CN107497470B - Nickel-loaded silicon carbide catalyst for methane and carbon dioxide reforming reaction and preparation method and application thereof - Google Patents
Nickel-loaded silicon carbide catalyst for methane and carbon dioxide reforming reaction and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 67
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 48
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 27
- 238000006057 reforming reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title description 6
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 239000013335 mesoporous material Substances 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000008096 xylene Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 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 11
- 238000000034 method Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 6
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005303 weighing Methods 0.000 description 21
- 239000013370 mesoporous silicon carbide Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 10
- 229920003257 polycarbosilane Polymers 0.000 description 10
- 230000008021 deposition Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000006004 Quartz sand Substances 0.000 description 7
- 238000001833 catalytic reforming Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000005245 sintering Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910003925 SiC 1 Inorganic materials 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910003923 SiC 4 Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/613—
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- B01J35/615—
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- B01J35/633—
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- B01J35/643—
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- B01J35/647—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The pore volume of the nickel-loaded silicon carbide catalyst for methane and carbon dioxide reforming reaction is 0.1-0.4 cm3A specific surface area of 95 to 400 m/g2The pore diameter is 1-11 nm, the nickel loading is 4-10 wt%, and the balance is silicon carbide ordered mesoporous material. The invention has the advantages of good thermal stability, long service life and good activity.
Description
Technical Field
The invention belongs to pollution emission reduction of two greenhouse gases of methane and carbon dioxide, and particularly relates to a nickel-loaded silicon carbide catalyst for methane and carbon dioxide reforming reaction, and a preparation method and application thereof.
Background
How to convert two greenhouse gases, methane and carbon dioxide, into high value-added chemical products has attracted extensive attention of researchers all over the world at present. The methane-carbon dioxide reforming reaction can convert carbon dioxide and natural gas methane into synthesis gas (carbon monoxide and hydrogen), and is beneficial to reducing the emission of greenhouse gases. This reactionNot only can protect environment, but also has low H2the/CO ratio is directly used as a raw material gas for synthesis reaction of carbonyl group and the like, and is capable of providing great economic benefits, and attention of researchers has been paid in recent years.
For the chemical reaction, noble metal catalysts have high activity and anti-carbon deposition performance, but because of high price and limited resources, non-noble metal catalysts are generally researched. The Ni-based catalyst is one of catalytic systems with excellent catalytic performance for reforming reactions of carbon dioxide and methane except for noble metal catalysts, but the catalyst is quickly deactivated due to easy carbon deposition and poor sintering resistance of the reforming reactions of the methane and the carbon dioxide.
Chinese patent CN105964261A discloses a Ni-based catalyst prepared by taking one of mesoporous silica-based materials such as silica sol, SBA-15, KIT-6, HMS and the like as a carrier and adding an alkaline complexing agent, wherein the catalyst improves the carbon deposition resistance and sintering resistance in the reforming reaction of methane and carbon dioxide by utilizing the limited domain effect of the mesoporous material on Ni particles, and the prepared catalyst has higher activity and stability.
Chinese patent CN106513000A provides a preparation method of a supported nickel-based catalyst, the catalyst mainly comprises transition metal, silicon dioxide and nickel, the catalyst prepared by the method has uniform appearance, good stability and good methane and carbon dioxide reforming reaction activity.
Chinese patent CN106000405A discloses a hierarchical pore supported nickel-based catalyst, wherein the carrier is at least one of inorganic oxides, and the catalyst is used for methane carbon dioxide reforming reaction, shows excellent sintering resistance and carbon deposition resistance, and has important practical significance for promoting methane carbon dioxide reaction industrialization.
Although the catalyst utilizes the confinement effect of the mesoporous material to limit the growth of Ni nanoparticles, the skeleton of the mesoporous silica material is obviously shrunk after high-temperature treatment, so that the parameters such as specific surface, pore volume, pore diameter and the like are severely reduced, and the low thermal stability of the mesoporous silica material enables the reaction activity of the catalyst to be reduced at high temperature, so that the catalyst is inactivated.
