CN101913654A - Method for preparing manganese oxide concentrate by utilizing manganese carbonate ore - Google Patents
Method for preparing manganese oxide concentrate by utilizing manganese carbonate ore Download PDFInfo
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- CN101913654A CN101913654A CN2010102623615A CN201010262361A CN101913654A CN 101913654 A CN101913654 A CN 101913654A CN 2010102623615 A CN2010102623615 A CN 2010102623615A CN 201010262361 A CN201010262361 A CN 201010262361A CN 101913654 A CN101913654 A CN 101913654A
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Abstract
The invention discloses a method for preparing manganese oxide concentrate by utilizing manganese carbonate ore, which relates to the technical field of extraction and processing of manganese carbonate, and is characterized in that manganese carbonate concentrate obtained by magnetic separation or medium-grade manganese carbonate raw ore is ground to be below 200 meshes, mineral powder is added with water and is subjected to size mixing to reach the concentration of 20-40%, calcium chloride with the theoretical amount of 3-6 times is added, and the calcium chloride is leached for 0.5-3 hours at the temperature of 200-280 ℃. Adding lime milk with the theoretical amount of 1.0-1.1 times into the manganese leaching solution, and stirring and reacting for 0.5-4 hours at the temperature of 70-110 ℃ to obtain a qualified manganese oxide product for metallurgy, wherein the Mn content is more than or equal to 48%, the P content is less than or equal to 0.05%, the Fe content is less than or equal to 0.3%, and the Si content is less than or equal to 0.1%. The method has simple production process, basically does not leach harmful impurities such as phosphorus, iron, silicon and the like, does not generate waste gas and waste water in the whole production process, and has little pollution to the environment.
Description
Technical field
The present invention relates to manganous carbonate and extract processing technique field, relate in particular to a kind of extraction working method low-grade, high phosphorus, high ferro, high-silicon type manganese carbonate ore.
Background technology
The manganese carbonate ore major part of China is low-grade high phosphorus poor manganese ore, and national manganese average grade is about 18%, and the rich ore (manganese carbonate ore Mn 〉=25%) that meets the international commodity level does not almost have.Along with Chinese manganese is the fast development of industry, industries such as metallurgy, chemistry, electronics increase year by year to the demand of manganese, and the manganese ore of domestic production can not meet the demands far away, need a large amount of imports every year.In accelerating industrialized process, the assurance degree of Chinese manganese ore will further reduce.
In the prior art, low-grade manganese carbonate ore is generally adopted magnetic concentration, sulfuric acid leaches the method for producing electrolytic manganese or manganous sulfate or the rich manganese slag of high melt production and utilizes.
As publication number is CN101372362, and the Chinese patent literature that open day is on February 25th, 2009 discloses a kind of preparation method and new purposes of high quality chemical manganese bioxide.Technology characteristics is earlier manganous carbonate pyrolysis in pyrolysis oven to be generated thick Manganse Dioxide, then thick Manganse Dioxide being carried out heaviness with sodium chlorate in the mixing solutions of sulfuric acid and manganous sulfate handles, obtain heaviness Manganse Dioxide particle, detrimental impurity such as wherein ammonium of water flush away, sodium obtains tap density greater than 2.4G/CM then
3, specific surface area is less than 30M
2/ G, NH
4+ and Na+ content less than 300PPM, crystal formation is even spheric high quality chemical manganese bioxide product.An important new purposes of the present invention is the production that is used for lithium cell anode material lithium manganate, and resulting lithium manganate initial discharge capacity is greater than 110MAH/G (discharge-rate 1C), and it is 70% that 500 circulation volumes are held rate.
But aforementioned production method, complex manufacturing, cost height, energy consumption height, environmental pollution are serious, and manganese phosphorus separating effect is poor.
Summary of the invention
For solving the problems of the technologies described above, the present invention proposes a kind of method of utilizing manganese carbonate ore to prepare manganese oxide concentrate, present method has solved complex manufacturing in the prior art, cost height, energy consumption height, the technical problem of the serious and manganese phosphorus separating effect difference of environmental pollution, the manganic concerntrate grade can be increased to more than 48%, detrimental impurity such as phosphorus, iron, silicon reach the quality standard of metallurgical grade manganic concerntrate.
The present invention realizes by adopting following technical proposals:
A kind of method of utilizing manganese carbonate ore to prepare manganese oxide concentrate is characterized in that comprising the steps:
1) with middle grade manganese carbonate ore, perhaps the manganous carbonate fine ore that obtains through magnetic separation is broken to below 200 orders, forms breeze;
2) in breeze, add water and size mixing, form ore pulp to 20%～40% concentration;
3) add calcium chloride in ore pulp, the add-on of calcium chloride is 3～6 times of theoretical amount;
4) ore pulp is added in the autoclave, and the leaching of under 200 ℃～280 ℃ condition, pressurizeing, extraction time is 0.5～3 hour, then the leach liquor that obtains is carried out filtration washing;
5) add milk of lime in the leach liquor after washing after filtration, the add-on of milk of lime is 1.0～1.1 times of theoretical amount, the granularity of milk of lime is controlled at below 200 orders, and stirring reaction 0.5～4 hour under 70 ℃～110 ℃ condition obtains manganese oxide concentrate product and calcium chloride solution then.
In the described step 5), stirring reaction obtained precipitation after 0.5～4 hour under 70 ℃～110 ℃ condition, and precipitation is filtered, and obtained manganous hydroxide precipitation and calcium chloride mother liquor, and the dehydration of manganous hydroxide precipitation drying obtains manganese oxide concentrate.
After described calcium chloride mother liquor carried out evaporation concentration, be added in the ore pulp described in the step 3) recycle once more.
Grade manganese carbonate ore in described, perhaps the grade of the manganous carbonate concentrate that obtains through magnetic separation is 18%～22%.
The add-on of described calcium chloride is that theoretical amount is meant the stoichiometric calculation numerical value that reacts in calcium chloride and the manganese ore in 3～6 times of theoretical amount.
Reaction equation is: MnCO
3+ CaCl
2=MnCl
2+ CaCO
3
The add-on of described milk of lime is that theoretical amount is meant the stoichiometric calculation numerical value of milk of lime and Manganous chloride tetrahydrate in 1.0～1.1 times of theoretical amount.
Reaction equation is: MnCl
2+ Ca (OH)
2=Mn (OH)
2+ CaCl
2
Compared with prior art, the beneficial effect that the present invention reached is as follows:
1, employing of the present invention 1)-5) technical scheme of step, technology is simple relatively, and cost is low, energy consumption is low, environment is not almost polluted, and manganese phosphorus good separation effect can be increased to the manganic concerntrate grade more than 48%, P≤0.05%, Fe≤0.3%, the qualified metallurgy manganese product of Si≤0.1%.
2, among the present invention, adopt the calcium chloride pressurization to leach, detrimental impurity phosphorus, iron, silicon etc. are not leached substantially, need not pass through loaded down with trivial details removal of impurities process, and technical process is short, helps lowering tooling cost.
3, among the present invention, whole process flow does not have waste gas and waste water produces, and it is neutral leaching the waste residue that produces, and environmental pollution is little.
4, among the present invention, described calcium chloride mother liquor carried out evaporation concentration after, be added to once more in the ore pulp described in the step 3), realized the reprocessing cycle use, and its regeneration rate can reach more than 95%, the production run cost is low.
5, the present invention, to phosphorus manganese good separating effect, product is phosphorous to reach the metallurgical manganese requirement of using.
Through experiment, through magnetic concentration to 18%～22% manganous carbonate concentrate (or middle grade manganous carbonate raw ore) leaching of pressurizeing, manganese recovery ratio can reach more than 90% to the low-grade manganese carbonate ore that contains manganese about 10% in the present invention; The manganese leach liquor adds milk of lime and precipitates, and the manganese deposition rate can reach more than 99%, and concrete experimental data and result are described with reference to embodiment.
Description of drawings
The present invention is described in further detail below in conjunction with specification drawings and specific embodiments, wherein:
Fig. 1 is a process flow sheet of the present invention
Embodiment
Embodiment 1:
Get manganous carbonate raw ore 100 grams of manganese content 19.2%, levigate to 200 orders, add water and size mixing to 30% pulp density, add 200g calcium chloride, add in the 1L lining titanium reactor, pressurization was leached 2 hours under the condition of 260 ℃ of temperature, the manganese leaching yield can reach 92.36%, soaks slag manganese content 1.54%.The milk of lime that leach liquor adds 1.07 times of theoretical amount precipitates 2 hours under the condition of 100 ℃ of temperature, the manganese deposition rate can reach 99.83%.Precipitation obtains manganic concerntrate 33.75 grams, manganic concerntrate grade 52.47%, and phosphorus content 0.0033%, iron 0.0072%, silicon 0.0067%, quality product has reached metallurgical grade manganese product quality standard.Whole flow process manganese recovery ratio can reach 92.20%.
Embodiment 2
Get manganese content 21.5% manganous carbonate magnetic concentrate 100 grams, levigate to 200 orders, adding water sizes mixing to 30% pulp density, add 200g calcium chloride, add in the 1L lining titanium reactor, pressurization was leached 2 hours under the condition of 280 ℃ of temperature, and the manganese leaching yield can reach 91.28%, soaks slag manganese content 1.95%.The milk of lime that leach liquor adds 1.04 times of theoretical amount precipitates 2 hours under the condition of 100 ℃ of temperature, the manganese deposition rate can reach 99.22%.Precipitation obtains manganic concerntrate 34.54 grams, manganic concerntrate grade 56.38%, and phosphorus content 0.0065%, iron 0.0032%, silicon 0.0046%, quality product has reached metallurgical grade manganese product quality standard.Whole flow process manganese recovery ratio can reach 90.56%, and precipitation manganese post chlorization mother liquor of calcium calcium chloride regeneration rate can reach 97.43%.
Embodiment 3
With embodiment 2 calcium chloride mother liquor evaporation concentration, add calcium chloride 5.1 grams.Get manganese content 21.5% manganous carbonate magnetic concentrate 100 grams, levigate to 200 orders.Size mixing to 30% pulp density with the calcium chloride mother liquor after concentrating, add in the 1L lining titanium reactor, pressurization was leached 2 hours under the condition of 280 ℃ of temperature, and the manganese leaching yield can reach 90.96%, soaks slag manganese content 2.05%.The milk of lime that leach liquor adds 1.04 times of theoretical amount precipitates 2 hours under the condition of 100 ℃ of temperature, the manganese deposition rate can reach 99.97%.Precipitation obtains manganic concerntrate 36.58 grams, manganic concerntrate grade 53.30%, and phosphorus content 0.0042%, iron 0.0072%, silicon 0.0063%, quality product has reached metallurgical grade manganese product quality standard.Whole flow process manganese recovery ratio can reach 90.68%, and precipitation manganese post chlorization mother liquor of calcium calcium chloride regeneration rate can reach 96.54%.
Embodiment 4
With embodiment 3 calcium chloride mother liquor evaporation concentration, add calcium chloride 6.9 grams.Get manganese content 21.5% manganous carbonate magnetic concentrate 100 grams, levigate to 200 orders.Size mixing to 30% pulp density with the calcium chloride mother liquor after concentrating, add in the 1L lining titanium reactor, pressurization was leached 2 hours under the condition of 280 ℃ of temperature, and the manganese leaching yield can reach 91.21%, soaks slag manganese content 1.97%.The milk of lime that leach liquor adds 1.04 times of theoretical amount precipitates 2 hours under the condition of 100 ℃ of temperature, the manganese deposition rate can reach 99.65%.Precipitation obtains manganic concerntrate 35.95 grams, manganic concerntrate grade 54.35%, and phosphorus content 0.0086%, iron 0.0091%, silicon 0.0057%, quality product has reached metallurgical grade manganese product quality standard.Whole flow process manganese recovery ratio can reach 90.89%, and precipitation manganese post chlorization mother liquor of calcium calcium chloride regeneration rate can reach 95.74%.
Embodiment 5
Get manganese content 21.5% manganous carbonate magnetic concentrate 1500 grams, levigate to 200 orders, adding water sizes mixing to 30% pulp density, add 3000g calcium chloride, add in the 10L lining titanium reactor, pressurization was leached 2 hours under the condition of 280 ℃ of temperature, and the manganese leaching yield can reach 92.63%, soaks slag manganese content 1.65%.The milk of lime that leach liquor adds 1.06 times of theoretical amount precipitates 2 hours under the condition of 100 ℃ of temperature, the manganese deposition rate can reach 99.76%.Precipitation obtains manganic concerntrate 565.9 grams, manganic concerntrate grade 52.68%, and phosphorus content 0.0041%, iron 0.0034%, silicon 0.0072%, quality product has reached metallurgical grade manganese product quality standard.Whole flow process manganese recovery ratio can reach 92.41%, and precipitation manganese post chlorization mother liquor of calcium calcium chloride regeneration rate can reach 96.52%.
Embodiment 6
With reference to Figure of description 1, the invention discloses a kind of method of utilizing manganese carbonate ore to prepare manganese oxide concentrate, its step is as follows:
1) with grade be 18%～22% middle grade manganese carbonate ore, perhaps the manganous carbonate fine ore that obtains through magnetic separation is broken to below 200 orders, forms breeze;
2) in breeze, add water and size mixing, form ore pulp to 20%～40% concentration;
3) add calcium chloride in ore pulp, the add-on of calcium chloride is 3～6 times of theoretical amount, and theoretical amount is meant the stoichiometric calculation numerical value that reacts in calcium chloride and the manganese ore.
Reaction equation is: MnCO
3+ CaCl
2=MnCl
2+ CaCO
3
4) ore pulp is added in the autoclave, and the leaching of under 200 ℃～280 ℃ condition, pressurizeing, moulding pressure is relevant with temperature, can directly convert according to temperature range to draw, and extraction time is 0.5～3 hour, then the leach liquor that obtains is carried out filtration washing;
5) add milk of lime in the leach liquor after washing after filtration, the add-on of milk of lime is 1.0～1.1 times of theoretical amount, and theoretical amount is meant the stoichiometric calculation numerical value of milk of lime and Manganous chloride tetrahydrate.
Reaction equation is: MnCl
2+ Ca (OH)
2=Mn (OH)
2+ CaCl
2
The granularity of milk of lime is controlled at below 200 orders, stirring reaction 0.5～4 hour under 70 ℃～110 ℃ condition then, obtain precipitation, precipitation is filtered, obtain manganous hydroxide precipitation and calcium chloride mother liquor, the dehydration of manganous hydroxide precipitation drying obtains manganese oxide concentrate, and certainly, manganous hydroxide can be oxidized to mixed oxidization manganese: Mn (OH) in the drying course
2+ O
2→ MnOMnO
2+ H
2O is added in the ore pulp described in the step 3) recycle after described calcium chloride mother liquor is carried out evaporation concentration once more.Described recycle concrete grammar is: calcium chloride solution is after evaporation concentration, return step 2) size mixing, and make pulp density identical with the preceding pulp density of once being transferred, add calcium chloride in the calcium chloride after evaporation concentration, the amount of adding calcium chloride is the amount of the calcium chloride of preceding primary sedimentation manganous hydroxide institute loss.
The invention is not restricted to above-mentioned embodiment; description according to the foregoing description; under the prerequisite that does not break away from concrete steps of the present invention; those skilled in the art also can make some conspicuous changes to above-mentioned embodiment; for example adjust each composition concrete add-on, adjust concrete reaction conditions etc., but these changes all should fall within the protection domain of claim of the present invention.
Claims (6)
1. a method of utilizing manganese carbonate ore to prepare manganese oxide concentrate is characterized in that comprising the steps:
1) with middle grade manganese carbonate ore, perhaps the manganous carbonate fine ore that obtains through magnetic separation is broken to below 200 orders, forms breeze;
2) in breeze, add water and size mixing, form ore pulp to 20%～40% concentration;
3) add calcium chloride in ore pulp, the add-on of calcium chloride is 3～6 times of theoretical amount;
4) ore pulp is added in the autoclave, and the leaching of under 200 ℃～280 ℃ condition, pressurizeing, extraction time is 0.5～3 hour, then the leach liquor that obtains is carried out filtration washing;
5) add milk of lime in the leach liquor after washing after filtration, the add-on of milk of lime is 1.0～1.1 times of theoretical amount, the granularity of milk of lime is controlled at below 200 orders, and stirring reaction 0.5～4 hour under 70 ℃～110 ℃ condition obtains manganese oxide concentrate product and calcium chloride solution then.
2. a kind of method of utilizing manganese carbonate ore to prepare manganese oxide concentrate according to claim 1, it is characterized in that: in the described step 5), stirring reaction is after 0.5～4 hour under 70 ℃～110 ℃ condition, obtain precipitation, precipitation is filtered, obtain manganous hydroxide precipitation and calcium chloride mother liquor, the dehydration of manganous hydroxide precipitation drying obtains manganese oxide concentrate.
3. a kind of method of utilizing manganese carbonate ore to prepare manganese oxide concentrate according to claim 2 is characterized in that: after described calcium chloride mother liquor is carried out evaporation concentration, be added in the ore pulp described in the step 3) recycle once more.
4. the method for utilizing manganese carbonate ore to prepare manganese oxide concentrate according to claim 1 is characterized in that: grade manganese carbonate ore in described, perhaps the grade of the manganous carbonate concentrate that obtains through magnetic separation is 18%～22%.
5. the method for utilizing manganese carbonate ore to prepare manganese oxide concentrate according to claim 1 is characterized in that: the add-on of described calcium chloride is that theoretical amount is meant the stoichiometric calculation numerical value that reacts in calcium chloride and the manganese ore in 3～6 times of theoretical amount.
6. the method for utilizing manganese carbonate ore to prepare manganese oxide concentrate according to claim 1 is characterized in that: the add-on of described milk of lime is that theoretical amount is meant the stoichiometric calculation numerical value of milk of lime and Manganous chloride tetrahydrate in 1.0～1.1 times of theoretical amount.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2010
- 2010-08-25 CN CN2010102623615A patent/CN101913654A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《全国第二届湿法冶金及第三届有色冶金物理化学学术会议》 19911231 黎海雁等 磁选-CaCl2浸出法处理高磷碳酸锰矿石 363-372 1-6 , 2 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Application publication date: 20101215 |