CN110975882A - Preparation method of catalyst for benzyl alcohol synthesis and catalytic hydrogenation system - Google Patents
Preparation method of catalyst for benzyl alcohol synthesis and catalytic hydrogenation system Download PDFInfo
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- CN110975882A CN110975882A CN201911192896.7A CN201911192896A CN110975882A CN 110975882 A CN110975882 A CN 110975882A CN 201911192896 A CN201911192896 A CN 201911192896A CN 110975882 A CN110975882 A CN 110975882A
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- catalyst
- active component
- activated carbon
- mesoporous activated
- benzyl alcohol
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 229
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 60
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 50
- 239000002002 slurry Substances 0.000 claims description 49
- 239000007864 aqueous solution Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 39
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 32
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 239000012018 catalyst precursor Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 230000002194 synthesizing effect Effects 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000004537 pulping Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 12
- 230000000087 stabilizing effect Effects 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 15
- 238000007865 diluting Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010606 normalization Methods 0.000 description 3
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 3
- 239000012465 retentate Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- JUVLYFQRUBLHEH-UHFFFAOYSA-N tert-butyl 4-(5-formyl-1,3-thiazol-2-yl)piperazine-1-carboxylate Chemical compound C1CN(C(=O)OC(C)(C)C)CCN1C1=NC=C(C=O)S1 JUVLYFQRUBLHEH-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910006297 γ-Fe2O3 Inorganic materials 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- C07C29/14—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 a —CHO group
- C07C29/141—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 a —CHO group 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a catalyst for benzyl alcohol synthesis and a catalytic hydrogenation system, wherein the catalyst comprises a carrier, and a first active component and a second active component which are dispersed on the carrier, wherein the carrier is mesoporous activated carbon, the first active component is palladium, the second active component is nickel, copper or cobalt, the mass percentage of the first active component in the catalyst is 5%, and the mass percentage of the second active component in the catalyst is 1-10%. According to the invention, mesoporous activated carbon is used as a catalyst carrier, so that the waste catalyst is favorably ashed, recycled and reused, and the purpose of controlling the activity of the catalyst and improving the selectivity of benzyl alcohol can be achieved by introducing a second group of active components into the catalyst; the catalytic hydrogenation system uses low-carbon alcohol and pure water as solvents and is matched with a catalyst, so that the catalytic hydrogenation efficiency can be improved, the overall selectivity of the system is greatly improved, the generation of over-hydrogenated products of toluene and ether is inhibited, the reaction time is shortened, and the production efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of precious metal catalyst preparation, and particularly relates to a preparation method of a catalyst for benzyl alcohol synthesis and a catalytic hydrogenation system.
Background
Benzyl alcohol is also called benzyl alcohol, is an important intermediate for synthesizing spices and medicines, and has wide application in the fields of sensitization, dyeing and finishing, cosmetics and the like. Currently, benzyl chloride hydrolysis, toluene oxidation, benzaldehyde reduction, yeast reduction and the like are used as methods for producing benzyl alcohol. The benzyl chloride hydrolysis method is a main method for producing benzyl alcohol at present, the production technology is mature, and can be divided into a batch method and a continuous method, the conversion rate of the batch method is low, and the reaction conditions of the continuous method are harsh; the toluene oxidation method has low conversion rate and more byproducts; the yeast reduction method has low conversion rate and long reaction time.
The catalytic hydrogenation of benzaldehyde to synthesize benzyl alcohol is a simple production technology, and has mild reaction conditions and environmental friendliness. The catalysts used are mostly palladium, platinum, copper and the like, wherein the palladium-catalyzed side reaction is less and is an ideal catalyst, the following formula is benzaldehyde catalytic hydrogenation reaction, target product phenethyl alcohol is obtained, but byproducts toluene and etherification products with excessive hydrogenation are generated, and the difficulty of improving the selectivity of the benzyl alcohol is the reaction.
Kotha et al reported a palladium catalyst with a stable binaphthyl skeleton (adv. Synth. Catal.2016,358,1694-1698) that can catalyze benzaldehyde in aqueous phase at normal temperature and pressure to give benzyl alcohol in 90% yield. However, this catalyst is not convenient to recover, and needs to be recovered by centrifugal filtration.
Patent CN 1379747A discloses a method for preparing benzyl alcohol by liquid phase hydrogenation of benzaldehyde, the catalyst carrier is silicon oxide or aluminum oxide, nickel is main catalyst, at least one of oxides of magnesium, barium, zirconium or calcium is cocatalyst, the finished catalyst is obtained by adopting an impregnation process through roasting at 400-700 ℃ and hydrogen reduction, the reaction is carried out for 5h under the operating conditions of 1.0-5.0MPa pressure and 120 ℃, the conversion rate of benzaldehyde is more than 93%, and the selectivity of phenethyl alcohol is more than 94%, thus obtaining better effect. Chinese patent CN 107442149A discloses a foam structure catalyst for the reaction of preparing benzyl alcohol by benzaldehyde hydrogenation, the catalyst reacts for 5 hours in absolute ethyl alcohol at 90 ℃ and 2.0MPa hydrogen pressure, the conversion rate of benzaldehyde reaches 99%, and the selectivity of benzyl alcohol reaches 96.2%. The two methods have the problems of complex catalyst preparation process, high temperature and high pressure required by operation conditions, long reaction time and poor production operation safety.
Patent CN 109824484A discloses a method for preparing benzyl alcohol by liquid-phase hydrogenation of benzaldehyde under mild conditions, and the catalyst adopted in the method is gamma-Fe2O3-HAP complex supported palladium catalyst gamma-Fe2O3The catalyst is-HAP-Pd, the water phase is catalyzed and hydrogenated by benzaldehyde under normal temperature and pressure to obtain benzyl alcohol with 100 percent of conversion rate and 99.3 percent of yield, the substrate conversion rate and the target product yield are ideal, the catalyst is easy to separate under the action of a magnetic field, and good effect is obtained under the operation condition of a laboratory. However, the process has potential problems in industrial application, the density of the core-shell carrier taking hydroxyapatite and ferric oxide as carriers is more than 3.0g/mL, the stirring in a laboratory is sufficient, the rotating speed of 1000r/min is very easy to reach, but the stirring rotating speed of an industrial production reaction kettle is very low, and the rotating speed of 100r/min is difficult to reach. Under the working conditions that stirring is insufficient and the catalyst cannot be uniformly dispersed in the system, the reaction time is long, the production efficiency is not improved, and in addition, the catalyst cannot be incinerated and enriched after being scrapped, a large amount of acid reagents are needed for dissolution, and certain recovery existsAnd (4) environmental protection.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a catalyst for benzyl alcohol synthesis, aiming at the defects of the prior art. The method adopts mesoporous activated carbon as a catalyst carrier, is beneficial to ashing, recycling and reusing of the waste catalyst, and can achieve the purpose of controlling the activity of the catalyst and improving the selectivity of the benzyl alcohol by introducing a second group of active components into the catalyst.
In order to solve the technical problems, the invention adopts the technical scheme that: the preparation method of the catalyst for benzyl alcohol synthesis is characterized in that the catalyst comprises a carrier, a first active component and a second active component, wherein the first active component and the second active component are dispersed on the carrier, the carrier is mesoporous activated carbon, the first active component is palladium, the second active component is nickel, copper or cobalt, the mass percentage of the first active component in the catalyst is 5%, and the mass percentage of the second active component in the catalyst is 1% -10%; the average pore diameter of the mesoporous activated carbon is 4 nm-10 nm;
the preparation method of the catalyst comprises the following steps:
step one, carrying out reflux treatment on mesoporous activated carbon for 2-4 h by using a sodium hydroxide aqueous solution under the microwave heating condition, washing the mesoporous activated carbon by using pure water until the pH value is 7.0-8.0, and drying the mesoporous activated carbon to obtain pretreated mesoporous activated carbon;
secondly, pulping the pretreated mesoporous activated carbon in the first step by using pure water, and stirring to obtain mesoporous activated carbon slurry;
adding a solution containing a first active component and a second active component into the mesoporous activated carbon slurry obtained in the second step under the stirring condition, continuously stirring for 1-2 h, then adjusting the pH value to 7.5-8.5 by using an inorganic alkali solution, and stabilizing for 2-4 h to obtain catalyst precursor slurry;
and step four, dropwise adding a sodium borohydride aqueous solution into the catalyst precursor slurry obtained in the step four, reducing for 2-4 h, filtering, and washing the intercepted matters to obtain the catalyst for synthesizing the benzyl alcohol.
The preparation method of the catalyst for benzyl alcohol synthesis is characterized in that the mass percentage of the second active component in the catalyst is 3% -7%.
The preparation method of the catalyst for benzyl alcohol synthesis is characterized in that the mass concentration of the sodium hydroxide aqueous solution in the step one is 3-10%.
The preparation method of the catalyst for benzyl alcohol synthesis is characterized in that the microwave heating temperature in the step one is 80-100 ℃.
The preparation method of the catalyst for benzyl alcohol synthesis is characterized in that the mass percentage of the pretreated mesoporous activated carbon in the mesoporous activated carbon slurry in the second step is 5-15%.
The preparation method of the catalyst for benzyl alcohol synthesis is characterized in that the solution containing the first active component and the second active component in the third step is prepared by uniformly mixing a hydrochloric acid solution of palladium chloride and an aqueous solution of nitrate of the second active component.
In addition, the invention also provides a catalytic hydrogenation system using the catalyst prepared by the method, which is characterized in that the solvent of the catalytic hydrogenation system is low-carbon alcohol and pure water, the mass of the catalyst is 0.1-0.7% of that of the substrate benzaldehyde, the catalytic hydrogenation reaction temperature is 40-100 ℃, the reaction pressure is 0.3-1.0 MPa, and the reaction time is 0.5-3.0 h.
The catalytic hydrogenation system is characterized in that the low-carbon alcohol is methanol, ethanol or propanol, the mass of the pure water is 15-60% of that of the low-carbon alcohol, and the mass of the substrate benzaldehyde is 10.0-50.0% of that of the solvent.
Compared with the prior art, the invention has the following advantages:
1. the method adopts mesoporous activated carbon as a catalyst carrier, and is beneficial to ashing, recycling and reusing of the waste catalyst; the pure palladium-carbon catalyst has high activity and poor benzyl alcohol selectivity, and the invention introduces a second group of active components to achieve the purpose of controlling the activity of the catalyst and improving the benzyl alcohol selectivity.
2. The catalytic hydrogenation system of the invention uses low-carbon alcohol and pure water as solvents, and is matched with the catalyst prepared by the invention, so that the catalytic hydrogenation efficiency can be improved, the overall selectivity of the system is greatly improved, the generation of over-hydrogenated products of toluene and ether is inhibited, the reaction time is shortened, and the production efficiency is improved.
3. The catalyst of the invention has simple preparation process, simple and convenient catalyst recovery, mild and easily realized catalytic hydrogenation system conditions and high production efficiency.
The technical solution of the present invention is further described in detail by the following examples.
Detailed Description
Example 1
The catalyst for synthesizing benzyl alcohol comprises a carrier, a first active component and a second active component, wherein the first active component and the second active component are dispersed on the carrier, the carrier is mesoporous activated carbon, the first active component is palladium, the second active component is nickel, the mass percent of palladium in the catalyst is 5%, and the mass percent of nickel in the catalyst is 5%; the average pore diameter of the mesoporous activated carbon is 4 nm;
the preparation method of the catalyst comprises the following steps:
step one, carrying out reflux treatment on mesoporous activated carbon for 3 hours by using a sodium hydroxide aqueous solution with the mass concentration of 5% under the microwave heating condition, washing the mesoporous activated carbon by using pure water until the pH value is 7.5, and drying the mesoporous activated carbon to obtain pretreated mesoporous activated carbon; the temperature of the microwave heating is 90 ℃;
step two, pulping 18.0g of the pretreated mesoporous activated carbon in the step one by using 162g of pure water, and stirring to obtain mesoporous activated carbon slurry;
dissolving palladium chloride containing 1.0g of palladium by using dilute hydrochloric acid to obtain a hydrochloric acid solution of the palladium chloride, dissolving nickel nitrate containing 1.0g of nickel by using 50g of pure water to obtain a nickel nitrate aqueous solution, mixing the hydrochloric acid solution of the palladium chloride and the nickel nitrate aqueous solution, and diluting to 200mL to obtain an active component solution; adding the active component solution into the mesoporous activated carbon slurry obtained in the second step under the stirring condition, continuously stirring for 1h, and then adjusting the pH value to 8.0 by using an inorganic alkali solution and stabilizing for 3h to obtain catalyst precursor slurry;
and step four, dripping 160mL of 5% sodium borohydride aqueous solution into the catalyst precursor slurry obtained in the step four, reducing for 3 hours, filtering, and washing the retentate to obtain the catalyst for synthesizing the benzyl alcohol.
Example 2
The catalyst for synthesizing benzyl alcohol comprises a carrier, a first active component and a second active component, wherein the first active component and the second active component are dispersed on the carrier, the carrier is mesoporous activated carbon, the first active component is palladium, the second active component is copper, the mass percentage of the palladium in the catalyst is 5%, and the mass percentage of the copper in the catalyst is 5%; the average pore diameter of the mesoporous activated carbon is 10 nm;
the preparation method of the catalyst comprises the following steps:
step one, carrying out reflux treatment on mesoporous activated carbon for 4 hours by using a sodium hydroxide aqueous solution with the mass concentration of 3% under the microwave heating condition, washing the mesoporous activated carbon by using pure water until the pH value is 7.0, and drying the mesoporous activated carbon to obtain pretreated mesoporous activated carbon; the temperature of the microwave heating is 80 ℃;
step two, pulping 18.0g of the pretreated mesoporous activated carbon in the step one by 342g of pure water, and stirring to obtain mesoporous activated carbon slurry;
dissolving palladium chloride containing 1.0g of palladium by using dilute hydrochloric acid to obtain a hydrochloric acid solution of the palladium chloride, dissolving copper nitrate containing 1.0g of copper by using 50g of pure water to obtain a copper nitrate aqueous solution, mixing the hydrochloric acid solution of the palladium chloride and the copper nitrate aqueous solution, and diluting to 200mL to obtain an active component solution; adding the active component solution into the mesoporous activated carbon slurry obtained in the second step under the stirring condition, continuously stirring for 1.5h, and then adjusting the pH value to 7.5 by using an inorganic alkali solution and stabilizing for 4h to obtain catalyst precursor slurry;
and step four, dropwise adding a sodium borohydride aqueous solution into the catalyst precursor slurry obtained in the step four, reducing for 2 hours, filtering, and washing the intercepted matters to obtain the catalyst for synthesizing the benzyl alcohol.
Example 3
The catalyst for synthesizing benzyl alcohol comprises a carrier, a first active component and a second active component, wherein the first active component and the second active component are dispersed on the carrier, the carrier is mesoporous activated carbon, the first active component is palladium, the second active component is cobalt, the mass percentage of palladium in the catalyst is 5%, and the mass percentage of cobalt in the catalyst is 5%; the average pore diameter of the mesoporous activated carbon is 8 nm;
the preparation method of the catalyst comprises the following steps:
step one, carrying out reflux treatment on mesoporous activated carbon for 2 hours by using a 10% sodium hydroxide aqueous solution in mass concentration under the microwave heating condition, washing the mesoporous activated carbon by using pure water until the pH value is 8.0, and drying the mesoporous activated carbon to obtain pretreated mesoporous activated carbon; the temperature of the microwave heating is 100 ℃;
step two, pulping 18.0g of the pretreated mesoporous activated carbon in the step one by using 102g of pure water, and stirring to obtain mesoporous activated carbon slurry;
dissolving palladium chloride containing 1.0g of palladium by using dilute hydrochloric acid to obtain a hydrochloric acid solution of the palladium chloride, dissolving cobalt nitrate containing 1.0g of cobalt by using 50g of pure water to obtain an aqueous solution of the cobalt nitrate, mixing the hydrochloric acid solution of the palladium chloride and the aqueous solution of the cobalt nitrate, and diluting to 200mL to obtain an active component solution; adding the active component solution into the mesoporous activated carbon slurry obtained in the second step under the stirring condition, continuously stirring for 2 hours, and then adjusting the pH value to 8.5 by using an inorganic alkali solution and stabilizing for 2 hours to obtain catalyst precursor slurry;
and step four, dropwise adding a sodium borohydride aqueous solution into the catalyst precursor slurry obtained in the step four, reducing for 4 hours, filtering, and washing the intercepted matters to obtain the catalyst for synthesizing the benzyl alcohol.
Example 4
The catalyst for synthesizing benzyl alcohol comprises a carrier, a first active component and a second active component, wherein the first active component and the second active component are dispersed on the carrier, the carrier is mesoporous activated carbon, the first active component is palladium, the second active component is copper, the mass percentage of the palladium in the catalyst is 5%, and the mass percentage of the copper in the catalyst is 2.5%; the average pore diameter of the mesoporous activated carbon is 10 nm;
the preparation method of the catalyst comprises the following steps:
step one, carrying out reflux treatment on mesoporous activated carbon for 4 hours by using a sodium hydroxide aqueous solution with the mass concentration of 3% under the microwave heating condition, washing the mesoporous activated carbon by using pure water until the pH value is 7.0, and drying the mesoporous activated carbon to obtain pretreated mesoporous activated carbon; the temperature of the microwave heating is 80 ℃;
step two, pulping 18.5g of the pretreated mesoporous activated carbon in the step one by using 166.5g of pure water, and stirring to obtain mesoporous activated carbon slurry;
dissolving palladium chloride containing 1.0g of palladium by using dilute hydrochloric acid to obtain a hydrochloric acid solution of the palladium chloride, dissolving copper nitrate containing 0.5g of copper by using 50g of pure water to obtain a copper nitrate aqueous solution, mixing the hydrochloric acid solution of the palladium chloride and the copper nitrate aqueous solution, and diluting to 200mL to obtain an active component solution; adding the active component solution into the mesoporous activated carbon slurry obtained in the second step under the stirring condition, continuously stirring for 1.5h, and then adjusting the pH value to 7.5 by using an inorganic alkali solution and stabilizing for 4h to obtain catalyst precursor slurry;
and step four, dropwise adding a sodium borohydride aqueous solution into the catalyst precursor slurry obtained in the step four, reducing for 2 hours, filtering, and washing the intercepted matters to obtain the catalyst for synthesizing the benzyl alcohol.
Example 5
The catalyst for synthesizing benzyl alcohol comprises a carrier, a first active component and a second active component, wherein the first active component and the second active component are dispersed on the carrier, the carrier is mesoporous activated carbon, the first active component is palladium, the second active component is copper, the mass percentage of the palladium in the catalyst is 5%, and the mass percentage of the copper in the catalyst is 7.5%; the average pore diameter of the mesoporous activated carbon is 10 nm;
the preparation method of the catalyst comprises the following steps:
step one, carrying out reflux treatment on mesoporous activated carbon for 4 hours by using a sodium hydroxide aqueous solution with the mass concentration of 3% under the microwave heating condition, washing the mesoporous activated carbon by using pure water until the pH value is 7.0, and drying the mesoporous activated carbon to obtain pretreated mesoporous activated carbon; the temperature of the microwave heating is 80 ℃;
step two, pulping 17.5g of the pretreated mesoporous activated carbon in the step one by 157.5g of pure water, and stirring to obtain mesoporous activated carbon slurry;
dissolving palladium chloride containing 1.0g of palladium by using dilute hydrochloric acid to obtain a hydrochloric acid solution of the palladium chloride, dissolving copper nitrate containing 1.5g of copper by using 50g of pure water to obtain a copper nitrate aqueous solution, mixing the hydrochloric acid solution of the palladium chloride and the copper nitrate aqueous solution, and diluting to 200mL to obtain an active component solution; adding the active component solution into the mesoporous activated carbon slurry obtained in the second step under the stirring condition, continuously stirring for 1.5h, and then adjusting the pH value to 7.5 by using an inorganic alkali solution and stabilizing for 4h to obtain catalyst precursor slurry;
and step four, dropwise adding a sodium borohydride aqueous solution into the catalyst precursor slurry obtained in the step four, reducing for 2 hours, filtering, and washing the intercepted matters to obtain the catalyst for synthesizing the benzyl alcohol.
Example 6
The catalyst for synthesizing benzyl alcohol comprises a carrier, a first active component and a second active component, wherein the first active component and the second active component are dispersed on the carrier, the carrier is mesoporous activated carbon, the first active component is palladium, the second active component is nickel, the mass percent of palladium in the catalyst is 5%, and the mass percent of nickel in the catalyst is 3%; the average pore diameter of the mesoporous activated carbon is 4 nm;
the preparation method of the catalyst comprises the following steps:
step one, carrying out reflux treatment on mesoporous activated carbon for 3 hours by using a sodium hydroxide aqueous solution with the mass concentration of 5% under the microwave heating condition, washing the mesoporous activated carbon by using pure water until the pH value is 7.5, and drying the mesoporous activated carbon to obtain pretreated mesoporous activated carbon; the temperature of the microwave heating is 90 ℃;
step two, pulping 18.4g of the pretreated mesoporous activated carbon in the step one by using 166g of pure water, and stirring to obtain mesoporous activated carbon slurry;
dissolving palladium chloride containing 1.0g of palladium by using dilute hydrochloric acid to obtain a hydrochloric acid solution of the palladium chloride, dissolving nickel nitrate containing 0.6g of nickel by using 50g of pure water to obtain a nickel nitrate aqueous solution, mixing the hydrochloric acid solution of the palladium chloride and the nickel nitrate aqueous solution, and diluting to 200mL to obtain an active component solution; adding the active component solution into the mesoporous activated carbon slurry obtained in the second step under the stirring condition, continuously stirring for 1h, and then adjusting the pH value to 8.0 by using an inorganic alkali solution and stabilizing for 3h to obtain catalyst precursor slurry;
and step four, dripping 160mL of 5% sodium borohydride aqueous solution into the catalyst precursor slurry obtained in the step four, reducing for 3 hours, filtering, and washing the retentate to obtain the catalyst for synthesizing the benzyl alcohol.
Example 7
The catalyst for synthesizing benzyl alcohol comprises a carrier, a first active component and a second active component, wherein the first active component and the second active component are dispersed on the carrier, the carrier is mesoporous activated carbon, the first active component is palladium, the second active component is copper, the mass percentage of the palladium in the catalyst is 5%, and the mass percentage of the copper in the catalyst is 10%; the average pore diameter of the mesoporous activated carbon is 10 nm;
the preparation method of the catalyst comprises the following steps:
step one, carrying out reflux treatment on mesoporous activated carbon for 4 hours by using a sodium hydroxide aqueous solution with the mass concentration of 3% under the microwave heating condition, washing the mesoporous activated carbon by using pure water until the pH value is 7.0, and drying the mesoporous activated carbon to obtain pretreated mesoporous activated carbon; the temperature of the microwave heating is 80 ℃;
step two, pulping 17.0g of the pretreated mesoporous activated carbon in the step one by using 150g of pure water, and stirring to obtain mesoporous activated carbon slurry;
dissolving palladium chloride containing 1.0g of palladium by using dilute hydrochloric acid to obtain a hydrochloric acid solution of the palladium chloride, dissolving copper nitrate containing 2.0g of copper by using 50g of pure water to obtain a copper nitrate aqueous solution, mixing the hydrochloric acid solution of the palladium chloride and the copper nitrate aqueous solution, and diluting to 200mL to obtain an active component solution; adding the active component solution into the mesoporous activated carbon slurry obtained in the second step under the stirring condition, continuously stirring for 1.5h, and then adjusting the pH value to 7.5 by using an inorganic alkali solution and stabilizing for 4h to obtain catalyst precursor slurry;
and step four, dropwise adding a sodium borohydride aqueous solution into the catalyst precursor slurry obtained in the step four, reducing for 2 hours, filtering, and washing the intercepted matters to obtain the catalyst for synthesizing the benzyl alcohol.
Example 8
The catalyst for synthesizing benzyl alcohol comprises a carrier, a first active component and a second active component, wherein the first active component and the second active component are dispersed on the carrier, the carrier is mesoporous activated carbon, the first active component is palladium, the second active component is cobalt, the mass percentage of palladium in the catalyst is 5%, and the mass percentage of cobalt in the catalyst is 7%; the average pore diameter of the mesoporous activated carbon is 8 nm;
the preparation method of the catalyst comprises the following steps:
step one, carrying out reflux treatment on mesoporous activated carbon for 2 hours by using a 10% sodium hydroxide aqueous solution in mass concentration under the microwave heating condition, washing the mesoporous activated carbon by using pure water until the pH value is 8.0, and drying the mesoporous activated carbon to obtain pretreated mesoporous activated carbon; the temperature of the microwave heating is 100 ℃;
step two, pulping 17.6g of the pretreated mesoporous activated carbon in the step one by using 150g of pure water, and stirring to obtain mesoporous activated carbon slurry;
dissolving palladium chloride containing 1.0g of palladium by using dilute hydrochloric acid to obtain a hydrochloric acid solution of the palladium chloride, dissolving cobalt nitrate containing 1.4g of cobalt by using 50g of pure water to obtain an aqueous solution of the cobalt nitrate, mixing the hydrochloric acid solution of the palladium chloride and the aqueous solution of the cobalt nitrate, and diluting to 200mL to obtain an active component solution; adding the active component solution into the mesoporous activated carbon slurry obtained in the second step under the stirring condition, continuously stirring for 2 hours, and then adjusting the pH value to 8.5 by using an inorganic alkali solution and stabilizing for 2 hours to obtain catalyst precursor slurry;
and step four, dropwise adding a sodium borohydride aqueous solution into the catalyst precursor slurry obtained in the step four, reducing for 4 hours, filtering, and washing the intercepted matters to obtain the catalyst for synthesizing the benzyl alcohol.
Example 9
The catalyst for synthesizing benzyl alcohol comprises a carrier, a first active component and a second active component, wherein the first active component and the second active component are dispersed on the carrier, the carrier is mesoporous activated carbon, the first active component is palladium, the second active component is copper, the mass percentage of the palladium in the catalyst is 5%, and the mass percentage of the copper in the catalyst is 1%; the average pore diameter of the mesoporous activated carbon is 10 nm;
the preparation method of the catalyst comprises the following steps:
step one, carrying out reflux treatment on mesoporous activated carbon for 4 hours by using a sodium hydroxide aqueous solution with the mass concentration of 3% under the microwave heating condition, washing the mesoporous activated carbon by using pure water until the pH value is 7.0, and drying the mesoporous activated carbon to obtain pretreated mesoporous activated carbon; the temperature of the microwave heating is 80 ℃;
step two, pulping 18.8g of the pretreated mesoporous activated carbon in the step one by using 170g of pure water, and stirring to obtain mesoporous activated carbon slurry;
dissolving palladium chloride containing 1.0g of palladium by using dilute hydrochloric acid to obtain a hydrochloric acid solution of the palladium chloride, dissolving copper nitrate containing 0.2g of copper by using 50g of pure water to obtain a copper nitrate aqueous solution, mixing the hydrochloric acid solution of the palladium chloride and the copper nitrate aqueous solution, and diluting to 200mL to obtain an active component solution; adding the active component solution into the mesoporous activated carbon slurry obtained in the second step under the stirring condition, continuously stirring for 1.5h, and then adjusting the pH value to 7.5 by using an inorganic alkali solution and stabilizing for 4h to obtain catalyst precursor slurry;
and step four, dropwise adding a sodium borohydride aqueous solution into the catalyst precursor slurry obtained in the step four, reducing for 2 hours, filtering, and washing the intercepted matters to obtain the catalyst for synthesizing the benzyl alcohol.
Comparative example
Step one, carrying out reflux treatment on mesoporous activated carbon for 3 hours by using a sodium hydroxide aqueous solution with the mass concentration of 5% under the microwave heating condition, washing the mesoporous activated carbon by using pure water until the pH value is 7.5, and drying the mesoporous activated carbon to obtain pretreated mesoporous activated carbon; the temperature of the microwave heating is 90 ℃;
pulping 19.0g of activated carbon by 171g of pure water, and stirring to obtain mesoporous activated carbon pulp; feeding;
dissolving palladium chloride containing 1.0g of palladium by using dilute hydrochloric acid, and adding water to dilute the solution to 200mL to obtain a palladium chloride solution; under the condition of stirring, adding a palladium chloride solution into the mesoporous activated carbon slurry obtained in the second step, continuously stirring for 1.0 hour, then adjusting the pH value to 8.0 by using an inorganic alkali solution, and stabilizing for 3.0 hours to obtain catalyst precursor slurry;
and step four, dripping 160mL of 5% sodium borohydride aqueous solution into the catalyst precursor slurry obtained in the step four, reducing for 3 hours, filtering, and washing the retentate to obtain the catalyst for synthesizing the benzyl alcohol.
Example 10
The catalyst prepared in the embodiments 1 to 9 and the comparative example of the invention is used for catalyzing benzaldehyde to synthesize benzyl alcohol, and the specific method comprises the following steps: sequentially adding 30.0g of benzaldehyde into a 300mL stainless steel high-pressure reaction kettle; ethanol: 100.0 g; 30.0g of pure water; 0.05g of catalyst; flushing the kettle with nitrogen and hydrogen sequentially for three times, keeping the hydrogen pressure at 0.6MPa, keeping the constant pressure, controlling the temperature at 60 ℃, and reacting for 2.0 h. After the reaction, sampling and carrying out gas chromatography analysis, and analyzing the contents of benzaldehyde, benzyl alcohol, methylbenzene and phenetole by adopting an area normalization method. The results are shown in Table 1.
Table 1 example 10 benzaldehyde hydrogenation results
As can be seen from table 1, the introduction of the second active component is effective to improve the selectivity of the system, and the introduction of the second active component has an optimal dosage; the activity of the catalyst cannot be effectively inhibited by introducing the second component at a low content, and the selectivity of the catalyst is affected by introducing the second component at a high content.
Example 11
The catalyst prepared in the embodiments 1 to 9 and the comparative example of the invention is used for catalyzing benzaldehyde to synthesize benzyl alcohol, and the specific method comprises the following steps: sequentially adding 30.0g of benzaldehyde into a 300mL stainless steel high-pressure reaction kettle; methanol: 100.0 g; 60g of pure water; 0.03g of catalyst; flushing the kettle with nitrogen and hydrogen sequentially for three times, keeping the hydrogen pressure at 0.3MPa, keeping the constant pressure, controlling the temperature at 40 ℃, and reacting for 3.0 h. After the reaction, sampling and carrying out gas chromatography analysis, and analyzing the contents of benzaldehyde, benzyl alcohol, methylbenzene and phenetole by adopting an area normalization method. The results are shown in Table 2.
Table 2 example 11 benzaldehyde hydrogenation results
| Examples | Benzaldehyde% | Benzyl alcohol% | Toluene% | Anisole% |
| Comparative example | 0.00 | 45.37 | 21.65 | 32.98 |
| Example 1 | 0.00 | 98.37 | 0.87 | 0.76 |
| Example 2 | 0.00 | 95.17 | 1.58 | 3.25 |
| Example 3 | 0.00 | 96.52 | 1.37 | 2.11 |
| Example 4 | 0.00 | 76.98 | 8.26 | 14.76 |
| Example 5 | 0.00 | 97.52 | 0.23 | 2.25 |
| Example 6 | 0.00 | 96.59 | 1.20 | 2.21 |
| Example 7 | 29.37 | 47.51 | 9.02 | 14.10 |
| Example 8 | 0.00 | 98.20 | 0.39 | 1.41 |
| Example 9 | 0.00 | 73.54 | 6.16 | 20.30 |
As can be seen from table 2, the introduction of the second active component affects the activity and selectivity of the catalyst after the system is modified; methanol is used as a solvent, and the proportion of the byproduct ether is higher than that of ethanol; but the problem can be solved by the adjustment of the catalyst.
Example 12
The catalyst prepared in the embodiments 1 to 9 and the comparative example of the invention is used for catalyzing benzaldehyde to synthesize benzyl alcohol, and the specific method comprises the following steps: sequentially adding 20.0g of benzaldehyde into a 300mL stainless steel high-pressure reaction kettle; propanol: 174.0 g; 26.0g of pure water; 0.14g of catalyst; flushing the kettle with nitrogen and hydrogen sequentially for three times, keeping the hydrogen pressure at 1.0MPa constant pressure, controlling the temperature at 100 ℃, and reacting for 0.5 h. After the reaction, sampling and carrying out gas chromatography analysis, and analyzing the contents of benzaldehyde, benzyl alcohol, methylbenzene and phenetole by adopting an area normalization method. The results are shown in Table 3.
Table 3 example 12 benzaldehyde hydrogenation results
| Examples | Benzaldehyde% | Benzyl alcohol% | Toluene% | Phenyl propyl ether% |
| Comparative example | 0.00 | 45.37 | 38.54 | 16.09 |
| Example 1 | 0.00 | 99.10 | 0.32 | 0.58 |
| Example 2 | 0.00 | 98.56 | 1.03 | 0.41 |
| Example 3 | 0.00 | 95.31 | 3.13 | 1.56 |
| Example 4 | 0.00 | 95.67 | 2.94 | 1.39 |
| Example 5 | 0.00 | 97.24 | 1.83 | 0.93 |
| Example 6 | 0.00 | 95.59 | 3.19 | 1.22 |
| Example 7 | 15.84 | 58.29 | 17.50 | 8.37 |
| Example 8 | 0.00 | 98.71 | 0.76 | 0.53 |
| Example 9 | 0.00 | 85.43 | 10.32 | 4.25 |
As can be seen from Table 3, the shorter the reaction time is controlled, the lower the by-product is relatively, under the conditions that the catalyst is matched with the reaction system.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the catalyst for benzyl alcohol synthesis is characterized in that the catalyst comprises a carrier, a first active component and a second active component, wherein the first active component and the second active component are dispersed on the carrier, the carrier is mesoporous activated carbon, the first active component is palladium, the second active component is nickel, copper or cobalt, the mass percentage of the first active component in the catalyst is 5%, and the mass percentage of the second active component in the catalyst is 1% -10%; the average pore diameter of the mesoporous activated carbon is 4 nm-10 nm;
the preparation method of the catalyst comprises the following steps:
step one, carrying out reflux treatment on mesoporous activated carbon for 2-4 h by using a sodium hydroxide aqueous solution under the microwave heating condition, washing the mesoporous activated carbon by using pure water until the pH value is 7.0-8.0, and drying the mesoporous activated carbon to obtain pretreated mesoporous activated carbon;
secondly, pulping the pretreated mesoporous activated carbon in the first step by using pure water, and stirring to obtain mesoporous activated carbon slurry;
adding a solution containing a first active component and a second active component into the mesoporous activated carbon slurry obtained in the second step under the stirring condition, continuously stirring for 1-2 h, then adjusting the pH value to 7.5-8.5 by using an inorganic alkali solution, and stabilizing for 2-4 h to obtain catalyst precursor slurry;
and step four, dropwise adding a sodium borohydride aqueous solution into the catalyst precursor slurry obtained in the step four, reducing for 2-4 h, filtering, and washing the intercepted matters to obtain the catalyst for synthesizing the benzyl alcohol.
2. The method for preparing a catalyst for benzyl alcohol synthesis according to claim 1, wherein the mass percentage of the second active component in the catalyst is 3-7%.
3. The method according to claim 1, wherein the concentration of the aqueous sodium hydroxide solution in step one is 3 to 10% by mass.
4. The method according to claim 1, wherein the microwave heating temperature in the first step is 80 ℃ to 100 ℃.
5. The method for preparing a catalyst for benzyl alcohol synthesis as claimed in claim 1, wherein the pretreated mesoporous activated carbon in the mesoporous activated carbon slurry in the second step is 5-15% by mass.
6. The method of claim 1, wherein the solution containing the first active component and the second active component in step three is prepared by uniformly mixing a hydrochloric acid solution of palladium chloride and an aqueous solution of a nitrate of the second active component.
7. A catalytic hydrogenation system using the catalyst prepared by the method of any one of claims 1 to 6, wherein the solvent of the catalytic hydrogenation system is low carbon alcohol and pure water, the mass of the catalyst is 0.1-0.7% of that of the benzaldehyde substrate, the catalytic hydrogenation reaction temperature is 40-100 ℃, the reaction pressure is 0.3-1.0 MPa, and the reaction time is 0.5-3.0 h.
8. The catalytic hydrogenation system of claim 7, wherein the lower alcohol is methanol, ethanol or propanol, the mass of the pure water is 15-60% of that of the lower alcohol, and the mass of the benzaldehyde substrate is 10.0-50.0% of that of the solvent.
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| CN111450836A (en) * | 2020-04-12 | 2020-07-28 | 浙江师范大学 | Method for synthesizing p-hydroxybenzyl alcohol |
| CN114950413A (en) * | 2022-06-08 | 2022-08-30 | 中国科学院化学研究所 | Preparation method of graphdiyne modified hydrophilic catalyst and application of graphdiyne modified hydrophilic catalyst in aqueous phase hydrogenation |
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