AROMATICS RICH AVIATION FUEL

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a catalytic process to convert renewable feedstock into aromatics rich aviation fuel. Particularly, the invention falls within the processing field of hydroconversion. More specifically, hydroprocessing of vegetable triglycerides and free fatty acids using a catalytic process to produce parafins, iso-parafins, cyclo-paraffins and aromatics.

BACKGROUND AND PRIOR ART OF THE INVENTION

Increased demand for cleaner fuel due to environmental concern and depleting petroleum reserves in the world coupled with deteriorating quality of the crude oil have led a surge of research for renewable and clean fuel sources. One of the renewable sources may be the oil originating from vegetables and animals such as waste restaurant oil, soybean oil, Jatropha oil, and algae oil etc. This also helps in rural development by providing better cost for their products. But these oils originating from vegetables and animals cannot be used directly in the engine due to the problems inherent with these oils such as higher viscosity and oxygen content and poor atomization and lubricity. Therefore before using in the engine these oils are to be converted into bio-diesel or green diesel. Bio- diesel which is Fatty Acid Methyl Esters (FAME) is produced by transesterification bf fatty acids in triglycerides. To use bio-diesel in the engine requires some modification and additional disadvantages are poor performance in cold weather and poor emission. Another way of effectively using these renewable oils is by converting these oils into hydrocarbons with

l much higher cetane value than conventional diesel fuel. This process involves conversion of fatty acids in triglycerides into linear and/or iso-alkanes. This may be obtained by hydrodeoxygenation, decarbonylation, decarboxylation, isomerisation and hydrocracking or a combination of two or more thereof.

The patented literature presents some documents in the hydrogenation of vegetable oil, but these documents do not consider in their scope the intended range covered by this invention.

Reference may be made to US patent No. 2,1631563 which discloses the hydrogenation of vegetable oils combined with mineral oil over a reduced Ni catalyst supported in alumina in the presence of hydrogen at high pressure [5 MPa to50.6 MPa (50 to 500 atmospheres)]. However, this patent does not involve hydrotreatment of a combined load of petroleum and vegetable oils through an HDT process.

Reference may be made to US Patent No.4, 300,009 which describes a process for generating the product having the boiling point at the range of gasoline boiling point range. This process involves catalytic conversion of anabolites (substances formed in the anabolic process) as resins, vegetable oils and fats in liquid hydrocarbons over zeolites with an effective pore size bigger than 5 Angstrom.

Reference may be made to US Patent No. 5,705,722 which describes a process to produce additives for diesel fuel which have higher cetane number and may improve ignition of the fuel. The process involves hydroprocessing of the biomass, containing a high proportion of unsaturated fatty acids, wood oils, animal fats and other mixtures in the presence of hydrogen over catalyst. This mixture is then separated and fractioned to obtain a hydrocarbon product with boiling point at the range of diesel's boiling point, being this product the additive with a high cetane number. However the addition of a petroleum hydrocarbon to the biomass load which is being hydroprocessed is not mentioned within this document.

Reference may be made to US Patent No.4,992, 605 which describes a process to obtain a stream with, a high cetane number to be added to the diesel in the refinery .The process involves hydroprocessing of vegetable oils such as canola or sunflower oil, palm and wood oil that is a waste product from the wood pulp industry, to produce hydrocarbon products in the diesel boiling range by using sulfided catalyst (NiMo and CoMo) in the presence of hydrogen (pressure of 4 to 15 MPa) and temperature in the range of 350° C to 450°C. This patent does not consider a mixture of a hydrocarbon with vegetable oil in the hydrorefining.

References may be made to Patents US7491858, US7,459,597B2, which describe production of diesel fuel from vegetable and animal oils and also the further isomerization of obtained hydrocarbons using catalysts known in the prior art. Patent WO 2008054442 describes a process for converting triglycerides to hydrocarbons. US Patent No. 4,300,009 describe the production of hydrocarbons such as gasoline and chemicals such as para- xylene from plant oils such as corn oil by using of crystalline aluminosilicate zeolites. US 2004/0230085 Al discloses a process for treating a hydrocarbon component of biological origin by hydrodeoxygenation followed by isomerization.

References may be made to WO 2009/039000, WO 2009/039335, WO/2009/039347, Energy and Environment Science 5 (2011 ) 1667-1671 which describe a process comprising of one or more steps to hydrogenate, decarboxylate, decarbonylate, (and/or hydrodeoxygenate) and isomerize the renewable feedstock, the consumption of hydrogen in the deoxygenation reaction zone is reduced by using at least one sulfur containing component which also operates to maintain the catalyst in a sulfided state. In spite of developments in the technology, there is still a need for a catalyst and process which can be economical for hydroconversion of vegetable oils triglycerides and free fatty acids to directly and selectively obtain iso-paraffins and aromatics in the kerosene range to produce aviation fuel. This will do away with the need for further hydrocracking and hydroisomerization treatments in second step followed by addition of aromatics to obtain desired products such as aviation and/or diesel fuel.

OBJECTIVES OF THE INVENTION

The main objective of the present invention is to provide a catalytic process to convert renewable feedstock into aromatics rich aviation fuel.

Another objective of the present invention is to provide a catalytic process to manufacture n-paraffins and iso-paraffins and aromatics for aviation fuel and diesel fuel from renewable source such as oils originating from vegetable and animal fats by processing these oil in petroleum refinery condition, over a hydroprocessing catalyst using high surface area hierarchically mesoporous zeolite and silica-alumina supports.

SUMMARY OF THE INVENTIO

Accordingly, the present invention provides a catalytic process to convert renewable feedstock into aromatics rich aviation fuel comprises processin of renewable feedstock in a fixed bed reactor with a nulphide catalyst at temperature ranging between 300 - 500°C, pressure in the range of 20-150 bar, space velocity in the range of 0.5-5 h ^"1 and hydrogen gas is in the range of 100- 5000 ml H ₂ / ml liquid feed for a period ranging between 30 -1200 hrs to obtain aromatics rich aviation range kerosene and diesel range. In one embodiment of the present invention catalyst used is selected from the group consisting of sulfided Ni- Mo/ZSM-5, sulfided Ni- Mo/silica- alumina, sulfided Ni-W /ZSM-5 and sulfided Ni-W/ silica- alumina.

In an embodiment of the present invention renewable feedstock used is selected from the group consisting of Jatropha oil, Algal oil and Jatropha and gas oil mixture.

In another embodiment of the present invention gas oil is in the range of 60 -90 wt % in Jatropha and gas oil mixture.

In another embodiment of the present invention diesel range is in the range of 25- 45%.

Still in another embodiment of the present invention aromatics rich aviation kerosene range is in the range of 35- 60 %.

Still in another embodiment of the present invention aromatics in aromatics rich kerosene range is in the range of 1 -18%.

Still in another embodiment of the present invention conversion of renewable feedstock is in the range of 92-99.9%. Still in another embodiment of the present invention catalyst used is selected from the group consisting of sulfided Ni- Mo/ZSM-5, sulfided Ni- Mo/silica- alumina, sulfided Ni-W /ZSM-5 and sulfided Ni-W/ silica- alumina, where the ZSM-5 and silica-alumina have well-defined mesoporosity.

Still in another embodiment of the present invention the temperature along the catalyst bed was kept at different temperatures, top of the catalyst bed at temperature ranging between 320 -400 °C, middle of the catalyst bed at temperature ranging between 400 -500 °C, bottom of the catalyst bed at temperature ranging between 420 -480 °C.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a catalytic process for the manufacture of the n-paraffins, isoparaffin, cyclo-paraffins and aromatics for the aviation turbine fuel and diesel range from renewable source such as oils originating from vegetable and animal fats as such or along with petroleum fraction. The renewable source as such or mixed with petroleum fraction is contacted with a catalyst in the presence of hydrogen at temperature and pressure and liquid hourly velocity of 320-450 °C, 30-150 atm and 0.5-5.0 h ^"1 respectively. The renewable feed stock is converted into paraffins by decarboxylation/decarbonylation, hydrodeoxygenation and hydroisomerization, into aromatics by aromatization, whereas sulfur of petroleum fraction reduces by hydrodesulfurization. The product selectivity is optimised by suitably selecting the catalyst and process conditions. The (re)sulfidation of the catalyst, during processing the pure vegetable oil, helps in maintaining the desired activity and in addition there is favorable changes in the product pattern i.e. resulfidation favours decarboxylation /decarbonylation as compared to hydrodeoxygenation thereby lowering hydrogen consumption. Non precious metals including nickel, cobalt, molybdenum and tungsten or a combination of two or more thereof are used as catalyst for this process. The supports used for this process are hierarchical mesoporous silica-alumina, zeolites, silicoaluminophosphates or a combination of two or more thereof. Preferably, high surface area mesoporous crystalline and amorphous silica-alumina are used as support due to high dispersion of nanoparticles of active metals in the mesopores and on the surface, and to have better diffusion of bulky reactant and product molecules. The process parameters H ₂ /Feed ratio, temperature, space velocity and hydrogen pressure are tuned to control the aromatics content in the final product.

An alternative option to effective use of the renewable source to produce clean fuels and to partly reduce the consumption of the crude oil is the co-processing of the oil from renewable source with petroleum fraction. The renewable source mixed with petroleum fraction and processed over catalyst under hydroprocessing conditions to convert the renewable source into n-paraffins, isoparaffins and aromatics along with hydroprocessing of petroleum fraction. The selectivity of the produced n-paraffins, iso-paraffins and aromatics range may be shifted to ATF and diesel by suitably selecting the active metals, support and process conditions. The reactions occurring during the process are hydrocracking, hydrodeoxygenation, . hydrodesulfurization, hydrodenitrogenation, decarboxylation and decarbonylation and /or combination thereof. Non- precious metals are used as active metals in the catalyst. The metal oxide or mixture of metal oxide, zeolite and/ or combination thereof is used as support. Renewable source includes but not limited to the oil originating from vegetable and animal fats. It includes, but not limited to, waste cooking oil, soyabean oil, jatropha oil, camelina oil, karanj oil, rice-bran oil and algae oil etc. These oils mainly contain free fatty acid and triglycerides. Petroleum fraction is the gas oil originating from the fossil fuels. It includes, but not limited to, kerosene oil, gas oil and vacuum gas oil. Non precious metals including nickel (Ni), cobalt (Co), molybdenum (Mo), tungsten (W), or combination thereof, e.g., nickel-molybdenum (Ni-Mo), cobalt-molybdenum (Co-Mo) nickel-tungsten (Ni-W) are used as active metals. These active metals are supported in mesoporous γ-alumina (γ-Α1 ₂ 0 ₃ ), silica- alumina, silicoaluminophosphates and /or zeolite or a combination thereof. The active metal(s) may be either in the reduced or suifided form. Catalyst is reduced in the reactor itself. The hydrogen flow is kept constant at a specified rate and temperature of the bed is increased to 280° C at a specified rate and keeps the bed this temperature under hydrogen flow for a specified period and then cool down the reactor to 50° C. The sulfidation of the reactor is also carried out in the reactor itself. The sulfidation is done by using the sulfur containing compound such as sulfides, disulfides, and dimethyldisulfides. The catalyst bed is dried out by maintaining the nitrogen flow and increasing the bed temperature to 175° C at a specified rate. The sulfiding agent mixed with straight run petroleum fraction is injected in the bed. Hydrogen flow is also maintained at specified rate. The temperature of the reactor bed is increased to the reaction temperature in a programmed way. After sulfidation, the sulfidation feed is replaced by actual feed.

Microporous molecular sieves such as zeolites possessing secondary mesopores are reported to overcome the diffusional problems of bulky reactants and products. Zeolite materials possessing large secondary pores, by infiltration of zeolite seed crystals into mesoporous diatomaceous earth (Angew. Chem. Int. Ed., 2000, 39, 2707), mesoporous materials from self assembly of preformed zeolite seed crystals in the presence of surfactant (U.S. Pat. No. 6,770,258 B2), zeolite seed crystals coating the mesopore walls of pre-synthesized mesoporous silica (U.S. Pat. No. 6,669,924 Bl), mesoporous zeolites prepared by crystallization in the presence of various solid templates such as carbon nanoparticles, nanofibers and polymer beads, (U.S. Pat. No. 6,680,013 Bl, U.S. Pat. No. 6,620,402 B2, Kaneko, K. et al., J. Am.Chem.Soc, 2003, 125, 6044) may exhibit an enhanced catalytic activity due to the facile molecular diffusion via the mesopores (Christensen, C. H. et al., J. Am.Chem. Soc, 2003, 125, 13370). Zeolite materials having both of micropores and mesopores in a particle have multiple advantages. The intrinsic micropores in the zeolite framework provide with molecule selectivity and active sites and the additional mesopores facilitate the molecule diffusion within micropores to improve the diffusion and adsorption of molecules as well as to modify the diffusion and adsorption of even larger molecules. Mesoporous zeolitic materials such as ZSM- 5 (Meso-ZSM-5) synthesized by using organosilane mesopore templates ( WO2007/ 043731A1 ) has advantages, of having tunable acidities and intra- crystalline micro- and meso- porosities, and can be cost-effective if synthesized from natural clays such as kaolin as inorganic precursors.

In one embodiment of this invention, vegetable oil and/or natural fats either in a pure state, or in a mixture with petroleum fraction, in the range of 0% to100% by volume, preferably between 0% and 60% by volume, and even more preferably between 10% and 40% of vegetable hydrocarbon oil over the total volume of the hydrocarbon mixture is contacted with disclosed catalyst in the presence of hydrogen at elevated temperature and pressure. The temperature range of the catalytic bed may vary from 250 ° C to 450° C, preferably between 300°C to 360°C. The pressure range of the catalytic bed may vary from 30 bar to 150 bar, preferably in the range of 40 to 100 bar. The space velocity range may be from 0.5 h ^"1 to 5 h ^" \ preferably between 1 h ^'1 and 4 h; ¹ . The hydrogen/ hydrocarbon ration in the reactor may vary from 100 NmL of hydrogen/mL of hydrocarbon to 5000 NmL of hydrogen/mL of hydrocarbon preferably between 200NmL of hydrogen/mL of hydrocarbon to 3000 NmL of hydrogen/mL of hydrocarbon. The products were analyzed by gas-chromatography. he . concentration of sulfur was determined by XRF analysis. Simulated distillations of the products were carried out according to the ASTM-2887-D86 procedure. Total acidity number (TAN) was determined following ASTMD974 method. In an alternative embodiment of this invention, pure triglycerides preferably jatropha oil containing free fatty acids, or algal oil is contacted with disclosed sulfided catalyst in the presence of hydrogen at elevated temperature and pressure. The temperature range of the catalytic bed may vary from 250° C to 400°C, preferably between 300°C to 360°C. The pressure range of the catalytic bed may vary from 30 to 150 bar, preferably in the range of 40 to 100 bar. The space velocity range may be from 0.5 h ^"1 to 5 h ^"1 , preferably between 1 h ^"1 and 4 h ^"1 . The hydrogen/ hydrocarbon ration in the reactor may vary from 100 NmL of hydrogen/mL of hydrocarbon to 5000 NmL of hydrogen/mL of hydrocarbon preferably between 200 NmL of hydrogen/mL of hydrocarbon to 3000 NmL of hydrogen/mL of hydrocarbon. With the indication of catalyst deactivation in terms of appearance of unreacted triglyceride as observed by GC, the catalyst is resulfided by putting 1000 ppm dimethyldisulfide in the vegetable oil. The products obtained with this resulfided catalyst have higher content of C17 as compared to C18. The products were analyzed by gas-chromatography. The concentration of sulfur was determined by XRF analysis. Simulated distillation of the products was carried out according to the ASTM-2887-D86 procedure. Total acidity number (TAN) was determined following ASTMD974 method.

