J Am Oil Chem Soc
DOI 10.1007/s11746-016-2902-x
REVIEW
Catalysts for Fatty Alcohol Production from Renewable
Resources
Deepak S. Thakur1 · Arunabha Kundu1 
Received: 7 April 2016 / Revised: 13 September 2016 / Accepted: 14 September 2016
© AOCS 2016
Abstract  Fatty alcohols may be produced through the pro-
cessing of fatty acids or their esters derived from palm or
coconut oils. Fatty alcohol technology can be classified into
two categories (a) a slurry-phase process in which the fatty
acid or its ester is converted into alcohol using a powdered
catalyst and (b) fixed bed technology in which the fatty
acid or its ester is processed over a formed catalyst, e.g.
tablets or extrudates. Historically copper-based catalysts
are employed for achieving ester hydrogenolysis. In recent
years, studies were also focused on precious metal catalysts
for this process. This paper will critically review existing
literature pertaining to the catalysts that operate at diverse
conditions, handle different feedstocks, and are compatible
with a variety of unit operations used by the fatty alcohol
manufacturers. There is an effort to develop environmen-
tally friendly non-chrome copper catalyst in this process.
Some recent progress on bimetallic Cu-Fe catalyst and
understanding Cu-Fe interaction has been reported. Current
development on homogenous catalysts in this process was
carefully reviewed. The catalyst deactivation mechanism
has been investigated and effect of different impurities,
mainly phosphorous, sulfur, chloride, water, glycerine and
free fatty acid was thoroughly reviewed.
Keywords  Oleochemistry · Hydrogenation · Processing
technology
* Deepak S. Thakur
ds.thakur@gmail.com
1
BASF R&D, 23800 Mercantile Road, Beachwood, OH
44122, USA
Introduction
Fatty alcohols are predominantly linear and monohydric
aliphatic alcohols with chain lengths between C8 and C22
containing saturated or with one or more unsaturated C=C
double bonds. The OH group is usually found in the pri-
mary position and provides a site for attaching strong
hydrophilic species. The hydrocarbon portion of the fatty
alcohol molecule is hydrophobic, thereby providing the
combination of hydrophobicity and hydrophilicity in the
same molecule, as is required for a good surfactant.
Commercially, fatty alcohols can be produced as linear
or branched, primary or secondary and saturated or unsatu-
rated alcohol, depending upon the manufacturing process
and the raw materials. When natural products (fatty acid
methyl or wax esters) and ethylene are used as raw mate-
rials, the products are linear, primary and even-numbered
alcohols. The oleochemical raw material can yield both sat-
urated and unsaturated fatty alcohols. When olefins such as
propylene are used as feed in oxo-process, branched alco-
hols with odd-numbered carbon chains can be produced.
Fatty alcohols made by using renewable sources such
as palm, palm kernel or coconut oil are termed as natural
alcohols. The carbon number in fatty alcohol depends on
the source of natural oil. For example, palm oil is rich in
C16–C18 while coconut and palm kernel oils are rich in C12–
C14. Detergent alcohols generally have a hydrocarbon chain
length of C12 minimum with at least 35 % linear chains.
Plasticizer alcohols generally have a chain length of C6–
C13 with a structure that is either linear or highly branched.
Synthetic alcohols are either produced by Ziegler process
via ethylene polymerization with tri-ethyl aluminum fol-
lowed by oxidation/hydrolysis, or by hydroformylation of
propylene or its oligomers followed by hydrogenation of
aldehydes.
13

Fig. 1  Schematic of oleochemical process chemistry
Although the fatty alcohol technology has been prac-
ticed for a longtime, there has been continuous improve-
ment in the process and catalysts. Special emphasis was
given to increase the lifetime of the catalyst. Therefore the
deactivation studies with various poisoning components
were studied. The current review will focus on the catalysts
used for the production of natural alcohols. The term fatty
alcohol will be used in the foregoing sections when refer-
ring to natural alcohols. The other objective of this review
is to discuss critically the poisoning effect and catalyst
deactivation.
Fatty Alcohol Market and Applications
With increasingly stringent environmental regulations and
the depletion of nonrenewable resources, the way has been
paved for oleochemicals to enter the market and replace
the conventional petroleum-based products being used
currently. The factors driving growth in the market are:
high demand coming from consumer markets, easy avail-
ability of raw materials, and a growing market for green
chemicals. The oleochemicals market is expected to expe-
rience huge growth due to the enormous potential offered
by these drivers [1–7]. Recent studies [2, 3] suggest that
the global fatty alcohols market demand was 2.4 million
tons in 2014 with C10–C14 fatty alcohols being the larg-
est product segment with a market share of over 55 %
and is expected to reach 3.3 million tons by 2022. On the
other hand, C16–C22 fatty alcohols are expected to witness
the highest growth rate of 4.5 % globally because of an
increase in demand for lubricant bases and personal care
products. Asia Pacific is the largest consumer as well as
producer of fatty alcohols. The region accounted for 35 %
13
J Am Oil Chem Soc
Fig. 2  Main applications of fatty alcohols [2–7]
of global demand in 2014 with an expected growth of
4.9 % from 2015 to 2022, which could be attributed to
the availability of key raw materials in this region. The
global fatty alcohols market is highly fragmented owing
to the presence of several small and medium scale com-
panies operating particularly in Asia Pacific and Central
and South America. Major companies operating in the
global fatty alcohols market include Ecogreen Oleochemi-
cals, Emery Oleochemicals, BASF, Kuala Lumpur Kepong
(KLK), Oleon, Sasol, PT Muslim Mas, Saudi Kayan Pet-
rochemical Company and Kao Chemicals.
Figure 1 presents at schematic of oleochemical technol-
ogy being practiced worldwide.
Applications of fatty alcohols depend upon the chain
length. About 80 % of the mid-cut C12–C14 alcohols are
used for production of detergents while the heavy-cut
C16–C18 alcohols are employed for the manufacture of
health/personal care products. Figure 2 illustrates the main
applications.
J Am Oil Chem Soc

Fatty Alcohol Chemistry Dehydration

The oldest method [8–10] for fatty alcohol production was 2RCH2 OH ⇋ R–CH2 − O –CH2 –R (7)
Fatty Alcohol − H2 O Ether
based on the reaction of triglycerides with sodium in the
presence of a reducing alcohol, such as amyl alcohol. A Dehydrogenation
disadvantage of this process was high processing costs due
RCH2 OH ⇋ R–CHO (8)
to the high price of sodium. Fatty Alcohol −H2 Carbonyl Compound
New processes were developed using hydrogen, which
is a cheaper and cleaner reducing agent than sodium. Com- A few studies have been conducted to elucidate the pos-
mercially, the fatty acids of palm, palm kernel or coconut sible mechanistic pathways. Norman [12] postulated that
oils are converted to esters by interesterification followed fatty acid ester hydrogenolysis proceeds through a hemiac-
by hydrogenolysis of esters to corresponding alcohols using etal intermediate:
copper-based catalysts [10–31]. However, the most com-
monly used catalyst appear to be based copper chromite.
Fatty acid (wax ester) and fatty methyl esters derived
from palm kernel or coconut oils are used as feeds. Fatty
acids are esterified with fatty alcohol at elevated tempera- (9)
tures to wax ester while triglycerides are transesterified
with methanol using sodium methylate solution or ion
exchange resin bed to form the methyl esters as shown by Commercially, both fatty acid wax ester and fatty acid
Eqs. (1) and (2), respectively. Commercially, the hydrog- methyl ester feeds are hydrogenated to fatty alcohol using
enolysis is carried out by using a copper-based catalyst slurry and fixed bed reactors. Table 1 gives the operating
(Eqs. 3 and 5). conditions used for each type of reactor to achieve opti-
mum performance.
Esterification/Transesterification
Catalytic Processes for Fatty Alcohol Production
RCOOH + RCH2 OH ⇋ RCOOR′ , (1)
Fatty Acid Fatty Alcohol Wax Ester
Earlier several groups in academia and industry [10–36]
where R′ = RCH2– were trying to develop catalytic processes for fatty alcohol
manufacture either from fatty acids or their corresponding
C3 H5 (OOCR)3 + 3CH3 OH ⇋ 3RCOOCH3 + C3 H5 (OH)3 esters. The pioneering work of Adkins et al. [11, 15, 16,
Triglyceride Methanol Methyl Ester Glycerin
(2) 23] documented an efficient way of producing fatty alco-
hols using copper chromite catalysts.
Ester Hydrogenolysis Initially, the fatty alcohol plants were installed by using
a high pressure continuous slurry process and copper chro-
RCOOR′ +H2 ⇋ 2RCH2 OH, (3) mite powder as catalyst. Procter & Gamble and the Kao
Wax Ester Fatty Alcohol
Soap used their own slurry methyl ester hydrogenation
where R′ = RCH2– process technology and in-house developed catalyst, while
Air Liquide (then Lurgi) licensed slurry fatty acid (via wax
RCOOCH3 +2H2 ⇋ RCH2 OH + CH3 OH ester) hydrogenation process with vendor supplied catalyst
Methyl Ester Fatty Alcohol Methanol (4)
to produce fatty alcohols. Air Liquide (then Lurgi) [37–39]
Interesterification developed a process that made it possible to hydrogenate
fatty acid by carrying out esterification to wax ester and
RCOOCH3 + RCH2 OH ⇋ RCOOR′ , (5) hydrogenation steps in one reactor using a copper chromite
Methyl Ester Fatty Alcohol Wax Ester
catalyst. The C=C double bonds present in the fatty acids
where R′ = RCH2– are hydrogenated to produce saturated fatty alcohols.
The undesired byproducts are formed during hydrogen- The slurry process is a continuous operation with fatty
olysis represented by Eqs. (5) to (7). ester feed, powder catalyst and hydrogen coming in contact
with each other under reaction conditions inside the reac-
Excessive Hydrogenation tor (Fig.3a). For the fatty acid or wax ester process(Fig.3b),
the wax ester is produced in situ by injecting fatty acid into
RCH2 OH −→ R–CH3 fatty alcohol and then hydrogenating to alcohol. The reac-
Fatty Alcohol +H2 Hydrocarbon (6) tor effluent goes through a few unit operations including

13

Table 1  Slurry phase and fixed bed process conditions
Process conditions Slurry reactor
Pressure (bar) 250–300
Temperature (°C) 280
Feed Methyl or wax ester
Catalyst shape Powder
H2/feed (molar ratio) 25–50
Configuration Continuous recycle, liquid phase
Fig. 3  Schematics of a methyl ester and b wax ester slurry processes [1]
gas–liquid separator to remove hydrogen, depressurizer to
reduce pressure to ambient conditions, and a continuous
filtration system to remove the catalyst from fatty alco-
hol. The catalyst withdrawal and addition rates (5–10 %
of total catalyst inventory in the reactor) are optimized for
maintaining desired conversion. The fresh catalyst is added
to the recycle catalyst slurry and gets activated in situ as
shown by Eq. (12).
While Air Liquide (then Lurgi) was building slurry fatty
alcohol plants, BASF [40–44] (then Henkel/Cognis) had
developed in-house technology for a fixed-bed high-pres-
sure process to hydrogenate fatty acid methyl ester (FAME)
to fatty alcohol using their own copper catalyst. In the
1990s, the fixed bed fatty alcohol processes [1, 2, 3, 45–49]
were introduced (Fig. 4) by Air-Liquide and Davy process
technologies. Air Liquide (Lurgi) technology is a high pres-
sure liquid phase process operating at 250 bar while Davy
process is a vapor phase process and operates at compara-
tively lower pressure (40 bar), as shown in Table 1.
The fixed bed operation is much simpler compared to
the slurry process. The catalyst is charged into the fixed
bed reactor either in pre-activated condition or is acti-
vated in situ before starting the feed. The trickle bed high
13
J Am Oil Chem Soc
Fixed bed
Liquid phase Gas phase
250–300 40
180–220 200–240
Methyl or wax ester Methyl ester
Tablets or extrudates Tablets or extrudates
40–100 250 and above
Down flow; trickle-bed, gas–liquid-solid Down flow; gas–solid
pressure process operates at slightly lower temperatures
and lower hydrogen to feed ratio. In the vapor phase pro-
cess, high temperatures and high hydrogen to feed ratios
are employed to keep the feed in gas phase (above dew
point). As expected, the capital costs are higher for the
high pressure process due to cost of reactor construc-
tion material. Davy’s low pressure process is carried out
at lower pressure which reduces the capital expenses.
However, the large volume of recycled hydrogen needed
to keep the reactant in the vapor phase requires a larger
compressor and could add some additional cost due to the
separator and compressor.
There were a few attempts made to develop processes
for direct one step hydrogenation of triglycerides to fatty
alcohols [27, 28, 43]. Haidegger et al. [27] and Karo-
lyi et al. [28] obtained the highest yields of fatty alcohol
by hydrogenation of triglycerides at 310–330 °C, 300 bar
pressure and 1–2 % catalyst concentration in a slurry pro-
cess, while Demmering et al. [43] patented a fixed bed pro-
cess operating at 200–230 °C and 250 bar hydrogen pres-
sure using a CuZn catalyst. This process, however, yields
a considerable amount of propylene glycol via glycerine
hydrogenation.
J Am Oil Chem Soc
Fig. 4  Schematics of methyl and wax ester fixed bed processes [1]
Catalytic ester hydrogenolysis is normally performed
in a multi-phase system. In such a system, because of low
hydrogen solubility in the liquid substrate and mass trans-
fer resistance, the hydrogen concentration at the catalyst is
low and limits the reaction rate. To overcome this limita-
tion, supercritical solvents such as various alkanes (Van de
Scheur et al. [50]) propane (van den Hark et al. [51, 52]),
butane (Brands et al. [53, 54]), n-pentane (Zhilong [55]),
and methanol (Liang et al. [56]) were used to make the
reaction happen at a lower operating pressure.
Zhilong [55] studied the effect of the molar ratio of
hydrogen to FAME, reaction temperature, space velocity
and operating pressure in a fixed bed reactor with 15 g Cu–
Cr catalyst at supercritical conditions for palm oil fatty acid
methyl ester hydrogenolysis. In order to be in supercritical
conditions, the typical weight ratio of the solvent to FAME
is 90, whereas the temperature, H2/FAME molar ratio,
space velocity and operating pressure are 230–260 °C, 4–7,
2–4 h−1 and 70–90 bar, respectively.
As the hydrogen flow required to hydrogenate the
methyl ester is very low under the supercritical condition,
Liang et al. [56] took advantage of using methanol not
only as a supercritical solvent but also as an in situ hydro-
gen donor. Cu/ZnO/Al2O3 served as both a reforming and
hydrogenation catalyst for this purpose. The conversion is
very much dependent on the methanol concentration. The
Table 2  Hydrogenation of Precursors of catalysts Conversion (%)
decanoic acid with Re oxide
[61]
Re2O7 31.0
Re2O7 + OsO4 94.4
OsO4 3.4
Re2O7 + 5 % Ru/C 62.3
Re2O7 + 5 % Pd/C 8.7
conversion is 65 % with the methanol to FAME mole ratio
of 5–15 and it is dropped to 35 % after the methanol/FAME
mole ratio is increased to 20. The selectivity is increased
with the increase of methanol/FAME mole ratio from 5 to
15 and it is maximum at 15 and then drops upon further
increasing the methanol/FAME mole ratio. As water helps
to produce hydrogen from methanol reforming, the pres-
ence of a small amount of water can enhance the conver-
sion of methyl laurate and the yield of lauryl alcohol. When
the molar ratio of water to methyl laurate was lower than 2,
the selectivity of lauryl alcohol did not change. The conver-
sion, yield, and selectivity were decreased when the molar
ratio of water to methyl laurate was higher than 2.
Most of the processes described above are based on
fatty ester conversion to fatty alcohol, Attempts were also
made to synthesize fatty alcohol by hydrogenation of fatty
acids using rhenium-ruthenium or ruthenium-tin cata-
lysts [57–70]. Broadbent et al. [57] conducted pioneering
work to demonstrate the ability of ReO2 for hydrogenation
of carboxylic acids to alcohol. Following this approach,
Trivedi et al. [58, 59] showed that rhenium in combina-
tion with palladium or ruthenium acts synergistically to
hydrogenate fatty acids to fatty alcohols. Yoshino et al. [61]
also confirmed these findings and reported that decanoic
acid hydrogenation to decanol can be achieved by using a
combination Re–Os oxides and pre-activation in hydrogen.
Table 2 reports the data generated at 130 °C and hydrogen
pressure of 100 bar with dioxane as a solvent.
Using a batch reactor, Tahara et al. [63] found that Ru–
Sn catalysts were effective for the liquid-phase hydrogena-
tion of the C=O group in carboxylic acids. Hydrogenation
activity was affected by the kind of tin compounds used for
the preparation of the Ru-Sn catalyst. Bis-tributyl tin oxide
((Bu3Sn)2O), K2SnO3 and Na2SnO3 were found to be the
appropriate materials for the hydrogenation of the C=O
group over the Ru–Sn catalysts. The C=O hydrogenation
activity for the hydrogenation of carboxylic acids increased
with the increasing amount of Sn added whereas, the C=C
hydrogenation activity decreased. Toba et al. [66] devel-
oped Ru–Sn/Al2O3 catalysts for hydrogenation carboxylic
acids including C6–C18 fatty acids to corresponding alco-
hols. The data shown in Table 3 compares the performance
of these catalysts for various substrates. Rozmslowicz
Products (%) Selectivity of alcohol (%)
Hydrocarbon Alcohol Ester
1.4 22.9 13.2 73.9
11.7 79.8 5.8 84.5
1.1 1.6 1.3 47.1
3.3 54.1 10.0 86.8
2.0 4.7 3.2 54.0
13
 J Am Oil Chem Soc

Table 3  Hydrogenation of fatty Substrate Carbon number H2 pressure (MPa) Acid conversion (%) Yield
acids over 2 wt% Ru/4.7 wt%
Sn catalysts [66] Alcohol Others

Valeric 5 5.6 52.0 50.4 1.6

Caproic 6 5.6 57.6 44.8 12.8
Caprylic 8 5.6 58.1 56.8 1.3
Capric 10 5.6 64.2 62.4 1.8
Lauric 12 5.6 65.0 64.4 0.6
Myristic 14 5.6 65.0 61.1 3.9
Palmitic 16 5.6 78.4 78.0 0.4
Stearic 18 5.6 77.2 76.3 0.9
Lauric 12 8.0 80.0 79.8 1.0
Myristic 14 8.0 84.9 83.5 1.4
Palmitic 16 8.0 82.2 75.3 6.8
Stearic 18 8.0 82.7 79.8 2.9

et al. [70] studied selective hydrogenation of stearic acid The fresh copper chromite was found to consist of CuO
over 4 % ReOx/TiO2 at temperatures of 180–210 °C and and CuCr2O4. In addition to the reactions (1)–(5), the fol-
20–40 bar with selectivity of 93 %. The use of reduc- lowing reactions occur during ester hydrogenolysis using
ible oxide support, such as TiO2 instead of alumina has copper catalysts:
increased the activity and selectivity due to Ru–Ti metal
support interaction. Cu2+ O / Support + H2 → Cu0 /Support +H2 O (Desired Reaction)
Catalyst Active Site
Although there have been more studies on the use of (12)
rhenium-ruthenium catalysts [63–70] for carboxylic acid
hydrogenation, these catalyst systems have not yet been
used in the fatty alcohol industry. This may be due to the Cu2+ O /Support + RCOOH → (RCOO)2 Cu2+ +H2 O
Catalyst Free Fatty Acid Copper Soap
catalyst price due to use of a precious metal and corro- (13)
(Undesired Reaction)
sion-resistant materials of construction for the process
requirements.
(RCOO)2 Cu2+ + H2 → 2RCH2 OH + Cu0
Catalyst Development for Slurry Process
 
Undesired Cu0 Sintering (14)

Initially, copper chromite had been the catalyst of choice,
prepared by several ways described in the literature [11,
13–16, 23, 31–36]. However, the method developed by
Adkins et al. [11, 15, 16] gave the most satisfactory cata-
lyst. Their procedure involves precipitation of an interme-
diate, which is a double hydroxide with copper and chro-
mium with ammoniacal specie—commonly referred to
as Adkins’ complex—followed by its decomposition to a
mixture of copper oxide and copper chromite. The reaction
schemes are illustrated by following Eqs. (10) and (11):
2 Cu(NO3 )2 + (NH4 )2 Cr2 O7 + 4NH4 OH
→ 2 NH4 CuCrO4 (OH) +4NH4 NO3 + H2 O (10)
Adkin’s Complex
During decomposition of Adkins’ complex, the ammo-
nia splits into nitrogen and hydrogen. The latter reduces
Cr6+ to Cr3+ species which is an exothermic reaction.
NH4 CuCrO4 (OH) → CuO · CuCr2 O4 + N2 + 5H2 O (11)
Finely dispersed metallic copper, formed by the reduc-
tion of CuO (Eq. 12), was found to be the active site for
ester hydrogenolysis.
Norman [12] used copper carbonate supported on a sil-
ica carrier for coconut oil hydrogenation at 310–315 °C and
pressures ranging from 120 to 500 bar. No hemiacetal was
isolated but the ester hydrogenation was found to depend
upon hydrogen pressure. Schrauth et al. [11]. established a
high pressure process operating at 320 °C and 300 bar pres-
sure using copper catalysts.
Church and Abdel-Gelil [26] studied the effect of copper
chromite catalyst concentration, and other process param-
eters such as temperature, pressure and agitation rate on
the rate of methyl laurate hydrogenation to lauryl alcohol.
Conversions of 90 % or higher were achieved at tempera-
tures and pressures ranging from 280 to 300 °C and 200–
250 bar, respectively with 4 % catalyst concentration. Cata-
lyst was recycled several times to determine reusability of
the catalyst for a continuous operation. Pantulu and Achaya

13
J Am Oil Chem Soc
Table 4  Effect of calcination temperature on physical properties of CuCr catalyst [79]
Catalyst number Calcination temperature (°C) BET area (m2/g)
1 399 44.8
2 427 35.9
3 460 25.8
4 516 18.5
5 538 13.4
[29] demonstrated that fatty alcohol can be produced by
hydrogenating fatty acids and fatty acid methyl esters using
copper soaps as the catalyst.
In the same time period, Muttzall [31, 32] studied the
kinetics of high pressure hydrogenolysis of wax esters to
fatty alcohols and found that ester hydrogenolysis is an
equilibrium reaction.
Keq
RCOOR′ + H2 ⇆ 2RCH2 OH (15)
He reported that the equilibrium constant (Keq) is
dependent upon temperature and slightly dependent on
the molecular weight of the fatty alcohol. The rate of ester
hydrogenation to fatty alcohol depends linearly on the reac-
tion rate constant, catalyst and ester concentration, and on
the square of the hydrogen pressure.
Boerma [35] has shown that the pH range for maximiz-
ing precipitation of copper and chromium hydroxide with
ammonium hydroxide is very narrow (around 5.3–5.8).
Beyond this range both species form soluble salts and end
up in the filtrate. According to Boerma [35], the presence
of barium in the copper chromite catalyst helps prolong the
catalyst life.
Challenges for Slurry Phase Catalyst Designer
In the slurry process, the overall production rate depends
upon catalyst activity and its separation/filtration rates.
While the reaction rate depends upon the catalyst composi-
tion and surface properties, the settling or separation rate
for continuous filtration is dictated by the physical proper-
ties such as particle size and skeletal liquid filled density.
Catalyst suffers severe attrition during the course of the
process, which also results in slower separation rate.
While designing a catalyst for continuous slurry-phase
systems, in addition to optimizing the activity, the catalyst
formulator is faced with the challenge of improving the
factors, namely: in situ activation, poison resistance, attri-
tion resistance and ease of separation of the catalyst from
the product, which can significantly impact the overall effi-
ciency of the process. In fatty acid process, the acid resist-
ance of the catalyst plays an important role in determining
the fate of the catalyst in the reactor, while in the methyl
Pore volume (mL/g) Pore size (Å) Catalyst diameter (μ)
0.31 276 1.66
0.24 268 1.58
0.19 296 1.28
0.16 344 1.23
0.09 280 1.02
ester hydrogenolysis, the presence of feed impurities, such
as glycerine, water etc., can adversely affect the catalyst
performance.
Activity/Selectivity
For optimum activity/selectivity, the copper chromite
(unpromoted or promoted by Ba or Mn) has met the above
requirements and has been the catalyst of choice for con-
tinuous slurry operation for several decades [11, 16,
71–80]. Rieke et al. [79, 80] found that both activity and
selectivity correlate well with the crystallinity of the cop-
per chromite surface; they increase with decreasing crys-
tallinity or increase in surface area. Table 4 provides calci-
nation temperatures and surface area for the catalysts used
in this study and Fig. (5a, b)illustrates their activity and
selectivity respectively.
The main goal of their laboratory investigation was to
develop a superior copper chromite catalyst for the slurry-
phase process. Two copper chromite catalysts, prepared by
different procedures, were tested for methyl ester hydrog-
enolysis activity, reusability, and filtration characteristics.
The first sample (CuCr-I) was prepared by simultaneous
precipitation at constant pH described in the patents granted
to Thakur et al. [77, 78], while the second sample (Cu–
Cr-II) was prepared by sequential precipitation in which pH
was varied with time. The former sample had narrow par-
ticle and pore size distribution while the latter had a broad
particle and pore size distribution. The reaction was carried
out in a batch autoclave at 280 °C and 140–210 bar hydro-
gen pressure. The reaction rates were calculated by assum-
ing a kinetic mechanism that was first-order in methyl ester
concentration. The catalyst prepared by procedures devel-
oped by Thakur et al. [77, 78] (CuCr-I; Fig.6) was 30 %
more active (Fig.6a), filtered faster (Fig.6c) and maintained
activity (Fig.6b) for several uses than the catalyst (CuCr-II)
with the broader particle size distribution. X-ray photoelec-
tron spectroscopy data showed higher surface copper con-
centrations for the former catalyst which may be attributed
for higher activity.
Prasad et al. [81, 82] have summarized several prepa-
ration techniques for synthesizing high activity copper
chromite catalysts. Among them (a) co-precipitation of
13

Fig. 5  Dependence of a activity and b selectivity on surface area [79]
ammoniacal copper-chromium hydroxide, (b) co-impreg-
nation of support with copper and chromium species, (c)
thermal decomposition of ammoniacal copper oxalate chro-
mate precursor are the most commonly used preparation
methods in the industry.
Acid Resistance
The presence of free fatty acid in the slurry process obvi-
ously makes great demands on the acid resistance of the
catalyst. The copper-based catalysts are susceptible to acid
attack as suggested in Eq. (13) and the copper metal can
elute as a soluble copper soap. In the presence of hydrogen,
the copper soap can be reduced to Cu0 metal as shown in
Eq. (14) and deposit on the catalyst particle or reactor ves-
sel. Re-deposition of Cu metal on the catalyst can lead to
formation of larger Cu0 crystallite size. Thus, copper leach-
ing not only impairs the catalyst performance due to Cu0
crystal growth (Fig. 7) but can also contaminate the fatty
alcohol.
There are a few patents [73–76] teaching the ways
to improve acid resistance by adding other components
including silica. Pohl et al. [73], Nierhaus et al. [74] and
Schneider et al. [75, 76] claim the processes of making acid
resistant copper chromite catalyst by incorporating silica
during precipitation step. Schneider et al. teach two ways
of improving acid tolerance. The first is by heat treatment
[75] and the second [76] by incorporating acid resistance
components such as silica and zirconia to copper chromite.
13
J Am Oil Chem Soc
However the heat-treated silica-free copper chromite cata-
lysts exhibit lower activity compared silica-based catalysts.
These results indicate that the presence of silica not only
improves acid resistance but also improves performance.
Open literature information [83, 84] discussing the cata-
lyst degradation by acid attack and the information on the
preparation of acid-resistant catalyst formulations is com-
paratively scanty. Ladebeck and Regula [83, 84] found
that copper chromite catalysts exhibit highest mechanical
stability and lowest copper solubility in feed/product. Alu-
mina supported copper catalysts show acid resistance close
to that of copper chromite catalysts. According to these
authors, the catalyst stability of the Cr-free copper catalysts
can be improved by avoiding high pressure in situ reduc-
tion or by applying an ex situ reduction technique so that
water produced at the time of CuO reduction is removed
from the catalyst pores before starting hydrogenation. In
other words, the presence of water formed by reduction of
CuO can impair catalyst performance.
Catalyst Filtration/Separation
The slurry processes were designed and optimized by tak-
ing flow or hydrodynamic properties into consideration.
Improvements in filtration rates were achieved by pre-
cipitating uniform sized spherical particles [77, 78]. By
optimizing the average particle size, Thakur et al. [77, 78]
were able to qualify copper chromite catalysts for various
filtration equipment used by fatty alcohol manufacturers.
J Am Oil Chem Soc

Fig. 6  Comparison of Cu–Cr catalyst preparation procedures: a activity, b life test, c filtration [80]

Fig. 7  Catalyst deactivation
due to copper crystallite growth
Well Dispersed Cu Particles Sintering of Cu° crystallite
More number of Cu active sites Fewer number of Cu active sites

Non‑Cr Copper Catalysts non-Cr-containing environmentally friendly catalysts. Vari-

The US Environmental Protection Agency, EPA and Euro-
pean Union, REACH (Registration, Evaluation, Authoriza-
tion and Restriction of Chemicals) regulations against the
use of Cr(VI)-containing catalysts warranted a search for
ous researchers [85–101] focused their attention of devel-
oping acid resistant highly active non-Cr catalysts based on
CuZn, CuMn and CuFe compositions. Ladebeck and Reg-
ula [83, 84] and Thakur et al. [87, 88] developed copper-
zinc-alumina catalyst systems that had equivalent or higher

13

activity and acceptable acid tolerance. Schneider et al. [85,
86] and Chen [99, 100] focused their attention on copper-
manganese-alumina formulations for ester hydrogenation.
Research work reported by researchers at Utrecht Univer-
sity [90], Kao Soap [89, 97, 98, 101] and Roberts et al. [91,
93] showed superior performance of CuFe supported on
silica and alumina carriers for methyl ester hydrogenoly-
sis to fatty alcohols. Figure 8 compares the performance of
various Cu catalysts with different promoters and also dem-
onstrates the beneficial effect of Fe as a promoter [101].
Van de Scheur and Staal [92], reported that the activity
and selectivity for methyl acetate hydrogenation improved
with increasing zinc content in CuZn systems. This increase
in activity was likely to be an effect that originates either
from finely dispersed copper particles in close contact with
the zinc oxide phase or from the promotion of copper metal
crystallites by zinc oxide particles. A decrease in hydrocar-
bon formation with higher zinc content was attributed to
the elimination of dehydrating surface sites (see Eq. 6).
On the other hand, a joint collaborative effort between
Avantium and the University of Malaysia [102–106]
screened various Cu catalysts with different promot-
ers and different catalyst supports for hydrogenoly-
sis of fatty acid methyl esters at 300 °C and 300 bar.
Their data showed the following trend for promoters
and supports respectively: Cu–Zn > Cu–Fe > Cu and
silica > zirconia > magnesia > alumina > titania.
Catalyst Development for Fixed Bed Catalyst
While Table 1 provides the operating conditions, Fig. 4
illustrates the schematic of the fixed bed fatty alco-
hol process. It is well recognized that the demand on the
Fig. 8  Effect of different promoters on Cu catalysts [101]
13
J Am Oil Chem Soc
catalyst used in the fixed bed process are different from
those employed for slurry phase catalysts. In addition to
meeting activity/selectivity targets, maldistribution of flow,
temperature profile and pressure drop in the bed, and parti-
cle degradation also play critical roles in running a smooth
production campaign. Therefore, the catalyst loading war-
rants special attention to avoid channeling through the bed
and proper pre-activation ensures long catalyst life. The
catalyst chemist optimizes the mechanical integrity of the
catalyst particles so as to minimize particle breakup that
could cause pressure buildup inside the reactor or reduced
flow or flow channeling through the bed.
Challenges for the Fixed Bed Catalyst Designer
Activity, selectivity and the particle integrity are of utmost
importance in determining the overall catalyst perfor-
mance. The catalyst formulator needs to choose a proper
combination of active ingredients and promoters/modifiers
for high activity/selectivity, as well as a binder system for
physical integrity and chemical tolerance in acidic environ-
ments. Higher activity per unit volume is manifested by
higher throughputs and hence, translates into higher pro-
duction for the fatty alcohol manufacturer. Improved physi-
cal integrity and attrition resistance minimize pressure drop
problems. The catalyst is expected to perform under a wide
variety of conditions, such as liquid-phase or vapor-phase;
hydrogen pressures ranging from 30 to 300 bar, and with
different feeds, namely, wax or methyl ester derived from
palm or coconut.
It is well known that methyl or wax ester hydrogen-
olysis is a pore diffusion controlled process. Thakur et al.
[6] demonstrated the advantages of a smaller and shaped
extrudate of 1.5 mm diameter as compared to the conven-
tional tablet technology of 3 or 4 mm diameter tablet in
terms of activity, selectivity and productivity. An increase
in void volume and higher surface area per unit volume in
the extrudates helps to decrease pressure drop problems
with the improvement of the performance over the tablets
as shown in Fig. 9. However, the shaped extrudates (tri-
lobe or star shaped) are traditionally weaker in mechanical
integrity as compared to the tablets because of their manu-
facturing process. Roberts et al. [107] developed a pro-
cess wherein an in situ calcium silicate (cement concrete)
is formed providing adequate mechanical strength to the
extrudates so that they can survive under operating condi-
tions and last for a long time in the reactor.
Extrudates were prepared by the process developed by
Roberts et al. [107] and Nebesh et al. [108] and evalu-
ated for high pressure fatty methyl ester hydrogenolysis at
250 bar, 180 °C and LHSV of 0.75 h−1. The product sam-
ples were analyzed for their saponification value as well
as by GC analysis. The saponification value in the liquid
J Am Oil Chem Soc
Saponification Value 50
40
30
20
10
0 Surface area/volume
0 25 50 75 100 125 150
Hours-on-stream
Fig. 9  Activity comparison of extrudates vs tablets (triangles extru-
dates; squares tablets) [6] (saponification value = mg of KOH/g of
sample)
product sample decreases as the conversion increases. The
properties of the extrudates and tablets are given in Table 5.
While designing catalysts for the vapor-phase low pres-
sure process, which operates at higher temperatures than
the liquid-phase high pressure process (Table 1), Thakur
and Carrick [109] showed that the addition of alkali metal
to a copper chromite catalyst during extruding steps mini-
mizes undesired hydrocarbon formation and increases
selectivity.
Catalyst Deactivation
The natural oils used for making fatty esters contain 1 to
5 ppm of various catalyst poisons, which have been studied
by several authors [110–118].
Small amounts of free fatty acids (Van de Scheur et al.
[112]), sulfur (Brands et al. [113], Twigg and Spencer [114],
Huang et al. [110]), chloride (Heldal and Mork [119], Twigg
and Spencer [114], Huang et al. [117]), water (Thakur et
al. [111], Huang et al. [116]), phosphorous (Huang et al.
[118]), and glycerine and monoglyceride (Thakur et al.
[111]) present in the fatty acid methyl ester and wax ester
feed may poison the catalyst and deactivate the reaction
rate. The deactivation may be reversible (temporarily reduce
the activity) or irreversible (permanently reduce the activity)
depending on the nature of the impurity molecule.
Effect of Free Acid on Catalyst Activity
Small amounts of free fatty acids may be present in fatty
acid methyl ester and wax ester even after extensive puri-
fication. Higher concentrations of free fatty acids present
in the feed may lead to soap formation. The effect of free
fatty acids was studied by Van de Scheur et al. [112] in a
tubular flow reactor for methyl palmitate hydrogenolysis
at 197 °C with 14 wt% Cu/9 wt% ZnO/SiO2 and 14 wt%
Cu/SiO2 catalysts. Various concentrations of lauric acid
(0.04–0.14 mmol/L) as free fatty acid spikes were used to
Table 5  Comparison of trilobe extrudate versus tablet properties [6]
Trilobe extrudate catalyst Tablet catalyst
Diameter, inches 1/16 1/8
Bulk density, g/cc 0.7–0.9 1.3–1.5
% void volume 43 34
204 100
175 200
Fig. 10  Effect of the addition of small amounts of lauric acid to a
feed containing methyl palmitate [112]. Conditions: (W/F) = 250 kg
catalyst (cat.) s/mol, C ester + acid (293 K, 1 atm) = 20 mmol/L,
T = 197 °C
see the effect on the activity of these two catalysts. As the
free fatty acid concentration was increased in the feed to
0.05 and 0.14 mmol/L, the conversion dropped from 41 %
with no fatty acids to 34 and 16 %, respectively (Fig. 10).
It is also found that the conversion of methyl palmitate is
stable over time on stream in all the cases. Therefore, the
detrimental effect of acid on the catalyst reactivity is due
to reaction inhibition rather than catalyst deactivation. The
original conversion level can be restored by switching from
free acid spiked feed to pure methyl ester feed.
Effect of Sulfur on Catalyst Activity
Little is known about the nature of the sulfur compounds
present in fatty acid methyl esters prepared from natural
fats and oils. Possible candidates are degradation products
of sulfur containing proteins (like thiols and sulfides) and
glucosinolates. The effect of sulfur poisoning for fatty ester
hydrogenolysis was reported by Brands et al. [113]. The
poisoning effect of sulfur on Cu based catalysts seems to be
permanent as it reacts with the copper site forming a strong
metal-sulfur bond, as indicated by the change in free energy
formation (Twigg and Spencer [114], Brands et al. [113]):
2Cu + H2 S → Cu2 S + H2 G0f = −122.1 kJ/mol (16)
13

Fig. 11  Sulfur deactivation mechanism adopted from Brands et al. [113]
The heat of adsorption of sulfur at the Cu crystal face
(−170 kJ/mol) is greater than the heat of formation of bulk
copper sulfide (−140 kJ/mol) and the fact that the rate-
determining step of bulk copper sulfide formation is the
solid state diffusion of sulfur in copper or copper in sulfur-
implies that preferentially surface sulfides are formed. The
difference in exothermicity between surface and bulk sulfi-
dation of copper catalysts is not very large, so concurrent
surface and bulk sulfidation is more likely. The mechanism
proposed by Brands et al. [113] can be schematically pro-
posed as in Fig. 11. Steps 1 and 2 are already discussed in
the earlier section. In step 3, blocking of active sites and
thereby inhibiting the adsorption of the reactant molecules
occurs. This could be due to either adsorbed sulfur and/or
the remainder of the (organic) sulfur containing molecule.
In this step, sulfur may cause an increase in surface self-
diffusion (surface mobility), thus reducing catalytic activity
by sintering or restructuring of the active metal.
Brands et al. [113] found that the type of sulfur com-
pound has a strong influence on the rate of deactivation.
For example, octadecanethiol and dihexadecyl disulfide
deactivate the catalyst at a slower rate than other types of
sulfur compounds (dihexadecyl sulfide, dibenzothiophene
and methyl p-toluene sulfonate). In view of the differences
in the deactivation behavior of the sulfur containing mol-
ecules tested, Brands et al. [113] suggested establishing the
13
J Am Oil Chem Soc
nature of the sulfur containing molecules in FAME feed-
stock for reliable estimation of catalyst life and reactor
design.
Zn and Mn are excellent sulfur traps, and limit poison-
ing of copper catalysts by the removal of S-containing
compounds with the formation of zinc sulfide and manga-
nese sulfide respectively. This is attributed to the lower free
energy of formation of bulk ZnS and MnS are −146 and
−213 kJ/mol than that of Cu2S. A similar phenomenon was
explained by Twigg and Spencer [114].
Zn + 1/2 S2 → ZnS �G0f = −146 kJ/mol (17)
MnO + H2 S → MnS + H2 O G0f = −213 kJ/mol (18)
Brand et al. [113] showed that deactivation is faster for
unpromoted Cu/SiO2 than Zn promoted Cu/SiO2 catalyst
in the presence of 356 ppm of 1-octadecanethiol in methyl
palmitate hydrogenolysis carried out in a fixed bed reac-
tor at 197 °C and 80 bar pressure (Fig. 12). The octade-
canethiol breakthrough in outlet is also seen after 120 min
with Zn promoted Cu/SiO2 catalyst compared to 80 min
with unpromoted Cu/SiO2 catalyst. Therefore, Zn acts as a
guard to the catalyst by preferentially adsorbing sulfur.
Huang et al. [110] studied the poisoning effect of alkyl
thiols and dialkyl disulfides on the activity of dodecyl
methyl ester hydrogenation over co-precipitated Cu/Zn
J Am Oil Chem Soc
Fig. 12  Deactivation profile for methyl palmitate hydrogenolysis in
the presence of 356 ppm 1-octadecanethiol [113] (fixed bed reactor;
200 mg catalyst; W/F = 2500 kgcat s mol−1
catalyst in a stirred tank reactor. Figure 13 compares the
conversion of dodecyl methyl ester at various concentra-
tion of sulfur species with different types of sulfur com-
pounds. The ester conversion decreased rapidly when the
catalyst was exposed to ethanethiol, n-butanethiol and
dodecanethiol. As the associated alkyl chain in the sulfide
becomes longer, the deactivation of the catalyst becomes
faster. Depending on the types of alkyl thiol, the effects
on the activity of the Cu/Zn catalyst were different. It was
found that the molecular toxicity increased continuously
with the chain length, due to steric hindrance of alkyl
chains. Similar deactivation profiles were observed when
Cu/Zn catalyst was exposed dialkyl disulfides but at much
Fig. 13  Conversion of dodecyl
methyl ester at different levels
of sulfur concentration in mmol/
gcatalyst and different types of
sulfur compounds [110]
lower sulfur concentrations. These results suggest that the
disulfide species are more poisonous than the thiols and
can deactivate the catalyst at much lower S concentration
on the catalyst. Catalyst characterization by XRD EDS and
XPS measurements indicated that the sulfur species at low
concentrations (e.g. 0.2 mmol/gcatalyst ethanethiol), attack
the ZnO of the Cu/Zn catalyst forming chemically adsorbed
Zn–SR (where R = alkane). This interaction weakens the
synergistic effect between copper and zinc. At higher sul-
fur concentrations, both alkyl thiols (e.g. 15.1 mmol/gcatalyst
ethanethiol) and dialkyl disulfides also attack the surface
Cu of the Cu/Zn catalyst forming Cu7S4 or Cu31S16 as con-
firmed from XRD (Fig. 14).
Effect of Chlorides on Catalyst Activity
The effect of chloride-containing species in the feed on the
Cu and copper chromite catalysts were studied by Heldel
and Mork [119], Twigg and Spencer [114] and Huang et al.
[117]. Heldal and Mork [119] found that the amounts corre-
sponding to 25, 50 and 90 ppm Cl markedly decreased the
rate of hydrogenation with 39 %Cu, 32 % Cr and 2.5 % Mn
catalyst at 170 °C for hydrogenation of soybean oil. The
presence of chloride species may exacerbate the poisoning
effect of other species (e.g. sulfur) as mentioned by Twigg
and Spencer [114]. They also noted that the deactivation
of the catalyst by chloride species may be due to blocking
or modifying of the catalytic sites. The low melting point
of CuCl (430 °C) compared to Cu2S (1100 °C) gives them
high surface mobility under operating conditions. This sug-
gests that even extremely small amounts of copper halides
are sufficient to provide mobile species that accelerate the
sintering of Cu crystallites. Twigg and Spencer [114] also
13

Fig. 14  XRD Patterns of Cu/Zn catalysts after reaction with: (1) no
sulfur species; (2) 0.2 mmol/gcatalyst ethanethiol; (3) 5 mmol/gcatalyst
ethanethiol; (4) 15.1 mmol/gcatalyst ethanethiol; (5) 14.6 mmol/gcatalyst
n-butanethiol; (6) 14.3 mmol/gcatalyst dodecanethiol [110]
pointed out that ZnO does not give any protection to Cu
against chloride poisoning in contrast to the case of sulfide
poisoning, as the heat of formation of ZnCl2(s) (−121.8 kJ/
mol) is much higher than that of CuCl(s) (−43.5 k/mol).
ZnCl2 has also low melting point (283 °C) and causes fur-
ther poisoning and sintering of the catalyst.
Huang et al. [117] investigated the effect of the presence
of mono and dialkyl chlorides on Cu/Zn catalyst prepared
by co-precipitation method for hydrogenation of methyl
laurate to dodecanol in a stirred tank reactor. The chloride
concentration was varied from 0 to 0.5 mmol/gcatalyst. With
the increase of chloride concentration from 0 to 0.2 mmol/
gcatalyst, the conversion of methyl laurate decreased slightly.
However, with a further increase in chloride concentration
from 0.2 to 0.5 mmol/gcatalyst the conversion dropped from
90 to ~20 %. As expected, the poisoning effect of dichloro-
alkane was more pronounced than monochloroalkane. They
proposed the following mechanism, based on the analy-
sis of the species found both in liquid and on the catalyst,
which is very similar to the other literature [114, 119]:
Scenario 1. Low chloride concentration:
(a) Migration of Cl− from Cu to ZnO:
2Cl− + ZnO → ZnCl2 + O2− (19)
2−
(b) Migration of O to Cu lattice:
2Cu + O2− → Cu2 O (20)
Scenario 2: High chloride concentration:
(a) H+ + Cl− + CH3 OH → CH3 O+ H2 + Cl− (21)
(b) + −
2CH3 O H2 + 2Cl → ZnCl2 + 2H2 O + 2CH3 OH
(22)
13
J Am Oil Chem Soc
(c) 2Cu + O2− → Cu2 O + 2H+ + 2Cl− → 2CuCl + H2 O
(23)
The formation of ZnCl2 and CuCl at 15 mmol chloride
concentration/gcatalyst decreases the BET surface area from
19.1 to <0.3 m2/g and increases Cu (111) crystal size from
16.5 to >30 nm of the catalyst.
Effect of Water on Catalyst Activity
The reaction inhibition by water for fatty acid methyl ester
hydrogenolysis was found to be reversible causing tem-
porary deactivation [111]. The reaction was carried out
in a 1 L stirred reactor with a 400 g C12 methyl ester and
4–7.2 g copper–chromite catalyst at 207 bar and 280 °C.
The conversion of C12 fatty acid ester remained the same
up to 10 % water in the feed and is dropped by 4 % with
100 ppm water in the feed as shown in Fig. 15.
The low activity of the Cu–Cr catalyst caused by
water is mainly due to blocking of active sites by occlu-
sions. It not only occludes the active sites, but also may
inhibit the reduction of cupric oxide to its zero valence
state active form. Fully reduced catalyst appears to be
relatively immune to low levels of water contamination
(500 ppm). Thakur et al. [111] also found that the mech-
anism by which soap (sodium laurate) deactivates the
catalyst is similar to that suggested for water, i.e. active
site occlusion and reduction inhibition (Fig. 14). Huang
et al. [116] had similar observations that the presence of
water in the feed resulted in lower activity of the Cu–
Zn catalyst due to blocking the catalytic active sites by
the water occlusion of active sites. The concentration of
water in the feed was increased from 0.1 to 2 wt%.and
the conversion was decreased from 95 to 71 %. Fully
pre-reduced catalyst appears to be relatively immune
to low levels of water contamination, e.g. 1000 ppm of
water in methyl laurate. On the other hand, Tike and
Mahajani [115] reported the enhanced hydrogenation
rate of palm stearin fatty acid for 5 % Ru/Al2O3 in the
presence of water (2 wt%) compared to Ni based cata-
lyst. Van der Scheur et al. [112] also reported no influ-
ence of added water on palmitate hydrogenolysis activ-
ity of Cu/ZnO/SiO2 catalyst. They also commented on
different effects (positive, negative or neutral) of water
on this kind of reaction, depending on the choice of the
catalyst and the experimental conditions. Ladebeck and
Regula [85] found that the addition of large quantity
(1–2 %) of water to the ester and the subsequent treat-
ment at 170 °C caused severe damage of the Cu/Al2O3
and Cu/ZnO/Al2O3 catalysts. This is mainly attributed to
free fatty acid generated from the hydrolysis of methyl
ester in the presence of water which leaches the metals
from the catalyst.
J Am Oil Chem Soc

Fig. 16  Relative conversion of dodecyl methyl ester vs millimoles/

kg of permanent catalyst poisons [111]. φ2P-C2H4-Pφ2, bis(diphenyl
Fig. 15  Relative conversion of dodecyl methyl ester vs level of water phospheno)ethane; C18SO3Me, n-octadecyl methane sulfonate; C18Br,
and soap contamination [111] n-octadecyl bromide; C18Cl, n-octadecyl chloride; C18SH, n-octade-
cyl thiol

Effect of Phosphorous on Catalyst Activity

Huang et al. [118] reported the effect of phosphorous as a

contaminant in the fatty acid methyl ester feed. As little is
known about the type of phosphorous compounds present
in fatty acid methyl ester, they used trimethyl phosphate as
representative phosphorous compound for the model reac-
tion of hydrogenation of dodecyl methyl ester to dodecanol
with CuZn catalyst. When the concentration of trimethyl
phosphate was increased from 0 to 0.5 mmol/g of catalyst,
the conversion was found to decrease from 97 to 54 % and
the selectivity from 96 to 56 %. No catalytic activity was
observed at the concentration of 1 mmol/g of catalyst. The
rapid loss of catalyst activity may be attributed to the phys-
ical adsorption of trimethyl phosphate on the CuZn cata-
lyst and also to decreased BET surface area by occlusion
of active sites of the CuZn catalyst, as evidenced by XRD,
EDS, SEM, XPS and BET characterization.
Thakur et al. [111] presented the data of the perma- Fig. 17  Effect of glycerine and monoglyceride on C12 methyl ester
nent deactivation by irreversible adsorption of various hydrogenolysis [111]
feed impurities including phosphorous onto copper sites
using copper chromite as a catalyst for C12 methyl ester
hydrogenation as shown in Fig. 16 Interestingly, the effect decomposition products (propanol and 1,2-propanediol). It
of these poisons follows one trend, if we plot the relative also appears that the rate of temporary deactivation of the
activity versus the mole of poisons per g of catalyst. catalyst with increased concentration of glycerin, mono-
glyceride or 1,2-propane diol in the feed is the same. This
Effect of Glycerine on Catalyst Activity suggests that the molecular interaction with the copper
chromite surface may be the same for these molecules. In
Thakur et al. [111] also confirmed the completely revers- other words, these molecules may form a common interme-
ible or temporary deactivation of copper chromite cata- diate that interacts with the surface sites. In addition, their
lyst with glycerine and monoglyceride (Fig. 17) and their results show that the fresh oxide catalyst suffers higher

13

activity loss when exposed to glycerine than the prereduced
catalyst.
Recent Developments on Catalysts for Fatty
Alcohol Chemistry
Recent development on catalysts for fatty alcohol chemis-
try is focused on searching for Cr free alternative formu-
lations both in fixed bed and slurry processes to reduce
the environmental pollution and to produce fatty alcohol
under milder process conditions. Kandel et al. [120] stud-
ied Fe-induced promotional effect on Cu on mesoporous
silica nanoparticles catalyst for hydrogenation of stearic
acid to 1-octadecanol in a batch reactor. The highest activ-
ity (100 % conversion) with moderately high selectivity
(>95 %) was obtained with Cu/Fe mole ratio of 1. Increas-
ing the relative loading of Fe in the catalyst leads to sig-
nificantly lower activity and selectivity. On the other hand,
increasing the loading of Cu leads to slightly lower activ-
ity (85 % conversion) but 100 % alcohol selectivity. Based
on this behavior, the authors have proposed a synergistic
hydrogenation mechanism where in situ-generated metal-
lic copper, which likely acts as a binding and activating
site for H2 and spills over to iron oxide creating an oxy-
gen vacancy. The carboxylic groups binds at the generated
oxygen vacancies and gets reduced by a second equivalent
of hydrogen. A similar catalyst was developed by He et al.
[121] for hydrogenation of ethyl stearate to stearyl alcohol
as a proof of concept carried out in an autoclave at 230 °C
and 30 bar pressure of hydrogen. The bimetallic catalyst
with a Cu/Fe mole ratio of 4/1 is more active than the cata-
lyst with a Cu/Fe mole ratio of 1/4. They have attributed
the higher activity of bimetallic catalyst with a Cu/Fe mole
ratio of 4/1 to the synergistic effects of Cu0/Cu+ species
and Fe3O4, a large surface area and Lewis acid sites.
Many reports in the literature [122–125] have given
importance recently to developing a homogenous catalyst
for fatty acid methyl ester hydrogenation as it might have
advantages in terms of selectivity and the ability to run at
milder process conditions. For example, Fairweather et al.
[124] obtained 98 % yield with 1.5 mol% five-coordinate
Ru(II) PNN-pincer catalyst loading at 300 psig H2, 135 °C
temperature and 2 h reaction time. Mainly Ru- or Os-based
catalysts are used with different types of ligands connected
to the metal (e.g. bidentate amino-phosphine, tetradentate
imino-phosphine). Chakraborty et al. [122] developed Iron
PNP-pincer complexes to avoid the precious metal to have
a more economical process. This catalyst showed compa-
rable alcohol yield to ruthenium catalysts, but not yet as
competitive as the most active ruthenium catalysts. The use
of homogeneous catalysts might have another advantage in
terms of application in direct hydrogenation of triglyceride
13
J Am Oil Chem Soc
to fatty alcohol as reported by Fairwether et al. [124] and
Acosta-Ramirez et al. [125]. The maximum yield of 91 %
of the desired alcohols were obtained with Milstein cata-
lyst for catalytic hydrogenation of coconut oil at 135 °C
at 750 psig pressure [124]. Despite many advantages, this
process has long way to make industrial process as several
problems needs to be resolved before scale-up e.g., catalyst
recovery, products separation, and disposal of toxic waste.
Conclusions
The literature pertaining to catalytic fatty alcohol processes
was critically reviewed in this paper with special empha-
sis on catalyst development for both slurry and fixed bed
processes using fatty ester feeds. Challenges faced by the
catalyst scientists while designing a catalyst for this com-
plex chemistry are also discussed in detail. Environmen-
tally-friendly non-Cr Copper catalysts have been developed
as an alternative to Cu–Cr catalyst, which are being used
commercially.
For the slurry process, a copper chromite catalyst pre-
pared by simultaneous precipitation at constant pH pro-
duces a catalyst with narrow particle size distribution and
pore size distribution. These properties help to produce
more activity and faster filterability. A CuCr catalyst is
susceptible to acid attack. Addition of SiO2 to CuCr cata-
lyst improves the acid resistance and performance. For the
fixed bed process, the new shape and design of the cata-
lyst was found to overcome the mass transfer limitation
thereby giving a higher performance at a lower tempera-
ture. In that case, the reactor design plays an important role
with efficient loading and minimized maldistribution of the
reactants.
As the use of Cr(VI) is restricted due to stringent envi-
ronmental regulations, recent focus has been to develop
non-chrome catalyst, mainly from CuZn, CuMn and CuFe
groups. Very recent investigations have studied the interac-
tion of Fe with Cu for higher activity. They have attributed
the higher activity of CuFe bimetallic catalyst to the syner-
gistic effects of Cu0/Cu+ species and Fe3O4, large surface
area and Lewis acid sites.
Catalyst deactivation studies point out that feed impuri-
ties such as P, S and Cl cause irreversible/permanent deac-
tivation of Cu catalysts. On the other hand, the free acid,
triglyceride and water act as temporary poisons; with a sub-
stantial recovery of activity upon switching to cleaner feed.
Much understanding is needed on this aspect, especially
on the exploration on the kinds of contaminants (e.g. type
of sulfur, phosphorous and chloride species present in the
feed).
There have been some studies devoted to direct fatty
acid hydrogenation to fatty alcohol with precious metal
J Am Oil Chem Soc
catalysts. The commercial applicability of this process is
limited as this process requires corrosion-resistant materi-
als of construction and relatively expensive catalyst.
Although there are a few researchers reporting advan-
tages of using supercritical solvents for fatty alcohol pro-
duction, no plant has been built using this technology. The
large solvent recycling and cumbersome product/solvent
separation may be the extra hurdles in order to bring it to
the plant scale.
Few attempts have been made to develop a homogenous
catalyst as this kind of catalyst can potentially exhibit very
high activity with a small amount of catalyst and possess no
mass transfer limitation. The process scale-up constraint of
separating the homogenous catalyst from the liquid product
and the difficulty to make bulk quantities of this catalyst
are the main obstacles for commercial viability.
References
1. Kenneally C (2001) Alcohols, higher aliphatic, survey. In: Kirk-
Othmer encyclopedia of chemical technology, vol 2. Wiley
2. Colin A (2013) Higher alcohols 2025. Houston Associates
report
3. Lo C, Cameron W (2012) Nexant ChemSystems PERP report
on “oleochemicals"
4. Suyenty E, Sentosa H, Agustine M, Anwar S, Lie A, Sutanto E
(2007) Catalyst in basic oleochemicals. Bull Chem React Eng
Catal 2:22–31
5. Behr A, Westfechtel A, Gomes JP (2008) Catalytic processes
for the technical use of natural fats and oils. Chem Eng Technol
31:700–714
6. Thakur D, Okonek D, Hoelzle M (2008) Paper presented at
PRO 3/EXH 2: processing exhibitor session; the 99th AOCS
annual meeting and expo
7. Noweck K, Grafahrend W (2012) Fatty alcohols. Ullmann’s
encyclopedia of industrial chemistry, vol 14. Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim, pp 117–141
8. Hansley V.L. (1937) Reduction of esters. US Patent 2,096,036
9. Hansley V.L (1939) Ester condensations. US Patent 2,158,071
10. Kastens M, Peddicord H (1949) Alcohols by sodium reduction.
Ind Eng Chem 41:438–446
11. Adkins H, Folkers K (1931) The catalytic hydrogenation of
esters to alcohols. J Am Chem Soc 53:1095–1097
12. Norman W (1931) Über die katalytische Reduktion der Carbox-
ylgruppe. Angew Chem 44:714–717
13. Schrauth W, Schenk O, Stickdorn K (1931) Über die Her-
stellung von Kohlenwasserstoffen und Alkoholen durch
Hochdruck-Reduktion von Fettstoffen. Ber Dtsch Chem Ges
64:1314–1318
14. Schmidt O (1931) Die Katalytische Hydrierung der Carbox-
ylgruppe in organischen Verbindungen, Insbesondere solchen
höheren Molekulargewichts. Ber Dtsch Chem Ges 64:2051–2053
15. Adkins H, Folker K, Conner R (1937) Method of hydrogenating
esters. US Patent 2,091,800
16. Adkins H (1940) Hydrogenation role of the catalyst. Ind Eng
Chem 32:1189–1192
17. Rittmeister W (1941) Process for the reduction of fatty acids to
alcohols. US Patent 2,248,465A
18. Rittmeister W (1959) Process for the production of unsaturated
fatty alcohols. US Patent 3,193,586A
19. Richardson A, Taylor J (1944) Process for forming alcohols or
esters. US Patent 2,340,343
20. Rabes IV, Schenck R (1948) Die Adkins’schen Kupfer-Chro-
mit-Katalysatoren und ihre Wirkungsursache. Zeitschrift für
Elektrochemie und angewandte physikalische Chemie 52:37–39
21. Reiner TW (1949) An improved laboratory preparation of cop-
per-chromium oxide catalyst. J Am Chem Soc 71:1130
22. Stroupe JD (1949) An X-ray diffraction study of the copper
chromites and of the “copper-chromium oxide” catalyst. J Am
Chem Soc 71:569–572
23. Adkins H, Burgoyne E, Schneider HJ (1950) The copper–
chromium oxide catalyst for hydrogenation. J Am Chem Soc
72:2626–2629
24. De Nora V, de Bartholomaeis E (1956) Continuous hydrogena-
tion of fatty material. US Patent 2,750,429
25. Toland W, Rafael S, Levine I (1957) Higher fatty alcohols. US
Patent 2,776,323
26. Church J, Abdel-Gelil M (1957) Catalytic hydrogenation of
methyl laurate to lauryl alcohol. Ind Eng Chem 49:813–817
27. Haidegger E, Karolyi J, Zalai A (1959) Die Erzeugung von Fet-
talkoholen durch katalytische Hochdruckhydrierung. I. Acta
Chim Acad Sci Hung 19:23
28. Karolyi J, Haidegger E, Hodossy L (1960) Erzeugung von fet-
talkoholen mittels katalytischer hochdruckhydrierung. II. Acta
Chim Acad Sci Hung 20:157
29. Pantulu AJ, Achaya KT (1964) Hydrogenolysis of saturated,
oleic and ricinoleic acids to the corresponding alcohols. J Am
Oil Chem Soc 41:511–514
30. Eisenlohr K-H, Voeste T (1965) Process for the production of
fatty alcohols by catalytic hydrogenation of fatty acids and their
derivatives. US Patent 3,180,898
31. Muttzall KMK (1966) High-pressure hydrogenation of fatty
acid esters to fatty alcohols. Ph. D. thesis, University of Delft,
The Netherlands
32. Muttzall KMK, van der Berg PJ (1971) Hydrogenation of fatty
acid esters to fatty alcohols. In: Proceedings of the European
symposium chemical reaction engineering (1968), 4th edn. Per-
gamon Press Ltd., Oxford, pp 277–285
33. Frazee JR, Martin B, Brundrett C (1973) Supported copper
chromite catalyst. US Patent 3,756,964
34. Montgomery S (1973) Process for producing copper chromite
catalysts. US Patent 3,767,595
35. Boerma H (1976) In: Delmon B, Jacobs P, Poncelet G (eds)
Preparation of copper and zinc chromium oxide catalysts for the
reduction of fatty esters to alcohols. In: International Sympo-
sium on preparation of catalysis, vol 1. Elsevier, pp 105-118
36. Monick JA (1979) Fatty alcohols. J Am Oil Chem Soc
56:853A–860A
37. Voeste T, Schmidt HJ, Marschner F (1981) Continuous process
of producing fatty alcohols. US Patent 4,259,536
38. Buchold H (1983) Natural fats and oils route to fatty alcohols.
Chem Eng 90:42–43
39. Voeste T, Buchold H (1984) Production of fatty alcohols from
fatty acids. J Am Oil Chem Soc 61:350–352
40. Kreutzer UR (1984) Manufacture of fatty alcohols based on
natural fats and oils. J Am Oil Chem Soc 61:343–348
41. Schuett H (1989) Process for obtaining fatty alcohols from free
fatty acids. US Patent 4,804,790
42. Fleckenstein T (1991) Process for the hydrogenation of fatty
acid methyl ester mixtures. US Patent 5,043,485
43. Demmering G, Heck S, Friesenhagen L (1994) Process for the
production of fatty alcohols. US Patent 5,364,986
44. Poels EK, Polman DRE, Vresswijk JJ (1992) Alcohol produc-
tion by the hydrogenation of fatty acid esters. GB 2,250,287 A1
45. Wilmott M, Harrison G, Scarlett J, Wood M, McKinley D
(1992) Fatty alcohols. US Patent 5,138,106
13

46. Wilmott M, Harrison G, Scarlett J, Wood M, McKinley D
(1992) Process for the production of fatty alcohols. US Patent
5,157,168
47. Buchold H, Gartner F-J, Mallok G, Schlichting E, Stonner H-M
(1997) Process for preparing wax esters and hydrogenation of
wax esters to fatty alcohols. US Patent 5,608,122
48. Boensch R, Noweck K (2013) Method for the production of
fatty alcohols. US Patent 8,426,654
49. Appleton P, Wood M, Wild R (2014) Process for producing
fatty alcohols from fatty acids. US Patent 8884078
50. van de Scheur FT, Vreeswijk JJ (1994) Process for the produc-
tion of alcohols. WO 1994006738 A1
51. van den Hark S, Härröd M, Møller P (1999) Hydrogenation of
fatty acid methyl esters to fatty alcohols at supercritical condi-
tions. J Am Oil Chem Soc 76:1363–1370
52. van den Hark S, Harrod M (2001) Hydrogenation of oleochemi-
cals at supercritical single-phase conditions: influence of hydro-
gen and substrate concentrations on the process. Appl Catal
210:207–215
53. Brands DS, Poels EK, Dimian AC, Bliek A (2002) Solvent-
based fatty alcohol synthesis using supercritical butane: thermo-
dynamic analysis. J Am Oil Chem Soc 79:75–83
54. Brands DS, Pontzen K, Poels E, Dimian A, Bliek A (2002) Solvent-
based fatty alcohol synthesis using supercritical butane: flowsheet
analysis and process design. J Am Oil Chem Soc 79:85–91
55. Zhilong Y (2011) Biodiesel quality, emissions and by-products.
In: Montero G (ed) Research on hydrogenation of FAME to
fatty alcohols at supercritical conditions, Ch. 11. INTECH, New
York, pp 170–180
56. Liang S, Liu H, Wang W, Jiang T, Zhang Z, Han B (2012)
Hydrogenation of methyl laurate to produce lauryl alcohol
over Cu/ZnO/Al2O3 with methanol as the solvent and hydrogen
source. Pure Appl Chem 84:779–788
57. Broadbent H, Campbell G, Bartley W, Johnson J (1959) Rhe-
nium and its compounds as hydrogenation catalysts. III. Rhe-
nium Heptoxide. J Org Chem 24:1847–1854
58. Trivedi BC (1978) Catalytic hydrogenation of fatty acids. US
Patent 4,104,478
59. Trivedi BC, Grote D, Mason ThO (1981) Hydrogenation of
carboxylic acids and synergistic catalysts. J Am Oil Chem Soc
58:17–20
60. Narasimhan CS, Deshpande VM, Ramnarayan K (1989) Selec-
tive hydrogenation of methyl oleate to oleyl alcohol on mixed
ruthenium-tin boride catalysts. Appl Catal 48:L1–L5
61. Yoshino K, Kajiwara Y, Takaishi N, Inamoto Y, Tsuji J (1990)
Hydrogenation of carboxylic acids by rhenium–osmium bimet-
talic catalyst. J Am Oil Chem Soc 67:21–24
62. Nagahara E, Itoi Y (1995) Catalyst for direct reduction of
carboxylic acid, process for preparation there of and pro-
cess for preparation of alcohol using the catalyst. US Patent
5,426,246
63. Tahara K, Nagahara E, Itoi Y, Nishiyama S, Tsuruya S, Masai
M (1997) Liquid-phase hydrogenation of carboxylic acid on
supported bimetallic Ru–Sn–alumina catalysts. Appl Catal A
154:75–86
64. Pouilloux Y, Autin F, Guimon C, Barrault J (1998) Hydrogena-
tion of fatty esters over ruthenium-tin catalysts; characterization
and identification of active centers. J Catal 176:215–224
65. Pouilloux Y, Autin F, Piccirilli A, Guimon C, Barrault J (1998)
Preparation of oleyl alcohol from the hydrogenation of methyl
oleate in the presence of cobalt-tin catalysts. Appl Catal A
16:65–75
66. Toba M, Tanaka S, Niwa S, Mizukami F, Koppany Z, Guczi L,
Cheah K-Y, Tang T-S (1999) Synthesis of alcohols and diols
by hydrogenation of carboxylic acids and esters over Ru–Sn–
Al2O3 catalysts. Appl Catal A 189:243–250
13
J Am Oil Chem Soc
67. Miyake T, Makino T, Taniguchi S-I, Watanuki H, Niki T,
Shimizu S, Kojima Y, Sano M (2009) Alcohol synthesis by
hydrogenation of fatty acid methyl esters on supported Ru–Sn
and Rh–Sn catalysts. Appl Catal A 364:108–112
68. Echeverri D, Marin J, Restrepo G, Rios L (2009) Characteri-
zation and carbonylic hydrogenation of methyl oleate over Ru–
Sn/Al2O3: effects of metal precursor and chlorine removal. Appl
Catal A 366:342–347
69. Zhang L, Zheng X, Li R (2015) Effect of Lanthanum on catalytic
performance of Ru/Al2O3 catalyst for hydrogenation of esters to
corresponding alcohols. Chem Res Chin Univ 31:615–620
70. Rozmysłowicz B, Kirilin A, Aho A, Manyar H, Hardacre C,
Warna J, Salmi T, Murzin D (2015) Selective hydrogenation of
fatty acids to alcohols over highly dispersed ReOx/TiO2 cata-
lyst. J Catal 328:197–207
71. Miya B, Sawamoto Y, Hashiba K, Hisamitsu H (1979) Process
for preparation for copper-iron-aluminium catalysts and cata-
lysts prepared by the process. US Patent 4,144,198
72. Miya B, Miya F, Nawashiro Y (1981) Process for preparation
of copper-iron-aluminium hydrogenation catalyst. US Patent
4,278,567
73. Pohl J, Carduck F-J, Goebel G (1989) Acid-resistant catalysts
for the direct hydrogenation of fatty acids to fatty alcohols. US
Patent 4,855,273
74. Nierhaus W, Pohl J, Goebel G (1992) Copper/manganese cata-
lysts. WO 1992/04119
75. Schneider M, Maletz G, Kochloeft K (1993) SiO2-containing
copper oxide-chromium oxide catalyst for the hydrogenation of
fatty acids and fatty esters. US Patent 5,217,937
76. Schneider M, Maletz G, Kochloeft K (1993) Acid-resistant cop-
per oxide-chromium oxide catalyst for the hydrogenation of
fatty acids and fatty esters. US Patent 5,206,203
77. Thakur D, Palka E, Sullivan T, Nebesh E, Roberts B (1992)
Process for preparing catalyst with copper or zinc and with
chromium, molybdenum, tungsten, or vanadium, and product
thereof. US Patent 5,134,108
78. Thakur D, Palka E, Sullivan T, Nebesh E, Roberts B (2000)
Hydrogenation catalyst, process for preparing and process of
using said catalyst. US Patent 6,054,627
79. Rieke RD, Thakur DS, Roberts BD, White GT (1997) Fatty
methyl ester hydrogenation to fatty alcohol part I: correlation
between catalyst properties and activity/selectivity. J Am Oil
Chem Soc 74:333–339
80. Rieke R, Thakur DS, Roberts BD, White GT (1997) Fatty
methyl ester hydrogenation to fatty alcohol part II: process
issues. J Am Oil Chem Soc 74:341–345
81. Prasad R (1993) A new precursor for the preparation of novel
copper chromite catalysts. Stud Surf Sci Catal 75:1747–1750
82. Prasad R, Singh P (2011) Applications and preparation methods
of copper chromite catalysts: a review. Bull Chem React Eng
Catal 6:63–113
83. Ladebeck J, Regula T (1999) Fatty methyl ester hydrogena-
tion: application of chrome free catalysts. Stud Surf Sci Catal
121:215–220
84. Ladebeck J, Regula T (2001) Catalysis of organic reactions. In:
Ford ME (ed) Copper-based chromium free hydrogenation cata-
lysts. Marcel Dekker (Publ), New York, pp 403–413
85. Schneider M, Kochloeft K, Maletz G (1995) Catalyst and pro-
cess for hydrogenation of carboxylic acid alkyl esters to higher
alcohols. US Patent 5,386,066
86. Schneider M, Kochloeft K, Maletz G (1995) Chromium-free
catalyst for the hydrogenation of organic compounds. US Patent
