CN101184548B - 用于膜滤器的化学清洗剂 - Google Patents
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Abstract
清洗具有原料侧和渗透侧的多孔聚合物膜的方法，该方法包括下述步骤：将含清洗剂的流体引入到膜的渗透侧；允许清洗剂接触膜的渗透侧预定时间，和接触膜的孔隙；或者将含清洗剂的流体引入到膜的原料侧；施加跨膜压力，强制含清洗剂的流体从膜的原料侧到渗透侧；允许清洗剂接触膜的渗透侧预定的时间，和接触膜的孔隙。优选地，在原料侧流体和含有清洗剂的内腔侧流体之间浓度梯度引起清洗剂扩散到原料侧流体中。可施加压力到含清洗剂的流体上，以便从膜的孔隙中移动(若存在的话)溶解和未溶解的固体。可以以脉冲的方式施加压力，和可借助在不大于膜的泡点的压力下的压缩空气。本发明的方法之前或者紧跟着可以是反洗。
Description
技术领域
本发明涉及适合于在过滤装置中使用的清洗方法。更特别地，本发明涉及清洗用于水过滤目的而使用的微滤或超滤膜的方法。
背景技术
微滤和超滤的膜滤器愈加用于城市饮用水处理和废水处理。采用典型的微滤或超滤操作，跨膜压力(TMP)是过滤工艺的主要驱动力。当工艺进行和过滤的水通过膜渗透时，大多数固体污染物或者保留在膜表面上，从而形成结垢层或者作为膜孔隙内的堵塞物保留，从而阻止过滤。存在结垢层或者堵塞的孔隙或者这两种情况可显著增加跨膜压力并最终增加过滤的能耗。
用或者滤液或者气体频繁地反洗可部分恢复膜的渗透率，然而，已知利用这些方法的情况下，污垢可继续累积在膜表上和孔隙内。连续反洗没有除去所有沉积的物质，因此随着时间流逝过滤器的渗透性将劣化。
通过使用化学清洗剂补充的清洗方案是已知的。选择化学清洗方法的一般标准是首先实现膜渗透性的良好恢复，第二最小化所要求的化学清洗剂的用量和所生成的所得废物量，和第三使得可容易操作。
一种清洗方法牵涉在化学清洗溶液内浸渍膜一段时间。化学反应将溶解在膜表面上累积和孔隙内堵塞的固体。可通过注入的空气冲刷膜或者通过循环化学溶液，从而促进清洗效果。这是膜性能的化学充分恢复常用的常见方法，然而，它的缺点是，要求显著大体积的化学溶液和该工艺生成大体积的化学废物。
在控制渗透性劣化的其他尝试中，常常采用膜滤器进行短暂的化学清洗(维护清洗)。US5403479公开了进行这一工艺的一种这样的方法。将清洗溶液引入到真空纤维膜的腔内，并在低于膜泡点的压力下在低的流速下循环。清洗溶液在低的跨膜压力和低速下渗透经过膜孔隙。作者还证明甚至当在没有速度下但在压力下流体保持在纤维内时，可发生清洗溶液经过膜扩散。在清洗过程中，膜浸渍在水内。这一方法要求储存足以填充渗透管线并循环的一定体积的化学溶液。在循环工艺过程中，增加量的化学溶液从内腔侧通过膜孔隙渗透到原料侧。
进行膜清洗的另一方法牵涉用化学清洗剂，反复反冲(backpulsing)膜，正如JP09313902和US6045698中所述。在美国专利申请20010052494A1、20030146153A1、20040007525A1、PCT申请WO0108790A1和US6547968中公开了浸渍膜体系的化学清洗反洗方法的类似方法。化学清洗反洗可以是连续或者脉冲的，且可在排放薄膜贮罐之后，排放薄膜贮罐的同时或者甚至不排放薄膜贮罐而在化学反洗之前进行。当膜垂直取向时，化学溶液通过泵经膜顶部处的集管(header)输送到体系内。化学清洗溶液在压力下强制通过膜到内腔侧。反复反冲可引起在渗透管线内的生物膜变回为膜。
以上提及的第二和第三种方法通常使用比第一种方法体积小的化学溶液，但它们要求化学溶液具有非常高的质量且不含固体，这是因为溶液被引入到渗透侧。
本发明的目的是克服或者减轻现有技术的至少一个缺点，或者提供有用的替代方案。
发明内容
根据本发明的第一方面，提供清洗具有原料侧和渗透侧的多孔聚合物膜的方法，该方法包括下述步骤：将含清洗剂的流体引入到膜的渗透侧；允许清洗剂接触膜的渗透侧预定时间，和接触膜的孔隙。
优选地，清洗剂在静压下接触渗透侧。
根据第二方面，本发明提供清洗具有原料侧和渗透侧的多孔聚合物膜的方法，该方法包括下述步骤：将含清洗剂的流体引入到膜的原料侧；施加跨膜压力，强制含清洗剂的流体从膜的原料侧到渗透侧；允许清洗剂接触膜的渗透侧预定的时间，和接触膜的孔隙。
优选地，跨膜压力的压差小。
根据本发明的第三方面，提供清洗具有原料侧和渗透侧的多孔聚合物膜的方法，该方法包括下述步骤：提供与膜的原料侧接触的原料侧流体；引入含清洗剂的流体到膜的渗透侧；允许清洗剂接触膜的渗透侧预定的时间，接触膜的孔隙并扩散到原料侧的流体内。
优选地，在本发明的这一方面中，通过在原料侧流体(优选清洗剂浓度低)和含有清洗剂的内腔侧流体之间的浓度梯度驱动溶液的扩散。最优选原料侧流体不含清洗剂。
优选地，本发明的方法进一步包括下述步骤：在渗透侧上施加压力到含清洗剂的流体上，从膜孔隙中移动(若存在的话)溶解和未溶解的固体。更优选，这一压力以脉冲方式施加。在一个尤其优选的实施方案中，压力源是压力不大于膜泡点的压缩空气。
优选地，本发明的方法之前全部进行反洗。
优选地，本发明的方法还紧跟着反洗，之后再开始过滤。
视需要，本发明的方法可反复循环。
本发明所述的清洗方法可应用于加压膜滤或者浸渍膜滤体系上。该膜可以是微滤、超滤或纳滤膜，且可以或者是毛细膜或者平片(flatsheet)膜。
优选地，膜是超滤或微滤膜。
在优选的实施方案中，本发明的膜是具有内腔侧(渗透侧)和模件(module)或外壳侧(原料侧)的中空纤维膜，其中多个中空纤维膜安装在模件外壳内。
最优选，多个膜排列在校直的纤管束(bundle)内。模件在纤管束末端装入，从而在中空纤维内部产生多个内腔空间和在中空纤维的外部或外壳侧上产生邻接的空间。排列内腔，以便过滤的水在其内累积并从多个内腔流入合并的过滤物流内。
流体可以是水。
在第一和第三方面中，含清洗剂的流体引入到这些中空纤维膜的内腔中。在第二方面中，含清洗剂的流体，优选通过部分填充模件的外壳侧而引入到膜的外壳侧，之后输送到内腔内。
优选地，在没有施加压力或者施加轻微压力的情况下，含可扩散的清洗剂的流体保留在膜的渗透侧内，可施加大致等于静态排出(head)压力的压力。
清洗溶液可以是任何常规的清洗溶液，它或者酸性、碱性或者为中性，或者可以是具有氧化性或者还原性，这取决于污垢的来源。清洗剂也可以是无机或有机的。优选的清洗剂包括溶解的卤素，例如氯，或者溶解的氧化或还原剂，例如亚硫酸盐基试剂。或者，清洗剂可以是螯合剂，例如柠檬酸或者EDTA。为了促进污垢的润湿和溶解，可将小量表面活性剂加入到清洗溶液中。
在膜体系中，化学清洗剂输送的优选方案随体系设计的变化而变化。例如，在一些膜滤体系中，优选输送化学清洗剂到膜的原料侧上。如果这样的话，制备化学溶液所使用的水就其固体含量来说，其要求不是特别地苛刻，和该清洗溶液可反复使用数次。然而，它可要求化学贮罐和化学转移泵。这一输送方法常常用于大的膜体系上。在其他膜体系中，优选输送化学清洗剂到渗透侧上，进一步降低化学溶液的体积和改进操作的容易程度。在这种情况下可使用计量泵。本发明的方法适合于处理或者原料侧或者内腔侧计量。
附图说明
图1示出了本发明的一个实施方案，其中该实施方案能使溶液输送到中空纤维膜的外壳侧并渗透通过内腔侧。
图2示出了本发明的一个实施方案，其中在外壳侧首先至少部分排放/过滤的情况下，该实施方案能使溶液输送到中空纤维膜的内腔侧。
图3示出了本发明的一个实施方案，其中该实施方案能使溶液输送到中空纤维膜的内腔侧，同时含固体的水保留在外壳侧上。
图4示出了维护清洗和清洗效率定义的试验曲线。
图5示出了采用不同试验方法的膜性能恢复率。
图6示出了对于许多清洗方法来说，相对化学清洗剂的消耗。
具体实施方式
参考成束排列并安装在模件内的中空纤维聚合物微滤和超滤膜，和参考采用从外侧向内侧的过滤模式的加压膜滤体系的维护清洗，公开本发明。然而，要理解本发明不限于这种实施方案，和可例如包括从内侧向外侧的过滤模式。
测试并比较包括将清洗剂计量到外壳侧或者内腔侧(滤液侧)的数种维护清洗(膜清洗)方案。以下将讨论这些方法及其性能。
优选在任何维护清洗之前进行反洗。在中空纤维膜的反洗工艺中，例如通过气体压力或者通过进一步的液体泵送，强制液体从内腔侧通过膜。作为反洗工艺的一部分，可在反洗期间和在引入任何清洗溶液之前，或者排放、部分排放或者用液体填充外壳侧。
进行反洗的正常工序通常包括起始的过滤或者排放工艺。更优选过滤。优选采用进入外壳侧的压缩空气作为过滤驱动力推动外壳侧液体通过膜并进入内腔，在低于膜泡点的压力下实现过滤。继续过滤，直到外壳侧的液体水平至少小于外壳侧液体保持体积的一半。在其中清洗之前没有进行反洗的情况下，作为维护清洗的起始步骤进行过滤。优选地，外壳侧的液体水平下降到采用压缩空气可以实现的过滤的最低水平，在大多数情况下，该水平通常仅仅高于较低的模件罐封(module potting)。过滤意味着外壳侧体积大大地下降，因此在不需要排放外壳侧的情况下，任何维护的清洗溶液可进入该体系内。对于浸渍的膜滤工艺来说，不要求压缩空气进行过滤。
紧跟着排放或者过滤之后，可进行液体的反洗，优选采用空气冲刷进行反洗。可按照不同的方式实现液体反洗。优选使用空气推动的反洗。低于膜泡点的压缩空气进入内腔并推动滤液以与过滤方向相反的方向通过膜。仅仅在过滤或者滤过最后保留在内腔内的滤液用于反洗。紧跟在反洗之后，内腔倒空且易于接收化学清洗溶液。
通常用结垢材料覆盖要求维护清洗的膜，和一些膜的孔隙也可能被堵塞。反洗的优点是，部分除去孔隙的堵塞物和结垢层，从而使清洗溶液能在较大的百分数下到达膜表面。当在没有反洗情况下使用维护清洗时，清洗溶液可借助未堵塞的路径优先扩散经过膜，所述未堵塞的路径可作为结垢较少的膜表面区域和未堵塞的膜孔隙的结果而存在。在采用充足的空气压力情况下，在内腔内的滤液在合理的速度下流经膜孔隙，并除去在膜表面上的一些结垢物质，和使一部分堵塞的孔隙打开。这使得化学溶液(当引入时)能在较大的百分数下到达膜孔隙。
在任何初步维护清洗反洗最后，外壳侧的液体可或者排放或者作为一部分反洗工艺保留。由于通过在先的过滤实现了外壳侧液体体积的下降，因此甚至当从反洗顺序最后取消排放时，在维护清洗之前，外壳侧的液体体积通常小于外壳侧液体保持体积的一半。在维护清洗之前排放外壳侧液体是任选的。
或者，在维护清洗之前，膜没有反洗，而是过滤或者排放外壳侧，以降低外壳侧体积，之后输送维护的清洗溶液。
取决于所选的特定方法，化学溶液或者优选借助较低的CIP(原地清洗)歧管输送到外壳侧，或者优选借助较低的滤液/CIP歧管，或者二者的串联，输送到滤液(内腔)侧。
在本发明的方法中，对于内腔侧的化学输送来说，溶液流速优选低(0.1-4m3/h/模件)，这取决于模件尺寸，以便最小化在这一阶段中可能出现的负面的跨膜压力。取决于特定的输送方法，在清洗中所使用的最大的清洗溶液体积优选不大于内腔体积、外壳体积或者二者的体积(加上任何管道容纳或者涨落体积)。对于控制化学溶液的消耗来说，这尤其重要。
可通过与合适的流体体积相连的任何已有的泵，例如装置CIP泵，输送清洗溶液。若清洗溶液主要输送到内腔侧，则清洗溶液的使用率非常低。在这一情况下，可在密封的贮罐内储存清洗溶液，和压缩空气可用作输送工具，推动溶液从贮罐进入中空纤维膜的内腔内。其优点是若贮罐配有流体液面传感器，或者若贮罐体积类似于总的内腔体积，则可大大地简化输送到体系中的溶液体积的控制。
一旦清洗溶液输送到体系中，则停止CIP泵或者除去气体压力源。取决于在清洗中所使用的化学品，视需要可在浸泡期间借助上部歧管放空外壳侧和内腔侧，或者在浸泡期间周期性放空。当放空时，外壳侧的通气可用于混合化学品并改进化学品与膜的接触。当将溶液计量到滤液(内腔)侧时，若溶液扩散通过膜壁并到达外壳侧，则可使用外壳侧通气。溶液扩散通过膜孔隙到达其中不存在液体或者很少存在液体或者其中溶液内清洗剂浓度低的一侧。
当外壳侧和内腔侧均被填充时，化学清洗剂仅仅通过浓度梯度扩散到膜孔隙内。膜孔隙浸泡在溶液内一段时间，对于典型的维护清洗来说优选30秒-20分钟，和对于充分的化学清洗来说要求较长的时间。视需要，可在浸泡期间借助上部歧管放空外壳侧和内腔侧，或者在浸泡期间周期性放空。由于在内腔或者外壳侧内蒸发导致的湿度损失非常低，和采用清洗溶液的情况下，膜孔隙保持湿润。
视需要，可进行反洗，从体系中除去残留的清洗溶液，之后开始过滤。
方法1：用化学清洗溶液部分填充膜的外壳侧
在这一方法中，化学溶液优选借助较低原料歧管进入外壳侧。然而，溶液进入外壳侧且所有的外壳出口阀门关闭，即在死端过滤模式下，强制清洗溶液进入内腔侧。若压力没有足够高到推动清洗溶液到达渗透侧，则可通过注入与压滤工艺一样的压缩空气，或者通过与浸渍膜过滤工艺一样的抽吸，来供应额外的跨膜压力。外壳侧仅仅用膜清洗溶液部分填充。到达外壳侧的溶液的最小输送体积略高于内腔体积加上渗透歧管体积。这一方法的化学品和滤液的消耗显著小于其中外壳侧用化学溶液填充的常规清洗方法。
这一方法的第一步优选是反洗，然后倒空外壳侧和内腔侧二者。清洗溶液借助较低的CIP阀门进入外壳侧。然而，由于外壳侧的上部CIP回流阀门关闭和内腔CIP回流阀打开，因此一旦在外壳侧内CIP溶液的液面高于下部的封装水平，通过外壳侧的压力强制CIP溶液进入内腔侧。还在外壳侧的液面以上形成压缩空气袋。取决于外壳侧的压力，CIP泵仅仅可运行短的时间段，和这使得来自空气袋的压力继续挤压溶液到内腔侧。可视需要供应额外的跨膜压力。取决于在进入外壳侧内之前溶液的混合，膜清洗溶液的过滤可仅仅填充内腔或者延伸，以输送一些溶液返回到CIP罐或者循环管道环路中。或者，CIP溶液可通过压缩空气推动到外壳侧内，从而省去CIP泵短的运行循环。
在用化学溶液填充内腔侧之后，然后打开外壳侧和内腔侧的排放阀，使压力相等。在内腔侧压力接近于外壳侧压力时，打开外壳侧排放阀，同时内腔侧排放阀可以或者打开、关闭，或者周期性打开，以控制扩散过程。当周期性打开内腔侧排放阀时，优选简单地在浸泡的起始阶段期间打开阀门。在整个浸泡期间，内腔侧可放空1-10次，其中每一次持续1秒-10分钟。在内腔侧内的溶液缓慢地经膜扩散，和当打开内腔侧排放阀时，可通过在内腔侧内的静压辅助扩散过程。膜部分浸泡在溶液内，然而，毛细作用有助于保持溶液在膜壁内。
也可采用任选的后通气操作。这一通气操作有助于悬浮的污物变得松散或者通过溶液除去。
可视需要反复以上的填充内腔和反扩散工序，以实现较高的清洗效率。
也可在浸泡之后使用任选的后膜清洗反洗。优选在充分地排放外壳侧化学废物最后，进行充分的反洗。如果优选的话，则从外壳侧排放的膜清洗化学品可通过排放到CIP管内再使用。
然后开始过滤。
现有技术的常规清洗方法典型地包括1)用化学溶液充分地填充外壳侧，2)短时间段地过滤化学溶液，3)允许膜浸泡，和4)排放随后的化学废物。以上所述的方法1可显著地降低化学品和化学废物的体积典型地大于50％。在没有额外的化学品的情况下，反复的内腔填充和反扩散工序有助于提高清洗效率。
图1示出了其中外壳侧和内腔倒空情况下的方法1。外壳侧用清洗溶液部分填充，然后加压，以便液体流到内腔内。
方法2：用化学溶液填充膜的渗透侧，和至少部分排放/过滤外壳侧
在这一方法中，输送化学溶液，填充膜内腔(渗透侧)，因此化学品和滤液的消耗非常低。
这一方案的第一步优选是借助以上所述的方法反洗膜。它使内腔侧倒空，和外壳侧或者倒空或者部分倒空。膜内腔侧然后准备用于接收清洗溶液。在通过反洗，膜内腔侧没有倒空的情况下，必须在压力下输送化学溶液，以取代膜内腔内残留的渗透物。
然后用膜清洗溶液填充内腔。化学计量泵或CIP泵用于优选借助较低的滤液/CIP阀门引入膜清洗溶液到内腔侧，和任何额外的溶液可借助上部的滤液/CIP阀门流出内腔侧，返回到CIP罐。在化学输送期间，外壳侧的上部CIP阀门可或者打开或者关闭。当用化学溶液填充内腔时，打开外壳侧排放阀，和可或者打开、关闭或者周期性打开内腔侧的排放阀。当周期性打开内腔侧的排放阀时，优选简单地在起始的浸泡阶段期间打开阀门。在整个浸泡期间，内腔侧可以放空1-10次和每一次持续5秒-10分钟。发生化学扩散，直到在内腔和外壳侧的化学品浓度相等。
当外壳侧倒空或者部分倒空时，在内腔侧内的一部分溶液缓慢地通过膜孔隙扩散，和当打开内腔侧的排放阀时，通过内腔侧内的静压辅助。在这一工艺过程中，外壳侧和内腔侧二者部分倒空，然而，毛细作用辅助保持溶液在膜壁内。进行浸泡和扩散工艺预定的时间，直到膜与希望的一样清洁，或者直到大多数清洗溶液被消耗。
视需要，在内腔侧内的溶液扩散到外壳侧内并消耗后，可反复用化学清洗溶液填充内腔的工序。或者可通过施加压缩空气到外壳侧，将扩散到外壳侧内的溶液推动回到内腔侧。可视需要反复这一工序。
图2示出了方法2，引入溶液到内腔侧，同时完全或部分排空外壳侧。
方法3：用化学溶液填充膜的渗透侧且外壳侧没有排放
这一方法类似于方法2，所不同的是，没有过滤外壳侧。若含有固体的水保留在外壳侧上(如图3所示，没有排放的罐)，则化学溶液在浓度梯度下扩散通过膜孔隙到达外壳侧，且扩散速度沿着膜模件相当均匀。继续扩散过程，直到在两侧上的化学品浓度达到平衡。
视需要，在内腔侧内的化学品浓度降低到一定水平之后，可反复用化学清洗溶液填充内腔的工序。
也可使用任选的后通气操作，这一通气操作有助于悬浮的污垢变得松散或者通过溶液除去。
也可在浸泡之后使用任选的膜的后清洗反洗操作。在排放化学废物最后优选利用充分的反洗。
然后开始过滤。
图3示出了方法3的示意图。用引入到内腔内的水或者其他流体和清洗溶液填充内腔。清洗物种经膜从内腔内的较高浓度的区域扩散到外壳侧内的较低浓度处。
图1-3示出了各种方法的管道和仪器示意图。
在附图中，P1是原料泵和P2是CIP泵。P2可被在容器顶部具有压缩空气入口的小型溶液存储容器替代。
如果要求通气，则SV1供应冲刷空气。SV2供应压缩的排放空气，以辅助在外壳侧或者过滤处辅助快速排放。SV3供应压缩的液体反洗空气，以与过滤方向相反的方向推动内腔内的滤液经过膜孔隙。AV1是下部的原料阀和AV2是上部的原料阀。AV4是下部的外壳侧排放阀和AV5是上部的外壳侧回流阀。
在图1所示的方法1中，输送清洗溶液到外壳侧。用化学溶液部分填充外壳侧，并允许溶液在TMP下渗透到渗透侧。
当CIP泵开始输送清洗溶液到外壳侧时，AV7和AV3打开和AV5关闭。在外壳侧上的压力缓慢增加，和一些化学溶液在压力下渗透到内腔侧。当在外壳侧上的溶液液面达到较低的罐封头和模件中间之间的位置时，停止化学品输送，或用化学溶液填满膜内腔。若在外壳侧上的压力没有足够高到推动溶液到达内腔侧，则可借助SV2注入压缩空气到外壳侧。在浸泡预定的时间段之后，可进行反洗，推动在渗透侧上的残留化学溶液返回到外壳侧。优选通过SV3引入压缩空气，以推动内腔内的残留溶液返回到外壳侧。
在方法2和3中，计量清洗剂到内腔侧。在计量阶段期间，AV9和AV3均打开，和在外壳侧出口上的AV5可或者打开或者关闭(图2和3)。在用该溶液填满渗透侧之后，终止化学品输送。然后化学溶液经膜孔隙渗透。在方法2中，通过液体的静压继续渗透，和化学溶液扩散返回到外壳侧。当外壳侧充满时，仅仅通过浓度梯度驱动扩散(图3)。优选在扩散时间段之后再次进行反洗。
实施例
为了对比试验，使用6模件的Memcor CMF-L中试试验。过滤工艺包括30分钟过滤，紧跟着气体推动的反洗。在进行维护清洗之前，反复循环数次。
如图4所示，通过膜阻力增加来判断膜的结垢速度。在过滤30分钟之后，膜的阻力上升。反洗可部分降低膜的阻力。然而，反洗没有充分地恢复膜的渗透性和阻力趋势继续上升。进行维护清洗进一步降低膜的阻力，因此较好地恢复膜的渗透性。一般趋势如图4所示。维护清洗效率定义为：
MC效率＝(R1-R2)/(R1-R0)
其中R0是直接在最后的化学清洗之后的阻力。
R1是直接在最后的反洗之后，维护清洗之前的阻力。
R2是在前一维护清洗之后的阻力。
图5示出了采用不同方法的维护清洗效率，其中：
MC0-常规清洗方法，其中用清洗溶液充分地填充外壳侧，
MC1-以上所述的方法1，外壳侧用清洗溶液部分填充，
MC2-以上所述的方法2，其外壳侧排空和清洗溶液填充渗透侧，
MC3-以上所述的方法3，其中没有排放外壳侧且清洗溶液填充渗透侧。
图6示出了与常规方法相比，相对的化学溶液消耗。
Claims (32)
1.清洗具有原料侧和渗透侧的中空纤维多孔聚合物膜的方法，该方法包括下述步骤：
将含清洗剂的流体引入到膜的渗透侧；
允许清洗剂在静压下接触膜的渗透侧预定时间，和接触膜的孔隙，
其中在没有施加压力情况下，含可扩散的清洗剂的流体保留在膜的渗透侧内，以用含所述清洗剂的所述流体填充膜渗透侧和膜孔隙浸泡在含所述清洗剂的所述流体中一段时间，以使所述清洗剂仅仅通过浓度梯度扩散到膜孔隙内。
2.清洗具有原料侧和渗透侧的中空纤维多孔聚合物膜的方法，该方法包括下述步骤：
将含清洗剂的流体引入到膜的原料侧；
施加跨膜压力，强制含清洗剂的流体从膜的原料侧到渗透侧；
允许清洗剂在静压下接触膜的渗透侧预定的时间，和接触膜的孔隙，其中在没有施加压力情况下，含可扩散的清洗剂的流体保留在膜的渗透侧内，以用含所述清洗剂的所述流体填充膜渗透侧和膜孔隙浸泡在含所述清洗剂的所述流体中一段时间，以使所述清洗剂仅仅通过浓度梯度扩散到膜孔隙内。
3.清洗具有原料侧和渗透侧的中空纤维多孔聚合物膜的方法，该方法包括下述步骤：
提供与膜的原料侧接触的原料侧流体；
引入含清洗剂的流体到膜的渗透侧；
允许清洗剂在静压下接触膜的渗透侧预定的时间，以接触膜的孔隙并扩散到原料侧的流体内，
其中在没有施加压力情况下，含可扩散的清洗剂的流体保留在膜的渗透侧内，以用含所述清洗剂的所述流体填充膜渗透侧和膜孔隙浸泡在含所述清洗剂的所述流体中一段时间，以使所述清洗剂仅仅通过浓度梯度扩散到膜孔隙内。
4.权利要求3的方法，其中在原料侧流体和含有清洗剂的内腔侧流体之间的浓度梯度引起清洗剂扩散到原料侧流体内。
5.权利要求4的方法，其中原料侧流体的清洗剂浓度低于内腔侧流体。
6.权利要求1、2或3的方法，它进一步包括下述步骤：在渗透侧上施加压力到含清洗剂的流体上，从膜孔隙中移去溶解和未溶解的固体，若存在的话。
7.权利要求6的方法，其中以脉冲方式施加压力，并且根据需要通过对所述原料侧流体施加压力可使该流体从原料侧脉冲返回到所述渗透侧。
8.权利要求6的方法，其中膜具有泡点，和压力是借助在不大于膜的泡点的压力下的压缩空气实现。
9.权利要求1、2或3的方法，在所述方法之前进行反洗。
10.权利要求1、2或3的方法，紧跟着反洗，之后重新开始过滤。
11.权利要求1、2或3的方法，其中反复循环所述方法。
12.权利要求1、2或3的方法，其中所述多孔聚合物膜是加压膜过滤或者浸渍膜过滤体系的一部分。
13.权利要求1、2或3的方法，其中所述膜选自微滤、超滤或纳滤膜。
14.权利要求1、2或3的方法，其中所述膜是毛细膜或者平片(flatsheet)膜。
15.权利要求1、2或3的方法，其中所述膜是具有内腔侧和模件(module)或外壳侧的中空纤维膜。
16.权利要求15的方法，其中多个中空纤维膜安装在模件外壳内。
17.权利要求16的方法，其中多个膜排列在校直的纤管束(bundle)内，从而在中空纤维内部产生多个内腔空间和在中空纤维的外部或外壳侧上产生邻接的空间，和其中排列内腔，以便过滤的流体在其内累积并从多个内腔流入合并的过滤物流内。
18.权利要求1、2或3的方法，其中流体是水。
19.权利要求17的方法，其中含清洗剂的流体引入到这些中空纤维膜的内腔中。
20.权利要求17的方法，其中含清洗剂的流体引入到膜的外壳侧。
21.权利要求20的方法，其中通过部分填充模件的外壳侧而引入含清洗剂的流体到膜的外壳侧，之后输送到内腔内。
22.权利要求1、2或3的方法，其中在压力等于静态排出压力的情况下，含可扩散的清洗剂的流体保留在膜的渗透侧内。
23.权利要求1、2或3的方法，其中清洗溶液是任何常规的清洗溶液。
24.权利要求23的方法，其中清洗溶液为酸性、碱性或中性。
25.权利要求23的方法，其中清洗溶液具有氧化或还原性。
26.权利要求23的方法，其中清洗剂是无机或有机的。
27.权利要求23的方法，其中清洗剂包括溶解的卤素。
28.权利要求27的方法，其中卤素是氯。
29.权利要求23的方法，其中清洗剂包括亚硫酸盐基试剂。
30.权利要求23的方法，其中清洗剂包括螯合剂。
31.权利要求30的方法，其中螯合剂是柠檬酸或EDTA。
32.权利要求23的方法，其中将表面活性剂加入到清洗溶液中。
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| CN2006800183237A Expired - Fee Related CN101184548B (zh) | 2005-04-29 | 2006-04-28 | 用于膜滤器的化学清洗剂 |
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| US (1) | US9675938B2 (zh) |
| EP (1) | EP1885475B1 (zh) |
| JP (1) | JP2008539054A (zh) |
| KR (1) | KR20080005993A (zh) |
| CN (1) | CN101184548B (zh) |
| CA (1) | CA2605757A1 (zh) |
| NZ (1) | NZ562786A (zh) |
| WO (1) | WO2006116797A1 (zh) |
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- 2006-04-28 JP JP2008508024A patent/JP2008539054A/ja active Pending
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| CN1333705A (zh) * | 1998-08-12 | 2002-01-30 | 三菱丽阳株式会社 | 用于固体－液体分离的薄膜组件、清洗该组件的方法和洗涤剂 |
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| US9675938B2 (en) | 2017-06-13 |
| EP1885475A4 (en) | 2011-03-09 |
| CA2605757A1 (en) | 2006-11-09 |
| EP1885475B1 (en) | 2015-03-25 |
| US20080203017A1 (en) | 2008-08-28 |
| WO2006116797A1 (en) | 2006-11-09 |
| CN101184548A (zh) | 2008-05-21 |
| KR20080005993A (ko) | 2008-01-15 |
| NZ562786A (en) | 2010-10-29 |
| EP1885475A1 (en) | 2008-02-13 |
| JP2008539054A (ja) | 2008-11-13 |
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