WO2017020401A1 - 用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂 - Google Patents

用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂 Download PDF

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WO2017020401A1
WO2017020401A1 PCT/CN2015/089535 CN2015089535W WO2017020401A1 WO 2017020401 A1 WO2017020401 A1 WO 2017020401A1 CN 2015089535 W CN2015089535 W CN 2015089535W WO 2017020401 A1 WO2017020401 A1 WO 2017020401A1
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solution
catalyst
stirring
stirred
added
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PCT/CN2015/089535
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English (en)
French (fr)
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李伟
倪保霞
关庆鑫
何良年
叶锋
崔晓莹
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南开大学
天津南开大学蓖麻工程科技有限公司
天津蓖能科技有限公司
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Publication of WO2017020401A1 publication Critical patent/WO2017020401A1/zh
Priority to US15/888,019 priority Critical patent/US10399069B2/en

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    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention relates to a catalyst for preparing bio-aviation kerosene for castor oil, in particular to a hydroisomerization and cracking catalyst for preparing bio-aviation kerosene for castor oil and a preparation method and application thereof.
  • TS-1 Al-modified titanium silicalite
  • urea is used as a dispersing agent when the active component is supported.
  • a high yield of bio-aviation kerosene can be obtained by the present invention.
  • the main component of aviation kerosene is a mixture of linear and branched paraffins with a carbon number of 8-16. Due to the influence of freezing point, branched paraffins are the main components of aviation kerosene.
  • the standard for aviation kerosene (from ASTM D7566) is less than -47 ° C freezing point, flash point greater than 38 ° C, viscosity less than 8.0 mm 2 S -1 , boiling point between 200-300 ° C, sulfur content less than 20 ppm, olefin content less than 2% The aromatic content is less than 1%.
  • the known jatropha bio-air kerosene has a freezing point of -49 ° C, a flash point of 44 ° C, a viscosity of 4.3 mm 2 S -1 , a boiling point of 200-300 ° C, and a sulfur content, an olefin content, and an aromatic content of 0.
  • the main component of castor oil is a glyceride of 9-alkenyl-12-hydroxyoctadecanoic acid.
  • castor oil removes a hydroxyl group and a double bond by hydrodeoxygenation to form a linear alkane having a carbon number of 17, 18.
  • the appropriate catalyst is then selected for hydroisomerization and cracking to effect carbon chain isomerization and cracking into linear and branched alkanes having a carbon number of 8-16. Therefore, in the hydroisomerization and cracking reaction, the selectivity of the product is crucial, and a high yield of aviation kerosene component can be obtained by selecting a suitable carrier and active component.
  • Chinese patent CN101952392A discloses a method for preparing aviation fuel for renewable raw materials such as vegetable oil and animal fat.
  • the raw material is contacted with a hydrogenation and deoxidation catalyst to prepare a linear alkane, and then contacted with an isomerization catalyst to isomerize at least a part of the linear chain.
  • the alkane is used to produce a branched alkane, which is then contacted with a selective cracking catalyst to obtain a C8-C16 alkane.
  • CN102482595A discloses a method for manufacturing an aviation fuel oil base material, which uses a plant and vegetable oil as a raw material, hydrogenates a raw material through a catalyst having a function of deoxidation and hydrogenation, and then performs hydroisomerization treatment as a raw material to obtain aviation fuel.
  • CN102676203A discloses a method for preparing biomass aviation fuel by using a process of oxidation, hydrolysis and decarboxylation of double bonds by using jatropha oil, rubber seed oil, palm oil and waste oil as raw materials.
  • CN102994138A discloses a method for preparing bio-aviation kerosene from waste oil.
  • CN201410080542.4 discloses a catalyst for preparing aviation kerosene from castor oil and a preparation method thereof, which mainly adopts 3-aminopropyltriethoxysilane and citric acid to modify a hydrodeoxygenation carrier, and introduces Fe as a method.
  • Auxiliary agent for hydrodeoxygenation catalyst discloses a preparation method for preparing bio-coal hydrodeoxygenation and hydroisomerization catalyst for castor oil, which mainly adopts modified MCM-41 as a carrier of hydrodeoxygenation catalyst;
  • the carrier selected for the catalyst is modified SAPO-11, and the selected active component is one of Pt, Pd or Ni.
  • TS-1 Al-modified titanium silicon molecular sieve
  • Ti and Al are introduced simultaneously, and the Al portion is removed after the synthesis is completed, and the amount of removal of Al is controlled, in particular, the synthetic interstitial metal compounds Ni x W and Ni x Mo are used as active centers, and the active components are supported.
  • Urea is used as a dispersing agent to obtain a hydroisomerization and cracking catalyst for preparing bio-aviation kerosene for castor oil.
  • a further object of the present invention is to provide an application of the above catalyst for the preparation of bio-aviation kerosene as a feedstock oil for hydroisomerization and cracking reaction after use in the anhydrous liquid product after hydrodeoxygenation of castor oil to obtain a high yield bio-aviation kerosene.
  • the Al: modified titanium silicalite has a Si:Ti molar ratio of 50-100 and a Si:Al molar ratio of 50-100.
  • the preparation method of the above catalyst provided by the present invention comprises the following steps:
  • the solid powder is calcined in an air atmosphere at 550-600 ° C for at least 2 h, then at a hydrogen flow rate of 200-300 mL/min, at 550-600 ° C for at least 3 h, and after cooling to room temperature, a volume ratio of 1% O 2 / The N 2 passivation gas was passivated for 3 hours to obtain the desired catalyst.
  • Si is calculated as SiO 2
  • Ti is calculated as TiO 2
  • urea is used as a dispersing agent in an amount of from 2 to 5%, preferably from 2 to 3%, by mass based on the mass of the carrier.
  • the invention provides the application of the above catalyst, and the specific application (use) method comprises the following steps:
  • Pretreatment of the catalyst The required amount of the catalyst is molded into a fixed bed reactor, and the temperature is raised to 400-450 ° C under a nitrogen purge at a space velocity of 800-1200 h -1 , and then switched to an equal volume. Space-speed hydrogen, maintained at 400-450 ° C for at least 3 hours, and then adjust the reactor temperature to the temperature of the hydroisomerization and cracking reaction;
  • the anhydrous liquid product after the hydrodeoxygenation of the castor oil comprises an alkane having a carbon number of 17, 18 and having a content of 95-97%, an alkane having a carbon number of 8-16 of 1-3%, and a carbon number.
  • the alkane content of 5-7 is 1-2%.
  • the preparation method of the anhydrous liquid product after the hydrodeoxygenation of castor oil is castor oil (the castor oil is purchased from Tianjin Guangfu Technology Co., Ltd., wherein 90% of the components are ricinoleic acid, and 10% of the components are Palmitic acid and stearic acid are used as raw materials for catalysts (with SAPO-11 as the carrier and Ni 2 P as the active component, wherein the active component accounts for 25% of the total mass of the catalyst) to obtain hydrodeoxygenated products (Reference Liu, S) .;Zhu,Q.;Guan,Q.;He,L.;Li,W.Bio-aviation fuel production from hydroprocessing castor oil promoted by the nickel-based bifunctional catalysts.Bioresour.Technol.2015,183,93-100 .), the water was removed by liquid separation with a separatory funnel to obtain an anhydrous liquid product after hydrodeoxygenation of castor oil.
