CN117225438A - Nickel-based catalyst and preparation method and application thereof - Google Patents
Nickel-based catalyst and preparation method and application thereof Download PDFInfo
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- CN117225438A CN117225438A CN202310802938.4A CN202310802938A CN117225438A CN 117225438 A CN117225438 A CN 117225438A CN 202310802938 A CN202310802938 A CN 202310802938A CN 117225438 A CN117225438 A CN 117225438A
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- silicon carbide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- YLZGECKKLOSBPL-UHFFFAOYSA-N indium nickel Chemical compound [Ni].[In] YLZGECKKLOSBPL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052738 indium Inorganic materials 0.000 claims abstract description 19
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims description 23
- 238000006057 reforming reaction Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 14
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001833 catalytic reforming Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 4
- 150000002471 indium Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003993 interaction Effects 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical compound O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002105 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
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
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- Catalysts (AREA)
Abstract
The invention discloses a nickel-based catalyst which is a silicon carbide-supported nickel-indium composite oxide, wherein a silicon carbide carrier is beta phase. The invention also discloses a preparation method and application of the catalyst. Indium promoter in the catalyst of the invention helps CO 2 Adsorption dissociation of (2) to improve the reaction efficiency; the addition of the indium auxiliary agent can enhance the interaction between the metal and the carrier, and plays roles in stabilizing nickel particles, preventing sintering, resisting carbon deposition and prolonging the service life of the catalyst, so that the prepared nickel-based catalyst has higher stability and no obvious carbon deposition after being used for 100 hours.
Description
Technical Field
The invention relates to the technical field of catalyst preparation for preparing synthesis gas by reforming methane and carbon dioxide, in particular to a nickel-based catalyst and a preparation method and application thereof.
Background
The energy and environment are the basis of the development of human economy and society and the forward driving force, and the adjustment and transformation of the energy consumption structure are the important strategic guidelines of the global energy and environment industry. Methane carbon dioxide catalytic reforming (DRM) technology can effectively convert two greenhouse gases CH 4 And CO 2 Conversion to important industrial raw material synthesis gas-H 2 And CO, the produced synthesis gas is further prepared into various liquid fuels and chemicals with high added value through Fischer-Tropsch synthesis, so that the DRM reaction can meet the energy consumption requirement and relieve the greenhouse effect, and takes an important energy strategic position in the economic and social development.
Literature reports of DRM catalysts began in 1928 and Fisher and Trosch et al reported that the transition metals Ni, co, fe had CH 4 Reforming activity. By the late 20 th century, DRM catalyst systems were established initially and can be generally divided into noble metal catalysts such as Ru, rh, pd, pt and non-noble metal catalysts such as Ni, co, fe, mo. Noble metal-based catalysts have high activity, but commercial applications are limited by high costs. In contrast, the non-noble metal-based catalyst represented by Ni has the advantages of catalytic performance, price and reserve, and has good industrial application prospect. Abdullah et al reviewed the progress of the study of Ni-based catalysts in DRM reactions, and authors considered the anti-carbon performance as a key indicator for evaluating the structure and performance of a Ni-based catalyst. The metal-support interaction force directly affects the anti-carbon properties of the catalyst. Therefore, the choice of support, promoter and reaction conditions is critical to the construction of the Ni-based catalyst.
Disclosure of Invention
Aiming at the defects existing in the prior art, the first technical problem to be solved by the invention is to provide a novel nickel-based catalyst with strong carbon deposition resistance, which is used for the reaction of preparing synthesis gas by reforming methane and carbon dioxide, can meet the requirement of the service life of the catalyst, and has the advantages of 800 ℃, normal pressure and space velocity of 36 L.h -1 ·g -1 Can be kept stable after 100 hours of use without obvious problemsCarbon deposition phenomenon.
The second technical problem to be solved by the invention is to provide a preparation method of the catalyst.
In order to solve the first technical problem, the nickel-based catalyst provided by the invention is a silicon carbide-supported nickel-indium composite oxide, and the silicon carbide carrier is beta phase.
In order to solve the second technical problem, the catalyst of the invention is prepared by adopting the following technical scheme:
1) The nickel salt and the indium salt are dissolved in an organic solvent to prepare a solution.
2) And (2) uniformly immersing the beta-phase silicon carbide carrier into the solution prepared in the step (1) for a plurality of times under the condition of full rotation in a rotary evaporator.
3) And after the impregnation is completed, drying the mixture in an oven, and then roasting the mixture in a muffle furnace to obtain the nickel-based catalyst, namely the silicon carbide-supported nickel-indium composite oxide catalyst.
Preferably, the nickel salt in the step 1) is nickel nitrate and its hydrate; the indium salt is nitrate of indium and hydrate thereof.
Preferably, the solvent in the step 1) is absolute ethanol.
Preferably, the mass ratio of nickel to indium in the step 1) is 10-15:1.
Preferably, the number of times of impregnation in the step 2) is 2 to 4.
Preferably, the mass ratio of the beta-phase silicon carbide to the nickel in the step 2) is 12-18:1.
Preferably, the muffle furnace roasting temperature in the step 3) is 700-800 ℃, and the programmed heating rate is 2-3 ℃/min.
The invention also provides application of the nickel-based catalyst in methane carbon dioxide reforming reaction, and the application process is as follows:
loading the catalyst into a reaction tube, and sequentially carrying out reduction and catalytic reforming reaction on a fixed bed reactor, wherein the reduction conditions are as follows:
1) And heating at a certain rate in an inert atmosphere.
2) Hydrogen is introduced for reduction.
Preferably, nitrogen is introduced to provide an inert atmosphere when the temperature is raised in the step 1).
Preferably, the temperature rising rate of the step 1) is 80-120 ℃/h.
Preferably, the reduction temperature of the step 2) is 550-700 ℃.
Preferably, the hydrogen flow rate in the step 2) is 20-40 ml/min.
The catalytic reforming reaction conditions are: 1) After the reduction is finished, the temperature is increased to 800 ℃ at a certain rate, 2) the inert atmosphere is gradually switched into CH with the total flow of 40 to 120ml/min at 800 DEG C 4 、CO 2 And a mixture gas of inert atmosphere provided gas is subjected to reforming reaction.
Preferably, the gas used in the heating in the step 1) is nitrogen, and the heating rate is 80-120 ℃/h.
Preferably, the reforming reaction condition of the step 2) is mixed gas CH 4 :CO 2 Gas to provide inert atmosphere = 1:1:2, atmospheric pressure.
The results show that at 800 ℃, normal pressure and space velocity of 36 L.h -1 ·g -1 Under the condition of CH 4 The conversion rate is more than 50 percent, CO 2 The conversion rate is more than 70%, no obvious carbon deposit exists after the catalyst is used for 100 hours, and the catalyst is still stable (CH after the reaction for 100 hours 4 Conversion was 67%, CO 2 Conversion was 72%).
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The nickel-indium/silicon carbide catalyst has higher stability, and the catalyst has no obvious carbon deposition after being used for 100 hours.
(2) The indium assistant of the invention is helpful for CO 2 And the adsorption and dissociation of the catalyst can improve the reaction efficiency.
(3) The addition of the indium auxiliary agent can enhance the interaction between metal and carrier, so that the addition of the indium auxiliary agent plays roles in stabilizing nickel particles, preventing sintering, resisting carbon deposition and prolonging the service life of the catalyst to a certain extent.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the nickel-indium/silicon carbide catalyst synthesized in example 1.
FIG. 2 is a high resolution transmission electron microscope (HR-TEM) photograph of the nickel-indium/silicon carbide catalyst synthesized in example 1.
FIG. 3 is a HAADF-STEM and EDS-Mapping graph of the nickel-indium/silicon carbide catalyst synthesized in example 1.
FIG. 4 shows hydrogen-temperature programmed reduction (H) of the nickel-indium/silicon carbide catalyst, nickel/silicon carbide catalyst and indium/silicon carbide catalyst synthesized in examples 1, 3 and 4 2 -TPR) profile;
FIG. 5 is the experimental results of the life of the nickel-indium/silicon carbide catalyst of example 5 in catalyzing methane carbon dioxide reforming reactions at 800 ℃.
FIG. 6 is the experimental results of the life of the nickel-indium/silicon carbide catalyst (water as solvent) of example 6 (comparative) at 800℃for the methane carbon dioxide reforming reaction.
FIG. 7 is the experimental results of the life of the nickel/silicon carbide catalyst of example 7 (comparative) at 800℃for the catalytic methane carbon dioxide reforming reaction.
FIG. 8 is the experimental results of the life of the indium/silicon carbide catalyst of example 8 (comparative) at 800℃for the catalytic methane carbon dioxide reforming reaction.
FIG. 9 is the result of thermogravimetric analysis of the nickel-indium/silicon carbide catalyst of example 5 after catalytic methane carbon dioxide reforming reaction at 800 ℃.
Detailed Description
The invention is further illustrated by the accompanying drawings and specific examples. It should be understood that the following examples are only for illustrating the technical scheme and effect of the present invention, and are not intended to limit the scope of the present invention.
Examples 1, 2, 3, and 4 are examples of the preparation of nickel-indium/silicon carbide catalyst, comparative catalyst nickel-indium/silicon carbide catalyst (water as solvent), comparative catalyst nickel/silicon carbide catalyst, and comparative catalyst indium/silicon carbide catalyst, respectively;
example 5 is an example of examining the life of the catalyst prepared in example 1 for methane carbon dioxide reforming reactions at 800 ℃;
examples 6, 7 and 8 (comparative examples) are examples for examining the service life of the catalysts prepared in examples 2, 3 and 4 for catalyzing methane carbon dioxide reforming reaction at 800 ℃.
Example 1
A preparation method of a nickel-indium/silicon carbide catalyst comprises the following steps:
0.446g of nickel nitrate hexahydrate and 0.021g of indium nitrate hydrate are dissolved In 2ml of absolute ethyl alcohol to obtain an impregnating solution, 1.40g of beta-phase silicon carbide carrier is uniformly impregnated into the above solution for 3 times under the condition of full rotation In a rotary evaporator, the solution is put into an oven at 80 ℃ to be dried for 12 hours, and then the solution is put into a muffle furnace to be heated to 750 ℃ at the speed of 2 ℃/min for roasting for 5 hours, so that the nickel-indium/silicon carbide catalyst disclosed by the invention is obtained and is marked as Ni-In/SiC.
The X-ray diffraction patterns before and after reduction of the nickel-indium/silicon carbide catalyst prepared in this example are shown in FIG. 1, the high resolution transmission electron microscope pictures are shown in FIG. 2, and the HAADF-STEM and EDS-Mapping pictures are shown in FIG. 3.
As can be seen from fig. 1, the fresh catalyst obtained in example 1 exhibited a characteristic diffraction peak of NiO, which was converted to a characteristic diffraction peak of Ni after reduction. As shown in fig. 2, a 0.24nm interplanar spacing can be observed in region 1 (right square block region of fig. 2), which is attributed to the NiO (111) crystal plane; region 2 (left box region of fig. 2) can observe a interplanar spacing of 0.26nm, ascribed to the SiC (111) crystal plane, while its diffraction peak is not observed in the XRD pattern because of the small content of indium. As shown in fig. 3, indium and nickel were successfully bonded together, and nickel particles were stabilized. In the Ni-In/SiC catalyst synthesized according to example 1, which is shown In FIGS. 2 and 3, the active metal Ni forms a semi-embedded structure, enhancing the metal-carrier interaction.
Example 2 (comparative example)
A preparation method of a nickel-indium/silicon carbide catalyst comprises the following steps:
0.446g of nickel nitrate hexahydrate and 0.021g of indium nitrate hydrate are dissolved In 2ml of water to obtain an impregnating solution, 1.40g of beta-phase silicon carbide carrier is uniformly impregnated into the solution for 3 times under the condition of full rotation In a rotary evaporator, the solution is put into an oven at 80 ℃ to be dried for 12 hours, and then the solution is put into a muffle furnace to be heated to 750 ℃ at a speed of 2 ℃/min for roasting for 5 hours, so that the nickel-indium/silicon carbide catalyst is obtained and is marked as Ni-In/SiC (water is taken as a solvent).
Example 3 (comparative example)
A preparation method of a nickel/silicon carbide catalyst comprises the following steps:
0.446g of nickel nitrate hexahydrate is dissolved in 2ml of absolute ethyl alcohol to obtain an impregnating solution, 1.41g of silicon carbide carrier is uniformly impregnated into the above solution for multiple times under the condition of full rotation in a rotary evaporator, the solution is put into an oven at 80 ℃ to be dried for 12 hours, and then the solution is put into a muffle furnace to be heated to 750 ℃ at a speed of 2 ℃/min for roasting for 5 hours, thus obtaining the nickel/silicon carbide catalyst which is marked as Ni/SiC.
Example 4 (comparative example)
A preparation method of an indium/silicon carbide catalyst comprises the following steps:
dissolving 0.021g of hydrated indium nitrate In 2ml of absolute ethyl alcohol to obtain an impregnating solution, uniformly impregnating 1.48g of silicon carbide carrier into the above-mentioned solution for many times under the condition of full rotation In a rotary evaporator, drying for 12h In an oven at 80 ℃, then placing into a muffle furnace, heating to 750 ℃ at a speed of 2 ℃/min, and roasting for 5h to obtain the indium/silicon carbide catalyst, which is marked as In/SiC.
The hydrogen-temperature programmed reduction patterns of the nickel-indium/silicon carbide catalyst, the nickel/silicon carbide catalyst and the indium/silicon carbide catalyst prepared in examples 1, 3 and 4 are shown in fig. 4, and the results show that the introduction of indium improves the reduction temperature and enhances the interaction between metal and a carrier, thereby improving the stability of nickel nano particles and prolonging the service life of the catalyst.
Example 5
0.2g of the Ni-In/SiC catalyst prepared In example 1 was weighed into a reaction tube, and reduction and catalytic reforming reactions were sequentially carried out on a fixed bed reactor. The reduction conditions are as follows: n (N) 2 In the atmosphere, the temperature is raised to 600 ℃ at a speed of 100 ℃/H, and then at the temperature, the flow rate of H is 30mL/min 2 Reducing for 3h in the atmosphere; the reforming reaction conditions are as follows: after the reduction is finished, the mixture is put under inert atmosphereRaising the temperature to 800 ℃ at the speed of 100 ℃/h, and gradually adding N at 800 DEG directly 2 Is switched to a mixed gas (CH) with the total flow rate of 120mL/min 4 :CO 2 :N 2 =1:1:2) and a space velocity of 36l·h -1 ·g -1 And (3) normal pressure. The product (H) 2 、CO、CO 2 、CH 4 ) After passing through the six-way valve, the catalyst was tested by GC-3000 gas chromatography, the detector was TCD, and the catalytic activity and life of the catalyst at 800℃were examined, and the results are shown in FIG. 5.
The experimental results are shown In FIG. 5, which shows that CH can be caused by using the Ni-In/SiC catalyst prepared In the present invention at a reaction temperature of 800 ℃C 4 The conversion rate of CO reaches more than 50 percent 2 The conversion rate of (C) reaches more than 70%, and remains stable within 100h (after 100h of reaction, CH 4 Conversion was 67%, CO 2 The conversion rate was 72%), and it was found from the TG result of the post-reaction catalyst of fig. 9 that the post-reaction catalyst had no significant carbon deposition, i.e., the Ni-In/SiC catalyst had excellent anti-carbon deposition performance. Therefore, the Ni-In/SiC catalyst can realize high stability of methane carbon dioxide reforming reaction.
Example 6 (comparative example)
0.2g of Ni-In/SiC (water as solvent) catalyst prepared In example 2 was weighed into a reaction tube, and reduction and catalytic reforming reactions were sequentially carried out on a fixed bed reactor. The reduction conditions are as follows: n (N) 2 In the atmosphere, the temperature is raised to 600 ℃ at a speed of 100 ℃/H, and then at the temperature, the flow rate of H is 30mL/min 2 Reducing for 3h in the atmosphere; the reforming reaction conditions are as follows: after the reduction is finished, the temperature is increased to 800 ℃ at the speed of 100 ℃/h under the inert atmosphere, and N is gradually added at 800 DEG directly 2 Is switched to a mixed gas (CH) with the total flow rate of 120mL/min 4 :CO 2 :N 2 =1:1:2) and a space velocity of 36l·h -1 ·g -1 And (3) normal pressure. The product (H) 2 、CO、CO 2 、CH 4 ) After passing through the six-way valve, the catalyst was tested by GC-3000 gas chromatography, the detector was TCD, and the catalytic activity and life of the catalyst at 800℃were examined, and the results are shown in FIG. 6.
Experimental results such asFIG. 6 shows the use of the catalyst CH prepared in the present invention at a reaction temperature of 800 ℃C 4 The conversion rate of (2) reaches about 30 percent, and CO 2 The conversion rate of the catalyst reaches more than 50%, the catalyst is stable within 25 hours, but the catalyst is compared with a Ni-In/SiC catalyst with ethanol as a solvent, and the conversion rate and H are compared 2 The CO is reduced.
Example 7 (comparative example)
0.2g of Ni/SiC catalyst is weighed and filled into a reaction tube, and reduction and catalytic reforming reactions are sequentially carried out on a fixed bed reactor. The reduction conditions are as follows: heating to 600 ℃ at a speed of 100 ℃/H, and then heating to the temperature at a flow rate of 30mL/min of H 2 Reducing for 3h in the atmosphere; the reforming reaction conditions are as follows: after the reduction is finished, the temperature is increased to 800 ℃ at the speed of 100 ℃/h, and N is gradually added at 800 DEG directly 2 The mixture gas with the total flow of 120mL/min is switched to carry out reforming reaction, and the airspeed is 36 L.h -1 ·g -1 And (3) normal pressure. The product (H) 2 、CO、CO 2 、CH 4 ) After passing through the six-way valve, the catalyst was tested by GC-3000 gas chromatography, the detector was TCD, and the catalytic activity and life of the catalyst at 800℃were examined, and the results are shown in FIG. 7.
The results are shown in FIG. 7, which shows that the comparative catalyst has lower catalytic activity. It is reflected that the introduction of indium of the present invention enhances the metal-carrier interaction and improves the catalytic activity.
Example 8 (comparative example)
An In/SiC catalyst (0.2 g) was used, and the activity and life of the catalyst were evaluated by performing tests under the same conditions as those In examples 5, 6 and 7. The results are shown in FIG. 8. The results show that the comparative catalyst has no catalytic activity at a reaction temperature of 800 ℃.
Claims (9)
1. A nickel-based catalyst, characterized in that the nickel-based catalyst is a silicon carbide supported nickel-indium composite oxide, and the silicon carbide carrier is beta phase.
2. A method for preparing a nickel-based catalyst, comprising the steps of:
1) Dissolving nickel salt and indium salt in an organic solvent to prepare a solution;
2) Uniformly dipping the beta-phase silicon carbide carrier into the solution prepared in the step 1) for a plurality of times under the condition of full rotation in a rotary evaporator;
3) And after the impregnation is completed, drying the mixture in an oven, and then roasting the mixture in a muffle furnace to obtain the nickel-based catalyst, namely the silicon carbide-supported nickel-indium composite oxide catalyst.
3. The method for preparing a nickel-based catalyst according to claim 2, wherein the nickel salt in the step 1) is a nitrate of nickel and a hydrate thereof; the indium salt is nitrate of indium and hydrate thereof.
4. A method for preparing a nickel-based catalyst according to claim 2 or 3, wherein the solvent in step 1) is absolute ethanol.
5. A method of preparing a nickel-based catalyst according to claim 2 or 3, wherein the mass ratio of nickel to indium in step 1) is 10 to 15:1.
6. A method of preparing a nickel-based catalyst according to claim 2 or 3, wherein the number of impregnations in step 2) is 2 to 4.
7. A method of preparing a nickel-based catalyst according to claim 2 or 3, wherein the ratio of beta-phase silicon carbide to nickel mass in step 2) is 12-18:1.
8. A method for preparing a nickel-based catalyst according to claim 2 or 3, wherein the muffle furnace baking temperature in step 3) is 700-800 ℃ and the programmed heating rate is 2-3 ℃/min. .
9. Use of the nickel-based catalyst according to claim 1 in a methane carbon dioxide reforming reaction, wherein the use is as follows:
loading a catalyst into a reaction tube, and sequentially carrying out reduction and catalytic reforming reactions on a fixed bed reactor;
wherein the reduction conditions are as follows:
1) Heating at a certain rate in an inert atmosphere;
2) Introducing hydrogen for reduction;
the catalytic reforming reaction conditions are:
1) Heating to 800 ℃ at a certain rate after the reduction is finished;
2) Gradually switching the gas providing inert atmosphere into CH with total flow of 40-120 ml/min at 800 DEG C 4 、CO 2 And a mixture gas of inert atmosphere provided gas is subjected to reforming reaction.
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