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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.
108
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).
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
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).
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
110
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.)
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)).
112
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)
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
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.
References
[1] Rye L, Blakey S, Wilson CW. Sustainability of supply or the planet: a review of
potential drop-in alternative aviation fuels. Energy Environ Sci 2010;3:1727.
[2] Uusitalo V, Vaisanen S, Havukainen J, Havukainen M, Soukka R, Luoranen.
Carbon footprint of renewable diesel from palm oil, Jatropha oil and rapeseed
oil. Renew Energy 2014;69:10313.
[3] Jakkula J, Niemi V, Purola VM. Process for producing a hydrocarbon component
of biological origin. US patent 0230085; 2004.
[4] Neste Oil Corporation. Neste oil completes the first phase of its microbial oil
pilot plant. Finland: Neste Oil; 2012.
[5] Kalnes TN, Koers KP, Marker T, Shonnard DR. A technoeconomic and
environmental life cycle comparison of green diesel to biodiesel and
syndiesel. Environ Prog Sustain Energy 2009;28:11120.
[6] Detoni C, Bertella F, Souza MMVM, Pergher SBC, Aranda DAG. Palladium
supported on clays to catalytic deoxygenation of soybean fatty acids. Appl Clay
Sci 2014;95:38895.
[7] Wang C, Liu Q, Song J, Li W, Li P, Xu R, et al. High quality diesel-range alkanes
production via a single-step hydrotreatment of vegetable oil over Ni/zeolite
catalyst. Catal Today 2014;234:15360.
[8] Herskowitz M, Landau MV, Reizner Y, Berger D. A commercially-viable, onestep process for production of green diesel from soybean oil on Pt/SAPO-11.
Fuel 2013;111:15764.
[9] Air Transport Action Group, Facts & figures; 2014. <www.atag.org/facts-andfigures.html>.
[10] Hari TK, Yaakob Z, Binitha NN. Aviation biofuel from renewable resources:
routes, opportunities and challenges. Renew Sustain Energy Rev
2015;41:123444.
[11] Choi I-H, Hwang K-R, Han J-S, Lee K-H, Yun JS, Lee J-S. The direct production of
jet-fuel from non-edible in a single-step process. Fuel 2015;158:98104.
[12] Zhao X, Wei L, Julson J, Aiao A, Dubey A, Anderson G. Catalytic cracking of nonedible sunflower oil over ZSM-5 for hydrocarbon bio-jet fuel. New Biotechnol
2015;32:30012.
[13] Galadima A, Muraza O. Catalytic upgrading of vegetable oils into jet fuels range
hydrocarbons using heterogeneous catalysts: a review. J Ind Eng Chem
2015;29:1223.
[14] Kubicka D. Future refining catalysis introduction of biomass feedstocks.
Collect Czech Chem Commun 2008;73:101544.
[15] Hermida L, Abdullah AZ, Mohamed AR. Deoxygenation of fatty acid to produce
diesel-like hydrocarbons: a review of process conditions, reaction kinetics and
mechanism. Renew Sustain Energy Rev 2015;42:122333.
[16] Snre M, Kubickova I, Mki-Arvela P, Ernen K, Murzin DY. Heterogeneous
catalytic deoxygenation of stearic acid for production of biodiesel. Ind Eng
Chem Res 2006;45:570815.
[17] Immer JG, Kelly MJ, Lamb HH. Catalytic reaction pathways in liquid-phase
deoxygenation of C18 free fatty acids. Appl Catal A 2010;375:1349.
[18] Fu J, Lu X, Savage PE. Hydrothermal decarboxylation and hydrogenation of
fatty acids over Pt/C. ChemSusChem 2011;4:4816.
[19] Vardon DR, Sharma BK, Jaramillo H, Kim D, Choe JK, Ciesielski PN, et al.
Hydrothermal catalytic processing of saturated and unsaturated fatty acids to
hydrocarbons with glycerol for in situ hydrogen production. Green Chem
2014;16:150720.
[20] Hollak SA, Ariens MA, de jong KP, van es DS. Hydrothermal deoxygenation of
triglycerides over Pd/C aided by in situ hydrogen production from glycerol
reforming. ChemSusChem 2014;7:105760.
[21] Matos J, Borodzinski A, Zychora AM, Kedzierzawski P, Mierzwa B, Juchniewicz
K, et al. Direct formic acid fuel cells on Pd catalysts supported on hybrid TiO2
C materials. Appl Catal B 2015;163:16778.
[22] Dos Anjos JRS, Gonzalez WDA, Lam YL, Frety R. Catalytic decomposition of
vegetable oil. Appl Catal 1983;5:299308.
[23] Kubickova I, Snre M, Ernen K, Arvela PM, Murzin DY. Hydrocarbons for diesel
fuel via decarboxylation of vegetable oils. Catal Today 2005;106:197200.