CN108137348A - 含氨废水的膜处理 - Google Patents
含氨废水的膜处理 Download PDFInfo
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- CN108137348A CN108137348A CN201580083865.1A CN201580083865A CN108137348A CN 108137348 A CN108137348 A CN 108137348A CN 201580083865 A CN201580083865 A CN 201580083865A CN 108137348 A CN108137348 A CN 108137348A
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Abstract
一种用于处理含氨废水的方法，包含以下步骤：i)使所述废水作为进料溶液通过第一RO膜(24)以产生第一渗透流(30)和第一废料流(32)，ii)将所述第一废料流(32)的pH调节到>9，iii)使所述第一废料流(32)通过第二RO膜(26)以产生含有氨的第二渗透流(36)和第二废料流(38)，以及iv)使所述第二渗透流(36)的至少一部分通过冷却塔(12)以蒸发至少一部分所述氨。
Description
技术领域
本发明涉及用于处理废水的膜基方法。
背景技术
化学加工废水的处理和再利用正在成为越来越受关注的活动。这类水包括各种污染物，包括成垢盐、氨和其它碎片。虽然已知减少氨的技术(例如微生物促进的去硝化)，但期望新的技术。
发明内容
本发明包括用于处理含氨废水的系统和方法，并且包含以下步骤：
i)使废水作为进料溶液通过第一反渗透(RO)膜以产生第一渗透流和第一废料流，
ii)将第一废料流的pH调节到>9，
iii)使第一废料流通过第二RO膜以产生含有氨的第二渗透流和第二废料流，以及
iv)使第二渗透流的至少一部分通过冷却塔以蒸发至少一部分氨。
在一个优选实施例中，废水包括从冷却塔排放的水，并且第二渗透流用作冷却塔的补充水。描述了各种实施例。
附图说明
附图不是按比例绘制的，并且包括理想化的视图以便于描述。在可能的情况下，在附图和书面描述中使用相同的数字来表示相同或相似的特征。
图1是本发明的第一实施例的示意图。
图2是本发明的第二实施例的示意图。
具体实施方式
本发明尤其可用于开放再循环(蒸发)冷却水系统方面。在这类系统中，来自冷却塔的水通过需要冷却的处理设备(热负载)，然后通过冷却剩余水的蒸发单元(冷却塔或蒸发冷凝器)返回。水通过系统再循环，其中加入足够的淡水补充以平衡从系统排出的蒸发和废水排放的水损失，以控制循环水的化学特征。在优选的实施例中，本发明还涉及一种含氨的水源，其为待处理废水的氨的主要来源。更具体来说，将含氨废水(pH小于9)作为进料溶液通过第一反渗透(RO)膜。在这一pH下，废水中存在的大部分(例如超过90％)氨被第一RO膜阻挡。因此，所述第一废料流更富集氨。然后将所述第一废料流的pH调节到高于9，更优选高于10并通过第二RO膜。在这一更高的pH下，第二RO膜仍然会阻挡大部分存在的溶解固体和盐。然而，大部分“氨”以氨(NH3)而不是铵(NH4 +)的形式存在，并且氨(NH3)很少被RO膜阻挡。在优选实施例中，将来自第二RO膜的渗透流(“第二渗透流”)的至少一部分作为补充水引入蒸发单元。在引入时，存在于第二渗透流中的氨大量蒸发到环境中。总体结果是在系统中不存在非所期望的氨浓度的情况下再利用废水作为补充。相比之下，第一渗透流优选经历不同用途，例如送至脱气机。
参考图1的实施例，大体上以10展示开放再循环冷却水系统的示意图，包括含有氨的水源(11)、排放管线(20)、补充线(22)和包括热负载(18)和具有蒸发排气口(14)的冷却塔(12)的冷却塔再循环回路(16)。在所示实施例中，排放管线(20)与含氨的水源(11)组合。通过至少两级反渗透膜单元处理含有氨的组合废水(21)，在上游单元(第一RO膜单元)(24)阻挡的情况下随后由下游单元(第二RO膜单元)(26)处理。虽然未示出，但是可以包括用于处理废水的另外的单元操作(例如，引入化学添加剂，如防垢剂、杀生物剂、还原剂、防腐蚀添加剂；过滤(介质，滤筒，超滤)和离子交换)。该系统还可以包括用于处理来自第二RO膜单元(26)的废料的蒸发器或冷凝器(28)。这允许系统(10)接近零液体排放。
在操作期间，含氨的水源(11)优选地与来自排放管线(20)的从水再循环回路(16)抽取的流体组合，例如从冷却塔(12)的底部，热负载(18)抽取等。在这一实施例中，将含有氨的组合废水作为进料溶液提供到第一RO膜单元(24)。废水的pH优选<9(更优选<8.5)。使废水通过第一RO膜(24)来处理，以产生第一渗透流(30)和第一废料流(32)。然后优选通过添加碱(例如NaOH、石灰等)将第一废料流的pH调节到>9(更优选>10)。定量泵(34)或类似装置可以用于计量碱的添加。在pH调节之后，使第一废料流(32)通过第二RO膜(26)以产生第二渗透流(36)和第二废料流(38)。第二废料流(38)可以任选地通过蒸发、正向渗透或结晶(28)来处理。将第二渗透流(36)的至少一部分作为补充水返回到冷却塔(12)。第一渗透流(30)的部分也可以用作补充或用于其它目的。一旦引入冷却塔(12)，存在于第二渗透流(36)中的至少一部分氨被蒸发并从冷却塔(12)排出(14)。在引入冷却塔之前，第二渗透流(36)中氨的浓度大于冷却塔再循环回路(16)中与到第一RO单元的进料溶液中的氨的平均浓度。更优选地，第二渗透流(36)中氨的浓度是第一渗透流(30)中氨的浓度的至少10倍。存在于冷却塔再循环回路(16)中的代表性氨浓度为0.1ppm至5ppm。取决于进料废水组成，第一(32)和第二渗透流(36)中的代表性氨浓度为0ppm至1ppm和0.5ppm至20ppm。
图2展示了本发明的第二实施例的示意图。在这一实施例中，例如来自地表水的含氨的水源(11)进入工业设备。在任选的预处理步骤(42)之后，可以将水源通过补充线(22)提供到工业加工(44)、脱矿站(48)和/或冷却塔(12)。在优选实施例中，脱矿站(48)可以包括RO系统(50)。脱矿站(48)中来自RO的渗透物(60)可用于锅炉(52)或工业过程(44)。含氨的组合废水(21)可以包含来自脱矿站中RO的浓缩流(62)、来自工业过程(42)的废物流(64)和来自冷却水排放管线(20)的流体。尤其，来自脱矿站(48)的浓缩流(62)可具有氨水平。在成为第一反向膜的进料并且通过第一RO膜(24)以产生第一渗透流(30)和第一废料流(32)之前，含氨废水(21)可以经历另外的预处理(46)。优选通过添加碱(例如NaOH、石灰等)将第一废料流的pH调节到>9(更优选>10)。定量泵(34)或类似装置可以用于计量碱的添加。在pH调节之后，使第一废料流(32)通过第二RO膜(26)以产生第二渗透流(36)和第二废料流(38)。第二废料流(38)可以任选地通过蒸发或结晶(28)来处理。将第二渗透流(36)的至少一部分作为补充水返回到冷却塔(12)。
本发明包括使用RO膜。虽然可以使用各种膜构型(例如中空纤维、管状、板和框架)，但螺旋缠绕组件(“元件”)是优选的。RO膜对几乎所有溶解盐为相对不可渗透的并且通常阻挡超过约95％的单价离子盐，如氯化钠。RO膜还通常阻挡超过约95％的无机分子以及分子量大于约100道尔顿的有机分子。纳米过滤(NF)膜比RO膜更为可渗透，并且通常阻挡小于约95％的单价离子盐，同时阻挡大于约50％(并且常常大于90％)的二价离子盐，这取决于二价离子的种类。NF膜还通常阻挡在纳米范围内的粒子以及分子量大于约200到500道尔顿的有机分子。除非另外陈述，否则术语“反渗透”用于涵盖RO(反渗透)和纳米过滤(NF)两者。
在别处(US 6881336、US 8142588和US 8496825)详细描述了螺旋卷绕组件构型。螺旋卷绕膜组件可通过围绕渗透收集管卷绕一个或多个膜包封和任选的进料通道间隔薄片(进料隔片)来形成。每一个膜包封优选包含在渗透通道间隔薄片(“渗透隔片”)周围的两个基本上矩形的膜片。这种夹层型结构例如通过密封剂沿三个边固定在一起，而第四边对接渗透收集管。渗透隔片与通过渗透收集管的开口处于流体接触。元件的外壳可由各种材料(包括不锈钢、胶带和PVC材料)构建。关于螺旋卷绕元件的不同部件和构型的额外细节提供于文献中，参见例如：US 5538642，描述了用于将渗透隔片附接到渗透收集管的技术；US7951295，描述了用于形成插入点密封的UV粘合剂的整平操作和使用；US 7875177，描述了可适用的叶片包。
膜片不受特定限制并且可使用多种材料，例如醋酸纤维素材料、聚砜、聚醚砜、聚酰胺、聚偏二氟乙烯等。优选的膜片为具有通过界面聚合形成的区别层的组合式结构。典型复合物超滤膜包括非织背衬网(例如购自阿波纸业公司(Awa Paper Company)的非织织物，如聚酯纤维织物)的背层(背侧)、包含典型厚度为约25-125μm的多孔载体的中间层和包含厚度通常小于约1微米(例如0.01微米到1微米，但更通常约0.01到0.1μm)的薄膜聚酰胺层的顶区别层(前侧)。背层不受特定限制，但优选包含包括可经定向的纤维的非织织物或纤维网。或者，可以使用诸如帆布之类的纺织织物。代表性实例描述于US 4,214,994；US 4,795,559；US 5,435,957；US 5,919,026；US 6,156,680；US 2008/0295951和US 7,048,855中。多孔载体通常为具有一定孔径的聚合材料，所述孔径具有足以准许渗透物基本上不受限制通过的尺寸，但并未大到足以干扰上面形成的薄膜聚酰胺层的桥接。举例来说，载体的孔径优选地介于约0.001到0.5μm范围内。多孔载体的非限制性实例包括由以下制成的多孔载体：聚砜、聚醚砜、聚酰亚胺、聚酰胺、聚醚酰亚胺、聚丙烯腈、聚(甲基丙烯酸甲酯)、聚乙烯、聚丙烯以及各种卤化聚合物(如聚偏二氟乙烯)。如US 4277344和US 6878278中所述，区分层优选通过多官能胺单体与多官能酰基卤单体之间的界面聚缩合反应在微孔聚合物层的表面上形成。
虽然组件有多种尺寸可供选择，但一个普通的工业RO组件可具有标准的8英寸(20.3厘米)直径和40英寸(101.6厘米)的长度。对于典型的8英寸直径组件，围绕渗透收集管卷绕26到30个单独的膜包封(即，对于具有从约1.5英寸到1.9英寸(3.8cm到4.8cm)的外径的渗透收集管)。
将一个或多个组件布置在压力容器内。用于本发明的压力容器不受特别限制，但优选包括能够承受与操作条件相关的压力的固体结构。容器结构优选地包括具有内周边的腔室，所述内周边对应于待容纳于腔室中的螺旋卷绕组件的外周边。腔室的长度优选地与待依次(轴向)装载的元件的组合长度一致，例如1到8个元件，参见Mickols的US2007/0272628。压力容器还可包括在装载有组件时密封腔室的一个或多个端板。容器还包括至少一个流体入口和出口，其优选位于腔室的相对末端。压力容器的定向不受特定限制，例如可使用水平和垂直定向两者。在US 6074595、US 6165303、US 6299772和US 2008/0308504中描述了适用的压力容器、组件布置和装载的实例。压力容器制造商包括明尼苏达州明尼阿波利斯(Minneapolis MN)的滨特尔(Pentair)、加利福利亚州维斯塔(Vista CA)的贝卡尔特和以色列贝尔谢瓦(Beer Sheva,Israel)的Bel Composite。单独的压力容器或一起工作的容器的群组，各配备有一个或多个组件，通常称作“串”或“通道(pass)”。通道内的(一个或多个)容器可布置在一个或多个阶段中，其中每个阶段含有相对于进料流体平行操作的一个或多个容器。多个阶段串联布置，从而来自上游阶段的浓缩流体用作用于下游阶段的进料流体，同时可收集来自每一阶段的渗透物，其不在通道内进一步再处理。如US4156645，US6187200和US7144511中所述，多通道超滤系统通过沿流体路径相互连接单独的通道来构建。
在优选实施例中，第一RO膜单元包括在公共压力容器内串联连接的FilmTecTMBW30XFR-400/34i组件，并且第二RO膜单元包括在公共压力容器中串联连接的FilmTecTMBW30XFR-400/34i、SW30HRLE-370/34i或SEAMAXX。压力容器可以使用标准管道、数值等进行连接。废水可以使用常规泵加压。
第一RO单元优选在5巴到35巴的压力和60％到85％的回收率下操作。第二RO单元优选在15巴到80巴的压力和60％到95％的回收率下操作。
尽管已经提到了氨(NH3)，但应该理解，视pH而定也将存在不同量的铵(NH4 +)。如此，除了在被指定为“氨(NH3)”时，术语“氨”或“氨类”的目前使用将被理解为还包括“铵”。
已经描述了本发明的多个实施例并且在一些情况下，已经将某些实施例、选择、范围、成分或其它特征表征为“优选的”。“优选”特征的这类指定决不应被解释为本发明的基本或关键方面。前述专利和专利申请中的每一者的全部内容以引用的方式并入本文中。
Claims (7)
1.一种处理含氨废水的方法，包含以下步骤：
i)使所述废水作为进料溶液通过第一RO膜以产生第一渗透流和第一废料流，
ii)将所述第一废料流的pH调节到>9，
iii)使所述第一废料流通过第二RO膜以产生含有氨的第二渗透流和第二废料流，
以及
iv)使所述第二渗透流的至少一部分通过冷却塔以蒸发至少一部分所述氨。
2.根据权利要求1所述的方法，其中所述废水包括来自脱矿站的废料流中的氨、地表水、来自冷却塔的排放水或其组合。
3.根据权利要求1所述的方法，其中所述第二渗透流中氨的浓度大于所述第一RO膜的所述进料溶液中氨的浓度。
4.根据权利要求1所述的方法，其中所述第二渗透流中氨的浓度为所述第一渗透流中氨的浓度的至少10倍。
5.根据权利要求1所述的方法，其中将所述第一废料流的pH调节到>10。
6.根据权利要求1所述的方法，其中在处理前所述废水的pH<8.5。
7.根据权利要求1所述的方法，其中通过蒸发或结晶进一步处理所述第二废料流。
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| EP2493598B1 (en) | 2009-10-27 | 2014-07-16 | Dow Global Technologies LLC | Method for applying tape layer to outer periphery of spiral wound module |
| US8496825B1 (en) | 2010-10-26 | 2013-07-30 | Dow Global Technologies Llc | Spiral wound module including membrane sheet with regions having different permeabilities |
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- 2015-10-30 WO PCT/CN2015/093347 patent/WO2017070927A1/en active Application Filing
- 2015-10-30 EP EP15906990.5A patent/EP3368482A4/en not_active Withdrawn
- 2015-10-30 US US15/758,552 patent/US10752533B2/en active Active
- 2015-10-30 CN CN201580083865.1A patent/CN108137348B/zh active Active
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| CN1552638A (zh) * | 2003-12-19 | 2004-12-08 | 天津市海跃水处理高科技有限公司 | 一种氯化铵废水零排放处理工艺 |
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| CN111252932A (zh) * | 2018-11-30 | 2020-06-09 | 广州中国科学院先进技术研究所 | 基于直接接触式微孔曝气强化的膜吸收脱氨方法及系统 |
| CN111252932B (zh) * | 2018-11-30 | 2022-07-05 | 广州中国科学院先进技术研究所 | 基于直接接触式微孔曝气强化的膜吸收脱氨方法及系统 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20180257965A1 (en) | 2018-09-13 |
| EP3368482A1 (en) | 2018-09-05 |
| WO2017070927A1 (en) | 2017-05-04 |
| EP3368482A4 (en) | 2019-07-03 |
| CN108137348B (zh) | 2021-02-05 |
| US10752533B2 (en) | 2020-08-25 |
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