Acetaldehyde 1

Acetaldehyde
Marc Eckert, Wacker Chemie AG, Werk Burghausen, Germany
Gerald Fleischmann, Wacker Chemie AG, Werk Burghausen, Germany (Chap. 1, 2, 3, 4, 5, 6, 7 and 8)
Reinhard Jira, Wacker Chemie AG, Werk Burghausen, Germany (Chap. 1, 2, 3, 4, 5, 6, 7 and 8)
Hermann M. Bolt, Institut für Arbeitsphysiologie an der Universität Dortmund, Dortmund, Germany
(Chap. 9)
Klaus Golka, Institut für Arbeitsphysiologie an der Universität Dortmund, Dortmund, Germany (Chap. 9)

1. Introduction . . . . . . . . . . . . . . . 1 4.3.3. Isomerization of Ethylene Oxide . . . 10

2. Physical Properties . . . . . . . . . . . 2 4.4. Production from C1 Sources . . . . . 11
3. Chemical Properties and Uses . . . . 3 4.5. Production from Hydrocarbons . . 11
3.1. Addition Reactions . . . . . . . . . . . 3 5. Quality and Analysis . . . . . . . . . . 11
3.2. Derivatives of Aldol Addition . . . . 3 6. Storage and Transportation . . . . . 11
3.3. Reaction with Nitrogen Compounds 3 6.1. Storage . . . . . . . . . . . . . . . . . . . 11
3.4. Oxidation . . . . . . . . . . . . . . . . . 4 6.2. Transportation . . . . . . . . . . . . . . 12
3.5. Reduction . . . . . . . . . . . . . . . . . 4 6.3. Other Regulations . . . . . . . . . . . 12
3.6. Miscellaneous Reactions . . . . . . . 4
7. Economic Aspects . . . . . . . . . . . . 12
3.7. Consumption . . . . . . . . . . . . . . . 4
8. Polymers of Acetaldehyde . . . . . . 13
4. Production . . . . . . . . . . . . . . . . 4
4.1. Production from Ethanol . . . . . . . 5 8.1. Paraldehyde . . . . . . . . . . . . . . . 13
4.2. Production from Acetylene . . . . . . 6 8.2. Metaldehyde . . . . . . . . . . . . . . . 13
4.3. Production from Ethylene . . . . . . 7 8.3. Polyacetaldehyde . . . . . . . . . . . . 14
4.3.1. Direct Oxidation of Ethylene . . . . . 7 9. Toxicology and Occupational Health 14
4.3.2. Acetaldehyde as Byproduct . . . . . . 10 10. References . . . . . . . . . . . . . . . . . 15

1. Introduction acetic acid between 1914 and 1918 in Germany

(Wacker-Chemie and Hoechst) and in Canada
Acetaldehyde (ethanal), CH3 CHO [75-07-0], (Shawinigan).
was observed in 1774 by Scheele during re- Acetaldehyde is an intermediate in the
action of black manganese dioxide and sulfuric metabolism of plant and animal organisms, in
acid with alcohol. Its constitution was explained which it can be detected in small amounts.
in 1835 by Liebig who prepared pure acetalde- Larger amounts of acetaldehyde interfere with
hyde by oxidation of ethanol with chromic acid biological processes. As an intermediate in al-
and designated this product “aldehyde,” a con- coholic fermentation processes it is present in
traction of the term “alcohol dehydrogenatus.” small amounts in all alcoholic beverages, such
Acetaldehyde is a mobile, low-boiling, as beer, wine, and spirits. Acetaldehyde also has
highly flammable liquid with a pungent odor. been detected in plant juices and essential oils,
Because of its high chemical reactivity, acet- roasted coffee, and tobacco smoke.
aldehyde is an important intermediate in Commercial production processes include
the production of acetic acid, acetic anhy- dehydrogenation or oxidation of ethanol, addi-
dride, ethyl acetate, peracetic acid, butanol, 2- tion of water to acetylene, partial oxidation of
ethylhexanol, pentaerythritol, chlorinated acet- hydrocarbons, and direct oxidation of ethylene.
aldehydes (chloral), glyoxal, alkyl amines, pyri- In the 1970s, the world capacity of this last pro-
dines, and other chemicals. The first commercial cess, the Wacker-Hoechst direct oxidation, in-
application was the production of acetone via creased to over 2×106 t/a. However, the impor-

c 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a01 031.pub2
2 Acetaldehyde
Heat capacity of liquid
tance of acetaldehyde as an organic intermediate
cp (l) at 0 ◦ C 2.18 J g−1 K−1
is now steadily decreasing, because new pro- at 20 ◦ C 1.38 J g−1 K−1
cesses for some acetaldehyde derivatives have For further values between −80 ◦ C (cp = 1.24 J g−1 K−1 )
been developed, such as the oxo process for and +120 ◦ C (cp = 1.50 J g−1 K−1 ), see [17].
Heat capacity of vapor
butanol and 2-ethylhexanol and the Monsanto
cp (g) at 25 ◦ C, 101.3 1.24 J g−1 K−1
process for acetic acid. In the future, new pro- kPa
cesses for acetic anhydride (Halcon, Eastman, For dependence on temperature (nonlinear) between 0 ◦ C (cp
Hoechst), for vinyl acetate (Halcon), and for = 1.17 J g−1 K−1 ) and 1000 ◦ C (cp = 2.64 J g−1 K−1 ), see
[17].
alkyl amines (from ethanol) will diminish the
use of acetaldehyde as a starting material. cp /cv (= κ) at 30 ◦ C, 1.145 [18]
101.3 kPa
Thermal conductivity
of liquid at 20 ◦ C 0.174 J m−1 s−1 K−1 ;
for more values, see
2. Physical Properties [19]
of vapor at 25 ◦ C 1.09×10−2 J m−1 s−1 K−1
Acetaldehyde, C2 H4 O, M r 44.054, is a color- for further values,
see [20].
less liquid with a pungent, suffocating odor that Cubic expansion 0.00169
is slightly fruity when diluted. coefficient per K (0 –
◦
20 C)
Heat of combustion of 1168.79 (1166.4 [12]) kJ/mol
bp at 101.3 kPa 20.16 ◦ C liquid at constant p
mp –123.5 ◦ C Heat of solution in water 17 906 J/mol
Critical temperature t crit 181.5 ◦ C (infinite dilution)
other values 187.8 ◦ C [12], 195.7 ◦ C [13] Latent heat of fusion 3246.3 J/mol
Critical pressure pcrit 6.44 MPa Latent heat of 25.73 kJ/mol
other values 5.54 MPa [12], 7.19 MPa [13] vaporization at 20.2 ◦ C
Relative density d4 = 0.8045−0.001325·t (t in ◦ C)
t
other values 27.2 [21], 30.41, 27.71 [12], 26.11 [22]
[3] kJ/mol
Refractive index ntD = 1.34240−0.0005635·t (t in For dependence on temperature (nonlinear) between -80 ◦ C
◦
C) [14] (32.46 kJ/mol) and 182 ◦ C (0 kJ/mol), see [17].
Molar volume of the gas Heat of formation ∆H from the elements at 25 ◦ C for gaseous
at 101.3 kPa and 23.40 L/mol acetaldehyde
20.16 ◦ C −166.47 (−166.4 [21]) kJ/mol
◦
at 25.0 C 23.84 L/mol For dependence of heat of formation for gaseous and liquid
For dependence on T (293.32 – 800 K) and p (0.1 – 30 acetaldehyde, and enthalpy of vaporization on temperature up to
MPa), see [15]. 800 K and 30 MPa, see [15].
Specific volume of the Gibbs free energy of formation ∆G from elements
vapor at 25 ◦ C for gaseous −133.81 kJ/mol
at 20.16 ◦ C 0.531 m3 /kg acetaldehyde
at 25.0 ◦ C 0.541 m3 /kg other values 133.72 [12], 132.9 [21] kJ/mol
Vapor density (air = 1) 1.52 Entropy for gaseous acetaldehyde
◦
Vapor pressure at 25 C 265.9 J mol−1 K−1
t, ◦ C −20 −0.27 5.17 14.76 50 100 Entropy for liquid acetaldehyde
p, kPa 16.4 43.3 67.6 82.0 279.4 1014.0 at 20.16 ◦ C 172.9 J mol−1 K−1
Entropy of vaporization
For further values between −60 and +180 ◦ C, see [14]
at 20.16 ◦ C 91.57 J mol−1 K−1
Viscosity of liquid η First ionization potential 10.5 eV
at 9.5 ◦ C 0.253 mPa · s Dissociation constant at 0.7×10−14 mol/L
at 20 ◦ C 0.21 mPa · s 0 ◦C (H3 CCHO− H2 CCHO + H+ )
Viscosity of vapor η For the second virial coefficient of the equation of state for gaseous
at 25 ◦ C 86×10−4 mPa · s acetaldehyde at 31 ◦ C, 66 ◦ C, and 85 ◦ C, see [23].

