CN102784721B - Enrichment and recovery method for selenium and mercury in toxic smelting fume - Google Patents
Enrichment and recovery method for selenium and mercury in toxic smelting fume Download PDFInfo
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- CN102784721B CN102784721B CN201210296461.9A CN201210296461A CN102784721B CN 102784721 B CN102784721 B CN 102784721B CN 201210296461 A CN201210296461 A CN 201210296461A CN 102784721 B CN102784721 B CN 102784721B
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- pulp
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- ore
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- 238000003723 Smelting Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 27
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title abstract description 26
- 229910052711 selenium Inorganic materials 0.000 title abstract description 24
- 239000011669 selenium Substances 0.000 title abstract description 24
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title abstract description 16
- 229910052753 mercury Inorganic materials 0.000 title abstract description 16
- 238000011084 recovery Methods 0.000 title abstract description 14
- 239000003517 fume Substances 0.000 title abstract description 5
- 231100000331 toxic Toxicity 0.000 title abstract 2
- 230000002588 toxic effect Effects 0.000 title abstract 2
- 238000005188 flotation Methods 0.000 claims abstract description 19
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- 239000012141 concentrate Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 3
- YQMLDSWXEQOSPP-UHFFFAOYSA-N selanylidenemercury Chemical compound [Hg]=[Se] YQMLDSWXEQOSPP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000428 dust Substances 0.000 claims description 18
- 239000000779 smoke Substances 0.000 claims description 18
- 231100000614 poison Toxicity 0.000 claims description 16
- 230000007096 poisonous effect Effects 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 235000019353 potassium silicate Nutrition 0.000 claims description 14
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- 239000003500 flue dust Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 abstract description 9
- 239000004088 foaming agent Substances 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003929 acidic solution Substances 0.000 abstract 1
- 230000003750 conditioning effect Effects 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 230000002000 scavenging effect Effects 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000008040 ionic compounds Chemical group 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- PKMXSWXQNCMWNG-UHFFFAOYSA-L lead(2+);selenate Chemical compound [Pb+2].[O-][Se]([O-])(=O)=O PKMXSWXQNCMWNG-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Abstract
The invention discloses enrichment and recovery technology for selenium and mercury in toxic smelting fume. The technology includes preparing flotation pulp after ores are ground; conditioning the flotation pulp so that the mass percent thereof ranges from 10% to 12%; stirring and uniformly mixing the flotation pulp; then adding acidic solution into the pulp until the pH (potential of hydrogen) value of the pulp ranges from 2 to 4; adding inhibitors into the pulp under the condition that collectors are not added; and sequentially performing roughing, concentration and scavenging for the mixture to obtain selenium and mercury concentrates. In the enrichment and recovery technology, only the inhibitors are added into the pulp, the collectors or foaming agents are omitted.
Description
Technical field
The present invention relates to a kind of from poisonous smelting smoke dust the technology of enriching and recovering selenium mercury, belong to the Mineral Processing Engineering field.
Background technology
2006～2007 years, world's selenium annual production reached 2200～2500t.The about 82000t of world's selenium reserves, Chile and China respectively account for 16000t, but callable selenium resource only can be estimated by the selenium content of copper mine.Therefore, the callable selenium resource of China and few.At present, the primary raw material that extracts selenium is the earth of positive pole of electrolytical refined copper, the flue dust of lead blast furnace, the flue dust of sulfuric acid plant and sour mud, fume from steel making, lead and zinc concentrate calcination fume, the waste material that pyrite roasting slag and mercury, gold are produced.Selenium mainly is to reclaim from copper pyrometallurgy, and on a small quantity in nickel, recovery when cobalt is smelted, but callable resource increment is little generally.Reclaim classical the technology----sulfating roasting method of selenium, though simple, seriously polluted, environmental protection pressure is large, the loss of simultaneous harmful element mercury.In addition, because the ratio of wet type copper smelting increasing, and the selenium of association is unrenewable in this part copper mine.Because above-mentioned factors has limited the dissipated metal industry and efficiently and has fast developed.The defective that exists in the prior art becomes those skilled in the art's technical problem anxious to be resolved.
Summary of the invention
The technology of the present invention purpose is to overcome the deficiencies in the prior art, solves tradition and reclaims environmental pollution and the not high problem of recovery utilization rate that exists in the selenium mercury method; Provide a kind of from poisonous smelting smoke dust the method for enriching and recovering selenium mercury, utilize rational regime of agent, thereby make the kohlerite thing float to reach the purpose of enrichment by flotation.
The present invention is achieved through the following technical solutions the object of the invention, the inventive method comprise ore grinding, selected, the step such as roughly select, scan, in sorting process, do not add any collecting agent and foaming agent, and only be to have added inhibitor.Be specially: prepare flotation pulp after collecting poisonous smelting smoke dust ore grinding, and the mass percentage concentration of regulating flotation pulp is 10～12%, stir and evenly mix, stirring intensity is 1000～1400 to turn/min, adding acid solution to the pH value of ore pulp is 2～4 in ore pulp, in the situation that does not add collecting agent, add inhibitor waterglass in the ore pulp and calgon is roughly selected successively, selected, scan, namely obtain selenium mercury concentrate, every kind of inhibitor is added in the ore pulp in the ratio that flue dust per ton adds 600～1000g when wherein roughly selecting, roughly select in two steps that (every kind of inhibitor total amount is 600～1000g) in two steps, and every kind of inhibitor is added in the ore pulp in the ratio that flue dust per ton adds 300～500g when scanning.
Acid solution described in the present invention is sulfuric acid, and its mass percent concentration is 5～10%, and at this, sulfuric acid also has activation to the kohlerite thing except regulating the pH value.
Inhibitor described in the present invention is commercial Conventional flotation medicament.
Among the present invention behind the ore grinding smoke granularity account for 85～95% for-400 orders.
Poisonous smelting smoke dust is to derive from the smelting smoke dust that produces in the mineral smelting processes such as copper, lead, zinc among the present invention.
Principle: elemental selenium belongs to oxygen group elements in the periodic table of elements, has the character similar with element sulphur, and its outermost electron number is 6, has the strong electronic capability that gets; And element mercury belongs to metallic element, and it often is combined with the form of ionic bond with nonmetalloid, exists with the ionic compound form, and mercuric sulphide is exactly one of sulfide of the common mercury of a class, and its native floatability is better.Therefore, the elemental selenium that has a similar quality with element sulphur also has preferably native floatability when forming mercury selenide with mercury.According to these characteristics, the present invention adopts without collecting agent selenium minerals is carried out flotation, has both realized the recovery to the mercury selenide mineral, has alleviated again the enrichment of gangue in concentrate.Therefore the present invention only adopts inhibitor to suppress gangue, and does not use collecting agent.
Advantage of the present invention and effect are as follows:
1, since this technology by method for floating enriching and recovering kohlerite thing from poisonous smelting smoke dust, it is as follows to have solved the Enriching Selenium mercury rate of recovery is not high in the past shortcoming advantage of the present invention and effect:
, in the technology that sorts, do not add collecting agent and foaming agent, and just adopted inhibitor, simplified technological process, by once sorting the sorting index that reaches higher, brought higher economic benefit;
2, than technology---the multiple recovery methods such as-sulfating roasting method of routine, the inventive method less pollution can not produce selenium dioxide in the process, and harmful element mercury also obtains enrichment simultaneously, becomes selenium mercury bulk concentrate.Thereby can effectively reach the purpose of environmental protection;
3, the traditional handicraft of Enriching Selenium---method of roasting can cause volatilization, the condensation of poisonous element mercury, thus contaminated environment, even enter and bring great harm in the human body; By this technology, the poisonous element mercury that exists in the ore is accompanied by selenium and is together got up to become selenium mercury bulk concentrate by enrichment, and this poisonous element is recycled, and has reduced the pollution to environment.
The specific embodiment
Below in conjunction with embodiment the present invention is described further, but protection domain of the present invention is not limited to described content, except specified otherwise, additive method is routine techniques among the embodiment.
Embodiment 1:The method of enriching and recovering selenium mercury from poisonous smelting smoke dust, concrete operations are as follows:
Collect the smelting smoke dust of Dongchuan District, Yunnan Province production of copper, this flue dust is red, and dust solid sample, former state Relative Size be thin (200 orders account for 90%); Learn that through multielement analysis, XRD analysis the selenium grade is 2.18% in this flue dust, the main existence form of selenium and mercury is mercury selenide and lead selenate.
Account for 95% to-400 orders with the 500g calcination fume is levigate, the inflatable mechanical stirring flotation machine is adopted in flotation, and stirring intensity is 1000 to turn/min; The mass percentage concentration of regulating flotation pulp is 10%; Adding sulfuric acid solution (mass percent concentration is 5%) adjusting slurry pH is 2, in the situation that does not add collecting agent, add inhibitor waterglass in the ore pulp and calgon roughly select successively, selected, scan, roughly select wherein that the waterglass addition is that 200g/t, calgon addition are 200g/t in one; Roughly select that the waterglass addition is that 600g/t, calgon addition are 600g/t in two; Scanning middle waterglass addition is that 400g/t, calgon addition are 400g/t.Through above-mentioned floatation process, can obtain containing selenium 5.254%, selenium recovery is 89%, and is mercurous 16.9%, the selenium mercury concentrate of the mercury rate of recovery 90.2%.
Embodiment 2: the method for enriching and recovering selenium mercury from poisonous smelting smoke dust, and concrete operations are as follows:
Get Huize, yunnan lead-zinc smelting flue dust, be dark-brown, the dust solid sample.Through multielement analysis, XRD analysis as can be known, wherein the selenium grade is 5.026%, and mercury mainly exists with the form of mercuric sulphide in this flue dust.
Account for 90% to-400 orders with this flue dust of 500g is levigate, the inflatable mechanical stirring flotation machine is adopted in flotation, and stirring intensity is 1200 to turn/min; The mass percentage concentration of regulating flotation pulp is 11%; Then adding sulfuric acid solution (mass percent concentration is 8%) adjusting slurry pH is 3, in the situation that does not add collecting agent, add inhibitor in the ore pulp and be waterglass and calgon roughly select, selected, scan, roughly select wherein that addition is that waterglass 200g/t, calgon addition are 800g/t in one; Roughly select that the waterglass addition is that 400g/t, calgon addition are 200g/t in two; Scanning middle waterglass addition is that 300g/t, calgon addition are 500g/t.Through above-mentioned floatation process, can obtain containing selenium 9.056%, selenium recovery 89%, mercurous 18.6%, the selenium mercury concentrate of the mercury rate of recovery 90.15%.
Embodiment 3: the method for enriching and recovering selenium mercury from poisonous smelting smoke dust, and concrete operations are as follows:
Get the plumbous zinc ore smelting smoke dust of Area, Gejiu District, Yunnan Province.Through multielement analysis, material phase analysis as can be known, mainly have bloodstone, sardinianite, cinnabar, horn silver, zincblende, mercury chloride etc. in this flue dust, wherein the selenium grade is 3.32%.
At Dongchuan pilot plant this flue dust of 10t is carried out pilot scale trial production, material is accounted for 85% by levigate to-400 orders, and the inflatable mechanical stirring flotation machine is adopted in flotation, and stirring intensity is 1400 to turn/min; The mass percentage concentration of regulating flotation pulp is 12%; Then adding sulfuric acid solution (mass percent concentration is 10%) adjusting slurry pH is 4, in the situation that does not add collecting agent, add inhibitor in the ore pulp and be waterglass and calgon roughly select, selected, scan, roughly select wherein that the waterglass addition is that 400g/t, calgon addition are 300g/t in one; Roughly select that the waterglass addition is that 600g/t, calgon addition are 300g/t in two; Scanning middle waterglass addition is that 500g/t, calgon addition are 300g/t.Through above-mentioned floatation process, can obtain concentrate and contain selenium 7.37%, selenium recovery 80.54%, mercurous 20.5%, the selenium mercury concentrate of the mercury rate of recovery 88.72%.
Claims (3)
1. the method for an enriching and recovering selenium mercury from poisonous smelting smoke dust, the method comprises ore grinding, roughly select, selected, scan, it is characterized in that: prepare flotation pulp after collecting poisonous smelting smoke dust ore grinding, and the mass percentage concentration of regulating flotation pulp is 10～12%, stir and evenly mix, stirring intensity is 1000～1400 to turn/min, adding acid solution to the pH value of ore pulp is 2～4 in ore pulp, in the situation that does not add collecting agent, add inhibitor waterglass in the ore pulp and calgon is roughly selected successively, selected, scan, namely obtain selenium mercury concentrate, every kind of inhibitor is added in the ore pulp in the ratio that flue dust per ton adds 600～1000g when wherein roughly selecting, roughly select and carry out twice, every kind of inhibitor is added in the ore pulp in the ratio that flue dust per ton adds 300～500g when scanning.
2. according to the method for enriching and recovering selenium mercury from poisonous smelting smoke dust of claim 1, it is characterized in that: acid solution is sulfuric acid solution, and its mass percent concentration is 5～10%.
3. according to claim 1 the method for enriching and recovering selenium mercury from poisonous smelting smoke dust, it is characterized in that: smoke granularity accounts for 85～95% for-400 orders behind the ore grinding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210296461.9A CN102784721B (en) | 2012-08-21 | 2012-08-21 | Enrichment and recovery method for selenium and mercury in toxic smelting fume |
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| CN201210296461.9A CN102784721B (en) | 2012-08-21 | 2012-08-21 | Enrichment and recovery method for selenium and mercury in toxic smelting fume |
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| CN102784721A CN102784721A (en) | 2012-11-21 |
| CN102784721B true CN102784721B (en) | 2013-10-16 |
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| CN104294052B (en) * | 2014-09-26 | 2017-06-16 | 中南大学 | A kind of preprocess method of noble metal metallurgy flue dust |
| CN115595433B (en) * | 2022-11-30 | 2023-02-28 | 昆明理工大学 | System for extracting valuable metals from acid mud with high selectivity by microwaves |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626647A (en) * | 1992-09-22 | 1997-05-06 | Geobiotics, Inc. | Method for recovering gold and other precious metals from carbonaceous ores |
| CN1421515A (en) * | 2001-11-23 | 2003-06-04 | 朱珍锦 | Method of reducing the exhausted toxic heavy metal pollutent in fume of coal-burning boiler |
| CN101342443A (en) * | 2007-07-12 | 2009-01-14 | 天津宝成机械集团有限公司 | Method for reducing hydrargyrum and chromium in flue gas discharged from coal-fired boiler |
-
2012
- 2012-08-21 CN CN201210296461.9A patent/CN102784721B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626647A (en) * | 1992-09-22 | 1997-05-06 | Geobiotics, Inc. | Method for recovering gold and other precious metals from carbonaceous ores |
| CN1421515A (en) * | 2001-11-23 | 2003-06-04 | 朱珍锦 | Method of reducing the exhausted toxic heavy metal pollutent in fume of coal-burning boiler |
| CN101342443A (en) * | 2007-07-12 | 2009-01-14 | 天津宝成机械集团有限公司 | Method for reducing hydrargyrum and chromium in flue gas discharged from coal-fired boiler |
Non-Patent Citations (2)
| Title |
|---|
| 分银炉烟尘银、硒综合回收新工艺;黎英等;《有色金属(冶炼部分)》;20111031(第10期);第34～36页 * |
| 黎英等.分银炉烟尘银、硒综合回收新工艺.《有色金属(冶炼部分)》.2011,(第10期),第34～36页. |
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