WO2022162680A1 - A multifunctional catalyst and its composition for single step conversion of triglycerides to transportation fuels - Google Patents

A multifunctional catalyst and its composition for single step conversion of triglycerides to transportation fuels Download PDF

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Publication number
WO2022162680A1
WO2022162680A1 PCT/IN2021/050364 IN2021050364W WO2022162680A1 WO 2022162680 A1 WO2022162680 A1 WO 2022162680A1 IN 2021050364 W IN2021050364 W IN 2021050364W WO 2022162680 A1 WO2022162680 A1 WO 2022162680A1
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Prior art keywords
acid
multifunctional catalyst
extrudates
oil
chelating agent
Prior art date
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PCT/IN2021/050364
Other languages
French (fr)
Inventor
Narasimharao KANNA
Srinivasa Rao GANAGALLA
Pradyut Kumar DHAR
Srikanth Dama
Valavarasu GNANASEKARAN
Ramachandrarao BOJJA
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Hindustan Petroleum Corporation Limited
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Publication of WO2022162680A1 publication Critical patent/WO2022162680A1/en

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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • 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
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel

Definitions

  • the present invention describes a multifunctional catalyst, a composition of the multifunctional catalyst, and use of the said multifunctional catalyst for producing different types of transportation fuels from a single feedstock. Wherein, different types of transportation fuels are produced as per their market demand through a single reaction step and a multifunctional catalyst.
  • biomass is treated under suitable reactor conditions and in the presence of a specific catalysts to breakdown the biomass into required hydrocarbons chains.
  • a specific catalysts to breakdown the biomass into required hydrocarbons chains.
  • such process involves many reaction steps and different types of catalysts are required to produce different types of transportation fuels with specific carbon chains.
  • US9790439B2 discloses a process and apparatus for producing mixture of fuel components through a feed of biological origin. The process comprising subjecting said feed of biological origin and a hydrogen gas feed to hydroprocessing in the presence of a catalyst system comprising dewaxing catalyst to form a mixture of fuel components.
  • US10351781B2 discloses a novel Pt/Pd sodalite caged catalyst combination with sulfided base metal catalyst for improved catalytic hydroprocessing of renewable feedstock.
  • the prior art also discloses a novel catalyst and a process for the preparation of the Pt/Pd encapsulated in sodalite cage with silica-alumina ZSM-5 synthesized around it supported with nickel, molybdenum, cobalt, tungsten or one or more thereof.
  • the prior art also discloses a process to convert vegetable oils, free fatty acids, and microbial lipids, bio-crude and conventional non- renewable crude based feed stocks such as diesel, naphtha, kerosene, gas oil, residue, etc., into gasoline, aviation, diesel, fuel and other hydrocarbons fuel with reduced coke formation and hydrogen generation due to formation of napthenes and aromatics using the novel catalyst.
  • WO2012088145A3 discloses a process for the conversion of oxygen-containing hydrocarbons into long-chain hydrocarbons suitable for use as a fuel. Such hydrocarbons are derived from biomass and these hydrocarbons may optionally be mixed with petroleum-derived hydrocarbons prior to conversion. The process utilizes a catalyst comprising Ni and Mo, but not Co, to convert a mixture comprising oxygenated hydrocarbons into product hydrocarbons containing from ten to thirty carbons.
  • US20140339134A1 discloses a process for preparing a hydroconversion catalyst, for example, a hydrocracking catalyst, and use of the catalyst thus obtained in a hydroconversion process.
  • the said hydroconversion catalyst is prepared by mixing a modified zeolite with an alumina binder, shaping the mixture and then calcinating, followed by impregnation of the shaped Zeolite with at least one compound of a catalytic metal chosen from compounds of a metal from group VIIIB and/or from group VIB in acidic medium.
  • the acidic medium acts as a complexing or chelating agent for at least one compound of a catalytic metal.
  • the catalyst as produced is useful in hydrocracking of Vacuum Gas Oil (VGO).
  • VGO Vacuum Gas Oil
  • US2015/0158018A1 discloses a catalyst for hydroprocessing a hydrocarbon feedstock under hydroprocessing conditions, methods for making the catalyst, and hydroprocessing processes using the catalyst.
  • the catalyst for hydroprocessing a hydrocarbon feedstock comprising a USY Zeolite component having a silica-alumina as an amorphous cracking component and at least one hydrogenation metal component selected from the group consisting of a Group VIB metal, a Group VIII metal, and mixtures thereof, along with optional binder. It is also disclosed that deposition of the hydrogenation metal on the catalyst is achieved in the presence of at least one organic oxygen-containing ligand.
  • US20190136140A1 discloses a method, a composition, and use of decarbonylation and decarboxylation catalysts to produce renewable hydrocarbons.
  • the method comprises at least one oxygenated organic compound, to form a hydrocarbon product, comprising the steps of: contacting the feedstock with a catalyst under conditions to promote deoxygenation of the at least one oxygenated compound.
  • the invention is useful in the production of renewable fuels, such as renewable diesel, and jet fuel.
  • Green diesel the triglycerides in biomass are hydrogenated and broken down into free fatty acids (FFAs).
  • FFAs free fatty acids
  • the fatty acid products are sent to deoxygenation steps, either through decarboxylation and decarbonylation route or hydrodeoxygenation route to remove oxygen content in the form of CO, CO2, or H2O.
  • the n-alkanes in the diesel range from C15 to C18, called Green diesel (GD) are produced.
  • the Green diesel (GD) as produced shows poorer cold flow properties and lubricity when compared to biodiesel.
  • the Green diesel (GD) should have high branching isomers obtained from hydroisomerization reaction.
  • Step 1 of hydrodeoxygenation and step 2 is hydrocracking and hydroisomerization of product of step 1.
  • SAF Sustainable Aviation Fuel
  • GD Green Diesel
  • the objective of the present invention is to provide a multifunctional catalyst and a composition of the multifunctional catalyst for producing a Green Diesel (GD) as well as a Sustainable Aviation Fuel (SAF) from a biomass feedstock.
  • GD Green Diesel
  • SAF Sustainable Aviation Fuel
  • the main objective of the present invention is single step production of Green Diesel (GD) and Sustainable Aviation Fuel (SAF) from biomass feedstock.
  • GD Green Diesel
  • SAF Sustainable Aviation Fuel
  • the specific objective of the present invention is to provide multifunctional catalyst for selective hydro deoxygenation, hydrocracking and hydroisomerization of used cooking oil/vegetable oil and thus producing Green Diesel (GD) and Sustainable Aviation Fuel (SAF) through single step reaction condition. Further, the present invention discloses multifunctional non-precious metal based single step catalyst for conversion of used cooking oil (UCO) to SAF/ Green Diesel selectively.
  • UAO used cooking oil
  • the present invention discloses a multifunctional catalyst having a catalytic support of a Zeolite component, SiO2-A12O3 and a binder selected from alumina or Pseudoboehmite alumina.
  • the catalytic support is sequentially loaded with at least one active metal selected from nickel (Ni), tungsten (W) and at least one chelating agent.
  • the chelating agent is selected from citric acid, nitrilotriacetic acid, glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid, succinic acid or a combination thereof.
  • the multifunctional catalyst of the present invention selectively produces transportation fuel from UCO and/or Vegetable oils.
  • the said transportation fuels are at least one of the Sustainable Aviation Fuel (SAF), or the Green Diesel (GD).
  • the Sustainable Aviation Fuel (SAF) as claimed in the present invention is produced by subjecting the said feedstock to a pressure of 80 bar at a temperature of 400°C with 1 WHSV at 1000Nm3/m3 H2/feed ratio in the presence of the said multifunctional catalyst.
  • the Green Diesel (GD) is produced by subjecting the said feedstock to a pressure of 60 bar at a temperature of 320°C with 1 WHSV at 500 Nm3/m3 H2/feed ratio in the presence of the said multifunctional catalyst.
  • the present invention discloses a multifunctional catalyst having a catalytic support of a Zeolite component, SiO2-A12O3 and a binder selected from alumina or Pseudoboehmite alumina.
  • the said Zeolite component is selected from one of a zeolite Y, Mesoporous Y zeolite, ZSM-5, Meso ZSM-5, MOR, SAPO-11, or SAPO-5.
  • MOR Mordenite
  • SAPO Silicoaluminophosphate
  • ZSM Zeolite Socony Mobil
  • ZSM-5 is a synthetic zeolite which contains silica (Si) and alumina (Al) with the ratio of silica greater than the alumina.
  • the catalyst is known as ZSM-5 because it has a pore diameter of 5 A (angstroms) and it has more than five Si/Al ratios.
  • the said catalytic support is in the form of extrudates.
  • the said extrudates of the catalytic support are sequentially loaded with at least one active metal selected from Group 6, Groups 8-10 of the Periodic Table and at least one chelating agent selected from citric acid, nitrilotriacetic acid, glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid, succinic acid or a combination thereof.
  • the at least one active metal selected from Group 6 of the Periodic Table is Tungsten (W) and at least one active metal selected from Groups 8-10 of the Periodic Table is Nickel (Ni).
  • the multifunctional catalyst of the present invention is subjected to sulfidation before using the said multifunctional catalyst for selectively preparing a plurality of transportation fuels such as the Sustainable Aviation Fuel (SAF), or the Green Diesel (GD).
  • SAF Sustainable Aviation Fuel
  • GD Green Diesel
  • the active metals include Nickel (Ni) and Tungsten (W) which are sequentially loaded on the above prepared extrudates in the following order:
  • Tungsten (W) loading A Tungsten (W) impregnating solution having Tungsten (W) and at least one chelating agent is prepared.
  • the source of Tungsten (W) is Ammonium meta tungstate, Sodium Tungstate, Tungsten Chloride, or Phoshphotungstic acid.
  • a spray impregnation step the above prepared extrudates are impregnated with the said Tungsten (W) impregnating solution.
  • pH of the Tungsten (W) impregnating solution should be between 5-5.2.
  • the obtained extrudates are aged at room temperature and dried at 90°C. The obtained extrudates are calcined at 500°C.
  • Nickel (Ni) loading is done through single step spray impregnation.
  • the source of Nickel (Ni) is Nickel Acetate, Nickel Carbonate, Nickel Formate, Nickel Nitrate, Nickel Chloride, Nickel Sulphate.
  • a Nickel (Ni) impregnating solution having Nickel (Ni) and at least one chelating agent is prepared.
  • spray impregnation step the Nickel (Ni) impregnating solution is impregnated onto extrudates obtained above.
  • the pH of the Nickel (Ni) impregnating solution should be between 5. The obtained extrudates are only dried.
  • the at least one chelating agent is selected from citric acid, nitrilotriacetic acid, glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid, succinic acid or a combination thereof.
  • the at least one chelating agent is a combination of citric acid with any one chelating agent selected from nitrilotriacetic acid (NTA), glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid or succinic acid.
  • NTA nitrilotriacetic acid
  • glutamic acid glutamic acid
  • hexamethylenetetramine hexamethylenetetramine
  • glucaric acids amino acid
  • ethylenediaminetetraacetic acid glutaric acid or succinic acid
  • the weight percent range of at least one chelating agent is 0.01-1.0 wt% of a total weight of said multifunctional catalyst.
  • the at least one chelating agent is a combination of citric acid with any one chelating agent selected from Nitrilotriacetic acid, Hexamethylenetetramine, Glucaric acids or Glutamic acids.
  • the at least one chelating agent is a combination of citric acid and Nitrilotriacetic acid.
  • the at least one chelating agent is a combination of amine and acid, acid and acid, amino acids and chemical derived acids.
  • Range of catalyst composition NiO- 4-8%, WO3- 19-25%, A12O3- 35-60%, SiO2-25-30%, C- 1.5-6%, H-l.0-3.0%, N- 0.1-1.0% Range of catalyst components: NiO- 4-8%, WO3- 19-25%, Mesoporous Y zeolite- 5-25%, 10% SiO2-A12O3- 25-55%, A12O3- 5-20%, Chelating agents- 3-8 %
  • N2 physisorption data of Catalyst The said multifunctional catalyst as obtained after sequentially loading of Tungsten (W) and Nickel (Ni) is subjected to sulfidation at 350°C for 20 hours before using the said multifunctional catalyst for selectively preparing a plurality of transportation fuels from the biomass feedstock.
  • the said feedstock is selected from Jatropha oil, Palm oil, Karanja oil, Sunflower oil, Cottonseed oil, Soybean oil, Mustard oil, coconut oil, Rapeseed oil, Tall oil, and/or Used Cooking Oil (UCO).
  • the multifunctional catalyst of the present invention selectively produces transportation fuel from UCO and/or Vegetable oils.
  • the plurality of transportation fuels is at least one of the Sustainable Aviation Fuel (SAF), or the Green Diesel (GD).
  • the multifunctional catalyst is sulfided at 350°C for 20 hours before application of the said multifunctional catalyst for producing the Sustainable Aviation Fuel (SAF), or the Green Diesel (GD), and wherein, the feedstock is used cooking oil with Oxygen content of 12.5%.
  • SAF Sustainable Aviation Fuel
  • GD Green Diesel
  • the optimum reaction conditions for producing Sustainable Aviation Fuel (SAF) are 400°C temperature, 80 bar Pressure, 1 WHSV, H2/feed ratio 1000 Nm3/m3.
  • * * * * * *NiW based catalyst with Alumina is prepared by adding required amounts of Nickel acetate and Ammonium meta tungstate in water and impregnating the solution on alumina extrudates. The obtained material is dried at 100°C for four hours and calcined at 500°C for four hours.
  • the optimum reaction conditions for producing Green Diesel (GD) are 320°C, 60 bar Pressure, 1 WHSV, H2/feed ratio 500 Nm3/m3.
  • NiW/Meso Y zeolite-SiO2-A12O3-A12O3 with citric acid and nitrilotriacetic acid (NTA) as chelating agent yields 95 vol% Green Diesel (GD) with oxygen percentage in the range 0.4-0.8 %.
  • the multifunctional catalyst of the present invention yields Sustainable Aviation Fuel (SAF) at maximum rate of -40-50 vol% at SAF reaction conditions while Green Diesel at maximum rate of -98 vol% at Diesel reaction conditions.
  • SAF Sustainable Aviation Fuel
  • the Graph- 1 shows percent TCD and temperature relation, wherein, condition (i) present invention catalyst and combination of chelating agents - citric acid and nitrilotriacetic acid; and condition (ii) present invention catalyst with only citric acid as chelating agent. Accordingly, it is also observed from above Graph- 1 that for condition (i) Tmax is 370°C while for condition (ii) Tmax is 390°C, hence, in condition (i) where the present invention catalyst and combination of chelating agents - citric acid and nitrilotriacetic acid, the %TCD reduces at lower temperature which shows enhancement in dispersion of active metals when compared to (ii). Specifically, the Graph- 1 depicts that the combination of chelating agent provides low temperature reduction of metals.
  • SAF Sudinable Aviation Fuel
  • Combination of chelating agent enhances metal dispersion and thus improves deoxygenation which is evident in Temperature programmed profiles.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The present invention discloses a multifunctional catalyst made up of a catalytic support of a Zeolite component, SiO2-Al2O3 and a binder selected from alumina or Pseudoboehmite alumina. The said catalytic support is in the form of extrudates and the said extrudates of the catalytic support are sequentially loaded with at least one active metal selected from tungsten (W), nickel (Ni) and at least one chelating agent. The at least one chelating agent is selected from citric acid, nitrilotriacetic acid, glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid, succinic acid or a combination thereof. Further, the multifunctional catalyst of the present invention is subjected to sulfidation before using the said multifunctional catalyst for selectively preparing a plurality of transportation fuels such as the Sustainable Aviation Fuel (SAF), or the Green Diesel (GD).

Description

A MULTIFUNCTIONAL CATALYST AND ITS COMPOSITION FOR SINGLE
STEP CONVERSION OF TRIGLYCERIDES TO TRANSPORTATION FUELS
FIELD OF THE INVENTION:
The present invention describes a multifunctional catalyst, a composition of the multifunctional catalyst, and use of the said multifunctional catalyst for producing different types of transportation fuels from a single feedstock. Wherein, different types of transportation fuels are produced as per their market demand through a single reaction step and a multifunctional catalyst.
BACKGROUND OF THE INVENTION:
As the world is economically growing, demand for clean and green energy is increasing day by day and such clean and green energy is derived from renewable energy resources. The demand for clean and green energy is high, especially, in transportation sector. In transportation sector, clean and green transportation fuels are required which can be derived from biomass.
To get continuous supply of such clean and green transportation fuels, biomass is treated under suitable reactor conditions and in the presence of a specific catalysts to breakdown the biomass into required hydrocarbons chains. However, such process involves many reaction steps and different types of catalysts are required to produce different types of transportation fuels with specific carbon chains.
US9790439B2 discloses a process and apparatus for producing mixture of fuel components through a feed of biological origin. The process comprising subjecting said feed of biological origin and a hydrogen gas feed to hydroprocessing in the presence of a catalyst system comprising dewaxing catalyst to form a mixture of fuel components.
US10351781B2 discloses a novel Pt/Pd sodalite caged catalyst combination with sulfided base metal catalyst for improved catalytic hydroprocessing of renewable feedstock. The prior art also discloses a novel catalyst and a process for the preparation of the Pt/Pd encapsulated in sodalite cage with silica-alumina ZSM-5 synthesized around it supported with nickel, molybdenum, cobalt, tungsten or one or more thereof. The prior art also discloses a process to convert vegetable oils, free fatty acids, and microbial lipids, bio-crude and conventional non- renewable crude based feed stocks such as diesel, naphtha, kerosene, gas oil, residue, etc., into gasoline, aviation, diesel, fuel and other hydrocarbons fuel with reduced coke formation and hydrogen generation due to formation of napthenes and aromatics using the novel catalyst.
WO2012088145A3 discloses a process for the conversion of oxygen-containing hydrocarbons into long-chain hydrocarbons suitable for use as a fuel. Such hydrocarbons are derived from biomass and these hydrocarbons may optionally be mixed with petroleum-derived hydrocarbons prior to conversion. The process utilizes a catalyst comprising Ni and Mo, but not Co, to convert a mixture comprising oxygenated hydrocarbons into product hydrocarbons containing from ten to thirty carbons.
US20140339134A1 discloses a process for preparing a hydroconversion catalyst, for example, a hydrocracking catalyst, and use of the catalyst thus obtained in a hydroconversion process. The said hydroconversion catalyst is prepared by mixing a modified zeolite with an alumina binder, shaping the mixture and then calcinating, followed by impregnation of the shaped Zeolite with at least one compound of a catalytic metal chosen from compounds of a metal from group VIIIB and/or from group VIB in acidic medium. The acidic medium acts as a complexing or chelating agent for at least one compound of a catalytic metal. The catalyst as produced is useful in hydrocracking of Vacuum Gas Oil (VGO).
US2015/0158018A1 discloses a catalyst for hydroprocessing a hydrocarbon feedstock under hydroprocessing conditions, methods for making the catalyst, and hydroprocessing processes using the catalyst. The catalyst for hydroprocessing a hydrocarbon feedstock comprising a USY Zeolite component having a silica-alumina as an amorphous cracking component and at least one hydrogenation metal component selected from the group consisting of a Group VIB metal, a Group VIII metal, and mixtures thereof, along with optional binder. It is also disclosed that deposition of the hydrogenation metal on the catalyst is achieved in the presence of at least one organic oxygen-containing ligand.
US20190136140A1 discloses a method, a composition, and use of decarbonylation and decarboxylation catalysts to produce renewable hydrocarbons. The method comprises at least one oxygenated organic compound, to form a hydrocarbon product, comprising the steps of: contacting the feedstock with a catalyst under conditions to promote deoxygenation of the at least one oxygenated compound. The invention is useful in the production of renewable fuels, such as renewable diesel, and jet fuel.
To produce green diesel the triglycerides in biomass are hydrogenated and broken down into free fatty acids (FFAs). The fatty acid products are sent to deoxygenation steps, either through decarboxylation and decarbonylation route or hydrodeoxygenation route to remove oxygen content in the form of CO, CO2, or H2O. Subsequently, the n-alkanes in the diesel range from C15 to C18, called Green diesel (GD) are produced. The Green diesel (GD) as produced shows poorer cold flow properties and lubricity when compared to biodiesel. In order to improve cold flow properties, the Green diesel (GD) should have high branching isomers obtained from hydroisomerization reaction.
Further, to meet the jet fuel specification with good cold flow properties, the hydrocracking and hydroisomerization of Green diesel (GD) over bifunctional catalysts under elevated temperature and pressure are required to produce Sustainable Aviation Fuel (SAF) with carbon chains ranging from C9 to C14.
The procedure as stated above constitute two steps involving two separate catalysts. Step 1 of hydrodeoxygenation and step 2 is hydrocracking and hydroisomerization of product of step 1. Hence, it is observed that single step production of Jet fuel and Green Diesel (GD) from vegetable oil with desired properties and high yield is limiting. Further, the state of art technique has their own disadvantages such as undesired freezing point of Sustainable Aviation Fuel (SAF) and higher oxygen content of the Green Diesel (GD).
OBJECTIVE OF THE PRESENT INVENTION:
The objective of the present invention is to provide a multifunctional catalyst and a composition of the multifunctional catalyst for producing a Green Diesel (GD) as well as a Sustainable Aviation Fuel (SAF) from a biomass feedstock.
The main objective of the present invention is single step production of Green Diesel (GD) and Sustainable Aviation Fuel (SAF) from biomass feedstock.
The specific objective of the present invention is to provide multifunctional catalyst for selective hydro deoxygenation, hydrocracking and hydroisomerization of used cooking oil/vegetable oil and thus producing Green Diesel (GD) and Sustainable Aviation Fuel (SAF) through single step reaction condition. Further, the present invention discloses multifunctional non-precious metal based single step catalyst for conversion of used cooking oil (UCO) to SAF/ Green Diesel selectively.
SUMMARY OF THE INVENTION:
The present invention discloses a multifunctional catalyst having a catalytic support of a Zeolite component, SiO2-A12O3 and a binder selected from alumina or Pseudoboehmite alumina. The catalytic support is sequentially loaded with at least one active metal selected from nickel (Ni), tungsten (W) and at least one chelating agent. The chelating agent is selected from citric acid, nitrilotriacetic acid, glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid, succinic acid or a combination thereof.
Further, the multifunctional catalyst of the present invention selectively produces transportation fuel from UCO and/or Vegetable oils. The said transportation fuels are at least one of the Sustainable Aviation Fuel (SAF), or the Green Diesel (GD).
The Sustainable Aviation Fuel (SAF) as claimed in the present invention is produced by subjecting the said feedstock to a pressure of 80 bar at a temperature of 400°C with 1 WHSV at 1000Nm3/m3 H2/feed ratio in the presence of the said multifunctional catalyst. The Green Diesel (GD) is produced by subjecting the said feedstock to a pressure of 60 bar at a temperature of 320°C with 1 WHSV at 500 Nm3/m3 H2/feed ratio in the presence of the said multifunctional catalyst.
DETAIEED DESCRIPTION OF THE INVENTION:
For promoting an understanding of the principles of the present disclosure, reference will now be made to the specific embodiments of the present invention further illustrated in the drawings and specific language will be used to describe the same. The foregoing general description and the following detailed description are explanatory of the present disclosure and are not intended to be restrictive thereof. It will nevertheless be understood that no limitation of the scope of the present disclosure is thereby intended, such alterations and further modifications in the illustrated composition, and such further applications of the principles of the present disclosure as illustrated herein being contemplated as would normally occur to one skilled in the art to which the present disclosure relates. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinarily skilled in the art to which this present disclosure belongs. The methods, and examples provided herein are illustrative only and not intended to be limiting.
The present invention discloses a multifunctional catalyst having a catalytic support of a Zeolite component, SiO2-A12O3 and a binder selected from alumina or Pseudoboehmite alumina. Wherein, the said Zeolite component is selected from one of a zeolite Y, Mesoporous Y zeolite, ZSM-5, Meso ZSM-5, MOR, SAPO-11, or SAPO-5.
Hereinafter, MOR is referred to as Mordenite (MOR) zeolites, SAPO is referred to as Silicoaluminophosphate (SAPO) zeolite and ZSM is referred to as Zeolite Socony Mobil, wherein, ZSM-5 is a synthetic zeolite which contains silica (Si) and alumina (Al) with the ratio of silica greater than the alumina. The catalyst is known as ZSM-5 because it has a pore diameter of 5 A (angstroms) and it has more than five Si/Al ratios.
The said catalytic support is in the form of extrudates. The said extrudates of the catalytic support are sequentially loaded with at least one active metal selected from Group 6, Groups 8-10 of the Periodic Table and at least one chelating agent selected from citric acid, nitrilotriacetic acid, glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid, succinic acid or a combination thereof.
Further, the at least one active metal selected from Group 6 of the Periodic Table is Tungsten (W) and at least one active metal selected from Groups 8-10 of the Periodic Table is Nickel (Ni).
Further, the multifunctional catalyst of the present invention is subjected to sulfidation before using the said multifunctional catalyst for selectively preparing a plurality of transportation fuels such as the Sustainable Aviation Fuel (SAF), or the Green Diesel (GD).
The preparation of the said multifunctional catalyst is explained hereinbelow.
Preparing extrudates of the catalytic support
Mesoporous Y Zeolite (5-20%), SiO2-A12O3 (50-80%) and Pseudoboehmite alumina (10-
20%) are mixed in a Kneader and a catalytic mixture is prepared. Further, extrudates of the catalytic support is prepared from the said catalytic mixture by adding IM acetic acid solution. The extrudates of the catalytic support are then dried at 100°C and the said dried extrudates are calcinated at 500 °C.
Preparation of NiW loaded MesoY/Si02-A1203/A1203
In the present invention, the active metals include Nickel (Ni) and Tungsten (W) which are sequentially loaded on the above prepared extrudates in the following order:
Tungsten (W) loading: A Tungsten (W) impregnating solution having Tungsten (W) and at least one chelating agent is prepared. The source of Tungsten (W) is Ammonium meta tungstate, Sodium Tungstate, Tungsten Chloride, or Phoshphotungstic acid. In a spray impregnation step, the above prepared extrudates are impregnated with the said Tungsten (W) impregnating solution. While loading Tungsten (W) source along with the chelating agents, pH of the Tungsten (W) impregnating solution should be between 5-5.2. The obtained extrudates are aged at room temperature and dried at 90°C. The obtained extrudates are calcined at 500°C. Nickel (Ni) loading: Nickel (Ni) loading is done through single step spray impregnation. Wherein, the source of Nickel (Ni) is Nickel Acetate, Nickel Carbonate, Nickel Formate, Nickel Nitrate, Nickel Chloride, Nickel Sulphate. A Nickel (Ni) impregnating solution having Nickel (Ni) and at least one chelating agent is prepared. In spray impregnation step, the Nickel (Ni) impregnating solution is impregnated onto extrudates obtained above. The pH of the Nickel (Ni) impregnating solution should be between 5. The obtained extrudates are only dried.
Wherein, the at least one chelating agent is selected from citric acid, nitrilotriacetic acid, glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid, succinic acid or a combination thereof.
In an embodiment, the at least one chelating agent is a combination of citric acid with any one chelating agent selected from nitrilotriacetic acid (NTA), glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid or succinic acid. Wherein, the said combination of citric acid with any one chelating agent is in a weight percent ratio of 50:50.
In a specific embodiment, the weight percent range of at least one chelating agent is 0.01-1.0 wt% of a total weight of said multifunctional catalyst. In another embodiment, the at least one chelating agent is a combination of citric acid with any one chelating agent selected from Nitrilotriacetic acid, Hexamethylenetetramine, Glucaric acids or Glutamic acids.
In another embodiment, the at least one chelating agent is a combination of citric acid and Nitrilotriacetic acid.
In another embodiment, the at least one chelating agent is a combination of amine and acid, acid and acid, amino acids and chemical derived acids. The composition analysis of the multifunctional catalyst as prepared hereinabove gives following results.
Range of catalyst composition: NiO- 4-8%, WO3- 19-25%, A12O3- 35-60%, SiO2-25-30%, C- 1.5-6%, H-l.0-3.0%, N- 0.1-1.0% Range of catalyst components: NiO- 4-8%, WO3- 19-25%, Mesoporous Y zeolite- 5-25%, 10% SiO2-A12O3- 25-55%, A12O3- 5-20%, Chelating agents- 3-8 %
N2 physisorption data of Catalyst:
Figure imgf000008_0001
The said multifunctional catalyst as obtained after sequentially loading of Tungsten (W) and Nickel (Ni) is subjected to sulfidation at 350°C for 20 hours before using the said multifunctional catalyst for selectively preparing a plurality of transportation fuels from the biomass feedstock. Wherein, the said feedstock is selected from Jatropha oil, Palm oil, Karanja oil, Sunflower oil, Cottonseed oil, Soybean oil, Mustard oil, Coconut oil, Rapeseed oil, Tall oil, and/or Used Cooking Oil (UCO).
In case, when Used Cooking Oil (UCO) is taken as the feedstock, the characterization of the UCO shows following results: Elemental analysis of UCO
Figure imgf000009_0001
temperature-SIMDIST analysis of UCO
Figure imgf000009_0002
*IBP referred to as Initial Boiling Point & **FBP referred to as Final Boiling Point
Other properties of UCO
Figure imgf000009_0003
In an embodiment, the multifunctional catalyst of the present invention selectively produces transportation fuel from UCO and/or Vegetable oils. The plurality of transportation fuels is at least one of the Sustainable Aviation Fuel (SAF), or the Green Diesel (GD).
Reaction and Results
The multifunctional catalyst is sulfided at 350°C for 20 hours before application of the said multifunctional catalyst for producing the Sustainable Aviation Fuel (SAF), or the Green Diesel (GD), and wherein, the feedstock is used cooking oil with Oxygen content of 12.5%.
The optimum reaction conditions for producing Sustainable Aviation Fuel (SAF) are 400°C temperature, 80 bar Pressure, 1 WHSV, H2/feed ratio 1000 Nm3/m3.
Table 1
Figure imgf000009_0004
Figure imgf000010_0001
* * *NiW based catalyst with Alumina is prepared by adding required amounts of Nickel acetate and Ammonium meta tungstate in water and impregnating the solution on alumina extrudates. The obtained material is dried at 100°C for four hours and calcined at 500°C for four hours.
The optimum reaction conditions for producing Green Diesel (GD) are 320°C, 60 bar Pressure, 1 WHSV, H2/feed ratio 500 Nm3/m3.
Table 2
Figure imgf000010_0002
Figure imgf000011_0002
From table 1 it is observed thatNiW/Meso Y zeolite-SiO2-A12O3-A12O3 with citric acid alone as chelating agent yields 38 vol% Sustainable Aviation Fuel (SAF) with freezing point -49.
Further, it is observed from table 2 that NiW/Meso Y zeolite-SiO2-A12O3-A12O3 with citric acid and nitrilotriacetic acid (NTA) as chelating agent yields 95 vol% Green Diesel (GD) with oxygen percentage in the range 0.4-0.8 %.
Moreover, it is specifically observed that the multifunctional catalyst of the present invention yields Sustainable Aviation Fuel (SAF) at maximum rate of -40-50 vol% at SAF reaction conditions while Green Diesel at maximum rate of -98 vol% at Diesel reaction conditions.
Furthermore, the Graph- 1 below shows percent TCD and temperature relation, wherein, condition (i) present invention catalyst and combination of chelating agents - citric acid and nitrilotriacetic acid; and condition (ii) present invention catalyst with only citric acid as chelating agent.
Figure imgf000011_0001
Accordingly, it is also observed from above Graph- 1 that for condition (i) Tmax is 370°C while for condition (ii) Tmax is 390°C, hence, in condition (i) where the present invention catalyst and combination of chelating agents - citric acid and nitrilotriacetic acid, the %TCD reduces at lower temperature which shows enhancement in dispersion of active metals when compared to (ii). Specifically, the Graph- 1 depicts that the combination of chelating agent provides low temperature reduction of metals.
Salient advantageous features of the multifunctional catalyst of the present invention
Only one catalyst is required to produce SAF or Diesel depending on the demand and only the reaction conditions required to be slightly changed.
The sequential loading of active metals as discussed hereinabove and specifically, the spray impregnation of Nickel (Ni) along with complexation agents and uncalcined final catalyst slows down the formation of NiS2 and apparently WS2 forms first followed by nickel substitution at edges. Thus, this maximizes availability of the active metal sites and improves overall catalytic activity of the multifunctional catalyst.
The product [Sustainable Aviation Fuel (SAF)] as obtained under optimum reaction conditions for producing Sustainable Aviation Fuel (SAF) meets the freezing point specification of SAF fuel (at least -47 °C) without additional second stage catalyst.
Combination of chelating agent enhances metal dispersion and thus improves deoxygenation which is evident in Temperature programmed profiles.

Claims

We Claim:
1. A multifunctional catalyst comprising a catalytic support of Mesoporous Y zeolite (5- 20%), SiO2-A12O3 (50-80%) and Pseudoboehmite alumina (10-20%), wherein, the catalytic support is sequentially loaded with at least one active metal selected from nickel (Ni), tungsten (W) and at least one chelating agent selected from citric acid, nitrilotriacetic acid, glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid, succinic acid or a combination thereof.
2. The multifunctional catalyst as claimed in claim 1, wherein, the at least one chelating agent is a combination of citric acid with any one chelating agent selected from nitrilotriacetic acid, glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid or succinic acid, and the said combination of citric acid with any one chelating agent is in a ratio of 50:50.
3. The multifunctional catalyst as claimed in claim 1, wherein, the at least one chelating agent is 0.01-1.0 wt% of a total weight of said multifunctional catalyst.
4. The multifunctional catalyst as claimed in claim 1, wherein, the said multifunctional catalyst composition is in a range of: NiO- 4-8%, WO3- 19-25%, A12O3- 35-60%, SiO2-25-30%, C- 1.5-6%, H-l.0-3.0%, N- 0.1-1.0%.
5. The multifunctional catalyst as claimed in claim 1, wherein, a surface area of the said multifunctional catalyst is 266.5 m2 /g.
6. The multifunctional catalyst as claimed in claim 5, wherein, a micropore surface area of the said multifunctional catalyst is 224.5 m2/g and a mesopore surface area of the said multifunctional catalyst is 42 m2 /g.
7. The multifunctional catalyst as claimed in claim 1, wherein, the said multifunctional catalyst having total pore volume of 0.375 cm3.
8. A process for preparing a multifunctional catalyst, the process comprising steps of: preparing extrudates of a catalytic support comprising a zeolite component, alumina-silica and a binder selected from alumina or Pseudoboehmite alumina; and sequential loading of said extrudates of the catalytic support with at least one active metal selected from Group 6, Groups 8-10 of the Periodic Table and at least one chelating agent selected from citric acid, nitrilotriacetic acid, glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid, succinic acid or a combination thereof.
9. The process as claimed in claim 8, wherein, the Zeolite component is selected from one of a zeolite Y, Mesoporous Y zeolite, ZSM-5, Meso ZSM-5, MOR, SAPO-11, or SAPO-5.
10. The process as claimed in claim 8, wherein, preparing extrudates of the catalytic support comprises: preparing a catalytic mixture of Mesoporous Y Zeolite (5-20%), SiO2-A12O3 (50- 80%) and Pseudoboehmite alumina (10-20%); preparing extrudates of the catalytic support from the said catalytic mixture by adding IM acetic acid solution; drying the said extrudates at 100°C; and calcinating the said dried extrudates at 500°C.
11. The process as claimed in claim 8, wherein at least one active metal selected from Group 6 of the Periodic Table is Tungsten (W) and at least one active metal selected from Groups 8-10 of the Periodic Table is Nickel (Ni).
12. The process as claimed in claim 8, wherein, sequential loading of said extrudates comprises: first Tungsten (W) loading step comprising preparing a Tungsten (W) impregnating solution having Tungsten (W) and at least one chelating agent, spray impregnation of the said Tungsten (W) impregnating solution onto extrudates of the catalytic support, aging the said extrudates at room temperature for at least 24 hours, drying the said extrudates at 90°C, and calcinating the said dried extrudates at 500°C; and second Nickel (Ni) loading step comprising preparing a Nickel (Ni) impregnating solution having Nickel (Ni) and at least one chelating agent, spray impregnation of the said Nickel (Ni) impregnating solution onto extrudates obtained above, drying the said extrudates at 90°C.
13. The process as claimed in claim 12, wherein, the Tungsten (W) impregnating solution having a pH value in between 5-5.2.
14. The process as claimed in claim 12, wherein, the Nickel (Ni) impregnating solution having a pH value of 5.
15. The process as claimed in claim 8, wherein, the said multifunctional catalyst comprises a plurality of components in a weight percentage range of: NiO- 4-8%, WO3- 19-25%, mesoporous Y zeolite- 5-25%, 10% SiO2-A12O3- 25-55%, A12O3- 5-20 % and chelating agents- 3-8 %.
16. A process for selectively preparing a plurality of transportation fuels from a single feedstock and a multifunctional catalyst, wherein, the plurality of transportation fuels is at least one of a Sustainable Aviation Fuel (SAF), or a Green Diesel (GD), the process comprising: producing the Sustainable Aviation Fuel (SAF) by subjecting the said feedstock to a pressure of 80 bar at a temperature of 400°C with 1 WHSV at 1000Nm3/m3 H2/feed ratio in the presence of the said multifunctional catalyst; producing the Green Diesel (GD) by subjecting the said feedstock to a pressure of 60 bar at a temperature of 320°C with 1 WHSV at 500 Nm3/m3 H2/feed ratio in the presence of the said multifunctional catalyst.
17. The process as claimed in claim 16, wherein, the said feedstock is selected from used or fresh cooking oil, vegetable oil, jatropha oil, palm oil, karanja oil, sunflower oil, cottonseed oil, soybean oil, mustard oil, coconut oil, rapeseed oil, tall oil or any triglyceride containing oil.
14
18. The process as claimed in claim 16, wherein, the said multifunctional catalyst comprises a catalytic support of Mesoporous Y zeolite (5-20%), SiO2-A12O3 (50- 80%) and Pseudoboehmite alumina (10-20%), wherein, the catalytic support is sequentially loaded with at least one active metal selected from nickel (Ni), tungsten
(W) and at least one chelating agent selected from citric acid, nitrilotriacetic acid, glutamic acid, hexamethylenetetramine, glucaric acids, amino acid, ethylenediaminetetraacetic acid, glutaric acid, succinic acid or a combination thereof.
19. The process as claimed in claim 18, wherein, the said multifunctional catalyst is subjected to sulfidation at 350°C for 20 hours before using the said multifunctional catalyst for selectively preparing a plurality of transportation fuels.
15
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Citations (8)

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WO2012088145A2 (en) 2010-12-20 2012-06-28 Conocophillips Company Production of renewable fuels
US20140339134A1 (en) 2011-10-24 2014-11-20 Total Raffinage France Process for preparing a hydroconversion catalyst, catalyst thus obtained and use thereof in a hydroconversion process
US20150158018A1 (en) 2013-12-09 2015-06-11 Bi-Zeng Zhan Hydrocracking catalyst and process for producing lube base stocks
WO2017112558A1 (en) * 2015-12-21 2017-06-29 Exxonmobil Research And Engineering Company Trim dewaxing of distillate fuel
US9790439B2 (en) 2010-05-25 2017-10-17 Upm-Kymmene Corporation Process and apparatus for producing fuel from a biological origin through a single hydroprocessing step in the presence of a NiW catalyst
US20190136140A1 (en) 2017-11-06 2019-05-09 Saskatchewan Research Council Process for the production of hydrocarbon biofuels
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* Cited by examiner, † Cited by third party
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US9790439B2 (en) 2010-05-25 2017-10-17 Upm-Kymmene Corporation Process and apparatus for producing fuel from a biological origin through a single hydroprocessing step in the presence of a NiW catalyst
WO2012088145A2 (en) 2010-12-20 2012-06-28 Conocophillips Company Production of renewable fuels
US20140339134A1 (en) 2011-10-24 2014-11-20 Total Raffinage France Process for preparing a hydroconversion catalyst, catalyst thus obtained and use thereof in a hydroconversion process
US20150158018A1 (en) 2013-12-09 2015-06-11 Bi-Zeng Zhan Hydrocracking catalyst and process for producing lube base stocks
US10351781B2 (en) 2015-12-14 2019-07-16 Council Of Scientific & Industrial Research Pt/Pd sodalite caged catalyst combination with sulfided base metal catalyst for the improved catalytic hydroprocessing of feedstock
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