CN114715943A - Process for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride and preparation method - Google Patents
Process for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride and preparation method Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 90
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 82
- 239000002351 wastewater Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 52
- 229910021380 Manganese Chloride Inorganic materials 0.000 title claims abstract description 35
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 title claims abstract description 35
- 239000011565 manganese chloride Substances 0.000 title claims abstract description 35
- 235000002867 manganese chloride Nutrition 0.000 title claims abstract description 35
- 229940099607 manganese chloride Drugs 0.000 title claims abstract description 35
- 230000008569 process Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title description 3
- 239000000243 solution Substances 0.000 claims abstract description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 22
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 19
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 19
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 9
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 8
- 239000012047 saturated solution Substances 0.000 claims abstract description 8
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical group [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 230000032683 aging Effects 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 230000008020 evaporation Effects 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 229910001424 calcium ion Inorganic materials 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 9
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 8
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 229940099596 manganese sulfate Drugs 0.000 description 9
- 239000011702 manganese sulphate Substances 0.000 description 9
- 235000007079 manganese sulphate Nutrition 0.000 description 9
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 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 description 3
- 239000002244 precipitate Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910014813 CaC2 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- UMRUNOIJZLCTGG-UHFFFAOYSA-N calcium;manganese Chemical compound [Ca+2].[Mn].[Mn].[Mn].[Mn] UMRUNOIJZLCTGG-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013048 microbiological method Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/06—Halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a process for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride, which comprises the steps of carrying out evaporation concentration treatment on the manganese-containing wastewater to obtain a saturated solution; adding ammonium bicarbonate into a saturated solution of manganese-containing wastewater, stirring and reacting, adjusting the pH value of the manganese-containing wastewater to 6.5-7, fully stirring, and filtering to obtain filter residue and filtrate; adding acidolysis agent into the filter residue manganese carbonate crude product, stirring at room temperature for dissolving, and completely dissolving manganese carbonate to obtain Mn2+A solution; in Mn2+Adding oxalic acid into the solution, carrying out water bath heating reaction for 1h at the temperature of 60-80 ℃, carrying out solid-liquid separation after aging for 2-4 h, filtering, washing and drying the solution, wherein the filter residue is calcium oxalate, and the filtrate is manganese chloride solution; and recrystallizing the manganese chloride solution to obtain pure manganese chloride crystals. The inventionThe manganese-containing wastewater is recycled, so that the manganese-containing wastewater is harmless and high-purity manganese chloride is produced, the resource utilization of the manganese-containing wastewater is realized, and a manganese product with higher value can be prepared.
Description
Technical Field
The invention relates to the technical field of recovery treatment of tail-end wastewater generated in electrolytic manganese industry, in particular to a process for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride.
Background
The manganese-containing wastewater is electrolytic manganese slag generated by an electrolytic manganese process, and acidic wastewater generated after solid waste is recycled through acidolysis, and a certain amount of wastewater containing manganese, calcium and magnesium ions and higher ammonia nitrogen can be generated in the mining and deep processing processes of manganese ores due to the restriction of the existing equipment and process. Manganese is one of important monitoring indexes of environmental water pollutants, the manganese concentration of a factory sewage outlet is regulated to be within 2.0mg/L by the state, and the manganese-containing wastewater treatment is always a research hotspot.
Large amounts of waste water are produced both during and at the end of production, such as: the tailings pond leachate, the surface runoff of a plant area, process cleaning wastewater and the like contain sulfate, ammonia nitrogen and Mn with higher concentration, and relevant indexes exceed national specified discharge standards, such as serious pollution to peripheral farmland soil and water sources without collection and harmless treatment, and harm to crop growth and human health.
The manganese-containing wastewater has complex sources, and various corresponding treatment methods are generated according to different types and contents of valuable metals contained in the manganese-containing wastewater, for example, aiming at the manganese-containing wastewater with high calcium and magnesium content, impurities can be removed by selecting a fluoride method, a solvent extraction method, a microbiological method and the like, and the calcium and magnesium content in a solution is reduced firstly, so that the separation effect is achieved. The various methods are also reported in the invention of related documents, but in the actual operation process, the economic benefit, the equipment maintenance, the cost and the complexity degree of the process of the produced products are also considered. The existing method for treating calcium and magnesium ions in manganese-containing wastewater comprises the steps of separating magnesium sulfate and manganese sulfate by utilizing the difference of the solubility of the magnesium sulfate and the manganese sulfate in an ethanol solution, but the separation rate is low, the practical value is low, and the safety in the actual industrial production is greatly reduced. The extraction method is used for separating manganese and magnesium ions, but the extraction rate of manganese and magnesium is not high, and the separation effect is not ideal. Manganese and magnesium are separated by a manganese sulfate solution fluorination precipitation method, excessive new impurities are introduced, the subsequent treatment is complicated, industrial equipment is corroded by fluoride in the actual production process, and the method has serious environmental pollution. Therefore, it is important to develop a simple, economical and efficient method for removing impurities in the manganese system.
Along with the development of electrolytic manganese industry in China and the demand of manganese, the manganese-containing wastewater generated by the electrolytic manganese industry is increased year by year, and the electrolytic manganese wastewater has the characteristic of high calcium and magnesium content. Therefore, the manganese-containing wastewater is selectively recycled, valuable metals are extracted and recycled, and the method has practical significance for reducing environmental pollution and resource waste. In order to fundamentally solve the problem of waste water generated in the production process, a process method which is low in cost and can be recycled needs to be found. In the prior art, the patent: CN110282662B discloses a method for removing calcium from a manganese sulfate solution, which adopts sulfuric acid as a calcium precipitation agent, combines calcium ions and sulfate ions to generate calcium sulfate precipitates by controlling the concentration of H ions in the sulfuric acid solution, and then obtains a relatively pure manganese sulfate solution by filtering and solid-liquid separation; then controlling the concentration of H ions to crystallize and precipitate manganese sulfate, wherein the concentration of calcium ions can be reduced to below 30ppm after primary precipitation; the patent: CN111392777A discloses a method for removing calcium from a manganese sulfate solution, wherein the pH value of the manganese sulfate solution is adjusted to 0.5-3, and an extractant P204 is mixed with sulfurized kerosene to obtain a manganese sulfate calcium-removing raffinate and a calcium-manganese-rich organic phase, so that the separation effect is achieved; however, the method has the problems of high energy consumption, poor equipment maintenance and separation effect and the like because the method is greatly limited in treating the magnesium-calcium-rich manganese-containing wastewater.
Disclosure of Invention
In order to solve the technical problems, the invention provides a process for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride, and provides a process method for harmlessly treating the manganese-containing wastewater and obtaining high-grade manganese chloride crystals at low cost.
In order to achieve the purpose, the invention adopts the following technical scheme: a process for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride, Mn in manganese-containing wastewater2+≤5g/L，Mg2+≤4g/L，Ca2+Less than or equal to 0.6g/L, comprising the following steps:
s1, carrying out evaporation concentration treatment on the manganese-containing wastewater to obtain a saturated solution;
s2, based on the step S1, adding ammonium bicarbonate into the saturated solution of the manganese-containing wastewater, stirring and reacting, wherein the stirring control temperature is 40-50 ℃, the stirring reaction time is 2-3 hours, the pH value of the manganese-containing wastewater is adjusted to 6.5-7, and filtering is carried out after full stirring to obtain filter residue and filtrate;
s3, based on S2, washing the filter residue with ultrapure water and drying to obtain a manganese carbonate crude product;
s4, based on S3, adding an acidolysis agent into the manganese carbonate crude product, and stirring at room temperature to dissolve the manganese carbonate completely to obtain Mn2+A solution;
s5, based on S4, at Mn2+Adding oxalic acid into the solution, carrying out water bath heating reaction for 1h at the temperature of 60-80 ℃, carrying out solid-liquid separation after aging for 2-4 h, filtering, washing and drying the solution, wherein the filter residue is calcium oxalate, and the filtrate is manganese chloride solution;
and S6, recrystallizing the manganese chloride solution based on S5 to obtain pure manganese chloride crystals.
Preferably, in step S2, the addition amount of ammonium bicarbonate is equal to Mn in the manganese-containing wastewater2+Is N (NH)4HCO3)：n(Mn2+)＝2～2.2：1。
Preferably, in the step S2, the stirring intensity is 300-500 rpm.
Preferably, in the step S4, the acidolysis agent is hydrochloric acid, and the concentration of the hydrochloric acid is 1 to 2 mol/L.
Preferably, the molar ratio of the addition amount of the hydrochloric acid to the manganese carbonate is n (HCl): n (MnCO)3)＝2：1。
Preferably, in the step S5, the addition amount of oxalic acid is equal to Ca in the manganese carbonate crude product2+Is n (H)2C2O4)：n(Ca2+)＝2～3：1。
Preferably, in the step S3, the drying temperature is 80 ℃ and the drying time is 6 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, manganese-containing wastewater is recycled, so that the manganese-containing wastewater is harmless and high-purity manganese chloride is produced, the resource utilization of the manganese-containing wastewater is realized, the manganese-containing wastewater can be discharged up to the standard, high-purity manganese chloride can be produced by recycling valuable metal manganese and can be sold as a product, and a byproduct calcium oxalate can also produce economic benefits;
(2) the invention passes through MgCO3And CaCO3、MnCO3According to the principle that the solubility difference is large, ammonium bicarbonate is added to remove calcium and magnesium ions, and recrystallization is utilized to further separate a small amount of magnesium and calcium ions in the solution, so that the process is simple and the effect is obvious;
(3) the method has simple process flow, reduces the complicated steps of equipment maintenance and inspection compared with the traditional extraction method, has less equipment material consumption, does not have strict requirements on equipment, and has low cost;
(4) the method has mild reaction conditions, common used medicaments and low price, and the generated by-products can also generate economic value, and the recovered and prepared high-purity manganese chloride has better quality.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention is further explained below.
Mn in manganese-containing wastewater used in the invention2+≤5g/L，Mg2+≤4g/L，Ca2+The recovery preparation process of manganese chloride is less than or equal to 0.6g/L and comprises the following steps:
s1, carrying out evaporation concentration treatment on the manganese-containing wastewater to obtain a saturated solution;
s2, based on the step S1, adding ammonium bicarbonate into a saturated solution of manganese-containing wastewater, stirring and reacting, controlling the stirring temperature to be 40-50 ℃, the stirring reaction time to be 2-3 h, adjusting the pH value of the manganese-containing wastewater to be 6.5-7, fully stirring and filtering, specifically, the stirring intensity is 300-500 rpm, the heating device is a water bath kettle, and a reduced pressure suction filtration device is used for hot suction filtration to obtain filter residues and filtrate;
s3, based on S2, washing the filter residue with ultrapure water and drying, wherein the drying temperature is 80 ℃, and the drying time is 6 hours, so as to obtain a manganese carbonate crude product;
due to MgCO3And CaCO3With MnCO3Property of large difference in solubility (Ksp [ CaCO ]3]＝2.9×10-9、Ksp[MgCO3]＝6.8×10-6、Ksp[MnCO3]＝2.2×10-11) The manganese precipitation can be carried out by adding ammonium bicarbonate, specifically, in the invention, the adding amount of the ammonium bicarbonate is equal to the Mn in the manganese-containing wastewater2+Is N (NH)4HCO3)：n(Mn2+) 2-2.2: 1, thereby realizing Mn2+、Ca2+、Mg2+And (5) carrying out primary separation to obtain crude manganese carbonate.
S4, based on S3, adding an acidolysis agent into the manganese carbonate crude product, specifically, in the invention, the acidolysis agent is hydrochloric acid, the concentration of the hydrochloric acid is 1-2 mol/L, and the molar ratio of the addition amount of the hydrochloric acid to the manganese carbonate is n (HCl): n (MnCO)3) 2: 1. stirring at room temperature to dissolve manganese carbonate completely to obtain Mn2+A solution;
s5, based on S4, at Mn2+Adding oxalic acid into the solution, performing water bath heating reaction for 1 hour at the temperature of 60-80 ℃, performing solid-liquid separation after aging for 2-4 hours, filtering, washing and drying, wherein the filter residue is calcium oxalate, the filtrate is manganese chloride solution, and the addition amount of oxalic acid is equal to Ca in a manganese carbonate crude product2+Is n (H)2C2O4)：n(Ca2+) 2-3: 1; the reaction equation is: CaCl2+H2C2O4＝CaC2O4(precipitate) + HCl. The equilibrium condition is moved to the right by heating, the reaction rate is accelerated, calcium oxalate is insoluble in water and soluble in hydrochloric acid and nitric acid, and the impurity calcium ions contained in the manganese carbonate crude product can be precipitated and separated by adding oxalic acid;
and S6, recrystallizing the manganese chloride solution based on S5 to obtain pure manganese chloride crystals.
The method can effectively recover manganese in the manganese-containing wastewater, make the manganese-containing wastewater harmless and produce high-purity manganese chloride, realize resource utilization of the manganese-containing wastewater, realize standard discharge of the manganese-containing wastewater, produce high-purity manganese chloride by recovering valuable metal manganese, sell the high-purity manganese chloride as a product, produce economic benefits by-product calcium oxalate, prepare a manganese product with higher value by using the process method, and have simple and convenient operation process, wherein the manganese chloride product is mainly used for manufacturing feed additives, analytical reagents, dyes and pigments. Can also be used as trace element fertilizer in agriculture. In addition, the product can be further processed to be further made into a chemical product with higher value, and the method has wide market prospect.
The above-mentioned embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and therefore, modifications, equivalent changes, improvements, etc. made in the claims of the present invention are still included in the scope of the present invention.
Claims (7)
1. The process for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride is characterized in that Mn in the manganese-containing wastewater2+≤5g/L，Mg2+≤4g/L，Ca2+Less than or equal to 0.6g/L, comprising the following steps:
s1, carrying out evaporation concentration treatment on the manganese-containing wastewater to obtain a saturated solution;
s2, based on the step S1, adding ammonium bicarbonate into the saturated solution of the manganese-containing wastewater, stirring and reacting, wherein the stirring control temperature is 40-50 ℃, the stirring reaction time is 2-3 hours, the pH value of the manganese-containing wastewater is adjusted to 6.5-7, and filtering is carried out after full stirring to obtain filter residue and filtrate;
s3, based on S2, washing the filter residue with ultrapure water and drying to obtain a manganese carbonate crude product;
s4, based on S3, adding an acidolysis agent into the manganese carbonate crude product, and stirring at room temperature to dissolve the manganese carbonate completely to obtain Mn2+A solution;
s5, based on S4, at Mn2+Adding oxalic acid into the solution, carrying out water bath heating reaction for 1h at the temperature of 60-80 ℃, carrying out solid-liquid separation after aging for 2-4 h, filtering, washing and drying the solution, wherein the filter residue is calcium oxalate, and the filtrate is manganese chloride solution;
and S6, recrystallizing the manganese chloride solution based on S5 to obtain pure manganese chloride crystals.
2. The process for selectively recovering manganese and preparing manganese chloride from manganese-containing wastewater according to claim 1, wherein the process comprises the following steps: in step S2, the amount of ammonium bicarbonate added is equal to the amount of Mn in the manganese-containing wastewater2+Is N (NH)4HCO3)：n(Mn2+)＝2～2.2：1。
3. The process for selectively recovering manganese and preparing manganese chloride from manganese-containing wastewater according to claim 2, characterized in that: in the step S2, the stirring intensity is 300-500 rpm.
4. The process for selectively recovering manganese and preparing manganese chloride from manganese-containing wastewater according to claim 1, wherein the process comprises the following steps: in the step S4, the acidolysis agent is hydrochloric acid, and the concentration of the hydrochloric acid is 1-2 mol/L.
5. The process of claim 4 for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride, wherein the process comprises the following steps: the molar ratio of the addition amount of the hydrochloric acid to the manganese carbonate is n (HCl): n (MnCO)3)＝2：1。
6. The process of claim 1 for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride, wherein the process comprises the following steps: in the step S5, the addition amount of oxalic acid and Ca in the manganese carbonate crude product2+Is n (H)2C2O4)：n(Ca2+)＝2～3：1。
7. The process for selectively recovering manganese and preparing manganese chloride from manganese-containing wastewater according to claim 1, wherein the process comprises the following steps: in the step S3, the drying temperature is 80 ℃ and the drying time is 6 h.
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