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Fuel 174 (2016) 107113

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Bio fuel production from crude Jatropha oil; addition effect of formic acid
as an in-situ hydrogen source
Kyung-Ran Hwang a,, Il-Ho Choi a,b, Hye-Young Choi a, Jeong-Sik Han c, Kyong-Hwan Lee a, Jin-Suk Lee a,
a

Biomass and Waste Energy Laboratory, Korea Institute of Energy Research, Daejeon 305-343, South Korea
Renewable Energy Engineering, University of Science and Technology, Daejeon 305-350, South Korea
c
Agency for Defense Development, Seoul 138-600, South Korea
b

h i g h l i g h t s
 Deoxygenation reaction of crude Jatropha oil was carried out to produce oxy-free hydrocarbons.
 Hydrocarbon was main product, about 97%, in the liquid product and deoxygenation degree was about 99.5%.
 Addition of formic acid as hydrogen donor is favorable deoxygenation reaction of oil and initial deactivation of catalyst.

a r t i c l e

i n f o

Article history:
Received 30 September 2015
Received in revised form 6 January 2016
Accepted 25 January 2016
Available online 3 February 2016
Keywords:
Oxy-free hydrocarbon
Bio-jet fuel
Crude Jatropha oil
In-situ hydrogen
Formic acid

a b s t r a c t
The catalytic deoxygenation reaction of crude Jatropha oil (CJO) was carried out to produce oxy-free
hydrocarbons in assistance with hydrogen in-situ produced from formic acid solution (30%) and addition
effect of formic acid was discussed on the deoxygenation reaction and product distribution. Mixing of formic acid with reactant yielded higher oil conversion and higher selectivity to normal hydrocarbon
(mainly C15 and C17) than those of the other cases (no mixing or water addition). Total surface area
and total pore volume of used catalysts in the batch reactor followed the order Pd/Cformic acid
solution > Pd/Cwater > Pd/Cno co-reactant under constant conditions. Moreover, significantly higher
degree of deoxygenation with a high initial resistance to catalyst deactivation was observed on Pd/C catalyst in the presence of formic acid during the continuous catalytic reaction. This means that addition of
formic acid solution as the hydrogen donor is favorable the deoxygenation reaction and the initial deactivation of catalyst. As results of continuous deoxygenation reaction using the mixture of oil and formic
acid, normal hydrocarbon in the liquid product was main product, about 97%, and the degree of deoxygenation was about 99.5%.
2016 Elsevier Ltd. All rights reserved.

1. Introduction
The production of bio-fuel from non-edible oils is an important
global issue to mitigate global warming and to secure alternatives
to fossil-based fuels [1,2]. Herein, Bio-diesel, fatty acid methyl
ester (FAME), produced by catalytic transesterification reaction of
oils and renewable hydrocarbons yielded by hydrotreating of oils
in NExBTL [3,4] and Ecofining [5] processes are well-known biofuels. Even so, many studies have been still carried out to improve
the fuel properties of FAME (heterogeneous catalyst, blending and
deoxygenation) and to secure economic feasibility of hydrotreated
fuels (pretreatment, unsulfied catalyst and hydrogen usage) [68].
Recently, aviation fuel has received considerable attention due to
Corresponding authors. Tel.: +82 428603504; fax: +82 428603496.
E-mail addresses: hkran@kier.re.kr (K.-R. Hwang), bmjslee@kier.re.kr (J.-S. Lee).
http://dx.doi.org/10.1016/j.fuel.2016.01.080
0016-2361/ 2016 Elsevier Ltd. All rights reserved.

the reports that the aviation accounts for approximately 12% of


carbon emissions from all transport sectors [9] and jet fuel usage
and world market will increase gradually for the next thirty years
[10]. These have encouraged studies on the production of bio-jet
fuel to mitigate transboundary air pollution originated from a
long-distance transportation [1113].
Generally, bio-jet fuel is produced from non-edible oils via previously mentioned commercial processes, where oils are hydrodeoxygenated and hydro-isomerized/cracked with hydrotreating
catalysts and then distillated in sequence. However, a great
amount of hydrogen is required to remove the oxygen in the molecules of oils (300420 m3 of H2/m3 of vegetable oil) [14]. For minimization of hydrogen consumption, decarboxylation reaction of
oils has been studied to take oxygen out of the oil molecules as
CO2 gas, instead of hydro-deoxygenation [15]. As shown in Fig. 1
(a), one mole of triglyceride (TG) converts into propane and free

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K.-R. Hwang et al. / Fuel 174 (2016) 107113

Fig. 1. Catalytic deoxygenation for the production of n-paraffin from triglyceride: (a) decarboxylation reaction from triglyceride and (b) decarboxylation reaction in
assistance with hydrogen in-situ produced from a hydrogen donor (glycerol).

fatty acids (FFAs) in the presence of three moles of hydrogen.


Oxy-free hydrocarbons can be produced from FFAs via catalytic
decarboxylation reaction without hydrogen supply. 5 wt.% Pd catalyst supported on activated carbon, screened by Murzin group,
was founded the representative catalyst for this reaction [16].
However, significant catalyst deactivation is inevitable in the environment of no hydrogen and it is difficult to regenerate the used
catalyst because activated carbon is used for support. Lamb and
co-workers [17] reported that Pd[5]/C stability during decarboxylation reaction could be enhanced by addition of 10% H2 and then
by preventing the formation of unsaturated hydrocarbon products.
More recently, deoxygenation reaction of TG over Pd[5]/C or Pt[5]/
C catalysts aided by in-situ produced hydrogen has been studied,
instead of external hydrogen supply [1820]. As shown in Fig. 1
(b), theoretically, TG is hydrolyzed into three moles of FFA and
one mole of glycerol, where glycerol is used as an in-situ hydrogen
source. Glycerol reforming makes seven moles of hydrogen and the
in-situ produced hydrogen is used for pre-hydrogenation of unsaturated FFAs into saturated FFAs. The hydrogenated FFAs are easily
deoxygenated to oxy-free hydrocarbons. Vardon et al. [19]
performed the coupled hydrothermal hydrogenation and deoxygenation of model FFA using Pt[5.2]Re[4.2]/C catalyst while
employing the hydrogen generated in situ from glycerol. However,
they found that the loading of hydrogen in the batch reactor at the
initial stage was necessary to complete the conversion of FFAs into
desirable hydrocarbons. Hollak et al. [20] examined the hydrothermal deoxygenation of TGs and FFAs over Pd[5]/C catalyst while
using hydrogen produced in situ from glycerol. However, the main
hydrocarbon products were long-chain olefins even though the
hydrogen produced in situ had a positive effect on the deoxygenation activity. Furthermore, additional external hydrogen sources
such as glycerol and methanol were needed to obtain more saturated hydrocarbons, since the conversion rate of glycerol using
Pd/C catalyst was relatively low, in spite of the long reaction time
(20 h).
Recently, the direct formic acid fuel cell has been developed for
portable power applications, where formic acid is a promising
alternative fuel because it can produce hydrogen at relatively low
temperatures over Pd/C catalyst (HCOOH ? CO2 + H2) [21]. Therefore, in the present study, formic acid was applied for catalytic

