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CN112473391A - 一种反渗透膜缺陷的修复方法 - Google Patents

一种反渗透膜缺陷的修复方法 Download PDF

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CN112473391A
CN112473391A CN202011534367.3A CN202011534367A CN112473391A CN 112473391 A CN112473391 A CN 112473391A CN 202011534367 A CN202011534367 A CN 202011534367A CN 112473391 A CN112473391 A CN 112473391A
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reverse osmosis
osmosis membrane
repairing
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membrane
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武少禹
刘星
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Nanjing Delnamem Technology Co ltd
Nanjing Shuilian Tianxia Seawater Desalination Technology Research Institute Co ltd
Anhui Encote Film Technology Co ltd
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Nanjing Delnamem Technology Co ltd
Nanjing Shuilian Tianxia Seawater Desalination Technology Research Institute Co ltd
Anhui Encote Film Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025Reverse osmosis; Hyperfiltration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D65/00Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02Membrane cleaning or sterilisation ; Membrane regeneration
    • 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
    • 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
    • B01D69/06Flat membranes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2311/00Details relating to membrane separation process operations and control
    • B01D2311/10Temperature control
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2311/00Details relating to membrane separation process operations and control
    • B01D2311/14Pressure control
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2311/00Details relating to membrane separation process operations and control
    • B01D2311/18Details relating to membrane separation process operations and control pH control
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2321/00Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16Use of chemical agents
    • B01D2321/168Use of other chemical agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124Water desalination
    • Y02A20/131Reverse-osmosis

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

本发明公开了一种反渗透膜缺陷的修复方法,具体地,聚酰胺类反渗透复合膜元件用含不同浓度染料及助剂的水溶液中作为原水,在一定压力、温度、回收率的条件下,循环运行一定时间后,利用染料优先染色复合膜的底膜材料的特性,将聚酰胺缺陷部分封住,从而获得脱盐能力的修复。

Description

一种反渗透膜缺陷的修复方法
技术领域
本发明属于分离膜材料的制备技术领域,涉及反渗透膜缺陷的修复方法,具体为利用水溶性染料封堵反渗透膜缺陷,提高膜的脱盐能力的方法。
背景技术
能源和环境问题,包括水安全、全球变暖和能源供应萎缩,近年来一直引起人们的极大关注。到目前为止,各种技术已经被初步探索,以获得清洁水,捕获“温室”气体,并找到替代能源。通过解决上述一些紧迫问题,膜分离已成为最重要的技术之一。膜分离技术在分离工业中越来越重要,可应用于气相或液相中各种分子量组分的分离,膜分离的特殊优点是不需要加热,因此能量的使用大大低于传统的热分离过程。液体分离膜包括微滤、超滤、纳滤和反渗透。
反渗透膜作为一种最高精度的水分离膜,尤其是第二代的聚酰胺类反渗透复合膜,能将水与水中的离子有效分离,但其制作过程中工艺控制失当产生的缺陷,或长时期运行过程造成的表面结构破坏,均会造成膜的脱盐能力下降。美国专利3853755和3866066公开了对此类缺陷的修复方法,该方法采用了水解性单宁作为修复剂,可一定程度修复膜的缺陷。另一个美国专利3877978则采用了乙酸乙烯酯作为修复剂,由于其对缺陷修复的非选择性,虽然可以修复缺陷,提高脱盐率,但膜表面也涂了一层该物质,增加水透过膜的阻力,降低了膜水通量。本发明提供了一种修复剂及修复方法,可选择性封堵膜表面缺陷部分。
发明内容
为了解决现有技术问题,针对反渗透膜表面缺陷,本发明旨在提出一种修复方法,通过该方法能有效修复膜表面缺陷,提高膜的脱盐性能。
为了实现上述目的,本发明公开了一种反渗透膜缺陷的修复方法。更具体地说,聚酰胺类反渗透膜元件用含不同浓度染料及助剂的水溶液中作为原水,在一定压力、温度、pH值、回收率的条件下,循环运行一定时间后,利用染料优先染色复合膜的底膜材料的特性,将聚酰胺缺陷部分封住,从而获得脱盐能力的修复。
所述膜元件包括卷式,蝶式及板框式膜元件。
所述染料为分子结构中包含羧基或磺酸基团,分子量大于400的染料,包括罗丹明、甲基蓝、甲基橙、刚果红和直接蓝,所述染料浓度为0.1-0.8% (wt%)。
所述助剂为水溶性有机溶剂。
所述有机溶剂包括乙醇、丙醇、异丙醇、丁醇、丙酮、丁酮、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮,所述助剂浓度为0-5.0% (wt%)。
所述压力范围0.2-10.0 Mpa、温度范围5-80℃、pH 1-14、回收率为5-95%。
本发明的技术方案具有以下有益效果:
本发明提供一种反渗透膜缺陷的修复方法,采用该方法能有效修复聚酰胺类复合膜的表面缺陷,使得膜的脱盐性能得到修复及提高,延长膜的使用寿命,降低膜的使用成本,可在膜应用现场实施,简单易行。
具体实施方式
以下为本发明的优选实施方式,仅用于解释本发明,而非用于限制本发明,且由该说明所作出的相关改进都属于本发明所附权利要求所保护的范围:
反渗透膜元件的准备:选用用过一定时间被替换下来的聚酰胺类反渗透复合膜元件,型号为4040,表面经清洗后,其对氯化钠的脱盐性能从大于99%降到85.0-94.5%。
膜的脱盐性能性测试:配制1500ppm 浓度的NaCl水溶液,测试压力1.0Mpa,温度25℃,回收率15%。
实施例1:选择脱盐率为85.5%的4040卷式反渗透膜元件见表1。0.1% 罗丹明B水溶液,温度为80℃,1.0Mpa压力,95%回收率,每分钟10升浓水,循环30分钟,所测脱NaCl脱盐率从87.5%提高到97.2%。
实施例2:其它条件与实施例1相同,罗丹明B浓度0.1%,异丙醇浓度5%。运行时间30分钟。修复前后脱盐率结果见表1。
实施例3-10:其它条件与实施例1相同,修复条件及结果见表1。
实施例11:其它条件与实施例1相同,温度5℃,用盐酸调节溶液pH值到1,回收率为5%。
实施例12:其它条件与实施例1相同,温度25℃,用氢氧化钠调节溶液pH值到14,回收率为5%。
表1 实施例1-12修复条件及结果
Figure 394116DEST_PATH_IMAGE001

Claims (7)

1.一种反渗透膜缺陷的修复方法,其特征在于,包括如下步骤:
聚酰胺类反渗透膜元件以含一定浓度染料及助剂的水溶液作为原水,在一定压力、温度、pH值、回收率的条件下,循环运行一定时间后,利用染料优先染色复合膜的底膜材料的特性,将聚酰胺缺陷部分封住,从而获得脱盐能力的修复。
2.根据权利要求1所述的一种反渗透膜缺陷的修复方法,其特征在于,所述膜元件包括卷式,蝶式及板框式膜元件。
3.根据权利要求1所述的一种反渗透膜缺陷的修复方法,其特征在于,所述染料为分子结构中包含羧基或磺酸基团,分子量大于400的染料。
4.根据权利要求3所述的一种反渗透膜缺陷的修复方法,其特征在于,所述染料包括罗丹明、甲基蓝、甲基橙、刚果红和直接蓝,所述染料浓度为0.1-0.8%(wt%)。
5.根据权利要求1所述的一种反渗透膜缺陷的修复方法,其特征在于,所述助剂为水溶性有机溶剂。
6.根据权利要求4所述的一种反渗透膜缺陷的修复方法,其特征在于,所述有机溶剂包括乙醇、丙醇、异丙醇、丁醇、丙酮、丁酮、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮,所述助剂浓度为0-5.0% (wt%)。
7.根据权利要求1所述的一种反渗透膜缺陷的修复方法,其特征在于,所述压力范围为0.2-10.0 Mpa、温度范围为5-80℃、pH为1-14、回收率为5-95%。
CN202011534367.3A 2020-12-23 2020-12-23 一种反渗透膜缺陷的修复方法 Withdrawn CN112473391A (zh)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853755A (en) * 1972-11-06 1974-12-10 Du Pont Osmosis efficiency from tannin treatment of non-porous semipermeable membranes having hydrous heavy metal coatings
US3877978A (en) * 1974-03-27 1975-04-15 Us Interior Semipermeable membranes
JPH06254358A (ja) * 1993-03-03 1994-09-13 Toyobo Co Ltd 逆浸透膜の欠陥検出方法
JPH10263539A (ja) * 1997-03-28 1998-10-06 Japan Organo Co Ltd 被処理水の膜処理方法及び膜処理装置
KR20110066383A (ko) * 2009-12-11 2011-06-17 코오롱건설주식회사 가염성 중공사 분리막
JP2012166202A (ja) * 2012-06-15 2012-09-06 Mitsubishi Rayon Co Ltd 中空糸膜モジュールの中空糸膜選別方法とこれを利用した中空糸膜モジュール製造方法
WO2013110458A1 (de) * 2012-01-27 2013-08-01 Sartorius Stedim Biotech Gmbh Verfahren zum nachweisen von fehlstellen in einer ultrafiltrationsmembran
CN104399374A (zh) * 2014-11-25 2015-03-11 贵阳时代沃顿科技有限公司 一种检测复合反渗透膜脱盐层完整性的方法及其检测装置
CN106925132A (zh) * 2017-04-19 2017-07-07 青岛天兰环境股份有限公司 反渗透膜修补剂及修补方法
US20190321785A1 (en) * 2018-04-20 2019-10-24 Korea University Research And Business Foundation Method of post-treating zeolite membranes by using dye molecules
CN111712317A (zh) * 2018-05-10 2020-09-25 株式会社Lg化学 反渗透膜、其制造方法及水处理模块

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853755A (en) * 1972-11-06 1974-12-10 Du Pont Osmosis efficiency from tannin treatment of non-porous semipermeable membranes having hydrous heavy metal coatings
US3877978A (en) * 1974-03-27 1975-04-15 Us Interior Semipermeable membranes
JPH06254358A (ja) * 1993-03-03 1994-09-13 Toyobo Co Ltd 逆浸透膜の欠陥検出方法
JPH10263539A (ja) * 1997-03-28 1998-10-06 Japan Organo Co Ltd 被処理水の膜処理方法及び膜処理装置
KR20110066383A (ko) * 2009-12-11 2011-06-17 코오롱건설주식회사 가염성 중공사 분리막
WO2013110458A1 (de) * 2012-01-27 2013-08-01 Sartorius Stedim Biotech Gmbh Verfahren zum nachweisen von fehlstellen in einer ultrafiltrationsmembran
JP2012166202A (ja) * 2012-06-15 2012-09-06 Mitsubishi Rayon Co Ltd 中空糸膜モジュールの中空糸膜選別方法とこれを利用した中空糸膜モジュール製造方法
CN104399374A (zh) * 2014-11-25 2015-03-11 贵阳时代沃顿科技有限公司 一种检测复合反渗透膜脱盐层完整性的方法及其检测装置
CN106925132A (zh) * 2017-04-19 2017-07-07 青岛天兰环境股份有限公司 反渗透膜修补剂及修补方法
US20190321785A1 (en) * 2018-04-20 2019-10-24 Korea University Research And Business Foundation Method of post-treating zeolite membranes by using dye molecules
CN111712317A (zh) * 2018-05-10 2020-09-25 株式会社Lg化学 反渗透膜、其制造方法及水处理模块

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