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CN114836632B - Method for extracting cadmium by using ionic liquid - Google Patents
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CN114836632B - Method for extracting cadmium by using ionic liquid - Google Patents

Method for extracting cadmium by using ionic liquid Download PDF

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Publication number
CN114836632B
CN114836632B CN202210670284.XA CN202210670284A CN114836632B CN 114836632 B CN114836632 B CN 114836632B CN 202210670284 A CN202210670284 A CN 202210670284A CN 114836632 B CN114836632 B CN 114836632B
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Prior art keywords
cadmium
leaching
ionic liquid
solution
extracting
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CN202210670284.XA
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CN114836632A (en
Inventor
蒋航宇
王璐
刘宇豪
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Tongxiang Siyuan Environmental Protection Technology Co ltd
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Tongxiang Siyuan Environmental Protection Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B17/00Obtaining cadmium
    • C22B17/04Obtaining cadmium by wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/387Cyclic or polycyclic compounds
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a method for extracting cadmium by using ionic liquid, which comprises the following steps: (1) Adding a leaching agent into the cadmium-containing material for leaching, and filtering after leaching to obtain a cadmium-containing leaching solution; (2) Adding an extractant into the cadmium-containing leaching solution to carry out cadmium extraction to obtain a cadmium-containing organic phase and raffinate, and returning the raffinate to the step (1) for cyclic leaching; (3) Washing impurities of the cadmium-containing organic phase by using impurity washing liquid to obtain a cadmium-containing organic phase after impurity washing; (4) Carrying out back extraction on the organic phase after washing impurities containing cadmium by using a back extractant to obtain a cadmium-containing rich solution; and (5) obtaining cadmium metal by using an electrodeposition process for the cadmium-containing pregnant solution. The method for extracting cadmium by using the ionic liquid has the advantages that the cadmium product with the purity of 99.99% can be obtained through simple processes of leaching, extracting, impurity washing, back extraction and electrodeposition, the process flow is short, and the leaching agent and the extracting agent can be recycled, so that the method is a novel environment-friendly process.

Description

Method for extracting cadmium by using ionic liquid
Technical Field
The invention relates to the technical field of metallurgy, in particular to a method for extracting cadmium by using ionic liquid.
Background
Cadmium is mainly an associated product in the smelting process of zinc-containing plumbite such as siderite, sulfur lead ore and the like, and is mainly applied to manufacturing cadmium-nickel alloy, pigment, plastic stabilizer, fluorescent powder, insecticide, bactericide, paint, electrical switch, automobile relay, battery and the like, and particularly has outstanding effects in the aspects of aviation industry, atomic reactor, electroplating corrosion prevention and the like. All these applications require very pure cadmium metal, typically 99.99% or more pure. The traditional cadmium refining process has complicated steps, involves multiple filtering, dissolving and replacing processes, and zinc, lead and copper are impurities which are difficult to remove in the cadmium refining process.
Disclosure of Invention
The invention aims to provide a method for extracting cadmium by using ionic liquid, which can obtain a cadmium product with purity up to 99.99% through simple processes of leaching, extracting, impurity washing, back extraction and electrodeposition.
In order to achieve the above object, the present invention provides a method for extracting cadmium by using an ionic liquid, comprising the following steps:
(1) Adding a leaching agent into the cadmium-containing material for leaching, and filtering after leaching to obtain a cadmium-containing leaching solution;
(2) Adding an extractant into the cadmium-containing leaching solution to carry out cadmium extraction to obtain a cadmium-containing organic phase and raffinate, and returning the raffinate to the step (1) for cyclic leaching; the extractant is ionic liquid;
(3) Washing impurities of the cadmium-containing organic phase by using impurity washing liquid to obtain a cadmium-containing organic phase after impurity washing;
(4) Carrying out back extraction on the organic phase after washing impurities containing cadmium by using a back extractant to obtain a cadmium-containing rich solution; the back extraction agent is one of alkaline, acidic or neutral back extraction agents;
(5) And (3) the cadmium-containing pregnant solution is subjected to an electrodeposition process to obtain cadmium metal, and the solution after the electrodeposition is returned to the step (4) for cyclic back extraction.
Preferably, the liquid-solid ratio of the cadmium-containing material to the leaching agent in the step (1) is 5-50, the leaching temperature is 20-100 ℃, and the reaction time is 0.5-4 h.
Preferably, the concentration of the leaching agent is 0-3 mol/L.
Preferably, the leaching agent is HCl, H 2 SO 4 、HNO 3 One or more of HBr, naCl aqueous solution.
Preferably, the ionic liquid is one or more of 1-hexyl-3-methylimidazolium hexafluorophosphate ionic liquid [ HMPSM ] [ PF6] and 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid [ BMPSM ] [ PF6 ].
Preferably, the cadmium-containing rich solution in the step (4) is Cd (NO) 3 ) 2 、CdCl 2 、CdSO 4 Is a mixture of one or more of the following.
Preferably, the stripping agent is NaOH or Ca (OH) 2 、KOH、HCl、HNO 3 、H 2 SO 4 One or more of ammonia water and pure water.
Therefore, the method for extracting cadmium by using the ionic liquid has the advantages of high ionic conductivity, nonflammability, non-volatility, high thermal stability, high solvent property, wide liquid phase temperature range and the like, is a green nonaqueous solution extractant, can realize a continuous and sustainable cadmium leaching extraction process, has the advantages of closed solution circulation in the whole process flow, simple operation and environment friendliness, and can achieve the aim of efficiently extracting cadmium in a green way.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a schematic process flow diagram of a method for extracting cadmium with an ionic liquid according to the present invention.
Detailed Description
The present invention will be further described with reference to examples in which various chemicals and reagents are commercially available unless otherwise specified.
Example 1
Configuration contains H 2 SO 4 The acid leaching agent is leached for 2 hours under the conditions that the liquid-solid ratio of the cadmium-containing material is 20:1 and the temperature is 30 ℃, and the leaching agent is filtered after the leaching is finished to obtain a cadmium-containing leaching solution, wherein the cadmium-containing leaching solution uses an extractant [ HMPSM ]][PF6]The ionic liquid is characterized in that the ratio of the ionic liquid to the ionic liquid is 1:1 for 50min, the extraction rate of cadmium is 90%, and the organic matter containing cadmium and raffinate are obtained after the extraction is completed. Washing the cadmium-containing organic matter with impurity washing liquid to obtain cadmium-containing washed organic matter, back extracting the cadmium-containing washed organic matter with sulfuric acid solution to obtain cadmium sulfate rich liquid, and electro-depositing the cadmium sulfate rich liquid to obtain cadmium metal and electro-deposited liquid, and back extracting the electro-deposited liquid circularly.
Example 2
Configuration contains H 2 SO 4 The acid leaching agent is leached for 2 hours under the conditions that the liquid-solid ratio of the cadmium-containing material is 20:1 and the temperature is 30 ℃, and the leaching agent is filtered after the leaching is finished to obtain a cadmium-containing leaching solution, wherein the cadmium-containing leaching solution adopts an extractant [ BMPSM ]][PF6]The ionic liquid is characterized in that the ratio of the ionic liquid to the ionic liquid is 1:1 for 30min, the extraction rate of cadmium is 90%, and the organic matter containing cadmium and raffinate are obtained after the extraction is completed. Washing the cadmium-containing organic matter with impurity washing liquid to obtain cadmium-containing washed organic matter, back extracting the cadmium-containing washed organic matter with sulfuric acid solution to obtain cadmium sulfate rich liquid, and electro-depositing the cadmium sulfate rich liquid to obtain cadmium metal and electro-deposited liquid, and back extracting the electro-deposited liquid circularly.
Example 3
Preparing an HCl-containing acidic leaching agent, leaching for 2 hours under the conditions that the liquid-solid ratio of a cadmium-containing material is 20:1 and the temperature is 30 ℃, filtering after leaching to obtain a cadmium-containing leaching solution, and comparing the cadmium-containing leaching solution with an extracting agent [ BMPSM ] [ PF6] ionic liquid according to the ratio of 1:1 for 30min, the extraction rate of cadmium is 80%, and the organic matter containing cadmium and raffinate are obtained after the extraction is completed. Washing the cadmium-containing organic matter with impurity washing liquid to obtain cadmium-containing washed organic matter, back extracting the cadmium-containing washed organic matter with sulfuric acid solution to obtain cadmium sulfate rich liquid, and electro-depositing the cadmium sulfate rich liquid to obtain cadmium metal and electro-deposited liquid, and back extracting the electro-deposited liquid circularly.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.

Claims (4)

1. A method for extracting cadmium by using ionic liquid, which is characterized by comprising the following steps:
(1) Adding a leaching agent into the cadmium-containing material for leaching, and filtering after leaching to obtain a cadmium-containing leaching solution;
the leaching agent is HCl, H 2 SO 4 、HNO 3 One or more of HBr, aqueous NaCl solution;
(2) Adding an extractant into the cadmium-containing leaching solution to carry out cadmium extraction to obtain a cadmium-containing organic phase and raffinate, and returning the raffinate to the step (1) for cyclic leaching; the extractant is ionic liquid;
the ionic liquid is one or more of 1-hexyl-3-methylimidazole hexafluorophosphate ionic liquid [ HMPSM ] [ PF6] and 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid [ BMPSM ] [ PF6 ];
(3) Washing impurities of the cadmium-containing organic phase by using impurity washing liquid to obtain a cadmium-containing organic phase after impurity washing;
(4) Carrying out back extraction on the organic phase after washing impurities containing cadmium by using a back extractant to obtain a cadmium-containing rich solution; the back extractant is alkaliOne of a sex, acidic or neutral stripping agent; the back extractant is NaOH, ca (OH) 2 、KOH、HCl、HNO 3 、H 2 SO 4 One or more of ammonia water and pure water;
(5) And (3) the cadmium-containing pregnant solution is subjected to an electrodeposition process to obtain cadmium metal, and the solution after the electrodeposition is returned to the step (4) for cyclic back extraction.
2. The method for extracting cadmium by using ionic liquid according to claim 1, wherein: in the step (1), the liquid-solid ratio of the cadmium-containing material to the leaching agent is 5-50, the leaching temperature is 20-100 ℃, and the reaction time is 0.5-4 h.
3. The method for extracting cadmium by using ionic liquid according to claim 1, wherein: the concentration of the leaching agent is 0-3 mol/L.
4. The method for extracting cadmium by using ionic liquid according to claim 1, wherein: the cadmium-containing rich solution in the step (4) is Cd (NO) 3 ) 2 、CdCl 2 、CdSO 4 Is a mixture of one or more of the following.
CN202210670284.XA 2022-06-14 2022-06-14 Method for extracting cadmium by using ionic liquid Active CN114836632B (en)

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CN116655472B (en) * 2023-04-17 2025-01-07 天津大学 Thioether-containing diammonium cationic liquid, preparation method and application thereof in Cd in aqueous solution2+And Pb2+Is separated by a separation method of (2)

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CN102513064A (en) * 2011-12-23 2012-06-27 广东工业大学 Preparation method and application of ionic liquid bonded silica adsorbent
CN104007099B (en) * 2014-06-04 2017-01-04 傅科杰 The detection method of cadmium in a kind of garment for children
CN107586959B (en) * 2017-09-11 2018-11-30 陕西科技大学 Utilize the method for heavy metal in intensified by ultrasonic wave functional ionic liquids extraction water
CN108977669B (en) * 2018-09-13 2020-07-17 中南大学 A method for deep removal of cadmium in high-concentration cobalt sulfate solution and recovery of cadmium
CN113260440B (en) * 2018-12-11 2023-07-14 艾尼股份公司 Method for selective recovery of transition metals from organic residues
CN110745900B (en) * 2019-11-04 2022-05-10 西安建筑科技大学 A kind of separation method of heavy metal hexavalent chromium and divalent cadmium
CN111041221B (en) * 2019-12-17 2022-07-12 中南大学 A method for recovering cadmium from cadmium-containing high-arsenic soot
CN112981104B (en) * 2021-02-05 2023-04-25 桐乡市思远环保科技有限公司 Method for treating cadmium-containing waste residues and recycling metal cadmium

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