WO2015128879A1 - An improved process for producing renewable diesel fuel - Google Patents

An improved process for producing renewable diesel fuel Download PDF

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Publication number
WO2015128879A1
WO2015128879A1 PCT/IN2015/000107 IN2015000107W WO2015128879A1 WO 2015128879 A1 WO2015128879 A1 WO 2015128879A1 IN 2015000107 W IN2015000107 W IN 2015000107W WO 2015128879 A1 WO2015128879 A1 WO 2015128879A1
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catalyst
range
hydrogen
hydrocarbon
mesoporous silica
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PCT/IN2015/000107
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French (fr)
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Srinivas Darbha
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Council Of Scientific And Industrial Research
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0325—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/043—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/86—Borosilicates; Aluminoborosilicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to an improved process for producing renewable diesel fuel.
  • the present invention provides an improved, hydrogen-free process for producing renewable hydrocarbon fuels of diesel range (C 12 -C2 0 ) from lipid feedstock in the presence of an ordered, high surface area, three-dimensional mesoporous silica-supported Pd or Pt catalyst.
  • the present invention relates to an improved process for producing renewable hydrocarbon-based diesel fuel with 100% theoretical yield and selectivity from lipids feedstocks.
  • hydrotreating of fatty compounds are purely hydrocarbons, fall in the range of diesel fuel with carbon numbers of 12 - 20, have high energy density and low pour point unlike the ester-based biodiesel.
  • the hydrocarbon-based fuels are more favorable for industrial applications. They are compatible with the current engines and avoid the need for blending with the conventional petro-fuels if isomerized. In other words, they can be used directly as standalone fuels.
  • Hydrodeoxygenation (HDO) and decarbonylation / decarboxylation (DCO) are the chemical steps involved in converting fatty compounds/lipids to hydrocarbon-based renewable fuels. In the latter two reactions, the final product contains one carbon less than the starting material.
  • Kiatkittipong et al. reported conversions of crude palm oil (CPO) and its physical refining including degummed palm oil (DPO) and palm fatty acid distillate (PFAD) to diesel fuel in presence of hydrogen by the , hydro-processing route using Pd/C and ⁇ / ⁇ - ⁇ 1 2 0 3 catalysts. It was found that hydroprocessing of CPO on a Pd/C catalyst at 400°C, 40 bar hydrogen, and reaction time of 3 hours provides the highest diesel yield of 51%. When gum which contains phospholipid compounds was removed from CPO, the highest diesel yield of 70% was obtained at a shorter reaction time (1 h). In the case of PFAD, which consisted mainly free fatty acids, a maximum diesel yield of 81% was observed at 375 °C and 0.5 hours.
  • CPO crude palm oil
  • DPO degummed palm oil
  • PFAD palm fatty acid distillate
  • Veriansyah et al. (Fuel, Vol. 94, Year 2012, pp. 578-585) reported the effects of various supported catalysts on converting soybean oil in presence of hydrogen.
  • the hydro- processing conversion order was found to be: sulfided ⁇ / ⁇ - ⁇ 1 2 0 3 (92.9%) > 4.29 wt.% Pd/y-Al 2 0 3 (91.9%) > sulfided CoMo/y-Al 2 0 3 (78.9%) > 57.6 wt.% Ni/Si0 2 - Al 2 O 3 (60.8%) > 4.95 wt.% ⁇ / ⁇ - ⁇ 1 2 0 3 (50.8%) > 3.06 wt.% Ru/Al 2 0 3 (39.7%) at a catalyst/oil weight ratio of 0.044.
  • Sari et al. (Appl. Catal. A: Gen. Vol. 467, Year 2013, pp. 261-269) reported the application of a highly active nanocomposite silica-carbon supported palladium (5 wt%) catalyst for decarbonylation of free fatty acids for green diesel production in the absence of hydrogen at 300°C and 15 bar. Although, a continuous supply of hydrogen was not needed, intermittent hydrogen treatment was essential to keep the catalyst's life in a continuous run. In spite of that, a loss in feed conversion was noted after 3 hours of a continuous run. Selectivity for the decarboxylated product (C 17) was between 40% and 90% only.
  • High surface area of silica perhaps enabled better dispersion of the noble metal (Pt Pd) in the present case and thereby, leading to efficient catalytic activity and requirement of lesser amounts of metal content. Further, sintering of metal is lower compared to that on reported supports.
  • Three-dimensional ordered mesoporosity of the support of the present invention perhaps enabled facile diffusion of the bulky fatty compounds/lipids and product hydrocarbon molecules compared to the one- and two-dimensional silica materials and thereby, led to high turnover frequency/initial reaction rate.
  • Three-dimensional pore architecture of the support of present invention is the possible reason, perhaps, enabled better access of the reactant molecules to the active metal sites.
  • the main objective of present invention is to provide an improved, hydrogen-free process for producing renewable hydrocarbon fuels of diesel range (C 12 -C2o) from lipid feedstock in the presence of an ordered, high surface area, three-dimensional mesoporous silica-supported Pd or Pt catalyst.
  • Another objective of present invention is to provide an improved, hydrogen-free process for producing renewable hydrocarbon fuels of diesel range (C 12 -C 20 ) from lipid feedstocks with 100% theoretical yield and selectivity in the absence of hydrogen.
  • the present invention provides an improved process for producing renewable hydrocarbon-based diesel fuel with carbon number in the range 12 to 20 with 100% theoretical yield and selectivity wherein the said process comprises the steps of:
  • step (b) venting out the gaseous product obtained in step (a), separating the liquid from the catalyst system and isolating the diesel range hydrocarbon fuel from the liquid by distillation and recycling of unreacted feed to step (a).
  • the said process is optionally carried out in presence of pure hydrogen or hydrogen containing inert gas.
  • the three-dimensional mesoporous silica support is SBA-12, SBA-16 and related three-dimensional mesoporous silica.
  • Pd or Pt content in the catalyst is in the range of 1 - 5 wt% of the support.
  • the three-dimensional mesoporous silica support may optionally contain heteroatoms Al, B, Sn or Ti in its composition with Si/heteroatom molar ratio in the range of 20 to 80.
  • the lipid feedstock is a fatty acid ester, fatty acid, fatty alcohol or the mixtures thereof.
  • the inert gas is nitrogen, helium or argon.
  • the lipid feedstock is obtained from vegetable oil, animal fat, algae oil or the mixtures thereof preferably selected from oleic acid' and soybean oil.
  • the solid catalyst has surface area of 400 - 2000 m /g and average mesopore diameter of 2 - 8 nm.
  • the present invention provides an improved, hydrogen-free process for producing renewable hydrocarbon fuels of diesel range (C 12 -C 2 o) from lipid feedstocks with 100% theoretical yield and selectivity in the absence of hydrogen.
  • the present invention provides an improved, hydrogen-free process for producing renewable hydrocarbon fuels of diesel range (Ci 2 - C 20 ) from lipid feedstocks with 100% theoretical yield and selectivity and a stable and reusable catalyst even in the absence of hydrogen.
  • the present invention provides an improved process for producing renewable hydrocarbon-based, diesel fuel with carbon number in the range 12 to 20, with 100% theoretical yield and selectivity wherein the said process comprises the steps of:
  • step (b) venting out the gaseous product obtained in step (a), separating of the liquid from the catalyst system and isolating the diesel range hydrocarbon fuel from the liquid by distillation and recycling of unreacted feed to step (a).
  • the three-dimensional mesoporous silica support is SBA-12, SBA-16, MCM-48 and related three-dimensional mesopore silica or silicate materials.
  • Pd and Pt contents in the catalyst are in the range 1.- 5 wt% of the support and the three-dimensional silica support optionally contains heteroatoms like Al, B, Sn and Ti in its composition with Si/heteroatom molar ratio in the range of 20 to 80.
  • the lipid feedstock is a fatty acid ester, fatty acid, vegetable oil, animal fat, algae oil, fatty alcohol or the mixtures there of.
  • the fatty acid ester is preferably selected from a fatty acid glyceride or fatty acid alcoholate.
  • the lipid feedstock is selected from oleic acid and soybean oil.
  • the solid catalyst has surface area in the range of 400 - 2000 m 2 /g and average mesopore diameter in the range 2 - 8 nm.
  • the hydrogen-containing gas if used optionally, has hydrogen content of 0.5 - 10 vol%.
  • the product hydrocarbon has number of carbons in the range of 12 - 20.
  • the conversion of lipid feedstock to renewable hydrocarbon is greater than 95 mol%.
  • the ordered, high surface area, three-dimensional mesoporous silica-supported Pd or Pt catalyst of the present invention is highly efficient, stable and reusable.
  • High dispersion of metal, prevention of sintering due to high surface area and higher activity due to three- dimensional mesoporous nature and better accessibility of Pd and Pt in the pores, high stability during reactions and hydrogen-free processing make the process of the current invention unique, advantageous and economical.
  • the catalyst of the present invention is highly efficient and provides diesel range hydrocarbons in 100 mol% theoretical yield and selectivity.
  • the catalyst of present invention that Pd or Pt is highly dispersed on the surface of the three-dimensional mesoporous silica or silicate support.
  • Metal dispersion on the support lies between 20% and 60%.
  • EXAMPLE 1 This example illustrates the preparation of SBA-12 supported Pd(5 wt%) catalyst.
  • 160 g of 2 M HC1 and 40 g of distilled water were taken a polypropylene beaker.
  • 8 g of Brij-76 [Ci 8 H 37 (OCH 2 CH 2 )i 0 OH, mol. wt. ⁇ 711] was dissolved in it while stirring the mixture at 40°C for 2 hours.
  • 17.6 g of tetraethyl orthosilicate was added over 30 min. Stirring was continued for 20 hours.
  • the gel formed was transferred into a Teflon-lined stainless-steel autoclave and heated at 100°C for 24 hours.
  • Pd(5 wt%) supported on SBA-16 [Pd(5 wt%)/SBA-16] was prepared as follows: 1.425 g of tetraatnminepalladium(II) nitrate [Pd(NH 3 ) 4 (N0 3 ) 2 , 10 wt% solution in water] was added drop- wise to 1 g of SBA-16 taken in a glass, beaker.
  • This example illustrates the preparation of diesel range hydrocarbon fuel in the absence of hydrogen using Pd(5 wt%)/SBA-12 catalyst.
  • This example illustrates the preparation of diesel range hydrocarbon fuel in the absence of hydrogen using Pd(5 wt%)/SBA-16 catalyst.
  • 2 g of oleic acid, 0.2 g of Pd(5 wt%)/SBA-16 and 30 g of n-decane were taken in a stainless steel Parr reactor (Parr 4848). The reactor was pressurized to 30 bar with inert gas nitrogen.
  • This example illustrates the preparation of diesel range hydrocarbon fuel in the presence of hydrogen using Pd(5 wt%)/SBA-16 catalyst.
  • EXAMPLE 6 This example illustrates the preparation of diesel range hydrocarbon fuel in the presence of hydrogen using Pd (3 wt%)/SBA-16 catalyst.
  • Pd (3 wt%)/SBA-16 catalyst.
  • 2 g of soybean oil (representative fatty acid alkyl glyceride ester), 0.2 g of Pd (3 wt%)/SBA-16 and 30 g of n-decane were taken in a Parr micro bench-top reactor (Parr 4848). The reactor was pressurized to 10 bar with hydrogen. Temperature of the reactor was raised to 325°C and the reaction was conducted for 5 hours. Then, the reactor was cooled to 25°C. Gas was vented out. Liquid portion was separated from the catalyst by centrifugation followed by decantation.
  • EXAMPLE 7 This example illustrates the preparation of renewable fuel in the presence of Pd(5 wt%) supported on Al-containing SBA-16 catalyst.
  • EXAMPLE 8
  • This example illustrates the preparation of diesel range hydrocarbon fuel in a continuous flow fixed bed reactor using Pd(5 wt%)/SBA-16 catalyst.
  • the catalyst powder was shaped into tablet form and placed in the reactor between alumina bead inert zones.
  • the temperature of the reactor was maintained at 325°C and oleic acid + n-decane mixture (1 :15 wt. ratio) was pumped over the catalyst bed at a weight hourly space velocity of 1 hour "1 while maintaining the reactor pressure at 30 bar using inert gas nitrogen.
  • Liquid product was collected continuously. Decane was distilled out and the product was subjected to analysis by gas chromatography and alkali titration. Such runs were conducted continuously for 100 h.
  • This example illustrates the preparation of diesel range hydrocarbon fuel in a continuous flow fixed bed reactor using Pd(5 wt%)/SBA-16 catalyst in presence of 5% hydrogen (and balance being nitrogen).
  • the catalyst powder was shaped into tablet form and placed in the reactor between alumina bead inert zones.
  • the temperature of the reactor was maintained at 300°C and oleic acid + n-decane mixture (1 : 15 wt. ratio) was pumped over the catalyst bed at a weight hourly space velocity of 1.5 hour "1 while maintaining the reactor pressure at 30 bar using 5 vol% hydrogen.
  • Liquid product was collected continuously. Decane was distilled out and the product was subjected to analysis by gas chromatography and alkali titration. Such runs were conducted continuously for 100 hour.
  • the catalyst is stable in the reaction even in the absence of hydrogen.

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  • Engineering & Computer Science (AREA)
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Abstract

The present invention disclosed an improved process for producing renewable hydrocarbon- based diesel fuel with 100% theoretical yield and selectivity from lipid feedstock in the presence of an ordered, high surface area, three-dimensional mesoporous silica-supported Pd or Pt catalyst.

Description

AN IMPROVED PROCESS FOR PRODUCING RENEWABLE DIESEL FUEL
FIELD OF THE INVENTION: The present invention relates to an improved process for producing renewable diesel fuel. Particularly, the present invention provides an improved, hydrogen-free process for producing renewable hydrocarbon fuels of diesel range (C12-C20) from lipid feedstock in the presence of an ordered, high surface area, three-dimensional mesoporous silica-supported Pd or Pt catalyst. More particularly, the present invention relates to an improved process for producing renewable hydrocarbon-based diesel fuel with 100% theoretical yield and selectivity from lipids feedstocks.
BACKGROUND AND PRIOR ART: Currently, most of the energy needs are met from fossil fuel resources which are nonrenewable. Their overly consumption, limited availability, escalating prices and most importantly their negative impact on environment necessitate exploration of renewable fuels. Lipids derived from vegetable and algae oils are suitable feedstock for producing renewable, transportation fuels. While these natural oils cannot be used directly as fuel, their chemical modification makes them suitable for use in the existing fuel combustion engines. Transesterification/esterification of fatty acid glycerides/fatty acids with methanol produces fatty acid methyl esters, known as biodiesel. High cold-flow properties of fatty acid methyl esters restrict their applications in cold climatic conditions. Several efforts have been made to lower the pour point of these esters by adding additives.
'
An alternative approach for renewable transportation fuels is hydrotreating of fatty compounds. These "renewable fuels are purely hydrocarbons, fall in the range of diesel fuel with carbon numbers of 12 - 20, have high energy density and low pour point unlike the ester-based biodiesel. The hydrocarbon-based fuels are more favorable for industrial applications. They are compatible with the current engines and avoid the need for blending with the conventional petro-fuels if isomerized. In other words, they can be used directly as standalone fuels. Hydrodeoxygenation (HDO) and decarbonylation / decarboxylation (DCO) are the chemical steps involved in converting fatty compounds/lipids to hydrocarbon-based renewable fuels. In the latter two reactions, the final product contains one carbon less than the starting material. Conventional hydrodesulfurization catalysts viz. sulfided Ni-Mo, Ni-W and Co-Mo supported on A1203 have been efficient catalysts for hydrotreating of vegetable oils. Leaching of sulfur compounds into the product which necessitate post desulfurization steps, catalyst deactivation and requirement of continuous sulfidation of the catalyst are some of the issues with these catalysts. Need for higher amount and high pressure of hydrogen makes this process more expensive. Further, requirement of large quantities of hydrogen make this process not suitable for commercialization at locations other than refinery.
Supported noble-metal catalysts have been reported for converting fatty compounds into hydrocarbon-based renewable fuels.
Lee et al (Chem. Central J., Vol. 7, Year 2013, page 149) reported deoxygenation of technical grade methyl oleate in presence of hydrogen (at 60 bar) producing diesel fuel aliphatic hydrocarbons (C15- Ci8) using a PdVSBA-15 catalyst. Maximum conversion and heptadecane (CI 7) selectivity were 57% and 95%, respectively.
Kiatkittipong et al. (Fuel Proc. Technol, Vol. 116, Year 2013, pp. 16-26) reported conversions of crude palm oil (CPO) and its physical refining including degummed palm oil (DPO) and palm fatty acid distillate (PFAD) to diesel fuel in presence of hydrogen by the , hydro-processing route using Pd/C and ΝϊΜο/γ-Α1203 catalysts. It was found that hydroprocessing of CPO on a Pd/C catalyst at 400°C, 40 bar hydrogen, and reaction time of 3 hours provides the highest diesel yield of 51%. When gum which contains phospholipid compounds was removed from CPO, the highest diesel yield of 70% was obtained at a shorter reaction time (1 h). In the case of PFAD, which consisted mainly free fatty acids, a maximum diesel yield of 81% was observed at 375 °C and 0.5 hours.
Veriansyah et al. (Fuel, Vol. 94, Year 2012, pp. 578-585) reported the effects of various supported catalysts on converting soybean oil in presence of hydrogen. The hydro- processing conversion order was found to be: sulfided ΝίΜο/γ-Α1203(92.9%) > 4.29 wt.% Pd/y-Al203 (91.9%) > sulfided CoMo/y-Al203 (78.9%) > 57.6 wt.% Ni/Si02- Al2O3(60.8%) > 4.95 wt.% Ρΐ/γ-Α1203 (50.8%) > 3.06 wt.% Ru/Al203 (39.7%) at a catalyst/oil weight ratio of 0.044. The most abundant composition in the liquid product was straight chain n-Cn and n-C 5 alkanes with Ni or Pd catalysts. Lesteri et al (Catal. Lett., Vol. 134, Year 2010, pp. 250-257) reported deoxygenation of stearic acid in dodecane as a solvent at 300°C under 17 bar of 5 vol% ¾ in argon in a semi -batch reactor over palladium on one-dimensional mesoporous SBA-15 catalyst. Stearic acid conversion of 96% and CI 7 product selectivity of 98% were observed. Turnover frequency of the catalyst was low (0.72 sec"1).
Lestari et al {Catal. Lett., Vol. 122, Year 2008, pp. 247-251) reported deoxygenation of stearic acid in dodecane over palladium on nanocomposite carbon Sibunit (Pd/C) catalyst in the temperature range of 270-300°C under 17 bar of helium. Pentadecane (CI 5), a cracking product of heptadecane (CI 7) was obtained in significant amounts (1 :1 ratio). Selectivity for heptadecane (CI 7) was around 50% irrespective of stearic acid conversion.
Decarboxylation of brown grease to diesel hydrocarbon fuel over a 5 wt% Pd/C catalyst was reported by Sari et al., (Ind. Eng. Chem. Res. Vol. 52, Year 2013, pp. 11527 - 1 1536). Brown grease conversion of 90% was obtained in a semi-batch mode reaction in 7 hours. But in a batch reactor, the conversion was only about 40% at similar reaction conditions. Presence of hydrogen improved the yield.
Sari et al. (Appl. Catal. A: Gen. Vol. 467, Year 2013, pp. 261-269) reported the application of a highly active nanocomposite silica-carbon supported palladium (5 wt%) catalyst for decarbonylation of free fatty acids for green diesel production in the absence of hydrogen at 300°C and 15 bar. Although, a continuous supply of hydrogen was not needed, intermittent hydrogen treatment was essential to keep the catalyst's life in a continuous run. In spite of that, a loss in feed conversion was noted after 3 hours of a continuous run. Selectivity for the decarboxylated product (C 17) was between 40% and 90% only.
