CN114086004A - Method for selectively and efficiently extracting manganese from manganese-rich slag - Google Patents
Method for selectively and efficiently extracting manganese from manganese-rich slag Download PDFInfo
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- CN114086004A CN114086004A CN202111403933.1A CN202111403933A CN114086004A CN 114086004 A CN114086004 A CN 114086004A CN 202111403933 A CN202111403933 A CN 202111403933A CN 114086004 A CN114086004 A CN 114086004A
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- rich slag
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- 239000011572 manganese Substances 0.000 title claims abstract description 158
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 141
- 239000002893 slag Substances 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 72
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000002386 leaching Methods 0.000 claims abstract description 56
- 239000002253 acid Substances 0.000 claims abstract description 50
- 239000000292 calcium oxide Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 27
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 17
- 150000002696 manganese Chemical class 0.000 claims abstract description 16
- 239000003607 modifier Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 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 abstract description 6
- 238000006011 modification reaction Methods 0.000 claims abstract description 6
- 235000012255 calcium oxide Nutrition 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- 235000019738 Limestone Nutrition 0.000 claims description 5
- 239000006028 limestone Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000011112 process operation Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 31
- 239000000243 solution Substances 0.000 description 26
- 238000004090 dissolution Methods 0.000 description 24
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 239000011575 calcium Substances 0.000 description 17
- 238000000605 extraction Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 230000002572 peristaltic effect Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000001502 supplementing effect Effects 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229910052918 calcium silicate Inorganic materials 0.000 description 5
- -1 ferrous metals Chemical class 0.000 description 5
- 229910001719 melilite Inorganic materials 0.000 description 5
- 229910052609 olivine Inorganic materials 0.000 description 5
- 239000010450 olivine Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910052909 inorganic silicate Inorganic materials 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 235000012241 calcium silicate Nutrition 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001678 gehlenite Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000914 Mn alloy Inorganic materials 0.000 description 2
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 2
- UMRUNOIJZLCTGG-UHFFFAOYSA-N calcium;manganese Chemical compound [Ca+2].[Mn].[Mn].[Mn].[Mn] UMRUNOIJZLCTGG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910020472 SiO7 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052840 fayalite Inorganic materials 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 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
- 239000012528 membrane Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052841 tephroite Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- 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
- C22B7/04—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)
- 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)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for selectively and efficiently extracting manganese resources from manganese-rich slag, and belongs to the technical field of metallurgical chemical industry. The method comprises the steps of fully mixing manganese-rich slag powder with a modifier containing calcium oxide, modifying for a period of time at the temperature higher than 1200 ℃, grinding to obtain calcium-modified manganese-rich slag powder, and finally performing acid leaching to extract manganese, wherein the modification reaction is heated to be molten in a reducing or inert atmosphere. The method can selectively separate manganese element from manganese-rich slag with low cost, high efficiency and convenience, has the advantages of high selectivity, low acid consumption, simple process operation and the like, and has important significance for the utilization of low-grade manganese ore resources.
Description
Technical Field
The invention belongs to the technical field of metallurgical chemical industry, and particularly relates to a method for selectively extracting and separating manganese resources from manganese-rich slag.
Background
China has relatively abundant manganese ore resources, but the main ore type is manganese carbonate ore with the manganese grade lower than 20 percent, high phosphorus, high iron and high silicon, and the high-grade ore reserves such as pyrolusite and limonite are very rare. In order to improve the utilization rate of lean ore resources, the lean manganese ore is enriched in a blast furnace by a common domestic pyrometallurgy ore dressing method to obtain manganese-rich slag. Because of the huge demand of manganese in the steel industry, the manganese-rich slag is mainly used as a smelting raw material of manganese-silicon alloy for a long time, and the additional value is low. In recent years, the demand of high-end industries for manganese is rapidly increased, such as the fields of energy sources and catalysis, the demand of high-purity manganese sulfate in China reaches 15 ten thousand tons in 2018, and the demand shows a trend of increasing year by year. Therefore, the manganese resource purified from the manganese-rich slag can be used as high added value of poor manganese ore in China.
The traditional process for extracting manganese from manganese-rich slag can be divided into a fire method and a wet method, wherein the fire method and the wet method are generally used for producing silicon-manganese alloy by using a submerged arc furnace and then obtaining manganese metal by smelting in an electric arc furnace, and the method has long flow and large energy consumption; the latter is usually carried out by acid leaching of manganese-rich residues, since manganese is present as olivine (Mn)2SiO4) Mainly exists in the form of Mn2+At the same time of dissolution, SiO4 4-Enter the solution to form gel silicic acid and adsorb Mn in large quantity2+Not only causes difficulty in solution filtration but also has a low extraction rate of manganese, on the other hand, Ca dissolved out synchronously in the acid leaching process2+,Mg2+,SiO4 4-,[AlO2]-The plasma brings burden to the subsequent solution impurity removal, and the method has the advantages of large acid consumption, difficult operation and low manganese extraction rate. Currently, there is still a lack of an economical and efficient process for selectively extracting manganese from manganese-rich slag.
Through search, the patent application with the Chinese patent application number of 201610320980.2 and the application publication date of 2016, 9, 7 discloses a method for extracting manganese from manganese-rich slag. The method of the patent comprises: (1) mixing the manganese-rich slag with a sulfuric acid solution to obtain a mixed slurry, wherein the mass fraction of sulfuric acid in the sulfuric acid solution is not lower than 70%, and the manganese-rich slag is a product obtained by producing iron-manganese alloy through pyrometallurgy of manganese ore; (2) preserving the heat of the mixed slurry at a temperature of not lower than 50 ℃; (3) roasting the product after heat preservation treatment, wherein the roasting temperature is controlled to be not lower than 150 ℃, and the roasting time is not less than 30 min; (4) leaching the roasted product, and carrying out solid-liquid separation to obtain a manganese sulfate solution. However, the manganese-rich slag in the process is not modified, and when the manganese is leached by directly adopting sulfuric acid, a large amount of elements such as calcium, silicon, aluminum and the like in the manganese-rich slag are dissolved out, the acid consumption is high, the impurity content in the solution is high, and the difficulty is brought to the subsequent separation and purification of manganese in the aqueous solution.
Chinese patent application No. 201910873691.9, whose publication date is 2019, 11 and 26, discloses a method for extracting manganese metal from manganese-rich slag. The method of this patent comprises the steps of: (1) grinding the manganese-rich slag ore to 250-mesh granularity by using a ball mill for later use, adding water into 100g of the grinded manganese-rich slag for size mixing to obtain mixed slurry, and adding the mixed slurry into a reaction vessel; (2) adding acid liquor in multiple steps in the reaction process, namely adding acid liquor dropwise for multiple times in the leaching time; (3) and (3) adding acid for multiple times at normal pressure for leaching, discharging to obtain an acid leaching mixture, and carrying out solid-liquid separation on the acid leaching mixture to separate out the metal manganese. However, the acid solution is still adopted for direct leaching in the process, elements such as silicon and aluminum are dissolved out synchronously, the acid consumption is large, and the economic benefit is poor.
In 2017, 6 and 12, in 2017, in 6 th and 74 th of 2017, in non-ferrous metals (smelting part), Role and the like disclose an article named as 'manganese slag harmless treatment technology based on quicklime strengthening treatment', the research uses acid leaching manganese slag as an object and quicklime as an additive, a manganese slag leachate is extracted by a turnover leaching method, the types and the concentrations of pollutants in the leachate are analyzed, and the influence and the optimal conditions of the addition amount of the quicklime, the water content of the manganese slag, the pre-reaction time and the like on the manganese slag harmless treatment are researched. The results show that the main pollutants in the manganese slag are manganese and ammonia nitrogen, and the concentration of the main pollutants is seriously exceeded. The hydration reaction of the quicklime forms a good alkaline environment, and plays a good role in harmless treatment by physical wrapping, adsorption and precipitation. However, the process only adopts the alkalinity of the quicklime to cure the pollutants in the manganese slag, does not modify the phase of the manganese slag, does not adopt manganese-rich slag as the raw material, and does not aim to separate valuable components from the manganese slag.
Therefore, there is a need for a method for selectively and efficiently extracting manganese from manganese-rich slag.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems in the existing method for extracting manganese from manganese-rich slag, the invention provides a method for selectively and efficiently extracting manganese from manganese-rich slag, which can be used for economically realizing the utilization of poor manganese ore resources in China by selectively separating manganese elements from manganese-rich slag with low cost, high efficiency and convenience, has the advantages of high selectivity, low acid consumption, simple process operation and the like, and has important significance for the utilization of low-grade manganese ore resources.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for selectively and efficiently extracting manganese from manganese-rich slag comprises the steps of fully mixing manganese-rich slag powder with a modifier containing calcium oxide, modifying at the temperature higher than 1200 ℃ for a period of time, grinding to obtain calcium-modified manganese-rich slag powder, and finally carrying out acid leaching to extract manganese, wherein a modification reaction is carried out under a reducing or inert atmosphere until the manganese is molten, so that manganese element is converted from insoluble olivine into manganese monoxide which is easily soluble in acid, and meanwhile, calcium-magnesium-silicon-aluminum is enriched in a spinel phase and an melilite phase; after the roasted product is cooled to room temperature, manganese elements are selectively leached from the roasted product by dilute acid by utilizing the solubility and dissolution rate difference of different phases.
Further, the modifier containing calcium oxide is calcium oxide, quicklime, limestone or hydrated lime.
Further, the content of CaO in the quicklime, limestone and hydrated lime is preferably higher, but the minimum content is not less than 40%. Mg, Al and Si in common impurities have influence on the modification effect; of course, other calcium salts can also be used as modifiers, such as calcium chloride, calcium sulfate, etc., but toxic gases are emitted in the process of using the calcium chloride and the calcium sulfate as the modifiers, and the problem of treating subsequent waste gas needs to be further solved.
Furthermore, the mass of the calcium oxide is 20-40% of that of the manganese-rich slag, and the calcium oxide is suitable for most of manganese-rich slag in China.
Further, the modification reaction temperature is 1200-1500 ℃.
Further, the modification time is 5 minutes to 180 minutes, and when the modification temperature is higher than 1000 ℃, the modification process is already started, and considering the time required for raising the temperature from 1000 ℃ to 1200 ℃ and the time required for lowering the temperature, the required modification time at 1200 ℃ is preferably short, and may be set to 5 minutes to 180 minutes.
Further, in order to promote the reaction in the low-temperature molten state, the particle size of the manganese-rich slag powder is preferably 100 mesh or less; the particle size of the calcium-modified manganese-rich slag powder is below 100 meshes.
Further, the acid used for acid leaching is hydrochloric acid, sulfuric acid or nitric acid.
Further, the pH value is controlled to be 1-5 during acid leaching, the pH value is controlled to be 1-5, the concentration of acid in the solution is low, the product of the concentrations of calcium ions and silicate ions is low, and the aim of selectively leaching manganese ions is fulfilled by inhibiting the leaching of impurity ions through pH regulation.
Further, the pickling time is at least 30 min.
The invention provides a method for selectively extracting and separating manganese element from manganese-rich slag, which comprises the following steps:
(1) crushing and ball-milling the manganese-rich slag to obtain manganese-rich slag powder, and then uniformly mixing the manganese-rich slag powder with a modifier containing calcium oxide, wherein the mass of the calcium oxide is 20-40% of that of the manganese-rich slag;
(2) heating the mixture to 1200-1500 ℃ in a reducing or inert atmosphere, preserving the heat for 1-3 hours, and naturally cooling to room temperature to obtain calcium-modified manganese-rich slag; wherein, the oxygen potential of the reducing atmosphere needs to be controlled, for example, pure CO gas can not be adopted, because MnO can be further reduced into metal manganese, the effect of acid leaching separation can not be achieved, and the reducing atmosphere is determined by CO/CO2Or H2/H2Composition of mixed gas of O and CO2The partial pressure ratio of CO should not be less than 5.6 x 10-5，H2O/H2Should not be less than 5.6 x 10-5。
(3) Crushing and grinding the calcium-modified manganese-rich slag to be below 100 meshes to obtain calcium-modified manganese-rich slag powder;
(4) 0.01-0.1mol/L HCl or sulfuric acid or nitric acid is adopted to leach the calcium modified manganese-rich slag powder at normal temperature, a peristaltic pump is adopted to supplement HCl in the leaching process, the pH value is controlled to be between 1 and 5, the dissolution of impurity ions is inhibited by utilizing the low concentration product of calcium ions and silicate ions in a dilute acid solution, the leaching time is 30min, the extraction rate of Mn can maximally reach over 95 percent, and the dissolution rates of Ca, Mg, Si and Al are all less than 25 percent.
