CN115282993B - Regenerated catalyst and preparation method and application thereof - Google Patents

Regenerated catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN115282993B
CN115282993B CN202211186838.5A CN202211186838A CN115282993B CN 115282993 B CN115282993 B CN 115282993B CN 202211186838 A CN202211186838 A CN 202211186838A CN 115282993 B CN115282993 B CN 115282993B
Authority
CN
China
Prior art keywords
solution
stirring
mixing
solvent
acid
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
CN202211186838.5A
Other languages
Chinese (zh)
Other versions
CN115282993A (en
Inventor
胡小夫
沈明忠
王凯亮
白永锋
耿宣
何佳
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.)
China Huadian Engineering Group Co Ltd
Huadian Environmental Protection Engineering and Technology Co Ltd
Original Assignee
China Huadian Engineering Group Co Ltd
Huadian Environmental Protection Engineering and Technology Co Ltd
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 Huadian Engineering Group Co Ltd, Huadian Environmental Protection Engineering and Technology Co Ltd filed Critical China Huadian Engineering Group Co Ltd
Priority to CN202211186838.5A priority Critical patent/CN115282993B/en
Publication of CN115282993A publication Critical patent/CN115282993A/en
Application granted granted Critical
Publication of CN115282993B publication Critical patent/CN115282993B/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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J35/613—10-100 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention relates to a regenerated catalyst, a preparation method and application thereof, belonging to CO 2 The technical field of trapping. The invention provides a method for preparing heteropoly acid @ mesoporous TiO 2 The method of the composite material is based on a sol-gel-solvent method and an in-situ assembly one-step method, and firstly, a template agent, a solvent and titanium salt are mixed to obtain mesoporous TiO 2 Precursor suspension, and then adding mesoporous TiO 2 Mixing the precursor suspension and at least two kinds of oxysalts, then carrying out acidification treatment to obtain gel containing heteropoly acid nanocrystals, then carrying out solvent thermal crystallization treatment on the gel to obtain a crystallization product, and finally roasting the crystallization product to obtain heteropoly acid @ mesoporous TiO 2 A composite material. The composite material is used as CO 2 The regenerated catalyst can provide CO at the same time 2 Desorbing the L acid site and the B acid site required by the reaction and reducing CO 2 The temperature required for the desorption reaction is reduced, thereby reducing CO 2 The thermal load required by the desorption process is solved, and CO is removed 2 High energy consumption in the trapping process.

