CN114471648B - Carrier and catalyst for integral tar cracking and preparation method thereof - Google Patents

Carrier and catalyst for integral tar cracking and preparation method thereof Download PDF

Info

Publication number
CN114471648B
CN114471648B CN202011164876.1A CN202011164876A CN114471648B CN 114471648 B CN114471648 B CN 114471648B CN 202011164876 A CN202011164876 A CN 202011164876A CN 114471648 B CN114471648 B CN 114471648B
Authority
CN
China
Prior art keywords
monolithic
carrier
tar cracking
producing
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011164876.1A
Other languages
Chinese (zh)
Other versions
CN114471648A (en
Inventor
张彪
宋永一
王鑫
吴斯侃
王博
蔡海乐
赵丽萍
刘继华
张长安
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN202011164876.1A priority Critical patent/CN114471648B/en
Publication of CN114471648A publication Critical patent/CN114471648A/en
Application granted granted Critical
Publication of CN114471648B publication Critical patent/CN114471648B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
    • 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
    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—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
    • 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
    • B01J23/70—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
    • B01J23/83—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 rare earths or actinides
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/866—Nickel and chromium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00—Details of gasification apparatus
    • C10J2200/06—Catalysts as integral part of gasifiers
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Toxicology (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Electromagnetism (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a carrier for integral tar cracking, a catalyst and a preparation method thereof. The catalyst prepared by the carrier has adjustable porosity, large specific surface area, high activity, high microwave absorptivity, good thermal shock resistance, strong water resistance at high temperature, sintering resistance, carbon deposit resistance and long-term high-efficiency use.

