CN100366326C - 从气体中除去汞的方法 - Google Patents
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- CN100366326C CN100366326C CNB018201970A CN01820197A CN100366326C CN 100366326 C CN100366326 C CN 100366326C CN B018201970 A CNB018201970 A CN B018201970A CN 01820197 A CN01820197 A CN 01820197A CN 100366326 C CN100366326 C CN 100366326C
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/56—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/89—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by mass-spectroscopy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
- C01P2006/33—Phase transition temperatures
- C01P2006/34—Melting temperatures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Gas Separation By Absorption (AREA)
Abstract
本发明涉及一种从包含有二氧化硫和氧的气体中以及从包含在气体中的硫酸蒸气中去除汞的方法,根据本发明,所述气体利用含有硒离子的水溶液来清洗,由此在氧中形成金属硒,该金属硒将气体和蒸气中的汞作为硒化物或在含氯的环境下作为硒和汞的双氯化物沉积出来。气体清洗发生在低于50℃的低温下。
Description
本发明涉及一种从包含有二氧化硫和氧的气体中除去汞和从包含在气体中的硫酸除去汞的方法。根据本方法,用包含硒离子的水溶液冲洗气体,由此在氧中形成金属硒,该金属硒将气体和蒸气中的汞作为硒化物或在含氯的环境下作为硒和汞的双氯化物沉积出来。气体冲洗在50摄氏度以下的温度下进行。
硫酸通常从例如那些来自锌和铜精矿的焙烧和熔炼中、且含二氧化硫的气体中生产出。在焙烧中产生的气体的汞含量在5-500mg/Nm3的数量级。从气体中最彻底地除去汞是生产高质量硫酸的先决条件。这意味着硫酸中最大汞含量可以在0.1mg/Kg H2SO4的数量级。
气体中除去汞已经在许多方面得到实施,根据其操作原则可以分成两组。第一组包括基于吸附和过滤基础上的方法,第二组包括基于沉积和过滤基础上的方法。
吸附-过滤方法仅仅适用于气体中汞含量处于低水平的情况,如,通常小于10mg/Nm3数量级。在这些方法中气体通过一个过滤器,而汞被吸收在接触面上。充满有硫的Y型沸石,活性炭和硒过滤器已经被用作吸附剂。硒过滤器的使用例如描述在专利US3 786 619中,该方法基于气态汞和固体硒之间的反应。在该方法中使用了惰性多孔过滤材料,含有二氧化硒(SeO2)的溶液吸收在该材料上并被干燥。二氧化硒由于气体中的二氧化硫而被还原,从而被洗成单质硒,该单质硒进一步与汞反应形成硒化物,HgSe。
沉积-过滤方法使用在气体中汞含量大于等于800mg/Nm3的情况下。在这些方法中,汞作为不可溶的化合物沉淀并作为被过滤的残渣从清洗器中除去。在专利US3 667 696中有该过滤方法的描述,其中汞在浓缩的冲洗酸中在160-220℃的温度下被硫酸化,并从循环的硫酸溶液中沉淀出来。US4640751公开了一种方法,其中利用氯化物溶液冲洗气体使汞作为氯化亚汞(Hg2Cl2)沉淀出来。
CA934131提供的方法是用重量百分比为1-67的硫酸在50-110℃的温度下清洗含汞的气体。因此所使用的清洗液是充满了以固体形态悬浮的活性硫磺或硒的硫酸溶液。对于在此所使用的术语的内涵,活性是指那些化合物可以以非常容易细小分离的形式存在,优选在刚刚生成的状态。在清洗之前最好给焙烧炉气加入硫或硒或者直接加到清洗酸液中。硒可以以二氧化硒的形式加入。当这个化合物与焙烧炉气中的二氧化硫接触时,二氧化硫在稀释的酸液中将二氧化硒还原成尤其是活性“原位”形式的单质硒。已经发现硫和硒在结合时有惊人的效果。该方法使得可能将硫酸中的汞含量减少到0.2mgHg/kg H2SO4的值。
从专利CA 983671中知道一种方法,该方法将硫代硫酸盐加到酸中并例如利用悬浮或过滤来分离所形成的硫化汞,从而从由二氧化硫气体所形成的硫酸溶液中去除汞。
本发明涉及一种利用硒从包含二氧化硫和氧的气体和从包含在气体中的硫酸蒸气中除去汞的方法。公知的事实是硒离子可以利用二氧化硫还原成金属,在本发明中利用了该事实。根据本发明,加有含硒离子的溶液的水将用作含氧的二氧化硫气体(如焙烧炉气)的清洗液。在二氧化硫和含在气体中的氧及清洗水中的硒化物之间的反应产生金属硒和硫酸。此外,硫酸蒸气存在于气体中。实践中,已经发现从焙烧炉气进入酸工厂的气体包括大部分的、溶解在酸蒸气中的汞和一小部分(小于10%)的气体汞或汞化物。硫酸将汞从气体中溶解到清洗水中,溶解的汞与在清洗液中的硒颗粒反应进一步产生略微溶解的Se、Hg化合物。该反应发生在低于50℃的温度下。清洗水中的硒含量被调整在100-1000mg Se/l。本发明的主要特征在所述的权利要求中将更清楚。
包含在清洗水中的硒化物利用焙烧炉气的还原反应可以用下述反应描述:
Se4++2SO2(g)+O2(g)+2H2O+4e-==>Se0+4H++2SO4 2- (1)
液滴(蒸气)形式的硫酸与清洗水中的硒化物根据下述反应进行反应:
Se4++2SO3 2-+2H2O==>Se0+4H++2SO4 2- (2)