Description

Regenerated catalyst and preparation method and application thereof
Technical Field
The invention relates to a regenerated catalyst, a preparation method and application thereof, belonging to CO 2 The technical field of trapping.
Background
The amine liquid chemical absorption method is the most widely applied CO in the thermal power plant at present 2 Trapping technology by means of an absorbent (i.e. amine liquid) with CO 2 CO generated by chemical reaction and absorbed by the absorbent under certain conditions 2 The desorption separation is carried out while the absorbent is regenerated. The technique has CO 2 High absorption efficiency, strong selectivity and simple process, but the CO of the absorbent 2 The desorption process usually needs a high temperature (generally 110 to 130 ℃) higher than 100 ℃, and if the absorption liquid using water as a solvent is desorbed at the temperature, a large amount of energy consumption is consumed, which accounts for about 60 to 70% of the energy consumption of the system, and a series of problems such as high energy consumption and high cost of the system are caused. Therefore, there is a need to reduce CO 2 The total heat load of the desorption process, including the latent heat of vaporization of the water and the sensible heat of the water.
If the CO can be developed and used as absorbent 2 CO of desorption process 2 Regeneration of the catalyst, CO reduction 2 The temperature in the desorption system, thereby enabling the absorbent to be regenerated at a lower temperature (lower than 100 ℃) to achieve CO saving 2 The energy consumption (latent heat of vaporization of water and sensible heat of water) required during desorption, and the purpose of minimizing corrosion of equipment and degradation of the absorbent.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing heteropoly acid @ mesoporous TiO 2 A method of compounding a material, the method comprising: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; dissolving the oxysalt A in a solvent B to obtain a dissolved solution B; dissolving the oxysalt B in a solvent B to obtain a dissolved solution C; mixing the solution B and the suspension, and stirring to obtain a mixed solution A(ii) a Mixing the dissolved solution C with the mixed solution A, and stirring to obtain a mixed solution B; dropwise adding an acid solution into the mixed liquid B while stirring until the pH value of the mixed liquid B is 1 to 3, stopping dropwise adding the acid solution, and continuously stirring to obtain a gel; crystallizing the gel, and roasting the crystallized product to obtain heteropoly acid @ mesoporous TiO 2 A composite material.
In one embodiment of the invention, the mass ratio of the template agent to the solvent A to the titanium salt to the solvent B to the oxysalt A to the oxysalt B to the acid solution is 0 to 2:5 to 100:0.5 to 10:5 to 100:0.5 to 2:0.05 to 1:5 to 20.
In one embodiment of the invention, the titanium salt is one or more of titanium tetrachloride, titanium sulfate or tetrabutyl titanate; the oxysalt A is Na 2 WO 4 And/or Na 2 MoO 4 (ii) a The oxysalt B is Na 2 HPO 4 、NaVO 3 And/or Na 2 SiO 3 (ii) a The heteropoly acid is alpha-H 3 PW 12 O 40 、α-H 4 SiW 12 O 40 、α-H 3 PMo 12 O 40 Or alpha-H 4 SiMo 12 O 40 One or more of the above; the template agent is one or more of P123, dodecyl sulfonic acid, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride or hexadecyl trimethyl ammonium.
In one embodiment of the invention, the method is as follows: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; dissolving the oxysalt A in a solvent B to obtain a dissolved solution B; dissolving the oxysalt B in a solvent B to obtain a dissolved solution C; mixing the solution B with the suspension, and heating and stirring at 40 to 90 ℃ for 0.5 to 2h to obtain a mixed solution A; mixing the solution C with the mixed solution A, and heating and stirring at 40-90 ℃ for 0.5-2h to obtain a mixed solution B; dropwise adding an acid solution into the mixed solution B, heating and stirring at 40-90 ℃ until the pH value of the mixed solution B is 1-3, stopping dropwise adding the acid solution, and continuing heating and stirring at 40-90 ℃ for 0.5-6 h to obtain a gel; crystallizing the gel, and roasting the crystallized product to obtain heteropoly acid @ mesoporous TiO 2 A composite material.
In one embodiment of the invention, the solvent a is one or more of water, ionic liquid or organic solvent; the solvent B is one or more of water, dilute sulfuric acid solution or hydrochloric acid solution; the acid solution is concentrated hydrochloric acid solution and/or dilute sulfuric acid solution.
In one embodiment of the present invention, when the oxoacid salt A is Na 2 WO 4 The oxysalt B is Na 2 HPO 4 The method comprises the following steps: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; na is mixed with 2 WO 4 Dissolving the mixture in a solvent B at 40 to 90 ℃ to obtain a solution B; mixing Na 2 HPO 4 Dissolving in a solvent B to obtain a dissolved solution C; mixing the solution B with the suspension, and heating and stirring at 40-90 ℃ for 0.5-2h to obtain a mixed solution A; mixing the solution C with the mixed solution A, and heating and stirring at 40-90 ℃ for 0.5-2h to obtain a mixed solution B; dropwise adding an acid solution into the mixed liquid B, heating and stirring at 40-90 ℃ until the pH value of the mixed liquid B is 1-3, stopping dropwise adding the acid solution, and continuously heating and stirring at 40-90 ℃ for 0.5-6 h to obtain a gel; crystallizing the gel, and roasting the crystallized product to obtain H 3 PW 12 O 40 @ mesoporous TiO 2 A composite material;
when the oxysalt A is Na 2 WO 4 The oxysalt B is Na 2 SiO 3 The method comprises the following steps: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; mixing Na 2 WO 4 Dissolving in a solvent B at 40 to 90 ℃ to obtain a solution B; mixing Na 2 SiO 3 Dissolving in a solvent B to obtain a dissolved solution C; mixing the solution B with the suspension, and heating and stirring at 40-90 ℃ for 0.5-2h to obtain a mixed solution A; mixing the solution C with the mixed solution A, and heating and stirring at 40 to 90 ℃ for 0.5 to 2h to obtain a mixed solution B; dropwise adding an acid solution into the mixed solution B, heating and stirring at 40-90 ℃ until the pH value of the mixed solution B is 1-3, stopping dropwise adding the acid solution, and continuing heating and stirring at 40-90 ℃ for 0.5-6 h to obtain a gel; crystallizing the gel, and roasting the crystallized product to obtain H 3 SiW 12 O 40 @ mesoporous TiO 2 A composite material;
when the oxysalt A is Na 2 MoO 4 The oxysalt B is Na 2 HPO 4 The method comprises the following steps: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; na is mixed with 2 MoO 4 Dissolving in a solvent B at 40 to 90 ℃ to obtain a solution B; mixing Na 2 HPO 4 Dissolving in a solvent B to obtain a dissolved solution C; mixing the solution B with the suspension, and heating and stirring at 40-90 ℃ for 0.5-2h to obtain a mixed solution A; mixing the solution C with the mixed solution A, and heating and stirring at 40 to 90 ℃ for 0.5 to 2h to obtain a mixed solution B; dropwise adding an acid solution into the mixed solution B, heating and stirring at 40-90 ℃ until the pH value of the mixed solution B is 1-3, stopping dropwise adding the acid solution, and continuing heating and stirring at 40-90 ℃ for 0.5-6 h to obtain a gel; crystallizing the gel, and roasting the crystallized product to obtain H 3 PMo 12 O 40 @ mesoporous TiO 2 A composite material;
when the oxysalt A is Na 2 MoO 4 The oxysalt B is Na 2 SiO 3 The method comprises the following steps: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; mixing Na 2 MoO 4 Dissolving in a solvent B at 40 to 90 ℃ to obtain a solution B; na is mixed with 2 SiO 3 Dissolving in a solvent B to obtain a dissolved solution C; mixing the solution B with the suspension, and heating and stirring at 40-90 ℃ for 0.5-2h to obtain a mixed solution A; mixing the solution C with the mixed solution A, and heating and stirring at 40-90 ℃ for 0.5-2h to obtain a mixed solution B; dropwise adding an acid solution into the mixed solution B, stirring until the pH value of the mixed solution B is 1 to 3, stopping dropwise adding the acid solution, and continuously heating and stirring at 40 to 90 ℃ for 0.5 to 6 hours to obtain a gel; crystallizing the gel, and roasting the crystallized product to obtain H 3 SiMo 12 O 40 @ mesoporous TiO 2 A composite material;
when the oxysalt A is Na 2 WO 4 The oxysalt B is Na 2 HPO 4 And NaVO 3 The method comprises the following steps: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing the titanium salt with solution A to obtain suspensionLiquid; na is mixed with 2 WO 4 Dissolving in a solvent B at 40 to 90 ℃ to obtain a solution B; mixing Na 2 HPO 4 Dissolving in a solvent B to obtain a solution A; naVO (sodium VO) 3 Dissolving in a solvent B to obtain a solution B; mixing the solution A and the solution B to obtain a mixture; adding an acid solution into the mixture to convert the color of the mixture into peach red to obtain a dissolved solution C; mixing the solution B with the suspension, and heating and stirring at 40 to 90 ℃ for 0.5 to 2h to obtain a mixed solution A; mixing the solution C with the mixed solution A, and heating and stirring at 40-90 ℃ for 0.5-2h to obtain a mixed solution B; dropwise adding an acid solution into the mixed liquid B, heating and stirring at 40-90 ℃ until the pH value of the mixed liquid B is 1-3, stopping dropwise adding the acid solution, and continuously heating and stirring at 40-90 ℃ for 0.5-6 h to obtain a gel; crystallizing the gel, and roasting the crystallized product to obtain H 4 PW 11 VO 40 @ mesoporous TiO 2 A composite material.
