Production method of high-efficiency boron-removing ion exchange membrane

Abstract

The invention discloses a production method of a high-efficiency boron-removing ion exchange membrane, which comprises the following steps of: weighing special CH-99 boron ion chelating resin, A-23 strong-base anion exchange resin and modified high-density polyethylene according to a ratio, putting into a high-speed mixing stirrer, uniformly mixing at normal temperature, mixing, cutting into small blocks of materials, and granulating to obtain the high-efficiency boron-removing ion exchange membrane. Feeding into an extruder, and calendering into sheets; according to the production method of the high-efficiency boron-removing ion exchange membrane, the total exchange capacity of the ion exchange membrane made of the boron-removing ion exchange resin reaches 0.8 meq / ml, the equilibrium boron content reaches 5.7 meq / ml, and the boron treatment capacity is improved by 2-3 times compared with that of a common membrane, so that no crystal is generated after most of boron elements are taken out from an electrode water chamber, a runner is ensured to be unblocked, and the service life of the membrane is prolonged. And the preparation method is simple and reasonable, and has the advantages of mild reaction conditions, high yield, low energy consumption, few pollutants and suitability for large-scale production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyurethane materials, in particular to a production method of high-efficiency boron ion exchange membrane. BACKGROUND

[0002] At present, the ion exchange membrane used on the electrodeionization membrane stack for producing industrial ultrapure water in the market is an ordinary industrial membrane, and the main function is to remove a small amount of monovalent ions such as sodium ions and chloride ions and other strong electrolytes in the secondary reverse osmosis product water. However, the boron content in the surface water in some areas of China is very high, and the residual amount of boron after the secondary reverse osmosis treatment still exceeds 15 ppm. Because the capacity of the electrodeionization membrane stack for treating boron is limited, boric acid is a slightly soluble substance in water and belongs to a weak electrolyte in the flow channel. Crystals are formed in the electrode water chamber of the electrodeionization membrane stack, which blocks the gap and flow channel in the resin, causes the water production of the electrode water chamber to decrease, and the heat generated by the electrode cannot be removed in time. The temperature in the flow channel rises, and the water distribution plate, ion exchange membrane, resin and electrode are all burned due to overheating, and the electrodeionization membrane stack is scrapped as a whole. Therefore, the present application provides a production method of high-efficiency boron-removing ion exchange membrane to solve the above problems. SUMMARY

[0003] The present application aims at the deficiencies of the prior art, and provides a production method of high-efficiency boron-removing ion exchange membrane to solve the problems proposed in the background.

[0004] To achieve the above-mentioned purpose, the present application provides the following technical scheme: a production method of high-efficiency boron-removing ion exchange membrane, comprising the following production steps:

[0005] S1: CH-99 boron ion special chelating resin, A-23 strong base type anion exchange resin and modified high-density polyethylene are weighed according to the ratio and then put into a high-speed mixing stirrer, and mixed uniformly at room temperature;

[0006] S2: the mixture obtained in S1 is put into a closed mixer, and heated to 160 DEG C in the closed mixing chamber by a heating device to make it in a viscous flow state. Plasticizer, antioxidant, anti-aging agent, paraffin and crosslinking agent are added in sequence during the mixing process, and a lump material is obtained after mixing for 30 min;

[0007] S3: the lump material obtained in S2 is taken out from the mixer, cut into small pieces, and the small pieces are less than 8 cm. After cooling, the small piece material is sent into a blade type pulverizer to be pulverized into granular material.

[0008] S4: the granular material obtained in S3 is put into a double screw extruder, and the material sheet is extruded at a temperature of 185-225 DEG C, and after calendering and cooling, the extruded material sheet is cut into pieces according to the marked size by a traction machine and a sheet cutting machine, to obtain the high-efficiency boron ion exchange membrane piece.

[0009] As a preferred scheme of the present application, the high-efficiency boron ion exchange membrane piece comprises the following component contents according to the mass component: CH-99 boron ion special chelating resin 58-75 parts, A-23 strong base type anion exchange resin 10-20 parts, modified high-density polyethylene 15-25 parts, plasticizer 3-6 parts, antioxidant 0.8-2.5 parts, anti-aging agent 0.4-1.6 parts, paraffin 3-7 parts, and crosslinking agent 2-3 parts.