  • the castor oil is purchased from Tianjin Guang
  • the invention is characterized in that in the process of preparing the catalyst, firstly, Ti and Al are simultaneously introduced into the TS-1, and after the synthesis is completed, the Al portion is removed, and the interstitial metal compound Ni x is synthesized by controlling the amount of Al removed.
  • W and Ni x Mo are used as active centers, and urea is used as a dispersing agent when the active component is supported, so that the precursor of the active component can be super-highly dispersed on the surface of the carrier, and the urea is decomposed and removed in the subsequent high-temperature roasting process, and the catalyst
  • the particle size is hindered by the dispersant, does not cause sintering at high temperatures, and causes the particle size of the metal component in the catalyst to be smaller and uniform.
  • Ni x W and Ni x Mo are the active centers of the catalysts. They are not ordinary bimetallic catalysts. W or Mo will enter the lattice of Ni during the preparation process, causing the lattice of Ni to expand and the bond length to be long. Can be weakened (see literature Li, R.; Guan, Q.; Wei, R.; Yang, S.; Shu, Z.; Dong, Y.; Chen, J.; Li, WA Potential Regularity for Enhancing the Hydrogenation Properties of Ni2P.J. Phys. Chem. C 2015, 119, 2557-2565.), thereby having better hydrogen dissociation activity, can provide a high yield of bio-aviation kerosene components.
  • the present invention has the following advantages and significant advantages over the prior art:
  • the present invention adopts Al-modified TS-1, and partially removes Al during the preparation process, thereby capable of forming a certain oxygen vacancy, which contributes to an increase in activity of the catalyst and selectivity of the product, and at the same time, by controlling the removal of Al.
  • the amount of Al-modified TS-1 can be adjusted.
  • urea is used as a dispersing agent, so that the precursor of the active component can be super-highly dispersed on the surface of the carrier, and the urea is decomposed and removed in the subsequent high-temperature roasting process.
  • the particle size of the catalyst is hindered by the dispersant, does not cause sintering at a high temperature, and causes the particle size of the metal component in the catalyst to be smaller and uniform, thereby improving the catalytic efficiency.
  • the present invention employs interstitial metal compounds Ni x W, Ni x Mo as active centers of the catalysts, which are not ordinary bimetallic catalysts, and W or Mo will enter the lattice of Ni during the preparation process, so that Ni The lattice expands, the bond length becomes longer, and the bond energy becomes weaker (see Li, R.; Guan, Q.; Wei, R.; Yang, S.; Shu, Z.; Dong, Y.; Chen, J. Li, WA Potential Regularity for Enhancing the Hydrogenation Properties of Ni 2 PJPhys. Chem. C 2015, 119, 2557-2565.), thereby having better hydrogen dissociation activity, can provide a high yield of bio-aviation kerosene component.
  • Example 1 is a powder X-ray diffraction pattern of Al-modified TS-1 synthesized in Example 1.
  • Example 2 is a scanning electron micrograph of the catalyst cat1 prepared in Example 1.
  • Example 3 is a bar graph of experimental results obtained by operating the catalysts cat1-2 and cat11-14 prepared in Comparative Example 11-2, Comparative Example 11-14, according to the method of Example 12.
  • Example 1 Preparation of a hydroisomerization and cracking catalyst comprising the following steps:
  • the sample was taken out and washed with deionized water until neutral. After drying, it is baked in a muffle furnace at 550 ° C for 6 h. After the sample is cooled to room temperature, it is put into 0.5 mol. /L HCl solution, heated and stirred at 60 ° C for 3 h, then the sample was separated by suction filtration, washed with deionized water until neutral, dried and then calcined at 550 ° C for 2 h under nitrogen atmosphere to obtain Al modified TS-1 Is the carrier A;
  • a hydroisomerization and cracking catalyst for kerosene designated as cat1.
  • Example 2 Preparation of a hydroisomerization and cracking catalyst comprising the following steps:
  • the solution B was slowly added dropwise to the solution A which was stirred at a high speed, and after the completion of the dropwise addition, 0.08 g of aluminum isopropoxide was added to the solution A, and stirring was continued. 3h, the solution C was obtained; the mass of the solution C was recorded, and then the solution C was heated and stirred in a constant temperature water bath at 80 ° C for 3 h to remove the isopropanol in the solution, and then the mass of the solution was added to the heated stirring with deionized water.
  • solution D The value before refluxing gives solution D; then, the solution D is placed in a high-pressure reaction vessel with a PTFE liner, sealed and aged at 100 ° C for 6 h, then heated to 160 ° C for 18 h, and the crystallization is completed.
  • the sample was taken out, washed with deionized water until neutral, dried and then calcined in a muffle furnace at 550 ° C for 6 h. After the sample was cooled to room temperature, it was placed in a 0.5 mol/L HCl solution, and heated and stirred at 60 ° C for 3 h.
  • the sample is separated by suction filtration, washed with deionized water to neutrality, dried and then calcined at 550 ° C for 2 h under a nitrogen atmosphere to obtain Al-modified TS-1, which is the carrier A;
  • a hydroisomerization and cracking catalyst for kerosene designated as cat2.
  • the sample was taken out and washed with deionized water until neutral. After drying, it is baked in a muffle furnace at 550 ° C for 6 h. After the sample is cooled to room temperature, it is put into 0.5 mol. /L HCl solution, heated and stirred at 60 ° C for 3 h, then the sample was separated by suction filtration, washed with deionized water until neutral, dried and then calcined at 550 ° C for 2 h under nitrogen atmosphere to obtain Al modified TS-1 Is the carrier A;
  • Example 4 Preparation of a hydroisomerization and cracking catalyst comprising the following steps:
  • the solution B was slowly added dropwise to the solution A which was stirred at a high speed, and 0.11 g of aluminum isopropoxide was added to the solution A after the completion of the dropwise addition, and stirring was continued.
  • the solution C was obtained; the mass of the solution C was recorded, and then the solution C was heated and stirred in a constant temperature water bath at 80 ° C for 3 h to remove the isopropanol in the solution, and then the mass of the solution was added to the heated stirring with deionized water.
  • solution D The value before refluxing gives solution D; then, the solution D is placed in a high-pressure reaction vessel with a PTFE liner, sealed and aged at 100 ° C for 6 h, then heated to 160 ° C for 18 h, and the crystallization is completed.
  • the sample was taken out, washed with deionized water until neutral, dried and then calcined in a muffle furnace at 550 ° C for 6 h. After the sample was cooled to room temperature, it was placed in a 0.5 mol/L HCl solution, and heated and stirred at 60 ° C for 3 h.
