CN115011800B - Method for separating indium and germanium from zinc oxide smoke dust - Google Patents
Method for separating indium and germanium from zinc oxide smoke dust Download PDFInfo
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 118
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 116
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 110
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 58
- 239000000779 smoke Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000428 dust Substances 0.000 title claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 134
- 238000002386 leaching Methods 0.000 claims abstract description 128
- 239000007788 liquid Substances 0.000 claims abstract description 82
- 239000011701 zinc Substances 0.000 claims abstract description 79
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 79
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000002893 slag Substances 0.000 claims abstract description 64
- SAZXSKLZZOUTCH-UHFFFAOYSA-N germanium indium Chemical compound [Ge].[In] SAZXSKLZZOUTCH-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002253 acid Substances 0.000 claims abstract description 34
- 238000009854 hydrometallurgy Methods 0.000 claims abstract description 26
- 238000001556 precipitation Methods 0.000 claims abstract description 21
- 238000011084 recovery Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000012141 concentrate Substances 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003723 Smelting Methods 0.000 claims description 48
- 239000011133 lead Substances 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 8
- 239000003517 fume Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000004071 soot Substances 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 6
- 238000005363 electrowinning Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000011268 mixed slurry Substances 0.000 claims description 5
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 238000000605 extraction Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000001648 tannin Substances 0.000 description 3
- 235000018553 tannin Nutrition 0.000 description 3
- 229920001864 tannin Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RQIPKMUHKBASFK-UHFFFAOYSA-N [O-2].[Zn+2].[Ge+2].[In+3] Chemical compound [O-2].[Zn+2].[Ge+2].[In+3] RQIPKMUHKBASFK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000247 postprecipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000638 solvent extraction 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
- 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
- C22B7/02—Working-up flue dust
-
- 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
- C22B41/00—Obtaining germanium
-
- 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
- C22B58/00—Obtaining gallium or indium
-
- 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
-
- 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
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
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- General Life Sciences & Earth Sciences (AREA)
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Abstract
Description
技术领域Technical field
本发明涉及一种氧化锌烟尘分离铟锗的方法，属于湿法冶金技术领域。The invention relates to a method for separating indium and germanium from zinc oxide smoke and belongs to the technical field of hydrometallurgy.
背景技术Background technique
湿法炼锌工艺的锌浸渣是当前提取铟锗的重要资源之一，含铟锗锌浸渣回收锗的方法主要为湿法高温高酸浸出和火法还原挥发-氧化锌烟尘浸出。目前我国的锌冶炼工艺以传统的常规工艺为主，因此铟锗的提取主要是从含铟锗氧化锌烟尘进行湿法提取。Zinc leaching residue from the hydrometallurgical zinc smelting process is currently one of the important resources for extracting indium and germanium. The main methods for recovering germanium from zinc leaching residue containing indium and germanium are wet high-temperature and high-acid leaching and fire reduction volatilization-zinc oxide fume leaching. At present, my country's zinc smelting process is mainly based on traditional conventional processes, so the extraction of indium and germanium is mainly wet extraction from zinc oxide smoke containing indium and germanium.
氧化锌烟尘是采用火法烟化挥发法处理湿法炼锌、火法炼铅渣后产出的主要含有锌、铅的一种中间原料，其中富含铟、锗等一种或多种稀有金属。当前的氧化锌烟尘处理工艺普遍采用的两段酸浸获得富铅浸出渣和富含稀有金属的浸出液，浸出渣再回收铅和银，浸出液进行稀有金属分离回收。Zinc oxide soot is an intermediate raw material mainly containing zinc and lead produced after the pyrotechnic zinc smelting and pyrotechnic lead smelting slags are processed by the fire smoke volatilization method. It is rich in one or more rare species such as indium and germanium. Metal. The two-stage acid leaching commonly used in the current zinc oxide soot treatment process obtains lead-rich leaching slag and rare metal-rich leaching liquid. The leaching slag then recovers lead and silver, and the leaching liquid is separated and recovered for rare metals.
