CN1016142B - 有机卤代产物的化学破坏方法 - Google Patents
有机卤代产物的化学破坏方法Info
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- CN1016142B CN1016142B CN88106409A CN88106409A CN1016142B CN 1016142 B CN1016142 B CN 1016142B CN 88106409 A CN88106409 A CN 88106409A CN 88106409 A CN88106409 A CN 88106409A CN 1016142 B CN1016142 B CN 1016142B
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Abstract
本发明涉及一种破坏卤化产物的方法，尤其是氯化的芳族产物，或者含有这些产物的油类，例如被多氯联苯污染的未氯化的介电质流体。
本方法的特征是使这些产物与一种烃氧基金属，最好是甲醇钠，在温度为250至290℃下起作用。
Description
本发明涉及一种破坏有机卤化产物的化学方法，尤其是氯化芳族产物，例如多氯联苯（PCB），它们往往是混合在未氯化的有机产品中。
在先有技术中已有人建议，利用甲醇提取来除去含在变压器的介电油类或润滑油类中的PCB（美国专利4387018）。甲醇然后通过蒸馏而与PCB分离，再循环使用。这一方法可除去70%PCB。欧洲专利EP99951建议用颗粒大于10微米的分散性钠来处理类似的产物。欧洲申请专利EP107404披露了用一种聚乙二醇的钠盐来处理含有652ppm PCB的变压器油。这些方法的缺点是需要进行分离和再循环作用以及使用钠。欧洲申请专利EP21294披露了破坏二喔星（dioxins），尤其是含39.7ppm的2，3，7，8-四氯二苯并-对-二喔星的氯代甲氧基苯，方法是在加压和160℃下在甲醇中用甲醇钠与这一产物进行反应。此外，匈牙利期刊MAGY.KEMFOLYOTRAT 71（8），343-6，（1965）中Gyuia Pfeifer和Terez Flora的一篇文章阐述了甲醇钠在120-140℃可开始分解。目前已找到一种更为简便和极为有效的方法。
本发明的目的是提供破坏卤化有机产物的方法，其特征为：
a）.将这些产物与至少一种烃氧基碱金属接触一段可使有机卤素转化为无机卤化物所需的时间。
b）.操作温度高于220℃。
本发明适用于一切囟化产物，但是更适用于含有可被氯和/或溴取代的芳香烃的产物。这类产物包括，例如，氯化的或溴化的二喔星，氯
化的或溴化的二苯并呋喃，多氯联苯，多溴联苯，多溴二苯醚，多氯二苯醚。这些产物可以是单一的纯产物，也可以是它们之间的混合产物，或者是与未卤化的有机产物的一种混合物，例如聚芳基烷，矿物油等。
虽然本发明可用以破坏一切卤化产物，但是用于含囟素在1%重量比以下，而最好在1000ppm以下的产物则更为有利。
虽然人们可以之用来由一元醇，二元醇，或三醇与一种碱金属所生成的任何一种烃氧基金属，其中包括甲醇金属，和乙二醇或聚乙二醇的烃氧基金属，但是较为有利的是采用甲醇、乙醇、丙醇或异丙醇的钠、锂、或钾的烃氧基金属，或者是这些产品的一种混合物，而最好是甲醇钠。
最好是将烃氧基金属加入卤化产物中，或含有卤化产物的混合物中。最好是采用粉末状的甲醇钠。按化学计量学的方法计算，每除去一个原子的卤素，就需要一个基团的烃氧基金属，所采用的烃氧基金属量要超过此化学计算量，过量五至十倍能得到极为良好的脱卤化作用。例如如果一种混合物含有100ppm以氯计算的PCB，采用的甲醇钠量为0.14%。
将另一种可将有机氯转化成无机氯化物的其他产品，例如碳酸钠或其他碱介质，与烃氧基金属同时加入，并不超出本发明的范围。
囟化有机产物与烃氧基金属的接触最好是在搅拌状态下进行，例如在一搅拌反应器或填充塔，或其他允许充分搅拌的装置中进行，以使烃氧基金属充分分散，并与卤化产物接触一段可使其破坏所需的时间。反应可以连续进行也可以间歇进行。反应速度随温度的升高而增加。操作温度可采用220至300℃，最好采用250至290℃。根据产物的物理特性（蒸汽压），可在大气压下或更高压力下操作，反应的停留时间与有机卤素的量、温度、烃氧基金属量以及能使反应物充分接触的搅拌条件等因素有关，一般需要30分钟至10小时。
本发明特别适用于破坏含在一种混合物中的芳族卤化产物，例如含有PCB的未氯化的介电液体或矿物油。本发明方法可用于此种含有PCB的产物或其他氯化产物，然后再用例如蒸馏的方法将无机卤化产物从其他产物中分离出来。这样就得到不含有机氯的矿物油、介电液体。
为了尽可能保证脱卤化作用的彻底进行，采用了过量的烃氧基金属。当处理一种含有数百ppm的介电液体时，在反应结束时，就可得到介电液体，NaCl氯化物，芳族氯化产物的转化产物，以及剩下的没有反应的烃氧基金属。最方便的是将此混合物加以蒸馏，以得到不再含有芳族氯的纯介电液体。当采用的烃氧基金属是甲醇钠时，就要注意不能使甲醇钠在295℃下在蒸馏设备中停留超过12小时，以避免甲醇金属分解。
本发明方法本身也可与碳酸钠方法结合使用。碳酸钠是极容易操作的，但只能除去脂族的卤素以及极不稳定的囟代芳烃。
本发明方法可获得卤代芳烃含量少于10ppm的产品。本发明方法的优点是，即使用于含有反应能力不强的卤素原子的产物，也不需要应用溶剂，也即是说，只要在例如含PCB的油中加入烃氧基金属，也就不必如欧洲专利EP21294中所述，除加入烃氧基金属外还加入与该烃氧基金属相应的醇类了。此方法在回收已除去卤代芳烃的产物之前，在处理完成时，不需要预先分离过量的烃氧基金属，特别是甲醇钠。
此法的另一优点，是所产生成的副产物如NaCl氯化物，由烃氧基金属转化成的芳族卤化产物，以及剩下的未反应的烃氧基金属等可以很容剔地用焚烧的方法加以销毁而不产生有毒产物。
以下是本发明的一些示例，但并不限于此。
例1
取1000克含300ppm以一氯苄基甲苯形式出现的氯代芳烃的二苄基甲苯（DBT）。将此混合物放入一个装有转动搅拌器、回流冷凝器和氮气喷
咀的反应器中。经过用100℃的氮气流吹扫15分钟后，加入1%重量比的甲醇钠（即10克）。将此混合物在285℃以及在搅拌和通入氮气吹扫的情况下加热回流3小时。然后在逐步减压下将所得到的产物进行蒸馏直到真空度为2毫米汞柱，以便使蒸馏塔底温度不超过300℃。所得的馏出物中芳族氯的总含量为3ppm。
作为对照，在用碳酸钠处理含有相同的氯化产物的同一产品时，所得的产物中氯代芳香烃的总含量为100ppm。
例2
对例1的DBT作相似的处理，但改用NaOC2H5，KOCH3，KOC2H5，NaOH（CH3）2，处理条件与例1相同。所得结果列于附表。
例3
a）.以1%的甲醇钠对含1000ppmPCB的DBT在280℃下处理3小时。所得的产物含氯量少于15ppm。
b）.与a）相同，但DBT中含1000ppm的四氯苄基甲苯。
以上的结果均列于附表。
例4
a）.以1%CH3ONa对含1000ppmPCB的矿物油在280℃下处理小时。所得产物含囟素量少于15ppm。
b）.与a）相同，但矿物油中含1000ppm八溴联苯。
以上的结果均列于附表。
例5
在一个装有转动搅拌器、冷凝器和氮气喷咀的反应器中通入1600克DBT和32克甲醇钠。整个体系在290℃以及通入氮气和搅拌的情况下回流。然后停止通入氮气，冷凝器的出口连在一个槽上。经过在290℃下处理70小时后，没有观察到有任何气体排出。反应混合物经过冷却和过滤后显示：
·经色谱分析后，在过滤液中没有发现有轻质产物，
·固体在经过用氯苯、正己烷洗涤后，并在不与空气接触下干燥后（所得的重量＝所用的甲醇金属重量的95%），经红外光谱分析证明的确是甲醇钠。
附表
使用的 处理和蒸馏后产品
处理产物的原始状态 烃氧基金属 中卤素的重量含量
例2
DBT含300ppm氯（以 1%C2H5ONa ＜15ppm
一氯苄基甲苯的形式存 0.5%CH3OK ＜15ppm
0.5%C2H5OK ＜15ppm
在） 0.5%（CH3）2CHONa 37ppm
例3
DBT含1000ppm PCB 1%CH3ONa ＜15ppm
（6.5氯）
DBT含1000ppm四氯 1%CH3ONa ＜15ppm
苄基甲苯
例4
矿物油含1000ppm 1%CH3ONa ＜15ppm
PCB 6.5氯（＊）
矿物油含1000ppm 1%CH3ONa ＜15ppm
八溴联苯（＊＊）
（＊）测定蒸馏残渣的580ppm氯（以氯化物的形式存在），以所用的矿物油量为基准。
（＊＊）测定蒸馏残渣的846ppm溴（以溴化物的形式存在），以所用的矿物油量为基准。
Claims (8)
1、一种破坏在有机油、介电油或矿物油中含有的有机卤化产物的方法，其特征为：a).将这些产物与至少一种烃氧基碱金属接触一段可使有机卤素转化为无机卤化物所需的时间，
b).烃氧基金属的用量超过按卤素的量计算的化学计算量，
c).温度要高于220℃，
d).用蒸馏的方法回收该不含所述卤化有机产物的油。
2、根据权利要求1的方法，其特征为烃氧基金属可在甲醇、乙醇、丙醇或异丙醇钠、锂、或钾中选用，最好采用甲醇钠。
3、根据权利要求1的方法，其特征为有机卤化产物是含有由氯和/或由溴取代的芳香烃的产物。
4、根据权利要求3的方法，其特征为含芳香烃的产物是苄基甲苯或三苯基甲烷或它们的高级同系物。
5、根据权利要求3的方法，其特征为含芳香烃的产物是多氯联苯（PCB）或二喔星，或联苯二苯并呋喃。
6、根据权利要求1的方法，其特征为，开始的有机卤化产物是与另一种有机产物以混合物的形式存在的。
7、根据权利要求1的方法，其特征为操作温度是在220至300℃之间，最好为250至290℃之间。
8、根据权利要求1至7之一的方法，其特征为使用的是粉末状无水的烃氧基金属。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8712248 | 1987-09-03 | ||
| FR8712248A FR2620055B1 (fr) | 1987-09-03 | 1987-09-03 | Procede chimique de destruction de produits organiques halogenes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1032109A CN1032109A (zh) | 1989-04-05 |
| CN1016142B true CN1016142B (zh) | 1992-04-08 |
Family
ID=9354601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88106409A Expired CN1016142B (zh) | 1987-09-03 | 1988-09-03 | 有机卤代产物的化学破坏方法 |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0306398B1 (zh) |
| JP (1) | JPH0667409B2 (zh) |
| KR (1) | KR910000196B1 (zh) |
| CN (1) | CN1016142B (zh) |
| AT (1) | ATE85229T1 (zh) |
| CA (1) | CA1336981C (zh) |
| DE (1) | DE3878098T2 (zh) |
| DK (1) | DK169377B1 (zh) |
| ES (1) | ES2053784T3 (zh) |
| FI (1) | FI97276C (zh) |
| FR (1) | FR2620055B1 (zh) |
| IE (1) | IE63083B1 (zh) |
| NO (1) | NO176749C (zh) |
| PT (1) | PT88421B (zh) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2656603B1 (fr) * | 1989-12-28 | 1993-05-21 | Atochem | Procedes de synthese de benzyltoluene et dibenzyltoluene a faible teneur en chlore. |
| US5490919A (en) * | 1990-08-14 | 1996-02-13 | State Of Isreal, Atomic Energy Commission | Process for the dehalogenation of organic compounds |
| US5093011A (en) * | 1990-12-12 | 1992-03-03 | Chemical Waste Management, Inc. | Process for dehalogenation of contaminated waste materials |
| JPH04253875A (ja) * | 1991-02-01 | 1992-09-09 | Chiyoda Kohan Kk | クロロホルム又はクロロジフルオロメタンの分解除去方法 |
| DE4109639C2 (de) * | 1991-03-23 | 1994-06-01 | Metallgesellschaft Ag | Verfahren zur Zersetzung von polyhalogenierten Organoverbindungen |
| JP2638483B2 (ja) * | 1994-06-30 | 1997-08-06 | 株式会社関西テック | 多塩素化芳香族化合物の処理方法 |
| ES2297829T3 (es) | 1994-09-30 | 2008-05-01 | Arkema France | Uso para los transformadores de distribucion de una composicion dielectrica a base de poliarilalcanos con propiedades dielectricas mejoradas. |
| JP4537539B2 (ja) * | 2000-06-20 | 2010-09-01 | 利夫 半谷 | 有害物質の分解処理方法と処理設備 |
| JP2003001220A (ja) * | 2001-06-25 | 2003-01-07 | Kansai Electric Power Co Inc:The | 汚染物からの多塩素化芳香族化合物分離方法 |
| RU2595971C2 (ru) | 2011-09-06 | 2016-08-27 | Бритиш Америкэн Тобэкко (Инвестментс) Лимитед | Нагревание курительного материала |
| GB201217067D0 (en) | 2012-09-25 | 2012-11-07 | British American Tobacco Co | Heating smokable material |
| GB201311620D0 (en) | 2013-06-28 | 2013-08-14 | British American Tobacco Co | Devices Comprising a Heat Source Material and Activation Chambers for the Same |
| GB201500582D0 (en) | 2015-01-14 | 2015-02-25 | British American Tobacco Co | Apparatus for heating or cooling a material contained therein |
| US11924930B2 (en) | 2015-08-31 | 2024-03-05 | Nicoventures Trading Limited | Article for use with apparatus for heating smokable material |
| US20170055584A1 (en) | 2015-08-31 | 2017-03-02 | British American Tobacco (Investments) Limited | Article for use with apparatus for heating smokable material |
| US20170055575A1 (en) | 2015-08-31 | 2017-03-02 | British American Tobacco (Investments) Limited | Material for use with apparatus for heating smokable material |
| US20170119047A1 (en) | 2015-10-30 | 2017-05-04 | British American Tobacco (Investments) Limited | Article for Use with Apparatus for Heating Smokable Material |
| US20170119046A1 (en) | 2015-10-30 | 2017-05-04 | British American Tobacco (Investments) Limited | Apparatus for Heating Smokable Material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4327027A (en) * | 1979-06-15 | 1982-04-27 | Vertac Chemical Corporation | Chemical detoxification of toxic chlorinated aromatic compounds |
| AU555461B2 (en) * | 1983-03-10 | 1986-09-25 | Sea Marconi Decontamination S.R.L. | Process for the decomposition and decontamination of organic substances and halogenated toxic materials |
| US4574013A (en) * | 1985-04-18 | 1986-03-04 | Galson Research Corporation | Method for decontaminating soil |
| CH668709A5 (de) * | 1985-12-06 | 1989-01-31 | Ciba Geigy Ag | Verfahren zur enthalogenierung von polyhalogenierten aliphatischen und aromatischen verbindungen. |
| DE3621175A1 (de) * | 1986-06-25 | 1988-01-07 | Huels Chemische Werke Ag | Verfahren zur enthalogenierung von kohlenwasserstoffoelen |
-
1987
- 1987-09-03 FR FR8712248A patent/FR2620055B1/fr not_active Expired - Lifetime
-
1988
- 1988-08-23 CA CA000575896A patent/CA1336981C/fr not_active Expired - Lifetime
- 1988-08-29 AT AT88402176T patent/ATE85229T1/de not_active IP Right Cessation
- 1988-08-29 DE DE8888402176T patent/DE3878098T2/de not_active Expired - Lifetime
- 1988-08-29 ES ES88402176T patent/ES2053784T3/es not_active Expired - Lifetime
- 1988-08-29 EP EP88402176A patent/EP0306398B1/fr not_active Expired - Lifetime
- 1988-09-01 NO NO883893A patent/NO176749C/no not_active IP Right Cessation
- 1988-09-01 JP JP63219600A patent/JPH0667409B2/ja not_active Expired - Lifetime
- 1988-09-02 FI FI884055A patent/FI97276C/fi not_active IP Right Cessation
- 1988-09-02 PT PT88421A patent/PT88421B/pt not_active IP Right Cessation
- 1988-09-02 DK DK488488A patent/DK169377B1/da not_active IP Right Cessation
- 1988-09-02 IE IE267088A patent/IE63083B1/en not_active IP Right Cessation
- 1988-09-03 CN CN88106409A patent/CN1016142B/zh not_active Expired
- 1988-09-03 KR KR1019880011407A patent/KR910000196B1/ko not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| NO883893D0 (no) | 1988-09-01 |
| FI97276C (fi) | 1996-11-25 |
| KR890004780A (ko) | 1989-05-09 |
| FR2620055B1 (fr) | 1991-05-10 |
| DE3878098T2 (de) | 1993-06-09 |
| DK488488A (da) | 1989-03-04 |
| CA1336981C (fr) | 1995-09-12 |
| FI884055A0 (fi) | 1988-09-02 |
| FR2620055A1 (fr) | 1989-03-10 |
| FI97276B (fi) | 1996-08-15 |
| IE63083B1 (en) | 1995-03-22 |
| JPS6470084A (en) | 1989-03-15 |
| DK488488D0 (da) | 1988-09-02 |
| FI884055A (fi) | 1989-03-04 |
| DE3878098D1 (de) | 1993-03-18 |
| EP0306398B1 (fr) | 1993-02-03 |
| PT88421A (pt) | 1989-07-31 |
| PT88421B (pt) | 1992-10-30 |
| IE882670L (en) | 1989-03-03 |
| ES2053784T3 (es) | 1994-08-01 |
| NO176749B (no) | 1995-02-13 |
| DK169377B1 (da) | 1994-10-17 |
| KR910000196B1 (ko) | 1991-01-23 |
| NO883893L (no) | 1989-03-06 |
| JPH0667409B2 (ja) | 1994-08-31 |
| CN1032109A (zh) | 1989-04-05 |
| ATE85229T1 (de) | 1993-02-15 |
| NO176749C (no) | 1995-05-24 |
| EP0306398A1 (fr) | 1989-03-08 |
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