CN103276217B - Comprehensive recycling process for polymetallic material containing gold and silver - Google Patents
Comprehensive recycling process for polymetallic material containing gold and silver Download PDFInfo
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- CN103276217B CN103276217B CN201310244873.2A CN201310244873A CN103276217B CN 103276217 B CN103276217 B CN 103276217B CN 201310244873 A CN201310244873 A CN 201310244873A CN 103276217 B CN103276217 B CN 103276217B
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- silver
- gold
- slag
- bismuth
- liquid
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 96
- 239000004332 silver Substances 0.000 title claims abstract description 96
- 239000010931 gold Substances 0.000 title claims abstract description 79
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000004064 recycling Methods 0.000 title claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 54
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000010949 copper Substances 0.000 claims abstract description 46
- 229910052802 copper Inorganic materials 0.000 claims abstract description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 44
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052718 tin Inorganic materials 0.000 claims abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011133 lead Substances 0.000 claims abstract description 24
- 238000002386 leaching Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 15
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 90
- 239000007788 liquid Substances 0.000 claims description 88
- 239000002893 slag Substances 0.000 claims description 63
- 238000007654 immersion Methods 0.000 claims description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 31
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 238000002791 soaking Methods 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 238000003723 Smelting Methods 0.000 claims description 13
- 229910052787 antimony Inorganic materials 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 12
- AHUBLGVDRKDHAT-UHFFFAOYSA-N [Bi]=O.[Cl] Chemical compound [Bi]=O.[Cl] AHUBLGVDRKDHAT-UHFFFAOYSA-N 0.000 claims description 11
- 235000017550 sodium carbonate Nutrition 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000004065 wastewater treatment Methods 0.000 claims description 8
- FQEZLJDDYYNLPP-UHFFFAOYSA-N carbonic acid;tin Chemical compound [Sn].OC(O)=O FQEZLJDDYYNLPP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 235000002505 Centaurea nigra Nutrition 0.000 claims description 5
- 241001073742 Mylopharodon conocephalus Species 0.000 claims description 5
- 229910001245 Sb alloy Inorganic materials 0.000 claims description 5
- 239000002140 antimony alloy Substances 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 3
- YGZCHNRGFZQAKR-UHFFFAOYSA-N [Sn].S(O)(O)=O Chemical compound [Sn].S(O)(O)=O YGZCHNRGFZQAKR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- DAFYMZZLYPHPNG-UHFFFAOYSA-N gold;thiourea Chemical compound [Au].NC(N)=S DAFYMZZLYPHPNG-UHFFFAOYSA-N 0.000 claims description 3
- 239000011499 joint compound Substances 0.000 claims description 3
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 150000003378 silver Chemical class 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 229910021607 Silver chloride Inorganic materials 0.000 abstract description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052946 acanthite Inorganic materials 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 abstract description 2
- 229940056910 silver sulfide Drugs 0.000 abstract description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 abstract 2
- 229910001923 silver oxide Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 description 6
- ZWFRZGJUJSOHGL-UHFFFAOYSA-N [Bi].[Cu].[Sn] Chemical compound [Bi].[Cu].[Sn] ZWFRZGJUJSOHGL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical compound [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 241000271566 Aves Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 208000029039 cyanide poisoning Diseases 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 231100000517 death Toxicity 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 thiourea peroxide Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material 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
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a comprehensive recycling process for polymetallic material containing gold and silver, belongs to the field of non-ferrous metal comprehensive recovery, and mainly comprises the following steps: ball-milling polymetallic material containing gold and silver, leaching bismuth, copper and tin from the polymetallic material by sulfuric acid leaching agent and ferric chloride, recovering the bismuth, copper and tin; retaining lead, gold and silver in the first leaching residue; and recovering the lead, gold and silver. According to the comprehensive recycling process provided by the invention, bismuth, copper and tin are leached from the polymetallic material by sulfuric acid leaching agent and ferric chloride, the oxidation of the ferric in the ferric chloride, and the chloride solution function of the chloride ion to bismuth and tin are creatively utilized, the addition of sulfuric acid and ferric chloride has the effect of changing silver oxide and silver sulfide into silver chloride, so as to reduce the chlorination step cost, and further reduce the dosage of sodium chlorate and hydrochloric acid, and the leaching rate of gold and silver is greatly improved accordingly. The comprehensive recycling process provided by the invention has the advantages that the technology is simple and practicable, the process is short, the device is simple, and the operation is convenient; and the adopted raw material is common, cheap and pollution free.
Description
Technical field
The present invention relates to a kind of comprehensive recycling process containing the many metalliferous materials of gold and silver, the invention belongs to non-ferrous metal and comprehensively reclaim field.
Background technology
Prior art is all to adopt with the laggard blast furnace of leaded high proportioning materials or oxygen enrichment system stove (as side-blown converter, bottom convertor etc.) melting to form lead-containing alloy or lead bullion containing the many metalliferous materials of gold and silver conventionally, its output after the operations such as electrolysis, anode sludge converter melting is slightly silver-colored, then obtains ingot, silver ingot through operations such as electrolytic silver, gold purifications; Need to just can obtain gold and silver through pyrometallurgical smelting repeatedly like this, and pyrometallurgical smelting only can make in system the heavy metals such as much volatile lead, antimony flow in flue gas serious environment pollution and make productive labor environment and poor repeatedly, very big to operator's human health damage, and its direct yield low (lower than 80%); Also have plenty of take sour pre-treatment after Cyanide Leaching will after gold and silver leaching wherein, reclaim, the prussiate such as the relatively high and sodium cyanide of production cost, potassium cyanide belongs to hypertoxic chemical substance like this, careless slightlyly just may cause cyanide poisoning, cause life injures and deaths, and contain cyanogen root material, serious harm environment in its generation processing wastewater.
Prior art related to the present invention has: on 02 27th, 2013, Chinese invention patent application publication number CN 102943180 A, the method that disclosed a kind of silver separating residue of copper anode slime gold and silver reclaims, is that silver separating residue of copper anode slime and Sulfothiorine are carried out to batch mixing and ball milling, obtains ball milling material; Ball milling material and reaction solvent are packed into and in hydrothermal reaction kettle, carry out hydro-thermal reaction; Hydrothermal product is filtered in the hydro-thermal liquid obtaining and adds thiourea peroxide to carry out reduction reaction, obtain thick metal(lic)powder.But this technique is only considered to reclaim gold and silver and directly process without pre-treatment, and cost is relatively large; Metal recovery is single, and recovery rate of valuable metals is relatively low.
In addition, the prior art that the present invention is relevant also has: on 03 27th, 2013, and Chinese invention patent application publication number CN 102994744 A, disclosed a kind of iron trichloride is processed the technique of lead matte, is that lead matte crushing grinding is screened to below 80 orders; Lead matte after grinding send leaching vat to carry out normal pressure leaching, controls FeCl
3concentration 200-400g/l, liquid-solid ratio 3-10:1, temperature 50-100 ℃, reaction times 4-8 hour.In order to improve leaching effect, shorten extraction time, can suitably blast air, and add a small amount of hcl acidifying.Under acidic conditions, utilize ferric ion to leach sulfide as oxygenant.In Oxidation Leaching process, the sulphur in lead matte is oxidized to elemental sulfur and transfers in slag, and copper is oxidized enters solution with ionic state, and lead is stayed in slag with form and the gold and silver of lead chloride; After leaching process completes, ore pulp carries out liquid-solid separation while hot, realizes the initial gross separation of copper-lead; In rich copper leach liquor, add scrap iron, displacement copper wherein, can obtain primary products copper sponge.
Summary of the invention
The object of this invention is to provide a kind of comprehensive recycling process containing the many metalliferous materials of gold and silver, by the Separation and Recovery from many metalliferous materials such as gold and silver, bismuth, copper, tin, the problem such as simultaneously solved that gold and silver direct yield is relatively low, technical process is long, turnover of funds is slow, waste gas, contaminated wastewater are serious.
Technical scheme of the present invention is: a kind of comprehensive recycling process containing the many metalliferous materials of gold and silver is by containing after many metalliferous materials of gold and silver ball milling, uses sulfuric acid leaching agent and iron(ic) chloride that bismuth wherein, copper, tin are leached from many metalliferous materials; After filtration, bismuth is present in an immersion liquid with the form of sulfurous acid tin with copper sulfate, tin with bismuth chloride, copper, and lead is stayed and once soaked in slag with the form of lead sulfate, and gold and silver is also stayed and once soaked in slag; In an immersion liquid, add alkali lye, bismuth just precipitates with the form of chlorine oxygen bismuth, and this chlorine oxygen bismuth just can obtain smart bismuth after by reverberatory smelting, bismuth refining; In liquid after heavy bismuth, add iron powder just the copper in solution can be precipitated at the form with copper sponge, this copper sponge just can obtain 1# copper after copper converting, electrolysis; In liquid after heavy copper, add soda ash, the form by the tin in solution with carbonic acid tin precipitates, and this carbonic acid tin just can obtain refined tin after reverberatory smelting, tin refining; Once soak hydrochloric acid for dreg and sodium chlorate and leach chlorination, the secondary after filtration soaks slag, and with silver after ammoniacal liquor leaching, the form with silver-colored ammonia is present in three immersion liquid, adds hydrazine hydrate reduction to obtain sponge silver powder in this silver ammino solution; With thiocarbamide, ferric sulfate and sulfuric acid, by after soaking gold in slag for three times and leaching, gold is present in four immersion liquid with the form of Gold Thiourea, with zinc powder, will after gold displacement, obtain gold and silver slag or gold mud, and gold and silver slag obtains ingot and silver ingot after purifying; Thiocarbamide leaches soaks slag for four times and enters pyrometallurgical smelting and obtain lead alloy or lead, antimony alloy;
Concrete technology flow process is:
(1) raw materials pretreatment
By containing the raw material of the many metalliferous materials of gold and silver with below grinding of ball grinder to 200 order;
(2) once leach
Toward adding sulfuric acid, iron(ic) chloride in the good raw material of ball milling, in quality liquid-solid ratio, be stirring reaction 3-4 hour under the condition of 3-4:1, temperature 85-95 ℃, filter, obtain once soaking slag and an immersion liquid, the add-on of sulfuric acid be raw material dry weight 40%, iron(ic) chloride add-on is 20% of raw material dry weight;
Principal reaction has: CuO+H
2sO
4=CuSO
4+ H
2o
PbO?+?2H
2SO
4?＝?PbSO
4↓+?2?H
2O
Bi
2O
3+6H
++6Cl
-?＝3H
2O?+2BiCl
3?
(3) separation of Bismuth, copper, tin
3a adds sodium hydroxide that pH is adjusted to 2.0-2.5 in an immersion liquid, under the condition of normal temperature, reacts 1-2 hour, filters and to obtain liquid after chlorine oxygen bismuth and heavy bismuth;
3b adds iron powder in liquid after heavy bismuth, the add-on of iron powder for heavy bismuth after in liquid containing the 1.1-1.2 of weight of copper doubly, stirring reaction 1-2 hour under the condition of normal temperature, filters and obtains liquid and copper sponge after heavy copper;
3c adds soda ash that pH is adjusted to 4.5-5.0 in liquid after heavy copper, and stirring reaction 1-2 hour under the condition of normal temperature filters and obtains liquid after hardhead and heavy tin, and after heavy tin, liquid liquid send waste water workshop to process;
Principal reaction has: BiCl
3+ 2NaOH → BiOCl ↓+2NaCl+H
2o
Fe+CuSO
4?→FeSO
4+Cu↓
SnSO
4?+2NaCO
3→Sn?CO
3↓+Na2SO
4
(4) chlorination
Toward once soaking in slag, adding hydrochloric acid and sodium chlorate, is to react after 3-4 hour under the condition of 4-5:1, temperature 85-95 ℃ in quality liquid-solid ratio, filters to obtain secondary and soak slag and secondary leach liquor; The access control amount of hydrochloric acid is for once soaking 40% of slag dry weight, and the access control amount of sodium chlorate is for once soaking 5% of slag dry weight; Secondary leach liquor recycles after sending wastewater treatment;
(5) ammoniacal liquor soaks silver and reclaims sponge silver
5a ammoniacal liquor soaks silver: toward secondary, soak and in slag, add under the condition that ammoniacal liquor is 5-6:1 in normal temperature, quality liquid-solid ratio after 3-4 hour stirring reaction time, filter and obtain soaking for three times slag and three immersion liquid; The add-on of ammoniacal liquor is 2 times that secondary soaks slag dry weight;
Principal reaction has: AgCl+2NH3.H2O → Ag (NH3) 2Cl+2H2O
5b reclaims sponge silver: in three immersion liquid, add hydrazine hydrate, the add-on of hydrazine hydrate is 2 times of silver amount in three immersion liquid, and under the condition of normal temperature, stirring reaction is 1 hour, filters, obtain sponge silver and silver-removing liquor, silver-removing liquor recycles after sending effluent treatment plant to process;
(6) soak after gold and ammoniacal liquor soak silver and remain in the silver in leached mud three times
Toward three times, soak in slag and add sulfuric acid that pH is adjusted to 2.0, then add thiocarbamide, ferric sulfate, quality liquid-solid ratio 5-7:1; The add-on of thiocarbamide be soak in slag gold and silver amount summation for three times 15-25 doubly, the add-on of ferric sulfate is to soak the 1-3% of slag amount three times; Under the condition of normal temperature, stir after 2-3 hour and filter and obtain four immersion liquid and soak slag four times, soak slag for four times and utilize the method for conventional pyrometallurgical smelting to reclaim lead, antimony valuable metal or lead, antimony alloy wherein;
Principal reaction has: Au+Fe
3++ 2SCN
2h
4→ [Au (SCN
2h
4)
2]
++ Fe
2+
Ag+Fe
3++2SCN
2H
4→[Ag(SCN
2H
4)
2]
++?Fe
2+
(7) reclaim the gold in four immersion liquid
In four immersion liquid, add zinc powder, the add-on of zinc powder is 15-25 times of golden amount in four immersion liquid, stirs after 1-2 hour and filter and obtain gold and silver slag and remove gold and silver liquid under the condition of normal temperature; Remove after gold and silver liquid send waste water workshop to process and recycle.
Compared with the existing technology, the present invention has following advantage: use acid lixiviant and iron(ic) chloride that bismuth wherein, copper, tin etc. are leached from many metalliferous materials; Creationaryly utilized ferric oxygenizement and chlorion in iron(ic) chloride to kill two birds with one stone to the chlorinating dissolution effect of bismuth, tin, and in the present invention, add sulfuric acid and iron(ic) chloride to also have an effect exactly silver suboxide and silver sulfide etc. to be become to silver chloride, reduce chlorinating step cost, and then can reduce sodium chlorate and hydrochloric acid consumption.Greatly improve gold and silver leaching rate.The present invention has simple for process, and flow process is short, and equipment is simple, simple to operate; Raw materials used more common and cheap, waste liquid recycles, the feature such as pollution-free.The present invention focuses on wastewater treatment, environmentally friendly, is conducive to environment protection.
Accompanying drawing explanation
Accompanying drawing 1 is process flow sheet.
Embodiment
Below in conjunction with accompanying drawing, with specific embodiment, the present invention is further described in detail.
Accompanying drawing 1 represents a kind of comprehensive recycling process containing the many metalliferous materials of gold and silver, is by containing after many metalliferous materials of gold and silver ball milling, uses sulfuric acid leaching agent and iron(ic) chloride that bismuth wherein, copper, tin are leached from many metalliferous materials; After filtration, bismuth is present in an immersion liquid with the form of sulfurous acid tin with copper sulfate, tin with bismuth chloride, copper, and lead is stayed and once soaked in slag with the form of lead sulfate, and gold and silver is also stayed and once soaked in slag; Toward adding alkali lye that pH is adjusted to the such bismuth of 2.0-2.5 in an immersion liquid, just with the form of chlorine oxygen bismuth, precipitate, this chlorine oxygen bismuth just can obtain smart bismuth after by reverberatory smelting, bismuth refining; In liquid after heavy bismuth, add iron powder just the copper in solution can be precipitated at the form with copper sponge, this copper sponge just can obtain 1# copper after copper converting, electrolysis; In liquid after heavy copper, add soda ash that pH is adjusted to 4.5-5.0, the form by the tin in solution with carbonic acid tin precipitates, and this carbonic acid tin just can obtain refined tin after reverberatory smelting, tin refining; Once soak hydrochloric acid for dreg and sodium chlorate and leach chlorination, the secondary after filtration soaks slag, and with silver after ammoniacal liquor leaching, the form with silver-colored ammonia is present in three immersion liquid, adds hydrazine hydrate reduction to obtain sponge silver powder in this silver ammino solution; With thiocarbamide, ferric sulfate and sulfuric acid, by after soaking gold in slag for three times and leaching, gold is present in four immersion liquid with the form of Gold Thiourea, with zinc powder, will after gold displacement, obtain gold and silver slag or gold mud, and gold and silver slag obtains ingot and silver ingot after purifying; Thiocarbamide leaches soaks slag for four times and enters pyrometallurgical smelting and obtain lead alloy or lead, antimony alloy.
Embodiment 1
A kind of comprehensive recycling process concrete steps containing the many metalliferous materials of gold and silver are as follows:
(1) raw materials pretreatment: get raw material 500g levigate, wherein bismuth-containing 6.32%, tin 7.58%, copper 8.12%, antimony 6.53%, lead 28.68%, silver-colored 836.26g/t, golden 9.36g/t;
(2) once leach: in this raw material, add sulfuric acid 200g, iron(ic) chloride 100g, water 2000g; Under the condition of temperature 85-95 ℃, stirring reaction filters after 3.5 hours and obtains leached mud 288.32g one time; A leach liquor 1953.00mL, wherein bismuth-containing 15.56g/L, cupric 19.86 g/L, tin 18.45 g/L;
(3) separation of Bismuth, copper, tin:
3a adds sodium hydroxide that pH is adjusted to 2.5 in a leach liquor, shares dehydrogenation sodium oxide 57.10g, filters and obtains removing wherein bismuth-containing 61.98% of bismuth liquid 1898.00 mL, chlorine oxygen bismuth 48.54g(), bismuth direct yield 96.18%;
3b is toward adding 43.00g iron powder except in bismuth liquid, and under the condition of normal temperature, stirring reaction filters after 1.5 hours and obtains except bismuth copper liquid 1843.00 mL, copper sponge 47.93g(cupric 80.12%), copper direct yield 95.53%;
3c, toward adding soda ash that pH is adjusted to 5.0 except in bismuth copper liquid, shares and removes soda ash 75.00g, obtains containing hardhead 78.35g(stanniferous 45.53%), except bismuth copper tin liquor 18.6.00 mL, this liquid recycles after sending Waste Water Treatment to process;
(4) chlorination: add hydrochloric acid 115.33g, sodium chlorate 14.42g in a leached mud, water 752.00g, under the condition of temperature 85-95 ℃, stirring reaction filters after 3.5 hours and obtains secondary leached mud 269.98g, secondary leach liquor 803.00.00mL, and secondary leach liquor recycles after sending wastewater treatment;
(5) soak silver:
5a adds ammoniacal liquor 539.96g, water 850g in secondary leached mud, reacts 2.5 hours under the condition of normal temperature, filters and obtains soaking for three times slag 259.32g, three immersion liquid, 1309.00 mL(argentiferous 0.31g/L);
5b adds hydrazine hydrate 1.00g in three immersion liquid, and under the condition of normal temperature, stirring reaction filters and obtains sponge silver 0.44g(argentiferous 91.58% for 1 hour);
(6) soak after gold and ammoniacal liquor soak silver and remain in the silver in leached mud three times: toward three times, soak in slag and add sulfuric acid that pH is adjusted to 2.0, add again thiocarbamide 0.27g, ferric sulfate 5.19g, water 1300g, under the condition of normal temperature, stir after 2.5 hours to filter and obtain four immersion liquid 1299.00 mL(containing golden 0.0036g/L, silver-colored 0.0083g/L), soak that slag 235.321g(is leaded 54.84% for four times, antimony 12.10%), lead recovery 93.83%, antimony recovery 90.88%;
(7) reclaim the gold and silver in four immersion liquid: in four immersion liquid, add 0.31g zinc powder, in the little stirring of condition of normal temperature, after 1 hour, filter and obtain gold and silver slag 0.16g(containing gold 2.90%, silver 6.74%), gold direct yield 99.14%, counts the sponge silver silver raising recovery rate 98.95% that soaks output in silver-colored step in.
Embodiment 2
A kind of comprehensive recycling process concrete steps containing the many metalliferous materials of gold and silver are as follows:
(1) raw materials pretreatment: get raw material 10kg levigate, wherein bismuth-containing 8.62%, tin 28.18%, copper 6.53%, antimony 9.28%, lead 10.06%, silver-colored 8362.48g/t, golden 50.34g/t;
(2) once leach: in this raw material, add sulfuric acid 4kg, iron(ic) chloride 2kg, water 40kg; Under the condition of temperature 85-95 ℃, stirring reaction filters after 3.5 hours and obtains leached mud 4.32kg one time; A leach liquor 39.22L, wherein bismuth-containing 21.31g/L, cupric 16.12g/L, stanniferous 69.91g/L;
(3) separation of Bismuth, copper, tin:
3a adds sodium hydroxide that pH is adjusted to 2.5 in a leach liquor, shares dehydrogenation sodium oxide 1.10 kg, filters and obtains removing wherein bismuth-containing 67.32% of bismuth liquid 37.38L, chlorine oxygen bismuth 1.23 kg(), bismuth direct yield 95.99%;
3b is toward adding 0.75 kg iron powder except in bismuth liquid, and under the condition of normal temperature, stirring reaction filters after 1.5 hours and obtains except bismuth copper liquid 35.93L, copper sponge 0.82 kg(cupric 76.53%), copper direct yield 95.85%;
3c, toward adding soda ash that pH is adjusted to 5.0 except in bismuth copper liquid, shares and removes soda ash 1.48g, obtains containing hardhead 5.88 kg(stanniferous 46.13%), tin recovery rate 96.25%, except bismuth copper tin liquor 34.02L, this liquid recycles after sending Waste Water Treatment to process;
(4) chlorination: add hydrochloric acid 1.73 kg, sodium chlorate 0.22 kg in a leached mud, water 15.98 kg, under the condition of temperature 85-95 ℃, stirring reaction filters after 3.5 hours and obtains secondary leached mud 3.93 kg, secondary leach liquor 15.63L, and secondary leach liquor recycles after sending wastewater treatment;
(5) soak silver:
5a adds ammoniacal liquor 7.86 kg, water 12.58 kg in secondary leached mud, reacts 2.5 hours under the condition of normal temperature, filters and obtains soaking for three times slag 3.06 kg, three immersion liquid 19.82L(argentiferous 4.00g/L);
5b adds hydrazine hydrate 170g in three immersion liquid, and under the condition of normal temperature, stirring reaction filters and obtains sponge silver 85.46g(argentiferous 93.23% for 1 hour);
(6) soak after gold and ammoniacal liquor soak silver and remain in the silver in leached mud three times: toward three times, soak in slag and add sulfuric acid that pH is adjusted to 2.0, share desulfuration acid 1.50 kg, add again thiocarbamide 93.00g, ferric sulfate 61.20g, water 16.00kg, under the condition of normal temperature, stir after 2.5 hours to filter and obtain four immersion liquid 15.43L(containing golden 0.032g/L, silver-colored 0.24g/L), soak slag 2.88 kg (leaded 31.44%, antimony 29.04%), lead recovery 90.01 %, antimony recovery 90.12% for four times;
(7) reclaim the gold and silver in four immersion liquid: in four immersion liquid, add 85.00g zinc powder, in the little stirring of condition of normal temperature, after 1 hour, filter and obtain gold and silver slag 46.32g(containing gold 1.06%, silver 8.00%), gold direct yield 97.54%, counts the sponge silver silver raising recovery rate 99.23% that soaks output in silver-colored step in.
Embodiment 3
A kind of comprehensive recycling process concrete steps containing the many metalliferous materials of gold and silver are as follows:
(1) raw materials pretreatment: get raw material 10kg levigate, wherein bismuth-containing 6.31%, tin 3.14%, copper 10.53%, antimony 12.52%, lead 8.63%, silver-colored 1032.23g/t, golden 89.53g/t;
(2) once leach: in this raw material, add sulfuric acid 4kg, iron(ic) chloride 2kg, 1 kg hydrochloric acid, water 40kg; Under the condition of temperature 85-95 ℃, stirring reaction filters after 3 hours and obtains leached mud 3.82kg one time; A leach liquor 38.68L, wherein bismuth-containing 15.65g/L, cupric 26.13g/L, stanniferous 7.86g/L;
(3) separation of Bismuth, copper, tin:
3a adds sodium hydroxide that pH is adjusted to 2.5 in a leach liquor, shares dehydrogenation sodium oxide 1.32kg, filters and obtains removing wherein bismuth-containing 68.53% of bismuth liquid 37.62L, chlorine oxygen bismuth 0.88kg(), bismuth direct yield 95.57%;
3b is toward adding 1.18 kg iron powders except in bismuth liquid, and under the condition of normal temperature, stirring reaction filters after 1 hour and obtains except bismuth copper liquid 35.88L, copper sponge 1.25kg(cupric 80.18%), copper direct yield 95.18%;
3c, toward adding soda ash that pH is adjusted to 5.0 except in bismuth copper liquid, shares and removes soda ash 1.52g, obtains containing hardhead 0.66kg(stanniferous 45.82%), tin recovery rate 96.30%, except bismuth copper tin liquor 34.15L, this liquid recycles after sending Waste Water Treatment to process;
(4) soak silver:
4a adds ammoniacal liquor 7.64kg, water 12.00 kg in secondary leached mud, reacts 3 hours under the condition of normal temperature, filters and obtains soaking for three times slag 3.00 kg, three immersion liquid 19.53L(argentiferous 0.27g/L);
4b adds hydrazine hydrate 10.55g in three immersion liquid, and under the condition of normal temperature, stirring reaction filters and obtains sponge silver 5.72g(argentiferous 91.98% for 1 hour);
(5) soak after gold and ammoniacal liquor soak silver and remain in the silver in leached mud three times: toward three times, soak in slag and add sulfuric acid that pH is adjusted to 2.0, share desulfuration acid 1.62 kg, add again thiocarbamide 120.00g, ferric sulfate 60.00 g, water 15.00kg, under the condition of normal temperature, stir after 3 hours to filter and obtain four immersion liquid 14.98L(containing golden 0.059g/L, silver-colored 0.33g/L), soak slag 2.55 kg (leaded 30.46%, antimony 37.18%), lead recovery 90.00%, antimony recovery 90.12% for four times;
(6) reclaim the gold and silver in four immersion liquid: in four immersion liquid, add 120g zinc powder, in the little stirring of condition of normal temperature, after 1 hour, filter and obtain gold and silver slag 30.53g(containing gold 2.83%, silver 15.87%), gold direct yield 96.50%, counts the sponge silver silver raising recovery rate 97.91% that soaks output in silver-colored step in.
Claims (1)
1. containing a comprehensive recycling process for the many metalliferous materials of gold and silver, it is characterized in that, by containing after many metalliferous materials of gold and silver ball milling, using sulfuric acid leaching agent and iron(ic) chloride that bismuth wherein, copper, tin are leached from many metalliferous materials; After filtration, bismuth is present in an immersion liquid with the form of sulfurous acid tin with copper sulfate, tin with bismuth chloride, copper, and lead is stayed and once soaked in slag with the form of lead sulfate, and gold and silver is also stayed and once soaked in slag; In an immersion liquid, add alkali lye, bismuth just precipitates with the form of chlorine oxygen bismuth, and this chlorine oxygen bismuth just can obtain smart bismuth after by reverberatory smelting, bismuth refining; In liquid after heavy bismuth, add iron powder just the copper in solution can be precipitated at the form with copper sponge, this copper sponge just can obtain 1# copper after copper converting, electrolysis; In liquid after heavy copper, add soda ash, the form by the tin in solution with carbonic acid tin precipitates, and this carbonic acid tin just can obtain refined tin after reverberatory smelting, tin refining; Once soak hydrochloric acid for dreg and sodium chlorate and leach chlorination, the secondary after filtration soaks slag, and with silver after ammoniacal liquor leaching, the form with silver-colored ammonia is present in three immersion liquid, adds hydrazine hydrate reduction to obtain sponge silver powder in this silver ammino solution; With thiocarbamide, ferric sulfate and sulfuric acid, by after soaking gold in slag for three times and leaching, gold is present in four immersion liquid with the form of Gold Thiourea, with zinc powder, will after gold displacement, obtain gold and silver slag or gold mud, and gold and silver slag obtains ingot and silver ingot after purifying; Thiocarbamide leaches soaks slag for four times and enters pyrometallurgical smelting and obtain lead alloy or lead, antimony alloy;
Concrete technology flow process is:
(1) raw materials pretreatment
By containing the raw material of the many metalliferous materials of gold and silver with below grinding of ball grinder to 200 order;
(2) once leach
In the good raw material of ball milling, add sulfuric acid, iron(ic) chloride, in quality liquid-solid ratio, be stirring reaction 3-4 hour under the condition of 3-4:1, temperature 85-95 ℃, filter, obtain once soaking slag and an immersion liquid, the add-on of sulfuric acid be raw material dry weight 40%, iron(ic) chloride add-on is 20% of raw material dry weight;
(3) separation of Bismuth, copper, tin
3a adds sodium hydroxide that pH is adjusted to 2.0-2.5 in an immersion liquid, under the condition of normal temperature, reacts 1-2 hour, filters and to obtain liquid after chlorine oxygen bismuth and heavy bismuth;
3b adds iron powder in liquid after heavy bismuth, the add-on of iron powder for heavy bismuth after in liquid containing the 1.1-1.2 of weight of copper doubly, stirring reaction 1-2 hour under the condition of normal temperature, filters and obtains liquid and copper sponge after heavy copper;
3c adds soda ash that pH is adjusted to 4.5-5.0 in liquid after heavy copper, and stirring reaction 1-2 hour under the condition of normal temperature filters and obtains liquid after hardhead and heavy tin, and after heavy tin, liquid liquid recycles after sending waste water workshop to process;
(4) chlorination
Toward once soaking in slag, adding hydrochloric acid and sodium chlorate, is to react after 3-4 hour under the condition of 4-5:1, temperature 85-95 ℃ in quality liquid-solid ratio, filters to obtain secondary and soak slag and secondary leach liquor; The access control amount of hydrochloric acid is for once soaking 40% of slag dry weight, and the access control amount of sodium chlorate is for once soaking 5% of slag dry weight; Secondary leach liquor recycles after sending wastewater treatment;
(5) ammoniacal liquor soaks silver and reclaims sponge silver
5a ammoniacal liquor soaks silver: toward secondary, soak in slag and add ammoniacal liquor, under the condition that is 5-6:1, after 3-4 hour stirring reaction time, filter and obtain soaking for three times slag and three immersion liquid in normal temperature, quality liquid-solid ratio; The add-on of ammoniacal liquor is 2 times that secondary soaks slag dry weight;
5b reclaims sponge silver: in three immersion liquid, add hydrazine hydrate, the add-on of hydrazine hydrate is 2 times of silver amount in three immersion liquid, and under the condition of normal temperature, stirring reaction is 1 hour, filters, obtain sponge silver and silver-removing liquor, silver-removing liquor recycles after sending effluent treatment plant to process;
(6) soak after gold and ammoniacal liquor soak silver and remain in the silver in leached mud three times
Toward three times, soak in slag and add sulfuric acid, pH is adjusted to 2.0, then add thiocarbamide, ferric sulfate, quality liquid-solid ratio 5-7:1; The add-on of thiocarbamide be soak in slag gold and silver amount summation for three times 15-25 doubly, the add-on of ferric sulfate is to soak the 1-3% of slag amount three times; Under the condition of normal temperature, stir after 2-3 hour and filter and obtain four immersion liquid and soak slag four times, soak slag for four times and utilize the method for conventional pyrometallurgical smelting to reclaim lead, antimony valuable metal or lead, antimony alloy wherein;
(7) reclaim the gold in four immersion liquid
In four immersion liquid, add zinc powder, the add-on of zinc powder is 15-25 times of golden amount in four immersion liquid, stirs after 1-2 hour and filter and obtain gold and silver slag and remove gold and silver liquid under the condition of normal temperature; Remove after gold and silver liquid send waste water workshop to process and recycle.
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| CN112391531B (en) * | 2020-10-30 | 2021-12-17 | 中南大学 | Method for recovering valuable metals by microwave pyrolysis of waste circuit boards |
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Address after: 423000 Chenzhou City, Hunan province Suxian District Bridge Town sub Jiashan tin Tao chemical industry Patentee after: CHENZHOU YANGTAO ENVIRONMENTAL TECHNOLOGY CO.,LTD. Address before: 423000 Chenzhou City, Hunan province Suxian District Bridge Town sub Jiashan tin Tao chemical industry Patentee before: CHENZHOU YANGTAO CHEMICAL Co.,Ltd. |