CN107413205B - Hollow fiber membrane for purifying dialysis waste liquid and processing method thereof - Google Patents
Hollow fiber membrane for purifying dialysis waste liquid and processing method thereof Download PDFInfo
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- CN107413205B CN107413205B CN201710808859.9A CN201710808859A CN107413205B CN 107413205 B CN107413205 B CN 107413205B CN 201710808859 A CN201710808859 A CN 201710808859A CN 107413205 B CN107413205 B CN 107413205B
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- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 37
- 238000000502 dialysis Methods 0.000 title claims abstract description 36
- 239000007788 liquid Substances 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title claims abstract description 26
- 238000003672 processing method Methods 0.000 title description 4
- 239000000463 material Substances 0.000 claims abstract description 90
- 238000001179 sorption measurement Methods 0.000 claims abstract description 74
- 239000002904 solvent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000009987 spinning Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000000654 additive Substances 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 4
- 239000004137 magnesium phosphate Substances 0.000 claims description 4
- 229960002261 magnesium phosphate Drugs 0.000 claims description 4
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 4
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 4
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 claims description 4
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000010808 liquid waste Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 108010046334 Urease Proteins 0.000 description 11
- -1 ammonium ions Chemical class 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000003053 toxin Substances 0.000 description 7
- 231100000765 toxin Toxicity 0.000 description 7
- 108700012359 toxins Proteins 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 description 6
- 239000002158 endotoxin Substances 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 208000001647 Renal Insufficiency Diseases 0.000 description 3
- 241000700605 Viruses Species 0.000 description 3
- 229940109239 creatinine Drugs 0.000 description 3
- 201000006370 kidney failure Diseases 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 2
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 208000020832 chronic kidney disease Diseases 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000001631 haemodialysis Methods 0.000 description 2
- 230000000322 hemodialysis Effects 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229940116269 uric acid Drugs 0.000 description 2
- 208000037157 Azotemia Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 208000028208 end stage renal disease Diseases 0.000 description 1
- 201000000523 end stage renal failure Diseases 0.000 description 1
- 210000003038 endothelium Anatomy 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 208000017169 kidney disease Diseases 0.000 description 1
- 230000003907 kidney function Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002054 transplantation Methods 0.000 description 1
- 208000009852 uremia Diseases 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
- A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
- A61M1/1654—Dialysates therefor
- A61M1/1656—Apparatus for preparing dialysates
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2626—Absorption or adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/18—Pore-control agents or pore formers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
Abstract
A hollow fiber membrane for purifying dialysis waste liquid relates to the field of dialysis waste liquid treatment devices, and is processed by the following raw materials: a film-based material, a pore-forming agent, a solvent and a specific nano adsorption material; the inner diameter of the hollow fiber membrane is 220-350 microns, the wall thickness is 40-60 microns, the membrane filaments are divided into an outer skin layer, a middle layer and an inner skin layer from outside to inside, specific nanometer adsorption materials are distributed in the outer skin layer and the middle layer of the membrane, the thickness of the outer skin layer is 5-10 microns, and the average filtration pore diameter is 4-6 nanometers; the inner skin layer has a thickness of 0.5-5 μm and an average filter pore size of 0.5-1 nm. Selecting a membrane-based material, a pore-forming agent, a solvent and a specific porous adsorption material, preparing a spinning solution at room temperature, extruding the spinning solution through a spinning nozzle, performing steam bath for 30-60cm at a temperature of 60-80 ℃, and finally performing water washing and drying to obtain a finished product. The invention has the advantages of large over-flow, long service life, strong single treatment capacity and the like.
Description
Technical Field
The invention relates to the field of dialysis waste liquid treatment devices, in particular to a hollow fiber membrane for dialysis waste liquid purification, which can effectively isolate urease and various toxin ions such as absorbed ammonium ions, free phosphate radicals, sulfate ions and the like without the adsorbent entering a circulating system, and a processing method thereof.
Background
It is known that kidney disease is a global public health problem, and about 240 million patients with renal failure need dialysis worldwide. The number of patients with renal failure is also increasing (7-8% per year) due to aging population and increasing incidence of diabetes. Chronic kidney disease affects one in ten of our people. For people who are unfortunate with renal failure, health is gradually engulfed. In China, patients with end-stage renal failure are called uremia by common people, and a plurality of patients replace renal functions by hemodialysis or kidney transplantation.
Renal patients often have many troubles in treatment, such as frequent hospital dialysis to remove accumulated toxins, but two dialysis methods are currently popular: hemodialysis and peritoneal dialysis, which take a long time and require a large amount of dialysate per dialysis, virtually increase the medical expense, and limit the development of these two dialysis methods to mobile dialysis, since several tens of liters of dialysate are carried per dialysis.
The dialysis waste liquid after dialysis mainly contains urea, creatinine, phosphate, β -microglobulin, and endotoxin substances such as viruses and bacteria brought in the long-term recycling process, and how to remove the substances is a key technical problem of the dialysis waste liquid purification and recycling.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provide a hollow fiber membrane for purifying dialysis waste liquid, which can effectively isolate urease and various toxin ions such as ammonium ions, free phosphate radicals, sulfate radicals and the like after urea decomposition without allowing an adsorbent to enter a circulating system, and a processing method thereof.
The technical scheme adopted by the invention for solving the defects of the prior art is as follows:
a hollow fiber membrane for purifying dialysis waste liquid is characterized by being processed from the following raw materials in parts by mass: the composite material comprises 15-20 parts of a film-based material, 3-10 parts of a pore-forming additive, 75-80 parts of a solvent and 2-4 parts of a specific nano adsorption material; the inner diameter of the hollow fiber membrane is 220-350 microns, the wall thickness is 40-60 microns, the membrane filaments are divided into an outer skin layer, a middle layer and an inner skin layer from outside to inside, the specific nano adsorption materials are distributed in the outer skin layer and the middle layer of the membrane, the particle size of the specific nano adsorption materials is 1-8nm, the density of the specific nano adsorption materials from the outer skin layer to the middle layer is gradually reduced, and no specific nano adsorption material exists in the inner skin layer; the thickness of the outer skin layer of the membrane silk is 5-10 microns, and the average filtering pore diameter is 4-6 nanometers; the inner skin layer of the membrane silk has a thickness of 0.5-5 microns, and the average filtration pore diameter is 0.5-1 nanometer.
The membrane base material is one or more of polysulfone, sulfonated polysulfone, polyether sulfone, sulfonated polyether sulfone, polyvinylidene fluoride, polylactic acid, polymethyl methacrylate and polyvinyl alcohol; the pore-forming additive is at least one of polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG); the solvent is one or more of Dimethylacetamide (DMAC), Dimethylformamide (DMF) and N-methylpyrrolidone (NMP).
The specific nano adsorption material is at least one of a silicon-based adsorption material, a zirconium-based adsorption material and a magnesium-based adsorption material.
The silicon-based adsorption material is at least one of silicon oxide, silicon chloride and silicon phosphate particles; the zirconium-based adsorption material is at least one of zirconia, zirconium chloride and zirconium phosphate particles. The magnesium-based adsorption material is at least one of magnesium oxide, magnesium carbonate and magnesium phosphate particles.
A preparation method of a hollow fiber membrane for purifying dialysis waste liquid is characterized by comprising the following steps:
a. selecting 15-20 parts of a film-based material, 3-10 parts of a pore-forming additive, 75-80 parts of a solvent and 2-4 parts of a specific porous adsorption material according to the mass part ratio;
b. adding a pore-forming additive into a solvent at room temperature, adding a membrane-based material and a specific porous adsorption material after the pore-forming additive is completely dissolved, heating to 70-100 ℃, fully stirring for 18-26h in a nitrogen atmosphere to fully and uniformly dissolve solid substances in the spinning solution, and vacuumizing and defoaming to prepare the spinning solution;
c. extruding the spinning solution and the core solution through a spinneret, then carrying out steam bath at the speed of 10-15 meters per minute by 30-60cm, keeping the temperature of the steam bath at 60-80 ℃, and finally carrying out water washing through a water washing system and drying through a drying system to obtain a finished product.
The core liquid in the invention is a mixed liquid of a solvent with the concentration of 10-20% and water. The bore fluid solvent can be at least one of dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
The water washing system provided by the invention is composed of four water washing devices with the temperature of 60 degrees, 70 degrees, 80 degrees and 90 degrees. During this water washing process all solvents, most of the porogen (e.g. polyvinylpyrrolidone) and specific nano-adsorbent material (e.g. silica-based or zirconium-based or magnesium-based nano-adsorbent material) in the dope will migrate towards the membrane outer skin layer and eventually phase separation will be completed.
When the hollow fiber membrane filter is used, urease and a porous adsorption material are matched for use, the urease decomposes urea in dialysis waste liquid into ammonium carbonate, the porous adsorption material adsorbs organic substances such as uric acid, creatinine and the like in the dialysis waste liquid, then the hollow fiber membrane filter is used for purifying the dialysis waste liquid, endotoxin such as bacteria and viruses and eluted micromolecular porous adsorption materials (active carbon, chitosan and montmorillonite) and the urease are filtered and intercepted, and the specific nano adsorption material can adsorb various toxin ions. The specific nano adsorption material is processed and fixed on the outer skin layer and the middle layer of the wall of the hollow fiber membrane, so that the function of the hollow fiber membrane is not influenced while the hollow fiber membrane is fixed, and the addition of the hierarchical specific nano adsorption material of the hollow fiber membrane enables the hollow fiber membrane to play a role in adsorbing various toxin ions such as ammonium ions, free phosphate radicals, sulfate radicals and the like after urea decomposition when the hollow fiber membrane is used for purifying dialysis waste liquid, and simultaneously can filter out micromolecular porous adsorption materials and urease eluted in the previous step; the device has the advantages of large over-flow, long service life, strong single treatment capacity and the like.
Drawings
FIG. 1 is a structural view of the outer surface of the outer skin layer of the present invention under SEM scanning electron microscope.
FIG. 2 is a structural diagram of an intermediate section of an intermediate layer (membrane filament wall) of the present invention under SEM scanning electron microscope.
FIG. 3 is a structural view of the inner surface of the inner skin layer of the present invention under SEM scanning electron microscope.
Detailed Description
A hollow fiber membrane for purifying dialysis waste liquid is characterized by being processed from the following raw materials in parts by mass: the composite material comprises 15-20 parts of a film-based material, 3-10 parts of a pore-forming additive, 75-80 parts of a solvent and 2-4 parts of a specific nano adsorption material; the inner diameter of the hollow fiber membrane (membrane wire) is 220-350 microns, the wall thickness is 40-60 microns, the membrane wire is divided into an outer skin layer, a middle layer and an inner skin layer from outside to inside, the filtering pore diameter of the inner skin layer of the membrane wire is smaller than that of the outer layer, the specific nano adsorption material is distributed in the outer skin layer and the middle layer of the membrane (wire) and has the particle size of 1-8nm, the density of the specific nano adsorption material from the outer skin layer to the middle layer is gradually reduced, the specific nano adsorption material does not exist in the inner skin layer, and the particle size of the specific nano adsorption material is preferably 2; the thickness of the outer skin layer of the membrane silk is 5-10 microns, and the average filtering pore diameter is 4-6 nanometers; the inner skin layer of the membrane silk has a thickness of 0.5-5 microns, and the average filtration pore diameter is 0.5-1 nanometer.
The membrane base material is one or more of polysulfone, sulfonated polysulfone, polyether sulfone, sulfonated polyether sulfone, polyvinylidene fluoride, polylactic acid, polymethyl methacrylate and polyvinyl alcohol; the pore-forming additive is at least one of polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG); the solvent is one or more of Dimethylacetamide (DMAC), Dimethylformamide (DMF) and N-methylpyrrolidone (NMP).
The specific nano adsorption material is at least one of a silicon-based adsorption material, a zirconium-based adsorption material and a magnesium-based adsorption material.
The silicon-based adsorption material is at least one of silicon oxide, silicon chloride and silicon phosphate particles; the zirconium-based adsorption material is at least one of zirconia, zirconium chloride and zirconium phosphate particles. The magnesium-based adsorption material is at least one of magnesium oxide, magnesium carbonate and magnesium phosphate particles.
A preparation method of a hollow fiber membrane for purifying dialysis waste liquid is characterized by comprising the following steps:
a. selecting 15-20 parts of a film-based material, 3-10 parts of a pore-forming additive, 75-80 parts of a solvent and 2-4 parts of a specific porous adsorption material according to the mass part ratio;
b. adding a pore-forming additive into a solvent at room temperature, adding a membrane-based material and a specific porous adsorption material after the pore-forming additive is completely dissolved, heating to 70-100 ℃, fully stirring for 18-26h in a nitrogen atmosphere to fully and uniformly dissolve solid substances in the spinning solution, and vacuumizing and defoaming to prepare the spinning solution;
c. putting the spinning solution and the core solution into a hollow fiber spinning machine, extruding the spinning solution and the core solution through a spinning nozzle, then carrying out 30-60cm long steam bath at the speed of 10-15 meters per minute, keeping the temperature of the steam bath at 60-80 ℃, finally carrying out water washing through a water washing system, drying through a drying system, and collecting the product by a winding device to obtain the finished product.
60-80 deg.C steam bath can make the outer skin layer form macroporous structure, and the steam bath can attract polyvinylpyrrolidone (pore-forming additive) at the inner skin layer of the membrane to the outer skin layer of the membrane, and polyvinyl pyrrolidone (pore-forming additive) is at the removal in-process from inside to outside, can drive the specific nanometer adsorption material of cortex department and move to the cortex, it reduces gradually to form cortex to intermediate level specific nanometer adsorption material density finally, the hollow fiber membrane structure of the interior no specific nanometer adsorption material of endothelium, the absorption or the interception advantage of each layer of performance that can be fine, the specific nanometer adsorption material in cortex and the intermediate level at first adsorbs some ions from the dislysate, the cortex then continues more efficient interception to the unable absorbent material of specific nanometer adsorption material, can improve absorption and interception efficiency greatly. The membrane after the steam bath sequentially enters four water washing systems of 60 degrees, 70 degrees, 80 degrees and 90 degrees, all solvents, most pore-forming additives (such as polyvinylpyrrolidone) and specific nano adsorption materials in the spinning solution move to the outer skin layer of the membrane in the water washing process, and finally phase separation is finished (the solvents and pore-forming additives in the spinning solution are eluted).
Because of the high-temperature water vapor bath, the specific nano-adsorption material is embedded in the middle layer and the outermost layer of the membrane, as shown in the SEM structural photographs of figures 1-3, the inner skin layer of the membrane forms a compact separation skin layer with the thickness of 1-2 microns, the average pore diameter of the membrane pores on the inner skin layer is 0.5-1nm, and all heat source substances such as bacteria, endotoxin and the like can not pass through the filter layer.
The core liquid in the invention is a mixed liquid of a solvent with the concentration of 10-20% and water. The bore fluid solvent can be at least one of dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
The water washing system provided by the invention is composed of four water washing devices with the temperature of 60 degrees, 70 degrees, 80 degrees and 90 degrees.
When the hollow fiber membrane filter is used, urease and a porous adsorption material are matched for use, the urease decomposes urea in dialysis waste liquid into ammonium carbonate, the porous adsorption material adsorbs organic substances such as uric acid, creatinine and the like in the dialysis waste liquid, then the hollow fiber membrane filter is used for purifying the dialysis waste liquid, endotoxin such as bacteria and viruses and eluted micromolecular porous adsorption materials (active carbon, chitosan and montmorillonite) and the urease are filtered and intercepted, and the specific nano adsorption material can adsorb various toxin ions. The specific nano adsorption material is processed and fixed on the outer skin layer and the middle layer of the wall of the hollow fiber membrane, so that the function of the hollow fiber membrane is not influenced while the hollow fiber membrane is fixed, and the addition of the hierarchical specific nano adsorption material of the hollow fiber membrane enables the hollow fiber membrane to play a role in adsorbing various toxin ions such as ammonium ions, free phosphate radicals, sulfate radicals and the like (after urea decomposition) when the hollow fiber membrane is used for purifying dialysis waste liquid, and simultaneously can filter out micromolecular porous adsorption materials and urease eluted in the previous step; the device has the advantages of large over-flow, long service life, strong single treatment capacity and the like.
According to the hollow fiber membrane for purifying dialysis waste liquid and the manufacturing method thereof provided by the invention, the specific nano adsorption materials (silicon-based, zirconium-based or magnesium-based adsorption materials) of the outer skin layer and the middle layer can adsorb ammonium ions after urea decomposition and free phosphate radicals and sulfate radicals, and almost all endotoxins can be trapped by the compact structure of the inner skin layer. The layered structure design can effectively fix the nano adsorption material, and the compact inner skin layer can effectively retain heat source substances such as bacteria, endotoxin and the like, and can retain activated carbon, urease eluted in the previous treatment process and even dropped silicon-based or zirconium-based adsorption particles again, thereby playing a role in multiple protection.
Claims (5)
1. A hollow fiber membrane for purifying dialysis waste liquid is characterized by being processed from the following raw materials in parts by mass: the composite material comprises 15-20 parts of a film-based material, 3-10 parts of a pore-forming additive, 75-80 parts of a solvent and 2-4 parts of a specific nano adsorption material; the inner diameter of the hollow fiber membrane is 220-350 microns, the wall thickness is 40-60 microns, the membrane filaments are divided into an outer skin layer, a middle layer and an inner skin layer from outside to inside, and the specific nano adsorption material is distributed in the outer skin layer and the middle layer of the membrane and has the particle size of 1-8 nm; the thickness of the outer skin layer of the membrane silk is 5-10 microns, and the average filtering pore diameter is 4-6 nanometers; the thickness of the inner skin layer of the membrane silk is 0.5-5 microns, and the average filtering pore diameter is 0.5-1 nanometer; the specific nano adsorption material is at least one of a silicon-based adsorption material, a zirconium-based adsorption material and a magnesium-based adsorption material; the silicon-based adsorption material is at least one of silicon oxide, silicon chloride and silicon phosphate particles; the zirconium-based adsorption material is at least one of zirconia, zirconium chloride and zirconium phosphate particles; the magnesium-based adsorption material is at least one of magnesium oxide, magnesium carbonate and magnesium phosphate particles.
2. The hollow fiber membrane for purifying dialysis waste liquid according to claim 1, wherein the membrane-based material is one or more of polysulfone, sulfonated polysulfone, polyethersulfone, sulfonated polyethersulfone, polyvinylidene fluoride, polylactic acid, polymethyl methacrylate, and polyvinyl alcohol; the pore-forming additive is at least one of polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG); the solvent is one or more of Dimethylacetamide (DMAC), Dimethylformamide (DMF) and N-methylpyrrolidone (NMP).
3. A preparation method of a hollow fiber membrane for purifying dialysis waste liquid is characterized by comprising the following steps:
a. selecting 15-20 parts of a film-based material, 3-10 parts of a pore-forming additive, 75-80 parts of a solvent and 2-4 parts of a specific porous adsorption material according to the mass part ratio;
b. adding a pore-forming additive into a solvent at room temperature, adding a membrane-based material and a specific porous adsorption material after the pore-forming additive is completely dissolved, heating to 70-100 ℃, fully stirring for 18-26h in a nitrogen atmosphere to fully and uniformly dissolve solid substances in the spinning solution, and vacuumizing and defoaming to prepare the spinning solution;
c. extruding the spinning solution and the core solution through a spinneret, then carrying out steam bath for 30-60cm at the temperature of 60-80 ℃, and finally carrying out water washing through a water washing system and drying through a drying system to obtain a finished product;
the specific nano adsorption material is at least one of silicon-based adsorption material, zirconium-based adsorption material and magnesium-based adsorption material; the silicon-based adsorption material is at least one of silicon oxide, silicon chloride and silicon phosphate particles; the zirconium-based adsorption material is at least one of zirconia, zirconium chloride and zirconium phosphate particles; the magnesium-based adsorption material is at least one of magnesium oxide, magnesium carbonate and magnesium phosphate particles.
4. The method for producing a hollow fiber membrane for dialysis waste liquid purification according to claim 3, wherein the water washing system comprises four water washing devices at 60 degrees centigrade, 70 degrees centigrade, 80 degrees centigrade and 90 degrees centigrade.
5. The method for producing a hollow fiber membrane for purifying a dialysis liquid waste according to claim 3 or 4, wherein the bore fluid solvent is at least one of dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
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| CN108816062A (en) * | 2018-06-27 | 2018-11-16 | 苏州市贝克生物科技有限公司 | polyamide-alginate fibre dialysis membrane and preparation method thereof |
| CN109316986B (en) * | 2018-11-07 | 2021-09-21 | 中南大学 | Acrylic acid and sulfonated dihydroxypropyl chitosan modified polysulfone membrane and preparation method thereof |
| US20220401889A1 (en) * | 2019-11-22 | 2022-12-22 | Stichting Voor De Technische Wetenschappen | Porous membranes comprising sorbent particles for improved urea capture |
| CN113457465A (en) * | 2021-07-16 | 2021-10-01 | 桐乡市健民过滤材料有限公司 | Polyvinylidene fluoride hollow fiber ultrafiltration membrane and preparation method thereof |
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