In one embodiment of the invention, the mass fraction of the dilute sulfuric acid solution is 1 to 30 percent; the mass fraction of the hydrochloric acid solution is 1 to 20 percent; the mass fraction of the concentrated sulfuric acid is 80 to 98 percent; the mass fraction of the concentrated hydrochloric acid is 20 to 38 percent.
In one embodiment of the invention, the ionic solution is 1-butyl-3-methylimidazolium boron tetrafluoride ([ C ] 4 MIM]BF 4 ) 1-butyl-3-methylimidazolium hexafluorophosphate ([ C) 4 MIm]PF 6 ) And/or 1-butyl-3-methylimidazolium tribromide ([ C ] 4 MIm]Br 3 ）。
In one embodiment of the present invention, the crystallizing the gel is: and (3) putting the gel into a crystallization kettle with a polytetrafluoroethylene lining, continuously heating to 80-120 ℃ at the speed of 2-20 ℃/min, and continuously crystallizing at 80-120 ℃ for 24-72h to obtain a crystallization product.
In one embodiment of the present invention, the taking crystallization product is roasted as follows: cooling the crystallized product to 20 to 35 ℃, adding ether, and centrifuging to obtain a precipitate; centrifuging and washing the precipitate for 2 to 5 times by using ethanol, centrifuging and washing the precipitate for 1 to 3 times by using water, drying the precipitate in an oven at 60 to 120 ℃ for 6 to 24h, and finally roasting the precipitate in a muffle at 250 to 400 ℃ for 1 to 8h to obtain heteropoly acid @ mesoporous TiO 2 A composite material.
The invention also provides heteropoly acid @ mesoporous TiO 2 The heteropoly acid @ mesoporous TiO 2 The composite material is prepared by the method.
The invention also provides CO 2 Regenerated catalyst of said CO 2 The regenerated catalyst comprises the heteropoly acid @ mesoporous TiO 2 Composite material and forming assistant.
The invention also provides a method for preparing the CO 2 A method of regenerating a catalyst, the method comprising: the heteropoly acid @ mesoporous TiO is mixed 2 Mixing the composite material and a forming auxiliary agent to obtain a wet material; compressing and molding the wet material, and roasting the molded product to obtain the CO 2 And (4) regenerating the catalyst.
In one embodiment of the present invention, the heteropoly acid @ mesoporous TiO 2 The mass ratio of the composite material to the forming auxiliary agent is 300 to 450:50 to 330.
In one embodiment of the present invention, the forming aid is one or more of glass fiber, polyethylene glycol, ethanol, ammonia water, water glass, aqueous nitric acid solution, aqueous acetic acid solution, or aqueous citric acid solution.
In one embodiment of the present invention, the compression molding is: and (3) compressing and molding the wet material at a molding pressure of 100 to 1000MPa by using a tablet press to obtain a molded product.
In one embodiment of the present invention, the molding product is calcined to: drying the molded product at 80 to 120 ℃ for 2 to 24h, and then roasting in a muffle furnace at 150 to 400 ℃ for 2 to 24h to obtain the CO 2 And (4) regenerating the catalyst.
In one embodiment of the invention, the shaped product and CO 2 The shape of the regenerated catalyst is cylindrical, raschig ring, porous plum blossom, seven-hole sphere or gear.
The invention also provides the heteropoly acid @ mesoporous TiO prepared by the method 2 Method for preparing composite material or heteropoly acid @ mesoporous TiO 2 Composite materials or CO mentioned above 2 Regenerated catalyst or above-mentioned CO preparation 2 Method for regenerating catalyst in CO 2 Use in the regeneration of an absorbent.
The technical scheme of the invention has the following advantages:
1. the invention provides a method for preparing heteropoly acid @ mesoporous TiO 2 The method is based on a sol-gel-solvent method and an in-situ assembly one-step method, and firstly, a template agent, a solvent and titanium salt are mixed to obtain mesoporous TiO 2 Precursor suspension, and then adding mesoporous TiO 2 Mixing the precursor suspension and at least two kinds of oxysalts, then carrying out acidification treatment to obtain gel containing heteropoly acid nanocrystals, then carrying out solvent thermal crystallization treatment on the gel to obtain a crystallization product, and finally roasting the crystallization product to obtain heteropoly acid @ mesoporous TiO 2 Composite material, wherein, during the acidification treatment, the mesoporous TiO 2 A sol-gel reaction takes place to form TiO 2 The crystal skeleton is acidified by oxysalt to form heteropoly acid nanocrystalline, which penetrates TiO formed by sol gel 2 In the crystal framework, in the thermal crystallization treatment process, heteropoly acid nanocrystalline is further doped into TiO formed by sol gel 2 In the crystal framework.
Heteropolyacid @ mesoporous TiO prepared by using method 2 The composite material has high specific surface area and large pore volume, and the heteropoly acid @ mesoporous TiO 2 Composite material as CO 2 The regenerated catalyst not only improves CO 2 The release rate can also provide CO 2 Desorption of the L acid site (mesoporous TiO) 2 Provided) and B acid sites (provided by heteropoly acids), wherein the L acid site is used for attaching the intermediate carbamate and the B acid site is used for promoting the cleavage of the intermediate carbamate, and the combined action of the two significantly reduces CO 2 The activation energy required for the desorption reaction, and thus the CO is significantly reduced 2 The heat load in the desorption process effectively solves the problem of CO 2 High energy consumption and low efficiency in the desorption process.
Note: CO 2 2 The desorption process can be divided into two main steps: cleavage of the intermediate Carbamate (Amine-COO) - ) And deprotonation of protonated amines (AmineH) + ) Wherein the ratio of B acid sites/L acid sites and the number of acid sites to CO 2 The influence of desorption properties is large, while AmineH + The basic position of L is required during deprotonation.
Moreover, the heteropoly acid is easy to dissolve in water, and if the conventional impregnation method is adopted, the heteropoly acid is directly loaded in the mesoporous TiO 2 Surface, generation of CO in amine liquids 2 During desorption reaction, the heteropoly acid is easy to run off and has poor reusability, and the method uses an in-situ assembly method to dope heteropoly acid nanocrystalline into TiO formed by sol gel 2 In the crystal framework, the problem that the heteropoly acid is easy to run off is solved, so that the heteropoly acid @ mesoporous TiO prepared by the method 2 The composite material has strong reusability.
Furthermore, the method uses solvents such as ionic liquid and absolute ethyl alcohol as solvothermal, and the solvothermal is more favorable for crystal formation than hydrothermal, so that the heteropoly acid @ mesoporous TiO prepared by the method 2 CO enhancement by composite materials 2 The efficiency of the desorption process is better.
2. The invention provides a CO 2 Regenerated catalyst, said CO 2 The regenerated catalyst is prepared from heteropoly acid @ mesoporous TiO 2 The preparation method of the heteropoly acid @ mesoporous TiO2 composite material is based on a sol-gel-solvent method and an in-situ assembly one-step method, and the template agent, the solvent and the titanium salt are mixed to obtain the mesoporous TiO2 composite material 2 Precursor suspension, and then adding mesoporous TiO 2 Mixing the precursor suspension and at least two kinds of oxysalts, then carrying out acidification treatment to obtain gel containing heteropoly acid nanocrystals, then carrying out solvent thermal crystallization treatment on the gel to obtain a crystallization product, and finally roasting the crystallization product to obtain heteropoly acid @ mesoporous TiO 2 Composite material, wherein, during the acidification treatment, the mesoporous TiO 2 The sol-gel reaction takes place to form TiO 2 The crystal skeleton is acidified by oxysalt to form heteropoly acid nanocrystalline, which penetrates TiO formed by sol gel 2 In the crystal framework, in the thermal crystallization treatment process, heteropoly acid nanocrystalline is further doped into TiO formed by sol gel 2 In the crystal framework.
Heteropolyacid @ mesoporous TiO prepared by using method 2 The composite material has high specific surface area and large pore volume, and the heteropoly acid @ mesoporous TiO 2 Composite material as CO 2 The regenerated catalyst not only improves CO 2 The release rate can also provide CO 2 Desorption of the L acid site (mesoporous TiO) 2 Provided) and B acid sites (provided by heteropoly acids), wherein the L acid site is used for attaching the intermediate carbamate and the B acid site is used for promoting the cleavage of the intermediate carbamate, and the combined action of the two significantly reduces CO 2 The activation energy required for the desorption reaction, and thus the CO is significantly reduced 2 The heat load in the desorption process effectively solves the problem of CO 2 High energy consumption and low efficiency in the desorption process.
