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Applied Catalysis A: General 345 (2008) 201212

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Applied Catalysis A: General


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Catalytic hydrogenation of linoleic acid to stearic acid over different


Pd- and Ru-supported catalysts
P. Maki-Arvela a, J. Kuusisto a, E.Mateos Sevilla a, I. Simakova b, J.-P. Mikkola a, J. Myllyoja c,
T. Salmi a, D.Yu. Murzin a,*
Process Chemistry Centre, Abo Akademi University, FI-20500 Turku/Abo, Finland
Boreskov Institute of Catalysis, Novosibirisk, Russia
c
Neste Oil, P.O. Box 310, FI-06101 Porvoo, Finland
a

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 29 February 2008
Received in revised form 15 April 2008
Accepted 30 April 2008
Available online 7 May 2008

Catalytic hydrogenation of linoleic acid in n-decane as a solvent was studied over several Pd- and Rusupported catalysts in order to achieve complete conversion of linoleic acid into stearic acid. Catalyst
deactivation by coking was, however, rather prominent. Supported ruthenium, was more prone to
deactivation than palladium, which was also conrmed in the catalyst reuse tests with technical grade
linoleic acid. The mesoporous structure of the catalyst was preferable to achieve fast hydrogenation of the
intermediate products, thus promoting formation of stearic acid.
2008 Elsevier B.V. All rights reserved.

Keywords:
Hydrogenation
Linoleic acid
Supported metals
Palladium
Ruthenium

1. Introduction
Catalytic hydrogenation of vegetable oils has been studied
intensively in the literature [1]. These oils contain fatty acids with
18 carbon atoms in the chain. The main emphasis in these studies
has been on hardening of vegetable oils in order to improve their
stability and melting behavior [1]. Furthermore, selective hydrogenation of di-unsaturated acids and their derivatives for
producing stereoselectively mono-unsaturated acids has been
the goal, i.e. both the formation of monounsaturated trans fatty
acids and saturated stearic acid should be inhibited due to their
adverse healthy effects on human body [1,2]. Supported Pd and Ni
catalysts have been used in fatty acid hydrogenation, and Pd has
been reported to be more active than Ni [3]. There are additionally
several studies, where catalyst properties have been optimized in
order to achieve selective production of oleic acid [26]. Oleic acid
selectivity in tall oil fatty acid hydrogenation was compared over
different active carbon-supported metal catalysts increasing as
follows: Ir < Ru < Pt < Rh < Pd, with the opposite order valid for
stearic acid formation [7]. In these studies one of the determining
factors for product selectivity has been the catalyst texture, i.e. the

* Corresponding author.
E-mail address: dmurzin@abo. (D.Yu. Murzin).
0926-860X/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2008.04.042

pore size and shape [5]. These properties can affect the residence
time of the unsaturated fatty acid inside the pores and at the same
time affect the product selectivity.
Stearic acid, which is formed in linoleic acid hydrogenation, is
industrially used in cosmetics [8] and in pharmaceuticals [9]. The
reaction scheme for hydrogenation of linoleic acid into stearic acid
is shown in Fig. 1. Hydrogenation of palm oil fatty acids to stearic
acid has been reviewed by [10]. Over monometallic catalysts
stearic acid can be obtained as the main product, for instance over
Ru/C a complete conversion of linoleic acid to stearic acid was
achieved at 100 8C under atmospheric hydrogen in 1-octanol as a
solvent [11]. Additionally Raney nickel has been used for
hydrogenation of unsaturated carboxylic acids to stearic acid
[12,13]. The main challenge in industrial production of stearic acid
is to have complete conversion of linoleic acid as well as maximum
selectivity to stearic acid in order to reduce separation costs of the
product. There are no systematic studies of the catalyst properties
suitable for production of stearic acid from linoleic acid.
In the current work the aim was to study complete
hydrogenation of linoleic acid to stearic acid and especially to
elucidate the catalyst deactivation. Several Pd- and Ru-supported
catalysts were characterized and tested in the hydrogenation of
linoleic acid. The purpose was to optimize the catalyst properties
for production of stearic acid and investigate the catalyst reuse and
deactivation. Prior to the screening tests the reaction conditions

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P. Maki-Arvela et al. / Applied Catalysis A: General 345 (2008) 201212

Fig. 1. Reaction scheme for hydrogenation of linoleic acid to stearic acid. The intermediate products are oleic acid and its isomers, elaidic and trans-vaccenic acid.

were optimized in order to avoid external mass transfer


limitations.
2. Experimental
2.1. Reactor setup
Linoleic acid hydrogenation was performed in a three-phase
300 ml steel Parr autoclave. The reactor was equipped with a
cooling coil and a 5 mm ltered reactor inlet line, which avoided
the pass of the catalyst particles through it. A stirring rate of
1500 rpm was used in the experiments. A bubbling and preheating
unit was installed upstream the reactor in order to feed the
reactant solution. A heating jacket could be warmed up to control
the temperature in the unit, and hydrogen or argon was introduced
in the reactor through it, therefore that the solution could be
ashed with argon to remove the dissolved oxygen, or with
hydrogen to reach the saturation state. The sample line was
rounded by an electrical heating to avoid plugging.
2.2. Chemicals and catalyst preparation
The catalytic hydrogenation was studied for analytical
(assay  99%) linoleic acid provided by Fluka. The composition
of the reactant was 97.4% linoleic acid, 1.6% oleic acid and 0.95%
stearic acid. n-Decane (assay  95%, Fluka) was used as a solvent,
and hydrogen (AGA, 99.999 %) was bubbled into the reactant
solution. The technical grade linoleic acid (Fluka, linoleic acid
68.5%, oleic acid 24.5%, stearic acid 2.1%, palmitic acid 5.0%) was
used as a reactant in the catalyst deactivation tests. Argon (AGA,
99.999%) was utilized to ash the reactor.
The following Pd- and Ru-supported catalysts were tested in the
hydrogenation of linoleic acid: 1 wt.% Pd/C (Aldrich), 1 wt.% Pd/C
(Alfa 89113), 5 wt.% Pd/Al2O3 (Aldrich), 3 wt.% Pd/C (Aldrich),
5 wt.% Pd/C (Aldrich), 1 wt.% Pd/C (Sibunit), 5 wt.% Pd/C (Sibunit),
2.5 wt.% Pd2 wt.% Au/C (self-synthesized), 5 wt.% Ru/charcoal
(Fluka), 5 wt.% Ru/charcoal (Johnson Matthey), 5 wt.% Ru/MgO
(self-synthesized), and 5 wt.% Ru0.5 wt.% Cu/C (self-synthesized).
The Pd/C (Sibunit) catalyst with 1 and 5 wt.% loading of Pd were
prepared by hydrolysis of H2PdCl4 at pH 56, which gives so-called
polynuclear hydroxo-complexes of palladium. The precursor was
adsorbed on carbon and the pH of the slurry was increased up to
Na/Pd ratio 1:2 [14].
The Pd/MgO with 5 wt.% loading of Pd was synthesized by the
precipitation of hydrated palladium oxide onto magnesia (spheri-

