CN114956955A - Synthesis method of beta-phenethyl alcohol - Google Patents
Synthesis method of beta-phenethyl alcohol Download PDFInfo
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- CN114956955A CN114956955A CN202110212128.4A CN202110212128A CN114956955A CN 114956955 A CN114956955 A CN 114956955A CN 202110212128 A CN202110212128 A CN 202110212128A CN 114956955 A CN114956955 A CN 114956955A
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- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims abstract description 57
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000002360 preparation method Methods 0.000 claims abstract description 41
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000001103 potassium chloride Substances 0.000 claims abstract description 10
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 52
- 229910020830 Sn-Bi Inorganic materials 0.000 claims description 43
- 229910018728 Sn—Bi Inorganic materials 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000012074 organic phase Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 9
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 9
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 9
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical group Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 150000001621 bismuth Chemical class 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- 239000005909 Kieselgur Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 238000011068 loading method Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- PEZDGNIESNXEDE-UHFFFAOYSA-N benzene;oxirane Chemical compound C1CO1.C1=CC=CC=C1 PEZDGNIESNXEDE-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000003889 eye drop Substances 0.000 description 1
- 229940012356 eye drops Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000003313 weakening effect Effects 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The application relates to the field of preparation of beta-phenethyl alcohol, and particularly discloses a synthesis method of beta-phenethyl alcohol. The synthesis method comprises the following steps: stirring and reacting a quaternary ammonium salt phase transfer catalyst, a metal oxide, potassium chloride, styrene and a hydrogen peroxide solution for 3-5 hours, extracting, then carrying out reduced pressure distillation, and collecting required fractions to obtain pure styrene oxide; and then adding alcohol, a ternary metal supported catalyst and the styrene oxide into a reactor, introducing hydrogen into the reactor, reacting at the reaction temperature of 40-60 ℃ for 3-5 h at the stirring speed of 600-800 r/min, reducing the temperature of the reactor to room temperature, releasing pressure to obtain a reacted mixture, filtering, distilling under reduced pressure, and collecting required fractions to obtain the target product beta-phenethyl alcohol. According to the method, the novel ternary metal supported catalyst is prepared, hydrogen is catalyzed to reduce styrene oxide, beta-phenethyl alcohol with high yield is obtained, and the reaction process is safe and efficient.
Description
Technical Field
The application relates to the field of preparation of beta-phenethyl alcohol, in particular to a synthetic method of beta-phenethyl alcohol.
Background
Beta-phenylethyl alcohol is colorless viscous liquid, the boiling point is 219 ℃, and the beta-phenylethyl alcohol is widely used in spices and tobacco essence due to fresh and sweet and lasting rose fragrance, is an additive for preparing rose fragrance type food, is also widely used in cosmetic water and perfumed soap, and can also be used in eye drops aqueous solution due to good antibacterial property of the beta-phenylethyl alcohol.
At present, the preparation method of beta-phenethyl alcohol mainly adopts a benzene-ethylene oxide method, namely, mixed solution of benzene and ethylene oxide reacts under the action of a catalyst (generally Lewis acid such as anhydrous aluminum trichloride and the like), after the reaction is finished, the mixed product is hydrolyzed, an organic phase is separated out, benzene is evaporated under normal pressure, and then the product is obtained after reduced pressure distillation. The reaction mechanism of the synthetic route for preparing the phenethyl alcohol is Friedel-Crafts reaction, and the method has low investment and low equipment requirement.
The related technologies have the disadvantages that when the benzene-ethylene oxide method is adopted to prepare the beta-phenethyl alcohol, the preparation yield is generally 40-60%, side reactions are more, products are not easy to separate, and the fragrance of the beta-phenethyl alcohol is influenced.
Disclosure of Invention
In order to improve the yield of the beta-phenethyl alcohol, the application provides a synthetic method of the beta-phenethyl alcohol.
The synthesis method of beta-phenethyl alcohol provided by the application adopts the following technical scheme:
a method for synthesizing beta-phenethyl alcohol comprises the following steps:
(1) preparation of styrene oxide:
1) taking 3-6 parts by weight of quaternary ammonium salt phase transfer catalyst, 1.2-1.8 parts by weight of metal oxide, 3-7 parts by weight of potassium chloride, 20-25 parts by weight of styrene and 52-60 parts by weight of hydrogen peroxide solution, and reacting for 3-5 hours at a stirring speed of 800-1000 r/min and a reaction temperature of 50-75 ℃ to obtain a crude product of styrene oxide;
2) after the reaction is finished, cooling the reaction solution, extracting the crude product of the styrene oxide in the step (1) by using 50-80 parts by weight of toluene for three times, and combining organic phases;
3) carrying out reduced pressure distillation on the organic phase in the step 2) under the condition of 0.3-0.52 kPa, and collecting fractions at 45-50 ℃ to obtain pure styrene oxide;
(2) preparing beta-phenethyl alcohol:
adding the pure styrene oxide prepared in the step 3) into a reactor, adding an alcohol and a ternary metal supported catalyst, filling 3-5MPa hydrogen into the reactor, reacting at the reaction temperature of 40-60 ℃ for 3-5 h at the stirring speed of 600-800 r/min, reducing the pressure of the reactor to room temperature to obtain a reacted mixture, filtering, distilling under reduced pressure, and collecting required fractions, wherein the weight ratio of the styrene oxide to the alcohol to the hydrogen to the ternary metal supported catalyst is 1: (1.4-1.6), (7-12) and (0.013-0.015).
By adopting the technical scheme, the hydrogen peroxide oxidizes the styrene into the styrene oxide under the common catalysis of the metal oxide and the quaternary ammonium salt phase transfer catalyst, in the process, firstly, carbon atoms in styrene are combined with oxygen atoms in hydrogen peroxide to form a three-membered ring transition state, then the O-O bond of the hydrogen peroxide is broken, a water molecule is removed, an O atom is exposed, the naked O atom is bonded with carbon atoms in the carbon-carbon double bond of styrene to form styrene oxide, the styrene is an organic phase, hydrogen peroxide, metal oxides and potassium chloride are inorganic phases, so that the substances are not easy to be fully contacted, the quaternary ammonium salt phase transfer catalyst in the system can lead the reactant and the catalyst to be in the same phase through a phase interface, thus leading the catalyst and the reactant to be fully contacted and leading the reaction to be more complete; in the reaction process, the product after the hydrogen peroxide reaction is water, which is beneficial to environmental cleaning.
The active epoxy group in the styrene oxide can generate functional group conversion through ring-opening reaction, so that the styrene oxide and hydrogen can generate reduction reaction by reasonably regulating and controlling reaction conditions to generate high-yield beta-phenethyl alcohol, and the catalytic reduction process of the styrene oxide firstly diffuses the hydrogen and adsorbs the hydrogen to micropores and the surface of a ternary metal supported catalyst; and then the ethylene oxide is fully contacted with the ternary metal loaded catalyst and effectively collides with hydrogen on the surface of the ternary metal loaded catalyst to generate a reduction reaction to generate beta-phenethyl alcohol, once the beta-phenethyl alcohol is formed, the beta-phenethyl alcohol falls off from the surface of the ternary metal loaded catalyst to form a free surface, the hydrogen in micropores of the ternary metal loaded catalyst escapes to the surface of the ternary metal loaded catalyst, and the catalytic cycle is repeatedly carried out. The hydrogen is loaded in the micropores of the ternary metal loaded catalyst as a reducing agent, so that the styrene oxide can be fully contacted with the hydrogen, and further the beta-phenethyl alcohol can be effectively hydrogenated to generate.
Optionally, the quaternary ammonium salt phase transfer catalyst in step 1) is any one of dodecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride.
By adopting the technical scheme, the quaternary ammonium salt is used as a phase transfer catalyst, has hydrophilicity and lipophilicity, the phase transfer characteristics of the quaternary ammonium salt are related to the length of a carbon chain and the carbon content of the long carbon chain, the length of the carbon chain in the dodecyl trimethyl ammonium chloride or the tetradecyl trimethyl ammonium chloride is moderate, the carbon chain is not easy to wrap the active part of the catalyst, namely the active part has small steric hindrance, and the quaternary ammonium salt is favorable for contacting with hydrogen peroxide and styrene, so that the styrene and the hydrogen peroxide are fully reacted to generate high-yield styrene oxide; in addition, dodecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride is used as a polar substance, so that a metal oxide catalyst with polarity is easily adsorbed, and the catalyst can better play a catalytic role.
Optionally, the concentration of the hydrogen peroxide solution in the step 1) is 10-12 mol/L.
By adopting the technical scheme, when the concentration of the hydrogen peroxide solution is 10-12 mol/L, water molecules in the hydrogen peroxide solution can participate in proton transfer between molecules in a reaction, and after the hydrogen peroxide solution and styrene form a seven-membered ring transition state under the combined action of hydrogen peroxide, the seven-membered ring transition state is more stable than a three-membered ring transition state, namely, the activation energy of the reaction can be reduced by adding the water molecules, the epoxidation reaction of the styrene is promoted to be more easily carried out, and if the concentration of the hydrogen peroxide solution is lower, the water content in a reaction system is higher, so that the generated epoxyphenylethane is easily hydrolyzed; if the concentration of the hydrogen peroxide solution is high, the water content in the reaction system is low, which is not favorable for sufficient water molecules to participate in the reaction.
Optionally, in the step 1), when the reaction starts, a hydrogen peroxide solution is dropwise added, and the dropwise addition of the hydrogen peroxide solution is completed within 2-3 hours.
By adopting the technical scheme, the hydrogen peroxide is added dropwise, so that the hydrogen peroxide is favorably and fully contacted with the catalytic catalyst and the styrene, and the hydrogen peroxide is further favorably oxidized by the styrene to generate the high-yield styrene oxide.
Optionally, the metal oxide in the step 1) adopts V 2 O 5 NiO or TiO 2 At least one of (a).
By adopting the technical scheme, V 2 O 5 NiO and TiO 2 The metal ions in the catalyst have more empty orbitals, which is helpful for containing electrons of oxygen atoms in hydrogen peroxide, and further is helpful for weakening the bond energy of O-H bonds in the hydrogen peroxide, so that O in the O-H bonds is easier to heterocrack, and the subsequent formation of styrene oxide by bonding exposed O and C atoms in styrene is facilitated.
Optionally, the ternary metal supported catalyst in step (2) is a Co-Sn-Bi diatomite supported catalyst, and the preparation method of the Co-Sn-Bi diatomite supported catalyst comprises the following steps:
a, dissolving 3-5 parts by weight of cobalt salt, 4-5 parts by weight of tin salt and 1-2.3 parts by weight of bismuth salt in 10-15 parts by weight of water to obtain a mixed solution, then dropwise adding ammonium carbonate at a stirring speed of 200-300 r/min until the pH value is 8-10, reacting for 30-60 min, filtering, and drying a filter cake at 120 ℃ to obtain a precursor;
and B, adding 12-15 parts of diatomite into the precursor in the step A, mixing and grinding for 10-15 min, and then sequentially aging, drying and roasting to obtain the Co-Sn-Bi diatomite supported catalyst.
By adopting the technical scheme, the precipitation method for preparing the catalyst has the advantage of simple operation, and the catalyst after aging, drying and roasting has larger crystal grains and higher catalytic activity; compared with the traditional reduction catalysts such as Pd-C, Ni-Al, Ni-Cu and the like, the Co-Sn-Bi kieselguhr load catalyst does not contain noble metals, has low cost and mild process conditions, and is easy to realize industrialization; secondly, the physical property and the chemical property of the catalyst can be further optimized through the interaction of Co-Sn-Bi, and the recycling performance of the catalyst is enhanced; in addition, the diatomite existing in large amount in the nature is used as a catalyst carrier, so that the cost is lower, the diatomite is low in density and porous, and the specific surface area and the pore volume are both larger, and the good load performance is reflected; the main component of the diatomite, namely the silicon dioxide, can play a stabilizing role in active components in Co-Sn-Bi, so that the Co-Sn-Bi catalyst is not easy to inactivate, the reduction of hydrogen to styrene oxide is promoted, and the catalytic cycle number of the Co-Sn-Bi diatomite supported catalyst can be further improved.
Optionally, the cobalt salt in the step a is cobalt chloride, the tin salt is tin chloride, and the bismuth salt is bismuth chloride.
By adopting the technical scheme, the chlorinated metal salt can meet the metal loading capacity in the catalyst, so that the Co-Sn-Bi kieselguhr loaded catalyst can better exert the catalytic performance, and the chlorinated metal salt has lower cost.
Optionally, the aging temperature in the step B is room temperature, and the aging time is 2-3 h; the drying temperature is 110-120 ℃, the drying time is 1-2 hours, the roasting temperature is 500-700 ℃, and the roasting time is 3-5 hours.
By adopting the technical scheme, the treated catalyst has more active sites and better catalytic performance due to proper post-treatment process parameters, and is beneficial to loading hydrogen, and further beneficial to the reduction reaction of the hydrogen and the styrene oxide.
Optionally, the alcohol in the step (2) is any one of methanol, ethanol or isopropanol.
By adopting the technical scheme, the dissolubility of the methanol, the ethanol or the isopropanol is good, the styrene oxide can be fully dissolved, and in addition, the methanol, the ethanol or the isopropanol are all low-polarity solvents, so that the reaction rate can be accelerated; the boiling point of the methanol, the ethanol or the isopropanol is low and has a large difference with the boiling point of the beta-phenethyl alcohol, so that the beta-phenethyl alcohol can be purified by adopting a distillation method, the purity of the beta-phenethyl alcohol is improved, and the purification process is simple and convenient.
Optionally, the reduced pressure distillation in the step (2) is to collect the fraction at the temperature of 50-55 ℃ under the pressure of 0.18-0.22 kPa.
By adopting the technical scheme, the product beta-phenethyl alcohol can be obtained by reduced pressure distillation, and the product separation process is simple and convenient.
In summary, the present application has the following beneficial effects:
1. the hydrogen and the styrene oxide are subjected to reduction reaction under the catalysis of a three-way metal catalyst, and the reaction condition is regulated and controlled to generate the high-yield beta-phenethyl alcohol by utilizing the characteristic that an active epoxy group in the styrene oxide is easy to open a ring.
2. By adopting the Co-Sn-Bi ternary metal load catalyst, precious metal is not contained, the cost is low, the process condition is mild, and the industrialization is easy to realize;
3. by loading the Co-Sn-Bi ternary metal on the kieselguhr, the catalyst embodies good loading performance, is not easy to inactivate, and can improve the catalytic cycle number of the Co-Sn-Bi kieselguhr loaded catalyst.
Detailed Description
The present application will be described in further detail with reference to examples.
Sources of raw materials used in the following embodiments:
styrene: xiong chemical corporation;
ammonium carbonate, methanol, ethanol, isopropanol, potassium chloride, hydrogen: shanghai Lingfeng Chemicals, Inc.;
cobalt chloride, tin chloride, bismuth chloride, hydrogen peroxide solution, V 2 O 5 、NiO、TiO 2 : chemical agents of the national drug group, ltd;
dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride: craine chemical Co., Ltd;
diatomite: lingshou county remittance mineral products ltd;
preparation example (preparation of Co-Sn-Bi diatomaceous earth supported catalyst)
Preparation example 1
A, dissolving 3kg of cobalt chloride, 5kg of tin chloride and 1kg of bismuth chloride in 15kg of water to obtain a mixed solution, dropwise adding ammonium carbonate at a stirring speed of 200r/min until the pH value is 10, reacting for 30min, filtering, and drying a filter cake at 120 ℃ to obtain a precursor;
and B, adding 15kg of kieselguhr into the precursor obtained in the step A, mixing and grinding for 15min, aging for 2h at room temperature, drying for 2h at the temperature of 120 ℃, and roasting for 5h at the temperature of 500 ℃ to obtain the Co-Sn-Bi kieselguhr supported catalyst.
Preparation example 2
Dissolving 5kg of cobalt chloride, 4kg of tin chloride and 2.3kg of bismuth chloride in 10kg of water to obtain a mixed solution, then dropwise adding ammonium carbonate at a stirring speed of 300r/min until the pH value is 8, reacting for 60min, filtering, and drying a filter cake at the temperature of 120 ℃ to obtain a precursor;
and B, adding 12kg of kieselguhr into the precursor in the step A, mixing and grinding for 15min, aging for 2h at room temperature, drying for 1h at the temperature of 120 ℃, and roasting for 3h at the temperature of 700 ℃ to obtain the Co-Sn-Bi kieselguhr supported catalyst.
Preparation example 3
Dissolving 4kg of cobalt chloride, 4.5kg of tin chloride and 2kg of bismuth chloride in 14kg of water to obtain a mixed solution, then dropwise adding ammonium carbonate at a stirring speed of 260r/min until the pH value is 9.5, reacting for 55min, filtering, and drying a filter cake at the temperature of 120 ℃ to obtain a precursor;
and B, adding 13kg of kieselguhr into the precursor in the step A, mixing and grinding for 13min, aging for 2.6h at room temperature, drying for 1.5h at the temperature of 115 ℃, and roasting for 4h at the temperature of 620 ℃ to obtain the Co-Sn-Bi kieselguhr supported catalyst.
Preparation example 4
Dissolving 4kg of cobalt chloride, 4kg of tin chloride and 2kg of bismuth chloride in 15kg of water to obtain a mixed solution, then dropwise adding ammonium carbonate at a stirring speed of 300r/min until the pH value is 9, reacting for 55min, filtering, and drying a filter cake at the temperature of 120 ℃ to obtain a precursor;
and B, adding 13kg of kieselguhr into the precursor in the step A, mixing and grinding for 15min, aging for 4h at room temperature, drying for 3h at the temperature of 150 ℃, and roasting for 5h at the temperature of 500 ℃ to obtain the Co-Sn-Bi kieselguhr supported catalyst.
Preparation example 5
A, dissolving 4kg of cobalt chloride and 4.5kg of stannic chloride in 14kg of water to obtain a mixed solution, then dropwise adding ammonium carbonate at a stirring speed of 260r/min until the pH value is 9.5, reacting for 55min, filtering, and drying a filter cake at 120 ℃ to obtain a precursor;
and B, adding 13kg of kieselguhr into the precursor in the step A, mixing and grinding for 13min, aging for 2.6h at room temperature, drying for 1.5h at the temperature of 115 ℃, and roasting for 4h at the temperature of 620 ℃ to obtain the Co-Sn-Bi kieselguhr supported catalyst.
Preparation example 6
Dissolving 4kg of cobalt chloride, 4.5kg of tin chloride and 2kg of bismuth chloride in 14kg of water to obtain a mixed solution, then dropwise adding ammonium carbonate at a stirring speed of 260r/min until the pH value is 9.5, reacting for 55min, filtering, and drying a filter cake at the temperature of 120 ℃ to obtain a precursor;
and B, mixing and grinding the precursor in the step A for 13min, aging at room temperature for 2.6h, drying at 115 ℃ for 1.5h, and roasting at 620 ℃ for 4h to obtain the Co-Sn-Bi kieselguhr supported catalyst.
Examples
Example 1
The following preparation method according to the present application was used to produce beta-phenylethyl alcohol:
(1) preparation of styrene oxide:
1) taking 3kg of dodecyl trimethyl ammonium chloride and 1.8kgV 2 O 5 3kg of potassium chloride and 25kg of styrene are put into a reactor, when the reaction starts, 52kg of hydrogen peroxide solution with the concentration of 12mol/L is dripped into the reactor at the stirring speed of 1000r/min, the hydrogen peroxide solution is dripped within 2 hours, and the mixed solution reacts for 3 hours at the reaction temperature of 50 ℃ to obtain a crude product of the styrene oxide;
2) after the reaction is finished, cooling the reaction solution, extracting the crude product of the styrene oxide in the step 1) by using 80kg of toluene for three times, and combining organic phases;
3) distilling the organic phase obtained in the step 2) under reduced pressure under the condition of 0.3kPa, and collecting fractions at 45-50 ℃ to obtain pure styrene oxide;
(2) preparing beta-phenethyl alcohol:
adding the pure styrene oxide prepared in the step 3) into a reactor, adding 40kg of methanol and 0.375kg of Co-Sn-Bi diatomite-loaded catalyst in the preparation example 1, filling 5MPa hydrogen (12 kg of hydrogen at this time) into the reactor, reacting for 5 hours at the reaction temperature of 40 ℃ at the stirring speed of 800r/min, reducing the pressure of the reactor after the reactor is cooled to room temperature to obtain a mixture after the reaction, filtering, distilling under reduced pressure of 0.18kPa, and collecting fractions at 50-55 ℃ to obtain beta-phenylethyl alcohol.
Example 2
Beta-phenylethyl alcohol was produced using the following preparation method according to the present application:
(1) preparation of styrene oxide:
1) taking 6kg of tetradecyltrimethyl ammonium chloride and 1kgV 2 O 5 0.2kgNiO, 7kg potassium chloride and 20kg styrene are put into a reactor, 60kg hydrogen peroxide solution with the concentration of 11mol/L is dripped into the reactor at the stirring speed of 800r/min when the reaction starts, the hydrogen peroxide solution is dripped in 2h, and the mixed solution reacts for 5h at the reaction temperature of 75 ℃ to obtain a crude product of the styrene oxide;
2) after the reaction is finished, cooling the reaction solution, extracting the crude product of the styrene oxide in the step 1) by using 50kg of toluene for three times, and combining organic phases;
3) carrying out reduced pressure distillation on the organic phase in the step 2) under the condition of 0.52kPa, and collecting fractions at 45-50 ℃ to obtain pure styrene oxide;
(2) preparing beta-phenethyl alcohol:
adding the pure styrene oxide prepared in the step 3) into a reactor, adding 28kg of ethanol and 0.26kg of Co-Sn-Bi diatomite supported catalyst in the preparation example 2, filling 3MPa hydrogen (7 kg of hydrogen at this time) into the reactor, reacting for 3h at the reaction temperature of 60 ℃ at the stirring speed of 800r/min, reducing the pressure of the reactor after the reactor is cooled to room temperature to obtain a mixture after reaction, filtering, distilling under reduced pressure of 0.22kPa, and collecting fractions at 50-55 ℃ to obtain beta-phenylethyl alcohol.
Example 3
Beta-phenylethyl alcohol was produced using the following preparation method according to the present application:
(1) preparation of styrene oxide:
1) 4kg of dodecyl trimethyl ammonium chloride and 0.9kgV kg of the mixture are taken 2 O 5 、0.4kgNiO、0.3kgTiO 2 5kg of potassium chloride and 23kg of styrene are put into a reactor, when the reaction starts, 55kg of hydrogen peroxide solution with the concentration of 10mol/L is dripped into the reactor at the stirring speed of 900r/min, the hydrogen peroxide solution is dripped within 3 hours, and the mixed solution reacts for 4.5 hours at the reaction temperature of 66 ℃ to obtain a crude product of the styrene oxide;
2) after the reaction is finished, cooling the reaction solution, extracting the crude product of the styrene oxide in the step 1) by using 70kg of toluene for three times, and combining organic phases;
3) carrying out reduced pressure distillation on the organic phase in the step 2) under the condition of 0.4kPa, and collecting fractions at 45-50 ℃ to obtain pure styrene oxide;
(2) preparing beta-phenethyl alcohol:
adding the pure styrene oxide prepared in the step 3) into a reactor, then adding 34.5kg of isopropanol and 0.322kg of Co-Sn-Bi diatomite-loaded catalyst in the preparation example 3, filling 4MPa hydrogen (9.72 kg of hydrogen at the moment) into the reactor, reacting for 4 hours at the reaction temperature of 58 ℃ at the stirring speed of 720r/min, cooling the reactor to room temperature, releasing pressure to obtain a mixture after reaction, and then filtering; carrying out reduced pressure distillation under the pressure of 0.2kPa, and collecting fractions at the temperature of 50-55 ℃ to obtain the beta-phenethyl alcohol.
Example 4
Beta-phenylethyl alcohol was produced using the following preparation method according to the present application:
(1) preparation of styrene oxide:
1) 4kg of dodecyl trimethyl ammonium chloride and 0.9kgV kg of the mixture are taken 2 O 5 、0.4kgNiO、0.3kgTiO 2 5kg of potassium chloride and 23kg of styrene were placed in a reactor, and at the start of the reaction, 58kg of a 10mol/L hydrogen peroxide solution was added dropwise to the reactor at a stirring rate of 900r/min, the hydrogen peroxide solution being 3After the dripping is finished in h, the mixed solution reacts for 4.5h at the reaction temperature of 66 ℃ to obtain a crude product of the styrene oxide;
2) after the reaction is finished, cooling the reaction solution, extracting the crude product of the styrene oxide in the step 1) by using 70kg of toluene for three times, and combining organic phases;
3) carrying out reduced pressure distillation on the organic phase in the step 2) under the condition of 0.4kPa, and collecting fractions at 45-50 ℃ to obtain pure styrene oxide;
(2) preparing beta-phenethyl alcohol:
adding the pure styrene oxide prepared in the step 3) into a reactor, then adding 34.5kg of isopropanol and 0.322kg of Co-Sn-Bi diatomite-supported catalyst in the preparation example 2, filling 3.8MPa hydrogen (8.21 kg of hydrogen at the moment) into the reactor, reacting for 5h at the reaction temperature of 50 ℃ at the stirring speed of 700r/min, reducing the pressure of the reactor after the reactor is cooled to room temperature to obtain a mixture after the reaction, and then filtering; carrying out reduced pressure distillation under the pressure of 0.18kPa, and collecting fractions at the temperature of 50-55 ℃ to obtain the beta-phenethyl alcohol.
Example 5
Beta-phenylethyl alcohol was produced using the following preparation method according to the present application:
the difference from example 3 is that: in the step (2), as the Co-Sn-Bi diatomaceous earth supported catalyst, a Co-Sn-Bi diatomaceous earth supported catalyst which had been circulated 5 times in the same manner as in example 3 was used.
Example 6
Beta-phenylethyl alcohol was produced using the following preparation method according to the present application:
the difference from example 3 is that: in the step (2), as the Co-Sn-Bi diatomaceous earth supported catalyst, a Co-Sn-Bi diatomaceous earth supported catalyst which had been circulated 10 times in the same manner as in example 3 was used.
Example 7
Beta-phenylethyl alcohol was produced using the following preparation method according to the present application:
the difference from example 3 is that: in the step (2), as the Co-Sn-Bi diatomaceous earth supported catalyst, a Co-Sn-Bi diatomaceous earth supported catalyst which had been circulated 20 times in the same manner as in example 3 was used.
Comparative example
Comparative example 1
The following preparation method is adopted to produce the beta-phenethyl alcohol:
(1) preparation of styrene oxide:
1) 4kg of dodecyl trimethyl ammonium chloride and 0.9kgV kg of the mixture are taken 2 O 5 、0.4kgNiO、0.3kgTiO 2 5kg of potassium chloride and 23kg of styrene are put into a reactor, 26kg of hydrogen peroxide solution with the concentration of 10mol/L is dripped into the reactor at the stirring speed of 900r/min when the reaction starts, the hydrogen peroxide solution is dripped out within 3h, and the mixed solution reacts for 4.5h at the reaction temperature of 66 ℃ to obtain a crude product of the styrene oxide;
2) after the reaction is finished, cooling the reaction solution, extracting the crude product of the styrene oxide in the step 1) by using 70kg of toluene for three times, and combining organic phases;
3) distilling the organic phase obtained in the step 2) under reduced pressure under the condition of 0.4kPa, and collecting fractions at 45-50 ℃ to obtain pure styrene oxide;
(2) preparing beta-phenethyl alcohol:
adding the pure styrene oxide prepared in the step 3) into a reactor, then adding 34.5kg of isopropanol and 0.322kg of Co-Sn-Bi kieselguhr supported catalyst in the preparation example 3, filling 2.5MPa hydrogen into the reactor (the pressure of the hydrogen is 5.72 kg), reacting for 4 hours at the reaction temperature of 58 ℃ at the stirring speed of 720r/min, reducing the pressure of the reactor to room temperature to obtain a mixture after reaction, and then filtering; carrying out reduced pressure distillation under the pressure of 0.2kPa, and collecting fractions at the temperature of 50-55 ℃ to obtain the beta-phenethyl alcohol.
Comparative example 2
The following preparation method is adopted to produce the beta-phenethyl alcohol:
the difference from example 3 is that the Co-Sn-Bi diatomaceous earth supported catalyst of preparation example 4 was added in step (2).
Comparative example 3
The following preparation method is adopted to produce the beta-phenethyl alcohol:
the difference from example 3 is that the Co-Sn-Bi diatomaceous earth supported catalyst of preparation example 5 was added in step (2).
Comparative example 4
The following preparation method is adopted to produce the beta-phenethyl alcohol:
the difference from example 3 is that the Co-Sn-Bi diatomaceous earth supported catalyst of preparation example 6 was added in step (2).
Performance test
Performance test (yield of target product and conversion of raw Material)
The yields of styrene oxide and β -phenylethyl alcohol and the conversion of styrene in examples 1 to 7 and comparative examples 1 to 4 were calculated, and the calculation results are shown in table 1.
TABLE 1
As can be seen from the above examples 1-7 and comparative examples 1-4, the preparation methods within the scope of the present application all give beta-phenylethyl alcohol in good yield;
the data of the comparative example 3 and the comparative example 4 show that the Co-Sn-Bi diatomite supported catalyst still has good catalytic effect on the reaction of reducing the styrene oxide by the hydrogen after being recycled for many times, and the results prove that the Co-Sn-Bi diatomite supported catalyst can be recycled, is energy-saving and environment-friendly, and can be related to the interaction between the Co-Sn-Bi and the strong supporting performance of the diatomite, and the data of the comparative example 3-4 show that the yield of the beta-phenethyl alcohol is greatly reduced when the catalyst does not contain Bi or diatomite, and the reaction activity of the Co-Sn-Bi diatomite supported catalyst is exerted by the cooperation of various substances.
It can be seen from the data of comparative example 3 and comparative example 1 that the material ratio also has a certain influence on the reaction in the process of reducing styrene oxide by hydrogen, and the optimization of the weight part of the raw material is beneficial to obtaining high-yield beta-phenylethyl alcohol.
Comparing the data of example 3 and comparative example 2, it was found that the post-treatment process parameters of the Co-Sn-Bi diatomaceous earth supported catalyst also affected the reaction, and the catalytic ability exhibited a reduced level and the yield of beta-phenylethyl alcohol was reduced using the Co-Sn-Bi diatomaceous earth supported catalyst prepared outside the range defined in the present application, probably due to the close relationship between the aging, drying and calcination modes on the active sites and the supporting ability of the Co-Sn-Bi diatomaceous earth supported catalyst.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The method for synthesizing the beta-phenethyl alcohol is characterized by comprising the following steps of:
(1) preparation of styrene oxide:
1) taking 3-6 parts by weight of quaternary ammonium salt phase transfer catalyst, 1.2-1.8 parts by weight of metal oxide, 3-7 parts by weight of potassium chloride, 20-25 parts by weight of styrene and 52-60 parts by weight of hydrogen peroxide solution, and reacting for 3-5 hours at a stirring speed of 800-1000 r/min and a reaction temperature of 50-75 ℃ to obtain a crude product of styrene oxide;
2) after the reaction is finished, cooling the reaction solution, extracting the crude product of the styrene oxide in the step (1) by using 50-80 parts by weight of toluene for three times, and combining organic phases;
3) distilling the organic phase obtained in the step 2) under reduced pressure under the condition of 0.3-0.52 kPa, and collecting fractions at 45-50 ℃ to obtain pure styrene oxide;
(2) preparing beta-phenethyl alcohol:
adding the pure styrene oxide prepared in the step 3) into a reactor, adding an alcohol and a ternary metal supported catalyst, filling 3-5MPa hydrogen into the reactor, reacting at the reaction temperature of 40-60 ℃ for 3-5 h at the stirring speed of 600-800 r/min, reducing the pressure of the reactor to room temperature to obtain a reacted mixture, filtering, distilling under reduced pressure, and collecting required fractions, wherein the weight ratio of the styrene oxide to the alcohol to the hydrogen to the ternary metal supported catalyst is 1: (1.4-1.6), (7-12) and (0.013-0.015).
2. The method for synthesizing beta-phenylethyl alcohol according to claim 1, wherein the method comprises the following steps: the quaternary ammonium salt phase transfer catalyst in the step 1) adopts any one of dodecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride.
3. The method for synthesizing beta-phenylethyl alcohol according to claim 1, wherein the method comprises the following steps: the concentration of the hydrogen peroxide solution in the step 1) is 10-12 mol/L.
4. The method for synthesizing beta-phenylethyl alcohol according to claim 1, wherein the method comprises the following steps: in the step 1), when the reaction starts, dropwise adding a hydrogen peroxide solution, wherein the dropwise adding of the hydrogen peroxide solution is completed within 2-3 h.
5. The method for synthesizing beta-phenylethyl alcohol according to claim 1, wherein the method comprises the following steps: the metal oxide in the step 1) adopts V 2 O 5 NiO or TiO 2 At least one of (a).
6. The method for synthesizing beta-phenylethyl alcohol according to claim 1, wherein the method comprises the following steps: the ternary metal supported catalyst in the step (2) adopts a Co-Sn-Bi kieselguhr supported catalyst, and the preparation method of the Co-Sn-Bi kieselguhr supported catalyst comprises the following steps:
a, dissolving 3-5 parts by weight of cobalt salt, 4-5 parts by weight of tin salt and 1-2.3 parts by weight of bismuth salt in 10-15 parts by weight of water to obtain a mixed solution, then dropwise adding ammonium carbonate at a stirring speed of 200-300 r/min until the pH value is 8-10, reacting for 30-60 min, filtering, and drying a filter cake at 120 ℃ to obtain a precursor;
and B, adding 12-15 parts of kieselguhr into the precursor in the step A, mixing and grinding for 10-15 min, and then sequentially aging, drying and roasting to obtain the Co-Sn-Bi kieselguhr supported catalyst.
7. The method for synthesizing beta-phenylethyl alcohol according to claim 6, wherein the method comprises the following steps: the cobalt salt in the step A is cobalt chloride, the tin salt is tin chloride, and the bismuth salt is bismuth chloride.
8. The method for synthesizing beta-phenylethyl alcohol according to claim 6, wherein the method comprises the following steps: the aging temperature in the step B is room temperature, and the aging time is 2-3 h; the drying temperature is 110-120 ℃, the drying time is 1-2 hours, the roasting temperature is 500-700 ℃, and the roasting time is 3-5 hours.
9. The method for synthesizing beta-phenylethyl alcohol according to claim 1, wherein the method comprises the following steps: the alcohol in the step (2) is any one of methanol, ethanol or n-propanol.
10. The method for synthesizing beta-phenylethyl alcohol according to claim 1, wherein the method comprises the following steps: the reduced pressure distillation in the step (2) is to collect fractions at the temperature of 50-55 ℃ under the pressure of 0.18-0.22 kPa.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050131258A1 (en) * | 2003-12-10 | 2005-06-16 | Council Of Scientific And Industrial Research | Process for preparation of 2-phenyl ethanol |
| CN1926124A (en) * | 2004-03-31 | 2007-03-07 | 科学与工业研究会 | Improved catalytic process for the preparation of epoxides from alkenes |
| CN103204830A (en) * | 2012-01-13 | 2013-07-17 | 中国石油化工股份有限公司 | Catalytic oxidation method of styrene |
| CN106905266A (en) * | 2017-03-13 | 2017-06-30 | 常州工程职业技术学院 | A kind of method that epoxidation of styrene prepares Styryl oxide |
| CN107266393A (en) * | 2017-06-28 | 2017-10-20 | 北京化工大学 | A kind of application of Cu bases non-noble metal composite oxide catalyst |
| CN109465011A (en) * | 2018-10-25 | 2019-03-15 | 山东新和成药业有限公司 | A kind of hydrogenation catalyst, preparation method and its application in benzyl carbinol is prepared in Styryl oxide open loop |
| CN109569633A (en) * | 2018-11-14 | 2019-04-05 | 万华化学集团股份有限公司 | Method three-dimensional hollow pipe microarray skeleton catalyst and prepare bata-phenethyl alcohol using it |
| CN109847754A (en) * | 2018-12-18 | 2019-06-07 | 万华化学集团股份有限公司 | A kind of catalyst and the method using the catalyst preparation bata-phenethyl alcohol |
-
2021
- 2021-02-25 CN CN202110212128.4A patent/CN114956955A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050131258A1 (en) * | 2003-12-10 | 2005-06-16 | Council Of Scientific And Industrial Research | Process for preparation of 2-phenyl ethanol |
| CN1926124A (en) * | 2004-03-31 | 2007-03-07 | 科学与工业研究会 | Improved catalytic process for the preparation of epoxides from alkenes |
| CN103204830A (en) * | 2012-01-13 | 2013-07-17 | 中国石油化工股份有限公司 | Catalytic oxidation method of styrene |
| CN106905266A (en) * | 2017-03-13 | 2017-06-30 | 常州工程职业技术学院 | A kind of method that epoxidation of styrene prepares Styryl oxide |
| CN107266393A (en) * | 2017-06-28 | 2017-10-20 | 北京化工大学 | A kind of application of Cu bases non-noble metal composite oxide catalyst |
| CN109465011A (en) * | 2018-10-25 | 2019-03-15 | 山东新和成药业有限公司 | A kind of hydrogenation catalyst, preparation method and its application in benzyl carbinol is prepared in Styryl oxide open loop |
| CN109569633A (en) * | 2018-11-14 | 2019-04-05 | 万华化学集团股份有限公司 | Method three-dimensional hollow pipe microarray skeleton catalyst and prepare bata-phenethyl alcohol using it |
| CN109847754A (en) * | 2018-12-18 | 2019-06-07 | 万华化学集团股份有限公司 | A kind of catalyst and the method using the catalyst preparation bata-phenethyl alcohol |
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