CN104016417A - Process for preparing electronic grade manganous-manganic oxide and byproduct nano-iron oxide red from pyrolusite - Google Patents
Process for preparing electronic grade manganous-manganic oxide and byproduct nano-iron oxide red from pyrolusite Download PDFInfo
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Abstract
The invention belongs to the technical field of wet metallurgy of manganese, and provides a process for preparing electronic grade manganous-manganic oxide and byproduct nano-iron oxide red from pyrolusite by means of wet reduction. The process is used for preparing an electronic grade manganous-manganic oxide product by steps of ball-mill screening, preparing (adding a reducing agent), acid pickling, ion exchanging by chelate resin, impurity removing, manganese precipitation, oxidizing, washing, baking and the like, wherein an ion exchange eluent is subjected to iron neutralizing precipitation, filtering, washing and drying, calcining and the like to produce a byproduct nano-iron oxide red; the leaching rate of manganese is over 98 percent, the comprehensive recycling rate is more than 90 percent, the content of manganese in the manganous-manganic oxide is 71 percent, the specific surface area is more than 20m<2>/g, the byproduct nano-iron oxide red product can be prepared, the purity of the nano iron red product is more than 95 percent, and the grain diameter of the nano iron red product is less than 100nm. Compared with the prior art, the purity of the manganous-manganic oxide product is increased, the product quality is more stable, and the production cost is reduced.
Description
Technical field
The invention belongs to the technical field of wet metallurgy of manganese, relate in particular to pyrolusite wet reducing and prepare the nanometer iron oxide red technique of electronic-grade trimanganese tetroxide by-product.
Background technology
Electronic-grade trimanganese tetroxide belongs to high performance structures material, is mainly used in electronic industry, is to produce one of required important raw and processed materials of soft magnetic ferrite.Particularly in recent years, along with the develop rapidly of electronics and information industry, the output of China's soft magnetic ferrite constantly increases progressively, for the trimanganese tetroxide as its raw material, not only quantitatively but also proposing more and more higher requirement qualitatively with in performance.The preparation method of trimanganese tetroxide can be divided into five classes by the difference of used manganese raw material: (1) manganese metal method; (2) value Mn conventional ceramic technique; (3) manganous carbonate method; (4) manganese salt method; (5) manganese ore method.Industrial, mostly adopting at present electrolytic metal Mn sheet is both at home and abroad raw material preparation, because manganese metal price is higher, causes trimanganese tetroxide production cost higher, and foreign matter selenium content is higher, only having direct is that raw material production trimanganese tetroxide just has larger price competitiveness with manganese ore.China's manganese resource is abundant, mainly contains rhodochrosite and pyrolusite, and along with the development development of electrolytic manganese, domestic rhodochrosite resource has approached exhausted, and pyrolusite resource is not well utilized.How rationally research and development utilize pyrolusite to prepare the approach that trimanganese tetroxide is an effective solution manganese resource problem, also for the production of high-end trimanganese tetroxide, find out the novel process of an efficient economy simultaneously.
The processing of pyrolusite mainly contains two kinds of prereduction Roasting And Leaching method (thermal process) and direct leachings (wet processing), the former carries out roasting to pyrolusite under the condition existing at reductive agent, make main component Manganse Dioxide in pyrolusite be reduced to acid-soluble manganese monoxide, then with leaching agents such as acid, leach and leach liquor is carried out to removal of impurities and obtain manganous salt solution, manganous salt solution obtains trimanganese tetroxide through heavy manganese and oxidation.The reductive agent using has pyrite, brown coal, carbon monoxide, gac and graphite etc.Directly the key distinction of leaching method and prereduction Roasting And Leaching method is that direct leaching is without the process high-temperature roasting stage, but utilizes reductive agent, in leaching agent solution, pyrolusite is carried out to direct-reduction, realizes the direct leaching of pyrolusite.The reductive agent using in direct leaching process has sulfurous gas, ferrous sulfate, hydrogen peroxide, pyrite, charcoal and organism class agriculture byproduct.Compare with prereduction Roasting And Leaching method, direct leaching has that technical process is shorter, energy consumption is less, the also advantage such as lower, environmental protection of cost, more meets the strategy of sustainable development of industry, is the focus of research both at home and abroad in recent years.
The method of prior art cannot realize when producing highly purified electronic-grade trimanganese tetroxide product, can also by-product purity be greater than the nanometer iron oxide red product that 95wt%, median size are less than 100nm.
Therefore, select suitable reductive agent to improve the leaching yield of manganese, and reduzate is recycled, reduce production costs, control applicable processing condition and prepare the trimanganese tetroxide of high purity, high-specific surface area, obtain highly purified nanometer iron oxide red product simultaneously, have important practical significance.
Summary of the invention
Pyrolusite wet reducing provided by the invention is prepared the nanometer iron oxide red technique of electronic-grade trimanganese tetroxide by-product, is intended to solve the problem that leaching yield is lower, metal recovery rate is low, quality product is not high, energy consumption is high, environmental pollution is serious and production cost is higher that existing pyrolusite is prepared manganese in trimanganese tetroxide technique.
At present for using resin for adsorbing iron ion ferromanganese solution, from the various polymeric adsorbent of quantity or resin, select desirable resin, require it can as far as possible optionally adsorb under given conditions iron ion and can reduce as far as possible the absorption for mn ion, other heavy metal ion, calcium, magnesium ion, this is a technical barrier simultaneously.Existing resin or polymeric adsorbent product cannot be competent at this requirement.
The inventor by improving technique, for example, adds hydrazine hydrate and dispersion agent in heavy manganese, oxidising process, and the purity of trimanganese tetroxide product is significantly improved; By using specific resin optionally to adsorb iron ion from ferromanganese solution, the by product that obtains high purity, high quality, high value is nanometer iron oxide red.
According to the first embodiment of the present invention, provide pyrolusite wet reducing to prepare the method for electronic-grade trimanganese tetroxide and by-product nanometer iron oxide red, the method comprises the following steps:
(1) ball milling sieves: by pyrolusite thing ball milling (for example to 80 order-300 order, preferably 90 order-200 orders), then sieve;
(2) batching: add reductive agent and stir, obtaining mixed mineral powder;
(3) acidleach: mixed mineral powder metering is dropped in acidleach pond and carries out acidleach, and then filtering separation, obtains filter residue and filtrate;
(4) ion-exchange: filtrate is adsorbed with the resin of inhaling iron (III), and water and polymeric adsorbent are separated, obtains containing the tail water of manganese and the polymeric adsorbent phase of iron content (III) ion; Preferably, use for the equilibrium adsorption capacity of iron (III) be greater than 117.0mg/g, be preferably greater than 118.0mg/g, more preferably greater than 118.5mg/g, be further preferably greater than 119.0mg/g, for the equilibrium adsorption capacity of mn ion lower than 6mg/g, preferably lower than 5mg/g, more preferably less than 4mg/g, further preferably adsorb lower than the resin of 3.5mg/g.More preferably, above-mentioned resin is to have aminophosphonic acid functional group-CH
2nHCH
2pO
3 -content is 1.30-1.53mmol/g, more preferably 1.33-1.50mmol/g, more preferably 1.36-1.48mmol/g, further preferred vinylbenzene-divinylbenzene crosslink multipolymer resin of 1.38-1.45mmol/g.Still more preferably, in the pH of filtrate value in 1.4-2.1 scope (preferably 1.5-2.0) and temperature at 10-42 ℃ of scope (preferred 20-41 ℃, more preferably 25-41 ℃, more preferably 30-40 ℃) condition under with the resin of above-mentioned suction iron (III), adsorb.
(5) removal of impurities: after deionizing exchange containing iron ion, heavy metal ion, calcium, magnesium ion in manganese tail water (being the aqueous solution);
(6) heavy manganese, oxidation: regulating the pH containing manganese tail water with ammoniacal liquor is 8.5-11, preferred 9-10, be settled out manganese, filter, water repetitive scrubbing throw out is to till sulfate radical-free ion or essentially no sulfate ion, obtain manganous hydroxide mud, for example, by chloride buffer solution (2-30wt% concentration, as 4-20wt% concentration) manganous hydroxide mud is deployed into containing manganese concentration is 0.08～1.0mol/L, preferred 0.09～0.8mol/L, preferably the solution of 0.1～0.5mol/L (, heavy manganese solution), add hydrazine hydrate (the 0.08-2.0 volume % based on liquor capacity for example, preferred 0.1vol%-0.5vol%, as 0.2vol% or 0.3vol%) to control the current potential of solution, stablize, add 0.08-10 volume %, the dispersion agent of preferred 0.1-5 volume % (volume based on solution), pass into air simultaneously and carry out reflux oxidation, in oxidising process, with the pH of ammoniacal liquor adjusting or control mixed solution, be 8.5-11, preferred 9-10, filter and obtain filter residue,
(7) washing, dry: wash filter residue that step (6) obtains with water to till sulfate radical-free ion or essentially no sulfate ion, then dry, obtain electronic-grade trimanganese tetroxide product.Its manganese content, higher than 71.5wt%, preferably higher than 71.8wt%, more preferably higher than 71.9wt%, even reaches 72.0wt%.
(8) prepare nanometer iron oxide red: for example, by hydrochloric acid soln (3-10wt% concentration, preferred 4-8wt% concentration) polymeric adsorbent of the iron content after ion-exchange (III) ion is carried out to desorb mutually, obtain stripping liquid, then that stripping liquid is nanometer iron oxide red for the preparation of byproduct.
Preferably, in described step (2) blending process, described reductive agent is the reductive agent containing elemental iron.It is 0.8-5.0:1, preferably 0.9-4.0:1, more preferably 1.0-3.0:1 that the addition of reductive agent makes in pyrolusite thing in manganese and reductive agent the consumption molar ratio of iron, more preferably 1.1-2.0:1, more preferably 1.2-1.8:1, further preferred 1.4-1.6:1.
Preferably, the acidleach process of described step (3) is carried out as follows: first mixed mineral powder metering is dropped in described acidleach pond, in acidleach pond, add 10-100% (the preferred 20-90% that is equivalent to mixed mineral powder weight, more preferably 30-80%, more preferably (for example sulfuric acid concentration is at 20-98.5wt% for sulfuric acid 35-70%), more preferably 30-90wt%, more preferably 40-80wt%, more preferably 45-70wt%, for example 50wt% or 60wt%), then add water and by solid-to-liquid ratio 1:1-10, preferred 1:1.5-8, more preferably 1:2-7 controls adding of the water yield, at 15-99 ℃, agitation leach 1-20h at preferred 20-90 ℃, preferred 2-10h, more preferably 3-6h, more preferably 4h-5h, then carry out filtering separation.
In above-described step 4) in, the polymeric adsorbent (or resin of suction iron (III)) as absorption iron (III) ion, is preferably used (the CH of aminophosphonic acid functional group
2nHCH
2pO
3 -) content is vinylbenzene-divinylbenzene crosslink multipolymer resin of 1.30-1.53mmol/g (more preferably 1.33-1.50mmol/g, more preferably 1.36-1.48mmol/g, further preferred 1.38-1.45mmol/g).When aminophosphonic acid functional group content is during higher than 1.53mmol/g, the interference of mn ion and calcium, magnesium ion strengthens.And when aminophosphonic acid functional group content is during lower than 1.30mmol/g, for the loading capacity of ferric ion, can decline.
This resin is generally to use with sodium-salt form, with the aminophosphonic acid sodium (CH of functional group
2nHCH
2pO
3na
2).This resin is rendered as the form of particle (preferably spherical particle).The median size of resin particle is generally within the scope of 0.3～1.2mm, more preferably in 0.4～1.0mm scope, more preferably in 0.5～0.9mm scope, more preferably in 0.6～0.8mm scope.Generally, the degree of crosslinking of vinylbenzene-divinylbenzene interpolymer is 6-9%, more preferably 7-8.5%.
As the resin of inhaling iron (III), when aminophosphonic acid functional group content is 1.30-1.53mmol/g (more preferably 1.33-1.50mmol/g, more preferably 1.36-1.48mmol/g, further preferred 1.38-1.45mmol/g) time, at pH=1.4-2.1 scope (preferred 1.5-2.0, 1.6-1.9) and 10-42 ℃ of temperature range (preferred 20-41 ℃ more preferably, more preferably 25-41 ℃, more preferably 30-40 ℃, more preferably 38-40 ℃), above-mentioned resin (the preferably resin of Na salt form) is greater than 117.0mg/g for the equilibrium adsorption capacity of iron (III), be preferably greater than 118.0mg/g, more preferably greater than 118.5mg/g, further be preferably greater than 119.0mg/g, for the equilibrium adsorption capacity of mn ion lower than 6mg/g, preferably lower than 5mg/g, more preferably less than 4mg/g, further preferably lower than 3.5mg/g.In addition, for the equilibrium adsorption capacity of calcium and magnesium ion lower than 5mg/g, preferably lower than 4mg/g, preferably lower than 3mg/g.
Most similar resin well known in the prior art at above-mentioned pH and temperature for the equilibrium adsorption capacity of iron (III) generally lower than 100mg/g, the most just can reach 115mg/g, but, for the equilibrium adsorption capacity of mn ion higher than 15mg/g, the most just can reach 8mg/g.Key is, as also higher in the equilibrium adsorption capacity of calcium, magnesium ion for interfering ion, generally higher than 10mg/g.
Preferably, the removal of impurities process of described step (5) is carried out as follows: described containing adding in the tail water of manganese manganous carbonate regulator solution pH value to 2.5-6, preferably 3-5, more preferably 3.5-4.5, making iron contamination ion a small amount of in solution be hydrolyzed to ferric hydroxide precipitate removes, adding alkali metalsulphide (as sodium sulphite) or passing into hydrogen sulfide makes the heavy metal ion in solution remove with sulfide precipitation, then add Manganous fluoride, make Ca2+ in filtrate, Mg2+ ion generate fluorochemical precipitation and remove.
Preferably, in described (6) heavy manganese and oxidising process, add 0.08-2.0 volume % with respect to heavy manganese solution volume, preferably 0.09-1.5 volume %, more preferably the hydrazine hydrate of 0.1-1.0 volume % is stable to control the current potential of solution, pass into the time 1-20h of air return oxidation, preferred 2-10h, oxidation control temperature is 15-98 ℃, preferably 20-90 ℃, more preferably 30-80 ℃, more preferably 40-70 ℃, for example 50 ℃ or 60 ℃.
Preferably, at the dispersion agent described in described step (6) oxidising process, be one or more in polystyrene, Xylitol, C2-C6 dibasic alcohol (as ethylene glycol, propylene glycol or butyleneglycol), the 0.08-10.0vol% that add-on is mixeding liquid volume, preferred 0.09-8.0vol%, preferred 0.1-5.0vol%.
Preferably, described step (8) is prepared nano grade iron oxide red process and is carried out as follows: described stripping liquid or iron (III) ion elutriant are neutralized to precipitate to obtain byproduct after tapping a blast furnace, filter, wash, be dried, calcine nanometer iron oxide red.Preferably, the purity of nanometer iron oxide red product is greater than 94wt%, is preferably greater than 95wt%, more preferably greater than 96wt%, be further preferably greater than 97wt%, still further preferred 98wt%.Its median size is less than 100nm, is preferably less than 90nm, is more preferably less than 80nm, is particularly preferably less than 70nm, is more preferably less than 60nm.
More preferably, described step (8) is prepared nano grade iron oxide red process and is carried out as follows: stripping liquid or iron (III) ion elutriant are heated to 30-90 ℃, preferred 35-80 ℃, for example, with ammoniacal liquor (concentration 5-28wt%, more preferably 7-20wt%) by the pH regulator of solution to 1.5-2.5 (as 2), using urea as precipitation agent, the quality (or molar weight) that adds precipitation agent urea is 10-20 times of iron ion Theoretical Mass (or molar weight) in solution, in temperature, be 60-98 ℃, (the preferred 1-6h of stirring reaction 0.5-10h under the condition of preferred 70-95 ℃ (as 90 ℃), as 3h), suction filtration, obtain ironic hydroxide presoma, after being dried, grinds evenly described ironic hydroxide presoma, calcining (is for example calcined 2-7h at 300-800 ℃ in retort furnace, preferred 3-4h), obtain byproduct nanometer iron oxide red.
Preferably, the concentration of the ammoniacal liquor in step (6) is 5-28wt%, more preferably 7-20wt%.In addition, described in step (8), the concentration of hydrochloric acid soln is 2-45wt%, preferably 3%-15wt%, more preferably 5%-10wt%.
Preferably, described reductive agent or be waste iron filing or iron powder containing the reductive agent of elemental iron.
Preferably, in the trimanganese tetroxide product obtaining, manganese content reaches 70-72wt% (as higher than 71.2%, preferred 71.5wt%, preferred 71.6wt%, more preferably 71.8wt%, further preferred 71.9wt%).Its specific surface area is greater than 20m
2/ g, preferably 20m
2/ g-50m
2/ g, more preferably 25m
2/ g-40
2/ g.Its dioxide-containing silica is less than 0.01wt%, and sulphur content is less than 0.05wt%, and the content of selenium is for being less than 0.001wt%, being preferably 0wt%.
As the pyrolusite using in the application, its main component is Manganse Dioxide, is generally 45%-67wt% containing manganese rate, and 50-65wt% for example, as 63wt%.
Useful technique effect of the present invention
In heavy manganese, oxidising process, by adding hydrazine hydrate, keep the current potential of solution to stablize and add specific dispersion agent, significantly improved the purity of trimanganese tetroxide product, by 92wt%-97wt%, be increased to 98.5wt%-99.93wt%, more preferably be increased to 99-99.93wt%, especially 99.5-99.9wt%, reaches electronic-grade purity.
By a large amount of selectivity tests, test, from a large amount of polymeric adsorbents or resin, select specific polymeric adsorbent, it mainly adsorbs iron (III) ion but adsorbs hardly the resin of mn ion, is conducive to the iron of solution (III) ion separated with mn ion.
Adopt the leaching yield of this technique manganese to reach more than 98%, the comprehensive recovery of manganese is greater than 90%, and in trimanganese tetroxide product, manganese content reaches 71.5-72% (theoretical content 72.05wt%), and specific surface area is greater than 20m
2/ g, containing selenium, dioxide-containing silica is not less than 0.01%, and sulphur content is less than 0.05%, simultaneously can the nanometer iron oxide red product of by-product, nanometer iron oxide red product purity is greater than 95%, and particle diameter is less than 100nm.
Because pyrolusite of the present invention does not need through the direct acidleach of roasting, reduzate is recovered as nanometer iron oxide red, energy consumption and production cost have been reduced, reduced environmental pollution, the electronic-grade trimanganese tetroxide constant product quality preparing, purity is high, and specific surface area is large, has stronger propagation and employment and is worth.
Accompanying drawing explanation
Accompanying drawing 1 is the production scheme of this technique.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
In an embodiment, the content analysis of manganese adopts ferrous ammonium sulfate titration (GB/T1506-2002), and the concentration of iron ion adopts potassium bichromate titrimetric method to measure.
In the following embodiments, the polymeric adsorbent (or resin of suction iron (III)) as absorption iron (III) ion, is used (the CH of aminophosphonic acid functional group
2nHCH
2pO
3 -) the content vinylbenzene-divinylbenzene crosslink multipolymer resin (being called for short polymeric adsorbent A) that is 1.42mmol/g.With sodium-salt form, use.This resin is rendered as the form of spherical particle.The median size of resin particle is 0.8mm.The degree of crosslinking of styrene-divinylbenzene copolymer is 7.5%.At pH=1.4-2.1 scope (preferably 1.5-2.0) and 10-42 ℃ of temperature range (preferred 20-41 ℃, more preferably 25-41 ℃, more preferably 30-40 ℃, more preferably 38-40 ℃), above-mentioned resin (Na salt form) for the equilibrium adsorption capacity of iron (III) be greater than 118.0mg/g, more preferably greater than 118.5mg/g, be further preferably greater than 119.0mg/g, for the equilibrium adsorption capacity of mn ion lower than 5mg/g, more preferably less than 4mg/g, further preferably lower than 3.5mg/g, in addition, for the equilibrium adsorption capacity of calcium and magnesium ion lower than 3mg/g.When in pH=1.7-1.8 scope and 38-40 ℃ of temperature range, above-mentioned resin (Na salt form) is greater than 119.0mg/g for the equilibrium adsorption capacity of iron (III), for the equilibrium adsorption capacity of mn ion lower than 3.5mg/g, in addition, for the equilibrium adsorption capacity of calcium and magnesium ion lower than 3mg/g.
Embodiment 1
After pyrolusite is milled to 80 orders, sieve, add iron iron filings as reductive agent and stir in screened material, wherein to make the consumption molar ratio of manganese and iron in pyrolusite thing be 1.5:1 to the addition of iron filings.Gained mixed mineral powder metering is dropped in acidleach pond, add the sulfuric acid of 60% the concentration 80wt% that is equivalent to mixed mineral powder weight.Then, add water, and control adding of the water yield by solid-to-liquid ratio 1:6.Filtering separation after agitation leach 5h at 80 ℃, obtains filtrate.First the pH regulator to 2.0 of gained filtrate and temperature are remained on to 38-40 ℃, then this filtrate is adsorbed (within 100 minutes, reaching balance) with the polymeric adsorbent A that inhales iron (III), water and polymeric adsorbent are separated, obtain containing the tail water of manganese and the polymeric adsorbent phase of iron content (III) ion.The polymeric adsorbent that has adsorbed iron is used 5% hydrochloric acid soln desorb mutually, obtains the stripping liquid of iron content.
Containing in manganese tail water after ion-exchange adds manganous carbonate to regulate the pH value to 4 of this solution (containing manganese tail water), makes iron contamination ion a small amount of in solution be hydrolyzed to ferric hydroxide precipitate and by removing by filter, obtains filtrate.Then in filtrate, add sodium sulphite that the heavy metal ion in solution is removed with sulfide precipitation.In removing the filtrate of heavy metal, add Manganous fluoride, make Ca in filtrate
2+, Mg
2+ion generates fluorochemical precipitation and removes.Then with ammoniacal liquor, regulate the pH of filtrate in 9-10 scope, precipitation manganese, filters and obtains filter residue, with clear water repetitive scrubbing filter residue, to till essentially no sulfate ion, obtains manganous hydroxide mud.With chloride buffer solution by the manganous hydroxide mud solution that to be deployed into containing manganese concentration be 0.4mol/L, add the current potential of the hydrazine hydrate control solution that is equivalent to heavy manganese solution volume 0.8% stable, add the Xylitol that is equivalent to heavy manganese solution volume 3.0%, pass into air return oxidation 5h simultaneously, it is 70 ℃ that oxidizing temperature is controlled, in oxidising process, with the pH that the ammoniacal liquor of concentration 20wt% is controlled mixed solution, be 9.5, filter and obtain filter residue, gained filter residue washs to sulfate radical-free ion with clear water.Filter residue is dried, and obtains electronic-grade trimanganese tetroxide product.Adopting ferrous ammonium sulfate titration (GB/T1506-2002), record the content 72wt% of manganese in trimanganese tetroxide product, is 99.93wt% corresponding to the purity of trimanganese tetroxide.
Iron (III) ion elutriant (being the stripping liquid of iron content) after ion-exchange is resolved is heated to 70 ℃, uses the ammoniacal liquor of concentration 25wt% by the pH regulator to 2 of solution.Using urea as precipitation agent, the quality (or molar weight) that adds precipitation agent urea be iron ion quality (or molar weight) 10-20 doubly.Then in temperature, be stirring reaction 3h under the condition of 90 ℃, suction filtration, obtains ironic hydroxide presoma, after presoma is dried, grinds evenly, in retort furnace, at 300-800 ℃, calcines 3-4h, obtains byproduct nanometer iron oxide red.
The leaching yield of manganese reaches 99%, and the comprehensive recovery of manganese reaches 93%.In trimanganese tetroxide product, manganese content reaches 72%, and specific surface area is 40m
2/ g.Not containing selenium.Dioxide-containing silica is less than 0.01%, and sulphur content is less than 0.05%.Simultaneously can the nanometer iron oxide red product of by-product, nanometer iron oxide red product purity is 98%, median size is 80nm.
Comparative example 1
Repeat embodiment 1, just in heavy manganese solution, do not add the Xylitol as dispersion agent.Adopting ferrous ammonium sulfate titration (GB/T1506-2002), record the content 68.8wt% of manganese, is 95.48wt% corresponding to the purity of trimanganese tetroxide.Nanometer iron oxide red product purity is 98%, and median size is 81.5nm.
Comparative example 2
Repeat embodiment 1, just in heavy manganese solution, do not add hydrazine hydrate and do not add the Xylitol as dispersion agent.Adopting ferrous ammonium sulfate titration (GB/T1506-2002), record the content 67.5wt% of manganese, is 93.69wt% corresponding to the purity of trimanganese tetroxide.Nanometer iron oxide red product purity is 98%, and median size is 80nm.
Embodiment 2
Repeat embodiment 1.Other condition is as follows:
According to above-mentioned ball milling sieve, the step such as batching, acidleach, ion-exchange, removal of impurities, heavy manganese, oxidation, washing, oven dry operates successively, wherein in burden process, to choose containing manganese grade be 35.8%, and pyrolusite and iron content 95.6% waste iron filing are raw material, and the ratio that is 1.4:1 in the mol ratio of the amount of iron substance in manganese amount of substance and reductive agent in pyrolusite batching, it is 98.6% that the leaching yield of manganese reaches, the comprehensive recovery of manganese is 92.5%, in trimanganese tetroxide product, manganese content is 71.5%, and specific surface is 23.6m
2/ g,, containing selenium, dioxide-containing silica is not 0.005%, and sulphur content is 0.032%, and in nanometer iron oxide red product, ferric oxide content is 98.0%, and particle diameter is 80nm.
Embodiment 3
Repeat embodiment 1, wherein use propylene glycol to replace Xylitol, other condition is as follows:
According to above-mentioned ball milling sieve, the step such as batching, acidleach, ion-exchange, removal of impurities, heavy manganese, oxidation, washing, oven dry operates successively, wherein in burden process, choosing containing the manganese grade pyrolusite that is 27.5% and the waste iron filing of iron content 93.6% is raw material, and the ratio that is 1.5:1 in the mol ratio of the amount of iron substance in manganese amount of substance and reductive agent in pyrolusite batching, it is 98.5% that the leaching yield of manganese reaches, the comprehensive recovery of manganese is 91.8%, in trimanganese tetroxide product, manganese content is 71.6%, and specific surface is 22.8m
2/ g,, containing selenium, dioxide-containing silica is not 0.006%, and sulphur content is 0.038%, and in nanometer iron oxide red product, ferric oxide content is 98.6%, and particle diameter is 90nm.
Embodiment 4
Repeat embodiment 1.Wherein use polystyrene to replace Xylitol, other condition is as follows:
According to above-mentioned ball milling sieve, the step such as batching, acidleach, ion-exchange, removal of impurities, heavy manganese, oxidation, washing, oven dry operates successively, wherein in burden process, to choose containing manganese grade be 35.8%, and pyrolusite and iron content 90.8% reduced iron powder are raw material, and the ratio that is 1.5:1 in the amount mol ratio of iron substance in manganese amount of substance and reductive agent in pyrolusite batching, it is 99.2% that the leaching yield of manganese reaches, the comprehensive recovery of manganese is 92.6%, in trimanganese tetroxide product, manganese content is 71.8%, and specific surface is 23.8m
2/ g,, containing selenium, dioxide-containing silica is not 0.005%, and sulphur content is 0.030%, and in nanometer iron oxide red product, ferric oxide content is 98.1%, and particle diameter is 80nm.
Claims (10)
1. pyrolusite wet reducing is prepared the method for electronic-grade trimanganese tetroxide and by-product nanometer iron oxide red, and the method comprises the following steps:
(1) ball milling sieves: by pyrolusite thing ball milling (for example to 80 order-300 order, preferably 90 order-200 orders), then sieve;
(2) batching: add reductive agent and stir, obtaining mixed mineral powder; Preferably, described reductive agent is for containing the reductive agent of elemental iron, and it is 0.8-5.0:1, preferred 0.9-4.0:1, more preferably 1.0-3.0:1 that the addition of reductive agent makes in pyrolusite thing in manganese and reductive agent the consumption molar ratio of iron;
(3) acidleach: mixed mineral powder metering is dropped in acidleach pond and carries out acidleach, and then filtering separation, obtains filter residue and filtrate;
(4) ion-exchange: the resin that filtrate use is inhaled iron (III) adsorbs, and water and polymeric adsorbent are separated, obtains containing the tail water of manganese and the polymeric adsorbent phase of iron content (III) ion; Preferably, use for the equilibrium adsorption capacity of iron (III) be greater than 117.0mg/g, be preferably greater than 118.0mg/g, more preferably greater than 118.5mg/g, be further preferably greater than 119.0mg/g, for the equilibrium adsorption capacity of mn ion lower than 6mg/g, preferably lower than 5mg/g, more preferably less than 4mg/g, further preferably adsorb lower than the resin of 3.5mg/g;
(5) removal of impurity: after deionizing exchange containing iron ion, heavy metal ion, calcium, magnesium ion in manganese tail water;
(6) heavy manganese, oxidation: regulating the pH containing manganese tail water with ammoniacal liquor is 8.5-11, preferred 9-10, be settled out manganese, filter, water repetitive scrubbing throw out is to till sulfate radical-free ion or essentially no sulfate ion, obtain manganous hydroxide mud, for example, by chloride buffer solution (2-30wt% concentration, as 4-20wt% concentration) manganous hydroxide mud is deployed into containing manganese concentration is 0.08～1.0mol/L, preferred 0.09～0.8mol/L, more preferably the solution of 0.1～0.5mol/L, add hydrazine hydrate to stablize to control the current potential of solution, add dispersion agent (0.08-10 volume % for example, the dispersion agent of preferred 0.1-5 volume % (volume based on solution)), pass into air simultaneously and carry out reflux oxidation, in oxidising process, with the pH of ammoniacal liquor adjusting or control mixed solution, be 8.5-11, preferred 9-10, filter and obtain filter residue,
(7) washing, dry: wash filter residue that step (6) obtains with water to till sulfate radical-free ion or essentially no sulfate ion, then dry, obtain electronic-grade trimanganese tetroxide product;
(8) prepare nanometer iron oxide red: the polymeric adsorbent of iron content (III) ion with hydrochloric acid soln after to ion-exchange carries out desorb mutually, obtains stripping liquid, then that stripping liquid is nanometer iron oxide red for the preparation of byproduct.
2. method according to claim 1, is characterized in that: in above-described step 4) in, as the polymeric adsorbent of absorption iron (III) ion or the resin of suction iron (III), use aminophosphonic acid functional group-CH
2nHCH
2pO
3 -content is 1.30-1.53mmol/g, more preferably 1.33-1.50mmol/g, more preferably 1.36-1.48mmol/g, further preferred vinylbenzene-divinylbenzene crosslink multipolymer resin of 1.38-1.45mmol/g.
3. method according to claim 1 and 2, it is characterized in that: the acidleach process of described step (3) is carried out as follows: first mixed mineral powder metering is dropped in described acidleach pond, (for example sulfuric acid concentration is at 20-98.5wt% in acidleach pond, to add the sulfuric acid of the 10-100% that is equivalent to mixed mineral powder weight, more preferably 30-90wt% scope), then add water and control adding of the water yield by solid-to-liquid ratio 1:1-10, preferred 1:1.5-8, at 15-99 ℃, preferred 20-90 ℃, agitation leach 1-20h, preferred 2-10h, then carry out filtering separation; And/or
In the pH of filtrate value, in 1.4-2.1 scope (preferably 1.5-2.0) and temperature, under the condition of 10-42 ℃ of scope (preferably 20-41 ℃, more preferably 25-41 ℃, more preferably 30-40 ℃), with the resin of inhaling iron (III), adsorb.
4. according to any one method in claim 1-3, it is characterized in that, the removal of impurities process of described step (5) is carried out as follows: described containing adding in the tail water of manganese manganous carbonate regulator solution pH value to 2.5-6, preferred 3-5, making iron contamination ion a small amount of in solution be hydrolyzed to ferric hydroxide precipitate removes, adding alkali metalsulphide (as sodium sulphite) or passing into hydrogen sulfide makes the heavy metal ion in solution remove with sulfide precipitation, then add Manganous fluoride, make Ca2+ in filtrate, Mg2+ ion generate fluorochemical precipitation and remove.
5. according to any one method in claim 1-4, it is characterized in that, in described (6) heavy manganese and oxidising process, add with respect to the 0.08-2.0% of heavy manganese solution volume, more preferably 0.09-1.5%, more preferably the hydrazine hydrate of 0.1-1.0% is stable to control the current potential of solution, pass into the time 1-20h of air return oxidation, preferred 2-10h, oxidation control temperature is 15-98 ℃, preferably 20-90 ℃, more preferably 30-80 ℃.
6. according to the method described in right 5, it is characterized in that the dispersion agent described in described (6) oxidising process is one or more in polystyrene, Xylitol, C2-C6 dibasic alcohol (as ethylene glycol, propylene glycol or butyleneglycol), the 0.08-10.0vol% that add-on is mixeding liquid volume, preferably 0.09-8.0vol%, more preferably 0.1-5.0vol%.
7. according to any one method in claim 1-6, it is characterized in that, described (8) are prepared nano grade iron oxide red process and are: described stripping liquid or iron (III) ion elutriant are neutralized to precipitate to obtain byproduct after tapping a blast furnace, filter, wash, be dried, calcine nanometer iron oxide red; Preferably, the purity of nanometer iron oxide red product is greater than 94wt%, is preferably greater than 95wt%, more preferably greater than 96wt%, and particle diameter is less than 100nm, is preferably less than 90nm, is more preferably less than 80nm, is particularly preferably less than 70nm.
8. method according to claim 7, it is characterized in that, described (8) are prepared nano grade iron oxide red process and are carried out as follows: stripping liquid or iron (III) ion elutriant are heated to 30-90 ℃, preferred 35-80 ℃, for example, with ammoniacal liquor (concentration 5-28wt%, more preferably 7-20wt%) by the pH regulator of solution for example, to 1.5-2.5 (2), using urea as precipitation agent, the quality that adds precipitation agent urea is 10-20 times of iron ion Theoretical Mass in solution, in temperature, be 60-98 ℃, (the preferred 1-6h of stirring reaction 0.5-10h under the condition of preferred 70-95 ℃ (as 90 ℃), as 3h), suction filtration, obtain ironic hydroxide presoma, after being dried, grinds evenly described ironic hydroxide presoma, calcining (for example calcining 3-4h at 300-800 ℃ in retort furnace), obtain byproduct nanometer iron oxide red.
9. according to the method described in any one in claim 1-8, it is characterized in that, the concentration of the ammoniacal liquor in step (6) is 5-28wt%, more preferably 7-20wt%; And/or
Described in step (8), the concentration of hydrochloric acid soln is 2-45wt%, preferably 3%-15wt%, more preferably 5%-10wt%.
10. according to the method described in any one in claim 1-9, it is characterized in that described reductive agent or be waste iron filing or iron powder containing the reductive agent of elemental iron; And/or
In the trimanganese tetroxide product obtaining, manganese content reaches 70-72wt% (preferably 71.5-72%), and specific surface area is greater than 20m
2/ g, preferably 20m
2/ g-50m
2/ g, more preferably 25m
2/ g-40
2/ g; Dioxide-containing silica is less than 0.01wt%, and sulphur content is less than 0.05wt%, and the content of selenium is for being less than 0.001wt%, being preferably 0wt%.
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| CN110396612A (en) * | 2019-08-29 | 2019-11-01 | 贵州大学 | A kind of method that pyrolusite reduction prepares manganese sulfate solution |
| CN113479938A (en) * | 2021-07-02 | 2021-10-08 | 内蒙古科技大学 | Method for preparing high-purity iron oxide by using iron oxide |
| CN113603150A (en) * | 2021-09-23 | 2021-11-05 | 广州大学 | Iron oxide red and preparation method thereof |
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| CN103205570A (en) * | 2013-04-26 | 2013-07-17 | 吉首大学 | Method for producing vanadium pentoxide and by-product manganese sulfate from by using coal vanadium ore and pyrolusite together |
| CN103739018A (en) * | 2013-12-31 | 2014-04-23 | 周建华 | Method for producing trimanganese tetroxide |
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| CN101880767A (en) * | 2010-06-07 | 2010-11-10 | 姚茂君 | Process for reducing leached pyrolusite ore by iron powder |
| CN102094119A (en) * | 2011-01-21 | 2011-06-15 | 吉首大学 | Method for preparing electrolytic manganese metal with low-grade pyrolusite wet leaching |
| CN103205570A (en) * | 2013-04-26 | 2013-07-17 | 吉首大学 | Method for producing vanadium pentoxide and by-product manganese sulfate from by using coal vanadium ore and pyrolusite together |
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| CN110203975A (en) * | 2019-04-25 | 2019-09-06 | 宁波行殊新能源科技有限公司 | The leaching method of manganese element and the preparation method of LITHIUM BATTERY manganese sulfate |
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| CN113479938A (en) * | 2021-07-02 | 2021-10-08 | 内蒙古科技大学 | Method for preparing high-purity iron oxide by using iron oxide |
| CN113603150A (en) * | 2021-09-23 | 2021-11-05 | 广州大学 | Iron oxide red and preparation method thereof |
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