydrous sec-butyl alcohol on a gen is further purified by deep temperature cool-
copper-based precipitation catalyst at 240 ing in a refrigerator system (Fig. 1).
260 C under normal pressure [24, 38]. By using The liquid stream still contains, beyond the
this technology, sec-butyl alcohol is produced desired MEK, some unconverted SBA, 5-meth-
via direct hydration of n-butenes, catalyzed by a yl-3-heptanone, higher ketones, and water. 5-
temperature-stabilized acidic ion-exchange res- Methyl-3-heptanone, higher ketones and water
in [45]. Beyond this improved heterogeneous are the only byproducts which are formed via an
procedure, worldwide SBA is still mainly pro- autocondensation of two or more MEK mole-
duced by use of concentrated sulfuric acid as a cules. In this case, the extent of autocondensation
catalyst via an indirect route. The resulting in- is still much lower compared to that of the
termediate mono- or di-sec-butylsulfate of the acetone process. Dehydration of SBA, which
first reaction step is hydrolyzed in a second results in n-butene formation, is practically not
reaction step. detectable.
The gas hourly space velocity (GHSV) of The MEK is purified in three consecutive
Deutsche Texacos dehydrogenation technology distillation steps, which operate under
is roughly 1 Nm3 per liter catalyst and hour. At a normal atmospheric pressure. In the first step,
relatively high selectivity far above 90 %, a an azeotropic MEKwater stream is taken as
conversion of approximately 90 % can be overhead stream, which is purified batchwise
achieved. Every 34 month time-on-stream, in a separate distillation column. The second
the catalyst has to be reactivated with air at column gives the desired pure MEK (with a
higher temperatures to get back the initial rate typical purity over 99 %) and SBA mixed with
of reaction. These operational facts make this the higher ketones as a bottom stream. In the last
process technology still economically highly distillation step, the unconverted SBA is distilled
attractive. off (overhead stream) and is sent back to the
Liquid sec-butyl alcohol is vaporized in an process feed tank. The bottom products are the
evaporator. The gaseous alcohol stream is sent to higher ketones formed as byproducts during
a multitube reactor, where the dehydrogenation synthesis.

Figure 1. Gas-phase dehydrogenation of sec-butyl alcohol (Deutsche Texaco AG process) a) Multitube reactor; b) Evaporator;
c) Condenser; d) Separator; e) Refrigerator; f) Distillation column system
436 2-Butanone Vol. 6

Reference
Table 4 summarizes all currently known pro-
cess technologies for the MEK production

[46]
[47]
[40]
[48]
[49]
[42]

[43]

[44]
[44]
by gas-phase dehydrogenation of sec-butyl
alcohol.

Yield, mol %

93 94

73 77
97.8c
4.2. MEK as a Byproduct of the

79.2
80

90

90
Fischer-Tropsch Coal-to-Liquid
Process

Selectivity,

93 96

86 92
mol %
In the Fischer-Tropsch process, carbon monox-

96.3
100
100

63b
97
99
ide and hydrogen the synthesis gas are cat-
alytically converted into liquid hydrocarbons
with a large spectrum of different chain

Conversion, %

92.5 93.5
lengths and a remarkable amount of several

96 97

88 93

81 85
byproducts.

57.3a
Developed in the 1920s by the German re-

80

96
90
searchers FRANZ FISCHER and HANS TROPSCH, this
process is commercially used and improved by
Pressure, MPa
South Africans SASOL Ltd. since 1955 to pro-

0.1 0.3
duce synthetic fuels from coal.
In a two-step process technique, mineral coal
0.3

0.6
0.6
is gasified to produce synthesis gas, which is
thereafter extensively purified by absorption in
Temperature,  C

scrubber systems (using the Rectisol technolo-


gy). The purified synthesis gas is catalytically
270 320

converted into hydrocarbons (! Coal


Table 4. Process technologies for MEK production by gas-phase dehydrogenation of 2-butanol

