CN103298737A - 从生物反应器淤渣回收硒 - Google Patents
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
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- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C02F2303/16—Regeneration of sorbents, filters
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Abstract
在生物反应器中处理含有可溶性硒的废水,例如烟道气脱硫排污水。反应器中的微生物将硒还原为不溶性元素硒。从反应器排放废淤渣中的元素硒,该废淤渣还包含生物质和其它悬浮的固体。通过酸溶解接着脱水,除去非微生物悬浮的固体。在低于硒氧化温度的温度下燃烧剩余的淤渣,以除去生物质,同时留下硒颗粒。
Description
发明领域
本说明书涉及废水处理,以从废水除去硒和回收硒。
发明背景
以下段落不是承认以下任何信息为常见的一般知识或可引用作为现有技术。
硒为人类健康必要的微量元素。硒也是具有若干可用性质的贵重的非金属。例如,硒具有光生伏打和传导性质,使其可用于光生伏打和电子产品。硒还在玻璃和维生素补充剂和肥料中用作颜料。
然而,在非常低的浓度下硒也变得具有毒性。硒在生长在被硒污染的水的植物和鱼的身体中蓄积,并且在吃那些植物和鱼的野生生物和人的身体中蓄积。在人类中,升高的硒浓度可引起神经病学破坏和毛发和指甲丧失。
在各种工业或农业操作中产生的废水中,硒可以可溶性形式(硒酸盐和亚硒酸盐)存在。例如,硒通常存在于在燃煤发电厂中产生的烟道气脱硫排污水中。硒也可存在于一些炼油和采矿废物中。硒的排放限度可设定在10份/十亿(ppb)-50 ppb之间。
国际公布号WO 2007/012181描述了一种用于从废水除去硒的生物反应器。硒除去反应器由General Electric Company,GE Water and Process Technologies销售,商标为ABMet。在这些反应器中,固定的介质床支撑硒还原性生物的生物膜。生物将废水中的硒酸盐和亚硒酸盐还原为元素硒,其从废水中沉淀。硒保留在反应器中,直至其通过周期性冲洗操作在废淤渣中被除去。
发明概述
以下发明概述旨在向读者介绍接下来的详细说明,并且不限制或限定任何要求保护的发明。
从硒生物反应器除去的淤渣含有元素硒,并且可分类为毒性废物。因此,淤渣必须储存或处置,以防止硒沥滤进入环境。储存或处置淤渣的成本是显著的。另一方面,淤渣中的硒为有价值的商品。因此,从淤渣回收硒生产有用的产品,并且降低废物处理和环境问题。
在本文描述的方法中,处理含有元素硒、微生物和其它固体(例如矿物)的淤渣,以回收硒。将淤渣与酸混合,以溶解一些固体。随后使淤渣增稠或脱水,以除去溶解的固体。将增稠的淤渣在低于350℃的温度下燃烧,以除去微生物。元素硒以在淤渣燃烧后剩余的灰分形式回收。
当与生物除污方法组合时,所述方法提供硒的再循环利用或硒从废物中的回收。回收的硒可用作工业应用的资源。
附图
图1为从废水回收硒的方法的示意性工艺流程图。
图2为元素硒和淤渣微生物的TGA分析。
发明详述
图1显示用于回收硒的方法10。含有硒的废水的进料流12进入生物反应器14。例如,进料流12可为来自燃煤发电厂的烟道气脱硫排污水。在生物反应器14中,微生物将可溶性形式的硒转化为不溶性元素硒。生物反应器14可为ABMet?反应器,可得自GE Water and Process Technologies,一家属于General Electric Company的企业。在这种形式的生物反应器14中,待处理的水流动通过支撑微生物的固定介质床。元素硒作为颗粒与生物质一起保留在生物反应器14中。经处理的水16流出生物反应器14,优选硒浓度降低至低于排放限度。将生物反应器14周期性冲洗,产生淤渣18,其含有生物质、元素硒和存在于进料流12中的悬浮的固体。其它生物除污方法也可产生含有硒的流出物或淤渣。例如,在含有悬浮生长的硒还原性生物的膜生物反应器中,硒可从废水中除去。在从处理罐的底部或单独的膜容器取出的淤渣中排放元素硒。
将淤渣18送至淤渣增稠装置20,以产生增稠的淤渣22。淤渣增稠装置20可为例如离心机、过滤压机或带式增稠器。从淤渣24释放的过量的水24可送至单独的废水处理设备或再循环至生物反应器14上游的点。增稠的淤渣22可含有10-30重量%固体。该固体包含从生物反应器14释放的微生物的细胞、存在于送至生物反应器14并且仍保留在增稠的淤渣22中的进料水12中的其它悬浮的固体和已被微生物还原的元素硒。在取自ABMet反应器的增稠的淤渣的一个样品中,增稠的淤渣22中的固体由约51%微生物细胞、约48%其它悬浮的固体和约1%的小百分比的硒组成,所述ABMet反应器处理来自燃煤发电厂的烟道气脱硫排污水。还存在痕量(小于0.1%)的镍。其它悬浮的固体主要为矿物质例如石膏颗粒、飞灰和石灰石颗粒。
由于其高的硒浓度,增稠的淤渣22不能像非有害废物一样处置。在美国,增稠的淤渣22必须通过毒性特性沥滤程序(TCLP)来确定增稠的淤渣22必须怎样处理。如果TCLP结果超过1.0mg/L,那么增稠的淤渣22可能必须至少在有害废物填埋区域中储存。如果TCLP结果超过5.7 mg/L,那么增稠的淤渣22可能必须被送至废物处理公司,花费巨大。然而,在方法10中,增稠的淤渣22在回收过程中被进一步处理,以除去至少一些剩余的硒,优选使得待排放的任何剩余的淤渣的TCLP为1 mg/L或更少。
在回收过程的第一部分中,将增稠的淤渣22送至混合罐24。在混合罐24中,加入酸26,以溶解至少一些非细胞或矿物悬浮的固体。混合罐24可保持在环境温度或室温,例如低于40℃或低于30℃的温度。酸26优选不是氧化物。例如,酸26可为盐酸(HCl)。优选将混合罐24搅拌,以增强反应。
部分溶解的淤渣28从混合罐24流动至固-液物理分离装置30。分离装置30可为例如离心机。将液体部分30除去,留下进一步增稠的淤渣34,其中固体(特别是非细胞和矿物固体)的比例降低。
进一步增稠的淤渣34随后被进一步处理,以除去微生物。在方法10中,将进一步增稠的淤渣34送至炉36并燃烧,优选在足够低以基本上防止硒氧化的温度下。参考图2的TGA分析,硒在约350℃的温度下氧化,而淤渣中的显著部分的生物质可在约200或250℃下燃烧。因此,在例如250℃-325℃的温度下燃烧淤渣,除去生物质,而通常没有将硒氧化。
在实验中,如上所述的ABMet淤渣的样品使用盐酸处理,在离心机中进一步增稠,随后在300℃下燃烧。样品中的固体的重量在下表2中给出。如表中所示,大多数淤渣被烧掉,但是大多数(超过70%)的硒保留。
表2
Claims (13)
1. 一种从生物反应器淤渣回收硒的方法,所述淤渣包含元素硒、能还原硒的可溶性形式的微生物和其它固体,所述方法包括以下步骤:
a) 溶解淤渣中的大多数其它固体;
b) 从淤渣中除去水;和
c) 在低于350℃的温度下燃烧淤渣。
2. 权利要求1的方法,其中步骤a)包括将酸混合到淤渣中。
3. 权利要求2的方法,其中所述酸不是氧化物。
4. 权利要求3的方法,其中在步骤a)期间所述淤渣保持在40℃或以下的温度。
5. 权利要求1的方法,其中步骤b)包括使淤渣通过淤渣增稠装置。
6. 权利要求1的方法,其中所述淤渣在250℃-325℃的温度下燃烧。
7. 一种用于处理烟道气脱硫排污水的方法,所述方法包括以下步骤:
a) 在含有硒还原性微生物的生物反应器中处理废水;
b) 取出淤渣,该淤渣包含元素硒的颗粒、微生物和来自反应器的矿物固体;
c) 溶解大多数矿物固体;
d) 从淤渣中除去含有溶解的矿物质的水;和
e) 在低于350℃的温度下燃烧淤渣。
8. 权利要求7的方法,其中步骤a)包括将酸混合到淤渣中。
9. 权利要求8的方法,其中所述酸不是氧化物。
10. 权利要求9的方法,其中在步骤a)期间所述淤渣保持在40℃或以下的温度。
11. 权利要求7的方法,其中步骤b)包括使淤渣通过淤渣增稠装置。
12. 权利要求7的方法,其中所述淤渣在250℃-325℃的温度下燃烧。
13. 权利要求7的方法,其中步骤a)包括使废水流动通过固定介质床,且步骤b)包括冲洗或反洗介质床。
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Application Number | Priority Date | Filing Date | Title |
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PCT/CN2010/002069 WO2012079201A1 (en) | 2010-12-17 | 2010-12-17 | Selenium recovery from bioreactor sludge |
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CN103298737A true CN103298737A (zh) | 2013-09-11 |
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US (1) | US20130248443A1 (zh) |
EP (1) | EP2651817A4 (zh) |
CN (1) | CN103298737A (zh) |
CA (1) | CA2819783A1 (zh) |
EA (1) | EA201390733A1 (zh) |
WO (1) | WO2012079201A1 (zh) |
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WO2016010419A1 (en) * | 2014-07-14 | 2016-01-21 | Wageningen Universiteit En Researchcentrum | Process for recovering elemental selenium from wastewater |
CN110255857B (zh) * | 2019-05-28 | 2021-12-14 | 路德环境科技股份有限公司 | 用于建筑泥浆深度脱水的低碱调理剂及脱水方法 |
US20240101456A1 (en) * | 2020-12-04 | 2024-03-28 | Arizona Board Of Regents On Behalf Of Arizona State University | Systems and methods for biological transformation, concentration, and recovery of selenium from wastewater |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3008806A (en) * | 1959-04-15 | 1961-11-14 | American Metal Climax Inc | Processing of selenium-containing metallurgical dusts and fumes |
US4377486A (en) * | 1980-12-24 | 1983-03-22 | Wrc Processing Company | Organic sludge dewatering process |
CN101223111A (zh) * | 2005-07-25 | 2008-07-16 | 泽农技术合伙公司 | 处理烟气脱硫排污或类似液体的设备和方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4519913A (en) * | 1984-06-01 | 1985-05-28 | Kerr-Mcgee Corporation | Process for the removal and recovery of selenium from aqueous solutions |
CA1337019C (en) * | 1988-10-14 | 1995-09-19 | Ronald Glen Lang Mccready | Biorecovery of selenium |
US6235204B1 (en) * | 1999-04-15 | 2001-05-22 | Radian International Llc | Method and system for removal of selenium from FGD scrubber purge water |
WO2003045851A1 (fr) * | 2001-11-29 | 2003-06-05 | Corporation Biolix | Procede de stabilisation et conditionnement de boues d'epuration municipales et industrielles |
WO2007012181A1 (en) * | 2005-07-25 | 2007-02-01 | Zenon Technology Partnership | Apparatus and method for treating fgd blowdown or similar liquids |
HUP0700480A2 (en) * | 2007-07-16 | 2010-01-28 | Aliment Kft Dr | Nanospheres of red and grey elemental selenium and production technology thereof |
-
2010
- 2010-12-17 CA CA 2819783 patent/CA2819783A1/en not_active Abandoned
- 2010-12-17 US US13/255,007 patent/US20130248443A1/en not_active Abandoned
- 2010-12-17 CN CN2010800707474A patent/CN103298737A/zh active Pending
- 2010-12-17 EA EA201390733A patent/EA201390733A1/ru unknown
- 2010-12-17 WO PCT/CN2010/002069 patent/WO2012079201A1/en active Application Filing
- 2010-12-17 EP EP10860878.7A patent/EP2651817A4/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3008806A (en) * | 1959-04-15 | 1961-11-14 | American Metal Climax Inc | Processing of selenium-containing metallurgical dusts and fumes |
US4377486A (en) * | 1980-12-24 | 1983-03-22 | Wrc Processing Company | Organic sludge dewatering process |
CN101223111A (zh) * | 2005-07-25 | 2008-07-16 | 泽农技术合伙公司 | 处理烟气脱硫排污或类似液体的设备和方法 |
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CA2819783A1 (en) | 2012-06-21 |
EP2651817A4 (en) | 2014-06-18 |
US20130248443A1 (en) | 2013-09-26 |
EP2651817A1 (en) | 2013-10-23 |
WO2012079201A8 (en) | 2013-06-06 |
EA201390733A1 (ru) | 2013-12-30 |
WO2012079201A1 (en) | 2012-06-21 |
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