Gas chromatography analysis of the product obtained after processing the triglycerides and their gas oil mixture shows the concentration of C15-C18 paraffin is 80-98% by weight. The sulfur analysis of the product after strippin the dissolved H ₂ S by XRF shows >90% HDS.

The products were analyzed by gas-chromatography ASTM D6730 DHAX analysis. The concentration of sulfur was determined by XRF analysis. Simulated distillation of the products was carried out according to the ASTM-2887-D86 procedure. Total acidity number (TAN) was determined following ASTMD974 method. Examples

The following examples are given by way of illustration and therefore should not be construed to limit the scope of the present invention.

EXAMPLE 1

Jatropha oil, gas oil mixtures (10:90) (1.5Kg jatropha : 13.5 Kg gas oil)were processed in a fixed bed reactor with sulfided Ni-Mo/Meso-ZSM-5, 150 gm (3% NiO and 18% Mo0 ₃ ). The reaction conditions for experiments were: 380 ^° C, 50 bar, 4 h ^"1 and 1500 ml H ₂ gas/ ml liquid feed, for 1200 hours continuously. The products were analyzed by gas-chromatography. The concentration of sulfur in product determined by XRF analysis was 132 ppm. Simulated distillation of the products carried out according to the ASTM-2887-D86 procedure showed 25% of product in diesel range and 45% in kerosene range. ASTM D6730 DHAX analysis showed around 5% aromatics in the kerosene range. Total acidity number (TAN) determined following ASTMD974 method was zero for the product.

EXAMPLE 2

Jatropha oil, gas oil mixtures (25:75) ίβ Kg Jatropha : 9.0 Kg gas oil) were processed in a fixed bed reactor with sulfided Ni-Mo/Meso-ZSM-5, 150 gm, (3% NiO and 18% M0O3). The reaction conditions for experiments were: 360 ^° C, 60 bar, 2 h ^{'1 ,} and 1500 ml H ₂ gas/ ml liquid feed for 1200 hours. The products were analyzed by gas-chromatography. The products had 45% of product in diesel range and 35% in kerosene range. ASTM D6730 DHAX analysis showed around 7% aromatics in the kerosene range. Total acidity number (TAN) determined following ASTMD974 method was zero for the product.

EXAMPLE 3

Jatropha oil, gas oil mixtures (25:75) (3.0 Kg Jatropha : 9.0 Kg gas oil) were processed in a fixed bed reactor with sulfided Ni-Mo/Meso-ZSM-5, 150 gm (3% NiO and 18% M0O3). The reaction conditions for hydrotreating experiments were: 380 ^° C, 60 bar, 2 h ^"1 and 1500 ml H ₂ gas/ ml liquid feed for 1200 hours. The products were analyzed by gas-chromatography. The concentration of sulfur in product determined by XRF analysis was 123 ppm. Simulated distillation of the products carried out according to the ASTM-2887-D86 procedure showed 35% of product in diesel range and 45% in kerosene range. ASTM D6730 DHAX analysis showed around 9% aromatics in the kerosene range.

EXAMPLE 4

Jatropha oil, gas oil mixtures (40:60) (6.0 Kg Jatropha : 9.0 Kg gas oil) were processed in a fixed bed reactor with sulfided Ni-W/Meso-ZSM-5, 150 gm (3% NiO and 18% Wo0 ₃ ). The reaction conditions for hydrotreating experiments were: 360 ^° C, 50 ₍ bar, 4 h ^"1 ' and 2750 ml H ₂ gas/ ml liquid feed for 1200 hoursThe products were analyzed by gas-chromatography. Simulated distillation of the products carried out according to the ASTM-2887-D86 procedure showed 45% of product in diesel range and 35% of product in kerosene range. ASTM D6730 DHAX analysis showed around 5% aromatics in the kerosene range. Total acidity number (TAN) determined following ASTMD974 method was zero for the product.

EXAMPLE 5

Jatropha oil, gas oil mixtures (25:75) (3.0 Kg Jatropha : 9.0 Kg gas oil) were processed in a fixed bed reactor with sulfided Ni-W/Meso-ZSM-5, 150 gm (3% NiO and 18% Wo0 ₃ ). The reaction conditions for hydrotreating experiments were: 360 ^° C, 60 bar, 2 h ^"1 and 1500 ml H ₂ gas/ ml liquid feed for 1200 hours. Simulated distillation of the products carried out according to the ASTM-2887- D86 procedure showed 35% of product in diesel range and 45% of product in kerosene (ATF) range. ASTM D6730 DHAX analysis showed around 6% aromatics in the kerosene range.

EXAMPLE 6

Jatropha oil, gas oil mixtures (40:60) (6.0 Kg Jatropha : 9.0 Kg gas oil) were processed in a fixed bed reactor with sulfided Ni-W/Meso-ZSM-5, 150gm (3% NiO and 18% W0O ₃ ). The reaction conditions for hydrotreating experiments were: 370 ^° C, 50 bar, 2 h ^"1 and 2750 ml H ₂ gas/ ml liquid feed for 1200 hours. The Simulated distillation of the products carried out according to the ASTM- 2887-D86 procedure showed 35% of product in diesel range and 60% of product in kerosene (ATF) range. ASTM D6730 DHAX analysis showed around 7% aromatics in the kerosene range.

EXAMPLE 7

Jatropha Oil (15.0 Kg) was processed in a fixed bed reactor with sulfided Ni- Mo/Meso-ZSM-5, 150 gm (3% NiO and 18% Mo0 ₃ ). The reaction conditions for hydrotreating experiments were: 360 ^° C, 80 bar, 2 h ^"1 and 500 ml H ₂ gas/ ml liquid feed for 1200 hours. The products were analyzed by gas-chromatography and showed 94% triglyceride conversion, with 47% of product in kerosene range (C9-C15) with isomer/normal hydrocarbon ratio being 0.6. ASTM D6730 DHAX analysis showed around 10% aromatics in the kerosene range.

EXAMPLE 8

Jatropha Oil (15.0 Kg) was processed in a fixed bed reactor with sulfided Ni- W/Meso-ZSM-5, 150 gm (3% NiO and 18% Wo0 ₃ ). The reaction conditions for experiments were: 380 ^° C, 50 bar, 2 h ^"1 and 500 ml H ₂ gas/ ml liquid feed for 1200 hours. The products were analyzed by gas-chromatography and showed 96% triglyceride conversion, with 41 % of product in kerosene range (C9-C15) with isomer/normal hydrocarbon ratio being 4.9. ASTM D6730 DHAX analysis showed around 1 1% aromatics in the kerosene range.

EXAMPLE 9

Jatropha Oil (15.0 Kg) was processed in a fixed bed reactor with sulfided Ni- Mo/Meso-ZSM-5, 150 gm (3% NiO and 18% Wo0 ₃ ). The reaction conditions for experiments were: 430 ^° C, 50 bar, 2 h ^"1 and 3300 ml H ₂ gas/ ml liquid feed for 1200 hours. The products were analyzed by gas-chromatography and showed 99% triglyceride conversion, with 38% of product in kerosene range (C9-C15) with isomer/normal hydrocarbon ratio being 13.5. ASTM D6730 DHAX analysis showed around 15% aromatics in the kerosene range. Resulfidation is done during reaction by removing the reactant feed and using the sulfidation feed under sulfidation conditions (12h), followed by restart of reaction.

EXAMPLE 10

Algal Oil (0.25 Kg) was processed in a fixed bed reactor with sulfided Ni- Mo/Meso-ZSM-5, 5gm (3% NiO and 18% Mo0 ₃ ). The reaction conditions for experiments were: 350 ^° C, 50 bar, 2 h ^"1 and 500 ml H ₂ gas/ ml liquid feed 30 hours. The products were analyzed by gas-chromatography and showed 92% triglyceride conversion, with 34% of product in kerosene range (C9-C15) with isomer/normal hydrocarbon ratio being 4.5. ASTM D6730 DHAX analysis showed around 8% aromatics in the kerosene range.

EXAMPLE 1 1

Algal Oil (0.25 Kg)was processed in a fixed bed reactor with sulfided Ni- Mo/Meso-ZSM-5, 5 gm (3% NiO and 18% Mo0 ₃ ). The reaction conditions for experiments were: 400 ^° C, 50 bar, 2 h ^"1 and 500 ml H ₂ gas/ ml liquid feed 30 hours. The products were analyzed by gas-chromatography and showed 98% triglyceride conversion, with 54% of product in kerosene range (C9-C15) with isomer/normal hydrocarbon ratio being 3.5. ASTM D6730 DHAX analysis showed around 18% aromatics in the kerosene range. Resulfidation is done during reaction by removing the reactant feed and using the sulfidation feed under sulfidation conditions (12h), followed by restart of reaction.

EXAMPLE 12

Jatropha Oil (1500 Kg) was processed in a fixed bed reactor with sulfided Ni- W/Meso-silica-alumina 1000 g (3% NiO and 18% Wo0 ₃ ). The reaction conditions for experiments were: 350 ^° C, 90 bar, 2 h ^"1 and 500 ml H ₂ gas/ ml liquid feed 1200 hours. The products were analyzed by gas-chromatography and showed 96% triglyceride conversion, with 41% of product in kerosene range (C9-C15) with isomer/normal hydrocarbon ratio being 4.9. ASTM D6730 DHAX analysis showed around 6% aromatics in the kerosene range.

EXAMPLE 13

Jatropha Oil (1500 Kg) was processed in a fixed bed reactor with sulfided Ni- Mo/Meso-silica-alumina 1000 g (3% NiO and 18% Mo0 ₃ ). The reaction conditions for experiments were: 340 ^° C, 75 bar, 1 h ^"1 and 1000 ml H ₂ gas/ ml liquid feed 1200 hours. The products were analyzed by gas-chromatography and showed 94% triglyceride conversion, with 38% of product in kerosene range (C9- C15) with isomer/normal hydrocarbon ratio being 6.5. ASTM D6730 DHAX analysis showed around 4% aromatics in the kerosene range. Resulfidation is done during reaction by removing the reactant feed and using the sulfidation feed under sulfidation conditions (12h), followed by restart of reaction.

EXAMPLE 14

Jatropha Oil (1500 Kg) was processed in a fixed bed reactor with sulfided Ni- Mo/Meso-silica-alumina 1000 g (3% NiO and 18% Mo0 ₃ ). The reaction conditions for experiments were: 100 bar, 1.5 h ^"1 and 2500 ml H ₂ gas/ ml liquid feed 1200 hours. The temperature of the catalysts bed was 350°C (top of catalyst bed), 470°C (middle of catalyst bed) and 440°C (bottom of the catalyst bed). The products were analyzed by gas-chromatography and showed 99.9% triglyceride conversion, with 35% of product in kerosene range (C9-C15) with isomer/normal hydrocarbon ratio being 11.5. ASTM D6730 DHAX analysis showed around 12% aromatics in the kerosene range. Resulfidation is done during reaction by removing the reactant feed and using the sulfidation feed under sulfidation conditions (12h), followed by restart of reaction.

EXAMPLE 15

Jatropha Oil (1500 Kg) was processed in a fixed bed reactor with sulfided Ni- Mo/silica-alumina 1000 g (3% NiO and 18% Mo0 ₃ ). The reaction conditions for experiments were: 450 ^" C, 25 bar, 1 h ^"1 and 700 ml H ₂ gas/ ml. liquid feed 1200 hours. The products were analyzed by gas-chromatography and showed 96% triglyceride conversion, with 30% of product in kerosene range (C9-C15) with isomer/normal hydrocarbon ratio being 8.5. ASTM D6730 DHAX analysis showed around 19% aromatics in the kerosene range. Resulfidation is done during reaction by removing the reactant feed and using the sulfidation feed under sulfidation conditions (12h), followed by restart of reaction.

COMPARATIVE EXAMPLE 16

Algal Oil (0.25 Kg) was processed in a fixed bed reactor with sulfided Ni- Mo/Meso-ZSM-5, 5 gm (3% NiO and 18% Mo0 ₃ ). The reaction conditions for experiments were: 400 ^° C, 80 bar, 1 h ^"1 and 1500 ml H ₂ gas/ ml liquid feed 30 hours. The products were analyzed by gas-chromatography and showed 99% triglyceride conversion, with 65% of product in kerosene range (C9-C15) with isomer/normal hydrocarbon ratio being 7.5. ASTM D6730 DHAX analysis showed no aromatics in the kerosene range.

Example 17: Catalyst Preparation:

Octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride (ODAC) was added to a conventional alkaline mixture for zeolite ZSM-5 synthesis taking tetrapropylammonium bromide (TPABr) as the micropore template. The molar composition of the mixture was 1 AI2O3/10 TPABr/ 10 Na20/38 Si ^' 02/1. -4.2 ODAC /7,200 H20. 2.0 g sodium aluminate, 28.0 g TPABr and 8.0 g NaOH were first dissolved in 1 ,350 g H20. To the resultant solution, a mixture of 85.7 g tetraethylorthosilicate, and 37.5g of ODAC (60% methanol solution) was added under vigorous stirring. Si/Al ratio was fixed to 19. The final mixture was further stirred for 2 h at room temperature ( 25°C) to obtain a homogeneous mixture. This mixture was heated hydrothermally at 140°C for 2 days, in an autoclave. The precipitated product was filtered and washed with distilled water. The product was dried in an oven at 100°C arid subsequently calcined in air at 550 C for a period 8 hrs. Hydroconversion reactions are carried out in fixed bed trickle reactor with sulfided catalysts. The catalysts were prepared by conventional impregnation of the support (3% NiO and 18% o0 ₃ ) using an aqueous solutions of (ΝΗ ₄ )6Μθ7θ ₂ 4 (Sigma Aldrich), and Ni(N0 ₃ ) ₂ (Sigma Aldrich). The support was mixed with the impregnation solution and after stirring for 1 h it was dried at 100 °C and calcined in an air stream at 400 °C for 1 h. The catalysts were presulfided using a mixture of dimethyl disulfide and gas oil at atmospheric pressure and 350 ^° C for 9h.

ADVANTAGES OF THE INVENTION

The present invention relates to a catalytic process for the manufacture of the n-paraffins, isoparaffin, cyclo-paraffins and aromatics of the aviation turbine fuel and diesel range from renewable source such as oils originating from plant, algae and animal fats along with hydrotreating of petroleum fraction. The renewable feed stock is converted into paraffins by decarboxylation /decarbonylation and hydrodeoxygenation along with cracking, isomerisation and aromatization whereas sulfur of petroleum fraction reduces by hydrodesulfurization. The product selectivity is optimised by suitably selecting the catalyst and process conditions. The (re)sulfidation of the catalyst, during processing the pure vegetable oil, helps in maintaining the desired activity and in addition there is favorable changes in the product pattern thereby lowering hydrogen consumption. The supports used for this process are mesoporous alumina, silica-alumina, zeolite or a combination of two or more thereof. Preferably, high surface area mesoporous zeolite is used as support due to high dispersion of nanoparticles of active metals in the mesopores and on the surface, and to have better diffusion _/ of bulky reactant and product molecules. The present invention is a more cost-effective and attractive route to prepare aviation fuel without need to add aromatics separately as the aromatics are produced in the process.