Device for removing anions and cations from resin solution

Abstract

The utility model relates to a device for removing anions and cations from a resin solution. The device comprises a preheater device, a feed mixing device, a liquid-liquid mass transfer separation device, an oil-water separation device, a qualified product solution tank and a wastewater treatment device. The preheater device is communicated with the feed mixing device and a to-be-treated resin solution, the feed mixing device is connected with the liquid-liquid mass transfer separation device, the liquid-liquid mass transfer separation device is respectively communicated with the oil-water separation device and the feed mixing device, and the oil-water separation device is respectively communicated with the qualified product solution tank and the wastewater treatment device. According to the device, the removal rate of cations and anions in a resin solution can be effectively improved, the content of cations and ions in the solution is reduced to be 5 mu g / g, the content of anions in the solution is reduced to be below 5 mu g / g, meanwhile, the time for removing cations and anions in the resin solution is shortened, the dosage of deionized water is reduced, and the device has an obvious effect on reducing the production cost of resin.

Description

Technical Field

[0001] The utility model relates to a device for removing cations and anions from a resin solution, in particular to a device for removing cations and anions from electronic material-grade resins and food-grade resins. The deionized resin meets industry and national standards, and belongs to the field of resin preparation and purification. Background Art

[0002] The device and method for removing cations and anions from resin solutions are widely used in various applications with strict requirements for metal ions or anions, such as electronic material manufacturing, electronic material packaging, food processing, and food packaging. The metal ion concentration in the product must be less than 10μg / g, and the anion concentration must be less than 10μg / g, or even lower.

[0003] There are two main methods for removing anions and cations from traditional resin solutions. One is to use ion exchange resin to remove metal ions or anions in the resin solution. The advantage of this method is that it does not produce a large amount of salt-containing wastewater during the removal of metal ions and anions, but the cost is high; the other is to use chelating agent (complexing agent) complexing method, in which the chelating agent is prepared into an aqueous solution and added to the resin solution. The chelating agent and the metal ions or anions in the resin solution are complexed to form a water-soluble complex, thereby removing the metal ions and anions in the resin solution. The advantage of this method is that the removal effect is better, but a large amount of salt-containing wastewater is produced.

[0004] U.S. Patent US20240157354A1 discloses a method and apparatus for manufacturing dry ion exchange resins, and a method and apparatus for purifying target liquids. This method can effectively remove anions and cations from target substances, but the ion exchange resins in the patent need to be activated with a strong acid and dried under reduced pressure, resulting in a relatively high processing cost.

[0005] CN117925270A discloses a method for preparing a demetallizing agent, an application method thereof, and a use of a demetallizing auxiliary agent. This patent uses a chelating agent to remove nickel and vanadium from a solution, and has a high demetallization efficiency. However, the amount of chelating agent used is large, requiring more than three solution washes, and a large amount of metal ion-containing wastewater is generated. In addition, the adaptability of different metal ions to the chelating agent needs to be investigated.

[0006] CN116655841B discloses a continuous solution polymerization method and system. The patent adopts a complexing agent to complex with target ions. In this method, the complexing temperature of the complexing agent and the solution ions is relatively high, reaching above 80°C, and the complexing agent solution is washed many times.

[0007] CN116655853A discloses a method for demetallizing a polymer. The patent adopts a combination of complexation and resin adsorption to remove ions from the polymer. This method is beneficial for ion removal, but the cost is relatively high. Utility Model Content

[0008] The technical problem to be solved by the present invention is that, in view of the high metal ion content in the resin solution, the large amount of deionized water used in the metal ion removal process, the high cost, and the difficulty in removal, the technical solution of the present invention can effectively improve the removal rate of metal ions in the resin solution, reduce the metal ion content in the solution to below 5μg / g, reduce the anion content to 5μg / g, shorten the deionization time of the resin solution, reduce the amount of deionized water used, and have a significant effect on reducing the cost of resin production.

[0009] In order to solve the above problems, the present invention adopts the following technical solutions:

[0010] A device for removing anions and cations from a resin solution, comprising a resin solution preheating device and a deionized water preheating device, a primary feed mixing device, a secondary feed mixing device and a tertiary feed mixing device, a primary liquid-liquid mass transfer separation device, a secondary liquid-liquid mass transfer separation device and a tertiary liquid-liquid mass transfer separation device, a primary oil-water separation device, a secondary oil-water separation device and a tertiary oil-water separation device, a qualified product solution tank, and a wastewater treatment device; the resin solution preheating device is respectively connected to a pipeline for a resin solution to be treated and the primary feed mixing device and the tertiary feed mixing device, the deionized water preheating device is respectively connected to a deionized water pipeline and the primary feed mixing device; the primary feed mixing device is respectively connected to the primary liquid-liquid mass transfer separation device and the resin solution pipeline; The fat solution preheating device is connected to the deionized water preheating device, the secondary feed mixing device is respectively connected to the primary purification resin solution pipeline and the secondary liquid-liquid mass transfer separation device and the tertiary external drainage, the tertiary feed mixing device is respectively connected to the resin solution preheating device, the tertiary liquid-liquid mass transfer separation device and the secondary purification resin solution pipeline and the tertiary purification resin solution; the primary liquid-liquid mass transfer separation device is connected to the primary oil-water separation device, the secondary liquid-liquid mass transfer separation device is connected to the secondary oil-water separation device, and the tertiary liquid-liquid mass transfer separation device is respectively connected to the tertiary oil-water separation device; the qualified product solution tank is connected to the tertiary purification resin solution pipeline; the wastewater treatment device is respectively connected to the primary external drainage and the secondary external drainage.

[0011] The first-stage, second-stage and third-stage liquid-liquid mass transfer separation devices all include a cylinder, fiber filaments, a feed port and a cylinder flange; the first-stage, second-stage and third-stage oil-water separation devices all include an oil-water separation tank, a level meter, a thermometer, a pressure gauge, a purified resin liquid outlet, a spare resin purification liquid outlet, a wastewater discharge outlet and a spare wastewater discharge outlet.

[0012] The material of the cylinder in the primary, secondary and tertiary liquid-liquid mass transfer separation devices is stainless steel; the material of the fiber filaments is stainless steel or polymer material, and the fiber filament diameter is 25μm~1000μm, preferably 100μm~500μm.

[0013] A method for removing anions and cations from a resin solution, characterized in that it comprises the following steps:

[0014] (1) The resin solution and deionized water to be treated at a certain concentration are heated to a certain temperature by a resin solution preheating device and a deionized water preheating device respectively. The two streams of materials are fully mixed by a first-stage feed mixer, and the mixed materials are transported to a first-stage liquid-liquid mass transfer separation device through a pipeline.

[0015] (2) The material is subjected to mass transfer-separation in the first-level liquid-liquid mass transfer separation device, and the anions and cations in the resin solution are quickly transferred to water, and then enter the first-level oil-water separation device; the oil-water mixture entering the first-level oil-water separation device is further settled and stratified; the oil-water interface is controlled by the interface meter to realize the first-level purification resin solution discharged from the top of the storage tank and enter the second-level feed mixing device, and the first-level external drainage containing anions and cations is discharged from the bottom of the tank and enters the wastewater treatment device.

[0016] (3) The first-stage purified resin solution and the third-stage external drainage enter the second-stage liquid-liquid mass transfer separation device through the feed second-stage mixing device. The oil-water mixture undergoes a mass transfer-separation process in the second-stage liquid-liquid mass transfer separation device to further remove the anions and cations in the resin solution, and then enters the second-stage oil-water separation device; the oil-water mixture entering the second-stage oil-water separation device is further settled and stratified; the oil-water interface is controlled by the interface meter to realize the discharge of the second-stage purified resin solution from the top of the storage tank and enter the third-stage feed mixing device, and the second-stage external drainage containing anions and cations is discharged from the bottom of the tank and enters the wastewater treatment device.

[0017] (4) The secondary purification resin solution and deionized water enter the tertiary liquid-liquid mass transfer separation device through the tertiary feed mixing device. The oil-water mixture undergoes a mass transfer-separation process in the tertiary liquid-liquid mass transfer separation device to further remove the anions and cations in the resin solution, and then enters the tertiary oil-water separation device; the oil-water mixture entering the tertiary oil-water separation device is further settled and stratified; the oil-water interface is controlled by the interface meter to realize the discharge of the tertiary purification resin solution from the top of the storage tank. After testing, the anion and cation content in the tertiary purification resin solution meets the standard and enters the qualified product tank. The tertiary external drainage is discharged from the bottom of the tank and enters the secondary feed mixing device, thereby achieving the goal of reducing the amount of deionized water used.

[0018] (5) If the anion and cation content of the three-stage purification resin solution does not meet the standards after testing, it will enter the three-stage feed mixer and repeat the steps until the product is qualified.

[0019] The heating medium of the preheating device in step (1) is one of hot water, thermal oil, steam or electric heating, preferably hot water or thermal oil, and the heating temperature is controlled at 20°C~90°C, preferably 40°C~70°C.

[0020] In step (1), the volume ratio of deionized water to the resin solution to be treated is (0.3-5):1, preferably (1-3):1.

[0021] In step (2), step (3) and step (4), the interface position in the oil-water separation tank is controlled at 10% to 80%, preferably 20% to 50%.

[0022] The mass concentration of the resin solution to be treated is 3% to 50%, preferably 5% to 20%.

[0023] The resin to be treated is polyphenylene ether resin, glycidyl ether epoxy resin, etc.

[0024] Features and beneficial effects of this utility model:

[0025] The present invention is different from the existing method of using chemical methods to remove anions or cations in the resin solution to purify the resin solution. The existing method of purifying resin solutions mainly uses chemical agents or ion exchange resins to remove cations and anions in the resin solution. The chemical agent reacts chemically with the cations and anions in the resin solution to generate a more water-soluble complex or ionic salt, thereby removing the cations and anions in the resin. Although this method can remove the target cations and anions in the resin solution, it has the following problems: ① The introduction of a chelating agent brings in new impurities, and subsequent repeated washing with a large amount of deionized water is required (the amount of deionized water used is 3 times that of the present invention), which increases the cost of wastewater treatment. ② Chelating agents are generally carboxylates and organic ammonium salts, which are highly toxic and carcinogenic, and are not conducive to the green and environmentally friendly production concept advocated by the country.

[0026] The traditional resin solution decationization can also meet the application scenario requirements of the existing resin field, but the amount of chelating agent used, the amount of deionized water used, the amount of ion exchange resin used, and the production cost are significantly higher than those of the utility model. The traditional method is not beneficial to the occupational health of employees, nor is it conducive to the green and environmentally friendly production concept advocated by the country.

[0027] Ion exchange resins are effective in removing alkali metals (lithium ions, sodium ions, potassium ions, etc.) or alkaline earth metals (magnesium ions, calcium ions, etc.), but are not very effective in removing heavy metal cations (copper ions, iron ions, chromium ions, cadmium ions, etc.) in resin solutions. In addition, ion exchange resins are expensive, and used ion exchange resins are difficult to regenerate, resulting in a large amount of solid waste. This is also not conducive to the green and environmentally friendly production concept advocated by the country.

[0028] The utility model relies on physical methods and utilizes a liquid-liquid mass transfer separation method. The principles are as follows: ① two different liquids (resin solution and deionized water) have different affinities under the same fixed medium (fiber filaments in the liquid-liquid mass transfer separation device), and the solubility of cations and anions in water is greater, thereby achieving the purpose of removing cations and anions in the resin solution; ② the liquid-liquid mass transfer separation device contains a large number of fiber filaments, which can significantly increase the contact area between the resin and the deionized water, divide the resin solution and the deionized water into several mass transfer units, improve the washing efficiency per unit volume of deionized water, significantly reduce the amount of deionized water used, and reduce or even avoid the use of chelating agents.

[0029] Without using a chelating agent, the utility model can achieve the goal of an ion removal rate greater than 99%, and the anion and cation contents in the resin solution after removal are both less than 5 μg / g, which can meet the application scenarios in the existing resin field.

[0030] 1. The utility model uses a feed mixing device to fully mix the resin solution and deionized water, and then transports the mixed liquid to a liquid-liquid mass transfer separation device. The liquid-liquid mass transfer separation device is equipped with a large number of fiber filaments to increase the contact area between anions and cations in the resin solution and deionized water, thereby improving the mass transfer efficiency and the anion and cation removal rate.

[0031] 2. The liquid-liquid mass transfer separation device in the present invention has a long service life and does not require deliberate maintenance during the production cycle, thereby achieving the goal of low production cost of high-purity resin products.

[0032] 3. The utility model addresses the problem that insufficient contact between the resin solution and deionized water results in long washing time and large deionized water consumption. By increasing the contact area and mass transfer efficiency between the resin solution and deionized water, the purpose of reducing washing time and water consumption is achieved.

[0033] 4. The utility model can be widely used in the purification of resins required in the fields of electronic material manufacturing, electronic material packaging, food processing, food packaging, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is a structural diagram of the present utility model.

[0035] Figure 2 Front view of the liquid-liquid mass transfer separation device and the oil-water separation device.

[0036] Figure 3 It is a top view of the liquid-liquid mass transfer separation device and the oil-water separation device. DETAILED DESCRIPTION

[0037] To facilitate understanding of the present invention, the present invention will be fully described below with reference to the accompanying drawings. The drawings illustrate preferred embodiments of the present invention. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and comprehensive understanding of the present invention.

[0038] It should be noted that when an element is referred to as being “disposed on” another element, it may be directly connected to the other element or there may be an intermediate element. When an element is referred to as being “connected to” another element, it may be directly connected to the other element or there may be an intermediate element.

[0039] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to be limited to the present invention.

[0040] The unit of the anion and cation content in the device and method for removing anions and cations from a resin solution described in the utility model is μg / g. An inductively coupled plasma mass spectrometer (ICP-MS) is used to detect metal ions in the sample, and a potentiometric titration method is used to detect anions in the sample.

[0041] The cation and anion removal rates described in the following examples are as follows:

[0042] Combined with the attached drawings Figure 1 、 Figure 2 and Figure 3A device for removing anions and cations from a resin solution, comprising a resin solution preheating device 2 and a deionized water preheating device 4, a primary feed mixing device 5, a secondary feed mixing device 6 and a tertiary feed mixing device 15, a primary liquid-liquid mass transfer separation device 9, a secondary liquid-liquid mass transfer separation device 13 and a tertiary liquid-liquid mass transfer separation device 17, a primary oil-water separation device 8, a secondary oil-water separation device 14 and a tertiary oil-water separation device 18, a qualified product solution tank 21, and a wastewater treatment device 11; the resin solution preheating device 2 is respectively connected to a pipeline of a resin solution to be treated 1 and the primary feed mixing device 5 and the tertiary feed mixing device 15, the deionized water preheating device 4 is respectively connected to a deionized water pipeline 3 and the primary feed mixing device 5; the primary feed mixing device 5 is respectively connected to the primary liquid-liquid mass transfer separation device 9 and the resin solution The preheating device 2 is connected to the deionized water preheating device 4, the secondary feed mixing device 6 is respectively connected to the primary purification resin solution 7 pipeline and the secondary liquid-liquid mass transfer separation device 13 and the tertiary external drainage 20, the tertiary feed mixing device 15 is respectively connected to the resin solution preheating device 2, the tertiary liquid-liquid mass transfer separation device 17 and the secondary purification resin solution 16 pipeline and the tertiary purification resin solution 19; the primary liquid-liquid mass transfer separation device 9 is connected to the primary oil-water separation device 8, the secondary liquid-liquid mass transfer separation device 13 is connected to the secondary oil-water separation device 14, and the tertiary liquid-liquid mass transfer separation device 17 is respectively connected to the tertiary oil-water separation device 18; the qualified product solution tank 21 is connected to the tertiary purification resin solution 19 pipeline; the wastewater treatment device is respectively connected to the primary external drainage 10 and the secondary external drainage 12.

[0043] The first-stage, second-stage and third-stage liquid-liquid mass transfer separation devices all include a cylinder 23, fiber filaments 24, a feed port 22, and a cylinder flange 25; the first-stage, second-stage and third-stage oil-water separation devices all include an oil-water separation tank 33, a level meter 26, a thermometer 27, a pressure gauge 28, a purified resin liquid outlet 29, a resin purified liquid spare port 30, a wastewater discharge port 31, and a wastewater discharge spare port 32.

[0044] The material of the cylinder 23 in the primary, secondary and tertiary liquid-liquid mass transfer separation devices is stainless steel; the material of the fiber filaments 24 is stainless steel or polymer material, and the fiber filament diameter is 25μm~1000μm, preferably 100μm~500μm.

[0045] The resin solution to be purified is preheated and then subjected to three-stage mass transfer-separation and three-stage oil-water separation treatments to obtain the purified resin.

[0046] Example 1

[0047] A toluene solution of polyphenylene ether resin is used as raw material, and the copper ion content in the resin solution is 783 μg / g. After being treated by a device and method for removing anions and cations from a resin solution described in the utility model, the material is heated to 40°C, the fiber diameter of the liquid-liquid mass transfer separation device is 25 μm, the material is 316L, the oil-water separation tank interface is controlled at 10%, and sampling and analysis from the purified resin solution tank show that the copper ion content is 1 μg / g and the target ion removal rate is 99.9%.

[0048] Example 2

[0049] A toluene solution of polyphenylene ether resin is used as raw material, and the copper ion content in the resin solution is 921 μg / g. After being treated by a device and method for removing anions and cations from a resin solution described in the utility model, the material is heated to 90°C, the fiber diameter of the liquid-liquid mass transfer separation device is 100 μm, the material is 316L, the oil-water separation tank interface is controlled at 50%, and sampling and analysis from the purified resin solution tank show that the copper ion content is 3 μg / g and the target ion removal rate is 99.7%.

[0050] Example 3

[0051] A toluene solution of polyphenylene ether resin is used as raw material, and the copper ion content in the resin solution is 1023 μg / g. After being treated by a device and method for removing anions and cations from a resin solution described in the utility model, the material is heated to 60°C, the fiber diameter of the liquid-liquid mass transfer separation device is 300 μm, the material is 316L, the oil-water separation tank interface is controlled at 80%, and sampling and analysis from the purified resin solution tank show that the copper ion content is 2 μg / g and the target ion removal rate is 99.8%.

[0052] Example 4

[0053] Using glycidyl ether epoxy resin solution as raw material, the chloride ion content in the resin solution is 876 μg / g. After being treated by a device and method for removing anions and cations from a resin solution described in the utility model, the material is heated to 30°C, the fiber diameter of the liquid-liquid mass transfer separation device is 500 μm, the material is 316L, the oil-water separation tank interface is controlled at 10%, and sampling and analysis from the purified resin solution tank show that the chloride ion content is 4 μg / g and the target ion removal rate is 99.5%.

[0054] Example 5

[0055] Using glycidyl ether epoxy resin solution as raw material, the chloride ion content in the resin solution is 983μg / g. After being treated by a device and method for removing anions and cations from a resin solution described in the utility model, the material is heated to 70°C, the fiber diameter of the liquid-liquid mass transfer separation device is 1000μm, the material is PTFE, the oil-water separation tank interface is controlled at 50%, and sampling and analysis from the purified resin solution tank show that the chloride ion content is 4μg / g and the target ion removal rate is 99.5%.

[0056] Example 6

[0057] Using glycidyl ether epoxy resin solution as raw material, the chloride ion content in the resin solution is 760 μg / g. After being treated by a device and method for removing anions and cations from a resin solution described in the utility model, the material is heated to 60°C, the fiber diameter of the liquid-liquid mass transfer separation device is 800 μm, the material is PTFE, the oil-water separation tank interface is controlled at 30%, and sampling and analysis from the purified resin solution tank show that the chloride ion content is 4 μg / g and the target ion removal rate is 99.5%.

[0058] Example 7

[0059] Using glycidyl ether epoxy resin solution as raw material, the chloride ion content in the resin solution is 801 μg / g. After being treated by a device and method for removing anions and cations from a resin solution described in the utility model, the material is heated to 60°C, the fiber diameter of the liquid-liquid mass transfer separation device is 500 μm, the material is PTFE, the oil-water separation tank interface is controlled at 20%, and sampling and analysis from the purified resin solution tank show that the chloride ion content is 3 μg / g and the target ion removal rate is 99.6%.

[0060] Example 8

[0061] Using glycidyl ether epoxy resin solution as raw material, the chloride ion content in the resin solution is 1203 μg / g. After being treated by a device and method for removing anions and cations from a resin solution described in the utility model, the material is heated to 60°C, the fiber diameter of the liquid-liquid mass transfer separation device is 300 μm, the material is PTFE, the oil-water separation tank interface is controlled at 50%, and sampling and analysis from the purified resin solution tank show that the chloride ion content is 4 μg / g and the target ion removal rate is 99.7%.

[0062] Example 9

[0063] Using polyphenylene ether resin solution as raw material, the copper ion content in the resin solution is 1358 μg / g. After being treated by a device and method for removing anions and cations from a resin solution described in the utility model, the material is heated to 60°C, the fiber diameter of the liquid-liquid mass transfer separation device is 200 μm, the material is PTFE, the oil-water separation tank interface is controlled at 10%, and sampling and analysis from the purified resin solution tank show that the copper ion content is 4 μg / g and the target ion removal rate is 99.7%.

[0064] The above-described embodiment merely represents one embodiment of the present invention. While the description is relatively specific and detailed, it should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art may make various modifications and improvements without departing from the scope of the present invention, and these modifications and improvements fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A device for removing anions and cations from a resin solution, characterized in that The invention comprises a resin solution preheating device (2) and a deionized water preheating device (4), a first-stage feed mixing device (5), a second-stage feed mixing device (6) and a third-stage feed mixing device (15), a first-stage liquid-liquid mass transfer separation device (9), a second-stage liquid-liquid mass transfer separation device (13) and a third-stage liquid-liquid mass transfer separation device (17), a first-stage oil-water separation device (8), a second-stage oil-water separation device (14) and a third-stage oil-water separation device (18), a qualified product solution tank (21), and a wastewater treatment device (11); the resin solution preheating device (2) is respectively connected to the pipeline of the resin solution to be treated (1) and the first-stage feed mixing device (5) and the third-stage feed mixing device (15); the deionized water preheating device (4) is respectively connected to the deionized water (3) pipeline and the first-stage feed mixing device (5); the first-stage feed mixing device (5) is respectively connected to the first-stage liquid-liquid mass transfer separation device (9) and the resin solution preheating device (2) and the deionized water preheating device (4); the secondary feed mixing device (6) is respectively connected to the primary purification resin solution (7) pipeline and the secondary liquid-liquid mass transfer separation device (13) and the tertiary external drainage (20); the tertiary feed mixing device (15) is respectively connected to the resin solution preheating device (2), the tertiary liquid-liquid mass transfer separation device (17) and the secondary purification resin solution (16) pipeline and the tertiary purification resin solution (19); the primary liquid-liquid mass transfer separation device (9) is connected to the primary oil-water separation device (8); the secondary liquid-liquid mass transfer separation device (13) is connected to the secondary oil-water separation device (14); the tertiary liquid-liquid mass transfer separation device (17) is respectively connected to the tertiary oil-water separation device (18); the qualified product solution tank (21) is connected to the tertiary purification resin solution (19) pipeline; the wastewater treatment device is respectively connected to the primary external drainage (10) and the secondary external drainage (12).

2. The device for removing anions and cations from a resin solution according to claim 1, characterized in that The liquid-liquid mass transfer separation device comprises a cylinder (23), fiber filaments (24), a feed port (22), and a cylinder flange (25).

3. The device for removing anions and cations from a resin solution according to claim 1, characterized in that The oil-water separation device comprises an oil-water separation tank (33), a level gauge (26), a thermometer (27), a pressure gauge (28), a purified resin liquid outlet (29), a resin purified liquid standby outlet (30), a wastewater discharge outlet (31), and a wastewater discharge standby outlet (32).

4. The device for removing anions and cations from a resin solution according to claim 2, characterized in that The material of the cylinder (23) in the liquid-liquid mass transfer separation device is stainless steel; the material of the fiber filament (24) is stainless steel or a polymer material, and the diameter of the fiber filament is 25 μm to 1000 μm.

5. The device for removing anions and cations from a resin solution according to claim 4, characterized in that The fiber filament has a diameter of 100 μm to 500 μm.

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