CN110498778A - The method that epoxidation of cyclohexene prepares 7-oxa-bicyclo[4.1.0 - Google Patents
The method that epoxidation of cyclohexene prepares 7-oxa-bicyclo[4.1.0 Download PDFInfo
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- CN110498778A CN110498778A CN201810472463.6A CN201810472463A CN110498778A CN 110498778 A CN110498778 A CN 110498778A CN 201810472463 A CN201810472463 A CN 201810472463A CN 110498778 A CN110498778 A CN 110498778A
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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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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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
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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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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- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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Abstract
The present invention provides a kind of method that epoxidation of cyclohexene prepares 7-oxa-bicyclo[4.1.0, mainly solves the problems, such as to exist in the prior art that catalyst activity is low, 7-oxa-bicyclo[4.1.0 is selectively low.This method is using cyclohexene as substrate, acetonitrile is reaction dissolvent, tert-butyl hydroperoxide solution is oxidant, epoxidation reaction of olefines is carried out on the Ti-MWW molecular sieve catalyst that lamellar spacing is no more than the thin layer of 20nm, framework titania molar content not less than 2%, high skeleton Ti content, after reaction by reaction solution rectification process, the fraction for taking 130~135 DEG C, obtains 7-oxa-bicyclo[4.1.0.Method cyclohexene conversion rate of the invention is high, target product 7-oxa-bicyclo[4.1.0 selectivity is high, can be used for the industrial production of 7-oxa-bicyclo[4.1.0.
Description
Technical field
The present invention relates to a kind of methods for preparing 7-oxa-bicyclo[4.1.0, belong to petrochemical industry.
Background technique
7-oxa-bicyclo[4.1.0 is important Organic Ingredients, is mainly used for synthetic hydrochloric acid benzhexol, propargite and 1,2- hexamethylene two
Alcohol etc. plays an important role in fields such as medicine, chemical industry.With continually developing for 7-oxa-bicyclo[4.1.0 purposes, to its demand
Amount also increases sharply.
It is recycled on a small quantity from the by-product of the technical process of cyclohexane oxidation preparing cyclohexanone, cyclohexanol currently, having both at home and abroad
The method of 7-oxa-bicyclo[4.1.0.Add hydrochloric acid to be converted into 2- chloro cyclohexanol as patent CN1128143C takes by-product, then separates
Low-boiling point material, then 2- chloro cyclohexanol is reacted with alkali and obtains 7-oxa-bicyclo[4.1.0 product.Epoxy hexamethylene in this recycling by-product
The method yield of alkane is not able to satisfy increasing demand.And the yield of tradition chlorohydrination synthesis epoxy cyclohexane is low, simultaneously
There are equipment seriously corroded, environmental pollution is serious the problems such as.Since green, Atom economy are higher relatively and catalyst is easy to divide
From the features such as, be the heterogeneous catalysis epoxidation of cyclohexene 7-oxa-bicyclo[4.1.0 technology of oxidant just by extensive using peroxide
Concern.
Patent CN102786500B discloses a kind of method that heterogeneous catalysis epoxidation prepares 7-oxa-bicyclo[4.1.0.It is with hexamethylene
Alkene is substrate, and acetonitrile is reaction dissolvent, and 30wt% hydrogen peroxide is oxidant, miscellaneous by the molecular sieve carried phosphorus molybdenum cobalt of Ti-MCM-41
Epoxidation reaction of olefines is carried out under the catalyst action of polyacid sodium salt, after reaction by reaction solution rectification process, take 130~
135 DEG C of fraction, obtains 7-oxa-bicyclo[4.1.0.But the cyclohexene conversion rate of this method and the selectivity of 7-oxa-bicyclo[4.1.0 be not high,
The highest yield of 7-oxa-bicyclo[4.1.0 also only has 50% or so.
Patent CN101348472B is using organic amine as template synthesizing mesoporous silicon dioxide carrier, in an inert atmosphere by nothing
Machine titanium source is grafted onto the catalyst that epoxidation reaction is made on meso-porous titanium dioxide silicon carrier through silanization treatment again, cyclohexene and has
Product 7-oxa-bicyclo[4.1.0 is made as substrate, epoxidation in machine hydrogen peroxide.This method preferably solves environmental pollution, equipment corruption
Lose the problems such as serious.But the preparation method of catalyst is more complicated, its stability also still needs to be further improved, these are all to big
It is unfavorable that technical scale metaplasia produces.
The micro porous molecular sieve material of titaniferous is also used for epoxidation of cyclohexene reaction.Patent CN103130749B discloses one
The method that kind cyclohexene oxide prepares 7-oxa-bicyclo[4.1.0, this method is under oxidation reaction condition, by cyclohexene, hydrogen peroxide or mistake
Aoxidizing aqueous solution of hydrogen and hollow TS-1 molecular sieve catalyst, haptoreaction obtains 7-oxa-bicyclo[4.1.0 in organic solvent.Although hollow
After change processing, reactants and products spread to improve to a certain extent in titanium-silicon molecular sieve TS-1, but hollow TS-1 molecule
The shell thickness of sieve is still above 100nm, and the diffusion restriction faced is still larger, and catalytic activity is still lower, needs larger
Catalyst amount and under the longer reaction time just have preferable cyclohexene conversion rate.
Documents and materials (M.Yoshioka, et al., Micro.Meso.Mater., 2014,200,11-18) report one
The method for twelve-ring is expanded in aperture by ten-ring between the Ti-MWW molecular sieve layer that lamellar spacing is 50nm by kind.Although organosilicon
After reaming, the performance of Ti-MWW molecular sieve catalytic epoxidation of cyclohexene is improved, but since lamella is thicker, unfavorable diffusion,
The conversion ratio of its cyclohexene is still less than 20%.In addition, epoxy product occurs certain due to the use of faintly acid hydrogen peroxide solution
The open loop of degree, the selectivity of 7-oxa-bicyclo[4.1.0 is also only less than 90%.Although titanium-silicon molecular sieve catalyst has preferable steady
It is qualitative, but these experimental datas show that it still has with a distance from no small from industrial application.
From the above it is found that the epoxidation of cyclohexene reported at present prepares the method for 7-oxa-bicyclo[4.1.0, all there is also certain
The problem of.Consider from industrialized production and application angle, develops high activity, highly selective and high stability epoxidation of cyclohexene
The new method that catalyst and epoxidation of cyclohexene prepare 7-oxa-bicyclo[4.1.0 will have great importance.
Summary of the invention
7-oxa-bicyclo[4.1.0 catalyst, which is prepared, the technical problem to be solved by the present invention is to existing epoxidation of cyclohexene there is work
Property the selectively low problem of low, 7-oxa-bicyclo[4.1.0, a kind of method that new epoxidation of cyclohexene prepares 7-oxa-bicyclo[4.1.0 is provided.It should
Method has the characteristics that catalyst activity is high, 7-oxa-bicyclo[4.1.0 is selectively high.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows: a kind of epoxidation of cyclohexene prepares epoxy
The method of hexamethylene, using cyclohexene as substrate, acetonitrile is reaction dissolvent, and tert-butyl hydroperoxide solution is oxidant, in lamella
Thickness is no more than the Ti-MWW molecular sieve catalyst of the thin layer of 20nm, framework titania molar content not less than 2%, high skeleton Ti content
Upper carry out epoxidation reaction of olefines takes 130~135 DEG C of fraction, obtains epoxide ring after reaction by reaction solution rectification process
Hexane.
In above-mentioned technical proposal, the Ti-MWW of cyclohexene, tert-butyl hydroperoxide, acetonitrile and thin layer, high skeleton Ti content
The mass ratio of molecular sieve catalyst is 1:(0.1~10): (0.2~5): (0.1~1), it is preferable that cyclohexene, t-butyl peroxy
Change hydrogen, acetonitrile and thin layer, high skeleton Ti content the mass ratio of Ti-MWW molecular sieve catalyst be 1:(1~5): (0.5~4):
(0.2~0.5).
In above-mentioned technical proposal, tert-butyl hydroperoxide solution be tert-butyl hydroperoxide aqueous solution or certain herbaceous plants with big flowers alkane solution, it is excellent
Selection of land, tert-butyl hydroperoxide solution are tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane solution.
In above-mentioned technical proposal, epoxidation reaction of olefines condition are as follows: 60~120 DEG C of reaction temperature, reaction pressure 0.01~
3MPa, 0.5~12h of reaction time, it is preferable that epoxidation reaction of olefines condition are as follows: 70~90 DEG C of reaction temperature, reaction pressure
0.02~2.5MPa, 0.5~6h of reaction time.
In above-mentioned technical proposal, thin layer, high skeleton Ti content Ti-MWW molecular sieve catalyst lamellar spacing be 10~
20nm, the molar content of framework titania are 2%~3.3%.
In above-mentioned technical proposal, thin layer, the Ti-MWW molecular sieve catalyst of high skeleton Ti content are obtained by three-step approach: the
One step, synthesis Ti-MWW molecular screen primary powder；Second step, acid processing Ti-MWW molecular screen primary powder；Third step, high-temperature roasting.
In above-mentioned technical proposal, the step of synthesizing Ti-MWW molecular screen primary powder is, first the SiO in silicon source in molar ratio2: titanium
TiO in source2: the B in boron source2O3: organic amine: H2O is 1:(0.02~0.5): (0.5~2): (1.2~2): (20~40) will
Water, organic amine, titanium source, boron source and silicon source are successively uniformly mixed into glue, in 20~50rpm, 130~170 DEG C of Dynamic Hydrothermal crystallization 2
~7 days, then the SiO in silicon source in molar ratio2: organosilicon is 1:(0.02~0.06) organosilicon is added in the molten/gel, in
20~50rpm, 130~170 DEG C Dynamic Hydrothermal crystallization 2~7 days, through centrifugation, washing, drying, obtain Ti-MWW molecular screen primary powder；
The silicon source is selected from least one of fumed silica or silica solution, and the titanium source is selected from tetra-n-butyl titanate or metatitanic acid
At least one of tetra-isopropyl, the boron source are selected from boric acid, and the organic amine is selected from piperidines, and the organosilicon is selected from dimethyl
At least one of diethoxy silane, dimethyldichlorosilane or dimethyl chloride bromo-silicane.
In above-mentioned technical proposal, sour the step of handling Ti-MWW molecular screen primary powder is Ti-MWW molecular screen primary powder and piperidines
And the acid solution that concentration is 1~5mol/L is 1:(0.1~0.5 in mass ratio): (20~40) are mixed, at 60~95 DEG C
Reason 10~30 hours, through centrifugation, washing, drying, obtains Ti-MWW molecular sieve acid-treated product；The acid solution be selected from nitric acid or
At least one of hydrochloric acid solution.
In above-mentioned technical proposal, the step of high-temperature roasting is, by Ti-MWW molecular sieve acid-treated product in 500~600 DEG C,
Air or oxygen atmosphere roasts 6~10 hours, obtains Ti-MWW zeolite product.
The present invention uses cyclohexene for substrate, and acetonitrile is reaction dissolvent, and tert-butyl hydroperoxide solution is oxidant, lamella
Thickness is no more than the method that the Ti-MWW molecular sieve of 20nm, framework titania molar content not less than 2% is catalyst and prepares epoxide ring
Hexane, for the high conversion rate of cyclohexene up to 96%, the selectivity of 7-oxa-bicyclo[4.1.0 is up to 98%, can be used for the industry of 7-oxa-bicyclo[4.1.0
Production.The present invention will be further described below by way of examples.
Specific embodiment
In the context of the present specification, it is included in embodiment below and comparative example, the lamella of Ti-MWW molecular sieve
Thickness and skeleton Ti content pass through transmissioning electric mirror test respectively and elemental analysis method determines.It is evaluated about catalytic perfomance,
The analysis respectively formed in reaction system is carried out using gas-chromatography, is quantified by correcting normalization method, can refer to existing skill
Art carries out, and calculates the evaluation indexes such as the conversion ratio of reactant, the selectivity of product on this basis.
In the present invention, the conversion ratio calculation formula of cyclohexene is as follows:
The selective calculation formula of 7-oxa-bicyclo[4.1.0 is as follows:
Wherein, X is conversion ratio, and S is selectivity, and m is the quality of component, and n is the amount of the substance of component, wherein m ° and n ° point
The amount of quality and substance before Biao Shi not reacting.
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
[embodiment 1]
Prepare Ti-MWW molecular sieve catalyst.The first step synthesizes Ti-MWW molecular screen primary powder.First SiO in molar ratio2:
TiO2: B2O3: piperidines: H2O is 1:0.05:0.67:1.4:30 by the water of corresponding amount, piperidines, tetra-n-butyl titanate, boric acid and 60
Gram fumed silica is successively uniformly mixed into glue, 150 DEG C of Dynamic Hydrothermal crystallization each 1 day in 30rpm, first after 130 DEG C, then presses
Molar ratio SiO2: dimethyl diethoxysilane is that dimethyl diethoxysilane is added in the molten/gel 1:0.035, in
30rpm, 170 DEG C Dynamic Hydrothermal crystallization 5 days, through centrifugation, washing, drying, obtain Ti-MWW molecular screen primary powder.Second step, to Ti-
MWW molecular screen primary powder carries out sour processing.The Ti-MWW molecular screen primary powder and piperidines and concentration that the first step is obtained are 2mol/L's
Nitric acid solution is that 1:0.2:30 is mixed in mass ratio, handles 24 hours in 75 DEG C, through centrifugation, washing, drying, obtains Ti-
MWW molecular sieve acid-treated product.Third step, high-temperature roasting.The Ti-MWW molecular sieve acid-treated product that second step is obtained is in 550
DEG C, air atmosphere roast 8 hours, obtain lamellar spacing be 10nm, framework titania molar content be 3.3% Ti-MWW molecular sieve produce
Product.
[embodiment 2]
Prepare Ti-MWW molecular sieve catalyst.The first step synthesizes Ti-MWW molecular screen primary powder.First SiO in molar ratio2:
TiO2: B2O3: piperidines: H2O is 1:0.05:0.67:1.4:30 by the water of corresponding amount, piperidines, tetra-n-butyl titanate, boric acid and 60
Gram fumed silica is successively uniformly mixed into glue, 150 DEG C of Dynamic Hydrothermal crystallization each 1 day in 30rpm, first after 130 DEG C, then presses
Molar ratio SiO2: dimethyl diethoxysilane is that dimethyl diethoxysilane is added in the molten/gel 1:0.035, in
30rpm, 170 DEG C Dynamic Hydrothermal crystallization 5 days, through centrifugation, washing, drying, obtain Ti-MWW molecular screen primary powder.Second step, to Ti-
MWW molecular screen primary powder carries out sour processing.The Ti-MWW molecular screen primary powder and piperidines and concentration that the first step is obtained are 2mol/L's
Nitric acid solution is that 1:0.15:30 is mixed in mass ratio, handles 24 hours in 75 DEG C, through centrifugation, washing, drying, obtains Ti-
MWW molecular sieve acid-treated product.Third step, high-temperature roasting.The Ti-MWW molecular sieve acid-treated product that second step is obtained is in 550
DEG C, air atmosphere roast 8 hours, obtain lamellar spacing be 15nm, framework titania molar content be 3.3% Ti-MWW molecular sieve produce
Product.
[embodiment 3]
Prepare Ti-MWW molecular sieve catalyst.The first step synthesizes Ti-MWW molecular screen primary powder.First SiO in molar ratio2:
TiO2: B2O3: piperidines: H2O is 1:0.05:0.67:1.4:30 by the water of corresponding amount, piperidines, tetra-n-butyl titanate, boric acid and 60
Gram fumed silica is successively uniformly mixed into glue, 150 DEG C of Dynamic Hydrothermal crystallization each 1 day in 30rpm, first after 130 DEG C, then presses
Molar ratio SiO2: dimethyl diethoxysilane is that dimethyl diethoxysilane is added in the molten/gel 1:0.035, in
30rpm, 170 DEG C Dynamic Hydrothermal crystallization 5 days, through centrifugation, washing, drying, obtain Ti-MWW molecular screen primary powder.Second step, to Ti-
MWW molecular screen primary powder carries out sour processing.The Ti-MWW molecular screen primary powder and piperidines and concentration that the first step is obtained are 2mol/L's
Nitric acid solution is that 1:0.1:30 is mixed in mass ratio, handles 24 hours in 75 DEG C, through centrifugation, washing, drying, obtains Ti-
MWW molecular sieve acid-treated product.Third step, high-temperature roasting.The Ti-MWW molecular sieve acid-treated product that second step is obtained is in 550
DEG C, air atmosphere roast 8 hours, obtain lamellar spacing be 20nm, framework titania molar content be 3.3% Ti-MWW molecular sieve produce
Product.
[embodiment 4]
Prepare Ti-MWW molecular sieve catalyst.The first step synthesizes Ti-MWW molecular screen primary powder.First SiO in molar ratio2:
TiO2: B2O3: piperidines: H2O is 1:0.05:0.67:1.4:30 by the water of corresponding amount, piperidines, tetra-n-butyl titanate, boric acid and 60
Gram fumed silica is successively uniformly mixed into glue, 150 DEG C of Dynamic Hydrothermal crystallization each 1 day in 30rpm, first after 130 DEG C, then presses
Molar ratio SiO2: dimethyl diethoxysilane is that dimethyl diethoxysilane is added in the molten/gel 1:0.035, in
30rpm, 170 DEG C Dynamic Hydrothermal crystallization 5 days, through centrifugation, washing, drying, obtain Ti-MWW molecular screen primary powder.Second step, to Ti-
MWW molecular screen primary powder carries out sour processing.The Ti-MWW molecular screen primary powder and piperidines and concentration that the first step is obtained are 2mol/L's
Nitric acid solution is that 1:0.3:30 is mixed in mass ratio, handles 24 hours in 75 DEG C, through centrifugation, washing, drying, obtains Ti-
MWW molecular sieve acid-treated product.Third step, high-temperature roasting.The Ti-MWW molecular sieve acid-treated product that second step is obtained is in 550
DEG C, air atmosphere roast 8 hours, obtain lamellar spacing be 10nm, framework titania molar content be 2.8% Ti-MWW molecular sieve produce
Product.
[embodiment 5]
Prepare Ti-MWW molecular sieve catalyst.The first step synthesizes Ti-MWW molecular screen primary powder.First SiO in molar ratio2:
TiO2: B2O3: piperidines: H2O is 1:0.05:0.67:1.4:30 by the water of corresponding amount, piperidines, tetra-n-butyl titanate, boric acid and 60
Gram fumed silica is successively uniformly mixed into glue, 150 DEG C of Dynamic Hydrothermal crystallization each 1 day in 30rpm, first after 130 DEG C, then presses
Molar ratio SiO2: dimethyl diethoxysilane is that dimethyl diethoxysilane is added in the molten/gel 1:0.035, in
30rpm, 170 DEG C Dynamic Hydrothermal crystallization 5 days, through centrifugation, washing, drying, obtain Ti-MWW molecular screen primary powder.Second step, to Ti-
MWW molecular screen primary powder carries out sour processing.The Ti-MWW molecular screen primary powder and piperidines and concentration that the first step is obtained are 2mol/L's
Nitric acid solution is that 1:0.5:30 is mixed in mass ratio, handles 24 hours in 75 DEG C, through centrifugation, washing, drying, obtains Ti-
MWW molecular sieve acid-treated product.Third step, high-temperature roasting.The Ti-MWW molecular sieve acid-treated product that second step is obtained is in 550
DEG C, air atmosphere roast 8 hours, obtain lamellar spacing be 10nm, framework titania molar content be 2% Ti-MWW molecular sieve produce
Product.
[embodiment 6]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane that 200g mass content is 50% it is molten
Liquid and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 75 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force
On blender.Start magnetic agitation, start to react, terminates after reacting 1h, filter to isolate catalyst.It is filtered with gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in liquid, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 96%, ring
The selectivity of oxygen hexamethylene is 98%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 7]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 2.8% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane that 200g mass content is 50% it is molten
Liquid and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 75 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force
On blender.Start magnetic agitation, start to react, terminates after reacting 1h, filter to isolate catalyst.It is filtered with gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in liquid, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 80%, ring
The selectivity of oxygen hexamethylene is 98%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 8]
Weigh three mouthfuls that the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 2% is loaded on 500mL
In vial, then sequentially add into container 50g acetonitrile, the tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane solution that 200g mass content is 50%
With 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 75 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force and stirs
It mixes on device.Start magnetic agitation, start to react, terminates after reacting 1h, filter to isolate catalyst.With gas chromatographic analysis filtrate
In cyclohexene, 7-oxa-bicyclo[4.1.0 content, to determine the catalytic performance of catalyst, the conversion ratio of cyclohexene is 60%, epoxy
The selectivity of hexamethylene is 98%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 9]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 15nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane that 200g mass content is 50% it is molten
Liquid and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 75 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force
On blender.Start magnetic agitation, start to react, terminates after reacting 1h, filter to isolate catalyst.It is filtered with gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in liquid, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 87%, ring
The selectivity of oxygen hexamethylene is 98%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 10]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 20nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane that 200g mass content is 50% it is molten
Liquid and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 75 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force
On blender.Start magnetic agitation, start to react, terminates after reacting 1h, filter to isolate catalyst.It is filtered with gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in liquid, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 76%, ring
The selectivity of oxygen hexamethylene is 98%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 11]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane that 200g mass content is 50% it is molten
Liquid and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 90 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force
On blender.Start magnetic agitation, start to react, terminates after reacting 0.5h, filter to isolate catalyst.Use gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in filtrate, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 96%,
The selectivity of 7-oxa-bicyclo[4.1.0 is 94%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 12]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane that 200g mass content is 50% it is molten
Liquid and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 60 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force
On blender.Start magnetic agitation, start to react, terminates after reacting 3h, filter to isolate catalyst.It is filtered with gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in liquid, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 95%, ring
The selectivity of oxygen hexamethylene is 98%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 13]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 25g acetonitrile, tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane that 200g mass content is 50% it is molten
Liquid and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 60 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force
On blender.Start magnetic agitation, start to react, terminates after reacting 2.5h, filter to isolate catalyst.Use gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in filtrate, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 94%,
The selectivity of 7-oxa-bicyclo[4.1.0 is 98%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 14]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 125g acetonitrile, the tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane that 200g mass content is 50%
Solution and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 60 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic
On power blender.Start magnetic agitation, start to react, terminates after reacting 5h, filter to isolate catalyst.Use gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in filtrate, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 95%,
The selectivity of 7-oxa-bicyclo[4.1.0 is 97%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 15]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane that 75g mass content is 50% it is molten
Liquid and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 75 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force
On blender.Start magnetic agitation, start to react, terminates after reacting 2h, filter to isolate catalyst.It is filtered with gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in liquid, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 95%, ring
The selectivity of oxygen hexamethylene is 97%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 16]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane that 150g mass content is 50% it is molten
Liquid and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 75 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force
On blender.Start magnetic agitation, start to react, terminates after reacting 1.5h, filter to isolate catalyst.Use gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in filtrate, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 94%,
The selectivity of 7-oxa-bicyclo[4.1.0 is 98%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 17]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane that 300g mass content is 25% it is molten
Liquid and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 75 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force
On blender.Start magnetic agitation, start to react, terminates after reacting 2.5h, filter to isolate catalyst.Use gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in filtrate, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 92%,
The selectivity of 7-oxa-bicyclo[4.1.0 is 97%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 18]
It weighs the Ti-MWW molecular sieve that 12.5g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on 500mL
Three mouthfuls of vials in, then sequentially add into container 50g acetonitrile, the tert-butyl hydroperoxide certain herbaceous plants with big flowers that 200g mass content is 50%
Alkane solution and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 75 DEG C of constant temperature oil baths, oil bath is placed in temperature control
On magnetic stirring apparatus.Start magnetic agitation, start to react, terminates after reacting 0.5h, filter to isolate catalyst.Use gas-chromatography
The content of cyclohexene in filtrate, 7-oxa-bicyclo[4.1.0 is analyzed, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene be
96%, the selectivity of 7-oxa-bicyclo[4.1.0 is 99%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product epoxy hexamethylene
Alkane.
[embodiment 19]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, the tert-butyl hydroperoxide aqueous solution that 200g mass content is 50%
With 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 90 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force and stirs
It mixes on device.Start magnetic agitation, start to react, terminates after reacting 2h, filter to isolate catalyst.With gas chromatographic analysis filtrate
In cyclohexene, 7-oxa-bicyclo[4.1.0 content, to determine the catalytic performance of catalyst, the conversion ratio of cyclohexene is 90%, epoxy
The selectivity of hexamethylene is 85%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 20]
It weighs the Ti-MWW molecular sieve that 20g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on 500mL
In three mouthfuls of vials, then sequentially add into container 50g acetonitrile, tert-butyl hydroperoxide that 200g mass content is 50% it is water-soluble
Liquid and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 90 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force
On blender.Start magnetic agitation, start to react, terminates after reacting 0.5h, filter to isolate catalyst.Use gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in filtrate, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 88%,
The selectivity of 7-oxa-bicyclo[4.1.0 is 87%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 21]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, the tert-butyl hydroperoxide aqueous solution that 150g mass content is 50%
With 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 75 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force and stirs
It mixes on device.Start magnetic agitation, start to react, terminates after reacting 6h, filter to isolate catalyst.With gas chromatographic analysis filtrate
In cyclohexene, 7-oxa-bicyclo[4.1.0 content, to determine the catalytic performance of catalyst, the conversion ratio of cyclohexene is 82%, epoxy
The selectivity of hexamethylene is 84%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[embodiment 22]
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 10nm, framework titania molar content is 3.3% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, the tert-butyl hydroperoxide aqueous solution that 300g mass content is 25%
With 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 75 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force and stirs
It mixes on device.Start magnetic agitation, start to react, terminates after reacting 10h, filter to isolate catalyst.It is filtered with gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in liquid, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 80%, ring
The selectivity of oxygen hexamethylene is 80%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
[comparative example 1] year-on-year embodiment 1
Prepare Ti-MWW molecular sieve catalyst.The first step synthesizes Ti-MWW molecular screen primary powder.First SiO in molar ratio2:
TiO2: B2O3: piperidines: H2O is 1:0.05:0.67:1.4:30 by the water of corresponding amount, piperidines, tetra-n-butyl titanate, boric acid and 60
Gram fumed silica is successively uniformly mixed into glue, 150 DEG C of Dynamic Hydrothermal crystallization each 1 day in 30rpm, first after 130 DEG C, then presses
Molar ratio SiO2: dimethyl diethoxysilane is that dimethyl diethoxysilane is added in the molten/gel 1:0.035, in
30rpm, 170 DEG C Dynamic Hydrothermal crystallization 5 days, through centrifugation, washing, drying, obtain Ti-MWW molecular screen primary powder.Second step, to Ti-
MWW molecular screen primary powder carries out sour processing.The Ti-MWW molecular screen primary powder that the first step is obtained and the nitric acid that concentration is 2mol/L are molten
Liquid is that 1:30 is mixed in mass ratio, is handled 24 hours in 75 DEG C, through centrifugation, washing, drying, obtains Ti-MWW molecular sieve acid
Handle product.Third step, high-temperature roasting.The Ti-MWW molecular sieve acid-treated product that second step is obtained is in 550 DEG C, air atmosphere
Roasting 8 hours, obtaining lamellar spacing is 50nm, the Ti-MWW zeolite product that framework titania molar content is 2.5%.
[comparative example 2] year-on-year embodiment 6
It weighs the Ti-MWW molecular sieve that 5g lamellar spacing is 50nm, framework titania molar content is 2.5% and is loaded on the three of 500mL
In mouthful vial, then into container sequentially add 50g acetonitrile, tert-butyl hydroperoxide certain herbaceous plants with big flowers alkane that 200g mass content is 50% it is molten
Liquid and 25g cyclohexene.Three mouthfuls of vials are connected into condensing reflux pipe and are put in 75 DEG C of constant temperature oil baths, oil bath is placed in temperature control magnetic force
On blender.Start magnetic agitation, start to react, terminates after reacting 1h, filter to isolate catalyst.It is filtered with gas chromatographic analysis
The content of cyclohexene, 7-oxa-bicyclo[4.1.0 in liquid, to determine that the catalytic performance of catalyst, the conversion ratio of cyclohexene are 50%, ring
The selectivity of oxygen hexamethylene is 98%.Filtrate rectifying collects 130~135 DEG C of fraction, obtains product 7-oxa-bicyclo[4.1.0.
Claims (10)
1. a kind of method that epoxidation of cyclohexene prepares 7-oxa-bicyclo[4.1.0, which is characterized in that using cyclohexene as substrate, acetonitrile is anti-
Solvent is answered, tert-butyl hydroperoxide solution is oxidant, is not less than in lamellar spacing no more than 20nm, framework titania molar content
2% thin layer, high skeleton Ti content Ti-MWW molecular sieve catalyst on carry out epoxidation reaction of olefines obtain 7-oxa-bicyclo[4.1.0.
2. the method that epoxidation of cyclohexene according to claim 1 prepares 7-oxa-bicyclo[4.1.0, which is characterized in that cyclohexene,
Tert-butyl hydroperoxide, acetonitrile and thin layer, high skeleton Ti content Ti-MWW molecular sieve catalyst mass ratio be 1:(0.1~
10): (0.2~5): (0.1~1).
3. the according to claim 1, method that epoxidation of cyclohexene described in 2 prepares 7-oxa-bicyclo[4.1.0, which is characterized in that hexamethylene
Alkene, tert-butyl hydroperoxide, acetonitrile and thin layer, high skeleton Ti content Ti-MWW molecular sieve catalyst mass ratio be 1:(1~
5): (0.5~4): (0.2~0.5).
4. the method that epoxidation of cyclohexene according to claim 1 prepares 7-oxa-bicyclo[4.1.0, which is characterized in that the alkene
Epoxidation reaction condition are as follows: 60~120 DEG C of reaction temperature, 0.01~3MPa of reaction pressure, 0.5~12h of reaction time.
5. the method that epoxidation of cyclohexene according to claim 4 prepares 7-oxa-bicyclo[4.1.0, which is characterized in that the alkene
Epoxidation reaction condition are as follows: 70~90 DEG C of reaction temperature, 0.02~2.5MPa of reaction pressure, 0.5~6h of reaction time.
6. the method that epoxidation of cyclohexene according to claim 1 prepares 7-oxa-bicyclo[4.1.0, which is characterized in that described thin
Layer, high skeleton Ti content the lamellar spacing of Ti-MWW molecular sieve catalyst be 10~20nm, the molar content of framework titania is 2%
~3.3%.
7. the method that epoxidation of cyclohexene according to claim 1 prepares 7-oxa-bicyclo[4.1.0, which is characterized in that thin layer, height
The preparation of the Ti-MWW molecular sieve catalyst of skeleton Ti content includes three steps: synthesis Ti-MWW molecular screen primary powder；Acid processing
Ti-MWW molecular screen primary powder；High-temperature roasting.
8. the method that epoxidation of cyclohexene according to claim 7 prepares 7-oxa-bicyclo[4.1.0, which is characterized in that synthesis Ti-
The step of MWW molecular screen primary powder is the SiO in first silicon source in molar ratio2: the TiO in titanium source2: the B in boron source2O3: organic amine:
H2O be 1:(0.02~0.5): (0.5~2): (1.2~2): (20~40) by water, organic amine, titanium source, boron source and silicon source successively
Be uniformly mixed into glue, in 20~50rpm, 130~170 DEG C Dynamic Hydrothermal crystallization 2~7 days, then the SiO in silicon source in molar ratio2:
Organosilicon is 1:(0.02~0.06) organosilicon is added in the molten/gel, in 20~50rpm, 130~170 DEG C of Dynamic Hydrothermals
Crystallization 2~7 days, through centrifugation, washing, drying, obtain Ti-MWW molecular screen primary powder；The silicon source be selected from fumed silica or
At least one of silica solution, the titanium source are selected from least one of tetra-n-butyl titanate or tetraisopropyl titanate, the boron
Source is selected from boric acid, and the organic amine is selected from piperidines, and the organosilicon is selected from dimethyl diethoxysilane, dimethyldichlorosilane
Or at least one of dimethyl chloride bromo-silicane.
9. the method that epoxidation of cyclohexene according to claim 7 prepares 7-oxa-bicyclo[4.1.0, which is characterized in that acid processing
The step of Ti-MWW molecular screen primary powder is that the acid solution that Ti-MWW molecular screen primary powder and piperidines and concentration are 1~5mol/L presses matter
Amount is than being 1:(0.1~0.5): (20~40) are mixed, and are handled 10~30 hours in 60~95 DEG C, through centrifugation, washing, are done
It is dry, obtain Ti-MWW molecular sieve acid-treated product；The acid solution is selected from least one of nitric acid or hydrochloric acid solution.
10. the method that epoxidation of cyclohexene according to claim 7 prepares 7-oxa-bicyclo[4.1.0, which is characterized in that high temperature roasting
The step of burning is to roast Ti-MWW molecular sieve acid-treated product 6~10 hours in 500~600 DEG C, air or oxygen atmosphere,
Obtain Ti-MWW zeolite product.
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