CN115957768A - Preparation method of isothermal methanation catalyst - Google Patents
Preparation method of isothermal methanation catalyst Download PDFInfo
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- CN115957768A CN115957768A CN202111187117.1A CN202111187117A CN115957768A CN 115957768 A CN115957768 A CN 115957768A CN 202111187117 A CN202111187117 A CN 202111187117A CN 115957768 A CN115957768 A CN 115957768A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 60
- 238000003756 stirring Methods 0.000 claims abstract description 46
- 238000001035 drying Methods 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 230000032683 aging Effects 0.000 claims abstract description 18
- 239000000084 colloidal system Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 16
- 238000004537 pulping Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 86
- 238000005303 weighing Methods 0.000 claims description 45
- 239000011259 mixed solution Substances 0.000 claims description 32
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [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 8
- 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 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 3
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 claims 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 1
- 239000000292 calcium oxide Substances 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 238000003483 aging Methods 0.000 abstract 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
A process for preparing isothermal methanation catalyst includes proportionally mixing Ni and Ce, adding the mixture to sodium carbonate solution for neutralizing, heating, stirring, ageing, laying aside and washing. Grinding silica and pseudo-boehmite by using a colloid mill to form a silica-alumina colloid, adding an active component into the silica-alumina colloid for pulping, filtering, drying, roasting, granulating and drying to obtain the isothermal catalyst. The catalyst has good activity stability in an isothermal reaction bed, and CO 2 Conversion rateCan reach more than 99.5 percent. The preparation method has the advantages of simple process, environmental protection, lower reaction temperature of the catalyst, lower energy consumption, simple operation, good stability, easy production and low cost, and has high catalytic activity and longer service life in an isothermal environment.
Description
Technical Field
The invention belongs to the technical field of catalysis, and relates to a preparation method of an isothermal methanation catalyst.
Background
Carbon neutralization refers to the total amount of greenhouse gas emission generated directly or indirectly in a certain time, and the carbon dioxide emission amount generated by the carbon dioxide neutralization is counteracted through the forms of afforestation, energy conservation, emission reduction and the like, so that zero emission of carbon dioxide is realized. Carbon neutralization is used as a novel environment-friendly form and adopted by more and more large-scale activities and meetings, so that green life and production are promoted, and green development of the whole society is realized.
China is a country rich in coal, poor in oil and less in gas, the development of the SNG technology for coal production and the construction of SNG devices for coal production have better economic benefits in the times with high oil prices, the problem of comprehensive utilization of coal resources is solved, the current situation of shortage of oil and gas resources in China is relieved, the energy safety in China is maintained, and CO is realized 2 The method has important significance for emission reduction and environmental protection.
In recent years, research on preparation of SNG methanation catalyst from coal-to-natural gas and coke oven gas by domestic scientific research institutes is more and more, but non-isothermal condition often occurs in the methanation reaction process, because methanation is exothermic reaction, and the overhigh temperature of a bed layer is not beneficial to the release of reaction heat and the methanation reaction, the aim needs to be fulfilledThe research on warm methanation catalytic technology, namely the southwest institute develops a Ni-based isothermal methanation catalyst, the catalyst prepares nitrates of magnesium and aluminum into a mixed salt solution according to n (Mg) n (Al) = 1:1, and a certain amount of gamma-Al is added 2 O 3 Powder (gamma-Al) 2 O 3 The powder accounts for 5 percent of the mass of the finished product carrier), a sodium carbonate solution is used for carrying out neutralization and precipitation reaction, and the end point pH of the reaction solution is controlled to be 8.5. Drying the precipitate at 120 deg.C, adding graphite as lubricant, tabletting, and roasting at 1200 deg.C for 4 hr to obtain the carrier. And (3) adding the carrier into a nickel nitrate solution with a certain concentration for dipping, drying at 120 ℃, and roasting at 350 ℃ for 4 hours to obtain the MgAl oxide-supported Ni-based catalyst, wherein the supported mass fraction of NiO is 15%. The catalyst is evaluated in an isothermal tube type integral reactor, and is mainly researched from the aspects of steam-gas ratio, pressure, temperature, airspeed, catalyst carbon deposition, catalyst characterization and the like, and the result shows that the catalyst has excellent performance. In addition, southwest institute filed a patent "an isothermal methanation catalyst and a preparation method thereof", application no: 201510725468.1 describes an isothermal catalyst preparation method using composite oxide formed from magnesium, aluminum and silicon as catalyst integer carrier and nickel as active component, which also shows good low-temperature activity in isothermal fixed bed.
