NL2033446B1 - Method for extracting manganese from modified manganese-rich slag by acid leaching - Google Patents
Method for extracting manganese from modified manganese-rich slag by acid leaching Download PDFInfo
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- manganese
- rich slag
- leaching
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- 239000011572 manganese Substances 0.000 title claims abstract description 139
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 121
- 239000002893 slag Substances 0.000 title claims abstract description 118
- 238000002386 leaching Methods 0.000 title claims abstract description 106
- 239000002253 acid Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 53
- 150000002696 manganese Chemical class 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 230000004048 modification Effects 0.000 claims abstract description 23
- 238000012986 modification Methods 0.000 claims abstract description 23
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 230000000051 modifying effect Effects 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003245 coal Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 238000007789 sealing Methods 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 235000002908 manganese Nutrition 0.000 description 99
- 239000000395 magnesium oxide Substances 0.000 description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 20
- 239000012298 atmosphere Substances 0.000 description 16
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 16
- 229940099596 manganese sulfate Drugs 0.000 description 15
- 239000011702 manganese sulphate Substances 0.000 description 15
- 235000007079 manganese sulphate Nutrition 0.000 description 15
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 15
- 239000012535 impurity Substances 0.000 description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 238000006011 modification reaction Methods 0.000 description 8
- 230000001603 reducing effect Effects 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000000292 calcium oxide Substances 0.000 description 7
- 235000012255 calcium oxide Nutrition 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910001720 Åkermanite Inorganic materials 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009850 completed effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 229910052909 inorganic silicate Inorganic materials 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012213 gelatinous substance Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 ca*% Chemical class 0.000 description 1
- UMRUNOIJZLCTGG-UHFFFAOYSA-N calcium;manganese Chemical group [Ca+2].[Mn].[Mn].[Mn].[Mn] UMRUNOIJZLCTGG-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical group [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 230000009466 transformation Effects 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
- 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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
-
- 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
-
- 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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- 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
The present disclosure discloses a method for extracting manganese from modified manganese—rich slag by acid leaching and belongs to the technical field of metallurgy and chemical industry. The method comprises the following steps: modification of manganese— 5 rich slag: modification of manganese—rich slag: mixing manganese— rich slag and a modifying agent uniformly according to a certain mass ratio, and placing the mixture in a container and covering a layer of carbonaceous material on the surface of the mixture, covering and sealing the container to keep the mixture in a molten 10 state, and keeping warm for a period of time; grinding; acid leaching, and separation, to obtain an acid leaching solution.
Description
METHOD FOR EXTRACTING MANGANESE FROM MODIFIED MANGANESE-RICH SLAG
BY ACID LEACHING
The present disclosure belongs to the technical field of met- allurgy and chemical industry, and more specifically relates to a method for extracting manganese from modified manganese-rich slag by acid leaching.
In recent years, with the development and transformation of the national economy, the demand for manganese in high-end indus- tries, such as the field of new energy battery, has increased rap- idly. As an important component of ternary cathode material of lithium-ion batteries, manganese plays an extremely important role in the safety and stability of lithium-ion batteries. High-purity manganese sulfate is the manganese source of the ternary precur- sor. In 2021, the consumption of high-purity manganese sulfate is 160,000 tons. If it is calculated based on 25 million new energy vehicles in the world in 2025, it is expected that the demand for high-purity manganese sulfate will reach 700,000 tons. Therefore, with the continuous development of new energy industry in China, the demand for manganese will have an increasing trend year by year.
Manganese ore is a strategic resource in the development of cutting-edge material industries such as new energy, chemical, steel in China, which has a very important position in the process of national economic growth and social development. However, the manganese ores are distributed extremely uneven across the world.
The existing reserves of manganese ore in China only account for approximately 6% of the global total reserves, and the main type of ore is manganese carbonate ore with manganese grade less than 20% and high phosphorus, high iron and high silicon. The reserves of high-grade ores such as pyrolusite and braunite are very scarce, therefore it is necessary to enrich manganese through ben-
eficiation. The blast furnace smelting of manganese-rich slag is a method of pyrometallurgical beneficiation to enrich manganese; ac- cording to the method, the refractory manganese ore with high iron and high phosphorus that cannot be directly used for smelting is subjected to selective reduction in the blast furnace, and the re- duction of manganese is suppressed on the premise of ensuring the sufficient reduction of elements such as Fe and P, thereby obtain- ing manganese-rich slag with high manganese and low iron. The man- ganese content in the manganese-rich slag is generally 30%-45%, and its main mineral phase is calcium manganese olivine.
The conventional technological process of extracting manga- nese from manganese-rich slag can be divided into two types: pyro- genic process and wet process. For pyrogenic process, generally silicon-manganese alloy is produced by high temperature furnace, for example, the Chinese patent with publication number
CN109295364A discloses a method and a device for preparing manga- nese-silicon alloy by using manganese-rich slag, but the pyrogenic process has a long process and high energy consumption, and is not widely used; for the wet process, generally manganese-rich slag is treated by acid leaching method, for example, the Chinese patent with publication number CN102605186A discloses a method for pro- ducing manganese sulfate by atmospheric leaching of manganese-rich slag, however, because manganese exists in the main form of Mn;SiO, in the manganese-rich slag, Sio,® enters the solution to form a gelatinous silicic acid when Mn® is dissolved and adsorb Mn* in a large amount, which make the solution difficult to filter, and the extraction rate of manganese is low. In addition, the ions such as ca*%, Mg?%, Al dissolved simultaneously in the acid leaching pro- cess bring a burden to the subsequent impurity removal of the so- lution. The method consumes a large amount of acid, is difficult to operate, and has a low extraction rate of manganese.
In order to solve this problem, the Chinese patent
CN114086004A discloses a method for selectively and efficiently extracting manganese from manganese-rich slag. According to the disclosure, manganese-rich slag powder is fully mixed with a modi- fying agent containing calcium oxide, modified for a period of time at a temperature higher than 1,200°C and then ground to obtain calcium-modified manganese-rich slag powder, and finally acid leaching is performed to extract manganese, wherein the mixture is heated to melting in a reducing or inert atmosphere in the modifi- cation reaction. However, this technology needs to be carried out in a reducing or inert atmosphere; and the atmosphere is prone to change or fluctuate during the experiment, which affects the ex- perimental results, leading to incapability to modify completely, low reproducibility, adaptability, stability, and poor applicabil- ity; and in the actual production process of manganese-rich slag, the slagging temperature is 1150~1250°C; while this technology re- quires a reaction temperature of 1200~1500°C, which is unable to meet the temperature requirement in case of no thermal compensa- tion, and thus complete modification cannot be achieved. In addi- tion, the Chinese patent CN105925812A discloses a method for ex- tracting manganese from manganese-rich slag. In order to effec- tively leaching high-valent manganese slag oxides (such as MnO;) contained in manganese-rich slag, reducing materials such as car- bon, FeS, etc., which are not higher than 10% by mass of manga- nese-rich slag, are added to the mixed slurry of manganese-rich slag and sulfuric acid solution. The disadvantage is that the add- ed reducing substance needs to be mixed with the slurry uniformly to react completely. The reducing substance is a solid powder, which is easy to agglomerate in the slurry and is difficult to distribute evenly, and cannot meet the kinetic conditions, so the reaction is incomplete. In addition, there is excessive local dis- tribution, leading to over-reduction, with an average leaching rate of Mn of only 91.8% in the four examples.
1. Problems to be solved
To solve the problem of incomplete modification of manganese- rich slag in the existing manganese extracting technology from manganese-rich slag, the present disclosure provides a method for extracting manganese from modified manganese-rich slag by acid leaching. The method can effectively improve the reaction atmos- phere and temperature conditions, provide necessary thermal com- pensation, reasonably utilize the sensible heat of the high-
temperature thermal state manganese-rich slag, and ensure that the high-temperature modification reaction is complete. 2. Technical solutions
In order to solve the above problem, the present disclosure adopts the following technical solutions:
A method for extracting manganese from modified manganese- rich slag by acid leaching specifically comprises the following steps:
Step S81, modification of manganese-rich slag: mixing manga- nese-rich slag and a modifying agent uniformly according to a cer- tain mass ratio, and placing the mixture in a container and cover- ing a layer of carbonaceous material on the surface of the mix- ture, covering and sealing the container to keep the mixture in a molten state, and keeping warm for a period of time;
Step 52, grinding: carrying out crushing and grinding after the modified manganese-rich slag is cooled to room temperature;
Step S3, acid leaching: leaching the modified manganese-rich slag with an acid solution, and stirring during the leaching pro- cess;
Step S4, separation: performing separation after completion of leaching to obtain an acid leaching solution.
After testing, in the acid leaching solution obtain in the step S4, the leaching rate of Mn is greater than 98%, the leaching rate of Ca and Mg is less than 10%, and the leaching rate of Si and Al is less than 1%.
Wherein, in the step 81, the modifying agent is MgO, and the
MgO has a purity of greater than 99.9% and a particle size of less than 100 meshes. The mass ratio of the modifying agent to the man- ganese-rich slag is (25-50): (75-50). The mass percentage of the modifying agent is 10-50%, and the mass percentage of manganese- rich slag is 50-90%.
The carbonaceous material can be carbon powder, or coke pow- der, coal powder or straw powder, preferably carbon powder. The particle size of the carbonaceous material is less than 100 mesh- es, and the addition amount of the carbonaceous material is 10 wt % to 100 wt % of the mixture, to achieve the effect of isolating oxygen.
In the prior art, calcium oxide, quicklime, limestone or slaked lime is used as a modifying agent, for example, in the Chi- nese patent CN114086004A, quicklime, limestone or slaked lime con- tain a large amount of impurity oxides such as Al;0: and 510; and 5 other trace elements, and Al.0; needs to be added in the modifica- tion reaction 2Ca0 + Mn.Si0; + Al;0:= Ca:Al1-Si0; + 2Mn0, which fur- ther increases the amount of impurity elements, resulting in a low average extraction rate of Mn of 92.46%; the average dissolution rate of Ca is 23.44%, the average dissolution rate of Si is 21.48%, and the average dissolution rate of Al is 16.94%; the high dissolution rate of impurity components will inhibit the dissolu- tion rate of Mn and cause the content of manganese sulfate in the solution to reduce greatly. Therefore, although the calcium oxide, quicklime, limestone or slaked lime as the modifying agent im- proves the dissolution rate of Mn, new impurities are introduced, the concentration of manganese sulfate in the solution is reduced, the amount of acid used is increased and subsequent removal of im- purities is required, having a certain negative role.
Therefore, the present disclosure uses MgO as the modifying agent, and MgO reacts chemically with glaucochroite CaMn[Si0:;] at 1100° €¢-1500° C to generate manganous oxide MnO and calcio aker- manite CaMg[SiO4]. In the process of sulfuric acid leaching of MgO- modified manganese-rich slag, the generation of gelatinous sub- stances is significantly reduced, thereby effectively reducing the amount of acid used, improving the leaching rate of Mn, and ob- taining high-purity manganese sulfate solution; in addition, high- purity MgO is used to avoid the introduction of a large amount of impurity elements, and the leaching rate of Ca, Mg, Si and Al is reduced, further increasing the concentration of manganese sul- fate. Its basic principle is as follows: manganese in manganese- rich slag mainly exists in the form of glaucochroite CaMn[3i0,].
Based on the fact that the binding ability of Mg and silicon- oxygen tetrahedron is greater than that of Mn and silicon-oxygen tetrahedron, Mg is used to replace Mn from the network structure of the silicon-oxygen tetrahedron, and high-purity magnesium oxide
MgO react with glaucochroite CaMn[SiO,4] chemically at 1100°C - 1500°C, to generate manganous oxide MnO and calcio akermanite
CaMg[SiO:], to complete the modification of manganese-rich slag, as shown in the reaction formula (1). Based on the difference in sol- ubility between manganous oxide MnC and calcio akermanite
CaMg [Si0;] in sulfuric acid, and [Si0,]% has a small solubility product and slow diffusion in the acid solution, low-concentration sulfuric acid is used to leach out manganese from modified manga- nese-rich slag to obtain a high-purity manganese sulfate solution.
MgO+CaMn [SiO0,;]=MnO+CaMg [SiO0:] (1)
In the prior art, the modification reaction is carried out in a reducing or inert atmosphere. For example, the patent
CN114086004A discloses a method for selectively and efficiently extracting manganese from manganese-rich slag, wherein the reduc- ing atmosphere is composed of CO/CO: or H:/H:0 gas mixture, the partial pressure ratio of CO:/CO should be not less than 5.6*10%, and the partial pressure ratio of H;0/H: should be not less than 5.6*10?. If the atmosphere changes or fluctuates during the exper- iment, it will produce a great impact on the experimental results, resulting in low reproducibility, adaptability and stability of the technology. In addition, it is necessary to introduce gas all the time during the reaction, resulting in a high cost and a poor applicability. Therefore, in the present disclosure, the surface of the mixture of manganese-rich slag and modifying agent is cov- ered with a layer of carbonaceous material, which can act as an oxygen barrier and can effectively avoid the impact of oxidative atmosphere on the modification reaction; and there is no need of reducing atmosphere or other atmosphere as a reaction condition; the heat released by the heating of carbonaceous substances such as carbon powder can effectively improve the reaction temperature conditions, provide necessary thermal compensation, reasonably utilize the deslagging sensible heat of the high-temperature ther- mal state manganese-rich slag, and ensure that the high- temperature modification reaction is complete; in addition, carbon powder, coke powder and coal powder are easy to obtain and store, which greatly improves the reproducibility, adaptability, stabil- ity and applicability of the technology.
The container can be a crucible, and the material of the cru- cible and the crucible cover is high-strength self-bonding silicon carbide, and the silicon carbide content is299%. Compared with the container made of Al:0:, the container made of silicon carbide can avoid the reaction between manganese-rich slag and the container.
In the reaction process, the crucible is covered and sealed, which can play the role of heat preservation and oxygen isolation, is conductive to saving the heat generated by the combustion of the carbonaceous material, and realizes the thermal compensation. In addition, the addition amount of the carbonaceous material is 10 wt$-100 wt% of the mixture in the present disclosure. The carbona- ceous material layer is relatively thin in this mass fraction range, and the sealing with a cover can reduce the amount of the introduced oxygen.
Wherein, the manganese-rich slag can be cold state manganese- rich slag, or high-temperature thermal state manganese-rich slag; when the manganese-rich slag is cold state manganese-rich slag, the cold state manganese-rich slag is crushed and ground to a cer- tain particle size before modification, mixed evenly with high- purity MgO in a certain mass ratio, placed into a container, cov- ered with a layer of carbonaceous material on the surface of the mixture, heated to 1100~1500°C to melt the mixture and kept warm for 10-180 min; when the manganese-rich slag is a high-temperature thermal state manganese-rich slag, the manganese-rich slag is di- rectly mixed with high-purity magnesium oxide MgO in a certain mass ratio, placed into a container, covered with a layer of car- bonaceous material on the surface of the mixture; there is no need to heat, and the heat released by carbon powder is used for heat compensation, and the temperature is kept for 10-180 min. There is no requirement on the atmosphere during the heating process.
Preferably, the cold state manganese-rich slag is crushed and ground to below 100 meshes, and the temperature of the high- temperature thermal state manganese-rich slag is 1150-1350°C.
Preferably, in the step $2, the modified manganese-rich slag is ground and crushed to below 150 meshes.
Preferably, the acid solution in the step 83 is sulfuric acid to obtain the manganese sulfate solution. The concentration of the acid solution is 0.1-1.0 mol/L, the leaching time is 10-180 min, and the leaching temperature is 50-90°C. In addition, the acid so-
lution can also be hydrochloric acid or nitric acid to obtain the manganese chloride or manganese nitrate solution. The type of acid and acid leaching process parameters are adjusted according to the desired product. 3. Beneficial effects
Compared with the prior art, the present disclosure has the following beneficial effects: (1) According to the present disclosure, the surface of the mixture is covered with a layer of carbonaceous material, which can act as an oxygen barrier and can effectively avoid the impact of oxidative atmosphere on the modification reaction; the heat re- leased by the heating of carbonaceous substances such as carbon powder can provide thermal compensation, utilize the deslagging sensible heat of the high-temperature thermal state manganese-rich slag, and ensure that the high-temperature modification reaction is complete; in addition, carbon powder, coke powder and coal pow- der are easy to obtain and store, which improves the reproducibil- ity, adaptability, stability and applicability of the technology; (2) According to the present disclosure, high-purity MgO is used to modify manganese-rich slag, and the leaching rate of Mn is significantly enhanced, wherein the leaching rate of Mn is greater than 928%, the leaching rate of Ca and Mg is less than 10%, and the leaching rate of Si and Al is less than 1%; various indicators have improved remarkably; (3) There is few impurity introduced in the present disclo- sure. On the one hand, the technology adopts high-purity MgO, the purity is »99.9%, and almost no impurity elements are introduced; on the other hand, since the acid solubility of divalent manganese is much better than manganese in other valence states, it is nec- essary to add an oxidizing agent or a reducing agent to bring in impurities in the conventional acid leaching process of manganese- rich slag. This technical solution avoids the impact of the atmos- phere; manganese is completely generated to manganous oxide MnO, and the valence state remains unchanged, avoiding the introduction of impurities; {4) The amount of acid used in the method of the present dis- closure is dramatically reduced; on the one hand, the leaching rate of the impurity element is low, acid is mainly used for acid leaching of manganous oxide MnO, reducing the acid consumption; on the other hand, the acid concentration for acid leaching modifica- tion of manganese-rich slag is only 0.05-1.0 mol/L, which is lower than the concentration of conventional acid leaching (>1mol/L).
The two factors make the acid consumption to drop dramatically; (5) The leaching rate of silicon and aluminum of the present disclosure is low. Compared with the acid leaching process of man- ganese-rich slag in the prior art, the leached silicon forms ge- latinous silicic acid in the solution, which is one of the main reasons for the low leaching rate of manganese. In the present disclosure, the leaching rate of Si and Al is less than 1%, almost no gelatinous silicic acid is generated, which significantly re- duces the consumption of acid, enhances the filterability, reduces the pressure of subsequent impurity removal, and provides conven- ience for the deep preparation of high-purity manganese sulfate.
The technical sclutions of the present disclosure will be further described in detail below with reference to the accompany- ing drawings and embodiments, but it should be appreciated that these drawings are designed for the interpretation only, and therefore are not intended to limit the scope of the present dis- closure. Furthermore, unless otherwise indicated, these drawings are intended only to conceptually illustrate the structural con- figurations described herein and are not necessarily drawn to scale.
FIG. 1 shows the XRD patterns of the manganese-rich slag be- fore modification and after modification, wherein the Line-A is the XRD pattern of the unmodified manganese-rich slag, and the
Line-B is the XRD pattern of modified manganese-rich slag;
FIG. 2 shows the acid leaching sclution of Example 1;
FIG. 3 shows the acid leaching solution of Comparative Exam- ple 1;
FIG. 4 shows the XRD pattern of the manganese-rich slag after modification of Example 2;
FIG. 5 shows the acid leaching solution of Example 2;
FIG. 6 shows the acid leaching solution of Example 3.
The following detailed description of exemplary embodiments of the present disclosure refers to the accompanying drawings, which form a part hereof, and illustrate, by way of example, exem- plary embodiments of the present disclosure in which the present disclosure may be implemented. Although these exemplary embodi- ments have been described in sufficient detail to enable those skilled in the art to implement the present disclosure, it should be understood that other embodiments may be realized and various changes may be made without departing from the spirit and scope of the present disclosure. The following more detailed description of embodiments of the present disclosure is not intended to limit the scope of the present disclosure as claimed, but is intended to il- lustrate and not limit the description of the features and charac- teristics of the present disclosure to propose the best embodi- ments of the present disclosure, and is sufficient to enable those skilled in the art to implement the present disclosure. Therefore, the scope of the present disclosure is to be limited only by the appended claims.
Example 1
Step S1, modification of manganese-rich slag: crush and grind the cold state manganese-rich slag to less than 200 meshes, take samples for X-ray fluorescence spectrometry (XRF) and X-ray dif- fraction (XRD) analysis. Its chemical components and phase compo- sitions are shown in Table 1 and FIG. 1 Line-A, respectively. It can be seen that the manganese in the manganese-rich slag before modification mainly exists in the form of glaucochroite
CaMn[Si04]. Mix 5 g of high-purity magnesium oxide MgO with 15 g of manganese-rich slag uniformly, place the mixture into a high- purity SiC crucible, and cover the surface of the mixture with a layer of carbon powder, wherein the particle size of the carbon powder is 200 meshes and the mass of the carbon powder is 20 g.
Cover the crucible with a high-purity SiC cover, heat to 1100°C, and keep warm for 180 min. There is no atmosphere requirement dur- ing the heating process. After the heat preservation is completed,
the temperature is reduced to room temperature to complete the modification of manganese-rich slag;
Table 1 Chemical components of manganese-rich slag (%) “Component MnO SiO, ALO; CaO MgO Fe,0, KO 50; Na0 TO,
Content 385 266 158 95 24 17 17 15 11 06
EE —
Step S2, grinding: carry out crushing and grinding to below 200 meshes after the modified manganese-rich slag is cooled to room temperature. The X-ray diffraction analysis (XRD) is carried out. The result is shown in FIG. 1 Line-B. Compared with before modification, manganous oxide MnO and calcio akermanite CaMg[Si04] are generated in the modified manganese-rich slag;
Step 83, acid leaching: leach the modified manganese-rich slag with 1.0 mol/L H;S0; at room temperature; wherein the leaching time is 180 min, and the leaching temperature is 80°C; stir during the leaching process;
Step S4, separation: perform suction filtration for separa- tion after completion of leaching to obtain an acid leaching solu- tion containing manganese sulfate, as shown in FIG. 2, the acid leaching solution is a flesh-colored solution.
The acid leaching solution is detected by an inductively cou- pled plasma spectrometer (ICP), and after calculation, the leach- ing rate of Mn is 98.6%, and the leaching rates of Ca, Mg, Si, and
Al are 8.6%, 9.8%, 0.58%, and 0.27%, respectively.
Comparative Example 1
A method for extracting manganese from manganese-rich slag by acid leaching is different from Example 1 in that the manganese- rich slag is an unmodified cold state manganese-rich slag. The method specifically comprises the following steps:
Step S1, grinding: crush and grind the cold state manganese- rich slag to below 200 meshes (75 microns);
Step S2, acid leaching: carry out acid leaching of 15 g of manganese-rich slag directly without modification treatment; leach the manganese-rich slag with 1.0 mol/L H-S0,4 at room temperature; wherein the leaching time is 180 min, and the leaching temperature is 80°C; stir during the leaching process;
Step S3, separation: perform suction filtration for separa- tion after completion of leaching to obtain an acid leaching solu- tion containing manganese sulfate, as shown in FIG. 3, there is a clear gelatinous substance produced. After testing, the leaching rate of Mn is 18.6%, and the leaching rates of Ca, Mg, Si and Al are 23.7%, 33.8%, 10.2% and 17.5%, respectively.
Example 2
A method for method for extracting manganese from modified manganese-rich slag by acid leaching specifically comprises the following steps:
Step S81, modification of manganese-rich slag: crush and grind manganese-rich slag to 150 meshes, take 30 g of manganese-rich slag and heat to 1250°C, simulate the deslagging process of blast furnace smelting of manganese-rich slag, place 15 g of high-purity magnesium oxide MgO at the bottom of the high-purity SiC crucible in advance, pour the high-temperature thermal state manganese-rich slag into a SiC crucible, stir evenly, and cover the surface of the mixture with a layer of coke powder, wherein the particle size of the carbon powder is 200 meshes and the mass of the carbon pow- der is 25 g. Cover the crucible with a high-purity SiC lid, keep warm at 1250°C for 100 min; there is no atmosphere requirement during the heating process. After the heat preservation is com- pleted, the temperature is reduced to room temperature to complete the modification of manganese-rich slag;
Step S2, grinding: carry out crushing and grinding to below 200 meshes after the modified manganese-rich slag is cooled to room temperature. The X-ray diffraction analysis (XRD) is carried out. The result is shown in FIG. 4. Compared with before modifica- tion, manganous oxide MnO and calcio akermanite CaMg[SiO,4] are gen- erated in the modified manganese-rich slag;
Step S3, acid leaching: leach the modified manganese-rich slag with 0.3 mol/L H,S0; at room temperature; wherein the leaching time is 100 min, and the leaching temperature is 90°C; stir during the leaching process;
Step S4, separation: perform suction filtration for separa-
tion after completion of leaching to obtain an acid leaching solu- tion containing manganese sulfate, as shown in FIG. 5, the acid leaching solution is a flesh-colored solution.
The acid leaching solution is detected by an inductively cou- pled plasma spectrometer (ICP), and after calculation, the leach- ing rate of Mn is 98.1%, and the leaching rates of Ca, Mg, Si, and
Al are 8.2%, 9.4%, 0.58%, 0.0%, respectively.
Example 3
A method for method for extracting manganese from modified manganese-rich slag by acid leaching specifically comprises the following steps:
Step S81, modification of manganese-rich slag: crush and grind cold state manganese-rich slag to less than 100 meshes, mix 50 g of high-purity magnesium oxide MgO with 50 g of manganese-rich slag, place them into a high-purity SiC crucible, cover the sur- face of the mixture with a layer of coke powder, wherein the par- ticle size of the coke powder is 200 meshes and the mass of the coke powder is 10 g. Cover the crucible with a high-purity SiC lid, heat to 1500°C, and keep warm for 10 min; there is no atmos- phere requirement during the heating process. After the heat preservation is completed, the temperature is reduced to room tem- perature to complete the modification of manganese-rich slag;
Step S82, grinding: carry out crushing and grinding to below 200 meshes after the modified manganese-rich slag is cooled to room temperature;
Step 83, acid leaching: leach the modified manganese-rich slag with 0.1 mol/L H.SC, at room temperature; wherein the leaching time is 60 min, and the leaching temperature is 50°C; stir during the leaching process;
Step S4, separation: perform suction filtration for separa- tion after completion of leaching to obtain an acid leaching solu- tion containing manganese sulfate, as shown in FIG. 6, the acid leaching solution is a flesh-colored solution.
The acid leaching solution is detected by an inductively cou- pled plasma spectrometer (ICP), and after calculation, the leach- ing rate of Mn is 98.3%, and the leaching rates of Ca, Mg, Si, and
Al are 8.5%, 9.9%, 0.38%, 0.05%, respectively.
Table 2 Parameters in each example of the present disclosure
Example 1 Example 2 Example 3 Comparative mm eT
Particle size of man- 200 meshes 150 meshes 100 meshes | 200 meshes ee ee ee eeen Woo we
Carbonaceous mate- | Carbon pow- Coke powder Coal powder
Modifying agent: 5:15 15:30 50:50
Ke
Carbonaceous mate- | 20:20 25:45 10: 100 rial: (manganese-rich slag+modifying agent)
Teper EE
Time of keeping 180 100 10
Ea A
Concentration 1.0 0.3 0.1 10 ma ese OE
Leaching tempera- 50
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| CN113832357B (en) * | 2021-09-24 | 2023-02-24 | 湖南金龙新材料有限公司 | Method for preparing high-performance oxygen-free copper by using reclaimed copper |
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