Disclosure of Invention
The invention aims to provide a nickel-loaded silicon carbide catalyst for methane and carbon dioxide reforming reaction, which has good thermal stability, long service life and good activity, and a preparation method and application thereof.
The catalyst improves the sintering resistance and carbon deposition resistance of active metal in the catalyst, and improves the high-temperature thermal stability of the catalyst.
The invention provides a method for preparing a Ni-based catalyst by using non-oxide mesoporous silicon carbide as a carrier of the Ni-based catalyst, which prevents the growth and aggregation of nickel metal particles, has a limited domain effect on Ni nano particles, has the specific high-temperature structural stability, improves the sintering resistance and the carbon deposition resistance of the catalyst, and utilizes the high thermal stability and the chemical inertness of the silicon carbide to ensure that the prepared catalyst still keeps good activity and stability under high-temperature reaction.
In order to achieve the purpose, the nickel-loaded silicon carbide catalyst for the reforming reaction of methane and carbon dioxide is prepared by firstly synthesizing a silicon carbide ordered mesoporous material taking SBA-15, KIT-6, MCM-41, SBA-16, MCM-48, ZSM-22 and ZSM-5 as templates, and then loading active metal particle nickel on a silicon carbide material by an adsorption impregnation method to form a supported nickel-based silicon carbide catalyst with ordered mesoporous channels.
The pore volume of the nickel-loaded silicon carbide catalyst for the reforming reaction of methane and carbon dioxide is 0.1-0.4 cm3A specific surface area of 95 to 400 m/g2The pore diameter is 1-11 nm, the nickel loading is 4-10 wt%, and the balance is silicon carbide ordered mesoporous material.
The preparation method of the nickel-loaded silicon carbide catalyst for the reforming reaction of methane and carbon dioxide comprises the following steps:
(1) according to the silicon carbide precursor: the weight ratio of the dimethylbenzene is 1: 5-20, mixing the silicon carbide precursor and xylene, dissolving under stirring, adding the ordered mesoporous template raw material after complete dissolution, and performing reduced pressure rotary evaporation or magnetic stirring until xylene is completely volatilized to obtain a sample 1;
(2) drying the sample 1 in the step (1) at 80-120 ℃ for 12-24 h, then heating to 200-400 ℃ at a heating rate of 0.5-5 ℃/min under a nitrogen atmosphere, keeping the temperature for 2-6 h, then heating to 600-900 ℃ at a heating rate of 0.5-5 ℃/min, keeping the temperature for 1-5 h, crosslinking and pyrolyzing the silicon carbide precursor, and finally heating to 1200-1400 ℃ at a heating rate of 0.5-5 ℃/min, keeping the temperature for 1-3 h, thus obtaining a sample 2;
(3) as per sample 2: the mixed solution is 1 g: 5-50 mL, adding the sample 2 obtained in the step (2) into the mixed solution, stirring for 12-24 h, filtering and washing with water, and finally drying at 80-120 ℃ for 12-24 h to obtain the silicon carbide ordered mesoporous material;
(4) dissolving a dispersing agent with the mass of nickel precursor salt and nickel precursor salt in water according to the composition of the catalyst, dropwise adding the dispersing agent into the silicon carbide ordered mesoporous material, continuously stirring, stirring for 2-24 h after all the dispersing agent is dropwise added, carrying out ultrasonic treatment for 10 min-2 h, drying at 80-120 ℃ for 12-24 h, heating to 500-750 ℃ at the heating rate of 0.5-5 ℃/min under the flowing inert atmosphere after drying, and removing residues to obtain the nickel-based silicon carbide catalyst.
In the step (1), the silicon carbide precursor is one or two of polysilane, polycarbosilane and polymethylsilane.
The medium pore template in the step (1) is prepared from one of SBA-15, KIT-6, MCM-41, SBA-16, MCM-48, ZSM-22 and ZSM-5 molecular sieves.