cally shaped grains of diameter ca. 100 mm). Dried magnesia was
impregnated with Na2PdCl4 solution and subsequently treated
with 0.1 mol/dm3 NaOH solution. Na2PdCl4 solution was prepared
a priori by mixing PdCl2 and NaCl (1:2.5, mol:mol) for 30 min,
followed by addition of MgO. The solution was stirred for 3 h and
decanted. Thereafter the precipitate was treated with 2 dl of 0.1 M
NaOH, washed with 600 ml of deionized H2O and dried at 60 8C for
24 h. After this the catalyst was reduced in owing hydrogen and
passivated in a quartz oven (2 8C/min to 100 8C, hold for 30 min,
2 8C/min to 250 8C, hold for 2 h. After cooling to room temperature
the catalyst was passivated for 24 h in 1% O2 in N2). The synthesis is
an adaptation from the method used in [15].
Preparation of 2.5 wt.% Pd2 wt.% Au/C was made in two
consecutive steps. As the rst step gold was deposited on charcoal
(Johnson Matthey peat based charcoal (ref. P/D), pre dried
overnight in oven at 80 8C) by means of urea deposition/
precipitation and using HAuCl4 as a precursor. The synthesis
details were described in [16]. In the second step Pd was
introduced in the catalyst: an aqueous solution of Pd(II)nitrate
hydrate (Degussa) was prepared utilizing deionized water (pH of
the solution 3.7) into which the dried Au/C catalyst was added. The
impregnation was carried out at 25 8C for 24 h. After decanting the
resulting bimetallic catalyst was reduced under hydrogen ow at
80 8C in an autoclave and kept under hydrogen atmosphere for
48 h.
Preparation of 5 wt.% Ru0.5 wt.% Cu/C catalyst was performed
as follows: active charcoal (as above) was pre-dried according to
the procedure above and added to the aqueous solution
(deionized water) of RuCl3H2O (Acros). The solution was placed
in a rotary evaporator and water evaporated under vacuum
(20 8C) for 20 h. The resulting dry catalyst was reduced in a quartz
oven under hydrogen ow (2 8C/min to 320 8C, 2 h) followed by
passivation (24 h, 1% O2 in N2). Subsequently, a MeOH solution of
Cu(acac)2 was prepared and the Ru/C catalyst was added into the
solution. The solution was evaporated (rotary evaporator, 30 8C)
for 30 min, again followed by reduction (2 8C/min to 100 8C, 3 h,
2 8C/min to 300 8C, 2 h) under hydrogen ow, and subsequent
passivation.
2.3. Experimental procedures
The catalysts were dried in the oven at 100 8C overnight and
sieved when needed before introducing in the reactor. Prior to
reaction the catalysts were reduced in situ under 5 bar of hydrogen
and a 20 ml/min outow. The reactor was ashed with argon in

P. Maki-Arvela et al. / Applied Catalysis A: General 345 (2008) 201212

order to remove the remaining oxygen. The catalyst was the prereduced prior to the reaction at a heating rate of 10 8C/min till
200 8C, kept at 200 8C for 2 h and cooled down. Thereafter the
deoxygenated reactant solution was preheated to 50 8C and fed
inside the reactor. Analytical grade linoleic acid (400 mg) was
dissolved in 140 ml of n-decane giving an initial reactant solution
concentration of 0.01 M. In the catalyst deactivation tests technical
grade linoleic acid was used as a reactant in n-decane as a solvent
with 0.17 mol/l initial concentration of linoleic acid.
Linoleic acid to catalyst ratio was selected in the range 20:15:1
and the reactor was operated between 80100 8C and 20 bar. Total
reaction time was 23 h depending on the metal loading, the
catalyst activity and the catalyst amount.
2.4. Sample analysis
The samples were silylated with BSTFA (N,O-bis(trimethylsilyl)triuoroacetamide) (98%, Fluka) at a constant ratio samplesilylation agent of 1:4. The mixtures (efcient mixing is needed)
were kept in the oven for more than 30 min at 60 8C and analyzed in
the GC using a HP 6890 gas chromatograph equipped with a DB-5
non-polar capillary column with dimensions of 60 m  0.32 mm
 0.5 mm and a ame ionization detector (FID) operating at 250 8C.
The carrier gas was helium with a ow rate of 2.3 ml/min. The
following temperature program was used in the analysis: 150 8C
(0.5 min)5 8C/min240 8C4 8C/min290 8C (10 min). The sample
analysis was conrmed by a gas chromatographmass spectrometer
technique (GCMS). Few samples obtained at different reaction
times and catalyst particle size over a 1 wt.% Pd/C (Aldrich) catalyst
were analyzed with a gas chromatograph HP 6890-5973 GCMSD
instrument, equipped with a HP-1 GC column of 25 m length,
0.20 mm of internal diameter and a lm thickness of 0.11 mm. A
carrier gas (helium) ow was 0.8 ml/min, and the following
temperature program was used: 80 8C (0.5 min)8 8C/min300 8C.
The injector temperature was 260 8C, and the mass spectrometer
used an electron impact (EI) ionization mode with 70 eV of electron
energy. In the gas chromatographic analysis linoleic acid, oleic acid
and stearic acid were calculated separately, whereas other C18:1
acids, i.e. trans-vaccenic acid, cis-vaccenic acid and elaidic acid were
lumped together, thus notated as C18:1 acids.
2.5. Catalyst characterization
2.5.1. Nitrogen adsorption
The specic surface areas of the catalysts were determined by
nitrogen (AGA, 99.999%) adsorption technique using a sorptometer
(Sorptomatic 1900, Carlo Erba Instruments). The mesoporous and
microporous materials specic surface area was calculated
according to the BET and the Dubinin equations, respectively.
The pore size distributions were calculated according to the
DollimoreHeal method.
2.5.2. Temperature programmed desorption of hydrogen (TPD-H2)
The hydrogen adsorption capacities of the catalysts were
studied by temperature programmed desorption of hydrogen (H2TPD) using an Autochem 2910 apparatus (Micrometrics).
Catalysts were reduced following the same procedure, e.g. they
were pre-treated prior to the reaction using a 50 ml/min ow of
hydrogen (AGA, 99.999%) (see above). After reduction, the catalysts
were ashed with a 50 ml/min ow of nitrogen (AGA, 99.999 %) for
30 min in order to remove the hydrogen adsorbed physically, and
under the same ow rate, the temperature was increased to 700 8C
with a heating rate of 10 8C/min and kept at 700 8C for 1 h to
remove the chemisorbed hydrogen. The gases desorbed from the
catalyst surface were detected by a quadrupole mass spectrometer

