CN113617358A - Preparation method of methanation catalyst - Google Patents
Preparation method of methanation catalyst Download PDFInfo
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- CN113617358A CN113617358A CN202111075934.8A CN202111075934A CN113617358A CN 113617358 A CN113617358 A CN 113617358A CN 202111075934 A CN202111075934 A CN 202111075934A CN 113617358 A CN113617358 A CN 113617358A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 13
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 3
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 150000004645 aluminates Chemical class 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 35
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- -1 nickel aluminate Chemical class 0.000 description 18
- 229910052746 lanthanum Inorganic materials 0.000 description 17
- 229910052759 nickel Inorganic materials 0.000 description 17
- 239000000463 material Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229960001484 edetic acid Drugs 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- OXHNIMPTBAKYRS-UHFFFAOYSA-H lanthanum(3+);oxalate Chemical compound [La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OXHNIMPTBAKYRS-UHFFFAOYSA-H 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- B01J23/83—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 rare earths or actinides
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention provides a preparation method of a methanation catalyst, which comprises the following steps: (1) mixing and reacting an aluminum nitrate aqueous solution, a lanthanum nitrate aqueous solution, an organic acid and polyethylene glycol to obtain sol, drying and roasting to obtain a perovskite composite oxide carrier; (2) mixing oxalic acid, polyvinylpyrrolidone, nickel chloride and cobalt chloride to obtain a mixed solution, and aging, carrying out solid-liquid separation, drying and roasting to obtain precursor powder; (3) mixing the obtained perovskite composite oxide carrier, precursor powder, inorganic acid and water to obtain catalyst powder. The catalyst prepared by the invention has high activity, good stability, strong carbon deposition resistance and sulfur resistance and high conversion rate.
Description
Technical Field
The invention belongs to the technical field of methanation reaction, and particularly relates to a preparation method of a methanation catalyst.
Disclosure of Invention
The methanation reaction is widely applied, not only to coal pyrolysis gas, coke oven gas, biomass pyrolysis gas and CO2The methanation reaction of (A) and the synthesis of ammonia and the industries of fuel cells and the like, for removing H-rich2A small amount of CO in the system to prevent catalyst poisoning. Large amounts of CO and H in coal gasified synthesis gas, pyrolysis gas and coke oven gas by methanation reaction using methanation catalyst2And converting into methane fuel gas, namely natural gas for standby. The methanation catalyst is required to have high thermal stability, high mechanical strength, good selectivity and the like because the playing requirements in the aspect of gas purification are extremely strict (up to a few ppm). The high thermal stability ensures that the catalyst can bear larger temperature fluctuation, the good toxicity resistance can ensure that the catalyst can be corroded by a certain amount of poisons such as sulfur, arsenic, chlorine and other impurities, the activity of the catalyst can be well maintained, the poisons can be prevented from penetrating through a bed layer to influence the next process, the good selectivity can promote the methanation reaction to smoothly proceed and reduce the occurrence of side reactions, and the high mechanical strength can ensure that the catalyst keeps complete particles under abnormal conditions (such as pressure change, instant temperature fluctuation, liquid carrying and the like caused by vehicle jumping) and avoids crushing or pulverization.
The catalyst is the core of the methanation process, and the catalytic performance directly determines the operation effect of the whole methanation process. At present, the supported metal oxide catalyst is mainly used for methanation reaction and generally comprises active components, a carrier, an auxiliary agent and the like. The Ru-based catalyst has the characteristics of good low-temperature activity, high reaction rate and high selectivity, and researches show that after high-temperature roasting, due to Ru/Al2O3The interaction between the solid catalyst solution and Ru is weak, so that the activity of the catalyst is increased. But in the reaction Ru (CO) is easily formedxRu (CO) at high temperaturexSublimation occurs, so that the loss of the active component Ru causes the activity of the catalyst to be reduced; due to Al2O3Cheap and easily available, has excellentStructural morphology and surface properties, therefore, commercial methanation catalysts are based mostly on Al2O3As a carrier, but during calcination of the catalyst, Al2O3The NiO is easy to generate a nickel aluminate spinel structure which is difficult to reduce, so that the catalyst is difficult to reduce, and the catalytic performance of the catalyst is reduced. The assistant is a substance added into the catalyst to remarkably improve the activity of the catalyst, but researches show that the assistant can block catalyst pore channels along with the increase of the contents of Zr and Sm, so that the specific surface area, the pore volume and the pore diameter of the catalyst tend to be reduced, and the catalytic effect is influenced.
Therefore, the preparation of efficient methanation catalyst is one of the important points of the research of methanation technology.
Aiming at the defects of low activity, poor high-temperature stability, easy carbon deposition, poor sulfur resistance and the like of the methanation catalyst, the invention aims to provide a preparation method capable of obtaining the methanation catalyst with high activity, good stability, strong carbon deposition resistance and strong sulfur resistance.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a methanation catalyst, which comprises the following steps:
(1) mixing and reacting an aluminum nitrate aqueous solution, a lanthanum nitrate aqueous solution, an organic acid and polyethylene glycol to obtain sol, drying and roasting to obtain a perovskite composite oxide carrier;
(2) mixing oxalic acid, polyvinylpyrrolidone, nickel chloride and cobalt chloride to obtain a mixed solution, and aging, carrying out solid-liquid separation, drying and roasting to obtain precursor powder;
(3) mixing the obtained perovskite composite oxide carrier, precursor powder, inorganic acid and water to obtain catalyst powder.
Further, the amount of the substance of aluminum nitrate in the aqueous solution of aluminum nitrate is 0.5 to 3mol, further 1 to 2 mol;
the amount of the lanthanum nitrate in the aqueous solution of lanthanum nitrate is 0.5 to 3mol, and further 1 to 2 mol.
Further, in the step (1), the mass ratio of the mixed mass of the aqueous aluminum nitrate solution and the aqueous lanthanum nitrate solution to the organic acid is 1:0.1 to 0.6, and further 1:0.1 to 0.49.
Further, in the step (1), the mass ratio of the mixed mass of the aluminum nitrate aqueous solution and the lanthanum nitrate aqueous solution to the polyethylene glycol is 1:1 to 5, and further 1:1 to 3.
Further, (1) the mixing reaction temperature is 40-120 ℃, and the reaction time is 2-10 h; further, the reaction temperature is 50-90 ℃, and the reaction time is 5-8 hours;
the drying temperature is 60-150 ℃, and the drying time is 2-10 h; further, the drying temperature is 80-120 ℃, and the drying time is 2-8 hours;
the roasting temperature is 200-700 ℃, and the roasting time is 0.5-5 h; further, the roasting temperature is 200-500 ℃, and the roasting time is 2-8 hours.
Further, in the step (2), the pH value of the mixed solution is 7.5 to 10, preferably 8.
Further, (2) aging at 40-80 ℃ for 5-24 h; the drying temperature is 80-200 ℃, and the drying time is 8-36 h; the roasting temperature is 150-300 ℃, and the roasting time is 1-8 h.
Furthermore, the stoichiometric ratio of the nickel chloride to the cobalt chloride is 1: 1-3, preferably 1: 2.
The stoichiometric ratio is the ratio of the amounts of the substances.
Further, the perovskite oxide: the mass ratio of the precursor transition metal element composite oxide is 1-10: 1-20; further 1-5: 4-15; further 1-3: 4-10.
Further, the method also comprises the steps of mixing, ball-milling and granulating the catalyst powder, aluminate and graphite;
the mass of the mixed perovskite composite oxide carrier and precursor powder is as follows: the quality of aluminate is as follows: the mass ratio of the graphite is 80-100: 5-15: 1-10.
The invention has the following beneficial effects:
the catalyst prepared by the invention has the advantages of large surface area, pore volume and pore diameter, high activity, good mechanical strength, low abrasion rate and strong anti-carbon deposition capability.
Secondly, the methanation catalyst prepared by compounding the carrier with the perovskite structure and nickel cobaltate is used for preparing methane by hydrogenating carbon monoxide and carbon dioxide, and has excellent CO and CO2The conversion rate of CO is 98.4-99.6 percent, and the conversion rate of CO is 98.4-99.6 percent2The conversion rate is 65.2-72.1%.
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1
(1) Preparation of lanthanum aluminate carrier with perovskite structure
100mL of 2mol/L aluminum nitrate aqueous solution and 100mL of 2mol/L lanthanum nitrate aqueous solution are measured, the solutions are mixed under the condition of 60 ℃ water bath, 60g of citric acid and 200g of polyethylene glycol 2000 are used for fully dissolving the substances, and the substances are reacted for 6 hours in a constant-temperature water area at the temperature of 60 ℃ to obtain the lanthanum aluminate sol. And drying the sol at 90 ℃ for 6 hours, and roasting at 400 ℃ for 2 hours to obtain lanthanum aluminate solid.
(2) Preparation of catalyst precursor Nickel cobalt oxide
20g of H2C2O4·2H2Dissolving O and 10g of polyvinylpyrrolidone (PVP) in a mixed solution of 100mL of deionized water; 100mL of 1mol/L NiCl2·6H2O and 100mL of 2mol/L CoCl2·6H2Adding the O mixed solution into the mixed solution by a metering pump in a constant flow manner; the reaction temperature is controlled at 60 ℃, and NH is dropwise added3·H2And adjusting the pH value of the reaction system to 8 by O, continuing constant-temperature aging for 12 hours after the charging is finished, washing precipitates with deionized water and filtering after aging, putting the precipitates into a vacuum drying oven at 100 ℃, drying for 8-36 hours to obtain nickel cobaltate precursor powder, and roasting the powder at 300 ℃ for 4 hours, preferably to obtain the fibrous porous nickel cobaltate powder.
(3) Preparation of catalyst powder
Mixing lanthanum aluminate solid powder and fibrous porous nickel cobaltate powder in the steps according to the weight ratio of 1: 5, grinding the mixture to a particle size of 30um by a ball mill, adding 15mL of deionized water and 5mL of phosphoric acid, and mixing.
(4) Catalyst formation
The catalyst powder, the pure calcium aluminate cement and the graphite in the steps are mixed according to the mass ratio of 86: 9: 5, adding the mixture into a ball mill for ball milling, adding deionized water into the ball-milled materials for uniformly mixing, then granulating, finally pressing and forming into phi 7 multiplied by 8 multiplied by 2mm Raschig rings, namely the formed catalyst particles, curing for 8 hours under the steam pressure of 0.6MPa, and curing the catalyst for 12 hours at the temperature of 200 ℃ to obtain the catalyst A.
Example 2
(1) Preparation of lanthanum aluminate carrier with perovskite structure
100mL of 1mol/L aluminum nitrate aqueous solution and 100mL of 1mol/L lanthanum nitrate aqueous solution are weighed, the solutions are mixed under the condition of 60 ℃ water bath, 40g of citric acid and 200g of polyethylene glycol 600 are fully dissolved, and the materials are reacted for 6 hours in a constant-temperature water area at the temperature of 60 ℃ to obtain the lanthanum aluminate sol. And drying the sol at 90 ℃ for 6 hours, and roasting at 400 ℃ for 2 hours to obtain lanthanum aluminate solid.
(2) Preparation of catalyst precursor Nickel cobalt oxide
10g of H2C2O4·2H2Dissolving O and 10g of polyvinylpyrrolidone (PVP) in a mixed solution of 100mL of deionized water; 50mL of 1mol/L NiCl was added2·6H2O and 100mL of 1mol/L CoCl2·6H2Adding the O mixed solution into the mixed solution by a metering pump in a constant flow manner; the reaction temperature is controlled at 60 ℃, and NH is dropwise added3·H2And adjusting the pH value of the reaction system to 8 by O, continuing constant-temperature aging for 12 hours after the addition is finished, washing precipitates with deionized water and filtering after aging, putting the precipitates into a vacuum drying oven for 100 ℃, drying for 8-36 hours, preferably 16 hours to obtain nickel cobaltate precursor powder, and roasting the powder at 300 ℃ for 4 hours, preferably to obtain the fibrous porous nickel cobaltate powder.
(3) Preparation of catalyst powder
Mixing lanthanum aluminate solid powder and fibrous porous nickel cobaltate powder in the steps according to the weight ratio of 3: 10, grinding the mixture to a particle size of 30um by a ball mill, adding 15mL of deionized water and 5mL of phosphoric acid, and mixing.
(4) Catalyst formation
The catalyst powder, the pure calcium aluminate cement and the graphite in the steps are mixed according to the mass ratio of 86: 9: 5, adding the materials into a ball mill together for ball milling, adding deionized water into the materials after ball milling, uniformly mixing, then granulating, finally pressing and forming into phi 7 multiplied by 8 multiplied by 2mm Raschig rings, namely the formed catalyst particles, curing for 8 hours under the steam pressure of 0.6MPa, and curing the catalyst for 12 hours at the temperature of 200 ℃ to obtain the catalyst B.
Example 3
(1) Support preparation and (2) nickel cobaltate preparation reference example 2.
(3) Preparation of catalyst powder
Mixing lanthanum aluminate solid powder and fibrous porous nickel cobaltate powder in the steps according to the weight ratio of 1: 9, grinding the mixture to a particle size of 30um by a ball mill, adding 15mL of deionized water and 5mL of phosphoric acid, and mixing.
(4) Catalyst formation
The catalyst powder, the pure calcium aluminate cement and the graphite in the steps are mixed according to the mass ratio of 86: 9: 5, adding the materials into a ball mill together for ball milling, adding deionized water into the materials after ball milling, uniformly mixing, then granulating, finally pressing and forming into phi 7 multiplied by 8 multiplied by 2mm Raschig rings, namely the formed catalyst particles, curing for 8 hours under the steam pressure of 0.6MPa, and curing the catalyst for 12 hours at the temperature of 200 ℃ to obtain the catalyst C.
Example 4
(1) Preparation of lanthanum aluminate carrier with perovskite structure
100mL of 1mol/L aluminum nitrate aqueous solution and 100mL of 1mol/L lanthanum oxalate aqueous solution are measured, the solutions are mixed under the condition of 60 ℃ water bath, 30g of Ethylene Diamine Tetraacetic Acid (EDTA) and 200g of polyethylene glycol 600 are fully dissolved, and the materials are reacted for 6 hours in a constant-temperature water area at the temperature of 60 ℃ to obtain the lanthanum aluminate sol. And drying the sol at 90 ℃ for 6 hours, and roasting at 400 ℃ for 2 hours to obtain lanthanum aluminate solid.
(2) Preparation of catalyst precursor Nickel cobalt oxide
10g of H2C2O4·2H2Dissolving O and 10g of polyvinylpyrrolidone (PVP) in a mixed solution of 100mL of deionized water; 50mL of 1mol/L Ni (NO)3)2·6H2O and 100mL of 1mol/L Co (NO)3)2·6H2Adding the O mixed solution into the mixed solution by a metering pump in a constant flow manner; the reaction temperature is controlled at 60 ℃, and NH is dropwise added3·H2And adjusting the pH value of the reaction system to 8 by O, continuing constant-temperature aging for 12 hours after the addition is finished, washing precipitates with deionized water and filtering after aging, putting the precipitates into a vacuum drying oven for 100 ℃, drying for 8-36 hours, preferably 16 hours to obtain nickel cobaltate precursor powder, and roasting the powder at 300 ℃ for 4 hours, preferably to obtain the fibrous porous nickel cobaltate powder.
(3) Preparation of catalyst powder
Mixing lanthanum aluminate solid powder and fibrous porous nickel cobaltate powder in the steps according to the weight ratio of 3: 10, grinding the mixture to a particle size of 30um by a ball mill, adding 15mL of deionized water and 5mL of phosphoric acid, and mixing.
(4) Catalyst formation
The catalyst powder, the pure calcium aluminate cement and the graphite in the steps are mixed according to the mass ratio of 86: 9: 5, adding the materials into a ball mill together for ball milling, adding deionized water into the materials after ball milling, uniformly mixing, then granulating, finally pressing and forming into phi 7 multiplied by 8 multiplied by 2mm Raschig rings, namely the formed catalyst particles, curing for 8 hours under the steam pressure of 0.6MPa, and curing the catalyst for 12 hours at the temperature of 200 ℃ to obtain the catalyst D.
Example 5
(1) Preparation of lanthanum aluminate carrier with perovskite structure
100mL of 1mol/L aluminum nitrate aqueous solution and 100mL of 1mol/L lanthanum oxalate aqueous solution are measured, the solutions are mixed under the condition of 60 ℃ water bath, 30g of Ethylene Diamine Tetraacetic Acid (EDTA) and 200g of polyethylene glycol 600 are fully dissolved, and the materials are reacted for 6 hours in a constant-temperature water area at the temperature of 60 ℃ to obtain the lanthanum aluminate sol. And drying the sol at 90 ℃ for 6 hours, and roasting at 400 ℃ for 2 hours to obtain lanthanum aluminate solid.
(2) Preparation of catalyst precursor Nickel cobalt oxide
10g of H2C2O4·2H2Dissolving O and 10g of polyvinylpyrrolidone (PVP) in a mixed solution of 100mL of deionized water; 50mL of 1mol/L Ni (NO)3)2·6H2O and 100mL of 1mol/L Co (NO)3)2·6H2Adding the O mixed solution into the mixed solution by a metering pump in a constant flow manner; the reaction temperature is controlled at 60 ℃, and NH is dropwise added3·H2And adjusting the pH value of the reaction system to 8 by O, continuing constant-temperature aging for 12 hours after the addition is finished, washing precipitates with deionized water and filtering after aging, putting the precipitates into a vacuum drying oven for 100 ℃, drying for 8-36 hours, preferably 16 hours to obtain nickel cobaltate precursor powder, and roasting the powder at 300 ℃ for 4 hours, preferably to obtain the fibrous porous nickel cobaltate powder.
(3) Preparation of catalyst powder
Mixing lanthanum aluminate solid powder and fibrous porous nickel cobaltate powder in the steps according to the weight ratio of 1: 4, grinding the mixture to a particle size of 30um by a ball mill, adding 15mL of deionized water and 5mL of phosphoric acid, and mixing.
(4) Catalyst formation
The catalyst powder, the pure calcium aluminate cement and the graphite in the steps are mixed according to the mass ratio of 86: 9: 5, adding the materials into a ball mill together for ball milling, adding deionized water into the materials after ball milling, uniformly mixing, then granulating, finally pressing and forming into phi 7 multiplied by 8 multiplied by 2mm Raschig rings, namely the formed catalyst particles, curing for 8 hours under the steam pressure of 0.6MPa, and curing the catalyst for 12 hours at the temperature of 200 ℃ to obtain the catalyst E.
The catalyst was evaluated under the following conditions: a reactor: phi 35 x 5mm quartz tube, 20mL catalyst loading, catalyst bed height 500mm, reaction pressure: 3.0MPa, reactor space velocity: 2000h-1The reaction temperature: 550 ℃; the analytical detection uses an Shimadzu 2014 gas chromatograph, a TCD detector and a chromatographic column TDX-01, the carrier gas is helium, and the main detection gas is as follows: methane, carbon monoxide and carbon dioxide.
The physical properties of the catalysts in the examples of the present invention are shown in Table 1.
TABLE 1 physicochemical Properties of the catalyst
The raw material composition gas is shown in Table 2.
TABLE 2 evaluation of plant feed gas composition
TABLE 3 evaluation results of catalysts
As can be seen from the catalyst evaluation structure in Table 3, the methanation catalyst prepared by compounding the support having the perovskite structure and nickel cobaltate is excellent in CO and CO2And (4) conversion rate.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the methanation catalyst is characterized by comprising the following steps of:
(1) mixing and reacting an aluminum nitrate aqueous solution, a lanthanum nitrate aqueous solution, an organic acid and polyethylene glycol to obtain sol, drying and roasting to obtain a perovskite composite oxide carrier;
(2) mixing oxalic acid, polyvinylpyrrolidone, nickel chloride and cobalt chloride to obtain a mixed solution, and aging, carrying out solid-liquid separation, drying and roasting to obtain precursor powder;
(3) mixing the obtained perovskite composite oxide carrier, precursor powder, inorganic acid and water to obtain catalyst powder.
2. The method according to claim 1, wherein the amount of the substance of aluminum nitrate in the aqueous solution of aluminum nitrate is 0.5 to 3mol, further 1 to 2 mol;
the amount of the lanthanum nitrate in the aqueous solution of lanthanum nitrate is 0.5 to 3mol, and further 1 to 2 mol.
3. The method according to claim 1, wherein the mass ratio of the mixed mass of the aqueous aluminum nitrate solution and the aqueous lanthanum nitrate solution to the organic acid in (1) is 1:0.1 to 0.6, and further 1:0.1 to 0.49.
4. The production method according to claim 1, wherein in (1), the mass ratio of the mixed mass of the aqueous aluminum nitrate solution and the aqueous lanthanum nitrate solution to the mass of the polyethylene glycol is 1:1 to 5, and further 1:1 to 3.
5. The preparation method according to claim 1, wherein in the step (1), the mixing reaction temperature is 40 to 120 ℃, and the reaction time is 2 to 10 hours; further, the reaction temperature is 50-90 ℃, and the reaction time is 5-8 hours;
the drying temperature is 60-150 ℃, and the drying time is 2-10 h; further, the drying temperature is 80-120 ℃, and the drying time is 2-8 hours;
the roasting temperature is 200-700 ℃, and the roasting time is 0.5-5 h; further, the roasting temperature is 200-500 ℃, and the roasting time is 2-8 hours.
6. The method according to claim 1, wherein the mixed solution in (2) has a solution pH of 7.5 to 10, preferably 8.
7. The method according to claim 1, wherein in (2), the aging temperature is 40 to 80 ℃, and the reaction time is 5 to 24 hours; the drying temperature is 80-200 ℃, and the drying time is 8-36 h; the roasting temperature is 150-300 ℃, and the roasting time is 1-8 h.
8. The method according to claim 1, wherein the stoichiometric ratio of nickel chloride to cobalt chloride is 1:1 to 3, preferably 1: 2.
9. The production method according to claim 1, wherein the perovskite oxide: the mass ratio of the precursor transition metal element composite oxide is 1-10: 1-20; further 1-5: 4-15; further 1-3: 4-10.
10. The preparation method according to claim 1, further comprising the steps of mixing, ball-milling and granulating the catalyst powder, aluminate and graphite;
the mass of the mixed perovskite composite oxide carrier and precursor powder is as follows: the quality of aluminate is as follows: the mass ratio of the graphite is 80-100: 5-15: 1-10.
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