CN111547892A - Treatment method of ammonia nitrogen wastewater in manganese chemical industry - Google Patents
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Abstract
The invention discloses a method for treating ammonia nitrogen wastewater in manganese chemical industry, which belongs to the field of treatment of wastewater in manganese chemical industry, and realizes recycling of ammonia nitrogen resources and manganese, wherein calcium hydroxide is added firstly to remove manganese ions and other metal ions and sulfate radicals, and then an analytic agent is added to remove residual calcium ions in filtrate, so that calcium and magnesium in the ammonia nitrogen treatment process are prevented from blocking equipment; the waste liquid is deaminated by adopting a mode of combining aeration stripping and a deamination tower, and then is filtered and ion-exchanged, so that the content of ammonia nitrogen and metal ions in the water is lower than the discharge standard GB 31573-2015 inorganic chemical industry pollutant discharge standard, the content of ammonia nitrogen in the waste water treated by the method is less than or equal to 10mg/L, the content of manganese is less than or equal to 1mg/L, the content of hexavalent chromium is less than or equal to 0.1mg/L, the total hardness of the waste water is less than or equal to 50mg/L, and the treated waste water can reach the standard and be discharged or returned to a production system for recycling.
Description
Technical Field
The invention belongs to the field of manganese chemical industry wastewater treatment, and particularly relates to a treatment method of ammonia nitrogen wastewater in manganese chemical industry.
Background
According to statistics, over 1000 million tons of manganese ore are mined in China every year, which is the first place in the world, and a large amount of leaching slag is usually generated in the electrolytic manganese production process (5-6 tons of manganese metal are generated per 1 ton of manganese metal). Electrolyte (the water content of general leaching slag is 20-28%, and the components of the general leaching slag mainly comprise manganese sulfate, ammonium sulfate and magnesium sulfate) contained in the leaching slag is leached and diluted along with rainwater in a rainwater season, and the leaching slag is converged into slag reservoir leachate to form manganese-ammonia nitrogen-containing wastewater, the wastewater is complex in water quality, contains a large amount of pollutants such as manganese ions, sulfate, ammonia nitrogen and the like, also contains a small amount of metal ions such as magnesium, calcium, iron, chromium, copper, nickel, zinc and the like, and can leak to an external environment if the wastewater is not treated in time, so that the water quality of the surrounding environment is seriously harmed, the ecological balance is damaged, and the human health is harm.
The patent CN 201911334057.4 discloses a method for treating lithium battery industrial wastewater, which comprises the steps of firstly adjusting the pH value of the lithium battery industrial wastewater in a wastewater adjusting tank to convert ammonia nitrogen into free ammonia, introducing high-temperature steam from the lower part of a deamination tower to make the deamination wastewater and the high-temperature steam in a medium to be in vapor-liquid contact, discharging ammonia-containing steam formed by the separated free ammonia and the high-temperature steam in the ammonia nitrogen wastewater from the top of the tower, discharging the separated ammonia nitrogen wastewater from the bottom of the tower, and controlling the concentration of condensed ammonia gas to generate concentrated ammonia water under the micro-negative pressure operation; adding alkali liquor into a reaction barrel to adjust the pH value of the ammonia nitrogen wastewater, adding a flocculating agent PAM and a coagulant aid PAC, inputting the ammonia nitrogen wastewater into a heat exchanger for preheating, and then sequentially evaporating in a falling film evaporator and a forced circulation evaporator to obtain industrial anhydrous sodium sulphate; although the patent has high treatment and recovery efficiency and low energy consumption and operation cost, the waste water contains a large amount of manganese ions, magnesium ions, calcium ions and the like, so that the deamination tower is easy to block in the ammonia nitrogen removal process, and the synchronous recovery of manganese resources and ammonia nitrogen resources can not be realized.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for treating ammonia nitrogen wastewater in manganese chemical industry.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a method for treating ammonia nitrogen wastewater in manganese chemical industry, which comprises the following steps:
(1) treating the manganese chemical ammonia nitrogen wastewater by regulating the water quantity and homogenizing the water quality, and entering the next process;
(2) adding excessive calcium hydroxide into the wastewater obtained in the step (1) to generate hydroxide precipitate and calcium sulfate precipitate which are insoluble in water, introducing air for aeration and stripping to separate free ammonia, collecting ammonia-containing gas, separating solid from liquid, recycling the precipitate, and allowing the filtrate to enter the next process;
(3) adding an analytical agent into the filtrate obtained in the step (2), removing residual calcium ions in the filtrate, carrying out solid-liquid separation, carrying out precipitation innocent treatment, and enabling the filtrate to enter the next working procedure;
(4) adding a pH regulator into the filtrate obtained in the step (3) to convert ionic ammonium in the filtrate into molecular ammonia, introducing the filtrate into the top of a deamination tower, introducing high-pressure gas into the bottom of the deamination tower, mixing and separating by virtue of multi-stage filling, discharging free ammonia from the top of the deamination tower, and obtaining deamination wastewater at the bottom of the deamination tower;
(5) merging ammonia-containing gas discharged from the top of the deamination tower with the ammonia-containing gas obtained in the step (2), and then feeding the merged ammonia-containing gas into a condenser to obtain ammonia water condensate, wherein part of the ammonia water condensate flows back to the top of the deamination tower, and the other part of the ammonia water condensate enters a recovery device to prepare concentrated ammonia water;
(6) introducing the deamination wastewater obtained in the step (4) into a filtering device to remove suspended matters and chromaticity;
(7) and (4) carrying out ion exchange treatment on the filtrate obtained in the step (6) to remove residual manganese ions and hexavalent chromium in the wastewater, and directly discharging or recycling the filtrate obtained after ion exchange to a production workshop.
In the preferable scheme, in the step (2), a calcium hydroxide solution with the mass fraction of 10% -30% is adopted, and excessive calcium hydroxide is added to react with metal ions such as manganese ions and sulfate radicals to generate hydroxide precipitates and calcium sulfate precipitates; and ammonia gas is generated after the calcium hydroxide is added for aeration and stripping and is pumped into a condenser, so that the pressure of the subsequent deamination process is reduced, and the recovery rate of ammonia nitrogen is improved.
Preferably, the precipitate obtained in step (2) is recycled, and specifically comprises:
s1, dissolving hydroxide precipitate and calcium sulfate precipitate in dilute sulfuric acid, and performing solid-liquid separation to obtain a manganese sulfate mixed solution;
s2, removing impurity ions such as magnesium ions and the like in the manganese sulfate mixed solution to obtain a pure manganese sulfate solution.
Preferably, in step (3), the resolving agent is one or more of sodium carbonate, ammonium carbonate, sodium bicarbonate and ammonium bicarbonate.
Further, the analysis agent is a composition of sodium carbonate and ammonium carbonate, and the molar ratio of the sodium carbonate to the ammonium carbonate is 0.1-10: 1.
preferably, in the step (3), the harmless treatment of the precipitate is specifically: and (4) carrying out filter pressing through a filter press, and reasonably stacking the obtained filter cakes.
In a preferable scheme, in the step (4), the pH regulator is any one of sodium hydroxide, potassium hydroxide and calcium hydroxide, and the pH value of the filtrate is regulated to 10-14.
Further, sodium hydroxide is used as the pH regulator.
In the preferable scheme, in the step (5), the mass concentration of the strong ammonia water is 8-20%; and part of ammonia water condensate flows back to the top of the deamination tower, so that the concentration of an ammonia water product is favorably improved.
Preferably, in the step (6), the filtering device adopts sand filtration and activated carbon filtration.
Preferably, in the step (7), cation exchange resin is adopted to adsorb manganese ions remaining in the wastewater, the resin is regenerated to obtain a manganese sulfate solution, and the manganese sulfate solution obtained in the step S2 are combined and recycled.
Further, the manganese content in the manganese sulfate solution obtained after regeneration is 10-40 g/L.
Preferably, in the step (7), anion exchange resin is adopted to adsorb residual hexavalent chromium in the wastewater, and sodium dichromate or potassium dichromate solution obtained after the resin is regenerated is returned to an electrolytic manganese workshop.
Furthermore, the content of hexavalent chromium in the sodium dichromate or potassium dichromate solution obtained after regeneration is 10-20 g/L.
The chemical reaction equation mainly related to the invention is as follows:
OH-+Mn2+→Mn(OH)2↓；
SO4 2-+Ca2+→CaSO4↓；
OH-+Mg2+→Mg(OH)2↓；
CO3 2-+Ca2+→CaCO3↓；
NH4 ++HO-→NH3·H2O；
NH3·H2O→NH3↑+H2O。
compared with the prior art, the invention has the beneficial technical effects that:
the invention relates to a method for treating ammonia nitrogen wastewater in manganese chemical industry, which realizes the recycling of ammonia nitrogen resources and manganese, and comprises the steps of firstly adding calcium hydroxide to remove manganese ions, magnesium ions and sulfate radicals, then adding an analytic agent to remove residual calcium ions in filtrate, and preventing calcium and magnesium from blocking equipment in the ammonia nitrogen treatment process; then, the waste liquid is deaminated by adopting a mode of combining aeration stripping and a deamination tower, and then is filtered and ion-exchanged, so that the ammonia nitrogen content and the metal ion content in the water are lower than the discharge standard GB 31573-2015 inorganic chemical industry pollutant discharge standard.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a process flow diagram of the treatment method of ammonia nitrogen wastewater in manganese chemical industry.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
The experimental procedures described in the following examples are conventional unless otherwise specified, and the reagents and materials described therein are commercially available without further specification.
The invention relates to a method for treating ammonia nitrogen wastewater in manganese chemical industry, which comprises the following steps as shown in figure 1:
(1) treating the manganese chemical ammonia nitrogen wastewater by regulating the water quantity and homogenizing the water quality, and entering the next process;
(2) adding excessive calcium hydroxide into the wastewater obtained in the step (1) to generate hydroxide precipitate and calcium sulfate precipitate which are insoluble in water, introducing air for aeration and stripping to separate free ammonia, collecting ammonia-containing gas, separating solid from liquid, recycling the precipitate, and allowing the filtrate to enter the next process;
(3) adding an analytical agent into the filtrate obtained in the step (2), removing residual calcium ions in the filtrate, carrying out solid-liquid separation, carrying out precipitation innocent treatment, and enabling the filtrate to enter the next working procedure;
(4) adding a pH regulator into the filtrate obtained in the step (3) to convert ionic ammonium in the filtrate into molecular ammonia, introducing the filtrate into the top of a deamination tower, introducing high-pressure gas into the bottom of the deamination tower, mixing and separating by virtue of multi-stage filling, discharging free ammonia from the top of the deamination tower, and obtaining deamination wastewater at the bottom of the deamination tower;
(5) merging ammonia-containing gas discharged from the top of the deamination tower with the ammonia-containing gas obtained in the step (2), and then feeding the merged ammonia-containing gas into a condenser to obtain ammonia water condensate, wherein part of the ammonia water condensate flows back to the top of the deamination tower, and the other part of the ammonia water condensate enters a recovery device to prepare concentrated ammonia water;
(6) introducing the deamination wastewater obtained in the step (4) into a filtering device to remove suspended matters and chromaticity;
(7) and (4) carrying out ion exchange treatment on the filtrate obtained in the step (6) to remove residual manganese ions and hexavalent chromium in the wastewater, and directly discharging or recycling the filtrate obtained after ion exchange to a production workshop.
The water quality of inlet water in the embodiment of the invention is as follows: the ammonia nitrogen content is 200-30000 mg/L; the manganese ion content is 200-10000 mg/L; the sulfate radical content is 1000-30000 mg/L; the content of magnesium ions is 100-20000 mg/L; the content of calcium ions is 200-2000 mg/L; the content of hexavalent chromium is 0.1-1000 mg/L; the total hardness of water is 200-22000 mg/L, and the pH is 2-7.
Example 1
The embodiment of the invention provides a method for treating ammonia nitrogen wastewater in manganese chemical industry, which comprises the following steps:
(1) treating the manganese chemical ammonia nitrogen wastewater by regulating the water quantity and homogenizing the water quality, and entering the next process;
(2) adding 20% by mass of calcium hydroxide solution (excessive) into the wastewater obtained in the step (1) to generate hydroxide precipitate and calcium sulfate precipitate which are insoluble in water, introducing air for aeration and stripping to separate free ammonia, collecting ammonia-containing gas, separating solid from liquid, recycling the precipitate, and allowing the filtrate to enter the next process;
(3) adding a composition of sodium carbonate and ammonium carbonate (the molar ratio is 1: 1) into the filtrate obtained in the step (2) as a resolving agent, removing residual calcium ions in the filtrate, carrying out solid-liquid separation, carrying out filter pressing on the precipitate through a filter press, reasonably stacking the obtained filter cakes, and feeding the filtrate into the next working procedure;
(4) adding sodium hydroxide into the filtrate obtained in the step (3), adjusting the pH value of the filtrate to 10-14, enabling the filtrate to enter the top of a deamination tower, introducing high-pressure gas into the bottom of the deamination tower, performing multi-stage filling and mixing separation, discharging free ammonia from the top of the deamination tower, and obtaining deamination wastewater at the bottom of the deamination tower;
(5) converging ammonia-containing gas discharged from the top of the deamination tower and the ammonia-containing gas obtained in the step (2), and then feeding the converged ammonia-containing gas into a condenser to obtain ammonia water condensate, wherein part of the ammonia water condensate flows back to the top of the deamination tower, and the other part of the ammonia water condensate enters a recovery device to prepare concentrated ammonia water with the mass concentration of 8-20%;
(6) introducing the deamination wastewater obtained in the step (4) into a filtering device, wherein the filtering device adopts sand filtration and activated carbon filtration to remove suspended matters and chromaticity;
(7) adsorbing residual manganese ions in the wastewater by adopting cation exchange resin, and regenerating the resin to obtain a manganese sulfate solution; adsorbing residual hexavalent chromium in the wastewater by adopting anion exchange resin, obtaining sodium dichromate solution after the resin is regenerated, and directly discharging or recycling filtrate obtained after ion exchange to a production workshop;
recycling the precipitate obtained in the step (2), specifically comprising:
s1, dissolving hydroxide precipitate and calcium sulfate precipitate in dilute sulfuric acid, and performing solid-liquid separation to obtain a manganese sulfate mixed solution;
s2, removing impurity ions such as magnesium ions and the like in the manganese sulfate mixed solution by adopting a fluoride method (see the literature: baiting, Qianliyi, Stadium and Stapf. research on deep removal of calcium and magnesium in industrial manganese sulfate by a fluorination method [ J ]. nonferrous metal (smelting part), 2018(7):1-4), so as to obtain a pure manganese sulfate solution which is convenient to match with subsequent procedures.
The ammonia nitrogen content in the wastewater treated in the embodiment 1 is 7.9 mg/L; the content of manganese ions is 0.5 mg/L; the sulfate radical content is 221 mg/L; the content of hexavalent chromium is less than or equal to 0.1 mg/L; the total hardness of water is 46mg/L, and the pH value is 6-9.
Example 2
The embodiment of the invention provides a method for treating ammonia nitrogen wastewater in manganese chemical industry, which comprises the following steps:
(1) treating the manganese chemical ammonia nitrogen wastewater by regulating the water quantity and homogenizing the water quality, and entering the next process;
(2) adding 10% by mass of calcium hydroxide solution (excessive) into the wastewater obtained in the step (1) to generate hydroxide precipitate and calcium sulfate precipitate which are insoluble in water, introducing air for aeration and stripping to separate free ammonia, collecting ammonia-containing gas, separating solid from liquid, recycling the precipitate, and allowing the filtrate to enter the next process;
(3) adding a composition of sodium carbonate and ammonium carbonate (the molar ratio is 10: 1) into the filtrate obtained in the step (2) as a resolving agent, removing residual calcium ions in the filtrate, carrying out solid-liquid separation, carrying out filter pressing on the precipitate through a filter press, reasonably stacking the obtained filter cakes, and feeding the filtrate into the next working procedure;
(4) adding sodium hydroxide into the filtrate obtained in the step (3), adjusting the pH value of the filtrate to 10-14, enabling the filtrate to enter the top of a deamination tower, introducing high-pressure gas into the bottom of the deamination tower, performing multi-stage filling and mixing separation, discharging free ammonia from the top of the deamination tower, and obtaining deamination wastewater at the bottom of the deamination tower;
(5) converging ammonia-containing gas discharged from the top of the deamination tower and the ammonia-containing gas obtained in the step (2), and then feeding the converged ammonia-containing gas into a condenser to obtain ammonia water condensate, wherein part of the ammonia water condensate flows back to the top of the deamination tower, and the other part of the ammonia water condensate enters a recovery device to prepare concentrated ammonia water with the mass concentration of 8-20%;
(6) introducing the deamination wastewater obtained in the step (4) into a filtering device, wherein the filtering device adopts sand filtration and activated carbon filtration to remove suspended matters and chromaticity;
(7) adsorbing residual manganese ions in the wastewater by adopting cation exchange resin, and regenerating the resin to obtain a manganese sulfate solution; adsorbing residual hexavalent chromium in the wastewater by adopting anion exchange resin, obtaining sodium dichromate solution after the resin is regenerated, and directly discharging or recycling filtrate obtained after ion exchange to a production workshop;
the ammonia nitrogen content in the wastewater treated in the embodiment 2 is 8.4 mg/L; the content of manganese ions is 0.7 mg/L; the sulfate radical content is 238 mg/L; the content of hexavalent chromium is less than or equal to 0.1 mg/L; the total hardness of water is 48mg/L, and the pH value is 6-9.
Example 3
The embodiment of the invention provides a method for treating ammonia nitrogen wastewater in manganese chemical industry, which comprises the following steps:
(1) treating the manganese chemical ammonia nitrogen wastewater by regulating the water quantity and homogenizing the water quality, and entering the next process;
(2) adding 30 mass percent of calcium hydroxide solution (excessive) into the wastewater obtained in the step (1) to generate hydroxide precipitate and calcium sulfate precipitate which are insoluble in water, simultaneously introducing air for aeration and stripping to separate free ammonia, collecting ammonia-containing gas, after solid-liquid separation, recycling the precipitate, and enabling the filtrate to enter the next process;
(3) adding a composition of sodium carbonate and ammonium carbonate (the molar ratio is 0.1: 1) into the filtrate obtained in the step (2) as a resolving agent, removing residual calcium ions in the filtrate, carrying out solid-liquid separation, carrying out filter pressing on the precipitate through a filter press, reasonably stacking the obtained filter cakes, and feeding the filtrate into the next working procedure;
(4) adding sodium hydroxide into the filtrate obtained in the step (3), adjusting the pH value of the filtrate to 10-14, enabling the filtrate to enter the top of a deamination tower, introducing high-pressure gas into the bottom of the deamination tower, performing multi-stage filling and mixing separation, discharging free ammonia from the top of the deamination tower, and obtaining deamination wastewater at the bottom of the deamination tower;
(5) converging ammonia-containing gas discharged from the top of the deamination tower and the ammonia-containing gas obtained in the step (2), and then feeding the converged ammonia-containing gas into a condenser to obtain ammonia water condensate, wherein part of the ammonia water condensate flows back to the top of the deamination tower, and the other part of the ammonia water condensate enters a recovery device to prepare concentrated ammonia water with the mass concentration of 8-20%;
(6) introducing the deamination wastewater obtained in the step (4) into a filtering device, wherein the filtering device adopts sand filtration and activated carbon filtration to remove suspended matters and chromaticity;
(7) adsorbing residual manganese ions in the wastewater by adopting cation exchange resin, and regenerating the resin to obtain a manganese sulfate solution; adsorbing residual hexavalent chromium in the wastewater by adopting anion exchange resin, obtaining sodium dichromate solution after the resin is regenerated, and directly discharging or recycling filtrate obtained after ion exchange to a production workshop;
the ammonia nitrogen content in the wastewater treated in the embodiment 3 is 9.6 mg/L; the content of manganese ions is 0.8 mg/L; the sulfate content is 247 mg/L; the content of hexavalent chromium is less than or equal to 0.1 mg/L; the total hardness of water is 44mg/L, and the pH value is 6-9.
Claims (10)
1. The method for treating ammonia nitrogen wastewater in manganese chemical industry is characterized by comprising the following steps:
(1) treating the manganese chemical ammonia nitrogen wastewater by regulating the water quantity and homogenizing the water quality, and entering the next process;
(2) adding excessive calcium hydroxide into the wastewater obtained in the step (1) to generate hydroxide precipitate and calcium sulfate precipitate which are insoluble in water, introducing air for aeration and stripping to separate free ammonia, collecting ammonia-containing gas, separating solid from liquid, recycling the precipitate, and allowing the filtrate to enter the next process;
(3) adding an analytical agent into the filtrate obtained in the step (2), removing residual calcium ions in the filtrate, carrying out solid-liquid separation, carrying out precipitation innocent treatment, and enabling the filtrate to enter the next working procedure;
(4) adding a pH regulator into the filtrate obtained in the step (3) to convert ionic ammonium in the filtrate into molecular ammonia, introducing the filtrate into the top of a deamination tower, introducing high-pressure gas into the bottom of the deamination tower, mixing and separating by virtue of multi-stage filling, discharging free ammonia from the top of the deamination tower, and obtaining deamination wastewater at the bottom of the deamination tower;
(5) merging ammonia-containing gas discharged from the top of the deamination tower with the ammonia-containing gas obtained in the step (2), and then feeding the merged ammonia-containing gas into a condenser to obtain ammonia water condensate, wherein part of the ammonia water condensate flows back to the top of the deamination tower, and the other part of the ammonia water condensate enters a recovery device to prepare concentrated ammonia water;
(6) introducing the deamination wastewater obtained in the step (4) into a filtering device to remove suspended matters and chromaticity;
(7) and (4) carrying out ion exchange treatment on the filtrate obtained in the step (6) to remove residual manganese ions and hexavalent chromium in the wastewater, and directly discharging or recycling the filtrate obtained after ion exchange to a production workshop.
2. The method for treating ammonia nitrogen wastewater in manganese chemical industry according to claim 1, wherein in the step (2), 10-30% by mass of calcium hydroxide solution is adopted, and excessive calcium hydroxide is added to react with metal ions such as manganese ions and sulfate radicals to generate hydroxide precipitate and calcium sulfate precipitate.
3. The method for treating ammonia nitrogen wastewater in manganese chemical industry according to claim 1, wherein the precipitate obtained in step (2) is recycled, and specifically comprises the following steps:
s1, dissolving hydroxide precipitate and calcium sulfate precipitate in dilute sulfuric acid, and performing solid-liquid separation to obtain a manganese sulfate mixed solution;
s2, removing impurity ions such as magnesium ions and the like in the manganese sulfate mixed solution to obtain the manganese sulfate solution.
4. The method for treating ammonia nitrogen wastewater in manganese chemical industry according to claim 1, wherein in step (3), the resolving agent is one or more of sodium carbonate, ammonium carbonate, sodium bicarbonate and ammonium bicarbonate.
5. The method for treating ammonia nitrogen wastewater in manganese chemical industry according to claim 4, wherein the desorption agent is a composition of sodium carbonate and ammonium carbonate, and the molar ratio of the sodium carbonate to the ammonium carbonate is 0.1-10: 1.
6. the method for treating ammonia nitrogen wastewater in manganese chemical industry according to claim 1, wherein in the step (4), any one of sodium hydroxide, potassium hydroxide and calcium hydroxide is used as the pH regulator, and the pH value of the filtrate is regulated to 10-14.
7. The method for treating ammonia nitrogen wastewater in manganese chemical industry according to claim 6, wherein the pH regulator is sodium hydroxide.
8. The method for treating ammonia nitrogen wastewater in manganese chemical industry according to claim 1, wherein in the step (6), the filtering device adopts sand filtration and activated carbon filtration.
9. The method for treating ammonia nitrogen wastewater in manganese chemical industry according to claim 1, wherein in step (7), a cation exchange resin is used for adsorbing residual manganese ions in the wastewater, a manganese sulfate solution is obtained after the resin is regenerated, and the manganese sulfate solution obtained in step S2 are combined and recycled.
10. The method for treating ammonia nitrogen wastewater in manganese chemical industry according to claim 1, wherein in step (7), anion exchange resin is used for adsorbing residual hexavalent chromium in the wastewater, and sodium dichromate or potassium dichromate solution obtained after the resin is regenerated is returned to an electrolytic manganese workshop.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113023997A (en) * | 2021-04-13 | 2021-06-25 | 南京简迪环境工程有限公司 | High-hardness ammonia-containing wastewater treatment process |
| CN114457234A (en) * | 2021-07-23 | 2022-05-10 | 江西离子型稀土工程技术研究有限公司 | Rare earth impurity removal and enrichment ion exchange system and process method |
| CN115057476A (en) * | 2022-07-23 | 2022-09-16 | 贵州金瑞新材料有限责任公司 | Process for preparing electronic-grade manganese sulfate by potassium-sodium-calcium-magnesium-free method |
| CN116835744A (en) * | 2023-08-30 | 2023-10-03 | 湘潭电化科技股份有限公司 | Treatment method of manganese-containing industrial wastewater |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0568389A1 (en) * | 1992-04-30 | 1993-11-03 | Tosoh Corporation | Process for removing oxidizable substance or reducible substance, composite supporting metal oxide or hydroxide, and process for production thereof |
| CN101838065A (en) * | 2010-01-26 | 2010-09-22 | 中国环境科学研究院 | Method for recycling hexavalent chromium in electrolytic manganese production tail end wastewater |
| CN102424491A (en) * | 2011-10-27 | 2012-04-25 | 中南大学 | Treatment method for recycling manganous-manganic oxide industrial wastewater |
| CN103496801A (en) * | 2013-09-11 | 2014-01-08 | 洛阳鼎力环保科技有限公司 | Electrolytic manganese chromium-containing wastewater treatment and hexavalent chromium recovery method |
| CN103553138A (en) * | 2013-11-01 | 2014-02-05 | 王文领 | Comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water |
| CN104005050A (en) * | 2014-06-06 | 2014-08-27 | 四川恒达环境技术有限公司 | Method for treating and recycling divalent manganese in electrolytic manganese wastewater |
| US8915301B1 (en) * | 2011-04-26 | 2014-12-23 | Mansour S. Bader | Treatment of saline streams |
| CN110304755A (en) * | 2019-05-07 | 2019-10-08 | 江苏创仕德环保科技有限公司 | A kind of wastewater treatment method and its processing system containing electrolytic manganese residues |
-
2020
- 2020-05-22 CN CN202010440419.4A patent/CN111547892A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0568389A1 (en) * | 1992-04-30 | 1993-11-03 | Tosoh Corporation | Process for removing oxidizable substance or reducible substance, composite supporting metal oxide or hydroxide, and process for production thereof |
| CN101838065A (en) * | 2010-01-26 | 2010-09-22 | 中国环境科学研究院 | Method for recycling hexavalent chromium in electrolytic manganese production tail end wastewater |
| US8915301B1 (en) * | 2011-04-26 | 2014-12-23 | Mansour S. Bader | Treatment of saline streams |
| CN102424491A (en) * | 2011-10-27 | 2012-04-25 | 中南大学 | Treatment method for recycling manganous-manganic oxide industrial wastewater |
| CN103496801A (en) * | 2013-09-11 | 2014-01-08 | 洛阳鼎力环保科技有限公司 | Electrolytic manganese chromium-containing wastewater treatment and hexavalent chromium recovery method |
| CN103553138A (en) * | 2013-11-01 | 2014-02-05 | 王文领 | Comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water |
| CN104005050A (en) * | 2014-06-06 | 2014-08-27 | 四川恒达环境技术有限公司 | Method for treating and recycling divalent manganese in electrolytic manganese wastewater |
| CN110304755A (en) * | 2019-05-07 | 2019-10-08 | 江苏创仕德环保科技有限公司 | A kind of wastewater treatment method and its processing system containing electrolytic manganese residues |
Non-Patent Citations (1)
| Title |
|---|
| 陶长元等: "《电解锰节能减排理论与工程应用》", 30 November 2018, 重庆大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113023997A (en) * | 2021-04-13 | 2021-06-25 | 南京简迪环境工程有限公司 | High-hardness ammonia-containing wastewater treatment process |
| CN114457234A (en) * | 2021-07-23 | 2022-05-10 | 江西离子型稀土工程技术研究有限公司 | Rare earth impurity removal and enrichment ion exchange system and process method |
| CN115057476A (en) * | 2022-07-23 | 2022-09-16 | 贵州金瑞新材料有限责任公司 | Process for preparing electronic-grade manganese sulfate by potassium-sodium-calcium-magnesium-free method |
| CN116835744A (en) * | 2023-08-30 | 2023-10-03 | 湘潭电化科技股份有限公司 | Treatment method of manganese-containing industrial wastewater |
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