Method for preparing epoxidized dicyclopentadiene, catalyst and preparation

Abstract

The invention relates to a synthesis method of dicyclopentadiene dioxide. According to the method, a heterogeneous catalysis process is adopted, the composition of a composite catalyst is FeCoaMnbXcOd / SiO2-[PW], under the catalysis of the catalyst, dicyclopentadiene is taken as a raw material, EDTA is taken as an auxiliary agent, hydrogen peroxide is taken as an oxidizing agent under the solvent-free condition, and dicyclopentadiene dioxide is generated through direct oxidation; and after the reaction is finished, cooling the reaction liquid, recycling the solid catalyst in the reaction liquid, filtering the organic phase by using activated carbon, and carrying out reduced pressure distillation to remove the solvent, thereby obtaining the dicyclopentadiene dioxide. The reaction method is simple, the reaction can be carried out under normal pressure, the catalyst is good in catalytic activity, long in service life, easy to recover, high in recovery rate, low in energy consumption and environmentally friendly, and the reaction yield reaches 90% or above.

Description

Technical Field

[0001] The invention belongs to the field of chemical industry, designs a supported polyacid catalyst, catalytic oxidation synthesis of organic epoxides Background Art

[0002] With the rapid development of my country's petrochemical industry, the production capacity of ethylene produced from liquid hydrocarbons is growing, and the comprehensive utilization rate of C5 is also increasing, especially in some developed countries abroad, where the comprehensive utilization rate is 70-80%, while the comprehensive utilization rate of C5 in my country is less than 20%. C5 is actually a valuable resource that can be used to produce a series of high value-added chemical products. Countries around the world generally pay attention to the development and utilization of C5 and have carried out a lot of research and development work.

[0003] In recent years, the utilization of C5 fraction has shifted from the initial mixed utilization to the utilization of separated single components, and has also developed towards the preparation of fine chemical products. Dicyclopentadiene is an important component of the C5 fraction of petroleum cracking, accounting for about 14%-19% of the C5 fraction. Its epoxidation product, dicyclopentadiene dioxide, is a high-performance epoxy resin material. The material made of it has the advantages of good heat resistance, high hardness, weather resistance and excellent electrical insulation performance. It can be used for potting glue of high-temperature resistant mutual inductors and micromotors, adhesives for structural parts, adhesives for glass fiber reinforced plastics and laminated plastics.

[0004] Dicyclopentadiene dioxide is prepared by epoxidation of dicyclopentadiene, and the raw materials are easily available. Traditional methods for preparing olefin epoxides include the chlorohydrin method and the peracid method, but these methods have the disadvantages of low selectivity, severe equipment corrosion, complex reaction process, acidic ring opening of epoxides, and the generation of a series of by-products. Compared with traditional production processes, epoxidation using H2O2 as an oxygen source has advantages. First, the by-product of the reaction is water; second, the proportion of active oxygen components in H2O2 is very high. Therefore, H2O2 has attracted widespread attention as a green and environmentally friendly oxygen source for olefin epoxidation. Among them, heteropoly compounds have attracted much attention in the field of catalysis because of their suitable acidity and alkalinity and redox properties, and their acidity and redox properties can be regulated at the atomic or molecular level. However, the catalyst recovery of homogeneous reactions catalyzed by heteropoly acids is difficult, and solid heteropoly acids cannot fully exert their catalytic activity due to their small specific surface area, which limits their application. By effectively loading heteropolyacids on manganese oxide carriers, heterogeneity of homogeneous catalytic reactions can be achieved, which is beneficial for the separation of products and catalysts. At the same time, the loading increases the available area of ​​the active components, thereby reducing the amount of heteropolyacid used and improving the utilization efficiency of the catalyst. Summary of the invention

[0005] In view of the problems existing in the prior art, the present invention provides a method for preparing dicyclopentadiene dioxide. The specific scheme is:

[0006] The multiphase catalytic oxidation process of dicyclopentadiene is adopted, with dicyclopentadiene as raw material, hydrogen peroxide as oxidant, composite oxide-supported heteropoly acid as catalyst, EDTA as auxiliary agent, and solvent-free conditions, under normal pressure, dicyclopentadiene dioxide can be obtained by reaction. After the reaction of dicyclopentadiene is completed, the catalyst is recycled, and the organic phase is filtered through activated carbon and then distilled under reduced pressure to remove the solvent to obtain pure dicyclopentadiene dioxide. The reaction process is simple, the amount of dicyclopentadiene used is small, and the product is easy to separate.