◦
For further values between 35.0 and 77.8 C and between 0.13 Acetaldehyde is completely miscible with
and 0.40 kPa, see [16].
Surface tension γ at 21.2×10−2 mN cm−1
water and most organic solvents. It forms no
20 ◦ C azeotrope with water, methanol, ethanol, ace-
Dipole moment (gas 2.69 ± 2 % D [12] tone, acetic acid, or benzene. Binary azeotropes
phase)
are formed with butane (bp −7 ◦ C, 84 wt % of
Dielectric constant butane) and diethyl ether (bp 18.9 ◦ C, 23.5 wt %
of liquid at 10 ◦ C 21.8
of vapor at 20.16 ◦ C, 1.0216
of ether).
101.3 kPa
 Acetaldehyde 3

Other Physical Data. Compressibility and forms crystalline acetaldehyde ammonia. Acet-
viscosity at higher pressure are given in [24], va- aldehyde and hydrocyanic acid react to give lac-
por pressure of aqueous acetaldehyde solutions tonitrile (α-hydroxypropionitrile), a possible in-
in [25]. For solubility of carbon dioxide, acety- termediate in acrylonitrile production [30].
lene, and nitrogen in acetaldehyde, see [11]; for Acetaldehyde reacts with acetic anhydride to
freezing points of aqueous acetaldehyde solu- give ethylidene diacetate, an intermediate in the
tions, see [11]; for vapor – liquid equilibria of vinyl acetate process of Celanese Corp. [31] (→
binary systems of acetaldehyde with water, eth- Vinyl Esters).
anol, acetic acid, and ethylene oxide, see [26,
pp. 392, 561, 565, and 570], with vinyl acetate,
see [27]. 3.2. Derivatives of Aldol Addition
Two molecules of acetaldehyde combine in
Safety Data. Flash point (Abel – Pensky; the presence of alkaline catalysts or dilute
DIN 51 755; ASTM 56 – 70) −20 ◦ C (−40 ◦ C acids at room temperature or with mod-
according to the safety regulations of the Berufs- erate heating to form acetaldol [107-89-1],
genossenschaft der Chemischen Industrie, Fed- CH3 CH(OH)CH2 CHO. At increased temper-
eral Republic of Germany). Ignition tempera- atures, water is cleaved easily from this ac-
ture (DIN 51 794; ASTM D 2155 – 66) 140 ◦ C; etaldol, forming crotonaldehyde (→ Aldehydes,
for ignition retardation when injected into a hot Aliphatic and Araliphatic). Further condensa-
air stream, see [28]. Explosive limits in air: 4 – tion under more stringent conditions to form
57 vol %; for influence of pressure on explosive aldehyde resins (e.g., synthetic shellac) now has
limits, see [29]. no industrial importance.
Urea and acetaldehyde condense in the
presence of H2 SO4 to form crotonylidenedi-
3. Chemical Properties and Uses urea (6-methyl-4-ureidohexahydropyrimidin-2-
one [1129-42-6]), which is used as a long-term
Acetaldehyde is a highly reactive compound nitrogen fertilizer (→ Fertilizers).
showing all of the typical aldehyde reactions as Acetaldehyde is also an intermediate in the
well as those of an alkyl group in which hydro- butadiene synthesis starting from acetylene and
gen atoms are activated by the carbonyl group in proceeding via acetaldol and its hydrogenation
the α position. When heated above 420 ◦ C acet- product, 1,3-butanediol [32]. This process was
aldehyde decomposes into methane and carbon introduced around 1918 and is still carried out
monoxide. on a commercial scale in some Eastern European
countries.
Acrolein is obtained by aldol condensation
3.1. Addition Reactions of acetaldehyde and formaldehyde and subse-
quent water elimination, analogous to the for-
With water, acetaldehyde forms an unstable mation of crotonaldehyde. This method is also
hydrate; isolable solid hydrates are known without commercial importance today, whereas
only with chlorinated acetaldehydes. Alcohols the production of pentaerythritol from acetalde-
add to acetaldehyde giving hemiacetals, which hyde and a fourfold amount of formaldehyde in
form acetals (→ Aldehydes, Aliphatic and Ar- the presence of Ca(OH)2 or NaOH is very im-
aliphatic) with additional alcohol in the presence portant industrially (→ Alcohols, Polyhydric).
of acids by removal of water. Diols give cyclic
acetals; for example, 2-methyl-1,3-dioxolane is
obtained from ethylene glycol and acetalde- 3.3. Reaction with Nitrogen Compounds
hyde, and 2-methyl-1,3-dioxane from 1,3-pro- With primary amines, Schiff bases,
panediol. CH3 CH=NR, are formed. Nitrogen compounds
Aqueous sodium bisulfite solution and acet- such as hydroxylamine, hydrazine, phenylhy-
aldehyde give a crystalline adduct from which drazine, and semicarbazide react with acetal-
acetaldehyde can be liberated. Dry ammonia dehyde to give easily crystallizable compounds
4 Acetaldehyde

that are used for the analytical determination 3.5. Reduction

and characterization of aldehydes (semicar-
bazone, mp 162 – 163 ◦ C; p-nitrophenylhy- Acetaldehyde is hydrogenated readily to etha-
drazone, mp 128.5 ◦ C; 2,4-dinitrophenylhydra- nol. Prior to 1939, that is, before petrochemically
zone, mp 168 ◦ C; oxime, mp 47 ◦ C). Many other produced ethylene became available in Europe,
aldehydes and ketones can be characterized in this reaction was used industrially to produce
the same way because their analogous deriva- ethanol from acetaldehyde and, therefore, from
tives generally have sharp melting points. acetylene.
The synthesis of pyridine and pyridine Mono-, di-, and triethylamine [75-04-7],
derivatives is of increasing importance. 5-Ethyl- [109-89-7], [121-44-8] can be produced from
2-methylpyridine is obtained in the presence of acetaldehyde, ammonia, and hydrogen in the
fluoride ions by the reaction of aqueous am- presence of a hydrogenation catalyst [33] (→
monia with acetaldehyde (or with paraldehyde, Amines, Aliphatic).
which slowly releases the monomer). In the
added presence of formaldehyde or acrolein,
mixtures of pyridine and alkylpyridines form (→ 3.6. Miscellaneous Reactions
Pyridine and Pyridine Derivatives).
The Tishchenko reaction of acetaldehyde gives
the commercially important solvent ethyl acetate
3.4. Oxidation (→ Acetic Acid); it is catalyzed by aluminum al-
coholate.
The major part of the acetaldehyde produced As a “radical trapping agent,” acetaldehyde
commercially is used for manufacturing acetic is used to control chain length in the polymer-
acid by oxidation with oxygen or air (→ Acetic ization of vinyl compounds.
Acid). Acetaldehyde monoperacetate is formed Oligomers of acetaldehyde are treated in
as an intermediate and decomposes into per- Chapter 8.
acetic acid and acetaldehyde at elevated temper-
atures and in the presence of catalytic amounts
of iron or cobalt salts. In the presence of Mn2+ 3.7. Consumption
salts, acetic acid is obtained from acetaldehyde
monoperacetate, and in the presence of Co2+ The consumption of acetaldehyde has changed
and Cu2+ salts, acetic anhydride can be formed. during the last few years. Since 1993 in the USA,
Oxidation with nitric acid gives glyoxal acetaldehyde is no longer used for the produc-
(→Glyoxal and → Glyoxylic Acid). Halo- tion of acetic acid, butanol, or 2-ethylhexanol,
genated acetaldehydes are prepared by halo- which are now produced by other routes (Table
genation. 1). The consumption of acetaldehyde for some
other chemicals like peracetic acid or pyridine
bases is increasing.

4. Production
Raw materials that have been used for the pro-
duction of acetaldehyde are:

Mono-, di-, and trichloroacetaldehydes (→ 1) Ethanol from fermentation of carbohydrates

Chloroacetaldehydes) and tribromoacetalde- or from hydration of ethylene
hyde (bromal) are useful for producing insec- 2) Acetylene
ticides (e.g., DDT, DDD), pharmaceuticals, and 3) Ethylene
dyes. 4) Lower hydrocarbons
5) Carbon monoxide and hydrogen
6) Methanol
 Acetaldehyde 5
Table 1. Consumption of acetaldehyde (103 t) in 2003 [56]

Product USA Mexico W. Europe Japan Total

Acetic acid/acetic anhydride 11 89 47 147
Acetate esters 35 8 54 224 321
Pentaerythritol 26 43 11 80
Pyridine and pyridine bases 73 10 * 83
Peracetic acid 23 * 23
1,3-Butylene glycol 14 * 14
Others 5 3 10 80 98
Total 176 22 206 362 766
* Included in others (glyoxal/glyoxalic acid, crotonaldehyde, lactic acid, n-butanol, 2-ethylhexanol).

The economy of the commercial processes 4.1. Production from Ethanol

depends essentially upon prices and the avail-
ability of raw materials. In highly industrialized For the production of acetaldehyde, ethanol can
countries maintaining high prices for ethanol by either be dehydrogenated or oxidized in the pres-
fiscal measures or where petrochemical ethanol ence of oxygen. Between 1918 and 1939, dehy-
was not available, as in Germany or Japan before drogenation took precedence over oxidation be-
1939, acetylene was the favored starting mate- cause of the simultaneous production of hydro-
rial for acetaldehyde. The acetylene process is gen. Later, however, the catalytic vapor-phase
still operated in some Eastern European coun- oxidation of ethanol became the preferred pro-
tries and also by companies where cheap acety- cess, probably because of the long catalyst life
lene is available. Petrochemically produced eth- and the possibility of recovering energy.
anol, however, was the favored raw material in
the other countries, whereas ethanol made by Dehydrogenation of Ethanol. In the first
fermentation was and still is used on a small work on ethanol dehydrogenation, published in
scale in countries with less chemical industry. 1886, ethanol was passed through glass tubes at
In Western countries, including Japan, all 260 ◦ C.
these processes have now been almost com- CH3 CH2 OH (l) →CH3 CHO (l) +H2 (g)
pletely replaced by the direct oxidation process ∆H = +82.5 kJ/mol
developed in the late 1950s by Wacker-Chemie
and Hoechst. This is because ethylene is avail- Improved yields are obtained in the presence
able at a lower price than acetylene. of catalysts such as platinum, copper, or oxides
Even the two-stage processes using ethanol of zinc, nickel, or cobalt. In later patents, zinc
from ethylene as starting material are no longer and chromium catalysts [34], oxides of rare earth
competitive because of the decreasing impor- metals [35], and mixtures of copper and chromi-
tance of acetaldehyde as an organic intermediate um oxides [36] have been reported. The lowest
(see Chap. 7). amounts of decomposition products are obtained
Generally, all processes based on acetylene, using copper catalysts. Frequent regeneration of
ethylene, and ethanol are more selective than the the catalysts is required, however.
oxidation of saturated hydrocarbons. This is be- Process Description. Ethanol vapor is
cause, in the latter case, other oxidation products passed at 260 – 290 ◦ C over a catalyst consist-
are formed in addition to acetaldehyde. Because ing of copper sponge or copper activated with
of the great expense of separating the product chromium oxide in a tubular reactor [37]. A con-
mixture, such processes are economical only in version of 25 – 50 % per run is obtained. By
large units and when all main and secondary washing with alcohol and water, acetaldehyde
products obtained in the process are utilized. and ethanol are separated from the exhaust gas,
which is mainly hydrogen. Pure acetaldehyde
is obtained by distillation; the ethanol is sepa-
rated from water and higher-boiling products by
6 Acetaldehyde

distillation and flows back to the reactor. The fi- The waste gas consists mainly of nitrogen,
nal acetaldehyde yield is ca. 90 %. Byproducts hydrogen, methane, carbon monoxide and car-
include butyric acid, crotonaldehyde, and ethyl bon dioxide; it is burned as lean gas with
acetate. low calorific value in steam generators. Small
amounts of acetic acid are obtained as a byprod-
Oxidation of Ethanol. Oxidation of ethanol uct.
is the oldest and the best laboratory method for
preparing acetaldehyde. In the commercial pro-
cess, ethanol is oxidized catalytically with oxy- 4.2. Production from Acetylene
gen (or air) in the vapor phase.
The most important catalysts for the industrial
CH3 CH2 OH (g) +1/2O2 (g) →CH3 CHO (l) +H2 O (l)
water addition (hydration) are mercury com-
∆H = −242.0kJ/mol
pounds:
Copper, silver, and their oxides or alloys are
the most frequently used catalysts [38].
For an example of a simultaneous oxidation
– dehydrogenation process, see [39].

Veba-Chemie Process (Fig. 1). Ethanol is This method only succeeds industrially when
mixed with air and passed over a silver catalyst the polymerization and condensation products
at 500 – 650 ◦ C (c). The temperature depends of acetaldehyde formed in the acid medium
on the ratio of alcohol to air and the flow rate are eliminated. To achieve this, the Consor-
of the gas through the catalyst. Alcohol conver- tium für elektrochemische Industrie in 1912 pro-
sion varies between 50 and 70 % and the yield posed a process using excess acetylene at an
is between 97 and 99 % depending on the reac- elevated temperature and removing the acetal-
tion conditions. Acetaldehyde and unconverted dehyde product immediately from the reaction
alcohol are removed from the waste gas by wash- liquid. At the same time, the heat of reaction
ing with cold alcohol (e) and separated by frac- is removed by distilling an appropriate amount
tional distillation (h); after concentration the al- of water. Secondary reactions, such as the oxi-
cohol returns to the reactor. Heat formed in the dation of acetaldehyde to form acetic acid and
reaction is utilized for steam production using carbon dioxide, result in reduction of Hg2+ to
a waste-heat recovery system immediately after metallic mercury. In Western countries, acetal-
the reaction zone. dehyde production from acetylene has now been
discontinued.

