Abstract:
Disclosed is a catalyst including metal phosphide for preparation of biodiesel, and a method of preparing biodiesel from feedstock comprising vegetable oil through hydrotreating using the catalyst. When the catalyst including metal phosphide is used as a catalyst for preparation of biodiesel, preparation activity of hydrotreated biodiesel is high even without continuous supply of sulfiding agent, and hydrotreating and isomerization reactions occur at the same time, thus obtaining high-quality hydrotreated biodiesel having a low pour point.

Description:
RELATED APPLICATIONS 
       [0001]    This is a §371 of International Application No. PCT/KR2010/002016, with an international filing date of Apr. 1, 2010 (WO 2010/114323, published Oct. 7, 2010), which is based on Korean Patent Application No. 10-2009-0028222 filed Apr. 1, 2009 and Korean Patent Application No. 10-2010-0028284 filed Mar. 30, 2010, the subject matter of which is incorporated herein by reference. 
     
    
     TECHNICAL FIELD 
       [0002]    The present disclosure relates to a catalyst including metal phosphide for preparing biodiesel and a method of preparing biodiesel using the same. 
       BACKGROUND 
       [0003]    With the continuation of high oil prices, the need for the development of alternative energies and the reduction of greenhouse gases has come to the forefront all over the world, and thus the development of bioenergy resources is under thorough study. Further, while domestic and foreign supplies of biodiesel increase depending on taxation and legislation all over the world, bioenergy-related markets have maintained a high growth rate of 8˜12% per year. 
         [0004]    A technique for preparing a diesel fraction from biomass is typically represented by preparation of FAME (Fatty Acid Methyl Ester). FAME is because it is alternative energy obtained from biomass, and, from the point of physical properties, its cetane number is higher than that of a diesel fraction obtained from conventional mineral oil. However, FAME has drawbacks such as poor oxidative stability and high preparation cost. 
         [0005]    In next-generation technology, there is proposed hydrotreated biodiesel (HBD) resulting from direct hydrotreating of a triglyceride. Although HBD has a higher production cost than that of diesel obtained from conventional mineral oil, it has lower production cost and imparts relatively high oxidative stability through hydrotreating, compared to conventional FAME. 
         [0006]    Also, HBD is capable of producing high-graded diesel oil having a cetane number approximate to 100, and is very in terms of energy efficiency or reduction of greenhouse gases, compared to mineral oil or FAME. 
         [0007]    The process of preparing HBD is largely classified into two, one of which is composed exclusively of hydrotreating, and the other of which is composed of hydrotreating and then isomerization. 
         [0008]    The ‘hydrotreating’ of the HBD indicates a process for converting fat or fatty acid into hydrocarbons through a reaction using hydrogen, and analogous terms thereof include hydrogenation, deoxygenation, hydrodeoxygenation, decarboxylation, and decarbonylation. As such, decarboxylation and decarbonylation cause hydrotreating while eliminating a carbon atom from fat or fatty acid of a feed, and are thus used as the term analogous to hydrotreating in the preparation of HBD. 
         [0009]    Vegetable oil, generally used as a feed for preparing biodiesel, consists of triglyceride. When triglyceride in an ester form is hydrotreated, a C 15 ˜C 18  paraffinic material is obtained. This material may be used as biodiesel because its boiling point belongs to the diesel range. 
         [0010]    However, the HBD which is paraffinic biodiesel undesirably has a high pour point. The pour point indicates the minimum temperature at which the flow of fuel is possible. Typically, if the pour point is high, there occurs a problem in which a feed cannot be maintained in a liquid state at a relatively low temperature. In the case of HBD which is paraffinic diesel, it has high pour point and therefore exhibits flow properties at low temperature inferior to that of FAME or mineral oil obtained from petroleum. The problem caused by the flow properties at low temperature is regarded as insignificant in high-temperature regions including South-East Asia where a feed is easy to obtain and the application of HBD is favorable, but must be solved in low-temperature regions including Europe or North America. 
         [0011]    Methods for solving the above problem have been two to date. One method is the addition of a small amount of biodiesel to mineral oil. In this case, biodiesel is dispersed in mineral oil, and thus high pour point problems of biodiesel may be solved to some degree. However, because the threshold amount of biodiesel to be added depending on the temperature is preset, an amount exceeding the standard amount cannot be added. The other method is to increase the pour point through isomerization. This method converts a paraffinic hydrocarbon into a hydrocarbon having many branches, thus decreasing the pour point. Thereby, biodiesel having the pour point equal to that of mineral oil may be prepared. In this case, however, high equipment cost is required, and also, because isomerization is a hydrotreating process, it demands a high maintenance cost. 
         [0012]    The other problem in the preparation of HBD is that sulfiding agent should be added to continuously maintain the active state of the catalyst. The catalyst for HBD is a conventional hydrotreating catalyst which is mainly provided in the form of a group VIB-VIII metal compound. The active sites of this catalyst have a mixture structure of VIB-VIII-sulfur/support. Because sulfur is continuously eliminated during the reaction, sulfur must be continuously supplied so that the active sites are maintained. 
         [0013]    In a conventional hydrotreating process, the feed itself contains sulfur, and thus the activity of the catalyst may be maintained even without additional use of sulfiding agent. However, in the preparation of HBD, because the vegetable oil used as a feed contains not sulfur but oxygen, the catalyst may be easily deactivated by reaction with oxygen. 
         [0014]    To overcome this problem, not more than 1% of a sulfur compound such as dimethyl disulfide (DMDS) may be mixed with the feed and then treated, or a sulfur-containing hydrocarbon may be mixed with the feed and then treated. 
         [0015]    In regard to the conventional preparation of HBD, U.S. Pat. No. 4,992,605 discloses a process of preparing biodiesel from crude palm oil using CoMo, NiMo or a transition metal as a commercially available hydrotreating catalyst. 
         [0016]    US 2007/0175795 discloses the use of Ni, Co, Fe, Mn, W, Ag, Au, Cu, Pt, Zn, Sn, Ru, Mo, Sb, V, Ir, Cr, or Pd as a component of a catalyst for hydrotreating triglyceride. 
         [0017]    U.S. Pat. No. 7,232,935 discloses a process of preparing HBD from vegetable oil through hydrotreating and then isomerization in that order using a catalyst. 
         [0018]    U.S. Pat. No. 7,279,018 discloses the preparation of a product by mixing HBD which is hydrotreated and then isomerized with about 0˜20% of an oxygen-containing component. 
         [0019]    Also, in US 2007/0010682, hydrotreating and isomerization are performed, using a feed containing 5 wt % or more of free fatty acid and a diluent, in which the ratio of diluent to feed is set to 5˜30:1. 
         [0020]    In US 2006/0207166, hydrotreating and isomerization are performed in a single step, using a catalyst obtained by supporting an active metal for a hydrotreating reaction on a support having an isomerization function such as zeolite. 
         [0021]    As mentioned above, in the production of HBD to date, the conventional hydrotreating catalyst which is commercially available may be employed in a state of being unchanged or improved, without requiring a specified hydrotreating catalyst. 
       SUMMARY 
       [0022]    Therefore, the present disclosure has been made keeping in mind the problems encountered in the related art and provides a catalyst including metal phosphide for preparation of high-quality biodiesel having a low pour point through only a hydrotreating process without additional isomerization process, while exhibiting high hydrotreating activity even without the addition of sulfiding agent. 
         [0023]    Also, the present disclosure provides a method of preparing biodiesel using the above catalyst. 
         [0024]    Also, the present disclosure provides biodiesel prepared using the above method. 
         [0025]    An aspect of the present disclosure provides a catalyst for preparation of biodiesel, including metal phosphide as an active component for hydrotreating or isomerization. 
         [0026]    In one embodiment, the metal phosphide as an active metal may be obtained by binding a group VIB metal, a group VIII metal, a group VIIB metal or a mixture thereof with P. 
         [0027]    In another embodiment, the catalyst may composed exclusively of the metal phosphide, or may further include as a support or a binder, carbon, an alkali earth metal oxide, an alkali metal oxide, alumina, silica, silica-alumina, zirconia, titania, silicon carbide, niobia, aluminum phosphate or a mixture thereof. 
         [0028]    In one embodiment, the metal phosphide obtained by binding the group VIB metal with P may include MoP or WP in which an amount of Mo or W is 1˜90 wt % and an amount of P is 10˜99 wt %. 
         [0029]    In one embodiment, the metal phosphide obtained by binding the group VIII metal with P may include Ni 2 P, PdP or PtP in which an amount of Ni, Pd or Pt is 1˜90 wt % and an amount of P is 10˜99 wt %. 
         [0030]    In one embodiment, the metal phosphide obtained by binding the group VIIB metal with P may include Co 2 P, RuP, FeP or MnP in which an amount of Co, Ru, Fe or Mn is 1˜90 wt % and an amount of P is 10˜99 wt %. 
         [0031]    In one embodiment, the catalyst containing P may include NiMoP, CoMoP, CoNiMoP, CoNiP, NiWP, CoWP, CoNiWP, or MoWP, in which an amount of the active metal is 1˜95 wt % and an amount of P is 5˜99 wt %. 
         [0032]    In one embodiment, an amount of the group VIB metal, the group VIII metal, the group VIIB metal or a mixture thereof is 1˜100 wt % based on support. 
         [0033]    Another aspect of the present disclosure provides a method of preparing biodiesel through hydrotreating or isomerization using the above catalyst. 
         [0034]    In one embodiment, in the method, the biodiesel may be prepared using, as a feed, biomass of vegetable oil, vegetable fat, animal fat, fish oil, recycled fat, vegetable fatty acid, animal fatty acid or a mixture thereof. 
         [0035]    In one embodiment, as such, the fat may include fat consisting of triglycerides each chain of which has 1˜28 carbon atoms, and the fatty acid may include fatty acid having 1˜28 carbon atoms. 
         [0036]    In another embodiment, in the method, the biodiesel may be prepared using, as the feed, a mixture of the biomass and 0˜99% of at least one hydrocarbon. 
         [0037]    In one embodiment, as such, the hydrocarbon may include kerosene, diesel, LGO, and recycled hydrotreated biodiesel. 
         [0038]    In another embodiment, the method further comprise pretreating the feed through hydrotreating, performing hydrodeoxygenation thus separating unreacted hydrogen, and cooling and separating produced hydrocarbon. 
         [0039]    A further aspect provides biodiesel prepared through the above method. 
         [0040]    According to the present disclosure, the catalyst for biodiesel can maintain high hydrotreating activity for a long period of time without the use of sulfiding agent, and can produce high-quality biodiesel having a low pour point while exhibiting extended high activity through only a hydrotreating process. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0041]      FIG. 1  shows a process of preparing HBD using 100% vegetable oil as a feed; and 
           [0042]      FIG. 2  shows a process of preparing HBD using a mixture composed of vegetable oil and hydrocarbon as a feed. 
       
    
    
     DETAILED DESCRIPTION 
       [0043]    Hereinafter, a detailed description will be given of the present disclosure. 
         [0044]    The present disclosure relates to a catalyst including metal phosphide for preparation of biodiesel through hydrotreating. 
         [0045]    As catalyst including metal phosphide, the catalyst may be used in form of metal phosphide alone, or in form of supporting the metal phosphide using support or binder. 
         [0046]    The catalyst including metal phosphide according to the present disclosure can maintain high hydrotreating activity for a long period of time even without the use of sulfiding agent, and also can reduce the pour point of HBD through only a hydrotreating process without performing an isomerization process. 
         [0047]    Therefore, the catalyst including metal phosphide according to the present disclosure may be applied not only to the HBD preparation process but also to the hydrotreating process in the absence of sulfuide. The catalyst including metal phosphide according to the present disclosure may be applied not only to the HBD preparation process but also to any process of reducing the pour point of a product obtained through hydrotreating. 
         [0048]    The metal phosphide which is an active component used in the present disclosure is obtained by binding P to a group VIB, VIII or VIIB metal or a mixture thereof as an active metal. 
         [0049]    The present disclosure can increase the acid sites of the metal by introducing the phosphide and thus increase the reaction efficiency for hydrotreating and also for isomerization in the preparation of biodiesel. 
         [0050]    Examples of the metal phosphide include but are not limited to MoP and WP in which the group VIB metal and P are bound, Ni 2 P, PdP and PtP in which the group VIII metal and P are bound, and Co 2 P, RuP, FeP and MnP in which the group VIIB metal and P are bound. 
         [0051]    Specific examples of the metal phosphide used in the present disclosure include MoP, NiMoP, CoMoP, CoNiMoP, CoNiP, Ni 2 P, Co 2 P, WP, NiWP, CoWP, CoNiWP and so on. 
         [0052]    In the present disclosure, the metal phosphide composed of a group VIB metal and P bound together includes 1˜90 wt % of the active metal. If the amount of the active metal is less than 1 wt %, the activity of the catalyst is very low and thus the catalyst does not function. In contrast, if the amount thereof exceeds 90 wt %, the preparation of the catalyst is impossible. 
         [0053]    The catalyst used in the present disclosure may be composed of metal phosphide or may be composed of a support or a binder and metal phosphide supported thereon. The support or binder may be carbon, an inorganic metal oxide, and mixtures thereof. Also, the inorganic metal oxide may be an alkali earth metal oxide, an alkali metal oxide, alumina, silica, silica-alumina, zirconia, titania, silicon carbide, niobia, aluminum phosphate and mixtures thereof. 
         [0054]    The metal phosphide composed of a group VIB, VIII or VIIB metal and P bound together includes 1˜90 wt % of the active metal. If the amount of the active metal is less than 1 wt %, the activity of the catalyst is very low and thus the catalyst does not function. In contrast, if the amount thereof exceeds 90 wt %, the preparation of the catalyst is impossible. 
         [0055]    In the present disclosure, the biodiesel may be prepared using, as a feed, biomass of vegetable oil, vegetable fat, animal fat, fish oil, recycled fat, vegetable fatty acid, animal fatty acid or mixtures thereof. 
         [0056]    As such, the fat may include fat consisting of triglycerides each chain of which has 1˜28 carbon atoms, and the fatty acid may include fatty acid having 1˜28 carbon atoms, but the present disclosure is not limited thereto. 
         [0057]    Alternatively, the biodiesel may be prepared using, as the feed, a mixture of the biomass and at least one hydrocarbon (0˜99%). Examples of the hydrocarbon include but are not limited to kerosene, diesel, LGO, and recycled HBD. 
         [0058]    The HBD preparation process may include a series of procedures for pretreatment of the feed through hydrotreating, hydrodeoxygenation thus separating unreacted hydrogen, and cooling and separation of produced hydrocarbon. As such, one or two steps may be added or omitted depending on predetermined purposes. 
         [0059]    The HBD preparation process using 100% vegetable oil as the feed is shown in  FIG. 1 , but the present disclosure is not limited thereto. 
         [0060]      FIG. 2  shows the HBD preparation process using a mixture of vegetable oil and hydrocarbon as the feed. This process is different from the process using 100% vegetable oil in that a fractionator for separating hydrocarbon is provided. 
         [0061]    The mixture of vegetable oil and 1% DMDS, serving as the feed, and hydrogen may be simultaneously supplied into a HBD reactor so that they are hydrotreated. The reaction mixture thus obtained may be distilled using a stripper and fractionated depending on boiling points, thus extracting only HBD. The other materials are recycled. 
         [0062]    Below, the specified catalyst for HBD according to the present disclosure and the method of preparing biodiesel from biomass through hydrotreating using the same are described in detail. 
       EXAMPLE 1 
     Preparation of MoP/ZrO 2  Catalyst 
       [0063]    A catalyst composed of about 5 wt % of Mo and about 3 wt % of P using a ZrO 2  support having a diameter of 1 mm was prepared. 
         [0064]    As a Mo precursor, ammonium heptamolybdate tetrahydrate (hereinafter, AHM) was used, and as a P precursor ammonium phosphate (hereinafter, AP) was used. 
         [0065]    AP and AHM were dissolved in distilled water, supported on the ZrO 2  support, dried at 150° C. for 2 hours, and continuously burned at 500° C. for 2 hours, thus preparing MoP/ZrO 2 . 
         [0066]    In addition to AHM as the Mo precursor, molybdenum acetate, molybdenum chloride, molybdenumhexacarbonyl, phosphomolybdic acid, molybdic acid and so on may be used, but the present disclosure is not limited thereto. Also, the P precursor is not limited to AP, and examples thereof may include phosphorous acid, red phosphorus, yellow phosphorus and so on. 
         [0067]    Then, a cylindrical reactor was packed with 6 cc of the catalyst thus obtained, after which the temperature thereof was increased to 650° C. while allowing H 2  to flow at a rate of 200 cc/min under conditions of room temperature and a pressure of 30 bar. When the temperature reached 650° C., pretreatment was performed for 2 hours. 
         [0068]    Using the pretreated MoP/ZrO 2  catalyst, under conditions of a reaction temperature of 320° C., a reaction pressure of 30 bar and H 2  supplied at 100 cc/min, a feed composed of 100% soybean oil was allowed to react at a rate of 0.1 cc/min (LHSV=1). The sampling was performed every 8 hours. The properties of the resultant reaction product were analyzed through SimDist, the leaching of the catalyst was analyzed through ICP, and the degree of isomerization was analyzed through GC. 
       EXAMPLE 2 
     Preparation of Ni 2 P/ZrO 2  Catalyst 
       [0069]    A catalyst composed of about 6 wt % of Ni and about 3 wt % of P using a ZrO 2  support having a diameter of 1 mm was prepared. As a Ni precursor, nickel nitrate (hereinafter, NN) was used, and as the P precursor, Ammonium phosphate (hereinafter, AP) was used. 
         [0070]    The Ni metal is not provided only in the form of NN, but various precursors such as nickel acetate, nickel acetylacetonate, nickel chloride, nickel hydroxide, nickel oxalate and so on may be used. 
         [0071]    The Ni 2 P/ZrO 2  catalyst was prepared through the following procedures. 
         [0072]    First, NN and AP were dissolved in distilled water, supported on the ZrO 2  support, dried at 150° C. for 2 hours, and continuously burned at 500° C. for 2 hours, thus preparing Ni 2 P/ZrO 2 . 
         [0073]    The pretreatment and reaction were performed under the same conditions as in Example 1, and analysis was carried out as in Example 1. 
       EXAMPLE 3 
     Preparation of WP Catalyst 
       [0074]    Without use of the support, a WP powder catalyst composed of W and P at a molecular ratio of 1:1 was prepared. As a W precursor, ammonium metatungstate (hereinafter, AMT) was used, and as the P precursor, ammonium phosphate (hereinafter, AP) was used. 
         [0075]    The W metal is not provided only in the form of AMT, but various precursors such as tungsten hexacarbonyl, tungsten chloride and so on may be used. 
         [0076]    The WP catalyst was prepared through the following procedures. 
         [0077]    First, AMT and AP were dissolved in distilled water, mixed at a molecular ratio, dried and continuously burned at 500° C. for 6 hours. 
         [0078]    The pretreatment and reaction were performed under the same conditions as in Example 1, and analysis was carried out as in Example 1. 
       EXAMPLE 4  
     Preparation of NiMoP/ZrO 2  Catalyst 
       [0079]    Using a ZrO 2  support having a diameter of 1 mm, a catalyst composed of about 5 wt % of Mo, about 5 wt % of Ni and about 3 wt % of P was prepared. As the Mo precursor, ammonium heptamolybdate tetrahydrate (hereinafter, AHM) was used, as the Ni precursor, Nickel nitrate (hereinafter, NN) was used, and as the P precursor, ammonium phosphate (hereinafter, AP) was used. 
         [0080]    First, AHM and AP were dissolved in distilled water, supported on the ZrO 2  support, dried at 150° C. for 2 hours, and continuously burned at 500° C. for 2 hours, thus preparing a MoP/ZrO 2  catalyst. 
         [0081]    Then, NN was dissolved in distilled water, supported on the MoP/ZiO 2  catalyst, dried at 150° C. for 2 hours, and continuously burned at 500° C. for 2 hours, thus preparing a NiMoP/ZrO 2  catalyst. 
         [0082]    The pretreatment and reaction were performed under the same conditions as in Example 1, and analysis was carried out as in Example 1. 
       EXAMPLE 5  
     Preparation of MoP/Al 2 O 3  Catalyst 
       [0083]    Using an Al 2 O 3  support having a diameter of 1 mm, a catalyst composed of about 5 wt % of Mo and about 3 wt % of P was prepared. As the Mo precursor, ammonium heptamolybdate tetrahydrate (hereinafter, AHM) was used, and as the P precursor, ammonium phosphate (hereinafter, AP) was used. 
         [0084]    The MoP/Al 2 O 3  catalyst was prepared through the following procedures. 
         [0085]    First, AHM and AP were dissolved in distilled water, supported on the Al 2 O 3  support, dried at 150° C. for 2 hours, and continuously burned at 500° C. for 2 hours, thus preparing the MoP/Al 2 O 3  catalyst. 
         [0086]    The pretreatment and reaction were performed under the same conditions as in Example 1, and analysis was carried out as in Example 1. 
       EXAMPLE 6 
     Reaction of Mixed Feed (80% Kero-20% Soybean Oil) using MoP/ZrO 2 Catalyst 
       [0087]    A MoP/ZrO 2  catalyst was prepared in the same manner as in Example 1. 
         [0088]    As a feed for preparation of HBD, a feed mixed with hydrocarbon (80% kero-20% soybean oil) was used. The pretreatment and reaction were performed under the same conditions as in Example 1. 
       EXAMPLE 7 
     Supply of Sulfur Compound in MoP/ZrO 2  Catalyst 
       [0089]    A MoP/ZrO 2  catalyst was prepared in the same manner as in Example 1. 
         [0090]    A cylindrical reactor was packed with 6 cc of the MoP/ZrO 2  catalyst, after which a mixed solution of R-LGO and 3% DMDS was supplied at a rate of 0.04 cc/min and the temperature was increased to 400° C. while allowing H 2  to flow at a rate of 16 cc/min under room temperature and a pressure of 45 bar. When the temperature reached 400° C., pretreatment was performed for 3 hours. 
         [0091]    Using the MoP/ZrO 2  catalyst thus pretreated, under conditions of a reaction temperature of 350° C., a reaction pressure of 30 bar and H 2  supplied at 100 cc/min, a feed composed of 1% DMDS-containing soybean oil was allowed to react at a rate of 0.1 cc/min (LHSV=1). The sampling was performed every 8 hours. The properties of the resultant reaction product were analyzed through SimDist, and the leaching of the catalyst was analyzed through ICP. 
       EXAMPLE 8 
     Supply of Sulfur Compound in CoMoP/TiO 2  Catalyst 
       [0092]    Using a TiO 2  support having a diameter of 1 mm, a catalyst composed of about 5 wt % of Mo and about 3 wt % of P was prepared in the same manner as in Example 1. 
         [0093]    As the Mo precursor, ammonium heptamolybdate tetrahydrate (hereinafter, AHM) was used, and as the P precursor, ammonium phosphate (hereinafter, AP) was used. 
         [0094]    Supported on the MoP/TiO 2  catalyst was 5 wt % of Co. The Co precursor was cobalt nitrate hexahydrate (hereinafter, CNH). 
         [0095]    The Co metal is not provided only in the form of CNH, but cobalt acetate, cobalt carbonate, cobalt chloride, cobalt phosphate and so on may be used. 
         [0096]    CNH was dissolved in distilled water, after which CoMoP/TiO 2  was prepared, dried at 150° C. for 2 hours, and continuously burned at 500° C. for 2 hours, giving CoMoP/TiO 2 . 
         [0097]    A cylindrical reactor was packed with 6 cc of the catalyst thus obtained, after which the temperature thereof was increased to 650° C. while allowing H 2  to flow at a rate of 200 cc/min under conditions of room temperature and a pressure of 30 bar. When the temperature reached 650° C., pretreatment was performed for 2 hours. 
         [0098]    Using the CoMoP/TiO 2  catalyst thus pretreated, under conditions of a reaction temperature of 320° C., a reaction pressure of 30 bar and H 2  supplied at 100 cc/min, a feed composed of 100% soybean oil was allowed to react at a rate of 0.1 cc/min (LHSV=1). The sampling was performed every 8 hours. The properties of the resultant reaction product were analyzed through SimDist, the leaching of the catalyst was analyzed through ICP, and the degree of isomerization was analyzed through GC. 
       COMPARATIVE EXAMPLE 1 
     Preparation of NiMo/Al 2 O 3  Catalyst 
       [0099]    Using an Al 2 O 3  support having a diameter of 1 mm, a catalyst composed of about 10 wt % of Mo and about 3 wt % of Ni was prepared. As the Mo precursor, ammonium heptamolybdate tetrahydrate (hereinafter, AHM) was used, and as the Ni precursor, nickel nitrate hexahydrate (hereinafter, NNH) was used. 
         [0100]    The NiMo/Al 2 O 3  catalyst was prepared through the following procedures. 
         [0101]    First, AHM was dissolved in distilled water, supported on the Al 2 O 3  support, dried at 150° C. for 2 hours, and continuously burned at 500° C. for 2 hours, thus preparing a Mo/Al 2 O 3  catalyst. 
         [0102]    Then, 3.06 g of NNH was dissolved in distilled water, supported on the Mo/Al 2 O 3  catalyst, dried at 150° C. for 2 hours, and continuously burned at 500° C. for 2 hours, thus preparing the NiMo/Al 2 O 3  catalyst. 
         [0103]    A cylindrical reactor was packed with 6 cc of the catalyst thus obtained, after which a mixed solution of R-LGO and 3% DMDS was supplied at a rate of 0.04 cc/min and the temperature was increased to 400° C. while allowing H 2  to flow at a rate of 16 cc/min under conditions of room temperature and a pressure of 45 bar. When the temperature reached 400° C., pretreatment was performed for 3 hours. 
         [0104]    Using the NiMo/Al 2 O 3  catalyst thus pretreated, under conditions of a reaction temperature of 350° C., a reaction pressure of 30 bar and H 2  supplied at 100 cc/min, a feed composed of 1% DMDS-containing soybean oil was allowed to react at a rate of 0.1 cc/min (LHSV=1). After 7 days, 1% DMDS supplied together with soybean oil was cut, and 100% soybean oil was supplied. The sampling was performed every 8 hours. The properties of the resultant reaction product were analyzed through SimDist, and the leaching of the catalyst was analyzed through ICP. 
       COMPARATIVE EXAMPLE 2 
     Preparation of CoMo/Al 2 O 3  Catalyst 
       [0105]    A catalyst composed of about 10 wt % of Mo and about 3 wt % of Co using an Al 2 O 3  support having a diameter of 1 mm was prepared. As the Mo precursor, ammonium heptamolybdate tetrahydrate (hereinafter, AHM) was used, and as the Co precursor, Cobalt nitrate hexahydrate (hereinafter, CNH) was used. 
         [0106]    The CoMo/Al 2 O 3  catalyst was prepared through the following procedures. 
         [0107]    First, a Mo/Al 2 O 3  catalyst was prepared in the same manner as in Comparative Example 1. 
         [0108]    Then, CNH was dissolved in distilled water, supported on the Mo/Al 2 O 3  catalyst, dried at 150° C. for 2 hours, and continuously burned at 500° C. for 2 hours, thus preparing the CoMo/Al 2 O 3  catalyst. 
         [0109]    The CoMo/Al 2 O 3  catalyst was pretreated as in Comparative Example 1. 
         [0110]    Using the CoMo/Al 2 O 3  catalyst thus pretreated, under conditions of a reaction temperature of 350° C., a reaction pressure of 30 bar and H 2  supplied at 100 cc/min, a feed composed of 1% DMDS-containing soybean oil was allowed to react at a rate of 0.1 cc/min (LHSV=1). After 7 days, 1% DMDS supplied together with soybean oil was cut, and 100% soybean oil was supplied. The sampling was performed every 8 hours. The properties of the resultant reaction product were analyzed through SimDist, and the leaching of the catalyst was analyzed through ICP. 
         [0111]    Table 1 below shows diesel selectivity of the product in the HBD preparation using the metal phosphide. 
         [0000]    
       
         
               
               
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                   
                 Component Diesel  
                   
                   
                   
               
               
                   
                 Catalyst 
                 Selectivity (%) 
                 1 day 
                 15 days 
                 30 days 
               
               
                   
                   
               
             
             
               
                   
                 Ex. 1 
                 MoP/ZrO 2   
                 97 
                 97 
                 96 
               
               
                   
                 Ex. 2 
                 Ni 2 P/ZrO 2   
                 92 
                 90 
                 84 
               
               
                   
                 Ex. 3 
                 WP 
                 93 
                 90 
                 85 
               
               
                   
                 Ex. 4 
                 NiMoP/ZrO 2   
                 94 
                 93 
                 93 
               
               
                   
                 Ex. 5 
                 MoP/Al 2 O 3   
                 93 
                 91 
                 89 
               
               
                   
                 Ex. 6 
                 MoP/ZrO 2   
                 99 
                 99 
                 99 
               
               
                   
                   
                 (Mixed Feed) 
                   
                   
                   
               
               
                   
                 Ex. 7 
                 MoP/ZrO 2    
                 94 
                 93 
                 93 
               
               
                   
                   
                 (containing DMDS) 
                   
                   
                   
               
               
                   
                 Ex. 8 
                 CoMoP/TiO 2   
                 93 
                 93 
                 93 
               
               
                   
                 C. Ex. 1 
                 NiMo/Al 2 O 3   
                 92 
                 91 
                 86 
               
               
                   
                 C. Ex. 2 
                 CoMo/Al 2 O 3   
                 91 
                 89 
                 88 
               
               
                   
                   
               
             
          
         
       
     
         [0112]    As is apparent from the results of Table 1, in the case of the MoP/ZrO 2  catalyst, the activity thereof could be seen to be uniformly maintained even without the use of a sulfur compound. 
         [0113]    Example 7 was executed to identify the catalyst poisoning effect of sulfur into the metal phosphide catalyst. Example 7 demonstrated that the metal phosphine catalyst maintains the catalytic activity when kerosene or diesel such as hydrocarbons including sulfur is used as co-feed in the preparation of biodiesel. 
         [0114]    Table 2 below shows the ratios of isomers in the product of Examples 1˜5, Examples 7˜8 and Comparative Examples 1˜2. Referring to Example 6, the ratios of product depend on the properties of R-kerosene mixed with vegetable oil. 
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 2 
               
               
                   
               
               
                   
                 I SO -C15/C15  
                 I SO -C16/C16  
                 I SO -C17/C17 
                 I SO -C18/C18  
               
               
                 Catalyst  
                 (%) 
                 (%) 
                 (%) 
                 (%) 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Ex. 1 
                 0 
                 7.6 
                 21.4 
                 30.3 
               
               
                 Ex. 2 
                 0 
                 6.8 
                 23.9 
                 28.3 
               
               
                 Ex. 3 
                 0 
                 2.3 
                 8.1 
                 11.9 
               
               
                 Ex. 4 
                 0 
                 8.2 
                 24.0 
                 29.3 
               
               
                 Ex. 5 
                 0 
                 7.1 
                 19.9 
                 29.8 
               
               
                 C. Ex. 1 
                 0 
                 0 
                 6.6 
                 8.2 
               
               
                 C. Ex. 2 
                 0 
                 0 
                 6.1 
                 7.5 
               
               
                   
               
             
          
         
       
     
         [0115]    As is apparent from the results of Table 2, the CoNiMo/Al 2 O 3  or NiMo/Al 2 O 3  catalyst of Comparative Example 1 or 2 had a very low isomerization ratio of 6˜8%. 
         [0116]    Thus, in the case of HBD prepared using the CoMo/Al 2 O 3  catalyst or NiMo/Al 2 O 3  catalyst, flow properties at low tempaerature should be additionally ensured. 
         [0117]    In the case of the HBD product prepared using the MoP/ZrO 2  catalyst of Example 1, the isomerization ratio was about 20˜30%. Accordingly, it was confirmed that HBD stable even at a relatively low temperature can be prepared. 
         [0118]    The foregoing examples are provided merely for the purpose of explanation and are in no way to be construed as limiting. While reference to various embodiments are shown, the words used herein are words of description and illustration, rather than words of limitation. Further, although reference to particular means, materials, and embodiments are shown, there is no limitation to the particulars disclosed herein. Rather, the embodiments extend to all functionally equivalent structures, methods, and uses, such as are within the scope of the appended claims.