Description:FIELD OF THE INVENTION
[0001] The present invention relates to a catalyst for the catalytic hydroprocessing of vegetable oils. The present disclosure also provides a method of preparation of a catalyst for catalytic hydroprocessing of vegetable oil. Further, the present disclosure also provides a method of preparation of alumina-silica (Al2O3­SiO2) support for preparation of supported catalyst suitable for catalytic hydroprocessing of vegetable oils.

BACKGROUND
[0002] Background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
[0003] CN106190280A discloses a method of preparation of jet fuel with renewable raw materials. The method includes that in hydrotreating reaction zone, vegetable oil and/or animal oil contacted with hydrogenation deoxidation catalyst and hydroisomerization catalyst successively to obtain hydrotreating reaction product. In hydroisomerizing pour point depression reaction zone, the obtained hydrotreating reaction product contacted with hydroisomerizing pour point depression catalyst together with hydrogen to obtain hydroisomerizing pour point depression reaction product. Further, in hydrofining reaction district, the obtained hydroisomerizing pour point depression reaction product contacted with hydrobon catalyst together with hydrogen to obtain hydrofining reaction product. The hydrofining reaction product is the most separated, jet fuel is obtained after fractional distillation.
[0004] US2010240942A1 discloses a process for hydrodeoxygenation of feeds derived from renewable sources with conversion by decarboxylation/decarbonylation limited to at most 10%, using a bulk or supported catalyst comprising an active phase constituted by at least one element from group VIB and at least one element from group VIII, said elements being in the sulphide form, and the atomic ratio of the metal (or metals) from group VIII to the metal (or metals) from group VIB being strictly more than 0 and less than 0.095, said process being carried out at a temperature in the range 120° C to 450° C., at a pressure in the range 1 MPa to 10 MPa, at an hourly space velocity in the range 0.1 h-1 to 10 h-1, and in the presence of a total quantity of hydrogen mixed with the feed such that the hydrogen/feed ratio is in the range 50 to 3000 Nm3 of hydrogen/m3 of feed.
[0005] US2011192765A1 discloses a catalyst comprising at least one IZM-2 zeolite, at least one amorphous matrix, at least one hydro-dehydrogenating element selected from the group formed by the elements from group VIB and from group VIII of the periodic table and excluding platinum and palladium. The catalyst also may optionally contain a controlled quantity of atleast one element selected from phosphorus, boron and silicon, optionally at least one element from group VB of the periodic table of the elements, and optionally a group VIIA element. The invention also relates to hydroprocessing and hydrotreatment processes using this catalyst.
[0006] Itoh et al. [J. Ceram. Soc. JAPAN 1993, 101, 9, 1081-1083] discloses a method for preparing SiO2-Al2O3 gels from aqueous solutions of tetraethoxysilane and aluminum chloride. Addition of propylene oxide to the solutions promoted gelation reaction, yielding translucent gels. It was found that the 4-coordinated Al incorporated in the framework of the gels was formed without heat treatment. Residual chloride ions were removed from the gels by heating.
[0007] Yabuki et al. [Phys. Chem. Chem. Phys., 2002, 4, 4830-4837] described amorphous silica–alumina catalysts prepared via sol–gel method by reacting tetraethoxysilane with aluminium nitrate and various organic additives, and the effects of the additives on both pore formation and acid-site generation were investigated. Macropores with bicontinuous morphology are formed when poly(ethylene oxide) (PEO) with an average molecular weight of 100000 was used as structure directing agent and, when a transitional structure of spinodal decomposition is fixed by sol–gel transition of inorganic components. In the systems with other organic additives with low molecular weight, such as ethylene glycol oligomers and citric acid, silica–alumina is obtained with only mesopores. Although their mesopore structures are not affected by organic additives, the catalytic activity varies depending on the kind of organic additives. It is found that organic additives with the ability to increase the interaction between silica oligomers and aluminium cations increase the dispersion of Al in the silica network, resulting in high catalytic activity in the cracking of cumene. PEO interacts with both silicon and aluminium cations in the sol–gel mixture, so that macroporous silica–alumina prepared in the presence of PEO shows excellent catalytic activity.
[0008] Thus, there is a need to develop cost effective and high performance indigenous catalyst for catalytic hydroprocessing of vegetable oils, preferably used cooking oil for meeting the euro-VI diesel and Bio-ATF fuel specification.

OBJECTIVES OF THE INVENTION
[0009] To provide a catalyst for catalytic hydroprocessing of vegetable oil.
[0010] To provide a method of preparation of a catalyst for catalytic hydroprocessing of vegetable oil.
[0011] Another objective of the present disclosure is to provide a method of preparation of alumina-silica (Al2O3­SiO2) support for preparation of supported catalysts suitable for catalytic hydroprocessing of vegetable oils

SUMMARY OF THE INVENTION
[0012] This summary is provided to introduce a selection of concepts in a simplified form that are further described below in detailed description section. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
[0013] Aspects of the present disclosure provide a catalyst for catalytic hydroprocessing of vegetable oils having a nickel (Ni) component; a metal component selected from molybdenum (Mo) and/or tungsten (W); a phosphorus (P) components; and an ?-alumina-silica (?-Al2O3­SiO2) support, wherein molar ratio of Ni/Mo and Ni/W is in the range of 0.5-2.0 and weight ratio of ?-Al2O3­SiO2 is 70:30.
[0014] In an aspects of the present disclosure provide a method of preparation of a catalyst for catalytic cracking of vegetable oil having a) impregnating a trilobe extrudates particle of ?-Al2O3­SiO2 support with 0.3-0.7 % wt % of a phosphorus acid under condition to obtain a phosphorus impregnated trilobe matetrial; b) impregnating 5-15 wt% of a metal precursor of Mo and/or W on the phosphorus impregnated trilobe material under condition to obtain a metal oxide supported P-trilobe material; and c) impregnating 10-20 wt % of a nickel precursor on the molybdenum oxide supported P-trilobe catalyst under condition to obtain a catalyst for catalytic cracking of vegetable oil, wherein molar ratio of Ni/Mo and Ni/W is in the range of 0.5-2.0 and weight ratio of ?-Al2O3­SiO2 is 70:30.
[0015] In an aspect, the present invention provides a method of preparation of an ?-alumina-silica (?-Al2O3­SiO2) support with following steps a) mixing an alumina solution with a silica solution to obtain a mixed solution; b) adding propylene oxide to the mixed solution under condition to obtain a wet gel; and c) processing the wet gel with anhydrous ethanol under condition to obtain a ?-alumina-silica (?-Al2O3­SiO2) support, wherein the weight ratio of ?-Al2O3:SiO2 is 70:30.
[0016] Other aspects of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learnt by the practice of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1: illustrates process flowchart of synthesizing ?-Al2O3­SiO2 support.
[0018] Figure 2: illustrates process flowchart for final catalyst synthesis.
[0019] Figure 3: illustrates viscosity & Pour Point of Deoxygenated Oil (DO).
[0020] Figure 4: illustrates (a) Kero/Diesel yield & UCO conversion and (b) yields of lighter hydrocarbons.
[0021] Figure 5: Pore size distribution of different supports.
DETAILED DESCRIPTION OF THE INVENTION
[0022] The following is a detailed description of embodiments of the disclosure. The embodiments are in such detail so as to clearly communicate the disclosure. However, the amount of detail offered is not intended to limit the anticipated variations of embodiments; on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the scope of the present disclosure.
[0023] All publications herein are incorporated by reference to the same extent as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. Where a definition or use of a term in an incorporated reference is inconsistent or contrary to the definition of that term provided herein, the definition of that term provided herein applies and the definition of that term in the reference does not apply.
[0024] Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
[0025] In some embodiments, numbers have been used for quantifying weights, percentages, ratios, and so forth, to describe certain embodiments of the invention and are to be understood as being modified in some instances by the term “about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable. The numerical values presented in some embodiments of the invention may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
[0026] Various terms as used herein are shown below. To the extent a term used is not defined below, it should be given the broadest definition persons in the pertinent art have given that term as reflected in printed publications and issued patents at the time of filing.
[0027] As used in the description herein that follow, the meaning of “a,” “an,” and “the” includes plural reference unless the context clearly dictates otherwise. Also, as used in the description herein, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise.
[0028] Unless the context requires otherwise, throughout the specification which follow, the word “comprise” and variations thereof, such as, “comprises” and “comprising” are to be construed in an open, inclusive sense that is as “including, but not limited to.”
[0029] The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein.
[0030] All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g. “such as”) provided with respect to certain embodiments herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention.
[0031] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member can be referred to individually or in any combination with other members of the group or other elements found herein. One or more members of a group can be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is herein deemed to contain the group as modified.
[0032] The description that follows, and the embodiments described therein, is provided by way of illustration of an example, or examples, of particular embodiments of the principles and aspects of the present disclosure. These examples are provided for the purposes of explanation, and not of limitation, of those principles and of the disclosure.
[0033] It should also be appreciated that the present disclosure can be implemented in numerous ways, including as a system, a method or a device. In this specification, these implementations, or any other form that the invention may take, may be referred to as processes. In general, the order of the steps of the disclosed processes may be altered within the scope of the invention.
[0034] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0035] The following discussion provides many example embodiments of the inventive subject matter. Although each embodiment represents a single combination of inventive elements, the inventive subject matter is considered to include all possible combinations of the disclosed elements. Thus, if one embodiment comprises elements A, B, and C, and a second embodiment comprises elements B and D, then the inventive subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.
[0036] In an embodiment, the present invention discloses a catalyst for catalytic hydroprocessing of vegetable oil comprising: a nickel (Ni) component; a metal component selected from molybdenum (Mo) and/or tungsten (W); a phosphorus (P) component; and an ?-alumina-silica (?-Al2O3­SiO2) support, wherein molar ratio of Ni/Mo and Ni/W is in the range of 0.5-2.0 and weight ratio of ?-Al2O3:SiO2 is 70:30.
[0037] In an embodiment, the present disclosure discloses that the catalyst having P-Mo-Ni components supported on ?-Al2O3­SiO2 gives selectivity towards diesel and the catalyst having P-Wo-Ni components supported ?-Al2O3­SiO2 gives selectivity towards kero range hydrocarbons. The diesel contains C13-C22 with boiling range 260-340°C and kero contains C10 to C16 with boiling range 175-290°C.
[0038] In an embodiment, the present invention discloses that Ni 1-5 wt% and Mo 10-15 wt% and W 15-21 wt% present in the catalyst.
[0039] In another embodiment, the present disclosure discloses a method of preparation of a catalyst for catalytic hydroprocessing of vegetable oils comprising: a) impregnating a trilobe extrudates particle of ?-Al2O3­SiO2 support with 0.3-0.7 % w/w of a phosphorus acid under condition to obtain a phosphorus impregnated trilobe support ; b) impregnating 5-15 % w/w of a metal precursor of Mo and/or W on the phosphorus impregnated trilobe support under condition to obtain a metal oxide supported P-trilobe catalyst; and c) impregnating 10-20 % w/w of a nickel precursor on the molybdenum oxide supported P-trilobe material under condition to obtain the final catalyst for catalytic hydroprocessing of vegetable oil, wherein molar ratio of Ni/Mo and Ni/W is in the range of 0.5-2.0 and weight ratio of ?-Al2O3­SiO2 is 70:30.
[0040] Another embodiment of the present disclosure discloses that the trilobe extrudates of ?-Al2O3­SiO2 were dried at a temperature in the range of 450-550 °C for a period in the range of 1-3 hrs prior to impregnation.
[0041] In another embodiment, the Mo precursor is selected from a group consisting of Ammonium heptamolybdate tetrahydrate, Ammonium Molybdate, Molybdic Acid (MA), Molybdenum trioxide (MTO), Sodium Molybdate (SM), Sodium molybdate, molybdenum di sulphide.
[0042] In another embodiment, the W precursor is selected from a group consisting of Silico Tungstic Acid, Tungstosilicic acid hydrate, Ammonium tungsten oxide hydrate and Hexaammonium tungstate hydrate. The W precursor is H3[P(W4O10)4].xH2O.
[0043] In another embodiment, the impregnation in steps (a)-(c) is carried out by spray method followed by drying for a period in the range of 10-14 hrs at a temperature in the range of 25-35 °C.
[0044] In another embodiment, the condition in steps (a)-(c) includes drying at a temperature in the range of 110-130 °C for a period of 10-14 hrs followed by calcination at a temperature in the range of 500-600 °C for a period in the range of 4-6 hrs.
[0045] In another embodiment, the present disclosure also discloses a method of preparation of an ?-alumina-silica (?-Al2O3­SiO2) support comprising: a) mixing an precursor solution of aluminium with a precursor of silicon to obtain a mixed solution; b) adding propylene oxide to the mixed solution under condition to obtain a wet gel; and c) processing the wet gel with anhydrous ethanol under condition to obtain an ?-alumina-silica (?-Al2O3­SiO2) support, wherein the weight ratio of ?-Al2O3­SiO2 is 70:30.
[0046] In another embodiment, the aluminium precursor solution is prepared by stirring the mixture of AlCl3•6H2O/EtOH/ H2O in a ratio of 1/12/35.
[0047] Another embodiment, the silicon precursor solution is prepared by stirring the mixture of TEOS/H2O/EtOH/HCl in a ratio of 1/4/6/7.5 10-3.
[0048] In another embodiment, the aluminium precursor solution and the silicon precursor solution is mixed at a temperature in the range of 25-35°C for 50-70 min.
[0049] In another embodiment, the condition in step b) includes stirring at a temperature in the range of 25-35°C for a period in the range of 10-20 min.
[0050] In another embodiment, the processing in step c) includes supercritical drying at a pressure in the range of 0.1 to 9.1 MPa and the temperature increased to 270 °C at a rate of 2°C/min.
[0051] In another embodiment, the ?-Al2O3­SiO2 support prepared by sol gel method has a pore size distribution in the range of 10-35 Å with an average maximum distribution of 22 Å.
Catalysts
[0052] In another embodiment, a series of nickel–molybdenum–phosphorous acid (Ni–Mo–P) and nickel–tungsten–phosphorous acid (Ni–W–P) impregnating solutions with various Ni/Mo molar ratios (0.5, 1.5 and 2.0) and Ni/W molar ratios (0.5, 1.5 and 2.0) were synthesized, by sequential pore filling on ?-Al2O3-SiO2 through an incipient wetness impregnation method. After impregnation, the samples were dried at 120 oC for 12h and then calcined in a muffle furnace under static air Vat 550 oC for 5h through ramping to obtain the required Ni–Mo–catalysts and Ni–W–catalysts. The total loading of metal oxide (MoO3 and NiO) was 25 wt%. The Ni–Mo–P catalysts with different Ni/Mo molar ratios were denoted as UCO-x (where x is the Ni/Mo molar ratios and x = 0.5, 1.5 and 2.0) and the total loading of metal oxide (WO3 and NiO) was 24 wt%. The Ni–W–P catalysts with different Ni/W molar ratios were denoted as UCO-x (where x is the Ni/W molar ratios and x = 0.5, 1.5 and 2.0). Impregnating solutions phosphoric acid, ammonium molybdenum and nickel nitrate solutions were added sequentially.
Support ?-Al2O3-SiO2 (70:30) preparation
[0053] In another embodiment, the process routing of synthesizing ?-Al2O3-¬SiO2 support is given in Fig. 1. The process involves three steps: (1) the synthesis of mixed sol; (2) the synthesis of wet gel and the process of aging treatment; (3) ethanol supercritical drying technology.
[0054] In the step 1, alumina sol and silica sol were prepared by stirring the mixture with the mole ratio of AlCl3·6H2O/EtOH/ H2O = 1/12/35 and TEOS/H2O/EtOH/HCl = 1/4/6/7.5 10-3 respectively. Then, mixed alumina sol and silica sol in a weight ratio of 70:30 for 60 min to complete the hydrolysis.
[0055] In the step 2, in order to promote the condensation, propylene oxide was added to the mixed sol. The mixture was quickly stirred at 30°C for 15 min and sealed at room temperature to form the wet gel. In the process of aging treatment, the wet gel was soaked in anhydrous ethanol at 50°C to strengthen the network and swap out the redundant water and organic matter.
[0056] In the step 3, the wet gel was placed in an autoclave which was sealed and filled with anhydrous ethanol. In order to ensure safety requirements, the autoclave was recharged with pure nitrogen gas to replace oxygen. The absolute pressure was controlled in the range of 0.1 to 9.1 MPa. The temperature was increased to 270°C at a rate of 2°C/min. The pressure of autoclave slowly reduced to 0.1 MPa before opening the autoclave. Finally, the samples were obtained at room temperature. The obtained support contains 70:30 weight ratio of ?-Al2O3 and SiO2. In order to investigate the effect of calcination temperature on structural and textural properties of ?-Al2O3­SiO2 aerogel, samples were calcined at 550, 600, 800, 1000, 1200 °C respectively for 2 h with a rate of 3°C/min.
NiMo/ ?-Al2O3-SiO2 Catalyst Preparation: Sequential Pore Filling
[0057] The support ?-alumina-silica (70:30), (Trilobe extrudates) were dried at 500 °C for 2 h prior to impregnation for removal of moisture.
[0058] Pore volume was measured with water wetting technique.
[0059] The Trilobe extrudates were then impregnated with a 0.5 wt% phosphorus-H2O solution by incipient wetness method. The solution was sprayed on to the extrudates and air dried for 12 hours at room temperature. Then dried at 120 °C/12 h in an air oven followed by calcination in muffle furnace at 550 °C/5h to get phosphorus impregnated trilobe catalyst.
[0060] 10 wt% of molybdenum was impregnated on P impregnated calcined trilobe support material with (NH4)6Mo7O24.4H2O solution. Sample is then dried in air and oven as done in step 3 followed by calcination at 550 °C/5h to get MoO3 oxide incorporated P-trilobe.
[0061] 15 wt% Nickel was impregnated onto this material using a nickel nitrate aqueous solution and material is dried at room temperature for 12 hours and 110 °C/12 h in oven and calcined at 550 °C/5h in a muffle furnace.
[0062] The obtained catalyst is NiMo/ alumina-Silica designated as NiMo-1.5 (Ni/Mo = 1.5 wt%, the weight % range of Ni/Mo is 0.2 to 1.5)
[0063] The other UCO-0.5 and 2.0 were prepared in the same procedure as UCO-1.5 with varying amounts of Ni and Molybdenum.
NiW/ ?-Al2O3-SiO2 Catalyst Preparation: Sequential Pore Filling
[0064] The support ?-alumina-silica (70:30), (Trilobe extrudates) were dried at 500 °C for 2 h prior to impregnation for removal of moisture.
[0065] Pore volume was measured with water wetting technique.
[0066] The Trilobe extrudates were then impregnated with a 0.5 wt% phosphorus-H2O solution by incipient wetness method. The solution was sprayed on to the extrudates and air dried for 12 hours at room temperature. Then dried at 120 °C/12 h in an air oven followed by calcination in muffle furnace at 550 °C/5h to get phosphorus impregnated trilobe catalyst.
[0067] 10 wt% of tungsten was impregnated on P impregnated calcined trilobe support material with H3[P(W4O10)4].xH2O solution. Sample is then dried in air and oven as done in step 3 followed by calcination at 550 °C/5h to get tungsten oxide incorporated P-trilobe.
[0068] 15 wt% Nickel was impregnated onto this material using a nickel nitrate aqueous solution and material is dried at room temperature for 12 hours and 110 °C/12 h in oven and calcined at 550 °C/5h in a muffle furnace.
[0069] The obtained catalyst is NiW/ alumina-Silica designated as NiW-1.5 (Ni/W = 1.5 wt%, the weight % range of Ni/W is 0.2 to 1.5)
[0070] The other UCO-0.5 and 2.0 were prepared in the same procedure as UCO-1.5 with varying amounts of Ni and W.
[0071] While the foregoing describes various embodiments of the disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof. The invention is not limited to the described embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the invention when combined with information and knowledge available to the person having ordinary skill in the art.
EXAMPLES
[0072] The disclosure will now be illustrated with working examples, which is intended to illustrate the working of disclosure and not intended to take restrictively to imply any limitations on the scope of the present disclosure. Although methods and materials similar or equivalent to those described herein can be used in the practice of the disclosed methods and compositions, the exemplary methods, devices and materials are described herein. It is to be understood that this disclosure is not limited to particular methods, and experimental conditions described, as such methods and conditions may vary.
Example 1
[0073] ?-Al2O3-SiO2 mixed oxide based supports prepared by co-precipitation and sol-gel methods and characterized for XRD, acidity, surface area & pore volume. Properties compared with ?-Al2O3 (Commercial grade 1) support and support from Aldrich.
Table 1: Characterization of supports.
Sr Support BET Surface area (m2/g) NH3-TPD Acid sites concentration (µmol/g)
Weak Acidity (<150 0C) Moderate Acidity (150 C-450 0C) Strong Acidity (450 0 + C) Total Acidity
1 ?-Al2O3 (Commercial grade 1) 250 - 483 295 778
2 SiO2 with Al2O3 (Commercial grade 3) 210 - 382 240 622
3 Al2O3-SiO2 (70/30)
(Mechanical grinding) 205 - 706 19 725
4 Al2O3-SiO2 (70/30)
(Co-precipitation method)-H2O 357 - 650 25 675
5 Al2O3-SiO2 (70/30)
(Co-precipitation method)-EtOH 371 - 715 56 771
6 Al2O3-SiO2 (70/30)
(Sol-Gel method) 361 - 547 278 825

[0074] Higher moderate acidities of mixed oxides (MOs) compared to single oxides Al2O3 and SiO2 - MOs can offer better cracking activity. It was also found that MOs prepared through chemical synthesis offer higher surface area as compared to their single oxide counterparts (Table 1).
[0075] Al2O3-SiO2 mixed oxide prepared indigenously showed more moderate acidity when compared with commercial grade Al2O3 on NH3-TPD analysis. The more acidity OF the supports will lead to more cracking and leads to more lighter fraction formation than the desired liquid yield, the low acidic supports do not crack the used cooking oil branch, optimum SiO2/Al2O3 generates minimum or moderate acidity required for cracking.
[0076] A catalyst pore is an important performance-defining characteristic that affects the available surface for reactions to occur. Used to refer to the internal structure or internal surface area of catalysts, the size and structure of this pore influences permeability—the ease with which gases and fluids can travel through a solid. Finer pores give rise to low permeability, resulting in higher resistance to fluid flow, used to limit unwanted reactions. Only molecules of desired sizes can enter and leave, creating a selective catalyst that will produce the desired product. The pore size distribution (PSD) of various supports which is computed by NLDFT method is depicted in Figure 5. The sample Al2O3-SiO2 (70/30) prepared by Sol-Gel method exhibited better mesoporosity and narrower PSD than other supports. The ?-Al2O3­SiO2 support prepared by sol gel method has a pore size distribution in the range of 10-35 Å with an average maximum distribution of 22 Å.
Example 2
[0077] All catalysts have a comparable surface area as shown in Table 2. However, Bromine No. found to be high for Al2O3-SiO2 (70/30) (Co-precipitation method (H2O) and mechanical grinded oxide supported catalysts (2-5). It has been observed from XRF analysis that Ni content found to be lower in the catalyst.
[0078] The low amount of nickel resulted in less hydrogenation leading to more unsaturated fatty acids resulting in more bromine nos.
Table 2: Characterization of Catalysts
Support and description of method Targeted Metal Composition (wt %) XRF Analysis
(Metal Content, wt %) BET SA (m2/g) Pore Volume (cm3/g)
P: 0.5%;
Mo: 14 %,
Co or Ni: 3 % % P %Ni % Co % Mo
?-Al2O3
(commercial grade 1) 0.52 0 0.2 16.2 177 0.5843
Al2O3-SiO2 (70/30)
(Mechanical grinding) 0.6 2 0 14 160 0.4262
Al2O3-SiO2 (70/30)
(Co-precipitation method)-EtOH 0.5 1.5 0 13 185 0.3734
Al2O3-SiO2 (70/30)
(Co-precipitation method)-H2O > 1 0.1 0 17 175 0.3684
Al2O3-SiO2 (70/30)
(Sol-Gel method) 0.5 2.9 0 17 186 0.3626
SiO2 with Al2O3 (Commercial grade 3) 0.5 2 0 17 180 0.3139

[0079] The Al2O3-SiO2 support of the present invention has more moderate acidity than commercial grades, though less than Co-precipitation but has increased surface area and the percentage of reduction in total surface area of present support is only 8% when compared with other supports. Support stability plays a major role in hydrodeoxygenation reactions, since the percentage water formed during this reaction is more and can destabilize the hydrothermal stability of support.
Example 3
[0080] Viscosity dropped from 44 Cst @ 40 C to 3 – 3.5 Cst @ 40 C. All catalysts resulted into similar drop in viscosity – Comparative HDO activity for all catalysts. Mixed Oxides (MOs) supported catalysts resulted into lower pour points compared to single oxide supported catalyst (??-Al2O3) – more acidity of MOs lowered the pour point. (Fig. 3).
[0081] Mixed Oxides (MOs) supported catalysts resulted into lower pour points compared to single oxide supported catalyst ?-Al2O3 – more acidity of MOs lowered the pour point (Fig. 3).
Example 4
[0082] It has been observed that MOs supported catalysts are more selective towards producing kerosene/ATF range hydrocarbon molecules. Highest kero yield and UCO conversion for commercial SiO2-Al2O3 support (commercial grade 3) (Fig. 4).
[0083] The more acidic support such as commercial grade-3 yields in more lighters formation due to more cracking.
Example 5
[0084] It has been observed that very low decrease in surface area in hybrid support Al2O3-SiO2 after hydrothermal stability test (Table 3).
Table 3: Supports Properties: Before & after Hydrothermal Stability Test
S. No. Catalyst TSA {m2/g} ESA
{m2/g} % Reduction in TSA
1. Commercial grade 1 250 234
2. Commercial grade 1 173 163 30
3. Commercial grade 3 210 180
4. Commercial grade 3 166 155 21
5. ?-Al2O3-SiO2 (70/30) 187 151
6. ?-Al2O3-SiO2 (70/30)-HST 171 164 8
7. Al2O3-TiO2 (70/30) 165 157
8. Al2O3-TiO2 (70/30) –HST 139 132 15
9. Al2O3-ZrO2 (70/30) 158 150
10. Al2O3-ZrO2 (70/30) –HST 131 126 17
11. Al2O3-MgO (70/30) 167 154
12. Al2O3-MgO (70/30) –HST 114 104 32

[0085] The hydrothermal stability for all the supports including commercially available supports has been tested and percentage reduction in surface area after hydrothermal stability test has been compared with the corresponding fresh support. From Table 3, it can see the in-house prepared support ?-Al2O3-SiO2 (70/30) shows more stability for hydrothermal reaction and less reduction in surface area.
Example 6
[0086] The prepared catalyst evaluation showed 94 % of UCO conversion with >75% selectivity to kero range hydrocarbon molecules as shown in Table 4.
[0087] From Table 4 it is clear, for diesel range hydrocarbon molecules formation, Al2O3-SiO2 (70/30) support with P, Mo and Ni loading in optimal range at the specified operating process yields mainly in 65% diesel with 90% UCO conversion and the same support with replacement of Mo with W yields in 75% Kero selective molecules with 95% UCO conversion.
Table 4: Results For 1st stage Hydro-deoxygenation
Catalyst Results
% Ni % Mo % W % P Viscosity @ 40 C PP Br No. % FFA % Gas % Gasoline % Kero % Diesel % Water % UCO Conv.
3 10 0 0.5 3.3 6 4.51 0.021 6.3 2.09 8.34 62.57 6.35 89.57
3 5 0 0.5 2.63 3 24.98 0.77 5.9 2 8 60 6 94.33
3 2 0 0.5 3.42 3 54.59 10.77 6.72 1.77 13.26 58.78 8.29 93.07
3 15 0 0.5 3.11 12 0.785 0.0027 5.14 1.09 5.84 59.11 6.25 85.42
3 14 30 0.5 3 15 0.635 0.016 4.56 1.22 64.84 9.32 6.95 86.69
3 14 0 0.5 2.87 12 0.425 0.02 11.92 4.48 10.19 54.20 5.14 87.37
3 10 10 0.5 2.95 12 0.435 0.023 14.11 1.28 72.38 5.96 5.43 95.47
3 14 15 0.5 2.9 9 0.28 0.017 15.62 1.31 73.20 6.97 5.07 95.34
3 14 0 0.5 2.96 6 0.535 0.01 17.02 1.56 7.06 62.76 4.96 90.98
3 14 0 0.5 2.89 9 0.54 0.14 10.09 0.78 16.24 89.08 7.00 95
3 0 21 0.5 3.3 12 0.32 0.005 12.39 2.25 75.28 78.41 6.83 95

[0088] This invention has been described in terms of specific embodiments set forth in detail, but it should be understood that these are by way of illustration only and that the invention is not necessarily limited thereto. Modifications and variations will be apparent from this disclosure and may be achieved without

departing from the scope of this invention, as those skilled in the art will readily understand. Accordingly, such variations and modifications of the disclosed embodiments are considered to be within the purview and scope of this invention and the following claims.

, Claims:1. A catalyst for catalytic hydroprocessing of vegetable oils comprising:
a nickel (Ni) component;
a metal component selected from molybdenum (Mo) and/or tungsten (W);
a phosphorus (P) component; and
an ?-alumina-silica (?-Al2O3­SiO2) support,
wherein molar ratio of Ni/Mo and Ni/W is in the range of 0.5-2.0 and weight ratio of ?-Al2O3­SiO2 is 70:30.
2. The catalyst as claimed in claim 1, wherein the catalyst having P-Mo-Ni gives selectivity towards diesel range hydrocarbon molecules.
3. The catalyst as claimed in claim 1, wherein the catalyst having P-Wo-Ni gives selectivity towards kero range hydrocarbon molecules.
4. A method of preparation of a catalyst for catalytic cracking of vegetable oil comprising:
a) impregnating a tribole extrudates particle of ?-Al2O3­SiO2 support with 0.3-07 % w/w of a phosphorus acid under condition to obtain a phosphorus impregnated trilobe catalyst;
b) impregnating 5-15 % w/w of a metal precursor of Mo and/or W on the phosphorus impregnated trilobe catalyst under condition to obtain a metal oxide supported P-trilobe material ; and
c) impregnating 10-20 % w/w of a nickel precursor on the molybdenum oxide supported P-trilobe catalyst under condition to obtain a catalyst for catalytic cracking of vegetable oil,
wherein molar ratio of Ni/Mo and Ni/W is in the range of 0.5-2.0 and weight ratio of ?-Al2O3­SiO2 is 70:30.
5. The method as claimed in claim 4, wherein the trilobe extrudates particle of ?-Al2O3­SiO2 were dried at a temperature in the range of 450-550 °C for a period in the range of 1-3 hrs prior to impregnation.
6. The method as claimed in claim 4, wherein Mo precursor is selected from a group consisting of Ammonium heptamolybdate tetrahydrate, Ammonium Molybdate, Molybdic Acid (MA), Molybdenum trioxide (MTO), Sodium Molybdate (SM), sodium molybdate, molybdenum di sulphide.
7. The method as claimed in claim 4, wherein W precursor is selected from a group consisting of Silico Tungstic Acid, Tungstosilicic acid hydrate, Ammonium tungsten oxide hydrate and Hexaammonium tungstate hydrate.
8. The method as claimed in claim 4, wherein the impregnation in steps (a)-(c) is carried out by spray method followed by drying for a period in the range of 10-14 hrs at a temperature in the range of 25-35 °C.
9. The method as claimed in claim 4, wherein the condition in steps (a)-(c) includes drying at a temperature in the range of 110-130 °C for a period of 10-14 hrs followed by calcinations at a temperature in the range of 500-600 °C for a period in the range of 4-6 hrs.
10. A method of preparation of an ?-alumina-silica (?-Al2O3­SiO2) support comprising:
a) mixing an ?-aluminium solution with a silica solution to obtain a mixed solution;
b) adding propylene oxide to the mixed solution under condition to obtain a wet gel;
c) processing the wet gel with anhydrous ethanol under condition to obtain an ?-alumina-silica (?-Al2O3­SiO2) support,
wherein weight ratio of ?-Al2O3­SiO2 is 70:30.
11. The method as claimed in claim 10, wherein the alumina solution is prepared by stirring the mixture of AlCl3·6H2O/EtOH/ H2O in a ratio of 1/12/35.
12. The method as claimed in claim 10, wherein the silica solution is prepared by stirring the mixture of TEOS/H2O/EtOH/HCl in a ratio of 1/4/6/7.5 10-3.
13. The method as claimed in claim 10, wherein the alumina solution and the silica solution is mixed at a temperature in the range of 25-35°C for 50-70 min to complete the hydrolysis.
14. The method as claimed in claim 10, wherein the condition in step b) includes stirring at a temperature in the range of 25-35°C for a period in the range of 10-20 min.
15. The method as claimed in claim 10, wherein the processing in step c) includes supercritical drying at a pressure in the range of 0.1 to 9.1 MPa and the temperature increased to 270 °C at a rate of 2°C/min.
16. The method as claimed in claim 10, wherein the ?-Al2O3­SiO2 support prepared by sol gel method has a pore size distribution in the range of 10-35 Å.