CN101314110A - Hollow fiber film and preparation method thereof - Google Patents
Hollow fiber film and preparation method thereof Download PDFInfo
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- CN101314110A CN101314110A CNA2008100538324A CN200810053832A CN101314110A CN 101314110 A CN101314110 A CN 101314110A CN A2008100538324 A CNA2008100538324 A CN A2008100538324A CN 200810053832 A CN200810053832 A CN 200810053832A CN 101314110 A CN101314110 A CN 101314110A
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Abstract
The invention relates to a hollow fibrous membrane and a preparation method thereof. The fibrous membrane is used for waste oil regeneration. The invention is characterized in that: the wall thickness of the membrane is between 300 and 800mm; the formula comprises the compositions of spinning dope in weight percentage: 10 to 30 percent of polysulphone, 60 to 85 percent of organic solvent, 5 to 15 percent of porogenic agent, and the sum of the compositions being 100 percent; the weight-average molecular weight of the polysulphone is between 40,000 and 100,000; the organic solvent is one or a plurality of compositions of dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide and N-methyl pyrrolidone; and the porogenic agent is one or a plurality of compositions of organic polyethylene glycol, polyglycerol and polyvinylpyrrolidone, or/and inorganic aluminum chloride, sodium chloride, calcium chloride, calcium carbonate, silicon dioxide and nitrate. The method for preparing the membrane adopts the formula in the invention and an optimized dry-wet spinning process for spinning. The membrane obtained from the invention has obvious regeneration or purification effect to used oil (lubricant).
Description
Technical field
The present invention relates to the diffusion barrier technology, being specially a kind of is the hollow-fibre membrane and preparation method thereof of membrane material with the polysulfones, this film is mainly used in oil reclaiming (comprising all kinds of discarded animals and plants oil products of purifying and petroleum-type product), and international monopoly Main classification number plan is Int.Cl.B01D 69/12 (2006.01).
Background technology
The source of waste oil is very extensive, and only the annual production of lubricating oil just reaches 5,000,000 tons at present.These oil derive from motor vehicle, transformer cleans the back wet goods with oil, steamer unit, part.Show that after deliberation remove extraneous inorganic impurity of sneaking in the waste oil, its most refuses are organic matters that oxidation produces, more vast scale is colloid, asphalitine and carbon element matter.The traditional renovation process of this type of oil product mainly adopts sulfuric acid carclazyte technology, after being about to waste oil and carrying out sedimentation and remove large granular impurity, removes colloid, asphalitine and other oxide in deoiling with 93% sulfuric acid earlier, neutralizes with alkali lye then, uses clay-filtered at last.Not only can emit the intense stimulus smell that oxidation generates in this technical process, but also give off acid sludge and alkaline residue, cause secondary environmental pollution.
Chinese patent technology CN1162007 discloses technology and the device that a kind of waste oil regeneration is neutral oil and bright stock.Its technology of waste oil regenerating flow process is: at first waste oil, carclazyte, vapour three-phase are mixed and fail, be heated to 300 ℃ in tube furnace circulation refining and distilling tower, flash off moisture, clear diesel oil; Oil with soil changes second tube furnace circulation refining and distilling tower over to then, and oil, soil, vapour three-phase heat under violent turbulent condition and be refined to 400 ℃; Filter after last heat exchange is cooled to 130 ℃, obtain neutral oil and bright stock.But this process also will realize down at high temperature (300 ℃ or 400 ℃), needs to consume lot of energy equally.The introducing of carclazyte can form a large amount of waste residues in addition, causes post processing very difficult.
Chinese patent literature CN 101070507 has reported a kind of renovation process and equipment of waste lubricating oil, renovation process comprises following technology successively: impurity sedimentation, particle coarse filtration, vacuum dehydration, it is characterized in that behind the impurity sedimentation process, heating process being arranged, also have post bake technology and membrane separation process after the vacuum dewatering technique; The temperature of heating process is 65～75 ℃; The temperature of post bake technology is 50～90 ℃; Described membrane separation process adopts hollow-fibre membrane, and average pore size is 0.01～0.5 μ m, can anti-80～90 ℃ of high temperature, and the oil resistant corrosion.This reclaim equiment is characterised in that it is applicable to the renovation process of this invention, comprises at least one preceding heater, a cover vacuum dewatering plant, intermediate storage tank, at least one post-heater and at least one hollow fiber film assembly.Adopt this inventive method and apparatus and process simple, processing ease is easy to control, energy transformation ratio height and good separating effect, and free from environmental pollution, energy consumption is low, can make the waste lubricating oil effective recycling.
Chinese patent literature CN 1585671 has reported and has been used for hollow-fiber film and the manufacture method thereof that waste lubrication oil is handled, the prescription of the hyperfiltration cellulose acetate hollow-fiber film that a kind of manufacturing has high water permeability is provided, and tunica fibrosa can carry out water-oil separating with the energy consumption of minimum and low obstruction tendency.This patent is in the U.S., world patent tissue and European Patent Organization's application.
Chinese patent CN 1557532 has reported the preparation method of in industrial wastewater, municipal wastewater, drinking water treatment water reuse and the employed polysulfone hollow fibre milipore filter of pharmaceuticals industry extraction and cleaning.It is characterized in that: in the common prescription of polysulfone hollow fibre milipore filter, add the polyvinylpyrrolidone K-15 of 2-6% and the mixture of K-30, the ratio of K-15: K-30 is 1: 3-3: 1, operating condition routinely is used for dry-wet spinning technology and makes the hollow fiber ultrafiltration membrane that internal diameter is 0.7mm-2.0mm, through in water behind the 4h washing by soaking, place the tubular type high-pressure reactor that contains oxidant, make polyvinyl pyrrolidone fully oxidation cross-linked.This film is placed more than 105 ℃ of dry 8h of baking oven, and this polysulfone hollow fibre milipore filter still had good hydrophilicity after taking-up was cooled to room temperature.
Reported for work a kind of polysulphone super-filter membrane of modification of Chinese patent CN1125635 is a polysulfones to carry out modified-reaction through acidylate-amination or chloromethylation-amination method and makes, and the rerum natura of this milipore filter is: average pore size 20-80 μ m; Hole density: 5 * 10
9-8 * 10
9Hole/cm
2, the skin thickness of film is 5-12 μ m; Supporting layer thickness: 50-120 μ m.This milipore filter, crosslinked action that can be by two valerals down and trypsase carry out crosslinked, also can be by diazo-reaction at 0-4 ℃ of following and immobilized affinity ultrafiltration film of making of trypsase, this film can be used for the purifies and separates trypsin inhibitor, makes its purity reach 98.5%.
Chinese patent CN1179354 has reported a kind of perforated membrane, is the solution that polysulfones and a kind of free radical can gather monomer is exposed in the ultraviolet light and forms the blend that is made of with the copolymer of interconnective polysulfones activation products of covalent bond and polymerization single polymerization monomer polysulfones and polymer segment.Described solution is divided into two-phase, comprises the porous solid phase that contains described film.
Above patent documentation report is the preparation of the ps hollow fiber uf membrane of water treatment field, yet there are no report at ps hollow fiber uf membrane of waste oil regeneration and preparation method thereof specially.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is: a kind of hollow-fibre membrane and preparation method thereof is provided, and this hollow-fibre membrane can effectively be removed impurity such as carbon granule in the waste oil, metal fillings, asphalitine, colloid, purifying waste oil; This preparation method has optimized dry-wet spinning technology, and technology is simple, is suitable for industrial applications.
The technical scheme that the present invention solves described membrane technology problem is, design a kind of hollow-fibre membrane, be used for waste oil regeneration, the wall thickness that it is characterized in that this film is the 300-800 micron, the prescription of spinning solution is polysulfones 10-30wt%, organic solvent 60-85wt%, pore-foaming agent 5-15wt%, each component sum is 100%; The weight average molecular weight of described polysulfones is 4000-100000; Described organic solvent is one or more of dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide and N-methyl pyrrolidone; Described pore-foaming agent is one or more in the following substances: organic matter polyethylene glycol, polyglycerol and polyvinylpyrrolidone, or/and inorganic matter aluminium chloride, sodium chloride, calcium chloride, calcium carbonate, silica and nitrate.
The technical scheme that the present invention solves described preparation method's technical problem is, design a kind of preparation method of hollow-fibre membrane, it is characterized in that this preparation method adopts hollow-fibre membrane spinning solution mass percent prescription of the present invention and the spinning of dry-wet spinning technology, process conditions are: the spinning solution temperature is 25-75 ℃, pump into the spinning of insertion tubular type spinneret through measuring pump, nozzle center feeds nitrogen, adjustable thermostatic circulation coagulating bath curing molding, the adjustable temperature of constant temperature circulation coagulating bath is 25-45 ℃, and spinning solution is exposed in the air gap of 0-40cm before entering coagulating bath admittedly by spinneret.
Compared with prior art, hollow-fibre membrane of the present invention has high oily permeation flux, strong-hydrophobicity, higher mechanical strength and good stable, can be with Impurity removals such as the carbon granule in the waste oil, metal fillings, asphalitine, colloid, various discarded animals and plants oil products of purifying and petroleum-type oil product effectively.Doughnut membrane preparation method of the present invention has been optimized dry-wet spinning technology, and simple, need not new equipment, is suitable for industrialization promotion and uses.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment, but claim of the present invention is not subjected to the restriction of embodiment:
The hollow-fibre membrane (abbreviation film) of the present invention's design, purpose is used for waste oil regeneration or purification, and the wall thickness that it is characterized in that this film is the 300-800 micron, and the prescription of spinning solution is: polysulfones 10-30wt%, organic solvent 60-85wt%, pore-foaming agent 5-15wt%, each component sum is 100%; The weight average molecular weight of described polysulfones is 4000-100000; Described organic solvent is one or more of dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide and N-methyl pyrrolidone; Described pore-foaming agent is one or more in the following substances: organic matter polyethylene glycol, polyglycerol and polyvinylpyrrolidone, or/and inorganic matter aluminium chloride, sodium chloride, calcium chloride, calcium carbonate, silica and nitrate.
The optimization formula of the spinning solution of film of the present invention is polysulfones 18-23wt%; Organic solvent 65-77wt%; Pore-foaming agent 5-12wt%, each component sum is 100%; The preferred dimethyl sulfoxide (DMSO) of described organic solvent; Add the preferred polyethylene glycol of (pore) agent.
The present invention has designed the preparation method of described film simultaneously, this preparation method adopts hollow-fibre membrane mass percent prescription of the present invention and dry-wet spinning technology to carry out spinning, concrete technology is as follows: according to film quality percentage formulated spinning solution of the present invention, under 25-75 ℃, spinning solution is pumped into the spinning of insertion tubular type spinneret (head) through measuring pump, nozzle center feeds nitrogen, after spinning solution is extruded by spinneret (head), after the air bath through the 0-40cm distance, enter curing molding in the adjustable thermostatic circulation coagulating bath, the adjustable temperature scope of constant temperature circulation coagulating bath is 25-45 ℃, is twined by spiral filament forming machine then and collects promptly.Regulate the rotating speed of spiral filament forming machine wire wrapping wheel, the size of control draft speed can be carried out in various degree stretching to hollow-fibre membrane, can obtain the hollow-fibre membrane of different wall.In addition, adopt spinning head (for example, 0.5mm, 0.7mm, the 0.8mm) spinning in different apertures, also can obtain the hollow-fibre membrane of different wall.The wall thickness that the present invention designs film is the 300-800 micron, and pure water permeability is 80-1000L/ (m2hbar).
Preparation method of the present invention optimizes traditional ps hollow fiber uf membrane dry-wet spinning technology; improvements are: feed nitrogen in nozzle center 1.; avoided spinning solution the frozen plug in spinning head exit (conventional ps hollow fiber uf membrane does-generally to adopt water be core liquid to wet method preparation process; regular meeting makes spinning solution cause spinning head to stop up at the exit of spinning head coagulation forming in the time of in spinning process), make the spinning process smooth and easy easy row that becomes.2. adopt the curing molding method of adjustable thermostatic circulation coagulating bath, make the temperature constant of coagulating bath system, guaranteed that prepared polysulfone hollow fibre has stable performance (in the spinning process of doughnut, water temperature in the coagulating bath is to raise along with the certain temperature of having of spinning process, make the environment of spinning polymer fluid coagulation forming change, thereby make the polysulfone hollow fibre unstable properties of preparing).
Ps hollow fiber uf membrane of the present invention's design and preparation method thereof, the gained film is mainly used in the regeneration or the purification of used oil (lubricating oil), has high oily permeation flux and good oil resistant contaminative.Carbon distribution in the lubricating oil, metal filings and impurity such as oxidation deterioration material such as gum asphalt are had the good effect of damming, not only can be used for the recovery of waste lubricating oil, can also be used for the refining processing of animal and plant fat.
The regeneration of gained film of the present invention or purification waste oil effect can adopt the direct-vision method check.Owing to have impurity such as some colloidal substances, asphalitine and some carbon granules in the waste oil, can make the color burn of oil product, impurity is many more, and color is dark more.Therefore, the clean-up effect of film can come the contained or degree of removing impurity such as colloid, asphalitine and carbon granule in the intuitive judgment oil by the color of oil product, and then judges the separating effect of described film.Certainly, the regeneration of film or purification waste oil effect also can adopt assorted or the removal of impurities situation (referring to embodiment 4) of containing of the quantitative detection oil product of spectrophotometer.
The present invention does not address part and is applicable to prior art.
Provide specific embodiments of the invention below:
Embodiment 1
(mass percent, down together) prescription of design hollow-fibre membrane is: 17wt% polysulfones, the organic solvent of 70wt%, the pore-foaming agent of 13wt%; Buying (homemade) on the described polysulfones market, its weight average molecular weight is 80000; Organic solvent is a dimethyl formamide, and pore-foaming agent is a polyethylene glycol.
Adopt dry-wet spinning technology to prepare ps hollow fiber uf membrane according to above-mentioned prescription, concrete technology is as follows: described formula rate material 65 ℃ of miscible 7 hours of stirrings down, and then leave standstill under 50 ℃, insulation, deaeration 6 hours; Under same temperature, spinning solution is pumped into spinning head (aperture is 0.8mm) extruding spinning with measuring pump, the spinning head center feeds nitrogen, the extruded velocity of spinning solution is 8ml/min, after the air bath of 35cm, enter temperature and be coagulation forming in 35 ℃ the thermostatic circulation bath, up-coiler drawing-off winding speed is 100m/min, can obtain film of the present invention.
After testing, the wall thickness of gained film is 750 microns, and pure water permeability is 250L/ (m
2H).
Embodiment 2
The prescription of design hollow-fibre membrane is: 19wt% polysulfones, the organic solvent of 72wt%, the pore-foaming agent of 9wt%; Described polysulfones market purchasing (BASF production), its weight average molecular weight is 80000, and organic solvent is 40wt% dimethyl formamide and 32wt% dimethyl formamide and mixed liquor, and pore-foaming agent is a polyethylene glycol.
Adopt dry-wet spinning technology to prepare ps hollow fiber uf membrane according to above-mentioned prescription, concrete technology is as follows: described formula rate material 65 ℃ of miscible 7 hours of stirrings down, and then leave standstill under 50 ℃, insulation, deaeration 6 hours; Under same temperature, spinning solution is pumped into spinning head (aperture is 0.8mm) extruding spinning with measuring pump, the spinning head center feeds nitrogen, the extruded velocity of spinning solution is 8ml/min, after the air bath of 30cm, enter temperature and be coagulation forming in 25 ℃ the thermostatic circulation bath, up-coiler drawing-off winding speed is 100m/min, can obtain film of the present invention.
After testing, the wall thickness of gained film is 750 microns, and pure water permeability is 198L/ (m
2H).
Embodiment 3
The prescription of design hollow-fibre membrane is: 23wt% polysulfones, the organic solvent of 70wt%, the pore-foaming agent of 7wt%; Described polysulfones picks up from market (BASF production), and its weight average molecular weight is 80000, and organic solvent is a dimethyl formamide, and pore-foaming agent is the mixed liquor of 6wt% polyethylene glycol and 1wt% sodium chloride.
Adopt dry-wet spinning technology to prepare ps hollow fiber uf membrane according to above-mentioned prescription, concrete technology is as follows: described formula rate material 65 ℃ of miscible 7 hours of stirrings down, and then leave standstill under 50 ℃, insulation, deaeration 6 hours; Under same temperature, spinning solution is pumped into spinning head (aperture is 0.8mm) extruding spinning with measuring pump, the spinning head center feeds nitrogen, the extruded velocity of spinning solution is 10ml/min, after the air bath of 40cm, enter temperature and be coagulation forming in 25 ℃ the thermostatic circulation bath, up-coiler drawing-off winding speed is 120m/min, can obtain film of the present invention.
After testing, the wall thickness of gained film is 750 microns, and pure water permeability is 110L/ (m
2H).
Embodiment 4
The check of waste oil clean-up effect.
The film of embodiment 1-3 gained is designated as respectively I, II, III number.Adopt I, the II of gained, the used oil that the III film is handled engine respectively.Utilize spectrophotometer to detect the absorbance A that leaches edible vegetable oil then, to judge the separating property or the effect of gained film.Its principle is: the A value is more little, and light transmittance is big more, and the separation efficiency of film is good more; In like manner, the A value is big more, and light transmittance is more little, and the separation efficiency of film is poor more.
The formula of the rejection of definition film is as follows: rejection (%)=(Ao-A)/Ao * 100%.
In the formula: Ao, the absorbance of former used oil; A, film separates the absorbance that obtains edible vegetable oil.
Waste oil is after separating by described I, II, III film, and resulting edible vegetable oil is designated as edible vegetable oil a, b, c respectively.Because the absorbance A value of used oil (lubricating oil) has surpassed spectrophotometric maximum, can't measure on spectrophotometer, so it is also diluted with 1: 4 volume ratio with cyclohexane.Wavelength is the 600nm place on spectrophotometer then, the absorbance of testing them respectively, and test result is listed in table 1.As can be seen from Table 1, the absorbance of used oil at the 600nm place is 1.433.After passing through the I film and the II film separates, oil product is reduced to 0.164 and 0.125 respectively at the absorbance at 600nm place, and by after the processing of III film, is reduced to 0.049 especially, only is 3.4% of initial value, and effect is very obvious.
The comparison sheet of table 1 oil product absorbance
| Oil product | Waste lubricating oil | Edible vegetable oil a | Edible vegetable oil b | Edible vegetable oil c |
| Absorbance | 1.433 | 0.164 | 0.125 | 0.049 |
| Interception capacity (%) | 0 | 88.6 | 91.3 | 99.6 |
Claims (4)
1. a hollow-fibre membrane is used for waste oil regeneration, and the wall thickness that it is characterized in that this film is the 300-800 micron, and the prescription of spinning solution is polysulfones 10-30wt%, organic solvent 60-85wt%, pore-foaming agent 5-150wt%, and each component sum is 100%; The weight average molecular weight of described polysulfones is 4000-100000; Described organic solvent is one or more of dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide and N-methyl pyrrolidone; Described pore-foaming agent is one or more in the following substances: organic matter polyethylene glycol, polyglycerol and polyvinylpyrrolidone, or/and inorganic matter aluminium chloride, sodium chloride, calcium chloride, calcium carbonate, silica and nitrate.
2. hollow-fibre membrane according to claim 1, the prescription that it is characterized in that the spinning solution of this film is polysulfones 18-23wt%; Organic solvent 65-77wt%; Pore-foaming agent 5-12wt%, each component sum is 100%; Described organic solvent is a dimethyl sulfoxide (DMSO); Pore-foaming agent is a polyethylene glycol.
3. hollow-fibre membrane according to claim 1 is characterized in that the prescription of the spinning solution of this film is: polysulfones 23wt%, organic solvent 70wt%, pore-foaming agent 7wt%; The weight average molecular weight of described polysulfones is 80000, and organic solvent is a dimethyl formamide, and pore-foaming agent is the mixed liquor of 6wt% polyethylene glycol and 1wt% sodium chloride.
4. the preparation method of a hollow-fibre membrane, it is characterized in that this preparation method adopts claim 1 or 2 described hollow-fibre membrane spinning solution mass percent prescription and the spinning of dry-wet spinning technology, process conditions are: the spinning solution temperature is 25-75 ℃, pump into the spinning of insertion tubular type spinneret through measuring pump, nozzle center feeds nitrogen, adjustable thermostatic circulation coagulating bath curing molding, the adjustable temperature of constant temperature circulation coagulating bath is 25-45 ℃, and spinning solution is exposed in the air gap of 0-40cm before entering coagulating bath admittedly by spinneret.
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|---|---|---|---|---|
| CN102260931A (en) * | 2010-05-31 | 2011-11-30 | 天津膜科力科技有限公司 | Composite hollow fiber for heat exchanger and preparation method thereof |
| CN102504932A (en) * | 2011-11-07 | 2012-06-20 | 豆远奎 | A method of purifying waste internal combustion engine oil by sodium chloride |
| CN102580556A (en) * | 2012-03-06 | 2012-07-18 | 北京科泰兴达高新技术有限公司 | Antipollution flat membrane and method for producing same |
| CN101721925B (en) * | 2010-01-21 | 2012-08-29 | 常州市美纤膜技术有限公司 | Domestic hollow fiber ultrafiltration membrane for purifying water and preparation method thereof |
| CN102698611A (en) * | 2012-06-27 | 2012-10-03 | 上海大学 | Method for preparing polysulfone amide hollow fiber separation membrane by wet spinning |
| CN103028330A (en) * | 2012-12-20 | 2013-04-10 | 北京碧水源膜科技有限公司 | Film with flocculent reinforced hollow fibers and preparation method of film |
| CN103463994A (en) * | 2013-07-23 | 2013-12-25 | 天津工业大学 | Hollow polysulfone fiber film for water purifying cup and preparation method thereof |
| CN105817147A (en) * | 2016-04-28 | 2016-08-03 | 湖南尔康制药股份有限公司 | Modified polysulfone membrane for refining propylene glycol and preparation method of modified polysulfone membrane |
| CN106268377A (en) * | 2015-05-26 | 2017-01-04 | 华东理工大学 | A kind of polysulfone hollow fibre hemodialysis membrane and preparation method thereof |
| RU2630486C1 (en) * | 2016-06-27 | 2017-09-11 | Общество с ограниченной ответственностью "Нитро-Технологии Саяны" (ООО "НТ Саяны") | Method of processing of worked liquid oil products for manufacture of mixtures explosive explosives containing oxidizer in the form of salts - nitrates |
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| CN112619437A (en) * | 2020-12-11 | 2021-04-09 | 天津海普尔膜科技有限公司 | Preparation method of lipophilic film for waste oil purification treatment |
| CN113769589A (en) * | 2021-09-02 | 2021-12-10 | 重庆大学 | Preparation process of integrated synthetic filter membrane suitable for suction filtration of jatropha curcas plant insulating oil |
| CN113828162A (en) * | 2020-06-23 | 2021-12-24 | 三达膜科技（厦门）有限公司 | Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane |
| CN113877424A (en) * | 2021-11-12 | 2022-01-04 | 杭州水处理技术研究开发中心有限公司 | Nanofiltration membrane and preparation method and application thereof |
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| CN101721925B (en) * | 2010-01-21 | 2012-08-29 | 常州市美纤膜技术有限公司 | Domestic hollow fiber ultrafiltration membrane for purifying water and preparation method thereof |
| CN102260931A (en) * | 2010-05-31 | 2011-11-30 | 天津膜科力科技有限公司 | Composite hollow fiber for heat exchanger and preparation method thereof |
| CN102504932A (en) * | 2011-11-07 | 2012-06-20 | 豆远奎 | A method of purifying waste internal combustion engine oil by sodium chloride |
| CN102580556B (en) * | 2012-03-06 | 2015-04-29 | 北京科泰兴达高新技术有限公司 | Antipollution flat membrane and method for producing same |
| CN102580556A (en) * | 2012-03-06 | 2012-07-18 | 北京科泰兴达高新技术有限公司 | Antipollution flat membrane and method for producing same |
| CN102698611A (en) * | 2012-06-27 | 2012-10-03 | 上海大学 | Method for preparing polysulfone amide hollow fiber separation membrane by wet spinning |
| CN103028330B (en) * | 2012-12-20 | 2015-08-19 | 北京碧水源膜科技有限公司 | Cotton-shaped enhancing hollow-fibre membrane of a kind of band and preparation method thereof |
| CN103028330A (en) * | 2012-12-20 | 2013-04-10 | 北京碧水源膜科技有限公司 | Film with flocculent reinforced hollow fibers and preparation method of film |
| CN103463994A (en) * | 2013-07-23 | 2013-12-25 | 天津工业大学 | Hollow polysulfone fiber film for water purifying cup and preparation method thereof |
| CN106268377A (en) * | 2015-05-26 | 2017-01-04 | 华东理工大学 | A kind of polysulfone hollow fibre hemodialysis membrane and preparation method thereof |
| CN105817147A (en) * | 2016-04-28 | 2016-08-03 | 湖南尔康制药股份有限公司 | Modified polysulfone membrane for refining propylene glycol and preparation method of modified polysulfone membrane |
| RU2630486C1 (en) * | 2016-06-27 | 2017-09-11 | Общество с ограниченной ответственностью "Нитро-Технологии Саяны" (ООО "НТ Саяны") | Method of processing of worked liquid oil products for manufacture of mixtures explosive explosives containing oxidizer in the form of salts - nitrates |
| CN107803120A (en) * | 2017-11-20 | 2018-03-16 | 天津工业大学 | Hollow polysulfone fiber film for water purifying cup and preparation method |
| CN113828162A (en) * | 2020-06-23 | 2021-12-24 | 三达膜科技（厦门）有限公司 | Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane |
| CN113828162B (en) * | 2020-06-23 | 2022-12-20 | 三达膜科技（厦门）有限公司 | Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane |
| CN112619437A (en) * | 2020-12-11 | 2021-04-09 | 天津海普尔膜科技有限公司 | Preparation method of lipophilic film for waste oil purification treatment |
| CN113769589A (en) * | 2021-09-02 | 2021-12-10 | 重庆大学 | Preparation process of integrated synthetic filter membrane suitable for suction filtration of jatropha curcas plant insulating oil |
| CN113877424A (en) * | 2021-11-12 | 2022-01-04 | 杭州水处理技术研究开发中心有限公司 | Nanofiltration membrane and preparation method and application thereof |
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