CN112522515A - Method for treating waste residue containing metal manganese - Google Patents
Method for treating waste residue containing metal manganese Download PDFInfo
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- CN112522515A CN112522515A CN202011287463.2A CN202011287463A CN112522515A CN 112522515 A CN112522515 A CN 112522515A CN 202011287463 A CN202011287463 A CN 202011287463A CN 112522515 A CN112522515 A CN 112522515A
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- manganese
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- potassium persulfate
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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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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- 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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- Mechanical Engineering (AREA)
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- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the field of hazardous waste treatment, in particular to a method for treating waste residues containing metal manganese, which mainly comprises the following steps: (1) adding water into industrial waste residues containing manganese carbonate, wherein the mass concentration range of the waste residues is 150-250g/L, and after uniformly stirring, heating the solution to 50-60 ℃; (2) adding potassium persulfate into the solution obtained in the step (1) in batches, controlling the solution to react until the pH value is 8-10 through sodium hydroxide, keeping the temperature of 50-65 ℃ while stirring for 2 hours after all the potassium persulfate and the sodium hydroxide are added, and keeping the pH value of the solution unchanged; (3) and (3) placing the solution in the step (2) in a filter, performing suction filtration under negative pressure, collecting a filter cake to obtain manganese dioxide, and completing conversion and recovery. The invention has the advantages that: the treatment equipment is simple, the cost is low, the conversion rate of the manganese metal into manganese dioxide after the treatment can reach 95.5-96.2%, and the high conversion rate of the manganese metal is realized; compared with the prior art, the method has the advantages of less waste water output and more energy saving.
Description
Technical Field
The invention belongs to the field of hazardous waste treatment, and particularly relates to a treatment method of waste residues containing metal manganese.
Background
At present, the industrial production is often accompanied by the output of waste residues, the existing waste residue treatment methods are various, such as waste residues generated after activated carbon adsorption, biochemical sludge generated by sewage biochemical treatment and the like, and the organic waste residues can be treated by burning and absorbing tail gas with good effect; the other part of the waste residues is industrial waste residues containing heavy metals, such as manganese residues (manganese carbonate, manganese phosphate, manganese ammonium phosphate, manganese hydroxide and the like) generated in an oxidation process when the acid dye blue 9# is prepared, the main component of the manganese residues is manganese carbonate, the waste residues contain the heavy metal manganese, so the waste residues have certain difficulty in waste residue treatment, and certain pollution is caused to the environment if the waste residues are not treated properly. In the prior art, patent application No.: 2014104479710, application publication number: the invention patent of CN104327533A discloses a clean production process of acid blue No. 9 dye, manganese slag is oxidized by hydrogen peroxide in a static mixer to prepare manganese dioxide, and the recovered manganese dioxide can be recycled, but the recovery process has high requirements on equipment and higher cost and generates a certain amount of waste water. How to treat and effectively recycle the waste residue containing the metal manganese through simple steps is a problem which needs to be solved urgently by the personnel in the field.
Disclosure of Invention
In order to solve the problems, the invention provides a method for treating waste residue containing metal manganese, which is characterized by comprising the following steps:
(1) pulping by using waste residue
Adding water into industrial waste residues containing manganese carbonate, wherein the mass concentration of the waste residues is 0.15-0.25g/ml, uniformly stirring, and heating the solution to 50-60 ℃;
(2) and oxidizing the mixture
Adding potassium persulfate into the solution obtained in the step (1) in 3-5 batches, controlling the solution to react until the pH value is 8-10 by sodium hydroxide, and keeping the temperature of 50-65 ℃ while stirring for 2 hours after all the potassium persulfate is added, and keeping the pH value of the solution unchanged;
(3) filtering the mixture
And (3) placing the solution in the step (2) in a filter, performing suction filtration under negative pressure, and collecting a filter cake to obtain manganese dioxide, thereby completing conversion and recovery.
Preferably, the mass concentration of the waste residue in the solution in the step (1) is 0.2g/ml, and after uniform stirring, the solution is heated to 50 ℃;
preferably, the molar ratio of the potassium persulfate to the manganese carbonate in the waste residue in the step (2) is in the range of 1-1.2;
the invention has the beneficial effects that:
1. compared with the prior art, the method has the advantages that the waste residue containing manganese carbonate is oxidized into recyclable manganese dioxide through simple steps, the time for processing one ton of waste residue is only 3-5 hours, the processing time is short, and the production efficiency is high; the whole treatment process does not need static mixer equipment, and the treatment method has low cost and good economic benefit.
2. In the treatment process of waste residues, an oxidant potassium persulfate has strong oxidizability and is easy to decompose at high temperature, and the solution can be ensured to fully react by adding in batches in the oxidation step; in the treatment process, the manganese slag is converted into manganese dioxide under the oxidation action: mn2++S2O3 2-→MnO2+SO4 2-(ii) a After the treatment is finished, the conversion of the manganese metal into manganese dioxide can reach 95.5-96.2%; the high conversion rate of the metal manganese is realized, the manganese dioxide can be recycled after being collected, the recycling of manganese-containing waste residues is realized, and the cost is saved for enterprises.
3. Compared with the waste water produced by using hydrogen peroxide to treat waste residues in the prior art, the waste water produced by the method is less, the subsequent waste water treatment amount is reduced, and the resource waste is reduced.
Detailed Description
While one embodiment of the present invention has been described in detail, the description is only a preferred embodiment of the invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Example 1:
1. 200ml of water is added into a beaker, 40g of industrial waste residue with the main component of manganese carbonate is added, wherein 0.2mol of manganese carbonate is contained, the solution is stirred and dispersed evenly, and the temperature of the solution is raised to 50 ℃ by external bath.
2. 54g of potassium persulfate is divided into three parts, the three parts are sequentially added into the solution obtained in the step 1, sodium hydroxide is used for controlling the reaction pH to be 8.0-9.0 after each addition, when the potassium persulfate is added for 3 times, the temperature is kept at 50-65 ℃ continuously, stirring is carried out for 2 hours until the reaction is completed, and the pH is kept to be 8.0-9.0.
3. And (3) placing the solution in the step (2) in a filter, performing suction filtration under negative pressure and collecting a filter cake to obtain manganese dioxide, wherein the amount of the manganese dioxide is 32.64g calculated by an iodometry method, and the conversion rate of the obtained manganese metal is 96%.
Example 2: step 1 the same as in example 1, except that,
2. 54g of potassium persulfate is divided into four parts, sequentially added into the solution in the step 1 in the example 1, sodium hydroxide is used for controlling the reaction pH to be 9.0-10.0 after each addition, and when 4 times of addition of the potassium persulfate is finished, the temperature is kept between 50 ℃ and 65 ℃ and stirring is carried out for 2 hours until the reaction is completed, and the system pH is kept to be 9.0-10.0.
3. The solution obtained in step 2 of this example was placed in a filter, filtered by suction under negative pressure and the filter cake was collected, and 32.47g of manganese dioxide was obtained by iodometry, and the oxidation conversion of manganese metal was calculated to be 95.5%.
Example 3: step 1 the same as in example 1, except that,
2. and (2) dividing 64.8g of potassium persulfate into three parts, sequentially adding the three parts into the solution in the step (1), using sodium hydroxide to adjust and control the reaction pH to be 8.0-9.0 in real time after each addition, continuing to keep the temperature of 50-65 ℃ and stirring for 2 hours after 3 times of addition of the potassium persulfate until the reaction is completed, and keeping the pH of the reaction system to be 8.0-9.0.
3. The solution obtained in step 2 of this example was placed in a filter, and 32.71g of manganese dioxide was obtained by iodometry by suction filtration under negative pressure and collecting a filter cake, and the oxidation conversion of manganese metal was calculated to be 96.2%.
Example 4: step 1 the same as in example 1, except that,
2. taking 64.8g of potassium persulfate, dividing into four parts, sequentially adding the four parts into the solution in the step 1 in the example 1, controlling the reaction pH to be 9.0-10.0 by using sodium hydroxide after each addition, continuing to keep the temperature of 50-65 ℃ and stirring for 2 hours after 4 times of addition of the potassium persulfate until the reaction is completed, and keeping the pH of the reaction system to be 9.0-10.0.
3. The solution obtained in step 2 of this example was placed in a filter, and 32.61g of manganese dioxide was obtained by iodometry by suction filtration under negative pressure and collecting a filter cake, and the oxidation conversion of manganese metal was calculated to be 95.9%.
Example 5: step 1 the same as in example 1, except that,
2. and (2) dividing 59.4g of potassium persulfate into five parts, sequentially adding the five parts into the solution in the step (1), using sodium hydroxide to adjust and control the reaction pH to be 8.0-9.0 in real time after each addition, continuing to keep the temperature of 50-65 ℃ and stirring for 2 hours after 5 times of addition of the potassium persulfate until the reaction is completed, and keeping the reaction system pH to be 8.0-9.0.
3. The solution from step 2 of this example was placed in a filter and filtered by suction at negative pressure and the filter cake was collected, 32.67g manganese dioxide was obtained by iodometry and the oxidation conversion of manganese metal was calculated to be 96.1%.
Example 6: the applicant also carries out pilot test experiments on the waste residues by using the technical scheme, and the quantity of the produced waste water is tested; the list is as follows:
| serial number | Manganese slag | Waste water from aquatic product with hydrogen peroxide | Adding potassium persulfate to produce wastewater |
| 1 | 800kg | About 1.28 tons | About 1.08 ton |
| 2 | 1000kg | About 1.62 ton | About 1.41 tons |
| 3 | 1500kg | About 2.35 tons | About 2.11 tons |
Therefore, the method can reduce the discharge of about 0.21 ton of waste water per ton of waste residue, the cost for treating industrial waste water is about 1500 yuan/ton at present, and the cost can be saved by 315 yuan/ton when the method is used for treating the waste residue.
Example 7: experimental data for examples 1-5 are given in the following Table
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Conversion rate | 96％ | 95.5％ | 96.2％ | 95.9％ | 96.1％ |
| Reaction time | 3.5 hours | 3.5 hours | 3.5 hours | 3.5 hours | 3.5 hours |
Example 8:
the content of manganese dioxide in examples 1-6 was calculated by iodometry, using manganese dioxide to quantitatively oxidize iodide ions to iodine in an acidic medium, and titrating iodine with a sodium thiosulfate standard solution using starch as an indicator to determine the manganese dioxide content, using the formula:
wherein, CNa2S2O3The concentration of the sodium thiosulfate standard solution is expressed in mol/L; vNa2S2O3The volume of the sodium thiosulfate standard solution consumed by the sample is expressed in mL; the millimolar mass of manganese dioxide equivalent to the standard solution of sodium thiosulfate is 0.04347; the unit is g/10-3(ii) a m represents the mass of the sample and is expressed in g.
It can be seen through above embodiment that, the hydrogen peroxide solution that uses potassium persulfate to handle the waste residue and compare prior art is handled, need not wash the waste residue at the in-process of handling the waste residue, and output waste water volume is less relatively, handles about saving cost 315 per ton of waste residue to have that reaction vessel is simple, easy production operation, the metal manganese conversion rate is high, characteristics that the process time is short.
Claims (2)
1. A method for treating waste slag containing metal manganese is characterized by comprising the following steps:
(1) pulping by using waste residue
Adding water into industrial waste residues containing manganese carbonate, wherein the mass concentration of the waste residues is 0.15-0.25g/ml, uniformly stirring, and heating the solution to 50-60 ℃;
(2) and oxidizing the mixture
Adding potassium persulfate into the solution obtained in the step (1) in 3-5 batches, controlling the solution to react until the pH value is 8-10 by sodium hydroxide, and keeping the temperature of 50-65 ℃ while stirring for 2 hours after all the potassium persulfate is added, and keeping the pH value of the solution unchanged;
(3) filtering the mixture
And (3) placing the solution in the step (2) in a filter, performing suction filtration under negative pressure, and collecting a filter cake to obtain manganese dioxide, thereby completing recovery.
2. The method for treating waste slag containing metal manganese according to claim 1, characterized in that: in the step (2), the molar ratio of the potassium persulfate to the manganese carbonate in the waste residue is 1-1.2.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011287463.2A CN112522515A (en) | 2020-11-17 | 2020-11-17 | Method for treating waste residue containing metal manganese |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011287463.2A CN112522515A (en) | 2020-11-17 | 2020-11-17 | Method for treating waste residue containing metal manganese |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880768A (en) * | 2010-06-14 | 2010-11-10 | 渤海大学 | Method for extracting high-purity manganese dioxide from manganese slag |
| US8586218B1 (en) * | 2011-11-21 | 2013-11-19 | Toxco, Inc. | Process for recycling alkaline batteries |
| CN104327533A (en) * | 2014-09-04 | 2015-02-04 | 恒升化工有限公司 | Clean production technology of acid blue 9 dye |
| CN108118151A (en) * | 2017-12-27 | 2018-06-05 | 昆明冶金研究院 | Potential-controlled oxidation removal of Mn in cobalt sulfate solution2+Method (2) |
-
2020
- 2020-11-17 CN CN202011287463.2A patent/CN112522515A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880768A (en) * | 2010-06-14 | 2010-11-10 | 渤海大学 | Method for extracting high-purity manganese dioxide from manganese slag |
| US8586218B1 (en) * | 2011-11-21 | 2013-11-19 | Toxco, Inc. | Process for recycling alkaline batteries |
| CN104327533A (en) * | 2014-09-04 | 2015-02-04 | 恒升化工有限公司 | Clean production technology of acid blue 9 dye |
| CN108118151A (en) * | 2017-12-27 | 2018-06-05 | 昆明冶金研究院 | Potential-controlled oxidation removal of Mn in cobalt sulfate solution2+Method (2) |
Non-Patent Citations (1)
| Title |
|---|
| 赵静: "低品位菱锰矿提制活性四氧化三锰和二氧化锰的工艺优化", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
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