CN111514897B - Application of high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst in carbon dioxide methanation reaction - Google Patents
Application of high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst in carbon dioxide methanation reaction Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 24
- 239000002620 silicon nanotube Substances 0.000 title claims abstract description 20
- 229910021430 silicon nanotube Inorganic materials 0.000 title claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 14
- 239000006185 dispersion Substances 0.000 title claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 22
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 16
- 150000002815 nickel Chemical class 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000004873 anchoring Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- JCGDCINCKDQXDX-UHFFFAOYSA-N trimethoxy(2-trimethoxysilylethyl)silane Chemical compound CO[Si](OC)(OC)CC[Si](OC)(OC)OC JCGDCINCKDQXDX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000002071 nanotube Substances 0.000 abstract description 7
- 125000003277 amino group Chemical group 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 150000001282 organosilanes Chemical class 0.000 abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention relates to application of a high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst in methanation reaction of carbon dioxide, belonging to the technical field of catalytic reaction. The catalyst of the invention carries out directional hydrolytic polycondensation on organosilane molecules containing amino in the presence of a soft template agent to form the organic silicon oxide nanotube containing ordered amino groups and having a mesoporous structure. The amino group can effectively cooperate and anchor metal ions, so that the active metal nickel can be highly dispersed and firmly loaded on the surface of the mesoporous organic silicon oxide. The carbon-doped carrier can improve the electron transfer efficiency of the active metal in the catalysis process, and further synergistically improve the catalytic activity of the catalyst in carbon dioxide methanation. The high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst prepared by the invention is applied to CO2The methanation reaction shows higher catalytic activity and selectivity, and has good application prospect.
Description
Technical Field
The invention relates to application of a high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst in methanation reaction of carbon dioxide, belonging to the technical field of catalytic reaction.
Background
The carbon dioxide methanation reaction is a process of generating methane by the reaction of carbon dioxide and hydrogen under the action of a catalyst. It is well known that Ru and Rh have the best carbon dioxide methanation properties, but they are scarce in reserves, expensive and difficult to implement for large-scale industrial applications. Co and Fe based catalysts have better reactivity, but methane selectivity is lower, and the catalyst is more used as a Fischer-Tropsch synthesis catalyst. The nickel-based catalyst not only has good catalytic performance, but also has large reserves and low price, so the nickel-based catalyst is widely applied to the methanation reaction of carbon dioxide. The activity of the nickel-based catalyst is influenced by factors such as a carrier, an auxiliary agent, a preparation method and the like.
SiO2The methanation catalyst carrier has good hydrothermal stability, large specific surface area and developed pore structure, is beneficial to the dispersion of active components on the surface of the carrier, forms small nano-crystalline grains and improves the active specific surface of active metal. However, SiO2The carrier is inactive in chemical property, is difficult to play a role in concerted catalysis with the metal active component, and the interaction force and the mechanical strength of the metal carrier are relatively weak; this prevents the catalyst from performing its optimum function during the reaction. The structure and the composition of the carrier are adjusted and improved by changing the preparation method and the like, so that some defects of the carrier can be effectively made up.
A Periodic Mesoporous organic silicon oxide material (PMO) is a novel organic-inorganic composite Mesoporous material. Under the directional action of a surfactant, hydrolyzed organosilane molecules are subjected to polycondensation to form a material with a specific microscopic morphology. The periodic mesoporous organic silicon oxide has important functions in the aspects of heterogeneous catalysis, substance adsorption, chromatographic phase, light absorption and emission, transmission of drugs and biomolecules and the like due to the regular pore channel structure, larger specific surface area, adjustable surface property and the self characteristics of different bridging functional groups. Besides the properties, the periodic organic silicon oxide nanotube also has the characteristics of higher specific surface area, higher mechanical stability, a hollow structure beneficial to molecular diffusion and nanotube confinement effect of a one-dimensional nanotube material, and can play an important role as a carrier in a heterogeneous catalytic reaction. The periodic mesoporous organic silicon oxide nanotube can also coordinate partial metal atoms through a bridging functional group so as to fix an active center on the carrier.
On the basis of the prior art, the invention develops the high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst for the first time, and applies the high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst to the methanation reaction of carbon dioxide. The catalyst of the invention carries out directional hydrolytic polycondensation on organosilane molecules containing amino in the presence of a soft template agent to form the organic silicon oxide nanotube containing ordered amino groups and having a mesoporous structure. The amino group can effectively cooperate and anchor metal ions, so that the active metal nickel can be highly dispersed and firmly loaded on the surface of the mesoporous organic silicon oxide. The carbon-doped carrier can improve the electron transfer efficiency of the active metal in the catalysis process, and further synergistically improve the catalytic activity of the catalyst in carbon dioxide methanation. The high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst prepared by the invention is applied to CO2The methanation reaction shows higher catalytic activity and selectivity, and has good application prospect.
Disclosure of Invention
The invention aims to provide an application of a highly-dispersed carbon-doped mesoporous silicon nanotube nickel-based catalyst in methanation reaction of carbon dioxide, and the specific application method comprises the following steps:
charging proper amount of catalyst into fixed bed reactor, and charging raw material gas H2、CO2The mixture is introduced into the reactor in a molar ratio of 1-10, and the feeding space velocity is maintained at 5000--1Keeping the total pressure of the reaction system at 0.1MPa, and carrying out CO reaction at 100-450 DEG C2Carrying out methanation catalytic reaction; the catalyst takes a carbon-doped mesoporous silicon nanotube as a carrier and loads active metal nickel, wherein the nickel accounts for 2-15 wt% of the catalyst in terms of metal.
Further, the molar ratio of the raw material gas is preferably 2 to 6, and more preferably 4; the feeding space velocity is preferably 5000--1More preferably 20000h-1。
Furthermore, the nickel accounts for 5-10wt% of the catalyst in terms of metal.
Further, the preparation method of the catalyst comprises the following preparation steps:
(1)PMO-NH2the synthesis of (2):
dissolving a certain amount of template Cetyl Trimethyl Ammonium Bromide (CTAB) in a mixed solution of water and ethanol, and dissolving by magnetic stirring; adding 3-Aminopropyltriethoxysilane (APTES) and 1, 2-bis (trimethoxysilyl) ethane (BTME) into the solution, wherein the mass ratio of the APTES to the BTME is 1:1-10, continuously stirring for 1-2h, pouring the mixture into a polytetrafluoroethylene inner container, and standing at 60-100 ℃ for reaction for 24-48 h; centrifuging the reactant, extracting the template agent by refluxing the obtained product at 40-80 ℃ by using a mixed solution of ethanol and hydrochloric acid, centrifuging and washing to obtain the amino-containing organic bridged PMO;
(2) loading of active metal nickel:
dissolving soluble nickel salt in ethanol solution to obtain 0.01-0.1M nickel salt precursor solution, and preparing PMO-NH from step (1)2Dipping the carrier serving as the carrier in the nickel salt precursor solution, and carrying out ultrasonic treatment for 2-4h to ensure that amino in PMO and metal nickel ions fully carry out coordination reaction, and anchoring the nickel ions on the surface of the carrier by coordination bonds; after the reaction is finished, centrifugally separating a product, fully washing the product by using deionized water and ethanol, and drying the product at the temperature of 60-100 ℃;
(3) roasting of the catalyst:
and (3) placing the product obtained in the step (2) in a tubular furnace, and roasting for 2-6h at the temperature rising rate of 2-5 ℃/min to 500-900 ℃ under the protection of nitrogen to obtain the carbon-doped mesoporous silicon nanotube nickel-based catalyst.
Further, the mass ratio of the template agent to the APTES in the step (1) is 1:1-5, and the mass ratio of the APTES to the BTME is 1: 3-8.
Further, the temperature of the standing reaction in the step (1) is preferably 60-90 ℃, and the time is preferably 24-36 h.
Further, the nickel salt in the step (2) is one or more of nickel nitrate, nickel chloride and nickel sulfate, and the concentration of the nickel salt precursor solution is preferably 0.02-0.05M.
Further, the calcination temperature in the step (3) is preferably 600-.
In the invention, in the presence of a soft template agent, organosilane molecules containing amino are subjected to directional hydrolytic polycondensation to form the organic silicon oxide nanotube containing ordered amino groups and having a mesoporous structure. The amino group can effectively cooperate and anchor metal ions, so that the active metal nickel can be firmly and firmly immobilized on the surface of the mesoporous organic silicon oxide in a high-dispersion manner, and the technical problem that the active metal is easy to fall off and agglomerate in the prior art is effectively solved. Further, due to the existence of organic groups, the organic groups can form carbon doping in the silicon oxide during the oxygen-free roasting process, and simultaneously reduce metallic nickel. The steps can omit the subsequent reduction step and simplify the preparation process of the catalyst.
The silicon nanotube material has a large specific surface area and a hollow structure, and is beneficial to the diffusion and mass transfer of reactant molecules, so that the catalytic reaction efficiency is improved. Meanwhile, the carbon-doped carrier can promote the electron transfer efficiency of the active metal in the catalysis process, so that the catalytic activity of the catalyst in carbon dioxide methanation is synergistically improved.