  • the sample is separated by suction filtration, washed with deionized water to neutrality, dried and then calcined at 550 ° C for 2 h under a nitrogen atmosphere to obtain Al-modified TS-1, which is the carrier A;
  • Example 5 Preparation of a hydroisomerization and cracking catalyst comprising the following steps:
  • the sample was taken out and washed with deionized water until neutral. After drying, it is baked in a muffle furnace at 550 ° C for 6 h. After the sample is cooled to room temperature, it is put into 0.5 mol. /L HCl solution, heated and stirred at 60 ° C for 3 h, then the sample was separated by suction filtration, washed with deionized water until neutral, dried and then calcined at 550 ° C for 2 h under nitrogen atmosphere to obtain Al modified TS-1 Is the carrier A;
  • the hydroisomerization and cracking catalyst is referred to as cat5.
  • Example 6 Preparation of a hydroisomerization and cracking catalyst comprising the following steps:
  • the solution B was slowly added dropwise to the solution A which was stirred at a high speed, and 0.11 g of aluminum isopropoxide was added to the solution A after the completion of the dropwise addition, and stirring was continued.
  • the solution C was obtained; the mass of the solution C was recorded, and then the solution C was heated and stirred in a constant temperature water bath at 80 ° C for 3 h to remove the isopropanol in the solution, and then the mass of the solution was added to the heated stirring with deionized water.
  • solution D The value before refluxing gives solution D; then, the solution D is placed in a high-pressure reaction vessel with a PTFE liner, sealed and aged at 100 ° C for 6 h, then heated to 160 ° C for 18 h, and the crystallization is completed.
  • the sample was taken out, washed with deionized water until neutral, dried and then calcined in a muffle furnace at 550 ° C for 6 h. After the sample was cooled to room temperature, it was placed in a 0.5 mol/L HCl solution, and heated and stirred at 60 ° C for 3 h.
  • the sample is separated by suction filtration, washed with deionized water to neutrality, dried and then calcined at 550 ° C for 2 h under a nitrogen atmosphere to obtain Al-modified TS-1, which is the carrier A;
  • Example 7 Preparation of a hydroisomerization and cracking catalyst comprising the following steps:
  • the sample was taken out and washed with deionized water until neutral. After drying, it is calcined in a muffle furnace at 550 ° C for 6 h. After the sample is cooled to room temperature, it is placed at 0.5 mol / The L HCl solution was heated and stirred at 60 ° C for 3 h, and then the sample was separated by suction filtration, washed with deionized water until neutral, dried and then calcined at 550 ° C for 2 h under a nitrogen atmosphere to obtain Al-modified TS-1. That is, the carrier A;
  • Example 8 Preparation of a hydroisomerization and cracking catalyst comprising the following steps:
  • the solution B was slowly added dropwise to the solution A which was stirred at a high speed, and after the completion of the dropwise addition, 0.06 g of aluminum isopropoxide was added to the solution A, and stirring was continued for 3 hours.
  • the solution C was obtained; the mass of the solution C was recorded, and then the solution C was heated and stirred in a constant temperature water bath at 80 ° C for 3 hours to remove the isopropanol in the solution, and then the mass of the solution was made up with deionized water until it was heated and stirred.
  • the value is obtained to obtain the solution D; then the solution D is placed in a high-pressure reaction vessel with a PTFE liner, sealed and aged at 100 ° C for 6 h, then heated to 160 ° C for 18 h, after crystallization is completed
  • the sample was taken out, washed with deionized water to neutrality, dried and then calcined in a muffle furnace at 550 ° C for 6 h.
  • the sample is separated by suction filtration, washed with deionized water to neutrality, dried and then calcined at 550 ° C for 2 h under a nitrogen atmosphere to obtain Al-modified TS-1, which is carrier A;
  • Example 9 Preparation of a hydroisomerization and cracking catalyst comprising the following steps:
  • the sample was taken out and washed with deionized water until neutral. After drying, it is calcined in a muffle furnace at 550 ° C for 6 h. After the sample is cooled to room temperature, it is placed at 0.5 mol / The L HCl solution was heated and stirred at 60 ° C for 3 h, and then the sample was separated by suction filtration, washed with deionized water until neutral, dried and then calcined at 550 ° C for 2 h under a nitrogen atmosphere to obtain Al-modified TS-1. That is, the carrier A;
  • Example 10 Preparation of a hydroisomerization and cracking catalyst comprising the following steps:
  • the solution B was slowly added dropwise to the solution A which was stirred at a high speed, and after the completion of the dropwise addition, 0.06 g of aluminum isopropoxide was added to the solution A, and stirring was continued for 3 hours.
  • the solution C was obtained; the mass of the solution C was recorded, and then the solution C was heated and stirred in a constant temperature water bath at 80 ° C for 3 hours to remove the isopropanol in the solution, and then the mass of the solution was made up with deionized water until it was heated and stirred.
  • the value is obtained to obtain the solution D; then the solution D is placed in a high-pressure reaction vessel with a PTFE liner, sealed and aged at 100 ° C for 6 h, then heated to 160 ° C for 18 h, after crystallization is completed
  • the sample was taken out, washed with deionized water to neutrality, dried and then calcined in a muffle furnace at 550 ° C for 6 h.
  • the sample is separated by suction filtration, washed with deionized water to neutrality, dried and then calcined at 550 ° C for 2 h under a nitrogen atmosphere to obtain Al-modified TS-1, which is carrier A;
  • Example 11 A method of using a hydroisomerization and cracking catalyst comprising the steps of:
  • the preparation method of anhydrous liquid product after hydrodeoxygenation of castor oil is according to the literature (Liu, S.; Zhu, Q.; Guan, Q.; He, L.; Li, W. Bio-aviation fuel production from hydroprocessing castor oil). Produced by the method shown by the method of Bioresour. Technol. 2015, 183, 93-100.), specifically castor oil (castor oil is purchased at Tianjin Guangfu Technology Co., Ltd., 90% of which The component is ricinoleic acid, 10% of which is palmitic acid and stearic acid.
  • the catalyst is based on SAPO-11, and Ni 2 P is the active component, wherein the active component accounts for 25% of the total mass of the catalyst.
  • the hydrodeoxygenation product is obtained, and the water therein is separated by a separating funnel to obtain an anhydrous liquid product after hydrodeoxygenation of the castor oil.
  • the obtained anhydrous liquid product is detected by gas chromatography-mass spectrometry (Agilent gas chromatography and mass spectrometry), which mainly includes: an alkane content of 95 to 97% of an alkane having a carbon number of 17, 18, and an alkane content of 8 to 16 carbon atoms.
  • the olefin content of 1-3% and having 5 to 7 carbon atoms is 1-2%.
  • Example 12 A method of using a hydroisomerization and cracking catalyst comprising the steps of:
  • Example 13 A method of using a hydroisomerization and cracking catalyst comprising the steps of:
  • Comparative Example 1 The purpose is to show that the preparation steps of the TS-1 catalyst which has not been subjected to Al modification are compared with Example 1:
  • TS-1 Preparation method of TS-1: 5.59 g of a 25% aqueous solution of TPAOH (tetrapropylammonium hydroxide) was added dropwise to 20 g of deionized water under stirring at 50 ° C, and stirred for 30 minutes, and then slowly added 5.83 g. Ethyl orthosilicate and stirring for 2h to obtain solution A; 0.14g of tetrabutyl titanate was added dropwise to 0.3g of isopropanol under stirring at 50 ° C, then stirring was continued for 0.5 h to obtain solution B; then the solution was B was slowly added dropwise to the solution A in high-speed stirring.
