CN109569617B - Catalyst for preparing synthesis gas by double reforming of coke oven gas and preparation method and application thereof - Google Patents
Catalyst for preparing synthesis gas by double reforming of coke oven gas and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 145
- 239000000571 coke Substances 0.000 title claims abstract description 38
- 238000002407 reforming Methods 0.000 title claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 28
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011777 magnesium Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000012153 distilled water Substances 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 16
- 238000003825 pressing Methods 0.000 claims abstract description 14
- 238000012216 screening Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 8
- 150000002815 nickel Chemical class 0.000 claims abstract description 8
- 159000000008 strontium salts Chemical class 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 74
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 28
- 239000001569 carbon dioxide Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 230000008021 deposition Effects 0.000 abstract description 11
- 238000001035 drying Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 58
- 239000000203 mixture Substances 0.000 description 32
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 11
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 10
- 229910000018 strontium carbonate Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000006057 reforming reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005272 metallurgy Methods 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 2
- 229910018107 Ni—Ca Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- -1 sulfate salt Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910001341 Crude steel Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910017906 NH3H2O Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/647—2-50 nm
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a catalyst for preparing synthesis gas by double reforming of coke oven gas and a preparation method thereof, wherein the catalyst comprises SryBx/Mg1‑xAnd O, wherein B is an active metal, x is 0.05-0.5, y is 0.01-0.2, and the granularity is 60-80 meshes. The preparation method of the catalyst comprises the following steps: sequentially adding three substances of nickel salt, strontium salt, magnesium salt or magnesium oxide into deionized water or distilled water at room temperature, and dissolving into a mixed solution; evaporating the mixed solution to dryness at constant temperature or stirring at room temperature, standing and filtering to obtain a solid substance; drying the solid substance at 90-130 ℃ for 2-5 hours, and then roasting to obtain a catalyst; grinding the catalyst into powder and then pressing into tablets; and crushing and screening the catalyst pieces after heat treatment to obtain the catalyst with 60-80 meshes. The catalyst has high catalytic activity, strong carbon deposition resistance and strong thermal stability.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for preparing synthesis gas by double reforming of coke oven gas, a preparation method and application thereof.
Background
CO in iron and steel industry2The discharge pressure is huge, the yield of crude steel in China reaches 4.89 hundred million tons in 2007, and CO is2The direct discharge amount reaches 10.3 hundred million tons, and occupies about CO in China2About 16 percent of the discharge amount is CO which is second only to the power industry in the industrial field of China2And (5) arranging the users in a large scale. The hydrogen metallurgy is to solve CO2The effective way of emission, hydrogen replaces carbon as a reducing agent, and CO is fundamentally solved2The problem of emissions. At present, the stable supply of a low-cost hydrogen-rich reducing gas source is an important guarantee for realizing a new hydrogen reduction metallurgy process. At this stage, large-scale hydrogen production still relies primarily on fossil fuels. The hydrogen-rich reducing gas required for direct reduction of iron is obtained mainly by reforming natural gas. However, natural gas resources in China are relatively in short supply, and the requirement of large-scale metallurgy application is difficult to meet.
China is a large coke-producing country, and the coke oven gas discharged by independent coke-oven plants only reaches 240 hundred million Nm/year3The natural gas quantity is equivalent to two natural gas quantities of 'west gas and east gas transportation'. Although the coke oven gas in China is rich in resources, the quantity and the level of practical utilization are low, and serious resource waste and environmental pollution are caused. Coke oven gas is a byproduct of the coking process and contains a large amount of H2、CH4And a CO component, which is an excellent hydrogen production raw material. If the coke oven gas is used for preparing the hydrogen-rich reducing gas, the problems of discharge and utilization of the coke oven gas are solved, the requirement of direct reduction gas of iron ore can be solved, and the method is an alternative method for obtaining the hydrogen-rich gas in the prior hydrogen metallurgy.
The key to realizing large-scale hydrogen production by coke oven gas is to reform the hydrocarbon (mainly methane) in the coke oven gas. At present, the hydrogen production/synthesis gas process by methane reforming mainly comprises the following steps: steam reforming, partial oxidation reforming and carbon dioxide dry gas reforming. By adopting the technology of double reforming of coke oven gas, carbon dioxide and water vapor to prepare hydrogen and synthesis gas, CO can be converted2The greenhouse gas is utilized, and has double benefits of environment and economy. The main disadvantage of the process is that the catalyst is easy to deposit carbon and deactivate, so the key to realize industrial application is to develop a catalyst with high activity, high selectivity and high stability.
For Ni-based catalysts, the improvement of the carbon deposition resistance and the stability of the catalysts can be started by adding an auxiliary agent and selecting a proper carrier. The assistant in the catalyst has the functions of improving the activity and selectivity of the main catalyst, improving the heat resistance, the toxicity resistance, the mechanical strength, the service life and the like of the catalyst. The addition of a small amount of the auxiliary agent is generally needed, so that a remarkable effect is achieved. The addition of the auxiliary agents such as alkali metal, alkaline earth metal, rare earth element and the like and the mixed addition of a plurality of auxiliary agents in the Ni-based catalyst can effectively improve the activity and the stability of the catalyst. The alkali metals (Li, Na and K) are mainly added as electronic type auxiliary agents, so that the acidity of the catalyst can be weakened, and carbon deposition inactivation of the catalyst can be inhibited. The rare earth metal oxide can improve the dispersion condition of the active component on the surface of the catalyst and improve the stability of the catalyst.
First reported Ni/Al by Jong Wook Bae et Al2O3The catalyst coke oven gas carbon dioxide water vapor double-integrated experiment is carried out at 750 ℃, 0.1Mpa and CH4/CO2/CO/H2/H2O1/0.38/0.29/2.09/1.2, i.e. the total molar amount M of water vapor and carbon dioxide(H2O(g)+CO2)Molar amount M with methaneCH4Has a ratio of M(H2O(g)+CO2)∶MCH4At 1.6: 1, the methane conversion was 85%, but the carbon dioxide conversion was very low, only 20%.
The alkaline earth metal oxide auxiliary agent can effectively prevent the sintering of the catalyst and can improve the reaction activity and the carbon deposition resistance of the catalyst. As reported by Wang Lai Yoon et al, Ni-Ca/MgAl2O4Double integral experiment of carbon dioxide and water vapor of catalyst coke oven gas to investigate Ni-Ca/MgAl with different Ca contents2O4Influence of the catalyst on the carbon deposition performance. As a result, it was found that 10Ni-5Ca/MgAl2O4The catalyst has the best activity in CH4:H2O:CO2:H2:CO:N21:1.2:0.4:2:0.3:0.3, i.e. the total molar amount M of steam and carbon dioxide(H2O(g)+CO2)Molar amount M with methaneCH4Has a ratio of M(H2O(g)+CO2)∶MCH4At 800 deg.C and 5atm at 1.6: 1, the methane conversion is 65%, the carbon dioxide conversion is 40%, but there is still about 2% carbon deposition.
Disclosure of Invention
The invention aims to provide a catalyst for preparing synthesis gas by double reforming of coke oven gas.
In order to realize the purpose, the specific technical scheme is as follows:
catalyst for preparing synthesis gas by double reforming of coke oven gas, wherein the catalyst comprises SryBx/Mg1-xAnd O, wherein B is an active metal, x is 0.05-0.5, y is 0.01-0.2, and the granularity is 60-80 meshes.
More preferably, the active metal B is any one metal or any two metal mixture of Co, Ni, Ru and Pt; more preferably, the active metal B is metal Ni.
The invention also aims to provide a preparation method of the catalyst for preparing the synthesis gas by double reforming of the coke oven gas.
The specific technical scheme is as follows:
a preparation method of a catalyst for preparing synthesis gas by double reforming of coke oven gas comprises the following steps: sequentially adding three substances of nickel salt, strontium salt, magnesium salt or magnesium oxide into deionized water or distilled water at room temperature, and dissolving into a mixed solution; evaporating the mixed solution to dryness at constant temperature, or stirring at room temperature, standing and filtering to obtain a solid substance; drying the solid substance at 90-130 ℃ for 2-5 hours, and then roasting to obtain a catalyst; grinding the catalyst into powder, and pressing the powder into catalyst tablets by using pressure; and (3) carrying out heat treatment on the catalyst sheet, taking out the catalyst sheet, crushing and screening to prepare catalyst particles with 60-80 meshes, namely the catalyst for preparing the synthesis gas by double reforming of the coke oven gas.
Further preferably, the molar ratio of the nickel salt, the strontium salt, the magnesium salt or the magnesium oxide is 0.05-0.5: 0.05-0.2: 0.95-0.5.
More preferably, the nickel salt, strontium salt and magnesium salt are respectively any one of nitrate, sulfate or carbonate of nickel, strontium and magnesium; more preferably, the nickel salt, strontium salt and magnesium salt are nitrates of nickel, strontium and magnesium respectively.
Further preferably, the constant-temperature evaporation to dryness means that the mixture is stirred at the constant temperature of 80-120 ℃ until the mixture is solidified, the stirring time of the stirring at the room temperature is 10-15 hours, and the standing time of the standing is 10-15 hours.
Further preferably, the roasting is one of first-stage heating roasting and second-stage heating roasting; the first-stage heating roasting comprises the following steps: raising the temperature to 700-900 ℃ at the rate of 2-8 ℃ per minute, preserving the heat for 3-6 hours, and cooling to room temperature along with the furnace; the two-stage heating roasting comprises the following steps: raising the temperature to 900 ℃ at the rate of 2-8 ℃ per minute, preserving the heat for 3-6 hours, then raising the temperature from 900 ℃ to 1300 ℃ at the rate of 1000 ℃ at the rate of 2-8 ℃ per minute, preserving the heat for 10-15 hours, and finally cooling the temperature to room temperature along with the furnace from 1300 ℃ at 1000 ℃ to 1300 ℃.
Further preferably, the heat treatment is: raising the temperature to 700-900 ℃ at the rate of 2-8 ℃ per minute, preserving the heat for 5-10 hours, and then cooling along with the furnace.
The invention also aims to provide application of the catalyst for preparing the synthesis gas by double reforming of the coke oven gas.
The specific technical scheme is as follows:
an application of the catalyst for preparing the synthesis gas by double reforming of the coke oven gas and the carbon dioxide and the steam in preparing the synthesis gas by double reforming of the coke oven gas.
Further preferably, the catalyst is applied under the process conditions: the reaction temperature is 800-900 ℃, the reaction pressure is 1atm, and the space velocity is 1.2 multiplied by 104~3.2×105mL/g.h; molar total amount M of water vapor and carbon dioxide(H2O(g)+CO2)Molar amount M with methaneCH4The ratio of (A) to (B) is: m(H2O(g)+CO2)∶MCH4=1∶1。
The invention has the following beneficial effects:
the catalyst is used for double reforming of coke oven gas, carbon dioxide and steam to prepare synthesis gas, and has the advantages of high catalytic activity (high conversion rate of methane and carbon dioxide), strong carbon deposition resistance, strong thermal stability and high economic value.
Drawings
FIG. 1 shows Sr contents of different Sr obtained in examples 1-9yNi0.25/Mg0.75X-ray diffraction pattern (XRD) of O (y ═ 0.05, 0.1, 0.15, 0.2) catalyst;
FIG. 2 shows Sr contents of different Sr obtained in examples 1-9yNi0.25/Mg0.75Temperature programmed reduction of O (y is 0.05, 0.1, 0.15, 0.2) catalyst (TPR);
FIG. 3 shows Sr contents of different Sr obtained in examples 1-9yNi0.25/Mg0.75O (y ═ 0.05, 0.1, 0.15, 0.2) graph of methane and carbon dioxide conversion after catalyst reforming reaction, (a) is methane conversion and (b) is carbon dioxide conversion;
FIG. 4 shows Sr contents of different Sr obtained in examples 1-9yNi0.25/Mg0.75Thermogravimetric analysis (TG) of O (y 0.05, 0.1, 0.15, 0.2) after catalyst reforming reaction.
Detailed Description
Example 1
0.25mol of Ni (NO)3)2·6H2Dissolving O in 100ml of distilled water to form a nickel nitrate solution; 0.05mol of Sr (NO)3)2Dissolving in the nickel nitrate solution; then 0.75mol of MgO is added into the mixed solution of the nickel nitrate and the strontium nitrate, the mixture is fully and uniformly stirred, then the mixture is placed on a constant-temperature magnetic stirrer at room temperature and fully stirred for 12 hours, then the mixture is kept stand for 12 hours, then the mixture is filtered, the obtained solid is placed into a 110 ℃ oven to be dried for 3 hours, then the solid is taken out and placed into a muffle furnace to be roasted, the temperature is increased to 800 ℃ at the rate of 5 ℃ per minute, the temperature is kept for 5 hours, and then the solid is cooled to room temperature along with the furnace to obtain the catalyst. The resulting catalyst was pulverized and then pulverized with 1.5X 108And pressing the catalyst into a catalyst sheet by the pressure of Pa. Putting the catalyst piece into a muffle furnace, raising the temperature to 800 ℃ at the same rate of 5 ℃ per minute, preserving the temperature for 5 hours, cooling along with the furnace, taking out the catalyst piece, crushing the catalyst piece, and screening the crushed catalyst piece to prepare the catalyst particles with the particle size of 60-80 meshes.
Example 2 (one-step method)
0.25mol of Ni (NO) are added to 100ml of distilled water3)2·6H2O, 0.05mol of Sr (NO)3)2And 0.75mol of Mg (NO)3)2·6H2And O, stirring until the solution is uniformly dissolved to form a mixed solution of nickel nitrate, strontium nitrate and magnesium nitrate. Fully and uniformly stirring the mixed solutionSlowly adding (NH) to the mixed solution by using a peristaltic pump4)2CO3The solution was dissolved and the dropwise addition was stopped immediately after white precipitation occurred. Then aging, filtering, washing, drying and preparing into Sr0.05Ni0.25/Mg0.75And (3) an O catalyst. Then placing the mixture into a muffle furnace for roasting, raising the temperature to 800 ℃ at the rate of 5 ℃ per minute, preserving the temperature for 10 hours, and then cooling the mixture to room temperature along with the furnace. Taking out, crushing and sieving to prepare the catalyst particles with 60-80 meshes.
Example 3 (coprecipitation method) sulfate salt
0.25mol of Ni (NO) are added to 100ml of distilled water3)2·6H2O, 0.05mol of Sr (NO)3)2And 0.75mol of MgSO4·7H2And O, stirring until the mixture is dissolved uniformly to form a mixed solution of nickel nitrate, strontium sulfate and magnesium sulfate heptahydrate. The mixed solution is fully stirred evenly and then (NH) is added4)2CO3And NH3H2O, addition was stopped until precipitation occurred. Filtering, washing and precipitating, putting the precipitate into a 110 ℃ oven, taking out the precipitate after 12 hours, putting the precipitate into a muffle furnace for roasting, raising the temperature to 800 ℃ at the rate of 5 ℃ per minute, preserving the temperature for 10 hours, then cooling the precipitate along with the furnace, taking out the precipitate, crushing and screening the precipitate to prepare the catalyst particles with the particle size of 60-80 meshes.
Example 4 (sulfate salt)
0.25mol of Ni (NO)3)2·6H2Dissolving O in 100ml of distilled water to form a nickel nitrate solution; then 0.05mol of SrSO is added4And 0.75mol of MgO in the nickel nitrate solution, fully and uniformly stirring, then placing the mixture on a constant-temperature magnetic stirrer at room temperature, fully stirring for 12 hours, then standing for 12 hours, then filtering, putting the obtained solid into a 110 ℃ drying oven to dry for 3 hours, then taking out and putting the solid into a muffle furnace to roast, raising the temperature to 800 ℃ at the rate of 5 ℃ per minute, preserving the heat for 5 hours, and then cooling the solid to room temperature along with the furnace to obtain the catalyst. The resulting catalyst was pulverized and then pulverized with 1.5X 108And pressing the catalyst into a catalyst sheet by the pressure of Pa. The catalyst piece is then placed in a muffle furnace, likewise heated to 800 ℃ at a rate of 5 ℃ per minute and held there for 5 hoursCooling with the furnace, taking out, crushing and sieving to prepare the catalyst particles with 60-80 meshes.
Example 5
0.25mol of Ni (NO) are added to 100ml of distilled water3)2·6H2O, 0.05mol of SrCO3And 0.75mol of Mg (NO)3)2·6H2O, stirring until the O is uniformly dissolved to form a mixed solution of nickel nitrate, strontium carbonate and magnesium nitrate; after uniformly mixing, putting the mixed solution on a constant-temperature magnetic stirrer, stirring and evaporating at 90-100 ℃, and then putting the mixed solution in a 110 ℃ oven for drying for 3 hours; then placing the mixture into a muffle furnace for roasting, firstly heating to 800 ℃ at the temperature rise rate of 5 ℃ per minute and preserving heat for 4 hours, then heating to 1200 ℃ at the temperature rise rate of 5 ℃ per minute and preserving heat for 12 hours, and finally cooling to room temperature along with the furnace; grinding the calcined catalyst into powder, and then using 1.5X 108Pressing the pressure of Pa into a catalyst sheet; and (3) putting the pressed catalyst piece into a muffle furnace, raising the temperature to 800 ℃ at the temperature rise rate of 5 ℃ per minute, preserving the temperature for 10 hours, cooling along with the furnace, taking out, crushing and screening to prepare 60-80-mesh catalyst particles.
