CN108330276A - Method for preparing high-purity iron powder using iron vitriol slag and products thereof and application - Google Patents
Method for preparing high-purity iron powder using iron vitriol slag and products thereof and application Download PDFInfo
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- CN108330276A CN108330276A CN201810091091.2A CN201810091091A CN108330276A CN 108330276 A CN108330276 A CN 108330276A CN 201810091091 A CN201810091091 A CN 201810091091A CN 108330276 A CN108330276 A CN 108330276A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B11/00—Making pig-iron other than in blast furnaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
Abstract
The invention discloses methods for preparing high-purity iron powder using iron vitriol slag and products thereof and application, it includes the following steps：（1）, pelletizing：Green-ball is obtained by iron vitriol slag and additive mixing, then through pelletizing；The additive includes the component of following parts by weight：Sodium humate 5% ~ 10%；Lime stone 25% ~ 40%；Dolomite 10% ~ 20%；Coal dust 30% ~ 45%；（2）, one-step method melting and reducing：Green-ball is dried at 200 DEG C ~ 400 DEG C, coke is added at 1450 DEG C ~ 1600 DEG C and carries out melting and reducing for the hot-bulb obtained after dry, obtains molten iron, melting and reducing time 40min ~ 80min；（3）, electrolysis：Molten iron is cast as anode plate, while using stainless steel plate as cathode, being electrolysed in electrolytic cell, high-purity iron powder is collected on cathode plate.The present invention comprehensively utilizes the iron in iron vitriol slag, prepares high-purity, and the iron powder of high added value improves process efficiency.
Description
Technical field
The present invention relates to metallurgical technology fields, more particularly to method for preparing high-purity iron powder using iron vitriol slag and products thereof and
Using.
Background technology
Currently, 80% or more metallic zinc is given birth to by the Zinc hydrometallurgy process of " roasting-leaching-purification-electrodeposition " in the world
Production.For the electricity Xin factories of 100,000 tons of zinc of an annual output, it is assumed that zinc concentrate iron-holder is in terms of 8%, if removing iron with jarosite process,
The quantum of output of iron vitriol slag is 5.3 ten thousand tons.Chinese zinc yield has reached 48,310,000 tons or so within 2006~2015 years.Thus can speculate
It is about 25,000,000 tons to go out the total iron vitriol slag volume of cargo in storage of last decade to be more than.Iron vitriol slag is in smeltery's Zinc hydrometallurgy process using Huang
A kind of solid industrial danger waste residue of krausite method iron removal step output.And most iron vitriol slag does not obtain effective profit
With generally construction cinder field stockpiling nearby occupies a large amount of land resource, while the heavy metal ion in iron vitriol slag（As zinc,
Copper, cadmium, lead, arsenic and tin etc.）, constantly dissolution leads to the destruction of ecological environment during stockpiling.Iron is main member in ferrovanadium slag
Element, content is usually 25%~30%, and China's iron ore average grade is only 29%.Therefore, iron vitriol slag is banked up extremely to lack iron resource
Weary and resource consumption big country China is greatly to waste.
Pyrogenic process extraction process is a kind of promising high efficient technology, extraction efficiency is high, waste water is few, secondary slag can realize it is harmless
Change and recycling, therefore a large amount of scholars study this.
The Chinese patent literature of Publication No. CN104911356A discloses a kind of solid waste gas ash, the synthesis of vanadium slag containing zinc-iron
Recovery process specifically discloses a kind of additive, for the one or several kinds in industrial silicon sand, lime, calcium hydroxide or calcium carbonate
Combination.By gas ash (mud) and Jarosite Residues according to (2 ~ 5)：1 ratio is uniformly mixed, by mixture and coke powder, life
Lime presses 1：0.18:0.03 carries out mixing, and after pelletizing in disk pelletizing machine, into being restored in rotary kiln.Also original product passes through
Three sections of gradient magnetic separations and three-level ore grinding, then output reduced iron powder and the Iron concentrate technique after the classification of high-efficiency helical grader.It should
Technological process is long, and investment is big, and ore grinding is of high cost.
The Chinese patent literature of Publication No. CN106755974 A discloses the system that a kind of iron vitriol slag freezes off knot reducting pellet
Standby and its recycling lead zinc-iron synchronizes the process of solid sulphur, specifically first mixes iron vitriol slag, reduction coal and sulphur-fixing agent and is pressed into iron
Alum slag freezes off knot reduction green pellets;Then cold bound pellet is dried;Dry pelletizing is carried out directly also at 1100-1250 DEG C
Original roasting, obtains leaded and the flue dust of zinc and the calcining of iron content and sulphur.Two stage grinding-magnetic separation is carried out to direct-reduction product
Method separation obtains iron ore concentrate.This method obtain iron ore concentrate Iron grade it is relatively low, only 75% or so, and iron recovery less than
60%, and sulfur content is higher in iron ore concentrate, is 0.3% or so, has seriously affected Iron Concentrate Quality.
The Chinese patent literature of Publication No. CN106011489A discloses a kind of method of processing iron vitriol slag, by iron vitriol slag
It is mixed with reducing agent, obtains mixed material；Mixed material is subjected to resolution process and reducing zone in reduction furnace resolver
Middle carry out reduction treatment, obtains the gaseous products containing lead, zinc and silver and the solid product containing metallic iron；Metal will be contained
The solid product of iron carries out ore grinding-magnetic separation, to obtain metallic iron and tailings.This method although iron in recyclable iron vitriol slag,
But iron powder grade is low, the rate of recovery is not high, and technological process is long, and investment is big.
The Chinese invention patent of Publication No. CN107267745A discloses a kind of extraction side of valuable element in iron vitriol slag
Method, specifically include pelletizing, oxidizing roasting desulfurization, direct-reduction, molten point, ingot casting, electrolysis.Additive includes organic adhesive
Agent, alkaline earth metal source, alkali metal source, carbonaceous fuel and ferriferous oxide.By the use of the additive, can strengthen pelletizing,
Improve pellet roasting desulfurization and consolidation effect, improve agglomerates intensity, improve agglomerates reproducibility, it is swollen to reduce pelletizing reduction
Swollen rate improves the mobility of slag, improves the desulphurizing ability of slag, coordinates the subsequent technique, it can be achieved that iron, gallium, zinc, indium, sulphur
Efficiently separating and extracting etc. a variety of valuable elements, but its emphasis is the recycling that solve a variety of valuable elements, the iron powder of acquisition
Grade is not high, it is impossible to be used in soft-magnetic parts, electronic component, high-performance and highdensity part, aviation, universe and atomic energy industry
The fields such as superalloy.
In conclusion in the published thermal process extraction wherein patent of ferro element utilized in relation to ferrovanadium slag, although
The iron in iron vitriol slag can be extracted, but technological process is long, of high cost, products obtained therefrom is Iron concentrate or molten iron, and product is additional
It is worth low, technique overall efficiency is relatively low.
Invention content
The technical problem to be solved by the present invention is to the existing method and process long flow path with iron vitriol slag extraction wherein ferro element, at
The iron powder grade of this height, acquisition is relatively low, provides a kind of method preparing high-purity iron powder using iron vitriol slag and products thereof thus and answers
With.
The technical scheme is that：The method for preparing high-purity iron powder using iron vitriol slag, it includes the following steps：（1）, make
Ball：Green-ball is obtained by iron vitriol slag and additive mixing, then through pelletizing；The additive includes the component of following parts by weight：It is rotten
Sodium phytate 5% ~ 10%；Lime stone 25% ~ 40%；Dolomite 10% ~ 20%；Coal dust 30% ~ 45%；（2）, one-step method melting and reducing：It will step
Suddenly green-ball made from (1) is dried at 200 DEG C ~ 400 DEG C, and coke is added at 1500 DEG C ~ 1600 DEG C for the hot-bulb obtained after dry
Charcoal carries out melting and reducing, obtains molten iron；（3）, electrolysis：The molten iron that step (2) obtains is cast as anode plate, while with stainless steel
Plate is cathode, is electrolysed in electrolytic cell, and high-purity iron powder is collected on cathode plate.
Step described in said program（1）Middle additive amount is the 10% ~ 15% of iron vitriol slag, green-ball pelletizing moisture 8% ~
10%, Balling time 10min ~ 15min.
Step described in said program（2）In drying carried out in rotary kiln, drying time be 6min ~ 10min.
Step described in said program（2）The granularity of coke is 10mm ~ 25mm；The quality proportioning of coke and hot-bulb be 5% ~
15%；Melting temperature is 1450 DEG C ~ 1600 DEG C, the melting and reducing time is 40min ~ 80min.
Step described in said program（3）Middle molten iron is cast as anode plate, the preparation of the sand mold mould with sand mold mould
Technique is as follows：Clay, waterglass and fire clay are uniformly mixed into punching press in sandbox, stand 40min ~ 60min, deviates from anode plate
Then model uniformly brushes a coating on its surface, 4h ~ 6h is placed in oven and dried, until its moisture removes completely.
Step described in said program（3）It is mirror-finished after the molding of Anodic plate casting, the material of cathode plate is not
Become rusty steel plate, and size ratio anode plate is big by 10% ~ 15%, and thickness is smaller than anode plate by 18% ~ 22%, and place is polished before cathode plate electrolysis
Reason.
Step described in said program（3）In electrolytic process used in electrolyte be FeSO4-(NH4)2SO4Solution, electrolysis
Condition is：Fe in electrolyte2+A concentration of 40 g/L ~ 60g/L, (NH4)2SO4A concentration of 135 g/L ~ 145g/L, electrolyte
PH value 3.5 ~ 4.5,40 DEG C ~ 60 DEG C of temperature, 100 A/m of current density2~300A/m2With 20 ~ 60mm of pole span.
Step described in said program（3）In the high-purity iron powder that is precipitated in cathode, it is primary every 40 ~ 60min scrapings, and
Obtained iron powder is repeatedly washed with deionized water, and dries iron powder 2h with vacuum drying chamber.
High-purity iron powder obtained in aforementioned manners, grade 99.95%.
The application of high-purity iron powder, the high-purity iron powder is for producing soft-magnetic parts, electronic component and superalloy.
The beneficial effects of the invention are as follows 1, additives except having good nucleation, absorbs water, the effect of fixed water, strengthens pelletizing
Process is conducive to sequential reduction；2, using the lime stone in additive, the flux such as dolomite strengthen smelting reduction process slag making,
The mobile performance for improving slag is conducive to the rate of recovery for improving iron；3, " one-step method " smelting reduction process is utilized, technique is shortened
Flow improves the rate of recovery of iron, reduces fixed investment；4, using electrolysis pig iron technology, high-purity iron powder is obtained, both comprehensive profit
It with iron vitriol slag, while obtaining high added value and obtaining product, improve technique overall efficiency.
Description of the drawings
Fig. 1 is the Fe-H2O current potentials-PH figures of the present invention.
Specific implementation mode
The method for preparing high-purity iron powder using iron vitriol slag, it includes the following steps：（1）, pelletizing：By iron vitriol slag and additive
Mixing, then obtain green-ball through pelletizing；The additive includes the component of following parts by weight：Sodium humate 5% ~ 10%；Lime stone
25%~40%；Dolomite 10% ~ 20%；Coal dust 30% ~ 45%；（2）, one-step method melting and reducing：By green-ball made from step (1),
It is dried at 200 DEG C ~ 400 DEG C, coke is added at 1500 DEG C ~ 1600 DEG C and carries out melting and reducing for the hot-bulb obtained after dry, obtains
To molten iron；（3）, electrolysis：The molten iron that step (2) obtains is cast as anode plate, while using stainless steel plate as cathode, in electrolytic cell
It is inside electrolysed, high-purity iron powder is collected on cathode plate.
In the present invention, step（1）Sodium humate in additive can strengthen pelletizing, improve green ball strength；Dolomite and stone
The flux such as lime stone can improve the mobility of slag in smelting reduction process, reduce slag viscosity and melting temperature, improve returning for iron
Yield reduces reduction and melts and divide temperature, saves energy consumption；The interior reduction that can strengthen ferriferous oxide with briquet.Step（2）In, it is raw
Ball is dry at 200 ~ 400 DEG C.By drying, greatly reduces green-ball and enter melting and reducing stage explosion ratio, convenient for improving
Roast yield.In step (3), electrolytic process suitably supplements sulfuric acid, to keep electrolyte PH value for 3.5 ~ 4.5.
The grade of high-purity iron powder produced by the present invention is 99.95%, and the quality of electrolytic iron is significantly improved, and can be height
The material of added value provides good raw material.Soft-magnetic parts, electronic component, high-performance and highdensity part, aviation, universe and
The iron powder requirement grade that the fields such as the superalloy of atomic energy industry use is higher than 99.9%, high-purity produced by the present invention
Iron powder is sufficient for above application requirement.
To facilitate the understanding of the present invention, it more comprehensively, is meticulously retouched below in conjunction with preferred embodiment to inventing to do herein
It states, but protection scope of the present invention is not limited to following specific examples.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention's
Protection domain.
Following embodiment and comparative example, unless specified or limited otherwise, used iron vitriol slag are derived from certain zinc hydrometallurgy factory, chemistry
Composition is as follows：TFe 28.25%, SiO20.50%, CaO 0.19%, MgO 0.46%, Al2O30.90%, LOI 49.33%.Institute
The use of anode board size is 200mm × 300 × 10mm（Length × width x thickness）, used cathode board size be 220mm × 330 ×
8mm（Length × width x thickness）.
Particle of each component less than 0.074mm of following embodiment and comparative example, additive accounts for 85% left side of respective weight
It is right.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：The additive for being 10% with addition of mass ratio in iron vitriol slag（Mass ratio is sodium humate 10%, agstone
25%, dolomite dust 20%, coal dust 45%）, after mixing, then pelletizing is carried out in disc balling machine, be prepared into granularity be 8 ~
16mm, aqueous 8.5% green-ball.Shatter strength of green pellet is 5.1 times/0.5m, compression strength of green pel let 10.8N/, green pellet cracking temperature
450 DEG C of degree.Green-ball is in rotary kiln to obtain dry bulb after 400 DEG C of dry 7min；Dry bulb is in the granularity of 1500 DEG C, coke
10mm carries out melting and reducing between amount of coke 10%, molten timesharing under the conditions of 60 min.Gained molten iron iron content 92.12%, the rate of recovery of iron
Respectively 92.21%.
Rich gallium molten iron, using stainless steel plate as cathode, is electrolysed by being cast into anode plate in electrolytic cell.Electrolytic condition
For Fe in electrolyte2+A concentration of 40g/L, 135g/L (NH4)2SO4, electrolyte ph 3.5,40 DEG C of temperature, current density
100A/m2, pole span 20mm.Gained electrolytic iron powder Iron grade is 99.92%, is electrolysed iron recovery 90.21%.
Embodiment 2：The additive for being 15% with addition of mass ratio in iron vitriol slag（Mass ratio is sodium humate 5%, agstone
40%, dolomite dust 10%, coal dust 45%）, after mixing, then pelletizing is carried out in disc balling machine, be prepared into granularity be 8 ~
16mm, aqueous 8.5% green-ball.Shatter strength of green pellet is 5.5 times/0.5m, compression strength of green pel let 12.2N/, green pellet cracking temperature
500 DEG C of degree.Green-ball in rotary kiln with 300 DEG C of dry 8min after；Dry bulb is 15mm, coke amount in the granularity of 1450 DEG C, coke
5%, between molten timesharing melting and reducing is carried out under the conditions of 40 min.Gained molten iron iron content 92.68%, the rate of recovery of iron are respectively
93.05%。
Rich gallium molten iron, using stainless steel plate as cathode, is electrolysed by being cast into anode plate in electrolytic cell.Electrolytic condition
For Fe in electrolyte2+A concentration of 60g/L, 140g/L (NH4)2SO4, electrolyte ph 4.5, temperature 50 C, current density
200A/m2, pole span 40mm.Gained electrolytic iron powder Iron grade is 99.95%, is electrolysed iron recovery 91.48%.
Embodiment 3：The additive for being 15% with addition of mass ratio in iron vitriol slag（Mass ratio is sodium humate 10%, agstone
25%, dolomite dust 20%, coal dust 45%）, after mixing, then pelletizing is carried out in disc balling machine, be prepared into granularity be 8 ~
16mm, aqueous 8.0% green-ball.Shatter strength of green pellet is 5.3 times/0.5m, compression strength of green pel let 11.6N/, green pellet cracking temperature
520 DEG C of degree.Green-ball in rotary kiln with 200 DEG C of dry 10min after；Dry bulb is 20mm, coke amount in the granularity of 1550 DEG C, coke
10%, between molten timesharing melting and reducing is carried out under the conditions of 50 min.Gained molten iron iron content 93.54%, the rate of recovery of iron are respectively
94.25%。
Rich gallium molten iron, using stainless steel plate as cathode, is electrolysed by being cast into anode plate in electrolytic cell.Electrolytic condition
For Fe in electrolyte2+A concentration of 50g/L, 145g/L (NH4)2SO4, electrolyte ph 4.0, temperature 60 C, current density
250A/m2, pole span 60mm.Gained electrolytic iron powder Iron grade is 99.93%, is electrolysed iron recovery 90.58%.
Embodiment 4：The additive for being 15% with addition of mass ratio in iron vitriol slag（Mass ratio is sodium humate 10%, agstone
40%, dolomite dust 20%, coal dust 30%）, after mixing, then pelletizing is carried out in disc balling machine, be prepared into granularity be 8 ~
16mm, aqueous 10% green-ball.Shatter strength of green pellet is 6.2 times/0.5m, compression strength of green pel let 10.8N/, cracking temperature of green pel let
550℃.Green-ball in rotary kiln with 400 DEG C of dry 6min after；Dry bulb is 25mm, coke amount in the granularity of 1600 DEG C, coke
15%, between molten timesharing melting and reducing is carried out under the conditions of 80 min.Gained molten iron iron content 92.11%, the rate of recovery of iron are respectively
95.09%。
Rich gallium molten iron, using stainless steel plate as cathode, is electrolysed by being cast into anode plate in electrolytic cell.Electrolytic condition
For Fe in electrolyte2+A concentration of 50g/L, 140g/L (NH4)2SO4, electrolyte ph 4.0, temperature 60 C, current density
300A/m2, pole span 40mm.Gained electrolytic iron powder Iron grade is 99.91%, is electrolysed iron recovery 91.82%.
Comparative example 1：The additive for being 15% with addition of mass ratio in iron vitriol slag（Mass ratio is sodium humate 10%, agstone
35%, dolomite dust 15%, coal dust 40%）, after mixing, then pelletizing is carried out in disc balling machine, be prepared into granularity be 8 ~
16mm, aqueous 1.0% green-ball.Shatter strength of green pellet is 6.2 times/0.5m, compression strength of green pel let 10.8N/.Green-ball is turning round
In kiln with 400 DEG C of dry 7min after；Dry bulb melt also between 1600 DEG C, mixed carbon comtent 15%, molten timesharing under the conditions of 50 min
It is former.The rate of recovery of gained molten iron iron content 92.11%, iron is respectively 95.09%.
Rich gallium molten iron, using stainless steel plate as cathode, is electrolysed by being cast into anode plate in electrolytic cell.Electrolytic condition
For Fe in electrolyte2+A concentration of 50g/L, 140g/L (NH4)2SO4, electrolyte ph 5.0, temperature 60 C, current density
300A/m2, pole span 40mm.Gained electrolytic iron powder Iron grade is 99.21%, is electrolysed iron recovery 90.32%.
Comparative example 2：The additive for being 15% with addition of mass ratio in iron vitriol slag（Mass ratio is sodium humate 10%, agstone
35%, dolomite dust 15%, coal dust 40%）, after mixing, then pelletizing is carried out in disc balling machine, be prepared into granularity be 8 ~
16mm, aqueous 1.0% green-ball.Shatter strength of green pellet is 6.2 times/0.5m, compression strength of green pel let 10.8N/.Green-ball is turning round
In kiln with 400 DEG C of dry 7min after；Dry bulb melt also between 1600 DEG C, mixed carbon comtent 15%, molten timesharing under the conditions of 50 min
It is former.The rate of recovery of gained molten iron iron content 92.11%, iron is respectively 95.09%.
Rich gallium molten iron, using stainless steel plate as cathode, is electrolysed by being cast into anode plate in electrolytic cell.Electrolytic condition
For Fe in electrolyte2+A concentration of 50g/L, 140g/L (NH4)2SO4, electrolyte ph 6.0, temperature 60 C, current density
300A/m2, pole span 40mm.Gained electrolytic iron powder Iron grade is 98.34%, is electrolysed iron recovery 89.87%.
Comparative example 3：The additive for being 15% with addition of mass ratio in iron vitriol slag（Mass ratio is sodium humate 10%, agstone
35%, dolomite dust 15%, coal dust 40%）, after mixing, then pelletizing is carried out in disc balling machine, be prepared into granularity be 8 ~
16mm, aqueous 1.0% green-ball.Shatter strength of green pellet is 6.2 times/0.5m, compression strength of green pel let 10.8N/.Green-ball is turning round
In kiln with 400 DEG C of dry 7min after；Dry bulb melt also between 1600 DEG C, mixed carbon comtent 15%, molten timesharing under the conditions of 50 min
It is former.The rate of recovery of gained molten iron iron content 92.11%, iron is respectively 95.09%.
Rich gallium molten iron, using stainless steel plate as cathode, is electrolysed by being cast into anode plate in electrolytic cell.Electrolytic condition
For Fe in electrolyte2+A concentration of 50g/L, 140g/L (NH4)2SO4, electrolyte ph 3.0, temperature 60 C, current density
300A/m2, pole span 40mm.Gained electrolytic iron powder Iron grade is 97.56%, is electrolysed iron recovery 90.21%.
Preferred melting and reducing temperature in the present invention is 1500 DEG C ~ 1550 DEG C, and the amount of allocating of coke is 10% ~ 15%, is melted
It is 40min-60min to melt the recovery time, the iron content in molten iron can be made to be greater than or equal to 92%, iron recovery is more than 90%.
It is sand mold mould that molten iron, which is cast into the mold used in anode plate process, will 35%- by weight when making mold
The fire clay of 55% clay, the waterglass of 10%-20% and 45%-65% uniformly mixes, and punching press stands 40-60min in sandbox,
Deviate from anode Slab；Then it is small ready-made sand mold mould to be placed in oven and dried 4-6 in its surface one coating of uniform brush
When, until the removing completely of its moisture obtains sand mold mould.Sand mold mould manufacture craft is significant.Because back molten iron needs electricity
How solution succinctly effectively prepares then anode plate prepares inevitable when electrolysis, is that it is crucial.Therefore, this patent
A kind of sand mold mould production method is provided, ferrovanadium slag can be poured into directly in mold after " one-step method melting " is reduced into molten iron,
Wait for that then anode plate tentatively prepares completion for its cooling.The raw materials such as clay, waterglass and fire clay, cheap used in the technique, holds
It easily obtains, and technique only need to be thus at low cost by punching press, drying.Anode plate and cathode plate polishing purpose be in order to
It is that electrolytic process uniformly carries out, improves current efficiency, reduces power consumption.The size of cathode plate is bigger 10%-15% than anode plate, thickness
Small 18%-22% is short-circuit caused by the generation of cathode plate periphery dendrite in order to prevent, while improving current efficiency, accelerates sun
Pole is electrolysed.
Selecting FeSO4- (NH4) 2SO4 solution, its purpose is to obtain chemical composition qualification, adsorptivity as electrolyte
Can stablize, be not easy the electrolytic iron to get rusty in air, while sulfate compares chlorination salt system, the requirement for anticorrosion of electrolytic cell compared with
It is low.Electrolytic condition setting is particularly significant to electrolytic process.Such as current density is too low, tank voltage is relatively low, what low potential was precipitated
The purity for influencing electrolytic iron is precipitated in impurity element；And be electrolysed under high current density, tank voltage increases, and hydrogen evolution phenomenon occurs, cathode
The hydrogen being precipitated on plate keeps electrolyte muddy, causes electrolyte Anodic mud to float, be attached to cathode plate, keep electrolytic iron impure,
Lead to the reduction of electrolytic iron purity.Concentric influence of the pole span to electrolytic process, too short to be then easy short circuit, long then resistance is big, electric current
Efficiency reduces.Low Fe2+It is electrolysed under concentration condition, although being conducive to the dissolving of anode, cell reaction is slow, current efficiency
It is low；High Fe2+It is electrolysed under mass concentration, is conducive to generate fine and close cathode deposition, current density improves, and can prevent hydrogen ion from putting
Electricity；But Fe2+Mass concentration is excessively high, and electrolytic process fluctuation is larger, it is more difficult to it controls, and electrolyte viscosity increases, electric conductivity reduces,
Also inhibit the dissolving of anode.Therefore, the setting of the electrolytic condition of this patent is the more excellent data obtained on the basis of many experiments.
The electrolytic separation iron dust of the pig iron containing gallium is in the electrorefining of crude metal.Make anode with the slightly pig iron containing gallium, stainless steel plate makees cathode, contains
Free Fe2+Aqueous solution make electrolyte, when passing to direct current, iron enters electrolyte from anodic solution at ionic condition, in the moon
Pure electrolytic iron is precipitated in pole.Valuable metal impurity in anode containing the pig iron enters solution with similar in ferroelectricity electrode potential in company with dissolved ferric iron
And be precipitated in cathode, other insoluble metals enter the earth of positive pole, to realize the separation with iron.From fig. 1, it can be seen that control pH exists
Within the scope of 3.2-5.4, iron can be made to be in Fe2+Stability region, with Fe2+Form is dissolved in electrolyte.Show further through comparative example
It is best in 3.5-4.5 ranges, once pH is equal less than 3.5 or higher than 4.5 gained electrolytic iron powder Iron grades and electrolysis iron recovery
It is greatly reduced, expected high-purity iron powder cannot be obtained, therefore the restriction of electrolytic condition is one of the innovative point of the present invention, it is existing
Technology does not provide the introduction or enlightenment for combining above-mentioned electrolytic condition.
Electrolytic iron, due to carrying acidic electrolysis bath, easily aoxidizes after cathode plate scrapes, influences the purity of electrolytic iron.Often
It is primary every 40 ~ 60min scrapings, it is repeatedly cleaned with deionized water immediately after taking-up, dries 2h under vacuum drying chamber, avoid electricity
Solution iron surface is aoxidized.By the collaboration of step (1) ~ step (3) each step, it is being matched with electrolytic condition of the present invention,
The Iron grade of the electrolytic iron powder of acquisition may be up to 99.9%, and the comprehensive recovery of iron is more than 80%.Publication No. CN107267745A
Acquisition molten iron to undergo 3 steps, i.e., pre- thermally desulfurizing；In and Zn and metallized pellet are recycled in prereduction；Metallized pellet
It is molten to get Fe-Ga molten iron, it can gradually recycle Fe, In, Zn and Ga, but its long flow path, high energy consumption, site requirements of founding the factory
More, investment is relatively large.The iron powder grade that the present invention obtains is far above the Publication No. of background technology part reference
97.5% Iron grade of CN107267745A, therefore the quality of electrolytic iron is significantly improved, and can be that the material of high added value carries
For good raw material.The present invention improves value-added content of product, passes through " one-step method " melting and reducing to obtain high-purity electrolytic iron
Technology obtains molten iron, shortens technological process, saves energy consumption, reduces cost.
Claims (10)
1. the method for preparing high-purity iron powder using iron vitriol slag, it is characterized in that it includes the following steps：（1）, pelletizing：
Green-ball is obtained by iron vitriol slag and additive mixing, then through pelletizing；The additive includes the component of following parts by weight：It is rotten
Sodium phytate 5% ~ 10%；Lime stone 25% ~ 40%；Dolomite 10% ~ 20%；Coal dust 30% ~ 45%；（2）, one-step method melting and reducing：It will step
Suddenly green-ball made from (1) is dried at 200 DEG C ~ 400 DEG C, and coke is added at 1450 DEG C ~ 1600 DEG C for the hot-bulb obtained after dry
Charcoal carries out melting and reducing, obtains molten iron, and the melting and reducing time is 40min ~ 80min；（3）, electrolysis：The iron that step (2) is obtained
Water is cast as anode plate, while using stainless steel plate as cathode, being electrolysed in electrolytic cell, and high purity iron is collected on cathode plate
Powder.
2. the method for preparing high-purity iron powder with iron vitriol slag as described in claim 1, it is characterized in that the step（1）Middle additive
Dosage is the 10% ~ 15% of iron vitriol slag, causes granularity for the green-ball of 8mm ~ 16mm through disc balling machine, green-ball pelletizing moisture 8% ~
The drop strength of 10%, Balling time 10min ~ 15min, green-ball are more than 4 times/0.5m, and compression strength is more than 10N/, and green-ball is quick-fried
Split 450 DEG C ~ 550 DEG C of temperature.
3. the method for preparing high-purity iron powder with iron vitriol slag as described in claim 1, it is characterized in that the step（2）In drying
It is carried out in rotary kiln, drying time is 6min ~ 10min.
4. the method for preparing high-purity iron powder with iron vitriol slag as described in claim 1, it is characterized in that the step（2）The grain of coke
Degree is 10mm ~ 25mm；The quality proportioning of coke and hot-bulb is 5% ~ 15%；Melting temperature be 1500 DEG C ~ 1550 DEG C, melting and reducing when
Between be 40min ~ 60min.
5. the method for preparing high-purity iron powder with iron vitriol slag as described in claim 1, it is characterized in that the step（3）Middle molten iron is used
Sand mold mould is cast as anode plate, and the preparation process of the sand mold mould is as follows：By the clay of 35%-55% by weight,
The waterglass of 10%-20% and the fire clay of 45%-65% uniformly mix punching press in sandbox, stand 40min ~ 60min, deviate from anode
Then Slab uniformly brushes a coating on its surface, 4h ~ 6h is placed in oven and dried, until its moisture removes completely.
6. the method for preparing high-purity iron powder with iron vitriol slag as described in claim 1, it is characterized in that the step（3）Middle-jiao yang, function of the spleen and stomach pole plate
It is mirror-finished after cast molding, the material of cathode plate is stainless steel plate, and size ratio anode plate is big by 10% ~ 15%, thickness ratio
Anode plate is small by 18% ~ 22%, is processed by shot blasting before cathode plate electrolysis.
7. the method for preparing high-purity iron powder with iron vitriol slag as described in claim 1, it is characterized in that the step（3）In electrolysis
Electrolyte used in process is FeSO4-(NH4)2SO4Solution, electrolytic condition are：Fe in electrolyte2+A concentration of 40 g/L ~ 60g/
L, (NH4)2SO4A concentration of 135 g/L ~ 145g/L, electrolyte ph 3.5 ~ 4.5,40 DEG C ~ 60 DEG C of temperature, current density 100
A/m2~300A/m2With 20 ~ 60mm of pole span.
8. the method for preparing high-purity iron powder with iron vitriol slag as described in claim 1, it is characterized in that the step（3）In in cathode
The high-purity iron powder of precipitation, it is primary every 40 ~ 60min scrapings, it is used in combination deionized water repeatedly to wash obtained iron powder, and with very
Empty drying box drying iron powder 2h.
9. as described in claim 1-10 is any prepare the method for high-purity iron powder with iron vitriol slag made from high-purity iron powder, feature
The grade for being the high-purity iron powder is 99.95%.
10. as claimed in claim 9 with iron vitriol slag prepare the method for high-purity iron powder made from high-purity iron powder application, feature
It is that the high-purity iron powder is used to produce soft-magnetic parts, electronic component and superalloy.
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| CN110965079A (en) * | 2019-09-10 | 2020-04-07 | 曾纪斌 | Method for efficiently and comprehensively recycling iron-rich metallurgical tailings |
| CN111809058A (en) * | 2019-04-10 | 2020-10-23 | 中国瑞林工程技术股份有限公司 | Method for one-step volatilization reduction treatment of smelting tailings |
| CN113755899A (en) * | 2021-08-06 | 2021-12-07 | 莫永明 | Sectional type electrolytic cell for recycling steel slag |
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