  • TPAOH tetrapropylammonium hydroxide
  • a hydroisomerization and cracking catalyst designated cat11.
  • TS-1 Preparation method of TS-1: 5.59 g of a 25% aqueous solution of TPAOH (tetrapropylammonium hydroxide) was added dropwise to 20 g of deionized water under stirring at 50 ° C, and stirred for 30 minutes, and then slowly added 5.83 g. Ethyl orthosilicate and stirring for 2h to obtain solution A; 0.14g of tetrabutyl titanate was added dropwise to 0.3g of isopropanol under stirring at 50 ° C, then stirring was continued for 0.5 h to obtain solution B; then the solution was B was slowly added dropwise to the solution A in high-speed stirring.
  • TPAOH tetrapropylammonium hydroxide
  • Example 3 The purpose of explaining the preparation steps of the catalyst which did not use urea as a dispersing agent in the preparation process was compared with Example 1:
  • the sample was taken out and washed with deionized water until neutral. After drying, it is baked in a muffle furnace at 550 ° C for 6 h. After the sample is cooled to room temperature, it is put into 0.5 mol. /L HCl solution, heated and stirred at 60 ° C for 3 h, then the sample was separated by suction filtration, washed with deionized water until neutral, dried and then calcined at 550 ° C for 2 h under nitrogen atmosphere to obtain Al modified TS-1 Is the carrier A;
  • the sample was taken out and washed with deionized water until neutral. After drying, it is baked in a muffle furnace at 550 ° C for 6 h. After the sample is cooled to room temperature, it is put into 0.5 mol. /L HCl solution, heated and stirred at 60 ° C for 3 h, then the sample was separated by suction filtration, washed with deionized water to medium , after drying, calcined at 550 ° C for 2 h under nitrogen atmosphere, to obtain Al modified TS-1, namely carrier A;
  • Example 5 Comparative Example 5. The purpose of the preparation is to demonstrate that the preparation steps of the Al-modified TS-1 catalyst for achieving different amounts of aluminum removal by controlling the heating and stirring reflux time are compared with Example 1:
  • the sample was taken out and washed with deionized water until neutral. After drying, it is baked in a muffle furnace at 550 ° C for 6 h. After the sample is cooled to room temperature, it is put into 0.5 mol. /L HCl solution, heated and stirred at 60 ° C for 1 h, then the sample was separated by suction filtration, washed with deionized water until neutral, dried and then calcined at 550 ° C for 2 h under nitrogen atmosphere to obtain Al modified TS-1 Is the carrier C;
  • Example 6 Comparative Example 6. The purpose is to demonstrate that the preparation steps of the Al-modified TS-1 catalyst for achieving different amounts of aluminum removal by controlling the heating and stirring reflux time are compared with Example 1:
  • the sample was taken out and washed with deionized water until neutral. After drying, it is baked in a muffle furnace at 550 ° C for 6 h, and the sample is cooled to room temperature. After being placed in a 0.5 mol/L HCl solution, the mixture was heated and stirred at 60 ° C for 5 h, and then the sample was separated by suction filtration, washed with deionized water until neutral, dried and then calcined at 550 ° C for 2 h under a nitrogen atmosphere to obtain Al.
  • Modified TS-1 which is carrier D;
  • Cat1 was operated according to the usage methods of Examples 11, 12 and 13, respectively, and the evaluation results are shown in Table 2:
  • the pure castor oil bio-aviation kerosene obtained by the reaction has a freezing point of -50 ° C, a flash point of 46 ° C, a viscosity of 3.5 mm 2 S -1 , a boiling point of 200-300 ° C, and a sulfur content, an olefin content, and an aromatic content of 0.
  • the indicators have reached the standard of aviation kerosene, which is similar to the indicators of the jatropha bio-jet fuel.

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Abstract

本发明涉及一种用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂与制备方法和应用。由Al改性的钛硅分子筛(TS-1)为载体，以NixW、NixMo为活性组分，其中x为Ni与W或Ni与Mo的原子比，x＝5-10，其中，活性组分的质量占催化剂总质量的5-30％；所述的Al改性的钛硅分子筛中的Si:Ti的摩尔比为50-100，Si:Al的摩尔比为50-100。负载活性组分时以尿素作为分散剂，使得活性组分的前体可以超高度分散在载体的表面，后续的高温焙烧过程尿素会被分解脱除，同时催化剂的粒径受到分散剂的阻碍，不会造成高温下的烧结，会使得催化剂中金属组分的粒径更小且均匀，从而提高催化效率。利用本发明可以得到高产率的生物航空煤油。

Description

用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂 技术领域
本发明涉及一种用于蓖麻油制备生物航空煤油的催化剂，具体是用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂与制备方法和应用。以Al改性的钛硅分子筛(TS-1)作为载体，NixW、NixMo(x＝5-10)为活性组分，负载活性组分时以尿素作为分散剂。利用本发明可以得到高产率的生物航空煤油。
背景技术
当今工业的快速发展造成了能源的巨大消耗，而石油的过渡开采使得能源问题日益凸显。为了缓解能源问题，开发可再生能源成了必要的手段。近年来，以动植物油脂通过加氢方法制备生物柴油和航空煤油的研究不断出现。蓖麻是一种易生长，产油量高的油品作物，同时蓖麻油是不可食用的，所以蓖麻油可作为很好的制备生物航空煤油的原料，具有广阔的应用前景。
航空煤油的主要成分是碳数为8-16的直链和支链烷烃的混合物，由于受冰点的影响，所以支链烷烃是航空煤油的主要成分。航空煤油的标准(来自ASTM D7566)是冰点小于-47℃，闪点大于38℃，粘度小于8.0mm2S-1，沸点在200-300℃之间，硫含量小于20ppm，烯烃含量小于2％，芳烃含量小于1％。已知的小桐子生物航空煤油的冰点是-49℃，闪点是44℃，粘度4.3mm2S-1，沸点在200-300℃之间，硫含量、烯烃含量、芳烃含量均为0。蓖麻油主要成分是9-烯基-12-羟基十八酸的甘油酯，首先蓖麻油通过加氢脱氧去掉羟基和双键生成碳数为17、18的直链烷烃。然后选择合适的催化剂通过加氢异构和裂化反应，使得碳链异构和裂化成碳数为8-16的直链和支链烷烃。所以在加氢异构和裂化反应中，产物的选择性至关重要，通过选择合适的载体和活性组分，才能够得到高产率的航空煤油组分。
中国专利CN101952392A公开了一种用于可再生原料如植物油和动物脂肪制备航空燃料的方法，原料接触加氢和脱氧催化剂制备直链烷烃，之后再接触异构化催化剂来异构化至少一部分直链烷烃来产生支链烷烃，然后再接触选择性裂化催化剂以得到C8-C16的烷烃。CN102482595A公开了一种航空燃料油基材的制造方法，以动植物油脂为原料，通过具有脱氧和氢化功能的催化剂对原料进行氢化处理，再以此为原料进行氢化异构化处理，获得航空燃料。CN102676203A公开了一种以小桐子油、橡胶籽油、棕榈油、地沟油为原料，经过双键氧化、水解、脱羧反应的工艺，制备生物质航空燃料的方法。CN102994138A公开了一种以地沟油为原料制备生物航空煤油的方法。CN201410080542.4公开了一种蓖麻油制备航空煤油的催化剂及其制备方法，其主要采用了3-氨丙基三乙氧基硅烷和柠檬酸对加氢脱氧载体进行改性，同时引入了Fe作为加氢脱氧催化剂的助剂。CN201510038506.6公开了一种用于蓖麻油制备生物航煤加氢脱氧和加氢异构催化剂的制备方法，其主要采用改性的MCM-41作为加氢脱氧催化剂的载体；对于加氢异构催化剂选用的载体是改性的SAPO-11，选择的活性组分是Pt、Pd或Ni中的一种。
上述文献的报道尽管提供了以生物质为原料制备生物航空煤油的可能，但是仍然存在生产工艺复杂、催化剂的活性低和产物的选择性差、成本较高与催化效率不高，特别是难以得到高产率的生物航空 煤油等问题。
发明内容
为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂。
本发明另一目的在于提供一种上述催化剂的制备方法。该制备方法借助于Al改性的钛硅分子筛(TS-1)作为载体，进一步负载NixW、NixMo(x＝5-10)活性组分，在制备钛硅分子筛(TS-1)的过程中同时引入Ti和Al，合成完成之后再将Al部分脱除，通过控制Al的脱除量，特别是合成填隙型金属化合物NixW、NixMo作为活性中心，负载活性组分时以尿素作为分散剂，从而得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂。
本发明再一目的在于提供上述催化剂在用于以蓖麻油加氢脱氧之后的无水液体产物作为加氢异构和裂化反应的原料油制备生物航空煤油的应用，得到高产率的生物航空煤油。
本发明的目的通过下述方案实现：
本发明提供的一种用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，该催化剂是由Al改性的钛硅分子筛(TS-1)为载体，以NixW、NixMo为活性组分，其中x为Ni与W或Ni与Mo的原子比，x＝5-10，其中，活性组分的质量占催化剂总质量的5-30％，优选10-25％，所述的Al改性的钛硅分子筛中的Si:Ti的摩尔比为50-100，Si:Al的摩尔比为50-100。
本发明提供的上述催化剂的制备方法经过以下步骤：
1)在40-55℃温度下将四丙基氢氧化铵的水溶液与正硅酸乙酯溶液充分搅拌混合0.5-2h，然后再加入钛酸四丁酯的异丙醇溶液，得到混合溶液，然后加入异丙醇铝，继续搅拌1-3h；
2)在75-85℃恒温水浴中将上述混合溶液加热搅拌回流1-3h，除去溶液中的异丙醇，之后用去离子水将回流后得到的溶液的质量补齐到加热搅拌回流前的数值；
3)上述溶液移入高压反应釜中95-105℃放置老化4-6h，然后升温至150-180℃晶化6-36h，晶化，取出样品用去离子水洗涤至中性，干燥之后在马弗炉中500-550℃焙烧4-6h，降温到室温后放入到0.5mol/L的HCl溶液中，50-60℃加热搅拌回流1-5h；
4)将上述得到的样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下500-550℃焙烧2-4h，即得到Al改性的TS-1载体；
5)室温搅拌条件下，按计量依次将硝酸镍、偏钨酸铵或钼酸铵加入到尿素的水溶液中，搅拌0.5-1h至完全溶解，然后加入上述得到Al改性的TS-1，搅拌至少2h，将混合物在旋转蒸发仪中80-90℃烘干；
6)将得到固体粉末于550-600℃空气气氛下焙烧至少2h，然后在200-300mL/min的氢气流速下，550-600℃还原至少3h，降温到室温后用体积比1％O2/N2钝化气钝化3小时，即得到所需的催化剂。
上述的制备方法中Si以SiO2计，Ti以TiO2计，步骤1)-步骤2)的各物料的摩尔比为SiO2:TiO2:TPAOH(四丙基氢氧化铵):异丙醇铝:异丙醇:H2O＝1:0.01-0.02:0.1-0.4:0.01-0.02:0.1-0.5:20-100。
步骤5)中尿素作为分散剂，其加入质量为载体质量的2-5％，优选2-3％。
本发明提供了上述催化剂的应用，具体应用(使用)方法包括以下步骤：
1)催化剂的预处理：将所需量的催化剂成型后装入固定床反应器内，在体积空速为800-1200h-1的氮气吹扫下升温到400-450℃，之后切换为等体积空速的氢气，400-450℃保持至少3小时，然后将反应器温度调节到加氢异构和裂化反应的温度；
2)加氢异构和裂化反应：采用蓖麻油加氢脱氧之后的无水液体产物作为加氢异构和裂化反应的原料油，调节反应体系的压力为2-4MPa，反应温度为270-350℃，氢油比为700-1500，原料油进料的体积空速为1-3h-1，每隔2小时收集反应得到的液体产物。
所述的蓖麻油加氢脱氧之后的无水液体产物包含碳原子数为17、18的烷烃含量为95-97％，碳原子数为8-16的烷烃含量为1-3％，碳原子数为5-7的烷烃含量为1-2％。
所述的蓖麻油加氢脱氧之后的无水液体产物制备方法是以蓖麻油(蓖麻油是在天津光复科技有限公司购买得到，其中90％的组分是蓖麻油酸，10％的组分是棕榈酸和硬脂酸)为原料采用催化剂(以SAPO-11为载体，Ni2P为活性组分，其中活性组分占催化剂总质量的25％)得到加氢脱氧产物(参考文献Liu,S.；Zhu,Q.；Guan,Q.；He,L.；Li,W.Bio-aviation fuel production from hydroprocessing castor oil promoted by the nickel-based bifunctional catalysts.Bioresour.Technol.2015,183,93-100.)，用分液漏斗分液除去其中的水分，即得到蓖麻油加氢脱氧之后的无水液体产物。
本发明的特点是在制备催化剂的过程中，首先合成TS-1中同时引入Ti和Al，合成完成之后再将Al部分脱除，通过控制Al的脱除量，合成填隙型金属化合物NixW、NixMo作为活性中心，负载活性组分时以尿素作为分散剂，使得活性组分的前体可以超高度分散在载体的表面，后续的高温焙烧过程尿素会被分解脱除，同时催化剂的粒径受到分散剂的阻碍，不会造成高温下的烧结，会使得催化剂中金属组分的粒径更小且均匀。特别是NixW、NixMo作为催化剂的活性中心，它们不是普通的双金属催化剂，W或Mo在制备过程中会进入Ni的晶格，使得Ni的晶格扩张，键长变长，键能变弱(见文献Li,R.；Guan,Q.；Wei,R.；Yang,S.；Shu,Z.；Dong,Y.；Chen,J.；Li,W.A Potential Regularity for Enhancing the Hydrogenation Properties ofNi2P.J.Phys.Chem.C 2015,119,2557-2565.)，从而具有更好氢解离的活性，能得到高产率的生物航空煤油组分。
总之，本发明与现有的技术相比，本发明具有如下优点和显著有益效果：
(1)本发明采用Al改性的TS-1，制备过程中部分脱除Al，从而能够形成一定的氧空位，有助于提高催化剂的活性和产物的选择性，同时通过控制Al的脱除量，可以调节Al改性的TS-1的酸性。
(2)在制备加氢异构和裂化催化剂时，使用了尿素作为分散剂，使得活性组分的前体可以超高度分散在载体的表面，后续的高温焙烧过程尿素会被分解脱除，同时催化剂的粒径受到分散剂的阻碍，不会造成高温下的烧结，会使得催化剂中金属组分的粒径更小且均匀，从而提高催化效率。
(3)本发明采用了填隙型金属化合物NixW、NixMo作为催化剂的活性中心，它们不是普通的双金属催化剂，W或Mo在制备过程中会进入Ni的晶格，使得Ni的晶格扩张，键长变长，键能变弱(见文献Li,R.；Guan,Q.；Wei,R.；Yang,S.；Shu,Z.；Dong,Y.；Chen,J.；Li,W.A Potential Regularity for Enhancing the Hydrogenation Properties ofNi2P.J.Phys.Chem.C 2015,119,2557-2565.)，从而具有更好氢 解离的活性，能得到高产率的生物航空煤油组分。
