CN113368859A - Nickel-zirconium co-doped mesoporous silica material and preparation method and application thereof - Google Patents
Nickel-zirconium co-doped mesoporous silica material and preparation method and application thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 49
- ZSJFLDUTBDIFLJ-UHFFFAOYSA-N nickel zirconium Chemical compound [Ni].[Zr] ZSJFLDUTBDIFLJ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000003756 stirring Methods 0.000 claims abstract description 25
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 20
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006057 reforming reaction Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 13
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 12
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000012265 solid product Substances 0.000 claims abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 31
- 239000007787 solid Substances 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000007605 air drying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 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
- 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
-
- B01J35/633—
-
- B01J35/647—
-
- B01J35/651—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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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 invention belongs to the technical field of catalytic materials, and discloses a nickel-zirconium co-doped mesoporous silica material and a preparation method and application thereof. The method comprises the following steps: 1) dissolving nickel nitrate in water, and adding ammonia water to obtain a nickel-containing solution; dissolving zirconyl nitrate in water to obtain a zirconium-containing solution; 2) mixing the zirconium-containing solution, the nickel-containing solution and the silica sol, heating and stirring, treating the product with water, and drying to obtain a solid product; 3) and (3) roasting the solid product at high temperature to obtain the nickel-zirconium co-doped mesoporous silica material. The method is simple, environment-friendly, low in material loss in the preparation process and high in yield. The nickel-zirconium co-doped mesoporous silica material is used in the field of catalysis, and particularly has good catalytic activity in the catalytic methane carbon dioxide reforming reaction.
Description
Technical Field
The invention belongs to the technical field of mesoporous materials, and particularly relates to a nickel-zirconium co-doped mesoporous silica material, and a preparation method and application thereof.
Background
Silica materials having a porous structure of micropores, mesopores, etc. are generally used as a carrier of a metal oxide catalyst due to their high specific surface area, good physical and chemical stability. Among transition metals, nickel (Ni), which is a group VIII in the fourth period, has excellent catalytic properties, and has been widely studied and applied to various important industrial catalytic reactions. Other metal assistants are doped into the nickel catalyst, so that the catalytic activity of the catalyst is obviously improved. In particular, related studies have demonstrated that doping with a moderate amount of zirconium can improve the catalytic performance of the nickel catalyst for methane reforming reactions.
The preparation method of the catalyst has important significance for improving the performance of the material and promoting the application of the catalytic reaction in industrial production. At present, the preparation method of the supported metal catalyst comprises the following steps: impregnation, precipitation, ion exchange, and chemical vapor deposition. Although the conventional impregnation method is simple in process and easy to control the stoichiometric ratio of each component, the catalyst prepared by the method has large and uneven metal particles, weak interaction between metal and a carrier, easy migration of active components in the drying process and low catalytic performance. Therefore, the search for a preparation method of a metal-doped mesoporous silica material with simple process, convenient operation and high yield has become a research hotspot and a significant challenge in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention mainly aims to provide a nickel-zirconium co-doped mesoporous silicon dioxide material and a preparation method thereof. The method not only simplifies the operation process, but also can reduce the loss of materials in the synthesis process, thereby saving the cost.
The invention also aims to provide application of the nickel-zirconium co-doped mesoporous silica material. The application of the nickel-zirconium co-doped mesoporous silica material in methane-carbon dioxide reforming reaction is used as a catalyst for the methane-carbon dioxide reforming reaction in the temperature range (650-800 ℃) and the flow rate range (20-100 mL/min). The nickel-zirconium co-doped mesoporous silica material has high catalytic activity of catalyzing the reaction of methane and carbon dioxide.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nickel-zirconium co-doped mesoporous silica material comprises the following steps:
1) dissolving nickel nitrate in water, and adding ammonia water to obtain a nickel-containing solution; dissolving zirconyl nitrate in water to obtain a zirconium-containing solution; the nickel nitrate is nickel nitrate containing crystal water or nickel nitrate without crystal water; the zirconyl nitrate is crystal water or does not contain crystal water;
2) mixing the zirconium-containing solution, the nickel-containing solution and the silica sol, heating and stirring, treating the product with water, and drying to obtain a solid product;
3) and (3) roasting the solid product at high temperature to obtain the nickel-zirconium co-doped mesoporous silica material.
The nickel nitrate containing the crystal water is nickel nitrate hexahydrate; the zirconyl nitrate is zirconyl nitrate hydrate.
Dissolving nickel nitrate in water, and adding ammonia water, wherein the volume ratio of water to ammonia water is (10-20) to (6-10);
the volume ratio of water to ammonia water in the zirconium-containing solution is (15-30) mL to (6-10).
The mass volume ratio of the silica sol to the ammonia water is (6-14) g to (6-10) mL.
The mass concentration of the ammonia water is 25-28%.
The mass percentage of silicon dioxide in the silica sol is 25-35%.
The molar ratio of Ni in the nickel-containing solution to silicon dioxide in the silica sol is (0.02-0.06) to 1; the molar ratio of Zr in the zirconium-containing solution to silica in the silica sol is (0.01-0.08) to 1.
The mixing in the step 2) is stirring mixing, the stirring time is 2-5 h, and the stirring temperature is room temperature.
The heating and stirring temperature in the step 2) is 60-100 ℃, and the heating and stirring time is 2-5 hours.
The step of treating the product with water refers to mixing the product with water, carrying out ultrasonic treatment, filtering and washing. The relationship between the amount of water and the amount of the raw material silica sol of the product is (20-50) mL to (6-14) g.
The ultrasonic treatment time is 5-10 min; the washing refers to washing with water.
The drying temperature in the step 2) is 90-110 ℃, and the drying time is 12-18 h;
step 3) the roasting atmosphere is static air instead of flowing air flow; the roasting temperature is 600-800 ℃, the roasting time is 4-7 h, and the heating rate is 3-6 ℃/min.
The molar ratio of Zr to Si in the nickel-zirconium co-doped mesoporous silica material is 0.01-0.08: 1, the molar ratio of Ni to Si is 0.02-0.06: 1.
the pore volume of the nickel-zirconium co-doped mesoporous silica material is 0.38-0.48 cm3The pore diameter is 7.06-7.9 nm, the specific surface area is 221-233 m2/g。
The nickel-zirconium co-doped mesoporous silica material is applied to methane-carbon dioxide reforming reaction and used as a catalyst for catalyzing methane-carbon dioxide reforming reaction.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the synthesis method adopted by the invention can synthesize the nickel-zirconium co-doped mesoporous silica material with high specific surface area and uniform aperture;
(2) the invention mainly adopts water, nickel nitrate hexahydrate, zirconyl nitrate hydrate, silica sol and other raw materials, has low price, is convenient and easy to obtain, is nontoxic and harmless to human bodies, and can not generate intermediate products harmful to the environment;
(3) the synthesis process is simple and clear, and the raw material loss in the intermediate synthesis process can not be caused;
(4) according to the invention, nickel and zirconium are codoped into the mesoporous silica material through a one-step synthesis method, so that the molar ratio of nickel to zirconium can be flexibly changed within a certain range;
(5) the nickel-zirconium co-doped mesoporous silica material provided by the invention is used as a catalyst, and has a good catalytic effect in catalyzing methane-carbon dioxide reforming reaction.
Drawings
FIG. 1 is a graph showing the relationship between the methane conversion rate and the flow rate of a reaction gas in the methane-carbon dioxide reforming reaction using the materials obtained in examples 1 to 4;
FIG. 2 is a graph showing the relationship between the methane conversion rate and the reaction temperature in the methane-carbon dioxide reforming reaction of the materials obtained in examples 1 to 4.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the mode of carrying out the invention is not limited thereto. In the embodiment of the invention, the mass percent of silicon dioxide in the silica sol is 30%.
Example 1
Nickel-zirconium co-doped mesoporous silicon dioxide material (recorded as Ni-0.01 Zr/SiO)2) (0.01 represents the molar ratio of Zr to Si), specifically comprising the steps of:
0.5056g of Ni (NO) were weighed out3)2·6H2Dissolving O in 10mL of deionized water, adding 6mL of concentrated ammonia water (the mass concentration of the ammonia water is 25-28%), stirring to obtain a bluish purple solution, and obtaining a nickel-containing solution; 0.1662g ZrO (NO) were weighed out3)2·H2Dissolving O in 15mL of deionized water to obtain a zirconium-containing solution; adding a zirconium-containing solution into a nickel-containing solution, then adding 13.334g of silica sol, stirring the obtained mixed solution for 2 hours, then carrying out oil bath heating, controlling the oil temperature at 60 ℃, and stirring for 2 hours to completely evaporate water; adding 20mL of deionized water, performing ultrasonic oscillation on an ultrasonic cleaner for 5min, performing suction filtration on the oscillated solution, and cleaning a filter cake by using 400mL of deionized water; drying the obtained solid in a forced air drying oven at 90 ℃ for 18 h; transferring the dried solid into a muffle furnace, heating the solid to 600 ℃ from room temperature at a heating rate of 3 ℃/min, roasting the solid for 7 hours, and naturally cooling the solid to room temperature to obtain the nickel-zirconium co-doped mesoporous silica material which is recorded as Ni-0.01Zr/SiO2。
Ni-0.01Zr/SiO synthesized in this example2Has a pore volume of 0.38cm3A pore diameter of 7.06nm and a specific surface area of 221m2/g。
Example 2
Nickel-zirconium co-doped mesoporous silicon dioxide material (recorded as Ni-0.02 Zr/SiO)2) (0.02 represents the molar ratio of Zr to Si), specifically comprising the steps of:
0.5158gNi (NO)3)2·6H2Dissolving O in 14mL of deionized water, adding 8mL of concentrated ammonia water (the mass concentration of the concentrated ammonia water is 25-28%), and stirring to obtain a bluish purple solution, namely a nickel-containing solution; 0.1662g ZrO (NO) were weighed out3)2·H2Dissolving O in 15mL of deionized water to obtain a zirconium-containing solution; adding a zirconium-containing solution into a nickel-containing solution, then adding 6.667g of silica sol, stirring the obtained mixed solution for 3h, then carrying out oil bath heating, controlling the oil temperature at 80 ℃, stirring for 3h to completely evaporate water, adding 30mL of deionized water, then carrying out ultrasonic oscillation on an ultrasonic wave cleaner for 5min, carrying out suction filtration on the oscillated solution, cleaning a filter cake with 500mL of deionized water, and drying the obtained solid in a blast drying box at 100 ℃ for 12 h; transferring the dried solid into a muffle furnace, heating the solid to 700 ℃ from room temperature at a heating rate of 5 ℃/min, roasting the solid for 5 hours, and naturally cooling the solid to room temperature to obtain the Ni-Zr co-doped mesoporous silica material which is recorded as Ni-0.02Zr/SiO2。
Ni-0.02Zr/SiO synthesized in this example2Has a pore volume of 0.40cm3A pore diameter of 7.10nm and a specific surface area of 223m2/g。
Example 3
Nickel-zirconium co-doped mesoporous silicon oxide material (recorded as Ni-0.04 Zr/SiO)2) (0.04 represents the molar ratio of Zr to Si), specifically comprising the steps of:
0.5362g of Ni (NO) were weighed out3)2·6H2Dissolving O in 16mL of deionized water, adding 9mL of strong ammonia water (the concentration of the strong ammonia water is 25-28%), and stirring to obtain a bluish purple solution, namely a nickel-containing solution; 0.4985g ZrO (NO) were weighed out3)2·H2Dissolving O in 20mL of deionized water to obtain a zirconium-containing solution; adding zirconium-containing solution into nickel-containing solution, adding 10.00g of silica sol, stirring the obtained mixed solution for 4h, heating in oil bath with the oil temperature controlled at 100 ℃,stirring for 4h to completely evaporate water, adding 40mL of deionized water, performing ultrasonic oscillation on an ultrasonic cleaner for 7min, performing suction filtration on the oscillated solution, cleaning a filter cake with 500mL of deionized water, and drying the obtained solid in a forced air drying oven at 110 ℃ for 14 h; transferring the dried solid into a muffle furnace, heating the solid to 800 ℃ from room temperature at a heating rate of 4 ℃/min, roasting the solid for 4 hours, and naturally cooling the solid to room temperature to obtain the Ni-Zr co-doped mesoporous silica material which is recorded as Ni-0.04Zr/SiO2。
Ni-0.04Zr/SiO synthesized in this example2Has a pore volume of 0.46cm3(ii)/g, pore diameter of 7.60nm, specific surface area of 233m2/g。
Example 4
Nickel-zirconium co-doped mesoporous silicon dioxide material (recorded as Ni-0.08 Zr/SiO)2) (0.08 represents a molar ratio of Zr to Si), specifically comprising the steps of:
0.5761g of Ni (NO) were weighed out3)2·6H2Dissolving O in 20mL of deionized water, adding 10mL of concentrated ammonia water, and stirring to obtain a bluish purple solution, namely a nickel-containing solution; 0.6647g ZrO (NO) were weighed out3)2·H2Dissolving O in 30mL of deionized water to obtain a zirconium-containing solution; adding a zirconium-containing solution into a nickel-containing solution, then adding 6.667g of silica sol, stirring the obtained mixed solution for 5 hours, then carrying out oil bath heating, controlling the oil temperature at 80 ℃, stirring for 5 hours to completely evaporate water, adding 50mL of deionized water, then carrying out ultrasonic oscillation on an ultrasonic cleaner for 10min, carrying out suction filtration on the oscillated solution, cleaning a filter cake with 500mL of deionized water, and drying the obtained solid in a blast drying box at 100 ℃ for 12 hours; and transferring the dried solid into a muffle furnace, heating the solid to 800 ℃ from room temperature at a heating rate of 6 ℃/min, roasting the solid for 6 hours, and naturally cooling the solid to room temperature to obtain the nickel-zirconium co-doped mesoporous silica material.
Ni-0.08Zr/SiO synthesized in this example2Has a pore volume of 0.48cm3A pore diameter of 7.90nm and a specific surface area of 228m2/g。
The products obtained in examples 1 to 4 were used in methane-carbon dioxide reforming reaction (CH)4/CO2In a molar ratio of 1: 1) the results of the relationship between the methane conversion and the flow rate of the reaction gas are shown in FIG. 1. Ni/SiO in FIG. 12: zr was not used and the other conditions were the same as in example 1.
As can be seen from FIG. 1, CH of methane dry reforming reaction by applying nickel-zirconium co-doped mesoporous silica catalyst is applied in a flow rate range of 20-100 mL/min (temperature is 750 ℃; flow rate refers to total flow rate of methane and carbon dioxide, wherein the flow rate of methane and carbon dioxide is half of the total flow rate), under the same flow rate4The conversion rate is higher than that of a nickel catalyst without Zr doping, which shows that the Zr doping is beneficial to improving the catalytic activity of the nickel-based catalyst; second, for the same catalyst, the greater the flow rate, the CH4The lower the conversion of (a); in addition, Ni-0.02Zr/SiO at the same flow rate2The conversion rate is the highest, which indicates that the catalytic activity of the catalyst is the best, namely when the molar ratio of Si to Zr is 1: 0.02, the catalytic activity of the synthesized Ni-Zr co-doped mesoporous silica material is the best.
The results of the relationship between the methane conversion rate and the reaction temperature when the products obtained in examples 1 to 4 were used in the methane-carbon dioxide reforming reaction are shown in fig. 2. Ni/SiO in FIG. 12: zr was not used and the other conditions were the same as in example 1.
As can be seen from FIG. 2, the CH temperature is within the range of 650-800 ℃ (the flow rate is 80mL/min specifically)4The conversion of (a) increases with increasing temperature; ni-0.02Zr/SiO at the usual dry reforming reaction temperature (750 ℃ C.) for methane2The catalyst still shows higher conversion rate, which indicates that the catalytic activity of the catalyst is the best, namely when the molar ratio of Si to Zr is 1: 0.02, the catalytic activity of the synthesized Ni-Zr co-doped mesoporous silica material is the best.
From a combination of FIGS. 1 and 2, it can be seen that Ni-0.02Zr/SiO2The catalytic activity of the catalyst is optimal.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a nickel-zirconium co-doped mesoporous silica material is characterized by comprising the following steps: the method comprises the following steps:
1) dissolving nickel nitrate in water, and adding ammonia water to obtain a nickel-containing solution; dissolving zirconyl nitrate in water to obtain a zirconium-containing solution; the nickel nitrate is nickel nitrate containing crystal water or nickel nitrate without crystal water; the zirconyl nitrate contains or does not contain crystal water;
2) mixing the zirconium-containing solution, the nickel-containing solution and the silica sol, heating and stirring, treating the product with water, and drying to obtain a solid product;
3) roasting the solid product at high temperature to obtain a nickel-zirconium co-doped mesoporous silica material; the roasting temperature is 600-800 ℃, and the roasting time is 4-7 h.
2. The preparation method of the nickel-zirconium co-doped mesoporous silica material according to claim 1, wherein the preparation method comprises the following steps: the molar ratio of Ni in the nickel-containing solution to silicon dioxide in the silica sol is (0.02-0.06) to 1; the molar ratio of Zr in the zirconium-containing solution to silicon dioxide in the silica sol is (0.01-0.08) to 1;
dissolving nickel nitrate in water, and adding ammonia water, wherein the volume ratio of water to ammonia water is (10-20) to (6-10);
the volume ratio of water in the zirconium-containing solution to ammonia water added in the nickel-containing solution is (15-30) to (6-10);
the mass volume ratio of the silica sol to the ammonia water is (6-14) g to (6-10) mL;
the mass percent of silicon dioxide in the silica sol is 25-35%; the mass concentration of the ammonia water is 25-28%.
3. The preparation method of the nickel-zirconium co-doped mesoporous silica material according to claim 1, wherein the preparation method comprises the following steps: step 3) the roasting atmosphere is static air instead of flowing air flow; the heating rate is 3-6 ℃/min;
the heating and stirring temperature in the step 2) is 60-100 ℃, and the heating and stirring time is 2-5 hours.
4. The preparation method of the nickel-zirconium co-doped mesoporous silica material according to claim 1, wherein the preparation method comprises the following steps:
the nickel nitrate containing the crystal water is nickel nitrate hexahydrate; the zirconyl nitrate is zirconyl nitrate hydrate; the mixing in the step 2) is stirring mixing, wherein the stirring time is 2-5 h, and the stirring temperature is room temperature;
the drying temperature in the step 2) is 90-110 ℃, and the drying time is 12-18 h;
the step 2) of treating the product with water refers to mixing the product with water, performing ultrasonic treatment, filtering and washing.
5. The preparation method of the nickel-zirconium co-doped mesoporous silica material according to claim 4, wherein the preparation method comprises the following steps: in the step 2), treating the product with water, wherein the relationship between the water consumption and the consumption of the raw material silica sol of the product is (20-50) mL to (6-14) g; the ultrasonic treatment time is 5-10 min; the washing refers to washing with water.
6. The preparation method of the nickel-zirconium co-doped mesoporous silica material according to claim 1, wherein the preparation method comprises the following steps: in the nickel-zirconium co-doped mesoporous silica material, the molar ratio of Zr to Si is 0.01-0.08: 1, and the molar ratio of Ni to Si is 0.02-0.06: 1.
7. the nickel-zirconium co-doped mesoporous silica material prepared by the preparation method of any one of claims 1 to 6.
8. The nickel-zirconium-codoped mesoporous silica material according to claim 7, wherein: the pore volume of the nickel-zirconium co-doped mesoporous silica material is 0.38-0.48 cm3A pore diameter of 7.06 to 7.9nm and a specific surface area of 221 to 233m2/g。
9. The application of the nickel-zirconium co-doped mesoporous silica material according to any one of claims 7 to 8, wherein: the nickel-zirconium co-doped mesoporous silica material is applied to methane-carbon dioxide reforming reaction and used as a catalyst.
10. Use according to claim 9, characterized in that: in the methane-carbon dioxide reforming reaction, the temperature is 650-800 ℃; the total flow rate of the methane and the carbon dioxide is 20-100 mL/min, and the flow rates of the methane and the carbon dioxide are the same.
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