Description

Carrier and catalyst for integral tar cracking and preparation method thereof
Technical Field
The invention belongs to the technical field of biomass energy treatment, and particularly relates to a catalytic material for preparing a hydrocarbon product and realizing tar conversion by biomass catalytic pyrolysis and a preparation method thereof.
Background
The biological tar components are complex and difficult to remove, and the pipeline blockage and environmental pollution caused by the biological tar components are one of the reasons for the stagnation of many biomass pyrolysis gasification processes. Catalytic cracking has been attracting attention as a tar removal process with great potential, and the complexity and removal effect of the process depend on the activity and life of the tar cracking catalyst.
The fixed bed process is simple, the technology is mature, and the catalytic cracking method is used for researching more reactor types, but the requirement on the performance of the catalyst is higher. The biological tar catalytic pyrolysis process is often followed by the biomass pyrolysis gasification process, and gasification gas carries biological tar with complex components, a large amount of water vapor and solid particles to pass through a catalyst bed, so that tar pyrolysis reaction is a collection of a series of complex reactions. The great dilution of the gasification gas and the great difference in bio-tar molecules require that the catalyst must possess a high specific surface area, thereby increasing the adsorption capacity and residence time of the tar molecules. Meanwhile, the tar cracking catalyst works at 600-1000 ℃ and also resists the impact and poisoning effects of solid particles and water vapor, so the tar cracking catalyst must have good permeability, high-temperature stability, corrosion resistance and the like.
Foam silicon carbide is a potential catalyst material due to its excellent high temperature properties, thermal shock resistance, wear resistance, corrosion resistance, oxidation resistance, creep resistance, low coefficient of thermal expansion and high thermal conductivity, and good stability even under severe conditions. However, the specific surface area of the conventional foam silicon carbide is often small, the chemical inertness of the surface of the conventional foam silicon carbide also causes weak bonding force between the active metal and the carrier, and poor dispersing and loading effects of the active metal, which are problems to be overcome when the foam silicon carbide is used as a catalyst carrier.
CN103055882a discloses a preparation method of a multi-metal monolithic tar cracking catalyst, which adopts cordierite after acid pretreatment as a carrier, and carries out loading of metals such as nickel, cobalt, molybdenum and the like, so as to prepare the monolithic tar cracking catalyst. CN107715884a discloses a metal supported biomass semicoke catalyst and a preparation method thereof, wherein the preparation method is that biomass precursors are immersed in water solution of soluble salt of metal active components in an equal volume, and are pyrolyzed after being dried, so as to obtain the catalyst for catalyzing tar steam reforming reaction. However, the catalyst cannot simultaneously achieve the performances of high specific surface area, active component stability, sintering resistance, high-temperature water resistance and the like, and has certain disadvantages.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a carrier for integral tar cracking, a catalyst and a preparation method thereof. The catalyst has the advantages of reduced pressure, adjustable porosity, large specific surface area, high activity, high microwave absorptivity, good thermal shock resistance, strong water resistance at high temperature, sintering resistance, carbon deposit resistance and long-term high-efficiency use. Solves the problems that the existing tar cracking catalyst can not simultaneously realize the performances of high-temperature stability, water resistance, high specific surface area, high load capacity, sintering resistance, carbon deposit resistance and the like.
The first aspect of the invention provides a preparation method of a carrier for monolithic tar cracking, which comprises the following steps:
(1) Mixing the carbon precursor, the activating agent and the auxiliary agent A solution uniformly to obtain slurry A;
(2) Adding polyurethane foam into the slurry A for soaking, and then roasting and washing to obtain a carbon template;
(3) Mixing a silicon source with the solution of the auxiliary agent B, and regulating and controlling the pH value of the system to be 1-10 to obtain slurry B;
(4) And (3) adding the carbon template obtained in the step (2) into the slurry B for soaking, adding a sample obtained after the soaking and roasting into hydrofluoric acid solution for treatment, and further washing to obtain the carrier.
In the above method for preparing the monolithic tar cracking carrier, the carbon precursor in the step (1) may be one or more of phenolic resin, starch, dextrin, glycerol, and water-soluble polysaccharide, preferably phenolic resin and/or starch, and more preferably water-soluble phenolic resin.
In the preparation method of the carrier for integral tar cracking, the activating agent in the step (1) is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, zinc chloride and phosphoric acid, preferably potassium hydroxide.
In the preparation method of the carrier for integral tar cracking, the auxiliary agent A solution in the step (1) comprises an auxiliary agent A, a solvent and water, wherein the auxiliary agent A is one or more of tetramethylammonium hydroxide, polyethylene glycol (with the molecular weight of 200-8000), tritonX100, ammonium polymethacrylate, polyethyleneimine, polyacrylamide, sodium lignin sulfonate, carboxymethyl cellulose, triglyceride and polyetherimide, preferably one or more of tetramethylammonium hydroxide, polyethylene glycol (with the molecular weight of 200-8000) and carboxymethyl cellulose. The solvent is an organic solvent, preferably an alcohol solvent, specifically one or more of ethanol, methanol, propanol, butanol, ethylene glycol, propylene glycol, glycerol and butanediol, and more preferably ethanol. Based on the mass of the auxiliary agent solution, the mass concentration of the auxiliary agent A is 0.1-10wt%, and the mass concentration of the solvent is 0.1-80wt%.
In the preparation method of the carrier for integral tar cracking, the mixing temperature in the step (1) is 20-80 ℃. Taking the dry basis mass of the activator as a reference, the dry basis content of the auxiliary agent A is 1-10wt%; the mass ratio of the activator to the carbon precursor is 0.2-5:1.
In the method for producing the monolithic tar cracking support, the polyurethane foam in the step (2) is a flexible polyurethane foam having pores with a pore size of 5 to 200 ppi (pore per inch) and interconnected pores. Further preferably, the polyurethane foam in the step (2) of the present invention may be obtained by modifying the existing polyurethane foam material by immersing the polyurethane foam material in an acid or alkali solution and then washing. The acid can be one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and citric acid, and the mass concentration of the acid is 1-20wt%; the alkali can be one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide, the mass concentration of the alkali is 1-20wt%, and the soaking time is 1-10 hours. The washing is carried out with deionized water for 2 to 6 times, and the washing is further preferably carried out under ultrasonic conditions.
In the preparation method of the carrier for integral tar cracking, the roasting temperature in the step (2) is 350-900 ℃, the roasting time is 2-10 hours, the roasting is performed in the presence of nitrogen or inert gas, and the inert gas is one or more of helium, neon, argon, krypton and xenon.
In the preparation method of the carrier for integral tar cracking, in the step (2), the washing is carried out by using an acid solution or deionized water until no activator ion is detected, wherein the acid can be one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and citric acid, the mass concentration of the acid solution is 1-20wt%, and the washing temperature is 20-80 ℃.
In the preparation method of the carrier for integral tar cracking, the impregnating step in the step (2) is as follows: and immersing polyurethane foam into the slurry A, taking out, draining, drying in a vacuum drier at 60-150 ℃ for 5-35 min, taking out, and repeating the above process for 5-10 times.
In the preparation method of the carrier for integral tar cracking, the silicon source in the step (3) is one or more of sodium silicate, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and isopropyl orthosilicate; sodium silicate and/or ethyl orthosilicate are preferred.
In the preparation method of the carrier for integral tar cracking, the auxiliary agent B solution in the step (3) comprises an auxiliary agent B, a solvent and water, wherein the auxiliary agent B is one or more of carboxymethyl cellulose, hydroxyethyl cellulose, microcrystalline cellulose, chitosan, sesbania powder, hydroxypropyl methyl cellulose, polyvinyl alcohol (molecular weight is 5000-150000), silicone oil, hexamethylenetetramine, silica sol and aluminum dihydrogen phosphate, and is preferably one or more of carboxymethyl cellulose, sesbania powder, polyvinyl alcohol (molecular weight is 5000-150000) and hexamethylenetetramine; the solvent is an organic solvent, preferably an alcohol solvent, specifically one or more of ethanol, methanol, propanol, butanol, ethylene glycol, propylene glycol, glycerol and butanediol, and more preferably ethanol. The mass concentration of the auxiliary agent B is 0.1-20wt% based on the mass of the auxiliary agent B solution, and the mass concentration of the solvent is 0.1-80wt%.
In the preparation method of the carrier for integral tar cracking, the pH value of the regulating system in the step (3) is 1-10, and the pH value can be regulated by adding acid or ammonia water, wherein the acid can be one or more of nitric acid, hydrochloric acid, phosphoric acid, oxalic acid and citric acid.
In the preparation method of the carrier for integral tar cracking, the mixing temperature in the step (3) is 20-120 ℃. The dry basis weight of the auxiliary agent B is 1-10wt% based on the dry basis weight of the silicon source.
