WO2021027019A1 - 多孔结构的硅铝磷载体加氢催化剂的制备方法及在制备生物燃料中的应用 - Google Patents

多孔结构的硅铝磷载体加氢催化剂的制备方法及在制备生物燃料中的应用 Download PDF

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WO2021027019A1
WO2021027019A1 PCT/CN2019/106883 CN2019106883W WO2021027019A1 WO 2021027019 A1 WO2021027019 A1 WO 2021027019A1 CN 2019106883 W CN2019106883 W CN 2019106883W WO 2021027019 A1 WO2021027019 A1 WO 2021027019A1
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aluminum
carrier
phosphorus
silicon
source
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French (fr)
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李伟
刘思阳
关庆鑫
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南开大学
天津蓖能科技有限公司
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/182—Phosphorus; Compounds thereof with silicon
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention belongs to the field of catalysts, and particularly relates to a preparation method of a porous structured silicon-aluminum-phosphorus carrier hydrogenation catalyst and its application in the preparation of biofuels.
  • Catalytic hydrogenation of animal and vegetable oils to prepare biofuels is commonly used as a two-step production process, namely, hydrodeoxygenation and hydroisomerization.
  • the feedstock oil is converted into normal long-chain alkanes through hydrodeoxygenation, and then through catalyst hydroisomerization to obtain products with branched chains and suitable carbon chain selectivity.
  • the catalyst can be used in the first and second steps of the reaction at the same time, and the acidic characteristics and pore structure of the carrier are used to hydrodeoxygenate oil and long-chain alkanes and moderate hydroisomerization to obtain alkanes products meeting different fuel standards.
  • Catalysts usually use molecular sieves as carriers, but molecular sieves need to use organic amine template in the synthesis, and then need to wash and roast to remove unreacted and product organic amine template. This process will cause N-containing wastewater and nitrogen oxide gas to be discharged into the environment, causing serious pollution.
  • the template-free method developed by the present invention to synthesize porous structured silicon-aluminum-phosphorus carrier can fundamentally solve this problem.
  • CN105347360B discloses a method for synthesizing super large particles of ZSM-5 zeolite molecular sieve without template. It adopts a rotating oven, a high-pressure synthesis kettle with angled rotation, and a method of adding pre-crystallization liquid to synthesize ZSM- with particles above 20 ⁇ m. 5 Zeolite molecular sieve. CN102502696B discloses a method for synthesizing ZSM-5 zeolite molecular sieve.
  • CN102285666B provides a method for preparing chabazite and a chabazite membrane under the condition of no template agent.
  • chabazite is formed by the induction of heterogeneous crystal nucleus T-type zeolite.
  • the formed chabazite is seeded on the outer surface of the porous support to induce the formation of a chabazite molecular sieve membrane.
  • the synthesized membrane shows good stability in the investigated acidic medium and can be widely used in the pervaporation separation process of acidic systems And pervaporation membrane reactor.
  • CN103638965B discloses a multi-stage porous ZSM-5 zeolite catalyst for preparing acrolein by glycerin dehydration and its preparation method and application.
  • the prepared catalyst has the characteristics of controllable acid sites, large specific surface area, short mass transfer path, etc., and can be used for glycerol dehydration to propylene In the aldehyde catalyzed reaction, it shows excellent catalytic activity, selectivity and stability.
  • the German BASF company J Mater Chem A, 2013, 1(10): 3254-3257) has produced Beta zeolite and intercalated chabazite using a template-free seed induction method. After that, they synthesized Fe-Beta zeolite by the template-free seeding method and used it to directly decompose N 2 O, showing good catalytic performance.
  • Lin et al. (Micro-porous Mesoporous Mater, 2000, 34(3):241-253) used a template-free secondary growth method to prepare silica-aluminum MFI molecular sieve membranes without the use of organic templates, reducing costs and avoiding molecular sieves
  • the membrane is calcined at high temperature to remove the defects produced in the process of template agent.
  • the template agent is reduced by seed induction method, pre-crystallization method, changing crystallization conditions and other methods to reduce environmental pollution.
  • Most of them are used in silica-alumina molecular sieve, and for hydrodeoxidation
  • suitable acid strength, acidic sites and pore structure are required. Therefore, the silico-aluminum-phosphorus porous structure material has a more suitable acidic center and pore structure, so that catalytic hydrogenation can achieve high yield and high selection.
  • Biofuels At present, there are many research methods for the synthesis of silicon-aluminum-phosphorus porous materials, but there are few reports on template-free methods.
  • the present invention proposes a method for preparing a porous structured silico-aluminum-phosphorus carrier hydrogenation catalyst and its application in the preparation of biofuels.
  • the silico-aluminum-phosphorus crystal carrier is synthesized by a template-free method and applied to grease Hydrogenation and isomerization of long-chain alkanes to produce biofuels.
  • the purpose is to hope that the catalyst can be used in industrial production, reduce pollution, produce no high-content organic wastewater in production, and efficiently produce renewable biofuels.
  • the technical scheme adopted by the present invention is: a porous structure of silicon-aluminum-phosphorus carrier, adding an alkali source to the mixed solution of silicon source, aluminum source, phosphorus source and water for crystallization reaction, water, silicon source, aluminum source, and phosphorus source
  • the alkali source is mixed with the oxide molar ratio of 50-100:1:1:0.1-1:0.5-2, and then treated with an ion exchanger to obtain a porous structured silicon-aluminum-phosphorus carrier.
  • the silicon source is one of sodium silicate, silica sol, ethyl orthosilicate, and white carbon black.
  • the alkali source is one of potassium hydroxide, sodium hydroxide, and calcium hydroxide.
  • the phosphorus source is phosphoric acid.
  • the ion exchanger is one of ammonium nitrate, ammonium chloride, ammonium sulfate, hydrochloric acid, and ammonium phosphate.
  • a porous structured silicon-aluminum-phosphorus carrier hydrogenation catalyst prepared by a porous structured silicon-aluminum-phosphorus carrier, and a porous structured silicon-aluminum-phosphorus carrier hydrogenation catalyst obtained by supporting active components on a porous structured silicon-aluminum-phosphorus carrier;
  • the active component is one of Ni x -Mo, Ni x -Co or Ni x -W, and the mass of the active component accounts for 10-30% of the total mass of the catalyst, wherein the range of x is 5-20.
  • Step 1 Mix and stir the deionized water, silicon source, aluminum source, phosphorus source and alkali source at a molar ratio of oxides of 50-100:1:1:0.1-1:0.5-2 to obtain the initial carrier after crystallization product;
  • Step 2 Use an ion exchanger to perform ion exchange on the initial product of the carrier to obtain a porous structured silicon-aluminum-phosphorus carrier;
  • Step 3 Add the soluble salt solution of the required active components to the porous silicon-aluminum-phosphorus carrier according to the ratio of 10-30% of the total mass of the active components to the total mass of the catalyst. After aging, drying and roasting, the porous structure is obtained. Silica-aluminum-phosphorus carrier hydrogenation catalyst;
  • step 2 the carrier initial product is added to the ion exchanger, and the mixture is fully stirred at 25-80°C for 3-12 hours, washed and dried, and recorded as one ion exchange, and ion exchange is 2-3 times;
  • the mass ratio of ion exchanger to carrier initial product in step 2 is 5-20:1;
  • the crystallization conditions in step one are crystallization at 160-200°C for 18-96 h.
  • the silicon source is one of sodium silicate, silica sol, ethyl orthosilicate, and white carbon black;
  • the alkali source is one of potassium hydroxide, sodium hydroxide, and calcium hydroxide;
  • the phosphorus source is phosphoric acid
  • the ion exchanger is one of ammonium nitrate, ammonium chloride, ammonium sulfate, hydrochloric acid, and ammonium phosphate.
  • the active component is one of Ni x -Mo, Ni x -Co or Ni x -W, and the mass of the active component accounts for 10-30% of the total mass of the catalyst, wherein the range of x is 5-20;
  • the soluble salt of the active component is dissolved in deionized water with twice the water absorption rate of the carrier mass to obtain the soluble salt solution of the active component;
  • the soluble salt of the active component is one of nickel nitrate, cobalt nitrate, ammonium metatungstate or ammonium molybdate.
  • porous structured silicon-aluminum-phosphorus carrier hydrogenation catalyst in palm oil, methyl esterified palm oil or waste fatty acid to prepare biofuels through hydrodeoxygenation, hydroisomerization.
  • the porous structure of silico-aluminum-phosphorus was obtained by introducing an alkali source and changing the feed ratio, and then subjected to ion exchange treatment to obtain a carrier with suitable acidic properties.
  • This method avoids the use of organic amine templates. , Reduce production costs, and avoid environmental pollution caused by organic amine pollutants or nitrogen oxides in the process of removing the template agent, and realize green and sustainable production;
  • the catalyst prepared by this scheme can be applied to the hydrodeoxygenation of fats and oils and the hydroisomerization and cracking reactions of long-chain alkanes, and the product fuel oil produced meets multiple combustion standards.
  • a biofuel product including gasoline, kerosene, and diesel can be obtained.
  • Figure 1 is a powder X-ray diffraction pattern of silicon aluminum phosphorus crystals synthesized with different crystallization time and aluminum hydroxide molar ratio at 0.5;
  • Figure 2 is a powder X-ray diffraction pattern of silicon aluminum phosphate crystals synthesized with different crystallization time and aluminum hydroxide molar ratio at 1.5;
  • Figure 3 is a scanning electron micrograph of the synthesized silicon aluminum phosphorus crystal, in which (a) the silicon source is silica sol (b) the silicon source is sodium silicate (c) the silicon source is tetraethyl orthosilicate.
  • the present invention provides a method for preparing a porous structured silicon-aluminum-phosphorus carrier hydrogenation catalyst and its application in the preparation of biofuels, especially the application in the hydrogenation of palm oil and other fats and oils to prepare biofuels.
  • the porous structure of silicon-aluminum-phosphorus crystals prepared by the template-free method can be obtained.
  • the crystals do not need to be roasted, and sodium ions, potassium ions or calcium ions in the crystals are removed by ion exchange, which can be used as a catalyst for the hydrodeoxygenation, hydroisomerization and hydrocracking of palm oil and other fats to prepare biofuels.
  • the method has simple synthesis process, green pollution-free, energy saving and environmental protection, and the prepared catalyst has high hydrogenation activity and high yield of catalyst and biofuel.
  • an alkali source is added to the mixture of silicon source, aluminum source, phosphorus source and water for reaction.
  • the water, silicon source, aluminum source, phosphorus source and alkali source are based on the mole of oxide.
  • the silicon source can be one of sodium silicate, silica sol, ethyl orthosilicate, and white carbon black;
  • the alkali source can be one of potassium hydroxide, sodium hydroxide, and calcium hydroxide;
  • the phosphorus source is Phosphoric acid.
  • the ion exchanger used in the ion exchange can be one of ammonium nitrate, ammonium chloride, ammonium sulfate, hydrochloric acid, and ammonium phosphate.
  • FIG. 1 shows the crystallinity and stability of silico-aluminum-phosphorus crystals.
  • Figure 3 shows the SEM picture of the synthesized silicon-aluminum-phosphorus crystals, where (a) is a porous silicon-aluminum-phosphorus carrier prepared from silica sol as a silicon source, and (b) is a porous silicon-aluminum-phosphorus carrier made of sodium silicate.
  • the structure of the silicon-aluminum-phosphorus carrier, (c) is a porous silicon-aluminum-phosphorus carrier whose silicon source is tetraethylorthosilicate; from the results of scanning electron microscopy, the template-free silicon-aluminum-phosphorus carrier has a spherical morphology.
  • the shape of the sphere prepared by the source is also slightly different, which is better than that of different silicon sources to form different gel micelles, so the crystal morphology is slightly different, but it has a similar hydrogenation effect when used as a catalyst carrier.
  • a porous silicon-aluminum-phosphorus carrier is used to prepare a porous structure of silicon-aluminum-phosphorus carrier hydrogenation catalyst, that is, a porous structure of silicon-aluminum-phosphorus carrier hydrogenation catalyst obtained by supporting active components on a porous structure of silicon-aluminum-phosphorus carrier;
  • the component is one of Ni x -Mo, Ni x -Co or Ni x -W, the mass of the active component accounts for 10-30% of the total mass of the catalyst, and the range of x is 5-20.
  • the main active metal component is Ni, and the synergistic components are Mo and W.
  • the preparation method of the porous structured silicon-aluminum-phosphorus carrier hydrogenation catalyst is as follows:
  • Step 1 Mix and stir the deionized water, silicon source, aluminum source, phosphorus source and alkali source at the oxide molar ratio of 50-100:1:1:0.1-1:0.5-2, and obtain the initial carrier after crystallization. product;
  • Step 2 Use an ion exchanger to perform ion exchange on the initial product of the carrier to obtain a porous structured silicon-aluminum-phosphorus carrier.
  • Step 3 Add the soluble salt solution of the required active component to the porous silicon-aluminum-phosphorus carrier according to the ratio of 10-30% of the total mass of the active component to the total mass of the catalyst. After aging, drying and roasting, the porous structure is obtained. Silica-aluminum-phosphorus carrier hydrogenation catalyst.
  • Step 1 Mix deionized water, silicon source, aluminum source, phosphorus source and alkali source at a molar ratio of oxides of 50-100:1:1:0.1-1:0.5-2, and stir at 20-50°C. 3- 5h; then transfer the mixture to a polytetrafluoroethylene-lined high-pressure crystallization kettle, and after sealing, crystallize at 160-200°C for 18-96h. After the reaction is completed, the solid product is centrifuged, washed and dried to obtain the initial carrier product.
  • the silicon source can be one of sodium silicate, silica sol, ethyl orthosilicate, and white carbon black;
  • the alkali source can be one of potassium hydroxide, sodium hydroxide, and calcium hydroxide;
  • the phosphorus source is Phosphoric acid.
  • Step 2 Use an ion exchanger to perform ion exchange on the initial product of the carrier, and add the initial product of the carrier to 0.2-2mol/L of the ion exchanger.
  • the mass ratio of the ion exchanger to the initial product of the carrier is 5-20:1.
  • the ion exchanger is one of ammonium nitrate, ammonium chloride, ammonium sulfate, hydrochloric acid, and ammonium phosphate.
  • Step 3 Dissolve the soluble salt of the required active component in the deionized water with double the water absorption rate of the carrier mass according to the ratio of 10-30% of the total mass of the active component in the total mass of the catalyst. After fully stirring for 2h, add it to the porous structure In the silicon-aluminum-phosphorus carrier, the mixture is dried after being allowed to stand for 24 hours and calcined in an air atmosphere at 500° C. for 3 hours to obtain a porous structure of the silicon-aluminum-phosphorus carrier hydrogenation catalyst.
  • the active component is one of Ni x -Mo, Ni x -Co or Ni x -W, the mass of the active component accounts for 10-30% of the total mass of the catalyst, and the range of x is 5-20; for example, Nickel nitrate, cobalt nitrate, ammonium metatungstate or ammonium molybdate.
  • the prepared porous structured silico-aluminum-phosphorus carrier hydrogenation catalyst can be used for the preparation of biofuels from fats, wherein the fats are one of palm oil, methyl esterified palm oil, and waste fatty acids.
  • the steps of hydrodeoxygenation and hydroisomerization are as follows:
  • Hydrodeoxygenation Load the weighed catalyst into the constant temperature zone of the reactor, and fill the upper end of the reaction tube with a porcelain ring to preheat the lower temperature raw materials. Before the reaction, the catalyst is pretreated in a H 2 atmosphere (160 mL min -1 ) at a certain temperature (generally 350°C) for 2 hours, so that the supported oxide is reduced to a zero valence state, and then the temperature required for the reaction is set. The pressure and hydrogen flow rate are evaluated (under 3-10MPa hydrogen pressure, the hydrogen-to-oil ratio is 800-2000, and the reaction temperature is 300-400°C). Receiving every hour, the product is analyzed by gas chromatography.
  • the evaluation of the catalyst was carried out in a continuous flow fixed-bed reactor, with the HDO product in the first step as the raw material, to investigate the isomerization and cracking effect of the catalyst.
  • the catalyst powder must be compressed (tabletting pressure is 20MPa) before being loaded into the reactor, crushed, and screened into 20-40 mesh particles as the catalyst for evaluation. Load the weighed catalyst into the constant temperature zone of the reactor, and fill the upper end of the reaction tube with a porcelain ring to fully preheat the low-temperature raw materials.
  • the catalyst Before the reaction, the catalyst is pretreated in a H 2 atmosphere (160mL min -1 ) at a certain temperature (generally 350°C) for 2h, so that the supported oxide is reduced to a zero valence state, and then the temperature and pressure required for the reaction are set And hydrogen flow rate (under 3-10MPa hydrogen pressure, hydrogen-oil ratio 800-2000, reaction temperature 300-400°C). Receiving every hour, the product is analyzed by gas chromatography.
  • Example 1 The preparation of a hydrodeoxygenation catalyst includes the following steps:
  • Example 2 The preparation of the hydrodeoxygenation catalyst includes the following steps:
  • Example 3 The preparation of a hydrodeoxygenation catalyst includes the following steps:
  • Example 4 The preparation of a hydrodeoxygenation catalyst includes the following steps:
  • Example 5 The preparation of a hydrodeoxygenation catalyst includes the following steps:
  • the mass ratio of the liquid to the solid was 15:1.
  • the mixture was fully stirred at 25°C for 12h, and the stirring was stopped and centrifuged to wash Drying is recorded as one ion exchange, and a total of 2 exchanges.
  • the final product is marked as carrier D;
  • Example 6 The preparation of a hydrodeoxygenation catalyst includes the following steps:
  • Example 7 The preparation of the hydroisomerization catalyst includes the following steps:
  • Preparation method of silico-aluminum-phosphorus carrier without template method mix 15g of deionized water, 2.21g of phosphoric acid, 1.38g of pseudo-boehmite, 0.77g of tetraethyl orthosilicate and 7.5g of sodium hydroxide. Stir at °C for 3h. Then the mixture was transferred to a high-pressure crystallization kettle lined with polytetrafluoroethylene, sealed and crystallized at 190°C for 72 hours. After the reaction, the solid product was centrifuged and washed and dried to obtain the initial product after being allowed to stand and cool down. Then use an ion exchanger to perform ion exchange on the product.
  • Example 8 The preparation of the hydroisomerization catalyst includes the following steps:
  • Preparation method of silico-aluminum-phosphorus carrier without template method mix 15g deionized water, 2.21g phosphoric acid, 1.38g pseudo-boehmite, 0.77g tetraethyl orthosilicate and 7.5g potassium hydroxide, and mix it in 20 Stir at °C for 3h. Then the mixture was transferred to a high-pressure crystallization kettle lined with polytetrafluoroethylene, sealed and crystallized at 190°C for 72 hours. After the reaction, the solid product was centrifuged and washed and dried to obtain the initial product after being allowed to stand and cool down. Then use an ion exchanger to perform ion exchange on the product.
  • Example 9 The preparation of the hydroisomerization catalyst includes the following steps:
  • Example 10 The preparation of the hydroisomerization catalyst includes the following steps:
  • Preparation method of silico-aluminum-phosphorus carrier without template method mix 15g deionized water, 2.21g phosphoric acid, 1.38g pseudo-boehmite, 0.77g white carbon black and 7.5g sodium hydroxide at 20°C Stir for 3h. Then the mixture was transferred to a high-pressure crystallization kettle lined with polytetrafluoroethylene, sealed and crystallized at 190°C for 72 hours. After the reaction, the solid product was centrifuged and washed and dried to obtain the initial product after being allowed to stand and cool down.
  • Example 11 The preparation of the hydroisomerization catalyst includes the following steps:
  • Preparation method of silico-aluminum-phosphorus carrier without template method mix 15g deionized water, 2.21g phosphoric acid, 1.38g pseudo-boehmite, 0.38g white carbon black and 6g potassium hydroxide, and stir at 20°C 3h. Then the mixture was transferred to a high-pressure crystallization kettle lined with polytetrafluoroethylene, sealed and crystallized at 190°C for 72 hours. After the reaction, the solid product was centrifuged and washed and dried to obtain the initial product after being allowed to stand and cool down.
  • Example 12 The preparation of the hydroisomerization catalyst includes the following steps:
  • Preparation method of silico-aluminum-phosphorus carrier without template method mix 15g deionized water, 2.21g phosphoric acid, 1.38g pseudo-boehmite, 0.38g white carbon black and 6g calcium hydroxide, and stir at 20°C 3h. Then the mixture was transferred to a high-pressure crystallization kettle lined with polytetrafluoroethylene, sealed and crystallized at 190°C for 72 hours. After the reaction, the solid product was centrifuged and washed and dried to obtain the initial product.
  • Comparative Example 1 The purpose is to illustrate the preparation steps of the template-free silico-aluminum-phosphorus carrier without adding an alkali source:
  • the preparation method of the template-free silico-aluminum-phosphorus carrier 15g of deionized water, 2.21g of phosphoric acid, 1.38g of pseudo-boehmite and 0.77g of silica sol were mixed, and stirred at 20°C for 3h. Then the mixture was transferred to a high-pressure crystallization kettle lined with polytetrafluoroethylene, sealed and crystallized at 190°C for 72 hours. After the reaction, the solid product was centrifuged and washed and dried to obtain the initial product after being allowed to stand and cool down. After that, the product was ion exchanged with an ion exchanger, and the solid was added to the 2mol/L ammonium sulfate solution.
  • the mass ratio of the liquid to the solid was 20:1.
  • the mixture was fully stirred at 25°C for 12 hours, and the stirring was stopped and centrifuged to wash and dry. , Marked as one ion exchange, 3 exchanges in total.
  • the final product is recorded as carrier J;
  • Comparative Example 2 The purpose is to illustrate the preparation steps of template-free silico-alumina-phosphorus carrier with alkali content less than 0.5 mol:
  • Comparative Example 3 The purpose is to illustrate the preparation steps of the silico-aluminum-phosphorus carrier by the method of excess alkali without template:
  • Preparation method of silico-aluminum-phosphorus carrier without template method mix 15g deionized water, 2.21g phosphoric acid, 1.38g pseudo-boehmite, 1.77g sodium silicate and 8.5g sodium hydroxide at 20°C Stir for 3h. Then the mixture was transferred to a high-pressure crystallization kettle lined with polytetrafluoroethylene, sealed and crystallized at 190°C for 72 hours. After the reaction, the solid product was centrifuged and washed and dried to obtain the initial product after being allowed to stand and cool down.
  • Comparative Example 4 The purpose is to illustrate the preparation steps of the template-free silicon-aluminum-phosphorus carrier with a crystallization time of less than 24 hours:
  • Preparation method of silico-alumina-phosphorus carrier without template method mix 15g deionized water, 2.21g phosphoric acid, 1.38g pseudo-boehmite, 0.77g silica sol and 5g sodium hydroxide, and stir at 20°C for 3h . Then the mixture was transferred to a high-pressure crystallization kettle lined with polytetrafluoroethylene, sealed and crystallized at 190°C for 20 hours. After the reaction, the solid product was centrifuged and washed and dried to obtain the initial product.
  • Comparative Example 5 The purpose is to illustrate the preparation steps of the template-free silico-aluminum-phosphorus carrier for too long crystallization time:
  • the above cat1-17 catalysts were used to evaluate palm oil, methyl esterified palm oil and waste fatty acid hydrodeoxygenation, and the results of hydroisomerization of their products are shown in Table 1-6.
  • the evaluation conditions of the hydrodeoxygenation reaction are space velocity 1h -1 , 350°C, and hydrogen-to-oil ratio 800; the hydroisomerization reaction evaluation conditions are space velocity 1h -1 , 350°C, and hydrogen-to-oil ratio 800.
  • the catalyst has high hydrodeoxygenation activity and high conversion rate under normal preparation conditions.
  • the resulting product is A biodiesel component based on long-chain alkanes C15-C18.
  • the catalyst synthesized with an unsuitable amount of alkali, such as cat13-14, has a very low hydrodeoxygenation conversion rate and a very low liquid yield.
  • the unsuitable alkali is The silicon-aluminum-phosphorus carrier with a porous structure has not been synthesized, so it does not have hydrodeoxygenation activity.
  • the porous structure of the silicon-aluminum-phosphorus carrier with suitable alkali content prepared by the template-free method has excellent hydrodeoxygenation activity.
  • Table 4-6 It can be seen from Table 4-6 that palm oil, methyl esterified palm oil, and waste fatty acid hydrodeoxygenation products are used as raw materials for the isomerization reaction.
  • Table 4-6 shows that the normally prepared catalyst has suitable acid strength and is suitable Pores and morphology, so it has excellent isomerization cracking activity, can obtain highly selective bio-jet fuel components and some bio-aviation gasoline components, and the catalyst in the comparative example due to improper alkali content, crystallization
  • the conditions result in the synthesis of the catalyst with very weak acidity, so the conversion rate is very low, and the selectivity of aviation fuel components is low. From the material aspect, it is explained that the unsuitable amount of alkali, crystallization conditions, etc.
  • the structured silicon-aluminum-phosphorus carrier has excellent hydroisomerization activity.
  • Catalysts 1-12 are all prepared by normal synthesis methods.
  • the carrier itself has suitable acid strength.
  • the synthesized catalysts are weakly cracked, and the conversion rate and selectivity performance are poor. Good, so the obtained biofuel has a low component conversion rate and low selectivity.

Abstract

一种多孔结构的硅铝磷载体加氢催化剂的制备方法及在制备生物燃料中的应用。载体的合成中不加入胺类模板剂，通过硅源与碱源的调节并寻找适合的水热合成条件，即可得到多孔结构的硅铝磷载体，得到的载体不用焙烧，通过离子交换去除晶体中的钠离子，即可作为植物油加氢脱氧、加氢异构制备生物燃料的催化剂。

Description

多孔结构的硅铝磷载体加氢催化剂的制备方法及在制备生物燃料中的应用 技术领域
本发明属于催化剂领域，尤其是涉及一种多孔结构的硅铝磷载体加氢催化剂的制备方法及在制备生物燃料中的应用。
背景技术
随着工业化时代的发展和社会文明的进步，能源危机问题和环境污染问题已经逐渐成为世界性的焦点问题。在世界范围尤其是工业化国家，都要大量消耗化石能源来满足工业发展、城市运营、交通运输等等基本需求。因此，可再生生物能源的探索迫在眉睫，例如采用催化剂将动植物油进行加氢脱氧，得到的长链烷烃产物进行加氢异构，从而得到高产率的生物燃油。
动植物油催化加氢制备生物燃油常用加氢脱氧和加氢异构即两步法生产工艺。首先通过加氢脱氧将原料油转化为正构的长链烷烃，再经过催化剂加氢异构得到带有支链、碳链选择性适宜的产物。采用催化剂可以同时应用在第一步和第二步反应中，并利用载体酸性特点和孔道结构对油脂以及长链烷烃进行加氢脱氧以及适度的加氢异构得到满足不同燃料标准的烷烃产物。
催化剂通常用分子筛作为载体，但分子筛在合成中需要用到有机胺模板剂，之后需要洗涤和焙烧分别去除未反应的和产物中的有机胺模板剂。这一过程会导致含N的废水和氮氧化物气体排放到环境中造成严重污染。本发明研发的无模板剂法合成多孔结构的硅铝磷载体可以从根本上解决这一问题，在不添加模板剂的基础上，通过引入具有导向功能的Na、K、Ca离子，并经过不同磷源、碱源、硅源的相互作用，得到了具有规则孔道的多孔硅铝磷，并且作为载体制备出的催化剂转化率高，可以得到高产率的生物汽油、生物航煤和生物柴油组分。目前无模板剂法合成硅铝分子筛材料的研究较多，但是硅铝磷系列晶体的无模板剂法合成的研究还尚未有报道。
CN105347360B公开了一种无模板剂超大颗粒ZSM-5沸石分子筛的合成方法，采用旋转烘箱，高压合成釜带有角度的旋转，预晶化液添加的方法，合成得到了颗粒在20μm以上的ZSM-5沸石分子筛。CN102502696B公开了一种ZSM-5沸石分子筛的合成方法，通过加入酸碱分别调节硅源和铝源的聚合度得到高活性的 反应物，能够在体系中大量快速成核得到纳米沸石，并且不局限于硅源和铝源的种类，对原料适应性强，通过简单调节改变原料活性，可在无模板剂和低廉价模板剂用量条件下快速合成结晶度良好的纳米ZSM-5沸石产物。CN102285666B提供了一种无模板剂条件下制备菱沸石及菱沸石膜的方法，在未添加有机模板剂的条件下，通过异相晶核T型沸石的诱导形成纯的菱沸石。以形成的菱沸石为晶种负载在多孔支撑体外表面，诱导形成菱沸石分子筛膜，合成的膜在考察的酸性介质中表现出较好的稳定性，可广泛应用于酸性体系的渗透汽化分离过程和渗透汽化膜反应器。CN103638965B公开了一种用于甘油脱水制丙烯醛的多级孔ZSM-5沸石催化剂及其制备方法与应用，仅需在一般合成体系中(硅源、铝源、碱源和水)，引少量MFI沸石晶种以及部分无机盐添加剂，调变合成配比和反应条件即可，所制备的催化剂具有酸性位的量可控、比表面积大、传质路径短等特性，可用于甘油脱水制丙烯醛催化反应中，表现出优良的催化活性、选择性和稳定性。
德国的BASF公司(J Mater Chem A，2013，1(10)：3254-3257)已经采用无模板剂晶种诱导法生产了Beta沸石和插晶菱沸石。此后，他们又采用无模板剂晶种导法合成了Fe-Beta沸石，并将其用于直接分解N 2O，显示出良好的催化性能。
Lin等(Micro-porous Mesoporous Mater,2000,34(3):241-253)利用无模板剂二次生长法制备出硅铝MFI分子筛膜，无需使用有机模板剂，降低了成本，并且避免了分子筛膜在高温煅烧脱除模板剂过程中所产生的缺陷。
以上发明和学术文章中，通过晶种诱导法、预晶化法、改变晶化条件等方法实现模板剂的减少从而减少对环境的污染，大部分应用在硅铝分子筛中，而对于加氢脱氧和加氢异构化反应，需要适宜的酸强度和酸性位点以及孔道结构，因此硅铝磷系列多孔结构材料具有更适合的酸性中心和孔道结构，从而催化加氢得到高收率以及高选择性的生物燃料。目前硅铝磷系列多孔材料有很多研究方法的合成，但无模板法鲜有报道。
发明内容
为解决上述技术问题，本发明提出了一种多孔结构的硅铝磷载体加氢催化剂的制备方法及在制备生物燃料中的应用，通过无模板剂法合成硅铝磷晶体载体， 并应用于油脂加氢以及长链烷烃异构化制备生物燃油。目的是希望该催化剂可以用于工业生产，减少污染，在生产中无高含量有机废水产生，高效产出可再生生物燃料。
本发明采用的技术方案是：多孔结构的硅铝磷载体，向硅源、铝源、磷源与水得混合液中加入碱源进行晶化反应，水、硅源、铝源、磷源和碱源以氧化物的摩尔比50-100:1:1:0.1-1:0.5-2进行混合，再经离子交换剂处理得到多孔结构的硅铝磷载体。
优选地，硅源为硅酸钠、硅溶胶、正硅酸乙酯、白炭黑中的一种。
优选地，碱源为氢氧化钾、氢氧化钠、氢氧化钙中的一种。
优选地，磷源为磷酸。
优选地，离子交换剂为硝酸铵、氯化铵、硫酸铵、盐酸、磷酸铵中的一种。
多孔结构的硅铝磷载体制备的多孔结构的硅铝磷载体加氢催化剂，将活性组分负载在多孔结构的硅铝磷载体上得到的多孔结构的硅铝磷载体加氢催化剂；
优选地，活性组分为Ni x-Mo、Ni x-Co或Ni x-W中的一种，活性组分质量占催化剂总质量的10-30％，其中x的范围为5-20。
多孔结构的硅铝磷载体加氢催化剂的制备方法，具体步骤为：
步骤一将去离子水、硅源、铝源、磷源和碱源以氧化物的摩尔比50-100:1:1:0.1-1:0.5-2进行混合并搅拌，晶化后获得载体初产物；
步骤二使用离子交换剂对载体初产物进行离子交换，得到多孔结构的硅铝磷载体；
步骤三按照活性组分质量占催化剂总质量的10-30％的配比，将所需活性组分的可溶性盐溶液加入到多孔结构的硅铝磷载体中，老化烘干焙烧后得到多孔结构的硅铝磷载体加氢催化剂；
优选地，步骤二中将载体初产物加入到离子交换剂中，25-80℃下充分搅拌3-12h，洗涤干燥后记为一次离子交换，离子交换2-3次；
优选地，步骤二中离子交换剂与载体初产物质量比为5-20:1；
优选地，步骤一中晶化条件为160-200℃下晶化18-96h。
优选地，硅源为硅酸钠、硅溶胶、正硅酸乙酯、白炭黑中的一种；
优选地，碱源为氢氧化钾、氢氧化钠、氢氧化钙中的一种；
优选地，磷源为磷酸；
优选地，离子交换剂为硝酸铵、氯化铵、硫酸铵、盐酸、磷酸铵中的一种。
优选地，活性组分为Ni x-Mo、Ni x-Co或Ni x-W中的一种，活性组分质量占催化剂总质量的10-30％，其中x的范围为5-20；
优选地，将活性组分的可溶性盐溶解到载体质量一倍吸水率的去离子水中获得活性组分的可溶性盐溶液；
优选地，活性组分的可溶性盐为硝酸镍、硝酸钴、偏钨酸铵或钼酸铵中的一种。
多孔结构的硅铝磷载体加氢催化剂在棕榈油，甲酯化棕榈油或废弃脂肪酸通过加氢脱氧加氢异构制备生物燃料中的应用。
本发明具有的优点和积极效果是：
1在无模板剂条件下，通过引入碱源并改变投料比例得到了多孔结构的硅铝磷，再经过离子交换处理，得到了具有适宜酸性性质的载体，该方法避免了有机胺模板剂的使用，降低生产成本，也避免了脱除模板剂的过程中产生有机胺污染物或氮氧化物造成的环境污染，实现绿色环保可持续性生产；
2本方案制备所得的催化剂可以应用于油脂加氢脱氧以及长链烷烃的加氢异构化与裂化反应，制的产物燃油满足燃烧多项标准。通过本发明中合成的催化剂，可以得到组分包括汽油、煤油、柴油的生物燃料产物。
附图说明
图1是不同晶化时间氢氧化铝摩尔比在0.5所合成的硅铝磷晶体的粉末X射线衍射图；
图2是不同晶化时间氢氧化铝摩尔比在1.5所合成的硅铝磷晶体的粉末X射线衍射图；
图3是所合成的硅铝磷晶体的扫描电镜图片，其中(a)硅源为硅溶胶(b)硅源为硅酸钠(c)硅源为正硅酸乙酯。
具体实施方式
本发明提出了一种多孔结构的硅铝磷载体加氢催化剂的制备方法及在制备生物燃料中的应用，尤其是棕榈油及其他油脂加氢制备生物燃料方面的应用，其中多孔结构的硅铝磷晶体的合成中并无胺类模板剂的加入，通过硅源与碱源的调 节并寻找到适合的水热合成条件，即可得到无模板法制备的多孔结构的硅铝磷晶体，制备所得的晶体不用焙烧，通过离子交换去除晶体中的钠离子，钾离子或钙离子，即可作为棕榈油及其他油脂加氢脱氧、加氢异构和加氢裂化制备生物燃料的催化剂。此方法合成工艺简单，绿色无污染，节能环保，而且制得的催化剂加氢活性高，催化剂，生物燃料收率高。
多孔结构的硅铝磷载体的制备过程，向硅源、铝源、磷源与水得混合液中加入碱源进行反应，水、硅源、铝源、磷源和碱源以氧化物的摩尔比50-100:1:1:0.1-1:0.5-2进行混合，晶化后获得多孔结构的硅铝磷载体初产物，再经离子交换剂处理得到多孔结构的硅铝磷载体。其中，硅源可以为硅酸钠、硅溶胶、正硅酸乙酯、白炭黑中的一种；碱源可以为氢氧化钾、氢氧化钠、氢氧化钙中的一种；磷源为磷酸。离子交换时采用的离子交换剂可以为硝酸铵、氯化铵、硫酸铵、盐酸、磷酸铵中的一种。如图1图2所示，硅铝磷晶体在高碱量和低碱量情况下，晶化72-96小时后，结晶度和稳定性均比较高，证明其催化活性和稳定性也比较高。如图3所示是所合成的硅铝磷晶体的扫描电镜图片，其中(a)是硅源为硅溶胶制备的多孔结构的硅铝磷载体，(b)是硅源为硅酸钠的多孔结构的硅铝磷载体，(c)是硅源为正硅酸乙酯的多孔结构的硅铝磷载体；从扫描电镜结果来看，无模板的硅铝磷载体具备球形的形貌，不同硅源制备出的球形状也有稍许的不同，优于不同硅源形成凝胶胶束不同，因此晶体形貌稍有区别，但用于催化剂载体具有相似的加氢效果。
采用多孔结构的硅铝磷载体制备多孔结构的硅铝磷载体加氢催化剂，即将活性组分负载在多孔结构的硅铝磷载体上得到的多孔结构的硅铝磷载体加氢催化剂；其中，活性组分为Ni x-Mo、Ni x-Co或Ni x-W中的一种，活性组分质量占催化剂总质量的10-30％，其中x的范围为5-20。其中主要活性金属组分为Ni，协同组分为Mo和W。
多孔结构的硅铝磷载体加氢催化剂的制备方法，步骤如下：
首先，多孔结构的硅铝磷载体的制备：
步骤一 将去离子水、硅源、铝源、磷源和碱源以氧化物的摩尔比50-100:1:1:0.1-1:0.5-2进行混合并搅拌，晶化后获得载体初产物；
步骤二 使用离子交换剂对载体初产物进行离子交换，得到多孔结构的硅铝 磷载体。
其次，多孔结构的硅铝磷载体加氢催化剂的制备：
步骤三 按照活性组分质量占催化剂总质量的10-30％的配比，将所需活性组分的可溶性盐溶液加入到多孔结构的硅铝磷载体中，老化烘干焙烧后得到多孔结构的硅铝磷载体加氢催化剂。
具体步骤如下：
步骤一 将去离子水、硅源、铝源、磷源和碱源以氧化物的摩尔比50-100:1:1:0.1-1:0.5-2混合，在20-50℃下搅拌3-5h；然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在160-200℃下晶化18-96h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到载体初产物。其中，硅源可以为硅酸钠、硅溶胶、正硅酸乙酯、白炭黑中的一种；碱源可以为氢氧化钾、氢氧化钠、氢氧化钙中的一种；磷源为磷酸。
步骤二 使用离子交换剂对载体初产物进行离子交换，将载体初产物加入到0.2-2mol/L的离子交换剂中，离子交换剂与载体初产物的质量比例为5-20:1，在25-80℃下充分搅拌3-12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换2-3次，最终得到的产物为多孔结构的硅铝磷载体。离子交换剂为硝酸铵、氯化铵、硫酸铵、盐酸、磷酸铵中的一种。
步骤三 按照活性组分质量占催化剂总质量的10-30％的配比，将所需活性组分的可溶性盐溶解到载体质量一倍吸水率的去离子水中，充分搅拌2h后加入到多孔结构的硅铝磷载体中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，得到多孔结构的硅铝磷载体加氢催化剂。其中，活性组分为Ni x-Mo、Ni x-Co或Ni x-W中的一种，活性组分质量占催化剂总质量的10-30％，其中x的范围为5-20；例如为硝酸镍、硝酸钴、偏钨酸铵或钼酸铵。
制备所得的多孔结构的硅铝磷载体加氢催化剂能够用于油脂制备生物燃料，其中，油脂为棕榈油，甲酯化棕榈油，废弃脂肪酸中的一种。加氢脱氧和加氢异构步骤如下：
加氢脱氧：将称好的催化剂装入反应器的恒温区间内，反应管上端装入瓷环填满，目的为将温度较低的原料进行预热。反应前，将催化剂在H 2气氛中(160mL min -1)一定温度下(一般为350℃)预处理2h，使得负载的氧化物被还原 为零价态，然后设定反应所需的温度，压力和氢气流速进行评价(3-10MPa氢气压力下，氢油比为800-2000，反应温度300-400℃)。每小时接料，产物通过气相色谱进行分析。
加氢异构化：催化剂的评价在连续流动固定床反应器上进行，以第一步HDO产物为原料，考察催化剂的异构化裂化效果。催化剂粉末在装入反应器前先要被压片(压片压力为20MPa)，破碎，筛选20–40目的颗粒作为评价用催化剂。将称好的催化剂装入反应器的恒温区间内，反应管上端装入瓷环填满，目的是对低温原料进行充分预热。反应前，将催化剂在H 2气氛(160mL min -1)一定温度下(一般为350℃)预处理2h，使得负载的氧化物被还原为零价态，然后设定反应所需的温度，压力和氢气流速(3-10MPa氢气压力下，氢油比为800-2000，反应温度300-400℃)进行评价。每小时接料，产物通过气相色谱进行分析。
下面通过具体实施例对本方案做出进一步说明，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作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做任何限定，包含于但不包括所有的请求保护的范围。
实施例1.加氢脱氧催化剂的制备，包括以下步骤：
(1)无模板剂法硅铝磷载体的制备方法：将12.5g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.77g硅溶胶和4g氢氧化钠混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在180℃下晶化96h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到0.8mol/L的硝酸铵溶液中，液体与固体的质量比例为15:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换2次。最终得到的产物记为载体A；
(2)活性组分的上载：将6.06g硝酸镍和0.74g钼酸铵溶解到8g去离子水中，充分搅拌2h后加入到8g载体A中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于油脂加氢脱氧制备生物燃油的催化剂，记作cat1。
实施例2.加氢脱氧催化剂的制备，包括以下步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g 拟薄水铝石、0.38g硅溶胶和4g氢氧化钾混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在180℃下晶化96h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到0.8mol/L的硝酸铵溶液中，液体与固体的质量比例为15:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换2次。最终得到的产物记为载体B；
(2)活性组分的上载：将7.58g硝酸镍和0.74g钼酸铵溶解到8g去离子水中，充分搅拌2h后加入到8g载体B中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于油脂加氢脱氧制备生物燃油的催化剂，记作cat2。
实施例3.加氢脱氧催化剂的制备，包括以下步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.77g硅溶胶和5g氢氧化钙混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化96h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到0.8mol/L的硝酸铵溶液中，液体与固体的质量比例为15:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换2次。最终得到的产物记为载体C；
(2)活性组分的上载：将7.58g硝酸镍和0.74g钼酸铵溶解到8g去离子水中，充分搅拌2h后加入到载体C中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于油脂加氢脱氧制备生物燃油的催化剂，记作cat3。
实施例4.加氢脱氧催化剂的制备，包括以下步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.77g硅酸钠和5g氢氧化钠混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化96h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到1.2mol/L的氯化铵溶液中，液体与固体的质量比例为15:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换2次。最终得到的产物记为载体D；
(2)活性组分的上载：将7.58g硝酸镍和0.74g硝酸钴溶解到8g去离子水中， 充分搅拌2h后加入到载体A中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于油脂加氢脱氧制备生物燃油的催化剂，记作cat4。
实施例5.加氢脱氧催化剂的制备，包括以下步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.77g硅酸钠和5g氢氧化钾混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化96h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到1.2mol/L的硝酸铵溶液中，液体与固体的质量比例为15:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换2次。最终得到的产物记为载体D；
(2)活性组分的上载：将7.58g硝酸镍和0.74g硝酸钴溶解到8g去离子水中，充分搅拌2h后加入到载体D中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于油脂加氢脱氧制备生物燃油的催化剂，记作cat5。
实施例6.加氢脱氧催化剂的制备，包括以下步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.77g硅溶胶和5g氢氧化钙混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化96h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到1.2mol/L的氯化铵溶液中，液体与固体的质量比例为15:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换2次。最终得到的产物记为载体E；
(2)活性组分的上载：将7.58g硝酸镍和0.74g硝酸钴溶解到8g去离子水中，充分搅拌2h后加入到载体E中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于油脂加氢脱氧制备生物燃油的催化剂，记作cat6。
实施例7.加氢异构催化剂的制备，包括以下步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.77g正硅酸乙酯和7.5g氢氧化钠混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化72h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交 换剂对该产物进行离子交换，将固体加入到0.5mol/L的盐酸溶液中，液体与固体的质量比例为15:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换2次。最终得到的产物记为载体F；
(2)活性组分的上载：将6.06g硝酸镍和0.65g偏钨酸铵溶解到8g去离子水中，充分搅拌2h后加入到载体F中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于长链烷烃加氢异构制备生物燃油的催化剂，记作cat7。
实施例8.加氢异构催化剂的制备，包括以下步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.77g正硅酸乙酯和7.5g氢氧化钾混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化72h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到0.5mol/L的盐酸溶液中，液体与固体的质量比例为15:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换2次。最终得到的产物记为载体G；
(2)活性组分的上载：将6.06g硝酸镍和0.74g偏钨酸铵溶解到8g去离子水中，充分搅拌2h后加入到载体G中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于长链烷烃加氢异构制备生物燃油的催化剂，记作cat8。
实施例9.加氢异构催化剂的制备，包括以下步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.77g正硅酸乙酯和7.5g氢氧化钙混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化72h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到0.5mol/L的盐酸溶液中，液体与固体的质量比例为10:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换2次。最终得到的产物记为载体H；
(2)活性组分的上载：将6.06g硝酸镍和0.74g偏钨酸铵溶解到8g去离子水中，充分搅拌2h后加入到载体H中，静置老化24h后，将混合物烘干，在500℃ 空气气氛中焙烧3h，即得到用于长链烷烃加氢异构制备生物燃油的催化剂，记作cat9。
实施例10.加氢异构催化剂的制备，包括以下步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.77g白炭黑和7.5g氢氧化钠混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化72h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到1mol/L的硫酸铵溶液中，液体与固体的质量比例为20:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换3次。最终得到的产物记为载体I；
(2)活性组分的上载：将6.06g硝酸镍和0.74g偏钨酸铵溶解到8g去离子水中，充分搅拌2h后加入到载体I中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于长链烷烃加氢异构制备生物燃油的催化剂，记作cat10。
实施例11.加氢异构催化剂的制备，包括以下步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.38g白炭黑和6g氢氧化钾混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化72h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到1mol/L的硫酸铵溶液中，液体与固体的质量比例为20:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换3次。最终得到的产物记为载体I；
(2)活性组分的上载：将6.06g硝酸镍和0.74g偏钨酸铵溶解到8g去离子水中，充分搅拌2h后加入到载体I中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于长链烷烃加氢异构制备生物燃油的催化剂，记作cat11。
实施例12.加氢异构催化剂的制备，包括以下步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.38g白炭黑和6g氢氧化钙混合，在20℃下搅拌3h。然后把混合 物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化72h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到1mol/L的硫酸铵溶液中，液体与固体的质量比例为20:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换3次。最终得到的产物记为载体I；
(2)活性组分的上载：将6.06g硝酸镍和0.74g偏钨酸铵溶解到8g去离子水中，充分搅拌2h后加入到载体I中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于长链烷烃加氢异构制备生物燃油的催化剂，记作cat12。
对比例1.目的在于说明不添加碱源的情况下无模板剂法硅铝磷载体的制备步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石和0.77g硅溶胶混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化72h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到2mol/L的硫酸铵溶液中，液体与固体的质量比例为20:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换3次。最终得到的产物记为载体J；
(2)活性组分的上载：将6.06g硝酸镍和0.74g钼酸铵溶解到8g去离子水中，充分搅拌2h后加入到载体J中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到加氢脱氧催化剂，记作cat13。
对比例2.目的在于说明碱量少于0.5mol的无模板剂法硅铝磷载体的制备步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、2g硅溶胶和3.5g氢氧化钠混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化72h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到2mol/L的硝酸铵溶液中，液体与固体的质量比例为15:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换 一次，共交换3次。最终得到的产物记为载体K；
