Purification device for dicyclopentadiene dioxide

Abstract

The utility model discloses a dicyclopentadiene dioxide purification device which comprises a dissolving kettle, a filter, rotary equipment and a cooler, the rotary equipment can rotate up and down, a filtering component is arranged in the rotary equipment, the filtering component comprises N filtering layers, an adsorption layer is arranged between every two adjacent filtering layers, and molecular sieves are filled in the adsorption layers. The purification device does not need to be in manual contact with materials, automatic operation can be achieved in pilot plant test and industrial devices, and safe and effective purification of dicyclopentadiene dioxide is achieved.

Description

Technical Field

[0001] The utility model belongs to the field of purification, in particular to a purification device, and specifically to a purification device for dicyclopentadiene dioxide. Background Art

[0002] Dicyclopentadiene (DCPD) is a key component of the C5 fraction from petroleum cracking, accounting for approximately 14-19% of the C5 fraction. The epoxidation product of DCPD, dicyclopentadiene dioxide (DCPDDO), is an alicyclic epoxide with excellent properties. Compared to conventional epoxy resins, DCPDDO exhibits superior performance in high-temperature resistance, heat resistance, weather resistance, UV resistance, electrical insulation, and high strength. Due to these properties, DCPDDO is widely used in high-temperature resistant castables, fiberglass reinforced plastics, adhesives, laminates, and electronic device packaging.

[0003] Alicyclic epoxides are generally generated by olefins through epoxidation, and conventional synthetic methods mainly include: organic peroxy acid method, inorganic peroxide method, alkyl peroxide method, hypochlorous acid addition method, hydrogen peroxide-heteropolyacid compound method. In the prior art, dicyclopentadiene dioxide is usually prepared by dicyclopentadiene through epoxidation using methods such as peracetic acid method, chlorohydrin method and hydroperoxide catalytic epoxidation method, but these three methods all have shortcomings at present, such as complex reaction process, serious equipment corrosion, easily cause the acidic ring-opening of epoxide to generate by-products, "three wastes" discharge amount and other shortcomings. In recent years, the green epoxidation process with hydrogen peroxide as oxygen source and heteropolyacid compound as catalyst has received extensive attention.

[0004] CN114426549A discloses a method for preparing dicyclopentadiene dioxide (DCPDDO) and 2-phenyl-2-propanol, comprising: reacting DCPD with CHP in the presence of an inert solvent using a titanium silicon molecular sieve as a catalyst to generate dicyclopentadiene dioxide and 2-phenyl-2-propanol; then using a double-tower series distillation separation process, collecting solvent and 2-phenyl-2-propanol from the tops of the first and second distillation towers, and collecting DCPDDO from the bottom of the second tower; the DCPDDO collected from the bottom of the tower is separated by crystallization to obtain solid DCPDDO, and the unreacted raw materials or dicyclopentadiene monooxide in the crystallization mother liquor are re-mixed with fresh reaction raw materials and fed into the reactor to continue the reaction. The preparation process of the present invention can reuse unreacted raw materials or dicyclopentadiene monooxide, has a high product yield, significantly reduces waste liquid discharge, and is safe to operate, providing a green reaction process for synthesizing DCPDDO.

[0005] Existing technologies are only suitable for small-scale preparation in the laboratory and rely on manual operations and sample transfer. There is a safety risk of organic solvents being exposed to the air, and they cannot be used in pilot and industrial-scale automated production. Utility Model Content

[0006] The purpose of the utility model is to address the technical defects of the existing technology that rely on manual operation, are only suitable for small-scale laboratory preparation and have safety risks. The utility model provides a purification device for dicyclopentadiene dioxide, which does not require manual contact with materials and can be automatically operated in pilot and industrial devices to achieve safe and effective purification of dicyclopentadiene dioxide.

[0007] One of the purposes of the present invention is to provide a purification device for dicyclopentadiene dioxide, which comprises (preferably in order along the material flow direction) a dissolving kettle, a filter, a rotary device and a cooler.

[0008] The rotary device can rotate 360 ​​degrees and has the functions of filtering, adsorbing, washing, drying and crystallizing.

[0009] In a preferred embodiment, a condenser is provided on the top of the dissolving kettle to condense the tail gas and recover the condensate in the tail gas.

[0010] In a further preferred embodiment, one end of the condenser is connected to the dissolution kettle, and the other end is connected to the condenser tail gas line.

[0011] In a preferred embodiment, a crude dicyclopentadiene dioxide feed line and a protective gas feed line are provided on the dissolving kettle, and the protective gas in the feed line is selected from at least one of nitrogen and an inert gas, preferably nitrogen and / or helium.

[0012] In a preferred embodiment, the filter has a filtration accuracy of 20 to 80 μm, preferably 30 to 50 μm.

[0013] In a preferred embodiment, the rotary device can rotate up and down, and a filtering component is provided on the inner wall of the rotary device.

[0014] In a further preferred embodiment, the filter component includes N filter layers, an adsorption layer is provided between adjacent filter layers, and the adsorption layer is filled with molecular sieves, where N≥2.

[0015] Preferably, the filter layer is a stainless steel wire mesh and / or a sintered plate; more preferably, the filter layer has a filtration accuracy of 20 to 80 μm, preferably 30 to 50 μm.

[0016] In a preferred embodiment, one or more feed ports are provided on the rotary device for feeding filtered crude dicyclopentadiene dioxide, protective gas and solvent.

[0017] In a further preferred embodiment, at least one feed port is connected to the discharge end of the filter via a pipeline.

[0018] In a preferred embodiment, the rotary device is further provided with a dicyclopentadiene dioxide product outlet, a post-rotation gas phase outlet, and a post-rotation liquid phase outlet.

[0019] In a further preferred embodiment, the post-rotation gas phase outlet is connected to the cooler via a pipeline; and / or a dicyclopentadiene dioxide product discharge pipeline is provided at the dicyclopentadiene dioxide product outlet.

[0020] In a further preferred embodiment, the liquid phase outlet after rotation is connected to the feed end of the dissolving kettle through a liquid phase circulation pipeline, and the liquid phase outlet after rotation is further provided with a liquid phase discharge pipeline after rotation.

[0021] In a preferred embodiment, the rotary device has a cone-like structure, one axial end of which is a cone, and the dicyclopentadiene dioxide product outlet is provided on the cone.

[0022] The solid discharge of the rotary device is connected to the product receiving device, the gas discharge is connected to the cooler, and the liquid discharge is connected to the dissolution kettle and the downstream processing system.

[0023] In a preferred embodiment, the rotary device includes an inner wall and an outer wall, and a sandwich is formed between the inner wall and the outer wall. The sandwich is a heat exchange space of the rotary device, and a refrigerant or a heat medium is introduced into the sandwich.

[0024] The interlayer of the rotary device is used for heat exchange with the interior of the device. Both a heat medium and a refrigerant can be introduced into the interlayer, but not both at the same time. The refrigerant and the heat medium of the rotary device are the same substance, preferably an ethylene glycol aqueous solution, water, or thermal oil.

[0025] In a preferred embodiment, the apparatus further optionally comprises a vacuum system.

[0026] In a further preferred embodiment, the vacuum system is connected to the cooler via a pipeline, or the cooler is further connected to a downstream processing system.

[0027] In the present invention, a method for purifying dicyclopentadiene dioxide by the above-mentioned device comprises the steps of:

[0028] (1) introducing crude dicyclopentadiene dioxide as solute into a dissolving kettle, adding cyclohexane as solvent, heating and dissolving to obtain a solution;

[0029] (2) filtering the solution in step (1) through a filter and then passing it into a rotary device, which rotates to absorb water in the solution using the adsorption function of the adsorption layer (molecular sieve);

[0030] (3) introducing a refrigerant into the interlayer of the rotary device to cool the solution and crystallize it; after crystallization, utilizing the filtering function of the rotary device, introducing nitrogen, and discharging the primary crystallization mother liquor for post-processing, leaving the primary crystallization residue after filtration in the rotary device;

[0031] (4) introducing cyclohexane into the primary crystallization residue of step (3), introducing a heat medium into the interlayer of the rotary device, heating and dissolving the mixture to obtain a solution, rotating the rotary device, and utilizing the adsorption function of the adsorption layer (molecular sieve) to adsorb water in the solution;

[0032] (5) introducing a refrigerant into the interlayer of the rotary device to cool the solution and crystallize it; after crystallization, utilizing the filtering function of the rotary device, introducing nitrogen, and circulating the secondary crystallization mother liquor through the liquid phase circulation pipeline to step (1) as a solvent, leaving the secondary crystallization residue after filtration in the rotary device;

[0033] (6) utilizing the drying function of the rotary device, introducing heat medium into the interlayer of the rotary device, raising the temperature, and using a vacuum system to evacuate the cyclohexane, thereby vaporizing the cyclohexane and desorbing the adsorption layer (molecular sieve). The tail gas, which is mainly cyclohexane and water, is cooled in a cooler and then pumped into the vacuum system. The discharge of the vacuum system is sent to downstream processing;

[0034] (6') utilizing the drying function of the rotary device, introducing heat medium into the interlayer of the rotary device, raising the temperature, and using nitrogen to purge the rotary device to vaporize cyclohexane and desorb the adsorption layer (molecular sieve). The tail gas, which is mainly cyclohexane and water, is cooled in a cooler and then discharged to downstream processing;

[0035] (7) The high-purity dicyclopentadiene dioxide material obtained by the rotary equipment in step (6) is discharged through the dicyclopentadiene dioxide product outlet to the product receiving equipment.

[0036] The rotary device can rotate 360 ​​degrees and has the functions of filtering, adsorbing, washing, drying and crystallizing.

[0037] Preferably, after the product is discharged in step (7), the rotary device is preferably flushed with cyclohexane, and the washing liquid is discharged for post-processing.

[0038] In a preferred embodiment, it is characterized in that the crude dicyclopentadiene dioxide material contains dicyclopentadiene dioxide and α,α-dimethylbenzyl alcohol, water and other substances, and optionally contains dicyclopentadiene monooxide and / or cumene hydroperoxide;

[0039] Preferably, based on 100 wt% of the dicyclopentadiene dioxide-containing material, the dicyclopentadiene dioxide is 30-95 wt%, α,α-dimethylbenzyl alcohol is 1-30 wt%, water is 0-1 wt%, dicyclopentadiene monooxide is 0-5 wt%, cumene hydroperoxide is 0-5 wt%, and other substances are 0-2 wt%.

[0040] In a preferred embodiment, the other substances include cumene, phenol, acetophenone and mechanical impurities.

[0041] In a preferred embodiment, the temperature of the dissolving kettle in step (1) is increased by electric heating or heat exchange with a heat medium.

[0042] The endpoints and any values ​​of the ranges disclosed in this utility model are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be considered as specifically disclosed herein. Hereinafter, in principle, the various technical solutions can be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] (1) By setting an adsorption layer in the rotary equipment filter element, the water content in the product can be reduced to a low level. Through the desorption step, the molecular sieve can be reused to solve the problem of excessive water content in the product. It also avoids the energy consumption and high investment caused by setting up a distillation tower for dehydration.

[0045] (2) High degree of automation, no manual handling of materials required, suitable for large-scale production in pilot and industrial plants;

[0046] (3) The crystallization, filtration, adsorption, and drying steps are all carried out in a rotary device, eliminating the need for transporting solids or solid-liquid mixtures and avoiding the risk of pipeline blockage.

[0047] (4) The entire process is carried out in closed equipment and pipelines. The materials only come into contact with nitrogen and not with air, thus avoiding safety risks. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 A structural schematic diagram showing an embodiment of the device of the present invention is shown.

[0049] exist Figure 1In the diagram, A-dissolving kettle, B-rotating equipment, C-filter, D-condenser, E-cooler, F-vacuum system. 1-crude dicyclopentadiene dioxide feed line, 2-dissolving kettle overhead gas, 3-shielding gas feed line, 4-condenser tail gas line, 5-dissolving kettle discharge, 6-filter discharge, 7-cyclohexane, 8-heating medium inlet to rotary equipment, 9-refrigerant inlet to rotary equipment, 10-heating medium outlet from rotary equipment, 11-refrigerant outlet from rotary equipment, 12-gas phase outlet after rotation, 13-cooler discharge, 14-vacuum system discharge, 15-liquid phase outlet after rotation, 16-liquid phase circulation line, 17-dicyclopentadiene dioxide product outlet, 18-nitrogen to rotary equipment, 19-liquid phase outlet after rotation.

[0050] In adopting Figure 1 When the system is shown:

[0051] The crude dicyclopentadiene dioxide material is introduced into the dissolving kettle A through the crude dicyclopentadiene dioxide feed pipeline 1, the top gas 2 of the dissolving kettle enters the condenser D to obtain the condensate and returns to the dissolving kettle A, the condenser tail gas is sent to the post-processing through the condenser tail gas pipeline 4, and cyclohexane 16 is added to the dissolving kettle A, and the temperature is raised to dissolve the solute in the solvent to obtain a solution.

[0052] Nitrogen is introduced into the dissolving kettle through the protective gas feed line 3, so that the dissolving kettle discharge 5 goes to the filter C, and the filter discharge 6 is introduced into the rotary device B. The rotary device B rotates and utilizes the adsorption function of the adsorption layer (molecular sieve) to adsorb the moisture in the solution.

[0053] A refrigerant 9 is introduced into the interlayer of the rotary device B to cool the solution and crystallize it. After heat exchange, the refrigerant 11 is discharged from the rotary device B. After crystallization, the filtering function of the rotary device is utilized, and nitrogen 18 is introduced from the feed port of the rotary device to discharge the primary crystallization mother liquor through the liquid phase discharge pipeline 15 after rotation for post-processing. The filtered primary crystallization residue remains in the rotary device.

[0054] Cyclohexane 7 is introduced into the primary crystallization residue, and heat medium 8 is introduced into the interlayer of rotary device B. The temperature is increased to dissolve to obtain a solution. After heat exchange, heat medium 10 is discharged from rotary device B. Rotary device B rotates and utilizes the molecular sieve adsorption function to adsorb water in the solution.

[0055] A refrigerant 9 is introduced into the interlayer of rotary device B to cool the solution and crystallize it. After heat exchange, the refrigerant 11 is discharged from rotary device B. After crystallization, the filtration function of the rotary device is utilized, and nitrogen 18 is introduced through the feed port of the rotary device. The secondary crystallization mother liquor is circulated through the liquid phase circulation pipeline 16 to dissolve the cyclohexane used as the solvent in kettle A. The filtered secondary crystallization residue remains in rotary device B.

[0056] Utilizing the drying function of the rotary device B, a heat medium 8 is introduced into the interlayer of the rotary device to increase the temperature. After heat exchange, the heat medium 10 is discharged from the rotary device B. A vacuum system F is used to evacuate the cyclohexane, desorbing the adsorbed water in the molecular sieve into gas. The gas phase of the rotary device enters the cooler E from the gas phase outlet 12 after rotation and is cooled. The cooler discharge 13 is then pumped to the vacuum system, and the discharge 14 of the vacuum system is sent to downstream processing.

[0057] The rotary device B obtains high-purity dicyclopentadiene dioxide product from the dicyclopentadiene dioxide product outlet 17 and discharges it to the product receiving device.

[0058] The rotary device B can rotate 360 ​​degrees and has the functions of filtering, adsorption, washing, drying and crystallization.

[0059] Figure 2 A schematic diagram showing another embodiment of the system of the present invention;

[0060] exist Figure 2 In the diagram, A-dissolving kettle, B-rotating equipment, C-filter, D-condenser, E-cooler. 1-crude dicyclopentadiene dioxide feed line, 2-dissolving kettle overhead gas, 3-shielding gas feed line, 4-condenser tail gas line, 5-dissolving kettle discharge, 6-filter discharge, 7-cyclohexane, 8-heating medium inlet to the rotary equipment, 9-refrigerant inlet to the rotary equipment, 10-heating medium outlet from the rotary equipment, 11-refrigerant outlet from the rotary equipment, 12-gas phase outlet after rotation, 13-cooler discharge, 15-liquid phase outlet after rotation, 16-liquid phase circulation line, 17-dicyclopentadiene dioxide product outlet, 18-nitrogen to the rotary equipment, 19-liquid phase outlet after rotation.

[0061] In adopting Figure 2 When the system is shown:

[0062] The crude dicyclopentadiene dioxide material is introduced into the dissolving kettle A through the crude dicyclopentadiene dioxide feed pipeline 1, the top gas 2 of the dissolving kettle enters the condenser D to obtain the condensate and returns to the dissolving kettle A, the condenser tail gas is sent to the post-processing through the condenser tail gas pipeline 4, and cyclohexane 16 is added to the dissolving kettle A, and the temperature is raised to dissolve the solute in the solvent to obtain a solution.

[0063] Nitrogen is introduced into the dissolving kettle through the protective gas feed line 3, so that the dissolving kettle discharge 5 goes to the filter C, and the filter discharge 6 is introduced into the rotary device B. The rotary device B rotates and utilizes the adsorption function of the adsorption layer (molecular sieve) to adsorb the moisture in the solution.

[0064] A refrigerant 9 is introduced into the interlayer of the rotary device B to cool the solution and crystallize it. After heat exchange, the refrigerant 11 is discharged from the rotary device B. After crystallization, the filtering function of the rotary device is utilized, and nitrogen 18 is introduced from the feed port of the rotary device to discharge the primary crystallization mother liquor through the liquid phase discharge pipeline 15 after rotation for post-processing. The filtered primary crystallization residue remains in the rotary device.

[0065] Cyclohexane 7 is introduced into the primary crystallization residue, and heat medium 8 is introduced into the interlayer of rotary device B. The temperature is increased to dissolve to obtain a solution. After heat exchange, heat medium 10 is discharged from rotary device B. Rotary device B rotates and utilizes the molecular sieve adsorption function to adsorb water in the solution.

[0066] A refrigerant 9 is introduced into the interlayer of rotary device B to cool the solution and crystallize it. After heat exchange, the refrigerant 11 is discharged from rotary device B. After crystallization, the filtration function of the rotary device is utilized, and nitrogen 18 is introduced through the feed port of the rotary device. The secondary crystallization mother liquor is circulated through the liquid phase circulation pipeline 16 to dissolve the cyclohexane used as the solvent in kettle A. The filtered secondary crystallization residue remains in rotary device B.

[0067] Utilizing the drying function of the rotary device B, a heat medium 8 is introduced into the interlayer of the rotary device to increase the temperature. After heat exchange, the heat medium 10 is discharged from the rotary device B. Nitrogen 18 is introduced into the rotary device B to blow and dry the secondary crystallization filter residue, gasify the cyclohexane, and desorb the adsorbed water in the molecular sieve into gas. The gas phase of the rotary device enters the cooler E from the gas phase outlet 12 after rotation to be cooled and sent to the downstream for processing as the cooler discharge 13.

[0068] The rotary device B obtains high-purity dicyclopentadiene dioxide product from the dicyclopentadiene dioxide product outlet 17 and discharges it to the product receiving device.

[0069] The rotary device B can rotate 360 ​​degrees and has the functions of filtering, adsorption, washing, drying and crystallization. DETAILED DESCRIPTION

[0070] The present invention is described in detail below with reference to specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the content of the present invention still fall within the scope of protection of the present invention.

[0071] It should also be noted that the various specific technical features described in the following specific embodiments can be combined in any appropriate manner without contradiction. To avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0072] In addition, the various embodiments of the present invention may be arbitrarily combined as long as they do not violate the concept of the present invention. The technical solutions thus formed belong to part of the original disclosure of this specification and also fall within the scope of protection of the present invention.

[0073] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0074]

[0075] [Example 1]

[0076] like Figure 1 As shown, raw materials containing, by weight, 20% α,α-dimethylbenzyl alcohol, 0.05% acetophenone, 0.05% water, and 79.90% dicyclopentadiene dioxide are introduced into a dissolution vessel as the solute. Cyclohexane, containing 180 ppm of water, is then added. Nitrogen pressure is maintained at 0.05 MPaG. The vessel is heated to 78°C via a heat medium, completely dissolving the solute and forming a solution. The solvent-to-raw material mass ratio is 4.27. The dissolution vessel discharge is filtered and then passed into a rotary device. The rotary device has two filter layers (stainless steel mesh) with an adsorption layer filled with 4A molecular sieve between them. Cooling and crystallization occur via refrigerant heat exchange at a temperature of 10°C and a pressure of 0.01 MPaG. After crystallization, the mother liquor from the primary crystallization is processed downstream. Cyclohexane is introduced into the primary crystallization residue, where it is heated and dissolved via heat exchange with a heat medium to form a solution at a temperature of 80°C and a pressure of 0.05 MPaG. The cyclohexane mass to raw material mass ratio is 4. The rotary device then cools and crystallizes via heat exchange with a refrigerant at a temperature of 10°C and a pressure of 0.01 MPaG. The mother liquor from the secondary crystallization is returned to the dissolution kettle as solvent. The secondary crystallization residue is vacuum dried at a temperature of 80°C and a pressure of 4 kPaA to obtain the dicyclopentadiene dioxide product.

[0077] In terms of weight percentage, the condenser tail gas composition is 13.50% cyclohexane, 1.49% water, and 85.01% nitrogen.

[0078] In terms of weight percentage, the composition of the primary crystallization mother liquor is 89.63% of cyclohexane, 0.01% of water, 4.45% of α,α-dimethylbenzyl alcohol, 0.01% of acetophenone, and 5.90% of dicyclopentadiene dioxide.

[0079] The final product composition, by weight percentage, was 74 ppm cyclohexane, 43 ppm water, 0.64% α,α-dimethylbenzyl alcohol, and 99.35% dicyclopentadiene dioxide. The recovery rate of dicyclopentadiene dioxide was 67.42%.

[0080] The device runs smoothly, there is no pipeline blockage problem, it is fully enclosed and automatically operated, and there is no risk of explosion.

[0081] [Example 2]

[0082] like Figure 1 As shown, raw materials containing, by weight, 20% α,α-dimethylbenzyl alcohol, 0.05% cumene hydroperoxide, 0.05% phenol, 0.1% water, and 79.80% dicyclopentadiene dioxide are introduced into a dissolution vessel as the solute. Cyclohexane, containing 150 ppm of water, is then added. Nitrogen pressure is maintained at 0.05 MPaG. The vessel is heated to 80°C via a heat medium, completely dissolving the solute and forming a solution. The solvent-to-raw material mass ratio is 4.29. The dissolution vessel discharge is filtered and then passed into a rotary device. The rotary device has three filter layers (stainless steel mesh), with an adsorption layer between each filter layer, for a total of two adsorption layers. Each adsorption layer is filled with 4A molecular sieve. Crystallization occurs by cooling via refrigerant heat exchange at a temperature of 15°C and a pressure of 0.01 MPaG. After crystallization, the mother liquor from the primary crystallization is processed downstream. Cyclohexane is introduced into the primary crystallization residue, where it is heated and dissolved by heat exchange with a heat medium to form a solution. The dissolution temperature is 80°C, the pressure is 0.05 MPaG, and the cyclohexane mass to raw material mass ratio is 4. The rotary equipment then cools and crystallizes the product by heat exchange with a refrigerant at a temperature of 15°C and a pressure of 0.01 MPaG. The mother liquor from the secondary crystallization is returned to the dissolution kettle as solvent. The secondary crystallization residue is vacuum dried at a temperature of 90°C and a pressure of 3 kPaA to obtain the dicyclopentadiene dioxide product.

[0083] In terms of weight percentage, the condenser tail gas composition is 14.79% cyclohexane, 1.88% water, and 83.33% nitrogen.

[0084] The composition of the primary crystallization mother liquor is, in weight percentage, 88.45% of cyclohexane, 0.01% of water, 4.43% of α,α-dimethylbenzyl alcohol, 0.01% of phenol, 0.01% of cumene hydroperoxide, and 7.09% of dicyclopentadiene dioxide.

[0085] The final product composition, by weight percentage, was 59 ppm cyclohexane, 27 ppm water, 0.43% α,α-dimethylbenzyl alcohol, and 99.56% dicyclopentadiene dioxide. The recovery rate of dicyclopentadiene dioxide was 60.26%.

[0086] The device runs smoothly, there is no pipeline blockage problem, it is fully enclosed and automatically operated, and there is no risk of explosion.

[0087] [Example 3]

[0088] like Figure 2As shown, raw materials containing, by weight, 21.8% α,α-dimethylbenzyl alcohol, 0.1% cumene hydroperoxide, 0.1% acetophenone, 0.2% water, and 77.8% dicyclopentadiene dioxide are introduced into a dissolution vessel as the solute. Cyclohexane, containing 130 ppm of water, is then added. Nitrogen pressure is maintained at 0.05 MPaG. The vessel is heated to 80°C via a heat medium, completely dissolving the solute to form a solution. The solvent-to-raw material mass ratio is 4.78. The dissolution vessel discharge is filtered and then passed into a rotary device. The rotary device has two filter layers (stainless steel mesh) with an adsorption layer filled with 5A molecular sieve between them. Cooling and crystallization occur via refrigerant heat exchange at a temperature of 12°C and a pressure of 0.01 MPaG. After crystallization, the mother liquor from the primary crystallization is processed downstream. Cyclohexane is introduced into the primary crystallization residue, where it is heated and dissolved by heat exchange with a heat medium to form a solution. The dissolution temperature is 80°C and the pressure is 0.05 MPaG. The cyclohexane mass to raw material mass ratio is 4.5. The rotary equipment then cools and crystallizes the product by heat exchange with a refrigerant at a temperature of 12°C and a pressure of 0.01 MPaG. The mother liquor from the secondary crystallization is returned to the dissolution kettle as solvent. The secondary crystallization residue is dried by nitrogen purge at a temperature of 150°C and a pressure of 0.01 MPaG to obtain the dicyclopentadiene dioxide product.

[0089] In terms of weight percentage, the condenser tail gas composition is 19.18% cyclohexane, 2.99% water, and 77.83% nitrogen.

[0090] In terms of weight percentage, the composition of the primary crystallization mother liquor is 89.40% of cyclohexane, 0.01% of water, 4.34% of α,α-dimethylbenzyl alcohol, 0.02% of isopropylbenzene hydroperoxide, 0.02% of acetophenone, and 6.21% of dicyclopentadiene dioxide.

[0091] The final product composition, by weight percentage, was 0.02% cyclohexane, 54 ppm water, 0.48% α,α-dimethylbenzyl alcohol, and 99.49% dicyclopentadiene dioxide. The recovery rate of dicyclopentadiene dioxide was 60.27%.

[0092] The device runs smoothly, there is no pipeline blockage problem, it is fully enclosed and automatically operated, and there is no risk of explosion.

[0093] [Example 4]

[0094] like Figure 2As shown, raw materials containing, by weight, 18% α,α-dimethylbenzyl alcohol, 0.1% phenol, 0.1% acetophenone, 0.5% water, and 81.3% dicyclopentadiene dioxide are introduced into a dissolution vessel as the solute. Cyclohexane, containing 100 ppm of water, is then added. Nitrogen pressure is maintained at 0.03 MPaG. The temperature is raised to 75°C via a heat medium, completely dissolving the solutes and forming a solution. The solvent-to-raw material mass ratio is 5.28. The dissolution vessel discharge is filtered and then passed into a rotary device. The rotary device has three filter layers (stainless steel mesh), with an adsorption layer between each filter layer, for a total of two adsorption layers. Each adsorption layer is filled with 5A molecular sieve. Crystallization occurs by cooling via refrigerant heat exchange at a temperature of 17°C and a pressure of 0.01 MPaG. After crystallization, the mother liquor from the primary crystallization is processed downstream. Cyclohexane is introduced into the primary crystallization residue, where it is heated and dissolved by heat exchange with a heat medium to form a solution at a temperature of 75°C and a pressure of 0.03 MPaG. The mass ratio of cyclohexane to raw material is 5. The rotary equipment then cools and crystallizes the product by heat exchange with a refrigerant at a temperature of 17°C and a pressure of 0.01 MPaG. The mother liquor from the secondary crystallization is returned to the dissolution kettle as solvent. The secondary crystallization residue is dried by nitrogen purge at a temperature of 160°C and a pressure of 0.01 MPaG to obtain the dicyclopentadiene dioxide product.

[0095] In terms of weight percentage, the condenser tail gas composition is 22.30% cyclohexane, 7.97% water, and 69.73% nitrogen.

[0096] Calculated by weight percentage, the composition of the primary crystallization mother liquor is 89.83% of cyclohexane, 0.01% of water, 3.26% of α,α-dimethylbenzyl alcohol, 0.02% of phenol, 0.02% of acetophenone, and 6.86% of dicyclopentadiene dioxide.

[0097] The final product composition, by weight percentage, was 0.02% cyclohexane, 68 ppm water, 0.18% α,α-dimethylbenzyl alcohol, and 99.79% dicyclopentadiene dioxide. The recovery rate of dicyclopentadiene dioxide was 53.52%.

[0098] The device runs smoothly, there is no pipeline blockage problem, it is fully enclosed and automatically operated, and there is no risk of explosion.

[0099] The present invention has been described in detail above with reference to specific embodiments and exemplary examples. However, these descriptions should not be construed as limiting the present invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications, or improvements may be made to the technical solutions and implementations of the present invention without departing from the spirit and scope of the present invention, and all of these modifications fall within the scope of the present invention. The scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A purification device for dicyclopentadiene dioxide, comprising a dissolving kettle, a filter, a rotary device and a cooler, wherein: A filter component is provided on the inner wall of the rotary device. The filter component includes N filter layers, where N is greater than or equal to 2. An adsorption layer is provided between adjacent filter layers. The adsorption layer is filled with a molecular sieve.

2. The purification device according to claim 1, characterized in that A condenser is provided on the top of the dissolving kettle.

3. The purification device according to claim 2, characterized in that One end of the condenser is connected to the dissolving kettle, and the other end is connected to the condenser tail gas line.

4. The purification device according to claim 1, characterized in that A crude dicyclopentadiene dioxide feeding pipeline and a protective gas feeding pipeline are provided on the dissolving kettle. The protective gas in the protective gas feeding pipeline is selected from at least one of nitrogen and inert gas.

5. The purification device according to claim 1, characterized in that The filter layer is a stainless steel wire mesh and / or a sintered plate.

6. The purification device according to claim 1, characterized in that One or more feed ports are provided on the rotary device, at least one of which is connected to the discharge end of the filter via a pipeline.

7. The purification device according to claim 1, characterized in that The rotary device is further provided with a dicyclopentadiene dioxide product outlet, a gas phase outlet after rotation, and a liquid phase outlet after rotation, wherein: The gas phase outlet after rotation is connected to the cooler via a pipeline; and / or, A dicyclopentadiene dioxide product discharge pipeline is provided at the dicyclopentadiene dioxide product outlet; and / or, The liquid phase outlet after rotation is connected to the feed end of the dissolving kettle through a liquid phase circulation pipeline, and the liquid phase outlet after rotation is further provided with a liquid phase external discharge pipeline after rotation.

8. The purification device according to claim 7, characterized in that The rotary device has a cone-like structure, one axial end of which is a cone, and the dicyclopentadiene dioxide product outlet is arranged on the cone.

9. The purification device according to any one of claims 1 to 8, characterized in that: The rotary device comprises an inner wall and an outer wall, and a sandwich is formed between the inner wall and the outer wall. The sandwich is a heat exchange space of the rotary device, and a refrigerant or a heat medium is introduced into the sandwich.

10. The purification device according to claim 9, characterized in that The device optionally comprises a vacuum system, and the vacuum system is connected to the cooler via a pipeline.

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