CN104016417B - The nanometer iron oxide red technique of electronic-grade trimanganese tetroxide by-product prepared by pyrolusite - Google Patents
The nanometer iron oxide red technique of electronic-grade trimanganese tetroxide by-product prepared by pyrolusite Download PDFInfo
- Publication number
- CN104016417B CN104016417B CN201410256547.8A CN201410256547A CN104016417B CN 104016417 B CN104016417 B CN 104016417B CN 201410256547 A CN201410256547 A CN 201410256547A CN 104016417 B CN104016417 B CN 104016417B
- Authority
- CN
- China
- Prior art keywords
- iron
- ion
- manganese
- oxide red
- iron oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of wet metallurgy of manganese, provide a kind of pyrolusite wet reducing and prepare the nanometer iron oxide red technique of electronic-grade trimanganese tetroxide by-product.The operations such as pyrolusite sieves through ball milling by this technique, prepare burden (adding reductive agent), acidleach, the ion-exchange of use resin, removal of impurities, heavy manganese, oxidation, washing and drying produce electronic-grade trimanganese tetroxide product.It is nanometer iron oxide red that ion-exchanging eluent produces byproduct through operations such as the heavy iron of neutralization, filtration, washing drying and calcinings.The leaching yield of manganese reaches more than 98%, and comprehensive recovery is greater than 90%, and in trimanganese tetroxide product, Fe content reaches 71%, and specific surface area is greater than 20m
2/ g, simultaneously can the nanometer iron oxide red product of by-product, and nanometer iron oxide red product purity is greater than 95%, and particle diameter is less than 100nm, compares with existing technique, and improve trimanganese tetroxide product purity, quality product is more stable, reduces production cost.
Description
Technical field
The invention belongs to the technical field of wet metallurgy of manganese, particularly relate 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 one of production important raw and processed materials needed for 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.Industrially, mostly adopt electrolytic metal Mn sheet to be raw material preparation both at home and abroad at present, because manganese metal price is higher, cause trimanganese tetroxide production cost higher, and foreign matter selenium content is higher, direct manganese ore is only had to be that raw material production trimanganese tetroxide just has larger price competitiveness.China's manganese resource enriches, and mainly contains rhodochrosite and pyrolusite, and along with the development of electrolytic manganese develops, domestic rhodochrosite resource is close to exhausted, and pyrolusite resource is not well utilized.How rationally research and development utilize pyrolusite to prepare trimanganese tetroxide is an approach effectively solving promoter manganese problem, simultaneously also for the novel process of an efficient economy is found out in the production of high-end trimanganese tetroxide.
The processing of pyrolusite mainly contains prereduction Roasting And Leaching method (thermal process) and direct leaching (wet processing) two kinds, the former carries out roasting to pyrolusite under reductive agent existent condition, main component Manganse Dioxide in pyrolusite is made to be reduced to acid-soluble manganese monoxide, then carry out leaching with leaching agents such as acid and carry out removal of impurities to leach liquor and obtain manganous salt solution, manganous salt solution obtains trimanganese tetroxide through heavy manganese and oxidation.The reductive agent used has pyrite, brown coal, carbon monoxide, gac and graphite etc.The key distinction of direct leaching method and prereduction Roasting And Leaching method is that direct leaching is without the need to through the high-temperature roasting stage, but utilizes reductive agent to carry out direct-reduction to pyrolusite in leaching agent solution, realizes the direct leaching of pyrolusite.The reductive agent used 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 have that technical process is shorter, energy consumption is less, the cost also advantage such as lower, environmental protection, more meeting 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 while the highly purified electronic-grade trimanganese tetroxide product of production, can also by-product purity is greater than 95wt%, median size is less than 100nm nanometer iron oxide red product.
Therefore, suitable reductive agent is selected to improve the leaching yield of manganese, and reduzate is recycled, reduce production cost, the processing condition controlling to be applicable to 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 prepares 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 manganese in trimanganese tetroxide technique prepared by existing pyrolusite.
Adsorb for iron ion from ferromanganese solution for use resin at present, desirable resin is selected the polymeric adsorbent various from quantity or resin, require it as far as possible optionally can adsorb iron ion under given conditions and can reduce the absorption for mn ion, other heavy metal ion, calcium, magnesium ion simultaneously as far as possible, this is a technical barrier.Existing resin or polymeric adsorbent product cannot be competent at this requirement.
The present inventor by improving technique, such as, adds hydrazine hydrate and dispersion agent, the purity of trimanganese tetroxide product is significantly improved in heavy manganese, oxidising process; By using specific resin optionally to adsorb iron ion from ferromanganese solution, the by product of acquisition 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 (such as to 80 order-300 order, preferably 90 order-200 orders), then sieve;
(2) prepare burden: add reductive agent and stir, obtain mixed mineral powder;
(3) acidleach: mixed mineral powder metering is dropped in acidleach pond and carries out acidleach, then filtering separation, obtain filter residue and filtrate;
(4) ion-exchange: filtrate is adsorbed with the resin inhaling iron (III), aqueous phase and polymeric adsorbent is separated, obtains containing the tail water of manganese and the polymeric adsorbent phase of iron content (III) ion; Preferably, use and the equilibrium adsorption capacity of iron (III) is greater than to 117.0mg/g, is preferably greater than 118.0mg/g, more preferably greater than 118.5mg/g, is preferably greater than 119.0mg/g further, for the equilibrium adsorption capacity of mn ion lower than 6mg/g, preferably lower than 5mg/g, adsorb more preferably less than 4mg/g, the further preferred resin lower than 3.5mg/g.More preferably, above-mentioned resin has 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 the styrene-divinylbenzene cross-linking copolymer resin of preferred 1.38-1.45mmol/g.Still more preferably, in the pH value of filtrate in 1.4-2.1 scope (preferred 1.5-2.0) and temperature at 10-42 DEG C of scope (preferred 20-41 DEG C, more preferably 25-41 DEG C, more preferably 30-40 DEG C) condition under adsorb with the resin of above-mentioned suction iron (III).
(5) removal of impurities: the iron ion, heavy metal ion, calcium, the magnesium ion that contain in manganese tail water (i.e. the aqueous solution) after deionizing exchanges;
(6) heavy manganese, oxidation: regulate the pH containing manganese tail water to be 8.5-11 with ammoniacal liquor, preferred 9-10, be settled out manganese, filter, with water repetitive scrubbing throw out to sulfate radical-free ion or essentially no sulfate ion, obtain manganous hydroxide mud, by ammonium chloride buffer solution (such as 2-30wt% concentration, as 4-20wt% concentration) to be deployed into containing manganese concentration by manganous hydroxide mud be 0.08 ~ 1.0mol/L, preferably 0.09 ~ 0.8mol/L, preferably the solution of 0.1 ~ 0.5mol/L (namely, heavy manganese solution), add hydrazine hydrate (such as based on the 0.08-2.0 volume % of liquor capacity, preferred 0.1vol%-0.5vol%, as 0.2vol% or 0.3vol%) stablize with the current potential controlling solution, 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, regulating with ammoniacal liquor or control the pH of mixed solution in oxidising process is 8.5-11, preferred 9-10, filter and obtain filter residue,
(7) wash, dry: wash filter residue that step (6) obtains with water to sulfate radical-free ion or essentially no sulfate ion, then dry, obtain electronic-grade trimanganese tetroxide product.Its Fe 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: by hydrochloric acid soln (such as 3-10wt% concentration, preferred 4-8wt% concentration) mutually desorb is carried out to the polymeric adsorbent of iron content (III) ion after ion-exchange, 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.The addition of reductive agent makes the consumption molar ratio of iron in manganese and reductive agent in pyrolusite thing be 0.8-5.0:1, preferably 0.9-4.0:1, more preferably 1.0-3.0:1, 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 drop in described acidleach pond by mixed mineral powder metering, 10-100% (the preferred 20-90% being equivalent to mixed mineral powder weight is added in acidleach pond, more preferably 30-80%, more preferably 35-70%) sulfuric acid (such as sulfuric acid concentration is at 20-98.5wt%, more preferably 30-90wt%, more preferably 40-80wt%, more preferably 45-70wt%, such as 50wt% or 60wt%), then add water and press 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 DEG C, agitation leach 1-20h at preferred 20-90 DEG C, preferred 2-10h, more preferably 3-6h, more preferably 4h-5h, then filtering separation is carried out.
In above-described step 4) in, as the polymeric adsorbent (or inhaling the resin of iron (III)) of absorption iron (III) ion, preferably use aminophosphonic acid functional group (-CH
2nHCH
2pO
3 -) content is the styrene-divinylbenzene cross-linking copolymer resin of 1.30-1.53mmol/g (more preferably 1.33-1.50mmol/g, more preferably 1.36-1.48mmol/g, further preferably 1.38-1.45mmol/g).When aminophosphonic acid functional group content is higher than 1.53mmol/g, the interference of mn ion and calcium, magnesium ion strengthens.And when aminophosphonic acid functional group content is lower than 1.30mmol/g, the loading capacity for ferric ion can decline.
This resin is generally use, namely with aminophosphonic acid sodium functional group (-CH with sodium-salt form
2nHCH
2pO
3na
2).This resin is rendered as the form of particle (preferred spherical particle).The median size of resin particle 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 styrene-divinylbenzene interpolymer is 6-9%, more preferably 7-8.5%.
As the resin 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, preferred 1.38-1.45mmol/g further) time, at pH=1.4-2.1 scope (preferred 1.5-2.0, more preferably 1.6-1.9) and 10-42 DEG C of temperature range (preferred 20-41 DEG C, more preferably 25-41 DEG C, more preferably 30-40 DEG C, more preferably 38-40 DEG C) under, above-mentioned resin (resin of preferred 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, be preferably greater than 119.0mg/g further, for the equilibrium adsorption capacity of mn ion lower than 6mg/g, preferably lower than 5mg/g, more preferably less than 4mg/g, preferred lower than 3.5mg/g further.In addition, for calcium and magnesium ion equilibrium adsorption capacity lower than 5mg/g, preferably lower than 4mg/g, preferably lower than 3mg/g.
Most similar resin well known in the prior art under above-mentioned pH and temperature for the equilibrium adsorption capacity of iron (III) generally lower than 100mg/g, optimally just can 115mg/g be reached, but, for the equilibrium adsorption capacity of mn ion higher than 15mg/g, optimally just can 8mg/g be reached.Key is, for interfering ion as the equilibrium adsorption capacity of calcium, magnesium ion is also higher, generally higher than 10mg/g.
Preferably, the dedoping step of described step (5) carries out as follows: add manganous carbonate regulator solution pH value to 2.5-6, preferably 3-5, more preferably 3.5-4.5 in described containing in the tail water of manganese, iron contamination ion a small amount of in solution is made to be hydrolyzed to ferric hydroxide precipitate removing, 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+, Mg2+ ion in filtrate generate the removing of fluorochemical precipitation.
Preferably, in described (6) heavy manganese and oxidising process, add and stablize with the current potential controlling solution relative to the hydrazine hydrate of the 0.08-2.0 volume % of heavy manganese solution volume, preferably 0.09-1.5 volume %, more preferably 0.1-1.0 volume %, pass into the time 1-20h of air return oxidation, preferably 2-10h, oxidation control temperature is 15-98 DEG C, preferably 20-90 DEG C, more preferably 30-80 DEG C, more preferably 40-70 DEG C, such as 50 DEG C or 60 DEG C.
Preferably, be one or more in polystyrene, Xylitol, C2-C6 dibasic alcohol (as ethylene glycol, propylene glycol or butyleneglycol) at the dispersion agent described in described step (6) oxidising process, add-on is 0.08-10.0vol%, preferably 0.09-8.0vol%, the preferably 0.1-5.0vol% of mixeding liquid volume.
