WO2012048528A1 - Procédé d'époxydation pour oléfine - Google Patents

Procédé d'époxydation pour oléfine Download PDF

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Publication number
WO2012048528A1
WO2012048528A1 PCT/CN2011/001702 CN2011001702W WO2012048528A1 WO 2012048528 A1 WO2012048528 A1 WO 2012048528A1 CN 2011001702 W CN2011001702 W CN 2011001702W WO 2012048528 A1 WO2012048528 A1 WO 2012048528A1
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Prior art keywords
catalyst
olefin
exchange resin
anion exchange
hydrogen peroxide
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PCT/CN2011/001702
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English (en)
Chinese (zh)
Inventor
李华
林民
何驰剑
王伟
伍小驹
高计皂
贺晓军
李旭柏
史春风
Original Assignee
中国石油化工股份有限公司
湖南长岭石化科技开发有限公司
中国石油化工股份有限公司石油化工科学研究院
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Priority claimed from CN201010511512.6A external-priority patent/CN102442975B/zh
Priority claimed from CN201010511546.5A external-priority patent/CN102442977B/zh
Application filed by 中国石油化工股份有限公司, 湖南长岭石化科技开发有限公司, 中国石油化工股份有限公司石油化工科学研究院 filed Critical 中国石油化工股份有限公司
Priority to SG2013027131A priority Critical patent/SG189877A1/en
Priority to RU2013120980/04A priority patent/RU2576620C2/ru
Publication of WO2012048528A1 publication Critical patent/WO2012048528A1/fr

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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
    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • 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
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/09—Organic material

Definitions

  • This invention relates to a process for the epoxidation of olefins. Background technique
  • Propylene oxide is the third largest organic chemical product in the production of propylene derivatives, which is second only to polypropylene and acrylonitrile. It is mainly used to produce polyether, propylene glycol, isopropanolamine, non-polyether polyol, etc., and then produces unsaturated Important raw materials such as polyester resin, polyurethane, surfactant, and flame retardant.
  • the conventional preparation methods of propylene oxide mainly include a chlorohydrin method and a co-oxidation method.
  • the equipment When propylene oxide is used to synthesize propylene oxide, the equipment is seriously corroded, consumes a large amount of Cl 2 , and generates a large amount of waste water and slag, which causes great pollution to the environment. With the increasing requirements of environmental protection, the process will eventually It is eliminated; the co-oxidation process is long, the investment is large, and the production is restricted by the application of by-products. Therefore, the preparation of these conventional propylene oxides restricts the production of propylene oxide.
  • the pH value in the reaction system is one of the most critical technical parameters in the whole process.
  • H 2 0 2 is acidic
  • the pH of the reaction system is small without adding a pH adjuster, and the reactivity in the reaction system is low, resulting in low production efficiency;
  • the pH in the reaction system is too high (for example, a pH of 9 or more)
  • a side reaction occurs, and the selectivity of propylene oxide is lowered.
  • hydrogen peroxide decomposes rapidly, resulting in a decrease in the utilization rate of hydrogen peroxide.
  • 6,300,506 discloses a process for the direct epoxidation of an olefin to produce an olefin oxide using hydrogen peroxide or a compound capable of forming hydrogen peroxide under the reaction conditions, wherein the epoxidation reaction is carried out in the presence of a catalyst system, the catalyst
  • the system consists of a titanium-containing zeolite and a buffer system for controlling the pH at 5.0-8.0, which consists of a salt of a base and a base of nitrogen and an organic or inorganic acid.
  • the pH-adjusting substance added to the epoxidation reaction system may cause the formation of nascent oxygen in the reaction system, the activity of the nascent oxygen is high, and the oxidation selectivity is poor, resulting in a reaction system.
  • the local reaction is severe, the side reaction is increased, the selectivity to propylene oxide is lowered, and the by-products produced cause a significant decrease in the service life of the catalyst.
  • the present invention provides a novel epoxidation process for olefins, in which hydrogen peroxide conversion and ring are used in the process of preparing epoxidized olefins by the process.
  • the selectivity to oxidized olefins is high and the useful life of the catalyst is long.
  • the present invention provides a process for the epoxidation of an olefin which comprises subjecting an olefin and hydrogen peroxide to an epoxidation reaction in the presence of a catalyst and a basic anion exchange resin under olefin epoxidation conditions.
  • the basic anion exchange resin may undergo an ion exchange reaction with a hydrogen ion in a reaction system of an olefin and hydrogen peroxide to appropriately increase the pH value in the reaction system. And it is possible to keep the pH in the reaction system from being too high.
  • the epoxidized olefin is synthesized by the method provided by the present invention, and the test results show that the hydrogen peroxide is less decomposed inefficient, the selectivity for the reaction to form an epoxidized olefin is better, and the by-products generated by the side reaction are less, thereby enabling Significantly improve the conversion of hydrogen peroxide
  • the rate, the selectivity of the epoxidized olefin, and the useful life of the catalyst are not intended to be limited by any theoretical limitations, but it is believed that the reason is that on the one hand, the decomposition of hydrogen peroxide can be inhibited due to the presence of the basic anion exchange resin.
  • the formation of ecological oxygen in the early stage; on the other hand, the ion exchange reaction between the hydrogen ion and the basic anion exchange resin in the reaction system is relatively gentle, so that the occurrence of side reactions can be effectively suppressed.
  • the process for epoxidizing the olefin provided by the present invention comprises subjecting an olefin and hydrogen peroxide to an epoxidation reaction in the presence of a catalyst and a basic anion exchange resin under olefin epoxidation conditions.
  • the process for epoxidizing the olefin according to the present invention may be carried out in various conventional reactors, which may, for example, include at least one of a fixed bed reactor, a moving bed reactor, a slurry bed reactor, and the like.
  • a fixed bed reactor a moving bed reactor or a continuous slurry bed reactor
  • the conditions of the olefin epoxidation reaction may further include a liquid volumetric space velocity of 1-1511 - 1 preferably 2-1011-1.
  • the conditions of the olefin epoxidation reaction may further include: the catalyst and the catalyst based on 100 parts by weight of the total weight of the olefin and hydrogen peroxide.
  • the basic anion exchange resin is used in an amount of from 3 to 10 parts by weight, preferably from 4 to 9 parts by weight, and the reaction time may be from 0.2 to 3 hours.
  • the fixed bed reactor, the moving bed reactor and the slurry bed reactor the fixed bed reactor is a widely used reactor in the industry, and refers to a fluid passing through a stationary solid material.
  • the formed bed layer is subjected to a reaction device;
  • the slurry bed reactor is also referred to as a slurry bed reactor, and refers to a reactor in which the catalyst micro-solid particles are suspended in a liquid shield, and the material of the slurry-bed reactor is back-mixed.
  • the catalyst is separated from the material to carry out the reaction of the next batch;
  • the moving bed reactor is a kind of back mixing of the material used in the bed reactor is small.
  • the process of the invention is preferably carried out in a fixed bed reactor.
  • the method of performing the epoxidation reaction comprises: passing a terpene hydrocarbon and hydrogen peroxide in a cocurrent stream or a mixture of the two through a fixed bed reactor, the bed containing a catalyst and an alkaline Anion exchange resin.
  • the mixing ratio of the catalyst and the basic anion exchange resin is not particularly limited as long as the amount of the basic anion exchange resin can adjust the pH of the reaction system to 3-9, preferably 4-8.
  • the amount of the basic anion exchange resin is relatively too low (e.g., the weight ratio of the catalyst to the basic anion exchange resin is greater than 1:0.05)
  • the basic anion exchange The effect of adjusting the pH of the resin is very weak, so that the conversion of hydrogen peroxide, the selectivity of the epoxidized olefin and the service life of the catalyst cannot be significantly improved; and when the amount of the basic anion exchange resin is relatively high (such as When the weight ratio of the catalyst to the basic anion exchange resin is less than 1: 1.5), the relative content of the catalyst in the system of the epoxidation reaction is too low, thereby causing a reaction in the reaction system.
  • the weight ratio of the catalyst to the basic anion exchange resin is preferably from 1:0.05 to 1.5, further preferably from 1:0.1 to 1, further more preferably from 1:0.2 to 0.8.
  • the pH in the epoxidation reaction system can be stably controlled within the range of 4-8,
  • the epoxidation reaction in the reaction system can be smoothly carried out without causing excessive local reaction, and can effectively inhibit the decomposition of hydrogen peroxide and the occurrence of side reactions, and improve the selectivity of the epoxidation product,
  • the catalyst life is also improved due to fewer side reactions.
  • the method for carrying out the epoxidation reaction comprises: passing an olefin and hydrogen peroxide in a cocurrent stream or a mixture of the two through a fixed bed, the catalyst bed comprising a plurality of catalyst beds a layer, at least a portion of the catalyst bed further comprises a basic anion exchange resin in addition to the catalyst; and along the flow direction of the olefin and hydrogen peroxide in the reactor, the basic anion exchange resin in each catalyst bed Weight percent The content is less than the weight percent of the basic anion exchange resin in the catalyst bed after the catalyst bed.
  • the content of the basic anion exchange resin is gradually increased by co-currently or in the form of a mixture of the olefin and hydrogen peroxide.
  • the increased number of catalyst beds can increase the conversion rate of hydrogen peroxide; in addition, since the basic anion exchange resin can react with hydrogen ions in the reaction system of olefin and hydrogen peroxide, the reaction can be appropriately increased.
  • the pH value in the system can keep the pH value in the reaction system from being too high, so that the hydrogen peroxide is less decomposed inefficient, the selectivity of the reaction to form epoxidized hydrazine is better, and the by-products formed by the side reaction are more Less, thereby significantly increasing the conversion of hydrogen peroxide, the selectivity of epoxidized olefins, and the useful life of the catalyst.
  • the content of the catalyst and the basic anion exchange resin in each of the catalyst beds may vary within a wide range. More preferably, along the flow direction of the olefin and hydrogen peroxide in the reactor, based on the total weight of the catalyst and the basic anion exchange resin in each catalyst bed, in the first catalyst bed
  • the weight percentage of the basic anion exchange resin is from 0 to 30% by weight
  • the weight percentage of the basic anion exchange resin in the last catalyst bed is from 30 to 100% by weight, preferably from 70 to 100% by weight.
  • the alkaline catalyst bed in order to increase the conversion of hydrogen peroxide during the epoxidation of the olefin, is alkaline in the flow direction of the olefin and hydrogen peroxide in the reactor.
  • the difference in the content of the anion exchange resin is 5 to 50% by weight, more preferably 10 to 30% by weight.
  • the height of each catalyst bed is not particularly limited. More preferably, the height of the catalyst bed per layer is from 0.5 to 95%, more preferably 2, of the total height of the catalyst bed along the flow direction of the olefin and hydrogen peroxide in the reactor. ⁇ 60%, still more preferably 2 to 50%, further preferably 10 to 40%.
  • the number of the catalyst beds is not particularly limited, however, when the number of the catalyst beds is gradually increased, the hydrogen peroxide in the epoxidation of the olefin may be gradually increased. Conversion rate, but the number of catalyst beds is also increased. It will increase the difficulty of production of the catalyst bed and the difficulty of regeneration of the catalyst bed. Accordingly, considering the cost of the olefin epoxidation process and the conversion of hydrogen peroxide, the catalyst bed preferably has from 2 to 20 catalyst beds, more preferably from 3 to 10 catalyst beds.
  • the basic anion exchange resin may be various basic anion exchange resins well known in the art, including strongly basic anion exchange resins and/or weakly basic anion exchange resins. Further, the basic anion exchange resin may be, for example, a styrene-based basic anion exchange resin and/or an acrylic-based basic anion exchange resin.
  • the basic anion exchange resin may be of a macroporous or gel type, preferably a macroporous type.
  • the basic anion exchange resin can be commercially available, for example, it can be purchased from Anhui Samsung Resin Co., Ltd.
  • the basic anion exchange resin may have a total exchange capacity of 0.5 to 3 mmol/ml, preferably 0.8 to 2.5 mmol/ml, and more preferably 1.1 to 1.6 mmol/ml.
  • the total exchange capacity refers to the total amount of all exchangeable groups per unit volume of the ion exchange resin.
  • the kind of the catalyst is not particularly limited, and may be appropriately selected among various catalysts conventionally used in the olefin epoxidation process, and may be, for example, a titanium-silicon molecular sieve catalyst or a modified titanium-silicon molecular sieve catalyst. Or a mixture thereof, and a heteropolyacid catalyst or the like.
  • the catalyst is a titanium-silicon molecular sieve catalyst.
  • the titanium-silicon molecular sieve may be, for example, a titanium-silicon molecular sieve of MFI structure, a titanium-silicon molecular sieve of MEL structure, a titanium-silicon molecular sieve of BETA structure, and a ZSM-12 type.
  • At least one of titanium silicon molecular sieves At least one of titanium silicon molecular sieves.
  • the structural formula of the titanium silicon molecular sieve is: xTi0 2 .Si0 2 , wherein X may be 0.0001-0.04, preferably 0.01-0.03.
  • the titanium silicon molecular sieve is commercially available or can be prepared, and a method for preparing the titanium silica molecular sieve is known to those skilled in the art. For example, a method for preparing a catalyst disclosed in CN 101279959A can be employed. be made of.
  • the catalyst is more preferably a titanium silicon molecular sieve having crystal grains of a hollow structure, and the diameter of the cavity portion of the hollow structure
  • the benzene adsorption amount is at least 70 mg/g
  • the titanium silicate molecular sieve has a length of 5 to 300 nm
  • the reaction raw material can easily enter the cavity portion of the catalyst to contact and react with the active component of the titanium silicon molecule, thereby further enhancing The activity of the catalyst; at the same time, the epoxidized olefin as an epoxidation product can also easily fall off from the active site of the titanium silicon molecule, and then diffuse into the cavity of the titanium silicon molecular sieve, shortening the epoxidized olefin in the titanium silicon.
  • the residence time at the active site of the molecular sieve further reduces the probability of side reactions of the epoxidized olefin, thereby further increasing the selectivity of the epoxidation reaction.
  • the epoxidation reaction can be carried out in the presence of an organic solvent.
  • the molar ratio of the organic solvent, olefin and hydrogen peroxide is preferably
  • the olefin is not particularly limited and, for example, may be an olefin having 3 to 8 carbon atoms.
  • the olefin may be one of propylene, butene and pentene, and preferably propylene.
  • the kind of the solvent is not particularly limited in the present invention, and may be, for example, at least one of a C1-C6 alcohol and a C2-C6 nitrile, preferably at least one of decyl alcohol, ethanol, propanol, butanol, and acetonitrile.
  • Preferred is sterol.
  • the hydrogen peroxide is usually used in the form of an aqueous solution, and the concentration of the hydrogen peroxide may be from 10 to 70% by weight, preferably from 20 to 50% by weight.
  • the conditions of the olefin epoxidation reaction may be conventional reaction conditions of the reaction, and the present invention does not In particular, however, in order to obtain a suitable conversion ratio of hydrogen peroxide and selectivity of an epoxidized olefin, the conditions of the olefin epoxidation reaction preferably include a temperature of 30 to 90 ° C, more preferably 40 °. 80 ° C; pressure is 0.5 ⁇ 4.5 MPa, further preferably 0.6 ⁇ 3 MPa; liquid volume space velocity is 1 ⁇ 15h, further preferably 2 ⁇ 1.
  • titanium silicalite powder purchased from Hunan Jianchang Co., Ltd., grade HTS
  • magnesium oxide 1 g
  • 20 g of silica sol (Si0) was added thereto. 2 content of 30% by weight
  • 2 grams of polyvinyl alcohol 1 gram
  • Tianjing powder purchased from Dongming County Zhujing Tianjing gum factory
  • 20 ml of water mixed uniformly and extruded into strips, size 2 x 2 mm, followed by drying at 70 ° C for 4 hours to obtain a molded product A.
  • calcined product B 100 g of the molded product A was placed in a three-necked bottle, 200 ml of a 20% by weight sodium hydroxide solution was added, heated to 90 ° C and kept for 6 hours, and then washed with deionized water until the washing water contained no sodium. Until the ions. Then, it was dried at 120 ° C for 3 hours and calcined at 550 ° C for 3 hours to obtain a calcined product B.
  • Example 1 100 g of calcined product B was placed in a three-necked flask, 200 ml of a 20% by weight sodium hydroxide solution and 10 ml of a 27.5% by weight hydrogen peroxide solution were added, and heated at 90 ° C for 2 hours under reflux, and then Wash with deionized water until the wash water contains no sodium ions. Finally, it was dried at 120 ° C for 3 hours and calcined at 550 ° C for 5 minutes to prepare a titanium-silicon molecular catalyst used in each of the examples and comparative examples of the present invention.
  • Example 1 100 g of calcined product B was placed in a three-necked flask, 200 ml of a 20% by weight sodium hydroxide solution and 10 ml of a 27.5% by weight hydrogen peroxide solution were added, and heated at 90 ° C for 2 hours under reflux, and then Wash with deionized water until the wash water contains no sodium ions. Finally, it was dried at 120 ° C
  • This example is intended to illustrate the method of epoxidation of the olefin provided by the present invention.
  • the titanium silicon molecular catalyst prepared in Preparation Example 1 and the macroporous strong basic styrene yin Ion exchange resin (purchased from Anhui Samsung Resin Co., Ltd., the total exchange capacity is
  • the method was carried out according to the method of Example 1, except that the catalyst bed charged in the fixed bed reactor did not include a macroporous strong basic styrene anion exchange resin, and the same weight of Preparation Example 1 was used.
  • the titanium silicalite catalyst prepared in the middle replaces the macroporous strong basic styrene anion exchange resin.
  • the hydrogen peroxide conversion rate and propylene oxide selectivity detected and calculated during the operation of the fixed bed reactor are shown in Table 2 below. Table 2
  • This example is intended to illustrate the method of epoxidation of the olefin provided by the present invention.
  • the titanium silicalite catalyst prepared in Preparation Example 1 and the macroporous strong basic styrene anion exchange resin (available from Anhui Samsung Resin Co., Ltd., total exchange capacity of 1.3 mmol/mL) were carried out at a weight ratio of 1:0.1.
  • the mixture was mixed and charged into a fixed bed reactor at a loading of 15 ml.
  • a catalyst bed was formed in the fixed bed reactor, and a ceramic ring packing was placed above and below the catalyst bed.
  • a reactant having a molar ratio of ethanol, propylene and hydrogen peroxide of 5:1.5:1 is injected into the fixed bed reactor at a liquid volume space ratio of 10 ° 1 to maintain the fixation.
  • the pressure in the bed reactor was IMPa, and the fixed bed reactor was continuously operated for 1,700 hours.
  • the hydrogen peroxide conversion rate and the propylene oxide selection were intermittently detected and calculated. The results are shown in Table 3 below. table 3
  • Comparative example 2 Performed according to the method of Example 2, except that in the catalyst bed charged in the fixed bed reactor, the same weight of Na 2 HP0 4 was used instead of the macroporous strong basic styrene anion exchange. Resin. Hydrogen peroxide conversion and propylene oxide selectivity were calculated and detected during the operation of the fixed bed reactor, and the results are shown in Table 4 below. Table 4
  • This example is intended to illustrate the method of epoxidation of the olefin provided by the present invention.
  • the titanium silicalite catalyst prepared in Preparation Example 1 and the macroporous strong basic acrylic anion exchange resin purchased from Hangzhou Zhengguang Resin Co., Ltd., with a total exchange capacity of 1.5 mmol/mL) were mixed at a weight ratio of 1:0.5. And charged into a fixed bed reactor at a loading of 15 ml, a catalyst bed was formed in the fixed bed reactor, and a ceramic ring packing was respectively placed above and below the catalyst bed.
  • a reactant having a molar ratio of acetonitrile, propylene and hydrogen peroxide of 10:2.5:1 is injected into the fixed bed reactor at a liquid volume of 21 T 1 to maintain the fixed bed.
  • the pressure in the reactor was 3 MPa, and the fixed bed reactor was continuously operated for 1,700 hours.
  • the hydrogen peroxide conversion rate and the propylene oxide selectivity were intermittently detected and calculated. The results are shown in Table 5 below. Reaction time (hours) Conversion of hydrogen peroxide (%) Selectivity of propylene oxide (%)
  • This example is intended to illustrate the method of epoxidation of the olefin provided by the present invention.
  • Titanium silicon molecular sieve powder purchasedd from Hunan Jianchang Co., Ltd., grade HTS
  • gel type strong alkaline styrene anion exchange resin purchasedd from Shandong Dongda Chemical Industry Co., Ltd., total exchange capacity of 1.3mmol/mL
  • the mixture was mixed at a weight ratio of 1:1, and continuously added from the top of the moving bed reactor (purchased from Chengdu Xindu Yongtong Machinery Factory), while the titanium silicalite catalyst and the gel type were strongly alkaline.
  • the mixture of the mixed titanium-silicon molecular sieve catalyst of the styrene-based anion exchange resin and the gel-type strongly basic styrene-based anion exchange resin is 15 ml; and the molar ratio of decyl alcohol, propylene and hydrogen peroxide is The 6:2:1 reactant was continuously injected from the bottom of the moving bed reactor at a liquid volume space of 7 h, and the temperature in the reactor was maintained at 60 ° C and the pressure was 2.5 MPa.
  • the fixed bed reactor was continuously operated for 1,700 hours, and during the operation of the fixed bed reactor, the hydrogen peroxide conversion rate and the propylene oxide selectivity were intermittently detected and calculated, and the results are shown in Table 6 below.
  • This example is intended to illustrate the method of epoxidation of the olefin provided by the present invention.
  • the titanium silicalite catalyst prepared in Preparation Example 1 and the macroporous strong basic styrene anion exchange resin (available from Anhui Samsung Resin Co., Ltd., with a total exchange capacity of 1.5 mmol/ml) were respectively 85:15 by weight.
  • the layers, with a total loading of 15 ml, were respectively filled with porcelain ring fillers under the catalyst bed.
  • Example 8 The method was carried out according to the method of Example 5, except that the catalyst bed charged in the fixed bed reactor did not include a macroporous strong basic styrene anion exchange resin, and the same weight of Preparation Example 1 was used.
  • the titanium silicalite catalyst prepared in the middle replaces the macroporous strong basic styrene anion exchange resin.
  • the hydrogen peroxide conversion and propylene oxide selectivity were measured and calculated during the operation of the fixed bed reactor, and the results are shown in Table 8 below. Table 8
  • the titanium silicalite catalyst prepared in Preparation Example 1 and the macroporous strong basic styrene anion exchange resin (purchased from Anhui Samsung Resin Co., Ltd., total exchange capacity of 1.3 mmol/mL) were respectively 90:10 by weight.
  • a four-layer catalyst bed of 1 with a total loading of 15 ml was placed under the catalyst bed with a ceramic ring packing.
  • the method was carried out according to the method of Example 7, except that in the process of forming the catalyst bed, only the titanium silicon molecular sieve catalyst prepared in Preparation Example 1 and the macroporous strong basic acrylic anion exchange resin (purchased from Hangzhou) were used.
  • the company has a total exchange capacity of 1.5 mmol/mL.
  • the mixture is mixed in a weight ratio of 95:5 and packed into a fixed bed reactor. Hydrogen peroxide conversion and propylene oxide selectivity were calculated and detected during operation of the fixed bed reactor, and the results are shown in Table 12 below. Table 12
  • the titanium silicon molecular sieve catalyst prepared in Preparation Example 1, the titanium silicon molecular sieve catalyst prepared in Preparation Example 1, and the gel type strong basic phenethyl anion exchange resin purchased from Shandong Dongda Chemical Industry Co., Ltd., total The exchange capacity was 1.3 mmol/mL.
  • a reactant having a molar ratio of methanol, propylene sulfide and hydrogen peroxide of 6:2:1 was injected into the fixed bed reactor at a liquid volume of 2 h at 40 ° C to maintain the fixed bed.
  • the pressure in the reactor was 2.5 MPa, and the fixed bed reactor was continuously operated for 1,700 hours.
  • the hydrogen peroxide conversion rate and the propylene oxide selection were intermittently detected and calculated. The results are shown in Table 13 below.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention porte sur un procédé d'époxydation pour des oléfines. Le procédé comprend une réaction d'époxydation entre une oléfine et du peroxyde d'hydrogène en présence d'un catalyseur et de résine échangeuse d'anions basique dans les conditions permettant l'époxydation d'oléfines. À l'aide dudit procédé de la présente invention, le taux de conversion du peroxyde d'hydrogène, la sélectivité pour la production d'oléfines époxydées et la durée de vie du catalyseur peuvent être considérablement accrus.
PCT/CN2011/001702 2010-10-11 2011-10-11 Procédé d'époxydation pour oléfine WO2012048528A1 (fr)

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Application Number Priority Date Filing Date Title
SG2013027131A SG189877A1 (en) 2010-10-11 2011-10-11 Epoxidation method for olefin
RU2013120980/04A RU2576620C2 (ru) 2010-10-11 2011-10-11 Способ эпоксидирования олефина

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CN201010511512.6A CN102442975B (zh) 2010-10-11 2010-10-11 一种烯烃环氧化的方法
CN201010511512.6 2010-10-11
CN201010511546.5 2010-10-11
CN201010511546.5A CN102442977B (zh) 2010-10-11 2010-10-11 一种烯烃环氧化的方法

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Publication number Priority date Publication date Assignee Title
WO2018205244A1 (fr) * 2017-05-12 2018-11-15 Evonik Degussa Gmbh Procédé d'époxydation de propène

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