CN116656952A - Method for treating and recovering manganese, magnesium and ammonium in leachate of electrolytic manganese slag warehouse - Google Patents
Method for treating and recovering manganese, magnesium and ammonium in leachate of electrolytic manganese slag warehouse Download PDFInfo
- Publication number
- CN116656952A CN116656952A CN202310643316.1A CN202310643316A CN116656952A CN 116656952 A CN116656952 A CN 116656952A CN 202310643316 A CN202310643316 A CN 202310643316A CN 116656952 A CN116656952 A CN 116656952A
- Authority
- CN
- China
- Prior art keywords
- filtrate
- manganese
- ammonium
- magnesium
- solid
- 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
- 239000011572 manganese Substances 0.000 title claims abstract description 66
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 52
- 239000002893 slag Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000011777 magnesium Substances 0.000 title claims abstract description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 23
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 title claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 28
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 21
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims description 75
- 238000005406 washing Methods 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 35
- 238000000926 separation method Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 18
- 239000011656 manganese carbonate Substances 0.000 claims description 16
- 235000006748 manganese carbonate Nutrition 0.000 claims description 16
- 229940093474 manganese carbonate Drugs 0.000 claims description 16
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 16
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 9
- 230000009615 deamination Effects 0.000 claims description 9
- 238000006481 deamination reaction Methods 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000004571 lime Substances 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000003337 fertilizer Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 229910052567 struvite Inorganic materials 0.000 abstract description 7
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical group [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910017958 MgNH Inorganic materials 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
- C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a method for treating and recycling manganese, magnesium and ammonium in leachate of an electrolytic manganese slag warehouse, which can effectively avoid secondary pollution, and the produced product can be directly reused for production and can also be used for fertilizer production or directly used as fertilizer. Calcium carbonate is used as an industrial raw material. The phosphate precipitate is magnesium ammonium phosphate commonly known as struvite, and can be used as fertilizer. The high-purity ammonium sulfate can be used as industrial raw materials and fertilizers. The method effectively recovers the manganese resources in the percolate, prepares the industrial-grade product, has simple process, recovers the resources to the maximum extent, does not cause secondary pollution, and is environment-friendly, low in cost and simple and convenient to operate.
Description
Technical Field
The invention belongs to the technical field of metal smelting, and particularly relates to a method for treating and recycling manganese, magnesium and ammonium in leachate of an electrolytic manganese slag warehouse.
Background
The electrolytic manganese industry in China starts late, but has rapid development, and is the largest national country for electrolytic manganese production, export and consumption. The waste water produced in the electrolytic manganese production has complex components and heavy pollution load, and contains various pollutants such as manganese, ammonia nitrogen, suspended matters and the like, and along with the high-speed development of the electrolytic manganese industry in recent years, the electrolytic manganese slag field has large occupied area, long pollution duration and serious influence on ecological environment, and gradually becomes the management key point of pollution in the electrolytic manganese industry. The electrolytic manganese slag contains a large amount of soluble salts, solid minerals, chromium, lead, arsenic and other heavy metal harmful elements, wherein iron, magnesium and the like form hydroxide colloid, so that the moisture in the electrolytic manganese slag is difficult to filter-press thoroughly, therefore, the electrolytic manganese slag has higher water content, heavy metals are easy to exude, and the heavy metals are infiltrated into soil along with surface runoff and continuously accumulated to cause serious pollution to ecological environment. A large amount of Mn (II) in the electrolytic manganese slag percolate is leached into surrounding soil, surface water and underground water through acid rain, so that the ecological environment is destroyed, and the ecological environment is threatened to human health. In addition, manganese is a strategic resource, and is necessary to be recycled, so that development of a harmless and recycling treatment method for electrolytic manganese slag percolate is urgently needed.