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 elution liquid are carried out neutralize to precipitate tap a blast furnace, filter, wash, to obtain byproduct after dry, calcining 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%, is preferably greater than 97wt% further, still further preferably 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 elution liquid are heated to 30-90 DEG C, preferred 35-80 DEG C, with ammoniacal liquor (such as 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) adding precipitation agent urea is 10-20 times of iron ion Theoretical Mass (or molar weight) in solution, be 60-98 DEG C in temperature, stirring reaction 0.5-10h (preferred 1-6h under the condition of preferred 70-95 DEG C (as 90 DEG C), as 3h), suction filtration, obtain ironic hydroxide presoma, after being dried by described ironic hydroxide presoma, grinding evenly, calcining (such as calcines 2-7h at 300-800 DEG C 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%, preferred 3%-15wt%, more preferably 5%-10wt%.
Preferably, described reductive agent or the reductive agent containing elemental iron are waste iron filing or iron powder.
Preferably, in the trimanganese tetroxide product obtained, Fe 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, preferred 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 used in the application, its main component is Manganse Dioxide, is generally 45%-67wt%, such as 50-65wt%, as 63wt% containing manganese rate.
Advantageous Effects of the present invention
In heavy manganese, oxidising process, the current potential of solution is kept to stablize and add specific dispersion agent by adding hydrazine hydrate, significantly improve the purity of trimanganese tetroxide product, 98.5wt%-99.93wt% is increased to by 92wt%-97wt%, more preferably 99-99.93wt% is increased to, especially 99.5-99.9wt%, reaches electronic-grade purity.
Tested by a large amount of selectivity tests, specific polymeric adsorbent is selected from a large amount of polymeric adsorbents or resin, its primary attachment iron (III) ion but adsorb the resin of mn ion hardly, is conducive to the iron of solution (III) ion to be 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, Fe content reaches 71.5-72% (theoretical content 72.05wt%), and specific surface area is greater than 20m
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, and 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, reduce energy consumption and production cost, decrease environmental pollution, the electronic-grade trimanganese tetroxide constant product quality prepared, 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, as the polymeric adsorbent (or inhaling the resin of iron (III)) of absorption iron (III) ion, aminophosphonic acid functional group (-CH is used
2nHCH
2pO
3 -) content is the styrene-divinylbenzene cross-linking copolymer resin (be called for short polymeric adsorbent A) of 1.42mmol/g.Use with sodium-salt form.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 (preferred 1.5-2.0) and 10-42 DEG C of temperature range (preferred 20-41 DEG C, more preferably 25-41 DEG C, more preferably 30-40 DEG C, more preferably 38-40 DEG C) under, above-mentioned resin (Na salt form) is greater than 118.0mg/g for the equilibrium adsorption capacity of iron (III), more preferably greater than 118.5mg/g, be preferably greater than 119.0mg/g further, for the equilibrium adsorption capacity of mn ion lower than 5mg/g, more preferably less than 4mg/g, preferred lower than 3.5mg/g further, 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 DEG C 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
Sieve after pyrolusite being milled to 80 orders, in screened material, adding iron iron filings as reductive agent stirs, and wherein the addition of iron filings makes the consumption molar ratio of manganese and iron in pyrolusite thing be 1.5:1.The metering of gained mixed mineral powder is dropped in acidleach pond, add be equivalent to mixed mineral powder weight 60% the sulfuric acid of concentration 80wt%.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 DEG C, obtains filtrate.First the pH regulator of gained filtrate is remained on 38-40 DEG C to 2.0 and temperature, then this filtrate carries out adsorbing (within 100 minutes, reaching balance) with the polymeric adsorbent A inhaling iron (III), aqueous phase 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 having adsorbed iron uses the hydrochloric acid soln desorb of 5% mutually, obtains the stripping liquid of iron content.
Containing in manganese tail water after ion exchange adds the pH value to 4 that manganous carbonate regulates this solution (namely containing manganese tail water), makes iron contamination ion a small amount of in solution be hydrolyzed to ferric hydroxide precipitate and pass through to filter, obtains filtrate.Then in filtrate, add sodium sulphite makes the heavy metal ion in solution be removed with sulfide precipitation.In the filtrate of removing heavy metal, add Manganous fluoride, make Ca in filtrate
2+, Mg
2+ion generates the removing of fluorochemical precipitation.Then regulate the pH of filtrate in 9-10 scope with ammoniacal liquor, precipitation manganese, filters and obtains filter residue, with clear water repetitive scrubbing filter residue to essentially no sulfate ion, obtain manganous hydroxide mud.Being deployed into containing manganese concentration with ammonium chloride buffer solution by manganous hydroxide mud is the solution of 0.4mol/L, the current potential adding the hydrazine hydrate control solution being equivalent to heavy manganese solution volume 0.8% is stablized, add the Xylitol being equivalent to heavy manganese solution volume 3.0%, pass into air return oxidation 5h simultaneously, it is 70 DEG C that oxidizing temperature controls, be 9.5 with the pH that the ammoniacal liquor of concentration 20wt% controls mixed solution in oxidising process, filter and obtain filter residue, gained filter residue with clear water washing to sulfate radical-free ion.Filter residue is dried, and obtains electronic-grade trimanganese tetroxide product.Adopt ferrous ammonium sulfate titration (GB/T1506-2002), record the content 72wt% of manganese in trimanganese tetroxide product, the purity corresponding to trimanganese tetroxide is 99.93wt%.
Iron (III) ion elution liquid (i.e. the stripping liquid of iron content) after ion-exchange being resolved is heated to 70 DEG C, with the ammoniacal liquor of concentration 25wt% by the pH regulator of solution to 2.Using urea as precipitation agent, the quality (or molar weight) adding precipitation agent urea is 10-20 times of the quality (or molar weight) of iron ion.Then be stirring reaction 3h under the condition of 90 DEG C in temperature, suction filtration, obtains ironic hydroxide presoma, and after being dried by presoma, grinding evenly, calcines 3-4h, obtain byproduct nanometer iron oxide red in retort furnace at 300-800 DEG C.
The leaching yield of manganese reaches 99%, and the comprehensive recovery of manganese reaches 93%.In trimanganese tetroxide product, Fe 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%, and median size is 80nm.
Comparative example 1
Repeat embodiment 1, the Xylitol just do not added in heavy manganese solution as dispersion agent.Adopt ferrous ammonium sulfate titration (GB/T1506-2002), record the content 68.8wt% of manganese, the purity corresponding to trimanganese tetroxide is 95.48wt%.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.Adopt ferrous ammonium sulfate titration (GB/T1506-2002), record the content 67.5wt% of manganese, the purity corresponding to trimanganese tetroxide is 93.69wt%.Nanometer iron oxide red product purity is 98%, and median size is 80nm.
Embodiment 2
Repeat embodiment 1.Other condition is as follows:
Sieve according to above-mentioned ball milling, prepare burden, acidleach, ion-exchange, removal of impurities, the step such as heavy manganese, oxidation, washing, oven dry operate successively, wherein in burden process, choose containing manganese grade be 35.8% pyrolusite and iron content 95.6% waste iron filing be raw material, and prepare burden in the ratio that the mol ratio of the amount of iron substance in manganese amount of substance in pyrolusite and reductive agent is 1.4:1, it is 98.6% that the leaching yield of manganese reaches, the comprehensive recovery of manganese is 92.5%, in trimanganese tetroxide product, Fe content is 71.5%, and specific surface is 23.6m
2/ g, not containing selenium, dioxide-containing silica is 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:
Sieve according to above-mentioned ball milling, prepare burden, acidleach, ion-exchange, removal of impurities, the step such as heavy manganese, oxidation, washing, oven dry operate successively, wherein in burden process, to choose containing manganese grade be the pyrolusite of 27.5% and the waste iron filing of iron content 93.6% is raw material, and prepare burden in the ratio that the mol ratio of the amount of iron substance in manganese amount of substance in pyrolusite and reductive agent is 1.5:1, it is 98.5% that the leaching yield of manganese reaches, the comprehensive recovery of manganese is 91.8%, in trimanganese tetroxide product, Fe content is 71.6%, and specific surface is 22.8m
2/ g, not containing selenium, dioxide-containing silica is 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:
Sieve according to above-mentioned ball milling, prepare burden, acidleach, ion-exchange, removal of impurities, the step such as heavy manganese, oxidation, washing, oven dry operate successively, wherein in burden process, choose containing manganese grade be 35.8% pyrolusite and iron content 90.8% reduced iron powder be raw material, and prepare burden in the ratio that the amount mol ratio of iron substance in manganese amount of substance in pyrolusite and reductive agent is 1.5:1, it is 99.2% that the leaching yield of manganese reaches, the comprehensive recovery of manganese is 92.6%, in trimanganese tetroxide product, Fe content is 71.8%, and specific surface is 23.8m
2/ g, not containing selenium, dioxide-containing silica is 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 (21)
1. pyrolusite wet reducing prepares 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: pyrolusite thing is milled to 80 order-300 orders, then sieves;
(2) prepare burden: add reductive agent and stir, obtain mixed mineral powder, described reductive agent is the reductive agent containing elemental iron, and the addition of reductive agent makes the consumption molar ratio of iron in manganese and reductive agent in pyrolusite thing be 0.8-5.0:1;
(3) acidleach: mixed mineral powder metering is dropped in acidleach pond and carries out acidleach, then filtering separation, obtain filter residue and filtrate;
(4) ion-exchange: the resin that filtrate use inhales iron (III) adsorbs, aqueous phase and polymeric adsorbent are separated, obtain containing the tail water of manganese and the polymeric adsorbent phase of iron content (III) ion, use and be greater than 117.0mg/g for the equilibrium adsorption capacity of iron (III), the equilibrium adsorption capacity for mn ion adsorbs lower than the resin of 6mg/g;
(5) removal of impurity: the iron ion, heavy metal ion, calcium, the magnesium ion that contain in manganese tail water after deionizing exchanges;
(6) heavy manganese, oxidation: regulate the pH containing manganese tail water to be 8.5-11 with ammoniacal liquor, be settled out manganese, filter, with water repetitive scrubbing throw out to sulfate radical-free ion, obtain manganous hydroxide mud, being deployed into containing manganese concentration with ammonium chloride buffer solution by manganous hydroxide mud is the solution of 0.08 ~ 1.0mol/L, add hydrazine hydrate to stablize with the current potential controlling solution, add dispersion agent, pass into air simultaneously and carry out reflux oxidation, regulating with ammoniacal liquor or control the pH of mixed solution in oxidising process is 8.5-11, filters and obtains filter residue;
(7) wash, dry: wash filter residue that step (6) obtains with water to sulfate radical-free ion or essentially no sulfate ion, then dry, obtain electronic-grade trimanganese tetroxide product;
(8) prepare nanometer iron oxide red: carry out desorb mutually with the polymeric adsorbent of hydrochloric acid soln to iron content (III) ion after ion-exchange, obtain stripping liquid, then that stripping liquid is nanometer iron oxide red for the preparation of byproduct;
Wherein, 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 the styrene-divinylbenzene cross-linking copolymer resin of 1.30-1.53mmol/g.
2. method according to claim 1, is characterized in that, in step (1), pyrolusite thing is milled to 90 order-200 orders.
3. method according to claim 1, is characterized in that, the addition of reductive agent makes the consumption molar ratio of iron in manganese and reductive agent in pyrolusite thing be 1.0-3.0:1.
4. method according to claim 1, is characterized in that, ammonium chloride buffer solution is 2-30wt% concentration.
5. method according to claim 1, is characterized in that, in step (6), being deployed into containing manganese concentration with ammonium chloride buffer solution by manganous hydroxide mud is the solution of 0.1 ~ 0.5mol/L.
6. method according to claim 1, is characterized in that, in step (6), adds the dispersion agent of the 0.08-10 volume % of the volume based on solution.
7. method according to claim 1, is characterized in that, in step (6), regulating with ammoniacal liquor or control the pH of mixed solution in oxidising process is 9-10.
8. method according to claim 1, is characterized in that, uses aminophosphonic acid functional group-CH
2nHCH
2pO
3 -content is the styrene-divinylbenzene cross-linking copolymer resin of 1.33-1.50mmol/g.
9. method according to claim 1, is characterized in that, uses aminophosphonic acid functional group-CH
2nHCH
2pO
3 -content is the styrene-divinylbenzene cross-linking copolymer resin of 1.38-1.45mmol/g.
10. 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 drop in described acidleach pond by mixed mineral powder metering, the sulfuric acid of the concentration 20-98.5wt% of the 10-100% being equivalent to mixed mineral powder weight is added in acidleach pond, then add water and control adding of the water yield by solid-to-liquid ratio 1:1-10, agitation leach 1-20h at 15-99 DEG C, then carries out filtering separation; And/or
Adsorb with the resin inhaling iron (III) under the condition of 10-42 DEG C of scope in 1.4-2.1 scope and temperature in the pH value of filtrate.
11. methods according to claim 10, it is characterized in that, in the acidleach of step (3), add water and control adding of the water yield by solid-to-liquid ratio 1:1.5-8, adsorbing with the resin inhaling iron (III) under the condition of 30-40 DEG C of scope in 1.5-2.0 scope and temperature in the pH value of filtrate.
12. methods according to claim 1, it is characterized in that, the dedoping step of described step (5) carries out as follows: add manganous carbonate regulator solution pH value to 2.5-6 in described containing in the tail water of manganese, iron contamination ion a small amount of in solution is made to be hydrolyzed to ferric hydroxide precipitate removing, adding alkali metalsulphide or passing into hydrogen sulfide makes the heavy metal ion in solution remove with sulfide precipitation, then add Manganous fluoride, make Ca in filtrate
2+, Mg
2+ion generates the removing of fluorochemical precipitation.
13. methods according to claim 1, it is characterized in that, in the heavy manganese of described step (6) and oxidising process, add and stablize with the current potential controlling solution relative to the hydrazine hydrate of the 0.08-2.0% of heavy manganese solution volume, pass into the time 1-20h of air return oxidation, oxidation control temperature is 15-98 DEG C.
14. methods according to right 13, is characterized in that: the dispersion agent described in oxidising process of described step (6) is one or more in polystyrene, Xylitol, C2-C6 dibasic alcohol, and add-on is the 0.08-10.0vol% of mixeding liquid volume.
15. methods according to claim 1, it is characterized in that, the nano grade iron oxide red process of preparation of described step (8) is: described stripping liquid or iron (III) ion elution liquid are carried out neutralize to precipitate tap a blast furnace, filter, wash, to obtain byproduct after dry, calcining nanometer iron oxide red.
16. methods according to claim 15, is characterized in that: the purity of nanometer iron oxide red product is greater than 94wt%, and particle diameter is less than 100nm.
17. methods according to claim 16, is characterized in that: the purity of nanometer iron oxide red product is greater than 96wt%, and particle diameter is less than 70nm.
18. methods according to claim 15, it is characterized in that, the nano grade iron oxide red process of preparation of described step (8) is carried out as follows: stripping liquid or iron (III) ion elution liquid are heated to 30-90 DEG C, with ammoniacal liquor by the pH regulator of solution to 1.5-2.5, using urea as precipitation agent, the quality adding precipitation agent urea is 10-20 times of iron ion Theoretical Mass in solution, be stirring reaction 0.5-10h under the condition of 60-98 DEG C in temperature, suction filtration, obtain ironic hydroxide presoma, after being dried by described ironic hydroxide presoma, grinding evenly, calcining, obtain byproduct nanometer iron oxide red.
19. methods according to claim 18, is characterized in that, the concentration of the ammoniacal liquor in step (6) is 5-28wt%; And/or
Described in step (8), the concentration of hydrochloric acid soln is 2-45wt%.
20. methods according to claim 1, is characterized in that, described reductive agent or the reductive agent containing elemental iron are waste iron filing or iron powder; And/or
In the trimanganese tetroxide product obtained, Fe content reaches 70-72wt%, and specific surface area is greater than 20m
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%.
21. methods according to claim 20, is characterized in that, in the trimanganese tetroxide product obtained, the content of selenium is 0wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410256547.8A CN104016417B (en) | 2014-06-10 | 2014-06-10 | The nanometer iron oxide red technique of electronic-grade trimanganese tetroxide by-product prepared by pyrolusite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410256547.8A CN104016417B (en) | 2014-06-10 | 2014-06-10 | The nanometer iron oxide red technique of electronic-grade trimanganese tetroxide by-product prepared by pyrolusite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104016417A CN104016417A (en) | 2014-09-03 |
| CN104016417B true CN104016417B (en) | 2016-02-03 |
Family
ID=51433479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410256547.8A Active CN104016417B (en) | 2014-06-10 | 2014-06-10 | The nanometer iron oxide red technique of electronic-grade trimanganese tetroxide by-product prepared by pyrolusite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104016417B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103739018A (en) * | 2013-12-31 | 2014-04-23 | 周建华 | Method for producing trimanganese tetroxide |
-
2014
- 2014-06-10 CN CN201410256547.8A patent/CN104016417B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103739018A (en) * | 2013-12-31 | 2014-04-23 | 周建华 | Method for producing trimanganese tetroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104016417A (en) | 2014-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108559843B (en) | Method for treating stone coal pickle liquor | |
| CN104016417B (en) | The nanometer iron oxide red technique of electronic-grade trimanganese tetroxide by-product prepared by pyrolusite | |
| CN106115768A (en) | A kind of comprehensive cyclic utilization method of steel plant zinc smoke ash | |
| CN108754191B (en) | Method for treating stone coal pickle liquor | |
| CN101817553B (en) | Method for treating arsenic-containing smoke dust | |
| CN102703715B (en) | Method for recovering rhenium and molybdenum from rhenium and molybdenum-containing concentrate calcination flue dust | |
| CN1908207A (en) | Method of comprehensive utilizing iron making blast furnace dust resources | |
| CN110090548B (en) | Method for wet desulphurization and zinc sulfate recovery of copper slag tailings and zinc smelting fly ash | |
| US8586218B1 (en) | Process for recycling alkaline batteries | |
| CN107012328A (en) | A kind of high ferro zinc leaching residue clean utilization method | |
| CN110734169B (en) | Method for removing chlorine from acid solution | |
| CN106115767A (en) | A kind of method of zinc oxide ore comprehensive utilization | |
| CN108502915A (en) | A method of nano zine oxide is prepared with high zinc dedusting ash | |
| CN105907960A (en) | Method for combined resourceful treatment of lead concentrate and zinc anode mud | |
| CN103074496B (en) | Method for separating and purifying magnesium dioxide from anode mud | |
| CN102465202B (en) | Cobalt copper sulfide ore processing method | |
| CN1532297A (en) | Method for wet zinc refining without iron slag | |
| CN109879323A (en) | It is a kind of to prepare ferritic method using electric furnace dust and mill scale | |
| CN108842053A (en) | The method of comprehensive utilization of Low grade manganese ore and electrolytic manganese crystallization double salt | |
| CN113000011A (en) | Heavy metal adsorption material and preparation method and application thereof | |
| KR20150050630A (en) | Method for producing high purity manganese oxide from byproduct of manganese steel alloy smelting furnace and electric furnace and high purity manganese oxide produced thereby | |
| CN108862372A (en) | A method of nano zine oxide and compound of calcium carbonate are produced using containing zinc ore crude | |
| CN103011295B (en) | Reduction method for producing manganese tetroxide | |
| CN112777642B (en) | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag | |
| CN108754140A (en) | A method of it is produced containing zinc complexes using containing zinc ore crude |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |