CN104556233B - Utilization method of manganese oxide ore - Google Patents
Utilization method of manganese oxide ore Download PDFInfo
- Publication number
- CN104556233B CN104556233B CN201410813834.4A CN201410813834A CN104556233B CN 104556233 B CN104556233 B CN 104556233B CN 201410813834 A CN201410813834 A CN 201410813834A CN 104556233 B CN104556233 B CN 104556233B
- Authority
- CN
- China
- Prior art keywords
- filtrate
- manganese oxide
- oxide ore
- manganese
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a utilization method of manganese oxide ore, which adopts a combined selection and metallurgy process to perform strong magnetic separation on manganese oxide ore to obtain manganese concentrate and magnetic separation tailings, and the magnetic separation tailings are leached and subjected to impurity removal to obtain high-purity manganese carbonate after precipitation. Compared with the traditional utilization method of manganese oxide ore, the method provided by the invention has the advantages of simple process and high recovery rate of manganese.
Description
Technical field
The present invention relates to field of hydrometallurgy, particularly relate to a kind of Application way of manganese oxide ore.
Background technology
China's manganese resource degree of protection is lower.According to United States Bureau of Mines " MineralCommoditySummaries2009 ", Chinese manganese ore proven reserve about 100,000,000 tons till ending in October, 2008,2% of Jin Zhan world total reserves, wherein poor manganese ore reserves account for 93.6% of national total reserves.The feature that China's manganese resource has " poor, assorted, thin ".The average grade of domestic manganese ore is approximately 21%, and there is no and meet other rich manganese ore of commercial grade.6.6% is only had for rich manganese ore in the explored manganese ore total reserves in the whole nation, and exhausted.In addition, China's manganese ore foreign matter content is higher, and impurity is in the majority with phosphorus, iron and sulphur.In the mineral deposit that China has found out, the mineral deposit that the content of iron exceedes national standard accounts for the per-cent of sum up to 72.9%, and the content of phosphorus account for 49.5% higher than the mineral deposit of standard, and can reach ANOMALY IN FINE QUALITY MANGANESE DEPOSITS standard approximately only account for 6.1%.
China is manganese ore country of consumption maximum in the world, annual consumption manganese ore more than 1,000 ten thousand tons.And the guaranteed extent of domestic manganese ore is about 50%, manganese ore breach amount is very large, and therefore, China need, from external a large amount of import, be manganese ore importer the biggest in the world every year.Whole nation manganese ore import volume in 2006 reaches 620.7 ten thousand tons, accounts for 36%, 2007 and China's Imported Manganese Ore 663.2 ten thousand tons and 758.1 tons respectively in 2008 of domestic manganese ore consumption.In view of the disparities between supply and demand relation of the growing tension of the lower and huge consumers demand of China's manganese resource degree of protection, actively must research and develop the enrichment of poor manganese ore and utilize technology, thus effectively utilize the low-grade manganese resource of rich reserves, to improving China's manganese resource degree of protection, promoting that the Sustainable development tool of manganese ore industry is of great significance.
Based on the manganese oxide ore of pyrolusite, psilomelane, hausmannite, brunite, manganite and meta-manganic acid ore, it generally adopts the beneficiation method such as washup, gravity treatment on producing.But because ore weathering is serious, containing a large amount of sludge, manganese mineral disseminated grain size is fine, and therefore the effect of mechanical beneficiation is not satisfactory, and concentrate manganese grade is difficult to reach 30%, and manganese recovery ratio is lower in addition.
Select manganese oxide ore for traditional difficulty, general fire reduction and the wet reducing of adopting is that main metallurgical method processes.But fire reduction technology also exists the problems such as energy consumption is high, exhaust emission is serious, is not suitable for the national policy policy of energy-saving and emission-reduction and pro-environmental society.For wet reducing, minority electrolytic manganese generates enterprise and adopts " two ore deposits add acid system " to prepare manganese sulfate solution, mainly add sulfuric acid by after troilite powder and manganese oxide powder mixing, chemical combination groove temperature is increased to about 95 DEG C and the manganese sulfate solution that redox reaction obtains containing a large amount of impurity occurs.This technique needs external heat source to maintain higher extraction temperature, introduces a large amount of iron ions, and increased the weight of follow-up removal of impurities load, affect quality product, the rate of recovery is lower.Therefore, traditional difficulty selects that the Application way manganese recovery ratio of manganese oxide ore is lower, environmental pollution is comparatively serious.
