Catalyst for preparing biological aviation kerosene with castor oil, preparation method and application thereof

Abstract

A hydrodeoxygenation catalyst takes self-made porous large-specific surface nano-alumina as a carrier, takes Ni.sub.xMoW, Ni.sub.xCoW or Ni.sub.xCoMo as an active component, and takes Mn as an assistant. Hydrothermal stability of the catalyst and dispersion of active components may be increased by enlarging a pore channel and a specific surface area of the carrier, thereby prolonging the life of the hydrodeoxygenation catalyst. A hydroisomerization catalyst takes multi-walled carbon nanotube composite hierarchical-pore-channel NiAPO-11 or NiSAPO-11 as a carrier and takes Ni.sub.xMoLa, Ni.sub.xCoLa or Ni.sub.xWLa as an active component. Due to the adding of the carbon nanotubes, the pore channel of the carrier is enriched, and connection between the active components and the carrier is effectively enhanced, thereby prolonging the life of the catalyst on a basis of increasing selectivity of aviation kerosene component. Moreover, the biological aviation kerosene satisfying usage conditions is prepared by virtue of mild reaction conditions.

Claims

1. A method for preparing a catalyst, the catalyst for preparing biological aviation kerosene with castor oil, comprising porous large-specific surface nano-alumina as a carrier, NixMoW, NixCoW or NixCoMo as an active component, and Mn as an assistant, wherein mass of the active component accounts for 10-30% of total mass of the catalyst; x is an atomic ratio and ranges from 2 to 20; mass of the component Mn accounts for 1-5% of the total mass of the catalyst; and a specific surface area of the porous large-specific surface nano-alumina carrier is 500-800 m2/g; the method comprising the following steps: 1) adding aluminum isopropoxide into 0.05 mol/L of nitric acid, refluxing and stirring at 80 C. for 3-5 hours, adding cetyl trimethyl ammonium bromide, and continuously stirring for 2-3 hours to obtain a mixed solution; 2) adding sodium silicate into the mixed solution, refluxing and stirring at 80 C. for 3-5 hours, and aging at a room temperature for 2 hours to obtain a mixed solution; 3) adding ethyl orthosilicate into the mixed solution, refluxing and stirring at 80 C. for 3-5 hours, and aging at the room temperature for 2 hours; 4) adding 1-5% of sodium hydroxide into the mixed solution obtained in the step 3), refluxing and stirring at 80 C. for 3-5 hours, performing centrifugal separation, drying the obtained solid precipitate at 100 C., and calcining in a nitrogen atmosphere at 500-600 C. for 4-6 hours, thereby obtaining the large-specific surface nano-alumina carrier; 5) adding an assistant manganese chloride into an aqueous solution in an amount of three times that of mass of the carrier according to a ratio for stirring for 3 hours under room-temperature stirring conditions, adding the large-specific surface nano-alumina carrier for stirring 3-5 hours to obtain a mixed solution, performing suction filtration on the mixed solution, drying a solid product at 100 C. for 8 hours, and calcining in the nitrogen atmosphere at 500-600 C. for 4-6 hours to obtain solid powder; and 6) sequentially adding an active component soluble salt into the aqueous solution of an amount of three times of mass of the carrier according to a ratio for stirring for 3 hours under the room-temperature stirring conditions, adding the solid powder in the step 5) for stirring 3-5 hours to obtain a mixed solution, standing for 10 hours, drying the standing mixed solution at 100 C. for 8 hours, calcining in the nitrogen atmosphere at 500-600 C. for 4-6 hours, and reducing the obtained solid powder at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydrodeoxygenation catalyst for preparing the biological aviation kerosene with castor oil.

2. The method according to claim 1, wherein a molar ratio of various raw materials in the steps 1) to 3) is: the aluminum isopropoxide to the 0.05 mol/L of nitric acid to the cetyl trimethyl ammonium bromide to the sodium silicate to the ethyl orthosilicate is (50-120):1:(0.5-5):(0.5-5):(0.5-5); and the active component soluble salt refers to a combination of nickel nitrate with cobalt nitrate, ammonium metatungstate or ammonium molybdate.

Description

DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a transmission electron microscope diagram of synthesized carbon nanotube supported hierarchical-pore-channel NiMoLa/NiSAPO-11;

(2) FIG. 2 is a transmission electron microscope diagram of synthesized carbon nanotube supported hierarchical-pore-channel NiWLa/NiSAPO-11;

(3) FIG. 3 is a transmission electron microscope diagram of synthesized carbon nanotube supported hierarchical-pore-channel NiCoLa/NiAPO-11;

(4) FIG. 4 is a nitrogen adsorption-desorption curve of a catalyst NiMoW/Al.sub.2O.sub.3;

(5) FIG. 5 is XRD diagram of hierarchical-pore-channel NiAPO-11 and NiSAPO-11;

(6) FIG. 6 is a scanning electron microscope diagram of NiMoW/Al.sub.2O.sub.3; and

(7) FIG. 7 is a scanning electron microscope diagram of large-specific surface nano-alumina.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(8) The present invention is described below in detail with reference to specific embodiments, while the illustrated embodiments do not make any limitation to a scope of technical solutions required to be protected by claims. Meanwhile, it is particularly indicated that experimental methods without marked specific conditions in embodiments are generally implemented according to routine conditions and conditions in a manual or according to conditions suggested by a manufacturer. The used general equipment, materials, reagents and the like may be obtained commercially.

