CN114713222B - Embedded zirconia nanotube catalyst and preparation method and application thereof - Google Patents
Embedded zirconia nanotube catalyst and preparation method and application thereof Download PDFInfo
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- CN114713222B CN114713222B CN202011526607.5A CN202011526607A CN114713222B CN 114713222 B CN114713222 B CN 114713222B CN 202011526607 A CN202011526607 A CN 202011526607A CN 114713222 B CN114713222 B CN 114713222B
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 239000002071 nanotube Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 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 39
- 239000010949 copper Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 30
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 11
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 14
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 5
- 208000012839 conversion disease Diseases 0.000 abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001431 copper ion Inorganic materials 0.000 abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 3
- 230000000670 limiting effect Effects 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000007598 dipping method Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000001384 succinic acid Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910001339 C alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QNZFKUWECYSYPS-UHFFFAOYSA-N lead zirconium Chemical compound [Zr].[Pb] QNZFKUWECYSYPS-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/72—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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/23—
-
- B01J35/51—
-
- 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
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides an embedded zirconia nanotube catalyst, which is prepared by the following steps: (1) ZrOCl 2 Mixing absolute ethyl alcohol and hydrogen peroxide to form sol; (2) Soaking spherical macroporous active alumina in sol, maintaining negative pressure soaking, filtering, drying and roasting; (3) And loading metallic copper by an impregnation method, filtering, drying and roasting to obtain the embedded zirconia nanotube catalyst. Is used for catalyzing maleic anhydride hydrogenation to prepare succinic anhydride. Zirconium is easy to give electrons when zirconium oxide interacts with metallic copper in the catalyst, so that the metallic copper tends to have positive charge trend, copper ions are easy to be reduced, and the H pair is improved 2 Is used for the adsorption capacity of the catalyst; the zirconia nanotube formed in the catalyst has good gas sensitivity and space limiting effect, so that the reactive gas has high concentration and adsorption effect in the local part of the reactive center, the catalyst has high catalytic activity, the mutual contact efficiency and mass transfer efficiency between the reaction materials are high, the reaction conversion rate and the product selectivity are high, and the catalyst has good stability.
Description
Technical Field
The invention relates to an embedded zirconia nanotube catalyst which is used in the reaction of preparing succinic anhydride by maleic anhydride catalytic hydrogenation.
Background
Succinic anhydride, also known as succinic anhydride, is a colorless needle-like or granular crystal with a slightly pungent odor; is easily dissolved in ethanol, chloroform and carbon tetrachloride, is slightly dissolved in water and diethyl ether, and can be hydrolyzed into succinic acid with hot water. The succinic anhydride is mainly used for the synthesis of resin, food processing aids, medicines, pesticides, esters and other fields, and can also be used for the synthesis and analysis reagent of succinic acid. The synthetic resin is mainly used for manufacturing alkyd resin and ion exchange resin, glass fiber and reinforced plastic in the plastic industry, and is mainly used for creating plant growth regulator and the like in the pesticide field, and is used for synthesizing intermediate of organic compound in the organic chemical industry. In recent years, succinic acid is well applied to the fields of full-biodegradable plastic polybutylene succinate, organic coating and the like, so that the demand of succinic anhydride is gradually increased.
The production method of succinic anhydride mainly includes biological fermentation method, succinic acid dehydration method and maleic anhydride hydrogenation method. At present, the direct hydrogenation method of maleic anhydride is the method with the highest conversion rate and purity of succinic anhydride, which improves a plurality of problems of a biological fermentation method and a succinic anhydride dehydration method in the process flow, the operation condition and the production cost, and provides a new method for industrialized production.
Chinese patent CN101502802B discloses a process for preparing a metal alloy from Al 2 O 3 Or SiO 2 As the maleic anhydride solution has certain acidity, the used carrier is easy to damage the structures of silicon and aluminum under the acidic condition, so that the catalyst framework collapses, and the service performance and the service life of the catalyst are seriously affected. U.S. Pat. nos. 5952514 and 5770744 disclose a method for preparing succinic anhydride by liquid phase hydrogenation of maleic anhydride, wherein the catalyst is prepared by pressing iron and inert elements such as aluminum, silicon, titanium or cobalt, nickel and carbon alloy powder, and has high requirements on equipment materials and special requirements on reactor design due to high reaction heat release. U.S. patent No. 1541210 and european patent No. EP0691335 disclose a method for preparing succinic anhydride by one-step hydrogenation of maleic anhydride, in which noble metal palladium is used as an active component in the catalyst, the content is 2-10 wt%, and the catalyst cost is high.
The nano catalytic material has the advantages of large specific surface area, high surface energy, multiple surface active sites, short diffusion channel in the crystal and the like, and therefore, the nano catalytic material has better catalytic performance in a plurality of chemical reactions. In recent years, researchers have synthesized catalytic materials such as carbon nanotubes, nano-metal clusters, nano-metal oxides, and nano-films, and have been applied to chemical reactions in many fields. At present, researches on embedded metal oxide nanotube catalysts are freshly reported, and the invention provides a preparation method of the embedded zirconia nanotube catalyst, which is used in the reaction of preparing succinic anhydride by maleic anhydride hydrogenation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an embedded zirconia nanotube catalyst, which adopts spherical macroporous activated alumina as a template, forms zirconia nanotubes in situ in pore channels of the spherical macroporous activated alumina, loads metal active components on the zirconia nanotubes to prepare the embedded zirconia nanotube catalyst, and then applies the embedded zirconia nanotube catalyst to the reaction of preparing succinic anhydride by hydrogenating maleic anhydride, so that the embedded zirconia nanotube catalyst has higher reaction efficiency and reaction conversion rate, higher product selectivity and better reaction effect.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the technical object of the first aspect of the present invention is to provide a method for preparing an embedded zirconia nanotube catalyst, comprising the following steps:
(1) ZrOCl 2 Dissolving in absolute ethanol, adding hydrogen peroxide, and stirring to form sol;
(2) Immersing spherical macroporous activated alumina in the sol in the step (1), maintaining the condition of negative pressure for immersion, filtering, drying and roasting;
(3) And (3) loading metallic copper on the product obtained in the step (2) by an impregnation method, and filtering, drying and roasting the product to obtain the embedded zirconia nanotube catalyst.
Further, the intermediate of spherical macroporous activated alumina-supported zirconia is obtained in the step (2), and accounts for 10% -30%, preferably 15% -25% of the total weight of the intermediate by weight of zirconia.
Further, zrOCl in step (1) 2 The molar concentration of the ethanol solution is 0.2 to 1.0mol/L, the mass percentage concentration of the hydrogen peroxide is 20 to 30 percent, and the molar ratio H of the hydrogen peroxide to the zirconium 2 O 2 : zr is 3:1 to 6:1.
further, in the step (1), the reaction temperature is 20-50 ℃, preferably 30-40 ℃, the stirring revolution is 200-600 r/min, preferably 400-500 r/min, and the reaction time is 1-2 hours, and after obtaining the zirconium sol, heating and stirring are stopped, and natural cooling is performed.
Further, the average diameter of the spherical macroporous activated alumina in the step (2) is 3-7 mm, preferably 3-5 mm; the average specific surface area is 280-380 cm 2 Preferably 300 to 320 cm/g 2 And/g, the average pore diameter is 10 to 50nm, preferably 20 to 40nm.
Furthermore, the spherical macroporous active alumina is preferably washed before being used, the solvent used for washing is absolute ethanol with the concentration of 95 percent, the washing times are 3-5 times, the washing temperature is 20-50 ℃, preferably 30-35 ℃, and the drying is carried out after washing, and the drying temperature is 50-100 ℃, preferably 70-90 ℃.
Further, the dipping time in the step (2) is 1 to 3 hours, and the dipping pressure is 1000 to 10000Pa, preferably 1500 to 3000Pa.
Further, the drying temperature in the step (2) is 30-40 ℃, the drying time is 12-24 hours, the roasting temperature is 500-550 ℃, and the roasting time is 1-3 hours.
Further, the catalyst obtained in the step (3) is 1 to 10% by weight of copper oxide, preferably 4 to 10% by weight of the total weight of the catalyst.
Further, the precursor solution used for loading the metallic copper in the step (3) is CuCl 2 Or Cu (NO 3) 2 Wherein the mass concentration of copper salt in the solution is 10 to 20wt%, preferably 10 to 15wt%.
Further, the drying temperature in the step (3) is 50-100 ℃, preferably 90-100 ℃, and the drying time is 8-12 hours; the roasting temperature is 400-500 ℃ and the roasting time is 8-12 hours.
The technical purpose of the second aspect of the invention is to provide the embedded zirconia nanotube catalyst prepared by the method. The invention adopts spherical macroporous active alumina as a template, and impregnates under the condition of negative pressure to lead zirconium sol to enter intoAnd (3) filtering, drying and roasting the alumina agent in the pore canal, and loading a metal active component by using a conventional impregnation method to obtain the embedded zirconia nanotube catalyst. Compared with the pore canal of the active alumina, the zirconia nanotube has the advantages of smooth surface, strong adsorption capacity, difficult aggregation and falling of metal active components, uniform load on the surface of the zirconia nanotube and high dispersity. Zirconium oxide has the characteristics of acidity, alkalinity, oxidability and reducibility, is easy to interact with metal active components, and when the zirconium is interacted with metal copper, electrons are easy to be given out by zirconium, so that the metal copper tends to have positive charge trend, copper ions are easy to be reduced, and the H-pair is improved 2 Is used for the adsorption capacity of the catalyst. In addition, due to the gas sensitivity and the space limiting effect of the zirconia nanotubes, the reaction gas has higher concentration and adsorption effect in the local part of the reactive center, so that the catalyst has stronger catalytic activity, the mutual contact efficiency and the mass transfer efficiency between the reaction materials are high, the reaction conversion rate and the product selectivity are higher, and the catalyst has good stability.
The technical purpose of the third aspect of the invention is to provide the application of the embedded zirconia nanotube catalyst, wherein the embedded zirconia nanotube catalyst is used for catalyzing the reaction of maleic anhydride hydrogenation to prepare succinic anhydride.
The catalyst is applied to the preparation of succinic anhydride by hydrogenation of maleic anhydride on a fixed bed, and gamma-butyrolactone is used as a solvent, the reaction temperature is 80-150 ℃, the reaction pressure is 2-6 MPa, the hydrogen-oil volume ratio is 100-300 (the volume ratio of hydrogen to gamma-butyrolactone containing maleic anhydride), the preferable reaction temperature is 90-130 ℃, the reaction pressure is 3-5 MPa, and the hydrogen-oil volume ratio is 120-150.
Compared with the prior art, the invention has the following advantages:
(1) The embedded zirconia nanotube catalyst adopts spherical macroporous active alumina as a template, is immersed under the negative pressure condition to enable zirconium sol to enter into spherical macroporous active alumina pore channels, and is filtered, dried and roasted to obtain active alumina spheres embedded with zirconia nanotubes with better continuity; and then the metal active components are loaded on the surface of the zirconia nanotube, so that the zirconia nanotube has smooth surface and strong adsorption capacity, and the metal active components are uniformly dispersed on the surface of the zirconia nanotube to form a stronger reactive center.
(2) Zirconium oxide has the characteristics of acidity, alkalinity, oxidability and reducibility, is easy to interact with metal active components, and zirconium is easy to give out electrons when interacting with metal copper, so that the metal copper tends to have positive charge trend, copper ions are easy to reduce, and the H-pair is improved 2 Is used for the adsorption capacity of the catalyst.
(3) The copper oxide nanotube formed in the catalyst has good gas sensitivity and space confinement effect, so that the reactive gas has high concentration and adsorption effect in the local part of the reactive center, the catalyst has high catalytic activity, the mutual contact efficiency and mass transfer efficiency between the reaction materials are high, the reaction conversion rate and the product selectivity are high, and the catalyst has good stability.
Detailed Description
The specific embodiments of the present invention are as follows: preparing an embedded zirconia nanotube catalyst, carrying out maleic anhydride hydrogenation reaction on a fixed bed continuous reaction device with the embedded zirconia nanotube catalyst, feeding reaction materials into the reactor from the top of the reactor under certain process conditions, carrying out hydrogenation reaction under the action of the embedded zirconia nanotube catalyst, and discharging reaction products from the bottom of the reactor, and then carrying out sampling analysis.
The following describes specific embodiments of the present invention in detail with reference to examples. Unless otherwise specified, the following examples and comparative examples are given in% by mass.
Example 1
In this example, an embedded zirconia nanotube catalyst was prepared and applied to the reaction of maleic anhydride hydrogenation to succinic anhydride:
preparing an embedded zirconia nanotube catalyst:
(1) 60g ZrOCl was added 2 Dissolving in 300mL of absolute ethanol at 30deg.C under stirringUnder the condition of 400r/min revolution, the reaction time is 1 hour, zirconium sol is obtained, and natural cooling is carried out for standby;
(2) 100g of macroporous activated alumina is immersed in the sol obtained in the step (1) for 3 hours under the condition of 1800Pa, filtered and dried for 12 hours at 40 ℃, and then baked for 2 hours at 450 ℃ to obtain activated alumina spheres embedded with zirconia nano tubes, wherein the zirconia accounts for 18.3% by weight.
(3) Cu (NO) 3 ) 2 Formulated as Cu (NO) at a concentration of 15% 3 ) 2 Immersing the activated alumina spheres obtained in the step (2) in Cu (NO) 3 ) 2 In the aqueous solution, the dipping time is 8 hours, after filtering, the catalyst is dried for 12 hours at 90 ℃, and then baked for 8 hours at 450 ℃ to obtain the embedded zirconia nanotube catalyst, wherein the copper oxide accounts for 5.1 percent of the total weight of the catalyst by weight.
Maleic anhydride hydrogenation to prepare succinic anhydride:
introducing maleic anhydride gamma-butyrolactone and hydrogen into a fixed bed continuous reactor filled with an embedded zirconia nanotube catalyst, wherein the materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 90 ℃, the reaction pressure is 3MPa, and the hydrogen-oil volume ratio is 120:1 and the reaction results are shown in Table 1.
Example 2
Preparing an embedded zirconia nanotube catalyst:
(1) 65g ZrOCl were added 2 Dissolving in 300mL absolute ethyl alcohol, reacting for 1.5 hours at the temperature of 30 ℃ and stirring revolution of 450r/min to obtain zirconium sol, and naturally cooling for standby;
(2) 100g of macroporous activated alumina is immersed in the sol obtained in the step (1), immersed for 3 hours under the pressure of 1900Pa, filtered, dried for 12 hours under the temperature of 40 ℃, and roasted for 2 hours under the temperature of 450 ℃ to obtain activated alumina spheres embedded with zirconia nano tubes, wherein the zirconia accounts for 19.8% by weight.
(3) Cu (NO) 3 ) 2 Formulated as Cu (NO) at a concentration of 20% 3 ) 2 Immersing the activated alumina spheres obtained in the step (2) in Cu (NO) 3 ) 2 In the aqueous solution, the dipping time is 8 hours, after filtering, the catalyst is dried for 12 hours at 90 ℃, and then baked for 8 hours at 450 ℃ to obtain the embedded zirconia nanotube catalyst, wherein the copper oxide accounts for 6.3% of the total weight of the catalyst by weight.
Maleic anhydride hydrogenation to prepare succinic anhydride:
introducing maleic anhydride gamma-butyrolactone and hydrogen into a fixed bed continuous reactor filled with an embedded zirconia nanotube catalyst, wherein the materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 100 ℃, the reaction pressure is 3MPa, and the hydrogen-oil volume ratio is 120:1 and the reaction results are shown in Table 1.
Example 3
Preparing an embedded zirconia nanotube catalyst:
(1) 70g ZrOCl were added 2 Dissolving in 300mL absolute ethyl alcohol, stirring at 30 ℃ for 1.5 hours at 400r/min to obtain zirconium sol, and naturally cooling for later use;
(2) 100g of macroporous activated alumina is immersed in the sol obtained in the step (1) for 3 hours under the condition of 2000Pa, filtered, dried for 12 hours at 40 ℃, and roasted for 2 hours at 500 ℃ to obtain activated alumina spheres embedded with zirconia nano tubes, wherein the zirconia accounts for 23.4% by weight.
(3) Cu (NO) 3 ) 2 Formulated as Cu (NO) at a concentration of 15% 3 ) 2 Immersing the activated alumina spheres obtained in the step (2) in Cu (NO) 3 ) 2 In the aqueous solution, the dipping time is 8 hours, after filtering, the catalyst is dried for 12 hours at 90 ℃, and then baked for 8 hours at 450 ℃ to obtain the embedded zirconia nanotube catalyst, wherein the copper oxide accounts for 5.6% of the total weight of the catalyst by weight.
Maleic anhydride hydrogenation to prepare succinic anhydride:
introducing maleic anhydride gamma-butyrolactone and hydrogen into a fixed bed continuous reactor filled with an embedded zirconia nanotube catalyst, wherein the materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 110 ℃, the reaction pressure is 4MPa, and the hydrogen-oil volume ratio is 130:1 and the reaction results are shown in Table 1.
Example 4
Preparing an embedded zirconia nanotube catalyst:
(1) 70g ZrOCl were added 2 Dissolving in 300mL absolute ethyl alcohol, stirring at 30 ℃ for 1.5 hours at 400r/min to obtain zirconium sol, and naturally cooling for later use;
(2) 100g of macroporous activated alumina is immersed in the sol obtained in the step (1) for 3 hours under the condition of 2000Pa, filtered, dried for 12 hours at 40 ℃, and roasted for 2 hours at 500 ℃ to obtain activated alumina spheres embedded with zirconia nano tubes, wherein the zirconia accounts for 23.8% by weight.
(3) Cu (NO) 3 ) 2 Formulated as Cu (NO) at a concentration of 20% 3 ) 2 Immersing the activated alumina spheres obtained in the step (2) in Cu (NO) 3 ) 2 In the aqueous solution, the dipping time is 8 hours, after filtration, the catalyst is dried for 12 hours at 90 ℃, and then baked for 8 hours at 500 ℃ to obtain the embedded zirconia nanotube catalyst, wherein the copper oxide accounts for 7.9% of the total weight of the catalyst by weight.
Maleic anhydride hydrogenation to prepare succinic anhydride:
introducing maleic anhydride gamma-butyrolactone and hydrogen into a fixed bed continuous reactor filled with an embedded zirconia nanotube catalyst, wherein the materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 120 ℃, the reaction pressure is 3MPa, and the hydrogen-oil volume ratio is 140:1 and the reaction results are shown in Table 1.
Example 5
Preparing an embedded zirconia nanotube catalyst:
(1) 60g ZrOCl was added 2 Dissolving in 300mL of absolute ethyl alcohol, reacting for 2 hours at the temperature of 30 ℃ and stirring revolution of 400r/min to obtain zirconium sol, and naturally cooling for standby;
(2) 100g of macroporous activated alumina is immersed in the sol obtained in the step (1) for 3 hours under the condition of 1800Pa, filtered and dried for 12 hours at 40 ℃, and then baked for 2 hours at 450 ℃ to obtain activated alumina spheres embedded with zirconia nano tubes, wherein the zirconia accounts for 17.5% by weight.
(3) Cu (NO) 3 ) 2 Formulated as Cu (NO) at a concentration of 25% 3 ) 2 Immersing the activated alumina spheres obtained in the step (2) in Cu (NO) 3 ) 2 In the aqueous solution, the dipping time is 8 hours, after filtering, the catalyst is dried for 12 hours at 90 ℃, and then baked for 8 hours at 500 ℃ to obtain the embedded zirconia nanotube catalyst, wherein the copper oxide accounts for 7.4% of the total weight of the catalyst by weight.
Maleic anhydride hydrogenation to prepare succinic anhydride:
introducing maleic anhydride gamma-butyrolactone and hydrogen into a fixed bed continuous reactor filled with an embedded zirconia nanotube catalyst, wherein the materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 120 ℃, the reaction pressure is 5MPa, and the hydrogen-oil volume ratio is 130:1 and the reaction results are shown in Table 1.
Example 6
Preparing an embedded zirconia nanotube catalyst:
(1) 65g ZrOCl were added 2 Dissolving in 300mL of absolute ethyl alcohol, reacting for 2 hours at the temperature of 30 ℃ and stirring revolution of 400r/min to obtain zirconium sol, and naturally cooling for standby;
(2) 100g of macroporous activated alumina is immersed in the sol obtained in the step (1), immersed for 3 hours under the pressure of 1900Pa, filtered, dried for 12 hours under the temperature of 40 ℃, and roasted for 2 hours under the temperature of 500 ℃ to obtain activated alumina spheres embedded with zirconia nanotubes, wherein the zirconia accounts for 19.5% by weight.
(3) Cu (NO) 3 ) 2 Formulated as Cu (NO) at a concentration of 15% 3 ) 2 Immersing the activated alumina spheres obtained in the step (2) in Cu (NO) 3 ) 2 In the aqueous solution, the dipping time is 8 hoursAfter filtration, drying for 12 hours at 90 ℃ and roasting for 8 hours at 450 ℃ to obtain the embedded zirconia nanotube catalyst, wherein the copper oxide accounts for 5.8% of the total weight of the catalyst by weight.
Maleic anhydride hydrogenation to prepare succinic anhydride:
introducing maleic anhydride gamma-butyrolactone and hydrogen into a fixed bed continuous reactor filled with an embedded zirconia nanotube catalyst, wherein the materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 120 ℃, the reaction pressure is 4MPa, and the hydrogen-oil volume ratio is 130:1 and the reaction results are shown in Table 1.
Comparative example 1
In the maleic anhydride hydrogenation reaction process, the catalyst used is a supported CuO/activated alumina sphere prepared by an impregnation method: cu (NO) was impregnated with the same spherical macroporous activated alumina as in example 4 3 ) 2 The solution gave a catalyst with copper oxide 9.6% by weight of the total weight of the catalyst, the other conditions being the same as in example 4 and the reaction results being shown in Table 1.
Comparative example 2
In the maleic anhydride hydrogenation reaction process, the catalyst used is a supported ZrO/activated alumina sphere catalyst prepared by an impregnation method: zr (NO) was impregnated with the same spherical macroporous activated alumina as in example 4 3 ) 4 The solution gave a catalyst with zirconia accounting for 22.3% by weight of the total weight of the catalyst, the other conditions being the same as in example 4, and the reaction results being shown in table 1.
Table 1 reaction results (conversion in moles) for the examples
Claims (16)
1. The preparation process of embedded zirconia nanotube catalyst includes the following steps:
(1) ZrOCl 2 Dissolving in absolute ethanol, adding hydrogen peroxide, and stirring to form sol;
(2) Impregnating spherical macroporous active alumina inSoaking in the sol in the step (1) under the negative pressure, filtering, drying and roasting; the average diameter of the spherical macroporous active alumina is 3-7 mm, and the average specific surface area is 280-380 cm 2 And/g, wherein the average pore diameter is 10-50 nm;
(3) And (3) loading metallic copper on the product obtained in the step (2) by an impregnation method, and filtering, drying and roasting the product to obtain the embedded zirconia nanotube catalyst.
2. The preparation method according to claim 1, wherein the spherical macroporous activated alumina-supported zirconia intermediate obtained in the step (2) accounts for 10% -30% of the total weight of the intermediate, based on the weight of zirconia.
3. The preparation method according to claim 1, wherein the catalyst obtained in the step (3) is 1-10% of the total weight of the catalyst based on the weight of copper oxide.
4. The method according to claim 1, wherein ZrOCl is used in the step (1) 2 The molar concentration of the ethanol solution is 0.2-1.0 mol/L.
5. The preparation method of claim 1, wherein in the step (1), the mass percentage concentration of the hydrogen peroxide is 20-30%, and the molar ratio of the hydrogen peroxide to the zirconium is 3:1 to 6:1.
6. the process according to claim 1, wherein the reaction temperature in step (1) is 20 to 50℃and the reaction time is 1 to 2 hours.
7. The method according to claim 1, wherein the average diameter of the spherical macroporous activated alumina in the step (2) is 3 to 5mm; the average specific surface area is 300-320 cm 2 And/g, the average pore diameter is 20-40 nm.
8. The preparation method according to claim 1, wherein the spherical macroporous activated alumina is subjected to a washing treatment before use, the solvent used for washing is absolute ethanol with a concentration of 95%, and the spherical macroporous activated alumina is dried after washing.
9. The process according to claim 1, wherein the impregnation pressure in step (2) is 1000 to 10000Pa.
10. The process according to claim 9, wherein the impregnation pressure in step (2) is 1500 to 3000Pa.
11. The method according to claim 1, wherein the firing temperature in the step (2) is 500 to 550 ℃ and the firing time is 1 to 3 hours.
12. The method according to claim 1, wherein the precursor solution for supporting metallic copper in the step (3) is CuCl 2 Or Cu (NO 3) 2 The mass concentration of copper salt in the solution is 10-20wt%.
13. The method according to claim 1, wherein the baking temperature in the step (3) is 400 to 500 ℃ and the baking time is 8 to 12 hours.
14. An embedded zirconia nanotube catalyst prepared by the method of any one of claims 1-13.
15. Use of the catalyst of claim 14 for catalyzing the hydrogenation of maleic anhydride to succinic anhydride.
16. The use according to claim 15, wherein the reaction for preparing succinic anhydride by hydrogenating maleic anhydride uses gamma-butyrolactone as solvent, the reaction temperature is 80-150 ℃, the reaction pressure is 2-6 MPa, and the hydrogen-oil volume ratio is 100-300.
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