CN104962747B - A kind of method of Copper making flue dust dearsenification - Google Patents
A kind of method of Copper making flue dust dearsenification Download PDFInfo
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- CN104962747B CN104962747B CN201510331231.5A CN201510331231A CN104962747B CN 104962747 B CN104962747 B CN 104962747B CN 201510331231 A CN201510331231 A CN 201510331231A CN 104962747 B CN104962747 B CN 104962747B
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- Prior art keywords
- flue dust
- dearsenification
- arsenic
- copper making
- copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 34
- 239000010949 copper Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003500 flue dust Substances 0.000 title claims abstract description 24
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 33
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 235000011149 sulphuric acid Nutrition 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 210000000481 breast Anatomy 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 235000019504 cigarettes Nutrition 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000002386 leaching Methods 0.000 abstract description 12
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 150000002506 iron compounds Chemical class 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Removal Of Specific Substances (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A kind of method of Copper making flue dust dearsenification, including collection, leaching, filtering, dearsenification and separation.The present invention makees arsenic oxidant using hydrogen peroxide, and oxidation efficiency after oxidation reaction is complete, only generates water, harmless to technological process, does not increase any removal of impurities flow.Short the present invention relates to flow, dearsenicating technology is directly added into high price iron compound, and dearsenification efficiency high, production arsenic scum amount is few, and production arsenic scum rate is less than other wet method dearsenication techniques about 30%, and environment protecting is good.
Description
Technical field
The invention belongs to technical field of wet metallurgy, and in particular to a kind of method of Copper making flue dust dearsenification.
Background technology
The method of a part of business processes Copper making flue dust is pyrogenic process, and pyrogenic attack is dearsenification first.Fire arsenic removal mistake
Cheng Jun is removing that arsenic volatilizees in the form of a vapor, and the gas arsenic generated is discharged into air, can cause environmental pollution, and fire
Method process, which can be produced in substantial amounts of flue gas, flue gas, contains SO2Deng pernicious gas, it is necessary to which handling could discharge after flue gas, and portion
Divide valuable metal(Such as indium, silver, lead)It is readily volatilized into flue gas at high temperature, cause the loss of valuable metal.
The method of processing Copper making flue dust is mostly wet method at present, and its technical process is to leach, except every, dearsenification, putting
Change, the process such as heavy zinc, heavy manganese, in leaching process, most methods are to be mixed with flue dust with industrial sulphuric acid, with MnO2Or Gao Meng
Sour potassium etc. makes substantial amounts of arsenic enter in leachate as oxidant, then adjusts pH value with milk of lime, is removed with+divalent iron
Arsenic.Use MnO2Make oxidant, make to add manganese ion in leachate, increased manganese ion, increase is accomplished by subsequent handling
Heavy manganese process, adds the yield of dangerous waste slag, and using potassium permanganate then toward potassium ion is added in filtrate, potassium ion is in liquid
In can not remove, always present in waste liquid.Therefore a kind of feasible flue dust arsenic removing method is found to Copper making dust treatment skill
Art has very important meaning.
The content of the invention
To solve the problem of above technology is present, the present invention provides a kind of method of the efficient dearsenification of Copper making flue dust.
Its technical scheme is:
A kind of method of Copper making flue dust dearsenification, it is characterised in that:Follow the steps below,
(1)Collect:Collect Copper making flue dust;
(2)Leach:Copper making flue dust is mixed with industrial sulphuric acid, 30~40% hydrogen peroxide are added in mixed liquor and are made
For oxidant, it is heated to 70 ~ 80 DEG C and is leached, extraction time is 2~3 hours;
(3)Filtering:Filter the product leached, separation leachate and leached mud;
(4)Dearsenification:After filtering, 50 ~ 60% high price iron is added in leachate, 80 ~ 90 DEG C are heated to, and use milk of lime
PH value is adjusted, is allowed to generate precipitated ferric arsenate precipitation, the dearsenification time is 3~4 hours;
(5)Separation:Isolate the ferric arsenate of Precipitation.
Such method, dearsenification efficiently facilitates, and does not introduce other elements, without be further added by unnecessary process come after removing how
Plus element, it is ensured that the removal efficiency of arsenic.
Further, industrial sulphuric acid concentration is 98g/L, by Copper making flue dust quality and sulfuric acid volume 1:3.5~4 ratio is entered
Row mixing.Being smoothed out for reaction has so been ensured, according to such ratio, maximum leaching has been can ensure that, reaction is abundant, also saves
Cost.
Further, quality containing arsenic and the hydrogen peroxide mass ratio added are 1 in Copper making flue dust:5.5~6.0.Ensure that oxidation is filled
Point, do not cause to waste, do not introduce new element.
Further, the terminal of regulation pH value is 0.8 ~ 1.0.This pH value is the best value range of dearsenification process.
Beneficial effect of the present invention:
(1)Technological process is simple, and flow is short.Because traditional arsenic oxidant has brought impurity element into, excessive remove is added
Miscellaneous flow, and the present invention only carries out efficient oxidation to the arsenic in Copper making flue dust by using hydrogen peroxide, shortens flow, reduces
Dangerous waste slag weight.
(2)Make arsenic oxidant using hydrogen peroxide, oxidation efficiency after oxidation reaction is complete, only generates water, to technological process without
Evil, does not increase any removal of impurities flow.
(3)The leaching rate of arsenic of the present invention is up to more than 70%, arsenic-removing rate and is up to more than 99%, higher than other wet method dearsenication techniques
Index.
(4)Short the present invention relates to flow, dearsenicating technology is directly added into high price iron compound, and dearsenification efficiency high produces arsenic scum
Amount is few, and production arsenic scum rate is less than other wet method dearsenication techniques about 30%, and environment protecting is good.
Embodiment
Copper making flue dust composition is:Copper:4.5%, lead:11.81%, zinc:15.15%, arsenic:9.91%, iron:2.39%, bismuth:
3.51%, indium:0.161%, silver:185.4g/t.
Embodiment 1
It is 98g/L to take concentration, and 350ml industrial sulphuric acids are poured into beaker, and take 100g Copper making flue dust to pour into beaker
Row stirring mixing, and 75 DEG C are heated to, and 35% hydrogen peroxide 50ml is slowly added dropwise toward beaker bottom, it is fully anti-at this temperature
Answer 2.5 hours.
The ammonium acetate drawn is:Copper 8.83g/L, zinc 25.42g/L, arsenic 13g/L, iron 0.805g/L.
Obtained leaching slag ingredient is:Copper 0.951%, zinc 3.7%, arsenic 7.15%, iron 2.24%, lead 23.52%.
The arsenic leaching rate of the experiment is 73.323%, and valuable metal leaching rate is:Copper 91.808%, zinc 90.707%.
By the leaching content of arsenic, with ferric amount needed for Chemical Calculation dearsenification.With above-mentioned produced leachate, after sampling
Remaining leachate, adds high price iron compound 45.5g mixing, is heated to 85 DEG C, and is stirred continuously, and adds milk of lime regulation
PH to 1.1, at this temperature, fully reaction 3 hours.
Obtained dearsenification liquid composition is:Copper 5.33g/L, zinc 16.52g/L, arsenic 0.3g/L, iron 5.1g/L.
The composition for obtaining arsenic scum is:Copper 0.154%, zinc 0.321%, arsenic 6.74%, iron 3.83%.
In the experiment, the arsenic-removing rate of leachate is 99.653%.
Embodiment 2
It is 98g/L to take concentration, and 700ml industrial sulphuric acids are poured into beaker, and take 200g Copper making flue dust to pour into beaker
Row stirring mixing, and 75 DEG C are heated to, and 30% hydrogen peroxide 100ml is slowly added dropwise toward beaker bottom, it is fully anti-at this temperature
Answer 3 hours.
The ammonium acetate drawn is:Copper 11.21g/L, zinc 23.67g/L, arsenic 16.1g/L, iron 1.16g/L.
Obtained leaching slag ingredient is:Copper 1.09%, zinc 3.53%, arsenic 6.72%, iron 1.8%, lead 23.71%.
The arsenic leaching rate of the experiment is 71.931%, and valuable metal leaching rate is:Copper 90.46%, zinc 89.89%.
By the leaching content of arsenic, with ferric amount needed for Chemical Calculation dearsenification.With above-mentioned produced leachate, after sampling
Remaining leachate, adds high price iron compound 105g mixing, is heated to 85 DEG C, and is stirred continuously, and adds milk of lime regulation
PH to 0.95, at this temperature, fully reaction 3 hours.
Obtained dearsenification liquid composition is:Copper 8.19g/L, zinc 25.05g/L, arsenic 0.6g/L, iron 3.02g/L.
The composition for obtaining arsenic scum is:Copper 0.234%, zinc 0.505%, arsenic 6.97%, iron 3.72%.
In the experiment, the arsenic-removing rate of leachate is 99.895%.
Claims (1)
1. a kind of method of Copper making flue dust dearsenification, it is characterised in that:Follow the steps below,
(1)Collect:Copper making flue dust is collected, flue dust composition is:Copper:4.5%, lead:11.81%, zinc:15.15%, arsenic:9.91%,
Iron:2.39%, bismuth:3.51%, indium:0.161%, silver:185.4g/t;
(2)Leach:Copper making flue dust is mixed with industrial sulphuric acid, 30~40% hydrogen peroxide are added in mixed liquor and are used as oxygen
Agent, is heated to 70 ~ 80 DEG C and is leached, and extraction time is 2~3 hours, and industrial sulphuric acid concentration is 98g/L, by Copper making cigarette
Dirt quality and sulfuric acid volume 1:3.5~4 ratio is mixed, quality containing arsenic and the dioxygen water quality added in Copper making flue dust
Than for 1:5.5~6.0;
(3)Filtering:Filter the product leached, separation leachate and leached mud;
(4)Dearsenification:After filtering, the high price iron of flue dust quality 50 ~ 60% is added in leachate, 80 ~ 90 DEG C are heated to, and use stone
Grey breast regulation pH value, is allowed to generate precipitated ferric arsenate precipitation, the dearsenification time is 3~4 hours, and regulation endpoint pH is 0.8 ~ 1.0;
(5)Separation:Isolate the ferric arsenate of Precipitation.
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CN106544513A (en) * | 2016-11-09 | 2017-03-29 | 河南中原黄金冶炼厂有限责任公司 | A kind of method of copper smelting by pyrometallurgy white cigarette dirt valuable metal recovery |
CN111334665B (en) * | 2020-03-12 | 2022-08-19 | 昆明理工大学 | Method for separating indium, copper, arsenic and zinc from multi-metal sulfuric acid solution |
CN112195346A (en) * | 2020-10-09 | 2021-01-08 | 长沙矿冶研究院有限责任公司 | Process for removing arsenic by conversion leaching of arsenic-containing soot in pyrometallurgy of copper and lead |
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CN103014355B (en) * | 2012-12-13 | 2014-12-24 | 马永涛 | Multi-metal comprehensive recycling process for copper smelting ash |
CN103014357A (en) * | 2013-01-18 | 2013-04-03 | 广西地博矿业集团股份有限公司 | Method for recovering arsenic from arsenic soot |
JP6139990B2 (en) * | 2013-06-11 | 2017-05-31 | Dowaメタルマイン株式会社 | Arsenic solution treatment method |
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