Snare et al (Ind. Eng. Chem. Res., Vol. 45, Year 2006, pp. 5708-5715) reported a method for production of diesel-like hydrocarbons via catalytic deoxygenation of fatty acid using several supported metal catalysts. A model compound stearic acid was deoxygenated to heptadecane. The deoxygenation reaction done in a semibatch reactor at 300°C and 6 bar. Pd/C showed complete conversion of stearic acid and hexadecane selectivity (C 17) of 95%.
The prior-art processes were expensive or needed additional process steps due to requirement of high amounts of hydrogen or continuous sulfidation of the catalyst. Deactivation and metal sintering were the issues that prohibit the use of known supported Pd catalysts in long time operations. Requirement of intermittent hydrogen gas injection was needed. Even then, the activity of the catalyst could not be retained. Selectivity of CI 7 hydrocarbon product was low with the reported ' catalysts. A highly active, selective and stable catalyst; that requires little or minimum amount of hydrogen makes the renewable fuel production economical.
In view of the importance of renewable transportation fuels and drawbacks of prior- art processes which include catalyst deactivation, metal sintering and requirement of high quantities of hydrogen, it is desirable to have an efficient solid catalyst and a hydrogen-free process for producing renewable fuels in an economic manner. The process of the present invention using ordered, three-dimensional, high surface area, mesoporous silica-supported Pd or Pt catalysts are highly efficient and overcome the deficiencies of prior-art processes. Unexpectedly, Pt and Pd (taken in similar quantities as of the prior art catalysts) on three- dimensional mesoporous silica/silicates showed exceptionally high selectivity at complete conversion of feedstock and with high turnover frequency / initial reaction rates.
High surface area of silica perhaps enabled better dispersion of the noble metal (Pt Pd) in the present case and thereby, leading to efficient catalytic activity and requirement of lesser amounts of metal content. Further, sintering of metal is lower compared to that on reported supports. Three-dimensional ordered mesoporosity of the support of the present invention perhaps enabled facile diffusion of the bulky fatty compounds/lipids and product hydrocarbon molecules compared to the one- and two-dimensional silica materials and thereby, led to high turnover frequency/initial reaction rate. Three-dimensional pore architecture of the support of present invention is the possible reason, perhaps, enabled better access of the reactant molecules to the active metal sites.
Cracking of formed deoxygenation hydrocarbon product over the catalyst of the present invention unlike the prior-art catalysts is little (CI 7 hydrocarbon is the only product from CI 8 fatty acids/esters). One cannot expect this simply by increasing the pore structural dimensionality of the support from one to three dimension.
OBJECTIVE OF INVENTION: The main objective of present invention is to provide an improved, hydrogen-free process for producing renewable hydrocarbon fuels of diesel range (C12-C2o) from lipid feedstock in the presence of an ordered, high surface area, three-dimensional mesoporous silica-supported Pd or Pt catalyst.
Another objective of present invention is to provide an improved, hydrogen-free process for producing renewable hydrocarbon fuels of diesel range (C12-C20) from lipid feedstocks with 100% theoretical yield and selectivity in the absence of hydrogen. SUMMARY OF THE INVENTION:
Accordingly, the present invention provides an improved process for producing renewable hydrocarbon-based diesel fuel with carbon number in the range 12 to 20 with 100% theoretical yield and selectivity wherein the said process comprises the steps of:
(a) contacting a lipid feedstock with an ordered, high surface area, three-dimensional mesoporous silica-supported Pd or Pt catalyst for 0.5 to 6 hrs in a batch reactor or at a weight hourly space velocity of 2 to 6 hr"1 in a continuous flow process, at a temperature in the range of 250 - 375°C and reactor pressure maintained in the range of 5 - 40 bar using an inert gas;
(b) venting out the gaseous product obtained in step (a), separating the liquid from the catalyst system and isolating the diesel range hydrocarbon fuel from the liquid by distillation and recycling of unreacted feed to step (a).
In an embodiment of the present invention the said process is optionally carried out in presence of pure hydrogen or hydrogen containing inert gas.
In an embodiment of the present invention 0.5 to 10 vol% hydrogen in hydrogen containing inert gas.
In one embodiment of the present invention the three-dimensional mesoporous silica support is SBA-12, SBA-16 and related three-dimensional mesoporous silica. In another embodiment of the present invention Pd or Pt content in the catalyst is in the range of 1 - 5 wt% of the support.
Still in another embodiment of the present invention the three-dimensional mesoporous silica support may optionally contain heteroatoms Al, B, Sn or Ti in its composition with Si/heteroatom molar ratio in the range of 20 to 80.
Still in another embodiment of the present invention the lipid feedstock is a fatty acid ester, fatty acid, fatty alcohol or the mixtures thereof.
Still in another embodiment of the present invention the inert gas is nitrogen, helium or argon.
Still in another embodiment of the present invention the lipid feedstock is obtained from vegetable oil, animal fat, algae oil or the mixtures thereof preferably selected from oleic acid' and soybean oil.
Still in another embodiment of the present invention the solid catalyst has surface area of 400 - 2000 m /g and average mesopore diameter of 2 - 8 nm.
Still in another embodiment of the present invention the present invention provides an improved, hydrogen-free process for producing renewable hydrocarbon fuels of diesel range (C12-C2o) from lipid feedstocks with 100% theoretical yield and selectivity in the absence of hydrogen.
DETAILED DESCRIPTION OF THE INVENTION:
The invention will now be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated.
The present invention provides an improved, hydrogen-free process for producing renewable hydrocarbon fuels of diesel range (Ci2 - C20) from lipid feedstocks with 100% theoretical yield and selectivity and a stable and reusable catalyst even in the absence of hydrogen.
The present invention provides an improved process for producing renewable hydrocarbon-based, diesel fuel with carbon number in the range 12 to 20, with 100% theoretical yield and selectivity wherein the said process comprises the steps of:
(a) contacting a lipid feedstock with an ordered, high surface area, three-dimensional mesoporous silica-supported Pd or Pt catalyst for 0.5 to 6 hours in a batch reactor or at a weight hourly space velocity in the range of 2 to 6 hour"1 in a continuous flow process, at a temperature in the range of 250 - 375 °C and reactor pressure maintained in the range of 5 .- 40 bar using an inert gas, wherein the lipid feedstock is a compound containing fatty acid glyceride or fatty acid or fatty alcohol or fatty acid alkyl ester or the mixtures thereof and the inert gas is nitrogen or helium;
(b) venting out the gaseous product obtained in step (a), separating of the liquid from the catalyst system and isolating the diesel range hydrocarbon fuel from the liquid by distillation and recycling of unreacted feed to step (a).
The three-dimensional mesoporous silica support is SBA-12, SBA-16, MCM-48 and related three-dimensional mesopore silica or silicate materials.
Pd and Pt contents in the catalyst are in the range 1.- 5 wt% of the support and the three-dimensional silica support optionally contains heteroatoms like Al, B, Sn and Ti in its composition with Si/heteroatom molar ratio in the range of 20 to 80.
The lipid feedstock is a fatty acid ester, fatty acid, vegetable oil, animal fat, algae oil, fatty alcohol or the mixtures there of.
The fatty acid ester is preferably selected from a fatty acid glyceride or fatty acid alcoholate.
In present invention, the lipid feedstock is selected from oleic acid and soybean oil. The solid catalyst has surface area in the range of 400 - 2000 m2/g and average mesopore diameter in the range 2 - 8 nm.
The hydrogen-containing gas, if used optionally, has hydrogen content of 0.5 - 10 vol%. The product hydrocarbon has number of carbons in the range of 12 - 20.
The conversion of lipid feedstock to renewable hydrocarbon is greater than 95 mol%.
The ordered, high surface area, three-dimensional mesoporous silica-supported Pd or Pt catalyst of the present invention is highly efficient, stable and reusable. High dispersion of metal, prevention of sintering due to high surface area and higher activity due to three- dimensional mesoporous nature and better accessibility of Pd and Pt in the pores, high stability during reactions and hydrogen-free processing make the process of the current invention unique, advantageous and economical.
The catalyst of the present invention is highly efficient and provides diesel range hydrocarbons in 100 mol% theoretical yield and selectivity.
The catalyst of present invention that Pd or Pt is highly dispersed on the surface of the three-dimensional mesoporous silica or silicate support. Metal dispersion on the support lies between 20% and 60%.
Examples: The following examples are given by way of illustration only and therefore should not be construed to limit the scope of the present invention.
EXAMPLE 1: This example illustrates the preparation of SBA-12 supported Pd(5 wt%) catalyst. In a typical preparation, 160 g of 2 M HC1 and 40 g of distilled water were taken a polypropylene beaker. Then, 8 g of Brij-76 [Ci8H37(OCH2CH2)i0OH, mol. wt. ~ 711] was dissolved in it while stirring the mixture at 40°C for 2 hours. Then, 17.6 g of tetraethyl orthosilicate was added over 30 min. Stirring was continued for 20 hours. The gel formed was transferred into a Teflon-lined stainless-steel autoclave and heated at 100°C for 24 hours. The solid formed was filtered, washed thoroughly with distilled water and dried at 100°C for 12 hours. Then, it was calcined at 550°C for 8 hours to get three-dimensional mesoporous silica SBA-12. Pd(5 wt%) > supported on SBA-12 [Pd(5 wt%)/SBA-12] was prepared as follows: 1.425 g of tetraamminepalladium(II) nitrate [Pd(NH3)4(N03)2, 10 wt% solution in water] was added drop-wise to 1 g of SBA-12 taken in a glass beaker. It was mixed thoroughly at 25°C, dried at 120°C for 5 hours till all the water evaporated and then, calcined at 400°C for 2 hours. Surface area = 804 m2/g, pore volume = 1.1 ml/g, average pore size 4.6 nm, average particle size = 4 - 5 nm.
EXAMPLE 2:
This example illustrates the preparation of SBA-16 supported Pd(5 wt%) catalyst. In a typical preparation, Pluronic F127 block-copolymer (EOIO6P070EOJO6; mol. wt. = 12600; 7.4 g) was dissolved in 384.3 g of 2 M HC1 solution at 40°C while stirring for 2 hours. To it, 28.34 g of TEOS was added over 30 min. Stirring was continued for 24 hours. The gel formed was transferred into a Teflon-lined stainless steel autoclave. It was crystallized at 100°C for 48 hours. The solid formed was filtered, washed thoroughly with distilled water, dried overnight at 100°C and calcined at 550°C for 8 hours to get three-dimensional mesoporous silica SBA-16. Pd(5 wt%) supported on SBA-16 [Pd(5 wt%)/SBA-16] was prepared as follows: 1.425 g of tetraatnminepalladium(II) nitrate [Pd(NH3)4(N03)2, 10 wt% solution in water] was added drop- wise to 1 g of SBA-16 taken in a glass, beaker. It was mixed thoroughly at 25 °C, dried at 120°C for 5 hours till all the water evaporated and then, calcined at 400°C for 2 hours. Surface area = 525 m /g, pore volume = 0.6 ml/g, average pore size = 3.2 nm, average particle size - 2 - 3 nm.
EXAMPLE 3:
This example illustrates the preparation of diesel range hydrocarbon fuel in the absence of hydrogen using Pd(5 wt%)/SBA-12 catalyst. In a typical experiment, 2 g of oleic acid, 0.2 g of Pd(5 wt%)/SBA-12 and 30 g of n-decane were taken in a stainless steel Pan- reactor (Parr 4848). The reactor was pressurized to 30 bar of nitrogen. Temperature of the reactor was raised to 325°C and the reaction was conducted for 5 hours. Then, the reactor was cooled to 25 °C. Gases were vented out. Liquid portion was separated from the catalyst by centrifugation followed by decantation. n-Decane was distilled out from the liquid portion and the diesel range hydrocarbon was isolated. Oleic acid conversion = 97 mol%, Hydrocarbon yield = 100% of converted oleic acid. Product selectivity: n-hept&decane = 98%, n-octadecane = 2%.
EXAMPLE 4:
This example illustrates the preparation of diesel range hydrocarbon fuel in the absence of hydrogen using Pd(5 wt%)/SBA-16 catalyst. In a typical experiment, 2 g of oleic acid, 0.2 g of Pd(5 wt%)/SBA-16 and 30 g of n-decane were taken in a stainless steel Parr reactor (Parr 4848). The reactor was pressurized to 30 bar with inert gas nitrogen.
Temperature of the reactor was raised to 325°C and the reaction was conducted for 5 hours.
Then, the reactor was cooled to 25°C. Gases were vented out. Liquid portion was separated from the catalyst by centrifugation followed by decantation. n-Decane was distilled out from the liquid portion and the diesel range hydrocarbon was isolated. Oleic acid conversion =
97.5 mol%, Hydrocarbon yield - 100% of converted oleic acid. Product selectivity: n- heptadecane = 98%, n-octadecane = 2%.
EXAMPLE 5:
This example illustrates the preparation of diesel range hydrocarbon fuel in the presence of hydrogen using Pd(5 wt%)/SBA-16 catalyst. In a typical experiment, 2 g of oleic acid, 0.2 g of Pd(5 wt%)/SBA-16 and 30 g of n-decane were taken in a Parr micro bench-top reactor (Parr 4848). The reactor was pressurized to 10 bar with hydrogen. Temperature of the reactor was raised to 325°C and the reaction was conducted for 5 hours. Then, the reactor was cooled to 25°C. Gas was vented out. Liquid portion was separated from the catalyst by centrifugation followed by decantation. n-Decane was distilled out from the liquid portion and the diesel range hydrocarbon was isolated. Oleic acid conversion = 100 mol%, Hydrocarbon yield = 100% of converted oleic acid. Product selectivity: n-heptadecane = 93.8%, n-octadecane = 6.2%.
EXAMPLE 6: This example illustrates the preparation of diesel range hydrocarbon fuel in the presence of hydrogen using Pd (3 wt%)/SBA-16 catalyst. In a typical experiment, 2 g of soybean oil (representative fatty acid alkyl glyceride ester), 0.2 g of Pd (3 wt%)/SBA-16 and 30 g of n-decane were taken in a Parr micro bench-top reactor (Parr 4848). The reactor was pressurized to 10 bar with hydrogen. Temperature of the reactor was raised to 325°C and the reaction was conducted for 5 hours. Then, the reactor was cooled to 25°C. Gas was vented out. Liquid portion was separated from the catalyst by centrifugation followed by decantation. n-Decane was distilled out from the liquid portion and the diesel range hydrocarbon was isolated. Oleic acid conversion = 97.4 mol%, Hydrocarbon yield = 100% of converted vegetable oil. Product selectivity: n-heptadecane = 46.3%, n-octadecane = 0.9%, n- pentadecane = 48.6%, n-octadecane = 1.0%, other hydrocarbons = 0.6%.