[0010] As a preferred scheme of the present application, the modified high-density polyethylene is obtained by surface treatment of nano ultra-fine calcium carbonate, dry mixing with high-density polyethylene in a high-speed mixer for 3-5 minutes, and then melt extruding, cooling, and granulating in a double screw extruder.

[0011] As a preferred scheme of the present application, the plasticizer is one or a mixture of two or more of dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, dioctyl phthalate, butyl benzyl phthalate, di(2-ethyl)hexyl phthalate, and diisononyl phthalate.

[0012] As a preferred scheme of the present application, the temperature of each zone of the double screw extruder in S4 is as follows: the temperature of the first zone is 185-190 DEG C, the temperature of the second zone is 190-195 DEG C, the temperature of the third zone is 195-200 DEG C, the temperature of the fourth zone is 200-205 DEG C, the temperature of the fifth zone is 205-210 DEG C, the temperature of the sixth zone is 215-215 DEG C, the temperature of the seventh zone is 215-220 DEG C, the temperature of the die is 220-225 DEG C, and the screw rotation speed is 100-120 r / min.

[0013] As a preferred scheme of the present application, the maximum diameter of the small block material is 8 cm, and the particle size of the granular material is 3-5 mm.

[0014] As a preferred scheme of the present application, the width of the material sheet is 400 mm, and the thickness is 0.6 mm.

[0015] Compared with the prior art, the present application provides a production method of a high-efficiency boron ion exchange membrane piece, which has the following beneficial effects:

[0016] 1. The production method of the high-performance boron ion exchange membrane, which uses CH-99 boron ion special chelating resin as raw material, has a functional group of multi-hydroxy amine capable of forming a complex with boron, and a backbone of a styrene and divinyl benzene crosslinked resin, and can selectively adsorb boron.

[0017] 2. The production method of the high-performance boron ion exchange membrane, which uses a de-boron ion exchange resin to make an ion exchange membrane, has a total exchange capacity of 0.8 meq / ml, an equilibrium boron capacity of 5.7 meq / ml, and a boron treatment capacity 2-3 times higher than that of an ordinary membrane, so that most of the boron elements in the polar water chamber are removed, and no crystallization occurs, ensuring smooth flow and preventing dry burning. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of the present application.

[0019] Embodiment 1: A production method of a high-performance boron ion exchange membrane, comprising the following production steps:

[0020] S1: CH-99 boron ion special chelating resin, A-23 strong alkali type anion exchange resin, and modified high-density polyethylene are weighed according to the ratio and then put into a high-speed mixing stirrer, and mixed uniformly at room temperature;

[0021] S2: The mixture obtained in S1 is put into a closed mixer, and heated to 160°C in a closed mixing chamber by a heating device to make it in a viscous flow state. Plasticizer, antioxidant, anti-aging agent, paraffin, and crosslinking agent are added in sequence during the mixing process, and a lump material is obtained after mixing for 30 min.

[0022] S3: The lump material obtained in S2 is taken out from the mixer, cut into small pieces, and the small pieces are cooled and then sent to a blade type pulverizer to be pulverized into granular material.

[0023] S4: The granular material obtained in S3 is put into a double screw extruder, and the material sheet is extruded at a temperature of 185-225℃. After calendering and cooling, the extruded material sheet is cut into pieces according to the specified size by a traction machine and a sheet cutting machine, to obtain the high-efficiency boron ion exchange membrane sheet.

[0024] Further, the high-efficiency boron ion exchange membrane sheet comprises the following component contents according to the mass component: 58 parts of CH-99 boron ion special chelating resin, 10 parts of A-23 strong base anion exchange resin, 15 parts of modified high-density polyethylene, 3 parts of plasticizer, 0.8 parts of antioxidant, 0.4 parts of anti-aging agent, 3 parts of paraffin, and 2 parts of crosslinking agent.

[0025] Further, the modified high-density polyethylene is obtained by surface treatment of nano ultra-fine calcium carbonate, dry mixing with high-density polyethylene in a high-speed mixer for 3-5 minutes, and then melting extrusion, cooling and granulation in a double screw extruder.

[0026] Further, the plasticizer is one or a mixture of two or more of dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, dioctyl phthalate, butyl benzyl phthalate, di(2-ethyl)hexyl phthalate, and diisononyl phthalate.

[0027] Further, the temperature of each zone of the double screw extruder in S4 is as follows: the temperature of the first zone is 185-190℃, the temperature of the second zone is 190-195℃, the temperature of the third zone is 195-200℃, the temperature of the fourth zone is 200-205℃, the temperature of the fifth zone is 205-210℃, the temperature of the sixth zone is 215-215℃, the temperature of the seventh zone is 215-220℃, the die temperature is 220-225℃, and the screw rotation speed is 100-120r / min.

[0028] Further, the maximum diameter of the small block material is 8cm, and the particle size of the granular material is 3-5mm.

[0029] Further, the width of the material sheet is 400mm, and the thickness is 0.6mm.

[0030] Embodiment 2: A production method of a high-efficiency boron ion exchange membrane sheet, comprising the following production steps:

[0031] S1: CH-99 boron ion special chelating resin and A-23 strong base anion exchange resin and modified high-density polyethylene are weighed according to the ratio and then put into a high-speed mixing stirrer, and mixed uniformly at room temperature.

[0032] S2: The mixture obtained in S1 is put into a closed mixer, and heated to 160°C by a heating device in the closed mixing chamber to make it in viscous flow state. During the mixing, plasticizer, antioxidant, anti-aging agent, paraffin and crosslinking agent are added in sequence, and the mass is obtained after mixing for 30 minutes.

[0033] S3: The mass obtained in S2 is taken out of the mixer, and cut into small pieces. The small pieces below 8 cm are cooled and sent into a blade pulverizer to be pulverized into granular material.

[0034] S4: The granular material obtained in S3 is put into a double screw extruder, and the material sheet is extruded at a temperature of 185-225°C. The extruded material sheet is cooled after calendering, and then cut into pieces according to the specified size by a traction machine and a cutting machine to obtain the high-efficiency boron ion exchange membrane sheet.

[0035] Further, according to the mass component, the high-efficiency boron ion exchange membrane sheet comprises the following component contents: 62 parts of CH-99 boron ion special chelating resin, 15 parts of A-23 strong base anion exchange resin, 20 parts of modified high-density polyethylene, 4 parts of plasticizer, 1.2 parts of antioxidant, 0.6 parts of anti-aging agent, 4 parts of paraffin and 2 parts of crosslinking agent.

[0036] Example 2 has the same material and processing steps as the above examples, except that the proportions of the two are different.

[0037] Example 3: A production method of a high-efficiency boron ion exchange membrane sheet, comprising the following production steps:

[0038] S1: CH-99 boron ion special chelating resin and A-23 strong base anion exchange resin and modified high-density polyethylene are weighed according to the ratio and put into a high-speed mixing stirrer to mix uniformly at room temperature;

[0039] S2: The mixture obtained in S1 is put into a closed mixer, and heated to 160°C by a heating device in the closed mixing chamber to make it in viscous flow state. During the mixing, plasticizer, antioxidant, anti-aging agent, paraffin and crosslinking agent are added in sequence, and the mass is obtained after mixing for 30 minutes.

[0040] S3: The mass obtained in S2 is taken out of the mixer, and cut into small pieces. The small pieces below 8 cm are cooled and sent into a blade pulverizer to be pulverized into granular material.

[0041] S4: The granular material obtained in S3 is put into a double screw extruder, and the material sheet is extruded at a temperature of 185-225°C. The extruded material sheet is cooled after calendering, and then cut into pieces according to the specified size by a traction machine and a cutting machine, to obtain the high-efficiency boron ion exchange membrane piece.

[0042] Further, according to the mass component, the high-efficiency boron ion exchange membrane piece comprises the following component contents: 67 parts of CH-99 boron ion special chelating resin, 18 parts of A-23 strong base anion exchange resin, 20 parts of modified high-density polyethylene, 5 parts of plasticizer, 1.8 parts of antioxidant, 0.8 parts of anti-aging agent, 5 parts of paraffin, and 2 parts of crosslinking agent.

[0043] Example 3 is the same as the above-mentioned example material and processing steps, except that the proportions of the two are different.

[0044] Example 4: A production method of a high-efficiency boron ion exchange membrane piece, comprising the following production steps:

[0045] S1: The CH-99 boron ion special chelating resin, the A-23 strong base anion exchange resin, and the modified high-density polyethylene are weighed according to the ratio and then put into a high-speed mixing stirrer to mix uniformly at room temperature;

[0046] S2: The mixture obtained in S1 is put into a closed mixer, and the heating device is used to heat to 160°C in the closed mixing chamber to make it in a viscous flow state. The plasticizer, antioxidant, anti-aging agent, paraffin, and crosslinking agent are added in sequence during the mixing process, and the mixed material is obtained after 30 minutes of mixing to form a mass.

[0047] S3: The mass material obtained in S2 is taken out of the mixer and cut into small pieces. The small pieces below 8 cm are cooled and then put into a blade grinder to be ground into granular material.

[0048] S4: The granular material obtained in S3 is put into a double screw extruder, and the material sheet is extruded at a temperature of 185-225°C. The extruded material sheet is cooled after calendering, and then cut into pieces according to the specified size by a traction machine and a cutting machine, to obtain the high-efficiency boron ion exchange membrane piece.

[0049] Further, according to the mass component, the high-efficiency boron ion exchange membrane piece comprises the following component contents: 67 parts of CH-99 boron ion special chelating resin, 18 parts of A-23 strong base anion exchange resin, 20 parts of modified high-density polyethylene, 5 parts of plasticizer, 1.8 parts of antioxidant, 0.8 parts of anti-aging agent, 5 parts of paraffin, and 2 parts of crosslinking agent.

[0050] Example 4 uses the same materials and processing steps as the examples above, but the ratio of the two is different.

[0051] Example 5: A method for producing a high-efficiency boron removal ion exchange membrane, comprising the following production steps:

[0052] S1: Weigh CH-99 boron ion chelating resin, A-23 strong base anion exchange resin and modified high-density polyethylene according to the ratio and put them into a high-speed mixer and mix them evenly at room temperature.

[0053] S2: The mixture obtained in S1 is fed into a closed mixer. In the closed mixing chamber, it is heated to 160°C by a heating device to make it in a viscous flow state. During the mixing process, plasticizer, antioxidant, anti-aging agent, paraffin and crosslinking agent are added in sequence. After mixing for 30 minutes, agglomerated material is obtained.

[0054] S3: Take the lumpy material obtained in S2 out of the mixer, cut it into small pieces of material, less than 8 cm in size, and after cooling, send the small pieces of material into a blade crusher to crush them into granular material.

[0055] S4: The granular material obtained in S3 is fed into a twin-screw extruder and extruded into a sheet at a temperature of 185℃-225℃. After the extruded sheet is calendered and cooled by a calender, it is then cut into sheets according to the specified size by a traction machine and a sheet cutter to obtain the high-efficiency boron removal ion exchange membrane.

[0056] Furthermore, based on the mass composition, the high-efficiency boron removal ion exchange membrane comprises the following components: 75 parts of CH-99 boron ion chelating resin, 20 parts of A-23 strong base anion exchange resin, 25 parts of modified high-density polyethylene, 6 parts of plasticizer, 2.5 parts of antioxidant, 1.6 parts of anti-aging agent, 7 parts of paraffin wax, and 3 parts of crosslinking agent.

[0057] Example 5 uses the same materials and processing steps as the examples above, but the ratio of the two is different.

[0058] This invention uses CH-99 boron ion-specific chelating resin as the raw material base. It has a functional group called polyhydroxyamine that can form a complex with boron. Its skeleton is a resin cross-linked with styrene and divinylbenzene. The polyhydroxy groups can complex with boron to achieve selective adsorption of boron. At the same time, CH-99 boron ion-specific chelating resin has the characteristics of high adsorption rate and strong adsorption capacity, which can reduce the overall use cost and has significant comprehensive economic benefits. It is especially suitable as a high-speed adsorption material for boron in low-concentration environments.

[0059] The ion exchange membrane made with boron-removing ion exchange resin has a total exchange capacity of 0.8 meq / ml and a balance boron capacity of 5.7 meq / ml. The boron treatment capacity is 2-3 times higher than that of ordinary membranes. This ensures that most of the boron is removed from the electrode chamber and no crystallization occurs, thus guaranteeing smooth flow and effectively preventing dry burning. Moreover, its preparation method is simple and reasonable, and has the advantages of mild reaction conditions, high yield, low energy consumption, low pollutants, and suitability for large-scale production.

[0060] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for producing a high-efficiency boron removal ion exchange membrane, characterized in that: The production process includes the following steps: S1: Weigh CH-99 boron ion chelating resin, A-23 strong base anion exchange resin and modified high-density polyethylene according to the ratio and put them into a high-speed mixer and mix them evenly at room temperature. S2: The mixture obtained in S1 is fed into a closed mixer. In the closed mixing chamber, it is heated to 160°C by a heating device to make it in a viscous flow state. During the mixing process, plasticizer, antioxidant, anti-aging agent, paraffin and crosslinking agent are added in sequence. After mixing for 30 minutes, agglomerated material is obtained. S3: Take the agglomerated material obtained in S2 out of the mixer, cut it into small pieces of material, less than 8 cm in size, and after cooling, send the small pieces of material into a blade crusher to crush them into granular material. S4: The granular material obtained in S3 is fed into a twin-screw extruder and extruded into a sheet at a temperature of 185℃-225℃. After the extruded sheet is calendered and cooled by a calender, it is then cut into sheets according to the specified size by a traction machine and a sheet cutter to obtain the high-efficiency boron removal ion exchange membrane.

2. The method for producing a high-efficiency boron removal ion exchange membrane according to claim 1, characterized in that, Based on the mass composition, the high-efficiency boron removal ion exchange membrane comprises the following components: 58-75 parts of CH-99 boron ion chelating resin, 10-20 parts of A-23 strong base anion exchange resin, 15-25 parts of modified high-density polyethylene, 3-6 parts of plasticizer, 0.8-2.5 parts of antioxidant, 0.4-1.6 parts of anti-aging agent, 3-7 parts of paraffin wax, and 2-3 parts of crosslinking agent.

3. The method for producing a high-efficiency boron removal ion exchange membrane according to claim 1, characterized in that, The modified high-density polyethylene is obtained by surface treatment of nano-ultrafine calcium carbonate, followed by dry mixing with high-density polyethylene in a high-speed mixer for 3-5 minutes, and then melt extrusion, cooling, and pelletizing in a twin-screw extruder.

4. The method for producing a high-efficiency boron removal ion exchange membrane according to claim 1, characterized in that, The plasticizer is one or a mixture of two or more of the following: dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, dioctyl phthalate, butyl benzyl phthalate, di(2-ethylhexyl) phthalate, and diisononyl phthalate.

5. The method for producing a high-efficiency boron removal ion exchange membrane according to claim 1, characterized in that, The temperatures of each zone of the twin-screw extruder in S4 are as follows: Zone 1: 185-190℃; Zone 2: 190-195℃; Zone 3: 195-200℃; Zone 4: 200-205℃; Zone 5: 205-210℃; Zone 6: 215-215℃; Zone 7: 215-220℃; Die temperature: 220-225℃; Screw speed: 100-120 r / min.

6. The method for producing a high-efficiency boron removal ion exchange membrane according to claim 1, characterized in that, The maximum diameter of the small pieces of material is 8 cm, and the particle size of the granular material is 3-5 mm.

7. The method for producing a high-efficiency boron removal ion exchange membrane according to claim 1, characterized in that: The material sheet has a width of 400 mm and a thickness of 0.6 mm.