CN104911356B - A kind of solid waste gas ash, the comprehensive recycling process of vanadium slag containing zinc-iron - Google Patents
A kind of solid waste gas ash, the comprehensive recycling process of vanadium slag containing zinc-iron Download PDFInfo
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Abstract
The present invention provides the technique that a kind of solid waste gas ash, slag for comprehensive containing bianchite are reclaimed.It utilizes the advantage that gas ash iron content is low, carbon is more than needed, had complementary advantages with reference to the characteristics of iron vitriol slag iron content is high, rare precious metal is enriched with, synthetical recovery is carried out to the material using ripe rotary kiln pyrogenic process fuming beneficiation technologies, it is equipped with the sophisticated equipments such as waste heat boiler, negative pressure bagroom, Pneumatic emulsifying desulfurizing tower to handle flue gas high efficiente callback and harmless environmental protection, reaches the purpose of clean manufacturing；And with beneficiation combined method technology to iron content kiln slag carry out high added value exploitation, not only solve resource disposal the difficult problem of environmental protection, also reached low energy consumption, in high yield, high added value comprehensive utilization effect.The technology of the present invention can solve the problem that in iron vitriol slag processing procedure short kiln age, high energy consumption, low concentration SO2The problem of harm, the problem for selecting that iron effect is poor, the secondary fluorine-containing chlorine of ZnO is too high in gas ash removal process can be also eliminated, with good economic benefit and higher popularization, practical value.
Description
Technical field
The invention belongs to metallurgical process secondary resource recycling field, be related to it is a kind of using cleaning pyrogenic process beneficiation technologies from low
Comprehensively recovering valuable metal in grade solid waste containing zinc slag, and carry out the technical process of harmless treatment, more particularly to it is a kind of from watt
The comprehensive metallurgical method for extracting non-ferrous metal in this mud (ash), vanadium slag containing zinc-iron.
Technical background
China is the first in the world big steel country, and production capacity accounts for more than the 60% of the whole world.Steel industry can all be produced greatly every year
The metallurgical dust of amount, and the solid wastes such as dirt, gravitational dust, converter ash, iron scale, grain slag, the slag overwhelming majority is sintered in steel
Effectively reclaimed and utilized in iron enterprise, blast furnace ironmaking gas ash (mud) because its complicated component is changeable, containing more lead,
Easily it is enriched with the heavy metals, and removal process such as zinc and significant damage is caused to blast furnace operation, product quality, turns into all the time
Restrict the great difficult problem of steel industry development.About 800~10,000,000 tons of the gas ash (mud) of the annual output of Iron and Steel Enterprises in China, this
A little solid wastes generally take directly outer row to store up, circulation is returned on a small quantity, send cement plant, brick field to do at the mode of dispensing
Reason, these Disposal Measures not only occupy a large amount of soils, also result in larger resource value and waste, easily to society and environment band
Carry out more serious heavy metal pollution burden, policy and wish that country recycles to regenerated resources are run counter to completely.
Mainly there are two major classes the country to gas ash treatment technology at present：That is rotary hearth furnace method and rotary kiln reduction volatilization technique.
Rotary hearth furnace method using domestic sunshine iron and steel enterprise as representative (Introduced from Japan Nippon Steel Corp technology), the technology be by blast furnace ironmaking and
Fume from steel making, iron ore concentrate, carbon dust, binding agent mixed pelletizing, are placed in rotary hearth furnace after drying, external heat makes Pb, Zn volatilization, collected,
Iron, which is reduced into after metallized pellet, simultaneously can be directly added into blast furnace utilization.The advantage of the technique is that material component utilizes relatively conjunction
Reason；Have the disadvantage also to contain higher impurity inside the metal pelletizing after processing, and can not individually handle gas ash, equipment investment and
Maintenance cost is higher.And rotary kiln reduction volatilization technique is then more universal, it makes full use of gas ash to contain the characteristics of remaining carbon is high, leads to
The a small amount of outer carbon measure of addition is crossed, progress high temperature reduction reaction in kiln will be added directly into after its simple dispensing, granulation.The technique
Advantage is that equipment is simple, and maintenance cost is low, and adaptability to raw material is strong；Shortcoming makes that equipment utilization efficiency of heat energy is low, and reducing atmosphere is weak.
China is lead-zinc production big country, with the fast development of lead zinc industry, and domestic zinc abstraction production capacity breaks through for continuous 3 years
5000000 tons.In recent years, with the aggravation of the nervous situation of global zinc ore resource, high temperature peracid jarosite process turns into place
The effective ways of the low zinc resource of high ferro are managed, the technology is because adaptability to raw material is strong, metal recovery rate is high, energy consumption is low, by state
Inside and outside more than 90% big-and-middle-sized zinc abstraction enterprise uses, and is increasingly becoming industry leading technology flow.Jarosite technology with often
Though advising wet processing and comparing has clear advantage, big there is also the leaching quantity of slag, iron content is low, and stability is poor, store up it is rear because
Attached heavy metal ion dissolution, seepage easily cause the deficiencies such as secondary pollution, and particularly it need to separately build Special slag, cause enterprise to pay
The environmentally friendly cost gone out is too high, has been increasingly becoming the important problem of influence enterprise development and economic benefit.
The disposal of iron vitriol slag is limited only to carry out harmless curing process and synthetical recovery non-ferrous metal in current zinc industry
Aspect, the effect for effective value of fully exploiting natural resources is poor, and its main recovery method is：Pyrogenic process solidification enrichment and wet method are integrated
Reclaim.Pyrogenic process solidification beneficiation technologies are mainly using high-temperature sintering process, reduction roasting-magnetic method as representative, and such technology is to pass through
The fuel such as additional Jiao, coal make alum slag obtain hot setting while fuming concentration of valuable metals, so as to reach innoxious store up
Characteristic, although this method solves the problems, such as to store up harm while enrichment, removal process energy consumption is larger, and cost is high, easily
Produce low concentration SO2Smoke pollution, the value of Efficient Development iron and rare precious metal is not fully demonstrated from slag.Iron vitriol slag wet method
Comprehensive Recovery Technology is, by using acid, base reagent and special activation process, to reach Selectively leaching, the purpose of separation, make slag
Valuable metal is efficiently separated and extracted, and reduces the Heavy Metal Pollution of slag；Although the recent years are dashed forward
Broken and application, but because its technological process is long, process control is cumbersome, and the toxicity to slag is not eliminated thoroughly, and noble metal selects smelting
Separating effect is low, and spent process water also needs to carry out environment protection standard processing, so as to constrain the process of industrialization technology exploitation, causes it
Economic benefit fails to fully demonstrate.
In recent years, as the whole world is to resource, the enhancing of environmental protection consciousness, the Chinese government also strengthens heavy metal pollution
The great attention of problem, heavy metal will be strengthened by promulgating and having put into effect successively a series of policies, regulation and file, and give strict orders enterprise
The preventing and controlling of pollution；Following national environmental protection policy will more strict and refinement, the technology not only disposed to jarosite waste residue
It is required that harsher and severe；Also the management of gas ash (mud) can be formally included in dangerous waste category simultaneously, caused at enterprise's waste residue
Being set to this will significantly rise, and seriously restriction production capacity and benefit lifting.In addition,《Long-term scientific and technological development rule in country
Draw outline》(2006~the year two thousand twenty) will " exploitation abnormal pollution control technology, the application technology as the second resource such as discarded object, weight
Industry clean manufacture integration technology is polluted, the show-how pattern developed a circular economy is set up " it is classified as and first develops theme；《Have
Non-ferrous metal industry medium ＆ long term sci-tech development program》(2006~the year two thousand twenty) also will " exploitation steel flue dust, the recovery of slag containing bianchite
Zinc, lead technology " is classified as important subject.Therefore, strengthen and promote to metallurgical row using synthesis, advanced, practical new technology
The reasonable disposal of industry solid waste (gas ash, iron vitriol slag), day is aobvious urgent and important；The utilization of secondary metal resource is not only solved simultaneously
Determine ample resources needs of problems, and be also the important feature measure of energy-saving and emission-reduction, will be that national " 12 " emphasis is helped
Hold strategic new industry.
In terms of 6.3 hundred million tons of steel are produced per year by China, annual steel industry is by more than nearly 800 ten thousand tons of output gas ash (mud), by per ton
Environmental protection disposal take 40 yuan and, the national processing cost paid every year will be more than 3.2 hundred million yuan.If these gas ash obtain integrating back
Receive that (composition is：Fe30%, C25%, Zn10%, comprehensive recovery is based on 85%), then the economic benefit produced will be more than 17,000,000,000
Member, the reduced iron powder and rare metal (such as In, Ga, Te) of high added value is extracted according to new technology, then direct economic benefit
Will be more than 20,000,000,000 yuan.
If by domestic 5,000,000 tons of calculating of zinc yield at present, every year by more than about 2,500,000 tons of output ferrovanadium slag, by slag per ton
Build and environmental protection disposal takes 60 yuan of meters, enterprise is every year by the environmentally friendly cost of 1.5 hundred million yuan of supplementary payments.As these iron vitriol slags are obtained
Recycle (slag ingredient：Zn6%, Fe32%, In, Ge, Cd, Pb0.8%, comprehensive recovery is based on 90%), then what is produced is straight
Connecing economic benefit will be more than 500,000,000 yuan, if considering, rare precious metal and iron resource are reclaimed, and overall economic efficiency is up to 1,000,000,000 yuan.
At present, the domestic recovery technology to gas ash (mud) and Jarosite Residues is all only limitted to be carried out according to the characteristic of material
Single processing procedure, such as：It is " a kind of to utilize rotary kiln from blast furnace that Gangcheng Enterprise General Co., Pangang Group Chen Tao et al. invents
The technique that zinc is extracted in gas mud " (patent No. CN101191159A), Honghe, Yunnan Xin Lian developments in science and technology Co., Ltd Wang Shu patterns,
" method of comprehensive recovery of iron and non-ferrous metal from steel plant's solid waste " (patent No. of Wang Hao oceans et al. invention
CN101078052A), " from blast furnace dust extract indium metal, zinc, the method for bismuth " (patent No. CN101078053A), " from
The patents such as blast furnace ironmaking flue dust producing iron powder and the method for reclaiming non-ferrous metal " (patent No. CN201210179548.8) are all pins
Raw material single to gas ash (mud) carries out professional treatment and recovery, takes full advantage of gas ash high-carbon (C18~25%), Gao Xin
The composition characteristic of (Zn9~18%), low iron (Fe23~29%) carries out fuming reduction enrichment, obtains rich in a variety of valuable metals
High-fluorine chlorine secondary zinc oxide product, is carried after zinc process though such technical scheme can thoroughly eliminate gas ash by hot setting reaction
It is innoxious store up problem, it is but low to the utilization ratio for carbon resource of being had more than needed in gas ash, because smelting is selected in the relatively low influence of Iron grade in slag
Separating effect, can only obtain the Iron concentrate of low yield extracting rate, and mixed economy development benefit is limited；Simultaneous reactions process waste heat fails
To effective recycling, cause energy consumption higher.And Guangxi University's grain seapeak, Wang Yuhong et al. invention is " a kind of to utilize yellow ammonium iron
The iron black method of alum slag oxygenerating " (patent No. CN102718267A), Guangxi Shen chess-playing circles, " the high indium high-iron-zinc of Qin Shuhong inventions
Concentrate is the new process for recovering metals such as indium, iron, silver, tin " (patent No. CN1074464C), Changsha Mining ＆ Metallurgy Inst Chen Zhi fly et al.
Patented technologies such as " technique of iron vitriol slag extracting indium by roasting and leaching " (patent No. CN1221800A) of invention is by autunezite
Slag is in, carry out the process of wet underwater welding zinc and rare precious metal again after low-temperature bake pretreatment.Its process characteristic is to be directed to siderotil
The low zinc of slag (Zn5~6%), high ferro (Fe28~36%), the spy of high rare precious metal (In0.05~0.1%, Ag300~600g/t)
Levy, it is outer to match somebody with somebody burnt (or coal) as fuel and reducing agent, volatilized by low temperature transformation of crystal or high temperature fuming, to reach separation, richness
The purpose of collection.Although such technology also can effectively extract the valuable metal in iron vitriol slag, a large amount of fuel need to be consumed, while because of slag
The decomposition of middle sulfate causes SO in flue gas2Concentration is higher (about 1~3% or so), not only etching apparatus and refractory material, and
Reclaim and difficulty of governance is big, influence kiln slag selects iron effect, easily causes kiln ring formation phenomenon, causes technological development cost too high.
Two class patented technologies, is all limited only to the angle from single material characteristic to be specialized in summary, causes
The value advantage of two class secondary resources is set to fail to give full play to, resource overall synthetic is relatively low using level, and to improving China's smelting
Golden industry energy-saving emission reduction, develop a circular economy, set up the production development pattern that cleans completely and promote dynamics limited.Therefore, working as
Under preceding technology and environmental condition, two kinds of solid waste resources of gas ash and ferrovanadium slag are taken into account into the innoxious synthetical recovery of progress, played
Complementary advantage, not only eliminates the harm to environment, also reduces environmental protection of enterprise cost, and can improve iron resource and coloured
The level of metal high added value exploitation, with very major and immediate significance.
The content of the invention
To solve above two resource deficiency present in recycling process, the present invention provides a kind of comprehensive utilization admittedly
The method that useless gas ash, ferrovanadium slag carry out cleaning recovery, the process according to gas ash carbon is high, iron is low and siderotil slag iron is high,
The characteristics of rare precious metal content is more, play material composition and have complementary advantages, synthetical recovery is reached and harmless using reaction self-heating condition
Change the purpose of processing.Good with reduction volatilization effect, valuable metal accumulation rate is high, and consumption fuel is few, comprehensive utilization of resources level
The advantage of reduced iron powder product that is high and obtaining high added value；Conventional equipment is used simultaneously, and operating process is simple, reduced investment, into
This is low, the characteristics of exhaust emissions is easily up to standard, can reach the demand of scale industrial production.
To reach above-mentioned purpose, the present invention is achieved by using following technical scheme：
Specific implementation step is：
(1) dispensing is pelletized：
By gas ash (mud) and Jarosite Residues according to (2~5): 1 ratio is well mixed, 15~30% are then incorporated
Coke powder (or anthracite), after 1~5% additive, be delivered to disk pelletizing machine and pelletized, control discharging-material size for 6~
12mm, moisture is 18~25%, and the material after granulation is stored up into dry 16~32h naturally；
(2) fuming is volatilized：
Pellet after above-mentioned natural drying is sent into rotary kiln by charging belt by kiln tail tremie pipe, reaction zone is controlled
Kiln temperature is 1150~1200 DEG C, 4~6h of reaction time, and kiln end temperature is 400~600 DEG C, and kiln tail negative pressure is 10~50Pa, kiln hood
Blast pressure is 0.05~0.15MPa, the zinc in raw material and other valuable metals is fully reacted and reduction volatilization；Kiln slag is by kiln
The laggard water-filling of head discharge is quenched cooling, and flue gas is discharged by kiln tail through air inducing to be gathered dust.
(3) scum is handled：
By the iron content kiln slag after being cooled down in above-mentioned rotary kiln fuming volatilization process, beneficiation combined method car is transported to by claw bucket sling
Between, 20% ore pulp of 100 mesh is made smaller than after two-stage crushing, screening, ball milling, is isolated and is more than containing Fe using strong magnetic separator
65% crude iron powder；Crude iron powder is again through three sections of ball mill ore grindings, output reduced iron powder and Iron concentrate after the classification of high-efficiency helical grader,
Reduced iron powder can obtain the commodity reduced iron powder that granularity is more than 92% less than 120 mesh, MFe after expansion drying and pneumatic classification.
Ore dressing tail mud carries out solid-liquor separation after Floatation of Removal Carbon, obtains carbon containing 68% carbon powder, returns dispensing recycling, tail mud is through pressure
Building Materials Factory can be delivered to as environment-friendly building materials raw material after filter dehydration.
(4) fume treatment：
The flue gas that kiln tail in above-mentioned rotary kiln fuming volatilization process is discharged, bulky grain flue dust is removed through gravity settling chamber,
And 130~200 DEG C are cooled to through waste heat boiler, dedusting is carried out subsequently into negative pressure bagroom, the tail gas after gathering dust is through drawing
Blower fan delivers to Pneumatic emulsifying desulfurizing tower and carries out desulphurization and denitration, and through 60m chimney qualified discharges.Expansion chamber gray back is buried through closed
Drag conveyor return to step (1) carries out dispensing, and the secondary zinc oxide flue dust that waste heat boiler and bagroom are collected is through water
Cold type embedded scraper transporter delivers to warehouse, and zinc and other rare precious metals are extracted for next step.
Gas ash (mud) in above-mentioned steps (1) produces dust-removal cloth-bag ash, its main component by iron and steel enterprise's blast furnace
Scope is：Fe20~32%；C15~25%；Zn4-20%；Pb0.03~1.5%；In0.02~0.15%；Bi0.1~
1.8%；S0.2~0.6%；CaO3.2~7.8%；SiO20.8~10.4%；Al2O32.1~5.8%；
Jarosite Residues in above-mentioned steps (1) produce leached mud by zinc abstraction industry high temperature peracid jarosite process,
Its main component scope is：Zn4.5-7.6%；Pb1.5~3.2%；In0.05~0.12%；Fe20~36.3%；Cu0.03
~0.16%；Cd0.008~0.03%；As0.5~0.8%；Mn0.6~0.8%；S7.58~12.63%；Ag60~350g/
t；
Additive used in above-mentioned steps (2) be industrial silicon sand, lime, calcium hydroxide or one kind in calcium carbonate or
Several combinations.
Medicament used in Floatation of Removal Carbon process in above-mentioned steps (3), collecting agent is kerosene, oil, light diesel fuel, paraffin, 2#
One or more of oil grade；Foaming agent is fusel, sec-octyl alcohol, fatty oil etc.；Regulator is waterglass, sodium carbonate, vulcanized sodium, hydrogen
One or more of sodium oxide molybdena, starch, lignin, humic acid.
Tail mud discarded object in above-mentioned steps (3) is the silicate glass body after rotary kiln hot setting, without molten again
Solution property is poisoned, and can be stored up or utilize for a long time, its main component is：Fe7.6-10.1%；Zn0.1~0.2%；Pb0.03~
0.06%；CaO8.6~12.6%；SiO218.6~23.4%；
Involved tail gas Pneumatic emulsifying desulfurizing tower sets for the environmental protection treatment that exclusive enterprise manufactures in above-mentioned steps (4)
Apply, the addition medicament of its circulating absorption solution is commercially available NaOH, calcium hydroxide or quick lime.
Resulting secondary zinc oxide product composition is in above-mentioned steps (4)：Zn50-60%；Pb8~10%；In0.07~
0.12%；Fe0.6~1.5%；Cl2.1~3.8%；F0.03~0.08%；
Its general principles：
Gas ash and iron vitriol slag, appropriate coke powder are made into after compound, are added to by kiln tail in rotary kiln, 1100~
The metallic compounds such as zinc, lead, indium in redox reaction, material are carried out under 1300 DEG C of high temperature is by carbon and Carbon monoxide reduction
Metal, volatilizees and enters gas phase at high temperature, and the air oxidation blasted is into oxide (ZnO, PbO, In2O3Deng), with furnace gas
Enter dust collecting system after cooling, be collected and reclaimed to be enriched with oxide product；Iron is reduced to fe or iron oxide,
The refractory metals such as arsenic, antimony and calcium, silicon carry out slag making, are able to solidify into slag.
Main chemical reactions：
In the bed of material：2C+O2=2CO (1)
C+O2=CO2 (2)
ZnO+CO=Zn (g)+CO2 (3)
ZnO+C=Zn(g)+CO (4)
3Fe2O3+CO=2Fe3O4+CO2 (5)
Fe3O4+CO=3FeO+CO2 (6)
FeO+CO=Fe+CO2 (7)
3(ZnO·Fe2O3)+C=2Fe3O4+3ZnO+CO (8)
ZnO·Fe2O3+CO=ZnO+2FeO+CO2 (9)
ZnS+3O2=2ZnO+2SO2 (10)
ZnSO4=ZnO+SO2+ 1/2O2 (11)
Gas phase layer：Zn+1/2O2=ZnO (8)
CO+1/2O2=CO2 (9)
Main economic and technical indices are during this：
Metal volatility：Zn>95%, Pb>95%, Bi>91%, In>93%；
Non-ferrous metal overall recovery>97%, Fe>99%；
Metal enrichment ratio is 8~10 times；
Rotary kiln unit volume productivity ratio：1.8~2.5 tons/m3·d；
Coal-fired (Jiao) ratio：15~20%, Second-rate zinc oxide powder output capacity：20~25%；
Iron concentrate grade>65%, a reduced iron powder output capacity>55%；
The inventive method can not only improve China's metallurgy industry metal secondary resource level of comprehensive utilization well, while
Resource reclaim present in two industry developments and the general character problem recycled are solved, energy-saving and emission-reduction, development circulation is reached
Economic effect, realizes the minimizing of waste resource, recycling, the purpose of recycling.
This process makes full use of the characteristics of resources advantage is complementary, not only solves gas mud and carry in implementation process
Secondary zinc oxide product fluorine chlorinity is high during zinc, the industry problem that subsequent treatment is difficult, scale additional processing cost is high；Also eliminate
Fuel cost is high during iron vitriol slag pyrogenic attack, kiln age is short, tail gas SO2The big crux of intractability, the solution of zero cost
Storing up for two class industry solid wastes, disposal difficulties；Simultaneously during non-ferrous metal is reclaimed, conventional fire reduction control is broken through
Key technology, can disposably obtain the reduced iron powder product of high added value, greatly improve the economic benefit of the utilization of resources, make
The total recovery utilization rate of resource valuable metal reaches more than 98%.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Embodiment
Below in conjunction with accompanying drawing and preferred embodiment, the present invention is described further.
Embodiment 1
Raw materials used composition is：
Steel plant's gas ash (mud) material composition is (wt, %)：Fe28.4, C21.3, Zn10.4, Pb0.6, In0.08,
Bi0.3, CaO5.27, SiO28.14, Al2O33.65, H2O16.3%；
Zinc abstraction factory Jarosite Residues material composition is (wt, %)：Zn6.35, Pb1.8, In0.10, Fe32.7,
Cu0.12, Cd0.018, As0.6, Mn0.62, Ag87g/t, H2O21.8%；
Coke powder composition：Fixed carbon 68.5%, volatile matter 4.68%, ash content 28.7%, S0.45%, H2O12%, calorific capacity
6300KCal/Kg；Granularity<10mm is (wherein<75%) 2mm's accounts for；
Quick lime composition：Ordinary metallurgical lime three-level product, CaO content>85%, the mesh of granularity 60~80；
(1) mentioned component gas ash and iron vitriol slag are first carried out batch mixing by dispensing granulation according to 3: 1 ratio, then will mixing
Material carries out stockpile burdening in 1: 0.18: 0.03 ratio with coke powder, quick lime with claw bucket sling, it is well mixed after, through disk feeder,
Pelletized in belt conveyer feeding φ 6000 × 500mm disk pelletizing machine, Control granularity for 8~10mm account for 85% with
On, pellet is sent into after indoor stock ground carries out natural drying ventilation, 24h and sends into feed bin by forklift by moisture 25% or so after granulation,
Through being reacted in kiln tail charging belt, tremie pipe feeding kiln.
(2) rotary kiln fuming volatilization controls 3.2 × 50m of φ reacting in rotary kiln band kiln temperature to be 1150~1200 DEG C, and material is anti-
Run time 4h, 0.5~1.2rpm of rotating speed are answered, kiln end temperature is 400~550 DEG C, and kiln tail negative pressure is 10~50Pa, kiln hood air blast
Pressure is 0.05~0.12MPa, makes the zinc in raw material and the abundant reduction volatilization of other valuable metals and reaction；Kiln slag is arranged by kiln hood
Go out laggard water-filling to quench cooling, flue gas is gathered dust by kiln tail through air inducing discharge.During metal volatility Zn>96.1%, Pb>
95.2%, In>93.6%；Metal enrichment ratio is up to 12, metal total recovery>98%, degree of metalization (Fe)>76.5%, kiln looks into Zn<
0.53%.
(3) the water quenching kiln slag after cooling down is transported to beneficiation combined method workshop by scum processing by grab bucket, broken through two grades
Broken, screening, 20% ore pulp that 100 mesh are made smaller than after wet ball-milling, using permanent-magnet drum type magnetic separator, control the magnetic flux to be respectively
1200~2500 Gausses, isolate after three sections of gradient magnetic separations and are more than 65% crude iron powder containing Fe；Crude iron powder passes through three-level ore grinding, then
Output reduced iron powder and Iron concentrate after being classified through high-efficiency helical grader, reduced iron powder can be obtained after expansion drying and pneumatic classification
Sold after being less than the commodity reduced iron powder that 120 mesh, MFe are more than 92%, categorized packaging to granularity；Iron content is less than 8% ore dressing
Tail mud carries out solid-liquor separation after Floatation of Removal Carbon, obtains carbon containing 68% carbon powder, returns dispensing recycling, tail mud is after press filtration
Building Materials Factory is sent to be used as environment-friendly building materials raw material.During obtained reduced iron powder mass component be：TFe95.4%, MFe92.3%,
As<0.03%, S<0.05%, P<0.03%；The overall recovery of iron is 99.3%, reduced iron powder output capacity 56.4%, Iron concentrate
Output capacity 23.7%.
(4) fume treatment rotary kiln high-temperature flue gas is discharged by kiln tail, after removing bulky grain flue dust through gravitational settling, via remaining
Heat boiler cooling down is to suction type bagroom is entered after 150~160 DEG C, and the flue gas after gathering dust is through 120,000 m3/ h air-introduced machines
Deliver to Pneumatic emulsifying desulfurizing tower and carry out desulfurization, and by chimney qualified discharge；Gravity settling chamber gray back is returned by embedded scraper transporter
The water cooled formula embedded scraper transporter of secondary zinc oxide product that dispensing, waste heat boiler and bagroom are collected delivers to warehouse.
The secondary zinc oxide composition of process output is (wt, %)：Zn56.8, Pb9.3, In0.09, Fe0.38, Cl2.3, F0.03；Tail gas
SO2Content is less than 80mg/Nm3, desulfuration efficiency is more than 99.5%.
After being handled using the art of this patent above-mentioned material, secondary zinc oxide output capacity is up to 28%, kiln slag of rotary kiln
Containing zinc less than 0.6%, F, Cl content are relatively low (it is 7~15% that gas mud, which produces zinc oxide F, Cl) in the secondary zinc oxide of output, warp
After alkali cleaning defluorinate chlorine, zinc hydrometallurgy ingredient requirement can be met.
Embodiment 2
Raw materials used composition is：
Steel plant's gas ash (mud) material composition is (wt, %)：Fe18.6, C19.3, Zn8.4, Pb0.3, In0.06,
Bi0.1, CaO6.18, SiO210.36, Al2O34.19, H2O17.5%；
Zinc abstraction factory Jarosite Residues material composition is (wt, %)：Zn5.68, Pb2.7, In0.08, Fe35.1,
Cu0.07, Cd0.021, As0.4, Mn0.37, Ag126g/t, H2O23.8%；
Coke powder composition：Fixed carbon 70.1%, volatile matter 3.21%, ash content 26.3%, S0.38%, H2O14%, calorific capacity
6500KCal/Kg；Granularity<10mm is (wherein<80%) 2mm's accounts for；
Quick lime composition：Ordinary metallurgical lime three-level product, CaO content>85%, the mesh of granularity 60~80；
(1) mentioned component gas ash and iron vitriol slag are first carried out batch mixing by dispensing granulation according to 5: 1 ratio, then will mixing
Material carries out dispensing in 1: 0.20: 0.02 ratio with coke powder, quick lime with forklift, after being well mixed, and is transported through disk feeder, belt
Pelletized in 6000 × 500mm of defeated machine feeding φ disk pelletizing machine, Control granularity is that 10~12mm accounts for more than 85%, moisture
20% or so, pellet is sent into after indoor stock ground carries out natural drying ventilation, 16h after granulation feed bin is sent into by forklift, through kiln tail
Reacted in charging belt, tremie pipe feeding kiln.
(2) rotary kiln fuming volatilization controls 3.2 × 50m of φ reacting in rotary kiln band kiln temperature to be 1200~1250 DEG C, and material is anti-
Run time 5h, 0.5~1.2rpm of rotating speed are answered, kiln end temperature is 550~600 DEG C, and kiln tail negative pressure is 30~50Pa, kiln hood air blast
Pressure is 0.07~0.15MPa, makes the zinc in raw material and the abundant reduction volatilization of other valuable metals and reaction；Kiln slag is arranged by kiln hood
Go out laggard water-filling to quench cooling, flue gas is gathered dust by kiln tail through air inducing discharge.During metal volatility Zn>95.3%, Pb>
96.4%, In>93.4%；Metal enrichment ratio is up to 10.5, metal total recovery>98.4%, degree of metalization (Fe)>77.6%, kiln slag
Zn<0.45%.
(3) the water quenching kiln slag after cooling down is transported to beneficiation combined method workshop by scum processing by grab bucket, broken through two grades
Broken, screening, 20% ore pulp that 100 mesh are made smaller than after wet ball-milling, using permanent-magnet drum type magnetic separator, control the magnetic flux to be respectively
1400~2500 Gausses, isolate after three sections of gradient magnetic separations and are more than 65% crude iron powder containing Fe；Crude iron powder passes through three-level ore grinding, then
Output reduced iron powder and Iron concentrate after being classified through high-efficiency helical grader, reduced iron powder can be obtained after expansion drying and pneumatic classification
Sold after being less than the commodity reduced iron powder that 120 mesh, MFe are more than 92%, categorized packaging to granularity；Iron content is less than 7.3% choosing
Ore deposit tail mud carries out solid-liquor separation after Floatation of Removal Carbon, obtains carbon containing 70% carbon powder, returns dispensing recycling, tail mud is through press filtration
Hou Song Building Materials Factories are used as environment-friendly building materials raw material.During obtained reduced iron powder mass component be：TFe96.3%,
MFe92.8%, As<0.03%, S<0.05%, P<0.03%；The overall recovery of iron is 99.1%, reduced iron powder output capacity
61.6%, Iron concentrate output capacity 24.9%.
(4) fume treatment rotary kiln high-temperature flue gas is discharged by kiln tail, after removing bulky grain flue dust through gravitational settling, via remaining
Heat boiler cooling down is to suction type bagroom is entered after 150~160 DEG C, and the flue gas after gathering dust is through 100,000 m3/ h air-introduced machines
Deliver to Pneumatic emulsifying desulfurizing tower and carry out desulfurization, and by chimney qualified discharge；Gravity settling chamber gray back is returned by embedded scraper transporter
The water cooled formula embedded scraper transporter of secondary zinc oxide product that dispensing, waste heat boiler and bagroom are collected delivers to warehouse.
The secondary zinc oxide composition of process output is (wt, %)：Zn60.2, Pb12.1, In0.08, Fe0.45, Cl1.8, F0.013；Tail gas
SO2Content is less than 52mg/Nm3, desulfuration efficiency is more than 99.7%.
After being handled using the art of this patent above-mentioned material, secondary zinc oxide output capacity is up to 29%, kiln slag of rotary kiln
Containing zinc less than 0.45%, F, Cl content are relatively low (it is 7~15% that gas mud, which produces zinc oxide F, Cl) in the secondary zinc oxide of output, warp
After hot wash defluorinate chlorine, the ingredient requirement of the electric zinc of secondary zinc oxide production can reach.
Claims (1)
1. a kind of solid waste gas ash, the comprehensive recycling process of vanadium slag containing zinc-iron, it is characterised in that it is comprised the following steps：
(1) dispensing granulation step：Solid waste gas ash and vanadium slag containing zinc-iron are mixed by weight 2: 1~5: 1, coke powder is added
Pelletized with after additive, it is 6~12mm to control discharging-material size, and presoma is obtained after spontaneously drying 16~32h；Described
Additive is one or several kinds of combinations in industrial silicon sand, lime or calcium hydroxide；Described solid waste gas ash is iron and steel enterprise
Blast furnace produces dust-removal cloth-bag ash, and its main component scope is：Fe20~32%；C15~25%；Zn4-20%；Pb0.03
~1.5%；In0.02~0.15%；Bi0.1~1.8%；S0.2~0.6%；CaO3.2~7.8%；SiO20.8~
10.4%；Al2O32.1~5.8%；Described vanadium slag containing zinc-iron produces leaching by zinc abstraction industry high temperature peracid jarosite process
Slag tap, its main component scope is：Zn4.5-7.6%；Pb1.5~3.2%；In0.05~0.12%；Fe20~36.3%；
Cu0.03~0.16%；Cd0.008~0.03%；As0.5~0.8%；Mn0.6~0.8%；S7.58~12.63%；Ag60
~350g/t；
(2) fuming volatilisation step：Above-mentioned presoma is subjected to fuming volatilization in rotary kiln, it is 1150 to control reaction zone kiln temperature
DEG C, 4~6h of reaction time, 400~600 DEG C of kiln end temperature, kiln tail 10~50Pa of negative pressure, kiln hood blast pressure 0.05~
0.15MPa, the kiln slag that reaction is produced continuously is discharged by kiln hood, and water quenching cools；The flue gas that reaction is produced is discharged by kiln tail air inducing；
(3) scum process step：The kiln slag that above-mentioned fuming volatilisation step is produced is handled, the kiln slag is through broken, ball milling
After ore pulp is made, then the ore pulp is separated through multi-stage magnetic separation, obtain containing Fe be more than 65% crude iron powder and mine tailing；Mine tailing therein
Through Floatation of Removal Carbon and solid-liquor separation, carbon containing 68% carbon powder and tail mud is obtained, carbon powder can return dispensing recycling, tail mud warp
Environment-friendly building materials raw material is used as after filter-press dehydration；Medicament used in the Floatation of Removal Carbon process, collecting agent be kerosene, oil, light diesel fuel,
One or more of paraffin, 2# oil；Foaming agent is fusel, sec-octyl alcohol, fatty oil；Regulator be waterglass, sodium carbonate, vulcanized sodium,
One or more of sodium hydroxide, starch, lignin, humic acid；
(4) fume treatment step：Flue gas produced by step (2) is handled, the flue gas is successively through gravitational settling, cooling
Desulphurization and denitration is carried out after cooling and bag collection, and by 60m smoke stack emissions；The gray back that gravitational settling is produced can return to dispensing system
Grain step is to adjust elemental constituent, and the flue dust collected by bag collection can be used as extracting zinc and the raw material of other rare precious metals.
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