JP6259319B2 - Film-forming solution composition for hollow fiber membrane - Google Patents
Film-forming solution composition for hollow fiber membrane Download PDFInfo
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Description
本発明は、中空糸膜用の製膜溶液組成物、前記組成物から得られた中空糸膜とその製造方法に関する。 The present invention relates to a membrane forming solution composition for a hollow fiber membrane, a hollow fiber membrane obtained from the composition, and a method for producing the same.
世界的な水資源の需要増大に対応するため、海水淡水化を目的とする海水淡水化施設の
大型化が求められており、近い将来には造水量が１００万ｍ3／日規模の施設が必要になると予想されている。
特許文献１、２には、高い脱塩能力を有する中空糸型ＮＦ膜の発明が記載されているが、これらの発明もさらなる造水能力の向上の観点からは改善の余地がある。
In order to respond to the worldwide increase in demand for water resources, an increase in the size of the seawater desalination facility for the purpose of seawater desalination has been required, concrete amount of water in the near future is a million m 3 / day scale of the facility Expected to be needed.
Patent Documents 1 and 2 describe inventions of hollow fiber type NF membranes having high desalting ability, but these inventions also have room for improvement from the viewpoint of further improvement of water production capacity.
本発明は、高い造水能力が得られる中空糸膜用として適した製膜溶液組成物、前記組成物から得られる中空糸膜、前記組成物を使用した中空糸膜の製造方法を提供することを課題とする。 The present invention provides a membrane-forming solution composition suitable for a hollow fiber membrane capable of obtaining a high water-forming ability, a hollow fiber membrane obtained from the composition, and a method for producing a hollow fiber membrane using the composition. Is an issue.
本発明は、課題の解決手段として、
（Ａ）スルホン化度が０．１０〜０．１８のスルホン化ポリエーテルスルホン１〜１５質量％、
（Ｂ）ポリエーテルスルホン１０〜２５質量％、
（Ｃ）ポリエチレングリコール１０〜３０質量％、
（Ｄ）残部割合の溶媒を含む中空糸膜用の製膜溶液組成物であって、
（Ａ）成分と（Ｂ）成分の合計量中の含有割合が、（Ａ）成分１５〜５０質量％、（Ｂ）成分８５〜５０質量％である、中空糸膜用の製膜溶液組成物を提供する。
As a means for solving the problems, the present invention
(A) 1-15% by mass of a sulfonated polyethersulfone having a degree of sulfonation of 0.10-0.18,
(B) 10-25% by mass of polyethersulfone,
(C) polyethylene glycol 10-30% by mass,
(D) A membrane-forming solution composition for a hollow fiber membrane containing a remaining proportion of a solvent,
A membrane-forming solution composition for a hollow fiber membrane, wherein the content ratio in the total amount of the component (A) and the component (B) is 15 to 50% by mass of the component (A) and 85 to 50% by mass of the component (B). I will provide a.
本発明は、他の課題の解決手段として、請求項１または２記載の中空糸膜用の製膜溶液組成物から得られた中空糸膜であって、純水透過係数が２００Ｌ／ｍ2・ｈ（０．１ＭＰａ）以上である、中空糸膜を提供する。 The present invention provides a hollow fiber membrane obtained from the membrane-forming solution composition for a hollow fiber membrane according to claim 1 or 2 as a means for solving another problem, wherein the pure water permeability coefficient is 200 L / m 2 · A hollow fiber membrane having h (0.1 MPa) or more is provided.
本発明は、さらに他の課題の解決手段として、請求項１または２記載の中空糸膜用の製膜溶液組成物を使用した中空糸膜の製造方法であって、
製膜溶液組成物を脱泡後、紡糸して中空糸を得る工程と、
紡糸した中空糸を乾燥する工程を有しているものであり、
前記製膜溶液組成物を脱泡後、紡糸する工程において、内部凝固液として水とポリエチレングリコールの混合溶液を使用する、中空糸膜の製造方法を提供する。
The present invention is a method for producing a hollow fiber membrane using the membrane-forming solution composition for a hollow fiber membrane according to claim 1 or 2 as a means for solving another problem,
Defoaming the film-forming solution composition and then spinning to obtain hollow fibers;
It has a step of drying the spun hollow fiber,
Provided is a method for producing a hollow fiber membrane, wherein a mixed solution of water and polyethylene glycol is used as an internal coagulating liquid in the spinning step after defoaming the membrane-forming solution composition.
本発明の製膜溶液組成物から得られた中空糸膜は、高い純水透過係数を有していることから、海水淡水化施設において使用したときは、高い造水能力が得られる。 Since the hollow fiber membrane obtained from the membrane-forming solution composition of the present invention has a high pure water permeability coefficient, when used in a seawater desalination facility, a high water production capacity is obtained.
＜中空糸膜用の製膜溶液組成物＞
［（Ａ）成分］
（Ａ）成分のスルホン化ポリエーテルスルホンは、スルホン化度が０．１０〜０．１８である。スルホン化度が前記範囲内であると、特に純水透過係数を高めることができる。
<Film forming solution composition for hollow fiber membrane>
[(A) component]
The sulfonated polyethersulfone as component (A) has a sulfonation degree of 0.10 to 0.18. When the sulfonation degree is within the above range, the pure water permeability coefficient can be particularly increased.
スルホン化ポリエーテルスルホンは、スルホ基が塩型および酸型のいずれも使用することができる。
スルホン化ポリエーテルスルホンは，例えば特開平０２―２０８３２２号公報、或いは米国特許４５０８８５２明細書に記載の製造方法、特開２０１３−２１５６４０号公報の実施例１〜４に記載の製造方法、特開２０１４−５６８号公報の実施例１〜４に記載の製造方法により製造することができる。
In the sulfonated polyethersulfone, either a salt type or an acid type of the sulfo group can be used.
Sulfonated polyethersulfone is, for example, a production method described in JP-A No. 02-208322 or US Pat. No. 4,508,852, a production method described in Examples 1 to 4 of JP-A-2013-215640, and JP-A-2014. -568 can be produced by the production methods described in Examples 1 to 4.
［（Ｂ）成分］
（Ｂ）成分は、ポリエーテルスルホンであり、重量平均分子量が１万〜１０万のものが好ましい。
（Ａ）成分と（Ｂ）成分が製膜成分となるものである。
[Component (B)]
The component (B) is polyethersulfone, preferably having a weight average molecular weight of 10,000 to 100,000.
The component (A) and the component (B) are film forming components.
［（Ｃ）成分］
（Ｃ）成分は、ポリエチレングリコールであり、（Ａ）および（Ｂ）成分の貧溶媒となるものである。（Ｃ）成分のポリエチレングリコールは、分子量１００〜４００のものが好ましい。
[Component (C)]
The component (C) is polyethylene glycol and serves as a poor solvent for the components (A) and (B). The component (C) polyethylene glycol preferably has a molecular weight of 100 to 400.
［（Ｄ）成分］
（Ｄ）成分の溶媒は、（Ａ）および（Ｂ）成分を溶解できるものであり（良溶媒）、Ｎ−メチル−２−ピロリドン、ジメチルスルホキシド、ジメチルアセトアミド、N、N・ジメチルホルムアミドなどを挙げることができる。
[(D) component]
The solvent of the component (D) can dissolve the components (A) and (B) (good solvent), and includes N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, N, N · dimethylformamide, and the like. be able to.
なお、本発明の組成物は、上記成分以外にも、少量の塩化リチウム、硝酸リチウムなどを含有することもできる。 In addition, the composition of this invention can also contain a small amount of lithium chloride, lithium nitrate, etc. besides the said component.
［各成分の含有割合］
組成物中の各成分の含有割合は、次のとおりである。
（Ａ）成分は、１〜１５質量％、好ましくは３〜１２質量％、より好ましくは５〜１０質量％であり、
（Ｂ）成分は、１０〜２５質量％、好ましくは１０〜２３質量％、より好ましくは１３〜２０質量％であり、
（Ｃ）成分は、１０〜３０質量％、好ましくは１３〜２５質量％、より好ましくは１５〜２５質量％であり、
（Ｄ）成分は、（Ａ）〜（Ｄ）成分で合計１００質量％となる残部割合である。
各成分を上記含有割合にすることで、特に純水透過係数を高めることができる。
[Content ratio of each component]
The content ratio of each component in the composition is as follows.
(A) component is 1-15 mass%, Preferably it is 3-12 mass%, More preferably, it is 5-10 mass%,
(B) component is 10-25 mass%, Preferably it is 10-23 mass%, More preferably, it is 13-20 mass%,
(C) component is 10-30 mass%, Preferably it is 13-25 mass%, More preferably, it is 15-25 mass%,
(D) component is a remainder ratio which becomes a total of 100 mass% with (A)-(D) component.
By making each component into the said content rate, a pure water permeability coefficient can be raised especially.
（Ａ）成分と（Ｂ）成分の合計量中の含有割合は、
（Ａ）成分は１５〜５０質量％、好ましくは１５〜４０質量％、より好ましくは１５〜３５質量％であり、
（Ｂ）成分は、８５〜５０質量％、好ましくは８５〜６０質量％、より好ましくは８５〜６５質量％である。
（Ａ）成分と（Ｂ）成分の割合が前記範囲内であると、特に純水透過係数を高めることができる。また、低ファウリング性、耐アルカリ性及び耐熱性も高めることができる。
The content ratio in the total amount of the component (A) and the component (B) is
(A) A component is 15-50 mass%, Preferably it is 15-40 mass%, More preferably, it is 15-35 mass%,
(B) A component is 85-50 mass%, Preferably it is 85-60 mass%, More preferably, it is 85-65 mass%.
When the ratio of the component (A) to the component (B) is within the above range, the pure water permeability coefficient can be particularly increased. Moreover, low fouling property, alkali resistance, and heat resistance can also be improved.
本発明の製膜溶液組成物の製造方法は、（Ｃ）成分と（Ｄ）成分からなる混合溶媒に対して、（Ａ）成分と（Ｂ）成分を一緒に添加溶解させる方法、（Ｃ）成分と（Ｄ）成分からなる混合溶媒に対して、先に（Ａ）成分を添加溶解させた後、（Ｂ）成分を添加溶解させる方法などを適用することができる。 The method for producing a film-forming solution composition of the present invention is a method in which (A) component and (B) component are added and dissolved together in a mixed solvent comprising component (C) and component (D), (C) A method of adding and dissolving the component (B) after adding and dissolving the component (A) in the mixed solvent composed of the component and the component (D) can be applied.
＜中空糸膜とその製造方法＞
本発明の中空糸膜は、上記した中空糸膜用の製膜溶液組成物を使用して製造する。以下、工程順に説明する。
最初に上記した中空糸膜用の製膜溶液組成物を用意する。
<Hollow fiber membrane and its manufacturing method>
The hollow fiber membrane of the present invention is produced using the above-described membrane-forming solution composition for a hollow fiber membrane. Hereinafter, it demonstrates in order of a process.
First, the membrane forming solution composition for the hollow fiber membrane described above is prepared.
次に、前記製膜溶液組成物を脱泡した後、紡糸して中空糸膜を得る。
紡糸は二重紡糸ノズルの外周部から製膜溶液を吐出させると同時に、中央孔からは製膜成分の非溶媒（内部凝固液）を吐出させる。
内部凝固液は、水とポリエチレングリコールの混合溶液を使用する。
水とポリエチレングリコールの混合溶液中の含有割合は、水４０〜６０質量％が好ましく、より好ましくは４５〜５５質量％、ポリエチレングリコール６０〜４０質量％が好ましく、より好ましくは５５〜４５質量％である。
内部凝固液の温度は１０〜５０℃が好ましく、２０〜４０℃がより好ましい。
Next, after defoaming the membrane-forming solution composition, spinning is performed to obtain a hollow fiber membrane.
In spinning, a film forming solution is discharged from the outer peripheral portion of the double spinning nozzle, and at the same time, a non-solvent (internal coagulation liquid) as a film forming component is discharged from the central hole.
As the internal coagulation liquid, a mixed solution of water and polyethylene glycol is used.
The content ratio in the mixed solution of water and polyethylene glycol is preferably 40 to 60% by mass of water, more preferably 45 to 55% by mass, and preferably 60 to 40% by mass of polyethylene glycol, more preferably 55 to 45% by mass. is there.
The temperature of the internal coagulating liquid is preferably 10 to 50 ° C, more preferably 20 to 40 ° C.
その後、紡糸した中空糸を二重紡糸ノズルから乾燥空間を通して凝固槽まで導いて凝固させ、中空糸膜を得る。
乾燥空間の温度は、５０〜９０℃が好ましい。
乾燥空間の距離は、１０〜１５０ｍｍが好ましい。
凝固槽中の凝固液は水を用いることができ、凝固槽の温度（凝固浴の温度）は５０〜９０℃が好ましい。
Thereafter, the spun hollow fiber is guided from the double spinning nozzle to the coagulation tank through the drying space and solidified to obtain a hollow fiber membrane.
The temperature of the drying space is preferably 50 to 90 ° C.
The distance of the drying space is preferably 10 to 150 mm.
Water can be used as the coagulation liquid in the coagulation tank, and the temperature of the coagulation tank (the temperature of the coagulation bath) is preferably 50 to 90 ° C.
本発明の中空糸膜用の製膜溶液組成物から得られた中空糸膜は、純水透過係数が２００Ｌ／ｍ2・ｈ（0.1MPa）以上のものであり、好ましくは５００Ｌ／ｍ2・ｈ（0.1MPa）以上のものである。 The hollow fiber membrane obtained from the membrane-forming solution composition for the hollow fiber membrane of the present invention has a pure water permeability coefficient of 200 L / m 2 · h (0.1 MPa) or more, preferably 500 L / m 2 · h (0.1 MPa) or more.
本発明の中空糸膜は、純水透過係数が高いものであることから、逆浸透膜と組み合わせる限外濾過膜として海水淡水化施設に使用することで、高い造水能力を発揮することができる。 Since the hollow fiber membrane of the present invention has a high pure water permeation coefficient, it can exhibit high water production capacity when used in a seawater desalination facility as an ultrafiltration membrane combined with a reverse osmosis membrane. .
（１）純水透過係数（PWP）
試験用中空糸膜の一端側を閉じた状態で、他端側から純水を０．１ＭＰａで供給し、中空糸膜から一定時間に透過する純水の容量を測定した。この容量を採取時間（ｈ）、中空糸膜内表面の膜面積（ｍ2）で除して、純水透過係数〔Ｌ／ｍ2・ｈ（０．１ＭＰａ）〕を求めた。
(1) Pure water permeability coefficient (PWP )
In the closed state of the one end of the test for the hollow fiber membrane, pure water is supplied at 0.1MPa from the other end was measured volume of pure water which passes through a predetermined time from the hollow fiber membrane. This volume was divided by the sampling time (h) and the membrane area (m 2 ) on the inner surface of the hollow fiber membrane to obtain a pure water permeability coefficient [L / m 2 · h (0.1 MPa)].
（２）スルホン化度（置換度）
精製、乾燥後のスルホン化ポリエーテルスルホンを重水素化ジメチルスルホキシドに溶解し、600MHz H-NMR（BRUKER AVANCE 600）より測定した。1H- NMRスペクトルで得られた芳香環水素のピーク積分値及び下記式より、スルホン化度（置換度）を算出した。
スルホン化度（置換度）
=[8.2〜8.5ppmの積分値(下記化学式中の(1))]/{([6.8〜8.2ppmの積分値(下記化学式中の(2)〜(5))]-[8.2〜8.5ppmの積分値]×2)/4+[8.2〜8.5ppmの積分値]｝
(2) Sulfonation degree (substitution degree)
The sulfonated polyethersulfone after purification and drying was dissolved in deuterated dimethylsulfoxide and measured by 600 MHz H-NMR (BRUKER AVANCE 600). The degree of sulfonation (degree of substitution) was calculated from the peak integrated value of the aromatic ring hydrogen obtained from the 1H-NMR spectrum and the following formula.
Sulfonation degree (substitution degree)
= [Integral value of 8.2 to 8.5 ppm ((1) in the following chemical formula)] / {([Integrated value of 6.8 to 8.2 ppm ((2) to (5) in the chemical formula below)]-[8.2 to 8.5 ppm Integral value] × 2) / 4 + [integral value of 8.2 to 8.5 ppm]}
（Ａ）成分のスルホン化ポリエーテルスルホン（SPES）
実施例１、２の塩型のＳＰＥＳは、特開２０１３−２１５６４０号公報の実施例３に準じて製造した。
実施例３、４、比較例１、２の酸型のＳＰＥＳは、特開２０１３−２１５６４０号公報の実施例１に準じて製造した。
（Ｂ）成分のポリエーテルスルホン（PES）
住友化学（株）製の住化エクセル５２００Ｐ（MW30,000）を使用した。
(A) Component sulfonated polyethersulfone (SPES)
The salt-type SPES of Examples 1 and 2 was produced according to Example 3 of JP2013-215640A.
The acid-type SPES of Examples 3 and 4 and Comparative Examples 1 and 2 were produced according to Example 1 of JP2013-215640A.
(B) Component polyethersulfone (PES)
Sumika Excel 5200P (MW30,000) manufactured by Sumitomo Chemical Co., Ltd. was used.
実施例および比較例
＜製膜容積組成物＞
表１に示すジメチルスルホキシド（DMSO）、ポリエチレングリコール（PEG；MW 200）からなる溶媒に対して、スルホン化ポリエーテルスルホン（SPES）を加え、９０℃で約１時間加熱して溶解させた。
次に、前記溶液にポリエーテルスルホン（PES）を加え、９０℃で約５時間加熱して溶解して、製膜溶液組成物を得た。
Examples and Comparative Examples <Film Formation Volume Composition>
To a solvent composed of dimethyl sulfoxide (DMSO) and polyethylene glycol (PEG; MW 200) shown in Table 1, sulfonated polyethersulfone (SPES) was added and heated to dissolve at 90 ° C. for about 1 hour.
Next, polyethersulfone (PES) was added to the solution and dissolved by heating at 90 ° C. for about 5 hours to obtain a film forming solution composition.
＜中空糸膜の製造＞
上記の製膜溶液組成物を８０℃で１５時間かけて脱泡した。
脱泡した製膜溶液組成物を用い、二重紡糸ノズルにより６０℃で紡糸した。内部凝固液として、ＰＥＧ（MW 200）と水との混合液を使用した。
二重紡糸ノズルから吐出させた後、距離１００ｍｍの乾燥空間（７０℃）を通して乾燥させ、７０℃の水が入った凝固槽を通過させた。
その後、さらに５０℃の水が入った水洗槽を通過させて中空糸膜を巻き取った。
<Manufacture of hollow fiber membrane>
The film forming solution composition was degassed at 80 ° C. for 15 hours.
Using the defoamed membrane-forming solution composition, spinning was performed at 60 ° C. with a double spinning nozzle. As the internal coagulation liquid, a mixed liquid of PEG (MW 200) and water was used.
After discharging from the double spinning nozzle, it was dried through a drying space (70 ° C.) at a distance of 100 mm, and passed through a coagulation tank containing 70 ° C. water.
Then, the hollow fiber membrane was wound up by passing through a washing tank containing 50 ° C. water.
実施例と比較例から明らかなとおり、製膜成分は同じであっても、製膜溶液組成物としてポリエチレングリコールを含有していることによって、高い純水透過係数を得ることができた。 As is apparent from the examples and comparative examples, even if the film forming components were the same, a high pure water permeability coefficient could be obtained by containing polyethylene glycol as the film forming solution composition.
Claims (2)
（Ｂ）ポリエーテルスルホン１０〜２５質量％、
（Ｃ）分子量２００〜４００のポリエチレングリコール１０〜３０質量％、
（Ｄ）残部割合の溶媒を含む中空糸膜用の製膜溶液組成物であって、
（Ａ）成分と（Ｂ）成分の合計量中の含有割合が、（Ａ）成分１５〜３５質量％、（Ｂ）成分８５〜６５質量％である、中空糸膜用の製膜溶液組成物。 (A) 1-15% by mass of a sulfonated polyethersulfone having a degree of sulfonation of 0.10-0.18,
(B) 10-25% by mass of polyethersulfone,
(C) 10 to 30% by mass of polyethylene glycol having a molecular weight of 200 to 400 ,
(D) A membrane-forming solution composition for a hollow fiber membrane containing a remaining proportion of a solvent,
A membrane-forming solution composition for a hollow fiber membrane, wherein the content ratio in the total amount of the component (A) and the component (B) is 15 to 35 % by mass of the component (A) and 85 to 65 % by mass of the component (B). .
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