CN107413205A - Dialysis effluent purifying hollow-fibre membrane and its processing method - Google Patents

Dialysis effluent purifying hollow-fibre membrane and its processing method Download PDF

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CN107413205A
CN107413205A CN201710808859.9A CN201710808859A CN107413205A CN 107413205 A CN107413205 A CN 107413205A CN 201710808859 A CN201710808859 A CN 201710808859A CN 107413205 A CN107413205 A CN 107413205A
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fibre membrane
parts
hollow
microns
film
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CN107413205B (en
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牟倡骏
代朋
徐天成
于亚楠
张洁敏
李敏
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Shandong Weigao Blood Purification Products Co Ltd
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Weihai Weigao Blood Purified Product Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES 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
    • A61M1/00Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
    • A61M1/14Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
    • A61M1/16Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
    • A61M1/1654Dialysates therefor
    • A61M1/1656Apparatus for preparing dialysates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane manufacture
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08Hollow fibre membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2311/00Details relating to membrane separation process operations and control
    • B01D2311/26Further operations combined with membrane separation processes
    • B01D2311/2626Absorption or adsorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2323/00Details relating to membrane preparation
    • B01D2323/15Use of additives
    • B01D2323/18Pore-control agents or pore formers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2325/00Details relating to properties of membranes
    • B01D2325/02Details relating to pores or porosity of the membranes

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical & Material Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Engineering & Computer Science (AREA)
  • Hematology (AREA)
  • Biomedical Technology (AREA)
  • Anesthesiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
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  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • External Artificial Organs (AREA)

Abstract

One kind dialysis effluent purifying hollow-fibre membrane, is related to dialysis liquid waste treating apparatus field, is formed by following Raw material processings:Film base material material, pore-foaming agent, solvent, specific nano sorbing material;Hollow-fibre membrane internal diameter is 220 350 microns, wall thickness is 40 60 microns, film wire ecto-entad is divided into exodermis, intermediate layer and endodermis three parts, specific nano sorbing material is distributed in the exodermis and intermediate layer of film, 5 10 microns of skin thickness, and its average filtration aperture is 46 nanometers;0.5 5 microns of endodermis thickness, its average filtration aperture are 0.5 1 nanometers.Film base material material, pore-foaming agent, solvent and specific porous adsorbing material to be chosen, spinning solution is made at room temperature, is bathed after spinning head is extruded by 30 60cm vapor, temperature maintains 60 80 degree, most afterwards through washing, drying, finished product.The present invention has the advantages that inflow-rate of water turbine is big, service life length, and single treatment ability is strong.

Description

Dialysis effluent purifying hollow-fibre membrane and its processing method
Technical field
The present invention relates to dialysis liquid waste treating apparatus field, say it is that a kind of adsorbent will not enter the circulatory system in detail, can The dialysis waste liquid of the effectively various toxin ions such as isolation urase, absorption ammonium ion, free phosphate radical and sulfate ion is net Change hollow-fibre membrane and its processing method.
Background technology
It is known that kidney trouble is a global public health problem, the whole world, which there are about 2,400,000 patients with renal failure, to be needed Dialyse.Due to aging population and the increase of diabetes illness probability, the quantity of patients with renal failure is also constantly rising(Often Year increase 7-8%).CKD can influence we 1/10th people.For unfortunately suffering from the people of renal failure, it is good for Health is gradually swallowed.At home, end stage renal failure patient, common people cry " uremia ", many patients by haemodialysis or Kidney transplant substitutes renal function.
Kidney patient often has many troubles in treatment, for example to arrive hospital regularly and be dialysed, with clear Except the toxin of accumulation, but two kinds of currently a popular dialysis:Hemodialysis and peritoneal dialysis therapy, it is time-consuming longer, And dialysis needs substantial amounts of dialyzate every time, this virtually adds the expenditure of medical expense, also limit two kinds of dialysis sides The development that formula is dialysed to packaged type, because dialysis needs to carry a few decaliter dialyzates every time.
To solve problem above, dialyzate purify and circulating repetition uses, is the main flow of technology today research.Enter Gone dialysis dialysis waste liquid in mainly contain urea, creatinine, phosphate, B2M, be recycled for a long time during band The endotoxin material such as virus and bacteria entered, how to remove these materials is that the key technology that dialysis effluent purifying is reused is asked Topic.With the development of dialyzate circulating technology, various new dialyzate recovery systems are developed, such as Temasek science and engineering The patent of institute() and Zhuhai Jian Fan scientific & technical corporation CN106111079A(CN205515729U patent) all propose using urase or Adsorbent carries out circular regeneration to dialysis waste liquid.Adsorbent mainly includes zirconium base, aluminium base and activated carbon, and enzyme used is mainly urea Enzyme.These materials are successively emitted in adsorbent equipment, and long-term use has the less adsorbent of particle diameter or urase entrance follows Loop system, causes the pollution of whole dialysis fluid circulation, and the dialysis to patient brings greater risk.
The content of the invention
Present invention aim to address above-mentioned the deficiencies in the prior art, there is provided and a kind of adsorbent will not enter the circulatory system, Urase can effectively be completely cut off, the various toxin such as ammonium ion, free phosphate radical and sulfate ion after absorption urea decomposes from The dialysis effluent purifying hollow-fibre membrane and its processing method of son.
Technical scheme is used by the present invention solves above-mentioned the deficiencies in the prior art:
One kind dialysis effluent purifying hollow-fibre membrane, it is characterised in that formed by the Raw material processing of following proportion by weight:Bag The specific nano for including the film base material material of 15-20 parts, the pore type additive of 3-10 parts, the solvent of 75-80 parts, and 2-4 parts is inhaled Enclosure material;Hollow-fibre membrane internal diameter is 220-350 microns, wall thickness is 40-60 microns, film wire ecto-entad be divided into exodermis, in Interbed and endodermis three parts, specific nano sorbing material is distributed in the exodermis and intermediate layer of film, its particle diameter 1-8nm, Exodermis to the specific nano sorbing material density in intermediate layer is gradually reduced, in endodermis without specific nano sorbing material; The skin thickness 5-10 microns of film wire, its average filtration aperture are 4-6 nanometers;The endodermis thickness 0.5-5 microns of film wire, its Average filtration aperture is 0.5-1 nanometers.
Heretofore described film base material material is polysulfones, SPSF, polyether sulfone, sulfonated polyether sulfone, Kynoar, poly- One or more in lactic acid, polymethyl methacrylate, polyvinyl alcohol;Described pore type additive is polyvinylpyrrolidine Alkanone(PVP)Or polyethylene glycol(At least one of PEG);Solvent is dimethyl acetamide (DMAC), dimethylformamide (DMF), one or more in 1-METHYLPYRROLIDONE (NMP).
Heretofore described specific nano sorbing material is silicon-based adsorption material material, zirconium base sorbing material and magnesium-based absorption At least one of material.
Silicon-based adsorption material material described in invention is at least one of silica, silicon chloride, phosphoric acid silicon grain;Described Zirconium base sorbing material is at least one of zirconium oxide, zirconium chloride, zirconium phosphate particles.Described magnesium-based sorbing material is oxidation At least one of magnesium, magnesium carbonate, phosphoric acid magnesium granules.
A kind of preparation method for effluent purifying hollow-fibre membrane of dialysing, it is characterised in that comprise the following steps:
A, by proportion by weight choose 15-20 parts film base material material, the pore type additive of 3-10 parts, the solvent of 75-80 parts, and The specific porous adsorbing material of 2-4 parts;
B, at room temperature, pore type additive is added in solvent, after pore type additive all dissolving, adds film base material material With specific porous adsorbing material, 70-100 degree is warming up to, 18-26h is sufficiently stirred in nitrogen atmosphere, makes consolidating in spinning solution The full and uniform dissolving of body material, vacuumizing and defoaming, is made spinning solution;
C, spinning solution is extruded with core liquid through spinning head, 30-60cm vapor is then passed through with the speed of 10-15 rice per minute Bath, the temperature of vapor bath maintain 60-80 degree, are most washed afterwards through water wash system, drying system drying, finished product.
Heretofore described core liquid is the mixed liquor of concentration 10-20% solvents and water.Described core liquid solvent can be diformazan At least one of base formamide, dimethyl acetamide, 1-METHYLPYRROLIDONE.
Heretofore described water wash system washing is made up of 60 degree, 70 degree, 80 degree and the water washing devices of 90 Du tetra-. All solvents in this water-washing process spinning solution, most perforating agents(Such as PVP) and specific nano Sorbing material(Such as silicon substrate or zirconium base or magnesium-base nano sorbing material)It can be moved to film exodermis, and be finally completed phase separation.
For the present invention in use, coordinating urase and porous adsorbing material to use, urase resolves into the urea in waste liquid of dialysing Ammonium carbonate, uric acid, the organic substance such as creatinine in porous adsorbing material absorption dialysis waste liquid, the then dialysis by the present invention are given up The endotoxin such as liquid purification doughnut membrane filtration, present invention filtering retention bacterium, virus and the small molecule eluted are porous Sorbing material(Activated carbon, chitosan, montmorillonite)And urase, specific nano sorbing material then adsorbable various toxin ions. The present invention is fixed on exodermis and the intermediate layer of doughnut membranous wall by the way that specific nano sorbing material is processed, and plays fixation While do not influence its function, the addition of the hierarchical specific nano sorbing material of hollow-fibre membrane, make the present invention to saturating The effluent purifying used time is analysed, it is various to play ammonium ion, free phosphate radical and sulfate ion after absorption urea decomposes etc. The effect of toxin ion, while the small molecule porous adsorbing material and urase eluted in previous step can be filtered out;With excessively stream The advantages that amount is big, service life length, and single treatment ability is strong.
Brief description of the drawings
Fig. 1 be exodermis of the present invention outer surface SEM ESEMs under structure chart.
Fig. 2 is this hair intermediate layer(Film wire wall)Mid-section structure chart under SEM ESEMs.
Fig. 3 be endodermis of the present invention inner surface SEM ESEMs under structure chart.
Embodiment
One kind dialysis effluent purifying hollow-fibre membrane, it is characterised in that by the Raw material processing of following proportion by weight Into:Film base material material including 15-20 parts, the pore type additive of 3-10 parts, the solvent of 75-80 parts, and the specificity of 2-4 parts are received Rice sorbing material;Hollow-fibre membrane(Film wire)Internal diameter is 220-350 microns, wall thickness is 40-60 microns, and film wire ecto-entad is divided into Exodermis, intermediate layer and endodermis three parts, the pore size filter of film wire endodermis are less than the pore size filter of outer layer, specific nano Sorbing material is distributed in film(Silk)Exodermis and intermediate layer in, its particle diameter 1-8nm, exodermis to intermediate layer specific nano inhale Enclosure material density is gradually reduced, preferred without specific nano sorbing material, the particle diameter of specific nano sorbing material in endodermis 2-4nm;The skin thickness 5-10 microns of film wire, its average filtration aperture are 4-6 nanometers;The endodermis thickness 0.5-5 of film wire Micron, its average filtration aperture is 0.5-1 nanometers.
Heretofore described film base material material is polysulfones, SPSF, polyether sulfone, sulfonated polyether sulfone, Kynoar, poly- One or more in lactic acid, polymethyl methacrylate, polyvinyl alcohol;Described pore type additive is polyvinylpyrrolidine Alkanone(PVP)Or polyethylene glycol(At least one of PEG);Solvent is dimethyl acetamide (DMAC), dimethylformamide (DMF), one or more in 1-METHYLPYRROLIDONE (NMP).
Heretofore described specific nano sorbing material is silicon-based adsorption material material, zirconium base sorbing material and magnesium-based absorption At least one of material.
Silicon-based adsorption material material described in invention is at least one of silica, silicon chloride, phosphoric acid silicon grain;Described Zirconium base sorbing material is at least one of zirconium oxide, zirconium chloride, zirconium phosphate particles.Described magnesium-based sorbing material is oxidation At least one of magnesium, magnesium carbonate, phosphoric acid magnesium granules.
A kind of preparation method for effluent purifying hollow-fibre membrane of dialysing, it is characterised in that comprise the following steps:
A, by proportion by weight choose 15-20 parts film base material material, the pore type additive of 3-10 parts, the solvent of 75-80 parts, and The specific porous adsorbing material of 2-4 parts;
B, at room temperature, pore type additive is added in solvent, after pore type additive all dissolving, adds film base material material With specific porous adsorbing material, 70-100 degree is warming up to, 18-26h is sufficiently stirred in nitrogen atmosphere, makes consolidating in spinning solution The full and uniform dissolving of body material, vacuumizing and defoaming, is made spinning solution;
C, spinning solution is put into hollow fiber spinning machine with core liquid, extruded through spinning head, then with the speed of 10-15 rice per minute Vapor bath of the degree by 30-60cm length, the temperature of vapor bath maintain 60-80 degree, most wash, dry through water wash system afterwards System is dried, and is collected by winding apparatus, finished product.
The vapor bath of 60-80 degree can make exodermis form macroporous structure, and this steam bath will can gather at the endodermis of film Vinyl pyrrolidone (pore type additive)It is attracted to the exodermis of film, and PVP(Pore type additive) In moving process from inside to outside, the specific nano sorbing material at endodermis can be driven to be moved to exodermis, most end form Be gradually reduced into exodermis to intermediate layer specific nano sorbing material density, in endodermis without specific nano sorbing material Hollow fiber film structure, it can be good at playing the absorption of each layer or retain advantage, the specificity in exodermis and intermediate layer is received Rice sorbing material adsorbs to some ions from dialyzate first, and endodermis then can not to specific nano sorbing material The material of absorption continues more efficient retention, is greatly improved absorption and retention efficiency.Sequentially entered by the film of steam bath In 60 degree, 70 degree, 80 degree and the water wash systems of 90 Du tetra-, all solvents in this water-washing process spinning solution, the overwhelming majority Pore type additive(Such as PVP) and specific nano sorbing material moved to film exodermis, it is and final complete Into phase separation(Solvent in spinning solution, pass additive are eluted).
Because high-temperature water vapor is bathed, specific nano sorbing material can be embedded in intermediate layer and the outermost layer of film, As shown in Fig. 1-Fig. 3 SEM structure photos, the endodermis of film forms the thick fine and close selective separating of 1-2 microns, film on its endodermis The average pore size in hole is that the heat source substance such as 0.5-1nm, all bacteriums, endotoxin can not all pass through the filter layer.
Heretofore described core liquid is the mixed liquor of concentration 10-20% solvents and water.Described core liquid solvent can be diformazan At least one of base formamide, dimethyl acetamide, 1-METHYLPYRROLIDONE.
Heretofore described water wash system washing is made up of 60 degree, 70 degree, 80 degree and the water washing devices of 90 Du tetra-.
For the present invention in use, coordinating urase and porous adsorbing material to use, urase resolves into the urea in waste liquid of dialysing Ammonium carbonate, uric acid, the organic substance such as creatinine in porous adsorbing material absorption dialysis waste liquid, the then dialysis by the present invention are given up The endotoxin such as liquid purification doughnut membrane filtration, present invention filtering retention bacterium, virus and the small molecule eluted are porous Sorbing material(Activated carbon, chitosan, montmorillonite)And urase, specific nano sorbing material then adsorbable various toxin ions. The present invention is fixed on exodermis and the intermediate layer of doughnut membranous wall by the way that specific nano sorbing material is processed, and plays fixation While do not influence its function, the addition of the hierarchical specific nano sorbing material of hollow-fibre membrane, make the present invention to saturating When analysing effluent purifying, play and adsorbing(After urea decomposes)Ammonium ion, free phosphate radical and sulfate ion etc. are various The effect of toxin ion, while the small molecule porous adsorbing material and urase eluted in previous step can be filtered out;With excessively stream The advantages that amount is big, service life length, and single treatment ability is strong.
The dialysis effluent purifying hollow-fibre membrane and its manufacture method of the offer of the present invention, its exodermis, intermediate layer Specific nano sorbing material(Silicon substrate, zirconium base or magnesium-based sorbing material)Ammonium ion after adsorbable urea decomposition, Yi Jiyou From phosphate radical and sulfate ion, the compact texture of endodermis can all retain almost all of endotoxin.This layering Structure design not only can effectively fix nano adsorption material and also densification endodermis in effectively catching bacterium, endotoxin Deng heat source substance simultaneously, moreover it is possible to inhale the activated carbon eluted in upper early stage processing procedure, urase or even the silicon substrate to come off or zirconium base Attached particle retains again, plays a part of multiple-protection.

Claims (8)

1. one kind dialysis effluent purifying hollow-fibre membrane, it is characterised in that formed by the Raw material processing of following proportion by weight: Film base material material including 15-20 parts, the pore type additive of 3-10 parts, the solvent of 75-80 parts, the specific nano of 2-4 parts are inhaled Enclosure material;Hollow-fibre membrane internal diameter is 220-350 microns, wall thickness is 40-60 microns, film wire ecto-entad be divided into exodermis, in Interbed and endodermis three parts, specific nano sorbing material is distributed in the exodermis and intermediate layer of film, its particle diameter 1-8nm; The skin thickness 5-10 microns of film wire, its average filtration aperture are 4-6 nanometers;The endodermis thickness 0.5-5 microns of film wire, its Average filtration aperture is 0.5-1 nanometers.
2. dialysis effluent purifying hollow-fibre membrane according to claim 1, it is characterised in that described film base material material is In polysulfones, SPSF, polyether sulfone, sulfonated polyether sulfone, Kynoar, PLA, polymethyl methacrylate, polyvinyl alcohol One or more;Described pore type additive is PVP(PVP)Or polyethylene glycol(PEG in) at least It is a kind of;Solvent is dimethyl acetamide (DMAC), dimethylformamide(DMF), one kind in 1-METHYLPYRROLIDONE (NMP) or It is a variety of.
3. dialysis effluent purifying hollow-fibre membrane according to claim 1, it is characterised in that described specific nano Sorbing material is at least one of silicon-based adsorption material material, zirconium base sorbing material and magnesium-based sorbing material.
4. dialysis effluent purifying hollow-fibre membrane according to claim 1, it is characterised in that described silicon-based adsorption material Expect at least one of silica, silicon chloride, phosphoric acid silicon grain;Described zirconium base sorbing material is zirconium oxide, zirconium chloride, phosphorus At least one of sour zirconium particle;Described magnesium-based sorbing material is at least one in magnesia, magnesium carbonate, phosphoric acid magnesium granules Kind.
5. a kind of preparation method for effluent purifying hollow-fibre membrane of dialysing, it is characterised in that comprise the following steps:
A, by proportion by weight choose 15-20 parts film base material material, the pore type additive of 3-10 parts, the solvent of 75-80 parts, and The specific porous adsorbing material of 2-4 parts;
B, at room temperature, pore type additive is added in solvent, after pore type additive all dissolving, adds film base material material With specific porous adsorbing material, 70-100 degree is warming up to, 18-26h is sufficiently stirred in nitrogen atmosphere, makes consolidating in spinning solution The full and uniform dissolving of body material, vacuumizing and defoaming, is made spinning solution;
C, spinning solution is extruded with core liquid through spinning head, then bathed by 30-60cm vapor, the temperature of vapor bath maintains In 60-80 degree, most washed afterwards through water wash system, drying system drying, finished product.
6. the preparation method of dialysis effluent purifying hollow-fibre membrane according to claim 5, it is characterised in that the present invention Described in water wash system washing by 60 degree, 70 degree, 80 degree and the water washing devices of 90 Du tetra- composition.
7. the preparation method of the dialysis effluent purifying hollow-fibre membrane according to claim 5 or 6, it is characterised in that described Core liquid for concentration 10-20% solvents and water mixed liquor.
8. the preparation method of dialysis effluent purifying hollow-fibre membrane according to claim 7, it is characterised in that described Core liquid solvent can be at least one of dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE.
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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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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
CN109316986A (en) * 2018-11-07 2019-02-12 中南大学 A kind of acrylic acid and sulfonation dihydroxypropylchitosan modified polysulfone film 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
CN115297953A (en) * 2019-11-22 2022-11-04 德国科技术基金会 Porous membranes comprising adsorbent 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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Address after: No.20, Xingshan Road, Weihai Torch hi tech Industrial Development Zone, Weihai City, Shandong Province, 264210

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Address before: No.20, Xingshan Road, torch hi tech Industrial Development Zone, Weihai City, Shandong Province 264200

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