CN1388764A - 用于除去石油储罐中淤浆所含烃类和/或用于处理含烃废料的等离子体方法以及适宜装 - Google Patents
用于除去石油储罐中淤浆所含烃类和/或用于处理含烃废料的等离子体方法以及适宜装 Download PDFInfo
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Abstract
本发明涉及一种等离子体方法以及适宜装置,其可有效地用来从不同物料如土壤、淤浆中除去有毒或有害有机化合物,诸如石油、原油、杀虫剂、除草剂以及各种烃类,所述化合物源自石油化学品泄露或不当丢弃/处理;所述方法以及适宜装置也可用来除去在石油储罐底部形成的淤浆中所含的烃类。与其他方法用来处理类似物料相比,本发明的目的等离子体方法,以及适宜装置具有以下优点:污染物除去低至土壤或淤浆的0.1%重量;连续操作;在需要时回收污染物的能力;工艺的能量效率高;以及非显著量的须处理气体。所述等离子体方法采用等离子体系统以向污染的土壤或淤浆提供足够的能量使烃类挥发,保持所述操作温度为400－900℃。离开等离子体反应器的所述挥发化合物被收集于冷凝器中,其中所述烃类可以液体烃(油)的形式被回收。所述污染物料由一端部连续地给入反应器,同时所述清洁物料由反应器的另一端部排出。在所述等离子体反应器中的气氛保持为中性或还原态,以防止烃类氧化。所述装置包括一给料系统、静态反应器、旋转反应器、用于传输反应器中废料的旋转螺杆、等离子体系统、排出挥发化合物的管子、设于等离子体反应器中的冷凝器、反应器上的清洁物料排出口以及收集所述清洁物料的储槽。
Description
发明背景
发明领域
本发明涉及一种等离子体方法以及适宜装置，其可有效地用于从石油储罐的底部形成的淤浆中除去所含的烃类，该淤浆含有原油和大量无机固体物料和水。该方法可用来处理污染的土壤和淤浆，除去有毒或有害有机化合物，诸如石油、原油、杀虫剂、除草剂以及各种烃类，所述化合物源自这些物料的泄露或不当丢弃/处理。
现有技术简介
石油或其他类型油类污染的土壤一般是突然泄露或管道维护的后果，并且通常可见于或接近石油化工厂以及炼油厂。通常能发现污染超过25％重量的石油或原油。此类石油或原油对环境极具威胁性，危害包括植物和人类在内的动物。在目录上可包括被其他有机化合物诸如杀虫剂和除草剂污染的土壤、淤浆以及类似物料，其中污染可达数十ppm(每百万份计)到较高百分数。在上述的所有污染中，其对环境极具危险性，有毒或有害有机化合物必须被从土壤或淤浆中除去并适当地处理。
另一个烃源是在石油储罐中形成的淤浆；其含有大量的无机固体物料以及水，并且在其排放至天然环境之前必须经适当处理。简明起见，上述不同类型的有机化合物、土壤污染物以及存在于不同淤浆中的那些都被称作烃类。
对于上述污染物料已有几种处理方法。最常用的包括焚烧和使用离心机。但是，如下示，两种都具有极大的局限性，本发明则提供了另一种优异且可行的方法。
焚烧是工程上常用的方法(参见《化学工程手册》R.H.Perry e C.H.Chilton编，McGraw-Hill Book Company，第5版，1973，第9-35到9-36)。特别地，用于处理含烃物料。所述含烃物料被给入具有耐火内衬的旋转炉中。使用气体或油燃烧器保持所述炉温为500-1000C；炉中必须具有空气，并且在此温度下空气中氧气使得烃类部分地或充分燃烧。在污染物料中所含的水挥发并与燃烧气体一起离开炉子。原则上，工艺的废料不含有机毒性或有害化合物，但焚烧工艺带来的问题在于：a)大量的废气需要处理(废气包括：工艺中给入的空气、有机毒性化合物燃烧产生的气体，来自燃烧器的气体和水蒸气)；b)能量效率低，由于油/气燃烧器中的大量热量与废气一起排出炉子；一般整个工艺的能量效率低于20％；c)由于烃类被焚烧，未能回收原始有机物料，这样带来极大损失。
采用离心机将液体与固体分离是常规的工程实践(参见《化学工程手册》R.H.Perry e C.H.Chilton编，McGraw-Hill Book Company，第5版，1973，第19-87到19-98)。采用离心机来处理烃类污染的土壤或淤浆(参见美国专利6149345-A，P E Atkins，“Remediation ofhydrocarbon-contaminated soil or groundwater by apparatus having acentrifugal separator，a vacuum source，a vent，a fractionator(FS)and a fillsensor，where the sepatrated liquid is fed to the FS Via a low-shearpump”)。在该例中，含有不同含量烃类和水的所述污染物料被给入旋转容器(称作离心机)中，其中离心力从污染的土壤或含在淤浆中的固体中将液体烃和水分离出来。理想地，该工艺将在回收此类有机液体后留下不含烃类和水的土壤或淤浆。离心机的缺点在于无法彻底除去烃类，处理后的土壤或淤浆一般仍将含有超过5％(重量)的有机污染物。
使用热等离子体是公认的方法，用于处理医疗垃圾、工业废物以及从铸造废物以及类似物中回收铝。在这方面，可参见R.N.Szente(AIPConference Proc.，n.345，pg.487，1995，)的论文。可采用电弧将普通气体加热至20,000℃而获得热等离子体。产生热等离子体的的装置为等离子体焰炬，其可为各种几何形状，诸如管状金属电极或替代的石墨电极。在任何情况下都是在电极间保持电弧来加热气体。在这些温度下，气体被部分离子化，并被称作等离子体，其与外部气体不同，并且当工艺需要高温或某一化学反应或材料改性需要离子化时使用等离子体。一般产生热等离子体的方法是使用直流电源，而不象在冶金电弧炉中那样使用交流电。确定的废料需要特定的等离子体系统和反应器。用于废料的等离子体方法需要约1500℃的温度，以将含在废料中无机化合物熔化，并且还氧化有机化合物，产生一氧化碳或二氧化碳以及水蒸气。
关于本发明，应当提及以下和铝废料的热等离子体处理有关的著作：G.Dube，J.P.Huni，W.Stevens，S.Lavoie，“Recovery of Non-FerrousMetals from Dross Using the Plasma Dross Process“，美国专利4,960,460，1990年10月2日，因为该方法在操作条件和热量传导机理方面与本发明类似。为了处理铝废料，物料被给入旋转反应器，关闭进门。在反应器中，等离子体焰炬或替代以直流电弧其间放电的石墨电极被用来保持控制气氛，并且同时提供工艺所需能量。等离子体焰炬或石墨电极一般设置于反应器的中心部位。该工艺基本上是在约700℃温度下非氧化气氛中从铝废料中熔出铝，以避免所回收金属的氧化。由于水在熔融铝中会被还原成氢气，会导致铝氧化甚至产生爆炸，因此铝废料中不含水。该工艺以间歇方式进行。一旦铝废料中铝被熔融，反应器被开启，液体金属被倒入模具中。其他化合物(主要是铝氧化物)从反应器中除去并装入另一批料。该工艺可有效地处理铝废料，但未能用于其他废料，因为它实质上为间歇工艺，不适用于废气，并且非常少的物料可在700℃熔融而实现所需的分离。
发明简述
本发明的目的是提供一种方法以及适宜装置，其可有效地用来处理有毒或有害化合物污染的土壤和/或淤浆，污染物诸如不同烃类、石油、原油和/或杀虫剂、除草剂以及类似有机化合物，或可用来除去在石油储罐底部形成的淤浆中所含的烃类；本发明的方法和适宜装置克服了以前工业设备的缺点。
更具体地，本发明的目的是提供一种等离子体方法以及适宜装置来处理烃类污染的土壤和/或淤浆，与用来处理类似物料的其他方法相比，本发明的技术特点带来以下优点：
a)污染物除去低至占土壤或淤浆的0.1％重量；
b)连续操作；
c)在需要时回收污染物的能力；
d)工艺的高能量效率；以及
e)少量或非显著量的须处理气体。
等离子体方法及适宜装置相对于其它方法的优点详述如下。
本发明人开发的等离子体方法采用的等离子体系统，其用来向污染土壤或淤浆提供足够的能量使烃类挥发。所采用的等离子体方法的正常操作温度为400-900℃，为了使须处理物料中的全部烃类挥发出来。当处理石油或原油污染的土壤/淤浆时，离开等离子体反应器的挥发化合物被收集于冷凝器中，于此所述烃类可以液体烃类(油)的形式得到回收。污染物料所含的任何水也在工艺过程中挥发出来并收集于冷凝器中。污染的土壤或淤浆将从一端部连续地给入反应器，同时无油土壤或废料由反应器的另一端部中除去。在等离子体反应器中的气氛保持为中性或还原态，以防止烃类氧化，并且它们在反应器中挥发以及在等离子体反应器外部冷凝后而进行回收。
相对于常规焚烧工艺，采用等离子体系统处理上述废料的主要优点在于：a)能量效率更高，由于等离子流比焚烧工艺中采用的油或气体燃烧器产生的火焰温度高得多(一般地，等离子流为15,000℃，而油或气体燃烧器为2,000℃)，而热传导取决于能量源和所加热的物质的温度，其在等离子体方法中明显要高一些，显著地增加了等离子体方法的能量效率。与油或气体燃烧器的20％相比，一般等离子体方法能量效率超过80％；b)当土壤或淤浆含有大于10％重量的烃类时，回收烃类污染物的能力对于工艺为其显著优点；c)须处理废气量较低，与在燃烧器中油或气体燃烧产生的气体相比，等离子体焰炬仅产生少量气体；而且等离子体方法的废气由挥发性有机化合物组成，极易于冷凝，从而产生少量的废气。与离心机工艺相比，采用等离子体系统处理上述废料的主要优点是其从土壤和淤浆中彻底除去污染物的能力，离心机工艺处理之后的烃类废料含量为5％(重量)。
在与现有的处理铝废料的等离子体方法相比，本发明的具有辅助装置的方法在处理污染的土壤或淤浆方面具有以下不同之处及优点：a)具有适宜装置的本发明方法可连续给入污染物料和排出清洁物料，这在铝废料工艺无法实现；b)在本发明工艺中，污染物被以气态连续地挥发并离开反应器，而在铝废料等离子体方法中，物料留在反应器中直到批量循环结束；c)在本发明的方法中，离开反应器的气体被冷凝以从污染物中回收烃类；d)在铝废料等离子体方法中产生少量的气体，在处理过程中其一般不从反应器中除去，也不被处理。
上述采用热等离子体工艺来处理烃类化合物污染的土壤或淤浆的方法所使用的装置的大致结构将结合附图进行描述，其中：
图1为本发明方法主要步骤的框图，包括以下部分：
A-在静态(非旋转)反应器中连续给入废料；
B-采用等离子体系统加热废料，非氧化气氛，温度400-900℃；
C-挥发存在于废料中的烃类和水分，并连续除去产生的气体；
D-在设于反应器外部的容器(冷凝器)中冷凝所述废气，或燃烧该废气产生能量；
E-排出不含烃类的固体物料。
图2为进行本发明工艺的设备联系图；图3为图2中设备的前视图。在图中的标号用来标识不同的装置。
所述装置包括给料系统1，静态(非旋转)反应器2，内部机构，诸如旋转螺杆3，以在反应器中传输废料，等离子体系统4包括保持直流电电弧5的石墨电极。在给料系统的同一端部为排出挥发化合物的管子6或其他装置。挥发化合物通过设于等离子体反应器外部的冷凝器7。使用常规的风扇或鼓风机从反应器中排出废气并传输到冷凝器中。去除烃类的物料依靠重力由排出口8排出；阀门9或类似装置防止空气进入反应器，清洁物料收集于储罐10。
参照附图，该方法可理解如下：含烃物料给入等离子体反应器，于此被加热至约700℃，使得废料中的烃类和水分挥发。当处理被石油、原油或类似烃类污染的土壤或淤浆时，排出的气体通过冷凝器而回收有用烃类。污染物料在通过反应器后有机化合物含量进一步减少，并且当它从反应器排出时已相当清洁。
用来处理有机污染土壤/淤浆的本发明装置和用来处理铝废料的上述装置有几个基本不同之处，特别指出如下：a)本发明装置为静态容器，在反应器内部具有传输物料的运动传输装置，而用来处理的铝废料的装置由旋转容器构成，其反应器内部无运动部件；b)本发明装置具有污染物料连续给料装置和另一连续排出清洁物料的装置，相比之下，铝废料处理装置为间歇工艺；c)本发明装置具有废气排出管、冷凝器和/或气体清洁系统；而处理铝废料的装置没有操作过程中排出和处理气体的装置。
明显地，可在权利要求的范围之内以及本发明的方法和目的之下对本发明进行修改。例如，已经公开传输系统包括旋转螺杆，但这只是一种可行的操作方式。其他方法可包括振动传输机。类似地，已经公开可进行本发明工艺的适宜装置包括设于固定容器一端部的等离子体系统；在长反应器的情况下，可设置超过一个等离子体焰炬或超过一对石墨电极来提供需要的处理能量。
本发明装置的样机经制备来实现本发明方法。污染的土壤，其含有5-90％重量的石油或原油，被给入类似的上述等离子体反应器。通过在设于反应器一端部的上述石墨电极之间使用直流电电弧，在等离子体反应器内部的温度保持为约700℃；污染物料给入如上述的反应器的相对一端部。清洁物料从反应器中排出，并且废气通过冷凝器后排放至大气中。物料在通过工序之前和之后均被分析。独立分析实验室(Labortorio Bauer-Abbo S/C Ltda，R.Aquininos 111，Sao Paulo，S.P.，Brazil，email：bauer@falcaobauer.com.br)进行的分析结果表明，无论在土壤中的有机化合物的初始成分或含量如何，等离子体方法处理后的清洁物料含有小于0.05％的有机化合物，可视为不含污染物。在实验中，所述烃类可于反应器外部的冷凝器中回收，并可另作它用。
Claims (6)
1.一种方法及适宜的装置，其用于处理被烃类化合物污染的土壤和/或淤浆，所述烃类化合物可为石油、原油、杀虫剂、除草剂以及类似化合物，其包括：
等离子体方法，其可加热污染物料直到有机化合物挥发，保持静态反应器中操作温度于400-900C；
等离子体方法，其可控制所述反应器中的气氛，使所述反应器中的气氛为还原态或中性以处理并回收有用物料；
等离子体方法，其可容许污染物料连续给入、去污染物料连续排出以及废气从工艺中连续除去；
等离子体方法，其可在需要时从所述反应器的独立容器回收在工艺过程中挥发的有用物料；
适宜的装置，包括具有运转传输装置的反应器；包括旋转螺杆，其用于将原料运输通过所述反应器和等离子系统；包括等离子体焰炬或一对石墨电极，用于提供处理能量；
装置，用于将污染物料连续地给入所述反应器，即具有旋转螺杆传输机的给料系统；
装置，用于将清洁物料连续地从所述反应器排出，所述排出系统，包括具有阀门的密封容器，阀门可防止外部空气进入所述反应器或所述工艺产生的蒸汽泄露至环境中；
装置，用于将废气从所述反应器中连续排出，其包括反应器中的排气管；
装置，用于冷凝所述废气并回收有用原料，其包括一个或多个冷凝器。
2.权利要求1的等离子体方法，其中，当不需要回收所述土壤或淤浆的有机污染物或需要通过烃类的燃烧来产生能量的时候，所述废气在位于所述反应器外部的独立容器中燃烧，通过或不通过所述冷凝器。
3.权利要求1的适宜装置，其中，具有一个以上的等离子体焰炬或一对以上所述石墨电极。
4.权利要求1的适宜装置，其中，在所述反应器中的传输装置包括振动床或传输皮带或具有叶片的旋转轴。
5.权利要求1的适宜装置，其中不设置冷凝器，并且所述气体在被排出之前在反应器外部燃烧以产生能量。
6.权利要求1的适宜装置，其中所述排出系统由封闭旋转螺杆或其他传输装置构成。
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| CN114409226A (zh) * | 2021-12-21 | 2022-04-29 | 中国光大绿色技术创新研究院有限公司 | 一种用于剩余污泥破壁消解的低温等离子体装置 |
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-
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- 2000-09-13 BR BR0006651A patent/BR0006651A/pt not_active Application Discontinuation
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- 2001-09-10 MX MXPA02004762A patent/MXPA02004762A/es not_active Application Discontinuation
- 2001-09-10 RU RU2002112481A patent/RU2308997C2/ru not_active IP Right Cessation
- 2001-09-10 EP EP20010964777 patent/EP1318859A2/en not_active Withdrawn
- 2001-09-10 CN CNB01802713XA patent/CN1251776C/zh not_active Expired - Fee Related
- 2001-09-10 WO PCT/BR2001/000116 patent/WO2002022215A2/en active Application Filing
- 2001-09-10 US US10/130,179 patent/US6767163B2/en not_active Expired - Fee Related
- 2001-09-10 JP JP2002526460A patent/JP2004507359A/ja active Pending
- 2001-09-10 AU AU2001285621A patent/AU2001285621A1/en not_active Abandoned
- 2001-09-10 CA CA 2390831 patent/CA2390831A1/en not_active Abandoned
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100457657C (zh) * | 2006-04-25 | 2009-02-04 | 大庆油田创业集团有限公司 | 一种含油污泥砂处理工艺 |
| CN100455521C (zh) * | 2007-04-23 | 2009-01-28 | 辽河石油勘探局 | 低温等离子体技术处理油田污水工艺装置 |
| CN102174334A (zh) * | 2009-07-06 | 2011-09-07 | Peat国际公司 | 用于处理废物的设备 |
| US8671855B2 (en) | 2009-07-06 | 2014-03-18 | Peat International, Inc. | Apparatus for treating waste |
| CN102174334B (zh) * | 2009-07-06 | 2014-04-02 | Peat国际公司 | 用于处理废物的设备 |
| CN102284172A (zh) * | 2011-06-08 | 2011-12-21 | 深圳市中科等离子体研究院有限公司 | 含半挥发性有机污染物的固体废物的处理方法和设备 |
| CN102284172B (zh) * | 2011-06-08 | 2013-04-24 | 深圳市迈科瑞环境科技有限公司 | 含半挥发性有机污染物的固体废物的处理方法和设备 |
| CN113443798A (zh) * | 2020-03-27 | 2021-09-28 | 宝峨资源有限公司 | 用于清洁污染材料的方法和处理设备 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1251776C (zh) | 2006-04-19 |
| EP1318859A2 (en) | 2003-06-18 |
| US6767163B2 (en) | 2004-07-27 |
| MXPA02004762A (es) | 2002-08-30 |
| WO2002022215A3 (en) | 2002-06-20 |
| US20020192030A1 (en) | 2002-12-19 |
| RU2308997C2 (ru) | 2007-10-27 |
| JP2004507359A (ja) | 2004-03-11 |
| WO2002022215A2 (en) | 2002-03-21 |
| BR0006651A (pt) | 2002-11-05 |
| RU2002112481A (ru) | 2004-03-27 |
| CA2390831A1 (en) | 2002-03-21 |
| AU2001285621A1 (en) | 2002-03-26 |
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