CN117443390A - Preparation method and application of aluminum-copper-based three-way catalyst for preparing methanol by carbon dioxide hydrogenation - Google Patents
Preparation method and application of aluminum-copper-based three-way catalyst for preparing methanol by carbon dioxide hydrogenation Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 111
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 46
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 24
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 29
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 22
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- 230000009467 reduction Effects 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000012046 mixed solvent Substances 0.000 claims description 34
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 241000282326 Felis catus Species 0.000 claims description 12
- 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 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 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 27
- 230000002431 foraging effect Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 241000894007 species Species 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 229910016570 AlCu Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 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 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing 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
- B01J23/70—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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
-
- 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
-
- 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 a preparation method and application of an aluminum-copper-based three-way catalyst for preparing methanol by carbon dioxide hydrogenation, wherein the method comprises the following steps: dispersing pseudo-boehmite in a solvent, adding hydrochloric acid, adding copper nitrate and an auxiliary metal precursor, stirring, aging, drying and roasting to obtain the aluminum-copper-based three-way catalyst. The preparation method of the aluminum-copper-based three-way catalyst is simple, the carbon dioxide conversion rate is close to the equilibrium conversion rate at high airspeed, the selectivity of methanol is close to 100%, and the method has industrial application prospect.
Description
Technical Field
The invention relates to a preparation method and application of an aluminum-copper-based three-way catalyst for preparing methanol by carbon dioxide hydrogenation, and belongs to the technical field of carbon dioxide resource conversion.
Background
Methanol is an important basic chemical raw material, and can be used for preparing bulk chemicals such as olefin, aromatic hydrocarbon and the like, gasoline, diesel oil and the like, and can also be directly used as fuel or fuel additive.
In CO 2 In the research of synthesizing methanol by catalytic hydrogenation, cuZnAl is regarded as a widely applied commercial catalyst, and is carried out under the reaction conditions of 5-10MPa and 200-350 ℃ from CO 2 、CO 2 And H 2 Catalytic production of methanol in the mixture of (a). However, the catalyst is specific to pure CO 2 Is insufficient in hydrolytic activity. The noble metal catalyst has the advantages of high activity and good stability, but the catalyst cost is higher. Composite oxide catalysts have been developed in recent years, and the reaction temperature is only about 300 ℃. The Chinese patent with the application number of 202110417516.6 discloses a solid solution Zn-CdZrOx catalyst for preparing methanol by carbon dioxide hydrogenation, but Cd metal has high toxicity and does not accord with the concept of green environmental protection.
Chinese patent application No. cn202010258502.X discloses a graphite-phase carbon nitride supported CuZnAl catalyst for synthesizing methanol by hydrogenation of carbon dioxide. The catalyst uses graphite phase carbon nitride as a carrier, so that the specific surface area of the catalyst is effectively increased, and the reaction gas is easier to adsorb on the surface of the catalyst. The CuZnAl solid solution catalyst can realize the methanol selectivity of more than 88 percent under the conditions of 3MPa,200 ℃ and the contact time W/F (the contact time of the catalyst and the raw material gas or the gas flow rate of the raw material gas entering a reaction tube) =10g.h/mol, but the single-pass conversion rate of carbon dioxide is less than 10 percent. Therefore, developing a carbon dioxide hydrogenation catalyst which is mild in reaction condition, low in cost, green and nontoxic, and has high catalytic activity is a problem to be solved urgently in the process route.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the aluminum-copper-based ternary catalyst with high catalytic activity, which has high catalytic activity, high methanol selectivity, simple preparation mode and low price, and has industrial application prospect.
For this purpose, the first technical solution provided by the present invention is as follows:
a preparation method of an aluminum-copper-based three-way catalyst for preparing methanol by carbon dioxide hydrogenation comprises the steps of dispersing pseudo-boehmite in a solvent, adding hydrochloric acid, adding copper nitrate and an auxiliary metal precursor into the solvent, and obtaining the aluminum-copper-based three-way catalyst after stirring, aging, drying, roasting and reduction;
further, the solvent is water, glycol or a mixture of the two.
Further, the invention also limits the solvent to be a mixture of water and glycol, wherein the mass ratio of water to glycol is 0.5:1-2:1, preferably the mass ratio is 1:1.
Furthermore, the invention also limits the mass ratio of the pseudo-boehmite to the mixed solvent to be 1:30-1:10, and preferably the mass ratio to be 1:25-1:15.
Further, the invention also limits the additive metal precursor to be one of zinc nitrate, cerium nitrate or zirconium nitrate;
furthermore, the invention also limits the mass ratio of the pseudo-boehmite to the copper nitrate to 8:1-1:1, and the preferable ratio is 5:1-2:1.
Furthermore, the invention also limits the mass ratio of the pseudo-boehmite to the auxiliary metal precursor to 20:1-5:1, and the preferable ratio is 15:1-10:1.
Further, the invention also limits the hydrochloric acid to be concentrated hydrochloric acid with the mass fraction of 37%; the mass ratio of the concentrated hydrochloric acid to the mixed solvent is 1:100.
Further, the invention also limits the stirring aging condition to 60 ℃ water bath, the stirring rotating speed to 300r/min and the stirring time to 6h; the drying condition is 130 ℃ for 48 hours.
Further, the invention also limits the roasting condition to roasting in a muffle furnace for 4 hours at 300-650 ℃, preferably 400-550 ℃.
Further, the present invention also limits the reduction conditions to 20% H 2 /N 2 The flow rate of the mixed gas is 50mL/min,the reduction temperature was 400℃and the reduction time was 4 hours.
The invention also provides application of the aluminum-copper-based three-way catalyst in preparing methanol by catalytic hydrogenation of carbon dioxide.
Preferably, the reaction conditions for preparing methanol by hydrogenating carbon dioxide by using the aluminum-copper-based three-way catalyst are as follows: the reaction pressure is 2-5 MPa, the reaction temperature is 180-340 ℃, and the reaction airspeed is 6000-24000 mL/(g) cat H), feed gas volume ratio V (H) 2 )∶V(CO 2 ) Is 3:1.
Compared with the prior art, the invention has the following advantages:
(1) The method adopts a mixed solvent mediated multi-metal gel mode to prepare the precursor of the multi-metal oxide, so that strong interaction is formed between Cu species, al and another metal auxiliary agent, and CuO nano particles are directly inlaid on A1 and the other metal oxide. Then CuO is converted into metallic Cu by a one-step reduction mode, and the metallic Cu in the state is stabilized by a limited domain, so that the falling off and migration of Cu species in the reaction process can be effectively avoided, and the catalyst has excellent catalytic activity.
(2) The prepared AlCu-based ternary catalyst enables trimetallics to form a thorough solid solution structure, and the trimetallics mutually generate lattice doping so as to generate more low-coordination metal sites, so that the AlCu-based ternary catalyst has more catalytic active centers and brings higher catalytic activity.
(3) The catalyst prepared by the invention has low price, simple preparation mode, suitability for large-scale preparation and excellent industrial application prospect.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, without limiting the invention to these specific embodiments. Any person skilled in the art, within the scope of the present disclosure, may apply to the present invention, and equivalents, alterations, modifications, etc. may be included in the scope of protection of the present invention.
Example 1
Adding 10g of pseudo-boehmite into waterIn the mixed solvent of the water and the glycol, the mass ratio of the water to the glycol is 1:1, the mass of the mixed solvent was 250g, then 2.5g of concentrated hydrochloric acid having a mass fraction of 37% was added thereto, and then 2g of copper nitrate and 0.67g of zinc nitrate were further added thereto. Then stirring the mixture for 6 hours in a water bath at 60 ℃ at a stirring speed of 300r/min. It was then transferred to an oven and dried at 130 ℃ for aging for 48h. After drying it was calcined in a muffle furnace at 400℃for 4h, then in a tube furnace at 20% H 2 /N 2 And (3) carrying out reduction treatment in a mixed atmosphere, wherein the gas flow is 50mL/min, the reduction temperature is 400 ℃, and the reduction time is 4h. Finally obtaining the AlCuZn ternary catalyst. It is used for hydrogenation reaction of carbon dioxide, the reaction pressure is 3MPa, the reaction temperature is 250 ℃, and the reaction space velocity is 15000 mL/(g) cat H), feed gas volume ratio V (H) 2 )∶V(CO 2 ) Is 3:1. After 30h of reaction, the conversion of carbon dioxide was 15.9% and the selectivity to methanol was 99.4%.
Example 2
10g of pseudo-boehmite is added into a mixed solvent of water and glycol, the mass ratio of the water to the glycol is 0.8:1, the mass of the mixed solvent is 300g, then 3g of concentrated hydrochloric acid with the mass fraction of 37% is added into the mixed solvent, and then 1.25g of copper nitrate and 0.5g of zirconium nitrate are added into the mixed solvent. Then stirring the mixture for 6 hours in a water bath at 60 ℃ at a stirring speed of 300r/min. It was then transferred to an oven and dried at 130 ℃ for aging for 48h. After drying it was calcined in a muffle furnace at 300℃for 4h, then in a tube furnace at 20% H 2 /N 2 And (3) carrying out reduction treatment in a mixed atmosphere, wherein the gas flow is 50mL/min, the reduction temperature is 400 ℃, and the reduction time is 4h. Finally obtaining the AlCuZr ternary catalyst. It is used for hydrogenation reaction of carbon dioxide, the reaction pressure is 2MPa, the reaction temperature is 180 ℃, and the reaction airspeed is 6000 mL/(g) cat H), feed gas volume ratio V (H) 2 )∶V(CO 2 ) Is 3:1. After 30h of reaction, the conversion of carbon dioxide was 12.9% and the selectivity to methanol was 96.3%.
Example 3
Adding 10g of pseudo-boehmite into a mixed solvent of water and glycol, wherein the mass ratio of the water to the glycol is 1.5:1, and the mass of the mixed solvent is100g, then 1g of concentrated hydrochloric acid having a mass fraction of 37% was added thereto, followed by further addition of 10g of copper nitrate and 2g of zinc nitrate thereto. Then stirring the mixture for 6 hours in a water bath at 60 ℃ at a stirring speed of 300r/min. It was then transferred to an oven and dried at 130 ℃ for aging for 48h. After drying it was calcined in a muffle furnace at 650℃for 4h, then in a tube furnace at 20% H 2 /N 2 And (3) carrying out reduction treatment in a mixed atmosphere, wherein the gas flow is 50mL/min, the reduction temperature is 400 ℃, and the reduction time is 4h. Finally obtaining the AlCuZn ternary catalyst. It is used for hydrogenation reaction of carbon dioxide, the reaction pressure is 5MPa, the reaction temperature is 340 ℃, and the reaction space velocity is 24000 mL/(g) cat H), feed gas volume ratio V (H) 2 )∶V(CO 2 ) Is 3:1. After 30h of reaction, the conversion of carbon dioxide was 12.1% and the selectivity to methanol was 95.7%.
Example 4
10g of pseudo-boehmite is added into a mixed solvent of water and glycol, the mass ratio of the water to the glycol is 0.5:1, the mass of the mixed solvent is 150g, then 1.5g of concentrated hydrochloric acid with the mass fraction of 37% is added into the mixed solvent, and then 5g of copper nitrate and 1g of cerium nitrate are added into the mixed solvent. Then stirring the mixture for 6 hours in a water bath at 60 ℃ at a stirring speed of 300r/min. It was then transferred to an oven and dried at 130 ℃ for aging for 48h. After drying it was calcined in a muffle furnace at 550℃for 4h, then in a tube furnace at 20% H 2 /N 2 And (3) carrying out reduction treatment in a mixed atmosphere, wherein the gas flow is 50mL/min, the reduction temperature is 400 ℃, and the reduction time is 4h. Finally obtaining the AlCuCe ternary catalyst. It is used for hydrogenation reaction of carbon dioxide, the reaction pressure is 3MPa, the reaction temperature is 250 ℃, and the reaction space velocity is 15000 mL/(g) cat H), feed gas volume ratio V (H) 2 )∶V(CO 2 ) Is 3:1. After 30h of reaction, the conversion of carbon dioxide was 16.1% and the selectivity to methanol was 98.9%.
Example 5
Adding 10g of pseudo-boehmite into a mixed solvent of water and glycol in a mass ratio of 1:1, wherein the mass of the mixed solvent is 200g, adding 2g of concentrated hydrochloric acid with a mass fraction of 37%, and then adding 2.5g of copper nitrateAnd 0.83g of zirconium nitrate. Then stirring the mixture for 6 hours in a water bath at 60 ℃ at a stirring speed of 300r/min. It was then transferred to an oven and dried at 130 ℃ for aging for 48h. After drying it was calcined in a muffle furnace at 500℃for 4h, then in a tube furnace at 20% H 2 /N 2 And (3) carrying out reduction treatment in a mixed atmosphere, wherein the gas flow is 50mL/min, the reduction temperature is 400 ℃, and the reduction time is 4h. Finally obtaining the AlCuZr ternary catalyst. It is used for hydrogenation reaction of carbon dioxide, the reaction pressure is 3MPa, the reaction temperature is 300 ℃, and the reaction airspeed is 20000 mL/(g) cat H), feed gas volume ratio V (H) 2 )∶V(CO 2 ) Is 3:1. After 30h of reaction, the conversion of carbon dioxide was 15.3% and the selectivity to methanol was 99.1%.
Example 6
10g of pseudo-boehmite is added into a mixed solvent of water and glycol in a mass ratio of 1:1, the mass of the mixed solvent is 270g, then 2.7g of concentrated hydrochloric acid with mass fraction of 37% is added into the mixed solvent, and then 3.3g of copper nitrate and 0.77g of cerium nitrate are added into the mixed solvent. Then stirring the mixture for 6 hours in a water bath at 60 ℃ at a stirring speed of 300r/min. It was then transferred to an oven and dried at 130 ℃ for aging for 48h. After drying it was calcined in a muffle furnace at 450℃for 4h, then in a tube furnace at 20% H 2 /N 2 And (3) carrying out reduction treatment in a mixed atmosphere, wherein the gas flow is 50mL/min, the reduction temperature is 400 ℃, and the reduction time is 4h. Finally obtaining the AlCuCe ternary catalyst. It is used for hydrogenation reaction of carbon dioxide, the reaction pressure is 4MPa, the reaction temperature is 280 ℃, and the reaction space velocity is 16000 mL/(g) cat H), feed gas volume ratio V (H) 2 )∶V(CO 2 ) Is 3:1. After 30h of reaction, the conversion of carbon dioxide was 15.7% and the selectivity to methanol was 99.3%.
Example 7
10g of pseudo-boehmite is added into a mixed solvent of water and glycol, the mass ratio of the water to the glycol is 2:1, the mass of the mixed solvent is 250g, then 2.5g of concentrated hydrochloric acid with the mass fraction of 37% is added into the mixed solvent, and then 3g of copper nitrate and 1g of zinc nitrate are added into the mixed solvent. Then stirring the mixture for 6 hours in a water bath at 60 ℃ at a stirring speed of 300r/min. Then transfer it toDrying and aging for 48 hours at 130 ℃ in an oven. After drying it was calcined in a muffle furnace at 500℃for 4h, then in a tube furnace at 20% H 2 /N 2 And (3) carrying out reduction treatment in a mixed atmosphere, wherein the gas flow is 50mL/min, the reduction temperature is 400 ℃, and the reduction time is 4h. Finally obtaining the AlCuZn ternary catalyst. It is used for hydrogenation reaction of carbon dioxide, the reaction pressure is 4MPa, the reaction temperature is 320 ℃, and the reaction space velocity is 22000 mL/(g) cat H), feed gas volume ratio V (H) 2 )∶V(CO 2 ) Is 3:1. After 30h of reaction, the conversion of carbon dioxide was 15.5% and the selectivity to methanol was 99.2%.
Example 8
10g of pseudo-boehmite is added into a mixed solvent of water and glycol in a mass ratio of 1:1, the mass of the mixed solvent is 240g, then 2.4g of concentrated hydrochloric acid with mass fraction of 37% is added into the mixed solvent, and then 5g of copper nitrate and 0.72g of zirconium nitrate are added into the mixed solvent. Then stirring the mixture for 6 hours in a water bath at 60 ℃ at a stirring speed of 300r/min. It was then transferred to an oven and dried at 130 ℃ for aging for 48h. After drying it was calcined in a muffle furnace at 550℃for 4h, then in a tube furnace at 20% H 2 /N 2 And (3) carrying out reduction treatment in a mixed atmosphere, wherein the gas flow is 50mL/min, the reduction temperature is 400 ℃, and the reduction time is 4h. Finally obtaining the AlCuZr ternary catalyst. It is used for hydrogenation reaction of carbon dioxide, the reaction pressure is 3.5MPa, the reaction temperature is 320 ℃, and the reaction airspeed is 10000 mL/(g) ca t.h), the volume ratio of raw material gas V (H) 2 )∶V(CO 2 ) Is 3:1. After 30h of reaction, the conversion of carbon dioxide was 15.8% and the selectivity to methanol was 99.1%.
Example 9
10g of pseudo-boehmite was added to 250g of water, followed by adding thereto 2.5g of concentrated hydrochloric acid having a mass fraction of 37%, followed by adding thereto 2g of copper nitrate and 0.67g of zinc nitrate. Then stirring the mixture for 6 hours in a water bath at 60 ℃ at a stirring speed of 300r/min. It was then transferred to an oven and dried at 130 ℃ for aging for 48h. After drying it was calcined in a muffle furnace at 400℃for 4h, then in a tube furnace at 20% H 2 /N 2 The reduction treatment is carried out in the mixed atmosphere,the gas flow rate is 50mL/min, the reduction temperature is 400 ℃, and the reduction time is 4h. Finally obtaining the AlCuZn ternary catalyst. It is used for hydrogenation reaction of carbon dioxide, the reaction pressure is 3MPa, the reaction temperature is 250 ℃, and the reaction space velocity is 15000 mL/(g) cat H), feed gas volume ratio V (H) 2 )∶V(CO 2 ) Is 3:1. After 30h of reaction, the conversion of carbon dioxide was 8.3% and the selectivity to methanol was 82.1%.
Example 10
10g of pseudo-boehmite was added to 250g of ethylene glycol, followed by adding thereto 2.5g of concentrated hydrochloric acid having a mass fraction of 37%, followed by adding thereto 2g of copper nitrate and 0.67g of zinc nitrate. Then stirring the mixture for 6 hours in a water bath at 60 ℃ at a stirring speed of 300r/min. It was then transferred to an oven and dried at 130 ℃ for aging for 48h. After drying it was calcined in a muffle furnace at 400℃for 4h, then in a tube furnace at 20% H2/N 2 And (3) carrying out reduction treatment in a mixed atmosphere, wherein the gas flow is 50mL/min, the reduction temperature is 400 ℃, and the reduction time is 4h. Finally obtaining the AlCuZn ternary catalyst. It is used for hydrogenation reaction of carbon dioxide, the reaction pressure is 3MPa, the reaction temperature is 250 ℃, and the reaction space velocity is 15000 mL/(g) cat H), feed gas volume ratio V (H) 2 )∶V(CO 2 ) Is 3:1. After 30h of reaction, the conversion of carbon dioxide was 7.8% and the selectivity to methanol was 25.8%.
Comparative example 1
Solution A was prepared by placing 10g of aluminum nitrate, 2g of copper nitrate, and 0.67g of zinc nitrate in a 200mL beaker, adding 150mL of deionized water, placing 4g of sodium hydroxide in the 200mL beaker, and adding 150mL of deionized water. And (3) slowly dripping the solution A and the solution B into a three-neck flask respectively, then heating the three-neck flask in a water bath at 80 ℃ for 4 hours, centrifugally washing the obtained precipitate, and drying and aging the precipitate in an oven at 130 ℃ for 48 hours. Calcining in a muffle furnace at 400 ℃ for 4h, and then in a tube furnace at 20% H 2 /N 2 And (3) carrying out reduction treatment in a mixed atmosphere, wherein the gas flow is 50mL/min, the reduction temperature is 400 ℃, and the reduction time is 4h. Finally obtaining the AlCuZn ternary catalyst. It is used for hydrogenation reaction of carbon dioxide, the reaction pressure is 3MPa, the reaction temperature is 250 ℃, and the reaction airspeed is15000mL/(g cat H), feed gas volume ratio V (H) 2 )∶V(CO 2 ) Is 3:1. After 30h of reaction, the conversion of carbon dioxide was 4.2% and the selectivity to methanol was 20.8%.
By the above examples 1 to 10, the catalyst provided in examples 1 to 8 provided by the present invention has higher catalytic performance than the catalyst prepared in examples 8 to 9, which may be because only water is used as a solvent in example 9, so that the number of hydroxyl groups in the whole system is insufficient, and more Al species cannot be complexed with hydroxyl groups, so that strong interaction cannot be generated between Al species and Cu species, and thus the active species are fallen off in the reaction process, resulting in lower conversion rate of the catalyst; in example 10, only ethylene glycol was used as the solvent, which resulted in a final synthesis catalyst with a high carbon content, and the active species were entrapped by carbon, resulting in a lower catalyst conversion, while due to the high carbon content, a large amount of byproducts such as CO were produced during the reaction, resulting in a lower catalyst selectivity.
Compared with the mode of preparing the catalyst by only adopting the common coprecipitation method in comparative example 1, the preparation method adopts the mode of adopting the mixed solvent mediated multi-metal gel to prepare the multi-metal oxide precursor, so that strong interaction is realized between metals, and the mixed solvent is adopted to ensure that the metal is dispersed more uniformly, thereby ensuring that Cu species are stabilized in a limited domain and effectively avoiding the falling off and migration of the Cu species in the reaction process.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (10)
1. A preparation method of an aluminum-copper-based three-way catalyst for preparing methanol by carbon dioxide hydrogenation is characterized in that pseudo-boehmite is dispersed in a solvent, hydrochloric acid is added, copper nitrate and an auxiliary agent metal precursor are added into the solvent, and the aluminum-copper-based three-way catalyst is obtained after stirring, aging, drying, roasting and reduction;
the solvent is one or a mixture of water and glycol;
the mass ratio of the pseudo-boehmite to the mixed solvent is 1:30-1:10;
the mass ratio of the pseudo-boehmite to the copper nitrate is 8:1-1:1;
the mass ratio of the pseudo-boehmite to the auxiliary agent metal precursor is 20:1-5:1.
2. The preparation method of the aluminum-copper-based three-way catalyst for preparing methanol by hydrogenation of carbon dioxide, which is characterized in that the solvent is formed by mixing water and glycol according to the mass ratio of 0.5:1-2:1.
3. The method for preparing the aluminum-copper-based three-way catalyst for preparing methanol by hydrogenation of carbon dioxide according to claim 1, wherein the mass ratio of the pseudo-boehmite to the mixed solvent is 1:25-1:15; the mass ratio of the pseudo-boehmite to the copper nitrate is 5:1-2:1; the mass ratio of the pseudo-boehmite to the auxiliary agent metal precursor is 15:1-10:1.
4. The method for preparing the aluminum-copper-based three-way catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the auxiliary metal precursor is one of zinc nitrate, cerium nitrate and zirconium nitrate.
5. The method for preparing the aluminum-copper-based three-way catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the hydrochloric acid is concentrated hydrochloric acid with the mass fraction of 37%; the mass ratio of the concentrated hydrochloric acid to the mixed solvent is 1:100.
6. the method for preparing the aluminum-copper-based three-way catalyst for preparing methanol by hydrogenation of carbon dioxide according to claim 1, wherein the stirring aging condition is water bath at 60 ℃, the stirring rotating speed is 300r/min, and the stirring time is 6h; the drying condition is 130 ℃ for 48 hours.
7. The method for preparing the aluminum-copper-based three-way catalyst for preparing methanol by hydrogenation of carbon dioxide according to claim 1, wherein the roasting condition is that the roasting time in a muffle furnace is 4 hours, and the roasting temperature is 300-650 ℃.
8. The method for preparing the aluminum-copper-based three-way catalyst for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein the reduction condition is 20% H 2 /N 2 The gas flow of the mixed gas is 50mL/min, the reduction temperature is 400 ℃, and the reduction time is 4h.
9. Use of the aluminum-copper-based three-way catalyst according to any one of claims 1-8 in the preparation of methanol by catalytic hydrogenation of carbon dioxide.
10. The use of the aluminum-copper-based three-way catalyst according to claim 9 in preparing methanol by catalytic hydrogenation of carbon dioxide, wherein the reaction pressure for preparing methanol by catalytic hydrogenation of carbon dioxide is 2-5 MPa, the reaction temperature is 180-340 ℃, and the reaction space velocity is 6000-24000 mL/(g) cat H), feed gas volume ratio V (H) 2 )∶V(CO 2 ) Is 3:1.
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