CN1146163A - 污染物质的处理方法 - Google Patents
污染物质的处理方法 Download PDFInfo
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Abstract
一种净化介质的方法,所述的介质包括被一种或多种金属种类污染的颗粒物质,本方法包括的步骤有:用微生物产生的硫酸处理所述的介质体,以使这些金属种类溶解为金属硫酸盐;用生物沉淀过程处理浸出的金属硫酸盐,该过程将所述的硫酸盐转化为不溶的硫化物;从不溶的金属硫化物中分离在生物沉淀期间产生的硫化氢;以及氧化分离出来的硫化氢以生成可再使用的含硫组分源。
Description
本发明涉及污染物质处理方法,特别涉及用生物化学方法从大量颗粒物质,诸如土地或土壤中去除金属,特别是重金属,污染物的方法。
在世界范围内,由于工业、废物处置以及其他活动的结果,大量土地已被金属污染。这些污染物的实例包括:汞、镉、钡、铬、锰和铅,放射性核素,例如锕系元素和裂变产物。这些污染物严重威胁地下水,并由此而严重威胁饮用水供给,以及在许多情况下限制或阻碍土地的再使用。此外,由于美国的现代立法和欧洲共同体范围内以及其他地方的大体类似的立法的结果,废物产生者们如果对于他们的废物没有负责任地行动的话,他们将要承担日益增加的法律责任和为再生与净化付出代价。因此,对于能帮助解决由于土地污染而引起的问题的技术有日益增长的需要。
迄今,已发展了若干技术以改良被污染土地。实例包括:土壤稳定、电迁移、玻璃化、挥发、焚烧、土壤洗涤、泵与处理***、土地耕种、污泥相生物改良等。许多这些已知技术具有一系列局限性,包括:
a)缺少对此问题的永久解决,例如转换此种物质为有毒的土地填埋,
或夹带在寿命有限的基体内;
b)不适宜处理宽范围污染物,例如金属污染的土地,就目前采用的
生物方法来说;
c)产生大体积的或难以管理的二次废物,例如土壤稳定和焚烧;
d)缺少就地或非就地操作的选择性以适宜于特定场所,例如在焚烧和
土壤洗涤时的情况;
e)高成本,例如焚烧、玻璃化和泵与处理***;
f)再使用污染物的有限能力,例如土壤稳定***应用于金属时。
本发明试图通过使生物***能够改善金属污染的土地非各别地解决这些问题。
根据本发明,提供了一种净化介质的方法,该介质包含有被一种或多种金属种类污染的颗粒物质,本方法包括以下步骤:用微生物产生的硫酸处理所述的介质体,以使这些金属种类溶解并以金属硫酸盐的形式浸化为不溶的硫化物;从不溶的金属硫化物中分离在生物沉淀期间产生的硫化氢;以及氧化分离出来的硫化氢以生成可再使用的含硫组分源。进行去除污染的介质可包括颗粒物质,例如土壤、岩石细粒、挖出的淤泥、沉积物、污泥、生产过程的残渣、热解过程的炉渣、加热炉粉尘及类似物。这些污染物可能包含在颗粒物质的表面或者被结合在其颗粒的内部。
在所述的介质中可能存在有一系列金属种类,这些金属种类可转化为各种金属硫酸盐和接着被生物沉淀为各种金属硫化物。此文所用的“金属种类”(“metal species”)这一术语包括金属、合金、金属盐、准金属以及含金属的化合物与配合物。
所述的金属种类污染物可包括:
i)锕系元素或它们的放射性衰变产物或其化合物;
ii)裂变产物;
iii)重金属或它们的化合物。
锕系元素是原子序数在89至104范围内的元素。
此处所用的术语“裂变产物”是指作为核燃料裂变时直接产物(或通常所说的“裂变碎片”)而形成的元素以及由这些直接产物经β衰变或内跃迁而形成的产物。裂变产物包括从硒至铈范围内的元素。
要求用本发明方法分离的非放射性重金属包括有毒金属如镍、锌、镉、铜和钴以及其它常见污染物。这些物质通常在使用含有这些元素的化学品的工厂附近以及在废物处置场地作为泥土污染物或在水的沉降物中被找到。在本发明方法中分离的这些金属污染物可以包括放射性的与非放射性的金属污染物的混合物。
如以下描述,本发明的方法可以扩展包括被处理介质中的有机污染物也被除去或被解毒的步骤。
