Journal of Food Engineering 84 (2008) 526–533

www.elsevier.com/locate/jfoodeng

Low temperature soybean oil hydrogenation by

an electrochemical process
Kanchan Mondal a,1, Shashi Lalvani b,*
a
Mechanical Engineering and Energy Processes, Southern Illinois University, Carbondale, IL 62901, United States
b
Paper and Chemical Engineering, Miami University, Oxford, OH 45056, United States

Received 1 February 2007; received in revised form 7 May 2007; accepted 5 June 2007
Available online 19 July 2007

Abstract

Hydrogenation of unsaturated fatty acids present in soybean oil is accomplished by chemical reduction under mild reaction conditions
using relatively very small concentrations (0.7 M) of sodium formate and formic acid. The formate ion is continuously regenerated at the
cathode by an electrochemical reaction, and hence it is described as a mediator-assisted electrochemical (MEH) process. The influence of
various process variables such as the addition of surfactant, catalyst, electrocatalyst (i.e. mediator or hydrogen donor), pH, nickel cat-
alyst on the extent of hydrogenation, trans fatty acid formation, and the fatty acid profile is described. As compared to the commercial
gaseous hydrogenation process, the application of MEH technique results in up to 80% reduction in trans fatty acid while accomplishing
the similar level of hydrogenation.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Hydrogenation; Formate; Electrochemical; trans Fatty acid

1. Introduction In the last decade, a report (Yusem & Pintauro, 1992)

Hydrogenation of unsaturated fatty acids present in veg-
etable oil is carried out to extend its shelf life and to pro-
vide the desired melting characteristics. Commercial
hydrogenation processes are accomplished in a batch mode
because of the high hydrogen gas pressure requirements
(10–60 psig). The temperature ranges from 150 to 225 °C,
which leads to the trans fatty acid formation. Current evi-
dence has implicated the intake of trans fatty acids to cor-
onary heart diseases, and the inhibition of arachidonic acid
biosynthesis, thus giving rise to issues related to growth
necessary for healthy children (Desci & Koletzko, 1995).
Beginning 2006, the US Food and Drug Administration
mandated that all food packages must mention the amount
of trans fatty acids.
*
Corresponding author. Tel.: +1 513 529 0763.
E-mail addresses: kmondal@siu.edu (K. Mondal), lalvansb@muo-
hio.edu (S. Lalvani).
1
Tel.: +1 618 453 7909.
detailing a low temperature electrochemical process for edi-
ble oil hydrogenation was published. Essentially, the tech-
nique involves water electrolysis, where the atomic
hydrogen produced at the cathode is employed for hydro-
genation. The authors have (Yusem, Pintauro, Cheng, &
An, 1996) investigated the use of a radial flow-through
reactors at temperatures ranging from 45 to 75 °C. In
another study, they (Yusem & Pintauro, 1997) reported
that while the amount of trans fatty acids in the hydroge-
nated oil was lowered, the separation of oil from the elec-
trolyte led to process economics that is unfavorable as
compared to the commercial hydrogen processes. In a
related study, investigators reported (An, Hong, Pintauro,
Warner, & Neff, 1998) electrochemically hydrogenated edi-
ble oils in a solid polymer electrolyte reactor. Their analysis
of the oil indicates that the electrochemically assisted
hydrogenation imparts aroma, which is much less in inten-
sity than that obtained by chemical hydrogenation meth-
ods. Electrochemical hydrogenation also results in low
trans fatty acid formation. In a recent paper, researchers

0260-8774/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2007.06.025
 K. Mondal, S. Lalvani / Journal of Food Engineering 84 (2008) 526–533 527

