CN114515592A - Ni-W catalyst, preparation method and application - Google Patents
Ni-W catalyst, preparation method and application Download PDFInfo
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- CN114515592A CN114515592A CN202210101790.7A CN202210101790A CN114515592A CN 114515592 A CN114515592 A CN 114515592A CN 202210101790 A CN202210101790 A CN 202210101790A CN 114515592 A CN114515592 A CN 114515592A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000001354 calcination Methods 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 19
- 239000011949 solid catalyst Substances 0.000 claims description 17
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003837 high-temperature calcination Methods 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
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- 238000004519 manufacturing process Methods 0.000 claims description 2
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- 230000002776 aggregation Effects 0.000 abstract description 5
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- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 13
- 238000009792 diffusion process Methods 0.000 description 10
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910018106 Ni—C Inorganic materials 0.000 description 1
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- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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- 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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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Abstract
The invention provides a Ni-W catalyst, a preparation method and application thereof. In the invention, hydrogen peroxide is used as a solvent, and active components are deposited on the surface of the SBA-15 molecular sieve by utilizing freeze drying and reducing atmosphere roasting, so that the high-dispersion Ni-W bimetallic catalyst is prepared. The application utilizes a small amount of metal W to realize high dispersion of auxiliary Ni active centers and increase reactants and active centersContact area, less active center agglomeration and improved CH4Conversion, selectivity and stability of catalyst activity.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a Ni-W catalyst, a preparation method and application thereof.
Background
Ni-based catalysts are the more common CO2A methanation catalyst. Compared with the noble with high activity and high selectivityThe metal Ru-based catalyst and the Ni-based catalyst have the advantages of low cost and good catalytic activity, and become main candidates for industrial application.
The problem that Ni is easy to sinter and agglomerate exists when the Ni-based catalyst only loads a single Ni species. To solve this problem, researchers have proposed two solutions. Firstly, a suitable porous material is adopted as a carrier, and Ni atoms are anchored through the strong interaction of the carrier and Ni, so that the aim of preventing agglomeration is fulfilled. The mesoporous molecular sieve SBA-15 has the characteristics of large aperture and high specific surface area, and is favorable for loading active components into a pore channel. Because the pore canal has a certain number of micropores, the active center can be uniformly dispersed, and the metal agglomeration is reduced. Meanwhile, the SBA-15 has the characteristic of high temperature resistance, so that the problem of pore canal collapse in the reaction process can be avoided, and the service life of the carrier is prolonged. And secondly, the electronic environment of Ni is adjusted by doping a second metal so as to improve the activity of the catalyst. For example, the Fe, Co, Mo, Mn and other metals are added into the Ni-based catalyst according to different proportions and different forms of ligands, and the doped second metal changes the chemical environment of Ni through geometric action, electronic action or the combined action of the two metals, so that the activity of the catalyst is improved. When the second metal additive is doped, the usage amount of the additive is higher, so that the second metal is easy to cover the surface of Ni in the reaction process, and the conversion activity is reduced.
Disclosure of Invention
The invention provides a Ni-W catalyst, a preparation method and application thereof, and aims to solve the problem of low conversion activity caused by high additive usage amount in the existing Ni-based catalyst preparation process.
The invention provides a Ni-W catalyst, the structural formula of which is Ni50W/SBA-15 with particle size of 2-5nm and CO bridge adsorption wavelength of 1988cm-1The CO multiple-bond adsorption wavelength is 1863cm-1。
For the above Ni-W catalyst, the present application also provides a method for preparing the catalyst, the method comprising:
s01: adding tungstic acid to H2O2Heating and dissolving in 50-60 deg.C metal bath to obtainSolution A.
Adding 4.3-215mg of tungstic acid into 6ml of 30% H2O2In solution. Then tungstic acid is reacted with H2O2And putting the mixed solution of the solution into a metal bath at the temperature of 50-60 ℃, heating, stirring and dissolving to obtain a solution A.
S02: adding Ni (NO) to the solution A3)2·6H2And O, heating to dissolve to obtain a solution B.
