CN113209974A - Mesoporous Cu-ZnO/Al2O3-ZrO2Composite catalyst and preparation method and application thereof - Google Patents
Mesoporous Cu-ZnO/Al2O3-ZrO2Composite catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002131 composite material Substances 0.000 claims abstract description 54
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910016341 Al2O3 ZrO2 Inorganic materials 0.000 claims abstract description 23
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 14
- MBBZMMPHUWSWHV-BDVNFPICSA-N N-methylglucamine Chemical compound CNC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO MBBZMMPHUWSWHV-BDVNFPICSA-N 0.000 claims abstract description 12
- 229960003194 meglumine Drugs 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000001338 self-assembly Methods 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 13
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims 8
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000007654 immersion Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000007707 calorimetry Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 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
- B01J23/70—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
-
- 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
-
- B01J35/647—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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 discloses Cu-ZnO/Al with a good mesoporous structure2O3‑ZrO2Composite catalyst and preparation method and application thereof, wherein carrier of catalyst is mesoporous Al2O3‑ZrO2The composite oxide contains Cu and ZnO as active components and has total loading10-20% of the total mass of the catalyst, and the mass ratio of Cu to ZnO is 1-3. Mesoporous Al in the invention2O3‑ZrO2The composite oxide is prepared by self-assembly in aqueous solution of meglumine, wherein Al is2O3And ZrO2The mass ratio is 9-7, and Cu-ZnO is loaded on mesoporous Al by an isometric immersion method2O3‑ZrO2The Cu-ZnO/Al with good mesoporous structure is finally obtained on the surface of the composite oxide2O3‑ZrO2The supported composite catalyst promotes the dispersion of Cu and ZnO and improves CO2Activity and selectivity of preparing methanol by catalytic hydrogenation.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to mesoporous Cu-ZnO/Al2O3-ZrO2Composite catalyst, preparation method thereof and application thereof in CO2Application in the reaction of preparing methanol by catalytic hydrogenation.
Background
Under the limitations of the current policy, CO2The emission of (2) greatly limits the development of industrial production, and CO is discharged2The preparation of methanol by catalytic hydrogenation not only can effectively reduce CO2The emission of the methanol can also relieve the environmental and energy crisis, more importantly, the methanol can also be used as a raw material for chemical production, and has great application prospect. Is currently used for CO2The industrial catalyst for preparing methanol by catalytic hydrogenation is mainly a Cu/ZnAlO catalyst, but the reactivity and selectivity of the catalyst under mild reaction conditions still face huge challenges, and the key point is to develop the catalyst with high activity and high selectivity. At present, the research proves that the CO exists2In the reaction of catalytic hydrogenation to prepare methanol, CO2The active sites are mainly on the Cu-ZnO interface, so the Cu-ZnO-based catalyst has better methanol yield (Science, 355, 2017, pages 1296-1299). The higher active surface area of the metal Cu in the catalyst can effectively promote the hydrogenation process in the reaction, thereby improving the CO in the reaction2The transformation of (1) (Journal of Catalysis, vol. 393 2021, pp. 207-214). In addition, the high specific surface of the catalyst can promote CO2Adsorption of (2), and strong surface alkalinity can increase CO2The adsorption strength on the surface of the catalyst is favorable for CO2Activation of (1) (Catalysis Today, volume 339, 2020, pages 352 to 361). Due to CO2Inevitable inverse water accompanied in the reaction process of preparing methanol by catalytic hydrogenationThe occurrence of steam shift and methanol decomposition reaction generates a large amount of byproduct CO which is not beneficial to the selectivity of methanol in the reaction, and the absorption calorimetric detection result of the CO proves that the surface alkalinity of the metal Cu catalyst can enhance the absorption of the CO, and the strong absorption can effectively inhibit reverse steam shift and methanol decomposition reaction, thereby improving the CO2Selectivity to methanol in catalytic hydrogenation reactions (Applied Catalysis a, General, volume 571, 2019, page 51-60). Therefore, CO is to be increased2The activity and selectivity of the catalytic hydrogenation for preparing the methanol need to prepare a Cu-ZnO-based catalyst with high specific surface area, high metal Cu active specific surface and strong alkaline surface.
