CN107254585A - It is a kind of that zinc, indium, iron, the method for gallium are reclaimed from iron vitriol slag - Google Patents

It is a kind of that zinc, indium, iron, the method for gallium are reclaimed from iron vitriol slag Download PDF

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Publication number
CN107254585A
CN107254585A CN201710366491.5A CN201710366491A CN107254585A CN 107254585 A CN107254585 A CN 107254585A CN 201710366491 A CN201710366491 A CN 201710366491A CN 107254585 A CN107254585 A CN 107254585A
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iron
gallium
zinc
indium
pelletizing
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CN107254585B (en
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朱德庆
潘建
李启厚
李紫云
梁钟仁
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Central South University
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Central South University
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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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • 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
    • 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
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/244—Binding; Briquetting ; Granulating with binders organic
    • 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
    • C22B1/248—Binding; Briquetting ; Granulating of metal scrap or alloys
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • 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
    • C22B58/00—Obtaining gallium or indium
    • 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
    • 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
    • Y02P10/20—Recycling

Abstract

The invention discloses a kind of method that zinc, indium, iron, gallium are reclaimed from iron vitriol slag, specifically include additive and mixed with iron vitriol slag, moisten mill, pelletizing, oxidizing roasting desulfurization, direct-reduction, molten step of grading.Special additive of the present invention is used in balling process, described additive includes organic binder bond, alkaline earth metal source, alkali metal source, carbonaceous fuel and ferriferous oxide.In the present invention, pass through numerous studies and experiment certification, pass through the use of described additive, it can strengthen and improve pellet roasting desulfurization and consolidation effect, improve agglomerates intensity, improve agglomerates reproducibility, reduction Swelling of Pellets During Reduction rate is efficiently separated and provide high-quality furnace charge to realize the pyrogenic process of a variety of valuable elements such as iron, gallium, zinc, indium, sulphur.

Description

It is a kind of that zinc, indium, iron, the method for gallium are reclaimed from iron vitriol slag
Technical field
The invention belongs to metallurgical technology field, and in particular to one kind is to make high efficiente callback zinc, indium, iron, gallium, sulphur in iron vitriol slag Deng the method for valuable element.
Background technology
Iron vitriol slag is that wet method is carried during zinc as the discarded object produced except iron, iron content 25%~30%, sulphur 8~12%, Zinc 3%~5%, the element such as silver-colored 50-100g/t and micro dissipated metal gallium, indium, germanium, with very high value.By Contain heavy metal in it, aqueous 30-50% is more unstable, is difficult to store up, the dangerous solid waste of category, it is therefore necessary to enter to it Row processing.
Pyrogenic process extraction process is a kind of promising high efficient technology, valuable element extract it is wide in variety, extraction efficiency is high, useless Water is few, secondary slag can realize innoxious and recycling.
Reduction roasting-molten point is the effective means of separation and Extraction zinc, indium and iron, gallium.Metal is reduced to using zinc, indium and is had The characteristics of having good volatile performance, zinc, indium reduction volatilization are enriched with and reclaimed in flue dust, are separated and are extracted as follow-up zinc indium Quality raw materials.Iron and gallium are reduced, and during molten point, iron is fused into molten iron, is separated with gangue.Because gallium has strongly Affinity for iron, gallium is effectively enriched with molten iron.Rich gallium molten iron is the quality raw materials for reclaiming separation iron and gallium.
But, because iron vitriol slag granularity is too thin, it is necessary to previously prepared to be used into pelletizing；But, its water content is high, especially It is that chemical combination water content is high, and loss on ignition is big, and green-ball heat endurance is poor.Iron vitriol slag sulfur-bearing is up to 12% or so, Direct Reduction It is middle to have a strong impact on the reduction volatilization of zinc and indium, so as to influence the separation of iron, gallium and zinc, indium, and cause serious secondary dirt Dye.In addition, the gangue in iron vitriol slag belongs to acid mineral, silicon, aluminium oxide content are high, and its iron vitriol slag pelletizing reproducibility is low, go back Former dilatancy is too high, and during pelletizing reduction roasting-molten point, zinc, indium reduction volatilization rate are low, in molten point of process of reducting pellet In, the poor fluidity of slag, desulphurizing ability is low, will cause Sulfur Content in Hot Iron content overproof, has a strong impact on follow-up iron gallium and separates and go back Former iron powder product quality.Therefore, reinforcing pellet roasting desulfurization and agglomerates direct-reduction are calcined zinc, indium during-molten point Reduction volatilization, promotes the slag sluicing system during molten point, it is ensured that the impurity that gallium at utmost enters in molten iron, control molten iron contains Amount, has decisive role to efficiently separating extraction iron, gallium, zinc, indium.
The method of comprehensive utilization of some iron vitriol slags, such as Chinese patent literature (Publication No. are also disclosed that in the prior art CN103710538A a kind of preparation method of zinc smelting dreg composite briquettes) is disclosed, by lead smelting gas, iron vitriol slag and blast furnace slag point Not Po Sui ball milling and portland cement make binding agent, mixed-forming carries out briquetting output moist mass under the conditions of 20~80Mpa, Output agglomerate is dried at a temperature of 30 DEG C~180 DEG C.But aqueous higher, silicate after the drying of portland cement binding agent agglomerate Cement bonding agent heat endurance is poor, easily rupturable in subsequent smelting, influences efficiency, and due to the introducing of silicon, increases and smelt The quantity of slag, causes the rise of energy consumption level cost.
Publication No. CN104911356A Chinese patent literature discloses a kind of solid waste gas ash, vanadium slag containing zinc-iron and integrated Recovery process, specifically discloses a kind of additive, is 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 well mixed, by compound and coke powder, raw stone Ash carries out stockpile burdening in 1: 0.18: 0.03 ratio with claw bucket sling, it is difficult to mix；Compound is delivered to disk pelletizing machine system Grain, control discharging-material size be 6~12mm, moisture be 18~25%, and by the material after granulation store up naturally drying 16~ 32h；Binding agent is done with lime and calcium hydroxide, grain low intensity is expected, it is broken in storing up and transporting, cause ring formation of rotary kiln.Green-ball Moisture is up to 25%, and compression strength is poor, is easily bonded and broken in storing up.Flue gas desulfurization by-product gypsum, it is difficult to further utilize.Also Original product is through three sections of gradient magnetic separations and three-level ore grinding, then output reduced iron powder and Iron concentrate after the classification of high-efficiency helical grader, Long flow path, investment is big, and ore grinding cost is high, the valuable element less varieties of recovery.
Publication No. CN106244817A Chinese patent literature discloses a kind of recycling pretreatment zinc abstraction low stain The technique of jarosite process iron vitriol slag, ball processed, Ran Houjin again are mixed by low stain jarosite process iron vitriol slag, bonding agent and broken coal Enter calcining kiln and be sintered at 1200~1400 DEG C to be restored to clinker sulfur-bearing below 2%, described bonding agent is calcium lime powder. The granularity of broken coal and binding agent is respectively less than 3mm, using calcium lime powder as binding agent, is pelletized on disk pelletizing machine, and raw material granularity is thick And binding agent viscosity is low, gained pellet strength is poor；Zinc reduction volatilization only 70% in iron vitriol slag；In addition, the low concentration cigarette produced Gas need to return to existing acid making system and carry out distribution relieving haperacidity, could recycle sulphur.
Publication No. CN106319209A Chinese patent literature discloses a kind of rotary hearth furnace processing lead cadmia iron-extracting process, A kind of pelletizing additives are specifically disclosed, are bentonite and liquid-containing binder.Water content in the liquid-containing binder for 90%~ 98%, its main component is one or more of mixtures in amidin, glue, syrup, pitch etc..By briquetting- Drying-direct-reduction-ore grinding-magnetic separation, obtains in reduced iron powder, iron powder metal Ferrum content up to 80%.Due to being glued using liquid Agent is tied, is added and using difficulty, and requires that raw material is dried compared with low moisture；In addition, the iron that the technique is recycled, Without considering to reclaim other valuable elements.Desulfurization is not accounted for yet, and iron powder Iron grade is relatively low, harmful element sulfur content It is high.
Publication No. CN106011489A Chinese patent literature discloses a kind of method for handling iron vitriol slag, by iron vitriol slag Mixed with reducing agent, obtain mixed material；Mixed material is subjected to resolution process and reducing zone in reduction furnace resolver Middle carry out reduction treatment, obtains the solid product containing lead, the gaseous products of zinc and silver and 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 iron although in recyclable iron vitriol slag, Lead, zinc and silver, but do not account for reclaiming gallium, indium, sulphur.
Publication No. CN104532013A Chinese patent literature discloses recovery method silver-colored in a kind of iron vitriol slag, by iron Alum slag is that 74 μm of -3mm coal dusts, desulfurizing agent lime are mixed with granularity, and batch mixing is carried out using grinder, extruder or cylindrical mixer And pressure ball, mixing spheroid (diameter is less than 100mm) is obtained, then mixing spheroid is fitted into vacuum distillation furnace in 1100-1300 DEG C heating is to isolate the silver in iron vitriol slag.But, do not recycle other valuable elements, such as iron, gallium, indium.
In summary, it has been disclosed that the thermal process patented technology that utilizes of relevant ferrovanadium slag or patent application in, be by Ferrovanadium slag is pelletized or briquetting with addition of the compound of other metallurgical slags and reducing agent or desulfurizing agent, and binding agent used is made a living stone Ash, calcium hydroxide, cement, bentonite, amidin, glue, syrup, pitch etc., do not account for the scattered of binding agent and mix The Blending Efficiency of Blending of material, and be that green briquette is directly entered high temperature smelting furnace and reduced mostly, without advance high-temperature roasting desulfurization and Process is consolidated, a large amount of powder are also easy to produce, causes to tie kiln.Raw material is directly entered reduction furnace and reduced, and desulfurized effect is poor in reduction process, Cause Zinc volatilization rate low, and inevitably lead to sulfur content severe overweight in reduced iron powder, do not reach high-quality reduced iron powder Technical requirements, and be unable to effective recycling sulphur；Reduzate obtains reduced iron powder, reduced iron by ore grinding-magnetic separation The quality of powder it is difficult to ensure that, because in ore grinding-magnetic separation iron-extracting process, metallic iron is easily reoxidized, and investment is big, long flow path, Cost is high；All techniques are recycled just for valuable element within one kind in iron vitriol slag or 2-3 kinds, comprehensively utilize journey Degree is low, and the particularly recycling to rare and scatter element indium, gallium is seldom related to.To sulfur-bearing cigarette in only two disclosed technical schemes Gas carries out desulfurization process, and one is to use lime-gypsum method, but accessory substance gypsum is difficult by；One is by low concentration SO2Flue gas is returned Return neighbouring acid plant's extracting sulfuric acid, the flexibility of technique and bad adaptability.
Therefore, the present invention in view of the above-mentioned problems, developing pelletizing-pellet roasting desulfurization, melt by-agglomerates direct-reduction- Point-electrolysis process of the pig iron containing gallium, and strengthen pellet roasting desulfurization especially by multifunction additive and consolidate, the sulphur in removing pelletizing And pellet strength is improved, above-mentioned technical barrier is not only solved, and realize the separation of iron, zinc, sulphur, gallium, indium simultaneously with carrying Take.
The content of the invention
To overcome the technical problem that prior art is present, reclaimed the invention provides one kind from iron vitriol slag zinc, indium, iron, The method of gallium, it is intended to the green-ball of high performance iron vitriol slag is prepared by additive provided by the present invention, especially by many Sulphur and raising pellet strength in functional additive reinforcing pellet roasting desulfurization consolidation, removing pelletizing, and then realize in iron vitriol slag Zinc, indium, the high efficiente callback of iron gallium.
Iron vitriol slag granularity is too thin, and -320 mesh reach more than 80%, and sulfur-bearing is too high, it is impossible to directly carry out desulfurization with roasting technique, sulphur master To exist with sulphate form, pellet roasting desulfurization is difficult, desulfurization temperature is high, the time is long, need to strengthen pellet roasting desulfurization；And siderotil Gangue in slag belongs to acid mineral, and silica, alundum (Al2O3) oxide content are high, and its pelletizing reproducibility is low, it is swollen to reduce Swollen property is too high, and during pelletizing reduction roasting-molten point, zinc, indium reduction volatilization rate are low, during molten point of reducting pellet, slag Poor fluidity, desulphurizing ability is low, will cause Sulfur Content in Hot Iron content overproof, has a strong impact on follow-up iron gallium separation problem.In view of A series of problems encountered in iron vitriol slag valuable resource removal process, the present inventor had found by numerous studies, by by iron The unique multifunction additive of the alum slag addition present invention is previously prepared to consolidate green-ball desulfurization with roasting technique into high-quality green-ball, takes off Except being reduced again after the sulphur in pelletizing and raising pellet strength, melting the reclaimer operation that grades, it can help to lift valuable element The rate of recovery, improves the quality of the metal reclaimed.
Technical solution of the present invention is：
It is a kind of that zinc, indium, the method for iron gallium are reclaimed from iron vitriol slag, comprise the following steps：
Step (1)：Pelletizing：
Iron vitriol slag and additive are mixed, profit mill, pelletizing obtain green-ball；
Described additive includes the component of following parts by weight：
Step (2)：Desulfurization：
By the oxidizing roasting at 1150~1300 DEG C after green-ball drying, preheating made from step (1), desulfurization pelletizing, oxygen are obtained Changing the flue gas of roasting is used to reclaim sulphur；
Step (3)：Direct-reduction：
Desulfurization pelletizing made from step (2) is incorporated reducing agent, the direct reduction reactor at 1100~1250 DEG C；Reduction is anti- The furnace charge answered obtains metallized pellet through cooling, magnetic separation；Reduction reaction flue gas dust collection is used to extract zinc, indium；
Step (4)：Molten point：
The metallized pellet that step (3) is obtained melts, slag-liquid separation obtains rich gallium molten iron.
In the present invention, by numerous studies and experiment certification, by the use of described additive, pelletizing can be strengthened, changed Kind pellet roasting desulfurization and consolidation effect, improve agglomerates intensity, improve agglomerates reproducibility, reduce Swelling of Pellets During Reduction Rate, improves the mobility of slag, improves the desulphurizing ability of slag, coordinates described subsequent technique, zinc, indium, sulphur, iron gallium etc. can be achieved many Plant efficiently separating and extracting for valuable element.
Key to the invention is that described additive and the pelletizing of described original creation, oxidizing roasting desulfurization, reduction-molten Division technique recovery train.
By the additive of described unique ingredient and parts by weight, moisture needed for can making iron vitriol slag pelletizing is reduced, and improvement is made Ball performance, improves green ball strength and heat endurance, pelletizing is carried out reinforcing desulfuration in the roasting of weak oxide atmosphere, also contributes to ball Group's intensity, reducing property, reduce Swelling of Pellets During Reduction rate, improve the mobility and desulphurizing ability of the slag of the molten timesharing of pelletizing, so that Improve the slag making performance of pelletizing.In addition, coordinated, can be further strong in present invention direct-reduction-molten technological parameter that grades again Change iron vitriol slag agglomerates and reduce-melt division technique progress zinc, indium reduction volatilization and the separation with iron, gallium, improve zinc, indium, iron, gallium The rate of recovery, improves zinc, indium and iron, the separating effect of gallium, is that high efficiente callback creates good using iron, gallium, zinc, indium, sulphur valuable element Good condition.
In the present invention, iron vitriol slag is previously dried dewater treatment, is easy to control and stablize pelletizing.
Preferably, in step (1), the water content for controlling described iron vitriol slag is 7~9wt%.
The present inventor's research finds that iron vitriol slag moisture is less than 7% after drying, and energy consumption needed on the one hand drying is higher, dries Time is long, and needs in follow-up balling process to add more water and can just make good shot, causes energy consumption further to increase, Er Qieshui Divide too low, workshop Dust Capacity is increased in transhipment and pelletizing, influence environment.But moisture is higher than 9%, easily causes and ground in batch mixing and profit Middle sizing, produces blocking, and influence flow is unimpeded.
In the present invention, the use of described additive can effectively lift the intensity of obtained green-ball, the follow-up roasting of improvement and take off The separation and recovery effect of sulphur, reduction and molten step of grading.
Preferably, described organic binder bond is at least one in sodium humate, polyacrylamide, carboxymethyl cellulose Kind.Three is organic polymer binding agent, available for iron vitriol slag pelletizing, improves greenball properties.But above-mentioned organic binder bond In, sodium humate best results.
Further preferably, described organic binder bond is sodium humate.Sodium humate is primarily due to belong to containing aromatic hydrocarbon Macromolecule organic, heat endurance is strong, more conducively lifts cracking temperature of green pel let.
Preferably, in described additive, described organic binder bond is sodium humate, and the parts by weight of sodium humate are excellent Elect 5~10 parts as.
Described alkaline earth metal source is the oxide of alkaline-earth metal, and/or can change into the alkaline earth oxide Salt.
Preferably, described alkaline earth metal source includes calcium source and/or magnesium source；Described calcium source be calcium oxide and/or The salt of calcium oxide can be changed into；Described magnesium source is magnesium oxide and/or can change into the salt of magnesium oxide.
Further preferably, described alkaline earth metal source includes calcium source and magnesium source, and wherein calcium source and the weight in magnesium source ratio is 15 ~40: 10-25.Calcium source and magnesium source compounding use of the weight than under, help further to improve the performance of obtained green-ball.
The described salt for changing into calcium oxide is preferably the carbonate of calcium.
The described salt for changing into magnesium oxide is preferably the carbonate of magnesium.
Most preferably, described alkaline earth metal source is calcium carbonate and magnesium carbonate；Or main component is calcium carbonate and/or carbonic acid The ore of magnesium, for example, lime stone, dolomite.
In described alkaline earth metal source, the parts by weight of lime stone are 15~40 parts；The parts by weight of dolomite are 10-25 parts.
Further preferably, in described additive, in described alkaline earth metal source, the parts by weight of lime stone are 15~40 Part；The parts by weight of dolomite are 15-25 parts.
Preferably, in described additive, the parts by weight of described alkaline earth metal source are preferably 40~55 parts；That is, The parts by weight sum of preferred lime stone and dolomite be 40~55 parts.
Described alkali metal source is the oxide of alkali metal, and/or can change into the salt of the oxide of alkali metal.
The salt of the described oxide for changing into alkali metal is preferably the carbonate of alkali metal.
Preferably, the oxide of described alkali metal is sodium oxide molybdena and/or potassium oxide.
The carbonate of described alkali metal source is sodium carbonate and/or potassium carbonate.
Further preferably, described alkali metal source is sodium carbonate.
In the present invention, described carbonaceous fuel is at least one of semi-coke powder, coke powder, anthracite.
Preferably, in described additive, the parts by weight of described carbonaceous fuel are 15~30 parts；Further preferably For 25~30 parts.
In described additive, particle of each component less than 0.074mm accounts for the 70-85% of respective weight.
In the present invention, described additive includes the component of following preferred weight part：
Above-mentioned preferred each component and its ratio can further improve the performance of green-ball, the desulfurization of lifting pellet roasting, roasting Pelletizing is reduced and zinc, indium volatilize, reducting pellet melts separation of timesharing iron, gallium and slag and other effects.
Sodium humate, sodium carbonate, lime stone, dolomite and carbonaceous fuel and its mutual synergy are to greenball properties With significantly affecting.Sodium humate is the netted organic polymer containing carboxyl and oh group, in siderotil dregs mixing material Iron mineral, calcic, magnesium mineral (lime stone, dolomite) surface produce chemisorbed, will be fine grain by netted bridge linking effect Miberal powder is bonded together, and plays cementation.And sodium carbonate is water-soluble sodium salt, in alkalescence, it can change each in siderotil dregs mixing material The surface potential of kind of mineral, strengthens the activity of sodium humate, can be produced between synergy reinforcing mineral grain with sodium humate Bond.In addition, carbonaceous fuel surface has hydrophobicity, and it is dispersed in iron vitriol slag, can be with the hydrocarbon chain in sodium humate molecule Van der Waals force is produced, strengthens netted bridge linking effect.Therefore, it can carry when being incorporated appropriate sodium humate and sodium carbonate in additive High green ball strength, and lime stone, dolomite, brown iron oxide and carbonaceous fuel can then play the strengthening action of auxiliary.Meanwhile, corruption is planted Sour sodium and carbonaceous fuel and lime stone, dolomite, brown iron oxide and sodium carbonate, also will be strong while collaboration improves greenball properties Change follow-up pellet roasting desulfurization, reduction and melt and divide.Lime stone and dolomite are added, the basicity of pelletizing can be not only adjusted, and And the content of magnesia in pelletizing can be adjusted, so as to improve pelletizing reproducibility, reduce low temperature reduction degradation during pelletizing reduction Rate, improves the mobility and desulphurizing ability of molten timesharing slag, improves molten steel quality, improve the rate of recovery of iron and gallium.Therefore, adjustment adds Plus the amount of allocating of each component ratio and additive in iron vitriol slag in agent, by the physical chemistry in influence green-ball, agglomerates Environment, pelletizing be microcosmic and macrostructure, includes mineral composition, pore size and the distribution of pores of pelletizing, so that it is strong to change pelletizing Degree, heat endurance, reproducibility, reduction swellability rate；Influence reducting pellet to melt the chemical analysis of timesharing slag, cause viscosity coefficient of dross, The change of surface tension and mobility, is that the separation of molten iron and slag creates good conditions, improves the rate of recovery of iron and gallium, improve Molten steel quality, improves iron and gallium grade, reduces molten iron impurity content.Each component ratio and additive are in iron vitriol slag in additive Amount of allocating is determined according to substantial amounts of research, to meet system peak optimization reaction dynamic conditions in technique, obtains best-of-breed technology Economic indicator.
Further preferably, described additive includes the component of following preferred mass percentage：
The mass ratio of lime stone and dolomite is 15~40: 10-25；
Each component sum is 100%.
Most preferably, described additive includes the component of following preferred mass percentage：
The mass ratio of lime stone and dolomite is 25~40: 15；
Each component sum is 100%.
In the present invention, described addition of the additive relative to iron vitriol slag has one to be fixed the performance of obtained green-ball Ring.Preferably, in step (1), additive adds 2~7wt% that weight is iron vitriol slag.
The present inventor has found that additive can further improve falling for green-ball under described addition by many experiments Lower intensity, compression strength and burst temperature.For example, when addition is less than 2%, drop strength, compression strength and the explosion of green-ball Temperature declines, when addition is higher than 7%, although the drop strength and compression strength of green-ball have been raised, but pelletizing operation is not Stable, cracking temperature of green pel let declines.
In step (1), under preferred iron vitriol slag water content, preferred additive add that weight is iron vitriol slag 5~ 7wt%.
In the present invention, the iron vitriol slag and additive of the proportioning are preferably fully mixed in intensive mixer, then in profit High force dispersion in grinding machine, then carries out pelletizing in disc balling machine again, and green-ball is made.
Suitable speed of agitator, mixing time, profit mill moisture, profit time consuming have certain influence on greenball properties.
It is preferred that speed of agitator be 1200-1800rpm, mixing time 60-90 seconds.Speed of agitator is fast, mixing time is long, mixes Even effect is good, and various additives are uniformly dispersed in iron vitriol slag, gives full play to the various effects of additive, is conducive to follow-up make Ball, pellet roasting, pelletizing reduction and molten point.But, speed of agitator is partially slow, and Blending Efficiency of Blending is poor, and speed of agitator is too fast, stirring vane Quick abrasion, accessory loss is big, and cost is high；Mixing time is short, and Blending Efficiency of Blending is poor, and mixing time is long, and mixer yield declines.Add Plus agent disperses uneven, quality of green pellets is unstable, so as to cause agglomerates quality, desulfurized effect, pelletizing reduction and molten point of effect Fruit is deteriorated.
It is preferred that profit mill moisture be 6-8%, profit time consuming 2-4min.Sticky strong, fine size this kind of to iron vitriol slag and addition The compound of organic polymer binding agent, except strength mixing makes material in addition to macroscopically fully dispersed, it is necessary to there is damp mill Coordinate and carry out the scattered of micro-scale, enhancing binding agent and other additive molecules are physico with iron vitriol slag mineral particle surface Act on, and improves green ball strength and its uniformity.
Currently preferred stirring mixing (strength is mixed) and profit mill synergy, in reduction consumption of binder and raising life Ball aspect of performance has remarkable result.But, when profit mill moisture is higher, compound is too viscous, and damp mill is easily blocked, and influence flow is steady Fixed operation.Profit mill moisture it is relatively low, between organic binder bond, sodium carbonate interaction and its subtract with the chemical action of mineral surfaces It is weak, cause greenball properties to be deteriorated, and require that degree height is pre-dried in iron vitriol slag, dust concentration is increased in production procedure, increase Energy consumption and influence environment.Profit time consuming length, interaction between organic binder bond, sodium carbonate is with its chemistry with mineral surfaces Effect enhancing, greenball properties are obviously improved.But, profit time consuming is long, and material is excessively good by levigate effect, micro-size fraction particle Increase, shatter strength of green pellet is improved, but compression strength of green pel let and burst temperature be decreased obviously, and damp mill yield is also significantly Decline, power consumption increase, production cost rise.Profit time consuming is too short, interaction between organic binder bond, sodium carbonate and with Not enough, Binder Properties can not give full play of the chemistry time of mineral surfaces, and green ball strength declines, and burst temperature is slightly There is rise.
Preferably, in step (1), the granularity of described green-ball is 10~25mm, water content control in 9.5~12wt% Between.
Under the preferred granularity and water rate control, can further it solve because of iron vitriol slag crystal water content and sulfur content mistake High, fire loss volume up to 49%, be easily caused the problem of pelletizing produces a large amount of contractions in roasting；Described green-ball fineness ratio is conventional Iron ore pellets granularity is thick, to ensure that agglomerates granularity is close with conventional iron ore concentrate agglomerates.
The inventors discovered that, under the collaboration of each parameter of step (1), the drop strength of obtained green-ball be more than 5 times/ 0.5m, compression strength is more than 15N/, 450~680 DEG C of cracking temperature of green pel let；With good performance.
In step (2), by described green-ball by continuous dry, preheating, baking and concretion process, desulfurization, raising pelletizing Intensity and improvement pelletizing metallurgical performance, are that follow-up pelletizing is reduced and molten point creates good conditions.
Preferably, green-ball is laid on belt type roasting machine, it is dried, preheats, oxidizing roasting.
Preferably, the bed depth 70-110mm of green-ball.
In the industrial production, step (2) is carried out preferably on belt type roasting machine, and the control of green-ball bed depth is in 70- 110mm is advisable.Because the iron vitriol slag crystallization water and sulfur content are higher, loss on ignition is big, and pelletizing is received in drying, preheating and roasting process Contracting amount and Strength Changes are big, suitable for the bed of geo-stationary, and sulphur mainly exists with sulphate form, sintering temperature height, because This selects belt type roasting machine；For example, green-ball exhausting at 250~450 DEG C on belt type roasting machine is dried 3~6min, then risen 5~10min is preheated at warm to 650~1100 DEG C, 20~80min of oxidizing roasting at 1150~1300 DEG C is warming up to afterwards again；Obtain The agglomerates of desulfurization；Recovery sulphur is carried out to the flue gas in step (2) processing procedure.The green-ball bed of material is too thin, during less than 70mm, raw Ball rate of drying is too fast, and the pelletizing ratio that top layer is cracked is high；The green-ball bed of material be higher than 110mm when, bed of material middle and lower part pelletizing because Overly moist is easily produced for water vapour condensation, causes cracking temperature of green pel let to decline and pelletizing cracking, two kinds of situations cause to be calcined ball Group's intensity declines, and powder is also easy to produce during sequential reduction, influences reduction process direct motion.
Further preferably, in step (2), green-ball bed depth is controlled in 80-110mm.
Preferably, in step (2), green-ball is dried at 250~450 DEG C.By drying, green-ball moisture is reduced to 2% Hereinafter, its burst temperature significantly rises, and greatly reduces green-ball and enters after preheating section the ratio for producing fragmentation, is easy to improve roasting Burn pellet strength and yield.If drying temperature is less than 250 DEG C, drying time will extend, and burning machine yield declines.If drying temperature Degree is higher than 450 DEG C, approaches and more than the burst temperature of green-ball, then in the drying process, green-ball largely produces rupture, agglomerates Yield and intensity significantly decline.Therefore, the drying of green-ball is suitable rate of drying under the conditions of Drying Dynamics and suitable Seek balance between agglomerates intensity.
Preferably, in step (2), dry temperature is preferably 250~350 DEG C.
Further preferably, in step (2), 3~6min is dried at described temperature.
Preferably, in step (2), green-ball is warming up at 650~1100 DEG C and preheated again after drying；More preferably exist Preheated at 850~1100 DEG C；Preheated most preferably at 1050~1100 DEG C.
In warm, the crystallization water, sulfide, carbonate and the yellow potassium iron in series of chemical, green-ball are produced Alum produces decomposition, and the carbonaceous fuel that additive is brought into starts burning, and ferriferous oxide produces crystallite connection, and suitable programming rate can Improve preheated pellets intensity.If preheating temperature is less than 650 DEG C, preheating and roasting time will extend, and burning machine yield declines.If Preheating temperature is higher than 1100 DEG C, shows that the rise of roasting process temperature is too fast, the crystallization water, sulfide, carbonate produce decomposition rate Pelletizing internal stress is caused very much to increase soon, final agglomerates intensity declines.
In step (2), 5~10min is preheated under described preheating temperature.
Preheat at preferred 850~1100 DEG C, preheating time preferably is 5~9min.
In step (2), the green-ball after the pre-heat treatment is warming up to 1150-1300 DEG C described of oxidizing roasting temperature again, carries out Oxidizing roasting, for the sulphur in deep removal green-ball, and further makes the ferriferous oxide progress solid-state diffusion in pelletizing tie again Brilliant and crystal grain is fully grown up, and solid phase consolidation is produced, in addition, CaO, MgO, SiO that iron vitriol slag and additive are brought into2、Al2O3Between Chemical reaction is mutually produced, a certain amount of slag phase is formed.Solid phase is consolidated and slag bonding collective effect shows agglomerates intensity It is bright to improve.Simultaneously because the synergy between additive, including carbonaceous fuel burning and carbonate decomposition release CO2, improve The dynamic conditions of sulphate decomposition, desulfurization degree is improved, and residual sulfur content declines in pelletizing.
Further preferably, the temperature of oxidizing roasting temperature is 1200-1300 DEG C.
Preferably, the time of oxidizing roasting is 20~80min.Pelletizing is leaned on based on solid diffusion bonding reaction, diffusion Speed is slowly, it is necessary to enough consolidation times.Roasting time is less than 20min, and consolidation time not enough, causes pellet strength low, is calcined When time is higher than 80min, roasting time is longer, and yield is lower, and energy consumption is higher.And roasting time it is long when pelletizing excessively cause It is close, the decline of pelletizing reproducibility is also resulted in, is had a negative impact to sequential reduction.
At a temperature of the preferred oxidizing roasting, the time of oxidizing roasting is more preferably 20~60min；Most preferably 20~40min.
The oxidizing roasting process of step (2) is carried out preferably under air atmosphere.
In step (2), the flue gas of desulfurization with roasting technique is gathered dust and desulfurization.The dust of removing returns to iron vitriol slag back tender Sequence.The SO that flue gas after dedusting is sprayed into the absorbing liquid absorption flue gas containing ammoniacal liquor2, it is passed through air oxidation SO2, generate ammonium sulfate.
Preferably, absorbing liquid containing ammonia (L) and flue gas (m3) volume ratio be 70~120L/m3；One in the absorbing liquid containing ammonia The concentration for being hydrated ammonia is 10~18g/L.By the absorption process of flue gas of the present invention, flue gas desulphuization rate may be up to 99.00%.Sulphur The rate of recovery is more than 96%.
In the present invention, in step (2), obtained desulfurization pelletizing sulfur-bearing control is below 1.0%, and pelletizing compression strength is more than 2000N/.
By the collaboration of parameter in each operation of step (2), the control of the pelletizing sulfur-bearing after roasting can be made below 1.0%, Pelletizing compression strength is more than 2000N/.The sulphur impurity of pelletizing is few made from step (2), and has good compression strength, more Beneficial to the reduction of step (3), the chip index in reduction process is reduced, it is to avoid knot kiln.
After step (2) processing terminates, obtained desulfurization pelletizing has higher temperature, without carrying out extra cooling processing, Rotary kiln is sent directly into, reducing agent is incorporated into kiln, reduction reaction is quickly carried out.Furnace charge hot charging can save energy consumption, improve yield, Reduce production cost.
In step (3), described reducing agent is preferably at least one of semi-coke, anthracite, bituminous coal.
Preferably, the granularity of described reducing agent is 5~30mm.In rotary kiln, reduction temperature and atmosphere are by spray The granular reduction dosage and the reasonable layout of air quantity entered is controlled.The granularity of reducing agent is too thin, and reducing agent is easily distributed in kiln hood, Cause in the middle part of kiln and afterbody reducing agent is few, influence reduction effect.Reducing agent granularity is excessive, and reducing agent is easily distributed in kiln tail, causes Kiln hood reducing agent is few, and temperature is low.
Preferably, supplying reducing agent in carbon and agglomerates in iron mass ratio be 0.50~0.80.
It that is to say, the reducing agent (being counted using carbon) of supplying is with the mass ratio of agglomerates (being counted using iron) as 0.50~0.80.
When carbon weight of iron ratio is less than 0.50, reducing atmosphere is weak, and reduction temperature is low, and reduction effect is deteriorated, zinc indium volatility Low, the degree of metalization of iron declines, and the separating effect of zinc indium and iron is deteriorated.When carbon weight of iron ratio is higher than 0.80, gone back due to a large amount of Former agent heat absorption causes reduction temperature to decline, and reduction effect is similarly deteriorated, reducing agent consumption increase, cost rise.
Further preferably, the reducing agent (being counted using carbon) of supplying and the mass ratio of agglomerates (being counted using iron) as 0.60~ 0.80。
Preferably, under described reducing agent, carbon weight of iron when reduction reaction temperature, direct reduction reactor preferably Time is 30~90min.When recovery time is less than 30min, ferriferous oxide reduction effect is poor, and the degree of metalization of iron declines, zinc indium Reduction volatilization degree also declines, and the separating effect of zinc indium and iron is deteriorated.When recovery time is higher than 90min, due to reducing agent supplying Amount is certain, is deteriorated in reduction later stage reducing atmosphere, is easily caused reoxidizing for metallic iron, and the yield of rotary kiln reduction also can Decline.
Preferably, direct-reduction temperature is 1200~1250 DEG C；Recovery time is 30~60min.
Red-hot iron vitriol slag agglomerates (desulfurization pelletizing) enter rotary kiln, add the reducing agent of the mass ratio, such as cigarette Coal or semi-coke, reduce the time under reduction temperature, make zinc oxide, indium redox be metallic zinc and indium metal, due to Its low boiling point, volatility is good, enters flue gas in steam state.It is oxidized to the oxide of zinc and indium again in flue gas, is returned by dedusting Receipts obtain zinc-rich indium flue dust.Iron, gallium oxidation are also reduced to metal, and the metallization of iron is more than 80%.But because iron, gallium metal boil Point is high, it is impossible to vaporizes, is retained in metallized pellet, so as to realize that zinc, indium and iron, gallium are efficiently separated.The cigarette of reduction reaction Zinc of the gas bag containing reduction volatilization, indium, carry out enriching and recovering of gathering dust by the flue gas to reduction reaction, realize valuable member in iron vitriol slag The recovery of plain zinc, indium.Zinc-rich indium flue dust is more than 58% containing zinc, is more than 0.016% containing indium, zinc, indium recovery are respectively greater than 96% With 85%.
By described reduction reaction, the ferriferous oxide in green-ball is largely reduced to metallic iron, included in reduction furnace In material, reduction furnace charge is carried out after cooling processing, by magnetic separation, collection obtains having magnetic metallized pellet and nonmagnetics (discarded object)；Due to the strong affinity for iron of gallium, gallium is enriched with metallized pellet.
The degree of metalization of metallized pellet is greater than or equal to 80%.
In step (4), the metallized pellet supplying reduction carbon materials obtained to magnetic separation carry out melt processed, are subsequently isolated out Ironmaking slag obtains rich gallium molten iron, by the collaboration of additive of the present invention and other steps, and, by molten slitting part preferably Lift the recovering effect of iron.
Described reduction carbon materials are preferably anthracite and/or coke.
Preferably, molten point temperature is 1450-1550 DEG C, the quality proportioning of reduction carbon materials is 1-5% (with metallized pellet On the basis of weight), it is 20-60min between molten timesharing.
Molten point of further preferred 1500-1550 DEG C of temperature, the amount of allocating of reduction carbon materials is 1~3%.
Under the conditions of described preferred molten point, the iron content in rich gallium molten iron can be made to be more than or equal to 94%, be more than containing gallium or Equal to 300g/t.It is the quality raw materials for producing cement after the direct water-spraying control of slag, realizes the recycling of iron vitriol slag and harmless Change and utilize.
In the present invention, existing method separating gallium, iron from obtained rich gallium molten iron can be used.
The present invention preferably casts positive plate by condensation, using stainless steel plate as negative electrode, is electrolysed in electrolytic cell.
In the present invention, electrolytic condition is：Electrolyte component is 45-55g/L FeSO4, 135-145g/L (NH4)2SO4, electricity Solve liquid pH value 4.0~5.0,40~60 DEG C of temperature, 100~300A/m of current density2, 1.0~2.5V of tank voltage and pole span 20~ 50mm。
In the present invention, by the collaboration of step (1)~step (4) each step, electrolysis bar of the present invention is being matched with Part, the Iron grade that iron powder is peeled off from minus plate may be up to the content of the gallium being enriched with 96.5%, the earth of positive pole and be more than or equal to 0.20%.Iron, the gallium rate of recovery are respectively greater than 90% and 80%.
In the prior art, easily formation mother bulb and mother bulb are difficult the problem grown up to iron vitriol slag in balling process, and the present invention is logical Under the collaboration for crossing the additive each component and weight part ratio, mother bulb synthesis speed can be effectively reduced, green-ball growth rate is controlled； In addition, can also effectively solve iron vitriol slag because the pellet quality that crystal water content height and heat endurance difference etc. are brought is poor and yields poorly The problems such as, it can effectively be cooperateed with by described additive and absorb the crystallization water discharged in iron vitriol slag thermal histories, so as to control life The vapour pressure that ball is produced in thermal histories in ball, reduces internal stress, also can control the migration rate and increase mineral of moisture The cohesive force of intergranular, when bringing high internal stress because of the vapour pressure of generation in green-ball, cohesive force can resist peace Weigh the internal stress produced in Pellets in Drying Process, keeps pelletizing not to be destroyed, and maintains high heat endurance and good strength.
Additive of the present invention is except possessing good nucleation, effect and cementation absorb water, fixed water etc. Outside beneficial to the effect of pelletizing, sulphur in the follow-up pelletizing oxidizing roasting desulfurization of collaboration enhancing, direct-reduction and molten operation break-down is also helped Removing, the reduction of catalytic metal oxide and promote scum separation etc. effect：
Sulphur in iron vitriol slag is mainly sulfate (autunezite), and sulfur content is too high, passes through addition of the present invention The use of agent, can prepare the collaboration of each component in the green-ball of excellent performance, green-ball, can effectively consume oxygen inside pelletizing and Discharge CO2, improve desulfurization atmosphere, then coordinated is in the sulfur removal technology of step (2), can efficient removal sulphur, moreover it is possible to improve desulfurization The intensity of pelletizing；Then again coordinated in the reducing process of step (3), can concerted catalysis reduction reaction, promote zinc, indium also Original is volatilized and enters flue gas, strengthens zinc, indium and iron, the separation of gallium.In addition, described additive helps to strengthen slag making performance, Contribute to the slag-liquid separation of step (5).
In the present invention, described additive is incorporated in iron vitriol slag, high-quality green-ball is prepared, then iron vitriol slag pelletizing is carried out High-temperature roasting desulfurization and consolidation, while desulfurization and pelletizing are consolidated, by the effect of additive, improve pelletizing porosity and ball Group's basicity, improves the reproducibility of agglomerates, so as to strengthen the reduction and volatilization of zinc and indium, improves the product of zinc and indium in flue dust Position and the rate of recovery；By improving pelletizing porosity, it is possible to decrease reduction swellability rate, reduce efflorescence of the pelletizing in reduction process and return Rotary kiln ring formation probability；By change the additional proportion of additive adjust agglomerates basicity (calcium oxide and dioxide-containing silica Ratio) and magnalium ratio, viscosity, mobility and the desulphurizing ability of slag during molten point are can adjust, and by improving iron in pelletizing Degree of metalization, the separating effect of reinforcing slag and iron improves the rate of recovery of iron and gallium, reduces the content of Sulfur Content in Hot Iron, improve iron Water quality.
Beneficial effect
Additive of the present invention has multi-functional, can not only improve green ball strength and heat endurance, and can be strong Change desulfurization, catalysis reduction and molten point of reinforcing.Additive raw material wide material sources, it is cheap, work well, with good popularization Application prospect.
The use of additive, successfully solves technical barrier present in iron vitriol slag pelletizing and follow-up pyrogenic process processing technology, Good basis has been laid to extract valuable element from iron vitriol slag.
With addition of multifunction additive iron vitriol slag pelletizing after desulfurization with roasting technique is consolidated pelletizing sulfur-bearing control 1.0% with Under, compression strength is more than 2000N/, and Iron grade 58% or so, reduction sex index is more than 70%, and reduction swellability rate is less than 12%, Strength after being reduced and cooled is more than 400N/, and performance is entirely capable of meeting follow-up direct-reduction-molten division technique requirement.
Flue gas desulfurization is carried out using ammonia absorption liquid, chemical fertilizer products ammonium sulfate is produced, sulphur is sufficiently recycled, Influence of the desulfurization with roasting technique to environment is eliminated, and the rate of recovery of sulphur is more than 95%.
Red-hot iron vitriol slag agglomerates (desulfurization pelletizing) pass through rotary kiln for directly reducing-indirect water-cooling-dry type magnetic separation-electricity Stove molten point of process, is successfully realized zinc, indium and iron, gallium and efficiently separates.Obtained zinc-rich indium flue dust is more than 58% containing zinc, containing indium More than 0.016%, zinc, indium recovery are respectively greater than 96% and 85%.Rich gallium pig iron iron content more than 96%, is more than 300g/ containing gallium The rate of recovery of t, iron and gallium is respectively greater than 95%, 92%.Zinc-rich indium flue dust and the richness gallium pig iron are to extract zinc, indium and iron, gallium respectively Quality raw materials.
Iron gallium separation is carried out to the electrolysis of the rich gallium pig iron.The rich gallium earth of positive pole more than 0.20% containing gallium is obtained, for next step Extract gallium.Iron powder Iron grade is more than 96.5%.Iron, the gallium rate of recovery are respectively greater than 90% and 80%.
The secondary slag that the present invention is obtained is the nonmagnetics and electroslag of direct-reduction technique output, is used equally for cement to give birth to Production, realizes the innoxious and recycling of secondary slag, and no solid waste is produced, and non-exhaust emission, whole technique is one It is individual to clean the new technology that recycling is efficiently utilized, and the elements such as iron, gallium, zinc, indium, sulphur is efficiently separated and is reclaimed.
Brief description of the drawings
Fig. 1 is iron vitriol slag recovery process schematic flow sheet of the present invention.
Embodiment
Following examples and comparative example, unless specified or limited otherwise, it is wet that used iron vitriol slag is derived from the coloured company of Tongling, Anhui Province Method zine-smelting plant, its chemical analysis is as follows：TFe 28.25%, S 12.78%, Zn3.61%, In490g/t, Ga 160g/t, SiO20.50%, CaO 0.19%, MgO 0.46%, Al2O30.90%LOI 49.33%.
Following examples and comparative example, particle of each component less than 0.074mm of additive account for the 70- of respective weight 85%.
Embodiment 1
The iron vitriol slag aqueous 7.2% of drying, with addition of the multifunction additive that mass ratio is 2%, (mass ratio is semi-coke powder 15%, agstone 40%, dolomite dust 15%, sodium humate dry powder 10%, brown iron oxide 10%, carbonic acid sodium powder 10%), 1min (1200-1800rpm) is mixed in intensive mixer, (profit mill moisture is 6-8%) the mixing 2min in damp mill, then in circle Pelletizing is carried out in disk pelletizer, granularity is prepared into for 8~16mm, aqueous 9.5% green-ball.Shatter strength of green pellet be 5.1 times/ 0.5m, compression strength of green pel let 15.3N/.
Green-ball is on belt type roasting machine (green-ball bed depth be 70mm) by preheating at 450 DEG C of drys 3min, 650 DEG C The 10min and oxidizing roasting 80min at 1150 DEG C, agglomerates residual sulfur content is 1.0%, and desulfurization degree reaches 92.2%, is calcined ball Group's compression strength is 2100N/.
The flue gas of belt type roasting machine pellet roasting desulfurization is gathered dust and desulfurization.The dust of removing returns to iron vitriol slag and dried Process.The SO that flue gas after dedusting is sprayed into the absorbing liquid absorption flue gas containing ammoniacal liquor2, it is passed through air oxidation SO2, generate sulfuric acid Ammonium.Absorbing liquid containing ammonia is 70L/m with flue gas volume ratio3；The concentration of a hydration ammonia is 10g/L in the absorbing liquid containing ammonia.Flue gas Desulfurization degree is 96.24%, sulfur recovery rate 94.3%.
Temperature is directly entered rotary kiln for 900 DEG C of red-hot pelletizing and reduced after desulfurization with roasting technique, add granularity for 5~ 25mm solid reductant bituminous coal, under conditions of 1100 DEG C of reduction temperature, recovery time 90min and carbon weight of iron ratio is 0.50 It is reduced directly, the metallization of pelletizing iron is 80.12%.Reclaimed by flue gas ash removal and obtain zinc-rich indium material, it contains zinc 58.23%, containing indium 0.0167%, zinc, indium recovery are respectively 96.25% and 85.56%.
It is reduced directly material and carries out indirect water-cooling, dry type magnetic separation, obtains metallized pellet and nonmagnetics.Metallized pellet Into electric furnace, melted and slag sluicing system under the conditions of 60min between 1450 DEG C, mixed carbon comtent 5%, molten timesharing.Because gallium has Strong affinity for iron, gallium, which enters in molten iron, obtains efficiently concentrating.The rich gallium pig iron is former as the high-quality of next step iron, gallium separation and Extraction Material.The rate of recovery of rich gallium molten iron iron content 96.34%, 358g/t containing gallium, iron and gallium is respectively 95.68%, 92.17%.
Rich gallium molten iron casts positive plate by condensation, using stainless steel plate as negative electrode, is electrolysed in electrolytic cell.It is electrolysed bar Part is that electrolyte component is 45-55g/L FeSO4, 135-145g/L (NH4)2SO4, pH value 4.0, temperature 60 C, current density 100A/m2, tank voltage 2.5V and pole span 50mm.Iron powder is periodically peeled off from minus plate, gallium sunk in the earth of positive pole, obtain be containing gallium The 0.26% rich gallium earth of positive pole, gallium is extracted for next step.Iron powder Iron grade is 96.58%.Iron, the gallium rate of recovery are respectively 91.35% and 80.32%.
Embodiment 2
The iron vitriol slag aqueous 8.3% of drying, with addition of the multifunction additive that mass ratio is 5%, (mass ratio is semi-coke powder 30%, agstone 40%, dolomite dust 15%, sodium humate dry powder 5%, brown iron oxide 5%, carbonic acid sodium powder 5%), strong 1min (1200-1800rpm) is mixed in power mixer, (profit mill moisture is 6-8%) mixing 2min, fully mixed in damp mill It is even, then pelletizing is carried out in disc balling machine, granularity is prepared for 8~16mm, aqueous 10.5% green-ball.Shatter strength of green pellet For 5.6 times/0.5m, compression strength of green pel let 16.0N/.
Green-ball is on belt type roasting machine (green-ball bed depth be 90mm) by preheating at 350 DEG C of drys 5min, 850 DEG C The 8min and oxidizing roasting 60min at 1200 DEG C, agglomerates residual sulfur content is 0.63%, and desulfurization degree reaches 96.2%, is calcined ball Group's compression strength is 2250N/.Compared with embodiment 1, additive formula brings up to 5% and semi-coke powder therein increase by 2% When 15%, green ball strength increase, shatter strength of green pellet by 5.1 times/0.5m rise be 5.6 times/0.5m, compression strength of green pel let by 15.3N/ increase to 16.0N/.While additives ratio increase, pre- thermal parameter is kept to change in optimized scope, will Pellet roasting temperature brings up to 1200 DEG C by 1150 DEG C, and both act synergistically, and is on the one hand to be adjusted by additive inside pelletizing The condition of atmosphere and chemical reaction, then by improving the synergy of temperature increasing reaction power, reinforcing desulfuration reaction promotes sulphur The decomposition of hydrochlorate, makes agglomerates residual sulfur content drop to 0.63% by 1%, desulfurization degree brings up to 96.2%, roasting by 92.2% Pelletizing compression strength increases to 2250N/ by 2100N/.
The flue gas of belt type roasting machine pellet roasting desulfurization is gathered dust and desulfurization.The dust of removing returns to iron vitriol slag and dried Process.The SO that flue gas after dedusting is sprayed into the absorbing liquid absorption flue gas containing ammoniacal liquor2, it is passed through air oxidation SO2, generate sulfuric acid Ammonium.Absorbing liquid containing ammonia is 90L/m with flue gas volume ratio3；The concentration of a hydration ammonia is 15g/L in the absorbing liquid containing ammonia.Flue gas Desulfurization degree is 97.68%, sulfur recovery rate 95.8%.Compared with embodiment 1, absorbing liquid containing ammonia is 70L/m with flue gas volume ratio3Increase It is added to 90L/m3And in absorbing liquid containing ammonia a hydration ammonia concentration when increasing to 15g/L by 10g/L, flue gas desulphuization rate by 96.24% increases to 97.68%, and sulfur recovery rate increases to 95.8% by 94.3%.Because the volume of absorbing liquid containing ammonia is bigger And in absorbing liquid containing ammonia one hydration ammonia concentration it is higher, it is longer with the smoke contacts time, be more conducive to the progress of absorbing reaction；Together Shi Hanyou effective ingredient ammonia is more, and absorbability is stronger, so as to cause desulfurization degree high, into absorbing, molten sulfur is more, sulfur recovery Rate is bigger.
Temperature is directly entered rotary kiln for 980 DEG C of red-hot pelletizing and reduced after desulfurization with roasting technique, add granularity for 5~ 25mm solid reductant bituminous coal, under conditions of 1200 DEG C of reduction temperature, recovery time 60min and charcoal weight of iron ratio is 0.50 It is reduced directly, the metallization of pelletizing iron is 88.12%.Reclaimed by flue gas ash removal and obtain zinc-rich indium material, it contains zinc 59.56%, containing indium 0.0175%, zinc, indium recovery are respectively 96.89% and 85.97%.Compared with embodiment 1, in reduction Between and charcoal weight of iron ratio be optimized scope in when, while additive is improved, reduction temperature brings up to 1200 DEG C by 1100 DEG C, Both synergies, increase the motive force of reduction reaction, the enhancing of reactant molecule diffusivity, iron, zinc, indium, gallium oxidation Thing reduction rate increase, promote their reduction, enhance the volatilization of zinc, indium with separating so that the metallization of pelletizing iron by for 80.12% increases to 88.12%, and Zinc from Flue Dust, indium recovery increase to 96.89% and by 96.25% and 85.56% respectively 85.97%.
It is reduced directly material and carries out indirect water-cooling, dry type magnetic separation, obtains metallized pellet and nonmagnetics.Metallized pellet Into electric furnace, melted and slag sluicing system under the conditions of 20min between 1550 DEG C, mixed carbon comtent 1%, molten timesharing.Because gallium has Strong affinity for iron, gallium, which enters in molten iron, obtains efficiently concentrating.The rich gallium pig iron is former as the high-quality of next step iron, gallium separation and Extraction Material.The rate of recovery of rich gallium molten iron iron content 96.67%, 460g/t containing gallium, iron and gallium is respectively 96.79%, 94.20%.With implementation Example 1 compares, when bringing up to 1550 DEG C with 1450 DEG C between mixed carbon comtent and molten timesharing in optimized scope, to melt point temperature, but rich gallium Molten iron iron content increases to 96.67% by 96.34%, and molten iron is brought up to 460g/t, iron and the gallium rate of recovery point containing gallium by 358g/t Not 96.79% and 94.20% are increased to by 95.68% and 92.17%.Adding suitable additive, it is ensured that suitable slag type On the premise of, improve a molten point temperature and be conducive to slag and iron to be completely melt, additive and molten point of temperature synergy are obtained well Slag, iron mobility, iron are separated thoroughly with slag, so as to be conducive to improving molten iron Iron grade, gallium content and iron, the gallium rate of recovery.
Rich gallium molten iron casts positive plate by condensation, using stainless steel plate as negative electrode, is electrolysed in electrolytic cell.It is electrolysed bar Part is that electrolyte component is 45-55g/L FeSO4, 135-145g/L (NH4)25O4, pH value 5.0,40 DEG C of temperature, current density 300A/m2, tank voltage 1.0V and pole span 50mm.Iron powder is periodically peeled off from minus plate, gallium sunk in the earth of positive pole, obtain be containing gallium The 0.22% rich gallium earth of positive pole, gallium is extracted for next step.Iron powder Iron grade is 96.79%.Iron, the gallium rate of recovery are respectively 91.68% and 80.97%.Compared with embodiment 1, be electricity in optimized scope in electrolyte ph, temperature and tank voltage and pole span When current density brings up to 300A/m2 by 100A/m2, iron powder Iron grade brings up to 96.79% by 96.58%.Iron, the gallium rate of recovery point Not 91.68% and 80.97% are increased to by 91.35% and 80.32%.This can because current density it is bigger there is provided electronics more Many, iron, gallium ion are more readily available electronics, become elemental metals and are deposited on minus plate, the rate of recovery is higher.
Embodiment 3
The iron vitriol slag aqueous 9.0% of drying, with addition of the multifunction additive that mass ratio is 7%, (mass ratio is blue to iron vitriol slag Powdered carbon 15%, agstone 40%, dolomite dust 15%, sodium humate dry powder 10%, brown iron oxide 10%, carbonic acid sodium powder 10%) 1min (1200-1800rpm), is mixed in intensive mixer, is mixed in damp mill (profit mill moisture is 6-8%) 2min, is fully mixed, then carries out pelletizing in disc balling machine, prepares granularity for 8~16mm, aqueous 12.0% green-ball. Shatter strength of green pellet is 7.3 times/0.5m, compression strength of green pel let 15.0N/.
Green-ball is on belt type roasting machine (green-ball bed depth be 110mm) by preheating at 250 DEG C of drys 6min, 1100 DEG C The 9min and oxidizing roasting 20min at 1300 DEG C, agglomerates residual sulfur content is 0.56%, and desulfurization degree reaches 98.3%, is calcined ball Group's compression strength is 2500N/.Compared with Examples 1 and 2, when additive formula brings up to 7% by 2% and 5%, green-ball is strong Degree further increase, shatter strength of green pellet is 7.3 times/0.5m, green-ball pressure resistance by 5.1 times/0.5m and 5.6 time/0.5m rises Degree is slightly decreased, but can meet manufacturing technique requirent (being more than 10N/).While additives ratio increase, pre- physochlaina infudibularis is kept Number changes in optimized scope, and pellet roasting temperature is brought up into 1300 DEG C by 1150 DEG C and 1200 DEG C, and both act synergistically, and one Aspect is the condition that pelletizing internal atmosphere and chemical reaction are adjusted by additive, then increases reaction power by improving temperature Synergy, reinforcing desulfuration reaction, promotes the decomposition of sulfate, agglomerates residual sulfur content is dropped to by 1% and 0.63% 0.56%, desulfurization degree brings up to 98.3% by 92.2% and 96.2%, and agglomerates compression strength is by 2100N/ and 2250N/ It is individual to increase to 2500N/.Thus further demonstrate that the synergy of additive and sintering temperature to improve agglomerates intensity and Improve desulfurization to play an important roll.
The flue gas of belt type roasting machine pellet roasting desulfurization is gathered dust and desulfurization.The dust of removing returns to iron vitriol slag and dried Process.The SO that flue gas after dedusting is sprayed into the absorbing liquid absorption flue gas containing ammoniacal liquor2, it is passed through air oxidation SO2, generate sulfuric acid Ammonium.Absorbing liquid containing ammonia is 120L/m with flue gas volume ratio3；The concentration of a hydration ammonia is 10g/L in the absorbing liquid containing ammonia.Flue gas Desulfurization degree is 96.89%, sulfur recovery rate 96.9%.Compared with embodiment 1, the concentration of a hydration ammonia is in absorbing liquid containing ammonia 10g/L is constant, and absorbing liquid containing ammonia is with flue gas volume ratio by 70L/m3Increase to 120L/m3When, flue gas desulphuization rate is increased by 96.24% 96.89% is added to, sulfur recovery rate increases to 96.9% by 94.3%.Because the volume of absorbing liquid containing ammonia is bigger, connect with flue gas The tactile time is longer, is more conducive to the progress of absorbing reaction；The effective ingredient ammonia contained simultaneously is more, is more conducive to desulphurization reaction Carry out, so as to cause desulfurization degree high, into absorbing, molten sulfur is more, and sulfur recovery rate is bigger.
Temperature is directly entered rotary kiln for 1050 DEG C of red-hot pelletizing and reduced after desulfurization with roasting technique, add granularity for 5~ 25mm solid reductant bituminous coal, under conditions of 1250 DEG C of reduction temperature, recovery time 30min and charcoal weight of iron ratio is 0.80 It is reduced directly, the metallization of pelletizing iron is 93.75%.Reclaimed by flue gas ash removal and obtain zinc-rich indium material, it contains zinc 61.23%, containing indium 0.0192%, zinc, indium recovery are respectively 97.35% and 87.12%.Compared with embodiment 1,2, in reduction When time is in optimized scope, while additive brings up to 7% by 2%, 5%, reduction temperature is carried by 1100 DEG C, 1200 DEG C Height is to 1250 DEG C, and charcoal weight of iron ratio brings up to 0.8 by 0.5, under the synergy of reduction temperature, reducing agent and additive, also Originality atmosphere strengthens, and the motive force of reduction reaction is substantially increased, the enhancing of reactant molecule diffusivity, iron, zinc, indium, gallium oxygen Compound reduction rate increase, promote their reduction, enhance the volatilization of zinc, indium with separating so that the metallization of pelletizing iron by 93.75% is increased to for 80.12%, 88.12%, Zinc from Flue Dust, indium recovery are increased to by 96.25% and 85.56% respectively 96.89% and 85.97%.
It is reduced directly material and carries out indirect water-cooling, dry type magnetic separation, obtains metallized pellet and nonmagnetics.Metallized pellet Into electric furnace, melted and slag sluicing system under the conditions of 40min between 1550 DEG C, mixed carbon comtent 3%, molten timesharing.Because gallium has Strong affinity for iron, gallium, which enters in molten iron, obtains efficiently concentrating.The rich gallium pig iron is former as the high-quality of next step iron, gallium separation and Extraction Material.The rate of recovery of rich gallium molten iron iron content 97.45%, 490g/t containing gallium, iron and gallium is respectively 98.00%, 95.00%.Embodiment 2 Compare, be in optimized scope in molten point of temperature and mixed carbon comtent, when bringing up to 40min by 20min between molten timesharing, rich gallium molten iron iron content Increase to 97.45%% by 96.34%, molten iron is brought up to 490g/t, iron and gallium rate of recovery difference containing gallium by 460g/t 96.79% and 94.20% increases to 98.00% and 95.00%.Adding suitable additive, it is ensured that before suitable slag type Put, be conducive to slag and iron fully to melt between the molten timesharing of extension, slag and iron spread, be layered, in additive and the association of molten point of temperature Same-action, it is ensured that thorough iron is separated with slag, so as to be conducive to improving molten iron Iron grade, gallium content and iron, the gallium rate of recovery.
Rich gallium molten iron casts positive plate by condensation, using stainless steel plate as negative electrode, is electrolysed in electrolytic cell.It is electrolysed bar Part is that electrolyte component is 45-55g/L FeSO4, 135-145g/L (NH4)2SO4, pH value 5.0,40 DEG C of temperature, current density 300A/m2, tank voltage 1.0V and pole span 20mm.Iron powder is periodically peeled off from minus plate, gallium sunk in the earth of positive pole, obtain be containing gallium The 0.221% rich gallium earth of positive pole, gallium is extracted for next step.Iron powder Iron grade is 97.21%.Iron, the gallium rate of recovery are respectively 92.69% and 81.33%.
Compared with embodiment 2, electrolyte ph, temperature and current density, tank voltage be optimized scope in, pole span by When 50mm is reduced to 20mm, iron powder Iron grade brings up to 97.21% by 96.79%.Iron, the gallium rate of recovery are respectively by 91.68% and 80.97% increases to 92.69% and 81.33%.Because pole span is smaller, electric field is stronger, and iron, the distance of gallium ion migration are got over Short, shorter from anode to cathodic migration required time, deposition is faster, and the rate of recovery is higher.
Embodiment 4
The iron vitriol slag aqueous 8.3% of drying, with addition of the multifunction additive that mass ratio is 5%, (mass ratio is burnt to iron vitriol slag Powder 30%, agstone 25%, dolomite dust 15%, sodium humate dry powder 10%, brown iron oxide 10%, carbonic acid sodium powder 10%), 1min (1200-1800rpm) is mixed in intensive mixer, 2min (profit mill moisture is 6-8%) is mixed in damp mill, fully Mix, then pelletizing is carried out in disc balling machine, prepare granularity for 8~16mm, aqueous 11.0% green-ball.Green-ball is fallen by force Spend for 5.5 times/0.5m, compression strength of green pel let 15.1N/.
Green-ball is on belt type roasting machine (green-ball bed depth be 90mm) by preheating at 300 DEG C of drys 6min, 1100 DEG C The 5min and oxidizing roasting 20min at 1300 DEG C, agglomerates residual sulfur content is 0.38%, and desulfurization degree reaches 99.0%, is calcined ball Group's compression strength is 2630N/.Compared with embodiment 2, additive formula is 5%, but wherein dosage of coke is improved 15%, unobvious is influenceed on green ball strength；When additives ratio is identical, pre- thermal parameter is kept to change in optimized scope, will Pellet roasting temperature brings up to 1300 DEG C by 1200 DEG C, and additive acts synergistically with improving both sintering temperatures, especially by Coke powder ratio in additive is improved, pelletizing internal oxidation atmosphere weakens, and promotes the decomposition of sulfate, makes agglomerates residual sulfur content Drop to 0.38% by 0.56%, desulfurization degree brings up to 99.0% by 98.3%, and agglomerates compression strength is carried by 2500N/ Height is to 2630N/.Thus further demonstrate that the synergy of additive and sintering temperature to improving agglomerates intensity and improvement Desulfurization plays an important roll.
The flue gas of belt type roasting machine pellet roasting desulfurization is gathered dust and desulfurization.The dust of removing returns to iron vitriol slag and dried Process.The SO that flue gas after dedusting is sprayed into the absorbing liquid absorption flue gas containing ammoniacal liquor2, it is passed through air oxidation SO2, generate sulfuric acid Ammonium.Absorbing liquid containing ammonia is 70L/m with flue gas volume ratio3；The concentration of a hydration ammonia is 18g/L in the absorbing liquid containing ammonia.Flue gas Desulfurization degree is 96.97%, sulfur recovery rate 95.2%.Compared with embodiment 1, be 70L/m in absorbing liquid containing ammonia and flue gas volume ratio3 When, when the concentration of a hydration ammonia increases to 18g/L by 10g/L in absorbing liquid containing ammonia, flue gas desulphuization rate is increased to by 96.24% 96.97%, sulfur recovery rate increases to 95.2% by 94.3%.Because the concentration of a hydration ammonia is higher in absorbing liquid containing ammonia, The effective ingredient ammonia contained is more, with SO in flue gas2Respond it is stronger, so as to cause desulfurization degree high, into absorbing molten sulfur More, sulfur recovery rate is bigger.
Temperature is directly entered rotary kiln for 1100 DEG C of red-hot pelletizing and reduced after desulfurization with roasting technique, add granularity for 5~ 25mm solid reductant bituminous coal, under conditions of 1250 DEG C of reduction temperature, recovery time 30min and carbon weight of iron ratio is 0.60 It is reduced directly, the metallization of pelletizing iron is 94.86%.Reclaimed by flue gas ash removal and obtain zinc-rich indium material, it contains zinc 60.92%, containing indium 0.0185%, zinc, indium recovery are respectively 97.00% and 86.11%.Compared with embodiment 2, in additive On the premise of proportioning is 5% and improves preheating temperature, by improving reduction temperature and carbon weight of iron ratio, improved reduction reaction Dynamic conditions, accelerates reduction reaction rate, so as to improve ferrous metal rate and iron, zinc, indium recovery.The metallization of pelletizing iron 94.86% is brought up to by 88.12%, zinc-rich indium material zinc, indium recovery bring up to 97.00% by 96.89% and 85.97% respectively With 86.11%.
It is reduced directly material and carries out indirect water-cooling, dry type magnetic separation, obtains metallized pellet and nonmagnetics.Metallized pellet Into electric furnace, melted and slag sluicing system under the conditions of 20min between 1550 DEG C, mixed carbon comtent 1%, molten timesharing.Because gallium has Strong affinity for iron, gallium, which enters in molten iron, obtains efficiently concentrating.The rich gallium pig iron is former as the high-quality of next step iron, gallium separation and Extraction Material.The rate of recovery of rich gallium molten iron iron content 97.45%, 490g/t containing gallium, iron and gallium is respectively 96.89%, 96.58%.With implementation Example 2 compares, although molten slitting part is identical, is due to that metallized pellet quality improves, degree of metalization improve 5 percentages account for On, cause rich gallium molten iron iron content, containing gallium rise, iron, the gallium rate of recovery have risen, a molten point effect is improved.Therefore, metallize Pellet quality has a significant effect to a molten point effect.Pass through the synergy between additive and reduction system optimization, molten point of effect of reinforcing Really, iron is separated with slag thoroughly, gallium is enriched in molten iron to greatest extent, improve the rate of recovery of iron and gallium.
Rich gallium molten iron casts positive plate by condensation, using stainless steel plate as negative electrode, is electrolysed in electrolytic cell.It is electrolysed bar Part is that electrolyte component is 45-55g/L FeSO4, 135-145g/L (NH4)2SO4, pH value 4.0, temperature 50 C, current density 300A/m2, tank voltage 2.0V and pole span 40mm.Iron powder is periodically peeled off from minus plate, gallium sunk in the earth of positive pole, obtain be containing gallium The 0.256% rich gallium earth of positive pole, gallium is extracted for next step.Iron powder Iron grade is 97.11%.Iron, the gallium rate of recovery are respectively 93.2% and 83.45%.Compared with embodiment 2, by improving tank voltage and reducing pole span, accelerate electron transfer and shorten electronics Migration distance so that iron, gallium ion fast deposition respectively obtain raising, iron powder iron in negative electrode, iron powder grade and iron, the gallium rate of recovery Grade brings up to 97.11% by 96.79%, and iron, the gallium rate of recovery increase to 93.2% and by 91.68% and 80.97% respectively 83.45%.
Embodiment 5
The iron vitriol slag aqueous 8.3% of drying, with addition of the multifunction additive that mass ratio is 5%, (mass ratio is blue to iron vitriol slag Powdered carbon 30%, agstone 40%, dolomite dust 10%, sodium humate dry powder 10%, brown iron oxide 5%, carbonic acid sodium powder 5%), 1min (1200-1800rpm) is mixed in intensive mixer, 2min (profit mill moisture is 6-8%) is mixed in damp mill fully Mix, then pelletizing is carried out in disc balling machine, prepare granularity for 8~16mm, aqueous 11.0% green-ball.Green-ball is fallen by force Spend for 5.4 times/0.5m, compression strength of green pel let 15.2N/.
Green-ball is on belt type roasting machine (green-ball bed depth be 90mm) by preheating at 300 DEG C of drys 6min, 1050 DEG C The 9min and oxidizing roasting 40min at 1300 DEG C, agglomerates residual sulfur content is 0.61%, and desulfurization degree reaches 98.8%, is calcined ball Group's compression strength is 2530N/.Compared with embodiment 4, green ball strength is substantially close to although preheating temperature is at 1100 DEG C 1050 DEG C are dropped to, but sintering temperature is constant and extends preheating time and roasting time, pelletizing is also had sufficient time progress Consolidation and desulfurization, therefore, agglomerates intensity and desulfurized effect are also more close.When additive formula is identical, optimization it is pre- Heat and roasting system can change within the specific limits, also can reach close effect.
The flue gas of belt type roasting machine pellet roasting desulfurization is gathered dust and desulfurization.The dust of removing returns to iron vitriol slag and dried Process.The SO that flue gas after dedusting is sprayed into the absorbing liquid absorption flue gas containing ammoniacal liquor2, it is passed through air oxidation SO2, generate sulfuric acid Ammonium.Absorbing liquid containing ammonia is 120L/m with flue gas volume ratio3；The concentration of a hydration ammonia is 18g/L in the absorbing liquid containing ammonia.Flue gas Desulfurization degree is 99.00%, sulfur recovery rate 97.5%.Compared with embodiment 4, a hydration ammonia is dense in identical absorbing liquid containing ammonia When spending for 18g/L, absorbing liquid containing ammonia is with flue gas volume ratio by 70L/m3Increase to 120L/m3When, flue gas desulphuization rate by 96.97%, Sulfur recovery rate 95.2% brings up to 99.00%, and sulfur recovery rate is increased to 97.5% by 95.2%.Because absorbing liquid containing ammonia with Flue gas volume is than bigger, SO in flue gas2It is longer with amino molecule time of contact in absorbing liquid, react more abundant, absorptivity is higher, most Whole desulfurized effect is better, and the ammonium sulfate of generation is more, and the sulphur of recovery is more, and sulfur recovery rate is just high.
Temperature is directly entered rotary kiln for 1090 DEG C of red-hot pelletizing and reduced after desulfurization with roasting technique, add granularity for 5~ 25mm solid reductant bituminous coal, under conditions of 1200 DEG C of reduction temperature, recovery time 30min and carbon weight of iron ratio is 0.80 It is reduced directly, the metallization of pelletizing iron is 93.79%.Reclaimed by flue gas ash removal and obtain zinc-rich indium material, it contains zinc 61.43%, containing indium 0.0182%, zinc, indium recovery are respectively 97.90% and 86.55%.Compared with embodiment 4, in additive With when when the recovery time is identical, in preferred scope, by the reduction of reduction temperature and carbon weight of iron than rise phase group Close, obtained reduction effect is substantially close.
It is reduced directly material and carries out indirect water-cooling, dry type magnetic separation, obtains metallized pellet and nonmagnetics.Metallized pellet Into electric furnace, melted and slag sluicing system under the conditions of 60min between 1500 DEG C, mixed carbon comtent 3%, molten timesharing.Because gallium has Strong affinity for iron, gallium, which enters in molten iron, obtains efficiently concentrating.The rich gallium pig iron is former as the high-quality of next step iron, gallium separation and Extraction Material.The rate of recovery of rich gallium molten iron iron content 97.34%, 480g/t containing gallium, iron and gallium is respectively 97.00%, 95.31%.With implementation Example 4 compares, the metallized pellet performance that additive formula is identical and obtains closely when, in preferred scope, pass through It between molten point of temperature of reduction, increase mixed carbon comtent and the molten timesharing of extension, can also strengthen molten point of reaction, obtain molten point of very close effect Really.
Rich gallium molten iron casts positive plate by condensation, using stainless steel plate as negative electrode, is electrolysed in electrolytic cell.It is electrolysed bar Part is that electrolyte component is 45-55g/L FeSO4, 135-145g/L (NH4)2SO4, pH value 5.0, temperature 60 C, current density 100A/m2, tank voltage 1.0V and pole span 20mm.Iron powder is periodically peeled off from minus plate, gallium is sunk in the earth of positive pole, obtain containing gallium The 0.264% rich gallium earth of positive pole, gallium is extracted for next step.Iron powder Iron grade is 97.18%.Iron, the gallium rate of recovery are respectively 93.32% and 82.83%.Compared with embodiment 4, in the performance of molten iron containing gallium that additive formula is identical and obtains closely When, in preferred scope, by improving electrolyte temperature, reduction current density, tank voltage and pole span, also can strengthening electronic move Move, obtain close electrolysis effectiveness.
Embodiment 6
The iron vitriol slag aqueous 8.3% of drying, with addition of the multifunction additive that mass ratio is 7%, (mass ratio is nothing to iron vitriol slag Bituminous coal powder 40%, agstone 15%, dolomite 25%, sodium humate dry powder 5%, brown iron oxide 10%, carbonic acid sodium powder 5%), 1min (1200-1800rpm) is mixed in intensive mixer, 2min (profit mill moisture is 6-8%) is mixed in damp mill, fully Mix, then pelletizing is carried out in disc balling machine, prepare granularity for 8~16mm, aqueous 11.0% green-ball.Green-ball is fallen by force Spend for 6.8 times/0.5m, compression strength of green pel let 15.7N/.
Green-ball is on belt type roasting machine (green-ball bed depth be 110mm) by preheating at 300 DEG C of drys 6min, 1050 DEG C The 9min and oxidizing roasting 60min at 1300 DEG C, agglomerates residual sulfur content is 0.58%, and desulfurization degree reaches 98.9%, is calcined ball Group's compression strength is 2480N/.Compared with embodiment 3, additive formula it is identical and preheating and roasting condition in preferred model When enclosing interior, although green-ball is reduced to 250 DEG C in preheating section drying temperature, but still in the range of preheating optimal conditions, therefore Obtained greenball properties, agglomerates performance and desulfurized effect is substantially close.Difference is in additive that dolomite is matched Improve, content of magnesia increase, does not have substantially in preferred scope to greenball properties, agglomerates performance and desulfurized effect in pelletizing Have an impact.
The flue gas of belt type roasting machine pellet roasting desulfurization is gathered dust and desulfurization.The dust of removing returns to iron vitriol slag and dried Process.The SO that flue gas after dedusting is sprayed into the absorbing liquid absorption flue gas containing ammoniacal liquor2, it is passed through air oxidation SO2, generate sulfuric acid Ammonium.Absorbing liquid containing ammonia is 120L/m3 with flue gas volume ratio；The concentration of a hydration ammonia is 10g/L in the absorbing liquid containing ammonia.Flue gas Desulfurization degree is 98.65%, sulfur recovery rate 96.85%.Compared with embodiment 3, flue gas desulfurization condition is identical, obtained very close Desulfurization degree and sulfur recovery rate, show that preferred times sulphur condition is reliable, favorable reproducibility.
Temperature is directly entered rotary kiln for 1090 DEG C of red-hot pelletizing and reduced after desulfurization with roasting technique, add granularity for 5~ 25mm solid reductant bituminous coal, under conditions of 1100 DEG C of reduction temperature, recovery time 60min and carbon weight of iron ratio is 0.80 It is reduced directly, the metallization of pelletizing iron is 91.65%.Reclaimed by flue gas ash removal and obtain zinc-rich indium material, it contains zinc 59.96%, containing indium 0.0165%, zinc, indium recovery are respectively 96.89% and 85.12%.Compared with embodiment 3, in carbon irony Amount than it is identical when, extend the recovery time when reduction temperature is declined by a relatively large margin, degree of metalization, zinc, the indium recovery of pelletizing iron Decline respectively, but in suitable index.Therefore, dolomite proportioning is improved in additive, content of magnesia in pelletizing Increased amplitude is small on pelletizing direct-reduction influence in preferred scope, and obtained index meets the requirements.But, with embodiment 1 Compare, in relatively low reduction temperature, by increasing additive formula and improving the synergy of charcoal weight of iron ratio, pelletizing iron It is close that metallization brings up to zinc, indium recovery in 91.65%, zinc-rich indium material by 80.12%.
It is reduced directly material and carries out indirect water-cooling, dry type magnetic separation, obtains metallized pellet and nonmagnetics.Metallized pellet Into electric furnace, melted and slag sluicing system under the conditions of 60min between 1450 DEG C, mixed carbon comtent 3%, molten timesharing.Because gallium has Strong affinity for iron, gallium, which enters in molten iron, obtains efficiently concentrating.The rich gallium pig iron is former as the high-quality of next step iron, gallium separation and Extraction Material.The rate of recovery of rich gallium molten iron iron content 96.95%, 465g/t containing gallium, iron and gallium is respectively 96.96%, 95.03%.With implementation Example 3 compares, when mixed carbon comtent is identical, will be between molten point of temperature drop and the molten timesharing of extension, rich gallium molten iron iron content, containing gallium, iron and gallium The rate of recovery declined respectively, but in suitable index.Compared with embodiment 1, when molten point of temperature and time is identical, Although mixed carbon comtent is reduced to 3% by 5%, rich gallium molten iron iron content brings up to 96.95% by 96.34%, is carried containing gallium by 358g/t Height arrives 465g/t, and the rate of recovery of iron and gallium is respectively by bringing up to 95.68%, 92.17% raising 96.96%, 95.03%.Mainly Reason is, because additives ratio has brought up to 7% by 2%, to improve the slag making performance of agglomerates so that molten slitting part is obtained To being obviously improved.Therefore, dolomite proportioning is improved in additive, and the increased amplitude of content of magnesia is in preferred scope in pelletizing To reducting pellet, molten point serves obvious invigoration effect.Additive and the synergy of molten point system have highly important work With.
Rich gallium molten iron casts positive plate by condensation, using stainless steel plate as negative electrode, is electrolysed in electrolytic cell.It is electrolysed bar Part is that electrolyte component is 45-55g/L FeSO4, 135-145g/L (NH4)2SO4, pH value 4.0,40 DEG C of temperature, current density 100A/m2, tank voltage 2.5V and pole span 50mm.Iron powder is periodically peeled off from minus plate, gallium is sunk in the earth of positive pole, obtain big containing gallium In the 0.263% rich gallium earth of positive pole, gallium is extracted for next step.Iron powder Iron grade is 97.76%.Iron, the gallium rate of recovery are respectively 93.00% and 84.12%.
Comparative example 1
The binding agent of the additive not added in aqueous 8%, compound in the present invention, only addition 2% is arrived in iron vitriol slag drying Bentonite, is mixed by conventional mixer, is pre-processed without intensive mixer and damp mill, then directly in disc balling machine Interior carry out pelletizing, prepares granularity for 8~16mm, aqueous 10.0% green-ball.Shatter strength of green pellet is 3.3 times/0.5m, green-ball Compression strength 10.0N/.Green-ball is on belt type roasting machine by preheating 9min at 250 DEG C of dry 7min, 1050 DEG C and 1200 Oxidizing roasting 60min at DEG C, agglomerates residual sulfur content is 2.3%, and desulfurization degree is 88.7%, and agglomerates compression strength is 1980N/.When as can be seen here, without using the additive of the present invention, green ball strength, agglomerates intensity and sulfur-bearing figureofmerit are equal Do not reach requirement, it is strong using green ball strength during 2-7% additives, agglomerates far below in 1~embodiment of above-described embodiment 6 Degree and sulfur-bearing figureofmerit.
The flue gas of belt type roasting machine pellet roasting desulfurization is gathered dust and desulfurization.The dust of removing returns to iron vitriol slag and dried Process.The SO that flue gas after dedusting is sprayed into the absorbing liquid absorption flue gas containing ammoniacal liquor2, it is passed through air oxidation SO2, generate sulfuric acid Ammonium.Absorbing liquid containing ammonia is 60L/m3 with flue gas volume ratio；The concentration of a hydration ammonia is 9g/L in the absorbing liquid containing ammonia.Flue gas takes off Sulphur rate is 83.00%, sulfur recovery rate 58.9%.Compared with 1~embodiment of embodiment 6, absorbing liquid containing ammonia is with flue gas volume than low The concentration of a hydration ammonia is less than preferred scope 10-18g/L in preferred 70-120L/m3, ammonia absorbing liquid, causes in flue gas SO2Shorten with amino molecule time of contact, effective ingredient amino molecule content declines in ammonia absorbing liquid, flue gas desulphuization rate and sulfur recovery rate Significantly decline, desulfurized effect is deteriorated.In addition, the residual sulphur of pelletizing is high, SO few into the sulphur in flue gas2Concentration declines, sulfur recovery rate Corresponding reduction.
Temperature is directly entered rotary kiln for 960 DEG C of red-hot pelletizing and reduced after desulfurization with roasting technique, add granularity for 5~ 25mm solid reductant bituminous coal, under conditions of 1200 DEG C of reduction temperature, recovery time 60min and carbon weight of iron ratio is 0.60 It is reduced directly, the metallization of pelletizing iron is 91.12%.Reclaimed by flue gas ash removal and obtain zinc-rich indium material, it contains zinc 45.69%, containing indium 0.0089%, zinc, indium recovery are respectively 80.82% and 57.37%.Compare with 1~embodiment of embodiment 6 Compared with only with the addition of bentonite adhesive, although pelletizing preheating, roasting parameter are carried out in preferred scope, but due to nothing in pelletizing The additive of the present invention, the residual sulphur of agglomerates is up to 2.3%.Sulfate translates into sulfide in reduction process, and is formed Stable zinc sulphide, indium sulfide etc., so as to have a strong impact on the reduction and volatilization of zinc, indium.Therefore, cause zinc-rich indium material to contain, indium and Zinc, indium recovery are far below 1~embodiment of embodiment 6.
It is reduced directly material and carries out indirect water-cooling, dry type magnetic separation, obtains metallized pellet and nonmagnetics.Metallized pellet Into electric furnace, melted and slag sluicing system under the conditions of 30min between 1550 DEG C, mixed carbon comtent 3%, molten timesharing.Because gallium has Strong affinity for iron, gallium enters to be enriched with molten iron.The rich gallium pig iron is as next step iron, the raw material of gallium separation and Extraction.Rich gallium iron The rate of recovery of water iron content 92.10%, 180g/t containing gallium, iron and gallium is respectively 90.25%, 80.20%.With embodiment 1~implementation Example 6 compares, and only with the addition of bentonite adhesive, although the degree of metalization of reducting pellet (metallized pellet) reaches 91.12%, but Due to the presence of zinc sulphide, indium sulfide, although molten point is carried out under the preferred conditions, and without the addition using the present invention Agent, the poor fluidity of slag causes the rate of recovery of rich gallium molten iron iron content, amount containing gallium and iron and gallium to be far below embodiment 1~implementation Example 6.
Rich gallium molten iron casts positive plate by condensation, using stainless steel plate as negative electrode, is electrolysed in electrolytic cell.It is electrolysed bar Part is electrolyte ph 3.0, temperature 70 C, current density 100A/m2, tank voltage 0.5V and pole span 10mm.It is fixed from minus plate Phase peels off iron powder, and gallium is sunk in the earth of positive pole, obtains the rich gallium earth of positive pole containing gallium 0.186%, and gallium is extracted for next step.Iron powder iron Grade is 93.18%.Iron, the gallium rate of recovery are respectively 92.45% and 68.16%.Compared with 1~embodiment of embodiment 6, due to richness Gallium molten steel quality declines, and the Quality Down of positive plate is cast in condensation, adds electrolytic condition not in preferred scope, and iron powder quality becomes Difference, iron, the gallium rate of recovery decline.
Therefore, in this comparative example, without the additive of the present invention, full-range technical indicator is produced significantly not Profit influence.The additive of the present invention has multi-functional, be reinforcing pelletizing, pellet roasting desulfurization, pelletizing direct-reduction-molten point and The effective means of the electrolysis of the pig iron containing gallium, is a core technology.
Comparative example 2
Iron vitriol slag arrives the swelling of the additive not added in aqueous 9%, compound in the present invention, only addition 2% with drying Native binding agent, is mixed by conventional mixer, is pre-processed without intensive mixer and damp mill, then directly in disk pelletizing Pelletizing is carried out in machine, granularity is prepared for 8~16mm, aqueous 11.0% green-ball.Shatter strength of green pellet is 3.9 times/0.5m, raw Ball compression strength 9.2N/.Green-ball on belt type roasting machine by preheated at 250 DEG C of drys 7min, 1050 DEG C 9min and Oxidizing roasting 10min at 1200 DEG C, agglomerates residual sulfur content is 3.6%, and desulfurization degree reaches 72.9%, agglomerates compression strength For 1500N/.In the additive without the present invention, the pellet roasting time is contracted by the 20-60min of 1~embodiment of embodiment 6 It is short to 10min, agglomerates residual sulfur content less than 1% by being steeply risen as 3.6%, and desulfurization degree is dropped to by more than 92% 72.9%, agglomerates intensity will produce unfavorable shadow by dropping to 1500N/ higher than 2500N/ to follow-up reduction process Ring.
The flue gas of belt type roasting machine pellet roasting desulfurization is gathered dust and desulfurization.The dust of removing returns to iron vitriol slag and dried Process.The SO that flue gas after dedusting is sprayed into the absorbing liquid absorption flue gas containing ammoniacal liquor2, it is passed through air oxidation SO2, generate sulfuric acid Ammonium.Absorbing liquid containing ammonia is 130L/m with flue gas volume ratio3；The concentration of a hydration ammonia is 10g/L in the absorbing liquid containing ammonia.Flue gas Desulfurization degree is 96.36%, sulfur recovery rate 94.52%.Compared with embodiment 1, absorbing liquid containing ammonia is with flue gas volume ratio beyond preferred Scope, but flue gas desulphuization rate and sulfur recovery rate are substantially at stable state, no longer as absorbing liquid containing ammonia and flue gas volume are than increasing Raise greatly.It is primarily due in flue gas flow and containing SO2The timing of concentration one, the total quantity of amino molecule needed for desulphurization reaction is Certain.When the concentration of a hydration ammonia is 10g/L in absorbing liquid containing ammonia, corresponding absorbing liquid containing ammonia compares the upper limit with flue gas volume For 120L/m3.When absorbing liquid containing ammonia and flue gas volume ratio are higher than this value, the total quantity of the amino molecule of physical presence is high in system In the total quantity of the amino molecule needed for desulphurization reaction, the escape of ammonia is easily caused, the waste and desulphurization cost rise of ammonia is caused, and Bring secondary pollution.
Temperature is directly entered rotary kiln for 890 DEG C of red-hot pelletizing and reduced after desulfurization with roasting technique, add granularity for 5~ 25mm solid reductant bituminous coal, under conditions of 1200 DEG C of reduction temperature, recovery time 40min and carbon weight of iron ratio is 0.80 It is reduced directly, the metallization of pelletizing iron is 92.68%.Reclaimed by flue gas ash removal and obtain zinc-rich indium material, it contains zinc 42.21%, containing indium 0.0079%, zinc, indium recovery are respectively 76.89% and 49.79%.Compare with 1~embodiment of embodiment 6 Compared with only with the addition of bentonite adhesive, although direct-reduction parameter is still in preferred scope, and the degree of metalization of reducting pellet reaches To 92.68%, but due to additive-free reinforcing desulfurization with roasting technique, agglomerates are significantly raised containing residual sulfur content, far above requiring Standard less than 1%, cause a large amount of zinc and indium in reducting pellet to be stabilized with zinc sulphide, indium sulfide, is unfavorable for zinc, indium Reduction and volatilization, so as to cause zinc-rich indium material zinc, indium content and zinc, indium recovery significantly to decline, far below embodiment 1~reality Apply example 6.
It is reduced directly material and carries out indirect water-cooling, dry type magnetic separation, obtains metallized pellet and nonmagnetics.Metallized pellet Into electric furnace, melted and slag sluicing system under the conditions of 60min between 1550 DEG C, mixed carbon comtent 3%, molten timesharing.Because gallium has Strong affinity for iron, gallium enters to be enriched with molten iron.The rich gallium pig iron is as next step iron, the quality raw materials of gallium separation and Extraction.It is rich The rate of recovery of gallium molten iron iron content 89.56%, 189g/t containing gallium, iron and gallium is respectively 86.55%, 76.30%.Although molten point excellent Carried out under conditions of choosing, due to without the additive using the present invention, the slag stream for causing reducting pellet to be formed during molten point Dynamic property is poor, causes the rate of recovery of rich gallium molten iron iron content, amount containing gallium and iron and gallium to be far below 1~embodiment of embodiment 6, while Significantly lower than comparative example 1.Thus enter one relate to show agglomerates sulfur content to pelletizing reduce in zinc, the reduction of indium and volatilization have Material impact, so as to have a strong impact on iron ectopic pregnancy and zinc, the separating effect of indium.Therefore, it is necessary to strictly control agglomerates sulfur-bearing Amount is less than 1%.
Rich gallium molten iron casts positive plate by condensation, using stainless steel plate as negative electrode, is electrolysed in electrolytic cell.It is electrolysed bar Part is electrolyte ph 3.0, temperature 70 C, current density 400A/m2, tank voltage 3.0V and pole span 10mm.It is fixed from minus plate Phase peels off iron powder, and gallium is sunk in the earth of positive pole, obtains the rich gallium earth of positive pole containing gallium 0.135%, and gallium is extracted for next step.Iron powder iron Grade is 91.53%.Iron, the gallium rate of recovery are respectively 89.75% and 64.26%.Contrasted with 1~embodiment of embodiment 6, though Right electrolyte, temperature and current density, tank voltage are in preferred scope, but pole span only 10mm, not in preferred scope.Due to pole Away from too small, short the time required to metal cation migration, fast in negative electrode deposition velocity, the foreign ion being mingled with increases, and causes iron powder Grade and iron, the gallium rate of recovery decline, far below 1~embodiment of embodiment 6.Further, since additive is not added, agglomerates Residual sulfur content is too high, causes the Iron grade of molten iron containing gallium to decline, impurity content rises, this is also influence electrolytic iron powder grade and iron, gallium The key factor of the rate of recovery.
Comparative example 3
The iron vitriol slag aqueous 8.3% of drying, with addition of the multifunction additive that mass ratio is 5%, (mass ratio is stone to iron vitriol slag Limestone flour 40%, coke powder 5%, dolomite 25%, sodium humate dry powder 10%, brown iron oxide 10%, carbonic acid sodium powder 10%), 1min is mixed in intensive mixer, 2min is mixed in damp mill, then compound is subjected to pelletizing in disc balling machine, is being made Under conditions of ball moisture 10%, Balling time 12min, prepare granularity be 8~16mm green-ball, drop strength be 5.4 times/ 0.5m, compression strength of green pel let 15.2N/.
Green-ball cloth is on belt type roasting machine, and first using agglomerates as grate-layer material in belt machine trolley, bed material thickness is fixed For 30mm, then green-ball is layered on bed material, the thickness of feed layer of green-ball is 80mm, and green-ball is done on belt type roasting machine by 300 DEG C Dry 6min, the 9min and oxidizing roasting 60min at 1250 DEG C is preheated at 1050 DEG C, agglomerates residual sulfur content is 1.82%, desulfurization Rate reaches 71.8%, and agglomerates compression strength is 1830N/.With embodiment 4 it was found that, it is multi-functional in this comparative example to add Plus dosage of coke only 5% in agent, far below optimum ratio value scope 15-30%, under the premise of other condition identicals, green-ball is strong Degree is substantially close, and the reduction of dosage of coke influences smaller to green ball strength, but mainly influence pellet roasting desulfurization and consolidation.This Agglomerates residual sulfur content rises to 1.82% by 0.38% in comparative example, and desulfurization degree drops to 71.8%, agglomerates by 99% Compression strength drops to 1830N/ by 2630N/.Therefore, carbonaceous fuel is one of essential dispensing in additive.
Because residual sulfur content significantly rises in agglomerates, the matter of-molten point and electrolytic iron powder will be reduced directly to pelletizing Figureofmerit and the rate of recovery produce obvious adverse effect.
Comparative example 4
The iron vitriol slag aqueous 8.3% of drying, with addition of the multifunction additive that mass ratio is 5%, (mass ratio is stone to iron vitriol slag Limestone flour 40%, semi-coke powder 25%, dolomite 15%, sodium humate dry powder 0%, brown iron oxide 10%, carbonic acid sodium powder 10%), 1min is mixed in intensive mixer, 2min is mixed in damp mill, is fully mixed, then compound is entered in disc balling machine Row pelletizing, under conditions of pelletizing moisture 10%, Balling time 12min, prepares the green-ball that granularity is 8~16mm, falls strong Spend for 3.0 times/0.5m, compression strength of green pel let 9.3N/.Green-ball cloth is on belt type roasting machine, first to roast in belt machine trolley Burning pelletizing is grate-layer material, and bed material thickness is fixed as 30mm, then green-ball is layered on bed material, and the thickness of feed layer of green-ball is 80mm, raw Ball on belt type roasting machine by the preheating 9min and oxidizing roasting 60min at 1250 DEG C at 300 DEG C of drys 6min, 1050 DEG C, Agglomerates residual sulfur content is 0.62%, and desulfurization degree reaches 97.67%, and agglomerates compression strength is 2000N/.
With embodiment 3 it was found that, it is multi-functional in this comparative example under the premise of multifunction additive addition identical The other 5 kinds of compositions of additive are in optimized scope, and simply without sodium humate dry powder, drop strength is under 7.3 times/0.5m 3.0 times/0.5m is dropped to, compression strength of green pel let drops to 9.3N/ by 15.0N/, and agglomerates compression strength is by 2500N/ Drop to 1900N/, pellet roasting desulfurization degree drops to 97.67% by 98.3%, due to no addition binding agent, cause life Ball intensity and agglomerates intensity can not meet requirement.Sodium humate dry powder, which is mainly, plays binding agent, not only improves life Ball intensity, and improve the heat endurance of green-ball.The raising of green-ball heat endurance is conducive to improving agglomerates intensity, reduces roasting Burn the risk of efflorescence and ring formation in pelletizing direct-reduction.Comparing result shows that sodium humate starchy binder is essential Composition.But proportioning is too high, and pelletizing compound viscosity is excessive, production operation is difficult, and production cost also significantly rises.
Comparative example 5
The iron vitriol slag aqueous 8.3% of drying, with addition of the multifunction additive that mass ratio is 5%, (mass ratio is stone to iron vitriol slag Limestone flour 40%, semi-coke powder 25%, dolomite 15%, sodium humate dry powder 10%, brown iron oxide 10%, carbonic acid sodium powder 0%), 1min is mixed in intensive mixer, 2min is mixed in damp mill, is fully mixed, then compound is entered in disc balling machine Row pelletizing, under conditions of pelletizing moisture 10%, Balling time 12min, prepares the green-ball that granularity is 8~16mm, falls strong Spend for 5.1 times/0.5m, compression strength of green pel let 14.2N/.Green-ball cloth is on belt type roasting machine, first to roast in belt machine trolley Burning pelletizing is grate-layer material, and bed material thickness is fixed as 30mm, then green-ball is layered on bed material, and the thickness of feed layer of green-ball is 80mm, raw Ball on belt type roasting machine by the preheating 5min and oxidizing roasting 20min at 1300 DEG C at 300 DEG C of drys 6min, 1100 DEG C, Agglomerates residual sulfur content is 0.50%, and desulfurization degree reaches 98.1%, and agglomerates compression strength is 2480N/.
Temperature is directly entered rotary kiln for 1100 DEG C of red-hot pelletizing and reduced after desulfurization with roasting technique, add granularity for 5~ 25mm solid reductant bituminous coal, under conditions of 1250 DEG C of reduction temperature, recovery time 30min and carbon weight of iron ratio is 0.60 It is reduced directly, the metallization of pelletizing iron is 89.21%.Reclaimed by flue gas ash removal and obtain zinc-rich indium material, it contains zinc 55.33%, containing indium 0.0132%, zinc, indium recovery are respectively 89.20% and 78.98%.
Contrast and invent with embodiment 4, in multifunction additive with the premise of being 5%, do not add carbon in this comparative example Sour sodium powder, other compositions are in preferred scope, shatter strength of green pellet, compression strength and agglomerates compression strength, residual sulphur Amount and desulfurization degree index have declined, but can meet manufacturing technique requirent.The influence of sodium carbonate, which is mainly, to be embodied in direct The promotion of reduction.Due to not adding sodium carbonate in this comparative example, although direct-reduction condition is in preferred scope, pelletizing The metallization of iron drops to 89.21% by 94.86%, and zinc-rich indium material zinc, indium recovery are respectively under 97.00% and 86.11% Drop to 89.20% and 78.98%.Therefore, sodium carbonate is the essential composition of multifunction additive.
Comparative example 6
The iron vitriol slag aqueous 8.0% of drying, with addition of the multifunction additive that mass ratio is 5%, (mass ratio is semi-coke powder 30%, agstone 40%, dolomite dust 0%, sodium humate dry powder 10%, brown iron oxide 10%, carbonic acid sodium powder 10%), 1min is mixed in intensive mixer, 2min is mixed in damp mill, is fully mixed, then pelletizing is carried out in disc balling machine, is made It is 8~16mm, aqueous 10.5% green-ball for granularity is gone out.Shatter strength of green pellet is 5.6 times/0.5m, compression strength of green pel let 15.3N/.Green-ball is aoxidized by preheating 8min at 350 DEG C of dry 5min, 850 DEG C on belt type roasting machine and at 1200 DEG C 60min is calcined, agglomerates residual sulfur content is 0.43%, desulfurization degree reaches 98.95%, and agglomerates compression strength is 2592N/ It is individual.
Temperature is directly entered rotary kiln for 1100 DEG C of red-hot pelletizing and reduced after desulfurization with roasting technique, add granularity for 5~ 25mm solid reductant bituminous coal, under conditions of 1250 DEG C of reduction temperature, recovery time 30min and carbon weight of iron ratio is 0.60 It is reduced directly, the metallization of pelletizing iron is 95.00%.Reclaimed by flue gas ash removal and obtain zinc-rich indium material, it contains zinc 60.77%, containing indium 0.0179%, zinc, indium recovery are respectively 96.20% and 85.41%.
It is reduced directly material and carries out indirect water-cooling, dry type magnetic separation, obtains metallized pellet and nonmagnetics.Metallized pellet Into electric furnace, melted and slag sluicing system under the conditions of 20min between 1550 DEG C, mixed carbon comtent 1%, molten timesharing.Because gallium has Strong affinity for iron, gallium, which enters in molten iron, obtains efficiently concentrating.The rich gallium pig iron is former as the high-quality of next step iron, gallium separation and Extraction Material.The rate of recovery of rich gallium molten iron iron content 93.32%, 310g/t containing gallium, iron and gallium is respectively 92.53%, 83.68%.
With embodiment 4 it was found that, in the other 6 kinds of compositions of multifunction additive in suitable ratio range, do not throw Plus dolomite, on the premise of multifunction additive addition is 5%, shatter strength of green pellet, compression strength, agglomerates resist Compressive Strength and desulfurization degree are close, without significant difference.But, reducting pellet fusing is had a significant effect, rich gallium molten iron iron content Drop to 93.32% by 97.45%, 310g/t dropped to by 490g/t containing gallium, the rate of recovery of iron and gallium respectively by 96.89%, 96.58% is reduced to 92.53%, 83.68%.
Dolomite Main Ingredients and Appearance is CaMg (CO3)2(roasting process changes into magnesia and calcium oxide), adds energy in pelletizing Change the basicity and content of magnesia of slag, so that improve the mobility of slag, the separation of reinforcing iron and slag.It is no in this comparative example to add Enter dolomite, cause slag sluicing system effect to be substantially deteriorated, melt timesharing molten iron grade, gallium content and iron, gallium rate of recovery index bright It is aobvious to decline.Therefore, the dolomite containing magnesium is to strengthen molten point of essential composition of reducting pellet.
Comparative example 7
The iron vitriol slag aqueous 8.3% of drying, with addition of the multifunction additive that mass ratio is 7%, (mass ratio is nothing to iron vitriol slag Bituminous coal powder 40%, agstone 5%, dolomite 25%, sodium humate dry powder 10%, brown iron oxide 10%, carbonic acid sodium powder 10%) 1min, is mixed in intensive mixer, 2min is mixed in damp mill, is fully mixed, then is carried out in disc balling machine Pelletizing, prepares granularity for 8~16mm, aqueous 11.0% green-ball.Shatter strength of green pellet is 6.7 times/0.5m, green-ball pressure resistance Spend 15.5N/.Green-ball is on belt type roasting machine by preheating 9min and the oxygen at 1300 DEG C at 300 DEG C of dry 6min, 1050 DEG C Change roasting 60min, agglomerates residual sulfur content is 0.59%, desulfurization degree reaches 98.7%, and agglomerates compression strength is 2500N/ It is individual.
Temperature is directly entered rotary kiln for 1090 DEG C of red-hot pelletizing and reduced after desulfurization with roasting technique, add granularity for 5~ 25mm solid reductant bituminous coal, under conditions of 1100 DEG C of reduction temperature, recovery time 60min and carbon weight of iron ratio is 0.80 It is reduced directly, the metallization of pelletizing iron is 89.97%.Reclaimed by flue gas ash removal and obtain zinc-rich indium material, it contains zinc 60.16%, containing indium 0.0169%, zinc, indium recovery are respectively 96.95% and 85.67%.
It is reduced directly material and carries out indirect water-cooling, dry type magnetic separation, obtains metallized pellet and nonmagnetics.Metallized pellet Into electric furnace, melted and slag sluicing system under the conditions of 60min between 1450 DEG C, mixed carbon comtent 3%, molten timesharing.Because gallium has Strong affinity for iron, gallium, which enters in molten iron, obtains efficiently concentrating.The rich gallium pig iron is former as the high-quality of next step iron, gallium separation and Extraction Material.The rate of recovery of rich gallium molten iron iron content 93.26%, 390g/t containing gallium, iron and gallium is respectively 93.49%, 87.03%.
Contrast and find with embodiment 6, on the premise of multifunction additive is 7% with addition of mass ratio, lime in additive Stone flour proportioning is reduced to 5% by 15%, and other 5 kinds of compositions are in preferred scope, shatter strength of green pellet, compression strength, roasting Pelletizing residual sulfur content, desulfurization degree and agglomerates compression strength index very close to, show when other compositions are in preferred scope, Lime stone influences unobvious with green-ball, agglomerates are compared.But, to agglomerates direct-reduction and reducting pellet, molten point has Significantly affect, because agstone proportioning is far below preferred scope, the metallization of pelletizing iron drops to 89.97% by 91.65%. Rich gallium molten iron iron content drops to 93.26% by 96.95%, drops to 390g/t, iron and the gallium rate of recovery point by 465g/t containing gallium Not be reduced to 93.49%, 87.03% by 96.96%, 95.03%.
Lime stone Main Ingredients and Appearance is calcium carbonate (roasting process changes into calcium oxide), can adjust the basicity of pelletizing, is improved Pelletizing reproducibility, improves pelletizing degree of metalization, improves reducting pellet and melts the mobility of timesharing slag, thus strengthen separation with slag and The recovery of iron, gallium.In this comparative example due to lime stone match it is relatively low, its invigoration effect is limited, thus cause pelletizing degree of metalization, The index such as iron quality and iron, the gallium rate of recovery is decreased obviously.
Comparative example 8
The iron vitriol slag aqueous 8.3% of drying, with addition of the multifunction additive that mass ratio is 5%, (mass ratio is burnt to iron vitriol slag Powder 30%, agstone 25%, dolomite dust 15%, sodium humate dry powder 10%, brown iron oxide 10%, carbonic acid sodium powder 10%), 1min (1200-1800rpm) is mixed in intensive mixer, 2min (profit mill moisture is 6-8%) is mixed in damp mill, fully Mix, then pelletizing is carried out in disc balling machine, prepare granularity for 8~16mm, aqueous 10.5% green-ball.Green-ball is fallen by force Spend for 5.4 times/0.5m, compression strength of green pel let 15.3N/.
Green-ball cloth is on belt type roasting machine, and first using agglomerates as grate-layer material in belt machine trolley, bed material thickness is fixed For 30mm, then green-ball is layered on bed material, the thickness of feed layer of green-ball is 60mm, and green-ball is done on belt type roasting machine by 300 DEG C Dry 6min, the 5min and oxidizing roasting 20min at 1300 DEG C is preheated at 1100 DEG C, agglomerates residual sulfur content is 1.10%, desulfurization Rate reaches 89.3%, and agglomerates compression strength is 1880N/.
Contrast and invent with embodiment 4, in multifunction additive with the premise of being 5%, green-ball is fallen in this comparative example Intensity, compression strength index are substantially close, but agglomerates compression strength and ball fractionating column residual sulfur content, desulfurization degree significantly under Drop, it is impossible to meet subsequent production technological requirement.Main cause is that green-ball bed depth is reduced to 60mm by 90mm, and the green-ball bed of material is too Thin, accumulation of heat effect is poor, and high temperature hold time is short, and the consolidation of ferriferous oxide, causes pelletizing in the decomposition of influence sulfate and pelletizing Intensity and desulfurization degree decline.
Due to the rise that caused agglomerates residual sulfur content is thinned and the decline of pelletizing compression strength of the green-ball bed of material, it will Zinc, the volatilization of indium and the separation of iron gallium bring adverse effect in being reduced to follow-up pelletizing.
Comparative example 9
The iron vitriol slag aqueous 8.3% of drying, with addition of the multifunction additive that mass ratio is 5%, (mass ratio is burnt to iron vitriol slag Powder 30%, agstone 25%, dolomite dust 15%, sodium humate dry powder 10%, brown iron oxide 10%, carbonic acid sodium powder 10%), 1min (1200-1800rpm) is mixed in intensive mixer, 2min (profit mill moisture is 6-8%) is mixed in damp mill, fully Mix, then pelletizing is carried out in disc balling machine, prepare granularity for 8~16mm, aqueous 10.6% green-ball.Green-ball is fallen by force Spend for 5.5 times/0.5m, compression strength of green pel let 15.2N/.
Green-ball cloth is on belt type roasting machine, and first using agglomerates as grate-layer material in belt machine trolley, bed material thickness is fixed For 30mm, then green-ball is layered on bed material, the thickness of feed layer of green-ball is 120mm, and green-ball is done on belt type roasting machine by 300 DEG C Dry 6min, the 5min and oxidizing roasting 20min at 1300 DEG C is preheated at 1100 DEG C, agglomerates residual sulfur content is 1.03%, desulfurization Rate reaches 89.8%, and agglomerates compression strength is 1910N/.
Invented with embodiment 4 and the contrast of comparative example 8, on the premise of multifunction additive is matched somebody with somebody and is 5%, in this comparative example Shatter strength of green pellet, compression strength index are substantially close, but agglomerates compression strength and ball point residual sulfur content, desulfurization degree are significantly Decline, it is impossible to meet subsequent production technological requirement.Main cause is that green-ball bed depth increases to 120mm, green-ball material by 90mm Layer is too thick, in belt type roasting machine drying process, because green-ball crystal water content is high, easily will produce serious mistake in material layer lower part Wet, green-ball is deformed or even bonded, and influences bed of material gas, the consolidation of ferriferous oxide in the decomposition of influence sulfate and pelletizing, Pellet strength and desulfurization degree is caused to decline.Therefore so that suitable green-ball thickness of feed layer should be controlled in 90-110mm.

Claims (10)

1. a kind of reclaim zinc, indium, iron, the method for gallium from iron vitriol slag, it is characterised in that comprises the following steps：
Step (1)：Pelletizing：
Iron vitriol slag is obtained into green-ball with additive mixing, again through profit mill, pelletizing；
Described additive includes the component of following parts by weight：
Described alkaline earth metal source is the oxide of alkaline-earth metal, and/or changes into the salt of the alkaline earth oxide；
Alkali metal source is the oxide of alkali metal, and/or changes into the salt of alkali metal oxide；
Step (2)：Desulfurization：
By the oxidizing roasting at 1150~1300 DEG C after green-ball drying, preheating made from step (1), desulfurization pelletizing, oxidation roasting are obtained The flue gas of burning is used to reclaim sulphur；
Step (3)：Direct-reduction：
Desulfurization pelletizing made from step (2) is incorporated reducing agent, direct reduction reactor is carried out at 1100~1250 DEG C；Reduction is anti- The furnace charge answered obtains metallized pellet through cooling, magnetic separation；Reduction reaction flue gas dust collection is used to extract zinc, indium；
Step (4)：Molten point：
The metallized pellet that step (3) is obtained melts, slag-liquid separation obtains rich gallium molten iron.
2. zinc, indium, iron, the method for gallium are reclaimed from iron vitriol slag as claimed in claim 1, it is characterised in that in step (1), Described alkaline earth metal source includes calcium source and magnesium source；Described calcium source is calcium oxide and/or can change into the salt of calcium oxide；
Described magnesium source is magnesium oxide and/or can change into the salt of magnesium oxide；
Calcium source and the weight in magnesium source ratio are 15~40: 10-25.
3. zinc, indium, iron, the method for gallium are reclaimed from iron vitriol slag as described in any one of claim 1~2, it is characterised in that institute The alkaline earth metal source stated is calcium carbonate and magnesium carbonate；Or the ore that main component is calcium carbonate and/or magnesium carbonate；
The carbonate of described alkali metal source is sodium carbonate and/or potassium carbonate；
Described carbonaceous fuel and reducing agent is independently chosen from least one of semi-coke powder, coke powder, anthracite；
Described organic binder bond is at least one of sodium humate, polyacrylamide, carboxymethyl cellulose.
4. zinc, indium, iron, the method for gallium are reclaimed from iron vitriol slag as claimed in claim 3, it is characterised in that described addition Agent includes the component of following parts by weight：
5. zinc, indium, the method for iron gallium are reclaimed from iron vitriol slag as described in any one of Claims 1 to 4, it is characterised in that step Suddenly in (1), additive add weight be iron vitriol slag 2~7wt%；Control the water content of described iron vitriol slag for 7~ 9wt%；The speed of agitator of blending process is 1200-1800rpm, mixing time 60-90 seconds；When profit mill moisture is 6-8%, profit mill Between 2-4min.
6. zinc, indium, iron, the method for gallium are reclaimed from iron vitriol slag as described in any one of Claims 1 to 5, it is characterised in that step Suddenly in (2), green-ball is laid on belt type roasting machine, is dried, preheats, the bed depth 70- of oxidizing roasting, wherein green-ball 110mm。
7. zinc, indium, iron, the method for gallium are reclaimed from iron vitriol slag as claimed in claim 6, it is characterised in that in step (2), 3~6min is dried at 250~450 DEG C；5~10min of the pre-heat treatment at 650~1100 DEG C is warming up to after drying again；Oxidation roasting The time of burning is 20~80min.
8. zinc, indium, iron, the method for gallium are reclaimed from iron vitriol slag as claimed in claim 7, it is characterised in that in step (2), Obtained desulfurization pelletizing sulfur-bearing control is below 1.0%, and pelletizing compression strength is more than 2000N/.
9. zinc, indium, iron, the method for gallium are reclaimed from iron vitriol slag as claimed in claim 1, it is characterised in that
In step (3), the granularity of described reducing agent is 5~30mm；Iron in carbon and agglomerates in the reducing agent of supplying Mass ratio is 0.50~0.80；The reduction reaction time is 30~90min.
10. zinc, indium, iron, the method for gallium are reclaimed from iron vitriol slag as claimed in claim 1, it is characterised in that in step (4), The metallized pellet supplying reduction carbon materials obtained to magnetic separation, carry out melt processed；Described reduction carbon materials are anthracite and/or Jiao Charcoal；
The quality proportioning that molten point temperature is 1450-1550 DEG C, reduce carbon materials is 1-5%, and it is 20-60min to melt between timesharing.
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