CN111632940A - Post-treatment rinsing method for electrolytic manganese dioxide - Google Patents
Post-treatment rinsing method for electrolytic manganese dioxide Download PDFInfo
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- CN111632940A CN111632940A CN202010489978.4A CN202010489978A CN111632940A CN 111632940 A CN111632940 A CN 111632940A CN 202010489978 A CN202010489978 A CN 202010489978A CN 111632940 A CN111632940 A CN 111632940A
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Abstract
The invention discloses a post-treatment rinsing method of electrolytic manganese dioxide, comprising the following steps of S1: putting the manganese dioxide particles into an acid washing rinsing barrel to carry out acid washing rinsing for multiple times; s2: conveying the acid washing rinsing water to a combination slurrying tank for preparing a manganese sulfate solution; s3: putting manganese dioxide particles into an alkali neutralization rinsing barrel, and adding alkali liquor into the alkali neutralization rinsing barrel to perform alkali neutralization rinsing; s4: conveying the alkali neutralization rinsing water to an alkali liquor preparation heat-insulating barrel to prepare alkali liquor, and conveying the prepared alkali liquor to an alkali neutralization rinsing barrel for alkali neutralization rinsing when alkali neutralization rinsing is carried out again; s5: putting manganese dioxide particles into an alkali washing rinsing barrel, and performing alkali washing rinsing for multiple times by newly heating water, and performing post-treatment rinsing; s6: when the acid washing rinsing is carried out again, the alkali washing rinsing water is conveyed to the acid washing rinsing barrel for acid washing rinsing. The invention reduces the treatment cost of the rinsing wastewater and realizes the high-valued recovery and utilization of useful and effective components in the wastewater.
Description
Technical Field
The invention relates to a post-treatment rinsing method for electrolytic manganese dioxide, in particular to a method for recovering rinsing water in a post-treatment rinsing stage of electrolytic manganese dioxide.
Background
The post-treatment rinsing process of the electrolytic manganese dioxide product generally comprises three stages of acid washing, alkali neutralization and alkali washing, and mainly aims to wash out impurities such as sulfuric acid, sulfate and the like on the surfaces of electrolytic manganese dioxide particles and permeating into pores of the electrolytic manganese dioxide particles, such as Mn2+, Ca2+, Mg2+, Cu2+ and carbon rod powder. Through three-stage rinsing, the product can improve the manganese dioxide content by 1.5-3%, ensure the discharge performance and improve the characteristic effect of electrolytic manganese dioxide. Therefore, the rinsing process can not only reduce the water consumption, but also increase the rinsing strength according to the detection and analysis conditions of the product, so as to ensure the quality of the electrolytic manganese dioxide product. The rinsing process adopts a three-stage rinsing process of acid washing, alkali neutralization and alkali washing, specifically as shown in figure 1, wherein wastewater of acid washing for multiple times in the acid washing process is discharged after being treated by a medicament in a wastewater collecting tank, and wastewater of alkali washing for 3-5 hours in the alkali neutralization process and wastewater of water washing for multiple times in the alkali washing process are discharged after being treated by the medicament in a wastewater collecting tank; acid washing and alkali washing in rinsing can be finished by washing for many times, the water consumption is very large, the generated waste water is quite large, 6-8 tons of fresh water are needed for 1 ton of electrolytic manganese dioxide products according to production practice, and 6-8 tons of waste water are discharged. The discharged wastewater is treated by adopting a traditional wastewater centralized treatment mode, so that the treatment capacity is large, a large amount of medicaments are required, the treatment cost is high, the water resource is also huge waste, and more importantly, the heat energy, the acid value and the valuable manganese element carried in the rinsing wastewater are greatly wasted. Therefore, how to formulate a reasonable recycling and utilizing process aiming at the characteristics of the wastewater in different rinsing stages, reduce the treatment cost of the rinsing wastewater and realize the high-valued recycling and utilization of useful and effective components in the wastewater has great significance for the electrolytic manganese dioxide enterprises.
Disclosure of Invention
The invention aims to solve the technical problem of providing a post-treatment rinsing method for electrolytic manganese dioxide, which reduces the waste of water resources, reduces the treatment cost of up-to-standard discharge of rinsing water in the three rinsing stages as production sewage, purposefully recycles acid radicals, alkali radicals, manganese ions, heat break and other valuable components loaded by the rinsing water in the three rinsing stages, reduces the treatment cost of rinsing wastewater, and realizes high-valued recycling and utilization of useful and effective components in the wastewater.