Example 6
0.25mol of Ni (NO) are added to 100ml of distilled water3)2·6H2O, 0.1mol of SrCO3And 0.75mol of MgO, stirring until the MgO is uniformly dissolved to form a mixed solution; putting the mixed solution on a constant-temperature magnetic stirrer at room temperature, fully stirring for 12 hours, standing for 12 hours, filtering, and putting the obtained solid into a 110 ℃ oven to be dried for 3 hours; then placing the mixture into a muffle furnace for roasting, raising the temperature to 800 ℃ at the rate of 5 ℃ per minute, preserving the temperature for 5 hours, and cooling the mixture to room temperature along with the furnace; grinding the calcined catalyst into powder, and grinding the powder into powder by using 1.5X 108Pressing the catalyst into a catalyst sheet under the pressure of Pa; and putting the catalyst piece into a muffle furnace, heating to 800 ℃ at the temperature rise rate of 5 ℃ per minute, preserving the temperature for 5 hours, cooling along with the furnace, taking out, crushing and screening to obtain the catalyst particles with the particle size of 60-80 meshes.
Example 7
0.25mol of Ni (NO) are added to 100ml of distilled water3)2·6H2O、0.15mol SrCO3And 0.75mol of MgO, and fully and uniformly stirring to form a mixed solution; putting the mixed solution on a constant-temperature magnetic stirrer at room temperature, fully stirring for 12 hours, standing for 12 hours, filtering, and putting the obtained solid in a drying oven at 110 ℃ for drying for 3 hours; then placing the mixture into a muffle furnace for roasting, raising the temperature to 800 ℃ at the rate of 5 ℃ per minute, preserving the temperature for 5 hours, and cooling the mixture to room temperature along with the furnace; grinding the calcined catalyst into powder, and grinding the powder into powder by using 1.5X 108Pressing the catalyst into a catalyst sheet under the pressure of Pa; and (3) putting the catalyst piece into a muffle furnace, raising the temperature to 800 ℃ at a temperature rise rate of 5 ℃ per minute, preserving the heat for 5 hours, cooling along with the furnace, taking out, crushing and screening to obtain the catalyst particles with the particle size of 60-80 meshes.
Example 8
0.25mol of Ni (NO) was weighed out3)2·6H2Dissolving the nickel nitrate into 100ml of distilled water to form a nickel nitrate solution; 0.2mol of SrCO is weighed3Dissolving the nickel nitrate in a nickel nitrate solution; then adding 0.75mol of MgO into the mixed solution of the nickel nitrate and the strontium carbonate, fully and uniformly stirring, fully stirring on a constant-temperature magnetic stirrer for 12 hours at room temperature, standing for 12 hours, filtering, putting the obtained solid into a 110 ℃ oven to be dried for 3 hours, then putting into a muffle furnace to be roasted, raising the temperature to 800 ℃ at a rate of 5 ℃ per minute, preserving the temperature for 5 hours, and then cooling to room temperature along with the furnace; grinding the calcined catalyst into powder, and grinding the powder into powder by using 1.5X 108Pressing the catalyst into a catalyst sheet under the pressure of Pa; and (3) putting the catalyst piece into a muffle furnace, raising the temperature to 800 ℃ at a temperature rise rate of 5 ℃ per minute, preserving the heat for 5 hours, cooling along with the furnace, taking out, crushing and screening to prepare the catalyst particles with the particle size of 60-80 meshes.
Example 9
0.25mol of Ni (NO) was weighed out3)2·6H2Dissolving the nickel nitrate into 100ml of distilled water to form a nickel nitrate solution; 0.05mol of SrCO is weighed3Dissolving the nickel nitrate in a nickel nitrate solution; then 0.75mol of MgO is added into the mixed solution of the nickel nitrate and the strontium carbonate, the mixture is fully and evenly stirred, the mixture is fully stirred for 12 hours on a constant temperature magnetic stirrer at room temperature, the mixture is kept stand for 12 hours, the mixture is filtered, and the obtained solid is placed into a baking oven at 110 ℃ to be baked for 3 hoursTaking out the mixture and putting the mixture into a muffle furnace for roasting, raising the temperature to 800 ℃ at the rate of 5 ℃ per minute, preserving the temperature for 5 hours, and cooling the mixture to room temperature along with the furnace; grinding the calcined catalyst into powder, and grinding the powder into powder by using 1.5X 108And pressing the catalyst into a catalyst sheet by the pressure of Pa. And putting the catalyst piece into a muffle furnace, heating to 800 ℃ at the temperature rise rate of 5 ℃ per minute, preserving the temperature for 5 hours, cooling along with the furnace, taking out, crushing and screening to prepare catalyst particles of 60-80 meshes.
Example 10
0.25mol of Ni (NO) are added to 100ml of distilled water3)2·6H2O, 0.1mol of Sr (NO)3)2And 0.75mol of Mg (NO)3)2·6H2And O, stirring until the solution is uniformly dissolved to form a mixed solution of nickel nitrate, strontium nitrate and magnesium nitrate. Fully and uniformly stirring the mixed solution, putting the mixed solution on a constant-temperature magnetic stirrer, stirring and evaporating the mixed solution to dryness at the temperature of between 90 and 100 ℃, and then putting the mixed solution into a 110 ℃ drying oven to dry the mixed solution for 3 hours; then placing the mixture into a muffle furnace for roasting, raising the temperature to 800 ℃ at the rate of 5 ℃ per minute, preserving the heat for 4 hours, raising the temperature to 1200 ℃ at the rate of 5 ℃ per minute, preserving the heat for 12 hours, and finally cooling the mixture to room temperature along with the furnace. Grinding the calcined catalyst into powder, and mixing with 1.5X 108And pressing the catalyst into a catalyst sheet by the pressure of Pa. And (3) putting the catalyst piece into a muffle furnace, raising the temperature to 800 ℃ at a temperature rise rate of 5 ℃ per minute, preserving the heat for 10 hours, cooling along with the furnace, taking out, crushing and screening to prepare the catalyst particles with the particle size of 60-80 meshes.
Example 11
0.25mol of Ni (NO) are added to 100ml of distilled water3)2·6H2O, 0.15mol of Sr (NO)3)2And 0.75mol of Mg (NO)3)2·6H2And O, stirring until the mixture is uniformly dissolved to form a mixed solution of nickel nitrate, strontium nitrate and magnesium nitrate. Fully and uniformly stirring the mixed solution, putting the mixed solution on a constant-temperature magnetic stirrer, stirring and evaporating the mixed solution to dryness at the temperature of between 90 and 100 ℃, and then putting the mixed solution into a 110 ℃ drying oven to dry the mixed solution for 3 hours; then placing the mixture into a muffle furnace for roasting, raising the temperature to 800 ℃ at the rate of 5 ℃ per minute and preserving the heat for 4 hours, then raising the temperature to 1200 ℃ at the rate of 5 ℃ per minute and preserving the heat for 12 hours, and finally, placing the mixture into a muffle furnace for roastingCooling to room temperature along with the furnace. Grinding the calcined catalyst into powder, and mixing with 1.5X 108And pressing the catalyst into a catalyst sheet by the pressure of Pa. And (3) putting the catalyst piece into a muffle furnace, raising the temperature to 800 ℃ at a temperature rise rate of 5 ℃ per minute, preserving the heat for 10 hours, cooling along with the furnace, taking out, crushing and screening to prepare the catalyst particles with the particle size of 60-80 meshes.
Example 12
0.25mol of Ni (NO) are added to 100ml of distilled water3)2·6H2O, 0.2mol of SrCO3And 0.75mol of Mg (NO)3)2·6H2And O, stirring until the mixture is uniformly dissolved to form a mixed solution of nickel nitrate, strontium carbonate and magnesium nitrate. Fully and uniformly stirring the mixed solution, then putting the mixed solution on a constant-temperature magnetic stirrer, stirring and evaporating the mixed solution to dryness at the temperature of between 90 and 100 ℃, and then putting the mixed solution into a 110 ℃ oven to bake for 3 hours; then placing the mixture into a muffle furnace for roasting, raising the temperature to 800 ℃ at the rate of 5 ℃ per minute and preserving the heat for 4 hours, then raising the temperature to 1200 ℃ at the rate of 5 ℃ per minute and preserving the heat for 12 hours, and finally cooling the mixture to room temperature along with the furnace. Grinding the calcined catalyst into powder, and mixing with 1.5X 108And pressing the catalyst into a catalyst sheet by the pressure of Pa. And (3) putting the catalyst piece into a muffle furnace, raising the temperature to 800 ℃ at a temperature rise rate of 5 ℃ per minute, preserving the heat for 10 hours, cooling along with the furnace, taking out, crushing and screening to prepare catalyst particles of 60-80 meshes.
Example 13: x-ray diffraction (XRD), Temperature Programmed Reduction (TPR), and specific surface area (BET) analysis of the catalyst
Sr contents different from those obtained in examples 1 to 9yNi0.25/Mg0.75The catalyst O (y 0.05, 0.1, 0.15, 0.2) was analyzed by X-ray diffraction (XRD), temperature-programmed reduction (TPR), and specific surface area (BET), and the results thereof were shown in fig. 1, fig. 2, and table 1, respectively.
TABLE 1 structural parameter Table for catalysts with different Sr contents
As can be seen from Table 1, Sr was obtained in the examplesyNi0.25/Mg0.75O (y ═ 0.05, 0.1, 0.15, 0.2) catalyst, wherein Sr is0.05Ni0.25/Mg0.75The specific surface area of O is the largest.
The addition of Sr reduces the specific surface area of the catalyst, and if the addition amount of Sr is increased from 0.05 to 0.2, the specific surface area of the SrNi/MgO catalyst is correspondingly reduced from 19.6 to 10m2(ii) in terms of/g. However, the pore volume of the catalyst is not changed, and the pore diameter is slightly changed.
As is clear from FIG. 1, Sr was synthesizedyNi0.25/Mg0.75The O catalyst mainly contains SrCO3MgNiO or Mg0.4Ni0.6An O solid solution phase. And SrCO3The stronger the diffraction peak intensity of the phase as the Sr content increases.
As can be seen from fig. 2, the catalyst showed a hydrogen consumption peak in the reduction of surface NiO at around 650 ℃. The hydrogen consumption peak is close to that of Ni/MgO solid solution catalyst when a small amount of SrO is added, which shows that the interaction between NiO and MgO is not greatly influenced when a small amount of SrO is added. When the amount of SrO is large, the hydrogen consumption peak near 1000 ℃ shifts to a higher temperature direction, indicating that SrO changes the interaction between NiO and MgO, making it more difficult for NiO to be reduced.
Example 14: activity evaluation test
The catalyst evaluation experiment was carried out on a fixed bed gas continuous flow reactor at atmospheric pressure. The reactant and product gases were analyzed by a gas chromatograph model GC9800, manufactured by shanghai scientific. The gas chromatograph is provided with TCD and Fid detectors and can be used for analyzing the content of products: CO, H2,CO2,CH4And C1~6The gas of (2). Before the reaction, 10% H is used2(45mL/min) at 800 ℃ for 2H, and then at this temperature coke oven gas (clean coke oven gas composition: 57.9 wt% H) is passed through231.6 wt% of CH47.4 wt% CO and 3.1 wt% CO2) And carbon dioxide, continuously and quantitatively feeding deionized water into a 350 ℃ gasification furnace by using a micro pump, converting the deionized water into water vapor, then feeding the water vapor into a reactor, and mixing the water vapor and the carbon dioxide in the mixed gas to obtain the total molar quantity M(H2O(g)+CO2)Molar amount M with methaneCH4The ratio of (A) to (B) is: m(H2O(g)+CO2)∶MCH41: 1; the reaction temperature is 800 ℃, the space velocity SV is 165000 mL/g.h, and the reaction temperature is 800 ℃. The catalyst used was 100 mg. In the reaction of CH4、CO2The conversion of (d) is calculated using the following formula:
CO2conversion rate:in the formula:intake CH4The flow rate of (a);-gas outlet CH4The flow rate of (a);
FIG. 3 shows Sr contents of different SryNi0.25/Mg0.75And (3) a graph of methane and carbon dioxide conversion rates after a coke oven gas carbon dioxide steam double reforming reaction experiment of an O (y is 0.05, 0.1, 0.15 and 0.2) catalyst. It can be seen from the figure that the activity of the catalyst gradually decreases as the Sr content increases. Sr0.05Ni0.25/Mg0.75The methane conversion rate of the O catalyst reaches about 75%, and the carbon dioxide conversion rate is about 72%. The strontium (Sr) content is strictly controlled, and the excessive strontium (Sr) content is not beneficial to the double reforming reaction of carbon dioxide and water vapor of the coke oven gas.
Example 15: carbon deposition analysis
The stability of the catalyst is an important condition for industrial application and is also an important index for measuring the performance of the catalyst. In the double reforming reaction of coke oven gas, carbon dioxide and water vapor, the important reason for the reduction of the catalyst stability is that the catalyst is deactivated by carbon deposition. In the experiment, the carbon dioxide and steam double-reforming experiment of coke oven gas is carried out on catalysts with different Sr contents SryNi0.25/Mg0.75O (y is 0.05, 0.1, 0.15 and 0.2), and the catalysts after the experiment are subjected to carbon deposition analysis. As shown in FIG. 4, no carbon was generated, and only one weight loss peak at 850-1000 ℃ appeared, which was detected by phase analysis and was a carbonate decomposition peak. The catalyst has strong anti-carbon deposition performance and has good application prospect when being applied to the industrial application of preparing the synthesis gas by double reforming of the coke oven gas, the carbon dioxide and the steam.
Claims (4)
1. The catalyst for preparing the synthetic gas by double reforming of the coke oven gas is characterized by comprising SryBx/Mg1-xO, wherein B is an active metal, x =0.05-0.5, y =0.05-0.2, particle size is 60-80 mesh; the active metal B is Ni; the preparation method comprises the following steps of adding three substances of nickel salt, strontium salt, magnesium salt or magnesium oxide into deionized water or distilled water at room temperature according to the mol ratio of 0.05-0.5: 0.05-0.2: 0.95-0.5 in sequence, and dissolving into a mixed solution; evaporating the mixed solution to dryness at a constant temperature of 80-120 ℃, or stirring at room temperature for 10-15h, standing for 10-15h and filtering to obtain a solid substance; baking the solid matter at 90-130 ℃ for 2-5 hours, and then adopting first-stage heating baking or second-stage heating baking; the first-stage heating roasting comprises the following steps: raising the temperature to 700-900 ℃ at the rate of 2-8 ℃ per minute, preserving the heat for 3-6 hours, and cooling to room temperature along with the furnace; the two-stage heating roasting comprises the following steps: raising the temperature to 900 ℃ at the rate of 2-8 ℃ per minute, preserving the heat for 3-6 hours, then raising the temperature from 900 ℃ to 1300 ℃ at the rate of 1000 ℃ at the rate of 2-8 ℃ per minute, preserving the heat for 10-15 hours, and finally cooling the temperature to room temperature along with the furnace from 1300 ℃ at 1000 ℃ to obtain the catalyst; grinding the catalyst into powder, and pressing the powder into catalyst tablets by using pressure; heat treating the catalyst piece, heating to 700-900 deg.C at 2-8 deg.C/min, holding for 5-10 hr, cooling, taking out, crushing and sieving to obtain 60-80 mesh catalystCatalyst particles, namely the catalyst for preparing the synthesis gas by double reforming of the coke oven gas.
2. The preparation method of the catalyst for preparing the synthesis gas by double reforming of the coke oven gas, which is disclosed by claim 1, is characterized by comprising the following steps of: sequentially adding three substances of nickel salt, strontium salt, magnesium salt or magnesium oxide into deionized water or distilled water at room temperature according to the mol ratio of 0.05-0.5: 0.05-0.2: 0.95-0.5, and dissolving into a mixed solution; evaporating the mixed solution to dryness at a constant temperature of 80-120 ℃, or stirring at room temperature for 10-15h, standing for 10-15h and filtering to obtain a solid substance; baking the solid matter at 90-130 ℃ for 2-5 hours, and then adopting first-stage heating baking or second-stage heating baking; the first-stage heating roasting comprises the following steps: raising the temperature to 700-900 ℃ at the rate of 2-8 ℃ per minute, preserving the heat for 3-6 hours, and cooling to room temperature along with the furnace; the two-stage heating roasting comprises the following steps: raising the temperature to 900 ℃ at the rate of 2-8 ℃ per minute, preserving the heat for 3-6 hours, then raising the temperature from 900 ℃ to 1300 ℃ at the rate of 1000 ℃ at the rate of 2-8 ℃ per minute, preserving the heat for 10-15 hours, and finally cooling the temperature to room temperature along with the furnace from 1300 ℃ at 1000 ℃ to obtain the catalyst; grinding the catalyst into powder, and pressing the powder into catalyst tablets by using pressure; and (3) carrying out heat treatment on the catalyst piece, heating to 700-900 ℃ at the speed of 2-8 ℃ per minute, preserving the heat for 5-10 hours, cooling along with the furnace, taking out, crushing and screening to prepare catalyst particles of 60-80 meshes, namely the catalyst for preparing the synthesis gas by double reforming of the coke oven gas.
3. The method for preparing the catalyst for the synthesis gas through double reforming of coke oven gas according to claim 2, wherein the nickel salt, strontium salt and magnesium salt are respectively any one of nitrate, sulfate or carbonate of nickel, strontium and magnesium.
4. The application of the catalyst for coke oven gas double reforming synthesis gas in the coke oven gas carbon dioxide steam double reforming synthesis gas of claim 1; the process conditions of the application are as follows: the reaction temperature is 800-900 ℃, the reaction pressure is 1atm, and the space velocity is 1.2 multiplied by 104~3.2×105mL/g.h; steam of waterMolar sum of M with carbon dioxide(H2O(g)+CO2)Molar amount M with methaneCH4The ratio of (A) to (B) is: m(H2O(g)+CO2)∶MCH4=1∶1。
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