CN109055748B - Defluorination chlorine agent and preparation method thereof and method for defluorination chlorine using same - Google Patents
Defluorination chlorine agent and preparation method thereof and method for defluorination chlorine using same Download PDFInfo
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- CN109055748B CN109055748B CN201811006287.3A CN201811006287A CN109055748B CN 109055748 B CN109055748 B CN 109055748B CN 201811006287 A CN201811006287 A CN 201811006287A CN 109055748 B CN109055748 B CN 109055748B
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
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- 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
Abstract
The invention discloses a defluorination chlorinating agent and a preparation method thereof and a method for removing fluorine and chlorine by using the defluorination chlorinating agent, belonging to the technical field of zinc hydrometallurgy, wherein the defluorination chlorinating agent comprises bismuth nitrate, aluminum nitrate and sodium silicate, and the mass ratio of the bismuth nitrate to the aluminum nitrate to the sodium silicate is 5-30:2-11: 1-9; the preparation method comprises heating for reaction, cooling and pulverizing; the method for removing fluorine and chlorine by using the composite material comprises slurrying for removing fluorine and chlorine, washing fluorine and chlorine-containing slag, washing water and washing slag with alkali, washing alkali and washing slag and recycling waste liquid. The invention can realize one-step fluorine and chlorine removal of the zinc hydrometallurgy system, has short process flow, simple operation, reusable reagent, less investment, environmental protection, economy, low cost and high fluorine and chlorine removal efficiency.
Description
Technical Field
The invention belongs to the technical field of zinc hydrometallurgy, and particularly relates to a defluorination chlorine agent, a preparation method thereof and a method for defluorination chlorine by using the defluorination chlorine agent.
Background
The global refined zinc yield is about 1400 million tons, and about 80 percent of the refined zinc is produced by a hydrometallurgical technology. With the rapid development of the zinc smelting industry, the zinc concentrate resources are in shortage, the zinc concentrate price is rising year by year, and most zinc smelting enterprises gradually adopt zinc-containing oxidation materials with more complex components and cheaper price to carry out electrogalvanizing production. Most zinc smelting plants adopt zinc-containing oxidation materials mainly from zinc oxide and outsourcing zinc oxide materials obtained by comprehensive utilization and harmless treatment of self-produced two slags (iron vitriol slag and lead silver slag), and compared with zinc concentrate calcine, the zinc concentrate calcine contains higher fluorine and chlorine, and the fluorine and the chlorine enter a zinc hydrometallurgy system along with the zinc-containing oxidation materials.
Fluorine and chlorine in the zinc-containing oxidation material can cause huge damage to a zinc hydrometallurgy smelting system and an acid making system, along with the continuous promotion of a zinc smelting process, part of fluorine and chlorine in the zinc-containing oxidation material can enter the acid making system along with flue gas, and the other part of fluorine and chlorine directly enters the zinc hydrometallurgy smelting system. Fluorine and chlorine entering a sulfuric acid system cause that acid outlet pipes of equipment such as an empty tower, a packed tower and a drying tower of the acid making system are corroded more seriously, so that spraying acid is extremely unevenly distributed, purifying, drying and absorbing effects are influenced, equipment such as a fan, a pump and a valve group are corroded, porcelain fillers in the towers are corroded to different degrees to cause catalyst pulverization, and finally, the zinc smelting acid making system is paralyzed. The other part of fluorine and chlorine enter the zinc hydrometallurgy smelting system along with the zinc oxide material, the content is gradually increased under the action of the accumulation effect, the serious corrosion of the whole zinc hydrometallurgy system equipment can be caused, the aging is accelerated, if effective removal measures are not taken in the leaching and purifying processes, the fluorine and chlorine can enter the electrodeposition system along with the flowing of the system solution, the high fluorine and chlorine in the electrolyte can cause serious damage to the zinc smelting electrodeposition process, and the passivation layer generated on the cathode aluminum and the anode lead plate can be damaged after the fluorine and chlorine in the solution exceed certain concentration, the zinc and the cathode aluminum plate are adhered and can not be peeled off in the electrodeposition process, even the cathode aluminum plate is broken and enters the electrolytic bath, when the concentration is too high, a large amount of lead and aluminum enter the electrolyte and are separated out at the cathode, so that the current efficiency and the quality of an electrozinc product are reduced, and finally the whole wet-process zinc smelting system is paralyzed. In addition, with the increase of the fluorine and chlorine concentration, a great amount of HCl, HF and Cl exist in the whole zinc hydrometallurgy process2When the gas overflows, the operation environment is deterioratedCausing unrecoverable injury to production personnel. Therefore, zinc smelting enterprises at home and abroad put forward strict limits on the fluorine and chlorine contents in the electrolyte, and generally require that fluorine ions are less than 50 mg/L and chlorine ions are less than 200 mg/L.
