CN116060024B - Ester hydrogenation catalyst, preparation method and application thereof - Google Patents
Ester hydrogenation catalyst, preparation method and application thereof Download PDFInfo
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- CN116060024B CN116060024B CN202111278953.0A CN202111278953A CN116060024B CN 116060024 B CN116060024 B CN 116060024B CN 202111278953 A CN202111278953 A CN 202111278953A CN 116060024 B CN116060024 B CN 116060024B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 57
- 150000002148 esters Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 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 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005751 Copper oxide Substances 0.000 claims abstract description 34
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 34
- 239000002071 nanotube Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 9
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 31
- 229910052750 molybdenum Inorganic materials 0.000 claims description 23
- 239000011733 molybdenum Substances 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- -1 diethyl nickel dichloride Chemical compound 0.000 claims description 17
- 239000012159 carrier gas Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 150000002431 hydrogen Chemical class 0.000 abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 230000003993 interaction Effects 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
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An ester hydrogenation catalyst is prepared by dipping alumina hollow spheres under negative pressure of Cu (OH) 2 sol, and depositing a NiMoO 4 film on a copper oxide nanotube substrate by a chemical vapor deposition method. The method forms a copper oxide nanotube structure with uniform and regular pore diameter in the spherical wall pore canal of the aluminum oxide hollow sphere, the copper oxide nanotube is communicated with the hollow part in the aluminum oxide hollow sphere, and the curved surface structure of the hollow part in the aluminum oxide hollow sphere has an enrichment effect on reaction hydrogen, so that the hydrogen has higher concentration and stronger adsorption effect in the reaction active center. The NiMoO 4 film deposited on the surface of the copper oxide nanotube has the synergistic effect of two excessive metal oxides to speed up the hydrogen absorption and release of the catalyst, greatly reduce the consumption and circulation of hydrogen and greatly reduce the consumption and energy consumption of hydrogen circulation, thereby reducing the production cost.
Description
Technical Field
The invention relates to a hydrogenation catalyst, in particular to an ester hydrogenation catalyst which takes hollow alumina balls as a carrier, embeds copper oxide nanotubes and deposits a metal oxide film, and belongs to the technical field of catalysts.
Background
The hydrogenation catalyst is prepared by uniformly dispersing hydrogenation metal active components and catalyst auxiliaries, loading the hydrogenation metal active components and the catalyst auxiliaries on a carrier through methods such as dipping, chemical deposition and the like, and carrying out subsequent processes such as extrusion, molding, drying, roasting and the like. The carrier of the hydrogenation catalyst is particles with different materials, different shapes and particle diameters, has a certain specific surface area and a proper pore diameter and pore canal structure, can reduce aggregation of active components during sintering, and enhances the mechanical strength of the catalyst. The support can sometimes also provide additional active sites, which can have different catalytic activities through interaction between the active component and the support. The common hydrogenation catalyst is prepared by taking alumina, a molecular sieve, active carbon and the like as carriers, noble metal or transition metal as an active component, adding a catalyst auxiliary agent, and adopting methods of dipping, coprecipitation and the like, wherein in the use process, the catalyst has different characteristics and effects, and the cost of the catalyst is different, but most hydrogenation catalysts require higher hydrogen-oil ratio in the reaction, have larger consumption and circulation amount of hydrogen, cause a large amount of energy loss, and also improve the production cost.
The ester hydrogenation reaction means that the ester compound can produce corresponding alcohol substances through hydrogenation reaction under certain process conditions. The alcohol substance has wide application range, can be used as a clean gasoline additive, a surfactant, a plasticizer, an anti-emulsifying agent, an extracting agent and the like, is a good chemical raw material, and has great economic value. At present, the method for preparing the corresponding alcohol by using the ester hydrogenation is a main method for producing alcohol substances. However, in the existing technology of ester hydrogenation, the problems of larger molar ratio of hydrogen ester, large hydrogen consumption and circulation amount and higher energy consumption still exist.
Patent CN1011934228A discloses a catalyst for preparing alcohol by hydrogenation of acetate, a preparation method and application thereof, the catalyst uses silicon oxide or aluminum oxide as a carrier, metallic copper as an active component, the liquid space velocity of the reaction is low, the hydrogen ester is high, and the reaction conversion rate and the selectivity are low. Patent CN111659375A discloses a catalyst for preparing 1, 6-hexanediol by hydrogenating dimethyl adipate, a preparation method and application thereof, wherein SiO 2/ZrO2 is used as a carrier, noble metal ruthenium or iridium is used as an active component, the preparation process is complex, the catalyst cost is high, and the problems of higher molar ratio of hydrogen ester and higher energy consumption exist. The catalyst prepared by the impregnation method and the coprecipitation method has the conditions of uneven distribution and easy loss of active components, has higher requirements on molar ratio of the hydrogen ester, and has higher energy consumption and unsatisfactory reaction effect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an ester hydrogenation catalyst which can obviously reduce the molar ratio of hydrogen to ester when being applied to ester hydrogenation reaction, has good catalyst activity and stability and has 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 preparation method of an ester hydrogenation catalyst, comprising the following steps:
(1) Dissolving CuCl 2 in deionized water, heating, forming Cu (OH) 2 sol in a stirring state, and naturally cooling;
(2) Immersing the alumina hollow spheres in Cu (OH) 2 sol in the step (1), keeping the immersed alumina hollow spheres under the negative pressure condition, filtering, drying and calcining to obtain the alumina hollow spheres with the inner parts and the sphere walls embedded with the copper oxide nanotube substrates;
(3) And depositing a NiMoO 4 film on the copper oxide nanotube substrate by adopting a chemical vapor deposition method to obtain the ester hydrogenation catalyst.
Further, in the step (1), the mass percentage concentration of CuCl 2 in the CuCl 2 solution is 10-30wt%, the heating temperature is 90-100deg.C, the stirring revolution is 100-350 r/min, preferably 200-250 r/min, after the solution changes color to form sol, the heating and stirring are stopped, and the solution is naturally cooled.
Further, the average diameter of the alumina hollow spheres in the step (2) is 0.5-2 mm, preferably 0.5-1 mm; the average specific surface area is 280-380 cm 2/g, preferably 300-320 cm 2/g, the thickness of the spherical wall is 0.1-0.2 mm, and the average pore diameter of the spherical wall is 10-40 nm, preferably 20-30 nm.
Further, the alumina hollow spheres are preferably washed before use, the solvent used for washing is absolute ethanol with the concentration of 95%, 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 calcining temperature is 150-200 ℃, and the calcining time is 1-3 hours.
Further, the metal source used in the chemical vapor deposition method in the step (3) is diethyl nickel dichloride and molybdenum naphthenate, and the oxygen source is high-purity oxygen.
Further, the carrier gas used by the diethyl nickel dichloride in the step (3) is hydrogen, the flow rate is 10-30 sccm, the carrier gas used by the molybdenum naphthenate is hydrogen, the flow rate is 20-40 sccm, and the flow rate of the oxygen is 100-500 sccm.
Further, the temperature of the chemical vapor deposition in the step (3) is 500-1000 ℃; the deposition time is 3-6 hours; the vacuum degree for deposition is 5000-10000 Pa.
Further, after the deposition in the step (3) is finished, the temperature is reduced to room temperature, a NiMoO 4 film is deposited on the copper oxide substrate, and the temperature reduction rate is 0.1-1.0 ℃/s.
The technical object of the second aspect of the present invention is to provide an ester hydrogenation catalyst prepared by the above method. The preparation method adopts the alumina hollow sphere as a template, impregnates the alumina hollow sphere under the condition of negative pressure, enables Cu (OH) 2 sol to enter the inside of the alumina hollow sphere and the sphere wall pore canal, obtains the alumina hollow sphere and the sphere wall pore canal embedded copper oxide nanotube substrate after filtering, drying and calcining, and then deposits the NiMoO 4 film on the copper oxide nanotube substrate by a chemical vapor deposition method to obtain the catalyst. The method forms a copper oxide nanotube structure with uniform and regular pore diameter in the wall pore canal of the aluminum oxide hollow sphere, the copper oxide nanotube is communicated with the hollow part in the aluminum oxide hollow sphere, and the curved surface structure of the hollow part in the aluminum oxide hollow sphere has an enrichment effect on reaction hydrogen, so that the reaction gas has higher concentration in the hollow sphere, and the hydrogen re-reaction active center has higher concentration and stronger adsorption effect due to the gas sensitivity and the space limiting effect of the copper oxide nanotube. In addition, the NiMoO 4 film deposited on the surface of the copper oxide nanotube has the synergistic effect of two excessive metal oxides to speed up the hydrogen absorption and release of the catalyst, greatly reduce the use amount and circulation amount of hydrogen, greatly reduce the consumption of hydrogen and the energy consumption of hydrogen circulation, and further reduce the production cost. The catalyst has stronger catalytic activity, high mutual contact efficiency and mass transfer efficiency between reaction materials, higher reaction conversion rate and product selectivity, and good stability.
The technical object of the third aspect of the present invention is to provide the use of the hydrogenation catalyst for catalyzing the reaction of preparing 1, 6-hexanediol by hydrogenating dimethyl adipate.
In the above application, the dimethyl adipate hydrogenation reaction conditions were as follows: the reaction temperature is 150-250 ℃, preferably 160-200 ℃; the reaction pressure is 2-8 MPa, preferably 3-6 MPa, and the volume airspeed of the dimethyl adipate is 0.2-2: 1, preferably 0.5 to 1:1, molar ratio of hydrogen ester is 50:1 to 100:1, preferably 60:1 to 80:1.
Compared with the prior art, the invention has the following advantages:
(1) According to the hydrogenation catalyst, alumina hollow spheres are adopted as templates, cu (OH) 2 sol enters the alumina hollow spheres and sphere wall channels under the condition of negative pressure, and after filtration, drying and calcination, the hydrogenation catalyst with copper oxide nanotubes with better continuity embedded in the alumina hollow spheres and sphere wall channels is obtained; the copper oxide nanotubes embedded in the pore canal of the spherical wall are communicated with the hollow part of the alumina sphere, so that the reaction materials and hydrogen can freely and smoothly enter and exit and react.
(2) In the catalyst, the curved surface structure of the hollow part inside the alumina hollow sphere has an enrichment effect on the reaction hydrogen, so that the reaction gas has higher concentration inside the hollow sphere, and the hydrogen re-reaction active center has higher concentration and stronger adsorption effect due to the gas sensitivity and the space confinement effect of the copper oxide nano tube. The consumption and the circulation amount of the hydrogen can be greatly reduced, and the consumption of the hydrogen and the energy consumption of hydrogen circulation are greatly reduced, thereby reducing the production cost.
(3) The catalyst compounded by the copper oxide and the NiMoO 4 film has stronger catalytic activity, high mutual contact efficiency and mass transfer efficiency between reaction materials, higher reaction conversion rate and product selectivity, and good stability.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
Example 1
The hydrogenation catalyst was prepared in this example and applied to the dimethyl adipate esterification reaction to prepare 1, 6-hexanediol:
Preparing a hydrogenation catalyst:
(1) Dissolving 60gCuCl 2 in 300g of deionized water, reacting at 95 ℃ under the condition of stirring revolution of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for standby;
(2) Immersing 150g of hollow alumina spheres in the sol obtained in the step (1), immersing for 3 hours under the condition that the pressure is 1800Pa, filtering, drying for 12 hours under the condition of 50 ℃, and calcining for 2 hours under the condition of 200 ℃ to obtain the hollow alumina spheres embedded in the copper oxide nanotube substrate.
(3) Placing the hollow alumina balls obtained in the step (2) into chemical vapor deposition reaction equipment, wherein the vacuum degree reaches 8000Pa, the temperature rises to 1000 ℃, diethyl nickel dichloride is used as a nickel source, molybdenum naphthenate is used as a molybdenum source, the flow rate of carrier gas of the nickel source is 10sccm, the flow rate of carrier gas of the molybdenum source is 20sccm, and the flow rate of oxygen is 400sccm; and (3) reacting for 3 hours, closing the organic source and oxygen, and cooling to room temperature at 0.5 ℃/s to obtain the hydrogenation catalyst.
Hydrogenation reaction of dimethyl adipate to prepare 1, 6-hexanediol:
Introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor provided with an embedded copper oxide nanotube catalyst, wherein materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 160 ℃, the reaction pressure is 3MPa, the volume airspeed of the dimethyl adipate is 0.8h -1, and the molar ratio of the hydrogen to the ester is 50:1 and the reaction results are shown in Table 1.
Example 2
The hydrogenation catalyst was prepared in this example and applied to the dimethyl adipate esterification reaction to prepare 1, 6-hexanediol:
Preparing a hydrogenation catalyst:
(1) Dissolving 60gCuCl 2 in 300g of deionized water, reacting at 95 ℃ under the condition of stirring revolution of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for standby;
(2) Immersing 150g of hollow alumina spheres in the sol obtained in the step (1), immersing for 3 hours under the condition that the pressure is 1800Pa, filtering, drying for 12 hours under the condition of 50 ℃, and calcining for 2 hours under the condition of 200 ℃ to obtain the hollow alumina spheres embedded in the copper oxide nanotube substrate.
(3) Placing the hollow alumina balls obtained in the step (2) into chemical vapor deposition reaction equipment, wherein the vacuum degree reaches 10000Pa, the temperature is raised to 900 ℃, diethyl nickel dichloride is used as a nickel source, molybdenum naphthenate is used as a molybdenum source, the carrier gas flow rate of the nickel source is 15sccm, the carrier gas flow rate of the molybdenum source is 30sccm, and the flow rate of oxygen is 300sccm; and (3) reacting for 4 hours, closing the organic source and oxygen, and cooling to room temperature at 0.5 ℃/s to obtain the hydrogenation catalyst.
Hydrogenation reaction of dimethyl adipate to prepare 1, 6-hexanediol:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor provided with an embedded copper oxide nanotube catalyst, wherein materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 170 ℃, the reaction pressure is 4MPa, the volume airspeed of the dimethyl adipate is 1.0h -1, and the molar ratio of the hydrogen to the ester is 60:1 and the reaction results are shown in Table 1.
Example 3
The hydrogenation catalyst was prepared in this example and applied to the dimethyl adipate esterification reaction to prepare 1, 6-hexanediol:
Preparing a hydrogenation catalyst:
(1) Dissolving 60gCuCl 2 in 300g of deionized water, reacting at 95 ℃ under the condition of stirring revolution of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for standby;
(2) Immersing 150g of hollow alumina spheres in the sol obtained in the step (1), immersing for 3 hours under the condition that the pressure is 1800Pa, filtering, drying for 12 hours under the condition of 50 ℃, and calcining for 2 hours under the condition of 200 ℃ to obtain the hollow alumina spheres embedded in the copper oxide nanotube substrate.
(3) Placing the hollow alumina balls obtained in the step (2) into chemical vapor deposition reaction equipment, wherein the vacuum degree reaches 9000Pa, the temperature rises to 8000 ℃, diethyl nickel dichloride is used as a nickel source, molybdenum naphthenate is used as a molybdenum source, the flow rate of carrier gas of the nickel source is 20sccm, the flow rate of carrier gas of the molybdenum source is 30sccm, and the flow rate of oxygen is 400sccm; and (3) reacting for 4 hours, closing the organic source and oxygen, and cooling to room temperature at 0.5 ℃/s to obtain the hydrogenation catalyst.
Hydrogenation reaction of dimethyl adipate to prepare 1, 6-hexanediol:
Introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor provided with an embedded copper oxide nanotube catalyst, wherein materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 170 ℃, the reaction pressure is 5MPa, the volume airspeed of the dimethyl adipate is 0.8h -1, and the molar ratio of the hydrogen to the ester is 70:1 and the reaction results are shown in Table 1.
Example 4
The hydrogenation catalyst was prepared in this example and applied to the dimethyl adipate esterification reaction to prepare 1, 6-hexanediol:
Preparing a hydrogenation catalyst:
(1) Dissolving 60gCuCl 2 in 300g of deionized water, reacting at 95 ℃ under the condition of stirring revolution of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for standby;
(2) Immersing 150g of hollow alumina spheres in the sol obtained in the step (1), immersing for 3 hours under the condition that the pressure is 1800Pa, filtering, drying for 12 hours under the condition of 50 ℃, and calcining for 2 hours under the condition of 200 ℃ to obtain the hollow alumina spheres embedded in the copper oxide nanotube substrate.
(3) Placing the hollow alumina balls obtained in the step (2) into chemical vapor deposition reaction equipment, wherein the vacuum degree reaches 8000Pa, the temperature rises to 1000 ℃, diethyl nickel dichloride is used as a nickel source, molybdenum naphthenate is used as a molybdenum source, the carrier gas flow rate of the nickel source is 20sccm, the carrier gas flow rate of the molybdenum source is 35sccm, and the flow rate of oxygen is 350sccm; and (3) reacting for 4 hours, closing the organic source and oxygen, and cooling to room temperature at 0.5 ℃/s to obtain the hydrogenation catalyst.
Hydrogenation reaction of dimethyl adipate to prepare 1, 6-hexanediol:
Introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor provided with an embedded copper oxide nanotube catalyst, wherein materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 180 ℃, the reaction pressure is 5MPa, the volume airspeed of the dimethyl adipate is 0.8h -1, and the molar ratio of the hydrogen to the ester is 70:1 and the reaction results are shown in Table 1.
Example 5
The hydrogenation catalyst was prepared in this example and applied to the dimethyl adipate esterification reaction to prepare 1, 6-hexanediol:
Preparing a hydrogenation catalyst:
(1) Dissolving 60gCuCl 2 in 300g of deionized water, reacting at 95 ℃ under the condition of stirring revolution of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for standby;
(2) Immersing 150g of hollow alumina spheres in the sol obtained in the step (1), immersing for 3 hours under the condition that the pressure is 1800Pa, filtering, drying for 12 hours under the condition of 50 ℃, and calcining for 2 hours under the condition of 200 ℃ to obtain the hollow alumina spheres embedded in the copper oxide nanotube substrate.
(3) Putting the hollow alumina balls obtained in the step (2) into chemical vapor deposition reaction equipment, wherein the vacuum degree reaches 10000Pa, the temperature rises to 1000 ℃, diethyl nickel dichloride is used as a nickel source, molybdenum naphthenate is used as a molybdenum source, the carrier gas flow rate of the nickel source is 25sccm, the carrier gas flow rate of the molybdenum source is 35sccm, and the flow rate of oxygen is 400sccm; and (3) reacting for 5 hours, closing the organic source and oxygen, and cooling to room temperature at 0.5 ℃/s to obtain the hydrogenation catalyst.
Hydrogenation reaction of dimethyl adipate to prepare 1, 6-hexanediol:
Introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor provided with an embedded copper oxide nanotube catalyst, wherein materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 180 ℃, the reaction pressure is 4MPa, the volume airspeed of the dimethyl adipate is 0.8h -1, and the molar ratio of the hydrogen to the ester is 80:1 and the reaction results are shown in Table 1.
Example 6
The hydrogenation catalyst was prepared in this example and applied to the dimethyl adipate esterification reaction to prepare 1, 6-hexanediol:
Preparing a hydrogenation catalyst:
(1) Dissolving 60gCuCl 2 in 300g of deionized water, reacting at 95 ℃ under the condition of stirring revolution of 250r/min until the solution changes color to form sol, stopping heating and stirring, and naturally cooling for standby;
(2) Immersing 150g of hollow alumina spheres in the sol obtained in the step (1), immersing for 3 hours under the condition that the pressure is 1800Pa, filtering, drying for 12 hours under the condition of 50 ℃, and calcining for 2 hours under the condition of 200 ℃ to obtain the hollow alumina spheres embedded in the copper oxide nanotube substrate.
(3) Placing the hollow alumina balls obtained in the step (2) into chemical vapor deposition reaction equipment, wherein the vacuum degree reaches 8000Pa, the temperature rises to 800 ℃, diethyl nickel dichloride is used as a nickel source, molybdenum naphthenate is used as a molybdenum source, the carrier gas flow rate of the nickel source is 15sccm, the carrier gas flow rate of the molybdenum source is 25sccm, and the flow rate of oxygen is 400sccm; and (3) reacting for 3 hours, closing the organic source and oxygen, and cooling to room temperature at 0.5 ℃/s to obtain the hydrogenation catalyst.
Hydrogenation reaction of dimethyl adipate to prepare 1, 6-hexanediol:
introducing dimethyl adipate and hydrogen into a fixed bed continuous reactor provided with an embedded copper oxide nanotube catalyst, wherein materials enter from the top of the reactor and flow out from the bottom of the reactor, the reaction temperature is 180 ℃, the reaction pressure is 3MPa, the volume airspeed of the dimethyl adipate is 1.0h -1, and the molar ratio of the hydrogen to the ester is 80:1 and the reaction results are shown in Table 1.
Comparative example 1
Alumina spheres embedded in a copper oxide nanotube substrate were prepared according to the methods of steps (1) and (2) in example 5, metallic nickel and metallic molybdenum were supported on the obtained alumina spheres by impregnation, a hydrogenation catalyst was prepared, and other conditions were copper example 5, and the reaction results are shown in table 1.
Comparative example 2
A hydrogenation catalyst was prepared by directly depositing a thin film of NiMoO 4 on the pore channels of hollow alumina spheres in the procedure of step (3) of example 5, with other conditions, copper example 5, and the reaction results shown in Table 1.
Table 1 reaction results (conversion in moles) for the examples
Claims (12)
1. A method for preparing an ester hydrogenation catalyst, comprising the steps of:
(1) Dissolving CuCl 2 in deionized water, heating, forming Cu (OH) 2 sol in a stirring state, and naturally cooling;
(2) Immersing the alumina hollow spheres in Cu (OH) 2 sol in the step (1), keeping the immersed alumina hollow spheres under the negative pressure condition, filtering, drying and calcining to obtain the alumina hollow spheres with the inner parts and the sphere walls embedded with the copper oxide nanotube substrates;
(3) And depositing a NiMoO 4 film on the copper oxide nanotube substrate by adopting a chemical vapor deposition method to obtain the ester hydrogenation catalyst.
2. The preparation method according to claim 1, wherein the mass percentage concentration of CuCl 2 in the CuCl 2 solution in the step (1) is 10-30wt%, the heating temperature is 90-100deg.C, and after the solution changes color to form sol, the heating is stopped and the solution is naturally cooled.
3. The method according to claim 1, wherein the alumina hollow spheres in the step (2) have an average diameter of 0.5 to 2mm, an average specific surface area of 280 to 380cm 2/g, a sphere wall thickness of 0.1 to 0.2mm, and a sphere wall average pore diameter of 10 to 40nm.
4. The method according to claim 1, wherein the dipping time in the step (2) is 1 to 3 hours and the dipping pressure is 1000 to 10000Pa.
5. The process according to claim 4, wherein the impregnation pressure in step (2) is 1500 to 3000Pa.
6. The method of claim 1, wherein the metal source used in the chemical vapor deposition process in step (3) is diethyl nickel dichloride and molybdenum naphthenate, and the oxygen source is high purity oxygen.
7. The method according to claim 6, wherein the carrier gas used in the diethyl nickel dichloride in the step (3) is hydrogen at a flow rate of 10-30 sccm, the carrier gas used in the molybdenum naphthenate is hydrogen at a flow rate of 20-40 sccm, and the oxygen source is at a flow rate of 100-500 sccm.
8. The method according to claim 1, wherein the chemical vapor deposition temperature in the step (3) is 500 to 1000 ℃; the deposition time is 3-6 hours; the vacuum degree for deposition is 5000-10000 Pa.
9. The method according to claim 1, wherein after the deposition in the step (3) is completed, the temperature is reduced to room temperature, and the NiMoO 4 film is deposited on the copper oxide substrate, and the rate of the temperature reduction is 0.1-1.0 ℃/s.
10. An ester hydrogenation catalyst prepared by the process of any one of claims 1-9.
11. Use of the ester hydrogenation catalyst of claim 10 for catalyzing the hydrogenation of dimethyl adipate to 1, 6-hexanediol.
12. The use according to claim 11, characterized in that the dimethyl adipate hydrogenation reaction conditions are as follows: the reaction temperature is 150-250 ℃, the reaction pressure is 2-8 MPa, the volume airspeed of the adipic acid dimethyl ester is 0.2-2 h -1, and the molar ratio of the hydrogen ester is 100:1 to 250:1.
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