CN107630147B - Method for removing chloride ions in electrolytic manganese solution - Google Patents
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Abstract
The invention discloses a method for removing chloride ions in electrolytic manganese solution, which is to remove R-Bi2O3Adding the chlorine removal agent into electrolytic manganese anode solution with the sulfuric acid content of 30-40g/l, stirring for 20-30 minutes to prepare slurry, adding the slurry into the electrolytic manganese solution to be treated, fully stirring for 40-60 minutes at the temperature of 40-60 ℃ at the stirring speed of 60 revolutions per minute, and filtering; injecting the filtrate into a qualified liquid system, and electrolyzing to obtain manganese metal; R-Bi2O3In the chlorine removing agent, R is silicon dioxide and manganese oxide, R-Bi2O3The mass of the added chlorine removal agent is 10-15 times of that of chloride ions in the electrolytic manganese solution; washing the filter residue with water, filtering, performing alkali washing on the chlorine-removed residue with alkaline solution for desorption and dechlorination, filtering, washing the filtered filter residue with water, filtering, and adding the filter residue into a chlorine-removed residue acidification tank for recycling; the invention can effectively and rapidly remove chlorine, and the chlorine removing agent can be recycled and reused, thereby having low cost.
Description
Technical Field
The invention belongs to the technical field of manganese hydrometallurgy, and relates to a method for removing chloride ions in electrolytic manganese solution.
Background
Because manganese ore contains a certain amount of chlorine elements, in the process of preparing solution by leaching manganese, the traditional solution preparation process can not separate the chloride ions, the chloride ions enter the electrolyte to influence the whole electrolytic process, and the chloride ions in the electrolytic manganese solution bring harm: (1) the product quality is influenced, and the operation environment is deteriorated by the generated chlorine; (2) the lead-based anode plate is corroded and damaged, and when the concentration of chloride ions reaches 200mg/L, the lead-based anode plate starts to be obviously corroded in a convex-concave manner; when the concentration of chloride ions reaches more than 300mg/L, the plate surface of the lead-based anode plate is seriously corroded, the thickness is quickly reduced, the damage is serious, and the service life of the lead-based anode is seriously influenced; (3) lead content in the electrolytic manganese product exceeds the standard while the anode plate is corroded.
The traditional dechlorination process comprises the following steps: (1) removing chlorine by using a manganese ore powder washing method: under certain conditions, the chlorine ions in the mineral powder are dissolved in water in a water washing process, and the content of the chlorine ions in the mineral powder is reduced through a solid-liquid separation process. (2) Ion exchange dechlorination of electrolytic manganese solution: d201 type anion exchange resin is adopted to carry out adsorption separation on chloride ions in the solution; however, the ion exchange dechlorination process of the electrolytic manganese solution has the following defects: the treatment time is long, the capacity of the resin is small, a treatment system is huge, large-scale production cannot be met, a large amount of high-acid wastewater is generated during resin regeneration, the environment-friendly discharge requirement is not met, a wastewater treatment process needs to be additionally added, the production cost is increased, manganese ions adsorbed in the resin enter the wastewater during resin regeneration, the manganese ions cannot be recovered, and the recovery rate is reduced. (3) Reducing the content of chloride ions by a solution open-circuit method: when the chloride ion content in the solution is accumulated to a certain degree, the anolyte with relatively low manganese content is led out, sodium bicarbonate is used for precipitation to obtain industrial manganese carbonate, and the industrial manganese carbonate is returned to a manganese sulfate leaching procedure, the chloride ions are remained in the aqueous solution, but a large amount of wastewater needs to be treated and discharged.
In summary, the problems of the prior art are as follows: the removal effect of chloride ions is poor, and the requirements of the production process cannot be met; the loss of manganese resources is large, and the production cost is increased; a large amount of waste water can not be treated, and the production process does not meet the requirements of national environmental protection policies, so that production enterprises face the crisis of falling closure.
Disclosure of Invention
In order to achieve the aim, the invention provides a method for removing chloride ions in electrolytic manganese solution, which adopts R-Bi2O3The chlorine removal agent removes chloride ions in the electrolytic manganese solution, can effectively and quickly remove chlorine, can be recycled, and is low in cost; solves the problems of large loss of manganese resources and difficult treatment of a large amount of wastewater in the prior art when chloride ions are removed.