203

(Balzers Omnistar GSD 300 O). Calibration of the quadrupole MS


on-line analysis was carried out introducing hydrogen pulses in the
equipment.
3. Results and discussion
3.1. Catalyst characterization results
3.1.1. Specic surface area and pore size distribution
The specic surface areas of the catalysts were determined by
nitrogen adsorption technique using BET and Dubinin equations
(Table 1). Comparing carbon-supported catalysts (both active
carbons and charcoal), it can be seen that they exhibited the
highest specic surface areas, varying from 875 to 1430 m2/g. The
specic surface areas decreased in the order Sibunit > Al2O3 > MgO, being considerably lower for the latter
(Table 1). Very high specic surface areas were measured for
1 wt.% Pd/C (Aldrich) and for 5 wt.% Ru/C (Fluka).
The pore size distributions of the catalysts are given in Table 2.
The 1 wt.% Pd/C (Aldrich) and the 5 wt.% Ru/MgO catalysts
exhibited the highest relative volumes of micropores. The largest
part of macro- and mesopores was in 5 wt.% Pd/Al2O3 (Aldrich),
96%, but the specic surface area of this catalyst was, however,
relatively low (115 m2/g) being a typical one for alumina (Table 1).
In a synthetic Sibunit carbon both large specic surface area,
380 m2/g (Table 1) and the large pore sizes could be achieved
simultaneously, since the pore volume of Sibunit support material
was 0.68 cm3/g and out of this value 97% of pores were of size
above 1.7 nm. Additionally it is known that Sibunit is a porous
carboncarbon composite material, which combines the advantages of graphite (chemical stability and electric conductivity) and
active coals (high specic surface area and adsorption capacity).
Sibunit presents some advantages compared to active carbons,
such as high mechanical strength, chemical and thermal stability,
high purity and a controllable narrow pore size distribution [17].
The specic surface area of one spent catalyst was measured in
order to study catalyst deactivation. A huge decrease in specic
surface area of 5 wt.% Ru/C (Fluka) catalyst was observed after the
deactivation tests (Section 3.2.5). The specic surface area of the
spent catalyst was 80% lower than that of the fresh catalyst
(Table 1). The relative volumes of micropores decreased after using
the catalyst, while the relative volumes of macropores increased
indicating blocking of pores.
3.1.2. Hydrogen desorption
The hydrogen adsorption capacities of 5 wt.% Ru/C (Fluka),
5 wt.% Ru/C (Johnson Matthey), 5 wt.% Pd/C (Aldrich), 1 wt.% Pd/C
Table 1
Characterization results of the catalyst specic surface areas
Catalyst

Pd-based catalysts
1 wt.% Pd/C (Aldrich)
1 wt.% Pd/ C (Alfa)
1 wt.% Pd/C (Sibunit)
5 wt.% Pd/Al2O3 (Aldrich)
5 wt.% Pd/C (Sibunit)
5 wt.% Pd/C (Aldrich)
2.5 wt.% Pd2 wt.% Au/C
Ru-based catalysts
5 wt.% Ru/C (Fluka)
5 wt.% Ru/C spent (Fluka)
5 wt.% Ru/C (Johnson Matthey)
5 wt.% Ru/MgO
5 wt.% Ru0.5 wt.% Cu/C

BET specic
surface area (m2/g)

Dubinin specic
surface area (m2/g)

1126
677
380
115
380
936
674

1429
945

735

937
175
1078
39
875

807
37
626

108
1214
850

P. Maki-Arvela et al. / Applied Catalysis A: General 345 (2008) 201212

204

Table 2
Characterization results of the catalyst pore size distribution
Catalyst

Macropores and mesopores

Micropores

% of macro- and mesopores

10010 (nm)

105 (nm)

52 (nm)

21.0 (nm)

<1.0 (nm)

1 wt.% Pd/C (Aldrich)


1 wt.% Pd/ C (Alfa)
5 wt.% Pd/Al2O3 (Aldrich)
5 wt.% Pd/C (Aldrich)
2.5 wt.% Pd2 wt.% Au/C

59
53
96
58
61

31
24
25
21
28

5
4
15
7
7

23
25
56
30
26

31
23
4
31
17

10
24
0
11
7

C (Sibunit)a
5 wt.% Ru/C (Fluka)
5 wt.% Ru/C spent (Fluka)
5 wt.% Ru/C (Johnson Matthey)
5 wt.% Ru/MgO
5 wt.% Ru0.5 wt.% Cu/C

97b
66
97
60
58
63

37
58
24
14
20

7
11
13
10
16

22
28
23
34
27

20
2
17
37
19

14
1
3
5
8

Relative volumes (%).


a
Support.
b
Pore volume in the pores >1.7 nm.

Table 3
Comparison of the H2-TPD results
Catalyst

Adsorption capacity
(mmol H2/gcat)

Adsorption capacity
at 200 8C (mmol H2/gcat)

Adsorption capacity
(mmol H2/gmetal)

T (8C) at max H2
desorbed

1 wt.%
1 wt.%
5 wt.%
5 wt.%
5 wt.%

0.086
0.009
0.173
0.208
0.223

0.086
0.006
0.168
0.201
0.201

8.64
0.85
3.46
4.15
4.45

464
25
267
131 (1), 335 (2)
144 (1), 371 (2)

Pd/C (Aldrich)
Pd/C (Alfa)
Pd/C (Aldrich)
Ru/C (Fluka)
Ru/C (JM)

(Aldrich) and 1 wt.% Pd/C (Alfa) catalysts were measured by means


of the H2-TPD technique. Temperatures measured at maximum
hydrogen capacities are shown in Table 3 and Fig. 2.
The total desorption of hydrogen as well as hydrogen desorbed
below 200 8C were calculated separately, since the lower
temperatures are of more interest due to the lower reaction
temperatures (between 80 and 100 8C) and additionally since the
catalysts were pre-reduced at 200 8C. No hydrogen was desorbed
below 200 8C from 1 wt.% Pd/C (Aldrich). 97% remained on the
5 wt.% Ru/C (Fluka) and on the 5 wt.% Pd/C (Aldrich) catalysts,
while 90% and 76% of hydrogen remained on the 5 wt.% Ru/C
(Johnson Matthey) and on the 1 wt.% Pd/C (Alfa), respectively, at
200 8C (Table 3).
In Ru/C catalysts two hydrogen desorption peaks clearly
appeared which correspond to different oxidation states of the

metal. In both 5 wt.% Ru/C (Fluka) and 5 wt.% Ru/C (Johnson


Matthey) the maximum amount of hydrogen adsorbed corresponded to the peak that appeared at the highest temperature.