附图说明
图1是实施例1合成的Al改性的TS-1的粉末X射线衍射图。
图2是实施例1制备得到的催化剂cat1的扫描电镜图。
图3是实施例1-2对比例11-14制备得到的催化剂cat1-2、cat11-14按照实施例12的使用方法进行操作得到的实验结果柱形图。
具体实施方式
以下实施例的目的是为了使本领域中普通技术人员更详细的理解本发明，或根据本发明的内容做出一些非本质的改进和调整，但所举实施例并不作为对本发明权利要求所要求保护的技术方案范围作任何限定，包含于但不包括所有的请求保护的范围。同时也特别指出实施例中未注明具体条件的实验方法，通常按照常规条件以及手册中所述的条件，或按照制造厂商所建议的条件；所用的通用设备、材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1.加氢异构和裂化催化剂的制备，包括以下步骤：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.14g钛酸四丁酯滴加到0.3g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.08g异丙醇铝加到溶液A中，继续搅拌3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流3h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体A；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于24g去离子水中，搅拌溶解后得到溶液E，然后加入7.5g硝酸镍并继续搅拌1h，之后加入0.73g偏钨酸铵搅拌至完全溶解，然后将8g载体A加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用体积比1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat1。
实施例2.加氢异构和裂化催化剂的制备，包括以下步骤：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.14g钛酸四丁酯滴加到0.3g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.08g异丙醇铝加到溶液A中，继续搅拌 3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流3h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体A；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于22.5g去离子水中，搅拌溶解后得到溶液E，然后加入10g硝酸镍并继续搅拌1h，之后加入0.93g钼酸铵搅拌至完全溶解，然后将7.5g载体A加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用体积比1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat2。
实施例3.加氢异构和裂化催化剂的制备，包括以下步骤：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.19g钛酸四丁酯滴加到0.4g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.11g异丙醇铝加到溶液A中，继续搅拌3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流3h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体A；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于27.6g去离子水中，搅拌溶解后得到溶液E，然后加入3g硝酸镍并继续搅拌1h，之后加入0.29g偏钨酸铵搅拌至完全溶解，然后将9.2g载体A加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用体积比1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat3。
实施例4.加氢异构和裂化催化剂的制备，包括以下步骤：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.19g钛酸四丁酯滴加到0.4g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.11g异丙醇铝加到溶液A中，继续搅拌 3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流3h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体A；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于21.9g去离子水中，搅拌溶解后得到溶液E，然后加入8.5g硝酸镍并继续搅拌1h，之后加入1.48g偏钨酸铵搅拌至完全溶解，然后将7.3g载体A加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用体积比1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat4。
实施例5.加氢异构和裂化催化剂的制备，包括以下步骤：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.19g钛酸四丁酯滴加到0.4g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.11g异丙醇铝加到溶液A中，继续搅拌3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流3h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体A；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于22.5g去离子水中，搅拌溶解后得到溶液E，然后加入10g硝酸镍并继续搅拌1h，之后加入0.93钼酸铵搅拌至完全溶解，然后将7.5g载体A加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用体积比1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat5。
实施例6.加氢异构和裂化催化剂的制备，包括以下步骤：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.19g钛酸四丁酯滴加到0.4g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.11g异丙醇铝加到溶液A中，继续搅拌 3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流3h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体A；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于27g去离子水中，搅拌溶解后得到溶液E，然后加入4.25g硝酸镍并继续搅拌1h，之后加入0.28钼酸铵搅拌至完全溶解，然后将9g载体A加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用体积比1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat6。
实施例7.加氢异构和裂化催化剂的制备，包括以下步骤：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.1g钛酸四丁酯滴加到0.2g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.06g异丙醇铝加到溶液A中，继续搅拌3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流3h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体A；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于27.6g去离子水中，搅拌溶解后得到溶液E，然后加入3g硝酸镍并继续搅拌1h，之后加入0.29g偏钨酸铵搅拌至完全溶解，然后将9.2g载体A加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用体积比1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat7。
实施例8.加氢异构和裂化催化剂的制备，包括以下步骤：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.1g钛酸四丁酯滴加到0.2g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.06g异丙醇铝加到溶液A中，继续搅拌3h， 得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流3h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体A；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于21.9g去离子水中，搅拌溶解后得到溶液E，然后加入8.5g硝酸镍并继续搅拌1h，之后加入1.48g偏钨酸铵搅拌至完全溶解，然后将7.3g载体A加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用体积比1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat8。
实施例9.加氢异构和裂化催化剂的制备，包括以下步骤：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.1g钛酸四丁酯滴加到0.2g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.06g异丙醇铝加到溶液A中，继续搅拌3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流3h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体A；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于22.5g去离子水中，搅拌溶解后得到溶液E，然后加入10g硝酸镍并继续搅拌1h，之后加入0.93钼酸铵铵搅拌至完全溶解，然后将7.5g载体A加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用体积比1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat9。
实施例10.加氢异构和裂化催化剂的制备，包括以下步骤：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.1g钛酸四丁酯滴加到0.2g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.06g异丙醇铝加到溶液A中，继续搅拌3h， 得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流3h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体A；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于27g去离子水中，搅拌溶解后得到溶液E，然后加入4.25g硝酸镍并继续搅拌1h，之后加入0.28g钼酸铵铵搅拌至完全溶解，然后将9g载体A加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用体积比1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat10。
实施例11.加氢异构和裂化催化剂的使用方法，包括以下步骤：
(1)催化剂的预处理：将6g实施例1中的催化剂cat1成型后装入固定床反应器内，在体积空速为1000h-1的氮气吹扫下升温到400℃，之后切换为等体积空速的氢气，400℃保持3小时，然后将反应器温度调节到280℃；
(2)加氢异构和裂化反应：采用蓖麻油加氢脱氧之后的无水液体产物作为加氢异构和裂化反应的原料油，调节反应体系的压力为4MPa，反应温度为280℃，氢油比为1400，原料油进料的体积空速为1h-1，每隔2小时收集反应得到的液体产物。通过气质联用(安捷伦气相色谱与质谱)分析检测产物中碳数为8-16的直链和支链烷烃的含量，结果如表2。
蓖麻油加氢脱氧之后的无水液体产物制备方法是按照文献(Liu,S.；Zhu,Q.；Guan,Q.；He,L.；Li,W.Bio-aviation fuel production from hydroprocessing castor oil promoted by the nickel-based bifunctional catalysts.Bioresour.Technol.2015,183,93-100.)所示的方法制备，具体是以蓖麻油(蓖麻油是在天津光复科技有限公司购买得到，其中90％的组分是蓖麻油酸，10％的组分是棕榈酸和硬脂酸)为原料采用催化剂(以SAPO-11为载体，Ni2P为活性组分，其中活性组分占催化剂总质量的25％)得到加氢脱氧产物，再用分液漏斗分液除去其中的水分，即得到蓖麻油加氢脱氧之后的无水液体产物。得到的无水液体产物通过气质联用(安捷伦气相色谱与质谱)分析检测，其中主要包括：碳原子数为17、18的烷烃含量为95-97％，碳原子数为8-16的烷烃含量为1-3％，碳原子数为5-7的烷烃含量为1-2％。
实施例12.加氢异构和裂化催化剂的使用方法，包括以下步骤：
(1)催化剂的预处理：将6g实施例1中的催化剂cat1成型后装入固定床反应器内，在体积空速为1000h-1的氮气吹扫下升温到400℃，之后切换为等体积空速的氢气，400℃保持3小时，然后将反应器温度调节到320℃；
(2)加氢异构和裂化反应：采用蓖麻油加氢脱氧之后的无水液体产物作为加氢异构和裂化反应的原料油，调节反应体系的压力为3MPa，反应温度为320℃，氢油比为1000，原料油进料的体积空速为 2h-1，每隔2小时收集反应得到的液体产物。通过气质联用(安捷伦气相色谱与质谱)分析检测产物中碳数为8-16的直链和支链烷烃的含量，结果如表2。
实施例13.加氢异构和裂化催化剂的使用方法，包括以下步骤：
(1)催化剂的预处理：将6g实施例1中的催化剂cat1成型后装入固定床反应器内，在体积空速为1000h-1的氮气吹扫下升温到400℃，之后切换为等体积空速的氢气，400℃保持3小时，然后将反应器温度调节到340℃；
(2)加氢异构和裂化反应：采用蓖麻油加氢脱氧之后的无水液体产物作为加氢异构和裂化反应的原料油，调节反应体系的压力为2MPa，反应温度为340℃，氢油比为800，原料油进料的体积空速为3h-1，每隔2小时收集反应得到的液体产物。通过气质联用(安捷伦气相色谱与质谱)分析检测产物中碳数为8-16的直链和支链烷烃的含量，结果如表2。
对比例1.目的在于说明未经过Al改性的TS-1催化剂的制备步骤与实施例1做对比：
(1)TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.14g钛酸四丁酯滴加到0.3g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后继续搅拌3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，即得到TS-1，即为载体B；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于24g去离子水中，搅拌溶解后得到溶液E，然后加入7.5g硝酸镍并继续搅拌1h，之后加入0.73g偏钨酸铵搅拌至完全溶解，然后将8g载体B加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat11。
对比例2.目的在于说明未经过Al改性的TS-1催化剂的制备步骤与实施例2做对比：
(1)TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.14g钛酸四丁酯滴加到0.3g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后继续搅拌3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，即得到TS-1，即为载体B；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于22.5g去离子水中，搅拌溶解后得到溶液E，然后加入10g硝酸镍并继续搅拌1h，之后加入0.93g钼酸铵搅拌至完全溶解，然后将7.5g载体B加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat12。
对比例3.目的在于说明制备过程中未采用尿素作为分散剂的催化剂的制备步骤与实施例1做对比：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.14g钛酸四丁酯滴加到0.3g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.08g异丙醇铝加到溶液A中，继续搅拌3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流3h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体A；
(2)活性组分的上载：在室温搅拌条件下，将7.5g硝酸镍溶解于24g去离子水中，并继续搅拌1h，之后加入0.73g偏钨酸铵搅拌至完全溶解，然后将8g载体A加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat13。
对比例4.目的在于说明制备过程中未采用尿素作为分散剂的催化剂的制备步骤与实施例2做对比：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.14g钛酸四丁酯滴加到0.3g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.08g异丙醇铝加到溶液A中，继续搅拌3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流3h，之后将样品抽滤分离，用去离子水洗涤至中 性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体A；
(2)活性组分的上载：在室温搅拌条件下，将10g硝酸镍溶解于22.5g去离子水中，并继续搅拌1h，之后加入0.93g钼酸铵搅拌至完全溶解，然后将7.5g载体A加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat14。
对比例5.目的在于说明通过控制加热搅拌回流时间实现不同铝脱除量的Al改性的TS-1催化剂的制备步骤与实施例1做对比：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.14g钛酸四丁酯滴加到0.3g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.08g异丙醇铝加到溶液A中，继续搅拌3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流1h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体C；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于24g去离子水中，搅拌溶解后得到溶液E，然后加入7.5g硝酸镍并继续搅拌1h，之后加入0.73g偏钨酸铵搅拌至完全溶解，然后将8g载体C加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用体积比1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat15。
对比例6.目的在于说明通过控制加热搅拌回流时间实现不同铝脱除量的Al改性的TS-1催化剂的制备步骤与实施例1做对比：
(1)Al改性的TS-1的制备方法：在50℃搅拌条件下，将5.69g 25％的TPAOH(四丙基氢氧化铵)水溶液滴加到20g去离子水中，搅拌30分钟后再缓慢加入5.83g正硅酸乙酯并继续搅拌2h得到溶液A；在50℃搅拌条件下，将0.14g钛酸四丁酯滴加到0.3g异丙醇中，之后继续搅拌0.5h得到溶液B；然后将溶液B缓慢滴加到高速搅拌的溶液A中，滴加完成后再将0.08g异丙醇铝加到溶液A中，继续搅拌3h，得到溶液C；记下溶液C的质量，然后将溶液C在80℃恒温水浴中加热搅拌回流3h，除去溶液中的异丙醇，之后用去离子水将溶液的质量补齐到加热搅拌回流前的数值，得到溶液D；然后将溶液D放入带聚四氟内衬的高压反应釜中，密封后在100℃的温度下老化6h，然后升温至160℃晶化18h，晶化完成后将样品取出，用去离子水洗涤至中性，干燥之后在马弗炉中550℃焙烧6h，待样品降温到室温 后放入到0.5mol/L的HCl溶液中，60℃加热搅拌回流5h，之后将样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下550℃焙烧2h，即得到Al改性的TS-1，即为载体D；
(2)活性组分的上载：在室温搅拌条件下，将0.2g尿素溶解于24g去离子水中，搅拌溶解后得到溶液E，然后加入7.5g硝酸镍并继续搅拌1h，之后加入0.73g偏钨酸铵搅拌至完全溶解，然后将8g载体D加入到溶液中并继续搅拌3h，然后将混合物在旋转蒸发仪中90℃烘干，之后将得到的固体粉末在600℃空气气氛下焙烧3h，然后在250mL/min的氢气流速下，600℃还原3h，待反应结束降温到室温后用体积比1％O2/N2钝化气钝化3小时后取出，即得到用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，记作cat16。
按照实施例12的使用方法进行操作，催化剂cat1-2、cat11-14的评价结果如表1：
表1
Figure PCTCN2015089535-appb-000001
cat1分别按照实施例11、12、13的使用方法进行操作，评价结果如表2：
表2
Figure PCTCN2015089535-appb-000002
按照实施例12的使用方法进行操作，催化剂cat1、cat15-16的评价结果如表3：
表3
Figure PCTCN2015089535-appb-000003
反应得到的纯蓖麻油生物航空煤油的冰点是-50℃，闪点是46℃，粘度3.5mm2S-1，沸点200-300℃，硫含量、烯烃含量、芳烃含量均为0，各项指标均达到航空煤油的标准，与小桐子生物航煤的各项指标相近。

Claims (9)

  1. 一种用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，其特征在于该催化剂由Al改性的钛硅分子筛(TS-1)为载体，以NixW、NixMo为活性组分，其中x为Ni与W或Ni与Mo的原子比，x＝5-10，其中，活性组分的质量占催化剂总质量的5-30％。
  2. 按照权利要求1所述的催化剂，其特征在于所述的Al改性的钛硅分子筛中的Si:Ti的摩尔比为50-100；Si:Al的摩尔比为50-100。
  3. 一种用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂，其特征在于该催化剂由Al改性的钛硅分子筛(TS-1)为载体，以NixW、NixMo为活性组分，其中x为Ni与W或Ni与Mo的原子比，x＝5-10，其中，活性组分的质量占催化剂总质量的5-30％；所述的Al改性的钛硅分子筛中的Si:Ti的摩尔比为50-100；Si:Al的摩尔比为50-100；
    具体制备方法经过以下步骤：
    1)在40-55℃温度下将四丙基氢氧化铵的水溶液与正硅酸乙酯溶液充分搅拌混合0.5-2h，然后再加入钛酸四丁酯的异丙醇溶液，得到混合溶液，然后加入异丙醇铝，继续搅拌1-3h；
    2)在75-85℃恒温水浴中将上述混合溶液加热搅拌回流1-3h，除去溶液中的异丙醇，之后用去离子水将回流后得到的溶液的质量补齐到加热搅拌回流前的数值；
    3)上述溶液移入高压反应釜中95-105℃放置老化4-6h，然后升温至150-180℃晶化6-36h，晶化，取出样品用去离子水洗涤至中性，干燥之后在马弗炉中500-550℃焙烧4-6h，降温到室温后放入到0.5mol/L的HCl溶液中，50-60℃加热搅拌回流1-5h；
    4)将上述得到的样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下500-550℃焙烧2-4h，即得到Al改性的TS-1载体；
    5)室温搅拌条件下，按计量依次将硝酸镍、偏钨酸铵或钼酸铵加入到尿素的水溶液中，搅拌0.5-1h至完全溶解，然后加入上述得到Al改性的钛硅分子筛，搅拌至少2h，将混合物在旋转蒸发仪中80-90℃烘干；所述的尿素加入量为载体质量的2-5％；
    6)将得到固体粉末于550-600℃空气气氛下焙烧至少2h，然后在200-300mL/min的氢气流速下，550-600℃还原至少3h，降温到室温后用体积比1％O2/N2钝化气钝化3小时，即得到所需的催化剂；步骤1)-步骤2)的各物料的摩尔比为SiO2:TiO2:TPAOH:异丙醇铝:异丙醇:H2O＝1:0.01-0.02:0.1-0.4:0.01-0.02:0.1-0.5:20-100。
  4. 权利要求1所述的用于蓖麻油制备生物航空煤油的加氢异构和裂化催化剂制备方法，其特征在于经过以下步骤：
    1)在40-55℃温度下将四丙基氢氧化铵的水溶液与正硅酸乙酯溶液充分搅拌混合0.5-2h，然后再加入钛 酸四丁酯的异丙醇溶液，得到混合溶液，然后加入异丙醇铝，继续搅拌1-3h；
    2)在75-85℃恒温水浴中将上述混合溶液加热搅拌回流1-3h，除去溶液中的异丙醇，之后用去离子水将回流后得到的溶液的质量补齐到加热搅拌回流前的数值；
    3)上述溶液移入高压反应釜中95-105℃放置老化4-6h，然后升温至150-180℃晶化6-36h，晶化，取出样品用去离子水洗涤至中性，干燥之后在马弗炉中500-550℃焙烧4-6h，降温到室温后放入到0.5mol/L的HCl溶液中，50-60℃加热搅拌回流1-5h；
    4)将上述得到的样品抽滤分离，用去离子水洗涤至中性，干燥之后在氮气气氛下500-550℃焙烧2-4h，即得到Al改性的TS-1载体；
    5)室温搅拌条件下，按计量依次将硝酸镍、偏钨酸铵或钼酸铵加入到尿素的水溶液中，搅拌0.5-1h至完全溶解，然后加入上述得到Al改性的TS-1，搅拌至少2h，将混合物在旋转蒸发仪中80-90℃烘干；
    6)将得到固体粉末于550-600℃空气气氛下焙烧至少2h，然后在200-300mL/min的氢气流速下，550-600℃还原至少3h，降温到室温后用体积比1％O2/N2钝化气钝化3小时，即得到所需的催化剂。
  5. 按照权利要求4所述的方法，其特征在于步骤1)-步骤2)的各物料的摩尔比为SiO2:TiO2:TPAOH:异丙醇铝:异丙醇:H2O＝1:0.01-0.02:0.1-0.4:0.01-0.02:0.1-0.5:20-100。
  6. 按照权利要求4所述的方法，其特征在于步骤5)所述的尿素的加入质量为Al改性的TS-1载体质量的2-5％。
  7. 按照权利要求4所述的方法，其特征在于步骤5)所述的尿素的加入质量为Al改性的TS-1载体质量的2-3％。
  8. 权利要求1-3任一所述的催化剂的使用方法，其特征在于包括以下步骤：
    1)催化剂的预处理：将所需量的催化剂成型后装入固定床反应器内，在体积空速为800-1200h-1的氮气吹扫下升温到400-450℃，之后切换为等体积空速的氢气，400-450℃保持至少3小时，然后将反应器温度调节到加氢异构和裂化反应的温度；
    2)加氢异构和裂化反应：采用蓖麻油加氢脱氧之后的无水液体产物作为加氢异构和裂化反应的原料油，调节反应体系的压力为2-4MPa，反应温度为270-350℃，氢油比为700-1500，原料油进料的体积空速为1-3h-1，每隔2小时收集反应得到的液体产物。
  9. 按照权利要求8所述的方法，其特征在于所述的蓖麻油加氢脱氧之后的无水液体产物主要包括:碳原子数为17、18的烷烃含量为95-97％，碳原子数为8-16的烷烃含量为1-3％，碳原子数为5-7的烷烃含量为1-2％。
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