The M-849 nickel-based methanation catalyst developed by Protecoratic technology Limited, purey, of Dajunghua, chinese academy of sciences for methanation of coke oven gas mainly takes metal Ni as an active component and additionally contains Al 2 O 3 、TiO 2 And Mn, zr, la and other elements, the catalyst has lower reaction temperature, avoids energy waste caused by repeated temperature rise and drop, and has high activity, high thermal stability, high mechanical strength, good toxicity resistance and good selectivity. The temperature is 250-600 ℃, the operation pressure is not limited, and the space velocity is 2000 h -1 ~10000h -1 ，CO、CO 2 The conversion rate is more than 95%. In 2011, the catalyst completes a full-flow continuous test for 1000h in a coke oven gas water-cooled low-temperature methanation project of cooperation of four units such as Shanxi Tongshidao, hangzhou Linda and the like, and the result shows that: at the temperature of 250-350 ℃, the pressure of 0.4MPa and the airspeed of 5000 h -1 ~7000h -1 Under the condition, the CO conversion rate reaches 100 percent, and CO 2 The conversion rate reaches more than 90 percent.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a preparation method of an isothermal methanation catalyst, and provides a catalyst which is simple in preparation process, green and environment-friendly, lower in reaction temperature, lower in energy consumption, simple to operate, good in stability, easy to produce, low in cost, high in catalytic activity and long in service life in an isothermal environment.
The main technical scheme of the invention is as follows: a preparation method of isothermal methanation catalyst is characterized by comprising the following steps: the preparation steps of the active phase are as follows: a, dissolving A, B metal salt in ionic water to obtain A, B ionic water solution; b, mixing the two solutions, and stirring to obtain a mixed solution; c, weighing the alkali solution prepared from the C, and heating; d, adding the mixed solution prepared in the step b into the step c for neutralization; e, adjusting the pH value of the neutralizing solution by using the prepared solution D; f, heating, stirring, aging, standing and washing; the preparation steps of the carrier are as follows: a, weighing E; b, weighing F; c, mixing the E and the F, slowly adding a nitric acid solution into the mixture, and grinding by using a colloid mill; (3) Adding the active phase prepared in the step (1) into the carrier prepared in the step (2) for pulping; and (4) filtering, drying, roasting, granulating and drying.
Further, the active phase is prepared into A, B mixed liquid, wherein a can be one or more of nickel nitrate, nickel carbonate, nickel oxide, nickel oxalate, ferric nitrate, ferric carbonate, zirconium nitrate and the like, and B can be one or more of lanthanum nitrate, cerium nitrate, lanthanum oxide, cerium oxide, palladium oxide and the like. The stirring time is 30min, the temperature is 60-90 ℃, and the optimal temperature is 70 ℃.
The active phase is prepared by preparing an alkali solution C from sodium carbonate or sodium bicarbonate at the temperature of 60-85 ℃, preferably 85 ℃.
And (c) preparing the active phase, wherein the neutralization time of the step d is 0.5-2h, and the temperature is 80-85 ℃, and preferably 85 ℃.
The active phase is prepared, the prepared D solution is ammonia solution, and the pH value is 7.2-7.5.
The active phase is prepared, the aging time is 1-4 h, and the temperature is increased to 85-90 ℃ after the neutralization is finished.
The carrier is prepared, wherein E is one or two of alumina and aluminum hydroxide, F is pseudo-boehmite, and nitric acid solution is added to adjust the pH to 1-3, preferably 1-2.
The loss on ignition of the roasting is less than 5 percent.
The catalyst prepared by the method has good activity stability in an isothermal reaction bed, and CO 2 The conversion rate can reach more than 99.5 percent. The preparation method has the advantages of simple process, environmental protection, lower reaction temperature of the catalyst, lower energy consumption, simple operation, good stability, easy production, low cost, high catalytic activity and long service life in an isothermal environment.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Weighing 168.75g of nickel nitrate to prepare 600mL of solution, weighing 34.5g of lanthanum nitrate to prepare 400mL of solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare a mixed solution, weighing 140g of sodium carbonate to prepare 2.8mL of solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1h at 85 ℃, adjusting the pH to 7.5 with ammonia water, stirring, and aging for 1h at 90 ℃. 18.9g of magnesium oxide and 66.6g of pseudo-boehmite are weighed and mixed, and nitric acid is slowly added into the mixture to adjust the pH to 2. Adding the active component into the magnesium-aluminum colloid, pulping for 0.5h at the temperature of 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 5%, and obtaining the isothermal catalyst labeled as sample 1.
Example 2
Weighing 168.75g of nickel nitrate to prepare 600mL of solution, weighing 34.5g of cerium nitrate to prepare 400mL of solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare a mixed solution, weighing 140g of sodium carbonate to prepare 2.8mL of solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1h at 85 ℃, adjusting the pH to 7.5 with ammonia water, stirring, and aging for 1h at 90 ℃. 18.9g of magnesium oxide and 66.6g of pseudo-boehmite are weighed and mixed, and nitric acid is slowly added into the mixture to adjust the pH to 2. Adding the active component into the magnesium-aluminum colloid, pulping for 0.5h at the temperature of 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 5%, and obtaining an isothermal catalyst labeled as sample 2.
Example 3
Weighing 168.75g of nickel nitrate to prepare 600mL of solution, weighing 34.5g of palladium oxide to prepare 400mL of solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare mixed solution, weighing 140g of sodium carbonate to prepare 2.8mL of solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1 hour at 85 ℃, adjusting the pH to 7.5 with ammonia water, stirring, and aging for 1h at 90 ℃. 18.9g of magnesium oxide and 66.6g of pseudo-boehmite are weighed and mixed, and nitric acid is slowly added to the mixture to adjust the pH to 2. Adding the active component into the magnesium-aluminum colloid, pulping for 0.5h at the temperature of 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 5%, and obtaining an isothermal catalyst labeled as sample 3.
Example 4
Weighing 168.75g of a mixture of ferric nitrate and nickel nitrate to prepare a 600mL solution, weighing 34.5g of zirconium nitrate to prepare a 400mL solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare a mixed solution, weighing 140g of sodium carbonate to prepare a 2.8mL solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1h at 85 ℃, adjusting the pH value to 7.5 with ammonia water, stirring, and aging for 1h at 90 ℃. 18.9g of magnesium oxide and 66.6g of pseudo-boehmite are weighed and mixed, and nitric acid is slowly added to the mixture to adjust the pH to 2. Adding the active component into the magnesium-aluminum colloid, pulping for 0.5h at 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 5%, and obtaining an isothermal catalyst labeled as sample 4.
Example 5
Weighing 168.75g of nickel nitrate to prepare 600mL of solution, weighing 34.5g of cerium nitrate to prepare 400mL of solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare a mixed solution, weighing 140g of sodium carbonate to prepare 2.8mL of solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1h at 85 ℃, adjusting the pH to 7.5 with ammonia water, stirring, and aging for 1h at 90 ℃. 18.9g of magnesium hydroxide and 66.6g of pseudo-boehmite are weighed and mixed, and nitric acid is slowly added to the mixture to adjust the pH to 2. Adding the active component into the magnesium-aluminum colloid, pulping for 0.5h at 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 5%, and obtaining an isothermal catalyst labeled as sample 5.
Example 6
Weighing 168.75g of nickel nitrate to prepare 600mL of solution, weighing 34.5g of cerium nitrate to prepare 400mL of solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare a mixed solution, weighing 140g of sodium carbonate to prepare 2.8mL of solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1h at 85 ℃, adjusting the pH to 7.5 by using ammonia water, stirring at 90 ℃, and aging for 1h. 18.9g of silica and 66.6g of pseudo-boehmite were weighed and mixed, and nitric acid was slowly added to the mixture to adjust the pH to 2. Adding the active component into the silicon-aluminum colloid for pulping for 0.5h at the temperature of 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 5%, and obtaining an isothermal catalyst labeled as sample 6.
Example 7
Weighing 168.75g of nickel nitrate to prepare 600mL of solution, weighing 34.5g of cerium nitrate to prepare 400mL of solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare mixed solution, weighing 140g of sodium carbonate to prepare 2.8mL of solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1h at 85 ℃, adjusting the pH to 7.5 with ammonia water, stirring, and aging for 1h at 90 ℃. 18.9g of silica and 66.6g of pseudo-boehmite were weighed and mixed, and nitric acid was slowly added to the mixture to adjust the pH to 3. Adding the active component into the silicon-aluminum colloid for pulping for 0.5h at the temperature of 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 5%, and obtaining an isothermal catalyst labeled as sample 7.