Fig. 2. H2-TPD curves for the following catalysts: (1) 5 wt.% Ru/C (JM), (2) 5 wt.% Ru/
C (Fluka), (3) 5 wt.% Pd/C (Aldrich), (4) 1 wt.% Pd/C (Aldrich) and (5) 1 wt.% Pd/C
(Alfa).

Fig. 3. Hydrogenation of linoleic acid in the absence of catalyst. Symbols: (^)


linoleic acid, (*) oleic acid, (&) 18:1 isomer and (~) stearic acid. Reaction
conditions: T = 80 8C, P H2 20 bar, stirring rate 1500 rpm.

3.2. Catalytic results


3.2.1. Hydrogenation without catalyst
Reaction was performed at 80 8C and 20 bar, using the stirring
rate of 1500 rpm in the absence of catalyst, to investigate whether
the reactor walls have a catalytic effect in the hydrogenation of
linoleic acid (Fig. 3). This test was of interest, since hydrogenation
of multiple bonds of 2-butyne-1,4-diol to produce 1,4-butanediol
was promoted by stainless steel at 50 8C, and the solvent can
inuence the hydrogenation rate [18]. Composition of the reaction
mixture was studied during 3 h, and the results showed that no

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205

3.2.2. Study of mass transfer limitations


Preliminary experiments with different catalyst masses and
particles sizes were performed in the steel reactor equipped with
an efcient stirrer over a 1 wt.% Pd/C (Aldrich) catalyst to study the
mass transfer limitations and to optimize reaction conditions. In
these experiments the temperature and pressure were 100 8C and
20 bar, respectively, and the initial linoleic acid concentration in ndecane was 0.01 M. The aim was to obtain 100% linoleic acid
conversion and 100% selectivity to stearic acid.
The ratio between the reactant to catalyst amount was studied
by keeping linoleic acid concentration constant (0.0.1 M) while the
catalyst mass was varied. Reactant-to-catalyst ratios 10:1, 7:1 and
5:1 were tested, which corresponded to 40, 60 and 80 mg,
respectively. The catalyst introduced into the reactor was
unsieved.
The linoleic acid molar fraction should coincide when using
different amounts of catalysts in a normalized plot, with time
multiplied by Pd mass as an abscissa (Fig. 4a) if gas to liquid mass
transfer limitations are absent. This was not, however, the case,
since the highest conversions of linoleic acid were obtained with
the lowest amount of catalyst. Thus the catalyst mass was
decreased to 20 mg in the catalyst screening experiments in order
to avoid the diffusion limitations.
The most important information from this study was that the
maximum yield to stearic acid was limited, between 63% and

90% depending on the catalyst mass and it was thus related to


the catalyst deactivation (Fig. 4b). The higher the amount of
catalyst was used the higher selectivity to stearic acid was
obtained, i.e. at 90% conversion of linoleic acid the selectivity to
stearic acid using 40, 60 and 80 mg catalysts was 55%, 74% and
85%, respectively. For the higher amounts of catalyst less
deactivation occurred due to the higher specic surface area
available.
The effect of catalyst particle size on the hydrogenation kinetics
was studied using the following catalyst fractions: below 63 mm,
below 90 mm and above 90 mm, as well as unsieved catalyst.
Reactant-to-catalyst ratio was 10:1 (400 mg of analytical grade
linoleic acid and 40 mg of catalyst). The initial hydrogenation rate
decreased with increasing catalyst particle diameters: 0.51, 0.41,
and 0.043 mol LA/gPd min for fractions below 63 mm, below and
above 90 mm, respectively. The reaction rate was almost similar
when particles below 63 mm and below 90 mm were used,
meaning that the experiments were performed close to the
chemical reaction regime (Fig. 5a). A catalyst particle diameter
below 63 mm was selected in order to avoid the internal mass
transfer limitations.
Catalyst deactivation was prominent after 1 h under the studied
reaction conditions, and the maximum yield to stearic acid was
80%. Mole fractions of linoleic acid and stearic acid are represented
in Fig. 5b. Coke deposition was suggested to be the most probable
catalyst deactivation mechanism. The use of analytical grade
linoleic acid guarantees that catalyst is not poisoned by substances
occurring in natural oils.

Fig. 4. Inuence of the catalyst amount in the (a) molar fraction of linoleic acid and
(b) the stearic acid formation over 1 wt.% Pd/C (Aldrich). Reaction conditions:
T = 100 8C, P H2 20 bar, stirring rate 1500 rpm. Symbols: reactant to catalyst ratio
10:1 (^), 7:1 (&) and 5:1 (~).

Fig. 5. Effect of catalyst particle size on the (a) hydrogenation kinetics of linoleic acid
and (b) formation of stearic acid at 100 8C, 20 bar, reactant to catalyst ratio 10:1 over
1 wt.% Pd/C (Aldrich), using (^) unsieved, (*) >90 mm, (~) <63 mm and (&)
<90 mm particles.

variation of the initial reactant concentration occurred indicating


complete absence of non-catalytic hydrogenation.

P. Maki-Arvela et al. / Applied Catalysis A: General 345 (2008) 201212

206

Table 4
Kinetics in linoleic acid hydrogenation using different loading in Pd/C (Aldrich)
catalysts. Conditions: 100 8C, 20 bar, the catalyst amount was 40 mg
Metal loading
(wt.%)

Initial rate
(mol LA/gPd- min)

Time needed
for 90% conversion
(min)

Selectivity to
stearic acid at
90% conversion (%)

1
3
5

0.23
0.27
0.022

30
9
4

55
80
91

loading. Pd/C catalysts are very sensitive to deactivation by coke


and high amounts of coke may deposit on the surface after
prolonged reaction times. Thus, the metal loading must be high
enough to diminish inuence of deactivation.
The impact of the metal loading in the formation of monounsaturated acids is shown in Fig. 7a and b as a function of stearic

3.2.3. Inuence of the metal loading


Three different Pd/C (Aldrich) catalysts with palladium loadings
of 1, 3 and 5 wt.% were compared. The initial hydrogenation rates for
these three catalysts are given in Table 4 decreasing in the following
order: 3 wt.% > 1 wt.% > 5 wt.%. The higher initial hydrogenation
rate obtained over 1 wt.% Pd/C compared to 5 wt.% Pd/C is correlated
with its higher hydrogen adsorption capacity calculated per gram Pd
(Table 3) being 2.5-fold of that for the latter catalyst.
The linoleic acid conversion after 5 min of reaction was 53%,
84% and 93%, respectively, increasing thus with increased
palladium content in the catalyst, as expected. Additionally it
should be pointed out here, that the complete conversion was
obtained only over 5 wt.% Pd/C, whereas over 1 and 3 wt.% Pd/C
catalysts the conversions were 97% and 93%, respectively (Fig. 6b).
The reaction times needed to convert 90% of linoleic acid followed
the order 1 wt.%  3 wt.% > 5 wt.% (Table 4). A profound catalyst
deactivation appeared when 1 wt.% Pd/C catalyst was used, and the
resistance towards deactivation increased with increasing metal

Fig. 6. Molar fraction of (a) linoleic acid, (b) stearic acid as a function of time with
(^) 1 wt.%, (&) 3 wt.% and (~) 5 wt.% Pd/C (Aldrich) catalysts. Reaction conditions:
T = 100 8C, P H2 20 bar, reactant to catalyst ratio 10:1, stirring rate 1500 rpm.

