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J Am Oil Chem Soc DOI 10.1007/s11746-016-2902-x

J Am Oil Chem Soc DOI 10.1007/s11746-016-2902-x REVIEW Catalysts for Fatty Alcohol Production from Renewable Resources
REVIEW
REVIEW

Catalysts for Fatty Alcohol Production from Renewable Resources

Deepak S. Thakur 1 · Arunabha Kundu 1

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 C 8 and C 22 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 C 16 –C 18 while coconut and palm kernel oils are rich in C 12 – C 14 . Detergent alcohols generally have a hydrocarbon chain length of C 12 minimum with at least 35 % linear chains. Plasticizer alcohols generally have a chain length of C 6 – C 13 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.

J Am Oil Chem Soc DOI 10.1007/s11746-016-2902-x REVIEW Catalysts for Fatty Alcohol Production from Renewable Resources

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J Am Oil Chem Soc DOI 10.1007/s11746-016-2902-x REVIEW Catalysts for Fatty Alcohol Production from Renewable Resources

J Am Oil Chem Soc

J Am Oil Chem Soc Fig. 1 Schematic of oleochemical process chemistry Although the fatty

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.

J Am Oil Chem Soc Fig. 1 Schematic of oleochemical process chemistry Although the fatty

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 [17]. Recent studies [2, 3] suggest that the global fatty alcohols market demand was 2.4 million tons in 2014 with C 10 –C 14 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, C 16 –C 22 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 %

Fig. 2 Main applications of fatty alcohols [27]

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 C 12 –C 14 alcohols are used for production of detergents while the heavy-cut C 16 –C 18 alcohols are employed for the manufacture of health/personal care products. Figure 2 illustrates the main applications.

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J Am Oil Chem Soc Fig. 1 Schematic of oleochemical process chemistry Although the fatty

J Am Oil Chem Soc

Fatty Alcohol Chemistry

The oldest method [810] for fatty alcohol production was based on the reaction of triglycerides with sodium in the presence of a reducing alcohol, such as amyl alcohol. A disadvantage of this process was high processing costs due to the high price of sodium. New processes were developed using hydrogen, which is a cheaper and cleaner reducing agent than sodium. Com- mercially, the fatty acids of palm, palm kernel or coconut oils are converted to esters by interesterification followed by hydrogenolysis of esters to corresponding alcohols using copper-based catalysts [1031]. 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- 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 Eqs. (1) and (2), respectively. Commercially, the hydrog- enolysis is carried out by using a copper-based catalyst (Eqs. 3 and 5).

Esterification/Transesterification

RCOOH + RCH 2 OH

Fatty Acid

Fatty Alcohol

RCOOR

,

Wax Ester

(1)

where R= RCH 2 C 3 H 5 (OOCR) 3 + 3CH 3 OH

Triglyceride

Methanol

3RCOOCH 3

Methyl Ester

+ C 3 H 5 (OH) 3

Glycerin

(2)

Ester Hydrogenolysis

RCOOR +H 2 2RCH 2 OH ,

Wax Ester

Fatty Alcohol

where R= RCH 2 RCOOCH 3 +2H 2 RCH 2 OH + CH 3 OH

Methyl Ester

Fatty Alcohol

Methanol

Interesterification

RCOOCH 3 + RCH 2 OH

RCOOR

,

Methyl Ester

Fatty Alcohol

Wax Ester

(3)

(4)

(5)

where R= RCH 2 – The undesired byproducts are formed during hydrogen- olysis represented by Eqs. (5) to (7).

Excessive Hydrogenation

RCH 2 OH −→ R–CH 3

Fatty Alcohol

+H 2

Hydrocarbon

(6)

Dehydration 2RCH 2 OH

Fatty Alcohol

H 2 O

R–CH 2 O –CH 2 –R

Ether

Dehydrogenation

RCH 2 OH

Fatty Alcohol

R–CHO

H 2 Carbonyl Compound

(7)

(8)

A few studies have been conducted to elucidate the pos- sible mechanistic pathways. Norman [12] postulated that fatty acid ester hydrogenolysis proceeds through a hemiac- etal intermediate:

J Am Oil Chem Soc Fatty Alcohol Chemistry The oldest method [ 8 – 10 ]
J Am Oil Chem Soc Fatty Alcohol Chemistry The oldest method [ 8 – 10 ]

(9)

Commercially, both fatty acid wax ester and fatty acid methyl ester feeds are hydrogenated to fatty alcohol using slurry and fixed bed reactors. Table 1 gives the operating conditions used for each type of reactor to achieve opti- mum performance.

Catalytic Processes for Fatty Alcohol Production

Earlier several groups in academia and industry [1036] were trying to develop catalytic processes for fatty alcohol manufacture either from fatty acids or their corresponding esters. The pioneering work of Adkins et al. [11, 15, 16, 23] documented an efficient way of producing fatty alco- hols using copper chromite catalysts. Initially, the fatty alcohol plants were installed by using a high pressure continuous slurry process and copper chro- mite powder as catalyst. Procter & Gamble and the Kao Soap used their own slurry methyl ester hydrogenation process technology and in-house developed catalyst, while Air Liquide (then Lurgi) licensed slurry fatty acid (via wax ester) hydrogenation process with vendor supplied catalyst to produce fatty alcohols. Air Liquide (then Lurgi) [3739] developed a process that made it possible to hydrogenate fatty acid by carrying out esterification to wax ester and hydrogenation steps in one reactor using a copper chromite catalyst. The C=C double bonds present in the fatty acids are hydrogenated to produce saturated fatty alcohols. The slurry process is a continuous operation with fatty ester feed, powder catalyst and hydrogen coming in contact with each other under reaction conditions inside the reac- 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 fatty alcohol and then hydrogenating to alcohol. The reac- tor effluent goes through a few unit operations including

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J Am Oil Chem Soc Fatty Alcohol Chemistry The oldest method [ 8 – 10 ]

J Am Oil Chem Soc

Table 1 Slurry phase and fixed bed process conditions

Process conditions

Slurry reactor

Fixed bed

 

Liquid phase

Gas phase

Pressure (bar)

250–300

250–300

40

Temperature (°C)

280

180–220

200–240

Feed Catalyst shape

Methyl or wax ester Powder

Methyl or wax ester Tablets or extrudates

Methyl ester Tablets or extrudates

H 2 /feed (molar ratio)

25–50

40–100

250 and above

Configuration

Continuous recycle, liquid phase

Down flow; trickle-bed, gas–liquid-solid

Down flow; gas–solid

J Am Oil Chem Soc Table 1 Slurry phase and fixed bed process conditions Process

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 [4044] (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, 4549] 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

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J Am Oil Chem Soc Table 1 Slurry phase and fixed bed process conditions Process

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

J Am Oil Chem Soc Fig. 4 Schematics of methyl and wax ester fixed bed processes

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, H 2 /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/Al 2 O 3 served as both a reforming and hydrogenation catalyst for this purpose. The conversion is very much dependent on the methanol concentration. The

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 [5770]. Broadbent et al. [57] conducted pioneering work to demonstrate the ability of ReO 2 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 ((Bu 3 Sn) 2 O), K 2 SnO 3 and Na 2 SnO 3 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/Al 2 O 3 catalysts for hydrogenation carboxylic acids including C 6 –C 18 fatty acids to corresponding alco- hols. The data shown in Table 3 compares the performance of these catalysts for various substrates. Rozmslowicz

Table 2 Hydrogenation of decanoic acid with Re oxide

[61]

Precursors of catalysts

Conversion (%)

Products (%)

Selectivity of alcohol (%)

 

Hydrocarbon

Alcohol

Ester

Re 2 O

7

31.0

1.4

22.9

13.2

73.9

Re 2 O 7 + OsO 4

94.4

11.7

79.8

5.8

84.5

OsO 4

3.4

1.1

1.6

1.3

47.1

Re 2 O 7 + 5 % Ru/C

62.3

3.3

54.1

10.0

86.8

Re 2 O 7 + 5 % Pd/C

8.7

2.0

4.7

3.2

54.0

 

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J Am Oil Chem Soc

Table 3 Hydrogenation of fatty acids over 2 wt% Ru/4.7 wt% Sn catalysts [66]

Substrate

Carbon number

H 2 pressure (MPa)

Acid conversion (%)

Yield

 

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 over 4 % ReO x /TiO 2 at temperatures of 180–210 °C and 20–40 bar with selectivity of 93 %. The use of reduc- ible oxide support, such as TiO 2 instead of alumina has increased the activity and selectivity due to Ru–Ti metal support interaction. Although there have been more studies on the use of rhenium-ruthenium catalysts [6370] for carboxylic acid hydrogenation, these catalyst systems have not yet been used in the fatty alcohol industry. This may be due to the catalyst price due to use of a precious metal and corro- sion-resistant materials of construction for the process requirements.

Catalyst Development for Slurry Process

Initially, copper chromite had been the catalyst of choice, prepared by several ways described in the literature [11, 1316, 23, 3136]. 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(NO 3 ) 2 + (NH 4 ) 2 Cr 2 O 7 + 4NH 4 OH 2 NH 4 CuCrO 4 (OH) +4NH 4 NO 3 + H 2 O

Adkin’s Complex

(10)

During decomposition of Adkins’ complex, the ammo- nia splits into nitrogen and hydrogen. The latter reduces Cr 6+ to Cr 3+ species which is an exothermic reaction.

NH 4 CuCrO 4 (OH) CuO · CuCr 2 O 4 + N 2 + 5H 2 O

(11)

The fresh copper chromite was found to consist of CuO and CuCr 2 O 4 . In addition to the reactions (1)–(5), the fol- lowing reactions occur during ester hydrogenolysis using copper catalysts:

Cu 2+ O / Support + H 2 Cu 0 /Support +H 2 O (Desired Reaction)

Catalyst

Active Site

(12)

Cu 2+ O /Support + RCOOH Acid (RCOO) 2 Cu 2+ +H 2 O

Catalyst

Free Fatty

Copper Soap

(Undesired Reaction)

(13)

(RCOO) 2 Cu 2+ + H 2 2RCH 2 OH + Cu 0 Undesired Cu 0 Sintering

(14)

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

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J Am Oil Chem Soc Table 3 Hydrogenation of fatty acids over 2 wt% Ru/4.7

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 (m 2 /g)

Pore volume (mL/g)

Pore size (Å)

Catalyst diameter (μ)

  • 1 399

44.8

0.31

276

1.66

  • 2 427

35.9

0.24

268

1.58

  • 3 460

25.8

0.19

296

1.28

  • 4 516

18.5

0.16

344

1.23

  • 5 538

13.4

0.09

280

1.02

[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.

RCOOR + H 2

K eq

2RCH 2 OH

(15)

He reported that the equilibrium constant (K eq ) 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

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, 7180]. 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

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J Am Oil Chem Soc Table 4 Effect of calcination temperature on physical properties of CuCr

J Am Oil Chem Soc

J Am Oil Chem Soc Fig. 5 Dependence of a activity and b selectivity on

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 Cu 0 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 Cu 0 crystallite size. Thus, copper leach- ing not only impairs the catalyst performance due to Cu 0 crystal growth (Fig. 7) but can also contaminate the fatty alcohol. There are a few patents [7376] 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.

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.

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J Am Oil Chem Soc Fig. 5 Dependence of a activity and b selectivity on

J Am Oil Chem Soc

J Am Oil Chem Soc Fig. 6 Comparison of Cu–Cr catalyst preparation procedures: a activity, b

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

J Am Oil Chem Soc Fig. 6 Comparison of Cu–Cr catalyst preparation procedures: a activity, b

Well Dispersed Cu Particles More number of Cu active sites

Sintering of Cu° crystallite Fewer number of Cu active sites

Non‑Cr Copper Catalysts

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

non-Cr-containing environmentally friendly catalysts. Vari- ous researchers [85101] 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

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J Am Oil Chem Soc Fig. 6 Comparison of Cu–Cr catalyst preparation procedures: a activity, b

J Am Oil Chem Soc

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 [102106] 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

J Am Oil Chem Soc activity and acceptable acid tolerance. Schneider et al . [

Fig. 8 Effect of different promoters on Cu catalysts [101]

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

1 3

J Am Oil Chem Soc activity and acceptable acid tolerance. Schneider et al . [

J Am Oil Chem Soc

50 40 30 20 10 0 0 25 50 75 100 125 150 175 200 Hours-on-stream
50
40
30
20
10
0
0
25
50
75
100
125
150
175
200
Hours-on-stream
Sap onificatio n Valu e

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 [110118]. 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/SiO 2 and 14 wt% Cu/SiO 2 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

Surface area/volume

204

100

J Am Oil Chem Soc 50 40 30 20 10 0 0 25 50 75 100

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]):

0

2Cu + H 2 S Cu 2 S + H 2 G = −122.1 kJ/mol

f

(16)

1 3

J Am Oil Chem Soc 50 40 30 20 10 0 0 25 50 75 100

J Am Oil Chem Soc

J Am Oil Chem Soc Fig. 11 Sulfur deactivation mechanism adopted from Brands et al

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

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 Cu 2 S. A similar phenomenon was explained by Twigg and Spencer [114].

0

Zn + 1 / 2 S 2 ZnS G = −146 kJ/mol

f

(17)

0

MnO + H 2 S MnS + H 2 O G = −213 kJ/mol

f

(18)

Brand et al. [113] showed that deactivation is faster for unpromoted Cu/SiO 2 than Zn promoted Cu/SiO 2 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/SiO 2 catalyst compared to 80 min with unpromoted Cu/SiO 2 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

1 3

J Am Oil Chem Soc Fig. 11 Sulfur deactivation mechanism adopted from Brands et al

J Am Oil Chem Soc

J Am Oil Chem Soc Fig. 12 Deactivation profile for methyl palmitate hydrogenolysis in the presence

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 kg cat 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

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/g catalyst 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/g catalyst ethanethiol) and dialkyl disulfides also attack the surface Cu of the Cu/Zn catalyst forming Cu 7 S 4 or Cu 31 S 16 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 Cu 2 S (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

Fig. 13 Conversion of dodecyl methyl ester at different levels of sulfur concentration in mmol/ g catalyst and different types of sulfur compounds [110]

1 3
1 3

J Am Oil Chem Soc

J Am Oil Chem Soc Fig. 14 XRD Patterns of Cu/Zn catalysts after reaction with:

Fig. 14 XRD Patterns of Cu/Zn catalysts after reaction with: (1) no sulfur species; (2) 0.2 mmol/g catalyst ethanethiol; (3) 5 mmol/g catalyst ethanethiol; (4) 15.1 mmol/g catalyst ethanethiol; (5) 14.6 mmol/g catalyst n-butanethiol; (6) 14.3 mmol/g catalyst 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 ZnCl 2 (s) (121.8 kJ/ mol) is much higher than that of CuCl(s) (43.5 k/mol).

ZnCl 2 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/g catalyst . With the increase of chloride concentration from 0 to 0.2 mmol/ g catalyst , the conversion of methyl laurate decreased slightly. However, with a further increase in chloride concentration from 0.2 to 0.5 mmol/g catalyst 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 ZnCl 2 + O 2

(19)

  • (b) Migration of O 2 to Cu lattice:

2Cu + O 2 Cu 2 O

(20)

Scenario 2: High chloride concentration:

  • (a) H + + Cl + CH 3 OH CH 3 O + H 2 + Cl

(21)

  • (b) 2CH 3 O + H 2 + 2Cl ZnCl 2 + 2H 2 O + 2CH 3 OH

 

(22)

1 3

1 3
  • (c) 2Cu + O 2 Cu 2 O + 2H + + 2Cl 2CuCl + H 2 O

(23)

The formation of ZnCl 2 and CuCl at 15 mmol chloride concentration/g catalyst decreases the BET surface area from

  • 19.1 to <0.3 m 2 /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 C 12 methyl ester and 4–7.2 g copper–chromite catalyst at 207 bar and 280 °C. The conversion of C 12 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/Al 2 O 3 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/SiO 2 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/Al 2 O 3 and Cu/ZnO/Al 2 O 3 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

J Am Oil Chem Soc Fig. 15 Relative conversion of dodecyl methyl ester vs level of

Fig. 15 Relative conversion of dodecyl methyl ester vs level of water and soap contamination [111]

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- nent deactivation by irreversible adsorption of various feed impurities including phosphorous onto copper sites using copper chromite as a catalyst for C 12 methyl ester hydrogenation as shown in Fig. 16 Interestingly, the effect of these poisons follows one trend, if we plot the relative activity versus the mole of poisons per g of catalyst.

Effect of Glycerine on Catalyst Activity

Thakur et al. [111] also confirmed the completely revers- ible or temporary deactivation of copper chromite cata- lyst with glycerine and monoglyceride (Fig. 17) and their

J Am Oil Chem Soc Fig. 15 Relative conversion of dodecyl methyl ester vs level of

Fig. 16 Relative conversion of dodecyl methyl ester vs millimoles/ kg of permanent catalyst poisons [111]. φ 2 P-C 2 H 4 -Pφ 2 , bis(diphenyl phospheno)ethane; C 18 SO 3 Me, n-octadecyl methane sulfonate; C 18 Br, n-octadecyl bromide; C 18 Cl, n-octadecyl chloride; C 18 SH, n-octade- cyl thiol

J Am Oil Chem Soc Fig. 15 Relative conversion of dodecyl methyl ester vs level of

Fig. 17 Effect of glycerine and monoglyceride on C 12 methyl ester hydrogenolysis [111]

decomposition products (propanol and 1,2-propanediol). It also appears that the rate of temporary deactivation of the catalyst with increased concentration of glycerin, mono- glyceride or 1,2-propane diol in the feed is the same. This suggests that the molecular interaction with the copper chromite surface may be the same for these molecules. In other words, these molecules may form a common interme- diate that interacts with the surface sites. In addition, their results show that the fresh oxide catalyst suffers higher

1 3

J Am Oil Chem Soc Fig. 15 Relative conversion of dodecyl methyl ester vs level of

J Am Oil Chem Soc

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 H 2 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 Cu 0 /Cu + species and Fe 3 O 4 , a large surface area and Lewis acid sites. Many reports in the literature [122125] 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 H 2 , 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

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 SiO 2 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 Cu 0 /Cu + species and Fe 3 O 4 , 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

1 3

J Am Oil Chem Soc activity loss when exposed to glycerine than the prereduced catalyst.

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.

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