CN107429314A - 从溶液中回收金 - Google Patents
从溶液中回收金 Download PDFInfo
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- 239000010931 gold Substances 0.000 title claims abstract description 94
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 85
- 238000010828 elution Methods 0.000 claims abstract description 53
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 36
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims abstract description 13
- 235000010262 sodium metabisulphite Nutrition 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 150000005690 diesters Chemical class 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000717 retained effect Effects 0.000 claims description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000012074 organic phase Substances 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000000658 coextraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OMVSWZDEEGIJJI-UHFFFAOYSA-N 2,2,4-Trimethyl-1,3-pentadienol diisobutyrate Chemical class CC(C)C(=O)OC(C(C)C)C(C)(C)COC(=O)C(C)C OMVSWZDEEGIJJI-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004879 Na2S2O5 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- 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
- 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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G7/00—Compounds of gold
- C01G7/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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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
- C22B11/00—Obtaining noble metals
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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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
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- 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
- C22B3/262—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds using alcohols or phenols
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C22B5/00—General methods of reducing to metals
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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
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Abstract
公开了一种用于从含有可溶性金的含金有机溶液中回收金的方法。所述方法包括使含金有机溶液与洗提水溶液接触,从而将金从含金有机溶液中萃取至洗提5水溶液中。从有机溶液中分离含金的洗提水溶液。使所分离的含金的洗提水溶液与含有焦亚硫酸钠的还原剂接触,从而从洗提水溶液中还原金。
Description
技术领域
示例性和限制性实施方案总体上涉及回收金,具体而言涉及从含金溶液中回收金的方法。
背景技术
金溶剂萃取方法可包括使用金萃取试剂,金萃取试剂是一种对于进料溶液(即浸提母液,PLS)的金属杂质具有高分离因子的有效金萃取剂。该方法涉及包含金萃取试剂的有机相。金萃取试剂从酸性氯化物溶液中萃取金,在该溶液中金以氯化金复合物H+AuCl4 -的形式存在。通过萃取获得含金有机相。将萃取至有机相中的金用1.5M至8M的HCl洗涤以除去杂质,然后通过洗提水溶液洗提,从而将金回收至水相中。从水相中可通过电解或使用草酸或硼氢化钠作为还原剂将金还原成固体形式来回收金。
在该方法中,用于洗涤的HCl的成本很高,因为用于洗涤使用至少3M的HCl,通常为5M的HCl,以使金的损失最小化并且使洗涤结果最大化。
发明内容
因此,一个目的是提供一种方法来减轻上述缺点。该目的通过一种特征在于如独立权利要求中所述的方法来实现。优选的实施方案公开于从属权利要求中。
一方面,从含有可溶性金的含金有机溶液中回收金的方法包括,使含金有机溶液与洗提水溶液接触,从而将金从含金有机溶液中萃取至洗提水溶液;从有机溶液中分离含金的洗提水溶液;以及使所分离的含金的洗提水溶液与含焦亚硫酸钠的还原剂接触,从而从洗提水溶液中还原金。
附图说明
在下文中,通过优选实施方案参考附图来更详细地描述解决方案,其中
图1示出了通过还原试验获得的还原固体金的SEM图像;
图2示出了通过还原试验获得的固体的SEM图像。
具体实施方式
以下实施方案为示例性的。尽管说明书在多个位置可能涉及“一个(an)”、“一个(one)”或“某些(some)”实施方案,但这不一定意味着每个此表述均是指相同的实施方案,或该特征仅适用于单个实施方案。不同实施方案的单个特征还可组合以提供其他的实施方案。此外,词语“包含”和“包括”应理解为不限于所描述的仅由那些已提及的特征所组成的实施方案,并且这些实施方案还含有并未具体提及的特征/结构。所有词语和表述均应广义地解释并且均旨在说明而不是限制实施方案。
金溶剂萃取方法可涉及金萃取试剂,其含有两种组分,有机二酯和有机醇(如2,2,4-三烷基-1,3-戊二醇的二酯(例如2,2,4-三甲基-1,3-戊二醇二异丁酸酯或其衍生物)以及长链醇(例如2-乙基己醇))。金萃取试剂可用于从酸性氯化物溶液中萃取金,在该溶液中金以氯化金复合物H+AuCl4 -的形式存在。通过用金萃取试剂萃取来获得含金有机相。含金有机相用盐酸洗涤以除去杂质,其中一些酸(即盐酸)被共萃取至有机相中。共萃取至有机相中的酸增加了有机相的酸度,因此妨碍了金洗提效率。在洗提步骤中洗提共萃取至有机相中的酸。经洗提的酸在该过程中被除去。
在一个示例性实施方案中,可省去洗涤步骤。相反,在一个示例性实施方案中,有机相中存在的金通过洗提水溶液直接洗提,以将金回收至水相中,从而获得含金水溶液。例如,在该方法中弱酸性NaCl水溶液可用作洗提水溶液。将溶剂相和水相(通过相沉淀)彼此分离。通过使用焦亚硫酸钠(SMBS,Na2S2O5)作为还原剂从分离的含金水溶液中回收金(还原为固体单质金)。还原的金可通过过滤以固体金属形式收集。
在该方法中,通过使用SMBS作为还原剂,在通过洗提水溶液洗提之前,含金有机相不必经过洗涤或清洗以除去杂质。通过使用合适剂量的SMBS,可将金从水相中以高纯度有效回收。杂质仍可溶并且可随滤液一起离开此过程。弱酸性的NaCl水溶液使得金在洗提步骤仍可溶(作为氯化金复合物H+AuCl4 -的形式)。
如果金可从洗提水溶液中以高纯度有效回收,则避开含金有机相的洗涤和/或清洗在技术上和经济上是可行的。这是因为除了杂质之外,洗涤还除去了在含金有机相中存在的一些金。因此,如果洗涤的话,需要将溶液循环回至该过程以回收从该过程中除去的金。
盐酸是一种昂贵的化学品。一个示例性实施方案使得最小化使用盐酸成为可能。
一个示例性实施方案能够省去洗涤步骤,从而得到简化的且更低成本的金回收方法。制备高纯度的金是可能的。SMBS剂量可等于或接近于SMBS∶Au的化学计量比。可使用有效的且选择性低成本的还原剂。可实现有效的杂质除去。
在一个实施方案中,所使用的焦亚硫酸钠与金的摩尔比小于焦亚硫酸钠与金的化学计量比,以在第一还原步骤中还原部分金。然后,在第二还原步骤中使用新鲜的含焦亚硫酸钠的还原剂,以还原在第一还原步骤之后保留在洗提水溶液中的金。在第二还原步骤中,焦亚硫酸钠与金的摩尔比可大于焦亚硫酸钠与金的化学计量比。
在一个实施方案中,洗提水溶液含有100g/l或更少的氯化钠,优选10g/l。
该方法可在室温下、在接近于室温的温度下或在稍高的温度下(例如10℃至80℃,优选10℃至50℃,更优选20℃)进行。可使用大气压或接近于大气压的压力。
洗提步骤可在混合器-沉降器装置中或在连续搅拌罐反应器(CSTR)中进行。洗提步骤可包括连续的过程。该过程可包括将组分(如洗提之后的有机相(上层)和/或还原之后的水相(下层))循环回至洗提步骤。相分离可例如在混合器-沉降器装置中进行。在沉降器部分,将有机相和水相分离并分别输送。有机相可循环回至萃取步骤,而水溶液/洗提溶液可循环回至洗提步骤(例如至CSTR)。固体物质(包括金)可通过过滤从在还原步骤中所得的浆料中分离。
实施例
进行实验室金萃取试验以测试SMBS从洗提水溶液中还原金的能力,使用上文公开的金萃取试剂(有机二酯+有机醇)作为有机相。制备合成的浸提母液。表1示出了浸提母液(PLS)的组成。
表1.PLS组成
Au | 30.1mg/l |
Ca | 67200mg/l |
Cu | 77400mg/l |
Fe | 184mg/l |
Mg | 559mg/l |
Pb | 529mg/l |
Zn | 441mg/l |
Br | 15g/l |
Cl | 214g/l |
酸 | 10g/l |
通过使用1∶4的有机相/水相比(以将金从水性浸提液中萃取至有机相中),将水性PLS(含金)和(有机)金萃取试剂一起在室温下摇动15min。随后,将有机相从水性浸提液中分离,并且分析由此获得的负载有机物的金含量。检测出的负载有机物的金含量(即含金有机相的金含量)为96.4mg/l。不洗涤和/或清洗含金有机相。
将未清洗的含金有机相用洗提水溶液(含有10g/l的NaCl的盐溶液)洗提两次(第一洗提和第二洗提)。使用3∶1的有机相/洗提水溶液比。洗提之后,移除有机相。将含金洗提水溶液(由第一洗提和第二洗提获得)合并。含金洗提溶液中的金浓度为259mg/l(见表2)。没有分析镁和铅,因为它们不被金萃取试剂所萃取,从而不进入洗提水溶液中。
表2.洗提之后的洗提水溶液组成
将含金洗提溶液分为两等份用于还原试验。第一还原试验以化学计量量的SMBS(即1.5mol的SMBS:1mol的Au)进行。第二还原试验以50%过量的SMBS(即2.25mol的SMBS:1mol的Au)进行。使用0.5M的SMBS溶液。两个还原试验的溶液均摇动15min。摇动后,溶液通过使用孔径为0.22μm的Whatman滤纸过滤,然后从两个滤液中取出分析样品(“15min”)。将通过过滤获得的两个滤液放置沉降过夜。然后将溶液再次过滤(Whatman 0.22μm),从两个“过夜”滤液中取出分析样品(“过夜”)。溶液(即滤液)的组成示于表3中。
表3.试验1和试验2的组成
试验1 | 试验2 | 试验1 | 试验2 | ||
15min | 15min | 过夜 | 过夜 | ||
Au | mg/l | 3 | <1 | <0.01 | 0.01 |
Ca | mg/l | 38 | 54 | 38 | 53 |
Cu | mg/l | 307 | 309 | 313 | 307 |
Fe | mg/l | 43 | 43 | 43 | 43 |
Mg | NA | NA | NA | NA | NA |
Pb | NA | NA | NA | NA | NA |
Zn | mg/l | 9.4 | 9.5 | 9.4 | 9.4 |
由表3可见,可溶性金均从两个过夜接触时间的溶液中消失。杂质(Ca、Cu、Fe、Zn)的浓度接近于其初始值。
通过15min的接触时间,在试验1中可溶性金的浓度降低了98.8%,而大概在试验2中可溶性金的浓度几乎降低了100%。
因此检测出,在短的接触时间(15min)内,甚至在Au-SX的洗提水溶液中相对于可溶性金(259mg/l)化学计量量的SMBS几乎完全(98.8%)将金还原至固态。在更长的接触时间后(过夜),洗提溶液中的金浓度低于ICP-MS(电感耦合等离子体质谱)分析装置的检出限(小于0.01mg/l)。基于SEM(扫描电子显微镜)分析,所制备的固体金不含杂质(仍见表1)。在洗提和还原步骤之前不洗涤含金有机相。
图1示出了通过试验115min的接触时间获得的还原的固体金的SEM图像。还原的固体金可见于图像中。
图2示出了通过试验115min的接触时间获得的固体的SEM图像。还原的固体金见于图像a)(亮图像)中。图像b)、c)、d)、e)、f)(暗图像)中没有见到杂质(Cu、Pb、Fe、Co、Zn);从而表明样品中不存在杂质(即其未被还原剂还原)。
对本领域技术人员显而易见的是,随着技术的进步,本发明的概念可以以多种方式实施。本发明及其实施方案并不限于上文所述的实施例,而是可在权利要求书的范围内变化。
Claims (12)
1.一种用于从含有可溶性金的含金有机溶液中回收金的方法,其中所述方法包括
使含有金的浸提母液与含有有机二酯和有机醇的金萃取试剂接触,从而获得含金有机溶液;
使含金有机溶液与洗提水溶液接触,从而将金从含金有机溶液中萃取至洗提水溶液中;
从有机溶液中分离含金的洗提水溶液;
使所分离的含金的洗提水溶液与含焦亚硫酸钠的还原剂接触,从而从洗提水溶液中还原金。
2.权利要求1的方法,其中所述方法包括通过过滤洗提水溶液从洗提水溶液中回收还原的固体金。
3.权利要求1或2的方法,其中所述洗提水溶液含有氯化钠。
4.权利要求1、2或3的方法,其中所述洗提水溶液为弱酸性的。
5.如前述权利要求中任一项要求保护的方法,其中所述方法包括在不洗涤含金有机溶液的情况下,从含金的洗提水溶液中还原金。
6.如前述权利要求中任一项要求保护的方法,其中所述方法包括在不洗涤含金有机溶液的情况下洗提含金有机溶液。
7.如前述权利要求中任一项要求保护的方法,其中
所述有机二酯包括2,2,4-三烷基-1,3-戊二醇的二酯,和/或
所述有机醇包括2-乙基己醇。
8.如前述权利要求中任一项要求保护的方法,其中所述浸提母液为酸性的氯化物溶液,其中金以氯化金复合物H+AuCl4 -的形式存在。
9.如前述权利要求中任一项要求保护的方法,其中所述方法包括
使用小于焦亚硫酸钠与金的化学计量比的焦亚硫酸钠与金的摩尔比,用于在第一还原步骤中还原部分金;
在第二还原步骤中使用新鲜的含有焦亚硫酸钠的还原剂,以还原在第一还原步骤之后保留在洗提水溶液中的金。
10.如前述权利要求1至8中任一项要求保护的方法,其中所述方法包括
使用焦亚硫酸钠与金的化学计量比,用于还原金。
11.如前述权利要求中任一项要求保护的方法,其中所述方法包括在连续搅拌罐反应器中洗提含金有机溶液。
12.如前述权利要求中任一项要求保护的方法,其中所述洗提水溶液含有100g/l或更少的氯化钠,优选10g/l。
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IN2014KN01462A (zh) * | 2011-12-15 | 2015-10-23 | Advanced Tech Materials |
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US3856507A (en) * | 1973-03-12 | 1974-12-24 | Owens Illinois Inc | Recovery of gold from solution in aqua regia |
RU2176278C1 (ru) * | 2000-05-03 | 2001-11-27 | ОАО "Красноярский завод цветных металлов имени В.Н. Гулидова" | Способ выделения золота из золотосодержащего цинкового осадка |
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CN103249849A (zh) * | 2010-08-20 | 2013-08-14 | 高级技术材料公司 | 从电子垃圾回收贵金属和贱金属的可持续方法 |
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MX2017011687A (es) | 2018-01-25 |
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ZA201706349B (en) | 2020-01-29 |
WO2016146892A1 (en) | 2016-09-22 |
PE20171520A1 (es) | 2017-10-20 |
CA2979307A1 (en) | 2016-09-22 |
EA033385B1 (ru) | 2019-10-31 |
AU2016232007B2 (en) | 2019-03-07 |
AU2016232007A1 (en) | 2017-09-28 |
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