CN111659256A - Scale inhibition filter membrane and preparation method thereof - Google Patents
Scale inhibition filter membrane and preparation method thereof Download PDFInfo
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- CN111659256A CN111659256A CN202010569247.0A CN202010569247A CN111659256A CN 111659256 A CN111659256 A CN 111659256A CN 202010569247 A CN202010569247 A CN 202010569247A CN 111659256 A CN111659256 A CN 111659256A
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- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005266 casting Methods 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000008187 granular material Substances 0.000 claims abstract description 17
- 239000003085 diluting agent Substances 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000005191 phase separation Methods 0.000 claims abstract description 10
- 238000002145 thermally induced phase separation Methods 0.000 claims abstract description 10
- 239000000110 cooling liquid Substances 0.000 claims abstract description 7
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 6
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 6
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 6
- 229920001529 polyepoxysuccinic acid Polymers 0.000 claims abstract description 6
- 239000008213 purified water Substances 0.000 claims abstract description 6
- 230000002401 inhibitory effect Effects 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 11
- -1 polypropylene Polymers 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000000578 dry spinning Methods 0.000 claims description 3
- 238000001891 gel spinning Methods 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 238000002166 wet spinning Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 150000003017 phosphorus Chemical class 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000000108 ultra-filtration Methods 0.000 description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000012621 metal-organic framework Substances 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000001471 micro-filtration Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 150000003751 zinc Chemical class 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- 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
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- 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
- B01D67/0002—Organic membrane manufacture
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
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- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- 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
- B01D71/48—Polyesters
Abstract
The invention provides a scale inhibition filter membrane and a preparation method thereof, wherein a scale inhibition material is mixed into a membrane casting solution in the scale inhibition filter membrane, and an ultramicro filter membrane is manufactured through a membrane manufacturing process; the scale inhibition material is a granular material with the grain diameter of 0.1-100 microns, the granular material comprises an organic solvent, a diluent and a cooling liquid which are insoluble in a casting solution, and the solubility of the granular material in purified water is 0.1-1000 mg/L of inorganic phosphorus, organic phosphorus, polyaspartic acid, polyacrylic acid and polyepoxysuccinic acid. The method includes a non-solvent induced phase separation method, a thermally induced phase separation method, or a melt-drawing method. The invention adopts the granular materials of inorganic phosphorus series, organic phosphorus series, polyaspartic acid, polyacrylic acid and polyepoxysuccinic acid, wherein the scale inhibition materials are insoluble in organic solvents, diluent and cooling liquid in the casting solution, and the solubility of the scale inhibition materials in pure water is 0.1-1000 mg/L. Under the condition that the saturation concentration of the scale inhibition material is 0-10ppm, the scale inhibition material can be effectively released along with water flow, so that the stable release speed and the good scale inhibition effect in the continuous water passing process are ensured.
Description
Technical Field
The invention relates to a scale inhibition filter membrane and a preparation method thereof.
Background
The ultrafiltration membrane technology is a novel filtering material technology developed in the 21 st century, can intercept particles with the molecular weight of 300-500000 daltons, is applied to household water treatment from the 90 s in the 20 th century in the industry, and has the history for more than 20 years. The ultrafiltration membrane can effectively remove substances such as iron rust, silt, colloid, part of macromolecular protein and the like in the household water, but because the ultrafiltration membrane cannot intercept scale forming ions such as calcium, magnesium, bicarbonate radical and the like in the water, the filtered water is still subjected to scale generation after being heated, even the scale is more obvious than that of tap water and is suspended on the surface, the sense of drinking water is influenced, and the development of the ultrafiltration membrane technology in the household water purification industry is further restricted.
At present, because scale forming ions such as calcium, magnesium, bicarbonate and the like in water cannot be intercepted by using an ultrafiltration membrane for filtration, scale inhibition modification is needed, for example, a preparation method of a metal organic framework material MOF loaded ZnO scale inhibition ultrafiltration membrane disclosed by Chinese patent publication No. CN 108854569A, and the scale inhibition ultrafiltration membrane is an ultrafiltration membrane capable of intercepting the scale forming ions such as calcium, magnesium, bicarbonate and the like in water. According to the method, metal salt and ligand are used as raw materials, MOF is prepared under the hydrothermal reaction condition, MOF and zinc salt are mixed and calcined to obtain MOF-loaded ZnO, and the MOF loaded ZnO, PVDF, PE and PES are dispersed or dissolved in a solvent to prepare the corresponding MOF scale inhibition ultrafiltration membrane loaded with ZnO. The membrane material comprises MOF loaded zinc oxide, and the MOF loaded zinc oxide antibacterial ultrafiltration membrane has high antibacterial adhesion. In addition, the ultrafiltration membrane has good filtering and separating performance; can exist stably in air and water; can be regenerated circularly; environment-friendly and non-corrosive. The experimental results show that: the ultrafiltration membrane provided by the invention has the anti-adhesion property of 80-90% to wastewater bacteria and the retention rate of more than 95% to bovine serum albumin. The scale inhibiting membrane has the disadvantages that the scale formation caused by calcium and magnesium precipitation cannot be prevented, and only biological fouling caused by adhesion of microorganisms can be organized.
The existing scale inhibition materials on the market have the following defects: the release amount of the scale inhibition factor is uncontrollable, the scale inhibition particles of the preposed silicophosphate scale inhibitor are used for inhibiting scale, the released effective components of the silicophosphate spheres are gathered in the filter element in the discontinuous use process, the concentration can be about 100 times higher than the normal concentration (3-5ppm), the effluent water has no scale inhibition effect, and a lot of white flocculent precipitates can appear after the water is heated. Causing adverse effects on the sense and health. After long-term soaking, the silicophosphate balls may generate white powdery precipitates to block the ultrafiltration membrane, so that normal use is influenced.
In addition, some scale inhibition materials with slow release rate of scale inhibition factors appear in the market at present, and the materials are characterized in that effective substances are released slowly, and the saturated concentration is relatively low, but two problems exist: 1) when water is continuously flushed, the releasing speed cannot keep up. 2) The material forming method is limited, and long-term soaking can cause the scale inhibiting material to be pulverized to cause the filter membrane to be blocked.
Disclosure of Invention
Aiming at the defect that the release amount of scale inhibition factors of the existing filtration and ultrafiltration membrane is uncontrollable, the invention provides a method for combining a scale inhibition material with an ultrafiltration membrane, fixing the scale inhibition material by using a developed network pore structure in the ultrafiltration/microfiltration membrane, simultaneously enabling the particle size of the scale inhibition material to be in a micron level, increasing the specific surface area of the scale inhibition material, effectively releasing the scale inhibition material along with water flow under the condition that the saturation concentration of the scale inhibition material is 0-10ppm, and ensuring stable release speed and good scale inhibition effect in the continuous water passing process. The ultrafiltration/microfiltration membrane with the scale inhibition function is formed by winding and combining the macromolecules of the ultrafiltration membrane with micron scale inhibition particles in a molten or/and dissolved state and the interaction of a pore-forming agent, a dispersing agent, a solvent, a diluting agent and the like in a casting solution formula in a mode of forming a membrane by melt stretching, thermally induced phase separation or non-solvent induced phase separation.
The technical scheme adopted by the invention for realizing the aim of the invention is as follows: a scale inhibition filter membrane is prepared by mixing a scale inhibition material into a membrane casting solution and preparing an ultramicro filter membrane through a membrane preparation process; the scale inhibition material is a granular material with the grain diameter of 0.1-100 microns, the granular material comprises an organic solvent, a diluent and a cooling liquid which are insoluble in a casting solution, and the solubility of the granular material in purified water is 0.1-1000 mg/L of inorganic phosphorus, organic phosphorus, polyaspartic acid, polyacrylic acid and polyepoxysuccinic acid.
Further, in the above scale inhibition filter membrane: the particle size of the granular material is 1-10 microns.
Further, in the above scale inhibition filter membrane: the solubility of the granular material in purified water is 0.5 mg/L-5 mg/L.
Further, in the above scale inhibition filter membrane: the film making process comprises dry spinning, wet spinning, melt-draw spinning and dry-wet spinning.
Further, in the above scale inhibition filter membrane: the raw materials of the casting solution comprise: polysulfone, polyethersulfone, polyvinylidene fluoride, polyvinyl chloride, polypropylene, polyethylene, polytetrafluoroethylene, polyester, polyacrylonitrile.
The invention also provides a preparation method of the scale inhibition filter membrane, which comprises the step of mixing the scale inhibition material into the membrane casting solution, and is characterized in that: the step of mixing the scale inhibiting material into the casting solution comprises the following steps: a non-solvent induced phase separation method, a thermally induced phase separation method, or a melt-drawing method.
Further, in the preparation method of the scale inhibition filter membrane, the following steps are carried out: the non-solvent induced phase separation method comprises the following steps:
a1, mixing the scale inhibition material and 0.5-5% of the total amount of the solvent, and uniformly dispersing to form a first mixture;
a2 and the rest solvent are added into a stirring tank, the polymer raw material is added, and after the polymer raw material is fully dissolved, the first mixture is added;
a3, continuously stirring until the mixture is uniformly mixed, and finally adding additives which can cause viscosity to increase.
Further, in the preparation method of the scale inhibition filter membrane, the following steps are carried out: the thermally induced phase separation method comprises the following steps:
b1, uniformly mixing the scale inhibition material and the polymer raw material to form a second mixture;
b2, adding the second mixture into a diluent;
b3, heating and stirring until the diluent and the polymer in the second mixture become homogeneous liquid.
Further, in the preparation method of the scale inhibition filter membrane, the following steps are carried out: the thermally induced phase separation method is to add a scale inhibiting material into the casting solution which is dissolved/melted fully.
Further, in the preparation method of the scale inhibition filter membrane, the following steps are carried out: in the melt-stretching method, the scale inhibiting material and the polymer raw material are mixed by a double screw, and then are subjected to melt-stretching after extrusion granulation.
In the invention, the scale inhibiting material is a granular material of inorganic phosphorus, organic phosphorus, polyaspartic acid, polyacrylic acid and polyepoxysuccinic acid, which is insoluble in organic solvent, diluent and cooling liquid in the casting solution and has the solubility in pure water of 0.1-1000 mg/L. Under the condition that the saturation concentration of the scale inhibition material is 0-10ppm, the scale inhibition material can be effectively released along with water flow, so that the stable release speed and the good scale inhibition effect in the continuous water passing process are ensured.
The present invention will be described in more detail with reference to specific examples.
Detailed Description
In the embodiment, the filter membrane with the scale inhibition function is manufactured by mixing a scale inhibition material into a membrane casting solution/powder and performing a membrane preparation process.
The scale inhibition material is a granular material with a scale inhibition function, such as an inorganic phosphorus system, an organic phosphorus system, polyaspartic acid, polyacrylic acid, polyepoxysuccinic acid and the like, with the grain diameter of 0.1-100 micrometers (preferably 1-10 micrometers). It is insoluble in organic solvent, diluent, cooling liquid, etc. in casting liquid. The solubility in purified water is 0.1mg/L to 1000mg/L, preferably 0.5mg/L to 5 mg/L.
The scale inhibiting material is added into the casting solution/powder in the following mode:
a) the non-solvent induced phase separation method comprises the steps of firstly adding a solvent, then adding a scale inhibition material, uniformly mixing and dispersing, then adding a polymer raw material and adding an additive. In order to disperse the scale inhibiting material uniformly, the scale inhibiting material can be mixed by ultrasonic wave, mechanical stirring, hydraulic power and other modes. In order to disperse the scale inhibiting material more uniformly, 0.5-5% of the total amount of the scale inhibiting material and the solvent are mixed and dispersed uniformly to form a first mixture. Adding the rest solvent into a stirring tank, adding the polymer raw material, adding the first mixture after full dissolution, continuously stirring until the mixture is uniformly mixed, and then adding the additive which can cause the viscosity to be increased.
b) The thermally induced phase separation method comprises the steps of uniformly mixing the scale inhibiting material and the polymer raw material, adding the mixture into a diluent, heating and stirring until the diluent and the polymer become homogeneous liquid, and uniformly dispersing the scale inhibiting material into the homogeneous liquid. Or adding the scale inhibiting material into the casting solution which is dissolved/melted fully.
c) The melt-drawing method is to mix the scale inhibiting material, the polymer material and the additive evenly and to granulate or use directly. Preferably, the scale inhibiting material and the polymer raw material are mixed by a double screw, extruded and granulated, and then subjected to a melt-stretching process.
A film making process: including dry spinning, wet spinning, melt-draw spinning, and dry-wet spinning.
The polymer raw material of the filter membrane comprises: polysulfone, polyethersulfone, polyvinylidene fluoride, polyvinyl chloride, polypropylene, polyethylene, polytetrafluoroethylene, polyester, polyacrylonitrile, or the like
The types of filter membranes are: flat sheet membrane, hollow fiber membrane, tubular membrane, etc
For the non-solvent induced phase separation method, in the film forming process of the high molecular material, a poor phase and a rich phase are generated in the casting solution, the rich phases of the high molecular material are connected with each other to form a main body structure of the film, and film holes are formed at the positions of the poor phase. After the scale inhibiting material is added, the scale inhibiting material cannot be dissolved in the casting solution, micron-sized particles of the scale inhibiting material can migrate along with the film forming process of the polymer, and the surface energy difference between the polymer and the scale inhibiting material is large, so that the affinity of the two materials is poor, the scale inhibiting material can be possibly remained in the interior or enter a coagulation bath in the migration process of the polymer, and the scale inhibiting material in the film material is less in retention or is wrapped in the coagulation bath and cannot be released. Therefore, the surfactant is added into the membrane casting solution to increase the affinity between the hydrophilic scale inhibiting material and the hydrophobic polymer molecules and ensure the retention of the scale inhibiting material in the ultrafiltration membrane.
EXAMPLE 1 film formation by non-solvent induced phase separation
60kg DMAc (dimethylacetamide) is added into an emulsification tank, 1kg polyphosphate scale inhibition material with the saturation solubility of 1.5ppm (calculated by total phosphorus) and the average particle size of 3 microns is added, emulsification is carried out for 5 minutes at 10000rpm, 15kg PES, 20kg PEG400 and 4kg PVP k30 are added, the emulsification tank is opened at 15000rpm for 15 minutes, and then 0.1kg Tween 80 is added. The temperature of the feed liquid is controlled to be lower than 60 ℃. Adding the casting solution into a spinning tank, stirring for 3 hours at 60 ℃, standing for defoaming for 2 hours, and spinning through a double-layer hole spinning nozzle. An ultrafiltration membrane with an inner diameter of 1mm and an outer diameter of 1.6mm was obtained. The pure water flux is 20 ℃, the scale inhibition rate is as follows under 0.1MPa and 450L/m < 2 > 2h, 0.01 square meter membrane is taken for testing:
| total water yield | Scale inhibition rate |
| 0L | 100％ |
| 10L | 100％ |
| 20L | 100％ |
| 30L | 100％ |
| 40L | 85％ |
| 50L | 50％ |
Example 2 thermally induced phase separation
Mixing 20kg of polyvinylidene fluoride (PVDF) crystalline material, 1kg of scale inhibiting material with the saturation solubility of 1ppm (calculated by total phosphorus) and the average specific particle size of 1.5 microns and 79kg of diluent tributyl phosphate to obtain a mixture; heating the obtained mixture to 380 ℃ to form a suspension, standing and defoaming; coating the defoamed homogeneous solution on a support net in a scraping mode to form a flat-plate-shaped membrane casting solution, then immersing the membrane casting solution into cooling liquid paraffin for cooling, enabling the membrane casting solution to be subjected to phase separation, and finally curing to form a membrane; and (3) placing the membrane in a supercritical CO2 extraction device, and extracting the diluent to form a finished product filter membrane. The test was carried out using a film having a diameter of 100mm, and the results are as follows
| Total water yield | Scale inhibition rate |
| 0L | 100％ |
| 10L | 100％ |
| 20L | 100％ |
| 30L | 100％ |
| 40L | 100％ |
| 50L | 100％ |
| 60L | 90％ |
Example 3 melt drawing Process
60kg of polypropylene particles, 20kg of polyethylene glycol modified polypropylene material and 8kg of scale inhibiting material with the saturation solubility of 3ppm (calculated by total phosphorus) and the average specific particle diameter of 5 microns are blended and placed in a melt spinning machine for spinning to prepare the hollow fiber external pressure type microfiltration membrane, the filtration precision is 0.5 micron, and the scale inhibiting rate test is carried out on the membrane with the 0.01 square meter, and the result is as follows
| Total water yield | Scale inhibition rate |
| 0L | 100％ |
| 10L | 100％ |
| 20L | 80％ |
Claims (10)
1. A scale inhibition filter membrane is prepared by mixing a scale inhibition material into a membrane casting solution and preparing an ultramicro filter membrane through a membrane preparation process, and is characterized in that:
the scale inhibition material is a granular material with the grain diameter of 0.1-100 microns, the granular material comprises an organic solvent, a diluent and a cooling liquid which are insoluble in a casting solution, and the solubility of the granular material in purified water is 0.1-1000 mg/L of inorganic phosphorus, organic phosphorus, polyaspartic acid, polyacrylic acid and polyepoxysuccinic acid.
2. The scale inhibiting filter membrane of claim 1 wherein: the particle size of the granular material is 1-10 microns.
3. The scale inhibiting filter membrane of claim 2, wherein: the solubility of the granular material in purified water is 0.5 mg/L-5 mg/L.
4. The scale inhibiting filter membrane of claim 1, 2 or 3 wherein: the film making process comprises dry spinning, wet spinning, melt-draw spinning and dry-wet spinning.
5. The scale inhibiting filter membrane of claim 1, 2 or 3 wherein: the raw materials of the casting solution comprise: polysulfone, polyethersulfone, polyvinylidene fluoride, polyvinyl chloride, polypropylene, polyethylene, polytetrafluoroethylene, polyester, polyacrylonitrile.
6. A preparation method of a scale inhibition filter membrane comprises the step of mixing a scale inhibition material into a membrane casting solution, and is characterized in that: the step of mixing the scale inhibiting material into the casting solution comprises the following steps: a non-solvent induced phase separation method, a thermally induced phase separation method, or a melt-drawing method.
7. The method for preparing a scale inhibiting filter membrane according to claim 6, wherein the method comprises the following steps: the non-solvent induced phase separation method comprises the following steps:
a1, mixing the scale inhibition material and 0.5-5% of the total amount of the solvent, and uniformly dispersing to form a first mixture;
a2 and the rest solvent are added into a stirring tank, the polymer raw material is added, and after the polymer raw material is fully dissolved, the first mixture is added;
a3, continuously stirring until the mixture is uniformly mixed, and finally adding the additive.
8. The method for preparing a scale inhibiting filter membrane according to claim 6, wherein the method comprises the following steps: the thermally induced phase separation method comprises the following steps:
b1, uniformly mixing the scale inhibition material and the polymer raw material to form a second mixture;
b2, adding the second mixture into a diluent;
b3, heating and stirring until the diluent and the polymer in the second mixture become homogeneous liquid.
9. The method for preparing a scale inhibiting filter membrane according to claim 6, wherein the method comprises the following steps: the thermally induced phase separation method is to add a scale inhibiting material into the casting solution which is dissolved/melted fully.
10. The method for preparing a scale inhibiting filter membrane according to claim 6, wherein the method comprises the following steps: in the melt-stretching method, the scale inhibiting material and the polymer raw material are mixed by a double screw, and then are subjected to melt-stretching after extrusion granulation.
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