(2)活性组分的上载：将6.06g硝酸镍和0.74g钼酸铵溶解到8g去离子水中，充分搅拌2h后加入到载体K中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到加氢脱氧催化剂，记作cat14。
对比例3.目的在于说明碱过量无模板剂法硅铝磷载体的制备步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、1.77g硅酸钠和8.5g氢氧化钠混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化72h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到2mol/L的硝酸铵溶液中，液体与固体的质量比例为15:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换3次。最终得到的产物记为载体L；
(2)活性组分的上载：将6.06g硝酸镍和0.74g钼酸铵溶解到8g去离子水中，充分搅拌2h后加入到载体L中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于长链烷烃加氢异构制备生物燃油的催化剂，记作cat15。
对比例4.目的在于说明晶化时间少于24小时无模板剂法硅铝磷载体的制备步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.77g硅溶胶和5g氢氧化钠混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化20h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物。之后使用离子交换剂对该产物进行离子交换，将固体加入到2mol/L的硝酸铵溶液中，液体与固体的质量比例为15:1，在25℃下充分搅拌12h，停止搅拌后离心洗涤干燥，记为离子交换一次，共交换3次。最终得到的产物记为载体M；
(2)活性组分的上载：将6.06g硝酸镍和0.74g钼酸铵溶解到8g去离子水中，充分搅拌2h后加入到载体M中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于长链烷烃加氢异构制备生物燃油的催化剂，记作cat16。
对比例5.目的在于说明晶化时间过长无模板剂法硅铝磷载体的制备步骤：
(1)无模板剂法硅铝磷载体的制备方法：将15g去离子水、2.21g磷酸、1.38g拟薄水铝石、0.77g硅溶胶和5g氢氧化钠混合，在20℃下搅拌3h。然后把混合物转移到聚四氟内衬的高压晶化釜中，密封后在190℃下晶化120h，反应结束静置降温后将固体产物经过离心洗涤干燥后得到初始产物，未进行离子交换，记为载体N；
(2)活性组分的上载：将6.06g硝酸镍和0.74g钼酸铵溶解到8g去离子水中，充分搅拌2h后加入到载体N中，静置老化24h后，将混合物烘干，在500℃空气气氛中焙烧3h，即得到用于长链烷烃加氢异构制备生物燃油的催化剂，记作cat17。
将上述cat1-17几种催化剂分别用于评价棕榈油，甲酯化棕榈油和废弃脂肪酸加氢脱氧以及其产物加氢异构化结果如表1-6所示。其中加氢脱氧反应评价条件为空速1h -1，350℃，氢油比800；加氢异构化反应评价条件为空速1h -1，350℃，氢油比800。
表1棕榈油加氢脱氧制备生物燃料的评价结果：
Figure PCTCN2019106883-appb-000001
表2甲酯化棕榈油加氢脱氧制备生物燃料的评价结果：
Figure PCTCN2019106883-appb-000002
表3废弃脂肪酸加氢脱氧制备生物燃料的评价结果：
Figure PCTCN2019106883-appb-000003
通过表1-3能够看出，从棕榈油、甲酯化棕榈油以及废弃脂肪酸的加氢脱氧表现，正常制备情况下催化剂的加氢脱氧活性很高，转化率也很高，得到的产物是以长链烷烃C15-C18为主的生物柴油组分。而不适宜的碱量合成出的催化剂如cat13-14，加氢脱氧转化率很低，液体收率也很低，产物中有很多没有反应完全的固态产物，从材料方面说明了不适宜的碱量并没有合成出多孔结构的硅铝磷 载体，因此不具备加氢脱氧活性，而通过无模板法制备出的适宜碱量的多孔结构的硅铝磷载体，具有优异的加氢脱氧活性。
表4棕榈油加氢脱氧产物加氢异构化制备生物燃料的评价结果：
Figure PCTCN2019106883-appb-000004
表5甲酯化棕榈油加氢脱氧产物加氢异构化制备生物燃料的评价结果：
Figure PCTCN2019106883-appb-000005
表6废弃脂肪酸加氢脱氧产物加氢异构化制备生物燃料的评价结果：
Figure PCTCN2019106883-appb-000006
通过表4-6能够看出，以棕榈油、甲酯化棕榈油、废弃脂肪酸加氢脱氧产物为原料，进行异构化反应，表4-6显示正常制备的催化剂具有适宜的酸强度，适宜的孔道和形貌，因此具有优异的异构化裂化活性，可以分别得到高选择性的生物航煤组分和部分生物航空汽油组分，而对比例中的催化剂由于不当的碱量、晶化条件导致合成出的催化剂具有很弱的酸性，因此转化率很低，航煤组分选择性低。从材料方面说明了不适宜的碱量、晶化条件等并没有合成出多孔结构的硅铝磷载体，因此不具备加氢异构化活性，而通过无模板法制备出的适宜碱量的多孔结构的硅铝磷载体，具有优异的加氢异构化活性。
催化剂1-12均通过正常合成方法制备得到，载体本身具有适宜的酸强度，对比例中由于缺少碱源、比例不当等原因，导致合成出的催化剂裂化很弱，转化率和选择性表现都不好，因此得到的生物燃料的成分转化率低，选择性低。
以上对本发明的一个实施例进行了详细说明，但所述内容仅为本发明的较佳实施例，不能被认为用于限定本发明的实施范围。凡依本发明申请范围所作的均等变化与改进等，均应仍归属于本发明的专利涵盖范围之内。

Claims (12)

  1. 多孔结构的硅铝磷载体，其特征在于：向硅源、铝源、磷源与水的混合液中加入碱源进行晶化反应，水、硅源、铝源、磷源和碱源以氧化物的摩尔比50-100:1:1:0.1-1:0.5-2进行混合，再经离子交换剂处理得到多孔结构的硅铝磷载体。
  2. 根据权利要求1所述的多孔结构的硅铝磷载体，其特征在于：所述硅源为硅酸钠、硅溶胶、正硅酸乙酯、白炭黑中的一种。
  3. 根据权利要求1所述的多孔结构的硅铝磷载体，其特征在于：所述碱源为氢氧化钾、氢氧化钠、氢氧化钙中的一种。
  4. 根据权利要求1所述的多孔结构的硅铝磷载体，其特征在于：所述磷源为磷酸。
  5. 根据权利要求1所述的多孔结构的硅铝磷载体，其特征在于：所述离子交换剂为硝酸铵、氯化铵、硫酸铵、盐酸、磷酸铵中的一种。
  6. 权利要求1-5中任一所述的多孔结构的硅铝磷载体制备的多孔结构的硅铝磷载体加氢催化剂，其特征在于：将活性组分负载在多孔结构的硅铝磷载体上得到的多孔结构的硅铝磷载体加氢催化剂；
    优选地，活性组分为Ni x-Mo、Ni x-Co或Ni x-W中的一种，活性组分质量占催化剂总质量的10-30％，其中x的范围为5-20。
  7. 多孔结构的硅铝磷载体加氢催化剂的制备方法，其特征在于：具体步骤为：
    步骤一 将去离子水、硅源、铝源、磷源和碱源以氧化物的摩尔比50-100:1:1:0.1-1:0.5-2进行混合并搅拌，晶化后获得载体初产物；
    步骤二 使用离子交换剂对载体初产物进行离子交换，得到多孔结构的硅铝磷载体；
    步骤三 按照活性组分质量占催化剂总质量的10-30％的配比，将所需活性组分的可溶性盐溶液加入到多孔结构的硅铝磷载体中，老化烘干焙烧后得到多孔结构的硅铝磷载体加氢催化剂。
  8. 根据权利要求7所述的多孔结构的硅铝磷载体加氢催化剂的制备方法，其特征在于：所述步骤二中将载体初产物加入到离子交换剂中，25-80℃下充分搅拌3-12h，洗涤干燥后记为一次离子交换，离子交换2-3次；
    优选地，所述步骤二中离子交换剂与载体初产物质量比为5-20:1；
    优选地，所述步骤一中晶化条件为160-200℃下晶化18-96h。
  9. 根据全能了要求7或8所述的多孔结构的硅铝磷载体加氢催化剂的制备方法，其特征在于：所述硅源为硅酸钠、硅溶胶、正硅酸乙酯、白炭黑中的一种；
    优选地，所述碱源为氢氧化钾、氢氧化钠、氢氧化钙中的一种；
    优选地，所述磷源为磷酸；
    优选地，所述离子交换剂为硝酸铵、氯化铵、硫酸铵、盐酸、磷酸铵中的一种。
  10. 根据权利要求7所述的多孔结构的硅铝磷载体加氢催化剂的制备方法，其特征在于：活性组分为Ni x-Mo、Ni x-Co或Ni x-W中的一种，活性组分质量占催化剂总质量的10-30％，其中x的范围为5-20。
  11. 根据权利要求10所述的多孔结构的硅铝磷载体加氢催化剂的制备方法，其特征在于：将活性组分的可溶性盐溶解到载体质量一倍吸水率的去离子水中获得活性组分的可溶性盐溶液；
    优选地，活性组分的可溶性盐为硝酸镍、硝酸钴、偏钨酸铵或钼酸铵中的一种。
  12. 权利要求6所述的多孔结构的硅铝磷载体加氢催化剂在棕榈油，甲酯化棕榈油或废弃脂肪酸通过加氢脱氧加氢异构制备生物燃料中的应用。
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