The current methods for removing fluorine and chlorine from a zinc sulfate solution system mainly comprise a precipitation method, an ion exchange method, an extraction method, an open-circuit hot-contact method and the like. Wherein the precipitation method is mainly characterized in that Cu capable of generating precipitate with fluorine and chlorine ions is added into zinc sulfate electrolyte1+、Ca2+Or an anion, to remove the fluorochloros from the solution. The dechlorinating agent of the method mainly comprises copper-containing slag and lime, and although the dechlorinating agent has a certain effect of removing chlorine in the zinc sulfate solution, the dechlorinating efficiency is low, the zinc loss is large, the prices of simple substance copper and silver slag are high, the process condition is difficult to control, and the dechlorinating agent is less in actual production. The ion exchange method has higher removal rate for fluorine and chlorine ions in the zinc sulfate solution, but the method has higher requirements for the selection of the exchange resin and the production parameter conditions in the dechlorination process, and a large amount of wastewater can be generated in the resin regeneration process, thereby limiting the application and popularization of the method. The extraction method adopts a zinc extractant, zinc in a zinc sulfate solution enters an organic phase, fluorine and chlorine are left in a water phase, and the aim of removing fluorine and chlorine is further fulfilled. The open-circuit hot-contact method is characterized in that zinc sulfate is dissolved and is contacted with hot air to form a zinc sulfate solution for removing fluorine and chlorine and a gas containing fluorine and chlorine, so that the aim of removing fluorine and chlorine in the zinc sulfate solution is fulfilled.
Disclosure of Invention
The invention aims to provide a defluorination chlorine agent and a preparation method thereof and a method for removing fluorine and chlorine by using the defluorination chlorine agent, so as to solve the problems of low dechlorination efficiency, large zinc loss, high cost, difficult control of process conditions, large amount of generated wastewater and excessive influence on zinc electrolysis and production energy consumption in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
the defluorination chlorinating agent comprises bismuth nitrate, aluminum nitrate and sodium silicate, wherein the mass ratio of the bismuth nitrate to the aluminum nitrate to the sodium silicate is 5-30:2-11: 1-9.
The mass ratio of the bismuth nitrate to the aluminum nitrate to the sodium silicate is 6:3: 1.
A preparation method of a defluorination chlorine agent comprises the following steps:
step one, heating reaction:
mixing bismuth nitrate, aluminum nitrate and sodium silicate, and heating to 500-1300 ℃ for reaction; under the heating condition, when the molar ratio is 1:1:1, a compound with the main component of bismuth aluminosilicate (Bi 2Al2SiO 8) is formed;
step two, cooling and crushing:
preserving the heat for 0.5 to 3 hours, naturally cooling, and crushing to obtain the defluorination chlorination agent. The fluorine and chlorine removal reagent with the granularity of less than 100 mu m is obtained after crushing and grinding.
In the first step, the heating rate is 10-50 ℃/min.
In the second step, the defluorination chlorine agent is crushed and then has the grain diameter of 0.1-100 mu m.
A method for removing fluorine and chlorine comprises the following steps:
step one, slurrying to remove fluorine and chlorine:
mixing a defluorination chlorine agent with a zinc waste electrolyte or dilute sulfuric acid, stirring for 10-30min, adding a low-acidity chlorine-containing zinc solution into a mixed solution, reacting for 0.3-2.5h to obtain fluorine-containing chlorine residues and defluorination chlorine solution, wherein the mass ratio of fluorine to the defluorination chlorine agent in the mixed solution is 10-45: 1;
step two, washing fluorine-containing chlorine residues:
washing the fluorine-containing chlorine slag with water, and filtering to obtain washing slag and washing liquid;
step three, washing slag with alkali:
washing the washing slag with alkali, and filtering to obtain alkali washing slag and alkali washing liquid;
step four, washing with alkaline washing slag:
washing the alkaline washing slag with water to obtain a regenerated fluorine and chlorine removal agent, and returning to the step one to be used as the fluorine and chlorine removal agent after the regenerated fluorine and chlorine removal agent is washed with water;
step five, waste liquid recovery:
and D, recovering zinc from the water washing liquid obtained in the step two, and treating the alkaline washing liquid obtained in the step three and the water washing liquid obtained in the step four as wastewater.
In the step one, the acidity of the zinc waste electrolyte or dilute sulfuric acid is 80-160g/L, the chlorine concentration in the chlorine-containing zinc solution is 0.2-10g/L, the fluorine concentration is 10-100mg/L, the zinc concentration is 20-160g/L, the temperature of the chlorine-containing zinc solution and the waste electrolyte is 20-40 ℃, the stirring speed is 150-400rad/min, and the pH value of the reaction end point is 0.5-4.
In the second step, the water is industrial water, the mass ratio of the industrial water to the fluorine-containing chlorine slag is 5-10:1, the washing temperature is 20-50 ℃, the washing time is 0.5-2.0h, and the stirring speed is 150-400 rad/min.
In the third step, the alkali washing adopts sodium hydroxide solution, the pH is not lower than 12, the mass ratio of the sodium hydroxide solution to the washing slag is 3-8:1, the reaction temperature is 10-50 ℃, and the stirring speed is 150-.
In the fourth step, the water is industrial water, the mass ratio of the water to the alkali washing slag is 4-6:1, the temperature is 20-80 ℃, and the stirring speed is 150-.
Compared with the prior art, the invention has the beneficial effects that:
the invention can realize one-step fluorine and chlorine removal of the zinc hydrometallurgy system, has short process flow, simple operation, reusable reagent, less investment, environmental protection, economy, low cost and high fluorine and chlorine removal efficiency.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The defluorination chlorinating agent comprises bismuth nitrate, aluminum nitrate and sodium silicate, wherein the mass ratio of the bismuth nitrate to the aluminum nitrate to the sodium silicate is 5-30:2-11: 1-9.
The mass ratio of the bismuth nitrate to the aluminum nitrate to the sodium silicate is 6:3: 1.
A preparation method of a defluorination chlorine agent comprises the following steps:
step one, heating reaction:
mixing bismuth nitrate, aluminum nitrate and sodium silicate, heating to 500-1300 ℃ for reaction, wherein the heating rate is 10-50 ℃/min;
step two, cooling and crushing:
preserving heat for 0.5-3h, naturally cooling, and pulverizing to particle size of 0.1-100 μm to obtain the final product.
A method for removing fluorine and chlorine comprises the following steps:
step one, slurrying to remove fluorine and chlorine:
mixing a defluorination chlorine agent with a zinc waste electrolyte or dilute sulfuric acid, stirring for 10-30min, adding a low-acidity chlorine-containing zinc solution into a mixed solution, reacting for 0.3-2.5h to obtain fluorine-containing chlorine residues and defluorination chlorine solution, wherein the mass ratio of fluorine to the defluorination chlorine agent in the mixed solution is 10-45: 1; the acidity of the zinc waste electrolyte or dilute sulfuric acid is 80-160g/L, the chlorine concentration in the chlorine-containing zinc solution is 0.2-10g/L, the fluorine concentration is 10-100mg/L, the zinc concentration is 20-160g/L, the temperature of the chlorine-containing zinc solution and the waste electrolyte is 20-40 ℃, the stirring speed is 150-400rad/min, and the pH value at the end of the reaction is 0.5-4;
step two, washing fluorine-containing chlorine residues:
washing the fluorine-containing chlorine slag with water, and filtering to obtain washing slag and washing liquid; the water is industrial water, the mass ratio of the industrial water to the fluorine-containing chlorine slag is 5-10:1, the washing temperature is 20-50 ℃, the washing time is 0.5-2.0h, and the stirring speed is 150-;
step three, washing slag with alkali:
washing the washing slag with alkali, and filtering to obtain alkali washing slag and alkali washing liquid; the alkaline washing adopts sodium hydroxide solution, the pH is not lower than 12, the mass ratio of the sodium hydroxide solution to the washing slag is 3-8:1, the reaction temperature is 10-50 ℃, and the stirring speed is 150-;
step four, washing with alkaline washing slag:
washing the alkaline washing slag with water to obtain a regenerated fluorine and chlorine removal agent, and returning to the step one to be used as the fluorine and chlorine removal agent after the regenerated fluorine and chlorine removal agent is washed with water; the water is industrial water, the mass ratio of the water to the alkali washing slag is 4-6:1, the temperature is 20-80 ℃, and the stirring speed is 150-;
step five, waste liquid recovery:
and D, recovering zinc from the water washing liquid obtained in the step two, and treating the alkaline washing liquid obtained in the step three and the water washing liquid obtained in the step four as wastewater.
Example 1
Mixing bismuth nitrate, aluminum nitrate and sodium silicate according to the mass ratio of 30:11:9, then putting the mixture into a heating furnace, heating the heating furnace to 1100 ℃ at the speed of 13 ℃/min, preserving heat for 0.5h, then naturally cooling to room temperature, taking out the mixture, and crushing and grinding the mixture to obtain the fluorine and chlorine removal reagent with the particle size of 50-100 mu m.
Mixing a defluorination chlorine agent with a zinc waste electrolyte or dilute sulfuric acid, stirring for 20min, adding a low-acidity chlorine-containing zinc solution into a mixed solution, reacting for 2.0h, and filtering to obtain fluorine-containing chlorine residues and defluorination chlorine solution, wherein the mass ratio of fluorine to the defluorination chlorine agent in the mixed solution is 35: 1; the acidity of the zinc waste electrolyte or dilute sulfuric acid is 140g/L, the chlorine concentration in the chlorine-containing zinc liquid is 2g/L, the fluorine concentration is 80mg/L, the zinc concentration is 130g/L, the temperature of the chlorine-containing zinc liquid and the waste electrolyte is 25 ℃, the stirring speed is 300rad/min, the pH at the end point of the reaction is 1.5, the chlorine content in the finally obtained defluorination chlorine liquid is 89mg/L, the fluorine content is 9.5mg/L, and the defluorination efficiency and the chlorine removal efficiency are respectively 95.55 percent and 88.2 percent.
Mixing fluorine-containing chlorine slag and industrial water according to a ratio of 7:1, cleaning for 1.5h at the temperature of 45 ℃ and at the stirring speed of 300rd/min, filtering to obtain water washing slag and zinc-containing water washing liquid, sending the water washing slag to alkaline washing, and returning the water washing liquid to leaching for utilization.
Mixing the washing slag with a sodium hydroxide solution with the pH value being more than 14 according to the liquid-solid ratio of 5:1, carrying out alkali washing at the temperature of 45 ℃ and the stirring speed of 300rd/min to obtain alkali washing slag and an alkali washing liquid, sending the alkali washing slag to water for washing, and sending the alkali washing liquid to wastewater for treatment.
Mixing the obtained alkaline washing slag with industrial clear water according to a liquid-solid ratio of 5:1, and then washing for 1h at the temperature of 50 ℃ and the stirring speed of 300rd/min to obtain a water washing liquid and a regenerated fluorine-chlorine removal reagent, wherein the regenerated fluorine-chlorine removal reagent participates in next fluorine-chlorine removal, and the water washing liquid is used for wastewater treatment.
Example 2
Mixing bismuth nitrate, aluminum nitrate and sodium silicate according to the mass ratio of 5:2:1, then putting the mixture into a heating furnace, heating the heating furnace to 500 ℃ at the speed of 10 ℃/min, preserving heat for 1h, then naturally cooling to room temperature, taking out the mixture, and crushing and grinding the mixture to obtain the fluorine and chlorine removal reagent with the particle size of 20-60 mu m.
Mixing a defluorination chlorine agent (containing a regeneration defluorination chlorine agent) with a zinc waste electrolyte or dilute sulfuric acid, stirring for 10min, mixing, adding a low-acidity zinc-containing liquid into a mixed solution, reacting for 0.3h, and filtering to obtain a defluorination chlorine residue and a defluorination chlorine liquid, wherein the mass ratio of fluorine to the defluorination chlorine agent in the mixed solution is 10; the acidity of the zinc waste electrolyte or dilute sulfuric acid is 80g/L, the chlorine concentration in the chlorine-containing zinc liquid is 0.2g/L, the fluorine concentration is 10mg/L, the zinc concentration is 20g/L, the temperature of the chlorine-containing zinc liquid and the waste electrolyte is 20 ℃, the stirring speed is 150rad/min, the pH at the end of the reaction is 0.5, the chlorine content in the finally obtained defluorination chlorine liquid is 45mg/L, the fluorine content is 3mg/L, and the defluorination efficiency and the chlorine removal efficiency are 77.5 percent and 70 percent respectively.