Liquefaction).
400
413
390

300
260

180

358
286
Besides the main products, i.e., olefins, syn-
thetic fuel, and waxes, a large variety of water-
H2O content,

soluble oxygenates are achieved as byproducts


with a selectivity of 3 - 6 % in the reaction water
vol %

stream [25].
90.4
0
0
0
0

0
0

Via traditional separation technologies, these


oxygenates (alcohols, organic acids, aldehydes,
22 % Cu, 8 % BaCrO4, 2 % Cr2O3,

MEK, and other ketones) are purified to high-


value solvent products.
60 % Cu, Cr2O3, MgO, 12 %

0.5 % Na2O, 61 % SiO2

5 % Cu, 5 % Cr/Al2O3
ZnO/Na2CO3/Al2O3

4.3. Liquid-Phase Oxidation


0.05 % Pt/Al2O3
SiO2, 10 % H2O
CuO/NaF/SiO2

of n-Butane
ZnO/Bi2O3

CuO/CrO
Catalyst

bronze

2-Butanone is a byproduct in the liquid-phase


Relative to di-sec -butyl ether.
Relative to sec-butyl alcohol.

oxidation of n-butane to acetic acid. Auto-oxi-


dation or direct oxidation of n-butane takes place
Esso Research & Eng.

in the liquid phase via a radical reaction pathway


Knapsack Griesheim

to give MEK as an intermediate product, which,


upon further oxidation, forms MEK hydroperox-
Veba-Chemie

Shell-Chemie
Shell-Chemie

Total yield.
Standard Oil

Maruzen Oil

Toyo Rayon
Ruhrchemie

ide that is subsequently cleaved into two mole-


Company

cules to give the desired acetic acid as the end


product.
a
b
c
Vol. 6 2-Butanone 437

The continuous plug-flow process developed The first attempt to overcome the negative
by Union Carbide Corp. allows the partial col- effect was described in 1987 according to [53].
lection of MEK intermediate [50]. MEK and By adding cumene hydroperoxide (CHP) as an
acetic acid (mass ratio 0.15/1.00.23/1.0) are initiator to sec-butylbenzene, the oxidation reac-
obtained by noncatalyzed liquid-phase oxida- tion rate could be increased to some extent, so
tion at 180 C and 5.3 MPa with some back- that the negative impact of the byproduct forma-
mixing. tion is reduced. Later, it was patented by Phe-
Continuous oxidation under plug-flow condi- nolchemie [54] to add only cumene in minor
tions at 150 C, 6.5 MPa, and a residence time of percentages (i.e., between 5 and 15 wt %), which
2.7 min forms MEK and acetic acid at mass allows the formation of acetophenone as the main
ratios of up to 3/1 [50]. byproduct.
Celanese Corp. uses acetic acid as a solvent According to Shells investigations, the de-
with cobalt acetate and sodium acetate as a crease in reaction rate in the oxidation of sec-
homogeneously dissolved oxidation catalyst butylbenzene is caused by the formation of
system [51]. It is a batch process performed cleaved products as radical scavenger in the
between 160 and 165 C at 5.7 MPa. MEK reaction mixture in the ppm range, i.e., the
and acetic acid are obtained in a mass ratio of formation of formic acid, acetic acid, and
0.4/1.0. phenol. To overcome this negative effect on the
The Celanese plant using this technology still rate of reaction, the following options are sug-
runs in the USA (Pampa, Texas). gested [29]:

. Using a mixture of sec-butylbenzene and cu-


4.4. Oxidation of sec-Butylbenzene mene to build up some initial amounts of CHP
According to the Hock Phenol in the first reaction step, which acts as an
Synthesis initiator
. Reducing the amounts of methanol or ethanol
Shells combined phenolacetoneMEK tech- created as cleaved products in recycle streams,
nology (SPAM technology) is based on oxidizing which lowers the formation of the above-men-
a mixture of sec-butylbenzene and cumene to the tioned scavenger acids
respective hydroperoxide molecules, which . Adding an aqueous solution of ammonia to
thereafter are cleaved traditionally with an inor- such extent that the acids can form their am-
ganic acid (preferable sulfuric acid) to give the monium salts, whereas phase splitting has to be
desired products, i.e., a mixture of phenol plus avoided.
MEK and acetone. The crude ketone stream is
separated by distillation from the phenol and is A schematic diagram of the reaction and
further purified to the desired pure ketone purification steps according to [29] is depicted
components. in Figure 2.
The catalytic cleavage of sec-butylbenzene
hydroperoxide (sBHP) with an inorganic acid to
produce phenol plus MEK has been well-known 4.5. Direct Oxidation of n-Butenes
for many years. It is described and patented (Hoechst-Wacker Process)
in [52].
Although MEK compared to acetone is the In the direct oxidation of n-butenes according to
industrially more important ketone, this alterna- the Hoechst-Wacker process, oxygen is trans-
tive route has not been commercialized because ferred in a homogeneous phase onto n-butenes
of a major problem which occurs in the oxidation using a redox salt pair, PdCl2/2 CuCl [55, 56].
step. The rate of reaction for the autocatalytic The salt pair is subsequently re-oxidized.
oxidation of sec-butylbenzene is several times
slower than that of cumene. Therefore, side
reactions have a negative impact on the overall
yield of the desired products.
438 2-Butanone Vol. 6

