WO2017124893A1 - 一种铜铟镓硒物料的回收方法 - Google Patents

一种铜铟镓硒物料的回收方法 Download PDF

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WO2017124893A1
WO2017124893A1 PCT/CN2016/112152 CN2016112152W WO2017124893A1 WO 2017124893 A1 WO2017124893 A1 WO 2017124893A1 CN 2016112152 W CN2016112152 W CN 2016112152W WO 2017124893 A1 WO2017124893 A1 WO 2017124893A1
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hydroxide
indium
copper
recovering
gallium
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French (fr)
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高永涛
刘军飞
王冠
吴国发
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Hanergy New Material Technology Co Ltd
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Hanergy New Material Technology Co Ltd
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Priority to KR1020187020415A priority Critical patent/KR20180095648A/ko
Priority to AU2016388068A priority patent/AU2016388068A1/en
Priority to EP16886152.4A priority patent/EP3382046A4/en
Priority to CA3011910A priority patent/CA3011910A1/en
Priority to JP2018538582A priority patent/JP2019502827A/ja
Priority to US16/067,182 priority patent/US20190010578A1/en
Priority to SG11201806239SA priority patent/SG11201806239SA/en
Publication of WO2017124893A1 publication Critical patent/WO2017124893A1/zh
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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
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/02—Elemental selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/10—Sulfates
    • 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
    • C22B1/005—Preliminary treatment of scrap
    • 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
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0086—Treating solutions by physical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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

Definitions

  • the invention relates to a method for recovering a copper indium gallium selenide photovoltaic module, in particular to a method for recovering copper indium gallium selenide material.
  • Copper indium gallium selenide thin film solar cells have many advantages and are favored by the market, especially in recent years, the biggest hotspot of thin film solar cell research and development, scale production and application.
  • the absorption layer of copper indium gallium selenide solar cell consists of copper, indium, gallium and selenium in the optimal proportion of chalcopyrite structure, which can absorb a wide range of wavelengths, except for the visible spectrum of light absorbed by amorphous silicon solar cells. It can also cover the near-infrared region with a wavelength between 700 and 2000 nm, that is, the longest power generation in one day.
  • the copper indium gallium selenide thin film solar cell can exceed 20% per day compared with the same wattage level crystalline silicon solar cell.
  • Crystalline silicon cells are inherently photo-attenuating, and their power generation efficiency will gradually decrease after prolonged exposure to sunlight.
  • the copper indium gallium selenide solar cell has no photo-induced attenuation characteristics and high power generation stability. Crystal silicon solar cells have hot spots after power generation for a long period of time, resulting in small power generation and increased maintenance costs.
  • the copper indium gallium selenide solar cell can adopt an internal connection structure to avoid this phenomenon, and the maintenance cost is lower than that of the crystalline silicon solar cell.
  • Copper indium gallium selenide thin film solar cells are produced by vacuum sputtering, distillation and non-vacuum coating. No matter which manufacturing method is used, some materials of copper indium gallium selenide are produced during the production process. In addition to heavy metal copper, it also contains rare metals such as indium, gallium and selenium. In order to facilitate the continuous utilization of rare metals such as indium, gallium and selenium and heavy metal copper, it needs to be separated and separately recovered to facilitate further recycling to ensure the sustainable development of copper indium gallium selenide thin film solar cell materials. In the prior art, the method for recovering copper indium gallium selenide material mainly includes acid dissolution method, extraction method and oxidation distillation method. A combination of wet or fire refining methods.
  • a method for recovering copper indium gallium selenide is disclosed in Chinese Patent Application Publication No. CN102296178A, and specifically discloses a method of dissolving a metal powder containing copper indium gallium selenide using a mixed solution of hydrochloric acid and hydrogen peroxide.
  • the method uses helium to reduce selenium, replaces copper with indium metal, and separates indium from gallium by a supported liquid membrane in combination with a dispersed stripping solution.
  • a method for recovering copper indium gallium selenide is disclosed in Chinese Patent Application Publication No. CN103184388A, which first breaks the copper indium gallium selenide thin film solar panel into pieces, and then uses the soaking process to use the sulphuric acid at a predetermined temperature by a soaking process.
  • the soaking solution is obtained by immersing in a mixed system with hydrogen peroxide for a predetermined period of time, and then indium, gallium, and selenium are recovered by processes such as extraction, back extraction, and electrolysis.
  • U.S. Patent No. 5,779,877 discloses a method of recovering copper indium selenide solar cell materials.
  • the method mainly comprises crushing, nitric acid leaching, electrolysis of copper, selenium and indium by two electrodes, followed by evaporation to obtain a mixture of indium and zinc oxides, and oxidative distillation to separate copper and selenium.
  • an object of the present invention is to provide a method for recovering copper indium gallium selenide materials capable of reducing environmental pollution, high indium recovery rate, and low production cost.
  • the method for recovering copper indium gallium selenide material of the invention adopts sulfuric acid and hydrogen peroxide leaching, the leaching rate is greatly improved, and the acid gas pollution is reduced; after the selenium reduction, the liquid ion is hydrolyzed by the metal ion, and the PH value can be finely adjusted to separate the copper.
  • the operation is simple and the cost is low; on the other hand, the invention adopts alkaline gallium, Indium gallium separation can be achieved only by adjusting the pH value of the solution, and the separation effect is good, and the obtained indium and gallium products have high purity.
  • the method for recovering copper indium gallium selenide material of the invention comprises the following steps:
  • step A the copper indium gallium selenide material is placed in a ball mill for ball milling.
  • step B the concentrated sulfuric acid is diluted, and the ball-milled alloy powder in step A is mixed with the diluted concentrated sulfuric acid, and the temperature is raised, and then hydrogen peroxide is introduced for leaching. After the leaching is completed, the residue is filtered to obtain a pure leachate.
  • the reactions involved are as follows:
  • step C the leaching solution is heated and then sulphur dioxide gas is introduced.
  • sulphur dioxide gas is introduced.
  • a red precipitate of bricks is formed in the container, which gradually turns black, and black selenium is obtained after filtration.
  • Step D after removing the selenium, the solution is directly added with sodium hydroxide solution to adjust the pH value, and the mixture is allowed to stand at room temperature after stirring, and then the supernatant is extracted, and directly filtered to obtain a precipitate of gallium hydroxide and indium hydroxide, and a supernatant of copper sulfate.
  • the responses included are as follows:
  • step E the copper sulfate supernatant is directly evaporated to obtain copper sulfate pentahydrate.
  • step F the precipitation of gallium hydroxide and indium hydroxide is added to the sodium hydroxide solution, the mixture is stirred at a constant temperature, and then the supernatant is taken, and the supernatant is directly filtered to obtain an indium hydroxide precipitate and a sodium gallate solution.
  • the responses included are as follows:
  • step G the sodium gallate solution is directly hydrolyzed to obtain potassium hydroxide precipitation.
  • a sulfuric acid solution may be added to adjust the pH to neutrality, the diluted polyacrylamide is added, and the mixture is subjected to flocculation and precipitation by constant temperature stirring. After the precipitation, the supernatant is extracted and directly filtered to obtain a precipitate of gallium hydroxide.
  • the responses included are as follows:
  • step H the indium hydroxide precipitate is reverse-dissolved with hydrochloric acid, heated, stirred at a constant temperature, replaced with a 4N zinc plate, and washed and filtered to obtain a sponge indium.
  • the responses included are as follows:
  • the method for recovering the copper indium gallium selenide material of the present invention further comprises: ball-milling the copper indium gallium selenide material in step A into a powder of 40 mesh or less, and drying at 100 ° C for 4 hours after ball milling.
  • the method for recovering the copper indium gallium selenide material of the present invention further comprises: diluting the concentrated sulfuric acid to 25% in step B, mixing 200 g of the drying material with 25% concentrated sulfuric acid according to a solid-liquid ratio of 1:5, and raising the temperature to 90.
  • hydrogen peroxide was introduced at a rate of 8 ml/min, the stirring rate was 600 r/min, and the temperature was leached for 3 hours.
  • the method for recovering the copper indium gallium selenide material of the present invention further comprises, after heating the leaching solution to 65 ° C in step C, introducing sulfur dioxide gas at a rate of 10 L/min and maintaining a constant temperature for 10 hours.
  • the method for recovering the copper indium gallium selenide material of the invention further comprises: adding the 8 mol/L sodium hydroxide solution directly to the solution in step D to adjust the pH value to 4.5, stirring at room temperature for 20 min, stirring at a rate of 200 r/min, and allowing to stand for 2 h. After the supernatant is extracted, it is washed repeatedly three times, and the water consumption of each wash water does not exceed 800 ml.
  • the method for recovering the copper indium gallium selenide material of the invention further comprises: adding the gallium hydroxide and the indium hydroxide precipitate in the step F to the 8 mol/L sodium hydroxide solution and heating to 80 ° C, stirring at a rate of 200 r/min, stirring at a constant temperature for 20 min, After standing for 2 h, the supernatant was extracted and washed repeatedly for three times. The water consumption per washing did not exceed 800 ml.
  • the method for recovering the copper indium gallium selenide material of the invention further comprises: adding the sodium gallate solution in the step G to the 1 mol/L sulfuric acid solution to adjust the pH value to neutrality, adding 20 ml of the diluted 10% polyacrylamide, and maintaining the temperature at 80 ° C, stirring. The rate is 200r/min, and the mixture is stirred for 10 minutes at a constant temperature for flocculation and sedimentation. After the sedimentation, the supernatant is extracted. After repeated washing and sedimenting three times, the supernatant is extracted, and the amount of washing water is not more than 800 mL. Finally, the gallium hydroxide precipitate is directly filtered, and gallium hydroxide is obtained. It can be obtained by placing it in a dry box at a constant temperature of 80 ° C and drying for more than 8 hours.
  • the method for recovering the copper indium gallium selenide material of the present invention further comprises: in step H, pre-dissolving the indium hydroxide precipitate with 600 ml of 10% hydrochloric acid, dissolving and adjusting the pH to 1.5, and heating to 55 ° C for constant temperature stirring, stirring rate 200 r /min.
  • the supernatant is sodium gallate solution, which can be directly hydrolyzed and filtered to obtain gallium hydroxide.
  • the indium hydroxide precipitate is directly dissolved in hydrochloric acid, and the zinc plate is replaced to obtain sponge indium.
  • the selenium recovery rate is 96%
  • the copper recovery rate is 92%
  • the indium and gallium recovery rate is 92%.
  • using the two sexes of gallium, directly adjusting the PH value to separate indium and gallium the cost is low, and the operation is simple.
  • FIG. 1 is a schematic flow chart of a method for recovering a copper indium gallium selenide material according to an embodiment of the present invention.
  • the method for recovering copper indium gallium selenide material includes the following main steps:
  • step A 200 g of copper indium gallium selenide material was placed in a ball mill, ball-milled to a powder of 40 mesh or less, and dried at 100 ° C for 4 hours.
  • Step B dilute concentrated sulfuric acid to 25%, mix 200g of dried material with 25% concentrated sulfuric acid according to a solid-liquid ratio of 1:5, raise the temperature to 90 ° C, and introduce hydrogen peroxide at a rate of 8 ml / min, stirring rate 600 r / Min, the temperature is leached for 3h, and after the leaching is finished, the residue is filtered to obtain a copper indium gallium selenide leaching solution.
  • step C after the leaching solution is heated to 65 ° C, sulfur dioxide gas is introduced at a rate of 10 L/min and the temperature is kept for 10 h. During the process of reducing selenium, a brick red precipitate is formed in the container, gradually becomes black, and black selenium is obtained after filtration.
  • Step D after removing selenium, directly add 8 mol/L sodium hydroxide solution to adjust the pH value to 4.5 to 4.7, stir at room temperature for 20 min, stir at a rate of 200 r/min, and after standing for 2 h, extract the supernatant, and wash and extract three times each time.
  • the washing water does not exceed 800 ml of water, and finally directly filtered to obtain a precipitate of gallium hydroxide and indium hydroxide, and a copper sulfate supernatant.
  • step E the copper sulfate supernatant is directly evaporated to obtain copper sulfate pentahydrate.
  • Step F adding gallium hydroxide and indium hydroxide precipitate to 8 mol/L sodium hydroxide solution and heating to 80 ° C, stirring rate 200 r / min, stirring at a constant temperature for 20 min, after standing for 2 h, extracting the supernatant, repeatedly washing and extracting three times, each The secondary washing water consumption does not exceed 800ml, and finally directly filtered to obtain indium hydroxide precipitate and sodium gallate Solution.
