CN116495701A - Method for preparing synthesis gas by photo-thermal driving methane dry reforming - Google Patents
Method for preparing synthesis gas by photo-thermal driving methane dry reforming Download PDFInfo
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 85
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 83
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002407 reforming Methods 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 88
- 239000000956 alloy Substances 0.000 claims abstract description 72
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 72
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 51
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- 229910002367 SrTiO Inorganic materials 0.000 claims description 49
- 238000005286 illumination Methods 0.000 claims description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 238000006057 reforming reaction Methods 0.000 claims description 9
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 8
- 229910052724 xenon Inorganic materials 0.000 claims description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052753 mercury Inorganic materials 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- -1 LED Chemical compound 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 59
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- 239000002994 raw material Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 150
- 238000001514 detection method Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 12
- 239000003345 natural gas Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000005431 greenhouse gas Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
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- 230000001699 photocatalysis Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a loaded high-entropy alloy in CO 2 The use of dry reforming of a source and a light alkane source as a catalyst in the preparation of synthesis gas. The invention also discloses a corresponding high-efficiency sustainable method for preparing the synthesis gas by photo-thermal driving methane dry reforming, and the specific supported high-entropy alloy catalyst has good photo-thermal conversion efficiency and can realize the preparation of the synthesis gas by DRM technology under mild conditions. The process is not only beneficial to relieving the greenhouse effect, but also improves the energy utilization efficiency, and greatly reduces the production cost and the energy consumption. The method provided by the invention has the raw material conversion rate of over 50 percent and the yield of the synthesis gas of 10mol g ‑1 h ‑1 The catalyst can stably run for more than 100 hours, has the advantages of simple reaction process, short period, low price and easy acquisition of the catalyst, repeated use, wide sources of reactant raw materials and wide industrial application, and has the selectivity of over 0.9 overall and no hydrocarbon or alcohol productsAnd (3) prospect.
Description
Technical Field
The invention belongs to the technical field of synthesis gas preparation by dry reforming of methane, and relates to a loaded high-entropy alloy in CO 2 Application of light alkane source dry reforming as catalyst in synthesis gas preparation and method for preparing synthesis gas by light alkane dry reforming, in particular to loaded high-entropy alloy in CO 2 Application of source and light alkane source in preparing synthetic gas by dry reforming as catalyst and methane driven by light heatA method for preparing synthesis gas by dry reforming.
Background
Natural gas is not only a high-quality clean energy source, but also an important chemical raw material. In the situation of increasingly serious environmental problems, clean and environment-friendly natural gas is attracting attention compared with fossil energy sources such as coal, petroleum and the like. Will be in CH 4 Natural gas, which is the main component, is converted into synthetic gas with a product selectivity close to 1 through a methane Dry Reforming (DRM) technology, and the process not only helps to relieve the greenhouse effect, but also improves the energy utilization efficiency.
However, since the DRM reaction is strongly endothermic, it generally requires a temperature of 700 ℃ or higher to drive the reaction, resulting in huge energy consumption and environmental pollution. In addition, at such high temperatures, side reactions such as coking and reverse water gas reactions are thermodynamically unavoidable, leading to catalyst deactivation and reduced selectivity.
Therefore, considering the cost of industrial production, energy crisis, environmental pollution and other problems, how to develop a new method of DRM technology with more environmental protection, mild reaction conditions and high selectivity has become one of the focus of attention of many prospective researchers in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a loaded high-entropy alloy in CO 2 The application of the light alkane source as a catalyst in the preparation of the synthesis gas by dry reforming and the method for preparing the synthesis gas by dry reforming of the light alkane, in particular to a method for preparing the synthesis gas by dry reforming of photo-thermal driven methane. The method for preparing the synthesis gas by applying the loaded high-entropy alloy to the DRM reaction obtains the method for preparing the synthesis gas by photo-thermal driving methane dry reforming, can realize high-efficiency and high-selectivity preparation of the synthesis gas under the mild condition, has simple steps and mild conditions, is suitable for large-scale production popularization and application, and has good practical prospect.
The invention provides a loaded high-entropy alloy in CO 2 The use of dry reforming of a source and a light alkane source as a catalyst in the preparation of synthesis gas.
Preferably, the metal in the high-entropy alloy comprises four or more of Co, ni, cu, zn, ru, rh, pd and Pt;
the supported carrier comprises a metal oxide carrier and/or a titanate carrier;
the light alkane comprises methane, ethane or propane.
Preferably, the molar ratio of the high-entropy alloy to the carrier is (0.005-0.1): 1, a step of;
the metal oxide support comprises TiO 2 、CeO 2 、CaO、ZnO、Al 2 O 3 MgO and SiO 2 One or more of the following;
the titanate carrier comprises SrTiO 3 、Sr x Ba 1-x TiO 3 (0＜x＜1)、SrBaTiO 3 、CaTiO 3 And SrZrO 3 One or more of the following;
the conditions for the preparation include performing the preparation under energized conditions.
Preferably, the preparation time is 0.1 to 300 hours;
the energizing means comprises illumination and/or heating;
the illumination intensity of the illumination is 10-5000mW/cm 2 。
Preferably, the light source for illumination comprises one or more of natural light, xenon lamp, LED lamp, tungsten lamp and mercury lamp;
the temperature of the illumination is normal temperature;
the heating temperature is 20-700 ℃.
Preferably, the CO 2 The source comprises CO 2 Or contains CO 2 Is a gas of (2);
the light alkane source comprises light alkane or gas containing light alkane;
the CO 2 The source and light alkane source include CO 2 And light alkanes or CO 2 And light alkane;
the molar ratio between metal elements in the high-entropy alloy is 1:1.
the invention provides a method for preparing synthesis gas by dry reforming of light alkane, which comprises the following steps:
under the energized condition, under the action of a supported catalyst loaded with high-entropy alloy, CO 2 The source and light alkane source are subjected to dry reforming reaction of methane to obtain CO and H 2 。
Preferably, the metal in the high-entropy alloy comprises four or more of Co, ni, cu, zn, ru, rh, pd and Pt;
the mol ratio of the high-entropy alloy to the loaded carrier is (0.005-0.1): 1, a step of;
the support comprises a metal oxide support and/or a titanate support.
Preferably, the CO 2 The pressure of the source is 0.1-10 MPa;
the pressure of the light alkane source is 0.1-10 MPa;
the means of energizing include illumination and/or heating.
Preferably, the illumination intensity of the illumination is 10-5000mW/cm 2 ；
The heating temperature is 20-700 ℃;
the preparation time is 0.1-300 h;
the reactor for performing the methane dry reforming reaction comprises one or more of a quartz reactor, a glass reactor, a fixed bed reactor and a mobile phase reactor.
The invention provides a loaded high-entropy alloy in CO 2 The use of dry reforming of a source and a light alkane source as a catalyst in the preparation of synthesis gas. Compared with the prior art, the invention is based on the international thermocatalytic DRM technology and photocatalytic CH 4 Conversion and CO 2 The development trend of reduction considers that taking photo-thermal driving DRM reaction as a research object, developing ideal design theory and preparation method of photo-thermal catalyst, and establishing reasonable and reliable photo-thermal driving DRM reaction is the technical direction of related research.
Based on the above, the invention creatively applies the supported high-entropy alloy as a catalyst to CO 2 Dry reforming of sources and light alkane sourcesDuring the preparation of synthesis gas. The invention also discloses a corresponding high-efficiency sustainable photo-thermal driven methane Dry Reforming (DRM) method for preparing the synthesis gas (CO and H) 2 ) The method uses high-entropy alloy supported by a metal oxide carrier or a titanate carrier as a catalyst, and two greenhouse gases (CH) are generated in a flow reactor under external energization (such as focused sunlight irradiation) 4 And CO 2 Gas) is converted to an equal volume of synthesis gas under mild conditions. The product synthesis gas can be used directly in the manufacture of high value chemicals in the fischer-tropsch synthesis.
The specific supported high-entropy alloy catalyst adopted by the invention has good photo-thermal conversion efficiency, and can realize the preparation of synthetic gas by DRM technology under mild conditions. The process is not only beneficial to relieving the greenhouse effect, but also improves the energy utilization efficiency, and greatly reduces the production cost and the energy consumption. In addition, the method has the advantages of simple reaction process, short period, cheap and easily available catalyst, repeated use and wide sources of reactant raw materials, can especially directly use combustible ice, shale gas and natural gas as raw material gas, and the like, provides a new synthesis path for preparing the synthetic gas by DRM, and has wide industrial application prospect.
The high-entropy alloy catalyst adopted by the invention has good photo-thermal conversion efficiency, can drive DRM technology to prepare synthetic gas under mild conditions, is high-efficiency, high-selectivity and high-stability synthetic gas production, has no hydrocarbon and alcohol products, and can be directly used for producing high-value hydrocarbon and oleochemicals by Fischer-Tropsch synthesis; the catalyst has high stability, can stably run for more than 100 hours, and does not generate catalyst sintering and carbon deposition; in addition, the catalyst can also drive ethane dry reforming and propane dry reforming to prepare synthesis gas. The process is not only beneficial to relieving the greenhouse effect, but also improves the energy utilization efficiency, and greatly reduces the production cost and the energy consumption. In addition, the method provided by the invention has the advantages of simple reaction process, short period, low price and easy availability of catalyst, repeated use, wide sources of reactant raw materials, direct use of combustible ice, shale gas and natural gas as raw material gas and the like, provides a new synthesis path for preparing synthesis gas by DRM reaction, and has wide industrial application prospect.
Experimental results show that the method for preparing the synthetic gas by dry reforming provided by the invention only irradiates with focused sunlight in a mobile phase reactor, and two equal volumes of greenhouse gases (CH 4 And CO 2 Gas) is converted to an equal volume of synthesis gas, CH, at room temperature 4 And CO 2 The conversion of (2) is above 50% overall and the yield of synthesis gas is 10mol g -1 h -1 The selectivity is generally above 0.9, hydrocarbon and alcohol products are not generated, and the catalyst can stably run for more than 100 hours.
Drawings
FIG. 1 is a graph showing the synthesis gas yield rate and selectivity obtained in the dry reforming of methane provided in example 1 of the present invention;
FIG. 2 shows SrTiO of the present invention 3 The re-use performance results of the supported high entropy alloy catalyst.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
The raw materials used in the present invention are not particularly limited in purity, and the present invention is preferably analytically pure or conventional purity in the field of Dry Reforming (DRM) application of methane.
All raw materials of the invention, the brands and abbreviations of which belong to the conventional brands and abbreviations in the field of the related application are clear and definite, and the person skilled in the art can purchase from the market or prepare by the conventional method according to the brands, abbreviations and the corresponding application.
All processes of the present invention, the abbreviations of which are conventional in the art, are each well-defined in the art of their relevant use, and the skilled artisan will be able to understand the conventional process steps thereof based on the abbreviations.
The invention provides a loaded high-entropy alloy in CO 2 The use of dry reforming of a source and a light alkane source as a catalyst in the preparation of synthesis gas.
In the present invention, the metal in the high-entropy alloy preferably includes four or more of Co, ni, cu, zn, ru, rh, pd and Pt, more preferably four, five or six of Co, ni, cu, zn, ru, rh, pd and Pt.
In the present invention, the supported carrier preferably includes a metal oxide carrier and/or a titanate carrier, more preferably a metal oxide carrier or a titanate carrier.
In the present invention, the light alkane preferably includes methane, ethane or propane. Specifically, methane is used.
In the present invention, the molar ratio of the high-entropy alloy to the carrier is preferably (0.005 to 0.1): 1, more preferably (0.05 to 0.09): 1, more preferably (0.06 to 0.08): 1.
in the present invention, the metal oxide support comprises TiO 2 、CeO 2 、CaO、ZnO、Al 2 O 3 MgO and SiO 2 More preferably TiO 2 、CeO 2 、CaO、ZnO、Al 2 O 3 MgO or SiO 2 。
In the present invention, the titanate support preferably comprises SrTiO 3 、Sr x Ba 1-x TiO 3 (0＜x＜1)、SrBaTiO 3 、CaTiO 3 And SrZrO 3 One or more of them, more preferably SrTiO 3 、Sr x Ba 1-x TiO 3 (0＜x＜1)、SrBaTiO 3 、CaTiO 3 Or SrZrO 3 。
In the present invention, the conditions for the preparation preferably include preparation under energized conditions.
In the present invention, the time for the preparation is preferably 0.1 to 300 hours, more preferably 1 to 200 hours, still more preferably 10 to 100 hours.
In the present invention, the means of energizing preferably includes illumination and/or heating, more preferably illumination or heating. In particular, it may be focused solar light.
In the present invention, the illumination intensity of the illumination is preferably 10 to 5000mW/cm 2 More preferably 100 to 4000mW/cm 2 More preferably 1000 to 3000mW/cm 2 。
In the present invention, the light source of illumination preferably includes one or more of natural light, a xenon lamp, an LED lamp, a tungsten lamp, and a mercury lamp, and more preferably is a natural light, a xenon lamp, an LED lamp, a tungsten lamp, or a mercury lamp.
In the present invention, the temperature of the illumination is preferably normal temperature.
In the present invention, the heating temperature is preferably 20 to 700 ℃, more preferably 100 to 500 ℃, and still more preferably 200 to 300 ℃.
In the present invention, the CO 2 The source preferably comprises CO 2 Or contains CO 2 Is a gas of (a) a gas of (b).
In the present invention, the light alkane source preferably includes a light alkane source or a gas containing a light alkane source.
In the present invention, the CO 2 The source and light alkane source preferably comprise CO 2 And light alkane source or CO 2 And a light alkane source.
In the present invention, the molar ratios between the metal elements in the high-entropy alloy are preferably each 1:1.
the invention provides a method for preparing synthesis gas by dry reforming of light alkane, which comprises the following steps:
under the energized condition, under the action of a supported catalyst loaded with high-entropy alloy, CO 2 The source and light alkane source are subjected to dry reforming reaction of methane to obtain CO and H 2 。
In the present invention, the high-entropy alloy is preferably a high-entropy alloy having c—h bond and c=o bond dissociation capability and photothermal conversion capability, and the metals in the high-entropy alloy preferably include four or more of Co, ni, cu, zn, ru, rh, pd and Pt, more preferably four of Co, ni, cu, zn, ru, rh, pd and Pt.
In the present invention, the molar ratio of the high-entropy alloy to the supported carrier is preferably (0.005 to 0.1): 1, more preferably (0.05 to 0.09): 1, more preferably (0.06 to 0.08): 1.
in the present invention, the support preferably includes a metal oxide support and/or a titanate support, more preferably a metal oxide support or a titanate support.
In the present invention, the light alkane preferably includes one or more of methane, ethane, and propane, and more preferably is methane, ethane, or propane. Specifically, methane is used.
In the present invention, the CO 2 The pressure of the source is preferably 0.1 to 10MPa, more preferably 1 to 8MPa, and still more preferably 3 to 6MPa.
In the present invention, the pressure of the light alkane source is preferably 0.1 to 10MPa, more preferably 1 to 8MPa, and still more preferably 3 to 6MPa.
In the present invention, the means of energizing preferably includes illumination and/or heating, more preferably illumination or heating.
In the invention, the illumination intensity of the illumination is 10-5000mW/cm 2 More preferably 100 to 4000mW/cm 2 More preferably 1000 to 3000mW/cm 2 。
In the present invention, the heating temperature is preferably 20 to 700 ℃, more preferably 100 to 500 ℃, and still more preferably 200 to 300 ℃.
In the present invention, the time for the preparation is preferably 0.1 to 300 hours, more preferably 1 to 200 hours, still more preferably 10 to 100 hours.
In the present invention, the reactor for performing the light alkane dry reforming reaction preferably includes one or more of a quartz reactor, a glass reactor, a fixed bed reactor and a mobile phase reactor, more preferably a quartz reactor, a glass reactor, a fixed bed reactor or a mobile phase reactor.
The invention relates to a complete and refined integral preparation process, which better ensures the performance and product composition of the light alkane dry reforming reaction, further improves the high efficiency, high selectivity and high stability of the light alkane dry reforming reaction, and the method for preparing the synthesis gas by photo-thermal driving of the light alkane dry reforming reaction preferably comprises the following steps:
new method for preparing synthesis gas by photo-thermal driven methane Dry Reforming (DRM) method using strontium titanate (SrTiO) 3 ) Supported high entropy alloy as catalyst, two greenhouse gases (CH 4 And CO 2 Gas) is converted to an equal volume of synthesis gas (CO and H) under mild conditions 2 )。
In particular, the feed gas used may be derived from pure CH 4 And CO 2 In the form of a gas, also containing CH 4 And CO 2 In the form of a gas. The term "CH-containing 4 And CO 2 The gas "means that it contains CH 4 And CO 2 Is a gas mixture of (a) and (b). In addition, the feed gas may also be derived directly from combustible ice, shale gas and natural gas.
Specifically, the catalyst carrier SrTiO 3 Commercially available SrTiO which is inexpensive and can be purchased directly 3 SrTiO of a specific structure can also be synthesized according to experimental requirements 3 。
In particular, the catalyst support includes, but is not limited to, srTiO 3 Other commercial oxides can be used instead of SrTiO 3 For example titanate materials (Sr) x Ba 1-x TiO 3 、SrBaTiO 3 、CaTiO 3 And SrZrO 3 Etc.) and oxide material (TiO 2 、CeO 2 、ZnO、Al 2 O 3 、MgO、SiO 2 Etc.).
Specifically, the components of the high-entropy alloy include, but are not limited to Co, ni, cu, zn, ru, rh, pd, pt and the like.
Specifically, the high-entropy alloy and SrTiO loaded in the catalyst 3 The molar ratio of (2) is 0.005-0.1:1.
Specifically, the illumination intensity of the illumination condition is 10-5000mW/cm 2 。
In particular, the light source for the lighting conditions is one or more selected from natural light, xenon lamp, LED lamp, tungsten lamp and mercury lamp.
Specifically, the reaction temperature is 20-600 ℃ and the reaction operation time is 0-200h.
Specifically, the reactor is a quartz reactor, a glass reactor, a fixed bed reactor or a mobile phase reactor.
Specifically, CH in the reactor 4 Gas and CO 2 The pressure of the gas is 0.1MPa to 10Mpa.
Further, the method comprises the steps of,
the invention provides a method for preparing synthesis gas by using a frontlight thermal drive DRM technology, which utilizes SrTiO 3 The supported high entropy alloy was used as a catalyst in a flow reactor under focused solar irradiation with two equal volumes of greenhouse gases (CH 4 And CO 2 Gas) is converted to an equal volume of synthesis gas at room temperature.
In a preferred embodiment, the feed gas used may be derived from pure CH 4 And CO 2 In the form of a gas, also containing CH 4 And CO 2 In the form of a gas. The term "CH-containing 4 And CO 2 The gas "means that it contains CH 4 And CO 2 Is a gas mixture of (a) and (b). In addition, the feed gas may also be derived directly from combustible ice, shale gas and natural gas. Preferably containing CH therein 4 And CO 2 The volume content of the gas is greater than 10% of the gas.
In a preferred embodiment, the feed gas CH 4 And CO 2 The flow rate of the gas is 5-60mL/min respectively. Preferably wherein CH 4 And CO 2 The gas flow rates were 10mLmin respectively -1 。
In a preferred embodiment, the catalyst support SrTiO 3 Commercially available SrTiO which is inexpensive and can be purchased directly 3 SrTiO of a specific structure can also be synthesized according to experimental requirements 3 。
In a preferred embodiment, the catalyst support includes, but is not limited to, srTiO 3 Other commercial oxides can be used instead of SrTiO 3 For example titanate materials (Sr) x Ba 1-x TiO 3 、SrBaTiO 3 、CaTiO 3 And SrZrO 3 Etc.) and oxide material (TiO 2 、CeO 2 、ZnO、Al 2 O 3 、MgO、SiO 2 Etc.). Preferably commercially available SrTiO 3 As a carrier.
The components of the high-entropy alloy include, but are not limited to Co, ni, cu, zn, ru, rh, pd, pt and the like. The preferred component is a high entropy alloy of CoNiRuRhPd.
In a preferred embodiment, the high entropy alloy and SrTiO supported in the catalyst 3 The molar ratio of (2) is 0.005-0.1:1. Preferably high entropy alloy and SrTiO supported in catalyst 3 The molar ratio of (2) is 0.05:1.
In a preferred embodiment, the illumination conditions have an illumination intensity of 10-5000mW/cm 2 . Preferably the illumination intensity is 4000mW/cm 2 。
In a preferred embodiment, the light source for the illumination conditions is one or more selected from natural light, xenon lamp, LED lamp, tungsten lamp and mercury lamp.
In a preferred embodiment, the reaction temperature is in the range of 20 to 600 ℃. Preferably, the reaction temperature is 25 ℃.
The continuous operation time of the reaction is 0-200h. Preferably the reaction is run continuously for 100 hours.
In preferred embodiments, the reactor is a quartz reactor, a glass reactor, a fixed bed reactor, or a mobile phase reactor. Preferably the reactor is a mobile phase reactor.
In a preferred embodiment, CH in the reactor 4 Gas and CO 2 The gas and the pressure are 0.1MPa to 10MPa. Preferably CH in said device 4 Gas and CO 2 The pressure of the gas was 0.1MPa.
The method of the invention can produce the synthesis gas with high efficiency, high selectivity and high stability, wherein CH 4 And CO 2 The conversion of (2) is above 50% overall and the yield of synthesis gas is 10mol g -1 h -1 The selectivity is generally above 0.9, hydrocarbon and alcohol products are not needed, and the catalyst can be directly used for producing high-value hydrocarbon and oleochemical by Fischer-Tropsch synthesis. The catalyst has high stability, can stably run for more than 100 hours, and does not generate catalyst sintering and carbon deposition. In addition, the catalyst can also drive ethane dry reforming and propane dry reforming to prepare synthesis gas.
The high-entropy alloy catalyst developed by the invention has good photo-thermal conversion efficiency, and can drive DRM technology to prepare synthesis gas under mild conditions. The process is not only beneficial to relieving the greenhouse effect, but also improves the energy utilization efficiency, and greatly reduces the production cost and the energy consumption.
In addition, the method has the advantages of simple reaction process, short period, cheap and easily available catalyst, repeated use and wide sources of reactant raw materials, can especially directly use combustible ice, shale gas and natural gas as raw material gas, and the like, provides a new synthesis path for preparing synthesis gas by DRM reaction, and has wide industrial application prospect.
Furthermore, through intensive studies of the present invention, it is preferable to have strong CO 2 Adsorption capacity catalyst supports including, but not limited to, for example, titanate materials (SrTiO 3 、Sr x Ba 1-x TiO 3 、SrBaTiO 3 、CaTiO 3 And SrZrO 3 Etc.) and oxide material (TiO 2 、CeO 2 、ZnO、Al 2 O 3 、MgO、SiO 2 Etc.). And screening out the high-entropy alloy catalyst with strong C-H bond and C=O bond dissociation capability and strong photothermal conversion capability. The components of the high-entropy alloy include, but are not limited to Co, ni, cu, zn, ru, rh, pd, pt and the like. The supported high-entropy alloy catalyst is utilized to realize the preparation of the synthetic gas by DRM with high efficiency, high selectivity and high stability under the condition of focusing sunlight.
The method for preparing the synthetic gas by photo-thermal driving DRM reaction comprises the following steps: by SrTiO 3 The supported high entropy alloy was used as a catalyst in a flow reactor under focused solar irradiation with two equal volumes of greenhouse gases (CH 4 And CO 2 Gas) is converted to an equal volume of synthesis gas at room temperature.
In the method of the invention, after the reaction is finished, the product is only synthesis gas, no extra separation step is needed, and the method can be directly used for producing high-value chemicals by Fischer-Tropsch synthesis.
In the method of the present invention, after the end of the reaction, the raw material gas CH can be detected by conventional means such as, but not limited to, using gas chromatography GC 4 And CO 2 And the rate and selectivity of the production of product synthesis gas. The stability of the catalyst can be detected by long-term operation under working conditions.
In the process of the present invention, srTiO is commercially available as such 3 SrTiO of a specific structure can be synthesized as a catalyst carrier according to experimental requirements 3 A carrier. The metal salt used may be one or more of nitrate, chloride, acetate.
In the method of the invention, the catalyst used is SrTiO supported by high-entropy alloy 3 A compound. In the catalyst of the present invention, srTiO as a base material 3 Not only has wide and cheap sources, but also has excellent optical property, chemical stability, thermal stability, super-hydrophilicity and non-migration. Meanwhile, the inventors have found that, in the preparation of the catalyst, srTiO supported by the obtained high-entropy alloy is obtained by simply supporting the high-entropy alloy 3 The compound can be used as a high-efficiency catalyst for reacting CH under specific reaction conditions 4 And CO 2 Gas or CH-containing 4 And CO 2 CH in gas 4 And CO 2 Highly selectively converted to synthesis gas. In addition, the inventors have found that the high entropy alloy loaded SrTiO used 3 The catalyst has good stability and can stably run for more than 100 hours under the working condition, so that the whole process has great industrial application prospect.
In the method of the present invention, preferably, the high entropy alloy and SrTiO supported in the catalyst 3 The molar ratio of (2) is 0.05:1.
In the process of the invention, the feed gas used may be derived from pure CH 4 And CO 2 In the form of a gas, also containing CH 4 And CO 2 In the form of a gas. The term "CH-containing 4 And CO 2 The gas "means that it contains CH 4 And CO 2 Is a gas mixture of (a) and (b). In addition, the feed gas may also be derived directly from combustible ice, shale gas and natural gas. Preferably containing CH therein 4 And CO 2 The volume content of the gas is greater than 10% of the gas.
In the process of the invention, although for CH in the reactor 4 And CO 2 Gas or CH-containing 4 And CO 2 The pressure of the gas is not particularly limited, but preferably CH in the reactor 4 And CO 2 Gas or CH-containing 4 And CO 2 The pressure of the gas was 0.1MPa.
In the method of the present invention, preferably, the illumination intensity of the illumination conditions used may be 10 to 5000mW/cm 2 . Preferably the illumination intensity is 4000mW/cm 2 。
In the method of the present invention, the light source for the illumination condition is not particularly limited as long as it is capable of emitting light radiation. Preferably, the light source for the illumination condition may be one or more selected from the group consisting of focused sunlight, a xenon lamp, an LED lamp (i.e., a light emitting diode), a tungsten lamp, and a mercury lamp.
In the process of the present invention, the reaction temperature of the reactor is generally from 20 to 600 ℃; preferably, the reaction temperature used may be from 20 to 600℃and most preferably the reaction is carried out at ambient temperature (i.e., about 25 to 30 ℃). The reactor may be heated to the desired reaction temperature by conventional means such as heating wires or jackets, if desired.
In the process of the present invention, the reaction is usually stably operated for 0 to 200 hours, more preferably for 100 hours, from the viewpoint of efficiency.
In the method of the present invention, the reactor to be used is not particularly limited as long as it can withstand a certain pressure and can be closed, and for example, a quartz reactor, a glass reactor, a fixed bed reactor, a fluidized reactor, or the like can be used.
In the method of the present invention, the catalyst carrier used is not particularly limited, and the catalyst carrier used includes, but is not limited to, srTiO 3 Other commercial oxide substitutes may also be usedSrTiO substitute 3 For example titanate materials (Sr) x Ba 1-x TiO 3 、SrBaTiO 3 、CaTiO 3 And SrZrO 3 Etc.) and oxide material (TiO 2 、CeO 2 、ZnO、Al 2 O 3 、MgO、SiO 2 Etc.). Preferably commercially available SrTiO 3 As a carrier.
In the method of the present invention, the high-entropy alloy used is not particularly limited, and the components of the high-entropy alloy include, but are not limited to Co, ni, cu, zn, ru, rh, pd, pt and the like. The preferred component is a high entropy alloy of CoNiRuRhPd.
The invention provides a loaded high-entropy alloy in CO 2 The use of a source and light alkane source for dry reforming to produce synthesis gas as a catalyst and a method for producing synthesis gas from photo-thermally driven methane dry reforming. The invention uses the loaded high-entropy alloy as the catalyst to be applied to CO 2 In the process of preparing the synthesis gas by dry reforming of the source and the light alkane source, the corresponding high-efficiency sustainable photo-thermal driving methane Dry Reforming (DRM) method for preparing the synthesis gas (CO and H) is also disclosed 2 ) Is a method of (2). The invention uses high entropy alloy loaded by metal oxide carrier or titanate carrier as catalyst, and in flow reactor, under external energy (such as focused sunlight irradiation), two kinds of greenhouse gases (CH) 4 And CO 2 Gas) is converted to an equal volume of synthesis gas under mild conditions. The product synthesis gas can be used directly in the manufacture of high value chemicals in the fischer-tropsch synthesis.
The specific supported high-entropy alloy catalyst adopted by the invention has good photo-thermal conversion efficiency, and can realize the preparation of synthetic gas by DRM technology under mild conditions. The process is not only beneficial to relieving the greenhouse effect, but also improves the energy utilization efficiency, and greatly reduces the production cost and the energy consumption. In addition, the method has the advantages of simple reaction process, short period, cheap and easily available catalyst, repeated use and wide sources of reactant raw materials, can especially directly use combustible ice, shale gas and natural gas as raw material gas, and the like, provides a new synthesis path for preparing the synthetic gas by DRM, and has wide industrial application prospect.
The high-entropy alloy catalyst adopted by the invention has good photo-thermal conversion efficiency, can drive DRM technology to prepare synthetic gas under mild conditions, is high-efficiency, high-selectivity and high-stability synthetic gas production, has no hydrocarbon and alcohol products, and can be directly used for producing high-value hydrocarbon and oleochemicals by Fischer-Tropsch synthesis; the catalyst has high stability, can stably run for more than 100 hours, and does not generate catalyst sintering and carbon deposition; in addition, the catalyst can also drive ethane dry reforming and propane dry reforming to prepare synthesis gas. The process is not only beneficial to relieving the greenhouse effect, but also improves the energy utilization efficiency, and greatly reduces the production cost and the energy consumption. In addition, the method provided by the invention has the advantages of simple reaction process, short period, low price and easy availability of catalyst, repeated use, wide sources of reactant raw materials, direct use of combustible ice, shale gas and natural gas as raw material gas and the like, provides a new synthesis path for preparing synthesis gas by DRM reaction, and has wide industrial application prospect.
Experimental results show that the method for preparing the synthetic gas by dry reforming provided by the invention only irradiates with focused sunlight in a mobile phase reactor, and two equal volumes of greenhouse gases (CH 4 And CO 2 Gas) is converted to an equal volume of synthesis gas, CH, at room temperature 4 And CO 2 The conversion of (2) is above 50% overall and the yield of synthesis gas is 10mol g -1 h -1 The selectivity is generally above 0.9, hydrocarbon and alcohol products are not generated, and the catalyst can stably run for more than 100 hours.
To further illustrate the invention, the following examples are provided in connection with the loading of high entropy alloys in CO 2 The use of source and light alkane sources as catalysts in the dry reforming of synthesis gas and a process for the dry reforming of light alkanes to produce synthesis gas are described in detail, but it should be understood that these examples are carried out with the technical solution of the present invention in mind, and detailed implementations and specific procedures are presented, only to further illustrate the features and advantages of the present invention and not to limit the scope of the claims of the present invention, nor to limit the scope of the present invention to the examples described below.
Catalyst preparation
The preparation of the catalyst used in the invention is as follows, srTiO supported by high entropy alloy 3 The following are examples:
2.3g commercial SrTiO was added to a 500mL glass beaker 3 And 100mL deionized water, after vigorous stirring for 30min, 5mL of 10mM each metal precursor solution was added. After stirring at room temperature for 1 hour, the resulting mixture was evaporated at 100 ℃ overnight to completely remove deionized water. Then, the resulting sample was subjected to 10% H 2 Calcining at 400 deg.C in 90% Ar atmosphere for 2 hr (heating rate 5 deg.C min -1 ). Finally, naturally cooling to room temperature, thereby obtaining SrTiO loaded by the high-entropy alloy 3 A catalyst. Wherein the high entropy alloy and SrTiO are supported in the catalyst 3 The molar ratio of (2) is 0.05:1.
Based on the same procedure as described above, only the amount of the metal precursor used is changed accordingly, thereby obtaining SrTiO with high entropy alloy loading 3 The molar ratio of (2) is 0.005-0.1:1.
Based on the same procedure as described above, only the amount of the metal precursor used is changed accordingly, thereby obtaining SrTiO with high entropy alloy loading 3 The molar ratio of (2) is 0.005-0.1:1.
Based on the same procedure as described above, only the kind of metal precursor used is changed accordingly, thereby obtaining SrTiO with different high-entropy alloy loads 3 Catalysts, including but not limited to CoNiCuPdRu/SrTiO 3 、CoNiCuPdRh/SrTiO 3 、CoNiCuPdPt/SrTiO 3 、CoNiCuPdAu/SrTiO 3 、CoNiCuPtRu/SrTiO 3 、CoNiCuRhRu/SrTiO 3 Etc.
Based on the same procedure as above, by using Sr x Ba 1-x TiO 3 、SrBaTiO 3 、CaTiO 3 And SrZrO 3 Iso-titanate material and TiO 2 、CeO 2 、ZnO、Al 2 O 3 、MgO、SiO 2 Isooxide material instead of SrTiO 3 As support material, other high entropy alloy supported catalysts with the same metal loading were prepared.
Example 1
In a mobile phase reactor (which is in communication controlled by a stainless steel valve and can apply a maximum pressure of 20 MPa), 5mg of SrTiO loaded with high-entropy alloy is added 3 Catalyst (CoNiRuRhPd/SrTiO) 3 Wherein CoNiRuRhPd and SrTiO 3 Molar ratio of 0.05:1) as catalyst, will contain 10% CH 4 /10％CO 2 A steel cylinder of/80 Ar was introduced into the mobile phase reactor via a pressure reducing valve. The pressure in the reactor is normal pressure, CH 4 And CO 2 The flow rates of (2) are 10mLmin each -1 The total flow rate was 20mLmin -1 . At room temperature (about 25 ℃ C.), at 4000mW/cm using focused sunlight as a light source 2 The reaction is carried out under irradiation with the illumination intensity of (2).
The product synthesis gas was evaluated by an on-line gas chromatograph (GC-2014ATFSPL,Ar carrier,Shimadzu) equipped with two Flame Ionization Detectors (FID) and one Thermal Conductivity Detector (TCD).
Referring to fig. 1, fig. 1 shows the synthesis gas yield rate and selectivity obtained in the dry reforming of methane provided in example 1 of the present invention. Wherein, FIG. 1a shows the conversion of CO and FIG. 1b shows the selectivity.
As can be seen from FIG. 1, the products were CO and H as determined by gas chromatography 2 Wherein CO and H 2 Is produced at a rate of 10mol g -1 h -1 Above, CH 4 And CO 2 The conversion of (a) is above 50% (figure 1 a) and the selectivity of the synthesis gas is above 0.9 (figure 1 b). In addition, the catalyst can continuously and stably run for more than 100 hours. The method has the potential of industrial application obviously by combining the generation rate, selectivity and catalyst stability of the synthesis gas.
Example 2
The specific reaction procedure and detection method were the same as in example 1, using CoNiRuRhPd/BaTiO 3 Substitute CoNiRuRhPd/SrTiO 3 As a catalyst.
Through detection, the generation rate of the synthesis gas of the target product is 8.0mol g -1 h -1 The selectivity was 0.92.
Example 3
Specific reaction process and detection methodThe method is the same as in example 1, using CoNiRuRhPd/Sr x Ba 1-x TiO 3 Substitute CoNiRuRhPd/SrTiO 3 As a catalyst.
Through detection, the generation rate of the synthesis gas of the target product is 9.0mol g -1 h -1 The selectivity was 0.95.
Example 4
The specific reaction procedure and detection method were the same as in example 1, using CoNiRuRhPd/CaTiO 3 Substitute CoNiRuRhPd/SrTiO 3 As a catalyst.
Through detection, the generation rate of the synthesis gas of the target product is 6.3mol g -1 h -1 The selectivity was 0.91.
Example 5
The specific reaction procedure and detection method were the same as in example 1, using CoNiRuRhPd/SrZrO 3 Substitute CoNiRuRhPd/SrTiO 3 As a catalyst.
Through detection, the generation rate of the synthesis gas of the target product is 5.0mol g -1 h -1 The selectivity was 0.90.
Example 6
The specific reaction procedure and detection method were the same as in example 1, using CoNiRuRhPd/MgO instead of CoNiRuRhPd/SrTiO 3 As a catalyst.
Through detection, the generation rate of the synthesis gas of the target product is 1.2mol g -1 h -1 The selectivity was 0.70.
Example 7
The specific reaction procedure and detection method were the same as in example 1, using CoNiRuRhPd/Al 2 O 3 Substitute CoNiRuRhPd/SrTiO 3 As a catalyst.
Through detection, the generation rate of the synthesis gas of the target product is 1.6mol g -1 h -1 The selectivity was 0.75.
Example 8
The specific reaction procedure was the same as in example 1, using a 300 xenon lamp instead of natural sunlight as the light source.
Through detection, the generation rate of the synthesis gas of the target product is 9.8mol g -1 h -1 The selectivity was 0.95.
Example 9
Specific reaction procedure and detection method the same as in example 1, 50% CH was used 4 /50％CO 2 Instead of 10% CH 4/ 10％CO 2 80% Ar was used as feed gas.
Through detection, the generation rate of the synthesis gas of the target product is 20mol g -1 h -1 The selectivity was 0.50.
Example 10
Specific reaction procedure and detection method the same as in example 1, using 1% CH 4 /1％CO 2 98% Ar for 10% CH 4 /10％CO 2 80% Ar was used as feed gas.
Through detection, the generation rate of the target product CO is 0.3mol g -1 h -1 The selectivity was 1.0.
Example 11
The specific reaction procedure and detection method were the same as in example 1, except that 50mLmin was used -1 Is replaced by 20mLmin -1 Is a flow rate of (c) a gas.
Through detection, the generation rate of the synthesis gas of the target product is 19mol g -1 h -1 The selectivity was 0.52.
Example 12
The specific reaction procedure and detection method were the same as in example 1, except that 5mL min was used -1 Flow rate instead of 20mL min -1 Is a flow rate of (c) a gas.
Through detection, the generation rate of the synthesis gas of the target product is 3.3mol g -1 h -1 The selectivity was 1.0.
Examples 13 to 23
The specific reaction procedure was the same as in example 1, and experiments were conducted using a batch reactor instead of a mobile phase reactor, and the catalyst recovered was used 1, 2, and 3 times up to 11 times (i.e., 10 times repeatedly).
Referring to FIG. 2, FIG. 2 shows SrTiO according to the present invention 3 The re-use performance results of the supported high entropy alloy catalyst.
As can be seen from fig. 2, the catalyst of the present invention has no significant decrease in catalytic efficiency (i.e., activity and selectivity of the target product) after 10 repeated uses.
The loaded high-entropy alloy provided by the invention is prepared by the method in CO 2 The use of sources and light alkane sources as catalysts in dry reforming to produce synthesis gas and a method for producing synthesis gas from photo-thermally driven methane dry reforming are described in detail, with specific examples being set forth herein to illustrate the principles and embodiments of the invention, the description of the examples above being only intended to aid in understanding the methods of the invention and its core ideas, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems, and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. Loaded high entropy alloy at CO 2 The use of dry reforming of a source and a light alkane source as a catalyst in the preparation of synthesis gas.
2. The use according to claim 1, wherein the metals in the high entropy alloy comprise four or more of Co, ni, cu, zn, ru, rh, pd and Pt;
the supported carrier comprises a metal oxide carrier and/or a titanate carrier;
the light alkane comprises methane, ethane or propane.
3. The use according to claim 2, characterized in that the molar ratio of the high-entropy alloy to the support is (0.005-0.1): 1, a step of;
the metal oxide support comprises TiO 2 、CeO 2 、CaO、ZnO、Al 2 O 3 MgO and SiO 2 One or more of the following;
the titanate carrier comprises SrTiO 3 、Sr x Ba 1-x TiO 3 (0＜x＜1)、SrBaTiO 3 、CaTiO 3 And SrZrO 3 One or more of the following;
the conditions for the preparation include performing the preparation under energized conditions.
4. The use according to claim 3, wherein the time of preparation is 0.1 to 300 hours;
the energizing means comprises illumination and/or heating;
the illumination intensity of the illumination is 10-5000mW/cm 2 。
5. The use of claim 4, wherein the source of illumination comprises one or more of natural light, xenon, LED, tungsten, and mercury lamps;
the temperature of the illumination is normal temperature;
the heating temperature is 20-700 ℃.
6. The use according to claim 1, wherein the CO 2 The source comprises CO 2 Or contains CO 2 Is a gas of (2);
the light alkane source comprises light alkane or gas containing light alkane;
the CO 2 The source and light alkane source include CO 2 And light alkanes or CO 2 And light alkane;
the molar ratio between metal elements in the high-entropy alloy is 1:1.
7. a method for preparing synthesis gas by dry reforming of light alkane, which is characterized by comprising the following steps:
under the energized condition, under the action of a supported catalyst loaded with high-entropy alloy, CO 2 The source and light alkane source are subjected to dry reforming reaction of methane to obtain CO and H 2 。
8. The method of claim 7, wherein the metals in the high entropy alloy comprise four or more of Co, ni, cu, zn, ru, rh, pd and Pt;
the mol ratio of the high-entropy alloy to the loaded carrier is (0.005-0.1): 1, a step of;
the support comprises a metal oxide support and/or a titanate support.
9. The method of claim 7, wherein the CO 2 The pressure of the source is 0.1-10 MPa;
the pressure of the light alkane source is 0.1-10 MPa;
the means of energizing include illumination and/or heating.
10. The method according to claim 8, wherein the illumination intensity of the illumination is 10 to 5000mW/cm 2 ；
The heating temperature is 20-700 ℃;
the preparation time is 0.1-300 h;
the reactor for performing the methane dry reforming reaction comprises one or more of a quartz reactor, a glass reactor, a fixed bed reactor and a mobile phase reactor.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117244563A (en) * | 2023-11-15 | 2023-12-19 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Coated Ni-based photo-thermal catalyst and preparation method and application thereof |
| CN117447197A (en) * | 2023-12-25 | 2024-01-26 | 上海南极星高科技股份有限公司 | Preparation method of high-entropy pseudobrookite titanate ceramic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117244563A (en) * | 2023-11-15 | 2023-12-19 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Coated Ni-based photo-thermal catalyst and preparation method and application thereof |
| CN117244563B (en) * | 2023-11-15 | 2024-02-09 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Coated Ni-based photo-thermal catalyst and preparation method and application thereof |
| CN117447197A (en) * | 2023-12-25 | 2024-01-26 | 上海南极星高科技股份有限公司 | Preparation method of high-entropy pseudobrookite titanate ceramic |
| CN117447197B (en) * | 2023-12-25 | 2024-02-27 | 上海南极星高科技股份有限公司 | Preparation method of high-entropy pseudobrookite titanate ceramic |
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