CN110004292B - Process for purifying waste manganese sulfate solution to reduce content of calcium and magnesium - Google Patents
Process for purifying waste manganese sulfate solution to reduce content of calcium and magnesium Download PDFInfo
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- CN110004292B CN110004292B CN201910318996.3A CN201910318996A CN110004292B CN 110004292 B CN110004292 B CN 110004292B CN 201910318996 A CN201910318996 A CN 201910318996A CN 110004292 B CN110004292 B CN 110004292B
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- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- 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
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- 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
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Abstract
The invention discloses a process for purifying waste manganese sulfate solution to reduce calcium and magnesium content, which comprises the following steps: s1, taking manganese sulfate waste liquid containing calcium and magnesium, heating the waste liquid to 30-40 ℃, adding a mixed solution of oxalic acid, sodium oxalate and ammonium oxalate, and stirring for reacting for 2-4 hours at a constant temperature; s2, standing the solution obtained after the reaction in the step S1, and removing the precipitate to obtain a purified manganese sulfate solution; wherein the mass ratio of oxalic acid, sodium oxalate and ammonium oxalate in the mixed solution is (2-3): 1: 1. according to the scheme, oxalic acid and oxalate solution are used for removing impurities from manganese sulfate, the influence of the traditional technology on environment caused by fluoride impurity removal is technically avoided, and the manganese sulfate produced in the hydrometallurgy process can be purified and reused without toxicity or low toxicity.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a process for purifying a waste manganese sulfate solution to reduce the content of calcium and magnesium.
Background
Hydrometallurgy is a process in which ores, concentrates enriched by mineral separation, or other raw materials are brought into contact with an aqueous solution or other liquid, useful metals contained in the raw materials are transferred to a liquid phase through a chemical reaction or the like, various useful metals contained in the liquid phase are separated and enriched, and finally, the various useful metals are recovered in the form of metal compounds. Copper and cobalt are two common chemical raw materials, and are usually extracted by a hydrometallurgy mode, and a large amount of manganese sulfate solution containing calcium and magnesium impurities is remained after copper, cobalt and other metals are extracted in the traditional hydrometallurgy process. If the industrial wastewater is directly discharged, heavy metal harm is caused to water flow and soil, and metal resources are wasted. Meanwhile, manganese sulfate is an important microelement fertilizer, can enable crops to grow well, is an important feed additive, is supplemented into the feed, has a fattening effect, and can enable livestock and poultry to grow well. In addition, manganese sulfate can be widely applied to medicines, paint driers, ceramics, printing and dyeing, production of electrolytic manganese, manufacture of other manganese salts and the like. Therefore, the manganese sulfate wastewater needs to be recycled from the aspects of environmental protection and resource recovery.
At present, there are three main methods for reducing Ca and Mg ions in manganese sulfate waste liquid: chemical precipitation method of inorganic salt, extraction method and concentration standing method. According to the literature, an inorganic salt chemical precipitation method is a main method for reducing Ca and Mg ions, but in the inorganic salt precipitation method in the prior art, new impurity ions are usually introduced, and higher requirements on the quality of manganese sulfate are also provided in the recycling of metallurgical waste liquid, and especially the requirements on the content of impurities in the manganese sulfate are quite strict. In the prior art, most researchers adopt fluoride to remove impurities from Ca and Mg ions in manganese sulfate, but the toxicity of the fluoride is harmful to human bodies and the environment, so that the method for reducing the Ca and Mg ions in the manganese sulfate waste liquid with low toxicity or even no toxicity is significant.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides an economic and environment-friendly process for purifying waste manganese sulfate solution to reduce the content of calcium and magnesium.
In order to solve the technical problems, the invention adopts the technical scheme that: a process for purifying waste manganese sulfate solution to reduce calcium and magnesium content comprises the following steps:
s1, taking manganese sulfate waste liquid containing calcium and magnesium, heating the waste liquid to 30-40 ℃, adding a mixed solution of oxalic acid, sodium oxalate and ammonium oxalate, and stirring for reacting for 2-4 hours at a constant temperature;
s2, standing the solution obtained after the reaction in the step S1, and removing the precipitate to obtain a purified manganese sulfate solution;
wherein the mass ratio of oxalic acid, sodium oxalate and ammonium oxalate in the mixed solution is (2-3): 1: 1.
preferably, the mass ratio of the oxalic acid to the sodium oxalate to the ammonium oxalate in the mixed solution is 2:1: 1.
Further, in the step S1, the heating operation is to place the container containing the waste liquid in an environment where the temperature is raised to 60 to 80 ℃.
Further, in the step S1, the stirring speed is 5 to 15 rad/S; preferably, the stirring speed is 10 rad/s.
Further, in the step S2, the standing time is 24-48 h.
Further, in the step S2, the operation of removing the precipitate is to remove magnesium oxalate and calcium oxalate precipitate by a filtering operation.
Further, in step S1, the manganese sulfate waste liquid containing calcium and magnesium is a hydrometallurgical waste liquid.
Further, in step S1, the waste liquid is manganese sulfate waste liquid remaining after copper and/or cobalt extraction.
Further, the standing operation is carried out at room temperature, wherein the room temperature is 15-35 ℃, and preferably 20-25 ℃.
The invention has the beneficial effects that: according to the scheme, the mixed solution of oxalic acid and oxalate is used for removing Ca and Mg in the manganese sulfate waste liquid, and an inorganic salt chemical precipitation method is combined with the traditional metallurgical industry, so that the method is economical and environment-friendly. Along with the rapid development of electronic chemicals in China in recent years, manganese sulfate is more and more emphasized by people as a main raw material for producing the electronic chemicals, so that MnSO subjected to impurity removal is4The solution waste residue has considerable recycling value and can be effectively recycled, and the scheme of the invention can effectively improve the utilization rate of limited metal resources and simultaneously can effectively reduce the pollution to the environment in the experimental process by recycling the waste; according to the scheme, a chemical reaction method is utilized, the industrial manganese sulfate waste liquid is subjected to impurity removal by utilizing the characteristic that oxalate is generated by oxalic acid, calcium and magnesium elements, the method is simple and easy to implement, the process of recycling industrial waste in the prior art is greatly shortened, the white calcium and magnesium oxalate mixed powder can be effectively obtained, meanwhile, the removal rate of calcium and magnesium in the solution treated by the scheme can reach more than 65% and 62%, and the solution treated by the scheme can be used for recycling manganese sulfate; the scheme of the invention can directly purify the waste liquid obtained after the traditional wet metallurgy, thereby greatly shortening the time of purifying the waste liquidAnd (5) recycling the waste.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
The embodiment of the invention is as follows: a process for purifying waste manganese sulfate solution to reduce calcium and magnesium content comprises the following steps:
s1, taking out residual MnSO after extracting metals such as copper, cobalt and the like4Pouring the waste liquid into a beaker, putting the waste liquid into a DF-101 series heat collection type constant temperature heating magnetic stirrer heated to 60-80 ℃ (so as to better ensure that the temperature inside the solution reaches 30-40 ℃), adding a mixed solution of oxalic acid, sodium oxalate and ammonium oxalate after the temperature of the solution reaches 30-40 ℃, adjusting the stirring speed of the DF-101 series heat collection type constant temperature heating magnetic stirrer by 10rad/s, recording the time, and stirring and reacting for 3 hours at constant temperature;
s2, standing the reacted beaker at room temperature for 36h, sampling, and filtering with 12.5cm qualitative filter paper and a funnel to obtain white precipitates of magnesium oxalate and calcium oxalate; collecting the filtrate to obtain the purified manganese sulfate solution.
MnSO for the same source4The waste liquid is subjected to calcium and magnesium removal operation by adopting a mixed solution containing oxalic acid, sodium oxalate and ammonium oxalate with different mass ratios, the concentrations of calcium and magnesium ions in the original waste liquid and precipitates are tested by Inductively coupled plasma mass spectrometry (ICP-MS), and the removal rates of calcium and magnesium are calculated as shown in the following table 1:
TABLE 1 removal ratio of calcium and magnesium from mixed solution of oxalic acid, sodium oxalate and ammonium oxalate with different mass ratios
The above table shows that the mixed solution of oxalic acid, sodium oxalate and ammonium oxalate with the mass ratio of (2-3): 1:1 can unexpectedly and effectively purify calcium and magnesium in the waste liquid, and when the mixed solution is used for purification treatment, the purification rate of calcium ions can reach more than 65.89%, and the removal rate of magnesium can reach more than 62.27%; the solution treated by the scheme of the invention has proper pH value and can be directly used for a manganese sulfate recycling process.
In order to observe the reaction condition of manganese sulfate, calcium sulfate and magnesium sulfate with oxalic acid, carrying out blank control experiments on the manganese sulfate, the calcium sulfate and the magnesium sulfate respectively; after 10g of a sulfate (manganese sulfate, calcium sulfate or magnesium sulfate) sample was placed in a beaker and dissolved in 100ml of tap water to prepare a solution, 15g of oxalic acid was added, and the reaction condition in the solution was observed while stirring with a glass rod, and the specific phenomenon was as shown in table 2 below:
TABLE 2 reaction phenomena of different sulfates with oxalic acid
Meanwhile, in comparison experiments on different types of oxalates, the results show that potassium oxalate solution and manganese precipitate violently, so that calcium and magnesium precipitates cannot be replaced, and other oxalates cause high cost.
In conclusion, the scheme of the invention is particularly suitable for extracting residual MnSO from metals such as copper, cobalt and the like in the traditional hydrometallurgy process4The solution reduces elements with calcium and magnesium contents, the scheme of the invention adopts oxalic acid, sodium oxalate and ammonium oxalate to be mixed according to a specific proportion, the effect of efficiently reducing the calcium and magnesium contents can be achieved, and the oxalic acid, the sodium oxalate and the ammonium oxalate have low cost, and are a waste liquid treatment mode with high economic benefit, environmental protection and low toxicity; according to the scheme, the oxalic acid solution is used for removing impurities from manganese sulfate, so that the damage to the environment caused by a fluoride impurity removal mode in the traditional technology is avoided, and the manganese sulfate generated in the hydrometallurgy process is purified and reusedCan also achieve non-toxicity or low toxicity.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (11)
1. A process for purifying waste manganese sulfate solution to reduce calcium and magnesium content is characterized in that: the method comprises the following steps:
s1, taking manganese sulfate waste liquid containing calcium and magnesium, heating the waste liquid to 30-40 ℃, adding a mixed solution of oxalic acid, sodium oxalate and ammonium oxalate, and stirring for reacting for 2-4 hours at a constant temperature;
s2, standing the solution obtained after the reaction in the step S1, and removing the precipitate to obtain a purified manganese sulfate solution;
wherein the mass ratio of oxalic acid, sodium oxalate and ammonium oxalate in the mixed solution is (2-3): 1: 1.
2. the process for purifying the waste manganese sulfate solution to reduce the content of calcium and magnesium, which is claimed in claim 1, is characterized in that: the mass ratio of oxalic acid, sodium oxalate and ammonium oxalate in the mixed solution is 2:1: 1.
3. The process for purifying the waste manganese sulfate solution to reduce the content of calcium and magnesium, which is claimed in claim 1, is characterized in that: in the step S1, the heating operation is to place the container containing the waste liquid in an environment where the temperature is raised to 60 to 80 ℃.
4. The process for purifying the waste manganese sulfate solution to reduce the content of calcium and magnesium, which is claimed in claim 1, is characterized in that: in the step S1, the stirring speed is 5 to 15 rad/S.
5. The process for purifying the waste manganese sulfate solution to reduce the content of calcium and magnesium, which is claimed in claim 4, is characterized in that: the stirring speed was 10 rad/s.
6. The process for purifying the waste manganese sulfate solution to reduce the content of calcium and magnesium, which is claimed in claim 1, is characterized in that: in the step S2, the standing time is 24-48 h.
7. The process for purifying the waste manganese sulfate solution to reduce the content of calcium and magnesium, which is claimed in claim 1, is characterized in that: in step S2, the operation of removing the precipitate is to remove magnesium oxalate and calcium oxalate precipitate by a filtering operation.
8. The process for purifying the waste manganese sulfate solution to reduce the content of calcium and magnesium according to any one of claims 1 to 7, wherein the process comprises the following steps: in the step S1, the manganese sulfate waste liquid containing calcium and magnesium is a hydrometallurgical waste liquid.
9. The process for purifying the waste manganese sulfate solution to reduce the content of calcium and magnesium, which is claimed in claim 8, is characterized in that: in the step S1, the waste liquid is manganese sulfate waste liquid remaining after copper and/or cobalt extraction.
10. The process for purifying the waste manganese sulfate solution to reduce the content of calcium and magnesium according to any one of claims 1 to 7, wherein the process comprises the following steps: the standing operation is carried out at room temperature, and the room temperature is 15-35 ℃.
11. The process for purifying the waste manganese sulfate solution to reduce the content of calcium and magnesium, which is claimed in claim 10, is characterized in that: the room temperature is 20-25 ℃.
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| CN103112901A (en) * | 2013-03-02 | 2013-05-22 | 湘潭大学 | Method for reducing contents of calcium ions, magnesium ions, potassium ions and sodium ions in manganese sulfate |
| WO2013138900A1 (en) * | 2012-03-19 | 2013-09-26 | Orbite Aluminae Inc. | Processes for recovering rare earth elements and rare metals |
| CN104649306A (en) * | 2014-12-26 | 2015-05-27 | 航天推进技术研究院 | Method for extracting aluminium oxide from coal ash |
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| AU2016200606A1 (en) * | 2015-02-13 | 2016-09-01 | Grirem Advanced Materials Co., Ltd | A method for recovering phosphorus and rare earth from rare earth containing phosphorite |
| CN107739040A (en) * | 2017-11-15 | 2018-02-27 | 韶关中弘金属实业有限公司 | Waste material containing lithium produces the production technology of high-purity lithium carbonate |
| CN108928852A (en) * | 2018-07-25 | 2018-12-04 | 郑州大学 | A kind of recoverying and utilizing method for the Mn-bearing waste water that sulfuric acid legal system titanium dioxide process generates |
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Patent Citations (7)
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|---|---|---|---|---|
| WO2013138900A1 (en) * | 2012-03-19 | 2013-09-26 | Orbite Aluminae Inc. | Processes for recovering rare earth elements and rare metals |
| CN103112901A (en) * | 2013-03-02 | 2013-05-22 | 湘潭大学 | Method for reducing contents of calcium ions, magnesium ions, potassium ions and sodium ions in manganese sulfate |
| CN104649306A (en) * | 2014-12-26 | 2015-05-27 | 航天推进技术研究院 | Method for extracting aluminium oxide from coal ash |
| AU2016200606A1 (en) * | 2015-02-13 | 2016-09-01 | Grirem Advanced Materials Co., Ltd | A method for recovering phosphorus and rare earth from rare earth containing phosphorite |
| CN105797785A (en) * | 2016-04-15 | 2016-07-27 | 西安向阳航天材料股份有限公司 | Pre-reduction type high-temperature methanation catalyst and preparation method thereof |
| CN107739040A (en) * | 2017-11-15 | 2018-02-27 | 韶关中弘金属实业有限公司 | Waste material containing lithium produces the production technology of high-purity lithium carbonate |
| CN108928852A (en) * | 2018-07-25 | 2018-12-04 | 郑州大学 | A kind of recoverying and utilizing method for the Mn-bearing waste water that sulfuric acid legal system titanium dioxide process generates |
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Denomination of invention: A process for purifying waste manganese sulfate solution and reducing calcium and magnesium content Effective date of registration: 20210831 Granted publication date: 20201229 Pledgee: Gaoxin sub branch of Bank of Changsha Co.,Ltd. Pledgor: HUNAN YACHENG NEW MATERIAL Co.,Ltd. Registration number: Y2021430000040 |
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Address after: 410600 Xinkang Road, Ningxiang Economic and Technological Development Zone, Changsha City, Hunan Province Patentee after: Hunan Yacheng New Energy Co.,Ltd. Address before: 410600 Xinkang Road, Ningxiang Economic and Technological Development Zone, Changsha City, Hunan Province Patentee before: HUNAN YACHENG NEW MATERIAL CO.,LTD. |
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