The invention adopts the technical scheme that the post-treatment rinsing method of the electrolytic manganese dioxide comprises the following steps: s1: putting the manganese dioxide particles into an acid washing rinsing barrel to carry out acid washing rinsing for multiple times; collecting the washing acid rinsing water after the multiple washing acid rinsing to a washing acid rinsing water heat-preserving container to obtain washing acid rinsing mixed water; s2: conveying the mixed washing acid and rinsing water from the washing acid and rinsing water heat-preserving barrel to a chemical combination slurrying tank for preparing a manganese sulfate solution; s3: putting the manganese dioxide particles subjected to acid washing and rinsing in an alkali neutralization rinsing barrel, and adding hot alkali liquor to perform alkali neutralization rinsing; collecting the alkali neutralization rinsing water after the alkali neutralization rinsing into an alkali neutralization rinsing water heat-preserving bucket; s4: conveying alkali neutralization rinsing water from an alkali neutralization rinsing water heat-preserving bucket to an alkali liquor preparation heat-preserving bucket to prepare hot alkali liquor, and conveying the prepared hot alkali liquor to the alkali neutralization rinsing bucket for alkali neutralization rinsing when alkali neutralization rinsing is carried out again; s5: putting the manganese dioxide particles subjected to alkali neutralization and rinsing in an alkali washing rinsing barrel, and performing alkali washing rinsing for multiple times by newly adding hot water to finish post-treatment rinsing of the manganese dioxide particles; s6: collecting the alkali-washing rinsing water after multiple alkali-washing rinsing into an alkali-washing rinsing water heat-preserving barrel to obtain alkali-washing rinsing mixed water, and conveying the alkali-washing rinsing mixed water from the alkali-washing rinsing water heat-preserving barrel to an acid-washing rinsing barrel for acid-washing rinsing when acid-washing rinsing is carried out again.
Further, when acid rinsing is performed in the step S1, conveying heat-preserving mixed alkali-rinsing water to an acid-rinsing barrel containing electrolytic manganese dioxide, then starting a circulating pump to circulate rinsing water in the barrel from bottom to top, and simultaneously opening a rinsing steam valve to heat and preserve heat of the rinsing water in the barrel; stopping the circulating pump after the circulation rinsing is carried out for a set time, closing the rinsing water circulating valve, opening the drain valve, and discharging the acid washing rinsing water to finish the primary acid washing rinsing; the first acid washing and rinsing cycle is carried out for 0.5 hour, and the acid washing and rinsing temperature is set to be 80-90 ℃ due to the fact that the concentration of the first acid washing and rinsing is higher; each wash-and-acid rinse cycle was 1 hour from the second wash-and-acid rinse, and the temperature was set at 90-100 ℃ from the second wash-and-acid rinse due to the decrease in acid concentration.
Further, in the process of performing acid washing and rinsing for multiple times in the step S1, acid washing and rinsing are completed when the acid content in the acid washing and rinsing water after the acid washing and rinsing is lower than 1 g/l; the number of times of acid washing and rinsing is 6-8, and the temperature of acid washing and rinsing water after acid washing and rinsing is 80-90 ℃; the temperature of the mixed water of acid washing and rinsing is kept at 75-85 ℃ by introducing steam into the heat-preserving barrel of the acid washing and rinsing water and the pH value of the mixed water of acid washing and rinsing is 5-6; the mixed water of alkali washing and rinsing with the pH value of 7-8 which is conveyed to the washing and acid rinsing barrel becomes mixed water of acid washing and rinsing with the pH value of 5-6 after washing and acid rinsing.
Further, the step S2 specifically includes: s21: mixing broken pyrite and manganese dioxide ore according to a proportion, and adding the mixture into a chemical combination slurrying tank; s22: adding sulfuric acid and mixed washing acid rinsing water into a chemical combination slurrying tank according to a ratio, heating the mixed washing acid rinsing water from the temperature of more than or equal to 75 ℃ to 100 ℃ through steam, carrying out leaching chemical combination reaction, carrying out solid-liquid separation through a filter press to obtain a rough manganese sulfate solution filtrate, and piling filter residues as waste residues after secondary filter pressing.
Further, when the alkali neutralization rinsing is performed in the step S3, the alkali neutralization rinsing is completed when the PH of the alkali neutralization rinsing water after the alkali neutralization rinsing is 7 to 8; the temperature range of alkali neutralization rinsing is 55-75 ℃, and the time is 4-6 hours; the temperature of the alkali neutralization rinsing water after the alkali neutralization rinsing is 60-70 ℃; the temperature of the alkali neutralization rinsing water is kept between 55 and 65 ℃ by the heat preservation barrel of the alkali neutralization rinsing water through introducing steam for heating.
