CN1345293A - 使用连续临界卤化方法净化空气和水 - Google Patents
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Abstract
这里描述了一种优化氧化过程速度的工艺,氧化过程使用氯这样的卤素来阻止不需要的氯化副产物的积累。控制氯的进料速度以保持所需的氧化还原势能(ORP),则氧化速度足以防止不需要的副产物的积累。通过保持连续临界卤化条件,可从水及周围空气中除去副产物。
Description
本发明涉及到同在申请中的、序号为()的专利申请内容，其标题为“使用连续临界卤化和过氧化方法净化空气和水”，其内容通过引证在这里被并入本文。
发明领域
本发明涉及水设施的维护，尤其涉及对氧化剂/消毒剂进料速度的优化，消除了不需要的卤化物的积累，由此提高了设施内空气和水的质量。
发明背景
在普通公用设施中使用的闭路再循环水系统，如游泳池、温泉浴、热水浴、装饰性喷泉、冷却水等，存在着各种各样的水质问题。例如，水中的化学失衡能导致各种类型的污染，包括细菌和病毒污染。
使用化学氧化剂/消毒剂是很普遍的水清洁方法。在水中添加像氯和溴这样所谓的卤素并维持在一定的浓度，它们就能有效地发挥作用。重要的是这些化学消毒剂的浓度不能过高，浓度过高会对使用者造成刺激并损害水系统。但用量不足又会造成水质污染。
由于对水的各种负载因素，虽然不是不可能、但却很难预测，因此要维持消毒剂处于适当的平衡状态就很困难。例如，游泳池的典型负载因素就是不断变化着的游泳者的数量。在热水浴中，喷气及高水温会破坏或除去水中的消毒剂。冷却水塔会受环境条件的影响，如环境温度的波动。室内装饰性喷泉会受建筑物内空气质量的影响，同时喷泉水也会影响建筑物内的空气质量。
有各种测试仪器可以测定游泳池、温泉等设施中水的化学平衡，如化学比色测试仪。它使用溶在水中的液滴、测试条或测试片来标定消毒剂的某一特定浓度。用勺或杯取一份从外观上看具有代表性的受测水样，然后用滴管加入染色剂。染色度与水中消毒剂的量有关，通过将水样与已有的测试标准样进行比色就可测定水中消毒剂的含量。此外，现在研究表明，水中游离卤素如氯的残留值与水的实际细菌量之间关系甚小，这就使得保持水系卫生清洁尤为艰难。而通常情况下用残留值来监测水体。长期以来，游泳池及温泉的维护人员认为游离氯的残留值为2毫克/升或2ppm，就可使水保持在安全卫生的状态。事实上，利用比色方法而测出的ppm值反映的是水中含有的游离氯和像氯胺这样的含氯化合物的总量，而这些含氯衍生物是不能阻止细菌和/或病毒对水的污染的。
此外，由于有机的和化学的负载物会大大降低游离氯的灭菌能力，因此现有的游离氯测试仪测得的值就不准确，除非已知受测水体的pH值及水中有机污染物的准确浓度。
美国4,752,740号专利提出采用监测氧化还原势能(ORP)的方法来测量水体的清洁度，氧化还原势能是指消毒剂如氯、溴或臭氧与各种污染物进行反应的潜在能力，这些化合物被称为氧化剂，有能力“烧掉”水中的不洁物，如人体排泄物、藻类和细菌。泳池的维护工程师使用氧化还原势能传感器测出的是消毒剂中活性组分所产生的势能，而不是其中含氯衍生物这些非活性组分所产生的势能。此外，监测氧化还原势能的一个优点是，监测过程是一个实时的电子过程，无需使用化学测试品或试剂，且对卫生水平的监测是按预定程序进行的连续过程。在公共游泳池和温泉场所，有机负载物造成疾病传播的可能性大为存在，使用氧化还原势能测试方法对于降低污染及疾病传播的危险是十分有益的。
根据世界卫生组织1972年制定的标准，维持氧化还原势能在650毫伏的水平被认为可以使水体处于清洁状态，水体中的病毒会立即失活。
氯是水工业中最为广泛使用的氧化剂，主要用于对游泳池和温泉场所的消毒。氯做为一种氧化剂，还可与有机物及含氮的物质如尿液、尿酸、氨基酸等进行氧化反应。氯的一个缺陷是它产生氯化副产物。氯化副产物会刺激眼睛、皮肤等，并产生异味及腐蚀空气净化设备。
为解决这一问题已做过多种尝试。“电击”游泳池中的水需要在水中投入化学计量浓度的氯以氧化这些物质，这种方法带来的一个问题是，当不需要的物质已经积累时，要达到所需的化学计量浓度的氯就会造成其在水中的浓度过高，这样的游泳池不能有游泳者存在。另一个问题是这种症状(即高浓度的结合氯、异味等)出现后带来的问题。同样，在很多情况下，此法不能除去水中的这些物质，因为氯的浓度充其量是一个粗略的估计值(包括了水中的结合氯)，水中结合氯的测量浓度并不包括累积在过滤介质及泳池壁上的结合氯。随着氯浓度的上升，就会产生部分累积物，这样便阻止了氯达到必要的化学计量浓度，阻止了水质达到“临界点”。
臭氧是消除这些不需要物质的次要手段。虽然臭氧是一种有效的氧化剂，但它不能用于泳池这样的大片水域。再者，泳池中污染物随时会添加进来，由于臭氧不可能在水体中保持残留浓度，因此不能被单独使用，而氯或溴才是主要的氧化剂。除费用昂贵及需用额外的除臭氧设备，如活性炭外，臭氧还会通过攻击次氯酸离子而破坏氯的氧化性，因而会进一步增加操作及维护费用。
有时用溴来代替氯，因为溴不会像氯那样产生不良气味的副产物。然而，虽然溴胺不像氯胺那样易挥发，但的确也有异味并刺激眼睛。使用溴还需要使用像氯或臭氧这样的氧化剂来激活溴化物离子，操作费用高，且没有简易的方法区分游离溴和结合溴，因此总是很难保证水质。再者，将氯和溴制成片剂时，通常使用己内酰脲做为添加剂。己内酰脲在水中积累后会降低溴的氧化能力，这会使消除不需要的溴化物的积累更加困难。
氧化还原势能是表明氧化或还原能力的定性指标。自1972年Stranco公司将此法引进到水处理工业后，此法一直被使用。尽管使用了氧化还原势能控制器，但仍然很难对不断变化的负载因素做出及时的反应，室内水设施中水及空气的质量控制依然是一个问题。
虽然氧化还原势能被认为是确定各种细菌和病毒失活率的主要指标，但在水中施用ppm级别的氯依然是公认的满足水系氧化要求的方法。例如，虽然650毫伏通常被认为是确保泳池或温泉处于卫生状态的最低氧化势能，但卫生部门依然要求使用ppm级别的氯。
按照产品说明及“合格泳池营业者”培训课程所指定的过氯化(临界氯化)方法，尽管氯的浓度达到卫生部门的要求或在氧化还原势能超过650毫伏下操作，但不完全氧化造成的问题依然是广泛的。
因此，如果发明一种既能清除水和空气中的污染物，又能保障所需的卫生水平的方法，这一长期的问题就能得到解决。
发明概要
本发明涉及对氧化速度的优化，这里的氧化使用卤素来阻止氯胺和溴胺这些不需要的卤化副产物的积累。控制卤素，如氯的进料速度，以保持所要求的氧化还原势能，则氧化速度足以避免副产物的积累。将此法用于室内的水设施，可除去空气及水中的副产物，由此使低劣的空气质量和水质得到转变。
使用必要的工艺控制方法和进料设备以保证设定的工艺参数，就可优化氧化还原势能，从而控制水中副产物的浓度。
本发明的一个目的是通过保持一定水平的氧化势能来消除水和空气中的挥发性卤化物。控制卤素的进料速度可阻止或清除卤化物和其他挥发性卤化物的积累，这些卤化物会对空气和水造成污染，对室内水系污染更为严重。
本发明的另一个目的是讲授在“连续临界卤化”条件下，操作水设施的工艺过程。
本发明再一个目的是，在用次氯酸(HOCL)氧化后，对卤化物进行再吸收，从而改善闭路水系中空气的质量。
本发明的其它目的和优势通过如下描述、图示、说明及实例等，会一目了然。图示包括部分工艺条件和实例实施方案，表明了本发明的各种性能和目的。
图示简介
图1表示本发明的工艺过程。
图2表示例2在使用本发明前的现场实际条件。
图3表示例2在使用本发明后的现场实际条件。
图4表示例1中空气及水在实验装置中的流程。
更适宜的实施方案的详细描述
应该明白这里图示表明的只是本发明的某些方面。本发明并不只限于这里所描述和表明的形式或结构。很明显，对于该领域内的技术人员来讲，在不超出本发明范围的条件下可进行各种修改。本发明不只限于这里的技术说明和图示所描述及展示的范围。
见图1，这是一个典型的室内水设施。泳池的水或温泉流经一个氧化还原势能传感器。可以选择水再流经一个传感器以测出其内的总溶解物(TDS)、水温及pH值。氧化还原势能传感器的测量结果被送到一个控制器，它可使卤素的供应源根据所设定的工艺参数向池水中添加卤素。
本发明涉及对氧化速度的优化，这里的氧化是使用卤素来阻止不需要的卤化副产物的积累。控制氯、次氯酸钙、次氯酸钠、次氯酸锂、溴化物或它们的混合物的进料速度，以保持所要求的氧化还原势能，则氧化速度足以避免副产物的积累。将此法用于室内的水设施，就可除去空气及水中的副产物，由此使低劣的空气质量和水质得到转变。
已经证明，将氧化还原势能定于750～850毫伏，更佳的是760～800毫伏，并使用必要的工艺控制手段及进料设备来保持该设定值，则水中的氧化速度足以控制副产物的浓度。维持上述条件，这些副产物造成的空气和/或水的质量低劣状况就可以得到转变。在另一实施方案中，总溶解物及pH值也在被监测中。
在泳池或温泉这样的大片水域中，即使有积累存在，本发明也能确保持续的高速氧化。已经发现，在这样的氧化还原势能下，即使副产物的浓度远远超过了试验中的浓度，它们也不可能维持存在。因此，按本发明进行操作，水设施就是在“连续临界卤化”条件下运行。
根据所述的工艺条件进行操作，氧化初期所形成的副产物不会积累起来。副产物只是连续氧化过程中的一个中间体。虽然初期会形成这些副产物，但他们没条件积累起来，此后很快便被连续氧化过程清除掉了。通过阻止这些挥发性副产物的积累，它们的分压被降至最低，因此解决了空气质量低劣的问题。同样，将此法用于目前存在这些问题的水设施中，经次氯酸氧化后再对挥发性氯化物进行吸收，这样就可转变由这些卤化物造成的空气质量低劣的状况。再吸收过程的动力学依据亨利扩散定律。
实验室和现场测试都已证明，像单氯胺这样的氯胺对氧化还原势能有缓冲效应。在一段时间内，氯的需要量才是氯的消耗量。氯胺需要化学计量的次氯酸进行初始氧化。氧化反应不会消耗氯，除非有一定的化学计量浓度的次氯酸存在。
虽然次氯酸在达到化学计量浓度前，结合氯不会消耗氯，但结合氯对次氯酸的氧化还原势能有缓冲效应。只要有结合氯存在，其产生的缓冲效应很难使氧化还原势能达到780～800毫伏。将氧化还原势能设定为760～800毫伏，向水中添加氯，直至达到这一势能水平。但只要有结合氯存在，就很难达到这一势能水平。缓冲效应会导致游离氯浓度的升高。此时，氧化反应的速度会加快，结合氯和其它氯化物被氧化。
这一进展对于水工业十分重要，因为这意味着可以通过控制氯的进料速度来阻止或消除结合氯及类似挥发性卤化物的积累，这些卤化物对水设施中的水及周围的空气造成污染，对室内水设施污染尤为严重。
实施方案1
设计并建造实验装置以模拟室内水设施中的水及空气环境，该系统要控制下列条件：
水温；
空气循环速度；
换气速度；
循环水速率(过滤后的水)；
换水速率。
图4表示水和空气在试验装置中的流程。
试验装置包括自动监测及记录氧化还原势能和pH值的仪表。
在空气循环系统中装有冷凝器，在冷凝器里对冷凝液进行规定的取样。
使用微量滴定法对各种试剂进行精确计量，这些试剂可调节氧化还原势能。
试验装置最初加水到分液器线的50％，缓冲罐充水到50％，罐盖是密封的。
在进入空气循环泵前对空气进行冷却以收集冷凝液样品。冷凝液收集时间为20分钟。受测样品用标准DPD方法进行氯的测试，标准DPD方法使用HACH DR2000型分光光度计。
试验使用实验级的氯化胺做为产生氯胺的氮源，称量后的氯化胺被加入到试验装置的水中。起动空气和水循环泵，并调节至所希望的循环和交换速度。
氯以浓度为5.25％的液态漂白剂的形式，经计量后加入到水中，以诱发结合氯的形成。经过充分接触后，增加漂白剂的用量，使氧化还原势能达到所希望的800毫伏。
使用标准方法定期对冷凝液和水样中的游离氯和总氯含量进行测量，并记录氧化还原势能和pH值。
表1表明了从空气(其后是水)中除去氯胺的速度。加入卤素(氯)使氧化还原势能维持在800毫伏，在试验期间，空气中氯胺的浓度持续下降，水中的氯胺浓度没有变化，但没有出现累积。物料平衡维持水中氯胺的消失速度与转换到冷凝液中的速度相等。水对氯胺的吸收遵循亨利定律。
表1
实施方案2
| 经过时间(分钟) | ppm结合氯(在水中) | ppm结合氯(在冷凝液中) |
| 0 | 1.57 | |
| 25 | 1.18 | |
| 70 | 0.56 | |
| 130 | 0.2 | 3.12 |
| 270 | 0.35 | 1.36 |
| 315 | 0.25 | |
| 375 | 0.3 | 0.92 |
一个95000加仑的室内游泳池长期以来由于空气和水中氯胺的浓度高而存在空气和水的质量问题。水处理系统已有氧化还原势能控制器，使用12％的液体漂白剂做为氧化剂和消毒剂。
为了达到临界条件，该游泳池经常使用符合工业标准的过氯化消毒方法以期达到临界状态，并由此改善低劣的水和空气质量。但游泳者普遍抱怨有皮肤刺激、皮疹及刺激眼睛的情况。从管理员的记录中可以看出，即使经过过氯化处理后，结合氯的浓度依然≥0.5ppm。
按照本发明的方法控制泳池水中的化学成分，氧化还原势能和pH值被自动控制并记录下来。图2和图3分别表明了使用本发明前、后的结果。氧化还原势能被设定为780毫伏，pH值设为7.5。根据氧化还原势能来控制氯的浓度和进料速度。使用标准DPD方法测定游离氯的浓度。要使氧化还原势能保持在设定值，游离氯的浓度通常为7～10ppm。经过7天后，用DPD比色方法测得的结合氯浓度为0.0。10天后，氯胺造成的异味消失了。连续运行4个多月后，空气中一直没有氯胺的异味，并且不再使用过氯化消毒方法。
虽然本发明是用特定的实施方案加以说明描述的，但很明显，对于这一领域的技术人员来讲，根据本发明的原理可以进行各种修改、重新安排和替换。本发明的范围由所附的权利要求书加以定义。
Claims (8)
1.从室内水设施的空气中除去挥发性卤化物的工艺过程，包括：
在与所述设施的水体连通的流体中放置一个氧化-还原势能(ORP)传感器；
连续监测所述水体的氧化还原势能；
将测得的氧化还原势能同有效范围内的设定值进行比较，确保所述的挥发性卤化物被氧化；
定量定速加入卤素源，使测得的氧化还原势能在所述的有效范围之内；
调整所述的卤素的加料速度，使氧化还原势能维持在所述的有效范围之内；
对所述水系内的所述的挥发性卤化物进行再吸收；
并对再吸收的化合物进行氧化。
2.如权利要求1所述的工艺，其中所述卤素源选自氯气、溴、次氯酸钙、次氯酸钠、次氯酸锂及它们的混合物。
3.如权利要求1所述的工艺，其中氧化还原势能的有效范围是750～850毫伏。
4.如权利要求1所述的过程，其中还包括监测pH值的步骤。
5.从循环水系中除去可溶性卤化物的工艺过程，包括：
在与所述的闭路循环水系连通的流体中放置一个氧化-还原势能传感器；
连续监测所述水体的氧化还原势能；
将测得的氧化还原势能同有效范围内的设定值进行比较，确保所述的卤化物被氧化；
定量定速加入卤素源，使测得的氧化还原势能在所述的有效范围之内；
调整所述的卤素的加料速度，使氧化还原势能维持在所述的有效范围之内；
其中所述的卤化物被连续地氧化。
6.如权利要求5所述的过程，其中卤素源选自氯气、溴、次氯酸钙、次氯酸钠、次氯酸锂及它们的混合物。
7.如权利要求5所述的过程，其中氧化还原势能的有效范围是750～850毫伏。
8.如权利要求5所述的过程，其中还包括监测和/或控制pH值的步骤。
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-
1999
- 1999-03-02 US US09/260,809 patent/US6143184A/en not_active Expired - Lifetime
-
2000
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- 2000-02-24 AU AU32444/00A patent/AU772131B2/en not_active Ceased
- 2000-02-24 WO PCT/US2000/004750 patent/WO2000051942A1/en not_active Application Discontinuation
- 2000-02-24 NZ NZ514225A patent/NZ514225A/en not_active IP Right Cessation
- 2000-02-24 KR KR1020017011161A patent/KR20010103789A/ko not_active Application Discontinuation
- 2000-11-06 US US09/707,421 patent/US6423234B1/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167453A (zh) * | 2011-01-05 | 2011-08-31 | 浙江省电力试验研究院 | 一种基于orp监测的除盐系统中二氧化氯的控制方法 |
| CN102167453B (zh) * | 2011-01-05 | 2012-10-10 | 浙江省电力试验研究院 | 一种基于orp监测的除盐系统中二氧化氯的控制方法 |
| CN110050189A (zh) * | 2016-12-08 | 2019-07-23 | 苏伊士集团 | 用于控制流体网络的流体中的挥发性有机化合物的浓度的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| NZ514225A (en) | 2003-10-31 |
| AU772131B2 (en) | 2004-04-08 |
| WO2000051942A1 (en) | 2000-09-08 |
| US6423234B1 (en) | 2002-07-23 |
| US6143184A (en) | 2000-11-07 |
| KR20010103789A (ko) | 2001-11-23 |
| AU3244400A (en) | 2000-09-21 |
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