Embodiment 1

(9) Preparation of a hydrodeoxygenation catalyst comprises the following steps:

(10) adding 16.2 g of aluminum isopropoxide into 32 mL of 0.05 mol/L of nitric acid, refluxing and stirring at 80 C. for 3-5 hours, adding 1.2 g of cetyl trimethyl ammonium bromide, and continuously stirring for 2-3 hours to obtain a mixed solution A; adding 0.27 g of sodium silicate into the mixed solution A, refluxing and stirring at 80 C. for 3-5 hours, and aging at a room temperature for 2 hours to obtain a mixed solution B; adding 0.66 g of ethyl orthosilicate into the mixed solution B, refluxing and stirring at 80 C. for 3-5 hours, and aging at the room temperature for 2 hours to obtain a mixed solution C; adding 1-5% of sodium hydroxide into the mixed solution C, refluxing and stirring at 80 C. for 3-5 hours, performing centrifugal separation, drying the obtained solid precipitate at 100 C. for 8 hours, and calcining in a nitrogen atmosphere at 500-600 C. for 4-6 hours to obtain a large-specific surface nano-alumina carrier; adding 2.3 g of manganese chloride into 24 g of distilled water under room-temperature stirring conditions, stirring for 3 hours and fully dissolving, adding 7.5 g of the large-specific surface nano-alumina carrier, stirring for 3 hours to obtain a mixed solution, performing suction filtration on the mixed solution, drying the mixed solution at 100 C. for 8 hours, and calcining in the nitrogen atmosphere at 500-600 C. for 4-6 hours to obtain solid powder, and recording the solid powder as D; adding 24 g of distilled water into 10 g of nickel nitrate, 0.45 g of ammonium molybdate and 0.32 g of ammonium metatungstate to stir for 3 hours under room-temperature stirring conditions, fully dissolving, adding the solid powder D, stirring for 3-5 hours to obtain a mixed solution, and standing the mixed solution for 10 hours; drying the mixed solution at 100 C. for 8 hours, calcining the obtained solid powder in the nitrogen atmosphere at 500-600 C. for 4-6 hours, and reducing the obtained solid powder at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydrodeoxygenation catalyst, i.e., cat1, for preparing biological aviation kerosene with castor oil.

Embodiment 2

(11) Preparation of a hydrodeoxygenation catalyst comprises the following steps:

(12) adding 16.2 g of aluminum isopropoxide into 32 mL of 0.05 mol/L of nitric acid, refluxing and stirring at 80 C. for 3-5 hours, adding 1.2 g of cetyl trimethyl ammonium bromide, and continuously stirring for 2-3 hours to obtain a mixed solution A; adding 0.27 g of sodium silicate into the mixed solution A, refluxing and stirring at 80 C. for 3-5 hours, and aging at a room temperature for 2 hours to obtain a mixed solution B; adding 0.66 g of ethyl orthosilicate into the mixed solution B, refluxing and stirring at 80 C. for 3-5 hours, and aging at the room temperature for 2 hours to obtain a mixed solution C; adding 1-5% of sodium hydroxide into the mixed solution C, refluxing and stirring at 80 C. for 3-5 hours, performing centrifugal separation, drying the obtained solid precipitate at 100 C. for 8 hours, calcining in a nitrogen atmosphere at 500-600 C. for 4-6 hours to obtain a large-specific surface nano-alumina carrier; adding 2.3 g of manganese chloride into 24 g of distilled water under room-temperature stirring conditions, stirring for 3 hours and fully dissolving, adding 7.5 g of the large-specific surface nano-alumina carrier, stirring for 3 hours to obtain a mixed solution, performing suction filtration on the mixed solution, drying the mixed solution at 100 C. for 8 hours, calcining in the nitrogen atmosphere at 500-600 C. for 4-6 hours to obtain solid powder, and recording the solid powder as D; adding 24 g of distilled water into 10 g of nickel nitrate, 0.25 g of cobalt nitrate and 0.32 g of ammonium metatungstate under room-temperature stirring conditions to stir for 3 hours, fully dissolving, adding the solid powder D, stirring for 3-5 hours to obtain a mixed solution, and standing the mixed solution for 10 hours; drying the mixed solution at 100 C. for 8 hours, calcining the obtained solid powder in the nitrogen atmosphere at 500-600 C. for 4-6 hours, and reducing the obtained solid powder at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydrodeoxygenation catalyst, i.e., cat2, for preparing biological aviation kerosene with castor oil.

