CN114620686B - Method for preparing synthesis gas through dry reforming reaction of methane and catalyst thereof - Google Patents
Method for preparing synthesis gas through dry reforming reaction of methane and catalyst thereof Download PDFInfo
- Publication number
- CN114620686B CN114620686B CN202210341662.XA CN202210341662A CN114620686B CN 114620686 B CN114620686 B CN 114620686B CN 202210341662 A CN202210341662 A CN 202210341662A CN 114620686 B CN114620686 B CN 114620686B
- Authority
- CN
- China
- Prior art keywords
- sba
- catalyst
- zro
- methane
- reforming reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000006057 reforming reaction Methods 0.000 title claims abstract description 37
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 73
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 239000010410 layer Substances 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004065 semiconductor Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000005470 impregnation Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 239000002356 single layer Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 52
- 238000001354 calcination Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 15
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000000935 solvent evaporation Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 2
- 230000007480 spreading Effects 0.000 abstract description 3
- 238000003892 spreading Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 17
- 239000010453 quartz Substances 0.000 description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 9
- 238000002407 reforming Methods 0.000 description 9
- 239000000376 reactant Substances 0.000 description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 7
- 229910010271 silicon carbide Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical class S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000035425 carbon utilization Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for preparing synthesis gas by dry reforming reaction of methane. The method comprises contacting raw materials of methane and carbon dioxide with a catalyst under the condition of dry reforming reaction of methane to produce H as a main product 2 And CO, wherein the catalyst comprises a composite carrier and an active metal component loaded on the composite carrier, and the composite carrier is ZrO 2 /SBA-15, the active metal component being nickel, denoted Ni/@ -ZrO 2 a/SBA-15 catalyst; wherein the support is ZrO 2 ZrO in/SBA-15 2 Spreading on SBA-15 molecular sieve in single layer or multiple layers by impregnation method to form semiconductor film layer, wherein the catalyst Ni/@ -ZrO 2 The active component nickel in the/SBA-15 is loaded on the semiconductor film layer through a precipitation method. The method provided by the invention can be used for reaction under a low-temperature condition (lower than 700 ℃), the conversion rate of the raw materials is higher, and the catalyst has good stability.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a method for preparing synthesis gas through a methane dry reforming reaction and a methane dry reforming catalyst.
Background
Natural gas is a clean energy with abundant reserves, high efficiency and no secondary pollution, which gradually occupies the energy market, methane is the main component of natural gas and is also a C1 component for producing chemicals, but the chemical property of the methane is stable and is difficult to be converted into high-value chemical products, and simultaneously the methane is greenhouse gas which can cause greenhouse effect. Carbon dioxide, another reactant of the dry reforming reaction of methane, is the most important greenhouse gas, and is abundant and cheap, so that carbon capture, carbon utilization and the like have become hot spots. Dry reforming of methane with carbon dioxide and methaneThe main product generated from the raw material is H 2 And the synthesis gas product of CO is an important raw material for synthesizing Fischer-Tropsch synthesis, methanol synthesis, eneyne hydroformylation reaction and the like, so that the dry reforming reaction of methane provides an effective way for the efficient utilization of methane and carbon dioxide.
The reaction formula for dry reforming of methane is: CH (CH) 4 +CO 2 →2H 2 +2CO, the reaction is theoretically fully converted, but since the reaction is a strongly endothermic reaction (Δ H =247.3 kJ/mol), up to 1000 ℃ is generally required for the reaction conversion. At present, the catalyst mainly used in the dry reforming technology of methane is a transition metal catalyst, but the reaction temperature is high, and the problems of easy carbon deposition and inactivation at low temperature, low conversion rate and the like exist. High temperature reaction operation, in addition to high operating costs, generally results in the sintering of metal active components to deactivate and coke more easily, thereby resulting in catalyst deactivation, failing to maintain efficient conversion of methane and carbon dioxide for a long time, hindering its industrial application, while development of catalysts for dry reforming of methane at low temperature (below 700 ℃) is relatively scarce.
Disclosure of Invention
The invention adopts an impregnation method to load zirconium oxide on the carrier SBA-15 molecular sieve in a single-layer or multi-layer mode and form a semiconductor film layer, and then loads active component nickel nano particles on the semiconductor film layer through a precipitation method, wherein the active component nickel nano particles and the ZrO 2 The semiconductor film layer generates the synergistic effect to prepare Ni/@ -ZrO 2 the/SBA-15 catalyst has excellent activity, and the conversion rate of methane and carbon dioxide can reach more than 90 percent.
In order to achieve the above object, the present invention provides a method for preparing synthesis gas by dry reforming of methane, which comprises contacting raw materials of methane and carbon dioxide with a catalyst under dry reforming reaction conditions of methane to produce H as a main product 2 And CO, the catalyst comprises a composite carrier and an active metal component loaded on the composite carrier, and the composite carrier is ZrO 2 /SBA-15, the active metal component being nickel, denoted Ni/@ -ZrO 2 a/SBA-15 catalyst; wherein the composite carrier ZrO 2 ZrO in SBA-15 2 Spreading on SBA-15 molecular sieve in single layer or multiple layers by impregnation method to form semiconductor film layer, wherein the catalyst Ni/@ -ZrO 2 The active component nickel in the/SBA-15 is loaded on the semiconductor film layer through a precipitation method.
In a specific embodiment, the catalyst further comprises an auxiliary agent Mo, wherein the auxiliary agent Mo is inlaid or loaded on the semiconductor film layer through a direct impregnation method, and the catalyst is marked as Ni-Mo/@ ZrO 2 catalyst/SBA-15, ni-Mo/@ ZrO 2 ZrO in/SBA-15 catalyst composite carrier 2 5-20% of active component Ni, 0.5-5% of auxiliary agent Mo.
In a specific embodiment, when the catalyst is Ni/@ -ZrO 2 When the catalyst is SBA-15, the reaction temperature of the methane dry reforming reaction condition is 500-800 ℃, and the molar ratio of the methane to the carbon dioxide raw material gas is 1:1, the reaction space velocity is 10000-100000 ml.g -1 ·h -1 (ii) a When the catalyst is Ni-Mo/@ ZrO 2 When the catalyst is SBA-15, the reaction temperature of the methane dry reforming reaction condition is 500-550 ℃, the molar ratio of methane to carbon dioxide raw material gas is 1:1, the reaction space velocity is 10000-100000 ml.g -1 ·h -1 。
In a specific embodiment, the Ni-Mo/@ ZrO 2 the/SBA-15 catalyst is prepared by the following method comprising:
1) Preparation of composite carrier @ -ZrO by impregnation method 2 SBA-15: dispersing zirconium precursor salt and molecular sieve SBA-15 in deionized water, regulating the pH to 8-14 by using alkali liquor under the condition of water bath stirring at 50-90 ℃, continuing water bath heating and stirring for a first preset time, and performing standing aging, solid-liquid separation, washing, drying and calcining on the obtained solution to obtain a composite carrier @ -ZrO 2 /SBA-15；
2) Loading Ni on the composite carrier by a precipitation method: firstly, composite carrier is firstly coated with @ -ZrO 2 /SBA-15 is dispersed in solvent by ultrasonic, then soluble Ni salt is added, alkali is used at room temperatureRegulating the pH value of the solution to be 8-14, stirring the solution in water bath at the temperature of 30-60 ℃ for a second preset time, and carrying out solid-liquid separation, washing, drying and calcining on the obtained solution to obtain a product Ni/@ -ZrO 2/ SBA-15；
3) Direct impregnation of Mo: first, the product Ni/@ -ZrO 2/ SBA-15 is ultrasonically dispersed in deionized water, then aqueous solution of molybdenum salt is dripped, stirring is carried out at room temperature for a third preset time, the obtained solution is subjected to solvent evaporation, drying and calcination to obtain Ni-Mo/@ ZrO 2 The catalyst is SBA-15.
In a specific embodiment, the alkali solution is one of a NaOH solution, an ammonia solution and a KOH solution, the first preset time is 2 to 6 hours, and the calcination process parameters are as follows: the heating rate is 1-7 ℃/min, the calcining temperature is 400-800 ℃, and the calcining time is 1-5 h.
In a specific embodiment, the solvent is one of deionized water, ethylene glycol and ethanol, the alkali solution is one of NaOH solution, ammonia water and KOH solution, the second preset time is 2-6 hours, and the calcination process parameters are as follows: the heating rate is 1-7 ℃/min, the calcining temperature is 400-800 ℃, and the calcining time is 4-6 h.
In a specific embodiment, in the step 3), the third preset time is 0.5 to 4 hours, and the calcination process parameters are as follows: the heating rate is 1-7 ℃/min, the calcining temperature is 400-800 ℃, and the calcining time is 2-8 h.
In a specific embodiment, the method further comprises, prior to performing the dry reforming reaction of methane, reducing the catalyst with a reducing agent of H 2 And Ar, wherein the content of hydrogen is 10-30 vol%, the reduction temperature is 500-700 ℃, and the reduction time is 0.5-4 h.
The invention also provides a methane dry reforming catalyst, which comprises a composite carrier and an active metal component loaded on the composite carrier, wherein the active metal component is nickel, and the composite carrier is ZrO 2 (SBA-15) as Ni/@ -ZrO 2 A SBA-15 catalyst; wherein the composite carrier ZrO 2 ZrO in/SBA-15 2 Spreading on the carrier SBA-15 molecular sieve in a single-layer form or a multi-layer form by a dipping methodForming a semiconductor film layer on the substrate, the catalyst Ni/@ -ZrO 2 The active component nickel in the/SBA-15 is loaded on the semiconductor film layer through a precipitation method.
In a specific embodiment, the catalyst further comprises an auxiliary agent Mo, wherein the auxiliary agent Mo is loaded on the semiconductor film layer through a direct impregnation method, and the catalyst is marked as Ni-Mo/@ ZrO 2 catalyst/SBA-15, wherein Ni-Mo/@ ZrO 2 ZrO in/SBA-15 catalyst composite carrier 2 5-20% of active component Ni, 0.5-5% of auxiliary agent Mo.
The beneficial effects of the invention at least comprise:
1. as the zirconia is a unique inorganic non-metallic material, the zirconia is a substance with both an acid center and a basic center on the surface, and has excellent ion exchange performance and surface enriched air oxygen sites. And the nano zirconia is an important oxide, and has an irreplaceable position in the field of catalysis due to large specific surface and high activity. And as the nano material has the unique properties of quantum size effect, small size effect, surface effect, macroscopic quantum tunneling effect and the like, the nano zirconia also has various unique physical characteristics and chemical characteristics.
SBA-15 is a molecular sieve with an ordered mesoporous structure, has a unique pore structure, is in a two-dimensional hexagon shape, and has a highly ordered structure. Has the advantages of good hydrothermal stability, strong adsorption capacity, large specific surface area, high microporosity, high pore volume and the like.
According to the invention, zirconia is loaded on the carrier SBA-15 molecular sieve in a single-layer or multi-layer form through an impregnation method to form a semiconductor film layer, and then nickel nano particles are loaded on the semiconductor film layer, because the carrier SBA-15 molecular sieve has a large specific surface area, zrO is formed 2 The area of the semiconductor film is large, and the active component nickel nano particles are loaded on the composite carrier ZrO 2 The SBA-15 has high surface dispersity, small particle size and excellent activity, and the conversion rate of methane and carbon dioxide can reach the conversion rate during the catalytic reforming reaction at 800 DEG CTo more than 90%.
2. The invention provides a hybrid nano-structure nickel catalyst (Ni-Mo/@ ZrO) 2 SBA-15) is applied to low-temperature (lower than 500-550 ℃) methane dry reforming reaction, compared with the existing high-temperature (higher than 700-900 ℃) methane dry reforming reaction process, the reaction energy consumption is low, and active component metals are not easy to sinter.
3. Ni-Mo/@ ZrO 2 When the SBA-15 catalyst is applied to low-temperature dry reforming, the catalyst can stably run for about 10 hours at a high space velocity (36000 mL & h < -1 & g < -1 >), the conversion rate of reactants still keeps high, and the stability is good (the conversion rate of methane is reduced from 9.1% to 8.4% initially, and the conversion rate of carbon dioxide is reduced from 13.5% to 12.5%).
Drawings
FIG. 1 shows Ni/SBA-15, ni/@ -ZrO catalysts prepared in comparative example 2, example 2 and example 4 respectively 2 /SBA-15、Ni-Mo/@-ZrO 2 XRD pattern after SBA-15 reduction;
FIG. 2 shows Ni/SBA-15, ni/@ -ZrO catalysts prepared in comparative example 2, example 2 and example 4 respectively 2 /SBA-15、Ni-Mo/@-ZrO 2 SBA-15 catalyst stability test plot at 500 deg.C, i.e., plot of conversion versus time;
FIG. 3 is a catalytic activity curve diagram of a pure SiC catalyst at 650-800 ℃.
Detailed Description
The invention is described in detail below with reference to the figures and examples, but can be implemented in many different ways, which are limited and covered by the claims.
Example 1
Preparing a catalyst:
0.581g of ZrOCl.8H is taken 2 Dissolving O powder in 30mL of deionized water, performing ultrasonic treatment for 30min, weighing 2g of SBA-15, adding the solution of ZrOCl, adjusting the pH to 9-10 by using ammonia water under stirring at 80 ℃ in a water bath, continuing stirring at 80 ℃ in the water bath for 4h, standing at room temperature overnight, filtering, washing, performing vacuum drying at 80 ℃, calcining at 600 ℃ in a muffle furnace at the heating rate of 5 ℃/min for 2h to obtain the composite carrier @ ZrO 2 and/SBA-15. Taking 0.3g of composite carrier @ ZrO 2 SBA-15 is dispersed by deionized water ultrasonic for 30min,0.129g of Ni (NO) was added dropwise 3 ) 3 ·6H 2 Adjusting pH to about 9-10 with ammonia water under stirring at room temperature, further stirring in water bath at 45 deg.C for 4 hr, filtering, washing, vacuum drying at 80 deg.C, calcining at 600 deg.C in muffle furnace at 5 deg.C/min for 4 hr to obtain catalyst 1 (8% of Ni/@ -ZrO) 2 /SBA-15)。
Dry reforming reaction of methane test catalyst activity:
the carbon dioxide methane reforming reaction is carried out on a fixed bed micro reaction device, and the inner diameter of the quartz tube is 15mm, and the length of the quartz tube is 930mm. The experimental conditions of the dry reforming reaction of methane are as follows: the raw material gas is methane and carbon dioxide (99.9%) provided by Dalianda gas company Limited; the gas chromatography model was Agilent 7890A.
(1) And (3) catalyst reduction: 200mg of catalyst 1 (8% Ni/@ -ZrO) 2 SBA-15) and 3g of silicon carbide are uniformly mixed, the mixture is filled in the middle of a quartz tube reactor to form a bed layer, ar is introduced to the mixture, the temperature is raised to 750 ℃, and then mixed gas of Ar and H2 (volume ratio Ar: h 2 =4: 1) Reducing for 2 hours to obtain the catalyst in an activated state, wherein the reduction temperature is 600 ℃;
(2) And (3) testing the activity of the catalyst: and introducing Ar into the reactor, respectively heating to activity test temperatures (550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ and 800 ℃), closing the Ar introduction, and introducing reaction gases of methane and carbon dioxide (the gas volume ratio is 1, the total flow is 120mL/min, and the space velocity is 36000mL · h -1 ·g -1 ). Collecting tail gas by using a gas sampling needle, pumping the tail gas into a gas chromatography for product analysis, and calculating and analyzing results, wherein the conversion rates of reactants are shown in tables 1 and 2, the table 1 is the conversion rate of methane at different temperatures, and the table 2 is the conversion rate of carbon dioxide at different temperatures.
Example 2
Same as example 1 except that Ni (NO) was added 3 ) 3 ·6H 2 The mass of O is 0.1652g, i.e. Ni/@ -ZrO 2 The mass fraction of Ni in the/SBA-15 was 10%, which was noted as catalyst 2 (10% Ni-10% ZrO) 2 /SBA-15)。
Example 3
Same as example 1 except that Ni (NO) was added 3 ) 3 ·6H 2 The mass of O is 0.203g, i.e. Ni/@ -ZrO 2 The mass fraction of Ni in the/SBA-15 is 12%, recorded as catalyst 3 (12% Ni-10% 2 /SBA-15)。
Example 4
Catalyst preparation
Taking 0.581g of ZrOCl.8H2O powder, adding 30mL of deionized water for dissolution, carrying out ultrasonic treatment for 30min, weighing 2g of SBA-15, adding the ZrOCl solution, adjusting the pH to be about 9-10 by using ammonia water under stirring at 80 ℃ in a water bath, continuing stirring in the water bath at 80 ℃ for 4H, standing overnight at room temperature, filtering and washing, carrying out vacuum drying at 80 ℃, calcining at 600 ℃ in a muffle furnace at the temperature rise rate of 5 ℃/min for 2H to obtain a carrier @ ZrO 2 2/ SBA-15. 0.3g of the above composite support (@ ZrO) was taken 2 /SBA-15) was dispersed with deionized water by ultrasonic for 30min, and 0.1652g of Ni (NO) was weighed dropwise 3 ) 3 ·6H 2 Regulating pH to 9-10 with ammonia water at room temperature while stirring, stirring in water bath at 45 deg.c for 4 hr, filtering, washing, vacuum drying at 80 deg.c, calcining in muffle furnace at 600 deg.c at 5 deg.c/min for 4 hr to obtain Ni/@ -ZrO product 2 and/SBA-15. Taking the product Ni/@ -ZrO 2 Dispersing SBA-15.3g with deionized water for 30min, dropping 0.0113g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O solution, then stirred in a 40 deg.C water bath for 30min, then stirred in a 60 deg.C water bath, the solvent evaporated, dried, calcined in a muffle furnace at 550 deg.C for 6h at a heating rate of 2 deg.C/min to obtain catalyst 4 (10% Ni-2% 2 /SBA-15)。
The catalyst activity was tested in the same manner as in example 1.
Referring to FIG. 1, FIG. 1 shows Ni/SBA-15, ni/@ -ZrO 2 /SBA-15、Ni-Mo/@-ZrO 2 XRD pattern after reduction of the/SBA-15 catalyst. Wherein the lower part and the upper part have SBA-15 characteristic peak and three Ni characteristic peaks, zrO 2 The dispersion was too high to detect its characteristic peak due to the lower content, while the Mo content was low and the characteristic peak was not detected even with high dispersion.
The results of the catalytic reactions of the catalysts of examples 1 to 4 when used for the dry reforming of methane are shown in tables 1 and 2.
TABLE 1 conversion of methane at different reaction temperatures
TABLE 2 conversion of carbon dioxide at different reaction temperatures
As is clear from tables 1 and 2, 10% of Ni/@ -ZrO 2 The activity of the/SBA-15 is highest in methane reforming reaction, the activity is better at high temperature, the methane conversion rate is 90.7% at 800 ℃, the catalytic activity of Mo is inhibited at high temperature, and the activity of Mo is not greatly influenced at low temperature.
Example 5
Preparation of catalyst As in example 2, catalyst 2 prepared in example 2 was used (10% Ni/@ -ZrO) 2 SBA-15) the stability of the catalysts was tested as follows:
experimental equipment and experimental conditions:
the carbon dioxide methane reforming reaction is carried out on a fixed bed micro reaction device, and the inner diameter of the quartz tube is 15mm, and the length of the quartz tube is 930mm. The experimental conditions of the dry reforming reaction of methane are as follows: the raw material gas is methane and carbon dioxide (99.9%) provided by Dalian special gas company Limited; the gas chromatography model was Agilent 7890A.
And (3) testing the stability of the catalyst: 200mg of catalyst 2 (10% Ni/@ -ZrO) 2 /SBA-15) and 3g of silicon carbide are uniformly mixed, filled in the middle of a quartz tube reactor to form a bed layer, and Ar is introduced to raise the temperature to 750 ℃. Introducing Ar and H 2 Mixed gas (volume ratio Ar: H) 2 =4: 1) Reducing for 2 hours to obtain an activated catalyst, introducing Ar into the reactor, heating to the reaction temperature of 500 ℃, closing Ar, introducing reaction gases of methane and carbon dioxide (the gas volume ratio is 1:1, the total flow is 120mL/min, and the space velocity is 36000mL h -1 ·g -1 ) And the reaction time is prolonged. The tail gas collected by a gas sampling needle is injected into a gas chromatograph for product analysis, and the result of calculating and analyzing the conversion rate of reactants along with time is shown in figure 2.
Example 6
Preparation of the catalyst As in example 4, the catalyst 4 prepared in example 4 was used (10% Ni-2% 2 SBA-15) the stability of the catalysts was tested as follows:
experimental equipment and experimental conditions:
the carbon dioxide methane reforming reaction is carried out on a fixed bed micro-reactor, and the quartz tube has an inner diameter of 15mm and a length of 930mm. The experimental conditions of the dry reforming reaction of methane are as follows: the raw material gas is methane and carbon dioxide (99.9%) provided by Dalian special gas company Limited; the gas chromatography model was Agilent 7890A.
And (3) testing the stability of the catalyst: 200mg of catalyst 2 (10% Ni/@ -ZrO) 2 /SBA-15) and 3g of silicon carbide are uniformly mixed, filled in the middle of a quartz tube reactor to form a bed layer, and Ar is introduced to raise the temperature to 750 ℃. Introduction of Ar and H 2 Mixed gas (volume ratio Ar: H) 2 =4: 1) Reducing for 2 hours to obtain an activated catalyst, introducing Ar into the reactor, heating to the reaction temperature of 500 ℃, and closing the Ar, introducing reaction gases of methane and carbon dioxide (the gas volume ratio is 1:1, the total flow is 120mL/min, and the space velocity is 36000mL h -1 ·g -1 ) And the reaction time is prolonged. The tail gas collected by the gas injection needle is injected into the gas chromatography for product analysis, and the result of calculating the conversion rate of the analyzed reactant along with the time is shown in figure 2.
As can be seen from fig. 2, the addition of Mo greatly improves the stability thereof at low temperatures.
From tables 1 and 2 and FIG. 2, the volume ratio CH of the reaction gas 4 :CO 2 1 at flow rate CH 4 ＝60mL/min； CO 2 =60mL/min, no N 2 Diluting with gas at the airspeed of 36000mL & h < -1 >. G < -1 >; catalyst amount 0.2g, catalyst 10% Ni/@ -ZrO 2 The activity of SBA-15 is the best, the methane conversion rate is 9.5 percent at 500 ℃, the carbon dioxide is 15.4 percent, the methane conversion rate is 90.7 percent at 800 ℃, and the carbon dioxide is 87.5 percent, but the stability at the low temperature of 500 ℃ is not good enough; at catalyst 10% of Ni/@ -ZrO 2 After the addition of the auxiliary Mo into the SBA-15, the stability of the modified molybdenum disulfide at the low temperature of 500 ℃ is obviously enhanced, and the modified molybdenum disulfide runs stably for about 10 hours and then is reversedThe conversion rate of the reactant is still kept high, and the conversion rate of methane is still stabilized at 8.4 percent (the conversion rate of methane is reduced from the initial 9.1 percent to 8.4 percent); the carbon dioxide conversion remained stable at 12.5% (carbon dioxide conversion decreased from the initial 13.5% to 12.5%).
Comparative example 1
The carbon dioxide methane reforming reaction is carried out on a fixed bed micro-reactor. The quartz tube had an inner diameter of 15mm and a length of 930mm. The experimental conditions of the dry reforming reaction of the methane are as follows: the raw material gas is methane and carbon dioxide (99.9%) provided by Dalianda gas company Limited; the gas chromatography model was Agilent 7890A.
3g of silicon carbide is filled in the middle of a quartz tube reactor to form a bed layer, and Ar is introduced to raise the temperature to 750 ℃. Introducing mixed gas of Ar and H2 (volume ratio Ar: H) 2 =4: 1) Reducing for 2 hours to obtain an activated catalyst, introducing Ar into the reactor, heating to the set temperature of activity test temperature (650 ℃, 700 ℃, 750 ℃ and 800 ℃), closing Ar, introducing reaction gas of methane and carbon dioxide (the gas volume ratio is 1:1, the total flow is 120mL/min, and the space velocity is 36000mL h -1 ·g -1 ). The tail gas collected by the gas injection needle is injected into the gas chromatography for product analysis, and the result of calculating and analyzing the conversion rate of the reactant along with the temperature is shown in figure 3.
Comparative example 2
Catalyst preparation
Weigh 0.3g of SBA-15 carrier, disperse with deionized water ultrasound for 30min, drop-weigh 0.1652g of Ni (NO) 3 ) 3 ·6H 2 O solution, then adjusting pH to about 9-10 with ammonia water at room temperature while stirring, continuing to stir in a water bath at 45 ℃ for 4 hours, filtering and washing, vacuum drying at 80 ℃, and calcining at 600 ℃ in a muffle furnace at a heating rate of 5 ℃/min for 4 hours to obtain catalyst 5 (10% Ni/SBA-15).
Catalyst stability test
The carbon dioxide methane reforming reaction is carried out on a fixed bed microreactor. The quartz tube had an inner diameter of 15mm and a length of 930mm. The experimental conditions of the dry reforming reaction of methane are as follows: the raw material gas is methane and carbon dioxide (99.9%) provided by Dalian special gas company Limited; the gas chromatography model was Agilent 7890A.
200mg of catalyst 5 (10% Ni/SBA-15) was mixed uniformly with 3g of silicon carbide, packed in the middle of a quartz tube reactor to form a bed, and heated to 750 ℃ by introducing Ar. Introduction of Ar and H 2 Mixed gas (volume ratio Ar: H) 2 =4: 1) Reducing for 2 hours to obtain an activated catalyst, introducing Ar into the reactor, heating to the set temperature of 500 ℃, and closing the Ar, introducing reaction gases of methane and carbon dioxide (the gas volume ratio is 1:1, the total flow is 120mL/min, and the space velocity is 36000mL h -1 ·g -1 ) And the reaction time is prolonged. The tail gas collected by the gas injection needle is injected into the gas chromatography for product analysis, and the result of calculating the conversion rate of the analyzed reactant along with the time is shown in figure 2.
As can be seen from the results of comparative example fig. 3, siC alone is hardly active for the reaction. SiC is not an active component of the reaction and has almost no influence on the reaction activity; from comparative example 2 it is known that the novel hybrid nanostructured catalyst 10% Ni-2% 2 /SBA-15 the activity and stability of which were stronger than those of the conventional precipitation method-supported catalyst 10% Ni/SBA-15.
The foregoing is a further detailed description of the present invention in connection with specific preferred embodiments thereof, and it is not intended to limit the invention to the specific embodiments thereof. For those skilled in the art to which the invention pertains, several simple deductions and substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (8)
1. A method for preparing synthesis gas by dry reforming reaction of methane is characterized by comprising the step of contacting raw materials of methane and carbon dioxide with a catalyst under the condition of dry reforming reaction of methane to produce H as a main product 2 And CO, wherein the catalyst comprises a composite carrier and an active metal component loaded on the composite carrier, and the composite carrier is ZrO 2 The active metal component is nickel and is marked as Ni/@ -ZrO 2 A SBA-15 catalyst; wherein the composite carrier ZrO 2 ZrO in SBA-15 2 In the form of a single layer or multiple layers by impregnationThe catalyst Ni/@ -ZrO is laid on the SBA-15 molecular sieve in a layer form and forms a semiconductor film layer 2 The active component nickel in the/SBA-15 is loaded on the semiconductor film layer through a precipitation method.
2. The method for preparing the synthesis gas through the dry reforming reaction of the methane as claimed in claim 1, wherein the catalyst further comprises an additive Mo, the additive Mo is inlaid or loaded on the semiconductor film layer through a direct impregnation method, and the catalyst is marked as Ni-Mo/@ ZrO 2 catalyst/SBA-15, ni-Mo/@ ZrO 2 ZrO in/SBA-15 catalyst composite carrier 2 5 to 20 percent of active component Ni and 0.5 to 5 percent of auxiliary agent Mo.
3. The method for preparing synthesis gas by dry reforming reaction of methane according to claim 2, wherein when the catalyst is Ni/@ -ZrO 2 When the catalyst is SBA-15, the reaction temperature of the dry reforming reaction condition of the methane is 500-800 ℃, and the molar ratio of the methane to the feed gas of the carbon dioxide is 1:1, the reaction space velocity is 10000-100000 ml.g -1 ·h -1 (ii) a When the catalyst is Ni-Mo/@ ZrO 2 When the catalyst is SBA-15, the reaction temperature of the methane dry reforming reaction condition is 500-550 ℃, and the molar ratio of the methane to the carbon dioxide raw material gas is 1:1, the reaction space velocity is 10000-100000 ml.g -1 ·h -1 。
4. The method for preparing syngas by dry reforming reaction of methane according to claim 2, wherein the Ni-Mo/@ ZrO 2 the/SBA-15 catalyst is prepared by the following method comprising:
1) Preparation of composite carrier @ -ZrO by impregnation method 2 SBA-15: dispersing zirconium precursor salt and molecular sieve SBA-15 in deionized water, regulating the pH to 8-14 by using alkali liquor under the condition of water bath stirring at 50-90 ℃, continuing water bath heating and stirring for a first preset time, and performing standing aging, solid-liquid separation, washing, drying and calcining on the obtained solution to obtain a composite carrier @ -ZrO 2 /SBA-15；
2) Loading Ni on the composite carrier by a precipitation method: firstly, composite carrier is firstly coated with @ -ZrO 2 dispersing/SBA-15 in solvent by ultrasonic, adding soluble Ni salt, adjusting pH to 8-14 with alkali liquor at room temperature, stirring in water bath at 30-60 ℃ for a second preset time, and carrying out solid-liquid separation, washing, drying and calcining on the obtained solution to obtain the product Ni/@ -ZrO 2/ SBA-15；
3) Direct impregnation of Mo: first, the product Ni/@ -ZrO 2/ SBA-15 is dispersed in deionized water by ultrasonic, then aqueous solution of molybdenum salt is dripped, stirred for a third preset time at room temperature, and the obtained solution is subjected to solvent evaporation, drying and calcination to obtain Ni-Mo/@ ZrO 2 The catalyst is SBA-15.
5. The method for preparing synthesis gas through dry reforming reaction of methane according to claim 4, wherein in the step 1), the alkali solution is one of NaOH solution, ammonia water and KOH solution, the first preset time is 2-6 h, and the calcination process parameters are as follows: the heating rate is 1-7 ℃/min, the calcining temperature is 400-800 ℃, and the calcining time is 1-5 h.
6. The method for preparing synthesis gas through dry reforming reaction of methane according to claim 4, wherein in the step 2), the solvent is one of deionized water, ethylene glycol and ethanol, the alkali liquor is one of NaOH solution, ammonia water and KOH solution, the second preset time is 2-6 h, and the calcination process parameters are as follows: the heating rate is 1-7 ℃/min, the calcining temperature is 400-800 ℃, and the calcining time is 4-6 h.
7. The method for preparing the synthesis gas through the dry reforming reaction of the methane according to claim 4, wherein in the step 3), the third preset time is 0.5-4 h, and the calcination process parameters are as follows: the heating rate is 1-7 ℃/min, the calcining temperature is 400-800 ℃, and the calcining time is 2-8 h.
8. The method for preparing synthesis gas by dry reforming reaction of methane according to any one of claims 1 to 7, wherein the method comprisesThe method also comprises the step of reducing the catalyst before the dry reforming reaction of the methane, wherein the reducing agent is H 2 And Ar, wherein the content of hydrogen is 10-30 vol%, the reduction temperature is 550-700 ℃, and the reduction time is 0.5-4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210341662.XA CN114620686B (en) | 2022-04-02 | 2022-04-02 | Method for preparing synthesis gas through dry reforming reaction of methane and catalyst thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210341662.XA CN114620686B (en) | 2022-04-02 | 2022-04-02 | Method for preparing synthesis gas through dry reforming reaction of methane and catalyst thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114620686A CN114620686A (en) | 2022-06-14 |
| CN114620686B true CN114620686B (en) | 2023-03-17 |
Family
ID=81906581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210341662.XA Active CN114620686B (en) | 2022-04-02 | 2022-04-02 | Method for preparing synthesis gas through dry reforming reaction of methane and catalyst thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114620686B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9610569B2 (en) * | 2014-07-07 | 2017-04-04 | Council Of Scientific And Industrial Research | Process for the preparation of Ni—CeMgAl2O4 catalyst for dry reforming of methane with carbon dioxide |
| CN107999116B (en) * | 2017-12-14 | 2020-11-03 | 湘潭大学 | Catalyst for catalyzing selective hydrogenation of chloro-aromatic nitro compound |
| CN109107603B (en) * | 2018-09-18 | 2021-07-27 | 湘潭大学 | Ni hybrid composite nano-structure catalyst, preparation method thereof and application thereof in hydrogenation reaction |
| CN111085241B (en) * | 2019-12-24 | 2022-08-12 | 湘潭大学 | Method for preparing aniline by nitrobenzene hydrogenation and preparation method of catalyst thereof |
| WO2022008942A1 (en) * | 2020-07-07 | 2022-01-13 | Sorbonne Universite | Ni-silica-based catalysts with highly dispersed nickel particles |
| CN113019439A (en) * | 2021-02-04 | 2021-06-25 | 上海大学 | Molybdenum-modified molecular sieve-loaded nickel-based methane dry reforming catalyst, and preparation method and application thereof |
| CN113135825B (en) * | 2021-04-23 | 2022-04-08 | 湘潭大学 | Method for preparing aniline by nitrobenzene hydrogenation and hybrid nano-structure nickel catalyst thereof |
-
2022
- 2022-04-02 CN CN202210341662.XA patent/CN114620686B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114620686A (en) | 2022-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Baamran et al. | Effect of support size for stimulating hydrogen production in phenol steam reforming using Ni-embedded TiO2 nanocatalyst | |
| CN109908903A (en) | A kind of high-specific surface area Lignin-Based Activated Carbon is nickel-base catalyst and its preparation and application of carrier | |
| Guo et al. | Confining Ni nanoparticles in honeycomb-like silica for coking and sintering resistant partial oxidation of methane | |
| CN109395735B (en) | Methanation catalyst, preparation method thereof and method for preparing methane by using methanation catalyst | |
| Wang et al. | The effect of NH3· H2O addition in Ni/SBA-15 catalyst preparation on its performance for carbon dioxide reforming of methane to produce H2 | |
| CN113117712B (en) | Methane dry reforming reaction under microwave condition and catalyst thereof | |
| KR102035714B1 (en) | Nickel catalysts for reforming hydrocarbons | |
| Zheng et al. | A highly active and hydrothermal-resistant Cu/ZnO@ NC catalyst for aqueous phase reforming of methanol to hydrogen | |
| CN114768859B (en) | Nickel-silicon catalyst suitable for methane dry reforming and preparation method thereof | |
| Wei et al. | Hydroxyl-promoter on hydrated Ni-(Mg, Si) attapulgite with high metal sintering resistance for biomass derived gas reforming | |
| Sorcar et al. | Design of coke-free methane dry reforming catalysts by molecular tuning of nitrogen-rich combustion precursors | |
| Bao et al. | Metal CuxNiy/2titania-ceria catalysts for effective syngas production in methanol steam reforming | |
| Gao et al. | Development and application of Ni–M/sepiolite (M= Ce, Pr, and La) catalysts in biomass pyrolysis for syngas production | |
| Deng et al. | NiCo composite catalysts for CO 2 methanation: the effect of preparation methods on catalyst structure and activity | |
| Zhu et al. | Seeded-growth preparation of high-performance Ni/MgAl 2 O 4 catalysts for tar steam reforming | |
| CN113441160A (en) | Nickel hydroxide/titanium carbide photo-thermal catalytic material and preparation method and application thereof | |
| Rezaei et al. | A highly stable catalyst in methane reforming with carbon dioxide | |
| CN110075889B (en) | Catalyst for hydrogen production by methanol reforming and preparation method thereof | |
| Tian et al. | Enhanced catalytic performance of CO methanation over VO x assisted Ni/MCF catalyst | |
| CN114620686B (en) | Method for preparing synthesis gas through dry reforming reaction of methane and catalyst thereof | |
| Ergazieva et al. | Catalytic decomposition of Methane to hydrogen over Al2O3 supported mono-and bimetallic catalysts | |
| Zhang et al. | Hydrogen production from complete dehydrogenation of hydrazine borane on carbon-doped TiO 2-supported NiCr catalysts | |
| CN114602449A (en) | ZnZrO2Surface solid solution catalyst and preparation method and application thereof | |
| KR101281228B1 (en) | Mesoporous xerogel nickel-alumina catalyst and method for amnufacturing the same, and method for manufacturing methane using said catalyst | |
| WANG et al. | Morphology effect of nano-hydroxyapatite as support for loading Ni in methane dry reforming |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |