CN113548944A - Method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde - Google Patents
Method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde Download PDFInfo
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- CN113548944A CN113548944A CN202110873410.7A CN202110873410A CN113548944A CN 113548944 A CN113548944 A CN 113548944A CN 202110873410 A CN202110873410 A CN 202110873410A CN 113548944 A CN113548944 A CN 113548944A
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- benzaldehyde
- benzyl alcohol
- reaction
- sodium
- catalytic hydrogenation
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 180
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000007868 Raney catalyst Substances 0.000 claims abstract description 28
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000564 Raney nickel Inorganic materials 0.000 claims abstract description 28
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 104
- 238000003756 stirring Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 235000019794 sodium silicate Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 235000013904 zinc acetate Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims 1
- 235000011150 stannous chloride Nutrition 0.000 claims 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims 1
- 238000013329 compounding Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- -1 aromatic alcohols Chemical class 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000686 essence Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 240000007436 Cananga odorata Species 0.000 description 1
- 241001632576 Hyacinthus Species 0.000 description 1
- 235000010254 Jasminum officinale Nutrition 0.000 description 1
- 240000005385 Jasminum sambac Species 0.000 description 1
- 235000014150 Myroxylon pereirae Nutrition 0.000 description 1
- 244000302151 Myroxylon pereirae Species 0.000 description 1
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 1
- 241000219925 Oenothera Species 0.000 description 1
- 235000004496 Oenothera biennis Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010656 jasmine oil Substances 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 239000008155 medical solution Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001157 myroxylon pereirae klotzsch resin Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde, wherein the benzaldehyde reacts with hydrogen in an organic solvent in the presence of a catalyst to obtain the benzyl alcohol; wherein the catalyst is a mixture of Raney nickel and inorganic salt, and the weight ratio of benzaldehyde to Raney nickel is 1: (0.05-0.3), wherein the weight ratio of the benzaldehyde to the inorganic salt is 1: (0.005-0.05). The catalyst is prepared by compounding Raney nickel and inorganic salt, so that the catalytic reaction condition is mild, the cost is low, no pollution is caused, the environment is protected, and the product yield is high.
Description
Technical Field
The invention relates to the technical field of benzyl alcohol synthesis, and particularly relates to a method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde.
Background
Benzyl alcohol is an important fragrance and intermediate, one of the simplest aromatic alcohols, and can be considered as phenyl-substituted carbinols. Most of the essential oils in nature exist in the form of esters, such as jasmine oil, hyacinth oil and peru balsam. Benzyl alcohol is a very useful fixative and is an essential perfume for blending of essences such as jasmine, evening primrose, ylang-ylang, etc. Meanwhile, the method is used for preparing perfumed soap and daily cosmetic essence. In the production of industrial chemicals, benzyl alcohol can be used as a coating solvent, photographic developer, polyvinyl chloride stabilizer, synthetic resin solvent, and preservative for ointments or medical solutions. Benzyl alcohol is a permissible flavorant.
At present, benzyl alcohol preparation methods comprise a benzyl chloride and sodium carbonate batch hydrolysis method and a continuous hydrolysis method, a toluene oxidation method, a methyl benzoate liquid phase reduction method, a gas-solid phase continuous hydrogenation method adopting a series reactor and a benzaldehyde hydrogenation method. Benzyl chloride hydrolysis is the main industrial production method, and the prominent disadvantages are that: benzyl chloride produces more by-products such as benzyl ether under basic conditions. The catalytic hydrogenation method of benzaldehyde is an environment-friendly synthesis process, has high yield and low synthesis cost, and is a high-efficiency clean production method.
At present, the route for synthesizing benzyl alcohol by catalytic hydrogenation of benzaldehyde is as follows:
chinese patent CN 103030528A discloses a method for preparing benzyl alcohol by liquid-phase hydrogenation of benzaldehyde, which takes cyclohexane as a solvent, benzaldehyde and hydrogen as raw materials, the reaction temperature is 140 ℃, the reaction pressure is 5.0MPa, the raw materials and a catalyst (15.0 percent of NiO, 3 percent of MgO, and 7.5 percent of P)2O5-71.5％SiO2) The contact reaction lasts for 4 hours, the conversion rate of benzaldehyde reaches over 93%, and the selectivity of benzyl alcohol reaches over 94%. However, in the above-mentioned technology, the preparation process of the catalyst is complicated, and the specific preparation process is as follows: weighing 10.0g Ni (NO)3)2·6H2O，8.0g Mg(NO3)2·6H2O is dissolved in 12.0g of distilled water, and a certain amount of NH 2.5g is added4H2PO4Or 3.6g (NH)4)2H2PO4Adding concentrated HNO dropwise thereto3Dissolving the precipitate, and adjusting the pH value to be 4-5 to form a solution I; heating the solution I to 70 ℃, and dropwise adding the solution I to 15.0g of SiO while the solution is hot2The carrier is dried at 120 ℃ and then roasted at 550 ℃ for 8 hours.
Chinese patent CN109824484A discloses a method for preparing benzyl alcohol by liquid phase hydrogenation of benzaldehyde under mild conditions, in the presence of a catalyst, benzaldehyde reacts with hydrogen in a solvent to obtain benzyl alcohol, and the catalyst adopted in the liquid phase hydrogenation reaction is gamma-Fe2O3-HAP complex supported palladium catalyst gamma-Fe2O3-HAP-Pd, and the catalyst can be used for catalytically hydrogenating benzaldehyde in a water phase at normal temperature and normal pressure to obtain benzyl alcohol with 100% conversion rate and 99.3% yield. The preparation method of the catalyst comprises the following steps: firstly, Hydroxyapatite (HAP) is utilized to wrap gamma-Fe2O3Obtaining the Gamma-Fe with the core-shell structure2O3HAP, then reacting it with Na2PdCl4Carrying out Pd2+And Ca2+Ion exchange, and finally reduction by sodium borohydride to obtain the catalyst gamma-Fe2O3-HAP-Pd。
In the prior art for synthesizing benzyl alcohol by catalytic hydrogenation of benzaldehyde, the common defects or defects are as follows:
(1) the catalyst has high preparation difficulty, high preparation cost, no environmental friendliness and high industrialization difficulty; (2) the technology for obtaining the benzyl alcohol with high yield adopts noble metals as catalysts, and the catalysis cost is high.
Disclosure of Invention
In order to solve the problems of complex preparation, environmental friendliness and high catalytic cost of the catalyst used for preparing the benzyl alcohol by catalytic hydrogenation of benzaldehyde at present, the invention provides the method for preparing the benzyl alcohol by catalytic hydrogenation of benzaldehyde, Raney nickel and inorganic salt are compounded as the catalyst, the catalytic reaction condition is mild, the cost is low, no pollution is caused, the method is green and environment-friendly, and the product yield is high.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde, wherein in the presence of a catalyst, benzaldehyde reacts with hydrogen in an organic solvent to obtain benzyl alcohol;
wherein the catalyst is a mixture of Raney nickel and inorganic salt, and the weight ratio of the benzaldehyde to the Raney nickel is 1: (0.05-0.3), wherein the weight ratio of the benzaldehyde to the inorganic salt is 1: (0.005-0.05).
Wherein the inorganic salt is one or a mixture of more of magnesium sulfate, sodium sulfate, copper sulfate, sodium bisulfate, sodium acetate, ammonium acetate, zinc acetate, stannic chloride, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, sodium tungstate, ammonium tungstate, sodium silicate, sodium sulfite, sodium bisulfite, zinc chloride and magnesium chloride.
Wherein the particle size of the Raney nickel is more than 50 meshes.
Wherein the weight ratio of the benzaldehyde to the organic solvent is 1: (0.5-3).
Wherein the organic solvent is one or a mixture of more of methanol, ethanol, isopropanol, propanol, toluene, octane, cyclohexane and ethylene glycol monobutyl ether.
Wherein, the reaction temperature is 40-130 ℃, the hydrogen pressure is 0.5-2MPa, and the reaction time is 3-6h in the catalytic reaction process.
Wherein, the method also comprises: before the catalytic reaction, air in the reaction system is replaced by inert gas.
Wherein the catalytic reaction is carried out under stirring conditions, and the stirring speed is 600-1000 rpm.
Wherein, the method also comprises: and filtering the mixed solution obtained after the catalytic reaction to obtain the catalyst, wherein the recovered catalyst can be recycled.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts cheap Raney nickel and inorganic salt as a catalyst to catalyze benzaldehyde to carry out hydrogenation reaction in an organic solvent to synthesize the benzyl alcohol, and has the advantages of mild reaction conditions, low cost, no pollution, 98.2-100% of benzaldehyde conversion rate and 98.4-99.5% of benzyl alcohol selectivity.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde, which comprises the following specific steps:
s1, adding benzaldehyde, an organic solvent and a catalyst into the reaction kettle, and sealing the reaction kettle;
wherein the catalyst is a mixture of Raney nickel (with particle size of more than 50 meshes) and inorganic salt;
the inorganic salt is one or more of magnesium sulfate, sodium sulfate, copper sulfate, sodium bisulfate, sodium acetate, ammonium acetate, zinc acetate, stannic chloride, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, sodium tungstate, ammonium tungstate, sodium silicate, sodium sulfite, sodium bisulfite, zinc chloride and magnesium chloride;
the organic solvent is one or a mixture of more of methanol, ethanol, isopropanol, propanol, toluene, octane, cyclohexane and ethylene glycol monobutyl ether;
the weight ratio of benzaldehyde to raney nickel is 1: (0.05-0.3), wherein the weight ratio of the benzaldehyde to the inorganic salt is 1: (0.005-0.05), wherein the weight ratio of the benzaldehyde to the organic solvent is 1: (0.5-3);
s2, replacing air in the reaction kettle with nitrogen, and then introducing hydrogen;
s3, starting the reaction kettle to stir and heat at the stirring speed of 600-1000rpm, heating to 40-130 ℃, then carrying out heat preservation reaction, controlling the hydrogen pressure in the reaction kettle to be 0.5-2MPa in the reaction process, reacting for 3-6h, sampling after the reaction is finished, detecting the composition and the content of each component by using a gas chromatography, and calculating the conversion rate of benzaldehyde and the selectivity of benzyl alcohol.
Wherein, the calculation formula of the benzaldehyde conversion rate is as follows:
the% conversion of benzaldehyde is (mass of benzaldehyde in the feed-mass of unreacted benzaldehyde in the product)/mass of benzaldehyde in the feed x 100%.
The equation for the selectivity of benzyl alcohol is:
the% selectivity to benzyl alcohol is defined as the mass of benzyl alcohol produced per total mass of products produced by the reaction x 100%.
And filtering the mixed solution obtained after the catalytic reaction to obtain the catalyst, wherein the recovered catalyst can be recycled.
Example 1
The method for preparing the benzyl alcohol by catalytic hydrogenation of benzaldehyde comprises the following specific steps:
s1, adding 150g of benzaldehyde, 450g of ethanol, 10g of Raney nickel and 0.75g of sodium sulfite into the reaction kettle, and sealing the reaction kettle;
s2, completely replacing air in the reaction kettle by using nitrogen (conventional inert gas replacement is adopted, and no special process requirement exists), then introducing hydrogen into the reaction kettle, and adjusting the pressure of the hydrogen to 0.5 MPa;
s3, starting the reaction kettle to stir and heat at the stirring speed of 600rpm to 65 ℃, then carrying out heat preservation reaction, controlling the hydrogen pressure in the reaction kettle to be 0.5MPa in the reaction process, reacting for 5 hours, sampling after the reaction is finished, detecting the composition and the content of each component by using gas chromatography, and calculating the conversion rate of benzaldehyde and the selectivity of benzyl alcohol.
Finally, the conversion rate of benzaldehyde in the embodiment is calculated to be 98.2%, and the selectivity of benzyl alcohol is calculated to be 99.5%.
Example 2
The method for preparing the benzyl alcohol by catalytic hydrogenation of benzaldehyde comprises the following specific steps:
s1, adding 150g of benzaldehyde, 75g of propanol, 20g of Raney nickel and 2g of magnesium sulfate into the reaction kettle, and sealing the reaction kettle;
s2, completely replacing air in the reaction kettle with nitrogen, introducing hydrogen into the reaction kettle, and adjusting the pressure of the hydrogen to 1.5 MPa;
s3, starting the reaction kettle to stir and heat at the stirring speed of 700rpm to 40 ℃, then carrying out heat preservation reaction, controlling the hydrogen pressure in the reaction kettle to be in a 1.5MPa state in the reaction process, reacting for 3 hours, sampling after the reaction is finished, detecting the composition and the content of each component by using a gas chromatography, and calculating the conversion rate of benzaldehyde and the selectivity of benzyl alcohol.
Finally, the conversion rate of benzaldehyde in the embodiment is 100% and the selectivity of benzyl alcohol is 99.1% through calculation.
Example 3
The method for preparing the benzyl alcohol by catalytic hydrogenation of benzaldehyde comprises the following specific steps:
s1, adding 150g of benzaldehyde, 200g of methanol, 40g of raney nickel and 7.5g of sodium acetate into the reaction kettle, and sealing the reaction kettle;
s2, completely replacing air in the reaction kettle with nitrogen, introducing hydrogen into the reaction kettle, and adjusting the pressure of the hydrogen to 2 MPa;
s3, starting the reaction kettle to stir and heat at the stirring speed of 800rpm to 130 ℃, then carrying out heat preservation reaction, controlling the hydrogen pressure in the reaction kettle to be 2MPa in the reaction process, reacting for 6 hours, sampling after the reaction is finished, detecting the composition and the content of each component by using gas chromatography, and calculating the conversion rate of benzaldehyde and the selectivity of benzyl alcohol.
Finally, the conversion rate of benzaldehyde in the embodiment is 100% and the selectivity of benzyl alcohol is 98.4% through calculation.
Example 4
The method for preparing the benzyl alcohol by catalytic hydrogenation of benzaldehyde comprises the following specific steps:
s1, adding 150g of benzaldehyde, 300g of octane, 30g of Raney nickel and 3.75g of sodium sulfite into the reaction kettle, and sealing the reaction kettle;
s2, completely replacing air in the reaction kettle with nitrogen, introducing hydrogen into the reaction kettle, and adjusting the pressure of the hydrogen to 1 MPa;
s3, starting the reaction kettle to stir and heat at the stirring speed of 1000rpm to 90 ℃, then carrying out heat preservation reaction, controlling the hydrogen pressure in the reaction kettle to be in a 1MPa state in the reaction process, reacting for 5 hours, sampling after the reaction is finished, detecting the composition and the content of each component by using gas chromatography, and calculating the conversion rate of benzaldehyde and the selectivity of benzyl alcohol.
Finally, the conversion rate of benzaldehyde in the embodiment is 100% and the selectivity of benzyl alcohol is 98.5% through calculation.
Example 5
The method for preparing the benzyl alcohol by catalytic hydrogenation of benzaldehyde comprises the following specific steps:
s1, adding 150g of benzaldehyde, 75g of propanol, 1g of raney nickel and sodium sulfite into the reaction kettle, and sealing the reaction kettle;
wherein, the raney nickel added in step S1 is raney nickel which can be recycled and 5g of raney nickel additionally added by filtering the mixed solution obtained after the catalytic reaction in example 2;
s2, completely replacing air in the reaction kettle with nitrogen, introducing hydrogen into the reaction kettle, and adjusting the pressure of the hydrogen to 1.5 MPa;
s3, starting the reaction kettle to stir and heat at the stirring speed of 600rpm to 50 ℃, then carrying out heat preservation reaction, controlling the hydrogen pressure in the reaction kettle to be 1.5MPa in the reaction process, reacting for 5 hours, sampling after the reaction is finished, detecting the composition and the content of each component by using gas chromatography, and calculating the conversion rate of benzaldehyde and the selectivity of benzyl alcohol.
Finally, the conversion rate of benzaldehyde in the embodiment is 100% and the selectivity of benzyl alcohol is 99.3%.
Example 6
The method for preparing the benzyl alcohol by catalytic hydrogenation of benzaldehyde comprises the following specific steps:
s1, adding 150g of benzaldehyde, 100 g of ethanol, 2g of raney nickel and sodium sulfite into the reaction kettle, and sealing the reaction kettle;
the raney nickel added in step S1 is raney nickel which can be recycled and 10g of raney nickel additionally added by filtering the mixed solution after the catalytic reaction in example 5;
s2, completely replacing air in the reaction kettle with nitrogen, introducing hydrogen into the reaction kettle, and adjusting the pressure of the hydrogen to 2 MPa;
s3, starting the reaction kettle to stir and heat at the stirring speed of 800rpm to 70 ℃, then carrying out heat preservation reaction, controlling the hydrogen pressure in the reaction kettle to be 2MPa in the reaction process, reacting for 5 hours, sampling after the reaction is finished, detecting the composition and the content of each component by using gas chromatography, and calculating the conversion rate of benzaldehyde and the selectivity of benzyl alcohol.
Finally, the conversion rate of benzaldehyde in the embodiment is 100% and the selectivity of benzyl alcohol is 98.5% through calculation.
Comparative example 1
The method for preparing the benzyl alcohol by catalytic hydrogenation of benzaldehyde comprises the following specific steps:
s1, adding 150g of benzaldehyde, 450g of ethanol and 10g of Raney nickel into the reaction kettle, and sealing the reaction kettle;
s2, completely replacing air in the reaction kettle with nitrogen, introducing hydrogen into the reaction kettle, and adjusting the pressure of the hydrogen to 0.5 MPa;
s3, starting the reaction kettle to stir and heat at the stirring speed of 800rpm to 65 ℃, then carrying out heat preservation reaction, controlling the hydrogen pressure in the reaction kettle to be 0.5MPa in the reaction process, reacting for 5 hours, sampling after the reaction is finished, detecting the composition and the content of each component by using gas chromatography, and calculating the conversion rate of benzaldehyde and the selectivity of benzyl alcohol.
Finally, the conversion rate of benzaldehyde in the embodiment is 80.4% and the selectivity of benzyl alcohol is 78% through calculation.
Comparing the results of the test of the conversion rate of benzaldehyde and the selectivity of benzyl alcohol in comparative example 1 and examples 1 to 6, it can be seen that when raney nickel is used together with inorganic salt as a catalyst, the conversion rate of benzaldehyde and the selectivity of benzyl alcohol can be significantly improved.
In conclusion, the invention adopts cheap Raney nickel and inorganic salt as the catalyst to catalyze benzaldehyde to carry out hydrogenation reaction in an organic solvent to synthesize the benzyl alcohol, and has the advantages of mild reaction conditions, low cost, no pollution, 98.2-100% of benzaldehyde conversion rate and 98.4-99.5% of benzyl alcohol selectivity.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (9)
1. A method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde is characterized in that benzaldehyde reacts with hydrogen in an organic solvent in the presence of a catalyst to obtain benzyl alcohol;
wherein the catalyst is a mixture of Raney nickel and inorganic salt, and the weight ratio of the benzaldehyde to the Raney nickel is 1: (0.05-0.3), wherein the weight ratio of the benzaldehyde to the inorganic salt is 1: (0.005-0.05).
2. The method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde according to claim 1, wherein the inorganic salt is one or more of magnesium sulfate, sodium sulfate, copper sulfate, sodium bisulfate, sodium acetate, ammonium acetate, zinc acetate, tin dichloride, tin tetrachloride, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, sodium tungstate, ammonium tungstate, sodium silicate, sodium sulfite, sodium bisulfite, zinc chloride, and magnesium chloride.
3. The method of claim 1, wherein the Raney nickel has a particle size of 50 mesh or more.
4. The method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde according to claim 1, wherein the weight ratio of benzaldehyde to organic solvent is 1: (0.5-3).
5. The method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde according to claim 1 or 4, wherein the organic solvent is one or a mixture of methanol, ethanol, isopropanol, propanol, toluene, octane, cyclohexane and ethylene glycol monobutyl ether.
6. The method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde according to claim 1, wherein the reaction temperature is 40-130 ℃, the hydrogen pressure is 0.5-2MPa, and the reaction time is 3-6 h.
7. The method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde according to claim 1, further comprising: before the catalytic reaction, air in the reaction system is replaced by inert gas.
8. The method of claim 1, wherein the catalytic reaction is carried out under stirring at a speed of 600-1000 rpm.
9. The method for preparing benzyl alcohol by catalytic hydrogenation of benzaldehyde according to claim 1, further comprising: and filtering the mixed solution obtained after the catalytic reaction to obtain the catalyst, wherein the recovered catalyst can be recycled.
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| 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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