Embodiment 3

(13) Preparation of a hydrodeoxygenation catalyst comprises the following steps:

(14) adding 16.2 g of aluminum isopropoxide into 32 mL of 0.05 mol/L of nitric acid, refluxing and stirring at 80 C. for 3-5 hours, adding 1.2 g of cetyl trimethyl ammonium bromide, and continuously stirring for 2-3 hours to obtain a mixed solution A; adding 0.27 g of sodium silicate into the mixed solution A, refluxing and stirring at 80 C. for 3-5 hours, and aging at a room temperature for 2 hours to obtain a mixed solution B; adding 0.66 g of ethyl orthosilicate into the mixed solution B, refluxing and stirring at 80 C. for 3-5 hours, and aging at the room temperature for 2 hours to obtain a mixed solution C; adding 1-5% of sodium hydroxide into the mixed solution C, refluxing and stirring at 80 C. for 3-5 hours, performing centrifugal separation, drying the obtained solid precipitate at 100 C. for 8 hours, calcining in a nitrogen atmosphere at 500-600 C. for 4-6 hours to obtain a large-specific surface nano-alumina carrier; adding 2.3 g of manganese chloride into 24 g of distilled water under room-temperature stirring conditions, stirring for 3 hours and fully dissolving, adding 7.5 g of the large-specific surface nano-alumina carrier, stirring for 3 hours to obtain a mixed solution, performing suction filtration on the mixed solution, drying the mixed solution at 100 C. for 8 hours, calcining in the nitrogen atmosphere at 500-600 C. for 4-6 hours to obtain solid powder, and recording the solid powder as D; adding 24 g of distilled water into 10 g of nickel nitrate, 0.35 g of cobalt nitrate and 0.45 g of ammonium molybdate under room-temperature stirring conditions to stir for 3 hours, fully dissolving, adding the solid powder D, stirring for 3-5 hours to obtain a mixed solution, and standing the mixed solution for 10 hours; drying the mixed solution at 100 C. for 8 hours, calcining the obtained solid powder in the nitrogen atmosphere at 500-600 C. for 4-6 hours, and reducing the obtained solid powder at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydrodeoxygenation catalyst, i.e., cat3, for preparing biological aviation kerosene with castor oil.

Embodiment 4

(15) Preparation of a hydroisomerization catalyst comprises the following steps:

(16) (1) a preparation method of multi-walled carbon nanotube composite hierarchical-pore-channel NiAPO-11 comprises the following steps: respectively mixing 15 g of deionized water, 0.36 g of nickel acetylacetonate, 2.07 g of phosphoric acid and 1.28 g of pseudo-boehmite together and uniformly stirring; adding 0.1 g of starch to carry out a hydrolysis reaction and stir for 5 hours, adding 0.54 g of di-n-propylamine and 0.36 g of diisopropylamine and stirring for 3 hours again; and adding the mixture into a high-pressure crystallization kettle with a polytetrafluoro lining, sealing, crystallizing at 200 C. for 24 hours, taking out the mixture, washing a solid product, drying at 120 C. for 12 hours, calcining in a muffle furnace at 600 C. for 12 hours to obtain the hierarchical-pore-channel NiAPO-11, i.e., E; dissolving 1 g of silane coupling agent in a 30 g of DMF solvent; adding 1 g of multi-walled carbon nanotube for continuously refluxing and stirring for 1-3 hours, adding the E to reflux and stir at 100-120 C. for 1-3 hours, performing suction filtration on the obtained mixed solution, drying at 120 C. for 5 hours, and calcining the obtained solid powder in a muffle furnace at 500 C. for 5-10 hours, thereby obtaining the multi-walled carbon nanotube composite hierarchical-pore-channel NiAPO-11 composite carrier, i.e., F, and

(17) (2) uploading active components under 30-50 C. stirring conditions, dissolving 1.41 g of nickel acetylacetonate, 1 g of lanthanum nitrate and 0.47 g of ammonium metatungstate into 30 g of N,N-dimethylformamide, and fully dissolving to obtain a solution T; adding the carrier F to continuously stir for 12 hours, standing for 10 hours, drying in a drying oven at 100 C., calcining the obtained solid powder at 600 C. in an air atmosphere for at least 4 hours, and reducing at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydroisomerization catalyst, i.e., cat4, for preparing the biological aviation kerosene with castor oil.

Embodiment 5

(18) Preparation of a hydroisomerization catalyst comprises the following steps:

(19) (1) a preparation method of multi-walled carbon nanotube composite hierarchical-pore-channel NiAPO-11 comprises the following steps: respectively mixing 15 g of deionized water, 0.36 g of nickel acetylacetonate, 2.07 g of phosphoric acid and 1.28 g of pseudo-boehmite together and uniformly stirring; adding 0.1 g of starch to carry out a hydrolysis reaction and stir for 5 hours, adding 0.54 g of di-n-propylamine and 0.36 g of diisopropylamine and stirring for 3 hours again; and adding the mixture into a high-pressure crystallization kettle with a polytetrafluoro lining, sealing, crystallizing at 200 C. for 24 hours, taking out the mixture, washing a solid product, drying at 1201 C. for 12 hours, calcining in a muffle furnace at 600 C. for 12 hours to obtain the hierarchical-pore-channel NiAPO-11, i.e., E; dissolving 1 g of silane coupling agent in a 30 g of DMF solvent; adding 1 g of multi-walled carbon nanotube (with a diameter of 15 nm and a specific surface area of 500 m.sup.2/g) for continuously refluxing and stirring for 1-3 hours, adding the E to reflux and stir at 100-1201 C. for 1-3 hours, performing suction filtration on the obtained mixed solution, drying at 120 C. for 5 hours, and calcining the obtained solid powder in a muffle furnace at 500 C. for 5-10 hours, thereby obtaining the multi-walled carbon nanotube composite hierarchical-pore-channel NiAPO-11 composite carrier, i.e., F; and

(20) (2) uploading active components under 30-50 C. stirring conditions, dissolving 1.41 g of nickel acetylacetonate, 1 g of lanthanum nitrate and 0.45 g of ammonium molybdate into 30 g of N,N-dimethylformamide, and fully dissolving to obtain a solution T; adding the carrier F to continuously stir for 12 hours, standing for 10 hours, drying in a drying oven at 100 C., calcining the obtained solid powder at 600 C. in an air atmosphere for at least 4 hours, and reducing at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydroisomerization catalyst, i.e., cat5, for preparing the biological aviation kerosene with castor oil.

