CN110639543A - Methanation catalyst and preparation method thereof - Google Patents
Methanation catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 216
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011029 spinel Substances 0.000 claims abstract description 24
- 229910026161 MgAl2O4 Inorganic materials 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004568 cement Substances 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 53
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 53
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 26
- 239000003513 alkali Substances 0.000 claims description 24
- 238000006386 neutralization reaction Methods 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000011265 semifinished product Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000002161 passivation Methods 0.000 claims description 6
- 229910002339 La(NO3)3 Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 5
- 229910020068 MgAl Inorganic materials 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 238000003878 thermal aging Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 239000003245 coal Substances 0.000 abstract description 10
- 239000003345 natural gas Substances 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000000571 coke Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002309 gasification Methods 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 carbon hydrocarbon Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides a methanation catalyst and a preparation method thereof, which belong to the technical field of preparation of natural gas by using coke oven gas or coal as a raw material, and comprise the following steps: (1) preparation of MgAl2O4A spinel carrier; (2) preparing catalyst powder; (3) adding catalyst powder, pure calcium aluminate cement and graphite into a ball mill together according to the mass ratio of 87-88: 8-9: 3-5 for ball milling, adding desalted water into the ball milled materials for mixing uniformly, then granulating, finally pressing and forming into a phi 3.5 multiplied by 3.5mm cylinder or a phi 11 multiplied by 8 multiplied by 2mm seven-hole column, namely formed catalyst particles, curing for 6-12 h under the steam pressure of 0.8MPa, and curing the catalyst for 8-20 h at the temperature of 100-200 ℃ to obtain an oxidation state finished catalyst; (4) physically dehydrating, reducing and passivating the oxidation state finished product catalyst to obtain the required pre-reduction type methanation catalyst. The catalyst has excellent low-temperature activity, high-temperature activity, hydrothermal stability and carbon deposition resistance, can be used for gas synthesis under the conditions of high temperature, high pressure and high space velocity, and is simple in preparation process and easy to control.
Description
Field of the method
The invention belongs to the technical field of natural gas preparation by using coke oven gas or coal as a raw material, and particularly relates to a methanation catalyst for a natural gas preparation technology and a preparation method thereof.
Background method
The basic energy pattern of China is characterized in that coal is rich, oil is poor and gas is little, coal accounts for more than 80% of the total reserves of energy resources, the recoverable reserves are in the third place of the world, the total amount of petroleum resources accounts for about 1.7% of the world, and the initial estimation of the natural gas resource amount is only about 1% of the total reserves of the world. However, in recent years, with the stricter national environmental protection requirements, the demand of natural gas as a high-quality and high-efficiency clean energy is continuously increased, and the serious 'gas shortage' mostly occurs in winter; how to solve the problem by using the existing resources is urgent, so that the domestic coal-based natural gas industry meets the vigorous development opportunity.
The coal-to-natural gas technology is an effective way for converting high-carbon energy into low-carbon and hydrogen-rich energy through processes of coal gasification, synthesis gas conversion, synthesis gas purification, methanation and the like, wherein the coal gasification and the methanation are key. At present, the coal gasification technology is mature, and the high-temperature methanation reaction is CO and CO2And H2Under the conditions of certain temperature, pressure and catalyst, the conversion process into methane, the methanation reactions are strong exothermic reactions, the temperature rise of about 72 ℃ can be caused by every 1 percent of CO conversion, and every 1 percent of CO2The conversion can cause the temperature rise of about 60 ℃, the content of the synthesis gas produced by coal gasification at present is higher and reaches 23-60%, and the high content of the synthesis gas produced by gasification puts higher requirements on methanation technology. Therefore, the key technologies to be solved by the current methanation technology are a high-temperature methanation catalyst and a high-temperature reactor. The selection of the high-temperature methanation catalyst is crucial, and the smooth proceeding of the reaction is directly determined.
In recent 10 years, a great deal of research work has been carried out on coal-based natural gas methanation catalysts by some domestic research institutions, universities and the like, and the main problems of poor high-temperature resistance and stability and easiness in sintering of the catalysts still exist; therefore, the development of a methanation catalyst with good high-temperature stability and strong sintering resistance is a main problem to be solved urgently by the technical personnel in the field.
Disclosure of Invention
Aiming at the defects of poor high-temperature resistance stability and easiness in sintering of the conventional methanation catalyst, the invention aims to provide the methanation catalyst and a preparation method thereof.
A preparation method of a methanation catalyst comprises the following steps:
(1) preparation of MgAl2O4A spinel carrier;
(2) the preparation method of the catalyst powder comprises the following steps:
a is Ni (NO)3)2、La(NO3)3、Zr(NO3)4And Mn (NO)3)2The nitrate mixed solution obtained by preparing the four solutions is metal liquid, the NiO content in the mixed solution is 60-120 g/L, and La2O3ZrO in an amount of 1 to 10g/L21-15 g/L, MnO2The content is 5-30 g/L;
b heating alkali liquor to 70-80 ℃ under stirring, carrying out neutralization reaction on the alkali liquor and the metal liquor, wherein the temperature of the neutralization reaction is 75-85 ℃, the time of the neutralization reaction is 60-120min, after the neutralization reaction is finished, carrying out thermal aging for 60-120min at 70-80 ℃, and then adding MgAl2O4Keeping the temperature of the spinel carrier at 70-80 ℃ and stirring for formation for 60-120 min;
after the formation of the catalyst C is finished, filtering and washing the material, drying the material at the temperature of 100-120 ℃ until the moisture of the material is lower than 5%, and finally roasting the material for 2-4 hours at the temperature of 550-700 ℃ to obtain catalyst powder;
(3) catalyst powder, pure calcium aluminate cement and graphite are mixed according to the mass ratio of 87-88: 8-9: 3-5, adding the materials into a ball mill for ball milling, adding desalted water into the materials after ball milling, uniformly mixing, granulating, finally pressing and forming the materials into a cylinder with the diameter of 3.5 multiplied by 3.5mm or a seven-hole column with the diameter of 11 multiplied by 8 multiplied by 2mm, namely the formed catalyst particles, maintaining the catalyst particles for 6-12 hours under the steam pressure of 0.8MPa, and maintaining the maintained catalyst for 8-20 hours at the temperature of 100-200 ℃ to obtain the oxidation state finished catalyst;
(4) and (3) dehydrating, reducing and passivating the oxidation state finished product catalyst to obtain the required pre-reduction type methanation catalyst.
In the technical scheme of the application: the catalyst carrier is Al with crystal phase2O3The (carrier) and MgO (auxiliary agent) are mixed, the thermal stability is good, the specific surface area is appropriate, and in addition, Al2O3MgO is a refractory material, and the strength and the thermal shock resistance of the carrier can be obviously improved by adding metal Ni, La, Zr and Mn, so that the strength activity and the high-temperature hydrothermal stability of the catalyst are improved; MgO is used as a reinforcing carrier, can be fully mixed with other components of the catalyst in the kneading process, and can form a solid solution carrier or a composite oxide with an alumina carrier in high-temperature roasting, so that the strength and the high-temperature hydrothermal stability of the catalyst are improved; preparation of MgAl2O4The auxiliary agent La is introduced after the spinel carrier, so that the dispersity of Ni and the anti-carbon deposition performance of the catalyst are improved, and the low-temperature activity and the high-temperature hydrothermal stability of the catalyst are improved; the water outlet time of the catalyst is effectively controlled in the physical dehydration step, so that the strength reduction of the complete methanation catalyst caused by a large amount of water outlet in a short time in the reduction process of the complete methanation catalyst can be avoided; the reduction degree of the complete methanation catalyst is improved through the reduction step, so that the reaction activity of the complete methanation catalyst is integrally improved; the stability of the catalyst is improved by passivation. The methanation catalyst prepared by the preparation method has excellent low-temperature activity, high-temperature activity, hydrothermal stability and anti-carbon deposition performance, and can be used for gas synthesis under the conditions of high temperature, high pressure and high airspeed; the preparation process is simple, easy to control, low in requirements on environmental conditions and equipment, and easy for industrial production, and the defects of poor high-temperature resistance stability and easy sintering of the existing methanation catalyst are overcome.
Preferably, MgAl is prepared in step (1)2O4The method of the spinel carrier is specifically：
adding pseudo-boehmite into desalted water, heating to 70-80 ℃, adding nitric acid under a stirring state, and strongly stirring for 1-3 hours under the condition that the stirring speed is 300 revolutions per minute to obtain an alumina gel solution;
b, adding active magnesium oxide into the desalted water, and grinding the active magnesium oxide by using a colloid mill until the active magnesium oxide completely passes through a specific granularity of 320 meshes to obtain magnesium oxide slurry;
c, slowly adding the magnesium oxide slurry into the aluminum solution, keeping the stirring speed at 300 r/min during the neutralization process, strongly stirring for 1-3h, heating to 70 ℃ after the addition, and aging for 1-3h to obtain MgAl2O4A spinel carrier.
Preferably, the mass ratio of the desalted water to the alumina and the nitric acid in the pseudo-boehmite in the step a is 18: 2.5: 0.15; the mass ratio of the active magnesium oxide to the desalted water in the step b is 12: 0.65: the mass of the active magnesium oxide is calculated by the mass of MgO.
Preferably, the NiO content in the step A is 70-110 g/L, and La2O3ZrO in an amount of 2 to 6g/L2The content is 2-6 g/L, and the NiO content is 8-20 g/L.
More preferably, the NiO content is 70-110 g/L, and the La content is2O3ZrO in an amount of 2 to 6g/L2MnO content of 2-6 g/L2The content is 8-20 g/L.
Preferably, in step B, the alkali liquor is Na2CO3And NaHCO3Mixed solution of Na2CO3And NaHCO3The mass of (2) is 3: 7-7: 3, the total concentration of the alkali liquor is 50-60 g/L.
Preferably, the material after ball milling in the step (3) needs to pass through a sieve with 250 meshes by more than 95 percent; the amount of the desalted water accounts for 30-50% of the mass ratio of the materials.
Preferably, the physical dehydration in step (4) is carried out by filling the oxidation state finished catalyst into a pre-reduction reactor and using N2Raising the temperature of the methanation catalyst to 120-150 ℃ at a temperature raising rate of 30-50 ℃/h, and removing physical water for 4-8 h; introducing H into the oxidation state methanation catalyst2-N2Mixed gas (es)Heating the temperature of the first oxidation state methanation catalyst to 450 ℃ at the heating rate of 20-30 ℃/h, preserving the heat for 15-20h to obtain a first methanation catalyst semi-finished product, heating the temperature of the methanation catalyst semi-finished product to 600 ℃ at the heating rate of 10-15 ℃/h, and preserving the heat for 6-10h to obtain a second methanation catalyst semi-finished product; introducing N into the second methanation catalyst semi-finished product2Air mixture of O2The content is 0.2%, the flow of air is controlled, the temperature of an air inlet of the reactor is not higher than 45 ℃, the temperature of the methanation catalyst bed layer is not higher than 50 ℃, the air is continuously introduced until the air is completely introduced and the temperature of the catalyst bed layer is not increased, namely the passivation is finished, and the material is discharged to obtain the required pre-reduction type methanation catalyst which is the finished product.
More preferably, H2-N2H in the mixed gas2The volume content is more than or equal to 70 percent.
Preferably, the methanation catalyst obtained by the method comprises the following components in parts by weight: 35-45 parts of Ni and La2O33 to 5 parts, MgO content of 4 to 6 parts, Al2O320 to 30 parts of ZrO24-8 parts of MnO2The content of the CaO is 5 to 10 parts, and the content of the CaO is 1 to 3 parts.
More preferably, the methanation catalyst obtained by the method is characterized in that: the methane catalyst comprises the following components in parts by weight: ni 40 parts, La2O34 parts of MgO, 5 parts of Al2O3Content 25 parts, ZrO2The content is 6 parts, MnO2The content is 7 parts, and the CaO content is 2 parts.
In the method scheme of the application:
compared with the prior art, the method has the beneficial effects that:
(1) the catalyst carrier is Al with crystal phase2O3The (carrier) and MgO (auxiliary agent) are mixed, the thermal stability is good, the specific surface area is appropriate, and A12O3MgO is a refractory material, and the strength and the thermal shock resistance of the carrier can be obviously improved and improved by adding metal Ni, La, Zr and MnStrength activity and high-temperature hydrothermal stability of the catalyst; MgO is used as a reinforcing carrier, can be fully mixed with other components of the catalyst in the kneading process, and can form a solid solution carrier or a composite oxide with an alumina carrier in high-temperature roasting, so that the strength and the high-temperature hydrothermal stability of the catalyst are improved; preparation of MgAl2O4After the spinel carrier is introduced, the assistant La, Zr and Mn are introduced to perform a synergistic effect, so that the dispersity of Ni and the anti-carbon deposition performance of the catalyst are improved, and the reducibility, low-temperature activity and high-temperature hydrothermal stability of the catalyst are improved;
(2) the methanation catalyst prepared by the preparation method has excellent low-temperature activity, high-temperature activity, hydrothermal stability and anti-carbon deposition performance, and can be used for gas synthesis under the conditions of high temperature, high pressure and high airspeed; the preparation process is simple, easy to control, low in requirements on environmental conditions and equipment, and easy for industrial production;
(3) the invention further adopts a two-stage heating reduction method in the reduction step to fully reduce the nickel oxide in the catalyst, and particularly can reduce the spinel nickel which is difficult to reduce in the prior art in the second-stage high-temperature reduction, so that the oxidation-state complete methanation catalyst is efficiently reduced into the simple substance-state complete methanation catalyst with high activity, the reduction degree of the complete methanation catalyst is improved, and the reaction activity of the complete methanation catalyst is integrally improved.
(4) The catalyst of the invention has stronger conversion capability to high carbon hydrocarbon, and not only increases CH4The yield of (2) and the cracking of the polycarbon to the desorbed carbon;
(5) the catalyst has high selectivity and conversion rate, no by-product is generated in the converted gas basically, the content of CO in the converted gas is low, and the CO is nearly completely converted;
(6) the catalyst has excellent heat resistance, can run for a long time at the temperature of 250-700 ℃, and does not shrink or deform; when the temperature fluctuation is large, the mechanical strength of the catalyst is stable and the catalyst is not easy to break;
(7) the catalyst has good strength and wear resistance, the catalyst is added with special auxiliary agents in the preparation process, the catalyst has high strength and good wear resistance, and the crushing and the wear of the catalyst can be effectively reduced in the use process, so that a catalyst bed layer can keep smaller and stable pressure drop.
Detailed Description
In order that those skilled in the art will better understand the method embodiments of the present invention, the present invention will be further described in detail with reference to the following specific examples.
Example 1
A preparation method of a methanation catalyst comprises the following steps:
(1) preparation of MgAl2O4A spinel carrier; preparation of MgAl2O4The method for preparing the spinel carrier comprises the following steps:
adding pseudo-boehmite into desalted water, heating to 70 ℃, adding nitric acid under a stirring state, and strongly stirring for 3 hours under the condition that the stirring speed is 300 r/min to obtain an alumina gel solution; the mass ratio of the alumina to the nitric acid in the desalted water and the pseudo-boehmite is 18: 2.5: 0.15; the mass ratio of the active magnesium oxide to the desalted water in the step b is 12: 0.65; the mass of the active magnesium oxide is calculated by the mass of MgO;
b, adding active magnesium oxide into the desalted water, and grinding the active magnesium oxide by using a colloid mill until the active magnesium oxide completely passes through 320 meshes of specific granularity to obtain magnesium oxide slurry;
c, slowly adding the magnesium oxide slurry into the aluminum solution, keeping the stirring speed at 300 r/min during the neutralization process, strongly stirring for 1h, heating to 70 ℃ after the addition, and aging for 1h to obtain MgAl2O4A spinel carrier;
(2) the preparation method of the catalyst powder comprises the following steps:
a is Ni (NO)3)2、La(NO3)3、Zr(NO3)4And Mn (NO)3)2The nitrate mixed liquor obtained by preparing the four solutions is the metal liquor, the NiO content in the mixed liquor is 60g/L, and La is contained in the mixed liquor2O3Content of 1g/L, ZrO2Content of 15g/L, MnO2The content is 30 g/L;
b, raising the alkali liquor with stirringHeating to 70 deg.C, performing neutralization reaction with metal liquid and alkali solution at 75 deg.C for 120min, heat aging at 70 deg.C for 120min, and adding MgAl2O4Keeping the temperature of the spinel carrier at 70-80 ℃ and stirring for formation for 60 min; the alkali liquor is Na2CO3And NaHCO3Mixed solution of Na2CO3And NaHCO3The mass of the alkali liquor is 3: 7, and the total concentration of the alkali liquor is 50 g/L;
after the formation of the catalyst C is finished, filtering and washing the material, drying the material at the temperature of 100-120 ℃ until the moisture of the material is lower than 5%, and finally roasting the material at the temperature of 550 ℃ for 4 hours to obtain catalyst powder;
(3) adding catalyst powder, pure calcium aluminate cement and graphite into a ball mill together according to the mass ratio of 87: 8: 5 for ball milling, adding desalted water into the ball milled materials for mixing uniformly, then granulating, finally pressing and forming into a phi 3.5 multiplied by 3.5mm cylinder or a phi 11 multiplied by 8 multiplied by 2mm seven-hole column, namely a formed catalyst particle, curing for 6 hours under the steam pressure of 0.8MPa, and curing the catalyst for 20 hours at the temperature of 100 ℃ to obtain an oxidation state finished catalyst; the passing rate of the ball-milled materials is more than 95% under 250 meshes; the amount of the desalted water accounts for 30 percent of the mass ratio of the materials;
(4) physically dehydrating, reducing and passivating the oxidation state finished product catalyst to obtain a required pre-reduction type methanation catalyst; the physical dehydration is specifically to fill an oxidation state finished product catalyst into a pre-reduction reactor and use N2Raising the temperature of the methanation catalyst to 120 ℃ at a temperature rise rate of 30 ℃/h, and removing the oxidation state methanation catalyst with physical water for 4-8 h; introducing H into the oxidation state methanation catalyst2-N2Mixing the gases, heating the temperature of the first oxidation state methanation catalyst to 400 ℃ at the heating rate of 20 ℃/h, preserving the heat for 20h to obtain a first methanation catalyst semi-finished product, heating the temperature of the methanation catalyst semi-finished product to 500 ℃ at the heating rate of 10 ℃/h, and preserving the heat for 10h to obtain a second methanation catalyst semi-finished product; introducing N into the second methanation catalyst semi-finished product2Air mixture of O2The content is 0.2%, and the flow rate of air is controlled to makeThe temperature of an air inlet of the reactor is not higher than 45 ℃, the temperature of the methanation catalyst bed layer is not higher than 50 ℃, the introduction is continued until the introduction of air is completed and the temperature of the catalyst bed layer is not increased, namely the passivation is finished, and the discharging is carried out to obtain the required pre-reduction type methanation catalyst which is a finished product; h2-N2H in the mixed gas2The volume content is more than or equal to 70 percent.
Example 2
A preparation method of a methanation catalyst comprises the following steps:
(1) preparation of MgAl2O4A spinel carrier; preparation of MgAl2O4The method for preparing the spinel carrier comprises the following steps:
adding pseudo-boehmite into desalted water, heating to 75 ℃, adding nitric acid under a stirring state, and strongly stirring for 2 hours under the condition that the stirring speed is 300 r/min to obtain an alumina gel solution; the mass ratio of the alumina to the nitric acid in the desalted water and the pseudo-boehmite is 18: 2.5: 0.15; the mass ratio of the active magnesium oxide to the desalted water in the step b is 12: 0.65; the mass of the active magnesium oxide is calculated by the mass of MgO;
b, adding active magnesium oxide into the desalted water, and grinding the active magnesium oxide by using a colloid mill until the active magnesium oxide completely passes through a specific granularity of 320 meshes to obtain magnesium oxide slurry;
c, slowly adding the magnesium oxide slurry into the aluminum solution, keeping the stirring speed at 300 r/min during the neutralization process, strongly stirring for 2 hours, heating to 70 ℃ after the addition, and aging for 2 hours to obtain MgAl2O4A spinel carrier;
(2) the preparation method of the catalyst powder comprises the following steps:
a is Ni (NO)3)2、La(NO3)3、Zr(NO3)4And Mn (NO)3)2The nitrate mixed liquor obtained by preparing the four solutions is the metal liquor, the NiO content in the mixed liquor is 90g/L, and La2O3ZrO in an amount of 6g/L2Content of 8g/L, MnO2The content is 17 g/L;
b, heating the alkali liquor to 75 ℃ while stirring, and performing neutralization reaction on the alkali liquor and the metal liquid, wherein the neutralization reaction is performedThe temperature of the neutralization reaction is 80 ℃, the time of the neutralization reaction is 90min, after the neutralization reaction is finished, the heat aging is carried out for 90min at the temperature of 75 ℃, and then MgAl is added2O4Keeping the temperature of the spinel carrier at 70-80 ℃ and stirring for 90 min; the alkali liquor is Na2CO3And NaHCO3Mixed solution of Na2CO3And NaHCO3The mass of the alkali liquor is 3: 2, and the total concentration of the alkali liquor is 55 g/L;
after the formation of the catalyst C is finished, filtering and washing the material, drying the material at the temperature of 100-120 ℃ until the moisture of the material is lower than 5%, and finally roasting the material at the temperature of 620 ℃ for 3 hours to obtain catalyst powder;
(3) adding catalyst powder, pure calcium aluminate cement and graphite into a ball mill together according to the mass ratio of 88: 8: 3 for ball milling, adding desalted water into the ball milled materials for mixing uniformly, then granulating, finally pressing and forming into a phi 3.5 x 3.5mm cylinder or a phi 11 x 8 x 2mm seven-hole column, namely a formed catalyst particle, curing for 9 hours under the steam pressure of 0.8MPa, and curing the catalyst for 14 hours at the temperature of 150 ℃ to obtain an oxidation state finished catalyst; the passing rate of the ball-milled materials is more than 95% under 250 meshes; the amount of the desalted water accounts for 40 percent of the mass ratio of the materials;
(4) physically dehydrating, reducing and passivating the oxidation state finished product catalyst to obtain a required pre-reduction type methanation catalyst; the physical dehydration is specifically to fill an oxidation state finished product catalyst into a pre-reduction reactor and use N2Raising the temperature of the methanation catalyst to 135 ℃ at the heating rate of 40 ℃/h, and removing the oxidation state methanation catalyst of physical water for 6 h; introducing H into the oxidation state methanation catalyst2-N2Mixing the gases, heating the temperature of the first oxidation state methanation catalyst to 420 ℃ at the heating rate of 25 ℃/h, preserving the heat for 17h to obtain a first methanation catalyst semi-finished product, heating the temperature of the methanation catalyst semi-finished product to 550 ℃ at the heating rate of 13 ℃/h, and preserving the heat for 8h to obtain a second methanation catalyst semi-finished product; introducing N into the second methanation catalyst semi-finished product2Air mixture of O2The content is 0.2 percent, the flow rate of the air is controlled, the temperature of the air inlet of the reactor is not higher than 45 ℃, and the methanation catalystThe temperature of the bed layer does not exceed 50 ℃, continuously introducing air until air is completely introduced and the temperature of the catalyst bed layer does not rise, namely, the passivation is finished, and discharging to obtain the required pre-reduction type methanation catalyst which is a finished product; h2-N2H in the mixed gas2The volume content is more than or equal to 70 percent.
Example 3
A preparation method of a methanation catalyst comprises the following steps:
(1) preparation of MgAl2O4A spinel carrier; preparation of MgAl2O4The method for preparing the spinel carrier comprises the following steps:
adding pseudo-boehmite into desalted water, heating to 80 ℃, adding nitric acid under a stirring state, and strongly stirring for 1h under the condition that the stirring speed is 300 r/min to obtain an alumina gel solution; the mass ratio of the alumina to the nitric acid in the desalted water and the pseudo-boehmite is 18: 2.5: 0.15; the mass ratio of the active magnesium oxide to the desalted water in the step b is 12: 0.65; the mass of the active magnesium oxide is calculated by the mass of MgO;
b, adding active magnesium oxide into the desalted water, and grinding the active magnesium oxide by using a colloid mill until the active magnesium oxide completely passes through a specific granularity of 320 meshes to obtain magnesium oxide slurry;
c, slowly adding the magnesium oxide slurry into the aluminum solution, keeping the stirring speed at 300 r/min during the neutralization process, strongly stirring for 3h, heating to 70 ℃ after the addition, and aging to obtain MgAl2O4A spinel carrier;
(2) the preparation method of the catalyst powder comprises the following steps:
a is Ni (NO)3)2、La(NO3)3、Zr(NO3)4And Mn (NO)3)2The nitrate mixed solution prepared from the four solutions is the metal solution, the NiO content in the mixed solution is 120g/L, and La is added2O3ZrO in an amount of 10g/L2Content of 1g/L, MnO2The content is 5 g/L;
b heating the alkali liquor to 80 ℃ while stirring, and performing neutralization reaction on the metal liquid and the alkali liquor, wherein the temperature of the neutralization reaction is 85 ℃, and the time of the neutralization reaction is 60minAfter the neutralization reaction is finished, the mixture is thermally aged for 60min at the temperature of 80 ℃, and then MgAl is added2O4Keeping the temperature of the spinel carrier at 70-80 ℃ and stirring for formation for 120 min; the alkali liquor is Na2CO3And NaHCO3Mixed solution of Na2CO3And NaHCO3The mass of the alkali liquor is 7: 3, and the total concentration of the alkali liquor is 60 g/L;
after the formation of the catalyst C is finished, filtering and washing the material, drying the material at the temperature of 100-120 ℃ until the moisture of the material is lower than 5%, and finally roasting the material at the temperature of 700 ℃ for 2 hours to obtain catalyst powder;
(3) adding catalyst powder, pure calcium aluminate cement and graphite into a ball mill together according to the mass ratio of 87: 9: 4 for ball milling, adding desalted water into the ball milled materials for mixing uniformly, then granulating, finally pressing and forming into a phi 3.5 x 3.5mm cylinder or a phi 11 x 8 x 2mm seven-hole column, namely a formed catalyst particle, curing for 12 hours under the steam pressure of 0.8MPa, and curing the catalyst for 8 hours at the temperature of 200 ℃ to obtain an oxidation state finished catalyst; the passing rate of the ball-milled materials is more than 95% under 250 meshes; the amount of the desalted water accounts for 50 percent of the mass ratio of the materials;
(4) physically dehydrating, reducing and passivating the oxidation state finished product catalyst to obtain a required pre-reduction type methanation catalyst; the physical dehydration is specifically to fill an oxidation state finished product catalyst into a pre-reduction reactor and use N2Heating the methanation catalyst to 150 ℃ at a heating rate of 50 ℃/h, and removing the oxidation state methanation catalyst with physical water for 4 h; introducing H into the oxidation state methanation catalyst2-N2Mixing the gases, heating the temperature of the first oxidation state methanation catalyst to 450 ℃ at the heating rate of 30 ℃/h, preserving the heat for 15h to obtain a first methanation catalyst semi-finished product, heating the temperature of the methanation catalyst semi-finished product to 600 ℃ at the heating rate of 15 ℃/h, and preserving the heat for 6h to obtain a second methanation catalyst semi-finished product; introducing N into the second methanation catalyst semi-finished product2Air mixture of O2The content is 0.2 percent, the flow rate of the air is controlled, the temperature of the air inlet of the reactor is not higher than 45 ℃, the temperature of the methanation catalyst bed layer is not higher than 50 ℃, and the introduction is continued until the completion of the methanation catalyst bed layerIntroducing air completely until the temperature of the catalyst bed layer does not rise, namely, considering that the passivation is finished, and discharging to obtain the required pre-reduction type methanation catalyst which is a finished product; h2-N2H in the mixed gas2The volume content is more than or equal to 70 percent.
Example 4
NiO content of 110g/L, La2O3ZrO in an amount of 6g/L2The contents were 2g/L and 8g/L, respectively, and the rest was the same as in example 2.
Example 5
NiO content is 70g/L, La2O3Content of 2g/L, ZrO2The contents were 6g/L and 20g/L, and the rest was the same as in example 1.
Example 6
The methanation catalyst obtained by the preparation method of the methanation catalyst based on any one of embodiments 1 to 5 comprises the following components in parts by weight: 35 parts of Ni, La2O33 parts of MgO, 4 parts of Al2O3Content 20 parts of ZrO2In an amount of 4 parts by weight, MnO2The content is 5 parts, and the CaO content is 1 part.
Example 7
The methanation catalyst obtained by the preparation method of the methanation catalyst based on any one of embodiments 1 to 5 comprises the following components in parts by weight: ni 40 parts, La2O34 parts of MgO, 5 parts of Al2O3Content 25 parts, ZrO2The content is 6 parts, MnO2The content is 7 parts, and the CaO content is 2 parts.
Example 8
The methanation catalyst obtained by the preparation method of the methanation catalyst based on any one of embodiments 1 to 5 comprises the following components in parts by weight: ni 45 parts, La2O35 parts of MgO, 6 parts of Al2O3Content of 30 parts, ZrO2In an amount of 8 parts by weight, MnO2The content is 10 parts, and the CaO content is 3 parts.
Test example 1
Harvesting the fruitThe specific surface areas (m) of the methanation catalysts obtained by the production methods of examples 1 to 5 were measured2The pore volume (mL/g), average pore diameter (nm) and side pressure crushing strength (N/particle) are shown in Table 1.
TABLE 1 physical parameters of methanation catalysts prepared by the preparation methods of examples 1 to 5 of the present application
As can be seen from Table 1, the physical parameters of the methanation catalysts prepared in examples 1 to 5 of the present application are superior to those of the methanation catalysts prepared by the conventional methods in the art.
Example 2
Activity measurement of methanation catalysts prepared in examples 1 to 5 of the present application, reactor size: the reactor is a stainless steel tube with phi 32 multiplied by 4mm, the size of the catalyst is phi 3.5 multiplied by 3.5mm, the loading amount of the original granularity is 20mL, the height of the catalyst bed layer is 500mm, and the activity of the catalyst is measured; an SC-2000 gas chromatograph, a thermal conductivity detector, a chromatographic column TDX-01, and a carrier gas H2Mainly analyzing CO and CO in the gas2、CH4。
Feed gas composition (v%) is shown in Table 2
TABLE 2 feed gas composition (v%)
| Name (R) | H2 | CH4 | CO | CO2 |
| Content (v%) | 41.0 | 46.0 | 9.0 | 4.0 |
The test conditions are shown in Table 3.
TABLE 3 test conditions
The test results are shown in table 4.
TABLE 4 test results of methanation catalysts prepared in examples 1 to 5 of the present application
| Catalyst and process for preparing same | CO conversion rate,% | CO2Conversion rate% |
| Example 1 | 99.3 | 65.8 |
| Example 2 | 99.7 | 67.4 |
| Example 3 | 99.4 | 66.9 |
| Example 4 | 99.5 | 65.5 |
| Example 5 | 99.2 | 66.3 |
As can be seen from Table 4, the methanation catalyst prepared herein compares to methanation catalyst prepared by conventional methods in the art, CO conversion and CO conversion2The conversion rate is high, the content of CO in the converted gas is low, the CO is nearly completely converted, and no by-product is generated in the converted gas, which shows that the methanation catalyst has better reaction performance.
Example 3
The methanation catalysts prepared in examples 1 to 5 of the present application were subjected to comparative tests before and after use, namely, the pressure of the new catalyst and the catalyst after 500 hours of operation were measured and shown in Table 5, the shrinkage was measured and shown in Table 6, the attrition was measured and shown in Table 7, and the carbon evolution resistance was measured and shown in Table 8.
TABLE 5 Strength test before and after use of the catalysts of examples 1 to 5 of the present application
As shown in Table 5, after the methanation catalysts prepared in examples 1 to 5 of the present application were operated for 500 hours, the methanation catalysts of the present application were stable in mechanical strength and less likely to be broken, compared with the methanation catalysts prepared by conventional methods in the art.
TABLE 6 measurement of shrinkage before and after use of the catalysts of examples 1 to 5 of the present application
As is apparent from Table 6, the methanation catalysts of the present application do not shrink or deform after 500 hours of operation compared with the methanation catalysts prepared by the conventional methods in the art, when the methanation catalysts prepared by examples 1 to 5 of the present application are operated.
Table 7 abrasion test before and after use of the catalysts of examples 1 to 5 of the present application
As shown in Table 7, after the methanation catalysts prepared in examples 1 to 5 of the present application run for 500 hours, the methanation catalysts of the present application have high strength and good wear resistance compared with the methanation catalysts prepared by conventional methods in the art.
TABLE 8 measurement of carbon deposition resistance before and after use of catalysts of examples 1 to 5 of the present application
As shown in Table 8, the methanation catalysts of the present application, which were prepared in examples 1 to 5 of the present application, were superior in carbon deposition resistance to the methanation catalysts prepared by the conventional method in the art after running for 500 hours.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the method of the present application, which fall within the scope of the present application.
Claims (10)
1. The preparation method of the methanation catalyst is characterized by comprising the following steps of:
(1) preparation of MgAl2O4A spinel carrier;
(2) the preparation method of the catalyst powder comprises the following steps:
a is Ni (NO)3)2、La(NO3)3、Zr(NO3)4And Mn (NO)3)2The nitrate mixed solution obtained by preparing the four solutions is metal liquid, the NiO content in the mixed solution is 60-120 g/L, and La2O3ZrO in an amount of 1 to 10g/L21-15 g/L, MnO2The content is 5-30 g/L;
b heating alkali liquor to 70-80 ℃ under stirring, carrying out neutralization reaction on the alkali liquor and the metal liquor, wherein the temperature of the neutralization reaction is 75-85 ℃, the time of the neutralization reaction is 60-120min, after the neutralization reaction is finished, carrying out thermal aging for 60-120min at 70-80 ℃, and then adding MgAl2O4Keeping the temperature of the spinel carrier at 70-80 ℃ and stirring for formation for 60-120 min;
after the formation of the catalyst C is finished, filtering and washing the material, drying the material at the temperature of 100-120 ℃ until the moisture of the material is lower than 5%, and finally roasting the material for 2-4 hours at the temperature of 550-700 ℃ to obtain catalyst powder;
(3) adding catalyst powder, pure calcium aluminate cement and graphite into a ball mill together according to the mass ratio of 87-88: 8-9: 3-5 for ball milling, adding desalted water into the ball milled materials for mixing uniformly, then granulating, finally pressing and forming into a phi 3.5 multiplied by 3.5mm cylinder or a phi 11 multiplied by 8 multiplied by 2mm seven-hole column, namely formed catalyst particles, curing for 6-12 h under the steam pressure of 0.8MPa, and curing the catalyst for 8-20 h at the temperature of 100-200 ℃ to obtain an oxidation state finished catalyst;
(4) and (3) dehydrating, reducing and passivating the oxidation state finished product catalyst to obtain the required pre-reduction type methanation catalyst.
2. The preparation method of methanation catalyst according to claim 1, wherein the MgAl is prepared in step (1)2O4The method for preparing the spinel carrier comprises the following steps:
adding pseudo-boehmite into desalted water, heating to 70-80 ℃, adding nitric acid under a stirring state, and strongly stirring for 1-3 hours under the condition that the stirring speed is 300 revolutions per minute to obtain an alumina gel solution;
b, adding active magnesium oxide into the desalted water, and grinding the active magnesium oxide by using a colloid mill until the active magnesium oxide completely passes through a specific granularity of 320 meshes to obtain magnesium oxide slurry;
c, slowly adding the magnesium oxide slurry into the aluminum solution, keeping the stirring speed at 300 r/min during the neutralization process, strongly stirring for 1-3h, heating to 70 ℃ after the addition, and aging for 1-3h to obtain MgAl2O4A spinel carrier.
3. The preparation method of a methanation catalyst according to claim 2, characterized in that the mass ratio of the desalted water to the alumina and the nitric acid in the pseudo-boehmite in the step a is 18: 2.5: 0.15; the mass ratio of the active magnesium oxide to the desalted water in the step b is 12: 0.65; the mass of the active magnesium oxide is calculated by the mass of MgO.
4. The preparation method of the methanation catalyst according to claim 1, wherein the NiO content in the step A is 70-110 g/L, and La is2O3ZrO in an amount of 2 to 6g/L2MnO content of 2-6 g/L2The content is 8-20 g/L.
5. The preparation method of methanation catalyst according to claim 1, wherein in step B, the alkali liquor is Na2CO3And NaHCO3Mixed solution of Na2CO3And NaHCO3The mass of the alkali liquor is 3: 7-7: 3, and the total concentration of the alkali liquor is 50-60 g/L.
6. The preparation method of the methanation catalyst according to claim 1, wherein the material subjected to ball milling in the step (3) has a passing rate of more than 95% at 250 meshes; the amount of the desalted water accounts for 30-50% of the mass ratio of the materials.
7. The preparation method of methanation catalyst as claimed in claim 1, wherein the physical dehydration in step (4) is carried out by filling the oxidation state finished catalyst into a pre-reduction reactor and using N2The methanation catalyst is heated at a temperature rise rate of 30-50 ℃/hThe temperature is raised to 120-150 ℃, and the physical water is removed for 4-8 hours; introducing H into the oxidation state methanation catalyst2-N2Mixing the gases, raising the temperature of the first oxidation state methanation catalyst to 450 ℃ at the temperature rise rate of 20-30 ℃/h, preserving the heat for 15-20h to obtain a first methanation catalyst semi-finished product, raising the temperature of the methanation catalyst semi-finished product to 600 ℃ at the temperature rise rate of 10-15 ℃/h, and preserving the heat for 6-10h to obtain a second methanation catalyst semi-finished product; introducing N into the second methanation catalyst semi-finished product2Air mixture of O2The content is 0.2%, the flow of air is controlled, the temperature of an air inlet of the reactor is not higher than 45 ℃, the temperature of the methanation catalyst bed layer is not higher than 50 ℃, the air is continuously introduced until the air is completely introduced and the temperature of the catalyst bed layer is not increased, namely the passivation is finished, and the material is discharged to obtain the required pre-reduction type methanation catalyst which is the finished product.
8. The preparation method of methanation catalyst according to claim 7, characterized in that H2-N2H in the mixed gas2The volume content is more than or equal to 70 percent.
9. The method according to any one of claims 1 to 8
The obtained methanation catalyst is characterized in that: the methane catalyst comprises the following components in parts by weight: 35-45 parts of Ni and La2O33 to 5 parts, MgO content of 4 to 6 parts, Al2O320 to 30 parts of ZrO24-8 parts of MnO2The content of the CaO is 5 to 10 parts, and the content of the CaO is 1 to 3 parts.
10. Methanation catalyst obtainable by the process according to claim 9, characterized in that: the methane catalyst comprises the following components in parts by weight: ni 40 parts, La2O34 parts of MgO, 5 parts of Al2O3Content 25 parts, ZrO2The content is 6 parts, MnO2The content is 7 parts, and the CaO content is 2 parts.
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Application publication date: 20200103 |