CN115382571B - Preparation method of silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst and application of catalyst in preparation of biofuel from kitchen waste oil - Google Patents

Preparation method of silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst and application of catalyst in preparation of biofuel from kitchen waste oil Download PDF

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CN115382571B
CN115382571B CN202211082709.1A CN202211082709A CN115382571B CN 115382571 B CN115382571 B CN 115382571B CN 202211082709 A CN202211082709 A CN 202211082709A CN 115382571 B CN115382571 B CN 115382571B
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molecular sieve
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silicon
phosphorus
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CN115382571A (en
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李伟
曾雪岑
关庆鑫
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Nankai University
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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

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

The invention discloses a preparation method of a silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst and application thereof in preparing biofuel from kitchen waste oil, wherein on the premise of not adding an organic template agent, water, a silicon source, an aluminum source, a phosphorus source, a Cs source and a Me source are mixed to prepare initial gel, crystallization is carried out, the silicon-aluminum-phosphorus molecular sieve can be synthesized under the crystallization temperature of 150-200 ℃, and the bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst is obtained after active components are loaded. The preparation method of the catalyst disclosed by the invention is environment-friendly, the template agent is not required to be removed by high-temperature roasting, the ion exchange is also not required, the output of harmful waste gas is avoided, the catalyst for preparing the biofuel by the hydrogenation of the biomass can be obtained after the carrier is loaded with the active components, the metal in the pore canal of the catalyst and on the framework of the molecular sieve and the loaded metal have high-efficiency synergistic effect, and the dispersity of Ni is improved by introducing the second metal, so that the catalyst has more active sites.

Description

Preparation method of silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst and application of catalyst in preparation of biofuel from kitchen waste oil
Technical Field
The invention belongs to the technical field of zeolite molecular sieve preparation, and particularly relates to a preparation method of a silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst and application of the catalyst in preparation of biofuel from kitchen waste oil.
Background
The exhaustion of fossil energy and the stringent emissions requirements of carbon dioxide make conventional aviation fuels a dual challenge in demand and emissions standards. The carbon dioxide gas generated after the traditional aviation kerosene is combusted is directly discharged at the stratosphere, and the caused greenhouse effect is far higher than that of other industries. In order to protect the living environment of human beings and reduce the emission of greenhouse gases, development of a new biological aviation kerosene, such as hydrodeoxygenation of vegetable oil and animal oil, including soybean oil, palm oil, castor oil, rapeseed oil, maple oil, lard, fish oil and the like, cracking isomerization into biofuel,
The natural grease can be processed into the biofuel through two steps. The natural oil contains a large amount of oxygen-containing functional groups such as aldehyde, hydroxy, phenol and the like, the oxygen content is too high, and the carbon chain also contains a large amount of unsaturated bonds, so that the biological oil has poor stability. The hydrodeoxygenation-hydrocracking/isomerisation technical route of the natural oil can be divided into two steps, wherein the first step is to deoxidize the biomass oil in the hydrogen atmosphere, so that oxygen elements in oxygen-containing functional groups leave in the form of H 2O、CO2 or CO, thereby improving the saturation of the biomass oil to obtain straight-chain alkane, and the second step is to crack and isomerise the long-chain alkane to obtain branched shorter-chain alkane, thereby reducing the viscosity of the biomass oil and improving the low-temperature fluidity, and reaching the oil standard of the biological aviation kerosene.
The hydrodeoxygenation catalyst for biological oil products consists of active metal and a molecular sieve carrier. A large amount of organic amine template is often required in the synthesis process of the traditional molecular sieve. Although the use of the template agent brings about the synthesis and structural development of the zeolite material, the use of the template agent brings about a great problem in industrial production: firstly, the synthesis cost is increased; in order to obtain open microporous channels, the organic template agent needs to be removed before zeolite is used, and the common removal method is high-temperature roasting, so that the emission of greenhouse gases is increased, and the method is contrary to national energy conservation and emission reduction national policies. On the other hand, a large amount of organic template agents are toxic and harmful, and the environmental pollution problem is serious.
PCT/CN2019/106883 discloses a preparation method of a template-free synthetic porous silicon-aluminum-phosphorus carrier. The synthesis does not add organic amine template agent, and the silicon-aluminum-phosphorus carrier with a porous structure is obtained through the adjustment of a silicon source and an alkali source and proper hydrothermal synthesis conditions. And roasting the mixture to obtain the vegetable oil hydrodeoxygenation and isomerization cracking biofuel. CN201711126785.7 discloses a hydrothermal synthesis method of Na-type zeolite molecular sieve. The method takes a silicon source, an aluminum source, sodium hydroxide and zeolite seed crystal as raw materials, then natural stilbite seed crystal is directly added into initial gel, and Na-type heulandite molecular sieve is hydrothermally synthesized under the conditions of shorter crystallization time (3-4 days) and lower crystallization temperature (130-170 ℃). And (3) carrying out solid-liquid separation on the obtained hydrothermal crystallization product, washing and drying to obtain the Na-type zeolite molecular sieve. The method can prepare Na-type zeolite flakes with high crystallinity and uniform particle size under milder conditions, and has great application prospect in the fields of gas adsorption and separation, cation exchange and the like. CN202011480960.4 discloses a template-free SAPO-34 molecular sieve and a preparation method thereof. The method provides a template-free SAPO-34 molecular sieve synthesized by a seed crystal method assisted by hydrothermal synthesis, wherein the template-free SAPO-34 molecular sieve comprises the following components in parts by weight: si0 2 -10 parts; 15.5-25.5 parts of Al 203: p 205 -75.5 weight portions, and then 1-6wt% of the total mass of the synthesized molecular sieve raw material needs to be added as seed crystal in the synthesis process.
CN202110764889.0 discloses a SAPO-11 molecular sieve, its preparation method and application. According to the method, co is doped in the SAPO-11 molecular sieve, the Co doping can influence the coordination between silicon and aluminum in the molecular sieve, so that the property of B acid in the molecular sieve is changed, co replaces aluminum to enter an SAP0-11 framework, an acid center is formed, and the acid strength is enhanced; and the Co doping can disperse silicon atoms in a crystal skeleton to generate new acid sites, and can increase the concentration of the total acid sites, so that the catalytic activity of the molecular sieve catalyst is improved, and the yield of isomers is improved. CN202110504195.3 discloses a preparation method and application of Au-Mg/SAPO-11 molecular sieve catalyst. The catalyst is prepared from SAPO-11 molecular sieve and composite nano metal Au-Mg. Adding a template agent into a silicon source, an aluminum source and a phosphorus source, crystallizing at a high temperature, and separating and purifying to obtain the SAPO-11 molecular sieve. Finally, au salt and Mg salt are loaded, and the Au-Mg/SAPO-11 molecular sieve is obtained after the reduction of sodium borohydride and is applied to the synthesis of bisphenol F and the oxidation reaction of alcohols
CN104549381a discloses a synthesis method and application of active silicon-phosphorus-aluminum material. The material has a pseudo-boehmite crystal phase, a silicon source and a phosphorus source are added into colloid formed by an aluminum source and alkali liquor, and the material is obtained after crystallization and roasting, wherein the composition of anhydrous compound is (0-0.2) Na 2O： (64-76)Al2O3：(23-35)SiO2：(1-7)P5O2 in terms of the weight ratio of oxide. The material has mesoporous characteristic, and is used as an active component or an active matrix material for macromolecule cracking and used in a heavy oil catalytic cracking agent or an auxiliary agent.
CN104815697a discloses a preparation method of a catalyst for preparing biological aviation kerosene by using castor oil. Deionized water, silica sol, phosphoric acid and pseudo-boehmite are mixed and stirred, and di-n-propylamine and diisopropylamine are added as templates to synthesize the carrier of the SAPO-11 with multistage pore canals. The method improves the dispersity of the active components by multiple times of impregnation. In the invention, the use of a template agent in the process of synthesizing the silicon-aluminum-phosphorus molecular sieve is reduced by a seed crystal induction method and an ion guide method.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst and application of the catalyst in preparation of biofuel from kitchen waste oil.
The technical scheme adopted by the invention is as follows: the preparation method of the silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst comprises the steps of mixing water, a silicon source, an aluminum source, a phosphorus source, a Cs source and a Me source to prepare initial gel, wherein the mole ratio of the water, the silicon source, the aluminum source, the phosphorus source, the Cs source and the Me source is 50-100:0.2-1:1:0.5-1.0:0.1-2:0.1-2; crystallizing to obtain the silicon-aluminum-phosphorus molecular sieve, and loading active metal to obtain the bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst.
Preferably, me is one of Li, na, K, mg, ba, cu and Mn.
Preferably, the Me source is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, barium hydroxide, copper hydroxide, and manganese hydroxide.
Preferably, the Cs source is a combination of one or more of cesium hydroxide, cesium carbonate, cesium oxalate, and cesium acetate.
Preferably, the silicon source is one or more of sodium silicate, silica sol, tetraethyl orthosilicate and white carbon black;
The aluminum source is one or a combination of more of sodium metaaluminate, aluminum hydroxide and pseudo-boehmite;
the phosphorus source is phosphoric acid.
Preferably, the crystallization temperature is 150-200 ℃.
Preferably, the active component is Ni-xCs, the mass of the active component accounts for 10-30% of the total mass of the catalyst, and x is the mass percent of simple substance Cs to simple substance Ni, wherein the range of x is 5-20.
Preferably, dissolving soluble salt of the active component into deionized water with the water absorption of twice the carrier mass, adding the silicon-aluminum-phosphorus molecular sieve, standing, aging, drying and roasting, and reducing with hydrogen to obtain the bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst.
The bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst is prepared by the preparation method of the silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst.
The application of the bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst in preparing biological fuel;
preferably, the method is applied to preparing the biofuel from the kitchen waste oil.
Preferably, the kitchen waste oil is pretreated firstly, specifically as follows:
Weighing phosphoric acid or citric acid solution with the mass of 0.5-1% of the kitchen waste oil, adding the phosphoric acid or citric acid solution into the oil, stirring and reacting at 80-85 ℃, adding distilled water with the mass of 5-8% of the kitchen waste oil, stirring and reacting at 70-75 ℃, standing at constant temperature, centrifuging, and collecting an oil layer;
Adding distilled water with the mass of 8-15% of the oil layer, vigorously stirring at 70-75 ℃, centrifuging, and collecting an oil layer for the second time;
adding acid clay with the mass of 8-10% of the oil layer collected for the second time, heating to 100-110 ℃ and stirring, centrifuging and collecting the treated kitchen waste oil.
The invention has the advantages and positive effects that: the molecular sieve synthesized by the preparation method is environment-friendly, does not need high-temperature roasting to remove the template agent, does not need ion exchange, and can be used in the fields of biomass hydrogenation preparation of biological fuel and the like after loading active components; the NiCs/CsMeAPO-11 molecular sieve obtained by construction has high-efficiency synergistic effect of Cs metal, me metal and load metal in pore channels and on a molecular sieve framework, has proper acid strength and acid quantity, and has wide prospect in the aspect of catalyzing biological oil hydroisomerization cracking to prepare biological aviation kerosene.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the products prepared in example 1, comparative examples 2-3 of the present invention;
FIG. 2 is a scanning electron micrograph of the product prepared in example 1 of the present invention.
Detailed Description
Embodiments of the present invention are described below with reference to the accompanying drawings.
The invention discloses a preparation method of a silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst, which is used for focusing template-free synthesis of a silicon-aluminum-phosphorus molecular sieve, takes a silicon source, an aluminum source, a phosphorus source, cesium salt and Me salt as raw materials, and is different from the traditional hydrothermal synthesis, and the bimetallic silicon-aluminum-phosphorus molecular sieve is synthesized under the microwave condition. The preparation method comprises the steps of firstly mixing water, a silicon source, an aluminum source, a phosphorus source, a Cs source and a Me source to prepare initial gel, wherein the mole ratio of the water, the silicon source, the aluminum source, the phosphorus source, the Cs source and the Me source is 50-100:0.2-1:1:0.5-1.0:0.1-2:0.1-2; then carrying out crystallization reaction for 1-6h at the temperature of 150-200 ℃ by microwaves to prepare the silicon-aluminum-phosphorus molecular sieve, and carrying active metal to obtain the bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst.
Wherein, me source is one of Li, na, K, mg, ba, cu and Mn; the Me source is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, barium hydroxide, copper hydroxide and manganese hydroxide; the cesium source is one or a combination of more of cesium hydroxide, cesium carbonate, cesium oxalate and cesium acetate; the silicon source is one or a combination of more of sodium silicate, silica sol, tetraethoxysilane and white carbon black; the aluminum source is one or a combination of more of sodium metaaluminate, aluminum hydroxide and pseudo-boehmite; the phosphorus source is phosphoric acid; each component in the molecular sieve forms a framework structure of the molecular sieve, and the loaded active components are attached to the framework structure to play a role in activating hydrogen bonds; wherein the active component is Ni-xCs, the mass of the active component accounts for 10-30% of the total mass of the catalyst, and x is the mass percentage of simple substance Cs to simple substance Ni, wherein the range of x is 5-20.
The preparation method comprises the following steps:
Step one: the water, the silicon source, the aluminum source, the phosphorus source, the Cs source and the Me source are mixed according to the mole ratio of oxide of 50-100: 0.2-1:1:0.5-1.0:0.1-2: mixing and stirring for 3-5h to obtain initial gel;
Step two: transferring the initial gel into a glass tube of a microwave synthesizer, and carrying out crystallization reaction for 1-24h, preferably 1-6h at 150-200 ℃ after sealing; after the reaction is finished, standing and cooling, centrifugally washing and drying a solid product to obtain the silicon-aluminum-phosphorus molecular sieve; the solid-liquid separation mode can adopt suction filtration or centrifugation, drying can be carried out at the temperature of 75-100 ℃, and the drying time can be set according to the drying temperature and can be generally 6-12h;
Step three: according to the proportion of the mass of the active simple substance component accounting for 10-30% of the total mass of the catalyst, dissolving soluble salt of the required active component into deionized water with the water absorption of one time of the mass of a molecular sieve carrier, fully stirring for 2 hours, adding the mixture into a washed silicon-aluminum-phosphorus molecular sieve, standing and ageing for 12 hours, drying the mixture, roasting for 3 hours in an air atmosphere at 500 ℃, and reducing with hydrogen at 400 ℃ for 2 hours to obtain the bimetallic silicon-aluminum-phosphorus carrier hydrogenation catalyst; wherein the active component is Ni-xCs, the mass of the active component accounts for 10-30% of the total mass of the catalyst, x is the mass percentage of simple substance Cs relative to simple substance Ni, and the range of x is 5-20. In certain embodiments of the present invention, the soluble salts of the active ingredient are nickel nitrate, cesium hydroxide.
The molecular sieve carrier synthesized by the method can load the precursor containing Ni and Cs without ion exchange, and is roasted to obtain NiCs/CsMeAPO dual-function catalyst, compared with the traditional synthesis of AlPO-11 molecular sieve and SAPO-11 molecular sieve, after hetero atoms are introduced into the AlPO-n molecular sieve, the number of acid sites B and L of the molecular sieve is greatly increased, and the acid strength of the molecular sieve carrier is effectively improved. While the supported Ni provides hydrogenation/dehydrogenation activity such that the isomerization process occurring at the acid center is the rate limiting step of the reaction. The introduction of the second metal Cs improves the dispersity of Ni, thereby improving the activity of hydrogenation dehydrogenation. Second, the presence of Cs further improves the reducibility of a portion of NiO, and also prevents Ni from sintering during the reaction. The constructed NiCs/CsMeAPO-11 molecular sieve has high-efficiency synergistic effect of Cs metal, me metal and load metal in pore channels and on a molecular sieve framework, has proper acid strength and acid quantity, and is suitable for preparing biological fuel.
In some embodiments of the invention, a microwave synthesizer can be used for microwave crystallization, the crystallization time is short, and the method is suitable for synthesizing small-dose samples; in other embodiments of the invention, crystallization can be performed by using a hydrothermal synthesis kettle, the crystallization time is longer, and generally can exceed 24 hours, such as 24-48 hours, so that a large number of samples can be synthesized, and the method is suitable for industrial production.
In certain embodiments of the invention, the prepared bimetallic silicon-aluminum-phosphorus carrier hydrogenation catalyst can be used for preparing biological fuel from grease.
The specific hydrodeoxygenation steps are as follows: the weighed catalyst is filled in a constant temperature zone of the reactor, and the upper end of the reaction tube is filled with a ceramic ring, so that the raw materials with lower temperature are preheated. Before the reaction, the catalyst is pretreated for 2 hours at a certain temperature (generally 400 ℃) in an H 2 atmosphere (160 mL/min) so that the loaded oxide is reduced to a zero-valent state, and then the temperature, the pressure and the hydrogen flow rate required by the reaction are set for evaluation (the hydrogen-oil ratio is 800-2000 under the hydrogen pressure of 3-10WPa, and the reaction temperature is 300-400 ℃). The material was taken up every hour and the product was analyzed by gas chromatography.
In some embodiments of the present invention, the grease is kitchen waste oil, and the pretreatment of the oil is performed before the oil is introduced into the reactor, and the pretreatment may be performed according to one or more of the following treatment methods, which are specifically as follows:
pretreatment of kitchen waste oil:
1. Weighing phosphoric acid or citric acid solution with the mass of 0.7% of the kitchen waste oil, adding the phosphoric acid or the citric acid solution into the oil, stirring and reacting for 30min at 85 ℃, then adding distilled water with the mass of 6% of the kitchen waste oil, stirring and reacting for 30min at 75 ℃, standing for 2h at constant temperature, centrifuging, and collecting an oil layer; in the first step, a three-neck flask, an oil bath, and a condensing device are used.
2. Adding distilled water with the mass of 10% of the oil layer, vigorously stirring for 15min at 70 ℃ and 600 r/s, centrifugally collecting the oil layer, and dehydrating at 105 ℃;
3. Adding acid clay with 10% of oil layer mass, heating to 110deg.C, stirring for 1 hr at 500 r, centrifuging, and collecting oil.
The following description of the present invention is made with reference to the accompanying drawings, wherein the experimental methods without specific description of the operation steps are performed according to the corresponding commodity specifications, and the instruments, reagents and consumables used in the embodiments can be purchased from commercial companies without specific description. The following examples are intended to enable those of ordinary skill in the art to more fully understand the invention or to make various insubstantial modifications and adaptations in light of the teachings of the invention and are not intended to limit the scope of what is claimed and include all such claims.
Example 1
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by a template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudo-boehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 0.22g of sodium hydroxide were mixed and stirred at 20℃for 1 hour. And transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, standing and cooling after the reaction is finished, and centrifugally washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: 10.79g of nickel nitrate and 0.71g of cesium hydroxide are dissolved in 8g of deionized water, fully stirred for 2h, added into 8g of carrier A, kept stand and aged for 24h, and the mixture is dried and roasted for 3h in an air atmosphere at 400 ℃ to obtain the catalyst for preparing the biofuel through grease hydrodeoxygenation, and the catalyst is denoted as cat1.
Fig. 1 and 2 show the cat1 catalyst X-ray powder diffraction pattern and scanning electron micrograph, respectively. As can be seen from XRD results, the synthesized molecular sieve has a good crystal structure, and Na and Cs enter a molecular sieve framework; the scanning electron microscope photo shows the grain size and morphology of the molecular sieve, the molecular sieve is in a quadrangular prism shape, and the grain size is 5-8 microns.
Example 2
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by a template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudo-boehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 0.31g of potassium hydroxide were mixed and stirred at 20℃for 1 hour. And transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, standing and cooling after the reaction is finished, and centrifugally washing and drying the solid product to obtain the initial product. And transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, standing and cooling after the reaction is finished, and centrifugally washing and drying the solid product to obtain an initial product A.
(2) Loading of active components: 10.79g of nickel nitrate and 0.71g of cesium hydroxide are dissolved in 8g of deionized water, fully stirred for 2h, added into 8g of carrier A, kept stand and aged for 24h, and the mixture is dried and roasted for 3h in an air atmosphere at 400 ℃ to obtain the catalyst for preparing the biofuel through grease hydrodeoxygenation, and the catalyst is marked as cat2.
Example 3
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by a template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudo-boehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 0.13g of lithium hydroxide were mixed and stirred at 20℃for 1 hour. Transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, standing and cooling after the reaction is finished, and centrifugally washing and drying a solid product to obtain an initial product A.
(2) Loading of active components: 10.79g of nickel nitrate and 0.71g of cesium hydroxide are dissolved in 8g of deionized water, fully stirred for 2h, added into 8g of carrier A, kept stand and aged for 24h, and the mixture is dried and roasted for 3h in an air atmosphere at 400 ℃ to obtain the catalyst for preparing the biofuel through grease hydrodeoxygenation, and the catalyst is marked as cat3.
Example 4
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by a template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudo-boehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 0.32g of magnesium hydroxide were mixed and stirred at 20℃for 1 hour. Transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, standing and cooling after the reaction is finished, and centrifugally washing and drying a solid product to obtain an initial product A.
(2) Loading of active components: 10.79g of nickel nitrate and 0.71g of cesium hydroxide are dissolved in 8g of deionized water, fully stirred for 2h, added into 8g of carrier A, kept stand and aged for 24h, and the mixture is dried and roasted for 3h in an air atmosphere at 400 ℃ to obtain the catalyst for preparing the biofuel through grease hydrodeoxygenation, and the catalyst is marked as cat4.
Example 5
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by a template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudo-boehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 1.74g of barium hydroxide were mixed and stirred at 20℃for 1 hour. Transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, standing and cooling after the reaction is finished, and centrifugally washing and drying a solid product to obtain an initial product A.
(2) Loading of active components: 10.79g of nickel nitrate and 0.71g of cesium hydroxide are dissolved in 8g of deionized water, fully stirred for 2h, added into 8g of carrier A, kept stand and aged for 24h, and the mixture is dried and roasted for 3h in an air atmosphere at 400 ℃ to obtain the catalyst for preparing the biofuel through grease hydrodeoxygenation, and the catalyst is denoted as cat5.
Example 6
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by a template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudo-boehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 0.538g of copper hydroxide were mixed and stirred at 20℃for 1 hour. Transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, standing and cooling after the reaction is finished, and centrifugally washing and drying a solid product to obtain an initial product A.
(2) Loading of active components: 10.79g of nickel nitrate and 0.71g of cesium hydroxide are dissolved in 8g of deionized water, fully stirred for 2h, added into 8g of carrier A, kept stand and aged for 24h, and the mixture is dried and roasted for 3h in an air atmosphere at 400 ℃ to obtain the catalyst for preparing the biofuel through grease hydrodeoxygenation, and the catalyst is marked as cat6.
Example 7
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by a template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudo-boehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 0.491g of manganese hydroxide were mixed and stirred at 20℃for 1 hour. Transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, standing and cooling after the reaction is finished, and centrifugally washing and drying a solid product to obtain an initial product A.
(2) Loading of active components: 10.79g of nickel nitrate and 0.71g of cesium hydroxide are dissolved in 8g of deionized water, fully stirred for 2h, added into 8g of carrier A, kept stand and aged for 24h, and the mixture is dried and roasted for 3h in an air atmosphere at 400 ℃ to obtain the catalyst for preparing the biofuel through grease hydrodeoxygenation, and the catalyst is denoted as cat7.
Comparative example 1
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by a template-free method comprises the following steps: 13g deionized water, 2.3g phosphoric acid, 1.42g pseudo-boehmite, 0.80g silica sol were mixed and stirred at 20℃for 1 hour. Transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, standing and cooling after the reaction is finished, and centrifugally washing and drying a solid product to obtain an initial product A.
(2) Loading of active components: 10.79g of nickel nitrate and 0.71g of cesium hydroxide are dissolved in 8g of deionized water, fully stirred for 2h, added into 8g of carrier A, kept stand and aged for 24h, and the mixture is dried and roasted for 3h in an air atmosphere at 400 ℃ to obtain the catalyst for preparing the biofuel through grease hydrodeoxygenation, and the catalyst is denoted as cat8.
Comparative example 2
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by a template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudo-boehmite, 0.80g of silica sol and 0.96g of cesium hydroxide were mixed and stirred at 20℃for 1 hour. Transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, standing and cooling after the reaction is finished, and centrifugally washing and drying a solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate and 0.71g of cesium hydroxide into 8g of deionized water, fully stirring for 2h, adding into 8g of carrier A, standing for aging for 24h, drying the mixture, and roasting in an air atmosphere at 400 ℃ for 3h to obtain a catalyst for preparing biofuel through grease hydrodeoxygenation, and recording as cat9
Comparative example 3
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by a template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudo-boehmite, 0.80g of silica sol and 0.44g of sodium hydroxide were mixed and stirred at 20℃for 1 hour. Transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, standing and cooling after the reaction is finished, and centrifugally washing and drying a solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate and 0.71g of cesium hydroxide into 8g of deionized water, fully stirring for 2h, adding into 8g of carrier A, standing for aging for 24h, drying the mixture, and roasting in an air atmosphere at 400 ℃ for 3h to obtain the catalyst for preparing the biofuel through grease hydrodeoxygenation, and recording as cat10
Comparative example 4
(1) The preparation method of the bimetallic silicon-aluminum-phosphorus carrier by a template-free method comprises the following steps: 13g of deionized water, 2.3g of phosphoric acid, 1.42g of pseudo-boehmite, 0.80g of silica sol, 0.96g of cesium hydroxide and 0.22g of sodium hydroxide were mixed and stirred at 20℃for 1 hour. Transferring the mixture into a microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, transferring the mixture into the microwave synthesizer, sealing, crystallizing at 190 ℃ for 2 hours, standing and cooling after the reaction is finished, and centrifugally washing and drying a solid product to obtain an initial product A.
(2) Loading of active components: dissolving 10.79g of nickel nitrate into 8g of deionized water, fully stirring for 2 hours, adding into 8g of carrier A, standing for aging for 24 hours, drying the mixture, roasting for 3 hours in an air atmosphere at 400 ℃ to obtain a catalyst for preparing the biofuel through grease hydrodeoxygenation, and recording as cat11
Example 8: catalyst evaluation
1. Pretreatment of kitchen waste oil
Weighing phosphoric acid or citric acid solution with the mass of 0.7% of the kitchen waste oil, adding the phosphoric acid or the citric acid solution into the oil, stirring and reacting for 30min at 85 ℃, then adding distilled water with the mass of 6% of the kitchen waste oil, stirring and reacting for 30min at 75 ℃, standing for 2h at constant temperature, centrifuging, and collecting an oil layer; a three-necked flask, an oil bath, and a condensing unit were used in this step. Then adding distilled water with the mass of 10% of the oil layer, vigorously stirring for 15min at 70 ℃ and 600 r/s, centrifugally collecting the oil layer, and dehydrating at 105 ℃; adding acid clay with the mass of 10% of the oil layer, heating to 110 ℃, stirring for 1h at 500 r, and centrifuging to collect grease.
2. Catalyst evaluation
The weighed catalyst is filled in a constant temperature zone of the reactor, and the upper end of the reaction tube is filled with a ceramic ring, so that the raw materials with lower temperature are preheated. Before the reaction, the catalyst is pretreated for 2 hours at a certain temperature (generally 400 ℃) in an H 2 atmosphere (160 mL/min) so that the loaded oxide is reduced to a zero-valent state, and then the temperature, the pressure and the hydrogen flow rate required by the reaction are set for evaluation (the hydrogen-oil ratio is 800-2000 under the hydrogen pressure of 3-10WPa, and the reaction temperature is 300-400 ℃). The pretreated kitchen waste oil is continuously injected into a fixed bed reactor through an infusion pump at the rate of 0.1-1.0mL/min, then is taken in every hour, and the product is analyzed through gas chromatography. Table 1 is a table of performance evaluation of the products prepared in examples 1-7 and comparative examples 1-4 of the present invention, and the performance of each example and comparative example in catalyzing hydrodeoxygenation of kitchen waste oil can be determined from Table 1.
TABLE 1
The evaluation results are shown in Table 1. Under the same temperature and space velocity conditions, the bimetallic-loaded catalyst product obtains better alkane yield which can reach 60-80 percent. The yield of alkane with single metal or no metal load is about 30-40%. Probably because the constructed bimetallic molecular sieve, the metals in the pore canal and on the molecular sieve framework and the load metal have high-efficiency synergistic effect, the reaction is facilitated to be carried out in the hydrodeoxygenation direction. Secondly, under the same reaction conditions, the bimetallic supported catalyst obtains higher selectivity of C9-C16 components, probably because of the introduction of the second metal, the dispersity of Ni is improved, and the catalyst has more active sites, thereby being beneficial to reaction isomerization cracking.
The foregoing describes the embodiments of the present invention in detail, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.

Claims (9)

1. A preparation method of a silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst is characterized by comprising the following steps of: mixing water, a silicon source, an aluminum source, a phosphorus source, a Cs source and a Me source to prepare initial gel, wherein the mole ratio of the water, the silicon source, the aluminum source, the phosphorus source, the Cs source and the Me source is 50-100 in terms of oxide: 0.2-1:1:0.5-1.0:0.1-2:0.1-2; crystallizing to obtain a silicon-aluminum-phosphorus molecular sieve, wherein the crystallization temperature is 150-200 ℃, and the active metal is loaded to obtain a bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst, wherein Cs metal and Me metal in a pore channel and on a molecular sieve framework have synergistic effect with the loaded active metal; the active metal is Ni-xCs, the mass of the active metal accounts for 10-30% of the total mass of the catalyst, and x is the mass percentage of simple substance Cs to simple substance Ni, wherein the range of x is 5-20;
wherein Me is one of Li, na, K, mg, ba, cu and Mn.
2. The method for preparing the silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst according to claim 1, which is characterized in that: the Me source is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, barium hydroxide, copper hydroxide and manganese hydroxide.
3. The method for preparing the silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst according to claim 1, which is characterized in that: the Cs source is one or a combination of more of cesium hydroxide, cesium carbonate, cesium oxalate and cesium acetate.
4. The method for preparing the silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst according to claim 1, which is characterized in that: the silicon source is one or a combination of more of sodium silicate, silica sol, tetraethoxysilane and white carbon black;
the aluminum source is one or a combination of more of sodium metaaluminate, aluminum hydroxide and pseudo-boehmite;
the phosphorus source is phosphoric acid.
5. The method for preparing the silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst according to claim 1, which is characterized in that: dissolving the soluble salt of the active metal into deionized water with the water absorption of twice the carrier mass, adding the silicon-aluminum-phosphorus molecular sieve, standing, aging, drying and roasting, and reducing with hydrogen to prepare the bimetallic silicon-aluminum-phosphorus molecular sieve hydrogenation catalyst.
6. A bimetallic silicoaluminophosphate molecular sieve hydrogenation catalyst prepared according to the method of preparing the silicoaluminophosphate molecular sieve hydrogenation catalyst of any one of claims 1-5.
7. Use of the bimetallic silicoaluminophosphate molecular sieve hydrogenation catalyst of claim 6 in the preparation of a biofuel.
8. The use of the bimetallic silicoaluminophosphate molecular sieve hydrogenation catalyst according to claim 7 in the preparation of biofuels, characterized in that: the method is applied to preparing the biofuel from the kitchen waste oil.
9. The use of the bimetallic silicoaluminophosphate molecular sieve hydrogenation catalyst according to claim 7 in the preparation of biofuels, characterized in that: firstly, the kitchen waste oil is pretreated, and the method comprises the following steps:
Weighing phosphoric acid or citric acid solution with the mass of 0.5-1% of the kitchen waste oil, adding the phosphoric acid or the citric acid solution into the kitchen waste oil, stirring and reacting at 80-85 ℃, adding distilled water with the mass of 5-8% of the kitchen waste oil, stirring and reacting at 70-75 ℃, standing at constant temperature, centrifuging, and collecting an oil layer;
adding distilled water with the mass of 8-15% of the oil layer, vigorously stirring at 70-75 ℃, centrifuging, and secondarily collecting the oil layer;
adding acid clay with the mass of 8-10% of the oil layer collected for the second time, heating to 100-110 ℃ and stirring, centrifuging and collecting the treated kitchen waste oil.
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