Adding 100-250mgNi (NO) into the solution A3)2·6H2And O, stirring and dissolving at the temperature of 50-60 ℃ to obtain a solution B.
S03: and dropwise adding the solution B to an SBA-15 carrier, and then carrying out ultrasonic treatment, standing and freeze drying to obtain the solid catalyst.
Solution B was added dropwise to the SBA-15 support to form a suspension. And (3) carrying out ultrasonic treatment on the suspension for 30min under the ultrasonic condition to promote the Ni and W metal ions to be dispersed rapidly and uniformly. And standing the suspension subjected to the ultrasonic treatment for 24 hours to achieve diffusion balance. And (4) freeze-drying the suspension reaching the diffusion equilibrium for 12 hours to obtain the solid catalyst. The freeze drying can remove the solvent and simultaneously can avoid the metal ion agglomeration caused by the conventional heating drying.
The commercial SBA-15 carrier mostly adopts sodium orthosilicate as a silicon source in the preparation process. The use of sodium orthosilicate introduces Na ions that affect the loading performance of the SBA-15 carrier. Based on this, the present application uses TEOS as a silicon source to prepare SBA-15 carrier to avoid the influence of Na ions. The SBA-15 carrier prepared by the method has good pore channel orderliness, and can improve the dispersibility of active components, so that the mass transfer process of the reaction is improved, and the reaction is promoted to be carried out.
Specifically, the preparation method of the SBA-15 carrier provided by the application comprises the following steps:
s031: adding the P123 template agent into deionized water, stirring for 3 hours in a water bath at 40 ℃, adding dilute hydrochloric acid, and continuously stirring to form a mixed solution A.
5.5-11g of P123 template agent is added into 30-50ml of deionized water and stirred for 3h in a water bath at 40 ℃. Wherein, the P123 template agent is fully called polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and the molecular formula is as follows: PEO-PPO-PEO. 5-33ml of concentrated hydrochloric acid with a concentration of 12mol/L are diluted into 100ml of deionized water to form dilute hydrochloric acid. After the P123 template agent is stirred in the water bath at the temperature of 40 ℃, dilute hydrochloric acid is added, and the stirring is continued in the water bath at the temperature of 40 ℃ for 3 hours to form a mixed solution A.
S032: TEOS is added dropwise into the mixed solution A at a speed of 1-2 drops/second, and slowly stirred to form a mixed solution B.
TEOS (tetraethyl orthosilicate) was added dropwise to the mixture A at a rate of 1-2 drops/sec, and slowly stirred to avoid foaming. After the dropping of TEOS is finished, the stirring speed is increased, and the stirring is continued in the water bath at the temperature of 40 ℃ for 24 hours to form a mixed solution B.
S033: and transferring the mixed solution B into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven, heating to 100 ℃ according to the heating rate of 1 ℃/min, and reacting at constant temperature for 48 hours to obtain a reaction product.
Transferring the mixed solution B into a 100ml hydrothermal reaction kettle, and putting the hydrothermal reaction kettle into an oven. Heating to 100 ℃ according to the heating rate of 1 ℃/min, and reacting for 48 hours at constant temperature to obtain a reaction product.
S034: and carrying out suction filtration, drying, calcining, cooling and grinding on the reaction product to obtain SBA-15.
After the hydrothermal reaction is finished, the reaction product is filtered by suction and dried for 12 hours at the temperature of 100 ℃. And after drying, putting the suction filtration product into a muffle furnace for high-temperature calcination. Wherein the heating rate of the muffle furnace is 1 ℃/min, the calcining temperature is 550 ℃, and the calcining temperature time is 6 h. And cooling and grinding after the calcination is finished to obtain SBA-15.
S04: and grinding and sieving the solid catalyst, and then putting the solid catalyst into a tubular furnace for high-temperature calcination to obtain the supported Ni-W catalyst.
Grinding the solid catalyst into particles with the granularity of 20-40 meshes, and then putting the particles into a tubular furnace for high-temperature calcination to obtain the supported Ni-W catalyst. Wherein the temperature rise rate of the tube furnace is 1 ℃/min and 5 percent of H2Ar is reducing gas, the calcining temperature is 550 ℃, and the calcining time is 2 h.
The Ni-W catalyst provided by the present applicationThe catalyst can be used for catalyzing CO2And (4) methanation. In the catalysis of CO2In the methanation process, CO2Conversion of (3%) was 93.3%, CH4The selectivity of (A) is 98.26-99.7%.
The technical scheme provided by the embodiment of the invention can have the following beneficial effects:
in the Ni-W catalyst, the preparation method and the application, hydrogen peroxide is used as a solvent, and active components are deposited on the surface of the SBA-15 molecular sieve by utilizing freeze drying and reducing atmosphere roasting, so that the high-dispersion Ni-W bimetallic catalyst is prepared. The application utilizes a small amount of metal W to realize the high dispersion of the Ni-assisted active center, increases the contact area of reactants and the active center, reduces the agglomeration of the active center, and improves the CH4Selectivity and stability of catalyst activity.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
Drawings
In order to more clearly describe the technical solution of the present application, the drawings required to be used in the embodiments will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without inventive labor.
FIG. 1 shows Ni according to an embodiment of the present invention50TEM (transmission electron Microscope, Chinese name: transmission electron Microscope) image and particle size distribution diagram of W/SBA-15;
FIG. 2 is a TEM image and a particle size distribution diagram of Ni/SBA-15 provided by an example of the present invention;
FIG. 3 shows Ni according to an embodiment of the present invention50W/SBA-15 at T400 deg.C, P0.1 MPa, GHSV 3000mL g-1·h-1CO of2Hydrogenation for preparing CH4A performance test chart;
FIG. 4 shows examples of the present invention with Ni/SBA-15 at T400 deg.C, P0.1 MPa and GHSV 3000mL g-1·h-1CO of2Hydrogenation for preparing CH4Performance test chart；
FIG. 5 shows Ni/SBA-15 and Ni according to an embodiment of the present invention50FTIR (Fourier-transformed spectrum) spectrum of W/SBA-15.
Detailed Description
The embodiment of the application provides a Ni-W catalyst, and the structural formula of the Ni-W catalyst is Ni50W/SBA-15. The Ni is described in detail below by way of specific examples50A preparation method of a W/SBA-15 catalyst.
Example 1
S101: 4.3mg of tungstic acid was added to 5.5ml of 30% H2O2In solution. Then tungstic acid is reacted with H2O2The mixed solution of the solution is put into a metal bath with the temperature of 60 ℃ to be heated, stirred and dissolved, and the solution A is obtained.
S102: to solution A was added 250mgNi (NO)3)2·6H2And O, stirring and dissolving at the temperature of 60 ℃ to obtain a solution B.
S103: solution B was added dropwise to 1g of SBA-15 support to form a suspension. And (3) carrying out ultrasonic treatment on the suspension for 30min under the ultrasonic condition to promote the Ni and W metal ions to be dispersed rapidly and uniformly. And standing the suspension subjected to the ultrasonic treatment for 24 hours to achieve diffusion balance. And (4) freeze-drying the suspension reaching the diffusion equilibrium for 12 hours to obtain the solid catalyst.
The preparation method of the SBA-15 carrier comprises the following steps:
s1031: 5.5g of P123 template was added to 30ml of deionized water and stirred in a water bath at 40 ℃ for 3 h. 16.5ml of concentrated hydrochloric acid having a concentration of 12mol/L was diluted into 100ml of deionized water to form diluted hydrochloric acid. After the P123 template agent is stirred in the water bath at the temperature of 40 ℃, dilute hydrochloric acid is added, and the stirring is continued in the water bath at the temperature of 40 ℃ for 3 hours to form a mixed solution A.
S1032: 12.5ml of TEOS was added dropwise to the mixture A at a rate of 1 drop/sec, and slowly stirred to avoid foaming. After the dropping of TEOS is finished, the stirring speed is increased, and the stirring is continued in the water bath at the temperature of 40 ℃ for 24 hours to form a mixed solution B.
S1033: transferring the mixed solution B into a 100ml hydrothermal reaction kettle, and putting the hydrothermal reaction kettle into an oven. Heating to 100 ℃ according to the heating rate of 1 ℃/min, and reacting for 48 hours at constant temperature to obtain a reaction product.
S1034: after the hydrothermal reaction is finished, the reaction product is filtered by suction and dried for 12 hours at the temperature of 100 ℃. And after drying, putting the suction filtration product into a muffle furnace for high-temperature calcination. Wherein the heating rate of the muffle furnace is 1 ℃/min, the calcining temperature is 550 ℃, and the calcining temperature time is 6 h. And cooling and grinding after the calcination is finished to obtain SBA-15.
S104: grinding the solid catalyst into particles with the granularity of 20 meshes, and putting the particles into a tubular furnace for high-temperature calcination to obtain the supported Ni-W catalyst. Wherein the temperature rise rate of the tube furnace is 1 ℃/min and 5 percent of H2the/Ar is reducing gas, the calcining temperature is 550 ℃, and the calcining time is 2 h.
Example 2
S201: 215mg of tungstic acid were added to 6ml of 30% strength H2O2In solution. Then tungstic acid is reacted with H2O2The mixed solution of the solution is put into a metal bath with the temperature of 50 ℃, heated, stirred and dissolved to obtain a solution A.
S202: to solution A was added 100mgNi (NO)3)2·6H2And O, stirring and dissolving at the temperature of 50 ℃ to obtain a solution B.
S203: solution B was added dropwise to 1g of SBA-15 support to form a suspension. And (3) carrying out ultrasonic treatment on the suspension for 30min under the ultrasonic condition to promote the Ni and W metal ions to be dispersed rapidly and uniformly. And standing the suspension subjected to the ultrasonic treatment for 24 hours to achieve diffusion balance. And (4) freeze-drying the suspension which reaches the diffusion equilibrium for 12 hours to obtain the solid catalyst.
The preparation method of the SBA-15 carrier comprises the following steps:
s2031: 11g of P123 template was added to 50ml of deionized water and stirred in a water bath at 40 ℃ for 3 h. 5ml of concentrated hydrochloric acid having a concentration of 12mol/L was diluted into 100ml of deionized water to form diluted hydrochloric acid. After the P123 template agent is stirred in the water bath at the temperature of 40 ℃, dilute hydrochloric acid is added, and the stirring is continued in the water bath at the temperature of 40 ℃ for 3 hours to form a mixed solution A.
S2032: 12.5ml of TEOS was added dropwise to the mixture A at a rate of 2 drops/sec, and slowly stirred to avoid foaming. After the dropping of TEOS is finished, the stirring speed is increased, and the stirring is continued in the water bath at the temperature of 40 ℃ for 24 hours to form a mixed solution B.
S2033: transferring the mixed solution B into a 100ml hydrothermal reaction kettle, and putting the hydrothermal reaction kettle into an oven. Heating to 100 ℃ according to the heating rate of 1 ℃/min, and reacting for 48 hours at constant temperature to obtain a reaction product.
S2034: after the hydrothermal reaction is finished, the reaction product is filtered by suction and dried for 12 hours at the temperature of 100 ℃. And after drying, putting the suction filtration product into a muffle furnace for high-temperature calcination. Wherein the heating rate of the muffle furnace is 1 ℃/min, the calcining temperature is 550 ℃, and the calcining temperature time is 6 h. And cooling and grinding after the calcination is finished to obtain SBA-15.
S204: grinding the solid catalyst into particles with the particle size of 40 meshes, and then putting the particles into a tubular furnace for high-temperature calcination to obtain the supported Ni-W catalyst. Wherein the temperature rise rate of the tube furnace is 1 ℃/min and 5 percent of H2the/Ar is reducing gas, the calcining temperature is 550 ℃, and the calcining time is 2 h.
Example 3
S301: 135mg of tungstic acid were added to 6ml of 30% strength H2O2In solution. Then tungstic acid is reacted with H2O2And putting the mixed solution of the solution into a metal bath at the temperature of 55 ℃, heating, stirring and dissolving to obtain a solution A.
S302: to solution A was added 200mgNi (NO)3)2·6H2And O, stirring and dissolving at the temperature of 55 ℃ to obtain a solution B.
S303: solution B was added dropwise to 1g of SBA-15 support to form a suspension. And (3) carrying out ultrasonic treatment on the suspension for 30min under the ultrasonic condition to promote the Ni and W metal ions to be dispersed rapidly and uniformly. And standing the suspension subjected to the ultrasonic treatment for 24 hours to achieve diffusion balance. And (4) freeze-drying the suspension reaching the diffusion equilibrium for 12 hours to obtain the solid catalyst.
The preparation method of the SBA-15 carrier comprises the following steps:
s3031: 8g of P123 template was added to 40ml of deionized water and stirred in a water bath at 40 ℃ for 3 h. 33ml of concentrated hydrochloric acid having a concentration of 12mol/L was diluted into 100ml of deionized water to form diluted hydrochloric acid. After the P123 template agent is stirred in the water bath at the temperature of 40 ℃, dilute hydrochloric acid is added, and the stirring is continued in the water bath at the temperature of 40 ℃ for 3 hours to form a mixed solution A.
S3032: 12.5ml of TEOS was added dropwise to the mixture A at a rate of 1-2 drops/sec, and slowly stirred to avoid foaming. After the dropping of TEOS is finished, the stirring speed is increased, and the stirring is continued in the water bath at the temperature of 40 ℃ for 24 hours to form a mixed solution B.
S3033: transferring the mixed solution B into a 100ml hydrothermal reaction kettle, and putting the hydrothermal reaction kettle into an oven. Heating to 100 ℃ according to the heating rate of 1 ℃/min, and reacting for 48 hours at constant temperature to obtain a reaction product.
S3034: after the hydrothermal reaction is finished, the reaction product is filtered by suction and dried for 12 hours at the temperature of 100 ℃. And after drying, putting the suction filtration product into a muffle furnace for high-temperature calcination. Wherein the heating rate of the muffle furnace is 1 ℃/min, the calcining temperature is 550 ℃, and the calcining temperature time is 6 h. And cooling and grinding after the calcination is finished to obtain SBA-15.
S304: grinding the solid catalyst into particles with the granularity of 30 meshes, and then putting the particles into a tubular furnace for high-temperature calcination to obtain the supported Ni-W catalyst. Wherein the temperature rise rate of the tube furnace is 1 ℃/min and 5 percent of H2the/Ar is reducing gas, the calcining temperature is 550 ℃, and the calcining time is 2 h.
To verify Ni provided in the examples of the present application50The W/SBA-15 catalyst has better CO2Conversion rate, CH4Selectivity, etc., the example of the present application uses Ni/SBA-15 catalyst as comparative example, and Ni prepared in example 1 of the present application50The W/SBA-15 catalyst is used for carrying out particle size, TEM and CO catalysis2And carrying out methanation and CO in-situ infrared characterization on the catalyst CO adsorption comparative experiment to obtain a result chart shown in the attached drawings 1-5.
Wherein, the preparation process of the Ni/SBA-15 comprises the following steps:
d01: mixing 250mgNi (NO)3)2·6H2O to 5.5ml of 30% H2O2In solution. Then adding Ni (NO)3)2·6H2O andH2O2and putting the mixed solution of the solution into a metal bath at the temperature of 60 ℃, heating, stirring and dissolving to obtain a solution A.
D02: solution A was added dropwise to 1g of SBA-15 support to form a suspension. And (3) carrying out ultrasonic treatment on the suspension for 30min under the ultrasonic condition to promote the Ni metal ions to be dispersed rapidly and uniformly. And standing the suspension subjected to the ultrasonic treatment for 24 hours to achieve diffusion balance. And (4) freeze-drying the suspension reaching the diffusion equilibrium for 12 hours to obtain the solid catalyst.