Wet Oxidation Process (Hoechst). The wet

oxidation process avoided direct handling of
the toxic mercury compounds. It was oper-
ated, among others, by Wacker-Chemie until the
changeover to ethylene as the starting material
in 1962.
In this method, iron(III) sulfate is added to
reoxidize the mercury metal to the mercury(II)
salt, thus ensuring sufficient concentrations of
active catalyst. The acetylene reacts at 90 –
95 ◦ C with the aqueous catalyst solution; bet-
ween 30 and 50 % of the injected acetylene re-
Figure 1. Acetaldehyde production by the Veba-Chemie
process acts in one run. The gas emerging from the reac-
a) Air compressor; b) Heat recovery system; c) Reactor; tor is cooled; mainly water and traces of mercury
d) Cooler; e) Waste-gas scrubber; f) Washing-alcohol and are separated and returned to the reactor. Acet-
return pump; g) Cooler; h) Acetaldehyde rectification aldehyde and water are condensed in additional
coolers and the acetaldehyde finally is washed
 Acetaldehyde 7

out with water from the cycle gas which has been 4.3. Production from Ethylene
cooled to 25 – 30 ◦ C. An 8 – 10 % aqueous acet-
aldehyde solution is obtained. Nitrogen is intro- Ethylene is now the most important starting ma-
duced with the feed gas while carbon dioxide is terial for the production of acetaldehyde. Most
formed as a byproduct; to avoid excessive accu- of the present capacity works by the direct oxi-
mulation, these gases are removed by withdraw- dation of ethylene (Wacker process).
ing a small stream of the cycle gas. Iron(II) sul-
fate is formed in the reaction and is oxidized in
a separate reactor with 30 % nitric acid at 95 ◦ C. 4.3.1. Direct Oxidation of Ethylene
Pure acetaldehyde is obtained by fractional dis-
tillation of the aqueous solution at about 200 This process was developed between 1957 and
kPa. For further details of this process, see [40]. 1959 by Wacker-Chemie and Hoechst [42]. For-
mally, the reaction proceeds as follows:
Chisso Process [41]. The Chisso process
C2 H4 +1/2O2 →CH3 CHO∆H = −244 kJ/mol
also uses sulfuric acid/mercury sulfate solution
as a catalyst. The acetylene reacts completely An aqueous solution of PdCl2 and CuCl2 is
with the catalyst solution at 68 – 78 ◦ C and a used as catalyst. Acetaldehyde formation had
gauge pressure of 140 kPa. A combination of already been observed in the reaction between
pressure and vacuum process stages at low tem- ethylene and aqueous palladium chloride. This
perature and without excess acetylene is used; reaction is almost quantitative:
pure acetaldehyde can be isolated and distilled
by utilizing the heat of the reaction. As in the C2 H4 +PdCl2 +H2 O→CH3 CHO+Pd+2HCl
Hoechst process, the catalyst can be regenerated
In the Wacker-Hoechst process, metallic pal-
with nitric acid. Production of acetaldehyde by
ladium is reoxidized by CuCl2 , which is then
this method was discontinued at Chisso Corp.
regenerated with oxygen:
more than a decade ago.
Pd+2CuCl2 →PdCl2 +2CuCl
Production via Vinyl Ether. Reppe at
BASF developed the process using vinyl ether 2CuCl+1/2O2 +2HCl→2CuCl2 +H2 O
[40]; it was operated in a pilot plant between
1939 and 1945. The use of toxic mercury com- Therefore only a very small amount of PdCl2
pounds is avoided altogether. Methanol is added is required for the conversion of ethylene. The
to acetylene at 150 – 160 ◦ C and 1600 kPa in reaction of ethylene with palladium chloride is
the presence of potassium hydroxide to form the rate-determining step.
methyl vinyl ether [107-25-5]. The methyl vinyl One- and two-stage versions of the process
ether is then hydrolyzed with dilute acid: are on stream. In the one-stage method, an eth-
ylene – oxygen mixture reacts with the catalyst
solution. During the reaction a stationary state
is established in which “reaction” (formation of
acetaldehyde and reduction of CuCl2 ) and “ox-
Production via Ethylidene Diacetate. Ad- idation” (reoxidation of CuCl) proceed at the
dition of acetic acid to acetylene in the pres- same rate. This stationary state is determined
ence of mercury(II) salts yields ethylidene di- by the degree of oxidation of the catalyst, as ex-
acetate [542-10-9], CH3 CH(OCOCH3 )2 , which pressed by the ratio cCu2+ / (cCu2+ +cCu+ ). In the
decomposes into acetaldehyde and acetic anhy- two-stage process the reaction is carried out with
dride at 130 – 145 ◦ C in the presence of acid cat- ethylene and then with oxygen in two separate
alysts (e.g., ZnCl2 ). This process was developed reactors. The catalyst solution is alternately re-
by the Societe Chimique des Usines du Rhône duced and oxidized. At the same time the degree
on an industrial scale in 1914 but is now without of oxidation of the catalyst changes alternately.
importance. Air is used instead of pure oxygen for the cata-
lyst oxidation.
8 Acetaldehyde

Reaction Mechanism. The first step of the re-

action is the complexation of ethylene to give a
palladium ethylene complex
The rate of reaction is diminished by the acid
[PdCl4 ]2− +H2 C = CH2
[(C2 H4 ) PdCl3 ]− +Cl− formed in the reduction of palladium chloride.
This can be prevented by buffering the acid with
Kinetic studies of this reaction show that
basic copper salts (copper oxychloride, copper
chloride ions have a inhibiting effect which is
acetate). Reformation of the basic copper salts
explained by the following substitution of a fur-
takes place during catalyst oxidation.
ther chloride ligand by a water molecule:
One-Stage Process (Fig. 2). Ethylene and
[(C2 H4 ) PdCl3 ]− +H2 O
[(C2 H4 ) PdCl2 (H2 O)] +Cl− oxygen are charged into the lower part of the re-
action tower (a); the catalyst is circulated via the
Dissociation of hydrogen ions explains the separating vessel (b) by the airlift principle and
inhibiting effect of acids: thoroughly mixed with the gas. Reaction con-
ditions are about 130 ◦ C and 400 kPa. An acet-
[(C2 H4 ) PdCl2 (H2 O)]
[(C2 H4 ) PdCl2 (OH)]− +H+
aldehyde – water vapor mixture, together with
It is assumed that the hydroxyl complex has unconverted gas, is withdrawn from the separat-
the trans geometry. Evidence for the trans – cis ing vessel; from this mixture the reaction prod-
isomerisation of this complex was revealed by a ucts are separated by cooling (c) and washing
detailed kinetic study of the reaction. π-Bonded with water (d); unconverted gas is returned to
ethylene ligands in the trans position weaken the the reactor. A small portion is discharged from
metal – chlorine bonds, so that the chloro ligand the cycle gas as exhaust gas to prevent accumu-
can be easily substituted by a water molecule lation of inert gases in the cycle gas; these inert
from which a hydrogen ion dissociates. gases are either introduced as contamination of
the feed gas (nitrogen, inert hydrocarbons) or
trans−[(C2 H4 ) PdCl2 (OH)]− +H2 O


− formed as byproducts (carbon dioxide). A par-
(C2 H4 ) PdCl(OH)2 +H+ +Cl− tial stream of catalyst is heated to 160 ◦ C (m) to
The OH− ligand in the trans position is re- decompose byproducts that have accumulated in
placed by a Cl− ion, leading to a cis complex: the catalyst.

−
Crude acetaldehyde obtained during washing
(C2 H4 ) PdCl(OH)2 +H+ +Cl−
of the reaction products is distilled in two stages.
cis−[(C2 H4 ) PdCl2 (OH)]− +H2 O The first stage (g) is an extractive distillation
with water in which lights ends having lower
The next reaction step is the formation of a
boiling points than acetaldehyde (chlorometh-
σ-bonded hydroxyethylpalladium species. This
ane, chloroethane, and carbon dioxide) are sep-
reaction has been regarded as a cis ligand inser-
arated at the top, while water and higher-boiling
tion reaction in which the OH− ligand attacks
byproducts, such as acetic acid, crotonaldehyde,
the π-bonded olefin:
or chlorinated acetaldehydes, are withdrawn to-
cis−[(C2 H4 ) PdCl2 (OH)]−
[HOCH2 CH2 PdCl2 ]− gether with acetaldehyde at the bottom. In the
second column (i) acetaldehyde is purified by
Hydride transfer to give an α-hydroxy- fractional distillation.
ethylpalladium complex is followed by reduc- Two-Stage Process (Fig. 3). Tubular reactors
tive elimination, which is the rate-determining (a), (d) are used for both “reaction” and “oxi-
step: dation”. The gases react almost completely in
the presence of the catalyst. Reaction of ethyl-
[HOCH2 CH2 PdCl2 ]−
[CH3 CH (OH) PdCl2 ]−
ene takes place at 105 – 110 ◦ C and 900 – 1000
kPa. Catalyst solution containing acetaldehyde
[CH3 CH (OH) PdCl2 ]− →CH3 CHO+Pd+H+ +2Cl− is then expanded in a flash tower (b) by reduc-
For a detailed description, see [43]. The rate ing the pressure to atmospheric level. An acetal-
of reaction can be given by the following equa- dehyde – water vapor mixture distills overhead
tion [44]: while catalyst is sent via the pump (c) to the ox-
idation reactor (d), in which it reacts with oxy-
 Acetaldehyde 9

Figure 2. One-stage process

a) Reactor; b) Separating vessel; c) Cooler; d) Scrubber; e) Crude aldehyde tank; f) Cycle-gas compressor; g) Light-ends
distillation; h) Condensers; i) Purification column; l) Product cooler; m) Regeneration

Figure 3. Two-stage process

a) Reactor; b) Flash tower; c) Catalyst pump; d) Oxidation reactor; e) Exhaust-air separator; f) Crude-aldehyde column;
g) Process-water tank; h) Crude-aldehyde container; i) Exhaust-air scrubber; k) Exhaust-gas scrubber; l) Light-ends distil-
lation; m) Condensers; n) Heater; o) Purification column; p) Cooler; q) Pumps; r) Regeneration

gen at about 1000 kPa. As oxidation and reaction exhaust air (nitrogen from the “oxidation”) in (i)
are carried out separately, no high-purity start- and exhaust gas (inert gas from the “reaction”)
ing gas is required. Generally, air is used instead in (k) free of acetaldehyde. Scrubber water then
of oxygen. Oxygen conversion is almost com- flows to the crude aldehyde column (f).
plete; the exhaust air from (e) can be used as A two-stage distillation of the crude acet-
inert gas for plant use. The oxidized catalyst so- aldehyde follows. In the first stage (l), low-
lution separated from exhaust air in the separator boiling substances, such as chloromethane,
(e) is reused for the reaction with ethylene in (a). chloroethane and carbon dioxide, are separated.
Acetaldehyde – water vapor mixture from In the second stage (o), water and higher-boiling
the flash tower (b) is preconcentrated in col- byproducts, such as chlorinated acetaldehydes
umn (f) to 60 – 90 % acetaldehyde by utilizing and acetic acid, are removed from acetaldehyde,
the heat of reaction. Process water discharged at and the latter is obtained in pure form over-
the bottom of (f) is returned to the flash tower head. Chlorinated acetaldehydes become con-
to maintain a constant catalyst concentration. A centrated within the column as medium-boiling
portion of the process water is used for scrubbing substances and are discharged laterally. From
10 Acetaldehyde

this mixture, monochloroacetaldehyde can be Construction Materials. During process

obtained as the hemihydrate. Residual byprod- development, serious problems have been
ucts can be returned to the catalyst for oxidative caused by the extremely corrosive aqueous
decomposition. This oxidative self-purification CuCl2 – PdCl2 solution. These problems have
is supported by thermal treatment of a partial been solved in the two-stage process either by
stream of catalyst at about 160 – 165 ◦ C (regen- constructing parts in contact with the catalyst
eration, r). solution entirely from titanium or by lining those
When gas mixtures obtained in naphtha parts with the metal. In the one-stage process,
cracking processes are used as raw material, con- the reactor is lined with acid-proof ceramic ma-
ventional towers are used as reactors instead of terial, the tubing is made of titanium, and certain
coiled pipes; So far, these processes have not other parts are of tantalum.
been developed industrially. Such mixtures con-
tain 30 – 40 % ethylene in addition to inert hy- Waste Air. The waste air from the oxidation
drocarbons and hydrogen [45]. process contains small amounts of unconverted
Comparison of the Two Methods. In both ethylene, some acetaldehyde, and side products
one- and two-stage processes the acetaldehyde from the reaction such as ethane, chlorometh-
yield is about 95 % and the production costs are ane, chloroethane, and methane. In Germany the
virtually the same. The advantage of using di- waste air must be purified of these side products
lute gases in the two-stage method is balanced to meet the criteria of TA-Luft [47]. The by-
by higher investment costs. Both methods yield products are oxidized over a chromium oxide
chlorinated hydrocarbons, chlorinated acetalde- catalyst. The hydrogen chloride generated is re-
hydes, and acetic acid as byproducts. Generally, moved by washing, so that the waste air contains
the choice of method is governed by the raw mainly carbon dioxide.
material and energy situations as well as by the
availability of oxygen at a reasonable price. Wastewater. Side products of the oxidation
process that enter the wastewater are acetic
Balance of Reaction and Side Products. acid, crotonaldehyde and chlorinated aldehy-
The yield in both type of process is nearly the des. Some of the chlorinated aldehydes are
same. The balance of the two stage process is as highly toxic and show high antimicrobial activ-
follows: ity. Therefore they must be treated before enter-
100 parts of ethylene gives: ing the wastewater plant to render them biolog-
ically degradable. Cleavage of organic chlorine
95 parts acetaldehyde by alkaline hydrolysis is a possible method. If
1.9 parts chlorinated aldehydes the chlorinated compounds can not be destroyed
1.1 parts unconverted ethylene the wastewater has to be incinerated.
0.8 parts carbon dioxide
0.7 parts acetic acid
0.1 parts chloromethane 4.3.2. Acetaldehyde as Byproduct
0.1 parts ethyl chloride
0.3 parts ethane, methane, crotonaldehyde Acetaldehyde is also formed in the production
and other minor side products of vinyl acetate from ethylene or acetylene (→
Vinyl Esters). It is separated by distillation and
The chlorinated aldehydes consist of chloro-
is normally converted to acetic acid for reuse. In
acetaldehyde, dichloroacetaldehyde, trichloro-
one version of the method starting from ethyl-
acetaldehyde, and 2-chloro-2-butenal.
ene, vinyl acetate and acetaldehyde are obtained
in a molar ratio of 1 : 1. This makes the process
Process Variant. An interesting variant of
nearly self-sufficient in acetic acid.
the process, although so far of no technical im-
portance, uses glycol as the reaction medium.
The cyclic acetal of acetaldehyde, namely the 4.3.3. Isomerization of Ethylene Oxide
easily hydrolyzable 2-methyl-1,3-dioloxane, is
obtained. An advantage of this method is the Research was carried out on this process [48] be-
high rate of reaction [46]. fore adopting the direct oxidation of ethylene.
 Acetaldehyde 11