Example 8
Weighing 168.75g of nickel nitrate to prepare 600mL of solution, weighing 34.5g of cerium nitrate to prepare 400mL of solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare a mixed solution, weighing 140g of sodium carbonate to prepare 2.8mL of solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1h at 85 ℃, adjusting the pH to 7.5 with ammonia water, stirring, and aging for 1h at 90 ℃. 18.9g of silica and 66.6g of pseudo-boehmite were mixed, and nitric acid was slowly added to the mixture to adjust the pH to 1. Adding the active component into the silicon-aluminum colloid for pulping for 0.5h at the temperature of 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 5%, and obtaining the isothermal catalyst labeled as sample 8.
Example 9
Weighing 168.75g of nickel nitrate to prepare 600mL of solution, weighing 34.5g of cerium nitrate to prepare 400mL of solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare a mixed solution, weighing 140g of sodium carbonate to prepare 2.8mL of solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1h at 85 ℃, adjusting the pH to 7.5 with ammonia water, stirring, and aging for 1h at 90 ℃. 18.9g of magnesium oxide and 66.6g of pseudo-boehmite are weighed and mixed, and nitric acid is slowly added into the mixture to adjust the pH to 2. Adding the active component into the magnesium-aluminum colloid, pulping for 0.5h at the temperature of 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 1%, and obtaining an isothermal catalyst labeled as sample 9.
Example 10
Weighing 168.75g of nickel nitrate to prepare 600mL of solution, weighing 34.5g of lanthanum nitrate to prepare 400mL of solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare a mixed solution, weighing 140g of sodium carbonate to prepare 2.8mL of solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1h at 85 ℃, adjusting the pH to 7.5 with ammonia water, stirring, and aging for 1h at 90 ℃. 18.9g of magnesium oxide and 66.6g of pseudo-boehmite are weighed and mixed, and nitric acid is slowly added into the mixture to adjust the pH to 2. Adding the active component into the magnesium-aluminum colloid, pulping for 0.5h at 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 3%, and obtaining an isothermal catalyst labeled as a sample 10.
Example 11
Weighing 168.75g of nickel nitrate to prepare 600mL of solution, weighing 34.5g of lanthanum nitrate to prepare 400mL of solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare mixed solution, weighing 140g of sodium carbonate to prepare 2.8mL of solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1 hour at 85 ℃, adjusting the pH to 7.5 with ammonia water, stirring, and aging for 1h at 90 ℃. 18.9g of magnesium oxide and 66.6g of pseudo-boehmite are weighed and mixed, and nitric acid is slowly added into the mixture to adjust the pH to 2. Adding the active component into the magnesium-aluminum colloid, pulping for 0.5h at the temperature of 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 3%, and obtaining an isothermal catalyst labeled as sample 11.
Example 12
Weighing 168.75g of nickel nitrate to prepare 600mL of solution, weighing 34.5g of zirconium nitrate to prepare 400mL of solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare a mixed solution, weighing 140g of sodium carbonate to prepare 2.8mL of solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1h at 85 ℃, adjusting the pH to 7.5 with ammonia water, stirring, and aging for 1h at 90 ℃. 18.9g of magnesium oxide and 66.6g of pseudo-boehmite are weighed and mixed, and nitric acid is slowly added into the mixture to adjust the pH to 2. Adding the active component into the magnesium-aluminum colloid, pulping for 0.5h at the temperature of 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 3%, and obtaining the isothermal catalyst labeled as sample 12.
Example 13
Weighing 168.75g of nickel nitrate to prepare 600mL of solution, weighing 34.5g of a mixture of cerium nitrate and lanthanum nitrate to prepare 400mL of solution, mixing the two solutions, heating to 70 ℃, stirring for 0.5h to prepare a mixed solution, weighing 140g of sodium carbonate to prepare 2.8mL of solution, heating to 80 ℃, adding the two mixed solutions into the sodium carbonate solution under the stirring condition, neutralizing for 1h at 85 ℃, adjusting the pH to 7.5 with ammonia water, stirring, and aging for 1h at 90 ℃. 18.9g of magnesium oxide and 66.6g of pseudo-boehmite are weighed and mixed, and nitric acid is slowly added into the mixture to adjust the pH to 2. Adding the active component into the magnesium-aluminum colloid, pulping for 0.5h at the temperature of 60 ℃, filtering, drying, roasting, granulating, drying, controlling the loss on ignition to be 3%, and obtaining the isothermal catalyst labeled as sample 13.
Reducing the sample catalyst at 400 deg.C for 4 hr, and reacting at 280 deg.C and 3.0 MPa CO 10% CO 2 5%、C 2 H 6 4%、H 2 55%, the balance being N 2 The space velocity is 8000 h －1 Under the condition, the methanation performance of the sample catalyst in the isothermal reaction bed is evaluated, the catalyst sample 6 has the optimal activity stability, the CO conversion rate reaches over 99.5 percent, and CO 2 The conversion rate reaches more than 99.5 percent, and obvious inactivation does not occur in the investigation time. The data are shown in table 1 below.
Table 1 example sample performance test data
| Sample | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 |
| Percent conversion of CO% | 94.5 | 92.5 | 96.8 | 97.6 | 99.3 | 99.8 | 99.4 | 99.6 | 99.7 | 95.6 | 99.6 | 99.7 | 99.6 |
| CO 2 Conversion rate% | 93.5 | 96.8 | 98.7 | 99.5 | 99.2 | 99.7 | 99.7 | 99.3 | 99.3 | 99.6 | 99.7 | 99.9 | 99.5 |
Claims (10)
1. A preparation method of an isothermal methanation catalyst is characterized by comprising the following steps: preparing an active phase: a, dissolving A, B metal salt in ionic water to obtain A, B ionic water solution; b, mixing the two solutions, and stirring to obtain a mixed solution; c, weighing the alkali solution prepared from the C, and heating; d, adding the mixed solution prepared in the step b into the step c for neutralization; e, adjusting the pH value of the neutralizing solution by using the prepared solution D; f, heating, stirring, aging, standing and washing; the preparation method of the carrier comprises the following steps: a, weighing E; b, weighing F; c, mixing the E and the F, slowly adding a nitric acid solution into the mixture, and grinding by using a colloid mill; adding the prepared active phase into a carrier, pulping, filtering, drying, roasting, granulating and drying to obtain the isothermal methanation catalyst.
2. The preparation method of the catalyst according to claim 1, wherein a mixed solution of A, B as an active phase is prepared, wherein a is selected from one or more of nickel nitrate, nickel carbonate, nickel oxide, nickel oxalate, iron nitrate, iron carbonate, zirconium nitrate, and the like, and wherein B is selected from one or more of lanthanum nitrate, cerium nitrate, lanthanum oxide, cerium oxide, palladium oxide, and the like.
3. The method for preparing the catalyst according to claim 1, wherein the stirring time for preparing the mixed solution of the active phase A, B is 30min, and the temperature is 60-90 ℃, and preferably 70 ℃.
4. The process for preparing the catalyst according to claim 1, wherein the alkaline solution C is sodium carbonate or sodium bicarbonate at a temperature of 60 ℃ to 85 ℃, preferably 85 ℃.
5. The process for preparing the catalyst according to claim 1, wherein the neutralization time in step d is 0.5 to 2 hours, and the temperature is 80 ℃ to 85 ℃, preferably 85 ℃.
6. The method for preparing the catalyst according to claim 1, wherein the prepared solution D is an ammonia solution and has a pH value of 7.2 to 7.5.
7. The method for preparing the catalyst according to claim 1, wherein in the step f, the aging time is 1h to 4h, and the temperature is raised to 85 ℃ to 90 ℃ after the neutralization is finished.
8. The method for preparing the catalyst according to claim 1, wherein E is one or two of magnesium oxide, calcium oxide, silicon oxide, aluminum oxide and aluminum hydroxide, F is pseudo-boehmite, and the nitric acid solution is added to the mixture to adjust the pH to 1-3.
9. The method for preparing the catalyst according to claim 8, wherein a nitric acid solution is added to the mixture to adjust the pH to 1 to 2.
10. The process of claim 1, wherein the calcined has a loss on ignition of less than 5%.
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| US20030144366A1 (en) * | 2002-01-29 | 2003-07-31 | Michel Daage | Catalyst regeneration |
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