CN113181940A - Methane reforming nickel-based catalyst and preparation method and application thereof - Google Patents
Methane reforming nickel-based catalyst and preparation method and application thereof Download PDFInfo
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- CN113181940A CN113181940A CN202110402806.3A CN202110402806A CN113181940A CN 113181940 A CN113181940 A CN 113181940A CN 202110402806 A CN202110402806 A CN 202110402806A CN 113181940 A CN113181940 A CN 113181940A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 140
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000002407 reforming Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- -1 transition metal salt Chemical class 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 230000032683 aging Effects 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims description 12
- 150000002815 nickel Chemical class 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910052728 basic metal Inorganic materials 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000006057 reforming reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 10
- 230000008021 deposition Effects 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910001038 basic metal oxide Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention relates to a methane reforming nickel-based catalyst, and a preparation method and application thereof, which are used for improving the activity and stability of the nickel-based catalyst in a methane reforming reaction process. The preparation method comprises the following steps: s1: dissolving a nickel-based active component and an alkaline metal salt in water, and uniformly stirring to obtain a mixed solution; s2: adding a transition metal salt, a carbon source and an active metal complexing agent into the mixed solution; s3: and aging, drying and calcining the mixed solution to obtain the methane reforming nickel-based catalyst. The prepared methane reforming nickel-based catalyst takes the alkaline oxide as a carrier, takes nickel as an active center, is added with the carbide as an active assistant, can be efficiently applied to methane full-component conversion synthesis gas, and has stable performance and high conversion rate.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a methane reforming nickel-based catalyst, and a preparation method and application thereof.
Background
Currently, energy issues make efficient methane and CO realization2The utilization of resources becomes an important and urgent task. There is a necessary trend for methanol to be an important chemical raw material and an ideal substitute for clean energy. Methanol is produced compared with other raw materialsBeing a hydrogen carrier has various advantages. Meanwhile, the methanol is mixed with water to generate high-purity hydrogen as hydrogen energy, so that the hydrogen can be produced and used, and the development of the hydrogen energy is promoted. The importance of methanol is self-evident, and the demand for methanol will therefore become more and more widespread, which opens up the possibility of replacing fossil energy sources, thus promoting the arrival of the "methanol economy" era. However, most of methanol is derived from non-renewable fossil fuels such as natural gas and coal. The main component of natural gas is methane, and the biogas is rich in methane and carbon dioxide and can be used as an ideal substitute of natural gas. At present, a large amount of organic waste can be used for producing biogas. The main components of the biogas are methane and carbon dioxide, wherein the content of the methane is 40-70 percent, and the content of the carbon dioxide is 30-60 percent. Although the main component of the biogas is similar to or different from that of natural gas, methane is a large amount of carbon dioxide. The methane steam reforming can be realized without great change on the prior natural gas steam reforming technology. At present, most of biogas cannot be utilized or the utilization rate is low, so that the resource is greatly wasted. Therefore, the method utilizes the methane to realize the preparation of the methanol from the whole components by the synthesis gas in a proper proportion, thereby providing sustainable energy guarantee for human society and having great significance.
In the reaction of converting the full components of the biogas into the synthesis gas, the development of an efficient and stable catalyst is very important. Heretofore, noble metal (Rh, Ru, Pt and Pd) catalysts have been widely studied and reported as highly efficient catalysts for activating the C-H bond of methane and the C-O bond of carbon dioxide. However, development is difficult and costly due to limited precious metal resources. The nickel-based catalyst has good activity and stability and low cost, and is widely researched, but the high-load nickel-based catalyst is easy to agglomerate at high temperature and has limited catalytic performance; easy carbon deposition and easy sintering at high temperature. Doctor of Zhanghua, in research on catalytic methane-burning carbon dioxide reforming reaction with molybdenum (tungsten) carbide on nickel-based catalyst, Ni/beta-Mo is prepared by coprecipitation method2C, the catalyst and the application thereof in the methane carbon dioxide reforming reaction are researched. The results show that beta-Mo2The addition of C improves the stability of the catalyst, and reduces the content of CSurface carbon deposition was reduced, but the catalytic activity began to decline a few hours from the beginning of the reaction, and finally the conversion of methane and carbon dioxide was only 55% and 69%, respectively.
Therefore, the improvement of the catalytic performance, especially the anti-carbon deposition performance, of the nickel-based catalyst and the improvement of the catalytic activity in the reaction of converting the methane into the synthesis gas by all components have important significance for the industrial application of the nickel-based catalyst.
Disclosure of Invention
The invention aims to solve the problems of limited catalytic performance and easy carbon deposition of a nickel-based catalyst in the reaction of converting full components of methane into synthesis gas, and provides a preparation method of a methane reforming nickel-based catalyst. The invention takes the alkaline metal oxide as a carrier, takes the nickel as an active component, takes the carbide as an active auxiliary agent, and optimizes the loading capacity of the nickel-based active component and the carbide, so that the prepared methane reforming nickel-based catalyst can be efficiently used for catalyzing the methane full-component conversion synthesis gas, and has low cost and high conversion rate.
The invention also aims to provide a methane reforming nickel-based catalyst.
The invention also aims to provide an application of the methane reforming nickel-based catalyst in the full-component conversion of synthesis gas of methane.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a methane reforming nickel-based catalyst comprises the following steps:
s1: dissolving nickel salt and alkaline metal salt, and uniformly stirring to obtain a mixed solution;
s2: adding a carbide precursor, a carbon source and an active metal complexing agent into the mixed solution; the carbide precursor is transition metal salt;
s3: and aging, drying and calcining the mixed solution to obtain the methane reforming nickel-based catalyst.
Reacting and calcining the nickel salt to obtain nickel particles, namely a nickel-based active component; reacting and calcining the alkali metal salt to obtain an alkali oxide carrier; the transition metal salt and the carbon source react and are calcined to obtain carbide.
The prepared methane reforming nickel-based catalyst takes alkaline metal oxide as a carrier, takes nickel as an active component, and is added with carbide as an active auxiliary agent.
In one aspect, the invention uses basic metal oxide as a carrier main body and nickel as an active component. The Lewis base on the carrier increases the alkalinity of the catalyst and can promote CO2The adsorption and dissociation of the catalyst can eliminate carbon deposition in the reaction process, and the alkalinity of the carrier can inhibit the growth of nickel metal particles at high temperature, thereby enhancing the activity, stability and carbon deposition resistance of the catalyst.
On the other hand, the carbide has similar adsorption performance and catalytic performance with the noble metal catalyst, and has excellent anti-carbon deposition performance; after the carbide is added as an active assistant, the catalytic activity of the nickel-based catalyst is further improved.
The invention optimizes from two aspects of alkaline metal oxide carrier and added carbide, combines the anti-carbon deposition capability of the alkaline metal oxide and the carbide with the catalytic performance of the nickel-based catalyst, and adjusts the load capacity of the nickel-based catalyst, so that the obtained methane reforming nickel-based catalyst has low cost, excellent performance, high conversion rate (the methane conversion rate can reach 98 percent at most, and the carbon dioxide conversion rate can reach 78 percent), and has good applicability in the aspect of converting the methane into the synthesis gas; and producing H in the synthesis gas2And CO at a molar ratio of 0.98, close to 1, are effective for oxo production of alcohols.
The loading amounts of the nickel-based active component and the carbide have certain influence on the reaction process of converting the whole components of the biogas into the synthesis gas, for example, the loading amount is too high, so that the distribution is not uniform or the active component is aggregated, so that the catalyst is inactivated; and if the loading amount is too low, the catalytic activity is low.
Therefore, the loading capacity optimization of the nickel-based active component and the carbide is realized by adjusting the molar ratio of the nickel salt to the carbide precursor to the alkaline metal salt, and the catalytic activity of the reaction for converting the methane full components into the synthesis gas can be further improved.
It is understood that the loading refers to the mass fraction of the nickel-based active component and the carbide in the basic oxide support.
Preferably, the total load of the nickel-based active component and the carbide is 4-9%; further preferably, the total loading of the nickel-based active component and the carbide is 8%.
It is to be understood that the mass of the basic metal oxide is calculated from the mass of the added basic metal salt; the mass of the carbide is calculated by mass correspondence of the carbide precursor.
Preferably, the nickel salt in S1 is one or more of nickel nitrate, nickel sulfate, nickel acetate, or nickel chloride.
Preferably, the basic metal salt in S1 is one of nitrates formed by Sr, Mg, Ca, Ba or any combination thereof.
Preferably, the carbide precursor in S2 is one of nitrates formed by Mo, W, Ta, Ti, Zr, Cr, Mn, Fe, or any combination thereof.
Preferably, the carbon source in S2 is one of glucose, sucrose or cyclodextrin or any combination thereof.
Preferably, the active metal complexing agent in S2 is one of citric acid, ethylene glycol or polyethylene glycol, or any combination thereof.
Preferably, the temperature of the mixed solution in S2 is adjusted to 60-80 ℃.
Preferably, the drying temperature in S3 is 120 ℃ and the time is 12 h.
Preferably, the calcining temperature in S3 is 500-700 ℃, and the time is 1-6 h; further preferably, the calcination temperature in S3 is 650 ℃ and the time is 3 h.
Preferably, the temperature increase rate of the calcination in S3 is 5 deg.C/min.
A methane reforming nickel-based catalyst, which is obtained by the preparation method.
The application of the methane reforming nickel-based catalyst in catalyzing the full-component conversion of the methane into the synthesis gas is also within the protection scope of the invention.
Compared with the prior art, the invention has the following remarkable effects:
the invention takes the alkaline metal oxide as a carrier, takes the nickel as an active ingredient, and adds the carbide as an active assistant, so that the obtained nickel particles are small, the dispersion degree is high, the dispersion is uniform, and the defects that the high-load nickel-based catalyst is easy to agglomerate at high temperature and the catalytic performance is limited are overcome. The prepared methane reforming nickel-based catalyst can be efficiently applied to methane full-component conversion synthesis gas, and has stable performance and high conversion rate.
Detailed Description
The invention is illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Examples
The embodiment provides a series of methane reforming nickel-based catalysts, and the preparation method specifically comprises the following steps:
s1: a certain mass of Ni (NO)3)2·6H2O and Mg (NO)3)2·6H2Dissolving O in deionized water, and uniformly stirring in a constant-temperature oil bath to obtain a mixed solution;
s2: adjusting the temperature of the mixed solution to 80 ℃; adding Mo (NO) with a certain mass into the mixed solution3)4·5H2O, and adding a certain mass of glucose and citric acid;
s3: uniformly stirring the mixed solution for 3h, then aging at room temperature for 2h, and drying in a 120 ℃ oven overnight; and then calcining for 3 hours in a muffle furnace air atmosphere at 650 ℃, wherein the temperature rise rate of the calcination is 5 ℃/min, and thus the methane reforming nickel-based catalyst is obtained.
By regulating and controlling the usage molar ratio of the nickel salt, the carbide precursor and the alkali metal salt, a series of products with the total loading of nickel-based active components and carbides of 5, 7 and 8 wt% in the nickel-based catalyst are finally obtained, and the mass of each component is shown in table 1.
Wherein, the mass of the nickel-based active component is obtained by correspondingly calculating the mass of the added nickel salt; the mass of the carbide is obtained by correspondingly calculating the mass of the carbide precursor; the mass of the basic metal oxide is calculated from the mass of the added basic metal salt.
Table 1 quality of each component in the methane reforming nickel-based catalyst prepared in examples 1 to 3
Comparative example
The preparation method of the methane reforming nickel-based catalyst in the comparative examples 1-3 is consistent with that in the examples, a series of products with the total loading amounts of the nickel-based active component and the carbide of 4, 6 and 9 wt% in the nickel-based catalyst are finally obtained by regulating and controlling the usage molar ratio of the nickel salt, the carbide precursor and the alkali metal salt, and the mass of each component is shown in table 2.
Table 2 comparative examples 1 to 3 each component mass of the methane reforming nickel-based catalyst
Performance testing
150mg of the methane reforming nickel-based catalyst prepared in each of the three groups of the examples and the comparative examples is added into the reactor, and the flow rate of methane is 60 mL/min. Before the reaction, the reaction was started after reducing the reaction mixture at 750 ℃ for 1 hour in a 5% hydrogen/nitrogen mixture. The obtained product gas is subjected to on-line detection by adopting gas chromatography.
During the reaction of the full-component conversion synthesis gas of the biogas, the conversion of methane and carbon dioxide is considered. The lower the content, the better the catalytic activity. The gas ratio at atmospheric pressure is CH4/CO21/1 at 850 deg.C,the results of the specific activity tests are shown in tables 3 and 4.
Table 3 results of activity test of the methane reforming nickel-based catalyst in example 3
Table 4 results of activity test of the nickel-based catalyst for methane reforming in comparative example
As can be seen from the data in tables 3 and 4, by optimizing the loading amount, example 3 has the highest activity in catalyzing full-component conversion of biogas into syngas when the total loading amount of nickel-based active component and carbide is 8%. Under the test condition of 850 ℃, the methane conversion rate of the methane reforming nickel-based catalyst prepared by the embodiment 3 of the invention can reach 98 percent at most, and the carbon dioxide conversion rate can reach 78 percent; and producing H in the synthesis gas2And CO at a molar ratio of 0.98, close to 1, are effective for oxo production of alcohols.
The methane reforming nickel-based catalyst prepared by the invention has the advantages of low cost, excellent performance and high conversion rate, and has high activity and stability in the aspect of catalyzing the methane full-component conversion to prepare synthesis gas.
Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (10)
1. The preparation method of the nickel-based catalyst for methane reforming is characterized by comprising the following steps of:
s1: dissolving nickel salt and alkaline metal salt, and uniformly stirring to obtain a mixed solution;
s2: adding a carbide precursor, a carbon source and an active metal complexing agent into the mixed solution; the carbide precursor is transition metal salt;
s3: and aging, drying and calcining the mixed solution to obtain the methane reforming nickel-based catalyst.
2. The preparation method according to claim 1, wherein the nickel salt in S1 is one of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride or any combination thereof.
3. The method according to claim 1, wherein the basic metal salt in S1 is one of nitrates formed from Sr, Mg, Ca, Ba or any combination thereof.
4. The preparation method according to claim 1, wherein the transition metal salt in S2 is one of nitrates formed from Mo, W, Ta, Ti, Zr, Cr, Mn, Fe or any combination thereof.
5. The method according to claim 1, wherein the carbon source in S2 is one of glucose, sucrose and cyclodextrin or any combination thereof.
6. The preparation method of claim 1, wherein the active metal complexing agent in S2 is one of citric acid, ethylene glycol or polyethylene glycol or any combination thereof.
7. A methane reforming nickel-based catalyst is characterized by being prepared by the preparation method of any one of claims 1 to 6.
8. The nickel-based catalyst for methane reforming as claimed in claim 7, wherein the nickel salt is reacted and calcined to obtain nickel particles, i.e. nickel-based active components; reacting and calcining the alkali metal salt to obtain an alkali oxide carrier; and the transition metal salt and a carbon source react and are calcined to obtain carbide.
9. The nickel-based catalyst for methane reforming as claimed in claim 8, wherein the total loading amount of the nickel-based active component and the carbide is 4-9 wt% based on the mass of the basic oxide carrier.
10. Use of the methane reforming nickel-based catalyst according to any one of claims 7 to 9 in full-component conversion of synthesis gas into methane.
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