CN114433242A - Embedded copper oxide nanotube catalyst - Google Patents
Embedded copper oxide nanotube catalyst Download PDFInfo
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- CN114433242A CN114433242A CN202011526635.7A CN202011526635A CN114433242A CN 114433242 A CN114433242 A CN 114433242A CN 202011526635 A CN202011526635 A CN 202011526635A CN 114433242 A CN114433242 A CN 114433242A
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- copper oxide
- oxide nanotube
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 59
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 59
- 239000002071 nanotube Substances 0.000 title claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 28
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229920005990 polystyrene resin Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 208000012839 conversion disease Diseases 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 239000012495 reaction gas Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 240000007594 Oryza sativa Species 0.000 abstract 1
- 235000007164 Oryza sativa Nutrition 0.000 abstract 1
- 235000009566 rice Nutrition 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J37/0211—Impregnation using a colloidal suspension
-
- 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
- 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- 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
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An embedded copper oxide nanotube catalyst prepared by the following method: adding CuCl2Dissolving in deionized water, heating, and stirring to form Cu (OH)2Sol and naturally cooling; the resin catalyst was washed, dried, and then immersed in Cu (OH)2And (3) soaking in sol under a negative pressure condition, filtering, drying and calcining to obtain the embedded copper oxide nanotube catalyst. The inside of the catalyst of the invention forms continuous copper oxide with uniform apertureThe rice tube structure is different from a 'dot' active center formed by a common dipping method, and the gas-sensitive performance and the space confinement effect of the copper oxide nano tube enable reaction gas to have higher concentration and adsorption action at the local part of the reaction active center, so that the catalyst has stronger catalytic activity, the mutual contact efficiency and the mass transfer efficiency between reaction materials are high, the reaction conversion rate and the product selectivity are higher, and the catalyst has good stability.
Description
Technical Field
The invention relates to an embedded copper oxide nanotube catalyst which is used for catalyzing ester hydrogenation to produce 1, 6-hexanediol.
Background
1, 6-Hexanediol (HDO) is a new fine chemical product with unique performance, can be mixed with various organic chemicals in any proportion, has no corrosiveness, can derive a series of novel fine chemicals, and has increasingly wide application in the fields of polyurethane, polyester, coil coating, photocuring and the like. For example: the modified urea-formaldehyde resin is applied to polyurethane elastomers, 1, 6-hexanediol is used for modifying the urea-formaldehyde elastomers, and the modified resin has excellent mechanical strength, water resistance, heat resistance and oxidation resistance; the polycarbonate can be prepared into fibers and films by the reaction of 1, 6-hexanediol and dimethyl carbonate; the polyester plasticizer is applied to polyester plasticizers, the traditional ester plasticizers have certain defects when manufacturing plastic polyvinyl chloride with fire resistance, and the polyester plasticizers prepared by 1, 6-hexanediol and related substances can exactly compensate and improve the defects; the water-resistant and oil-resistant modified polyester is applied to an acid ester plasticizer to improve the water resistance and oil resistance of the plasticizer; can be used for pyrethrin pesticide.
The main processes for producing 1, 6-hexanediol include adipate production, hydrogenation, adipic acid direct hydrogenation, acrylic acid production, and hydroformylation. Although there are many technical routes for the preparation of 1, 6-hexanediol, these technical routes are not all suitable for industrial production. The direct adipic acid hydrogenation method has high requirements on the acid resistance of catalysts and equipment; the process of dimerizing acrylic esters and then hydrogenating them to 1, 6-hexanediol provides a process for preparing 1, 6-hexanediol from lower hydrocarbons (C3), but is currently in the laboratory exploration phase; 1, 6-hexanediol is prepared by a hydroformylation method, and the selectivity is low; the epoxybutadiene method has too complex reaction process and rare raw materials. Therefore, the more mature 1, 6-hexanediol production process is still an adipate and hydrogenation process.
Patent CN102372604A discloses a method for preparing 1, 6-hexanediol by hydrogenation of dimethyl adipate, which takes oxide-supported noble metal as a catalyst, the reaction is carried out in a high-pressure kettle, the problems of discontinuous reaction, high catalyst cost and difficult impurity separation exist, and the conversion rate and selectivity of the product are low. The patent CN111659375A discloses a catalyst for preparing 1, 6-hexanediol by hydrogenation of dimethyl adipate, a preparation method and application thereof, wherein the method uses SiO2/ZrO2The catalyst is used as a carrier, and noble metal ruthenium or iridium is used as an active component, so that the preparation process is complex, the cost of the catalyst is high, and a large amount of organic solvent is used in the preparation process, so that the environmental pollution is easily caused.
Therefore, the prior method for preparing 1, 6-hexanediol by ester hydrogenation has the problems of low reaction conversion rate, poor product selectivity, difficult separation of product and catalyst impurities and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an embedded copper oxide nanotube catalyst, which is applied to the ester hydrogenation production of 1, 6-hexanediol by using a resin catalyst as a template and forming a copper oxide nanotube in situ in a pore channel, and has the advantages of higher reaction efficiency and reaction conversion rate, higher product selectivity and better reaction effect.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the technical purpose of the first aspect of the invention is to provide a preparation method of an embedded copper oxide nanotube catalyst, which comprises the following steps:
(1) washing the resin catalyst, and drying for later use;
(2) adding CuCl2Dissolving in deionized water, heating, and stirring to form Cu (OH)2Naturally cooling the sol for later use;
(3) impregnating the resin catalyst obtained in the step (1) with Cu (OH) obtained in the step (2)2And (3) soaking in sol under a negative pressure condition, filtering, drying and calcining to obtain the embedded copper oxide nanotube catalyst.
In one embodiment of the present invention, the embedded copper oxide nanotube catalyst obtained in step (3) accounts for 10% to 30% of the total weight of the catalyst, preferably 7% to 12% of the total weight of the catalyst, based on the weight of copper oxide.
In one embodiment of the present invention, the resin catalyst in step (1) is a polystyrene resin catalyst, and the average diameter thereof is 0.5 to 1.2mm, preferably 0.8 to 1.0 mm; the average specific surface area is 600-1000 cm2Preferably 700 to 900 cm/g2(iv)/g, the average pore diameter is 5 to 30nm, preferably 10 to 20nm, and the average pore volume is 0.01 to 0.1mL/g, preferably 0.03 to 0.05 mL/g.
In one embodiment of the present invention, the washing in step (1) is performed 3 to 5 times, the solvent used for washing is 95% absolute ethanol, the washing temperature is 20 to 50 ℃, preferably 30 to 35 ℃, and the drying temperature is 50 to 100 ℃, preferably 60 to 70 ℃.
In one embodiment of the present invention, CuCl is used in the step (2)2CuCl in solution2The mass percentage concentration of the organic solvent is 10-30 wt%, the heating temperature is 90-100 ℃, the stirring revolution is 100-350 r/min, preferably 200-250 r/min, the heating and stirring are stopped after the solution discolors to form sol, and the solution is naturally cooled.
In one embodiment of the present invention, the impregnation time in step (3) is 1 to 3 hours, and the impregnation pressure is 1.0 to 10.0kPa, preferably 1.5 to 3.0 kPa.
In one embodiment of the present invention, the drying temperature in step (3) is 30 to 40 ℃, the drying time is 12 to 24 hours, the calcination temperature is 150 to 200 ℃, and the calcination time is 1 to 3 hours.
The technical purpose of the second aspect of the invention is to provide the embedded copper oxide nanotube catalyst prepared by the method. The invention adopts styrene resin catalyst as template, and the template is dipped under the condition of negative pressure to ensure that Cu (OH)2And (3) allowing the sol to enter a pore channel of the resin catalyst, and filtering, drying and calcining to obtain the embedded copper oxide nanotube catalyst. The method forms a copper oxide nanotube structure with uniform and continuous aperture in the resin catalyst, which is different from a 'dot' active center formed by a common impregnation method, and the gas-sensitive performance and the space confinement effect of the copper oxide nanotube enable reaction gas to have higher concentration and adsorption action at the local part of the reaction active center, so that the catalyst has stronger catalytic activity, the mutual contact efficiency and mass transfer efficiency between 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 an application of the embedded copper oxide nanotube catalyst, wherein the embedded copper oxide nanotube catalyst is used for catalyzing a reaction for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate.
In the above application, the dimethyl adipate hydrogenation reaction conditions are as follows: the reaction temperature is 180-260 ℃, and preferably 190-200 ℃; the reaction pressure is 2-8 MPa, preferably 3-6 MPa, and the volume space velocity of dimethyl adipate is 0.2-2: 1, preferably 0.5-1: 1, hydrogen-ester molar ratio of 150: 1-350: 1, preferably 200: 1-300: 1.
compared with the prior art, the invention has the following advantages:
(1) the embedded copper oxide nanotube catalyst adopts styrene resin catalyst as a template, and is impregnated under the condition of negative pressure to ensure that Cu (OH)2The sol enters a pore channel of the resin catalyst, and is filtered, dried and calcined to obtain an embedded copper oxide nanotube catalyst; the embedded copper oxide nanotube has better continuity and forms a stronger reactive center.
(2) The copper oxide nanotube formed in the catalyst has better gas-sensitive performance and space confinement effect, so that reaction gas has higher concentration and adsorption action at the local part of a reaction active center, the catalyst has stronger catalytic activity, the mutual contact efficiency and mass transfer efficiency of reaction materials are high, the reaction conversion rate and the product selectivity are higher, and the catalyst has good stability.
Detailed Description
The specific embodiment of the invention is as follows: preparing an embedded copper oxide nanotube catalyst, carrying out ester hydrogenation reaction on a fixed bed continuous reaction device with the embedded copper oxide nanotube catalyst, under a certain process condition, enabling reaction materials to enter a reactor from the top of the reactor, carrying out ester hydrogenation reaction under the action of the embedded copper oxide nanotube catalyst, enabling reaction products to flow out of the bottom of the reactor, and then carrying out sampling analysis.
The following examples are provided to illustrate specific embodiments of the present invention. In the following examples and comparative examples,% represents mass% unless otherwise specified.
Example 1
In this example, an embedded copper oxide nanotube catalyst was prepared and applied to the esterification of adipic acid and methanol to prepare 1, 6-hexanediol:
preparing an embedded copper oxide nanotube catalyst:
(1) measuring 100mL of resin catalyst, measuring 300mL of 95% absolute ethyl alcohol, washing for 3 times at 35 ℃, and drying for 12 hours at 70 ℃ for later use;
(2) 60g of CuCl2Dissolving in 300g of deionized water, reacting at 95 ℃ and the stirring speed of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for later use;
(3) and (3) soaking the resin catalyst obtained in the step (1) in the sol obtained in the step (2) under the condition of 1.8kPa for 3 hours, filtering, drying at 40 ℃ for 12 hours, and calcining at 200 ℃ for 2 hours to obtain the embedded copper oxide nanotube catalyst, wherein the copper oxide accounts for 9.1% of the total weight of the catalyst.
Preparing 1, 6-hexanediol by dimethyl adipate hydrogenation:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor filled with an embedded copper oxide nanotube catalyst, feeding materials from the top of the reactor, and discharging the materials from the bottom of the reactor, wherein the reaction temperature is 200 ℃, the reaction pressure is 3MPa, and the volume space velocity of the dimethyl adipate is 0.8h-1The molar ratio of hydrogen to ester is 200: the reaction results are shown in Table 1.
Example 2
Preparing an embedded copper oxide nanotube catalyst:
(1) measuring 100mL of resin catalyst, measuring 300mL of 95% absolute ethyl alcohol, washing for 3 times at 30 ℃, and drying for 12 hours at 60 ℃ for later use;
(2) 70g of CuCl2Dissolving in 300g of deionized water, reacting at 95 ℃ and stirring speed of 200r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for later use;
(3) and (2) soaking the resin catalyst obtained in the step (1) in the sol obtained in the step (2) under the condition of the pressure of 1.7kPa for 3 hours, filtering, drying at 40 ℃ for 12 hours, and calcining at 200 ℃ for 2 hours to obtain the embedded copper oxide nanotube catalyst, wherein the copper oxide accounts for 8.6% of the total weight of the catalyst by weight.
Preparing 1, 6-hexanediol by dimethyl adipate hydrogenation:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor filled with an embedded copper oxide nanotube catalyst, feeding materials from the top of the reactor, and discharging the materials from the bottom of the reactor, wherein the reaction temperature is 210 ℃, the reaction pressure is 3MPa, and the volume space velocity of the dimethyl adipate is 1.0h-1The molar ratio of hydrogen to ester is 250: the reaction results are shown in Table 1.
Example 3
Preparing an embedded copper oxide nanotube catalyst:
(1) measuring 100mL of resin catalyst, measuring 300mL of 95% absolute ethyl alcohol, washing for 3 times at 35 ℃, and drying for 12 hours at 70 ℃ for later use;
(2) 75g of CuCl2Dissolving in 300g of deionized water, reacting at 95 ℃ and the stirring speed of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for later use;
(3) and (2) soaking the resin catalyst obtained in the step (1) in the sol obtained in the step (2) under the condition of the pressure of 1.5kPa for 3 hours, filtering, drying at 40 ℃ for 12 hours, and calcining at 200 ℃ for 2 hours to obtain the embedded copper oxide nanotube catalyst, wherein the copper oxide accounts for 8.4% of the total weight of the catalyst by weight.
Preparing 1, 6-hexanediol by dimethyl adipate hydrogenation:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor filled with an embedded copper oxide nanotube catalyst, feeding materials from the top of the reactor, and discharging the materials from the bottom of the reactor, wherein the reaction temperature is 220 ℃, the reaction pressure is 6MPa, and the volume space velocity of the dimethyl adipate is 0.8h-1The molar ratio of hydrogen to ester is 250: the reaction results are shown in Table 1.
Example 4
Preparing an embedded copper oxide nanotube catalyst:
(1) measuring 100mL of resin catalyst, measuring 300mL of 95% absolute ethyl alcohol, washing for 3 times at 35 ℃, and drying for 12 hours at 70 ℃ for later use;
(2) 65g of CuCl2Dissolving in 300g of deionized water, reacting at 95 ℃ and the stirring speed of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for later use;
(3) and (2) soaking the resin catalyst obtained in the step (1) in the sol obtained in the step (2) under the condition of the pressure of 1.6kPa for 3 hours, filtering, drying at 40 ℃ for 12 hours, and calcining at 200 ℃ for 2 hours to obtain the embedded copper oxide nanotube catalyst, wherein the copper oxide accounts for 9.7 percent of the total weight of the catalyst.
Preparing 1, 6-hexanediol by dimethyl adipate hydrogenation:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor filled with an embedded copper oxide nanotube catalyst, feeding materials from the top of the reactor, and discharging the materials from the bottom of the reactor, wherein the reaction temperature is 220 ℃, the reaction pressure is 3MPa, and the volume space velocity of the dimethyl adipate is 1.0h-1The molar ratio of hydrogen to ester is 250: the reaction results are shown in Table 1.
Example 5
Preparing an embedded copper oxide nanotube catalyst:
(1) measuring 100mL of resin catalyst, measuring 300mL of 95% absolute ethyl alcohol, washing for 3 times at 35 ℃, and drying for 12 hours at 70 ℃ for later use;
(2) 60g of CuCl2Dissolving in 300g of deionized water, reacting at 95 ℃ and the stirring speed of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for later use;
(3) and (2) soaking the resin catalyst obtained in the step (1) in the sol obtained in the step (2) under the condition of the pressure of 1.8kPa for 3 hours, filtering, drying at 40 ℃ for 12 hours, and calcining at 200 ℃ for 2 hours to obtain the embedded copper oxide nanotube catalyst, wherein the copper oxide accounts for 10.1% of the total weight of the catalyst by weight.
Preparing 1, 6-hexanediol by dimethyl adipate hydrogenation:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor filled with an embedded copper oxide nanotube catalyst, feeding materials from the top of the reactor, and discharging the materials from the bottom of the reactor, wherein the reaction temperature is 220 ℃, the reaction pressure is 4MPa, and the volume space velocity of the dimethyl adipate is 1.5h-1The molar ratio of hydrogen to ester is 300: the reaction results are shown in Table 1.
Example 6
Preparing an embedded copper oxide nanotube catalyst:
(1) measuring 100mL of resin catalyst, measuring 300mL of 95% absolute ethyl alcohol, washing for 3 times at 35 ℃, and drying for 12 hours at 70 ℃ for later use;
(2) 80g of CuCl2Dissolving in 300g of deionized water, reacting at 95 ℃ and the stirring speed of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for later use;
(3) and (2) soaking the resin catalyst obtained in the step (1) in the sol obtained in the step (2) under the pressure of 1500Pa for 3 hours, filtering, drying at 40 ℃ for 12 hours, and calcining at 200 ℃ for 2 hours to obtain the embedded copper oxide nanotube catalyst, wherein the copper oxide accounts for 10.5% of the total weight of the catalyst by weight.
Preparing 1, 6-hexanediol by dimethyl adipate hydrogenation:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor filled with an embedded copper oxide nanotube catalyst, feeding materials from the top of the reactor, and discharging the materials from the bottom of the reactor, wherein the reaction temperature is 210 ℃, the reaction pressure is 3MPa, and the volume space velocity of the dimethyl adipate is 0.8h-1The molar ratio of hydrogen to ester is 200: the reaction results are shown in Table 1.
Comparative example 1
In the process of dimethyl adipate hydrogenation, the catalyst used is a supported CuO/resin catalyst, copper oxide accounts for 11.2% of the total weight of the catalyst by weight, other conditions are the same as those in example 4, and the reaction results are shown in Table 1.
Comparative example 2
In the process of dimethyl adipate hydrogenation, the catalyst used was a supported CuO/alumina catalyst, copper oxide accounted for 9.8% by weight of the total catalyst weight, the other conditions were the same as in example 4, and the reaction results are shown in Table 1.
TABLE 1 reaction results (conversion in moles) of the examples
Claims (13)
1. A preparation method of an embedded copper oxide nanotube catalyst comprises the following steps:
(1) washing the resin catalyst, and drying for later use;
(2) adding CuCl2Dissolving in deionized water, heating, and stirring to form Cu (OH)2Naturally cooling the sol for later use;
(3) impregnating the resin catalyst obtained in the step (1) with Cu (OH) obtained in the step (2)2And (3) soaking in sol under a negative pressure condition, filtering, drying and calcining to obtain the embedded copper oxide nanotube catalyst.
2. The method according to claim 1, wherein the weight of the copper oxide in the embedded copper oxide nanotube catalyst is 10-30%, preferably 7-12% of the total weight of the catalyst.
3. The method according to claim 1, wherein the resin catalyst in step (1) is a polystyrene resin catalyst having an average diameter of 0.5 to 1.2 mm.
4. The method according to claim 1, wherein the resin catalyst in the step (1) has an average specific surface area of 600 to 1000cm2Preferably 700 to 900 cm/g2(iv)/g, the average pore diameter is 5 to 30nm, preferably 10 to 20nm, and the average pore volume is 0.01 to 0.1mL/g, preferably 0.03 to 0.05 mL/g.
5. The method according to claim 1, wherein in the step (2), CuCl is used2CuCl in solution2The mass percentage concentration of (A) is 10-30 wt%.
6. The method according to claim 1, wherein the heating temperature in the step (2) is 90 to 100 ℃.
7. The method according to claim 1, wherein the dipping time in the step (3) is 1 to 3 hours.
8. The production method according to claim 1, wherein the impregnation pressure in the step (3) is 1.0 to 10.0kPa, preferably 1.5 to 3.0 kPa.
9. The method according to claim 1, wherein the drying temperature in the step (3) is 30 to 40 ℃ and the drying time is 12 to 24 hours.
10. The method according to claim 1, wherein the calcination temperature in the step (3) is 150 to 200 ℃ and the calcination time is 1 to 3 hours.
11. The embedded copper oxide nanotube catalyst prepared by the preparation method of any one of claims 1 to 10.
12. The use of the embedded copper oxide nanotube catalyst of claim 11 to catalyze the hydrogenation of dimethyl adipate to produce 1, 6-hexanediol.
13. The use of claim 12, wherein the dimethyl adipate hydrogenation conditions are as follows: the reaction temperature is 180-260 ℃, the reaction pressure is 2-8 MPa, and the volume space velocity of dimethyl adipate is 0.2-2: 1, hydrogen-ester molar ratio of 150: 1-350: 1.
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| US20100069236A1 (en) * | 2006-11-10 | 2010-03-18 | Hae Jin Kim | Methods for manfacturing li-doped silica nanotube using anodic aluminum oxide template and use of the li-doped silica nanotube for energy storage |
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Effective date of registration: 20231221 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |