CN107376915B - Carbon dioxide methanation catalyst and preparation method thereof - Google Patents
Carbon dioxide methanation catalyst and preparation method thereof Download PDFInfo
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- CN107376915B CN107376915B CN201710739812.1A CN201710739812A CN107376915B CN 107376915 B CN107376915 B CN 107376915B CN 201710739812 A CN201710739812 A CN 201710739812A CN 107376915 B CN107376915 B CN 107376915B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 38
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 79
- 239000010455 vermiculite Substances 0.000 claims abstract description 79
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 79
- 239000002994 raw material Substances 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004568 cement Substances 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 17
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 17
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 17
- 238000005470 impregnation Methods 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000003837 high-temperature calcination Methods 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000000748 compression moulding Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000007781 pre-processing Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 3
- 238000007385 chemical modification Methods 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical group [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 238000011068 loading method Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 238000012216 screening Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000006004 Quartz sand Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 229910001453 nickel ion Inorganic materials 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-YPZZEJLDSA-N carbane Chemical group [10CH4] VNWKTOKETHGBQD-YPZZEJLDSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
Abstract
The invention discloses a carbon dioxide methanation catalyst and a preparation method thereof, wherein the carbon dioxide methanation catalyst comprises a carrier and an active component, and the carrier is composed of the following raw materials in parts by weight: 70-80 parts of vermiculite and Al2O38 to 15 parts of SiO25-10 parts of carbon powder, 5-10 parts of carbon powder and 5-15 parts of cement powder, wherein the active component is one or a combination of at least two of Ni, Fe and Co, the catalyst is prepared by the steps of carrier pretreatment, molding, crushing, loading and the like, and an excess impregnation method is adopted to prepare the loaded carbon dioxide methanation catalyst.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide methanation, and particularly relates to a carbon dioxide methanation catalyst and a preparation method thereof.
Background
With the rapid development of global economy and the gradual reduction of natural resources, carbon dioxide discharged to the nature by human beings has already seriously influenced the ecological environment, so that the recycling of the carbon dioxide and the conversion of the carbon dioxide into fuel with high added value have very important significance. The carbon dioxide is methanated, and the carbon dioxide and the hydrogen are used as raw materials to synthesize the clean fuel methane with high calorific value (the combustion calorific value is 891kJ/mol), so that on one hand, the carbon dioxide in the nature is reduced, the effective utilization of resources is realized, on the other hand, the clean energy methane is synthesized, and the method has the characteristics of simple process, less investment and high return.
Chinese patent CN106311242A discloses a carbon dioxide methanation catalyst and a preparation method thereof, wherein the catalyst consists of a composite carrier and an active component, wherein the weight ratio of the composite carrier to the active component is 84-90 wt% and 10-16 wt%; wherein the composite carrier is composed of gamma-Al2O3With water-soluble metal oxides, gamma-Al2O3The mass ratio of the water soluble metal oxide to the water soluble metal oxide is 77-86: 2-10; the active component is Ni and exists in the catalyst in the form of NiO, and the carbon dioxide methanation catalyst prepared by the method is used under normal pressure conditions, but the activity is not high,The stability is not good.
Chinese patent CN101773833A discloses a carbon dioxide methanation catalyst and a preparation method thereof, the catalyst is prepared by taking aerogel oxide as a carrier and adding an auxiliary agent, the active component is nickel, the auxiliary agent is alkali metal or alkaline earth metal, the aerogel oxide carrier is silicon dioxide, titanium dioxide, zirconium dioxide, aluminum oxide or a compound thereof, and the catalyst comprises the following components in percentage by weight: the nickel content is 5-40 wt%, and the auxiliary agent content is 0.01-30 wt%. The catalyst prepared by the method can effectively catalyze the hydrogenation of carbon dioxide to produce methane under the reaction conditions of normal pressure, a space velocity of 2000-20000H-1, a H2/CO 2: 4:1 and a temperature of 300-500 ℃, but the carrier is an inert carrier, and the loaded active component is not uniformly distributed on the surface of the carrier, so that the activity is insufficient and the stability is poor.
Disclosure of Invention
The invention aims at the problems and provides a carbon dioxide methanation catalyst and a preparation method thereof.
The technical scheme adopted by the invention for solving the problems is as follows:
the carbon dioxide methanation catalyst comprises a carrier and active components, wherein the carrier is composed of the following raw materials in parts by weight: 70-80 parts of vermiculite, 78-15 parts of Al2O38, 25-10 parts of SiO, 5-10 parts of carbon powder and 5-15 parts of cement powder, wherein the active component is one or a combination of at least two of Ni, Fe and Co.
Further, the carrier is composed of the following raw materials in parts by weight: 75 parts of vermiculite, 310 parts of Al2O, 27 parts of SiO, 7 parts of carbon powder and 10 parts of cement powder.
The preparation method comprises the following steps:
step S10, preprocessing vermiculite: putting vermiculite into a muffle furnace, and performing high-temperature calcination expansion, wherein the temperature in the muffle furnace is controlled to be 600-750 ℃, and the calcination time is 1-2 hours;
step S20, crushing of raw materials: mixing vermiculite and Al2O3、SiO2Crushing, ball milling, filtering with 1000 mesh sieve to obtain powder with diameter less than 15 microns, ball milling the cement powder and carbon powder to obtain the final productA powder having a diameter of less than 15 microns;
step S30, forming of raw materials: putting the raw material powder into an oven at 95-105 ℃ for drying treatment, weighing the raw materials according to the weight parts, adding distilled water for mixing and stirring, and performing compression molding by using a molding machine;
step S40, pretreatment of the carrier: drying the molded raw materials in an oven at 95-105 ℃ for 6-12 hours, naturally airing, and then carrying out vacuum-pumping treatment;
step S50, preparation of catalyst: the active ingredient is deposited on the support using an excess impregnation process.
Further, in step S10, before placing into a muffle furnace for high-temperature calcination, acid treatment is performed, and the treatment process includes:
step S11, putting vermiculite into a 3-10% nitric acid solution, and treating for 2 hours at 45 ℃;
and step S12, putting the acidified vermiculite into deionized water for cleaning.
Further, in step S30, the raw material is compressed and molded, and then oxidized for 10 to 15 days in an environment with an air humidity of 100%.
Further, in step S40, the pre-treatment of the carrier includes crushing the molded carrier, and screening carrier particles having a size of 20 to 40 mesh.
Further, in step S40, the pretreatment of the carrier is to perform a chemical modification treatment on the carrier, specifically, a treatment with a 3-10% nitric acid solution at 45 ℃ for 2 hours.
Further, in step S50, the immersion method includes the steps of:
step S51, preparing a metal salt solution with the cation concentration of 5-10 mol/L; step S52, placing the treated carrier into a metal salt solution, and stirring and mixing for 10-20 minutes; step S53, after dipping, putting the dipped material into an oven at the temperature of 95-105 ℃ for drying for 2 hours; and step S54, calcining the dried catalyst in a furnace at 300-600 ℃.
Further, in step S53, the impregnated catalyst was sealed and cured at room temperature for 24 hours.
Further, the metal salt is one or a combination of at least two of soluble salts of nickel, iron and cobalt.
The invention has the advantages that:
1. according to the invention, natural ore vermiculite is used as a catalyst carrier, the dispersibility of active components in a bulk phase is high, and the catalytic activity of the catalyst is further improved by loading the active components through an impregnation method;
2. the vermiculite used in the invention has low cost, the production cost of the catalyst is greatly reduced, the universality is improved, and the low-load active component can have higher conversion rate;
in addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below with reference to specific embodiments.
Detailed Description
The invention is described in detail below with reference to examples, but the invention can be implemented in many different ways as defined and covered by the claims.
Example 1
Carbon dioxide methanation catalyst and preparation method thereof
The catalyst carrier consists of the following raw materials in parts by weight: 75 parts of vermiculite and Al2O310 parts of SiO27 parts of carbon powder and 10 parts of cement powder.