In the step (1), the mass ratio of the silicon carbide precursor to the mesoporous template raw material is 1: 0.4-1.2.
The mixed liquid in the step (3) consists of ethanol, water and hydrofluoric acid, wherein the volume ratio of the ethanol to the water to the hydrofluoric acid is 1: 1-2: 0.5-2.
The nickel salt in the step (4) is one of nickel nitrate, nickel chloride and nickel acetylacetonate.
The dispersant in the step (4) is one of polyethylene glycol, polyoxyethylene-polyoxypropylene-polyoxyethylene, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone.
The addition amount of water in the step (4): the mass of the silicon carbide ordered mesoporous material is 3-10 mL: 1g of the total weight of the composition.
And (4) the flowing inert atmosphere in the step (4) is one of flowing nitrogen, argon or helium.
The application conditions of the catalyst in the methane carbon dioxide reforming reaction are as follows:
the reaction is carried out in a fixed bed reactor, and the reaction conditions are as follows: the pressure is 1-5 atm, the temperature is 700-750 ℃, and the gas space velocity GHSV is 2-96 L.g-1·h-1，CH4:CO2The volume ratio of (A) to (B) is 0.8-1.2: 1.
the nickel-loaded ordered mesoporous silicon carbide catalyst prepared by the method can ensure that the methane conversion rate is more than or equal to 82 percent and the deactivation rate of the catalyst is less than 2 percent at the temperature of 700-750 ℃.
The invention has the advantages and beneficial effects that:
(1) the invention provides a non-oxide mesoporous silicon carbide material as a carrier of a catalyst, which has the advantages of no acidity or alkalinity, no strong induced adsorption and coking capacity on carbon sources such as methane, carbon dioxide and the like, and carbon deposition inhibition;
(2) compared with the traditional supported catalyst, the supported nickel catalyst prepared by using the mesoporous silicon carbide material as the carrier has large pore diameter, specific surface and pore volume, and is particularly favorable for the dispersion and the confinement of active metal due to the ordered pore canal and narrow pore size distribution;
(3) the strong interaction between the metal and the carrier improves the sintering resistance of the active metal of the catalyst and causes a small amount of carbon deposition, and the strong interaction anchors the active metal in the ordered pore channel to prevent the movement of the nickel nano-particles.
(4) Compared with the mesoporous silicon oxide carrier, the silicon carbide has high thermal stability and chemical inertia, so that the skeleton of the mesoporous material can not shrink or collapse obviously after high-temperature treatment, and the prepared catalyst still keeps good stability and anti-carbon deposition performance under long-time high-temperature reaction.
(5) Compared with the traditional oxide supported catalyst, the active metal in the catalyst prepared by the invention exists in a metal state after being calcined, and the reforming reaction can be directly carried out without reduction.
Drawings
FIG. 1 shows Ni/m-N of SiC-1 catalyst2An adsorption-desorption curve;
FIG. 2 is a high resolution transmission electron micrograph of the Ni/m-SiC-2 catalyst.
FIG. 3 is an XRD pattern of the Ni/m-SiC-3 catalyst.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1: weighing 6g of polysilane and 30g of xylene solution at room temperature, mixing, dissolving under stirring, adding 7.2g of mesoporous template raw material SBA-15 after complete dissolution, and stirring by reduced pressure rotary evaporation until xylene is basically volatilized to obtain a sample 1. Sample 1 was transferred to a drying oven at 80 ℃ for 24 h. Then heating to 200 ℃ at a heating rate of 1 ℃/min under a nitrogen atmosphere, keeping the temperature for 5h, then heating to 600 ℃ at a heating rate of 0.5 ℃/min, keeping the temperature for 1h to crosslink and pyrolyze the polysilane, and finally heating to 1200 ℃ at a heating rate of 1 ℃/min, keeping the temperature for 3h to obtain a sample 2. And (2) adding 10g of sample 2 into 50mL of mixed solution of ethanol, water and hydrofluoric acid at a volume ratio of 1: 0.5, stirring for 12h, filtering and washing with water, and finally drying at 80 ℃ for 24h to obtain the ordered mesoporous silicon carbide carrier m-SiC-1 with the SBA-15-like template pore channel structure. Weighing 0.33g of nickel chloride and a polyethylene glycol dispersant with the same mass as the nickel chloride, adding 30mL of water to dissolve the nickel chloride and then dropwise adding the mixture into 3g of the prepared ordered mesoporous silicon carbide carrier, continuously stirring the mixture, stirring the mixture for 24 hours after all the mixture is dropwise added, then carrying out ultrasonic treatment on the sample for 10 minutes, drying the sample for 24 hours at 80 ℃, heating the sample to 500 ℃ at the heating rate of 1 ℃/min under the flowing nitrogen atmosphere, and removing residues to obtain the ordered mesoporous nickel-based silicon carbide catalyst Ni/m-SiC-1.
