AU2020102180A4 - Method for leaching manganese from electrolytic manganese anode slag - Google Patents
Method for leaching manganese from electrolytic manganese anode slag Download PDFInfo
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- manganese
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- slag
- electrolytic manganese
- sulfuric acid
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 171
- 239000011572 manganese Substances 0.000 title claims abstract description 171
- 238000002386 leaching Methods 0.000 title claims abstract description 129
- 239000002893 slag Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000005303 weighing Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 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
- 239000012141 concentrate Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 14
- 239000002699 waste material Substances 0.000 abstract description 12
- 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 14
- 238000010438 heat treatment Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 4
- 229910052683 pyrite Inorganic materials 0.000 description 4
- 239000011028 pyrite Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 3
- 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
- 230000003213 activating effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 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 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 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
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000720 Silicomanganese Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000005265 energy consumption 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
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing 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
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention discloses a method for leaching manganese from electrolytic
manganese anode slag, specifically comprising the following steps: weighing electrolytic
manganese anode slag, sulfur powder and concentrated sulfuric acid as required for later use;
adding the sulfur powder and the concentrated sulfuric acid to the electrolytic manganese anode
slag, mixing evenly, and performing curing to obtain clinker; and adding water to the clinker for
leaching, and performing liquid-solid separation to obtain manganese-containing leaching
solution and leaching slag. The method disclosed by the present invention has the advantages of
wide sources of reducing agents, low price, simple process, high manganese leaching rate, low
operating costs, no secondary waste slag pollution and waste gas pollution, etc., and can
effectively solve the problems of high manganese leaching costs, secondary pollution produced
in the leaching process and the like in the prior art.
1
Description
Description
Technical Field
The present invention relates to the technical field of recovery of hydrometallurgical waste slag, particularly to a method for leaching manganese from electrolytic manganese anode slag.
Background
Electrolytic manganese anode slag is the waste slag produced in the production process of electrolytic metal manganese, of which the main component is manganese, wherein the content of manganese dioxide accounts for about 40-50%, and the content of lead is also high, that is, accounts for 4-6, both of the two are valuable secondary resources that can be reused. However, the mineral composition and the structure of the electrolytic manganese anode slag are complex, and the symbiotic relationship between lead and manganese hydrated oxide is very close, so it is difficult to separate manganese and lead by means of a mechanical sorting method. Therefore, except for a small amount is used for ferromanganese and silicomanganese alloy smelting, most of electrolytic manganese anode slag are deserted and are not well developed and comprehensively utilized, only causing waste of resources, but also causing environmental pollution due to improper handling. Therefore, the problem to be urgently solved by those skilled in the art is how to efficiently separate and comprehensively utilize the main valuable components, i.e. manganese and lead of electrolytic manganese anode slag economically and environmentally.
However, the existing resource utilization methods of electrolytic manganese anode slime mainly include reduction method and method for activating anode slime, which have the problems of high operating costs, easy causation of secondary pollution, and inability to be industrialized. In the reduction method, charcoal, graphite, etc. are used as reducing agents to perform high-temperature roasting reaction or biomass, sulfurous acid, pyrite, sulfur dioxide, etc. are used as reducing agents to convert tetravalent manganese in anode slime into divalent manganese so as to enter the solution, and impurities such as lead and the like are present in solid phase, so the comprehensive utilization of manganese can be realized by solid-liquid separation. However, in the high-temperature roasting process, there is a need to consume high energy,
Description which is easy to cause environmental pollution, and may cause a substantial increase in operating cost. The method for activating anode slime includes: removing impurity elements in anode slime by acid leaching, roasting acid leaching, alkali oxidation, etc., changing the crystal form of manganese dioxide in the anode slime, promoting manganese sesquioxide or permanganate to regenerate manganese dioxide through hydrogen ions or reducing agents, and then obtaining an active manganese dioxide product which has the disadvantages of easy causation of secondary pollution, high operating costs and inability to be industrialized.
For example, a method for preparing manganese sulfate electrolyte and recycling lead using electrolytic manganese anode slime disclosed in CN201410054653.8, comprising: performing reduction leaching, impurity removal and filtration to obtain manganese sulfate electrolyte by using electrolytic manganese anode slime, pyrite beneficiation concentrate with sulfur content of more than or equal to 45% and concentrated sulfuric acid as raw materials, and performing reduction leaching, impurity removal, filtration, and slag filtration to obtain qualified lead concentrate by using leaching slag as a raw material and using the processed pyrite beneficiation concentrate with sulfur content of more than or equal to 45%, hydrochloric acid and nitric acid raw materials. Although having the characteristics of small usage amount of pyrite as reducing agent, low costs, and the ability to recycle manganese and lead, the method also has the defects that: on the one hand, the amount of waste slag produced in the leaching process is large, and the waste slag needs to be further processed, increasing the processing cost; and on the other hand, the content of iron in the leaching solution is high, so a complicated purification process is required to obtain a qualified manganese sulfate solution.
Therefore, the problem to be urgently solved by those skilled in the art is to provide a method for leaching manganese from electrolytic manganese anode slag by sulfuric acid curing with the advantages of low operating costs and no secondary pollution.
Summary
In view of this, the present invention provides a method for leaching manganese from electrolytic manganese anode slag, which has the advantages of wide sources of reducing agents, low price, simple process, high manganese leaching rate, low operating costs, no secondary waste slag pollution and waste gas pollution, etc., and can effectively solve the problems of high manganese leaching costs, secondary pollution produced in the leaching process and the like in the prior art.
Description
To achieve the above purpose, the present invention adopts the following technical solution:
A method for leaching manganese from electrolytic manganese anode slag, specifically comprising the following steps:
(1) weighing electrolytic manganese anode slag, sulfur powder and concentrated sulfuric acid as required for later use;
(2) adding the sulfur powder and the concentrated sulfuric acid to the electrolytic manganese anode slag, mixing evenly, and performing curing to obtain clinker; and
(3) adding water to the clinker for leaching, and performing liquid-solid separation to obtain manganese-containing leaching solution and leaching slag.
The above-mentioned preferred technical solution has the advantageous effect that in the present invention, manganese dioxide in electrolytic manganese anode slag is reduced by using sulfur powder and concentrated sulfuric acid first, then water leaching is performed, and the reduced manganese sulfate is dissolved in water to realize leaching and separation. Because the sulfur powder is used as a reducing agent and is combined with the concentrated sulfuric acid, the manganese leaching rate can be effectively increased.
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, in the step (1), the mass ratio of the sulfur powder to the electrolytic manganese anode slag is (10-16):100; and the mass ratio of the electrolytic manganese anode slag to the concentrated sulfuric acid is (0.8-1.4):1.
The above-mentioned preferred technical solution has the advantageous effect that in the present invention, the concentrated sulfuric acid with a mass concentration greater than 95% is used for curing reaction, to prevent excessive moisture from affecting the normal curing reaction, thereby increasing the conversion rate of manganese dioxide, and then increasing the manganese leaching rate; the usage amount of the electrolytic manganese anode slag, sulfur powder and concentrated sulfuric acid is reasonable, so the utilization rate of raw materials can be increased on the premise of guaranteeing the manganese leaching rate.
Further preferably, in the step (2), the temperature of the mixing is 15-30°C.
Preferably, in the step (2), the temperature of the curing is 100-150°C, and the duration is -24h.
Description The above-mentioned preferred technical solution has the advantageous effect that in the present invention, the temperature and duration of the curing reaction are limited, to guarantee that manganese dioxide in the electrolytic manganese anode slag reacts quickly and effectively to produce manganese sulfate, so that the manganese leaching rate of the electrolytic manganese anode slag can be increased.
Preferably, in the step (3), water is added until the liquid-solid volume mass ratio is (2-3) L:1 Kg, the leaching temperature is 15-30°C, the pressure is 1.0*105 Pa, and the duration is 0.5-lh.
The above-mentioned preferred technical solution has the advantageous effect that in the present invention, water is added to adjust the liquid-solid ratio, so that the manganese sulfate obtained by the reaction is completely dissolved into the water to achieve separation from lead, and the leaching temperature, pressure and duration are controlled to increase the leaching rate and efficiency.
Preferably, further comprising a step (4): removing heavy metals from the manganese-containing leaching solution to obtain manganese sulfate solution, drying the leaching slag, and thus obtaining lead concentrate.
It can be known from the above technical solution that compared with the prior art, the present invention discloses and provides a method for leaching manganese from electrolytic manganese anode slag, and has the following advantageous effects:
( 1 ) As a reducing agent, the sulfur powder used in the present invention has wide source and low price, and is combined with concentrated sulfuric acid for curing reaction, the reaction temperature is about 100°C, and the consumed energy is relatively low, reducing operating costs.
( 2 ) Moreover, by using the reducing agent for curing reaction, the present invention can increase the manganese leaching rate, has no secondary waste slag pollution and waste gas pollution, etc., and can simplify the process flow, being beneficial to being industrialized.
Detailed Description
The technical solution in embodiments of the present invention will be clearly and fully described below. Apparently, the described embodiments are merely part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments in the present
Description invention, all other embodiments obtained by those ordinary skilled in the art without contributing creative labor will belong to the protection scope of the present invention.
Embodiments of the present invention disclose a method for leaching manganese from electrolytic manganese anode slag, specifically comprising the following steps:
(1) weighing sulfur powder and electrolytic manganese anode slag respectively in a mass ratio of (10-16):100, and weighing concentrated sulfuric acid in a mass ratio of (0.8-1.4):1 of the concentrated sulfuric acid to the electrolytic manganese anode slag for later use;
(2) adding the sulfur powder and the concentrated sulfuric acid to the electrolytic manganese anode slag, stirring evenly, and performing curing to obtain clinker, wherein the temperature of the curing is 100-150°C, and the duration is 10-24h; and
(3) adding water to the clinker until the liquid-solid volume mass ratio is (2-3) L:1 Kg, leaching for 0.5-1h at 15-25°C and 1.0*105 Pa, and performing liquid-solid separation to obtain manganese-containing leaching solution and leaching slag.
To further optimize the technical solution, further comprising a step (4): removing heavy metals from the manganese-containing leaching solution to obtain manganese sulfate solution; and drying the leaching slag to obtain lead concentrate.
Embodiment 1
A method for leaching manganese from electrolytic manganese anode slag, specifically comprising the following steps:
(1) weighing 1 Kg of electrolytic manganese anode slag, 0.16 Kg of sulfur powder and 1 Kg of concentrated sulfuric acid (mass concentration > 95%) respectively;
(2) adding the sulfur powder and the concentrated sulfuric acid to the electrolytic manganese anode slag, stirring to be mixed evenly; heating to 125°C and curing for 20h to obtain clinker; and
(3) adding water to the clinker to adjust the slurry to a liquid-solid ratio of 2:1, stirring and leaching for lh at room temperature, and filtering to obtain manganese-containing leaching solution and leaching slag, wherein the manganese leaching rate is 92.0%.
Description
Embodiment 2
A method for leaching manganese from electrolytic manganese anode slag, specifically comprising the following steps:
(1) weighing 1 Kg of electrolytic manganese anode slag, 0.16 Kg of sulfur powder and 1 Kg of concentrated sulfuric acid (mass concentration > 95%) respectively;
(2) adding the sulfur powder and the concentrated sulfuric acid to the electrolytic manganese anode slag, stirring to be mixed evenly; heating to 150°C and curing for 20h to obtain clinker; and
(3) adding water to the clinker to adjust the slurry to a liquid-solid ratio of 2:1, stirring and leaching for 1h at room temperature, andfiltering to obtain manganese-containing leaching solution and leaching slag, wherein the manganese leaching rate is 95.6%.
Embodiment 3
A method for leaching manganese from electrolytic manganese anode slag, specifically comprising the following steps:
(1) weighing 1 Kg of electrolytic manganese anode slag, 0.16 Kg of sulfur powder and 1 Kg of concentrated sulfuric acid (mass concentration > 95%) respectively;
(2) adding the sulfur powder and the concentrated sulfuric acid to the electrolytic manganese anode slag, stirring to be mixed evenly; heating to 150°C and curing for 24h to obtain clinker; and
(3) adding water to the clinker to adjust the slurry to a liquid-solid ratio of 2:1, stirring and leaching for lh at room temperature, andfiltering to obtain manganese-containing leaching solution and leaching slag, wherein the manganese leaching rate is 97.8%.
Embodiment 4
A method for leaching manganese from electrolytic manganese anode slag, specifically comprising the following steps:
Description (1) weighing 1 Kg of electrolytic manganese anode slag, 0.16 Kg of sulfur powder and 1.2 Kg of concentrated sulfuric acid (mass concentration > 95%) respectively;
(2) adding the sulfur powder and the concentrated sulfuric acid to the electrolytic manganese anode slag, stirring to be mixed evenly; heating to 150°C and curing for 24h to obtain clinker; and
(3) adding water to the clinker to adjust the slurry to a liquid-solid ratio of 2:1, stirring and leaching for 1h at room temperature, and filtering to obtain manganese-containing leaching solution and leaching slag, wherein the manganese leaching rate is 99.0%.
Embodiment 5
A method for leaching manganese from electrolytic manganese anode slag, specifically comprising the following steps:
(1) weighing 1 Kg of electrolytic manganese anode slag, 0.12 Kg of sulfur powder and 1 Kg of concentrated sulfuric acid (mass concentration > 95%) respectively;
(2) adding the sulfur powder and the concentrated sulfuric acid to the electrolytic manganese anode slag, stirring to be mixed evenly; heating to 150°C and curing for 24h to obtain clinker; and
(3) adding water to the clinker to adjust the slurry to a liquid-solid ratio of 2:1, stirring and leaching for lh at room temperature, and filtering to obtain manganese-containing leaching solution and leaching slag, wherein the manganese leaching rate is 92.8%.
Experimental Test
1. Test and calculation of manganese leaching rates of embodiments 1-5 and reference examples
Control group: method disclosed in CN201310396867.9;
(1) Performing determination of manganese content on the electrolytic manganese anode slag in the raw materials of embodiments 1-5 and the control group respectively; and performing determination of manganese content on the obtained leaching slag, the results being shown in
Description
Table 1 below, wherein the determination of manganese content is performed using the national standard method "GBT 1506-2016 Manganese ores-Determinationof manganese content".
(2) Calculating the manganese leaching rates of various embodiments and reference examples according to the following formula, the results obtained being shown in Table 1 below:
Manganese Leaching Rate = (Content of Manganese in Anode Slag - Content of Manganese in Leaching Slag)+ Content of Manganese in Anode Slag * 100%
Table 1
Content of lead Content of Content of Manganese in anode slag manganese in manganese in leaching rate anode slag leaching slag
Embodiment 1 5.5% 48.6% 11.5% 92.0%
Embodiment 2 5.5% 48.6% 11.2% 95.0%
Embodiment 3 5.5% 48.6% 10.8% 97.8%
Embodiment 4 5.5% 48.6% 10.5% 98.2%
Embodiment 5 5.5% 48.6% 10.2% 99.0%
Control group - 40% 2.53% 92.0%
2. Comparison of operating costs
Control group: method disclosed in CN201310396867.9;
(1) For the usage amount and cost of reducing agent required to treat 100 tons of electrolytic manganese anode slag using the methods of embodiments 1-5 and control group 1 respectively, the results are shown in Table 2 and Table 3 below.
Table 2 Cost of reducing agent
Usage amount of Unit price of reducing Cost of reducing reducing agent (Kg) agent (Yuan/Kg) agent (Yuan/Kg)
Embodiment 1 0.16 2.6 0.42
Description
Embodiment 2 0.16 2.6 0.42
Embodiment 3 0.16 2.6 0.42
Embodiment 4 0.16 2.6 0.42
Embodiment 5 0.12 2.6 0.31
Control group 0.5-0.8 4.5 2.3-3.6
Table 3 Cost of sulfuric acid
Usage amount of Unit price of sulfuric Cost of sulfuric acid sulfuric acid (Kg) acid (Yuan/Kg) (Yuan/Kg)
Embodiment 1 1.0 0.5 0.5
Embodiment 2 1.0 0.5 0.5
Embodiment 3 1.0 0.5 0.5
Embodiment 4 1.2 0.5 0.6
Embodiment 5 1.0 0.5 0.5
Control group 1 0.2-0.3 0.5 0.1-0.2
As shown in Table 2 and Table 3, the raw material cost of the reducing agent obtained using the methods of embodiments 1-5 of the present invention is significantly lower than the raw material cost of the reducing agent obtained using the method of the control group (CN201310396867.9); and the cost of sulfuric acid is slightly higher than that of the control group (CN201310396867.9). However, it is known through comprehensive accounting that the raw material cost of embodiments 1-5 of the present invention is lower than that of the control group (CN201310396867.9); moreover, it is analyzed that other costs are not much different, the present invention requires a longer heat preservation duration so the fuel cost is slightly higher, but does not require long-term stirring so power consumption is lower, the total energy consumption is similar, and the equipment investment is also similar. Therefore, compared with
Description the control group (CN201310396867.9), the operating cost of the present invention is significantly reduced.
Embodiment 6 Influence of mass of sulfur powder on manganese leaching rate
According to the method for leaching manganese from electrolytic manganese anode slag disclosed in embodiment 2, adjusting the mass of the sulfur powder weighed in the step (1) to 0.08, 0.10, 0.12, 0.14 and 0.18 Kg respectively, with other experimental conditions are unchanged, to obtain control groups 1-5 respectively.
Observing the manganese leaching rates of the electrolytic manganese anode slag in the curing and leaching process of the control groups 1-5, the results being shown in Table 4.
Table 4
Mass of sulfur powder (Kg) Manganese leaching rate (%)
Embodiment 2 0.16 95.6
Control group 1 0.08 89.4
Control group 2 0.10 91.5
Control group 3 0.12 92.6
Control group 4 0.14 94.3
Control group 5 0.18 95.8
It can be seen from the experimental results in the above Table 4 that if the mass of the sulfur powder added to 1 Kg of electrolytic manganese anode slag is less than 0.10 Kg, the manganese leaching rate is low, less than 90%; and if the mass of the sulfur powder added to 1 Kg of electrolytic manganese anode slag is 0.10 Kg, the manganese leaching rate is greater than %; moreover, as the mass of the sulfur powder is increased, the manganese leaching rate is increased continually, when the mass of the sulfur powder is increased to 0.16 Kg, if the mass of the sulfur powder is continued to be increased, the increase in manganese leaching rate is not obvious, indicating that determining the mass ratio of electrolytic manganese anode slag to sulfur powder in the present invention can meet the requirements for manganese leaching rate in actual
Description
production, and further increasing the adding amount of sulfur powder may cause waste and increase costs.
Embodiment 7 Influence of mass of concentrated sulfuric acid on manganese leaching rate
According to the method for leaching manganese from electrolytic manganese anode slag disclosed in embodiment 3, adjusting the mass of the concentrated sulfuric acid weighed in the step (1) to 0.6, 0.8, 1.2, 1.4 and 1.6 Kg respectively, with other experimental conditions are unchanged, to obtain control groups 1-5 respectively.
Calculating the manganese leaching rates of the electrolytic manganese anode slag in the curing and leaching process of embodiment 3 and control groups 1-5, the results being shown in Table 5.
Table 5
Mass of concentrated sulfuric acid (Kg) Manganese leaching rate (%)
Embodiment 3 1.0 97.8
Control group 1 0.6 89.4
Control group 2 0.8 91.8
Control group 3 1.2 99.0
Control group 4 1.4 99.5
Control group 5 1.6 99.5
It can be seen from the experimental results in the above Table 5 that if the mass of the concentrated sulfuric acid added to 1 Kg of electrolytic manganese anode slag is less than 0.8 Kg, the manganese leaching rate is low, less than 90%; and if the mass of the concentrated sulfuric acid added to 1 Kg of electrolytic manganese anode slag is 1.0 Kg, the manganese leaching rate is greater than 90%; moreover, as the mass of the concentrated sulfuric acid is increased, the manganese leaching rate is increased sharply, when the mass of the concentrated sulfuric acid is increased to 1.4 Kg, the manganese leaching rate is up to 99.5%, if the mass of the concentrated sulfuric acid is continued to be increased, the manganese leaching rate is not increased any
Description longer, indicating that controlling the mass of the concentrated sulfuric acid within the range of 0.8-1.4 Kg can meet the requirements for manganese leaching rate in actual production, and further increasing the adding amount of concentrated sulfuric acid may cause waste and increase costs.
Embodiment 8 Influence of heating temperature on manganese leaching rate
According to the method for leaching manganese from electrolytic manganese anode slag disclosed in embodiment 3, adjusting the heating temperature in the step (2) to 90, 100, 125 and 160°C respectively, with other experimental conditions are unchanged, to obtain control groups 1-4 respectively.
Calculating the manganese leaching rates of the electrolytic manganese anode slag in the curing and leaching process of embodiment 3 and control groups 1-4, the results being shown in Table 6.
Table 6
Heating temperature (°C) Manganese leaching rate (%)
Embodiment 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
It can be seen from the results in the above Table 6 that if the heating temperature is 90C, the manganese leaching rate is low, only 88.5%, which is less than 90%; and if the heating temperature reaches 100C, the manganese leaching rate is greater than 90%, if the heating temperature rises to 1500 C, the manganese leaching rate reaches 97.8%; and if the temperature continues to rise, the increase in manganese leaching rate is not obvious, indicating that controlling the heating temperature within the range of 100-150 0 C in the present invention can
Description meet the requirements for manganese leaching rate in actual production, and further raising the temperature may cause waste of energy and increase costs.
Embodiment 9 Influence of duration of curing on manganese leaching rate
According to the method for leaching manganese from electrolytic manganese anode slag disclosed in embodiment 4, adjusting the duration of the curing in step (2) to 8, 10, 15, 20, and 26h respectively, with other experimental conditions are unchanged, to obtain experimental groups 1-6 respectively.
Observing the manganese leaching rates of the electrolytic manganese anode slag in the curing and leaching process of the experimental groups 1-6, the results being shown in Table 7.
Table 7
Duration of curing (h) Manganese leaching rate (%)
Embodiment 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
It can be seen from the results in the above Table 7 that if the duration of curing is 9h, the manganese leaching rate is low, only 88.7%, which is less than 90%; if the duration of curing reaches 10h, the manganese leaching rate is greater than 90%; if the duration of curing is prolonged to 24h, the manganese leaching rate reaches 99.0%, and if the duration of curing is continued to be prolonged, the increase in manganese leaching rate is not obvious, indicating that controlling the duration of curing within the range of 10-24h in the present invention can meet the requirements for manganese leaching rate in actual production, and further prolonging the duration of curing may cause waste of energy and increase costs.
Description
Each embodiment in the description is described in a progressive way. The difference of each embodiment from each other is the focus of explanation. The same and similar parts among all of the embodiments can be referred to each other. For the device disclosed by the embodiments, because the device corresponds to a method disclosed by the embodiments, the device is simply described. Refer to the description of the method part for the related part.
The above description of the disclosed embodiments enables those skilled in the art to realize or use the present invention. Many modifications to these embodiments will be apparent to those skilled in the art. The general principle defined herein can be realized in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown herein, but will conform to the widest scope consistent with the principle and novel features disclosed herein.
Claims (5)
- Claims 1. A method for leaching manganese from electrolytic manganese anode slag, specifically comprising the following steps:(1) weighing electrolytic manganese anode slag, sulfur powder and concentrated sulfuric acid as required for later use;(2) adding the sulfur powder and the concentrated sulfuric acid to the electrolytic manganese anode slag, mixing evenly, and performing curing to obtain clinker; and(3) adding water to the clinker for leaching, and performing liquid-solid separation to obtain manganese-containing leaching solution and leaching slag.
- 2. The method for leaching manganese from electrolytic manganese anode slag according to claim 1, wherein the mass concentration of the concentrated sulfuric acid is greater than 95%, and the purity of the sulfur powder is greater than 99%; in the step (1), the mass ratio of the sulfur powder to the electrolytic manganese anode slag is (10-16):100; and the mass ratio of the electrolytic manganese anode slag to the concentrated sulfuric acid is (0.8-1.4):1.
- 3. The method for leaching manganese from electrolytic manganese anode slag according to claim 2, wherein in the step (2), the temperature of the mixing is 15-30°C; the temperature of the curing is 100-150°C, and the duration is 10-24h.
- 4. The method for leaching manganese from electrolytic manganese anode slag according to claim 1, wherein in the step (3), water is added until the liquid-solid volume mass ratio is (2-3) L:1 Kg, the leaching temperature is 15-30°C, the pressure is 1.0*105 Pa, and the duration is 0.5-lh.
- 5. The method for leaching manganese from electrolytic manganese slag according to any one of claims 1-4, further comprising a step (4): removing heavy metals from the manganese-containing leaching solution to obtain manganese sulfate solution, and drying the leaching slag to obtain lead concentrate.
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