The preparation steps are as follows:
step S10, preprocessing vermiculite: firstly, putting vermiculite into 6% nitric acid solution, treating for 2 hours at 45 ℃, and putting acidified vermiculite into deionized water for cleaning; then putting the vermiculite into a muffle furnace, and carrying out high-temperature calcination expansion, wherein the temperature in the muffle furnace is controlled at 680 ℃, and the calcination time is 1.5 hours;
the vermiculite can be subjected to high-temperature calcination to remove volatile impurities, the volume of the vermiculite can be expanded by 6-20 times, the rich specific surface area of the vermiculite is beneficial to loading of active components on the inner surface and the outer surface of the vermiculite, soluble liquid substances in the vermiculite can be dissolved by acid washing, the inner surface area of the vermiculite is further improved, the dispersibility of the active components is improved, and the activity of the catalyst is increased.
Step S20, crushing of raw materials: mixing vermiculite and Al2O3、SiO2Firstly crushing and then ball-milling, filtering by using a 1000-mesh sieve to obtain powder with the diameter of less than 15 microns, and further ball-milling the cement powder and the carbon powder to obtain powder with the diameter of less than 15 microns;
step S30, forming of raw materials: putting the raw material powder into a 105 ℃ oven for drying treatment, weighing the raw materials according to the weight parts, adding distilled water for mixing and stirring, performing compression molding by using a molding machine, and then, oxidizing for 10-15 days in an environment with the air humidity of 100%;
step S40, pretreatment of the carrier: crushing the formed raw materials, screening carrier particles with the size of 20-40 meshes, putting the carrier particles into a drying oven with the temperature of 105 ℃ for drying for 8 hours, naturally drying the carrier particles, and then vacuumizing the carrier particles;
before catalyst impregnation, the carrier is vacuumized, gas in the carrier is pumped out, the adsorption capacity of the carrier is improved, and the loading capacity of metal is guaranteed.
Step S50, preparation of catalyst: depositing the active component on the support by means of an excess impregnation: 1. preparing a nickel nitrate solution with the nickel ion concentration of 8 mol/L; 2. placing the treated carrier into a nickel nitrate solution, and stirring and mixing for 15 minutes; 3. after dipping, putting the mixture into a 105 ℃ oven for drying for 2 hours; 4. the dried catalyst was calcined in a furnace at 500 ℃.
Example 2
Carbon dioxide methanation catalyst and preparation method thereof
The catalyst carrier consists of the following raw materials in parts by weight: 80 parts of vermiculite and Al2O38 parts of SiO25 parts of carbon powder, 10 parts of cement powder.
The preparation steps are as follows:
step S10, preprocessing vermiculite: firstly, putting vermiculite into a 3% nitric acid solution, treating for 2 hours at 45 ℃, and putting acidified vermiculite into deionized water for cleaning; then putting the vermiculite into a muffle furnace, and carrying out high-temperature calcination expansion, wherein the temperature in the muffle furnace is controlled at 600 ℃, and the calcination time is 2 hours;
the vermiculite can be subjected to high-temperature calcination to remove volatile impurities, the volume of the vermiculite can be expanded by 6-20 times, the rich specific surface area of the vermiculite is beneficial to loading of active components on the inner surface and the outer surface of the vermiculite, soluble liquid substances in the vermiculite can be dissolved by acid washing, the inner surface area of the vermiculite is further improved, the dispersibility of the active components is improved, and the activity of the catalyst is increased.
Step S20, crushing of raw materials: mixing vermiculite and Al2O3、SiO2Firstly crushing and then ball-milling, filtering by using a 1000-mesh sieve to obtain powder with the diameter of less than 15 microns, and further ball-milling the cement powder and the carbon powder to obtain powder with the diameter of less than 15 microns;
step S20, forming of raw materials: putting the raw material powder into a 95 ℃ oven for drying treatment, weighing the raw materials according to the weight parts, adding distilled water for mixing and stirring, performing compression molding by using a molding machine, and then, oxidizing for 10-15 days in an environment with the air humidity of 100%;
step S40, pretreatment of the carrier: crushing the formed raw materials, screening carrier particles with the size of 20-40 meshes, putting the carrier particles into an oven with the temperature of 95 ℃ for drying for 12 hours, naturally airing the carrier particles, and then vacuumizing the carrier particles;
before catalyst impregnation, the carrier is vacuumized, gas in the carrier is pumped out, the adsorption capacity of the carrier is improved, and the loading capacity of metal is guaranteed.
Step S50, preparation of catalyst: depositing the active component on the support by means of an excess impregnation: 1. preparing a nickel nitrate solution with the nickel ion concentration of 3 mol/L; 2. placing the treated carrier into a nickel nitrate solution, and stirring and mixing for 10 minutes; 3. the impregnated catalyst is sealed and maintained for 24 hours at room temperature; 4. the dried catalyst was calcined in a furnace at 600 ℃.
Example 3
Carbon dioxide methanation catalyst and preparation method thereof
The catalyst carrier consists of the following raw materials in parts by weight: 70 parts of vermiculite and Al2O310 parts of SiO210 parts of carbon powder, 5 parts of cement powder and 15 parts of cement powder.
The preparation steps are as follows:
step S10, preprocessing vermiculite: firstly, putting vermiculite into 10% nitric acid solution, treating for 2 hours at 45 ℃, and putting acidified vermiculite into deionized water for cleaning; then putting the vermiculite into a muffle furnace, and carrying out high-temperature calcination expansion, wherein the temperature in the muffle furnace is controlled at 650 ℃, and the calcination time is 1 hour;
the vermiculite can be subjected to high-temperature calcination to remove volatile impurities, the volume of the vermiculite can be expanded by 6-20 times, the rich specific surface area of the vermiculite is beneficial to loading of active components on the inner surface and the outer surface of the vermiculite, soluble liquid substances in the vermiculite can be dissolved by acid washing, the inner surface area of the vermiculite is further improved, the dispersibility of the active components is improved, and the activity of the catalyst is increased.
Step S20, crushing of raw materials: mixing vermiculite and Al2O3、SiO2Firstly crushing and then ball-milling, filtering by using a 1000-mesh sieve to obtain powder with the diameter of less than 15 microns, and further ball-milling the cement powder and the carbon powder to obtain powder with the diameter of less than 15 microns;
step S20, forming of raw materials: putting the raw material powder into a 105 ℃ oven for drying treatment, weighing the raw materials according to the weight parts, adding distilled water for mixing and stirring, performing compression molding by using a molding machine, and then, oxidizing for 10-15 days in an environment with the air humidity of 100%;
step S40, pretreatment of the carrier: crushing the formed raw materials, screening carrier particles with the size of 20-40 meshes, putting the carrier particles into a drying oven with the temperature of 105 ℃ for drying for 6 hours, naturally airing the carrier particles, and then vacuumizing the carrier particles;
before catalyst impregnation, the carrier is vacuumized, gas in the carrier is pumped out, the adsorption capacity of the carrier is improved, and the loading capacity of metal is guaranteed.
Step S50, preparation of catalyst: depositing the active component on the support by means of an excess impregnation: 1. preparing a nitric acid solution with the total concentration of nickel ions and iron ions being 5 mol/L; 2. placing the treated carrier into the mixed solution, and stirring and mixing for 20 minutes; 3. after dipping, putting the mixture into a 105 ℃ oven for drying for 2 hours; 4. the dried catalyst was calcined in a furnace at 300 ℃.
Example 4
Carbon dioxide methanation catalyst and preparation method thereof
The catalyst carrier consists of the following raw materials in parts by weight: 80 parts of vermiculite and Al2O315 parts of SiO210 parts of carbon powder and 5 parts of cement powder.
The preparation steps are as follows:
step S10, preprocessing vermiculite: firstly, putting vermiculite into 10% nitric acid solution, treating for 2 hours at 45 ℃, and putting acidified vermiculite into deionized water for cleaning; then putting the vermiculite into a muffle furnace, and carrying out high-temperature calcination expansion, wherein the temperature in the muffle furnace is controlled at 600 ℃, and the calcination time is 2 hours;
the vermiculite can be subjected to high-temperature calcination to remove volatile impurities, the volume of the vermiculite can be expanded by 6-20 times, the rich specific surface area of the vermiculite is beneficial to loading of active components on the inner surface and the outer surface of the vermiculite, soluble liquid substances in the vermiculite can be dissolved by acid washing, the inner surface area of the vermiculite is further improved, the dispersibility of the active components is improved, and the activity of the catalyst is increased.
Step S20, crushing of raw materials: mixing vermiculite and Al2O3、SiO2Firstly crushing and then ball-milling, filtering by using a 1000-mesh sieve to obtain powder with the diameter of less than 15 microns, and further ball-milling the cement powder and the carbon powder to obtain powder with the diameter of less than 15 microns;
step S20, forming of raw materials: putting the raw material powder into a 105 ℃ oven for drying treatment, weighing the raw materials according to the weight parts, adding distilled water for mixing and stirring, performing compression molding by using a molding machine, and then, oxidizing for 10-15 days in an environment with the air humidity of 100%;
step S40, pretreatment of the carrier: crushing the formed raw materials, screening carrier particles with the size of 20-40 meshes, carrying out chemical modification treatment on the carrier, and treating for 2 hours at 45 ℃ by using a 3-10% nitric acid solution;
before catalyst impregnation, the carrier is subjected to acid treatment to remove impurities in the carrier, increase the specific surface area of the carrier, improve the adsorption capacity of the carrier and ensure the loading capacity of metals.
Step S50, preparation of catalyst: depositing the active component on the support by means of an excess impregnation: 1. preparing a cobalt nitrate solution with the cobalt ion concentration of 10 mol/L; 2. placing the treated carrier into a cobalt nitrate solution, and stirring and mixing for 10 minutes; 3. after dipping, putting the mixture into a 105 ℃ oven for drying for 2 hours; 4. the dried catalyst was calcined in a furnace at 500 ℃.
Example 5
Carbon dioxide methanation catalyst and preparation method thereof
The catalyst carrier consists of the following raw materials in parts by weight: 75 parts of vermiculite and Al2O310 parts of SiO28 parts of carbon powder, 8 parts of cement powder and 10 parts of cement powder.
The preparation steps are as follows:
step S10, preprocessing vermiculite: firstly, putting vermiculite into 6% nitric acid solution, treating for 2 hours at 45 ℃, and putting acidified vermiculite into deionized water for cleaning; then putting the vermiculite into a muffle furnace, and carrying out high-temperature calcination expansion, wherein the temperature in the muffle furnace is controlled at 600 ℃, and the calcination time is 2 hours;
the vermiculite can be subjected to high-temperature calcination to remove volatile impurities, the volume of the vermiculite can be expanded by 6-20 times, the rich specific surface area of the vermiculite is beneficial to loading of active components on the inner surface and the outer surface of the vermiculite, soluble liquid substances in the vermiculite can be dissolved by acid washing, the inner surface area of the vermiculite is further improved, the dispersibility of the active components is improved, and the activity of the catalyst is increased.
Step S20, crushing of raw materials: mixing vermiculite and Al2O3、SiO2Firstly crushing and then ball-milling, filtering by using a 1000-mesh sieve to obtain powder with the diameter of less than 15 microns, and further ball-milling the cement powder and the carbon powder to obtain powder with the diameter of less than 15 microns;
step S30, forming of raw materials: putting the raw material powder into a 105 ℃ oven for drying treatment, weighing the raw materials according to the weight parts, adding distilled water for mixing and stirring, performing compression molding by using a molding machine, and then, oxidizing for 10-15 days in an environment with the air humidity of 100%;
step S40, pretreatment of the carrier: crushing the formed raw materials, screening carrier particles with the size of 20-40 meshes, putting the carrier particles into a drying oven with the temperature of 105 ℃ for drying for 12 hours, naturally airing the carrier particles, and then vacuumizing the carrier particles;
before catalyst impregnation, the carrier is vacuumized, gas in the carrier is pumped out, the adsorption capacity of the carrier is improved, and the loading capacity of metal is guaranteed.
Step S50, preparation of catalyst: depositing the active component on the support by means of an excess impregnation: 1. preparing mixed solution with the concentration sum of nickel ions, iron ions and cobalt ions being 10 mol/L; 2. placing the treated carrier into the mixed solution, and stirring and mixing for 10 minutes; 3. after dipping, putting the mixture into a 105 ℃ oven for drying for 2 hours; 4. the dried catalyst was calcined in a furnace at 600 ℃.
Comparative example 1
Carbon dioxide methanation catalyst and preparation method thereof
The catalyst carrier is quartz sand, and the main component is SiO2。
The preparation steps are as follows:
step S10, preprocessing: firstly, putting quartz sand into 6% nitric acid solution, treating for 2 hours at 45 ℃, and putting the acidified quartz sand into deionized water for cleaning; then, putting the quartz sand into a muffle furnace, and carrying out high-temperature calcination expansion, wherein the temperature in the muffle furnace is controlled at 600 ℃, and the calcination time is 2 hours;
step S20, crushing of raw materials: crushing quartz sand, then performing ball milling, filtering by using a 1000-mesh sieve to obtain powder with the diameter of less than 15 microns, and further performing ball milling on the cement powder and the carbon powder to obtain powder with the diameter of less than 15 microns;
step S30, forming of raw materials: putting the raw material powder into a 105 ℃ oven for drying treatment, weighing the raw materials according to the weight parts, adding distilled water for mixing and stirring, and performing compression molding by using a molding machine;
step S40, pretreatment of the carrier: crushing the formed raw materials, screening carrier particles with the size of 20-40 meshes, putting the carrier particles into a drying oven with the temperature of 105 ℃ for drying for 12 hours, naturally airing the carrier particles, and then vacuumizing the carrier particles;
step S50, preparation of catalyst: depositing the active component on the support by means of an excess impregnation: 1. preparing a mixed solution with the nickel ion concentration of 8 mol/L; 2. placing the treated carrier into the mixed solution, and stirring and mixing for 10 minutes; 3. after dipping, putting the mixture into a 105 ℃ oven for drying for 2 hours; 4. the dried catalyst was calcined in a furnace at 600 ℃. Examples of the experiments
Evaluation of catalyst Activity
Weighing 1g of catalyst, placing the catalyst into a fixed bed reactor, heating to 300-500 ℃, keeping constant temperature, and introducing H2And CO2Control H2And CO2The gas amount is 4:1, the gas component composition in the produced gas is detected, the carbon dioxide conversion rate and the methane selectivity are calculated, and the experimental results are shown in table 1.
TABLE 1 catalyst Activity
The experimental result shows that compared with the catalyst with the SiO2 as the carrier, the catalyst prepared by the vermiculite compound as the carrier has higher carbon dioxide conversion rate and methane selectivity than the inert carrier, so that the preparation method of the catalyst has very obvious catalytic effect on methanation of carbon dioxide and has high conversion rate and high selectivity. The preparation method of the carbon dioxide methanation catalyst is simple and easy to operate, low in raw material cost, remarkable in catalysis effect and suitable for large-scale popularization.
The above description is only a preferred embodiment and an experimental example of the present invention, and is not intended to limit the present invention, and it is obvious to those skilled in the art that various modifications and variations can be made in the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The carbon dioxide methanation catalyst is characterized by comprising a carrier and an active component, wherein the carrier is composed of the following raw materials in parts by weight: 70-80 parts of vermiculite and Al2O38 to 15 parts of SiO25-10 parts of carbon powder, 5-10 parts of cement powder and 5-15 parts of active components, wherein the active components are one or a combination of at least two of Ni, Fe and Co; the preparation method comprises the following steps:
step S10, preprocessing vermiculite: putting vermiculite into a muffle furnace, carrying out high-temperature calcination expansion, controlling the temperature in the muffle furnace at 600-750 ℃, carrying out calcination time for 1-2 hours, and carrying out acid treatment before putting the vermiculite into the muffle furnace for high-temperature calcination, wherein the treatment process comprises the following steps: step S11, putting vermiculite into a 3-10% nitric acid solution, and treating for 2 hours at 45 ℃; step S12, putting the acidified vermiculite into deionized water for cleaning;
step S20, crushing of raw materials: mixing vermiculite and Al2O3、SiO2Firstly crushing and then ball-milling, filtering by using a 1000-mesh sieve to obtain powder with the diameter of less than 15 microns, and further ball-milling the cement powder and the carbon powder to obtain powder with the diameter of less than 15 microns;
step S30, forming of raw materials: putting the raw material powder into an oven at 95-105 ℃ for drying treatment, weighing the raw materials according to the weight parts, adding distilled water for mixing and stirring, and performing compression molding by using a molding machine;
step S40, pretreatment of the carrier: drying the molded raw materials in an oven at 95-105 ℃ for 6-12 hours, naturally airing, and then carrying out vacuum-pumping treatment;
step S50, preparation of catalyst: depositing the active component on the carrier by an excess impregnation method; the impregnation method comprises the following steps: step S51, preparing a metal salt solution with the cation concentration of 5-10 mol/L; step S52, placing the treated carrier into a metal salt solution, and stirring and mixing for 10-20 minutes; step S53, after dipping, putting the dipped material into an oven at the temperature of 95-105 ℃ for drying for 2 hours; and step S54, calcining the dried catalyst in a furnace at 300-600 ℃.
2. The carbon dioxide methanation catalyst according to claim 1, wherein the carrier is composed of the following raw materials in parts by weight: 75 parts of vermiculite and Al2O310 parts of SiO27 parts of carbon powder and 10 parts of cement powder.
3. The carbon dioxide methanation catalyst according to claim 1, wherein in step S30, the raw material is compressed, molded, and then placed in an environment with an air humidity of 100% to be oxidized for 10-15 days.
4. The carbon dioxide methanation catalyst according to claim 1, wherein in step S40, the pretreatment of the carrier comprises crushing the shaped carrier and sieving carrier particles with a size of 20-40 mesh.
5. The carbon dioxide methanation catalyst according to claim 1, wherein in step S40, the pretreatment of the carrier further comprises a chemical modification treatment of the carrier, specifically, a treatment with a 3-10% nitric acid solution at 45 ℃ for 2 hours.
6. The carbon dioxide methanation catalyst according to claim 1, wherein in step S53, the impregnated catalyst is sealed and cured at room temperature for 24 hours.
7. The carbon dioxide methanation catalyst of claim 1, wherein the metal salt is one or a combination of at least two of a soluble salt of nickel, a soluble salt of iron, and a soluble salt of cobalt.
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| GB1564004A (en) * | 1975-07-16 | 1980-04-02 | Nl Industries Inc | Manufacture of nickel-containing catalysts and process of catalytic methanation |
| CN101380581A (en) * | 2007-09-07 | 2009-03-11 | 新奥科技发展有限公司 | Novel methanation catalyst and preparation method thereof |
| CN104741125A (en) * | 2015-04-08 | 2015-07-01 | 石河子大学 | Catalyst as well as preparation method and application thereof |
| CN106311242A (en) * | 2015-07-06 | 2017-01-11 | 中国石油化工股份有限公司 | Carbon dioxide methanation catalyst and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1564004A (en) * | 1975-07-16 | 1980-04-02 | Nl Industries Inc | Manufacture of nickel-containing catalysts and process of catalytic methanation |
| CN101380581A (en) * | 2007-09-07 | 2009-03-11 | 新奥科技发展有限公司 | Novel methanation catalyst and preparation method thereof |
| CN104741125A (en) * | 2015-04-08 | 2015-07-01 | 石河子大学 | Catalyst as well as preparation method and application thereof |
| CN106311242A (en) * | 2015-07-06 | 2017-01-11 | 中国石油化工股份有限公司 | Carbon dioxide methanation catalyst and preparation method thereof |
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