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SURVEY AND NATURAL ALCOHOLS MANUFACTURE

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SURVEY AND NATURAL ALCOHOLS MANUFACTURE

The monohydric aliphatic alcohols of six or more carbon atoms are generally referred to as higher alcohols. Historically, the higher alcohols, particularly
those of 12 or more carbon atoms, were derived from natural fats, oils, and waxes and were called fatty alcohols (see FATS AND FATTY OILS); but now similar
alcohols are widely available from synthetic processes using petrochemical feedstocks (qv). Although the natural and synthetic alcohols are used
interchangeably for many applications, for some applications the distinction still remains. The higher alcohols can be separated into the plasticizer range
alcohols, generally 611 carbon atoms, and the detergent range alcohols, 12 or more carbon atoms. There is, however, considerable overlap in use.
Production of higher alcohols in North America, Europe, and Japan in 1985 was about 2,600,000 tons and United States production was 35% of that
total. About three-fourths of the U.S. output was plasticizer range alcohols, which are used primarily as ester derivatives in plasticizers (qv) and lubricants
(see LUBRICATION AND LUBRICANTS). The detergent range alcohols are used mainly as sulfate, ethoxy, and ethoxysulfate derivatives in a wide variety of
detergent and surfactant applications (see DETERGENCY; SURFACTANTS).
Most higher alcohols of commercial importance are primary alcohols; secondary alcohols have more limited specialty uses. Detergent range
alcohols are apt to be straight chain materials and are made either from natural fats and oils or by petrochemical processes. The plasticizer range alcohols
are more likely to be branched chain materials and are made primarily by petrochemical processes. Whereas alcohols made from natural fats and oils are
always linear, some petrochemical processes produce linear alcohols and others do not. Industrial manufacturing processes are discussed in SYNTHETIC
PROCESSES.
Detergent Range Alcohols. Natural or synthetic detergent range alcohols are usually described as middle cut (1215 carbon atoms) or
heavy cut (1618 carbon atoms), corresponding to the distillation fractions of coconut alcohol from which these alcohols were first derived. Because
middle cut alcohols are preferred for most detergent applications, manufacturers maximize this production through feedstock choice (natural alcohols),
or by manipulating processing conditions (synthetic alcohols). The coproduct light cut (611 carbon atoms) and heavy cut alcohols are also valuable
products. Only a small percentage of detergent range alcohols are sold as pure single carbon chain materials.
The higher alcohols occur in minor quantities primarily as the wax ester (ester of a fatty alcohol and a fatty acid) in many oilseed and marine
sources. Free alcohols octacosanol [557-61-9], C28H58O, and triacontanol [28351-05-5], C32H66O, have been isolated in very small amounts from
sugarcane and its products (1). Oil from the sperm whale is rich in wax esters of hexadecanol, octadecenol, and eicosenol; this oil was formerly a major
commerical source of these alcohols. The oil of the North Atlantic barracudina fish contains 85% wax esters that consist mainly of hexadecanol and
octadecenol (2). Minor amounts of alcohols having 1226 carbon atoms have been found in both ancient and recent marine sediments, probably having
their origin in ocean marine life (3). Wool grease from sheep also contains higher alcohols as wax esters, and is a minor commercial source of alcohol.
The seeds of the shrub jojoba which grows in the North American desert give an oil which contains esters of eicosenol and docosenol [629-98-1], and the
natural waxes such as carnauba wax [8015-86-9] and candelilla wax [8006-44-8] contain wax esters with alcohols of 2634 carbon atoms (4). Although
higher alcohols could be obtained from any of these plant sources by saponification of the esters, they are not commercially important sources.
Plasticizer Range Alcohols. Commercial products from the family of 611 carbon alcohols that make up the plasticizer range are available
both as commercially pure single carbon chain materials and as complex isomeric mixtures. Commercial descriptions of plasticizer range alcohols are
rather confusing, but in general a commercially pure material is called "-anol," and the mixtures are called "-yl alcohol" or "iso...yl alcohol." For example,
2-ethylhexanol [104-76-7] and 4-methyl-2-pentanol [108-11-2] are single materials whereas isooctyl alcohol [68526-83-0] is a complex mixture of branched
hexanols and heptanols. Another commercial product contains linear alcohols of mixed 6-, 8-, and 10-carbon chains.

Physical Properties
Table 1 provides physical property data for selected pure alcohols (5). The homologous series of primary normal alcohols exhibits definite trends in
physical properties: for each additional CH2 unit the normal boiling point increases by about 20C, the specific gravity increases by about 0.003 units, and
the melting point increases by about 10C in the lower end of the range and about 4C in the upper end. The water solubility decreases with increasing
molecular weight and the oil solubility increases. In general, the higher alcohols are soluble in lower alcohols such as ethanol and methanol and in diethyl
ether and petroleum ether. The solubility of water in 1-hexanol and 1-octanol is appreciable, but drops off rapidly as alcohol molecular weight increases.
Enough solubility remains, however, to make even 1-octadecanol slightly hygroscopic. Mixtures of alcohols, such as 1-octadecanol and 1-hexadecanol,
are considerably more hygroscopic. Below C12 the normal alcohols are colorless, oily liquids with light, rather fruity odors. At room temperature pure
1-dodecanol solidifies to soft, crystalline platelets and the physical form of higher molecular weight alcohols progresses from these soft platelets to
crystalline waxes. Although 1-dodecanol has a slight odor, the higher homologues are essentially odorless. The secondary and branched primary alcohols
are oily liquids at room temperature and have light, fruity odors. They are soluble in alcohol solvents and diethyl ether, and also show less affinity for
water as molecular weights increase. The members of this group do not have well-defined freezing points; they set to a glass at very low temperatures.
Physical properties are often ill-defined because of difficulties in obtaining pure samples.
Table 1. Physical Properties of Pure Alcohols
Solubility, %
by wt

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SURVEY AND NATURAL ALCOHOLS MANUFACTURE

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1-hexanol

Molecula Other common Specific Refractiv Bp, C,


Mp,
r
names
gravity, e index, 101.3 kPab C
a
a
formula
20C
20C
Primary normal aliphatic
44
[111-27-3] C6H14O n-hexyl alcohol 0.8212 1.4181
157

1-heptanol
1-octanol

[111-70-6] C7H16O
[111-87-5] C8H18O

1-nonanol
1-decanol

[143-08-8] C9H20O n-nonyl alcohol


[112-30-1] C10H22O n-decyl alcohol

1-undecanol

[112-42-5] C11H24O n-undecyl


alcohol
[112-53-8] C12H26O n-dodecyl
alcohol, lauryl
alcohol
[112-70-9] C13H28O n-tridecyl
alcohol
[112-72-1] C14H30O n-tetradecyl
alco-hol,
myristyl alcohol
[629-76-5] C15H32O n-pentadecyl
alcohol
[36653-82- C16H34O cetyl alcohol,
4]
palmityl alcohol

IUPAC name

1-dodecanol
1-tridecanol
1-tetradecanol
1-pentadecanol
1-hexadecanol
1-heptadecanol

CAS
Registry
Number

Viscosit in water of Solubility in other


y,
wa
solvents
ac
ter
mPas ,
5.9

0.5920
0.1018
0.0625

1.4242
1.4296

176
195

35

7.4
8.4

0.8295
0.8312

1.4338
1.4371

213
230

11.7
13.8

0.8339

1.4402

243

16

17.2

1381.33

24

18.8

1552.0

30.5

n-heptyl alcohol 0.8238


n-octyl alcohol 0.8273

0.83062 1.4428

15:5

<0:02

0.82383

7.2 petroleum ether,


ethanol
4.5 ethanol,
petroleum ether
2.8 glacial acetic acid,
benzene, ethanol,
petro-leum ether
1.3 petroleum ether,
ethanol

0.81655 1.435850 1581.33

38

<0:02

nil petroleum ether,


ethanol

0.0620

nil ethanol,
methanol, diethyl
ether, benzene

1.440850

44

0.81576 1.439260 1771.33

49

5375

[1454-85-9] C17H36O margaryl alcohol 0.81676 1.439260

54

1-octadecanol
1-nonadecanol
1-eicosanol
1-hexacosanol
1-hentriacontanol
9-hexadecen-1-ol
9-octadecen-1-ol

[112-92-5] C18H38O stearyl alcohol, 0.81376 1.438860


0
n-octadecyl
alcohol
[1454-84-8] C19H40O n-nonadecyl
alcohol
[629-96-9] C20H42O eicosyl alcohol,
arachidyl alcohol
[506-52-5] C26H54O ceryl alcohol
[26444-39- C31H64O melissyl alcohol, 0.77849
3]
myricyl alcohol 5
[10378-01- C16H32O palmitoleyl
5]
alcohol
[143-28-2] C18H36O oleyl alcohol
0.85045 1.447360

2031.33

58

nil

nil benzene, ethanol,


petroleum ether
ethanol, ether

62
2511.33

66

3052.67

79.5
87

i
nil

2052102.0
ethanol, diethyl
ether

10-eicosen-1-ol

[28061-39- C20H40O eicosoyl alcohol


4]
Primary branched aliphatic
2-methyl-1-pentanol [105-30-6] C6H14O 2-methylpentyl 0.8254 1.4190
148
alcohol
2-ethyl-1-butanol
[97-95-0] C6H14O 2-ethylbutyl
0.8348 1.4224
146.5
alcohol
2-ethyl-1-hexanol
[104-76-7] C8H18O 2-ethylhexyl
0.8340 1.4316
184
alcohol
3,5-dimethyl-1-hexan [13501-73- C8H18O
0.8297 1.4250
182.5
ol
0]
2,2,4-trimethyl-1-pent [123-44-4] C8H18O
0.839 1.4300
168
anol
Secondary aliphatic
4-methyl-2-pentanol [108-11-2] C6H14O methylamyl
0.8083 1.4112
132
alco-hol,

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition)

6.6

0.31

5.4

9.8

0.07

2.6 ethanol, diethyl


ether

114
70

70
90

ethanol
5.2

1.7

5.8 ethanol, diethyl


ether

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

2-octanol

[123-96-6] C8H18O

methyliso-butylc
arbinol
capryl alcohol

0:83515=4

Vol 1

1.4256

178179

38

8.2

65
2,6-dimethyl-4-heptan [108-82-7] C9H20O diisobutylcar-bin 0.8121 1.4231
178
14.3
ol
ol
60
0.8193 1.4345
225
21
2,6,8-trimethyl-4-nona [123-17-1] C12H26O
nol
a
Temperature, C, if other than 20C, is noted as superscript.
b
Pressure, kPa, if other than 101.3 kPa, is noted as superscript. To convert kPa to mm Hg, multiply by 7.50.
c
mPas =cP.

0.09625
0.06
<0:02

ethanol,
petroleum ether
0.9 ethanol, diethyl
9 ether
0.6
0

Chemical Properties
The higher alcohols undergo the same chemical reactions as other primary or secondary alcohols. Similar to other chemicals having long carbon chains,
however, reactivity decreases as molecular weight or chain branching increase. This lower reactivity and concommitant decreased solubility in water and
in other solvents means that more rigorous reaction conditions, or even use of different reaction schemes as compared to shorter chain alcohols, are
generally required. Typical reactions of the higher alcohols are as shown.
Esterification
ROH + R 0 COOH ! R 0 COOR + H 2 O
Sulfation
ROH + SO 3 ! ROSO 3 H
alkyl sulfuric acid

ROSO 3 H + NaOH ! ROSO 3 Na + H 2 O


sodium alkyl sulfate

Etherification

Halogenation
3 ROH + PCl 3 ! 3 RCl + P(OH) 3
Dehydration
RCH 2 CH 2 OH ! RCH|CH 2 + H 2 O
Oxidation
1
RCH 2 OH + =2 O 2 ! RCH|O + H 2 O

Amination
ROH + R 0 NH 2 ! RNHR 0 + H 2 O
Oxidation (6,7) and amination (8,9) are discussed in detail elsewhere.

Shipment and Storage


Detergent range alcohols are available in 208-L (55-gal) drums of approximately 160-kg or 23,000-L (6000-gal) tank trucks, in tank cars of 75,000 L

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(20,000 gal) containing about 60,000 kg, and in marine barges. The tank trucks and cars are usually insulated and equipped with an external heating jacket;
the barges have coils for melting and heating the alcohols. High melting alcohols such as hexadecanol and octadecanol are also available as flaked material
in three-ply, polyethylene-lined 22.7 kg (50 lb) bags. Detergent range alcohols have a U.S. Department of Transportation classification as nonhazardous
for shipment. The perfume-grade alcohols, such as specially purified octanol and decanol, are available in bottles and cans; other plasticizer range
materials are available in 208-L drums, 23,000-L tank trucks, 75,000-L tank cars, and in marine barges. Because of low melting points, most of these
materials do not require transports having heating equipment. Bulk shipments are usually described by the commercial name of the material, such as
methylisobutylcarbinol for 4-methyl-2-pentanol. The names hexyl, octyl, or decyl alcohol are used as freight descriptions for the linear or branched
alcohols of corresponding carbon number. Linear and branched alcohols of 69 carbon atoms, and mixtures containing them, are classified as
combustible for shipment by the U.S. DOT because of their low flash points. Alcohols of 10 carbons and above are classified as nonhazardous.
The higher alcohols are not corrosive to carbon steel, and equipment suitable for handling solvents or gasoline is also suitable for the alcohols.
However, special storage conditions are often needed to maintain alcohol quality. Lined carbon steel tanks having nitrogen blankets to exclude both
moisture and oxygen are recommended for storage of detergent range alcohols (10). Preferred storage temperature is no higher than 10C above the
alcohol melting point and repeated cycles of melting and solidifying must be avoided. Low pressure steam is generally used for heating; for the high
melting hexadecanol and octadecanol, hot water can be used in order to reduce exposure to high temperature heating surfaces. Although they are
generally considered quite stable, alcohols which are stored either for long periods of time or under improper conditions can undergo such subtle changes
as deterioration of color, increase in carbonyl level, or a decrease in acid heat stability. It is sometimes preferable to store high melting alcohols as flakes in
bags at ambient temperature rather than melted in a tank at higher temperature.
To prevent rusting and moisture pickup resulting from the hygroscopic nature of plasticizer range alcohols, tanks should be protected from
moisture by such devices as a drying tube on the tank or a dry air blanket; nitrogen is usually not needed because ambient storage temperature is adequate
for these lower melting materials. In general, plasticizer range alcohols are more storage-stable than the detergent range alcohols. However, to avoid the
danger of fire resulting from the low flash points of plasticizer range alcohols, tanks should be grounded, have no interior sources of ignition, be filled
from the bottom or have a filling line extending to the bottom to prevent static sparks, and be equipped with flame arrestors.

Economic Aspects
United States production of detergent range alcohol was 354,000 t in 1987, according to the U.S. International Trade Commission, compared to 263,000 t
in 1974. About 60% was sold as alcohol on the merchant market; most of the rest was ethoxylated by the producers, then sold as the ethoxylated alcohol
or sulfated and sold as the ethoxysulfate surfactant. In the 1960s and early 1970s ethylene-based synthetic alcohols appeared to be the wave of the future.
Increases in petroleum prices and stabilization in the price of coconut and palm kernel oils, the primary raw materials for higher alcohols, have led back
to natural production. Most alcohol capacity installed in the 1980s uses catalytic hydrogenolysis processes employing natural fats and oils as feedstock to
make alcohol. Fatty alcohol capacity is increasingly being built in the coconut and palm oil producing countries. A number of natural alcohol plants have
started up or are in various stages of construction in the Philippines, Malaysia, and Indonesia. In the United States however, the lion's share of detergent
range alcohol production is by synthetic processes; Shell Chemical is the largest producer in a plant having a 270,000-t capacity. Linear synthetic alcohols
can be used interchangeably with natural alcohols except where the presence of minor amounts of chain branching or secondary alcohols preclude use of
the synthetics. The more highly branched alcohols are used where branching is not a problem, is desired, or the alcohols are ethoxylated. Ethoxylation
reduces the physical and chemical effects of chain branching. Domestic detergent range alcohol producers are shown in Table 2; representative prices are
given in Table 3. Manufacturers often adjust coproduct alcohol prices to compensate for shortages or surpluses, keeping the price of the primary material
stable.
Table 2. U.S. Manufacturers of Detergent Range Alcohols
Manufacturer
Procter & Gamble

Process
catalytic hydrogenolysis
catalytic hydrogenolysis
modified oxo

Feedstock
coconut and palm kernel oils,
tallow, palm oil
tallow
ethylene/olefins

Sherex
Shell Chemical

C9C15

Vista

Ziegler

ethylene

C6C22

Ethyl

modified Ziegler

ethylene

Exxon

modified oxo

olefins

C6C22
C13, C15

Table 3. Prices of Detergent Range Alcohols

Products
C6C18
C16, C18, oleyl

Alcohol
lauryl alcohol, fob
dodecanol/tridecanol, delivered

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition)

Price, U.S.$/kg
1.54
1.26

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

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hexadecanol, fob
octadecanol, fob
a
November 1989 list prices.

2.01
2.01

United States production of plasticizer range alcohols was estimated to be 690,000 t in 1988 (11), 44% of which was 2-ethylhexanol. Domestic
manufacturers and prices of representative plasticizer range alcohols are given in Table 4. The previous decade has seen a reduction in the number of
manufacturers of 2-ethylhexanol and other branched chain alcohols. The volume of most branched alcohols has been static, however, and 2-ethylhexanol
volume has doubled; the volume of linear alcohols has also grown. A substantial portion of these materials is used in plasticizers for poly(vinyl chloride)
(PVC), so plasticizer range alcohol fortunes are tied to variations in the PVC industry. The plasticizers are mainly diesters of the alcohols and phthalic
acid; di(2-ethylhexyl) phthalate [117-81-7] is the highest volume product. Recent price and volume history of 2-ethylhexanol is given in Table 5. Other
branched alcohols tend to be priced at, or slightly above, the price of 2-ethylhexanol; the linear alcohols are several cents per kilogram higher. Production
costs of plasticizer range alcohols, manufactured either by oxo or Ziegler processes, are strongly dependent on the cost of the ethylene or propylene
feedstocks, making them dependent on the cost of crude oil and natural gas.
Table 4. Prices and Manufacturers of Plasticizer Range Alcohols
Material
hexanol

Price, U.S.$/kg
1.74

4-methyl-2-pentanol
octanol

1.32
2.01

octanol, perfumer's grade


isooctyl alcohol
2-ethylhexanol

3.09
0.97
0.93

decanol

1.34

Manufacturer
Ethyl
Vista
Union Carbide
Ethyl
Vista
Exxon
BASF
Eastman
Shell Chemical
Tenn-USS
Union Carbide
Ethyl
Vista

decanol, perfumer's grade


1.65
Delivered price May 1989. The listed price is not necessarily the price listed by the indicated manufacturer.

Table 5. Price and Production Volume of 2-Ethylhexanol


Year
1988
1987
1986
1985
1984
1983
a
Ref. 12.

Price, U.S.$/kg
0.73
0.60
0.55
0.60
0.71
0.71

Volume, 103 t/yr


337
300
259
243
245
175

Most manufacturers sell a portion of their alcohol product on the merchant market, retaining a portion for internal use, typically for the
manufacture of plasticizers. Sterling Chemicals' linear alcohol of 7, 9, and 11 carbons is all used captively. Plasticizer range linear alcohols derived from
natural fats and oils, for instance, octanol and decanol derived from coconut oil and 2-octanol derived from castor oil, are of only minor importance in
the marketplace. The 13carbon tridecyl alcohol is usually considered to be a plasticizer range alcohol because of its manufacture by the oxo process and
its use in making plasticizers. On the other hand, some types of linear 9- and 11-carbon alcohols find major application in detergents.

Analysis
Because the higher alcohols are made by a number of processes and from different raw materials, analytical procedures are designed to yield three kinds
of information: the carbon chain length distribution, or combining weight, of the alcohols present; the purity of the material; and the presence of minor

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impurities and contaminants that would interfere with subsequent use of the product. Analytical methods and characterization of alcohols have been
summarized (13).
For the detergent range alcohols, capillary gas chromatography, fast, accurate, and simple to use, is by far the most useful method for determining
composition and purity (14). By the proper choice of the capillary stationary phase, carbon chain distribution and the amount of unsaturated, chain
branched, or secondary alcohols, as well as the level of minor materials such as esters and hydrocarbons, can be determined. Hydroxyl Value (HV = mg
of KOH equivalent to the hydroxyl content of 1 g of alcohol) measures the |OH end group and reflects both the combining weight and the purity of the
sample. Saponification Value (SV = mg of KOH required to saponify the esters and acids in 1 g of alcohol), Acid Value (AV = mg of KOH required to
neutralize the free fatty acid in 1 g of alcohol), and Ester Value (EV = SV minus AV) are measures of the carboxylic acid impurities present as the free
acids or esters. Iodine Value (IV = g of iodine absorbed by 100 g of alcohol) is a measure of carboncarbon unsaturation present in the alcohol. HV, SV,
AV, EV, and IV can all be calculated from the capillary GC analysis. Moisture is also an important criterion of alcohol quality, and the color of the
alcohol, usually determined by the APHA (PtCo) method, should be as close to water-white as possible. A number of other tests measure attributes
important to specific uses. Examples are melting point for the heavy cut alcohols, cloud point of unsaturated alcohols, odor, carbonyl content, peroxide
content, and various color stability tests. One of these last is the acid heat stability test. It determines the color change of middle cut alcohol in contact
with concentrated sulfuric acid at an elevated temperature as an index of the color of alkyl sulfates that would be made from the alcohol. Test outcome is
affected by carbonyl at a level of a few hundred parts per million, and by traces of iron, rust, and dirt particles.
As for detergent range alcohols, extensive use of capillary gas chromatography is also made for composition and purity determination of the
plasticizer range materials. For those products that are a broad mixture of various isomers, however, distillation range and Hydroxyl Value are more
useful characterizations. From the HV the combining weight can be calculated for subsequent chemical reactions. Carbonyl content is important,
especially for those alcohols manufactured from aldehydes by the oxo process. It is often expressed similarly to HV: as the mg of KOH equivalent to the
carbonyl oxygen in 1 g of sample. Acidity, expressed in terms of the equivalent weight percent of acetic acid, is used to determine the quality of the
alcohol, as are moisture and APHA color. As with the detergent range alcohols, tests which measure color stability in the presence of sulfuric acid are
employed to predict the color changes that may occur in subsequent reactions utilizing acid catalysts. Additionally, analytical determinations such as odor,
chloride level, hydrocarbon content, and trace metal content, are required for specific uses.

Specifications and Standards


Most of the detergent range alcohols used commercially consist of mixtures of alcohols, and a wide variety of products is available. Table 6 shows the
approximate carbon chain length composition of both the commonly used mixtures and single carbon materials; typical properties are given in Table 7.
The range of commercially available materials is further described in sales brochures published by the manufacturers (15), who usually can also provide
specially tailored blends to meet individual customer needs. Although only even-carbon alcohols are available from natural fats and oils and the Ziegler
process, the development of the oxo process for linear alcohols has made odd-carbon alcohols a commercial reality, albeit with some chain branching.
Commercial mixtures of these latter alcohols contain both odd and even numbered chain lengths. The major production of detergent range alcohols is in
the 1218 carbon range. Alcohols with 20 carbons and above are available in mixtures such as Vista's Alfol 20+ and Ethyl's Epal 20+. Behenyl alcohol
(docosanol) [661-19-8], C22H46O, can be made from rapeseed oil. Except for oleyl alcohol, all commercial alcohols are fully saturated.

Table 6. Composition of Commercial Detergent Range Alcohols


Alcohol
commercial name
lauryl

myristyl
cetyl
tallow
stearyl
oleyl

Representative trade name


b

CO-1214 [67762-41-8]
c
Alfol 1214
d
Epal 1214
e
Neodol 23
Epal 1218 [67762-25-8]
f
Lauryl Alcohol Special-Type
Epal 12
Alfol 14
CO-1695 [36653-82-4]
Epal 16
b
TA-1618 [67762-30-5]
g
Adol 64
CO-1897
f
HD Oleyl Alcohol D
Adol 80

Derived from
coconut, palm kernel
ethylene
ethylene
ethylene
ethylene
coconut
ethylene
ethylene
vegetable oil
ethylene
tallow
fats
vegetable oil
fats
fats

C12
68
55
66
41
49
72
99
1

C13

C14

C16
6

57

26
45
27
1
20
27
1
99
1
2
4

C18

C20

7
17
1
1
98
98
27
26
1
5
14

14

2
1
h
70
70
98
i
94
i
81

1
1
1
1

Approximate composition by wt %, 100% alcohol basis.


Registered trademark for Procter & Gamble alcohols.
c
Registered trademark for Vista alcohols.
b

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SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

Registered trademark for Ethyl Corporation alcohols.


Registered trademark for Shell alcohols.
f
Registered trademark for Henkel alcohols.
h
Includes 1% C17 alcohol.
e

g
i

Registered trademark for Sherex alcohols.


Primarily unsaturated.

Table 7. Properties of Commercial Linear Detergent Range Alcohols


Commercial
descriptive name

Hydroxyl
Value

Saponification
Value

lauryl (99% C12)


lauryl (68% C12)

301
285
289

0.2
0.2

C12C13
cetyl
229
tallow
208
stearyl
206
oleyl
206
a
Neodol 23 (registered trademark for Shell alcohols).

0.4
1.8
0.5
0.5

Acid
Valu
e
0.02
0.01
0.02

Iodin
e
Value
0.2
0

0
0
0

0.6
0.5
0.7
94

Melting
point, C

Color,
APHA

Moisture,
%

2325
22

5
3
5

0.03
0.04
0.02

610
1020
615

0.04
0.03
0.03

1822
49
53
58
4

Both detergent range and plasticizer range alcohols and their derivatives have been accepted by the U.S. government for use in a number of drug
and food contact or food additive areas, and plasticizer range alcohols have been accepted as flavoring agents in foods (16). They must meet rigid
manufacture, quality control, and record keeping requirements. Hexadecanol and octadecanol are used extensively in drug and cosmetic areas which
require drug-grade raw materials. For this application they are produced to the specifications of the National Formulary (NF) in facilities registered by the
U.S. Food and Drug Administration. The NF requirements for hexadecanol are 4550C melting point, 2.0 max AV, 5.0 max IV, and 218238 HV. The
NF requirements for octadecanol are 5560C melting point, 2.0 max AV, 2.0 max IV, 200220 HV, and 90% min. octadecanol.
Besides the linear detergent range alcohols, a number of highly branched alcohols of 12 or more carbon atoms made by the oxo process are of
commercial importance. Tridecyl alcohol [27458-92-0], C13H28O, consisting mainly of tetramethyl-1-nonanols, is one such material; it is generally
considered to be a plasticizer range alcohol because of its manufacturing process and use in making plasticizers. Primary alcohols made by the Guerbet
process, consisting of alcohols characterized as 2,2-dialkyl-1-ethanols, are available as hexadecyl [68526-87-4], C16H34O, octadecyl [27458-93-1], C18H38O,
eicosyl [52655-10-4], C20H42O, and hexacosyl [70693-05-9], C26H54O, materials sold by Exxon under the Exxal brand name (17). They should not be
confused with linear alcohols having similar names. Isostearyl alcohol [27458-93-1] is a highly branched natural alcohol containing a mixture of C18
alcohols derived from isostearic acid.
The sales brochures of the manufacturers describe the plasticizer range alcohols available on the merchant market (18). Typical properties of
several commercial plasticizer range alcohols are presented in Table 8. Because in most cases these are mixtures of isomers or alcohols with several
carbon chains, the properties of a particular material can vary somewhat from manufacturer to manufacturer. Both odd and even carbon chain alcohols
are available, in both linear and highly branched versions. Examples of the composition of several mixtures are given in Table 9.
Table 8. Typical Properties of Commercial Plasticizer Range Alcohols
Name
hexyl
2-ethylhexanol
isooctyl
isononyl
hexyl decyl
octanol
decanol

Molecular
formula
(C6H14O)
C8H18O)
(C8H18O)
(C9H20O)
(C8H18O)
(C10H22O)

Hydroxyl
Value

Acidity, %
as acetic
0.001

431

<0:007

0.001
0.001
408
431
355

<0:004
<0:005
<0:01

Carbonyl,
wt % O

Boiling range,
C

<0:003

152160
182186
184190
202213
168203
184195
226230

<0:02
<0:003
<0:003

0.003
0.003
0.003

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition)

Color,
APHA
5

Moisture,
%
0.05

<10

<0:10

5
5
5
5
5

0.05
0.05
0.01
0.03
0.03

Flash point ,
C
63
84

84
91
c

81
c
88
113

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

tridecyl

(C13H28O)

283

<0:003

0.001

Vol 1

254263

<0:05

127

Pensky-Martens closed cup unless otherwise noted.


Cleveland open cup.
c
Tag close cup.
b

Table 9. Composition of Commercial Plasticizer Range Alcohols


Material
isooctyl

Component
3,4-dimethyl-1-hexanol [19138-79-5]
3,5-dimethyl-1-hexanol [69778-63-8]
4,5-dimethyl-1-hexanol [60564-76-3]
3-methyl-1-heptanol [31367-46-1]
5-methyl-1-heptanol [7212-53-5]

hexyl decyl
(Epal 610)
octyl decyl
(Alfol 810)

3-ethyl-1-hexanol [41065-95-6]
other primary alcohols
hexanol
octanol
decanol
octanol
decanol

Composition, wt %
9
=

54

25
13
8
10
44
46
42
58

Toxicological Properties
The higher alcohols are among the less toxic of commonly used chemicals and, in general, their toxic effects are reduced as the number of carbon atoms
is increased. Table 10 gives data representative of the toxicological properties of the higher alcohols (1923). Slight differences in material purity,
methodology, and grading of results may account for variations in data from different sources, and these data should not be regarded as representing a
consistent series. Because the data pertain to animals and not necessarily to humans, they should be used only as a guide. The values for acute oral toxicity
may be compared to an LD50 of about 3.75 g/kg for sodium chloride ingested by rats. A substance with an LD50 of 15 g/kg or above is generally
considered to be "practically nontoxic."
Table 10. Toxicological Properties of Higher Alcohols
Material

Acute oral LD50 rats,


a

Eye irritation, rabbits

g/kg
hexanol
severe
3.24.4
octanol
18
severe
decanol
severe
2026
>40
moderate
dodecanol
>8
tetradecanol
mild
>20
hexadecanol
mild
>20
octadecanol
mild
4-methyl-2-pentanol
2.6
slight
2-ethylhexanol
3.7
severe
mixed isomers
hexyl
3.7
severe
>2
isooctyl
severe
decyl
4.7
severe
tridecyl
4.7
moderate
a
The lethal dose for 50% of the test animals, expressed in terms of g of material per kg of body weight.
b
Evaluation of the irritation elicited from 0.1 mL of the material applied to the eyes without rinsing.
c
Evaluation of the irritation elicited from an application of full-strength alcohol left in contact with the skin for 24 h.

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition)

Primary skin irritation, rabbits


moderate
moderate
moderate
slight
mild
mild
mild
moderate
moderate
moderate
moderate
moderate
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Primary human skin irritation of tetradecanol, hexadecanol, and octadecanol is nil; they have been used for many years in cosmetic creams and
ointments (24). Based on human testing and industrial experience, the linear, even carbon number alcohols of 618 carbon atoms are not human skin
sensitizers, nor are the 7-, 9- and 11-carbon alcohols and 2-ethylhexanol. Neither has industrial handling of other branched alcohols led to skin problems.
Inhalation hazard, further mitigated by the low vapor pressure of these alcohols, is slight. Sustained breathing of alcohol vapor or mist should be avoided,
however, as aspiration hazards have been reported (25).

Manufacture from Fats and Oils


Fats and oils from a number of animal and vegetable sources are the feedstocks for the manufacture of natural higher alcohols. These materials consist of
triglycerides: glycerol esterified with three moles of a fatty acid. The alcohol is manufactured by reduction of the fatty acid functional group. A small
amount of natural alcohol is also obtained commercially by saponification of natural wax esters of the higher alcohols, such as wool grease.
The carbon chain lengths of the fatty acids available from natural fats and oils range from 622 and higher, although a given material has a
narrower range. Each triglyceride has a random distribution of fatty acid chain lengths and unsaturation, but the proportion of the various acids is fairly
uniform for fats and oils from a common source. Any triglyceride or fatty acid may be utilized as a raw material for the manufacture of alcohols, but the
commonly used materials are coconut oil, palm kernel oil, lard, tallow, rapeseed oil, and palm oil, and to a lesser extent soybean oil, corn oil and babassu
oil. Coconut and palm kernel oil are the primary sources of dodecanol and tetradecanol; lard, tallow, and palm oil are the primary sources of hexadecanol
and octadecanol. Producers of natural fatty alcohols typically make a broad range of alcohol products having various carbon chain lengths. They vary
feedstocks to meet market needs for particular alcohols and to take advantage of changes in the relative costs of the various feedstock materials.
The first commercial production of fatty alcohol in the 1930s employed the sodium reduction process using a methyl ester feedstock. The process
was used in plants constructed up to about 1950, but it was expensive, hazardous, and complex. By about 1960 most of the sodium reduction plants had
been replaced by those employing the catalytic hydrogenolysis process. Catalytic hydrogenation processes were investigated as early as the 1930s by a
number of workers; one of these is described in reference 26.
Hydrogenolysis Process. Fatty alcohols are produced by hydrogenolysis of methyl esters or fatty acids in the presence of a heterogeneous
catalyst at 20,70031,000 kPa (30004500 psi) and 250300C in conversions of 9098%. A higher conversion can be achieved using more rigorous
reaction conditions, but it is accompanied by a significant amount of hydrocarbon production.
RCOOCH 3 + 2 H 2 ! catalyst
high pressure RCH 2 OH + CH 3 OH
RCH 2 CH 2 OH + H 2 ! RCH 2 CH 3 + H 2 O
Fatty esters (wax esters), formed by ester interchange of the product alcohol and the starting material in the hydrogenolysis reactors, are later separated
from the product by distillation. Unreacted methyl esters are also converted to fatty esters in the distillation step
RCOOCH 3 + R 0 OH ! RCOOR 0 + CH 3 OH
so that they too can be separated from the product. Fatty esters are recycled to the hydrogenolysis reactors since they can undergo hydrogenation in a
manner similar to methyl esters, in this case yielding two moles of fatty alcohol per mole of ester. Fatty acids can also be used for the higher alcohol
production. The fatty acid is pumped into the high pressure reactor and esterified in situ using previously made fatty alcohol; the resulting fatty ester then
undergoes hydrogenolysis to two moles of fatty alcohol. A recently disclosed process uses the naturally occurring triglyceride ester as the feedstock for
hydrogenolysis (27). Although the manufacturing process is simplified by eliminating the production of a methyl ester or fatty acid, degradation of
glycerol to 1,2-propanediol also occurs in the high temperature of the reaction and thus degrades a valuable coproduct.
To prepare methyl ester feedstock for making fatty alcohols, any free fatty acid must first be removed from the fat or oil so that the acid does not
react with the catalyst used in the subsequent alcoholysis step. Fatty acid removal may be accomplished either by refining or by converting the acid
directly to a methyl ester (28). Refining is done either chemically, by removal of a soap formed with sodium hydroxide or sodium carbonate (alkali
refining), or physically, by steam distillation of the fatty acids (steam refining) (29). In the case of chemical refining, the by-product soap is acidified to
give a fatty acid and these "foots" are used as animal feed or upgraded for industrial fatty acid use. The by-product fatty acid from steam refining is of a
higher grade than acidified foots and is used directly as an industrial fatty acid or as animal feed. In either case, the fatty acid can also be converted to the
methyl ester and used as additional alcohol feedstock. Refined oil is dried to prevent the reaction of water with the catalyst during alcoholysis.
Alcoholysis (ester interchange) is performed at atmospheric pressure near the boiling point of methanol in carbon steel equipment. Sodium
methoxide [124-41-4], CH3ONa, the catalyst, can be prepared in the same reactor by reaction of methanol and metallic sodium, or it can be purchased in
methanol solution. Usage is approximately 0.31.0 wt % of the triglyceride.
C 3 H 5 (OOCR) 3 + 3 CH 3 OH ! NaOCH 3 3 RCOOCH 3 + C 3 H 5 (OH)3
The alcoholysis reaction may be carried out either batchwise or continuously by treating the triglyceride with an excess of methanol for 3060 min in a
well-agitated reactor. The reactants are then allowed to settle and the glycerol [56-81-5] is recovered in methanol solution in the lower layer. The sodium
methoxide and excess methanol are removed from the methyl ester, which then may be fed directly to the hydrogenolysis process. Alternatively, the ester
may be distilled to remove unreacted material and other impurities, or fractionated into different cuts. Fractionation of either the methyl ester or of the
product following hydrogenolysis provides alcohols that have narrow carbon-chain distributions.
High Pressure Hydrogenolysis. There are three major hydrogenolysis processes in worldwide use: the methyl ester, slurry catalyst process
operated by Procter & Gamble, Henkel, and Kao; the methyl ester, fixed-bed catalyst process operated by Henkel and Oleofina; and the fatty acid, slurry
catalyst process developed by Lurgi and operated by several licensees. Each process typically uses a copper chromite or copperzinc catalyst that is

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modified to meet the needs of the individual producer. Copper chromite when prepared is nominally a complex mixture of primarily copper(II) oxide and
copper(II) chromite. But in use it is believed to be reduced to a mixture of metallic copper, copper(II) oxide, and copper(II) chromite, the metallic copper
playing an important, but as yet undefined, role in the catalysis of the reaction. The catalyst is made by reaction of copper nitrate and chromic oxide with
ammonia followed by vacuum filtering of the precipitate, water washing, and then roasting in air. The resulting material is a very fine black powder. The
roasting operation is continuous, utilizing accurate temperature control to give a catalyst of long life and high activity. Barium, manganese, or other metal
ions are sometimes added to improve stability, and silica or other binders may be put in to make a physically strong, fixed-bed catalyst pellet. Hydrogen
[1333-74-0] is usually generated on site from methane or propane. The hydrogen should be of high purity to avoid catalyst poisons, such as sulfur and
carbon dioxide, and to prevent buildup of inert gases in the system; pressure swing adsorption (PSA) is often used to remove gaseous impurities.
Methyl Ester Hydrogenolysis. The flow sheet for the continuous methyl ester, catalyst slurry process is shown in Figure 1. The dry methyl
ester, hydrogen, and catalyst slurry are fed cocurrently to a series of four vertical reactors operated at 250300C and 20,700 kPa (3000 psi). The reactors
are unagitated, empty tubes, designed to provide adequate residence time, minimum backmixing, and a reasonable column height. Fresh catalyst powder
is slurried with fatty alcohol and recycled catalyst in a weigh tank and metered into the bottom of the first reactor at approximately 3% of the ester feed
rate. The heated hydrogen is fed through a distributor in the bottom of the first reactor. Besides serving as the reducing agent, the hydrogen also provides
the principal source of heat and agitation for the reaction, and its flow conveys the mixture of ester, alcohol, and catalyst from one reactor to another.
Approximately 30 moles of hydrogen are fed per mole of ester. The product stream from the last reactor, consisting of fatty alcohol, methanol, hydrogen,
catalyst, and unreacted ester, enters a gravity separator where the vapor portion, consisting of hydrogen, methanol, and some fatty alcohol, goes
overhead. The underflow stream of crude alcohol and catalyst is heat-interchanged with ester feed and depressurized, and the catalyst is removed. Most
of the catalyst slurry is recycled but a small amount, to match the amount of fresh catalyst feed, is purged. This keeps a constant catalyst activity. The
purged catalyst can be regenerated (30) or sold to a reclaimer to recover copper values. The overhead stream is heat-interchanged with hydrogen feed,
cooled, and separated from hydrogen before being depressurized and filtered. An atmospheric stripping column removes methanol from the combined
underflow/overhead stream of crude alcohol, and the methanol is recycled to the alcoholysis process. The stripped crude fatty alcohol is distilled in a
vacuum column, or fractionated in a series of vacuum columns, to give the finished alcohol. The still bottoms, primarily fatty ester, are mainly recycled,
and a small amount of still bottoms is removed from the system as a purge.

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Fig. 1. Methyl ester, slurry catalyst process.


The process is controlled by the reaction temperature, feed rate (residence time), catalyst rate, and fresh catalyst usage. It is operated to provide the
highest production rate commensurate with high yield and product quality, as well as lowest temperature and fresh catalyst usage. Heat interchange is
used wherever possible to minimize energy consumption; low pressure steam is generated from coolers and condensers for use elsewhere in the process.
Recycling from the two blowdown tanks recovers the hydrogen dissolved in those streams and reduces the usage of hydrogen feedstock. A fat trap is
used to recover minor amounts of fatty alcohol and ester from process water streams and spills to reduce COD (chemical oxygen demand) loadings in
the process sewer. The recovered material is then recycled to the process. A minor amount of still bottoms and unusable process remnants is burned as
fuel.
The methyl ester, fixed-bed catalyst process is shown in Figure 2. A large excess of hydrogen is mixed with the methyl ester, part of which
vaporizes and is carried through one or more fixed beds of catalyst at 200250C and a pressure similar to that used in the slurry process (31). After
leaving the reactor, the mixture is cooled, then separated into a gaseous phase of mostly hydrogen, which is recycled, and a liquid phase of methanol and
fatty alcohol. The liquid phase is depressurized into a blowdown tank, which removes the methanol; the fatty alcohol that remains does not require
further purification. The alcohol is fractionated, however, if a product having a narrower carbon chain distribution is desired. The high rate of
recirculating hydrogen in this process is claimed to provide fast removal of heat, providing high yields and minimizing side reactions such as hydrocarbon
formation.

Fig. 2. Methyl ester, fixed-bed catalyst process.

Fatty Acid Hydrogenolysis. The fatty acid, slurry catalyst process operates at 315C and a pressure of 31,000 kPa (4500 psi); it is shown in
Figure 3 (32,33). This process uses a single large reactor with internal baffles and a complex flow system. First, previously prepared fatty alcohol reacts
with the acid feed to make a fatty ester via the alcoholysis reaction. A mole of water is also released. Then, the fatty ester reacts with hydrogen to give two
moles of fatty alcohol per mole of ester. One exits the reactor, the other is recycled to react with the fatty acid feed. In two stages of cooling and
separation, the excess hydrogen is separated from the reactor effluent for recycle, the reaction water is separated, and the catalyst containing fatty alcohol
is recovered. The catalyst is removed as a slurry in a centrifugal separator for recycle. A small amount of catalyst is continuously purged from the process;
an equivalent amount of fresh catalyst is added. After a final polish filtration, the crude fatty alcohol is sent to distillation: single-stage distillation for a
broad range of carbon alcohols; fractionation for a narrower range of carbon alcohols.

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Fig. 3. Fatty acid, slurry catalyst process.

Production of Unsaturated Alcohols


Unsaturated higher alcohols may be produced by saponification, sodium reduction, or hydrogenolysis of unsaturated fatty acids or esters. Saponification
of oil from the sperm whale was a former source, but bans on the slaughter of whales by some nations and a general reduction in whaling have made this
method obsolete. Alcohol made by saponification of wool grease (lanolin) is a minor product; sodium reduction of unsaturated esters is no longer an
economic process for manufacturing unsaturated alcohols. Hydrogenolysis of unsaturated fatty acids or esters to produce alcohol without loss of the
double bond has been a subject of interest for many years. Literature through the mid-1960s has been reviewed (34); and there has also been other work
reported (35). In general, the key to double bond retention is a specially designed catalyst to give selectivity coupled with reaction conditions adjusted for
the poorer reactivity of this catalyst compared to the copperchromite catalysts. Cadmium modified catalysts are claimed to be effective, as are zinc
chromite and a zinclanthanum catalyst (36). A zincaluminum catalyst reportedly avoids isomerization of the cis double bond of octadecenoic acid,
soybean fatty acid, and linseed fatty acid methyl esters during hydrogenolysis (37). The known commercial hydrogenolysis processes for the production of
octadecenol and other unsaturated alcohols are practiced by Sherex Chemical Company in the United States, Henkel K.-G.a.A. in Germany, and the New
Japan Chemical Company in Japan. In at least one procedure (38), an unsaturated fatty acid reacts in a continuous process over a fixed catalyst bed at
270290C and 19,600 kPa (2800 psi). The catalyst is a complex aluminumcadmiumchromium oxide that has high activity and exceptionally long life.
The process is claimed to give a conversion of ester to alcohol of about 99% retaining essentially all of the original double bonds.

Uses of Detergent Range Alcohols


The detergent range alcohols and their derivatives have a wide variety of uses in consumer and industrial products either because of surface-active
properties, or as a means of introducing a long chain moiety into a chemical compound. The major use is as surfactants (qv) in detergents and cleaning
products. Only a small amount of the alcohol is used as-is; rather most is used as derivatives such as the poly(oxyethylene) ethers and the sulfated ethers,
the alkyl sulfates, and the esters of other acids, eg, phosphoric acid and monocarboxylic and dicarboxylic acids. Major use areas are given in Table 11.
Table 11. Uses of Detergent Range Alcohols
Industry
detergent

Use as alcohol
emollient, foam control, opacifier,

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition)

Use as derivative
surfactant, softener

12

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petroleum and lubrication

softener
drilling mud

agriculture
plastics

evaporation suppressant
mold release agent, antifoam, emulsion
polymerization agent, lubricant

textile

lubricant, foam control, anti-static agent,


ink ingredient
softener, emollient

cosmetics
pulp and paper
food
rubber
paint and coatings
metal working
mineral processing

foam control
plasticizer, dispersant
foam control
lubricant, rolling oil
flotation agent

Vol 1

emulsifier, lubricant, dispersant, viscosity


index improver, oil field chemical,
pour-point depressant, drag reducing agent
pesticide, emulsifier, soil conditioner
plasticizer, emulsion polymerization
surfactant, lubricant dispersant, antioxidant,
stabilizer, uv absorber
emulsifier, finish, softener, lubricant,
scouring agent
emulsifier, biocide, hair conditioner,
emollient
deresination agent, de-inking agent
emulsifier, antioxidant, disinfectant
plasticizer
emulsifier
degreaser, lubricant
surfactant

Surfactants. The detergent range alcohols can be used as building blocks for all of the surfactant types: anionics, cationics, nonionics, and
zwitterionics. These alcohols are used for their emulsifying, dispersing, wetting, and cleaning properties and most surfactants (qv) made from them are
readily biodegradable. Formulation of nonphosphate heavy duty liquid laundry detergents was made possible by use of these materials as the primary
surfactant. The alkyl sulfates derived from C12 through C15 alcohols are widely used in consumer products such as shampoos, toothpastes, hand
dishwashing detergents, and light duty household cleaners. Sodium dodecyl sulfate [151-21-3] is the optimum material for many cleaning compounds
because of cleaning ability, mildness, and foaming capability. The alkyl sulfates of C16 and C18 alcohols are used in powder laundry detergents and other
heavy-duty cleaners. Minor amounts of unsulfated alcohol left in the alkyl sulfate detergents serve as foam stabilizers. Surfactants made from
polyethoxylated alcohols are in wider use than the alkyl sulfates. They tend to be less irritating to the skin than the alkyl sulfates and perform better in
liquid systems such as hand dishwashing detergents and liquid laundry detergents. The ethoxylated materials may be used underivatized as nonionic
surfactants. Alternatively, they may be sulfated and then neutralized using a base such as sodium or ammonium hydroxide to give ethoxysulfate anionic
surfactants, the largest usage category of detergent range alcohols. Although the amount of ethylene oxide [75-21-8], C2H4O, can range from 1 to about
45 moles per mole of alcohol, the degree of ethoxylation of the anionic surfactants is typically 6 to 12, whereas that of the ethoxysulfates typically ranges
from 3 to 12. Additionally, ethoxylation yields a broad range of species: for instance, a nominal 3-mole ethoxylate has some alcohol molecules containing
up to 14 units of ethylene oxide, yet it also includes about 15% unreacted alcohol, giving the effect of a mixed surfactant system. Varying the number of
parent alcohol carbons, the amount of ethylene oxide used, and to some extent the breadth of the ethylene oxide distribution, gives wide latitude in the
hydrophilelipophile balance (HLB) of the resulting surfactant, which may be used as a nonionic surfactant or sulfated to give an anionic one. This
versatility accounts for the broad use of ethoxylates in consumer cleaning products and in industrial applications as wetting agents, cleaning products,
dispersing agents, and emulsifiers.
Alkyl glyceryl ether sulfonates are very mild, high foaming surfactants used in bar soaps and shampoos; they are made from the sulfonated alkyl
chlorohydrin ether of detergent range alcohols. Alkyldimethyl amines are made from alcohols and then oxidized to give the amine oxide which is used as
a mild surfactant in hand dishwashing products, shampoos, and some cosmetic applications. Some specialty cationic quaternary nitrogen surfactants are
also made from the alcohols. Specialty phosphate ester surfactants are made from detergent range alcohols and ethoxylated alcohols; these find use
mainly as lubricants and wetting agents in the textile industry.
In other surfactant uses, dodecanoltetradecanol is employed to prepare porous concrete (39), stearyl alcohol is used to make a polymer concrete
(40), and lauryl alcohol is utilized for froth flotation of ores (41). A foamed composition of hexadecanol is used for textile printing (42) and a foamed
composition of octadecanol is used for coating polymers (43). On the other hand, foam is controlled by detergent range alcohols in applications: by lauryl
alcohol in steel cleaning (44), by octadecanol in a detergent composition (45), and by eicosanoldocosanol in various systems (46).
Cosmetics and Pharmaceuticals. The main use of hexadecanol (cetyl alcohol) is in cosmetics (qv) and pharmaceuticals (qv), where it and
octadecanol (stearyl alcohol) are used extensively as emollient additives and as bases for creams, lipsticks, ointments, and suppositories. Octadecenol
(oleyl alcohol) is also widely used (47), as are the nonlinear alcohols. The compatibility of heavy cut alcohols and other cosmetic materials or active drug
agents, their mildness, skin feel, and low toxicity have made them the preferred materials for these applications. Higher alcohols and their derivatives are
used in conditioning shampoos, in other personal care products, and in ingested materials such as vitamins (qv) and sustained release tablets (see
CONTROLLED RELEASE TECHNOLOGY).
Lubricants and Petroleum. Methacrylate esters of detergent range alcohols find use as viscosity index improvers, pour-point depressants,
and dispersants (qv) in automobile engine lubricants. The free alcohol, particularly dodecanol (lauryl alcohol), is widely used in aluminum rolling, and also
in other metalworking (48). A composition of octadecenol and sodium lauryl sulfate is used for petroleum oil recovery (49). Esters of docosanol are used
as drag reducing agents for pipelining of crude petroleum oil, which reduces the power requirements for pumping.
Other Applications. Alkylbenzyldimethylammonium salts are made from alcohols in the C12C16 range and find use as biocides and
disinfectants in a number of areas. Dodecanol, tetradecanol, octadecanol, and tridecyl alcohol esters of thiodipropionic acid are employed as part of the
antioxidant system of polyolefin plastics. Higher alcohols are used as antistatic agents (qv), mold release agents, and as additives in olefin polymerization
(50); other uses have been reviewed (51). Esters of detergent range alcohols and fatty acids, lactic acid, and maleic acid are used for cosmetics and

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lubricants. Phosphites and phosphates of detergent range alcohols are also articles of commerce. Triacontanol (C32) has activity as a plant growth
regulator, but results have not been consistent enough for commercial use (52). Hexadecanol and octadecanol can be used to retard evaporation of water
from reservoirs in arid regions (53). Detergent range alcohols also find application in antifoulant coatings, adhesives, and fabric softeners (54).

Uses of Plasticizer Range Alcohols


The plasticizer range alcohols are utilized primarily in plasticizers, but they also have a wide range of uses in other industrial and consumer products, as
shown in Table 12. As in the case of the detergent range alcohols, the plasticizer range materials are little used as is, but rather are employed as the ester
derivatives of acids such as phthalic, adipic, and trimellitic.
Table 12. Uses of Plasticizer Range Alcohols
Industry
plastics

Use as alcohol
emulsion polymerization

petroleum and lubrication

defoamer

agriculture

stabilizer, tobacco sucker control, herbicide,


fungicide
solvent, extractant, antifoam
leveling agent, defoamer
solvent, smoothing agent
solvent, lubricant, protective coating
antifoam, solvent

mineral processing
textile
coatings
metal working
chemical processing
food
cosmetics

Use as derivative
plasticizer, flame retardant, oxidation and uv
stabilizer, heat stabilizer, polymerization
initiator
lubricant, grease, lubricant additive, hydraulic
fluid, diesel fuel additive
surfactant, insecticide, herbicide
extractant, surfactant
surfactant
surfactant, drying agent, solvent
lubricant, surfactant
solvent
flavoring agent

perfume ingredient

Plasticizers. Over 70% of plasticizer range alcohols are ultimately consumed as plasticizers for PVC and other resins. Of this amount, 80% is
used as the diester of phthalic acid, for instance di-2-ethylhexyl phthalate (DOP) or diisodecyl phthalate (DIDP) [26761-40-0]. Other plasticizers made
from these alcohols are the diesters of adipic acid, azeleic acid, and sebacic acid, plus the triesters of phosphoric acid and trimellitic acid. A small amount
of alcohol is used as the terminating agent in specialty polyester plasticizers. The adipates, azelates, and sebacates are employed as specialty materials in
some food contact applications and in areas where low temperature flexibility is important, such as automobile interiors; eg, the diadipate ester of hexanol
is the plasticizer in poly(vinyl butyral) used for automobile safety glass. The phosphates find application as good low temperature plasticizers and as flame
retardant additives, whereas the trimellitates are used for high temperature applications such as the insulation of electrical wiring. The phthalates,
however, are the general purpose plasticizers. Phthalate esters of alcohols from 413 carbons are available although most are in the C8 through C10 range.
All plasticizers are chosen on the basis of performance, cost, and ease of processing; DOP and DIDP are the workhorses of the industry. When
compared to DOP, phthalates of mixed linear alcohols (for instance, mixed heptyl, nonyl, and undecyl alcohols) give improved low temperature
properties and resistance to volatile loss whereas those made of higher molecular weight alcohols (for instance, isodecyl or tridecyl alcohols) give
improved resistance to extraction and volatile loss but exhibit some loss of plasticizing ability. In general, esters of mixtures of alcohols are favored as
plasticizers because they give a broader range of properties than esters of a single alcohol.
Other Plastics Uses. The plasticizer range alcohols have a number of other uses in plastics: hexanol and 2-ethylhexanol are used as part of
the catalyst system in the polymerization of acrylates, ethylene, and propylene (55); the peroxydicarbonate of 2-ethylhexanol is utilized as a polymerization
initiator for vinyl chloride; various trialkyl phosphites find usage as heat and light stabilizers for plastics; organotin derivatives are used as heat stabilizers
for PVC; octanol improves the compatibility of calcium carbonate filler in various plastics; 2-ethylhexanol is used to make expanded polystyrene beads
(56); and acrylate esters serve as pressure sensitive adhesives.
Lubricants, Fuels, and Petroleum. The adipate and azelate diesters of C6 through C11 alcohols, as well as those of tridecyl alcohol, are
used as synthetic lubricants, hydraulic fluids, and brake fluids. Phosphate esters are utilized as industrial and aviation functional fluids and to a small
extent as additives in other lubricants. A number of alcohols, particularly the C8 materials, are employed to produce zinc dialkyldithiophosphates as
lubricant antiwear additives. A small amount is used to make viscosity index improvers for lubricating oils. 2-Ethylhexyl nitrate [24247-96-7] serves as a
cetane improver for diesel fuels and hexanol is used as an additive to fuel oil or other fuels (57). Various enhanced oil recovery processes utilize
formulations containing hexanol or heptanol to displace oil from underground reservoirs (58); the alcohols and derivatives are also used as defoamers in
oil production.
Agricultural Chemicals. Plasticizer range alcohols are used as intermediates in the manufacture of a number of herbicides (qv) and
insecticides, the largest use being that of 2-ethylhexanol and isooctyl alcohol to make the octyl ester of 2,4-dichlorophenoxyacetic acid (2,4-D) [94-75-7]
for control of broadleaf weeds. Surfactants made from these alcohols are used as emulsifiers and wetting agents for agricultural chemicals. A mixture of
octanol and decanol and the proper surfactants is able to kill the young meristemic tissue of some plants without harming more mature tissue. This is the
basis for formulations that kill unwanted buds (suckers) in tobacco (59) and other plants and serve as a selective herbicide. Both decanol and
4-methyl-2-pentanol can be used as fungicides (qv) (60).
Surfactants. A number of surfactants are made from the plasticizer range alcohols, employing processes similar to those for the detergent

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range materials such as sulfation, ethoxylation, and amination. These surfactants find application primarily in industrial and commercial areas: ether
amines and trialkyl amines are used in froth flotation of ores, and the alcohols are also used to dewater mineral concentrates or break emulsions (61). The
dialkyl sulfosuccinates of many of the C8 through C13 alcohols also have surfactant applications. Octanol has found an application in a cleaning
composition for engine carburetors, and decanol in a detergent for cleaning cotton (62).
Other Applications. The alcohols through C8 have applications as specialty solvents, as do derivatives of linear and branched hexanols. Inks,
coatings, and dyes for polyester fabrics are other application areas for 2-ethylhexanol (63). Di(2-ethylhexyl) phthalate is used as a dielectric fluid to replace
polychlorinated biphenyls. Trialkyl amines of the linear alcohols are used in solder fluxes, and hexanol is employed as a solvent in a soldering flux (64).
Quaternary ammonium compounds of the plasticizer range alcohols are used as surfactants and fungicides, similarly to those of the detergent range
alcohols.

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General References
Fatty Alcohols, Raw Materials, Methods, Uses, Henkel K.-G.a.A., Dsseldorf, 1982. Also published in German as Fettalkohole.
J. A. Monick, Alcohols, Their Chemistry, Properties and Manufacture, Reinhold Book Corp., New York, 1968.
E. J. Wickson, ed., Monohydric Alcohols, ACS Symp. Ser. 159, American Chemical Society, Washington, D.C., 1981.
Richard A. Peters
The Procter & Gamble Company

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