A process for the preparation of epoxidized dicyclopentadiene, catalysts and preparations thereof

Abstract

A synthesis method of dicyclopentadiene dioxide is invented herein. The method adopts a heterogeneous catalytic process, and the composite catalyst comprises FeCo a Mn b X c O d / SiO2-[PW]. Under the catalysis of the above catalyst, dicyclopentadiene is directly oxidized into dicyclopentadiene dioxide by using EDTA as an auxiliary agent, hydrogen peroxide as an oxidant under a solvent-free condition. After the reaction is completed, the reaction liquid is cooled, the solid catalyst in the reaction liquid is recycled, and the organic phase is filtered through activated carbon, and then solvent is removed by distillation under reduced pressure to obtain dicyclopentadiene dioxide. The reaction method is simple, the reaction can be carried out at normal pressure, the catalyst has good catalytic activity, long service life, and is easy to recover with high recovery rate, low energy consumption, friendly to the environment, and high reaction yield of more than 90%.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of chemical industry, and designs a supported polyacid catalyst for catalytic oxidation synthesis of organic epoxides BACKGROUND

[0002] With the rapid development of China's petrochemical industry, the production capacity of ethylene produced from liquid hydrocarbon as raw material is increasing, and the comprehensive utilization rate of C5 is also increasing. Especially in some developed countries abroad, the comprehensive utilization rate is as high as 70-80%, while the comprehensive utilization rate of C5 in China is less than 20% at present. C5 is actually a valuable resource, and a series of high value-added chemical products can be produced from it. The development and utilization of C5 are widely concerned by countries all over the world, and a large amount of research and development work has been carried out.

[0003] In recent years, the utilization of C5 fraction has been changed from the initial mixed utilization to the utilization of separated single components, and has developed towards the preparation of fine chemical products. Dicyclopentadiene is an important component of C5 fraction from petroleum cracking, accounting for about 14%-19% of C5 fraction. Its epoxidation product dicyclopentadiene dioxide is a high-performance epoxy resin material. The material made from it has the advantages of good heat resistance, high hardness, excellent weather resistance and excellent electrical insulation performance, and can be used for potting adhesive of high-temperature mutual inductor and micro motor, structural adhesive, glass steel and laminated plastic adhesive.

[0004] Dicyclopentadiene dioxide is prepared from dicyclopentadiene by epoxidation reaction, and the raw material is easy to obtain. The traditional method for preparing olefin epoxides includes chlorohydrination method and peracid method, but these methods have the disadvantages of low selectivity, serious equipment corrosion, complex reaction process, acidic ring-opening of epoxides, generation of series of by-products and the like. Compared with the traditional production process, the epoxidation reaction using H2O2 as oxygen source has advantages. Firstly, the by-product of the reaction is water; secondly, the proportion of active oxygen components in H2O2 is very high, so H2O2 as a green and environmentally friendly oxygen source for olefin epoxidation reaction has been widely concerned. Among them, heteropoly compounds have suitable acidity and redox properties, and the acidity and redox properties can be regulated at the atomic or molecular level, so that its application in the field of catalysis has attracted much attention. However, the homogeneous reaction catalyst catalyzed by heteropoly acid is difficult to recover, and the specific surface area of solid heteropoly acid is small, so it cannot fully exert the catalytic activity, which limits its application. The effective loading of heteropoly acid on manganese oxide carrier can realize the heterogeneous of homogeneous catalytic reaction, which is beneficial to the separation of product and catalyst. At the same time, the loading increases the available area of active components, so as to reduce the amount of heteropoly acid and improve the utilization efficiency of catalyst. SUMMARY

[0005] In view of the problems in the prior art, the present application provides a preparation method of dicyclopentadiene dioxide. The specific scheme is as follows:

[0006] The process of multi-phase catalytic oxidation of dicyclopentadiene is adopted, dicyclopentadiene is used as raw material, hydrogen peroxide is used as oxidant, composite oxide supported heteropoly acid is used as catalyst, EDTA is used as additive, and dicyclopentadiene can be obtained under normal pressure without solvent, the catalyst can be recycled after the reaction is completed, and pure dicyclopentadiene can be obtained by filtering the organic phase through activated carbon and distilling off the solvent under reduced pressure. The reaction process is simple, the amount of dicyclopentadiene is less, and the product is easy to separate.

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

[0008] The amount of the additive EDTA is 0.005-0.01 times the mass of the catalyst.

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

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

[0011] The reaction temperature is controlled to be 40-80℃, and the reaction time is controlled to be 4-9h.

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

[0013] After the reaction is completed, the catalyst is recovered by suction filtration or centrifugation and can be reused.

[0014] The present application has the advantages of simple industry, low raw material and oxidant ratio, low production cost, low energy consumption, environmental friendliness, easy catalyst recovery, and convenient product separation and purification. DETAILED DESCRIPTION

[0015] The present application will be further described in detail through examples, but the present application is not limited to the examples.

[0016] Example 1

[0017] Composite oxide precursor modification: 40.4g of iron nitrate nonahydrate, 3.66g of cobalt nitrate hexahydrate, 16.9g of manganese sulfate monohydrate and 15.5g of aluminum nitrate nonahydrate are weighed, dissolved in 350mL of deionized water, stirred and dissolved, 100g of nitric acid is slowly added dropwise, stirred and dissolved, then 150g of acid silica sol (mass concentration 40%, pH=3.5) is slowly added under stirring, stirred uniformly at 60℃ for 24h, and solution A is obtained;

[0018] Spray drying at 260°C to obtain catalyst precursor. The catalyst was put into the atmosphere furnace. High temperature calcination at 400°C for 5h to obtain precursor A. 5g of sodium phosphotungstate was dissolved in 200mL water to form solution B.

[0019] A was immersed in B for 24h, filtered, and dried to obtain catalyst A, which was composed of FeCo 0.125 MnAl 0.0413 O 2.687 / SiO2-[PW]

[0020] Example 2

[0021] Composite oxide precursor modification: 40.4g of iron nitrate nonahydrate, 9.15g of cobalt nitrate hexahydrate, 33.8g of manganese sulfate monohydrate, and 12.8g of magnesium nitrate hexahydrate were weighed and dissolved in 350mL of deionized water, stirred and dissolved, 100g of nitric acid was slowly added dropwise, stirred and dissolved, then 200g of acidic silica sol (mass concentration 40%, pH=3.5) was slowly added under stirring, stirred uniformly, and stirred at 60°C for 24h to obtain solution A;

[0022] Spray drying at 260°C to obtain catalyst precursor. The catalyst was put into the atmosphere furnace. High temperature calcination at 400°C for 5h to obtain precursor A. 10g of sodium phosphotungstate was dissolved in 200mL water to form solution B.

[0023] A was immersed in B for 24h, filtered, and dried to obtain catalyst B, which was composed of FeCo 0.314 Mn2Mg 0.5 O 2.964 / SiO2-[PW]

[0024] Example 3

[0025] Composite oxide precursor modification: 40.4g of iron nitrate nonahydrate, 13.73g of cobalt nitrate hexahydrate, 25.35g of manganese sulfate monohydrate, and 10.44g of barium nitrate were weighed and dissolved in 350mL of deionized water, stirred and dissolved, 100g of nitric acid was slowly added dropwise, stirred and dissolved, then 150g of acidic silica sol (mass concentration 40%, pH=3.5) was slowly added under stirring, stirred uniformly, and stirred at 60°C for 24h to obtain solution A;

[0026] Spray drying at 260°C to obtain catalyst precursor. The catalyst was put into the atmosphere furnace. High temperature calcination at 400°C for 5h to obtain precursor A. 5g of sodium phosphotungstate was dissolved in 200mL water to form solution B.

[0027] A was immersed in B for 24h, filtered, and dried to obtain catalyst C, which was composed of FeCo 0.472 Mn1.5 Ba 0.4 O 3.872 / SiO2-[PW]

[0028] Example 4

[0029] In a 250 mL three-necked flask, 0.3 g of catalyst (catalysts prepared in Examples 1-3, respectively), 0.15 g of EDTA and 37.2 g of dicyclopentadiene (mass concentration of 97%) were added, and 30 g of 30% H2O2 was added dropwise using a constant pressure dropping funnel, and the reaction was carried out at 55°C for 7 h. After the reaction liquid was cooled to room temperature, the catalyst was recovered by centrifugation, the liquid was separated in a separatory funnel, the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by distillation under reduced pressure to obtain a white solid powder, which was detected by melting point and H-NMR to be 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] In a 250 mL three-necked flask, 0.4 g of catalyst (catalysts prepared in Examples 1-3, respectively), 0.16 g of EDTA and 40.2 g of dicyclopentadiene (mass concentration of 97%) were added, and 30 g of 30% H2O2 was added dropwise using a constant pressure dropping funnel, and the reaction was carried out at 60°C for 7 h. After the reaction liquid was cooled to room temperature, the catalyst was recovered by centrifugation, the liquid was separated in a separatory funnel, the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by distillation under reduced pressure to obtain a white solid powder, which was detected by melting point and H-NMR to be 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] In a 250 mL three-necked flask, 0.5 g of catalyst (catalysts prepared in Examples 1-3, respectively), 0.18 g of EDTA and 40.2 g of dicyclopentadiene (mass concentration of 97%) were added, and 27.3 g of 33% H2O2 was added dropwise using a constant pressure dropping funnel, and the reaction was carried out at 65°C for 6 h. After the reaction liquid was cooled to room temperature, the catalyst was recovered by centrifugation, the liquid was separated in a separatory funnel, the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by distillation under reduced pressure to obtain a white solid powder, which was detected by melting point and H-NMR to be 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] In a 250 mL three-necked flask, 0.6 g of catalyst (catalysts prepared in Examples 1-3, respectively), 0.19 g of auxiliary EDTA and 40.2 g of dicyclopentadiene (mass concentration 97%) were added, 27.3 g of H2O2 with mass percentage of 33% was added dropwise by constant pressure dropping funnel, and the reaction was carried out at 65°C for 6 h. After the reaction liquid was cooled to room temperature, the catalyst was recovered by centrifugation, the liquid was separated in a separatory funnel, the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by distillation under reduced pressure to obtain white solid powder, which was detected by melting point and H-NMR to be 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] In a 250 mL three-necked flask, 0.7 g of catalyst (catalysts prepared in Examples 1-3, respectively), 0.21 g of auxiliary EDTA and 45 g of dicyclopentadiene (mass concentration 97%) were added, 30 g of H2O2 with mass percentage of 35% was added dropwise by constant pressure dropping funnel, and the reaction was carried out at 70°C for 5 h. After the reaction liquid was cooled to room temperature, the catalyst was recovered by centrifugation, the liquid was separated in a separatory funnel, the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by distillation under reduced pressure to obtain white solid powder, which was detected by melting point and H-NMR to be 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] In a 250 mL three-necked flask, 0.8 g of catalyst (catalysts prepared in Examples 1-3, respectively), 0.21 g of auxiliary EDTA and 47 g of dicyclopentadiene (mass concentration 97%) were added, 30 g of H2O2 with mass percentage of 35% was added dropwise by constant pressure dropping funnel, and the reaction was carried out at 80°C for 5 h. After the reaction liquid was cooled to room temperature, the catalyst was recovered by centrifugation, the liquid was separated in a separatory funnel, the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by distillation under reduced pressure to obtain white solid powder, which was detected by melting point and H-NMR to be 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] In a 250 mL three-necked flask, 1.0 g of catalyst (catalyst prepared in Example 1-3, respectively), 0.21 g of EDTA and 50 g of dicyclopentadiene (mass concentration of 97%) were added, 30 g of 35% H2O2 was added dropwise by constant pressure dropping funnel, and the reaction was carried out at 80°C for 4 h. After the reaction liquid was cooled to room temperature, the catalyst was recovered by centrifugation, the liquid was separated in a separatory funnel, the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by distillation under reduced pressure to obtain a white solid powder, which was detected by melting point and H-NMR to be 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] Example 11

[0050] In a 250 mL three-necked flask, 1.0 g of catalyst (catalyst prepared in Example 1-3, respectively), 0.21 g of EDTA and 50 g of dicyclopentadiene (mass concentration of 97%) were added, 30 g of 35% H2O2 was added dropwise by constant pressure dropping funnel, and the reaction was carried out at 80°C for 4 h. After the reaction liquid was cooled to room temperature, the catalyst was recovered by centrifugation, the liquid was separated in a separatory funnel, the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by distillation under reduced pressure to obtain a white solid powder, which was detected by melting point and H-NMR to be 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] In a 250 mL three-necked flask, the catalyst in Example 11 was recovered, 5% catalyst, 0.15 g of EDTA and 37.2 g of dicyclopentadiene (mass concentration of 97%) were added, 30 g of 30% H2O2 was added dropwise by constant pressure dropping funnel, and the reaction was carried out at 55°C for 7 h. After the reaction liquid was cooled to room temperature, the catalyst was recovered by centrifugation, the liquid was separated in a separatory funnel, the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by distillation under reduced pressure to obtain a white solid powder, which was detected by melting point and H-NMR 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, 5% catalyst, 0.18 g of the auxiliary EDTA and 40.2 g of dicyclopentadiene (mass concentration 97%) were added, 227.3 g of 33% mass fraction H2O was added dropwise by a constant pressure dropping funnel, and the reaction was carried out at 65°C for 6 h. After the reaction liquid was cooled to room temperature, the catalyst was recovered by centrifugation, the liquid was separated in a separating funnel, the organic phase was filtered through activated carbon to remove impurities, and the pure product was obtained by distillation under reduced pressure to obtain a white solid powder, which was detected by melting point and H-NMR to be dicyclopentadiene dioxide.

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

[0058] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A catalyst for catalyzing the epoxidation of dicyclopentadiene, characterized in that: The catalyst includes 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 ratios of Co, Mn and X respectively. The value range of a is 0.01-5; The value range of b is 0.1-8; The value range of c is 0.04-1; d is the ratio of oxygen atoms required to satisfy the oxidation states of metals Fe, Co, Mn, and X; The weight content of [PW] in the catalyst is 0.1-20%, and the weight content of SiO2 is 30-80%.

2. The catalyst according to claim 1, characterized in that The catalyst includes 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 ratios of Co, Mn and X respectively. The value range of a is 0.02-1; The value range of b is 1-3; The value range of c is 0.1-1; d is the ratio of oxygen atoms required to satisfy the oxidation states of metals Fe, Co, Mn, and X; The weight content of [PW] in the catalyst is 1-10%, and the weight content of SiO2 is 50-70%.

3. A method for synthesizing the catalyst according to claim 1, characterized in that: The specific process is: (1) Disperse or dissolve the silicon source precursor and metal precursor salt in water, add nitric acid, stir evenly, and stir at 20-100°C for 5-48 hours to obtain solution A; (2) Solution A is spray-dried at 250-300°C to obtain a catalyst precursor; (3) The catalyst precursor is placed in an atmosphere furnace and calcined at 100-1000 °C for 3-10 hours to obtain precursor A; (4) Dissolve sodium phosphotungstate PW in water to form solution B; (5) Immerse precursor A in solution B for 2-48 hours, filter, and dry the solid to obtain the catalyst.

4. The synthesis method according to claim 3, wherein The metal salt of Mn in the catalyst is sulfate, and the precursors of other metals are nitrates, wherein the value of a of Co is in the range of 0.02-1; the value of b of Mn is in the range of 1-3; X is selected from one or more of Al, Mg, and Ba; the value of c is in the range of 0.4-0.8; and the silicon source precursor in the catalyst is acidic silica sol with a pH of 2.0-4.

0.

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

6. The method for preparing dicyclopentadiene dioxide according to claim 5, wherein: 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.

7. The method for preparing dicyclopentadiene dioxide according to claim 5, wherein: The amount of catalyst used is 0.001-1 times the mass of hydrogen peroxide; The dosage of the additive EDTA is 0.001-0.05 times the mass of the catalyst; The mass ratio of hydrogen peroxide to dicyclopentadiene is 1:0.5~4.

8. The method for preparing dicyclopentadiene dioxide according to claim 5, wherein: The reaction temperature is controlled at 20-100 °C, and the reaction time is controlled at 2-12 h.

9. The method for preparing dicyclopentadiene dioxide according to any one of claims 5 to 8, wherein: The mass concentration of hydrogen peroxide is controlled at 20~50%.

10. The method for preparing dicyclopentadiene dioxide according to claim 5 or 6, wherein: The conversion rate of dicyclopentadiene is greater than 95%, and the conversion rate of dicyclopentadiene after catalyst recycling is greater than 90%.

11. The method for preparing dicyclopentadiene dioxide according to claim 5 or 6, wherein: After the reaction is completed, the catalyst is recovered by filtration or centrifugation for further reuse.