CN107649137B - Catalyst for preparing hydrogen by reforming methanol steam at high temperature, preparation method and application - Google Patents
Catalyst for preparing hydrogen by reforming methanol steam at high temperature, preparation method and application Download PDFInfo
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- CN107649137B CN107649137B CN201711039557.6A CN201711039557A CN107649137B CN 107649137 B CN107649137 B CN 107649137B CN 201711039557 A CN201711039557 A CN 201711039557A CN 107649137 B CN107649137 B CN 107649137B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 148
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 123
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000001257 hydrogen Substances 0.000 title claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 29
- 238000002407 reforming Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 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 27
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 27
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 38
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- 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
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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Abstract
The invention discloses a catalyst for preparing hydrogen by methanol steam high-temperature reforming, a preparation method and application thereof, wherein the catalyst is TiO2/Al2O3As carrier, with CeO loaded on the carrier2And/or ZrO2The catalyst is used as a cocatalyst, a ZnO-NiO double-activity center dispersed on a carrier is used as a catalyst active component, the mass of the catalyst active component accounts for 15-30% of the total mass of the catalyst, the mass ratio of ZnO to NiO in the ZnO-NiO double-activity center is (70-90): (10-30), the mass ratio of the cocatalyst to the carrier is (5-15): 85-95), precious metals are not used as raw materials, the defects of the traditional Zn-Cr catalyst can be overcome, the catalyst can be applied to a high-temperature range of 350-550 ℃, and the catalyst is high in activity, high in selectivity and stable in catalytic performance.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for preparing hydrogen by methanol steam high-temperature reforming, a preparation method and application thereof.
Background
The methanol has the advantages of low price, easy obtaining, high energy density, low carbon content, convenient transportation and storage and the like, and is praised as the most promising high-energy-carrying fuel; the hydrogen production by reforming methanol and water vapor is the reaction with the highest hydrogen content in the reformed gas, and has the advantages of low cost, mild condition, less product components, easy separation, etc.
The core of the methanol steam reforming hydrogen production technology lies in catalysts, and related catalysts are widely and deeply researched, wherein copper-based catalysts are mainly researched, but the copper-based catalysts are mainly suitable for low-temperature environments of 210-300 ℃ and are not suitable for high-temperature environments of 300-550 ℃ required by small-sized mobile hydrogen production equipment and fuel cells. In recent years, catalysts suitable for hydrogen production in high temperature environments have been mainly studied on Zn — Cr catalysts and noble metal catalysts. Among them, noble metal catalysts have high activity and stability and are concerned with, but the expensive price is still difficult to meet the demand of the current hydrogen production market; the Zn-Cr catalyst of non-noble metal basically adopts a coprecipitation preparation technology, the consumption of Cr is large, the content of Cr is still maintained at about 10 percent even if an impregnation method is adopted, the use of heavy metal Cr can cause important influence on the environment and the personal safety of operators, and the Zn-Cr catalyst is not environment-friendly and is not beneficial to the development needs of the current society.
Disclosure of Invention
In view of this, the application provides a catalyst for hydrogen production by methanol steam high-temperature reforming, a preparation method and an application thereof, which do not use noble metals as raw materials, can overcome the defects of the traditional Zn-Cr catalyst, can be applied in a high-temperature range of 350-550 ℃, and has high activity, high selectivity and stable catalytic performance.
In order to solve the technical problems, the technical scheme provided by the invention is a catalyst for preparing hydrogen by reforming methanol steam at high temperature, wherein the catalyst uses TiO2/Al2O3As carrier, with CeO loaded on the carrier2And/or ZrO2The catalyst is used as a cocatalyst, a ZnO-NiO double-active center dispersed on a carrier is used as a catalyst active component, the mass of the catalyst active component accounts for 15-30% of the total mass of the catalyst, the mass ratio of ZnO to NiO in the ZnO-NiO double-active center is (70-90): 10-30), and the mass ratio of the cocatalyst to the carrier is (5-15): 85-95).
