Beruflich Dokumente
Kultur Dokumente
Ethylene Glycol
SIEGFRIED REBSDAT, Hoechst Aktiengesellschaft, Gendorf, Federal Republic
of Germany
DIETER MAYER, Hoechst Aktiengesellschaft, Frankfurt, Federal Republic of Germany
1.
2.
3.
4.
4.1.
4.1.1.
4.1.2.
4.2.
4.2.1.
4.2.2.
5.
6.
Introduction. . . . . . . . . . . . . . . . . . . . . . .
Physical Properties . . . . . . . . . . . . . . . . .
Chemical Properties . . . . . . . . . . . . . . . .
Production . . . . . . . . . . . . . . . . . . . . . . . .
Ethylene Oxide Hydrolysis. . . . . . . . . . . .
Current Production Method . . . . . . . . . . . .
Possible Developments . . . . . . . . . . . . . . .
Alternative Methods of Ethylene Glycol
Production . . . . . . . . . . . . . . . . . . . . . . . .
Direct Oxidation of Ethylene . . . . . . . . . . .
Synthesis from C1 Units. . . . . . . . . . . . . . .
Environmental Protection and Ecology . .
Quality Specifications and Analysis . . . . .
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531
531
532
534
534
534
535
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536
536
537
538
538
7.
8.
8.1.
8.2.
9.
10.
11.
11.1.
11.2.
538
538
539
539
540
541
542
542
543
544
1. Introduction
2. Physical Properties
bp at 101.3 kPa
fp
Density at 20 C
Refractive index, n20
D
Heat of vaporization at 101.3 kPa
Heat of combustion
Critical data
Temperature
Pressure
Volume
197.60 C
13.00 C
1.1135 g/cm3
1.4318
52.24 kJ/mol
19.07 MJ/kg
372 C
6515.73 kPa
0.186 L/mol
532
Ethylene Glycol
Flash point
Ignition temperature
Lower explosive limit
Upper explosive limit
Viscosity at 20 C
Cubic expansion coefficient at 20 C
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111 C
410 C
3.20 vol %
53 vol %
19.83 mPa s
0.62103 K1
3. Chemical Properties
Ethylene glycol, like other alcohols, undergoes
the reactions typical of its hydroxyl groups,
which are described elsewhere ( ! Alcohols,
Aliphatic). Thus, only the special chemical
Figure 2. Temperature dependence of the thermal conductivity of ethylene glycol water mixtures
Ethylene glycol content, mol %: a) 0; b) 25; c) 55;
d) 75; e) 100
characteristics and industrially important reactions of ethylene glycol are considered here. The
two adjacent hydroxyl groups allow cyclization,
and polycondensation; one or both of these
functional groups may, of course, also react to
give other derivatives.
Oxidation. Ethylene glycol is easily
oxidized to form a number of aldehydes and
carboxylic acids by oxygen, nitric acid, and other
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Ethylene Glycol
533
77.7 C
90.3 C
0.30
6.61
11.30
14.70
17.10
18.81
20.16
21.45
22.98
25.08
28.04
0.52
11.65
19.68
25.45
29.68
32.92
35.58
37.92
40.05
41.91
43.34
1.20
19.73
33.01
42.49
49.37
54.60
58.87
62.60
65.98
68.93
71.10
534
Ethylene Glycol
Ether and Ester Formation. Ethylene glycol can be alkylated or acylated by the customary methods to form ethers or esters, respectively. However, the presence of two hydroxyl
groups leads to the formation of both monoand diethers and mono- and diesters, depending
on the initial concentrations of the individual
reactants. The esterification of ethylene glycol
with terephthalic acid [100-21-0] to form
polyesters is especially important (! Fibers,
4. Synthetic Organic; ! Polyesters).
Vol. 13
4. Production
Although ethylene glycol has been known since
1859 (WURTZ) [1], it was not produced industrially until World War I. Its synthesis was then
based on the hydrolysis of ethylene oxide [7521-8] produced by the chlorohydrin process
(! Chlorohydrins, Chap. 4.). Production from
formaldehyde [50-00-0] and carbon monoxide
was also used commercially from 1940 to 1963
[14]. Neither of these methods is now used,
however; the older literature should be consulted for details [2, 12]. Direct oxidation of
ethylene [74-85-1] to ethylene glycol was also
employed commercially for a short time [15],
but was abandoned, probably due to problems
caused by corrosion [16].
Only one method is currently used for the industrial production of ethylene glycol. This method
is based on the hydrolysis of ethylene oxide
obtained by direct oxidation of ethylene with air
or oxygen (! Ethylene Oxide). The ethylene
oxide is thermally hydrolyzed to ethylene glycol
without a catalyst. Figure 6 shows a simplified
scheme of a plant producing ethylene glycol
by this method. The ethylene oxide water
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Ethylene Glycol
535
After leaving the reactor, the product mixture is purified by passing it through successive
distillation columns with decreasing pressures.
Water is first removed and returned to the
reactor, the mono-, di-, and triethylene glycols
are then separated by vacuum distillation. The
yield of tetraethylene glycol is too low to
warrant separate isolation. The heat liberated
in the reactor is used to heat the distillation
columns. A side stream must be provided to
prevent the accumulation of secondary products, especially small amounts of aldehydes,
which are produced during hydrolysis. The
shape of the reactor affects the selectivity
of the reaction. Plug-flow reactors are superior
to both agitator-stirred tanks and column
reactors [18].
536
Ethylene Glycol
Vol. 13
According to a Halcon patent, ethylene oxide can be extracted from the aqueous solution,
formed during its production, with supercritical carbon dioxide [29]. An ethylene oxide
carbon dioxide solution is obtained, which
reacts to form ethylene carbonate. Hydrolysis
of the ethylene carbonate then yields ethylene
glycol. Possible catalysts for this reaction are
quaternary ammonium and phosphonium salts,
such as R4NHal, R4PHal, or Ph3PCH3I. Problems such as product separation and catalyst
feedback still need to be resolved, but this
method for the selective synthesis of ethylene
glycol from ethylene oxide seems to be
the most promising for industrial-scale
application.
Vol. 13
Ethylene Glycol
537
Figure 8. Production of ethylene glycol from carbon monoxide (percentages indicate approximate yields)
538
Ethylene Glycol
Vol. 13
8. Derivatives
Only the most important of the many derivatives
of ethylene glycol will be discussed in this sec-
Purity, %
Diethylene glycol
content, wt %
Boiling range
(at 101.3 kPa), C
Density (20 C), g/cm3
Refractive index, n20
D
Water content, wt %
Acid number, mg
of KOH/g
Method
Monoethylene glycol
Antifreeze
grade
Fiber
grade
Diethylene
glycol
Triethylene
glycol
Gas chromatography
Gas chromatography
>98.00
<0.50.
>99.80
<0.10
99.60
99.50
DIN 53171,
D 1078
DIN 51757,
D 1122
DIN 53491,
DIN 51777,
DIN 53402,
ASTM
195 200
196 199
242 247
285 295
ASTM
1.113 1.115
1.1135 1.1140
1.1160 1.1175
1.1235 1.1245
ASTM 1747
ASTM E 203
ASTM D 1613
1.431 1.433
<0.50
<0.01
1.4315 1.4320
<0.100
<0.005
1.4460 1.4475
<0.20
<0.05
1.4555 1.4565
<0.10
<0.05
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Ethylene Glycol
539
Table 3. Physical properties of mono-, di-, tri-, and tetraethylene glycols [4, 5, 46]
Property
Monoethylene glycol
Diethylene glycol
Triethylene glycol
Tetraethylene glycol
Molecular formula
CAS registry number
Mr
bp(at 101.3 kpa), o C
fp, C
Vapor pressure (20 C), Pa
Density (20 C), g/cm3
Refractive index, n 20 d
Heat of combustion, MJ/kg
Heat of vaporization (101.3 kPa), kJ/mol
Viscosity (20 C) mPa*s
Surface tension, N/m2
Flash point, C
Ignition temperature, C
Lower explosive limit, vol %
HOCH2CH2OH
[107-21-1]
c62.7
197.6
13
5.3
1.1130
1.4318
19.07
52.24
19.83
4.84 (20 C)
119
410
3.2
H(OCH2CH2)2OH
[111-46-6]
106.12
244.8
8
2.7
1.1160
1.4470
22.32
52.26
36.0
4.85 (20 C)
141
390
0.7
H(OCH2CH2)3OH
[112-27-6]
150.17
287.4
7
0.5
1.1230
1.4560
23.68
61.04
49.0
4.22 (25 C)
177
370
0.9
H(OCH2CH2)4OH
[112-60-7]
194.23
decomp.
4.1
<1.3
1.1247
1.4598
62.63
61.9
191
with the appropriate alcohol. A mixture of homologues is obtained, all displaying the following
general structure:
RO(CH2CH2O)nH
fp, C
Refractive
index,
n70
D
Viscosity,
mPa s*
200
600
1000
2000
10 000
20 000
35 000
ca. 50
17 22
35 40
48 52
55 60
ca. 60
ca. 60
1.458 (25 C)
1.452
1.453
1.454
1.456
1.456
1.456
60 70 (100 %)
16 19
24 29
50 60
530 1000
2700 3500
11 000 14 000
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Ethylene Glycol
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Table 5. Physical properties of some ethylene glycol monoalkyl ethers, RO(CH2CH2O)nH [4, 5]
R
n CAS
registry
number
Mr
fp, C
bp
Density Refractive Specific heat Vapor
Flash point, Ignition
Explosive
(101.3 kPa), (20 C), index, n20
pressure
C
temperature, limits,
D (20 C),
C
kg/m3
J g1 K1
(20 C), Pa
C
vol %
CH3
C2H5
C4H9
CH3
C2H5
C4H9
CH3
C2H5
1
1
1
2
2
2
3
3
76.094
90.120
118.172
120.146
134.172
162.224
164.198
178.224
85.1
100.0
70.4
50.0
54.0
68.1
38.2
18.7
124.50
135.10
171.20
194.10
201.90
230.60
249.00
255.50
[109-86-4]
[110-80-5]
[111-76-2]
[111-77-3]
[111-90-0]
[112-34-5]
[112-35-6]
[112-50-5]
964.6
929.7
900.8
1021.0
989.0
953.0
1047.5
1020.0
1.4024
1.4079
1.4194
1.4265
1.4275
1.4316
1.4381
1.4380
2.24
930
2.32
530
2.44
80
2.15
24
2.31
17
2.29
4
2.18
2.17 (15 C)
0.4
38
40
66
90
93
99
118
195
285
215
225
215
190
195
2.4
1.8
1.1
1.6
1.8
0.7
20.6
15.7
10.6
16.1
12.2
5.9
9. Uses
Ethylene glycol lowers the freezing point of
water (see Fig. 1). Its ease of handling makes it
a perfect antifreeze [51], which accounts for over
50 % of its commercial uses (! Antifreezes).
Commercial antifreezes based on glycol also
contain corrosion inhibitors and are used, for
example, in motor vehicles, solar energy units,
heat pumps, water heating systems, and industrial cooling systems. Protection against freezing is
directly related to the glycol concentration; 60 %
glycol prevents freezing down to a temperature
of 55 C. There is little point using higher
concentrations because the freezing point then
starts to increase (Fig. 1).
Table 6. Physical properties of some ethylene glycol dialkyl ethers RO(CH2CH2O)n-R [2, 4, 50]
R
n CAS
registry
number
Mr
fp, C bp
Density Refractive Specific heat Vapor
Flash point, Ignition
Lower
(20 C),
pressure
C
temperature, explosive
(101.3 kPa), (20 C), index, n20
D
C
kg/m3
J g1 K1
(20 C), Pa
C
limit,
vol %
CH3
C2H5
C4H9
CH3
C2H5
C4H9
CH3
1
1
1
2
2
2
3
90.120
118.172
174.276
134.172
162.224
218.328
178.224
58.0
74.0
69.1
64.0
44.3
60.2
45.0
[110-71-4]
[629-14-1]
[112-48-1]
[111-96-6]
[112-36-7]
[112-73-2]
[112-35-6]
85.2
121.4
203.6
163.0
188.4
254.6
216.0
867.0
841.0
836.0
944.0
906.6
883.8
987.0
1.3796
1.3920
1.4131
1.4078
1.4115
1.4233
1.4233
2.01
2.04
2.10
1.80
8100.0
1250.0
27.0
267.0
(15 C)
51.0
(13 C)
1.3
120.0
6
35
85
51
82
118
113
200
205
1.6
1.4
195
0.7
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Ethylene Glycol
541
Table 7. Physical properties of some ethylene glycol acetates and ether acetates [4]
Compound
CAS registry Mr
number
fp, C bp
Density Refractive Ignition Flash Explosive
(101.3 kPa), (20 C), index, n20
tempera- point, limits,
D
C
kg/m3
ture, C C
vol %
[542-59-6]
[111-55-7]
[110-49-6]
[111-15-9]
[112-07-2]
[629-38-9]
[112-15-2]
[124-17-4]
80.0
31.0
65.1
61.7
63.5
99.3
25.0
32.2
104.10
146.10
118.13
132.16
160.21
162.19
176.21
204.26
Ethylene glycol is also a commercially important raw material for the manufacture of
polyester fibers, chiefly poly(ethylene terephthalate) (! Fibers, 4. Synthetic Organic).
This application consumes ca. 40 % of the total
ethylene glycol production. Polyesters are,
however, used for other purposes, e.g., for
producing recyclable bottles (! Polyesters).
Other minor uses of ethylene glycol are as a
humectant (moisture-retaining agent), plasticizer, softener, hydraulic fluid, and solvent
[52].
Ethylene Glycol Derivatives, mainly the
ethers and esters, are frequently employed as
reaction media, as absorption fluids, and as
solvents for dyes, lacquers, and various cellulose
products (cellulose esters, ethers, and nitrocellulose) [53].
Diethylene Glycol serves as a solvent, softener (cork, adhesives, paper, etc.), dye additive
(printing and stamping inks), deicing agent for
runways and aircraft [54], and a drying agent for
gases (e.g., natural gas) [55].
Triethylene Glycol is used for the same
purposes as diethylene glycol (e.g., as a solvent,
plasticizer, and drying agent for gases) [56].
Poly(ethylene Glycols) with varying molecular masses find numerous uses in the pharmaceutical industry (e.g., in ointments, liquids,
and tabletting) and the cosmetic industry (e.g.,
creams, lotions, pastes, cosmetic sticks, and
soaps). They are also used in the textile industry
(e.g., cleaning and dyeing aids), in the rubber
industry (e.g., lubricants and mold parting
182.0
190.5
145.0
156.4
192.3
209.1
217.4
246.7
1110
1106
1006
974
942
1041
1011
981
1.4209
1.4159
1.4019
1.4058
1.4138
1.4209
1.4213
1.4262
410
390
355
290
102
105
49
54
74
110
112
116
7.8 27.7
1.7 8.2
3.18 10.1
1.66 8.37
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Ethylene Glycol
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Ethylene Glycol
543
Table 8. Toxicity data and exposure limits for ethylene glycols and ethylene glycol derivatives
Compound
Ethylene glycols
Monoethylene glycol
Diethylene glycol
Triethylene glycol
Tetraethylene glycol
Monoethylene glycol derivatives
Monomethyl ether
(methoxyethanol)
Monomethyl ether acetate
(methoxyethyl acetate)
Monoethyl ether
(ethoxyethanol)
Monoethyl ether acetate
(ethoxyethyl acetate)
Monobutyl ether
(butoxyethanol)
Monobutyl ether acetate
(butoxyethyl acetate)
*
mL/kg
Single oral
LD50 in rats,
g/kg
Reference
MAK,
ppm
TLV-TWA,
ppm
8
20.8
22.1
30.8*
[61]
[61]
[61]
[83, p. 3843]
10
10
50
3.4
[84]
3.93
[61]
5.5
[84]
5.1
[61]
2.5
[84]
20
25
20
544
Ethylene Glycol
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Further Reading
G. P. Chiusoli, P. M. Maitlis (eds.): Metal-catalysis in Industrial Organic Processes, Royal Society of Chemistry,
Cambridge, UK 2006.
R. J. Farn (ed.): Chemistry and Technology of Surfactants,
Blackwell, Oxford, UK 2006.
M. W. Forkner, J. H. Robson, W. M. Snellings, A. E. Martin,
F. H. Murphy, T. E. Parsons: Glycols, Kirk Othmer
546
Ethylene Glycol
Vol. 13
H. K. Phlegm: The Role of the Chemist in Automotive Design,
CRC Taylor & Francis, Boca Raton, FL 2009.
J. Tulla-Puche, F. Albericio: The Power of Functional
Resins in Organic Synthesis, Wiley-VCH, Weinheim
2008.
U. Zoller, P. Sosis: Handbook of Detergents, CRC Press,
Boca Raton, FL 2009.