(Pintauro, Gil, Warner, List, & Neff, 2005) have carried out Table 1
soybean oil hydrogenation in a proton exchange membrane Fatty acid profiles of as received oil
(PEM) electrochemical reactor, with hydrogen gas as the Fatty acid Soybean
anode feed and source of protons for fatty acid reduction. 16:0 13.53
In their experiments, the trans isomer formation was found 18:0 4.0
to be significantly lower than 10%. 18:1 20.2
A paper (Mondal & Lalvani, 2003a) details the use of 18:2 53.5
18:3 8.0
formic acid and formate ion as a source of hydrogen for
Iodine value 130
the reduction of fatty acids via a low temperature electro- % trans 1.01
chemical process. The formate ion (mediator) is regener-
ated at the cathode and thus it acts as a shuttle for
transferring hydrogen. In addition to soybean, in a sepa- Fluka (St. Louis, MO). Sodium formate (99.8%) and for-
rate study (Mondal & Lalvani, 2003b), researchers have mic acids (97%) were supplied by Alfa Essar (Ward Hill,
also examined canola oil hydrogenation using a media- MA). Nickel (7.1 wt.%) slurry catalyst on silicon support
tor-assisted electrochemical approach. This paper examines with a surface area of 770 m2/g was obtained from Degussa
the role of various process variables, such as surfactant and Corp (Calvert City, KY).
hydrogen donor concentrations, and the catalyst addition
on hydrogenation characteristics. 2.2. Fatty acid determination

2. Experimental procedures Methyl esters of oil samples were prepared according to

Soybean oil hydrogenation was carried out in the cath-
ode compartment of a batch electrochemical reactor (Mon-
dal & Lalvani, 2003a). The cathode chamber was separated
from the anode by a fine glass frit that prevented any oil
from entering the anode compartment. Both the cathode
and anode consisted of platinum mesh with the surface
areas of 1 and 2.25 cm2, respectively. A magnetic stirrer
provided agitation to disperse the oil in the electrolyte.
Experiments involved the addition of a predetermined
amount of formate ion, the hydrogen transfer reagent
(i.e. mediator or electrocatalyst) to a mixture of oil and
water. This was followed by the addition of surfactant
(i.e., emulsifier), didoceyl diethyl ammonium bromide
(DDAB). The total mixture volume was 150 cm3. The
amount of electrocatalyst added is provided in the appro-
priate sections of the paper, tables and figures. The mixture
was then stirred and heated to the desired temperature in a
water bath. This was followed by the addition of a nickel
hydrogenation catalyst. A 750 potentiostat/galvanostat
(Gamry Instruments) was employed as a source of current
(V). Experiments were conducted for 12 h unless otherwise
specified. At the end of the experiment, the oil–water-cata-
lyst mixture was filtered through a filter paper of medium
pore size of 2.5 lm to separate out most of the aqueous
phase as the filtrate. The oil-catalyst mixture was subjected
the AOCS method Ce 2-66 (AOCS, 1997), and the esters
were analyzed by gas chromatography in accordance to
the AOCS method Ce 1-62 (Helrich, 1990). The iodine
value was evaluated using the GC composition using the
AOCS Cd 1c-85 method in accordance with the process
described by Metcalfe, Schmidt, and Pelka (1966).
3. Results and discussion
3.1. Addition of surfactant
The influence of the DDAB addition on iodine value
and fatty acid profile for reactions carried out for a period
of 12 h is shown in Fig. 1. DDAB was used since it forms a
good microemulsion, which is necessary for contact
between the three phases. Another advantage of using this
surfactant is that it is easy to separate the oil from the
aqueous phase after the reaction is over. The data show
that in the absence of surfactant addition, negligible hydro-
genation occurred. An increase in the emulsifier amount
130 7
6
125
Percent Composition

5
to an n-heptane wash. The heptane layer was centrifuged 120
Iodine Value

for about 30 min to separate the catalyst and any remain- 4

115
ing water from oil solution dissolved in n-heptane. After 3
evaporation of the n-heptane, the oil fatty acid profile 110
IV
Stearic Acid
was determined. % Trans 2

