CN1128961A - 含有金属的物质的溶剂萃取 - Google Patents
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Abstract
一种从含有金属物质的介质中萃取金属物质的方法，包括使介质与含有超临界流体和用于溶解所述介质中的金属物质的络合剂以及用于改变金属物质的氧化态的调节剂的萃取溶剂接触。
Description
本发明涉及含有金属的物质的溶剂萃取。
含有金属的物质的溶剂萃取用于各种分析过程和工业领域，特别是化学工程和废物处理领域。例如，在固体或液体介质中存在的有害放射性和非放射性物质，可以通过萃取进入溶剂体系，然后进行分离和处理，如果合适还可以循环。
已用于含金属物质的溶剂萃取的一种已知技术是超临界流体萃取(SFE)。这一技术在大量的文献中有报道，如：Hawthorne，S B Anal.chem.1990，62，633A；Fahmy；T、M；Paulaitis，M E；Johnson，D M；McNally，M E P Anal.chem.1963，65，1462；Lin，Yuehe；Brauer，R D；Laintz，K E；Wai，C M Anal.Chem.1993，65，2549；和Hedrick，J L；Mulcahey，L J Taylor L T，In″SupercriticalFluid Technology--Theoretical and Applied Approaches toAnalytical Chemistry″，Bright F V and McNally M E，Eds.；ACS Symposium Series 488；Amer.Chem.Soc.，Washington，DC，199l，p206-220.
在SFE中，萃取溶剂包括超临界流体如二氧化碳，和用于通过形成可溶性络合物而溶解金属物质的络合剂或鳌合剂。
本发明提供一种从含有金属物质的介质中萃取金属物质的方法，包括使介质与含有超临界流体和络合剂以及调节剂(conditioning agent)的萃取溶剂接触，其中络合剂用于溶解所述介质中的金属物质，而调节剂用于改变金属物质的氧化态。
调节剂可包括氧化剂或还原剂，并且它的存在用于通过改变金属物质的氧化态以促进金属物质在络合剂中的溶解。因此，调节剂的存在可以有利地提高溶剂体系溶解金属物质的效率。
当调节剂为氧化剂时，可以选自过氧化物，如H2O2，高氯酸盐，如NaClO3、氧气、臭氧和高锰酸钾，或复合氧化剂。
当调节剂为还原剂时，可以选自氢气、水合肼或含有可氧化性金属物质如Fe++、Cu+的溶液，或复合还原剂。
希望使用本发明的方法从中脱除金属物质的介质可以是固体或液体介质。当介质为固体时，它可以包括颗粒性材料，如可以是泥土，污泥和工业残渣，工业矿渣或类似物质。金属物质可以存在于颗粒的表面和/或结合于颗粒的内部。介质也可以是待去污染的材料，如金属或混凝土结构；废建筑材料，如废砖石；或污染的废弃材料，如橡胶、塑料或织物材料。当介质为液体时，它可以例如包括工艺溶剂或工业废液。
例如，本发明的方法可以用于分析液体或固体样品中有意义的金属物质的浓度。例如，当分析污染物的存在时，可以制备成备用溶液，然后分成多个样品以进行不同的分析。
本发明还可以用于使由放射性或非放射性有毒重金属物质污染的表面脱污染。
例如，本发明可以用于土壤改良目的的泥土清理。
本发明还可以用于使用常规溶剂萃取的工艺中，如在辐射过的核燃料的再加工过程中溶解锕系元素，或在铀矿石的精炼处理过程中溶解铀。
将使用本发明的方法萃取的金属物质可包括放射性物质，可以包括：
(i)锕系元素，或其放射性衰变产物，或其化合物；
(ii)裂变产物；
(iii)重金属或其化合物。
锕系元素是元素周期序数89-104，并包括89和104的元素。
在此所用术语″裂变产物″是指在核燃料的裂变过程中作为直接产物形成的元素(或称为裂变碎片)和这种直接产物经过β衰变所形成的产物。裂变产物包括从硒到铈范围内的元素，如56Ba、40Zr和52Te、55Cs和58Ce。
将使用本发明萃取的金属物质也可以包括非放射性重金属物质。希望用本发明方法分离的非放射性重金属包括有毒金属，如钴、铬、铅、镉和汞，这些物质通常以土地污染物形式存在于工厂附近或废物处理场上，以及使用含这些元素的化学物质的水沉积物中。
用于本发明方法的络合剂根据所要萃取的金属物种选择。要求络合剂要具有高的挥发性，且在不同温度下在超临界流体中的溶解度要有显著的变化。这样使得将要形成的络合物可以通过已知的方法如沉淀法从溶剂中分离出来。
例如，对于萃取例如汞、铅和镉等金属，已知氟代二硫代氨基甲酸酯(fluorinated dithiocarbamate)为适宜的络合物。对于萃取例如铀和钍等锕系元素，已知氯代β-二酮衍生物为适宜的络合剂，而对于锕系元素和镧系元素，冠醚是适宜的。
前述络合剂常包括带负电的配位体。络合剂可包括多种这样的配体。它还包括一种或多种中性配体作为任选添加剂，例如有机磷酸酯，如三丁基磷酸酯。
在本发明的方法中，包括溶剂混合物的组合物可以下述的相对比例包括：
(a)超临界流体，从80V％-99.99V％(体积百分比，下同)；
(b)络合剂，从0.01V％到10V％；
(c)调节剂，从0.01V％到10V％。
在萃取溶剂中还可以包括其他的任选添加剂。例如，少量的水性添加剂，如水(至多为含上述(a)、(b)和(c)的组合物的10V％)和少量的有机添加剂，如乙醇，至多10V％。
在本发明的方法中，络合剂和调节剂可以各自在接触含金属的物质之前或接触期间的任何时间加到超临界流体中。例如，络合剂和调节剂可以各自分别加入萃取剂混合物中，然后再加到在萃取剂贮槽中的超临界流体中，形成的萃取溶剂可在压力下通过管道进入接触器，在此与要处理的介质接触。含金属的溶液可进一步转移到萃取器，在此金属物质通过沉淀与溶液分离。例如，萃取器包括有收集槽，并装有各种相关装置，以调节含超临界流体的溶液的压力和/或温度，从而使其中的金属物质沉淀出来。收集槽中可以含有有机溶剂，如氯仿。随后使用已知的方法将沉淀分离出来，如通过过滤、离心分离、絮凝或旋液分离或其它已知的方法。
锕系元素和其它的有害物质可以由此以高度浓缩的形式得到。如果需要，特殊的锕系元素，如钚，还可以进一步使用已知的方法与其它分离的物质分离，如通过在辐射核燃料再加工工艺中所用的常规方法。分离出的高活性辐射元素可以通过已知的方法进行密封，如通过已知的玻璃化工艺。在任何情况下，处理浓缩的钚和其它有害元素的全部过程都要在辐射屏蔽器中进行远距离操作。
使用本发明的方法萃取金属的过程中，可以有利地使用本身对环境没有危害的化学品，这样基本上不产生二次水溶性废物，与先有技术不同。
下面参考附图，通过实施例描述本发明的实施方案，其中
图1是体现本发明的超临界流体萃取工艺流程示意图。
如图1所示，被锕系元素污染的颗粒材料，如砂子，经洗涤，冲洗，空气干燥，然后置于市售接触槽1中的一个不锈钢容器中。包括等比例的络合剂氟代β-二酮(例如六氟乙酰丙酮)和氧化剂如H2O2混合物的萃取剂在高压萃取剂罐3中形成。将接触槽1和萃取剂罐3放入一个炉中，加热到精确控制的温度60℃。超临界二氧化碳在150atm的压力下，从源5通过熔凝的氧化硅管7泵入槽3，在此与萃取剂混合。
含有超临界流体的萃取溶剂进一步通过管道9流过槽1中的颗粒材料，从而锕系元素被氧化和溶解。形成的溶液通过管道11进入萃取器13，在此，将超临界流体的压力降低到1atm，而锕系元素，如铀和钚的颗粒沉淀出来。然后通过过滤，在分离器15中分离出锕系元素颗粒，滤液使用已知的方式进行安全密封和处理。
Claims (11)
1.一种从含有金属物质的介质中萃取金属物质的方法，包括使介质与含有超临界流体和用于溶解于所述介质中的金属物质的络合剂以及用于改变金属物质的氧化态的调节剂的萃取溶剂接触。
2.根据权利要求1的方法，其中调节剂包括氧化剂或还原剂，并且其存在有助于通过改变金属物质的氧化态来使金属物质溶于络合剂中。
3.根据权利要求1或2的方法，其中从中将要脱除金属物质的介质包括固体或液体介质。
4.根据权利要求3的方法，其中介质为固体，并包括颗粒材料，所述颗粒材料又包括泥土、污泥、工业残渣或工业矿渣。
5.根据权利要求3的方法，其中介质为待去污染的固体物质，并包括金属或混凝土结构物、废建筑材料、碎砖石或被污染的废物。
6.根据权利要求3的方法，其中介质为液体，并且包括工艺溶剂或工业废物流。
7.根据上述权利要求任何一项的方法，用于分析液体或固体样品中有意义的金属物质的浓度。
8.根据权利要求1-6中任何一项的方法，其中所述方法用于对被放射性或非放射性的有毒重金属物质污染的表面脱污染。
9.根据权利要求3的方法，并且所述方法用于土地改良目的的土地清洗。
10.根据上述权利要求任何一项的方法，其中含有溶剂混合物的组合物包括下述百分比的下述成分：
a)超临界流体，80V％-99.99V％(体积百分比)；
b)络合剂，0.01V％-10V％；
c)调节剂，0.01V％-10V％。
11.根据权利要求1的方法，基本上是参考具体实施方案之一描述的方法。
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| GB9407892A GB9407892D0 (en) | 1994-04-21 | 1994-04-21 | Solvent extraction of metal containing species |
| GB9407892.0 | 1994-04-21 |
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| EP (1) | EP0705127B1 (zh) |
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| KR (1) | KR960703031A (zh) |
| CN (1) | CN1082826C (zh) |
| AT (1) | ATE169509T1 (zh) |
| AU (1) | AU2312095A (zh) |
| DE (1) | DE69503998T2 (zh) |
| GB (1) | GB9407892D0 (zh) |
| WO (1) | WO1995028999A1 (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102706723A (zh) * | 2012-02-16 | 2012-10-03 | 南京晓庄学院 | 用于农产品中重金属汞快速检测的前处理试剂及方法 |
| CN103480351A (zh) * | 2012-06-13 | 2014-01-01 | 梁明在 | 受金属或/与清洁剂污染的活性碳再生方法 |
| CN103586276A (zh) * | 2013-11-25 | 2014-02-19 | 辽宁石油化工大学 | 一种修复镉污染土壤的淋洗方法 |
| CN113102485A (zh) * | 2021-03-24 | 2021-07-13 | 中国科学院工程热物理研究所 | 一种基于超临界流体的重金属污染土壤修复系统及方法 |
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| US5965025A (en) * | 1991-06-12 | 1999-10-12 | Idaho Research Foundation, Inc. | Fluid extraction |
| US5606724A (en) * | 1995-11-03 | 1997-02-25 | Idaho Research Foundation, Inc. | Extracting metals directly from metal oxides |
| US5840193A (en) * | 1996-07-26 | 1998-11-24 | Idaho Research Foundation | Fluid extraction using carbon dioxide and organophosphorus chelating agents |
| US6416682B1 (en) | 1999-11-04 | 2002-07-09 | Ceramic Oxides International B.V. | Method of producing minerals under near-critical, critical and supercritical conditions |
| ES2184630B1 (es) * | 2001-08-03 | 2004-01-16 | Soc Es Carburos Metalicos Sa | Procedimiento de lixiviacion selectiva de metales. |
| US7128840B2 (en) | 2002-03-26 | 2006-10-31 | Idaho Research Foundation, Inc. | Ultrasound enhanced process for extracting metal species in supercritical fluids |
| CN1308470C (zh) * | 2005-03-15 | 2007-04-04 | 深圳市伟雄机械设备有限公司 | 贵金属的无毒低成本提炼方法 |
| EP2300032A4 (en) | 2008-05-13 | 2012-12-05 | Univ Kansas | MARKER PRESENTING IN THE FORM OF A MAP PEPTIDE (METAL ABSTRACTION PEPTIDE) AND ASSOCIATED METHODS |
| CN101886175B (zh) * | 2010-07-02 | 2012-07-18 | 李志伟 | 从含铀稀土渣中提取铀生产重铀酸盐的方法 |
| WO2013181461A2 (en) | 2012-06-01 | 2013-12-05 | University Of Kansas | Metal abstraction peptide with superoxide dismutase activity |
| US10422023B2 (en) * | 2015-04-23 | 2019-09-24 | Carnegie Mellon University | Recovery of rare earth elements by liquid-liquid extraction from fresh water to hypersaline solutions |
| RU2631806C2 (ru) * | 2015-10-20 | 2017-09-26 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Пермский государственный национальный исследовательский университет" | Новый вариант расслаивания в системе антипирин (АП) - вода - сульфат натрия |
| US20210140010A1 (en) * | 2019-05-21 | 2021-05-13 | Seth G.P. Babcock | Devices, methods, and systems for combined ore reduction and metals stripping |
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| US2830066A (en) * | 1947-12-31 | 1958-04-08 | Lawrence B Magnusson | Separation process for transuranic element and compounds thereof |
| US4529503A (en) * | 1982-08-05 | 1985-07-16 | Phillips Petroleum Company | Demetallization of hydrocarbon containing feed streams with phosphorous compounds |
| US4464251A (en) * | 1983-01-12 | 1984-08-07 | Phillips Petroleum Company | Removal of contaminants from organic compositions |
| US4518484A (en) * | 1984-02-16 | 1985-05-21 | Phillips Petroleum Company | Metals removal with a light hydrocarbon and an organophosphorous compound |
| DE3708751C2 (de) * | 1987-03-18 | 1994-12-15 | Kernforschungsz Karlsruhe | Verfahren zur nassen Auflösung von Uran-Plutonium-Mischoxid-Kernbrennstoffen |
| CA2031750A1 (en) * | 1989-12-15 | 1991-06-16 | Marc Lemaire | Method for separating by using crown compounds plutonium from uranium and from fission products in the initial stages for the reprocessing of irradiated nuclear fuels |
| US5225173A (en) * | 1991-06-12 | 1993-07-06 | Idaho Research Foundation, Inc. | Methods and devices for the separation of radioactive rare earth metal isotopes from their alkaline earth metal precursors |
| US5356538A (en) * | 1991-06-12 | 1994-10-18 | Idaho Research Foundation, Inc. | Supercritical fluid extraction |
| US5376714A (en) * | 1991-12-31 | 1994-12-27 | Yates; John B. | Flow polymer alloys |
| US5322644A (en) * | 1992-01-03 | 1994-06-21 | Bradtec-Us, Inc. | Process for decontamination of radioactive materials |
-
1994
- 1994-04-21 GB GB9407892A patent/GB9407892D0/en active Pending
-
1995
- 1995-04-20 WO PCT/GB1995/000891 patent/WO1995028999A1/en active IP Right Grant
- 1995-04-20 KR KR1019950705784A patent/KR960703031A/ko not_active Application Discontinuation
- 1995-04-20 CN CN95190460A patent/CN1082826C/zh not_active Expired - Fee Related
- 1995-04-20 AU AU23120/95A patent/AU2312095A/en not_active Abandoned
- 1995-04-20 EP EP95916744A patent/EP0705127B1/en not_active Expired - Lifetime
- 1995-04-20 DE DE69503998T patent/DE69503998T2/de not_active Expired - Fee Related
- 1995-04-20 US US08/571,846 patent/US5750081A/en not_active Expired - Fee Related
- 1995-04-20 JP JP52744995A patent/JP3822904B2/ja not_active Expired - Fee Related
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102706723A (zh) * | 2012-02-16 | 2012-10-03 | 南京晓庄学院 | 用于农产品中重金属汞快速检测的前处理试剂及方法 |
| CN102706723B (zh) * | 2012-02-16 | 2014-10-08 | 南京晓庄学院 | 用于农产品中重金属汞快速检测的前处理试剂及方法 |
| CN103480351A (zh) * | 2012-06-13 | 2014-01-01 | 梁明在 | 受金属或/与清洁剂污染的活性碳再生方法 |
| CN103586276A (zh) * | 2013-11-25 | 2014-02-19 | 辽宁石油化工大学 | 一种修复镉污染土壤的淋洗方法 |
| CN113102485A (zh) * | 2021-03-24 | 2021-07-13 | 中国科学院工程热物理研究所 | 一种基于超临界流体的重金属污染土壤修复系统及方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9407892D0 (en) | 1994-06-15 |
| EP0705127A1 (en) | 1996-04-10 |
| KR960703031A (ko) | 1996-06-19 |
| WO1995028999A1 (en) | 1995-11-02 |
| DE69503998D1 (de) | 1998-09-17 |
| JPH09501353A (ja) | 1997-02-10 |
| DE69503998T2 (de) | 1998-12-17 |
| ATE169509T1 (de) | 1998-08-15 |
| EP0705127B1 (en) | 1998-08-12 |
| AU2312095A (en) | 1995-11-16 |
| US5750081A (en) | 1998-05-12 |
| JP3822904B2 (ja) | 2006-09-20 |
| CN1082826C (zh) | 2002-04-17 |
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