IE41867B1 - Removing metals from sulphide ores - Google Patents
Removing metals from sulphide oresInfo
- Publication number
- IE41867B1 IE41867B1 IE2239/75A IE223975A IE41867B1 IE 41867 B1 IE41867 B1 IE 41867B1 IE 2239/75 A IE2239/75 A IE 2239/75A IE 223975 A IE223975 A IE 223975A IE 41867 B1 IE41867 B1 IE 41867B1
- Authority
- IE
- Ireland
- Prior art keywords
- lead
- solution
- silver
- zinc
- chloride
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 150000002739 metals Chemical class 0.000 title claims abstract description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 96
- 239000011133 lead Substances 0.000 claims abstract description 69
- 229910052709 silver Inorganic materials 0.000 claims abstract description 60
- 239000004332 silver Substances 0.000 claims abstract description 60
- 239000011780 sodium chloride Substances 0.000 claims abstract description 48
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 45
- 239000012141 concentrate Substances 0.000 claims abstract description 45
- 239000011701 zinc Substances 0.000 claims abstract description 45
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 41
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims abstract description 34
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005864 Sulphur Substances 0.000 claims abstract description 24
- 238000002386 leaching Methods 0.000 claims abstract description 17
- 150000004763 sulfides Chemical class 0.000 claims abstract description 16
- 229910052949 galena Inorganic materials 0.000 claims abstract description 15
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 11
- 229910052969 tetrahedrite Inorganic materials 0.000 claims abstract description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 3
- 230000008025 crystallization Effects 0.000 claims abstract description 3
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 101
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 49
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 239000012535 impurity Substances 0.000 claims description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 23
- 239000000460 chlorine Substances 0.000 claims description 23
- 229910052801 chlorine Inorganic materials 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 9
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical class [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 229910001510 metal chloride Inorganic materials 0.000 claims description 7
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 239000011667 zinc carbonate Substances 0.000 claims description 4
- 235000004416 zinc carbonate Nutrition 0.000 claims description 4
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- UKUVVAMSXXBMRX-UHFFFAOYSA-N 2,4,5-trithia-1,3-diarsabicyclo[1.1.1]pentane Chemical compound S1[As]2S[As]1S2 UKUVVAMSXXBMRX-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- GACNLEQHDKHHQR-UHFFFAOYSA-M chlorolead Chemical compound [Pb]Cl GACNLEQHDKHHQR-UHFFFAOYSA-M 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000010310 metallurgical process Methods 0.000 abstract 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 18
- 239000012267 brine Substances 0.000 description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 11
- 239000011592 zinc chloride Substances 0.000 description 9
- 235000005074 zinc chloride Nutrition 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical class ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000010269 sulphur dioxide Nutrition 0.000 description 3
- 239000004291 sulphur dioxide Substances 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- PGWMQVQLSMAHHO-UHFFFAOYSA-N sulfanylidenesilver Chemical class [Ag]=S PGWMQVQLSMAHHO-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/16—Halides
-
- 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
- C22B1/08—Chloridising roasting
-
- 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
-
- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
1516127 Recovering metals from sulphide ores CYPRUS METALLURGICAL PROCESSES CORP 27 Aug 1975 [21 Oct 1974] 35281/75 Heading C1A Lead, silver and zinc values are recovered from sulphide ores or concentrates by chlorinating to convert the sulphides into chlorides and sulphur, leaching with sodium chloride solution to extract the chlorides, removing lead chloride from the leach solution by crystallization, recovering silver from the lead depleted solution, preferably by cementation, and removing zinc from the lead- and-silver-depleted solution e.g. by precipitating the carbonate using Na 2 CO 3 . A portion of leach solution is returned to the leaching step after removing the lead and some or all of the silver and optionally the zinc. Part of the depleted solution may be electrolysed to produce chlorine gas for the chlorination step. Antimony in a galena/tetrahedrite ore concentrate is volatilized as the chloride if the chlorination is carried out at 50-150‹C.
Description
This invention relates'to'processes-for recovering metals from sulphide ores containing lead, silver and zinc sulphides. . .
It has been proposed hitherto to convert metallic 5 sulphides into chlorides in metal recovery processes.
For example metal sulphide concentrates can be chlorinated with ferric chloride and chlorine gas in aqueous sodium chlorido or calcium chloride, (see ,U.S. Patent 1,736,659)· It has also been proposed hitherto (Tho Dry Chlorina10 tion of Complex Ores" by Ionides in Mining and Scientific Press, Volume 112, May 27, 1916} to chlorinate dry concentrates of metal sulphides containing lead, zinc and silver sulphides, using chlorine gas. A final chlorination is effected in a roasting step in the presence of air, ferric chloride formed in the chlorination step being decomposed to produce chlorine which completes the chlorination of the metal sulphides. This latter hitherto proposed process can be used for the production of zinc chloride, and it is not . a pollution-free prooess as sulphur dioxide is produced in the roasting step and it is released into the atmosphere. Furthermore, when the chlorination product is treated with sodium chloride to solubilize the metal chlorides, an undesir• able build-up ofimpurities, particularly zinc chloride, occurs in the brine leach solution. This adversely, affects the ability of the solution after a period of tine to solubilize silver and lead-chlorides from the chlorinated ore product.
According to the present invention there is provided a process for recovering metalj values from a sulphide ore 5Q concentrate containing lead, silver and zinc sulphides, the process - 2 41867 comprising the steps of: (a) chlorinating the concentrate to convert the metal sulphides into metal chlorides and to convert sulphide sulphur into elemental sulphur; (b) leaching the non gaseous product from step (a) with aqueous sodium chloride to dissolve lead and silver chlorides therein thereby to enable separation of these chlorides from insoluble solids; (c) cooling the sodium chloride leach solution to precipitate substantially all of the lead chloride therein followed by separating the precipitated lead chloride from the leach solution; (d) recovering silver from the lead chloride-depleted leach solution obtained in step (c); (e) removing a portion of the solution produced in step (d) and passing the remainder of the solution to the leach solution of step (b); (f) removing substantially all of the. zinc and other impurities from the portion of solution removed in step (e); . (g) part electrolysing the removed portion of the solution to produce chlorine gas while leaving a weakened sodium chloride solution; (h) passing the remaining electrolyte solution-to step (b); and (i) passing chlorine gas produce in step (g) to step (a), According to another aspect of the present invention there is provided a process for recovering metal values from a galena/tetrahedrite ore concentrate containing lead, silver, antimony and zinc sulphides, the process comprising the steps of: - 3 41867 (a) dry chlorinating the pulverized concentrate with chlorine gas at a temperature of from 50 to 150°C to convert the sulphides into chlorides, to volatilize antimony chloride produced, and to convert the sulphide sulphur into elemental sulphur; (b) leaching the non gaseous product from step (a) at a temperature of from 80 to 100°C with an aqueous solution containing from 250 to 300 grams/litre of sodium chloride to dissolve lead chloride and silver chloride, and to extraot ' these chlorides from the remaining solids; (c) cooling the sodium chloride leach solution from step (b) to about 20°C to precipitate substantially all of the lead chloride and separating the precipitated lead chloride therefrom; (d) fusing the lead chloride from step (c) and electrolyzing the fused salt to produce chlorine gas and lead; (e) passing the chlorine gas from step (d) to step (a); (f) recovering Silver from the lead chloride-depleted leach solution Remaining from step (c) by cementation with metallic iron; (g) removing from 5 to 15% by weight of the silver and lead-depleted leach solution from step (f), and passing the remainder of the depleted leach solution to the leach solution of step (b); (h) removing any lead and silver remaining in the removed portion of the metal-depleted solution by iron cementation; (i) precipitating zinc and other impurities from said' removed portion of the metal-depleted solution using sodium carbonate; (J) part electrolysing sodium chloride in said removed - 4 41867 portion of the metal-depleted solution to produce chlorine gas while leaving a weakened sodium chloride solution; (k) passing the chlorine gas from step (j) to step (a); (l) carbonating sodium hydroxide formed in step (j) to produce sodium carbonate and passing the sodium carbonate to step (i); and (m) passing the remaining sodium chloride solution from step (j) to step (b), According to a further aspect of the present invention there is provided a process for recovering metals from an ore containing lead, silver, and zinc sulphides, the process comprising chlorinating the sulphide ore to produce the chlorides of the metals and liberate elemental sulphur, leaching the chlorides with sodium chloride to remove lead and silver chlorides, separating lead chloride from silver chloride by cooling the leach solution, recovering silver by cementation of the lead chloride-depleted solution, reducing the concentration of zinc and other impurities in a portion of the lead and silver-depleted leach solution, and passing both the zinc-depleted and non zinc-depleted portions of the lead and silver depleted leach solution to the leaching step.
According to a yet further aspect of the present invention there is provided a process for recovering metals from a sulphide ore containing at least the sulphides of lead, silver, and zinc, the process comprising converting the sulphides into chlorides by chlorination, leaching the chlorides into sodium chloride solution, removing lead chloride from the leach solution by crystallization for the recovering of lead, recovering silver from the leach solution by cemen- 5 41867 tation, removing zinc from a portion of the reaulting lead and silver-depleted solution as zinc carbonate, returning the untreated portion of the lead and silver-depleted solution to the leaching step, electrolyzing the zinc-depleted solution containing sodium chloride to produce chlorine, the chlorination step being effected using dry chlorine gas to convert the metal sulphides to chlorides and sulphide sulphur to elemental sulphur.
Using a process employing the present invention, sulphide ore concentrates containing lead, silver and zinc sulphides can be treated in particular to recover silver and lead. The recovery of metals from their chlorides resulting from the chlorination step is effected so as to prevent the build-up of impurities, including zinc chloride, in the - 6 41867 sodium chloride leach solution used to solubilize the metal chlorides formed in the chlorination step. As an alternative to wet chlorination of the sulphides, drychlorination can be effected using dry chlorine gas, with heating to convert the sulphides to chlorides and to volatilize the chlorides of arsenic and antimony, if these metals are present. Dry chlorination has been found particularly effective with sulphides of the tetrahedritetennantite series either alone or combined with some other mineral such as galena.
After chlorination of the sulphides by any method, metal chlorides are leached into warm sodium chloride solution and separated from the resulting solution. The metals, lead and silver, which are of principal interest are then recovered from the separated aqueous chlorides. Lead chloride is crystallized by cooling, and lead can be recovered from the lead chloride by fused salt electrolysis with the chlorinejroduced being passed to the chlorination step. Silver can be removed from the lead chloride-depleted solution by cementation. The resulting lead and silver-', depleted solution, from which a portion has been separated, is passed to the sodium chloride brine leach. The separated portion of the metal-depleted solution, after removal of lead and silver therefrom by iron cementation, is preferably neutralized with sodium carbonate to remove zinc and other metal impurities as carbonates. Part electrolysis of the resulting solution produces chlorine which is passed to the ore chlorination step while some of the weak sodium chloride electrolyte remanining is concentrated and passed to the sodium chloride brine leach to prevent the build-up of zinc - 7 41867 and other impurities when the process is being effected continuously. Sodium hydroxide from the electrolysis is preferably carbonated and the resulting sodium carbonate used in the neutralization step.
The recycling to the initial sodium chloride leach solution of a portion of the lead and silver chloride depleted sodium chloride leach solution after the removal of zinc and other metal impurities, enables zinc chloride to be removed from the brine leach solution at substantially the same rate that it is added thereto by the ore. This can prevent its build-up in the brine leach solution, which would otherwise inhibit the solubilization of lead chloride. In addition, chlorine is retained in the system, so that substantially no chlorine leaves the system as chloride in impurities or otherwise. Any chlorine which is removed is removed as chlorine gas in the electrolysis and it is passed to the chlorination step without substantial loss of chlorine. Thejresent invention provides a substantially pollution-free process, with no chlorine or lead vapours or compounds being released into the atmosphere. Substantially all of the sulphide sulphur is converted into elemental Bulphur rather than sulphur dioxide, unlike pyromefcallurgical processes.
A process employing the present invention will now be described by way of example, with reference to the accompanying diagrammatic drawings in which:Figure 1 is a flow diagram showing the various steps in the exemplified process; and Figure 2 is a flow diagram showing chlorination of a concentrate containing lead, silver, zinc and antimony in a kiln. - 8 41867 The concentrate was a galena/tetrahedrite concentrate having the following analysis:Silver 0.50 -0.35% Lead 68 - 70% Antimony 0.80 - 1.4% Sulphur (Total) 14 - 17% Zinc 4 6% Iron 2-4% It is to be understood that other ores containing sulphides of lead, silver and zinc can be treated. The reactions ocurring in the chlorination step are: MS + Clg—iMOlp; (M » Pb, Zn, Ou, Fe, or Ag, etc.) S2 + MS + S2C12->MO12 + 3/2 S2 Sb2S2 + 5 012—>2 SbOl^ + 3/2 S2 The ore concentrate was ground before chlorination to -65 U.S. Standard Mesh, and the ground concentrate was dried.
Efficient utilization of chlorine gas was achieved by contacting pulverized concentrate with the chlorine in a countercurrent system. As shown in Fig. 2, the finelydivided concentrate enters the upper end of a rotary kiln, and dry chlorine gas is introduced at the bottom, concentrate discharge end of the tube, so that the highest concentration of chlorine gas contacts the more nearly completely chlorinated concentrate. An inert sweep gas, for example nitrogen, is fed into the kiln with the chlorine to remove sulphur chlorides, as is explained hereinafter.
The length of the kiln is divided into two zones. The zone nearer the discharge (Zone 2) was operated at a temperature of approximately 115°C, and the upper end of the - 9 41867 tube, (Zone 1) was operated, at a temperature of from 80 to 115°C. Chlorination occurred primarily in Zone 1, and sulphur chloride gases were evolved in Zone 2. The gases leaving the kiln, and containing volatilized antimony pentachloride (SbClj), were treated in a scrubber to remove antimony compounds, which were recovered therefrom. Similarly arsenic can be removed if the concentrate contains arsenic sulphide.
A definite amount of chlorine gas per unit weight of concentrate was metered into the kiln to convert substantially all the lead, and silver values in the concentrate into their respective chlorides, in a continuous process. Kiln temperatures of from 50 to 150°C have been found satisfactory, a preferable range being from 80 to 115°C. e.g. from 80 to 100°C.
Excessive stickiness of the concentrate in the kiln can be avoided if the temperature within the kiln is maintained below the melting point of sulphur, which is about 119°C. Since the reaction between lead sulphide (pbS) and. chlorine is exothermic, some cooling may be required in Zone 1.
Alternatively, an inert material such as sand, or recycled product can be added as a diluent for the concentrate. In Zone 2, heat can be applied in order to increase the vapour pressures of sulphur chlorides, so that they can be swept forward by the sweep gas such as nitrogen.
A minimum of sulphur chlorides is desirable in the chlorinated product, to avoid their being hydrolysed in the subsequent sodium chloride leach.' Such a hydrolysis reaction for SgOlg can be represented as follows: ®2°^2 + + h2® + SO2^or polythionic acids) The amount of chlorine gas required depends upon the - 10 41867 composition of the concentrate being treated. For galena/ tetrahedrite concentrates, most of the chlorine is used to chlorinate the galena (PbS). Such concentrates usually assay approximately 70% lead, and the theoretical chlorine requirement for the reaction PbS + Clg " PbClg + S per metric ton of concentrate is 215 kg. The remaining 45-65 kg. of chlorine (the total chlorine addition being from 260-280 kg. of chlorine per metric tone of concentrate) chlorinates the tetrahedrite and some of the sulphides of other metals present such as zinc, iron, copper and others. The following Example illustrates the dry chlorination of a lead sulphide concentrate, and the subsequent solubilization of the resultant metal chlorides with aqueous sodium chloride solution (which preferably has a concentration within the range 250 to 300 grams per litre of sodium chloride).
EXAMPLE Chlorination Conditions; Apparatus 5 Compartment rotary kiln Zone 1 Reaction: ClnAddition 260-270 kg/metric t of PbS ore Inert Gas Nitrogen N-:C15 = 1:1 Vol. d d Ratio Temperature 80° Time 2 Hr. Zone 2 Reaction: Inert Gas Nitrogen Temperature 110-115°C Time 1.5 Hr. Leach Conditions: Pulp Density 50 g Chlorinated Product per litre of Leach Solution. leach Solution 290 g/1 NaCl,pH 1.5 Temperature 95°C Time 1.5 to 3 Hi's. - 11 41867 Results: Assay, % PbS Concentrate Chlorinated Product Leached Residue 100 κ 121 Κ 18.6 κ Ag 0.54 0.28 0.012 Pb 70 58 0.12 Sb 1.2 0.41 0.098 Zn 4.5 3.7 16 Ee 2.7 2.3 7.9 Cu 0.94 0.80 0.18 01 <0.1 23 % Sb Volatilized During Chlorination = 59 % Extracted During RaOl leach -Ag = 99· 3 Pb « 99.9 Sb ·96 Zn » 33 Ee - 47 Cu - 97 These results show that more than 99 percent of the lead and silver present in the concentrate were converted into the chloride and extracted during the brine leach. In addition a substantial amount 6f( the antimony was recovered. Substantially all of th^>; gj^Ljihide sulphur was converted into elemental sulphur in the dry chlorination step.
Using dry chlorination at a low temperature (80° to 115°C) with controlled chlorine addition (260-280 kg of chlorine per metric ton of concentrate), followed by a sodium chloride leach at 90 to 95°C for an hour, 99% of the silver, 99.9% of the lead, 33% of the zinc, 47% of the iron, 97% of the copper and 96% of the antimony were extracted. During the chlorination, antimony was volatilized, probably - 12 41867 as SbCl^, and recovered from the waste gases. Arsenic, when present, can also be recovered in this manner. Substantially all of the sulphide sulphur in the metal sulphides was converted into elemental sulphur, unlike pyrometallurgical processes in which sulphur is released as the pollutant sulphur dioxide.
Referring to the flow sheet shown in Fig. 1, leaching described hereinbefore in the Example can be performed as follows. Irrespective of whether dry or wet chlorination is used, the flow sheet of Fig. 1 can be followed beyond the chlorination step. The chlorinated product is leached in the brine leach with sodium chloride solution to solubilize lead and silver chlorides, and other metal chlorides which act as impurities. After start-up, the brine leach solution is supplemented with recycled sodium chloride in a continuous process, as shown. The leach solution for the tetrahedrite/ galena concentrate during operation ordinarily contains from 260 to 280 grams per litre of sodium chloride, approximately 40 grams per litre of lead, .about 0.15 grams per litre of silver, 15 to 30 grams'per litre o'f ^inc, 15 to 50 grams per litre of ferrous iron, and lessletamouhts of copper, antimony, l Z /· calcium, magnesium, manganese,...aliimifiiuin, etc. The brine leach step, irrespective of the'concentrate being processed, is preferably performed at a temperature of from about 80 to 100°C. The leach slurry is filtered hot, and the residue discarded or if desired processed to recover elemental sulphur.
The recovery of lead then follows. Solubilized lead chloride is crystallized from the sodium chloride leach solution by cooling from a temperature of 80 to 100°C to - 13 41867 approximately 15 to 20°C. The resulting crystalline lead chloride is separated from the solution, for example hy centrifuging, dried, and electrolyzed in a fused salt cell to produce product lead, and chlorine gas which is recyled to the chlorination step.
Silver can then he recovered hy cementation from the lead chloride-depleted sodium chloride leach solution using metallic iron or lead to produoe an impure silver sponge containing some copper, lead, iron and other trace impurities Pure silver can be produced by refining this sponge. The lead and silver-depleted leach solution produced, minus a portion thereof, is passed to brine leach as shown.
About 5 to 15% of the metal-depleted leach solution is treated to remove impurities therefrom, especially zinc chloride, and the resulting impurity-depleted solution is fed to the brine leach. Hiis enables the concentration of zinc chloride and other impurities in the leach solution to be controlled, since zinc chloride appreciably decreases the solubility of lead chloride in sodium chloride solutions. Accordingly, in order to dissolve large amounts of lead chloride, zinc chloride and other impurities are preferably removed from a portion of the metal-depleted leach solution at substantially the same' rate as they are introduced in the chlorination step.
Treatment of a portion of the metal-depleted solution also enables impurities to be removed in a form other than as chlorides, which would otherwise result in a loss of chlorine from the system. Chlorine is recovered as a gas and it is passed to the chlorination step, thereby avoiding loss of chlorine from the system. - 14 41867 As shown in Fig. l lead, remaining in the portion of the metal-depleted solution is removed by cementation with metallic iron, and the resultant sponge lead is recycled to the silver cementation step. Any silver cemented out will also be recyled, and the lead concentration in solution in said portion of the solution decreased from about 15 grams to 0.2 grams per litre.
The said separated portion of the solution is then neutralized with sodium carbonate at a pH of about 8.5 and at a temperature of about 50 to 80°0 to precipitate zinc, iron and other metal impurities in a readily filterable form as carbonates. Sodium carbonate is used because it reacts with zinc chloride to produce sodium chloride, which is subsequently electrolysed so that no chlorine is lost from the system in removing zinc and other impurities. part The bleed solution, after solids removal, is/electrolysed hydrogen gas, to produce chlorine gas, /sodium hydroxide, and a weak sodium chloride solution. The prior removal of zinc and other impurities from the solution greatly' facilitates the electrolysis, as the electrolysis is'almost physically · K ι ,λ ; ' impossible if zinc and the other impurities are present in the electrolyte. The sodium hydroxide is carbonated to produce sodium carbonate which is recyled to the neutralization step. The chlorine gas is passed to the chlorination step, and the impurity-depleted sodium chloride solution is concentrated and passed to the leach step to prevent zinc build-up in the leach solution.
Processes employing the present invention can, of course, be performed either continuously or batch-wise.
Based on the results obtained using dry chlorination, - 15 41867 a material balance for a typical commercially available lead sulphide concentrate (galena/tetrahedrite) is as follows: ESTIMATED MATERIAL BALANCE FOR GALENA/TETRAHEDRITE Kg/metric Ton of Concentrate Ag Pb Sb Zn Fe Ou ό Input PbS Concentrates 3*00 618 10.6 39*7 23.7 S.3 140 Iron Powder 16 3.00 618 10.6 39.7 39.7 8.3 140 Products Lead 611.4 Ag Sponge 2.96 2.2 4.0 2.2 7.9 Sb Chloride 6.2 /v4 Leach Residue 0.04 3.5 0.4 26.5 12.8 0.4 Λ136 Impurities Carbonates ,, ,.0.+9 .3^2. 24.7 3.00 618 10.6 39.7 39.7 8.3 140 All the chlorine gas added .was used.internally.
This Table shows,, 'that' in theory/ail of the lead and 1 ·« silver can be recovered waSfebthe„fc£lorine. being lost from the system. After start-up,xv-irtuallyiio 'Chloride has to be added to a continuously operated process, subject to losses resulting for example from mechanical operations, such as filtration, concentration, etc.
While the invention has been illustrated in relation to treating a tetrahedrite/galena concentrate containing lead, silver and zinc and tbe use of a dry chlorination procedure, it is not limited to treating this ore or to using dry chlorination. Thus dry or wet chlorination can be used on ores in general containing lead, zinc and silver. The flow sheet of Fig. 1 can then be followed beyond the - 16 41867 chlorination step, irrespective of the method, of chlorination. Furthermore, metals can he recovered from their chlorides which have been produced by wet chlorination of their sulphides, and results comparable to those obtained in the Example hereinbefore can be achieved.
Claims (24)
1. A process for recovering metal values from a sulphide ore concentrate containing lead, silver and zinc sulphides, the process comprising the steps of: 5 (a) chlorinating the concentrate to convert the metal sulphides into metal chlorides and to convert sulphide sulphur into elemental sulphur; (b) leaching the non-gaseous product from step (a) with aqueous sodium chloride to dissolve lead and silver 10 chlorides therein thereby to enable separation of these chlorides from insoluble solids; (c) cooling the sodium ohloride leach solution to precipitate substantially all of the lead chloride therein followed by separating the precipitated lead chloride from 15 the leach solution; (d) recovering silver from the lead chloride-depleted leach solution obtained in step (c); (e) removing a portion of the solution produced in step (d) and passing the remainder of the solution to the 20 leach solution of step (b); (f) removing substantially all of the zinc and other impurities from the portion of solution removed in step (e); Cg) part electrolysing the removed portion of the solution to produce chlorine gas while leaving a weakened 25 sodium chloride solution; (h) passing the remaining electrolyte solution to step (b); and (i) passing chlorine gas produced in'step (g) to step (a). -1841867
2. A process as claimed in claim 1, performed continuously.
3., A process as claimed in claim 1 or claim 2, in which lead and silver remaining in the said portion removed in 5 step (e) are removed by iron cementation before zinc is removed in step (f).
4. A process as claimed in any of the preceding claims, in which zinc is removed from said portion in step (f) by neutralization with sodium carbonate to form sodium chloride 10 and zinc carbonate.
5. A process as claimed in claim 4, in which sodium hydroxide formed in the electrolysis of the sodium chloride in step (g) is carbonated to form sodium carbonate which is used to effect the neutralization. 15
6. , A process as claimed in any of the preceding claims, in which eaid portion removed in step (h) is concentrated before being passed to step (b).
7. A process as claimed in any of the preceding claims, in which the concentrate is chlorinated in step (a) using 2o dry chlorination with dry chlorine gas.
8. A process as claimed in claim 7, in which the dry chlorination is effected at a temperature below the melting point of elemental sulphur. -1941867
9. A process as claimed in claim 7, in which the dry chlorination is effected at a temperature of 50 to 150°C.
10. A process as claimed in any of the preceding claims, in which the sodium chloride leach solution contains from 5 250 to 300 grams per litre of sodium chloride.
11. A process as claimed in any of the preceding claims, in which step (b) is effected at a temperature of 80 to 100°C.
12. A process as claimed in any of the preceding claims, in which the Sodium chloride leach solution from step (c) 10 is cooled to about 20°G to precipitate lead chloride.
13. A process as claimed in any of the preceding claims, in which silver is recovered in step (d) by cementation with metallic iron.
14. A process as claimed in any of the preceding claims, 15 in which the concentrate is a galena/tetrahedrite ore.
15. A process for recovering metal yaluea from a galena/ tetrahedrite ore concentrate containing lead, silver, antimony and Zinc sulphides, the process comprising the steps of: (a) dry chlorinating the pulverized concentrate with 20 chlorine gas at a temperature of from 50 to 150°C to convert the sulphides into chlorides, to volatilize antimony chloride produced, and to convert the sulphide sulphur into elemental sulpnur -2041867 (b) leaching the non gaseous product from step (a) at a temperature of from 80 to 100°G with an aqueous solution containing from 250 to 300 grams/litre of eodium Chloride to dissolve lead chloride and silver chloride, 5 and to extract these chlorides from the remaining solids; (c) cooling the sodium chloride leach solution from step (b) to about 20°0 to precipitate substantially all of the lead chloride and separating the precipitated lead chloride therefrom; 10 (d) fusing the lead chloride from step (c) and electrolyzing the fused salt to produce chlorine gas and lead; (e) passing the chlorine gas from step (d) to step (a)! jg (f) recovering silver from the lead chloride-depleted leach solution remaining from step (c) by cementation with metallic iron; (g) removing from 5 to 1% by weight of the silver and lead-depleted leach solution from step (f), and passing 20 the remainder of the depleted leach solution to the leach solution of step (b); (h) removing any lead and silver remaining in the removed portion of the metal-depleted solution by iron cementation; 25 (i) precipitating zinc and other impurities from said removed portion of the metal-depleted solution using sodium carbonate; (j) part electrolysing sodium chloride in said removed portion of the metal-depleted solution to produce 30 chlorine gas while leaving a weakened sodium chloride solution; (k) passing the chlorine gas from step (j) to step (a); (l) carbonating sodium hydroxide formed in step (j) to produce sodium carbonate and passing the sodium carbonate 5 to step (i); and Cm) passing the remaining sodium chloride solution from, step (j) to step (b).
16. * A process as claimed in claim I5, in Which the concentrate includes arsenic sulphide and arsenic is 10 volatilized in step (a).
17. A process for recovering metals from an ore containing lead, silver, and zinc sulphides, the process comprising chlorinating the sulphide ore to produce the chlorides of the metals and liberate elemental sulphur, leaching the ]5 chlorides with sodium chloride to remove lead and silver chlorides, separating lead chloride from silver chloride by cooling the leach solution, recovering silver by cementation of the lead chloride-depleted solution, reducing the concentration of zinc and other impurities in a portion of 20 the lead and silver-depleted leach solution, and passing both the zinc-depleted and non zinc-depleted portions of the lead and silver depleted leach solution to the leaching step.
18. A process for recovering metals from a sulphide ore 25 containing at least the sulphides of lead, silver, and zinc, the process comprising converting the sulphides into chlorides -2241867 by chlorination, leaching the chlorides into sodium chloride solution, removing lead chloride from the leach solution by crystallization for the recovery of lead, recovering silver from the leach solution by cementation, 5 removing zinc from a portion of the resulting lead and silver depleted solution as zinc carbonate, returing the untreated portion of the lead and silver-depleted solution to the leaching step, electrolysing the zinc-depleted solution containing solution sodium chloride to produce chlorine, 10 the chlorination step being effected using dry chlorine gas to convert the metai sulphides to chlorides and sulphide sulphur to elemental sulphur.
19. A process as claimed in claim 18, in which zinc is removed from a portion of the lead and silver-depleted solution, and the resulting portion is added to the leaching solution in the leaching step,
20. A process as claimed in. claim 19, in which the said portion is electrolysed after removal of zinc therefrom to produce chlorine gas, which is passed to the dry chlorination 20 step,
21. A process as claimed in claim 20, in which sodium carbonate is added to precipitate the zinc as zinc carbonate, sodium hydroxide produced in the electrolysis is carbonated to produce sodium carbonate and the sodium carbonate produced 25 is passed to the zins carbonate precipitation step. -2341867
22. A process as claimed in claim 1, substantially as herein described.
23. A process for recovering metals from an ore containing lead,silver and zinc sulphides, the process being 5 substantially as herein described with reference to the accompanying drawing.
24. Lead, silver or zinc values when recovered by a process as claimed in any of the preceding Dated this 14th day of October, 1975.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US51645074A | 1974-10-21 | 1974-10-21 |
Publications (2)
Publication Number | Publication Date |
---|---|
IE41867L IE41867L (en) | 1976-04-21 |
IE41867B1 true IE41867B1 (en) | 1980-04-09 |
Family
ID=24055652
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE2239/75A IE41867B1 (en) | 1974-10-21 | 1975-10-14 | Removing metals from sulphide ores |
Country Status (7)
Country | Link |
---|---|
JP (1) | JPS5953335B2 (en) |
CA (1) | CA1064708A (en) |
DE (1) | DE2542877A1 (en) |
ES (1) | ES441060A1 (en) |
FR (1) | FR2288788A1 (en) |
GB (1) | GB1516127A (en) |
IE (1) | IE41867B1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4087340A (en) * | 1977-02-16 | 1978-05-02 | Uop Inc. | Production of metallic lead |
FR2446863A1 (en) * | 1979-01-22 | 1980-08-14 | Uop Inc | Lead recovery from sulphidic source - comprises halogenation, brine leaching and purification of leach soln. by redn., then oxidn. |
CA1336862C (en) * | 1989-09-28 | 1995-09-05 | Christopher A. Pickles | Recovery of silver values from chlorides including silver chloride |
ES2248615T3 (en) | 2001-10-03 | 2006-03-16 | Umicore | STATE CHLORINE PRODUCTION PROCEDURE FOR THE SEPARATION AND RECOVERY OF CINC. |
-
1975
- 1975-07-04 CA CA230,782A patent/CA1064708A/en not_active Expired
- 1975-08-27 GB GB35281/75A patent/GB1516127A/en not_active Expired
- 1975-09-18 ES ES441060A patent/ES441060A1/en not_active Expired
- 1975-09-25 DE DE19752542877 patent/DE2542877A1/en not_active Ceased
- 1975-10-07 FR FR7531322A patent/FR2288788A1/en active Granted
- 1975-10-14 IE IE2239/75A patent/IE41867B1/en unknown
- 1975-10-20 JP JP50126250A patent/JPS5953335B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS5953335B2 (en) | 1984-12-24 |
ES441060A1 (en) | 1977-03-16 |
CA1064708A (en) | 1979-10-23 |
IE41867L (en) | 1976-04-21 |
GB1516127A (en) | 1978-06-28 |
DE2542877A1 (en) | 1976-04-29 |
JPS5164403A (en) | 1976-06-03 |
FR2288788A1 (en) | 1976-05-21 |
FR2288788B1 (en) | 1981-02-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4097271A (en) | Hydrometallurgical process for recovering copper and other metal values from metal sulphides | |
US4011146A (en) | Process for separation and recovery of metal values from sulfide ore concentrates | |
US20080124269A1 (en) | Purified molybdenum technical oxide from molybdenite | |
US3798026A (en) | Copper hydrometallurgy | |
US4230487A (en) | Method of selectively bringing into solution the non-ferrous metals contained in sulphurized ores and concentrates | |
US5238662A (en) | Processes for recovering precious metals | |
Subramanian et al. | Review of the hydrometallurgy of chalcopyrite concentrates | |
CA1098481A (en) | Zinc recovery by chlorination leach | |
AU2004270530B2 (en) | Method of separation/purification for high-purity silver chloride and process for producing high-purity silver by the same | |
US4082629A (en) | Hydrometallurgical process for treating metal sulfides containing lead sulfide | |
EP0155250B1 (en) | A method for recovering the metal values from materials containing iron | |
CA1213735A (en) | Chlorination of copper, lead, zinc, iron, silver and gold | |
IE41867B1 (en) | Removing metals from sulphide ores | |
US4135993A (en) | Recovery of lead values | |
US4038066A (en) | Method of stripping base metals from fused salts | |
US4206023A (en) | Zinc recovery by chlorination leach | |
US3853543A (en) | Process for producing elemental copper by reacting molten cuprous chloride with zinc | |
US4135997A (en) | Electrolytic production of metallic lead | |
US4124461A (en) | Production of metallic lead | |
US629856A (en) | Process of extracting lead, zinc, or silver from complex sulfidic ores. | |
US3523787A (en) | Hydrometallurgical process for the recovery of high pure copper values from copper and zinc bearing materials and for the incidental production of potassium sulfate | |
US3980752A (en) | Precipitation of nickel, cobalt, lead sulphides in presence of iron oxides or hydroxides | |
KR20040060939A (en) | A method for purifying the solution in the hydrometallugical processing of copper | |
CA1106309A (en) | Production of metallic lead | |
US2425995A (en) | Process for treating oxidized ores of zinc |