Embodiment 6

(21) Preparation of a hydroisomerization catalyst comprises the following steps:

(22) (1) a preparation method of multi-walled carbon nanotube composite hierarchical-pore-channel NiAPO-11 comprises the following steps: respectively mixing 15 g of deionized water, 0.36 g of nickel acetylacetonate, 2.07 g of phosphoric acid and 1.28 g of pseudo-boehmite together and uniformly stirring; adding 0.1 g of starch to carry out a hydrolysis reaction and stir for 5 hours, adding 0.54 g of di-n-propylamine and 0.36 g of diisopropylamine and stirring for 3 hours again; and adding the mixture into a high-pressure crystallization kettle with a polytetrafluoro lining, sealing, crystallizing at 2000 C. for 24 hours, taking out the mixture, washing a solid product, drying at 120 C. for 12 hours, calcining in a muffle furnace at 600 C. for 12 hours to obtain the hierarchical-pore-channel NiAPO-11, i.e., E; dissolving 1 g of a silane coupling agent in 30 g of DMF solvent; adding 1 g of multi-walled carbon nanotube for continuously refluxing and stirring for 1-3 hours, adding the E to reflux and stir at 100-120 C. for 1-3 hours, performing suction filtration on the obtained mixed solution, drying at 120 C. for 5 hours, and calcining the obtained solid powder in a muffle furnace at 5001 C. for 5-10 hours, thereby obtaining the multi-walled carbon nanotube composite hierarchical-pore-channel NiAPO-11 composite carrier, i.e., F; and

(23) (2) uploading active components under 30-50 C. stirring conditions, dissolving 1.41 g of nickel acetylacetonate, 1 g of lanthanum nitrate and 0.29 g of cobalt nitrate into 30 g of N,N-dimethylformamide, and fully dissolving to obtain a solution T; adding the carrier F to continuously stir for 12 hours, standing for 10 hours, drying in a drying oven at 100 C., calcining the obtained solid powder at 600 C. in an air atmosphere for at least 4 hours, and reducing at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydroisomerization catalyst, i.e., cat6, for preparing the biological aviation kerosene with castor oil.

Embodiment 7

(24) Preparation of a hydroisomerization catalyst comprises the following steps:

(25) (1) a preparation method of multi-walled carbon nanotube composite hierarchical-pore-channel NiSAPO-11 comprises the following steps: respectively mixing 15 g of deionized water, 0.36 g of nickel acetylacetonate, 0.36 g of silica sol, 2.07 g of phosphoric acid and 1.28 g of pseudo-boehmite together and uniformly stirring; adding 0.1 g of starch to carry out a hydrolysis reaction and stir for 5 hours, adding 0.54 g of di-n-propylamine and 0.36 g of diisopropylamine and stirring for 3 hours again; and adding the mixture into a high-pressure crystallization kettle with a polytetrafluoro lining, sealing, crystallizing at 2000 C. for 24 hours, taking out the mixture, washing a solid product, drying at 120 C. for 12 hours, calcining in a muffle furnace at 600 C. for 12 hours to obtain the hierarchical-pore-channel NiAPO-11, i.e., E; dissolving 1 g of silane coupling agent in 30 g of DMF solvent; adding 1 g of multi-walled carbon nanotube for continuously refluxing and stirring for 1-3 hours, adding the E to reflux and stir at 100-120 C. for 1-3 hours, performing suction filtration on the obtained mixed solution, drying at 120 C. for 5 hours, and calcining the obtained solid powder in a muffle furnace at 500 C. for 5-10 hours, thereby obtaining the multi-walled carbon nanotube composite hierarchical-pore-channel NiSAPO-11 composite carrier, i.e., F; and

(26) (2) uploading active components under 30-50 C. stirring conditions, dissolving 1.41 g of nickel acetylacetonate, 1 g of lanthanum nitrate and 0.47 g of ammonium metatungstate into 30 g of N,N-dimethylformamide, and fully dissolving to obtain a solution T; adding the carrier F to continuously stir for 12 hours, standing for 10 hours, drying in a drying oven at 100 C., calcining the obtained solid powder at 600 C. in an air atmosphere for at least 4 hours, and reducing at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydroisomerization catalyst, i.e., cat7, for preparing the biological aviation kerosene with castor oil.