The invention relates to a process method for extracting manganese from manganese-rich slag, which adopts the basic principle that Ca and SiO are utilized4]、[AlO4]The binding energy of the tetrahedron is larger than that of Mn, and the Mn-rich slag is modified at high temperature by CaO, and Mn is stripped from the network structure (fayalite) of the silicon-oxygen tetrahedron under the protective atmosphere, so that manganese is enriched in manganese monoxide which is easy to dissolve in dilute acid, and calcium, magnesium, aluminum and silicon are enriched in a spinel phase and a melilite phase which are difficult to dissolve in acid. Then use Ca2+And [ SiO ]4]4-、[AlO2]-Small solubility product in aqueous solution, and [ SiO ]4]4-、[AlO2]-The characteristic of slow diffusion in the Helmholtz layer is that low-concentration acid (1) is adopted<pH<5) Mn is leached from the modified slag, and selective and efficient separation is realized.
3. Advantageous effects
Compared with the prior art, the invention has the following beneficial effects:
(1) the method has the advantages of high manganese extraction rate: under the preferred conditions described above, the manganese extraction of the modified slag is up to 95%, while the manganese extraction of the unmodified manganese-rich slag is less than 20% under the same leaching conditions, for example 1;
(2) the acid dosage in the acid leaching process is greatly reduced: under the process condition, on one hand, the dissolution rate of impurity elements is low, and the acid is mainly used for dissolving out MnO phase; on the other hand, the acid concentration in the leaching process is only 0.05mol/L and is far lower than that in the conventional leaching process (the acid concentration is more than 1mol/L), and the acid consumption is greatly reduced due to two factors;
(3) the acid leaching process does not consume a reducing agent: because of the poor solubility of trivalent and quadrivalent manganese, a reducing agent needs to be added in the process of acid leaching of the manganese-rich ore, not only new impurities are brought to the acid leaching solution, but also the cost is increased, the process enables manganese to be separated out in a divalent state through the precise regulation and control of the phase, has good acid solubility, and does not need to add the reducing agent;
(4) the alkali consumption in the post-treatment process of the pickle liquor is greatly reduced: when the manganous-manganic oxide is prepared from the acid leaching solution, the pH value of the solution needs to be adjusted to 9-10, and the neutralization alkali consumption of the acid leaching solution is greatly reduced because the acid concentration is extremely low (1< pH <5) in the acid leaching process of the process;
(5) the process of the invention is simple to operate: a great deal of silicon and aluminum are dissolved out in the direct acid leaching process of the manganese-rich slag, flocculent gel (as shown in figure 1A) is formed in the solution along with the increase of the pH value of the solution, and not only a great deal of Mn is adsorbed2+The manganese extraction rate is low, and the micropores of the filter membrane are blocked, so that the solution filtration is quite difficult, the silicon-aluminum leaching rate in the process is low, the pickle liquor is clear liquor (shown in figure 1B), the filterability is high, and the operation is simple;
(6) the invention can fully utilize the sensible heat of the manganese-rich slag: at present, the manganese-rich slag produced by a small blast furnace mostly adopts a natural slow cooling mode, the sensible heat of the slag cannot be utilized, a modifier can be doped in the slag discharging process, and the sensible heat of the slag is fully utilized to realize the modification purpose.
Drawings
FIG. 1 is a comparison of an original manganese-rich slag and a modified slag leach solution;
FIG. 2 shows XRD patterns and matching results of original manganese-rich slag and modified slag prepared in example 1;
FIG. 3 shows the SEM results of the modified manganese-rich slag obtained in example 1 (sintering conditions: 25% CaO,1200 ℃ C., 1 hour);
FIG. 4 shows the extraction rates of different elements (extraction rates of Mn, Ca, Si, Al in the modified slag A; and extraction rates of Mn in the original slag and the modified slag B) in the original manganese-rich slag and the modified slag obtained in example 1.
FIG. 5 shows the XRD results of the modified manganese-rich slag obtained in example 2 (calcination conditions: 20% CaO,1200 ℃ C., 1 hour);
FIG. 6 shows the XRD results of the modified manganese-rich slag obtained in example 3 (calcination conditions: 40% CaO,1200 ℃ C., 1 hour);
FIG. 7 shows the XRD results of the modified manganese-rich slag obtained in example 4 (calcination conditions: 25% CaO,1500 ℃ C., 1 hour);
FIG. 8 shows the SEM results for the modified manganese-rich slag obtained in example 5 (calcination conditions: 36.7% hydrated lime, 1200 ℃ C., 1 hour).
FIG. 9 shows the XRD results (calcination conditions: 25% CaO,1000 ℃ C., 1 hour) of the modified manganese-rich slag obtained in comparative example 1.
Detailed Description
The invention is further described with reference to specific examples.
The main principle of the invention is as follows:
(1) using Ca and SiO4]、[AlO4]The binding energy of the tetrahedron is larger than that of Mn, CaO and manganese-rich slag are co-melted at 1200 ℃, a MnO phase and a gehlenite phase are separated out under a protective atmosphere, and the main reaction equation in the process is as follows:
2CaO+Mn2SiO4+Al2O3＝Ca2Al2SiO7+2MnO (1)
(2) by utilizing the solubility and dissolution rate difference of the manganese monoxide, the spinel and the melilite in a dilute acid solution and adopting the dilute acid to selectively leach manganese elements from the modified manganese-rich slag, the aim of low-cost and high-efficiency separation is fulfilled.
Example 1
Drying the manganese-rich slag, placing the manganese-rich slag into a powder tank for grinding for 120s, taking 100g of manganese-rich slag powder and 25g of analytically pure calcium oxide, uniformly mixing the manganese-rich slag powder and the analytically pure calcium oxide, placing the mixture into a crucible, heating the mixture to 1200 ℃ in a box-type reaction furnace, preserving the heat for 1 hour, cooling the mixture to room temperature along with the furnace, and obtaining a phase analysis result of a roasted product as shown in figure 2. The manganese-rich slag mainly comprises an olivine phase and a magnesia-alumina spinel phase, and is converted into a manganese monoxide phase and an melilite phase after roasting modification. The scanning electron microscope results of the roasted slag are shown in fig. 3.
Grinding the roasted product to be below 100 meshes, putting 10g of roasted slag into a beaker, adding 200mL of 0.05mol/LHCl, leaching for 30min under the condition of electromagnetic stirring, supplementing HCl by using a peristaltic pump in the leaching process, controlling the pH value to be between 1 and 5, analyzing the content of different elements in a solution after leaching by adopting ICP-AES (inductively coupled plasma-atomic emission spectrometry), wherein the dissolution rate of the different elements is shown in figure 4A, the extraction rate of Mn in the modified slag is 96.5%, the dissolution rates of Ca, Si and Al are respectively 19.1%, 17.7% and 15.6%, and the dissolution rates of Ca, Si and Al are all less than 20%. Under the same acid leaching condition, the leaching rate of manganese in the original manganese-rich slag is less than 20%, and the leaching rate of manganese in the manganese-rich slag after calcium modification is greatly increased under the condition of dilute acid leaching.
Example 2
The manganese-rich slag is dried and put in a powder tank for grinding for 120s, 100g of manganese-rich slag powder is uniformly mixed with 20g of analytically pure calcium oxide, the mixture is put in a crucible, the mixture is heated to 1200 ℃ in a box-type reaction furnace, the temperature is kept for 1 hour, the mixture is cooled to room temperature along with the furnace, and the phase analysis result of the obtained roasted product is shown in figure 5. The manganese-rich slag after roasting is converted into the calcium-manganese olivine, the calcium-aluminum melilite and the manganese monoxide.
Grinding the roasted product to be below 100 meshes, putting 10g of roasted slag into a beaker, adding 200mL of 0.05mol/LHCl, leaching for 30min under the condition of electromagnetic stirring, supplementing HCl by adopting a peristaltic pump in the leaching process, controlling the pH value to be between 1 and 5, and leaching the solution, namely the modified slag has the extraction rate of Mn of 88.1%, the dissolution rate of Ca of 21.6%, the dissolution rate of Si of 25.2% and the dissolution rate of Al of 16.7%.
Example 3
The manganese-rich slag is dried and put in a powder tank for grinding for 120s, 100g of manganese-rich slag powder is uniformly mixed with 40g of analytically pure calcium oxide, the mixture is put in a crucible, the crucible is heated to 1200 ℃ in a box-type reaction furnace, the temperature is kept for 1 hour, the mixture is cooled to room temperature along with the furnace, and the phase analysis result of the obtained roasted product is shown in figure 6. The manganese-rich slag after roasting is converted into calcium manganese olivine, calcium aluminum yellow feldspar and manganese monoxide.
Grinding the roasted product to be below 100 meshes, putting 10g of roasted slag into a beaker, adding 200mL of 0.05mol/L HCl, leaching for 30min under the condition of electromagnetic stirring, supplementing HCl by adopting a peristaltic pump in the leaching process, controlling the pH value to be between 1 and 5, and leaching the medium solution, namely the modified slag has the Mn extraction rate of 94.3%, the Ca dissolution rate of 33.3%, the Si dissolution rate of 20.5% and the Al dissolution rate of 17.9%.
Example 4
Drying the manganese-rich slag, placing the manganese-rich slag into a powder tank, grinding the manganese-rich slag for 120s, taking 100g of manganese-rich slag powder, uniformly mixing the manganese-rich slag powder with 25g of analytically pure calcium oxide, placing the mixture into a crucible, heating the mixture in a box-type reaction furnace to 1500 ℃, preserving the heat for 1 hour, cooling the mixture to room temperature along with the furnace, and converting the phase analysis result of the obtained roasted product into dicalcium silicate, gehlenite and manganese monoxide in the roasted manganese-rich slag as shown in figure 7.
Grinding the roasted product to be below 100 meshes, putting 10g of roasted slag into a beaker, adding 200mL of 0.05mol/L HCl, leaching for 30min under the condition of electromagnetic stirring, supplementing HCl by adopting a peristaltic pump in the leaching process, controlling the pH value to be between 1 and 5, and leaching the medium solution, namely the modified slag has the extraction rate of Mn of 90.3%, the dissolution rate of Ca of 22.3%, the dissolution rate of Si of 19.6% and the dissolution rate of Al of 14.7%.
Example 5
In this embodiment, hydrated lime, which is a salt containing calcium oxide, is used as a modifier, and of course, other salts containing calcium oxide, such as quicklime, limestone, and the like, can be used as modifiers, which is not illustrated in the present invention to avoid redundancy.
The manganese-rich slag is dried and put in a powder tank for grinding for 120s, 100g of manganese-rich slag powder is uniformly mixed with 36.7g of hydrated lime (the content of calcium hydroxide is 95 percent), the mixture is put in a crucible, heated to 1200 ℃ in a box-type reaction furnace, kept for 1 hour, cooled to room temperature along with the furnace, the obtained roasted products are dicalcium silicate, gehlenite and manganese monoxide, and the scanning electron microscope picture and the energy spectrum analysis result of the modified slag are shown in figure 8.
Grinding the roasted product to be below 100 meshes, putting 10g of roasted slag into a beaker, adding 200mL of 0.05mol/L HCl, leaching for 30min under the condition of electromagnetic stirring, supplementing HCl by adopting a peristaltic pump in the leaching process, controlling the pH value to be between 1 and 5, and leaching the solution, namely the modified slag has the extraction rate of Mn of 93.1%, the dissolution rate of Ca of 20.9%, the dissolution rate of Si of 24.4% and the dissolution rate of Al of 19.8%.
Comparative example 1
The manganese-rich slag is dried and put in a powder tank for grinding for 120s, 100g of manganese-rich slag powder is uniformly mixed with 25g of analytically pure calcium oxide, the mixture is put in a crucible, heated to 1000 ℃ in a box-type reaction furnace, kept for 1 hour, cooled to room temperature along with the furnace, and the phase analysis result of the obtained roasted product is shown in figure 9. The manganese-rich slag after roasting is converted into trimanganese tetroxide and calcium silicate, and simultaneously a large amount of calcium oxide remains, which shows that CaO can not completely react at 1000 ℃, and the manganese monoxide is not matched in the product.
Grinding the roasted product to be below 100 meshes, putting 10g of roasted slag into a beaker, adding 200mL of 0.05mol/L HCl, leaching for 30min under the condition of electromagnetic stirring, supplementing HCl by adopting a peristaltic pump in the leaching process, controlling the pH value to be between 1 and 5, and leaching the medium solution, namely the modified slag has the extraction rate of Mn of 28.5%, the dissolution rate of Ca of 66.4%, the dissolution rate of Si of 18.3% and the dissolution rate of Al of 15.3%.
It is worth to say that the modification reaction time of the method is preferably 1 to 3 hours, and the full modification process can be basically completed, and the experiment after 1 hour of modification is taken as an example in the embodiment, and the result shows that the extraction rate of Mn can reach 96.5% to the maximum.
The examples described herein are merely illustrative of the preferred embodiments of the present invention and do not limit the spirit and scope of the present invention, and various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A method for selectively and efficiently extracting manganese from manganese-rich slag is characterized by comprising the following steps: fully mixing the manganese-rich slag powder with a modifier containing calcium oxide, modifying at the temperature higher than 1200 ℃ for a period of time, grinding to obtain calcium-modified manganese-rich slag powder, and finally performing acid leaching to extract manganese, wherein the modification reaction is heated to be molten in a reducing or inert atmosphere.
2. The method for selectively and efficiently extracting manganese from manganese-rich slag according to claim 1, characterized by comprising the following steps: the modifier containing calcium oxide is calcium oxide, quicklime, limestone or hydrated lime.
3. The method for selectively and efficiently extracting manganese from manganese-rich slag according to claim 2, characterized in that: the CaO content in the quick lime, the limestone and the hydrated lime is not lower than 40 percent.
4. The method for selectively and efficiently extracting manganese from manganese-rich slag according to any one of claims 1 to 3, characterized by comprising the following steps: the mass of the calcium oxide is 20-40% of that of the manganese-rich slag.
5. The method for selectively and efficiently extracting manganese from manganese-rich slag according to claim 4, wherein the method comprises the following steps: the modification reaction temperature is 1200-1500 ℃.
6. The method for selectively and efficiently extracting manganese from manganese-rich slag according to claim 4, wherein the method comprises the following steps: the modification time is 5 minutes to 180 minutes.
7. The method for selectively and efficiently extracting manganese from manganese-rich slag according to claim 4, wherein the method comprises the following steps: the particle size of the calcium-modified manganese-rich slag powder is below 100 meshes.
8. The method for selectively and efficiently extracting manganese from manganese-rich slag according to claim 4, characterized by comprising the following steps: the acid used for acid leaching is hydrochloric acid, sulfuric acid or nitric acid.
9. The method for selectively and efficiently extracting manganese from manganese-rich slag according to claim 4, wherein the method comprises the following steps: controlling the pH value to be 1-5 during acid leaching.
10. The method for selectively and efficiently extracting manganese from manganese-rich slag according to claim 1, characterized by comprising the following steps: the pickling time is at least 30 min.
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