CN1304302C - 用于原位修复受卤代烃污染的土壤、地下水以及土壤和地下水的混合物的方法及其所用的组合物或载体催化剂 - Google Patents
用于原位修复受卤代烃污染的土壤、地下水以及土壤和地下水的混合物的方法及其所用的组合物或载体催化剂 Download PDFInfo
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- CN1304302C CN1304302C CNB038165627A CN03816562A CN1304302C CN 1304302 C CN1304302 C CN 1304302C CN B038165627 A CNB038165627 A CN B038165627A CN 03816562 A CN03816562 A CN 03816562A CN 1304302 C CN1304302 C CN 1304302C
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- soil
- carried catalyst
- iron
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Treating Waste Gases (AREA)
Abstract
本发明提供一种用于原位修复受卤代烃污染的土壤和/或地下水的载体催化剂，它包含浸渍有零价铁的吸附剂，其中该吸附剂能够吸附该卤代烃。本发明进一步提供用于原位生物修复受卤代烃污染的土壤和/或地下水的生物修复组合物，它包含能够吸附所述烃的吸附剂，能在硫酸盐还原条件下代谢所述烃的兼性厌氧菌混合物，在一段时间内释放硫酸根的含硫酸根化合物，以及促进所述厌氧菌生长的营养系统，其中所述营养系统包含硫化物清除剂。
Description
技术领域
本发明涉及用于原位修复污染的环境的组合物和方法，特别是涉及修复受卤代烃污染的土壤和/或地下水，和生物修复受烃污染的土壤和/或地下水。
背景技术
随着对环境保护和公众健康与安全关注的增加，如今鉴定并去除环境，特别是地下水中的污染物质已成为最重要的环境问题之一。多年来无节制地倾倒有害物质已经引起许多地区地下水的严重污染，产生重大的健康问题并引起区域生态系统的大范围破坏。因此，近年来非常强调污染的地下水和垃圾堆存处周围环境的净化与修复，这导致环境净化和修复新工业的产生。然而，目前用于污染场所修复的常规技术常常非常昂贵，可能需要进行多年，而且并不总是有效。
由于氯化溶剂和石油烃类的广泛使用，全世界许多地方已发现污染的地下水。氯化溶剂，如三氯乙烷(TCE)和全氯乙烯(PCE)用于诸如干洗的目的，并且在许多工业中用作脱脂剂和清洁剂。通常在地下水中发现的石油烃类包括汽油成分，如苯、甲苯、乙苯和二甲苯。地下水的其它常见污染物包括萘和氯化溶剂。其他地下水和土壤污染物包括由燃烧、煤炼焦、石油加工和木材处理操作产生的多环芳烃(PAH)；以及曾广泛用于电器变压器和电容器以及多种其它工业目的、杀虫剂和除草剂的多氯联苯(PCB)。
各种离位(ex situ)和原位方法已用于处理、修复或处置污染的土壤。离位方法一般包括将污染的土壤永久转移到安全的填埋场、焚化、间接热处理、通气、通风以及空气喷射。由于昂贵的挖掘、运输和处置费用，以及潜在的残留责任，将污染的土壤转移到填埋场已不再是有吸引力的选择。焚化和间接热处理可通过就地或区外(off-site)实现，但不管在那种情况下都涉及挖掘、操作和处理基本上所有污染的土壤以及与该污染的土壤相邻的大量土壤。接着必须将土壤运输到处理设备处，或者必须现场安装处理装置。其它已采用的精细而昂贵的技术涉及利用多步骤单元操作挖掘和处理污染的土壤，以分离土壤和污染物并回收土壤。
其它现有净化方法和技术包括“抽吸并处理”方法，其中将污染的地下水抽吸到表面，进行化学净化，或者使该地下水通过生物反应器，接着再注入地下水。这样的方法一般在长时间内实施，通常为一至十年或更长。受氯代烃污染的地下水的常见修复处理包括从井或蓄水层中将水抽吸出来，在气提塔中挥发污染物，并将净化的水注回土地中。环境修复的相关类型是“挖掘和拖运”方法，其中将污染的土壤转移并接着处理或填埋。
抽吸和处理系统的最大问题在于，随着时间过去，它们变得越来越无效，以至出现稳定的残余物浓度。当这发生时，称该系统为“平台(flat-lined)”，几乎不再获得利益。另外，沟渠经常出现，以至大量污染遗留，并且在关掉泵后经常发生再污染(rebound)。
已评价许多物质和方法用于原位修复氯代烃，包括零价铁(ZVI)、高锰酸钾和过氧化氢。ZVI通过还原脱卤，即用氢取代氯取代基，而降低氯代烃的毒性。在此方法中，通过沿着卷流迁移路径(plumemigration path)挖掘沟渠并充入铁屑而构建反应壁。用打板桩或一些其它引导地下水流的方法引导污染的地下水通过屑壁。当地下水流过该壁时，氯代烃和铁元素反应，理论上，净化水出现在该壁的下斜侧。壁方法的缺点在于，难以在有效深度引入大量的固体反应物质，如铁颗粒。常规挖掘方法的实际工作深度一般限于约30英尺，而发现的地下水污染物深达300英尺。
氧气释放材料(ORM)是诸如夹层过氧化镁的组合物，它们缓慢释放氧，并推动烃污染物原位需氧降解。ORM用于改善时，在机械系统平台后最有效，而在还没有实施其它修复措施的新场所效率最低。它们的缺点是ORM昂贵，并且需要大量以彻底氧化。另外，为达到净化目的，常需要多步处理，要完成该方法可能需要二或三年。
氢气释放化合物(HRC)是在缺氧条件下经还原脱卤原位修复氯代烃的另一选择。当与地表下的水分接触时，HRC被水解，缓慢释放乳酸。本地厌氧菌(如产乙酸菌)代谢该乳酸，持续产生低浓度溶解氢。由此生成的氢接着为其它地表下微生物利用(还原脱卤)以夺取溶剂分子的氯原子并允许进一步生物降解。在加压下向污染的环境中注入HRC，每次处理持续大约六至九个月。与ORM相似，HRC昂贵，并且需要大量以彻底降解。另外，为达到净化目的，常需要多步处理，并且要完成该方法可能需要二或三年。
另一新兴净化技术是“生物修复”，其中将天然或基因工程微生物施加到污染的场所如地下水、土壤或岩石。在此技术中，开发了专门的细菌菌株，它们代谢各种烃类，如汽油、原油或其它烃基污染物，并逐步将它们还原成二氧化碳和水。然而，这种细菌修复需要使细菌与烃在细菌将作用来代谢烃的条件下密切接触。这需要大量劳力和努力以将细菌分布于土壤上，并接着持续治理和再治理污染的区域，翻耕土壤，直到细菌充分与所有污染的烃颗粒接触。另一缺点是由于井周围细菌吸附和生长引起堵塞，因而不能有效分布注入的细菌。
上述技术均具有一个或多个以下缺点。(1)要实现污染物浓度持续下降需要很长时间。(2)虽然可以实现下降，但很少达到土壤和地下水的规定净化标准或目标。(3)性能不定，并且很大程度上取决于场所条件和污染水平。(4)就活动系统而言，污染物经常从一种介质(例如地下水)除去并接着释放到另一种介质，如空气中。结果，污染物没有被破坏，而只是从一个地方转移到另一个地方。(5)就处理氯化溶剂的被动系统而言，常释放出比原污染物毒性更大的副产物，产生比处理前更恶劣的过渡情况。
仍需要有效净化受烃和/或卤代烃污染的土壤和/或地下水的修复方法，它快速、低成本并有效，并且不向土壤、空气或地下水中释放有毒副产物。
发明内容
本发明提供能快速将污染物浓度降低到规定净化标准的用于原位修复土壤和/或地下水的组合物和方法。该组合物和方法用于多种土壤和地下水情况，并适于修复许多污染物。本发明的方法和组合物不向土壤、地下水或空气中释放有毒副产物，并且对土壤性质或地下水质量没有影响。本发明的组合物低成本并有效，因为它们长时间保持活性，因此只需要一次处理。
因此，本发明一方面提供一种组合物，当将它加入诸如受一种或多种卤代烃污染的土壤和/或地下水的场所时，它吸附卤代烃，并将它们还原成毒性较小的副产物。更具体地说，本发明的一个实施方案提供一种用于原位修复受卤代烃污染的土壤和/或地下水的载体催化剂，它包含浸渍有零价铁的吸附剂，其中该吸附剂能够吸附该卤代烃污染物以及由该污染物降解生成的中间体副产物。
本发明另一方面提供一种用于修复受氯代烃污染的环境的方法，它包括向所述污染的环境的一个或多个位置加入本发明的载体催化剂，其中实现卤代烃化合物的还原脱卤。
本发明进一步提供一种生物修复组合物，当将该组合物加入受汽油或其它烃污染的水和/或土壤中时，它从土壤和/或水中吸附烃，并降解该烃。更具体地说，本发明提供一种生物修复组合物，它包含能够吸附所述烃的吸附剂，能在硫酸盐还原条件下代谢所述烃的兼性厌氧菌混合物，在一段时间内释放硫酸根的含硫酸根化合物，促进所述厌氧菌生长的营养系统，其中所述营养系统包含硫化物清除剂。
本发明另一方面提供一种用于生物修复受烃污染的环境的方法，它包括向所述污染的环境的一个或多个位置加入本发明的生物修复组合物，其中该兼性厌氧菌混合物代谢该烃污染物。
本发明的其它优点和新特征部分在以下的描述和实施例中阐述，而部分将在验证以下后对本领域技术人员而言变得清晰，或者可以通过实践本发明而得知。本发明的目的和优点可以依靠工具，并结合所附权利要求中所特别指出的内容实现和得到。
具体实施方式
本发明涉及用于原位修复受诸如烃或卤代烃污染的土壤或地下水的环境的组合物和方法。本发明的组合物和方法能将污染物浓度快速降低到规定净化标准，并可用于多种土壤和地下水条件。本发明的方法和组合物不向土壤、地下水或空气中释放有毒副产物，并且对土壤性质或地下水质量没有影响。本发明的组合物长时间保持活性，因此只需要一次处理。本发明的方法和组合物适用于修复多种污染物，并且相对于现有修复方法而言是低成本并有效的。
更具体地说，本发明的一个实施方案提供一种用于卤代烃还原脱卤的载体催化剂，它包含浸渍有零价铁的吸附剂，其中该吸附剂对卤代烃具有亲合力。该吸附剂可以是对卤代烃具有亲合力，并因此能够吸附卤代烃的任何物质。另外，该吸附剂能够吸附由污染物还原脱卤产生的有毒中间体副产物(例如，中间体，如三氯乙烷分解的副产物二氯乙烷和氯乙烯中间体)。该吸附剂提供将污染物浓缩到新介质中的方法，该介质中有高表面积的铁，如下文中详细讨论。本发明的载体催化剂通过将卤代烃污染物与其有毒中间体副产物降解成无毒副产物(如乙烷、乙炔等)而实现土壤和地下水中卤代烃的处理。
本发明的载体催化剂用每单位重量具有高表面积并对卤代烃具有高亲合力的吸附剂制备。用于本发明目的的合适的吸附剂包括，但不限于，活性炭、蛭石、氧化铝和沸石。因此，尽管采用活性炭作为该吸附剂描述制备本发明的载体催化剂的方法，但应该理解本发明的方法和载体催化剂不限于此吸附剂。活性炭从水中吸附有机物的能力增强其作为载体的效用。然而，尽管炭能捕获烃污染物，但炭本身不能长时间稳定，即它经历侵蚀等，在那种情况下，污染物随炭移动，而不真正被捕获并去除。
在一个非限制性实施方案中，该载体催化剂包含活性炭作为浸渍有零价铁的载体。活性炭提供吸附氯代烃污染物的有效基质。用零价铁浸渍活性炭在炭的孔结构内提供亚微铁沉积，将金属的可利用表面积最大化，并将金属置于吸附的污染物分子浓度最高的地方。在优选的实施方案中，所述铁是铁粉、铁屑或铁碎片。因此，该载体催化剂使铁与吸附的化学污染物有效接触，因为铁与该污染物非常接近。本发明的载体催化剂通过将氯代烃降解成无毒副产物而实现土壤和地下水中这些化学物质的处理。
活性炭由多种物质生产，包括，但不限于，煤、椰壳、泥煤和木材。本发明的载体催化剂实际上可用任何来源的活性炭生产。全部所需要的只是稍微调整系统设计参数以解决不同形式的炭。当产品用于修复地下水时，酸洗的炭是优选的，因为酸洗从炭中去除可能是环境问题的外来金属。
当吸附剂是活性炭时，可用于吸附的表面积范围为约800m2/gm至1800m2/gm。在浸渍过程中炭表面积可能有一些损失，但是当通过吸附等温线测量时测试表明该损失并不显著。在一个实施方案中，本发明的载体催化剂中零价铁的表面积范围为约50-400m2/(gm沉积铁)。沉积在炭基质内的铁的重量百分比范围为约1-20重量％。
如上所述，首先污染物被活性炭吸附，接着通过还原脱氯机理被降解。然而，在处理过程中形成有毒反应副产物如氯乙烯和顺-二氯乙烯。在常规修复系统中，即使这些副产物与铁反应，它们反应速率也低，其最初浓度可能升高。事实上，可能产生相当大的蓄积，产生比原有污染更严重的危险。本发明的载体催化剂的优点之一是这些有毒副产物也容易地被该载体催化剂的活性炭所吸附。结果，即使有也是很少的副产物脱离该炭基质，在整个净化周期中地下水质量都得到保护。此外，该载体催化剂将中间体副产物降解成无毒副产物如乙烷、乙烯和乙炔。
生产该载体催化剂包括用金属铁浸渍吸附剂如活性炭。这些催化剂可采用本领域技术人员熟知的许多方法制备。生产本发明的载体催化剂的方法之一包括将该吸附剂与计算量的水合铁盐如硝酸铁混合，同时加热熔融该水合铁盐。铁可以为二价铁盐或三价铁盐。干燥并热解该混合物以使铁盐分解成氧化铁，形成包含浸渍有氧化铁形式的吸附剂的中间产物。接着将该中间产物置于还原条件下，使氧化铁还原成元素铁，由此产生浸渍有元素铁的吸附剂。
制备该载体催化剂的第二种方法包括通过加入碳酸氢钠稀溶液而将针铁矿(氢氧化铁)从铁盐(如硫酸亚铁)溶液中缓慢沉淀出来。沉淀在吸附剂如活性炭的悬浮液中在剧烈混合下进行。形成的中间产物包含浸渍有氧化铁形式的吸附剂。接着洗涤并干燥该中间产物，最后将其还原以使氧化铁转化成元素铁，由此生产浸渍有元素铁的吸附剂。
除了沉积在载体吸附剂基质孔内的铁之外，或者代替之，本发明的载体催化剂还可以包含另一种反应剂。因此，本发明的其它载体催化剂包含浸渍有铁和/或其它金属的吸附剂，所述其它金属包括，但不限于，铝、镁、铂、钯、镍、锌、铜、钴、铬、钼和锰。
例如，浸渍有铝的炭非常有效地吸附并降解二氯甲烷。在一个实施方案中，通过将载体催化剂的pH提高到碱性pH，如通过向该载体催化剂中加入小百分比的氢氧化镁，可增强浸渍有铝的炭的有效性。
本发明的载体催化剂可应用于受多种可与水混溶的或可溶于水的卤代有机化合物污染的水的处理。氯化溶剂是蓄水层和其它地表下含水环境中特别常见的污染物。可被有效处理的污染物包括卤化溶剂，例如，但不限于，(TCE)、二氯乙烯(DCE)、四氯乙烯、二氯乙烷、三氯乙烷、全氯乙烯(PCE)、氯乙烯(VC)、氯乙烷、四氯化碳、氯仿、二氯甲烷和氯甲烷。可被有效处理的其它类污染物包括溴代甲烷、溴代乙烷、溴代乙烯、氟氯甲烷、氟氯乙烷、氟氯乙烯、多氯联苯(PCBs)和农药。
本发明进一步提供修复受卤代烃污染的场所的方法，它包括向该污染的场所的一个或多个位置中注入本发明的载体催化剂。可用本发明的载体催化剂处理的污染的环境的说明性实施例包括，但不限于，土壤、沉积物、沙地、砂砾、地下水、蓄水层物质和垃圾填埋场。例如，在一个实施方案中，可在蓄水层内多个场所注入该载体催化剂，如实施例3中所述。在此实施方案中，施用方法可使该载体催化剂在污染物卷流中充分均匀分布，与常规方法产生的屏障或填充沟渠相反。因此，根据实施例3中描述的实施方案采用载体催化剂的修复方法不依赖于地下水扩散以进行有效处理。相反，该载体催化剂的吸附剂成分将污染物浓缩在具有高表面积的铁的吸附剂基质内，由此提高污染物降解速率。该场所的污染的地下水接着与载体催化剂接触，由此实现卤代烃化合物的还原脱卤。
本发明的载体催化剂提供优于常规修复产品和方法的许多优点。例如它快速降低地下水中污染物的浓度，因此可以在短时间内接近或达到规定标准(例如在几天或几周内，而用常规方法需要几个月或几年)。另外，该载体催化剂无毒，不随时间而分解，并且不释放有毒降解副产物，因此在整个处理过程中地下水质量都得到保护。该载体催化剂能够处理多种氯代化学物质，并且对所有类型的土壤和地下水条件都有效。它长时间保持活性，因此一般只需要一次处理。材料易于使用，并且不需要任何特殊的安全控制或安装设备。
本发明进一步提供用于原位生物修复受烃污染的环境的生物修复组合物。受燃料烃污染的大部分场所天然处于无氧状态。本发明的生物修复组合物利用此条件，并被设计成通过硫酸盐还原机理促进烃的无氧氧化。另外，本发明的生物修复组合物包含对烃污染物具有亲合力的吸附剂，由此提供浓缩该污染物并提高生物修复速率的方法。
因此，用于原位生物修复受烃污染的环境的本发明的生物修复组合物包含能够吸附烃的吸附剂，两种或多种能在硫酸盐还原条件下代谢所述烃的兼性厌氧菌种混合物，在一段时间内释放硫酸根离子的含硫酸根化合物，以及所述兼性厌氧菌代谢的营养系统，其中所述营养混合物包含硫化物清除剂。
本发明的生物修复组合物的说明性实例包含表1中列出成分的混合物。
表1
| 成份 | 含量(重量％) |
| 吸附剂 | 51.3-77 |
| 微量元素养分 | 3.8-10.2 |
| 含硫酸根化合物 | 19.2-38.5 |
| 兼性厌氧菌混合物 | 1×108CFU/gm炭 |
该吸附剂提供在污染场所浓缩该兼性厌氧菌混合物的方法。另外，该吸附剂提供吸附并因此浓缩该烃污染物的有效基质。结果，生物修复速率相对于使用常规方法获得的速率而言得到大大提高。在一个实施方案中，该吸附剂是对烃具有高亲合力的活性炭。另外，活性炭对兼性厌氧菌具有亲合力，这有利于期望厌氧菌生长的场所的原位生物修复。
兼性厌氧菌混合物包含在硫酸盐还原条件下代谢该烃污染物的烃降解体。兼性厌氧菌是诸如细菌和真菌的能在有氧和无氧代谢类型间切换的微生物。在无氧条件下，它们通过发酵或无氧呼吸生长。此外，由于氧对兼性厌氧菌无毒，用于本发明的组合物中的兼性厌氧菌对污染的场所常存在的低水平氧并不敏感。在一个实施方案中，兼性厌氧菌混合物包含相互合作的共生兼性厌氧菌。也就是说，一种类型的兼性厌氧菌将烃污染物分解成第一中间体，而另一种类型的兼性厌氧菌将把第一中间体分解成第二中间体或最终副产物等。
在一个实施方案中，兼性厌氧菌混合物至少包含一种为硫酸盐还原细菌的厌氧菌。一般而言，硫酸盐还原细菌广泛分布在缺氧条件为主的自然界中。例如，已在污水、污染的水、湖泊和海洋沉积物、海洋泥浆、油井等中发现这种细菌。在一个实施方案中，本发明的组合物被设计成通过向污染的环境中引入培养的细菌而显著增加天然存在的硫酸盐还原细菌的活性。将该吸附剂的水悬浮液与包含为降解烃而特别培养的细菌的兼性厌氧菌混合物混合，而不依靠本地细菌占据注入的吸附剂。将此混合物在注入污染的场所之前搅拌片刻，以确保所有微量元素养分都已溶解，以提供均匀混合物。另外，该预混合使培养的细菌比本地细菌更有优势，使培养的细菌占主导地位的机会最大。通过不依赖于本地细菌来分解烃污染物，本发明的组合物提供在短得多的时间内去除烃污染物的方法。
兼性厌氧菌的商品培养混合物变化很大，加入量取决于来源和它是否是干的矿物基产品，或者它是否是液体浓缩物。不管其来源，加入足量兼性厌氧菌混合物，以使目标悬浮液浓度达到每毫升五百万至一千万CFU(菌落形成单位)。
一般而言，培养的细菌包含多种细菌种或菌株。细菌种或菌株有利地来自假单胞菌属(Pseudomonas)、苯基菌属(Phenylobacterium)、寡养单胞菌属(Stenotrophomonas)、葡糖杆菌属(Gluconobacter)、土壤杆菌属(Agrobacterium)、弧菌属(Vibrio)、不动杆菌属(Acinetobacter)或微球菌属(Micrococcus)，也可采用酵母或其它菌属。细菌菌株的实例包括类产碱假单胞菌(Pseudomonas pseudoalkaligenes)、不动苯基杆菌(Phenylobacterium immobile)、嗜麦芽糖寡养单胞菌(Stenotrophomonasmaltophilia)、蜡状葡糖杆菌(Gluconobacter cerinus)、放射形土壤杆菌(Agrobacterium radiobacter)或产碱假单胞菌(Pseudomonas alcaligenes)。
如上讨论，本发明的生物修复组合物在硫酸盐还原条件下代谢烃污染物，其中在该过程中一些或所有兼性厌氧菌将硫酸盐还原成硫化氢并代谢(氧化)至少一些烃污染物。因此，在硫酸盐还原条件下的烃分解需要硫酸根离子源。所以，本发明的生物修复组合物包含含硫酸根化合物。该含硫酸根化合物优选具有低水溶性并且无毒。合适的含硫酸根化合物的代表性实例为无毒、在土壤中天然存在的化合物石膏(硫酸钙)。由于石膏具有低水溶性，它随时间而分解，缓慢释放硫酸根离子，因此在使用本发明的组合物进行生物修复期间可维持低但稳定的硫酸根水平。以此方式，石膏用作“定时释放的”硫酸根离子源，这是有利的，因为兼性厌氧菌混合物在一段时间内消耗烃污染物。只要有溶解的硫酸根的足够供应，兼性厌氧菌的活性就将得到优化。因此，任何以与石膏相似的方式释放硫酸根离子的无毒含硫酸根化合物都适用于本发明的目的。如本文所用，“无毒”指如美国环保局规定和由职业健康和安全部门定义的饮用水标准。
将支持培养的兼性厌氧菌生长所需的低水平微量元素养分与该生物修复组合物的其它成分混合。兼性厌氧菌的适当营养系统包括氮源如铵盐，和磷源如碱金属磷酸盐化合物。微量元素养分源优选不含沙地、砂砾、填料或商品肥料中存在的其它不溶产物。用于本发明目的的适当微量元素养分源的一个实例含有氮(例如24重量％的氨和硝酸铵，二者比例为约2∶1)、磷(例如10重量％的磷酸铵)、钾(例如2重量％的氯化钾)、硫(例如5重量％的硫酸铵)和铁(例如2重量％的硫酸亚铁)。该营养系统还包含硫化物清除剂。在一个实施方案中，该硫化物清除剂是亚铁盐如硫酸铁。
该生物修复组合物在注入污染的土壤或地下水中之后快速降低土壤和/或地下水中的烃污染物浓度。烃污染物分子被该组合物吸附，并因此与培养的兼性厌氧菌一起位于吸附剂基质的孔中。吸附剂基质内烃污染物浓度因此充分高于土壤或地下水中存在的水平。结果，降解速率显著快于通常采用现有技术观察到的速率。由于吸附的污染物被降解，活性位点又可用于吸附新的污染物，循环往复直到微生物用完食物(即烃)。
硫酸盐还原的副产物包括二氧化碳、水、多种发酵产物如短链醇(乙醇、丙醇、异丙醇、丁醇等)和硫化氢。在典型装置中，并不出现高浓度的硫化氢，因为硫化物清除剂(例如硫酸铁)作为一种微量元素养分掺入。例如，铁盐可以清除硫化氢并形成不溶性硫化铁，从而防止有毒水平的硫化氢蓄积。因此，硫化氢的瞬时浓度很好地维持在规定阈值以下，保护地下水质量。
本发明的组合物中包含的兼性厌氧菌混合物能够生物降解各种脂族烃、芳香烃和多环芳烃、多环烃。例如，该组合物可以用于生物降解汽油中存在的芳香烃如苯、甲苯、乙苯和二甲苯。可以使用本发明的生物修复组合物生物降解的多环芳烃的实例一般而言包括含多环结构的各种芳香化合物。一些极毒(致癌)的芳香烃(多环芳烃)相当抗生物降解，需要长时间吸收，但是它们紧紧地被活性炭吸附。多环芳烃一般存在于并且来自矿物燃料，特别是煤和石油。煤焦油沥青、石油和煤焦油石脑油，和各种其它高沸点石油馏分，以及来自其的各种产品，包括屋顶沥青、密封剂、筑路焦油、沥青、管道涂料、防水材料、染料、农药、油漆添加剂和木材防腐剂中存在相对高浓度的多环芳烃。一次大量溢出这种含有高浓度多环芳烃的物质可引起严重污染，需要快速修复措施。另外，各种燃料，如煤油和汽油，或其它含有低浓度多环芳烃的物质具有累积效应。本发明的潜在应用包括煤气厂场所、炼焦炉场所、炼油厂、煤矿仓库、加油站和其它工业场所的土壤生物修复。
如所描述，在本发明的生物组合物的制备中，在注入污染环境前，将兼性厌氧菌和吸附剂与水短时间混合，然后使该兼性厌氧菌占据吸附剂基质的孔。结果，“吸附剂微环境(adsorbent microcosm)”预先被大量为燃料烃快速吸收特制的兼性厌氧菌占据，使这种厌氧菌在“硫酸盐还原”小环境中比本土微生物占主导地位的机会最大。
本发明进一步提供用于生物修复受烃污染的场所的方法，它包括向该污染的场所的一个或多个位置中注入本发明的生物修复组合物。可用本发明的生物修复组合物处理的污染的环境的说明性实例包括，但不限于，土壤、沉积物、沙地、砂砾、地下水、蓄水层物质和垃圾填埋场。例如，在一个实施方案中，可以将该生物修复组合物注入蓄水层内的多个部位，如实施例3中所述。根据实施例3描述的方法，在整个污染物卷流中施以多处注入的方法提供该生物修复组合物的充分均匀分布。因此，实施例3中描述的方法不依赖于地下水移动来有效去除污染物，而是该生物修复组合物吸附并分解整个卷流中的污染物。结果，本发明的方法能够在几周或几个月内修复污染的土壤，而不是如采用反应层的常规方法那样需要多年来充分彻底修复。
本发明的生物修复组合物与常规生物修复方法和组合物相比具有几个优点。例如，与现有技术相比，可很快接近规定净化标准。所需时间取决于土壤类型，淤泥/粘土需要较长时间。在高传导性土壤(沙土或砂砾土壤)中，污染物浓度在几天内可实现99％的降低。
该生物修复组合物的另一个优点是污染物充分降解成无毒产物如二氧化碳、水和甲烷。此外，该生物修复产物无毒。因此，不产生有毒副产物，作为安置组合物结果的对地下水的影响是偶发的，在处理期间的任何时间一般都不超过饮用水或地下水标准。土壤和地下水污染可同时进行处理，采用工业中常见的设备易于安置该组合物。实施例1：通过低温分解金属硝酸盐而制备载体催化剂
将定量活性炭和定量水合硝酸铁混合，所述量是计算以在最终产物中提供所需重量百分比的元素铁的量。铁盐一般是潮湿的，且加热易于熔融，因此产生均匀混合物。在搅拌下，将混合物加热到约50℃，使盐熔融。如果需要，可以加入少量水以使该混合物产生具有奶油稠度的该混合物。接着在90-110℃的温度下干燥该混合物，以使该混合物可被压碎成自由流动的粒状粉末。在这一过程中发生一些硝酸盐的分解。
接着将干燥的粉末装入炉中，并按温度程序加热，同时一直保持还原条件。首先将温度缓慢升到150-200℃，以彻底干燥催化剂，并继续降解硝酸铁。继续升温到300℃，硝酸盐彻底分解成氧化物。
一旦硝酸盐彻底降解成氧化物，向炉气氛中通入还原气体如甲烷气或氢气，温度接着升高到550-800℃，彻底将氧化物还原成元素铁。甲烷气比氢气使用安全，因此优选甲烷。温度升到400-450℃时氧化物彻底还原时通常形成理论量的水。
催化剂的最后性质受最后的还原温度的影响。例如，当催化剂在低于700℃的温度下还原，并接着在冷却后暴露于空气时，可能发生放热反应，氧化部分还原的铁。然而，当最后的还原在高温，例如约700-800℃下进行时，催化剂稳定，暴露于空气没有影响。如果还原在低于450℃的温度下完成，该材料可能是自燃性的。在约450-700℃的还原温度下可获得各种催化剂活性。实施例2：通过沉淀过程制备包含浸渍有元素铁的活性炭的载体催化剂
适量水合硫酸铁在搅拌下于罐中溶解在去离子水中，加入定量的活性炭。加完后继续搅拌，向罐施加真空使炭脱气。一旦炭脱气后，缓慢加入足量碳酸氢钠稀溶液引发针铁矿和其它铁氧化物在悬浮的炭上沉淀。在加入碳酸氢盐期间给罐加压可以促进浸渍过程。加完碳酸氢盐后，继续再混合几小时。当测试等分试样亚铁离子是阴性时结束该过程。接着用去离子水洗涤浆液并过滤几次。最后，在110℃下干燥收集的催化剂。这时，炭中浸渍氧化铁并可以用于还原。
向炉中装入干燥的粉末并根据温度程序加热，同时一直保持还原条件。首先将温度缓慢升到150-200℃，以彻底干燥催化剂，并继续降解硝酸铁。继续升温到300℃，硝酸盐彻底分解成氧化物。
一旦硝酸盐彻底降解成氧化物，向炉气氛中通入还原气体如甲烷气或氢气，温度升高到550-800℃，彻底将氧化物还原成元素铁。甲烷气比氢气安全，因此优选甲烷。温度升到400-450℃时氧化物彻底还原时通常形成理论量的水。
实施例3：本发明的组合物的应用
将小直径(例如，直径约为0.75-2英寸)注射棒插入目标深度(例如5-150英尺)。深度取决于钻孔机的功率和土壤硬度。液压传动直推式钻孔机用于打击/推注射棒至所需深度，接着抽回约6英寸，以在注射点下方打开小空隙。在加压下沿着该棒注入本发明的载体催化剂或生物修复组合物的预混合水悬浮液。地岩层中压力增加，浆液开始流入地层。没有尝试控制液流途径，但是目标是在地岩层内实现充分均匀的悬浮液分布。悬浮液趋于从注射点向所有方向溢出，影响的平均或有效半径通过抽吸入棒的液体量控制。
注入第一批悬浮液后，可制备第二批(新鲜的)悬浮液，安置新的注射棒，并重复该过程。在整个卷流中持续进行这种方式的处理，随着处理进程的发展，地下水中污染物浓度下降。如果能够观察地层的横截面，则处理方案用于产生物质的三维网络，随机分散，在整个处理的地岩层中相当均匀。
许多处理技术，例如ZVI，只有当安置在地下水(饱和的土壤)中时才能很好地起的作用，但对处理渗流地区(不饱和的)土壤无效。由于活性炭从蒸汽中极有效地吸附有机化合物，当安置在渗流区时，本发明的组合物性能同样很好。结果，产品能同样很好地用于处理污染的土壤和地下水。
前面的描述只说明本发明的原理。用于本说明书和所附权利要求中的词语“包含”， “含有”， “包括”等用于说明存在一个或多个所述的特征、整数、成分或步骤，但它们不排除一个或多个其它特征、整数、成分、步骤或它们的组的存在。此外，由于对本领域技术人员而言，许多修饰和改变将使清楚的，所以不期望将本发明限于上面描述的确切结构和方法。因此，所有可以采取的适当修饰和等同手段都如权利要求定义的本发明的范围内。
Claims (28)
1.用于原位修复受卤代烃污染的土壤、地下水以及土壤和地下水的混合物的载体催化剂，它基本上由浸渍有零价铁的吸附剂组成，其中该吸附剂能够吸附该卤代烃。
2.权利要求1的载体催化剂，其中所述吸附剂是活性炭。
3.权利要求2的载体催化剂，其中所述活性炭具有约800-1800m2/gm的表面积。
4.权利要求1的载体催化剂，其中所述卤代烃选自卤代脂族烃、卤代芳香烃和卤代多环烃。
5.权利要求1的载体催化剂，其中所述铁是铁粉、铁屑或铁碎片。
6.权利要求1的载体催化剂，其中所述铁的暴露表面积为约50至400m2/gm。
7.权利要求1的载体催化剂，其中所述载体催化剂包含约1-20重量％的所述铁。
8.权利要求7的载体催化剂，其中所述载体催化剂包含约15-20重量％的所述铁。
9.用于原位修复受卤代烃污染的土壤、地下水以及土壤和地下水的混合物的载体催化剂，它基本上由(i)浸渍有零价铁的吸附剂和(ii)足以使催化剂的pH大于7的量的金属氢氧化物组成，其中该活性炭能够吸附该卤代烃。
10.权利要求9的载体催化剂，其中该吸附剂是活性炭。
11.权利要求1的载体催化剂，其中所述吸附剂是活性炭，其由包括以下步骤的方法制备：
(a)将所述活性炭与水合铁盐混合；
(b)加热所述混合物，使所述水合铁盐熔融，由此形成均匀混合物；
(c)在足以将所述铁盐还原成氧化铁的温度下热解所述均匀混合物，由此提供浸渍有所述氧化铁的所述活性炭；和
(d)将所述浸渍有氧化铁的活性炭置于还原条件下，将所述铁还原成零价铁。
12.权利要求11的载体催化剂，其中所述水合铁盐是硝酸铁。
13.权利要求11的载体催化剂，其中所述热解条件包括将所述混合物加热到约150-300℃的温度。
14.权利要求11的载体催化剂，其中所述还原条件包括将所述浸渍有氧化铁的炭加热到约450-800℃的温度。
15.权利要求1的载体催化剂，其由包括以下步骤的方法制备：
(a)将已知量的水合铁盐溶解在去离子水中；
(b)在此溶液中悬浮已知量的活性炭；
(c)通过施加真空将悬浮液脱气；
(d)在一段时间内向来自步骤(c)的所述悬浮液中加入碳酸氢钠稀溶液，引发氧化铁沉淀到所述悬浮的炭上，提供所述浸渍有氧化铁的炭；
(e)收集所述浸渍有氧化铁的炭；和
(f)将所述浸渍有氧化铁的活性炭置于还原条件下，将所述铁还原成零价铁。
16.用于原位生物修复受烃污染的土壤、地下水以及土壤和地下水的混合物的组合物，其包含能够吸附烃的吸附剂、能在硫酸盐还原条件下代谢所述烃的兼性厌氧菌混合物、在一段时间内释放硫酸根的含硫酸根化合物，以及促进所述厌氧菌生长的营养系统，其中所述营养系统包含硫化物清除剂。
17.权利要求16的组合物，其中所述吸附剂包含活性炭。
18.权利要求16的组合物，其中所述含硫酸根化合物是硫酸钙。
19.权利要求16的组合物，其中所述兼性厌氧菌是共生的。
20.权利要求16的组合物，其中所述营养系统包括氮源和磷源。
21.权利要求16的组合物，其中所述氮源是铵盐，而所述磷源是碱金属磷酸盐化合物。
22.权利要求16的组合物，其中所述氮源是摩尔比为约2∶1的氨和硝酸铵。
23.权利要求16的组合物，其中所述硫化物清除剂是硫酸铁。
24.权利要求16的组合物，其中所述烃选自脂族烃、芳香烃和多环烃。
25.用于原位修复受卤代烃污染的土壤、地下水以及土壤和地下水的混合物的方法，其包括向污染的土壤中引入载体催化剂的水悬浮液，所述载体催化剂包含能够吸附卤代烃且浸渍有零价铁的吸附剂。
26.权利要求25的方法，其中所述引入包括：
(a)在污染的土壤中插入小直径注射棒，插入深度为约5-150英尺；
(b)部分抽回所述棒，在注射点下方打开空隙；
(c)沿着所述棒在压力下注射所述水悬浮液，直到所述空隙中的压力增加到所述悬浮液从所述空隙中流出的点；和
(d)在所有所述污染的土壤中重复步骤(a)至(c)，直到所有所述污染的土壤中充分均匀分布所述水悬浮液。
27.用于原位生物修复受烃污染的土壤、地下水以及土壤和地下水的混合物的方法，它包括向该污染的土壤中引入一种组合物的水悬浮液，所述组合物包含能够吸附所述烃的吸附剂、在硫酸盐还原条件下能代谢所述烃的兼性厌氧菌混合物、在一段时间内释放硫酸根的含硫酸根化合物，以及促进所述厌氧菌生长的营养系统，其中所述营养系统包含硫化物清除剂。
28.权利要求27的方法，其中所述引入包括：
(a)在污染的土壤中插入小直径注射棒，插入深度为约5-150英尺；
(b)部分抽回所述棒，在注射点下方打开空隙；
(c)沿着所述棒在压力下注射所述水悬浮液，直到所述空隙中的压力增加到所述悬浮液从所述空隙中流出的点；
(d)在所有所述污染的土壤中重复步骤(a)至(c)，直到所有所述污染的土壤中充分均匀分布所述水悬浮液。
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- 2003-06-30 FI FIEP03764339.2T patent/FI1521723T4/fi active
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| CN103635265A (zh) * | 2011-05-16 | 2014-03-12 | 雪佛龙美国公司 | 使用电子受体盐原位生物修复污染的地下水 |
| CN103635265B (zh) * | 2011-05-16 | 2016-06-22 | 雪佛龙美国公司 | 使用电子受体盐原位生物修复污染的地下水 |
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| US6787034B2 (en) | 2004-09-07 |
| MXPA05000466A (es) | 2005-08-16 |
| CA2790114A1 (en) | 2004-01-22 |
| EP1521723B1 (en) | 2019-08-21 |
| US20040007524A1 (en) | 2004-01-15 |
| DK1521723T3 (da) | 2019-11-18 |
| ES2754812T5 (es) | 2023-01-30 |
| CA2790114C (en) | 2014-07-29 |
| CA2492116C (en) | 2012-11-27 |
| EP1521723B2 (en) | 2022-11-02 |
| DK1521723T4 (da) | 2022-12-12 |
| EP1521723A4 (en) | 2009-05-20 |
| EP2390234A1 (en) | 2011-11-30 |
| CN1668535A (zh) | 2005-09-14 |
| FI1521723T4 (fi) | 2023-02-28 |
| DK2390234T3 (da) | 2013-07-01 |
| ES2417010T3 (es) | 2013-08-05 |
| AU2003256353A1 (en) | 2004-02-02 |
| EP2390234B1 (en) | 2013-03-27 |
| WO2004007379A1 (en) | 2004-01-22 |
| ES2754812T3 (es) | 2020-04-20 |
| CA2492116A1 (en) | 2004-01-22 |
| EP1521723A1 (en) | 2005-04-13 |
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