CN117964150A - 一种从高铜高银氰化黄金氰化废水资源综合回收方法 - Google Patents
一种从高铜高银氰化黄金氰化废水资源综合回收方法 Download PDFInfo
- Publication number
- CN117964150A CN117964150A CN202410153528.6A CN202410153528A CN117964150A CN 117964150 A CN117964150 A CN 117964150A CN 202410153528 A CN202410153528 A CN 202410153528A CN 117964150 A CN117964150 A CN 117964150A
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- CN
- China
- Prior art keywords
- copper
- silver
- cyanide
- gold
- wastewater
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010949 copper Substances 0.000 title claims abstract description 108
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 103
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000002351 wastewater Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000011084 recovery Methods 0.000 title claims abstract description 34
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229940098221 silver cyanide Drugs 0.000 title claims abstract description 21
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 claims abstract description 58
- 239000004332 silver Substances 0.000 claims abstract description 57
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000010931 gold Substances 0.000 claims abstract description 45
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052737 gold Inorganic materials 0.000 claims abstract description 41
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000002386 leaching Methods 0.000 claims abstract description 21
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000010802 sludge Substances 0.000 claims abstract description 15
- 238000003795 desorption Methods 0.000 claims abstract description 12
- 238000000605 extraction Methods 0.000 claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 9
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 8
- 239000010440 gypsum Substances 0.000 claims abstract description 8
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000018044 dehydration Effects 0.000 claims abstract description 6
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000007670 refining Methods 0.000 claims abstract description 5
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010979 pH adjustment Methods 0.000 claims abstract description 3
- 229940108928 copper Drugs 0.000 claims description 95
- 238000006243 chemical reaction Methods 0.000 claims description 54
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
- 238000001556 precipitation Methods 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 26
- 239000002244 precipitate Substances 0.000 claims description 22
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 14
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 14
- 239000013225 prussian blue Substances 0.000 claims description 14
- 229960003351 prussian blue Drugs 0.000 claims description 14
- 238000003723 Smelting Methods 0.000 claims description 13
- 239000002562 thickening agent Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 11
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 8
- 229960004887 ferric hydroxide Drugs 0.000 claims description 8
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 6
- 239000008394 flocculating agent Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 239000008267 milk Substances 0.000 claims description 5
- 210000004080 milk Anatomy 0.000 claims description 5
- 235000013336 milk Nutrition 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000005189 flocculation Methods 0.000 claims description 4
- 230000016615 flocculation Effects 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 229910052946 acanthite Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 241001062472 Stokellia anisodon Species 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 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 claims description 2
- QOGLYAWBNATGQE-UHFFFAOYSA-N copper;gold;silver Chemical compound [Cu].[Au][Ag] QOGLYAWBNATGQE-UHFFFAOYSA-N 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- NTVYFDOMBHOLGP-UHFFFAOYSA-N gold nitric acid Chemical compound [Au].O[N+]([O-])=O NTVYFDOMBHOLGP-UHFFFAOYSA-N 0.000 claims description 2
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229940056910 silver sulfide Drugs 0.000 claims description 2
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 208000034699 Vitreous floaters Diseases 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 abstract description 38
- 239000007789 gas Substances 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 6
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 9
- 230000020477 pH reduction Effects 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 206010017740 Gas poisoning Diseases 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- XKGUKYPCHPHAJL-UHFFFAOYSA-N methanetetracarbonitrile Chemical compound N#CC(C#N)(C#N)C#N XKGUKYPCHPHAJL-UHFFFAOYSA-N 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZUGQCBSESBUZIZ-UHFFFAOYSA-N [Ag]C#N.[Au] Chemical compound [Ag]C#N.[Au] ZUGQCBSESBUZIZ-UHFFFAOYSA-N 0.000 description 1
- XYTMPUOTTZHYSW-UHFFFAOYSA-N [Cu](C#N)C#N.[Ag] Chemical compound [Cu](C#N)C#N.[Ag] XYTMPUOTTZHYSW-UHFFFAOYSA-N 0.000 description 1
- XEKFEPUDBSRQBO-UHFFFAOYSA-N [Cu].[Ag]C#N Chemical compound [Cu].[Ag]C#N XEKFEPUDBSRQBO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229910001779 copper mineral Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910001739 silver mineral Inorganic materials 0.000 description 1
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/06—Chloridising
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/003—Bath smelting or converting
- C22B15/0039—Bath smelting or converting in electric furnaces
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0056—Scrap treating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0073—Leaching or slurrying with acids or salts thereof containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
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Abstract
本发明涉及一种从高铜高银氰化黄金氰化废水资源综合回收方法,包括如下步骤:(1)脱泥及铜银吸附;(2)活性炭解吸电解;(3)金泥提纯精炼;(4)废水一段沉铜;(5)废水二段沉铜银;(6)银铜产品浓密沉淀;(7)铜泥脱水;(8)溢流液pH调节;(9)石膏浆浓密及脱水。本发明不仅实现废水有价资源的回用,还有效净化了黄金氰化浸出循环液,而且高游离氰净化回水回用于氰化提金流程后,氰化浸出工艺中的金、银、铜回收率显著提升,尾液含银也得到有效控制。更重要的是,在回收过程中没有有毒氰化氢气体逸出,为多金属黄金矿山氰化废水中有价元素的综合回收提供了一种绿色经济安全的处置方法,具有广阔的应用前景。
Description
技术领域
本发明属于冶金废水资源回收技术领域,具体涉及一种从高铜高银氰化黄金氰化废水资源综合回收方法。
背景技术
近年来,随着易选、易浸金矿资源日趋减少,高铜、银等复杂金矿被不断采出及使用,氰化提金工艺是目前全世界黄金冶炼的主要工艺,氰化炭浆法是主要流程之一,其主要采用“矿石—磨矿—氰化浸出及活性炭吸附—载金炭解吸电解—金泥提纯精炼—合质金”的技术路线。因成矿差异,矿石中除了含较低品位的Au外,还会伴生有银矿物、铜矿物、铁矿物、砷矿物等,不同矿床的金矿中的银、铜含量相差较大,近年来随着深部资源不断开采,金矿石性质、成分变化较大,给后端资源高效利用和生产管理带来了不少问题。
在处理高铜高银金矿时,因氰化炭浆工艺废水为全流程闭路循环使用,同时矿石中银、铜品位较高,氰化废水中铜、银含量不断累积,导致挤占金银氰化浸出空间、吸附过程银与铜竞争吸附,造成银、铜回收率低,尾液银大于1mg/L,液相中的银、铜随尾渣夹带与流失情况严重。因此,提供一种安全、高效综合回收利用氰化废水资源方法,是国内黄金矿山面临的主要课题之一。
传统的氰化废水处理方法,如“酸化吹脱法”和“SART法”。2018-2022年,某矿山先后采用“酸化吹脱法”和“SART法”对高铜银氰化废水处理进行了研究,其回收效果并不理想,造成资源浪费,而且氰化氢安全问题也未能得到有效控制。其中,“酸化吹脱法”,氰化氢气体溢出的安全风险高,银铜回收率低,且需要增加氢氧化钠溶液吸收环节,流程长、安全操作要求高。“SART法”,在酸化与沉淀过程中,铜泥产品浓密沉降效果差、铜银泥水分高,铜、银、氰化物的回收率不稳定,铜泥脱水时易产生氰化氢气体扩散到作业环境,容易发生氰化氢气体中毒;作业pH低,生产控制要求高,易产生大量的SCN-有害离子,同时难以处理跑浑的含氰废水(处理残破积型氧化矿等含泥重难沉降矿石会大量产生);净化废水中和反应槽槽壁、水泵叶轮以及输送管道内极易产生大量的硫酸钙结垢物,清垢工作量大。
发明内容
针对上述问题,本发明提供一种从高铜高银氰化黄金氰化废水资源综合回收方法。
具体技术方案是:一种从高铜高银氰化黄金氰化废水资源综合回收方法,包括如下步骤:
(1)脱泥及铜银吸附:氰化浸出尾矿经过浓密沉降后,得到的溢流液即为高铜高银黄金氰化废水,首先将废水泵送通过管道过滤器,截留掉漂浮物和污泥,尤其是一些难沉淀物,再将其输送至多个串联的静态活性炭吸附装置,使废水中的部分金氰、银氰、铜氰络合离子被活性炭吸附回收,得到载金银铜活性炭。
(2)活性炭解吸电解:将步骤(1)获得载金银铜活性炭定期转至解吸电解系统提取银铜,得到金泥中间产品和解吸贫炭,贫炭返回至活性炭吸附装置重复使用,含金、银、铜、铁、钙的金泥进入提纯精炼。
(3)金泥提纯精炼:将步骤(2)获得的金泥转入台车炉中进行高温焙烧,焙烧后转入中频熔炼炉中造渣熔炼,熔化液再进行水淬,获得合金片;合金片进入硝酸分金反应釜进行金与银、铜、铁分离,通过多次分离和热水洗涤获得金粉,金粉高温熔炼后铸锭成金锭;硝酸铜、硝酸银、硝酸铁采用盐酸进行复分解反应和铁粉置换反应,在分银釜内进行铜与银、铁分离,获得银粉和硝酸铁-硝酸铜溶液;硝酸铁-硝酸铜溶液进入铜置换反应装置进行铜沉淀,反应结束后经脱水获得HNO3-Fe(NO3)2-Fe(NO3)3废水和海绵铜产品。
其中,金银分离采用硝酸法,使银及其他贱金属与硝酸反应,生成可溶性的硝酸盐,而金不与硝酸反应,沉积在反应容器底部,从而达到金银分离的目的。主要化学反应式为:
3Ag+4HNO3(稀)=3AgNO3+NO↑+2H2O
3Cu+8HNO3(稀)=3Cu(NO3)2+2NO↑+4H2O
3Fe+8HNO3(稀)=3Fe(NO3)2+2NO↑+4H2O
含Cu、Ag、Fe硝酸盐溶液根据盐酸与银结合生成氯化银的复分解反应进行分离,氯化银采用铁粉置换,硝酸铜同样采用铁粉置换。主要化学反应式为:
AgNO3+HCl=AgCl↓十HNO3
AgCl+Fe+Cl-=Ag↓+FeCl2
Cu(NO3)2+Fe=Fe(NO3)2+Cu↓
(4)废水一段沉铜:将步骤(1)活性炭吸附装置中残留的高铜银氰化废水输送至一段沉铜反应釜(该反应釜为带搅拌、密闭,以及耐酸的装置,反应釜上端设有应急用的微负压抽风管),并向该反应釜中加入步骤(3)获得的HNO3-Fe(NO3)2-Fe(NO3)3废水和Na2S溶液,反应得到滕氏蓝、普鲁士蓝深蓝色沉淀物、氢氧化铁以及硫化铜沉淀物。
多次小试、中试研究表明,金属氰化物络合分解过程,根据氰氢酸分解动力学(溶解度、稳定常数)原理,可通过有效控制酸化酸浓(PH控制)、药剂量和药剂添加速度,使分解后的氰化氢和氰根实现相对稳定地溶解于溶液中或反应釜内。主要化学反应式为:
2CN-+HNO3=HCN+NO3 2-
CN-+Na+=NaCN
向氰化废水中加入含有二价、三价铁离子的HNO3-Fe(NO3)2-Fe(NO3)3溶液,即可生成深蓝色沉淀(滕氏蓝)和深蓝色沉淀(普鲁士蓝)。主要化学反应式为:
滕氏蓝沉淀:3Fe2++2[Fe(CN)6]3-=Fe3[Fe(CN)6]2
普鲁士蓝沉淀:4Fe3++3[Fe(CN)6]4-=Fe4[Fe(CN)6]2
酸化分解后的铜离子发生硫化沉淀反应,硫化物沉淀法是利用重金属离子与其中的S2-反应生成M2SX沉淀物,根据不同金属硫化物溶度积差异,KspAg2S(1.6x10-49)<KspCuS(8.5x10-45)<KspPbS(83.4x10-28)<KspZnS(1.2x10-23)<KspFeS(3.7x10-19)达到去除或回收重金属的目的。主要化学反应式为:
MX++S2-→M2SX↓
多次试验研究表明,溶液中的深蓝色沉淀(滕氏蓝)、深蓝色沉淀(普鲁士蓝)与硫化铜可以发生很好的“互凝与团聚”效应,有利于二段沉铜以及后续沉降分离和产品水分控制。同时,由于一段PH控制较低,部分酸化分解后的氰化氢和氰根能够稳定溶解在液相中或稳定至反应釜内部密闭空间。
(5)废水二段沉铜银:将步骤(5)的一段沉铜溶液转入二段沉铜银反应釜中间区域,二段沉铜银反应釜为2个串联反应釜,且均为带搅拌、密闭,以及耐酸的反应装置,2个反应釜上端均设有应急用的微负压抽风管。
向沉铜银反应釜中添加H2SO4和Na2S溶液至反应釜的一半高度,反应得到硫化铜沉淀、硫化银沉淀、滕氏蓝沉淀、氢氧化铁以及普鲁士蓝沉淀。
一段沉铜后的银铜氰络合离子继续进行二段“酸化+硫化沉铜”,其原理为:根据氰氢酸分解动力学(溶解度、稳定常数)原理,可通过有效控制硫酸用量、添加速度(最为关键)和硫化钠,使分解后的氰化氢和氰根实现相对稳定地溶解于溶液中或反应釜内(多次试验研究已充分表明),铜、银离子发生硫化沉淀反应。主要化学反应式为:
2CN-+H2SO4=HCN+SO4 2-
Cu2++S2-=CuS↓
Ag++S2-=Ag2S↓
(6)银铜产品浓密沉淀:将步骤(5)的二段沉铜银溶液流经设置有文丘里混合节的管道,并与文丘里混合节内加入的絮凝剂充分混合后进入浓密机(浓密机为耐酸和全密闭设计,上端设有应急用微负压抽风装置)进行浓缩沉淀,如此通过“文丘里式絮凝+高密度沉淀”技术,利用较高密度沉淀物(滕氏蓝沉淀+普鲁士蓝沉淀+硫化铜+絮凝剂)的重力及载体的“吸附”“团聚”效应,加快絮体的生长及沉淀。
浓缩后的溢流液进入pH调节槽,浓密机底流上部1/4处的浓缩液返回至一段沉铜反应釜,其余下部3/4的浓缩浆液底流进入底流缓冲槽;向缓冲槽内加入氢氧化钠和石灰乳混合液进行调节pH,以防止铜泥脱水过程中氰化氢气体中毒事故发生(试验研究表明,在pH=7-8,氰化氢分解能力较为微弱,较为安全可控),获得含滕氏蓝、普鲁士蓝深蓝色沉淀物、氢氧化铁和硫化铜的浆液。
(7)铜泥脱水:将步骤(6)获得含滕氏蓝、普鲁士蓝深蓝色沉淀物、氢氧化铁和硫化铜的浆液通过板框压榨及风干压滤机进行深度脱水,滤液返回至一段沉铜反应釜,滤饼为呈深蓝色的铜泥,进入铜冶炼系统冶炼得到铜产品和银锭。
(8)溢流液pH调节:对步骤(6)获得的溢流液进行pH调节,向pH调节槽中添加石灰乳,将pH调节为10.5-11后,启动超声波装置,反应得到石膏浆。
该过程主要目的是稳定液相中的游离氰根离子,使之不生成氰化氢气体,采用石灰乳进行pH调节。主要化学反应式为:
H2SO4+Ca(OH)2=CaSO4+H2O
反应过程需重点考虑硫酸钙结垢问题,防止发生堵管等问题,因此采用机械搅拌+超声波进行调节pH以及除垢。其原理是利用超声波的空化效应、化学效应、剪切效应、抑制效应,使超声场处理流体,让管道、反应釜中成垢物质在超声场作用下,其物理形态和化学形态发生一系列变化,使之分散、粉碎、松散脱落,而不易附着在反应釜内壁和管道上,形成积垢。
(9)石膏浆浓密及脱水:将步骤(8)获得的石膏浆输送至浓密机,并向浓密机内添加絮凝剂进行絮凝沉淀,浓密机的溢流液返回磨矿、氰化浸出等氰化提金流程,实现氰化物的高效回用;沉淀底流浆液进入板框压榨及风干压滤机进行脱水,滤液返回磨矿、氰化浸出等氰化提金流程,实现废水中氰化物的高效回用,硫酸钙滤饼运至氰化浸出前的半自磨机等磨矿系统。
进一步,步骤(1)中活性炭吸附装置的进出液管均设置有18目筛管;废水在活性炭吸附装置中停留的时间控制在2-4h。
进一步,步骤(2)中活性炭解吸电解时间为13-16h,电解电压为3-5V,解吸过程中添加的氰化钠浓度为0.2%-0.5%。
进一步,步骤(3)中台车炉的焙烧温度控制在550-700℃,中频熔炼炉的熔炼温度控制在1200-1300℃。
进一步,步骤(4)中反应pH值为4-5,反应时间为10-20min,Na2S用量为溶液中铜金属含量的0.2倍。
进一步,步骤(5)中反应pH为3-4,反应时间为5-10min。
进一步,步骤(6)中文丘里混合节内絮凝剂添加量为3-5g/m3,缓冲槽中的pH调为7-8。
进一步,步骤(7)所述风干压滤机的风干时间为15-20分钟/次。
进一步,步骤(8)中超声波装置的超声波频率控制为10-25KHz,反应时间为10-30分钟。
进一步,所述方法适用于含Cu700-3000mg/L、Ag1-4mg/L、Fe0.5-10mg/L、Au0.02-0.04mg/L、总CN-700-3200mg/L的氰化废水。
本发明的有益效果:本发明提供了一种高铜高银黄金氰化废水安全、高效、绿色的综合回收方法,废水中银、铜、氰化物的回收率高达90以上,不仅实现废水有价资源的回用,还有效净化了黄金氰化浸出循环液,而且高游离氰净化回水回用于氰化提金流程后,氰化浸出工艺中的金、银、铜回收率显著提升,尾液含银也得到有效控制。更重要的是,在回收过程中没有有毒氰化氢气体逸出,为多金属黄金矿山氰化废水中有价元素的综合回收提供了一种绿色经济安全的处置方法,具有广阔的应用前景。
该方法的技术优势具体体现如下:
(1)该方法的反应条件均在常温常压进行,反应条件较为温和,更利于实施。
(2)含氰废水酸化前,先进行“管道过滤+活性炭吸附与脱泥”预处理,保证了废水洁净度,使原液适应性更强,也可避免因原液含泥量多,需要使用大量的硫酸引起铜、银、氰化物回收率不稳定的问题。
(3)采用硝酸进行金银分离、盐酸和铁粉还原银,既得到金银产品,又得到可作为一段沉铜用的HNO3-Fe(NO3)2-Fe(NO3)3废水,有利于降低成本,避免新的环境问题。
(4)一段酸化与沉铜采用HNO3-Fe(NO3)2-Fe(NO3)3废水和硫化钠,通过控制pH和5,药剂溶液加入位置和加速速度,同时采用密闭反应釜,氰根能相对稳定地溶解在反应釜及液相溶液中,得到团聚效果较好的“膝氏蓝沉淀+普鲁士蓝沉淀+硫化铜”沉淀物,氰化氢安全风险低。
(5)二段沉铜银通过精准控制硫酸量和反应pH,在前面几个步骤的加持下,酸化和沉铜效果明显,银、铜、氰的回收率较高且稳定,银回收率>98%、铜回收率>91%、氰化物回收率>92%,净化回水中的SCN-较低且可稳定控制在800mg/L以内。
(6)采用“高密度沉淀+文丘里式絮凝”技术,利用较高密度沉淀物(膝氏蓝沉淀+普鲁士蓝沉淀+硫化铜+絮凝剂)的重力及载体的“吸附”“团聚”效应,加快絮体的生长及沉淀,保证铜泥水分,水分可稳定控制在40%以内。
(7)净化高氰溢流回水调节pH采用超声波技术,彻底解决了反应釜、搅拌叶轮和管道硫酸钙结垢严重的问题。
(8)最后得到的石膏渣返回磨矿系统,高氰净化回水返回氰化提金流程,全流程无废渣、废水零排放,而且现场无氰化氢气体溢出,保证作业安全环保。
(9)高铜银氰化废水资源的综合回收利用,解决了含氰水“涨液”“铜离富集”问题,避免资源浪费。高氰净化水的回用,有利于提高矿石中铜、银的回收率指标,稳定控制尾液中Ag浓度在1mg/L以下,大幅减少尾液Ag、Cu随尾渣和水夹带流失。
附图说明
图1是本发明一种从高铜高银氰化黄金氰化废水资源综合回收方法的流程图;
具体实施方式
为了使本发明所解决的技术问题、技术方案更加清楚明白,以下结合附图及实施例,对本发明进一步详细说明。应当理解,此处所描述的具体实施例仅仅用于解释本发明,并不用于限定本发明。
实施例1
我国南方某多金属黄金矿山的高银高铜氰化废水,该废水是由炭浆厂氰化浸出、吸附、磁选铁、尾矿压滤产生的回水。其主要含Au0.024mg/L、Ag4.02mg/L、Cu1114mg/L、总CN-1399mg/L、SCN-894mg/L、Fe0.22mg/L,pH为11。
采用本发明所述的方法对高银高铜氰化废水进行综合回收处理,处理过程中各阶段的溶液成分具体如下表所示:
根据上表的数据可以得出:
①步骤(1)至(6)产生的铜泥,铜回收率达95.51%(1-50/1114×100%),银回收率达98.75%(1-0.05/4.02×100%);而且经过对铜泥进行成分检测,得到铜泥含Ag1800g/t、Cu56.5%、Fe0.1%、Ca2%,铜泥水分为38%。
②步骤(4)至(9)产生的氰化溢流液,总氰回收率达90.06%(1260/1399×100%),硫氰根稳定在896mg/L。
③生产现场通过现场安装的24小时氰化氢在线检测设备均未检测到氰化氢气体。
④高氰回水回用于氰化提金流程,相较于原工艺,Au浸出率提高0.58%,银浸出率提高0.4%,铜浸出率提高达1.5%;尾液Ag稳定在0.6mg/L以下。
实施例2
我国南方某多金属黄金矿山的高银高铜氰化废水,该废水是由炭浆厂氰化浸出、吸附、磁选铁、尾矿压滤产生的回水。其主要含Au0.021mg/L、Ag1.30mg/L、Cu800mg/L、总CN-942mg/L、SCN-700mg/L、Fe0.22mg/L,pH为11。
采用本发明所述的方法对高银高铜氰化废水进行综合回收处理,处理过程中各阶段的溶液成分具体如下表所示:
根据上表的数据可以得出:
①步骤(1)至(6)产生的铜泥,铜回收率达95.00%(1-40/800×100%),银回收率达98.46%(1-0.02/1.3×100%);而且经过对铜泥进行成分检测,得到铜泥含Ag850g/t、Cu50%、Fe0.2%、Ca2.5%,铜泥水分为40%。
②步骤(4)至(9)产生的氰化溢流液,总氰回收率达95.54%(900/942×100%),硫氰根稳定在705mg/L。
③生产现场通过现场安装的24小时氰化氢在线检测设备均未检测到氰化氢气体。
④高氰回水回用于氰化提金流程,相较于原工艺,Au浸出率提高0.3%,银浸出率提高0.5%,铜浸出率提高达2%;尾液Ag稳定在0.5mg/L以下。
综上所述,采用该方法氰化废水资源中的Ag、Cu、氰化物实现了高效回收利用,产品水分得到大幅下降,净化后的溶液中硫氰根较低,无大幅增加。更重要的是,在回收过程中没有有毒氰化氢气体溢出,安全问题得到有效解决。同时,该回水回用于氰化提金流程,相较于原工艺,金、银、铜的浸出率均得到提升,尾液含银也得到有效控制,减少资源损失。经过多次生产应用进一步表明,采用该工艺指标好且稳定,适应性较强,为多金属黄金矿山氰化废水中有价元素的综合回收提供了一种绿色经济安全的处置方法,具有广阔的应用前景。
以上通过具体的和优选的实施例详细地描述了本发明,但本领域技术人员应该明白,本发明并不局限于以上所述实施例,凡在本发明的精神和原则之内,所做的任何修改、等同替换等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种从高铜高银氰化黄金氰化废水资源综合回收方法,其特征在于,包括如下步骤:
(1)脱泥及铜银吸附:氰化浸出尾矿经过浓密沉降后,得到的溢流液即为高铜高银黄金氰化废水,首先将废水泵送通过管道过滤器,截留掉漂浮物和污泥,再将其输送至多个串联的静态活性炭吸附装置,使废水中的部分金氰、银氰、铜氰络合离子被活性炭吸附回收,得到载金银铜活性炭;
(2)活性炭解吸电解:将步骤(1)获得载金银铜活性炭定期转至解吸电解系统提取银铜,得到金泥中间产品和解吸贫炭,贫炭返回至活性炭吸附装置重复使用,含金、银、铜、铁、钙的金泥进入提纯精炼;
(3)金泥提纯精炼:将步骤(2)获得的金泥转入台车炉中进行高温焙烧,焙烧后转入中频熔炼炉中造渣熔炼,熔化液再进行水淬,获得合金片;合金片进入硝酸分金反应釜进行金与银、铜、铁分离,通过多次分离和热水洗涤获得金粉,金粉高温熔炼后铸锭成金锭;硝酸铜、硝酸银、硝酸铁采用盐酸进行复分解反应和铁粉置换反应,在分银釜内进行铜与银、铁分离,获得银粉和硝酸铁-硝酸铜溶液;硝酸铁-硝酸铜溶液进入铜置换反应装置进行铜沉淀,反应结束后经脱水获得HNO3-Fe(NO3)2-Fe(NO3)3废水和海绵铜产品;
(4)废水一段沉铜:将步骤(1)活性炭吸附装置中残留的高铜银氰化废水输送至一段沉铜反应釜,并向该反应釜中加入步骤(3)获得的HNO3-Fe(NO3)2-Fe(NO3)3废水和Na2S溶液,反应得到滕氏蓝、普鲁士蓝深蓝色沉淀物、氢氧化铁以及硫化铜沉淀物;
(5)废水二段沉铜银:将步骤(5)的一段沉铜溶液转入二段沉铜银反应釜中间区域,二段沉铜银反应釜为2个串联反应釜,向沉铜银反应釜中添加H2SO4和Na2S溶液至反应釜的一半高度,反应得到硫化铜沉淀、硫化银沉淀、滕氏蓝沉淀、氢氧化铁以及普鲁士蓝沉淀;
(6)银铜产品浓密沉淀:将步骤(5)的二段沉铜银溶液流经设置有文丘里混合节的管道,并与文丘里混合节内加入的絮凝剂充分混合后进入浓密机进行浓缩沉淀,浓缩后的溢流液进入pH调节槽,浓密机底流上部1/4处的浓缩液返回至一段沉铜反应釜,其余下部3/4的浓缩浆液底流进入底流缓冲槽;向缓冲槽内加入氢氧化钠和石灰乳混合液进行调节pH,获得含滕氏蓝、普鲁士蓝深蓝色沉淀物、氢氧化铁和硫化铜的浆液;
(7)铜泥脱水:将步骤(6)获得含滕氏蓝、普鲁士蓝深蓝色沉淀物、氢氧化铁和硫化铜的浆液通过板框压榨及风干压滤机进行深度脱水,滤液返回至一段沉铜反应釜,滤饼为呈深蓝色的铜泥,进入铜冶炼系统冶炼得到铜产品和银锭;
(8)溢流液pH调节:对步骤(6)获得的溢流液进行pH调节,向pH调节槽中添加石灰乳,将pH调节为10.5-11后,启动超声波装置,反应得到石膏浆;
(9)石膏浆浓密及脱水:将步骤(8)获得的石膏浆输送至浓密机,并向浓密机内添加絮凝剂进行絮凝沉淀,浓密机的溢流液返回氰化提金流程,沉淀底流浆液进入板框压榨及风干压滤机进行脱水,滤液返回氰化提金流程,硫酸钙滤饼运至氰化浸出前的磨矿系统。
2.根据权利要求1所述的一种从高铜高银氰化黄金氰化废水资源综合回收方法,其特征在于,步骤(1)中活性炭吸附装置的进出液管均设置有18目筛管;废水在活性炭吸附装置中停留的时间控制在2-4h。
3.根据权利要求1所述的一种从高铜高银氰化黄金氰化废水资源综合回收方法,其特征在于,步骤(2)中活性炭解吸电解时间为13-16h,电解电压为3-5V,解吸过程中添加的氰化钠浓度为0.2%-0.5%。
4.根据权利要求1所述的一种从高铜高银氰化黄金氰化废水资源综合回收方法,其特征在于,步骤(3)中台车炉的焙烧温度控制在550-700℃,中频熔炼炉的熔炼温度控制在1200-1300℃。
5.根据权利要求1所述的一种从高铜高银氰化黄金氰化废水资源综合回收方法,其特征在于,步骤(4)中反应pH值为4-5,反应时间为10-20min,Na2S用量为溶液中铜金属含量的0.2倍。
6.根据权利要求1所述的一种从高铜高银氰化黄金氰化废水资源综合回收方法,其特征在于,步骤(5)中反应pH为3-4,反应时间为5-10min。
7.根据权利要求1所述的一种从高铜高银氰化黄金氰化废水资源综合回收方法,其特征在于,步骤(6)中文丘里混合节内絮凝剂添加量为3-5g/m3,缓冲槽中的pH调为7-8。
8.根据权利要求1所述的一种从高铜高银氰化黄金氰化废水资源综合回收方法,其特征在于,步骤(7)所述风干压滤机的风干时间为15-20分钟/次。
9.根据权利要求1所述的一种从高铜高银氰化黄金氰化废水资源综合回收方法,其特征在于,步骤(8)中超声波装置的超声波频率控制为10-25KHz,反应时间为10-30分钟。
10.根据权利要求1-9任意一项所述的一种从高铜高银氰化黄金氰化废水资源综合回收方法,其特征在于,所述方法适用于含Cu700-3000mg/L、Ag1-4mg/L、Fe0.5-10mg/L、Au0.02-0.04mg/L、总CN-700-3200mg/L的氰化废水。
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