In the preparation method of the monolithic tar cracking carrier, the impregnating step in the step (4) is as follows: immersing the carbon template obtained in the step (2) into the slurry B, taking out, blowing off redundant slurry among holes by using compressed air, drying in a vacuum dryer at 60-150 ℃ for 5-35 min, taking out, and repeating the process for 5-10 times.
In the preparation method of the carrier for integral tar cracking, the roasting temperature in the step (4) is 1200-1900 ℃; the roasting time is 3 to 24 hours, preferably 7 to 15 hours, and the roasting is further preferably performed in the presence of nitrogen or an inert gas, wherein the inert gas is one or more of helium, neon, argon, krypton and xenon. The calcination is further preferably calcination under microwave conditions.
In the preparation method of the carrier for integral tar cracking, the concentration of the hydrofluoric acid solution in the step (4) is 20-40 wt% and the treatment time is 5-12 hours.
In the above method for preparing a carrier for monolithic tar cracking, the washing in step (4) is carried out 2 to 6 times with deionized water, and the washing is further preferably carried out under ultrasonic conditions.
The second aspect of the invention provides a method for preparing a second monolithic tar cracking carrier, which further comprises the steps of (5) carrying out high-temperature treatment on the carrier obtained in the step (4) in the presence of oxygen-containing gas, mixing the treated material with alkaline solution or hydrofluoric acid solution for treatment, and then washing, drying and roasting to obtain the carrier.
In the above method for producing a monolithic tar cracking support, the high-temperature treatment temperature in step (5) is 800 to 1300 ℃, preferably 950 to 1300 ℃, more preferably 1000 to 1300 ℃, and the treatment time is 0.5 to 8 hours, preferably 4 to 6 hours.
In the preparation method of the carrier for integral tar cracking, the oxygen-containing atmosphere in the step (5) may be any one of air, oxygen, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and inert gas, wherein the volume content of oxygen in the mixed gas is 5-100%; the inert gas is one or more of helium, neon, argon, krypton and xenon.
In the above method for preparing the monolithic tar cracking support, the alkaline solution in step (5) is an inorganic alkaline solution, and may be one or more of sodium hydroxide, potassium hydroxide, and lithium hydroxide, preferably sodium hydroxide and/or potassium hydroxide, and more preferably sodium hydroxide.
In the preparation method of the carrier for integral tar cracking, the mass ratio of the material obtained after the high-temperature treatment in the step (5) to the alkaline solution or the hydrofluoric acid solution is 1:80-1:10, the concentration of the alkaline solution is 0.1-20wt%, and the concentration of the hydrofluoric acid solution is 0.01-5wt%.
In the preparation method of the carrier for integral tar cracking, the mixing treatment temperature in the step (5) is 60-120 ℃ and the treatment time is 0.5-5 hours.
In the above method for preparing a carrier for monolithic tar cracking, the washing in step (5) is carried out 2 to 6 times with deionized water, and the washing is further preferably carried out under ultrasonic conditions. The drying temperature in the step (5) is 100-150 ℃, and drying is preferably carried out under the microwave condition; the calcination temperature in the step (5) is 650 to 1000 ℃ and the calcination time is 3 to 9 hours, and the calcination is preferably performed under nitrogen or inert gas, and more preferably under microwave conditions.
In a third aspect, the present invention provides a method for preparing a third monolithic tar cracking support, the method further preferably comprising the step (6), adding the support obtained in the step (5) into a carbon-containing precursor solution for impregnation, and then drying and roasting the mixture to obtain the support, wherein the roasting is performed under a nitrogen atmosphere.
In the preparation method of the monolithic tar cracking carrier, in the step (6), the carbon-containing precursor is one or more of monosaccharide, disaccharide, water-soluble polysaccharide, phenolic resin, starch, dextrin and glycerol, preferably sucrose and/or phenolic resin.
In the preparation method of the carrier for integral tar cracking, the mass fraction of the carbon-containing precursor solution in the step (6) is 1-25%, and the impregnation temperature in the step (6) is 20-90 ℃.
In the above-mentioned method for producing a carrier for monolithic tar cracking, the drying temperature in the step (6) is 100 to 150 ℃, and drying is preferably performed under microwave conditions.
In the above method for producing a monolithic tar cracking support, the baking temperature in step (6) is 1000 to 1600 ℃, preferably 1100 to 1500 ℃, and the treatment time is 0.5 to 4 hours, and more preferably baking under microwave conditions.
The fourth aspect of the invention provides a monolithic tar cracking carrier, which is obtained by the first preparation method, and is foam silicon carbide.
In a fifth aspect, the present invention provides a monolithic tar cracking support, the support being obtainable by the second preparation method described above. The carrier is modified foam silicon carbide, and the modified foam silicon carbide comprises foam silicon carbide and silicon oxide dispersed on the surface of the foam silicon carbide.
The sixth aspect of the invention provides a monolithic tar cracking carrier, which is obtained by the third preparation method. The carrier is modified foam silicon carbide, and the modified foam silicon carbide comprises foam silicon carbide, and silicon oxide and silicon nitride dispersed on the surface of the foam silicon carbide.
In a seventh aspect, the present invention provides a monolithic tar cracking catalyst comprising a support and an active metal component, the catalyst support employing the support provided in the fourth aspect above.
In the monolithic tar cracking catalyst, the content of the carrier is 60-99%, preferably 80-98% by weight, and the content of the active metal component is 1-40% by weight, preferably 2-20% by weight, based on the weight of the catalyst.
The specific properties of the monolithic tar cracking catalyst are as follows: specific surface area of 55-600m 2 And/g, the pore volume is larger than 0.01mL/g.
An eighth aspect of the present invention provides a monolithic tar cracking catalyst comprising a support and an active metal component, the catalyst support employing the support provided in the fifth aspect above.
In the monolithic tar cracking catalyst, the content of the carrier is 60-99%, preferably 80-98% by weight, and the content of the active metal component is 1-40% by weight, preferably 2-20% by weight, based on the weight of the catalyst.
The specific properties of the monolithic tar cracking catalyst are as follows: specific surface area of 55-600m 2 And/g, the pore volume is larger than 0.01mL/g.
A ninth aspect of the present invention provides a monolithic tar cracking catalyst comprising a support and an active metal component, the catalyst support employing the support provided in the sixth aspect above.
In the monolithic tar cracking catalyst, the content of the carrier is 60-99%, preferably 80-98% by weight, and the content of the active metal component is 1-40% by weight, preferably 2-20% by weight, based on the weight of the catalyst.
The specific properties of the monolithic tar cracking catalyst are as follows: specific surface area of 55-600m 2 And/g, the pore volume is larger than 0.01mL/g.
In the three tar cracking catalysts, the active metal component is the firstGroup metal, th->Group B metal->One or more of B group metals, wherein VIII group metal is one or more of iron, nickel, cobalt and palladium, and +.>The B group metal is one or more of chromium, molybdenum and tungsten, and is +.>The B group metal is one or more of manganese and rhenium; the active metal component is further preferably iron and/or nickel.
In the integral tar cracking catalyst, the catalyst further comprises an auxiliary agent, wherein the auxiliary agent is one or more of magnesium, strontium, cerium, zirconium, lanthanum, ytterbium and copper compounds. The content of the auxiliary agent is 0.01-1% based on the weight of the catalyst.
The tenth aspect of the present invention provides a method for preparing the monolithic tar cracking catalyst, which comprises the following steps: and adding the prepared carrier into impregnating solution, and drying and roasting after the impregnation is finished to obtain the catalyst.
In the preparation method of the integral tar cracking catalystThe components of the impregnating solution are as followsGroup metal salt solution, th->Group B metal salt solution, +.>One or more of group B metal salt solutions, preferably iron salts and/or nickel salts; wherein the ferric salt is one or more of ferric nitrate, ferrous acetate, ferrous nitrate and ferric acetylacetonate, and is further preferably ferric nitrate and/or ferrous acetate; the nickel salt is one or more of nickel chloride, nickel nitrate, nickel acetate and nickel acetylacetonate, and further preferably is nickel nitrate and/or nickel acetate. The pH value of the impregnating solution is 1-10, and the pH value of the impregnating solution can be regulated by acid, and can be one or more of nitric acid, hydrochloric acid, phosphoric acid, oxalic acid and citric acid.
In the preparation method of the integral tar cracking catalyst, the impregnating solution can also contain an auxiliary agent precursor, and the auxiliary agent precursor can be one or more of magnesium acetate, strontium nitrate, cerium nitrate, zirconyl nitrate, lanthanum nitrate, ytterbium nitrate and copper nitrate.
In the preparation method of the integral tar cracking catalyst, the impregnation temperature is between normal temperature and 90 ℃.
In the preparation method of the integral tar cracking catalyst, the drying temperature is 100-150 ℃, and drying is preferably carried out under the microwave condition; the roasting temperature is 650-1000 ℃ and the roasting time is 3-9 hours, wherein the roasting is preferably performed under the condition of nitrogen or inert gas, and more preferably under the condition of microwaves.
Compared with the prior art, the carrier for integral tar cracking, the catalyst and the preparation method thereof have the following advantages:
