CN111482170B - Catalyst for hydrogen production from methane, preparation method and application thereof - Google Patents
Catalyst for hydrogen production from methane, preparation method and application thereof Download PDFInfo
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- CN111482170B CN111482170B CN202010386467.XA CN202010386467A CN111482170B CN 111482170 B CN111482170 B CN 111482170B CN 202010386467 A CN202010386467 A CN 202010386467A CN 111482170 B CN111482170 B CN 111482170B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 73
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 57
- 239000001257 hydrogen Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 36
- -1 silicon-aluminum-titanium Chemical compound 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003365 glass fiber Substances 0.000 claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 21
- 238000001125 extrusion Methods 0.000 claims abstract description 19
- 238000005470 impregnation Methods 0.000 claims abstract description 14
- 238000000465 moulding Methods 0.000 claims abstract description 14
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000003345 natural gas Substances 0.000 claims description 10
- 238000002407 reforming Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 14
- 229910003445 palladium oxide Inorganic materials 0.000 abstract 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 20
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 18
- 239000004115 Sodium Silicate Substances 0.000 description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 17
- 229910052911 sodium silicate Inorganic materials 0.000 description 17
- 239000007788 liquid Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical group [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/394—
-
- B01J35/56—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a methane hydrogen production catalyst, a preparation method and application thereof. The catalyst of the invention comprises the effective components of silicon-aluminum-titanium composite oxide as a carrier and palladium oxide as an active component, preferably honeycomb molding and glass fiber as a reinforcing agent. The preparation method of the catalyst comprises the following steps: firstly, preparing the silicon-aluminum-titanium composite oxide by a coprecipitation method, secondly, loading palladium on the silicon-aluminum-titanium composite oxide by an excess impregnation method, then carrying out extrusion molding on the honeycomb catalyst, and finally carrying out post-molding treatment on the honeycomb catalyst. The hydrogen production catalyst prepared by the invention has high mechanical strength, good activity and reliable production process, and can meet the demand of miniaturized methane hydrogen production.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a methane hydrogen production catalyst, and a preparation method and application thereof.
Background
The miniaturized CH 4-containing gas reforming (reaction of CH4 and H2O) hydrogen production is one of the most important innovative technologies in the future energy technology revolution, the hydrogen energy with the characteristics of environmental protection and high energy is not yet important in the energy system of China, the hydrogen energy fuel cell technology has a major breakthrough in recent years, the service life, reliability and practical performance of vehicles are basically met, fuel cell automobiles begin to be put on the market in a large scale, and the innovation development of a new generation of distributed hydrogen production technology is encouraged. By 2020, the scale of hydrogen energy utilized by energy forms in China reaches 720 hundred million m3, the number of hydrogenation stations reaches 100, the total industrial output reaches 3000 million yuan, and the hydrogen energy may have explosive growth by 2025.
The development of the fuel automobile industry and the construction of a hydrogenation station are the key points. The technical routes of the urban hydrogen station can be divided into three categories: water electrolysis hydrogen production, natural gas reforming hydrogen production and external hydrogen supply technology. The hydrogen production by reforming natural gas has the advantage of low hydrogen production cost, and the hydrogen energy infrastructure can be developed by fully relying on the existing natural gas infrastructure experience, but the initial investment of equipment is large, and the prepared hydrogen can meet the requirements of fuel cells by a purification process. Large-scale hydrogen production by reforming natural gas (>1000Nm3/h) is widely applied to the chemical industry, and a hydrogen production technology by reforming natural gas on a scale (50-200Nm3/h) for a hydrogen station is currently under development. Similar to the water electrolysis hydrogen production device, the whole device is integrated in a frame, so that the transportation and the field installation are convenient.
Disclosure of Invention
The invention aims to solve the problems, provides a catalyst for preparing hydrogen from methane, can be applied to preparing hydrogen from methane, and also provides a preparation method of the catalyst for preparing hydrogen from methane, so that the excellent performance of the prepared catalyst is ensured.
The technical content of the invention is as follows:
a catalyst for preparing hydrogen from methane takes silicon-aluminum-titanium composite oxide as a carrier and palladium as an active component;
the catalyst is prepared by the following method: preparing a silicon-aluminum-titanium composite oxide by using a titanium source, an aluminum source and a silicon source by adopting a coprecipitation method, loading a palladium source precursor on the silicon-aluminum-titanium composite oxide, roasting to obtain catalyst powder, and processing the catalyst powder into a catalyst finished product through a forming step;
in the preparation process of the catalyst, the raw materials of a titanium source, an aluminum source, a silicon source and a palladium source are fed according to TiO2、Al2O3、SiO2And PdO, the mass ratio is as follows: 20-80: 50-100: 10-60: 0.5 to 3.
In a specific embodiment of the invention, the molding step is a honeycomb molding step, glass fiber and deionized water are added in the molding process, and the molding comprises the following components in percentage by mass: 63% -70% of catalyst powder, 5.0% -8.0% of glass fiber and 25% -30% of deionized water; and drying and calcining the formed product to obtain the product.
In one embodiment of the invention, the finished catalyst has 32 holes per square inch and a wall thickness of 1.4 mm.
The invention also comprises a preparation method of the methane hydrogen production catalyst, which comprises the following steps:
(1) preparing the silicon-aluminum-titanium composite oxide: adding titanium source, aluminum source and silicon source solution into a reaction container, adjusting the pH of the mixed solution at a certain temperature to form a precipitate, aging for a certain time, filtering, washing and drying the precipitate to obtain silicon-aluminum-titanium composite oxide;
(2) preparation of powder catalyst: dispersing the silicon-aluminum-titanium composite oxide prepared in the step (1) in a palladium source impregnation solution, stirring for a certain time at a certain temperature, evaporating to remove water, continuously drying, and calcining to obtain a powder catalyst;
(3) mixing the powder catalyst prepared in the step (2) with forming auxiliary agent glass fiber and deionized water, and preparing a forming sample through material mixing, mud mixing, aging and extrusion forming;
(4) after-treatment of the honeycomb catalyst: drying and calcining the extrusion molding sample again to obtain the product.
In one embodiment of the preparation method, in the step (1), the reaction temperature of the reaction container is controlled to be 60-80 ℃, the pH value when a precipitate is formed is 8-10, and the aging time is 1-2 hours.
In one specific example of the production method of the present invention, the pH of the mixed solution is adjusted by adding an alkaline solution of potassium carbonate in step (1).
In a specific embodiment of the preparation method, in the step (2), stirring is carried out for at least 4 hours at the temperature of 60-80 ℃ in the dipping process, then the water is evaporated to dryness at the temperature of 80-100 ℃, the evaporated material is dried for 12-24 hours at the temperature of 80-120 ℃, and then the material is calcined for at least 4.0 hours at the temperature of 500-600 ℃ to prepare the powder catalyst.
In a specific embodiment of the preparation method of the invention, in the step (4), the extrusion molding sample is dried at 80-100 ℃ for 12-24h, and then calcined at 500-600 ℃ for 4-12h, so as to obtain the product.
In one embodiment of the preparation method of the present invention, in the step (1) and the step (2), the raw materials of the titanium source, the aluminum source, the silicon source and the palladium source are fed according to the TiO2、Al2O3、SiO2And PdO, the mass ratio is as follows: 20-80: 50-100: 10-60: 0.5 to 3; in the step (3), the components have the following mass percentage: 63 to 70 percent of catalyst powder, 5.0 to 8.0 percent of glass fiber and 25 to 30 percent of deionized water.
The invention also provides the application of the catalyst in reforming the natural gas to produce hydrogen for the hydrogenation station.
Due to the adoption of the technical scheme, the invention has the advantages that:
1) the invention adopts silicon-aluminum-titanium composite oxide as a carrier and SiO2Has large specific surface area and easy forming performance, Al2O3Has high mechanical strength, high overall strength of catalyst, TiO2The catalyst has higher stability, is used for prolonging the long-time service life of the catalyst, and promotes the dispersion of active components on the carrier due to the electronic effect of each component of the composite oxide carrier;
2) the preparation of the silicon-aluminum-titanium composite oxide adopts a coprecipitation method, so that all components are uniformly distributed, the structure of the carrier is stable, and the dispersion of active components on the carrier is further promoted by the preparation method by stirring and dipping the powder of the silicon-aluminum-titanium composite oxide and a palladium source solution in excess volume;
3) the catalyst is preferably prepared into a honeycomb shape, has modularization, lighter relative mass, easily controlled length and large specific surface area, is beneficial to exerting excellent catalytic performance in a small device and is beneficial to recycling;
4) the catalyst for preparing hydrogen from methane prepared by the invention has high-efficiency activity and sulfur resistance, can be used for a hydrogen adding station for preparing hydrogen from natural gas, the conventional large-scale natural gas reforming hydrogen preparation adopts two-stage catalyst reaction, the temperature in the hydrogen preparation process is usually over 800 ℃, the requirement on the activity of the catalyst is relatively low due to high temperature, the hydrogen adding station is limited by small devices and the designed temperature is not too high, the catalyst adopting a large device can not meet the requirement on low-temperature activity, and the catalyst for preparing hydrogen from methane prepared by the invention has excellent low-temperature activity, can perform reaction at about 500 ℃ and has higher reaction activity.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
The embodiment discloses a catalyst for hydrogen production from methane, which takes silicon-aluminum-titanium composite oxide as a carrier and palladium as an active component;
the catalyst is prepared by the following method: preparing a silicon-aluminum-titanium composite oxide by using a titanium source, an aluminum source and a silicon source by adopting a coprecipitation method, loading a palladium source precursor on the silicon-aluminum-titanium composite oxide, roasting to obtain catalyst powder, and processing the catalyst powder into a catalyst finished product through a forming step;
in the preparation process of the catalyst, the raw materials of a titanium source, an aluminum source, a silicon source and a palladium source are fed according to TiO2、Al2O3、SiO2And PdO, the mass ratio is as follows: 20-80: 50-100: 10-60: 0.5 to 3.
The titanium source, the aluminum source, and the silicon source may preferably be titanium nitrate, aluminum nitrate, and sodium silicate solutions, but are not limited to the use of other chloride or sulfide precursors. Palladium is selected as a main active component, the using amount is small, the low-temperature catalytic performance is excellent, and in the embodiment, the palladium source is preferably a palladium nitrate solution.
Further, the forming step is a honeycomb forming step, glass fiber and deionized water are added in the forming process, and the forming process comprises the following components in percentage by mass: 63% -70% of catalyst powder, 5.0% -8.0% of glass fiber and 25% -30% of deionized water; and drying and calcining the formed product to obtain the product. The honeycomb catalyst has the characteristics of modularization, light relative weight, easy control of length and large specific surface area, is particularly suitable for exerting excellent catalytic performance in a small device, and is beneficial to recovery.
Furthermore, the number of holes of the finished catalyst product is preferably 32 holes/square inch, and the wall thickness is preferably 1.4mm, so that the stability and the pressure resistance of the finished catalyst product are ensured, and the continuous exertion of the catalytic activity is ensured.
The embodiment also provides a preparation method of the catalyst for producing hydrogen from methane, which comprises the following steps:
(1) preparing the silicon-aluminum-titanium composite oxide: adding titanium source, aluminum source and silicon source solution into a reaction container, adjusting the pH of the mixed solution at a certain temperature to form a precipitate, aging for a certain time, filtering, washing and drying the precipitate to obtain silicon-aluminum-titanium composite oxide;
(2) preparation of powder catalyst: dispersing the silicon-aluminum-titanium composite oxide prepared in the step (1) in a palladium source impregnation solution, stirring for a certain time at a certain temperature, evaporating to remove water, continuously drying, and calcining to obtain a powder catalyst;
(3) mixing the powder catalyst prepared in the step (2) with forming auxiliary agent glass fiber and deionized water, and preparing a forming sample through material mixing, mud mixing, aging and extrusion forming;
(4) after-treatment of the honeycomb catalyst: drying and calcining the extrusion molding sample again to obtain the product.
Selecting three composite materials of silicon, aluminum and titanium, SiO2Has large specific surface area and easy forming performance, Al2O3Has high mechanical strength, high overall strength of catalyst, TiO2The catalyst has high stability and is used for prolonging the long-term service life of the catalyst, the three components are prepared by a coprecipitation method, the ratio of the components is optimized, the components are uniformly distributed and have compact structures, and the dispersion of active components on a carrier is promoted due to the electronic effect of the components.
Further, in the step (1), the reaction temperature of the reaction container is controlled to be 60-80 ℃, the pH value of the formed precipitate is 8-10, and the aging time is 1-2 hours.
Further, in the step (1), the pH of the mixed solution is adjusted by adding an alkaline solution of potassium carbonate. In the alkaline pH adjustment process, including but not limited to the adjustment using carbonate or hydroxide, potassium carbonate is preferred in this embodiment, and it is found that potassium carbonate has more excellent catalytic performance than other pH adjusting agents, possibly due to the electronic regulation effect of K element on the main active component or between carriers.
Further, in the step (2), stirring for at least 4 hours at the temperature of 60-80 ℃ in the dipping process, evaporating water to dryness at the temperature of 80-100 ℃, drying the evaporated material for 12-24 hours at the temperature of 80-120 ℃, and calcining for at least 4.0 hours at the temperature of 500-600 ℃ to obtain the powder catalyst. Because the prepared silicon-aluminum-titanium composite oxide is powdery and is not suitable for direct isometric impregnation, and meanwhile, if the palladium source solution is formed in advance, a forming step is added, and the dispersion of the active component during loading is not facilitated, the palladium source solution and the carrier powder are uniformly mixed by adopting an over-volume stirring impregnation method, and the dispersion of the active component on the carrier is further promoted in the preparation method.
Further, in the step (4), the extrusion molding sample is dried at 80-100 ℃ for 12-24h, and then calcined at 500-600 ℃ for 4-12h, so as to obtain the product.
Further, in the step (1) and the step (2), the raw materials of the titanium source, the aluminum source, the silicon source and the palladium source are fed according to TiO2、Al2O3、SiO2And PdO, the mass ratio is as follows: 20-80: 50-100: 10-60: 0.5 to 3; in the step (3), the components have the following mass percentage: 63 to 70 percent of catalyst powder, 5.0 to 8.0 percent of glass fiber and 25 to 30 percent of deionized water.
The invention also provides the application of the catalyst in reforming the natural gas to produce hydrogen for the hydrogenation station. Due to the high strength, excellent low-temperature activity and sulfur resistance of the catalyst, the catalyst meets the hydrogen production application of a miniaturized hydrogen station, and the reaction effect can be achieved by only adopting one-stage reforming.
The following specific example implementation was carried out using the above preparation method:
example 1
(1) Taking 1L of mixed solution of titanium nitrate, aluminum nitrate and sodium silicate, wherein the concentration of the titanium nitrate is TiO2Calculated as 20g/L, the concentration of aluminum nitrate is calculated as Al2O3Calculated as 100g/L, the concentration of sodium silicate is SiO2The weight is 40 g/L. Adding the mixed solution into a constant-temperature reaction kettle, controlling the temperature in the constant-temperature reaction kettle to be 65 ℃, and dropwise adding K with the solute mass fraction of 20% into the constant-temperature reaction kettle under the condition of electric stirring2CO3And (3) adding the aqueous solution at a dropping rate of 4mL/min, and adjusting the pH value of the mixed solution in the constant-temperature reaction kettle to 8.0. And continuously stirring for 1.5h at constant temperature, and filtering the mixed solution in the constant-temperature reaction kettle to obtain a solid substance. And washing the solid for 4 times, and drying at the temperature of 80 ℃ for 8.0h to obtain the silicon-aluminum-titanium composite oxide.
(2) 0.5L of palladium nitrate impregnation liquid is taken, and the concentration of the palladium nitrate is 8 g/L. And (2) grinding the silicon-aluminum-titanium composite oxide prepared in the step (1), sieving with a 200-mesh sieve, placing into the impregnation liquid, stirring at 65 ℃ for 4.0h, and then heating to 80 ℃ until no liquid substance flows (i.e. evaporation drying). And drying the evaporated material at 100 ℃ for 8.0h, and calcining at 600 ℃ for 4.0h to obtain the powder catalyst.
(3) Extrusion molding of the honeycomb catalyst: and (3) mixing the powder catalyst prepared in the step (2) with glass fiber and deionized water. The mass content of each component is as follows: 64% of a powder catalyst; 6.0% of glass fiber; 30% of deionized water. Mixing the mixed materials in a ceramic mixer for 1.0h, then refining mud in a vacuum pugmill for 1.5h, and then aging for 24 h. And extruding and molding the aged pug to obtain a molded sample, wherein the number of holes of a finished catalyst product is 32 holes/square inch, and the wall thickness is 1.4 mm.
(4) After-treatment of the honeycomb catalyst: drying the extrusion molding sample at 80 ℃ for 12h, and then calcining at 600 ℃ for 8h to obtain the honeycomb catalyst I.
Example 2
(1) Taking 1L of mixed solution of titanium nitrate, aluminum nitrate and sodium silicate, wherein the concentration of the titanium nitrate is TiO240g/L, the concentration of aluminum nitrate is Al2O3Calculated as 80g/L, the concentration of sodium silicate is SiO2The weight is 60 g/L. Adding the mixed solution into a constant-temperature reaction kettle, controlling the temperature in the constant-temperature reaction kettle to be 75 ℃, and dropwise adding K with solute mass fraction of 50% into the constant-temperature reaction kettle under the condition of electric stirring2CO3And (3) adding the aqueous solution at the dropping speed of 2mL/min, and adjusting the pH value of the mixed solution in the constant-temperature reaction kettle to 10.0. And continuously stirring for 1.5h at constant temperature, and filtering the mixed solution in the constant-temperature reaction kettle to obtain a solid substance. And washing the solid for 4 times, and drying at the temperature of 100 ℃ for 8.0h to obtain the silicon-aluminum-titanium composite oxide.
(2) 0.5L of palladium nitrate impregnation liquid is taken, and the concentration of the palladium nitrate is 3 g/L. And (2) grinding the silicon-aluminum-titanium composite oxide prepared in the step (1), sieving with a 200-mesh sieve, placing into the impregnation liquid, stirring at 65 ℃ for 4.0h, and then heating to 90 ℃ until no liquid substance flows (i.e. evaporating to dryness). And drying the evaporated material at 100 ℃ for 8.0h, and calcining at 600 ℃ for 4.0h to obtain the powder catalyst.
(3) Extrusion molding of the honeycomb catalyst: and (3) mixing the powder catalyst prepared in the step (2) with glass fiber and deionized water. The mass content of each component is as follows: 68% of a powder catalyst; 7.0% of glass fiber; 25% of deionized water. Mixing the mixed materials in a ceramic mixer for 1.0h, then refining mud in a vacuum pugmill for 1.5h, and then aging for 24 h. And extruding and molding the aged pug to obtain a molded sample, wherein the number of holes of a finished catalyst product is 32 holes/square inch, and the wall thickness is 1.4 mm.
(4) After-treatment of the honeycomb catalyst: and drying the extrusion molding sample at 80 ℃ for 12h, and calcining at 500 ℃ for 8h to obtain the honeycomb catalyst II.
Example 3
(1) Taking 1L of mixed solution of titanium nitrate, aluminum nitrate and sodium silicate, wherein the concentration of the titanium nitrate is TiO2Calculated as 60g/L, the concentration of aluminum nitrate is calculated as Al2O3Calculated as 60g/L, the concentration of sodium silicate is SiO2The weight is 60 g/L. And adding the mixed solution into a constant-temperature reaction kettle, controlling the temperature in the constant-temperature reaction kettle to be 80 ℃, dropwise adding a K2CO3 aqueous solution with the solute mass fraction of 30% into the constant-temperature reaction kettle under the condition of electric stirring, wherein the dropwise adding speed is 3mL/min, and adjusting the pH value of the mixed solution in the constant-temperature reaction kettle to be 9.5. And continuously stirring for 1.5h at constant temperature, and filtering the mixed solution in the constant-temperature reaction kettle to obtain a solid substance. And washing the solid for 4 times, and drying at the temperature of 100 ℃ for 8.0h to obtain the silicon-aluminum-titanium composite oxide.
(2) 0.5L of palladium nitrate impregnation liquid is taken, and the concentration of the palladium nitrate is 7 g/L. And (2) grinding the silicon-aluminum-titanium composite oxide prepared in the step (1), sieving with a 200-mesh sieve, placing into the impregnation liquid, stirring at 65 ℃ for 4.0h, and then heating to 90 ℃ until no liquid substance flows (i.e. evaporating to dryness). And drying the evaporated material at 100 ℃ for 8.0h, and calcining at 600 ℃ for 4.0h to obtain the powder catalyst.
(3) Extrusion molding of the honeycomb catalyst: and (3) mixing the powder catalyst prepared in the step (2) with glass fiber and deionized water. The mass content of each component is as follows: 70% of a powder catalyst; 6.0% of glass fiber; 25% of deionized water. Mixing the mixed materials in a ceramic mixer for 1.0h, then refining mud in a vacuum pugmill for 1.5h, and then aging for 24 h. And extruding and molding the aged pug to obtain a molded sample, wherein the number of holes of a finished catalyst product is 32 holes/square inch, and the wall thickness is 1.4 mm.
(4) After-treatment of the honeycomb catalyst: and drying the extrusion molding sample at 100 ℃ for 12h, and calcining at 500 ℃ for 8h to obtain the honeycomb catalyst III.
Example 4
(1) Taking 1L of mixed solution of titanium nitrate, aluminum nitrate and sodium silicate, wherein the concentration of the titanium nitrate is TiO2Calculated as 30g/L, the concentration of the aluminum nitrate is calculated as Al2O3Calculated as 100g/L, the concentration of sodium silicate is SiO2The weight is 10 g/L. Adding the mixed solution into a constant-temperature reaction kettle, controlling the temperature in the constant-temperature reaction kettle to be 65 ℃, and dropwise adding K with solute mass fraction of 40% into the constant-temperature reaction kettle under the condition of electric stirring2CO3And (3) adding the aqueous solution at a dropping rate of 3mL/min, and adjusting the pH value of the mixed solution in the constant-temperature reaction kettle to 10.0. And continuously stirring for 1.5h at constant temperature, and filtering the mixed solution in the constant-temperature reaction kettle to obtain a solid substance. And washing the solid for 4 times, and drying at the temperature of 100 ℃ for 8.0h to obtain the silicon-aluminum-titanium composite oxide.
(2) 0.5L of palladium nitrate impregnation liquid is taken, and the concentration of the palladium nitrate is 2.5 g/L. And (2) grinding the silicon-aluminum-titanium composite oxide prepared in the step (1), sieving with a 200-mesh sieve, placing into the impregnation liquid, stirring at 70 ℃ for 4.0h, and then heating to 90 ℃ until no liquid substance flows (i.e. evaporating to dryness). And drying the evaporated material at 100 ℃ for 8.0h, and calcining at 600 ℃ for 4.0h to obtain the powder catalyst.
(3) Extrusion molding of the honeycomb catalyst: and (3) mixing the powder catalyst prepared in the step (2) with glass fiber and deionized water. The mass content of each component is as follows: 70% of a powder catalyst; 5.0% of glass fiber; 25% of deionized water. Mixing the mixed materials in a ceramic mixer for 1.0h, then refining mud in a vacuum pugmill for 1.5h, and then aging for 24 h. And extruding and molding the aged pug to obtain a molded sample, wherein the number of holes of a finished catalyst product is 32 holes/square inch, and the wall thickness is 1.4 mm.
(4) After-treatment of the honeycomb catalyst: and drying the extrusion molding sample at 80 ℃ for 12h, and then calcining at 500 ℃ for 8h to obtain the honeycomb catalyst IV.
Example 5
On the basis of example 1, two steps of extrusion molding of the honeycomb catalyst and aftertreatment of the honeycomb catalyst are eliminated, and the catalyst obtained in the step (2) is directly prepared into a solid cylindrical granular structure by a tabletting method.
Comparative example 1
On the basis of example 3, without adding titanium nitrate, the aluminum nitrate and the sodium silicate are enlarged in the same proportion, i.e. 1L of the aluminum nitrate and the sodium silicate are mixed and dissolvedLiquid, concentration of aluminum nitrate as Al2O3Calculated as 90g/L, the concentration of sodium silicate is SiO2It was calculated as 90g/L, and the remaining conditions were in accordance with example 3.
Comparative example 2
On the basis of example 3, without adding aluminum nitrate, the titanium nitrate and sodium silicate were scaled up in the same ratio, i.e., 1L of a mixed solution of titanium nitrate and sodium silicate was taken, the concentration of titanium nitrate was TiO2Calculated as 90g/L, the concentration of sodium silicate is SiO2It was calculated as 90g/L, and the remaining conditions were in accordance with example 3.
Comparative example 3
On the basis of example 3, without adding sodium silicate, the titanium nitrate and the aluminum nitrate are enlarged in the same proportion, that is, 1L of mixed solution of titanium nitrate and aluminum nitrate is taken, and the concentration of the titanium nitrate is TiO2Calculated as 90g/L, the concentration of the aluminum nitrate is calculated as Al2O3It was calculated as 90g/L, and the remaining conditions were in accordance with example 3.
Comparative example 4
Based on example 3, without adding sodium silicate and titanium nitrate, 1L of aluminum nitrate solution was taken, the concentration of aluminum nitrate being Al2O3It was calculated as 180g/L, and the remaining conditions were in accordance with example 3.
Comparative example 5
On the basis of example 1, the potassium carbonate solution was replaced with a sodium carbonate solution of the same concentration, and the remaining conditions were unchanged.
Comparative example 6
On the basis of example 1, the potassium carbonate solution was replaced with a potassium hydroxide solution of the same concentration, and the remaining conditions were unchanged.
Measurement of the intensity
The axial compressive strength of the honeycomb catalysts of each example and comparative example is shown in table 1, and it can be seen that the honeycomb catalyst for methane hydrogen production of the present application has better strength.
TABLE 1 axial compressive Strength of the different catalysts
| Catalyst type | Compressive strength (Kg/cm)2) |
| Example 1 | 7.64 |
| Example 2 | 6.96 |
| Example 3 | 6.82 |
| Example 4 | 8.81 |
| Example 5 | 6.31 |
| Comparative example 1 | 4.78 |
| Comparative example 2 | 4.16 |
| Comparative example 3 | 6.38 |
| Comparative example 4 | 5.44 |
| Comparative example 5 | 5.80 |
| Comparative example 6 | 6.43 |
Activity assay
The activity and stability of the catalysts prepared in the above examples were tested in a laboratory mini fixed bed reaction unit and analyzed on-line by a Thermal Conductivity Detector (TCD) and a hydrogen flame detector (FID) of an Agilent model 7890 gas chromatograph. The reaction conditions are as follows: the inlet temperature of the bed layer is 500 ℃, the pressure is 1Mpa, the steam-gas ratio (water vapor to methane) is 0.2, and the space velocity is 3000h-1。
The results of the correlation measurements are shown in table 2:
TABLE 1 reactivity of different catalysts
| Catalyst type | CH4Conversion rate |
| Example 1 | 91.4％ |
| Example 2 | 92.5％ |
| Example 3 | 93.6％ |
| Example 4 | 91.7％ |
| Example 5 | 90.5％ |
| Comparative example 1 | 76.6％ |
| Comparative example 2 | 73.9％ |
| Comparative example 3 | 77.4％ |
| Comparative example 4 | 85.3％ |
| Comparative example 5 | 77.8％ |
| Comparative example 6 | 83.1％ |
From the measurement results, the hydrogen production catalyst prepared by the method has the advantages of high mechanical strength, good activity and reliable production process, and can meet the demand of miniaturized methane hydrogen production. And through a sulfur resistance test, the sulfur resistance of the catalyst of the embodiment is more excellent than that of the catalyst of the comparative example and the catalyst of the prior art, and the sulfur resistance is possibly improved due to the performance of the multi-component composite carrier, so that the service life is prolonged.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (10)
1. The catalyst for preparing hydrogen from methane is characterized in that the catalyst takes silicon-aluminum-titanium composite oxide as a carrier and palladium as an active component;
the catalyst is prepared by the following method: preparing a silicon-aluminum-titanium composite oxide by using a titanium source, an aluminum source and a silicon source by adopting a coprecipitation method, loading a palladium source precursor on the silicon-aluminum-titanium composite oxide, roasting to obtain catalyst powder, and processing the catalyst powder into a catalyst finished product through a forming step;
in the preparation process of the catalyst, the raw materials of a titanium source, an aluminum source, a silicon source and a palladium source are fed according to TiO2、Al2O3、SiO2And PdO, the mass ratio is as follows: 20-80: 50-100: 10-60: 0.5 to 3.
2. The catalyst for hydrogen production from methane according to claim 1, wherein the molding step is a honeycomb molding step, and glass fiber and deionized water are added during the molding step, and the molding step comprises the following components in percentage by mass: 63% -70% of catalyst powder, 5.0% -8.0% of glass fiber and 25% -30% of deionized water; and drying and calcining the formed product to obtain the product.
3. The methane hydrogen production catalyst according to claim 2, wherein the finished catalyst has a pore count of 32 pores per square inch and a wall thickness of 1.4 mm.
4. The preparation method of the catalyst for preparing hydrogen from methane is characterized by comprising the following steps:
(1) preparing the silicon-aluminum-titanium composite oxide: adding titanium source, aluminum source and silicon source solution into a reaction container, adjusting the pH of the mixed solution at a certain temperature to form a precipitate, aging for a certain time, filtering, washing and drying the precipitate to obtain silicon-aluminum-titanium composite oxide;
(2) preparation of powder catalyst: dispersing the silicon-aluminum-titanium composite oxide prepared in the step (1) in a palladium source impregnation solution, stirring for a certain time at a certain temperature, evaporating to remove water, continuously drying, and calcining to obtain a powder catalyst;
(3) mixing the powder catalyst prepared in the step (2) with forming auxiliary agent glass fiber and deionized water, and preparing a forming sample through material mixing, mud mixing, aging and extrusion forming;
(4) after-treatment of the honeycomb catalyst: drying and calcining the extrusion molding sample again to obtain a product;
wherein, in the step (1) and the step (2), raw materials of a titanium source, an aluminum source, a silicon source and a palladium source are addedAccording to TiO2、Al2O3、SiO2And PdO, the mass ratio is as follows: 20-80: 50-100: 10-60: 0.5 to 3.
5. The preparation method of the catalyst for hydrogen production from methane according to claim 4, wherein in the step (1), the reaction temperature of the reaction container is controlled to be 60-80 ℃, the pH value of the formed precipitate is 8-10, and the aging time is 1-2 h.
6. The method for preparing the catalyst for producing hydrogen from methane according to claim 4, wherein the pH of the mixed solution is adjusted by adding an alkaline solution of potassium carbonate in step (1).
7. The preparation method of the catalyst for hydrogen production from methane according to claim 4, characterized in that in the step (2), the catalyst is stirred for at least 4 hours at 60-80 ℃ in the dipping process, the water is evaporated at 80-100 ℃, the evaporated material is dried for 12-24 hours at 80-120 ℃, and then calcined for at least 4.0 hours at 500-600 ℃ to prepare the powder catalyst.
8. The method for preparing the catalyst for hydrogen production from methane according to claim 4, wherein in the step (4), the extrusion molded sample is dried at 80-100 ℃ for 12-24h, and then calcined at 500-600 ℃ for 4-12h, so as to obtain the product.
9. The preparation method of the catalyst for hydrogen production from methane according to claim 4, wherein in the step (3), the mass percentage of each component is as follows: 63-70% of catalyst powder, 5.0-8.0% of glass fiber and 25-30% of deionized water.
10. The catalyst of any one of claims 1 to 3 is applied to reforming of natural gas for hydrogen production in a hydrogen station.
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