Catalysts were Al2 O3 , SiO2 , and acid salts of [54]. If the importance of acetaldehyde as an or-
mineral acids, such as sulfuric acid, phosphoric ganic intermediate were to decrease in the future
acid, or molybdic acid. Yields of 90 – 95 % have as outlined in Chapter 8, this method might be
been reported, but the process has not gained in- of some interest for the economical production
dustrial importance. of small quantities of acetaldehyde.

4.4. Production from C1 Sources 4.5. Production from Hydrocarbons

Since the increases in oil price in 1973/74 and Acetaldehyde is a byproduct of the production
1977, C1 material has gained interest as a feed- of acrolein, acrylic acid, and propene oxide from
stock for organic chemicals and as a substitute propene. It is also formed in the oxidation of sat-
for petrochemicals. However, for acetaldehyde urated hydrocarbons (e.g., propane or butane) in
production, C1 material seems to be of minor im- the gas phase as operated by Celanese in the
portance because most of the classical acetalde- United States [55] (→ Acetic Acid).
hyde derivatives can be made from C1 sources.

Production Directly from Synthesis Gas. 5. Quality and Analysis

Acetaldehyde is formed with low selectivity and
a yield of ca. 30 % from synthesis gas, together High demands on acetaldehyde purity generally
with acetic acid, ethanol, and saturated hydro- are made; a typical specification is:
carbons, mainly methane. Catalysts are cobalt
Color practically colorless
and rhodium compounds activated by iodine Acetaldehyde more than 99.5 wt %
compounds or magnesium chloride and sup- Acid (as acetic acid) less than 0.1 wt %
ported on a silicate carrier [49]. There is so far Water less than 0.02 wt %
no industrial use of this process. Chlorine less than 30 mg/kg
Dry residue less than 10 mg/kg

Production via Methanol, Methyl Ac- The acid content is determined directly by
etate, or Acetic Anhydride. Hydroformylation titration, water content using the Karl Fischer
of methanol with CO/H2 has been well known reagent or empirically from the cloud point of
since the discovery of the oxo process [50]. It a carbon disulfide – acetaldehyde mixture, and
takes place in the presence of hydroformyla- chlorine content (mostly in the form of organic
tion catalysts, such as cobalt, nickel, and iron chlorine compounds) by combustion in a hydro-
salts (e.g., CoBr2 , CoI2 ) or the corresponding gen stream and determination of the hydrochlo-
metal carbonyls, at increased temperature (180 ric acid in the condensate.
– 200 ◦ C) and high pressure (30 – 40 MPa). An
acetaldehyde selectivity of 80 % or more has
been claimed using an iron – cobalt carbonyl 6. Storage and Transportation
or alternatively a cobalt – nickel catalyst in the
presence of tertiary amines, phosphines, or ni- 6.1. Storage
triles as the catalyst [51, 52].
Similarly, high selectivity has been claimed For storage of acetaldehyde, the national regu-
for the hydrocarbonylation of methyl acetate lations must be observed. In Germany the or-
with palladium or rhodium catalysts in the pres- dinance on operational safety (Betriebssicher-
ence of tertiary phosphines and iodine com- heitsverordnung) applies, under which acetalde-
pounds as well as cobalt – ruthenium catalysts hyde is classified as highly inflammable liquid
in the presence of methyl and sodium iodides (F+). In the USA, loading and storage of acetal-
[53]. dehyde are governed by the EPA.
Some patents describe the formation of acet- In Japan the Fire Defense Law and the sup-
aldehyde by reduction of acetic anhydride with plement “Cabinet Order for Control of Danger-
hydrogen over palladium or platinum on a car- ous Articles” applies. According to these regu-
rier at low pressures and moderate temperatures lations, outer storage tanks must not be made of
12 Acetaldehyde

copper, magnesium, silver, mercury, or alloys of population is specified, for which the concen-
these metals. They must be equipped with cool- tration of the material in the air is limited. The
ing facilities in order to keep the temperature maximum level of acetaldehyde allowed at the
below 15 ◦ C, and also with an inert-gas sealing boundary of the factory or place where acetal-
system. dehyde is handled is 0.5 ppm.
For safety data, see Chapter 2. Environmental problems are dealt with by
the respective national laws (see above). If acet-
aldehyde is highly diluted with water it can eas-
6.2. Transportation ily be degraded biologically. In higher concen-
trations it kills bacterial flora.
International Regulations. Acetaldehyde
is classified as a flammable liquid. Transporta-
tion is governed by: 7. Economic Aspects
IMDG Code (sea transport): class 3, UN 1089,
packing group I Today the most important production process
RID (rail): class 3, UN 1089, packing group I worldwide is the direct oxidation of ethylene. In
ADR (road): class 3, UN 1089, packing group Western Europe there is also some capacity for
I the production of acetaldehyde by oxidation of
ADNR (inland waterways), class 3, UN 1089, ethanol (7 %) and hydration of acetylene (17 %).
packing group I In South America the entire capacity for produc-
IATA-DGR (air transportation): class 3, UN tion of acetaldehyde is based on the oxidation of
1089, packing group I, PAC forbidden, CAC ethanol.
packing instruction 304, 30 L max. However, the demand for acetaldehyde
worldwide has continued to decrease primar-
ily as a result of less consumption for acetic
National Regulations. Germany: GGVSE acid manufacture, as the industry continues to
(road and rail); GGVSee (sea). USA: Regula- move toward the more efficient methanol car-
tions of the U.S. Department of Transportation: bonylation process. All manufacture of acetic
CFR 49. acid from acetaldehyde in North America has
Types and sizes of packaging and containers been discontinued, and in Europe significant ca-
are recommended by the regulations mentioned pacity for this transformation has been perma-
above. nently shut down. Acetaldehyde use for acetic
acid manufacture in Asia continues but is under
pressure and will decline because of the estab-
6.3. Other Regulations lishment of methanol carbonylation technology.
Since 1995, some 360 000 t of acetaldehyde ca-
In Germany, any accidental release of acetalde- pacity has been shut down in Western Europe,
hyde into the air, water, or soil must be reported and Mexico has eliminated its acetaldehyde ca-
to the appropriate authorities according to the pacity. New acetaldehyde capacity has been in-
ordinance on operational safety (Betriebssicher- stalled in China, but this is the only area where
heitsverordnung) or the regulations on units for new capacity has been added. Further carbon-
storing, filling, and moving materials danger- ylation capacity will be added between 2006 and
ous to water supplies (Hazardous Incident Or- 2008, but afterward the demand for acetaldehyde
dinance, Störfallverordnung, 2005). for acetic acid will eventually be phased out. Ca-
In the United States, a similar regulation ap- pacity in China is expected to be around 860 000
plies according to the Comprehensive Environ- t by 2008 and is expected to remain at those lev-
mental Response, Compensation, and Liability els for at least five more years.
Act of 1980. Incidents must be reported to the Table 2 gives production data for acetalde-
National Response Center for Water Pollution. hyde.
In Japan, acetaldehyde is specified as an Of- Important producers and their production ca-
fensive Odor Material by the Offensive Odor pacities (103 t) are listed in the following [56]:
Control Law. Under this law a district of dense
 Acetaldehyde 13
Table 2. Production of acetaldehyde (103 t) [56]