1. the catalyst for integral tar cracking takes the modified foam silicon carbide material as a carrier, and the carrier has good chemical stability, thermal stability, strength, heat conduction and electric conduction. The monolithic tar cracking catalyst obtained by loading the metal with the carrier has stable performance in a high-temperature environment of tar cracking reaction, and has higher catalyst activity and longer catalyst life.
2. According to the preparation method of the carrier for integral tar cracking, provided by the invention, under the action of an activating agent, the high specific surface area carbon template is prepared by in-situ pyrolysis carbonization by using an organic template impregnation process, and then the high specific surface area foam silicon carbide carrier is prepared by using a template method taking high specific surface area foam carbon as a template, wherein the specific surface area of the carrier can be controlled by different pyrolysis carbonization conditions. The high specific surface area of the foam silicon carbide improves the metal loading, so that the catalyst has higher catalytic cracking tar activity. Meanwhile, the drying and sintering treatment under the microwave condition solves the problems of easy deformation and collapse of the carrier structure caused by uneven sintering under the low-auxiliary agent condition, and ensures that the foam silicon carbide carrier with high specific surface area has higher mechanical strength.
3. The integral type carrier for tar cracking has uniform pores, the shape and the porosity of the carrier can be regulated and controlled by selecting polyurethane foams with different shapes and pore diameters, and the modified foam silicon carbide material has good permeability, so that the bed lamination can be reduced, the occurrence probability of channeling is reduced, the utilization rate of the catalyst is improved, and the high-flux gas treatment reaction with higher solid particle content can be tolerated. Meanwhile, the modified foam silicon carbide material has a three-dimensional network open-cell structure which is communicated with each other, the continuity of the structure is favorable for exerting the advantages of high silicon carbide heat conductivity and high far infrared emissivity, the reaction heat can be effectively transferred in the catalytic reaction process, and the modified foam silicon carbide material is suitable for tar cracking which is a strong endothermic reaction. The modified foam silicon carbide material has strong microwave absorption capacity because microwaves are continuously absorbed, reflected and lost in the three-dimensional network structure.
4. According to the preparation method of the carrier for integral tar cracking, disclosed by the invention, the problems that the binding force between active metal and the carrier is weak, the active metal is easy to agglomerate and even fall off and the like caused by chemical inertness of silicon carbide are solved by modifying foam silicon carbide. The high-temperature oxidation atmosphere treatment enables a controllable extremely thin oxide layer to be formed on the surface of the carrier, so that acting force between the carrier and the active metal component can be effectively improved, and stability of the active metal is ensured. The high temperature nitriding atmosphere treatment in another embodiment forms weak alkaline centers with silicon nitride as a main component on the surface of the carrier, and helps to improve the carbon deposit resistance and catalytic activity of the catalyst, so that the catalyst has longer service life.
Drawings
Figure 1 shows the XRD pattern of the support obtained in example 3 of the present invention.
FIG. 2 is an XRD pattern of the support obtained in example 5 of the present invention.
Detailed Description
The details and effects of the method of the present invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
The water-soluble phenolic resin, potassium hydroxide, polyethylene glycol (molecular weight 400) and carboxymethyl cellulose are slowly dissolved in deionized water containing 30wt% of ethanol under stirring at 25 ℃ to obtain slurry A. Wherein, based on potassium hydroxide, the content of polyethylene glycol (molecular weight is 400) is 1wt%, the content of carboxymethyl cellulose is 1.5wt%, and the mass ratio of potassium hydroxide to water-soluble phenolic resin is 1:1.
A soft polyurethane foam with a pore size of 50 ppi (pore per inch) and mutually communicated pores is selected as a template, firstly cut into a certain shape, then soaked in 10wt% NaOH solution for 5 hours, finally placed in deionized water for ultrasonic treatment for 5 minutes, then washed by the deionized water and repeated for 5 times. Immersing the polyurethane foam into the slurry A, taking out, draining, drying in a vacuum drier at 120 ℃ for 35min, taking out, repeating the process for 5 times, keeping the temperature at 600 ℃ for 3 hours in a nitrogen atmosphere, cooling, and washing with 5wt% hydrochloric acid solution at 25 ℃ until no activator ion is detected, thus obtaining the carbon template.
Sesbania powder and polyvinyl alcohol (average molecular weight is 22000) are dissolved in deionized water containing 25wt% of ethanol, the pH is adjusted to 3 by oxalic acid, and ethyl orthosilicate is slowly added under stirring at 60 ℃ to enable the solution to be slowly changed into slurry, so that slurry B is obtained. Wherein, the weight percent of sesbania powder is 5 percent and the weight percent of polyvinyl alcohol is 1 percent based on the weight of tetraethoxysilane. Immersing the carbon template into the slurry B, taking out, blowing off redundant slurry among holes by using compressed air, drying in a vacuum dryer at 120 ℃ for 35min, taking out, and repeating the process for 5 times. The dried carrier is sent into a microwave roasting furnace, kept at the constant temperature of 1700 ℃ for 15 hours in an argon atmosphere, soaked in 40wt% hydrofluoric acid solution for 12 hours, placed into deionized water for ultrasonic treatment for 5 minutes, and then washed by the deionized water and repeated for 5 times.
The carrier prepared above was put into an impregnating solution at 80 ℃. The impregnating solution contains ferric nitrate, nickel nitrate and lanthanum nitrate, and the pH value is adjusted to 3 by nitric acid. Based on the weight of the catalyst, the iron content is 8%, the nickel content is 2%, and the lanthanum content is 0.5%. Drying the impregnated catalyst at 120 ℃, then sending the catalyst into a microwave roasting oven, and keeping the temperature at 800 ℃ for 3 hours in a nitrogen atmosphere.
Example 2
Glycerin, potassium hydroxide, and carboxymethyl cellulose were slowly dissolved in deionized water containing 0.1wt% ethanol with stirring at 120 ℃ to obtain slurry a. Wherein, based on potassium hydroxide, the content of carboxymethyl cellulose is 1wt%, and the mass ratio of potassium hydroxide to glycerin is 0.2:1.
A soft polyurethane foam with a pore size of 5ppi (pores per inch) and mutually communicated pores is selected as a template, firstly cut into a certain shape, then soaked in a KOH solution with the weight of 1 percent for 1 hour, finally placed in deionized water for ultrasonic treatment for 5 minutes, then washed by the deionized water and repeated for 5 times. Immersing the polyurethane foam into the slurry A, taking out, draining, drying in a vacuum drier at 150 ℃ for 5min, taking out, repeating the process for 10 times, keeping the temperature at 900 ℃ for 2 hours in a nitrogen atmosphere, cooling, and washing with 1wt% hydrochloric acid solution at 25 ℃ until no activator ion is detected, thus obtaining the carbon template.
Hydroxypropyl methylcellulose and polyvinyl alcohol (average molecular weight 22000) were dissolved in deionized water containing 10wt% ethanol, the pH was adjusted to 5 with citric acid, and isopropyl orthosilicate was slowly added with stirring at 80℃to make the solution slowly into a slurry, to obtain slurry B. Wherein, the content of hydroxypropyl methylcellulose is 0.5wt% and the content of polyvinyl alcohol is 0.2wt% based on the mass of isopropyl orthosilicate. Immersing the carbon template into the slurry B, taking out, blowing off redundant slurry among holes by using compressed air, drying in a vacuum dryer at 100 ℃ for 35min, taking out, and repeating the process for 10 times. The dried carrier is sent into a microwave roasting furnace, kept at the constant temperature of 1900 ℃ for 15 hours in an argon atmosphere, soaked in 40wt% hydrofluoric acid solution for 12 hours, placed into deionized water for ultrasonic treatment for 5 minutes, and then washed by the deionized water and repeated for 5 times.
The carrier prepared above was put into an impregnating solution at 80 ℃. The impregnating solution contains ferric nitrate, nickel nitrate and chromium nitrate, and the pH value is adjusted to 5 by nitric acid. Based on the weight of the catalyst, the iron content is 0.5%, the nickel content is 1.5%, and the chromium content is 0.5%. Drying the impregnated catalyst at 120 ℃, then sending the catalyst into a microwave roasting oven, and keeping the temperature at 800 ℃ for 3 hours in a nitrogen atmosphere.
Example 3
The water-soluble phenolic resin, potassium hydroxide, polyethylene glycol (molecular weight 400) and carboxymethyl cellulose are slowly dissolved in deionized water containing 30wt% of ethanol under stirring at 25 ℃ to obtain slurry A. Wherein, based on potassium hydroxide, the content of polyethylene glycol (molecular weight is 400) is 1wt%, the content of carboxymethyl cellulose is 1.5wt%, and the mass ratio of potassium hydroxide to water-soluble phenolic resin is 1:1.
A soft polyurethane foam with a pore size of 50 ppi (pore per inch) and mutually communicated pores is selected as a template, firstly cut into a certain shape, then soaked in 10wt% NaOH solution for 5 hours, finally placed in deionized water for ultrasonic treatment for 5 minutes, then washed by the deionized water and repeated for 5 times. Immersing the polyurethane foam into the slurry A, taking out, draining, drying in a vacuum drier at 120 ℃ for 35min, taking out, repeating the process for 5 times, keeping the temperature at 600 ℃ for 3 hours in a nitrogen atmosphere, cooling, and washing with 5wt% hydrochloric acid solution at 25 ℃ until no activator ion is detected, thus obtaining the carbon template.