At present, a plurality of industrial methods for treating electrolytic manganese slag percolate still have the problems of high cost, immature technology and the like in the whole technical research, and have great difference from industrial application. In the prior art, manganese and ammonia nitrogen are mostly removed as harmful substances, and the resource utilization is difficult. The environmental pollution is a serious problem faced in the current development of China, the China can never go to the old road of 'pollution first and treatment later', and practical and effective measures must be taken to increase the working strength of environmental protection. The clean production is a new mode of modern industrial development, advocates to eliminate pollution as much as possible, reduce environmental hazard and reasonable utilization of resources and slow down resource exhaustion, and can be summarized to try to produce pollution at the lowest level and utilize resources at the highest level. The electrolytic manganese industry is taken as a typical three-high-one-low industry with high investment, high energy consumption, high pollution and low benefit, and the method has great significance for the green sustainable development of the industry by being greatly promoted and implementing clean production.
Disclosure of Invention
The invention aims to provide a treatment method for recycling manganese, magnesium and ammonium from electrolytic manganese slag pool leachate, which is environment-friendly, low in cost and simple and convenient to operate.
The invention relates to a method for treating and recycling manganese, magnesium and ammonium in leachate of an electrolytic manganese slag library, which comprises the following steps:
(1) Adding carbonate with the theoretical amount of 1.1-1.3 times of that required by manganese precipitation into the percolate of the manganese slag warehouse, stirring for 1 hour for one time, carrying out solid-liquid separation to obtain filtrate I, washing manganese carbonate slag to obtain washing water I, and drying the solid at 60-80 ℃ to obtain a product I with the main component of manganese carbonate;
(2) Adding alkali into the first filtrate after primary stirring to adjust the pH value to 9-10, carrying out secondary stirring, simultaneously quantitatively and continuously adding phosphate, obtaining a second filtrate after solid-liquid separation, washing filter residues after solid-liquid separation to generate second washing water, and drying the solid after washing to obtain a second product, and precipitating the phosphate;
(3) Mixing the filtrate II with the washing water I and the washing water II, adding lime for stirring reaction, performing solid-liquid separation after precipitation to obtain waste residue and filtrate III, conveying the filter residue to a residue warehouse for landfill, and continuing the subsequent treatment of the filtrate III;
(4) Adding sodium carbonate into the filtrate III, stirring, and adding Ca 2+ Converting into calcium carbonate precipitate, and performing solid-liquid separation to obtain filtrate IV and calcium carbonate;
(5) And the filtrate IV enters a membrane deamination system, is converted into an ammonium sulfate solution after being absorbed by a gaseous membrane, and the effluent reaches the emission standard, and the ammonium sulfate solution is evaporated and crystallized after being enriched to a certain concentration to obtain the high-purity ammonium sulfate.
The method for treating and recovering manganese, magnesium and ammonium from the electrolytic manganese slag library percolate comprises the step (1) of preparing carbonate from sodium bicarbonate.
The method for treating and recovering manganese, magnesium and ammonium in the electrolytic manganese slag library percolate comprises the step (2), wherein phosphate is one or more of disodium hydrogen phosphate, monosodium hydrogen phosphate and sodium phosphate;
the method for treating and recovering manganese, magnesium and ammonium from the electrolytic manganese slag library percolate comprises the step (2) of adding the total phosphate according to the mass concentration of magnesium substances in the solution of 1:1.
The method for treating and recovering manganese, magnesium and ammonium in the leachate of the electrolytic manganese slag pool comprises the step (3) of adding lime according to Mn in the solution 2+ 、Mg 2+ The addition amount is 1.2-1.5 times of the theoretical amount.
The method for treating and recovering manganese, magnesium and ammonium from the electrolytic manganese slag library percolate comprises the step (3) of adding sodium carbonate in an amount which is 1.1-1.3 times of the theoretical weight of the filtrate.
