CN112792086A - Method for harmless treatment of electric field reinforced electrolytic manganese slag - Google Patents
Method for harmless treatment of electric field reinforced electrolytic manganese slag Download PDFInfo
- Publication number
- CN112792086A CN112792086A CN201911109621.2A CN201911109621A CN112792086A CN 112792086 A CN112792086 A CN 112792086A CN 201911109621 A CN201911109621 A CN 201911109621A CN 112792086 A CN112792086 A CN 112792086A
- Authority
- CN
- China
- Prior art keywords
- electrolytic manganese
- ore pulp
- filtrate
- manganese slag
- pulp system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
Abstract
The invention discloses a method for harmless treatment of electrolytic manganese slag by electric field strengthening, which is characterized by fully mixing the electrolytic manganese slag with water according to a certain proportion to obtain mixed ore pulp; then, adjusting the pH value of the ore pulp system by using an alkaline material, aerating the ore pulp system for a period of time, performing solid-liquid separation, recycling filter residues, and absorbing overflowed gas by using dilute sulfuric acid; and finally, adding sodium hypochlorite and an electric field into the filtrate, fully reacting for a period of time, and then carrying out solid-liquid separation, wherein the filtrate is used for leaching the next batch of electrolytic manganese residues. Compared with the prior art, the method has the advantages of thorough harmlessness, simple flow, high removal rate of manganese and ammonia nitrogen, few byproducts and the like.
Description
Technical Field
The invention relates to the field of harmless treatment of solid waste, in particular to a harmless treatment method of electrolytic manganese slag by electric field strengthening.
Background
The electrolytic manganese residue is acidic residue generated after acid leaching, neutralization and filter pressing in the process of producing metal manganese by an electrolytic method. For historical and technical reasons, most of the electrolytic manganese slag in China is currently discharged in open-air stockpiling, the electrolytic manganese slag is washed by rainwater or naturally permeates in the stockpiling process to form a large amount of percolate, the percolate contains high-concentration manganese (1000-3000 mg/L) and ammonia nitrogen (500-2000 mg/L), and once the pollutants enter the environment, the pollutants seriously threaten the surrounding ecological environment.
To date, scholars at home and abroad carry out a great deal of research work on harmless treatment of electrolytic manganese residues, wherein the research work mainly comprises a sulfuric acid back leaching method, a biological reduction leaching method, a counter-current washing method, a clear water washing-ammonium salt precipitation method and the like. A method for harmlessly treating the leachate of electrolytic manganese slag (application No. 201610528699.8) has been proposed by Taogjinjing et al, which has little secondary pollution to the environment and simple operation, but the reaction efficiency still needs to be improved. The Caoxing proposed harmless treatment method for the electrolytic manganese slag (application number: 201811585423.9) has high economic benefit and small secondary pollution to the environment, but does not carry out pretreatment on ammonia nitrogen and manganese in the electrolytic manganese slag, thereby influencing the subsequent resource utilization of the electrolytic manganese slag. The royal resolute proposed method for treating the electrolytic manganese slag in a harmless way (application number: 201710916632.6) has good treatment effect and little pollution to the environment, and the treated manganese slag can be directly used in agriculture.
Sodium hypochlorite is an alkaline strong oxidant which can oxidize manganese ions to form manganese oxide precipitates, and the relevant reaction principle is H2O+Mn2++ClO-→MnO2+Cl-+2H+(ii) a In addition, sodium hypochlorite can be oxidized to remove ammonia nitrogen, and the main reaction principle is 3ClO-+2NH4 +→N2+3Cl-+H2O+2H+. The addition of sodium hypochlorite can accelerate the reaction rate, shorten the treatment time, has obvious treatment effect and greatly improves the removal efficiency of manganese and ammonia nitrogen. However, when excessive sodium hypochlorite is added, a large amount of by-products such as nitrate, nitrite, residual chlorine and free chlorine remain in the wastewater, and serious secondary pollution is caused.
DSA electrode is the key point of electrocatalytic oxidation reaction at present, and electrodes of Ti-based lead oxide, iridium oxide, tin-antimony oxide and the like areCurrently, there are DSA electrodes of research value. This patent will be Ti/RuO2-IrO2The electrode is used as an anode, the Cu polar plate mainly reduces nitrate radicals into ammonia nitrogen, and the ammonia nitrogen is oxidized by sodium hypochlorite to form nitrogen for removal. In aqueous solution, NH4 +the-N can be oxidized by direct or indirect means. Direct oxidation refers to NH4 +Adsorbed to the surface of the anode and directly oxidized to form N2(ii) a Indirect oxidation means Cl in the presence of chloride ions-Is oxidized to form ClO-Or oxides such as HClO and the like, and then oxidizing to remove ammonia nitrogen.
At present, the harmless treatment research of the electrolytic manganese slag still has the problems of low treatment capacity, incomplete treatment of manganese and ammonia nitrogen, more byproducts after treatment and the like. Therefore, it is urgent to find a method which has high processing ability, less by-products, low cost and is suitable for sustainable development.
Disclosure of Invention
According to the method, firstly, alkaline materials are used for removing high-concentration ammonia nitrogen and manganese in the electrolytic manganese slag leachate, so that the cost for removing manganese and ammonia nitrogen in the leachate wastewater of the field strengthening at the rear end is reduced. In addition, the invention adopts DSA material as the anode plate and the copper plate as the cathode plate, has excellent electrocatalytic oxidation capability, and can further cooperate with hypochlorite to strengthen the high-efficiency removal of manganese and ammonia nitrogen in the leachate.
A method for harmless treatment of electric field reinforced electrolytic manganese slag comprises the following steps:
(1) uniformly mixing electrolytic manganese slag and water according to a certain mass ratio to obtain an ore pulp system 1 #; wherein the electrolytic manganese slag and water are mixed according to the mass ratio of = 1: 5-10 mixing;
(2) adjusting the pH value of the ore pulp system No. 1 by using an alkaline material, and ensuring that the pH value of the slurry is maintained at 8.5-11.5 to obtain an ore pulp system No. 2; wherein the alkaline material is one or more of 0.2-2.0 parts by weight of firing raw material, 0.2-2.0 parts by weight of calcium oxide and 0.5-2.0 parts by weight of low-grade magnesium oxide;
(3) aerating the ore pulp system No. 2 for 1-4 h, collecting overflowed gas by using dilute sulfuric acid, performing solid-liquid separation by plate-and-frame filter pressing to obtain filter residue and filtrate No. 3, and recycling the filter residue; wherein the liquid-gas ratio of aeration is 0.38-0.85, and the mass ratio of dilute sulfuric acid is 15-30%;
(4) adding a sodium hypochlorite solution with the volume ratio of 0.1-1.0% into the filtrate 3#, and introducing a current density of 0-40 mA/cm2Reacting for 1-3 h, and performing solid-liquid separation by plate-and-frame filter pressing to obtain filtrate No. 4;
(5) and recycling the obtained filtrate 4# for leaching the electrolytic manganese slag of the next batch. The burning raw material in the invention refers to an intermediate product of a novel dry-method rotary cement kiln decomposing furnace in the cement production process, and the main components of the burning raw material are CaO (67-75%), SiO2（6~11%），SO3（3~5%），Al2O3(3-6%) and Fe2O3(2-6%), compared with industrial calcium oxide, the burning raw material used by the invention has the advantages of high activity, low cost and the like.
Drawings
FIG. 1 is a process flow chart of a method for harmless treatment of electric field reinforced electrolytic manganese slag provided by the invention.
Detailed Description
Example 1:
(1) uniformly mixing 20kg of electrolytic manganese slag and 200kg of water to obtain a pulp system 1 #; the manganese content measured in the system is 2800mg/L, the ammonia nitrogen content is 2994mg/L, and the manganese content and the ammonia nitrogen content exceed the discharge threshold value specified in the Integrated wastewater discharge Standard (GB 8978-1996) by multiple times;
(2) adjusting the pH value of the ore pulp system No. 1 by adopting 2 parts by weight of sodium hydroxide to ensure that the pH value of the slurry is maintained at 11.0 to obtain an ore pulp system No. 2;
(3) aerating the ore pulp system No. 2 for 3 hours, wherein the liquid-gas ratio of aeration is 0.55, collecting overflowed gas by using dilute sulfuric acid with the concentration of 30%, performing solid-liquid separation by plate-and-frame filter pressing to obtain filter pressing residue and filtrate No. 3, and recycling the filter residue;
(4) to filtrate No. 3 was added a 0.8% sodium hypochlorite solution and a current density of 25mA/cm2Reacting for 2 hours, and performing solid-liquid separation by plate-and-frame filter pressing to obtain filtrate No. 4;
(5) and recycling the obtained filtrate 4# for the next batch of electrolytic manganese residue leaching. After treatment, the pH value of the leachate is 7.6, the manganese content is 1.5mg/L, and the ammonia nitrogen content is 10mg/L, which all reach the primary discharge standard specified in the Integrated wastewater discharge Standard (GB 8978-1996).
Example 2:
(1) uniformly mixing 20kg of electrolytic manganese slag and 200kg of water to obtain a pulp system 1 #; the manganese content measured in the system is 2800mg/L, the ammonia nitrogen content is 2994mg/L, and the manganese content and the ammonia nitrogen content exceed the discharge threshold value specified in the Integrated wastewater discharge Standard (GB 8978-1996) by multiple times;
(2) 2 parts by weight of firing raw materials are adopted to adjust the pH value of the ore pulp system No. 1, so that the pH value of the pulp is maintained at 10.5, and the ore pulp system No. 2 is obtained;
(3) aerating the ore pulp system No. 2 for 3 hours, wherein the liquid-gas ratio of aeration is 0.65, collecting overflowed gas by using dilute sulfuric acid with the concentration of 30%, performing solid-liquid separation by plate-and-frame filter pressing to obtain filter pressing residue and filtrate No. 3, and recycling the filter residue;
(4) to filtrate No. 3 was added a 0.7% sodium hypochlorite solution and a current density of 35mA/cm2Reacting for 3 hours, and performing solid-liquid separation by plate-and-frame filter pressing to obtain filtrate No. 4;
(5) and recycling the obtained filtrate 4# for the next batch of electrolytic manganese residue leaching. After treatment, the pH value of the leachate is 9.14, the manganese content is 0.8mg/L, and the ammonia nitrogen content is 5mg/L, which all reach the primary discharge standard specified in the Integrated wastewater discharge Standard (GB 8978-1996).
Example 3:
(1) uniformly mixing 20kg of electrolytic manganese slag and 200kg of water to obtain a pulp system 1 #; the manganese content measured in the system is 2800mg/L, the ammonia nitrogen content is 2994mg/L, and the manganese content and the ammonia nitrogen content exceed the discharge threshold value specified in the Integrated wastewater discharge Standard (GB 8978-1996) by multiple times;
(2) adjusting the pH value of the ore pulp system No. 1 by adopting 2 parts by weight of sodium hydroxide to ensure that the pH value of the slurry is maintained at 11.0 to obtain an ore pulp system No. 2;
(3) aerating the ore pulp system No. 2 for 4 hours, wherein the liquid-gas ratio of aeration is 0.75, collecting overflowed gas by using dilute sulfuric acid with the concentration of 30%, performing solid-liquid separation by plate-and-frame filter pressing to obtain filter pressing residue and filtrate No. 3, and recycling the filter residue;
(4) to filtrate No. 3, a 1.0% sodium hypochlorite solution was added, and a current density of 40mA/cm was added2Reacting for 3 hours, and performing solid-liquid separation by plate-and-frame filter pressing to obtain filtrate No. 4;
(5) and recycling the obtained filtrate 4# for the next batch of electrolytic manganese residue leaching. After treatment, the pH value of the leachate is 6.7, and manganese and ammonia nitrogen are not detected, so that the leachate reaches the primary discharge standard specified in the Integrated wastewater discharge Standard (GB 8978-1996).
Claims (5)
1. Uniformly mixing electrolytic manganese slag and water according to a certain mass ratio to obtain an ore pulp system 1 #; wherein the electrolytic manganese slag and water are mixed according to the mass ratio of = 1: 5 to 10.
2. Adjusting the pH value of the ore pulp system No. 1 by using an alkaline material, and ensuring that the pH value of the slurry is maintained at 8.5-11.5 to obtain an ore pulp system No. 2; wherein the alkaline material is one or more of 0.2-2.0 parts by weight of burning raw material, 0.2-2.0 parts by weight of calcium oxide and 0.5-2.0 parts by weight of low-grade magnesium oxide.
3. Aerating the ore pulp system No. 2 for 1-4 h, collecting overflowed gas by using dilute sulfuric acid, performing solid-liquid separation by plate-and-frame filter pressing to obtain filter residue and filtrate No. 3, and recycling the filter residue; wherein the liquid-gas ratio of aeration is 0.38-0.85, and the mass ratio of dilute sulfuric acid is 15-30%.
4. Adding a sodium hypochlorite solution with the volume ratio of 0.1-1.0% into the filtrate 3#, and introducing a current density of 0-40 mA/cm2Reacting for 1-3 h, and performing solid-liquid separation by plate-and-frame filter pressing to obtain filtrate No. 4.
5. And recycling the obtained filtrate 4# for leaching the electrolytic manganese slag of the next batch.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911109621.2A CN112792086A (en) | 2019-11-14 | 2019-11-14 | Method for harmless treatment of electric field reinforced electrolytic manganese slag |
| PCT/CN2020/120186 WO2021093491A1 (en) | 2019-11-14 | 2020-10-10 | Method for electric field enhanced harmless treatment of electrolytic manganese residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911109621.2A CN112792086A (en) | 2019-11-14 | 2019-11-14 | Method for harmless treatment of electric field reinforced electrolytic manganese slag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112792086A true CN112792086A (en) | 2021-05-14 |
Family
ID=75803576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911109621.2A Pending CN112792086A (en) | 2019-11-14 | 2019-11-14 | Method for harmless treatment of electric field reinforced electrolytic manganese slag |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112792086A (en) |
| WO (1) | WO2021093491A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277654A (en) * | 2021-05-28 | 2021-08-20 | 金川集团股份有限公司 | Method and device for treating electrodeposition high-purity manganese waste liquid by using electrochemical method |
| CN114871240A (en) * | 2022-03-30 | 2022-08-09 | 湖南博一环保科技有限公司 | Electrolytic manganese filter-press residue for removing ammonia nitrogen and desulfurization as well as preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03225753A (en) * | 1990-01-30 | 1991-10-04 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolytic secondary battery |
| JP2011129336A (en) * | 2009-12-17 | 2011-06-30 | Tosoh Corp | Recovery method of manganese from battery |
| US20140042029A1 (en) * | 2012-08-13 | 2014-02-13 | Enviro Water Minerals Company, Inc. | System for rinsing electrodialysis electrodes |
| CN104083845A (en) * | 2014-07-11 | 2014-10-08 | 广西大学 | Method for stabilizing water-soluble manganese ions in manganese ore leaching residue |
| CN105039718A (en) * | 2015-09-11 | 2015-11-11 | 长沙矿冶研究院有限责任公司 | Comprehensive recycling method of electrolytic manganese anolyte |
| CN106186455A (en) * | 2016-07-06 | 2016-12-07 | 重庆大学 | A kind of method of electrolytic manganese residues percolate harmless treatment |
| CN108262336A (en) * | 2018-02-24 | 2018-07-10 | 昆明理工大学 | A kind of solidification processing method of electrolytic manganese residues |
| CN109554546A (en) * | 2018-10-24 | 2019-04-02 | 西南科技大学 | A kind of method of electrolytic manganese residues harmless treatment and resource utilization |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4192205B2 (en) * | 2007-04-09 | 2008-12-10 | メタウォーター株式会社 | Membrane cleaning method and membrane cleaning apparatus |
| CN103820647B (en) * | 2014-03-22 | 2015-07-01 | 重庆大学 | Method for secondary leaching of electrolytic manganese residue and manganese recovery |
| CN109384359A (en) * | 2018-12-24 | 2019-02-26 | 烟台盛泽环保科技有限公司 | A kind of manganese slag extraction wastewater recovery processing equipment and process |
-
2019
- 2019-11-14 CN CN201911109621.2A patent/CN112792086A/en active Pending
-
2020
- 2020-10-10 WO PCT/CN2020/120186 patent/WO2021093491A1/en active Application Filing
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03225753A (en) * | 1990-01-30 | 1991-10-04 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolytic secondary battery |
| JP2011129336A (en) * | 2009-12-17 | 2011-06-30 | Tosoh Corp | Recovery method of manganese from battery |
| US20140042029A1 (en) * | 2012-08-13 | 2014-02-13 | Enviro Water Minerals Company, Inc. | System for rinsing electrodialysis electrodes |
| CN104083845A (en) * | 2014-07-11 | 2014-10-08 | 广西大学 | Method for stabilizing water-soluble manganese ions in manganese ore leaching residue |
| CN105039718A (en) * | 2015-09-11 | 2015-11-11 | 长沙矿冶研究院有限责任公司 | Comprehensive recycling method of electrolytic manganese anolyte |
| CN106186455A (en) * | 2016-07-06 | 2016-12-07 | 重庆大学 | A kind of method of electrolytic manganese residues percolate harmless treatment |
| CN108262336A (en) * | 2018-02-24 | 2018-07-10 | 昆明理工大学 | A kind of solidification processing method of electrolytic manganese residues |
| CN109554546A (en) * | 2018-10-24 | 2019-04-02 | 西南科技大学 | A kind of method of electrolytic manganese residues harmless treatment and resource utilization |
| 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 (2)
| Title |
|---|
| 陈红亮: "电氧化法去除电解锰渣滤液中NH_4_N试验研究", 《湿法冶金》 * |
| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277654A (en) * | 2021-05-28 | 2021-08-20 | 金川集团股份有限公司 | Method and device for treating electrodeposition high-purity manganese waste liquid by using electrochemical method |
| CN114871240A (en) * | 2022-03-30 | 2022-08-09 | 湖南博一环保科技有限公司 | Electrolytic manganese filter-press residue for removing ammonia nitrogen and desulfurization as well as preparation method and application thereof |
| CN114871240B (en) * | 2022-03-30 | 2023-05-30 | 湖南博一环保科技有限公司 | Electrolytic manganese filter pressing slag for ammonia nitrogen removal and desulfurization as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021093491A1 (en) | 2021-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101533649B1 (en) | Wastewater treatment method using micro-electrolysis reaction and its micro-electrolysis matter | |
| CN109554546B (en) | Method for harmless treatment and resource utilization of electrolytic manganese slag | |
| CN108128917B (en) | Method for removing various pollutants in copper smelting waste acid by using Bayer process red mud | |
| CN101633982A (en) | Method for circularly removing chlorine in zinc sulphate solution by copper slag | |
| CN101845562A (en) | Improved device and method for producing electrolytic manganese metal by two-ore method | |
| CN104018184A (en) | Brand new method of producing electrolytic manganese metal | |
| CN106396056A (en) | Method for treating electrolytic manganese wastewater containing manganese and magnesium and recovering manganese from wastewater | |
| CN112792086A (en) | Method for harmless treatment of electric field reinforced electrolytic manganese slag | |
| CN111206257B (en) | Alkaline waste residue dealkalization method based on electrochemistry | |
| CN107188292B (en) | Method for purifying arsenic-containing waste liquid by utilizing cyaniding silver extraction waste residues | |
| CN111186887A (en) | Method for removing and recovering thallium from industrial wastewater | |
| CN100402442C (en) | High-efficient environment treating method for acidic etching waste liquid | |
| CN110396595B (en) | Efficient decomposition method of manganese dithionate in manganese ore sulfur dioxide leaching solution | |
| CN110607451B (en) | System and process for treating waste contact bodies and slurry residues generated in organic silicon production process | |
| CN112794510A (en) | Method for harmlessly treating low-concentration manganese-containing ammonia-nitrogen wastewater in electrolytic manganese industry | |
| CN116426976A (en) | Method and equipment for resource utilization and innocent treatment of manganese slag | |
| CN116656952A (en) | Method for treating and recovering manganese, magnesium and ammonium in leachate of electrolytic manganese slag warehouse | |
| CN111333222A (en) | Method for removing COD in landfill leachate | |
| CN1958462A (en) | Method for preparing potassium ferrate by using waste liquid from acid washing steel | |
| CN114524462A (en) | Method for preparing potassium ferrate and cementing material by utilizing waste incineration fly ash and iron tailings | |
| CN110255784B (en) | Method for synchronously removing nitrogen and phosphorus in pig-raising wastewater | |
| CN114558440A (en) | Process for efficiently extracting zinc by high-chlorine zinc ash ammonia-ammonium sulfate method and flue gas desulfurization and carbon fixation by coupled slurry method | |
| CN103466686A (en) | Method for quickly removing arsenic in zinc oxide with high arsenic content and producing zinc sulfate by using zinc ash and sodium peroxycarbonate of iron and steel plant | |
| CN113751476A (en) | Method for cooperative treatment and cyclic utilization of metallurgical solid waste and municipal waste incineration fly ash | |
| CN102634656A (en) | Method for preparing electrolytic manganese/electrolytic manganese dioxide by cyclically leaching manganese oxide with sulfur and calcium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210514 |
|
| WD01 | Invention patent application deemed withdrawn after publication |