由于氧化锌烟尘中稀有金属含量和技术经济指标等条件的限制，氧化锌烟尘中通常只有一种稀有金属具有回收的经济价值，因此已有公知技术，对氧化锌烟尘的处理只是针对其中的某一种稀有金属进行单一回收，如对含铟较高的氧化锌烟尘主要是采用浸出液中和沉淀富集铟，获得富铟渣，再对富铟渣进行硫酸浸出-萃取-电积回收铟；对含锗较高的氧化锌烟尘主要是采用对浸出液进行单宁沉淀富集锗，获得锗精矿，再对锗精矿进行盐酸浸出-氯化蒸馏-水解回收锗。Due to the limitations of rare metal content and technical and economic indicators in zinc oxide smoke, usually only one rare metal in zinc oxide smoke has economic value for recycling. Therefore, there are already known technologies, and the treatment of zinc oxide smoke is only for certain of them. A single type of rare metal is recycled. For example, for zinc oxide smoke with high indium content, the leach solution is mainly used to neutralize and precipitate to enrich indium to obtain indium-rich slag. The indium-rich slag is then subjected to sulfuric acid leaching-extraction-electrodeposition to recover indium; For zinc oxide fumes with high germanium content, the leachate is mainly subjected to tannin precipitation to enrich germanium to obtain germanium concentrate, and then the germanium concentrate is subjected to hydrochloric acid leaching-chlorination distillation-hydrolysis to recover germanium.
伴随行业对综合回收要求的提高，氧化锌烟尘中铟、锗的回收，尤其是同时含有铟、锗的氧化锌烟尘中铟、锗的分离回收显得至关重要，单一回收铟或锗的技术难以满足企业原料变化和冶炼要求。因此，开发含铟锗氧化锌烟尘分离回收铟锗的方法具有重要意义。As the industry's requirements for comprehensive recycling increase, the recovery of indium and germanium from zinc oxide smoke, especially the separation and recovery of indium and germanium from zinc oxide smoke that contain both indium and germanium, is crucial. It is difficult to use a single technology to recover indium or germanium. Meet the changes in raw materials and smelting requirements of enterprises. Therefore, it is of great significance to develop a method for separating and recovering indium and germanium from zinc oxide smoke containing indium and germanium.
发明内容Contents of the invention
本发明针对铟锗氧化锌烟尘中分离回收铟锗的问题，提供一种氧化锌烟尘分离铟锗的方法，利用铟、锗浸出特性的不同，通过调控反应过程酸度，分步浸出铟、锗，并通过铟、锗萃取特性的不同，进一步分离回收铟、锗，从而实现氧化锌烟尘中铟、锗的分离提取。Aiming at the problem of separating and recovering indium and germanium from zinc oxide smoke, the present invention provides a method for separating indium and germanium from zinc oxide smoke. By utilizing the different leaching characteristics of indium and germanium, and by regulating the acidity of the reaction process, indium and germanium are leached out step by step. And through the different extraction characteristics of indium and germanium, indium and germanium are further separated and recovered, thereby realizing the separation and extraction of indium and germanium from zinc oxide smoke.
一种氧化锌烟尘分离铟锗的方法，具体步骤如下：A method for separating indium and germanium from zinc oxide smoke. The specific steps are as follows:
(1)将含铟锗氧化锌烟尘与湿法炼锌低浓度硫酸溶液混合调浆，混合矿浆进行中性浸锗至终点pH值为2.5～3.5，得到中浸液和中浸渣；(1) Mix the indium-germanium-containing zinc oxide soot with the low-concentration sulfuric acid solution of hydro-zinc smelting to make a slurry. The mixed slurry is neutrally leached with germanium until the end-point pH value is 2.5 to 3.5 to obtain a medium leaching liquid and a medium leaching residue;
(2)步骤(1)所得中浸液进行锗的沉淀分离得到锗精矿和沉锗后液，沉锗后液送往湿法炼锌系统回收；(2) The mid-leaching liquid obtained in step (1) is subjected to precipitation and separation of germanium to obtain germanium concentrate and a liquid after precipitation of germanium, and the liquid after precipitation of germanium is sent to the wet zinc smelting system for recovery;
(3)步骤(1)所得中浸渣与湿法炼锌高浓度硫酸溶液混合，进行低酸浸铟至终点pH值为0.5～1.0，得到低浸液和低浸渣；(3) The medium leaching slag obtained in step (1) is mixed with a high-concentration sulfuric acid solution for zinc hydrometallurgy, and low-acid leaching of indium is performed until the end-point pH value is 0.5 to 1.0 to obtain a low leaching liquid and a low leaching slag;