Compared with the prior art, the method has obvious beneficial effects, and the scheme proves that secondary pollution can be effectively avoided by treating the leachate of the electrolytic manganese slag warehouse, the main substances in the leachate are comprehensively recycled, and the produced product can be directly reused for production and also can be used for fertilizer production or directly used as fertilizer. Calcium carbonate is used as an industrial raw material. The phosphate precipitate is magnesium ammonium phosphate commonly known as struvite, and can be used as fertilizer. The high-purity ammonium sulfate can be used as industrial grade raw materials or fertilizers. The method can effectively recover the manganese resources in the percolate, recycle or prepare industrial-grade products, has simple process, furthest recovers the resources, does not cause secondary pollution, is environment-friendly, has low cost and is simple and convenient to operate.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Example 1
A treatment method for recovering manganese, magnesium and ammonium from electrolytic manganese slag pool leachate comprises the following steps:
(1) Adding sodium bicarbonate with the theoretical amount of 1.3 times of that required by manganese precipitation into the percolate of the manganese slag warehouse, stirring for 1 hour for one time, performing solid-liquid separation to obtain filtrate I, washing manganese carbonate slag to obtain washing water I, and drying the solid at 60 ℃ to obtain a product I with the main component of manganese carbonate;
(2) Adding alkali into the first filtrate after primary stirring to adjust the pH to be between 10, carrying out secondary stirring, simultaneously quantitatively and continuously adding sodium phosphate, carrying out solid-liquid separation to obtain a second filtrate, washing filter residues after the solid-liquid separation to generate second washing water, and drying the solid after the washing is finished to obtain a second product, and precipitating phosphate;
(3) Mixing the filtrate II with the washing water I and washing water II, adding Mn into the solution 2+ 、Mg 2+ Stirring lime with the theoretical amount of 1.5 times, performing solid-liquid separation after precipitation to obtain waste residue and filtrate III, conveying the filter residue to a residue warehouse for landfill, and continuing the post-treatment of the filtrate III;
(4) Adding sodium carbonate 1.1 times of the theoretical weight of the filtrate into the filtrate III, stirring, and adding Ca 2+ Converting into calcium carbonate precipitate, and performing solid-liquid separation to obtain filtrate IV and calcium carbonate;
(5) The filtrate IV enters a membrane deamination system, is converted into an ammonium sulfate solution after being absorbed by a gaseous membrane, the pH value is regulated to 6 by adding sulfuric acid, the effluent reaches the discharge standard, and the ammonium sulfate solution is evaporated and crystallized after being enriched to a certain concentration, so that the high-purity ammonium sulfate is obtained.
Example 2
A treatment method for recovering manganese, magnesium and ammonium from electrolytic manganese slag pool leachate comprises the following steps:
(1) Adding sodium bicarbonate with the theoretical amount of 1.2 times of that required by manganese precipitation into the percolate of the manganese slag warehouse, stirring for 1 hour for one time, performing solid-liquid separation to obtain filtrate I, washing manganese carbonate slag to obtain washing water I, and drying the solid at 70 ℃ to obtain a product I with the main component of manganese carbonate;
(2) Adding alkali into the first filtrate after primary stirring to adjust the pH to be between 10, carrying out secondary stirring, simultaneously quantitatively and continuously adding sodium phosphate monobasic, carrying out solid-liquid separation to obtain a second filtrate, washing filter residues after the solid-liquid separation to generate second washing water, and drying the solid after the washing is finished to obtain a second product, and precipitating phosphate;
(3) Mixing the filtrate II with the washing water I and washing water II, adding Mn into the solution 2+ 、Mg 2+ Stirring lime with the theoretical amount of 1.4 times, performing solid-liquid separation after precipitation to obtain waste residue and filtrate III, conveying the filter residue to a residue warehouse for landfill, and continuing the post-treatment of the filtrate III;
(4) Adding sodium carbonate 1.2 times of the theoretical weight of the filtrate into the filtrate III, stirring, and adding Ca 2+ Converting into calcium carbonate precipitate, and performing solid-liquid separation to obtain filtrate IV and calcium carbonate;
(5) The filtrate IV enters a membrane deamination system, is converted into an ammonium sulfate solution after being absorbed by a gaseous membrane, the pH value is regulated to 6 by adding sulfuric acid, the effluent reaches the discharge standard, and the ammonium sulfate solution is evaporated and crystallized after being enriched to a certain concentration, so that the high-purity ammonium sulfate is obtained.
Example 3
A treatment method for recovering manganese, magnesium and ammonium from electrolytic manganese slag pool leachate comprises the following steps:
(1) Adding sodium bicarbonate with the theoretical amount of 1.3 times of that required by manganese precipitation into the percolate of the manganese slag warehouse, stirring for 1 hour for one time, performing solid-liquid separation to obtain filtrate I, washing manganese carbonate slag to obtain washing water I, and drying the solid at 60 ℃ to obtain a product I with the main component of manganese carbonate;
(2) Adding alkali into the first filtrate after primary stirring to adjust the pH value to 9-10, carrying out secondary stirring, simultaneously quantitatively and continuously adding disodium hydrogen phosphate, carrying out solid-liquid separation to obtain a second filtrate, washing filter residues after the solid-liquid separation to generate second washing water, and drying the solid after the washing is finished to obtain a second product, and precipitating phosphate;
(3) Mixing the filtrate II with the washing water I and washing water II, adding Mn into the solution 2+ 、Mg 2+ Stone of 1.2 times theoretical amountStirring the ash for reaction, performing solid-liquid separation after precipitation to obtain waste residue and filtrate III, conveying the filter residue to a residue warehouse for landfill, and continuing the post-treatment of the filtrate III;
(4) Adding sodium carbonate 1.3 times of the theoretical weight of the filtrate into the filtrate III, stirring, and adding Ca 2+ Converting into calcium carbonate precipitate, and performing solid-liquid separation to obtain filtrate IV and calcium carbonate;
(5) The filtrate IV enters a membrane deamination system, is converted into an ammonium sulfate solution after being absorbed by a gaseous membrane, the pH value is regulated to 9 by adding sulfuric acid, the effluent reaches the discharge standard, and the ammonium sulfate solution is evaporated and crystallized after being enriched to a certain concentration, so that the high-purity ammonium sulfate is obtained.
The following are examples of the relevant tests of the present invention:
test example 1
Taking 100m of percolate of a manganese slag warehouse 3 In the reaction tank, the conditions of the main components in the percolate obtained by sampling and analysis are as follows:
| composition of the components | Mn 2+ | Mg 2+ | (NH 4 ) 2 SO 4 | Ca |
| Data | 10.2g/L | 6.6g/L | 28.3g/L | 0.6g/L |
Adding 3970kg of industrial sodium bicarbonate into the solution, stirring and reacting for 1h, and then carrying out solid-liquid separation by using a plate-and-frame filter press with a washing function, wherein the first filtrate enters into subsequent treatment;
adding clear water into a plate-and-frame filter press to wash residues to obtain washed manganese carbonate wet materials, drying to obtain 1881kg of industrial manganese carbonate, and feeding washing water into a subsequent wastewater treatment process;
the manganese carbonate composition is as follows:
| composition of the components | Mn/％ | Chloride (in Cl)/% | Sulfate (in SO) 4 Meter)/% |
| Data | 41.6 | 0.006 | 0.68 |
Adding caustic soda flakes into the filtrate I after manganese precipitation to adjust the pH value to 9-10, and continuously adding 3000kg of disodium hydrogen phosphate under stirring to obtain filtrate II and magnesium ammonium phosphate precipitate;
the sulfate precipitate is subjected to solid-liquid separation, washing and drying to obtain 3401kg of magnesium ammonium phosphate for industry or agriculture, and the ingredients are shown in the following table:
| composition of the components | P/％ | N/％ | MgO/％ | MgNH 4 PO 4 /％ |
| Data | 18.1 | 3.2 | 10.1 | 60.8 |
The primary stirring and secondary stirring solid-liquid separation washing water I and washing water II are mixed with the filtrate II and then enter a post-treatment process, and the total of the obtained filtrate is 110m < 3 >, and the main components are as follows:
| composition of the components | Mn 2+ | Mg 2+ | (NH4) 2 SO 4 | Ca |
| Data | 0.8g/L | 1.0g/L | 10.1g/L | 0.6g/L |
Adding 1213kg of lime into the mixed solution of the filtrate II, the washing water I and the washing water II, stirring and reacting to obtain a precipitate, then performing solid-liquid separation to obtain filtrate III, entering a post-treatment process, and directly entering a slag field for landfill;
continuously stirring the filtrate III for reaction, adding 262kg of sodium carbonate into the filtrate III, carrying out solid-liquid separation to obtain a product IV, and simultaneously producing the filtrate IV, wherein the main component of the product IV is calcium carbonate which can be used as an industrial raw material, and the filtrate IV continuously enters a post-treatment process;
and the filtrate IV enters a deamination membrane system, sulfuric acid is added into the gaseous membrane system, NH3-N of the filtrate IV after being treated by the gaseous membrane reaches the emission standard, the pH value is regulated to be between 6 and 9 by adding sulfuric acid, and the standard-reaching emission can be achieved, wherein the main components of standard-reaching emission water are as follows:
| project | Mn(mg/L) | NH 3 -N(mg/L) | pH |
| Data | 0.95 | 9.0 | 7.6 |
NH4 < + > in the solution after membrane deamination is converted into a high-concentration ammonium sulfate solution, and the ammonium sulfate with higher purity can be obtained by MVR evaporation and crystallization and can be used as an industrial raw material.
Test example 2
Taking 100m of percolate of a manganese slag warehouse 3 In the reaction tank, the conditions of the main components in the percolate obtained by sampling and analysis are as follows:
| composition of the components | Mn 2+ | Mg 2+ | (NH 4 ) 2 SO 4 | Ca |
| Data | 6.3g/L | 4.2g/L | 16.7g/L | 0.5g/L |
Adding 2016.6kg of industrial sodium bicarbonate into the mixture, stirring the mixture for reaction for 1h, then carrying out solid-liquid separation by using a plate-and-frame filter press with a washing function, and carrying out subsequent treatment on filtrate I;
adding clear water into a plate-and-frame filter press to wash residues to obtain washed manganese carbonate, drying to obtain 1129.1kg of industrial manganese carbonate, and adding washing water into a subsequent wastewater treatment process;
the manganese carbonate composition is as follows:
| composition of the components | Mn/％ | Chloride (in Cl)/% | Sulfate (in SO) 4 Meter)/% |
| Data | 40.8 | 0.006 | 0.52 |
Adding NaOH aqueous solution into the filtrate I after manganese precipitation to adjust the pH value to 9-10, and continuously adding 2000.0kg of monosodium phosphate under the stirring condition to obtain phosphate precipitation;
the sulfate precipitate is subjected to solid-liquid separation, washing and drying to obtain 2288.5kg of magnesium ammonium phosphate for industry or agriculture, and the ingredients are shown in the following table:
| composition of the components | P/％ | N/％ | MgO/％ | MgNH 4 PO4/％ |
| Data | 18.1 | 3.2 | 10.1 | 60.8 |
The washing water obtained by the primary stirring and secondary stirring solid-liquid separation was mixed with the filtrate and then subjected to a post-treatment step to obtain a total filtrate of 110m3, and the main components were as follows:
| composition of the components | Mn 2+ | Mg 2+ | (NH 4 ) 2 SO 4 | Ca |
| Data | 0.8g/L | 1.0g/L | 10.1g/L | 0.6g/L |
Adding 1213.0kg of lime into the mixed solution of the filtrate II, the washing water I and the washing water II, stirring and reacting to obtain a precipitate, then performing solid-liquid separation to obtain filtrate III, entering a post-treatment process, and directly entering a slag field for landfill;
continuously stirring the filtrate III for reaction, adding 218kg of sodium carbonate into the filtrate III, carrying out solid-liquid separation to obtain a product IV, and simultaneously producing the filtrate IV, wherein the main component of the product IV is calcium carbonate which can be used as an industrial raw material, and the filtrate IV continuously enters a post-treatment process;
and the filtrate IV enters a deamination membrane system, sulfuric acid is added into the gaseous membrane system, NH3-N of the filtrate after the treatment of the gaseous membrane reaches the discharge standard, the pH value is regulated to be between 6 and 9 by adding sulfuric acid, and the standard discharge can be achieved, wherein the main components of standard discharge water are as follows:
| project | Mn(mg/L) | NH 3 -N(mg/L) | pH |
| Data | 1.25 | 9.6 | 8.2 |
NH4 < + > in the solution after membrane deamination is converted into a high-concentration ammonium sulfate solution, and the ammonium sulfate with higher purity can be obtained by MVR evaporation and crystallization and can be used as an industrial raw material.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any simple modification, equivalent variation and variation of the above embodiment according to the technical matter of the present invention still fall within the scope of the technical scheme of the present invention.
Claims (6)
1. A method for treating and recovering manganese, magnesium and ammonium from leachate of an electrolytic manganese slag pool comprises the following steps:
(1) Adding carbonate with the theoretical amount of 1.1-1.3 times of that required by manganese precipitation into the percolate of the manganese slag warehouse, stirring for 1 hour for one time, carrying out solid-liquid separation to obtain filtrate I, washing manganese carbonate slag to obtain washing water I, and drying the solid at 60-80 ℃ to obtain a product I with the main component of manganese carbonate;
(2) Adding alkali into the first filtrate after primary stirring to adjust the pH value to 9-10, carrying out secondary stirring, simultaneously quantitatively and continuously adding phosphate, obtaining a second filtrate after solid-liquid separation, washing filter residues after solid-liquid separation to generate second washing water, and drying the solid after washing to obtain a second product, and precipitating the phosphate;
(3) Mixing the filtrate II with the washing water I and the washing water II, adding lime for stirring reaction, performing solid-liquid separation after precipitation to obtain waste residue and filtrate III, conveying the filter residue to a residue warehouse for landfill, and continuing the subsequent treatment of the filtrate III;
(4) Adding sodium carbonate into the filtrate III, stirring, and adding Ca 2+ Converting into calcium carbonate precipitate, and performing solid-liquid separation to obtain filtrate IV and calcium carbonate;
(5) And the filtrate IV enters a membrane deamination system, is converted into an ammonium sulfate solution after being absorbed by a gaseous membrane, and the effluent reaches the emission standard, and the ammonium sulfate solution is evaporated and crystallized after being enriched to a certain concentration to obtain the high-purity ammonium sulfate.
2. A method for treating and recovering manganese, magnesium and ammonium from an electrolytic manganese slag pool leachate according to claim 1, wherein the carbonate in the step (1) is sodium bicarbonate.
3. The method for treating and recovering manganese, magnesium and ammonium from electrolytic manganese slag pool leachate according to claim 1, wherein the phosphate in the step (2) is one or more of disodium hydrogen phosphate, monosodium hydrogen phosphate and sodium phosphate.
4. A method for treating and recovering manganese, magnesium and ammonium from an electrolytic manganese slag pool leachate according to claim 1, wherein the total amount of phosphate added in step (2) is added according to the amount concentration of magnesium in solution of 1:1.
5. A method for treating and recovering manganese, magnesium and ammonium from electrolytic manganese slag pool leachate according to claim 1, wherein the lime addition amount in step (3) is based on Mn in solution 2+ 、Mg 2+ The addition amount is 1.2-1.5 times of the theoretical amount.
6. The method for treating and recovering manganese, magnesium and ammonium from electrolytic manganese slag pool leachate according to claim 1, wherein the sodium carbonate in the step (3) is added in an amount which is 1.1-1.3 times of the theoretical weight of the filtrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310643316.1A CN116656952A (en) | 2023-06-01 | 2023-06-01 | Method for treating and recovering manganese, magnesium and ammonium in leachate of electrolytic manganese slag warehouse |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310643316.1A CN116656952A (en) | 2023-06-01 | 2023-06-01 | Method for treating and recovering manganese, magnesium and ammonium in leachate of electrolytic manganese slag warehouse |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116656952A true CN116656952A (en) | 2023-08-29 |
Family
ID=87727370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310643316.1A Pending CN116656952A (en) | 2023-06-01 | 2023-06-01 | Method for treating and recovering manganese, magnesium and ammonium in leachate of electrolytic manganese slag warehouse |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116656952A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117401851A (en) * | 2023-11-06 | 2024-01-16 | 宜昌胜创新材料有限公司 | Treatment and resource recovery process of manganese-containing wastewater |
-
2023
- 2023-06-01 CN CN202310643316.1A patent/CN116656952A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117401851A (en) * | 2023-11-06 | 2024-01-16 | 宜昌胜创新材料有限公司 | Treatment and resource recovery process of manganese-containing wastewater |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108483501B (en) | Comprehensive utilization method of electrolytic manganese slag washing liquid | |
| CN102674278B (en) | Method for pre-treating phosphorus rock by titanium dioxide waste acid | |
| CN103213964A (en) | Method for producing wet-process phosphoric acid by utilizing low-grade phosphorite | |
| CN100519783C (en) | Technique for comprehensive utilization clean production of phosphorus block ore and extracting rare earth form the phosphorus block ore | |
| CN104860279A (en) | Method for extracting phosphate concentrate from phosphate tailings and cooperatively producing calcium ammonium nitrate and magnesium ammonium sulphate | |
| CN103213960A (en) | Method for producing phosphoric acid by decomposing low-grade phosphate rock with wet-process phosphoric acid | |
| CN109179457B (en) | Method for extracting lithium from electrolytic aluminum waste residues | |
| CN112279227B (en) | Chemical magnesium removal method for collophanite and tailings-free production | |
| CN104071818A (en) | Method for separating calcium, magnesium and phosphorus elements from phosphate tailings by adopting water leaching and ammonium leaching | |
| CN116656952A (en) | Method for treating and recovering manganese, magnesium and ammonium in leachate of electrolytic manganese slag warehouse | |
| CN102795641A (en) | Novel method for direct extraction recovery of ammonia nitrogen from electrolyzed manganese slag | |
| CN101486481A (en) | Method for coproduction of ammonia sulfate and superfine light calcium carbonate from fluorgypsum | |
| CN103613181A (en) | Method for treating phosphogypsum slag dump pool water by using low-grade lime | |
| CN113620689A (en) | Method for preparing magnesium oxysulfate building material by using boron mud | |
| CN111807905A (en) | Method for preparing soil conditioner by using industrial solid wastes | |
| CN102701611A (en) | Precipitation conversion method for removing sulfates from electrolytic manganese slag | |
| CN115432714B (en) | Comprehensive utilization method of electrolytic manganese slag and demanganization building material | |
| CN115583655B (en) | Method for classifying, extracting, utilizing and converting high-calcium and high-iron gasification slag elements | |
| CN103588345A (en) | Chemical recycling method for treating phosphorus-containing wastewater from electrode foil production | |
| CN113234941B (en) | High-value utilization method of electrolytic manganese anode slime | |
| CN113145612B (en) | Method for solidifying electrolytic manganese slag heavy metal by utilizing coal gasification process tail gas and carbide slag in cooperation | |
| CN109399723A (en) | A method of electrolytic manganese dioxide is produced using manganese tailing and Titanium white waste sulfuric acid | |
| CN101880773B (en) | Manufacturing process for producing synthetic reducing agent by using waste slag of electrolytic manganese and application of synthetic reducing agent | |
| CN104017998B (en) | A kind of manganese slag for comprehensive Application way | |
| CN110734093B (en) | Method for co-producing manganese hydroxide and sulfuric acid or ammonium sulfite by electrolyzing metal manganese waste residue |
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 |