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Fuel 94 (2012) 578–585

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Fuel
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Production of renewable diesel by hydroprocessing of soybean oil: Effect of catalysts
Bambang Veriansyah a, Jae Young Han a,b, Seok Ki Kim a, Seung-Ah Hong a, Young Jun Kim a,c, Jong Sung Lim b, Young-Wong Shu c, Seong-Geun Oh c, Jaehoon Kim a,⇑
a Clean Energy Research Center, National Agenda Research Division, Korea Institute of Science and Technology (KIST), Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791, Republic of Korea b Department of Chemical and Biomolecular Engineering, Sogang University, 1 Sinsu-dong, Mapo-gu, Seoul 121-742, Republic of Korea c Department of Chemical Engineering, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul 133-791, Republic of Korea

a r t i c l e

i n f o

a b s t r a c t
The effects of various supported catalysts on the hydroprocessing of soybean oil were studied. Several parameters were taken into account when evaluating the hydroprocessed products, including the conversion, selectivity (naphtha, kero/jet, and diesel), free-fatty acid content, oxygen removal, and saturation of double bonds. The hydroprocessing conversion order was found to be sulfided NiMo/c–Al2O3 (92.9%) > 4.29 wt.% Pd/c-Al2O3 (91.9%) > sulfided CoMo/c-Al2O3 (78.9%) > 57.6 wt.% Ni/SiO2–Al2O3 (60.8%) > 4.95 wt.% Pt/c-Al2O3 (50.8%) > 3.06 wt.% Ru/Al2O3 (39.7%) at a catalyst/oil weight ratio of 0.044. The most abundant composition in the liquid product was straight chain n-C17 and n-C15 alkanes when the Ni or Pd catalysts were used. Enhanced isomerization and cracking reaction activity on the CoMo catalyst may produce lighter and isomerized hydrocarbons. By combining gas-phase and liquid product analyses, decarboxylation was a dominant reaction pathway when the Pd catalyst was used, while hydrodeoxygenation was favored when the NiMo or CoMo catalyst was used. Crown Copyright Ó 2011 Published by Elsevier Ltd. All rights reserved.

Article history: Received 8 June 2011 Received in revised form 21 October 2011 Accepted 21 October 2011 Available online 7 November 2011 Keywords: Hydroprocessing Renewable diesel Vegetable oil Catalysts

1. Introduction The hydroprocessing of natural triglycerides into hydrocarbons is a promising alternative technology for the production of renewable diesel with a higher energy density, lower nitrogen oxide (NOx) emissions, and better oxidation stability when compared to the fatty acid methyl esters (FAMEs) synthesized by transesterification of triglycerides with methanol [1–3]. Depending on the reaction conditions and type of catalyst used, a series of complex reactions occur during the hydroprocessing. This includes the saturation of double bonds, breakage of C–C bonds, heteroatom (sulfur, nitrogen, or oxygen) removal, isomerization, and cyclization [4,5]. The liquid product generally contains straight chain n-alkanes with C15–C18 as major compounds via three different reaction pathways: decarbonylation, decarboxylation, and hydrodeoxygenation. The content of iso-alkanes, cycloalkanes, and aromatics is typically not significant at a mild synthetic condition. These paraffin-rich hydrocarbons are known to have better fuel properties than the FAMEs produced via transesterification [3]. The n-alkanes produced by hydroprocessing retain a much higher cetane number (>70) than that of petroleum diesel fuel ($45), and the boiling point range is comparable to typical petroleum based-diesel. In addition, the production of
⇑ Corresponding author. Tel.: +82 2 958 5874; fax: +82 2 958 5205.
E-mail address: jaehoonkim@kist.re.kr (J. Kim).

renewable diesel using hydroprocessing can be employed in the existing infrastructure of petroleum refineries, which can reduce the initial capital investment [6–8]. The reaction conditions and types of catalysts have significant effects on the composition and quality of the liquid product. Gusmao et al. investigated the hydrocracking of soybean and babassu oils for the production of hydrocarbons over sulfided NiMo/c-Al2O3 and a reduced Ni/SiO2 catalyst in a batch reactor at temperatures of 350–400 °C and hydrogen pressures of 1–20 MPa [9]. The main reaction products were aliphatic hydrocarbons via total decarbonylation, decarboxylation, or hydrogenation. Da Rocha Filho et al. investigated the hydrocracking reaction of soybean oil and other vegetable oils such as maracuja, tucuma, buriti, and babassu oils over sulfided NiMo/c-Al2O3 in a batch reactor [10]. The reaction products were n-alkanes (66–76 wt.%), cycloalkanes (up to 13 wt.%), and alkyaromatics (up to 4 wt.%) after a 2-h reaction at 360 °C and an initial hydrogen pressure of 14 MPa. Huber et al. studied the hydrotreating of sunflower oil using a flow-type reactor with a sulfide NiMo/Al2O3 catalyst at temperatures of 300–450 °C and a hydrogen pressure of 5 MPa [4]. Under optimal conditions, the molar yield of carbons from n-C15 to n-C17 was 71%. Simácek et al. investigated the hydroprocessing of rapeseed oil using a flow type reactor at temperatures of 260–340 °C and a hydrogen pressure of 7 MPa using three different types of commercial NiMo/Al2O3 catalysts [11]. At 340 °C and 7 MPa, the liquid product contained more than 70 wt.% of n-C15 and n-C17. Moreover, n-alkanes with a carbon

0016-2361/$ - see front matter Crown Copyright Ó 2011 Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2011.10.057

3. flame ionization detector (FID). The reac- tor was then pressurized with H2 to the pressure desired for the experiment (9. Netherland). Ru. The average diameter of the particles was defined as the arithmetic average of the diameters of the hemispherically shaped particles in the images. The high-pressure reactor was cylindrical in shape. or Ni catalyst was used. iso-alkanes of C16–C18. The Ni metal loading was measured using a UNICAM M series atomic absorption spectrophotometer (AAS.% Pt/c-Al2O3 were purchased from Strem Chemical (MA. The reactor temperature was then decreased to room temperature.5 wt. The size of the metal particles was estimated by analyzing the TEM images using Canvas by ACD systems (Miami. with a boiling point higher than 360 °C. the reactor was purged with H2 for at least 10 min and then pressurized with H2 at 2 MPa. the liquid product was analyzed using a Perkin-Elmer model Clarus 600 gas chromatograph (GC) equipped with an on-column injector. After the temperature of the reactor decreased to $35 °C and the pressure decreased to atmospheric pressure. hydrotreating reaction conversion (%). the soybean oil in the feed tank was transferred to the reactor. Korea). and Sim Dis capillary column (polymethylsiloxane. The temperature of the reactor was then increased and kept at 400 °C for 1 h to activate the CoMo or NiMo catalyst via sulfidation. air. nitrogen (purity of 99. and 5. were tested in a batch mode. and pore volumes of the supported catalysts were measured using a BELSORP-mini II apparatus (Bel Japan.0 lm). and naphtha were determined using simulated distillation. The hydrotreating selectivity of naphtha. Hydrogen (purity of 99. 2.% Ru/Al2O3 were purchased from Alfa-Aesar (MA. First. Pd.53 mm  1.9 vol. The morphology of each catalyst was characterized using a Philips Model CM30 transmission electron microscope (TEM. In addition. followed by purging with H2 for at least 10 min. Once the desired initial H2 pressure was reached. 5. average pore diameters. USA). with an inside diameter of 34. A known amount of the supported catalyst was charged into the reactor. The reactor was then vented to atmospheric pressure. Catalyst characterization The surface areas. USA) inductively coupled plasma-emission spectrometry (ICP-ES). / Fuel 94 (2012) 578–585 579 number lower than 15 (n-C15). Pd. linoleic acid. and the liquid product was collected and analyzed. 2. 80.0 wt. including supported NiMo and CoMo hydrotreating catalysts and noble metal (i.0 ± 3 wt. UNICAM. or Ru metal loading and CoO. stearic acid. After the reaction temperature reached 400 °C. C18:2. When the Pt. The hydroprocessing conversion and selectivity to diesel.9999%). The choice of catalyst is crucial to determine the composition and fuel properties of hydroprocessed triglycerides.9%).% H2S in Ar for at least 10 min and then pressurized with 14.9%). Inc. free-fatty acid content. The metal loadings were given by the vendors.% Pd/c-Al2O3. Naphtha selectivityð%Þ ¼ Product Feed 40À200 À Feed 40À200 360þ 360þ À Product  100 ð2Þ Kero=jet selectivityð%Þ ¼ Product Feed 170À270 À Feed 170À270 360þ 360þ À Product À Feed  100 ð3Þ Diesel selectivityð%Þ ¼ Product Feed 180À360 180À360 360þ 360þ À Product  100 ð4Þ . respectively. NH and USA) with an air/acetylene flame. oleic acid. 28. giving it a volume of 109 cm3. and double bond content.0 wt. C18:1.%(CoO)/14. Materials The soybean oil used was a commercial product manufactured by CJ Cheiljedang Co. the reactor was purged with 14. alpha linolenic acid. and NiO2 loading on the support were measured using A Varian 170 ES (Varian. Prior to each experiment. C18:3. jet/kerosene.9 vol. helium (purity of 99. Various types of catalysts. The present study focused on the effects of various supported catalysts on the hydroprocessing of soybean oil.98 wt. while the second largest fatty acid component was palmitic acid (C16:0. When the CoMo or NiMo catalyst was used. This assumption is valid when the amount of oxygenated species in the liquid product is low. 2. (Seoul. with the dimensions of 10 m  0. S1 in the Supplementary data shows a schematic diagram of the apparatus. oxygen content. or diesel is defined based on its boiling point range as follows.1. Apparatus and procedure The hydroprocessing experiments were conducted using a custom-built.9 MPa.% H2S in H2 were purchased from the Shinyang Sanso Company (Seoul. Pt. was determined in detail.. the reaction was carried out for an hour. The Pt. 2. high-pressure batch reactor system. Fig. Conversionð%Þ ¼ Feed 360þ À Product 360þ 360þ Feed  100 ð1Þ where Feed360+ and Product360+ are the weight percent values for the feed and product. and 14.2. The largest fatty acid component of the soybean oil consisted of the C18 species (C18:0. including the n-alkane content. which is used to evaluate hydroprocessing efficiency. Eindhoven. Pd. NiMo/c-Al2O3 was obtained from a petroleum refinery company in Korea. Product analysis Two different gas chromatographs were used to evaluate the liquid product composition. is defined as the percentage of the feed fraction with a boiling point higher than 360 °C that has been converted into lighter hydrocarbons with a boiling point lower than 360 °C.e.5 mm and an inside height of 117 mm. The simulated distillation of hydroprocessed products was carried out according to the ASTM D-7213 procedure under an assumption that the areas of each distillation fraction were proportional to the amount of carbon in that fraction.% (MoO) and 5. USA). 10. The reactor was then purged again with N2 for at least 20 min. Veriansyah et al. and the temperature of the reactor was increased to the temperature desired for the experiment (400 °C) for an hour.1 g of soybean oil was introduced into the oil feed tank and then the feed tank was purged with N2 for at least 30 min to remove any oxygen that might have been dissolved in the oil and present in the oil feed tank.93 wt.%).%). The temperature of the reactor was then increased and kept at 400 °C for 1 h to reduce the catalyst. and cycloalkanes formed as the minor the liquid product. Florida). Experimental methods 2.9 vol.0 wt. which was characterized using gas chromatography (GC) according to BS EN14103 [12]. the mixture in the reactor was stirred using the magnetically driven stirrer.0 wt. Japan).B. CA. The gas product was collected and analyzed using gas chromatographs (GC). MoO3.. and then the reactor was purged with N2 for at least 30 min. Table S1 in the Supplementary data lists the composition of fatty acids in the soybean oil. In this study.% Ni/SiO2–Al2O3.% H2S in H2 at 2.2 MPa). Extensive stirring of the oil and supported catalysts in the reactor was achieved using a magnetically driven stirrer with a DC geared motor. 66. Osaka. CoMo/c-Al2O3 with 3. kero/jet. Ni and Ru) supported catalysts.4. the composition of the liquid products. Different reaction mechanisms on the various catalysts were also presented. Korea).

As the temperature increased.25 lm). respectively. and lighter hydrocarbons.044. 1. As shown in Fig.580 B. linoleic acid (C18:2). the hydrodeoxygenation pathway produces alkanes with even numbers of carbons by converting the carboxylic acid with hydrogen and releasing water. stearic acid (C18:0). Effects of catalysts ð6Þ ð7Þ ð8Þ A series of experiments was conducted to investigate the effects of catalysts on the hydroprocessing efficiency and product composition. The catalyst/oil weight ratio was 0. Reaction pathway Fig. When the methanation reaction is negligible. TX.% Ni/SiO2–Al2O3. The detailed description of both GC methods is described in the previous paper [14]. USA) equipped with a flame ionization detector (FID) and an Oxygen Separation Column (SS. The carbon. respectively. The free fatty acid (FFA) content in the liquid product was measured according to the official method of the American Oil Chemists Society (AOCS) (Cd 3a-63) [13]. oleic acid (C18:1). Inc. Methanation of CO2 : CO2 þ 4H2 $ CH4 þ 2H2 O Methanation of CO : CO þ 3H2 $ CH4 þ H2 O Water-gas shift reaction : H2 þ CO2 $ CO þ H2 O 3. Second. The compositions of the gaseous products were analyzed using two gas chromatographs (GC). Feed170–270 and Product170–270 are the weight percent values for the feed and product. MA.. USA). The oxygen was analyzed using a Fisons-EA-1108 (Thermo Scientific. carbon monoxide. the double bonds that were present in the triglycerides were saturated with hydrogen. which were transformed into palmitic acid (C16:0). Vici Valco Instruments Co. including saturation. In this step. hydrogen. respectively. with the dimensions of 60 m  0. It is not necessary to use hydrogen in the decarboxylation reaction.2. USA) equipped with a flame ionization detector (FID) and a Multiseparation Column (PTFE. 1 m  6 mm  5 mm). diglycerides. which was followed by the conversion of the intermediates into deoxygenated products. In addition to the major reactions of decarboxylation. Light gaseous compounds such as carbon dioxide. the most abundant component is n-C17 and the second most abundant component is nC15 if decarboxylation and/or decarbonylation are the dominant reaction pathways. Triglyceride conversions over hydrotreating catalysts in the presence of hydrogen have complex reaction pathways and consist of parallel and/or consecutive reaction steps. the concentration of n-alkanes in the liquid products was analyzed using a Hewlett-Packard model 5890 Series II gas chromatograph (GC) equipped with a flame ionization detector (FID) and a nonpolar column (HP-1. decarbonylation. the molar ratio of CO2/CO can serve as an indicator for evaluating the reaction pathways of decarboxylation and decarbonylation.6 wt. In this second step. and arachidic acid (C20:0).% Ni/SiO2–Al2O3.6 wt. a second drop in hydrogen pressure was observed at temperatures in the range of 270–330 °C. and Feed180–360 and Product180–360 are weight percent values for the feed and product. In contrast. The first GC was a Hewlett-Packard model 5890 Series II GC with a thermal conductivity detector (TCD) and the second GC was a Young Lin model ACME 6100 GC with a pulsed discharge helium ionization detector (PDHID. and eicosenoic acid (C20:1). decarbonylation. and/or hydrodeoxygenation [4]. MA.1. 2 m  6 mm  5 mm). with a boiling point between 180 and 360 °C (diesel fraction). In the case of soybean oil. with a boiling point between 40 and 200 °C (naphtha fraction). the ratio of n-alkanes with odd numbers of carbon atoms to n-alkanes with even numbers of carbon atoms (e. The concentration of n-alkanes (wt. aromatics. and Mp is the total weight of the liquid product. the hydrogenated triglyceride degraded into various intermediates. including monoglycerides. with a boiling point between 170 and 270 °C (kero/jet fraction). cracking. Six different types of supported catalysts were tested: . and cracking can result in iso-alkanes. 1 shows representative pressure and temperature changes with reaction time during the soybean oil hydrotreating using 57. Representative pressure and temperature profile during hydrotreating of soybean oil using 57. The formation of n-alkanes from free fatty acid can take place by one or a combination of three different reaction pathways: decarboxylation. It should be noted that the methanation reaction is undesirable because it consumes expensive hydrogen during hydroprocessing. The decarboxylation pathway converts the carboxylic acid group in the free fatty acids to straight chain alkanes by releasing CO2. / Fuel 94 (2012) 578–585 where Feed360+ and Product360+ are the weight percent values for the feed and product. and water generated by the hydroprocessing reaction can participate in a methanation reaction and water–gas-shift reaction. The n-alkanes of n-C5–n-C7 could not be analyzed because of the peak overlapping with the solvent peak. decarboxylation. and free fatty acids. cyclization.g.. The fatty acids containing double bonds in the chain included palmitoleic acid (C16:1). with a boiling point higher than 360 °C.%) in the liquid product is defined as follows: Fig. competitive reactions of isomerization. decarbonylation. Concentration of n À alkanes in the liquid productðwt%Þ 20 P M nÀC Mp  100% ð5Þ ¼ i¼8 P where 20 MnÀC is the total weight of the n-alkanes (from n-C8 to ni¼8 C20) in the liquid product. The decarbonylation pathway produces alkanes by reacting the carboxylic acid group in the free fatty acids with hydrogen and forming CO and water.32 mm  0. alpha linolenic acid (C18:3). and/or hydrodeoxygenation (see Fig. respectively. and hydrodeoxygenation. 1. 3. 2). USA). Thus. The alkanes produced by decarboxylation and decarbonylation contain odd numbers of carbons in their chains. respectively. n-C17/n-C18) can serve as an indicator for evaluating the reaction pathways of decarboxylation/ decarbonylation and hydrodeoxygenation. a significant drop in hydrogen pressure was observed at temperatures in the range of 100–130 °C. and sulfur were analyzed using a Flash 2000 Series CHNSO Analyzer (Thermo Scientific. MA. nitrogen. The water content in the liquid products was measured using an Orion AF8 Volumetric Karl Fischer titrator (Thermo Scientific. Veriansyah et al. Feed40–200 and Product40–200 are the weight percent values for the feed and product. Results and discussion 3.

% of the petroleum diesel was distilled at the narrow boiling points of 183–359 °C. The catalyst/oil weight ratio was 0. metal particle sizes. 4. 3 and 4 and listed in Table 1. The low hydroprocessing activity of the Ru catalyst . This indicates the predominate formation of high-molecular-weight species. approximately 80 wt. pore diameters. The pure soybean oil was distilled mainly at 590–615 °C. The catalyst/oil weight ratio was 0. Pt/c-Al2O3. In contrast.B. Ru/Al2O3. Fig. The similarity of the final boiling points of the hydroprocessed products to that of soybean oil may be the result of unreacted triglycerides. 1). 3.044. and metal loadings of the catalysts. CoMo/c-Al2O3. after which the reaction proceeded for another one hour at 400 °C. and NiMo/c-Al2O3. which were characterized using BET. / Fuel 94 (2012) 578–585 581 Fig. The effects of the catalysts on the hydrotreating efficiency and product composition were examined at a catalyst/oil weight ratio of 0. Ni/SiO2–Al2O3. When the soybean oil was hydrotreated using the Pd or NiMo catalyst. (a) Effects of catalysts on conversion and selectivity and (b) effects of catalysts on the dry gas composition. 2. S2 shows TEM images of the metal-supported catalysts and Table S2 lists the surface areas.% of the liquid product using the Ru catalyst was over the diesel fuel boiling point range. Another possibility for Fig. Possible reaction pathways of triglycerides over hydrotreating catalyst. probably as a result of the polymerization of the double bonds present in the triglycerides. The current batch reactor required an hour to reach the experimentally desired temperature of 400 °C (see Fig. which fall into the diesel fuel boiling point range. and TEM measurements. the distillation profiles were flat over a wide recovery range at the narrow boiling points of 290–330 °C. Fig. pore volumes. Over 85 wt. the heavy fraction in the liquid product might be related to oligomerization or aromaticization of reaction intermediates containing double bonds in their molecular structures [15]. Veriansyah et al. Pd/c-Al2O3. The distillation profiles of the soybean oil and petroleum diesel are shown in Fig.044 and the results are shown in Figs. The fractions of higher boiling points from 380 °C to 450 °C may be partially reacted intermediates between triglycerides and alkanes. Simulated distillation curves of hydrotreated products of various catalysts.044. 3 for comparison purposes. ICP-ES.

2 MPa.8%) > Ru/Al2O3 (39.2 23.%) n-C11 (wt.26 0. As was the case with the Pd and NiMo catalysts.81 0. the order of the n-C17/n-C18 ratio was Ru/Al2O3 (39.21 0. 5.3) > Pd/c-Al2O3 (11.%) compared to that with the Pd catalyst.16 NiMo 0.7%).%) n-C20 (wt. Fig.%) and n-C15 (8. Pt. / Fuel 94 (2012) 578–585 Table 1 Effects of catalysts on product composition.51 0. CoMo.37 0. Pt. In addition. In contrast.4).8%. while the product was a colorless liquid when the Pd catalyst was used and a yellowish liquid when the NiMo or CoMo catalyst was used. Soybean oil Free fatty acid content (wt.%).7 1.21 0.%) n-alkanes content (wt.49) % CoMo/c-Al2O3 (2. the contents of the n-C17 (41.22 0.87 8.%) n-C10 (wt.3 0. Bifunctional catalysis. The higher hydrocracking activity with the CoMo catalyst may have resulted in a much higher naphtha selectivity of 17.044.7–9. The catalyst/oil weight ratio was 0. or Pt catalyst was used.8 1.14 2.06 wt. Simulated distillation curves of hydrotreated products of various catalysts.84 0.4 wt.059 Ru 21.4 0. However.21 0.08 0.25 0.66 wt. and catalyst/oil weight ratio of 0.021 66. and dehydration on the acid sites may be responsible for the enhanced hydrodeoxygenation reaction [4].03 0.8%) > Pt/c-Al2O3 (50. or Ru catalyst was used. As will be discussed in the later section.28 0.93 0.21 0.5 5. When the NiMo catalyst was used.088.49 0. A higher amount of isoalkane. as can be inferred from the low naphtha selectivity.83 1.7) or NiMo (15.01 0.43 0. The much higher value of CO2/CO with the Pt (13. This indicates that decarboxylation and/or decarbonylation were the dominant reaction pathways when the Ru.3 Pd 4.4 0.66 5.4 2.9%) > CoMo/c-Al2O3 (78.%) n-C8 (wt.%) n-C14 (wt.%) n-C17 (wt.42 1.88 0.%) when the Pd catalyst was used.4 1. Note that a non-negligible amount of free-fatty acid was present in the liquid product when the Pd catalyst was used.49 wt.4) suggests that decarboxylation Fig. Typically naphtha consists of C5– C12 hydrocarbons mixtures. When the Pd catalyst was used. the amount of oxygen in the hydroprocessed liquid using the Ni.7 0.023 43. Ru catalysts was high (oxygen content was 4.04 0. . cycloalkanes. the product was solid when the Ni.%) n-C17/n-C18 0.96 – 46.43 0.9%) > Ni/SiO2-Al2O3 (60.27 0.5 0.96 1. so the analysis can have a large error.67 0.5 8. the diesel selectivity was high.3%.71 0.58 0. the dominating reaction pathway was found to be decarbonylation with the Pd catalyst because the CO2/CO molar ratio was very low (0.70 63.47 31.93 15.90 0.12 0.0%). cycloalkanes.7% and a lower diesel selectivity of 82.%) n-C9 (wt.2 39.47 1.18 4.58 wt.92 Ni 7.52 – 41.90 0.%) Moisture (wt. the much smaller n-alkane content may suggest that the formation of iso-alkane. or aromatic carbon species in the hydroprocessed vegetable oil is desirable because it can enhance low temperature flow properties [4. Veriansyah et al.3 1.33 0.41 0. the straight chain n-alkane content from n-C8 to n-C20 in the liquid product was 85.97 29. in the range of 93.072 85. At room temperature.7 wt.15] . As listed in Table 1. A small amount of shorter chain hydrocarbons from n-C8 to n-C12 formed by hydrocracking of the longer chain n-alkanes.16 2. which was used as the GC solvent.8 0.0 16.6) > Ni/SiO2-Al2O3 (29.82 5.77 0.%) than when using the Pd catalyst. When the Pd or NiMo catalyst was used. while hydrodeoxygenation was more important when the NiMo.89 0.16) > Pt/c-Al2O3 (0.01 5.89 17. the compositions of the hydrotreated products were quite different. diesel production was mostly favored when the Ni or Pt catalyst was used (diesel selectivity of 95.%) and n-C15 (4.00 1.46 2.5–97. The two most predominating n-alkanes were n-C17 (63.49 may have been the result of deactivation by unsaturated deoxygenation and cracking species [16]. the n-alkane content from C8 to C20 in the liquid product was much smaller (66.%) species were also much smaller compared to those with the Pd catalyst.9 CoMo 0.49 1.9) > NiMo/ c-Al2O3 (2.3 0. reaction temperature of 400 °C.0–96. or aromatic carbon species was enhanced by the NiMo catalyst.1 0.92). a shift in the distillation curve toward lower boiling points was observed when the CoMo catalyst was used (see Fig 3). The free-fatty acid content of the liquid produced using the NiMo catalyst was also smaller (0.%) n-C18 (wt. Ni.582 B.9%) > Pd/c-Al2O3 (91.55 0.44 2.%) n-C16 (wt.42 0.%. hydrogenation on the NiMo or CoMo sites. the content of the n-C5 to n-C7 species may not have been significant.%) n-C15 (wt.0 0.6 Pt 13.10 11. All of the experiments were performed at a hydrogen pressure of 9.6 0.32 2. as shown in Table 1. Even though the distillation profiles of the liquid products using the Pd and NiMo catalysts were very similar.%) n-C12 (wt.92 0. the order of hydroprocessing conversion was NiMo/c-Al2O3 (92. When the gas-phase analysis was combined with the liquid-phase analysis. reaction time of 2 h. By taking into account the similar hydrotreating conversions of the soybean oil using the Pd and NiMo catalysts.2 1. or Pd catalyst was used. suggesting that the hydrocracking reaction was negligible at the given reaction condition.%) n-C19 (wt. The conversion and the selectivity estimation using the simulated distillation are based on the assumption that the amount of oxygenated species in the liquid product is low.0 wt.69 1.0 0.80 0.2–6.5%) was produced.%) n-C13 (wt. but no further analysis was performed to identify their compositions.3 wt. 4b shows the effects of various catalysts on the dry gas composition.33 0.06 0.35 0.37 41.51 16. 4.68 – 39.58 2. We were not able to quantify the n-C5 to n-C7 species because the GC peaks of the n-C5 to n-C7 species overlapped with that of dichloromethane.26 1. Only a small amount of lighter hydrocarbons (naphtha selectivity of 3. As shown in Fig.

The effect of the amount of catalyst was examined by increasing the catalyst/oil weight ratio to 0.%) n-C13 (wt. Veriansyah et al. the use of Pt catalyst resulted in lower naphtha selectivity (which is also the result of hydrocracking reaction) when compared to the CoMo catalyst.69 0.9 0.%) n-C20 (wt. The methanation reaction was not very active when the Pd.01 1. The CoMo catalyst seems to have more proper active sites to convert vegetable oil to the naphtha fraction.% to 0.23 mol%.%) n-C17 (wt.% as the Ni catalyst/oil weight ratio increased from 0.39 46.9 mol%. 5 and 6 and Table 2.76 0.65 0.9%).77 8.43 59. the larger amount of C2–C4 species (including propane) indicates that a more active hydrocracking reaction occurred with the Pt catalyst. 6.065 87. kero/jet.49 0. CH4 was the major gas compound (69.89 0.68 0.59 0. Propane.8% to 95.55 wt. 2. reaction time of 2 h. The free fatty acid content was very low (0.%) n-C18 (wt. A methanation reaction by the consumption of CO and CO2 in the gas-phase was responsible for the formation of CH4 (see Eqs. reaction temperature of 400 °C.74 Pd 0.02 0. An increase in the amount of catalyst did not lead to the conversion of species with boiling points higher than 360 °C. 49. Pd.03 0. and Ni catalysts. Ru catalyst). Compared to the Ni catalyst/oil weight ratio of 0. NiMo.84 9.8 mol%.023 82. The n-alkane content in the liquid products increased slightly.40 2.44 1.44 2.00 0.11 23.05–0.38 1.3 mol%.02 0. marginal changes in hydroprocessing conversion were observed when the Pd.026 82.76 mol%) when compared to the other catalysts (Ru.65 0. All of the experiments were performed at a hydrogen pressure of 9.90 0. The most significant change in conversion was observed when the Ni catalyst was used: the conversion increased significantly from 60.9% and the free fatty acid content decreased significantly from 7. It is not clear what is causing different hydrocracking activity to produce C2–C4 species and naphtha fraction when the Pd and CoMo catalysts were used. Since the hydroprocessing conversion with the Pt catalyst is lower than the NiMo.%) n-C8 (wt.71 0. 5).64 0. This was because Ru and Ni are preeminent methanation catalysts [17–19]. CoMo. The order of hydroprocessing conversion was Ni/ SiO2–Al2O3 (95.07 57. which indicated that the hydroprocessed products could be regarded as hydrocarbon mixtures.6%) % NiMo/c-Al2O3 (95.088.77 1. or CoMo catalyst was used. was preferred over decarbonylation.30 .2 MPa. This indicates that the hydrocracking reaction was more favored when the CoMo catalyst was used.04 6.29 0.71 0. indicating better conversion of the carboxylic acid groups.44 2.45 0.B. Soybean oil Free fatty acid content (wt.32 0.03 3.92 10. the free fatty acid contents were much lower compared to those of liquid products with the catalyst/oil ratio of 0. and catalyst/oil weight ratio of 0. The formation of the C2–C4 species in the gaseous product indicated that a cracking reaction took place during the hydroprocessing of the soybean oil.%) n-C16 (wt.80 0.7%). A comparison of the naphtha.044. Pt. Pd.66 1.%) n-C10 (wt. the distillation profile was much flatter over a wide recovery range at the narrow boiling points of 270–330 °C.1 0.044.044 to 0. When the Ni.088. The order of diesel selectivity was Ni/SiO2–Al2O3 (98. and diesel selectivity resulting from hydroprocessed soybean oil is shown in Fig.43 3.55 wt.088. or CoMo catalyst was used. 6a for the different catalysts tested.14 21.%) n-C12 (wt.%) n-C19 (wt.66 0. Ni 0.44 0.61 0.89 mol%.%) n-C17/n-C18 0.65 0. The results are shown in Figs.95 0.9%) > Pd/c-Al2O3 (90. As listed in Table 2.3 1. (6)–(8)).088.68 20.9%) > NiMo/c-Al2O3 (91.05 0. CoMo.%) n-alkane content (wt. 0.96 wt. as discussed previously. However.34 mol%.67 0.15 2.84 2. We did not test the Pt and the Ru catalysts because of their low hydroprocessing activities. When the Pd catalyst was used. In contrast.%) Moisture (wt. / Fuel 94 (2012) 578–585 583 Fig. When the Ni or Ru catalyst was used.20 5. 2. or NiMo catalyst Table 2 Effects of catalysts on product composition.22 1. Pd. (a) Effects of catalysts on conversion and selectivity and (a) Effects of catalysts on the dry gas composition.9%) > Pd/c-Al2O3 (95. was produced in a larger quantity with the Pt catalyst (7.60 6.059 Ni 0. Ni catalyst.%).9 0.80 6. NiMo. A larger amount of C2–C4 species formed when the Pt catalyst was used compared to the other catalysts. The catalyst/oil weight ratio was 0.82 CoMo 0.9%) > CoMo/c-Al2O3 (79.86 1. which fall into the diesel fuel boiling point range (see Fig. This may arise from different reaction pathways and different catalytic adsorption sites of each catalyst.%) n-C11 (wt.%) n-C9 (wt.019 52.%) n-C14 (wt.8 mol%).%) n-C15 (wt.55 0.10 9. one of the main byproducts formed by hydroprocessing of the vegetable oil. NiMo. 2.61 1. the composition of the hydroprocessed soybean oil varied widely with the different catalysts.6%) > CoMo/c-Al2O3 (88.34 NiMo 0.

4 0. 4.5 15.088 77.7 14. Conclusions The effects of various catalysts on the hydroprocessing of soybean oil to produce a paraffin-rich mixture of hydrocarbons were examined using a batch reactor system. as shown in Fig. The most significant increase in oxygen removal was observed when the Ni catalyst was used.3 11.7%) > Pd/c-Al2O3 (90. / Fuel 94 (2012) 578–585 Table 3 Effects of catalysts on carbon. and the results are listed in Table 3. the H/C ratios of the CoMo and NiMo catalysts were higher than that of the Pd catalyst.5%). The effects of the catalysts on the hydroprocessed product composition are given by a van Krevelen diagram.0 14. 7.044.8 14. When the catalyst/oil weight ratio of 0.3 84. the O/C ratio decreased more than 17.0 9. Because of their preeminent oxygen removal and saturation capabilities.3 NiMo 84.3 weight ratio = 0. along with high conversion and low cost.088. the soybean oil had a higher oxygen content and lower hydrogen content than all of the hydroprocessed products.9%) > Pd (91. and sulfur contents in the soybean oil and liquid products were measured using the elemental analyzer.6%) % CoMo/cAl2O3 (92.3 <0.1%) > Ni/SiO2–Al2O3 (95.9%) > Ni (60.4%) > Ru/Al2O3 (15. As discussed previously. When the catalyst/oil ratio was increased to 0.1 15. or aromatics was more favored with the CoMo catalyst. When the catalyst/oil ratio was 0. NiMo.088. along with the low cost.3 <0.%) Ru Pt 81.088.6 – 11.9%) > CoMo (79. cyclic hydrocarbons. The catalyst effect on the saturation extent can be observed via the hydrogen to carbon (H/C) molar ratio in the van Krevelen diagram.5 <0.6 77.044.9%).9%) > Pd (90. For the liquid product obtained at the lowest conversion with the Ru catalyst. and CoMo catalysts make them suitable for use in the hydroprocessing of natural triglycerides. This indicates that the formation of iso-alkanes. Even though the CoMo and NiMo catalysts were sulfided prior to hydrotreating. while at the highest conversion with the NiMo catalyst.% with the Pd or Ni catalyst. NiMo. This indicates that a better hydrogenation reaction occurred on the metal catalysts. the O/C ratio was reduced by $120 times with the CoMo and NiMo catalysts.584 B. The low amount of n-alkane content and the higher naphtha selectivity of the CoMo catalyst suggested that isomerization and the cracking reaction were more enhanced.%) O (wt. The CoMo and NiMo catalysts were very effective at deoxygenating the soybean oil.1 1.2. In contrast.3 – – – – Ni 80. associated with the Ni.6 <0.8 <0. However.088.8%) > Ru (39.8 14. When the catalyst/oil weight ratio was increased to 0.044. Effect of catalysts on hydrogen to carbon (H/C) and oxygen to carbon (O/C) molar ratio of hydrotreated products (a) at the catalyst/oil weight ratio of 0.8%) > Pt (50.3 Pd 84.0 – 11. Veriansyah et al.%) H (wt.2 times.1%) % CoMo/c-Al2O3 (99.4 <0.6 0. oxygen. and Ni catalysts are promising catalysts for producing renewable diesel from natural triglycerides. and sulfur contents.3 CoMo 83. The higher naphtha selectivity with the CoMo catalyst suggests that the cracking reaction was more favored compared to the Ni.3 4.3 – decrease in oxygen content in the hydroprocessed products from the soybean oil.3 wt.%) when the CoMo catalyst was used.3%) > Pt/cAl2O3 (56.7 <0. 7.0 0. Pd.4 1. the CoMo.3 84. Acknowledgment This project was supported by the Korea Ministry of the Environment as a ‘‘Converging technology project.9 wt. was used. the n-alkane content from n-C8 to n-C20 in the liquid product was high (82.8 <0. while the n-alkane content was low (52. Fig.%). while it was less than 55 wt.%) H (wt.7%) at the catalyst/oil weight ratio of 0.4 <0.044 77. As expected. at the higher catalyst/oil ratio of 0. and Ni (95.4 4.3 15.1–87.044 was tested.5 <0. The order of the hydroprocessing conversion was found to be NiMo (92.3 weight ratio = 0.%) S (wt. the oxygen to carbon (O/C) molar ratio was reduced by 1. The Ni catalyst showed the highest H/C value of 2.%) Catalyst/oil C (wt. The straight-chain n-alkane content was more than 80 wt. the metal-supported catalysts exhibited higher H/C values than those of the CoMo and NiMo catalysts.0 <0.3 84. and (b) at the catalyst/oil weight ratio of 0.7 14.9 13.3 15. and a . the order of oxygen removal was NiMo/c-Al2O3 (93.%) S (wt. The composition of the liquid products was strongly influenced by the type of catalyst.8 11.3 84. and NiMo catalysts.%) O (wt.9 – <0.044.% when the CoMo catalyst was used. the saturation of the double bonds that are present in the triglycerides is another important reaction in the hydroprocessing process.9%) > NiMo (91. hydrogen.088.5%) > Pd/c-Al2O3 (90. It is obvious that there was an increase in carbon and hydrogen content. hydrogen.’’ Additional support from the Korea Institute of Science and Technology was also appreciated. the oxygen removal with the Pd catalyst increased marginally with an increase in the catalyst/oil weight ratio.0%) > Ni/SiO2-Al2O3 (57. the sulfur content in the liquid products was below the detection limit.7 <0. The higher conversion and higher oxygen removal capabilities.9%) at the catalyst/oil weight ratio of 0.0 times at a catalyst/oil weight ratio of 0. oxygen. Soybean oil Catalyst/oil C (wt.4 <0. The carbon. the oxygen removal order was NiMo/c-Al2O3 (99.9%) > CoMo (78.

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