CN106277037A - Tellurium and the method for cadmium is reclaimed from cadmium telluride waste material - Google Patents
Tellurium and the method for cadmium is reclaimed from cadmium telluride waste material Download PDFInfo
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 29
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002699 waste material Substances 0.000 title claims abstract description 29
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 24
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 21
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 18
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims abstract description 17
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 44
- 239000002244 precipitate Substances 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 15
- 238000002386 leaching Methods 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract 3
- 238000003756 stirring Methods 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- C01B19/004—Oxides; Hydroxides
-
- 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/04—Binary compounds including binary selenium-tellurium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G11/00—Compounds of cadmium
- C01G11/02—Sulfides
-
- 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
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Abstract
Description
技术领域technical field
本发明涉及湿法冶金领域，尤其涉及一种从碲化镉中回收碲和镉的方法。The invention relates to the field of hydrometallurgy, in particular to a method for recovering tellurium and cadmium from cadmium telluride.
背景技术Background technique
碲化镉广泛应用于红外探测器、太阳能电池、光伏材料和X8射线探测器。目前，碲化镉薄膜太阳能行业发展迅速，被认为最有发展前景的太阳能技术之一，预计随着碲化镉薄膜太阳能行业发展，碲化镉的需求量将持续高速增长。Cadmium telluride is widely used in infrared detectors, solar cells, photovoltaic materials and X8-ray detectors. At present, the cadmium telluride thin-film solar industry is developing rapidly and is considered one of the most promising solar technologies. It is expected that with the development of the cadmium telluride thin-film solar industry, the demand for cadmium telluride will continue to grow rapidly.
目前碲化镉的生产方法主要集中液相合成和气相合成。在此过程中会产生碲化镉废料。中国专利申请CN200710049888.8公布了一种碲化镉的回收装置及其回收方法，利用火法冶炼直接回收碲化镉产品。此外，还未有一种从碲化镉废料中回收碲和镉的方法的公开文献报道。At present, the production methods of cadmium telluride mainly focus on liquid phase synthesis and gas phase synthesis. Cadmium telluride waste is produced in the process. Chinese patent application CN200710049888.8 discloses a cadmium telluride recovery device and its recovery method, using pyrometallurgy to directly recover cadmium telluride products. In addition, there is no published literature report on a method for recovering tellurium and cadmium from cadmium telluride waste.
因此，有必要提出一种从碲化镉废料中回收碲和镉的方法。Therefore, it is necessary to propose a method for recovering tellurium and cadmium from cadmium telluride waste.
发明内容Contents of the invention
本发明的目的在于提供一种工艺简单，操作安全，成本低廉，回收率高的从碲化镉废料中回收碲和镉的方法。The purpose of the present invention is to provide a method for recovering tellurium and cadmium from cadmium telluride waste with simple process, safe operation, low cost and high recovery rate.
为实现前述目的，本发明采用如下技术方案：一种从碲化镉废料中回收碲和镉的方法，其特征在于：其包括如下步骤：In order to achieve the aforementioned object, the present invention adopts the following technical scheme: a method for reclaiming tellurium and cadmium from cadmium telluride waste, characterized in that: it comprises the following steps:
步骤S1：将碲化镉废料破碎过筛后与水混合均匀，形成第一混合液；Step S1: crushing and sieving the cadmium telluride waste material and mixing them evenly with water to form a first mixed solution;
步骤S2：向第一混合液中加入酸，反应一段时间后，再加入氧化剂形成第二混合液；Step S2: adding an acid to the first mixed solution, and after reacting for a period of time, adding an oxidizing agent to form a second mixed solution;
步骤S3：过滤第二混合液，得到第一溶液和二氧化碲沉淀；Step S3: filtering the second mixed solution to obtain the first solution and tellurium dioxide precipitate;
步骤S4：向第一溶液中引入Cl-后加入亚硫酸钠还原净化，过滤得到粗碲沉淀和第二溶液；Step S4: introducing Cl- into the first solution, adding sodium sulfite for reduction purification, and filtering to obtain crude tellurium precipitate and the second solution;
步骤S5：再向第二溶液中加入硫化物，过滤得到硫化镉沉淀。Step S5: add sulfide to the second solution, and filter to obtain cadmium sulfide precipitate.
作为本发明的进一步改进，其包括如下步骤：As a further improvement of the present invention, it includes the following steps:
步骤S1：将碲化镉废料破碎过100目筛后，按液固比（7~3）：1与水,混合均匀，形成第一混合液；Step S1: After the cadmium telluride waste is crushed and passed through a 100-mesh sieve, it is mixed with water according to the liquid-solid ratio (7~3): 1 to form the first mixed liquid;
步骤S2：向第一混合液中加入化学计量比的1.4~1.7倍的质量分数为98%的浓硫酸，在60~70℃下反应1~6h后，滴加化学计量比的1.1~1.3倍的双氧水，80℃下保温反应1~2h，形成第二混合液；Step S2: Add concentrated sulfuric acid with a mass fraction of 98% of 1.4 to 1.7 times the stoichiometric ratio to the first mixed solution, react at 60 to 70°C for 1 to 6 hours, then add dropwise 1.1 to 1.3 times the stoichiometric ratio Hydrogen peroxide, heat preservation reaction at 80°C for 1~2h to form the second mixed solution;
涉及的化学反应式为：The chemical reactions involved are:
主反应：；Main response: ;
副反应：；side effects: ;
步骤S3：过滤第二混合液，得到第一溶液和二氧化碲沉淀；Step S3: filtering the second mixed solution to obtain the first solution and tellurium dioxide precipitate;
步骤S4：向第一溶液中引入Cl-后加入亚硫酸钠还原净化，过滤得到粗碲沉淀和第二溶液；Step S4: introducing Cl- into the first solution, adding sodium sulfite for reduction purification, and filtering to obtain crude tellurium precipitate and the second solution;
步骤S5：再向第二溶液中加入硫化物，过滤得到硫化镉沉淀。Step S5: add sulfide to the second solution, and filter to obtain cadmium sulfide precipitate.
作为本发明的进一步改进，所述步骤S2中滴加双氧水的过程中控制第一混合液电位在300mv~560mv之间，终点电极电位控制在500mv~550mv。As a further improvement of the present invention, in the process of adding hydrogen peroxide in the step S2, the potential of the first mixed solution is controlled between 300mv and 560mv, and the potential of the terminal electrode is controlled between 500mv and 550mv.
作为本发明的进一步改进，用于测量电位的电位计的参比电极为银/氯化银电极，测量电极为铂电极。As a further improvement of the present invention, the reference electrode of the potentiometer used for measuring potential is a silver/silver chloride electrode, and the measuring electrode is a platinum electrode.
作为本发明的进一步改进，步骤S3得到的二氧化碲沉淀经洗涤烘干后，得到纯度为2N~3N的 TeO2。As a further improvement of the present invention, the tellurium dioxide precipitate obtained in step S3 is washed and dried to obtain TeO 2 with a purity of 2N-3N.
作为本发明的进一步改进，步骤S5得到的硫化镉沉淀经洗涤烘干后，得到纯度为2N~3N的 CdS。As a further improvement of the present invention, the cadmium sulfide precipitate obtained in step S5 is washed and dried to obtain CdS with a purity of 2N-3N.
作为本发明的进一步改进，步骤S2中所加入的酸为硫酸、盐酸、硝酸其中之一。As a further improvement of the present invention, the acid added in step S2 is one of sulfuric acid, hydrochloric acid, and nitric acid.
作为本发明的进一步改进，步骤S2中所加入的氧化剂为过氧化氢、氯酸钠、氯气其中之一。As a further improvement of the present invention, the oxidizing agent added in step S2 is one of hydrogen peroxide, sodium chlorate and chlorine gas.
作为本发明的进一步改进，步骤S5中所加入的硫化物为硫化氢、硫化钠、硫化钾中的一种或多种。As a further improvement of the present invention, the sulfide added in step S5 is one or more of hydrogen sulfide, sodium sulfide, and potassium sulfide.
本发明通过控制碲化镉废料浸出过程中的氧化电位，实现碲和镉的分离回收，最终得到的二氧化碲和硫化镉纯度都能达到2 N~3N，工艺简单，操作安全，成本低廉，回收率高。The present invention realizes the separation and recovery of tellurium and cadmium by controlling the oxidation potential in the leaching process of cadmium telluride waste, and the purity of the finally obtained tellurium dioxide and cadmium sulfide can reach 2 N~3N, the process is simple, the operation is safe, and the cost is low. High recovery rate.
具体实施方式detailed description
下面将结合本发明实施例对技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solution will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
本发明提出一种从碲化镉废料中回收碲和镉的方法，步骤如下：The present invention proposes a method for reclaiming tellurium and cadmium from cadmium telluride waste, the steps are as follows:
步骤S1：将碲化镉废料破碎过100目筛后，按液固比（7~3）：1与水,混合均匀，形成第一混合液；Step S1: After the cadmium telluride waste is crushed and passed through a 100-mesh sieve, it is mixed with water according to the liquid-solid ratio (7~3): 1 to form the first mixed liquid;
步骤S2：向第一混合液中加入化学计量比1.4~1.7倍的质量分数为98%硫酸，在60~70℃下反应1~6h后，滴加化学计量比的1.1~1.3倍的双氧水，80℃下保温反应1~2h，形成第二混合液；Step S2: adding 98% sulfuric acid with a mass fraction of 1.4 to 1.7 times the stoichiometric ratio to the first mixed solution, reacting at 60 to 70°C for 1 to 6 hours, then adding hydrogen peroxide dropwise at 1.1 to 1.3 times the stoichiometric ratio, Insulate and react at 80°C for 1~2h to form the second mixed solution;
涉及的化学反应式为：The chemical reactions involved are:
主反应： Main response:
副反应： side effects:
步骤S3：过滤第二混合液，得到第一溶液和二氧化碲沉淀；Step S3: filtering the second mixed solution to obtain the first solution and tellurium dioxide precipitate;
步骤S4：向第一溶液中引入Cl-后加入亚硫酸钠还原净化，过滤得到粗碲沉淀和第二溶液；Step S4: introducing Cl- into the first solution, adding sodium sulfite for reduction purification, and filtering to obtain crude tellurium precipitate and the second solution;
步骤S5：再向第二溶液中加入硫化物，过滤得到硫化镉沉淀。Step S5: add sulfide to the second solution, and filter to obtain cadmium sulfide precipitate.
步骤S2中所加入的氧化剂过氧化氢可用氯酸钠、氯气其中之一代替。The oxidant hydrogen peroxide added in step S2 can be replaced by one of sodium chlorate and chlorine.
步骤S2中所加入的硫酸可用硝酸或者盐酸代替。The sulfuric acid added in step S2 can be replaced by nitric acid or hydrochloric acid.
步骤S5中所加入的硫化物为硫化氢、硫化钠、硫化钾中的一种或多种。The sulfide added in step S5 is one or more of hydrogen sulfide, sodium sulfide and potassium sulfide.
实施例1。Example 1.
取50g破碎过100目筛后的碲化镉废料，加入350ml的去离子水搅拌均匀后形成第一混合液，加入30g 98%浓硫酸，在60~70℃温度下，搅拌反应1h，再缓慢滴加50g 50% H2O2溶液形成第二混合液，过程中用电位计实时测量第一混合液的电位，将电位维持在300mv~560mv之间，电位计参比电极为银/氯化银电极，测量电极为铂电极，加完H2O2溶液后，在80℃下保温反应2h，过滤，得到第一溶液和二氧化碲沉淀，其中Te有少量入液，二氧化碲沉淀经过洗涤烘干，得到纯度为99.38%的TeO2，TeO2的直收率达96.69%，Cd浸出率达100%。向第一溶液中加入盐酸和亚硫酸钠还原进入溶液中的Te，过滤得到粗碲沉淀和第二溶液。再向第二溶液中通入硫化氢，过滤得到硫化镉沉淀，硫化镉沉淀经洗涤烘干得到纯度为99.9%的CdS，镉的回收率达100%。Take 50g of cadmium telluride waste crushed through a 100-mesh sieve, add 350ml of deionized water and stir evenly to form the first mixed solution, add 30g of 98% concentrated sulfuric acid, stir and react at 60~70°C for 1 hour, then slowly Add 50g of 50% H 2 O 2 solution dropwise to form the second mixed solution. During the process, use a potentiometer to measure the potential of the first mixed solution in real time, and maintain the potential between 300mv and 560mv. The reference electrode of the potentiometer is silver/chlorine Silver electrode, measuring electrode is platinum electrode, after adding H 2 O 2 solution, keep it warm at 80°C for 2 hours, filter to get the first solution and tellurium dioxide precipitate, in which a small amount of Te enters the liquid, and tellurium dioxide precipitates After washing and drying, TeO 2 with a purity of 99.38% was obtained, the direct recovery rate of TeO 2 was 96.69%, and the leaching rate of Cd was 100%. Add hydrochloric acid and sodium sulfite to the first solution to reduce Te in the solution, and filter to obtain crude tellurium precipitate and the second solution. Add hydrogen sulfide into the second solution, filter to obtain cadmium sulfide precipitate, wash and dry the cadmium sulfide precipitate to obtain CdS with a purity of 99.9%, and the recovery rate of cadmium reaches 100%.
实施例2。Example 2.
取600g破碎过100目筛后的碲化镉废料，加入1800ml的去离子水搅拌均匀后形成第一混合液，加入600g 98%浓硫酸，在60~70℃温度下，搅拌反应2h，再缓慢滴加360g 50%H2O2溶液形成第二混合液，加入H2O2溶液的过程中用电位计实时测量第一混合液的电位，将电位维持在300mv~560mv之间，电位计参比电极为银/氯化银电极，测量电极为铂电极，加完H2O2溶液后，在80℃下保温反应2h，过滤，得到第一溶液和二氧化碲沉淀，其中Te有少量入液，二氧化碲沉淀洗涤烘干，得到纯度为99.68%的TeO2，TeO2的直收率达96.9%，Cd浸出率达100%。向第一溶液中加入盐酸和亚硫酸钠还原进入溶液中的Te，过滤得到粗碲沉淀和第二溶液。再向第二溶液中加入硫化钠，过滤得到硫化镉沉淀，硫化镉沉淀经洗涤烘干得到纯度为99.9%的CdS，镉的回收率达100%。Take 600g of cadmium telluride waste crushed through a 100-mesh sieve, add 1800ml of deionized water and stir evenly to form the first mixed solution, add 600g of 98% concentrated sulfuric acid, and stir for 2 hours at a temperature of 60~70°C, then slowly Add 360g 50% H 2 O 2 solution dropwise to form the second mixed solution. During the process of adding the H 2 O 2 solution, use a potentiometer to measure the potential of the first mixed solution in real time, and maintain the potential between 300mv and 560mv. The reference electrode is a silver/silver chloride electrode, and the measuring electrode is a platinum electrode. After adding the H 2 O 2 solution, keep the reaction at 80°C for 2 hours, and filter to obtain the first solution and tellurium dioxide precipitate, in which Te has a small amount Enter the liquid, tellurium dioxide is precipitated, washed and dried to obtain TeO 2 with a purity of 99.68%, the direct recovery rate of TeO 2 is 96.9%, and the leaching rate of Cd is 100%. Add hydrochloric acid and sodium sulfite to the first solution to reduce Te in the solution, and filter to obtain crude tellurium precipitate and the second solution. Add sodium sulfide to the second solution, filter to obtain cadmium sulfide precipitate, wash and dry the cadmium sulfide precipitate to obtain CdS with a purity of 99.9%, and the recovery rate of cadmium reaches 100%.
实施例3。Example 3.
取600g破碎过100目筛后的碲化镉废料，加入3000ml的去离子水搅拌均匀后形成第一混合液，加入600g 98%浓硫酸，在60~70℃温度下，搅拌反应6h，再缓慢滴加360g 50%H2O2溶液形成第二混合液，加入H2O2溶液的过程中用电位计实时测量第一混合液的电位，将电位维持在300mv~560mv之间，电位计参比电极为银/氯化银电极，测量电极为铂电极，加完H2O2溶液后，在80℃下保温反应1h，过滤，得到第一溶液和二氧化碲沉淀，其中Te有少量入液，二氧化碲沉淀洗涤烘干，得到纯度为99.982%的TeO2，TeO2的直收率达97.24%，Cd浸出率达100%。向第一溶液中加入盐酸和亚硫酸钠还原进入溶液中的Te，过滤得到粗碲沉淀和第二溶液。再向第二溶液中加入硫化钾，过滤得到硫化镉沉淀，硫化镉沉淀经洗涤烘干得到纯度为99.9%的CdS，镉的回收率达100%。Take 600g of cadmium telluride waste crushed through a 100-mesh sieve, add 3000ml of deionized water and stir evenly to form the first mixed solution, add 600g of 98% concentrated sulfuric acid, stir and react at 60~70℃ for 6h, then slowly Add 360g 50% H 2 O 2 solution dropwise to form the second mixed solution. During the process of adding the H 2 O 2 solution, use a potentiometer to measure the potential of the first mixed solution in real time, and maintain the potential between 300mv and 560mv. The reference electrode is a silver/silver chloride electrode, and the measuring electrode is a platinum electrode. After adding the H 2 O 2 solution, keep the reaction at 80°C for 1 hour, and filter to obtain the first solution and tellurium dioxide precipitate, in which Te has a small amount Enter the liquid, tellurium dioxide is precipitated, washed and dried to obtain TeO 2 with a purity of 99.982%, the direct recovery rate of TeO 2 is 97.24%, and the leaching rate of Cd is 100%. Add hydrochloric acid and sodium sulfite to the first solution to reduce Te in the solution, and filter to obtain crude tellurium precipitate and the second solution. Add potassium sulfide to the second solution, filter to obtain cadmium sulfide precipitate, wash and dry the cadmium sulfide precipitate to obtain CdS with a purity of 99.9%, and the recovery rate of cadmium reaches 100%.
本发明通过控制碲化镉废料浸出过程中的氧化电位，实现碲和镉的分离回收，并且最终得到的二氧化碲和硫化镉纯度都能达到2 N~3N，工艺简单，操作安全，成本低廉，回收率高。The invention realizes the separation and recovery of tellurium and cadmium by controlling the oxidation potential in the leaching process of cadmium telluride waste, and the purity of the finally obtained tellurium dioxide and cadmium sulfide can reach 2 N~3N, the process is simple, the operation is safe, and the cost is low , high recovery rate.
尽管为示例目的，已经公开了本发明的优选实施方式，但是本领域的普通技术人员将意识到，在不脱离由所附的权利要求书公开的本发明的范围和精神的情况下，各种改进、增加以及取代是可能的。Although preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various Improvements, additions, and substitutions are possible.
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