CN104846209B - A kind of system and method for step-by-step reduction recovery ferrum and coal gasification recovery waste heat from molten copper slag - Google Patents
A kind of system and method for step-by-step reduction recovery ferrum and coal gasification recovery waste heat from molten copper slag Download PDFInfo
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Abstract
A kind of system and method for step-by-step reduction recovery ferrum and coal gasification recovery waste heat from molten copper slag, belongs to resource and environment field.This system includes reduction and carries iron furnace, coal gasifier, granulation and waste-heat recovery device, flue gas heat-exchange unit, gas separation dust arrester, waste heat boiler, cyclone dust extractor, gas chamber, feeding device；Method is divided into 3 steps：Step-by-step reduction puies forward ferrum and coal-gas recovering；Coal gasification and coal-gas recovering；Granulation and waste heat recovery.System and method of the present invention achieve the link of copper ashes dry granulation, waste heat reclaiming process and copper ashes valuable metal extraction process; can ferrum in efficient recovery copper ashes; iron recovery reaches more than 90%; and the CO gas that removal process produces can carry out self-loopa use; while environmental protection economizes on resources, solve the series of problems of high temperature copper ashes processing procedure.
Description
Technical field
The invention belongs to resource and environment field is and in particular to one kind step-by-step reduction from molten copper slag reclaims ferrum and coal gas
Change the system and method for recovery waste heat.
Background technology
In recent years, global Copper making industry development is rapid, and the total annual production of world's copper in 1980 is 7,500,000 tons, and complete at present
World's copper annual production has broken through 16,000,000 tons.While world's copper yield rapid growth, China's copper metallurgy industry has also obtained front institute
Not some development, China in 2007 leaps to and becomes the first in the world big copper manufacturing country, has accounted for global copper to China's copper yield in 2012
The 30% of yield.
The smelting of copper mainly includes pyrogenic process and hydrometallurgy, because hydrometallurgy is limited by grade and the type of Ore, fire
Method smelting is applied widely, and the therefore global copper that there are about 80% uses pyrogenic process smelting, and even more accounts in China's pyrometallurgical smelting
To more than 97%.It is known that metallurgy industry belongs to energy intensive industry, the loss to resource and the energy is larger, and secondary
Energy utilization rate is low, often results in serious waste, and this is particularly problematic for the pyrometallurgical smelting process of copper.And pyrometallurgical smelting mistake
Its main component of a large amount of copper ashes that journey produces is fayalite and magnetic iron ore, iron content therein up to 30%～45%, has
Higher recycling is worth, and the iron content in part copper ashes is even more than the mining grade of iron ore, and different method of smelting produce
Raw copper ashes each constituent mass percentage ratio is as shown in table 1.According to relevant statistics, the whole world often produces 1 ton of copper and can produce 2.2～3
The copper ashes of ton, the copper ashes being often only China's generation is just up to 15,000,000 tons.Additionally, the tapping temperature of copper ashes is up to 1200～1300
DEG C, and be using storing up slow cooling and water quenching to the conventional process mode of copper ashes, the copper ashes after two ways is processed is stored up in a large number,
Not only the waste heat of copper ashes is not recycled, and the valuable metal such as the ferrum in copper ashes, copper, cobalt, nickel is also wasted.
In addition water quenching processing procedure needs to consume substantial amounts of water, the H of generation2The harmful gass such as S and SOx also enter air with steam,
Cause serious environmental pollution.Review China iron deposit stone current resources situation：Iron ore resource critical shortage, far from meeting China's steel
The demand of ferrum industry, per capita ownership be only the world per capita iron ore deposit amount 34.8%, and be available for develop iron ore
Resource is only the 53% of total resources, and iron ore resource inferior quality, and lean ore is many, and high-grad iron ore deposit is less, and lean ore reserves accounts for total storage
The 80% of amount.Therefore, transform traditional copper residues processing technique, the ferrum component in efficient recovery copper ashes, for alleviation China iron ore
The situation of resource long-term shortage is significant.
With the attention to the energy and environment for the people, the research utilizing for valuable metal recovery in copper ashes is also progressively deep
Enter.The recovery method to ferrum component in copper ashes of existing report mainly includes oxidizing process, reducing process, wet method and magnetic method.
Oxidizing process, refers to carry out oxidation processes to molten state copper ashes, realizes in copper ashes ferrum component to magnetic iron ore phase selectivity
Enrichment, reclaims ferrum by magnetic separation mode after crushing through supercooling at low temperature.Patent CN101100708 first reported this recovery
Method.Find during follow-up study, react later stage, because FeO component constantly reduces in copper ashes, Si-O network in melt oxidation
Close ion cluster to be constantly polymerized, and Fe3O4Constantly agglomeration, leads to viscosity coefficient of dross and fusing point to gradually rise, hinders reaction
Proceed and the growing up of magnetic iron ore phase, lead to iron recovery low.
The method that in reducing process, mainly copper ashes, Fe containing component reduces precipitation in the presence of additional reducing agent.To not
Congener reducing agent, its addition manner is different, specific smelting reduction process difference.Patent CN101736112B is open
A kind of method of blowing inert gas stirring reduction iron production from molten copper slag, can carry out secondary to flue gas while reclaiming ferrum
Burning Mist heat recovering.CN102952952A disclose one kind at high temperature with natural gas reduction copper ashes obtain copper alloy melt
Body and the method for metallic iron.The key of reducing process is to change enriched form in copper ashes for the ferrum by controlling reducing atmosphere, will
Fayalite is recycled after being changed into metallic iron again, but reducing process requires bath temperature high.
Wet method, is using the chemical agent comprehensively recovering valuable metal such as sulphuric acid or chloric acid, this method has good selectivity,
And the valuable metal such as recyclable zinc, lead, nickel, cobalt.But Wet technique needs, using substantial amounts of chemical agent, not only equipment to be produced
Corrosion, will also result in environmental pollution.
