A method for preparing dicyclopentadiene dioxide and alkylene oxide by using titanium silicon molecular sieve catalyst

Abstract

The invention discloses a method for preparing dicyclopentadiene dioxide and alkylene oxide by using titanium silicon molecular sieve catalyst, comprising: first reacting DCPD with an excess of organic peroxide to generate dicyclopentadiene dioxide, then adding an olefin having 3 to 10 carbon atoms to the reaction product, and continuing to react the excess organic peroxide with the olefin to generate alkylene oxide, thereby effectively removing the organic peroxide in the reaction product. The preparation method is used for the synthesis of dicyclopentadiene dioxide, and not only has high DCPD conversion rate and product selectivity, but also has simple process operation, and can also synthesize alkylene oxide, and the organic peroxide in the reactant is fully utilized, effectively solving the problem of separating organic peroxide in the reaction product, and also providing a green reaction process for synthesizing alkylene oxide.

Description

Technical Field

[0001] The invention belongs to the technical field of catalytic oxidation synthesis of organic epoxy compounds and catalytic oxidation of olefins, and specifically relates to a method for jointly preparing dicyclopentadiene dioxide and alkylene oxide by using titanium silicon molecular sieve catalyst. Background Art

[0002] Dicyclopentadiene is an important component in the C5 fraction of petroleum cracking, accounting for about 14% to 19% of the C5 fraction. The epoxidation product of dicyclopentadiene, dicyclopentadiene dioxide, is an alicyclic epoxide with excellent performance. Compared with ordinary epoxy resins, dicyclopentadiene dioxide has better performance in high temperature resistance, heat resistance, weather resistance, UV resistance, electrical insulation, high strength, etc. Based on the above properties, dicyclopentadiene dioxide is widely used in high temperature resistant castings, fiberglass, adhesives, laminated materials and electronic device packaging.

[0003] In the prior art, dicyclopentadiene dioxide is usually prepared by epoxidation of dicyclopentadiene using methods such as peracetic acid method, chlorohydrin method and hydroperoxide catalytic epoxidation method. However, these three methods currently have shortcomings, such as complex reaction process, severe equipment corrosion, easy acidic ring opening of epoxide to generate by-products, and high emission of "three wastes". In recent years, the green epoxidation process using hydrogen peroxide as the oxygen source and heteropolyacid compounds as catalysts has received widespread attention. According to the catalytic mechanism, the catalyst can be divided into homogeneous catalysts and heterogeneous catalysts. The homogeneous catalytic reaction is to directly add the heteropolyacid or its salts to the reaction system, which has high catalytic efficiency, but the catalyst is not easy to recover, the cost is high and there are many "three wastes"; while the heterogeneous catalytic reaction can achieve the recycling of the catalyst while maintaining a relatively high catalytic efficiency, and has therefore received widespread attention and in-depth research from domestic and foreign scientific researchers. Venturello et al. reported that Na 2 WO 4 / H 3 PO 4 / H 2 O 2 In the presence of a phase transfer catalyst, the two-phase catalytic epoxidation reaction system has a conversion rate of 95% for most olefins such as cyclohexene and styrene, and a selectivity for epoxides of about 80% (J. Org. Chem, 1983, 48 (21): 3831-3833). Ishii et al. reported that heteropolyacid H 3 PW 12 O 40 or H 3 PMo 12 O 40 In the presence of a catalyst composed of hexadecylpyridinium chloride, 35% H 2 O2 The epoxidation reaction of various organic substrates can be effectively carried out in a homogeneous or two-phase system. However, when this catalyst system is used for the synthesis of dicyclopentadiene dioxide, it has the disadvantages of easy loss of heteropolyacid, difficulty in catalyst separation and recovery, and limited number of reuses, making it difficult to use in industrial equipment (J. Org. Chem, 1998, 53 (15): 3587-3593). Li Li et al. reported that H 3 PW 12 O 40 Impregnate the silica surface with H 2 O 2 It is an oxidant for the synthesis of dicyclopentadiene dioxide, and the initial activity of the catalyst is very high, but in the reaction process, the heteropoly acid adsorbed on the surface of silicon dioxide is easily lost, and the catalyst cannot be reused (the green synthesis new process of preparing dicyclopentadiene dioxide by heteropoly acid catalysis dicyclopentadiene [D]. Jilin, Northeast Normal University, 2007.). It can be seen from this that by impregnation method and sol-gel method, heteropoly acid is loaded on the surface of silicon dioxide, although the catalyst recovery problem can be solved, heteropoly acid is easy to fall off from the catalyst support surface during the reaction, resulting in a short catalyst life, and generally after being reused 5 to 6 times, the catalyst activity significantly decreases, and it is not easy to be used for industrial generation devices. In summary, by heterogeneous catalytic oxidation method, epoxypentadiene dioxide is prepared, although the recycling of the catalyst is realized, there is a problem that heteropoly acid is easy to fall off and causes a short catalyst life.

[0004] Since the DCPD molecule has two double bonds, in order to completely convert DCPD into dicyclopentadiene dioxide, an excess of organic peroxide must be used. However, an excess of organic peroxide brings many problems to the separation and purification of the product and also has many adverse effects on the activity of the catalyst. Summary of the invention

[0005] In order to solve the defects of the synthesis process of dicyclopentadiene dioxide, the inventors found that by using titanium silicon molecular sieve catalyst and organic peroxide as oxidant, dicyclopentadiene can be effectively synthesized into dicyclopentadiene dioxide (DCPDDO), and the reaction yield can reach 95% to 100%. The existing Ti-HMS molecular sieve catalyst is used for DCPDDO synthesis, and the initial activity is good, but the reaction activity decreases significantly with the increase of the number of uses. The important reason is that excessive organic peroxide will introduce more water into the reaction system, and the organic peroxide itself will also partially decompose during the reaction to produce water and acid, which is easy to cause the reaction product to polymerize itself, causing the catalyst pores to be blocked, the HMS skeleton to rupture, and the titanium to be lost, thereby deactivating the catalyst, which limits the use of Ti-HMS for the synthesis of dicyclopentadiene dioxide.

[0006] In order to solve this problem, the present invention improves the titanium-containing molecular sieve catalyst Ti-HMS with mesoporous characteristics, introduces hydrotalcite or hydrotalcite-like and nano-carbon fiber into the catalyst, and greatly improves the performance of Ti-HMS.

[0007] The technical solution of the present invention is specifically described as follows.

[0008] The present invention provides a method for jointly preparing dicyclopentadiene dioxide and alkylene oxide by using titanium silicon molecular sieve catalyst, comprising:

[0009] (1) First, dicyclopentadiene DCPD is used as a reaction raw material and an organic peroxide is used as an oxidant. In an inert solvent, DCPD is subjected to a catalytic oxidation reaction under the action of a titanium silicon molecular sieve catalyst to generate dicyclopentadiene dioxide, and then an olefin having a carbon number of 3 to 10 is added to continue the reaction to obtain a mixed solution of dicyclopentadiene dioxide and alkylene oxide;

[0010] The titanium silicon molecular sieve catalyst is a modified Ti-HMS molecular sieve catalyst with mesoporous characteristics, and its components include: Ti mass fraction of 0.1% to 6%, nano carbon fiber mass fraction of 50% to 70%, SiO 2 The mass fraction is 25% to 45%, the mass fraction of the metal oxide introduced by the hydrotalcite or the hydrotalcite-like substance is 0.01% to 3%, and the UV-vis spectrum of the catalyst has a strong absorption peak at 220nm.

[0011] The catalytic oxidation reaction temperature is 50-150°C, the pressure is 0-10MPa (gauge pressure), the molar ratio of organic peroxide to DCPD is 6:1-2:1, the molar ratio of organic peroxide to olefins with carbon atoms of 3-10 is 1:5-1:20; the volume ratio of inert solvent to DCPD or olefins with carbon atoms of 3-10 is 3:1-33:1;

[0012] (2) The mixed solution obtained in step (1) is subjected to conventional distillation, with a reflux ratio of 3 to 10:1, a bottom temperature of 50 to 140° C., and a top temperature of 20 to 100° C., and an alkylene oxide product with a purity of 60% to 99% is obtained at the top of the tower, and a dicyclopentadiene dioxide product with a purity of 50% to 85% is obtained at the bottom of the tower.

[0013] Furthermore, the olefin having 3 to 10 carbon atoms is an aliphatic monoolefin having 3 to 6 carbon atoms.

[0014] Furthermore, the catalytic oxidation reaction temperature is 60-100° C., the pressure (gauge pressure) is 0.3-3 MPa, and the molar ratio of the organic peroxide to DCPD is 3:1-2:1.

[0015] Furthermore, the catalytic oxidation reaction adopts an intermittent reaction process or a fixed bed continuous reaction process; in the intermittent reaction process, the mass ratio of the catalyst to DCPD or the olefin having 3 to 10 carbon atoms is 0.01:100 to 20:100, and the reaction time is 2 to 10 hours; in the fixed bed continuous reaction process, the total material volume space velocity is 0.1 to 4.22 h -1 .

[0016] Furthermore, the mass ratio of the catalyst to DCPD or the olefin having 3 to 10 carbon atoms is 0.5:100 to 10:100, and the reaction time is 3 to 6 hours.

[0017] Furthermore, the oxidant is selected from any one of benzoyl hydroperoxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, and isopropylbenzene hydroperoxide.

[0018] Furthermore, the oxidant is cumene hydroperoxide.

[0019] Furthermore, the inert solvent is selected from any one of benzene, toluene, ethylbenzene, isopropylbenzene, acetone, petroleum ether, cyclohexane, n-heptane and dodecane.

[0020] Furthermore, the inert solvent is cumene.

[0021] Furthermore, the modified Ti-HMS molecular sieve catalyst is prepared by the following method:

[0022] a) Under an inert atmosphere, a silicon source, a titanium source and a template are dissolved in a mixed solvent of water and an organic alcohol, stirred and crystallized at room temperature for 0.5-10 hours, nano-carbon fibers are added and stirred for 10-72 hours, and then crystallized at 150-200° C. for 1-7 days. The crystallized product is separated, washed and dried to obtain Ti-HMS loaded with nano-carbon fibers;

[0023] b) putting the Ti-HMS supported by nano-carbon fibers into an aqueous solution of hydrotalcite or other hydrotalcite-like substances, stirring at room temperature for 10 to 48 hours, separating the solid, washing the solution with water until it is neutral, drying, and then calcining at 300 to 800° C. for 2 to 20 hours in an inert atmosphere to obtain a Ti-HMS catalyst matrix modified by metal oxide and supported by nano-carbon fibers;

[0024] c) Treating the Ti-HMS catalyst matrix with an organosilicon solution at a temperature of 25 to 300° C. for 0.5 to 20 hours; the amount of organosilicon used is 10% to 70% of the weight of the Ti-HMS catalyst matrix; then filtering and separating the solid catalyst, washing with an inert solvent, and then baking the solid catalyst in an environment of a pressure of 0.133 to 1.33 KPa and a temperature of 80 to 200° C. for 10 to 24 hours to obtain a titanium silicon molecular sieve catalyst with nano-carbon fibers as a carrier.

[0025] Further, in step a), the silicon source is one or both of orthosilicate or hydrocarbon silicate; the titanium source is titanate; and the template is of the general formula RNH 2 An organic amine, R is a chain hydrocarbon group of 6 to 18 carbon atoms; RNH 2 The molar ratio of Si in the silicon source is 0.01-0.5:1, the molar ratio of Si in the silicon source to Ti in the titanium source is 5-200:1, the molar ratio of water to the silicon source is 4-20:1, the volume ratio of alcohol to the silicon source is 1-4:1, and the molar ratio of nano-carbon fiber to the silicon source is 5-20:1.

[0026] Furthermore, the titanate used is selected from any one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, and tetraisobutyl titanate.

[0027] Furthermore, in step a), the nano-carbon fibers used are prepared from a carbon-containing gas source, preferably CO, CH 4 , C 2 H 6 , C 3 H 8 Any one of the following is used as the reaction raw material, and an element of Group VIII of the periodic table, more preferably any single metal element or alloy of multiple elements selected from Fe, Co, and Ni is used as the catalyst. Nano-carbon fibers are formed by catalytic cracking reaction of a carbon-containing gas source, and the temperature for catalytic growth of the nano-carbon fibers is 550 to 650°C.

[0028] Furthermore, in step b), the volume ratio of Ti-HMS supported by nanocarbon fibers to hydrotalcite or other hydrotalcite-like aqueous solution is 1:1 to 1:3, and the molar ratio of hydrotalcite or other hydrotalcite-like aqueous solution to the silicon source used in step a) is 0.01:100 to 3:100; the calcination temperature is 300 to 600°C, and the calcination time is 3 to 8 hours.

[0029] Further, in step b), the general formula of the hydrotalcite-like compound is as follows: 1-X 2+ N X 3+ (OH) 2 (A n- ) x / n .m H 2 O, of which: M 2+ Selected from Mg 2+ 、Ni 2+ 、Co 2+ 、Zn 2+ , Ca 2+ , Fe 2+ , Cu 2+ Any one of N 3+ Selected from Al3+ , Fe 3+ Cr 3+ Sc 3+ Any one of A n- Selected from CO 3 2- 、NO 3 - , Cl – or OH - Any one of the following; x represents M +3 The fraction of the total number of cations is between 0.20 and 0.33, where m represents the number of crystals and n represents the charge number of the anion.

[0030] Furthermore, in step c), the organosilicon solution used, the organosilicon is selected from any one of halosilanes, silazanes or silylamines.

[0031] Furthermore, in step c), the organosilicon is selected from any one of trimethylchlorosilane, hexamethyldisilazane or N-trimethylsilylimidazole.

[0032] Furthermore, in step c), the solvent of the organic silicon solution used is selected from any one or a mixture of benzene, toluene, cumene, ethylbenzene, cyclohexane, n-heptane, octane and dodecane.

[0033] Furthermore, in step c), washing with an inert solvent comprises: washing the solid catalyst three times with an inert solvent such as toluene, benzene, or alkane, wherein the volume of the inert solvent used in each washing is 5 to 10 times the volume of the solid catalyst.

[0034] Excessive organic peroxide not only affects the catalyst reaction activity, but also is difficult to separate from the reaction product. If it is not separated, it will cause safety problems in the post-processing of the product, affect the product quality index, and increase the consumption of organic peroxide. The present invention provides a method for effectively solving the problem, the process of which is as follows: firstly, DCPD is reacted with excessive organic peroxide to generate dicyclopentadiene dioxide, then an olefin with 3 to 10 carbon atoms is added to the reaction product, and the excessive organic peroxide continues to react with the olefin to generate alkylene oxide, thereby effectively removing the organic peroxide in the reaction product.

[0035] The preparation process of the present invention, if adopting the intermittent process, firstly synthesizes dicyclopentadiene dioxide in a reactor, then adds olefins with carbon number of 3 to 10 in the reactor, does not change the reaction temperature and pressure operation range, and performs the second step reaction to generate alkylene oxide. If adopting the fixed bed continuous reaction, then adopts the double reactor series reaction, first synthesizes dicyclopentadiene dioxide in the first reactor, after the reaction product leaves the first reactor, mixes with olefins with carbon number of 3 to 10 and enters the second reactor, and the excess organic peroxide reacts with olefins to generate alkylene oxide. By controlling the injection amount of olefins, the conversion rate of the unreacted organic peroxide in the reactor reaches 99% to 100%. The two stages of reaction temperature and pressure operation range are the same, the reaction yield of dicyclopentadiene dioxide is 95% to 100%, and the reaction yield of alkylene oxide is 98% to 100%, the process operation is simple, the product yield is high, and it is easy to realize industrialization.

[0036] Compared with the prior art, the present invention has the following advantages:

[0037] According to the preparation method provided by the present invention, for the synthesis of dicyclopentadiene dioxide, not only the DCPD conversion rate and product selectivity are high, and the process operation is simple, but also alkylene oxide can be synthesized at the same time, the organic peroxide in the reactant is fully utilized, the problem of separating the organic peroxide in the reaction product is effectively solved, and a green reaction process is provided for the synthesis of alkylene oxide. Specific embodiments

[0038] The present invention is further described below with reference to the examples, but the present invention is not limited to the examples. The product yield in this patent specification is defined as:

[0039] DCPDDO yield = number of moles of DCPDDO in the reaction product / number of moles of DCPD raw material involved in the reaction * 100%.

[0040] Alkylene oxide yield = number of moles of alkylene oxide in the product / number of moles of organic peroxide reacted with olefin having 3 to 10 carbon atoms * 100%.

[0041] The organic peroxides in the reaction products were determined by iodine titration, and DCPDDO and alkylene oxides were quantified by gas chromatography external standard method.

[0042] Example 1 Preparation of modified Ti-HMS molecular sieve catalyst

[0043] In a 500 ml reactor, add 25 g of hexadecylamine, 45 ml of water and 250 ml of ethanol in turn at room temperature and under stirring conditions, and stir; add 65 g of ethyl orthosilicate and 5.5 g of diethyl diethyl silicate dissolved in 30 ml of ethanol to the above solution and stir for 60 minutes; add 14.2 g of tetraethyl titanate, stir and crystallize for 10 hours; add 74.9 g of nano-carbon fibers and continue stirring for 10 to 72 hours. Raise the temperature, and after crystallizing the material in the reactor at 200°C for 4 days, filter to obtain a solid, extract with ethanol to remove the template in the catalyst, and then wash with pure water until the eluent is neutral. Dry the washed solid at 110°C for 12 hours to obtain Ti-HMS with nano-carbon fibers as the carrier;

[0044] 300 ml of pure water, 3.0 g of magnesium aluminum hydrotalcite (Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O), room temperature, stirred for 48 hours, separated the solid, washed with pure water until the water washing liquid was neutral, dried at 80°C for 20 hours, and then calcined at 400°C in a helium atmosphere for 20 hours to obtain Ti-HMS modified with alkali metal oxide and nano-carbon fiber as the carrier;

[0045] In a 100 ml reactor, 20 g of the catalyst matrix prepared above was added, 10 g of trimethylchlorosilane and 50 ml of toluene were added, and the nitrogen of 0.3 MPa was replaced three times. Silylation reaction was carried out at 180°C under mechanical stirring for 10 hours, and the reaction was terminated. The liquid was cooled to room temperature, and the solid catalyst was separated and rinsed with 50 ml of toluene three times to remove trimethylchlorosilane from the catalyst. It was vacuum dried at 0.133 KPa and 200°C for 5 hours to obtain a Ti-HMS catalyst modified with alkali metal oxide and nano-carbon fiber as a carrier.

[0046] Examples 2 to 8 Synthesis of DCPDDO, 1,2-epoxypentane and 2,3-epoxypentane

[0047] 20 grams of the catalyst prepared in Example 1 were respectively loaded into two 100 ml dual isothermal fixed bed reactors connected in series, and the reaction liquid was pumped into the reactor by a metering pump. A continuous reaction process with two reactors in series was adopted to investigate the effects of temperature, pressure, material ratio, and space velocity on the reaction yield of the reaction product DCPDDO, 1,2-epoxypentane or 2,3-epoxypentane. One reactor synthesized dicyclopentadiene dioxide, and the second reactor was a reactor in which an excess of organic peroxide in the first reactor reacted with 1-pentene or 2-pentene to generate 1,2-epoxypentane or 2,3-epoxypentane. The olefin raw material used in the second-stage reaction of Examples 2 to 5 was 1-pentene, and the olefin raw material used in the second-stage reaction of Examples 6 to 8 was 2-pentene. The results are shown in Tables 1 and 2.

[0048] Table 1 One-stage reaction process

[0049]

[0050] Table 2 Two-stage reaction process

[0051]

[0052] Examples 9 to 15 Synthesis of DCPDDO and Cyclopentene Oxide

[0053] 20 grams of the catalyst prepared in Example 1 were respectively loaded into two 50 ml dual isothermal fixed bed reactors, and the reaction liquid was fed into the reactor by a metering pump. A two-stage continuous reaction process was adopted to investigate the effects of temperature, pressure, material ratio, and space velocity on the reaction yields of the reaction products DCPDDO and cyclopentene oxide. The first stage reactor synthesized dicyclopentadiene dioxide, and the second stage reactor was a reactor in which excess organic peroxide reacted with cyclopentene to generate cyclopentene oxide. The results are shown in Tables 3 and 4.

[0054] Table 3 One-stage reaction process

[0055]

[0056] Table 4 Two-stage reaction process

[0057]

[0058] Examples 16-22 Synthesis of DCPDDO and Propylene Oxide

[0059] 20 grams of catalyst prepared in Example 1 were loaded into two 50 ml dual isothermal fixed bed reactors, respectively, and a two-stage reactor was used in series to form a continuous reaction process. The reaction liquid was transported to the reactor by a metering pump, and propylene was mixed with the outlet material of the first reactor before entering the second reactor to investigate the effects of temperature, pressure, material ratio, and space velocity on the reaction yield of the reaction product DCPDDO and propylene oxide. The first reactor synthesized dicyclopentadiene dioxide, and the second reactor was used for the reaction of excess organic peroxide in the first reactor with propylene to generate propylene oxide. The results are shown in Tables 5 and 6.

[0060] Table 5. Process conditions for the first stage reaction

[0061]

[0062]

[0063] Table 6 Second stage reaction process conditions

[0064]

[0065] Examples 23-29 Synthesis of DCPDDO and cyclohexene oxide

[0066] 20 grams of catalyst prepared in Example 1 were respectively loaded into 50 ml of two series-connected isothermal fixed-bed reactors. A two-stage reactor series connection process was adopted. DCPD, organic peroxide CHP and solvent were mixed and pumped into a first-stage reactor. Cyclohexene was mixed with the outlet material of the first-stage reactor and pumped into a second-stage reactor by a metering pump. The effects of temperature, pressure, material ratio and space velocity on the reaction yield of the reaction product DCPDDO and cyclohexene oxide were investigated. The first-stage reactor synthesized dicyclopentadiene dioxide, and the second-stage reactor was a reactor in which excess cumene hydroperoxide reacted with cyclohexene to generate cyclohexene oxide. The results are shown in Tables 7 and 8.

[0067] Table 7 Process conditions for the first stage reaction

[0068]

[0069] Table 8 Second stage reaction process conditions

[0070]

[0071]

[0072] The preferred embodiments of the present invention have been specifically described above, but the present invention is not limited to the embodiments. Those skilled in the art may make various equivalent modifications or substitutions without violating the spirit of the present invention. These equivalent modifications or substitutions are all included in the scope defined by the claims of this application.

Claims

1. A method for preparing dicyclopentadiene dioxide and alkylene oxide by using titanium silicon molecular sieve catalyst, comprising: (1) First, dicyclopentadiene DCPD is used as a reaction raw material and an organic peroxide is used as an oxidant. In an inert solvent, DCPD is subjected to a catalytic oxidation reaction under the action of a titanium silicon molecular sieve catalyst to generate dicyclopentadiene dioxide, and then an olefin having a carbon number of 3 to 10 is added to continue the reaction to obtain a mixed solution of dicyclopentadiene dioxide and alkylene oxide; The titanium silicon molecular sieve catalyst is a modified Ti-HMS molecular sieve catalyst with mesoporous characteristics, and its components include: Ti mass fraction of 0.1% to 6%, nano-carbon fiber mass fraction of 50% to 70%, SiO2 mass fraction of 25% to 45%, and metal oxide mass fraction introduced by hydrotalcite or hydrotalcite-like is 0.01% to 3%; The titanium silicon molecular sieve catalyst is prepared by the following method: a) Under an inert atmosphere, a silicon source, a titanium source and a template are dissolved in a mixed solvent of water and an organic alcohol, stirred and crystallized at room temperature for 0.5-10 hours, nano-carbon fibers are added and stirred for 10-72 hours, and then crystallized at 150-200° C. for 1-7 days. The crystallized product is separated, washed and dried to obtain Ti-HMS loaded with nano-carbon fibers; b) putting the Ti-HMS supported by nano-carbon fibers into an aqueous solution of hydrotalcite or other hydrotalcite-like substances, stirring at room temperature for 10 to 48 hours, separating the solid, washing the solution with water until it is neutral, drying, and then calcining at 300 to 800° C. for 2 to 20 hours in an inert atmosphere to obtain a Ti-HMS catalyst matrix modified by metal oxide and supported by nano-carbon fibers; c) treating the Ti-HMS catalyst matrix with an organic silicon solution at a temperature of 25 to 300° C. for 0.5 to 20 hours; the amount of organic silicon used is 10% to 70% of the weight of the Ti-HMS catalyst matrix; then filtering and separating the solid catalyst, washing it with an inert solvent, and then baking the solid catalyst in an environment of a pressure of 0.133 to 1.33 KPa and a temperature of 80 to 200° C. for 10 to 24 hours to obtain a titanium silicon molecular sieve catalyst with nano-carbon fibers as a carrier; The catalytic oxidation reaction temperature is 50-150°C, the pressure is 0-10MPa, the molar ratio of organic peroxide to DCPD is 6:1-2:1, the molar ratio of organic peroxide to olefins with carbon atoms of 3-10 is 1:5-1:20; the volume ratio of inert solvent to DCPD or olefins with carbon atoms of 3-10 is 3:1-33:1; (2) The mixed solution obtained in step (1) is subjected to conventional distillation, with a reflux ratio of 3 to 10:1, a bottom temperature of 50 to 140°C, and a top temperature of 20 to 100°C, to obtain an alkylene oxide product with a purity of 60% to 99% at the top of the tower, and a dicyclopentadiene dioxide product with a purity of 50% to 85% at the bottom of the tower.

2. The method according to claim 1, characterized in that: The olefin having 3 to 10 carbon atoms is an aliphatic monoolefin having 3 to 6 carbon atoms.

3. The method according to claim 1, characterized in that: The catalytic oxidation reaction temperature is 60-100° C., the pressure (gauge pressure) is 0.3-3 MPa, and the molar ratio of the organic peroxide to DCPD is 3:1-2:

1.

4. The method according to claim 1, characterized in that: The catalytic oxidation reaction adopts a batch reaction process or a fixed bed continuous reaction process; in the batch reaction process, the mass ratio of the catalyst to DCPD or the olefin with 3 to 10 carbon atoms is 0.01:100 to 20:100, and the reaction time is 2 to 10 hours; in the fixed bed continuous reaction process, the total material volume space velocity is 0.1 to 4.22 h -1 .

5. The method according to claim 1, characterized in that: The mass ratio of the catalyst to DCPD or the olefin with 3 to 10 carbon atoms is 0.5:100 to 10:100, and the reaction time is 3 to 6 hours.

6. The method according to claim 1, characterized in that: The oxidant is selected from any one of benzoyl hydroperoxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide and isopropylbenzene hydroperoxide.

7. The method according to claim 6, characterized in that: The oxidant is cumene hydroperoxide.

8. The method according to claim 1, characterized in that: The inert solvent is selected from any one of benzene, toluene, ethylbenzene, isopropylbenzene, acetone, petroleum ether, cyclohexane, n-heptane and dodecane.

9. The method according to claim 8, characterized in that: The inert solvent is cumene.

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