CN110846512B - A kind of method of electrolytic manganese anode slag sulfuric acid ripening leaching manganese - Google Patents
A kind of method of electrolytic manganese anode slag sulfuric acid ripening leaching manganese Download PDFInfo
- Publication number
- CN110846512B CN110846512B CN201911158655.0A CN201911158655A CN110846512B CN 110846512 B CN110846512 B CN 110846512B CN 201911158655 A CN201911158655 A CN 201911158655A CN 110846512 B CN110846512 B CN 110846512B
- Authority
- CN
- China
- Prior art keywords
- manganese
- leaching
- sulfuric acid
- anode slag
- electrolytic
- 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.)
- Active
Links
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 157
- 239000011572 manganese Substances 0.000 title claims abstract description 157
- 238000002386 leaching Methods 0.000 title claims abstract description 121
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000002893 slag Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000005070 ripening Effects 0.000 title claims 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 41
- 229940099596 manganese sulfate Drugs 0.000 claims description 9
- 239000011702 manganese sulphate Substances 0.000 claims description 9
- 235000007079 manganese sulphate Nutrition 0.000 claims description 9
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims 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 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 11
- 239000002912 waste gas Substances 0.000 abstract description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 4
- 239000011028 pyrite Substances 0.000 description 4
- 229910052683 pyrite Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ZAOZLVZZPKAGCY-UHFFFAOYSA-N [Si].[Mn].[Mn].[Fe] Chemical compound [Si].[Mn].[Mn].[Fe] ZAOZLVZZPKAGCY-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000010198 maturation time Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010561 standard procedure Methods 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
- C22B7/04—Working-up slag
-
- 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
- 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
- C22B7/007—Wet processes by acid leaching
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开了一种电解锰阳极渣硫酸熟化浸出锰的方法，具体包括如下步骤：按所需称量电解锰阳极渣、硫粉和浓硫酸，备用；在电解锰阳极渣中加入硫粉和浓硫酸，混合均匀，经熟化反应得熟料；向熟料中加水浸出，经液固分离后得到含锰浸出溶液和浸出渣。本发明公开的方法，具有还原剂来源广、价格低、工艺简单、锰浸出率高、运行成本低、无二次废渣污染和废气污染等优点，可有效解决现有技术中存在的锰浸出成本较高、浸出过程产生二次污染等问题。The invention discloses a method for leaching and leaching manganese from electrolytic manganese anode slag by sulfuric acid aging. Concentrated sulfuric acid, mixed evenly, and subjected to aging reaction to obtain clinker; adding water to the clinker for leaching, and obtaining manganese-containing leaching solution and leaching residue after liquid-solid separation. The method disclosed by the invention has the advantages of wide source of reducing agent, low price, simple process, high manganese leaching rate, low operating cost, no secondary waste residue pollution and waste gas pollution, etc., and can effectively solve the manganese leaching cost existing in the prior art. high, secondary pollution in the leaching process, etc.
Description
Technical Field
The invention relates to the technical field of wet metallurgy waste residue recovery, in particular to a method for leaching manganese from electrolytic manganese anode residue by sulfuric acid curing.
Background
The anode slag of the electrolytic manganese is waste slag generated by an anode in the production process of electrolytic manganese metal, the main component of the anode slag is manganese, the content of manganese dioxide accounts for about 40-50%, the content of lead accounts for about 4-6%, and the manganese dioxide and the lead are precious secondary resources which can be recycled. However, the mineral composition and structure of the electrolytic manganese anode slag are complex, wherein the symbiotic relationship of lead and hydrated oxides of manganese is very close, and the manganese and the lead are difficult to separate by adopting a mechanical separation method. Therefore, most of the manganese-iron-silicon-manganese alloy is abandoned, and better development and comprehensive utilization are not obtained, so that not only is the resource waste caused, but also the environmental pollution is easily caused due to improper treatment. Therefore, how to economically and environmentally efficiently separate and comprehensively utilize the main valuable components of manganese and lead in the electrolytic manganese anode slag is a problem to be solved by the technical personnel in the field.
However, the existing resource utilization methods of electrolytic manganese anode slime mainly comprise a reduction method and an activated anode slime method, and have the problems of high operation cost, easy secondary pollution, incapability of industrial popularization and the like. The reduction method takes charcoal, graphite and the like as reducing agents to carry out high-temperature roasting reaction or takes biomass, sulfurous acid, pyrite, sulfur dioxide and the like as reducing agents, so that tetravalent manganese in anode mud is converted into bivalent manganese to enter a solution, impurities such as lead exist in a solid phase, and the solid-liquid separation can realize the comprehensive utilization of the manganese; however, the high-temperature roasting process needs high energy consumption, easily causes environmental pollution, and can cause the operation cost to be greatly increased. The method for activating the anode slime comprises the steps of removing impurity elements in the anode slime by acid leaching, roasting acid leaching, alkali oxidation and the like, changing the crystal form of manganese dioxide in the anode slime, promoting manganese dioxide or permanganate to regenerate the manganese dioxide by hydrogen ions or reducing agents, and then obtaining an active manganese dioxide product; the product is easy to generate secondary pollution, the operation cost is high, and the industrial popularization cannot be carried out.
For example, in the method for preparing manganese sulfate electrolyte and recovering lead by using electrolytic manganese anode slime disclosed in CN201410054653.8, electrolytic manganese anode slime, pyrite beneficiation concentrate with sulfur content of not less than 45% and concentrated sulfuric acid are used as raw materials, manganese sulfate electrolyte is obtained by reduction leaching, impurity removal and filtration, leached slag is used as a raw material, pyrite beneficiation concentrate with sulfur content of not less than 45%, hydrochloric acid and nitric acid are processed as raw materials, and filter residue is qualified lead concentrate by reduction leaching, impurity removal and filtration. Although the method has the characteristics of less consumption of the reducing agent pyrite, low cost and capability of recycling manganese and lead, the method also has the defects that: on one hand, the amount of waste residues generated in the leaching process is large, the waste residues need to be further treated, and the treatment cost is increased; on the other hand, the iron content in the leachate is high, so that a qualified manganese sulfate solution can be obtained only by adopting a complicated purification process subsequently.
Therefore, the problem to be solved by the technical personnel in the field is to provide a method for sulfuric acid curing leaching of manganese from electrolytic manganese anode slag, which has low operation cost and does not generate secondary pollution.
Disclosure of Invention
In view of the above, the invention provides a method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing, which has the advantages of wide source of reducing agents, low price, simple process, high manganese leaching rate, low operation cost, no secondary waste residue pollution and waste gas pollution and the like, and can effectively solve the problems of high manganese leaching cost, secondary pollution generated in the leaching process and the like in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing specifically comprises the following steps:
(1) weighing electrolytic manganese anode slag, sulfur powder and concentrated sulfuric acid as required for later use;
(2) adding sulfur powder and concentrated sulfuric acid into electrolytic manganese anode slag, uniformly mixing, and carrying out curing reaction to obtain clinker;
(3) adding water into the clinker for leaching, and obtaining manganese-containing leaching solution and leaching slag after liquid-solid separation.
The beneficial effects of the preferred technical scheme are as follows: the method comprises the steps of reducing manganese dioxide in electrolytic manganese anode slag by using sulfur powder and concentrated sulfuric acid, and leaching out the manganese dioxide in water to dissolve the manganese sulfate obtained by reduction in water, so as to realize leaching separation. As the sulfur powder is used as a reducing agent and is matched with concentrated sulfuric acid, the leaching rate of manganese can be effectively improved.
Preferably, the mass concentration of the concentrated sulfuric acid is greater than 95%, and the purity of the sulfur powder is greater than 99%.
Preferably, the mass ratio of the sulfur powder to the electrolytic manganese anode slag in the step (1) is (10-16): 100, respectively; the mass ratio of the electrolytic manganese anode slag to the concentrated sulfuric acid is (0.8-1.4): 1.
the beneficial effects of the preferred technical scheme are as follows: according to the invention, concentrated sulfuric acid with the mass concentration of more than 95% is adopted for carrying out the curing reaction, so that the influence of excessive water on the normal curing reaction is avoided, the conversion rate of manganese dioxide is improved, and the leaching rate of manganese is further improved; the electrolytic manganese anode slag, the sulfur powder and the concentrated sulfuric acid are reasonable in dosage, and the utilization rate of raw materials can be improved on the premise of ensuring the leaching rate of manganese.
Further preferably, the mixing temperature in the step (2) is 15-30 ℃.
Preferably, the curing temperature in the step (2) is 100-150 ℃, and the curing time is 10-24 hours.
The beneficial effects of the preferred technical scheme are as follows: the invention limits the temperature and time of the curing reaction, ensures that manganese dioxide in the electrolytic manganese anode slag can quickly and effectively react to generate manganese sulfate, and thus, the manganese leaching rate of the electrolytic manganese anode slag can be realized.
Preferably, in the step (3), water is added until the liquid-solid volume-mass ratio is (2-3) L: 1Kg, the leaching temperature is 15-30 ℃, and the pressure is 1.0 multiplied by 105Pa, the time is 0.5-1 h.
The beneficial effects of the preferred technical scheme are as follows: according to the method, water is added to adjust the liquid-solid ratio, so that the manganese sulfate obtained by reaction is completely dissolved in the water, the separation from the lead is realized, the leaching temperature, pressure and time are controlled, and the leaching rate and efficiency are improved.
Preferably, the method also comprises the step (4) of removing heavy metal from the manganese-containing leaching solution to obtain a manganese sulfate solution, and drying leaching slag to obtain lead concentrate.
According to the technical scheme, compared with the prior art, the invention discloses a method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing, which has the following beneficial effects:
(1) the sulfur powder adopted by the invention is used as a reducing agent, the source is wide, the price is low, the sulfur powder is matched with concentrated sulfuric acid to carry out curing reaction, the reaction temperature is about 100 ℃, the consumed energy is relatively low, and the operation cost is reduced;
(2) in addition, the invention adopts the reducing agent to carry out curing reaction, can improve the leaching rate of manganese, has no secondary waste residue pollution, waste gas pollution and the like, can simplify the process flow, and is beneficial to industrialized popularization.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing, which specifically comprises the following steps:
(1) the weight ratio of (10-16): 100, respectively weighing sulfur powder and electrolytic manganese anode slag, and according to the mass ratio of concentrated sulfuric acid to electrolytic manganese anode slag being (0.8-1.4): 1, measuring concentrated sulfuric acid for later use;
(2) adding sulfur powder and concentrated sulfuric acid into electrolytic manganese anode slag, uniformly stirring, and carrying out curing reaction to obtain clinker; curing at 100-150 ℃ for 10-24 h;
(3) adding water into the clinker until the volume-to-solid mass ratio of the liquid to the solid is (2-3) L: 1Kg at 15-25 ℃ and 1.0X 105Leaching for 0.5-1 h under the Pa condition, and performing liquid-solid separation to obtain a manganese-containing leaching solution and leaching residues.
In order to further optimize the technical scheme, the method also comprises the step (4) of removing heavy metal impurities from the manganese-containing leaching solution to obtain a manganese sulfate solution; and drying the leached slag to obtain lead concentrate.
Example 1
A method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing specifically comprises the following steps:
(1) respectively weighing 1Kg of electrolytic manganese anode slag, 0.16Kg of sulfur powder and 1Kg of concentrated sulfuric acid (the mass concentration is more than 95%);
(2) adding sulfur powder and concentrated sulfuric acid into the electrolytic manganese anode slag, and stirring until the sulfur powder and the concentrated sulfuric acid are uniformly mixed; heating to 125 ℃ and curing for 20h to obtain clinker;
(3) adding water into the clinker, mixing the slurry until the liquid-solid ratio is 2: 1, stirring and leaching for 1h at room temperature, and filtering to obtain manganese-containing leaching solution and leaching residues. The leaching rate of manganese is 92.0%.
Example 2
A method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing specifically comprises the following steps:
(1) respectively weighing 1Kg of electrolytic manganese anode slag, 0.16Kg of sulfur powder and 1Kg of concentrated sulfuric acid (the mass concentration is more than 95%);
(2) adding sulfur powder and concentrated sulfuric acid into the electrolytic manganese anode slag, and stirring until the sulfur powder and the concentrated sulfuric acid are uniformly mixed; heating to 150 ℃ and curing for 20h to obtain clinker;
(3) adding water into the clinker, mixing the slurry until the liquid-solid ratio is 2: 1, stirring and leaching for 1h at room temperature, and filtering to obtain manganese-containing leaching solution and leaching residues. The leaching rate of manganese was 95.6%.
Example 3
A method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing specifically comprises the following steps:
(1) respectively weighing 1Kg of electrolytic manganese anode slag, 0.16Kg of sulfur powder and 1Kg of concentrated sulfuric acid (the mass concentration is more than 95%);
(2) adding sulfur powder and concentrated sulfuric acid into the electrolytic manganese anode slag, and stirring until the sulfur powder and the concentrated sulfuric acid are uniformly mixed; heating to 150 ℃ for curing for 24h to obtain clinker;
(3) adding water into the clinker, mixing the slurry until the liquid-solid ratio is 2: 1, stirring and leaching for 1h at room temperature, and filtering to obtain manganese-containing leaching solution and leaching residues. The leaching rate of manganese is 97.8%.
Example 4
A method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing specifically comprises the following steps:
(1) respectively weighing 1Kg of electrolytic manganese anode slag, 0.16Kg of sulfur powder and 1.2Kg of concentrated sulfuric acid (the mass concentration is more than 95%);
(2) adding sulfur powder and concentrated sulfuric acid into the electrolytic manganese anode slag, and stirring until the sulfur powder and the concentrated sulfuric acid are uniformly mixed; heating to 150 ℃ for curing for 24h to obtain clinker;
(3) adding water into the clinker, mixing the slurry until the liquid-solid ratio is 2: 1, stirring and leaching for 1h at room temperature, and filtering to obtain manganese-containing leaching solution and leaching residues. The leaching rate of manganese was 99.0%.
Example 5
A method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing specifically comprises the following steps:
(1) respectively weighing 1Kg of electrolytic manganese anode slag, 0.12Kg of sulfur powder and 1Kg of concentrated sulfuric acid (mass concentration is more than 95%);
(2) adding sulfur powder and concentrated sulfuric acid into the electrolytic manganese anode slag, and stirring until the sulfur powder and the concentrated sulfuric acid are uniformly mixed; heating to 150 ℃ for curing for 24h to obtain clinker;
(3) adding water into the clinker, mixing the slurry until the liquid-solid ratio is 2: 1, stirring and leaching for 1h at room temperature, and filtering to obtain manganese-containing leaching solution and leaching residues. The leaching rate of manganese is 92.8%.
Experimental detection
1. The manganese leaching rates of examples 1 to 5 and comparative examples were detected and calculated.
Control group: the method disclosed in CN 201310396867.9;
(1) respectively detecting the manganese content of the electrolytic manganese anode slag in the raw materials of the examples 1-5 and the control group; and, the manganese content of the obtained leaching residue is detected, and the result is shown in the following table 1; wherein the manganese content is measured by adopting a national standard method of GBT 1506-2016 manganese ore manganese content.
(2) The manganese leaching rates of the respective examples and comparative examples were calculated according to the following formulas, and the results are shown in table 1 below.
The leaching rate of manganese is (the amount of manganese in the anode slag-the amount of manganese in the leaching slag) ÷ the amount of manganese in the anode slag multiplied by 100 percent
TABLE 1
| Lead content of anode slag | Manganese content of anode slag | Manganese content in leached residue | Leaching rate of manganese | |
| Example 1 | 5.5％ | 48.6％ | 11.5％ | 92.0％ |
| Example 2 | 5.5％ | 48.6％ | 11.2％ | 95.0％ |
| Example 3 | 5.5％ | 48.6％ | 10.8％ | 97.8％ |
| Example 4 | 5.5％ | 48.6％ | 10.5％ | 98.2％ |
| Example 5 | 5.5％ | 48.6％ | 10.2％ | 99.0％ |
| Control group | —— | 40％ | 2.53％ | 92.0％ |
2. Running cost comparison
Control group: the method disclosed in CN 201310396867.9;
(1) the method of examples 1-5 and the method of comparative group 1 were respectively adopted to treat the reducing agent dosage and cost required by 100 tons of electrolytic manganese anode slag, and the results are shown in the following tables 2 and 3.
TABLE 2 cost of reducing agent
TABLE 3 sulfuric acid cost
From the above tables 2 and 3, it can be seen that: the raw material cost of the reducing agent obtained by the method of the embodiment 1-5 is obviously lower than that of the reducing agent obtained by the method of the control group (CN 201310396867.9); the cost of sulfuric acid is slightly higher than that of the control group (CN 201310396867.9). However, the cost of the raw materials in examples 1 to 5 of the present invention was found to be lower than that in the control group (CN201310396867.9) by comprehensive examination; and other costs are not greatly different in analysis, the invention has slightly higher fuel cost due to longer heat preservation time, but does not need long-time stirring, has lower power consumption, similar total energy consumption and equivalent equipment investment. Therefore, compared with the control group (CN201310396867.9), the running cost of the invention is obviously reduced.
Example 6 influence of the quality of Sulfur powder on the manganese Leaching Rate
According to the method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing, disclosed in embodiment 2, the mass of the sulfur powder weighed in the step (1) is respectively adjusted to 0.08 Kg, 0.10Kg, 0.12Kg, 0.14 Kg and 0.18Kg, and other experimental conditions are unchanged, so that 1-5 control groups are respectively obtained.
The results of observing the leaching rate of the manganese in the electrolytic manganese anode slag in the aging leaching process of the experimental groups 1-5 are shown in the table 1.
TABLE 4
From the results experiment of table 4 above, it is evident that: when the mass of the sulfur powder added into 1Kg of electrolytic manganese anode slag is less than 0.10Kg, the leaching rate of manganese is lower and is lower than 90%; when the mass of the sulfur powder added into 1Kg of electrolytic manganese anode slag is 0.10Kg, the leaching rate of manganese is more than 90 percent, the leaching rate of manganese is continuously increased along with the increase of the mass of the sulfur powder, and when the mass of the sulfur powder is increased to 0.16Kg, the mass of the sulfur powder is continuously increased, and the leaching rate of manganese is not obviously increased. The mass ratio of the electrolytic manganese anode slag to the sulfur powder determined by the invention can meet the requirement of manganese leaching rate in actual production, and further increase of the addition of the sulfur powder can cause waste and increase of cost.
Example 7 influence of quality of concentrated sulfuric acid on manganese leaching Rate
According to the method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing, disclosed in embodiment 3, the mass of concentrated sulfuric acid weighed in the step (1) is respectively adjusted to 0.6 Kg, 0.8Kg, 1.2Kg, 1.4Kg and 1.6Kg, and other experimental conditions are unchanged, so that 1-5 control groups are respectively obtained.
The leaching rate of manganese in the electrolytic manganese anode slag in the aging leaching process of the comparative examples 1 to 5 and 3 was calculated, and the results are shown in table 5.
TABLE 5
As is evident from the experimental results in table 5 above: when the mass of concentrated sulfuric acid added into 1Kg of electrolytic manganese anode slag is less than 0.8Kg, the leaching rate of manganese is lower and is lower than 90%; when the mass of concentrated sulfuric acid added into 1Kg of electrolytic manganese anode slag is 1.0Kg, the leaching rate of manganese is more than 90 percent, and the leaching rate of manganese is increased sharply along with the increase of the mass of the concentrated sulfuric acid, and when the mass of the concentrated sulfuric acid is increased to 1.4Kg, the leaching rate of manganese is as high as 99.5 percent, the mass of the concentrated sulfuric acid is continuously increased, and the leaching rate of manganese is not increased any more. The quality control of the concentrated sulfuric acid within the range of 0.8-1.4 Kg can meet the requirement of manganese leaching rate in actual production, and further increase of the addition of the concentrated sulfuric acid can cause waste and increase of cost.
EXAMPLE 8 Effect of heating temperature on manganese Leaching Rate
According to the method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing disclosed in embodiment 3, the heating temperatures in the step (2) are respectively adjusted to 90 ℃, 100 ℃, 125 ℃ and 160 ℃, and other experimental conditions are unchanged, so that control groups 1-4 are respectively obtained.
The results of calculating the leaching rate of manganese in the electrolytic manganese anode slag in the aging leaching process of the comparative examples 3 and 1 to 5 are shown in table 6.
TABLE 6
| Heating temperature (. degree.C.) | Leaching rate of manganese (%) | |
| Example 3 | 150 | 97.8 |
| Control group 1 | 90 | 88.5 |
| Control group 2 | 100 | 91.2 |
| Control group 3 | 125 | 93.6 |
| Control group 4 | 160 | 98.0 |
As is apparent from the results in table 6 above: when the heating temperature is 90 ℃, the leaching rate of manganese is low, only 88.5 percent and lower than 90 percent; when the heating temperature reaches 100 ℃, the leaching rate of manganese is more than 90%, when the heating temperature is increased to 150 ℃, the leaching rate of manganese reaches 97.8%, and the leaching rate of manganese is not obviously increased when the temperature is continuously increased. The invention is proved that the heating temperature is controlled within the range of 100-150 ℃, the requirement of manganese leaching rate in actual production can be met, and the cost is increased due to energy consumption waste caused by further increasing the temperature.
Example 9 Effect of aging time on manganese Leaching Rate
According to the method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing, disclosed in the embodiment 4, the curing time in the step (2) is respectively adjusted to 8 hours, 10 hours, 15 hours, 20 hours and 26 hours, and other experimental conditions are not changed, so that experimental groups 1-6 are respectively obtained.
The results of observing the leaching rate of manganese in the electrolytic manganese anode slag in the aging leaching process of the experimental groups 1 to 6 are shown in Table 7.
TABLE 7
| Maturation time (h) | Leaching rate (%) | |
| Example 4 | 24 | 99.0 |
| Control group 1 | 9 | 88.7 |
| Control group 2 | 10 | 90.6 |
| Control group 3 | 15 | 93.5 |
| Control group 4 | 20 | 96.7 |
| Control group 5 | 26 | 99.5 |
As is evident from the results in table 7 above: when the curing time is 9 hours, the leaching rate of manganese is low, only 88.7 percent and lower than 90 percent; when the curing time reaches 10 hours, the leaching rate of manganese is more than 90 percent; when the aging time is prolonged to 24 hours, the leaching rate of manganese reaches 99.0 percent, the aging time is continuously prolonged, and the leaching rate of manganese is not obviously increased. The method disclosed by the invention has the advantages that the curing time is controlled within the range of 10-24 h, the requirement on the manganese leaching rate in actual production can be met, and the energy consumption is wasted and the cost is increased due to the further extension of the curing time.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911158655.0A CN110846512B (en) | 2019-11-22 | 2019-11-22 | A kind of method of electrolytic manganese anode slag sulfuric acid ripening leaching manganese |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911158655.0A CN110846512B (en) | 2019-11-22 | 2019-11-22 | A kind of method of electrolytic manganese anode slag sulfuric acid ripening leaching manganese |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110846512A CN110846512A (en) | 2020-02-28 |
| CN110846512B true CN110846512B (en) | 2021-11-02 |
Family
ID=69603928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911158655.0A Active CN110846512B (en) | 2019-11-22 | 2019-11-22 | A kind of method of electrolytic manganese anode slag sulfuric acid ripening leaching manganese |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110846512B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114645300B (en) * | 2022-03-21 | 2024-04-05 | 吉首大学 | Preparation method for directly dechlorinating cuprous chloride and circularly regenerating copper |
| CN115806318B (en) * | 2022-12-13 | 2024-06-21 | 大连融科储能集团股份有限公司 | Production method of manganese sulfate |
| AU2023446727B2 (en) * | 2023-07-28 | 2025-03-06 | Gem Co., Ltd. | Treatment method for laterite nickel ore by curing and roasting-water leaching-atmospheric pressure acid leaching |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5625978A (en) * | 1979-08-07 | 1981-03-12 | Nippon Steel Corp | Manufacture of electrolytic manganese dioxide |
| CN103789551A (en) * | 2014-02-18 | 2014-05-14 | 广西大学 | Method for preparing manganese sulfate electrolyte and recycling lead by using electrolytic manganese anode mud |
| CN104762466A (en) * | 2015-04-17 | 2015-07-08 | 北京矿冶研究总院 | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore |
| CN104817116A (en) * | 2015-04-21 | 2015-08-05 | 北京矿冶研究总院 | Method for producing manganese sulfate from manganese oxide ore |
| CN106544511A (en) * | 2016-12-12 | 2017-03-29 | 株洲冶炼集团股份有限公司 | A kind of method of synthetical recovery manganese, lead, silver and selenium from Manganese anode slime |
| CN110408786A (en) * | 2019-08-29 | 2019-11-05 | 贵州大学 | A kind of electrolytic manganese anode slag catalysis prepares the method for manganese sulfate solution and recovers lead |
-
2019
- 2019-11-22 CN CN201911158655.0A patent/CN110846512B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5625978A (en) * | 1979-08-07 | 1981-03-12 | Nippon Steel Corp | Manufacture of electrolytic manganese dioxide |
| CN103789551A (en) * | 2014-02-18 | 2014-05-14 | 广西大学 | Method for preparing manganese sulfate electrolyte and recycling lead by using electrolytic manganese anode mud |
| CN104762466A (en) * | 2015-04-17 | 2015-07-08 | 北京矿冶研究总院 | Liquid preparation method for producing electrolytic manganese or manganese dioxide from low-grade manganese oxide ore |
| CN104817116A (en) * | 2015-04-21 | 2015-08-05 | 北京矿冶研究总院 | Method for producing manganese sulfate from manganese oxide ore |
| CN106544511A (en) * | 2016-12-12 | 2017-03-29 | 株洲冶炼集团股份有限公司 | A kind of method of synthetical recovery manganese, lead, silver and selenium from Manganese anode slime |
| CN110408786A (en) * | 2019-08-29 | 2019-11-05 | 贵州大学 | A kind of electrolytic manganese anode slag catalysis prepares the method for manganese sulfate solution and recovers lead |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110846512A (en) | 2020-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2020102180A4 (en) | Method for leaching manganese from electrolytic manganese anode slag | |
| CN110482511B (en) | Method for recovering anode material of waste lithium iron phosphate battery | |
| CN101509077B (en) | Method for extracting platinum, palladium, rhodium from automotive catalyst of ore phase reconstruction | |
| CN109554549B (en) | Method for leaching and recovering rare earth in neodymium iron boron waste at high temperature and high pressure | |
| CN110846512B (en) | A kind of method of electrolytic manganese anode slag sulfuric acid ripening leaching manganese | |
| CN109055757B (en) | Method for recovering manganese dioxide and lead in anode slag of electrolytic manganese or electrolytic zinc | |
| CN109110826B (en) | Production method of battery-grade nickel sulfate | |
| CN103194768B (en) | High ferro high-phosphorus manganese is utilized to prepare the method for electrolytic metal Mn | |
| CN104261445A (en) | Method for harmlessly treating aluminum ash and preparing sandy alumina | |
| CN105772486A (en) | Method for removing cyanide in waste cathode carbon in aluminum electrolysis cell | |
| CN103911514B (en) | The recovery and treatment method of scrap hard alloy grinding material | |
| CN102321809A (en) | Method for extracting cobalt and copper from cobalt-copper-iron alloy | |
| WO2020107670A1 (en) | Method for concentrating iron by comprehensively utilizing steelmaking dust | |
| CN114318417A (en) | Method for producing electrolytic manganese by using low-grade manganese oxide three-ore method | |
| CN110029220B (en) | Method for preparing metal chromium powder by reducing chromium oxide through two-step method | |
| CN103131864B (en) | Method for pre-treating complex indium-containing smoke dust by microwave roasting | |
| CN116995327B (en) | A method for recovering lithium from ternary cathode waste | |
| CN113862464A (en) | Method for recovering copper and scattered metal in black copper sludge | |
| CN111074076B (en) | Comprehensive utilization system and method for metallurgical solid waste | |
| CN110042230B (en) | Method for chemically strengthening metal leaching in secondary zinc oxide powder by mechanochemical coupling ultrasonic | |
| CN112553482A (en) | Method for efficiently extracting iron from neodymium iron boron waste to enrich rare earth elements | |
| CN108866354B (en) | A kind of method for efficiently extracting vanadium from vanadium-bearing ore | |
| CN116854062A (en) | Efficient recycling method for waste residues after lithium extraction | |
| CN110512082B (en) | A kind of recycling method of waste metal sludge | |
| CN115466848A (en) | A method for extracting multiple elements from vanadium-rich slag and its application |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| OL01 | Intention to license declared | ||
| OL01 | Intention to license declared |