As the mesoporous material has the characteristics of controllable appearance, high specific surface area and good thermal stability, the mesoporous material has good application prospect as a carrier of the catalyst, and meanwhile, Al2O3Cheap and easily available, good thermal stability, and wide application in the industrial catalysis field (microporouus and mesorouus Materials, volume 91 in 2006, pages 293-295). And ZrO2It is also widely used as CO due to its unique chemical properties and weak hydrophilicity2A carrier for preparing a methanol catalyst by catalytic hydrogenation (Energy Conversion and Management, volume 118 2016, page 21-31). Furthermore, ZrO2Also has strong surface alkalinity, and can effectively promote CO2And the interaction between the metal Cu and the carrier is enhanced to improve the dispersion degree of the active metal Cu on the surface of the catalyst (Chemical Engineering Journal, volume 293 in 2016, pages 327-336). But ZrO2The specific surface area of the carrier is not high, and the thermal stability is required to be improved.
Disclosure of Invention
The invention aims to provide mesoporous Cu-ZnO/Al2O3-ZrO2Composite catalyst, carrier Al thereof2O3-ZrO2The composite oxide has good mesoporous structure and higher specific surface area, can promote the dispersion of active component metals Cu and ZnO, and has mesoporous Cu-ZnO/Al2O3-ZrO2The composite catalyst has higher catalytic activity, selectivity and thermal stability; another object of the present invention is to provide a method for preparing the composite catalyst; book (I)The invention also aims to provide the application of the catalyst in the reaction of preparing methanol by catalytic hydrogenation of carbon dioxide.
The invention is realized by the following technical scheme:
Cu-ZnO/Al2O3-ZrO2The carrier of the composite catalyst is Al with a good mesoporous structure2O3-ZrO2The composite oxide comprises active components of Cu and ZnO, and the total loading capacity of the composite oxide is 10-20%, wherein the molar ratio of Cu to ZnO is 1-3, and Al2O3-ZrO2ZrO in composite oxides2The mass fraction of the component (A) is 10% -20%.
The invention further improves the scheme as follows:
Cu-ZnO/Al2O3-ZrO2The preparation method of the composite catalyst comprises the following steps:
(1) preparation of mesoporous Al2O3-ZrO2Composite oxide: respectively weighing aluminum isopropoxide and zirconium nitrate, fully dissolving the aluminum isopropoxide and the zirconium nitrate in a meglumine aqueous solution, regulating and controlling the pH value of the solution by using a dilute nitric acid solution, drying and removing water after self-assembly is finished, and finally calcining to obtain white powdery mesoporous Al2O3-ZrO2A composite oxide;
(2) preparation of Cu-ZnO/Al2O3-ZrO2Composite catalyst: weighing copper nitrate and zinc nitrate, dissolving in absolute ethyl alcohol to prepare a mixed solution, and soaking the mixed solution into the mesoporous Al prepared in the step (1)2O3-ZrO2Drying and reducing the composite oxide solid powder to obtain Cu-ZnO/Al2O3-ZrO2And (3) compounding a catalyst.
The invention further improves the scheme as follows:
in the step (1), Al is obtained2O3-ZrO2ZrO in composite oxides2The mass fraction of the component (A) is 10% -20%.
Further, in the step (1), meglumine is used as a pore-forming agent, and the mass concentration of the meglumine aqueous solution is 10-50%.
Further, in the step (1), the pH value of the solution is regulated to 5 by using a dilute nitric acid solution.
Further, in the step (1), the calcining temperature is 600 ℃, and the calcining time is 4-6 hours.
In the step (2), the amount of the copper nitrate and the zinc nitrate is calculated by the molar amount of Cu and ZnO contained in the copper nitrate and the zinc nitrate, and the molar ratio of Cu to ZnO is 1-3.
Further, in the step (2), the total loading amount of Cu and ZnO is 10% -20%.
Further, in the step (2), the reduction temperature is 280-320 ℃, and the reduction gas is 10-20% of H2/N2The time is 2 h.
The invention has the further improvement scheme that:
mesoporous Cu-ZnO/Al2O3-ZrO2The composite catalyst is applied to the reaction of preparing methanol by catalytic hydrogenation of carbon dioxide.
In the invention, the loading capacity is the total mass of Cu and ZnO and the prepared mesoporous Cu-ZnO/Al2O3-ZrO2Percentage of the total mass of the composite catalyst.
The invention has the beneficial effects that:
the invention can load Cu-ZnO in mesoporous Al2O3-ZrO2Surface of composite oxide using mesoporous Al2O3As a structural assistant of the catalyst, the catalyst is endowed with a good mesoporous structure, the thermal stability and the specific surface area of the catalyst are improved, the dispersion degree of Cu and ZnO is promoted, and the active specific surface area of metal Cu and a Cu-ZnO active interface are improved. ZrO2Can endow the catalyst with a stronger alkaline surface, regulate and control the interaction strength of the metal Cu and the carrier in the catalyst, further promote the dispersion degree and the active specific surface area of the metal Cu, and finally improve the CO2Activity and selectivity of catalytic hydrogenation for preparing methanol.
Al prepared by self-assembly method in the invention2O3-ZrO2Composite oxide using meglumine as template agent, Zr4+With meglumineThe amido generates coordination in the aqueous solution and interacts with micelle generated by hydrolysis of aluminum isopropoxide under the acidic condition to finally generate Al with a mesoporous structure2O3-ZrO2The composite oxide has a good mesoporous structure and a higher specific surface area, and can promote the dispersion of metal Cu and ZnO: .
The invention utilizes Al2O3And ZrO2The mass ratio of (A) to (B) regulates the structure and/or surface properties of the catalyst, ZrO2The more the mass of (A), the stronger the surface alkalinity, which is favorable for CO2Selectivity for methanol production by catalytic hydrogenation, but excess ZrO2Can destroy the mesoporous structure of the substance, resulting in a reduction in the specific surface area. The invention provides Cu-ZnO/Al2O3-ZrO2The composite catalyst has higher catalytic activity and selectivity:
in the preparation method of the invention, mesoporous Al is used2O3-ZrO2The composite oxide is used as a carrier to prepare Cu-ZnO/Al by an impregnation method2O3-ZrO2The composite catalyst makes Cu-ZnO uniformly distributed in mesoporous Al with controllable surface structure and property2O3-ZrO2The catalytic activity of the catalyst is optimized to the maximum extent by the surface of the composite oxide.
The mesoporous Cu-ZnO/Al of the invention2O3-ZrO2Use of composite catalyst for CO2Hydrogenation reaction for preparing methanol. The data show a 7800 mL h pressure at 5 MPa, 240 ℃ temperature and space velocity−1 g-1Lower, mesoporous Cu-ZnO/Al2O3-ZrO2CO on composite catalyst2The conversion rate reaches 14.5%, and the selectivity is 75%. Has good industrial application prospect.
Drawings
FIG. 1 shows Al produced by the present invention2O3-ZrO2Composite oxide catalyst carrier and Al prepared in reference example2O3Scanning electron micrographs of the support;
wherein (A) is the mesoporous Al prepared in reference example 22O3Scanning electron microscope images of the carrier; (B) scanning Electron microscope for AlZrO-9 from example 1A drawing; (C) scanning electron micrographs of AlZrO-8 obtained in example 3; (D) scanning electron micrographs of AlZrO-7 obtained in example 5;
FIG. 2 shows the CO on the surface of the catalyst prepared by the invention at the temperature of 150 DEG C2The result of the adsorption calorimetry detection.
Detailed Description
Reference ratio 1
For comparison, a Cu/ZnAlO industrial catalyst with a loading of 58% was first prepared by a coprecipitation method. 11.0 g of Cu (NO) was weighed3)2·3H2O、5.9 g Zn(NO3)2·6H2O and 3.7 g Al (NO)3)3.9H2Dissolving O in 100 mL of water; another 9.3 g of anhydrous Na is taken2CO3Dissolve in another 100 mL of water. Then adding dropwise into deionized water containing 200 mL of water at 80 deg.C under vigorous stirring, vigorously stirring in 80 deg.C water bath for 0.5 hr, repeatedly filtering and washing to neutrality, drying in oven at 100 deg.C, and drying with 10% H2/N2Reducing the mixed gas for 2 h at the temperature of 300 ℃ to obtain the Cu/ZnAlO catalyst with the Cu loading of 58 percent, wherein the molar mass ratio of the metal Cu to the ZnO is 7: 3.
Reference ratio 2
Weighing 15 g of meglumine and dissolving in 300 mL of water; another 4.0 g of aluminum isopropoxide was dissolved in it. Vigorously stirring at room temperature for 6 h, adjusting pH to 5 with 10% dilute nitric acid solution, drying at 100 deg.C in a oven, and calcining at 600 deg.C in a muffle furnace for 4 h to obtain mesoporous Al2O3The surface pore structure of the carrier is detected by a scanning electron microscope and is shown in figure 1 (A), which shows that the carrier has a good mesoporous structure.
Reference ratio 3
Firstly, 0.8 g of mesoporous Al in reference ratio 2 is weighed2O30.26 g of Zn (NO) was weighed out separately3)3·6H2O and 0.49 g Cu (NO)3)2·3H2O was dissolved in 3 mL of absolute ethanol. Immersing the mesoporous Al in an ethanol solution containing Zn and Cu2O3Adding into powder, removing ethanol in oven at 80 deg.C, and adding 10% H2/N2Reducing the mixed gas at 300 DEG C2 h, obtaining the mesoporous Cu-ZnO/Al with the total loading capacity of Cu and ZnO of 20 percent2O3The catalyst comprises Cu metal and ZnO with a molar mass ratio of 7: 3. The surface of which is alkaline by CO2Higher CO, in the detection of adsorption calorimetry2The initial heat of adsorption indicates greater surface alkalinity and greater CO2The adsorption saturation indicates more CO2The result of the adsorption of the sites is shown in FIG. 2.
Example 1
Weighing 15 g of meglumine and dissolving in 300 mL of water; another 3.6 g of aluminum isopropoxide and 0.35 g of Zr (NO) are taken3)4.5H2O is dissolved therein. Vigorously stirring at room temperature for 6 h, adjusting pH to 5 with 10% dilute nitric acid solution, drying at 100 deg.C in a oven, and calcining at 600 deg.C in a muffle furnace for 4 h to obtain mesoporous Al2O3And ZrO2Composite oxide support, wherein Al2O3And ZrO2The mass ratio of (A) to (B) was 9:1, and the sample number was AlZrO-9. The surface pore structure of the mesoporous silica gel is detected by a scanning electron microscope and is shown in figure 1 (B), which shows that the mesoporous silica gel has a good mesoporous structure.
Example 2
0.8 g of AlZrO-9 in the medium pores of example 1 was weighed out first, and 0.26 g of Zn (NO) was weighed out separately3)3·6H2O and 0.49 g Cu (NO)3)2·3H2O was dissolved in 3 mL of absolute ethanol. Soaking Zn and Cu-containing ethanol solution into mesoporous AlZrO-9 powder, removing ethanol in an oven at 80 deg.C, and adding 10% H2/N2Reducing the mixed gas for 2 hours at the temperature of 300 ℃ to obtain the mesoporous Cu-ZnO/AlZrO-9 catalyst with the total loading capacity of Cu and ZnO of 20 percent, wherein the molar mass ratio of the metal Cu to the ZnO is 7: 3. The surface of which is alkaline by CO2Higher CO, in the detection of adsorption calorimetry2The initial heat of adsorption indicates greater surface alkalinity and greater CO2The adsorption saturation indicates more CO2The result of the adsorption of the sites is shown in FIG. 2.
Example 3
Weighing 15 g of meglumine and dissolving in 300 mL of water; another 3.2 g of aluminum isopropoxide and 0.70 g of Zr (NO) are taken3)4.5H2O is dissolved therein.Vigorously stirring at room temperature for 6 h, adjusting pH to 5 with 10% dilute nitric acid solution, drying at 100 deg.C in a oven, and calcining at 600 deg.C in a muffle furnace for 4 h to obtain mesoporous Al2O3And ZrO2Composite oxide support, wherein Al2O3And ZrO2The mass ratio of (A) to (B) is 8:2, and the sample number is AlZrO-8. The surface pore structure of the mesoporous silica gel is detected by a scanning electron microscope and is shown in figure 1 (C), which shows that the mesoporous silica gel has a good mesoporous structure.
Example 4
0.8 g of AlZrO-8 as medium pore in example 3 was weighed out first, and 0.26 g of Zn (NO) was weighed out separately3)3·6H2O and 0.49 g Cu (NO)3)2·3H2O was dissolved in 3 mL of absolute ethanol. Soaking Zn and Cu-containing ethanol solution into mesoporous AlZrO-9 powder, removing ethanol in an oven at 80 deg.C, and adding 10% H2/N2Reducing the mixed gas for 2 hours at the temperature of 300 ℃ to obtain the mesoporous Cu-ZnO/AlZrO-8 catalyst with the total loading capacity of Cu and ZnO of 20 percent, wherein the molar mass ratio of the metal Cu to the ZnO is 7: 3. The surface of which is alkaline by CO2Higher CO, in the detection of adsorption calorimetry2The initial heat of adsorption indicates greater surface alkalinity and greater CO2The adsorption saturation indicates more CO2The result of the adsorption of the sites is shown in FIG. 2.
Example 5
Weighing 15 g of meglumine and dissolving in 300 mL of water; another 2.8 g of aluminum isopropoxide and 1.0 g of Zr (NO) are taken3)4.5H2O is dissolved therein. Vigorously stirring at room temperature for 6 h, adjusting pH to 5 with 10% dilute nitric acid solution, drying at 100 deg.C in a oven, and calcining at 600 deg.C in a muffle furnace for 4 h to obtain mesoporous Al2O3And ZrO2Composite oxide support, wherein Al2O3And ZrO2The mass ratio of (A) to (B) was 7:3, and the sample number was AlZrO-7. The surface pore structure detected by a scanning electron microscope is shown in FIG. 1 (D), which shows that compared with other samples in the examples, the AlZrO-7 has obvious agglomeration on the surface, which results in the generation of flaky substances and the disappearance of pores on the surface, so that Al2O3And ZrO2The mesoporous structure of the composite oxide is excessively ZrO2And (4) destroying.
Example 6
0.8 g of AlZrO-7 in the medium pores of example 5 was weighed out first, and 0.26 g of Zn (NO) was weighed out separately3)3·6H2O and 0.49 g Cu (NO)3)2·3H2O was dissolved in 3 mL of absolute ethanol. Soaking Zn and Cu-containing ethanol solution into mesoporous AlZrO-9 powder, removing ethanol in an oven at 80 deg.C, and adding 10% H2/N2Reducing the mixed gas for 2 hours at the temperature of 300 ℃ to obtain the mesoporous Cu-ZnO/AlZrO-9 catalyst with the total loading capacity of Cu and ZnO of 20 percent, wherein the molar mass ratio of the metal Cu to the ZnO is 7: 3. The surface of which is alkaline by CO2Higher CO, in the detection of adsorption calorimetry2The initial heat of adsorption indicates greater surface alkalinity and greater CO2The adsorption saturation indicates more CO2The result of the adsorption of the sites is shown in FIG. 2.
Reference ratio 4
Weighing 0.5 g of Cu/ZnAlO catalyst with the load of 58 percent in reference ratio 1, loading the Cu/ZnAlO catalyst into a micro fixed bed reactor, wherein the inner diameter of a reaction tube is 6 mm, heating to 300 ℃ at 1 ℃/min, and then using 10 percent H2/N2And reducing for 2 h. The reaction pressure is 5 MPa, the reaction temperature is 240 ℃, and V (H) is2)/V(CO2) = 3/1，GHSV = 7800 mL h−1 g−1The results of the conversion and selectivity analysis of the reaction are shown in Table 1.
Reference ratio 5
0.5 g of the mesoporous Cu-ZnO/Al in reference example 3 was weighed2O3Loading the catalyst into a miniature fixed bed reactor, heating the inner diameter of a reaction tube to 300 ℃ at 1 ℃/min, and then adding 10% H2/N2And reducing for 2 h. The reaction pressure is 5 MPa, the reaction temperature is 240 ℃, and V (H) is2)/V(CO2) = 3/1，GHSV = 7800 mL h−1 g−1The results of the conversion and selectivity analysis of the reaction are shown in Table 1.
Example 7
0.5 g of the mesoporous Cu-ZnO/AlZrO-9 catalyst in the example 2 is weighed and loaded into a micro fixed bed reactor, the inner diameter of the reaction tube is 6 mm, the temperature is raised to 30 ℃ at 1 ℃/min0 ℃ and 10% H2/N2And reducing for 2 h. The reaction pressure is 5 MPa, the reaction temperature is 240 ℃, and V (H) is2)/V(CO2) = 3/1，GHSV = 7800 mL h−1 g−1The results of the conversion and selectivity analysis of the reaction are shown in Table 1.
Example 8
0.5 g of the mesoporous Cu-ZnO/AlZrO-8 catalyst in example 4 was weighed and loaded into a micro fixed bed reactor, the inner diameter of the reaction tube was 6 mm, the temperature was raised to 300 ℃ at 1 ℃/min, and then 10% H was added2/N2And reducing for 2 h. The reaction pressure is 5 MPa, the reaction temperature is 240 ℃, and V (H) is2)/V(CO2) = 3/1，GHSV = 7800 mL h−1 g−1The results of the conversion and selectivity analysis of the reaction are shown in Table 1.
Example 9
0.5 g of the mesoporous Cu-ZnO/AlZrO-7 catalyst in example 6 was weighed and loaded into a micro fixed bed reactor, the inner diameter of the reaction tube was 6 mm, the temperature was raised to 300 ℃ at 1 ℃/min, and then 10% H was added2/N2And reducing for 2 h. The reaction pressure is 5 MPa, the reaction temperature is 240 ℃, and V (H) is2)/V(CO2) = 3/1，GHSV = 7800 mL h−1 g−1The results of the conversion and selectivity analysis of the reaction are shown in Table 1.
TABLE 1 Cu-ZnO based catalyst vs. CO2Conversion rate and selectivity of catalytic hydrogenation for preparing methanol
As can be seen from Table 1, the pressure at 5 MPa, the temperature at 240 ℃ and the space velocity were 7800 mL h−1 g-1In the invention, the prepared mesoporous Cu-ZnO/Al2O3-ZrO2CO on composite catalyst2The conversion rate can reach 14.5%, and the selectivity can reach 75%. Has good industrial application prospect.
Claims (10)
1. Cu-ZnO/Al2O3-ZrO2The composite catalyst is characterized in that the carrier of the catalyst is Al with a good mesoporous structure2O3-ZrO2The composite oxide comprises active components of Cu and ZnO, and the total loading capacity of the composite oxide is 10-20%, wherein the molar ratio of Cu to ZnO is 1-3, and Al2O3-ZrO2ZrO in composite oxides2The mass fraction of the component (A) is 10% -20%.
2. Preparation of a Cu-ZnO/Al alloy according to claim 12O3-ZrO2A method of compounding a catalyst, comprising the steps of:
(1) preparation of mesoporous Al2O3-ZrO2Composite oxide: respectively weighing aluminum isopropoxide and zirconium nitrate, fully dissolving the aluminum isopropoxide and the zirconium nitrate in a meglumine aqueous solution, regulating and controlling the pH value of the solution by using a dilute nitric acid solution, drying and removing water after self-assembly is finished, and finally calcining to obtain white powdery mesoporous Al2O3-ZrO2A composite oxide;
(2) preparation of Cu-ZnO/Al2O3-ZrO2Composite catalyst: weighing copper nitrate and zinc nitrate, dissolving in absolute ethyl alcohol to prepare a mixed solution, and soaking the mixed solution into the mesoporous Al prepared in the step (1)2O3-ZrO2Drying and reducing the composite oxide solid powder to obtain Cu-ZnO/Al2O3-ZrO2And (3) compounding a catalyst.
3. The Cu-ZnO/Al alloy of claim 22O3-ZrO2The preparation method of the composite catalyst is characterized by comprising the following steps: in the step (1), Al is obtained2O3-ZrO2ZrO in composite oxides2The mass fraction of the component (A) is 10% -20%.
4. The Cu-ZnO/Al alloy of claim 22O3-ZrO2The preparation method of the composite catalyst is characterized by comprising the following steps: in the step (1), meglumine is used as a pore-forming agent, and the mass concentration of the meglumine aqueous solution is 10-50%.
5. The Cu-ZnO/Al alloy of claim 22O3-ZrO2The preparation method of the composite catalyst is characterized by comprising the following steps: in the step (1), the pH value of the solution is regulated to 5 by using a dilute nitric acid solution.
6. The Cu-ZnO/Al alloy of claim 22O3-ZrO2The preparation method of the composite catalyst is characterized by comprising the following steps: in the step (1), the calcining temperature is 600 ℃, and the calcining time is 4-6 h.
7. The Cu-ZnO/Al alloy of claim 22O3-ZrO2The preparation method of the composite catalyst is characterized by comprising the following steps: in the step (2), the dosage of the copper nitrate and the zinc nitrate is calculated by the molar weight of Cu and ZnO contained in the copper nitrate and the zinc nitrate, and the molar ratio of the Cu to the ZnO is 1-3.
8. The Cu-ZnO/Al alloy of claim 22O3-ZrO2The preparation method of the composite catalyst is characterized by comprising the following steps: in the step (2), the total loading amount of Cu and ZnO is 10% -20%.
9. The Cu-ZnO/Al alloy of claim 22O3-ZrO2The preparation method of the composite catalyst is characterized by comprising the following steps: in the step (2), the reduction temperature is 280-320 ℃, and the reduction gas is 10-20% of H2/N2The time is 2 h.
10. The mesoporous Cu-ZnO/Al of claim 12O3-ZrO2The composite catalyst is applied to the reaction of preparing methanol by catalytic hydrogenation of carbon dioxide.
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