Note: CO 2 2 The desorption process can be divided into two main steps: cleavage of the intermediate Carbamate (Amine-COO) - ) And deprotonation of protonated amines (AmineH) + ) Wherein the ratio of B acid sites/L acid sites and the number of acid sites to CO 2 The influence of desorption properties is large, while AmineH + The basic position of L is required during deprotonation.
Moreover, the heteropoly acid is easy to dissolve in water, and if the conventional impregnation method is adopted, the heteropoly acid is directly loaded in the mesoporous TiO 2 Surface, generation of CO in amine liquids 2 During desorption reaction, the heteropoly acid is easy to run off and has poor reusability, and the method uses an in-situ assembly method to dope heteropoly acid nanocrystalline into TiO formed by sol gel 2 In the crystal framework, the problem that the heteropoly acid is easy to run off is solved, so that the heteropoly acid @ mesoporous TiO prepared by the method 2 The composite material has strong reusability.
Furthermore, the method uses solvents such as ionic liquid and absolute ethyl alcohol as solvothermal, and the solvothermal is more favorable for crystal formation than hydrothermal, so that the heteropoly acid @ mesoporous TiO prepared by the method 2 CO enhancement by composite materials 2 The effect of the desorption process efficiency is better.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The following examples do not show specific experimental procedures or conditions, and can be performed according to the procedures or conditions of the conventional experimental procedures described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
P123, anhydrous ethanol, tiCl referred to in the examples below 4 Sodium tungstate dihydrate, tetrabutyl titanate and Na 2 HPO 4 ·12H 2 O, concentrated hydrochloric acid, acetic acid aqueous solution, naVO 3 ·2H 2 O, concentrated sulfuric acid, industrial grade titanium dioxide and 1-butyl-3-methylimidazolium boron tetrafluoride ([ C ] 4 MIM]BF 4 ) All purchased from the national pharmaceutical group chemical agents limited.
Example 1: CO 2 2 Regenerated catalyst and preparation thereof
This example provides a CO 2 The preparation method of the regenerated catalyst comprises the following steps:
1、H 3 PW 12 O 40 @ mesoporous TiO 2 Preparation of composite materials
Dissolving 10g of P123 in 200mL (158 g) of absolute ethanol to obtain a solution A; 20g of TiCl 4 Mixing with the solution A, and stirring at 800rpm for 2h to obtain a suspension; 6.7g of sodium tungstate dihydrate is dissolved in 150g of water at the temperature of 80 ℃ to obtain a dissolved solution B; 0.9g of Na 2 HPO 4 ·12H 2 Dissolving O in 20g of water to obtain a solution C; mixing the solution B with the suspension, heating and stirring at 60 deg.C and 1000rpm for 60min to obtain mixed solution A; mixing the dissolved solution C with the mixed solution A, and heating and stirring at 60 deg.C and 1000rpm for 60min to obtain mixed solution B; adding concentrated hydrochloric acid with mass fraction of 38% into the mixed solution B, heating and stirring at 60 deg.C and 1200rpm until mixingStopping dripping concentrated hydrochloric acid after the pH value of the solution B reaches 2, and continuously heating and stirring at 60 ℃ and 800rpm for 40min to obtain gel; putting the gel into a crystallization kettle with a polytetrafluoroethylene lining, continuously heating to 80 ℃ at a speed of 10 ℃/min, and continuously crystallizing for 36 hours at 80 ℃ to obtain a crystallized product; cooling the crystallized product to room temperature (25 ℃), adding 36g of diethyl ether, centrifuging and taking precipitate; centrifuging and washing the precipitate with ethanol for 3 times, centrifuging and washing with water for 1 time, drying in a 100 deg.C oven for 12H, and calcining in a 350 deg.C muffle furnace for 4H to obtain H 3 PW 12 O 40 @ mesoporous TiO 2 A composite material.
2、CO 2 Preparation of regenerated catalyst
200g of H 3 PW 12 O 40 @ mesoporous TiO 2 Mixing the composite material with 50g of acetic acid aqueous solution with the mass fraction of 5%, adding the mixture into a mixer, and stirring for 2 hours at 2500r/min to obtain wet materials; compressing and molding the wet material under 500MPa pressure by using a tablet press, drying the cylindrical molded product at 100 ℃ for 12h, and then roasting in a muffle furnace at 300 ℃ for 12h to obtain CO 2 And (4) regenerating the catalyst.
Example 2: CO 2 2 Regenerated catalyst and preparation thereof
This example provides a CO 2 The preparation method of the regenerated catalyst comprises the following steps:
1、H 4 PW 11 VO 40 @ mesoporous TiO 2 Preparation of composite materials
Dissolving 10g of P123 in 200mL (158 g) of absolute ethanol to obtain a solution A; 20g of TiCl are added 4 Mixing with the solution A, and stirring at 800rpm for 2h to obtain a suspension; 6.7g of sodium tungstate dihydrate is dissolved in 150g of water at the temperature of 80 ℃ to obtain a dissolved solution B; 0.6g of Na 2 HPO 4 ·12H 2 Dissolving O in 20g of water to obtain a solution A; 0.6g of NaVO 3 ·2H 2 Dissolving O in 20g of water to obtain a solution B; mixing the solution A and the solution B to obtain a mixture; adding 1.8g of concentrated sulfuric acid with the mass fraction of 98% into the mixture to enable the color of the mixture to be changed into peach red, and obtaining a dissolved solution C; mixing solution B and the suspension at 60 deg.CHeating and stirring at 1000rpm for 60min to obtain a mixed solution A; mixing the solution C with the mixed solution A, and heating and stirring at 80 deg.C and 1000rpm for 60min to obtain mixed solution B; dropwise adding 38% concentrated hydrochloric acid into the mixed solution B, heating and stirring at 60 deg.C and 1200rpm until the pH value of the mixed solution B reaches 2, stopping dropwise adding concentrated hydrochloric acid, and continuously heating and stirring at 60 deg.C and 800rpm for 60min to obtain gel; putting the gel into a crystallization kettle with a polytetrafluoroethylene lining, continuously heating to 80 ℃ at the speed of 5 ℃/min, and continuously crystallizing for 36 hours at 80 ℃ to obtain a crystallized product; cooling the crystallized product to room temperature (25 ℃), adding 36g of diethyl ether, centrifuging and taking precipitate; centrifuging and washing the precipitate with ethanol for 3 times, centrifuging and washing with water for 1 time, drying in an oven at 100 deg.C for 12H, and calcining in a muffle furnace at 350 deg.C for 4H to obtain H 4 PW 11 VO 40 @ mesoporous TiO 2 A composite material.
2、CO 2 Preparation of regenerated catalyst
200g of H 4 PW 11 VO 40 @ mesoporous TiO 2 Mixing the composite material with 100g of a nitric acid aqueous solution with the mass fraction of 5%, adding the mixture into a mixer, and stirring for 2 hours at 2500r/min to obtain a wet material; compressing and molding the wet material under 500MPa pressure by using a tablet press, drying the cylindrical molded product at 100 ℃ for 12h, and then roasting in a muffle furnace at 300 ℃ for 12h to obtain CO 2 And (4) regenerating the catalyst.
Example 3: CO 2 2 Regenerated catalyst and preparation thereof
This example provides a CO 2 The preparation method of the regenerated catalyst comprises the following steps:
1、H 3 PW 12 O 40 @ mesoporous TiO 2 Preparation of composite materials
Dissolving 10g of hexadecyl trimethyl ammonium bromide in 150mL of deionized water to obtain a dissolved solution A; 20g of TiCl are added 4 Mixing with the solution A, and stirring at 1200rpm for 2h to obtain a suspension; 6.7g of sodium tungstate dihydrate is dissolved in 150g of water at the temperature of 80 ℃ to obtain a dissolved solution B; 0.9g of Na 2 HPO 4 ·12H 2 Dissolving O in 20g of water to obtain a solution C; mixing solution B withMixing the suspension, heating and stirring at 40 deg.C and 1200rpm for 60min to obtain mixed solution A; mixing the solution C with the mixed solution A, and heating and stirring at 60 deg.C and 1200rpm for 80min to obtain mixed solution B; dropwise adding 38% concentrated hydrochloric acid into the mixed solution B, heating and stirring at 60 deg.C and 1200rpm until the pH value of the mixed solution B reaches 2, stopping dropwise adding concentrated hydrochloric acid, and continuously heating and stirring at 60 deg.C and 1200rpm for 40min to obtain gel; putting the gel into a crystallization kettle with a polytetrafluoroethylene lining, continuously heating to 80 ℃ at the speed of 20 ℃/min, and continuously crystallizing for 36 hours at 80 ℃ to obtain a crystallized product; cooling the crystallized product to room temperature (25 ℃), adding 50g of diethyl ether, centrifuging and taking precipitate; centrifuging and washing the precipitate with ethanol for 3 times, centrifuging and washing with water for 1 time, drying in an oven at 100 deg.C for 12H, and calcining in a muffle furnace at 350 deg.C for 6H to obtain H 3 PW 12 O 40 @ mesoporous TiO 2 A composite material.
2、CO 2 Preparation of regenerated catalyst
200g of H 3 PW 12 O 40 @ mesoporous TiO 2 Mixing the composite material with 100g of a nitric acid aqueous solution with the mass fraction of 5%, adding the mixture into a mixer, and stirring for 2 hours at 2500r/min to obtain a wet material; compressing and molding the wet material under 600MPa pressure by using a tablet press, drying the cylindrical molded product at 100 ℃ for 12h, and then roasting in a muffle furnace at 300 ℃ for 12h to obtain CO 2 And (4) regenerating the catalyst.
Example 4: CO 2 2 Regenerated catalyst and preparation thereof
This example provides a CO 2 The preparation method of the regenerated catalyst comprises the following steps:
1、H 3 PW 12 O 40 @ mesoporous TiO 2 Preparation of composite materials
10g of P123 and 10g of 1-butyl-3-methylimidazolium boron tetrafluoride ([ C ] 4 MIM]BF 4 ) Dissolving in 140g of deionized water to obtain a solution A; 20g of TiCl 4 Mixing with the solution A, and stirring at 1200rpm for 2h to obtain a suspension; 6.7g of sodium tungstate dihydrate is dissolved in 150g of water at the temperature of 80 ℃ to obtain a dissolved solution B; 0.9g of Na 2 HPO 4 ·12H 2 Dissolving O in 20g of water to obtain a solution C; mixing the solution B with the suspension, and heating and stirring at 40 deg.C and 1200rpm for 60min to obtain mixed solution A; mixing the solution C with the mixed solution A, and heating and stirring at 50 deg.C and 1200rpm for 80min to obtain mixed solution B; dropwise adding 38% concentrated hydrochloric acid into the mixed solution B, heating and stirring at 60 deg.C and 1000rpm until the pH value of the mixed solution B reaches 2, stopping dropwise adding concentrated hydrochloric acid, and continuously heating and stirring at 60 deg.C and 1000rpm for 60min to obtain gel; putting the gel into a crystallization kettle with a polytetrafluoroethylene lining, continuously heating to 80 ℃ at a speed of 20 ℃/min, and continuously crystallizing for 36 hours at 80 ℃ to obtain a crystallized product; cooling the crystallized product to room temperature (25 ℃), adding 36g of diethyl ether, centrifuging and taking precipitate; centrifuging and washing the precipitate with ethanol for 3 times, centrifuging and washing with water for 1 time, drying in an oven at 100 deg.C for 12H, and calcining in a muffle furnace at 350 deg.C for 6H to obtain H 3 PW 12 O 40 @ mesoporous TiO 2 A composite material.
2、CO 2 Preparation of regenerated catalyst
200g of H 3 PW 12 O 40 @ mesoporous TiO 2 Mixing the composite material with 100g of a nitric acid aqueous solution with the mass fraction of 5%, adding the mixture into a mixer, and stirring for 2 hours at 2500r/min to obtain a wet material; compressing and molding the wet material under 800MPa pressure by using a tablet press, taking a cylindrical molding product, drying the cylindrical molding product at 100 ℃ for 12h, and then roasting the cylindrical molding product in a muffle furnace at 300 ℃ for 12h to obtain CO 2 And (4) regenerating the catalyst.
Example 5: CO 2 2 Regenerated catalyst and preparation thereof
The present example provides a CO 2 The preparation method of the regenerated catalyst comprises the following steps:
1、H 3 PW 12 O 40 @ mesoporous TiO 2 Preparation of composite materials
Dissolving 10g of P123 in 200mL (158 g) of absolute ethanol to obtain a solution A; mixing 35.8g of tetrabutyl titanate with the dissolving solution A, and stirring at 800rpm for 2 hours to obtain a suspension; 6.7g of sodium tungstate dihydrate is dissolved in 150g of water at the temperature of 80 ℃ to obtain a dissolved solution B; 0.9g of Na 2 HPO 4 ·12H 2 Dissolving O in 20g of water to obtain a solution C; mixing the solution B with the suspension, heating and stirring at 60 deg.C and 1000rpm for 60min to obtain mixed solution A; mixing the dissolved solution C with the mixed solution A, and heating and stirring at 60 deg.C and 1000rpm for 60min to obtain mixed solution B; dropwise adding 38% concentrated hydrochloric acid into the mixed solution B, heating and stirring at 60 deg.C and 1200rpm until the pH value of the mixed solution B reaches 2, stopping dropwise adding concentrated hydrochloric acid, and continuously heating and stirring at 60 deg.C and 800rpm for 40min to obtain gel; putting the gel into a crystallization kettle with a polytetrafluoroethylene lining, continuously heating to 80 ℃ at a speed of 10 ℃/min, and continuously crystallizing for 36 hours at 80 ℃ to obtain a crystallized product; cooling the crystallized product to room temperature (25 ℃), adding 36g of diethyl ether, centrifuging and taking precipitate; centrifuging and washing the precipitate with ethanol for 3 times, centrifuging and washing with water for 1 time, drying in a 100 deg.C oven for 12H, and calcining in a 350 deg.C muffle furnace for 4H to obtain H 3 PW 12 O 40 @ mesoporous TiO 2 A composite material.
2、CO 2 Preparation of regenerated catalyst
200g of H 3 PW 12 O 40 @ mesoporous TiO 2 Mixing the composite material with 50g of acetic acid aqueous solution with the mass fraction of 5%, adding the mixture into a mixer, and stirring for 2 hours at 2500r/min to obtain wet materials; compressing and molding the wet material under 500MPa pressure by using a tablet press, drying the cylindrical molding product at 100 ℃ for 12h, and then roasting in a muffle furnace at 300 ℃ for 12h to obtain CO 2 And (4) regenerating the catalyst.
Comparative example 1: CO 2 2 Regenerated catalyst and preparation thereof
This comparative example provides a CO 2 The preparation method of the regenerated catalyst comprises the following steps:
1. mesoporous TiO2 2 Preparation of the Material
Dissolving 10g of P123 in 200mL (158 g) of absolute ethanol to obtain a solution; 20g of TiCl are added 4 Mixing with the solution, and stirring at 1000rpm for 60min to form gel; placing the gel into a crystallization kettle with polytetrafluoroethylene lining, continuously heating to 80 ℃ at a speed of 10 ℃/min, and holding at 80 DEG CContinuously crystallizing for 36 hours to obtain a crystallized product; centrifugally washing the crystallized product with ethanol for 2 times, centrifugally washing with water for 2 times, drying in a 100 ℃ oven for 12 hours, and roasting in a 350 ℃ muffle furnace for 4 hours to obtain mesoporous TiO 2 A material.
2、CO 2 Preparation of regenerated catalyst
200g of mesoporous TiO 2 Mixing the material with 100g of nitric acid aqueous solution with the mass fraction of 5%, adding the mixture into a mixer, and stirring for 2 hours at the speed of 2500r/min to obtain a wet material; compressing and molding the wet material under 500MPa pressure by using a tablet press, drying the cylindrical molding product at 100 ℃ for 12h, and then roasting in a muffle furnace at 300 ℃ for 12h to obtain a carrier; 10.00g of sodium tungstate dihydrate and 1.30g of Na 2 HPO 4 ·12H 2 Dissolving O in 15mL of boiling water at 100 ℃ to obtain a solution; dropwise adding 8mL of concentrated hydrochloric acid with the mass fraction of 38% into the dissolved solution, stirring at 1000rpm for 60min, and after adding the concentrated hydrochloric acid, beginning to precipitate phosphotungstic acid to obtain a mixture; cooling the mixture to room temperature (25 ℃), adding 6mL of diethyl ether, shaking, and taking the lower phosphotungstic acid diethyl ether complex; washing the phosphotungstic acid ether complex with water for 3 times by centrifugation, and then drying the complex in an oven at 70 ℃ to constant weight to obtain 5.89g of phosphotungstic acid; drying 5g of carrier in a 120 ℃ oven for 2 hours, weighing, then putting the carrier into a watch glass, slowly dripping distilled water until the carrier does not absorb water any more, slightly absorbing the excessive water on the surface of the carrier by using filter paper, weighing again, and calculating the water absorption of the carrier, wherein the calculation formula of the water absorption is as follows: w = (B-G)/G × 100% (where B is the mass of the sample saturated with water and G is the mass of the sample after drying), and the water absorption of the obtained carrier was calculated as: 60 percent; dissolving 5g of phosphotungstic acid in 20g of deionized water to obtain a mixed solution; continuously heating the mixed solution to 50 ℃ at 1200rpm, and continuously stirring for 2 hours at 1200rpm to obtain an impregnation solution; weighing an impregnation liquid according to the water absorption rate of a carrier, mixing 60mL of the impregnation liquid with 100g of the carrier, standing for 1h, then placing the mixture into a 120 ℃ drying oven for drying for 12h, and finally roasting in a 350 ℃ muffle furnace for 4h to obtain CO 2 And (4) regenerating the catalyst.
Comparative example 2: CO 2 2 Regenerated catalyst and preparation thereof
This comparative example provides a CO 2 The preparation method of the regenerated catalyst comprises the following steps:
1、H 4 SiW 12 O 40 @TiO 2 preparation of composite materials
Dissolving 6.7g of sodium tungstate dihydrate in 100g of water at 80 ℃ to obtain a dissolved solution; adding 50g of industrial titanium white (TiO) powder into the dissolved solution 2 ) Stirring at 800rpm for 20min to obtain mixed solution A; 0.9g of Na 2 HPO 4 ·12H 2 Mixing the O and the mixed solution A, and heating and stirring at 60 ℃ and 800rpm for 20min to obtain a mixed solution B; dropwise adding concentrated hydrochloric acid with the mass fraction of 38% into the mixed solution B, and continuously heating and stirring at 60 ℃ and 1200rpm until the pH value of the mixed solution B is 2 to obtain gel; cooling the gel to room temperature (25 ℃), adding 50g of diethyl ether, centrifuging and taking a precipitate; drying the precipitate in an oven at 80 deg.C for 12H, centrifuging with ethanol for 2 times, centrifuging with water for 2 times, drying in an oven at 120 deg.C for 12H, and calcining in a muffle furnace at 350 deg.C for 6H to obtain H 4 SiW 12 O 40 @TiO 2 A composite material.
2、CO 2 Preparation of regenerated catalyst
200g of H 4 SiW 12 O 40 @TiO 2 Mixing the composite material with 100g of a nitric acid aqueous solution with the mass fraction of 5%, adding the mixture into a mixer, and stirring the mixture for 2 hours at 1500r/min to obtain a wet material; compressing and molding the wet material under 600MPa pressure by using a tablet press, drying the cylindrical molded product at 100 ℃ for 12h, and then roasting in a muffle furnace at 300 ℃ for 12h to obtain CO 2 And (4) regenerating the catalyst.
Comparative example 3: CO 2 2 Regenerated catalyst and preparation thereof
This comparative example provides a CO 2 The preparation method of the regenerated catalyst comprises the following steps:
1. mesoporous TiO2 2 Preparation of the Material
Dissolving 10g of P123 in 200mL (158 g) of absolute ethanol to obtain a solution; 20g of TiCl are added 4 Mixing with the solution, and stirring at 1000rpm for 60min to form gel; will coagulateThe glue is put into a crystallization kettle with a polytetrafluoroethylene lining, the temperature is continuously raised to 80 ℃ at the speed of 10 ℃/min, and then crystallization is continuously carried out for 36 hours at 80 ℃ to obtain a crystallization product; centrifugally washing the crystallized product with ethanol for 2 times, centrifugally washing with water for 2 times, drying in an oven at 100 ℃ for 12 hours, and finally roasting in a muffle furnace at 350 ℃ for 4 hours to obtain mesoporous TiO 2 A material.
2、CO 2 Preparation of regenerated catalyst
200g of mesoporous TiO 2 Mixing the material with 100g of 5% nitric acid aqueous solution, adding the mixture into a mixer, and stirring for 2 hours at 2500r/min to obtain wet material; compressing and molding the wet material under 500MPa pressure by using a tablet press, drying the cylindrical molded product at 100 ℃ for 12h, and then roasting in a muffle furnace at 300 ℃ for 12h to obtain CO 2 And (4) regenerating the catalyst.
Experimental example 1: CO 2 2 Performance validation of regenerated catalyst
Detection of CO in examples 1 to 5 and comparative examples 1 to 3 2 The physicochemical properties of the regenerated catalyst and the detection results are shown in Table 1. Wherein the texture properties are measured by a Tristar model 2020 adsorber available from Micromeritics, USA, the specific surface area is measured by the BET method (the BET method is described in "science publishers, xue, as written in" molecular Sieve and porous Material chemistry ", page 151)," the micropore pore volume and pore size are measured by the t-Plot method (the t-Plot method is described in "science publishers, xue, as written in" molecular Sieve and porous Material chemistry ", page 152)," the mesopore pore volume and pore size are measured by the BJH method (the BJH method is described in "science publishers, xue, as written in" molecular Sieve and porous Material chemistry ", pages 150 and 155").
Detection of CO in examples 1 to 5 and comparative examples 1 to 3 2 The catalytic performance of the regenerated catalyst and the detection results are shown in Table 2. The method for detecting the catalytic performance comprises the following steps:
detection of CO by regeneration experiments 2 The catalytic performance of the regenerated catalyst; the amine liquid used in the regeneration experiment is CO 2 CO-riched obtained under the conditions of partial pressure of 0.15MPa and temperature of 40 DEG C 2 (iii) an amine solution (monoethanolamine concentration of the amine solution is 1 mol/L); for regeneration experimentsThe instrument consists of an oil bath pan, a thermometer, a mechanical stirrer, a condenser tube and an electric energy meter; 1000mL of amine solution was charged to a four-necked flask in an oil bath with CO 2 The regenerated catalyst is placed in a four-neck flask, and a condenser is placed at the top of the four-neck flask, so that the loss of amine and water caused by evaporation is reduced; the oil bath temperature was set at 90 ℃ (regeneration temperature), at which the amine solution was maintained for 2 hours, and the amine solution was stirred at 1600 rpm; the energy cost in the amine liquid regeneration process is recorded by a digital display single-phase electric energy meter (purchased from ancorui electrical gas company, ltd); calculating CO according to the experimental result of the regeneration experiment 2 Regenerated catalyst circulation capacity, heat load and CO 2 The desorption rate, calculated as follows:
circulation capacity (CC, mol) = (a) r −a l ）×C×V；
Wherein, a r Initial CO representing amine liquid 2 Loaded (mol CO) 2 Per mol of amine), a) l CO representing regenerated amine liquids 2 Loaded (mol CO) 2 Per mol of amine), C (mol/L) and V (L) are the concentration and volume of the amine liquid, respectively; the circulating capacity represents the amine capture and CO release 2 The maximum capacity of (c); measuring the absorption amount of carbon dioxide in the amine liquid by an acid-base titration method;
CO 2 desorption rate (Rd, mol/min) = n co2 /t d =CC/120；
Wherein n is co2 Represents CO 2 Amount of (mol), t d Represents the desorption time (2 h); total energy requirement (H) in solution regeneration t ) Supplied by electric heaters, meaning per mole of CO released 2 Energy consumption of the medium amine;
thermal load (H, KJ/mol CO) 2 ）=（H t /time）/（n co2 /time）=Q E /CC；
Wherein H t Representing the total energy input, Q E Representing the total energy consumption (kJ, electric energy meter reading).
Detection of CO in examples 1 to 5 and comparative examples 1 to 3 2 The regeneration performance of the regenerated catalyst and the detection results are shown in Table 3. Wherein the content of the first and second substances,the method for detecting the regeneration performance comprises the following steps:
repeated catalytic performance detection is carried out to obtain CO 2 The regenerated catalyst desorbs CO after different times 2 The desorption rate.
As can be seen from Table 1, P123 was used as a template, absolute ethanol as solvent A and TiCl 4 H prepared as titanium source 3 PW 12 O 40 @ mesoporous TiO 2 The specific surface area of the composite catalyst (example 1) is as high as 95.8m 2 G, average pore diameter of 3.6nm and total pore volume of 0.18cm 3 (g) a texture superior to heteropoly acid @ mesoporous TiO prepared using cetyltrimethylammonium bromide as a template (example 3), 1-butyl-3-methylimidazolium boron titanium tetrafluoride solution as solvent A (example 4), or tetrabutyl ester as a titanium source (example 5) 2 Composite material, can be CO 2 The desorption reaction provides more catalytically active sites. The composite material catalyst prepared by adopting industrial titanium dioxide as a titanium source (comparative example 2) has the specific surface area of only 53.8m 2 /g。
As can be seen from Table 2, P123 was used as a template, absolute ethanol as solvent A and TiCl 4 H prepared as titanium source 3 PW 12 O 40 @ mesoporous TiO 2 The composite catalyst (example 1) had higher CO 2 Catalytic desorption performance, desorption rate of 0.66mol/h, circulation capacity of 1.32mol, heat load of 889.4KJ/mol CO 2 (ii) a And adopts mesoporous TiO 2 The desorption rate of the catalyst is only 0.44mol/h, the circulating capacity is 0.88mol, and the heat load is 1321.7KJ/mol CO 2 (comparative example 3). This indicates that heteropoly acid as an active component favors CO 2 The desorption reaction occurs because the heteropolyacid can provide the B acid site, which is favorable for the intermediate carbamate (Amine-COO) - ) Cleavage of the N-C bond.
As can be seen from Table 3, P123 was used as a template, absolute ethanol as solvent A and TiCl 4 H prepared as titanium source 3 PW 12 O 40 @ mesoporous TiO 2 The composite catalyst (example 1) can still maintain higher cycle capacity after being recycled for more than 5 times; but is prepared by an immersion methodThe composite catalyst (comparative example 1) and the composite catalyst (comparative example 2) prepared by adopting the industrial titanium dioxide as the raw material have poor recycling performance. The catalyst is prepared by adopting a dipping method and the catalyst is prepared by adopting industrial titanium dioxide as a raw material, the active component heteropoly acid is only dispersed on the surface of the carrier and is not doped into a mesoporous titanium dioxide crystal skeleton structure, and the heteropoly acid is dissolved in water and is added into CO 2 The loss is more easy in the desorption process, and the active component heteropoly acid can be doped into the mesoporous TiO of the composite material synthesized by the in-situ assembly one-step method 2 In the crystal skeleton structure, in CO 2 The loss is not easy to occur in the desorption process, and the reusability is strong.
Figure 127133DEST_PATH_IMAGE001
Figure 941505DEST_PATH_IMAGE002
Figure 534658DEST_PATH_IMAGE003
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the invention.

Claims (6)

1. Heteropolyacid @ mesoporous TiO 2 Composite material in CO 2 The application of the heteropoly acid @ mesoporous TiO in absorbent regeneration is characterized in that 2 The preparation method of the composite material comprises the following steps: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; dissolving the oxysalt A in the solventAgent B to obtain solution B; dissolving the oxysalt B in a solvent B to obtain a dissolved solution C; mixing the dissolving solution B and the suspension, and stirring to obtain a mixed solution A; mixing the dissolved solution C with the mixed solution A, and stirring to obtain a mixed solution B; dropwise adding the acid solution into the mixed solution B while stirring until the pH value of the mixed solution B reaches 1-3, stopping dropwise adding the acid solution, and continuously stirring to obtain gel; crystallizing the gel, and roasting the crystallized product to obtain heteropoly acid @ mesoporous TiO 2 A composite material; the mass ratio of the template agent, the solvent A, the titanium salt, the solvent B, the oxysalt A, the oxysalt B and the acid solution is 0-2: 5 to 100:0.5 to 10:5 to 100:0.5 to 2:0.05 to 1:5 to 20.
2. The use of claim 1, wherein the titanium salt is one or more of titanium tetrachloride, titanium sulfate or tetrabutyl titanate; the template agent is one or more of P123, dodecyl sulfonic acid, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride or hexadecyl trimethyl ammonium.
3. The use according to claim 1, wherein the oxoacid salt a is Na 2 WO 4 And/or Na 2 MoO 4 (ii) a The oxysalt B is Na 2 HPO 4 、NaVO 3 And/or Na 2 SiO 3 。
4. The use of claim 1, wherein said heteropoly acid @ mesoporous TiO 2 The preparation method of the composite material comprises the following steps: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; dissolving the oxysalt A in a solvent B to obtain a dissolved solution B; dissolving the oxysalt B in a solvent B to obtain a dissolved solution C; mixing the solution B with the suspension, and heating and stirring at 40-90 ℃ for 0.5-2 h to obtain a mixed solution A; mixing the dissolved solution C with the mixed solution A, and heating and stirring at 40-90 ℃ for 0.5-2 h to obtain a mixed solution B; dropwise adding the acid solution into the mixed solution B, heating and stirring at 40-90 ℃ until the pH value of the mixed solution B reaches 1-3, stopping dropwise adding the acid solution, andcontinuously heating and stirring for 0.5-6 h at 40-90 ℃ to obtain gel; crystallizing the gel, and roasting the crystallized product to obtain heteropoly acid @ mesoporous TiO 2 A composite material.
5. The use according to claim 1, wherein the solvent A is one or more of water, ionic liquid or organic solvent; the solvent B is one or more of water, dilute sulfuric acid solution or hydrochloric acid solution; the acid solution is concentrated hydrochloric acid and/or concentrated sulfuric acid.
6. Use according to any one of claims 1 to 5, wherein when the oxoacid salt A is Na 2 WO 4 The oxysalt B is Na 2 HPO 4 The heteropoly acid @ mesoporous TiO 2 The preparation method of the composite material comprises the following steps: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; mixing Na 2 WO 4 Dissolving the mixture in a solvent B at the temperature of between 40 and 90 ℃ to obtain a dissolved solution B; mixing Na 2 HPO 4 Dissolving in a solvent B to obtain a dissolved solution C; mixing the solution B and the suspension, and heating and stirring at 40-90 ℃ for 0.5-2 h to obtain a mixed solution A; mixing the dissolved solution C with the mixed solution A, and heating and stirring at 40-90 ℃ for 0.5-2 h to obtain a mixed solution B; dropwise adding an acid solution into the mixed solution B, heating and stirring at 40-90 ℃ until the pH value of the mixed solution B reaches 1-3, stopping dropwise adding the acid solution, and continuously heating and stirring at 40-90 ℃ for 0.5-6 h to obtain gel; crystallizing the gel, and roasting the crystallized product to obtain H 3 PW 12 O 40 @ mesoporous TiO 2 A composite material;
when the oxysalt A is Na 2 WO 4 The oxysalt B is Na 2 SiO 3 The heteropoly acid @ mesoporous TiO 2 The preparation method of the composite material comprises the following steps: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; mixing Na 2 WO 4 Dissolving the mixture in a solvent B at the temperature of between 40 and 90 ℃ to obtain a dissolved solution B; mixing Na 2 SiO 3 Dissolving in a solvent B to obtain a dissolved solution C; mixing the solution B with the suspensionThen heating and stirring the mixture for 0.5 to 2 hours at the temperature of between 40 and 90 ℃ to obtain mixed liquor A; mixing the dissolved solution C with the mixed solution A, and heating and stirring at 40-90 ℃ for 0.5-2 h to obtain a mixed solution B; dropwise adding an acid solution into the mixed solution B, heating and stirring at 40-90 ℃ until the pH value of the mixed solution B reaches 1-3, stopping dropwise adding the acid solution, and continuously heating and stirring at 40-90 ℃ for 0.5-6 h to obtain gel; crystallizing the gel, and roasting the crystallized product to obtain H 3 SiW 12 O 40 @ mesoporous TiO 2 A composite material;
when the oxysalt A is Na 2 MoO 4 The oxysalt B is Na 2 HPO 4 The heteropoly acid @ mesoporous TiO 2 The preparation method of the composite material comprises the following steps: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; mixing Na 2 MoO 4 Dissolving the mixture in a solvent B at the temperature of between 40 and 90 ℃ to obtain a dissolved solution B; na is mixed with 2 HPO 4 Dissolving in a solvent B to obtain a dissolved solution C; mixing the solution B and the suspension, and heating and stirring at 40-90 ℃ for 0.5-2 h to obtain a mixed solution A; mixing the dissolved solution C with the mixed solution A, and heating and stirring at 40-90 ℃ for 0.5-2 h to obtain a mixed solution B; dropwise adding an acid solution into the mixed solution B, heating and stirring at 40-90 ℃ until the pH value of the mixed solution B reaches 1-3, stopping dropwise adding the acid solution, and continuously heating and stirring at 40-90 ℃ for 0.5-6 h to obtain gel; crystallizing the gel, and roasting the crystallized product to obtain H 3 PMo 12 O 40 @ mesoporous TiO 2 A composite material;
when the oxysalt A is Na 2 MoO 4 The oxysalt B is Na 2 SiO 3 The heteropoly acid @ mesoporous TiO 2 The preparation method of the composite material comprises the following steps: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; na is mixed with 2 MoO 4 Dissolving the mixture in a solvent B at the temperature of between 40 and 90 ℃ to obtain a dissolved solution B; na is mixed with 2 SiO 3 Dissolving in a solvent B to obtain a dissolved solution C; mixing the solution B and the suspension, and heating and stirring at 40-90 ℃ for 0.5-2 h to obtain a mixed solution A; mixing the solution C with the mixed solution A, heating and stirring at 40-90 ℃ for 0.5-2 h to obtainTo mixed solution B; dropwise adding an acid solution into the mixed solution B while stirring until the pH value of the mixed solution B reaches 1-3, stopping dropwise adding the acid solution, and continuously heating and stirring at 40-90 ℃ for 0.5-6 h to obtain gel; crystallizing the gel, and roasting the crystallized product to obtain H 3 SiMo 12 O 40 @ mesoporous TiO 2 A composite material;
when the oxysalt A is Na 2 WO 4 The oxysalt B is Na 2 HPO 4 And NaVO 3 The heteropoly acid @ mesoporous TiO 2 The preparation method of the composite material comprises the following steps: dissolving a template agent in a solvent A to obtain a dissolved solution A; mixing titanium salt with the solution A to obtain a suspension; na is mixed with 2 WO 4 Dissolving the mixture in a solvent B at the temperature of between 40 and 90 ℃ to obtain a dissolved solution B; mixing Na 2 HPO 4 Dissolving in a solvent B to obtain a solution A; naVO (sodium VO) 3 Dissolving in a solvent B to obtain a solution B; mixing the solution A and the solution B to obtain a mixture; adding an acid solution into the mixture to convert the color of the mixture into peach red to obtain a dissolved solution C; mixing the solution B with the suspension, and heating and stirring at 40-90 ℃ for 0.5-2 h to obtain a mixed solution A; mixing the dissolved solution C with the mixed solution A, and heating and stirring at 40-90 ℃ for 0.5-2 h to obtain a mixed solution B; dropwise adding an acid solution into the mixed solution B, heating and stirring at 40-90 ℃ until the pH value of the mixed solution B reaches 1-3, stopping dropwise adding the acid solution, and continuously heating and stirring at 40-90 ℃ for 0.5-6 h to obtain gel; crystallizing the gel, and roasting the crystallized product to obtain H 4 PW 11 VO 40 @ mesoporous TiO 2 A composite material.
CN202211186838.5A 2022-09-28 2022-09-28 Regenerated catalyst and preparation method and application thereof Active CN115282993B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211186838.5A CN115282993B (en) 2022-09-28 2022-09-28 Regenerated catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211186838.5A CN115282993B (en) 2022-09-28 2022-09-28 Regenerated catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115282993A CN115282993A (en) 2022-11-04
CN115282993B true CN115282993B (en) 2023-02-03

