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Fatty Alcohols
Klaus Noweck, Condea Chemie GmbH, Brunsbüttel, Federal Republic of Germany
IUPAC name Common name CAS registry Molecular Mr Hydroxyl mp, bp, ◦ C Density, Refractive
◦
number formula number C (p, kPa) g/cm3 index
(t, ◦ C) (t, ◦ C)
1-Hexanol caproic alcohol [111-27-3] C6 H14 O 102.2 548 −52 157 0.819 (20) 1.4181 (20)
1-Heptanol enanthic alcohol [111-70-6] C7 H16 O 116.2 482 −30 176 0.822 (20) 1.4242 (20)
1-Octanol caprylic alcohol [111-87-5] C8 H18 O 130.2 430 −16 195 0.825 (20) 1.4296 (20)
1-Nonanol pelargonic alcohol [143-08-8] C9 H20 O 144.3 388 − 4 213 0.828 (20) 1.4338 (20)
1-Decanol capric alcohol [112-30-1] C10 H22 O 158.3 354 7 230 0.829 (20) 1.4371 (20)
1-Undecanol [112-42-5] C11 H24 O 172.3 326 16 245 0.830 (20) 1.4402 (20)
1-Dodecanol lauryl alcohol [112-53-8] C12 H26 O 186.3 300 23 260 0.822 (40) 1.4428 (20)
1-Tridecanol [112-70-9] C13 H28 O 200.4 280 30 276
1-Tetradecanol myristyl alcohol [112-72-1] C14 H30 O 214.4 261 38 172 (2.67) 0.823 (40) 1.4358 (50)
1-Pentadecanol [629-76-5] C15 H32 O 228.4 245 44 1.4408 (50)
1-Hexadecanol cetyl alcohol [36653-82-4] C16 H34 O 242.5 230 49 194 (2.67) 0.812 (60) 1.4392 (60)
1-Heptadecanol margaryl alcohol [1454-85-9] C17 H36 O 256.5 218 54
1-Octadecanol stearyl alcohol [112-92-5] C18 H38 O 270.5 207 58 214 (2.67) 0.815 (60) 1.4388 (60)
1-Nonadecanol [1454-84-8] C19 H40 O 284.5 196 62 1.4328 (70)
1-Eicosanol arachidyl alcohol [629-96-9] C20 H42 O 298.6 187 64 215 (1.33) 0.806 (70)
1-Heneicosanol [15594-90-8] C21 H44 O 312.6 179 68
1-Docosanol behenyl alcohol [661-19-8] C22 H46 O 326.6 171 71 241 (1.33) 0.807 (80)
1-Tricosanol [3133-01-5] C23 H48 O 340.6 164 74
1-Tetracosanol lignoceryl alcohol [506-51-4] C24 H50 O 354.7 158 77
1-Pentacosanol [26040-98-2] C25 H52 O 368.7 152 78
1-Hexacosanol ceryl alcohol [506-52-5] C26 H54 O 382.7 146 81
1-Heptacosanol [2004-39-9] C27 H56 O 396.8 141 82
1-Octacosanol montanyl alcohol [557-61-9] C28 H58 O 410.8 136 84
1-Nonacosanol [6624-76-6] C29 H60 O 424.8 132 85
1-Triacontanol myricyl alcohol [593-50-0] C30 H62 O 438.8 128 87
1-Hentriacontanol melissyl alcohol [544-86-5] C31 H64 O 452.9 124 87
1-Dotriacontanol lacceryl alcohol [6624-79-9] C32 H66 O 466.9 120 89
1-Tritriacontanol [71353-61-2] C33 H68 O 480.9 116
1-Tetratriacontanol geddyl alcohol [28484-70-0] C34 H70 O 494.9 113 92
Fatty Alcohols
3
4 Fatty Alcohols
sperm oil with concentrated sodium hydroxide Molten sodium is dispersed in an inert sol-
at ca. 300 ◦ C and distilling the alcohol from the vent and the carefully dried ester and alcohol
sodium soap. are added. When the reaction is complete, the
alkoxides are split by stirring in water, and the
alcohols are washed and distilled [25].
The added alcohol R3 OH, preferably a sec-
ondary alcohol, acts as a hydrogen donor. Be-
The distillate consists of partially unsaturated cause of side reactions, the consumption of
C16 – C20 alcohols, which are hardened by cat- sodium can be as much as 20 % above the stoi-
alytic hydrogenation to prevent autoxidation. chiometric requirement.
Since sperm oil contains only ca. 70 % wax es- The reduction proceeds selectively without
ters, the alcohol yield is about 35 %. production of hydrocarbons and isomerization
or hydrogenation of double bonds. Extensive
safety measures are required due to the large
2.3.2. Reduction of Wax Esters with Sodium quantity of metallic sodium used. The process
was used until the 1950s to produce unsaturated
The reduction of esters with sodium was first fatty alcohols, especially oleyl alcohol from
described in 1902 by Bouveault and Blanc sperm oil. These alcohols can now be produced
(for a review, see [24]). Large-scale application by selective catalytic hydrogenation processes
of this process was achieved in 1928 (Dehydag). using cheap raw materials, and the sodium re-
duction process is of interest only in special
cases. A fully continuous plant with a produc-
tion capacity of 3600 t/a was built in Japan in
1973 for the reduction of sperm oil [26].
Fatty Alcohols 5
2.3.3. Hydrogenation of Natural Raw acid number (milligrams of KOH needed to neu-
Materials tralize one gram of substance) is used as a qual-
ity characteristic and for process control. Batch
2.3.3.1. Raw Materials and Pretreatment and continuous processes give esters of simi-
lar quality, but the continuous process uses less
For the production of C12 – C14 alcohols, only methanol and the residence time is reduced. The
coconut oil and palm kernel oil can be used. Palm methyl ester is subsequently distilled for purifi-
oil, soybean oil, and tallow are the main sources cation.
for C16 – C18 alcohols. Rapeseed oil rich in eru- Transesterification of Triglycerides. This re-
cic acid yields fatty alcohols with 20 or 22 car- action is carried out continuously with alkaline
bon atoms. Bifunctional fatty alcohols can be catalysts. Like esterification, transesterification
obtained from castor oil and other special oils is an equilibrium reaction and is shifted toward
(see Chap. 5). More than 90 % of the vegetable the desired ester by excess methanol or removal
oils are used in food applications. of glycerol:
Before hydrogenation, contaminants such as
phosphatides, sterols, or oxidation products and
impurities such as seed particles, dirt, and water
are removed in a cleaning stage, which includes
refining with an adsorption agent (→ Fats and
Fatty Oils, Chap. 6.).
The refined triglycerides are then hydrolyzed
to yield fatty acids (→ Fatty Acids) or transes- If the reaction is carried out under mild con-
terified with lower alcohols to yield fatty acid ditions (50 – 70 ◦ C, atmospheric pressure, ex-
esters. cess methanol), free fatty acids present in the
Both refined free fatty acids and fatty acid oils must first be removed or pre-esterified,
esters (mostly methyl esters and, more rarely, e.g., with glycerol. Under more severe con-
butyl esters) are used for hydrogenation. Direct ditions (i.e., at 9 – 10 MPa and 220 – 250 ◦ C),
hydrogenation of triglycerides is also possible; pre-esterification is unnecessary, and less pure,
however, under the reaction conditions, glycerol cheaper raw materials can be used. Disadvan-
is reduced to propylene glycol and propanol and tages of this process are the need for high-pres-
therefore makes no commercial contribution as sure equipment, a greater excess of methanol,
a byproduct. More hydrogen is needed and cat- and the energy-intensive further processing of
alyst costs increase. Therefore, triglyceride hy- the aqueous methanol. The methyl esters are pu-
drogenation is not used industrially. rified by distillation.
Fatty acid esters are produced either by es- Figure 2 demonstrates the production tree of
terification of free fatty acids or by transesteri- physical and chemical processing of fats and
fication of triglycerides (see also → Esters, Or- oils.
ganic).
Esterification of Fatty Acids. Esterification
is an equilibrium reaction: 2.3.3.2. Hydrogenation Processes
on the integration into existing plants and the catalyst is required, and catalyst consumption is
choice of raw materials. In all cases, hydro- increased.
genation is carried out with copper-containing, A variant that is particularly suitable for the
mixed-oxide catalysts at 200 – 300 ◦ C and 20 – hydrogenation of fatty acids has been developed
30 MPa. Oleofina/B uses a proprietary fixed by Lurgi (Fig. 3) [28], [29] and is used by several
bed catalyst which operates at 170 – 250 ◦ C and manufacturers, including Condea Chemie [30].
< 10 MPa [27]. This process employs a large excess of fatty al-
cohol in the hydrogenation reactor. Hydrogen,
Suspension Hydrogenation. This process is fatty alcohol – catalyst slurry, and fatty acids are
applicable to fatty acid methyl esters as well as fed separately into the reactor; the ester forms
to fatty acids. almost instantaneously [31] and is then hydro-
Hydrogen (ca. 50 mol per mole of ester) and genated in the same reactor in a slower, second
the heated methyl ester are fed separately into reaction step. Hydrogenolysis is carried out at
the bottom of a narrow reactor. The reaction is ca. 30 MPa and 260 – 300 ◦ C. Catalyst consump-
carried out at ca. 25 MPa and 250 – 300 ◦ C in the tion is 5 – 7 kg/t fatty acid. The catalyst is sep-
presence of a fine powdery copper catalyst; the arated by centrifugation, and the crude fatty al-
LHSV (liquid hourly space velocity) is approx- cohol, which has an acid number of < 0.1 and a
imately 1. The excess hydrogen serves to circu- saponification number of 2 – 5, is purified by dis-
late the reaction mixture. The product mixture is tillation. The selectivity of the process is > 99 %.
separated into a gas phase, which is recycled to By continuously replacing part of the spent
the reactor, and a liquid phase, from which the catalyst, the activity of the copper chromite con-
methanol is stripped. The crude product, which tact can be held constant.
still has a saponification number of 6 – 10 (mil-
ligrams of KOH required to saponify one gram Gas-Phase Hydrogenation. This process
of substance), is distilled off after removal of the requires a vaporized substrate and is therefore
catalyst. If a stainless steel reactor is used, this particularly suitable for methyl esters, prefer-
process can be applied to the direct hydrogen- ably with a chain length of 12 – 14 C-atoms.
ation of fatty acids. In this case, an acid-resistant Figure 4 shows a simplified flow diagram of the
process. Characteristics of the process are an ex-
Fatty Alcohols 7
tremely large excess of recycle gas (ca. 600 mol and about 250 ◦ C, with an LHSV of ca. 0.2.
of H2 per mole of ester), high gas velocities and Normally, catalysts based on copper, chromi-
the addition of methanol to aid evaporation [32], um- or copper-zinc mixed oxides are employed.
[33]. Decomposition of methanol creates signif- More rarely, supported catalysts such as copper
icant quantities of carbon monoxide, water, and chromite on silica are used. Catalyst consump-
dimethyl ether. Admixture of an inert gas to the tion is about 0.3 % based on the feed. Further
hydrogen is claimed to make the addition of treatment of the product is identical to that de-
methanol superfluous and to reduce the excess scribed for gas-phase hydrogenation (see Fig. 4).
of recycle gas [34]. Catalysts like copper-zinc or
copper-chrome mixed oxides are used in a fixed Comparison of Hydrogenation Processes.
bed. The conditions required are < 10 MPa pres- In the case of the fixed-bed processes (gas-
sure and 230 – 250 ◦ C, with an LHSV of about phase and trickle-bed hydrogenation), the cat-
0.3. Alcohol yields of > 99 % are achieved. Cat- alyst need not be separated from the crude fatty
alyst consumption is about 0.3 % based on the alcohol. However, a gradual decrease in the hy-
feed. The product mixture is separated into a drogenating activity due to catalyst poisons such
gas and a liquid phase; the hydrogen is recy- as sulfur, phosphorus, or chlorine is observed,
cled and the methanol stripped from the fatty whereas continuous replacement of the catalyst
alcohol. New developments of, e.g., Davy Mc- in the suspension process ensures constant ac-
Kee (DE 439 5501). A 30 000 t/a unit has been tivity. If methyl esters are employed, separation
constructed by Prime Chem, Philippines. and further processing of the methanol is neces-
sary.
Trickle-Bed Hydrogenation. In this pro- Catalysts that contain noble metals, espe-
cess, the products to be reduced are used in their cially rhenium, may allow hydrogenation at
liquid form. The process is therefore also suit- lower pressures, which would reduce capital and
able for non-vaporizable substrates such as wax operating costs [36–38].
esters and fatty acids. Corrosive effects of acids Further modifications of the processes
can be neutralized by hydrogenation in the pres- were developed by Metallgesellschaft
ence of amines [35]. If a considerably lower ex- (DE 93-4343320) and Davy McKee/Kvaerner
cess of recycle gas (ca. 100 mol of H2 per mole (DE 4395501) using wax esters as feed.
of ester) is used, a different plant design is nec-
essary. The reaction is carried out at 20 – 30 MPa
8 Fatty Alcohols
Figure 4. Flow diagram of the gas-phase and trickle-bed hydrogenation of fatty acid methyl esters
a) Heater; b) Reactor; c) Cooler; d) Separator; e) Flash drum
chain lengths, ranging from C2 to beyond C26 high-purity aluminum sulfate as a coproduct.
[41]. An optimal yield of the C12 – C14 alcohols, The crude alcohols are finally fractionated into
which are important in the surfactant sector, re- marketable blends and single cuts.
quires addition of about four molecules of eth-
ylene per aluminum – carbon bond (see also Ta- Epal Process (see Fig. 6). Many attempts
ble 2). A small percentage of olefins are formed have been made to achieve a narrower distribu-
as byproducts. tion of chain lengths in the growth reaction [40].
The only process that has been used on an indus-
Table 2. Typical alcohol distributions in Alfol and Epal processes trial scale is the Epal process developed by the
Distribution, %
Ethyl Corporation (today BP/Amoco). The re-
action steps resemble those of the Alfol process,
Alcohol Alfol process Epal process
but the growth reaction is not carried as far. The
Ethanol 0.5 traces product of the growth reaction is subjected to
Butanol 3.4 0.1 transalkylation (290 ◦ C, 3.5 MPa) with C4 – C10
Hexanol 9.5 1.5
Octanol 16.1 3.5
olefins. The chain lengths of the resulting tri-
Decanol 19.5 8.0 alkylaluminum compounds are predominantly
Dodecanol 18.4 34.0 C4 – C10 . Excess olefins are removed in a strip-
Tetradecanol 14.1 26.0 ping column and then fractionated. The trialky-
Hexadecanol 9.1 16.0
Octadecanol 5.1 8.8 laluminum compound is subjected to a second
Eicosanol 2.5 1.9 growth reaction and then transalkylated (200 ◦ C,
Docosanol 1.1 0.2 35 kPa) with C12 – C18 olefins. Again the olefins
are separated in a stripper and fractionated. At
this stage, the trialkylaluminum compound con-
Because of the varying reactivity of partially sists largely of alkyl chains with 12 – 18 carbon
oxidized trialkylaluminum compounds, oxida- atoms.
tion is carried out stepwise by passing through The alcohol distributions achieved in the Epal
carefully dried air. Cooling is necessary, espe- and Alfol processes are shown in Table 2 [44].
cially at the start of the reaction. Alkanes and The Epal process offers greater flexibility than
oxygen-containing compounds are formed as the Alfol process because both the alcohols
byproducts [39]. and the α-olefins that are formed as interme-
Prior to hydrolysis, the solvent is removed by diates can be marketed [45]. Disadvantages of
distillation. Hydrolysis with water gives high- the Epal process are the higher capital and op-
purity hydrated alumina ( Pural by Condea, Cat- erating costs, a considerably more complicated
apal by Condea Vista) as a coproduct, which has process control, and an increased proportion of
many industrial applications, e.g., in catalytic branched-chain olefins and alcohols.
processes (→ Aluminium Oxide, Chap. 6.2.3.)
and in ceramics. In the 1960s, hydrolysis was
carried out with hot sulfuric acid at Conoco’s and 2.4.2. Oxo Process
Ethyl Corporation’s plants. Conoco changed to
neutral hydrolysis, but the sulfuric acid method The oxo process (hydroformylation) consists of
is still used in the Epal process and leads to the reaction of olefins with an H2 – CO gas mix-
ture in the presence of suitable catalysts. This
10 Fatty Alcohols
reaction was discovered in 1938 by O. Roelen internal olefins, which are all important in the
at Ruhrchemie during work on the Fisher – area of surfactants [56], [57].
Tropsch synthesis. Although the first production Heterogeneous hydrogenation of the oxo al-
plant was constructed before 1945 [46], the oxo dehydes at 5 – 20 MPa and 150 – 250 ◦ C in the
process achieved industrial importance only in presence of catalysts based on nickel, molybde-
the 1950s, with the increasing demand for plas- num, copper, or cobalt yields the corresponding
ticizers and detergents. The process is based on alcohols. Alternatively, the aldehyde can be sub-
the following reaction (for details on the reaction jected to an aldol reaction as in the production of
mechanism, see [47] and → Oxo Synthesis): 2-ethylhexanol (→ 2-Ethylhexanol, Chap. 3.). A
flow sheet of the oxo process is depicted in Fig-
ure 7. Worldwide there are three variants of the
oxo process [49]: (1) the classical process us-
ing HCo(CO)4 as catalyst; (2) the Shell process
based on a cobalt carbonyl – phosphine complex
α-Olefins yield approximately equal amounts [48]; and (3) a process using a rhodium catalyst.
of straight-chain and branched aldehydes (see The key parameters of these processes are com-
also Fig. 11). Internal and branched alkenes can pared in Table 3.
also be used in this reaction. Internal olefins give The classical, cobalt-catalyzed oxo process
a product containing some primary aldehyde be- involves the following steps: oxo reaction, cat-
cause the catalyst effects double-bond isomer- alyst separation and regeneration, aldehyde hy-
ization. drogenation, and alcohol distillation. Variants of
For a long time paraffin-based processes were this process differ mainly in the catalyst separa-
predominant as a source of olefins, especially for tion and regeneration steps [50], [51].
detergents [45], [54]. With the development of In the Shell process, alcohols are obtained di-
the SHOP process ( Shell’s Higher Olefin Pro- rectly because of the greater hydrogenating ac-
cess), ethylene has become the preferred raw tivity of the catalyst; the aldehyde hydrogenation
material [55]. The principal steps in the SHOP step is unnecessary. Linearity is improved and
process are ethylene oligomerization, isomer- the 2-methyl isomer is the main byproduct. A
ization, and metathesis (→ Hydrocarbons). The disadvantage is the loss of olefins due to hydro-
products are C12 – C18 α-olefins and C11 – C14 genation to alkanes.
Fatty Alcohols 11
Table 3. Typical process parameters of the oxo processes
Hydroformylation based on a rhodium cata- hols, 25 % of which are secondary. These alco-
lyst has been used by Union Carbide since the hols can be obtained by hydrolysis.
1970s for the production of n-butanol and 2-
ethylhexanol [52]. The higher activity of the cat-
alyst enables operation at lower temperature and 2.4.4. Bashkirov Oxidation
pressure. For butanol, the linearity is over 90 %.
The disadvantage is the high price of rhodium. A variant of paraffinic hydrocarbon oxidation
For a review of the oxo synthesis, see [53]. was developed in the 1950s in the Soviet Union
by Bashkirov [1], [3]. The paraffins are oxi-
dized in the presence of boric acid, which scav-
2.4.3. Hydrogenation of Fatty Acids enges the hydroperoxides that are formed as
Produced by Oxidation of Paraffinic intermediates. This results in the formation of
Hydrocarbons boric acid esters of secondary alcohols. These
esters are relatively stable to heat and oxida-
The process for the oxidation of paraffinic hy- tion. Hydrolysis leads to a statistical distribu-
drocarbons, developed in Germany before 1940, tion of secondary alcohols in which the hydroxyl
is used on an industrial scale in the Come- function may occupy any position on the carbon
con countries, particularly in the former Soviet chain.
Union, for the manufacture of fatty acids. About Industrial oxidation is carried out at about
5 – 10 % of these synthetic fatty acids are con- 160 ◦ C with a nitrogen – air mixture containing
verted to fatty alcohols. The products are mainly about 3.5 % oxygen [59], [60] (→ Alcohols,
linear, primary alcohols, with 5 – 15 % branched Aliphatic, Chap. 2.3.6.). The conversion of
alcohols. An overview is given in [58]. paraffins is limited to a maximum of 20 % in
A mixture of paraffins is oxidized above order to minimize side reactions. The principle
100 ◦ C in the presence of manganese catalysts. reaction steps are depicted in Figure 8.
The complex product mixture consists of al- The process is used in the former Soviet
dehydes, ketones, esters, carboxylic acids, and Union and in Japan (Nippon Shokubai). A plant
other compounds. Since the byproducts cannot operated by Union Carbide in the United States
be completely removed during further process- since 1964 is closed.
ing and distillation of the carboxylic acids, the
uses of fatty alcohol produced by this method are
limited. As with the natural fatty acids, hydro- 2.4.5. Other Processes
genation is carried out after esterification with
methanol or butanol. The suspension hydrogen- Fatty alcohols can also be obtained by reaction
ation process is used (see page 6). The distilla- of α-olefins with hydroperoxides in the presence
tion residue contains esters of C10 – C20 alco- of transition-metal catalysts, especially molyb-
denum [62]:
12 Fatty Alcohols
the water reserves. Field tests in Europe and in sunflower or soybean oils are produced. Unsat-
Africa have proved the effectiveness. The evap- urated alcohols with iodine numbers > 150 are
oration can be reduced to up to 50 %. produced, e.g., from linseed oil.
The same higher fatty alcohols can also be The hydrogenation processes described in
used as defoamer systems for papers to be pro- Section 2.3.3.2 are suitable for the large-scale
duced in modern, fast operating paper machines. production of unsaturated fatty alcohols. The
Products on the basis of fatty alcohols show the fixed-bed processes are preferred because of the
following advantages compared to silicon-based mild reaction conditions. In suspension hydro-
defoamers: high effectiveness, good biodegrad- genation, the prolonged contact between fatty al-
ability, good drainage and deaeration, water re- cohol and catalyst results in side reactions such
cycling, and high cost effectiveness. Each pa- as saturation of the double bond and formation
per quality and each production facility de- of trans isomers, which leads to a higher solid-
mands different defoamer qualities, which con- ification point and, hence, loss of quality. With
tain emulsifiers and additives in addition to the polyunsaturated fatty acids, the formation of
alcohol. conjugated double bonds cannot be completely
prevented.
Hydrogenation is generally carried out at
3. Unsaturated Fatty Alcohols 250 – 280 ◦ C and a pressure of 20 – 25 MPa. Cat-
alysts include zinc oxide in conjunction with
fatty alcohols are special products and can only aluminum oxide, chromium oxide, or iron ox-
be obtained from natural sources; petrochemi- ide, and possibly other promoters [81–86]; cop-
cal processes for their manufacture do not ex- per chromite whose activity has been reduced by
ist. Unsaturated fatty alcohols contain at least the addition of cadmium compounds; and cad-
one olefinic group in addition to the hydroxyl mium oxide on an alumina carrier [87]. Selective
function. Therefore they can react both as al- hydrogenation can also be carried out in a homo-
cohols and as olefins. The physical properties geneous phase with metallic soaps as catalysts.
of the most important unsaturated fatty alcohols An overview of early catalyst developments is
are listed in Table 4. The melting points are be- given in [75]; further references can be found in
low those of the corresponding saturated alco- [76–80]. Patent applications of the 1980s indi-
hols and are influenced by the configuration of cate great interest in selective catalysts [88–93].
the double bond. Unsaturated fatty alcohols are produced in
the Federal Republic of Germany (Henkel,
Production. The first large-scale hydrogen- Salim) and in Japan (New Japan Chemical).
ation plant (Henkel) went into operation in the
late 1950s. Previously, unsaturated fatty alco- Uses. Unsaturated fatty alcohols are used in
hols could be obtained only by hydrolysis of detergents, in cosmetic ointments and creams,
whale oil (Section 2.3.1) or by the Bouveault – as plasticizers and defoamers and in textile and
Blanc reduction (Section 2.3.2). leather processing [23], [94–96]. Oleyl alcohol
Today, a broad range of raw materials based is also used as an additive in petroleum and lu-
on animal or vegetable fats and oils are avail- bricating oils.
able. Both market factors and the degree of un-
saturation (iodine number) required in the final
product influence the selection. 4. Guerbet Alcohols
For products with iodine numbers around 50,
cheap beef tallow or vegetable raw materials Condensation of primary alcohols at 180 –
are available. Products with iodine numbers of 300 ◦ C in the presence of alkaline condensa-
80 – 100 can be produced from technical oleic tion agents leads to primary, a-branched dimeric
acid (animal or vegetable based). Polyunsatu- alcohols. The difference in structure between
rated products are undesirable as they tend to Guerbet and other branched fatty alcohols is
autoxidation. For special applications products shown in Figure 9. The physical and chemical
with higher iodine numbers (> 110) based on properties of Guerbet alcohols are listed in Ta-
ble 5.
Table 4. Physical and chemical properties of primary unsaturated fatty alcohols
IUPAC name Common name CAS Molecular Mr Hydroxyl Iodine mp, ◦ C bp, ◦ C Density, Refractive
registry formula number number (p, kPa) g/cm3 index
number (t, ◦ C) (t, ◦ C)
10-Undecen-1-ol [112-43-6] C11 H22 O 170.3 329 149 −2 133 (2.1) 0.8495 (15) 1.4509 (20)
(Z)-9-Octadecen-1-ol oleyl alcohol [143-28-2] C18 H36 O 268.4 209 95 −7.5 208 – 210 (2.0) 0.8489 (20) 1.4606 (20)
(E)-9-Octadecen-1-ol elaidyl alcohol [506-42-3] C18 H36 O 268.4 209 95 36 – 37 216 (2.4) 0.8388 (20) 1.4552 (40)
(Z,Z)-9,12-Octadecadien-1-ol linoleyl alcohol [506-43-4] C18 H34 O 266.5 211 191 –5 to –2 153 – 154 (0.4) 0.8612 (20) 1.4782 (20)
(Z,Z,Z)-9,12,15-Octadecatrien-1-ol linolenyl alcohol [506-44-5] C18 H32 O 264.5 212 288 133 (0.27) 0.8708 (25) 1.4775 (25)
(Z)-13-Docosen-1-ol erucyl alcohol [629-98-1] C22 H44 O 324.6 173 78 34 – 35 240 – 242 (1.3) 0.8416 (33)
(E)-13-Docosen-1-ol brassidyl alcohol [5634-26-4] C22 H44 O 324.6 173 78 53 – 54 238 – 243 (1.05)
IUPAC name CAS registry Molecular Mr Hydroxyl mp, ◦ C bp, ◦ C Density, g/cm3 Refractive
number formula number (p, kPa) (t, ◦ C) index (t, ◦ C)
2-Methyl-1-pentanol [105-30-6] C6 H14 O 102.18 549 147.9 (101.3) 0.8263 (20) 1.4182 (20)
2-Ethyl-1-hexanol [104-76-7] C8 H18 O 130.23 431 <−76 118 (10.7) 0.8328 (20) 1.4328 (20)
2-Propyl-1-heptanol [10042-59-8] C10 H22 O 158.29 354 117 (2.7)
2-Butyl-1-octanol [3913-02-8] C12 H26 O 186.34 301 126 – 128 (1.5) 1.4457 (20)
2-Pentyl-1-nonanol [5333-48-2] C14 H30 O 214.39 262 154 (1.7) 0.8352 (24) 1.4460 (24)
2-Hexyl-1-decanol [2425-77-6] C16 H34 O 242.45 231 –30 to –26 175 (1.5) 0.8380 (20) 1.4476 (25)
2-Heptyl-1-undecanol [5333-44-8] C18 H38 O 270.50 207 –26 198 (2.0) 0.8446 (15) 1.4550 (15)
2-Octyl-1-dodecanol [5333-42-6] C20 H42 O 298.56 188 –20 135 – 137 (0.007) 0.8329 (21) 1.4545 (19)
2-Nonyl-1-tridecanol [54439-52-0] C22 H46 O 326.61 172 164 – 167 (0.013) 0.8476 (17.5) 1.4582 (17)
2-Decyl-1-tetradecanol [58670-89-6] C24 H50 O 354.67 158 173 – 175 (0.007) 0.8413 (17) 1.4606 (17)
2-Undecyl-1-pentadecanol [79864-02-1] C26 H54 O 382.72 147
2-Dodecyl-1-hexadecanol [72388-18-2] C28 H58 O 410.77 137 203 – 207 (0.007)
2-Tridecyl-1-heptadecanol C30 H62 O 438.83 128
2-Tetradecyl-1-octadecanol [32582-32-4] C32 H66 O 466.88 120 38 – 39 308 – 310 (2.0)
2-Pentadecyl-1-nonadecanol C34 H70 O 494.94 113
2-Hexadecyl-1-eicosanol [17658-63-8] C36 H74 O 522.99 107 43 – 45 270 – 280 (0.013)
2-Heptadecyl-1-heneicosanol C38 H78 O 551.05 102
2-Octadecyl-1-docosanol C40 H82 O 579.11 98
2-Nonadecyl-1-tricosanol C42 H86 O 607.16 95
Fatty Alcohols
The condensation reaction was first observed – Chemical intermediates, e.g., for production
by M. Guerbet [97]. Its mechanism and selec- of branched carboxylic acids
tion of catalysts has been thoroughly studied [3], – Starting materials for textile auxiliaries, e.g.,
[5]. Figure 10 illustrates the reaction mechanism esters, sulfates, phosphates, ethersulfates
in simplified terms. The Guerbet alcohols C32 − 36 , which can be
Today this reaction is performed on a tech- manufactured from C16 − 18 -alcohols, are used
nical scale with a worldwide production capac- as:
ity of several thousand tons per year. The al-
– Esterification components for the manufac-
cohol which is to be dimerized is mixed with
ture of specialty waxes
an alkaline condensation agent and a hydrogen-
– Raw materials for cosmetic stick prepara-
ation/dehydrogenation catalyst and then heated
tions
to 180 – 300 ◦ C. The water formed in the reac-
tion is distilled off continuously together with
the monomeric alcohol. Since the reaction pro-
ceeds faster at higher temperatures, especially 5. Bifunctional Fatty Alcohols
the reaction of short-chain monomeric alcohols Some natural oils which contain double bonds,
(C6 – C10 alcohols) is performed under pressure hydroxyl groups, or other functional groups
to perform it in a suitable temperature range. can be converted into long-chain diols. These
However, low-molecular, α-branched dimeric are usually α,ω-diols or diols whose hydroxyl
alcohols, e.g., 2-ethyl-1-hexanol, can be pro- groups lie far apart. Table 6 lists physical prop-
duced more economically by other methods erties of bifunctional fatty alcohols.
(→ 2-Ethylhexanol). 1,2-Diols can be produced by epoxidation of
internal or α-olefins with subsequent hydrolytic
Physical Properties. The physicochemical cleavage of the epoxide ring (→ Alcohols, Poly-
properties of Guerbet alcohols can be summa- hydric).
rized as follows [98]: Dimerization of unsaturated fatty acids such
– Melting point or pour point are considerably as soybean, linseed, and tallow fatty acid, fol-
lower than those of linear alcohols with the lowed by esterification and catalytic hydrogen-
same molecular mass. ation, gives saturated diols [99].
– Volatility and vapor pressure are significantly α,ω-unsaturated fatty alcohols can be pro-
lower than those of linear alcohols with com- duced by pyrolysis of castor oil (Atochem)
parable consistency (but lower molecular or by metathesis of oleic acid methyl es-
mass). ter (Warwel, PCT/WO96/19287; Noweck
– As compared with other liquid unsaturated PCT/DE/95/01846).
alcohols the Guerbet alcohols are stable Thermal or catalytic dimerization of unsatu-
against oxidation and autoxidation. rated alcohols yields viscous dimers with com-
plex structure and an average of two hydroxyl
Uses. Based on these properties Guerbet al- groups per molecule [100], [101].
cohols in the range of C12 − 36 can be used in the 1,12-Octadecanediol, 1,10-decanediol, and
following application areas: 9-octadecene-1,12-diol are obtained from cas-
tor oil by transesterification and hydrogenation,
– Cosmetic-pharmaceutical oil components or by alkali splitting, esterification, and hydro-
with high stability against autoxidation (ran- genation. α,ω-Diols with high purity can be pro-
cidity) duced from the corresponding dicarboxylate es-
– Plasticizers for synthetic resins, e.g., nitro- ters (DE 38 43956, Hüls AG), e.g.,
cellulose lacquers (for the production of per-
manent templates) Suberate → 1,8-Octanediol
Sebacate → 1,10-Decanediol
– Solvents or solution aids for printing inks and Dodecanedioate → 1,12-Dodecanediol
specialty inks
– Lubricant components, e.g., for metal pro-
cessing oils and fiber preparations Sebacic acid is based on castor oil. Nature
offers today new plants and new renewable raw
Table 6. Physical and chemical properties of bifunctional fatty alcohols
IUPAC name CAS registry number Molecular formula Mr Hydroxyl mp, ◦ C bp, ◦ C Density, g/cm3
number (p, kPa) (t, ◦ C)
Oxo alcohols from statistical, cracked Guerbet alcohols are primary, α-branched
olefins or from paraffin dehydrogenation by fatty alcohols with two straight-chain alkyl
the Pacol process or SHOP olefins contain a groups of approximately equal length.
large number of isomers that cannot be com-
pletely separated, even in the most efficient cap-
illary columns. Both odd- and even-numbered 7. Storage and Transportation
isoalcohols occur. Oxo alcohol mixtures can be
identified by spectroscopic determination of the During production, processing, and storage,
degree of branching, i.e., the ratio of n-alcohols fatty alcohols are handled as liquids. Fatty al-
to isoalcohols, which depends on the production cohols starting from C12 OH solidify at ambi-
process and the raw materials used. ent temperatures. Products with a melting point
Fatty acids obtained by oxidation of paraf- above 40 ◦ C can therefore be transferred to,
finic hydrocarbons yield even- and odd- stored, and handled as flakes or pastilles.
numbered primary alcohols with a low degree Fatty alcohols are sensitive to oxidation and
of branching. Branched alkanes present in the should be stored under an inert gas; the tem-
original paraffins are lost by oxidative degrada- perature should not be higher than 20 ◦ C above
tion. the melting point. Low-pressure steam or warm
The boric acid-catalyzed process ( Bashkirov water are recommended for heating. Water in-
oxidation) yields secondary alcohols with a sta- creases stability to autoxidation; as little as 0.1 %
tistical distribution of isomers. has a stabilizing effect. The use of antioxidants
20 Fatty Alcohols
Table 7. Analytical methods for the characterization of fatty alcohols
depends on further processing and quality re- wide production and consumption are estimated
quirements. at 1.5 × 106 t/a for 1998. In Europe only approx.
Stainless steel or an Al – Mg – Mn alloy 5 % of this volume is used directly as fatty alco-
(DIN 1725/1745) is used as container material; hols. A share of 70 – 75 % is used in surfactants
ordinary steel should have a zinc silicate coat- exclusively [73], [74], [105–109].
ing, e.g., Dimetcote. Pumps, valves, and pipes In the United States the synthetic fatty alcohol
exposed to the product should be made of stain- capacities predominate with ca. 70 % share of
less steel. the total capacity. The largest producers of syn-
Fatty alcohols are considered as flammable thetic alcohols are Shell (SHOP/oxo process),
materials and are classified according to proper- Amoco (Ziegler/Epal process) and Condea Vista
ties such as flash point and boiling point. Their (Ziegler/Alfol process). Natural fatty alcohols
transport is governed by national and interna- are produced by Procter & Gamble and Cognis
tional regulations dealing with volatile and com- (formerly Henkel).
bustible materials. In Western Europe, approx. 60 % of the pro-
duction capacity is based on natural raw ma-
terials. The largest manufacturer is the Condea
8. Economic Aspects Group (today SASOL), exploiting all three tech-
nologies, i.e., Ziegler, oxo and natural produc-
The economic significance of fatty alcohols is tion processes. Other European manufacturers,
reflected by the worldwide installed production such as BASF, ICI, Exxon, and Shell, predomi-
capacities of ca. 2.0 × 106 t/a in 1998, which will nantly use the oxo process. As the second largest
increase to ca. 2.3 × 106 t/a by the year 2000. Western European manufacturer for fatty alco-
Table 8 shows these production capacities cat- hols, Cognis, produces exclusively from natural
egorized by volume, location and raw materi- raw materials using high pressure hydrogenation
als. In summary, approx. 50 % of the fatty al- processes.
cohols are produced from natural raw materi- In the Far East the share of production ca-
als, however, the split per geographical region is pacities from natural raw materials is ca. 75 %.
different from continent to continent. The world- This share will further increase by planned ad-
Fatty Alcohols 21
Table 8. Estimated production capacities for fatty alcohols in 1998, 103 t
ditional capacities of about 50 000 t. The cur- 1974 and 1979 – 1980 and subsequently for sec-
rently largest manufacturers of natural fatty al- ondary products such as naphtha, paraffins, and
cohols are the Salim Group and Kao Soap Corp. ethylene. On the long run the price increase rate
Synthetic fatty alcohols are manufactured by the for fats and oils was considered to be lower than
oxo process, e.g., by Mitsubishi Chemical, Mit- for crude oil [73], [74], [111], [112], [115–122],
subishi Petrochemical and Fushun, or by the leading to an expansion of the natural production
Ziegler process, used in Jilin. capacities. In the beginning of 1999 the price for
In Eastern Europe fatty alcohols are manufac- crude oil was again nearly as low as the price
tured predominantly on the basis of the paraffin in 1974. Therefore, fatty alcohols on the basis
oxidation process. of petrochemical raw materials had a cost ad-
Considering the existing production capac- vantage over natural based fatty alcohols. This
ities and based on the announced capacity in- changed again in the second half of 1999.
creases, assuming an estimated yearly increase The long-term estimate was based on an in-
of the fatty alcohol demand of 2 % to 3 %, ca. crease in crop yields for fats and oils, new hy-
80 to 90 % of the capacities will be utilized brids of oil plants, a wider geographical distribu-
through the year 2005 [73], [74], [112], [114]. tion of their cultivation areas, and the renewable
The planned new capacities will be based on character of these raw materials in contrast to
fats and oils and on petrochemical or Fischer- crude oil. All of this guaranteed a reliable supply.
Tropsch raw materials, respectively. Therefore, the ratio of the production capacities
The capacity utilization of each production of synthetic to natural fatty alcohols changed
unit depends on the overall economic develop- in favor of natural products to a current ratio
ment, the product mix and the prices for the used (2001) of 1 : 1. In spite of production increases
raw materials. Figure 12 shows the differences for coconut oils, increased utilization of palm
in price for raw materials based on crude oil, kernel and babassu oils, and the new hybrids of
fats, and oils. C12 -rich oils like cuphea varieties, natural prod-
ucts are mainly limited to the C16 – C18 range
(90 % of all products) [123]. Synthetic alcohols,
however, show their strength especially in the
C12 – C15 range, which plays an important role
in surfactant applications. Therefore, the C16 –
C18 C-chain range is predominantly based on
natural, the C12 – C15 range on petrochemical
based raw materials. However, due to logistical,
economical and political reasons, overlapping
and reversals can occur [73], [111], [112].
city (after single intake of the substance) and ity cannot unmistakably be attributed to a direct
regarding local effects (skin- and mucous mem- substance effect, but can possibly be induced by
brane irritation, data on sensitization effects), physical effects as well. A complete separation
especially data regarding the toxicity after re- of the aqueous solution from undissolved but
peated intake of small amounts of a substance finely dispersed dodecanol is virtually impossi-
need to be taken into account for the toxicologi- ble. Therefore, a rest of undissolved dodecanol
cal characterization. This is especially valid for always remains in the water.
substances which have virtually no acute toxic-
ity as e.g. fatty alcohols. Questions regarding a
possible carcinogenic effect or regarding a pos- 9.2. Toxicology
sible reproduction damage or teratogenic effects
are the main focus point today when the toxi- Linear fatty alcohols are predominantly metabo-
cological properties of chemical substances are lized by oxidation. The resulting fatty acids can
assessed. be subsequently integrated into the fatty acid
For the assessment of the properties of fatty metabolism. A further metabolic reaction is con-
alcohols Condea data and data from scientific jugation of the fatty alcohols with glucuronic
publications were used. Here especially the acid and subsequent excretion.
IUCLID-data [124] were consulted, which were Fatty alcohols possess virtually no acute toxi-
compiled by the manufacturers according to the city after oral intake or after exposure to the skin.
ECAltstoffverordnung (EEC 793/93). Especially fatty alcohols with a shorter C-chain
length irritate the skin in higher concentrations,
in animal tests eye irritations were observed as
9.1. Ecotoxicology and Environmental well. The irritating effect decreases with increas-
Aspects ing C-chain length. In studies with volunteers
some fatty alcohols show a considerably lower
Linear fatty alcohols are in general eas- skin irritating effect. This has, at least in part,
ily biodegradable. The biological degradation to be attributed to the different test conditions of
of secondary fatty alcohols proceeds slightly studies with volunteers as compared with animal
slower, however, the decomposition rates in experiments. The available data and the chemi-
standardized lab tests are comparatively high. cal structure of fatty alcohols do not indicate a
For the assessment of the data it has to be con- sensitizing potential of fatty alcohols. From to-
sidered that the solubility of fatty alcohols in day’s point of view even after long-term intake
water decreases with increasing C-chain length. of the typical linear fatty alcohols, substance in-
Therefore, the alcohols are present only in an duced damage is not to be expected. The avail-
extremely low concentration in aquatic environ- able data show that fatty alcohols do not pos-
ments. Effects, which are detected in various test sess genotoxicity, which is not to be expected
systems, often have to be regarded as secondary anyway on grounds of their chemical structure.
effects caused by undissolved, finely dispersed Valid data regarding a carcinogenic effect are not
substance particles, and therefore have to be dis- available. But, based on structure-effect consid-
tinguished from “real” substance effects. erations, it can be assumed that fatty alcohols do
For aquatic organisms fatty alcohols possess not have a carcinogenic potential.
only moderate acute toxicity. In general, in the For some of the fatty alcohols at least guid-
concentration range of their water solubility no ance data on reproduction toxicity are available.
toxic effects are observed. However, a number These data show that under the study conditions
of studies was performed with concentrations fatty alcohols neither reduced the fertility nor
which are considerably above the water solu- had an embryo or fetotoxic effect.
bility. The observed toxic effects can also be In Table 9 data on the toxicity of fatty acids
attributed to the aforementioned secondary ef- after short-term exposure are listed. Table 10
fects. The available data for the chronic toxicity summarizes data on the acute toxicity to aquatic
neither indicate a special toxicological potential organisms and degradability data [124–129].
of fatty alcohols. Dodecanol shows a more dis-
tinct toxicity in the studies. However, this toxic-
Fatty Alcohols 23
10. References
General References
no sensitization (human data)
no sensitization (human data)
no sensitization
Stuttgart 1975.
Sensitization
human data)
human data)
-
-
Specific References
moderately irritant
slightly irritant
slightly irritant
not irritant
not irritant
not irritant
-
-
moderately irritant
2051 – 2053.
slightly irritant
slightly irritant
not irritant
not irritant
not irritant
not irritant
no. 4, 145.
12. Alfol-Alkohole, Typische Analysendaten,
irritant
3, 111.
> 5000 – > 42 000 mg/kg (rat)
no. 3, 31.
2-Octyldodecanol
Octadecanol
Docosanol
1-Hexanol
Substance
1-Octanol
Eicosanol
Decanol
no. 4, 42.
29. Th. Voeste, H. Buchold, J. Am. Oil Chem. Soc.
61 (1984) no. 2, 350.
24 Fatty Alcohols
Table 10. Ecotoxicity of fatty alcohols
Substance Bio-Degradability Acute Fish Toxicity Acute Daphnia Algae Toxicity Bacteria Toxicity
Toxicity
1-Hexanol biodegradable > 100 mg/L > 100 mg/L 10 – 100 mg/L 3000 – 10 000 mg/L
1-Octanol biodegradable 10 – 100 mg/L 10 – 100 mg/L 10 – 100 mg/L 350 – > 10 000 mg/L
Decanol easily biodegradable 1 – 10 mg/L 1 – 10 mg/L - > 10 000 mg/L
Dodecanol easily biodegradable < 1 mg/L < 1 mg/L < 1 mg/L > 10 000 mg/L
Tetradecanol biodegradable - - - -
Hexadecanol biodegradable - - > 100 mg/L -
Octadecanol biodegradable > 100 mg/L > 100 mg/L > 100 mg/L > 10 000 mg/L
Eicosanol - - - - -
Docosanol - - - - -
2-Butyloctanol biodegradable - - - -
2-Hexyl-1-decanol easily biodegradable > 100 mg/L - - -
C16 – C20 -Branched - - - - -
Alcohols
2-Octyldodecanol biodegradable > 100 mg/L - 100 mg/L > 10 000 mg/L
2-Decyltetradecanol biodegradable - - - -
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