Sesbania powder and polyvinyl alcohol (average molecular weight is 22000) are dissolved in deionized water containing 25wt% of ethanol, the pH is adjusted to 3 by oxalic acid, and ethyl orthosilicate is slowly added under stirring at 60 ℃ to enable the solution to be slowly changed into slurry, so that slurry B is obtained. Wherein, the weight percent of sesbania powder is 5 percent and the weight percent of polyvinyl alcohol is 1 percent based on the weight of tetraethoxysilane. Immersing the carbon template into the slurry B, taking out, blowing off redundant slurry among holes by using compressed air, drying in a vacuum dryer at 120 ℃ for 35min, taking out, and repeating the process for 5 times.
The dried carrier is sent into a microwave roasting furnace, kept at the constant temperature of 1700 ℃ for 15 hours in an argon atmosphere, soaked in 40wt% hydrofluoric acid solution for 12 hours, placed into deionized water for ultrasonic treatment for 5 minutes, and then washed by the deionized water and repeated for 5 times. The carrier is sent into a microwave roasting oven and kept at a constant temperature of 1300 ℃ for 4 hours in an oxygen atmosphere. Cooling, putting into NaOH solution with concentration of 2wt%, heating slowly to 120 deg.C, treating for 2 hours, cooling, putting into deionized water, ultrasonic treating for 5 min, washing with deionized water, repeating for 5 times, taking out, drying at 120 deg.C, and roasting at 800 deg.C for 3 hours.
The carrier prepared above was put into an impregnating solution at 80 ℃. The impregnating solution contains ferric nitrate, nickel nitrate and lanthanum nitrate, and the pH value is adjusted to 3 by nitric acid. Based on the weight of the catalyst, the iron content is 8%, the nickel content is 2%, and the lanthanum content is 0.5%. Drying the impregnated catalyst at 120 ℃, then sending the catalyst into a microwave roasting oven, and keeping the temperature at 800 ℃ for 3 hours in a nitrogen atmosphere.
Example 4
Phenolic resin, zinc chloride, polyethylene glycol (molecular weight 4000) and tetramethylammonium hydroxide were slowly dissolved in deionized water containing 80wt% ethanol with stirring at 60 ℃ to give slurry a. Wherein, based on zinc chloride, the content of polyethylene glycol (molecular weight is 4000) is 5wt%, the content of tetramethylammonium hydroxide is 0.5wt%, and the mass ratio of zinc chloride to phenolic resin is 0.5:1.
A soft polyurethane foam with a pore size of 20 ppi (pore per inch) and mutually communicated pores is selected as a template, firstly cut into a certain shape, then soaked in 10wt% hydrochloric acid solution for 1 hour, finally placed in deionized water for ultrasonic treatment for 5min, then washed with deionized water and repeated for 5 times. Immersing the polyurethane foam into the slurry A, taking out, draining, drying in a vacuum dryer at 120 ℃ for 25min, taking out, repeating the process for 7 times, keeping the temperature at 350 ℃ for 10 hours in a nitrogen atmosphere, cooling, and washing with a 20wt% hydrochloric acid solution at 85 ℃ until no activator ions are detected, thus obtaining the carbon template.
The sesbania powder and the silicone oil are dissolved in deionized water containing 5wt% of ethanol, the pH value is regulated to 1 by phosphoric acid, and methyl orthosilicate is slowly added under normal temperature stirring, so that the solution is slowly changed into slurry, and slurry B is obtained. Wherein, based on the mass of methyl orthosilicate, the sesbania powder content is 9wt percent, and the silicone oil content is 0.5wt percent. Immersing the carbon template into the slurry B, taking out, blowing off redundant slurry among holes by using compressed air, drying in a vacuum dryer at 120 ℃ for 15min, taking out, and repeating the process for 8 times.
The dried carrier is sent into a microwave roasting furnace, kept at the constant temperature of 1200 ℃ for 7 hours in an argon atmosphere, soaked in 40wt% hydrofluoric acid solution for 12 hours, placed into deionized water for ultrasonic treatment for 5 minutes, and then washed by the deionized water and repeated for 5 times. The carrier was fed into a microwave oven and kept at a constant temperature of 800℃for 8 hours in an air atmosphere. Cooling, putting into 0.5wt% hydrofluoric acid solution for 2 hours, then putting into deionized water for ultrasonic treatment for 5 minutes, then washing with deionized water, repeating for 5 times, taking out, drying at 120 ℃, and roasting at 800 ℃ for 3 hours.
The carrier prepared above is put into impregnating solution, and the impregnating temperature is 90 ℃. The impregnating solution contains ferric acetate and nickel nitrate, and the pH value is adjusted to 3 by citric acid. Based on the weight of the catalyst, the iron content is 12% and the nickel content is 3%. Drying the impregnated catalyst at 120 ℃, then sending the catalyst into a microwave roasting oven, and keeping the temperature at 800 ℃ for 3 hours in a nitrogen atmosphere.
Example 5
The water-soluble phenolic resin, potassium hydroxide, polyethylene glycol (molecular weight 400) and carboxymethyl cellulose are slowly dissolved in deionized water containing 30wt% of ethanol under stirring at 25 ℃ to obtain slurry A. Wherein, based on potassium hydroxide, the content of polyethylene glycol (molecular weight is 400) is 1wt%, the content of carboxymethyl cellulose is 1.5wt%, and the mass ratio of potassium hydroxide to water-soluble phenolic resin is 1:1.
A soft polyurethane foam with a pore size of 50 ppi (pore per inch) and mutually communicated pores is selected as a template, firstly cut into a certain shape, then soaked in 10wt% NaOH solution for 5 hours, finally placed in deionized water for ultrasonic treatment for 5 minutes, then washed by the deionized water and repeated for 5 times. Immersing the polyurethane foam into the slurry A, taking out, draining, drying in a vacuum drier at 120 ℃ for 35min, taking out, repeating the process for 5 times, keeping the temperature at 600 ℃ for 3 hours in a nitrogen atmosphere, cooling, and washing with 5wt% hydrochloric acid solution at 25 ℃ until no activator ion is detected, thus obtaining the carbon template.
Sesbania powder and polyvinyl alcohol (average molecular weight is 22000) are dissolved in deionized water containing 25wt% of ethanol, the pH is adjusted to 3 by oxalic acid, and ethyl orthosilicate is slowly added under stirring at 60 ℃ to enable the solution to be slowly changed into slurry, so that slurry B is obtained. Wherein, the weight percent of sesbania powder is 5 percent and the weight percent of polyvinyl alcohol is 1 percent based on the weight of tetraethoxysilane. Immersing the carbon template into the slurry B, taking out, blowing off redundant slurry among holes by using compressed air, drying in a vacuum dryer at 120 ℃ for 35min, taking out, and repeating the process for 5 times.
The dried carrier is sent into a microwave roasting furnace, kept at the constant temperature of 1700 ℃ for 15 hours in an argon atmosphere, soaked in 40wt% hydrofluoric acid solution for 12 hours, placed into deionized water for ultrasonic treatment for 5 minutes, and then washed by the deionized water and repeated for 5 times. The carrier is sent into a microwave roasting oven and kept at a constant temperature of 1300 ℃ for 4 hours in an oxygen atmosphere. Cooling, putting into NaOH solution with concentration of 2wt%, heating slowly to 120 deg.C, treating for 2 hours, cooling, putting into deionized water, ultrasonic treating for 5 min, washing with deionized water, repeating for 5 times, taking out, drying at 120 deg.C, and roasting at 800 deg.C for 3 hours. Then the carrier is put into impregnating solution containing 5% of sucrose, impregnated at normal temperature, dried at 120 ℃, and then sent into a microwave roasting oven, and the carrier is kept at constant temperature for 4 hours under the condition of 1400 ℃ in nitrogen atmosphere.
The carrier prepared above was put into an impregnating solution at 80 ℃. The impregnating solution contains ferric nitrate, nickel nitrate and lanthanum nitrate, and the pH value is adjusted to 3 by nitric acid. Based on the weight of the catalyst, the iron content is 8%, the nickel content is 2%, and the lanthanum content is 0.5%. Drying the impregnated catalyst at 120 ℃, then sending the catalyst into a microwave roasting oven, and keeping the temperature at 800 ℃ for 3 hours in a nitrogen atmosphere.
Example 6
Starch, potassium hydroxide, ammonium polymethacrylate, tritonX100 were slowly dissolved in deionized water containing 2wt% ethanol with stirring at 80℃to give slurry A. Wherein, based on potassium hydroxide, the content of the ammonium polymethacrylate is 2wt%, the content of TritonX100 is 0.5wt%, and the mass ratio of the potassium hydroxide to the starch is 3:1.
A soft polyurethane foam with a pore size of 100 ppi (pore per inch) and mutually communicated pores is selected as a template, firstly cut into a certain shape, then soaked in a 20wt% NaOH solution for 10 hours, finally placed in deionized water for ultrasonic treatment for 5min, then washed with the deionized water and repeated for 5 times. Immersing the polyurethane foam into the slurry A, taking out, draining, drying in a vacuum dryer at 60 ℃ for 35min, taking out, repeating the process for 10 times, keeping the temperature at 500 ℃ for 8 hours in a nitrogen atmosphere, cooling, and washing with a 10wt% nitric acid solution at 25 ℃ until no activator ions are detected, thus obtaining the carbon template.
Sesbania powder and carboxymethyl cellulose are dissolved in deionized water containing 0.1wt% of ethanol, the pH value is regulated to 1 by nitric acid, sodium silicate is slowly added under stirring at 80 ℃ to enable the solution to be slowly changed into slurry, and slurry B is obtained. Wherein, based on the mass of sodium silicate, the sesbania powder content is 5wt% and the carboxymethyl cellulose content is 4wt%. Immersing the carbon template into the slurry B, taking out, blowing off redundant slurry among holes by using compressed air, drying in a vacuum dryer at 80 ℃ for 35min, taking out, and repeating the process for 10 times.
The dried carrier is sent into a microwave roasting furnace, kept at the constant temperature of 1600 ℃ for 24 hours in an argon atmosphere, soaked in 40wt% hydrofluoric acid solution for 12 hours, placed into deionized water for ultrasonic treatment for 5 minutes, and then washed by the deionized water and repeated for 5 times. The silicon carbide carrier is sent into a microwave roasting furnace, and the temperature is kept constant for 0.5 hours under the condition of 1300 ℃ in the mixed gas atmosphere of oxygen and nitrogen with the oxygen content of 5 percent. Cooling, putting into NaOH solution with concentration of 2wt%, heating slowly to 60 deg.C, treating for 0.5 hr, cooling, putting into deionized water, ultrasonic treating for 5min, washing with deionized water, repeating for 5 times, taking out, oven drying at 120deg.C, and roasting at 800 deg.C for 3 hr. Then the carrier is put into impregnating solution containing 1wt% of starch, impregnated at 50 ℃, dried at 120 ℃, and then sent into a microwave roasting oven to be kept at the constant temperature of 1400 ℃ for 0.5 hour in nitrogen atmosphere.
The carrier prepared above is put into impregnating solution, and the impregnating temperature is 60 ℃. The impregnating solution contains ferric nitrate, nickel nitrate and magnesium acetate, and the pH value is regulated to 1 by hydrochloric acid. Based on the weight of the catalyst, the iron content is 5%, the nickel content is 1% and the magnesium content is 0.5%. Drying the impregnated catalyst at 120 ℃, then sending the catalyst into a microwave roasting oven, and keeping the temperature at 800 ℃ for 3 hours in a nitrogen atmosphere.
Example 7
Dextrin, phosphoric acid, polyethylene glycol (molecular weight 400) and carboxymethyl cellulose are slowly dissolved in deionized water containing 20wt% of ethanol under stirring at 40 ℃ to obtain slurry A. Wherein, based on phosphoric acid, the content of polyethylene glycol (molecular weight is 400) is 4wt%, the content of carboxymethyl cellulose is 6wt%, and the mass ratio of phosphoric acid to dextrin is 0.8:1.
A soft polyurethane foam with a pore size of 150 ppi (pore per inch) and mutually communicated pores is selected as a template, firstly cut into a certain shape, then soaked in an oxalic acid solution with 20wt% for 7 hours, finally placed in deionized water for ultrasonic treatment for 5min, then washed by the deionized water and repeated for 5 times. Immersing the polyurethane foam into the slurry A, taking out, draining, drying in a vacuum drier at 120 ℃ for 35min, taking out, repeating the process for 6 times, keeping the temperature at 800 ℃ for 3 hours in a nitrogen atmosphere, cooling, and washing with 15wt% oxalic acid solution at 80 ℃ until no activator ion is detected, thus obtaining the carbon template.
Sesbania powder and hexamethylenetetramine are dissolved in deionized water containing 80wt% of ethanol, the pH value is regulated to 7 by oxalic acid, and propyl orthosilicate is slowly added under stirring at 20 ℃ to enable the solution to be slowly changed into slurry, so that slurry B is obtained. Wherein, based on the mass of the propyl orthosilicate, the sesbania powder content is 0.5 weight percent, and the hexamethylenetetramine content is 0.01 weight percent. Immersing the carbon template into the slurry B, taking out, blowing off redundant slurry among holes by using compressed air, drying in a vacuum dryer at 120 ℃ for 35min, taking out, and repeating the process for 8 times.
The dried carrier is sent into a microwave roasting furnace, kept at the constant temperature of 1300 ℃ for 24 hours in an argon atmosphere, soaked in 40wt% hydrofluoric acid solution for 12 hours, placed into deionized water for ultrasonic treatment for 5 minutes, and then washed by the deionized water and repeated for 5 times. The silicon carbide carrier is sent into a microwave roasting furnace, and the temperature is kept for 6 hours under the condition of 1000 ℃ in the mixed gas atmosphere of oxygen with the oxygen content of 60 percent and helium. Cooling, putting into NaOH solution with concentration of 20wt%, heating slowly to 120deg.C, treating for 0.5 hr, cooling, putting into deionized water, ultrasonic treating for 5 min, cleaning with deionized water, repeating for 5 times, taking out, oven drying at 120deg.C, and roasting at 800deg.C for 3 hr. Then the carrier is put into impregnating solution containing 5wt% of glucose, impregnated at 90 ℃, dried at 120 ℃, and then sent into a microwave roasting oven to be kept at the constant temperature of 1100 ℃ for 4 hours in nitrogen atmosphere.
The carrier prepared above was put into an impregnating solution at 50 ℃. The impregnating solution contains ferrous acetate, nickel acetate, chromium nitrate and lanthanum nitrate, and the pH value is regulated to 10 by phosphoric acid. Based on the weight of the catalyst, the iron content is 15%, the nickel content is 0.5%, the chromium content is 4.5%, and the lanthanum content is 0.1%. Drying the impregnated catalyst at 120 ℃, then sending the catalyst into a microwave roasting oven, and keeping the temperature at 800 ℃ for 3 hours in a nitrogen atmosphere.
Example 8
The water-soluble phenolic resin, potassium hydroxide, tritonX100 and carboxymethyl cellulose are slowly dissolved in deionized water containing 5wt% of ethanol under the stirring of 60 ℃ to obtain slurry A. Wherein, based on potassium hydroxide, the content of TritonX100 is 1wt%, the content of carboxymethyl cellulose is 9wt%, and the mass ratio of potassium hydroxide to water-soluble phenolic resin is 5:1.
A soft polyurethane foam body with the pore size of 200 and ppi (pores per inch) and mutually communicated pores is selected as a template, firstly cut into a certain shape, then soaked in a nitric acid solution with the weight percent of 1 for 10 hours, finally placed in deionized water for ultrasonic treatment for 5 minutes, then washed by the deionized water and repeated for 5 times. Immersing the polyurethane foam into the slurry A, taking out, draining, drying in a vacuum dryer at 140 ℃ for 10min, taking out, repeating the process for 7 times, keeping the temperature at 700 ℃ for 6 hours in a nitrogen atmosphere, cooling, and washing with deionized water at 50 ℃ until no activator ion is detected, thus obtaining the carbon template.
Microcrystalline cellulose and silica sol are dissolved in deionized water containing 2wt% of ethanol, the pH value is adjusted to 10 by ammonia water, and ethyl orthosilicate is slowly added under stirring at 120 ℃ to enable the solution to be slowly changed into slurry, so that slurry B is obtained. Wherein, the content of microcrystalline cellulose is 0.5wt% and the content of silica sol is 5wt% based on the mass of the tetraethoxysilane. Immersing the carbon template into the slurry B, taking out, blowing off redundant slurry among holes by using compressed air, drying in a vacuum dryer at 150 ℃ for 5min, taking out, and repeating the process for 6 times.
The dried carrier is sent into a microwave roasting furnace, kept at the constant temperature of 1600 ℃ for 7 hours in an argon atmosphere, soaked in 40wt% hydrofluoric acid solution for 12 hours, placed into deionized water for ultrasonic treatment for 5 minutes, and then washed by the deionized water and repeated for 5 times. The silicon carbide carrier is sent into a microwave roasting furnace and kept at the constant temperature for 8 hours under the condition of 1200 ℃ in the mixed gas atmosphere of oxygen with 80% of oxygen content and argon. Cooling, putting into NaOH solution with concentration of 0.1wt%, heating slowly to 120 deg.C, treating for 5 hours, cooling, putting into deionized water, ultrasonic treating for 5min, washing with deionized water, repeating for 5 times, taking out, drying at 120 deg.C, and roasting at 800 deg.C for 3 hours. Then the carrier is put into impregnating solution containing 25wt% of glycerin, impregnated at 40 ℃, dried at 120 ℃, and then sent into a microwave roasting oven, and kept at a constant temperature of 1500 ℃ for 0.5 hour in nitrogen atmosphere.
The carrier prepared above was put into an impregnating solution at an impregnating temperature of 25 ℃. The impregnating solution contains ferric nitrate, nickel nitrate, cerium nitrate and zirconyl nitrate, and the pH value is regulated to 3 by oxalic acid. Based on the weight of the catalyst, the iron content is 8%, the nickel content is 1%, the cerium content is 0.5%, and the zirconium content is 0.5%. Drying the impregnated catalyst at 120 ℃, then sending the catalyst into a microwave roasting oven, and keeping the temperature at 800 ℃ for 3 hours in a nitrogen atmosphere.
Catalyst performance evaluation:
the pore structure properties of the supports prepared in examples 1 to 8 were measured by an ASAP 2460 type specific surface area and porosity analyzer, and the results are shown in Table 1:
TABLE 1 catalyst pore structure Properties
Catalyst Specific surface area (m) 2 /g） Pore volume (cm) 3 /g）
Example 1 225 0.66
Example 2 94 0.23
Example 3 236 0.63
Example 4 108 0.28
Example 5 217 0.61
Example 6 318 0.81
Example 7 203 0.53
Example 8 427 0.95
Toluene, phenol and naphthalene are used as tar model compounds, simulated biomass gasification gas and steam are simultaneously introduced, and a fixed bed evaluation device is used for evaluating the activity and service life of the catalyst. The simulated biomass gasification gas flow is 500mL/min, and the proportion of each component is H 2 20%、CO 29.5%、CH 4 10.2%、CO 2 15%、N 2 25.3%，H 2 O flow was 0.15 mL/min, tar model compound flow was 0.15 mL/min, where toluene: phenol: the molar ratio of naphthalene is 10:2:0.5. And (3) adding a certain amount of quartz sand into the catalyst for dilution, loading the catalyst into a quartz tube reactor at the reaction temperature of 650-750 ℃, and introducing biomass gasification gas, water and tar model compound for continuous experiment after the catalyst is heated to the reaction temperature, wherein the evaluation time is 48 hours. Reaction tail gas is passed through cold organicAnd after the solvent is absorbed, online continuous monitoring is carried out by using Micro 490 gas chromatography, the yield of tar cracking gas is calculated according to the flow of each gas component before and after the reaction, and the organic solvent is subjected to offline analysis by adopting GC-MS after the reaction to calculate the tar cracking conversion rate. The evaluation results of the catalysts obtained in examples 1 to 8 are shown in Table 2.
In order to further examine the service life of the catalyst, the catalyst obtained in example 5 was used as a sample to examine the tar cracking conversion after 100 hours of operation, and after 100 hours of evaluation experiment, the tar cracking conversion of the catalyst obtained in example 5 was still maintained at 98.7%.
Table 2 catalyst evaluation results
Catalyst Average tar cracking conversion Average tar cracking gas yield
Example 1 95.63 95.42
Example 2 94.16 94.03
Example 3 98.37 98.04
Example 4 98.14 97.93
Example 5 99.91 99.78
Example 6 99.84 99.67
Example 7 99.21 99.13
Example 8 99.47 99.23

Claims (51)

1. A preparation method of a carrier for integral tar cracking is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Mixing the carbon precursor, the activating agent and the auxiliary agent A solution uniformly to obtain slurry A;
(2) Adding polyurethane foam into the slurry A for soaking, and then roasting and washing to obtain a carbon template;
(3) Mixing a silicon source with the solution of the auxiliary agent B, and regulating and controlling the pH value of the system to be 1-10 to obtain slurry B;
(4) Adding the carbon template obtained in the step (2) into slurry B for soaking, adding a sample obtained after the soaking and roasting into hydrofluoric acid solution for treatment, and further washing to obtain a carrier;
(5) In the presence of oxygen-containing gas, carrying out high-temperature treatment on the carrier obtained in the step (4), mixing the treated material with alkaline solution or hydrofluoric acid solution for treatment, and then washing, drying and roasting to obtain the carrier;
(6) Adding the carrier obtained in the step (5) into a carbon-containing precursor solution for impregnation, and then drying and roasting to obtain the carrier, wherein the roasting is carried out under a nitrogen atmosphere;
wherein the auxiliary agent A solution in the step (1) comprises an auxiliary agent A, a solvent and water, wherein the auxiliary agent A is tetramethylammonium hydroxide, and the molecular weight of the auxiliary agent A is one or more of polyethylene glycol, tritonX100, ammonium polymethacrylate, polyethyleneimine, polyacrylamide, sodium lignin sulfonate, carboxymethyl cellulose, triglyceride and polyetherimide, and the solvent is an organic solvent; the carbon precursor in the step (1) is one or more of phenolic resin, dextrin, glycerol and water-soluble polysaccharide; the polyurethane foam in the step (2) is soft polyurethane foam with the pore size of 5-200 ppi and mutually communicated pores; the auxiliary agent B solution in the step (3) comprises an auxiliary agent B, a solvent and water, wherein the auxiliary agent B is one or more of carboxymethyl cellulose, hydroxyethyl cellulose, microcrystalline cellulose, chitosan, sesbania powder, hydroxypropyl methyl cellulose, polyvinyl alcohol, silicone oil, hexamethylenetetramine, silica sol and aluminum dihydrogen phosphate, and the solvent is an organic solvent; the carbon-containing precursor in the step (6) is one or more of monosaccharide, disaccharide, water-soluble polysaccharide, phenolic resin, dextrin and glycerol.
2. The method for producing a monolithic tar cracking carrier according to claim 1, wherein the carbon precursor in the step (1) is a phenolic resin.
3. The method for producing a monolithic tar cracking carrier according to claim 1 or 2, wherein the carbon precursor in step (1) is a water-soluble phenol resin.
4. The method for preparing a carrier for monolithic tar cracking as defined in claim 1, wherein the activator in step (1) is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, zinc chloride, and phosphoric acid.
5. The method for producing a monolithic tar cracking carrier according to claim 1 or 4, wherein the activator in step (1) is potassium hydroxide.
6. The method for preparing a carrier for monolithic tar cracking according to claim 1, wherein the auxiliary agent A is one or more of tetramethylammonium hydroxide, polyethylene glycol with molecular weight of 200-8000 and carboxymethyl cellulose; the solvent is an alcohol solvent.
7. The method for preparing a carrier for monolithic tar cracking as recited in claim 6, wherein the solvent is one or more of ethanol, methanol, propanol, butanol, ethylene glycol, propylene glycol, glycerin, and butylene glycol.
8. The method for producing a monolithic tar cracking carrier according to claim 7, wherein the solvent is ethanol.
9. The method for producing a carrier for monolithic tar cracking as defined in claim 1, wherein the mass concentration of the auxiliary A is 0.1 to 10% by weight, and the mass concentration of the solvent is 0.1 to 80% by weight, based on the mass of the auxiliary A solution.
10. The method for preparing a carrier for monolithic tar cracking according to claim 1, wherein the mixing temperature in the step (1) is 20-80 ℃, and the dry basis content of the auxiliary agent A is 1-10 wt% based on the dry basis mass of the activating agent; the mass ratio of the activator to the carbon precursor is 0.2-5:1.
11. The method for preparing a carrier for monolithic tar cracking according to claim 1, wherein the polyurethane foam in the step (2) is obtained by modifying an existing polyurethane foam material, wherein the modification is obtained by immersing the polyurethane foam material in an acid or alkali solution and then washing; the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and citric acid, and the mass concentration of the acid is 1-20wt%; the alkali is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide, and the mass concentration of the alkali is 1-20wt%.
12. The method for producing a carrier for monolithic tar cracking according to claim 1, wherein the baking temperature in step (2) is 350 to 900 ℃ and the baking time is 2 to 10 hours, the baking is performed in the presence of nitrogen or an inert gas, and the inert gas is one or more of helium, neon, argon, krypton, and xenon.
13. The method for preparing a carrier for monolithic tar cracking according to claim 1, wherein the washing in the step (2) is carried out by washing with an acid solution or deionized water until no activator ion is detected, the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and citric acid, the mass concentration of the acid solution is 1-20wt%, and the washing temperature is 20-80 ℃.
14. The method for producing a monolithic tar cracking carrier according to claim 1, wherein the impregnating step in the step (2) is: and immersing polyurethane foam into the slurry A, taking out, draining, drying in a vacuum drier at 60-150 ℃ for 5-35 min, taking out, and repeating the above process for 5-10 times.
15. The method for producing a carrier for monolithic tar cracking as defined in claim 1, wherein the silicon source in step (3) is one or more of sodium silicate, methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate.
16. The method for producing a monolithic tar cracking carrier according to claim 1 or 15, wherein the silicon source in step (3) is sodium silicate and/or tetraethyl orthosilicate.
17. The method for preparing the carrier for monolithic tar cracking according to claim 1, wherein the auxiliary agent B is one or more of carboxymethyl cellulose, sesbania powder, polyvinyl alcohol and hexamethylenetetramine; the solvent is an alcohol solvent.
18. The method for preparing a monolithic tar cracking carrier according to claim 17, wherein the solvent is one or more of ethanol, methanol, propanol, butanol, ethylene glycol, propylene glycol, glycerin, and butylene glycol.
19. The method for producing a monolithic tar cracking carrier according to claim 18, wherein the solvent is ethanol.
20. The method for producing a carrier for monolithic tar cracking as defined in claim 1, wherein the mass concentration of the auxiliary B is 0.1 to 20% by weight, and the mass concentration of the solvent is 0.1 to 80% by weight, based on the mass of the auxiliary B solution.
21. The method for preparing a carrier for monolithic tar cracking according to claim 1, wherein the mixing temperature in step (3) is 20 to 120 ℃; the dry basis weight of the auxiliary agent B is 1-10wt% based on the dry basis weight of the silicon source.
22. The method for producing a monolithic tar cracking carrier according to claim 1, wherein the impregnating step in the step (4) is: immersing the carbon template obtained in the step (2) into the slurry B, taking out, blowing off redundant slurry among holes by using compressed air, drying in a vacuum dryer at 60-150 ℃ for 5-35 min, taking out, and repeating the process for 5-10 times.
23. The method for producing a carrier for monolithic tar cracking as defined in claim 1, wherein the firing temperature in step (4) is 1200 to 1900 ℃; the roasting time is 3-24 hours, and the roasting is performed in the presence of nitrogen or inert gas, wherein the inert gas is one or more of helium, neon, argon, krypton and xenon.
24. The method for producing a monolithic tar cracking carrier according to claim 23, wherein the firing time in the step (4) is 7 to 15 hours, and firing is performed under microwave conditions.
25. The method for producing a carrier for monolithic tar cracking as defined in claim 1, wherein the concentration of the hydrofluoric acid solution in the step (4) is 20 to 40% by weight, and the treatment time is 5 to 12 hours.
26. The method for producing a monolithic tar cracking carrier according to claim 1, wherein the high-temperature treatment temperature in step (5) is 800 to 1300 ℃.
27. The method for producing a monolithic tar cracking carrier according to claim 1 or 26, wherein the high-temperature treatment temperature in step (5) is 950 to 1300 ℃.
28. The method for producing a monolithic tar cracking carrier according to claim 1 or 26, wherein the high-temperature treatment temperature in step (5) is 1000 to 1300 ℃.
29. The method for producing a carrier for monolithic tar cracking according to claim 1, wherein the oxygen-containing gas in step (5) is any one of air, oxygen, a mixture of oxygen and nitrogen, and a mixture of oxygen and an inert gas, and the oxygen content by volume is 5 to 80%; the inert gas is one or more of helium, neon, argon, krypton and xenon.
30. The method for producing a carrier for monolithic tar cracking as defined in claim 1, wherein the alkaline solution in step (5) is an inorganic alkaline solution, and the inorganic alkaline solution is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
31. The method for producing a monolithic tar cracking carrier according to claim 30, wherein the inorganic alkaline solution is sodium hydroxide and/or potassium hydroxide.
32. The method for producing a monolithic tar cracking carrier according to claim 30, wherein the inorganic alkaline solution is sodium hydroxide.
33. The method for producing a carrier for monolithic tar cracking according to claim 1, wherein the mass ratio of the material obtained after the high-temperature treatment in step (5) to the alkaline solution or hydrofluoric acid solution is 1:80 to 1:10, the concentration of the alkaline solution is 0.1 to 20wt%, and the concentration of the hydrofluoric acid solution is 0.01 to 5wt%.
34. The method for producing a carrier for monolithic tar cracking as defined in claim 1, wherein the mixing treatment temperature in step (5) is 60 to 120℃and the treatment time is 0.5 to 5 hours.
35. The method for producing a carrier for monolithic tar cracking as defined in claim 1, wherein the drying temperature in step (5) is 100 to 150 ℃, the firing temperature in step (5) is 650 to 1000 ℃, and the firing time is 3 to 9 hours.
36. The method for producing a monolithic tar cracking carrier according to claim 1 or 35, wherein the drying in step (5) is performed under microwave conditions; the roasting in the step (5) is carried out under the condition of nitrogen or inert gas.
37. The method for producing a monolithic tar cracking carrier according to claim 36, wherein the firing in step (5) is performed under microwave conditions.
38. The method for producing a carrier for monolithic tar cracking as defined in claim 1, wherein the carbonaceous precursor in step (6) is sucrose and/or a phenolic resin.
39. The method for producing a carrier for monolithic tar cracking as defined in claim 1, wherein the mass fraction of the carbon-containing precursor solution in the step (6) is 1 to 25%, and the impregnation temperature in the step (6) is 20 to 90 ℃.
40. The method for producing a monolithic tar cracking carrier according to claim 1, wherein the drying temperature in the step (6) is 100 to 150 ℃.
41. The method for producing a monolithic tar cracking carrier according to claim 1 or 40, wherein the drying in step (6) is performed under microwave conditions.
42. The method for producing a carrier for monolithic tar cracking as defined in claim 1, wherein the baking temperature in step (6) is 1000 to 1600 ℃ and the treatment time is 0.5 to 4 hours.
43. The method for producing a monolithic tar cracking carrier according to claim 1 or 42, wherein the firing temperature in step (6) is 1100 to 1500℃and firing is conducted under microwave conditions.
44. A carrier for monolithic tar cracking, which is obtained by the preparation method of any one of claims 1-43, wherein the carrier for monolithic tar cracking is modified foam silicon carbide, and the modified foam silicon carbide comprises foam silicon carbide, and silicon oxide and silicon nitride dispersed on the surface of the foam silicon carbide.
45. A monolithic tar cracking catalyst comprising a support and an active metal component, wherein the support is a monolithic tar cracking support according to claim 44.
46. The monolithic tar cracking catalyst as recited in claim 45, wherein the carrier is present in an amount of 60 to 99% and the active metal component is present in an amount of 1 to 40% by weight, based on the weight of the catalyst.
47. The monolithic tar cracking catalyst as recited in claim 45, wherein the support is present in an amount of 80 to 98 wt% and the active metal component is present in an amount of 2 to 20wt% based on the weight of the catalyst.
48. The monolithic tar cracking catalyst of claim 45 wherein the monolithic tar cracking catalyst has the following properties: specific surface area of 55-600 m 2 And/g, the pore volume is larger than 0.01mL/g.
49. The monolithic tar cracking catalyst of claim 45 wherein the active metal component is one or more of a group VIII metal, a group VIB metal, and a group VIIB metal, wherein the group VIII metal is one or more of iron, nickel, cobalt, and palladium, the group VIB metal is one or more of chromium, molybdenum, and tungsten, and the group VIIB metal is one or more of manganese, and rhenium.
50. The monolithic tar cracking catalyst of claim 49 wherein the active metal component is iron and/or nickel.
51. The monolithic tar cracking catalyst of any of claims 45-50 further comprising an adjunct that is one or more of a magnesium, strontium, cerium, zirconium, lanthanum, ytterbium, and copper-containing compound; the content of the auxiliary agent is 0.01-1% based on the weight of the catalyst.
CN202011164876.1A 2020-10-27 2020-10-27 Carrier and catalyst for integral tar cracking and preparation method thereof Active CN114471648B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011164876.1A CN114471648B (en) 2020-10-27 2020-10-27 Carrier and catalyst for integral tar cracking and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011164876.1A CN114471648B (en) 2020-10-27 2020-10-27 Carrier and catalyst for integral tar cracking and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114471648A CN114471648A (en) 2022-05-13
CN114471648B true CN114471648B (en) 2023-09-01

Family

ID=81471139

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011164876.1A Active CN114471648B (en) 2020-10-27 2020-10-27 Carrier and catalyst for integral tar cracking and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114471648B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116060016A (en) * 2022-12-19 2023-05-05 东风汽车集团股份有限公司 Preparation method of oxygen storage material, oxygen storage material and application of oxygen storage material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5958831A (en) * 1996-10-21 1999-09-28 Pechiney Recherche SiC foam catalyst carrier with a reinforced skin and corresponding catalytic systems
US6217841B1 (en) * 1991-11-21 2001-04-17 Pechiney Recherche Process for the preparation of metal carbides having a large specific surface from activated carbon foams
CN111375399A (en) * 2018-12-29 2020-07-07 中国石油化工股份有限公司 Heavy oil hydrotreating catalyst and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090275791A1 (en) * 2008-05-05 2009-11-05 Saudi Arabian Oil Company Ceramic foam catalyst support for gasoline alkylation
DE102008036724A1 (en) * 2008-08-07 2010-02-11 Uhde Gmbh Highly porous foam ceramics as catalyst supports for the dehydrogenation of alkanes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6217841B1 (en) * 1991-11-21 2001-04-17 Pechiney Recherche Process for the preparation of metal carbides having a large specific surface from activated carbon foams
US5958831A (en) * 1996-10-21 1999-09-28 Pechiney Recherche SiC foam catalyst carrier with a reinforced skin and corresponding catalytic systems
CN111375399A (en) * 2018-12-29 2020-07-07 中国石油化工股份有限公司 Heavy oil hydrotreating catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Fabircation of lightweight and porous silicon carbide foams as excellent microwave susceptor for heat generation;saroj kumari et al.;《Materials Chemistry and Physics》;第1-8页 *

Also Published As

Publication number Publication date
CN114471648A (en) 2022-05-13

Similar Documents

Publication Publication Date Title
CN110890558B (en) Supported platinum-based core-shell catalyst and preparation method thereof
JP4431027B2 (en) Mesoporous carbon molecular sieve and supported catalyst using the same
CN1970442B (en) Mesoporous carbon, method of preparing the same, and fuel cell using the carbon
CN114471648B (en) Carrier and catalyst for integral tar cracking and preparation method thereof
CN111905767B (en) Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof
CN113117710B (en) Catalyst carrier for biomass pyrolysis, catalyst and preparation method thereof
CN110745825A (en) Preparation method of high-performance biomass-based shaddock peel oriented activated carbon VOCs adsorbent
CN113457657A (en) Carbon-based methanol hydrogen production catalyst and preparation method and application thereof
CN111437859A (en) High-efficiency non-metal carbon-based catalyst and preparation method and application thereof
CN113181921B (en) High-activity Ni/ACP catalyst and preparation method and application thereof
CN110723720A (en) Light broadband electromagnetic wave absorbing material and preparation method thereof
CN114570361A (en) Ru-based catalyst for ammonia decomposition hydrogen production and preparation method thereof
CN114471647B (en) Tar cracking catalyst carrier, catalyst and preparation method thereof
CN111807346B (en) Preparation method of broadband efficient wave-absorbing macroporous thin-layer carbon material
CN110152666B (en) Porous carbon supported copper-based catalyst and preparation method thereof
CN107857250B (en) Melamine foam in-situ growth carbon nanotube composite super-hydrophobic material and preparation method thereof
CN116689008A (en) Transition metal doping defective g-C for lignin depolymerization 3 N 4 Photocatalytic material and preparation method thereof
CN113117715B (en) Catalyst carrier for tar cracking, catalyst and preparation method thereof
CN114749199B (en) NiFe 2 O 4 Preparation method and application of-MCS composite microwave catalyst
CN113117716B (en) Carrier of catalyst for cracking biological tar, catalyst and preparation method
CN111484002B (en) Preparation method and application of porous graphene film
CN113318737A (en) Copper/porous carbon catalyst and preparation method and application thereof
CN113117711B (en) Biological tar cracking catalyst carrier, catalyst and preparation method thereof
CN111013572B (en) Method for expanding pores and loading photocatalyst on activated carbon fiber
CN112952119A (en) Transition metal doped two-dimensional carbon nanosheet and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20231215

Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee after: CHINA PETROLEUM & CHEMICAL Corp.

Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd.

Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee before: CHINA PETROLEUM & CHEMICAL Corp.

Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp.