A system for producing dicyclopentadiene acrylate without alkaline wastewater

Abstract

The application discloses a dicyclopentadiene acrylate preparation system without alkaline wastewater generation, which comprises a first feeding pipe, a first feeding pump, a second feeding pipe, a second feeding pump, a mixer, a third pipe body, a reaction preheater, a fourth pipe body, a fixed bed reactor and a reactant receiving tank, wherein one end of the third pipe body is connected with an output port of the mixer, an input port of the reaction preheater is connected with the third pipe body, one end of the fourth pipe body is connected with the reaction preheater, an input port at the bottom of the fixed bed reactor is connected with the other end of the fourth pipe body, an acidic catalyst layer is filled in the fixed bed reactor, one end of a fifth pipe body is connected with an output port at the top of the fixed bed reactor, and an input port of the reactant receiving tank is connected with the other end of the fifth pipe body; and the acidic catalyst layer is composed of sulfonic acid resin catalyst particles. Through the above mode, the sulfonic acid resin catalyst particles are filled in the fixed bed reactor, the catalyst can be recycled, neutralization treatment of the catalyst is not needed after the reaction, alkaline wastewater is not generated, and the environment is not polluted.

Description

Technical Field

[0001] This invention relates to the field of dicyclopentadiene acrylate preparation technology, specifically a dicyclopentadiene acrylate preparation system that does not produce alkaline wastewater. Background Technology

[0002] Dicyclopentenyl acrylate (DCPA) is a colorless or pale yellow transparent liquid with the molecular formula: C 13 H 16 O2, CAS number 33791-58-1, is a monomer with excellent properties and broad application prospects. Its structure incorporates a large dicyclopentadiene group, resulting in a high glass transition temperature (Tg) for its homopolymer. It exhibits good performance in terms of hardness, water resistance, and transparency, and can be widely used in coatings, adhesives, plastic surfaces, and optical materials requiring insulation and high hardness. It is an ideal reactive diluent for photocurable materials.

[0003] Currently, the existing methods for synthesizing DCPA mainly involve slowly adding dicyclopentadiene dropwise to an acrylic acid solution containing a strong acid catalyst to undergo an electrophilic addition reaction to obtain a crude reaction solution, which is then post-treated or vacuum distilled to obtain the product dicyclopentenyl acrylate.

[0004] However, in the traditional method, the synthesis stage of commercially available dicyclopentenyl acrylate often uses a liquid sulfonic acid catalyst, which is used once and there is no recycling. The liquid sulfonic acid catalyst needs to be neutralized with sodium hydroxide aqueous solution and then washed with water, but this easily generates a large amount of alkaline wastewater, polluting the environment. Summary of the Invention

[0005] (a) Technical problems to be solved

[0006] To address the shortcomings of existing technologies, this invention provides a dicyclopentadiene acrylate preparation system that generates no alkaline wastewater, thereby solving the aforementioned technical problems.

[0007] (II) Technical Solution

[0008] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a dicyclopentadiene acrylate preparation system without alkaline wastewater generation, characterized in that it comprises: a first feed pipe for conveying a dicyclopentadiene solution; a first feed pump, the inlet of which is connected to one end of the first feed pipe; a second feed pipe for conveying an acrylic acid solution containing a strong acid catalyst; a second feed pump, the inlet of which is connected to one end of the second feed pipe; and a mixer, wherein the output port of the first feed pump is connected to the mixer through a first pipe body, and the output port of the second feed pump is connected to the mixer through a second pipe body. The system comprises: a mixer connection; a third tube, one end of which is connected to the output port of the mixer; a reaction preheater, the inlet of which is connected to the other end of the third tube; a fourth tube, one end of which is connected to the output port of the reaction preheater; a fixed-bed reactor, the bottom inlet of which is connected to the other end of the fourth tube, wherein the fixed-bed reactor is filled with an acidic catalyst layer; a fifth tube, one end of which is connected to the output port at the top of the fixed-bed reactor; and a reactant receiving tank, the inlet of which is connected to the other end of the fifth tube; wherein the acidic catalyst layer is composed of sulfonic acid resin catalyst particles.

[0009] Furthermore, the sulfonic acid resin catalyst particles are spherical in shape, and the diameter of the sulfonic acid resin catalyst particles ranges from 0.5 to 5 mm.

[0010] Furthermore, the temperature range within the fixed-bed reactor is 80-90 degrees Celsius, and the pressure range within the fixed-bed reactor is 0.1-0.2 MPa.

[0011] Furthermore, the first pipe body is provided with a first switching valve for controlling the opening and closing of the first pipe body, the second pipe body is provided with a second switching valve for controlling the opening and closing of the second pipe body, the first pipe body is also provided with a first one-way valve that allows the dicyclopentadiene solution to flow only into the mixer, and the second pipe body is also provided with a second one-way valve that allows the acrylic acid solution to flow only into the mixer.

[0012] Furthermore, the reaction preheater is U-shaped, and includes a first preheating tube and a second preheating tube in the shape of an elongated strip. The first and second preheating tubes are connected and have the same length. The second preheating tube is located above the first preheating tube. The first preheating tube is connected to the other end of the third tube body, and one end of the fourth tube body is connected to the second preheating tube.

[0013] Furthermore, the reaction preheater is also provided with an insulation layer wrapped around the first preheating tube and the second preheating tube, wherein the insulation layer forms a flow cavity with the outer wall of the first preheating tube and the second preheating tube, and the insulation layer at the first preheating tube is provided with a steam inlet communicating with the flow cavity and for inputting high-temperature steam, and the insulation layer at the second preheating tube is provided with a steam outlet communicating with the flow cavity and for inputting high-temperature steam.

[0014] Furthermore, the fixed-bed reactor is provided with a receiving cavity, wherein the acidic catalyst layer is disposed in the middle of the receiving cavity to divide the receiving cavity into a first receiving cavity and a second receiving cavity above the first receiving cavity, and the other end of the fourth tube is connected to the first receiving cavity, and one end of the fifth tube is connected to the second receiving cavity.

[0015] Furthermore, the outer wall of the fixed-bed reactor is also provided with a vibrator, and the acidic catalyst layer is provided with a first vibrating rod in the horizontal direction, a second vibrating rod above the first vibrating rod, and a third vibrating rod below the first vibrating rod, wherein the vibrator is connected to the first vibrating rod so as to drive the first vibrating rod to vibrate in the acidic catalyst layer.

[0016] Furthermore, the acidic catalyst layer is composed of multiple layers of filter layers spaced apart. The filter layers include a receiving plate, a first filter screen disposed above the receiving plate, and a second filter screen disposed below the receiving plate. The receiving plate is provided with multiple through holes spaced apart, and the sulfonic acid resin catalyst particles are disposed in the through holes.

[0017] Furthermore, the through holes of two adjacent filter layers are not corresponding to each other, and the outer wall of the fixed bed reactor is also provided with a circulation pump, wherein the inlet of the circulation pump is connected to the second receiving cavity through a first circulation pipe, and the outlet of the circulation pump is located in the middle of the acidic catalyst layer through a second circulation pipe.

[0018] (III) Beneficial Effects

[0019] Compared with existing technologies, this invention provides a dicyclopentadiene acrylate preparation system that produces no alkaline wastewater, possessing the following beneficial effects: The dicyclopentadiene acrylate preparation system disclosed in this invention, which produces no alkaline wastewater, includes: a first feed pipe; a first feed pump; a second feed pipe; a second feed pump; a mixer; a third pipe body, one end of which is connected to the output port of the mixer; a reaction preheater, the input port of which is connected to the third pipe body; a fourth pipe body, one end of which is connected to the reaction preheater; a fixed-bed reactor, the bottom input port of which is connected to the other end of the fourth pipe body, the fixed-bed reactor being filled with an acidic catalyst layer; a fifth pipe body, one end of which is connected to the top output port of the fixed-bed reactor; and a reactant receiving tank, the input port of which is connected to the other end of the fifth pipe body; wherein, the acidic catalyst layer is composed of sulfonic acid resin catalyst particles. Through the above method, this invention fills the fixed-bed reactor with sulfonic acid resin catalyst particles, allowing for catalyst recycling. After the reaction, no catalyst neutralization treatment is required, no alkaline wastewater is generated, and there is no environmental pollution. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of the dicyclopentadiene acrylate preparation system of the present invention, which produces no alkaline wastewater.

[0021] Figure 2 for Figure 1 Schematic diagram of the structure of the intermediate reaction preheater;

[0022] Figure 3 for Figure 1 A schematic diagram of the first embodiment of the fixed-bed reactor;

[0023] Figure 4 for Figure 1 A schematic diagram of the second embodiment of the fixed-bed reactor;

[0024] Figure 5 for Figure 1 A schematic diagram of the third embodiment of the fixed-bed reactor;

[0025] Figure 6 for Figure 5 A schematic diagram of the filter layer in a fixed-bed reactor. Detailed Implementation

[0026] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] like Figure 1-3As shown, the dicyclopentadiene acrylate preparation system without alkaline wastewater production disclosed in this invention includes a first feed pipe 11, a second feed pipe 12, a first feed pump 13, a second feed pump 14, a mixer 15, a third pipe body 16, a reaction preheater 17, a fourth pipe body 18, a fixed bed reactor 19, a fifth pipe body 20, and a reactant receiving tank 21.

[0028] The first feed pipe 11 is used to transport the dicyclopentadiene solution.

[0029] The inlet of the first feed pump 13 is connected to one end of the first feed pipe 11.

[0030] The second feed pipe 12 is used to transport an acrylic acid solution containing a strong acid catalyst.

[0031] The inlet of the second feed pump 14 is connected to one end of the second feed pipe 12.

[0032] In this embodiment, the output port of the first feed pump 13 is connected to the mixer 15 through the first pipe 131, and the output port of the second feed pump 14 is connected to the mixer 15 through the second pipe 141. It should be understood that in this embodiment, the dicyclopentadiene solution is pumped into the mixer 15 through the first feed pipe 11 by the first feed pump 13, and the acrylic acid solution is pumped into the mixer 15 through the second feed pipe 12 by the second feed pump 14, so that the acrylic acid solution and the dicyclopentadiene solution are mixed within the mixer 15.

[0033] Preferably, a first switching valve 132 for controlling the opening and closing of the first pipe body 131 is provided in the first pipe body 131, and a second switching valve 142 for controlling the opening and closing of the second pipe body 141 is provided in the second pipe body 141.

[0034] Furthermore, the first tube 131 is also provided with a first one-way valve 133 that allows the dicyclopentadiene solution to flow only into the mixer 15, while the second tube 141 is also provided with a second one-way valve 143 that allows the acrylic acid solution to flow only into the mixer 15.

[0035] One end of the third tube 16 is connected to the output port of the mixer 15.

[0036] The inlet of the reaction preheater 17 is connected to the other end of the third tube 16, so that the mixture output from the mixer 15 enters the reaction preheater 17 through the third tube 16 for heating.

[0037] One end of the fourth tube 18 is connected to the output port of the reaction preheater 17.

[0038] In this embodiment, the reaction preheater 17 is U-shaped and is placed horizontally.

[0039] Specifically, the reaction preheater 17 includes a first preheating tube 171 in the shape of an elongated strip and a second preheating tube 172 in the shape of an elongated strip. The first preheating tube 171 and the second preheating tube 172 are connected and have the same length. The second preheating tube 172 is positioned above the first preheating tube 171. The first preheating tube 171 is connected to the other end of a third tube body 16, allowing the mixed liquid to enter from the first preheating tube 171. One end of a fourth tube body 18 is connected to the second preheating tube 172, allowing the preheated mixed liquid to exit from the second preheating tube 171. It should be understood that the first preheating tube 171 and the second preheating tube 172 are parallel and arranged in a horizontal direction.

[0040] Furthermore, the reaction preheater 17 is also provided with an insulation layer 173 surrounding the first preheating pipe 171 and the second preheating pipe 172. The insulation layer 173 forms a flow cavity 1730 with the outer walls of the first and second preheating pipes 171 and 172. The insulation layer 173 at the first preheating pipe 171 has a steam inlet communicating with the flow cavity 1730 for inputting high-temperature steam, and the insulation layer 173 at the second preheating pipe 172 has a steam outlet communicating with the flow cavity 1730 for inputting high-temperature steam. It should be understood that the mixture will exchange heat with high-temperature steam within the reaction preheater 17 to achieve preheating.

[0041] The inlet at the bottom of the fixed-bed reactor 19 is connected to the other end of the fourth tube 18. It should be understood that the mixture heated by the reaction preheater 17 enters the fixed-bed reactor 19 through the fourth tube 18 and reacts in the fixed-bed reactor 19 to form dicyclopentenyl acrylate.

[0042] In this embodiment, the fixed-bed reactor 19 is filled with an acidic catalyst layer 190, which is composed of sulfonic acid resin catalyst particles 1901, so that the sulfonic acid resin catalyst particles 1901 can neutralize the solution after the reaction of acrylic acid and dicyclopentadiene to remove the acidic catalyst.

[0043] One end of the fifth tube 20 is connected to the outlet at the top of the fixed bed reactor 19.

[0044] Specifically, the fixed bed reactor 19 is provided with a receiving cavity, wherein an acidic catalyst layer 190 is disposed in the middle of the receiving cavity to divide the receiving cavity into a first receiving cavity 191 and a second receiving cavity 192 located above the first receiving cavity 191, and the other end of the fourth tube 18 is connected to the first receiving cavity 191, and one end of the fifth tube 20 is connected to the second receiving cavity 192.

[0045] It is worth noting that the mixture heated by the reaction preheater 17 enters the first containment chamber 191 of the fixed bed reactor 19 through the fourth tube 18. At this time, acrylic acid and dicyclopentadiene react in the first containment chamber 191 to generate dicyclopentenyl acrylate. After passing through the acidic catalyst layer 190 for neutralization reaction and removing the acidic catalyst, it rises to the second containment chamber 192 and is discharged from the second containment chamber 192 through the fifth tube 20. The product dicyclopentenyl acrylate without alkaline wastewater is discharged from the second containment chamber 192.

[0046] The inlet of the reactant receiving vessel 21 is connected to the other end of the fifth tube 20 to contain the product dicyclopentenyl acrylate.

[0047] Preferably, the fifth tube 20 is provided with a third switching valve 201 for controlling the channel of the fifth tube 20.

[0048] In this embodiment, the sulfonic acid resin catalyst particles 1901 are spherical in shape, and the diameter of the sulfonic acid resin catalyst particles 1901 ranges from 0.5 to 5 mm.

[0049] Preferably, the temperature range within the fixed-bed reactor 19 is 80-90 degrees Celsius, and the pressure range within the fixed-bed reactor 19 is 0.1-0.2 MPa. That is, when the dicyclopentadiene solution and the acrylic acid solution react in the fixed-bed reactor 19, the temperature range within the fixed-bed reactor 19 is 80-90 degrees Celsius, and the pressure range within the fixed-bed reactor 19 is 0.1-0.2 MPa.

[0050] It should be understood that, since the acidic catalyst is neutralized and removed in the acidic catalyst layer 190, therefore... Figure 4 As shown, in some embodiments, the outer wall of the fixed bed reactor 19 is also provided with a vibrator 30. The acidic catalyst layer 190 is provided with a first vibrating rod 31 in the horizontal direction, a second vibrating rod 32 above the first vibrating rod 31, and a third vibrating rod 33 below the first vibrating rod 31. The vibrator 30 is connected to the first vibrating rod 31 so that the first vibrating rod 31 can be driven to vibrate in the acidic catalyst layer 190 by the vibrator 30, so that the reaction can be accelerated and more uniform, and the neutralization reaction effect can be improved.

[0051] It should be understood that, since the acidic catalyst rises slowly from the acidic catalyst layer 190 and neutralizes the reaction, therefore... Figure 5As shown, in some embodiments, the acidic catalyst layer 190 consists of multiple layers of spaced-apart filter layers 193. Each filter layer 193 includes a receiving plate 1931, a first filter screen 1932 disposed above the receiving plate 1931, and a second filter screen 1933 disposed below the receiving plate 1931. The receiving plate 1931 has multiple through holes spaced apart, and sulfonic acid resin catalyst particles 1901 are disposed in the through holes. It should be understood that the receiving plate 1931 seals the receiving cavity, therefore the reaction liquid can only rise through the through holes.

[0052] It should be understood that the outer diameter of the sulfonic acid resin catalyst particles 1901 is larger than the pore size of the first filter screen 1932 and the second filter screen 1933.

[0053] Preferably, the through holes of two adjacent filter layers 193 are not mutually corresponding, resulting in a longer path for the reaction solution and a better reaction effect. It is worth noting that each filter layer 193 has a needle 1930 on its bottom surface, and the needle 1930 of each filter layer 193 corresponds to the through hole of the filter layer 193 below it. This causes the solution flowing in from the through hole of the filter layer 193 below to flow towards the needle 1930, effectively improving the neutralization reaction effect.

[0054] Furthermore, the outer wall of the fixed-bed reactor 19 is also equipped with a circulation pump 40, wherein the inlet of the circulation pump 40 is connected to the second receiving cavity 192 through the first circulation pipe 41, and the outlet of the circulation pump 40 is located in the middle of the acidic catalyst layer 190 through the second circulation pipe 42, so that the neutralized solution is drawn away by the circulation pump 40 again and transported back to the acidic catalyst layer 190 for multiple neutralization reactions, making the neutralization reaction more effective and the reaction more uniform.

[0055] It should be noted that the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0056] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A system for preparing dicyclopentadiene acrylate without producing alkaline wastewater, characterized in that, include: The first feed pipe is used to convey the dicyclopentadiene solution; The first feed pump has its inlet connected to one end of the first feed pipe; Second feed pipe; The second feed pump has its inlet connected to one end of the second feed pipe; The mixer, wherein the output port of the first feed pump is connected to the mixer via a first pipe, and the second feed pump... The output port of the feed pump is connected to the mixer through a second pipe. The third tube has one end connected to the output port of the mixer; The inlet of the reaction preheater is connected to the other end of the third tube. The fourth tube has one end connected to the output port of the reaction preheater; A fixed-bed reactor, the inlet at its bottom of which is connected to the other end of the fourth tube, wherein the fixed-bed reactor is filled with an acidic catalyst layer; The fifth tube is connected at one end to the outlet at the top of the fixed-bed reactor; A reactant receiving vessel, the inlet of which is connected to the other end of the fifth tube; The acidic catalyst layer is composed of sulfonic acid resin catalyst particles; the acidic catalyst layer is composed of multiple layers of filter layers spaced apart, the filter layer including a receiving plate, a first filter screen disposed above the receiving plate and a second filter screen disposed below the receiving plate, wherein the receiving plate is provided with multiple through holes spaced apart, and the sulfonic acid resin catalyst particles are disposed in the through holes, the outer diameter of the sulfonic acid resin catalyst particles being larger than the pore diameter of the first filter screen and the second filter screen. The through holes of two adjacent filter layers are not corresponding to each other. The outer wall of the fixed bed reactor is also provided with a circulation pump. The inlet of the circulation pump is connected to the second receiving cavity through a first circulation pipe, and the outlet of the circulation pump is located in the middle of the acid catalyst layer through a second circulation pipe.

2. The dicyclopentadiene acrylate preparation system without alkaline wastewater generation according to claim 1, characterized in that, The sulfonic acid resin catalyst particles are spherical in shape, and the diameter of the sulfonic acid resin catalyst particles ranges from 0.5 to 5 mm.

3. The dicyclopentadiene acrylate preparation system without alkaline wastewater generation according to claim 2, characterized in that, The temperature range inside the fixed-bed reactor is 80-90 degrees Celsius, and the pressure range inside the fixed-bed reactor is 0.1-0.2 MPa.

4. The dicyclopentadiene acrylate preparation system without alkaline wastewater generation according to claim 2, characterized in that, The first pipe is provided with a first switching valve for controlling the opening and closing of the first pipe, and the second pipe is provided with a second switching valve for controlling the opening and closing of the second pipe. The first pipe is also provided with a first one-way valve that allows the dicyclopentadiene solution to flow only into the mixer, and the second pipe is also provided with a second one-way valve that allows the acrylic acid solution to flow only into the mixer.

5. The dicyclopentadiene acrylate preparation system without alkaline wastewater generation according to claim 4, characterized in that, The reaction preheater is U-shaped, and includes a first preheating tube and a second preheating tube that are both elongated. The first and second preheating tubes are connected and have the same length, with the second preheating tube positioned above the first preheating tube. The first preheating tube is connected to the other end of the third tube body, and one end of the fourth tube body is connected to the second preheating tube.

6. The dicyclopentadiene acrylate preparation system without alkaline wastewater generation according to claim 5, characterized in that, The reaction preheater is further provided with an insulation layer wrapped around the first preheating tube and the second preheating tube, wherein the insulation layer forms a flow cavity with the outer wall of the first preheating tube and the second preheating tube, and the insulation layer at the first preheating tube is provided with a steam inlet communicating with the flow cavity and for inputting high-temperature steam, and the insulation layer at the second preheating tube is provided with a steam outlet communicating with the flow cavity and for inputting high-temperature steam.

7. The dicyclopentadiene acrylate preparation system without alkaline wastewater generation according to claim 6, characterized in that, The fixed-bed reactor is provided with a receiving cavity, wherein the acidic catalyst layer is disposed in the middle of the receiving cavity to divide the receiving cavity into a first receiving cavity and a second receiving cavity above the first receiving cavity, and the other end of the fourth tube is connected to the first receiving cavity, and one end of the fifth tube is connected to the second receiving cavity.

8. The dicyclopentadiene acrylate preparation system without alkaline wastewater generation according to claim 7, characterized in that, The outer wall of the fixed bed reactor is also provided with a vibrator. The acidic catalyst layer is provided with a first vibrating rod in the horizontal direction, a second vibrating rod above the first vibrating rod, and a third vibrating rod below the first vibrating rod. The vibrator is connected to the first vibrating rod so as to drive the first vibrating rod to vibrate in the acidic catalyst layer.

Images