CN100548451C - 膜过滤系统中的清洗 - Google Patents
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Abstract
清洗排列型的可渗透中空膜(6)的方法，其中在浸在悬浮液中的可渗透中空膜(6)的壁(15)的两侧施加压差，该悬浮液施加到多孔中空膜(6)的外表面上以引发和维持透过膜壁(15)的过滤，其中一些悬浮液穿过膜(6)的壁(16)以从中空膜内腔(7)中作为澄清的液体或渗透物排出，且至少一些固体留在中空膜(6)上或留在中空膜(6)中或作为悬浮固体留在膜(6)周围的液体中。该清洗方法包括下列步骤：对膜壁(15)一侧施加清洗溶液(14)；在膜壁(15)两侧施加压差以使清洗溶液(14)透过壁(15)从膜壁(15)的一侧流向膜壁(15)的另一侧，并在膜壁(15)两侧施加反向压差以使清洗溶液(14)透过壁(15)从膜壁(15)的另一侧流回膜壁(15)的一侧。还公开了确定所需的化学清洗溶液的量的方法。
Description
发明领域
本发明涉及在膜过滤系统中使用的中空可透膜的回洗，并特别涉及回洗和清洗中空可透膜的改进方法。
背景技术
整篇说明书中关于现有技术的任何讨论决不应该被认为是承认这类现有技术是公知的或构成本领域内普通常识的一部分。
已知的回洗系统包括我们早先的国际申请No.WO 93/02779中描述的那些，其主题通过交叉引用并入本文。
在膜清洗过程中，清洗溶液通常穿过膜及其可渗透壁流动以从膜上清洗污垢。在压力下施加清洗溶液有助于从表面上去除污垢。
用于膜的典型已知清洗方法包括原位清洗膜。这种方法将指定浓度的化学品，通常是2％柠檬酸然后200-1000ppm次氯酸钠，添加到在滤液溶液中的膜中。这通常在两小时清洗周期开始时发生，此后清洗剂透过膜过滤并留下来浸泡。
由于膜污垢的性质随进料品质和类型、透膜通量和运行小时数而变，每种情况下所需的化学清洗的量和持续时间也改变。这通常导致一个方法适用于所有处理，其中无论污垢量如何都使用标准化学清洗阶段。这会导致不必要地使用大量清洗溶液，结果造成清洗完成之后废液处置中的额外成本和环境影响。
发明内容
本发明的目的是克服或至少改善现有技术的一个或多个缺点或至少提供可用的替代方案。
根据第一方面，本发明提供了清洗排列型的可渗透中空膜的方法，其中在浸在悬浮液中的可渗透中空膜壁的两侧施加压差，所述悬浮液施加到多孔中空膜的外表面上以引发和维持透过膜壁的过滤，其中：
(a)一些悬浮液穿过膜壁以从中空膜内腔中作为澄清的液体或渗透物排出，且
(b)至少一些固体留在中空膜上或留在中空膜中或作为悬浮固体留在膜周围的液体中，
该清洗方法包括下列步骤：
i)从膜的滤液侧至少部分去除液体；
ii)从膜的外侧至少部分去除液体；
iii)对膜的外侧施加清洗溶液；
iv)在所述膜壁两侧施加压差以使所述清洗溶液透过所述壁从膜的外侧流入膜内腔，以使所述内腔至少部分被清洗溶液填充；
v)隔离膜外侧；
vi)对膜壁的滤液侧施加加压气体以使清洗溶液透过膜壁流回外侧；
vii)积聚由于清洗溶液的所述流动而在膜外侧上产生的增压；
viii)释放由所述加压气体施加到膜壁的所述滤液侧上的压力，以使所述清洗溶液在膜壁外侧上的所述积聚压力的作用下透过所述膜从外侧流向滤液侧。
优选地，清洗溶液是化学清洗溶液。
优选地，在步骤vi)中，施加气体，通常为空气，以使膜内腔基本排空清洗溶液。优选地，在步骤vii)中，压力积聚在位于膜壁外侧上的气体空间中或积聚在气囊装置中。
通过对膜壁外侧施加气压或通过对滤液侧施加真空，可以提供步骤iv)的压差。
根据本发明的另一方面，提供了清洗排列型的可渗透中空膜的方法，其中在浸在悬浮液中的可渗透中空膜壁的两侧施加压差，所述悬浮液施加到多孔中空膜的外表面上以引发和维持透过膜壁的过滤，其中：
(a)一些悬浮液穿过膜壁以从中空膜内腔中作为澄清的液体或渗透物排出，且
(b)至少一些固体留在中空膜上或留在中空膜中或作为悬浮固体留在膜周围的液体中，
该清洗方法包括下列步骤：
i)对膜壁的一侧施加清洗溶液；
ii)在所述膜壁两侧施加压差以使所述清洗溶液透过所述壁从膜壁的所述一侧流向膜壁的另一侧；
iii)在所述膜壁两侧施加反向压差以使所述清洗溶液透过所述壁从膜壁的所述另一侧流回膜壁的所述一侧。
根据本发明的再一方面，提供了清洗排列型的可渗透中空膜的方法，其中在浸在悬浮液中的可渗透中空膜壁的两侧施加压差，所述悬浮液施加到多孔中空膜的外表面上以引发和维持透过膜壁的过滤，其中：
(a)一些悬浮液穿过膜壁以从中空膜内腔中作为澄清的液体或渗透物排出，且
(b)至少一些固体留在中空膜上或留在中空膜中或另外作为悬浮固体留在膜周围的液体中，
该清洗方法包括下列步骤：
i)从膜的滤液侧至少部分去除液体；
ii)从膜的外侧至少部分去除液体；
iii)对膜的外侧施加清洗溶液；
iv)在所述膜壁两侧施加压差以使所述清洗溶液透过所述壁从膜的外侧流入膜内腔，以使所述内腔至少部分被清洗溶液填充；
v)在所述膜壁两侧施加压差以使所述清洗溶液透过所述壁从膜的内腔侧流回膜内腔的外侧。
优选地，通过对膜壁的滤液侧施加加压气体来产生步骤v)中的压差，从而使清洗溶液透过膜壁流回外侧。
清洗过程可以循环反复以使清洗溶液透过膜壁交替地从膜一侧移向另一侧。
该方法可用于浸在敞口容器中的膜以及加压膜过滤系统。
根据本发明的另一方面，提供了控制膜的化学清洗的方法，包括：
测量用于至少一部分所述的清洗的膜的pH值和/或膜电阻；和
当pH值和/或膜电阻达到预定值时，终止所述化学清洗。
根据本发明的另一方面，提供了控制膜的化学清洗的方法，包括：
测量用于至少一部分所述的清洗的膜的pH值和/或膜电阻；
测量清洗时间；
计算pH值相对于时间的变化率(dpH/dt)和/或膜电阻相对于时间的变化率(dR/dt)；和
当dpH/dt和/或dR/dt达到预定值时终止所述化学清洗。
根据本发明的另一方面，提供了控制过滤系统的化学清洗的方法，包括下列步骤：
测量用于至少一部分所述的清洗的膜的膜电阻；
测量清洗时间；
计算相对于时间的膜电阻变化速率(dR/dt)；和
使用dR/dt计算完成清洗所用的持续时间。
根据本发明的另一方面，提供了控制膜的化学清洗的方法，包括：
增加在清洗中存在的化学清洗剂的量；
测量用于至少一部分所述的清洗的膜的膜电阻；
在膜电阻达到预定值时终止化学清洗剂的增加。
优选地，递增地增加清洗剂的量。优选地，该预定值接近膜电阻的稳态值。优选地，膜是微滤或超滤型膜。
附图简述
参照附图仅以实例描述本发明的优选实施方案，其中：
图1a显示了膜组件的简化截面侧视图，其中该组件的下部浸在化学清洗溶液中并对膜内腔施加吸力；
图1b显示了图1a的所示区域中的膜的放大截面图；
图1c显示了图1a的所示区域中的膜的放大截面图；
图2a显示了图1的膜组件的简化截面侧视图，其中该组件的下部浸在化学清洗溶液中并对膜内腔施加加压气体；
图2b显示了图2a的所示区域中的膜的放大截面图；
图3a显示了图1的膜组件的简化截面侧视图，其中该组件的下部浸在化学清洗溶液中并对膜内腔施加吸力；
图3b显示了图3a的所示区域中的膜的放大截面图；
图3c显示了图3a的所示区域中的膜的放大截面图；
图4a显示了膜组件的另一实施方案的简化截面侧视图，其中该组件的下部浸在化学清洗溶液中并对膜内腔施加吸力；
图4b显示了图4a的所示区域中的膜的放大截面图；
图4c显示了图4a的所示区域中的膜的放大截面图；
图5a显示了图4的膜组件的简化截面侧视图，其中该组件的下部浸在化学清洗溶液中并对膜内腔施加加压气体；
图5b显示了图5a的所示区域中的膜的放大截面图；
图6a显示了膜组件的另一实施方案的简化截面侧视图，其中该组件的下部浸在化学清洗溶液中并对膜内腔施加吸力；
图6b显示了图6a的所示区域中的膜的放大截面图；
图6c显示了图6a的所示区域中的膜的放大截面图；
图7a显示了图6的膜组件的简化截面侧视图，其中该组件的下部浸在化学清洗溶液中并对膜内腔施加加压气体；
图7b显示了图7a的所示区域中的膜的放大截面图；
图8a显示了在敞口容器中的膜组件的实施方案的简化截面侧视图，其中该组件的下部浸在化学清洗溶液中并对膜内腔施加吸力；
图8b显示了图8a的所示区域中的膜的放大截面图；
图8c显示了图8a的所示区域中的膜的放大截面图；
图9a显示了图8的实施方案中的膜组件的简化截面侧视图，其中该组件的下部浸在化学清洗溶液中并对膜内腔施加加压气体；
图9b显示了图9a的所示区域中的膜的放大截面图；
图10显示了对于使用本发明的方法进行化学清洗的图8和9中所示类型的膜组件，随时间测得的透膜压力(TMP)图；
图11显示了对于在清洗过程中添加的化学清洗剂的体积递增的两种类型的化学清洗过程，随时间测得的膜电阻图；和
图12显示了在清洗过程中添加的化学清洗剂的体积递增的情况下，随时间测得的膜电阻图。
优选实施方案描述
参照图1至7，显示了具有多个中空纤维膜6的膜组件5。纤维膜6具有下端封闭在下方罐(lower pot)8中的内腔7，并在其上端通过上方罐(upper pot)9敞开。组件5装在容器10中，该容器具有用于使容器10向大气敞开/封闭的可控阀11。上方罐8连接到具有开口13的滤液收集室12上。
现在参照图1至3描述根据本发明的清洗方法的一个实施方案。最佳地如图1a至1c中所示，过滤后将留在内腔7中的液体排出，同时将留在容器10中的液体也至少部分排出。然后最佳地如图1a中所示，容器10至少部分用清洗溶液14填充。然后在膜壁15两侧施加压差，在此实施方案中通过对出口13施加真空来进行，从而使清洗溶液14透过膜壁15(如图1b中所示)排出并沿膜内腔7向上直至内腔至少部分被清洗溶液填充。
如图2a和2b中所示，随后关闭阀11以隔离容器10，同时通过开口13对填充膜内腔7的清洗溶液施加加压气体并且该加压气体透过膜壁15排出直至内腔7基本排空清洗溶液。在容器10隔离的情况下，清洗溶液14透过膜壁15向膜6外侧的转移导致容器内的压力随着容器10内的气体空间16被压缩而提高。
如图3a至3c中所示，使膜的内腔侧向大气排气。最佳如图3b所示，气体空间16中积聚的压力随后迫使清洗溶液14透过膜壁15流回。
图4a至7b显示了本发明的实施方案，其中可以使用气囊装置代替气体空间16以积聚压力。
参照图4a至4c，操作与图3a至3c中所示的类似，但是，在该实施方案中，当膜的内腔侧通过阀17向大气排气时，气囊16对容器10的进料侧输送压力，从而最佳地如图4b和4c中所示，迫使清洗溶液14透过膜壁15并沿膜内腔7行进。
参照图5a和5b，显示了内腔/滤液侧的加压。通过管道18和阀17向开口13加入加压气体，由此对膜6的内腔/滤液侧施加加压气体。加压气体使内腔7内的清洗溶液透过膜壁15流向膜的外侧，从而使容器10内的压力提高，并转移到经由管道19和阀11连接到容器10上的气囊16中。
图6a至6c显示了与图4a至4c类似的设置，但是在此实施方案中，从外部来源而非气囊16，经由管道19和阀11对容器10施加气压。如图6a中所示，使用气囊16积聚膜6内腔侧上的压力。
如图7a和7b中所示，当需要清洗溶液的反向流动时，容器10经由管道19和阀11向大气排气，且气囊16对内腔侧释放积聚的压力，迫使内腔内的清洗溶液14透过内腔壁15反洗(参见图7b)。
参照图8和9，显示了根据本发明的清洗过程的一个实施方案，其中容器10向大气敞开。在此实施方案中，通过对膜6的内腔侧交替施加吸力/真空或压力，使清洗溶液透过膜壁15流动。再将膜组件5至少部分浸在化学清洗溶液14中，并对纤维膜内腔7的开口端施加吸力。最佳地如图8b中所示，清洗溶液14透过膜壁15进入纤维膜内腔7。然后使清洗溶液14通过内腔7向上抽吸，直至内腔如图8c中所示完全填满。如图9a和9b中所示，然后对填充膜内腔7的清洗溶液14施加加压气体，清洗溶液如前所述透过膜壁15转移。
实施方案中所示的过程可以循环反复以使清洗溶液交替地从膜壁15一侧移向另一侧。清洗溶液向和从模内腔7以及沿内腔长度的流动导致膜组件5的有效化学清洗。
图10显示了对容器10向大气敞开的这种类型的膜组件使用根据本发明的清洗方案的结果。该清洗法如下进行：
1.通过从内腔侧向外壳侧的回填，使膜容器被滤液填充，同时向滤液管道定量加入氯。容器滤液含量为大约30％，清洗溶液(NaOCl)的目标体积为30毫升。
2.然后使滤液短暂地通过该系统再循环以确保获得充分混合的清洗溶液。
3.然后通过对滤液管道施加100kPa空气，排空内腔中的液体。这能够使清洗溶液透过孔隙并沿纤维长度向下扩散，这提高了滤液容器液面。当液面停止升高时，可以结束该步骤。
4.然后使用施加到膜的内腔侧上的真空空气，使内腔被清洗溶液填充。在此步骤中，随着液体被抽入到纤维腔中，滤液槽中的液面下降。当液面停止下降时，可以结束该步骤。
5.重复内腔填充和排空步骤直至接触时间达到1800秒。
6.在1800秒的清洗溶液接触之后，用进料装满该容器。这能够使清洗溶液中剩余的游离氯与清洗过程中暴露的组件部分接触。
7.然后将该系统充气以使溶液与组件的接触最大化。
8.然后排空该槽并在重新使用之前用滤液冲洗。
图10中绘制的数据显示了每24过滤小时进行一次清洗并连续进行4天的周期，其中该组件以1.7m3/hr和30分钟的回洗间隔运行。使用次氯酸钠(NaOCl)形式的氯，清洗过程中的平均游离氯浓度为100ppm。进料水浊度始终为60-90NTU。
图10中所示的数据显示了每次清洗后透膜压力(TMP)的有规律的降低。
本发明的一个实施方案寻求通过如下方法使所需化学品的量最小化：将化学品递增地添加到膜槽中，同时在清洗过程的再循环阶段监测透膜电阻。当化学品的进一步添加导致膜电阻的变化在预定水平以下时，可以终止化学品添加，由此使清洗过程中使用的过量化学剂的量最小化。
可以在滤液再循环过程中监测电阻值。通常，在标准清洗方法中，仅在清洗开始时使化学清洗溶液再循环，然后膜最多浸泡48小时。在本实施方案中，在浸泡/充气步骤中，每15-30分钟使化学清洗溶液再循环数分钟(例如-3分钟)，从而在整个清洗过程中定期测量膜电阻。
当每3次再循环的电阻变化降至低于预定值(例如-0.1)时，清洗法恢复了该化学品浓度下的最大性能，并进一步添加化学剂。当每3次再循环中，化学剂的进一步添加对电阻变化的影响低于预定值(例如-0.1)时，不能实现进一步的恢复，并因此立即终止清洗过程。相反地，通过延长清洗过程以使每3次循环的电阻变化低于某一预定值，可以使清洗能力最大化。图11显示了对于使用柠檬酸(CIP1)和氯(CIP2)清洗剂的两种不同清洗方案，清洗过程持续期间的电阻值变化图。
参照图12中所示的图，化学剂的体积从如在A所示的大约100毫升开始，其导致膜电阻显著降低。如在B和C所示进一步增加化学剂的量以进一步降低膜电阻。一旦化学剂的体积达到大约250毫升，膜电阻变化如在D所示基本达到稳态，化学剂的进一步增加(E)具有最小的效果。在此阶段，可以终止化学剂的添加而不会对清洗过程和透膜流的恢复产生负面影响。
要认识到，使用上述测量方法可以针对特定膜设置或构造确定在清洗过程中的电阻分布图。然后使用该电阻分布图预测清洗时间的终点、半衰期、并减少类似系统的同时清洗中的化学品使用。可以进一步使用该电阻分布图确定在清洗过程中是否需要添加化学品，化学品的类型和量取决于进料和污垢品质。
可以使用的典型清洗溶液包括酸、苛性碱溶液和氧化溶液(例如氯)。
在与前述国际申请No.WO93/02779中所述类似的并根据本发明的方法进行适当修改以运行的装置中具体实施本发明。
要认识到，不脱离所述发明的精神或范围的本发明的其它实施方案和示例是可行的。
Claims (7)
1.清洗排列型的可渗透中空膜的方法，其中在浸在悬浮液中的可渗透中空膜壁的两侧施加压差，所述悬浮液施加到多孔中空膜的外表面上以引发和维持透过膜壁的过滤，其中：
(a)一些悬浮液穿过膜壁以从中空膜内腔中作为澄清的液体或渗透物排出，且
(b)至少一些固体留在中空膜上或留在中空膜中或作为悬浮固体留在膜周围的液体中，
该清洗方法包括下列步骤：
i)从膜的滤液侧至少部分去除液体；
ii)从膜的外侧至少部分去除液体；
iii)对膜的外侧施加清洗溶液；
iv)在所述膜壁两侧施加压差以使所述清洗溶液透过所述壁从膜的外侧流入膜内腔，以使所述内腔至少部分被清洗溶液填充；
v)隔离膜外侧；
vi)对膜壁的滤液侧施加加压气体以使清洗溶液透过膜壁流回外侧；
vii)积聚由于清洗溶液的所述流动而在膜外侧上产生的增压；
viii)释放由所述加压气体施加到膜壁的所述滤液侧上的压力，以使所述清洗溶液在膜壁外侧上的积聚压力的作用下透过所述膜从外侧流向滤液侧。
2.根据权利要求1的方法，其中清洗溶液是化学清洗溶液。
3.根据权利要求1的方法，其中在步骤vi)中，施加气体以使膜内腔基本排空清洗溶液。
4.根据权利要求1的方法，其中在步骤vii)中，压力积聚在位于膜壁外侧的气体空间中。
5.根据权利要求1的方法，其中在步骤vii)中，压力积聚在气囊装置中。
6.根据权利要求1的方法，其中通过对膜壁外侧施加气压，提供步骤iv)中的压差。
7.根据权利要求1的方法，其中通过对滤液侧施加真空，提供步骤iv)中的压差。
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- 2005-12-19 CN CN200910141120.2A patent/CN101623599B/zh not_active Expired - Fee Related
- 2005-12-19 CA CA2591408A patent/CA2591408C/en not_active Expired - Fee Related
- 2005-12-19 NZ NZ583228A patent/NZ583228A/en not_active IP Right Cessation
- 2005-12-19 US US11/722,411 patent/US8496828B2/en not_active Expired - Fee Related
- 2005-12-19 NZ NZ555856A patent/NZ555856A/en not_active IP Right Cessation
- 2005-12-19 SG SG2014010789A patent/SG2014010789A/en unknown
- 2005-12-19 JP JP2007547083A patent/JP4763718B2/ja not_active Expired - Fee Related
- 2005-12-19 AT AT05818584T patent/ATE549076T1/de active
- 2005-12-19 AU AU2005318930A patent/AU2005318930B2/en not_active Ceased
- 2005-12-19 WO PCT/AU2005/001919 patent/WO2006066319A1/en active Application Filing
- 2005-12-19 CN CN200580046369.5A patent/CN100548451C/zh not_active Expired - Fee Related
- 2005-12-19 EP EP05818584A patent/EP1835985B1/en not_active Not-in-force
- 2005-12-19 SG SG200900958-0A patent/SG150505A1/en unknown
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2009
- 2009-12-14 JP JP2009283150A patent/JP5410942B2/ja not_active Expired - Fee Related
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2013
- 2013-04-30 US US13/874,151 patent/US20130334136A1/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540490A (en) * | 1982-04-23 | 1985-09-10 | Jgc Corporation | Apparatus for filtration of a suspension |
| US4767539A (en) * | 1983-09-30 | 1988-08-30 | Memtec Limited | Cleaning of hollow fiber filters utilized in lumenal gas flow |
| US6045698A (en) * | 1995-11-22 | 2000-04-04 | Omnium De Traitements Et De Valorization (Otv) | Method for cleaning a filtration installation of the type with immersed membranes |
| CN1548219A (zh) * | 2003-05-13 | 2004-11-24 | 天津膜天膜工程技术有限公司 | 一种外压中空纤维膜分离装置运行方法 |
| CN1852760A (zh) * | 2003-09-22 | 2006-10-25 | 美国废水过滤集团公司 | 反洗和清洁方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1835985A1 (en) | 2007-09-26 |
| AU2005318930A1 (en) | 2006-06-29 |
| CA2591408A1 (en) | 2006-06-29 |
| ATE549076T1 (de) | 2012-03-15 |
| JP5410942B2 (ja) | 2014-02-05 |
| CN101098746A (zh) | 2008-01-02 |
| SG2014010789A (en) | 2014-06-27 |
| WO2006066319A1 (en) | 2006-06-29 |
| US20130334136A1 (en) | 2013-12-19 |
| EP2394731A1 (en) | 2011-12-14 |
| EP1835985A4 (en) | 2009-07-08 |
| JP2008525165A (ja) | 2008-07-17 |
| CN101623599A (zh) | 2010-01-13 |
| NZ555856A (en) | 2010-03-26 |
| JP2010058120A (ja) | 2010-03-18 |
| CA2591408C (en) | 2015-07-21 |
| SG150505A1 (en) | 2009-03-30 |
| US20110114557A2 (en) | 2011-05-19 |
| US20080203016A1 (en) | 2008-08-28 |
| JP4763718B2 (ja) | 2011-08-31 |
| NZ583228A (en) | 2012-05-25 |
| AU2005318930B2 (en) | 2010-06-03 |
| US8496828B2 (en) | 2013-07-30 |
| CN101623599B (zh) | 2013-01-16 |
| EP1835985B1 (en) | 2012-03-14 |
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