Example 2: weighing 6.0g of polycarbosilane and 60g of xylene solution at room temperature, mixing, dissolving under stirring, adding 5.0g of mesoporous template raw material KIT-6 after complete dissolution, and stirring by magnetic force until xylene is basically volatilized to obtain a sample 1. Sample 1 was transferred to a drying oven at 100 ℃ for 18 h. Then heating to 300 ℃ at a heating rate of 2 ℃/min under a nitrogen atmosphere, keeping the temperature for 4h, then heating to 700 ℃ at a heating rate of 0.5 ℃/min, keeping the temperature for 2h to crosslink and pyrolyze the polycarbosilane, and finally heating to 1250 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h to obtain a sample 2. And (2) adding 10g of sample 2 into 225mL of mixed solution of ethanol, water and hydrofluoric acid at a volume ratio of 1: 1, stirring for 18h, filtering and washing, and drying at 100 ℃ for 18h to obtain the ordered mesoporous silicon carbide carrier m-SiC-2 with a KIT-6-like template pore channel structure. Weighing 1.35g of nickel nitrate and a polyoxyethylene-polyoxypropylene-polyoxyethylene dispersing agent which is equal to the nickel nitrate in mass, adding 9mL of water to dissolve the nickel nitrate and the polyoxyethylene-polyoxypropylene-polyoxyethylene dispersing agent, dropwise adding the mixture into 3g of the prepared ordered mesoporous silicon carbide carrier, continuously stirring, stirring for 20h after all the mixture is dropwise added, then carrying out ultrasonic treatment on the sample for 30min, drying for 18h at 100 ℃, heating to 600 ℃ at a heating rate of 2 ℃/min under a flowing argon atmosphere, and removing residues to obtain the ordered mesoporous nickel-based silicon carbide catalyst Ni/m-SiC-2.
Example 3: weighing 6.0g of polymethylsilane and 90g of xylene solution at room temperature, mixing, dissolving under stirring, adding 4.0g of mesoporous template material MCM-41 after complete dissolution, and stirring by reduced pressure rotary evaporation until xylene is basically volatilized to obtain a sample 1. Sample 1 was transferred to a drying oven at 110 ℃ for 16 h. Then heating to 350 ℃ at a heating rate of 4 ℃/min under a nitrogen atmosphere, keeping the temperature for 2h, then heating to 800 ℃ at a heating rate of 1 ℃/min, keeping the temperature for 3h to crosslink and pyrolyze the polymethyl silane, and finally heating to 1300 ℃ at a heating rate of 4 ℃/min, keeping the temperature for 2.5h to obtain a sample 2. And (2) adding 10g of sample 2 into 300mL of mixed solution of ethanol, water and hydrofluoric acid at a volume ratio of 1: 2, stirring for 20h, filtering and washing, and finally drying at 110 ℃ for 16h to obtain the ordered mesoporous silicon carbide carrier m-SiC-3 with the MCM-41-like template pore channel structure. Weighing 1.05g of nickel acetylacetonate and a hexadecyl trimethyl ammonium bromide dispersing agent which is equal to the nickel acetylacetonate in mass, adding 18mL of water to dissolve the mixture, dropwise adding the mixture into 3g of the prepared ordered mesoporous silicon carbide carrier, continuously stirring, stirring for 18h after all the mixture is dropwise added, then carrying out ultrasonic treatment on the sample for 60min, drying for 16h at 110 ℃, heating to 650 ℃ at a heating rate of 4 ℃/min under a flowing helium atmosphere, and removing residues to obtain the ordered mesoporous nickel-based silicon carbide catalyst Ni/m-SiC-3.
Example 4: weighing 6.0g of a mixture of polysilane and polycarbosilane with the same mass as the mixture and 120g of xylene solution at room temperature, mixing the mixture and the xylene solution under stirring, adding 3.0g of mesoporous template raw material SBA-16 after the mixture is completely dissolved, and stirring the mixture by reduced pressure rotary evaporation until xylene is basically volatilized to obtain a sample 1. Sample 1 was transferred to a 120 ℃ dry box for 12 h. Then heating to 400 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, keeping the temperature for 1h, then heating to 900 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 4h to crosslink and pyrolyze the polysilane and the polycarbosilane, and finally heating to 1350 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 3h to obtain a sample 2. And (3) adding 10g of sample 2 into 400mL of mixed solution of ethanol, water and hydrofluoric acid at a volume ratio of 1: 2: 0.5, stirring for 24h, filtering and washing, and finally drying at 120 ℃ for 12h to obtain the ordered mesoporous silicon carbide carrier m-SiC-4 with the SBA-16-like template pore channel structure. Weighing 0.69g of nickel chloride and a polyvinylpyrrolidone dispersing agent with the same mass as the nickel chloride, adding 15mL of water to dissolve the nickel chloride and then dropwise adding the mixture into 3g of the prepared ordered mesoporous silicon carbide carrier, continuously stirring, stirring for 14h after all the components are dropwise added, then carrying out ultrasonic treatment on the sample for 1.5h, drying for 12h at 120 ℃, heating to 700 ℃ at a heating rate of 5 ℃/min under a flowing nitrogen atmosphere to remove residues, and obtaining the ordered mesoporous nickel-based silicon carbide catalyst Ni/m-SiC-4.
Example 5: weighing 6.0g of a mixture of polysilane and polymethylsilane with equal mass at room temperature, mixing the mixture with 100g of xylene solution, dissolving the mixture under stirring, adding 4.5g of mesoporous template raw material MCM-48 after the mixture is completely dissolved, and stirring the mixture by magnetic force until the xylene is basically volatilized to obtain a sample 1. Sample 1 was transferred to a drying cabinet at 110 ℃ for 20 h. Then heating to 350 ℃ at a heating rate of 3 ℃/min under a nitrogen atmosphere, keeping the temperature for 2.5h, then heating to 850 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 5h to crosslink and pyrolyze the polysilane and the polymethylsilane, and finally heating to 1400 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 1h to obtain a sample 2. And (2) adding 10g of sample 2 into 500mL of mixed solution of ethanol, water and hydrofluoric acid at a volume ratio of 1: 2: 1, stirring for 22h, filtering and washing, and finally drying at 110 ℃ for 20h to obtain the ordered mesoporous silicon carbide carrier m-SiC-5 with the MCM-48-like template pore channel structure. Weighing 1.77g of nickel nitrate and a polyethylene glycol dispersant with the same mass as the nickel nitrate, adding 21mL of water to dissolve the nickel nitrate and then dropwise adding the mixture into 3g of the prepared ordered mesoporous silicon carbide carrier, continuously stirring the mixture, stirring the mixture for 8 hours after all the mixture is dropwise added, then ultrasonically treating the sample for 2 hours, drying the sample for 20 hours at 110 ℃, heating the sample to 750 ℃ at a heating rate of 3 ℃/min under a flowing argon atmosphere, and removing residues to obtain the ordered mesoporous nickel-based silicon carbide catalyst Ni/m-SiC-5.
Example 6: weighing 6.0g of a polycarbosilane and polymethylsilane mixture with the same mass at room temperature, mixing the polycarbosilane and polymethylsilane mixture with 70g of xylene, dissolving the mixture under stirring, adding 2.4g of mesoporous template raw material ZSM-22 after the mixture is completely dissolved, and stirring the mixture by magnetic force until the xylene is basically volatilized to obtain a sample 1. Sample 1 was transferred to a drying oven at 100 ℃ for 18 h. Then heating to 300 ℃ at a heating rate of 2.5 ℃/min under a nitrogen atmosphere, keeping the temperature for 3h, then heating to 750 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 3.5h to crosslink and pyrolyze polycarbosilane and polymethylsilane, and finally heating to 1300 ℃ at a heating rate of 2.5 ℃/min, keeping the temperature for 2.5h to obtain a sample 2. And (3) adding 10g of sample 2 into 350mL of mixed solution of ethanol, water and hydrofluoric acid at a volume ratio of 1: 2, stirring for 18h, filtering and washing, and finally drying at 80 ℃ for 12h to obtain the ordered mesoporous silicon carbide carrier m-SiC-6 with a ZSM-22-like template pore channel structure. Weighing 1.32g of nickel acetylacetonate and a polyoxyethylene-polyoxypropylene-polyoxyethylene dispersing agent which is equal to the nickel acetylacetonate in mass, adding 12mL of water to dissolve the mixture, dropwise adding the mixture into 3g of the prepared ordered mesoporous silicon carbide carrier, continuously stirring, stirring for 4 hours after all the mixture is dropwise added, then carrying out ultrasonic treatment on the sample for 1 hour, drying for 12 hours at 100 ℃, heating to 650 ℃ at a heating rate of 2.5 ℃/min under a flowing helium atmosphere, and removing residues to obtain the ordered mesoporous nickel-based silicon carbide catalyst Ni/m-SiC-6.
Example 7: weighing 6.0g of polycarbosilane and 50g of xylene at room temperature, mixing, dissolving under stirring, adding 6.0g of mesoporous template raw material ZSM-5 after complete dissolution, and stirring by reduced pressure rotary evaporation until xylene is basically volatilized to obtain a sample 1. Sample 1 was transferred to a drying oven at 90 ℃ for 14 h. Then heating to 250 ℃ at a heating rate of 0.5 ℃/min under a nitrogen atmosphere and keeping for 5h, then heating to 650 ℃ at a heating rate of 2.5 ℃/min and keeping for 2.5h to crosslink and pyrolyze the polycarbosilane, and finally heating to 1200 ℃ at a heating rate of 0.5 ℃/min and keeping for 5h to obtain a sample 2. And (3) adding 10g of sample 2 into 100mL of mixed solution of ethanol, water and hydrofluoric acid at a volume ratio of 1: 0.5, stirring for 16h, filtering and washing with water, and finally drying at 90 ℃ for 14h to obtain the ordered mesoporous silicon carbide carrier m-SiC-7 with a ZSM-5-like template pore channel structure. Weighing 0.9g of nickel nitrate and 24mL of polyvinylpyrrolidone dispersing agent with the same mass as the nickel nitrate, adding water to dissolve the nickel nitrate and the polyvinylpyrrolidone dispersing agent, dropwise adding the dissolved mixture into 3g of the prepared ordered mesoporous silicon carbide carrier, continuously stirring, stirring for 2h after all the components are dropwise added, then carrying out ultrasonic treatment on the sample for 30min, drying the sample at 100 ℃ for 12h, heating to 550 ℃ at a heating rate of 0.5 ℃/min under a flowing nitrogen atmosphere, and removing residues to obtain the ordered mesoporous nickel-based silicon carbide catalyst Ni/m-SiC-7.
Physicochemical characteristic parameters of the nickel-based silicon carbide-supported catalysts prepared in examples 1 to 7 are shown in Table 1.
TABLE 1 physicochemical Properties of Nickel-based silicon carbide Supported catalysts
The use of the catalysts of examples 1-7 in the reforming reaction of methane and carbon dioxide is further illustrated below.
Application 1: weighing 0.5g of 20-60 meshes of catalyst particles in example 1, uniformly mixing the catalyst particles with 2.5g of quartz sand, putting the mixture into a reaction tube, introducing methane and carbon dioxide under normal pressure to perform catalytic reforming reaction, wherein the gas inlet component is CH4︰CO21: 1.2, the reaction temperature is 700 ℃, and the gas space velocity GHSV is 96L g-1·h-1The reaction time was 50h, and the product was analyzed by gas chromatography.
Application 2: weighing 0.5g of 20-60 meshes of catalyst particles in example 2, uniformly mixing the catalyst particles with 2.5g of quartz sand, putting the mixture into a reaction tube, introducing methane and carbon dioxide under 1.5atm to perform catalytic reforming reaction, wherein the gas inlet component is CH4︰CO21: 1.1, reaction temperature is 750 ℃,the gas space velocity GHSV is 80L g-1·h-1The reaction time was 50h, and the product was analyzed by gas chromatography.
Application 3: weighing 0.5g of 20-60 meshes of catalyst 3 particles in example 3, uniformly mixing with 2.5g of quartz sand, putting into a reaction tube, introducing methane and carbon dioxide under 2atm for catalytic reforming reaction, and introducing a gas inlet component CH4︰CO21: 1.0, the reaction temperature is 725 ℃, and the gas space velocity GHSV is 60L g-1·h-1The reaction time was 50h, and the product was analyzed by gas chromatography.
Application 4: weighing 0.5g of 20-60 meshes of catalyst particles in example 4, uniformly mixing the catalyst particles with 2.5g of quartz sand, putting the mixture into a reaction tube, introducing methane and carbon dioxide under 3atm to perform catalytic reforming reaction, wherein the gas inlet component is CH4︰CO21: 0.9, reaction temperature 710 ℃, and gas space velocity GHSV of 40L g-1·h-1The reaction time was 50h, and the product was analyzed by gas chromatography.
Application 5: weighing 0.5g of 20-60 meshes of the catalyst particles in the example 5, uniformly mixing the catalyst particles with 2.5g of quartz sand, putting the mixture into a reaction tube, introducing methane and carbon dioxide under 4atm to perform catalytic reforming reaction, wherein the gas inlet component is CH4︰CO2At a reaction temperature of 740 ℃ and a gas space velocity GHSV of 20L g ═ 1: 0.8-1·h-1The reaction time was 50h, and the product was analyzed by gas chromatography.
Application 6: weighing 0.5g of 20-60 meshes of the catalyst particles in the example 6, uniformly mixing the catalyst particles with 2.5g of quartz sand, putting the mixture into a reaction tube, introducing methane and carbon dioxide under 5atm to perform catalytic reforming reaction, wherein the gas inlet component is CH4︰CO21: 1.0, the reaction temperature is 700 ℃, and the gas space velocity GHSV is 10L g-1·h-1The reaction time was 50h, and the product was analyzed by gas chromatography.
Application 7: weighing 0.5g of 20-60 meshes of the catalyst particles of example 7, uniformly mixing the catalyst particles with 2.5g of quartz sand, putting the mixture into a reaction tube, introducing methane and carbon dioxide under 2atm to perform catalytic reforming reaction, wherein the gas inlet component is CH4︰CO21: 1.2, reaction temperature 730 deg.CThe gas space velocity GHSV is 2L g-1·h-1The reaction time was 50h, and the product was analyzed by gas chromatography.
The results of the reactivity tests using the nickel-based silicon carbide supported catalysts prepared in examples 1 to 7 are shown in Table 2.
TABLE 2 deactivation rate of nickel-based silicon carbide supported catalyst 1-7
Claims (8)
1. A nickel-loaded silicon carbide catalyst for methane and carbon dioxide reforming reaction is characterized in that the pore volume of the nickel-loaded silicon carbide catalyst is 0.1-0.4 cm3A specific surface area of 95 to 400 m/g2The pore diameter is 1-11 nm, the nickel loading is 4-10 wt%, and the balance is silicon carbide ordered mesoporous material.
2. The method of claim 1, wherein the method comprises the steps of:
(1) according to the silicon carbide precursor: the weight ratio of the dimethylbenzene is 1: 5-20, mixing the silicon carbide precursor and xylene, dissolving under stirring, adding the ordered mesoporous template raw material after complete dissolution, and performing reduced pressure rotary evaporation or magnetic stirring until xylene is completely volatilized to obtain a sample 1;
(2) drying the sample 1 in the step (1) at 80-120 ℃ for 12-24 h, then heating to 200-400 ℃ at a heating rate of 0.5-5 ℃/min under a nitrogen atmosphere, keeping the temperature for 2-6 h, then heating to 600-900 ℃ at a heating rate of 0.5-5 ℃/min, keeping the temperature for 1-5 h, crosslinking and pyrolyzing the silicon carbide precursor, and finally heating to 1200-1400 ℃ at a heating rate of 0.5-5 ℃/min, keeping the temperature for 1-3 h, thus obtaining a sample 2;
(3) as per sample 2: the mixed solution is 1 g: 5-50 mL, adding the sample 2 obtained in the step (2) into the mixed solution, stirring for 12-24 h, filtering and washing with water, and finally drying at 80-120 ℃ for 12-24 h to obtain the silicon carbide ordered mesoporous material;
(4) dissolving a dispersing agent with the mass of nickel precursor salt and nickel precursor salt in water according to the composition of the catalyst, dropwise adding the dispersing agent into the silicon carbide ordered mesoporous material, continuously stirring, stirring for 2-24 h after all the dispersing agent is dropwise added, carrying out ultrasonic treatment for 10 min-2 h, drying at 80-120 ℃ for 12-24 h, heating to 500-750 ℃ at the heating rate of 0.5-5 ℃/min under the flowing inert atmosphere after drying, and removing residues to obtain a nickel-based silicon carbide catalyst;
the silicon carbide precursor in the step (1) is one or two of polysilane and polymethylsilane;
the raw material of the medium pore template in the step (1) is one of MCM-41, SBA-16, MCM-48, ZSM-22 and ZSM-5 molecular sieves;
in the step (1), the mass ratio of the silicon carbide precursor to the mesoporous template raw material is 1: 0.4-1.2.
3. The method according to claim 2, wherein the mixed solution in step (3) comprises ethanol, water and hydrofluoric acid, wherein the volume ratio of ethanol to water to hydrofluoric acid is 1: 1 to 2: 0.5 to 2.
4. The method of claim 2, wherein the nickel salt in the step (4) is one of nickel nitrate, nickel chloride and nickel acetylacetonate.
5. The method of claim 2, wherein the dispersant in the step (4) is one of polyethylene glycol, polyoxyethylene-polyoxypropylene-polyoxyethylene, cetyltrimethylammonium bromide, and polyvinylpyrrolidone.
6. The method for producing a nickel-supported silicon carbide catalyst for reforming reaction of methane and carbon dioxide as set forth in claim 2, wherein the amount of water added in the step (4) is: the mass of the silicon carbide ordered mesoporous material is 3-10 mL: 1g of the total weight of the composition.
7. The method of claim 2, wherein the inert gas flowing in the step (4) is one of nitrogen, argon and helium.
8. Use of a nickel-supported silicon carbide catalyst for methane and carbon dioxide reforming reactions according to claim 1, comprising the steps of:
the reaction is carried out in a fixed bed reactor, and the reaction conditions are as follows: the pressure is 1-5 atm, the temperature is 700-750 ℃, and the gas space velocity GHSV is 2-96 L.g-1·h-1，CH4:CO2The volume ratio of (A) to (B) is 0.8-1.2: 1.
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