CN108530393A - A kind of synthetic method of epoxides - Google Patents
A kind of synthetic method of epoxides Download PDFInfo
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- CN108530393A CN108530393A CN201810222684.8A CN201810222684A CN108530393A CN 108530393 A CN108530393 A CN 108530393A CN 201810222684 A CN201810222684 A CN 201810222684A CN 108530393 A CN108530393 A CN 108530393A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- 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
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- 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
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The invention discloses a kind of synthetic methods of epoxides, using hydrogen peroxide as oxidant, the reactant synthesizing epoxy compound containing carbon-to-carbon double bond and at least one other functional group is catalyzed in the catalyst system and catalyzing that catalysts and solvents form, solvent is the mixture of alcohol and water in catalyst system and catalyzing, catalyst is the metal ion-modified mixture being made of MWW structure titanium silicon molecular sieves and carrier；Titanium Sieve Molecular Sieve weight percent is not less than the 20% of total catalyst weight in catalyst, and the type of metal ion is expressed as M with the molecular formula of metal oxideXO, wherein X=1 or 2, weight percent account for the 0.05 ~ 3% of total catalyst weight with metallic atom M content meters, and carrier is at least one of silica, aluminium oxide and the aluminum phosphate of counterpoise.The application of invention catalyst system, can with high activity, highly selective catalyze and synthesize epoxides；Its reaction process is simple, environmental-friendly, low energy consumption, is easy to industrialized production and application.
Description
Technical field
The invention belongs to chemical technology fields, are related to a kind of synthetic method of epoxides, specifically, be related to it is a kind of with
Hydrogen peroxide is oxidant, is catalysis with the metal ion-modified mixture being made of MWW structure titanium silicon molecular sieves and carrier
The catalyst system and catalyzing of agent and solvent alcohol composition, highly active catalytic aoxidize the change containing carbon-to-carbon double bond and at least one other functional group
The method for closing object synthesizing epoxy compound.
Background technology
Epoxides is a kind of important organic synthesis intermediate, such as propylene oxide, epoxychloropropane, is widely used in
The fields such as petrochemical industry, fine chemistry industry and organic synthesis.The method of conventional synthesis epoxides is chlorohydrination, and there are technological processes
Long, the shortcomings of by-product is more, three waste discharge is big.To solve the above-mentioned problems, be developed using Titanium Sieve Molecular Sieve as catalyst,
Using hydrogen peroxide as oxidant, epoxides novel technique is catalyzed and synthesized.Since the by-product during this is water, do not generate
Environmental pollution is environmental-friendly Green Chemical Engineering Process.
It is being oxidant using Titanium Sieve Molecular Sieve as catalyst, hydrogen peroxide, catalysis oxidation contains carbon-to-carbon double bond and at least
In a kind of compound synthesis epoxides green chemical industry technology of other functional groups, the selection of suitable solvent is to play titanium silicon
The key of the high catalysed oxidn of molecular sieve.Such as, Fan etc.（J.Catal.,2008,256:62-73）Research find for just oneself
For alkene epoxidation reaction, the Titanium Sieve Molecular Sieve with MFI structure, optimum solvent is methanol, the activity when acetonitrile is solvent
It is very low；And the Titanium Sieve Molecular Sieve with MWW structures, optimum solvent are acetonitrile, activity is also very low when using methanol as solvent.It closes
In the effect of solvent, Clerici etc.（J.Catal.,1992,133:220-230;1993,140:71-83）It is ground first
Study carefully, it is proposed that solvent has cooperatively formed the reactive intermediate of five-membered ring structure, Fan etc. with Titanium Sieve Molecular Sieve and hydrogen peroxide
（J.Catal.,2008,256:62-73）Further system research finds that the effect of solvent is in addition to the property phase with solvent itself
Outside the Pass, also related with the factors such as the structure of Titanium Sieve Molecular Sieve and surface nature and the property of reactant, but the specific effect of solvent
Principle is not currently fully understood.Thus, at present for the Titanium Sieve Molecular Sieve of different structure, there is not specific directiveness also
Principle selects suitable solvent, and is mainly based upon experiment to select and determine that different structure Titanium Sieve Molecular Sieve is most suitable molten
Agent.
For the Titanium Sieve Molecular Sieve with MWW structures, Wu etc.（Chemistry letter,2000,774-775;
J.Catal.,2001,202:245-255）Disclose first with MWW structure titanium silicon molecular sieves and its synthetic method with synthesizing
Application in epoxides finds that its optimum solvent is acetonitrile.Thus, in subsequent open source literature, for MWW structure titanium silicons
Molecular sieve is that catalyst aoxidizes the compound synthesis epoxides containing carbon-to-carbon double bond and at least one other functional group
Method in, one of acetonitrile is formed as indispensable solvent.ZL200480015961.4 discloses a kind of 1,2 epoxy prapane
Preparation method, it is characterised in that porous oxidation material is the zeolite of MWW types, and solvent is a kind of nitrile or includes at least one nitrile
Mixture, at least one nitrile are acetonitrile.In order to further enhance the catalytic oxidation performance of MWW structure titanium silicon molecular sieves, it is based on
To the understanding in Ti catalytic oxidation activities center source in Titanium Sieve Molecular Sieve, Fang etc.（Phys.Chem.Chem.Phys.,2013,
15,4930-4938）Disclose fluorine implantation MWW structure titanium silicon molecular sieves（F-Ti-MWW）Catalytic oxidation performance, it is found that acetonitrile
It is preferred solvent, and is further introduced into alkali metal cation in the reaction system（Li+、Na+、K+、Rb+、Cs+）When, it is catalyzed oxygen
Change activity to increase substantially again.CN105813741A discloses the method for preparing propylene oxide, and feature includes that catalyst includes
Titanium zeolite with framework structure type MWW, solvent are acetonitrile, the another additive potassium dihydrogen phosphate containing in addition to reactant, together
When also disclose a kind of catalyst system and catalyzing, it includes potassium dihydrogen phosphate and containing optionally comprising zinc structure type MWW titanium zeolite
Catalyst.CN105579137A discloses the method for preparing propylene oxide, and feature includes that catalyst includes to have skeleton knot
The titanium zeolite of structure type MWW, solvent are acetonitrile, and the another additive at least one sylvite containing in addition to reactant is also disclosed simultaneously
A kind of catalyst system and catalyzing, the catalysis of the titanium zeolite it includes at least one sylvite and containing the structure type MWW optionally comprising zinc
Agent.It is found that in prior art, the titanium molecular sieve catalysis oxidation with MWW containing carbon-to-carbon double bond and it is at least one its
The compound of its functional group（Such as propylene）Synthesizing epoxy compound（Such as propylene oxide）Method in, acetonitrile is at least one of solvent,
And when the titanium zeolite of the structure type MWW containing zinc is catalyst, catalyst system and catalyzing must be formed at least one sylvite.
From the point of view of the physicochemical property of solvent, small molecule alcohol general toxicity is low, as methanol is hypotoxicity, the tert-butyl alcohol is micro- poison
Property, and acetonitrile is moderate toxicity.For industrialized production, green chemistry is met using toxicity solvent low as possible and is wanted
It asks.Meanwhile it is always that titanium molecular sieve catalysis is answered that research and development, which can give full play to the suitable solvent of titanium molecular sieve catalysis oxidation,
One of key technology.Therefore, carbon-to-carbon double bond is contained for the catalyst oxidation with the structure titanium silicon molecular sieve containing MWW
For the compound synthesis epoxides technology of at least one other functional group, develop using nonnitriles compound as solvent
Highly active catalytic synthesizing epoxy compound technical method have important research meaning, meet industrialization Green Development needs.So
And there is not document report at present.
Invention content
The purpose of the present invention is contain carbon-to-carbon for existing with the catalyst oxidation of the structure titanium silicon molecular sieve containing MWW
The deficiency of double bond and the compound synthesis epoxides technology of at least one other functional group is solved to contain MWW structure titaniums
The catalyst of si molecular sieves not high problem of activity when nonnitriles compound is solvent, the titanium silicon found is studied based on inventor
The microstructure at molecular sieve Ti catalytic oxidation activities center proposes with small the understanding for having selected key effect of suitable solvent
Molecule alcohol and water is solvent and the metal ion-modified mixture being made of MWW structure titanium silicon molecular sieves and carrier is catalyst
Catalyst system and catalyzing, the highly active catalytic of composition aoxidize the production of chemicals ring containing carbon-to-carbon double bond and at least one other functional group
The technique effect of the method for oxide, the method for the present invention has reached and exceeded MWW structure titanium silicon molecular sieves when using acetonitrile as solvent
The technique effect of catalyst synthesizing epoxy compound.
The existing technical solution that the present invention will be described in detail.
A kind of synthetic method of epoxides, the catalytic body formed using hydrogen peroxide as oxidant, in catalysts and solvents
The reactant synthesizing epoxy compound containing carbon-to-carbon double bond and at least one other functional group is catalyzed in system, solvent in catalyst system and catalyzing
It is the metal ion-modified mixture being made of MWW structure titanium silicon molecular sieves and carrier for the mixture of alcohol and water, catalyst；
Titanium Sieve Molecular Sieve weight percent is not less than the 20% of total catalyst weight in catalyst, and the type of metal ion is aoxidized with metal
The molecular formula of object is represented by MXO, wherein x=1 or 2, weight percent account for total catalyst weight with metallic atom M content meters
0.05 ~ 3%, carrier be counterpoise at least one of silica, aluminium oxide and aluminum phosphate；Concrete operation step：
The first step by reactant, catalyst, solvent, hydrogen peroxide to reactor, stirs evenly successively, obtains reaction system, instead
Answer object:Catalyst:The weight ratio of solvent is 1:(0.03~0.15):(1~20), reactant:The molar ratio of hydrogen peroxide is (1
~3):1, the reactant is the compound containing carbon-to-carbon double bond and at least one other functional group, other officials
It is at least one of alkyl, alkenyl, alkynyl, aryl, aryl, hydroxyl, halogeno-group, aldehyde radical that can roll into a ball.
The reaction system of the second step first step is at 30~100 DEG C, 0.1~5MPa of reaction pressure, and reaction 0.5~5 is small
When, routinely filter method isolates catalyst, then routinely operates, detach product to get epoxides.
The preparation method of the catalyst includes step in detail below：
It is prepared by first step mixture
Titanium Sieve Molecular Sieve, carrier, auxiliary agent, alkali and water are uniformly mixed and prepare mixture, charge ratio is titanium silicon point by weight
Son sieve:Metallic atom M in auxiliary agent:Alkali:H2O is 100: (0.10~10) : (0.05~10) :(500~5000), it is described
Titanium Sieve Molecular Sieve be MWW structure titanium silicon molecular sieves, the carrier be silica, aluminium oxide and aluminum phosphate at least one
Kind, it is at least one of+1 or+2 soluble metal salt or metal hydroxides that the auxiliary agent, which is chemical valence, described
Alkali be molecular formula meet N-RnCompound, wherein n=1,2,3, R be H or CyH2y+1(natural numbers of y=1 ~ 6)；
Second step post-processes
The mixture that the first step is obtained is handled 0.5 hour~48 hours under the conditions of room temperature ~ 200 DEG C, is obtained through being filtered, washed
After-treatment products obtain catalyst after conventional drying, roasting.
The alkali is that alkali is NH3, ethamine, di-n-propylamine, Tri-n-Propylamine, n-butylamine, piperidines or hexamethylene imine.
Metallic atom in the auxiliary agent is Na, K, Mg, Ca, Zn or Ni.
Alcohol is the saturated alcohols that carbon atom number is not more than 4 in the solvent.
In the present invention, the MWW structure titanium silicon molecular sieves refer to having MWW topological structures, backbone element in crystallography
At least molecular sieve containing titanium elements in addition to silicon and oxygen element.
Compared with existing technology, the present invention has following remarkable advantage：
1, the catalyst system be applied to epoxides synthesis in, can with high activity, it is highly selective catalyze and synthesize epoxides, carry
The high atom utilization of reactant, reduces the difficulty and production cost of product separation；
2, component of the alcohol as solvent, it is environmental-friendly instead of the higher solvent acetonitrile of toxicity, meet green chemistry trend
It is needed with industrialized production；
3, reaction process is simple, environmental-friendly, low energy consumption, is easy to industrialized production and application.
Specific implementation mode
The operating procedure of all embodiments according to the above technical scheme is operated.
In embodiment, MWW structure titanium silicon molecular sieves are according to patent document（CN 1321061C）Prepared by disclosed method, titanium
Si molecular sieves remove volatile material through 550 DEG C of high-temperature roastings；The content of metallic atom M uses elemental analysis in catalyst
Instrument（Perkin-Elmer series II 2400 CHNS analyzer）Analysis；The analysis of reactants and products uses gas phase
Chromatography（Shimadzu GC14B, DB-1 capillary column 30m × 0.25mm × 0.25 μm）The analysis of analysis, hydrogen peroxide uses cerous sulfate
Analyzing purity.
Embodiment 1~13 is the preparation method of catalyst.
Embodiment 1
It is prepared by first step mixture
Titanium Sieve Molecular Sieve, carrier, auxiliary agent, alkali and water are uniformly mixed and prepare mixture, charge ratio is titanium silicon point by weight
Son sieve:Metallic atom M in auxiliary agent:Alkali:H2O is 100: 2 : 5 :2000, the Titanium Sieve Molecular Sieve is MWW structure titaniums
Si molecular sieves, weight are the 85% of total catalyst weight, and the carrier is the silica of counterpoise, the auxiliary agent
For potassium chloride, the alkali is piperidines；
Second step post-processes
The mixture that the first step is obtained is handled 24 hours under the conditions of 170 DEG C, and after-treatment products are obtained through being filtered, washed, then
After conventional drying, 550 DEG C of roastings, catalyst is obtained, elemental analysis shows that potassium content is 1.58% in catalyst.
Embodiment 2
Except for the following differences, remaining is the same as embodiment 1：
In the first step, Titanium Sieve Molecular Sieve:Metallic atom M in auxiliary agent:Alkali:H2O is 100: 2 : 0.5 :5000, it is described
Auxiliary agent is potassium hydroxide, and the alkali is that mass concentration is 25% ammonium hydroxide；In second step, handles 5 hours, obtain at ambient temperature
To catalyst, elemental analysis shows that potassium content is 1.62% in catalyst.
Embodiment 3
Except for the following differences, remaining is the same as embodiment 1：
In the first step, Titanium Sieve Molecular Sieve:Metallic atom M in auxiliary agent:Alkali:H2O is 100: 0.5 : 5 :3000, it is described
Auxiliary agent is potassium acetate, and the alkali is hexamethylene imine；In second step, handles 48 hours, be catalyzed under the conditions of 150 DEG C
Agent, elemental analysis show that potassium content is 0.35% in catalyst.
Embodiment 4
Except for the following differences, remaining is the same as embodiment 1：
In the first step, Titanium Sieve Molecular Sieve:Metallic atom M in auxiliary agent:Alkali:H2O is 100: 1 : 5 :3000, described helps
Agent is sodium acetate；In second step, is handled 48 hours under the conditions of 120 DEG C, obtain catalyst, elemental analysis shows in catalyst
Sodium content is 0.72%.
Embodiment 5
Except for the following differences, remaining is the same as embodiment 1：
In the first step, Titanium Sieve Molecular Sieve:Metallic atom M in auxiliary agent:Alkali:H2O is 100: 1.5 : 10:4000, it is described
Auxiliary agent is zinc acetate；In second step, is handled 48 hours under the conditions of 160 DEG C, obtain catalyst, elemental analysis shows catalyst
Middle Zn content is 1.18%.
Embodiment 6
Except for the following differences, remaining is the same as embodiment 1：
In the first step, the alkali is ethamine；In second step, is handled 48 hours under the conditions of 100 DEG C, obtain catalyst, element
Analysis shows potassium content is 1.52% in catalyst.
Embodiment 7
Except for the following differences, remaining is the same as embodiment 2：
In second step, is handled 0. 5 hours under the conditions of 80 DEG C, obtain catalyst, elemental analysis shows potassium content in catalyst
It is 1.56%.
Embodiment 8
Except for the following differences, remaining is the same as embodiment 1：
In the first step, the Titanium Sieve Molecular Sieve is MWW structure titanium silicon molecular sieves, and weight is the 70% of total catalyst weight, institute
The carrier stated is the aluminium oxide of counterpoise；It in second step, is handled 12 hours under the conditions of 150 DEG C, obtains catalyst, element point
Analysis shows that potassium content is 1.33% in catalyst.
Embodiment 9
Except for the following differences, remaining is the same as embodiment 1：
In the first step, the Titanium Sieve Molecular Sieve is MWW structure titanium silicon molecular sieves, and weight is the 50% of total catalyst weight, institute
The carrier stated is the aluminum phosphate of counterpoise；It in second step, is handled 48 hours under the conditions of 150 DEG C, obtains catalyst, element point
Analysis shows that potassium content is 0.93% in catalyst.
Embodiment 10
Except for the following differences, remaining is the same as embodiment 1：
In the first step, the Titanium Sieve Molecular Sieve is MWW structure titanium silicon molecular sieves, and weight is the 70% of total catalyst weight, institute
The carrier stated is the aluminium oxide of counterpoise, and the auxiliary agent is that weight ratio is 3:7 potassium chloride and the mixture of zinc acetate,
Catalyst is obtained, elemental analysis shows that potassium content is 0.38% in catalyst, Zn content 0.92%.
Embodiment 11
Except for the following differences, remaining is the same as embodiment 1：
In the first step, the auxiliary agent is magnesium acetate, obtains catalyst, and elemental analysis shows that content of magnesium is 1.35% in catalyst.
Embodiment 12
Except for the following differences, remaining is the same as embodiment 1：
In the first step, the auxiliary agent is calcium acetate, obtains catalyst, and elemental analysis shows that calcium content is 1.32% in catalyst.
Embodiment 13
Except for the following differences, remaining is the same as embodiment 1：
In the first step, the auxiliary agent is nickel acetate, obtains catalyst, elemental analysis shows that Nickel Content In Catalyst is 1.49%.
Embodiment 14~24 is the method for prepared catalyst synthesizing epoxy compound.
Embodiment 14
Catalyst is catalyst prepared by embodiment 1, and reactant is n-hexylene.
First step alcohol is methanol, and hydrogen peroxide mass concentration is 30.1%, water therein and methanol as mixed solvent,
Catalyst, solvent, reactant and hydrogen peroxide are added in reactor successively, stirred, reactant:Catalyst:The weight of solvent
Than being 1:0.05:5, reactant:The molar ratio of hydrogen peroxide is 1:1；
The reaction system of the second step first step is reacted 2 hours at normal pressure, 60 DEG C, and routinely filter method isolates catalyst,
Then routinely operate, detach product to get oxepane corresponding with n-hexylene.
Analysis result shows that n-hexylene conversion ratio is 56.5%, and oxepane is selectively 99.5%.
Embodiment 15 ~ 19
Except for the following differences, remaining is the same as embodiment 14：
15 catalyst of embodiment is catalyst prepared by embodiment 5.
16 catalyst of embodiment is catalyst prepared by embodiment 8.
17 catalyst of embodiment is catalyst prepared by embodiment 10.
18 catalyst of embodiment is catalyst prepared by embodiment 11.
19 catalyst of embodiment is catalyst prepared by embodiment 12.
Analysis result shows
15 n-hexylene conversion ratio of embodiment is 35.1%, and oxepane is selectively 99.2%.
16 n-hexylene conversion ratio of embodiment is 54.3%, and oxepane is selectively 99.5%.
17 n-hexylene conversion ratio of embodiment is 49.8%, and oxepane is selectively 99.7%.
18 n-hexylene conversion ratio of embodiment is 33.7%, and oxepane is selectively 99.5%.
19 n-hexylene conversion ratio of embodiment is 34.5%, and oxepane is selectively 99.6%.
Embodiment 20
Except for the following differences, remaining is the same as embodiment 14.
Reactant is chloropropene.
Analysis result shows that chloropropene conversion ratio is 55.4%, and epoxychloropropane is selectively 97.5%.
Embodiment 21
Except for the following differences, remaining is the same as embodiment 14.
Reactant is propylene, reactant in the first step:The molar ratio of hydrogen peroxide is 2:1
The reaction system of the second step first step is reacted 2 hours at 3.0MPa, 40 DEG C
Analysis result shows that propylene conversion is 41.8%, and propylene oxide is selectively 97.1%.
Embodiment 22
Except for the following differences, remaining is the same as embodiment 14.
Alcohol is the tert-butyl alcohol in the first step.
Analysis result shows that n-hexylene conversion ratio is 48.3%, and oxepane is selectively 99.8%.
Embodiment 23
Except for the following differences, remaining is the same as embodiment 21.
Alcohol is the tert-butyl alcohol in the first step.
Analysis result shows that propylene conversion is 42.5%, and propylene oxide is selectively 99.7%.
Embodiment 24
The technique effect that catalyst system and catalyzing of the present invention catalyzes and synthesizes propylene oxide is carried out using fixed bed reactors.Catalyst is to implement
Catalyst prepared by example 1, is shaped to 40 ~ 60 mesh catalyst granules, and 4 grams of catalyst granules is taken to be placed in the stainless steel that internal diameter is 8mm
In reaction tube, alcohol is the tert-butyl alcohol, and hydrogen peroxide mass concentration is 30.1%, according to the weight ratio tert-butyl alcohol:Hydrogen peroxide is 15:1
Reaction mixture is configured, according to molar ratio propylene:Hydrogen peroxide is 3:1, hydrogen peroxide weight space velocity is 0.4h-1, pass through meter
Reaction mixture and propylene are added continuously in reactor by amount pump respectively, with water bath with thermostatic control controlling reaction temperature for 40 DEG C,
It is 3MPa with reactor outlet counterbalance valve control reaction pressure, the experimental results showed that, when reaction continuous-stable 450 hours, analysis
The results show that hydrogen peroxide conversion is 99.2%, propylene conversion 28.5%, propylene oxide selectivity 99.1%, do not occur
Apparent deactivation phenomenom.
From above-described embodiment result it is found that the effect of the technology of the present invention is, using solvent as the mixture and catalysis of alcohol and water
Agent is the catalyst system and catalyzing that the metal ion-modified mixture being made of MWW structure titanium silicon molecular sieves and carrier forms, Ke Yigao
It is active, highly selective to catalyze and synthesize epoxides.
Claims (5)
1. a kind of synthetic method of epoxides, which is characterized in that formed using hydrogen peroxide as oxidant, in catalysts and solvents
Catalyst system and catalyzing in be catalyzed the reactant synthesizing epoxy compound containing carbon-to-carbon double bond and at least one other functional group, catalytic body
Solvent is the mixture of alcohol and water in system, catalyst is metal ion-modified to be made of MWW structure titanium silicon molecular sieves and carrier
Mixture；Titanium Sieve Molecular Sieve weight percent is not less than the 20% of total catalyst weight in catalyst, the type of metal ion with
The molecular formula of metal oxide is expressed as MXO, wherein x=1 or 2, weight percent account for catalyst with metallic atom M content meters
The 0.05 ~ 3% of total weight, carrier are at least one of silica, aluminium oxide and the aluminum phosphate of counterpoise；Concrete operations
Step：
Reactant, catalyst, solvent, hydrogen peroxide are added in reactor by the first step successively, are stirred evenly, and reactant is obtained
System, reactant:Catalyst:The weight ratio of solvent is 1:(0.03~0.15):(1~20), reactant:The molar ratio of hydrogen peroxide
For (1~3):1, the reactant is the compound containing carbon-to-carbon double bond and at least one other functional group, described its
Its functional group is at least one of alkyl, alkenyl, alkynyl, aryl, aryl, hydroxyl, halogeno-group, aldehyde radical；
The reaction system of the second step first step is at 30~100 DEG C, 0.1~5MPa of reaction pressure, reacts 0.5~5 hour, presses
Customary filtration methods isolate catalyst, then routinely operate, detach product to get epoxides.
2. synthetic method according to claim 1, which is characterized in that the preparation of the catalyst includes walking in detail below
Suddenly：
It is prepared by first step mixture
Titanium Sieve Molecular Sieve, carrier, auxiliary agent, alkali and water are uniformly mixed and prepare mixture, charge ratio is by weight：Titanium silicon point
Son sieve:Metallic atom M in auxiliary agent:Alkali:H2O is 100: (0.10~5) : (0.05~10) :(500~5000), it is described
Titanium Sieve Molecular Sieve be MWW structure titanium silicon molecular sieves, the carrier be silica, aluminium oxide and aluminum phosphate at least one
Kind, it is at least one of+1 or+2 soluble metal salt or metal hydroxides that the auxiliary agent, which is chemical valence, described
Alkali be that molecular formula meets the compound of N-Rn, wherein n=1,2,3, R be H or CyH2y+1；The natural number of y=1 ~ 6；
Second step post-processes
The mixture that the first step is obtained is handled 0.5 hour~48 hours under the conditions of room temperature ~ 200 DEG C, is obtained through being filtered, washed
After-treatment products obtain the catalyst after conventional drying, roasting.
3. synthetic method according to claim 2, is further characterized by, alkali NH3, ethamine, di-n-propylamine, three positive third
Amine, n-butylamine, piperidines or hexamethylene imine.
4. synthetic method according to claim 2, is further characterized by, the metallic atom in auxiliary agent is Na, K, Mg,
Ca, Zn or Ni.
5. synthetic method according to claim 1, is further characterized by, alcohol is carbon atom number no more than 4 in solvent
Saturated alcohols.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109513455A (en) * | 2018-12-04 | 2019-03-26 | 红宝丽集团股份有限公司 | Epoxidation catalyst and preparation method thereof and application method |
| CN111848550A (en) * | 2019-04-30 | 2020-10-30 | 华东师范大学 | Preparation method of epoxide |
| CN114426551A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene dioxide DCPDO |
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| CN111848550A (en) * | 2019-04-30 | 2020-10-30 | 华东师范大学 | Preparation method of epoxide |
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| CN114426551B (en) * | 2020-10-15 | 2024-02-02 | 中国石油化工股份有限公司 | Method for preparing dicyclopentadiene dioxide DCPDO |
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