CN104447626A - Alkene oxidation method - Google Patents

Alkene oxidation method Download PDF

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Publication number
CN104447626A
CN104447626A CN201310413018.XA CN201310413018A CN104447626A CN 104447626 A CN104447626 A CN 104447626A CN 201310413018 A CN201310413018 A CN 201310413018A CN 104447626 A CN104447626 A CN 104447626A
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oxygenant
hts
alkene
index
selectivity
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CN104447626B (en
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朱斌
史春风
林民
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Epoxy Compounds (AREA)

Abstract

The invention relates to an alkene oxidation method. Specifically, under alkene oxidation reaction conditions, alkene and an oxidizing agent undergo contact reaction with a catalyst on a fixed bed. The method is characterized by comprising the steps that whenever index (a) the conversion rate of the oxidizing agent drops and reaches 90% in the reaction process, and/or index (b) the selectivity of the target product oxidized alkene drops and reaches 92%, the space velocity of the oxidizing agent is reduced at an amplitude of 0.001-0.15h<-1>/d, so that when index (c) the conversion rate of the oxidizing agent rises and reaches 94%, and/or index (d) the selectivity of the target product oxidized alkene rises and reaches 94%, the space velocity of the oxidizing agent is maintained. The method can keep the total conversion rate of the oxidizing agent and the target product selectivity in the reaction contact process, lengthens the total running time, simultaneously delays deactivation of the catalyst, and prolongs the service life of the catalyst.

Description

A kind of method of olefin oxidation
Technical field
The present invention relates to a kind of method of olefin oxidation.
Background technology
Olefin oxide is the important oxygen-containing organic compound of a class, and as propylene oxide, be also called propylene oxide (propylene oxide is called for short PO), be a kind of important basic organic chemical industry raw material, in acryloyl derivative, output is only second to polypropylene.The maximum purposes of PO produces polyether glycol, with further processing and manufacturing urethane, also can be used for producing broad-spectrum propylene glycol.In addition, propylene oxide also can be used for tensio-active agent, the production of oil field demulsifier etc.
Along with the widespread use of polyurethane material etc., the demand of propylene oxide is rising year by year.At present, the technique of industrial production propylene oxide also exists drawback, does not especially meet the requirement of green chemistry chemical technology.Therefore, people are in the urgent need to exploitation i.e. economy and but also environment amenable production method.
The appearance of titanium-silicon molecular sieve TS-1 (US4410501), for the oxidation etc. of alkene epoxidation, phenol hydroxylation, keto-alcohol opens up a new way, particularly in alkene epoxidation, achieves good catalytic oxidation effect.Take hydrogen peroxide as oxygenant, in the methyl alcohol reaction system that is solvent, HTS has higher catalytic activity to propylene, and at present, Dow/BASF and Degussa/Uhde pushes this technique to industrialization.
But the common problem existed is that device operates after for some time, and the activity and selectivity of catalyzer can reduce, and namely catalyzer deactivation phenomenom can occur in operation process.The mode mainly solved at present adopts in-situ regeneration and ex-situ regeneration two kinds of modes to make renewing catalyst activity.Wherein, in-situ regeneration is mainly for the situation that level of deactivation is lighter, and general solvent and/or the oxygenant of adopting floods at a certain temperature or rinse certain hour to realize; Ex-situ regeneration is mainly for the situation that level of deactivation is more serious, and the general modes such as roasting that adopt realize.General industrially employing first makes renewing catalyst activity through in-situ regeneration, after in-situ regeneration cannot make catalyst activity recover by the time, then adopts ex-situ regeneration.Such regeneration Problems existing is when reruning after regeneration, when particularly reruning after in-situ regeneration, the activity and selectivity fluctuation of catalyzer is larger, need could stablize for a long time, the smooth operation of realization response will be carried out in conjunction with operations such as improving temperature of reaction simultaneously, but the further accelerator activator inactivation of meeting and reduction object selectivity of product, affect subsequent product refining spearation, be also unfavorable for safety in production like this.
CN101279959A discloses a kind of method of synthesizing epoxypropane, it is characterized in that the low-carbon alcohol of mol ratio 1 ~ 15:0.5 ~ 5:1, propylene, hydrogen peroxide are in the reactor that catalyzer is housed, propylene and hydrogen peroxide initial ring oxidizing reaction obtain propylene oxide, wherein solution ph and temperature of reaction regulate according to hydrogen peroxide transformation efficiency at any time in whole reaction process, hydrogen peroxide transformation efficiency one is reduced to 88.5%, just improves solution ph and temperature of reaction.This invention can single run life-span of extending catalyst by regulator solution pH value and temperature of reaction, and catalyzer single pass life can reach more than 1200 hours.But this method is unfavorable for the repeated multiple times regeneration of catalyzer, namely affect the operation entire life of catalyzer.
Summary of the invention
Namely object of the present invention is to provide a kind of method of olefin oxidation.
The present inventor experimental studies have found that through a large amount of, when oxygenant low conversion rate in epoxidation reaction of olefines operational process in 90% and/or object product olefin oxide selectivity lower than 92% time, the air speed of system oxygenant is reduced with certain amplitude, other material air speed remains unchanged, the selectivity of the transformation efficiency and object product olefin oxide that can maintain oxygenant in higher level, and then extends alkene epoxidation parallel-adder settle-out time.Based on this, complete the present invention.
Method provided by the invention, under olefin hydrocarbon oxidation reaction condition, alkene and oxygenant is made to carry out contact reacts with catalyzer on a fixed bed, the transformation efficiency that it is characterized in that comprising oxygenant in index (a) reaction process reduces, touch 90% and/or the selectivity of index (b) object product olefin oxide reduces, when touching 92%, with 0.001 ~ 0.15h -1the amplitude of/d reduces the air speed of oxygenant, make the transformation efficiency when index (c) oxygenant increase, touch 94% and/or index (d) object product olefin oxide selectivity rising, when touching 94%, the step of the air speed of maintenance oxygenant.
In method provided by the invention, These parameters percentage ratio all refers to the form of molecular fraction, and namely index (a) is the transformation efficiency (molecular fraction) of oxygenant in reaction process; The selectivity (molecular fraction) of index (b) object product olefin oxide; The transformation efficiency (molecular fraction) of index (c) oxygenant; The selectivity (molecular fraction) of index (d) object product olefin oxide.
In method provided by the invention, said catalyzer take HTS as active component, and catalyst grain size is preferably 0.5 ~ 20000 micron.The present invention is not particularly limited for the content of titanium atom in HTS, can be that the routine of this area is selected.Particularly, HTS chemical formula xTiO 2siO 2during expression, x can be 0.0001 ~ 0.04, is preferably 0.01 ~ 0.03, is more preferably 0.015 ~ 0.025.Described HTS can for the common HTS with various topological framework, such as: described HTS can be selected from the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.
Preferably, described HTS is selected from the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure.More preferably, described HTS is the titanium-silicon molecular sieve TS-1 of MFI structure.From improving the effective rate of utilization of oxygenant and the angle of selectivity of product further, the crystal grain of described HTS is hollow structure, and the radical length of the chamber portion of this hollow structure is 5 ~ 300 nanometers, and described HTS is at 25 DEG C, P/P 0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.Herein, the HTS with this structure is called hollow HTS HTS.Described hollow HTS can be commercially available (be such as purchased from the trade mark of Sinopec Hunan Jianchang Petrochemical Co., Ltd be the molecular sieve of HTS), also method can prepare disclosed in CN1132699C.
In most preferred embodiment of the present invention, said catalyzer is set to HTS and TS-1 two portions in said fixed bed, and said alkene is first contacted with HTS with oxygenant, then contacts with TS-1.The mass ratio of said HTS and said TS-1 is 1 ~ 20:1, preferably 2 ~ 10:1.
In method provided by the invention, the amount of catalyzer is without particular determination, and satisfied reaction requires, bed is honest and kind can carry out flexible according to reaction needed.And can, according to reaction needed, utilize inert filler such as quartz sand, ceramic ring, potsherd etc. to dilute catalyzer.
In said method, said alkene is the alkene being not more than 12 carbon atoms, and preferred carbonatoms is the alkene of 2 ~ 6, more preferably propylene and butylene.
In said method, the specific examples of oxygenant can include but not limited to: hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid.Preferably, described oxygenant is hydrogen peroxide, can reduce separation costs further like this.Be normally that the form of the aqueous hydrogen peroxide solution of 5 ~ 70% adds in reaction system with mass percentage concentration, the aqueous hydrogen peroxide solution of such as technical grade has 27.5%, 30%, 55% and 70% etc.
In said method, in order to improve the efficiency of reaction, solvent can also be introduced in reaction system, solvent used comprises ketone, alcohols, nitrile, such as be selected from one or more the mixing in methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone, acetonitrile, vinyl cyanide, wherein particular methanol, acetone or the trimethyl carbinol.Wherein, said solvent selected from methanol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol or acetone.Particular methanol, the trimethyl carbinol or acetone, more preferably solvent is methyl alcohol.
Method provided by the invention, wherein, said olefin hydrocarbon oxidation reaction condition is temperature 0 ~ 120 DEG C, pressure 0.01 ~ 5MPa, the mol ratio of alkene and oxygenant is 1 ~ 10:1, and the mol ratio of solvent and alkene is 0 ~ 100:1, and in system, the weight hourly space velocity of oxygenant is 0.05 ~ 20h -1.Preferably, said temperature is 20 ~ 80 DEG C, and pressure is 0.1 ~ 3MPa, and the mol ratio of alkene and oxygenant is 0.2 ~ 5:1, and the mol ratio of solvent and alkene is 0.2 ~ 80:1, and in system, the weight hourly space velocity of oxygenant is 0.1 ~ 10h -1.
In method provided by the invention, said with the air speed of oxygenant in certain amplitude reduction system, in weight hourly space velocity, the air speed reducing system oxygenant can arrive 0.02h -1below, even 0.01h can be reached -1below, the present invention does not have particular requirement to this.If but the air speed reducing system oxygenant is excessive, product yield is lower, angularly considers from economy, and the air speed of system oxygenant can be reduced to 0.02h -1.
In said method, be preferred embodiment the transformation efficiency changing into oxygenant in reaction process when index (a) reduce, touch 92% and/or when the selectivity that index (b) changes into object product olefin oxide reduce, touch 94% time, the amplitude of air speed of reduction oxygenant is 0.02 ~ 0.10h -1/ d, makes the transformation efficiency changing into oxygenant when index (c) rise, touches 95% and/or index (d) selectivity of changing into object product olefin oxide rises, when touching 95%, keep the air speed of oxygenant.
Method provided by the present invention, can maintain the total transformation efficiency of oxygenant and object selectivity of product, total working time be extended, delays catalyst deactivation simultaneously, improve catalyst life in reaction contact process.In use object selectivity of product is high simultaneously, and catalyst activity good stability, process is simple and easy to control, is beneficial to suitability for industrialized production and application.
Embodiment
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.
In embodiment and comparative example, agents useful for same is commercially available chemical pure or analytical reagent.
In comparative example and embodiment, HTS (TS-1) used is by prior art Zeolites, and the TS-1 sieve sample that the method described in 1992, Vol.12 943rd ~ 950 pages is prepared, its titanium oxide content is 2.5 % by weight.Hollow HTS HTS is that Sinopec Hunan Jianchang Petrochemical Co., Ltd produces, and is the Industrial products of HTS described in Chinese patent CN1301599A.By analysis, this HTS is MFI structure, its titanium oxide content is 2.5 % by weight, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, and crystal grain is hollow crystal grain and the radical length of chamber portion is 15 ~ 180 nanometers; This HTS sample at 25 DEG C, P/P 0=0.10, adsorption time is the benzene adsorptive capacity recorded under the condition of 1 hour is 78 milligrams/gram.
In embodiment and comparative example, the preparation method of microspherical catalyst used is as follows: under normal pressure and 60 DEG C of conditions, is first joined in the TPAOH aqueous solution by silicoorganic compound tetraethoxy and mixes, and stirs hydrolysis 5h and obtains colloidal solution; Then HTS is added to mix among above-mentioned gained colloidal solution and obtain slurries, and the mass ratio of HTS, silanes, TPAOH and water is 100:25:5:250; After above-mentioned slurries are continued to stir 2h, after conventional mist projection granulating, roasting can obtain the catalyzer (granularity 20 ~ 80 microns) of the present invention's microballoon shape used.
In embodiment and comparative example, olefin hydrocarbon oxidation reaction is all carry out in common micro fixed-bed reactor.
In comparative example and embodiment, adopt gas-chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate oxygenant transformation efficiency, oxygenant effective rate of utilization and olefin oxide selectivity on this basis respectively:
Comparative example 1
This comparative example illustrates epoxidation of propylene situation when not adopting the inventive method.
Be 3:1 by propylene, hydrogen peroxide, solvent and TS-1 microspherical catalyst according to the mol ratio of propylene and hydrogen peroxide, the mol ratio of solvent acetone and propylene is 10:1, and in system, the weight hourly space velocity of oxygenant is 5.0h -1, react under be 40 DEG C of pressure being 2.5MPa in temperature.The result of reacting 2 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 90%; Propylene oxide selectivity is 96%.The result of reacting 240 hours is as follows: hydrogen peroxide conversion 92%; Effective utilization ratio of hydrogen peroxide is 87%; Propylene oxide selectivity is 93%.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 85%; Effective utilization ratio of hydrogen peroxide is 83%; Propylene oxide selectivity is 88%.
Embodiment 1
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition with comparative example 1, unlike in reaction after 240 hours, with 0.02 ~ 0.2h -1the amplitude of/d reduces the air speed of system oxygenant, make the transformation efficiency when oxygenant increase, touch 94% and object product olefin oxide selectivity rising, when touching 94%, the air speed of maintenance system oxygenant, until the air speed of oxygenant is reduced to 0.02h in system -1.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 88%; Propylene oxide selectivity is 94%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 92%; Effective utilization ratio of hydrogen peroxide is 87%; Propylene oxide selectivity is 93%.
Embodiment 2
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition with embodiment 1, when reducing the air speed of system oxygenant, make the transformation efficiency when oxygenant increase, touch 95% or object product olefin oxide selectivity rising, when touching 95%, the air speed of maintenance system oxygenant.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 96%; Effective utilization ratio of hydrogen peroxide is 90%; Propylene oxide selectivity is 95%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 93%; Effective utilization ratio of hydrogen peroxide is 88%; Propylene oxide selectivity is 95%.
Comparative example 2
This comparative example illustrates epoxidation of propylene situation when not adopting the inventive method.
Be 2:1 by propylene, hydrogen peroxide, solvent and HTS microspherical catalyst according to the mol ratio of propylene and hydrogen peroxide, the mol ratio of solvent methanol and propylene is 9:1, and system oxygenant weight hourly space velocity is 2.0h -1, react under be 50 DEG C of pressure being 2.5MPa in temperature.The result of reacting 2 hours is as follows: hydrogen peroxide conversion 96%; Effective utilization ratio of hydrogen peroxide is 92%; Propylene oxide selectivity is 97%.The result of reacting 240 hours is as follows: hydrogen peroxide conversion 94%; Effective utilization ratio of hydrogen peroxide is 89%; Propylene oxide selectivity is 91%.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 90%; Effective utilization ratio of hydrogen peroxide is 85%; Propylene oxide selectivity is 89%.
Embodiment 3
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition with comparative example 2, unlike in reaction after 240 hours, 0.02 ~ 1.0h -1the air speed of oxygenant in the amplitude reduction system of/d, make the transformation efficiency when oxygenant increase, touch 95% and object product olefin oxide selectivity rises, when touching 95%, the air speed of oxygenant in maintenance system, until system oxygenant air speed reaches 0.02h -1.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 90%; Propylene oxide selectivity is 95%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 88%; Propylene oxide selectivity is 94%.The result of reacting 960 hours is as follows: hydrogen peroxide conversion 92%; Effective utilization ratio of hydrogen peroxide is 86%; Propylene oxide selectivity is 92%.
Embodiment 4
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition is with embodiment 3, HTS and TS-1 being 10:1 by mass ratio unlike catalyzer substitutes, and said alkene is first contacted with HTS with oxygenant, then contacts with TS-1.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 97%; Effective utilization ratio of hydrogen peroxide is 93%; Propylene oxide selectivity is 97%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 90%; Propylene oxide selectivity is 95%.The result of reacting 960 hours is as follows: hydrogen peroxide conversion 94%; Effective utilization ratio of hydrogen peroxide is 89%; Propylene oxide selectivity is 95%.
Embodiment 5
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition, with embodiment 4, unlike making said alkene first contact with TS-1 with oxygenant, then contacts with HTS.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 93%; Effective utilization ratio of hydrogen peroxide is 89%; Propylene oxide selectivity is 92%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 90%; Effective utilization ratio of hydrogen peroxide is 85%; Propylene oxide selectivity is 88%.The result of reacting 960 hours is as follows: hydrogen peroxide conversion 85%; Effective utilization ratio of hydrogen peroxide is 82%; Propylene oxide selectivity is 82%.
Embodiment 6
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition is with embodiment 4, HTS and TS-1 being 1:1 by mass ratio unlike catalyzer substitutes, and said alkene is first contacted with HTS with oxygenant, then contacts with TS-1.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 90%; Propylene oxide selectivity is 94%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 92%; Effective utilization ratio of hydrogen peroxide is 88%; Propylene oxide selectivity is 91%.The result of reacting 960 hours is as follows: hydrogen peroxide conversion 88%; Effective utilization ratio of hydrogen peroxide is 84%; Propylene oxide selectivity is 89%.
Embodiment 7
The present embodiment illustrates epoxidation of propylene situation when adopting the inventive method.
Epoxidation of propylene condition is with embodiment 4, HTS and TS-1 being 15:1 by mass ratio unlike catalyzer substitutes, and said alkene is first contacted with HTS with oxygenant, then contacts with TS-1.The result of reacting 360 hours is as follows: hydrogen peroxide conversion 97%; Effective utilization ratio of hydrogen peroxide is 91%; Propylene oxide selectivity is 95%.The result of reacting 720 hours is as follows: hydrogen peroxide conversion 95%; Effective utilization ratio of hydrogen peroxide is 88%; Propylene oxide selectivity is 92%.The result of reacting 960 hours is as follows: hydrogen peroxide conversion 91%; Effective utilization ratio of hydrogen peroxide is 85%; Propylene oxide selectivity is 90%.
Embodiment 8
The present embodiment illustrates butylene epoxidation situation when adopting the inventive method.
Alkene epoxidation condition, with embodiment 4, substitutes propylene unlike alkene by butylene, and oxygenant replaces hydrogen peroxide by tertbutyl peroxide.The result of reacting 360 hours is as follows: tertbutyl peroxide transformation efficiency 92%; Oxygenant effective rate of utilization is 87%; Butylene oxide ring selectivity is 93%.The result of reacting 720 hours is as follows: tertbutyl peroxide transformation efficiency 90%; Oxygenant effective rate of utilization is 85%; Butylene oxide ring selectivity is 93%.The result of reacting 960 hours is as follows: tertbutyl peroxide transformation efficiency 87%; Oxygenant effective rate of utilization is 86%; Butylene oxide ring selectivity is 91%.
As can be seen from embodiment and comparative example: production method maintenance oxygenant effective rate of utilization of the present invention and object selectivity of product, in higher scope, delay catalyst deactivation, make extend total working time, improve the entire life of catalyzer simultaneously.

Claims (16)

1. the method for an olefin oxidation, under olefin hydrocarbon oxidation reaction condition, alkene and oxygenant is made to carry out contact reacts with catalyzer on a fixed bed, the transformation efficiency that it is characterized in that comprising oxygenant in index (a) reaction process reduces, touch 90% and/or the selectivity of index (b) object product olefin oxide reduces, when touching 92%, with 0.001 ~ 0.15h -1the amplitude of/d reduces the air speed of oxygenant, make the transformation efficiency when index (c) oxygenant increase, touch 94% and/or index (d) object product olefin oxide selectivity rising, when touching 94%, the step of the air speed of maintenance oxygenant.
2., according to the process of claim 1 wherein, said olefin hydrocarbon oxidation reaction condition is temperature 0 ~ 120 DEG C, pressure 0.01 ~ 5MPa, the mol ratio of alkene and oxygenant is 1 ~ 10:1, and the mol ratio of solvent and alkene is 0 ~ 100:1, and in system, the weight hourly space velocity of oxygenant is 0.05 ~ 20h -1.
3. according to the method for claim 2, wherein, said temperature is 20 ~ 80 DEG C, and pressure is 0.1 ~ 3MPa, and the mol ratio of alkene and oxygenant is 0.2 ~ 5:1, and the mol ratio of solvent and alkene is 0.2 ~ 80:1, and in system, the weight hourly space velocity of oxygenant is 0.1 ~ 10h -1.
4. according to the method for claim 1 or 2, wherein, said alkene to be carbonatoms be 2 ~ 6 alkene.
5. according to the method for claim 4, wherein, said alkene is propylene or butylene.
6. according to the method for one of claims 1 to 3, wherein, said oxygenant to be mass concentration be 5 ~ 70% aqueous hydrogen peroxide solution.
7. according to the method for Claims 2 or 3, wherein, said solvent selected from methanol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol or acetone.
8., according to the process of claim 1 wherein, the transformation efficiency that said index (a) changes into oxygenant in reaction process reduces, touches 92%; The selectivity that said index (b) changes into object product olefin oxide reduces, touches 94%.
9., according to the process of claim 1 wherein, the amplitude of the air speed of said reduction oxygenant is 0.002 ~ 0.10h -1/ d.
10., according to the process of claim 1 wherein, the transformation efficiency that said index (c) changes into oxygenant rises, touches 95%; The selectivity that said index (d) changes into object product olefin oxide rises, touches 95%.
11. according to the process of claim 1 wherein, said catalyzer take HTS as active component.
12. according to the method for claim 11, and wherein, said HTS is selected from TS-1.
13. according to the method for claim 12, and wherein, said TS-1 is HTS, and its crystal grain is hollow structure, and the radical length of the chamber portion of this hollow structure is 5 ~ 300 nanometers, and described HTS is at 25 DEG C, P/P 0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.
14. according to the process of claim 1 wherein, said catalyzer is set to HTS and TS-1 two portions in said fixed bed, and said alkene is first contacted with HTS with oxygenant, then contact with TS-1.
15. according to the method for claim 14, and wherein, the mass ratio of said HTS and said TS-1 is 1 ~ 20:1.
16. according to the method for claim 15, and wherein, the mass ratio of said HTS and said TS-1 is 2 ~ 10:1.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301599A (en) * 1999-12-24 2001-07-04 中国石油化工集团公司 Titanium-silicon molecular sieve and its preparing method
CN101279959A (en) * 2008-05-21 2008-10-08 湖南长岭石化科技开发有限公司 Method for synthesizing epoxypropane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301599A (en) * 1999-12-24 2001-07-04 中国石油化工集团公司 Titanium-silicon molecular sieve and its preparing method
CN101279959A (en) * 2008-05-21 2008-10-08 湖南长岭石化科技开发有限公司 Method for synthesizing epoxypropane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
姚明恺等: "《Ti-MWW催化氯丙烯环氧化固定床工艺研究》", 《催化学报》, vol. 29, no. 12, 31 December 2008 (2008-12-31), pages 1271 - 1276 *

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