Applied Catalysis A: General 329 (2007) 120–129 www.elsevier.

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Processing biomass in conventional oil refineries: Production of high quality diesel by hydrotreating vegetable oils in heavy vacuum oil mixtures
George W. Huber a, Paul O’Connor b, Avelino Corma c,*
a

Chemical Engineering Department, University of Massachusetts-Amherst, Amherst, MA 01003, USA b BIOeCON BV Hogebrinkerweg 15e, 3871KM Hoevelaken, The Netherlands c ´ ´ Instituto de Tecnologıa Quımicia, UPV-CSIC, Universidad Politenica de Valencia, Valencia, Spain Received 5 March 2007; received in revised form 3 July 2007; accepted 3 July 2007 Available online 7 July 2007

Abstract Renewable liquid alkanes can be produced by hydrotreating of vegetable oils and vegetable oil–heavy vacuum oil (HVO) mixtures at standard hydrotreating conditions (i.e. 300–450 8C) with conventional hydrotreating catalysts (sulfided NiMo/Al2O3). The reaction pathway involves hydrogenation of the C C bonds of the vegetable oils followed by alkane production by three different pathways: decarbonylation, decarboxylation and hydrodeoxygenation. The straight chain alkanes can undergo isomerization and cracking to produce lighter and isomerized alkanes. The carbon molar yield of straight chain C15–C18 alkanes was 71% on a carbon basis (the maximum theoretical yield for these products is 95%) for hydrotreating of pure vegetable oil under optimal reaction conditions. The rate of alkane production from pure sunflower oil is greater than the rate of hydrodesulfurization of a HVO with a 1.48 wt% sulfur content (e.g. 100% conversion of sunflower oil at 350 8C compared to 41% conversion of sulfur). The yield of straight chain alkanes increases when sunflower oil is mixed with HVO, illustrating that dilution of HVO can improve the reaction chemistry. For example, with a 5 wt% sunflower oil–95 wt% HVO feed the maximum theoretical straight chain C15–C18 yield from the sunflower oil was higher (87%) than it was with the pure sunflower oil (75%). Mixing the sunflower oil with HVO does not decrease the rate of desulfurization indicating that sunflower oil does not inhibit the hydrotreating of HVO. # 2007 Elsevier B.V. All rights reserved.
Keywords: Hydrotreating; Biofuels; Biodiesel; Vegetable Oils; Catalysis

1. Introduction Vegetable oils are a renewable feedstock currently being used for production of biofuels from sustainable biomass resources. There are many benefits of biofuels including domestic production of fuels, decreased greenhouse gas emissions, decreased dependence on fossil fuels, improvement of rural economies and increased national security [1–4]. For these reasons the European Commission has set a goal that by 2010, 5.75% of transportation fuels in the EU will be biofuels. Biodiesel production from trans-esterification of vegetable oils is currently the primary route for production of biofuels from vegetable oils. This process has many benefits, however, new biodiesel plants must be built requiring a large capital

* Corresponding author. E-mail addresses: huber@ecs.umass.edu (G.W. Huber), acorma@itq.upv.es (A. Corma). 0926-860X/$ – see front matter # 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2007.07.002

investment [1,5,6]. The economics of biodiesel production depend on selling byproduct glycerol, and increased biodiesel production will cause the price for glycerol to decrease [7]. Another option for biofuels production is to use existing petroleum refineries [8–10]. Petroleum refineries are already built and using this existing infrastructure for biofuels production would require little capital cost investment. In this paper, we discuss the feasibility of production of biofuels by hydrotreating of vegetable oils. Hydrotreating is used in the petroleum refinery to remove S, N and metals from petroleum-derived feedstocks including heavy gas-oil or vacuum gas-oil [11]. Hydrotreating has previously been used to produce straight chain alkanes ranging from n-C15–n-C18, from a fatty acid fraction of tall oil (produced during kraft refining), and other vegetable oils [12– 14]. The normal alkanes produced have a high cetane number (above 98) whereas typical diesel fuel has a cetane number around 45. The normal alkanes produced also have good cold flow properties. In fact a 10-month on-road test of six postal

this assumption is not as valid for distillation fractions that have high oxygen containing species (i. The pure sunflower oil is mainly in the 520–1000 8C range as shown in Table 2. all the sunflower oil is converted into the boiling oil fractions shown in Fig. engine compatibility and feedstock flexibility [14].e.9081 0.44 to 0. HVO. 3.15 464 12. Experimental Sunflower oil. The hydrodesulfurization conversion (HDS conversion) was calculated by subtracting the sulfur in the feed minus the sulfur in the product and divided by the sulfur in the feed. which were separated in a 15 m molecular sieve column. we used simulated distillation to analyze the wide range of products that occur under hydrotreating conditions. Standard edible grade sunflower oil (Califour brand) was used for this study. The fraction distillated from 250 to 380 8C was the major distillation fraction. All yields in this paper are reported on a molar carbon percent basis. The concentrations of sulfur and nitrogen in the original feed chromatograph equipped with a Petrocol-100 fused silica column connected to a FID detector following PIONA procedure. At a reaction temperature of 350 8C and above no acidity was detected in the products. Then. HVO (88 wt% C and 1. The reaction conditions for catalytic hydrotreating experiments were as follows: temperatures 300–450 8C. and discuss strategies as to how HVO and vegetable oils could be processed in the same reactor within a petroleum refinery. The carbon yields reported in this paper are defined as the moles of carbon in each product divided by the carbon in the feed. 1. atmospheric pressure and 400 8C for 9 h. a Thermal Conductivity Table 1 Properties of heavy vacuum gas-oil used in this study Density 288 K (g/cm3) Sulfur (wt%) N2 (ppm) Carbon Conradson (wt%) Average molecular weight (g/mol) KUOP Distillation curve D-1160 vol% K 0. We first discuss the reaction pathway and products for hydrotreating of pure sunflower oil. To use the existing petroleum refinery infrastructure for vegetable oil conversion to diesel fuel.97 hÀ1 and H2 to feed ratio of 1600 ml H2 gas/ml liquid feed. we report the results for hydrotreating mixtures of HVO and vegetable oil. The advantages of hydrotreating over trans-esterification are that it has compatibility with current infrastructure. Huber et al. The reaction gases were analyzed using a Varian 3800-GC equipped with three detectors. However. The acidity of the effluent.W. and 65 cm in length). The catalysts were presulfided using a mixture of H2S/H2 (9 vol% H2S) at a gas flow-rate of 450 ml/min. We also analyzed some of specific products including the straight chain alkanes. In this study.9% NiO. In analyzing the simulated distillation results it was assumed that the areas of each distillation fraction were proportional to the amount of carbon in that fraction. We believe this assumption is valid for experiments in this paper which was collected at high tri-glyceride conversion. / Applied Catalysis A: General 329 (2007) 120–129 121 delivery vans showed that engine fuel economy was greatly improved by a blend of petrodiesel with hydrotreated tall oil [14]. At a reaction temperature of 350 8C and LHSV of 5. 2. Haldor-Topsoe TK-525) was loaded into a stainless steel tubular reactor (2. Finally. This procedure involves titrating the oil with a KOH standard. Acrolein and glycerol were not detected in the gas or liquid phase of the reaction products. 1 shows the product yields (on a molar carbon basis) for hydrotreating of pure sunflower oil as a function of distillation temperature (based on simulated distillation).11 5 638 10 673 30 704 50 729 70 763 90 824 Detector (TCD) for analysis of H2 and N2. Hydrotreating of pure vegetable oils Fig. Total acidity number (TAN) was determined following ASTMD974 method. TAN is defined as the mg of KOH/g of oil. CO and CO2. with carbon yields from 47 to 75%. Liquid samples were analyzed with a Varian 3900-GC for normal alkane. In addition. LHSV 4. The simulated distillation of the different feeds in this study is shown in Table 2. The . which was used as an internal standard. The catalyst (NiMo/ Al2O3.35 1614 0. The concentrations of sulfur and nitrogen in the original feed and liquid products were determined by elemental analysis in a Fisons 1108 CHNS-O instrument. The gas inlet was 91% H2 with the balance being Ar. The purpose of this paper is to show how hydrotreating could be used to produce diesel fuel from vegetable oil and vegetable oil mixed with HVO. This assumption is typically reasonable for hydrocarbons (and petroleum-derived products) which have similar sensitivities.54 cm i.07. we hydrotreat a petroleum feedstock. The TAN of the initial sunflower oil was 0.d.48 wt% S) was supplied by CEPSA and the properties of the HVO are given in Table 1.1.2 hÀ1.G. HVO and sunflower oil–HVO mixtures were processed in a fixed bed reactor with a sulfided NiMo/Al2O3 catalyst (3. simulated distillation of the hydrotreated products were carried out using a Varian 3800-GC chromatograph according to the ASTM-2887-D86 procedure.00 as the reaction temperature increases from 300 to 350 8C. pressure 50 bar. Finland oil-refinery that produces diesel fuel from vegetable oil by a modified hydrotreating process [15]. measured as the TAN (total acidity number defined as mg KOH/g oil product) decreased from 2. Neste Oil Corporation is currently adding 3500 barrels per day unit to their Porvoo Kilpilahti. 18. Results and discussion 3.0 wt% MoO3). the vegetable oils need to be hydrotreated with petroleum-derived feedstocks such as heavy vacuum oil (HVO). distillation fraction of 380–520 and 520–1000 8C for feeds that have high vegetable oil components and low conversions). and a Flame Ionization Detector (FID) for C1–C6 hydrocarbons separated in a 30 m Plot/Al2O3 column. to compare hydrotreating of vegetable oil and petroleum-derived products.

27 0. decarbonylation and hydrodexogenation (or dehydration/hydrogenation). The fraction of straight chain C9–C14 alkanes in the 150–250 8C fraction decreases from 50 to 34% as the reaction temperature increases from 300 to 450 8C.46 4. The other products in this distillation fraction are primarily isomers of the alkanes. This fraction corresponds primarily to light alkanes. n-C18.e.00 0. maximum in this fraction occurred at a reaction temperature of 350 8C. and the percentage of straight chain alkanes in this fraction also decreases.1 1.00 0. 380–520 8C: open squares.5 11 0.14 0. The distillation cut from À50 to 65 8C increases from 4. We attempted to collect data at lower conversion by operating at a LHSV of 17.48% as the reaction temperature increases from 300 to 450 8C (Fig. The cut from 150 to 250 8C increases from 0. CO and CO2.6 70. At this higher space velocity a solid white wax product formed.2 hÀ1) no evidence of the polymer was seen indicating that all polymers were converted into alkane products. The fraction of CO. 1A). The yield of these two alkanes goes through a maximum at 350 8C. n-C17. but they are most likely oxygenated intermediates between the tri-glyceride and the alkanes.9 0.50 42. and 50 atm H2. Figs.00 0.10 66.W.09 0.00 Calculated.16 to 5.00 0.20 57. The yields of the fractions that distill below 250 8C increase with increasing reaction temperature probably due to cracking reactions.10 (380–520 8C) 73. i.72% as the reaction temperature increases from 300 to 450 8C.00 (150–250 8C) 0 0. n-C17 and n-C18. We have not yet identified these .80 5%a 10%a 15%a 30%a 50%a 0 0 0 0.16 6. Huber et al. The 380 to 520 8C fraction decreases from 14 to 4% as the reaction temperature increases from 300 to 350 8C. Table 2 Simulated distillation results of feeds Distillation (area%) (À50 to 65 8C) HVO Oleic acid pure Sunflower pure HVO 95% sunflower HVO 90% sunflower HVO 85% sunflower HVO 70% sunflower HVO 50% sunflower a (65–150 8C) 0 0 0 0. CO2 and propane decreases from 93 to 53% as the reaction temperature increases from 300 to 450 8C. The 65–150 8C fraction increases from 0. 520–1000 8C: open circles and (B) simulated distillation results for 250–380 8C. the yield of the 250–380 8C fraction decreases. This fraction is most likely alkanes ranging from C5 to C8.7 7. CO. Each data point collected after 6 h time-on-stream.00 0. At lower space velocity (5. waxes being formed each time. 150–250 8C: filled triangles.8 86 96.5 hÀ1 and 350 8C.60 30.9 0. This experiment was repeated two times with the same result.122 G.65 (520–1000 8C) 18.45 (250–380 8C) 7. 3.07 37.00 0.48 5.05 0. / Applied Catalysis A: General 329 (2007) 120–129 Fig. which are produced from the free fatty acids of the tri-glycerides. CO2 and propane.89 52. As the reaction temperature increases. nC16.82 6. These experiments showed that the reaction must be operated at conditions that do not favor wax formation.49 62. We have not been able to identify the components of the fraction from 380 to 520 8C.16 to 10. Product carbon molar yields from simulated distillation for hydrotreating of sunflower oil with NiMo/Al2O3 catalyst at LHSV 5. A reaction pathway for conversion of tri-glycerides into alkanes is shown in Fig.7 to 15. and at higher reaction temperatures the straight chain alkanes are isomerized. These intermediates are then converted into alkanes by three different pathways: decarboxylation. (A) Simulated distillation results for À50 to 60 8C: filled circles.70 26. nC16. 2A and B show the product carbon yields for n-C15. In the first step of this reaction pathway the tri-glyceride is hydrogenated and broken down into various intermediates which we presume are monoglycerides. The wax was not soluble in liquid alkanes or HVO.00 0. 60–150 8C: filled squares. This fraction is mostly (between 75 and 95%) n-C15. diglycerides and carboxylic acids. Heptadecane and octadecane are the two most abundant liquid alkanes. This fraction is primarily alkanes ranging from C9 to C14.3% as the reaction temperature increases from 300 to 450 8C.7 2. and then slightly increases to 6% as the reaction temperature is increased further to 450 8C.2 hÀ1.8 22. 1. The wax had a chemical structure similar to the tri-glyceride and free fatty acid intermediates (as determined by GCMS). which accumulated in our reactor causing reactor plugging.00 0.

No hydrogen is required to convert a carboxylic acid group to an alkane by the decarboxylation pathway. and 50 atm H2. filled circle. (2). The decarboxylation pathway involves converting a carboxylic acid into a methyl group and CO2 as shown in Eq. Fig. n-C18. Product carbon molar yields of n-C15–n-C16 alkanes (Fig. intermediates and future work is needed to better understand this reaction pathway. It is . This pathway involves bifunctional catalysis that contains sites for hydrogenation reactions (possibly NiMo sites) and for dehydration reactions (acid catalytic sites). n-C16. 2. Each data point collected after 6 h time-onstream. Huber et al. CO2. dior tri-glycerides. 2C) and isomerized and cracked products (Fig. open squares.2 hÀ1. 2B). We have used carboxylic acid to represent our feedstock and similar equations can be written for alkane production from mono-. 2D) for hydrotreating of sunflower oil with NiMo/Al2O3 catalyst at LHSV 5. 2B: filled triangle. For the sunflower oil the decarbonylation and decarboxylation liquid alkane products are primarily n-C17. Molar carbon yields in Fig. 2A). gaseous products (Fig. propane. Reaction pathway for conversion of tri-glycerides to alkanes. molar carbon yields in Fig. n-C17 and filled squares. (3). The hydrodeoxygenation pathway involves converting the carboxylic acid with hydrogen to produce an alkane and water as shown by Eq.G. RÀCH2 ÀCOOH ! RÀCH3 þ CO2 RÀCH2 ÀCOOH þ H2 ! RÀCH3 þ CO þ H2 O RÀCH2 ÀCOOH þ 3H2 ! RÀCH2 ÀCH3 þ 2H2 O (1) (2) (3) Eqs.W. filled squares. 3. filled triangles. / Applied Catalysis A: General 329 (2007) 120–129 123 Fig. (1–3) show the different pathways for alkane production with carboxylic acids as the reactant. 2A: open circles. Carbon monoxide is produced by a decarbonylation pathway where the carboxylic group is reacted with hydrogen to produce a methyl group. (1). CO and water as shown by Eq. CO. n-C15. maximum theoretical carbon yields (Fig.

Thus. . The yield of products in the 520+ 8C also decreases with temperature from 13 to 6% as the reaction temperature increases from 300 to 450 8C. This occurs when all the vegetable oil is converted into a straight chain alkane (n-C18) and propane by the hydrodeoxygenation pathway. No sulfur was detected in the vegetable oil feedstock. If straight chain alkanes are desired then the isomerization and cracking reactions should be minimized.0011 mol S/(gcat h) and 0. as the reaction temperature increases the relative rate of decarbonylation plus decarboxylation versus hydrodeoxygenation increases. However. The simulated distillation of the HVO feed is shown Table 2. Furthermore. we calculate the theoretical straight chain carbon n-C15–n-C18 yield (TSCY).2. 3. n-C18 and propane from hydrotreating the pure HVO feed are all less than 1% as shown in Fig. 4D. CO2 and H2. and at a reaction temperature of 450 8C the yields of the two products are the same. Importantly an industrial reactor must be designed so that acids do not cause corrosion problems [10]. which is due to conversion of straight chain alkanes to isomers and cracked products. the conversion of tri-glycerides to alkanes was close to 100% at 350 8C (Figs. diglycerides and monoglycerides. Under our conditions (catalysts tested for 8 h and treated before each run with H2S–H2 mixtures) no catalyst deactivation was observed. we have identified the major reaction products for hydrotreating of vegetable oils as shown in Fig. and it is likely that under long-term conditions the sulfur would leach out of the sulfided NiMo catalysts. 4C). n-C16. The branched products in the diesel range are also highly valuable. The yields of the cracked products were estimated as all products in the distillation range below 250 8C except CO. This illustrates that under hydrotreating conditions in this paper the rate of desulfurization is slower than alkane production from vegetable oils. Three different pathways produce normal alkanes: decarboxylation. The yields of the isomerized versus cracked products is shown in Fig. if pure vegetable oils were used sulfur would need to be added to the feed if sulfided catalysts are used for hydrotreating reactions. During hydrotreating. The large alkanes produced from the free fatty acids can be converted into branched isomers or cracked into smaller products. and both increase by approximately the same value with increasing temperature. n-C16. The hydrogen requirements decreases as hydrodeoxygenation > decarbonylation pathway > decarboxylation pathway. n-C17 and n-C18 divided by the maximum alkane yield that would be theoretically possible. respectively. which is ideal for diesel fuel additives.124 G. These results indicate that the rates of these two reactions are similar. free fatty acids and oxygenated intermediates to alkanes. In Fig. The sulfur conversion increases from 15 to 90% as the reaction temperature increases from 300 to 450 8C (Fig. The relative rate of the decarbonylation plus the decarboxylation versus the hydrodeoxygenation pathway can be compared by analyzing the yields of n-C17 (the decarbonylation and decarboxylation product) and n-C18 (the hydrodeoxygenation product) since tri-glyceride do not contain any odd number free fatty acids. diglycerides and monoglycerides also can form waxes in the reactor. The yields of n-C15. The molar flowrates of sulfur and tri-glycerides divided by the amount of catalysts are 0. The yields of the isomerized products were estimated as alkanes in the 250–380 8C range which were not straight chain n-C15–n-C18. which is the sum of only the n-C15. The relative rates of the decarbonylation versus decarboxylation pathway can be compared by looking at the CO and CO2 yields. and future work should focus on how to selectively produce branched isomers ranging from C15 to C18 from straight chain alkanes during the hydrotreating without cracking the alkanes to lighter products. / Applied Catalysis A: General 329 (2007) 120–129 possible that the free fatty acid intermediates are catalyzing the dehydration reaction. 2B these two yields are relatively equal. The maximum alkane yield possible from hydrotreating sunflower oil is 94%.0056 molsunflower oil/(gcat h). respectively. n-C17. 2C. The straight chain alkanes can undergo isomerization and cracking to produce isomerized and lighter alkanes. large amounts of straight chain alkanes in the diesel fuel fraction may also increase the cloud point of diesel fuel. Straight chain alkanes have a high cetane number. and these waxes can cause plugging if they are not removed or converted into alkanes.W. Huber et al. The TSCY increases from 54 to 75% as the reaction temperature increases from 300 to 350 8C. The catalytic properties and reaction conditions can be modified to produce a range of products from hydrotreating of vegetable oils. 3. Therefore. and these reactions could be occurring by a similar mechanism. and isomerization of the straight chains may be desired [10]. decarbonylation and hydrodeoxygenation pathway. In comparison. In this section. The first step in this pathway is the hydrogenation of the C C bonds of the vegetable oils. Clearly more research is needed to understand and optimize the reaction pathway. The TSCY then decreases to 36% as the reaction temperature increases to 450 8C. The yield of the À50 to 380 8C distillation fractions all increase with increasing reaction temperature. 4. The acids. This increase is due to an increase in the conversion of tri-glycerides. Hydrotreating of heavy vacuum oil HVO was hydrotreated at the same conditions as the sunflower oil and the results are shown in Fig. As shown in Fig. 2D. The optimal catalytic pathway for hydrotreating of vegetable oils is an economic question that depends on the price of hydrogen and the desired products. The relative ratio of n-C17–n-C18 increases with increasing temperature. the yield of products in the 380–520 8C distillation range only slightly decreases (from 60 to 50% as temperature increases from 300 to 450 8C) with reaction temperature. The hydrogenated vegetable oils also form free fatty acids. 1 and 2). The TSCY shows how close we are to the maximum theoretical yield of long straight chain alkanes. and as could be expected no CO or CO2 are found in the reaction products when hydrotreating HVO.

The percentage of straight chain alkanes in the 150–250 8C cut is less than 16%. 5.W.2 hÀ1. This fraction is mainly (over 40%) CO. and 50 atm H2. 4. Hydrotreating of HVO–vegetable oil mixtures Mixtures of HVO and sunflower oil ranging from 5 to 50 wt% sunflower oil were hydrotreated at reaction temperatures ranging from 300 to 450 8C.2 hÀ1. 3. Simulated distillation results from hydrotreating of mixtures of heavy vacuum oil (HVO) and sunflower oil with NiMo/Al2O3 catalyst at LHSV 5. Each data point collected after 6 h time-on-stream. Each data point collected after 6 h time-on-stream. Hydrotreating of heavy vacuum oil (HVO) with NiMo/Al2O3 catalyst at LHSV 5. The simulated distillation results for hydrotreating these mixtures are shown in Fig. CO2 and propane. The yield of the À50 to 60 8C fraction increases with increasing temperature and increasing sunflower oil content in the mixture. Huber et al. This cut also increases with increasing temperature when the mixture contains less than 30 wt% Fig. 5.3.G. The yields of the other two low boiling cuts (65–150 and 150–250 8C) also increase with temperature. / Applied Catalysis A: General 329 (2007) 120–129 125 Fig. and 50 atm H2. . but does increase with increasing vegetable oil content. The yield of the 250–380 8C fraction (which is the fraction containing n-C15–n-C18) increases with increasing sunflower oil content. and only slightly increase with increasing content of sunflower oil.

and then decreases as the reaction temperature increases to 450 8C. 10 shows the HDS activity of different sunflower oil– HVO mixtures.W. Thus. The vegetable oil in our case had a significantly higher activity for alkane production than the rate of desulfurization. The majority of these products are produced from vegetable oils. The TAN of the products obtained at 300 8C reaction temperature increases with sunflower oil content. CO2. except for n-C17 and n-C18. 3. the acidity of the products should also be minimized to meet fuel specifications. The n-C17 and n-C18 yields for the 15 wt% sunflower oil feed initially increase as the reaction temperature increases from 300 to 350 8C followed by a decreases as the reaction temperature further increases. The addition of sunflower oil does not decrease the HDS activity for HVO feeds. Fig. then the catalyst should be adjusted. At a reaction temperature of 350 8C the yield of the 500+ 8C fraction decreases with increasing vegetable oil content. but it does cause a dilution effect which would have to be compensated under industrial conditions by increasing the reactor flow-rate.11]. and 50 atm H2. This indicates that the vegetable oils (and vegetable oil products) should have a shorter residence time than the HVO feed. Dilution of the sunflower oil with HVO increases the TSCY from 70 to 85% as the HVO feed concentration increases from 50 to 95 wt%. The TSCY could probably be improved further by increasing the space velocity of the tri-glycerides as at 350 8C all triglycerides appear to be converted. 7 that shows the yields for CO. The TSCY for the sunflower oil–HVO mixtures is a function of both reaction temperature and concentration of sunflower oil as shown in Fig. Huber et al. If straight chain alkanes are the desired product then the cracking and isomerization reactions of the alkanes should be minimized. the sulfur content of the petroleum feedstock. the yield of the heaviest fraction increases with increasing sunflower oil concentration. Thus. The yields of these products increase with increasing vegetable oil concentration in the feed. mg KOH/g oil). Therefore. sunflower oil. 6. The decreases in the yield of this cut with increasing sunflower oil concentration is mainly due to a dilution effect of the sunflower oil. Thus. The yield of all products in Fig. The selectivity to decarbonylation/ decarboyxlation products increases with temperature and increasing sunflower oil content. Each data point collected after 6 h time-onstream. To analyze the effect of dilution on the relative rate of decarbonylation/decarboxylation versus hydrodeoxygenation pathways. again we see that the HVO changes the product selectivity of the sunflower oil products. / Applied Catalysis A: General 329 (2007) 120–129 Fig. as shown in Fig. increases with reaction temperature. Optimal conditions for co-feeding of vegetable oils with petroleum feedstocks Typical operation of hydrotreating reactors involves increasing the reaction temperature as the catalyst activity decreases [10. The TSCY increases as the reaction temperature increases from 300 to 350 8C for all feeds containing sunflower oil. For the mixture with 50 wt% sunflower oil this fraction increases as the reaction temperature initially increases from 300 to 350 8C.126 G. Total acidity number (TAN) for hydrotreating of mixtures of heavy vacuum oil (HVO) and sunflower oil mixtures with NiMo/Al2O3 catalyst at LHSV 5. 6 shows the acidity of the various products defined as total acidity number (TAN. The yield of the 380–520 8C fraction decreases with increasing reaction temperature and increasing sunflower oil concentration. 9. vegetable oils may be injected into the reactor after the HVO. the vegetable oil should be injected into the hydrotreating reactor at different locations depending on reaction temperature. The injection location of the vegetable oils should be chosen so that all free fatty acids are converted to alkanes. The 520+ 8C fraction mostly contains the sunflower oil and free fatty acids (Table 2). Catalysts and reaction conditions also influence . 7. Fig. All feeds appear to go through a maximum at a reaction temperature of 350–400 8C. due to an increase in the conversion of tri-glycerides. This distilled fraction mainly contains products in HVO. and isomerized/cracked alkanes from vegetable oils may be an important component of jet fuel in the future. propane and the straight chain alkanes ranging from C8 to C18. If isomerization or cracked products are desired. This indicates the hydrotreating of sunflower oil and hydrodesulfurization probably occur on different catalytic sites.4. and the concentration of vegetable oil. At sunflower oil concentrations of 5 and 10 wt% the n-C17 and nC18 yields increase as the reaction temperature increases (from 300 to 400 8C) with only a slight drop when the reaction temperature increases to 450 8C. due to an increase in the free fatty acids. we define the decarbonylation/decarboxylation selectivity as the yields of the decarbonylation/ decarboxylation alkane products (n-C15 and n-C17) divided by the yields of the hydrodeoxygenation (n-C16 and n-C18) plus decarbonylation/decarboxylation (n-C15 and n-C17) alkane products. and this injection point will depend on temperature.2 hÀ1. At a reaction temperature of 300 8C. This can be deduced from results in Fig. and the alkane products are minimized. As the reaction temperature increases fatty acids are converted into alkanes and consequently the TAN decreases. In addition. dilution of the vegetable oil with HVO can positively influence the reaction chemistry of hydrotreating of vegetable oils. Importantly sunflower oil addition does not decrease the rate of HDS. 8.

which need to be explored in more detail in the future. and can increase the yield (based on theoretical yield) to straight chain alkanes. The hydrodeoxygenation route requires more hydrogen. 7. the yield of the decarbonylation. Product yields for hydrotreating of heavy vacuum oil–sunflower oil mixtures with NiMo/Al2O3 catalyst at LHSV 5. / Applied Catalysis A: General 329 (2007) 120–129 127 Fig. Huber et al. Diluting the vegetable oil with the HVO has a strong influence on the product chemistry. and 50 atm H2.G. decarboxylation and hydrodeoxygenation pathways.2 hÀ1. It is probable that the most realistic scenario for hydrotreating of HVO–vegetable oil mixtures is to add small amounts of vegetable oils (ranging from 5 to 10 wt%) to the HVO. Each data point collected after 6 h time-on-stream. vegetable oil. and the desirable route will depend on the price of hydrogen.W. subsidies and reaction product. This .

Percentage of maximum yield of n-C15–n-C18 for hydrotreating mixtures of HVO and sunflower oil with NiMo/Al2O3 catalyst at LHSV 5. and 50 atm H2. The straight chain alkanes can undergo isomerization and cracking to produce lighter and isomerized alkanes. at 350 8C the sunflower oil conversion was 100% in comparison the sulfur conversion was 41% at this temperature. The selectivity to the decarbonylation plus decarboxylation products (as compared to the hydrodeoxygenation pathway) increases with increasing temperature. The straight chain alkanes can undergo isomerization and cracking to produce lighter and isomerized alkanes. 10. Fig. The selectivity to decarbonylation plus decarboxylation products increases with increasing temperature and sunflower oil content (for the HVO–sunflower oil mixture). Importantly dilution with HVO will decrease the acidity in the reaction intermediates. Dilution of the vegetable oils with HVO increases the yield of straight chain alkanes. Desulfurization is significantly slower than alkane production from vegetable oils under standard hydrotreating conditions. which can accumulate in the reactor and cause plugging. unless they are converted into alkanes. For example. and 50 atm H2. and 50 atm H2.2 hÀ1. Effect of temperature and mixing of vacuum gas-oil with sunflower on decarbonylation plus decarboxylation selectivity (yields of n-C15 + n-C17/(nC15 + n-C16 + n-C17 + n-C18)*100) with NiMo/Al2O3 catalyst at LHSV 5. Fig. and the straight chain alkanes have high cetane number. 8. In conclusion. Each data point collected after 6 h time-on-stream. Conclusion The general conclusions of this work are that vegetable oils and vegetable oil–HVO mixtures can be converted into liquid alkanes by hydrotreating with standard hydrotreating catalysts. Sulfur conversion for hydrotreating of heavy gas-oil–sunflower mixtures with NiMo/Al2O3 catalyst at LHSV 5.2 hÀ1. This dilution does not decrease the rate of desulfurization (under the conditions in this study). Waxes can also form under reaction conditions. We believe these conclusions can be extrapolated to the use of the other vegetable oils. this study has indicated hydrotreating of vegetable oils is a promising technology for production of liquid biofuels.128 G. Mixing the sunflower oil with HVO does not decrease the rate of desulfurization. Huber et al. and for a 5 wt% sunflower oil–95 wt% HVO feed the maximum theoretical straight chain C15–C18 yield from the sunflower oil was higher (87%) than it was with the pure sunflower oil (75%). but will require that the HVO space velocity be increased if the reactor is to have the same throughput. We have obtained a yield of straight chain C15–C18 alkanes of 71% on a carbon basis (which is 75% of the maximum theoretical yield for these products) for hydrotreating of pure vegetable oil.W. Organic acids produced in the hydrotreating process may catalyze the isomerization and cracking reactions. Each data point collected after 6 h time-on-stream. Fig. it is also possible to hydrotreat vegetable oils with petroleum feedstocks like HVO. . It is likely that further advances will be made as this chemistry is understood in more detail and improved catalysts are developed. Each data point collected after 6 h time-on-stream. 4. The reaction pathway involves hydrogenation of the C C bonds of the vegetable oils followed by alkane production by three different pathways: decarbonylation. This effect is probably due to a dilution of the free fatty acids which may cause polymerization and cracking reactions. 9. As shown in this paper. The products produced are already in diesel fuel.2 hÀ1. This has the advantage of using existing petroleum refineries for biofuels production without the need to purchase additional capital equipment. / Applied Catalysis A: General 329 (2007) 120–129 would allow refineries to quickly meet government mandates on using biofuels. decarboxylation and hydrodeoxygenation (or dehydration/ hydrogenation).

L. / Applied Catalysis A: General 329 (2007) 120–129 129 Acknowledgements The authors thank Ruth Sanchis for performing catalytic tests. Champaign. Lopez. C. McCall. Ed. Liu.com/ (access year 2007). Jerosky. News 83 (2005) 19. Conversion of biomass feedstock to diesel fuel additive assigned to natural resources Canada.605 (1991). Czernik. [10] R. Y. Wong. Krawczyk. M. Science 251 (1991) 1318. Huber et al. Lotero. Chapman & Hall. US Patent 4. [6] E. [9] G. Mackowiak. [12] W.W. L.R. Marinangeli. http://www. Huber.E. UOP (2006). Klass. Farrauto. Reagan. [11] R. D. J. Thanks are also given at MAT200614274-C02-01 for financial support. R. Technol. Iborra. [7] M. IL. Biomass for Renewable Energy. [13] J.722 (1998).V. McCoy. Knothe.. Suwannakarn. London. UK. S. Soveran. A. Monnier. Bartholomew. 1997. [3] L. Nemeth. Academic Press. A. Stumborg. J. 1998. Petri. Appl. Huber. Opportunities for Biorenewables in Oil Refineries. The Biodiesel Handbook. J. Shonnard. Stumborg. Wyman. Nichols. .A. Neste Oil (2006). E. B.W. 106 (2006) 4044. 44 (2005) 5353.E. [5] G. San Diego. J. US Patent 5. K. Res.W. Biotechnol. in press. AOCS Press. J. Chem. Eng. O’Connor. A. [14] M. Wong.992. Ind.N. T. Catal. Chem. [15] Neste Oil. Chem. Huber.W. Biochem. Rev. Corma. E. [8] A. Craig. Elliott. J. [2] D. G.K. D.L. References [1] G. D. and to BIOeCON for supporting the work and giving permission for publication. T. M. D.W. G.nesteoil. Goodwin. Tourigny. 45–46 (1994) 897. 2005.J. Fuels and Chemicals. Kalnes. Krahl.G. D.E. Corma. D. Hogan. Corma. Chem. Cushman. Hogan. 247 (2007) 307. B. S. Introduction to Industrial Catalytic Processes. Production of hydrocarbons with a relatively high cetane rating. Wyman. DOE Award #DE-FG36-05GO15085.H.J. Eng. A.G. Lynd.705. Bioresour. Angew. Soveran. P. 56 (1996) 13. Bruce.W. Marker. D. [4] C. C. Int. M. Gerpen. Sauvanaud.