The high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst prepared by the invention is applied to CO2In methanation reactionShows higher catalytic activity and selectivity, the yield of methane can reach 79.6 percent at 400 ℃, and the catalytic effect is obviously better than that of the traditional Ni/SiO2The catalyst has good application value.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1)PMO-NH2The synthesis of (2):
dissolving a template CTAB in a mixed solution of water and ethanol, and dissolving by magnetic stirring; adding APTES and BTME into the solution, wherein the mass ratio of CTAB to APTES to BTME is 1:2:8, continuously stirring for 2h, pouring the mixture into a polytetrafluoroethylene inner container, and standing at 80 ℃ for reaction for 30 h; centrifuging the reactant, extracting the template agent by refluxing the obtained product at 60 ℃ by using a mixed solution of ethanol and hydrochloric acid, centrifuging and washing to obtain the amino-containing organic bridged PMO;
(2) loading of active metal nickel:
dissolving nickel nitrate in ethanol solution to obtain 0.02M nickel salt precursor solution, and preparing PMO-NH prepared in step (1)2Soaking the carrier in the nickel salt precursor solution, performing ultrasonic treatment for 2h, after the reaction is finished, performing centrifugal separation on the product, fully washing the product by using deionized water and ethanol, and drying the product at 80 ℃;
(3) roasting of the catalyst:
placing the product obtained in the step (2) in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and roasting for 3h to obtain the carbon-doped mesoporous silicon nanotube nickel-based catalyst of the embodiment, which is marked as a number S-1; wherein, calculated by metal, the mass fraction of nickel in the catalyst is 7 wt%.
Example 2
(1)PMO-NH2The synthesis of (2):
dissolving a template CTAB in a mixed solution of water and ethanol, and dissolving by magnetic stirring; adding APTES and BTME into the solution, wherein the mass ratio of CTAB to APTES to BTME is 1:1:5, continuously stirring for 2h, pouring the mixture into a polytetrafluoroethylene inner container, and standing at 100 ℃ for reaction for 28 h; centrifuging the reactant, extracting the template agent by refluxing the obtained product at 80 ℃ by using a mixed solution of ethanol and hydrochloric acid, centrifuging and washing to obtain the amino-containing organic bridged PMO;
(2) loading of active metal nickel:
dissolving nickel nitrate in ethanol solution to obtain 0.05M nickel salt precursor solution, and dissolving the PMO-NH prepared in the step (1)2Soaking the carrier in the nickel salt precursor solution, performing ultrasonic treatment for 2h, after the reaction is finished, performing centrifugal separation on the product, fully washing the product by using deionized water and ethanol, and drying the product at 80 ℃;
(3) roasting of the catalyst:
placing the product obtained in the step (2) in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and roasting for 3h to obtain the carbon-doped mesoporous silicon nanotube nickel-based catalyst, which is marked as a number S-2; wherein, calculated by metal, the mass fraction of nickel in the catalyst is 10 wt%.
Example 3
(1)PMO-NH2The synthesis of (2):
dissolving a template CTAB in a mixed solution of water and ethanol, and dissolving by magnetic stirring; adding APTES and BTME into the solution, wherein the mass ratio of CTAB to APTES to BTME is 1:2:6, continuously stirring for 2h, pouring the mixture into a polytetrafluoroethylene inner container, and standing and reacting for 24h at 100 ℃; centrifuging the reactant, extracting the template agent by refluxing the obtained product at 80 ℃ by using a mixed solution of ethanol and hydrochloric acid, centrifuging and washing to obtain the amino-containing organic bridged PMO;
(2) loading of active metal nickel:
dissolving nickel nitrate in ethanol solution to obtain 0.04M nickel salt precursor solution, and dissolving the PMO-NH prepared in the step (1)2Impregnating the carrier in the nickel salt precursor solutionPerforming ultrasonic treatment for 2h, after the reaction is finished, performing centrifugal separation on a product, fully washing the product by using deionized water and ethanol, and drying the product at 80 ℃;
(3) roasting of the catalyst:
placing the product obtained in the step (2) in a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and roasting for 3 hours to obtain the carbon-doped mesoporous silicon nanotube nickel-based catalyst, which is marked as the number S-3; wherein, calculated by metal, the nickel accounts for 5wt percent of the mass fraction of the catalyst
Example 4
CO treatment of the prepared catalyst by using a fixed bed reactor2And (4) evaluating the methanation reaction. Weighing 0.5g of catalyst, loading into a reactor, and feeding a raw material gas H2/CO24, and feeding the mixture into a reactor at a feed space velocity GHSV of 20000h-1Keeping the total pressure of the reaction system at 0.1MPa, and carrying out CO reaction at 400 DEG C2And (4) carrying out methanation catalytic reaction. And calculating the catalytic reaction result by using the gas chromatographic analysis data of the tail gas when the reaction reaches a steady state. The results of the experiment are shown in table 1.