Table 5. ASTM specifications for MEK [65]

Specification
Type I Type II method

Commercial regular urethane


reference grade
Acidity, wt % max. 0.005 max. 0.003 D 1613
Alcohol, wt % max. 0.5 D 2804
Color, Pt-Co scale max. 10 max. 10 D 1209
Distillation range D 1078
(760 mm Hg)
Initial boiling min. 78.5 min. 78.5
point,  C
Dry point,  C max. 81.0 max. 81.0
Nonvolatile matter, max. 5 max. 5 D 1353
mg/100 mL
Purity, wt % min. 99.5 min. 99.5 D 2804
Apparent specific D 268 or
gravity D 4052
20/20 C or 0.8050.807 0.8050.807
25/25 C 0.8010.803 0.8010.803
Water, wt % max. 0.2 max. 0.05 D 1364

Figure 2. Process for co-producing phenol and methyl ethyl


ketone (Shell Chemicals, according to [29]) A long permanganate time according to
ASTM D 1363 indicates high purity.
Storage life of MEK is limited because of
n-Butenes can be converted into the following discoloration. Since MEK is somewhat hygro-
reaction products (conversions of up to 95% are scopic, water is absorbed from the air.
attained): Carbon steel, stainless steel (CrNi and CrNiMo),
and aluminum containers are suitable for storage
and transportation [66, 67]. Carbon steel or contain-
ers with zinc silicate lining are recommended for
Reaction products: Selectivities, mol %
MEK 86 long-term storage. Only a few plastics such as poly
n-Butanal 4 (tetrafluoroethylene) (PTFE), ethylenepropene
Chlorinated products 6 diene terpolymer (EPDM), ethylenechlorotri-
Carbon dioxide 1 fluoroethylene (ECFTFE), perfluoroalkoxy (PFA)
polymers, butyl rubber, or polyamide are compati-
The main disadvantages are: formation of ble for gasket materials [67].
chlorinated butanones and n-butanal and corro- The following regulations for transportation of
sion caused by free acids. MEK must be observed. Classification and defi-
The Maruzen process is similar [57, 58]. nitions of classes of dangerous goods see [68].
Oxygen is transferred by an aqueous solution of
palladium sulfate and ferric sulfate. Other pro- Land transport ADR/RID
cesses employing the same oxygen transfer prin- UN number 1193
ciple were developed by Consortium f ur Elek- Class 3
Packaging group II
trochemie [59] and Eastman Kodak [60]. For Inland waterways transport ADNR
further processes, see [6164]. UN number 1193
Class 3
Packaging group II
Marine transport IMDG
5. Quality, Storage, Transportation UN number 1193
Class 3.2
MEK is industrially produced in high quality Packaging group II
Air transport ICAO/IATA
according to ASTM D 740, DIN 53247 and BS UN number 1193
1940. Class 3
ASTM standard specifications for MEK are Packaging group II
given in Table 5. USA 49 CFR 172.101
Vol. 6 2-Butanone 439

