CN111420565A - Acid-resistant ion exchange membrane and preparation method thereof - Google Patents
Acid-resistant ion exchange membrane and preparation method thereof Download PDFInfo
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- CN111420565A CN111420565A CN202010282185.5A CN202010282185A CN111420565A CN 111420565 A CN111420565 A CN 111420565A CN 202010282185 A CN202010282185 A CN 202010282185A CN 111420565 A CN111420565 A CN 111420565A
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- ion exchange
- acid
- linear low
- density polyethylene
- membrane
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- 239000002253 acid Substances 0.000 title claims abstract description 57
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 38
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 99
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 99
- 239000000843 powder Substances 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000004113 Sepiolite Substances 0.000 claims abstract description 21
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 21
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 21
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 18
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 18
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 18
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 18
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 17
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 17
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 82
- 239000012528 membrane Substances 0.000 claims description 67
- 238000002156 mixing Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 16
- 239000003729 cation exchange resin Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 13
- 229920000573 polyethylene Polymers 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 239000003957 anion exchange resin Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910000077 silane Inorganic materials 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000003490 calendering Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000000413 hydrolysate Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical group OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 14
- 238000005260 corrosion Methods 0.000 abstract description 14
- 238000005342 ion exchange Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 38
- 239000011347 resin Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 20
- 239000007822 coupling agent Substances 0.000 description 18
- 239000003963 antioxidant agent Substances 0.000 description 13
- 230000003078 antioxidant effect Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
- 150000002500 ions Chemical group 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 8
- 238000009296 electrodeionization Methods 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 229920002367 Polyisobutene Polymers 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 230000009967 tasteless effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RQBWMLFHMVFSBS-UHFFFAOYSA-N 2,4-dinitrophenol;sodium Chemical group [Na].OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RQBWMLFHMVFSBS-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 238000013475 authorization Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005370 electroosmosis Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Urology & Nephrology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of diaphragm materials, in particular to an acid-resistant ion exchange diaphragm and a preparation method thereof, and solves the problem of poor acid corrosion resistance of the traditional ion exchange diaphragm. The acid-resistant ion exchange membrane comprises the following components in parts by weight: 6000 parts of ion exchange resin powder 5000-; the modified linear low-density polyethylene is prepared by modifying linear low-density polyethylene by nano silicon dioxide, sepiolite powder, microcrystalline cellulose and a silane coupling agent; melting of linear low density polyethyleneThe index is 2.0g/10min, and the density is 0.9225g/cm3. The acid-resistant ion exchange membrane provided by the invention has the effects of good acid corrosion resistance, good ion exchange performance and long service life.
Description
Technical Field
The invention relates to the technical field of diaphragm materials, in particular to an acid-resistant ion exchange diaphragm and a preparation method thereof.
Background
The ion exchange membrane is a high molecular membrane which contains ion groups and has selective permeability to ions in a solution, and is mainly used for desalting brackish water, desalting and concentrating the solution, softening and desalting boiler water and the like, wherein Electrodeionization (EDI) is one of innovative and innovative technologies in the field of water treatment in recent years, and is a water treatment technology combining electroosmosis and ion exchange, generally, the water purification process mainly comprises three times of filtration, namely ① primary filtration for removing substances such as insoluble silt and the like in water through a primary filtration membrane, ② secondary filtration for removing soluble divalent ions such as calcium ions and magnesium ions in water through a reverse osmosis membrane, ③ tertiary filtration for removing monovalent ions such as sodium ions and chloride ions in water through an ion exchange membrane, and ultrapure water can be obtained after the tertiary filtration.
In the prior art, a chinese patent with an authorization publication number of CN105870485B discloses an ion exchange membrane and a preparation process thereof, wherein the ion exchange membrane comprises the following raw material components in parts by weight: 5600-6400 parts of anion/cation exchange resin powder, 1450-1500 parts of modified polyethylene, 480 parts of polyisobutylene 460-480 parts, 40-60 parts of visible light initiator, 35-175 parts of cross-linking agent, 65-195 parts of coupling agent and 50-80 parts of antioxidant; the coupling agent is one of a zirconium coupling agent, a magnesium coupling agent and a tin coupling agent. The antioxidant is 2, 4-dinitrophenol sodium. A preparation process of an ion exchange membrane comprises the following steps: s1, weighing the nano zinc oxide modified high-density polyethylene, the polyisobutylene, the coupling agent, the visible light initiator and the cross-linking agent according to a ratio, putting the weighed materials into a high-speed mixing stirrer, fully and uniformly mixing the materials at normal temperature, and then adding anion/cation exchange resin powder according to a ratio; s2, preparing a sheet from the mixture in the S1, and attaching polymer mesh cloth to two sides of the sheet; s3, putting the sheet with the macromolecular material mesh cloth in the S2 into a multi-layer electric heating template, and heating and pressing the sheet at 180-220 ℃ for molding, wherein the time is controlled to be 1.0-2.5 h; and S4, after the sheet material in the S3 is heated, cooling and shaping the sheet material, and finally demolding. The preparation process can prepare the material with exchange capacity of about 4.6mol/kg and membrane surface resistance of 5.02 omega cm2And ion exchange membranes having high performance on the left and right sides, and which are suitable for deep desalination of industrial pure water, and thus are widely used.
Generally, after primary filtration and secondary filtration, divalent ions such as calcium ions and magnesium ions in water can be removed, so that the hardness of the water is reduced to below 1 ppm; but in the secondary filtration, when the reverse osmosis membrane is broken, the capacity of the reverse osmosis membrane for removing the divalent ions in water is reduced, so that the hardness of the water is higher than 1 ppm; at this time, after the high-hardness water enters the electrodeionization membrane stack and is filtered by the ion exchange membrane, although divalent ions and monovalent ions in the water can be filtered, the interior of the membrane stack generates scale due to the action of calcium ions and magnesium ions as time goes on, and in order to improve the working efficiency of the membrane stack, the scale in the membrane stack needs to be cleaned by hydrochloric acid; because the antioxidant and the coupling agent containing metal ions are added into the raw materials of the traditional ion exchange membrane, although the antioxidant and the coupling agent can improve the thermal oxidation resistance of the ion exchange membrane during high-temperature processing and improve the compatibility of the ion resin and the polyethylene resin, the components containing the metal ions can react with hydrochloric acid in the acid washing process, so that the ion exchange membrane is corroded to form micropores inside, the problems of strength reduction, water permeability increase and water production resistivity reduction of the ion exchange membrane are caused, and the performance and the service life of the ion exchange membrane are greatly influenced. If the antioxidant and the coupling agent which do not contain metal ions are replaced, the polarity of the ion exchange resin is influenced due to certain active groups in the antioxidant and the coupling agent, the ion exchange performance of the membrane is influenced, and the exchange capacity is lower than 2.0mol/kg of an industry standard value. Therefore, how to improve the acid corrosion resistance of the ion exchange membrane without affecting the ion exchange performance of the ion exchange membrane is a problem to be solved.
Disclosure of Invention
Aiming at the defects in the prior art, the first object of the invention is to provide an acid-resistant ion exchange membrane which has the advantages of good acid corrosion resistance, good ion exchange performance and long service life.
The second purpose of the invention is to provide a preparation method of the acid-resistant ion exchange membrane, which has the advantages of simple processing technology and easy control.
In order to achieve the first object, the invention provides the following technical scheme: an acid-resistant ion exchange membrane comprises the following components in parts by weight:
6000 parts of ion exchange resin powder 5000-; the modified linear low-density polyethylene is prepared by modifying linear low-density polyethylene by nano silicon dioxide, sepiolite powder, microcrystalline cellulose and a silane coupling agent;
the linear low density polyethylene has a melt index of 2.0g/10min and a density of 0.9225g/cm3。
By adopting the technical scheme, the linear low-density polyethylene has good flexibility, strength, heat resistance and processability, the linear low-density polyethylene is used for replacing common polyethylene, the mechanical properties such as tensile strength, tensile strength and the like of the membrane can be improved, and the required strength can be achieved without hot-press molding of the membrane and mesh cloth; the modified linear low-density polyethylene has good compatibility with ion exchange resin powder, and can remove the coupling agent in the raw material; the polyethylene wax is used as a macromolecular dispersing agent, so that the dispersing uniformity of the ion exchange resin powder and the modified linear low-density polyethylene can be further improved; the raw materials of the ion exchange membrane do not need to be added with an antioxidant and a coupling agent containing metal ions, so that the membrane can not react with hydrochloric acid, when the ion exchange membrane is applied to an electrodeionization membrane stack, the membrane can not be corroded by the hydrochloric acid after scaling and is chemically cleaned, the water production resistivity of the membrane can still be above 16M omega cm, the performance and the service life of the membrane can not be influenced by the hydrochloric acid, and the service life of the membrane can be greatly prolonged.
The nano silicon dioxide is non-toxic, tasteless and pollution-free, has good ultraviolet resistance, can improve the ageing resistance, strength and acid corrosion resistance of a polyethylene material, the sepiolite is fibrous hydrous magnesium silicate, is non-toxic and nonradioactive, has good high temperature resistance, salt resistance and rheological property, can be dissolved in hydrochloric acid, is odorless and tasteless, mainly comprises β -1, 4-glucoside bond-combined straight-chain polysaccharide substance, has a lower polymer and a larger specific surface area, is insoluble in dilute acid, is modified by using the nano silicon dioxide, sepiolite powder, microcrystalline cellulose and a silane coupling agent, can enhance the linear low-density polyethylene to improve the mechanical strength of the linear low-density polyethylene, can still have good high-temperature oxidation resistance during membrane processing under the premise of removing an antioxidant, is beneficial to the fiber structure of the sepiolite powder and the reticular particle structure of the nano silicon dioxide after melt blending modification treatment, can also improve the mechanical strength of the linear low-density polyethylene and the ion exchange resin compatibility, can also improve the mechanical property of the linear low-density polyethylene, and can further improve the mechanical aging resistance and the mechanical aging resistance of the linear low-density polyethylene after melt blending modification.
Further, the ion exchange resin powder includes cation exchange resin powder and anion exchange resin powder; the cation exchange resin powder is styrene sulfonic acid type cation exchange resin, and the anion exchange resin powder is styrene quaternary ammonium type anion exchange resin.
By adopting the technical scheme, the styrene sulfonic acid type cation exchange resin and the styrene quaternary ammonium type anion exchange resin have better chemical and physical stability, and have the advantages of high strength, high exchange capacity and good selectivity.
The modified linear low-density polyethylene is further prepared by the following method, by weight, ① taking 15-20 parts of nano silicon dioxide, 3-7 parts of sepiolite powder and 1 part of microcrystalline cellulose, mixing the nano silicon dioxide, the sepiolite powder and the microcrystalline cellulose to obtain a blend, placing the blend in a hydrochloric acid solution, soaking for 3-5 hours, then carrying out suction filtration on the blend, washing the blend to be neutral by using distilled water to obtain an acid-treated blend;
② taking 0.5 part of silane coupling agent and 100 parts of 120 parts of ethanol solution with volume fraction of 75-95%, and obtaining silane hydrolysate after ultrasonic dispersion;
③ adding the acid treated blend into silane hydrolysate, stirring at 90-100 deg.C for 2-3h, vacuum filtering, washing with distilled water to neutrality, and drying to obtain modified blend;
④ adding modified blend 10-20% of the weight of the linear low density polyethylene, mixing at high speed, melting, extruding and granulating to obtain the modified linear low density polyethylene.
By adopting the technical scheme, the acid-soluble substances in the nano silicon dioxide, the sepiolite powder and the microcrystalline cellulose can be removed after the nano silicon dioxide, the sepiolite powder and the microcrystalline cellulose are subjected to acid treatment; after the silane coupling agent and an ethanol solution are subjected to ultrasonic dispersion to obtain silane hydrolysate, the acid treatment blend is subjected to modification treatment, so that the modification efficiency of the silane coupling agent on the acid treatment blend is improved; and then the modified blend and the linear low density polyethylene are subjected to melt blending modification, so that the modified blend is dispersed in a molecular chain network of the linear low density polyethylene, and the mechanical property of the linear low density polyethylene is improved.
Further, the silane coupling agent is one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
By adopting the technical scheme, the chemical name of the silane coupling agent is gamma-aminopropyltriethoxysilane, the chemical name of the silane coupling agent KH560 is gamma-glycidoxypropyltrimethoxysilane, and the chemical name of the silane coupling agent KH570 is gamma- (methacryloyloxy) propyltrimethoxysilane; the silane coupling agents KH550, KH560 and KH570 can be used for coupling the blend consisting of nano silicon dioxide, sepiolite powder and microcrystalline cellulose and the linear low-density polyethylene, and the dispersibility and compatibility of the blend and the linear low-density polyethylene can be improved, so that the obtained modified linear low-density polyethylene has good tensile strength and good compatibility with ion exchange resin; therefore, the coupling agent and the antioxidant containing metal ions can be removed in the formula of the product, so that the acid resistance of the membrane is improved.
Further, the ultrasonic dispersion frequency of step ② is 80-100kHz, and the dispersion time is 20-30 min.
By adopting the technical scheme, the dispersibility of the silane coupling agent in the ethanol solution is favorably improved under the condition that the ultrasonic dispersion frequency is 80-100 kHz.
Further, the drying temperature of the step ③ is 80-90 ℃, and the drying time is 8-10 h.
By adopting the technical scheme, the modified blend is dried at the temperature of 80-90 ℃, so that the moisture in the modified blend can be removed, and the stability of the performance of the membrane is improved.
Further, in the step ④, after the linear low density polyethylene and the modified blend are blended at a high speed, the blend is placed in a twin-screw extruder, and the temperatures of the zones of the twin-screw extruder are respectively 135-140 ℃, 140-145 ℃, 145-150 ℃, 150-155 ℃, 155-160 ℃, 165-170 ℃, 160-160 ℃, 155-160 ℃, 160-160 ℃ and 120-r/min.
In order to achieve the second object, the invention provides the following technical scheme:
a preparation method of an acid-resistant ion exchange membrane comprises the following steps:
s1, weighing the ion exchange resin powder and the modified linear low-density polyethylene according to the proportion, and mixing at a high speed to obtain a mixture;
s2, mixing the mixture for 8-10min at the temperature of 180-200 ℃, then adding polyethylene wax, and mixing uniformly to obtain a mixed material;
s3, heating the mixture in a two-roller machine to 210 ℃ and 230 ℃, adding the mixed mixture, extruding and shearing the mixture for 20-30min through a roller, adjusting the distance between the two rollers, and pulling out a first-stage membrane;
s4, adjusting the distance between rollers of the calender, adjusting the temperature of the rollers of the calender to 185-220 ℃, putting the primary membrane into the calender, and obtaining the acid-resistant ion exchange membrane after calendering, drawing, stripping, cooling, forming and cutting.
By adopting the technical scheme, after the ion exchange resin powder and the modified linear low-density polyethylene are mixed at a high speed, the mixing uniformity of the ion exchange resin powder and the modified linear low-density polyethylene can be improved, then the added polyethylene wax is divided into the high-molecular dispersing agent, the mixing uniformity of the raw materials can be improved, the massive mixed material with certain toughness is formed, the obtained mixed material can be further mixed after being extruded and sheared, and the prepared membrane has good acid corrosion resistance, ion exchange performance and long service life.
Further, the high-speed mixing speed of S1 is 3000-4000r/min, and the mixing time is 5-10 min.
By adopting the technical scheme, the raw materials are mixed at the speed of 3000-4000r/min, which is beneficial to improving the uniformity of the raw material mixing.
In summary, compared with the prior art, the invention has the following beneficial effects:
1. after the antioxidant and the coupling agent containing metal ions are removed from the raw materials of the ion exchange membrane, the ion exchange membrane still has good mechanical properties such as tensile yield strength and the like, and can reach the required strength without hot-press molding of the membrane and mesh cloth; after the linear low-density polyethylene is modified, the dispersion uniformity of the ion exchange resin in the polymer can be improved; the acid-resistant ion exchange membrane prepared by the invention is applied to the electrodeionization membrane stack, the membrane is not corroded by hydrochloric acid after being chemically cleaned after scaling, the water production resistivity of the electrodeionization membrane stack is not changed, and the membrane stack type performance and the service life are not influenced by hydrochloric acid;
2. the linear low-density polyethylene is modified by adopting the nano silicon dioxide, the sepiolite powder, the microcrystalline cellulose and the silane coupling agent, the raw materials are nontoxic and tasteless, secondary pollution to a water body is avoided, and the modified linear low-density polyethylene also has certain light aging resistance, so that the service life of the diaphragm is further prolonged.
Detailed Description
The present invention will be described in further detail below.
Preparation examples the nano-silica in the following preparation examples was selected from nanoscale spherical silica with a fineness of 2000 mesh, model R202, provided by corridor morning kun chemical building materials ltd; the sepiolite powder is sepiolite powder with the fineness of 400 meshes provided by Hebei Hemiangguan mineral products GmbH; the microcrystalline cellulose is selected from the group consisting of cellulose provided by Hibei Koron-Kelong-Biotech, Inc.; silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH570 are prepared from south AmericaThe linear low density polyethylene is selected from LL DPE of model L D100AC provided by Yanshan petrochemical company, the melt index is 2.0g/10min, and the density is 0.9225g/cm3。
Preparation example 1 of modified Linear Low Density polyethylene ① A blend is obtained by mixing 15kg of nano-silica, 3kg of sepiolite powder and 1kg of microcrystalline cellulose, immersing the blend in 20 wt% hydrochloric acid solution for 3h, then carrying out suction filtration, washing with distilled water to neutrality, and obtaining an acid treated blend;
② dispersing 0.5kg of silane coupling agent KH550 and 100kg of 75% ethanol solution under the ultrasonic frequency of 80kHz for 20min to obtain silane hydrolysate;
③ adding the acid treated blend into silane hydrolysate, stirring for 2h at 90 deg.C, vacuum filtering, washing with distilled water to neutrality, and drying to obtain modified blend;
④ adding modified blend with 10% of the weight of the linear low density polyethylene, mixing at 3000r/min for 20min, putting the mixture into a double screw extruder, wherein the temperatures of the zones of the screw extruder are 135 ℃ in the first zone, 140 ℃ in the second zone, 145 ℃ in the third zone, 150 ℃ in the fourth zone, 155 ℃ in the fifth zone, 165 ℃ in the sixth zone, 155 ℃ in the seventh zone, 155 ℃ in the die orifice and 100r/min in the screw, melting, extruding and granulating to obtain the modified linear low density polyethylene.
Preparation example 2 of modified Linear Low Density polyethylene ① A blend was obtained by mixing 17.5kg of Nano silica, 5kg of sepiolite powder and 1kg of microcrystalline cellulose, immersing the blend in 20 wt% hydrochloric acid solution for 4 hours, then suction-filtering, washing with distilled water to neutrality, and then obtaining an acid-treated blend;
② dispersing 0.5kg of silane coupling agent KH560 and 110kg of ethanol solution with volume fraction of 85% under the ultrasonic frequency of 90kHz for 25min to obtain silane hydrolysate;
③ adding the acid treated blend into silane hydrolysate, stirring for 2.5h at 95 deg.C, vacuum filtering, washing with distilled water to neutrality, and drying to obtain modified blend;
④ adding a modified blend accounting for 15 percent of the weight of the linear low density polyethylene, mixing at a high speed of 3000r/min for 20min, placing the mixture into a double-screw extruder, wherein the temperatures of the zones of the screw extruder are respectively 138 ℃ in the first zone, 142 ℃ in the second zone, 148 ℃ in the third zone, 152 ℃ in the fourth zone, 158 ℃ in the fifth zone, 168 ℃ in the sixth zone, 158 ℃ in the seventh zone, 158 ℃ in the die orifice and 110r/min in the screw, and melting, extruding and granulating the mixture to obtain the modified linear low density polyethylene.
Preparation example 3 of modified Linear Low Density polyethylene ① preparation example 20kg of Nano silicon dioxide, 7kg of sepiolite powder and 1kg of microcrystalline cellulose were taken and mixed to obtain a blend, the blend was placed in a 20 wt% hydrochloric acid solution to be soaked for 5 hours, then the blend was filtered by suction and washed to neutrality with distilled water to obtain an acid treated blend;
② dispersing 0.5kg of silane coupling agent KH570 and 120kg of 95% ethanol solution under 100kHz ultrasonic frequency for 30min to obtain silane hydrolysate;
③ adding the acid treated blend into silane hydrolysate, stirring for 3h at 100 deg.C, vacuum filtering, washing with distilled water to neutrality, and drying at 90 deg.C for 10h to obtain modified blend;
④ adding a modified blend accounting for 20 percent of the weight of the linear low density polyethylene into the linear low density polyethylene, mixing the mixture at a high speed of 3000r/min for 20min, placing the mixture into a double-screw extruder, wherein the temperatures of all zones of the screw extruder are respectively 140 ℃ in the first zone, 145 ℃ in the second zone, 150 ℃ in the third zone, 155 ℃ in the fourth zone, 160 ℃ in the fifth zone, 170 ℃ in the sixth zone, 160 ℃ in the seventh zone, 160 ℃ in a die orifice and 120r/min in the screw, and melting, extruding and granulating the mixture to obtain the modified linear low density polyethylene.
Preparation example 4 of modified linear low density polyethylene this preparation example differs from preparation example 1 of modified linear low density polyethylene in that the raw material of step ① is obtained by replacing nano silica and sepiolite powder with an equal amount of microcrystalline cellulose.
Preparation of modified linear low density polyethylene 5 this preparation differs from preparation 1 of modified linear low density polyethylene in that the blend of step ① has not been acid treated.
Preparation example 6 of modified Linear Low Density polyethylene this preparation differs from preparation example 1 of modified Linear Low Density polyethylene in that the modified blend was added in an amount of 9% by weight of the linear low density polyethylene in step ④.
Preparation example 7 of modified Linear Low Density polyethylene this preparation example differs from preparation example 1 of modified Linear Low Density polyethylene in that the modified blend was added in an amount of 21% by weight of the linear low density polyethylene in step ④.
Examples
The cation exchange resin in the following examples is selected from styrene sulfonic acid type cation exchange resin of type 001 × 7 provided by Tianjin Kaishu resin technology Co., Ltd, the anion exchange resin is selected from styrene quaternary ammonium type anion exchange resin of type 201 × 7 provided by Tianjin Kaishu resin technology Co., Ltd, and the polyethylene wax is provided by Yanshan petrochemical company.
Example 1: the acid-resistant ion exchange membrane is prepared by the following method:
s1, drying the cation resin until the water content is 5%, grinding and sieving the cation resin to obtain cation exchange resin powder with the fineness of 200 meshes; taking 5000kg of cationic resin and 3000kg of modified linear low density polyethylene (selected from preparation example 1 of the modified linear low density polyethylene), putting into a high-speed mixing stirrer, adjusting the rotating speed of high-speed mixing stirring to 3000r/min, and mixing at normal temperature for 10min to obtain a mixture;
s2, heating the closed mixer to 180 ℃, adding the mixture, melting and banburying the mixture for 8min, adding 50kg of polyethylene wax, and banburying the mixture for 20min to obtain a mixed material;
s3, heating the open type two-roller mixing mill to 210 ℃, adding the mixed materials, extruding and shearing the mixed materials for 20min through a roller, adjusting the distance between the two rollers, and drawing a first-stage membrane with the thickness of 1.5 mm;
s4, adjusting the distance between the rollers of the four-roller calender, adjusting the rotating speed of the four rollers of the four-roller calender to 7.8m/min, adjusting the temperature of the four rollers to 185 ℃, 195 ℃, 210 ℃ and 220 ℃, respectively, putting the primary membrane with the thickness of 1.5mm into the four-roller calender, and obtaining the acid-resistant ion exchange membrane with the thickness of 0.4mm, the length of 1600mm and the width of 800mm after calendering, film forming, traction stripping, cooling, forming and cutting.
Example 2: the acid-resistant ion exchange membrane is prepared by the following method:
s1, drying the cation resin until the water content is 5%, grinding and sieving the cation resin to obtain cation exchange resin powder with the fineness of 200 meshes; 5500kg of cationic resin and 3500kg of modified linear low density polyethylene (selected from preparation example 2 of modified linear low density polyethylene) are put into a high-speed mixing stirrer, the rotating speed of high-speed mixing stirring is adjusted to 3500r/min, and the mixture is mixed for 12min at normal temperature to obtain a mixture;
s2, heating the closed mixer to 190 ℃, adding the mixture, melting and banburying the mixture for 9min, adding 65kg of polyethylene wax, and banburying the mixture for 20min to obtain a mixed material;
s3, heating the open type two-roller mixing mill to 220 ℃, adding the mixed materials, extruding and shearing the mixed materials for 25min through a roller, adjusting the distance between the two rollers, and drawing a first-stage membrane with the thickness of 1.5 mm;
s4, adjusting the distance between the rollers of the four-roller calender, adjusting the rotating speed of the four rollers of the four-roller calender to 7.8m/min, adjusting the temperature of the four rollers to 185 ℃, 195 ℃, 210 ℃ and 220 ℃, respectively, putting the primary membrane with the thickness of 1.5mm into the four-roller calender, and obtaining the acid-resistant ion exchange membrane with the thickness of 0.4mm, the length of 1600mm and the width of 800mm after calendering, film forming, traction stripping, cooling, forming and cutting.
Example 3: the acid-resistant ion exchange membrane is prepared by the following method:
s1, drying the cation resin until the water content is 5%, grinding and sieving the cation resin to obtain cation exchange resin powder with the fineness of 200 meshes; putting 6000kg of cationic resin and 4000kg of modified linear low density polyethylene (selected from preparation example 3 of the modified linear low density polyethylene) into a high-speed mixing stirrer, adjusting the rotating speed of high-speed mixing stirring to 4000r/min, and mixing at normal temperature for 15min to obtain a mixture;
s2, heating the closed mixer to 200 ℃, adding the mixture, melting and banburying the mixture for 10min, adding 80kg of polyethylene wax, and banburying the mixture for 20min to obtain a mixed material;
s3, heating the open type two-roller mixing mill to 230 ℃, adding the mixed materials, extruding and shearing the mixed materials for 30min through a roller, adjusting the distance between the two rollers, and drawing a first-stage membrane with the thickness of 1.5 mm;
s4, adjusting the distance between the rollers of the four-roller calender, adjusting the rotating speed of the four rollers of the four-roller calender to 7.8m/min, adjusting the temperature of the four rollers to 185 ℃, 195 ℃, 210 ℃ and 220 ℃, respectively, putting the primary membrane with the thickness of 1.5mm into the four-roller calender, and obtaining the acid-resistant ion exchange membrane with the thickness of 0.4mm, the length of 1600mm and the width of 800mm after calendering, film forming, traction stripping, cooling, forming and cutting.
Example 4: this example differs from example 1 in that the amount of cationic resin used was 5000kg, the amount of modified linear low density polyethylene used was 4000kg and the amount of polyethylene wax used was 65 kg.
Example 5: this example is different from example 1 in that the cationic resin was used in an amount of 6000kg, the modified linear low density polyethylene was used in an amount of 3000kg, and the polyethylene wax was used in an amount of 65 kg.
Example 6: this example differs from example 1 in that the cationic resin was replaced with an anionic resin.
Example 7: this example differs from example 2 in that the cationic resin was replaced with an anionic resin.
Example 8: this example differs from example 3 in that the cationic resin was replaced with an anionic resin.
Comparative example
Comparative example 1 using example 1 of chinese patent (an ion exchange membrane and a process for preparing the same) having an authorization publication No. CN105870485B, a process for preparing an ion exchange membrane, comprising the steps of: s1, weighing 145kg of nano zinc oxide modified high-density polyethylene, 46kg of polyisobutylene, 6.5kg of zirconium coupling agent, 4kg of bis (pentafluorophenyl) titanocene and 3.5kg of maleimide derivative, putting into a high-speed mixing stirrer, fully and uniformly mixing at normal temperature, automatically weighing 5kg of 2, 4-dinitrophenol sodium and 560kg of cation exchange resin powder by a computer, and adding into the high-speed mixing stirrer for mixing again; s2, preparing a sheet from the mixture in the S1, and attaching polymer mesh cloth to two sides of the sheet; s3, putting the sheet material adhered with the polymer material mesh cloth in the S2 into a multi-layer electric heating template with a light source for heating and pressing molding, wherein the heating temperature is controlled to be 180-220 ℃, and the time is kept between 1.0h and 2.5 h; and S4, after the sheet material in the S3 is heated, cooling and shaping the sheet material by utilizing the circulating condensed water, and finally demolding.
Comparative example 2 this comparative example differs from example 1 in that the modified linear low density polyethylene was replaced by a linear low density polyethylene selected from LL DPE supplied by Yanshan petrochemical under model number L D100AC, having a melt index of 2.0g/10min and a density of 0.9225g/cm3。
Comparative example 3: this comparative example is different from example 1 in that the modified linear low density polyethylene was selected from the modified linear low density polyethylene prepared in preparation example 4.
Comparative example 4: this comparative example is different from example 1 in that the modified linear low density polyethylene was selected from the modified linear low density polyethylene prepared in preparation example 5.
Comparative example 5: this comparative example is different from example 1 in that the modified linear low density polyethylene was selected from the modified linear low density polyethylene prepared in preparation example 6.
Comparative example 6: this comparative example is different from example 1 in that the modified linear low density polyethylene was selected from the modified linear low density polyethylene prepared in preparation example 7.
Comparative example 7: this comparative example differs from example 1 in that the amount of the modified linear low density polyethylene used was 2900 kg.
Comparative example 8: this comparative example differs from example 1 in that the modified linear low density polyethylene was used in an amount of 4100 kg.
Performance testing
According to HY/T034.2-1994 & lt & gt electrodialysis technology heterogeneous ion exchange membrane & gt, the technical indexes of the positive and negative membranes meet the requirements of Table 1, the performance of the membranes prepared in examples 1-8 and comparative examples 1-8 is tested, and the test results are shown in Table 2.
Acid corrosion resistance: the membrane was immersed in a 5 wt% hydrochloric acid solution for 96 hours, then removed, and its surface was rinsed with deionized water to pH 7 and tested for performance.
TABLE 1 Main technical indices of ion exchange membranes
Table 2 film performance test table in examples and comparative examples
According to the data in Table 2, the exchange capacity of the ion exchange membrane prepared by the invention is more than or equal to 2.5mol/kg, and the membrane surface resistance is less than or equal to 10 omega cm2The tensile strength is more than or equal to 4.8MPa, and various properties of the ion exchange membrane are not obviously changed after the ion exchange membrane is soaked in acid liquor, which shows that the ion exchange membrane prepared by the invention has good acid corrosion resistance; although the performance of the exchange capacity and the membrane area resistance of the membrane sheets in examples 1 to 8 is inferior to that of the membrane sheet in comparative example 1, the membrane sheets meet the industrial standards, and have acid corrosion resistance which cannot be compared with that of comparative example 1, when the membrane sheets are applied to an electrodeionization membrane stack,after scaling, the membrane is not corroded by hydrochloric acid after chemical cleaning, the water production resistivity of the electrodeionization membrane stack is not changed, and the membrane stack type energy and the service life are not influenced by hydrochloric acid.
Comparative example 2 the modified linear low density polyethylene was replaced with a linear low density polyethylene selected from LL DPE model L D100AC supplied by Yanshan petrochemical having a melt index of 2.0g/10min and a density of 0.9225g/cm3(ii) a The performance of the membrane of the comparative example 2 is not obviously changed after acid corrosion, but the exchange capacity, the membrane surface resistance and the tensile strength of the membrane of the comparative example 2 are obviously reduced compared with those of the membrane of the example 1, which shows that after only linear low density polyethylene is added to the raw material of the membrane but no auxiliaries such as a coupling agent containing metal ions, an antioxidant and the like are added, although the problem of the reduction of the performance of the membrane caused by the corrosion of hydrochloric acid can be avoided, the dispersion uniformity of the ion exchange resin in the common linear low density polyethylene can be influenced due to the lack of the coupling agent and the antioxidant, so that the overall performance of the membrane is obviously reduced.
The modified linear low density polyethylene of comparative example 3 was prepared from preparation example 4 of modified linear low density polyethylene, in which nano-silica and sepiolite powder were replaced with the same amount of microcrystalline cellulose; through comparison of the example 1, the comparative example 2 and the comparative example 3, the exchange capacity and the tensile strength of the membrane in the comparative example 3 are obviously lower than those of the membrane in the example 1, but are better than those of the membrane in the comparative example 2, which shows that when the linear low-density polyethylene is simultaneously modified by adopting the nano silicon dioxide, the sepiolite powder and the microcrystalline cellulose, the modified linear low-density polyethylene has good mechanical strength under the condition of removing the antioxidant and the coupling agent, and the ion exchange resin has good dispersion uniformity in the modified linear low-density polyethylene, so that the prepared membrane can keep excellent acid corrosion resistance under the condition of keeping good exchange capacity, tensile strength and membrane surface resistance.
The modified linear low density polyethylene of comparative example 4 was prepared from preparation example 5 of modified linear low density polyethylene, in which the blend was not acid-treated; compared with example 1, the exchange capacity, tensile strength and film surface resistance of the membrane in comparative example 4 have no obvious change, but the exchange capacity, tensile strength and film surface resistance after acid corrosion test are obviously reduced, which shows that after the blend is subjected to acid treatment, the linear low-density polyethylene is subjected to modification treatment, so that the acid corrosion resistance of the membrane can be obviously improved.
The modified linear low density polyethylene of comparative example 5 was prepared from preparation example 6 in which the modified linear low density polyethylene was selected from 9% by weight of the linear low density polyethylene in step ④, and the modified linear low density polyethylene of comparative example 6 was prepared from preparation example 7 in which the modified linear low density polyethylene was selected from 21% by weight of the linear low density polyethylene in step ④, and the performance of the film sheet was slightly decreased as compared with those of example 1, comparative example 5 and comparative example 6, indicating that the film sheet obtained according to the present invention has excellent properties in various aspects when the modified blend was added in an amount of 10 to 20%.
The amount of the modified linear low density polyethylene in comparative example 7 was 2900 kg; the amount of the modified linear low density polyethylene in comparative example 8 was 4100 kg; compared with example 1, the performance of the membranes in comparative example 7 and comparative example 8 is slightly reduced, which shows that the membranes prepared by the formulation of the invention have better performance in all aspects.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (9)
1. An acid-resistant ion exchange membrane characterized by: the paint comprises the following components in parts by weight:
6000 parts of ion exchange resin powder 5000-;
the modified linear low-density polyethylene is prepared by modifying linear low-density polyethylene by nano silicon dioxide, sepiolite powder, microcrystalline cellulose and a silane coupling agent;
the linear low density polyethylene has a melt index of 2.0g/10min and a density of 0.9225g/cm3。
2. The acid-resistant ion exchange membrane of claim 1, wherein: the ion exchange resin powder comprises cation exchange resin powder and anion exchange resin powder; the cation exchange resin powder is styrene sulfonic acid type cation exchange resin, and the anion exchange resin powder is styrene quaternary ammonium type anion exchange resin.
3. The acid-resistant ion exchange membrane of claim 1, wherein the modified linear low density polyethylene is prepared by mixing ① parts by weight of nano silicon dioxide 15-20 parts, sepiolite powder 3-7 parts and microcrystalline cellulose 1 part to obtain a blend, soaking the blend in hydrochloric acid solution for 3-5h, filtering, washing with distilled water to neutrality to obtain an acid treated blend;
② taking 0.5 part of silane coupling agent and 100 parts of 120 parts of ethanol solution with volume fraction of 75-95%, and obtaining silane hydrolysate after ultrasonic dispersion;
③ adding the acid treated blend into silane hydrolysate, stirring at 90-100 deg.C for 2-3h, vacuum filtering, washing with distilled water to neutrality, and drying to obtain modified blend;
④ adding modified blend 10-20% of the weight of the linear low density polyethylene, mixing at high speed, melting, extruding and granulating to obtain the modified linear low density polyethylene.
4. The acid-resistant ion exchange membrane of claim 1, wherein: the silane coupling agent is one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
5. The acid-resistant ion exchange membrane of claim 3, wherein the ultrasonic dispersion frequency of step ② is 80-100kHz and the dispersion time is 20-30 min.
6. The acid-resistant ion exchange membrane of claim 3, wherein the drying temperature of step ③ is 80-90 ℃ and the drying time is 8-10 h.
7. The acid-resistant ion exchange membrane as claimed in claim 3, wherein the linear low density polyethylene and the modified blend are blended at a high speed in step ④, and then placed in a twin-screw extruder, wherein the temperatures of the zones of the twin-screw extruder are 135-140 ℃ in the first zone, 145-145 ℃ in the second zone, 150-150 ℃ in the third zone, 150-155 ℃ in the fourth zone, 160-155 ℃ in the fifth zone, 165-170 ℃ in the sixth zone, 160-155 ℃ in the seventh zone, 160-155 ℃ in the die orifice and 160-100-120 r/min in the screw speed.
8. A method for preparing an acid-resistant ion exchange membrane sheet according to any one of claims 1 to 7, wherein: the method comprises the following steps:
s1, weighing the ion exchange resin powder and the modified linear low-density polyethylene according to the proportion, and mixing at a high speed to obtain a mixture;
s2, mixing the mixture for 8-10min at the temperature of 180-200 ℃, then adding polyethylene wax, and mixing uniformly to obtain a mixed material;
s3, heating the mixture in a two-roller machine to 210 ℃ and 230 ℃, adding the mixed mixture, extruding and shearing the mixture for 20-30min through a roller, adjusting the distance between the two rollers, and pulling out a first-stage membrane;
s4, adjusting the distance between rollers of the calender, adjusting the temperature of the rollers of the calender to 185-220 ℃, putting the primary membrane into the calender, and obtaining the acid-resistant ion exchange membrane after calendering, drawing, stripping, cooling, forming and cutting.
9. The method of claim 8, wherein the acid-resistant ion exchange membrane is prepared by the following steps: the high-speed mixing speed of S1 is 3000-4000r/min, and the mixing time is 5-10 min.
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