5,403,962
87. Thakur D, Roberts B, Sullivan T, Vlacheck A (1992) Hydrogen-
ation catalyst, process for preparing and process of using said
catalyst. US Patent 5,155,086
J Am Oil Chem Soc
88. Thakur D, Roberts B, Sullivan T, Vlacheck A (1994) Hydrogen-
ation catalyst, process for preparing and process of using said
catalyst. US Patent 5, 345,005
89. Matsuda M, Horio M, Tsukada K (1992) Process for producing
hydrogenation catalyst. US patent 5,120,700
90. van Beijnum J, van Dillen AJ, Geus J (1993) Hydrogenolysis
reaction and catalyst suitable therefor. US Patent 5,198,512 A
91. Roberts BD, Thakur DS, Sullivan TJ, Plundo RA (1993) Hydro-
genation catalyst, process for preparing and process for using
said catalyst. US Patent 5,243,095
92. van de Scheur F, Th Staal L H (1994) Effects of zinc addition
to silica supported copper catalysts for the hydrogenolysis of
esters. Appl Catal 108:63–83
93. Roberts BD, Thakur DS, Sullivan TJ, Plundo RA (1995) Hydro-
genation catalyst and process for preparing same. US Patent
5,418,201
94. Brands DS, Poels EK, Bliek A (1996) The relation between pre-
treatment of promoted copper catalysts and their activity in hydro-
genation reactions. Stud Surf Sci Catal 101:1085–1094
95. Chen Y, Chang C (1997) Cu-B2O3/SiO2, an effective catalyst
for synthesis of fatty alcohol from hydrogenolysis of fatty acid
esters. Catal Lett 48:101–104
96. Brands DS (1998) The hydrogenolysis of esters to alcohols over
copper containing catalysts. Ph. D. thesis, University of Amster-
dam, The Netherlands
97. Tsukada K, Hattori Y, Mimura T (1996) Method for preparing
copper-containing hydrogenation reaction catalyst and method
for producing alcohol. US Patent 5,554,574
98. Matsuda M, Horio M, Tsukada K, Sotoya K, Abe H, Tsushima
R (1994) The production of fatty alcohols and their amino
derivatives from Coco fatty acid methyl esters In: Applewhite
T (ed) Proceedings of the World conference on lauric oils:
sources, processing, and applications, chapter 7, pp 64–71
99. Chen J. P. (2005) Preparation and use of non-chrome catalysts
for Cu/Cr catalyst applications. US Patent 6,916,457
100. Chen JP (2014) Copper catalyst for dehydrogenation applica-
tion. US Patent 8,828,903
101. Hattori Y, Yamamoto K, Kaita J, Matsuda M, Yamada S (2000)
The development of nonchromium catalyst for fatty alcohol
production. J Am Oil Soc 77:1283–1288
102. Zuzaniuk V, Gruter G-J, Veringa M, Sijpkes A, van der Puil N,
De Keijzer J, Hamid SBA (2007) Catalyst and process develop-
ment for production of oleochemicals from palm oil using high
throughput experimentation. North American Catalysis Society
meeting
103. Spikes A, van der Puil N, van der Brink P-J, de Keijzer AHJF,
Hamid SBA (2005) Chromium-free catalysts of metallic Cu and at
least one second metal. WO 2005070537 A1
104. bin Ma’amor A, Hamid SBA (2006) Combinatorial technology
in heterogenous copper-based catalysts. In: Proceedings of the
1st international conference on natural resources engineering
and technology; Putrajaya, Malaysia, pp 255–261
105. Spikes A, van der Puil N, van der Brink P-J, Hamid SBA, de
Keijzer AHJF (2007) Chromium-free catalysts of metallic Cu
and at least one second metal. US 2007/0207921 A1
106. Spikes A, van der Puil N, van der Brink P-J, Hamid SBA,
de Keijzer AHJF (2010) Chromium-free catalysts of metal-
lic Cu and at least one second metal. US Patent Application
2010/0087312 A1
107. Roberts BD, Carrick WJ, Thakur DS (1999) Shaped hydrogena-
tion catalyst and processes for their preparation and use. US
Patent 5,977,010
108. Nebesh E, Kelly DG, Novak LT (1992) Copper chromite
catalyst and process for preparation said catalyst. US Patent
5,124,295
109. Thakur DS, Carrick WJ (2015) Copper chromite hydrogenation
catalysts for production of fatty alcohols. US Patent 9,120,086
110. Huang H, Cao G, Wang S (2014) An evaluation of alkylthi-
ols and dialkyl disulfides on deactivation of Cu/Zn catalyst in
hydrogenation of dodecyl methyl ester to dodecanol. J Ind Eng
Chem 20:988–993
111. Thakur DS, Roberts BD, White GT, Rieke RD (1999) Fatty
methyl ester hydrogenation to fatty alcohol: reaction inhibi-
tion by glycerine and monoglyceride. J Am Oil Chem Soc
76:995–1000
112. van de Scheur FT, Sai GU-A, Bliek A, Staal L (1995) The effect
of free fatty acid on the reactivity of copper-based catalysts for
the hydrogenolysis of fatty acid methyl esters. J Am Oil Chem
Soc 72:1027–1031
113. Brands DS, Sai GU-A, Poels EK, Bliek A (1999) Sulfur
deactivation of fatty ester hydrogenolysis catalysts. J Catal
186:169–180
114. Twigg MV, Spencer MS (2001) Deactivation of supported cop-
per metal catalysts for hydrogenation reactions. Appl Catal A
212:161–174
115. Tike MA, Mahajani VV (2007) Kinetics of hydrogenation of
palm stearin fatty acid over Ru/Al2O3 catalyst in presence of
small quantity of water. Ind J Chem Technol 14:52–63
116. Huang H, Cao G, Fan C, Wang S, Wang S (2009) Effect of
water on Cu/Zn catalyst for hydrogenation of fatty methyl ester
to fatty alcohol. Korean J Chem Eng 26:1574–1579
117. Huang H, Wang S, Wang S, Cao G (2010) Deactivation mech-
anism of Cu/Zn catalyst poisoned by organic chlorides in
hydrogenation of fatty methyl ester to fatty alcohol. Catal Lett
134:351–357
118. Huang H, Cao G, Wang S (2013) An evaluation of trimethyl
phosphate on deactivation of Cu/Zn catalyst in hydrogenation
of dodecyl methyl ester. Korean J Chem Eng 30:1710–1715
119. Haldal JA, Mork P (1982) Chlorine-containing compounds as
copper catalyst poisons. J Am Oil Chem Soc 59:396–398
120. Kandel K, Chaudhary U, Nelson NC, Slowing II (2015) Syner-
gistic interaction between oxides of copper and iron for produc-
tion of fatty alcohols from fatty acids. ACS Catal 5:6719–6723
121. He L, Li X, Lin W, Li W, Cheng H, Yu Y, Fujita S-I, Arai M,
Zhao F (2014) The selective hydrogenation of ethyl stearate to
stearyl alcohol over Cu/Fe bimetallic catalysts. J Mol Catal A:
Chem 392:143–149
122. Chakraborty S, Dai H, Bhattacharya P, Fairweather NT, Gib-
son MS, Krause JA, Guan H (2014) Iron-based catalysts
for the hydrogenation of esters to alcohols. J Am Chem Soc
136:7869–7872
123. Tan X, Wang Y, Liu Y, Wang F, Shi L, Lee K-H, Lin Z, Lv H,
Zhang X (2015) Highly efficient tetradentate ruthenium catalyst
for ester reduction: especially for hydrogenation of fatty acid
esters. Org Lett 17:454–457
124. Fairweather NT, Gibson MS, Guan H (2014) Homogeneous
hydrogenation of fatty acid methyl esters and natural oils under
neat conditions. Organometallics 34:335–339
125. Acosta-Ramirez A, Bertoli M, Gusev DM, Schlaf M (2012)
Homogenous catalytic hydrogenation of long-chain esters by
an osmium pincer complex and its potential application in the
direct conversion of triglycerides into fatty alcohols. Green
Chem 4:1178–1188
13