Fig. 7. Molar fraction of (a) oleic acid, (b) 18:1 isomers and (c) selectivity to stearic
acid as a function of linoleic acid conversion with (^) 1 wt.%, (&) 3 wt.% and (~)
5 wt.% Pd/C (Aldrich) catalysts. Reaction conditions: T = 100 8C, P H2 20 bar,
reactant to catalyst ratio 10:1, stirring rate 1500 rpm.

P. Maki-Arvela et al. / Applied Catalysis A: General 345 (2008) 201212

207

3.2.4. Catalyst screening


The performance of various palladium and ruthenium catalysts
including bimetallic ones, in the hydrogenation of linoleic acid was
studied. Active carbon was the most frequently used support; in
addition Sibunit, alumina and magnesium oxide were also tested.
The reaction conditions selected for the screening were 100 8C,
20 bar of hydrogen pressure, the linoleic acid initial concentration
0.01 M (400 mg of analytical grade linoleic acid in 140 ml n-decane
as solvent), the stirring rate 1500 rpm, the reactant-to-catalyst
ratio 20:1 and the catalyst particle diameter below 63 mm. The
catalyst mass was reduced to 20 mg.

Fig. 8. Molar fraction of (a) linoleic acid, (b) stearic acid as a function of time with
1 wt.% (*) Pd/C (Alfa), (~) 1 wt.% Pd/C (Aldrich) and (^) 1 wt.% Pd/C (Sibunit).
Reaction conditions: T = 100 8C, PH2 20 bar, reactant to catalyst ratio 20:1,
stirring rate 1500 rpm.

acid mole fraction. More monounsaturated acids were formed


when the metal loading was 1 wt.% than when using either 3 or
5 wt.% metal loadings. The maximum mole fraction of oleic acid
was 0.12 obtained over 1 wt.% Pd/C, while no oleic acid appeared
when 5 wt.% metal loading was used.
The selectivity to stearic acid as a function of linoleic acid
conversion using Pd/C catalysts with different metal loadings is
shown in Fig. 7c. At lower conversion levels the selectivity to
stearic acid was lower with 1 and 3 wt.% Pd/C than over 5 wt.% Pd/
C. The selectivity to stearic acid increased, however, with
increasing conversion of linoleic acid, as expected for consecutive
reactions.

3.2.4.1. Palladium-based catalysts. The hydrogenation of linoleic


acid over three different 1 wt.% palladium-based catalysts is
compared in Fig. 8a. The 1 wt.% Pd/C (Alfa) with high surface area of
the support, exhibited very low reaction rates, which can be
correlated with the low amount of hydrogen adsorbed (Table 3).
Active carbon and Sibunit supports were compared. The initial
hydrogenation rate over 1 wt.% Pd/C (Sibunit) catalyst was almost
two-fold higher the corresponding value for the 1 wt.% Pd/C
catalyst being 1.13 mol LA/gPd min and 0.62 mol LA/gPd min,
respectively.
The performance of Pd/C (Alfa) was not very good, since the
maximum linoleic acid conversion of only 30% and the maximum
yield to stearic acid of 10% after 3 h of reaction time over 1 wt.% Pd/
C (Alfa) were achieved (Fig. 8a and b). The initial activity of the
catalyst was also very low, 0.008 mmol LA/gPd min (Table 5).
The maximum yield to stearic acid was for both 1 wt.% Pd/C
(Sibunit) and for 1 wt.% Pd/C (Aldrich) 87%, although the selectivity
to stearic acid was higher with the Pd/C (Aldrich) catalyst
compared with the Pd/C (Sibunit) catalyst, 98% and 89%
(Table 5), respectively. Both catalysts deactivated due to the low
metal loading. The Pd/C (Aldrich) catalyst deactivated more
profoundly than the Pd/C (Sibunit) catalyst. The maximum linoleic
acid conversions were 98% with the Pd/C (Sibunit) catalyst and 88%
with the Pd/C (Aldrich) catalyst, respectively. The 1 wt.% Pd/C
(Aldrich) catalyst is considered to be the better catalyst of these
two, since it resulted in stearic acid with fewer impurities.
The low loaded Pd/C catalysts (1 wt.%) deactivated after
prolonged reaction times giving maximally close to 90% conversion
and thus catalysts with higher metal loadings were tested (Table 5,
Fig. 9a). The normalized abscissa was referred to the reaction time
multiplied by the palladium mass, in order to fairly compare the
catalysts with low metal loadings.
The initial hydrogenation rates were 0.47 and 0.42 mol LA/
gPd min when using 5 wt.% Pd/C (Sibunit) and 5 wt.% Pd/C
(Aldrich), respectively. The initial catalyst activities of 1 wt.% Pd/

Table 5
Kinetic data from catalyst comparison in linoleic acid hydrogenation at 100 8C and 20 bar hydrogen
Max linoleic acid
conversion (%)

Max stearic
acid yield (%)

Selectivity to
stearic acid at
80 conversion (%)

Selectivity to
stearic acid at
max. conversion (%)

0.31
2.1
0.14
1.7
0.11
0.27
2.4

88
30.5
98
89
99
100
88

87
10.5
87
88
99
100
85

79
70
55
98
86
59

98.5
34.5
89
98.5
100
100
97

0.45
0.44
1.5
1.0

90
87
84.5
88.5

90
87
55
88

72
95
59
70

100
100
65.5
99

Initial rate
(mol LA/gPdRu min)

Conversion of
linoleic acid at
normalized time
5 min mg Pd (%)

r0,mono/r0,

1 wt.% Pd/C (Aldrich)


1 wt.% Pd/ C (Alfa)
1 wt.% Pd/C (Sibunit)
5 wt.% Pd/Al2O3 (Aldrich)
5 wt.% Pd/C (Sibunit)
5 wt.% Pd/C (Aldrich)
2.5 wt.% Pd2 wt.% Au/C

0.62
0.008
1.13
0.34
0.42
0.47
0.13

61
2.3
60
70
78
99
35

5 wt.%
5 wt.%
5 wt.%
5 wt.%

0.075
0.013
0.002
0.04

62
49
5
13

Ru/C (Fluka)
Ru/C (Johnson Matthey)
Ru/MgO
Ru0.5 wt.% Cu/C

SA

208

P. Maki-Arvela et al. / Applied Catalysis A: General 345 (2008) 201212

Fig. 9. Molar fraction of linoleic acid, (b) stearic acid as a function of time and (c)
selectivity to stearic acid as a function of linoleic acid conversion in the
hydrogenation of linoleic acid over (*) 5 wt.% Pd/C (Sibunit), (^) 2.5 wt.% Pd
2 wt.% Au/C, (~) 1 wt.% Pd/C (Aldrich), (*) 5 wt.% Pd/C (Aldrich), (^) 5 wt.% Pd/
Al2O3 (Aldrich). Conditions: reaction conditions: T = 100 8C, P H2 20 bar, reactant
to catalyst ratio 20:1, stirring rate 1500 rpm.

oil increases [19]. Additionally the H2/triglyceride ratio was of


minor importance in the range of 4:150:1 (mol), when hydrogenating palm oil over a 1 wt.% Pd/C at temperatures of 65135 8C
[20].
The 5 wt.% Pd/Al2O3 catalyst exhibited a slightly lower initial
activity than 5 wt.% Pd/C (Sibunit) and 5 wt.% Pd/C (Aldrich) being
0.34 mol LA/gPd min, which is caused most probably by the lower
Pd dispersion on low surface area alumina compared to the carbon
support.
The addition of gold did not improve the performance of the
catalyst and 2.5 wt.% Pd2 wt.% Au/C catalyst showed a considerably low activity of 0.13 mol LA/gPd min, compared to the other
palladium-supported catalysts.
Complete conversion of linoleic acid to produce pure stearic
acid was possible in 10 min of reaction time over both 5 wt.% Pd/C
(Sibunit) and the 5 wt.% Pd/C (Aldrich) catalysts (Fig. 9a), while the
rest of catalysts deactivated. The reason for the deactivation of
5 wt.% Pd/Al2O3 (Aldrich) can be the low specic surface area of
alumina compared to carbons (Table 1), thus coke may block easily
the active sites on alumina supports. The catalyst exhibiting
mesoporous structure, like 5 wt.% Pd/C (Sibunit), were active after
prolonged reaction times to hydrogenate linoleic acid. This result is
in accordance with literature since catalyst supports with the pore
diameter between 7 and 8 nm were found to be more active than
supports with lower pore diameters in the hydrogenation of
sunower oil and canola oil over Pd supported on structured silica
[21]. The obtained maximum linoleic acid conversion and the
maximum stearic acid yield of 2.5 wt.% Pd2 wt.% Au/C were
comparable to those corresponding to the 1 wt.% Pd/C (Aldrich)
and the 5 wt.% Pd/Al2O3 (Aldrich) catalysts.
The kinetics of the formation and disappearance of the
intermediate products, monohydrogenated acids was also studied.
The ratio between the initial formation rate of monounsaturated
acids to initial formation rate of stearic acid was calculated for all
tested catalysts (Table 5). The ratio was the highest for 2.5 wt.% Pd
2 wt.% Au/C followed by 1 wt.% Pd/C (Alfa) and 5 wt.% Pd/Al2O3.
These are the same catalysts, which gave the highest molar
fractions of monounsaturated acids also after prolonged reaction
times corresponding to about 0.150.5 M fraction of stearic acid.
Additionally only close to 90% conversion of linoleic acid was
achieved over these catalysts (Fig. 9a). This result indicated that
there is a correlation between the amount of the formed
monounsaturated acids and catalyst deactivation. It is known
that unsaturated compounds, like squalene and oleic acid ester can
undergo isomerization and dehydrogenation under hydrogenation
conditions being thus precursors for coke [22]. Noteworthy is that
over 5 wt.% Pd/C (Sibunit) no oleic acid could be detected
indicating that its hydrogenation was very fast over this catalyst,
which gave 100% conversion of linoleic acid.

C (Aldrich) and the 1 wt.% Pd/C (Sibunit) were higher than the ones
obtained over 5 wt.% Pd/C (Table 5), but the low metal loadings
limited the complete hydrogenation of double bonds due to
catalyst deactivation. A correlation between the initial hydrogenation rate over Pd/C 1 wt.% (Aldrich) and 5 wt.% Pd/C (Aldrich)
as well as for 1 wt.% Pd/C (Alfa) (Table 5) and the amount of
hydrogen adsorbed per metal (Table 3) can be made despite of the
fact that only a small amount of metal is needed to activate the
small amount of hydrogen required for the reaction (5 g of
hydrogen per 1 kg of vegetable oil). For instance a 100-fold
increase in the palladium content in a Pd/Al2O3 catalyst only
doubled the hydrogenation rate [19]. Hence, the oil to metal ratio
affects only the catalyst lifetime, as increasing the amount of active
metal, the number of centers capable of reacting with poisons from

3.2.4.2. Ruthenium-based catalysts. Four different ruthenium-supported catalysts were studied for the hydrogenation of linoleic
acid: 5 wt.% Ru/C (Fluka), 5 wt.% Ru/C (Johnson Matthey), 5 wt.%
Ru0.5 wt.% Cu/C and 5 wt.% Ru/MgO (Table 5).
The initial hydrogenation rate was higher using the 5 wt.% Ru/C
(Fluka) compared to the 5 wt.% Ru/C (Johnson Matthey) (0.075 and
0.013 mol LA/gRu min, respectively), whereas signicantly lower
initial hydrogenation rates were achieved over 5 wt.% Ru0.5 wt.%
Cu/C and 5 wt.% Ru/MgO (Table 5). The amount of hydrogen
desorbed was about the same from the two most active Rucatalysts (Table 3), although 5.7-fold higher initial rate was
achieved over 5 wt.% Ru/C (Fluka) compared to 5 wt.% Ru/C (JM).
The low activity of Ru/MgO can be explained by the low surface
area of the support, MgO thus most probably giving low metal
dispersion.

P. Maki-Arvela et al. / Applied Catalysis A: General 345 (2008) 201212

209

and 5 wt.% Pd/C (Aldrich). This result differs from those obtained
with 5 wt.% Ru/C catalysts, which showed deactivation. This result
indicated that alumina supported Pd catalyst does not give long
term stability and that Ru metal does not retain its activity in the
hydrogenation of linoleic acid, since 5 wt.% Pd/C catalysts gave
complete conversion of linoleic acid. It is known from literature,
that alumina is able to dissociatively adsorb linoleic acid and form
water [23], thus indicating that the catalyst deactivation over Pd/
Al2O3 could be expected. The differences in the nature of active
carbon could not, however, be totally excluded, since the detailed
analysis of their acidities, etc., was beyond the scope of this study.
The selectivity to stearic acid increased with increasing linoleic
acid conversion over supported Ru-catalysts (Fig. 10c). Three Rusupported catalysts, 5 wt.% Ru/C (Fluka), 5 wt.% Ru/C (JM) and
5 wt.% Ru0.5 wt.% Cu/C followed the same pattern in the
selectivity plot, whereas considerable lower selectivity was
achieved over Ru/MgO, which in turn produced larger molar
fractions of monounsaturated acids (gures not presented here).

Fig. 10. Molar fraction of linoleic acid, (b) stearic acid as a function of time and (c)
stearic acid selectivity as a function of linoleic acid conversion in the hydrogenation
of linoleic acid over (&) 5 wt.% Ru/C (Fluka), (~) 5 wt.% Ru/C (JM), (^) 5 wt.% Ru
0.5 wt.Cu/C and (*) 5 wt.% Ru/MgO. Conditions: T = 100 8C, P = 20 bar, reactant to
catalyst ratio 20:1, stirring rate 1500 rpm, dp < 63 mm.

Final conversion of linoleic acid over 5 wt.% Ru/C (Fluka), 5 wt.%


Ru/C (Johnson Matthey) and 5 wt.% Ru0.5 wt.% Cu/C was about
the same being close to 90% (Table 5) giving the 90% maximum
stearic acid yield and corresponding to 100% selectivity to stearic
acid (Table 5, Fig. 10a). On the other hand the reaction rate was
very low over Ru/MgO up to the time multiplied by metal mass
value of 50 min  mg Ru, thereafter it proceeded faster (Fig. 10a).
When comparing the hydrogenation rates over supported 5 wt.%
Ru catalysts (Fig. 10a) with the performance of the supported
5 wt.% Pd catalysts (Fig. 9a) a clear difference can be seen: catalyst
deactivation after prolonged reaction times was quite prominent
over 5 wt.% Pd/Al2O3 (Fig. 9a), but not over 5 wt.% Pd/C (Sibunit)

3.2.4.3. Comparison of Pd- and Ru-supported catalysts. In the


selection of the best catalyst for the catalyst deactivation tests
both conversion and selectivity to stearic acid were considered.
The selectivity to stearic acid increased with the linoleic acid
conversion and 100% conversion of linoleic acid together with
100% selectivity to stearic acid was possible to achieve with both
5 wt.% Pd/C (Aldrich) and 5 wt.% Pd/C (Sibunit) catalysts (Table 5).
Furthermore lower amounts of monounsaturated acids (oleic acid
and its isomers, mainly elaidic acid and trans-vaccenic acid) were
formed with the best 5 wt.% Pd catalysts compared to the best
5 wt.% Ru catalysts. A decrease in the palladium loading from 5 to
1 wt.% resulted in more monounsaturated compounds formed
(Table 5).
In general, palladium-based catalysts were more active than
ruthenium ones for the hydrogenation of linoleic acid, and
especially the 1 wt.% Pd/C (Sibunit) displays high initial rate
(Table 5). Nevertheless, using low metal loadings cannot be
recommended under these reaction conditions due to catalyst
deactivation. Increasing the linoleic acid mass or the reaction
temperature could accelerate the reaction rate and diminish the
risk of deactivation at prolonged reaction times.
Compared to palladium, ruthenium catalysts exhibited stronger
deactivation, although different carbons were used as supports.
The high activities of the 5 wt.% Pd/C (Aldrich) and the 5 wt.% Pd/C
(Sibunit) catalysts, their resistance towards deactivation, and the
complete hydrogenation of linoleic acid to stearic acid achieved
with both of them lead to consider these catalysts as the best ones
for the hydrogenation of linoleic acid.
3.2.5. Catalyst deactivation studies
The deactivation features of the most promising catalysts
5 wt.% Pd/C (Aldrich) and 5 wt.% Ru/C (Johnson Matthey) catalysts
were studied. The experiments were performed with reactant to
catalyst ratio 20:1 similarly to the catalyst screening experiments.
The hydrogen pressure was also the same, 20 bar, whereas the
temperature was only 80 8C, since extensive catalyst deactivation
over Ru-supported catalysts was observed in the screening
experiments.
The initial hydrogenation rate decreased over 5 wt.% Pd/C
catalyst in the second use. The initial hydrogenation rates were,
however, the same in the second and in the third use (Table 6).
Over 5 wt.% Ru/C the same initial rates were achieved in the rst
and in the second experiment, whereas slightly decreased rate was
observed in the third experiment. When comparing these rates
obtained at 80 8C (Table 6) with the rates achieved in the catalyst
screening series performed at 100 8C (Table 5), it can be seen that

P. Maki-Arvela et al. / Applied Catalysis A: General 345 (2008) 201212

210

Table 6
Catalyst deactivation kinetics in the hydrogenation of technical grade linoleic acid at 80 8C and 20 bar
Catalyst

Initial rate
(mol LA/gPdRu min)

Init. relative
rate rmonoa

Init. relative
rate rstearica

Time needed for


90% conversion (min)

Selectivity to stearic acid


at 90% conversion (%)

5 wt.%
5 wt.%
5 wt.%
5 wt.%
5 wt.%
5 wt.%

0.21
0.10
0.11
0.14
0.14
0.11

1
0.4
0.03
0.15
0.14
0.17

0.65
0.65
0.59
0.07
0.08
0.18

<2
6
8
4
6
8

86
70
62
86
70
74

Pd/C (Aldrich) I
Pd/C (Aldrich) II
Pd/C (Aldrich) III
Ru/C (Fluka) I
Ru/C (Fluka) II
Ru/C (Fluka) III

The reactant-to-catalyst amount was 20:1.


a
The maximum rate for mono and stearic acid formations rates was given value 1 and all other rates were related to that value.

Fig. 11. Catalyst deactivation test with the hydrogenation of technical grade linoleic
acid over 5 wt.% Pd/C (Aldrich). Molar fraction of (a) linoleic acid, (b) stearic acid as a
function of time and (c) stearic acid selectivity as a function of linoleic acid
conversion. Reaction conditions: T = 80 8C, P = 20 bar, dp < 63 mm reactant to
catalyst ratio 20:1, stirring rate 1500 rpm. Symbols: experiment I (&), experiment II
(~) and experiment III (^).

the initial hydrogenation rate for 5 wt.% Pd/C (Aldrich) was 2.2-fold
larger in the latter series. The initial rates with 5 wt.% Ru/C were
not, however, correlating with temperature, since lower initial rate
was achieved at a higher reaction temperature, 100 8C compared to
80 8C. From these values it can be concluded that the catalyst
deactivation over 5 wt.% Ru/C (Fluka) was very prominent at 100 8C
and the true temperature effect on the initial rates was not
observed due to deactivation.
Linoleic acid and stearic acid molar fractions were exactly the
same for the palladium-based and the ruthenium-based catalysts
corresponding to complete conversion and 100% yield of stearic
acid, respectively, in the second and third runs (Figs. 11a and b and
12a and b). A slight decrease of activity appeared for both catalysts
in the second run, compared to the rst run.
Coke deposition, which was conrmed by the decrease of the
specic surface area of a spent catalyst and blocking of the
micropores in Ru/C catalyst (Tables 1 and 2) explains the profound
catalyst deactivation in the catalyst screening and in the
preliminary tests. Either the small amounts of catalyst used or
the low metal loadings imply relatively long reaction times, thus,
more coking and deactivation may appear. Poisoning of the
catalyst is not probable, when the analytical grade linoleic acid was
used as the raw material. Reaction temperatures were not high
enough to allow thermal catalyst deactivation due to the support
sintering, and the small amounts of catalyst used make highly
improbable that mechanical stirring caused catalyst attrition.
Catalyst deactivation in the hydrogenation of methyl esters of
sunower oil has been studied in [24], where palladium and
platinum catalysts deactivated due to coke formation. In this case
the supports were a-Al2O3 and g-Al2O3. In the latter case less coke
was formed in the same conditions, and the catalyst exhibited a
lower surface area than a-Al2O3 and it was less acidic than the
former catalyst. Carbon used as one of the catalyst supports in the
current work has a slightly acidic character, since it contains
carboxylic groups. The acidity of 5 wt.% Pd/C (Aldrich) was found to
be 36.4 mmol/gcat and thus catalyst deactivation is probable.
Furthermore, strong catalyst deactivation was as well shown in the
hydrogenation of palm oil over 1 wt.% Pd/C using a continuous
xed-bed reactor between 65 and 135 8C with hydrogen to
triglyceride ratio of 450 mol/mol [20].
The initial formation rates of monounsaturated acids (oleic and
isomer acid) and stearic acid were compared for Pd/C and Ru/C
(Table 6). The formation rate for monounsaturated acids decreased
progressively and the stearic acid formation rates were quite
constant over Pd/C in consecutive experiments. For Ru/C the
situation was different: the formation rates for monounsaturated
acids were about the same, whereas stearic acid formation rate
increased in the third experiment. These results indicated that
there is a progressive deactivation of Pd/C, whereas the initial
deactivation of Ru/C was more prominent than for Pd/C.
The kinetic patterns for intermediate products, oleic acid and
monounsaturated fatty acids in the catalyst deactivation series for
Pd/C catalyst as well as for Ru/C catalyst (gures not presented

P. Maki-Arvela et al. / Applied Catalysis A: General 345 (2008) 201212

211

monounsaturated acids over Pd/C and Ru/C, since for Pd/C catalyst
the total amount of monounsaturated acid at 60% molar fraction of
stearic acid decreased in the consecutive experiments IIII as
follows: 0.7 > 0.35 > 0.3, whereas over Ru/C the corresponding
levels of monounsaturated acids were 0.25, 0.32 and 0.3 indicating
that there is a large decrease in the molar fractions of the
intermediate products in consecutive experiments in the former
case, while for Ru/C catalysts their amounts were quite constant.
Additionally the higher amounts of monounsaturated acids formed
on Pd/C compared to Ru/C are in line with the results of [6]
according to which Ru was less selective to oleic acid than Pd. In
that work [6] only linoleic, oleic and stearic acid were taken into
account in the analysis. It should, however, be pointed out here,
that although Pd has high selectivity to monounsaturated acids, it
is capable to hydrogenate them in the consecutive reaction step to
stearic acid.
The selectivity to stearic acid as a function of linoleic acid
conversion is shown in Figs. 11c and 12c. Over Pd/C there was a
progressive catalyst deactivation, since at a given linoleic acid
conversion lower selectivity to stearic acid was achieved in the
consecutive experiments (Fig. 11c). Over Ru/C the most selective
catalyst at higher linoleic acid conversions was the fresh one, while
the difference in stearic acid selectivity in the second and third
experiment was not very large (Fig. 12c). Finally 100% selectivity to
stearic acid was achieved over Ru/C at 100% conversion.
4. Conclusions

Fig. 12. Catalyst deactivation test with the hydrogenation of technical grade linoleic
acid over 5 wt.% Ru/C (Fluka). Molar fraction of (a) linoleic acid, (b) stearic acid as a
function of time and (c) selectivity to stearic acid as a function of conversion.
Reaction conditions: T = 80 8C, P = 20 bar, dp < 63 mm reactant to catalyst ratio
20:1, stirring rate 1500 rpm. Symbols: experiment I (&), experiment II (~) and
experiment III (^).

here) were studied. Over Pd/C the largest amount of oleic acid was
formed in the rst experiment thereafter the amount of oleic acid
decreased to a constant level in the second and third experiments.
For formation of monounsaturated C18:1 acids there was a
decreasing trend in consecutive experiments. The reaction rate for
oleic acid was the same in the consecutive experiments over Ru/C,
whereas more C18:1 acids were formed in the second and in the
third experiment compared to rst one. From these results it can be
concluded that Ru/C catalyst initially deactivated very fast, since
there were no difference with the oleic acid molar fractions,
whereas a progressive catalyst deactivation was more prominent
over Pd/C. The same trend is visible from the total amount of

Catalytic hydrogenation of linoleic acid was studied over


several Pd- and Ru-supported catalysts as well as some bimetallic
catalysts. The main aim was to achieve complete conversion of
linoleic acid as well as to maximize the selectivity to stearic acid.
The best catalyst was 5 wt.% Pd/C, whereas 5 wt.% Ru/C catalysts
gave only 90% conversion and yield of stearic acid indicating that
catalyst deactivation was more prominent in the latter case. When
using a lower metal loading for Pd catalysts the catalyst
deactivation was more profound compared to 5 wt.% loading. At
the same time the conversion of linoleic acid was limited with low
loaded Pd catalyst to 90%. The origin for catalyst deactivation was
coking.
Catalyst reuse and deactivation were studied over 5 wt.% Pd/C
and Ru/C catalysts. The former one deactivated progressively,
whereas over the latter catalyst the initial catalyst deactivation
was more prominent. Despite of catalyst deactivation complete
conversion and 100% selectivity towards stearic acid were
obtained at 100 8C and 20 bar hydrogen over both catalysts. There
was a correlation between the formation of monounsaturated acid
and the catalyst deactivation, i.e. the more monounsaturated acids
were observed in the reaction mixture the more extensive was
catalyst deactivation. Coke formation is the origin for the declined
catalytic activity after prolonged reaction times. The use of
mesoporous carbon support material promoted catalytic activity
and the consecutive hydrogenation of monounsaturated was very
fast over these catalysts.
Acknowledgement
This work is part of activities at the Abo Akademi Process
Chemistry Centre of Excellence Programmes (20002011) nanced
by the Academy of Finland.
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