Family

ID=83833676

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211186838.5A Active CN115282993B (en) 2022-09-28 2022-09-28 Regenerated catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115282993B (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5300703A (en) * 1993-04-05 1994-04-05 Texaco Chemical Company Alkylphenol synthesis using heteropoly acid catalysts
US5919725A (en) * 1993-11-19 1999-07-06 Exxon Research And Engineering Co. Heteropoly salts or acid salts deposited in the interior of porous supports
CN1958153A (en) * 2006-11-01 2007-05-09 南京师范大学 Hybridization materials of polymetallic salts of oxygen and acid / mesoporous molecular sieve, and preparation method
RU2009126236A (en) * 2009-07-09 2011-01-20 Общество с ограниченной ответственностью "УНИСИТ" (RU) NANOCOMPOSITE MATERIAL AND METHOD FOR PRODUCING IT
CN103191786A (en) * 2013-04-23 2013-07-10 浙江师范大学 Preparation method of MIL-100(Fe) packaged phosphotungstic heteropolyacid catalyst
WO2015052325A1 (en) * 2013-10-11 2015-04-16 Nilu - Stiftelsen Norsk Institutt For Luftforskning Capture of carbon dioxide
CN108126719A (en) * 2017-12-21 2018-06-08 西安理工大学 A kind of preparation method of phosphotungstic acid doped titanium dioxide photocatalyst
CN109513313A (en) * 2017-09-20 2019-03-26 中国石油化工股份有限公司 A kind of low-temperature catalyzed regeneration method of collecting carbonic anhydride solvent
CN111804335A (en) * 2020-07-09 2020-10-23 长春工业大学 Phosphotungstic acid and propylsulfonic acid functionalized silicon oxide composite material in non-hydrochloric acid system and preparation method thereof
CN113491941A (en) * 2020-04-08 2021-10-12 中石化南京化工研究院有限公司 Aqueous solution for removing carbon dioxide from reaction circulating gas
CN113856412A (en) * 2021-08-25 2021-12-31 南京工业大学 Method and device for desorbing carbon dioxide by using alcohol amine rich solution

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI378089B (en) * 2009-12-30 2012-12-01 Ind Tech Res Inst Method for preparing citraconic anhydride and method for isomerizing/dehydrating itaconic acid

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5300703A (en) * 1993-04-05 1994-04-05 Texaco Chemical Company Alkylphenol synthesis using heteropoly acid catalysts
US5919725A (en) * 1993-11-19 1999-07-06 Exxon Research And Engineering Co. Heteropoly salts or acid salts deposited in the interior of porous supports
CN1958153A (en) * 2006-11-01 2007-05-09 南京师范大学 Hybridization materials of polymetallic salts of oxygen and acid / mesoporous molecular sieve, and preparation method
RU2009126236A (en) * 2009-07-09 2011-01-20 Общество с ограниченной ответственностью "УНИСИТ" (RU) NANOCOMPOSITE MATERIAL AND METHOD FOR PRODUCING IT
CN103191786A (en) * 2013-04-23 2013-07-10 浙江师范大学 Preparation method of MIL-100(Fe) packaged phosphotungstic heteropolyacid catalyst
WO2015052325A1 (en) * 2013-10-11 2015-04-16 Nilu - Stiftelsen Norsk Institutt For Luftforskning Capture of carbon dioxide
CN109513313A (en) * 2017-09-20 2019-03-26 中国石油化工股份有限公司 A kind of low-temperature catalyzed regeneration method of collecting carbonic anhydride solvent
CN108126719A (en) * 2017-12-21 2018-06-08 西安理工大学 A kind of preparation method of phosphotungstic acid doped titanium dioxide photocatalyst
CN113491941A (en) * 2020-04-08 2021-10-12 中石化南京化工研究院有限公司 Aqueous solution for removing carbon dioxide from reaction circulating gas
CN111804335A (en) * 2020-07-09 2020-10-23 长春工业大学 Phosphotungstic acid and propylsulfonic acid functionalized silicon oxide composite material in non-hydrochloric acid system and preparation method thereof
CN113856412A (en) * 2021-08-25 2021-12-31 南京工业大学 Method and device for desorbing carbon dioxide by using alcohol amine rich solution

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《介孔二氧化钛负载硅钨杂多酸的制备及其催化性能》;周华锋;《过程工程学报》;20120615;第12卷(第3期);第522-526页 *
Silvana R. Matkovic et al.,.《Tailored Brønsted and Lewis surface acid sites of the phosphotungstic Wells Dawson heteropoly-acid》.《Applied Surface Science》.2019,第495卷第143565页. *

Also Published As

Publication number Publication date
CN115282993A (en) 2022-11-04

Similar Documents

Publication Publication Date Title
CN102698812B (en) Solid super acid-ionic liquid composite solid supported catalyst and preparation method thereof
CN107638870A (en) A kind of preparation method and application of ionic liquid and metal organic frame compound adsorbent
CN106984333A (en) The preparation method of the loaded catalyst regenerated for carbon dioxide enriched amine aqueous solution
CN104289255B (en) Solid borne ionic liquid low-temperature denitration catalyst and preparation method thereof
CN101830474A (en) Method for preparing white carbon black
CN106268806B (en) A kind of catalyst of methanol carbonyl and its preparation and application
CN103337327A (en) Heterogeneous FeO34/Co metal organic skeleton material as well as preparation method and application thereof
CN104209115A (en) Vanadium-series loading type high-temperature SCR catalyst and preparation method thereof
CN104353504A (en) Preparing method of spherical titanium-aluminum composite carrier
CN106000463B (en) The preparation method and application of immobilized Tricesium dodecatungstophosphate salt catalyst
CN106012018A (en) Preparation method for bismuth vanadate mesoporous single crystal
CN105665018A (en) Preparation method and application of composite solid superacid catalyst
CN110255594B (en) Preparation method of active alumina
CN108295871A (en) A kind of compound micron bouquet of bismuth tungstate-molybdenum sulfide and its preparation method and application
CN115282993B (en) Regenerated catalyst and preparation method and application thereof
CN101723333A (en) Method for preparing mesoporous metallic oxides with different appearances
CN107792888A (en) A kind of high-specific surface area ZnCo2O4Preparation method
CN103127957B (en) Mesoporous PW/MoO3-TiO2-SiO2 catalyst and preparation method and application thereof
CN109331800A (en) A kind of nanoporous TiO prepared with citric acid2For the preparation method of the vanadium based denitration catalyst of carrier
CN108970611A (en) Natural gas organic sulfur hydrolyst and preparation method thereof
CN107970918B (en) Spherical denitration catalyst and preparation method thereof
CN106311201B (en) It is a kind of using mesoporous carbon containing Sn as dehydrogenation of isobutane Pt bases catalyst, preparation method and its application of carrier
CN108002403B (en) A kind of synthetic method of CHA molecular sieve
CN111286408A (en) Method for preparing biodiesel by catalyzing jatropha curcas oil through zirconium-based MOFs material loaded with ionic liquid
CN106179359A (en) A kind of effective catalyst purifying adipic acid plant tail gas and moulding technique 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