EXAMPLE 7: This example illustrates the preparation of renewable fuel in the presence of Pd(5 wt%) supported on Al-containing SBA-16 catalyst. In a typical experiment, 2 g of oleic acid, 0.2 g of catalyst and 30 g of n-decane were taken in a Parr reactor (Parr 4848). The reactor was pressurized to 10 bar with nitrogen. Temperature of the reactor was raised to 325°C and the reaction was conducted for 3 hours. Then, the reactor was cooled to 25°C. Gas was vented out. Liquid portion was separated from the catalyst by centrifugation followed by decantation. n-Decane was distilled out from the liquid portion and the diesel range hydrocarbon was isolated. Oleic acid conversion = 95.5 mol%, Hydrocarbon yield = 100% of converted vegetable oil. Product selectivity: n-heptadecane = 94%, n-octadecane = 6%. EXAMPLE 8:
This example illustrates the preparation of diesel range hydrocarbon fuel in a continuous flow fixed bed reactor using Pd(5 wt%)/SBA-16 catalyst. The catalyst powder was shaped into tablet form and placed in the reactor between alumina bead inert zones. The temperature of the reactor was maintained at 325°C and oleic acid + n-decane mixture (1 :15 wt. ratio) was pumped over the catalyst bed at a weight hourly space velocity of 1 hour"1 while maintaining the reactor pressure at 30 bar using inert gas nitrogen. Liquid product was collected continuously. Decane was distilled out and the product was subjected to analysis by gas chromatography and alkali titration. Such runs were conducted continuously for 100 h. Oleic acid conversion = 100 mol%, Hydrocarbon yield = 100%. Product selectivity: n- heptadecane = 93%, n-octadecane = 7%. Catalyst showed stable activity and reusable throughout the 100 hour run. EXAMPLE 9:
This example illustrates the preparation of diesel range hydrocarbon fuel in a continuous flow fixed bed reactor using Pd(5 wt%)/SBA-16 catalyst in presence of 5% hydrogen (and balance being nitrogen). The catalyst powder was shaped into tablet form and placed in the reactor between alumina bead inert zones. The temperature of the reactor was maintained at 300°C and oleic acid + n-decane mixture (1 : 15 wt. ratio) was pumped over the catalyst bed at a weight hourly space velocity of 1.5 hour"1 while maintaining the reactor pressure at 30 bar using 5 vol% hydrogen. Liquid product was collected continuously. Decane was distilled out and the product was subjected to analysis by gas chromatography and alkali titration. Such runs were conducted continuously for 100 hour. Oleic acid conversion = 100 mol%, Hydrocarbon yield = 100%. Product selectivity: n-heptadecane ' = 91%, n-octadecane = 9%. Catalyst showed stable activity and reusable throughout the 100 hour run. Advantages of invention:
1. Highly stable and reusable catalyst
2. Hydrogen-free process
3. 100% hydrocarbon yield and selectivity
4. Versatile process applicable for a range of feedstocks.
5. The catalyst is stable in the reaction even in the absence of hydrogen.

Claims

An improved process for producing renewable hydrocarbon-based diesel fuel with carbon number in the range 12 to 20 with 100% theoretical yield and selectivity wherein the said process comprises the steps of:
(a) contacting a lipid feedstock with an ordered, high surface area, three- dimensional mesoporous silica-supported Pd or Pt catalyst for 0.5 to 6 hrs in a batch reactor or at a weight hourly space velocity of 2 to 6 hr"1 in a continuous flow process, at a temperature in the range of 250 - 375°C and reactor pressure maintained in the range of 5 - 40 bar using an inert gas;
(b) venting out the gaseous product obtained in step (a), separating the liquid from the catalyst system and isolating the diesel range hydrocarbon fuel from the liquid by distillation and recycling of unreacted feed to step (a).
The process as claimed in claim 1, wherein the said process is optionally carried out in presence of pure hydrogen or hydrogen containing inert gas.
The process as claimed in claim 2, wherein 0.5 to 10 vol% hydrogen in hydrogen containing inert gas.
The process as claimed in claim 1 , wherein the three-dimensional mesoporous silica support is SBA-12, SBA-16 and related three-dimensional mesoporous silica.
The process as claimed in claim 1, wherein Pd or Pt content in the catalyst is in the range of 1 - 5 wt% of the support.
The process as claimed in claim 1, wherein the three-dimensional mesoporous silica support may optionally contain heteroatoms Al, B, Sn or Ti in its composition with Si/heteroatom molar ratio in the range of 20 to 80.
The process as claimed in claim 1, wherein the lipid feedstock is a fatty acid ester, fatty acid, fatty alcohol or the mixtures thereof.
The process as claimed in claim 1, wherein the inert gas is nitrogen, helium or argon.
The process as claimed in claim 1, wherein the lipid feedstock is obtained from vegetable oil, animal fat, algae oil or the mixtures thereof preferably selected from oleic acid and soybean oil.
The process as claimed in claim 1 , wherein the solid catalyst has surface area of 400 -
2000 m 2 /g and average mesopore diameter of 2 - 8 nm.
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