借助由此形成的硫酸来从气体中清洗汞,这样溶解在清洗水中的汞进一步反应,从而在硒颗粒的表面上形成略微溶解的Se、Hg化合物。清洗阶段可以与例如关于单质汞的完整反应共同存在:
Hg+H2SO4==>Hg2+SO4 2-+2H++2e- (3)
发生在清洗时所形成的单质硒表面上的反应根据是在无氯还是在含氯的环境下来去除汞。当在无氯的情况下,汞在硒颗粒的表面上反应形成略微溶解的硒化物。在含氯的情况下,产品是Hg、Se的双氯化物。反应可以表示如下:
Hg2+Se+2e-==>HgSe (4)
3Hg2+2Se+2Cl-+4e-==>2HgSe*HgCl2 (5)
在实验中已经注意到当在清洗液中保持高的硒含量时,例如为100-1000mg Se/l时,去除汞是非常好的。调整硒含量使得在与从液体中形成金属硒有关的所有条件下硒含量为饱和的。硒含量的控制与连续的供给同时进行。在清洗阶段,硫酸并没有被加入到清洗溶液中而是用于清洗的清洗液为纯粹的水,并且在所有反应中所需要的酸可以作为酸蒸气存在于气体中或者是通过二氧化硫与气体中的硒离子反应而生成的。在反应(2)中产生的高水平的硒和酸足以产生用于有效去除汞的合适环境。这样,本方法几乎可以在纯水中工作,这是因为从汞去除的观点而言,由硒的还原反应而生成的酸产生了足够使单质硒在相当长的时间内保持稳定的条件。实践中,已经发现利用本发明的方法可能获得商业规模程度的、且汞含量小于0.1mg/kg H2SO4的硫酸。
Claims (4)
1.一种从包含有二氧化硫和氧的气体中以及从包含在气体中的硫酸蒸气中去除汞的方法,其特征在于,所述气体利用水作为清洗液被清洗,并且液态硒化合物被供给到清洗液中从而在低于50℃的温度下其中的硒含量在100-1000mgSe/l的范围内。
2.如权利要求1所述的方法,其特征在于,通过连续供给来控制硒含量。
3.如权利要求1所述的方法,其特征在于,在无氯的环境下,汞被还原成硒化汞HgSe。
4.如权利要求1所述的方法,其特征在于,在含氯的环境下,汞被还原成双氯化物HgSe*HgCl2。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20002698A FI117617B (fi) | 2000-12-08 | 2000-12-08 | Menetelmä elohopean poistamiseksi kaasusta |
| FI20002698 | 2000-12-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1479647A CN1479647A (zh) | 2004-03-03 |
| CN100366326C true CN100366326C (zh) | 2008-02-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018201970A Expired - Lifetime CN100366326C (zh) | 2000-12-08 | 2001-12-07 | 从气体中除去汞的方法 |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US7481865B2 (zh) |
| EP (1) | EP1347818B1 (zh) |
| JP (1) | JP2004515431A (zh) |
| KR (1) | KR100840170B1 (zh) |
| CN (1) | CN100366326C (zh) |
| AT (1) | ATE531443T1 (zh) |
| AU (2) | AU1717002A (zh) |
| BR (1) | BR0116029A (zh) |
| CA (1) | CA2429837C (zh) |
| EA (1) | EA004577B1 (zh) |
| ES (1) | ES2376993T3 (zh) |
| FI (1) | FI117617B (zh) |
| MX (1) | MXPA03005116A (zh) |
| NO (1) | NO336277B1 (zh) |
| PE (1) | PE20030633A1 (zh) |
| WO (1) | WO2002045825A1 (zh) |
| ZA (1) | ZA200304051B (zh) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100462354C (zh) * | 2001-01-18 | 2009-02-18 | 天济药业(深圳)有限公司 | 治疗免疫疾病的新的1,2-二苯基乙烯衍生物 |
| JP5040324B2 (ja) * | 2007-01-17 | 2012-10-03 | 住友金属鉱山株式会社 | 銅製錬排ガスの冷却洗浄方法 |
| JP2008190950A (ja) * | 2007-02-02 | 2008-08-21 | Horiba Ltd | 試料中の酸化セレン除去方法と除去装置、およびこれを用いた石炭燃焼排気ガス中の水銀測定方法および測定装置 |
| WO2009108220A1 (en) * | 2008-02-28 | 2009-09-03 | Brown University | Nanostructured sorbent materials for capturing environmental mercury vapor |
| US8491865B2 (en) * | 2008-02-28 | 2013-07-23 | Brown University | Nanostructured sorbent materials for capturing environmental mercury vapor |
| US20110049045A1 (en) * | 2008-10-07 | 2011-03-03 | Brown University | Nanostructured sorbent materials for capturing environmental mercury vapor |
| CN104032137B (zh) * | 2014-06-05 | 2016-06-22 | 东北大学 | 一种以硒化物形式从含汞尾渣中回收汞的方法 |
| CN105056733B (zh) * | 2015-07-30 | 2017-06-06 | 中南大学 | 一种冶炼烟气洗涤过程中汞再释放抑制剂及其应用 |
| US11077425B2 (en) | 2016-09-02 | 2021-08-03 | Regents Of The University Of Minnesota | Systems and methods for body-proximate recoverable capture of mercury vapor during cremation |
| CN107051405B (zh) * | 2017-04-10 | 2019-05-31 | 浙江工业大学 | 一种负载纳米硒的海绵及其化学制备与应用 |
| CN106902776B (zh) * | 2017-04-10 | 2019-01-08 | 浙江工业大学 | 一种用于高汞行业车间的除汞壁纸及其制备方法 |
| CN106975289B (zh) * | 2017-04-10 | 2019-05-28 | 浙江工业大学 | 一种高汞车间空气净化器核心滤网及其制备方法与应用 |
| CN115715973A (zh) * | 2019-05-31 | 2023-02-28 | 贵州重力科技环保有限公司 | 一种原位级纳米硒炭基脱汞吸附材料及其制备方法和应用 |
| CN113521979B (zh) * | 2021-08-12 | 2024-01-12 | 上海交通大学 | 一种通过氯硒汞沉积从含硫含汞烟气中捕集汞的方法 |
| CN115957614B (zh) * | 2022-12-30 | 2025-04-15 | 华中科技大学 | 一种烟气重金属自调和式脱除方法 |
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| DE2025389A1 (en) * | 1969-09-01 | 1971-03-04 | Boliden Ab | Purifying mercury compounds containing - gases |
| US3954451A (en) * | 1971-09-10 | 1976-05-04 | Mitsui Mining & Smelting Co., Ltd. | Method for the manufacture of mercury free sulfuric acid |
| JPS58114728A (ja) * | 1981-12-28 | 1983-07-08 | Mitsubishi Metal Corp | 水銀除去剤およびその製造方法 |
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| FI45767C (fi) | 1970-07-03 | 1972-09-11 | Outokumpu Oy | Menetelmä elohopean ja/tai seleenin poistamiseksi ja talteenottamiseks i elohopea- ja/tai seleenipitoisista kaasuista. |
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| US4057423A (en) * | 1971-09-10 | 1977-11-08 | Mitsui Mining & Smelting Co., Ltd. | Method for the manufacture of mercury free sulfuric acid |
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2000
- 2000-12-08 FI FI20002698A patent/FI117617B/fi not_active IP Right Cessation
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2001
- 2001-11-30 PE PE2001001209A patent/PE20030633A1/es active IP Right Grant
- 2001-12-07 CN CNB018201970A patent/CN100366326C/zh not_active Expired - Lifetime
- 2001-12-07 JP JP2002547599A patent/JP2004515431A/ja active Pending
- 2001-12-07 AU AU1717002A patent/AU1717002A/xx active Pending
- 2001-12-07 CA CA002429837A patent/CA2429837C/en not_active Expired - Lifetime
- 2001-12-07 US US10/433,844 patent/US7481865B2/en not_active Expired - Lifetime
- 2001-12-07 BR BR0116029-0A patent/BR0116029A/pt not_active Application Discontinuation
- 2001-12-07 ES ES01999417T patent/ES2376993T3/es not_active Expired - Lifetime
- 2001-12-07 EA EA200300649A patent/EA004577B1/ru not_active IP Right Cessation
- 2001-12-07 EP EP01999417A patent/EP1347818B1/en not_active Expired - Lifetime
- 2001-12-07 KR KR1020037007639A patent/KR100840170B1/ko not_active Expired - Fee Related
- 2001-12-07 MX MXPA03005116A patent/MXPA03005116A/es active IP Right Grant
- 2001-12-07 WO PCT/FI2001/001064 patent/WO2002045825A1/en not_active Ceased
- 2001-12-07 AT AT01999417T patent/ATE531443T1/de active
- 2001-12-07 AU AU2002217170A patent/AU2002217170B2/en not_active Ceased
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2003
- 2003-05-26 ZA ZA200304051A patent/ZA200304051B/en unknown
- 2003-06-03 NO NO20032507A patent/NO336277B1/no not_active IP Right Cessation
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|---|---|---|---|---|
| DE2025389A1 (en) * | 1969-09-01 | 1971-03-04 | Boliden Ab | Purifying mercury compounds containing - gases |
| US3954451A (en) * | 1971-09-10 | 1976-05-04 | Mitsui Mining & Smelting Co., Ltd. | Method for the manufacture of mercury free sulfuric acid |
| JPS58114728A (ja) * | 1981-12-28 | 1983-07-08 | Mitsubishi Metal Corp | 水銀除去剤およびその製造方法 |
| WO1993000983A1 (de) * | 1991-07-13 | 1993-01-21 | L. & C. Steinmüller Gmbh | Verfahren zum reinigen eines schwefeldioxid und ggf. andere schadstoffe enthaltenden abgases |
| WO1998006478A1 (en) * | 1996-08-14 | 1998-02-19 | Noranda Inc. | Process for the removal of mercury from smelter gases |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2376993T3 (es) | 2012-03-21 |
| AU1717002A (en) | 2002-06-18 |
| FI117617B (fi) | 2006-12-29 |
| BR0116029A (pt) | 2003-10-07 |
| US7481865B2 (en) | 2009-01-27 |
| FI20002698L (fi) | 2002-06-09 |
| FI20002698A0 (fi) | 2000-12-08 |
| MXPA03005116A (es) | 2003-09-05 |
| KR20040010575A (ko) | 2004-01-31 |
| ZA200304051B (en) | 2004-02-27 |
| WO2002045825A1 (en) | 2002-06-13 |
| EP1347818B1 (en) | 2011-11-02 |
| EA004577B1 (ru) | 2004-06-24 |
| NO336277B1 (no) | 2015-07-06 |
| ATE531443T1 (de) | 2011-11-15 |
| CA2429837C (en) | 2009-09-01 |
| NO20032507D0 (no) | 2003-06-03 |
| NO20032507L (no) | 2003-06-03 |
| PE20030633A1 (es) | 2003-08-19 |
| US20040081605A1 (en) | 2004-04-29 |
| CA2429837A1 (en) | 2002-06-13 |
| CN1479647A (zh) | 2004-03-03 |
| EA200300649A1 (ru) | 2003-12-25 |
| AU2002217170B2 (en) | 2006-07-20 |
| JP2004515431A (ja) | 2004-05-27 |
| EP1347818A1 (en) | 2003-10-01 |
| KR100840170B1 (ko) | 2008-06-23 |
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