CN113151694A - Method for purifying zinc sulfate electrolyte by using metal aluminum powder - Google Patents

Method for purifying zinc sulfate electrolyte by using metal aluminum powder Download PDF

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Publication number
CN113151694A
CN113151694A CN202110227473.5A CN202110227473A CN113151694A CN 113151694 A CN113151694 A CN 113151694A CN 202110227473 A CN202110227473 A CN 202110227473A CN 113151694 A CN113151694 A CN 113151694A
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aluminum powder
purifying agent
purifying
zinc sulfate
acid
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CN202110227473.5A
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Inventor
叶乾旭
张明倩
蔡金明
荆煜涵
李婷
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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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
    • C22B19/00Obtaining zinc or zinc oxide
    • C22B19/20Obtaining zinc otherwise than by distilling
    • C22B19/26Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
    • 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
    • C22B3/44Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06Operating or servicing
    • 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)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to a method for purifying zinc sulfate electrolyte by using metal aluminum powder. It is characterized in that: the metal aluminum powder is taken as a main purifying agent, or a substance containing copper or antimony is added as an auxiliary purifying agent; firstly, activating aluminum powder in an acidic or alkaline solution with certain PH; adding a proper amount of purifying agent into a zinc sulfate solution to be purified with certain acidity and temperature, fully mixing and reacting under a certain atmosphere, and then carrying out liquid-solid separation; obtaining zinc electrolyte with qualified impurity metal ions and leaching residue containing high-grade valuable metals such as Ni, Co, Cu, Cd and the like. The invention has simple process, takes the metal aluminum powder with more negative potential than the standard electrode potential of the zinc powder (the traditional purifying agent) as the purifying agent, can shorten the purifying process flow, greatly reduces the using amount of the purifying agent, and produces the slag phase which is easy to recover the impurity valuable metal.

Description

Method for purifying zinc sulfate electrolyte by using metal aluminum powder
Technical Field
The invention relates to the field of leachate purification in hydrometallurgy, and can purify impurity metal ions in a zinc sulfate solution to be qualified by using metal aluminum powder as a purifying agent and produce leaching slag which is easy to recover impurity valuable metals.
Background
Impure metal ions (Cu) in unpurified zinc sulphate solution in zinc smelting enterprises2+、Cd2+、Co2+、Ni2+、Sb2+、Ge2+) The concentration is too high, which has great negative effect on the economic and technical indexes of zinc electrodeposition and the quality of zinc electroplating.
At present, a zinc powder replacement method is mainly adopted for purifying the impurity ions, but the using amount of the zinc powder is usually 6-10 times of the theoretical amount, the obtained slag phase has high zinc content and large slag amount, and the enrichment of valuable metals such as Cu, Cd, Co, Ni and the like is insufficient. The fundamental reason for this phenomenon is that the zinc powder used has a large particle size (about tens of microns), a small specific surface area and is liable to settle, and the impurity ions, which are not much in total in solution, are extremely dispersed, so that the effective utilization rate of the zinc powder is low. And submicron or nanometer zinc powder with smaller granularity has poor dispersibility in the solution, serious agglomeration and lower effective utilization rate.
Standard electrode potential of aluminum (Al)3+Al, -1.66V) far negative than Zn (Zn)2+Zn, -0.76V). The purification of zinc sulfate solution by using metal aluminum powder has two principle advantages: firstly, the electrode potential is lower than that of zinc, the thermodynamic condition of the replacement reaction with impurity metal ions is better, and the purification is more thorough; secondly, Zn can be converted from metal aluminum powder2+The replacement is performed by nano-grade zinc crystal grains with extremely good dispersibility, so that the kinetic condition of the replacement of impurity metal ions is greatly improved, and the utilization rate of aluminum is improved by multiple times. The process has three benefits: the purifying agent cost is greatly reduced, because the molar mass of the aluminum is 41.26 percent of that of the zinc, the electron quantity provided by each mole of the aluminum is 1.5 times that of the zinc, and the price of the metal aluminum is 78.16 percent of that of the zinc, so even if the purifying efficiency of the aluminum and the metal aluminum is the same, the cost of the aluminum consumption is only 21.46 percent of that of the zinc consumption; the slag quantity is reduced by times, and the valuable metals such as Cu, Cd, Co, Ni and the like in the slag phase have higher grades.
2 patent (application No. 201510507426.0, 201510507841.6) all propose a method of using high aluminum alloy zinc powder (Al content 0.5-25%, Cu content 0.05-0.4%, Pb content 1.5-10%, Sb content 0.01-0.15%, and Zn balance) as zinc sulfate solution scavenger. The method has certain effect, but the preparation process of the purifying agent is complex and the defect of using zinc powder cannot be avoided.
Although the metal aluminum powder has many advantages as a cleaning agent, the current use methods are not all satisfactory. Therefore, it is significant to develop a method of using metal aluminum powder as a zinc sulfate solution purifying agent under a wider range of conditions to exert the advantages of aluminum to the utmost and obtain a greater and more comprehensive purifying effect.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the method for purifying the zinc sulfate electrolyte by the metal aluminum powder is provided. The method takes metal aluminum powder as a main purifying agent or adds a substance containing copper or antimony as an auxiliary purifying agent, realizes the deep purification of the zinc sulfate solution at low cost under wider conditions, and produces a slag phase with high enrichment degree of valuable metals. The invention is realized by the following technical scheme.
A method for purifying zinc sulfate electrolyte by using metal aluminum powder comprises the following specific steps:
the metal aluminum powder is taken as a main purifying agent, or a substance containing copper or antimony is added as an auxiliary purifying agent; firstly, activating aluminum powder in an acidic or alkaline solution with certain PH; adding a proper amount of purifying agent into the zinc sulfate solution to be purified with certain acidity and temperature, fully mixing and reacting under a certain atmosphere, and then carrying out liquid-solid separation.
In the step [0009], the purity of the main purifying agent metal aluminum powder is more than 60 percent, the auxiliary purifying agents are copper-containing or antimony-containing substances such as metal copper, metal antimony, copper sulfate, antimony sulfate, copper oxide, antimony oxide and the like, and the particle sizes of the purifying agents are all-100 meshes.
In step [0009], the acidic solution is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, carbonic acid, citric acid, formic acid, propionic acid, etc., having a PH of about 1.0 to 5.5.
In the step [0009], the alkaline solution is a solution of sodium/potassium/calcium hydroxide, ammonia water, sodium carbonate and the like with the pH value of 7.5-11.
In the step [0009], the activation treatment temperature is 10-60 ℃, and the treatment time is 1-60 min.
In the step [0009], the proper amount of the activated metal aluminum powder is 1-6 times of the theoretical consumption required by purifying the zinc sulfate solution, and the addition amount of the depurative Cu or Sb is 0-250 mg/L.
In the step [0009], the zinc sulfate solution to be purified with certain acidity and temperature is the zinc sulfate solution to be purified with the temperature of 30-95 ℃ and the PH of 1-6.
Step [0009]]Wherein the atmosphere is an open atmosphere or a closed atmosphere (e.g., O)2、H2、SO2Etc.).
In the step [0009], the activated aluminum powder may be added at one time, or may be added in 2 or 3 times, and liquid-solid separation is performed each time.
In the step [0009], the mixing manner includes stirring, ultrasonic, flowing, heating, and the like.
The invention has the beneficial effects that: the application condition is wide, the using amount of the purifying agent is greatly reduced, impurities in the zinc sulfate solution can be deeply purified, the slag amount is small, and the enrichment degree of valuable metals in a slag phase is high.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1.
The method for purifying the zinc sulfate electrolyte by using the metal aluminum powder comprises the following steps:
adding 0.35g (1.1 times of theoretical consumption) of activated aluminum powder (-300 meshes, purity of 99.9% and activation in hydrochloric acid solution with pH of 2.0 for 5min) into 1L of zinc sulfate solution to be purified (containing Zn-148g/L, Cu-635mg/L, Cd 812mg/L, Co-6.5mg/L and Ni-21mg/L) at 73 deg.C and pH of 5.0 at one time, stirring for 50min, filtering to obtain filtrate and slag phase, wherein the components of the filtrate meet the zinc electrodeposition requirements (Cu-0.11mg/L, Cd-0.53mg/L, Co-0.32mg/L and Ni-0.59mg/L), and the enrichment degree of valuable metals in the slag phase is high (Zn-7.2%, Cu-39.55%, Cd-50.75%, Co-0.38%, Ni-1.25% and the rest is 0.87%).
Example 2.
The method for purifying the zinc sulfate electrolyte by using the metal aluminum powder comprises the following steps:
in 1L zinc sulfate solution to be purified (containing Zn-146g/L, Cu-820mg/L, Cd-649mg/L, Co-18.3mg/L, Ni-12.8mg/L) at 50 ℃ and pH 5.0, 0.45g (0.24 g added for the second time and 2.0 times of theoretical consumption) of metal aluminum powder (-300 meshes, 99.9% purity and 10min activation in sodium hydroxide solution at pH 11.0) and 0.108g of CuSO are added for the first time4(purity 99.9%) and 0.05g of SbSO4(purity 95%), stirring for 20min, and filtering to obtain primary filtrate and primary slag phase; adding 0.24g of activated metal aluminum powder into the primary filtrate at 38 ℃ (same as the primary filtrate), stirring for 10min, and filtering to obtain a secondary filtrate and a secondary slag phase, wherein the secondary filtrate comprises the components (Cu-0.12mg/L, Cd-0.28mg/L, Co-0.25mg/L and Ni-0.05mg/L), the enrichment degree of valuable metals in the primary slag phase is high (Zn-27.02%, Cu-39.53%, Cd-31.47%, Co-0.89%, Ni-0.59% and the other 0.50%), and the secondary slag phase mainly contains Zn.
Example 3.
The method for purifying the zinc sulfate electrolyte by using the metal aluminum powder comprises the following steps:
0.636g (1.06 times of theoretical consumption) of activated metal aluminum powder (-100 meshes, the purity of 62 percent and the balance of impurity Si) is added into 1L of zinc sulfate solution to be purified (containing Zn-138g/L, Cu-1020mg/L, Cd 510mg/L, Co-8.5mg/L and Ni-3.9mg/L) with the temperature of 85 ℃ and the pH of 3.5 at one time, the solution is activated in sodium hydroxide solution with the pH of 11.0 for 10min, a filtrate and a slag phase are obtained by filtering after stirring for 70min, wherein the components of the filtrate meet the zinc electrodeposition requirements (Cu-0.15mg/L, Cd-0.74mg/L, Co-0.41mg/L and Ni-0.63mg/L), the enrichment degree of valuable metals in the slag phase is high (Zn-6.09%, Cu-53.73%, Cd-0.43%, Co-0.43% and Ni-0.17%, the other 12.73%).

Claims (10)

1. A method for purifying zinc sulfate electrolyte by using metal aluminum powder is characterized by comprising the following steps:
the metal aluminum powder is taken as a main purifying agent, or a substance containing copper or antimony is added as an auxiliary purifying agent; firstly, activating aluminum powder in an acidic or alkaline solution with certain PH; adding a proper amount of purifying agent into the zinc sulfate solution to be purified with certain acidity and temperature, fully mixing and reacting under a certain atmosphere, and then carrying out liquid-solid separation.
2. The apparatus of claim 1, wherein: the purity of the metal aluminum powder is more than 60 percent, the purifying agent is copper-containing or antimony-containing substances such as metal copper, metal antimony, copper sulfate, antimony sulfate, copper oxide, antimony oxide and the like, and the granularity of the purifying agent is-100 meshes.
3. The apparatus of claim 1, wherein: the acidic solution is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, carbonic acid, citric acid, formic acid, propionic acid, etc. with pH of about 1.0-5.5.
4. The apparatus of claim 1, wherein: the alkaline solution is a solution of sodium/potassium/calcium hydroxide, ammonia water, sodium carbonate and the like with the pH value of 7.5-11.
5. The apparatus of claim 1, wherein: the activation treatment temperature is 10-60 ℃, and the treatment time is 1-60 min.
6. The apparatus of claim 1, wherein: the proper amount of the activated metal aluminum powder is 1-6 times of the theoretical consumption amount needed by purifying the zinc sulfate solution, and the addition amount of the auxiliary purifying agent Cu or Sb is 0-250 mg/L.
7. The apparatus of claim 1, wherein: the zinc sulfate solution to be purified with certain acidity and temperature is the zinc sulfate solution to be purified with the temperature of 30-95 ℃ and the PH of 1-6.
8. The apparatus of claim 1, wherein: the atmosphere is an open atmosphere or a closed atmosphere (e.g. O)2、H2、SO2Etc.).
9. The apparatus of claim 1, wherein: the activated aluminum powder can be added at one time, or added in 2 or 3 times, and liquid-solid separation is carried out each time.
10. The apparatus of claim 1, wherein: the mixing mode comprises stirring, ultrasonic, flowing, heating and the like.
CN202110227473.5A 2021-03-01 2021-03-01 Method for purifying zinc sulfate electrolyte by using metal aluminum powder Pending CN113151694A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1133228A (en) * 1980-10-24 1982-10-12 Robert C. Kerby Purification of zinc sulphate solution
US5453111A (en) * 1992-01-15 1995-09-26 Metals Recycling Technologies, Inc. Method for separation of metals from waste stream
CN104016403A (en) * 2013-12-16 2014-09-03 宁波市镇海新东方精细化工有限公司 Zinc sulfate impurity removal method
CN108277345A (en) * 2018-01-29 2018-07-13 昆明理工大学 A method of the copper removal cadmium from zinc sulfate leaching liquid
CN110129585A (en) * 2019-06-06 2019-08-16 何耀 A kind of method of Purification of zinc sulfate solution removing heavy metals
CN111254292A (en) * 2020-01-20 2020-06-09 昆明瀚创科技有限公司 Method for removing nickel, cobalt and germanium by zinc sulfate aqueous solution purification

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1133228A (en) * 1980-10-24 1982-10-12 Robert C. Kerby Purification of zinc sulphate solution
US5453111A (en) * 1992-01-15 1995-09-26 Metals Recycling Technologies, Inc. Method for separation of metals from waste stream
CN104016403A (en) * 2013-12-16 2014-09-03 宁波市镇海新东方精细化工有限公司 Zinc sulfate impurity removal method
CN108277345A (en) * 2018-01-29 2018-07-13 昆明理工大学 A method of the copper removal cadmium from zinc sulfate leaching liquid
CN110129585A (en) * 2019-06-06 2019-08-16 何耀 A kind of method of Purification of zinc sulfate solution removing heavy metals
CN111254292A (en) * 2020-01-20 2020-06-09 昆明瀚创科技有限公司 Method for removing nickel, cobalt and germanium by zinc sulfate aqueous solution purification

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Application publication date: 20210723