CN109939832A - A kind of manganese ore enrichment method of selecting smelting combination - Google Patents
A kind of manganese ore enrichment method of selecting smelting combination Download PDFInfo
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Abstract
The invention discloses a kind of manganese ore enrichment method of selecting smelting combination, include the following steps: that manganese ore ore pulp is made in water and manganese ore mixed grinding by (1)；(2) manganese ore ore pulp and leaching agent are mixed, control its pH value be 3~5.5 leached after, isolated manganese chats and leachate；(3) manganese chats is subjected to Counterfloatating desiliconization, obtains manganese iron ore concentrate；(4) regenerative agent quick lime and sulfuric acid are successively added in leachate, obtains regenerated leaching agent return step (2) and uses, sold outside magnesium hydroxide and calcium sulfate.Rich manganese method flow of the invention is short, not sewage effluent and waste residue, do not need heating or pressurized equipment and to the requirement for anticorrosion of equipment low, production safety, it is environmentally protective, it can be achieved that manganese and iron, calcium, silicon step by step arithmetic.
Description
Technical field
The invention discloses a kind of manganese ore especially ferrous manganese ore, magnetic separation manganese mine tailings selecting smelting combination manganese ore enrichment side
Method, the invention belongs to chemical metallurgy Minerals manufacture fields, and in particular to a kind of ore dressing of manganese ore and chemical combined enrichment side
Method.
Background technique
Chinese promoter manganese rich reserves, but grade is not high, and silicon, aluminium, iron, calcium mineral content are larger, and manganese belongs to iron family element, contains
Amount accounts for about the 0.1% of the earth's crust, and physicochemical properties are close with iron phase.Manganese is distributed in nature with various compound forms.
Manganese-base alloy is essential important source material in steel and iron industry, and manganese is also used to produce manganese metal, manganese alloy and manganese
Compound, be widely used in industry, agricultural and military affairs etc..China is the poor country of promoter manganese, the self-supporting amount of promoter manganese
Wretched insufficiency, for the manganese ore reserve in China, most of is poor manganese ore, rich manganese ore account for gross reserves less than 10%.Therefore,
The research for comprehensively utilizing low lean manganese ore resources is more and more important, the synthetical recovery of manganese ore dressing tailings and low lean manganese resource, in economy
There is positive effect in construction.
Manganese ore is divided into manganese carbonate ore, manganese oxide ore, mixed type by the natural type and contained accompanying element of mineral
Ore and polymetallic ore.Although the type comparison of manganese ore is more, the ore dressing side of basic beneficiation method and weak-magnetic iron ore
Method is close, its main feature is that beneficiation method is more, and is used in combination more, but concentration ratio is low and the rate of recovery is not high；Mineral Processing For Manganese Ore it is another
A feature is gradation grade ore dressing, to obtain the concentrate of size fractionated.To improve sorting index, coarse fraction magnetic after Chang Jinhang desliming
Choosing, then grade gravity treatment in carrying out, finally carry out fine fraction flotation, separate or extract accompanying element to realize manganese ore with gangue, subtract
Few production cost.
The type of China's manganese ore accounts for about the 73% of gross reserves based on carbonate manganese ore.The grade of this kind of ore is very low,
General manganese grade is 20% hereinafter, more category marine deposit types and metamorphosed sedimentary type manganese ore deposit, about 400,000,000 tons of reserves, main
It is distributed across the ground such as Yunnan, Sichuan, Hunan, Hubei, Guangxi.
Manganese ore has the characteristics that hardness is lower, property is crisp, causes it to exploit, easy argillization in transport and shattering process.According to manganese
The difference of mine type, beneficiation method difference.Currently, cannot using beneficiation methods such as conventional gravity treatment, magnetic separation, flotation
Obtain preferable production, result of management, it is more difficult to achieve the purpose that resource-effective and environmental-friendly.