Year USA W. Europe Mexico Japan China Total

1990 283 603 190 384 1460
1995 111 668 271 395 400 1845
2000 155 370 113 401 400 1439
2003 142 212 57 362 500 1273

Celanese Chemicals Europe GmbH, Germany 120

Eastman Chemical Company, USA 225
Production. Paraldehyde is produced from
ECROS, SA, Spain 90 acetaldehyde in the presence of acid catalysts,
Japan Aldehyde Company Ltd., Japan 69 such as sulfuric acid, phosphoric acid, hy-
Jilin Chemical Industrial Company, China 180 drochloric acid, or acid cation exchangers. In the
Kyowa Yuka Company Ltd., Japan 61
Showa Denko K.K., Japan 300
homogeneous reaction, acetaldehyde is added,
Sinopec Yangzi Petrochemical Co., China 78 (400 planned) with stirring and cooling, to paraldehyde con-
Wacker Chemie AG, Germany 65 taining a small amount of sulfuric acid. After
the addition is completed, stirring is continued
for some time to establish the equilibrium; the
sulfuric acid is exactly neutralized with a sodium
8. Polymers of Acetaldehyde salt, such as sodium acetate, sodium carbonate,
or sodium bicarbonate; the reaction mixture is
8.1. Paraldehyde separated into acetaldehyde, water, and paralde-
hyde by fractional distillation [57].
Paraldehyde, 2,4,6-trimethyl-1,3,5-trioxane For continuous production, liquid acetalde-
[123-63-7], C6 H12 O3 , M r 132.161, is a cyclic hyde at 15 – 20 ◦ C or acetaldehyde vapor at 40
trimer of acetaldehyde: – 50 ◦ C is passed over an acid cation exchanger
[58]. Conversion is greater than 90 %. Acetal-
dehyde and paraldehyde are separated by dis-
tillation. For depolymerization, acetaldehyde is
slowly distilled off in the presence of acid cat-
alysts. Paraldehyde also can be decomposed in
the gas phase. Catalysts are HCl, HBr, H3 PO4 ,
Properties. Paraldehyde is colorless and has or cation exchangers. The reaction is first or-
an ethereal, penetrating odor. der. Other catalysts described in the literature
are Al2 O3 , SiO2 , ZnSO4 , and MgSO4 [59].
bp 124.35 ◦ C
mp 12.54 ◦ C Uses. Paraldehyde is used in chemical syn-
Critical temperature t crit 290 ◦ C thesis as a source of acetaldehyde whereby resin
Solubility in 100 g water at 12 g
13 ◦ C formation and other secondary reactions are
◦
at 75 C 5.8 g largely eliminated. Such synthetic reactions are,
In the solid state, four different crystal forms exist; transition for instance, used for the production of pyridines
points: 230.3 K, 147.5 K, 142.7 K.
Paraldehyde is miscible with most organic solvents. and chlorination of chloral. Between 1939 and
Density d204 0.9923 1945 paraldehyde was used as a motor fuel.
Refractive index n20 D 1.4049
◦
Viscosity at 20 C 1.31 mPa · s
Heat of combustion at constant 3405 kJ/mol
pressure 8.2. Metaldehyde
Heat capacity cp at 25 ◦ C 1.947 J g−1 K−1
Entropy (l) at 25 ◦ C 2.190 J g−1 K−1 Metaldehyde [9002-91-9], C8 H16 O4 , M r
Free energy (l) at 25 ◦ C 276.4 J/g 176.214, is the cyclic tetramer of acetaldehyde:
Heat of vaporization 41.4 kJ/mol
Latent heat of melting 104.75 J/g
Heat of formation from −113.0 kJ/mol
acetaldehyde(calculated from
combustion enthalpies)
The equilibrium 3 acetaldehyde
paraldehyde is 94.3 % on the
paraldehyde side at 150 ◦ C.
14 Acetaldehyde

Properties. Metaldehyde forms tetragonal HNO3 , CF3 COOH, AlCl3 in ether, and partic-
prisms, mp (closed capillary) 246.2 ◦ C, subli- ularly BF3 in liquid ethylene [61]. Al2 O3 and
mation temperature (decomp.) 115 ◦ C, heat of SiO2 also seem to be good initiators [62].
combustion at constant volume 3370 kJ/mol. The polymer has a rubber-like consistency
Metaldehyde is insoluble in water, acetone, and is soluble in common organic solvents. It
acetic acid, and carbon disulfide. depolymerizes at room temperature, liberating
Depolymerization of metaldehyde to acetal- acetaldehyde. It evaporates completely within a
dehyde begins at 80 ◦ C, and is complete above few days or weeks. Acidic compounds accel-
200 ◦ C. Depolymerization takes place faster and erate depolymerization, and amines (e.g., pyri-
at lower temperatures in the presence of acid dine) stabilize polyacetaldehyde to a certain ex-
catalysts, such as dilute H2 SO4 or H3 PO4 . Met- tent. A complete stabilization (as, for instance, in
aldehyde does not show the typical acetaldehyde the case of polyformaldehyde) has not yet been
reactions. It is stabilized by ammonium carbon- achieved, so the polymer is still of no practical
ate or other weakly basic compounds which neu- importance.
tralize acidic potential catalysts. Copolymers with propionaldehyde, butyr-
aldehyde, and allylacetaldehyde also have been
Production. Metaldehyde is obtained in ad- produced [63]. Crystalline, isotactic polymers
dition to large amounts of paraldehyde during have been obtained at low temperatures (for ex-
polymerization of acetaldehyde in the presence ample, −75 ◦ C) by using anionic initiators [64].
of HBr and alkaline earth metal bromides, such Suitable initiators are alkali metal alkoxides, al-
as CaBr2 , at temperatures below 0 ◦ C. However, kali metals, or metal alkyls in hydrocarbon sol-
yields are scarcely higher than 8 %. Yields of vents. The products are insoluble in common or-
14 – 20 % have been reported when working in ganic solvents but have an acetal structure like
the presence of 7 – 15 % of an aliphatic or cyclic the amorphous polymers’ [65]. Polymerization
ether at 0 – 20 ◦ C [60]. Insoluble metaldehyde is of acetaldehyde to poly(vinyl alcohol), which in
filtered out. Acetaldehyde is then distilled from contrast to polyacetaldehyde has a pure carbon
the filtrate following depolymerization of the backbone, has not yet been achieved [66].
paraldehyde and is returned to the polymeriza-
tion. Recycling of the large amounts of acetal-
dehyde results in losses that increase the process 9. Toxicology and Occupational
costs. Health
Uses. Metaldehyde in pellet form is marketed Acetaldehyde. At higher concentrations (up
as a dry fuel (Meta). Mixed with a bait, metalde- to 1000 ppm), acetaldehyde irritates the mucous
hyde is used as a molluscicide. membranes. The perception limit of acetalde-
hyde in air is in the range between 0.07 and 0.25
ppm [67, 68]. At such concentrations the fruity
8.3. Polyacetaldehyde odor of acetaldehyde is apparent. Conjunctival
irritations have been observed after a 15-min ex-
Polyacetaldehyde [9002-91-9] is a high-mo- posure to concentrations of 25 and 50 ppm [69],
lecular-mass polymer with an acetal structure but transient conjunctivitis and irritation of the
(polyoxymethylene structure): respiratory tract have been reported after expo-
sure to 200 ppm acetaldehyde for 15 min [69,
70]. The penetrating odor, the low perception
limit, and the irritation that acetaldehyde causes,
By using cationic initiators, mainly an amor- give an effective warning so that no serious cases
phous polymer is obtained. Temperatures be- of acute intoxication with pure acetaldehyde
low −40 ◦ C are preferred in this case. Above have been reported. Acute acetaldehyde intoxi-
−30 ◦ C, mainly paraldehyde and metaldehyde cation can also be observed following combined
are produced. The initiator activity also depends ingestion of disulfiram (Antabuse) and ethanol
on the solvent used. Suitable initiators include [73]. In animal experiments at high concentra-
H3 PO4 in ether and pentane, as well as HCl, tions (3000 – 20 000 ppm), pulmonary edema
 Acetaldehyde 15

and a narcotic effect become evident. The clin- nism of action is assumed to be analogous to that
ical course is similar to alcohol intoxication. of formaldehyde, acetaldehyde is regarded as a
Death occurs by breath paralysis or — with re- suspected carcinogen [80].
tardation — by pulmonary edema. When taken up by the organism, acetalde-
For rats, the LC50 (30 min inhalation) is hyde is metabolized rapidly in the liver to acetic
20 500 ppm [71]. No studies on subchronic or acid. Only a small proportion is exhaled un-
chronic toxicity of acetaldehyde in humans are changed. After intravenous injection, the halflife
available. Investigations of sister chromatid ex- in the blood is approximately 90 s [81].
change in cell cultures [72] and in human lym-
phocytes [74] and studies of single- and double- Paraldehyde acts as a sedative with few side
strand breaks in human lymphocytes incubated effects. Ingested paraldehyde partly is metabo-
with acetaldehyde [75] have revealed mutagenic lized to carbon dioxide and water and partly is
effects of acetaldehyde. Long-term exposures of exhaled unchanged. It generates an unpleasant
Syrian golden hamsters to concentrations in the odor in the expired air and therefore is not much
range 1650 – 2500 ppm have resulted in inflam- used.
matory hyperplastic and metaplastic alterations
of the upper respiratory tract with an increase Metaldehyde decomposes slowly to acetal-
in carcinomas of the nasal mucosa and the lar- dehyde in the presence of acids, so ingestion may
ynx [76]. Male and female Wistar rats were ex- cause irritation of the gastric mucosa with vom-
posed to aldehyde concentrations of 0 ppm, 750 iting. As characteristic signs of a metaldehyde
ppm, 1500 ppm for 6 h daily, 5 d per week for 52 intoxication, especially in children, heavy con-
weeks. In the highest dose group, the initial alde- vulsions (sometimes lasting several days) have
hyde concentration of 3000 ppm was reduced to been reported, with lethal outcomes, after in-
1000 ppm in the course of the study due to toxic gestion of several grams of metaldehyde [82].
effects. The dose-dependent effects found were For these reasons, those molluscicides and solid
increased mortality in all dose groups and de- fuels which contain metaldehyde must be kept
layed growth in the middle- and highest-dose away from children.
group. Adenocarcinomas were observed at all
three investigated concentrations. An increased
rate of squamous epithelial carcinomas was only 10. References
seen at 1500 ppm or more. Histological signs of
irritation were observed in the larynx region in General References
most animals from the medium- and high-dose 1. Beilstein 1 594; 1, 1st suppl., 1, 321; 1, 2nd
groups [77]. Concomitant exposure to acetalde- suppl., 1, 654; 1, 2nd suppl., 1, 654; 1, 3rd
hyde also considerably increases the number of suppl., 1, 2617; 1, 4th suppl., 3094.
tracheal carcinomas induced by instillation of 2. S. A. Miller (ed.): Acetylene, E. Benn, London
benzo[a]pyrene [72]. This suggests that chronic 1965.
tissue injury is a prerequisite for tumor forma- 3. S. A. Miller (ed.): Ethylene, E. Benn, London
tion by acetaldehyde. Tumors probably do not 1969.
develop if doses are not sufficient to cause tis- 4. R. Jira in 3: pp. 639 and 650.
sue necrosis. In male Wistar rats exposed to 150 5. R. Sieber in 3: pp. 659 and 668.
ppm or 500 ppm for 6 h per day, 5 d per week 6. R. Page in 3: p. 767.
for 4 weeks, morphological changes in the olfac- 7. W. Reppe: Chemie und Technik der
tory epithelium were observed in the high-dose Acetylen-Druck-Reaktionen, Verlag Chemie,
group [78]. However, long-term toxicity data at Weinheim 1951.
lower exposure concentrations are not yet avail- 8. Review on Manufacturing Processes of
able. Wacker, Lonza, IG-Farben factories Hüls,
Gendorf, Schkopau and Ludwigshafen,
Currently, the TLV is 25 ppm (STEL/ceiling
Stickstoff AG, Knapsack, BIOS Final Report
value) [79], and the MAK is 50 ppm [80]; the
1049, item no. 22 (1946).
latter value is preliminary. At 50 ppm acetalde- 9. Report on the IG Works Hüls and Gendorf,
hyde, no irritation or local tissue damage in the FIAT Final Report 855 (1946).
nasal mucosa is observed. Because the mecha-
16 Acetaldehyde

10. Acetaldehyde from Acetylene, BIOS Final 36. Knapsack-Griesheim, DE 1 097 969, 1954 (W.
Report 370. Opitz, W. Urbanski);
11. Kirk-Othmer, 3rd ed., 1, 97 – 112. DE 1 108 200, 1955 (W. Opitz, W. Urbanski).
Specific References 37. W. L. Faith, D. B. Keyes, R. L. Clarks:
12. R. C. Weast, H. J. Astle (eds.): CRC Handbook Industrial Chemicals, 3rd ed., J. Wiley &
of Chemistry and Physics, 60th ed., CRC Sons, New York 1965, p. 2.
Press, Boca Raton, Florida 1979 – 1980. 38. Shell Development Co., US 2 883 426, 1957
13. D’Ans-Lax, Taschenbuch für Chemiker und (W. Brackman).
Physiker, 3rd ed., Springer Verlag, Berlin Eastman Kodak Co., US 3 106 581, 1963
1964. (S.D. Neely).
14. Th. F. Smith, R. F. Bonner, Ind. Eng. Chem. 43 Veba-Chemie, DE 1 913 311, 1969 (W. Ester,
(1951) 1169. W. Hoitmann).
15. T. R. Das, N. R. Kuloor, J. Indian Inst. Sci. 50 39. Petroleum Refiner 36 (1957) 249.
(1968) 45. 40. Ullmann, 3rd ed., 3, 4.
16. P. M. Craven, J. D. Lambert, Proc. R. Soc. 41. K. Kon, T. Igarashi, Ind. Eng. Chem. 48 (1956)
(London) 205 A (1951) 439 and 444. 1258.
17. R. W. Gallant, Hydrocarbon Process. 47 42. Consortium für elektrochemische Industrie,
(1968) no. 5, 151. DE 1 049 845, 1957 (W. Hafner, J. Smidt, R.
18. A. K. Shaka, Indian J. Phys. 6 (1931) 449. Jira, R. Rüttinger, J. Sedlmeier).
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