CN102892714B - 用于电化学产生次氯酸盐的系统 - Google Patents
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Abstract
本发明涉及一种按照需要以宽的体积与浓度范围在使用端电化学产生次氯酸盐的系统。该系统装有调节电解液组成、电流密度和电解时间的处理器和能够在需要更换电极时预先报警的警报系统。还可以提供几种收集容器的插入与正确类型的自动检测,由此触发电解参数的设置。
Description
技术领域
本发明涉及电化学产生次氯酸盐的系统。
背景技术
由碱金属氯化物的稀释盐水电解生产次氯酸盐,例如通过电解氯化钠水溶液或海水电解生产次氯酸钠是工业电化学领域中最常见的工艺之一。次氯酸盐的生产常常伴随着来自于氯化物的氧化的各种副产物的产生(通常以“活性氯”为名归类),在某些情况下产生氧化物质,如过氧化物,其大多数具有非常有限的寿命;为简短起见,本文中水溶液中的此类产品的整体(主要由碱金属次氯酸盐和次氯酸以主要取决于pH的比例组成)称为次氯酸盐。在许多用途中,恰恰是极少非常活性的物质的内在不稳定性和短保存期使次氯酸盐的原位生产引人注意,允许立即使用该产品溶液。在医疗/医院领域(纱布或外科手术器械的消毒)、在酒店/服务行业(白色织物消毒、供给到淋浴间和卫生洁具的水的预处理)、在食品和饮料中(固体和液体食品的处理与包装)、在洗衣店中和在养殖与肉类加工业中这尤其是真实的。在许多此类环境中,希望尽可能灵活地提供即用型次氯酸盐产生系统以便能用单一装置响应不同的需求。例如,在工业化养殖领域中,可以要求不同体积和浓度的次氯酸盐用于消毒相应的机械设备或用于处理动物皮肤,同样在旅馆环境中,不同的次氯酸盐溶液可用于亚麻制品漂白或用于引入淋浴间和卫生洁具的水的消毒;因此有用的是提供一种能够根据时机需要而设置所需产品的特性的装置。电化学生产次氯酸盐的最简单和最有效的方法是在未分隔型电解槽中电解,所述电解槽具有各种形状与几何形状的电极,例如具有交错的平面电极。在电解槽中,通过氯化物的阳极氧化生产次氯酸盐,同时氢在阴极处析出;当待电解的氯化物溶液含有显著量的钙或镁离子时,如民用水加氯的情况,阴极表面附近电解质的自然碱化导致碳酸盐的局部沉淀,这趋于使阴极失活并在一段时间后迫使其失效。在建议消除该问题的各种解决方案中,非常有效的一种解决方案包括对于电极施以周期性电势反转,使它们交替用作阴极和阳极。以这种方式,当反应环境趋于酸化时,在阴极操作下沉降在电极表面上的碳酸盐沉积物在随后作为阳极的操作过程中溶解。由于析氢反应在许多金属材料上在足够适度的电势下发生,用设计以最大化更关键的次氯酸盐产生阳极反应的效率的催化剂来活化必须在交替电极极化下工作的电解氯化器的电极。在交替极化条件下电极的功能允许以良好的效率运行,同时保持电极表面足够干净,不受不溶性沉积物污染;不过,在这种类型的电极构造的氢析出下的阴极操作招致低于最佳的操作寿命,因为在这些条件下涂层对基材的粘合趋于受损。这种类型的电极的失活机理(根本上是由于催化层从基材上脱离)致使在没有明显的征兆的情况下突然失效。为了防止严重的不便之处,通常在统计基础上对电解槽中电极的剩余寿命进行预估,以便在快速和不可逆的失效发生之前对它们进行替换。由于在这种类型的操作条件下发生的电极失活受多种因素影响,其变化性相当高,并且保持足够的安全裕度意味着更换已经运行了一段显著的剩余时间的电极。此类变化性(对于在恒定工作条件下运行的电解池而言其本身也是高的)对于在经常变化的条件下施以工作循环的电解池而言变得几乎不可控制,以便能够根据不同需要快速制造可变体积与浓度的次氯酸盐溶液。在这种情况下,许多电解槽上的甚至重要历史数据的收集在电极剩余寿命的预测中也不是非常有用,该电极剩余寿命极大取决于它们经受的诱发类型,后者又受个别使用者的操作需求的影响。
由此表明需要提供新的次氯酸盐电化学产生系统,其特征在于提高的使用灵活性并同时预测电极失活的可能性,并随之需要提前一段时间安排其替换干预。
发明概述
在所附权利要求书中显示了本发明的各个方面。
在一种实施方案中,电化学产生次氯酸盐的系统包括以预定浓度将碱金属氯化物溶液,例如氯化钠溶液送入未分隔的电解槽中的投配室,所述未分隔的电解槽装有一个或多个包含用两种不同组成的外覆催化层活化的阀金属基材的电极对,用于在每对的两个电极之间以预定周期施加具有交替极化的电流的装置,连接到警报装置上的用于测量每对的两个电极之间的电势差的传感器,在电解槽出口处的次氯酸盐溶液收集容器,适于控制和检查下列项的处理器:
-碱金属氯化物溶液的剂量和任选稀释度;
-其在电解槽内在预定电流密度下持续预定时间的电解;
-电解的溶液向收集容器内部的排放;
-由传感器实施的电势差测量与作为电解溶液浓度和施加的电流密度的函数的一组临界值的比较;
-所述电势差结果高于相应临界值时警报装置的启动。
在本文中,词语“处理器”是指适于进行上述测量和调节的普通可编程装置。使用包含两个不同组成的外覆催化层的电极的优点可在于,能够对给定的一组操作参数在第一电解槽电压水平下进行该过程,直到最外层仍然存在并起作用,并且在第二电解槽电压水平下该最外催化层因使用立刻耗损或脱离。在一种实施方案中,不同组成的外覆催化层包含催化活性较低的内层,例如含有钌和铱的氧化物以及20-35摩尔%的选自钽和铌的阀金属的氧化物,和催化活性较高的外层,例如含有钌和铱的氧化物以及70-80摩尔%的氧化钛的混合物,以致于与一组参比参数相比,在电解质浓度和电流密度方面,外催化层在与内催化层相比显著降低,例如低500-800毫伏的总电解槽电压下运行。其优点可在于改善了电极对的电极之间电势差与由处理器计算得到的临界值的比较灵敏度,由此提高了警报系统的有效性,该警报系统必须仅在外催化层失活后但是远早于内催化层失活的时候被激发。在一种实施方案中,以金属表示的铱与钌的总含量在内层中为2-5克/米2,在外层中高于7克/米2,以便最大化贵金属在更活性层中的使用,同时在内层中分配足够量的贵金属,其必须运行足够长的时间以允许安排更换该电极。在本文中,短语“更换电极”对某些实施方案而言包括任选替换其中安装电极的整个电解槽。在一种实施方案中,用于产生次氯酸盐的系统包括外部选择器装置以便根据所需用途以连续或离散方式改变产物溶液的浓度和/或体积。连续选择装置的优点在于表现最大可用操作灵活性,满足甚至非常特殊的使用需求(难以先验地预测);另一方面,离散选择装置(例如能够按照需要进行三到十次预置程序)的优点可以在于覆盖足够宽的可能用途范围,同时显著简化处理器进行的电势测量值比较任务。在一种实施方案中,处理器编程为检测收集容器的插入和识别收集容器的类型并设置选自要送入所述电解槽中的溶液的体积与盐浓度、电流密度和电解时间的至少一种参数。其优点可在于简化使用并消除操作者导致的可能的错误源,该操作者可例如具有两个或更多个可用容器,涉及不同的用途(例如,1000毫升的壶可用于制造涉及工作面消毒的溶液,200毫升容器用于消毒工具),一旦插入该系统中可以通过芯片或条形码识别该可用容器,并基于预期的用途充以恰当体积的预定浓度的次氯酸盐溶液。产品溶液的体积的调节允许防止任何浪费或产品过剩(其随后需要储存或处置)。在一种实施方案中,待送入未分隔的电解槽中的碱金属氯化物溶液的剂量和任选稀释度可以通过该处理器调节以便在100至1000毫升的总体积范围内获得2至30克/升的碱金属氯化物浓度。在一种实施方案中,可以通过所述处理器调节电解参数以便在30秒至30分钟的时间内在100至2500安培/平方米的电流密度下获得5毫克/升至10克/升的活性氯浓度。上述参数覆盖了宽范围的可能用途,如对本领域技术人员清楚的那样,但是此类范围可以以几种方式扩展或缩小以应对不同市场或应用领域的需要。在一种实施方案中,例如通过可以由外部选择装置访问的预置程序调节该电解参数以获得50-200毫克/升的活性氯浓度,而剩余NaCl浓度为8-10克/升。其优点在于能够容易地生产可用于人或动物皮肤消毒的等渗(isotonic)溶液。以交替极化施加电流的装置可以设定为在分钟或秒的量级的固定时间反转电极的极性。在一种实施方案中,在每个生产周期或每2-5个周期实现各电极对的两个电极的极性反转;实际上可以以更简单的方式进行短暂生产,例如低于30分钟,而无需在电解过程中反转电极极性,然后通过随后的阳极操作将清洁阴极的任务留给下一生产周期。
本文包括下列实施例以证明本发明的特定实施方案,其实用性已经在要求保护的值的范围内在很大程度上得到核实。本领域技术人员应理解,下列实施例中公开的组合物和技术代表在本发明实践中发挥良好作用的发明人发现的组合物和技术;但是本领域技术人员根据本公开内容应当理解,可以在公开的具体实施方案中进行许多改变并仍然获得类似的结果,而不会背离本发明的范围。
实施例1
未分隔的电解槽装有两对电极,所述电极获自面积为10平方厘米且厚度为0.5毫米的钛板,其通过在强制空气循环炉中在590℃下热处理5小时和在27%的H2SO4中在87℃下2小时的蚀刻处理预处理过。通过如下方式制备第一对的电极:通过以3道涂层刷涂和随后在每次涂布后在510℃下热分解以47%Ru、24.7%Ir和28.3%Ta的摩尔比含有RuCl3、H2IrCl6、TaCl5和2-丙醇并用HCl酸化的第一水醇前体溶液直至获得以Ir和Ru之和表示的3克/平方米贵金属载量,在由此处理过的钛板上首先施加内部催化涂层;随后,通过以14道涂层刷涂和随后在每次涂布后在510℃下热分解以15%Ru、7.9%Ir和77.1%Ti的摩尔比含有RuCl3,H2IrCl6,TiOCl2和2-丙醇并用HCl酸化的第二水醇前体溶液直至获得以Ir和Ru之和表示的12克/平方米贵金属载量,在内部催化涂层上施加外部催化涂层。第二对的电极通过以下方法制备:通过以17道涂层刷涂和随后在每次涂布后在510℃下热分解以与前述相同的摩尔比含有RuCl3、H2IrCl6、TiOCl2和2-丙醇并用HCl酸化的相同的第二前体溶液,直至获得以Ir和Ru之和表示的15克/平方米贵金属载量,向预处理的钛板施加催化涂层。
在采用每对电极周期性极性反转制造次氯酸盐时在加速寿命试验中运行该电解槽。在1千安培/平方米的电流密度下在由含有4克/升的NaCl和70克/升的Na2SO4的水溶液组成并将温度调节在25±1℃的电解质中进行该加速试验,在每60秒后反转该电极的极性。在相对于工业应用而言的此类放大的操作条件下,具有单催化层的第二电极对在约3伏的电解槽电压下在恒定条件中运行约220小时,随后电池电压的突然提高表明其失活并被迫将其从电路中撤出。带有两个外覆的催化层的第一电极对在恒定条件中在约3伏的电解槽电压下工作约210小时,接着电解槽电压递增,在总共225小时后稳定至新的恒定值,比前一值高680毫伏。在附加测试30小时后检测到完全失活。
实施例2
将装有一对与实施例1的第一对等效的电极的未分隔电解槽放入到由微处理器控制的次氯酸盐产生系统,其包括:
-投配室,其预载有浓度为30克/升的氯化钠溶液,经装有流量计的阀连接到自来水管并经配料泵连接到电解槽,该阀和该配料泵连接到微处理器并受该微处理器控制
-整流器,其能够以100至2500安培/平方米的电流密度向该电解槽的电极通电,并能够在固定的时间或在预定的工作周期数量后反转该极性,该整流器连接到微处理器并受该微处理器控制
-连接到该电解槽的电极的电压表和发光警报信号器,均连接到该微处理器
-体积分别为100、500和1000毫升的一组三个收集容器,适于经连接到该微处理器的检测与识别条形码型系统连接到该电解槽出口管。
该微处理器进一步装有能够操纵三个不同的工作周期的自动执行的程序库,每个工作周期与一种容器类型相联,并具有一组适于矫正电势差值的比较曲线,该电势差值由电压表在对1千安培/平方米的参比电流密度的各自编程(programme)的不同电流密度下读取。调节警报信号以便每当校正后电压表读数比起始工作电压高400毫伏时受到触发。设定三个程序以便分别在下列条件下进行次氯酸盐生产:
-对于100毫升容器:在100安培/平方米的电流密度下,6000毫克/升活性氯溶液,在没有自来水稀释的情况下从30克/升的氯化钠溶液开始
-对于500毫升容器:在500安培/平方米的电流密度下,100毫克/升活性氯溶液,从稀释到9克/升的氯化钠溶液开始
-对于1000毫升容器:在2000安培/平方米的电流密度下1000毫克/升活性氯溶液,从稀释到25克/升的氯化钠溶液开始。
在第一场试验中运行该系统,在此过程中,每个预置程序与每分钟电极极性反转相关;在一天的过程中按照随机序列实施不同容器的插入(由操作者)和相关的次氯酸盐生产程序的执行,保持每5-8个生产周期追踪整体运行时间并随机分析活性氯浓度。总共运行约900小时后,记录到第一警报信号;在四个附加生产周期后,警报保持持续被触发。电解槽保持规律工作,以预定浓度生产预期体积的次氯酸盐另外40小时,随后电极完全失活迫使其关机。
在替换电解槽中的电极后,进行第二场试验,在此过程中,运行各预置程序直到结束而没有极性反转;电极极性然后在周期开始时反转。同样在这种情况下,在一天的过程中按照随机序列实施不同容器的插入和相关的次氯酸盐生产程序的执行,保持每5-8个生产周期追踪整体运行时间并随机分析活性氯浓度。在总计运行约4700小时后,记录到第一警报信号;在九个另外的生产周期后,警报保持持续被触发。电解槽继续规律运行,以预定浓度生产预期体积的次氯酸盐另外150小时,随后电极完全失活迫使其关机。
前面的描述并非旨在限制本发明,其可以按照不同的实施方案使用而不会背离其范围,并且其范围仅由所附权利要求限定。
在本申请的说明书和权利要求书中,术语“包含”及其变体如“含有”和“包括”并非旨在排除其它元素或添加剂的存在。
对文献、行动、材料、装置、制品等等的讨论仅为提供本发明的背景而包括在本说明书中。并非暗示或代表这些内容的任何或全部在本申请各权利要求优先权日之前构成部分现有技术基础或是本发明相关领域的公知常识。
Claims (9)
1.电化学产生次氯酸盐的系统,包括:
-碱金属氯化物溶液的投配室;
-未分隔的电解槽,装有至少一对包含阀金属基材和至少两种不同组成的外覆催化层的电极,用来自所述投配室的所述碱金属氯化物溶液进料;
-用于在所述对的所述电极之间以预定周期施加具有交替极化的电流的装置;
-用于测量所述对的所述电极之间的电势差的传感器,其连接到警报装置;
-至少一个用于来自所述电解槽的次氯酸盐溶液的收集容器;
-编程为控制和检查下列项的处理器:所述碱金属氯化物溶液的剂量和任选稀释度,其在所述电解槽内部在预定电流密度下持续预定时间的电解,电解的溶液向所述收集容器内部的排放,由所述传感器实施的电势差测量与作为电解的溶液浓度和施加的电流密度的函数的一组临界值的比较,所述电势差高于相应临界值时所述警报装置的启动。
2.根据权利要求1所述的系统,包括外部选择装置以便以连续或离散的方式根据所需用途改变产品溶液的浓度和/或体积。
3.根据权利要求1所述的系统,其中所述处理器编程为识别所述至少一种收集容器的插入和类型以及设置选自待送入所述电解槽的溶液的体积与盐浓度、电流密度和电解持续时间的至少一种参数。
4.根据权利要求1所述的系统,其中送入所述未分隔的电解槽中的所述碱金属氯化物溶液的剂量与任选稀释度能够通过所述处理器调节,以致在100至1000毫升的总体积范围内获得2至30克/升的碱金属氯化物浓度。
5.根据权利要求1所述的系统,其中所述电解的参数能够通过所述处理器调节,以致在30秒至30分钟的时间内在100至2500安培/平方米的电流密度下获得5毫克/升至10克/升的活性氯浓度。
6.根据权利要求1所述的系统,其中所述电解的参数能够通过所述处理器调节,以致获得50-200毫克/升的活性氯浓度,而剩余NaCl浓度为8-10克/升。
7.根据权利要求1所述的系统,其中用于施加具有交替极化的电流的所述装置在每个生产周期处反转所述对的电极的极性。
8.根据前述权利要求任一项所述的系统,其中所述至少两种不同组成的外覆催化层包含内层和外层,所述内层含有铱、钌的氧化物和选自钽和铌的阀金属,并且所述外层含有铱、钌与钽的氧化物的混合物。
9.根据权利要求8所述的系统,其中以金属表示的铱和钌的总含量在所述内层中为2-5克/平方米,并在所述外层中高于7克/平方米。
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JP4740080B2 (ja) * | 2006-09-26 | 2011-08-03 | 三洋電機株式会社 | 空気除菌装置 |
JP5105406B2 (ja) * | 2007-02-27 | 2012-12-26 | 学校法人同志社 | 逆電解用電極 |
TW200840120A (en) * | 2007-03-20 | 2008-10-01 | Industrie De Nora Spa | Electrochemical cell and method for operating the same |
EP2132144A4 (en) * | 2007-04-05 | 2012-08-15 | Siemens Industry Inc | METHOD AND SYSTEM FOR ELECTROLYSIS PROCESSING |
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2010
- 2010-06-17 IT IT001100A patent/ITMI20101100A1/it unknown
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2011
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Also Published As
Publication number | Publication date |
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JP2013534567A (ja) | 2013-09-05 |
ES2528009T3 (es) | 2015-02-03 |
JP5841138B2 (ja) | 2016-01-13 |
EA022522B1 (ru) | 2016-01-29 |
CN102892714A (zh) | 2013-01-23 |
BR112012031910A2 (pt) | 2020-09-24 |
ITMI20101100A1 (it) | 2011-12-18 |
EP2582633B1 (en) | 2014-10-22 |
IL222675A0 (en) | 2012-12-31 |
AU2011267000A1 (en) | 2012-11-08 |
KR20130121689A (ko) | 2013-11-06 |
AU2011267000B2 (en) | 2014-06-26 |
IL222675A (en) | 2016-07-31 |
EP2582633A1 (en) | 2013-04-24 |
WO2011157812A1 (en) | 2011-12-22 |
TWI540224B (zh) | 2016-07-01 |
CL2012003399A1 (es) | 2013-06-28 |
MX2012013813A (es) | 2013-03-05 |
TW201200635A (en) | 2012-01-01 |
US20130087449A1 (en) | 2013-04-11 |
KR101833203B1 (ko) | 2018-03-02 |
EA201291313A1 (ru) | 2013-04-30 |
US9090980B2 (en) | 2015-07-28 |
BR112012031910B1 (pt) | 2021-03-23 |
HK1181029A1 (zh) | 2013-11-01 |
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