CN112080764A - Method for removing chlorine from zinc electrolyte - Google Patents

Method for removing chlorine from zinc electrolyte Download PDF

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Publication number
CN112080764A
CN112080764A CN202010967003.8A CN202010967003A CN112080764A CN 112080764 A CN112080764 A CN 112080764A CN 202010967003 A CN202010967003 A CN 202010967003A CN 112080764 A CN112080764 A CN 112080764A
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China
Prior art keywords
bismuth
zinc
chlorine
electrolyte
filtering
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CN202010967003.8A
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Chinese (zh)
Inventor
彭涛嘉
王军
后洁琼
臧佳克
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Northwest Research Institute of Mining and Metallurgy
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Northwest Research Institute of Mining and Metallurgy
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    • 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
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00—Compounds of bismuth
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

The invention discloses a method for removing chlorine from zinc electrolyte, belongs to the field of zinc electrolysis, and solves the problems of difficulty in control, high cost and secondary pollution in the conventional method. The invention comprises the following steps: adding bismuth subcarbonate into sulfuric acid solution, wherein the adding amount of the bismuth subcarbonate is 1-2 times of the theoretical mass of bismuth calculated according to the chlorine amount, adjusting the pH value of a system to 2-4 by using alkali, gradually converting the precipitate formed by reaction from yellow solid particles into white flocculent precipitate-monohydrate alkali type bismuth sulfate, and filtering; and (4) adding the wet slag filtered in the step one into zinc electrolyte, stirring and reacting for 1-5h at room temperature, and filtering. The method has the advantages that the chlorine removal rate of the electrolyte is over 93 percent, the concentration of chloride ions in the treated zinc sulfate electrolyte is lower than 0.3g/L, and the residual trace chloride ions can not influence the system. The method has the advantages of easy operation, easy control of process parameters, easy obtainment of raw materials, low cost, no new environmental pollution and the like.

Description

Method for removing chlorine from zinc electrolyte
Technical Field
The invention belongs to the field of zinc electrolysis, and particularly relates to a method for removing chlorine from zinc electrolyte.
Background
Chlorine is used as a harmful element in a zinc hydrometallurgy system, when the chlorine content is high, the cathode plate and the anode plate are corroded in electrolysis, the service life of the cathode plate and the anode plate is shortened, the zinc stripping is difficult, the power consumption is increased, and the equipment is also seriously corroded. When the anode plate is corroded by chlorine, the lead content in the electrolyte is also high, and when the lead content in the electrolyte exceeds 5mg/L, the quality of the cathode zinc sheet is directly influenced. In addition, when the chlorine content in the electrolyte is high, the generated chlorine gas deteriorates the operating environment and affects the health of operators. Therefore, the concentration of chloride ions in the electrolytic solution is controlled before electrolysis. The methods for removing chlorine from the electrolyte mainly include silver sulfate precipitation, copper slag chlorine removal, ion exchange and the like.
The silver sulfate precipitation method has good dechlorination effect, but the silver salt is expensive, the silver regeneration rate is low, and the method is not suitable for industrial production.
The cuprous chloride precipitation method is widely applied in industrial production at present, cuprous chloride can be recycled after regeneration treatment, but the method has long treatment time, difficult control of operation parameters and large amount of generated copper slag, and the solution after dechlorination needs to be subjected to copper removal treatment by using zinc powder.
The ion exchange method has the advantages of simple equipment and convenient operation, but the chlorine removal by adopting ion exchange can not meet the requirement of electrolytic zinc on chloride ions, and simultaneously, the regeneration of the resin has large water consumption and generates a large amount of waste water.
Disclosure of Invention
The invention aims to provide a method for removing chlorine from a zinc electrolyte, which aims to solve the problems of difficult control, high cost and secondary pollution generation in the existing method.
The technical scheme of the invention is as follows: a method for removing chlorine from a zinc electrolyte, characterized by comprising the steps of:
step one, preparing monohydrate caustic soda type bismuth sulfate: bismuth oxycarbonate (Bi)2O2CO3) Adding into sulfuric acid solution, adding bismuth subcarbonate in an amount of 1-2 times of theoretical mass of bismuth calculated according to chlorine amount, adjusting system pH to 2-4 with alkali, gradually converting precipitate formed by reaction from yellow solid particles into white flocculent precipitate-monohydrate alkali type bismuth sulfate, and filtering;
step two, chlorine removal test: and (4) adding the wet slag filtered in the step one into zinc electrolyte, stirring and reacting for 1-5h at room temperature, and filtering.
As a further improvement of the present invention, in the first step, the alkali may be one of sodium hydroxide, basic zinc carbonate and basic zinc sulfate.
As a further improvement of the invention, the preparation method of the bismuth subcarbonate comprises the following steps: dissolving bismuth citrate in ammonia water, stirring to dissolve completely, and adding sodium carbonate (Na) dropwise2CO3) And (3) allowing a solution to generate a white precipitate, reacting for 12-24h, filtering, washing with absolute ethyl alcohol and distilled water in sequence, and drying the product at 50-90 ℃ for 2-6h to obtain a bismuthyl carbonate product.
Further, the mass concentration of ammonia water was 5%.
The basic reaction formula for dechlorinating bismuth subcarbonate is as follows:
Bi2O2CO3+6H+→2Bi3++3H2O+CO2
Bi3++3Cl-→BiCl3
BiCl3+H2O→BiOCl↓+2HCl
the overall reaction formula is:
Bi2O2CO3+2Cl-+2H+＝2BiOCl↓+H2O+CO2↑
the invention has the beneficial effects that: the dechlorination of bismuth subcarbonate is based on that bismuth subcarbonate generates free bismuth ions under the acidic condition, the bismuth ions are combined with chloride ions in electrolyte to generate bismuth trichloride, the bismuth trichloride is hydrolyzed to generate bismuth oxychloride which is insoluble in water and sulfuric acid, and the solubility product of the bismuth oxychloride is low (1.8 multiplied by 10)-31) And is easy to separate from the solution. The method has the advantages that the chlorine removal rate of the electrolyte is over 93 percent, the concentration of chloride ions in the treated zinc sulfate electrolyte is lower than 0.3g/L, and the residual trace chloride ions can not influence the system. The method has the advantages of easy operation, easy control of process parameters, easy obtainment of raw materials, low cost, no new environmental pollution and the like.
At present, Bi2O2CO3The synthesis of (2) still focuses on hydrothermal reactions. This is mainly because the reaction usually uses Bi (NO)3)3As a precursor, Bi (NO)3)3Is easily hydrolyzed, and the hydrolysate is insoluble in water, so thatSo that the reaction with the relevant carbon source proceeds slowly. To suppress Bi (NO)3)3Hydrolysis of (2) acid (HNO) is currently frequently used3Or HAC) or organic solvents (EG or DMF); however, the use of acid as solvent requires the addition of an excess of carbon source, which results in Bi2O2CO3The appearance of the nanocrystalline is not easy to control; using an organic solvent, since Bi3+The release rate is slow, the growth of the nanocrystal is affected, and the reaction can be carried out under the condition of heating in most cases. The hydrothermal synthesis method has laggard development of crystal face and structure control means, and the performance is still poorer, especially because the absorption in a visible light region is weaker, the photocatalytic performance under visible light still needs to be improved. The invention adopts a very simple room temperature preparation method, uses bismuth citrate as a precursor, can be completely dissolved in ammonia water, can easily react with sodium carbonate after the solution, and obtains the carbonate oxygen Terma nanocrystal with excellent and controllable appearance by adjusting the proportion of raw materials and the reaction time, thereby realizing the room temperature controllable synthesis.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1, a method for removing chlorine from a zinc electrolyte comprising the steps of:
preparing bismuth subcarbonate: dissolving bismuth citrate in 5% ammonia water by mass, stirring to completely dissolve, and adding sodium carbonate (Na) dropwise2CO3) The solution is subjected to reaction for 12 hours, then is filtered, is washed for three times by using absolute ethyl alcohol and distilled water in sequence, and the product is dried for 6 hours at 50 ℃ to obtain a bismuth oxycarbonate preparation product;
preparing monohydrate basic bismuth sulfate: adding Bi2O2CO3Adding into sulfuric acid solution, Bi2O2CO3The addition amount of (A) is 1 time of the theoretical mass of bismuth calculated according to the chlorine amount, and Bi is2O2CO3The molar ratio of the sodium hydroxide to the sulfuric acid is 1:3, the mixture is stirred and reacted for 5 hours at the temperature of 50 ℃, and the pH value of the system is adjusted to be about 2 by using sodium hydroxide in the reaction process. The precipitate formed by the reaction gradually changed from yellow solid particles to white slightly flocculentPrecipitating monohydrate basic bismuth sulfate, and filtering;
chlorine removal test: and directly adding the filtered wet slag into 1L of zinc sulfate electrolyte, stirring and reacting for 1h at room temperature, and filtering. The filter residue is treated in the next step, the filtrate is analyzed and detected to obtain the chloride ion concentration, and the chloride ion removal rate is 89.24 percent
Example 2 a method for removing chlorine from a zinc electrolyte comprising the steps of:
preparation of bismuth oxycarbonate: dissolving bismuth citrate in 5% ammonia water by mass, stirring to completely dissolve, and adding sodium carbonate (Na) dropwise2CO3) Reacting the solution for 15 hours, filtering, washing the solution for three times by using absolute ethyl alcohol and distilled water in sequence, and drying the product at 70 ℃ for 5 hours to obtain a bismuth oxycarbonate preparation product;
preparing monohydrate basic bismuth sulfate: adding Bi2O2CO3Adding into sulfuric acid solution, Bi2O2CO3The addition amount of (A) is 1.5 times of the theoretical mass of bismuth calculated according to the chlorine amount, and Bi is2O2CO3The molar ratio of the zinc carbonate to the sulfuric acid is 1:3.2, the mixture is stirred and reacted for 5 hours at the temperature of 50 ℃, and the pH value of the system is adjusted to be about 2 by using basic zinc carbonate in the reaction process. Gradually changing the precipitate formed by the reaction from yellow solid particles into white slightly flocculent precipitate-monohydrate basic bismuth sulfate, and filtering;
chlorine removal test: and directly adding the filtered wet slag into 1L of zinc sulfate electrolyte, stirring and reacting for 2h at room temperature, and filtering. The filter residue is treated in the next step, the filtrate is analyzed and detected to obtain the chloride ion concentration, and the chloride ion removal rate is 90.18%.
Example 3 a method for removing chlorine from a zinc electrolyte comprising the steps of:
preparation of bismuth oxycarbonate: dissolving bismuth citrate in 5% ammonia water by mass, stirring to completely dissolve, and adding sodium carbonate (Na) dropwise2CO3) The solution is subjected to reaction for 18 hours, then is filtered, is washed by absolute ethyl alcohol and distilled water for three times, and the product is dried for 4 hours at 80 ℃ to obtain a bismuth oxycarbonate preparation product;
preparing monohydrate basic bismuth sulfate: adding Bi2O2CO3Adding into sulfuric acid solution, Bi2O2CO3The addition amount of (A) is 1.8 times of the theoretical mass of bismuth calculated according to the chlorine amount, and Bi is2O2CO3The molar ratio to sulfuric acid is 1: 3.5, stirring and reacting for 3 hours at the temperature of 60 ℃, and adjusting the pH of the system to be about 3 by using basic zinc sulfate in the reaction process. Gradually changing the precipitate formed by the reaction from yellow solid particles into white slightly flocculent precipitate-monohydrate basic bismuth sulfate, and filtering;
chlorine removal test: and directly adding the filtered wet slag into 1L of zinc sulfate electrolyte, stirring and reacting for 3h at room temperature, and filtering. The filter residue is treated in the next step, the filtrate is analyzed and detected to obtain the chloride ion concentration, and the chloride ion removal rate is 91.57%.
Example 4 a method for removing chlorine from a zinc electrolyte comprising the steps of:
preparation of bismuth oxycarbonate: dissolving bismuth citrate in 5% ammonia water by mass, stirring to completely dissolve, and adding sodium carbonate (Na) dropwise2CO3) Reacting the solution for 24 hours, filtering, washing the solution for three times by using absolute ethyl alcohol and distilled water in sequence, and drying the product at 90 ℃ for 2 hours to obtain a bismuth oxycarbonate preparation product;
preparing monohydrate basic bismuth sulfate: adding Bi2O2CO3Adding into sulfuric acid solution, Bi2O2CO3The addition amount of (A) is 2 times of the theoretical mass of bismuth calculated according to the chlorine amount, and Bi is2O2CO3The molar ratio of the sodium hydroxide to the sulfuric acid is 1:4, the mixture is stirred and reacted for 1 hour at the temperature of 70 ℃, and the pH value of the system is adjusted to be about 4 by using sodium hydroxide in the reaction process. Gradually changing the precipitate formed by the reaction from yellow solid particles into white slightly flocculent precipitate-monohydrate basic bismuth sulfate, and filtering;
chlorine removal test: and directly adding the filtered wet slag into 1L of zinc sulfate electrolyte, stirring and reacting for 5 hours at room temperature, and filtering. The filter residue is treated in the next step, the filtrate is analyzed and detected to obtain the chloride ion concentration, and the chloride ion removal rate is 93.52%.

Claims (4)

1. A method for removing chlorine from a zinc electrolyte, characterized by comprising the steps of:
step one, preparing monohydrate caustic soda type bismuth sulfate: adding bismuth subcarbonate into sulfuric acid solution, wherein the adding amount of the bismuth subcarbonate is 1-2 times of the theoretical mass of bismuth calculated according to the chlorine amount, adjusting the pH value of a system to 2-4 by using alkali, gradually converting the precipitate formed by reaction from yellow solid particles into white flocculent precipitate-monohydrate alkali type bismuth sulfate, and filtering;
step two, chlorine removal test: and (4) adding the wet slag filtered in the step one into zinc electrolyte, stirring and reacting for 1-5h at room temperature, and filtering.
2. A method according to claim 1 for removing chlorine from a zinc electrolyte, characterized in that: in the first step, the alkali can be one of sodium hydroxide, basic zinc carbonate and basic zinc sulfate.
3. A method according to claim 1 or 2 for removing chlorine from a zinc electrolyte, characterized in that: the preparation method of the bismuthyl carbonate comprises the following steps: dissolving bismuth citrate in ammonia water, then dropwise adding a sodium carbonate solution, reacting for 12-24h, filtering, washing with absolute ethanol and distilled water in sequence, and drying the product at 50-90 ℃ for 2-6h to obtain a bismuthyl carbonate product.
4. A method according to claim 3 for removing chlorine from a zinc electrolyte, characterized in that: the mass concentration of the ammonia water is 5%.
CN202010967003.8A 2020-09-15 2020-09-15 Method for removing chlorine from zinc electrolyte Pending CN112080764A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102154552A (en) * 2011-03-17 2011-08-17 云南祥云飞龙有色金属股份有限公司 Method for removing chlorine from chlorine-containing zinc sulfate solution by using bismuth trioxide
CN102527420A (en) * 2012-02-17 2012-07-04 重庆工商大学 Bismuth subcarbonate photocatalyst and preparation method thereof
CN108220998A (en) * 2018-03-08 2018-06-29 中南大学 A kind of method of manganese sulfate electrolyte purification dechlorination
JP2019195775A (en) * 2018-05-10 2019-11-14 国立大学法人 大分大学 Catalyst of oxygen generation reaction and oxygen reduction reaction
CN110734169A (en) * 2019-12-23 2020-01-31 长沙华时捷环保科技发展股份有限公司 Method for removing chlorine from acidic solutions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102154552A (en) * 2011-03-17 2011-08-17 云南祥云飞龙有色金属股份有限公司 Method for removing chlorine from chlorine-containing zinc sulfate solution by using bismuth trioxide
CN102527420A (en) * 2012-02-17 2012-07-04 重庆工商大学 Bismuth subcarbonate photocatalyst and preparation method thereof
CN108220998A (en) * 2018-03-08 2018-06-29 中南大学 A kind of method of manganese sulfate electrolyte purification dechlorination
JP2019195775A (en) * 2018-05-10 2019-11-14 国立大学法人 大分大学 Catalyst of oxygen generation reaction and oxygen reduction reaction
CN110734169A (en) * 2019-12-23 2020-01-31 长沙华时捷环保科技发展股份有限公司 Method for removing chlorine from acidic solutions

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Title
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Application publication date: 20201215