Mixing fluorine-containing chlorine slag and industrial water according to a ratio of 5:1, cleaning for 0.5h at the temperature of 20 ℃ and the stirring speed of 150rd/min, filtering to obtain water washing slag and zinc-containing water washing liquid, sending the water washing slag to alkaline washing, and returning the water washing liquid to leaching for use.
Mixing the washing slag with a sodium hydroxide solution with the pH value being more than 12 according to the liquid-solid ratio of 3:1, carrying out alkali washing at the temperature of 10 ℃ and the stirring speed of 150rd/min to obtain alkali washing slag and an alkali washing liquid, sending the alkali washing slag to water for washing, and sending the alkali washing liquid to wastewater for treatment.
Mixing the obtained alkaline washing slag with industrial clear water according to a liquid-solid ratio of 4:1, and then washing for 1h at the temperature of 20 ℃ and the stirring speed of 400rd/min to obtain a water washing liquid and a regenerated fluorine-chlorine removal reagent, wherein the regenerated fluorine-chlorine removal reagent participates in next fluorine-chlorine removal, and the water washing liquid is used for wastewater treatment.
Example 3
Mixing bismuth nitrate, aluminum nitrate and sodium silicate according to the mass ratio of 6:3:1, then putting the mixture into a heating furnace, heating the heating furnace to 1300 ℃ at the speed of 50 ℃/min, preserving the heat for 2 hours, then naturally cooling to room temperature, taking out the mixture, and crushing and grinding the mixture to obtain the fluorine and chlorine removal reagent with the particle size of less than 0.1-30 mu m.
Mixing a defluorination chlorine agent (containing a regeneration defluorination chlorine agent) with a zinc waste electrolyte or dilute sulfuric acid, stirring for 30min, mixing, adding a low-acidity zinc-containing liquid into a mixed solution, reacting for 2.5h, and filtering to obtain a defluorination chlorine residue and a defluorination chlorine liquid, wherein the mass ratio of fluorine to the defluorination chlorine agent in the mixed solution is 45: 1; the acidity of the zinc waste electrolyte or dilute sulfuric acid is 160g/L, the chlorine concentration in the chlorine-containing zinc liquid is 10g/L, the fluorine concentration is 100mg/L, the zinc concentration is 160g/L, the temperature of the chlorine-containing zinc liquid and the waste electrolyte is 40 ℃, the stirring speed is 400rad/min, the pH at the end point of the reaction is 4, the chlorine content in the finally obtained defluorination chlorine liquid is 105mg/L, the fluorine content is 8.5mg/L, and the defluorination efficiencies of fluorine and chlorine are respectively 98.95 percent and 91.5 percent.
Mixing fluorine-containing chlorine slag and industrial water according to a ratio of 10:1, cleaning for 2.0h at a temperature of 50 ℃ and a stirring speed of 400rd/min, filtering to obtain water washing slag and zinc-containing water washing liquid, sending the water washing slag to alkaline washing, and returning the water washing liquid to leaching for use.
Mixing the washing slag with a sodium hydroxide solution with the pH value of more than 12 according to the liquid-solid ratio of 8:1, carrying out alkali washing at the temperature of 50 ℃ and the stirring speed of 400rd/min to obtain alkali washing slag and an alkali washing liquid, carrying out water washing on the alkali washing slag, and carrying out wastewater treatment on the alkali washing liquid.
Mixing the obtained alkaline washing slag with industrial clear water according to a liquid-solid ratio of 6:1, and then washing for 1h at the temperature of 80 ℃ and the stirring speed of 400rd/min to obtain a water washing liquid and a regenerated fluorine-chlorine removal reagent, wherein the regenerated fluorine-chlorine removal reagent participates in next fluorine-chlorine removal, and the water washing liquid is used for wastewater treatment.
Claims (9)
1. A method for removing fluorine and chlorine is characterized in that: the preparation method of the defluorination chlorine agent comprises the following steps:
step one, heating reaction:
mixing bismuth nitrate, aluminum nitrate and sodium silicate, wherein the mass ratio of the bismuth nitrate to the aluminum nitrate to the sodium silicate is 5-30:2-11:1-9, heating to 1100-1300 ℃ for reaction to form bismuth aluminosilicate Bi serving as a main component2Al2SiO8A compound of (1);
step two, cooling and crushing:
preserving the heat for 0.5 to 3 hours, naturally cooling, and crushing to obtain the defluorination chlorination agent.
2. The method for removing fluorine and chlorine according to claim 1, wherein: the mass ratio of the bismuth nitrate to the aluminum nitrate to the sodium silicate is 6:3: 1.
3. The method for removing fluorine and chlorine according to claim 1 or 2, wherein: in the first step, the heating rate is 10-50 ℃/min.
4. The method for removing fluorine and chlorine according to claim 3, wherein: in the second step, the defluorination chlorine agent is crushed and then has the grain diameter of 0.1-100 mu m.
5. A method for removing fluorine and chlorine by using the defluorination agent prepared by any one of claims 1 to 4, which is characterized by comprising the following steps:
step one, slurrying to remove fluorine and chlorine:
mixing a defluorination chlorine agent with a zinc waste electrolyte or dilute sulfuric acid, stirring for 10-30min, adding a low-acidity chlorine-containing zinc solution into a mixed solution, reacting for 0.3-2.5h to obtain fluorine-containing chlorine residues and defluorination chlorine solution, wherein the mass ratio of fluorine to the defluorination chlorine agent in the mixed solution is 10-45: 1;
step two, washing fluorine-containing chlorine residues:
washing the fluorine-containing chlorine slag with water, and filtering to obtain washing slag and washing liquid;
step three, washing slag with alkali:
washing the washing slag with alkali, and filtering to obtain alkali washing slag and alkali washing liquid;
step four, washing with alkaline washing slag:
washing the alkaline washing slag with water to obtain a regenerated fluorine and chlorine removal agent and water washing liquid, and returning the regenerated fluorine and chlorine removal agent to the first step for use as the fluorine and chlorine removal agent after washing;
step five, waste liquid recovery:
and D, recovering zinc from the water washing liquid obtained in the step two, and treating the alkaline washing liquid obtained in the step three and the water washing liquid obtained in the step four as wastewater.
6. The method for removing fluorine and chlorine according to claim 5, wherein: in the step one, the acidity of the zinc waste electrolyte or dilute sulfuric acid is 80-160g/L, the chlorine concentration in the chlorine-containing zinc solution is 0.2-10g/L, the fluorine concentration is 10-100mg/L, the zinc concentration is 20-160g/L, the temperature of the chlorine-containing zinc solution and the waste electrolyte is 20-40 ℃, the stirring speed is 150-400rad/min, and the pH value of the reaction end point is 0.5-4.
7. The method for removing fluorine and chlorine according to claim 6, wherein: in the second step, the water is industrial water, the mass ratio of the industrial water to the fluorine-containing chlorine slag is 5-10:1, the washing temperature is 20-50 ℃, the washing time is 0.5-2.0h, and the stirring speed is 150-400 rad/min.
8. The method for removing fluorine and chlorine according to claim 7, wherein: in the third step, the alkali washing adopts sodium hydroxide solution, the pH is not lower than 12, the mass ratio of the sodium hydroxide solution to the washing slag is 3-8:1, the reaction temperature is 10-50 ℃, and the stirring speed is 150-.
9. The method for removing fluorine and chlorine according to claim 8, wherein: in the fourth step, the water is industrial water, the mass ratio of the water to the alkali washing slag is 4-6:1, the temperature is 20-80 ℃, and the stirring speed is 150-.
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| CN105861844A (en) * | 2016-03-30 | 2016-08-17 | 湖南麓云达环境科技有限公司 | Comprehensive recycling method for non-ferrous metal metallurgy acidic wastewater and zinc-containing residues |
| CN106756010A (en) * | 2016-12-29 | 2017-05-31 | 郴州丰越环保科技有限公司 | The method that fluorine in solution of zinc sulfate is removed after the roasting of zinc metallurgy white residue |
| CN107475530A (en) * | 2017-08-16 | 2017-12-15 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Dechlorination process in zinc hydrometallurgy |
| CN107998814A (en) * | 2017-11-24 | 2018-05-08 | 中南大学 | The processing system and its application process of a kind of smoking gas containing fluorine |
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