The preparation method of the SBA-15 carrier comprises the following steps:
d021: 5.5g of P123 template was added to 30ml of deionized water and stirred in a water bath at 40 ℃ for 3 h. 16.5ml of concentrated hydrochloric acid having a concentration of 12mol/L was diluted into 100ml of deionized water to form diluted hydrochloric acid. After the P123 template agent is stirred in the water bath at the temperature of 40 ℃, dilute hydrochloric acid is added, and the stirring is continued in the water bath at the temperature of 40 ℃ for 3 hours to form a mixed solution A.
D022: 12.5ml of TEOS was added dropwise to the mixture A at a rate of 1 drop/sec, and slowly stirred to avoid foaming. After the dropping of TEOS is finished, the stirring speed is increased, and the stirring is continued in the water bath at the temperature of 40 ℃ for 24 hours to form a mixed solution B.
D023: transferring the mixed solution B into a 100ml hydrothermal reaction kettle, and putting the hydrothermal reaction kettle into an oven. Heating to 100 ℃ according to the heating rate of 1 ℃/min, and reacting for 48 hours at constant temperature to obtain a reaction product.
D024: after the hydrothermal reaction is finished, the reaction product is filtered by suction and dried for 12 hours at the temperature of 100 ℃. And after drying, putting the suction filtration product into a muffle furnace for high-temperature calcination. Wherein the heating rate of the muffle furnace is 1 ℃/min, the calcining temperature is 550 ℃, and the calcining temperature time is 6 h. And cooling and grinding after the calcination is finished to obtain SBA-15.
D03: grinding the solid catalyst into particles with the granularity of 20 meshes, and then putting the particles into a tubular furnace for high-temperature calcination to obtain the supported Ni catalyst. Wherein the temperature rise rate of the tube furnace is 1 ℃/min and 5 percent of H2the/Ar is reducing gas, the calcining temperature is 550 ℃, and the calcining time is 2 h.
Catalyzing CO2The specific process of methanation comprises the following steps:
by using CO2Hydrogenation for preparing CH4The reaction was evaluated for catalyst performance and the reaction was carried out on a fixed bed. Respectively putting 0.1g of catalyst into quartz tubes with the outer diameter of 7.5mm and the inner diameter of 5mm, wherein the catalyst content is 5% H2Reducing at 550 deg.C for 2h in Ar atmosphere, and performing temperature programming when the temperature is reduced to test temperature, wherein the raw material gas is 20% CO2+80％H2Sampling every 20min at test temperature for 3 times, detecting gas composition at gas outlet by gas chromatography (FID detector TDX-01 and TCD detector TDX-01), averaging, and calculating CO2Conversion and CH4And (4) selectivity.
The CO in-situ infrared characterization catalyst CO adsorption specific process comprises the following steps:
the catalyst CO adsorption was characterized by CO in situ infrared and tested using a Nicolet6700 Fourier Infrared spectrometer. And introducing Ar into the high-temperature in-situ pool for purging, and collecting the background. Taking 10mg of catalyst, tabletting, preparing a sample, putting the sample into a high-temperature in-situ pool, and using 10% H2and/Ar, setting the flow rate to be 40sccm, setting the temperature rise rate to be 10 ℃/min, and keeping the temperature at 550 ℃ for 1 h. The temperature is cooled to 30 ℃, and after blowing Ar and purging for 1h, a CO adsorption test is carried out.
As can be seen from FIGS. 1 and 2, Ni50The particle size of the W/SBA-15 catalyst is 2-5nm, and the particles on a TEM picture are fine and are uniformly distributed; the particle diameter of the Ni/SBA-15 catalyst is 5-12nm, and the particles are thicker and are distributed unevenly on a TEM image. The smaller the particle size of the catalyst, the higher the catalytic activity. Thus, Ni is considered from the aspect of particle diameter50The catalytic activity of the W/SBA-15 catalyst is higher than that of the Ni/SBA-15 catalyst.
As can be seen from FIGS. 3 and 4, Ni50Catalysis of CO by W/SBA-15 catalyst2In the methanation process, CO2The conversion at 400 ℃ was 93.3%, CH4The selectivity was 99.7%. Catalysis of CO by Ni/SBA-15 catalyst2In the methanation process, CO2The conversion at 400 ℃ was 85.89%, CH4The selectivity was 98.96%. It can be seen that in catalyzing CO2During methanation, Ni50CO of W/SBA-15 catalyst2Conversion rate, CH4The selectivity is obviously higher than that of Ni/SBA-15 catalysisCO of agent2Conversion rate, CH4And (4) selectivity.
As can be seen from FIG. 5, the CO bridge adsorption and multi-bond adsorption wavelengths of the Ni/SBA-15 catalyst are 1975cm-1、1858cm-1，Ni50The CO bridge adsorption and the multi-bond adsorption wavelengths of the W/SBA-15 catalyst are respectively 1988cm-1、1863cm-1This indicates that blue shift occurs after addition of W metal. This variation may be due to adjacent WOxElectronic modification of Ni by species reduces the d-charge electron density of Ni. The blue shift phenomenon shows that the Ni-C bond is weakened, which is beneficial to further hydrogenation to generate CH4Decrease CO production and increase CH4And (4) selectivity. Thus, only a small amount of Ni is used50The W/SBA-15 catalyst can catalyze CO2Methanation greatly reduces the using amount of the auxiliary agent and has higher transformation activity.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It is to be understood that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. The invention is not limited to the precise arrangements described above and shown in the drawings, and various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (10)
1. The Ni-W catalyst is characterized in that the particle size of the Ni-W catalyst is 2-5nm, and the CO bridge adsorption wavelength is 1988cm-1CO multiple bond adsorption wavelength of1863cm-1。
2. The Ni-W catalyst of claim 1, wherein the Ni-W catalyst has a structural formula of Ni50W/SBA-15。
3. A method for preparing a Ni-W catalyst is characterized by comprising the following steps:
adding tungstic acid to H2O2Heating and dissolving in a metal bath at 50-60 ℃ to form a solution A;
adding Ni (NO) to the solution A3)2·6H2Heating to dissolve to obtain solution B;
dropwise adding the solution B into an SBA-15 carrier, and then carrying out ultrasonic treatment, standing and freeze drying to obtain a solid catalyst;
and grinding and sieving the solid catalyst, and then putting the solid catalyst into a tubular furnace for high-temperature calcination to obtain the supported Ni-W catalyst.
4. The method of preparing the Ni-W catalyst of claim 3, wherein the SBA-15 is prepared by a method comprising:
adding a P123 template agent into deionized water, stirring for 3 hours in a water bath at 40 ℃, adding dilute hydrochloric acid, and continuously stirring to form a mixed solution A;
dropping TEOS into the mixed solution A at the speed of 1-2 drops/second, and slowly stirring to form mixed solution B;
transferring the mixed solution B into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a drying oven, heating the mixed solution B to 100 ℃ at a heating rate of 1 ℃/min, and reacting for 48 hours at a constant temperature to obtain a reaction product;
and carrying out suction filtration, drying, calcining, cooling and grinding on the reaction product to obtain SBA-15.
5. The method for preparing a Ni-W catalyst according to claim 4, wherein the calcination temperature is 550 ℃ and the calcination time is 6 hours.
6. Ni-W catalyst preparation according to claim 4Method, characterized in that said H2O2The concentration of (2) is 30%.
7. The method of claim 3, wherein the tube furnace has a ramp rate of 1 ℃/min, 5% H2the/Ar is reducing gas, the calcining temperature is 550 ℃, and the calcining time is 2 h.
8. The Ni-W catalyst production method according to claim 3, wherein the particle size of the solid catalyst is 20 to 40 mesh.
Use of Ni-W catalyst for catalyzing CO2And (4) methanation.
10. Use of the Ni-W catalyst according to claim 9, wherein the Ni-W catalyst catalyzes CO at 400 ℃2Conversion of (3%) was 93.3%, CH4The selectivity of (a) was 99.7%.
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