CN1688728A - 用氯化物浸析和萃取回收金属的方法 - Google Patents
用氯化物浸析和萃取回收金属的方法 Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims abstract description 55
- 238000002386 leaching Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 150000002739 metals Chemical class 0.000 title claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 12
- 238000011084 recovery Methods 0.000 title claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 86
- 229910052802 copper Inorganic materials 0.000 claims abstract description 85
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000002994 raw material Substances 0.000 claims abstract description 26
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000005363 electrowinning Methods 0.000 claims abstract description 10
- 238000000622 liquid--liquid extraction Methods 0.000 claims abstract description 5
- 238000000638 solvent extraction Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 59
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 13
- 239000010931 gold Substances 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- -1 Platinum Group Metals Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 238000005188 flotation Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 6
- 229910021653 sulphate ion Inorganic materials 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- QYFMQRSFRCFZNM-UHFFFAOYSA-K copper;sodium;trichloride Chemical compound [Na+].[Cl-].[Cl-].[Cl-].[Cu+2] QYFMQRSFRCFZNM-UHFFFAOYSA-K 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- GJCXHYNLSNVSQZ-UHFFFAOYSA-L [Cu](Cl)Cl.Cl Chemical compound [Cu](Cl)Cl.Cl GJCXHYNLSNVSQZ-UHFFFAOYSA-L 0.000 description 1
- ZHDZZQCPMPRKFO-UHFFFAOYSA-N [Fe].[Ni].[Cu].[Co] Chemical compound [Fe].[Ni].[Cu].[Co] ZHDZZQCPMPRKFO-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 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
-
- 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
-
- 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
-
- 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
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
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- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
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- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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- 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
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Abstract
本发明涉及一种从含铜的原料中回收金属特别是铜的方法,因此将原料浸析到含氯化物的溶液中。原料的浸析在氧化和足够高的氧化还原电势下进行,以致浸析得到的氯化铜溶液中的铜主要为二价。得到的氯化物溶液含有铜和潜在的其他有价值金属,将它送去液-液萃取。在萃取中,铜首先用萃取转移到有机相,然后在汽提中转移到硫酸盐溶液中,然后将它送去铜电解冶金。
Description
本方法涉及从含铜的原料中回收金属特别是铜,为此将原料浸析在含氯化物的溶液中。原料的浸析在氧化和足够高的氧化还原电势下进行,因而铜在浸析得到的氯化铜溶液中主要为二价。将得到的含有铜和潜在的其他有价值金属的氯化物溶液送去液-液萃取。在萃取中,铜通过萃取首先转移到有机相中,然后在汽提中转移到硫酸盐溶液中,然后将它送去铜电解冶金。
US 6007600公开了一种由含铜的原料例如硫化铜精矿湿法冶金生产铜的方法。根据这一方法,将原料与氯化钠-氯化铜(II)浓溶液按几段逆流浸析,生成一价氯化铜溶液。在浸析过程中,铁和硫从溶液中沉淀出来。用适合的试剂使经纯化的氯化亚铜溶液沉淀为氧化亚铜(copper oxidule),然后将氧化亚铜进一步还原成元素铜。
在US 6007600中,铜精矿的浸析在这样的条件下进行,其中在浸析过程中铁从溶液中沉淀出来,而浸析方法的特征是,使最大可能数量的铜以一价形式进入氯化物溶液。
US 4023964公开了一种生产电解铜的方法。在这一方法中,将硫化铜精矿浸析到氯化铜(II)-氯化钠溶液中。溶液的NaCl含量为100-300克/升,而pH值最大为1,从而铁溶解。将制得的溶液分成两部分,铁作为针铁矿从其中一部分溶液中沉淀出来,而将沉淀过程中生成的氯化铜溶液返回精矿浸析。将另一部分溶液与萃取溶液接触,同时将空气送入溶液,以便使一价铜氧化成二价铜。在萃取中,铜将本身结合进入有机相,而将贫铜的氯化物溶液送回精矿浸析。在汽提中,有机相和结合到有机相的铜与硫酸水溶液接触。将如此制得的硫酸铜溶液送去生产元素铜,而将有机相循环回萃取段。
US 4023964中公开方法的可行性在于,硫化铜精矿浸析为氯化物,将氯化物送去液-液萃取,而铜作为硫酸铜溶液从萃取中回收。硫酸铜溶液例如在电解冶金中的进一步处理是公知的技术,并生产纯铜。但是,这一方法弱点是精矿浸析,它在这样的条件下进行,其中铁也溶解,并且铁必需在单独段中从溶液中沉淀出来。同时,来自浸析的氯化铜溶液中的铜主要为一价铜,因此它必需在萃取过程中单独氧化。在萃取过程中发生氧化时,存在萃取剂同时也被氧化的危险,从而使它不再适合使用。在这一方法中,推荐在60℃下进行萃取,实际上这一温度太高,会引起萃取剂分解。
现在,已开发了这样一种从还含有铁和硫的含铜原料中回收金属特别是铜的方法。根据这一方法,在这样的条件下,对含铜的原料逆流进行基于氯化物的氧化浸析,其中精矿中的铁被沉淀,而硫作为元素硫也回收到沉淀物中。如果原料含有金和/或铂族金属(PGM),那么用硫将它们沉淀,然后从硫沉淀物中回收。此后,术语贵金属将用于指称金和/或铂族金属(PGM)。在浸析制得的氯化铜溶液中的铜主要为二价铜。在氧化物质、二价铜和盐酸的溶液中,在足够高的氧化还原电势下,通过浸析含铜的原料,铜以二价形式进入溶液,所述溶液中溶解的铜仍为二价,可直接送去萃取,而不需要氧化段。氧化还原电势优选为480-500毫伏,用Ag/AgCl电极测量。推荐在温度最高为40℃下进行萃取。将铜从有机溶液中汽提到硫酸水溶液中,然后送去电解,以便作为元素铜回收。
在附后的权利要求书中,本发明的必要特征将变得十分清楚。
含铜的原料例如可为硫化铜精矿,除铜以外它通常还含有其他有价值的金属。在本发明中,术语有价值的金属主要指镍、钴和锌。在浸析过程中,其他有价值的金属也溶解。因此,得到的水溶液含有主要为二价氯化铜的铜,以及其他有价值的金属。因为已知的铜萃取剂主要对二价铜有选择性,所以氯化铜溶液可直接送去萃取,而不需要氧化段。
本发明的方法用图1进一步说明,图1表示本发明的一个优选实施方案的流程图。
将含铜的原料送入浸析段,在那里用氯化铜-盐酸溶液进行浸析。在实践中浸析通常作为多段工艺进行,但为了简化,流程图示为一段。用添加的氧化剂将浸析的氧化还原电势调节到480-500毫伏(对Ag/AgCl)。氧化剂可为氧气或空气。将浸析得到的浆液送去固体和溶液分离。将来自所述分离的氯化铜溶液送去萃取,沉淀物送去硫浮选。
在萃取中,将氯化铜水溶液与有机萃取剂接触,将铜转移到有机相。萃取段包含通常的混合和沉降部,虽然它们在图中未详细示出。在流程图中所示的萃取按两段进行,但视条件而定,萃取也可按一段进行。在图中,水溶液用实线标出,而有机溶液用虚线表示。萃取段的温度为最高40℃。
将一部分来自第一萃取段的含氯化物的水溶液(萃余物)送回原料浸析,它已含有很少的铜,而有升高的酸含量。将其余的水溶液送去第二萃取段以前先将它中和。其他有价值金属的回收从第二萃取段取出的水溶液进行。萃取段排出的有机溶液通过洗涤后送入汽提。在汽提中,将含有二价铜离子的有机溶液与硫酸水溶液接触,将铜作为硫酸盐转移到水相中,通过电解从中回收铜。当在电解冶金中进行铜回收时,从电解冶金返回的酸可用作汽提中的硫酸水溶液。
任何已知的铜萃取剂都适合用作萃取剂,例如肟类,将它稀释到适合的溶剂中,例如煤油。当萃取按两段进行时,最多一半的铜在第一段中萃取。第一段萃余物的铜含量减少,同时其盐酸含量按以下反应增加。
在反应中,R表示萃取剂的烃部分,它与有机溶液中的铜形成配合物,而氢离子部分与水溶液中的氯化物形成盐酸。
将来自第一萃取段的大部分萃余物循环回含铜原料的浸析。但是,将一部分萃余物送去中和,在那里用碱性氢氧化物中和第一萃取段中产生的盐酸。例如氢氧化钠NaOH或石灰CaCO3可用作碱性氢氧化物。
将中和的氯化铜水溶液送至第二萃取段,在那里将尽可能仔细地从水溶液中萃取铜。将有机溶液从汽提段送至所述两萃取段,即这些段相对于有机溶液进料并连操作。已进行萃取时,将来自两段的萃取溶液合并,然后通过洗涤段送去汽提。用含硫酸盐的水溶液例如来自铜电解冶金的返回酸进行汽提。
将来自第二萃取段的水溶液即第二萃余物送去进一步处理,在那里从溶液中回收原料中所含的其他有价值金属,例如镍、钴和锌。用碱性氢氧化物将有价值的金属从溶液中沉淀出来。首先通过还原从生成的沉淀物中回收镍,随后回收原料中所含的其他金属。也可在铜萃取以后用选择性液-液萃取来回收钴和镍。
原料的浸析在高氧化还原电势和pH值为至少1.5下进行,因此几乎所有的铁都沉淀出来。在这些条件下,硫也沉淀出来。如果原料含有金和铂族金属(PGM),那么它们也留在沉淀物中。对沉淀物进行硫浮选,从而得到还含有贵金属(金+PGM)的含硫浓缩物。按已知的方法从含硫浓缩物中分离硫,并得到含贵金属的PGM浓缩物。得到的浓缩物的PGM含量是如此地高,以致它可销售到专门冶炼铂族金属的工厂。
在原料含有相当大数量镍的情况下,两段萃取是特别有利的。如果在原料中有很少的镍,那么可进行铜一段萃取。在这种情况下,将萃取排出的水溶液(萃余物)直接泵送回浸析。仅对小部分萃余物进行溶液中有价值物质的共沉淀,或当有价值金属的含量升高得如此多,以致它使铜的溶解度开始下降时,使用例如石灰按需要进行有价值物质的共沉淀。在氢氧化物沉淀以后,用硫酸处理氯化钙溶液,从而得到盐酸,将它送回原料浸析。
现在开发的方法也适用于除硫化铜精矿外的其他材料。上述方法适用于含有贵金属的精矿,但含金和PGM的铜-镍-钴-铁锍也可用本发明的方法有利地处理。
用以下实施例进一步说明本发明的方法。
实施例1
按本发明的方法处理组成包含12%Cu、2.3%Ni、23%Fe和25%S以及120ppm Pd和14ppm Au的硫化物精矿。将精矿在90℃和氧化还原电势为500毫伏(对Ag/AgCl)下浸析,同时保持吹氧。结果表明,镍和铜很好地浸析到溶液中,而只有小部分硫被氧化成硫酸盐。只有在氧化还原电势升至500毫伏以上(对Ag/AgCl)以后,贵金属才开始溶解。反应速度大,而仅在6小时内,铜和镍的反应程度超过90%。浸析残留物的组成为:Cu 1.5%、Ni 0.1%、Fe 30%、S 24%。进料溶液的铜含量为41克/升,镍含量为26克/升和其数量为2.28升/公斤精矿。除此以外,每公斤精矿加入0.59公斤纯盐酸,即1.48升25%盐酸/公斤精矿。浸析生成铜含量为59克/升、镍含量为26克/升的溶液,其数量为3.76升/公斤精矿。
在萃取中,约30%的铜在第一萃取段中被萃取,未中和,此后将大部分溶液泵送回浸析。在第一萃取段以后,水溶液的铜含量为41克/升。将第一萃取段得到的更少量水溶液(其比例由镍含量决定,在本情况下为约40%)送入第二萃取段。用碱液(lye)中和溶液中的硫酸,并在第二萃取段中萃取剩余的铜。
在两个萃取段中,将温度保持在40℃以下,并避免碱液和有机相之间的直接接触。这就使萃取剂的负荷减到最小,同时使它的使用寿命延长。
将两个萃取段得到的有机相合并,然后用稀硫酸水洗涤,除去铁和氯化物残留物。将洗涤的溶液泵送去浸析。洗涤以后,将含铜的有机溶液送去汽提,在那里将铜从有机溶液汽提到来自铜电解冶金的返回酸中。将汽提后的有机相返回萃取段。
每公斤精矿,铜电解冶金生成120克超纯阴极铜,即与萃取得到的和作为精矿送入所述工艺的相同数量。第二萃取段得到的萃余物含有镍和钴以及少量铜,将它送去氢氧化物沉淀。用碱液将镍、钴、铜和其他金属阳离子沉淀。所需的碱液数量为0.22公斤/公斤精矿,其中大部分用于酸中和。每公斤精矿生成0.06公斤氢氧化物沉淀物。氢氧化物沉淀物的组成为Ni 60%、Cu 0.3%、Co 2.8%。
过滤以后,将在浸析中生成的硫酸盐用石灰从盐溶液中除去。此后,在氯碱法电解以前,可将溶液送去最后纯化。在氯碱法电解中,生成的氯和氢经燃烧生成盐酸,然后送至浸析。其数量为1.48升25%盐酸/公斤精矿。
在浸析中生成浸析残渣,它含有精矿的PGM、大部分作为元素硫的硫化物硫、大部分作为针铁矿和赤铁矿的铁以及几乎没有变化的硅酸盐矿物。通过浮选将硫和PGM与硅酸盐和铁氧化物分离。首先通过分离大部分硫的方法来处理得到的含硫浓缩物,然后用浸析法进一步处理,以便将溶液返回工艺的开始步骤。PGM浓缩物的组成为Pd 17%、Pt 4%、Au 2%、Cu 10%、Ni 2%、Fe 14%,它易于销售用于进一步精炼或进一步加工成纯金属。其数量为0.7克/公斤精矿。
Claims (13)
1.一种从含有铁和硫的含铜原料中回收金属尤其是铜的方法,其中将所述的原料浸析到氯化铜和盐酸的水溶液中,从而使铁和硫留在浸析生成的沉淀物中,其特征在于,用氧化剂将含铜原料浸析的氧化还原电势相对于Ag/AgCl电极调节到480-500毫伏的范围,从而来自浸析的氯化铜溶液中的铜和其他有价值的金属主要为二价,将氯化铜溶液送去液-液萃取,将铜从氯化物溶液中分离出来,然后在汽提中转移到硫酸水溶液中,将它送去电解冶金,以便回收元素铜。
2.根据权利要求1的方法,其特征在于,氧化剂为氧气。
3.根据权利要求1的方法,其特征在于,氧化剂为空气。
4.根据任意上述权利要求的方法,其特征在于,氯化铜溶液的萃取按两段进行。
5.根据权利要求4的方法,其特征在于,将一部分来自第一萃取段的水溶液送回含铜原料的浸析。
6.根据权利要求4或5的方法,其特征在于,送入第二萃取段的水溶液的所述部分在送入所述萃取段以前先进行中和。
7.根据任意权利要求4-6的方法,其特征在于,相对于有机溶液,萃取段按平行连接进行操作。
8.根据任意上述权利要求的方法,其特征在于,萃取温度为最高40℃。
9.根据任意上述权利要求的方法,其特征在于,送入汽提的硫酸水溶液为来自铜电解冶金的返回酸。
10.根据任意上述权利要求的方法,其特征在于,在萃取以后,采用碱性氢氧化物沉淀将含铜原料中其他有价值的金属例如镍、钴和锌从水溶液中沉淀。
11.根据任意上述权利要求的方法,其特征在于,含铜原料含有贵金属,例如金和/或铂族金属(PGM)。
12.根据权利要求11的方法,其特征在于,由于原料浸析,金和/或铂族金属(PGM)沉淀在硫和铁沉淀物中,并在硫浮选中从沉淀物中回收。
13.根据任意上述权利要求的方法,其特征在于,含铜原料浸析中的pH值为至少1.5。
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FI125388B (en) | 2013-06-07 | 2015-09-30 | Outotec Finland Oy | Method for the recovery of copper and precious metals |
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