Magnetic method, mainly for the recovery of ferrum in cold conditions copper ashes.Ferrum is mainly distributed on olivine phase and magnetic oxygen in copper ashes
Change in iron mineral, iron ore concentrate can be obtained with the method for magnetic separation.But copper ashes thing is mutually complicated, the bad copper ashes of degree of crystallinity each thing phase
Between there is adhesion and parcel phenomenon, lead to valuable metal to separate difficulty with gangue content, thus magnetic separation effect on driving birds is not good.
Above technical method all can reclaim the metal component in copper ashes to a certain extent, but while reclaiming metal,
Copper ashes high-grade waste heat fails effectively utilizes.The mode of particularly wet method and magnetic method recovery metal is directed to cold conditions copper ashes,
Copper ashes heat recovery technology and metal recovery technology are difficult to effectively link.CN103537480A reports a kind of molten copper slag reduction
The method of low-carbonization comprehensive utilization afterwards, the method carries the copper ashes slag after ferrum and carries out water-spraying control solidification mechanical disruption to reduction
Broken, then the copper ashes after to crush, as thermal source, recycles copper ashes waste heat by way of gasification of biomass.The method can
Reclaim the waste heat of below 900 DEG C of copper ashes, but in water-spraying control process of setting, the waste heat of 1500 DEG C of slag～900 DEG C of temperature sections
Fail effectively utilizes, system waste heat organic efficiency is difficult to improve further.Therefore, exploitation copper ashes resource utilization efficiency is high and remaining
The high new method of heat recovery efficiency is significant.
Copper ashes each constituent mass percentage ratio that the different method of smelting of table 1 produces
Note：In copper ashes, the existence form of ferrum is mainly Fe3O4And FeO, in Fe3O4And in FeO ferrum element mass percent
Sum is 30%～45%.
Content of the invention
The problem existing for prior art, the present invention provides a kind of step-by-step reduction recovery ferrum and coal gas from molten copper slag
Change the system and method for recovery waste heat, it is possible to achieve the target of copper and iron component and copper ashes waste heat in high efficiente callback copper ashes, solve
In copper ashes, iron recovery is low and copper ashes melting slag waste heat reclaims difficult technical problem.Technical scheme is as follows：
A kind of system of step-by-step reduction recovery ferrum and coal gasification recovery waste heat from molten copper slag, carries iron furnace including reduction,
Coal gasifier, granulation and waste-heat recovery device, flue gas heat-exchange unit, gas separation dust arrester, waste heat boiler, cyclone dust extractor,
Gas chamber, feeding device, wherein gas chamber connect reduction and carry iron furnace, and reduction carries iron furnace upper end and connects gas by flue gas heat-exchange unit
Separate dust arrester, separate dust arrester top and be provided with pipeline connection gas chamber, the slag notch that reduction carries iron furnace connects coal gasification
Stove, coal gasifier connects one end of cyclone dust extractor by waste heat boiler, and the cyclone dust extractor other end connects gas chamber, coal gasification
The slag notch of stove connects granulation and waste-heat recovery device, and granulation and waste-heat recovery device connect feeding device.
Reduction carries the molten bath bottom of iron furnace or furnace wall sidepiece is provided with reductant nozzle；Furnace wall side is simultaneously provided with coal gas and burns
Mouth and jet for gas, and coal gas burner be located at molten bath above, jet for gas stretches into molten bath bottom.
Coal gasifier is provided with coal nozzle and gasifying agent nozzle, stretches in the molten bath of coal gasifier, nozzle quantity is at least 4
Individual, it is located at coal gasifier molten bath upper and lower respectively.
Granulation and waste-heat recovery device include pelletizer, and slag particle is collected and waste-heat recovery device two parts, and top is granulation
Device, bottom is collected and waste-heat recovery device for slag particle；Pelletizer is located at granulation and waste-heat recovery device center, and pelletizer passes through steel
Plate weld is on the metal inner surface of slag particle collection and waste-heat recovery device；Slag particle is collected and waste-heat recovery device top is infundibulate
Shape, bottom is drum, and internal and external walls face is metal water-cooling wall, is respectively provided with downward-sloping on lower cylindrical wall
Endless metal deflection plate, 5～7 grades, deflection plate length is 0.4～0.8m, and spacing is 0.4～0.6m, is 10 with horizontal plane angle
～30 °.Its work process is as follows：Slag is crushed and is cooled to granule slag by pelletizer, and granule slag does whereabouts fortune after upper collection
Dynamic, the granule slag of whereabouts makees "the" shape motion on endless metal deflection plate, granule slag and metal water cold wall in collision process
Carry out heat exchange, metal wall transfers heat to the cooling water of inside, cooling water temperature raises, and granule slag is in sluggish flow process
Middle temperature reduces, and granule slag waste heat is able to efficient recovery, enters and transport dress after the granule slag after bottom of device, cooling is collected
Put.
Granulation and waste-heat recovery device also can be provided with blower fan and waste heat boiler, and blower fan is located at granulation and waste-heat recovery device bottom
Portion, waste heat boiler is located at granulation and waste-heat recovery device upper right quarter.Its work process is as follows：Air is from granulation and waste heat recovery dress
Bottom set portion blasts, and carries out heat convection with the granule slag falling, and raises in flow process air temperature, and the cooling of granule slag is cold
But；Hot-air enters waste heat boiler from granulation and waste-heat recovery device upper right quarter, and waste heat boiler reclaims the heat entrained by hot-air
Amount produces hot water, and air is discharged from waste heat boiler.
A kind of method that step-by-step reduction reclaims ferrum and coal gasification recovery waste heat from molten copper slag, including following technique step
Suddenly：
(1) step-by-step reduction puies forward ferrum and coal-gas recovering：
1200～1300 DEG C discharged from copper smelter of molten state copper ashes is flowed into reduction and carries iron furnace, by gas chamber
CO is burnt by coal gas burner, treats that bath temperature rises to 1450 DEG C～1500 DEG C, from jet for gas injection CO, copper ashes is entered
Row CO reduction reaction, CO consumption is 1: 3～1: 2.5 with Fe amount in copper ashes according to mol ratio, and the injection time is 20～30min, spray
Blow pressure power is 0.5～1.0MPa；Reaction stops injection CO after terminating, and adds flux, flux consumption and SiO in copper ashes2Amount according to
Mol ratio is 1.2: 1, is blown reducing agent by reductant nozzle simultaneously and copper ashes is carried out with reducing agent reduction reaction, reducing agent consumption
It is 1: 1～1.2: 1 with Fe amount in copper ashes according to mol ratio, the injection time is 20～40min；Reaction stops injection reduction after terminating
Agent, by the copper ashes insulation standing 20～40min of reduction, the copper ashes after sedimentation is divided into two-layer, and lower floor carries iron furnace for molten iron from reduction
Lower curtate flows out, and upper strata is that reduced blast furnace flows into coal gasifier from slag notch；
CO burning and the CO of two step reduction reactions generation2And CO gaseous mixture, after flue gas heat-exchange unit recovery waste heat, passes through
Gas separation dust arrester removes CO2Gas, CO returns gas chamber and continues cycling through use；
(2) coal gasification and coal-gas recovering：
The initial temperature that reduced blast furnace flows into coal gasifier is 1450～1500 DEG C, is blown particle diameter by coal nozzle and exists
The mass ratio of the coal dust of below 1mm, coal dust and reduced blast furnace is 1: 0.02, is blown gasifying agent CO by gasifying agent nozzle2, CO2With
Amount and pulverized coal consumption are 1: 1 according to mol ratio, and the temperature of monitoring reduced blast furnace treats that temperature is down to about 1200 DEG C, by reduced blast furnace
Enter granulation and waste-heat recovery device from slag notch；
The CO that coal gasification course produces enters cyclone dust extractor dedusting after waste heat boiler recovery waste heat, clean after dedusting
Net CO enters gas chamber and continues cycling through use；
(3) granulation and waste heat recovery：
Reduced blast furnace is introduced into pelletizer and carries out dry method centrifugal breaking, forms the granule slag of diameter about 1mm, in centrifugation masterpiece
It is thrown out of entrance slag particle with lower granule slag to collect and waste-heat recovery device, and "the" shape fortune is made on endless metal deflection plate
Dynamic, be passed through in air or water-cooling wall and be passed through cooling water, by granule slag and the air being passed through or water-cooling wall carry out heat exchange Lai
Collect the waste heat of granule slag, the granule slag after recovery waste heat falls into bottom of device, and temperature is down to 100 DEG C about, enters and transports dress
Put.
It is limestone or dolomite or quick lime that described step-by-step reduction carries ferrum and the flux of coal-gas recovering process.
It is coal dust or coke or graphite that described step-by-step reduction carries ferrum and the reducing agent of coal-gas recovering process.
In described gas separation dust arrester, the solution of assembling is NaOH solution or Ca (OH)2Solution, absorbs CO2After gas
Soda or CaCO can be prepared respectively3；And the CaCO preparing3Reduction can be put into as flux and propose recycling in iron furnace.
The gasifying agent CO of described slag coal gasification course2The waste gas producing from industrial furnace.
The chemical equation that the processing step that the inventive method comprises is related to is as follows：
(1) step-by-step reduction carries ferrum：
Ferric iron in copper ashes is reduced into ferrous irons by CO first, sees reaction 1.；Sharp with elder generation before carbonaceous reducing agent
With the SiO in flux and copper ashes22. reaction, to promote ferrum silicon to separate, be shown in reaction；It is subsequently adding carbonaceous reducing agent by ferrous irons also
3. and 4. former one-tenth fe, is shown in reaction.
Fe3O4+ CO=3FeO+CO2(g) ①
CaO+SiO2=CaO SiO2(②
2FeO·SiO2+ 2C=2Fe+2CO (g)+SiO2③
FeO+C=Fe+CO (g) is 4.
(2) coal gasification：
Coal dust and gasifying agent CO25. reaction, be shown in reaction.
C+CO2G ()=2CO (g) is 5.
Below based on 1kg copper ashes, according to the conservation of mass and law of conservation of energy to copper ashes step-by-step reduction and coal gasification
During the product of required material and generation calculated, method is as follows：
Molten state copper ashes temperature：1250℃；Copper ashes chemical composition：Cu=0.7%, FeO=37.5%, Fe3O4=
10.2%, SiO2=32.0%, CaO=0.2%, Al2O3=1.0%, other impurities 18.4%；Metal recovery rate is according to 100%
Calculate.