deoxygenation reaction, as not only a co-reactant but also a hydrogen donor. We conducted the catalytic decarboxylation reaction of
crude Jatropha oil (CJO) over Pd/C catalyst to produce oxy-free
hydrocarbons, assisted with hydrogen in-situ produced from formic acid solution (30%). Deoxygenation reactions of CJO according
to variables were investigated to describe the addition effect of formic acid solution on the degree of deoxygenation and product
distribution.
2. Methods
2.1. Materials
CJO was supplied from Dr. Rajeev K. Sukumaran (India). Distilled
water (D.W.) was produced by using lPure water purification system (Human Co. Ltd.) and formic acid (P85.0%) was employed from
OCI Company Ltd. N,O-Bis(trimethylsilyl)trifluoro-acetamide
(BSTFA, P98.0%) and pyridine (P99.0%) were purchased from Acros
Organic and Samchun Chemicals, respectively, to analyze liquid
products at gas chromatography (GC, Shimadzu GC2010 plus). Ethyl
acetate (P99.5%, Samchun Chemicals) was utilized as a dilution
co-reactant for GC/mass spectrometer (GC/MS, Shimadzu GCMSQP2010 SE) analysis. Palladium on activated charcoals (5% Pd basis,
powder) were purchased from SigmaAldrich Co. Ltd. Before reactions, the catalysts were reduced at 473 K for 2 h with 30% H2/N2.
2.2. Catalytic reaction
A batch-type reactor (50 mL) made by Hanwoul Engineering
Co., Ltd. (South Korea) was used for deoxygenation reaction of
CJO. 3 g of CJO and 0.3 g of catalyst (Pd/C) were added into the vessel. After the vessel was closed, the reactor was purged with 30 ml/
min of N2 for 10 min and co-reactant (D.W. or formic acid solution
(30%)) was injected into the vessel. For the batch reaction, coreactant was injected after N2 purging because formic acid solution, one of co-reactants, reacts immediately with Pd/C even at
room temperature. The reaction pressure was started from atmospheric pressure. When the temperature of the reactor was
reached at setting value, then, agitation was started (300 rpm)
and the reaction was conducted for 4 h. When the reaction time

K.-R. Hwang et al. / Fuel 174 (2016) 107113

was over, the reactor was cooled to room temperature and liquid
and gas products were collected on a vial and a tedlar bag (SKC
Inc.), respectively.
The continuous catalytic reaction of CJO in the fixed bed reactor
is very important, because the reaction is 3-phase reaction. Therefore, a continuous deoxygenation reaction was carried out in a
fixed bed reactor made by T-ENG Engineering Co., Ltd. (South
Korea). 5 g of catalyst (Pd/C) was filled in a stainless steel reactor
(I.D = 19 mm) and both ends of the reactor were filled with quartz
wool and inert ceramic ball (45 mm in diameter) for homogeneous distribution of reactants. The length of the catalyst bed
was 15 mm. The reactant was diluted with co-reactants
(reactant:co-reactant = 2:3 wt.%) and was injected with micro
pump (Young Lin Instrument Co., Ltd, SP930D) at 0.3 ml/min. The
reaction temperature was maintained at 633 K and the system
pressure, 4 MPa, was controlled by a back-pressure regulator,
located in the stream of gas outlet, to allow the sufficient time to
contact and then react between the liquid reactant and in-situ generated hydrogen over the surface of Pd/C catalyst. The reaction was
carried out under a fixed flow of N2 (20 ml/min) and weight hourly
space velocity (WHSV) was 1.35 h 1.
2.3. Analysis
The liquid product was analyzed by two methods (quantifying
the acid number and GC/MS). Quantifying the acid number was utilized to evaluate the ratio of free fatty acid in the liquid product and
GC/MS analysis identified the compositions and their fraction of the
liquid product. For the more information on liquid product analysis
such as pretreatment methods of the liquid sample, detailed GC
program and analysis method of the acid number, refer to our previous work [11]. The C, H, N and S contents in the reactant were
measured by element analyzer (Thermo Scientific, Flash 2000 serie)
and the oxygen contents in the reactant and the liquid product were
measured by O2-element analyzer (EA, Thermo Finnigan, FlashEA
1112). The analysis of gas product was conducted by using GC (Agilent technologies, 7890A GC system) equipped with thermal conductivity detector (TCD) and flame ionization detector (FID). The
columns for TCD and FID were Supelco packed column (carboxen
1004) and Agilent J&W capillary column (GS-Alumina), respectively. The injector temperature was 523 K and detectors one was
523 K (TCD) and 573 K (FID), respectively. Oven temperature was
kept at 323 K for 5 min, increased from 323 K to 443 K with a ramp
rate of 303 K min 1 and then kept for 2 min. In order to measure the
exact amount of each gas product, we employed a standard gas
manufactured by Special Gas (South Korea), which is composed of
H2, N2, CO, CO2, CH4, C2H6, C3H8, and C4H10.

109

Fig. 2. Results of reforming reaction of formic acid solution with or without Pd[5]/C
catalyst: gray bar for reaction without catalyst and dark gray bar for reaction with
catalyst (catalyst: 0.3 g, formic acid solution (30%): 3 g, reaction temperature:
340 C and reaction time: 0.5 h).

accounted for around 80% in the composition of the oil, while


saturated fatty acids, C16:0 and C18:0, made up around 20%. Unsaturated ones should be hydrogenated to saturated ones prior to
the catalytic deoxygenation in order to accelerate the reaction rate
and also to prevent severe deactivation of catalysts [18]. The

3. Results and discussion


3.1. Characterization of CJO
CJO is dark brown. The composition of CJO, which was measured by GC analysis of FAME converted from the oil, is summarized in Table. 1. Unsaturated free fatty acids, C18:1 and C18:2,
Table 1
Distribution of fatty acids (mol%) and ratio of FFA (%) in CJO.

Fatty acid (X:Y)a

CJO

Palmitic (16:0)
Stearic (18:0)
Oleic (18:1)
Linoleic (18:2)
Linolenic (18:3)
Ratio of FFA (%)

12.2
7.3
42.2
37.3
0
4.4

X:Y = carbon number:number of double bonds.

Fig. 3. Results of catalytic deoxygenation reaction of CJO according to the


co-reactants in the batch reactor: (a) distribution of liquid product: brown for
paraffin, black for olefin, mustard for aromatic, blue for saturated FFAs, green for
unsaturated FFAs and pink for oxygen-containing and unidentified compounds, and
(b) distribution of gas product (catalyst: 0.3 g, CJO: 3 g, co-reactant: 3 g, reaction
temperature: 340 C, and reaction time: 4 h). (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this article.)

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K.-R. Hwang et al. / Fuel 174 (2016) 107113

elemental composition of CJO comprised 77.16% carbon, 11.59%


hydrogen and 11.25% oxygen. The acid number of CJO was 4.4%,
indicating that TG was predominant in CJO. The pH value was
6.71 and density was 0.897 g/ml at room temperature.
3.2. Catalytic deoxygenation reaction of CJO
3.2.1. Hydrogen in-situ produced from formic acid solution
Formic acid generates hydrogen via its reforming reaction on
Pd/C catalyst even at room temperature, as reported previously
[21]. Fig. 2 shows the results of the reforming reaction of formic
acid solution (30%) with or without Pd/C catalyst. Reforming
products, H2 and CO2, were produced at 613 K in the absence of
catalyst and in assistance of Pd/C, the larger amount of hydrogen
was produced and traces such as CH4 and CO were detected. This
means that the formic acid solution can be a good hydrogen donor
to hydrogenate unsaturated FFAs into saturated ones.
3.2.2. Catalytic deoxygenation reaction of CJO
Fig. 3 shows the results of catalytic deoxygenation reaction of
CJO according to the co-reactants at 613 K in the batch reactor.
When no co-reactant was added to the reactant, oxy-free hydrocarbons accounted for around 79% (51% for paraffin, 5% for olefin,
and 22% for aromatics) in the liquid-phase product, as shown in

Fig. 4. Results of catalytic deoxygenation reaction of CJO according to the amount


of formic acid in the batch reactor: (a) distribution of liquid product and percentage
of FFAs in the liquid product: brown for paraffin, black for olefin, mustard for
aromatic, blue for saturated FFAs, green for unsaturated FFAs, pink for oxygencontaining and unidentified compounds and yellow dot for FFAs percentage and (b)
distribution of gas product (catalyst: 0.3 g, CJO: 3 g, reaction temperature: 340 C,
and reaction time: 4 h). (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)

Fig. 3(a). The produced paraffin and olefin were normal hydrocarbon in the range of C10C18 (mostly C15 and C17). However,
oxygen-containing molecules such as ketone and alcohol and
unidentified compounds were found in the liquid product (about
10%). Fig. 3(b) showed that CO2 was predominant in the gasphase product, indicating that decarboxylation reaction was
occurred over Pd/C catalyst [16]. Some light gases were also
detected, which appeared to be originated from the cracking reaction of the reactant. In case D.W. was used as co-reactant, a little
bit higher amount of hydrocarbons (around 88%) was produced
than no co-reactant test, but olefin hydrocarbon was not detected
in the liquid product. This means that hydrogen in-situ produced
from the given reaction condition assists to hydrogenate unsaturated FFAs to saturated ones, as reported in the literatures [18].
Some trances containing oxygen in their molecules were founded
in the liquid product. Amount of gas products were larger than
the result of no co-reactant test and CO2 was still dominant gas
product (Fig. 3(b)). Even though some hydrogen was generated
from the given reaction condition and then assisted the hydrogenation reaction, FFAs in the liquid product were still remained.
Whereas, when formic acid solution was used as a co-reactant,
the liquid product was all paraffinic hydrocarbons (pentadecane
and heptadecane) and the percentage of FFAs was near to zero.
After deoxygenation reaction, an extremely larger amount of
hydrogen and carbon dioxide were occurred. Compared with the
amount of gases in Fig. 2 (in case of no reactant added), the amount
of hydrogen decreased while carbon dioxide increased. Some

Fig. 5. Results of catalytic deoxygenation reaction of CJO in the batch reactor: (a)
distribution of liquid product and percentage of FFAs in the liquid product: brown
for paraffin, black for olefin, mustard for aromatic, blue for saturated FFAs, green for
unsaturated FFAs, pink for oxygen-containing and unidentified compounds and
yellow dot for FFAs percentage and (b) distribution of gas product (catalyst: 0.3 g,
CJO: 3 g, co-reactant (DW or formic acid solution): 3 g, reaction temperature:
300 C, 340 C, and reaction time: 4 h). (For interpretation of the references to color
in this figure legend, the reader is referred to the web version of this article.)

K.-R. Hwang et al. / Fuel 174 (2016) 107113

111

Fig. 6. Results of catalytic deoxygenation reaction of FFAs originated from CJO in the fixed bed reactor: (a-1) distribution of liquid product yielded from the reaction using
D.W. as co-reactant, (a-2) GC peak of liquid product yielded from the reaction using D.W. as co-reactant, (b-1) distribution of liquid product yielded from the reaction using
formic acid solution as co-reactant and (b-2) GC peak of liquid product yielded from the reaction using formic acid solution as co-reactant (catalyst: 5 g, FFAs/co-reactant =
2/3(w/w%), feed rate: 0.3 ml/min, N2: 20 ml/min, reaction temperature: 340 C, and initial pressure: 40 bar (N2)).

hydrogen appeared to be consumed for hydrogenation of


unsaturated FFAs and carbon dioxide seemed to add as product
gas of decarboxylation reaction of saturated FFAs (C16 and C18
FFAs ? C15 and C17 hydrocarbons + CO2).
Fig. 4 shows the results of catalytic deoxygenation reaction of
CJO according to the amount of formic acid at 613 K in the batch

reactor. A small amount addition of formic acid solution (1 g)


induced lower FFA percentage and higher percentage of saturated
hydrocarbons than those in case of D.W. addition. This indicates
that in-situ generated hydrogen make deoxygenation reaction
more favorable by converting unsaturated FFAs into saturated
FFA. With increase of the amount of formic acid solution in the

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K.-R. Hwang et al. / Fuel 174 (2016) 107113

reactants, the amount of total gases occurred steadily increased, as


shown in Fig. 4(b).
The effect of reaction temperatures on deoxygenation reaction
of CJO is shown in Fig. 5. Regardless of co-reactants used, the lower
the reaction temperature is the lower the degree of deoxygenation
of CJO. At 573 K, when formic acid solution was added into reactant, the percentage of hydrocarbons in the liquid product was 2
times higher in case of D.W. addition and aromatics were not found
at tested all reaction temperatures. Whereas, oxygen-containing
molecules such as ketone and alcohol and unidentified compounds
were observed in the liquid product from D.W. added reactant.
Deoxygenation reactions of FFAs, originated from CJO, were carried out in the fixed bed reactor according to the co-reactants, D.W.
and formic acid solution, and their results are shown in Fig. 6. In
here, the liquid products obtained at 7 h after reaction (time-onstream = 7 h) were analyzed and compared. After reaction with
D.W., the liquid product went hard at room temperature, indicating that a large amount of FFAs was still present in it. Indeed, the
percentage of FFA calculated from the acid number was 71% in
the liquid phase. From the analysis results of GC, it is observed that
the most of them was saturated FFAs such as stearic acid and palmitic acid. As shown in Fig. 6(a-1), hydrocarbons occupied about
65% in the liquid product, but about 26% of them were unsaturated
hydrocarbons, which is different from the results in the batch reaction. This might be due to the short residence time in the fixed bed
reactor. Furthermore, oxygen-containing compounds were
observed in the wide range of carbon number, as shown in Fig. 6
(a-2). In particular, the oxygen-containing compounds detected
under about 27 min were identified as FFAs having much lower
molecular weight than those in CJO, which might be products of
cracking reaction of FFAs originated from CJO. Whereas, when
using formic acid solution, the liquid product kept remained liquefied at room temperature and the percentage of FFA was below
0.9%. The liquid yield was 93.13%, significantly higher than that
(62.5%) in case of DW addition as the co-reactant. Note that the
weight of co-reactant was excluded from the calculation of the liquid yield. Based on the results of GC analysis, normal hydrocarbon
was main product, about 97%, and traces was detected (Fig. 6(b-2)).
Dos Anjos et al. [22] reported that the degree of unsaturation of the
oil significantly affected on the products and saturated FFAs
yielded pure hydrocarbons. Indeed, based on the results, the formic
solution was effective as hydrogen donor and effectively prehydrogenated unsaturated FFAs to saturated ones, which induced hydrocarbon products with high selectivity, as shown in Fig. 6(b-2).
Interestingly, some hydrogen took part in the deoxygenation reaction of FFAs (C16 and C18 FFAs + H2 ? C16 and C18 hydrocarbons
+ H2O), based on the result of liquid product (Fig. 6(b-2)). When
considering the liquid yield, net production of oxy-free hydrocarbon was above 90%, which was much higher than that (about
40%) in case of DW addition as the co-reactant. EA analysis showed
that the liquid product was contained a small amount of oxygen,
about 0.05%, meaning that the degree of deoxygenation was about
99.5%.

Fig. 7. Results of catalytic deoxygenation reaction of FFAs originated from CJO in


the fixed bed reactor as a function of time-on-stream. (catalyst: 5 g, FFAs/coreactant = 2/3(w/w%), feed rate: 0.3 ml/min, N2: 20 ml/min, reaction temperature:
340 C, and initial pressure: 40 bar (N2)).

3.3. Catalyst deactivation


Catalyst deactivation is inevitable during the catalytic reaction.
In case of reactions with long chain reactants like crude oils,
adsorption, accumulation and blocking of reactants, intermediates
and products in the pores of catalyst are commonly occurred [23].
In particular, if the reactants contain a large amount of poly unsaturated compounds, the degree of deactivation is more accelerated
because the heavy intermediates are dominantly occurred in the
absence of hydrogen.
In the present work, catalysts used for deoxygenation reaction
of CJO in the batch reactor were separated, washed with acetone
and then dried in order to analyze the surface area and texture
parameters of catalysts and then to reveal the degree of catalyst
deactivation. Table 2 summarizes the BET surface area, pore volume and mean pore diameter of used catalysts. The fresh Pd/C catalyst has high total surface area of 690 m2/g and total pore volume
of 0.68 cm3/g. After the reactions, total surface area and total pore
volume of used catalysts followed the order Pd/Cformic acid solution > Pd/CD.W. > Pd/Cno co-reactant under constant conditions.
After catalytic deoxygenation reactions with either no co-reactant
or D.W., pore volume in micro-size was zero, surface area was near
to zero and mean pore diameter increased 3.94 nm to above
10 nm. This means that most of micro-pores are blocked by longchain reactants, intermediates and products. In contrast, about
66% of total pore volume of the fresh catalyst was alive and meso
and macro pores were kept like fresh catalyst, even though the
micro pore was also significantly diminished, in case of the reaction assisted by formic acid solution as the hydrogen donor. Based
on the results of texture parameters of spend catalysts, it can be

Table 2
Surface area and texture parameters of catalysts used for catalytic deoxygenation reaction with different solvents in the batch reactor.
Catalyst

Pd/Ca
Pd/C-noneb
Pd/C-D.W.c
Pd/C-formicd
a
b
c
d

SBET (m2/g)

Pore volume (cm3/g)

Mean pore size (nm)

Total

Micro

Meso

Macro

Total

Micro

Meso

Macro

690.0
94.6
131.6
251.4

455.6
2.7
5.2
65.2

135.4
65.7
85.4
112.7

99.0
26.2
41.0
73.5

0.68
0.28
0.33
0.45

0.21
0.00
0.00
0.04

0.30
0.16
0.20
0.25

0.17
0.12
0.13
0.16

Reduced catalyst.
No solvent was used for the reaction.
D.W. was used for the reaction.
Formic acid solution was used for the reaction.

3.94
11.97
10.19
7.10

K.-R. Hwang et al. / Fuel 174 (2016) 107113

expected higher catalyst resistance to deactivation in the presence


of formic acid solution during the continuous catalytic reaction.
Fig. 7 shows the results of catalytic deoxygenation reactions in
the presences of two different co-reactants in the fixed bed reactor
as a function of time-on-stream. The addition of formic acid solution in the catalytic deoxygenation reaction promoted significantly
the degree of deoxygenation in the initial stage (7 h of time-onstream). Although the rapid decrease in the degree of deoxygenation was observed after 7 h of time-on-stream, about 50% reduction in the initial degree of deoxygenation was observed at
around 11 h of time-on-stream. On the other hand, the initial
degree of deoxygenation in the continuous catalytic reaction with
D.W. co-reactant was relatively low and at around 7 h of time-onstream, about 50% reduction in the initial degree of deoxygenation
was observed. This indicates that it is favorable to use formic acid
solution in terms of both the catalytic deoxygenation reaction and
initial deactivation of the catalyst. Of However, different deactivation reasons including Pd sintering should be further examined and
effective catalyst regeneration methods should be investigated.
4. Conclusion
The catalytic deoxygenation reaction of CJO was carried out to
produce oxy-free hydrocarbons in assistance with in-situ produced
hydrogen, without any external hydrogen supply and addition
effect of formic acid was discussed on the deoxygenation reaction
and product distribution. In the present investigation, formic acid
solution (30%) was used as a co-reactant and also a hydrogen donor
with commercialized Pd[5]/C catalyst. For comparison purpose, D.
W. was also used for the reaction. When D.W. was added as coreactant in the batch reactor for deoxygenation test of CJO, the
liquid-phase product contained oxy-free hydrocarbons of around
88%, where the produced paraffin was normal hydrocarbon in the
range of C10C18 (mostly C15 and C17). Whereas, mixing of formic
acid into reactant yielded higher oil conversion and higher selectivity to normal hydrocarbon (mainly C15 and C17) than those of
the other cases (no mixing or water addition). In the fixed bed reaction using the mixture of oil and formic acid, normal hydrocarbon
was main product, about 97%, in the liquid product and the degree
of deoxygenation was about 99.5%.
After the reactions in the batch reactor, total surface area and
total pore volume of used catalysts followed the order Pd/Cformic
acid solution > Pd/Cwater > Pd/Cno co-reactant under constant
conditions. As results of continuous reaction in the fixed bed reactor, significantly higher degree of deoxygenation with a high initial
resistance to catalyst deactivation was observed on Pd/C catalyst in
the presence of formic acid. This means that addition of formic acid
solution as the hydrogen donor is favorable the deoxygenation
reaction and the initial deactivation of catalyst.
Acknowledgements
We would like to acknowledge the financial support from the
R&D Convergence Program of the MSIP (Ministry of Science, ICT

113

and Future Planning) and ISTK (Korea Research Council for Industrial Science and Technology) of the Republic of Korea (CMP-1306-KIER). We are grateful to Dr. Rajeev K Sukumaran in India
who supplied Jatropha oil.
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