CN104032137A - Method for recovering mercury from mercury-contained tailings in form of selenide - Google Patents
Method for recovering mercury from mercury-contained tailings in form of selenide Download PDFInfo
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- CN104032137A CN104032137A CN201410246637.9A CN201410246637A CN104032137A CN 104032137 A CN104032137 A CN 104032137A CN 201410246637 A CN201410246637 A CN 201410246637A CN 104032137 A CN104032137 A CN 104032137A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention belongs to the field of environmental protection; and aiming at problems of complex components and no proper method for treatment of mercury-contained tailings produced in a nonferrous metal smelting process, the invention discloses a method for recovering mercury from the mercury-contained tailings in a form of selenide. The mercury contained in the mercury-contained tailings is leached out by adopting thiosulfate; and alkali metal selenide is added in solution containing the mercury and thiosulfuric acid radical complex ions, so that the mercury is converted to mercury selenide precipitates with stability, low solubility and low toxicity. The method is simple in operation; after the complex leaching treatment is performed with the thiosulfate solution, the transfer-state mercury in the mercury-contained tailings is largely decreased; and the mercury is finally converted to the precipitates in the form of stored and stable mercury selenide, so that the pollution harm of the mercury in the mercury-contained tailings to the environment is eliminated.
Description
Technical field
The invention belongs to field of environment protection, relate to a kind of method that adopts selenide form to reclaim mercury from mercurous tailings.
Background technology
Mercury, as the typical global pollution thing of one, can threaten environment for human survival by Transport And Transformation and accumulation.For this reason, various countries all very pay close attention to the harm of mercury, require to reduce the discharge of mercury, the supply and demand of subduing mercury, control product mercury quantity, the exposure that prevents mercury, raising control mercury consciousness, promote the world to control mercury.
Discharge to mercurous waste gas and mercury-containing waste water at present, national environmental protection department has formulated clear and definite emission standard.The demercuration processing before discharge about mercurous waste gas and mercury-containing waste water, each state all develops rationally effectively method for removing mercury.As adopted absorption process, absorption method, gas-phase reaction method, method of cooling and combined purifying method to remove mercury to containing mercury gas.For mercurous waste water, can adopt the processing such as reduction method, chemical precipitation method, ion exchange method and active carbon adsorption.
For mercurous solid waste, relatively be typically the waste that various mercurous products use rear output, as PVC industry has produced a large amount of useless mercury catalysts, mercurous gac in process of production, medical industry is still partly used mercurous thermometer, sphygmomanometer etc. at present, and the luminescent lamp that the widely used mercury line of electric light source industry excites all contains a small amount of mercury.For this type of mercury-containing wastes, in category set after, can adopt roasting-condensation method to reclaim mercury.As required handled mercury-containing wastes is carried out to break process, and with medicament carries out carrying out washing treatment, then add appropriate alkali lye, by mixing, damping carries out granulation; Again the particulate materials making is sent into stoving oven roasting, maturing temperature is 400～800 DEG C, sends into condenser condenses to reclaim mercury after the mercury vapour dedusting of generation.The Chinese patent that is 200420082423.4 as the patent No. provides a kind for the treatment of unit of waste slag containing mercury, and mercurous waste fluorescent light tube is heated in Sealing Arrangement, makes mercury be evaporated to mercury vapour, then mercury metal is reclaimed in condensation.The Chinese patent that the patent No. is 200420082125.5 provides a kind of process furnace for waste slag containing mercury processing, adopts a kind of airtight process furnace, and waste slag containing mercury is removed to mercury through heating evaporation.Application number is that 201310671649 Chinese patent discloses a kind of useless mercury catalyst mercury chloride recovery process, in gas retort by heating, condensation to reclaim mercury chloride and gac simultaneously.
In the smelting production process of non-ferrous metal, because part raw mineral materials self contains a small amount of mercury, the also mercurous waste residue of output in Metallurgy Process.As due to historical reasons, use amalgam process to extract gold from certain areas, the application of mercury causes the output of a large amount of mercurous tailings.In addition, adopting cyanide process to extract in golden smelting flow process, because mercury grade in part gold mine raw ore is higher, after cyaniding is processed, mercury is mainly dispersed in cyaniding tail washings and cyanidation tailings.In nonferrous metallurgical process, at present of greatest concern is the processing of mercury-containing waste water and mercury-containing waste water, for the mercurous tailings of output, due to complicated component, temporarily without effective ways processing.
Summary of the invention
The object of the invention is in the smelting production process for non-ferrous metal, mercurous tailings is without the problem of effective ways processing, a kind of method that reclaims mercury with selenide form from mercurous tailings is provided, the method is simple to operate, after thiosulfate solution complexation leaching is processed, transportable state mercury in mercurous tailings greatly reduces, and mercury is finally converted into easy storage, stable mercury selenide form precipitates in order to reclaim, and has eliminated the pollution hazard of mercury to environment in mercurous tailings.
For achieving the above object, the technical solution used in the present invention is:
A method that reclaims mercury with selenide form from mercurous tailings, comprises following steps:
1, the thiosulfate solution that is 8～20g/L by concentration carries out agitation leach to mercurous tailings, the mercurous tailings of per kilogram adds 3～10L thiosulfate solution, extraction temperature is 20～50 DEG C, extraction time is 0.5～3.0h, reaction finishes, after liquid-solid separation, to obtain leached mud, leach liquor and washings;
2, leached mud is stored up, merged leach liquor and washings, obtain the solution containing soluble mercury complex compound;
3, basic metal selenide is added in the solution containing soluble mercury complex compound, it is 0.6～1.0 times of mercury quality in solution that selenide adds quality, after reaction 5～10min, add flocculation agent to solution, its concentration is 1～2g/L, add-on is every cubic metre and adds 10～20L flocculation agent containing soluble mercury complex solution, through liquid-solid separation, obtains decomposed solution and mercury selenide precipitation;
Wherein, described basic metal selenide is sodium selenide; Described flocculation agent is polyacrylamide slurries;
4, the mercury selenide obtaining is the product reclaiming, and decomposed solution is supplied and returned to step 1 after thiosulphate and recycle as thiosulfate solution.
The above-mentioned method that reclaims mercury with selenide form from mercurous tailings, described thiosulphate is Sulfothiorine and/or ammonium thiosulfate.
Principle of the present invention is: different with metallurgy technique according to non-ferrous metal material characteristic, the mercury of smelting in remaining mercurous tailings can exist in a variety of forms, but generally can be divided into zunsober that the soluble red precipitate of mercury chloride, diluted acid of water-soluble form and Mercury bisulfate, residual form exist etc., and the mercury content existing with metallic state is very micro-.For extract in mercurous tailings to body of groundwater, plant-growth harm maximum be the mercury that move state, and by the mercury safety storing proposing, the present invention is converted into mercury selenide and precipitates being the mercury that moves state.Because selenide cost is higher, the present invention utilizes mercury and sulfate sulfatase root can form the feature of stable comple, adopt the transportable state mercury in the mercurous tailings of thiosulphate complexation leaching, the particularly mercury of water soluble and diluted acid, thus the transportable mercury pollution hazard to environment in the time of follow-up storing up of mercurous tailings eliminated; Then, by the complex compound of the mercury in leach liquor and thiosulfate anion, by adding the method for basic metal selenide, be converted into mercury selenide, mercury selenide has more stable, more low solubility, more hypotoxic characteristic compared with zunsober, is conducive to the stored safely of mercury.
Advantage of the present invention is:
1, the method is simple to operate, adopts thiosulfate solution, and after agitation leach is processed, transportable state mercury leaching yield is 99%, and the transportable state mercury in mercurous tailings is almost all removed, and has greatly reduced the pollution hazard of mercury to environment in mercurous tailings; And the mercury being leached is finally converted into highly stable mercury selenide form and precipitates, the mercury that storage that can safety is dissolved.
2, mercury selenide has extremely low solubleness, under normal condition, the thiosulfuric acid salt complex of mercury can be converted into mercury selenide precipitation, and this speed of response is fast.
3, present method is processed in mercurous tailings process without mercurous waste gas and mercury-containing waste water discharge, and leach liquor can recycle in the method, environmental protection, safe, pollution-free.
Specific implementation method
Following embodiment is only in order to further illustrate the present invention, instead of limits the scope of the invention.
Mercurous tailings is gold mine cyanidation tailings, and wherein total mercury amount is 1570mg/kg, and adopting 1mol/L sodium acetate solution (adding glacial acetic acid to adjust pH is 5) to leach and measuring transportable state mercury content in this cyanidation tailings is 706.5mg/kg.
Agents useful for same is industrial goods.
Embodiment 1
Get the mercurous tailings of 1kg, adding 3L concentration is the hypo solution of 20g/L, and agitation leach 0.5h at 50 DEG C, obtains leached tailings, leach liquor and washings after liquid-solid separation; Sampling analysis, in leached tailings, the leaching yield of transportable mercury is 99%;
Leached tailings after separating is stored up; Merge leach liquor and washings, obtain the solution of 4L containing soluble mercury complex compound, wherein mercurous 700mg, in solution, add 0.42g sodium selenide, after reaction 5min, add 1g/L polyacrylamide slurries 0.08L, carry out liquid-solid separation, obtain decomposed solution and mercury selenide precipitation, mercury selenide is precipitated as the product of recovery, and in solution, 99.98% mercury is converted into mercury selenide precipitation.
Embodiment 2
Get the mercurous tailings of 1kg, adding wherein concentration is the Sulfothiorine of 8g/L and the ammonium thiosulfate mixing solutions of 6g/L, and add-on is 6L; Agitation leach 2h at 35 DEG C, obtains leached tailings, leach liquor and washings after liquid-solid separation; Sampling analysis, in leached tailings, the leaching yield of transportable mercury is 99%;
Leached tailings after separating is stored up; Merge leach liquor and washings, obtain the solution of 7L containing soluble mercury complex compound, wherein mercurous 700mg, in solution, add after 0.54g sodium selenide reaction 10min, add 2g/L polyacrylamide slurries 0.09L, carry out liquid-solid separation, obtain decomposed solution and mercury selenide precipitation, mercury selenide is precipitated as the product of recovery, and in solution, 99.99% mercury is converted into mercury selenide precipitation;
The decomposed solution obtaining, adds Sulfothiorine and ammonium thiosulfate, and making solution is that concentration is the mixing solutions of the Sulfothiorine of 8g/L and the ammonium thiosulfate of 6g/L, returns to agitation leach step and recycles as thiosulfate solution.
Embodiment 3
Get the mercurous tailings of 1kg, adding 10L concentration is the hypo solution of 8g/L, and agitation leach 3h at 20 DEG C, obtains leached tailings, leach liquor and washings after liquid-solid separation; Sampling analysis, in leached tailings, the leaching yield of transportable mercury is 99%;
Leached tailings after separating is stored up; Merge leach liquor and washings, obtain the solution of 11L containing soluble mercury complex compound, wherein mercurous 700mg, in solution, add 0.70g sodium selenide, reaction 7min, adds 1.5g/L polyacrylamide slurries 0.22L, carry out liquid-solid separation, obtain decomposed solution and mercury selenide precipitation, mercury selenide is precipitated as the product of recovery, and in solution, 99.99% mercury is converted into mercury selenide precipitation.
Embodiment 4
Get the mercurous tailings of 1kg, adding 10L concentration is the thiosulfuric acid ammonium solution of 8g/L, and agitation leach 1h at 40 DEG C, obtains leached tailings, leach liquor and washings after liquid-solid separation; Sampling analysis, in leached tailings, the leaching yield of transportable mercury is 99%;
Leached tailings after separating is stored up; Merge leach liquor and washings, obtain the solution of 11L containing soluble mercury complex compound, wherein mercurous 700mg, in solution, add 0.64g sodium selenide, reaction 5min, adds 2g/L polyacrylamide slurries 0.11L, carry out liquid-solid separation, obtain decomposed solution and mercury selenide precipitation, mercury selenide is precipitated as the product of recovery, and in solution, 99.99% mercury is converted into mercury selenide precipitation;
The decomposed solution obtaining, adds ammonium thiosulfate, and making solution is that concentration is the thiosulfuric acid ammonium solution of 8g/L, returns to agitation leach step and recycles as thiosulfate solution.
Claims (10)
1. a method that reclaims mercury with selenide form from mercurous tailings, is characterized in that, comprises following steps:
(1) with thiosulfate solution, mercurous tailings is carried out to agitation leach, reaction finishes, after liquid-solid separation, to obtain leached mud, leach liquor and washings;
(2) leached mud is stored up, merged leach liquor and washings, obtain the solution containing soluble mercury complex compound;
(3) basic metal selenide is added in the solution containing soluble mercury complex compound, after reaction finishes, through liquid-solid separation, obtain decomposed solution and mercury selenide precipitation, mercury selenide is the product reclaiming.
2. a kind of method that reclaims mercury with selenide form from mercurous tailings according to claim 1, is characterized in that, the described thiosulphate of step (1) is Sulfothiorine and/or ammonium thiosulfate.
3. a kind of method that reclaims mercury with selenide form from mercurous tailings according to claim 1, is characterized in that, the described thiosulfate solution concentration of step (1) is 8～20g/L.
4. a kind of method that reclaims mercury with selenide form from mercurous tailings according to claim 1, it is characterized in that, in described step (1), the ratio of mercurous tailings and thiosulfate solution is: the mercurous tailings of per kilogram adds 3～10L thiosulfate solution.
5. a kind of method that reclaims mercury with selenide form from mercurous tailings according to claim 1, is characterized in that, in described step (1), the condition of agitation leach reaction is: 20～50 DEG C of extraction temperatures, extraction time 0.5～3.0h.
6. a kind of method that reclaims mercury with selenide form from mercurous tailings according to claim 1, is characterized in that, in step (3), described basic metal selenide is sodium selenide; Described basic metal selenide add-on is: basic metal selenide quality is 0.6～1.0 times of mercury quality in solution.
7. a kind of method that reclaims mercury with selenide form from mercurous tailings according to claim 1, is characterized in that, in described step (3), basic metal selenide is 5～10min with the reaction times containing soluble mercury complex compound.
8. a kind of method that reclaims mercury with selenide form from mercurous tailings according to claim 1, is characterized in that, in described step (3), after reaction finishes, adds after flocculation agent, then carry out solid-liquid separation in solution.
9. a kind of method that reclaims mercury with selenide form from mercurous tailings according to claim 8, it is characterized in that, flocculation agent described in step (3) is polyacrylamide slurries, its concentration is 1～2g/L, and its add-on is: every cubic metre adds 10～20L containing soluble mercury complex solution.
10. a kind of method that reclaims mercury with selenide form from mercurous tailings according to claim 1, it is characterized in that, the decomposed solution of described step (3) is returned to step (1) and is recycled as thiosulfate solution after supplying thiosulphate.
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| CN201410246637.9A CN104032137B (en) | 2014-06-05 | 2014-06-05 | A kind of method reclaiming hydrargyrum with selenides form from mercurous tailings |
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| CN201410246637.9A CN104032137B (en) | 2014-06-05 | 2014-06-05 | A kind of method reclaiming hydrargyrum with selenides form from mercurous tailings |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104722574A (en) * | 2015-02-13 | 2015-06-24 | 苏州久王环保科技股份有限公司 | New method for repairing mercury polluted soil by using byproduct ammonium thiosulfate recycled from coking desulfurization waste solution |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS515341B1 (en) * | 1970-11-26 | 1976-02-19 | ||
| CN1479647A (en) * | 2000-12-08 | 2004-03-03 | ���п�ķ�����Ϲɷݹ�˾ | Method for removing mercury from gas |
| CN102560098A (en) * | 2012-02-09 | 2012-07-11 | 苏州久王多铵盐科技有限公司 | Purpose of by-product ammonium thiosulfate generated in steel-making waste water treatment process as complexing agent for leaching silver and its application method |
| CN103097495A (en) * | 2010-09-16 | 2013-05-08 | 雪佛龙美国公司 | Process, method, and system for removing heavy metals from fluids |
| CN103249814A (en) * | 2010-11-19 | 2013-08-14 | 雪佛龙美国公司 | Process, method, and system for removing heavy metals from fluids |
| CN103548631A (en) * | 2013-10-24 | 2014-02-05 | 中国科学院高能物理研究所 | Method for reducing mercury content in rice |
-
2014
- 2014-06-05 CN CN201410246637.9A patent/CN104032137B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS515341B1 (en) * | 1970-11-26 | 1976-02-19 | ||
| CN1479647A (en) * | 2000-12-08 | 2004-03-03 | ���п�ķ�����Ϲɷݹ�˾ | Method for removing mercury from gas |
| CN103097495A (en) * | 2010-09-16 | 2013-05-08 | 雪佛龙美国公司 | Process, method, and system for removing heavy metals from fluids |
| CN103249814A (en) * | 2010-11-19 | 2013-08-14 | 雪佛龙美国公司 | Process, method, and system for removing heavy metals from fluids |
| CN102560098A (en) * | 2012-02-09 | 2012-07-11 | 苏州久王多铵盐科技有限公司 | Purpose of by-product ammonium thiosulfate generated in steel-making waste water treatment process as complexing agent for leaching silver and its application method |
| CN103548631A (en) * | 2013-10-24 | 2014-02-05 | 中国科学院高能物理研究所 | Method for reducing mercury content in rice |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104722574A (en) * | 2015-02-13 | 2015-06-24 | 苏州久王环保科技股份有限公司 | New method for repairing mercury polluted soil by using byproduct ammonium thiosulfate recycled from coking desulfurization waste solution |
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