105 1
2.1. Materials
100 0
0 0.2 0.4 0.6 0.8 1 1.2
The unhydrogenated soybean oil was obtained from
Emulsifier Amount (g)
Archer Daniel Midland Inc (ADM). The fatty acid profile
of the oil is shown in Table 1. DDAB was obtained from Fig. 1. Iodine value vs. emulsifier content.
528 K. Mondal, S. Lalvani / Journal of Food Engineering 84 (2008) 526–533
from 0 to 0.24 g per 150 ml of the reaction volume resulted
in a corresponding increase in hydrogenation. The iodine
value of the hydrogenated soybean oil decreased from
127 to 106, representing a 17% increase in the extent of
hydrogenation. A further increase in the surfactant amount
did result in only very modest additional reduction in the
iodine value. Approximately 8% decrease in the iodine
value was noted when the DDAB amount in the reaction
mixture was increased from 0.24 to 1 g. As the amount of
surfactant was increased, concomitant difficulty in the
phase separation was encountered.
The trend for the increase in the stearic acid and trans
isomer composition with the surfactant content is similar
to the one found for the corresponding increase in the
hydrogenation extent. However, the trans fatty acid con-
tent was found to be fairly modest (<5%) even for the
experiment in which the iodine value was found to be as
low as 103. In most of the experiments, the stearic acid con-
tent was found to be less than 6%.
In comparison to the oleic acid hydrogenation to stearic
acid, the trans isomer formation was found to be more sen-
sitive to an increase in the surfactant amount added to the
reactor. Increases of up to 12.5% and 8.75% per g of surfac-
tant in the trans isomer and the stearic acid contents were
observed, respectively. Based upon the results obtained in
this set of experiments, it was concluded that 0.24 g of sur-
factant in a 150 ml of water–oil mixture is a reasonable
amount to be employed in hydrogenation experiments.
The main purpose of employing the emulsifier in our
experiment was to ensure the formation of a uniform phase
while the mixture was adequately agitated. Surfactants,
particularly, emulsifiers markedly lower the interfacial sur-
face tension between the two phases. This has an influence
on the droplets of both liquids; they become smaller, and,
therefore, the overall liquid/liquid interface area is greatly
increased. This causes the formation of a nearly single
phase (visual observation).
The hydrogenation takes place when the acceptor
(unsaturated oil) and the donors (water and formate) are
adsorbed on to the catalyst. The absence of the acceptor
would result in loss of donor in the form of carbon dioxide
while the lack of the donor would result in no hydrogena-
tion. Increasing the aqueous layer/oil layer interface by the
use of an emulsifier increases the probability that both the
acceptor as well as the donor are adsorbed simultaneously
and thus resulting in enhanced extent and rapid rate of
hydrogenation.
In a previous research paper (Mondal & Lalvani,
2003a), authors have shown that the hydrogenation rate
increases proportionally to the amount of catalyst. Conse-
quently, the addition of emulsifier directly influences the
reaction rate by increasing the interfacial area along with
the concentration of the catalyst exposed to the oil.
It has been claimed in the past (Balakos & Hernandez,
1997) that trans isomers are formed when the triglyceride
desorbs from the catalyst surface without being hydroge-
nated. This can explain the larger increase in the rate of
trans isomer formation as compared to the rates of stearic
acid formation with emulsifier concentration. On increas-
ing the exposed surface of the catalyst to the oil, a larger
proportion of unsaturated fatty acids is desorbed without
being hydrogenated in spite of the increase in the hydroge-
nation rate. Oleic acid hydrogenation, on the other hand,
competes with linolenic and linoleic acid hydrogenation.
This results in a lower amount of stearic acid formation
in comparison to the trans fatty acid formation.
3.2. Addition of hydrogen donor (electrocatalyst)
The hydrogen donor agent of the formate ion was
employed. The source of the formate ion was a combina-
tion of formic acid and sodium formate. The relative
amount of the two sources of hydrogen was determined
by the solution pH consideration. It has been shown (Mon-
dal & Lalvani, 2000) that the catalytic transfer hydrogena-
tion can be described by a pseudo-second order kinetic
expression, the rate of reaction being dependent on the
donor concentration. Thus, a high concentration of the
electrocatalyst is expected to result in a corresponding fas-
ter rate of hydrogenation.
Fig. 2 contains data on the extent of hydrogenation. In
the absence of hydrogen donor, almost no hydrogenation
was realized. When the electrocatalyst concentration was
increased to 0.1 M, the corresponding iodine value of the
hydrogenated soybean oil was found to decrease to 113
from an initial value of 130 (i.e. 13% reduction). A further
increase in the donor concentration to 0.52 M resulted in a
total of 23% decrease in the iodine value. A corresponding
increase in the hydrogenation extent was noted with a fur-
ther increase in the hydrogen donor content from 0.52 to
0.70 M. However, the use of electrocatalyst concentrations
greater than 0.7 M did not result in additional hydrogena-
tion. The molar concentration of 0.7 corresponds to the
case when the number of unsaturated bonds are equal to
the number of electrocatalyst (donor) molecules. It has
been shown earlier that this condition provided the maxi-
mum rate of conversion in the catalytic transfer hydrogena-
135 14
130
IV 12
125 Stearic Acid
% Trans
Percent Composition
10
120
Iodine Value
8
115
110 6
105
4
100
2
95
90 0
0 0.5 1 1.5 2
Electrocatalyst Concentration (M)
Fig. 2. Iodine value vs. electrocatalyst amount.
 K. Mondal, S. Lalvani / Journal of Food Engineering 84 (2008) 526–533
tion (Weiner, Blum, & Sasson, 1991). Thus, a further
increase in the donor concentration beyond 0.7 M did
not increase the hydrogenation extent.
The trans fatty acid decreased from 11.1% to 4.03% as
the electrocatalyst concentration was increased from 0.1
to 0.52 M. It is interesting to observe that the trans isomer
content decreased with increasing degree of hydrogenation.
A decrease of 64% in the trans isomer content of the hydro-
genation product is observed corresponding to a 26% addi-
tional decrease in the iodine value when the electrocatalyst
concentration is increased from 0.1 to 0.52 M. It has been
shown earlier by Coenen (1976) that the trans fatty acid
formation is primarily a result of geometric isomerization
during the adsorption and desorption of unhydrogenated
fatty acids. Thus, if there is a relatively a large concentra-
tion of fatty acids with double bonds adsorbed onto the
surface in relation to the donor amount, a large number
of these molecules would then get desorbed without getting
hydrogenated. Based on the conclusions by Coenen (1976),
an enhancement in the number of unreacted double bonds
desorbed could result in a concomitant increase in the trans
isomers formation. Thus, a significant amount of the fatty
acids is free from the hydrogenation process at any time
and that the fatty acids are being constantly adsorbed
and desorbed from the catalyst surface as trans double
bonds.
It must be noted that the electrocatalyst amount used in
the current process is significantly lower than the amount
used in catalytic transfer hydrogenation, which also accom-
plished similar degree of hydrogenation (at a much faster
rate). As the amount of electrocatalyst is increased, more
of the fatty acids participate in the hydrogenation process,
thereby reducing the amount of geometric isomerization
(Balakos & Hernandez, 1997). The trans fatty acid vs. elect-
rocatalyst concentration data show that the trans fatty acid
produced is minimal when the electrocatalyst concentra-
tion of 0.52 M was employed. However, on increasing the
electrocatalyst content to more than 0.52 M, higher levels
of isomers in the final product were observed. Trans isom-
erization also occurs due to hydrogenation of polyunsatu-
rated fatty acids being partially hydrogenated. The
unhydrogenated double bonds in these polyunsaturated
fatty acids are desorbed as trans forms. Thus, a decrease
in the extent of hydrogenation as the electrocatalyst con-
centration is increased results in an increase in the trans
fatty acids formation.
The concentration of 0.7 M corresponds to the number
of moles of formate ion, which is also equal to the moles of
the unsaturated fatty acid double bonds in soybean oil. It
has been observed in the transfer hydrogenation of 4-nitro-
phenol (Weiner et al., 1991), that the conversion and initial
rate of reaction attained a maximum value when the ratio
of the formate ion to the acceptor concentrations was stoi-
chiometric (3:1). It is observed (Arkad, Weiner, Garti, &
Sasson, 1987) that molar ratio of 2 (between formate and
double bond) is required for chemical transfer hydrogena-
tion (CTH) of soybean oil esters for maximum conversion.
529
They attributed the higher requirement to decomposition
of the formate ion at the catalyst surface. In the present
case, a molar ratio of 1 provided the maximum degree of
hydrogenation.
The models employed in this study have been published
in Mondal and Lalvani (2000, 2003a); and the following
narrative in part is a reflection of these studies. The
decrease in the iodine value of the hydrogenated product
with the electrocatalyst concentration can be explained by
assuming that hydrogenation kinetic expression can be
described by a first order dependence on each, the formate
as well as the fatty acid concentration. The increase in
iodine value when the electrocatalyst concentration in the
reaction mixture was greater than 0.7 M indicates a more
complex mechanism than that suggested by considering
an elementary second order reaction mechanism. One
probable explanation is that on increasing the formate
ion concentration, more of the active sites are blocked by
the formate ions and become unavailable to the fatty acids,
whose adsorption is hypothesized to be kinetically sluggish
due to the high molecular weight. The fatty acids are thus
adsorbed onto the inactive support (silica). On desorption,
the isomerization of fatty acids take place and is reflected in
the increase in the trans isomer formation.
The stearic acid concentration, i.e. saturated fat, in the
hydrogenated oil increased with decreasing iodine value
when the electrocatalyst concentration was increased from
0.1 to 0.7 M (Fig. 2). The stearic acid fraction in the hydro-
genated oil remained relatively constant when the initial
electrocatalyst concentration of 0.7 M was used.
Fig. 3 is a plot of the fatty acid profile as a function of
the initial electrocatalyst concentration. The data on lino-
lenic acid content showed that it decreased linearly rather
steeply with the electrocatalyst concentration in the range
(0.1–1.75 M). The oleic acid formation increased when
the hydrogen donor concentration was increased up to
0.25 M. At electrocatalyst concentrations greater than
0.5 M, the oleic acid concentration was found to increase
only modestly. Due to hydrogenation, the linoleic fatty
acid content decreased with the electrocatalyst concentra-
60 9
8
50
7
Fatty Acid Content (%)
Fatty Acid Content (%)
40 6
5
30
4
Oleic
20 Linoleic 3
Linolenic
2
10
1
0 0
0 0.5 1 1.5 2
Electrocatalyst Concentration (M)
Fig. 3. Fatty acid profile vs. electrocatalyst amount.
530 K. Mondal, S. Lalvani / Journal of Food Engineering 84 (2008) 526–533
tion up to a value 0.7 M. However, when the initial hydro-
gen donor concentration was kept greater than 0.7 M, the
linoleic acid content increased somewhat due to further
linolenic acid reduction. The data suggest that oleic acid
reduction to stearic fatty acid is sluggish in comparison
to the hydrogenation of linolenic and linoleic fatty acids.
3.3. Kinetic studies
The hydrogenation of soybean oil was carried out with
formic acid at 45 °C at 0.5 V vs. saturated calomel elec-
trode (SCE). At the end of 24 h, the product had an IV
of 106. The data on the fatty acid profile as a function of
time are provided in Table 2. The individual selectivity is
defined as the absolute value of the percent change in the
fatty acid content per unit decrease in the iodine value.
The selectivities were calculated based on the following
equation where S is the selectivity and j is the percent com-
position of fatty acids (i.e. 18:0, 18:3, trans).
The increase in trans isomer formation with time sup-
ports our data presented above. Even though the data
show an apparent relationship between the decrease in
linolenic acid and increase in trans isomer content, a stron-
ger correlation exists between the increase in oleic acid (by
hydrogenation of linoleic acid) and the formation of trans
isomers. The increase in the trans isomer content and selec-
tivity beyond 18 h of reaction also follows a similar trend.
This concurs with our earlier observation that trans isomer
content in the hydrogenated product is a function of the
amount of linoleic acid hydrogenated.
The ratio of linolenic acid hydrogenation rate constant
to that of oleic acid hydrogenation rate constant was calcu-
lated to be 4.76 (as compared to around 2.5 in gaseous
hydrogenation). The calculation for the ratio was based
on the kinetic model reported in the literature (Mondal &
Lalvani, 2000) with appropriate adjustment for the electro-
chemical regeneration of the electrocatalyst while that of
the gaseous hydrogenation is generally based on the model
    described by Bailey (Bailey, 1949). Thus, it can be con-
 jfinal jinitial 
 jinitial  cluded that the oleic acid reduction selectivity is approxi-
S j ¼ ABS 
IVfinal IVinitial  mately two times as great in the case of the mediator-
 IV
initial
In the above equation, ABS stands for the absolute value of
the function. It is seen from the table that the 18:0 selectivity
is high for a short reaction time (1.5 h), reaches a minimum
at around 12 h and then increases with time. The trans selec-
tivity data (Table 2) show an initial rapid rise in the selectiv-
ity after which the rate of increase in selectivity is somewhat
slow. The data show that the trans selectivity remains fairly
constant for over 15 h (from 3 h to 18 h of reaction time) of
the reaction. At reaction times over 18 h, the trans selectiv-
ity is observed to rise sharply. The 18:3 selectivity is ob-
served to increase monotonously from 3.44 to 4.24 with
time, albeit slowly. The reason for the initial high value of
18:0 selectivity is that the adsorption of fatty acids onto
the surface of the catalyst is non-selective. However, with
time the surface monopolization of the fatty acids occurs
in the decreasing order of: linolenic > linoleic acid > oleic
acid (Coenen, 1976). At the end of 12 h, the linolenic and
linoleic acid contents are significantly reduced such that
oleic acid hydrogenation predominates resulting in an in-
crease in the stearic acid selectivity.
assisted electrochemical hydrogenation (MEH) process
described here as compared to the gaseous hydrogenation.
The above data illustrate the specific advantage of the
mediator-assisted electrochemical process over the conven-
tional gaseous hydrogenation process with respect to the
formation of stearic acid.
3.4. Influence of catalyst
The fatty acid profiles in experiments carried out under
identical conditions involving nickel and palladium cata-
lysts are shown in Table 3. The extent of hydrogenation
as evidenced by a decrease in the iodine value is 32.39%
greater when palladium was used instead of nickel. How-
ever, the relative percent increase in stearic acid content
per unit decrease in the iodine value is observed to be
1.83 times higher when the palladium catalyst was used
(13.54% stearic acid in product) than due to the use of
nickel catalyst (7.95% stearic acid in product). In addition,
the trans selectivity is also increased by the use of palla-
dium catalyst resulting in larger amounts of the deleterious

Table 2
Kinetic studies with 0.26 M formic acid
Time (h) 16:0 (%) 18:0 (%) 18:1 (%) 18:2 (%) 18:3 (%) 20:0 (%) IV % trans Selectivity
18:0 18:3 % trans
0 12.48 4.18 21.33 52.77 7.76 0.28 130.0 1.0 – –
1.5 11.84 5.31 23.33 50.19 6.55 0.34 124.1 1.3 5.96 3.44 6.61
3 12.6 5.36 27.36 47.35 5.8 0.29 120.7 2.0 3.95 3.53 13.98
6 12.45 5.48 29.7 45.45 4.91 0.27 117.1 2.5 3.13 3.70 15.12
12 11.75 5.49 31.33 44 3.79 0.23 113.1 2.9 2.41 3.94 14.62
18 12.07 6.02 33.32 42.27 3.27 0.28 110.4 3.5 2.92 3.84 16.58
24 11.94 6.42 37.26 40.27 1.81 0.28 106.5 5.0 2.96 4.24 22.13
Nickel catalyst (1 g/l), oil–water ratio (0.3 g/g), DDAB (0.24 g), 0.5 V vs. SCE, 45 °C.
 K. Mondal, S. Lalvani / Journal of Food Engineering 84 (2008) 526–533 531

Table 3 Stimac, & Kobe, 1992) shows that the use of sodium formate
Fatty acid profiles of the product of electrochemical hydrogenation of soy in water provides the maximum reduction in the iodine
oil using 1 g/l nickel catalyst and 0.5 g/l of palladium catalyst.
value of vegetable oil. However, the data (Fig. 4) show that
Nickel Palladium Selectivity ratio a high degree of hydrogenation is achieved at low pH. While
(Pd/Ni)
it is true that lowering the pH could destabilize the emulsion,
16:0 (%) 12.81 12.95 – no such effect was observed at pH values as low as 3 in our
18:0 (%) 7.95 13.54 1.83
18:1 (%) 39.93 36.35 0.62
experiments. In general, the extent of hydrogenation as evi-
18:2 (%) 35.25 33.28 0.83 denced by a decrease in the iodine value, increased with low-
18:3 (%) 2.61 1.62 0.91 ering the reaction mixture pH. In addition, an increase in the
IV 102.22 93.13 – reaction temperature resulted in a corresponding decrease in
% trans 5.53 14.73 2.29 the iodine value. The increase in the hydrogenation extent is
Nickel catalyst (1 g/l), oil–water ratio (0.4 g/g), DDAB (0.24 g), 0.5 V vs. independent of temperature when the initial reaction mix-
SCE, 45 °C. ture was kept at a pH of 9.5. At a pH of 1 and 45 °C, a reduc-
tion in the iodine value of 20 representing a 16% increase in
the hydrogenation extent was achieved. Due to significant
isomer in the product. It can be seen from the data pro- proton availability at low pH, the rate of hydrogen donor,
vided in Table 3 that the incremental increase in trans iso- i.e., formate regeneration from the bicarbonate ion is
mer content in the product when palladium was used increased leading to lower iodine value. The bicarbonate
(0.36% trans/DIV) per unit decrease in the iodine value is anion is produced due to chemical hydrogenation of oil by
2.29 times the corresponding incremental increase observed the formate ion. However, at very high pH values, such as
when nickel was used as the catalyst (0.16% trans/DIV). 9.5, the rate of formate regeneration is severely limited by
Thus, the use of nickel appears to be a better choice than the relative unavailability of protons, and therefore an
the palladium catalyst for the partial hydrogenation of edi- increase in temperature has no influence on enhancing the
ble oils for reducing the linolenic acid content without sig- rate of hydrogenation.
nificantly increasing the stearic acid or total trans isomer Table 4 data illustrate the higher degree of hydrogena-
content. It should be noted here that the 14.73% trans iso- tion by the mediator-assisted electrochemical method
mer content in the hydrogenated product (when palladium (MEH) as compared to the CTH one when equal concen-
catalyst was used) is relatively low as compared to those trations of formic acid were used. The iodine value reduc-
obtained via alternative methods of hydrogenation as tion in the case of MEH is nearly 3.6 times greater than the
explained below. corresponding reduction obtained by the CTH method.
Table 5 contains the data on fatty acid profiles of soybean
3.5. A comparison with other techniques oil hydrogenated by CTH and MEH processes in the pres-
ence of sodium formate at 45 °C. Negligible lowering of
In order to evaluate the enhancement in the degree of iodine value was observed for catalytic transfer hydrogena-
hydrogenation by the mediator enhanced electrochemical tion when 0.5 M formate ion was used. On the other hand,
process, methods involving chemical transfer hydrogena- the hydrogenation process involving donor regeneration
tion (CTH) and mediator-assisted electrochemical hydroge- (i.e. MEH) provided a significant reduction in the iodine
nation (MEH) were studied. The CTH process was studied value. At the end of 12 h, the iodine value decreased from
under the open circuit conditions (i.e. no impressed current) an initial value of 130.4 to 100.52 (Table 4) and 111.72
and formic acid/formate acted as a source of hydrogen (Table 5) when equal concentrations of formic acid and
donor. The data are shown in Fig. 4. A study (Smidnovik, sodium formate were used (MEH process). It must be
noted here that catalytic transfer hydrogenation (CTH)
25
does provide significant hydrogenation rates albeit at much