(4)步骤(3)所得低浸液经含铟锗氧化锌烟尘中和沉铟锗至终点pH值为4.0～5.0，得到中和后液和铟锗中和渣；铟锗中和渣中铟含量不小于1wt％时(即铟锗中和渣为富铟锗渣)，送往铟回收系统进行浸出-萃取-电积，得到精铟产品和含锗萃余液；铟锗中和渣中铟含量小于1wt％时，返回步骤(3)进行低酸浸铟；中和后液与含锗萃余液作为湿法炼锌低浓度硫酸溶液返回步骤(1)替换湿法炼锌低浓度硫酸溶液用于含铟锗氧化锌烟尘混合调浆；(4) The low-soaking liquid obtained in step (3) is neutralized with indium-germanium-containing zinc oxide fumes and the indium-germanium is precipitated until the end-point pH value is 4.0 to 5.0 to obtain a neutralized liquid and an indium-germanium neutralized slag; the indium-germanium neutralized slag is obtained When the indium content is not less than 1wt% (that is, the indium-germanium neutralization slag is an indium-germanium-rich slag), it is sent to the indium recovery system for leaching-extraction-electrowinning to obtain refined indium products and germanium-containing raffinate; indium-germanium neutralization slag When the indium content is less than 1wt%, return to step (3) for low-acid leaching of indium; the neutralized liquid and the germanium-containing raffinate are used as a low-concentration sulfuric acid solution for zinc hydrometallurgy and return to step (1) to replace the low-concentration zinc hydrometallurgy. Sulfuric acid solution is used to mix slurry containing indium, germanium and zinc oxide smoke;
(5)步骤(3)所得低浸渣与湿法炼锌电解废液混合，进行高酸强化浸出至终点pH值为0.1～0.3，得到高浸液和高浸渣，高浸液作为湿法炼锌高浓度硫酸溶液返回步骤(3)替换湿法炼锌高浓度硫酸溶液用于低酸浸铟，将高浸渣进行洗涤、压滤，产出洗水和铅银渣产品，洗水返回步骤(3)替换湿法炼锌高浓度硫酸溶液用于低酸浸铟。(5) The low-leaching slag obtained in step (3) is mixed with the wet zinc smelting electrolytic waste liquid, and high-acid enhanced leaching is performed until the end-point pH value is 0.1 to 0.3 to obtain high-leaching liquid and high-leaching slag. The high-leaching liquid is used as the wet-process zinc smelting electrolytic waste liquid. The high-concentration sulfuric acid solution of zinc smelting is returned to step (3) to replace the high-concentration sulfuric acid solution of wet zinc smelting for low-acid leaching of indium. The high-concentration sulfuric acid slag is washed and filtered to produce washing water and lead and silver slag products. The washing water is returned Step (3) replaces the high-concentration sulfuric acid solution of wet zinc smelting for low-acid leaching of indium.
所述步骤(1)含铟锗氧化锌烟尘中含锗0.03～0.20wt％、含铟0.02～0.15wt％；In the step (1), the indium-germanium-containing zinc oxide smoke contains 0.03-0.20wt% germanium and 0.02-0.15wt% indium;
所述含铟锗氧化锌烟尘中还含有锌、铁、铅和银；The indium-germanium-containing zinc oxide smoke also contains zinc, iron, lead and silver;
所述步骤(1)湿法炼锌低浓度硫酸溶液中硫酸浓度为30～50g/L，中性浸锗的温度为80～90℃，时间为1.5～2h；In the step (1) of wet zinc smelting, the sulfuric acid concentration in the low-concentration sulfuric acid solution is 30-50g/L, the neutral germanium leaching temperature is 80-90°C, and the time is 1.5-2h;
所述步骤(2)锗的沉淀分离可采用公知的单宁沉锗或其他已知的沉锗方法；The precipitation and separation of germanium in step (2) can adopt the known tannin precipitation of germanium or other known germanium precipitation methods;
所述步骤(3)湿法炼锌高浓度硫酸溶液中硫酸浓度为60～80g/L，低酸浸铟的温度为80～90℃，时间为2～2.5h；In the step (3) of wet zinc smelting, the sulfuric acid concentration in the high-concentration sulfuric acid solution is 60-80g/L, the temperature of low-acid leaching indium is 80-90°C, and the time is 2-2.5 hours;
所述步骤(4)含铟锗氧化锌烟尘与低浸液的固液比g:L为20～40:1；The solid-liquid ratio g:L of the indium-germanium-containing zinc oxide smoke and the low-immersion liquid in step (4) is 20 to 40:1;
所述步骤(5)湿法炼锌电解废液中硫酸浓度为140～180g/L，高酸强化浸出的温度为80～90℃，时间为2.5～3h。The concentration of sulfuric acid in the wet zinc smelting electrolytic waste liquid in step (5) is 140-180g/L, and the temperature of high-acid enhanced leaching is 80-90°C and the time is 2.5-3 hours.
本发明的有益效果是：The beneficial effects of the present invention are:
(1)本发明通过三段浸出，利用铟、锗浸出特性的不同，通过调控反应过程酸度，分步浸出铟、锗，首段浸出控制较高pH进行中性浸锗，使大部分锗浸出获得可沉淀回收锗的溶液，而铟不浸出；二段浸出控制较低pH进行低酸浸铟，使铟和首段浸出残留的少部分锗浸出；三段高酸强化浸出，进一步提高铟、锗浸出率；(1) Through three-stage leaching, the present invention utilizes the different leaching characteristics of indium and germanium, and leaches indium and germanium step by step by regulating the acidity of the reaction process. The first stage of leaching controls a higher pH for neutral leaching of germanium, so that most of the germanium is leached. Obtain a solution that can precipitate and recover germanium without indium leaching; the second-stage leaching controls a lower pH to leaching indium with low acid, so that indium and a small part of the germanium remaining in the first-stage leaching are leached; the third-stage high acid leaching strengthens the leaching to further improve indium, Germanium leaching rate;
(2)本发明对于二段低酸浸铟的含铟锗溶液，先通过沉淀分离富集获得富铟锗渣，再进行铟锗浸出获得含铟锗溶液，再利用铟、锗萃取特性的不同，通过溶剂萃取分离回收铟、锗，铟萃取分离富集获得纯净含铟溶液，而使锗留在溶液中，以萃余液形式返回首段中性浸锗，获得可沉淀回收锗的溶液，从而实现氧化锌烟尘中铟、锗的分离提取。(2) In the present invention, for the second-stage low-acid leaching indium-containing indium-germanium solution, the indium-rich germanium slag is first obtained through precipitation, separation and enrichment, and then the indium-germanium leaching is performed to obtain the indium-germanium-containing solution, and then the difference in extraction characteristics of indium and germanium is used. , indium and germanium are recovered through solvent extraction, separation and enrichment. Indium is extracted, separated and enriched to obtain a pure indium-containing solution, while the germanium is left in the solution and returned to the first neutral leaching germanium in the form of raffinate to obtain a solution that can precipitate and recover germanium. This enables the separation and extraction of indium and germanium from zinc oxide smoke.
附图说明Description of the drawings
图1为本发明的工艺流程图。Figure 1 is a process flow diagram of the present invention.
具体实施方式Detailed ways
下面结合具体实施方式对本发明作进一步详细说明，但本发明的保护范围并不限于所述内容。The present invention will be further described in detail below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the content described.
实施例1：一种氧化锌烟尘分离铟锗的方法，具体步骤如下：Example 1: A method for separating indium and germanium from zinc oxide smoke. The specific steps are as follows:
(1)将含铟锗氧化锌烟尘与湿法炼锌低浓度硫酸溶液混合调浆，混合矿浆在温度80℃下进行中性浸锗2h至终点pH值为3.06，得到中浸液和中浸渣；含铟锗氧化锌烟尘中含有锌45.89wt％、铁6.31wt％、铅11.62wt％、银156g/t、锗0.03wt％、铟0.08wt％；湿法炼锌低浓度硫酸溶液为加水调节后的湿法炼锌电解废液，湿法炼锌低浓度硫酸溶液中硫酸浓度为42.56g/L；(1) Mix indium-germanium-containing zinc oxide soot and hydro-zinc smelting low-concentration sulfuric acid solution to make a slurry. The mixed slurry is neutrally leached with germanium at a temperature of 80°C for 2 hours until the end-point pH value is 3.06 to obtain the mid-leaching solution and the mid-leaching solution. Slag; zinc oxide dust containing indium and germanium contains 45.89wt% zinc, 6.31wt% iron, 11.62wt% lead, 156g/t silver, 0.03wt% germanium, and 0.08wt% indium; the low-concentration sulfuric acid solution of hydrometallurgical zinc is made by adding water After adjustment, the sulfuric acid concentration in the low-concentration sulfuric acid solution of zinc hydrometallurgy is 42.56g/L;
(2)步骤(1)所得中浸液经单宁沉锗法进行锗的沉淀分离得到锗精矿和沉锗后液，沉锗后液送往湿法炼锌系统回收；(2) The mid-leaching liquid obtained in step (1) is subjected to germanium precipitation and separation by the tannin precipitation method to obtain germanium concentrate and the post-precipitation liquid of germanium. The post-precipitation liquid of germanium is sent to the wet zinc smelting system for recovery;
(3)步骤(1)所得中浸渣与湿法炼锌高浓度硫酸溶液混合，在温度90℃下进行低酸浸铟2h至终点pH值为0.72，得到低浸液和低浸渣；湿法炼锌高浓度硫酸溶液为加水调节后的湿法炼锌电解废液，湿法炼锌高浓度硫酸溶液中硫酸浓度为71.52g/L；(3) The medium leaching slag obtained in step (1) is mixed with a high-concentration sulfuric acid solution of wet zinc smelting, and low-acid leaching of indium is performed at a temperature of 90°C for 2 hours until the end-point pH value is 0.72 to obtain a low leaching liquid and a low leaching slag; The high-concentration sulfuric acid solution of zinc smelting is the electrolytic waste liquid of wet zinc smelting adjusted by adding water. The sulfuric acid concentration in the high-concentration sulfuric acid solution of wet zinc smelting is 71.52g/L;
(4)步骤(3)所得低浸液经含铟锗氧化锌烟尘在温度70℃下中和沉铟锗1.5h至终点pH值为4.96，得到中和后液和铟锗中和渣，其中含铟锗氧化锌烟尘与低浸液的固液比g:L为30:1；铟锗中和渣中铟含量为0.051wt％，返回步骤(3)进行低酸浸铟，重复步骤(3)和(4)得到的铟锗中和渣中铟含量为1.46wt％时(即铟锗中和渣为富铟锗渣)，送往铟回收系统进行浸出-萃取-电积，得到精铟产品和含锗萃余液；中和后液与含锗萃余液作为湿法炼锌低浓度硫酸溶液返回步骤(1)替换湿法炼锌低浓度硫酸溶液用于含铟锗氧化锌烟尘混合调浆；(4) The low immersion liquid obtained in step (3) is neutralized with zinc oxide dust containing indium germanium for 1.5 hours at a temperature of 70°C until the end-point pH value is 4.96, to obtain a neutralized liquid and an indium germanium neutralized slag, wherein The solid-to-liquid ratio g:L of the indium-germanium zinc oxide soot and the low-leaching liquid is 30:1; the indium content in the indium-germanium neutralization slag is 0.051wt%. Return to step (3) to perform low-acid leaching of indium, and repeat step (3) ) and (4), when the indium content in the indium-germanium neutralization slag obtained is 1.46wt% (that is, the indium-germanium neutralization slag is an indium-germanium-rich slag), it is sent to the indium recovery system for leaching-extraction-electrowinning to obtain refined indium The product and the germanium-containing raffinate; the neutralized liquid and the germanium-containing raffinate are returned to step (1) as a low-concentration sulfuric acid solution for zinc hydrometallurgy to replace the low-concentration sulfuric acid solution for zinc hydrometallurgy for mixing with zinc oxide fumes containing indium and germanium. mixing;
(5)步骤(3)所得低浸渣与湿法炼锌电解废液混合，在温度90℃下进行高酸强化浸出2.5h至终点pH值为0.23，得到高浸液和高浸渣，其中湿法炼锌电解废液中硫酸浓度为168g/L；高浸液作为湿法炼锌高浓度硫酸溶液返回步骤(3)替换湿法炼锌高浓度硫酸溶液用于低酸浸铟，将高浸渣进行洗涤、压滤，产出洗水和铅银渣产品，洗水返回步骤(3)替换湿法炼锌高浓度硫酸溶液用于低酸浸铟；(5) The low leaching slag obtained in step (3) is mixed with the wet zinc smelting electrolytic waste liquid, and high-acid enhanced leaching is performed at a temperature of 90°C for 2.5 hours until the end-point pH value is 0.23 to obtain high leaching liquid and high leaching slag, wherein The sulfuric acid concentration in the electrolytic waste liquid of zinc hydrometallurgy is 168g/L; the high leaching liquid is returned to step (3) as the high-concentration sulfuric acid solution of zinc hydrometallurgy to replace the high-concentration sulfuric acid solution of zinc hydrometallurgy for low-acid leaching of indium. The leaching residue is washed and filtered to produce washing water and lead and silver slag products. The washing water is returned to step (3) to replace the high-concentration sulfuric acid solution of wet zinc smelting for low-acid leaching of indium;
本实施例氧化锌烟尘中锗的回收率为85.76％，锗精矿品位为4.73％；铟的回收率为86.25％，精铟产品的纯度为99.995％。In this example, the recovery rate of germanium in zinc oxide dust is 85.76%, and the grade of germanium concentrate is 4.73%; the recovery rate of indium is 86.25%, and the purity of the refined indium product is 99.995%.
实施例2：一种氧化锌烟尘分离铟锗的方法，具体步骤如下：Example 2: A method for separating indium and germanium from zinc oxide smoke. The specific steps are as follows:
(1)将含铟锗氧化锌烟尘与湿法炼锌低浓度硫酸溶液(实施例1步骤(4)产出的中和后液与含锗萃余液)混合调浆，混合矿浆在温度85℃下进行中性浸锗2h至终点pH值为3.48，得到中浸液和中浸渣；含铟锗氧化锌烟尘中含有锌37.51wt％、铁13.15wt％、铅13.62wt％、银218g/t、锗0.20wt％、铟0.15wt％；湿法炼锌低浓度硫酸溶液中硫酸浓度为31.05g/L；(1) Mix the zinc oxide dust containing indium and germanium with the low-concentration sulfuric acid solution of hydrometallurgy zinc (the neutralized liquid and the germanium-containing raffinate produced in step (4) of Example 1) to make a slurry. The mixed slurry is heated at a temperature of 85 Conduct neutral leaching of germanium at ℃ for 2 hours until the end-point pH value is 3.48, and obtain the mid-leaching liquid and mid-leaching slag; the indium-germanium-containing zinc oxide smoke contains 37.51wt% zinc, 13.15wt% iron, 13.62wt% lead, and 218g silver/ t, germanium 0.20wt%, indium 0.15wt%; the sulfuric acid concentration in the low-concentration sulfuric acid solution of zinc hydrometallurgy is 31.05g/L;
(2)步骤(1)所得中浸液经中和沉锗法进行锗的沉淀分离得到锗精矿和沉锗后液，沉锗后液送往湿法炼锌系统回收；(2) The mid-leaching liquid obtained in step (1) is subjected to germanium precipitation and separation by the neutralization and germanium precipitation method to obtain germanium concentrate and the post-precipitated germanium liquid. The post-precipitated germanium liquid is sent to the wet zinc smelting system for recovery;
(3)步骤(1)所得中浸渣与湿法炼锌高浓度硫酸溶液(实施例1步骤(5)产出的高浸液和洗水)混合，在温度85℃下进行低酸浸铟2.5h至终点pH值为0.51，得到低浸液和低浸渣；湿法炼锌高浓度硫酸溶液中硫酸浓度为79.58g/L；(3) Mix the intermediate leaching residue obtained in step (1) with the high-concentration sulfuric acid solution of zinc hydrometallurgy (the high leaching liquid and washing water produced in step (5) of Example 1), and perform low-acid leaching of indium at a temperature of 85°C. After 2.5 hours, the end-point pH value is 0.51, and low-leaching liquid and low-leaching slag are obtained; the sulfuric acid concentration in the high-concentration sulfuric acid solution of zinc hydrometallurgy is 79.58g/L;
(4)步骤(3)所得低浸液经含铟锗氧化锌烟尘在温度80℃下中和沉铟锗2.0h至终点pH值为4.91，得到中和后液和铟锗中和渣，其中含铟锗氧化锌烟尘与低浸液的固液比g:L为40:1；铟锗中和渣中铟含量为1.13wt％时(即铟锗中和渣为富铟锗渣)，送往铟回收系统进行浸出-萃取-电积，得到精铟产品和含锗萃余液；中和后液与含锗萃余液作为湿法炼锌低浓度硫酸溶液返回步骤(1)替换湿法炼锌低浓度硫酸溶液用于含铟锗氧化锌烟尘混合调浆；(4) The low immersion liquid obtained in step (3) is neutralized with zinc oxide dust containing indium germanium for 2.0 hours at a temperature of 80°C until the end pH value is 4.91 to obtain a neutralized liquid and an indium germanium neutralized slag, wherein The solid-to-liquid ratio g:L of indium-germanium-containing zinc oxide smoke and low-immersion liquid is 40:1; when the indium content in the indium-germanium neutralization slag is 1.13wt% (that is, the indium-germanium neutralization slag is an indium-germanium-rich slag), send Go to the indium recovery system for leaching-extraction-electrowinning to obtain refined indium products and germanium-containing raffinate; the neutralized liquid and the germanium-containing raffinate are returned to step (1) as a wet zinc smelting low-concentration sulfuric acid solution to replace the wet method Low-concentration sulfuric acid solution from zinc smelting is used to mix slurry containing indium, germanium and zinc oxide fumes;
(5)步骤(3)所得低浸渣与湿法炼锌电解废液混合，在温度80℃下进行高酸强化浸出3.0h至终点pH值为0.12，得到高浸液和高浸渣，其中湿法炼锌电解废液中硫酸浓度为179g/L；高浸液作为湿法炼锌高浓度硫酸溶液返回步骤(3)替换湿法炼锌高浓度硫酸溶液用于低酸浸铟，将高浸渣进行洗涤、压滤，产出洗水和铅银渣产品，洗水返回步骤(3)替换湿法炼锌高浓度硫酸溶液用于低酸浸铟；(5) The low leaching slag obtained in step (3) is mixed with the wet zinc smelting electrolytic waste liquid, and high-acid enhanced leaching is performed at a temperature of 80°C for 3.0 hours until the end-point pH value is 0.12 to obtain high leaching liquid and high leaching slag, wherein The concentration of sulfuric acid in the electrolytic waste liquid of zinc hydrometallurgy is 179g/L; the high leaching liquid is returned to step (3) as the high-concentration sulfuric acid solution of hydrometallurgical zinc smelting to replace the high-concentration sulfuric acid solution of hydrometallurgical zinc smelting for low-acid leaching of indium. The leaching residue is washed and filtered to produce washing water and lead and silver slag products. The washing water is returned to step (3) to replace the high-concentration sulfuric acid solution of wet zinc smelting for low-acid leaching of indium;
本实施例氧化锌烟尘中锗的回收率为84.96％，锗精矿品位为2.96％；铟的回收率为85.37％，精铟产品的纯度为99.995％。In this example, the recovery rate of germanium in zinc oxide dust is 84.96%, and the grade of germanium concentrate is 2.96%; the recovery rate of indium is 85.37%, and the purity of the refined indium product is 99.995%.
实施例3：一种氧化锌烟尘分离铟锗的方法，具体步骤如下：Example 3: A method for separating indium and germanium from zinc oxide smoke. The specific steps are as follows:
(1)将含铟锗氧化锌烟尘与湿法炼锌低浓度硫酸溶液(实施例2步骤(4)产出的中和后液与含锗萃余液)混合调浆，混合矿浆在温度90℃下进行中性浸锗1.5h至终点pH值为2.52，得到中浸液和中浸渣；含铟锗氧化锌烟尘中含有锌56.74wt％、铁2.31wt％、铅8.57wt％、银70g/t、锗0.09wt％、铟0.02wt％；湿法炼锌低浓度硫酸溶液中硫酸浓度为49.27g/L；(1) Mix the zinc oxide dust containing indium and germanium with the low-concentration sulfuric acid solution of wet zinc smelting (the neutralized liquid and the germanium-containing raffinate produced in step (4) of Example 2) to make a slurry. The mixed slurry is heated at a temperature of 90 Conduct neutral leaching of germanium at ℃ for 1.5 hours until the end-point pH value is 2.52, and obtain the mid-leaching liquid and mid-leaching slag; the zinc oxide dust containing indium germanium contains 56.74wt% zinc, 2.31wt% iron, 8.57wt% lead, and 70g silver. /t, germanium 0.09wt%, indium 0.02wt%; the sulfuric acid concentration in the low-concentration sulfuric acid solution of zinc wet smelting is 49.27g/L;
(2)步骤(1)所得中浸液经锌粉沉锗法进行锗的沉淀分离得到锗精矿和沉锗后液，沉锗后液送往湿法炼锌系统回收；(2) The mid-leaching liquid obtained in step (1) is subjected to germanium precipitation and separation by zinc powder precipitation and germanium method to obtain germanium concentrate and germanium precipitation liquid, and the germanium precipitation liquid is sent to the wet zinc smelting system for recycling;
(3)步骤(1)所得中浸渣与湿法炼锌高浓度硫酸溶液(实施例2步骤(5)产出的高浸液和洗水)混合，在温度80℃下进行低酸浸铟2.5h至终点pH值为1.0，得到低浸液和低浸渣；湿法炼锌高浓度硫酸溶液中硫酸浓度为60.63g/L；(3) Mix the medium leaching residue obtained in step (1) with the high-concentration sulfuric acid solution of zinc hydrometallurgy (the high leaching liquid and washing water produced in step (5) of Example 2), and perform low-acid leaching of indium at a temperature of 80°C. After 2.5 hours, the end-point pH value is 1.0, and low-leaching liquid and low-leaching residue are obtained; the sulfuric acid concentration in the high-concentration sulfuric acid solution of zinc hydrometallurgy is 60.63g/L;
(4)步骤(3)所得低浸液经含铟锗氧化锌烟尘在温度60℃下中和沉铟锗1.0h至终点pH值为4.08，得到中和后液和铟锗中和渣，其中含铟锗氧化锌烟尘与低浸液的固液比g:L为20:1；铟锗中和渣中铟含量为0.032wt％，返回步骤(3)进行低酸浸铟，重复步骤(3)和(4)得到的铟锗中和渣中铟含量为1.05wt％时(即铟锗中和渣为富铟锗渣)，送往铟回收系统进行浸出-萃取-电积，得到精铟产品和含锗萃余液；中和后液与含锗萃余液作为湿法炼锌低浓度硫酸溶液返回步骤(1)替换湿法炼锌低浓度硫酸溶液用于含铟锗氧化锌烟尘混合调浆；(4) The low immersion liquid obtained in step (3) is neutralized with indium germanium-containing zinc oxide fumes at a temperature of 60°C for 1.0 h until the end-point pH value is 4.08, and a neutralized liquid and an indium germanium neutralized slag are obtained, wherein The solid-to-liquid ratio g:L of the indium-germanium zinc oxide soot and the low-leaching liquid is 20:1; the indium content in the indium-germanium neutralization slag is 0.032wt%. Return to step (3) to perform low-acid leaching of indium, and repeat step (3) ) and (4) When the indium content in the indium-germanium neutralization slag obtained is 1.05wt% (that is, the indium-germanium neutralization slag is an indium-germanium-rich slag), it is sent to the indium recovery system for leaching-extraction-electrowinning to obtain refined indium The product and the germanium-containing raffinate; the neutralized liquid and the germanium-containing raffinate are returned to step (1) as a low-concentration sulfuric acid solution for zinc hydrometallurgy to replace the low-concentration sulfuric acid solution for zinc hydrometallurgy for mixing with zinc oxide fumes containing indium and germanium. mixing;
(5)步骤(3)所得低浸渣与湿法炼锌电解废液混合，在温度85℃下进行高酸强化浸出3.0h至终点pH值为0.29，得到高浸液和高浸渣，其中湿法炼锌电解废液中硫酸浓度为143g/L；高浸液作为湿法炼锌高浓度硫酸溶液返回步骤(3)替换湿法炼锌高浓度硫酸溶液用于低酸浸铟，将高浸渣进行洗涤、压滤，产出洗水和铅银渣产品，洗水返回步骤(3)替换湿法炼锌高浓度硫酸溶液用于低酸浸铟；(5) The low leaching slag obtained in step (3) is mixed with the wet zinc smelting electrolytic waste liquid, and high-acid enhanced leaching is performed at a temperature of 85°C for 3.0 hours until the end-point pH value is 0.29 to obtain high leaching liquid and high leaching slag, wherein The sulfuric acid concentration in the electrolytic waste liquid of zinc hydrometallurgy is 143g/L; the high leaching liquid is returned to step (3) as the high-concentration sulfuric acid solution of hydrometallurgical zinc smelting to replace the high-concentration sulfuric acid solution of hydrometallurgical zinc smelting for low-acid leaching of indium. The leaching residue is washed and filtered to produce washing water and lead and silver slag products. The washing water is returned to step (3) to replace the high-concentration sulfuric acid solution of wet zinc smelting for low-acid leaching of indium;
本实施例氧化锌烟尘中锗的回收率为87.13％，锗精矿品位为3.26％；铟的回收率为85.86％，精铟产品的纯度为99.996％。In this example, the recovery rate of germanium in zinc oxide dust is 87.13%, and the grade of germanium concentrate is 3.26%; the recovery rate of indium is 85.86%, and the purity of the refined indium product is 99.996%.
以上对本发明的具体实施方式作了详细说明，但是本发明并不限于上述实施方式，在本领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。The specific embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above-described embodiments. Various changes can be made within the scope of knowledge of those of ordinary skill in the art without departing from the gist of the present invention. .
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|---|
| 湿法炼锌过程中铟锗的综合回收;张博亚等;云南冶金;第36卷(第05期);25-28 * |
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| CN115011800A (en) | 2022-09-06 |
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