According to the technical scheme, the ZnO-NiO double-activity center is used as an active component of the catalyst, no noble metal or heavy pollution metal is used, and high activity and high selectivity can be maintained at high temperature. By using TiO2Modified Al2O3Formation of TiO2/Al2O3Support, TiO2The addition of the catalyst improves the pore volume of the carrier, greatly increases the amount of mesopores (10-200 nm) in the carrier under the condition of little influence on the surface area, reduces the amount of micropores (less than or equal to 2nm) with little effect, and is beneficial to the improvement of the activity of the catalyst; using CeO supported on a carrier2And/or ZrO2Is a cocatalyst, and separates active component from Al by the synergistic effect between the cocatalyst and the active component of the catalyst2O3The high activity of the active components of the catalyst is increased, and the stability of the activity of the catalyst is improved. In addition, ZnO-NiO bimetal is used as an active center, the catalyst is directly heated to the use temperature without reduction when in use, the raw material gas can be used, no physical water is discharged basically in the heating process, the volume of the catalyst is almost not shrunk, and the use of the catalyst is greatly simplified.
Preferably, the catalyst is spherical, the diameter of the catalyst is 2-4 mm, the water pore volume of the catalyst is 30-50%, and the specific surface area of the catalyst is more than or equal to 120m2The strength is not less than 150N/g, and the bulk density is 0.8-1.0 kg/L.
The technical scheme of the application also provides a preparation method of the catalyst for hydrogen production by methanol steam high-temperature reforming, and the preparation method comprises the following steps:
(1) mixing and ball-milling aluminum hydroxide, titanium dioxide and cellulose in a mass ratio of (85-90) to (6-8) to (1.5-3), adding water after ball-milling, uniformly mixing and granulating, preparing a spherical carrier, curing the spherical carrier by using steam until the strength reaches more than 120N/particle, and calcining to obtain TiO2/Al2O3A carrier;
(2) dissolving cerium nitrate and/or zirconium nitrate in deionized water to prepare a metal nitrate solution, wherein the total concentration of the metal nitrate mixed solution is 1.5-3 mol/L, and mixing the TiO in the step (1)2/Al2O3Soaking the carrier in the nitrate solution, drying, calcining and cooling to obtain CeO2And/or ZrO2Modified TiO2/Al2O3A carrier;
(3) dissolving zinc nitrate and nickel nitrate in deionized water to prepare a mixed solution of metal nitrate, wherein the total concentration of the mixed solution of metal nitrate is 2-4 mol/L, and adding the CeO obtained in the step (2)2And/or ZrO2Modified TiO2/Al2O3And (3) soaking the carrier in the mixed solution of the metal nitrate, and drying, calcining and cooling the soaked carrier to obtain a finished catalyst.
Preferably, the calcining temperature in the step (1) is 500-700 ℃, and the time is 2-6 h.
Preferably, the impregnation temperature in the step (2) is 50-90 ℃, the impregnation time is 30-60 min, and the drying, calcining and cooling specifically comprise: drying at 120-200 ℃ for 2-6 h, calcining at 400-550 ℃ for 3-10 h, and cooling.
Preferably, the dipping temperature in the step (3) is 50-90 ℃, the dipping time is 30-60 min, and the drying, calcining and cooling specifically comprise: drying at 120-200 ℃ for 2-6 h, calcining at 400-550 ℃ for 3-10 h, and cooling.
The technical scheme of the application also provides an application of the catalyst for preparing hydrogen by reforming methanol steam at high temperature, and the using conditions of the catalyst are as follows: the molar ratio of the methanol to the water is 0.5-3.0, the reaction pressure is 0.1-4.0 MPa, and the airspeed of the material feeding liquid is 0.5-4.0.
Preferably, the catalyst is used under the following conditions: the molar ratio of the methanol to the water is 0.8-1.5, the reaction pressure is 0.1-3.0 MPa, and the airspeed of the material feeding liquid is 0.8-3.0.
Preferably, the use temperature of the catalyst is 350-550 ℃.
Compared with the prior art, the application has the beneficial effects that: (1) the catalyst does not adopt noble metal, so that the cost is saved; heavy pollution metal is not used, which is beneficial to environmental protection and personnel safety; (2) the catalyst is prepared without a coprecipitation method in the preparation process, so that active metals are saved, and the consumption is low; (3) the catalyst can be applied to the high temperature range of 350-550 ℃, and has high activity and high selectivityThe catalytic performance is stable; (4) the catalyst is in a spherical shape, is simple and convenient to fill in the using process and has high mechanical strength; (5) the catalyst can be fed and used by directly heating to the use temperature without heating reduction, so that the operation difficulty of the catalyst is greatly simplified; (6) the catalyst can be used for mixing liquid with an airspeed of 3.0h-1Long-term operation under the condition.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to specific embodiments.
Example 1
The catalyst for producing hydrogen by methanol steam high-temperature reforming described in this embodiment has the preparation method:
(1) and (2) mixing the following components in percentage by mass: 6: 1.5, mixing and ball-milling aluminum hydroxide, titanium dioxide and cellulose, adding water after ball milling, uniformly mixing and granulating, then preparing a spherical carrier, curing the spherical carrier by steam until the strength reaches more than 120N/particle, and calcining for 2 hours at 500 ℃ to obtain TiO2/Al2O3A carrier;
(2) preparing a cerium nitrate solution according to the content of the finally generated oxide, wherein the total concentration of the mixed solution of the metal nitrate is 2 mol/L, and reacting the TiO in the step (1) at 70 DEG C2/Al2O3Soaking the carrier in the metal nitrate solution for 45min, drying at 160 deg.C for 4 hr, calcining at 450 deg.C for 6 hr, and cooling to obtain CeO2And/or ZrO2Modified TiO2/Al2O3A carrier;
(3) preparing a mixed solution of nickel and zinc nitrates according to the content of the finally generated oxides, wherein the total concentration of the mixed solution of the nitrates is 3 mol/L, and carrying out the CeO prepared in the step (2) at the temperature of 70 DEG C2And/or ZrO2Modified TiO2/Al2O3Soaking the carrier in the mixed solution of metal nitrate for 45min, drying at 160 deg.C for 4 hr, and calcining at 500 deg.CAnd standing and cooling after 8 hours of burning to obtain the catalyst finished product.
The mass of the active components of the catalyst in the prepared catalyst finished product accounts for 15% of the total mass of the catalyst, in the ZnO-NiO double-activity center, the mass ratio of ZnO to NiO is 70:30, the mass ratio of the cocatalyst to the carrier is 5:95, the catalyst is spherical, the diameter is 2-4 mm, the water pore volume is 30-50%, and the specific surface area is more than or equal to 120m2The strength is not less than 150N/g, and the bulk density is 0.8-1.0 kg/L.
The using conditions of the catalyst are as follows: the molar ratio of methanol to water is 0.5-3.0, the reaction pressure is 0.1-4.0 MPa, the airspeed of a material feeding liquid is 0.5-4.0, and the use temperature of the catalyst is 350-550 ℃.
Example 2
The catalyst for producing hydrogen by methanol steam high-temperature reforming described in this embodiment has the preparation method:
(1) and (3) mixing the components in a mass ratio of 90: 8: 3, mixing and ball-milling the aluminum hydroxide, the titanium dioxide and the cellulose, adding water after ball milling, uniformly mixing and granulating, then preparing a spherical carrier, curing the spherical carrier by steam until the strength reaches more than 120N/particle, and calcining for 6 hours at 700 ℃ to obtain TiO2/Al2O3A carrier;
(2) preparing a cerium nitrate solution according to the content of the finally generated oxide, wherein the total concentration of the mixed solution of the metal nitrate is 1.5 mol/L, and reacting the TiO described in the step (1) at the temperature of 50 DEG C2/Al2O3Soaking the carrier in the metal nitrate solution for 30min, drying at 120 deg.C for 2 hr, calcining at 400 deg.C for 3 hr, and cooling to obtain CeO2And/or ZrO2Modified TiO2/Al2O3A carrier;
(3) preparing a mixed solution of nickel and zinc nitrates according to the content of the finally generated oxides, wherein the total concentration of the mixed solution of the nitrates is 2 mol/L, and carrying out the CeO prepared in the step (2) at the temperature of 50 DEG C2And/or ZrO2Modified TiO2/Al2O3Immersing the carrier in the mixed solution of metal nitrate, and immersingThe time is controlled to be 30min, the catalyst is dried for 2h at 120 ℃ after the impregnation is finished, then calcined for 3h at 450 ℃, and then placed and cooled to obtain the finished product of the catalyst.
The mass of the active components of the catalyst in the prepared catalyst finished product accounts for 30% of the total mass of the catalyst, in the ZnO-NiO double-activity center, the mass ratio of ZnO to NiO is 90:10, the mass ratio of the cocatalyst to the carrier is 15:85, the catalyst is spherical, the diameter is 2-4 mm, the water pore volume is 30-50%, and the specific surface area is more than or equal to 120m2The strength is not less than 150N/g, and the bulk density is 0.8-1.0 kg/L.
The using conditions of the catalyst are as follows: the molar ratio of methanol to water is 0.5-3.0, the reaction pressure is 0.1-4.0 MPa, the airspeed of a material feeding liquid is 0.5-4.0, and the use temperature of the catalyst is 350-550 ℃.
Example 3
The catalyst for producing hydrogen by methanol steam high-temperature reforming described in this embodiment has the preparation method:
(1) mixing and ball-milling aluminum hydroxide, titanium dioxide and cellulose in a mass ratio of 88:7:2, adding water after ball-milling, uniformly mixing and granulating, then preparing a spherical carrier, curing the spherical carrier by steam until the strength reaches more than 120N/particle, and calcining for 4 hours at 600 ℃ to obtain TiO2/Al2O3A carrier;
(2) preparing a cerium nitrate solution according to the content of the finally generated oxide, wherein the total concentration of the mixed solution of the metal nitrate is 3 mol/L, and reacting the TiO in the step (1) at 90 DEG C2/Al2O3Soaking the carrier in the nitrate metal salt solution for 60min, drying at 120-200 ℃ for 2-6 h after soaking, calcining at 550 ℃ for 10h, and standing for cooling to obtain CeO2And/or ZrO2Modified TiO2/Al2O3A carrier;
(3) preparing a mixed solution of nickel and zinc nitrates according to the content of the finally generated oxides, wherein the total concentration of the mixed solution of the nitrates is 4 mol/L, and carrying out the CeO prepared in the step (2) at the temperature of 90 DEG C2And/or ZrO2Modified TiO2/Al2O3And (3) soaking the carrier in the mixed solution of the metal nitrate for 60min, drying at 200 ℃ for 6h after soaking, calcining at 550 ℃ for 10h, standing and cooling to obtain a finished catalyst.
The mass of the active components of the catalyst in the prepared catalyst finished product accounts for 25% of the total mass of the catalyst, the mass ratio of ZnO to NiO is 80:20, the mass ratio of the cocatalyst to the carrier is 10:90, the catalyst is spherical, the diameter is 2-4 mm, the water pore volume is 30-50%, and the specific surface area is more than or equal to 120m2The strength is not less than 150N/g, and the bulk density is 0.8-1.0 kg/L.
The using conditions of the catalyst are as follows: the molar ratio of methanol to water is 0.5-3.0, the reaction pressure is 0.1-4.0 MPa, the airspeed of a material feeding liquid is 0.5-4.0, and the use temperature of the catalyst is 350-550 ℃.
Experimental example 1
Catalyst Activity test A
1. Experimental parameters:
the size of the reaction tube is a stainless steel tube with phi 25 × 3 × 500 mm;
the loading of the catalyst is 30m L;
detecting pressure: 1.2 +/-0.1 MPa; the detection temperature is 400 +/-2 ℃; space velocity of feeding liquid: 2.0h-1(ii) a Raw material liquid: the mass ratio of the methanol to the desalted water is 1: 1.
2. Experimental samples: as shown in Table 1, each catalyst sample takes a ZnO-NiO double-active center as a catalyst active component, the content of the catalyst active component is 20% of the total weight of the catalyst, and the mass ratio of ZnO to NiO is 80: 20; all with CeO2As a cocatalyst, with CeO2The mass ratio of the carrier to the carrier is 10: 90. TiO in the control Carrier2The activity of each catalyst sample was tested at different weight addition levels.
3. The experimental steps comprise the steps of putting each catalyst sample in table 1 into a reactor, wherein the reactor is a stainless steel tube type reactor with the thickness of 25 × 3 × 60mm, the filling amount of the catalyst is 30m L, heating the catalyst to the reaction temperature by using nitrogen as a medium, controlling the heating rate to be 40-60 ℃, keeping the reaction temperature at 400 ℃, introducing a mixed liquid of methanol and water into a steam generator, heating the mixed liquid to 400 ℃, introducing a mixed gas of vaporized methanol steam and water steam into the reactor, and starting analysis after stabilizing for 2 hours.
4. The experimental results are as follows: the results of the catalyst activity tests are shown in table 1.
Table 1 experimental example 1 results of catalyst activity test
As can be seen from the data above, no TiO is added2The methanol conversion rate of the carrier is low, the activity stability of the catalyst is poor, and the activity attenuation can occur after the carrier is operated for 5 hours; to which TiO is added2The methanol conversion rate of the carrier is improved, and the activity stability is good; when TiO is present2When the amount exceeds 20%, the carrier strength is lowered, the catalyst is easily pulverized, and the activity stability are lowered. Thus, TiO2The optimum amount of (B) is 7%.
Experimental example 2
Catalyst Activity test B
1. Experimental parameters:
the size of the reaction tube is a stainless steel tube with phi 25 × 3 × 500 mm;
the loading of the catalyst is 30m L;
detecting pressure: 1.2 +/-0.1 MPa; the detection temperature is 400 +/-2 ℃; space velocity of feeding liquid: 2.0h-1(ii) a Raw material liquid: the mass ratio of the methanol to the desalted water is 1: 1.
2. Experimental samples: as shown in Table 2, each catalyst sample takes a ZnO-NiO double-active center as a catalyst active component, the content of the catalyst active component is 20% of the total weight of the catalyst, and the mass ratio of ZnO to NiO is 80: 20; with TiO2/Al2O3As a carrier, wherein TiO is2The amount of (B) is 7% by weight. And comparing the different mass ratios of the cocatalyst to the carrier in the catalyst and the different types of the cocatalyst, and testing the activity of each catalyst sample.
3. The experimental steps are as follows: as in experimental example 1.
4. The experimental results are as follows: the results of the catalyst activity tests are shown in table 2.
Table 2 experimental example 2 results of catalyst activity test
As can be seen from the data in the table above, when no cocatalyst is added, the conversion rate of methanol is low, and the activity stability of the catalyst is poor; when the promoter is added, the conversion rate of methanol and the activity stability of the catalyst are both improved, the strength of the carrier is basically unchanged along with the increase of the addition amount of the promoter, the activity of the catalyst is obviously increased, when the content of the promoter exceeds 20%, the activity and the strength of the catalyst are not further increased, and the specific surface area of a catalytic product is reduced; in summary, the addition amount of the cocatalyst is preferably 10 to 15%; comparative CeO2、ZrO2And the sample in which both were mixed as a cocatalyst, 10% CeO was observed2When used as a cocatalyst, the catalyst has better indexes.
Experimental example 3
Catalyst Activity test C
1. Experimental parameters:
the size of the reaction tube is a stainless steel tube with phi 25 × 3 × 500 mm;
the loading of the catalyst is 30m L;
detecting pressure: 1.2 +/-0.1 MPa; the detection temperature is 400 +/-2 ℃; space velocity of feeding liquid: 2.0h-1(ii) a Raw material liquid: the mass ratio of the methanol to the desalted water is 1: 1.
2. Experimental samples: as shown in Table 3, each catalyst sample was made of TiO2/Al2O3As a carrier, wherein TiO is2The weight addition amount of (A) is 7%; all with CeO2As cocatalyst, CeO2The mass ratio of the carrier to the carrier is 10: 90. Comparing different catalyst active components, different weight proportions of ZnO-NiO in the catalyst active components, catalyzingWhen the active components of the catalyst account for different percentages of the total weight of the catalyst, the activity test result of each catalyst sample is obtained.
3. The experimental steps are as follows: as in experimental example 1.
4. The experimental results are as follows: the results of the catalyst activity tests are shown in Table 3.
Table 3 experimental example 3 results of catalyst activity test
Note: h2Selectivity to the percentage of actual hydrogen production to theoretical hydrogen production;
as can be seen from the data in the above table, when the catalyst active component is ZnO, the methanol conversion rate and the catalyst activity stability are poor, and when the catalyst active component is NiO, the methanol conversion rate is good, but H is2The selectivity is poor, and the hydrogen production effect is limited; when the ZnO-NiO double-activity center is used as the active component of the catalyst, the conversion rate of methanol and the activity stability of the catalyst are greatly improved, and when the mass ratio of ZnO to NiO is 80:20, each index is optimal, and the total content of the active component is preferably controlled to be about 20% in consideration of practical application.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. The catalyst for preparing hydrogen by reforming methanol steam at high temperature is characterized in that: the catalyst is made of TiO2/Al2O3As carrier, with CeO loaded on the carrier2And/or ZrO2The catalyst is used as a cocatalyst, a ZnO-NiO double-active center dispersed on a carrier is used as a catalyst active component, the mass of the catalyst active component accounts for 15-30% of the total mass of the catalyst, the mass ratio of ZnO to NiO in the ZnO-NiO double-active center is (70-90): 10-30), and the mass ratio of the cocatalyst to the carrier is (5-15): 85-95).
2. The catalyst for high-temperature reforming of methanol steam to produce hydrogen according to claim 1, which is characterized in that: the catalyst is spherical, the diameter of the catalyst is 2-4 mm, the water pore volume of the catalyst is 30-50%, and the specific surface area of the catalyst is more than or equal to 120m2The strength is not less than 150N/g, and the bulk density is 0.8-1.0 kg/L.
3. A method for preparing a catalyst for high-temperature reforming of methanol steam to produce hydrogen according to claim 1 or 2, which is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) mixing and ball-milling aluminum hydroxide, titanium dioxide and cellulose in a mass ratio of (85-90) to (6-8) to (1.5-3), adding water after ball-milling, uniformly mixing and granulating, preparing a spherical carrier, curing the spherical carrier by using steam until the strength reaches more than 120N/particle, and calcining to obtain TiO2/Al2O3A carrier;
(2) dissolving cerium nitrate and/or zirconium nitrate in deionized water to prepare a metal nitrate solution, wherein the total concentration of the metal nitrate mixed solution is 1.5-3 mol/L, and mixing the TiO in the step (1)2/Al2O3Soaking the carrier in the nitrate solution, drying, calcining and cooling to obtain CeO2And/or ZrO2Modified TiO2/Al2O3A carrier;
(3) dissolving zinc nitrate and nickel nitrate in deionized water to prepare a mixed solution of metal nitrate, wherein the total concentration of the mixed solution of metal nitrate is 2-4 mol/L, and adding the CeO obtained in the step (2)2And/or ZrO2Modified TiO2/Al2O3And (3) soaking the carrier in the mixed solution of the metal nitrate, and drying, calcining and cooling the soaked carrier to obtain a finished catalyst.
4. The preparation method of the catalyst for producing hydrogen by methanol steam high-temperature reforming according to claim 3, characterized by comprising the following steps: the calcining temperature in the step (1) is 500-700 ℃, and the time is 2-6 h.
5. The preparation method of the catalyst for producing hydrogen by methanol steam high-temperature reforming according to claim 3, characterized by comprising the following steps: in the step (2), the dipping temperature is 50-90 ℃, the dipping time is 30-60 min, and the drying, calcining and cooling specifically comprise the following steps: drying at 120-200 ℃ for 2-6 h, calcining at 400-550 ℃ for 3-10 h, and cooling.
6. The preparation method of the catalyst for producing hydrogen by methanol steam high-temperature reforming according to claim 3, characterized by comprising the following steps: the dipping temperature in the step (3) is 50-90 ℃, the dipping time is 30-60 min, and the drying, calcining and cooling specifically comprise the following steps: drying at 120-200 ℃ for 2-6 h, calcining at 400-550 ℃ for 3-10 h, and cooling.
7. The use of the catalyst for producing hydrogen by high-temperature reforming of methanol steam according to claim 1 or 2, characterized in that: the using conditions of the catalyst are as follows: the molar ratio of the methanol to the water is 0.5-3.0, the reaction pressure is 0.1-4.0 MPa, and the airspeed of the material feeding liquid is 0.5-4.0.
8. The application of the catalyst for preparing hydrogen by high-temperature reforming of methanol steam according to claim 7 is characterized in that: the using conditions of the catalyst are as follows: the molar ratio of the methanol to the water is 0.8-1.5, the reaction pressure is 0.1-3.0 MPa, and the airspeed of the material feeding liquid is 0.8-3.0.
9. The application of the catalyst for preparing hydrogen by high-temperature reforming of methanol steam according to claim 7 is characterized in that: the use temperature of the catalyst is 350-550 ℃.
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| KR20200101028A (en) * | 2019-02-19 | 2020-08-27 | 현대자동차주식회사 | A nanocomposite for hydrogen production of hydrogen which has improved longevity and the method of manufacture thereof |
| CN112871175A (en) * | 2021-01-14 | 2021-06-01 | 广东醇氢新能源研究院有限公司 | Non-noble metal methanol hydrogen production catalyst without reduction and preparation method thereof |
| CN114602494B (en) * | 2022-05-12 | 2022-07-29 | 中国环境科学研究院 | Method for preparing multi-metal ozone catalyst by blending-impregnation combined method |
| CN115555009A (en) * | 2022-08-31 | 2023-01-03 | 海南巨澜新能源有限公司 | Catalyst for alcohol-hydrogen fuel and preparation method thereof |
| CN115518654B (en) * | 2022-09-30 | 2023-07-25 | 四川蜀泰化工科技有限公司 | Catalyst for preparing hydrogen by reforming methanol and preparation process thereof |
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