Summary of the invention
Based on this, be necessary to select for traditional difficulty the problem that the Application way manganese recovery ratio of manganese oxide ore is lower, the Application way of the manganese oxide ore that a kind of manganese recovery ratio is higher is provided.
An Application way for manganese oxide ore, comprises the steps:
Step one, manganese oxide ore is levigate after carry out high intensity magnetic separation and obtain manganic concerntrate, magnetic tailing left after retaining magnetic separation;
Step 2, described magnetic tailing step one obtained is levigate is less than 0.15mm to granularity, sulphuric acid soln is mixed with described magnetic tailing, pass into sulfur dioxide gas and maintain Leaching reaction, leach filtration completely and obtain the first filter residue and the first filtrate, described first filtrate is the solution containing manganous sulfate, judges described containing Mn in the solution of manganous sulfate
2+concentration whether reach 102g/L, if, then represent that described first filtrate is qualified, end step two, if not, then represent that described first filtrate is defective, described first filtrate is mixed with the described magnetic tailing do not leached and the above-mentioned leaching operation repeated in step 2 until Mn in described first filtrate
2+concentration reach 102g/L;
Add oxygenant in step 3, described first filtrate that obtains to step 2, fully regulate pH to 4.95 ~ 6.0 after reaction, then filter and retain the second filtrate; Add bicarbonate of ammonia in step 4, described second filtrate that obtains to step 3, fully filters and retains the second filter residue after reaction, described second filter residue is manganous carbonate.
In one of them embodiment, in step one, described manganese oxide ore is based on the manganese oxide ore of pyrolusite, brunite, manganite, psilomelane or meta-manganic acid ore.In one of them embodiment, in step one, by being operating as of levigate for manganese oxide ore rear magnetic separation: carry out wet high-intensity magnetic separation after adopting coarse aggregate ore-dressing technique that manganese oxide ore is levigate.
In one of them embodiment, in step one, the magneticstrength of high intensity magnetic separation is 721kA/m ~ 1112kA/m.
In one of them embodiment, in step 2, the liquid-solid mass ratio of described sulphuric acid soln and described magnetic tailing is 2.5:1 ~ 6:1, and the concentration of described sulfuric acid is 0.30mol/L ~ 1.08mol/L.
In one of them embodiment, in step 2, in the operation mix described first filtrate with described magnetic tailing, the liquid-solid mass ratio of described first filtrate and described magnetic tailing is 2.5:1 ~ 6:1.
In one of them embodiment, in step 2, pass into sulfur dioxide gas and maintain in the operation of Leaching reaction, the flow of described sulfur dioxide gas is 0.2L/min ~ 20L/min, and the reaction times is 20min ~ 80min, and temperature of reaction is 0 DEG C ~ 30 DEG C.
In one of them embodiment, in step 3, described oxygenant is hydrogen peroxide, chlorine or Manganse Dioxide.
In one of them embodiment, in step 3, fully regulate being operating as of pH to 4.95 ~ 6.0 after reaction: fully add pH adjusting agent after reaction and regulate pH to 4.95 ~ 6.0, described pH adjusting agent is ammoniacal liquor, Na
2cO
3, NaHCO
3, (NH
4)
2cO
3, NH
4hCO
3or NaOH.
In one of them embodiment, in step 4, described second filtrate and described bicarbonate of ammonia fully react rear filtration and retain the 3rd filtrate, and carry out evaporative crystallization to described 3rd filtrate, the crystalline solid obtained is ammonium sulfate.
What the Application way of above-mentioned manganese oxide ore adopted is selecting smelting combination technique, namely obtains manganic concerntrate and magnetic tailing by carrying out high intensity magnetic separation to manganese oxide ore, and above-mentioned magnetic tailing is carried out leachings also removal of impurities, precipitates and obtains highly purified manganous carbonate.Compared with the Application way of traditional manganese oxide ore, method technique provided by the invention is simple, and the rate of recovery of manganese is higher.
Accompanying drawing explanation
Fig. 1 is the schema of the Application way of the manganese oxide ore of an embodiment.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public specific embodiment.
Unless otherwise defined, all technology used herein and scientific terminology are identical with belonging to the implication that those skilled in the art of the present invention understand usually.The object of term used in the description of the invention herein just in order to describe specific embodiment, is not intended to be restriction the present invention.Term as used herein " and/or " comprise arbitrary and all combinations of one or more relevant Listed Items.
The Application way of the manganese oxide ore of an embodiment as shown in Figure 1, comprises the steps:
S10 (step one), manganese oxide ore is levigate after carry out high intensity magnetic separation and obtain manganic concerntrate, magnetic tailing left after retaining magnetic separation.
In step one, manganese oxide ore is based on the manganese oxide ore of pyrolusite, brunite, manganite, psilomelane or meta-manganic acid ore.Manganese oxide ore can be the mine tailing in primary ore or dressing-works.Wherein, the content of manganese is lower than 24%.
In step one, by being operating as of levigate for manganese oxide ore rear magnetic separation: carry out wet high-intensity magnetic separation after adopting coarse aggregate ore-dressing technique that manganese oxide ore is levigate.
In step one, be 721kA/m ~ 1112kA/m by the magneticstrength of levigate for manganese oxide ore rear high intensity magnetic separation.Manganic concerntrate and magnetic tailing is obtained after above-mentioned high intensity magnetic separation operation.
Manganese oxide ore forms by connate deposit manganese ore layer or containing manganese rock downward enrichment after weathering, silt content is higher, argillization phenomenon is serious, be easy to cracked argillization under mechanical action, and coarse fraction is high containing manganese, fine fraction is low containing manganese, and manganese mineral disseminated grain size is fine, and therefore manganese oxide ore sorting result is undesirable.Fineness refers in material the percentage composition of all particles being less than certain granularity.The impact of grinding fineness on high intensity magnetic separation is as shown in table 1:
Table 1 grinding fineness is on the impact of high intensity magnetic separation
As can be seen from Table 1, along with grinding fineness attenuates, the productive rate of concentrate drops to 26.86% by 46.58%, and the rate of recovery drops to 40.72% by 66.10%, and productive rate and the rate of recovery decline rapidly.As can be seen here, ore grinding can worsen the sorting result of high intensity magnetic separation on the contrary.This destroys manganese mineral coarse aggregate because granularity is levigate.Therefore, need protection manganese mineral coarse aggregate in ore grinding process, avoid the mechanical effects such as ore grinding, strong mixing, strong scouring to the destruction of aggregate as far as possible, thus realize coarse aggregate high intensity magnetic separation raising sorting index.
The present invention is according to this feature; under the prerequisite of the rich manganese mineral coarse aggregate of protection, coarse grain rich manganese aggregate high intensity magnetic separation is carried out to manganese oxide ore; namely simple coarse aggregate ore-dressing technique is adopted to sort the manganese oxide ore aggregate of coarse grain; can preconcentration recovery part manganic concerntrate; sorting result is desirable; manganic concerntrate grade is greater than 29%, and recovery rate in ore-dressing is greater than 55%.This method avoids ore overbreak, thus improves sorting index.
Ore grade refers to the content of useful component or valuable mineral in unit volume or unit weight ore.
S20 (step 2), magnetic tailing step one obtained is levigate is less than 0.15mm to granularity, sulphuric acid soln is mixed with magnetic tailing, pass into sulfur dioxide gas and maintain Leaching reaction, leach filtration completely and obtain the first filter residue and the first filtrate, first filtrate is the solution containing manganous sulfate, judges Mn in the solution containing manganous sulfate
2+concentration whether reach 102g/L, if so, then represent that the first filtrate is qualified, end step two, if not, then represent that the first filtrate is defective, the first filtrate is mixed with the magnetic tailing do not leached and the above-mentioned leaching operation repeated in step 2 until Mn in the first filtrate
2+concentration reach 102g/L.
In step 2, the liquid-solid mass ratio of sulphuric acid soln and magnetic tailing is 2.5:1 ~ 6:1.The concentration of sulfuric acid is 0.30mol/L ~ 1.08mol/L.
In step 2, in the operation mix the first filtrate with magnetic tailing, the liquid-solid mass ratio of the first filtrate and magnetic tailing is 2.5:1 ~ 6:1.
If the first filtrate is defective in step 2, then except the first filtrate being mixed with magnetic tailing and repeating except subsequent step, the first washings is retained after also can washing the first filter residue, first washings, the first filtrate are mixed with magnetic tailing, repeats subsequent operations until Mn in the first filtrate
2+concentration reach 102g/L.Now, the liquid-solid mass ratio of the first washings, the first filtrate and magnetic tailing is 2.5:1 ~ 6:1.
In step 2, pass into sulfur dioxide gas and maintain in the operation of reaction, the flow of sulfur dioxide gas is 0.2L/min ~ 20L/min.The reaction of sulfur dioxide gas generation reducing leaching can generate manganese sulfate solution.
In step 2, pass into sulfur dioxide gas and maintain in the operation of Leaching reaction, the reaction times is 20min ~ 80min, and temperature of reaction is 0 DEG C ~ 30 DEG C.Above-mentioned technique does not need extra heating to provide thermal source, and can simplify the operation step, saves process costs.
The operation of step 2 is called that cross-flow is leached, and cross-flow is leached and referred to that a collection of leaching agent is leaching a collection of new ore deposit and after carrying out solid-liquid separation, going again to process another batch of new ore deposit, is very suitable for processing low grade ore.Such as, take three grades of cross-flows to leach to the manganese oxide ore that Mn content is 16.02%, in leach liquor, Mn content brings up to 70.56g/L by 29.86g/L.The progression that cross-flow is leached is by Mn in single-stage leach liquor
2+concentration decide, work as Mn
2+concentration when reaching 102g/L, can leaching operation be stopped and entering next step.Adopt cross-flow Leaching way can significantly improve the concentration of manganese in leach liquor, reduce the stripping of impurity, reduce the solution-treated amount of subsequent step.After the operation of step 2, the leaching yield of manganese is 95% ~ 99%.
Add oxygenant in S30 (step 3), the first filtrate of obtaining to step 2, fully regulate pH to 4.95 ~ 6.0 after reaction, then filter and retain the second filtrate.
In step 3, oxygenant can be hydrogen peroxide, chlorine or Manganse Dioxide.The object using oxygenant is by Fe
2+be oxidized to Fe
3+.When adopting hydrogen peroxide or Manganse Dioxide to be oxidized as oxygenant, not only oxidation effectiveness is better, also can not introduce other impurity simultaneously.
In step 3, after reacting completely, regulate being operating as of pH to 4.95 ~ 6.0: add pH adjusting agent after reacting completely and regulate pH to 4.95 ~ 6.0.PH adjusting agent can be ammoniacal liquor, Na
2cO
3, NaHCO
3, (NH
4)
2cO
3, NH
4hCO
3or NaOH.These pH adjusting agents can with above-mentioned containing the Fe in the solution of manganous sulfate
3+, Al
3+generate precipitation Deng impurity reaction, ensure Mn simultaneously
2+be not hydrolyzed and generate precipitation.In addition, due to Fe (OH)
3with Al (OH)
3colloid is with positive charge, (iso-electric point of orthosilicic acid is near pH=2 for the adsorbable silicic acid with negative charge or poly silicic acid, when pH is greater than 2, the poly silicic acid that orthosilicic acid dissociation, polymerization etc. can occur and formed with negative charge) and silicon is removed from the first filtrate.
Add bicarbonate of ammonia in S40 (step 4), the second filtrate of obtaining to step 3, fully filters and retains the second filter residue after reaction, the second filter residue is manganous carbonate.
The quality of bicarbonate of ammonia is reaction required stoichiometric 105% ~ 120%.
Filter and the step retaining the second filter residue can also comprise and to wash the second filter residue and dry, the purity of the manganous carbonate obtained is higher.
In the process of sulfur dioxide gas reducing leaching reaction, side reaction inevitably occurs and generates dithionic acid root, the present invention adopts ammonium bicarbonate precipitation mn ion, achieves being separated of manganese and dithionic acid root.
In addition, in step 4, the second filtrate and bicarbonate of ammonia fully react rear filtration and retain the 3rd filtrate, and carry out evaporative crystallization to the 3rd filtrate, the crystalline solid obtained is ammonium sulfate.
Carrying out dry temperature to crystalline solid is 140 DEG C ~ 250 DEG C.Impurity dithionic acid root in step 4 enters ammonium sulfate in above-mentioned evaporation and crystal process, and under above-mentioned drying temperature, dithionic acid root decomposes, thus eliminates the impact of dithionic acid root impurity.
Compared with the Application way of traditional manganese oxide ore, the Application way of manganese oxide ore of the present invention adopts the low-grade manganese oxide ore of above-mentioned selecting smelting combination art breading, technique is simple, and can significantly improve manganese recovery ratio, in the manganous carbonate obtained, the total yield of manganese is greater than 95%.Not only can obtain manganese grade higher than the manganic concerntrate of 29%, the manganous carbonate that purity is greater than 97% can also be obtained.In addition, can also ammonium sulfate be obtained, thus reclaim byproduct of ammonium sulfate.
Be embodiment below:
Embodiment 1
Manganese oxide ore in the present embodiment selects the mine tailing of factory for manganese oxide ore, and manganese mineral is wherein based on pyrolusite, manganite and brunite, and disseminated grain size is fine, and part is with rich manganese coarse aggregate form output, and its chemical composition analysis is as shown in table 2.
The main component of the manganese oxide ore plant tailing of table 2 embodiment 1
| Composition | Mn | Fe | K | CaO | MgO | Na | S |
| Content (%) | 21.53 | 8.86 | 0.77 | 3.16 | 1.00 | 0.048 | 0.35 |
| Composition | Al 2O 3 | SiO 2 | Ba | TiO 2 | Ni | Co | P |
| Content (%) | 4.08 | 33.47 | 0.25 | 0.20 | 0.030 | 0.012 | 0.14 |
The Application way of manganese oxide ore plant tailing is as follows:
Step one, take 25kg manganese oxide ore plant tailing, to plant tailing dispersed with stirring under the prerequisite of the rich manganese mineral coarse aggregate of protection, ore grain size is less than 2mm.Under the magneticstrength of 1112kA/m, carry out wet high-intensity magnetic separation, obtain 11.3kg manganic concerntrate and 13.7kg magnetic tailing.In manganic concerntrate, the grade of Mn is 31.00%, and in magnetic tailing, the grade of Mn is 13.73%.
Step 2, magnetic tailing step one obtained is levigate is less than 0.15mm to granularity, 0.22L sulfuric acid, 16.22L water are mixed with 2.74kg magnetic tailing, pass into sulfur dioxide gas, and the flow maintaining sulfur dioxide gas is 10.96L/min, at room temperature carry out reducing leaching reaction, filter after reaction 20min and obtain the first filter residue and the first filtrate, the first filtrate is the solution containing manganous sulfate.Containing Mn in the solution of manganous sulfate
2+concentration do not reach 102g/L, represent that the first filtrate is defective.First filter residue is washed, stored up, and retains the first washings.Above-mentioned first washings and the first filtrate are mixed with the 2.74kg magnetic tailing do not leached according to the liquid-solid mass ratio of 6:1, the above-mentioned leaching operation in continuation repeating step two four times, obtains Mn in the first filtrate
2+concentration be 114g/L, represent that the first filtrate is now qualified, the leaching yield of manganese reaches 95%.
129g hydrogen peroxide (H is added in step 3, the first filtrate of obtaining to step 2
2o
2concentration is 30wt%), make Fe
2+be oxidized to Fe
3+, fully add 0.43L ammoniacal liquor adjust ph to 6.0 after reaction, the reaction that is hydrolyzed generates Fe (OH)
3with Al (OH)
3precipitation, filters after reacting completely and retains the second filtrate.In this second filtrate, the clearance of Fe, Al and Si is respectively 100%, 99.44% and 98.91%.
Add 6.47kg bicarbonate of ammonia in step 4, the second filtrate of obtaining to step 3, fully filters and retains the second filter residue and the 3rd filtrate after reaction.Above-mentioned second filter residue obtains 3.84kg manganous carbonate after washing, drying.Carry out evaporative crystallization to the 3rd filtrate at 250 DEG C, the crystalline solid obtained is ammonium sulfate.
Embodiment 2
Manganese oxide ore in the present embodiment selects the mine tailing of factory for manganese oxide ore, and manganese mineral is wherein based on pyrolusite, manganite and brunite, and disseminated grain size is fine, and part is with rich manganese coarse aggregate form output, and its chemical composition analysis is as shown in table 2.
The Application way of manganese oxide ore plant tailing is as follows:
Step one, take 25kg manganese oxide ore plant tailing, to plant tailing dispersed with stirring under the prerequisite of the rich manganese mineral coarse aggregate of protection, ore grain size is less than 2mm.Under the magneticstrength of 721kA/m, carry out wet high-intensity magnetic separation, obtain 9.1kg manganic concerntrate and 15.9kg magnetic tailing.In manganic concerntrate, the grade of Mn is 31.16%, and in magnetic tailing, the grade of Mn is 16.03%.
Step 2, magnetic tailing step one obtained is levigate is less than 0.15mm to granularity, 0.64L sulfuric acid, 19.23L water are mixed with 7.95kg magnetic tailing, pass into sulfur dioxide gas, and the flow maintaining sulfur dioxide gas is 10.96L/min, at room temperature carry out reducing leaching reaction, filter after reaction 60min and obtain the first filter residue and the first filtrate, the first filtrate is the solution containing manganous sulfate.Containing Mn in the solution of manganous sulfate
2+concentration do not reach 102g/L, represent that the first filtrate is defective.First filter residue is washed, stored up, and retains the first washings.Above-mentioned first washings and the first filtrate are mixed with the 7.95kg magnetic tailing newly do not leached according to the liquid-solid mass ratio of 2.5:1, continues the above-mentioned leaching operation in repeating step two, obtain Mn in the first filtrate
2+concentration be 121.8g/L, represent that the first filtrate is now qualified, the leaching yield of manganese reaches 99%.
139g hydrogen peroxide (H is added in step 3, the first filtrate of obtaining to step 2
2o
2concentration is 30wt%), make Fe
2+be oxidized to Fe
3+, fully add 0.5L ammoniacal liquor adjust ph to 4.95 after reaction, the reaction that is hydrolyzed generates Fe (OH)
3with Al (OH)
3precipitation, filters after reacting completely and retains the second filtrate.In this second filtrate, the clearance of Fe, Al and Si is respectively 100%, 99.44% and 98.91%.
Add 7.31kg bicarbonate of ammonia in step 4, the second filtrate of obtaining to step 3, fully filters and retains the second filter residue and the 3rd filtrate after reaction.Above-mentioned second filter residue obtains 4.96kg manganous carbonate after washing, drying.Carry out evaporative crystallization to the 3rd filtrate at 140 DEG C, the crystalline solid obtained is ammonium sulfate.
Embodiment 3
Manganese oxide ore in the present embodiment is for Guangxi manganese oxide ore, and manganese mineral is wherein based on pyrolusite, psilomelane, manganite and brunite, and disseminated grain size is fine, and part is with rich manganese coarse aggregate form output, and its chemical composition analysis is as shown in table 3.
The main component of the Guangxi manganese oxide ore of table 3 embodiment 3
| Composition | Mn | Fe | Al 2O 3 | SiO 2 | Ni | Co | P | S |
| Content (%) | 22.59 | 10.21 | 3.65 | 24.65 | 0.05 | 0.07 | 0.246 | 0.048 |
The Application way of Guangxi manganese oxide ore is as follows:
Step one, take 25kg Guangxi manganese oxide ore, Guangxi manganese oxide ore dispersed with stirring under the prerequisite of the rich manganese mineral coarse aggregate of protection, ore grain size is less than 2mm.Under the magneticstrength of 887kA/m, carry out wet high-intensity magnetic separation, obtain 11.8kg manganic concerntrate and 13.2kg magnetic tailing.In manganic concerntrate, the grade of Mn is 30.98%, and in magnetic tailing, the grade of Mn is 15.07%.
Step 2, magnetic tailing step one obtained is levigate is less than 0.15mm to granularity, 0.35L sulfuric acid, 17.25L water are mixed with 4.4kg magnetic tailing, pass into sulfur dioxide gas, and the flow maintaining sulfur dioxide gas is 5.5L/min, at room temperature carry out reducing leaching reaction, filter after reaction 80min and obtain the first filter residue and the first filtrate, the first filtrate is the solution containing manganous sulfate.Containing Mn in the solution of manganous sulfate
2+concentration do not reach 102g/L, represent that the first filtrate is defective.First filter residue is washed, stored up, and retains the first washings.Above-mentioned first washings and the first filtrate are mixed with the 4.4kg magnetic tailing do not leached according to the liquid-solid mass ratio of 4:1, continues the above-mentioned leaching operation twice in repeating step two, obtain Mn in the first filtrate
2+concentration be 110.8g/L, represent that the first filtrate is now qualified, the leaching yield of manganese reaches 98%.
114g hydrogen peroxide (H is added in step 3, the first filtrate of obtaining to step 2
2o
2concentration is 30wt%), make Fe
2+be oxidized to Fe
3+, fully add 0.46L ammoniacal liquor adjust ph to 5.55 after reaction, the reaction that is hydrolyzed generates Fe (OH)
3with Al (OH)
3precipitation, filters after reacting completely and retains the second filtrate.In this second filtrate, the clearance of Fe, Al and Si is respectively 100%, 99.91% and 97.69%.
Add 6.16kg bicarbonate of ammonia in step 4, the second filtrate of obtaining to step 3, fully filters and retains the second filter residue and the 3rd filtrate after reaction.Above-mentioned second filter residue obtains 3.99kg manganous carbonate after washing, drying.Carry out evaporative crystallization to the 3rd filtrate at 200 DEG C, the crystalline solid obtained is ammonium sulfate.
Purity and the foreign matter content of manganous carbonate sample embodiment 1 ~ 3 obtained are analyzed, and result is as shown in table 4:
The compositional analysis of the manganous carbonate sample that table 4 embodiment 1 ~ 3 obtains
| Composition content (%) | Embodiment 1# | Embodiment 2# | Embodiment 3# |
| Mn | 46.80 | 46.60 | 46.44 |
| Cl | 0.0012 | 0.0010 | 0.0015 |
| SO 4 2- | 0.72 | 0.65 | 0.60 |
| Ca | 0.63 | 0.71 | 0.57 |
| SiO 2 | 0.015 | 0.029 | 0.019 |
| Al | 0.016 | 0.044 | 0.026 |
| K | 0.011 | 0.016 | 0.017 |
| Na | 0.095 | 0.079 | 0.083 |
| Mg | 0.012 | 0.017 | 0.016 |
| Pb | 0.0043 | 0.0068 | 0.0055 |
| Fe | 0.0071 | 0.0064 | 0.0069 |
As can be seen from Table 4, utilize the Application way of manganese oxide ore of the present invention can produce the higher manganous carbonate of purity, other foreign matter contents are lower simultaneously, can reach the index request of technical grade manganous carbonate standard HG/T4203-2011.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. an Application way for manganese oxide ore, is characterized in that, comprises the steps:
Step one, manganese oxide ore is levigate after carry out high intensity magnetic separation and obtain manganic concerntrate, magnetic tailing left after retaining magnetic separation;
Step 2, described magnetic tailing step one obtained is levigate is less than 0.15mm to granularity, sulphuric acid soln is mixed with described magnetic tailing, pass into sulfur dioxide gas and maintain Leaching reaction, leach filtration completely and obtain the first filter residue and the first filtrate, described first filtrate is the solution containing manganous sulfate, judges described containing Mn in the solution of manganous sulfate
2+concentration whether reach 102g/L, if, then represent that described first filtrate is qualified, end step two, if not, then represent that described first filtrate is defective, described first filtrate is mixed with the described magnetic tailing do not leached and the above-mentioned leaching operation repeated in step 2 until Mn in described first filtrate
2+concentration reach 102g/L;
Add oxygenant in step 3, described first filtrate that obtains to step 2, fully regulate pH to 4.95 ~ 6.0 after reaction, then filter and retain the second filtrate;
Add bicarbonate of ammonia in step 4, described second filtrate that obtains to step 3, fully filters and retains the second filter residue after reaction, described second filter residue is manganous carbonate;
In step 2, in the operation mix described first filtrate with described magnetic tailing, the liquid-solid mass ratio of described first filtrate and described magnetic tailing is 2.5:1 ~ 6:1.
2. the Application way of manganese oxide ore according to claim 1, is characterized in that, in step one, described manganese oxide ore is based on the manganese oxide ore of pyrolusite, brunite, manganite, psilomelane or meta-manganic acid ore.
3. the Application way of manganese oxide ore according to claim 1, is characterized in that, in step one, by being operating as of levigate for manganese oxide ore rear magnetic separation: carry out wet high-intensity magnetic separation after adopting coarse aggregate ore-dressing technique that manganese oxide ore is levigate.
4. the Application way of manganese oxide ore according to claim 3, is characterized in that, in step one, the magneticstrength of high intensity magnetic separation is 721kA/m ~ 1112kA/m.
5. the Application way of manganese oxide ore according to claim 1, is characterized in that, in step 2, the liquid-solid mass ratio of described sulphuric acid soln and described magnetic tailing is 2.5:1 ~ 6:1, and the concentration of described sulfuric acid is 0.30mol/L ~ 1.08mol/L.
6. the Application way of manganese oxide ore according to claim 1, it is characterized in that, in step 2, pass into sulfur dioxide gas and maintain in the operation of Leaching reaction, the flow of described sulfur dioxide gas is 0.2L/min ~ 20L/min, reaction times is 20min ~ 80min, and temperature of reaction is 0 DEG C ~ 30 DEG C.
7. the Application way of manganese oxide ore according to claim 1, is characterized in that, in step 3, described oxygenant is hydrogen peroxide, chlorine or Manganse Dioxide.
8. the Application way of manganese oxide ore according to claim 1, is characterized in that, in step 3, fully regulates being operating as of pH to 4.95 ~ 6.0 after reaction: fully add pH adjusting agent after reaction and regulate pH to 4.95 ~ 6.0, described pH adjusting agent is ammoniacal liquor, Na
2cO
3, NaHCO
3, (NH
4)
2cO
3, NH
4hCO
3or NaOH.
