CN104447627B - A kind of olefin epoxidation method - Google Patents
A kind of olefin epoxidation method Download PDFInfo
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- CN104447627B CN104447627B CN201310413508.XA CN201310413508A CN104447627B CN 104447627 B CN104447627 B CN 104447627B CN 201310413508 A CN201310413508 A CN 201310413508A CN 104447627 B CN104447627 B CN 104447627B
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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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- 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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Abstract
A kind of olefin epoxidation method, is under the reaction condition of alkene epoxidation, alkene and oxidant is carried out haptoreaction with catalyst on a fixed bed, it is characterised in that including whenever index（a）The conversion ratio of oxidant reduces, touches 90% and/or index in course of reaction（b）When the selectivity of purpose product oxyalkylene reduces, touches 92%, with 0.01~0.5h‑1/ d total the air speed of amplitude reduction system so that work as index（c）The conversion ratio of oxidant rises, touches 94% and/or index（d）When the selectivity of purpose product oxyalkylene rises, touches 94%, the step of keeping system total air speed.This method can maintain the total conversion ratio of oxidant and purpose product selectivity in reaction contact process, extend total run time, while delaying catalyst inactivation, and then improve catalyst life.
Description
Technical field
The present invention relates to a kind of olefin epoxidation method.
Background technology
Oxyalkylene is the important oxygen-containing organic compound of a class, also known as such as propylene oxide, expoxy propane
（Propylene oxide, abbreviation PO）, it is a kind of important basic organic chemical industry raw material, yield is only secondary in acryloyl derivative
In polypropylene.Purposes maximum PO is production PPG, to be processed further manufacturing polyurethane, it can also be used to produce purposes
Extensive propane diols.In addition, expoxy propane can be additionally used in surfactant, the production of oil field demulsifier etc..
With the extensive use of polyurethane material etc., the demand of expoxy propane is rising year by year.At present, industrial production
The technique of expoxy propane has drawback, and the requirement of green chemistry chemical technology is not met especially.Therefore, people are in the urgent need to developing
Economic and environment amenable production method.
Titanium-silicon molecular sieve TS-1（US4410501）Appearance, be oxidation of alkene epoxidation, phenol hydroxylation, keto-alcohol etc.
Open up a new way, particularly in terms of alkene epoxidation, achieve good catalytic oxidation effect.With peroxidating
In the reaction system that hydrogen is oxidant, methanol is solvent, HTS has higher catalytic activity to propylene, at present,
Dow/BASF and Degussa/Uhde push the technique to industrialization.
But common problem is, device was operated after a period of time, and the activity and selectivity of catalyst can be reduced, that is, be urged
Deactivation phenomenom can occur in operation process for agent.The mode mainly solved at present is to use two kinds of in-situ regeneration and ex-situ regeneration
Mode makes renewing catalyst activity.Wherein, in-situ regeneration is primarily directed to the lighter situation of level of deactivation, typically using solvent
And/or oxidant impregnates or rinsed certain time to realize at a certain temperature；Ex-situ regeneration primarily directed to level of deactivation compared with
Serious situation is general to be realized using modes such as roastings.Typically industrially, using first making catalyst extensive through in-situ regeneration
It is active, after in-situ regeneration can not recover catalyst activity, then using ex-situ regeneration.So regenerating the problem of existing is
When reruning after regeneration, when particularly being reruned after in-situ regeneration, the activity and selectivity fluctuation of catalyst is larger, needs
Stabilization is lot more time to, improves the operation such as reaction temperature to realize the steady operating of reaction, but so meeting while to combine
Catalyst inactivation and reduction purpose product selectivity are further speeded up, subsequent product refining spearation is influenceed, is also unfavorable for safety
Production.
CN101279959A discloses a kind of method of synthesizing epoxypropane, it is characterised in that solution ph and reaction temperature
Adjusted at any time according to hydrogen peroxide conversion ratio in whole course of reaction, as soon as hydrogen peroxide conversion ratio is reduced to 88.5%, improve molten
Liquid pH value and reaction temperature.The invention can extend the single run life-span of catalyst by adjusting solution ph and reaction temperature.
But this method is unfavorable for the repeated multiple times regeneration of catalyst, that is, influences the entire life of catalyst, because improving after reaction temperature,
The speed of catalyst inactivation is accelerated, and this catalyst inactivated after rise temperature is difficult to carry out in-situ regeneration, and again
Activity is difficult to obtain complete recovery after life.
The content of the invention
The purpose of the present invention be for existing process exist not enough there is provided a kind of preparation method of oxyalkylene.This
The inventor of invention has found by substantial amounts of research, in the preparation process of oxyalkylene, when epoxidation reaction of olefines carries out one
, can be with the choosing of the conversion ratio of maintenance reaction thing and purpose product by total air speed of appropriate amplitude reduction system after the section time
Selecting property is in higher scope, while extending the one way duration of runs of catalyst.More surprisingly, effective profit of oxidant
Also it is improved with rate.In this way catalyst can multiple in-situ regeneration repeatedly, the total run time of catalyst is also
To greatly prolonging, so as to reduce further the unit consumption of catalyst, cost has been saved.Based on this, the present invention is completed.
The olefin epoxidation method that the present invention is provided, is under the reaction condition of alkene epoxidation, to make alkene and oxidation
Agent carries out haptoreaction with catalyst on a fixed bed, it is characterised in that including whenever index（a）Oxidant in course of reaction
Conversion ratio reduces, touches 90% and/or index（b）The selectivity reduction of purpose product oxyalkylene, when touching 92%, with 0.01~
0.5h-1/ d total the air speed of amplitude reduction system so that work as index（c）The conversion ratio of oxidant rises, touches 94% and/or index
（d）When the selectivity of purpose product oxyalkylene rises, touches 94%, the step of keeping system total air speed.
In the method that the present invention is provided, These parameters percentage refers both to the form of mole percent, i.e. index（a）It is reaction
During oxidant conversion ratio（Mole percent）；Index（b）The selectivity of purpose product oxyalkylene（Mole percent）；
Index（c）The conversion ratio of oxidant（Mole percent）；Index（d）The selectivity of purpose product oxyalkylene（Mole percent
Number）.
In the method that the present invention is provided, described catalyst is using HTS as active component, and catalyst grain size is excellent
Elect 0.5~20000 micron as.The present invention is not particularly limited for the content of titanium atom in HTS, can be ability
The conventional selection in domain.Specifically, HTS chemical formula xTiO2·SiO2During expression, x can be 0.0001~0.04, excellent
Elect 0.01~0.03, more preferably 0.015~0.025 as.The HTS can have various topology knots for common
The HTS of structure, for example：The HTS can be selected from the HTS of MFI structure（Such as TS-1）, MEL structures
HTS（Such as TS-2）, BEA structures HTS（Such as Ti-Beta）, MWW structures HTS（Such as Ti-
MCM-22）, hexagonal structure HTS（Such as Ti-MCM-41, Ti-SBA-15）, MOR structures HTS（Such as Ti-
MOR）, TUN structures HTS（Such as Ti-TUN）With the HTS of other structures（Such as Ti-ZSM-48）.
Preferably, the HTS is selected from HTS, the HTS and BEA of MEL structures of MFI structure
The HTS of structure.It is highly preferred that the HTS is the titanium-silicon molecular sieve TS-1 of MFI structure.From further carrying
The effective rate of utilization of hyperoxia agent and the angle of selectivity of product are set out, and the crystal grain of the HTS is hollow-core construction,
The radical length of the chamber portion of the hollow-core construction is 5~300 nanometers, and the HTS is in 25 DEG C, P/P0=0.10、
Adsorption time is that the benzene adsorbance measured under conditions of 1 hour is at least 70 milligrams per grams, the nitrogen absorption under low temperature of the HTS
Adsorption isotherm and desorption isotherm between there is hysteresis loop.Herein, the HTS with the structure is referred to as hollow
HTS HTS.The hollow HTS is commercially available（For example feldspathization stock is built commercially available from Sinopec Hunan
The molecular sieve that the trade mark of part Co., Ltd is HTS）, method that can also be according to disclosed in CN1132699C prepares.
The present invention most preferred embodiment in, described catalyst be set in described fixed bed HTS and
TS-1 two parts, and described alkene and oxidant is first contacted with HTS, then contacted with TS-1.Described HTS with it is described
TS-1 mass ratio is 1~20：1st, preferably 2~10：1.
In the method that the present invention is provided, the amount of catalyst is not particularly limited, and is met reaction and is required that bed is honest and kind can
To be needed to carry out flexible modulation according to reaction.And can according to reaction needs, using inert filler for example quartz sand, ceramic ring,
Potsherd etc. is diluted to catalyst.
In described method, described alkene is the alkene of no more than 12 carbon atoms, and preferably carbon number is 2~6
Alkene, more preferably propylene and butylene.
In described method, the instantiation of oxidant can include but is not limited to：Hydrogen peroxide, tert-butyl hydroperoxide
Hydrogen, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant is peroxidating
Hydrogen, so can further reduce separation costs.Typically using mass percentage concentration as 5~70% aqueous hydrogen peroxide solution
Form is added in reaction system, such as the aqueous hydrogen peroxide solution of technical grade has 27.5%, 30%, 55% and 70%.
In described method, solvent is may be incorporated into the efficiency of reaction, reaction system in order to improve, solvent bag used
Ketone, alcohols, nitrile are included, methanol, ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone, second is selected from
One or more mixing in nitrile, acrylonitrile, wherein it is preferred that methanol, acetone or the tert-butyl alcohol.Wherein, described solvent is selected from first
Alcohol, ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol or acetone.More preferably solvent is methanol.
The method that the present invention is provided, wherein, described olefin hydrocarbon oxidation reaction condition is 0~120 DEG C of temperature, pressure 0.01~
The mol ratio of 5MPa, alkene and oxidant is 1~10：1, the mol ratio of solvent and alkene is 0~100：1, in system during gross weight
Air speed is 0.1~20h-1.Preferably, described temperature is 20~80 DEG C, pressure is 0.1~3MPa, and alkene and oxidant rub
You are than being 0.2~5：1, the mol ratio of solvent and alkene is 0.2~80：1, total weight (hourly) space velocity (WHSV) is 0.5~15h in system-1。
It is described with certain total air speed of amplitude reduction system in the method that the present invention is provided, in terms of weight (hourly) space velocity (WHSV), drop
The low total air speed of system can arrive 0.5h-1Below, it might even be possible to reach 0.2h-1Hereinafter, the present invention does not have particular/special requirement to this.But
If reducing, the total air speed of system is excessive, and product yield is relatively low, angularly considers from economy, and the total air speed of system can be reduced to
0.5h-1。
It is preferred embodiment to work as index in described method（a）Change into the conversion ratio of oxidant in course of reaction
Reduce, touch 92% and/or work as index（b）When changing into the selectivity reduction of purpose product oxyalkylene, touching 94%, with 0.02
~0.2h-1/ d total the air speed of amplitude reduction system so that work as index（c）The conversion ratio for changing into oxidant rises, touches 95%
And/or index（d）When the selectivity for changing into purpose product oxyalkylene rises, touches 95%, the total air speed of system is kept.
The preparation method of oxyalkylene provided by the present invention, can maintain turn of oxidant always in reaction contact process
Rate and purpose product selectivity, extend total run time, while delaying catalyst inactivation, improve catalyst life.And
And purpose product selectivity is high in use, catalyst activity stability is good, and process is simple and easy to control, beneficial to industrial metaplasia
Production and application.
Embodiment
Following embodiment will be further described to the present invention, but and be not so limited present disclosure.
In embodiment and comparative example, agents useful for same is commercially available chemical pure or AR.
HTS used in embodiment and comparative example（TS-1）It is by prior art Zeolites 1992,
What the method described in Vol.12 pages 943~950 was prepared（TS-1）Sieve sample, its titanium oxide content is 2.5 weights
Measure %；Hollow HTS HTS produces for Sinopec Hunan Jianchang Petrochemical Co., Ltd, is Chinese patent
The industrial products of HTS described in CN1301599A.Through analysis, the HTS is MFI structure, its titanium oxide content
For 2.5 weight %, there is hysteresis loop between the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of the HTS, it is brilliant
Grain is that the radical length of hollow crystal grain and chamber portion is 15~180 nanometers；The HTS sample is in 25 DEG C, P/P0=
0.10, adsorption time is that the benzene adsorbance measured under conditions of 1 hour is 78 milligrams per grams.
In embodiment and comparative example, the preparation method of microspherical catalyst used is as follows：Under the conditions of normal pressure and 60 DEG C, first will
Organo-silicon compound tetraethyl orthosilicate is added in the TPAOH aqueous solution and mixed, and stirring hydrolysis 5h obtains gluey molten
Liquid；Then HTS is added to be well mixed among above-mentioned gained colloidal solution and obtains slurries, and it is HTS, organic
The mass ratio of silicide, TPAOH and water is 100:25:5:250；Above-mentioned slurries are continued to stir after 2h, through routine
Roasting can obtain the catalyst of the microballoon shape used in the present invention after mist projection granulating（20~80 microns of granularity）.
In embodiment and comparative example, olefin hydrocarbon oxidation reaction is carried out in common micro fixed-bed reactor.
In comparative example and embodiment, the content of each composition in obtained reaction solution is analyzed using gas-chromatography, herein
On the basis of below equation is respectively adopted calculate oxidant conversion ratio, oxidant effective rate of utilization and oxyalkylene selectivity：
Comparative example 1
Epoxidation of propylene situation when this comparative example illustrates not use the inventive method.
By propylene, hydrogen peroxide, solvent and TS-1 microspherical catalysts according to propylene and hydrogen peroxide mol ratio be 3：1,
Solvent acetone and the mol ratio of propylene are 10：1, the total weight (hourly) space velocity (WHSV) of system is 5.5h-1, it is under 45 DEG C of pressure are 2.0MPa in temperature
Reacted.The result of reaction 2 hours is as follows：Hydrogen peroxide conversion 98%；Effective utilization ratio of hydrogen peroxide is 90%；Epoxy third
Alkane is selectively 95%.The result of reaction 240 hours is as follows：Hydrogen peroxide conversion 95%；Effective utilization ratio of hydrogen peroxide is
86%；Expoxy propane is selectively 90%.The result of reaction 360 hours is as follows：Hydrogen peroxide conversion 81%；Hydrogen peroxide is effective
Utilization rate is 81%；Expoxy propane is selectively 86%.
Embodiment 1
This example demonstrates that using epoxidation of propylene situation during the inventive method.
Epoxidation of propylene condition with comparative example 1, unlike reaction 240 hours after, with 0.02~0.2h-1/ d amplitude
The total air speed of reduction system so that when oxidant conversion ratio rise, touch 94% and purpose product oxyalkylene selectivity on
When rising, touching 94%, the total air speed of system is kept, until the total air speed of system is reduced to 0.5h-1.The result of reaction 360 hours is as follows：
Hydrogen peroxide conversion 96%；Effective utilization ratio of hydrogen peroxide is 89%；Expoxy propane is selectively 95%.The knot of reaction 720 hours
Fruit is as follows：Hydrogen peroxide conversion 93%；Effective utilization ratio of hydrogen peroxide is 87%；Expoxy propane is selectively 94%.
Embodiment 2
This example demonstrates that using epoxidation of propylene situation during the inventive method.
Epoxidation of propylene condition be the same as Example 1, during the reduction total air speed of system so that rise when the conversion ratio of oxidant, touch
And 95% or the selectivity of purpose product oxyalkylene rise, when touching 95%, keep the total air speed of system.The knot of reaction 360 hours
Fruit is as follows：Hydrogen peroxide conversion 97%；Effective utilization ratio of hydrogen peroxide is 90%；Expoxy propane is selectively 96%.Reaction 720
The result of hour is as follows：Hydrogen peroxide conversion 95%；Effective utilization ratio of hydrogen peroxide is 88%；Expoxy propane is selectively 95%.
Comparative example 2
Epoxidation of propylene situation when this comparative example illustrates not use the inventive method.
By propylene, hydrogen peroxide, solvent and HTS microspherical catalysts according to propylene and hydrogen peroxide mol ratio be 2：1, it is molten
The mol ratio of agent methanol and propylene is 10:1, the total weight (hourly) space velocity (WHSV) of system is 8.0h-1, it is that 50 DEG C of pressure are to enter under 2.5MPa in temperature
Row reaction.The result of reaction 2 hours is as follows：Hydrogen peroxide conversion 97%；Effective utilization ratio of hydrogen peroxide is 92%；Expoxy propane
Selectivity is 97%.The result of reaction 240 hours is as follows：Hydrogen peroxide conversion 95%；Effective utilization ratio of hydrogen peroxide is 88%；
Expoxy propane is selectively 92%.The result of reaction 360 hours is as follows：Hydrogen peroxide conversion 91%；Hydrogen peroxide is effectively utilized
Rate is 85%；Expoxy propane is selectively 90%.
Embodiment 3
This example demonstrates that using epoxidation of propylene situation during the inventive method.
Epoxidation of propylene condition with comparative example 2, unlike reaction 240 hours after, 0.02~1.0h-1/ d amplitude drop
The low total air speed of system so that when oxidant conversion ratio rise, touch 95% and purpose product oxyalkylene selectivity rise,
When touching 95%, the total air speed of system is kept, until the total air speed of system reaches 0.5h-1.The result of reaction 360 hours is as follows：Peroxidating
Hydrogen conversion ratio 96%；Effective utilization ratio of hydrogen peroxide is 90%；Expoxy propane is selectively 95%.The result of reaction 720 hours is such as
Under：Hydrogen peroxide conversion 95%；Effective utilization ratio of hydrogen peroxide is 89%；Expoxy propane is selectively 95%.Reaction 960 hours
Result it is as follows：Hydrogen peroxide conversion 92%；Effective utilization ratio of hydrogen peroxide is 86%；Expoxy propane is selectively 93%.
Embodiment 4
This example demonstrates that using epoxidation of propylene situation during the inventive method.
Epoxidation of propylene condition be the same as Example 3, the difference is that catalyst is 10 by mass ratio:1 HTS and TS-1 is substituted,
And described alkene and oxidant is first contacted with HTS, then contacted with TS-1.The result of reaction 360 hours is as follows：Hydrogen peroxide
Conversion ratio 98%；Effective utilization ratio of hydrogen peroxide is 92%；Expoxy propane is selectively 97%.The result of reaction 720 hours is as follows：
Hydrogen peroxide conversion 96%；Effective utilization ratio of hydrogen peroxide is 90%；Expoxy propane is selectively 96%.The knot of reaction 960 hours
Fruit is as follows：Hydrogen peroxide conversion 95%；Effective utilization ratio of hydrogen peroxide is 88%；Expoxy propane is selectively 95%.
Embodiment 5
This example demonstrates that using epoxidation of propylene situation during the inventive method.
Epoxidation of propylene condition be the same as Example 4, unlike described alkene and oxidant is first contacted with TS-1, then with
HTS is contacted.The result of reaction 360 hours is as follows：Hydrogen peroxide conversion 94%；Effective utilization ratio of hydrogen peroxide is 90%；Epoxy
Propane selectivity is 92%.The result of reaction 720 hours is as follows：Hydrogen peroxide conversion 90%；Effective utilization ratio of hydrogen peroxide is
85%；Expoxy propane is selectively 90%.The result of reaction 960 hours is as follows：Hydrogen peroxide conversion 84%；Hydrogen peroxide is effective
Utilization rate is 81%；Expoxy propane is selectively 83%.
Embodiment 6
This example demonstrates that using epoxidation of propylene situation during the inventive method.
Epoxidation of propylene condition be the same as Example 4, the difference is that catalyst is 1 by mass ratio:1 HTS and TS-1 is substituted, and
Described alkene and oxidant is first contacted with HTS, then contacted with TS-1.The result of reaction 360 hours is as follows：Hydrogen peroxide turns
Rate 96%；Effective utilization ratio of hydrogen peroxide is 90%；Expoxy propane is selectively 95%.The result of reaction 720 hours is as follows：Cross
Hydrogen oxide conversion ratio 92%；Effective utilization ratio of hydrogen peroxide is 86%；Expoxy propane is selectively 92%.The result of reaction 960 hours
It is as follows：Hydrogen peroxide conversion 89%；Effective utilization ratio of hydrogen peroxide is 83%；Expoxy propane is selectively 90%.
Embodiment 7
This example demonstrates that using epoxidation of propylene situation during the inventive method.
Epoxidation of propylene condition be the same as Example 4, the difference is that catalyst is 15 by mass ratio:1 HTS and TS-1 is substituted,
And described alkene and oxidant is first contacted with HTS, then contacted with TS-1.The result of reaction 360 hours is as follows：Hydrogen peroxide
Conversion ratio 98%；Effective utilization ratio of hydrogen peroxide is 91%；Expoxy propane is selectively 96%.The result of reaction 720 hours is as follows：
Hydrogen peroxide conversion 94%；Effective utilization ratio of hydrogen peroxide is 87%；Expoxy propane is selectively 94%.The knot of reaction 960 hours
Fruit is as follows：Hydrogen peroxide conversion 90%；Effective utilization ratio of hydrogen peroxide is 85%；Expoxy propane is selectively 90%.
Embodiment 8
This example demonstrates that using butylene epoxidation situation during the inventive method.
Alkene epoxidation condition be the same as Example 4, the difference is that alkene substitutes propylene by butylene, oxidant is by t-butyl peroxy
Change hydrogen and replace hydrogen peroxide.The result of reaction 360 hours is as follows：TBHP conversion ratio 93%；Oxidant is effectively utilized
Rate is 89%；Epoxy butane is selectively 94%.The result of reaction 720 hours is as follows：TBHP conversion ratio 92%；Oxygen
Agent effective rate of utilization is 87%；Epoxy butane is selectively 92%.The result of reaction 960 hours is as follows：TBHP
Conversion ratio 90%；Oxidant effective rate of utilization is 85%；Epoxy butane is selectively 90%.
It can be seen that from embodiment and comparative example：The production method of the present invention maintains oxidant effective rate of utilization and purpose production
Thing selectivity, while delaying catalyst inactivation, extends total run time in higher scope, and then improves catalyst
Entire life.
Claims (8)
1. a kind of olefin epoxidation method, is under the reaction condition of alkene epoxidation, to make alkene and oxidant in fixed bed
Upper and catalyst carries out haptoreaction, it is characterised in that reduced including the conversion ratio whenever oxidant in index (a) course of reaction,
Touch 90% and/or index (b) purpose product oxyalkylene selectivity reduction, when touching 92%, with 0.01~0.5h-1/ d's
The total air speed of amplitude reduction system so that when index (c) oxidant conversion ratio rise, touch 94% and/or index (d) purpose production
When the selectivity of compound oxyalkylene hydrocarbon rises, touches 94%, the step of keeping system total air speed；Described catalyst is consolidated in described
HTS and TS-1 two parts are set in fixed bed, described HTS and described TS-1 mass ratio is 2~10：1, and make described
Alkene and oxidant are first contacted with HTS, then are contacted with TS-1；Described HTS, crystal grain is hollow-core construction, the sky of the hollow-core construction
The radical length of cavity segment is 5~300 nanometers, and the HTS is in 25 DEG C, P/P0=0.10, adsorption time is 1 small
When under conditions of the benzene adsorbance that measures be at least 70 milligrams per grams, the adsorption isotherm of the nitrogen absorption under low temperature of the HTS
There is hysteresis loop between desorption isotherm, described alkene is the alkene that carbon number is 2~6；Described alkene epoxidation
Reaction condition be that the mol ratio that temperature is 0~120 DEG C, pressure is 0.01~5MPa, alkene and oxidant is 1~10：1, it is molten
The mol ratio of agent and alkene is 2~80：1, the total weight (hourly) space velocity (WHSV) of system is 0.2~20h-1。
2. according to the method for claim 1 wherein, described reaction temperature is 20~80 DEG C, and reaction pressure is 0.1~3MPa,
The mol ratio of alkene and oxidant is 1~5.0：1, the mol ratio of solvent and alkene is 2~80：1, the total weight (hourly) space velocity (WHSV) of system is
0.5~15h-1。
3. according to the method for claim 1 wherein described alkene is propylene or butylene.
4. according to the method for claim 1 or 2, wherein, described oxidant is the aquae hydrogenii dioxidi that mass concentration is 5~70%
Solution.
5. according to the method for claim 1 or 2, wherein, described solvent is selected from methanol, ethanol, normal propyl alcohol, isopropanol, tertiary fourth
Alcohol, isobutanol or acetone.
6. according to the method for claim 1 wherein index (a) is the conversion ratio reduction of oxidant in course of reaction, touched
92%, index (b) reduces for the selectivity of purpose product oxyalkylene, touches 94%.
7. according to the method for claim 1 wherein the amplitude of the described total air speed of reduction system is 0.02~0.2h-1/d。
8. according to the method for claim 1 wherein index (c) rises for the conversion ratio of oxidant, touches 95%；Described finger
Mark (d) rises for the selectivity of purpose product oxyalkylene, touches 95%.
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