Further, the step S4 specifically includes: detecting the content of impurity metal ions in the alkali neutralization rinsing water, and if the content of the impurity metal ions is higher than a set standard, conveying the alkali neutralization rinsing water to a wastewater treatment tank to be added as alkali liquor for wastewater treatment; if the content of the impurity metal ions is equal to or lower than the set calibration standard, the mixed hot alkali liquor is conveyed to an alkali liquor preparation heat-preserving barrel to be prepared into hot alkali liquor, and when alkali neutralization rinsing is carried out again, the prepared hot alkali liquor with the temperature of 55-65 ℃ can be directly conveyed to an alkali neutralization rinsing barrel to be subjected to alkali neutralization rinsing.
Further, when preparing the alkali liquor, if the alkali neutralization rinsing water is insufficient, the mixed water of the alkali washing and rinsing in the alkali washing and rinsing water heat-preserving barrel is conveyed to the alkali liquor preparation heat-preserving barrel for preparing the alkali liquor.
Further, in the process of performing multiple alkali washing rinsing in step S5, when the PH of the alkali washing rinsing water after the alkali washing rinsing is 7, the alkali washing rinsing is completed; the temperature range of the alkali washing rinsing is 85-95 ℃, and the number of the alkali washing rinsing is 6-8; the temperature of the alkali washing and rinsing water after the alkali washing and rinsing in the step S6 is 80-90 ℃; the temperature of the mixed water for washing alkali and rinsing is kept at 75-85 ℃ by introducing steam into the heat-preserving barrel for heating, and the pH value of the mixed water for washing alkali and rinsing is 7-8; the newly heated water becomes alkali washing and rinsing mixed water after alkali washing and rinsing.
Compared with the prior art, the invention has the following beneficial effects: the invention provides an electrolytic manganese dioxide post-treatment rinsing method, rinse water of three stages of electrolytic manganese dioxide post-treatment rinsing is collected and insulated, and is respectively sent to a recycled slurry mixing tank, an alkali liquor preparation insulating barrel or a wastewater treatment tank and an acid washing rinsing barrel, so that waste of water resources is reduced, the disposal cost of standard discharge of the rinse water of the three stages as production sewage disposal is reduced, acid radicals, alkali radicals, manganese ions, heat break and other valuable components loaded by the rinse water of the three stages are recycled in a targeted manner, and meanwhile, according to the pH values and chemical components of the rinse water of different stages of rinsing, recycling points are selected in a targeted manner, the slurrying and washing leaching efficiency of the slurry mixing tank at the recycling points is accelerated, the manganese content of leaching residues is reduced, and the leaching recovery rate of manganese is improved; the reaction effect of the alkali liquor preparation heat-preserving barrel or the wastewater treatment pool is improved, and the use amount of NaOH for alkali liquor preparation and wastewater treatment is reduced; the reaction effect of the acid washing rinsing barrel is improved, and the rinsing time is shortened.
Drawings
FIG. 1 is a schematic structural diagram of a conventional post-treatment rinsing method for electrolytic manganese dioxide;
FIG. 2 is a schematic structural diagram of a post-treatment rinsing method of electrolytic manganese dioxide in an embodiment of the present invention.
Detailed Description
The invention is further described below with reference to the figures and examples.
FIG. 2 is a schematic structural diagram of a post-treatment rinsing method of electrolytic manganese dioxide in an embodiment of the present invention.
Referring to fig. 2, the method for post-treating and rinsing electrolytic manganese dioxide according to the embodiment of the present invention includes the following steps:
s1: putting the manganese dioxide particles into an acid washing rinsing barrel to carry out acid washing rinsing for multiple times; collecting the washing acid rinsing water after the multiple washing acid rinsing to a washing acid rinsing water heat-preserving container to obtain washing acid rinsing mixed water;
s2: conveying the mixed washing acid and rinsing water from the washing acid and rinsing water heat-preserving barrel to a chemical combination slurrying tank for preparing a manganese sulfate solution;
s3: putting the manganese dioxide particles subjected to acid washing and rinsing in an alkali neutralization rinsing barrel, and adding hot alkali liquor to perform alkali neutralization rinsing; collecting the alkali neutralization rinsing water after the alkali neutralization rinsing into an alkali neutralization rinsing water heat-preserving bucket;
s4: conveying alkali neutralization rinsing water from an alkali neutralization rinsing water heat-preserving bucket to an alkali liquor preparation heat-preserving bucket to prepare hot alkali liquor, and conveying the prepared hot alkali liquor to the alkali neutralization rinsing bucket for alkali neutralization rinsing when alkali neutralization rinsing is carried out again;
s5: putting the manganese dioxide particles subjected to alkali neutralization and rinsing in an alkali washing rinsing barrel, and performing alkali washing rinsing for multiple times by newly adding hot water to finish post-treatment rinsing of the manganese dioxide particles;
s6: collecting the alkali-washing rinsing water after multiple alkali-washing rinsing into an alkali-washing rinsing water heat-preserving barrel to obtain alkali-washing rinsing mixed water, and conveying the alkali-washing rinsing mixed water from the alkali-washing rinsing water heat-preserving barrel to an acid-washing rinsing barrel for acid-washing rinsing when acid-washing rinsing is carried out again.
The acid washing and rinsing barrel is provided with a circulating pump, a rinsing steam valve, a rinsing water circulating valve and a drain valve, when acid washing and rinsing are carried out, alkali washing and rinsing water is conveyed into the acid washing and rinsing barrel containing electrolytic manganese dioxide, then the circulating pump is started to enable the rinsing water in the barrel to circulate from bottom to top, and meanwhile, the rinsing steam valve is opened to heat and insulate the rinsing water in the barrel; and stopping the circulating pump after circulating for 0.5 hour, closing the rinsing water circulating valve, opening the drain valve, and discharging the acid washing rinsing water, wherein the acid washing rinsing temperature is set to be higher than 80 ℃, for example, 80-90 ℃ due to the fact that the concentration of the acid washing acid for the first time is higher. Then, the acid washing is carried out for the second time, the acid washing temperature is controlled to be 90-100 ℃ each time after the second time due to the reduction of the acid concentration from the second acid washing rinsing, and the acid washing effect is ensured, if the acid washing temperature is low, the acid washing effect is also reduced; circulating for 1 hour each time, and circulating until the acid content of the acid washing and rinsing water is lower than 1g/l, determining that the acid content reaches the standard, and continuing the acid washing and rinsing if the acid content does not reach the standard; if the acid content of the washing acid and rinsing water is higher than 1g/l, the washing acid work does not reach the standard, and the time and the difficulty of the alkali neutralization process are increased. The temperature of the washing acid rinsing water after washing acid rinsing is more than or equal to 80 ℃, such as 80-90 ℃; the temperature of the mixed water of the acid washing and rinsing is kept to be more than or equal to 75 ℃, such as 75-85 ℃ by the heat preservation barrel of the acid washing and rinsing water through introducing steam for heating; the pH value of the mixed washing and rinsing water is 5-6; the mixed water of alkali washing and rinsing with the pH value of 7-8 which is conveyed to the washing and acid rinsing barrel becomes mixed water of acid washing and rinsing with the pH value of 5-6 after washing and acid rinsing.
The acid washing rinsing is generally performed for 6-8 times, so that acid radicals and other impurity components are washed away, the standard for judging the acid washing reaching the standard is that the acid content of the acid washing rinsing water is lower than 1g/l, and the times are increased if the acid washing rinsing water does not reach the standard; the acid washing and rinsing water heat-preserving barrel collects the acid washing and rinsing water for many times and sends the heat-preserved acid washing and rinsing mixed water to the chemical combination pulping tank through a delivery pump and a pipeline.
The amount of water added for acid washing and rinsing was 3.26 cubic meters per ton of product, and 3.16 cubic meters per ton of product was discharged for acid washing and rinsing. In order to efficiently utilize the heat value brought by the temperature (75 ℃) of mixed washing and rinsing water and fully recover valuable components such as manganese ions, sulfate ions and the like in the mixed washing and rinsing water, the crushed pyrite and manganese dioxide ore are mixed according to a proportion before the mixed washing and rinsing water is added, then the mixed crushing and rinsing water is added into a chemical combination slurrying tank, sulfuric acid and the mixed washing and rinsing water are added into the chemical combination slurrying tank according to a proportion, the mixed washing and rinsing water is heated to 100 ℃ through steam for leaching and chemical combination reaction, a rough manganese sulfate solution filtrate is obtained through solid-liquid separation of a filter press, and filter residues are piled up as waste residues after secondary filter pressing; then adding the crude manganese sulfate solution into a chemical combination tank, adjusting the pH value of manganese sulfate chemical combination liquid, and removing impurities in the chemical combination liquid through a settling process; then removing the precipitated impurities by liquid-solid separation and purification of a filter press, and transferring the filter pressing residue into a chemical combination slurrying tank for reuse; and adding a purifying agent into the manganese sulfate solution after impurity removal for purification and impurity removal, and electrolyzing the purified manganese sulfate solution to obtain the electrolytic manganese dioxide.
If the mixed water of the alkali washing and the rinsing is not enough in the acid washing and rinsing process, new water is added. The temperature of the mixed water of acid washing and rinsing is above 75 ℃, the pH value is 5-6, the mixed water is acidic, the mixed water is rich in manganese ions 0.14g/l and contains sulfate radical 1.12g/l, the chemical combination pulping tank needs to be added with sulfuric acid and water, and the operation temperature is 100 ℃. Therefore, the pulping and washing leaching of manganese oxide ore can be realized quickly by recycling the acid-containing high-temperature rinsing water, the separation speed of manganese ions in the combined leaching slag is facilitated, the manganese content of the leaching slag is reduced, the leaching recovery rate of manganese is improved, 3.16 cubic meters of rinsing mixed water per ton of product is recycled, the heat value of more than 75 ℃ of 3.16 cubic meters is recycled, 456 g/ton of product of valuable manganese ions and 3651.20 g/ton of product of valuable sulfate radicals are recycled.
In the alkali neutralization rinsing stage, when alkali neutralization rinsing is carried out, the alkali neutralization rinsing is completed when the pH value of alkali neutralization rinsing water after the alkali neutralization rinsing is more than or equal to 7; the temperature of the alkali neutralization rinsing water after the alkali neutralization rinsing is more than or equal to 60 ℃, such as 60-70 ℃; the temperature of the alkali neutralization rinsing water in the heat-insulating barrel is kept to be greater than or equal to 55 ℃, such as 55-65 ℃, by introducing steam into the heat-insulating barrel to heat, the temperature of the alkali neutralization rinsing water is controlled to be between 55-75 ℃, the temperature is lower than 55 ℃, the alkali neutralization effect can be influenced, and energy waste is caused by overhigh temperature.
The alkali neutralization rinsing needs heating alkali liquor for rinsing for 4-6 hours, aiming at regulating the pH value by using alkali neutralization, and keeping the pH value of rinsing water to be 7-8, if the pH value cannot be reached, continuously adding the alkali liquor for rinsing; and the alkali neutralization rinsing water heat-preserving tank collects the alkali neutralization rinsing water and sends the heat-preserved alkali neutralization rinsing water to the alkali liquor preparation heat-preserving tank or the wastewater treatment pool through a delivery pump and a pipeline.
Adding hot alkali liquor into the alkali neutralization rinsing for 0.38 cubic meter per ton of product, discharging alkali neutralization rinsing water for 0.35 cubic meter per ton of product, extracting the alkali neutralization rinsing water after rinsing for 4-6 hours to analyze the alkali concentration, and when the alkali concentration is lower than 1g/l or the pH value of the alkali neutralization rinsing water is 7-8, determining that the product reaches the standard, and if the product does not reach the standard, continuously adding alkali liquor for rinsing until the product reaches the standard. After reaching the standard, alkali neutralizing and rinsing water is discharged. And detecting the content of impurity metal ions in the alkali neutralization rinsing water, if the content of the impurity metal ions is higher than a set standard, conveying the alkali neutralization rinsing water to a wastewater treatment tank to be used as alkali liquor to be added for wastewater treatment, and if the content of the impurity metal ions is equal to or lower than a set calibration standard, conveying the alkali liquor to an alkali liquor preparation heat-preserving container to prepare the alkali liquor. When preparing the alkali liquor, conveying the alkali washing rinsing water in the alkali washing rinsing water heat-insulating barrel to the alkali liquor preparation heat-insulating barrel for preparing the alkali liquor. The temperature of the alkali neutralizing and rinsing water is above 55 ℃, the pH value is 7-8, the alkali neutralizing and rinsing water is alkaline, the alkali solution needs to be added during the alkali solution preparation and the production wastewater disposal, and the process effect is also facilitated by increasing the temperature, so that the reaction effect of the alkali solution preparation and the production wastewater disposal can be improved by the high-temperature alkali neutralizing and rinsing water, and the usage amount of NaOH for the alkali solution preparation and the production wastewater disposal is reduced. Meanwhile, 0.35 cubic meter/ton of product of the mixed water is neutralized and rinsed by alkali, the heat value of more than 55 degrees of 0.35 cubic meter is recycled, and 0.14Kg of valuable alkali/ton of product is recycled.
In the alkali washing and rinsing stage, when alkali washing and rinsing are carried out, the temperature range of the alkali washing and rinsing is 85-95 ℃, and the alkali washing and rinsing is finished when the pH value of alkali washing and rinsing water after the alkali washing and rinsing is 7; the temperature of the alkali washing rinsing water after the alkali washing rinsing is more than or equal to 80 ℃; the temperature of the mixed water for washing alkali and rinsing is kept to be more than or equal to 75 ℃, such as 75-85 ℃ by introducing steam into the heat-preserving barrel for washing alkali and rinsing.
Rinsing for 6-8 times to remove alkali root and other impurity components, wherein the standard for determining alkali washing is that the pH value of the alkali washing rinsing water is 7, and increasing the number of times if the alkali washing rinsing water does not reach the standard; the alkali-washing rinsing water heat-preserving barrel collects the alkali-washing rinsing water for 6-8 times and sends the heat-preserving alkali-washing rinsing mixed water to the acid-washing rinsing barrel through a delivery pump and a pipeline.
Caustic rinse is rinsed by adding fresh water and circulating heat. The specific rinsing process is similar to acid rinse, with about 1 hour per rinse cycle. Adding 3.26 cubic meters of fresh water per ton of product, discharging 3.16 cubic meters of washing alkali rinsing water per ton of product, and testing the pH value of the washing alkali rinsing water to be 7 according to the standard of alkali washing, and continuously adding water for rinsing if the washing alkali rinsing water does not reach the standard. The collected 6-8 times of alkali washing and rinsing water has the temperature of over 75 ℃, the pH value of about 7-8 and alkalinity, new water needs to be added in the acid washing stage and the temperature needs to be raised to over 90 ℃, and the alkalinity is favorable for the process effect of acid washing, so the acid washing effect of the acid washing process can be accelerated by the high-temperature alkaline alkali washing and rinsing water, and the acid washing time can be shortened. Meanwhile, 3.16 cubic meters of rinsing mixed water per ton of product is recycled, and the calorific value of more than 75 degrees of 3.16 cubic meters is recycled.
In summary, the electrolytic manganese dioxide post-treatment rinsing method provided by the embodiment of the invention has the following advantages:
1) 6.67 cubic meters of water is recycled for each ton of products, so that the waste of water resources and the environmental pollution are reduced;
2) the treatment cost of the production wastewater of 6.67 cubic meters per ton of the product is reduced, and the treatment cost of the production wastewater of 76.71 yuan per ton of the product can be reduced per ton of the product according to the treatment cost of the wastewater of 11.5 yuan per ton;
3) 6.32 cubic meters of high-temperature water (more than 75 ℃) can be recovered and the heat value of 0.35 cubic meters of high-temperature water (more than 55 ℃) can be recovered per ton of products, according to the specific heat capacity of water being 4.2 multiplied by 1000J/kg per DEG C, the heat value of the standard coal being 2.926 multiplied by 1000000J/kg, the price of the standard coal being 1300 yuan/ton, and the effective rate of each ton of products can be 3.16 multiplied by 2 multiplied by 4.2/(2.926 multiplied by 1000000)/1000 multiplied by 1300) +0.35 multiplied by (75-25) < 4.2 multiplied by 1000/(2.926 multiplied by 1000000)/1000 multiplied by 351300 > -71.33 yuan;
4) 3.5392Kg of sulfate radical, 0.4424Kg of manganese ion and 0.14Kg of alkali radical can be recovered from each ton of product.
5) Because the mixed water is washed by acid and rinsed at the temperature (over 75 ℃), the pH value is 5-6, the mixed water is acidic, the mixed water is rich in manganese ions 0.14g/l and contains sulfate radical 1.12g/l, the slurrying and washing leaching of manganese oxide ore can be realized quickly, the manganese ion separation speed in the combined leaching slag is facilitated, the manganese content of the leaching slag is reduced from 3.0-3.5% to 2.5-3.0%, and the manganese leaching recovery rate is improved.
Although the present invention has been described with respect to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The post-treatment rinsing method of electrolytic manganese dioxide is characterized by comprising the following steps of:
s1: putting the manganese dioxide particles into an acid washing rinsing barrel to carry out acid washing rinsing for multiple times; collecting the washing acid rinsing water after the multiple washing acid rinsing to a washing acid rinsing water heat-preserving container to obtain washing acid rinsing mixed water;
s2: conveying the mixed washing acid and rinsing water from the washing acid and rinsing water heat-preserving barrel to a chemical combination slurrying tank for preparing a manganese sulfate solution;
s3: putting the manganese dioxide particles subjected to acid washing and rinsing in an alkali neutralization rinsing barrel, and adding hot alkali liquor to perform alkali neutralization rinsing; collecting the alkali neutralization rinsing water after the alkali neutralization rinsing into an alkali neutralization rinsing water heat-preserving bucket;
s4: conveying alkali neutralization rinsing water from an alkali neutralization rinsing water heat-preserving bucket to an alkali liquor preparation heat-preserving bucket to prepare hot alkali liquor, and conveying the prepared hot alkali liquor to the alkali neutralization rinsing bucket for alkali neutralization rinsing when alkali neutralization rinsing is carried out again;
s5: putting the manganese dioxide particles subjected to alkali neutralization and rinsing in an alkali washing rinsing barrel, and performing alkali washing rinsing for multiple times by newly adding hot water to finish post-treatment rinsing of the manganese dioxide particles;
s6: collecting the alkali-washing rinsing water after multiple alkali-washing rinsing into an alkali-washing rinsing water heat-preserving barrel to obtain alkali-washing rinsing mixed water, and conveying the alkali-washing rinsing mixed water from the alkali-washing rinsing water heat-preserving barrel to an acid-washing rinsing barrel for acid-washing rinsing when acid-washing rinsing is carried out again.
2. The method for post-treatment rinsing of electrolytic manganese dioxide as claimed in claim 1, wherein in the step S1, during the acid rinsing, the method comprises conveying the heat-preserved mixed water of alkali-washing and rinsing into an acid-washing rinsing barrel containing the electrolytic manganese dioxide, then starting a circulating pump to circulate the rinsing water in the barrel from bottom to top, and simultaneously opening a rinsing steam valve to heat and preserve the heat of the rinsing water in the barrel; stopping the circulating pump after the circulation rinsing is carried out for a set time, closing the rinsing water circulating valve, opening the drain valve, and discharging the acid washing rinsing water to finish the primary acid washing rinsing; the first acid washing and rinsing cycle is carried out for 0.5 hour, and the acid washing and rinsing temperature is set to be 80-90 ℃ due to the fact that the concentration of the first acid washing and rinsing is higher; each wash-and-acid rinse cycle was 1 hour from the second wash-and-acid rinse, and the temperature was set at 90-100 ℃ from the second wash-and-acid rinse due to the decrease in acid concentration.
3. The method for post-treating and rinsing electrolytic manganese dioxide according to claim 2, wherein in the step S1, in the multiple acid-washing rinsing processes, the acid-washing rinsing is completed when the acid content in the acid-washing rinsing water after the acid-washing rinsing is less than 1 g/l; the number of times of acid washing and rinsing is 6-8, and the temperature of acid washing and rinsing water after acid washing and rinsing is 80-90 ℃; the temperature of the mixed water of acid washing and rinsing is kept at 75-85 ℃ by introducing steam into the heat-preserving barrel of the acid washing and rinsing water and the pH value of the mixed water of acid washing and rinsing is 5-6; the mixed water of alkali washing and rinsing with the pH value of 7-8 which is conveyed to the washing and acid rinsing barrel becomes mixed water of acid washing and rinsing with the pH value of 5-6 after washing and acid rinsing.
4. The method for post-treatment rinsing of electrolytic manganese dioxide according to claim 3, wherein step S2 specifically comprises:
s21: mixing broken pyrite and manganese dioxide ore according to a proportion, and adding the mixture into a chemical combination slurrying tank;
s22: adding sulfuric acid and mixed washing acid rinsing water into a chemical combination slurrying tank according to a ratio, heating the mixed washing acid rinsing water from the temperature of more than or equal to 75 ℃ to 100 ℃ through steam, carrying out leaching chemical combination reaction, carrying out solid-liquid separation through a filter press to obtain a rough manganese sulfate solution filtrate, and piling filter residues as waste residues after secondary filter pressing.
5. The electrolytic manganese dioxide post-treatment rinsing method according to claim 1, wherein in the alkaline neutralization rinsing in step S3, the alkaline neutralization rinsing is completed when the PH of the alkaline neutralization rinsing water after the alkaline neutralization rinsing is 7 to 8; the temperature range of alkali neutralization rinsing is 55-75 ℃, and the time is 4-6 hours; the temperature of the alkali neutralization rinsing water after the alkali neutralization rinsing is 60-70 ℃; the temperature of the alkali neutralization rinsing water is kept between 55 and 65 ℃ by the heat preservation barrel of the alkali neutralization rinsing water through introducing steam for heating.
6. The method for post-treatment rinsing of electrolytic manganese dioxide according to claim 5, wherein said step S4 specifically comprises: detecting the content of impurity metal ions in the alkali neutralization rinsing water, and if the content of the impurity metal ions is higher than a set standard, conveying the alkali neutralization rinsing water to a wastewater treatment tank to be added as alkali liquor for wastewater treatment; if the content of the impurity metal ions is equal to or lower than the set calibration standard, the mixed hot alkali liquor is conveyed to an alkali liquor preparation heat-preserving barrel to be prepared into hot alkali liquor, and when alkali neutralization rinsing is carried out again, the prepared hot alkali liquor with the temperature of 55-65 ℃ can be directly conveyed to an alkali neutralization rinsing barrel to be subjected to alkali neutralization rinsing.
7. The method for post-treatment rinsing of electrolytic manganese dioxide as claimed in claim 6, wherein when preparing the alkali solution, if the alkali neutralization rinsing water is insufficient, the mixed washing and rinsing water in the washing and rinsing water holding tank is transported to the alkali solution preparation holding tank for alkali solution preparation.
8. The method for post-treatment rinsing of electrolytic manganese dioxide as claimed in claim 1, wherein in the multiple alkali-washing rinsing processes of step S5, the alkali-washing rinsing is completed when the PH of the alkali-washing rinsing water after the alkali-washing rinsing is 7; the temperature range of the alkali washing rinsing is 85-95 ℃, and the number of the alkali washing rinsing is 6-8; the temperature of the alkali washing and rinsing water after the alkali washing and rinsing in the step S6 is 80-90 ℃; the temperature of the mixed water for washing alkali and rinsing is kept at 75-85 ℃ by introducing steam into the heat-preserving barrel for heating, and the pH value of the mixed water for washing alkali and rinsing is 7-8; the newly heated water becomes alkali washing and rinsing mixed water after alkali washing and rinsing.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477521A (en) * | 2021-12-31 | 2022-05-13 | 广西大新汇元新能源科技有限责任公司 | Electrolytic manganese dioxide wastewater treatment and manganese recycling method |
| CN114634207A (en) * | 2022-03-17 | 2022-06-17 | 广西下田锰矿有限责任公司 | Rinsing and drying process and crushing and drying device for electrolytic manganese dioxide powder |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6321225A (en) * | 1986-07-15 | 1988-01-28 | Japan Metals & Chem Co Ltd | Production of electrolytic manganese dioxide |
| CN101830513A (en) * | 2010-05-26 | 2010-09-15 | 中信大锰矿业有限责任公司 | Method for preparing low-sodium electrolytic manganese dioxide |
| JP2011068552A (en) * | 2009-08-24 | 2011-04-07 | Tosoh Corp | Electrolytic manganese dioxide, method for producing the same, and use of the same |
| CN102220490A (en) * | 2011-05-06 | 2011-10-19 | 广西桂柳化工有限责任公司 | Production method of electrolytic manganese dioxide |
| CN103555940A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Preparation method of special electrolytic manganese dioxide for automobile power battery |
| CN103572315A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Preparation method of special electrolytic manganese dioxide for button/manganese dioxide battery |
| CN103572317A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Method for refining electrolytic manganese dioxide product |
| CN106241880A (en) * | 2016-06-21 | 2016-12-21 | 中国石油大学(华东) | Method for recovering high-purity manganese dioxide from waste manganese dry batteries and application |
| JP2019183236A (en) * | 2018-04-12 | 2019-10-24 | パナソニックＩｐマネジメント株式会社 | Method for producing refined electrolytic manganese dioxide |
-
2020
- 2020-06-02 CN CN202010489978.4A patent/CN111632940A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6321225A (en) * | 1986-07-15 | 1988-01-28 | Japan Metals & Chem Co Ltd | Production of electrolytic manganese dioxide |
| JP2011068552A (en) * | 2009-08-24 | 2011-04-07 | Tosoh Corp | Electrolytic manganese dioxide, method for producing the same, and use of the same |
| CN101830513A (en) * | 2010-05-26 | 2010-09-15 | 中信大锰矿业有限责任公司 | Method for preparing low-sodium electrolytic manganese dioxide |
| CN102220490A (en) * | 2011-05-06 | 2011-10-19 | 广西桂柳化工有限责任公司 | Production method of electrolytic manganese dioxide |
| CN103555940A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Preparation method of special electrolytic manganese dioxide for automobile power battery |
| CN103572315A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Preparation method of special electrolytic manganese dioxide for button/manganese dioxide battery |
| CN103572317A (en) * | 2013-11-07 | 2014-02-12 | 广西桂柳化工有限责任公司 | Method for refining electrolytic manganese dioxide product |
| CN106241880A (en) * | 2016-06-21 | 2016-12-21 | 中国石油大学(华东) | Method for recovering high-purity manganese dioxide from waste manganese dry batteries and application |
| JP2019183236A (en) * | 2018-04-12 | 2019-10-24 | パナソニックＩｐマネジメント株式会社 | Method for producing refined electrolytic manganese dioxide |
Non-Patent Citations (3)
| Title |
|---|
| 娄金生 等: "《水污染治理新工艺与设计》", 31 March 1999, 海军出版社 * |
| 张成松 等: "电解二氧化锰漂洗废水的循环利用探索", 《大众科技》 * |
| 赵大传 等: "《工业环境学》", 30 September 2004, 中国环境科学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477521A (en) * | 2021-12-31 | 2022-05-13 | 广西大新汇元新能源科技有限责任公司 | Electrolytic manganese dioxide wastewater treatment and manganese recycling method |
| CN114477521B (en) * | 2021-12-31 | 2024-05-28 | 广西大新汇元新能源科技有限责任公司 | Electrolytic manganese dioxide wastewater treatment and manganese recycling method |
| CN114634207A (en) * | 2022-03-17 | 2022-06-17 | 广西下田锰矿有限责任公司 | Rinsing and drying process and crushing and drying device for electrolytic manganese dioxide powder |
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