CN115461136A - 防污且半透的膜 - Google Patents
防污且半透的膜 Download PDFInfo
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- CN115461136A CN115461136A CN202080096426.5A CN202080096426A CN115461136A CN 115461136 A CN115461136 A CN 115461136A CN 202080096426 A CN202080096426 A CN 202080096426A CN 115461136 A CN115461136 A CN 115461136A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及一种防污半透膜,所述防污半透膜包括多孔支撑层、形成在所述支撑层的表面上的薄膜复合(TFC)层和形成在所述TFC层的顶部上的交联聚乙烯醇(PVA)层,其中所述交联PVA层是PVA和交联剂的反应产物,所述交联剂是包括三个或更多个酸基团或其前体的多元酸。所获得的膜示出高水通量和低粗糙度,适合于显著用于具有污染膜倾向的进料溶液的有效膜。
Description
技术领域
本公开涉及一种防污且半透的膜并且更特别地涉及一种防污半透膜,该防污半透膜包括多孔支撑层、形成在该支撑层的表面上的薄膜复合(TFC)层和形成在该TFC层的顶部上的交联聚乙烯醇(PVA)层。此外,本发明涉及包括防污且半透的膜的模块以及这些模块用于处理源自液体食品的流如乳清、咖啡提取物、果汁、椰奶等的用途。
背景技术
反渗透(RO)通常用于处理包含溶解盐的水。应用反渗透技术的实例是使用海水或半咸水生产脱盐饮用水。近年来,正渗透(FO)变得越来越流行。在正渗透设备中,进料通常被脱水以浓缩进料流,而汲取溶液被迁移穿过膜的水稀释。
对于RO膜以及FO膜,在使用一段时间后,膜表面上的沉积物变得明显。这种现象通常被称为污染,并且通常导致膜性能下降。
聚乙烯醇(PVA)已在US2005077243(A1)中用作涂层以防止或延迟污染在反渗透膜上的沉积。PVA涂层由水可溶胀但不溶于水的聚合物制备。由于聚合物不溶于水,所以涂层沉积后不需要交联。应用PVA层使表面平滑并减少颗粒物沉积的倾向。
US6413425 BA公开了一种RO膜,包括支撑膜和聚酰胺薄膜复合(TFC)层。分离层的表面涂有PVA(平均聚合度n=2,600)层以减小比表面积,从而降低污染倾向。PVA在25℃时不溶于水,但在80℃时可溶于水,并且具有的皂化度在99%至100%的范围内。反渗透复合膜具有高污染耐受性,并允许在相对低的压力下实际脱盐。
US2010224555(A1)公开了一种纳米复合膜,其包括具有聚合物基质与设置在该聚合物基质内的纳米颗粒的PVA膜。可以使膜与包含交联剂(例如二醛和二元酸)和催化剂(例如,2.4wt%乙酸)的溶液接触(例如,从PVA侧)约1秒。然后可以在烘箱中以预定温度将膜加热预定时间段。PVA溶液中的各种交联剂(戊二醛、PVA-戊二醛混合物、多聚甲醛、甲醛、乙二醛)和添加剂(甲醛、乙醇、四氢呋喃、氯化锰和环己烷)可用于制备在现有膜上流延的PVA膜,结合对制备的PVA膜进行热处理以改变膜特性。US2010320143(A1)和US2011027599(A1)公开了一种将纳米颗粒封闭在PVA层中的类似技术。
US2010178489(A1)公开了一种复合半透膜,其具有包括聚酰胺树脂的表层和支撑该表层的多孔支撑物。表层可以涂有包含银基抗菌剂和PVA的抗菌层。为了将PVA层附着到表层的基于聚酰胺的树脂上,聚乙烯醇可以交联。聚乙烯醇的交联包括在表层上形成抗菌层,以及然后将抗菌层浸入包含用盐酸酸化的戊二醛的溶液中。
现有技术中建议的PVA层可由于由PVA层提供的增加的平滑度而降低膜的污染倾向。然而,膜上的附加层也有降低水通量的倾向。本发明旨在保持高表面平滑度以防止或减少进料中颗粒物的沉积,而同时获得更高的水通量。
发明内容
本发明涉及防污半透膜,所述防污半透膜包括多孔支撑层、形成在所述支撑层的表面上的薄膜复合(TFC)层和形成在所述TFC层的顶部上的交联聚乙烯醇(PVA)层,其中所述交联PVA层是PVA和交联剂的反应产物,所述交联剂是包括三个或更多个酸基团或其前体的多元酸。
现有技术的交联剂集中于将PVA层附着到膜的TFC层以确保膜的长寿命。本发明建议使用包括三个或更多个酸基团或其前体的多元酸作为交联剂以打开PVA层的结构,而同时保持或甚至增加表面平滑度。PVA层的打开结构允许增加水的渗透,以及因此将对水通量的速率限制较少。增加的平滑度降低了膜的污染倾向。
在本发明的防污且半透的膜中使用的多孔支撑层是多孔基底,例如基本上不抑制水渗透的纳米多孔或微多孔层。在一些情况下,多孔支撑层可以通过流延在例如由聚酯纤维形成的织造或非织造片材上来进一步增强。多孔支撑层通常由聚醚砜(PES)、聚砜(PS)、聚苯砜、聚醚酰亚胺、聚乙烯吡咯烷酮和聚丙烯腈(包括其共混物和混合物)制备。在本发明的实施方式中,多孔支撑膜由包含溶解在溶剂中的聚合物的涂料制备。在将涂料流延成所需厚度的层后,通过在非溶剂如水中淬灭进行转相。
多孔支撑层通过在其面上例如通过界面聚合来形成薄膜复合(TFC)层来改性。TFC层可以使用水性溶液中的胺反应物,优选芳族胺,诸如二胺或三胺,例如1,3-二氨基苯(间苯二胺-MPD)和溶解在有机溶剂中的酰卤反应物,诸如二酰氯或三酰氯,优选芳族酰卤,例如苯-1,3,5-三羰基氯(TMC)来制备,其中所述反应物在界面聚合反应中组合。
在本发明的某个实施方式中,TFC层包括纳米多孔水通道,诸如水通道蛋白水通道。纳米多孔水通道理想地具有仅允许水渗透的配置。然而,实际上也有较少量回流的溶质从进料溶液渗透TFC层,到达汲取溶液或渗透物。纳米多孔水通道减少或消除了所有或大部分其他溶质从进料溶液中的重吸收。优选的是,TFC层包括水通道蛋白水通道,由于其高度选择性,这些水通道仅允许水分子通过。水通道蛋白水通道可以在引入到TFC层之前稳定。
囊泡是水通道蛋白水通道的自然环境,并且囊泡可以由许多不同的囊泡形成材料(包括天然存在的磷脂)形成。适当地,稳定的水通道蛋白可以呈在水通道蛋白蛋白质制剂存在下通过两亲性基质形成化合物的自组装形成的囊泡的形式,如WO2018/141985或WO18087289中公开的。替代地,水通道蛋白水通道可以通过PEI(聚乙烯亚胺)来稳定,如WO2017137361 A1中公开的。使用这些稳定的水通道蛋白水通道制备的膜已被证明是稳健的,具有高水输送能力和离子的低反向通量。在本发明的某个实施方式中,水通道蛋白水通道存在于囊泡中。
适当地,囊泡是由一种或多种聚合物制备的聚合物囊泡。聚合物囊泡可以承受相对高的压力,使其适合于反渗透过程。聚合物囊泡的聚合物可以适当地选择为PMOXA-PDMS二嵌段共聚物(聚(2-甲基噁唑啉)-嵌段-聚(二甲基硅氧烷)二嵌段共聚物),以形成具有跨膜蛋白(诸如水通道蛋白水通道)的自组装囊泡。然后这些囊泡可用于生产其中引入或固定化了跨膜蛋白并对于允许水分子通过膜为活性的TFC层。例如,为了生产包括水通道蛋白水通道的膜,可以将囊泡添加到包括芳族胺,诸如二胺或三胺,例如1,3-二氨基苯(MPD)的水性液体组合物中,施加到多孔支撑膜的表面,其当与酰卤在有机溶剂中的溶液接触时,将参与界面聚合反应,在所述支撑物上形成薄膜复合层,从而形成其中所述囊泡已固定化或引入的分离膜。
在某个方面,囊泡的PMOXAa-b-PDMSc-d选自由PMOXA10-40-PDMS25-70及其混合物组成的组。为了增加囊泡的稳健性,可以优选使用至少包括通式PMOXA10-28-PDMS25-70的第一两亲性二嵌段共聚物和通式PMOXA28-40-PDMS25-70的第二两亲性二嵌段共聚物的混合物。第一和第二两亲性二嵌段共聚物之间的重量比例通常在0.1:1至1:0.1的范围内。液体组合物中两亲性二嵌段共聚物的浓度一般在0.1至50mg/ml,诸如0.5至20mg/ml,以及优选1至10mg/ml的范围内。
囊泡的反应性端基官能化的PDMSe-f(反应性端基官能化的聚(二甲基硅氧烷))通常以包括囊泡的液体组合物的约0.05%至约1%v/v的浓度存在。反应性端基官能化的PDMSe-f可以被胺、羧酸和/或羟基基团中的一种、两种或更多种官能化。适当地,整数e选自20至40的范围,诸如30,并且整数f选自40至80的范围,诸如50。在本发明的某个方面,反应性端基官能化的PDMSe-f是双(氨基烷基)、双(羟烷基)或双(羧酸烷基)封端的PDMSe-f,诸如聚(二甲基硅氧烷)、双(3-氨基丙基)或聚(二甲基硅氧烷)、双(3-羟丙基)。此外,反应性端基官能化的PDMSe-f可选自由H2N-PDMS30-50、HOOC-PDMS30-50和HO-PDMS30-50及其混合物组成的组。所述末端官能化的PDMSe-f(其中e-f代表30至50的范围)的实例是具有以下在此所示式的双(氨基丙基)封端的聚(二甲基硅氧烷),其中(CAS号106214-84-0,Aldrich产品号481246,平均Mn~5,600或CAS号106214-84-0,产品号481696Aldrich,平均Mn~27,000:
以及具有以下在此所示式的双(羟烷基)封端的聚(二甲基硅氧烷),其中n为约30至50,并且m和p均为2和5之间的整数,诸如3或4,(CAS号156327-07-0,Aldrich产品号481246,平均Mn~5,600):
囊泡可进一步包含约1%v/v至约12%v/v的PMOXAa-b-PDMSc-d-PMOXAa-b型的三嵌段共聚物以增加其完整性。通常,所述囊泡包括约8%v/v至约12%v/v的PMOXAa-b-PDMSc-d-PMOXAa-b型的三嵌段共聚物。PMOXAa-b-PDMSc-d-PMOXAa-b型的三嵌段共聚物通常选自PMOXA10-20-PDMS25-70-PMOXA10-20。
本发明的液体制剂中的囊泡可进一步包括通量改善剂以增加水通量或降低反向盐通量或两者。通量改善剂可选自一大组化合物,但通常优选为亚烷基二醇单烷基醚烷基化物(alkylene glycol monoalkyl ether alkylat)、β环糊精或聚乙二醇(15)-羟基硬脂酸酯。通量增加剂通常以液体组合物的按重量计0.1%至1%的量存在。
不希望受任何特定理论的束缚,据信在表面上包含游离的可用反应性基团的囊泡将不仅物理引入或固定化(吸附)在,而且此外化学结合在TFC层中,因为反应性游离端基诸如氨基基团、羟基基团和羧基基团将参与与酰氯诸如均苯三甲酰氯(TMC)的界面聚合反应。以这种方式,据信囊泡将共价结合在TFC层中,导致相对较高的囊泡负载量,并且因此通过膜的水通量较高。此外,据信当引入到选择性膜层中时,TFC层中囊泡的共价偶联导致水通道蛋白水通道和包含水通道蛋白水通道的囊泡的更高的稳定性和/或寿命。
聚乙烯醇(PVA)通常由聚(乙酸乙烯酯)制备。聚(乙酸乙烯酯)的聚合度通常为100至5000。聚(乙酸乙烯酯)的酯基团易于碱水解,其将聚(乙酸乙烯酯)转化为聚乙烯醇和乙酸。该过程在本文中称为水解,但在现有技术中也可称为皂化。
在本发明的某个实施方式中,PVA衍生自聚乙酸乙烯酯的水解,聚乙酸乙烯酯的水解度为90%至99.9%。优选地,水解度在95%至99.5%之间,诸如98.0至99.0%。因此,PVA聚合物实际上是乙烯醇与少比例的乙酸乙烯酯共聚单体的共聚物。
聚合度通常以粘度测量,因为粘度随着聚合度的增加而增加。在某个方面,在20℃下作为4%水性溶液测量的PVA的粘度在20和80mPa·s之间。在优选实施方式中,聚合度适当地在50和70mPa·s之间以获得高水通量。聚乙烯醇可以从各种供应商获得,但目前从Kuraray Poval获得。合适的等级包括完全水解的等级,即98至99mol-%的水解物,具有约30或约60mPa·s的粘度。
PVA聚合物可以利用化学剂诸如醛和酸以及紫外线照射交联。根据本发明,使用多元酸,即具有三个或更多个酸基团或这样的酸基团的前体的化合物。酸基团的前体基团包括例如醛(-CHO)、酰卤(-COOX,其中X为Cl、Br或I)和羧酸的碱金属盐(-COOM,其中M为Li、Na或K)。通常,优选脂肪族交联剂,即使在一些情况下也可以使用芳族交联剂如均苯三甲酸。适当地,多元酸选自由柠檬酸、1,2,3,4-丁烷四羧酸、2,3,5-己烷三羧酸和1,2,3-丁烷三羧酸组成的组。在优选的方面,多元酸是柠檬酸。柠檬酸具有高的生物耐受性,并且因此可以毫无保留地用于制备食品。因此,使用柠檬酸作为交联剂生产的膜通常被认为具有更广泛的应用领域,其还包括食品处理。
多元酸的量通常被调节为可用于在PVA聚合物上反应的羟基基团的量。因此,在某个实施方式中,调节多元酸的量使得PVA聚合物上的至少40%的羟基基团可以反应。在本发明的优选方面,多元酸的量为PVA聚合物上羟基基团的至少60%,诸如至少80%。在优选实施方式中,调节多元酸的量使得约100%的可用羟基基团可以与多元酸的酸基团反应。
多孔支撑膜可以是中空纤维膜或平板膜。目前,平板膜适用于并可能用于生产各种模块,如板框模块或螺旋卷式模块。
本发明还涉及一种制备防污半透膜的方法,该方法包括以下步骤:
提供包括多孔支撑层的半透膜,所述多孔支撑层具有形成在其表面上的薄膜复合(TFC)层,
将聚乙烯醇和交联剂的水性PVA混合物的层施加到所述膜的所述TFC层表面,以及
使所述混合物反应,
其中所述交联剂是具有三个或更多个酸基团或其前体的多元酸。
虽然水性混合物可以在不进行预处理下施加到半透膜,但合适的是,在施加水性PVA混合物之前用甘油水性溶液处理包括支撑层的半透膜,该支撑层具有形成在其表面上的薄膜复合层。可以在施加水性PVA混合物之前将甘油水性溶液施加到多孔侧、TFC层侧或两者,但通常在施加水性PVA混合物之前仅将甘油溶液施加到TFC膜的支撑层表面。将水性甘油溶液施加到膜的多孔侧仅允许生产更能耐受例如甘油浓度的变化和水通量变化较小。
适当地,甘油溶液中甘油的浓度可以在5%和50%之间,诸如10至40。通常,优选的是甘油溶液中甘油的浓度为按重量计13%至按重量计80%。
可以使用多种方法将水性PVA混合物施加到TFC膜上,包括浇注和喷涂。在优选方法中,为了获得更高的水通量,通过喷涂将水性PVA混合物施加到TFC膜上。
通常,多元酸选自由柠檬酸、1,2,3,4-丁烷四羧酸、2,3,5-己烷三羧酸和1,2,3-丁烷三羧酸组成的组。在某个方面,多元酸是柠檬酸。多元交联剂被认为打开了PVA层的结构,从而增加了水通量。
在某个实施方式中,多元酸的按重量计的浓度等于或高于水性PVA混合物中PVA的按重量计的浓度。优选地,柠檬酸的按重量计的浓度是水性混合物中PVA的浓度的至少两倍。
向水性PVA混合物中添加多元酸出人意料地导致当膜用PVA层涂覆时平均粗糙度降低。此外,当将多元酸添加到PVA溶液中时,接触角和ζ电位显著降低。低表面粗糙度和低ζ电位通常被认为改善膜的防污特性。当柠檬酸添加到PVA溶液中时,表面电荷趋于中性这一事实也被认为改善防污性能。
实施例
实施例1.1:生产支撑膜
将17%聚砜(Solvay P3500 MB7 LCD)溶解在从TACT Chemie获得的83%DMF(N,N-二甲基甲酰胺)中来制备涂料。将涂料在45℃的密闭容器中以90rpm的混合速度混合8小时以获得均匀的粘度。
使用230μm的流延间隙,将涂料以辊衬刀(knife over roll)流延模式流延在从Mitsubishi获得的非织造聚酯片材(型号PMB-SKC)上。在暴露时间1.9s后,通过在13℃的水中淬灭16s来进行转相。随后,将支撑膜在60℃的水中洗涤120s。获得约130μm的厚度。
实施例1.2:生产水通道蛋白水通道
来自粳稻(Oryza sativa Japonica)(日本水稻)的组氨酸标记的水通道蛋白在大肠杆菌中的表达及其使用固定化金属亲和色谱法(IMAC)纯化
使用Geneart(Thermo Fischer Scientific的子公司)的服务对来自粳稻的编码水通道蛋白的基因(UNIPROT:A3C132)进行密码子优化,以改善大肠杆菌中的表达。通过在C末端添加十个组氨酸编码密码子以及分别在N末端和C末端添加侧翼NdeI/XhoI限制性位点来合成所得基因(基因ID:aquaporin_Oryza_sativa_Japonica)。合成的基因片段用NdeI/XhoI限制酶消化并连接到NdeI/XhoI消化和纯化的载体pUP1909片段。将得到的连接混合物转化到大肠杆菌DH10B中,并在具有卡那霉素的LB琼脂板上选择卡那霉素抗性转化子。通过遗传构建体的测序确认转化子。随后将分离的载体DNA转移到生产宿主大肠杆菌BL21中。
为了在大肠杆菌中异源表达水通道蛋白,使生产宿主在由以下组成的基本培养基中生长:30g/L甘油、6g/L(NH4)2HPO4、3g/L KH2PO4、5g/L NaCl、0.25g/L MgSO4·7H2O、0.4g/L柠檬酸Fe(III)和1mL/L无菌过滤痕量金属溶液。痕量金属溶液由以下组成:1g/LEDTA、0.8g/L CoCl2·6H2O、1.5MnCl2·4H2O、0.4g/L CuCl2·2H2O、0.4g/L H3BO3、0.8g/LNa2MoO4·2H2O、1.3g/L Zn(CH3COO)2·2H2O。接种和过夜生长后,添加附加的0.25g/LMgSO4·7H2O。
大肠杆菌在具有ez-Control的3L Applikon生物反应器中在分批发酵过程中培养。通过在约30的光密度(OD 600nm)下添加IPTG至0.5mM的最终浓度来诱导蛋白质产生。将培养物诱导约24小时,并在5300g下离心20min收获细菌细胞。
将包括大肠杆菌细胞的沉淀重悬于缓冲液(蛋白酶抑制剂PMSF和EDTA的水性溶液)中,并在Stansted nm-GEN 7575匀化器中在1000巴下均化。温度保持在约10-15℃。将混合物以5300g的最大速度离心30分钟。沉淀包含膜蛋白,并且弃去上清液。
将沉淀重悬于0.9%氯化钠溶液中以获得约50mg/ml的总蛋白质浓度。通过将28LTRIS结合缓冲液和4.5升5%正月桂基二甲胺N-氧化物(LDAO)添加到5L重悬的沉淀材料中来溶解膜蛋白。在室温和温和搅拌下,使混合物温育2至24小时。
在溶解过程之后,将混合物在2L容器中以5300g离心90分钟。回收上清液并通过添加稀释缓冲液将LDAO浓度调节至0.2%。
溶解和澄清后,将蛋白质使用IMAC捕获并在包含1000mM咪唑和0.2%w/v LDAO的洗脱缓冲液中洗脱。洗脱部分通过SDS Page分析,并且仅显示在27kDa处迁移的单个主要带,这对应于来自日本水稻的水通道蛋白的大小。此外,通过与来自用空载体转化的大肠杆菌的阴性对照纯化进行比较,证实了该结果。阴性对照导致没有纯化的蛋白质。使用对组氨酸标签特异性的抗体(TaKaRa Bio)进行的蛋白质印迹分析如预期的那样导致来自纯化的蛋白质的清晰信号以及没有来自阴性对照的信号,证实纯化的蛋白质的来源为组氨酸标记的膜蛋白。
通过添加包含2%LDAO的冰冷无咪唑缓冲液将蛋白质浓度调节至5mg/ml,制备储备溶液。最后,将水通道蛋白储备溶液通过0.45μM灭菌杯过滤灭菌,并在4℃冰箱中储存用于在一个月内使用,或者在-80℃冰柜中储存。
实施例1.3:生产水通道蛋白制剂
1.通过将5g KHS溶解在1l PBS(通过将8g NaCl、0.2g KCl、1.44g Na2HPO4和0.24g KH2PO4溶解在800mL MiliQ纯化H2O中,用HCl将pH调节至7.2并完成体积至1L来制备)中来制备按重量计0.5%的HS 15(聚乙二醇(15)-羟基硬脂酸酯)(KHS)溶液。
2.通过将0.05g LDAO溶解在100mL PBS中来制备PBS中按重量计0.05%的LDAO溶液。
3.在制备容器中,称取0.5g聚(2-甲基噁唑啉)-嵌段-聚(二甲基硅氧烷)二嵌段共聚物(PDMS65PMOXA24)/升制备的制剂。
4.在同一制备容器中,称取聚(2-甲基噁唑啉)-嵌段-聚(二甲基硅氧烷)二嵌段共聚物(PDMS65PMOXA32),以达到0.5g/L制备的制剂(PDMS65PMOXA24和PDMS65PMOXA32的重量比为1:1)的浓度。
5.在同一制备容器中,添加聚(2-甲基噁唑啉)-嵌段-聚(二甲基硅氧烷)-嵌段-聚-(2-甲基噁唑啉)三嵌段共聚物PMOXA12PDMS65PMOXA12,以达到0.12g/L制备的制剂的浓度。
6.以100mL/L制备的制剂的比例添加步骤2制备的LDAO 0.05%。
7.添加具有的分子量为2500Da的双(3-氨基丙基)封端的聚(二甲基硅氧烷)以达到最终浓度为0.1%。
8.添加水通道蛋白储备溶液,以达到5mg/L制备的制剂的浓度,以及1/400的蛋白质:聚合物比率。
9.添加按重量计3%的步骤1中制备的KHS溶液,以达到所制备的制剂的所需体积减去步骤6和8中添加的LDAO、双(3-氨基丙基)封端的聚(二甲基硅氧烷)和水通道蛋白的体积。
10.在室温下以每分钟170转搅拌来自步骤9的混合物过夜(不超过20小时)以获得制剂。
11.次日早晨取按步骤1至10的顺序获得的制备的制剂,以及通过200nm孔径过滤器过滤它对其灭菌,将其放入封闭密封瓶中并且在室温下保存它不超过12个月。
实施例1.4:生产支撑膜上的TFC层
a.通过在DI水中混合以下来制备水性溶液
i.3.0%MPD
ii.0.75%ε-己内酰胺(CAP)
iii.3%水通道蛋白制剂
b.在Isopar E中制备具有0.13%TMC的有机溶液。
c.TFC形成
i.将支撑膜浸入水性溶液中50秒,
ii.将膜用气枪在1巴下干燥,
iii.添加有机溶液20-22秒
iv.将膜用气枪在约0.1巴下干燥
d.将具有TFC层的膜置于70℃10%柠檬酸中4min,以及然后置于60℃的DI水中2min。
e.将膜浸入2000ppm次氯酸钠溶液中2min,然后浸入室温DI水中1min,以及最后浸入1%亚硫酸氢钠(SBS)中
实施例2:PVA层之前的甘油处理
制备10%和20%甘油水性溶液。在第一次运行中,将实施例1.4中获得的膜浸入甘油溶液中1min,用气刀处理以去除过量的甘油溶液,以及然后通过浇注有0.35%PVA水性溶液(Kuraray Poval,60-98型)处理30s,用1巴的气刀处理以去除过量的PVA溶液,并在60℃的烘箱中干燥4min。
结果示出于下表1中:
表1:
甘油浸渍 | A[LMH/巴] | 截留率[%] |
10%,1min | 5.0±0.5 | 99.0±0.0 |
20%,1min | 5.3±0.4 | 98.8±0.2 |
通过将施加方法从将整个膜浸入甘油溶液中改变为仅将甘油溶液施加到实施例1.4中获得的膜的背面,进行了另一次测试运行。结果示出于下表2中:
表2:
背面甘油 | A[LMH/巴] | 截留率[%] |
10%,1min | 4.7±0.5 | 98.9±0.0 |
20%,1min | 5.1±0.4 | 98.9±0.1 |
表1和2中显示的结果表明,与10%甘油相比,使用20%甘油时的通量改善。观察到对甘油浸渍的截留率略有下降。然而,对于背面甘油,甘油浓度的变化似乎不影响截留率。与甘油浸渍相比,通量的偏差也更小。
重复测试运行,并且包括甘油溶液的3min的较长反应时间。结果示出于表3中。
表3
背面甘油 | A[LMH/巴] | 截留率[%] |
10%,1min | 4.7±0.0 | 98.9±0.0 |
10%,3min | 4.9±0.1 | 98.9±0.1 |
20%,1min | 5.1±0.3 | 98.9±0.1 |
20%,3min | 5.6±0.1 | 98.9±0.0 |
表3中的结果示出,用20%甘油溶液处理和PVA溶液的3min的反应时间提供了最高通量和相同的截留率。
实施例3:PVA溶液的反应时间和类型
将在背面上用20%甘油处理3分钟的膜浇注有0.35%PVA 60-98溶液10s或30s,用1巴的气刀处理,以及然后在60℃的烘箱中干燥4分钟。
结果示出于表4中:
表4:
背面甘油 | A[LMH/巴] | 截留率[%] |
对照(无PVA) | 5.7±0.0 | 98.9±0.1 |
PVA涂层,10s | 4.5±0.1 | 99.3±0.2 |
PVA涂层,30s | 4.5±0.1 | 99.2±0.3 |
结果示出,通量和截留率基本保持不变。因此,为了进一步研究,使用了10s PVA反应时间。
将可从Kuraray获得的多种类型的PVA使用上述测试运行的经验进行筛选,即20%甘油背面处理3min,0.35%PVA溶液采用浇注方法并允许反应10s,用1巴的气刀处理以去除过量的PVA溶液,以及然后在60℃烘箱中干燥4min。多种PVA类型和品质的结果示出于下表5中。
表5:
命名法中的第一个数字表示4%水性溶液在20℃下的粘度,作为PVA的摩尔质量的相对量度。第二个数字表示衍生PVA的聚乙酸乙烯酯的水解度。
表5中示出的结果示出,PVA 30-98和PVA 60-98是良好的候选物,因为它们示出高通量和截留率,以及同时低偏差。这些候选物与市售的Hypershell DOW膜(基准)进行了比较。结果示出于下表6中。
表6:
N=4 | A[LMH/巴] | 截留率[%] |
对照(无PVA) | 5.8±0.1 | 99.0±0.1 |
PVA 30-98 | 4.2±0.1 | 99.2±0.1 |
PVA 60-98 | 4.4±0.2 | 99.4±0.0 |
DOW Hypershell | 3.5±0.1 | 99.5±0.1 |
基于表6中示出的结果,由于与PVA 30-98相比更高的通量和截留率,因此选择了PVA 60-98进行进一步开发。截留率基本上处于与基准相同的水平,然而通量要高约25%。
实施例4:PVA施加方法
通过PVA染料测试观察到涂膜的PVA层相当厚。与对照膜相比,相对厚的层可能是通量下降相对高的原因。因此,使用了施加PVA溶液的喷涂方法,并与浇注方法进行了比较。通量的结果示出于下表7中。
表7:
测试条件:
*)10巴,25C,RO水
**)15.5巴,25C,2000ppm NaCl进料,1.8LPM流速。
表7的结果示出,具有通过喷涂施加的PVA溶液的膜相对于浇注方法将PWP通量改善约20%,以及相对于来自DOW的基准改善60%。
实施例5:柠檬酸(CA)交联剂
试图进一步改善通量,将柠檬酸添加到PVA溶液中作为交联剂或成孔剂。
如上所述制备的PVA溶液补充有按重量计0.42%的柠檬酸,当与PVA的可用OH基团反应时,对应于50%交联度。PVA通过喷涂方法施加并使其反应10s,然后用气刀去除过量的PVA溶液。结果示出于下表8中。
表8:
柠檬酸 | A[LMH/巴] | 截留率[%] |
PVA | 4.5 | 99.1 |
PVA+CA(50%) | 4.9 | 99.1 |
测试条件:2000ppm NaCl进料,15.5巴,1.8LPM流速
结果示出,通过向PVA溶液中添加柠檬酸可获得约9%的通量改善。
研究了PVA膜以及PVA+CA(50%)的表面粗糙度Ra(nm)、接触角和ζ电位(mV),并与未用PVA处理的对照膜进行了比较。结果示出于下表9中。
表9:
平均粗糙度(nm) | 接触角 | ζ电位(mV) | |
PVA | 35.6 | 70.4 | -9.00 |
PVA+CA(50%) | 22.4 | 61.2 | -6.33 |
对照 | 53.9 | 55.3 | -22.05 |
表9中的结果示出,当膜涂有PVA层时,平均粗糙度降低。通过将柠檬酸添加到PVA溶液获得了粗糙度的进一步降低。此外,当将柠檬酸添加到PVA溶液中时,接触角和ζ电位显著降低。低表面粗糙度和ζ电位通常被认为改善膜的防污特性。当柠檬酸添加到PVA溶液中时,表面电荷趋于中性这一事实也被认为改善防污性能。
设计了进一步的实验来比较50%和100%的交联度。100%交联度的PVA溶液包含按重量计0.84%的柠檬酸。结果示出于下表10中。
表10:
柠檬酸 | A[LMH/巴] | 截留率[%] |
PVA+CA(50%) | 4.6 | 99.3±0.2 |
PVA+CA(100%) | 5.0 | 99.2±0.2 |
测试条件:2000ppm NaCl进料,15.5巴,1.8LPM流速
表10中所示的结果示出,当PVA溶液中柠檬酸的量从50%交联度增加到100%交联度时,可以获得约9%的改善的通量。
已经结合本文的多种实施方式描述了多种方面和实现方式。然而,通过研究公开内容和所附权利要求,本领域技术人员在实践要求保护的主题时可以理解和实现对所公开的实施方式的其他变化。在权利要求中,词语“包括(comprising)”不排除其他元素或步骤,并且不定冠词“一个/一种(a)”或“一个/一种(an)”不排除复数。
Claims (15)
1.一种防污半透膜,包括多孔支撑层、形成在所述支撑层的表面上的薄膜复合(TFC)层和形成在所述TFC层的顶部上的交联聚乙烯醇(PVA)层,其中所述交联PVA层是PVA和交联剂的反应产物,所述交联剂是包括三个或更多个酸基团或其前体的多元酸。
2.根据权利要求1所述的防污膜,其中所述TFC层包括水通道蛋白水通道。
3.根据权利要求1或2所述的防污膜,其中所述水通道蛋白水通道存在于囊泡中。
4.根据权利要求1至3中任一项所述的防污膜,其中所述囊泡是由一种或多种聚合物制备的聚合物囊泡。
5.根据权利要求1至4中任一项所述的防污膜,其中所述PVA衍生自聚乙酸乙烯酯的水解,所述聚乙酸乙烯酯的水解度为90%至99.9%。
6.根据权利要求1至5中任一项所述的防污膜,其中所述多元酸选自由柠檬酸、1,2,3,4-丁烷四羧酸、2,3,5-己烷三羧酸和1,2,3-丁烷三羧酸组成的组。
7.根据权利要求6所述的防污膜,其中所述多元酸为柠檬酸。
8.一种制备防污半透膜的方法,包括以下步骤:
提供包括多孔支撑层的半透膜,所述多孔支撑层具有形成在其表面上的薄膜复合(TFC)层,
将聚乙烯醇和交联剂的水性PVA混合物的层施加到所述膜的所述TFC层表面,以及
使所述混合物反应,
其中所述交联剂是具有三个或更多个酸基团或其前体的多元酸。
9.根据权利要求8所述的方法,其中在施加所述水性PVA混合物之前用甘油水性溶液处理所述包括支撑层的半透膜,所述支撑层具有形成在其表面上的薄膜复合层。
10.根据权利要求9所述的方法,其中在施加水性PVA混合物之前将甘油溶液施加到所述TFC膜的所述支撑层表面。
11.根据权利要求9或10所述的方法,其中所述甘油溶液中甘油的浓度为按重量计13%至按重量计80%。
12.根据权利要求8-11中任一项所述的方法,其中所述多元酸选自由柠檬酸、1,2,3,4-丁烷四羧酸、2,3,5-己烷三羧酸和1,2,3-丁烷三羧酸组成的组。
13.根据权利要求12所述的方法,其中所述多元酸为柠檬酸。
14.根据权利要求12或13中任一项所述的方法,其中所述多元酸的按重量计的浓度等于或高于所述水性PVA混合物中所述PVA的按重量计的浓度。
15.根据权利要求14所述的方法,其中所述柠檬酸的按重量计的浓度是所述水性混合物中所述PVA的浓度的至少两倍。
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