6. Uses portance. Methyl ethyl ketone peroxide is used as


a polymerization initiator for unsaturated polye-
MEK is an important solvent with properties sters. The perfume industry reacts MEK with
similar to those of acetone. MEK has the follow- citral to obtain perfume components such as
ing advantages in comparison to other solvents methylpseudoionone. Since 1962 MEK is per-
with comparable rates of evaporation: very high mitted as an alcohol denaturant in the Federal
power of dissolution, high ratio of dissolved Republic of Germany (by decree of Bundesmo-
matter/viscosity, miscibility with a large number nopolverwaltung in Offenbach).
of hydrocarbons without impairing the solids
content or viscosity, favorable volume/mass ratio
due to its low density. 7. Economic Aspects
The following natural substances, plastics,
and resins can be dissolved in MEK: rosin, ester Global demand of MEK was published to be
resins, pentaerythritol ester resins, Congo ester, 950 000 t/a in 2001 [72]. The annual growth of
dammar (dewaxed), nitrocellulose, low-molecu- the market is estimated to be around 3 % after a
lar cellulose acetate, cellulose acetobutyrate, decline in 2001. The withdrawal of MEK from
cellulose acetostearate, methyl cellulose, epoxy the HAP list, as well as the economic growth in
resins, nearly all alkyd and phenolic resins, poly China will positively impact MEK consumption
(vinyl acetate), vinyl chloride/acetate mixed figures.
polymerizates, viny lchloride/vinylidene chlo- Table 6 shows estimated sales volumes per
ride mixed polymerizates, coumarone indene application [72].
resins, sulfonamide resins, cyclohexanone re- The approximated breakdown of worldwide
sins, acrylic resins, polystyrene, chlorinated rub- consumption of 1  106 t MEK in 2001
ber, polyurethane. amounted to 170 000 t for Western Europe,
Cellulose triacetate, high-molecular cellulose Eastern Europe 10 000 t, North America
acetate, poly(vinyl chloride), poly(vinyl butyral), 200 000 t, Central and South America
polysulfide rubber cannot be dissolved in MEK. 30 000 t, China 220 000 t, Japan 140 000 t,
Shellac is only partially soluble. Asia 200 000 t (except China and Japan), and
Other areas of application [69, 70] are pro- 30 000 t in other regions.
duction of paints, lacquers, varnishes, paint thin- MEK is also available under the following
ners and removers, adhesives, cements, sealants, names:
magnetic tapes, artificial leather, transparent pa- Butanone, 2-butanone, methylacetone, meet-
per, printing inks, cleaner for electronic equip- co, butan-2-one.
ment, cosmetics, pharmaceuticals; degreasing of
metal surfaces; extraction of fats, oils, waxes,
natural resins; dewaxing of mineral oils [71] or 8. Toxicology and Occupational
lube oils. Additionally, it is used as synthetic Health
flavoring agent in foods and pharmaceuticals and
as a sterilizer for bacterial spores on surgical 8.1. Occupational Exposure
instruments, hypodermic needles and syringes,
and dental instruments; manufacturing of smoke- The NIOSH (National Institute for Occupational
less powder. Safety and Health) National Occupational Expo-
In contrast to its uses as a solvent, use as a sure Survey (1981-1983) reported an estimated
chemical feedstock is of minor importance de-
spite the great number of possible reactions;
Table 6. Volumes per application (2001)
however, condensation with formaldehyde to
obtain methyl isopropenyl ketone, autoconden- %
sation to form ethyl amyl ketone, and mixed
Paints, lacquers, aluminum foil lacquers 63
condensation with acetone to obtain methyl amyl Adhesives 11
ketone are of interest. MEK is used to produce Chemical industry (incl. sound carrier) 12
perfumes, antioxidants, catalysts, peroxides, and Dewaxing 5
Printing inks 2
diacetal. Methyl ethyl ketoxime, used as an
Miscellaneous 7
antiskinning agent in lacquers, is of minor im-
440 2-Butanone Vol. 6

1 447 456 workers exposed to MEK, of which arm, MEK was detected within 30 s in the ex-
245 372 were female. In occupational settings, haled air and a maximum concentration was
the primary routes of exposure to MEK are reached in 10-15 min Permeability rates were
inhalation and skin contact. [73]. For different 0.46 and 0.59  106 g cm2 min1 for in vivo
workplaces (e.g., electronic parts plant, plants studies and 88.3  106 g cm2 min1 for in
manufacturing or applying surface coatings, shoe vitro studies. The dermal uptake to MEK from
factories) the maximum MEK concentration was the vapor phase contributes approximately 3-
376 ppm (shoe factory). Most values were much 3.5% of the total body burden [75].
lower [74]. Lesser amounts of MEK are lost to the
air with concurrent worker exposure during man-
ufacture, shipping, repacking, and preparation of 8.2.2. Distribution
coatings and adhesives. Industrial exposure from
contact with liquid MEK does not appear an In MEK exposed workers, the MEK blood levels
important problem [74]. were significantly correlated with the environ-
mental MEK concentrations, which indicates
rapid transfer from the lungs to the blood. MEK
8.2. Toxicokinetics and Metabolism tissue/air solubility ratio for human kidney,
liver, muscle, lung, heart, fat, and brain revealed
8.2.1. Absorption similar solubility in all these tissues, with the
tissue/air ratio ranging from 147 (lung) to 254
8.2.1.1. Oral Exposure (heart). MEK does not accumulate in fatty tis-
sues in humans. Blood/tissue solubility ratios
MEK is absorbed by the gastrointestinal tract for several tissues approach unity. Thus, MEK is
following oral exposure in humans. Experimen- not expected to accumulate in any particular
tal data from rodents indicate that orally admin- tissue, which is confirmed in animal studies
istered MEK is absorbed from the gastrointesti- [75].
nal tract and rapidly eliminated. Oral adminis-
tration to rats resulted in a mean peak plasma
concentration after 4 h that decreased to less than 8.2.3. Metabolism
1/10 of the peak value after 18 h [75].
Metabolism of MEK in humans and experimen-
8.2.1.2. Inhalation Exposure tal animals is very similar. The majority of MEK
is metabolized to 3-hydroxy-2-butanone, which
MEK is well absorbed during inhalation expo- is subsequently metabolized to 2,3-butanediol.
sure because of its high blood/air solubility ratio. A small portion is converted to 2-butanol. In
In MEK exposed workers, the alveolar air con- humans exposed to MEK in air, 2-butanol and
centration was highly correlated with the envi- 2,3-butanediol were identified in serum, while
ronmental air concentration and averaged 30% of 3-hydroxy-2-butanone and 2,3-butanediol have
the latter. Pulmonary retention rates are between been identified as urinary metabolites of MEK. In
5 and 70 % (MEK between < 100 ppm and animal studies, the majority of MEK is oxidized
300 ppm in air) [75]. by the cytochrome P450 monooxygenase sys-
tem. After exposure, 2-butanol is metabolized
8.2.1.3. Dermal Exposure to MEK rapidly. Ultimately, 2-butanol and
MEK are metabolized through the same inter-
The percutaneous absorption of MEK is rapid. mediates [75].
MEK was present in the exhaled air of humans
within 3 min after application to normal skin of
the forearm. A plateau concentration was 8.2.4. Elimination and Excretion
reached within 2 h. The absorption rate was
slower when MEK was applied to the dry skin, In human studies involving acute inhalation
where a plateau was attained in 4-5 h. By con- exposure, the urinary excretion of MEK and
trast, after absorption of MEK to the moist fore- metabolites and the exhalation of unchanged
Vol. 6 2-Butanone 441

MEK account for only a small percentage of the 8.2.6.2. Inhalation Exposure
absorbed dose. The remainder of the absorbed
dose is rapidly transformed to carbon dioxide and Evidence for neurotoxic effects following inha-
water through intermediary metabolic pathways lation exposure to MEK is limited to a small
[74]. Nevertheless, unchanged MEK in urine is number of case reports of neurological im-
used as a marker of exposure since strong posi- pairment in occupationally-exposed humans and
tive correlations have been reported between in one study of problematic design reporting
MEK levels in urine and MEK levels in air increased incidence of subjectively reported neu-
[75, 76]. rological symptoms in MEK-exposed workers.
Behavioral effects and narcosis after single or
limited number of inhalation experiments in rats
8.2.5. Mechanism of Action
and mice were observed. However, several well-
conducted studies provided no evidence for neu-
Ketone solvents are odorous and slightly irritat-
rological effects of MEK in animals.
ing to mucuos membranes and the skin [77]. The
Developmental effects following exposure to
range of acceptable odor thresholds concentra-
MEK have not been described in humans. In
tions for MEK varies from 285 ppm. The odor
rodents MEK caused developmental toxicity in
quality is sharp and sweet [78]. Information on
the presence of maternal toxicity in rats and mice
the mechanisms of toxic action of MEK is rare.
and in one study in rats in the absence of maternal
Very high inhalation concentrations (500-
toxicity. Inhalational studies provide evidence
10 000 ppm) caused pulmonary vasoconstric-
for developmental effects (decreased fetal
tions and hypertension in animals. Interactions
weight, increased incidence of certain skeletal
leading to the potentiation off effects, particular-
variants) in rats and mice exposed to 3000 ppm
ly neurotoxicity, by other toxic substances con-
MEK, 7 h per day during gestation, but not at
stitute the main hazard of MEK [74]. Studies
1000 ppm and lower.
regarding the induction of the mixed function
Available data provide no clear evidence for
oxidase system showed contradictory results
other systemic effects resulting from inhalation
[79]. The toxicity of MEK may be a result of
exposure to MEK. A subchronic inhalation study
exposure to concentrations that exceed the ca-
of MEK found no persistent body weight
pacity for detoxification by a saturable enzyme
changes, gross behavioral changes or histologi-
mechanism. The mechanism by which MEK
cal changes in major tissues and organs in rats
potentiates the neurotoxicity of hexacarbon sol-
exposed 6 h per day, 5 days per week for 90
vents is not entirely clear, although it appears to
days to concentrations as high as 5000 ppm.
involve the biotransformation of these solvents to
Some changes in organ weight and clinical pa-
their toxic metabolites [75].
thology parameters were observed; however,
these were not supported by histological changes.
8.2.6. Toxic Effects There is no evidence for portal of entry effects
following inhalation exposure to MEK. MEK
8.2.6.1. Oral Exposure exposures up to 200 ppm for up to 4 h did not
cause irritations. Exposure to 300 ppm MEK was
Oral exposure of humans to MEK in form of an reported as intolerable. Nasal irritation was noted
accidental ingestion of MEK had no persistent in rats exposed to 6000 ppm MEK for 15 weeks,
adverse health effects. LD50 values for adult mice but not in other studies involving somewhat
and rats are 2-6 g per kilogram body weight, lower exposure concentrations. No exposure-
with death occurring within 1-14 days following related upper respiratory irritation could be eval-
a single oral dose. The lowest, nonlethal acute uated in rats exposed up to 5000 ppm MEK for
oral dose producing an adverse effect (renal 90 days. In addition, respiratory irritation was not
tubule necrosis) is 1082 mg/kg MEK in corn oil. reported in dams exposed to 3000 ppm MEK,
Information on the effects of MEK following 7 h per day for days 6-15 of gestation. In preg-
repeated oral exposure is limited to data for 2- nant rodents developmental effects are the most
butanol (a metabolic precursor of MEK) and for sensitive, toxicologically relevant endpoints for
3-hydroxy-2-butanone (a metabolite). inhalation exposure to MEK.
442 2-Butanone Vol. 6

The few available epidemiological studies of Although MEK appears a relatively safe or-
MEK-exposed workers provide no clear evi- ganic solvent, its use in combination with other
dence of cancer hazard, but the studies are gen- solvents, in particular haloalkanes or unbranched
erally inadequate to discern an association be- aliphatic hydrocarbons, should be avoided. All
tween MEK exposure and an increased incidence necessary precautions have to be taken to ensure
of cancer. Epidemiological evidence is based on that workers are not exposed to both MEK and
a small number of site-specific deaths, only, and solvents whose toxicity is potentiated by MEK
studies are confounded by exposure to multiple [74]. In the case of accident spills, personnel
chemicals. A case control study examining the should wear protective clothing including
association between paternal exposures to sever- respiratory protection. Contaminated clothing
al solvents, including MEK, and childhood leu- should be removed promptly, and the exposed
kemia is exploratory in scope and cannot be used areas of the body should therefore be thoroughly
to reliably support the existence of any such flushed with water. MEK may be absorbed
association. Although there is some suggestion through the skin. Therefore, caution should be
of increased risk for certain cancers (including exercised to avoid repeated or prolonged skin
bone and prostate) involving multiple solvent contact [78].
exposure that include MEK, there is no clear Under normal occupational conditions, ambi-
evidence for a relationship between these cancers ent MEK air concentrations and urinary concen-
and MEK exposure alone. There are no chronic trations of MEK correlate significantly. There-
toxicity studies or cancer bioassays of inhalation fore, a biological limit value (BLV) could be
exposure to MEK in experimental animals. evaluated. Given an air concentration of
MEK is not mutagenic in a number of con- 200 ppm MEK, the individual urinary MEK
ventional short-term assays for genotoxic poten- concentration may range from 2.15.4 mg/L.
tial [75]. Urinary MEK concentration may be measured
using headspace gas chromatography [76].
8.2.6.3. Occupational Health

Chronic co-exposure to MEK and either un- 8.2.6.4. Regulations


branched aliphatic hexacarbon or haloalkane
solvents represents a significant potential occu- The OSHA PEL, the NIOSH REL TWA and the
pational hazard. Serious toxic effects could occur ACGIH TLV-TWA for MEK as well as the
[74]. Symptoms produced by an overexposure threshold limit value (MAK value) in Germany
include irritation of the eyes, nose, and throat, are 200 ppm [81, 82]. The ACGIH TLV-STEL
headache, nausea, vertigo, uncoordination, cen- and the NIOS REL STEL are 300 ppm [78].
tral nervous system depression, narcosis, and The biological limit value (BAT value) for
cardiorespiratory failure. Recovery is usually MEK in urine is 5 mg MEK per liter in Germany
rapid and without residual toxic effects [78]. The [76]. Potential exposures to MEK emitted
potential exists for increased susceptibility to from industrial processes may not reasonably be
neurotoxicity, hepatotoxicity, and renal toxicity anticipated to cause human health or environ-
following exposure to MEK in combination with mental problems. Therefore, MEK was
certain other solvents. MEK potentiates the neu- removed from the list of hazardous air pollutants
rotoxicity of hexacarbon solvents (n-hexane, (HAPs) [83].
methyl-n-butyl ketone, and 2,5-hexanedione)
and the liver and kidney toxicity of haloalkane
solvents. Although the mode by which MEK References
potentiates the neurotoxicity of hexacarbon sol-
vents is not entirely clear, it appears to involve
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1000 ppm) [75, 80]. 3 J. Mellan: Ketones, Chemical Publ., New York 1968.
Vol. 6 2-Butanone 443

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444 2-Butanone Vol. 6

summary information on the integrated risk information 83 US Environmental Protection Agency (EPA), Federal Reg-
system (IRIS). Washington, DC 2003. ister: December 19, 2005, Vol. 70, Number 242, Rules and
76 DFG: 2-Butanon in H. Drexler, H. Greim (eds.): Bio- Regulations, pp. 75047 75059, Washington, DC 2005.
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77 J. Liira, V. Riihimaki, P. Pfaffli: Kinetics of methyl ethyl
ketone in man: absorption, distribution and elimination in A. E. Comyns: Encyclopedic Dictionary of Named Processes
inhalation exposure, Int. Arch. Occup. Environ. Health in Chemical Technology, 3rd ed., CRC Press, Boca Raton,
60 (1988) 195 200. FL 2007.
78 Pattys Toxicology, Fifth Edition, Volume 6, Morgott, T. S. S. Dikshith: Safe Use of Chemicals, CRC Press, Boca
Topping & ODonoghue, pp. 117 156, 2001. Raton, FL 2009.
79 R. S. H. Yang: The toxicology of methyl ethyl ketone S. Ebnesajjad (ed.): Adhesives Technology Handbook, 2nd
Res. Rev. 97 (1986) 121 143. ed., William Andrew Publ., Norwich, NY 2008.
80 J. Noraberg, P. Arlien-Soborg: Neurotoxic interaction of C. M. Hansen: Hansen Solubility Parameters, 2nd ed., CRC
industrially used ketones, Neurotoxicology 21 (2000) Press, Boca Raton, FL 2007.
409 418. P. Patnaik: A Comprehensive Guide to the Hazardous Prop-
81 National Institute for Occupational Safety and Health erties of Chemical Substances, 3rd ed., Wiley, Hoboken,
(NIOSH): Pocket Guide to Chemical Hazards, US De- NJ 2007.
partment of Health and Human Services, Public Health E. M. Petrie: Epoxy Adhesive Formulations, McGraw-Hill,
Service, Centers for Disease Control and Prevention. New York, NY 2006.
Cincinnati, OH, 2005. P. A. Schweitzer: Paint and Coatings, CRC Taylor & Francis,
82 DFG: 2-Butanon in H. Greim (ed.): Gesundheitssch a- Boca Raton, FL 2006.
dliche Arbeitsstoffe. Toxikologisch-arbeitsmedizinische Z. W. Wicks, F. N. Jones, S. P. Pappas, D. A. Wicks: Organic
Begr undungen von MAK-Werten (Maximale Arbeitsplatz- Coatings, 3rd ed., Wiley-Interscience, Hoboken, NJ
konzentrationen), Lfg. 30, Wiley-VCH, Weinheim, 2000. 2007.