所述的颗粒物质最理想的处理是用加入水溶液以生物产生的硫酸浸出。
当被清除污染的介质包括土壤或土地时,土壤或土地可就地或非就地处理。对于后者来说,土壤可先预处理,例如除去或压碎大块物如砾石、石块和类似物。含有生物产生的硫酸水溶液和/或可生物转化为硫酸的含硫物质源的适当混合物可被注入土壤或与土壤混合。其他组分如富氮或富磷物质以及空气可选择性地加入。形成硫酸的生物转化可由存在于土壤中的微生物媒体以已知方式实现。含硫物质可包括单质硫或者硫的其他还原形式。
当土壤或其他颗粒物质,例如生产过程的残渣或炉渣,进行非就地处理时,其处理可在一个或多个适宜的已知生物反应器中进行。可以加入前面提到的组分以促进酸的产生。
当产生硫酸根离子的生物转化是在被处理的土壤中进行时,此生物转化可由自然发生的硫氧化微生物的作用而引起,硫氧化微生物包括:Thiobacillus ferooxidans(氧化铁硫杆菌),Thiobacillus thiooxidans(氧化硫硫杆菌)和Thiobacillus neapolitanus(那不勒斯硫杆菌)。这些微生物存在例如像联合体(consortium)一样。这些微生物通过硫还原形式的被氧化获得它们生长所必需的能量,由此而产生硫酸盐和硫酸,或者通过氧化二价铁为三价铁获得能量。如果土壤缺少合适的微生物或者所述的颗粒物质在分开的生物反应器中处理时,这些微生物可以作为从相似土壤环境中得到的混合联合体而被加入。
除上述酸浸出外,金属释出还可通过以下的一个或多个作用过程而发生:
a)金属硫化物的直接化学浸蚀;
b)电化学过程(原电池转化(Galvanic conversion)),此过程产生于浸在
适当电解质,如硫酸,中的两种不同的金属种类之间的接触;或
c)硫酸铁的氧化作用。
作为另一种可选择方法,在实施本发明方法中浸出步骤所需要的硫酸可在分开的生物反应器中化学地或生物化学地产生,以及在产生之后被加到土壤或其它颗粒物质中。
在过程开始工作期间,可以使用单质硫或硫酸(通过就地生物产生酸)作为浸出的酸来源。此后,单质硫,或单质硫与硫酸的结合将是主要的硫来源。可加入单质硫或硫酸以补充从***中以金属硫化物形式损失的有用硫。
可使浸出溶液从所述的颗粒物体中渗过和排出,和被收集起来。
如此收集起来的浸出溶液之后可以或者再循环通过该颗粒物质,或者用泵输送至反应器以进行本方法的生物沉淀步骤。
在本发明方法中应用的生物沉淀步骤可能与已知的硫酸盐还原方法相似。这些方法在现有技术中已经使用,例如,处理硫酸盐和重金属两相似。这些方法在现有技术中已经使用,例如,处理硫酸盐和重金属两者,从废水中或者除去其中之一或者两者一起除去。例如,在EP426254A中描述的方法就是适用的,此方法使用乙醇作为基质和使用产甲烷生物,用两者转化绝氧产生的醋酸盐为甲烷。此外,这种过程在许多绝氧环境中可以自然发生。
本发明的生物沉淀过程可使用非模拟(disimulatory)的硫酸盐还原细菌(SRBs)的自然发生的联合体,以转化含水金属硫酸盐为金属硫化物。造成这种转化的微生物包括:Desulfovibrio(脱硫弧菌属)和Desulfomonas(脱硫红曲霉菌属),这些微生物可以在地面上封闭的生物反应器***中生长。这些生物氧化简单的有机化物,例如乳酸和乙醇,以获得它们生长必需的能量。然而,有时也应用较复杂的碳源,例如酚的化合物,或应用生物浸出期间可能从土壤中浸出的有机物。由于这种氧化作用的结果,硫酸盐被还原为硫化物和水。因为许多重金属硫化物在水溶液中溶解度低,所以这些金属硫化物与一些生物一起在反应器内作为泥浆沉淀下来。这些金属硫化物通常作为泥浆被分离出来和有可能出售以回收金属,对于有毒的或有放射性的金属将在后续过程中进一步被固定。
由金属溶解相进入生物沉淀反应器的硫酸的还原将导致产生硫化氢和理所当然的减少硫酸的浓度。这将导致在生物沉淀反应器内维持pH接近中性,并由此维持对于SRB活性最佳的pH。此外,大体上中性的pH将使硫化氢保留在溶液中,从而可保持使SRB存活的足够低的氧化还原电位,即<-300mV。通常用此方法保持适当的氧化还原电位。虽然此方法以前已用于维持适宜的反应器pH(例如在EP436254A中),但以前从未用于缓冲低pH1.0的液流,这有可能从本文描述的酸浸出步骤遇到。
由于生物沉淀期间产生硫化氢和金属硫化物的结果,从生物沉淀过程可产生三种不同的产物流:
(a)含有被沉淀的金属硫化物与生物体的泥浆;
(b)硫化氢和可溶的金属硫化物以及某些生物组分共同在一起的水溶
液;
(c)气体硫化氢。
气体硫化氢可由安装在反应器顶部或接近顶部的排出装置抽出。硫化氢水溶液在其它可溶硫化物可从泥浆分离出来。
金属硫化物泥浆可借外力通过反应器的适当排出口取出。此泥浆可去脱水和再循环以回收金属,或可用适当的包封过程处理,例如生物增强的金属固定。
分离出的气体的和含水的硫化氢是可再利用的硫的有价值的来源,且可应用于下文描述的生物化学氧化过程。
根据本发明的方法,在金属浸出阶段初始操作期间,参加生物沉淀的浸出液将具有大体中性的pH。因此,这种液体一部分可用于溶解生物沉淀产生的硫化氢气体。
从生物沉淀过程引出的这两种硫化氢水溶液液流可单独地使用或合并一起,且可在封闭的生物反应器***中被氧化。此生物反应器***可含有自然发生的硫化物氧化微生物联合体。已知的氧化可溶硫化物的微生物实例包括:Thiobacillus thioparus(排硫硫杆菌)、T.neapolitanus(那不勒斯硫杆菌)、T.dentificans(脱氮硫杆菌)和Thiomicrospira。对于硫化物氧化可能有两个途径:
(a)直接氧化为硫酸和/或硫酸盐;
(b)氧化为单质硫,如果合适,而后还可将其加至,例如撒在,被污
染的土壤中以产生硫酸。
氧化为单质硫要求限氧环境,但是具有可提供无硫化物、pH中性溶液的优点,该溶液可用于溶解来自生物沉淀过程的硫化氢气体。直接氧化产生的硫酸溶液广泛适用于随后接触被污染土壤。
本发明的方法可扩展包括从所述的被污染介质中除去有机污染物的一个或多个步骤,而且这可连同除去金属过程应用于生物降解,如在申请人共同未决的UK Patent Application Nos.9402975.8和9414425.0中所述(该方法是与此同一日期的共同未决的PCT申请的研究主题)。
本发明进一步提供下列优于现有技术方法的优点:(1)对污染问题提供一种永久性解决方法;(3)允许同时处理金属污染物与有机污染物;(4)就地与非就地处理***均可适用,并可按需要选择;(6)可减少二次废物的流出量以及由此而降低了处理这些废物的成本;(2)减少了能危害环境的粗糙化学品的使用;(5)提供了再使用某些金属污染物的可能性。
现将通过实例和参考附图的方法对本发明的实施方案予以描述,其中:
图1是用体现本发明的方法就地进行改良处理的土地区域以及此方法中所用装备的断面示意图。
地下含水层3。土壤层1包括金属污染区4,此污染区是由于设置在层1地面中的废物贮存槽5的污染物的迁移造成的。区域4扩展到地下含水层3之内。监测井6向下伸出通过区域4以测量在区域4中的污染程度。污染区域4的深度和面积大小采用适当的已知的分析技术预先已经测定。地平线用数字18表示。
来自营养源22的营养素和酸可载带在合适的液体载体,如含气水,中施加于空贮存槽5的基底。这一操作由喷洒器7完成。此液体还可经适当安置的注入井8和通过渗流通道9施用,以便渗入污染区的物质中,和加速土壤的酸化。单质硫也可加入和混合进入浅层污染区,如贮存槽5的基底,以进一步促进如上所述的就地生物浸出过程。
为了在污染区域4的范围内能形成和保持有氧的条件,用鼓风机21连接一系列通风井10(已示出其中之一)吹入空气,或抽空气通过层1的污染区域4或吹空气进入含水层3的地下水中或两者均有之。此外,营养素的加入速度可以改变,以避免在污染区域4的范围内造成缺氧条件。供给以营养素和酸的层1和含水层3的羽状地带或区域由参考号数20标出。这羽状地带包括层1中的污染区域4和含水层3。
此处理过程以上述方式在区域4引起金属的酸浸出。此过程可持续数星期或数月以上,直至在污染区域4的土壤中达到基本没有污染金属,此间以适当分析方法时时进行测定。
金属浸出处理过程的产物被收集在含水层3的部分之内,此部分在x方向上或自然发生或人工造成,同时用合适的泵(未示出)通过一系列回收井11(已示出其中之一)将此产物接收和回送至层1的地面上。含水层3的水平面2可通过渗流通道24加进水来调节,以加速x方向的水流。
收集的溶液而后输送至下述的选择之一:
(a)缓冲罐12,为了在重新施加到污染区域之前充气和加入适当营养素,这是此方法操作初期的主要路线;
(b)生物沉淀反应器13;
(c)气液接触器14,以洗提来自生物沉淀过程的废气中的硫化氢。
液体从底部进入反应器13和向上流动通过反应器13。如此进行时,存在于反应器13中的硫酸盐还原微生物以上述方式将流入的硫酸盐转化为硫化物。
在反应器13中生物沉淀反应期间产生的废气通过与反应器13相通的气液接触器14。接触器14可使硫化氢回收。离开接触器14的气流通过二次涤气装置19和排放至大气中。
含有不溶硫化物的生物沉淀反应的泥浆收集在反应器13的底部,并通过管线15输送至分离处理过程,例如生物增强的金属固定,或脱水和收集与输送到另外地方以进行金属回收。泥浆脱水所得溶液或可返回生物浸出过程以重新使用,或可进一步处理和排出。
来自生物沉淀过程的含有溶解硫化物的流出液被抽出并与来自气/液接触器14的硫化物水溶液会合。会合后的硫化物水溶液之后用泵输送通过气/液接触器16和进入硫化物氧化反应器17。接触器16确保在反应器17中被酸释放出的任何硫化氢气能被流入的碱液再溶解。
在氧化反应器17内,含有硫化物的溶液与适当的微生物紧密混合并以前述方式氧化为硫酸盐。产生的酸液之后输送至缓冲罐或生物反应器12,在此如果需要可由硫源23进一步加入单质硫和由反应器17带来的微生物将其氧化为硫酸,之后以前述方式重新加至土壤层1的被污染物质中(通过井8和通道9以及喷洒器7)。
由以上可知,此去除金属的处理过程是循环的,在土壤层1的部分3中的金属污染物在去除金属过程的不同循环期间,逐渐地被含有生物产生硫酸的浸提液浸蚀出来,并且以在生物沉淀反应器13中形成的不溶硫化物形式被回收。部分硫通过在氧化反应器17中硫化物的氧化而回收,并且在土壤金属污染物酸浸出过程中重新使用。
Claims (10)
1、一种净化介质的方法,所述的介质包括被一种或多种金属种类污染的颗粒物质,本方法包括如下步骤:用微生物产生的硫酸处理所述的介质体,以使这些金属种类溶解为金属硫酸盐;用生物沉淀过程处理浸出的金属硫酸盐,该过程将所述的硫酸盐转化为不溶的硫化物;从不溶的金属硫化物中分离在生物沉淀期间产生的硫化氢;以及氧化分离出来的硫化氢以生成可再使用的含硫组分源。
2、权利要求1的方法,其中各种金属种类存在于所述的介质中和这些金属种类转化为各种金属硫酸盐以及其后生物沉淀为各种金属硫化物。
3、权利要求1或2的方法,其中所述的一种或多种金属包括放射性种类。
4、权利要求1至3的任一方法,其中被净化的介质包括颗粒物质,选自于:土壤、岩石细粒、挖出的淤泥、沉积物、污泥、生产过程的残渣、热解过程的炉渣和加热炉粉尘,所述的污染物可包含在所述的颗粒物质的表面或结合在其颗粒的内部。
5、前述任一权利要求的方法,其中所述的颗粒物质用浸提剂水溶液以生物产生的硫酸进行浸出处理。
6、权利要求5的方法,其中所述的硫酸是在包括所述颗粒物的物质中就地以生物产生的。
7、权利要求5的方法,其中所述的硫酸是在分开的生物反应器中产生的和被施加在包括所述的颗粒物的物质中。
8、权利要求5或6的方法,其中所述的方法应用于就地处理土壤或土地。
9、前述任一权利要求的方法,其中产生于生物沉淀过程的一种或多种不溶硫化物被提取和包封。
10、权利要求l的方法,其中所述的方法为循环操作,所述的可再使用的含硫组分源重新施用于该介质的净化,以保证在其中的金属进一步被硫酸浸出。
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1995
- 1995-02-13 JP JP7521648A patent/JPH09509096A/ja active Pending
- 1995-02-13 AU AU15873/95A patent/AU693512B2/en not_active Ceased
- 1995-02-13 US US08/693,069 patent/US5895832A/en not_active Expired - Lifetime
- 1995-02-13 EP EP95907784A patent/EP0788394B1/en not_active Expired - Lifetime
- 1995-02-13 AT AT95907784T patent/ATE192938T1/de not_active IP Right Cessation
- 1995-02-13 CA CA002183585A patent/CA2183585A1/en not_active Abandoned
- 1995-02-13 CZ CZ962418A patent/CZ241896A3/cs unknown
- 1995-02-13 DE DE69517045T patent/DE69517045D1/de not_active Expired - Lifetime
- 1995-02-13 CN CN95192576A patent/CN1146163A/zh active Pending
- 1995-02-13 WO PCT/GB1995/000285 patent/WO1995022374A1/en active IP Right Grant
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104245165A (zh) * | 2012-02-24 | 2014-12-24 | 格兰特·格克勒 | 用于环境修复和分解污染物的先进导热式加热器*** |
CN110026431A (zh) * | 2019-05-20 | 2019-07-19 | 成都科泰技术有限公司 | 一种利用微生物纳米材料原位修复镉污染土壤的方法 |
CN110026431B (zh) * | 2019-05-20 | 2020-12-22 | 成都科泰技术有限公司 | 一种利用微生物纳米材料原位修复镉污染土壤的方法 |
Also Published As
Publication number | Publication date |
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EP0788394B1 (en) | 2000-05-17 |
DE69517045D1 (de) | 2000-06-21 |
AU1587395A (en) | 1995-09-04 |
EP0788394A1 (en) | 1997-08-13 |
CA2183585A1 (en) | 1995-08-24 |
CZ241896A3 (en) | 1997-03-12 |
ATE192938T1 (de) | 2000-06-15 |
AU693512B2 (en) | 1998-07-02 |
US5895832A (en) | 1999-04-20 |
WO1995022374A1 (en) | 1995-08-24 |
MX9603459A (es) | 1997-12-31 |
JPH09509096A (ja) | 1997-09-16 |
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