CN112452328B - Ni@SiO2@Co-Al2O3Preparation method of multistage core-shell catalyst - Google Patents
Ni@SiO2@Co-Al2O3Preparation method of multistage core-shell catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 45
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 45
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 45
- 229910052905 tridymite Inorganic materials 0.000 title claims abstract description 45
- 239000011258 core-shell material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000000243 solution Substances 0.000 claims abstract description 73
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910002706 AlOOH Inorganic materials 0.000 claims abstract description 43
- 239000008367 deionised water Substances 0.000 claims abstract description 40
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 32
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 18
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 39
- 238000005406 washing Methods 0.000 claims description 37
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 34
- 230000035484 reaction time Effects 0.000 claims description 19
- 230000009467 reduction Effects 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 230000008021 deposition Effects 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005245 sintering Methods 0.000 abstract description 6
- 235000019441 ethanol Nutrition 0.000 description 45
- 239000000047 product Substances 0.000 description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 21
- 239000002245 particle Substances 0.000 description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- 238000002407 reforming Methods 0.000 description 10
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 7
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910003266 NiCo Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention discloses NiO @ SiO2The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized in that a nickel source and polyvinylpyrrolidone are dissolved in an alcohol solution to react to obtain NiO nano-particles; adding the mixture into a mixed solution of ethanol, deionized water, ammonia water and hexadecyl trimethyl ammonium bromide, and adding tetraethoxysilane to obtain NiO @ SiO2Dispersing the alumina sol in the alumina sol, repeating for many times to obtain NiO @ SiO with different alumina sol coating thicknesses2@ AlOOH; mixing a cobalt source with NH4F is dissolved in deionized water, NiO @ SiO is added2@ AlOOH, reaction; drying, roasting and reducing to obtain Ni @ SiO2@Co‑Al2O3A multi-stage core-shell catalyst. The invention has a multi-stage core-shell structure, can improve the carbon deposition resistance and sintering resistance of Ni to a greater extent, and greatly improves the stability and service life of the catalyst.
Description
Technical Field
The invention belongs to the technical field of energy utilization and environment, and relates to NiO @ SiO2A preparation method of a @ CoAl-LDH multi-stage core-shell catalyst and application thereof in methane carbon dioxide reforming reaction.
Background
To solve the problem of greenhouse gas (CH)4、CO2) Global warming problem caused by rising concentration, CH4And CO2Has been the focus of research. Methane carbon dioxide Dry Reforming (DRM) is not only capable of converting these two major greenhouse gases into industrially valuable synthesis gas (V)H2/VCO1) and the synthesis gas is availableIn the synthesis of long-chain hydrocarbons or oxygenates. Ni-based catalysts are considered to be the most promising catalysts for industrialization due to their low economic cost and high activity. However, under severe reforming conditions, Ni-based catalysts are susceptible to deactivation by sintering and carbon deposition. Therefore, the development of a highly stable and anti-carbon deposition, anti-sintering Ni catalyst is the main objective of the study herein.
The improved approach mainly comprises the following aspects: the method comprises the following steps of reducing the size of Ni particles, improving the dispersity of the Ni particles, controlling the acidity and alkalinity of the catalyst, selectively passivating active metal Ni, designing and regulating the structure of the catalyst, and the like. In recent years, novel multifunctional core-shell composite materials are widely applied to the research in the field of catalysis due to unique structure and properties of the composite materials, and the core-shell catalyst plays a certain protection role because nano metal active particles are coated by an outer layer, and can effectively inhibit the growth of active metal nano particles in the process of catalytic reaction, particularly in high-temperature reaction. Therefore, the design and synthesis of the nano Ni-based catalyst with the core-shell structure can be expected to solve the key problems of carbon deposition and sintering of the catalyst which greatly limit the application of the Ni-based catalyst in the reaction of methane and carbon dioxide.
The patent CN107262097A discloses a NiCo/SiO2A preparation method of a core-shell catalyst. Firstly, preparing NiCo alloy nano particles, then adding a silicon source, stirring for reaction, settling a solid product by using methanol, centrifugally washing, drying a washed sample, and roasting at high temperature to obtain NiCo/SiO2A core-shell catalyst. The reactivity is high, but the reaction life is not long enough, the Ni particle size is not controllable, and the synergy of NiCo alloy needs a certain distance to exert the function to the maximum extent.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to improve the sintering resistance and the carbon deposition resistance of the existing Ni active center.
In order to solve the technical problem, the invention provides NiO @ SiO2The preparation method of the @ CoAl-LDH multistage core-shell catalyst is characterized by comprising the following steps of:
step 1): dissolving a nickel source and polyvinylpyrrolidone in an alcohol solution, stirring until the nickel source and the polyvinylpyrrolidone are dissolved, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, filtering after the reaction is finished, washing and drying to obtain NiO nano-particles;
step 2): preparing a mixed solution of ethanol, deionized water, ammonia water and hexadecyl trimethyl ammonium bromide, then adding the NiO nano-particles obtained in the step 1) into the mixed solution, ultrasonically dispersing for 10-60min, and continuously stirring for 0.5-3h at room temperature to uniformly disperse the NiO nano-particles in the solution; slowly adding tetraethoxysilane into the NiO solution under vigorous stirring, reacting at room temperature, washing the obtained product with ethanol, drying and roasting to obtain NiO @ SiO2;
And step 3): NiO @ SiO obtained in step 2)2Dispersing in alumina sol, stirring vigorously, filtering, washing with anhydrous alcohol, drying at room temperature to obtain NiO @ SiO2@ AlOOH; the obtained NiO @ SiO2The @ AlOOH is dispersed in the alumina sol again, and the operation is repeated for a plurality of times as required to obtain NiO @ SiO with different alumina sol coating thicknesses2@AlOOH;
And step 4): mixing a cobalt source with NH4F is dissolved in deionized water to prepare a solution, and the NiO @ SiO obtained in the step 3) is added2Adding @ AlOOH into the solution, transferring the obtained solution into a hydrothermal kettle with a polytetrafluoroethylene lining, and reacting in an oven; then centrifugally washing the obtained product to be neutral, and drying the product in an oven to finally obtain NiO @ SiO2@CoAl-LDH;
Step 5): NiO @ SiO obtained in the step 4)2Baking @ CoAl-LDH in muffle furnace to obtain oxide catalyst, and reacting in reactor via H2After gas reduction, Ni @ SiO is prepared2@Co-Al2O3A multistage core-shell catalyst.
Preferably, the nickel source in step 1) is nickel acetate; the alcohol solution is at least one aqueous solution of methanol, ethanol, propanol and glycol, and the volume ratio of the alcohol to the water is 1 (0.1-1); the ratio of nickel acetate to polyvinylpyrrolidone was 1 mmol: (1-8 g); the ratio of nickel to alcoholic solution is 1 mmol: (50-400) mL; the molecular weight of polyvinylpyrrolidone is 54,000.
Preferably, the temperature of the hydrothermal reaction in the step 1) is 100-180 ℃, and the time is 6-16 h.
Preferably, the ratio of nickel to the sum of the volumes of ethanol and deionized water in the step 2) is 1 mmol: (50-300) mL; the volume ratio of ethanol, deionized water and ammonia water in the mixed solution is 50: 50: (1-8); the molar ratio of hexadecyl trimethyl ammonium bromide to Ni is (1-10): 1; the usage amount of the tetraethoxysilane is as follows according to the molar ratio of Si to Ni (0.5-4): 1 is the standard.
Preferably, the reaction time in the step 2) is 12-36 h, and the roasting temperature is 400-700 ℃.
Preferably, the alumina sol in the step 3) is AlOOH, NiO @ SiO2The ratio of AlOOH to AlOOH is 1 mmol: 10-50 mL; the number of repetition is 2-20.
Preferably, the time for vigorous stirring in the step 3) is 1 h; the drying time was 1 h.
Preferably, the cobalt source in the step 4) is cobalt nitrate; NiO @ SiO2@ AlOOH, cobalt, NH4The molar ratio of F is (0.3-1.5): 1: 1.5; the ratio of cobalt to deionized water was 1 mmol: 20-60 mL.
Preferably, the reaction temperature in the step 4) is 80-150 ℃ and the reaction time is 12-60 h.
Preferably, the roasting temperature in the step 5) is 400-800 ℃, and the time is 4-12 h.
Compared with the prior art, the invention has the following advantages:
(1) the hydrothermal method can easily control the size of Ni by controlling conditions such as reaction temperature, reaction time and the like, and ensures that Ni has smaller particle size, thereby having better catalytic performance and stability.
(2) The catalyst has a multi-stage core-shell structure, can improve the carbon deposition resistance and sintering resistance of Ni to a greater extent, and greatly improves the stability and service life of the catalyst.
(3) The preparation method of the catalyst can realize industrial amplification in each step, and the yield of the prepared catalyst is high, thereby avoiding resource waste.
(4) The catalyst contains magnetic metal Co, so that the magnet can be used for recovering the catalyst, and the problem of industrial catalyst recovery is more conveniently realized.
Drawings
FIG. 1 is a schematic diagram of the synthesis of the catalyst provided by the present invention.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
NiO @ SiO prepared in example2@ CoAl-LDH catalyst and NiO, Co prepared in comparative examples3O4And Al2O3Loaded on SiO2The evaluation process of the supported catalyst for the carbon dioxide reforming reaction of methane was as follows:
0.1g (80-100 meshes) of catalyst and 0.9g (80-100 meshes) of quartz sand are weighed and mixed evenly in H2/N2Atmosphere (50% each by volume, flow rate 120mL/min), 700 ℃ pre-reduction for 2 h. After the reduction is finished, the reaction temperature is 850 ℃, the ratio of methane to carbon dioxide in the raw material gas is 1.2, and N23% as internal standard. The flow rate of the raw material gas is 141.7mL/min, the space velocity is 85000mL/(gh), and the raw material gas directly passes through the catalyst bed layer. CH can be obtained by gas chromatography TCD and calculation with internal standard method4,CO2Conversion and products CO and H2The ratio of (a) to (b). The evaluation data shown in all examples are evaluation data after 500 hours of evaluation reaction.
Example 1
First, 1.25g of nickel acetate tetrahydrate and 10g of polyvinylpyrrolidone are dissolved in a propanol solution, the volume ratio of alcohol to water being 1: 1. stirring until the mixture is dissolved, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the volume of an propanol solution is 1500mL, the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 16 h. Filtering and washing to obtain NiO nano particles.
Carrying out ultrasonic treatment on the NiO nano-particles for 60min, uniformly dispersing the NiO nano-particles in the solution, sequentially adding ethanol and deionized water into the solution,ammonia, and cetyltrimethylammonium bromide (CTAB); the volumes of the mixed solution of ethanol, deionized water and ammonia water are respectively 250mL, 250mL and 10 mL; the addition amount of hexadecyl trimethyl ammonium bromide is 7.29 g; stirring was continued for 3h at room temperature to disperse the NiO nanoparticles uniformly in the solution. Then, ethyl orthosilicate was slowly added thereto in an amount of 3.12 g. Then reacting for 24 hours at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting for 6 hours at 700 ℃ to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of the AlOOH is 250 mL; then washing with absolute ethyl alcohol, and drying in the air to finish the first alumina sol coating; repeating the above operation 10 times to obtain NiO @ SiO2@AlOOH。
Then continuously adding cobalt nitrate hexahydrate and NH4F is dissolved in deionized water to prepare solution, and NiO @ SiO is added2Uniformly dispersing the @ AlOOH in the solution, cobalt nitrate hexahydrate and NH4F were added 2.43g and 0.46g, respectively. The volume of the deionized water is 200 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 100 ℃, and the reaction time is 12 h. And centrifugally washing, drying and roasting the product at 400 ℃ for 4 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
The average particle diameter of the Ni particles was found to be 13.6nm by XRD, TEM and the like. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion was 78.56%, CH4Conversion 81.73%, H2The ratio of/CO was 0.80.
Example 2
Firstly, 1.25g of nickel acetate tetrahydrate and 5g of polyvinylpyrrolidone are dissolved in a methanol solution, the volume ratio of alcohol to water being 1: 0.3. stirring until the solution is dissolved, transferring the solution into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the volume of the methanol solution is 2000mL, the hydrothermal reaction temperature is 100 ℃, and the hydrothermal reaction time is 8 h. Filtering and washing to obtain NiO nano particles.
The NiO nano-particles are subjected to ultrasonic treatment for 60min to be uniformDispersing in the solution, and sequentially adding ethanol, deionized water, ammonia water, and Cetyl Trimethyl Ammonium Bromide (CTAB); the volumes of the mixed solution of the ethanol, the deionized water and the ammonia water are respectively 750mL, 750mL and 15 mL; the addition amount of hexadecyl trimethyl ammonium bromide is 3.65 g; stirring was continued for 3h at room temperature to disperse the NiO nanoparticles uniformly in the solution. Then, ethyl orthosilicate was slowly added thereto in an amount of 2.60 g. Then reacting for 12h at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting for 6h at 500 ℃ to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of AlOOH is 100 mL; then washing with absolute ethyl alcohol, and drying in the air to finish the first alumina sol coating; repeating the above operation for 5 times to obtain NiO @ SiO2@AlOOH。
Then continuously adding cobalt nitrate and NH4F is dissolved in deionized water to prepare a solution, and NiO @ SiO is added2@ AlOOH is uniformly dispersed in solution, cobalt nitrate hexahydrate and NH4F were added to 1.46g and 0.28g, respectively. The volume of the deionized water is 150 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 150 ℃, and the reaction time is 12 h. And centrifugally washing, drying and roasting the product at 400 ℃ for 8 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
The average particle diameter of the Ni particles was found to be 12.1nm by XRD, TEM and the like. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion 80.12%, CH4Conversion 84.37%, H2The ratio of/CO was 0.81.
Example 3
Firstly, 1.25g of nickel acetate tetrahydrate and 20g of polyvinylpyrrolidone are dissolved in an ethanol solution, wherein the volume ratio of alcohol to water is 1: 0.5. stirring until the mixture is dissolved, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the volume of the ethanol solution is 500mL, the hydrothermal reaction temperature is 140 ℃, and the hydrothermal reaction time is 8 h. Filtering and washing to obtain NiO nano particles.
Carrying out ultrasonic treatment on the NiO nano-particles for 60min, uniformly dispersing the NiO nano-particles in a solution, and sequentially adding ethanol, deionized water, ammonia water and Cetyl Trimethyl Ammonium Bromide (CTAB); the volumes of the mixed solution of the ethanol, the deionized water and the ammonia water are respectively 250mL, 250mL and 20 mL; the addition amount of hexadecyl trimethyl ammonium bromide is 9.11 g; stirring is continued for 3h at room temperature to uniformly disperse the NiO nano particles in the solution. Then, ethyl orthosilicate was slowly added thereto in an amount of 2.08 g. Then reacting for 24 hours at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting for 6 hours at 500 ℃ to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of AlOOH is 100 mL; then washing with absolute ethyl alcohol, and drying in the air to finish the first alumina sol coating; repeating the above operation 10 times to obtain NiO @ SiO2@AlOOH。
Then continuously adding cobalt nitrate and NH4F is dissolved in deionized water to prepare solution, and NiO @ SiO is added2Uniformly dispersing the @ AlOOH in the solution, cobalt nitrate hexahydrate and NH4F were added to the flask 1.46g and 0.28g, respectively. The volume of the deionized water is 250 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 100 ℃, and the reaction time is 48 h. And centrifugally washing, drying and roasting the product at 700 ℃ for 8 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
As a result of characterization by XRD, TEM, etc., it was found that the Ni particles were small in size and had an average particle diameter of 7.4 nm. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion was 90.36%, CH4Conversion 94.51%, H2the/CO is 0.89, and the catalyst has no inactivation within 1000h of evaluation and very good catalytic performance.
Example 4
Firstly, 1.25g of nickel acetate tetrahydrate and 40g of polyvinylpyrrolidone are dissolved in an ethylene glycol solution, wherein the volume ratio of alcohol to water is 1: 0.1. stirring until the solution is dissolved, transferring the solution into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the volume of the ethanol solution is 250mL, the hydrothermal reaction temperature is 180 ℃, and the hydrothermal reaction time is 6 h. Filtering and washing to obtain NiO nano particles.
After the NiO nano-particles are subjected to ultrasonic treatment for 60min, uniformly dispersing the NiO nano-particles in the solution, and sequentially adding ethanol, deionized water, ammonia water and Cetyl Trimethyl Ammonium Bromide (CTAB); the volumes of the mixed solution of the ethanol, the deionized water and the ammonia water are respectively 125mL, 125mL and 20 mL; the adding amount of hexadecyl trimethyl ammonium bromide is 18.22 g; stirring was continued for 3h at room temperature to disperse the NiO nanoparticles uniformly in the solution. Ethyl orthosilicate, in an amount of 0.52g, was then slowly added thereto. Then reacting for 36h at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting at 400 ℃ for 6h to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of AlOOH is 50 mL; then washing with absolute ethyl alcohol, and drying in the air to finish the first alumina sol coating; repeating the above operation for 20 times to obtain NiO @ SiO2@AlOOH。
Then continuously adding cobalt nitrate and NH4F is dissolved in deionized water to prepare solution, and NiO @ SiO is added2Uniformly dispersing the @ AlOOH in the solution, cobalt nitrate hexahydrate and NH4F were added in an amount of 0.97g and 0.19g, respectively. The volume of the deionized water is 300 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 80 ℃, and the reaction time is 60 h. And centrifugally washing, drying and roasting the product at 800 ℃ for 12 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
The average particle diameter of the Ni particles was found to be 15.4nm by XRD, TEM and the like. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion 75.12%, CH4Conversion was 78.51%, H2the/CO was 0.80.
Example 5
Firstly, 1.25g of nickel acetate tetrahydrate and 20g of polyvinylpyrrolidone are dissolved in an ethanol solution, and the volume ratio of alcohol to water is 1: 0.7. stirring until the mixture is dissolved, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the proportion of an ethanol solution is 500mL, the hydrothermal reaction temperature is 120 ℃, and the hydrothermal reaction time is 8 h. Filtering and washing to obtain NiO nano particles.
Carrying out ultrasonic treatment on NiO nano particles for 60min, uniformly dispersing the NiO nano particles in the solution, and sequentially adding ethanol, deionized water, ammonia water and Cetyl Trimethyl Ammonium Bromide (CTAB), wherein the volumes of the mixed solution of the ethanol, the deionized water and the ammonia water are 500mL, 500mL and 40mL respectively; the addition amount of hexadecyl trimethyl ammonium bromide is 12.75 g; stirring is continued for 3h at room temperature to uniformly disperse the NiO nano particles in the solution. Ethyl orthosilicate was then added slowly in an amount of 4.16 g. Then reacting for 24h at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting at 500 ℃ for 6h to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of AlOOH is 100 mL; then washing with absolute ethyl alcohol, and drying in the air to finish the first alumina sol coating; repeating the above operation for 2 times to obtain NiO @ SiO2@AlOOH。
Then continuously adding cobalt nitrate and NH4F is dissolved in deionized water to prepare a solution, and NiO @ SiO is added2@ AlOOH is uniformly dispersed in solution, cobalt nitrate hexahydrate and NH4F was added in an amount of 2.43g and 0.46g, respectively. The volume of the deionized water is 250 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 120 ℃, and the reaction time is 48 h. And centrifugally washing, drying and roasting the product at 600 ℃ for 8 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
The average particle diameter of the Ni particles was found to be 9.7nm by XRD, TEM and the like. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion was 82.11%, CH4Conversion 85.86%, H2the/CO was 0.82.
Example 6
Firstly, 1.25g of nickel acetate tetrahydrate and 20g of polyvinylpyrrolidone are dissolved in an ethanol solution, and the volume ratio of alcohol to water is 1: 0.9. stirring until the mixture is dissolved, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the proportion of ethanol solution is 1000mL, the hydrothermal reaction temperature is 160 ℃, and the hydrothermal reaction time is 8 h. Filtering and washing to obtain NiO nano particles.
Carrying out ultrasonic treatment on NiO nano particles for 60min, uniformly dispersing the NiO nano particles in the solution, and sequentially adding ethanol, deionized water, ammonia water and Cetyl Trimethyl Ammonium Bromide (CTAB), wherein the volumes of the mixed solution of the ethanol, the deionized water and the ammonia water are 250mL, 250mL and 30mL respectively; the adding amount of hexadecyl trimethyl ammonium bromide is 16.40 g; stirring was continued for 3h at room temperature to disperse the NiO nanoparticles uniformly in the solution. Then, ethyl orthosilicate was slowly added thereto in an amount of 1.04 g. Then reacting for 24h at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting at 600 ℃ for 6h to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of AlOOH is 100 mL; then washing with absolute ethyl alcohol, and drying in the air to finish the first alumina sol coating; repeating the above operation for 2 times to obtain NiO @ SiO2@AlOOH。
Then continuously adding cobalt nitrate and NH4F is dissolved in deionized water to prepare solution, and NiO @ SiO is added2@ AlOOH is uniformly dispersed in solution, cobalt nitrate hexahydrate and NH4F were added to 1.46g and 0.28g, respectively. The volume of the deionized water is 100 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 100 ℃, and the reaction time is 48 h. And centrifugally washing, drying and roasting the product at 700 ℃ for 6 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
The average particle diameter of the Ni particles was found to be 8.3nm by XRD, TEM and the like. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion was 84.24%, CH4Conversion was 86.68, H2the/CO was 0.82.
Example 7
Firstly, 1.25g of nickel acetate tetrahydrate and 20g of polyvinylpyrrolidone are dissolved in an ethanol solution, and the volume ratio of alcohol to water is 1: 0.5. stirring until the mixture is dissolved, transferring the mixture into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, wherein the proportion of an ethanol solution is 500mL, the hydrothermal reaction temperature is 140 ℃, and the hydrothermal reaction time is 8 h. Filtering and washing to obtain NiO nano particles.
Carrying out ultrasonic treatment on NiO nano particles for 60min, uniformly dispersing the NiO nano particles in the solution, and sequentially adding ethanol, deionized water, ammonia water and Cetyl Trimethyl Ammonium Bromide (CTAB), wherein the volumes of the ethanol, deionized water and ammonia water mixed solution are 250mL, 250mL and 35mL respectively; the addition amount of hexadecyl trimethyl ammonium bromide is 9.11 g; stirring was continued for 3h at room temperature to disperse the NiO nanoparticles uniformly in the solution. Then, ethyl orthosilicate was slowly added thereto in an amount of 2.08 g. Then reacting for 24h at room temperature with vigorous stirring, washing the obtained product with ethanol, drying in an oven, and roasting at 700 ℃ for 6h to finally obtain NiO @ SiO2。
NiO@SiO2Dispersing in AlOOH sol and violently stirring in a beaker for 1h, wherein the volume of AlOOH is 100 mL; then washing with absolute ethyl alcohol, and drying in the air to finish the first alumina sol coating; repeating the above operation for 10 times to obtain NiO @ SiO2@AlOOH。。
Then continuously adding cobalt nitrate and NH4F is dissolved in deionized water to prepare a solution, and NiO @ SiO is added2Uniformly dispersing the @ AlOOH in the solution, cobalt nitrate hexahydrate and NH4F were added to 4.85g and 0.93g, respectively. The volume of the deionized water is 250 mL; the solution is subjected to hydrothermal reaction in an oven. The reaction temperature is 100 ℃, and the reaction time is 48 h. And centrifugally washing, drying and roasting the product at 700 ℃ for 8 hours to obtain the multistage core-shell structure catalyst. The reduction temperature in the reactor was 700 ℃ and the reduction time was 2 h.
The average particle diameter of the Ni particles was found to be 7.9nm by XRD, TEM and the like. Then the obtained product is loaded into a methane reforming evaluation device, and the evaluation result shows that the obtained product has CO2Conversion was 86.51%, CH4Conversion was 88.97, H2The ratio/CO was 0.84.
Comparative example 1
Mixing nickel nitrate, cobalt nitrate and aluminum nitrate according to the proportion of Ni: co: the molar ratio of Al is 1: 1: 1 in 50mL of deionized water, and then impregnating the solution into commercial SiO by an equal volume impregnation method2On a carrier, SiO2The molar ratio of Ni to Ni is 1: 1. the operation can load three elements of Ni, Co and Al on SiO uniformly2On a carrier. Then roasting the mixture for 4 hours at 700 ℃ in a muffle furnace under static air to obtain NiO and Co3O4And Al2O3Loaded on SiO2A supported catalyst.
As a result of characterization by XRD, TEM, etc., it was found that the Ni particles were very non-uniform in size and that agglomeration phenomenon occurred, and the average particle size was 25 nm. Then the catalyst is loaded into a methane reforming evaluation device, and the evaluation result shows that the catalyst has CO2Conversion was only 50.48%, CH4Conversion was 55.89%, H2the/CO is 0.73, and within 50h of evaluation, the activity is continuously reduced, and finally the reaction tube is seriously blocked due to carbon deposition, which indicates that the catalytic performance and the stability are poor.
Claims (10)
1. Ni @ SiO2@Co-Al2O3The preparation method of the multistage core-shell catalyst is characterized by comprising the following steps:
step 1): dissolving a nickel source and polyvinylpyrrolidone in an alcohol solution, stirring until the nickel source and the polyvinylpyrrolidone are dissolved, transferring the solution into a hydrothermal kettle with a polytetrafluoroethylene lining for hydrothermal reaction, filtering after the hydrothermal reaction is finished, washing and drying to obtain NiO nano-particles;
step 2): preparing a mixed solution of ethanol, deionized water, ammonia water and hexadecyl trimethyl ammonium bromide, then adding the NiO nano particles obtained in the step 1) into the mixed solution, performing ultrasonic dispersion for 10-60min, and continuously stirring at room temperature for 0.5-3h to uniformly disperse the NiO nano particles in the solution; slowly adding tetraethoxysilane into the NiO solution under vigorous stirring, reacting at room temperature, washing the obtained product with ethanol, drying and roasting to obtain NiO @ SiO2;
And step 3): subjecting the product of step 2)Obtaining NiO @ SiO2Dispersing in alumina sol, stirring vigorously, filtering, washing with anhydrous alcohol, drying at room temperature to obtain NiO @ SiO2@ AlOOH; the obtained NiO @ SiO2The @ AlOOH is dispersed in the alumina sol again, and the operation is repeated for a plurality of times as required to obtain NiO @ SiO with different alumina sol wrapping thicknesses2@AlOOH;
And step 4): mixing a cobalt source with NH4F is dissolved in deionized water to prepare a solution, and the NiO @ SiO obtained in the step 3) is added2Adding @ AlOOH into the solution, transferring the obtained solution into a hydrothermal kettle with a polytetrafluoroethylene lining, and reacting in an oven; then centrifugally washing the obtained product to be neutral, and drying the product in an oven to obtain NiO @ SiO2@CoAl-LDH;
Step 5): NiO @ SiO obtained in the step 4)2Baking @ CoAl-LDH in muffle furnace to obtain oxide catalyst, and then passing through H in reactor2After gas reduction, Ni @ SiO is prepared2@Co-Al2O3A multistage core-shell catalyst.
2. The Ni @ SiO of claim 12@Co-Al2O3The preparation method of the multistage core-shell catalyst is characterized in that a nickel source in the step 1) is nickel acetate; the alcohol solution is at least one aqueous solution of methanol, ethanol, propanol and glycol, and the volume ratio of the alcohol to the water is 1 (0.1-1); the ratio of nickel acetate to polyvinylpyrrolidone was 1 mmol: (1-8 g); the ratio of nickel to alcoholic solution is 1 mmol: (50-400) mL; the molecular weight of polyvinylpyrrolidone is 54,000.
3. The Ni @ SiO of claim 12@Co-Al2O3The preparation method of the multistage core-shell catalyst is characterized in that the temperature of hydrothermal reaction in the step 1) is 100-180 ℃, and the time is 6-16 h.
4. The Ni @ SiO of claim 12@Co-Al2O3Preparation of multistage core-shell catalystThe preparation method is characterized in that the ratio of nickel to the sum of the volumes of ethanol and deionized water in the step 2) is 1 mmol: (50-300) mL; the volume ratio of ethanol, deionized water and ammonia water in the mixed solution is 50: 50: (1-8); the molar ratio of hexadecyl trimethyl ammonium bromide to Ni is (1-10): 1; the usage amount of the tetraethoxysilane is as follows according to the molar ratio of Si to Ni (0.5-4): 1 is the standard.
5. The Ni @ SiO of claim 12@Co-Al2O3The preparation method of the multistage core-shell catalyst is characterized in that the reaction time in the step 2) is 12-36 hours, and the roasting temperature is 400-700 ℃.
6. The Ni @ SiO of claim 12@Co-Al2O3The preparation method of the multistage core-shell catalyst is characterized in that the aluminum sol in the step 3) is AlOOH, and the repetition times are 2-20 times.
7. The Ni @ SiO of claim 12@Co-Al2O3The preparation method of the multistage core-shell catalyst is characterized in that the time of vigorous stirring in the step 3) is 1 h; the drying time was 1 h.
8. The Ni @ SiO of claim 12@Co-Al2O3The preparation method of the multistage core-shell catalyst is characterized in that the cobalt source in the step 4) is cobalt nitrate.
9. The Ni @ SiO of claim 12@Co-Al2O3The preparation method of the multistage core-shell catalyst is characterized in that the reaction temperature in the step 4) is 80-150 ℃ and the reaction time is 12-60 hours.
10. The Ni @ SiO of claim 12@Co-Al2O3The preparation method of the multistage core-shell catalyst is characterized in that the roasting temperature in the step 5) is 400-800 ℃, and the roasting time is 4-12 hours.
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