Since late nineteenth century, people just study extracts manganese with hydrometallurgical method from raw material containing manganese.But research
Direction is nearly all to leach, extract manganese, mainly selects chemical raw material appropriate that the manganese in ore is made to be changed into soluble shape
State enters solution, separates with gangue mineral, and then purified solution removes dissolved impurity such as Fe, Al, Si, P, Cu together with manganese
Deng finally producing required manganese product, such as electrolytic manganese, manganese oxide and various manganese salts with the methods of electrodeposition, precipitating or crystallization.So
And all there is the defects of long flow path, operation is difficult, at high cost in these methods, and be not suitable for the low lean manganese that manganese content is lower than 10%
Mine.It can be used for the low grade based on psilomelane or Ferromanganese Ore, the beneficiation method of low-grade poor manganese ore yet there are no successful example.
Semi-manganese oxide ore, psilomelane, Ferromanganese Ore are all typical complicated difficult manganese ores, the manganese ore mineral deposit of such ore at
Because generally falling into appositional pattern or metamorphosed sedimentary type mineral deposit, calcium, magnesium, iron tramp etc. are disseminated in manganese ore with isomorphous particulate,
Have the characteristics that disseminated grain size is thin and symbiosis is complicated, wants ore grinding at 5~10 μm hereinafter, to increase monomer dissociation
The difficulty of minerals separation, causes also to be difficult to separate with the method for magnetic separation, gravity treatment, flotation combined ore dressing.Therefore, it only develops
Difficulty selects manganese ore key technology, is just able to achieve the higher value application of such resource.
Document " recycling of low-grade manganese carbonate ore is studied " mentions a kind of method for handling low-grade manganese, i.e., will
The raw ore of Mn8.11%, Fe3.41% are handled using sulfuric acid leaching, and optimization experiment condition reaches to product quality requirement；Document
" research that Magnetization reductive roasting handles low-grade ferrous manganese ore " refers to a kind of method for handling low-grade manganese, by Fe30-
45%, the Ferromanganese Ore of Mn7-15% carries out reduction roasting in reducing atmosphere and under certain temperature system, and roasting material is carried out again
Sulfuric acid leaching；Document " recycling of low-grade manganese carbonate ore is studied " and document " the low-grade manganese iron of Magnetization reductive roasting processing
The method that the research of mine " is mentioned has used sulfuric acid leaching.The equal process of these methods is complicated, requires equipment anticorrosion high；Through sulphur
In the liquid containing manganese of Ore Leaching, impurity content is high, increases the cost of subsequent handling.
Patent (application number CN200710062305.5) discloses a kind of method for handling low-grade manganese powder, by poor manganese ore
Powder is by selected raw material, crushing, fine grinding, sieving, mixing, stirring, micro-wave oven preheating, carbon monoxide prereduction, eventually reduction, high temperature
Refining, nitrogen cooling protection, magnetic separation purification directly prepare low-carbon manganese metal iron.This method process is longer, needs high temperature and microwave
Heating, special gas reduction and protection, it is difficult to industrial applications.
Patent (application number CN200810143103.8) discloses a kind of beneficiation method of low ore grade manganous carbonate ore, the hair
Bright is to add water to be tuned into ore pulp Raw Ore grind into powder, under certain pH value, is proportionally added into medicament, carries out closed circuit follow
Ring flotation.The rate of recovery of this method manganese is up to 85%, but flotation operation concentration ratio is only 1.5, cannot obtain high-grade manganese ore.
Patent (application number CN201010300557.9) discloses a kind of beneficiation method of low ore grade manganous carbonate ore, the hair
Bright technical solution is characterized in that: being used thickness grading magnetic cobbing fine particles flotation recovery process, can be obtained step by step grade and reach
26% manganese magnetic concentrate and manganese flotation concentrate 18%, to realize that the comprehensive recovery of 8% low-grade manganese carbonate ore reaches 80%
More than, but the method actual recovered rate is not high, it is also difficult to obtain high-grade manganic concerntrate.
Patent (application number CN201110300784.6) discloses a kind of method of preparing manganeisen from low grade manganese mine, will
The low-grade manganese that metal manganese content is 15-30% is dried, and mixes with addition of reducing agent, catalyst, flux and binder, this is answered
It closes in raw material merging rotary kiln or tunnel oven, using coal gas or natural gas as the energy, weakly reducing atmosphere in furnace is kept, certain
It is reacted under temperature schedule, reacting rear material obtains manganeisen and tailings through cooling, magnetic separation.This method also needs kiln
Equipment carries out high temperature reduction, and energy consumption is high, at high cost, is difficult to reach relevant criterion requirement through the manganeisen that magnetic separation obtains.
Patent (application number CN201510413971.3) discloses the low of a kind of a small amount of limonite of high silicon association and psilomelane
The beneficiation method of poor manganese ore, this method simple process, but restricted application, the rate of recovery are low.
Patent (application number CN201710687368.3) discloses manganese, iron isochronous resources in a kind of low-grade manganese carbonate ore
The method utilized, the essence of this method are sulfuric acid leachings, then are settled out from manganese sulfate solution with the form that ammonium jarosite precipitates
Iron.The invention can solve in low-grade manganese carbonate ore the high problem of iron content in sulphuric leachate, but relative to manganese-base alloy
For, it is reduction of the utility value of iron, and there is still a need for other process to remove other impurity in leachate.
Summary of the invention
In order to solve the problems in the existing technology, the object of the present invention is to provide a kind of manganese of selecting smelting combination richnesses
Set method, this method process is short, not sewage effluent and waste residue, do not need heating or pressurized equipment, and the requirement for anticorrosion to equipment
Low, production safety, it is environmentally protective, it can be achieved that manganese and iron, calcium, silicon step by step arithmetic.
To achieve the goals above, the present invention provides a kind of manganese ore enrichment method of selecting smelting combination, include the following steps:
(1) manganese ore ore pulp is made in water and manganese ore mixed grinding；
(2) manganese ore ore pulp and leaching agent are mixed, controlling its pH value is 3~5.5, after being leached, isolated leaching
Liquid and manganese chats；
(3) manganese chats is subjected to Counterfloatating desiliconization, obtained flotation froth concentrate is silicon concentrate, and underflow tailing is manganese iron essence
Mine；
(4) regenerative agent quick lime and sulfuric acid are successively added in leachate, obtaining regenerated leaching agent return step (2) makes
With magnesium hydroxide and calcium sulfate are sold outside.
Preferably, the manganese ore is pyrolusite, psilomelane, hausmannite, manganese spar, todorokite, calcimangite and manganese sparring
At least one of mine；More preferably at least one of manganese spar, todorokite and calcimangite.
Preferably, in step (1), the solvent and solute weight ratio of water and manganese ore is 2~6:1；The liquid of more preferably water and manganese ore is solid
Weight ratio is 3~5:1.
Preferably, in step (1), be mixed to prepare manganese ore ore pulp for manganese ore and water are ground, wherein granularity be -74 μ m≤
70%；More preferable granularity is -74 μm of accountings 80%~90%.
Preferably, in step (2), the pH value is 4.5~5.5.Inventors have found that the energy in currently preferred range
Further promote the grade of manganese in the overall recovery and manganese iron ore concentrate of manganese.
Preferably, in step (2), leaching agent is the hydrochloric acid of 1~10wt%；The more preferably hydrochloric acid of 5~8wt%.This hair
Bright strict control leaches pH value dexterously under dilute hydrochloric acid leaching condition, has preferentially leached the carbonate of calcium, magnesium, manganese in manganese ore,
Less than 5%, calcium carbonate and magnesium carbonate are preferentially reacted with leaching agent generation the leaching rate of iron, silicon etc. as follows:
CaCO3+ 2HCl=CaCl2+H2O+CO2
MgCO3+ 2HCl=MgCl2+H2O+CO2
The manganese chats being enriched with after reaction has dissolved carbonate in manganese ore and other mineral (quartz, mica, brown iron
Mine etc.) in cementation, make it possible the independent flotation of other mineral.
For the present invention under dilute hydrochloric acid leaching condition, needing strict control to leach pH value will cause the dissolution of manganese when pH is too low
Into leachate, the loss of manganese is generated；When pH is excessively high, it will cause the dissolution of calcium, magnesium is incomplete, it is difficult to realize silicate mineral
With the dissociation of manganese mineral, the rate of recovery and grade of subsequent flotation manganese are reduced.
Preferably, in step (3), reverse flotation condition are as follows: the solvent and solute weight ratio of water and manganese chats is 3~8:1, pH value 7
~11, floating agent is one of C12~C18 kiber alkyl amine salt or combinations thereof, and dosage is 20~500 g tons.
Preferably, in step (4), Ca in leaching agent is regenerated2+Concentration is not less than 0.5g/L, Mg2+Concentration is not less than 0.2g/
L.Following reaction occurs for leachate regenerative process of the present invention:
MgCl2+Ca(OH)2=Mg (OH)2↓+CaCl2
CaCl2+H2SO4=CaSO4↓+2HCl
Implement in this step, inventor is the study found that Mg2+When concentration is less than 0.2g/L, lime and sulfuric acid dosage will cause
Increase, to increase preparation cost；Ca2+When concentration is less than 0.5g/L, sulfuric acid dosage, and regenerated leaching agent not only will increase
In can have sulfuric acid, thus in the leaching process of step (2), generate calcium sulfate colloid in mineral particle surface, influence to leach
Effect.
Preferably, after above-mentioned steps are handled, the overall recovery of manganese is 90%~95%, the quality of manganese in manganese iron ore concentrate
Content is 25%~35%.
The present invention regenerates process by ore grinding-leaching-reverse flotation-immersion liquid, and manganese ore ore pulp is made in manganese ore first；Manganese
Mine ore pulp under conditions of strict control pH, preferentially leaches the carbonate of calcium, magnesium, manganese, iron, silicon in manganese ore through dilute hydrochloric acid leaching agent
Deng leaching rate less than 5%, obtain manganese chats and leachate to leach；Manganese chats obtains silicon concentrate after reverse flotation flowsheet again
With manganese iron ore concentrate；Leachate is regenerated by immersion liquid, and obtained regeneration leaching agent returns to manganese ore ore pulp and leaches, obtained byproduct hydrogen
Magnesia, gypsum etc. after dewatering can direct marketings.Process through the invention reaches a variety of valuable in comprehensive utilization raw ore
Ingredient and the purpose for improving economic value, extraction process are that a kind of green selects smelting new technology substantially without solid waste discharge.
Compared with prior art, the beneficial effects of the present invention are:
(1) compared with manganese ore magnetic method process of enriching, manganese, iron the rate of recovery improve 20% or more.
(2) compared with manganese ore floatation process of enriching, the step by step arithmetic of manganese and iron, calcium, silicon is realized.
(3) compared with manganese ore gravity separation method process of enriching, 50% or more concentration ratio is improved.
(4) compared with hydrometallurgy technique, the method for the present invention process is short, production safety, do not need heating or pressurized equipment,
And it is low to the requirement for anticorrosion of equipment.
(5) present invention has preferentially leached the carbonate of calcium, magnesium, has dissolved it in manganese ore under low-concentration hcl leaching condition
With the cementation in other mineral (quartz, mica, limonite etc.), make it possible the independent flotation of other mineral.
(6) present invention removes impurity using sulfuric acid, lime of low value etc., realizes the regeneration of leaching agent and recycles,
To realize not sewage effluent.
(7) present invention is while enrichment manganese and iron, also using calcium, magnesium, silicon as byproduct step by step arithmetic, substantially without solid
Waste discharge is that a kind of green selects smelting new technology.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Embodiment 1
A kind of manganese ore enrichment method of selecting smelting combination, concrete operations are as follows:
Yunnan difficulty selects manganese ore ore, the mass percent of chemical component are as follows:
1 manganese ore multielement analysis result of table/%
| Mn | TFe | P | SiO2 | MgO | CaO | Al2O3 | Igloss |
| 14.89 | 2.65 | 0.16 | 4.79 | 4.82 | 32.67 | 0.35 | 31.58 |
(1) ore is crushed, after adding water to enter ball milling, obtains -74 μm of granularity and account for 85.3%, the manganese that liquid-solid ratio is 3
Mine ore pulp；
(2) above-mentioned manganese ore ore pulp is added in agitator, under 300r/min stirring, being uniformly added into mass concentration is 6%
The leaching agent of HCl, holding slurry pH are 4.5-5.5, leach 3 hours, obtain and leach slurry；
(3) slurry will be leached to precipitate 1 hour, and will release top leachate, bottom is manganese chats；
(4) clear water mining in the manganese of bottom is washed 3 times, after being dehydrated and drying, obtains dry manganese chats, analyzes wherein each element
Leaching rate is respectively as follows: Mn 2.62%, Fe 3.54%, Ca 92.3%, Mg 90.6%；The grade of dry manganese chats is analyzed, is Mn
35.6%, it can reach manganic concerntrate grade without flotation.
Embodiment 2
A kind of manganese ore enrichment method of selecting smelting combination, concrete operations are as follows:
Manganite magnetic separation manganese ore tailing, the mass percent of chemical component are built in Yunnan are as follows:
2 raw ore multielement analysis result of table/%
| Mn | TFe | P | SiO2 | MgO | CaO | Al2O3 | Igloss |
| 9.81 | 3.15 | 0.14 | 15.16 | 5.12 | 30.09 | 0.35 | 32.10 |
(1) ore is crushed, after ore grinding processing, obtains -74 μm of granularity and accounts for 86.0%, the manganese ore mine that liquid-solid ratio is 3
Slurry；
(2) above-mentioned manganese ore ore pulp is added in stirred tank, under 300r/min stirring, being uniformly added into mass concentration is
The leaching agent of 3.5%HCl, control slurry pH are 4.5~5.0, and room temperature leaches 3 hours, obtains and leaches slurry；
(3) slurry centrifugal dehydration will be leached, obtaining solid is manganese chats；
(4) clear water mining in manganese is washed 3 times, after being dehydrated and drying, detects manganese chats output capacity and calcium, magnesium, manganese content,
The rate of recovery is calculated to be as follows:
Leaching effect/% of 3 pH=4.5~5.0 of table
(5) clear water mining in manganese is sized mixing to liquid-solid ratio is 4, and flotation slurry is made；
(6) flotation device is added in flotation slurry, uses NaCO3Adjust pH=9.5-10.0；
(7) use acetic acid lauryl amine: dodecyl trimethyl ammonium chloride=1:1 is collecting agent, and dosage is mine amount 350 per ton
Gram, row reverse flotation is swept by 4 thick 1, obtaining froth concentrate is silicon concentrate, analyzes its ingredient, SiO2Content is 75.1%, calculates it
The rate of recovery is 82.6%；
(8) above-mentioned floatation underflow being dehydrated, obtains manganese iron ore concentrate, analysis manganese iron ore concentrate contains Mn 26.6%, TFe 9.1%,
Calculating metal recovery rate is Mn 93.0%, iron 93.6%.
Embodiment 3
A kind of manganese ore enrichment method of selecting smelting combination, concrete operations are as follows:
Selecting smelting combination enrichment experiment is carried out to Xiangxi low-grade manganese.Mn content is 10.15% in the mineral, arteries and veins
Stone ore object is mainly silicate mineral and quartz, and mass component is as follows:
6 manganese ore multielement analysis result of table/%
| SiO2 | Al2O3 | MgO | CaO | P | Mn | Pb | Ni | Fe | Cu |
| 38.52 | 10.69 | 1.65 | 6.01 | 0.18 | 10.15 | 0.021 | 0.011 | 0.041 | 0.0027 |
(1) low-grade manganese comminution to -0.074mm is accounted for 80% or more, it is 4 that ore pulp, which is sized mixing with clear water to liquid-solid ratio,；
(2) above-mentioned manganese ore slurry is added in agitator, in 400rmin-1Under stirring, it is uniformly added into mass concentration 3.8%
The leaching agent of HCl, keeping slurry pH is 5.0~5.5, and room temperature leaches 4 hours, obtains and leaches slurry；
(3) slurry vacuum filtration will be leached, filtrate is leachate, and filter cake is manganese chats；
(4) after washing clear water mining in manganese 3 times, then being sized mixing with clear water to liquid-solid ratio is 3, and flotation slurry is made；
(5) flotation device is added in flotation slurry, adjusts pH value 9~10 with NaOH；
It (6) is collecting agent with hydrochloric acid lauryl amine, dosage is 250 grams of mine amount per ton, sweeps into row flotation by 3 thick 1, obtains foam
Concentrate is silicon concentrate.Analyze its ingredient, SiO2Content is 81.6%, and calculating its rate of recovery is 80.5%；
(7) above-mentioned floatation underflow is dehydrated to get manganic concerntrate is arrived, analysis manganic concerntrate contains Mn 31.9%, calculates metal recovery
Rate is Mn 91.7%.
Embodiment 4
A kind of manganese ore enrichment method of selecting smelting combination, concrete operations are as follows:
The rich manganese test of selecting smelting combination is carried out to the poor Ferromanganese Ore in Yunnan.Mn content is 15.6% in the mineral, gangue
Mineral are mainly silicate mineral and quartz, and mass component is as follows:
7 manganese ore multielement analysis result of table/%
| SiO2 | Mn | TFe | Al2O3 | CaO | MgO | K2O | Na2O |
| 32.0 | 15.6 | 23.4 | 5.5 | 6.5 | 0.4 | 1.5 | 0.04 |
In addition, manganese only has minimal amount of manganese carbonate in sample ore, and wherein most is with soft manganese from the point of view of material phase analysis situation
The form presence of mine, manganite, vernadite and manganese iron chemical combination mineral；The material phase analysis of iron shows iron mainly with bloodstone, brown
Iron ore exists.More mechanisms are such to the ore almost without separating effect studies have shown that conventional magnetic separation, gravity treatment and flotation
Sample ore, which belongs to, extremely difficult selects ferrous manganese ore.
(1) low-grade manganese is added into water for ball milling, obtaining granularity is that -0.074mm accounts for the manganese ore slurry that 85.6%, liquid-solid ratio is 4；
(2) above-mentioned manganese ore slurry is added in agitator, in 500rmin-1Under stirring, it is uniformly added into mass concentration 4.1%
The leaching agent of HCl, keeping slurry pH is 4.5~5.0, and room temperature leaches 4 hours, obtains and leaches slurry；
(3) slurry vacuum filtration will be leached, filtrate is leachate, and filter cake is manganese chats；
(4) clear water mining in manganese is sized mixing to liquid-solid ratio is 4, and flotation slurry is made；
(5) flotation device is added in flotation slurry, uses NaCO3Adjusting pH value is 9~9.5；
(6) use hydrochloric acid lauryl amine: acetic acid octadecylamine=2:1 is collecting agent, and dosage is 350 grams of mine amount per ton, is swept by 3 thick 1
Flotation is carried out, obtaining froth concentrate is silicon concentrate, analyzes its ingredient, SiO2Content is 79.1%, calculates its rate of recovery and is
81.8%；
(7) above-mentioned floatation underflow is dehydrated to get manganese iron ore concentrate is arrived, analysis manganese iron ore concentrate contains Mn 30.6%, TFe
42.1%, calculating metal recovery rate is Mn 91.7%, iron 93.0%.
Embodiment 5
A kind of manganese ore enrichment method of selecting smelting combination, concrete operations are as follows:
1 liter of leachate of gained, analyzes its ion concentration: Ca in Example 12+For 36.1g/L, Mg2+For 5.2g/L.
Leaching liquid is added 15 grams of calcium lime powder by 1 gram of speed per minute, after the completion, continues stirring 30 minutes, obtains
To magnesium sinking liquid；
By magnesium sinking liquid precipitate, after clarification 90 minutes, top magnesium sinking clear liquid is released, wherein Mg is examined2+Concentration is 0.28g/L；
Bottom sediment is washed 2 times with clear water, and dehydration is magnesium hydroxide.
Continue under agitation, it is 200 grams of 50% sulfuric acid that mass concentration is uniformly instilled into magnesium sinking clear liquid, and sulfuric acid is added dropwise
After the completion, continue stirring 30 minutes, obtain heavy calcium liquid；
After sixty minutes by heavy calcium liquid precipitate, clarification, the heavy calcium clear liquid in top is released, wherein Ca is examined2+For 0.57g/L；Bottom
Sediment is washed 2 times with clear water, and dehydration is calcium sulfate (gypsum).
The namely regenerated leaching agent of resulting heavy calcium clear liquid.
Comparative example 1
A kind of manganese ore enrichment method of selecting smelting combination, concrete operations are as follows:
(a) the resulting manganese ore ore pulp of step (1) in Example 2.
(b) above-mentioned manganese ore ore pulp is added in stirred tank, under 300r/min stirring, being uniformly added into mass concentration is
The leaching agent of 3.9%HCl, control slurry pH are 1.5-2.0, and room temperature leaches 3 hours, obtain and leach slurry；
(c) slurry centrifugal dehydration will be leached, obtaining solid is manganese chats；
(d) clear water mining in manganese is washed 3 times, after being dehydrated and drying, detects manganese chats output capacity and calcium, magnesium, manganese content,
The rate of recovery is calculated separately to be as follows:
Leaching effect/% of 4 pH=1.5~2.0 of table
As can be seen from the above table, it since the pH value of leaching is too low, causes manganese chats metal recovery rate and is reduced to 87.3%.
(e) clear water mining in manganese is sized mixing to liquid-solid ratio is 4, and flotation slurry is made；
(f) flotation device is added in flotation slurry, uses NaCO3Adjust pH=9.5-10.0；
(g) use acetic acid lauryl amine: dodecyl trimethyl ammonium chloride=1:1 is collecting agent, and dosage is mine amount 350 per ton
Gram, row reverse flotation is swept by 4 thick 1, obtaining froth concentrate is silicon concentrate, analyzes its ingredient, SiO2Content is 82.2%, calculates it
The rate of recovery is 84.6%；
(h) above-mentioned floatation underflow is dehydrated to get manganese iron ore concentrate is arrived.It analyzes manganese iron ore concentrate and contains Mn 27.0%, TFe
9.5%, calculating metal recovery rate is Mn 81.2%, iron 90.2%.
The present embodiment leaches at low ph values, and gained concentrate grade remains basically stable with embodiment 2, but manganese iron recovery is more real
Apply example 2 (Mn 93.0%, iron 93.6%) significant decrease.
Comparative example 2
A kind of manganese ore enrichment method of selecting smelting combination, concrete operations are as follows:
(a) the resulting manganese ore ore pulp of step (1) in Example 2.
(b) above-mentioned manganese ore ore pulp is added in stirred tank, under 300r/min stirring, being uniformly added into mass concentration is
The leaching agent of 3.5%HCl, control slurry pH are 6.0-6.5, and room temperature leaches 3 hours, obtain and leach slurry；
(c) slurry centrifugal dehydration will be leached, obtaining solid is manganese chats；
(d) clear water mining in manganese is washed 3 times, after being dehydrated and drying, detects manganese chats output capacity and calcium, magnesium, manganese content,
The rate of recovery is calculated to be as follows:
Leaching effect/% of 5 pH=6.0-6.5 of table
As can be seen from the above table, since the pH value of leaching is excessively high, it is higher to cause MgO and CaO content in manganese chats, MgO
Leaching rate is only that 46.3% and CaO leaching rate is only 56.8%.
(e) clear water mining in manganese is sized mixing to liquid-solid ratio is 4, and flotation slurry is made；
(f) flotation device is added in flotation slurry, uses NaCO3Adjust pH=9.5-10.0；
(g) use acetic acid lauryl amine: dodecyl trimethyl ammonium chloride=1:1 is collecting agent, and dosage is mine amount 350 per ton
Gram, row reverse flotation is swept by 4 thick 1, obtaining froth concentrate is silicon concentrate, analyzes its ingredient, SiO2Content is 69.3%, calculates it
The rate of recovery is 82.9%；
(h) above-mentioned floatation underflow is dehydrated to get manganese iron ore concentrate is arrived.
It analyzes manganese iron ore concentrate and contains Mn 20.7%, TFe 7.0%, calculating metal recovery rate is Mn 90.1%, TFe
90.2%.Manganese iron concentrate grade is substantially reduced compared with embodiment 2 (Mn 26.6%, TFe 9.1%).
Claims (9)
1. a kind of manganese ore enrichment method of selecting smelting combination, includes the following steps:
(1) manganese ore ore pulp is made in water and manganese ore mixed grinding；
(2) manganese ore ore pulp and leaching agent are mixed, controlling its pH value is 3~5.5, after being leached, isolated manganese chats and
Leachate；
(3) manganese chats is subjected to Counterfloatating desiliconization, obtained flotation froth concentrate is silicon concentrate, and underflow tailing is manganese iron ore concentrate；
(4) regenerative agent quick lime and sulfuric acid are successively added in leachate, obtains regenerated leaching agent return step (2) and uses,
It is sold outside magnesium hydroxide and calcium sulfate.
2. the manganese ore enrichment method of selecting smelting combination according to claim 1, it is characterised in that: the manganese ore be pyrolusite,
Psilomelane, hausmannite, manganese spar, todorokite, calcimangite, manganosiderite.
3. the manganese ore enrichment method of selecting smelting combination according to claim 1, it is characterised in that: in step (1), water and manganese ore
Solvent and solute weight ratio be 2~6:1.
4. the manganese ore enrichment method of selecting smelting combination according to claim 1, it is characterised in that: in step (1), by manganese ore and
Water is ground to be mixed to prepare manganese ore ore pulp, and wherein granularity is -74 μ m≤70%.
5. the manganese ore enrichment method of selecting smelting combination according to claim 1, it is characterised in that: in step (2), the pH value
It is 4.5~5.5.
6. the manganese ore enrichment method of selecting smelting combination according to claim 1, it is characterised in that: in step (2), leaching agent is
The hydrochloric acid of 1~10wt%.
7. the manganese ore enrichment method of selecting smelting combination according to claim 1, it is characterised in that: in step (3), reverse flotation item
Part are as follows: the solvent and solute weight ratio of water and manganese chats is 3~8:1, and pH value is 7~11, and floating agent is C12~C18 kiber alkyl amine salt
One of or combinations thereof, dosage is 20~500 g tons.
8. the manganese ore enrichment method of selecting smelting combination according to claim 1, it is characterised in that: by step (4) regenerated leaching
Ca in agent out2+Concentration is not less than 0.5g/L, Mg2+Concentration is not less than 0.2g/L.
9. the manganese ore enrichment method of selecting smelting combination according to claim 1-8, it is characterised in that: by processing
Afterwards, the overall recovery of manganese is 90%~95%, and the mass content of manganese is 25%~35% in manganese iron ore concentrate.
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