CN101422708B - Recovery method of polyvinylidene fluoride hollow fiber membrane - Google Patents
Recovery method of polyvinylidene fluoride hollow fiber membrane Download PDFInfo
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- CN101422708B CN101422708B CN2008102272240A CN200810227224A CN101422708B CN 101422708 B CN101422708 B CN 101422708B CN 2008102272240 A CN2008102272240 A CN 2008102272240A CN 200810227224 A CN200810227224 A CN 200810227224A CN 101422708 B CN101422708 B CN 101422708B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a recycling method of a hollow PVDF fibrous membrane, which mainly comprises following steps: a. waste PVDF membrane yarns are preprocessed by rinsing, drying and smashing; b. a spinning solution is prepared; c. solids and impurities in a PVDF membrane solution are filtered and removed; and d. the PVDF spinning solution is prepared into the hollow fibrous membrane by using dry-wet spinning technique.
Description
[technical field]
The invention belongs to the recycling field of macromolecular material, more specifically, the present invention relates to the recovery method of Kynoar hollow-fibre membrane.
[technical background]
Kynoar (PVDF) is a kind of macromolecular material with high chemical stability and weatherability, at normal temperatures by acid, alkali, strong oxidizer or halogen corrosion, can be exposed to outdoor for a long time and does not have aging phenomenon.These characteristics of PVDF make it obtain gradually paying attention to and using in membrane separation technique.With PVDF is that the hollow-fibre membrane that raw material makes has the intensity height, anti-absorption contaminative is good, chemically-resistant cleans and the loading density advantages of higher, can be applicable to food industry, Biochemical Engineering, pharmaceuticals industry and water treatment, the especially very abominable sewage disposal of service condition.
The consumption of PVDF in water treatment field increases and to be exceedingly fast, and the whole world PVDF that is used to make doughnut every year is worth and reaches multi-billion dollar at present.Be about 3-7 the service life of PVDF doughnut, so will produce a large amount of useless film silks every year.Because PVDF has extremely strong stability, can not handle with conventional method, as buried and burning, deal with improperly and will cause serious environmental to pollute.The inventive method is by recycling the PVDF hollow-fibre membrane, and the environmental pollution of having avoided the useless film of PVDF to cause has farthest utilized resource.
[summary of the invention]
[technical problem that will solve]
The recoverying and utilizing method that the purpose of this invention is to provide a kind of Kynoar hollow-fibre membrane.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to the recoverying and utilizing method of a kind of Kynoar (PVDF) hollow-fibre membrane, it is characterized in that this method may further comprise the steps:
A) described useless pvdf membrane silk preliminary treatment comprises rinsing, drying and pulverizing;
B) dissolving: with above-mentioned steps a) pretreated useless pvdf membrane silk, pore former and low molecular weight additives be dissolved in the solvent, obtain spinning solution;
C) solids and the impurity that exist in spinning solution filtration: remove by filter above-mentioned steps b) obtain useless pvdf membrane silk solution;
D) spinning hollow-fibre membrane: with above-mentioned steps c) the useless pvdf membrane silk solution that obtains adopts dry-wet spinning technology to make the PVDF hollow-fibre membrane.
In the present invention, the preliminary treatment of described useless pvdf membrane silk comprises uses the cleaning agent that is selected from clear water, acid, alkali and clorox to soak 12-24 hour, with the thorough rinsing of clear water, carries out drying then under temperature 50-80 ℃ again, then pulverizes.
In the present invention, the grinding particle size of useless pvdf membrane silk is not crucial, just is convenient to its dissolving just passable.Pulverizing the equipment that uses is the disintegrating apparatus of selling in the market, also is the disintegrating apparatus that those skilled in the art know.
A preferred embodiment of the invention, described solvent are two or more solvent mixtures that is selected from dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone, trimethyl phosphate, triethyl phosphate, oxolane, acetone, tetramethylurea, Methylethyl acetone or dimethyl sulfoxide (DMSO).
Preferably, described solvent is two or more solvent mixture that is selected from dimethyl formamide, dimethylacetylamide, oxolane, acetone or N-methyl pyrrolidone.
According to the present invention, the filter screen aperture of using when filtering spinning solution is the 100-1000 order.
According to another kind of preferred implementation of the present invention, the useless pvdf membrane silk solution concentration that obtains in step c) is 10-30 weight %.
According to the present invention, described pore former is one or more macromolecule pore formers that are selected from polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol.
In the present invention, the concentration of described pore former in spinning solution is 5-30 weight %.
Described low molecular weight additives is one or more additives that are selected from lithium nitrate, calcium nitrate, sodium nitrate, lithium chloride, calcium chloride, sodium chloride, magnesium chloride, ammonium chloride, water, acetone, glycerine, ethylene glycol, ethanol.
In the present invention, the concentration of described low molecular weight additives in spinning solution is 0.1-5 weight %.
To illustrate in greater detail the present invention below.
The present invention relates to the recoverying and utilizing method of a kind of Kynoar (PVDF) hollow-fibre membrane.This method comprises the steps.
A) described useless pvdf membrane silk preliminary treatment comprises rinsing, drying and pulverizing.
Described useless pvdf membrane can be the substandard products that produce in the spinning process, and the broken film silk that produces in the pleurodiaphragmatic in terspace spare process also can be the useless film that Sewage Plant is replaced.For substandard products that produce in the manufacture process and broken film silk, soaked 12-24 hour with the liquor natrii hypochloritis earlier, again with the thorough rinsing of clear water, then temperature 50-80 ℃ of oven dry down.The useless film of replacing for Sewage Plant, the general washing with clear water earlier, remove the mud and the partial organic substances of film silk surface attachment, soaked successively 12-24 hour with liquor natrii hypochloritis, acid and alkali then, with drying down at temperature 50-80 ℃ after the thorough rinsing of clear water, then the dry film silk is pulverized again.
Described acid is one or more inorganic acids that are selected from sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.
Described alkali is one or more inorganic bases that are selected from NaOH, potassium hydroxide, calcium hydroxide, sodium carbonate or sodium acid carbonate.
The concentration of described clorox, acid and aqueous slkali is respectively 2000ppm, 1000ppm and 500ppm.
In the present invention, the grinding particle size of useless pvdf membrane silk is not crucial, just is convenient to its dissolving just passablely, and its film silk granularity generally is 10-0.2mm.Certainly, its film silk granularity also allows above described scope.Pulverizing the equipment that uses is the disintegrating apparatus of selling in the market, also is the disintegrating apparatus that those skilled in the art know.
B) dissolving: with above-mentioned steps a) the useless pvdf membrane silk, pore former and the low molecular weight additives that obtain of preliminary treatment be dissolved in the solvent, obtain spinning solution.
A preferred embodiment of the invention, described solvent are two or more solvent mixtures that is selected from dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone, trimethyl phosphate, triethyl phosphate, oxolane, acetone, tetramethylurea, Methylethyl acetone or dimethyl sulfoxide (DMSO).
In the present invention, described solvent mixture can be the solvent mixture that two or more described solvent mixes with any ratio.In the present invention, described solvent mixture should be appreciated that it is two or more solvent, the product that mixes according to certain rules.Two or more solubility property solvent different with the scope of application (comprising water) mixed resulting solution, because their interaction, can improve its solvability significantly, the advantage of each solvent is not fully exerted, so that more effectively dissolve its pvdf membrane.Certainly, those skilled in the art can select these solvents according to solvent property, useless pvdf membrane silk granularity, treatment facility and various factors such as processing place situation, the security of using solvent and cost, and determine these solvent usage ratios easily, however, these solvent mixtures all should be effective and feasible to dissolving useless pvdf membrane silk.
Preferably, described solvent is two or more solvent mixture that is selected from dimethyl formamide, dimethylacetylamide, oxolane, acetone or N-methyl pyrrolidone.
On meaning of the present invention, described pore former should be appreciated that it is to help Polymer Solution to form the material in hole in the gel solidification process.This pore former should have the character that can be come out by water or clorox rinsing.Therefore except the example of enumerating below, every chemical products with these character can use in the present invention, and some products are all within protection scope of the present invention like this.
A preferred embodiment of the invention, described pore former for example are one or more macromolecule pore formers that are selected from polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol.Described polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol all are product solds in the market, and for example polyvinylpyrrolidone is that sea, Jiaozuo City source Fine Chemical Co., Ltd is with trade name K60 product sold; Polyethylene glycol is that Xiaoshan, Hangzhou three river Fine Chemical Co., Ltd are with trade name PEG600 product sold; Polyvinyl alcohol be in the Suzhou chemical industry Co., Ltd far away with trade name polyvinyl alcohol (specification 1799) product sold.
In the present invention, the concentration of described pore former in spinning solution is 5-30 weight %.
On meaning of the present invention, described low molecular weight additives should be appreciated that it is can help at polymeric membrane surface and the inner material that forms the hole.Similarly, therefore except the example of enumerating below, every chemical products with these character can use in the present invention, and some products are all within protection scope of the present invention like this.
Described low molecular weight additives is one or more additives that are selected from lithium nitrate, calcium nitrate, sodium nitrate, lithium chloride, calcium chloride, sodium chloride, magnesium chloride, ammonium chloride, water, acetone, glycerine, ethylene glycol, ethanol.
Preferably, described low molecular weight additives is one or more additives that are selected from sodium nitrate, lithium chloride, calcium chloride, sodium chloride, ammonium chloride, water, acetone, glycerine, ethylene glycol, ethanol.
In the present invention, the concentration of described low molecular weight additives in spinning solution is 0.1-5 weight %.
Be dissolved in the specific solvent with pore former and micromolecule additive by a certain percentage through pretreated pvdf membrane, make spinning solution.The 5-100 weight % that useless pvdf membrane silk used in the present invention can be the PVDF gross weight, and PVDF is the 10-30 weight % of spinning solution gross weight.
For the solid impurity of avoiding large-size impacts spun film silk, all dry-wet spinning all have the filtration operation one.Introduced filter among the present invention equally, filter is installed between spinning head and the spinning still.Filter screen can be selected the 100-1000 order for use, and filter screen order number can be selected according to the wall thickness of spinning doughnut.
The filter of Shi Yonging for example is that the imperial accurate filter of anti-element (Changshu) Co., Ltd is with commodity stainless steel melt filter product sold by name in the present invention.
After spinning solution prepared, available dry-wet spinning technology was spun into hollow-fibre membrane.
The manufacturer who implements spinning equipment that described dry-wet spinning is used is a Tianjin new three-dimensional films technology Co., Ltd, and its spinning technique flow process as shown in Figure 1.
The spinning solution of above-mentioned preparation is extruded simultaneously by spinning head and the core liquid in the pore of spinning head center, through entering in the outer coagulating bath after one section dried journey.Feed liquid still 2 is equipped with the spinning solution of above-mentioned preparation, and core flow container 3 is equipped with core liquid.Described core liquid is made up of dimethyl formamide, dimethylacetylamide and water, is to prepare after these several materials fully mix.
The spinning solution of above-mentioned preparation enters spinning head 4 under 1 applied pressure of nitrogen steel cylinder, described core liquid enters in the center pore of spinning head.Described spinning solution and described core liquid are extruded through spinning head 4 simultaneously, through entering in the coagulating tank 5 after one section dried journey.Described coagulating bath is made up of dimethyl formamide, dimethylacetylamide and water, is to prepare after these several materials fully mix.
By with the exchange of coagulating bath, the solvent in the described spinning solution enters coagulating bath mutually with pore former, and the non-solvent in the coagulating bath spreads in spinning solution.Polymer in the spinning solution is separated out because of solubility reduces by the phase transfer precipitation, thereby forms the Kynoar hollow-fibre membrane.Made hollow-fibre membrane is wrapped on the wire wrapping wheel 8 through guide wheel 7.Wire wrapping wheel is in rotation process, and the pure water in hollow-fibre membrane and the wrapping wire rinse bath is had an effect and further solidified.
Hollow-fibre membrane will experience a phase transition behavior in forming process, i.e. non-solvent in the coagulating bath and the solvent in the feed liquid and the exchange between the pore former and make the feed liquid gel solidification.In spinning process, this phase transition behavior mainly is to finish with coagulating bath or contacting of core liquid by feed liquid.Contain the non-solvent that can not dissolve Kynoar in coagulating bath or the core liquid, for example water, acetone, glycerine, ethylene glycol, ethanol, methyl alcohol etc.Preferably, described non-solvent is water or alcohols.In order to regulate the gelation rate of feed liquid, can also in core liquid and coagulating bath, add a certain proportion of solvent, for example dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO) etc.
The pure water flux of described hollow-fibre membrane is measured under 20 ℃ of conditions according to People's Republic of China's ocean industry standard " doughnut miillpore filter method of testing HY/T 051-1999 ".
Average pore size is that the model that adopts U.S. Merck ﹠ Co., Inc to produce is that the micropore Structure Analysis instrument (mercury injection apparatus) of 9310 types is measured.
Internal diameter and external diameter are to use the light microscope determining of band scale, and used light microscope is that the XTT that Beijing section instrument electric light instrument plant produces becomes times stereomicroscope.
The testing arrangement of hot strength is the product of the WDT-5 type electronics pulling experiment machine of Shijiazhuang Zhongshi Detection Equipment Co., Ltd.'s sale.The effective length of laboratory sample is 15cm, and draw speed is 100mm/min.
[description of drawings]
Fig. 1 is the spinning technique flow process of PVDF hollow-fibre membrane.
Wherein: 1, nitrogen pressure steel cylinder; 2, feed liquid still; 3, core flow container; 4, spinning head; 5, coagulating tank; 6, hollow-fibre membrane guide wheel; 7, guide wheel; 8, wire wrapping wheel; 9, wrapping wire rinse bath.
[specific embodiment]
Following non-limiting example illustrates in greater detail the present invention.
Embodiment 1:
The PVDF waste silk that produces in the spinning process was soaked 2 hours in the liquor natrii hypochloritis of 5000ppm, use the clear water rinsing clean then.Pulverize film silk oven dry back.Spinning solution is prepared by following proportioning in its gross weight: 20%PVDF (being made up of useless film fully), 5% polypyrrole alkane ketone, 4% polyethylene glycol, 6% polyvinyl alcohol, 1% lithium chloride, 40% dimethylacetylamide, 24% dimethyl formamide.Being dissolved as uniform spinning solution in solvent after, PVDF and various additive use dry-wet spinning.Dried journey is 3 centimetres, and the spinning solution temperature is 80 ℃, and core liquid is adopted as 40% the dimethylacetylamide aqueous solution, and coagulating bath employing weight concentration is 20% the dimethylacetylamide aqueous solution, and coagulation bath temperature is 30 ℃.With the aperture is 200 purpose strainer filtering spinning solutions.The interior external diameter of gained PVDF doughnut is respectively 1.0/2.0mm, and pure water flux is 380L/m2.h.atm, and average pore size is 0.04 micron, and the hot strength of single film silk is 5.9N.
Embodiment 2:
The PVDF waste silk that produces in the spinning process was soaked 1 hour in the liquor natrii hypochloritis of 5000ppm, use the clear water rinsing clean then.Pulverize film silk oven dry back.Spinning solution is prepared by following proportioning in its gross weight: 19%PVDF (being made up of useless film fully), 5% polypyrrole alkane ketone, 5% polyethylene glycol, 6% polyvinyl alcohol, 1% lithium chloride, 40% dimethylacetylamide, 24% dimethyl formamide.Being dissolved as uniform spinning solution in solvent after, PVDF and various additive use dry-wet spinning.Dried journey is 3 centimetres, and the spinning solution temperature is 80 ℃, and core liquid is adopted as 40% the dimethylacetylamide aqueous solution, and coagulating bath employing weight concentration is 20% the dimethylacetylamide aqueous solution, and coagulation bath temperature is 30 ℃.With the aperture is 200 purpose strainer filtering spinning solutions.The interior external diameter of gained PVDF doughnut is respectively 1.0/2.0mm, and pure water flux is 440L/m2.h.atm, and average pore size is 0.05 micron, and the hot strength of single film silk is 5.4N.
Embodiment 3:
The broken film silk of the PVDF that produces in the membrane component process was soaked 2 hours in the liquor natrii hypochloritis of 5000ppm, use the clear water rinsing clean then.Pulverize film silk oven dry back.Spinning solution is prepared by following proportioning in its gross weight: 20%PVDF (40% useless film silk+60%PVDF virgin material), 5% polypyrrole alkane ketone, 4% polyethylene glycol, 6% polyvinyl alcohol, 1% lithium chloride, 40% dimethylacetylamide, 24% dimethyl formamide.It is 3 centimetres that PVDF and various additive are dissolved as in solvent behind the uniform spinning solution with the dry-wet spinning dry-spinning path, the spinning solution temperature is 80 ℃, core liquid employing weight concentration is 40% the dimethylacetylamide aqueous solution, coagulating bath employing weight concentration is 20% the dimethylacetylamide aqueous solution, and coagulation bath temperature is 30 ℃.With the aperture is 200 purpose strainer filtering spinning solutions.The interior external diameter of gained PVDF doughnut is respectively 1.0/2.0mm, and pure water flux is 420L/m2.h.atm, and average pore size is 0.05 micron, and the hot strength of single film silk is 5.8N.
Embodiment 4:
Clean with clear water the pvdf membrane silk surface clean in 1 year of operation in Sewage Plant.The film silk soaked in the liquor natrii hypochloritis of 5000ppm after 4 hours, was that 2 hydrochloric acid and pH value are to soak 20 minutes in 10 the sodium hydroxide solution at pH value successively.The film silk is taken out from sodium hydroxide solution with the thorough rinsing of clear water clean back oven dry and pulverizing.Spinning solution is prepared by following proportioning in its gross weight: 20%PVDF (40% useless film silk+60%PVDF virgin material), 5% polypyrrole alkane ketone, 4% polyethylene glycol, 6% polyvinyl alcohol, 1% lithium chloride, 40% dimethylacetylamide, 24% dimethyl formamide.It is 3 centimetres that PVDF and various additive are dissolved as in solvent behind the uniform spinning solution with the dry-wet spinning dry-spinning path, the spinning solution temperature is 80 ℃, core liquid employing weight concentration is 40% the dimethylacetylamide aqueous solution, coagulating bath employing weight concentration is 60% the dimethylacetylamide aqueous solution, and coagulation bath temperature is 30 ℃.With the aperture is 200 purpose strainer filtering spinning solutions.The interior external diameter of gained PVDF doughnut is respectively 1.0/2.0mm, and pure water flux is 360L/m2.h.atm, and average pore size is 0.06 micron, and the hot strength of single film silk is 6.0N.
Embodiment 5:
Clean with clear water the pvdf membrane silk surface clean in 1 year of operation in Sewage Plant.The film silk soaked in the liquor natrii hypochloritis of 5000ppm after 4 hours, was that 2 hydrochloric acid and pH value are to soak 20 minutes in 10 the sodium hydroxide solution at pH value successively.The film silk is taken out from sodium hydroxide solution with the thorough rinsing of clear water clean back oven dry and pulverizing.Spinning solution is prepared by following proportioning in its gross weight: 19%PVDF (30% useless film silk+70%PVDF virgin material), 5% polypyrrole alkane ketone, 5% polyethylene glycol, 6% polyvinyl alcohol, 1% lithium chloride, 30% dimethylacetylamide, 34% dimethyl formamide.It is 3 centimetres that PVDF and various additive are dissolved as in solvent behind the uniform spinning solution with the dry-wet spinning dry-spinning path, the spinning solution temperature is 80 ℃, core liquid employing weight concentration is 40% the dimethylacetylamide aqueous solution, coagulating bath employing weight concentration is 60% the dimethylacetylamide aqueous solution, and coagulation bath temperature is 30 ℃.With the aperture is 200 purpose strainer filtering spinning solutions.The interior external diameter of gained PVDF doughnut is respectively 1.0/2.0mm, and pure water flux is 400L/m2.h.atm, and average pore size is 0.07 micron, and the hot strength of single film silk is 5.2N.
Claims (9)
1. the recoverying and utilizing method of a Kynoar hollow-fibre membrane is characterized in that this method may further comprise the steps:
A) described useless pvdf membrane silk preliminary treatment;
B) dissolving: with above-mentioned steps a) pretreated useless pvdf membrane silk, pore former and low molecular weight additives be dissolved in the solvent, obtain spinning solution, described low molecular weight additives is to help at polymeric membrane surface and the inner material that forms the hole;
C) solids and impurity in spinning solution filtration: remove by filter at above-mentioned steps b) obtain useless pvdf membrane silk solution;
D) spinning hollow-fibre membrane: with above-mentioned steps c) the useless pvdf membrane silk solution that obtains is made the PVDF hollow-fibre membrane.
2. method according to claim 1, it is characterized in that the preliminary treatment of described useless pvdf membrane silk comprises uses the cleaning agent be selected from clear water, acid, alkali and clorox to soak 12-24 hour, with the thorough rinsing of clear water, under temperature 50-80 ℃, carry out drying then and handle, pulverize again.
3. method according to claim 1 is characterized in that described solvent is the mixture that is selected from two or more solvent of dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone, trimethyl phosphate, triethyl phosphate, oxolane, acetone, tetramethylurea, Methylethyl acetone or dimethyl sulfoxide (DMSO).
4. method according to claim 1, the filter screen aperture of using when it is characterized in that filtering spinning solution is the 100-1000 order.
5. method according to claim 1 is characterized in that the useless pvdf membrane silk solution concentration that obtains in step c) is 10-30 weight %.
6. method according to claim 1 is characterized in that described pore former is one or more macromolecule pore formers that are selected from polyvinylpyrrolidone, polyethylene glycol or polyvinyl alcohol.
7. method according to claim 1 is characterized in that the concentration of described pore former in even spinning solution is 5-30 weight %.
8. method according to claim 1 is characterized in that described low molecular weight additives is one or more additives that are selected from lithium nitrate, calcium nitrate, sodium nitrate, lithium chloride, calcium chloride, sodium chloride, magnesium chloride, ammonium chloride, water, acetone, glycerine, ethylene glycol, ethanol.
9. according to claims 1 described method, it is characterized in that the concentration of described low molecular weight additives in spinning solution is 0.1-5 weight %.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| FR3107661A1 (en) * | 2020-03-02 | 2021-09-03 | Suez Groupe | Process for separating polymeric materials |
| WO2023117971A1 (en) * | 2021-12-23 | 2023-06-29 | Solvay Specialty Polymers Italy S.P.A. | Method for the purification of vinylidene fluoride polymers |
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| WO2012079231A1 (en) * | 2010-12-15 | 2012-06-21 | Rhodia (China) Co., Ltd. | Fluoropolymer compositions |
| CN103282478B (en) * | 2010-12-15 | 2014-12-10 | 罗地亚（中国）投资有限公司 | Fluoropolymer compositions |
| CN102489184B (en) * | 2011-11-28 | 2013-11-20 | 北京碧水源膜科技有限公司 | Polyvinylidene difluoride hollow fiber micro-filtration membrane with permanent hydrophilicity, and preparation method thereof |
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| CN110253789B (en) * | 2019-06-13 | 2023-11-28 | 天津汉晴环保科技有限公司 | PVDF membrane silk waste silk recovery processing system |
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| CN115612169B (en) * | 2022-10-08 | 2024-09-10 | 北京碧水源膜科技有限公司 | Method for recycling PVDF in membrane wire material, application, freeze separation device and application |
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| CN1608718A (en) * | 2003-10-17 | 2005-04-27 | 天津膜天膜工程技术有限公司 | Hollow fiber film and its prepn process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| FR3107661A1 (en) * | 2020-03-02 | 2021-09-03 | Suez Groupe | Process for separating polymeric materials |
| WO2021176175A1 (en) * | 2020-03-02 | 2021-09-10 | Suez Groupe | Method for separating polymeric materials |
| WO2023117971A1 (en) * | 2021-12-23 | 2023-06-29 | Solvay Specialty Polymers Italy S.P.A. | Method for the purification of vinylidene fluoride polymers |
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