CN1136971A - 含卤素、磷、硫和/或金属元素的有机化合物的处理方法 - Google Patents
含卤素、磷、硫和/或金属元素的有机化合物的处理方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 12
- 150000002367 halogens Chemical class 0.000 title claims abstract description 12
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 title abstract 2
- 238000000909 electrodialysis Methods 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
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- BSZGRVOHARVEBR-UHFFFAOYSA-N ClOC1=CC(=C(C=C1)C(C(=O)O)C)C Chemical compound ClOC1=CC(=C(C=C1)C(C(=O)O)C)C BSZGRVOHARVEBR-UHFFFAOYSA-N 0.000 description 1
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- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- 231100000167 toxic agent Toxicity 0.000 description 1
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Abstract
为处理在原子键上除了碳、氢和氧元素外,还包括卤素、磷、硫和/或金属元素的危险或有毒有机化合物,提出了使该有机化合物电离,紧接着进行电渗析的方法,此离子态的最终反应产物可容易操作,并且可毫无问题地进一步使用或以填埋或焚烧方式处理。在电离辐射作用下发生电离。本发明方法特别适合处理含卤素的芳族化合物如各种农药。
Description
本发明的主题涉及有机化合物的处理方法及实施所述方法的设备,其中的有机化合物在原子键中除了碳、氢和氧元素外,还包括卤素、磷、硫和/或金属元素。
包括卤素、磷、硫以及金属原子如汞、砷等的物质用途广泛。它们可用作致冷剂、气溶胶抛射剂、杀虫剂、药剂、变压器油等。对此特别关键的领域是化学战剂。在所有这些情况下其中包括存在这些常常极为危险的有毒化合物的处理问题。鉴于此必须破坏生产废弃物、贮存品、生产后可能被法规限制的产品、消费废弃物等。
在这方面通常做法是通过焚烧处理。仅含碳、氢和氧的有机化合物在充分供给氧气的情况下可毫无问题地焚烧为二氧化碳和水。然而特别涉及卤化物时,人们注意到在焚烧过程中,产生的危险二喔星构成对此抵消作用的阻碍。
仍然需要一种破坏、抵消及处理这类物质的低危险方法。
本发明基于带电离子或分子部分可通过电渗析法相互分离的知识,在具有干扰元素的原子(即非极性)键的有机化合物中,仅当这种键被极化并处于能被电能离解的条件下这样的分离才是可能的。
因此,根据本发明,建议对要处理的有机化合物进行电离,于是带电荷的电离产品通过电渗析分离,同时将离子态的最终产物以及余下的有机物质发挥已知用途或以填埋形式或经焚烧处理。
电离可在电离辐射作用下进行。
在这种方法中原子键被极化,要处理的物质离解成离子态产品,而不同电荷颗粒的分离可在电能作用下进行。原来通过原子键相互键合的元素一旦以离子形式存在,它们便可容易操作并且容易处理或用作其它目的。按此方式,存在对危险化合物的抵消而不会产生在前面热破坏中引起的危险。
按此方式,防害剂如杀虫剂、除草剂、杀菌剂以及卤代烃、氯代变压器油、药剂或化学战剂都可按此有利方法处理。
已经证明这种方法对有机卤化物,尤其是卤素与芳香环、优选与苯环键合的有机卤化物特别有利。
例如,这类化合物包括被氯、溴和/或碘取代的苯衍生物,此衍生物优选被一个或多个羟基、氰化物、烷基或任意性酯化的羧基或羧基链烯基基团取代。
具体的例子是二溴或二碘代苯甲腈和氯甲苯基-2-氧代丙酸。这些物质的组合在农业上用作除草剂,其名称为ANITENR。
本发明的方法还可用于卤化多苯基化合物,优选多卤代联苯(PCB),它用作变压器油。
另外的处理上的问题是由脂族卤代烃(CFCs)造成的,这些卤代烃用作致冷剂和气溶胶抛射剂。对它们的处理也是本发明目的。
要处理的化合物的电离可通过X-射线,任意地与β和γ射线相配合进行。
在最简单的形式中,常规X射线仪用于此目的,其中除去了为了不需要的β和/或γ射线而***的铝板。
要处理的物质优选以液体状态、特别是以溶液形式,优选以水溶液形式存在。
优选地,电离和渗析装置在空间上结合在一起,因为产生的电离产物的寿命,特别是涉及用辐射电离时,常常相当短。
电离产生500μm(微姆)的溶液最小导电率以取得所需的效果。
本发明的另一主题是实施所述方法的设备。
此设备参考所给附图进行解释,其中:
图1表示实施此方法的优选电离渗析装置;
图2表示这种装置在用于此目的的整个装置中的通常布局;
图3表示具有增强多室电渗析体系的精确装置。
图1表示包括下列部件的优选多室装置:
中心室1,其中原料溶液通过物料管线2加入;在所述室1中发生电离。电离优选在电离辐射作用下进行。通过阳极3和阴极4施加直流电,并且由于直流电的作用,出现电离组分的分离。中心室1与阳极电解液室7和阴极电解液室8相邻,此两室分别被隔膜5和6从中心室分隔。无机带出液通过排料管线9和10从所述室7和8中作为浓缩物排出。
电离后留在室1中的并且不能通过隔膜5、6渗出的有机物料通过排料管线11作为稀释液从所述室中排出。
阳极电解液室7和阴极电解液室8分别与阳极室14和阴极室15相邻,它们之间分别通过隔膜12和13分隔,并通过进料管线16和17加入苛性或盐溶液以稳定贮存离子。
阳极电解液室7和阴极电解液室8也通过进料管线18和19加入苛性或盐溶液(即离子),优选通过管线18和19加入约1wt%的NaOH。
隔膜5和13构成阳极隔膜AM,隔膜6和12构成阴极隔膜KM。
使用两极隔膜是电渗析领域普通技术人员熟知的知识。
本发明优选实施方案之一是使除草剂ANITENR无害的方法,该除草剂由2-(4-氯-邻甲苯氧基)丙酸、3,5-二碘-4-羟基苯甲腈和3,5-二溴-4-羟基苯甲腈以重量比5∶1∶1的混合物组成。中心室1加入浓度为约525g/l的此物质混合物的水溶液。
以尽可能简单的方式借助原医用的X射线设置(除去其用于屏蔽射线的铝板)的装置实现电离。
当然,在操作设备中必须遵守按照技术状态和VE规则(Aus-trian Association of Electrical Engineering)要求的辐射保护措施。
优选使设备连续运行,使原料溶液以17l/h的速度通过室1。
阳极电解液室7中由含1%化学纯NaOH的去离子水组成的溶液,开始试验时绝对不含氯,经过2分钟试验期间后,显示氯含量为24.5mg/l,碘含量为0.15mg/l和溴含量0.25mg/l。
该溶液卤素含量的确定优选通过分光光度法进行。
在所述连续进行此方法中,通过管线16和17加入4至8wt%的氢氧化钠溶液。
阳极或阴极电解溶液通过加入NaOH:卤素为约1∶1的约8wt%的NaOH溶液连续取换。
如图1所示,渗析装置优选为多室装置,然而在某些情况下,仅有一个室的简单渗析装置就足够了。
优选地,渗析装置包括至少一个双极隔膜。
渗析在图1所示的设备中以30至200伏特的电压进行。在这种情况下对于每kg液体流过约21瓦的电能。
在实施方法中,电离和渗析优选在压力下进行。
还可以加入盐溶液如钠盐溶液代替加入的氢氧化钠溶液。
图2表示整个装置,其中排列有电离和渗析设备,在这种情况下两种设备相互分开排列。
在装置部分I中,从槽20中通过管线21加入原料混合物,其中设有所需的泵和阀门。
由于在电离部分II中电离装置的作用,将要处理的物质离解并在渗析装置中分离。
渗析部分III表示从渗析设备23经管线24排出的稀释的有机物质,同时通过环路25和26排出无机反应产物/浓缩物。为了在27和28处排出这些物质,必须将苛性或盐溶液加入管线29和30中。
未完全处理的溶液可在此过程中回收。
图3以原理图形式表示更复杂的多室体系,此图表示出现在设备中的离子流动原理。回收部分的稀释液只要还没有完全处理,就可以回到使用原料溶液的设备中。
隔膜3′至8′排列在阳极1′与阴极2′之间,隔膜3′、5′和7′是阴极隔膜,而隔膜4′、6′和8′是阳极隔膜。在此实施方案中,阳极电解液9′和阴极电解液10′是硫酸钠溶液。盐的水溶液(例如NaCl、Na2SO4)或碱液(例如NaOH)通过管线11′作为接受溶液加入,而浓缩物通过管线13′、15′和17′排出。
CFC、杀虫剂或除草剂的原料溶液在12′处加入。稀释液通过管线14′、16′排出或回到12′。
实施本方法的进一步细节在于电渗析领域熟练技术人员的经验,本文不必更详细地解释。
Claims (22)
1.一种处理有机化合物的方法,该有机化合物的原子键中除了碳、氢和氧元素处,还包括卤素、磷、硫和/或金属元素,其特征在于对要处理的化合物进行电离,将得到的电离产品通过电渗析分开并将最终的离子产品和余下的有机物质发挥已知用途或以填埋方式或通过焚烧处理。
2.如权利要求1的方法,其特征在于处理有机卤化物。
3.如权利要求1或2的方法,其特征在于处理其中卤素与芳环、优选与苯环键合的化合物。
4.如权利要求1至3之一的方法,其特征在于处理被氯、溴和/或碘取代的苯衍生物。
5.如权利要求1至4之一的方法,其特征在于处理苯化合物,该化合物除了卤素外,还被一个或多个羟基、氰化物、烷基或任意性酯化的羧基或羧基链烯基基团取代。
6.如权利要求1至5之一的方法,其特征在于处理二溴或二碘代羟基苯甲腈。
7.如权利要求1至5之一的方法,其特征在于处理氯甲苯基-2-氧基丙酸。
8.如权利要求1至7之一的方法,其特征在于处理二溴-或二碘-羟基苯甲腈与氯甲苯基-2-氧基丙酸的混合物。
9.如权利要求1至3之一的方法,其特征在于处理卤代多苯基化合物,优选多卤代联苯(PCB)。
10.如权利要求1或2之一的方法,其特征在于处理脂族卤化物。
11.如权利要求1至10之一的方法,其特征在于电离通过X-射线与非必须的β和/或γ射线相结合完成。
12.如权利要求1至11之一的方法,其特征在于要处理的物质在液态下电离。
13.如权利要求1至12之一的方法,其特征在于要处理的物质以溶液形式、优选以水溶液形式电离。
14.如权利要求1至13之一的方法,其特征在于通过电离产生500μm(微姆)的最小导电率。
15.如权利要求1至14之一的方法,其特征在于电渗析在30至200伏特的电压下进行。
16.如权利要求1至15之一的方法,其特征在于电离和渗析在压力下进行。
17.如权利要求1至16之一的方法,其特征在于为增加导电率,在阳极或阴极区域的渗析液中加入碱金属氢氧化物,优选氢氧化钠或碱金属盐。
18.一种用于实施如权利要求1至17之一的方法的设备,其特征在于它包括在空间位置上相互结合的电离装置和渗析装置。
19.如权利要求18的设备,其特征在于常规X射线装置用作电离装置,其中除去为屏蔽不符合需要的β和γ辐射而***的铝板。
20.如权利要求18或19的设备,其特征在于渗析设备为多室装置。
21.如权利要求18至20之一的设备,其特征在于渗析装置包括至少一个双极隔膜。
22.如权利要求18至21之一的设备,它包括一发生电离的中心室(1),在相邻于该中心室(1),在阳极(3)与阴极(4)的方向上有一阳极电解液室(7)和阴极电解液室(8),它们通过隔膜(5,6)与中心室(1)分开,与阳极电解液室(7)和阴极电解液室(8)相邻,还有一阳极室(14)和阴极室(15),它们通过隔膜(12、13)分离,该设备还包括原料溶液的进料管线(2)、将苛性或盐溶液加入阳极或阴极电解液室(7,8)或加入阳极或阴极室(14、15)的进料管线(16,17,18,19)和排出有机物(稀释液)的排料管线(11)以及排出无机物(浓缩物)的排料管线(9、10)。
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AT0040295A AT402199B (de) | 1995-03-08 | 1995-03-08 | Verfahren und vorrichtung zur entsorgung von organischen verbindungen |
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EP (1) | EP0730885B1 (zh) |
JP (1) | JPH0975709A (zh) |
CN (1) | CN1136971A (zh) |
AT (1) | AT402199B (zh) |
CA (1) | CA2170710A1 (zh) |
DE (1) | DE59604072D1 (zh) |
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US20110011727A1 (en) * | 2009-07-15 | 2011-01-20 | Sackinger William M | System and method for conversion of molecular weights of fluids |
US20110011728A1 (en) * | 2009-07-15 | 2011-01-20 | Sackinger William M | System and method for conversion of molecular weights of fluids |
US10479711B2 (en) * | 2016-05-05 | 2019-11-19 | Remediation Products, Inc. | Composition with a time release material for removing halogenated hydrocarbons from contaminated environments |
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US4917785A (en) * | 1987-07-28 | 1990-04-17 | Juvan Christian H A | Liquid processing system involving high-energy discharge |
US5116509A (en) * | 1989-09-08 | 1992-05-26 | Millipore Corporation | Electrodeionization and ultraviolet light treatment method for purifying water |
RU1810300C (ru) * | 1991-04-22 | 1993-04-23 | Филиал научно-исследовательского физико-химического института им.Л.Я.Карпова | Способ очистки сточных вод от недиссоциирующих загр знений |
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- 1996-03-01 EP EP96890031A patent/EP0730885B1/de not_active Expired - Lifetime
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- 1996-03-06 UA UA96030899A patent/UA50709C2/uk unknown
- 1996-03-06 RU RU96104465A patent/RU2146567C1/ru not_active IP Right Cessation
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RU2146567C1 (ru) | 2000-03-20 |
EP0730885A1 (de) | 1996-09-11 |
EP0730885B1 (de) | 2000-01-05 |
MX9600905A (es) | 1997-07-31 |
CA2170710A1 (en) | 1996-09-09 |
AT402199B (de) | 1997-02-25 |
DE59604072D1 (de) | 2000-02-10 |
JPH0975709A (ja) | 1997-03-25 |
ATA40295A (de) | 1996-07-15 |
UA50709C2 (uk) | 2002-11-15 |
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