DDAB-25 C
20 Table 4
Change In Iodine Value

DDAB-45 C

Fatty acid profile of hydrogenated soy oil using 0.5 M formic acid as a
hydrogen donor
15
CTH MEH

10
16:0 (%) 13.7 13.81
18:0 (%) 4.34 7.82
18:1 (%) 25.18 38.31
5 18:2 (%) 48.91 35.07
18:3 (%) 5.99 2.61
0 IV 122.04 100.52
0 2 4 6 8 10 % trans 4.84 5.03
pH
Nickel catalyst (1 g/l), oil–water ratio (0.3 g/g), DDAB (0.24 g), 0.5 V vs.
Fig. 4. Change in iodine value vs. pH. SCE, 45 °C, 12 h of operation, pH 1.9.
532 K. Mondal, S. Lalvani / Journal of Food Engineering 84 (2008) 526–533

Table 5 cesses, because they are primarily limited by the rate of

Fatty acid profile of hydrogenated soy oil using 0.5 M sodium formate as
donor
CTH
16:0 (%) 13.68
18:0 (%) 5.28
18:1 (%) 26.89
18:2 (%) 47.43
18:3 (%) 5.02
IV 118.41
% trans 6.84
Nickel catalyst (1 g/l), oil–water ratio (0.3 g/g), DDAB (0.24 g), 0.5 V vs.
SCE, 45 °C, 12 h of operation, pH 6.8.
higher formate concentrations (Smidnovik, Kobe, Les-
koovsek, & Koloini, 1994). The two sets of experiments
comparing the CTH and MEH methods used identical for-
mate ion concentration (0.5 M). However, the iodine value
reduction for the MEH process indicates a 60% increase in
the case when formic acid (pH 1.9) was used as opposed to
the use of sodium formate (pH of 6.8). It can thus be con-
cluded that the hydrogenation rates are higher at lower pH
values for the MEH process. However, it is also observed
in the same tables (Tables 4 and 5) that the use of the
CTH process resulted in a 43% increase in the reduction
of iodine value when sodium formate was used instead of
formic acid. This observation is consistent in nature with
those made by (Smidnovik et al., 1992). The trans fatty acid
content showed a modest rise to 5.03% and 3.25% for the
MEH process when formic acid and sodium formate were
used, respectively from an initial value of about 1%. This
corresponds to 0.141reduction in IV as compared to the
corresponding 0.48% and 0.5% increase in trans isomer
content per unit reduction in IV obtained for transfer
hydrogenation (CTH) process.
Fig. 5 provides a comparison of the trans isomer content
vs. IV values for the various methods as compared to the
process described in this paper. The reaction rates are signif-
icantly slower than for commercial hydrogenation pro-
formate regeneration. It is true that by lowering the temper-
ature for commercial hydrogenation, the trans formation
MEH would be reduced, however, it has implications on not just
13.13 the intrinsic reaction rate but also on the mobility of the
6.14 hydrogen gas. Due to mass transfer limitations, the overall
28.22
44.30
rate of gaseous hydrogenation is expected to decrease signif-
4.1 icantly. The data show that in a typical commercial hydro-
genation process, the increase in percent trans isomers per
111.72
3.25 unit decrease in iodine value is approximately 0.89, while
the corresponding values for the electrocatalytic hydroge-
nation (EH) process (Yusem & Pintauro, 1992) and cata-
lytic transfer hydrogenation – CTH (Smidnovik et al.,
1994) are 0.52 and 0.77, respectively. The corresponding
value obtained for the mediator-assisted electrochemical
hydrogenation (i.e. MEH), on the other hand was found
to be approximately 0.17. Thus, the latter process results
in about 80% reduction in trans isomer content as compared
to the commercial gaseous hydrogenation process for the
same degree of hydrogenation. Statistical comparison of
the change in trans isomer levels with changes in component
fatty acids was also carried out. It was found that the
increase in trans isomer content is more strongly correlated
(correlation coefficient = 0.92) to the amount of linoleic
acid hydrogenated than to the change in linolenic acid con-
tent (correlation coefficient = 0.83). The correlation coeffi-
cient is a measure of the departure of two variables from
independence. Values closer to one indicate dependence.
The straight line obtained by plotting the amount of linoleic
acid hydrogenated vs. change in percent trans isomers
yielded an r2 value of 0.95. A similar statistical analysis
for linolenic acid provided an r2 value of 0.78. The r2 value
was 0.95 was obtained when both the amount of linolenic
acid hydrogenation and linoleic acid hydrogenation were
used as the independent variables. This suggests that the
trans isomer formation is mainly a result of a single double
bond hydrogenation of linoleic acid.
4. Conclusions

70
Very significant reduction in trans fatty acid content of
soybean oil via a low temperature electrochemical process
60 Electrochemical
is demonstrated. Formate anion is used for transferring
Hydrogenation
(MEH)
hydrogen to the unsaturated fatty acid, while the electrical
50 current is employed to regenerate continuously the formate
Commerical
Hydrogenation ion at the cathode. The data suggest that the increase in
(Molecular)
trans isomer is related to the linoleic acid hydrogenation.
Trans %

40
Electrolytic
Hydrogenation
30 Catalytic Transfer
Hydrogenation Acknowledgement
(CTH)
20
Funding for the Project was provided by the USDA
10 Grant No. 2005-35503-15369, and CFAR, IL.

0
0 30 60 90 120 150
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