  • Step G adding 1 mol/L sulfuric acid solution to the sodium gallate solution to adjust the pH value to neutrality, adding 20 ml of diluted 10% polyacrylamide, constant temperature 80 ° C, stirring rate 200 r / min, stirring at a constant temperature for 10 min for flocculation precipitation, after precipitation
  • the supernatant is extracted, and the same step F is repeated. After washing and sedimenting three times, the supernatant is extracted, and the amount of washing water is not more than 800 mL each time.
  • the gallium hydroxide precipitate is directly filtered, and the gallium hydroxide is placed in a dry box at a constant temperature of 80 ° C, and dried.
  • Gallium hydroxide can be obtained for more than 8 hours.
  • Step H the indium hydroxide precipitate is reversely dissolved with 600 ml of 10% hydrochloric acid, dissolved to adjust the pH to 1.5, and the temperature is raised to 55 ° C with constant temperature stirring, the stirring rate is 200 r / min, and the replacement is performed with 4N zinc plate, the replacement time is 6 h, and the replacement is performed. After washing and filtering, a sponge indium can be obtained.

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Abstract

一种铜铟镓硒物料的回收方法，主要包括硫酸+双氧水浸出、二氧化硫还原硒、水解分铜、碱分铟镓、置换铟、水解镓等步骤。采用硫酸配合双氧水浸出，浸出率大大提高，且较少酸气污染；利用金属离子水解PH差分铜，成本低；另外采用碱性分镓，只需调节溶液PH值，即可实现铟镓分离，且分离效果好，得到的铟、镓产品纯度较高。

Description

一种铜铟镓硒物料的回收方法 技术领域
本发明涉及一种铜铟镓硒光伏组件的回收方法，尤其涉及一种铜铟镓硒物料的回收方法。
背景技术
铜铟镓硒薄膜太阳能电池具备众多优势而备受市场青睐，尤其是最近几年薄膜太阳能电池研发、规模生产、应用的最大热点。铜铟镓硒太阳能电池的吸收层由铜、铟、镓、硒四种元素按照最佳比例组成黄铜矿结构，可吸收光谱波长范围广，除了非晶硅太阳能电池可吸收光的可见光谱范围，还可以涵盖波长在700～2000nm之间的近红外区，即一天内发电的时间最长，铜铟镓硒薄膜太阳能电池与同一瓦数级别的晶硅太阳能电池相比，每天可以超出20％比例的总发电量。晶硅电池本质上有光致衰减的特性，经过阳光的长时间暴晒，其发电效能会逐渐减退。而铜铟镓硒太阳能电池则没有光致衰减特性，发电稳定性高。晶硅太阳能电池经过较长一段时间发电后存在热斑现象，导致发电量小，增加维护费用。而铜铟镓硒太阳能电池能采用内部连接结构，可避免此现象的发生，较晶体硅太阳能电池比所需的维护费用低。
铜铟镓硒薄膜太阳能电池的制作方式有真空溅镀法、蒸馏法和非真空涂布法，无论采用哪种制作方法，其制作过程中都会产生一些铜铟镓硒的物料，而这些物料中除含重金属铜之外，还含有铟、镓和硒等稀有金属。为有利于铟、镓和硒等稀有金属和重金属铜的持续利用，需要将其进行分离并分别回收，以方便进一步地循环利用，以保证铜铟镓硒薄膜太阳能电池材料的可持续发展。现有技术中，铜铟镓硒物料的回收方法主要有酸溶解法、萃取法、氧化蒸馏法 等湿法或火法精炼组合方法。
公开号为CN102296178A的中国专利申请中公开了一种铜铟镓硒的回收方法，具体公开了利用盐酸与过氧化氢的混合液来溶解包含有铜铟镓硒金属粉体的方法。该方法使用肼还原硒，以铟金属置换铜，并通过支撑式液膜结合分散反萃液将铟与镓分离。
公开号为CN103184388A的中国专利申请中公开了一种铜铟镓硒的回收方法，该方法首先破碎所述铜铟镓硒薄膜太阳能板成碎片，而后利用浸泡工序将所述碎片用规定温度的硫酸与过氧化氢的混合体系浸泡规定时间得到浸泡液，随后利用萃取，反萃取，电解等工艺回收铟、镓、硒元素。
美国专利号US5779877公开了一种铜铟硒太阳能电池物料的回收方法。所述方法主要包括破碎、硝酸浸出，两电极电解分离铜、硒和铟，然后蒸发分解得到铟和锌的氧化物的混合物，氧化蒸馏分离铜和硒。
在上述现有技术术中，使用盐酸和过氧化氢浸出会消耗大量的氧化剂，且盐酸易挥发，在浸出反应过程中是放热反应，造成盐酸大量挥发，污染较为严重。同时，萃取铟时使用的萃取剂对镓产生共萃现象，造成铟、镓分离困难，从而降低了镓的回收率。另一方面采用铟置换铜处理方法，生产成本过于高昂。
发明内容
为解决现有技术中的上述缺陷，本发明的目的在于提供一种能够减少环境污染，且铟回收率高，生产成本较低的铜铟镓硒物料的回收方法。
本发明的铜铟镓硒物料的回收方法采用硫酸配合双氧水浸出，浸出率大大提高，且减少酸气污染；还原硒后液利用金属离子水解PH差，精细化调整PH值可以先分出铜，操作简单，且成本较低；另一方面，本发明采用碱性分镓， 只需要调节溶液PH值，即可实现铟镓分离，分离效果好，所得到的铟、镓产品纯度较高。
本发明的铜铟镓硒物料的回收方法，包括如下步骤：
步骤A，将铜铟镓硒物料放置于球磨机中进行球磨。
步骤B，将浓硫酸稀释，将步骤A中球磨后的合金粉末与稀释后的浓硫酸混合，升温后通入双氧水进行浸出，浸出结束后滤出残渣，即可得到纯净浸出液。其所包括的反应如下：
Figure PCTCN2016112152-appb-000001
Figure PCTCN2016112152-appb-000002
Figure PCTCN2016112152-appb-000003
Figure PCTCN2016112152-appb-000004
Figure PCTCN2016112152-appb-000005
步骤C，将浸出液升温后通入二氧化硫气体，还原硒过程中会看到容器内有砖红色沉淀生成，逐渐变成黑色，过滤后得到黑硒。其包括的反应如下：
Figure PCTCN2016112152-appb-000006
步骤D，除硒后液直接加入氢氧化钠溶液调节PH值，常温搅拌后静置，随后抽取上清液，直接过滤得到氢氧化镓和氢氧化铟沉淀，以及硫酸铜上清液。其包括的反应如下：
6NaOH+In2(SO4)3→3Na2SO4+2In(OH)3
6NaOH+Ga2(SO4)3→3Na2SO4+2Ga(OH)3
步骤E，硫酸铜上清液直接蒸发结晶即可得到五水硫酸铜。
步骤F，将氢氧化镓和氢氧化铟沉淀加入氢氧化钠溶液加热，恒温搅拌后静置，随后抽取上清液，直接过滤得到氢氧化铟沉淀和镓酸钠溶液。其包括的反应如下：
Ga(OH)3+OH-→GaO2 -+2H2O
步骤G，镓酸钠溶液直接水解，即可得到氢氧化钾沉淀。
更具体地，可加入硫酸溶液调节PH值至中性，加入稀释后的聚丙烯酰胺，恒温搅拌进行絮凝沉淀，沉淀后抽取上清液，直接过滤得到氢氧化镓沉淀。其包括的反应如下：
GaO2 -+H++H2O→2Ga(OH)3
步骤H，将氢氧化铟沉淀用盐酸反溶，升温后恒温搅拌，用4N锌板进行置换，置换后洗涤过滤即可得到海绵铟。其包括的反应如下：
In(OH)3+3HCl→InCl3+3H2O
3Zn+2InCl3→3ZnCl2+2In
本发明的铜铟镓硒物料的回收方法，还包括，步骤A中的铜铟镓硒物料球磨成40目以下的粉末，球磨后在100℃下烘干4小时。
本发明的铜铟镓硒物料的回收方法，还包括，步骤B中将浓硫酸稀释至25％，将200g烘干料与25％浓硫酸按照固液比1：5混合，将温度升至90℃，按8ml/min速率通入双氧水，搅拌速率600r/min，恒温浸出3h。
本发明的铜铟镓硒物料的回收方法，还包括，步骤C中将浸出液升温至65℃后，通入二氧化硫气体，速率10L/min，恒温10h。
本发明的铜铟镓硒物料的回收方法，还包括，步骤D中除硒后液直接加入8mol/L氢氧化钠溶液调节PH值至4.5，常温搅拌20min，搅拌速率200r/min，静置2h后抽取上清液，反复洗涤抽取三次，每次洗涤水用水量不超过800ml。
本发明的铜铟镓硒物料的回收方法，还包括，步骤F中氢氧化镓和氢氧化铟沉淀加入8mol/L氢氧化钠溶液加热至80℃，搅拌速率200r/min，恒温搅拌20min后，静置2h后抽取上清液，反复洗涤抽取三次，每次洗涤用水量不超过800ml。
本发明的铜铟镓硒物料的回收方法，还包括，步骤G中镓酸钠溶液加入1mol/L硫酸溶液调节PH值至中性，加入稀释后10％聚丙烯酰胺20ml，恒温80℃，搅拌速率200r/min，恒温搅拌10min进行絮凝沉淀，沉淀后抽取上清液，反复洗涤沉降三次后抽取上清液，每次洗涤水用量不超过800mL，最后直接过滤得到氢氧化镓沉淀，氢氧化镓放在干燥箱中恒温80℃，干燥8h以上即可得到氢氧化镓。
本发明的铜铟镓硒物料的回收方法，还包括，步骤H中将氢氧化铟沉淀用10％盐酸600ml反溶，溶解后调节PH值至1.5，升温至55℃时恒温搅拌，搅拌速率200r/min。
本发明的铜铟镓硒物料的回收方法，球磨制样后，采用稀释后的浓硫酸配合适量过氧化氢浸出，浸出率非常高，可达到95％以上；通入二氧化硫气体或者加入亚硫酸钠还原硒，对除硒后的溶液加入适量的氢氧化钠调pH值至4.5ˉ4.7，进行洗涤过滤，得到的硫酸铜上清液可直接蒸发结晶得到硫酸铜；得到的氢氧化铟、氢氧化镓沉淀直接调pH大于13，随后静置分离，上清液为镓酸钠溶液，可直接水解、过滤得到氢氧化镓，氢氧化铟沉淀直接用盐酸溶解后，锌板置换，得到海绵铟。采用本发明方法，硒回收率96％、铜回收率92％、铟、镓回收率92％ 以上；利用镓的两性，直接调节PH值分离铟、镓，成本低，操作简单。
附图说明
图1是本发明实施例的铜铟镓硒物料的回收方法的流程示意图。
具体实施方式
以下结合附图对本发明实施方式做进一步阐述。
如图1所示，本发明实施例的铜铟镓硒物料的回收方法包括如下主要步骤：
步骤A，将200g铜铟镓硒物料放置于球磨机中，球磨至40目以下的粉末，100℃下烘干4小时。
步骤B，将浓硫酸稀释至25％，将200g烘干料与25％浓硫酸按照固液比1：5混合，将温度升至90℃，按8ml/min速率通入双氧水，搅拌速率600r/min，恒温浸出3h，浸出结束后滤出残渣，即可得到铜铟镓硒浸出液。
步骤C，将浸出液升温至65℃后，通入二氧化硫气体，速率10L/min，恒温10h，还原硒过程中会看到容器内有砖红色沉淀生成，逐渐变成黑色，过滤后得到黑硒。
步骤D，除硒后液直接加入8mol/L氢氧化钠溶液调节PH值至4.5～4.7，常温搅拌20min，搅拌速率200r/min，静置2h后抽取上清液，反复洗涤抽取三次，每次洗涤水用水量不超过800ml，最后直接过滤得到氢氧化镓和氢氧化铟沉淀，以及硫酸铜上清液。
步骤E，硫酸铜上清液直接蒸发结晶即可得到五水硫酸铜。
步骤F，氢氧化镓和氢氧化铟沉淀加入8mol/L氢氧化钠溶液加热至80℃，搅拌速率200r/min，恒温搅拌20min后，静置2h后抽取上清液，反复洗涤抽取三次，每次洗涤用水量不超过800ml，最后直接过滤得到氢氧化铟沉淀和镓酸钠 溶液。
步骤G，对镓酸钠溶液加入1mol/L硫酸溶液调节PH值至中性，加入稀释后10％聚丙烯酰胺20ml，恒温80℃，搅拌速率200r/min，恒温搅拌10min进行絮凝沉淀，沉淀后抽取上清液，同步骤F，反复洗涤沉降三次后抽取上清液，每次洗涤水用量不超过800mL，最后直接过滤得到氢氧化镓沉淀，氢氧化镓放在干燥箱中恒温80℃，干燥8h以上即可得到氢氧化镓。
步骤H，将氢氧化铟沉淀用10％盐酸600ml反溶，溶解后调节PH值至1.5，升温至55℃时恒温搅拌，搅拌速率200r/min，用4N锌板进行置换，置换时间6h，置换后洗涤过滤即可得到海绵铟。
以上实施例仅用于对本发明进行具体说明，其并不对本发明的保护范围起到任何限定作用，本发明的保护范围由权利要求确定。根据本领域的公知技术和本发明所公开的技术方案，可以推导或联想出许多变型方案，所有这些变型方案，也应认为是本发明的保护范围。

Claims (9)

  1. 一种铜铟镓硒物料的回收方法，其特征在于包括如下步骤：
    步骤A，将铜铟镓硒物料放置于球磨机中进行球磨；
    步骤B，将步骤A中球磨后的合金粉末与稀释后的浓硫酸混合，升温后通入双氧水进行浸出，浸出结束后滤出残渣，得到浸出液；
    步骤C，将浸出液升温后通入二氧化硫气体，进行还原硒；
    步骤D，过滤除硒后的余液直接加入氢氧化钠溶液，常温搅拌后静置，随后抽取上清液，过滤得到氢氧化镓和氢氧化铟沉淀，以及硫酸铜上清液；
    步骤E，硫酸铜上清液直接蒸发结晶得到五水硫酸铜；
    步骤F，将步骤D中得到的氢氧化镓和氢氧化铟沉淀加入氢氧化钠溶液并加热，恒温搅拌后静置，随后抽取上清液，直接过滤得到氢氧化铟沉淀和镓酸钠溶液；
    步骤G，对镓酸钠溶液直接水解，得到氢氧化镓沉淀；
    步骤H，将氢氧化铟沉淀用盐酸反溶，升温后恒温搅拌，用4N锌板进行置换，得到海绵铟。
  2. 如权利要求1所述的铜铟镓硒物料的回收方法，还包括，步骤A中的铜铟镓硒物料球磨成40目以下的粉末，球磨后在100℃下烘干4小时。
  3. 如权利要求1所述的铜铟镓硒物料的回收方法，还包括，步骤B中将浓硫酸稀释至25％，将200g烘干料与25％浓硫酸按照固液比1：5进行混合，将温度升至90℃，按8ml/min速率通入双氧水，搅拌速率600r/min，恒温浸出3h。
  4. 如权利要求1所述的铜铟镓硒物料的回收方法，还包括，步骤C中将浸 出液升温至65℃后，以10L/min速率通入二氧化硫气体，恒温10h，进行还原硒。
  5. 如权利要求1所述的铜铟镓硒物料的回收方法，还包括，步骤D中除硒后余液直接加入8mol/L氢氧化钠溶液调节PH值至4.5，常温搅拌20min，搅拌速率200r/min，静置2h后抽取上清液，反复洗涤抽取三次，每次洗涤水用水量不超过800ml。
  6. 如权利要求1所述的铜铟镓硒物料的回收方法，还包括，步骤F中氢氧化镓和氢氧化铟沉淀加入8mol/L氢氧化钠溶液加热调节PH值至4.5，升温至80℃，搅拌速率200r/min，恒温搅拌20min后，静置2h后抽取上清液，反复洗涤抽取三次，每次洗涤用水量不超过800ml。
  7. 如权利要求1所述的铜铟镓硒物料的回收方法，还包括，步骤G中镓酸钠溶液加入1mol/L硫酸溶液调节PH值至中性，加入10％聚丙烯酰胺20ml，恒温80℃，搅拌速率200r/min，恒温搅拌10min进行絮凝沉淀，沉淀后抽取上清液，反复洗涤沉降三次后抽取上清液，每次洗涤水用量不超过800mL，直接过滤得到氢氧化镓沉淀。
  8. 如权利要求1或7所述的铜铟镓硒物料的回收方法，还包括，步骤G中氢氧化镓沉淀放在干燥箱中恒温80℃，干燥8h以上即可得到氢氧化镓。
  9. 如权利要求1所述的铜铟镓硒物料的回收方法，还包括，步骤H中将氢氧化铟沉淀用600ml 10％盐酸反溶，溶解后调节PH值至1.5，升温至55℃时恒温搅拌，搅拌速率200r/min。
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