For comparison, the conventional Ni/SiO were tested under the same test conditions2(Ni content 7% by mass, designated as D-1) by CO2The results of the methanation reaction are shown in Table 1.
TABLE 1 catalyst in CO2Catalytic activity data in methanation reactions
As can be seen from Table 1, the highly dispersed carbon-doped mesoporous silicon nanotube nickel-based catalyst prepared by the method is applied to CO2The methanation reaction shows higher catalytic activity and selectivity, the yield of the methane can reach 79.6 percent at 400 ℃, and the catalytic effect is obviously better than that of the traditional Ni/SiO2A catalyst. Thus, the bookThe inventive catalyst has excellent CO2The methanation catalysis effect has good application prospect.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (6)
1. An application of a high-dispersion carbon-doped mesoporous silicon nanotube nickel-based catalyst in methanation reaction of carbon dioxide is characterized in that the application method comprises the following steps:
charging proper amount of catalyst into fixed bed reactor, and charging raw material gas H2、CO2The mixture is introduced into the reactor in a molar ratio of 1-10, and the feeding space velocity is maintained at 5000--1Keeping the total pressure of the reaction system at 0.1MPa, and carrying out CO reaction at 100-450 DEG C2Carrying out methanation catalytic reaction; the catalyst takes a carbon-doped mesoporous silicon nanotube as a carrier and loads active metal nickel, wherein the nickel accounts for 5-10wt% of the catalyst in terms of metal;
the preparation method of the catalyst comprises the following preparation steps:
(1)PMO-NH2the synthesis of (2):
dissolving a certain amount of template Cetyl Trimethyl Ammonium Bromide (CTAB) in a mixed solution of water and ethanol, and dissolving by magnetic stirring; adding 3-aminopropyltriethoxysilane APTES and 1, 2-bis (trimethoxysilyl) ethane BTME into the solution, wherein the mass ratio of APTES to BTME is 1:1-10, continuously stirring for 1-2h, pouring the mixture into a polytetrafluoroethylene inner container, and standing at 60-100 ℃ for reaction for 24-48 h; centrifuging the reactant, extracting the template agent by refluxing the obtained product at 40-80 ℃ by using a mixed solution of ethanol and hydrochloric acid, centrifuging and washing to obtain the amino-containing organic bridged PMO;
(2) loading of active metal nickel:
dissolving soluble nickel saltDissolving in ethanol solution to obtain 0.01-0.1M nickel salt precursor solution, and mixing the PMO-NH prepared in step (1)2Dipping the carrier serving as the carrier in the nickel salt precursor solution, and carrying out ultrasonic treatment for 2-4h to ensure that amino in PMO and metal nickel ions fully carry out coordination reaction, and anchoring the nickel ions on the surface of the carrier by coordination bonds; after the reaction is finished, centrifugally separating a product, fully washing the product by using deionized water and ethanol, and drying the product at the temperature of 60-100 ℃;
(3) roasting of the catalyst:
and (3) placing the product obtained in the step (2) in a tubular furnace, and roasting for 2-6h at the temperature rising rate of 2-5 ℃/min to 500-900 ℃ under the protection of nitrogen to obtain the carbon-doped mesoporous silicon nanotube nickel-based catalyst.
2. The use according to claim 1, wherein the molar ratio of the feed gases is 2-6; the feeding airspeed is 5000--1。
3. The use according to claim 1, wherein the mass ratio of the template to the APTES in step (1) of the catalyst preparation method is 1:1-5, and the mass ratio of the APTES to the BTME is 1: 3-8.
4. The use according to claim 1, wherein the temperature of the standing reaction in step (1) in the preparation method of the catalyst is 60-90 ℃ and the time is 24-36 h.
5. The use according to claim 1, wherein the nickel salt in step (2) of the preparation method of the catalyst is one or more of nickel nitrate, nickel chloride and nickel sulfate, and the concentration of the nickel salt precursor solution is 0.02-0.05M.
6. The use as claimed in claim 1, wherein the calcination temperature in step (3) of the preparation method of the catalyst is 600-800 ℃ and the time is 3-4 h.
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