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WO1998006478A1 - Procede d'extraction du mercure des gaz de creuset - Google Patents

Procede d'extraction du mercure des gaz de creuset Download PDF

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Publication number
WO1998006478A1
WO1998006478A1 PCT/CA1997/000551 CA9700551W WO9806478A1 WO 1998006478 A1 WO1998006478 A1 WO 1998006478A1 CA 9700551 W CA9700551 W CA 9700551W WO 9806478 A1 WO9806478 A1 WO 9806478A1
Authority
WO
WIPO (PCT)
Prior art keywords
mercury
selenium
gases
process according
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CA1997/000551
Other languages
English (en)
Inventor
Denys Pinard
Jean Guimont
Rémi LAPOINTE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Noranda Inc
Original Assignee
Noranda Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Noranda Inc filed Critical Noranda Inc
Priority to AU37637/97A priority Critical patent/AU3763797A/en
Publication of WO1998006478A1 publication Critical patent/WO1998006478A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B43/00—Obtaining mercury

Definitions

  • the present invention is concerned with a process for removing mercury from smelter gases during the treatment of concentrates, wastes and the like.
  • the concentrates like zinc and lead concentrates are generally completely oxidized, while for other concentrates like copper concentrates, they are partly oxidized. In either case however, mercury and mercury-containing
  • Mercury may also be precipitated as sulphide by injecting H 2 S in the gases, as disclosed in US 3,855,387, or precipitated as Hg 2 Cl 2 by adding HgCl 2 (calomel precipitation), or adsorbing with activated carbon.
  • the ratio of the various mercury species, whether elemental or compounds, will vary in the cooled gases (t ⁇ 400 °C).
  • the process comprises the addition of selenium, whether in the metallic form or as a selenium compound, in a chamber containing the smelter gases maintained at a temperature sufficiently high to volatilize the selenium under oxidizing conditions.
  • Smelter gases already contain oxygen, and accordingly, there is no need to add any further oxidizer.
  • the gases are then cooled, preferably at a temperature between 250°C and 450°C, although lower temperatures may be possible, and contacted with a reductive scrubbing aqueous solution.
  • the oxidized selenium is reduced in the solution to form a suspension of nascent metallic selenium which readily reacts with mercury and mercury-containing compounds, whether in suspension or dissolved, to form a suspension of HgSe in the solution.
  • the solution may then either be disposed of in an environmentally responsible manner, for example in a tailing pond, or the HgSe may be filtrated and the solution released as an effluent, provided that no other toxic substances are present
  • the selenium is added in the metallic form as a pulp in water, and the temperature of the gases is at least 685 °C. Further, the aqueous solution is saturated with SO 2 , the latter acting as the reducing agent.
  • smelter and roaster gases contain oxygen, which acts as the oxidizer in the gases, and sulphur dioxide, which acts as a reducing agent in the aqueous solution. It is therefore not necessary to add neither during the process.
  • oxygen or reducing agents are absent from the gases and the aqueous solution respectively, then they must be added.
  • oxygen sources include air, ozone, hydrogen peroxide and the like, while the reducing agent may be any organic or inorganic reagent soluble in water, as long as its reducing potential is sufficiently strong to reduce selenium oxide.
  • the temperature of a copper smelting primary vessel is generally in the area of 1200°C, and therefore, as the feed material enters the vessel, elemental mercury is quickly volatilized and reports relatively completely to the gaseous phase. In this metallic vapor form, mercury is also in the presence of molecules of oxygen, water and sulphur dioxide. The gases then penetrate in the spray chamber wherein vaporization of water causes the
  • the mercury- containing compounds Upon contacting the aqueous solution, the mercury- containing compounds will ultimately dissolve therein.
  • gas cleaning system comprising, for example, a Venturi scrubber and primary and secondary mist prccipitators, before being forwarded to the sulphuric acid plant. Any traces of mercury remaining in the gases may be removed at this stage by conventional techniques
  • selenium is added in the gas phase of the primary vessel, preferably just before the gases penetrate in the spray chamber.
  • the selenium may be added in the solid state but the disadvantage is that some selenium will
  • a selenium pulp is preferred. Such pulp is prepared by mixing a selenium powder with a
  • Preferred grain size of about 1-50 ⁇ m, and most preferably 5 ⁇ m, in water, and the pulp is then injected in the gases of the primary vessel
  • Preferred concentrations of selenium in the pulp are from about 11 to 19 wt%, and most preferably 15 wt%.
  • selenium compounds like selenium oxide, selenium chloride, selenium sulphide etc. which may also be used as the selenium source.
  • This selenium pulp is injected in the primary vessel while the gases are maintained at a temperature high enough to instantly volatilize the selenium. For example, if metallic selenium is used as the selenium source, the minimum temperature is 685 °C.
  • the temperature at the entrance of the spray chamber is about 1000°C.
  • the selenium injection may therefore be made at that point, or directly in the gases of the primary vessel. Because of the presence of 9-12 wt% of oxygen in the gases of the primary vessel, substantially all the selenium is readily oxidized to SeO 2 .
  • the site for the injection of selenium in the primary vessel is critical to ensure the maximum efficiency thereof. As stated above, the injection most preferably takes place in the gases, and the reason is that if it is injected in the solid phase, either the slag or the matte, of the primary vessel, an average of only 7.1% of selenium is available in the gases. TABLE 2 Distribution of selenium if added in the solid phase of the primary vessel
  • the selenium oxide formed in the gases is then absorbed in the weak acid that is saturated with SO 2 , Le., with a concentration of about 3-5 g/L.
  • the weak acid may also contain about 0.5-2 wt.% of H 2 SO 4 .
  • the weak acid is therefore a reductive media wherein the selenium species, whether SeO 2 or H 2 SeO 3 , will be reduced to nascent metallic selenium.
  • the gas scrubbing tower is designed for a liquid/gas contact process and therefore, elemental mercury in the gaseous phase will react with the highly reactive nascent metallic selenium in suspension in the weak acid. Further, mercury-containing compounds,
  • mercury/selenium indicates that selenium should theoretically immobilize 2,54 times its weight of mercury. Experimental results have shown that this ratio can be as high as 3.0, which could mean that compounds like Hg, 5 Se may be formed.
  • HgSe in the gas scrubbing tower is conventional, and is generally carried out by adding metallic selenium in the water purification step.
  • Such method requires a concentration of sulphuric acid higher than 10%, preferably between 20-40%, in the scrubbing solution. And even when complying with this constraint the efficiency of mercury removal does not exceed 90%, mainly because of the limited
  • the present process may be performed in an aqueous media containing sulphuric acid in concentrations as low as 1%, and even lower.
  • the steps involved in the process namely injection of selenium, metallic or as a selenium compound,
  • the concentration of residual mercury in the treated weak acid can be up to 500 times lower if nascent metallic selenium is used instead of ordinary metallic selenium.
  • the present process also prevents the overconsumption of reagent
  • the control of the injection of selenium, as well as where it is injected allow, in addition to obtaining an excellent dispersion in the gaseous phase, to precisely inject the required concentration of selenium in the primary vessel to eliminate substantially all the mercury in the gases, because the initial concentration of mercury in the feed material to the primary vessel is known, and nearly all of it will volatilize.
  • the following examples are provided to illustrate the present invention rather
  • the concentration of selenium in the feed material to the primary vessel is sufficient to remove all the mercury therefrom.
  • the concentration of each element in the feed is such that selenium is fed at a rate of 25 kg/h while mercury is fed at a rate of 1.75 kg/h.
  • selenium is fed at a rate of 25 kg/h while mercury is fed at a rate of 1.75 kg/h.
  • Example 2 The experimental conditions of Example 2 are repeated, but selenium is injected
  • analysis of the weak acid retention tank may reliably be used to give an instant indication on the efficiency of the mercury removal process, since the analysis of the Hg/Se ratio is necessarily lower than 2.54 when enough selenium is present.
  • the Hg/Se ratio should be between 0.5 and 2.
  • the analysis of the weak acid solution will also give the concentration of mercury remaining therein, if any. Because the present process is effective in removing both metallic mercury and solubilized mercury-containing compounds, any lack of selenium will instantly be reflected in the concentration of mercury dissolved in the weak acid.
  • HgSe HgSe
  • the cleaned gases can be recycled to other industrial processes, such as the generation of sulphuric acid, or further treated to remove any residual mercury that may remain therein before releasing the gases in the atmosphere.
  • the present process allows the removal of at least 97% of mercury from the gas, and this yield can be increased up to 99.95% if the process is combined with conventional mercury removal techniques such as those mentioned previously herein. Accordingly, although the feed material to the primary vessel may contain several hundreds ppm of mercury, the treated gases produced can be used for the synthesis of high grade products, for example sulphuric acid, containing less than 0.3 ppm of mercury. Further, the aqueous gas cleaning solution contains very little mercury, if any, dissolved therein, and may therefore be disposed of in a tailing pond in an
  • the HgSe may be filtrated, and the solution may be released as an effluent of the smelter.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention a pour objet un procédé d'extraction du mercure et des composés à base de mercure des gaz de creuset et de four de grillage. Le sélénium est injecté dans les gaz dans des conditions d'oxydation, et ces gaz sont maintenus à une température suffisamment élevée pour assurer la volatilisation du sélénium. Ces gaz sont ensuite placés en contact avec une solution aqueuse de réduction. On obtient ainsi une suspension de sélénium métallique naissant dans la solution qui réagit avec le mercure, et les composés à base de mercure, en suspension ou dissous dans la solution, pour former du HgSe qui peut être mis au rebut en toute sécurité dans les bassins à schistes.
PCT/CA1997/000551 1996-08-14 1997-08-05 Procede d'extraction du mercure des gaz de creuset Ceased WO1998006478A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU37637/97A AU3763797A (en) 1996-08-14 1997-08-05 Process for the removal of mercury from smelter gases

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US68982896A 1996-08-14 1996-08-14
US08/689,828 1996-08-14

Publications (1)

Publication Number Publication Date
WO1998006478A1 true WO1998006478A1 (fr) 1998-02-19

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5828312A (en) * 1995-07-13 1998-10-27 Nec Corporation Reminder apparatus and method
CN100366326C (zh) * 2000-12-08 2008-02-06 奥托库姆普联合股份公司 从气体中除去汞的方法
US7906027B2 (en) 2008-09-26 2011-03-15 Conocophillips Company Mercury removal process
US8409535B2 (en) 2010-11-03 2013-04-02 Calpine Corporation System and method for removing a contaminant from a gas stream
CN106902776A (zh) * 2017-04-10 2017-06-30 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
CN106975289A (zh) * 2017-04-10 2017-07-25 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
CN107051405A (zh) * 2017-04-10 2017-08-18 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
CN109603410A (zh) * 2019-02-11 2019-04-12 中南大学 一种高效脱除烟气中单质汞的方法
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
PL238448B1 (pl) * 2019-07-15 2021-08-23 Politechnika Krakowska Im Tadeusza Kosciuszki Sposób zagospodarowania zużytych sorbentów selenowych
CN114538656A (zh) * 2022-02-23 2022-05-27 湖北楚星化工股份有限公司 一种控制含汞废水处理除汞剂加入量的装置及方法
CN115957614A (zh) * 2022-12-30 2023-04-14 华中科技大学 一种烟气重金属自调和式脱除方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4884728A (fr) * 1972-02-16 1973-11-10
US3786619A (en) * 1971-06-04 1974-01-22 Boliden Ab Method of purifying gases containing mercury compounds and elementary mercury
AU448507B2 (en) * 1970-10-23 1974-05-06 Boliden Aktiebolag A process for purifying gases from mercury compounds
EP0655794A1 (fr) * 1993-11-25 1995-05-31 Boliden Mineral Ab Procédé et installation pour le traitement de déchet contenant du mercure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU448507B2 (en) * 1970-10-23 1974-05-06 Boliden Aktiebolag A process for purifying gases from mercury compounds
US3786619A (en) * 1971-06-04 1974-01-22 Boliden Ab Method of purifying gases containing mercury compounds and elementary mercury
JPS4884728A (fr) * 1972-02-16 1973-11-10
EP0655794A1 (fr) * 1993-11-25 1995-05-31 Boliden Mineral Ab Procédé et installation pour le traitement de déchet contenant du mercure

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 7406, Derwent World Patents Index; AN 74-10174v, XP002047578 *
GEORG STEINTVEIT: "The Boliden-Norzink mercury removal process for purification of roaster gases", LEAD-ZINC-TIN '80, February 1980 (1980-02-01), LAS VEGAS, USA, pages 85 - 96, XP002047577 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5828312A (en) * 1995-07-13 1998-10-27 Nec Corporation Reminder apparatus and method
CN100366326C (zh) * 2000-12-08 2008-02-06 奥托库姆普联合股份公司 从气体中除去汞的方法
KR100840170B1 (ko) * 2000-12-08 2008-06-23 오또꿈뿌 오와이제이 가스로부터 수은을 제거하는 방법
US7481865B2 (en) * 2000-12-08 2009-01-27 Outotec Oyj Method for removing mercury from gas
EP1347818B1 (fr) * 2000-12-08 2011-11-02 Outokumpu Oyj Procede d'extraction de mercure a partir d'un gaz
US7906027B2 (en) 2008-09-26 2011-03-15 Conocophillips Company Mercury removal process
US8409535B2 (en) 2010-11-03 2013-04-02 Calpine Corporation System and method for removing a contaminant from a gas stream
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
CN106975289A (zh) * 2017-04-10 2017-07-25 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
CN107051405A (zh) * 2017-04-10 2017-08-18 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
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
CN106902776A (zh) * 2017-04-10 2017-06-30 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
CN109603410A (zh) * 2019-02-11 2019-04-12 中南大学 一种高效脱除烟气中单质汞的方法
PL238448B1 (pl) * 2019-07-15 2021-08-23 Politechnika Krakowska Im Tadeusza Kosciuszki Sposób zagospodarowania zużytych sorbentów selenowych
CN114538656A (zh) * 2022-02-23 2022-05-27 湖北楚星化工股份有限公司 一种控制含汞废水处理除汞剂加入量的装置及方法
CN114538656B (zh) * 2022-02-23 2023-12-22 湖北楚星化工股份有限公司 一种控制含汞废水处理除汞剂加入量的装置及方法
CN115957614A (zh) * 2022-12-30 2023-04-14 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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Publication number Publication date
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