CN1587423A - Method for recovering manganese from low content manganese carbonate raw ore - Google Patents
Method for recovering manganese from low content manganese carbonate raw ore Download PDFInfo
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000011572 manganese Substances 0.000 title claims abstract description 75
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 74
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 title claims abstract description 51
- 239000011656 manganese carbonate Substances 0.000 title claims abstract description 49
- 235000006748 manganese carbonate Nutrition 0.000 title claims abstract description 49
- 229940093474 manganese carbonate Drugs 0.000 title claims abstract description 49
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 44
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 239000012141 concentrate Substances 0.000 claims description 17
- 238000002386 leaching Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 235000010755 mineral Nutrition 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 235000002867 manganese chloride Nutrition 0.000 claims description 6
- 229940099607 manganese chloride Drugs 0.000 claims description 6
- 229940099596 manganese sulfate Drugs 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 235000019270 ammonium chloride Nutrition 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 2
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 235000002908 manganese Nutrition 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 238000011161 development Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910000616 Ferromanganese Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to ferrous metal chemical ore dressing technology, and is the method of recovering manganese from low content manganese carbonate ore. The technological process includes ammonium salt roasting mode to convert manganese in manganese carbonate ore material of content 10-25 wt% into soluble manganese salt, the precipitation reaction of ammonia and CO2 produced during roasting and soluble manganese salt in leached liquid to form the concentrated ore manganese with manganese content over 50 wt% in the manganese recovering rate up to 82 % without waste gas and waste effluent produced. The ammonium salt in solution may be sued as the roasting material to realize closed circulation. In the temperature of 300-800 deg.c, SiO2, Al2O3 and Fe2O3 do not react with NH4Cl and (NH4)2SO4, and manganese is recovered selectively in the green technological process.
Description
Technical Field
The invention belongs to the technical field of black metal chemical beneficiation, and particularly relates to a method for recovering manganese from low-content manganese carbonate ore.
Technical Field
China accumulatively finds that the reserves of manganese ore are 6.4 hundred million tons, and the reserves of manganese metal are 4000 ten thousand tons, which are second to south Africa, Ukrainian and Ganjia and are the fourth place in the world. And the distribution is relatively centralized, 90% of manganese ore resources are concentrated in 6 provinces, wherein the Guangxi accounts for 38.6%, the Hunan accounts for 18.5%, and the Guizhou accounts for 13.1%, so that the large-scale development is easy. But the manganese ore resource in China is characterized by being poor, fine and impurity, the average grade contains about 21 percent of manganese, and rich ore only accounts for 6.43 percent of the national reserves; the cause type of the manganese ore is mainly deposition type manganese ore, which accounts for more than 80 percent of the total reserve, and the deposition metamorphic type, the layer control type and the weathering type manganese are less. The manganese ore type is mainly manganese carbonate ore which accounts for about 73 percent of the total reserves, and is composed of ferromanganese ore and manganese oxide ore, and the manganese-containing limestone and ferromanganese ore are few. 70% of the currently produced ores are manganese oxide ores, along with the exploitation for many years, the manganese oxide ores are rich, and many old mines are gradually depleted in manganese resources, so that a large amount of imported manganese ores are needed to meet the requirement of national economic development. 45-50 wt% of high-grade manganese ore imported by China is matched with 25-30 wt% of manganese contained in domestic ores from 80 years of the 20 th century. At present, the yield of manganese ore in China is about 550 ten thousand tons every year, and the yield of imported manganese ore is about 170 ten thousand tons every year. Of these, 90% are used in the metallurgical industry and about 10% are used in the chemical industry, light industry, defense industry, building material industry, electronic industry, environmental protection, agriculture and animal husbandry, etc. With the rapid development of related industries, particularly the ambitious goal of doubling the total value of national production, a large amount of manganese-rich ores are urgently needed, and the supply and demand have larger gaps, but the current resource condition is difficult to meet the continuous requirement, which is not suitable for the manganese ore resource reserves in China.
The mineral separation of 10-25% manganese carbonate ore is not substantially broken through at home and abroad, and the enrichment degree of manganese carbonate ore can be only improved by about 5% by using a magnetic separation method commonly used in domestic mineral separation. Foreign manganese ore is generally better in innate endowment, and a flotation method is adopted for recycling the tailing mud of manganese carbonate ore, so that the effect is better than that of a magnetic separation method. The latest foreign research adopts an electric immersion method, electricity is conducted in manganese carbonate ore, and meanwhile, the temperature is also heated to 700-; the Russian expert uses a radiometric method to increase the manganese carbonate ore with the content of less than 10 wt% to 31-32 wt%; CO gas is filled into the bottom of the test tank, and the temperature is kept at 900-; the hot liquid leaching method and the like are all exploratory studies on the development and utilization of manganese carbonate ore. In a word, no mature molding technology with high recovery rate and less environmental pollution exists for treating the low-content manganese carbonate ore. From the development trend of manganese carbonate ore utilization at home and abroad, the method has strong development selectivity and low impurity content, realizes recycling and clean production, and is an important direction for developing and utilizing manganese ore resources.
Disclosure of Invention
The invention aims to provide a method for recovering manganese from low-content manganese carbonate raw ore. The method is characterized in that: selectively converting manganese in the minerals into soluble manganese salt by adopting an ammonium salt roasting mode, further precipitating and reacting ammonia gas and carbon dioxide generated in the roasting process with the soluble manganese salt in the leachate, recovering to obtain a manganese carbonate product, and further using the ammonium salt in the solution as a roasting raw material after evaporation and crystallization, thereby realizing closed cycle of a reaction reagent; the method for recovering manganese from low-content manganese carbonate raw ore by adopting an ammonium salt method comprises the following steps:
1) grinding 10-25 wt% of manganese carbonate raw ore to be below 100 meshes so as to be mixed with NH4Cl or (NH)4)2SO4Mixing;
2) mixing the ground manganese carbonate ore with NH4Cl or (NH)4)2SO4Mixing at the ratio of manganese carbonate raw ore to NH4Cl or (NH)4)2SO4Grinding and mixing the materials in a mortar according to the volume ratio of 1 to (0.5-2.0), and mixing the materials by using a ball mill industrially;
3) the evenly mixed materials are put into a crucible and roasted for 0.5 to 6 hours in a tubular furnace at the temperature of between 300 and 800 ℃, and NH is generated4The optimal roasting temperature and time of the Cl system are 350 ℃ and 1 hour; and (NH)4)2SO4The optimal roasting temperature and time of the system are 500 ℃ and 1 hour. Introducing ammonia gas and carbon dioxide gas generated by decomposing ammonium salt in the roasting process into the leaching solution of the previous time through a closed pipeline, and precipitating manganese chloride or manganese sulfate;
4) leaching the roasted product for 10-20 minutes by adopting hot water with the temperature of 60-90 ℃ under the condition that the liquid-solid ratio is (3-10) to 1 to obtain a manganese chloride or manganese sulfate leaching solution which is used as an absorption liquid in the next roasting process;
5) filtering and drying the precipitate in the absorption solution to obtain manganese concentrate with the content of more than 50 wt%;
6) filtering the absorption liquid to obtain filtrate, evaporating and concentrating the filtrate, and crystallizing to obtain NH4Cl or (NH)4)2SO4And (5) solid, recycling and reusing.
The method has the beneficial effects that the process can directly adopt the low-grade manganese carbonate ore with the content of 10-25 wt% as the raw material, concentrate with the manganese content of more than 50 wt% is obtained by recycling, and the reaction reagent is recycled, so that no waste gas or waste liquid is discharged, thereby being a green, environment-friendly and brand-new process. As minerals, manganese carbonate ore generally contains silicic acidThe thermodynamic analysis of the components of salt, iron, calcium, aluminum and the like shows that SiO in the mineral is in the temperature range of 300-800 DEG C2，Al2O3And Fe2O3Not in contact with NH4Cl and (NH)4)2SO4And (4) reacting. Therefore, the method for recovering manganese by adopting ammonium salt can achieve the aim of selectively recovering manganese; the recovery rate of manganese reaches more than 82 percent.
Drawings
FIG. 1 is a schematic view of a process flow for enriching and recovering manganese from low-content manganese carbonate.
Detailed Description
The invention provides a method for recovering manganese from low-content manganese carbonate raw ore. Selectively converting manganese in the minerals into soluble manganese salt by adopting an ammonium salt roasting mode, further precipitating and reacting ammonia gas and carbon dioxide generated in the roasting process with the soluble manganese salt in the leachate, and recovering to obtain a manganese carbonate product, wherein the ammonium salt in the solution can be further used as a roasting raw material, so that closed cycle of the reaction reagent ammonium salt is realized; according to the schematic process flow shown in fig. 1, the method for recovering manganese from low-content manganese carbonate raw ore by adopting an ammonium salt method comprises the following steps:
1) grinding raw manganese carbonate ore with the content of 10-25 wt% or concentrate with the content of more than 20-2 wt%Down to 100 mesh for reacting with NH4Cl or (NH)4)2SO4Mixing;
2) mixing the ground manganese carbonate ore with NH4Cl or (NH)4)2SO4Mixing manganese carbonate ore and NH4Cl or (NH)4)2SO4Grinding and mixing the materials in a mortar according to the volume ratio of 1 to (0.5-2.0), and mixing the materials by using a ball mill industrially;
3) the evenly mixed materials are put into a crucible and roasted for 0.5 to 6 hours in a tubular furnace at the temperature of between 300 and 800 ℃, and NH is generated4The optimal roasting temperature and time of the Cl system are 350 ℃ and 1 hour; and (NH)4)2SO4The optimal roasting temperature and time of the system are 500 ℃ and 1 hour. Introducing ammonia gas and carbon dioxide gas generated by decomposing ammonium salt in the roasting process into the leaching solution of the previous time in vacuum to precipitate manganese chloride or manganese sulfate;
4) leaching the roasted product for 10-20 minutes by adopting hot water with the temperature of 60-90 ℃ under the condition that the liquid-solid ratio is (3-10) to 1 to obtain a manganese chloride or manganese sulfate leaching solution which is used as an absorption liquid in the next roasting process;
5) filtering and drying the precipitate in the absorption solution to obtain manganese ore concentrate with the content higher than 50 wt%;
6) filtering the absorption liquid to obtain filtrate, evaporating and concentrating the filtrate, and crystallizing to obtain NH4Cl or (NH)4)2SO4And (5) solid, recycling and reusing.
The specific embodiment is that manganese carbonate concentrate of new manganese ore in Guangxi province is adopted, the manganese content is about 21 wt%, the ore is high-silicon low-ferro manganese ore mainly comprising rhodochrosite, caltropane and manganese calcite, and the structure mainly comprises cementing materials of compact massive bean-shaped manganese carbonate ore. The manganese carbonate phase composition and the main chemical components of manganese carbonate ore are shown in tables 1 and 2.
The main chemical reactions of the method for recovering manganese from low-content manganese carbonate raw ore by adopting the ammonium salt method are as follows:
or:
table 1 Guangxi brand manganese carbonate concentrate manganese phase distribution (%)
Manganese pyrolusite summation in phase rhodochrosite manganese calcite manganese silicate manganese limonite ore
Manganese content 15.434.381.330.750.0821.97
Distribution 70.2319.946.053.410.37100
Table 2 analysis results of main chemical components (%) -of the Guangxi Daxin manganese carbonate concentrate
Element Mn Fe Al2O3SiO2CaO MgO Pb S K P
Content 20.876.243.0624.966.791.540.030.130.070.016
Example 1
Weighing 10 g of manganese carbonate concentrate of Guangxi Daxin manganese ore and 12 g of NH4The Cl is ground and mixed evenly in a mortar and put into a 50ml quartz boat for roasting at 400 ℃ in a tube furnace for 1 h. The calcine was leached with 100ml of water at 80 ℃ for 20min with stirring, and washed 3 times with a small amount. And analyzing the manganese concentration in the filtrate, calculating the manganese recovery rate to be 98%, and taking the leaching solution as the next absorption solution. Re-weighing 10 g of manganese carbonate concentrate and 12 g of NH4Cl is uniformly mixed and roasted at 400 ℃ in a tubular furnace, gas generated in the roasting process is introduced into the leaching solution of the previous time in vacuum, manganese in the leaching solution absorbs ammonia gas and carbon dioxide generated in roasting to generate precipitate, after the roasting is finished, the absorption solution is filtered, and a filter cake is dried to obtain manganese with the manganese content of 52 wt%Concentrate, and analyzing the concentration of manganese in the filtrate to obtain the manganese precipitation rate of 95%; further evaporating and crystallizing the filtrate to obtain ammonium chloride solid, and drying the crystals obtained after evaporation and crystallization at 100 ℃ for 3 hours to obtain NH412.2 g of Cl crystal (containing a small amount of impurities) can be used as a material for next roasting.
Example 2
Weighing 10 g of manganese carbonate concentrate of Guangxi Daxin manganese ore and 20 g of (NH)4)2SO4Grinding and mixing in mortarHomogenizing, and calcining in 50ml quartz boat at 500 deg.C for 1 hr. The calcine is leached with 80ml of water at 90 ℃ for 20min with stirring and washed 3 times with a small amount. And analyzing the manganese concentration in the filtrate, calculating the manganese recovery rate to be 82%, and taking the leaching solution as the next absorption solution. Re-weighing 10 g of manganese carbonate concentrate and 20 g (NH)4)2SO4Uniformly mixing the raw materials, roasting the raw materials at 350 ℃ in a tubular furnace, introducing gas generated in the roasting process into the leachate of the previous time in a vacuum manner, absorbing ammonia gas and carbon dioxide generated in roasting by manganese in the leachate to generate precipitate, filtering the absorption solution after roasting is finished, drying a filter cake to obtain manganese concentrate with 51% of manganese content, and analyzing the concentration of manganese in the filtrate to obtain the manganese precipitation rate of 93%; further evaporating the filtrate for crystallization to obtain ammonium sulfate solid, and drying the crystal obtained after evaporation crystallization at 100 deg.C for 3 hr to obtain (NH)4)2SO420.6 g of crystals (possibly containing a small amount of impurities) can be used as a material for the next roasting.
Example 3
Weighing 10 g of manganese carbonate concentrate of Guangxi Daxin manganese ore and 12 g of multiplexing NH obtained by evaporative crystallization4The Cl is ground and mixed evenly in a mortar and put into a 50ml quartz boat for roasting at 350 ℃ for 1h in a tube furnace. Introducing gas generated in the roasting process into the leaching solution in the last time in vacuum, absorbing ammonia gas and carbon dioxide generated in roasting by manganese in the leaching solution to generate precipitate, filtering the absorbing solution after roasting is completed, and drying a filter cake to obtain manganese concentrate; 5 times of circulation are combined into a group, filtrate obtained by 5 times of absorption is evaporated and concentrated, 5 g of ammonium bicarbonate is added to completely precipitate manganese, and ammonium chloride solid can be obtained by further evaporation, concentration and crystallizationAnd can be used as the ingredient for the next roasting. The results obtained by three sets of experiments are shown in table 3.
TABLE 3 enrichment cycle test results for low manganese carbonate content
Number of cycles first, second and third
Manganese concentrate/g 101010101010101010101010101010
NH4Cl/g 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12
NH4Total Cl 6060 g 60 g
Leaching Rate/% 989992979698999898989697989898
Precipitation/% 939492939389909797959892889194
Mn recovery/% 89.691.990.2
NH4HCO3Consuming 3 g, 4 g, 5 g
NH4Cl recovery 65 g, 68 g, 64 g
Claims (2)
1. A method for recovering manganese from low-content manganese carbonate raw ore is characterized by comprising the following steps: selectively converting manganese in the minerals into soluble manganese salt by adopting a salt plating roasting mode, further precipitating and reacting ammonia gas and carbon dioxide generated in the roasting process with the soluble manganese salt in the leachate, and recovering to obtain a manganese carbonate product, wherein ammonium salt in the solution can be further used as a roasting raw material, so that closed cycle of a reaction reagent is realized; the method for recovering manganese from low-content manganese carbonate raw ore by adopting an ammonium salt method comprises the following steps:
1) grinding manganese carbonate ore with the content of 10-25 wt% to be below 100 meshes so as to be mixed with NH4Cl or (NH)4)2SO4Mixing;
2) mixing the ground manganese carbonate ore with NH4Cl or (NH)4)2SO4Mixing, wherein the proportion is that manganese carbonate raw ore: NH (NH)4Cl or (NH)4)2SO4Grinding and mixing the materials in a mortar according to the volume ratio of 1 to (0.5-2.0), and mixing the materials by using a ball mill industrially;
3) placing the uniformly mixed materials into a crucible, roasting the materials in a tubular furnace at 300-800 ℃ for 0.5-6 hours, introducing ammonia gas and carbon dioxide gas generated by decomposing ammonium salt in the roasting process into the last leaching solution through a closed pipeline, and precipitating manganese chloride or manganese sulfate;
4) leaching the roasted product for 10-20 minutes by adopting hot water with the temperature of 60-90 ℃ under the condition that the liquid-solid ratio is (3-10) to 1 to obtain a manganese chloride or manganese sulfate leaching solution which is used as an absorption liquid in the next roasting process;
5) filtering and drying the precipitate in the absorption solution to obtain manganese concentrate with the content of more than 50 wt%;
6) filtering the absorption liquid to obtain filtrate, evaporating and concentrating the filtrate, and crystallizing to obtain NH4Cl or (NH)4)2SO4And (5) solid, recycling and reusing.
2. The method for recovering manganese from low-content manganese carbonate raw ore according to claim 1, wherein: roasting the uniformly mixed material in a tube furnace, NH4The optimal roasting temperature of the Cl system is 350 ℃ and 1 hour; and (NH)4)2SO4The optimal roasting temperature and time of the system are 500 ℃ and 1 hour.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436332C (en) * | 2006-11-08 | 2008-11-26 | 孙光辉 | Method for producing manganese sulfate by using continuous pipeline method |
| CN101579685B (en) * | 2009-06-10 | 2010-10-27 | 重庆大学 | Method for processing and utilizing electrolytic manganese waste residue |
| CN102021346A (en) * | 2011-01-06 | 2011-04-20 | 中国环境科学研究院 | Method for recovering soluble manganese in electrolytic manganese waste residue |
| CN102302977A (en) * | 2011-09-20 | 2012-01-04 | 长沙达华矿业技术开发有限公司 | Beneficiation method for improving grade of manganese in rhodochrosite ores |
| CN103757247A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN105669427A (en) * | 2016-02-26 | 2016-06-15 | 程洪光 | Recover method for acid mist generated by acid hydrolysis reaction in citric acid production |
| CN105967396A (en) * | 2016-06-29 | 2016-09-28 | 贵州铜仁金瑞锰业有限责任公司 | Method for treating manganese-containing wastewater |
| CN106319211A (en) * | 2015-07-02 | 2017-01-11 | 阿克陶科邦锰业制造有限公司 | Production technique for leaching manganese carbonate ore through double sulfate salt |
| CN106756127A (en) * | 2016-12-19 | 2017-05-31 | 北京科技大学 | A kind of method of iron and manganese in extraction solid |
| CN112174180A (en) * | 2020-09-06 | 2021-01-05 | 桂林理工大学 | Preparation method and application of calcite-rhodochrosite solid solution |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2023268646A1 (en) * | 2022-05-13 | 2024-11-21 | Innovative Manganese Technologies Sa (Pty) Ltd. | Beneficiation of manganese-bearing ore |
| GB202212989D0 (en) * | 2022-09-06 | 2022-10-19 | Manganese Metal Company Pty Ltd | A process for producing manganese sulphate monohydrate |
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2004
- 2004-07-21 CN CN 200410069373 patent/CN1238534C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436332C (en) * | 2006-11-08 | 2008-11-26 | 孙光辉 | Method for producing manganese sulfate by using continuous pipeline method |
| CN101579685B (en) * | 2009-06-10 | 2010-10-27 | 重庆大学 | Method for processing and utilizing electrolytic manganese waste residue |
| CN102021346A (en) * | 2011-01-06 | 2011-04-20 | 中国环境科学研究院 | Method for recovering soluble manganese in electrolytic manganese waste residue |
| CN102302977A (en) * | 2011-09-20 | 2012-01-04 | 长沙达华矿业技术开发有限公司 | Beneficiation method for improving grade of manganese in rhodochrosite ores |
| CN103757247A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN106319211A (en) * | 2015-07-02 | 2017-01-11 | 阿克陶科邦锰业制造有限公司 | Production technique for leaching manganese carbonate ore through double sulfate salt |
| CN105669427A (en) * | 2016-02-26 | 2016-06-15 | 程洪光 | Recover method for acid mist generated by acid hydrolysis reaction in citric acid production |
| CN105967396A (en) * | 2016-06-29 | 2016-09-28 | 贵州铜仁金瑞锰业有限责任公司 | Method for treating manganese-containing wastewater |
| CN106756127A (en) * | 2016-12-19 | 2017-05-31 | 北京科技大学 | A kind of method of iron and manganese in extraction solid |
| CN112174180A (en) * | 2020-09-06 | 2021-01-05 | 桂林理工大学 | Preparation method and application of calcite-rhodochrosite solid solution |
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