The technical scheme adopted by the invention is that the method for removing chloride ions in the electrolytic manganese solution specifically comprises the following steps:
step 1, adding R-Bi2O3Adding the chlorine removal agent into electrolytic manganese anode solution with sulfuric acid concentration of 30-40g/l to obtain R-Bi2O3The mass ratio of the chlorine removal agent to the electrolytic manganese anode solution is 1: 4-6, stirring for 20-30 minutes to prepare slurry, and adjusting the pH value of the slurry reaction end point to 1-3 by using dilute sulfuric acid; adding the slurry into an electrolytic manganese solution to be treated, fully stirring at the stirring speed of 60 revolutions per minute for 40-60 minutes at the temperature of 40-60 ℃, adjusting the pH value of the dechlorination reaction end point to be 4.8 by using dilute sulfuric acid, and filtering; injecting the filtrate into a qualified liquid system, and electrolyzing to obtain manganese metal;wherein, R-Bi2O3In the chlorine removing agent, R is silicon dioxide and manganese oxide, R-Bi2O3The adding mass of the chlorine removal agent is 10-15 times of the mass of chloride ions in the electrolytic manganese solution to be treated;
step 2, washing and filtering the filter residue obtained in the step 1 in sequence, and storing the filtrate after washing for continuous use when washing next time; when the manganese in the washing liquid is accumulated to 25-30g/l, returning to the qualified liquid system in the step 1;
3, carrying out alkali washing, resolving and dechlorinating on the dechlorination slag filtered in the step 2 by adopting alkali liquor with the pH value of more than 12, filtering, and sequentially washing, filtering and adding the filtered filter residue into a dechlorination slag acidification tank for recycling; storing the filtrate after washing for the next time, and performing centralized treatment and discharging when the concentration of chloride ions in the filtrate reaches 20-25 g/l.
The present invention is also characterized in that, further, in the step 1, R-Bi2O3The chlorine removing agent is prepared from silicon dioxide, manganese oxide and Bi2O3According to the mass ratio of 1: 1: 8, mixing, calcining and grinding by a Raymond mill to obtain the powder.
Further, said R-Bi2O3The fineness of the type dechlorinating agent is 200-400 meshes.
Further, in the step 1, the pH value of the electrolytic manganese solution to be treated is 6.4-6.8.
Further, in the step 3, an alkali liquor is an NaOH solution.
The invention has the beneficial effects that: the invention has the following advantages:
(1) the method is safer: no harmful substances are generated in the chlorine removal process;
(2) more environment-friendly: the chlorine removal agent body does not contain water-soluble impurities, the chlorine removal process does not have negative influence on the solution, the impurities in the manganese sulfate solution are not increased, and the chlorine removal amount is small;
(3) the dechlorination efficiency is high: the modified functional group in the chlorine removal agent can ensure higher removal efficiency of chloride ions;
(4) can be regenerated and used: the dechlorinating agent has better regeneration capability, can be recycled for many times, and has small loss in the regeneration process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow chart of the operation of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The chemical principle for removing chloride ions in the electrolytic manganese solution is as follows:
acidifying: R-Bi2O3+H2SO4＝(R-BiO)2SO4+H2O
Dechlorination: (R-BiO)2SO4+MnCl＝2R-BiOCl+MnSO4
And (3) analysis: R-BiOCl + NaOH ═ R-BiOOH + NaCl
The method for removing chloride ions in the electrolytic manganese solution specifically comprises the following steps:
step 1, the electrolytic manganese anolyte is composed of MnSO433-42g/l，(NH4)2SO490-120g/l，H2SO435-40 g/l; the electrolytic manganese solution to be treated has the composition MnSO4105-120g/l，(NH4)2SO490-120g/l, MnCl, pH6.4-6.8; R-Bi2O3Adding the chlorine removal agent into electrolytic manganese anode solution with sulfuric acid content of 30-40g/l to obtain R-Bi2O3The mass ratio of the anode solution to the electrolytic manganese anode solution with the sulfuric acid content of 30-40g/l is 1: 4-6, stirring for 20-30 minutes to prepare slurry, adjusting the pH value of the slurry reaction end point to 1-3 by using dilute sulfuric acid, adding the slurry into the electrolytic manganese solution to be treated, fully stirring for 40-60 minutes at the stirring speed of 60 revolutions per minute at the temperature of 40-60 ℃, adjusting the pH value of the dechlorination reaction end point to 4.8 by using dilute sulfuric acid, and filtering; the main component of the filtrate is MnSO4、(NH4)2SO4(ii) a Injecting the filtrate into a qualified liquid system, and electrolyzing to obtain manganese metal; wherein, R-Bi2O3In the chlorine removing agent, R is silicon dioxide and manganese oxide, R-Bi2O3The added mass of the chlorine removal agent is 10-15 times of that of chloride ions in the electrolytic manganese solution to be treated, and R-Bi2O3The excessive dosage of the chlorine removal agent causes unnecessary waste, and the too small dosage can not achieve the expected effect of chlorine removal;
step 2, washing and filtering the filter residue obtained in the step 1 in sequence, and washing MnSO attached to the chlorine residue with water4、(NH4)2SO4The consumption of alkaline washing liquid and the precipitation of ammonia gas can be reduced in the water washing process; storing the filtrate after washing for further use after next washing; when the manganese in the washing liquid is accumulated to 25-30g/l, returning to the qualified liquid system in the step 1;
step 3, carrying out alkali washing, resolving and dechlorinating on the dechlorination slag filtered in the step 2 by adopting alkali liquor (NaOH solution) with the pH value being more than 12, filtering, and adding the filtered filter residue into a dechlorination slag acidification tank for recycling after washing and filtering in sequence; storing the filtrate after washing for the next time, and performing centralized treatment and discharging when the concentration of chloride ions in the filtrate reaches 20-25 g/l. The purpose of the alkali wash analysis is to remove R-Bi2O3The water washing function after the alkali washing analysis of the chloride ions adsorbed on the chlorine removal agent ensures that the chloride ions after the alkali washing analysis do not return to the chlorine removal process, and the alkali washing analysis does not influence the chlorine removal efficiency when the chlorine removal agent is reused.
Because the oxide of bismuth has larger specific gravity, the reaction process is easy to precipitate, and the silicon dioxide, the manganese oxide and the Bi are2O3According to the mass ratio of 1: 1: 8 mixing, calcining, usingGrinding the powder by a Raymond mill to the fineness of 200-400 meshes; R-Bi2O3The chlorine removing agent is a gray black solid, takes an inorganic material as a matrix, is a composite inorganic chemical body synthesized by modifying functional groups, and leads R-Bi to be2O3The density of the agent is improved to 2.4g/cm, the reaction condition is greatly improved, and the generated R-BiOCl is more beneficial to filtration.
Compared with the prior art which contains bismuth and adopts R-Bi2O3The chlorine removal agent has the advantages that: 1. the R-inorganic group does not react in the solution, and new hetero ions cannot be brought into the solution; 2. change Bi2O3The specific gravity of R-BiOCl enables the R-BiOCl to participate in dechlorination reaction more effectively; 3. the molecular volume of the R-BiOCl is increased, and the filtering performance of solid-liquid separation is improved; by modifying the functional agent with Bi2O3The combination of (A) and (B) greatly improves the R-Bi2O3The frequency of the circular use of the chlorine removal agent is that the single Bi salt is used for removing chlorine for dozens of times, and the method is circularly used for nearly 1000 times in the application of chlorine removal in a certain plant and is also in continuous circulation; the dechlorination cost is greatly reduced.
Example 1, 17 g of R-Bi2O3Adding the type chlorine removal agent into 68g of electrolytic manganese anode solution with the sulfuric acid content of 35g/l, starting a stirrer, stirring for 20 minutes to prepare slurry, adjusting the pH value of the end point of the slurry reaction to be 2 by using dilute sulfuric acid, adding the slurry into 1000 ml of electrolytic manganese solution to be treated with the chlorine ion content of 1160 mg/L, fully stirring for 60 minutes at the temperature of 52 ℃ at the stirring speed of 60 revolutions per minute, adjusting the pH value of the end point of the chlorine removal reaction to be 4.6 by using dilute sulfuric acid, and filtering; the content of chloride ions in the filtrate was 87 g/l, and the removal rate of chlorine was 92.5%.
Example 2, 18 g of R-Bi2O3Adding the type chlorine removal agent into 90g of electrolytic manganese anode solution with the sulfuric acid content of 40g/l, starting a stirrer, stirring for 25 minutes to prepare slurry, adjusting the pH value of the end point of the slurry reaction to be 3 by using dilute sulfuric acid, adding the slurry into 1000 ml of electrolytic manganese solution to be treated with the chlorine ion content of 1230 mg/L, fully stirring for 45 minutes at the temperature of 55 ℃ at the stirring speed of 60 revolutions per minute, adjusting the pH value of the end point of the chlorine removal reaction to be 4.8 by using dilute sulfuric acid, and filtering; filtrateThe content of chloride ions in the product is 71.34 g/L, and the removal rate of chlorine is 94.2%.
Example 3, 11 g of R-Bi2O3Adding the type chlorine removal agent into 66g of electrolytic manganese anode solution with sulfuric acid content of 30g/l, starting a stirrer, stirring for 30 minutes for slurrying, adjusting the pH value of the end point of the slurrying reaction to be 1 by using dilute sulfuric acid, adding the slurry into 1000 ml of electrolytic manganese solution to be treated with the chloride ion content of 863 g/l, fully stirring for 55 minutes at the temperature of 51 ℃ at the stirring speed of 60 revolutions/minute, adjusting the pH value of the end point of the chlorine removal reaction to be 4.4 by using dilute sulfuric acid, adjusting the chloride ion content in the filtrate to be 100.11 g/l, and removing the chlorine at 88.4%.
Example 4, 17 g of R-Bi2O3Adding the type chlorine removal agent into 85g of electrolytic manganese anode solution with the sulfuric acid content of 35g/l, starting a stirrer, stirring for 25 minutes to prepare slurry, adjusting the pH value of the end point of the slurry reaction to be 2 by using dilute sulfuric acid, adding the slurry into 1000 ml of electrolytic manganese solution to be treated with the chloride ion content of 1162 g/l, fully stirring for 60 minutes at the temperature of 54 ℃ at the stirring speed of 60 revolutions/minute, adjusting the pH value of the end point of the chlorine removal reaction to be 4.6 by using dilute sulfuric acid, adjusting the chloride ion content in the filtrate to be 102.26 g/l, and controlling the chlorine removal rate to be 91.2%.
Example 5, 14 g of R-Bi2O3Adding the type chlorine removal agent into 70g of electrolytic manganese anode solution with the sulfuric acid content of 40g/l, starting a stirrer, stirring for 30 minutes for slurrying, adjusting the pH value of the end point of the slurrying reaction to be 3 by using dilute sulfuric acid, adding the slurry into 1000 ml of electrolytic manganese solution to be treated with the chloride ion content of 975 g/l, fully stirring for 60 minutes at 58 ℃ at the stirring speed of 60 revolutions/minute, adjusting the pH value of the end point of the chlorine removal reaction to be 4.8 by using dilute sulfuric acid, adjusting the chloride ion content in the filtrate to be 74.1 g/l, and controlling the chlorine removal rate to be 92.4%.
Through analysis of experimental data, the temperature range is controlled to be 40-60 ℃, the energy consumption is increased when the reaction temperature is too high, the consumption of the chlorine removal agent is increased, and the chlorine removal efficiency is influenced when the temperature is too low; the stirring speed of the stirrer is 60 revolutions per minute; R-Bi2O3The dosage of the chlorine removal agent is controlled to be 10-15 times of the total amount of chloride ions, over-low affects the chlorine removal efficiency, and over-high causes the chlorine removal agentWaste; in the operation process, the pH value of the end point of the dechlorination reaction (namely when the filter is carried out after the filter is fully stirred for 60 minutes at the stirring speed of 60 revolutions per minute) is strictly controlled to be 4.4-4.8, the reaction time is about 40-60 minutes, the longer the reaction, the higher the dechlorination efficiency is, but after the reaction time exceeds 60 minutes, the improvement range of the dechlorination efficiency is not obvious, the energy consumption is increased, and the advisability is avoided.
The device for removing chloride ions in the electrolytic manganese solution consists of a stirring synthesis barrel, a filter press pump, a liquid transfer pump and a liquid storage tank; the stirring synthesis barrel is connected with a filter press, the filter press is connected with a filter press pump, and a filtrate outlet of the filter press is connected with a liquid storage tank through a liquid transfer pump; the stirring synthesis barrel and the liquid storage tank are made of PP materials, and the equipment volume and the required stirring strength are determined after single calculation according to different capacity characteristics of each production line; the filter press adopts high-temperature acid-resistant equipment, the filter press pump and the liquid transfer pump generally adopt high-temperature acid-resistant pumps, and the parameters of the equipment are determined after single calculation according to different productivity characteristics of each production line.
The main advantages of the production device are: the dechlorination reaction adopts a continuous treatment mode of continuous feeding and discharging; an automatic control chip is planned to be developed, an automatic operation mode is adopted, the processing efficiency is improved, the labor cost is saved, and the fixed investment is saved.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (5)
1. The method for removing chloride ions in electrolytic manganese solution is characterized by comprising the following steps:
step 1, adding R-Bi2O3Adding the chlorine removal agent into electrolytic manganese anode solution with sulfuric acid concentration of 30-40g/l to obtain R-Bi2O3The mass ratio of the chlorine removal agent to the electrolytic manganese anode solution is 1: 4-6, stirring for 20-30 minutes to prepare slurry, and adjusting the pH value of the slurry reaction end point to 1-3 by using dilute sulfuric acid; adding the slurry into electrolytic manganese solution to be treated at 40-60 deg.CFully stirring the mixture for 40 to 60 minutes at a stirring speed of 60 revolutions per minute, adjusting the pH value of the chlorine removal reaction endpoint to be 4.8 by using dilute sulfuric acid, and filtering the mixture to obtain filtrate with the main component of MnSO4、(NH4)2SO4(ii) a Injecting the filtrate into a qualified liquid system, and electrolyzing to obtain manganese metal; wherein, R-Bi2O3In the chlorine removing agent, R is silicon dioxide and manganese oxide, R-Bi2O3The adding mass of the chlorine removal agent is 10-15 times of the mass of chloride ions in the electrolytic manganese solution to be treated;
step 2, washing and filtering the dechlorination slag obtained in the step 1 in sequence, and storing the filtrate after washing for continuous use when washing next time; when the manganese in the washing liquid is accumulated to 25-30g/l, returning to the qualified liquid system in the step 1;
3, carrying out alkali washing, resolving and dechlorinating on the dechlorination slag filtered in the step 2 by adopting alkali liquor with the pH value of more than 12, filtering, and sequentially washing, filtering and adding the filtered filter residue into a dechlorination slag acidification tank for recycling; storing the filtrate after washing for the next time, and performing centralized treatment and discharging when the concentration of chloride ions in the filtrate reaches 20-25 g/l.
2. The method for removing chloride ions from an electrolytic manganese solution according to claim 1, wherein in step 1, R-Bi2O3The chlorine removing agent is prepared from silicon dioxide, manganese oxide and Bi2O3According to the mass ratio of 1: 1: 8, mixing, calcining and grinding by a Raymond mill to obtain the powder.
3. The method of claim 2, wherein the R-Bi is selected from the group consisting of2O3The fineness of the type dechlorinating agent is 200-400 meshes.
4. The method for removing chloride ions from an electrolytic manganese solution according to claim 1, wherein in the step 1, the electrolytic manganese solution to be treated has a pH of 6.4-6.8.
5. The method for removing chloride ions from an electrolytic manganese solution according to claim 1, wherein in step 3, NaOH solution is used as the alkali solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07267643A (en) * | 1994-02-14 | 1995-10-17 | Natl Inst For Res In Inorg Mater | Bismuth compound, method for producing the same and inorganic anion exchange material |
| CN103272410A (en) * | 2013-05-31 | 2013-09-04 | 青海华信冶炼有限公司 | Circular removal process for chloride ions in manganese sulfate electrolyte and application of cuprous hydroxide as dechlorinating agent |
| CN104487169A (en) * | 2012-06-21 | 2015-04-01 | 东亚合成株式会社 | Amorphous inorganic anion exchanger, resin composition for sealing electronic component, and method for producing amorphous bismuth compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07267643A (en) * | 1994-02-14 | 1995-10-17 | Natl Inst For Res In Inorg Mater | Bismuth compound, method for producing the same and inorganic anion exchange material |
| CN104487169A (en) * | 2012-06-21 | 2015-04-01 | 东亚合成株式会社 | Amorphous inorganic anion exchanger, resin composition for sealing electronic component, and method for producing amorphous bismuth compound |
| CN103272410A (en) * | 2013-05-31 | 2013-09-04 | 青海华信冶炼有限公司 | Circular removal process for chloride ions in manganese sulfate electrolyte and application of cuprous hydroxide as dechlorinating agent |
Non-Patent Citations (1)
| Title |
|---|
| 用氧化铋从锌电解液中除氯;吴文花等;《湿法冶金》;20141220;第33卷(第06期);第480-482页 * |
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