CN104447626A - Alkene oxidation method - Google Patents

Abstract

A method for oxidizing olefins, which is to make olefins and oxidants contact with a catalyst on a fixed bed under olefin oxidation reaction conditions, which is characterized in that whenever the conversion rate of oxidants in the indicator (a) is reduced and reaches 90% during the reaction process And/or index (b) when the selectivity of the target product oxidized olefins decreases and reaches 92%, reduce the space velocity of the oxidant in the range of 0.001 to 0.15h ^-1 /d, so that when the index (c) the conversion rate of the oxidant increases, The step of maintaining the space velocity of the oxidant when reaching 94% and/or when the selectivity of target product oxidized olefins in the indicator (d) rises and reaches 94%. The method can maintain the total conversion rate of the oxidant and the selectivity of the target product during the reaction contact process, prolong the total operation time, delay the deactivation of the catalyst and improve the service life of the catalyst.

Description

A kind of method of olefin oxidation

technical field

The present invention relates to a method for oxidizing olefins.

Background technique

Alkylene oxide is an important class of oxygen-containing organic compounds, such as propylene oxide, also known as propylene oxide (PO for short), is an important basic organic chemical raw material, and its output in propylene derivatives is second only to poly propylene. The biggest use of PO is to produce polyether polyols for further processing to make polyurethane, and it can also be used to produce propylene glycol which is widely used. In addition, propylene oxide can also be used in the production of surfactants, oilfield demulsifiers, etc.

With the wide application of polyurethane materials, etc., the demand for propylene oxide is increasing year by year. At present, there are disadvantages in the process of producing propylene oxide in industry, especially it does not meet the requirements of green chemical industry. Therefore, there is an urgent need to develop economical and environmentally friendly production methods.

The appearance of titanium silicon molecular sieve TS-1 (US4410501) has opened up a new way for olefin epoxidation, phenol hydroxylation, ketone alcohol oxidation, etc., especially in olefin epoxidation, and achieved good catalytic oxidation Effect. In the reaction system using hydrogen peroxide as oxidant and methanol as solvent, titanium-silicon molecular sieves have high catalytic activity for propylene. At present, Dow/BASF and Degussa/Uhde have pushed this process to industrialization.

However, there is a general problem that after a period of operation of the device, the activity and selectivity of the catalyst will decrease, that is, the catalyst will be deactivated during operation. At present, the main solution is to use two methods of internal regeneration and external regeneration to restore the activity of the catalyst. Among them, in-device regeneration is mainly for the case of relatively mild deactivation, which is generally realized by dipping or washing with solvent and/or oxidant at a certain temperature for a certain period of time; out-of-device regeneration is mainly for the case of severe deactivation It is achieved by means of roasting and the like. Generally, in the industry, the catalyst is reactivated by in-device regeneration first, and then the out-of-device regeneration is used after the in-device regeneration fails to restore the catalyst activity. The problem with this kind of regeneration is that when re-running after regeneration, especially when re-running after in-device regeneration, the activity and selectivity of the catalyst fluctuate greatly, and it takes a long time to stabilize. The smooth operation of the reaction, but this will further accelerate the deactivation of the catalyst and reduce the selectivity of the target product, which will affect the refining and separation of subsequent products, and is also not conducive to safe production.

CN101279959A discloses a method for synthesizing propylene oxide, which is characterized in that low-carbon alcohol, propylene, and hydrogen peroxide in a molar ratio of 1 to 15:0.5 to 5:1 are in a reactor equipped with a catalyst, and propylene and hydrogen peroxide are epoxidized Propylene oxide is obtained through the reaction, wherein the pH value of the solution and the reaction temperature are adjusted according to the conversion rate of hydrogen peroxide at any time during the entire reaction process. Once the conversion rate of hydrogen peroxide is reduced to 88.5%, the pH value of the solution and the reaction temperature are increased. The invention can prolong the single operation life of the catalyst by adjusting the pH value of the solution and the reaction temperature, and the single operation life of the catalyst can reach more than 1200 hours. However, this method is not conducive to the repeated regeneration of the catalyst, that is, it affects the total operating life of the catalyst.

Contents of the invention

The object of the present invention is to provide a method for oxidizing olefins.

The inventors of the present invention have found through a large number of experimental studies that when the oxidant conversion rate is lower than 90% and/or the selectivity of the target product oxidized olefins is lower than 92% during the operation of the olefin epoxidation reaction, the system will be reduced to a certain extent. The space velocity of the oxidant and the space velocity of other materials remain constant, which can maintain the conversion rate of the oxidant and the selectivity of the target product oxidized olefin at a relatively high level, thereby prolonging the stable operation time of olefin epoxidation. Based on this, the present invention has been accomplished.

The method provided by the present invention is to make olefins and oxidants contact with catalysts on a fixed bed under the conditions of olefin oxidation reaction, which is characterized in that whenever the conversion rate of oxidants in the indicator (a) reaction process decreases, reaches 90% and / or index (b) when the selectivity of the target product oxidized olefins decreases and reaches 92%, reduce the space velocity of the oxidant in the range of 0.001 to 0.15h ^-1 /d, so that when the index (c) the conversion rate of the oxidant increases and reaches The step of maintaining the space velocity of the oxidant when the selectivity of 94% and/or the selectivity of target product oxidized alkenes of the indicator (d) rises and reaches 94%.

In the method provided by the present invention, the above index percentages all refer to the form of mole percentage, that is, index (a) is the conversion rate (mole percentage) of the oxidant in the reaction process; index (b) the selectivity of the target product oxidized olefin (mole percentage) ; Index (c) the conversion rate of the oxidant (mole percent); index (d) the selectivity of the target product oxidized olefin (mole percent).

In the method provided by the present invention, the catalyst uses titanium-silicon molecular sieve as an active component, and the particle size of the catalyst is preferably 0.5-20000 microns. The present invention has no special limitation on the content of titanium atoms in the titanium-silicon molecular sieve, which can be a conventional choice in the field. Specifically, when the titanium-silicon molecular sieve is represented by the chemical formula xTiO ₂ ·SiO ₂ , x may be 0.0001-0.04, preferably 0.01-0.03, and more preferably 0.015-0.025. The titanium-silicon molecular sieve can be a common titanium-silicon molecular sieve with various topological structures, for example: the titanium-silicon molecular sieve can be selected from a titanium-silicon molecular sieve with an MFI structure (such as TS-1), a titanium-silicon molecular sieve with a MEL structure (such as TS-2), titanium-silicon molecular sieves with BEA structure (such as Ti-Beta), titanium-silicon molecular sieves with MWW structure (such as Ti-MCM-22), titanium-silicon molecular sieves with hexagonal structure (such as Ti-MCM-41, Ti-SBA -15), titanium-silicon molecular sieves with MOR structure (such as Ti-MOR), titanium-silicon molecular sieves with TUN structure (such as Ti-TUN) and titanium-silicon molecular sieves with other structures (such as Ti-ZSM-48).

Preferably, the titanium-silicon molecular sieve is selected from titanium-silicon molecular sieves with MFI structure, titanium-silicon molecular sieves with MEL structure and titanium-silicon molecular sieves with BEA structure. More preferably, the titanium-silicon molecular sieve is titanium-silicon molecular sieve TS-1 with MFI structure. From the perspective of further improving the effective utilization rate of the oxidant and product selectivity, the grains of the titanium-silicon molecular sieve are hollow structures, and the radial length of the cavity part of the hollow structure is 5 to 300 nanometers, and the titanium-silicon molecular sieve The molecular sieve has a benzene adsorption capacity of at least 70 mg/g measured under the conditions of 25°C, P/P ₀ =0.10, and an adsorption time of 1 hour. The adsorption isotherm and desorption isotherm of the low-temperature nitrogen adsorption of the titanium-silicon molecular sieve There is a hysteresis loop between them. Herein, the titanium-silicon molecular sieve with this structure is called hollow titanium-silicon molecular sieve HTS. The hollow titanium-silicon molecular sieve can be obtained commercially (for example, the molecular sieve with the trademark HTS purchased from Sinopec Hunan Jianchang Petrochemical Co., Ltd.), or can be prepared according to the method disclosed in CN1132699C.

In the most preferred embodiment of the present invention, said catalyst is set as HTS and TS-1 two parts in said fixed bed, and makes said olefin and oxygenant contact with HTS first, then with TS-1 touch. The mass ratio of said HTS to said TS-1 is 1-20:1, preferably 2-10:1.

In the method provided by the present invention, the amount of the catalyst is not particularly limited, as long as it meets the reaction requirements, and the thickness of the bed can be flexibly adjusted according to the reaction requirements. Moreover, the catalyst can be diluted with inert fillers such as quartz sand, ceramic rings, ceramic fragments, etc. according to the needs of the reaction.

In said method, said olefins are not more than 12 carbon atoms, preferably olefins with 2 to 6 carbon atoms, more preferably propylene and butene.

In said method, specific examples of the oxidizing agent may include, but are not limited to: hydrogen peroxide, t-butyl hydroperoxide, cumene peroxide, cyclohexyl hydroperoxide, peracetic acid and peroxypropionic acid. Preferably, the oxidizing agent is hydrogen peroxide, which can further reduce the separation cost. It is usually added to the reaction system in the form of aqueous hydrogen peroxide solution with a concentration of 5-70% by mass. For example, industrial-grade hydrogen peroxide solutions include 27.5%, 30%, 55% and 70%.

In said method, in order to improve the efficiency of reaction, can also introduce solvent in the reaction system, used solvent comprises ketones, alcohols, nitriles, for example is selected from methanol, ethanol, n-propanol, isopropanol, t-butyl Alcohol, isobutanol, acetone, butanone, acetonitrile, acrylonitrile or a mixture of one or more, wherein methanol, acetone or tert-butanol are preferred. Wherein, said solvent is selected from methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol or acetone. Preferably methanol, tert-butanol or acetone, more preferably the solvent is methanol.

The method provided by the present invention, wherein the olefin oxidation reaction conditions are a temperature of 0-120°C, a pressure of 0.01-5 MPa, a molar ratio of olefin to oxidant of 1-10:1, and a molar ratio of solvent to olefin of 0-100 : 1. The weight hourly space velocity of the oxidizing agent in the system is 0.05～20h ^-1 . Preferably, the temperature is 20-80°C, the pressure is 0.1-3 MPa, the molar ratio of olefin to oxidant is 0.2-5:1, the molar ratio of solvent to olefin is 0.2-80:1, and the weight of oxidant in the system is The hourly space velocity is 0.1～10h ^-1 .

In the method provided by the present invention, the space velocity of the oxidant in the system is reduced to a certain extent, in terms of weight hourly space velocity, the space velocity of the oxidant in the system can be reduced to below 0.02h ^-1 , even can reach 0.01h ^-1 Hereinafter, the present invention has no special requirements for this. However, if the space velocity of the oxidant in the reduced system is too large, the product yield will be low. Considering economical efficiency, the space velocity of the oxidant in the system can be reduced to 0.02h ^-1 .

In said method, the preferred embodiment is when the index (a) is changed to reduce the conversion rate of the oxidant in the reaction process, reaching 92% and/or when the index (b) changes to the selectivity of the target product oxidized olefins, reducing, reaching At 94%, the range of reducing the space velocity of the oxidant is 0.02～0.10h ^-1 /d, so that when the index (c) changes to the conversion rate of the oxidant, it reaches 95% and/or the index (d) changes to the oxidation of the target product The oxidant space velocity is maintained as the olefin selectivity rises to 95%.

The method provided by the invention can maintain the total conversion rate of the oxidant and the selectivity of the target product during the reaction contact process, prolong the total operation time, delay the deactivation of the catalyst, and increase the service life of the catalyst. At the same time, in the process of use, the selectivity of the target product is high, the activity and stability of the catalyst are good, the process is simple and easy to control, and it is beneficial to industrial production and application.

Detailed ways

The following examples will further illustrate the present invention, but do not limit the content of the present invention thereby.

In Examples and Comparative Examples, all reagents used are commercially available chemically pure or analytically pure reagents.

The titanium-silicon molecular sieve (TS-1) used in the comparative examples and examples is the TS-1 molecular sieve sample prepared by the method described in the prior art Zeolites, 1992, Vol.12 pages 943-950, and its titanium oxide The content is 2.5% by weight. Hollow titanium-silicon molecular sieve HTS is produced by Sinopec Hunan Jianchang Petrochemical Co., Ltd. It is an industrial product of titanium-silicon molecular sieve described in Chinese patent CN1301599A. After analysis, the titanium-silicon molecular sieve has an MFI structure, and its titanium oxide content is 2.5% by weight. There is a hysteresis loop between the adsorption isotherm and the desorption isotherm of the low-temperature nitrogen adsorption of the titanium-silicon molecular sieve. The radial length of the cavity part is 15-180 nanometers; the benzene adsorption capacity of the titanium-silicon molecular sieve sample measured under the conditions of 25°C, P/P ₀ =0.10, and adsorption time of 1 hour is 78 mg/g.

In the examples and comparative examples, the preparation method of the microsphere catalyst used is as follows: under the condition of normal pressure and 60°C, the organosilicon compound ethyl orthosilicate was first added to the tetrapropylammonium hydroxide aqueous solution and mixed, stirred and hydrolyzed for 5h Obtain a colloidal solution; then add titanium-silicon molecular sieves to the above-mentioned colloidal solution and mix uniformly to obtain a slurry, and the mass ratio of titanium-silicon molecular sieves, organic silicon compounds, tetrapropylammonium hydroxide and water is 100:25:5: 250; After the above slurry is continuously stirred for 2 hours, the catalyst in the shape of microspheres (particle size 20-80 microns) used in the present invention can be obtained by conventional spray granulation and then roasting.

In Examples and Comparative Examples, the olefin oxidation reaction is carried out in a common miniature fixed-bed reactor.

In comparative examples and examples, gas chromatography is used to analyze the content of each component in the reaction solution obtained, and on this basis, the following formulas are used to calculate the conversion rate of oxidant, the effective utilization rate of oxidant and the selectivity of oxidized olefins:

Comparative example 1

This comparative example illustrates the epoxidation of propylene without using the method of the present invention.

The molar ratio of propylene, hydrogen peroxide, solvent and TS-1 microsphere catalyst is 3:1 between propylene and hydrogen peroxide, the molar ratio of solvent acetone and propylene is 10:1, and the weight hourly space velocity of the oxidant in the system is 5.0 h ^-1 , the reaction is carried out at a temperature of 40°C and a pressure of 2.5 MPa. The results of the reaction for 2 hours were as follows: the conversion rate of hydrogen peroxide was 95%; the effective utilization rate of hydrogen peroxide was 90%; the selectivity of propylene oxide was 96%. The results of the reaction for 240 hours were as follows: the conversion rate of hydrogen peroxide was 92%; the effective utilization rate of hydrogen peroxide was 87%; the selectivity of propylene oxide was 93%. The results of the reaction for 360 hours were as follows: the conversion rate of hydrogen peroxide was 85%; the effective utilization rate of hydrogen peroxide was 83%; the selectivity of propylene oxide was 88%.

Example 1

This example illustrates the epoxidation of propylene using the method of the present invention.

The propylene epoxidation conditions are the same as in Comparative Example 1, the difference is that after 240 hours of reaction, the space velocity of the oxidant in the system is reduced in the range of 0.02 to 0.2h ^-1 /d, so that when the conversion rate of the oxidant rises and reaches 94% and the target When the selectivity of the product oxidized olefins increases and reaches 94%, the space velocity of the oxidant in the system is maintained until the space velocity of the oxidant in the system decreases to 0.02h ^-1 . The results of the reaction for 360 hours were as follows: the conversion rate of hydrogen peroxide was 95%; the effective utilization rate of hydrogen peroxide was 88%; the selectivity of propylene oxide was 94%. The results of the reaction for 720 hours were as follows: the conversion rate of hydrogen peroxide was 92%; the effective utilization rate of hydrogen peroxide was 87%; the selectivity of propylene oxide was 93%.

Example 2

This example illustrates the epoxidation of propylene using the method of the present invention.

Propylene epoxidation condition is the same as embodiment 1, when reducing the space velocity of system oxidant, make when the conversion ratio of oxidant rises, touches 95% or the selectivity of target product oxidized olefin rises, touches 95%, keep the space velocity of system oxidant . The results of the reaction for 360 hours were as follows: the conversion rate of hydrogen peroxide was 96%; the effective utilization rate of hydrogen peroxide was 90%; the selectivity of propylene oxide was 95%. The results of the reaction for 720 hours were as follows: the conversion rate of hydrogen peroxide was 93%; the effective utilization rate of hydrogen peroxide was 88%; the selectivity of propylene oxide was 95%.

Comparative example 2

This comparative example illustrates the epoxidation of propylene without using the method of the present invention.

The molar ratio of propylene, hydrogen peroxide, solvent and HTS microsphere catalyst is 2:1 between propylene and hydrogen peroxide, the molar ratio of solvent methanol to propylene is 9:1, and the weight hourly space velocity of the system oxidant is 2.0h ^-1 , The reaction was carried out at a temperature of 50° C. and a pressure of 2.5 MPa. The results of the reaction for 2 hours were as follows: the conversion rate of hydrogen peroxide was 96%; the effective utilization rate of hydrogen peroxide was 92%; the selectivity of propylene oxide was 97%. The results of the 240-hour reaction were as follows: the conversion rate of hydrogen peroxide was 94%; the effective utilization rate of hydrogen peroxide was 89%; the selectivity of propylene oxide was 91%. The results of the reaction for 360 hours were as follows: the conversion rate of hydrogen peroxide was 90%; the effective utilization rate of hydrogen peroxide was 85%; the selectivity of propylene oxide was 89%.

Example 3

This example illustrates the epoxidation of propylene using the method of the present invention.

The propylene epoxidation conditions are the same as those in Comparative Example 2, the difference is that after 240 hours of reaction, the space velocity of the oxidant in the system is reduced by 0.02 to 1.0h ^-1 /d, so that when the conversion rate of the oxidant rises and reaches 95% and the target When the selectivity of the product oxidized olefins increases and reaches 95%, the space velocity of the oxidant in the system is maintained until the space velocity of the oxidant in the system reaches 0.02h ^-1 . The results of the reaction for 360 hours are as follows: the conversion rate of hydrogen peroxide is 95%; the effective utilization rate of hydrogen peroxide is 90%; the selectivity of propylene oxide is 95%. The results of the reaction for 720 hours were as follows: the conversion rate of hydrogen peroxide was 95%; the effective utilization rate of hydrogen peroxide was 88%; the selectivity of propylene oxide was 94%. The result of reacting for 960 hours is as follows: the conversion rate of hydrogen peroxide is 92%; the effective utilization rate of hydrogen peroxide is 86%; the selectivity of propylene oxide is 92%.

Example 4

This example illustrates the epoxidation of propylene using the method of the present invention.

Propylene epoxidation conditions are the same as in Example 3, except that the catalyst is replaced by HTS and TS-1 with a mass ratio of 10:1, and the olefin and oxidant are first contacted with HTS and then with TS-1. The results of the reaction for 360 hours were as follows: the conversion rate of hydrogen peroxide was 97%; the effective utilization rate of hydrogen peroxide was 93%; the selectivity of propylene oxide was 97%. The result of reacting for 720 hours is as follows: the conversion rate of hydrogen peroxide is 95%; the effective utilization rate of hydrogen peroxide is 90%; the selectivity of propylene oxide is 95%. The result of reacting for 960 hours is as follows: the conversion rate of hydrogen peroxide is 94%; the effective utilization rate of hydrogen peroxide is 89%; the selectivity of propylene oxide is 95%.

Example 5

This example illustrates the epoxidation of propylene using the method of the present invention.

Propylene epoxidation conditions were the same as in Example 4, except that said olefin and oxidant were first contacted with TS-1 and then with HTS. The results of the reaction for 360 hours were as follows: the conversion rate of hydrogen peroxide was 93%; the effective utilization rate of hydrogen peroxide was 89%; the selectivity of propylene oxide was 92%. The results of the reaction for 720 hours are as follows: the conversion rate of hydrogen peroxide is 90%; the effective utilization rate of hydrogen peroxide is 85%; the selectivity of propylene oxide is 88%. The result of reacting for 960 hours is as follows: the conversion rate of hydrogen peroxide is 85%; the effective utilization rate of hydrogen peroxide is 82%; the selectivity of propylene oxide is 82%.

Example 6

This example illustrates the epoxidation of propylene using the method of the present invention.

The propylene epoxidation conditions are the same as in Example 4, except that the catalyst is replaced by HTS and TS-1 with a mass ratio of 1:1, and the olefin and oxidant are first contacted with HTS and then with TS-1. The results of the reaction for 360 hours were as follows: the conversion rate of hydrogen peroxide was 95%; the effective utilization rate of hydrogen peroxide was 90%; the selectivity of propylene oxide was 94%. The results of the reaction for 720 hours were as follows: the conversion rate of hydrogen peroxide was 92%; the effective utilization rate of hydrogen peroxide was 88%; the selectivity of propylene oxide was 91%. The result of reacting for 960 hours is as follows: the conversion rate of hydrogen peroxide is 88%; the effective utilization rate of hydrogen peroxide is 84%; the selectivity of propylene oxide is 89%.

Example 7

This example illustrates the epoxidation of propylene using the method of the present invention.

Propylene epoxidation conditions are the same as in Example 4, except that the catalyst is replaced by HTS and TS-1 with a mass ratio of 15:1, and said olefin and oxidant are first contacted with HTS and then with TS-1. The results of the reaction for 360 hours were as follows: the conversion rate of hydrogen peroxide was 97%; the effective utilization rate of hydrogen peroxide was 91%; the selectivity of propylene oxide was 95%. The results of the reaction for 720 hours were as follows: the conversion rate of hydrogen peroxide was 95%; the effective utilization rate of hydrogen peroxide was 88%; the selectivity of propylene oxide was 92%. The result of reacting for 960 hours is as follows: the conversion rate of hydrogen peroxide is 91%; the effective utilization rate of hydrogen peroxide is 85%; the selectivity of propylene oxide is 90%.

Example 8

This example illustrates the epoxidation of butene using the method of the present invention.

The olefin epoxidation conditions are the same as in Example 4, except that the olefin is replaced by butene for propylene, and the oxidant is replaced by tert-butyl hydroperoxide for hydrogen peroxide. The result of reacting for 360 hours is as follows: the conversion rate of tert-butyl hydroperoxide is 92%; the effective utilization rate of oxidant is 87%; the selectivity of butylene oxide is 93%. The result of reacting for 720 hours is as follows: the conversion rate of tert-butyl hydroperoxide is 90%; the effective utilization rate of oxidant is 85%; the selectivity of butylene oxide is 93%. The result of reacting for 960 hours is as follows: the conversion rate of tert-butyl hydroperoxide is 87%; the effective utilization rate of oxidant is 86%; the selectivity of butylene oxide is 91%.

As can be seen from the examples and comparative examples: the production method of the present invention maintains the effective utilization rate of the oxidant and the selectivity of the target product in a relatively high range, while delaying catalyst deactivation, prolonging the total running time, and improving the total life of the catalyst .

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.