You are on page 1of 16

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

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 Mp, Viscosit in water of Solubility in other y, wa solvents C ac ter mPas ,

IUPAC name

CAS Registry Number

Molecul Other common Specifi Refracti ar names c ve formula gravity, index, a a 20C 20C

Bp, C, 101.3 b kPa

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

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

1-hexanol 1-heptanol 1-octanol 1-nonanol 1-decanol 1-undecanol 1-dodecanol 1-tridecanol 1-tetradecanol 1-pentadecanol 1-hexadecanol 1-heptadecanol 1-octadecanol 1-nonadecanol 1-eicosanol 1-hexacosanol 1-hentriacontanol 9-hexadecen-1-ol 9-octadecen-1-ol 10-eicosen-1-ol

[111-27-3] C6H14O n-hexyl alcohol

Primary normal aliphatic 0.8212 1.4181 157 176 195 213 230 243 1381.33 1552.0

44 35 5 15:5

5.9 7.4 8.4 11.7 13.8 17.2 18.8

0.5920 0.1018 0.0625

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

[111-70-6] C7H16O n-heptyl alcohol 0.8238 1.4242 [111-87-5] C8H18O n-octyl alcohol 0.8273 1.4296 [143-08-8] C9H20O n-nonyl alcohol 0.8295 1.4338 [112-30-1] C10H22O n-decyl alcohol 0.8312 1.4371 [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 [1454-85-9 C17H36O margaryl alcohol ] [112-92-5] C18H38O stearyl alcohol, 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, 3] myricyl alcohol [10378-01- C16H32O palmitoleyl 5] alcohol [143-28-2] C18H36O oleyl alcohol 0.8339 1.4402 0.83062 1.4428
5

16 24 30.5 38 44 49 54 58 62

<0:02

0.82383
1 0

0.81655 1.435850 1581.33 1.440850 0.81576 1.439260 1771.33


0

<0:02

nil petroleum ether, ethanol

5375

0.0620

nil ethanol, methanol, diethyl ether, benzene nil

0.81676 1.439260
0

0.81376 1.438860 2031.33


0

2511.33 3052.67 0.7784


5 9

66 79.5 87

i i nil

nil benzene, ethanol, petroleum ether ethanol, ether

2052102.
0

0.85045 1.447360
8

ethanol, diethyl ether

[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-pen [123-44-4] C8H18O 0.839 1.4300 168 tanol Secondary aliphatic 4-methyl-2-pentanol [108-11-2] C6H14O methylamyl 0.8083 1.4112 132 alco-hol, methyliso-butyl carbinol 0:83515=4 1.4256 2-octanol [123-96-6] C8H18O capryl alcohol 178179 2,6-dimethyl-4-hepta [108-82-7] C9H20O diisobutylcar-bi 0.8121 1.4231 nol nol 2,6,8-trimethyl-4-non [123-17-1] C12H26O 0.8193 1.4345 178 225

6.6
114 70

0.31

5.4

9.8

0.07

2.6 ethanol, diethyl ether ethanol

70 90

5.2

1.7

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

38 65 60

8.2 14.3 21

0.09625 0.06
<0:02

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

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

anol 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.
a

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 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.
1

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 (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

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

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

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 Sherex Shell Chemical Vista Ethyl Exxon Process catalytic hydrogenolysis catalytic hydrogenolysis modified oxo Ziegler modified Ziegler modified oxo Feedstock coconut and palm kernel oils, tallow, palm oil tallow ethylene/olefins ethylene ethylene olefins Products C6C18 C16, C18, oleyl C9C15 C6C22 C6C22 C13, C15

Table 3. Prices of Detergent Range Alcohols Alcohol lauryl alcohol, fob dodecanol/tridecanol, delivered hexadecanol, fob octadecanol, fob a November 1989 list prices.

Price, U.S.$/kg 1.54 1.26 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.

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

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

Table 4. Prices and Manufacturers of Plasticizer Range Alcohols Material hexanol 4-methyl-2-pentanol octanol octanol, perfumer's grade isooctyl alcohol 2-ethylhexanol Price, U.S.$/kg 1.74 1.32 2.01 3.09 0.97 0.93
a

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

decanol
a

1.34

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 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,

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

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

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.
a

Table 6. Composition of Commercial Detergent Range Alcohols Alcohol commercial name lauryl Representative trade name 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
b

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 26 45 27 1 20 27 1 99 1 2 4

C16 6 7 17 1 1 98 98 27 26 1 5 14

C18

C20

57

14

myristyl cetyl tallow stearyl oleyl


a

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. d Registered trademark for Ethyl Corporation alcohols. e Registered trademark for Shell alcohols. f Registered trademark for Henkel alcohols. h Includes 1% C17 alcohol.
b g i

Registered trademark for Sherex alcohols. Primarily unsaturated.

Table 7. Properties of Commercial Linear Detergent Range Alcohols Commercial descriptive name lauryl (99% C12) lauryl (68% C12) C12C13 cetyl tallow
a

Hydroxy l Value 301 285 289 229 208

Saponification Value 0.2 0.2 0.4 1.8

Acid Valu e 0.02 0.01 0.02 0 0

Iodin e Value 0.2 0 0.6 0.5

Melting point, C 2325 22 1822 49 53

Color, APH A 5 3 5 610 1020

Moisture, % 0.03 0.04 0.02 0.04 0.03

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

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

stearyl 206 0.5 oleyl 206 0.5 a Neodol 23 (registered trademark for Shell alcohols).

0.7 94

58 4

615

0.03

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 tridecyl
a b

Molecular formula (C6H14O) C8H18O) (C8H18O) (C9H20O) (C8H18O) (C10H22O) (C13H28O)

Hydroxy l Value

Acidity, % as acetic 0.001

Carbonyl, wt % O
<0:003 <0:02 <0:003 <0:003

Boiling range, C 152160 182186 184190 202213 168203 184195 226230 254263

Color, APH A 5
<10

Moisture, % 0.05
<0:10

Flash point , C 63 84
b

431

<0:007

0.001 0.001 408 431 355 283


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

0.003 0.003 0.003


<0:003

0.001

5 5 5 5 5 5

0.05 0.05 0.01 0.03 0.03


<0:05

84 91 81 c 88 113 127
c

Pensky-Martens closed cup unless otherwise noted. Cleveland open cup. c Tag close cup.

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] 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

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

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

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

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, g/kg 3.24.4
a

Eye irritation, rabbits

hexanol severe 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 moderate >2 isooctyl severe moderate decyl 4.7 severe moderate tridecyl 4.7 moderate 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.

Primary skin irritation, c rabbits moderate moderate moderate slight mild mild mild moderate moderate

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

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

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

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 ! NaOCH 3 3 RCOOCH 3 + C 3 H 5 (OH)3 C 3 H 5 (OOCR) 3 + 3 CH 3 OH 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 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.

purchased in methanol solution. Usage is approximately 0.31.0 wt % of the triglyceride.

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

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

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.

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

10

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

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.

Fig. 3. Fatty acid, slurry catalyst process.

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

11

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

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 petroleum and lubrication agriculture plastics textile cosmetics pulp and paper food rubber paint and coatings metal working mineral processing Use as alcohol emollient, foam control, opacifier, softener drilling mud evaporation suppressant mold release agent, antifoam, emulsion polymerization agent, lubricant lubricant, foam control, anti-static agent, ink ingredient softener, emollient foam control plasticizer, dispersant foam control lubricant, rolling oil flotation agent Use as derivative surfactant, softener 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

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

12

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

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 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 petroleum and lubrication agriculture mineral processing textile coatings metal working chemical processing food cosmetics Use as alcohol emulsion polymerization defoamer stabilizer, tobacco sucker control, herbicide, fungicide solvent, extractant, antifoam leveling agent, defoamer solvent, smoothing agent solvent, lubricant, protective coating antifoam, solvent perfume ingredient 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

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

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

13

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

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 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.

BIBLIOGRAPHY
"Alcohols, Higher" in ECT 1st ed., Vol. 1, pp. 315321, by H. B. McClure, Carbide and Carbon Chemicals Corporation, Unit of Union Carbide and Carbon Corporation; "Alcohols, Higher, Fatty" in ECT, 2nd ed., Vol. 1, pp. 542559, by K. R. Ericson and H. D. Van Wagenen, The Procter & Gamble Company; "Alcohols, Higher, Synthetic" in ECT, 2nd ed., Vol. 1, pp. 560569, by R. W. Miller, Eastman Chemical Products, Inc. "Alcohols, Higher Aliphatic, Survey and Natural Alcohols Manufacture" in ECT 3rd ed., Vol. 1, pp. 716739, by R. A. Peters, Procter & Gamble Company. 1. Braz. Pat. Pedido 86 2469A (Jan. 27, 1987), S. Inada and co-workers (to Seitetsu Kagaku Co., Ltd., Shinko Seito Co., Ltd., and Shinko Sugar Production Co., Ltd.); Chem. Abstr. 107, 236087n (1987). 2. R. G. Ackman, S. N. Hooper, S. Epstein, and M. Kelleher, J. Am. Oil Chem. Soc. 49, 378382 (1972). 3. J. Sever and P. L. Parker, Science 164, 10521054 (1969). 4. T. K. Miwa, J. Am. Oil Chem. Soc. 48, 259 (1971); A. P. Tulloch, J. Am. Oil Chem. Soc. 50, 367371 (1973). 5. R. C. Wilhoit and B. J. Zwolinski, J. Phys. Chem. Ref. Data 2 (1) (1973). 6. U.S. Pat. 4,097,535 (June 27, 1978), K. Yang, K. L. Motz, and J. D. Reedy (to Continental Oil Co.). 7. D. Landini, F. Montanari, and F. Rolla, Synthesis 2, 134136 (1979). 8. Eur. Pat. Appl. EP 281,417 (Sept. 14, 1988), P. Y. Fong, K. R. Smith, and J. D. Sauer (to Ethyl Corp.). 9. U.S. Pat. 4,683,336 (July 28, 1987), C. W. Blackhurst (to Sherex Chemical Co.). 10. Storage and Handling of Shell Neodol Detergent Alcohols, Ethoxylates, and Ethoxysulfates, SC:133179, Shell Chemical Company, Houston, Tex., 1979. 11. T. Gibson, CEH Marketing Research Report: Plasticizer Alcohols, SRI International, Menlo Park, Calif, 1989. 12. Data from U.S. International Trade Commission. 13. J. A. Monick, Alcohols, Their Chemistry, Properties and Manufacture, Reinhold Book Corp., New York, 1968, pp. 519579. 14. R. E. Oborn and A. H. Ullman, J. Am. Oil Chem. Soc. 63, 9597 (1986). 15. Products from the Chemicals Division, Procter & Gamble Company, Cincinnati, Ohio, 1987; Adol Fatty Alcohols, Sherex Chemical Company, Dublin, Ohio, 1986; Vista Surfactants, Industrial Chemicals, and Plastics, Vista Chemical Company, Houston, Texas, 1987; Epal Linear Primary Alcohols, Ethyl Corporation, Baton Rouge, Louisiana, 1985; Neodol, Shell Chemical Company, Houston, Texas, 1987; Henkel Fat Raw Materials, Henkel K.-G.a.A., Dsseldorf, Fed. Rep. Germany. 16. The United States Pharmacopeia, 21st rev. The National Formulary, 16th ed., United States Pharmacopeial Convention, Rockville, Md., 1984; Food Chemicals Codex, 3rd ed., National Academy Press, Washington, D.C., 1981.

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

14

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

17. 18.

19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36.

37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48.

49. 50.

51. 52. 53. 54. 55.

56. 57. 58. 59. 60.

Exxal Guerbet Alcohols, Exxon Corporation, Houston, Texas, 1988. Vista Surfactants, Industrial Chemicals, and Plastics, Vista Chemical Company, Houston, Texas, 1987; Epal Linear Primary Alcohols, Ethyl Corporation, Baton Rouge, Louisiana, 1985; Exxal Alcohols, Exxon Chemical Company, Houston, Texas, 1988; Aristech Alcohols, 2-Ethlyhexanol, Aristech Chemical Corporation, Pittsburgh, Pa., 1988; Technical Bulletin, 2-Ethylhexanol, BASF Corporation, Parsippany, N.J., 1987. D. L. J. Opdyke, ed., Monographs on Fragrance Raw Materials, Pergamon Press, Oxford, 1974, pp. 8, 35, 39, 42. R. A. Scala and E. G. Burtis, J. Am. Ind. Hyg. Assn. 34, 493499 (1973). Epal Linear Primary Alcohols, Ethyl Corporation, Baton Rouge, Louisiana, 1985. V. K. Rowe and S. B. McCollister in G. D. Clayton and F. E. Clayton, eds., Patty's Industrial Hygiene and Toxicology, Vol. 2C, 3rd ed., John Wiley & Sons, Inc., New York, 1982, pp. 42574708. MSDS for Alfol Alcohols, Vista Chemical Company, Houston, Texas, 1984, 1985. J. Am. Coll. Toxicol. 7, 359423 (1988). H. W. Gerarde and D. B. Ahlstrom, Arch. Environ. Health 13, 457461 (1966). U.S. Pat. 2,091,800 (Aug. 31, 1937), H. Adkins, K. Folkers, and R. Connor (to Rohm & Haas Co.). Ger. Offen. 3,624,812 (Jan. 28, 1988), F.-J. Carduck, J. Falbe, T. Fleckenstein, and J. Pohl (to Henkel K.-G.a.A.). U.S. Pat. 4,608,202 (Aug. 26, 1986), H. Lepper and L. Friesenhagen (to Henkel K.-G.a.A.). F. E. Sullivan, Chem. Eng. New York 81, 56 (April 15, 1974). U.S. Pat. 4,533,648 (Aug. 6, 1985), P. J. Corrigan, R. M. King, and S. A. Van Diest (to The Procter & Gamble Co.). U. R. Kreutzer, J. Am. Oil Chem. Soc. 61, 343348 (1984). H. Buchold, Chem. Eng. New York 90, 42, 43 (1983). U.S. Pat. 4,259,536 (Mar. 31, 1981), T. Voeste, H. J. Schmidt, and F. Marschner (to Metallgesellschaft A.-G.). H. Bertsch, H. Reinheckel, and K. Haage, Fette Seifen Anstrichm. 66, 763773 (1964); E. S. Lower, Spec. Chem. 2(1), 30 (1982). U.S. Pat. 3,193,586 (July 6, 1965), W. Rittmeister (to Dehydag, Deutsche Hydrierwerke); J. D. Richter and P. J. Van Den Berg, J. Am. Oil Chem. Soc., 46, 158162, 163166 (1969). Brit. Pat. 1,076,855 (July 26, 1967), A. J. Pantulu, K. T. Achaya, G. S. Sidhu, and S. H. Laheer (to Council of Scientific and Industrial Research, India); Jpn. Kokai 58 210,035 (Dec. 7, 1983) (to Kao Corp.); Ger. Pat. 2,513,377 (Sept. 9, 1976), G. Demmering (to Henkel & Cie.). U.S. Pat. 3,729,520 (Apr. 24, 1973), H. Rutzen and W. Rittmeister (to Henkel & Cie.). Brit. Pat. 1,335,173 (Oct. 24, 1973) (to New Japan Chemical Co.). Eur. Pat. Appl. 296,941 (Dec. 28, 1988), G. Dion Biro and R. De Bona Biro; Ger. Offen. 3,807,250 (Sep. 15, 1988), J. Sulkiewicz (to Anthes Industries, Inc.). Jpn. Kokai 63 176,345 (July 20, 1988), C. Tomizawa and S. Narisawa (to Sumitomo Chemical Co.). Ger. Offen. 3,517,154 (Nov. 13, 1986), W. Von Rybinski and R. Koester (to Henkel K.-G.a.A.). Ger. Offen. 3,535,454 (Apr. 9, 1987), W. Braeuer and P. Diewald (to Bayer A.-G.). Jpn. Kokai 53 101,061 (Sep. 4, 1978), E. Sugawara, S. Shioume, and K. Yorikane (to Dainichi Nippon Cables, Ltd.). Jpn. Kokai 58 221,300 (Dec. 22, 1983) (to Nippon Kokan K.K. and Kao Corp.). Eur. Pat. Appl. 210,721 (Feb. 4, 1987), P. M. Burrill (to Dow Corning Corp.). Ger. Offen. 3,001,387 (July 23, 1981), R. Peppmoeller (to Chemische Fabrik Stockhausen und Cie.). U. Ploog, Seife. Oele. Fette. Wachse, 109, 225229 (1983). Eur. Pat. Appl. 182,552 (May 28, 1986), M. K. Budd and M. H. Foster (to Alcan International Ltd.); Jpn. Kokai 63 393 (Jan. 5, 1988), K. Nabatake, M. Ogawa, Y. Iwasaki, and T. Mizuta (to Nippon Steel Corp. and Daido Chemical Industry Co., Ltd.); N. P. Korotkova, I. G. Turyanchik, G. I. Cherednichenko, and V. P. Temnenko, Neftepererab. Neftekhim. (Kiev), 34, 1618 (1988); Chem. Abstr. 110, 98392s (1989). U.S. Pat. 4,213,500 (July 22, 1980), R. L. Cardenas and J. T. Carlin (to Texaco, Inc.). Jpn. Kokai 59 217,782 (Dec. 7, 1984) (to Lion Corp.); U.S. Pat. 4,239,862 (Dec. 16, 1980), D. N. Matthews, W. Nudenberg, and H. A. Petersen (to Uniroyal, Inc.); Jpn. Kokai 61 138,606 (June 26, 1986), T. Tsutsui, M. Kioka, and N. Kashiwa (to Mitsui Petrochemical Industries, Ltd.). E. S. Lower, Polym. Paint Colour J. 173, 506 (1983). S. K. Ries, CRC Crit. Rev. Plant Sci. 2, 239285 (1985); S. K. Ries and R. Houtz, HortScience 18, 654662 (1983). U.S. Pat. 3,415,614 (Dec. 10, 1968), R. R. Egan and S. R. Sheeran (to Ashland Oil and Refining Co.). Jpn. Kokai 62 13,471 (Jan. 22, 1987), Y. Yonehara and Y. Nanishi (to Kansai Paint Co., Ltd.); Jpn. Kokai 58 101,182 (June 16, 1983) (to Toshiba Silicone Co., Ltd.); Belg. Pat. 904,142 (July 30, 1986), J. P. Grandmaire and A. Jacques (to Colgate-Palmolive Co.). Eur. Pat. Appl. 190,892 (Aug. 13, 1986), C. J. Chang (to Rhom and Haas Co.); Jpn. Kokai 62 135,501 (June 18, 1987), Y. Kondo, M. Mori, Y. Naito, and T. Chigusa (to Toyo Soda Mfg. Co., Ltd.); Jpn. Kokai 63 89,507 (Apr. 20, 1988), M. Terano, H. Soga, and M. Inoue (to Toho Titanium Co., Ltd.). Jpn. Kokai 58 122,935 (July 21, 1983) (to Sekisui Kaseihin Kogyo K. K. and Eslen Kako K. K.); Fr. Demande 2,531,971 (Feb. 24, 1984), H. P. Schlumpf, C. Stock, and P. Trouve (to Pluess-Staufer A.-G.). Ger. Offen. 2,910,011 (Sep. 20, 1979), M. J. Rose; Ger. Offen. 3,626,102 (Feb. 11, 1988), M. L. Nelson and O. L. Nelson, Jr. (to Polar Molecular Corp.). U.S. Pat. 4,485,871 (Dec. 4, 1984), B. W. Davis (to Chevron Research Co.); Brit. Pat. 1,542,166 (Mar. 14, 1979), Y.-C. Chiu (to Shell Internationale Research Maatschappij B.V.); U.S. Pat. 4,193,452 (Mar. 18, 1980), P. M. Wilson and J. Pao (to Mobil Oil Corp.). Off-Shoot-T, Cochrane Corporation, Memphis, Tenn., 1984. U.S. Pat. 3,778,509 (Dec. 11, 1973), H. L. Lewis (to Cotton, Inc.); Ger. Offen. 2,330,596 (Jan. 10, 1974), E. L. Frick and R. T. Burchill (to National Research Development Corp.).

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

15

SURVEY AND NATURAL ALCOHOLS MANUFACTURE

Vol 1

61. 62. 63.

64.

Ger. Offen. 3,018,758 (Dec. 17, 1981), R. Peppmoeller (to Chemische Fabrik Stockhausen und Cie.); U.S. Pat. 4,206,063 (June 3, 1980), C. Dugan, M. E. Lewellyn, and S. S. Wang (to American Cyanamid Co.). Jpn. Kokai 60 155,299 (Aug. 15, 1985), H. Murata and R. Hidaka (to Nitto Chemical Industry Co., Ltd.); U.S. Pat. 4,056,355 (Nov. 1, 1977), J. H. Kolaian, F. C. McCoy, and J. A. Patterson (to Texaco, Inc.). U.S. Pat. 4,711,802 (Dec. 8, 1986), H. P. Tannenbaum (to E. I. du Pont de Nemours & Co., Inc.); Ger. Offen. 3,508,419 (Sep. 11, 1986), G. Neubert, M. Melan, and W. Schultze (to BASF A.-G.); Ger. Offen. 2,413,866 (Oct. 2, 1975), M. Vescia, M. Daeuble, and R. Widder (to BASF A.-G.). Ger. Offen. 3,513,424 (Oct. 23, 1986), W. Kellberg (to Siemens A.-G.).

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

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

16