Embodiment 8

(27) Preparation of a hydroisomerization catalyst comprises the following steps:

(28) (1) a preparation method of multi-walled carbon nanotube composite hierarchical-pore-channel NiSAPO-11 comprises the following steps: respectively mixing 15 g of deionized water, 0.36 g of nickel acetylacetonate, 0.36 g of silica sol, 2.07 g of phosphoric acid and 1.28 g of pseudo-boehmite together and uniformly stirring; adding 0.1 g of starch to carry out a hydrolysis reaction and stir for 5 hours, adding 0.54 g of di-n-propylamine and 0.36 g of diisopropylamine and stirring for 3 hours again; and adding the mixture into a high-pressure crystallization kettle with a polytetrafluoro lining, sealing, crystallizing at 2000 C. for 24 hours, taking out the mixture, washing a solid product, drying at 120 C. for 12 hours, calcining in a muffle furnace at 600 C. for 12 hours to obtain the hierarchical-pore-channel NiAPO-11, i.e., E; dissolving 1 g of silane coupling agent in 30 g of DMF solvent; adding 1 g of multi-walled carbon nanotube for continuously refluxing and stirring for 1-3 hours, adding the E to reflux and stir at 100-120 C. for 1-3 hours, performing suction filtration on the obtained mixed solution, drying at 120 C. for 5 hours, and calcining the obtained solid powder in a muffle furnace at 500 C. for 5-10 hours, thereby obtaining the multi-walled carbon nanotube composite hierarchical-pore-channel NiSAPO-11 composite carrier, i.e., F; and

(29) (2) uploading active components under 30-50 C. stirring conditions, dissolving 1.41 g of nickel acetylacetonate, 1 g of lanthanum nitrate and 0.45 g of ammonium molybdate into 30 g of N,N-dimethylformamide, and fully dissolving to obtain a solution T; adding the carrier F to continuously stir for 12 hours, standing for 10 hours, drying in a drying oven at 100 C., calcining the obtained solid powder at 600 C. in an air atmosphere for at least 4 hours, and reducing at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydroisomerization catalyst, i.e., cat8, for preparing the biological aviation kerosene with castor oil.

Embodiment 9

(30) Preparation of a hydroisomerization catalyst comprises the following steps:

(31) (1) a preparation method of multi-walled carbon nanotube composite hierarchical-pore-channel NiSAPO-11 comprises the following steps: respectively mixing 15 g of deionized water, 0.36 g of nickel acetylacetonate, 0.36 g of silica sol, 2.07 g of phosphoric acid and 1.28 g of pseudo-boehmite together and uniformly stirring; adding 0.1 g of starch to carry out a hydrolysis reaction and stir for 5 hours, adding 0.54 g of di-n-propylamine and 0.36 g of diisopropylamine and stirring for 3 hours again; and adding the mixture into a high-pressure crystallization kettle with a polytetrafluoro lining, sealing, crystallizing at 200 C. for 24 hours, taking out the mixture, washing a solid product, drying at 120 C. for 12 hours, calcining in a muffle furnace at 600 C. for 12 hours to obtain the hierarchical-pore-channel NiAPO-11, i.e., E; dissolving 1 g of a silane coupling agent in 30 g of DMF solvent; adding 1 g of multi-walled carbon nanotube for continuously refluxing and stirring for 1-3 hours, adding the E to reflux and stir at 100-120 C. for 1-3 hours, performing suction filtration on the obtained mixed solution, drying at 120 C. for 5 hours, and calcining the obtained solid powder in a muffle furnace at 500 C. for 5-10 hours, thereby obtaining the multi-walled carbon nanotube composite hierarchical-pore-channel NiSAPO-11 composite carrier, i.e., F; and

(32) (2) uploading active components under 30-50 C. stirring conditions, dissolving 1.41 g of nickel acetylacetonate, 1 g of lanthanum nitrate and 0.29 g of cobalt nitrate into 30 g of N,N-dimethylformamide, and fully dissolving to obtain a solution T; adding the carrier F to continuously stir for 12 hours, standing for 10 hours, drying in a drying oven at 100 C., calcining the obtained solid powder at 600 C. in an air atmosphere for at least 4 hours, and reducing at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydroisomerization catalyst, i.e., cat9, for preparing the biological aviation kerosene with castor oil.

Embodiment 10

(33) A using method of a hydrodeoxygenation catalyst comprises the following steps:

(34) 1) pretreatment of the catalyst: forming a catalyst in embodiment 1, filling the catalyst in a fixed bed reactor, heating to 400 C. under nitrogen purging with volume space velocity of 500 h.sup.1, changing into hydrogen with the same volume space velocity, maintaining a temperature of 400 C. for at least 3 hours, and regulating a temperature of the reactor to 300 C.; and

(35) 2) hydrodeoxygenation reaction: taking the castor oil (analytically pure, purity of 99%, and purchased from Tianjin Guangfu Reagent Co., Ltd.) as raw oil of the hydrodeoxygenation reaction, and regulating a pressure of a reaction system to 3 MPa, wherein a reaction temperature is 300 C., a hydrogen-oil ratio is 800, and volume space velocity of the fed raw oil is 2 h.sup.1; and collecting a liquid product obtained in the reaction every 2 hours. A method for analyzing the product comprises the following steps: testing by gas chromatography-mass spectrometry, adopting an Agilent gas chromatograph and mass spectrometer, and dividing the temperature of an injection oven into three phases; a phase of maintaining 50 C. for 10 minutes, a phase of heating to 100 C. at a speed of 30 C./min and maintaining for 10 minutes and a phase of heating to 200 C. at a speed of 30 C./min and maintaining for 10 minutes.

Embodiment 11

(36) A using method of a hydrolsomerization catalyst comprises the following steps:

(37) 1) pretreatment of the catalyst: forming a catalyst in embodiment 6, filling the catalyst in a fixed bed reactor, heating to 400 C. under nitrogen purging with volume space velocity of 500 h.sup.1, changing into hydrogen with the same volume space velocity, maintaining a temperature of 400 C. for at least 3 hours, and regulating a temperature of the reactor to 300 C.; and

(38) 2) hydroisomerization reaction: taking a dehydration product obtained by hydrodeoxygenation (composition:90% of C.sub.17-C.sub.18 and 10% of C.sub.5-C.sub.16) as a raw material (a preparation method: the hydrodeoxygenation catalyst in embodiments 1-3 is used as a catalyst, conditions in embodiment 10 are used as the conditions, and a method in embodiment 10 is used as an analysis method), and regulating a pressure of a reaction system to 3 MPa, wherein a reaction temperature is 320 C. a hydrogen-oil ratio is 800, and volume space velocity of the fed raw oil is 2 h.sup.1; and collecting a liquid product obtained in the reaction every 2 hours.

Embodiment 12

(39) A preparation method of an anhydrous liquid product through hydrodeoxygenation of castor oil comprises the following steps:

(40) pouring a castor oil hydrodeoxygenation product in embodiment 10 into 500 ml of separating funnel, standing for 5 hours, and separating a lower water layer to obtain an upper transparent solution layer, i.e., the anhydrous hydrodeoxygenation product, wherein the composition of the product comprises 90% of C.sub.17-C.sub.18 and 10% of C.sub.5-C.sub.16.

Reference Example 1

(41) The purpose is to compare preparation steps of an ordinary alumina carrier and a hydrodeoxygenation catalyst without an assistant Mn with embodiment 1:

(42) adding 24 g of distilled water into 10 g of nickel acetylacetonate, 0.45 g of ammonium molybdate and 0.32 g of ammonium metatungstate under room-temperature stirring conditions, stirring for 3 hours, and fully dissolving; adding ordinary alumina, stirring for 3-5 hours to obtain a mixed solution, standing the mixed solution for 10 hours, drying at 100 C. for 8 hours, calcining the obtained solid powder in a nitrogen atmosphere at 500-600 C. for 4-6 hours, and reducing the obtained solid powder at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydrodeoxygenation catalyst, i.e., cat10, for preparing biological aviation kerosene with castor oil.

Reference Example 2

(43) The purpose is to compare preparation steps of an ordinary nickel salt and a hydrodeoxygenation catalyst without an assistant Mn with embodiment 2:

(44) adding 24 g of distilled water into 10 g of nickel nitrate, 0.45 g of ammonium molybdate and 0.32 g of ammonium metatungstate under room-temperature stirring conditions, stirring for 3 hours, and fully dissolving; adding self-made large-specific surface nano-alumina, stirring for 3-5 hours to obtain a mixed solution, standing the mixed solution for 10 hours, drying at 100 C. for 8 hours, calcining the obtained solid powder in a nitrogen atmosphere at 500-600 C. for 4-6 hours, and reducing the obtained solid powder at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydrodeoxygenation catalyst, i.e., cat11, for preparing biological aviation kerosene with castor oil.

Reference Example 3

(45) The purpose is to compare preparation steps of a microporous SAPO-11 catalyst with embodiment 4:

(46) (1) a preparation method of SAPO-11: respectively mixing 15 g of deionized water, 0.36 g of silica sol, 2.07 g of phosphoric acid and 1.28 g of pseudo-boehmite together and uniformly stirring; adding 0.54 g of di-n-propylamine and 0.36 g of diisopropylamine and stirring for 3 hours again; and adding the mixture into a high-pressure crystallization kettle with a polytetrafluoro lining, sealing, crystallizing at 200 C. for 24 hours, taking out the mixture, washing a solid product, drying at 120 C. for 12 hours, and calcining in a muffle furnace at 600 C. for 12 hours, thereby obtaining the hierarchical-pore-channel SAPO-11, i.e., sample C; and

(47) (2) uploading of active components: dissolving 1.41 g of nickel acetylacetonate and 0.32 g of cobalt nitrate into 22 g of ethanol under 30-50 C. stirring conditions, and fully dissolving to obtain a solution T; adding 7.52 g of the sample C into the solution T, stirring for at least 12 hours, standing for 10 hours, drying the obtained solution in an air atmosphere at 1200 C., and calcining in the air atmosphere at 600 C. for at least 4 hours, thereby obtaining the hydroisomerization catalyst, i.e., cat12, for preparing biological aviation kerosene with castor oil.

Reference Example 4

(48) The purpose is to compare preparation steps of a multi-walled-carbon-nanotube-free composite hierarchical-pore-channel NiAPO-11 catalyst with embodiment 5:

(49) a preparation method of hierarchical-pore-channel NiAPO-11: respectively mixing 15 g of deionized water, 0.36 g of nickel acetylacetonate, 2.07 g of phosphoric acid and 1.28 g of pseudo-boehmite together and uniformly stirring; adding 0.1 g of starch to carry out a hydrolysis reaction and stir for 5 hours, adding 0.54 g of di-n-propylamine and 0.36 g of diisopropylamine and stirring for 3 hours again; and adding the mixture into a high-pressure crystallization kettle with a polytetrafluoro lining, sealing, crystallizing at 200 C. for 24 hours, taking out the mixture, washing a solid product, drying at 120 C. for 12 hours, and calcining in a muffle furnace at 600 C. for 12 hours to obtain the hierarchical-pore-channel NiAPO-11, i.e., E; and

(50) uploading active components under 30-50 C. stirring conditions, dissolving 1.41 g of nickel acetylacetonate, 1 g of lanthanum nitrate and 0.45 g of ammonium molybdate into 30 g of N,N-dimethylformamide, and fully dissolving to obtain a solution T; adding the carrier E to continuously stir for 12 hours, standing for 10 hours, drying in a drying oven at 100 C., calcining the obtained solid powder at 600 C. in an air atmosphere for at least 4 hours, and reducing at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydroisomerization catalyst, i.e., cat13, for preparing the biological aviation kerosene with castor oil.

Reference Example 5

(51) The purpose is to compare preparation steps of a multi-walled-carbon-nanotube-free composite hierarchical-pore-channel NiSAPO-11 catalyst with embodiment 7:

(52) (1) a preparation method of multi-walled carbon nanotube composite hierarchical-pore-channel NiSAPO-11 comprises the following steps: respectively mixing 15 g of deionized water, 0.36 g of nickel acetylacetonate, 0.36 g of silica sol, 2.07 g of phosphoric acid and 1.28 g of pseudo-boehmite together and uniformly stirring; adding 0.1 g of starch to carry out a hydrolysis reaction and stir for 5 hours, adding 0.54 g of di-n-propylamine and 0.36 g of diisopropylamine and stirring for 3 hours again; and adding the mixture into a high-pressure crystallization kettle with a polytetrafluoro lining, sealing, crystallizing at 200 C. for 24 hours, taking out the mixture, washing a solid product, drying at 120 C. for 12 hours, and calcining in a muffle furnace at 600 C. for 12 hours to obtain the hierarchical-pore-channel NiSAPO-11, i.e., E; and

(53) (2) uploading active components under 30-501 C. stirring conditions, dissolving 1.41 g of nickel acetylacetonate, 1 g of lanthanum nitrate and 0.47 g of ammonium metatungstate into 30 g of N,N-dimethylformamide, and fully dissolving to obtain a solution T; adding the carrier E to continuously stir for 12 hours, standing for 10 hours, drying in a drying oven at 100 C., calcining the obtained solid powder at 600 C. in an air atmosphere for at least 4 hours, and reducing at 550-6001 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydroisomerization catalyst, i.e., cat14, for preparing the biological aviation kerosene with castor oil.

Reference Example 6

(54) The purpose is to compare preparation steps of a multi-walled carbon-nanotube composite hierarchical-pore-channel NiAPO-11 catalyst without adding an assistant La with embodiment 6:

(55) (1) a preparation method of multi-walled carbon nanotube composite hierarchical-pore-channel NiAPO-11 comprises the following steps: respectively mixing 15 g of deionized water, 0.36 g of nickel acetylacetonate, 2.07 g of phosphoric acid and 1.28 g of pseudo-boehmite together and uniformly stirring; adding 0.1 g of starch to carry out a hydrolysis reaction and stir for 5 hours, adding 0.54 g of di-n-propylamine and 0.36 g of diisopropylamine and stirring for 3 hours again; and adding the mixture into a high-pressure crystallization kettle with a polytetrafluoro lining, sealing, crystallizing at 200 C. for 24 hours, taking out the mixture, washing a solid product, drying at 120 C. for 12 hours, calcining in a muffle furnace at 600 C. for 12 hours to obtain the hierarchical-pore-channel NiAPO-11, i.e., E; dissolving 1 g of a silane coupling agent in 30 g of DMF solvent; adding 1 g of multi-walled carbon nanotube for continuously refluxing and stirring for 1-3 hours, adding the E to reflux and stir at 100-120 C. for 1-3 hours, performing suction filtration on the obtained mixed solution, drying at 120 C. for 5 hours, and calcining the obtained solid powder in a muffle furnace at 500 C. for 5-10 hours, thereby obtaining the multi-walled carbon nanotube composite hierarchical-pore-channel NiAPO-11 composite carrier, i.e., F; and

(56) (2) uploading active components under 30-50 C. stirring conditions, dissolving 1.41 g of nickel acetylacetonate and 0.29 g of cobalt nitrate into 30 g of N,N-dimethylformamide, and fully dissolving to obtain a solution T; adding the carrier F to continuously stir for 12 hours, standing for 10 hours, drying in a drying oven at 100 C., calcining the obtained solid powder at 600 C. in an air atmosphere for at least 4 hours, and reducing at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydroisomerization catalyst, i.e., cat15, for preparing the biological aviation kerosene with castor oil.

Reference Example 7

(57) The purpose is to compare preparation steps of a multi-walled carbon-nanotube composite hierarchical-pore-channel NiSAPO-11 catalyst without adding an assistant La with embodiment 8:

(58) (1) a preparation method of multi-walled carbon nanotube composite hierarchical-pore-channel NiSAPO-11 comprises the following steps: respectively mixing 15 g of deionized water, 0.36 g of nickel acetylacetonate, 0.36 g of silica sol, 2.07 g of phosphoric acid and 1.28 g of pseudo-boehmite together and uniformly stirring; adding 0.1 g of starch to carry out a hydrolysis reaction and stir for 5 hours, adding 0.54 g of di-n-propylamine and 0.36 g of diisopropylamine and stirring for 3 hours again; and adding the mixture into a high-pressure crystallization kettle with a polytetrafluoro lining, sealing, crystallizing at 2001 C. for 24 hours, taking out the mixture, washing a solid product, drying at 120 C. for 12 hours, calcining in a muffle furnace at 600 C. for 12 hours to obtain the hierarchical-pore-channel NiAPO-11, i.e., E; dissolving 1 g of a silane coupling agent in 30 g of DMF solvent; adding 1 g of multi-walled carbon nanotube for continuously refluxing and stirring for 1-3 hours, adding the E to reflux and stir at 100-1201 C. for 1-3 hours, performing suction filtration on the obtained mixed solution, drying at 120 C. for 5 hours, and calcining the obtained solid powder in a muffle furnace at 500 C. for 5-10 hours, thereby obtaining the multi-walled carbon nanotube composite hierarchical-pore-channel NiSAPO-11 composite carrier, i.e., F; and

(59) (2) uploading active components under 30-50 C. stirring conditions, dissolving 1.41 g of nickel acetylacetonate and 0.45 g of ammonium molybdate into 30 g of N,N-dimethylformamide, and fully dissolving to obtain a solution T; adding the carrier F to continuously stir for 12 hours, standing for 10 hours, drying in a drying oven at 100 C., calcining the obtained solid powder at 600 C. in an air atmosphere for at least 4 hours, and reducing at 550-600 C. at hydrogen flow velocity of 200-300 mL/min for at least 3 hours, thereby obtaining the hydroisomerization catalyst, i.e., cat16, for preparing the biological aviation kerosene with castor oil.

(60) TABLE-US-00001 TABLE 1 evaluation results of the catalysts cat1-cat16 are as follows: evaluation conditions of cat1-cat3 include 300 C., 3 MPa and 1-2 h.sup.1; and evaluation conditions of cat6-cat16 include 300-360 C., 3 MPa and 1-2 h.sup.1. Evaluation standards are as follows: a conversion rate of castor oil and C.sub.8-C.sub.16 selectivity are calculated according to a peak area ratio of gas chromatography; and quality of the catalysts directly affects the conversion rate and selectivity of the aviation kerosene, and also affects life of the catalyst. Conversion rate C.sub.8-C.sub.16 Catalyst of Caster oil (%) Liquid yield (%) Life/h selectivity (%) Cat 1 99.5 85.7 350 85.8 Cat 2 98.4 86.4 350 85.7 Cat 3 98.7 87.5 284 88.6 Cat 4 98.7 80.2 350 78.7 Cat 5 98.5 82.5 350 80.6 Cat 6 97.6 86.3 350 85.6 Cat 7 95.7 84.5 350 84.3 Cat 8 96.6 86.8 350 90.1 Cat 9 99.7 87.6 296 91.5 Cat 10 80.3 80.6 50 20.4 Cat 11 75.6 82.4 70 32.4 Cat 12 68.3 86.7 60 29.7 Cat 13 76.4 82.6 54 46.3 Cat 14 80.7 83.5 32 68.7 Cat 15 78.2 86.1 46 56.0 Cat 16 78.2 86.1 40 51.0

(61) TABLE-US-00002 TABLE 2 Comparison of physical and chemical properties of the biological aviation kerosene of the castor oil with those of biological aviation kerosene of jatropha curcas and jet 3# aviation kerosene: Aviation kerosene Aviation kerosene Items Jet 3# of castor oil of jatropha curcas Freezing point ( C.) <47 50 52 Density (Kg .Math. m.sup.3) 775-830 780 790 Flash point ( C.) >38 46 46 V kinematic viscosity <8.0 3.5 2.6 (mm.sup.2S.sup.1) Sulfur content (%) <20 ppm 0 <20 ppm Olefin content (%) 1-2 0 <1 Aromatic hydrocarbon <1 0 <1 content (%)

(62) Cat1-cat9 in Table 1 are modified catalysts and have extremely high life, conversion rates of castor oil and selectivity of aviation kerosene components, while unmodified catalysts have extremely low conversion rates and selectivity, which indicates that modification of the hydrodeoxygenation catalyst really increases hydrothermal stability, thereby increasing the life of the catalyst. For the hydroisomerization catalyst, due to the introduction of the hierarchical pore channel and multi-walled carbon nanotubes, the life of the catalyst is greatly increased while increasing the selectivity of the aviation kerosene, thereby proving effects after modification.

(63) In Table 2, it can be seen from comparison that all items are within standards except the density. For the density, since the components in the biological aviation kerosene with castor oil are C.sub.8-C.sub.18 alkanes, the density may not exceed 790. However, the biological aviation kerosene can be used when doped with petroleum-based aviation kerosene, so the density after doping may be within the standard.