9. the Application way of manganese oxide ore according to claim 1, it is characterized in that, in step 4, described second filtrate and described bicarbonate of ammonia fully react rear filtration and retain the 3rd filtrate, carry out evaporative crystallization to described 3rd filtrate, the crystalline solid obtained is ammonium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410813834.4A CN104556233B (en) | 2014-12-23 | 2014-12-23 | Utilization method of manganese oxide ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410813834.4A CN104556233B (en) | 2014-12-23 | 2014-12-23 | Utilization method of manganese oxide ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104556233A CN104556233A (en) | 2015-04-29 |
| CN104556233B true CN104556233B (en) | 2016-04-20 |
Family
ID=53073438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410813834.4A Active CN104556233B (en) | 2014-12-23 | 2014-12-23 | Utilization method of manganese oxide ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104556233B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109939832B (en) * | 2019-04-10 | 2021-04-09 | 南华大学 | Manganese ore enrichment method combining selection and smelting |
| CN110668502A (en) * | 2019-10-31 | 2020-01-10 | 青川县青云上锰业有限公司 | Method for preparing manganese sulfate by purification |
| CN111302400A (en) * | 2019-10-31 | 2020-06-19 | 青川县青云上锰业有限公司 | Method for preparing manganese sulfate by purification |
| CN115094230B (en) * | 2022-06-23 | 2024-03-08 | 中国地质科学院矿产综合利用研究所 | Method for extracting rare earth, phosphorus and manganese elements from deep sea rare earth-rich sediment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02248327A (en) * | 1989-03-20 | 1990-10-04 | Chuo Denki Kogyo Kk | Production of manganese sulfate solution |
| AU776180B2 (en) * | 2000-04-04 | 2004-09-02 | Tosoh Corporation | Treated manganese ore, process for producing the same, and use thereof |
| CN102390868B (en) * | 2011-08-22 | 2013-06-26 | 青海华信冶炼有限公司 | Method for producing manganese sulfate from smelting furnace gas |
-
2014
- 2014-12-23 CN CN201410813834.4A patent/CN104556233B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104556233A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101875129B (en) | Method for comprehensive utilization of high-iron bauxite | |
| CN102703715B (en) | Method for recovering rhenium and molybdenum from rhenium and molybdenum-containing concentrate calcination flue dust | |
| CN112410556B (en) | Method for recovering waste lithium iron phosphate powder | |
| CN103789551B (en) | Prepare manganese sulfate electrolyte with electrolytic manganese anode mud and reclaim plumbous method | |
| CN102828025B (en) | Method for extracting V2O5 from stone coal navajoite | |
| CN103205570B (en) | Bone coal navajoite and pyrolusite together produce the method for Vanadium Pentoxide in FLAKES by-product manganese sulfate | |
| CN104556233B (en) | Utilization method of manganese oxide ore | |
| CN107555442B (en) | Method for refining high-purity quartz sand by using common quartz sand | |
| CN102557086B (en) | Method for recovering phosphorus from phosphorite tailings and preparing light magnesium oxide | |
| CN112522512B (en) | Method for preparing battery-grade cobalt sulfate by using organic cobalt slag of zinc smelting plant | |
| CN101693543B (en) | High value-added greening comprehensive utilization method of boron concentrate, boron-containing iron concentrate and ludwigite | |
| CN102432071A (en) | Method for integrally utilizing high-iron-content bauxite | |
| CN112760487A (en) | Method for recovering manganese and lead from electrolytic manganese anode slag | |
| CN110735032A (en) | vanadium-titanium-iron paragenetic ore treatment process | |
| CN113772734A (en) | Method for recovering manganese and iron resources from manganese slag | |
| CN107574308A (en) | A kind of method of Manganese anode slime manganese lead separation | |
| CN104611541B (en) | A kind of method leaching rare earth in iron selection tailings | |
| CN110255591A (en) | The method of phosphorus ore de-magging co-production magnesium carbonate and calcium carbonate | |
| CN105399132A (en) | Technology for preparing tribasic copper chloride and tetrabasic zinc chloride by utilization of brass slag and zinc-containing flue ash | |
| CN115786732A (en) | Method for extracting lithium resource from clay type lithium ore | |
| CN109852811A (en) | A kind of zinc-iron efficient separation method | |
| CN108950239A (en) | A method of it produces using containing zinc ore crude containing zinc complexes | |
| CN108588413A (en) | A method of producing nano zine oxide using containing zinc ore crude | |
| CN114192274A (en) | Manganese ore resource utilization method combining smelting and selecting materials | |
| CN103526054A (en) | Method for preparing rare earth ore concentrates by using low-grade light rare earth tailings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |