CN108722423B - Preparation method of biomass tar cracking catalyst - Google Patents

Preparation method of biomass tar cracking catalyst Download PDF

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CN108722423B
CN108722423B CN201810464748.5A CN201810464748A CN108722423B CN 108722423 B CN108722423 B CN 108722423B CN 201810464748 A CN201810464748 A CN 201810464748A CN 108722423 B CN108722423 B CN 108722423B
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mixture
rice hulls
preparation
catalyst
cracking catalyst
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CN108722423A (en
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高恒东
胡佳佳
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Wuhu Chuangyuan New Materials Co ltd
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Wuhu Chuangyuan New Materials Co ltd
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention discloses a preparation method of a biomass tar cracking catalyst, which is prepared from ferroferric oxide nanoparticles, octadecyl triethoxysilane, high-carbon organic matters, rice hulls, sodium metaaluminate, nickel nitrate and other raw materials, ferroferric oxide magnetic materials are inserted in the preparation of the catalyst, so that the catalyst is convenient to recover and reuse, deposited carbon is diffused and mixed horizontally by burning the high-carbon organic matters, the doping is more uniform and ordered, more catalytic activity sites and adsorption sites can be reserved, meanwhile, mayenite and a nickel-based catalyst are prepared for compounding, the free oxygen structure is utilized to improve the carbon deposition resistance of the nickel-based catalyst, enhance the catalytic performance and realize the high-efficiency degradation of biomass tar, the raw materials are wide in source, the preparation method is simple, the applicability is strong, the stability of a biomass gasification process can be greatly increased, and the gasification cost is reduced, has higher economic value and environmental value and is suitable for popularization and use of production enterprises.

Description

Preparation method of biomass tar cracking catalyst
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method of a biomass tar cracking catalyst.
Background
In recent years, with the reduction of traditional fossil fuels and the aggravation of environmental pollution problems, biomass energy sources with wide sources and zero emission of CO2 are receiving more and more attention. The biomass gasification technology is one of the most effective and most promising biomass energy utilization means, but not only combustible gas with high calorific value is generated in the biomass gasification process, but also a byproduct, namely tar is generated, and the tar easily blocks a pipeline of a biomass gasification reaction device, so that the normal operation of a system is influenced, and the gasification efficiency is reduced. Therefore, the removal of tar in the gasification process has been a hot issue in the field of biomass gasification. At present, the methods for removing tar at home and abroad are divided into three major categories, namely a biological method, a physical method and a chemical method, wherein the catalytic conversion in the chemical method is considered to be a technically and economically more feasible method.
In the research of catalytic cracking tar of catalysts at home and abroad, the nickel-based catalyst can effectively improve the yield of synthesis gas and has excellent catalytic cracking performance of benzene series and other organic pollutants, so that the nickel-based catalyst is widely concerned by researchers at home and abroad, and when the nickel-based catalyst is inserted into the preparation of the tar cracking catalyst, the quantity of the active centers on the surface of the organic catalytic cracking catalyst can be increased, the breaking rate of carbon-hydrogen bonds in the tar can be improved, and the degradation of the tar can be realized. In the research of biomass gasification, because the catalyst is subjected to carbon deposition and hydrogen sulfide generation in the reaction process, the nickel-based catalyst is always in the risk of inactivation, so that a good compound material and a good carrier are required to be found to enable the catalyst to have the capability of resisting the carbon deposition and the hydrogen sulfide, thereby enhancing the service performance of the catalyst.
The calcium aluminate material has a special free oxygen structure and can react with carbon deposition generated by cracking of organic matters to generate carbon monoxide, so that the stability can be effectively improved by compounding the calcium aluminate material with a nickel-based catalyst. Rice is a typical silicic acid plant, the genetic characteristic of the rice determines that the rice selectively absorbs and enriches more silicon, and the rice has strong adsorbability and large adsorption capacity after carbonization modification treatment. Based on the method, the calcium aluminate material and the rice after carbonization modification treatment are compounded with the nickel-based catalyst and then applied to the preparation of the catalyst, so that the performance of the catalyst can be effectively expanded, the requirements of people are met, and the catalyst has a better use prospect.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a preparation method of a biomass tar cracking catalyst.
The invention is realized by the following technical scheme:
a preparation method of a biomass tar cracking catalyst comprises the following steps:
(1) mixing ferroferric oxide nanoparticles, anhydrous toluene and octadecyltriethoxysilane, uniformly stirring, placing the mixture into a reaction kettle, heating to 130 ℃ and 150 ℃, reacting for 4-6 hours, collecting a product, drying, crushing and sieving by a sieve of 60-80 meshes for later use;
(2) and (3) mixing the high-carbon organic matter with the product obtained in the step (1) according to the mass ratio of (4-5): 1, calcining the mixture in an anoxic state at the calcining temperature of 550-650 ℃ for 3-4 hours, and naturally cooling the mixture to room temperature after the calcining is finished to obtain carbon deposition modified particles for later use;
(3) cleaning rice hulls with water, drying the rice hulls in the sun, crushing the rice hulls, sieving the rice hulls with a 60-80-mesh sieve, sending the rice hulls into a calcining furnace, heating the rice hulls to 600-650 ℃, carrying out aerobic calcination for 4-5 hours, cooling the rice hulls to room temperature, mixing the rice hulls with sodium metaaluminate, adding the mixture into 2mol/L sodium hydroxide solution with the mass being 8-10 times that of the mixture, stirring the mixture for 90-120 minutes in water bath at the temperature of 25-30 ℃, then filling the mixed solution into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, placing the kettle in a drying oven for crystallization for 10-12 hours at the temperature of 120-130 ℃, removing the mixed solution after the crystallization is finished, washing the mixed solution with water until;
(4) calcium hydroxide and aluminum hydroxide are mixed according to a molar ratio of (5-6): 7, putting the materials into a ball mill together, grinding the materials for 4 to 5 hours at 300-: 1: (10-11) adding the mixture into water with the mass of 15-20 times, stirring until solid and liquid are fully mixed, drying the mixture in a drying box at 110 ℃ under 105-;
(5) and (3) stirring and compounding the product obtained in the step (2) and the catalyst obtained in the step (4) according to the mass ratio of (5-10) to (2-6) to obtain the biomass tar cracking catalyst.
The dosage ratio of the ferroferric oxide nanoparticles, the octadecyl triethoxysilane and the anhydrous toluene in the step 1 is (10-12) mmol: (2-3) mmol: (14-16) mL.
And the high-carbon organic matter in the step 2 is any one of glucose, citric acid and malic acid.
In the step 3, the using amount of sodium metaaluminate accounts for 20-25% of the mass of the rice hulls.
And in the step 4, the two times of calcining in the muffle furnace are carried out in an air atmosphere.
The carbon deposition modified particles and the rice hull-based zeolite-supported nickel/mayenite catalyst in the step 5 are mixed according to a mass ratio of 7:3 mixing and treating for 60-90 minutes under 240-300 turns/minute mechanical stirring.
The invention has the advantages that:
the ferroferric oxide magnetic material is inserted into the preparation of the catalyst, so that the catalyst is convenient to recover and reuse, deposited carbon is diffused and mixed horizontally by burning high-carbon organic matters, the doping is more uniform and ordered, more catalytic activity sites and adsorption sites can be reserved, meanwhile, the mayenite is prepared by the calcium hydroxide and the aluminum hydroxide and is compounded with the nickel-based catalyst, the anti-carbon deposition property of the nickel-based catalyst is improved by utilizing the free oxygen structure in the mayenite, the catalytic performance is enhanced, and the multi-step treatment of the rice husk is added to be used as a load to provide a carrying site for the nickel/mayenite catalyst, so that the stability of the combination of the nickel-based catalyst is improved, the strength of a composite material is improved, the number of active centers on the surface of organic catalytic cracking is increased, and the efficient degradation of the biomass tar is realized. The gasification cost is reduced, and the gasification furnace has higher economic value and environmental value and is suitable for popularization and use of production enterprises.
Detailed Description
A preparation method of a biomass tar cracking catalyst comprises the following steps:
(1) ferroferric oxide nano particles, anhydrous toluene and octadecyl triethoxysilane according to the dosage ratio of 11 mmol: 15mL of: 2mmol, stirring uniformly, placing in a reaction kettle, heating to 130 ℃, reacting for 4 hours, collecting the product, drying, crushing and sieving with a 60-mesh sieve for later use;
(2) and (3) mixing glucose with the product obtained in the step (1) according to a mass ratio of 4: 1, calcining the mixture in an anoxic state at 550 ℃ for 3 hours after mixing, and naturally cooling the mixture to room temperature after calcining to obtain carbon deposition modified particles for later use;
(3) washing rice hulls with water, drying the rice hulls in the sun, crushing the rice hulls, sieving the rice hulls with a 60-mesh sieve, feeding the rice hulls into a calcining furnace, heating the rice hulls to 600 ℃, carrying out aerobic calcination for 4 hours, cooling the rice hulls to room temperature, mixing the rice hulls with sodium metaaluminate accounting for 25 percent of the mass of the rice hulls, adding the mixture into 2mol/L sodium hydroxide solution accounting for 8 times of the mass of the rice hulls, stirring the mixture in water bath at 25 ℃ for 90 minutes, then filling the mixed solution into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a drying oven for crystallization at 120 ℃ for 10 hours, removing the mixed solution after the crystallization;
(4) calcium hydroxide and aluminum hydroxide are mixed according to a molar ratio of 5: 7, putting the mixture into a ball mill together, grinding the mixture for 4 hours at 300 revolutions per minute, then calcining the mixture for 3 hours at 700 ℃ in a muffle furnace, and grinding the mixture to obtain the nickel nitrate and the product obtained in the step 3 according to the mass ratio of 3: 1: 11, adding the mixture into water with the mass 15 times that of the mixture, stirring the mixture until solid and liquid are fully mixed, drying the mixture in a drying box at 105 ℃, and then sending the dried mixture into a muffle furnace to calcine the mixture for 4 hours at 800 ℃, wherein the two times of the calcination in the muffle furnace are carried out in the air atmosphere to obtain the nickel/mayenite catalyst loaded on the rice hull-based zeolite for later use;
(5) and (3) mixing the product obtained in the step (2) with the catalyst obtained in the step (4) according to the mass ratio of 7:3, and treating for 80 minutes under the mechanical stirring of 260 revolutions per minute to obtain the biomass tar cracking catalyst.

Claims (5)

1. The preparation method of the biomass tar cracking catalyst is characterized by comprising the following steps: (1) mixing ferroferric oxide nanoparticles, anhydrous toluene and octadecyltriethoxysilane, uniformly stirring, placing the mixture into a reaction kettle, heating to 130 ℃ and 150 ℃, reacting for 4-6 hours, collecting a product, drying, crushing and sieving by a sieve of 60-80 meshes for later use; (2) mixing glucose with the product obtained in the step 1 according to the mass ratio of (4-5): 1, calcining the mixture in an anoxic state at the calcining temperature of 550-650 ℃ for 3-4 hours, and naturally cooling the mixture to room temperature after the calcining is finished to obtain carbon deposition modified particles for later use; (3) cleaning rice hulls with water, drying the rice hulls in the sun, crushing the rice hulls, sieving the rice hulls with a 60-80-mesh sieve, sending the rice hulls into a calcining furnace, heating the rice hulls to 600-650 ℃, carrying out aerobic calcination for 4-5 hours, cooling the rice hulls to room temperature, mixing the rice hulls with sodium metaaluminate, adding the mixture into 2mol/L sodium hydroxide solution with the mass being 8-10 times that of the mixture, stirring the mixture for 90-120 minutes in water bath at the temperature of 25-30 ℃, then filling the mixed solution into a hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, then placing the hydrothermal reaction kettle in an oven, crystallizing the mixture for 10-12 hours at the temperature of 120-130 ℃, removing the mixed solution after the crystallization is finished, washing the mixed; (4) calcium hydroxide and aluminum hydroxide are mixed according to a molar ratio of (5-6): 7, putting the materials into a ball mill together, grinding for 4-5 hours at 300-: 1: (10-11) adding the mixture into water with the mass of 15-20 times, stirring until solid and liquid are fully mixed, drying the mixture in a drying box at 110 ℃ under 105-; (5) and (3) stirring and compounding the product obtained in the step (2) and the catalyst obtained in the step (4) according to the mass ratio of (5-10) to (2-6) to obtain the biomass tar cracking catalyst.
2. The preparation method of the biomass tar cracking catalyst according to claim 1, wherein the usage ratio of the ferroferric oxide nanoparticles, the octadecyl triethoxysilane, and the anhydrous toluene in the step 1 is (10-12) mmol: (2-3) mmol: (14-16) mL.
3. The preparation method of the biomass tar cracking catalyst according to claim 1, wherein the amount of sodium metaaluminate used in the step 3 is 20-25% of the mass of the rice hulls.
4. The method for preparing the biomass tar cracking catalyst according to claim 1, wherein the two times of the calcination in the muffle furnace in the step 4 are both performed in an air atmosphere.
5. The method for preparing a biomass tar cracking catalyst according to claim 1, wherein the carbon deposit modified particles and the rice husk based zeolite supported nickel/mayenite catalyst in the step 5 are mixed in a mass ratio of 7:3 mixing and treating for 60-90 minutes under 240-300 turns/minute mechanical stirring.
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CN102179247A (en) * 2011-03-21 2011-09-14 上海大学 Method for preparing hollow spherical nickel-based catalyst for catalytic pyrolysis of oil tar
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