[0007] The amount of catalyst used is 0.01 to 0.1 times the mass of hydrogen peroxide.

[0008] The dosage of the auxiliary agent EDTA is 0.005 to 0.01 times the mass of the catalyst.

[0009] The mass ratio of hydrogen peroxide to dicyclopentadiene is 1.5-2.5:1.

[0010] The mass concentration of hydrogen peroxide is controlled at 25-35%

[0011] The reaction temperature is controlled at 40-80°C, and the reaction time is controlled at 4-9h.

[0012] The conversion rate of dicyclopentadiene is greater than 95%, the conversion rate of dicyclopentadiene recycled after the catalyst is recovered is greater than 90%, and the catalyst recovery rate is greater than 90%.

[0013] After the reaction is completed, the catalyst is recovered by filtration or centrifugation for further reuse.

[0014] The invention is simple in industry, has a low ratio of raw materials to oxidants, effectively reduces production costs, has low energy consumption, is environmentally friendly, is easy to recover the catalyst, and is convenient for product separation and purification. DETAILED DESCRIPTION

[0015] The present invention is further described in detail below by way of examples, but the present invention is not limited to the examples.

[0016] Example 1

[0017] Modification of composite oxide precursor: Weigh 40.4 g of ferric nitrate nonahydrate, 3.66 g of cobalt nitrate hexahydrate, 16.9 g of manganese sulfate monohydrate, and 15.5 g of aluminum nitrate nonahydrate, dissolve in 350 mL of deionized water, stir to dissolve, slowly drop 100 g of nitric acid thereto, stir to dissolve, then slowly add 150 g of acidic silica sol (mass concentration 40%, pH = 3.5) under stirring, stir evenly, and stir at 60 ° C for 24 h to obtain solution A;

[0018] The catalyst precursor was obtained by spray drying at 260°C. The catalyst was placed in an atmosphere furnace. The precursor A was obtained by high temperature calcination at 400°C for 5 hours. 5 g of sodium phosphotungstate was dissolved in 200 mL of water to form solution B.

[0019] A was immersed in B for 24 hours, filtered, and dried to obtain catalyst A, whose composition is FeCo 0.125 MnAl 0.0413 O 2.687 / SiO2-[PW]

[0020] Example 2

[0021] Modification of composite oxide precursor: Weigh 40.4 g of ferric nitrate nonahydrate, 9.15 g of cobalt nitrate hexahydrate, 33.8 g of manganese sulfate monohydrate, and 12.8 g of magnesium nitrate hexahydrate, dissolve in 350 mL of deionized water, stir to dissolve, slowly drop 100 g of nitric acid thereto, stir to dissolve, then slowly add 200 g of acidic silica sol (mass concentration 40%, pH = 3.5) under stirring, stir evenly, and stir at 60 ° C for 24 h to obtain solution A;

[0022] The catalyst precursor was obtained by spray drying at 260°C. The catalyst was placed in an atmosphere furnace. The precursor A was obtained by high temperature calcination at 400°C for 5 hours. 10 g of sodium phosphotungstate was dissolved in 200 mL of water to form solution B.

[0023] A was immersed in B for 24 hours, filtered, and dried to obtain catalyst B, whose composition is FeCo 0.314 Mn2Mg 0.5 O 2.964 / SiO2-[PW]

[0024] Example 3

[0025] Modification of composite oxide precursor: Weigh 40.4 g of ferric nitrate nonahydrate, 13.73 g of cobalt nitrate hexahydrate, 25.35 g of manganese sulfate monohydrate, and 10.44 g of barium nitrate, dissolve in 350 mL of deionized water, stir to dissolve, slowly drop 100 g of nitric acid thereto, stir to dissolve, then slowly add 150 g of acidic silica sol (mass concentration 40%, pH = 3.5) under stirring, stir evenly, and stir at 60 ° C for 24 h to obtain solution A;

[0026] The catalyst precursor was obtained by spray drying at 260°C. The catalyst was placed in an atmosphere furnace. The precursor A was obtained by high temperature calcination at 400°C for 5 hours. 5 g of sodium phosphotungstate was dissolved in 200 mL of water to form solution B.

[0027] A was immersed in B for 24 hours, filtered, and dried to obtain catalyst C, whose composition is FeCo 0.472 Mn1.5 Ba 0.4 O 3.872 / SiO2-[PW]

[0028] Example 4

[0029] 0.3 g of catalyst (the catalysts prepared in Examples 1-3, respectively), 0.15 g of auxiliary EDTA and 37.2 g of dicyclopentadiene (mass concentration of 97%) were added to a 250 mL three-necked flask, and 30 g of H2O2 with a mass percentage of 30% was added dropwise using a constant pressure dropping funnel. The mixture was reacted at 55 ° C for 7 h. After the reaction solution was cooled to room temperature, the catalyst was recovered by centrifugation. The liquid was separated into layers in a separatory funnel, and the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by vacuum distillation to obtain a white solid powder. After melting point and H-NMR detection, it was dicyclopentadiene dioxide.

[0030] catalyst Conversion(%) Yield(%) Example 1 99.4 95.2 Example 2 98.9 98.0 Example 3 100 96.4

[0031] Example 5

[0032] 0.4 g of catalyst (the catalysts prepared in Examples 1-3, respectively), 0.16 g of auxiliary EDTA and 40.2 g of dicyclopentadiene (mass concentration of 97%) were added to a 250 mL three-necked flask, and 30 g of H2O2 with a mass percentage of 30% was added dropwise using a constant pressure dropping funnel. The mixture was reacted at 60° C. for 7 h. After the reaction solution was cooled to room temperature, the catalyst was recovered by centrifugation. The liquid was separated into layers in a separatory funnel, and the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by vacuum distillation to obtain a white solid powder. After melting point and H-NMR detection, it was dicyclopentadiene dioxide.

[0033] catalyst Conversion(%) Yield(%) Example 1 98.3 95.8 Example 2 99.2 97.9 Example 3 97.6 96.6

[0034] Example 6

[0035] 0.5 g of catalyst (the catalysts prepared in Examples 1-3, respectively), 0.18 g of auxiliary EDTA and 40.2 g of dicyclopentadiene (mass concentration of 97%) were added to a 250 mL three-necked flask, and 27.3 g of H2O2 with a mass percentage of 33% was added dropwise using a constant pressure dropping funnel. The mixture was reacted at 65 ° C for 6 h. After the reaction solution was cooled to room temperature, the catalyst was recovered by centrifugation. The liquid was separated into layers in a separatory funnel, and the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by vacuum distillation to obtain a white solid powder. After melting point and H-NMR detection, it was dicyclopentadiene dioxide.

[0036] catalyst Conversion(%) Yield(%) Example 1 99.9 97.4 Example 2 97.8 95.9 Example 3 97.7 95.5

[0037] Example 7

[0038] 0.6 g of catalyst (the catalysts prepared in Examples 1-3, respectively), 0.19 g of auxiliary EDTA and 40.2 g of dicyclopentadiene (mass concentration of 97%) were added to a 250 mL three-necked flask, and 27.3 g of H2O2 with a mass percentage of 33% was added dropwise using a constant pressure dropping funnel. The mixture was reacted at 65 ° C for 6 h. After the reaction solution was cooled to room temperature, the catalyst was recovered by centrifugation. The liquid was separated into layers in a separatory funnel, and the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by vacuum distillation to obtain a white solid powder. After melting point and H-NMR detection, it was dicyclopentadiene dioxide.

[0039] catalyst Conversion(%) Yield(%) Example 1 99.5 98.9 Example 2 98.5 98.2 Example 3 99.1 99.0

[0040] Example 8

[0041] 0.7 g of catalyst (the catalysts prepared in Examples 1-3, respectively), 0.21 g of auxiliary EDTA and 45 g of dicyclopentadiene (mass concentration of 97%) were added to a 250 mL three-necked flask, and 30 g of H2O2 with a mass percentage of 35% was added dropwise using a constant pressure dropping funnel. The mixture was reacted at 70° C. for 5 h. After the reaction solution was cooled to room temperature, the catalyst was recovered by centrifugation. The liquid was separated into layers in a separatory funnel, and the organic phase was filtered through activated carbon to remove impurities, and a pure product was obtained by vacuum distillation to obtain a white solid powder. After melting point and H-NMR detection, it was dicyclopentadiene dioxide.

[0042] catalyst Conversion(%) Yield(%) Example 1 99.5 98.9 Example 2 98.5 98.2 Example 3 99.1 99.0

[0043] Example 9

[0044] 0.8 g of catalyst (the catalysts prepared in Examples 1-3, respectively), 0.21 g of auxiliary EDTA and 47 g of dicyclopentadiene (mass concentration of 97%) were added to a 250 mL three-necked flask, and 30 g of H2O2 with a mass percentage of 35% was added dropwise using a constant pressure dropping funnel. The mixture was reacted at 80° C. for 5 h. After the reaction solution was cooled to room temperature, the catalyst was recovered by centrifugation. The liquid was separated into layers in a separatory funnel, and the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by vacuum distillation to obtain a white solid powder. After melting point and H-NMR detection, it was dicyclopentadiene dioxide.

[0045] catalyst Conversion(%) Yield(%) Example 1 99.2 97.2 Example 2 99.4 99.1 Example 3 98.6 96.8

[0046] Example 10

[0047] 1.0 g of catalyst (the catalysts prepared in Examples 1-3, respectively), 0.21 g of auxiliary EDTA and 50 g of dicyclopentadiene (mass concentration of 97%) were added to a 250 mL three-necked flask, and 30 g of H2O2 with a mass percentage of 35% was added dropwise using a constant pressure dropping funnel. The mixture was reacted at 80° C. for 4 h. After the reaction solution was cooled to room temperature, the catalyst was recovered by centrifugation. The liquid was separated into layers in a separatory funnel, and the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by vacuum distillation to obtain a white solid powder. After melting point and H-NMR detection, it was dicyclopentadiene dioxide.

[0048] catalyst Conversion(%) Yield(%) Example 1 99.6 97.5 Example 2 97.2 97.1 Example 3 97.9 95.8

[0049] Embodiment 11

[0050] 2.0 g of catalyst (the catalysts prepared in Examples 1-3, respectively), 0.21 g of auxiliary EDTA and 52 g of dicyclopentadiene (mass concentration of 97%) were added to a 250 mL three-necked flask, and 30 g of H2O2 with a mass percentage of 35% was added dropwise using a constant pressure dropping funnel. The mixture was reacted at 80° C. for 4 h. After the reaction solution was cooled to room temperature, the catalyst was recovered by centrifugation. The liquid was separated into layers in a separatory funnel, and the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by vacuum distillation to obtain a white solid powder. After melting point and H-NMR detection, it was dicyclopentadiene dioxide.

[0051] catalyst Conversion(%) Yield(%) Example 1 99.7 99.5 Example 2 99.4 97.8 Example 3 97.8 97.2

[0052] Example 12

[0053] The catalyst in Example 11 was recovered in a 250 mL three-necked flask, and 5% catalyst, 0.15 g auxiliary agent EDTA and 37.2 g dicyclopentadiene (mass concentration of 97%) were added. 30 g of H2O2 with a mass percentage of 30% was added dropwise using a constant pressure dropping funnel. The mixture was reacted at 55° C. for 7 h. After the reaction solution was cooled to room temperature, the catalyst was recovered by centrifugation. The liquid was separated into layers in a separating funnel. The organic phase was filtered through activated carbon to remove impurities, and a pure product was obtained by vacuum distillation to obtain a white solid powder. After melting point and H-NMR detection, it was found to be dicyclopentadiene dioxide.

[0054] catalyst Conversion(%) Yield(%) Example 1 99.9 98.5 Example 2 97.8 95.9 Example 3 99.6 98.1

[0055] Example 13

[0056] The catalyst in Example 12 was recovered in a 250 mL three-necked flask, and 5% catalyst, 0.18 g auxiliary agent EDTA and 40.2 g dicyclopentadiene (mass concentration of 97%) were added. 27.3 g of H2O2 with a mass percentage of 33% was added dropwise using a constant pressure dropping funnel. The mixture was reacted at 65° C. for 6 h. After the reaction solution was cooled to room temperature, the catalyst was recovered by centrifugation. The liquid was separated into layers in a separating funnel. The organic phase was filtered through activated carbon to remove impurities, and a pure product was obtained by vacuum distillation to obtain a white solid powder. After melting point and H-NMR detection, it was found to be dicyclopentadiene dioxide.

[0057] catalyst Conversion(%) Yield(%) Example 1 98.8 98.5 Example 2 99.3 97.6 Example 3 99.4 97.2

[0058] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A catalyst for catalyzing the epoxidation of dicyclopentadiene, characterized in that: The composite catalyst comprises the following elements: FeCo a Mn b X c O d / SiO2-[PW], Wherein X is selected from one or more of Al, Mg and Ba; a, b and c are the molar weights of Co, Mn and X respectively. The value range of a is 0.01-5 (preferably 0.02-1); The value range of b is 0.1-8 (preferably 1-3); The value range of c is 0.04-1 (preferably 0.1-1, more preferably 0.4-0.8); d is the ratio of oxygen atoms required to satisfy the oxidation state of the metal (Fe, Co, Mn, and X); The weight content of [PW] in the composite oxide catalyst is 0.1-20% (preferably 1-10%), and the weight content of SiO2 is 30-80% (preferably 50-70%).

2. The method for synthesizing the catalyst according to claim 1, characterized in that: The specific process is: (1) dispersing or dissolving a silicon source precursor and a metal precursor salt in water, adding nitric acid, stirring evenly, and stirring at 20-100° C. for 5-48 hours to obtain a solution A; (2) spray drying solution A at 250-300° C. to obtain a catalyst precursor; (3) placing the catalyst precursor in an atmosphere furnace and calcining it at 100-1000° C. (preferably 300-900° C.) for 3-10 h to obtain a precursor A; (4) dissolving sodium phosphotungstate (PW) in water to form solution B; (5) Precursor A is immersed in solution B for 2-48 hours, filtered, and the solid is dried to obtain a catalyst.

3. The synthesis method according to claim 2, characterized in that The metal salt of Mn in the catalyst is sulfate, and the precursors of other metals are nitrates, wherein the value range of a of Co is 0.02-1; the value range of b of Mn is 1-3; X is selected from one or more of Al, Mg, and Ba; the value range of c is 0.4-0.8; and the silicon source precursor in the catalyst is acidic silica sol (pH2.0-4.0).

4. A method for preparing dicyclopentadiene dioxide using the catalyst according to claim 1, comprising: Dicyclopentadiene is directly oxidized to dicyclopentadiene dioxide using hydrogen peroxide as an oxidant in the presence of a catalyst and an EDTA auxiliary.

5. The method for preparing dicyclopentadiene dioxide according to claim 4, characterized in that: After the reaction is completed, the catalyst is recycled, and the organic phase is filtered through activated carbon and then distilled under reduced pressure to remove the solvent to obtain dicyclopentadiene dioxide.

6. The method for preparing dicyclopentadiene dioxide according to claim 4, characterized in that: The amount of catalyst used is 0.001-1 times (preferably 0.01-0.1 times) the mass of hydrogen peroxide; The dosage of the auxiliary agent EDTA is 0.001-0.05 times (preferably 0.005-0.01) the mass of the catalyst; The mass ratio of hydrogen peroxide to dicyclopentadiene is 1:0.5-4 (preferably 1:1-1.5).

7. The method for preparing dicyclopentadiene dioxide according to claim 4, characterized in that: The reaction temperature is controlled at 20-100°C (preferably 40-80°C), and the reaction time is controlled at 2-12h (preferably 4-9h).

8. The method for preparing dicyclopentadiene dioxide according to any one of claims 4 to 7, characterized in that: The mass concentration of hydrogen peroxide is controlled at 20-50% (preferably 25-35%).

9. The method for preparing dicyclopentadiene dioxide according to claim 4 or 5, characterized in that: The conversion rate of dicyclopentadiene is greater than 95%, and the conversion rate of dicyclopentadiene after the catalyst is recycled is greater than 90%.

10. The method for preparing dicyclopentadiene dioxide according to claim 4 or 5, characterized in that: After the reaction is completed, the catalyst is recovered by filtration or centrifugation for further reuse.