(1) step-by-step reduction process
In reduction process, CO completes to Fe3O4Reduction, see reaction 1., the amount of material of CO and volume needed for copper ashes reduction
It is respectively：
VCO=nCO × 0.0224=0.010m3
Reducing agent reduces to ferrous irons in copper ashes, and ferrous irons are produced by two parts, and a part is reduction Fe3O4Gained,
3. and 4. another part is originally to contain in copper ashes, sees reaction, and needed for copper ashes reduction, the amount of reducing agent material and quality are respectively：
MC=nC × 0.012=0.078kg
The amount of required flux (CaO) theory material and quality are respectively, and see reaction 2.：
MCaO=nCaO × 0.056=0.299kg
Heat income item is as follows：(physical thermal that CO, reducing agent and flux are brought into is ignored)
Slag making exothermic heat of reaction：
Reaction is 2.：Δ H=91.990kJ/mol
Qin-1=nCaO × 91.99=5.333 × 91.99=490.6kJ
The physical thermal that copper ashes is brought into：
Qin-2=Cm3×1×Δt1=0.755 × 1 × (1250-20)=928.7kJ
CO combustion heat release：The volume that CO burning consumes is represented with V ' CO
Qin-3=V ' CO × 12754
Heat expenditure item is as follows：(not considering that system radiating loses)：
Copper ashes reduction reaction is absorbed heat：
Reaction is 1.：Δ H=92.351kJ/mol
Reaction is 3.：Δ H=233.683kJ/mol
The physical thermal that ferroalloy is taken out of：
Qout-2=Cm1(mFe+mCu)×Δt2=
0.460 × (0.102 × 168/232+0.375 × 56/72+0.007) × (1500-20)=305.0kJ
The physical thermal that slag is taken out of：
Qout-3=Cm2(1-mFeO-mFe3O4-mCu+mCaO)×Δt1
=1.050 × (1-0.375-0.102-0.007+0.299) × (1500-20)=1266.5kJ
The physical thermal (flue-gas temperature is set to 1600 DEG C) that flue gas is taken out of：
Qout-4=CFlue gas(V′CO+VCO+nC×0.0224)×Δt3
=[2.364 × (V ' CO+0.01+0.146) × 1580] kJ
According to law of conservation of energy, Qin=Qout, can calculate to carry in iron furnace in reduction and often process 1kg copper ashes, need to burn
CO volume be V ' CO=0.171m3.It is as shown in table 2 that reduction puies forward material input amount and product quantum of output result of calculation in iron furnace.
Table 2 reduction puies forward material input amount and product quantum of output result of calculation in iron furnace
(2) coal gasification course
In coal gasifier, coal gasification reaction is carried out for thermal source with reduced blast furnace, see reaction 5..
Reaction is 5.：Δ H=-173.4kJ/mol
Slag quality is 0.873kg, and the temperature entering coal gasifier is 1500 DEG C, and discharge temperature is set as 1200 DEG C, stove
Slag release heat be：Q=Cm2mSlag×Δt1=1.050 × 0.873 × (1500-1200)=275.0kJ
According to law of conservation of energy：The heat that the heat=gasification reaction of slag release absorbs, coal needed for coal gasification reaction
The amount of the material of powder is：
nCCoal gasification=Q/173.4=1.586mol
Then coal gasification gasification reaction needs the quality of the coal dust consuming is 0.0190kg, and the CO2 volume of consumption is
0.035m3, the CO volume of generation is 0.070m3.
(3) coal-gas recovering process
Carry ferrum in step-by-step reduction and coal gasification course all refers to coal-gas recovering, wherein step-by-step reduction carries the CO of ferrum process generation
For 0.146m3, CO2For 0.170m3, after separating dust arrester washing and separating, residual gas is CO pure gas, and volume is
0.146m3, producible Na in separating dust arrester2CO3Quality is 0.804kg；Coal gasification course produce CO volume be
0.070m3.The CO cumulative volume of two process generations is 0.216m3, the demand of CO during ferrum is put forward more than step-by-step reduction
(0.181m3), therefore CO gas disclosure satisfy that its own system needs.In sum, step-by-step reduction carries ferrum and coal gasification course system
System material input amount and product quantum of output result of calculation are as shown in table 3
Table 3 step-by-step reduction puies forward ferrum, coal gasification and coal-gas recovering procedures system material input amount and product quantum of output calculates knot
Really
Additionally, reduction carries the CO of iron furnace generation2And CO gaseous mixture carries out waste heat recovery through flue gas heat-exchange unit, and coal gasification
The high temperature CO producing in stove carries out waste heat recovery through waste heat boiler, is 70% calculating by waste heat recovery efficiency, can be separately recovered
Waste heat is about 597kJ, and 79kJ, is roughly equal to the standard coal of 0.023kg.
The gasifying agent that coal gasification course adopts be industrial furnace or boiler produce containing CO2Waste gas, CO2Consumption is
0.035m3, being converted into quality is 0.0694kg, often processes 1kg copper ashes using the method for the present invention it is possible to absorb
The CO of 0.0694kg2Waste gas, then the 15000000 tons of copper ashes producing for annual China are up to 1,040,000 tons of CO it is possible to absorb2
Waste gas.
Can by the theory analysis and calculating that copper ashes step melting is reduced with the system reclaiming ferrum and coal gasification waste heat recovery
Know, the present invention is that Component seperation, waste heat recovery and the utilization of resources of copper ashes provide brand-new thinking.The present invention's is beneficial
Effect is：(1) utilize the high temperature section waste heat of chemical method high efficiente callback molten copper slag, using low temperature in Physical high efficiente callback copper ashes
Duan Yure it is achieved that the link of copper ashes dry granulation, waste heat reclaiming process and copper ashes valuable metal extraction process, in protection ring
While border economizes on resources, solve the series of problems of high temperature copper ashes processing procedure again；(2) utilize step-by-step reduction method also native copper
Slag, the ferrum in efficient recovery copper ashes, iron recovery reaches more than 90%, wherein in the molten iron of generation iron-holder up to 92% with
On, copper content is 1.5% about, meets the requirement smelting extraordinary weathering steel, can be directly entered pneumatic steelmaking, iron content fall in slag
To less than 3.4%, copper content is down to 0.08% about；(3) reduction puies forward the CO gas process that ferrum process and coal gasification course produce
Self-loopa use can be carried out after separating, greatly reduce energy resource consumption；(4) in gas fractionation unit, assembling NaOH solution absorbs
The CO of reduction process2Gas can prepare the higher soda of purity；Assembling Ca (OH)2Solution absorbs the CO of reduction process2Gas can be made
Standby CaCO3Repeat to reclaim and be used in reduction process it is achieved that becoming waste gas recycling into precious and resource；(5) coal gasification course
Using gasifying agent be industrial furnace or boiler produce containing CO2Waste gas, can give up to industrial generation while energy-saving and emission-reduction again
Gas is effectively treated；(6) granule slag after reduction, recovery ferrum and recovery waste heat for the copper ashes can be transported to cement plant, uses
It is worth high, be truly realized the recycling of copper ashes.
Brief description
Fig. 1 be step-by-step reduction from molten copper slag in the embodiment of the present invention 1 reclaim ferrum and coal gasification recovery waste heat be
System structural representation, in figure 1, reduction carry iron furnace, and 2, copper ashes entrance, 3, flue, 4, flux entrance, 5, slag outlet, 6, reduction
Agent nozzle, 7, molten iron outlet, 8, jet for gas, 9, coal gas burner, 10, high-temperature heat-exchanging, 11, cryogenic heat exchanger, 12, blower fan,
13rd, coal gasifier, 14, gasifying agent nozzle, 15, coal nozzle, 16, waste heat boiler, 17, cyclone dust extractor, 18, gas chamber, 19,
Pressurization air distributing device, 20, water-cooling wall, 21, pelletizer, 22, granulation and waste-heat recovery device, 23, blower fan, 24, deflection plate, 25,
Feeding device, 26, waste heat boiler, 27, gas separation dust arrester, 28, slag particle collects and waste-heat recovery device.
Fig. 2 is the process chart of the method that step-by-step reduction reclaims ferrum and coal gasification recovery waste heat from molten copper slag.
Specific embodiment
The copper ashes that the present invention implements to adopt derives from the deslagging of certain Tong Ye company limited flash smelting furnace domestic, main component
As shown in table 4.
Table 4 copper ashes each constituent mass percentage ratio
Note：In copper ashes given in table, iron content is 36.6%, and other impurities are mainly Anhydrite and calcium and magnesium silicate etc.
Material.
The present invention implements the gasifying agent CO adopting2From certain limekiln flue gas, mainly consist of CO2、N2And vapor,
Its constituent content is respectively 32.2%, 59.6% and 8.2%.
Embodiment 1
From molten copper slag, step-by-step reduction reclaims ferrum and the system of coal gasification recovery waste heat carries as shown in Fig. 2 including reduction
Iron furnace 1, coal gasifier 13, granulation and waste-heat recovery device 22, flue gas heat-exchange unit 10,11, gas separation dust arrester 27, waste heat
Boiler 16,24, cyclone dust extractor 17, gas chamber 18, feeding device 25, wherein gas chamber 18 connect reduction and carry iron furnace 1, and reduction carries
Iron furnace 1 upper end connects gas separation dust arrester 27 by flue gas heat-exchange unit 10,11, separates dust arrester 27 top and is provided with pipeline
Connect gas chamber 18, the slag notch that reduction carries iron furnace 1 connects coal gasifier 13, coal gasifier 13 passes through waste heat boiler 16 and connects rotation
One end of wind cleaner unit 17, cyclone dust extractor 17 other end connects gas chamber 18, the slag notch of coal gasifier 13 connect granulation and
Waste-heat recovery device 22, granulation and waste-heat recovery device 22 connect feeding device 25.
The molten bath bottom that reduction carries iron furnace 1 is provided with reductant nozzle 6；It is sequentially provided with coal gas burner from top to bottom on the left of furnace wall
9, jet for gas 8 and molten iron outlet 7；It is provided with flux entrance 4, slag outlet 5 from top to bottom on the right side of furnace wall；Upper right side is provided with flue
3；Coal gas burner 9 is located above molten bath, and jet for gas 8 stretches into molten bath bottom.
The both sides furnace wall of coal gasifier 13 is respectively equipped with 2 coal nozzles 15 and 2 gasifying agent nozzles 14, and nozzle all stretches into
In the molten bath of coal gasifier.
Granulation and waste-heat recovery device 22 include pelletizer 21, and slag particle is collected and waste-heat recovery device 28 two parts, top
For pelletizer 21, bottom is located in granulation and waste-heat recovery device 22 for slag particle collection and waste-heat recovery device 28, pelletizer 21
The heart, pelletizer 21 is welded in slag particle collection and the metal inner surface of waste-heat recovery device 28 by steel plate；Slag particle is collected and waste heat
Retracting device 28 top is funnel shaped, and bottom is drum, and internal and external walls face is metal water-cooling wall, in lower cylindrical
24,5 grades of downward-sloping endless metal deflection plate is respectively provided with wall, deflection plate length is 0.6m, and spacing is 0.5m, with level
Face angle is 20 °；Granulation and waste-heat recovery device are additionally provided with blower fan 23 and waste heat boiler 26, and blower fan 23 is located at granulation and waste heat returns
Receiving apparatus 22 bottom, waste heat boiler 26 is located at granulation and waste-heat recovery device 22 upper right quarter.
Using said apparatus, from molten copper slag, step-by-step reduction reclaims ferrum and coal gasification recovery waste heat, comprises the following steps that：
(1) step-by-step reduction puies forward ferrum and coal-gas recovering：
1200～1300 DEG C discharged from copper smelter of molten state copper ashes is flowed into reduction and carries iron furnace, by gas chamber
CO is burnt by coal gas burner, treats that bath temperature rises to 1450 DEG C～1500 DEG C, from jet for gas injection CO, copper ashes is entered
Row CO reduction reaction, CO consumption is 1: 3 with Fe amount in copper ashes according to mol ratio, and the injection time is 25min, and jetting pressure is
0.5Mpa；Reaction stops injection CO after terminating, and adds limestone, amount of lime and SiO in copper ashes2Measure and according to mol ratio be
1.2: 1, reducing agent reduction reaction, pulverized coal consumption and Fe amount in copper ashes are carried out by reductant nozzle coal injection to copper ashes simultaneously
It is 1.1: 1 according to mol ratio, the injection time is 30min；Reaction stops coal injection after terminating, by the copper ashes insulation standing of reduction
20min, the copper ashes after sedimentation is divided into two-layer, and lower floor is that molten iron carries iron furnace lower curtate from reduction and flows out, and upper strata is reduced blast furnace from going out
Cinder notch flows into coal gasifier.
CO burning and the CO of two step reduction reactions generation2And CO gaseous mixture, after flue gas heat-exchange unit recovery waste heat, passes through
NaOH solution in gas separation dust arrester removes CO2Gas, is the higher soda of purity after evaporative crystallization；CO returns
Return gas chamber and continue cycling through use.
(2) coal gasification and coal-gas recovering：
The initial temperature that reduced blast furnace flows into coal gasifier is 1450～1500 DEG C, is blown particle diameter by coal nozzle and exists
The mass ratio of the coal dust of below 1mm, coal dust and reduced blast furnace is 1: 0.02, is blown gasifying agent CO by gasifying agent nozzle2, CO2With
Amount and pulverized coal consumption are 1: 1 according to mol ratio, and the temperature of monitoring reduced blast furnace treats that temperature is down to about 1200 DEG C, by reduced blast furnace
Enter granulation and waste-heat recovery device from slag notch.
The CO that coal gasification course produces enters cyclone dust extractor dedusting after waste heat boiler recovery waste heat, clean after dedusting
Net CO enters gas chamber and continues cycling through use.
(3) granulation and waste heat recovery：
Reduced blast furnace is introduced into pelletizer and carries out dry method centrifugal breaking, forms the granule slag of diameter about 1mm, in centrifugation masterpiece
It is thrown out of entrance slag particle with lower granule slag to collect and waste-heat recovery device, and "the" shape fortune is made on endless metal deflection plate
Dynamic, it is passed through air, the waste heat that granule slag is collected in heat exchange is carried out with the air being passed through by granule slag, the air after heat exchange is from grain
Change and waste-heat recovery device upper right quarter enters waste heat boiler, the heat that waste heat boiler reclaims entrained by hot-air produces hot water, returns
Receive the granule slag after waste heat and fall into bottom of device, temperature is down to 100 DEG C about, enters feeding device, and granule slag can be used as building
Materials'use.
Reclaim ferrum and the waste heat in molten copper slag using this system, iron recovery, up to 92%, can obtain copper-iron alloy melt
Up to more than 90%, copper content is 1.7% to iron-holder, and in slag, iron content is 3.1%, and copper content is 0.11%；Every kilogram of copper ashes
Absorbable CO20.035m3, produce CO 0.035m3；The calorific value of gas that coal gasification and coal-gas recovering stage produce 4500kJ with
On, up to 85%, granulation and waste heat recovery stage waste heat recovery efficiency are up to 65% for waste heat recovery efficiency.
Embodiment 2
From molten copper slag, with embodiment 1, difference exists the system of step-by-step reduction recovery ferrum copper and coal gasification recovery waste heat
In：Granulation and waste-heat recovery device do not set blower fan 23 and waste heat boiler 26,7 grades of its endless metal deflection plate, and deflection plate length is
0.4m, spacing is 0.4m, is 10 ° with horizontal plane angle；Carry out heat exchange using being passed through cold water in metal water cold wall；
Using said apparatus, from molten copper slag, step-by-step reduction reclaims ferrum copper and coal gasification recovery waste heat, and concrete steps are such as
Under：
(1) step-by-step reduction puies forward ferrum and coal-gas recovering：
1200～1300 DEG C discharged from copper smelter of molten state copper ashes is flowed into reduction and carries iron furnace, by gas chamber
CO is burnt by coal gas burner, treats that bath temperature rises to 1450 DEG C～1500 DEG C, from jet for gas injection CO, copper ashes is entered
Row CO reduction reaction, CO consumption is 1: 2.5 with Fe amount in copper ashes according to mol ratio, and the injection time is 30min, and jetting pressure is
1.0Mpa；Reaction stops injection CO after terminating, and adds flux dolomite, dolomite consumption and SiO in copper ashes2Amount is according to mol ratio
For 1.2: 1, coke is blown by reductant nozzle simultaneously and copper ashes is carried out with reducing agent reduction reaction, coke consumption and F in copper ashese
Amount is 1.2: 1 according to mol ratio, and the injection time is 20min；Reaction stops injection coke after terminating, will be quiet for the copper ashes insulation of reduction
Put 40min, the copper ashes after sedimentation is divided into two-layer, lower floor be molten iron from reduction carry iron furnace lower curtate flow out, upper strata be reduced blast furnace from
Slag notch flows into coal gasifier.
CO burning and the CO of two step reduction reactions generation2And CO gaseous mixture, after flue gas heat-exchange unit recovery waste heat, passes through
Ca (OH) in gas separation dust arrester2Solution removes CO2Gas, the precipitate of formation is CaCO3, CaCO3Through filtration drying
After can as flux put into reduction carry iron furnace repeat recycle；CO returns gas chamber and continues cycling through use.
(2) coal gasification and coal-gas recovering：
The initial temperature that reduced blast furnace flows into coal gasifier is 1450～1500 DEG C, is blown particle diameter by coal nozzle and exists
The mass ratio of the coal dust of below 1mm, coal dust and reduced blast furnace is 1: 0.02, is blown gasifying agent CO by gasifying agent nozzle2, CO2With
Amount and pulverized coal consumption are 1: 1 according to mol ratio, and the temperature of monitoring reduced blast furnace treats that temperature is down to about 1200 DEG C, by reduced blast furnace
Enter granulation and waste-heat recovery device from slag notch.
The CO that coal gasification course produces enters cyclone dust extractor dedusting after waste heat boiler recovery waste heat, clean after dedusting
Net CO enters gas chamber and continues cycling through use.
(3) granulation and waste heat recovery：
Reduced blast furnace is introduced into pelletizer and carries out dry method centrifugal breaking, forms the granule slag of diameter about 1mm, in centrifugation masterpiece
It is thrown out of entrance slag particle with lower granule slag to collect and waste-heat recovery device, and "the" shape fortune is made on endless metal deflection plate
Dynamic, it is passed through cooling water in water-cooling wall, the waste heat that granule slag is collected in heat exchange is carried out by granule slag and water-cooling wall, after recovery waste heat
Granule slag fall into bottom of device, temperature is down to 100 DEG C about, enters feeding device, and granule slag can use as construction material.
Reclaim ferrum and the waste heat in molten copper slag using this system, iron recovery, up to 96%, can obtain copper-iron alloy melt
Up to more than 94%, copper content is 1.9% to iron-holder, and in slag, iron content is 1.6%, and copper content is 0.08%.；Every kilogram of copper ashes
Absorbable CO20.035m3, produce CO 0.035m3；The calorific value of gas that coal gasification and coal-gas recovering stage produce 4500kJ with
On, up to 85%, granulation and waste heat recovery stage waste heat recovery efficiency are up to 70% for waste heat recovery efficiency.
Embodiment 3
From molten copper slag, with embodiment 1, difference exists the system of step-by-step reduction recovery ferrum copper and coal gasification recovery waste heat
In：Granulation and waste-heat recovery device do not set blower fan 23 and waste heat boiler 26, its endless metal deflection plate, 7 grades, and deflection plate length is
0.8m, spacing is 0.6m, is 30 ° with horizontal plane angle；Carry out heat exchange using being passed through cold water in metal water cold wall.
Using said apparatus, from molten copper slag, step-by-step reduction reclaims ferrum copper and coal gasification recovery waste heat, and concrete steps are such as
Under：
(1) step-by-step reduction puies forward ferrum and coal-gas recovering：
1200～1300 DEG C discharged from copper smelter of molten state copper ashes is flowed into reduction and carries iron furnace, by gas chamber
CO is burnt by coal gas burner, treats that bath temperature rises to 1450 DEG C～1500 DEG C, from jet for gas injection CO, copper ashes is entered
Row CO reduction reaction, CO consumption is 1: 3 with Fe amount in copper ashes according to mol ratio, and the injection time is 20min, and jetting pressure is
1.0Mpa；Reaction stops injection CO after terminating, and adds quick lime, quick lime consumption and SiO in copper ashes2Amount is 1 according to mol ratio:
1, graphite is blown by reductant nozzle simultaneously and copper ashes is carried out with reducing agent reduction reaction, graphite levels and Fe amount in copper ashes according to
Mol ratio is 1: 1, and the injection time is 40min；Reaction stops injection graphite after terminating, by the copper ashes insulation standing 30min of reduction,
Copper ashes after sedimentation is divided into two-layer, and lower floor is that molten iron proposes the outflow of iron furnace lower curtate from reduction, and upper strata is reduced blast furnace from slag notch stream
Enter coal gasifier.
CO burning and the CO of two step reduction reactions generation2And CO gaseous mixture, after flue gas heat-exchange unit recovery waste heat, passes through
Ca (OH) in gas separation dust arrester2Solution removes CO2Gas, the precipitate of formation is CaCO3, CaCO3Through filtration drying
After can as flux put into reduction carry iron furnace repeat recycle；CO returns gas chamber and continues cycling through use.
(2) coal gasification and coal-gas recovering：
The initial temperature that reduced blast furnace flows into coal gasifier is 1450～1500 DEG C, is blown particle diameter by coal nozzle and exists
The mass ratio of the coal dust of below 1mm, coal dust and reduced blast furnace is 1: 0.02, is blown gasifying agent CO by gasifying agent nozzle2, CO2With
Amount and pulverized coal consumption are 1: 1 according to mol ratio, and the temperature of monitoring reduced blast furnace treats that temperature is down to about 1200 DEG C, by reduced blast furnace
Enter granulation and waste-heat recovery device from slag notch.
The CO that coal gasification course produces enters cyclone dust extractor dedusting after waste heat boiler recovery waste heat, clean after dedusting
Net CO enters gas chamber and continues cycling through use.
(3) granulation and waste heat recovery：
Reduced blast furnace is introduced into pelletizer and carries out dry method centrifugal breaking, forms the granule slag of diameter about 1mm, in centrifugation masterpiece
It is thrown out of entrance slag particle with lower granule slag to collect and waste-heat recovery device, and "the" shape fortune is made on endless metal deflection plate
Dynamic, it is passed through cooling water in water-cooling wall, the waste heat that granule slag is collected in heat exchange is carried out by granule slag and water-cooling wall, after recovery waste heat
Granule slag fall into bottom of device, temperature is down to 100 DEG C about, enters feeding device, and granule slag can use as construction material.
Reclaim ferrum and the waste heat in molten copper slag using this system, iron recovery, up to 94%, can obtain copper-iron alloy melt
Up to more than 92%, copper content is 1.7% to iron-holder, and in slag, iron content is 2.4%, and copper content is 0.08%；Every kilogram of copper ashes
Absorbable CO20.074m3, produce CO 0.074m3；The calorific value of gas that coal gasification and coal-gas recovering stage produce 4500kJ with
On, up to 85%, granulation and waste heat recovery stage waste heat recovery efficiency are up to 65% for waste heat recovery efficiency.
Claims (7)
1. a kind of from molten copper slag step-by-step reduction reclaim the system of ferrum and coal gasification recovery waste heat it is characterised in that this system bag
Include reduction and carry iron furnace, coal gasifier, granulation and waste-heat recovery device, flue gas heat-exchange unit, gas separation dust arrester, waste heat pot
Stove, cyclone dust extractor, gas chamber, feeding device；
Described reduction carries the molten bath bottom of iron furnace or furnace wall sidepiece is provided with reductant nozzle；Furnace wall side is simultaneously provided with coal gas and burns
Mouth and jet for gas, and coal gas burner be located at molten bath above, jet for gas stretches into molten bath bottom；
Described flue gas heat-exchange unit includes high-temperature heat-exchanging and cryogenic heat exchanger；
Described granulation and waste-heat recovery device include pelletizer, and slag particle is collected and waste-heat recovery device two parts, and top is granulation
Device, bottom is collected and waste-heat recovery device for slag particle；Pelletizer is located at granulation and waste-heat recovery device center, and pelletizer passes through steel
Plate weld is on the metal inner surface of slag particle collection and waste-heat recovery device；Described slag particle is collected and waste-heat recovery device top is leakage
Bucket shape shape, bottom is drum, and internal and external walls face is metal water-cooling wall, is respectively provided with and dips down on lower cylindrical wall
Oblique endless metal deflection plate；
Gas chamber connects reduction and carries iron furnace, and reduction carries iron furnace upper end and connects gas separation dust arrester by flue gas heat-exchange unit, point
It is provided with pipeline and connects gas chamber above dust arrester, the slag notch that reduction carries iron furnace connects coal gasifier, and coal gasifier passes through
Waste heat boiler connects one end of cyclone dust extractor, and the cyclone dust extractor other end connects gas chamber, and the slag notch of coal gasifier connects
Granulation and waste-heat recovery device, granulation and waste-heat recovery device connect feeding device.
2. according to claim 1 a kind of from molten copper slag step-by-step reduction reclaim ferrum and coal gasification recovery waste heat be
System, it is characterised in that described coal gasifier is provided with coal nozzle and gasifying agent nozzle, stretches in the molten bath of coal gasifier, nozzle number
Amount at least 4, is located at coal gasifier molten bath upper and lower respectively.
3. according to claim 1 a kind of from molten copper slag step-by-step reduction reclaim ferrum and coal gasification recovery waste heat be
It is characterised in that described endless metal deflection plate is 5～7 grades, length is 0.4～0.8m to system, and spacing is 0.4～0.6m, with water
Plane included angle is 10～30 °.
4. a kind of step-by-step reduction from molten copper slag of the system described in employing claim 1 reclaims ferrum and coal gasification recovery waste heat
Method is it is characterised in that comprise the following steps that：
(1) step-by-step reduction puies forward ferrum and coal-gas recovering：
1200～1300 DEG C discharged from copper smelter of molten state copper ashes is flowed into reduction and carries iron furnace, the CO in gas chamber is led to
Cross coal gas burner to be burnt, treat that bath temperature rises to 1450 DEG C～1500 DEG C, from jet for gas injection CO, CO is carried out to copper ashes
Reduction reaction, CO consumption is 1: 3～1: 2.5 with Fe amount in copper ashes according to mol ratio, and the injection time is 20min～30min, injection
Pressure is 0.5～1.0Mpa；Reaction stops injection CO after terminating, and adds flux, flux consumption and SiO in copper ashes2Amount is according to rubbing
Your ratio is 1.2: 1, is blown reducing agent by reductant nozzle simultaneously and copper ashes is carried out with reduction reaction, in reducing agent consumption and copper ashes
Fe amount is 1: 1～1.2: 1 according to mol ratio, and the injection time is 20～40min；Reaction stops injection reducing agent after terminating, will be also
Former copper ashes insulation standing 20～40min, the copper ashes after sedimentation is divided into two-layer, and lower floor carries iron furnace lower curtate stream for molten iron from reduction
Go out, upper strata is that reduced blast furnace flows into coal gasifier from slag notch；
CO burning and the CO of two step reduction reactions generation2And CO gaseous mixture, after flue gas heat-exchange unit recovery waste heat, is divided by gas
Remove CO from dust arrester2Gas, CO returns gas chamber and continues cycling through use；
(2) coal gasification and coal-gas recovering：
Reduced blast furnace flow into coal gasifier initial temperature be 1450～1500 DEG C, by coal nozzle be blown particle diameter 1mm with
Under coal dust, the mass ratio of coal dust and reduced blast furnace is 1: 0.02, is blown gasifying agent CO by gasifying agent nozzle2, CO2Consumption with
Pulverized coal consumption is 1: 1 according to mol ratio, the temperature of monitoring reduced blast furnace, treats that temperature is down to about 1200 DEG C, by reduced blast furnace from going out
Cinder notch enters granulation and waste-heat recovery device；
The CO that coal gasification course produces enters cyclone dust extractor dedusting, the clean CO after dedusting after waste heat boiler recovery waste heat
Enter gas chamber and continue cycling through use；
(3) granulation and waste heat recovery：
Reduced blast furnace is introduced into pelletizer and carries out dry method centrifugal breaking, forms the granule slag of diameter about 1mm, under the action of the centrifugal force
Granule slag is thrown out of entrance slag particle and collects and waste-heat recovery device, and makees "the" shape motion on endless metal deflection plate, leads to
Enter in air or water-cooling wall and be passed through cooling water, heat exchange is carried out by granule slag and the air being passed through or water-cooling wall and collects
The waste heat of grain slag, the granule slag after recovery waste heat falls into bottom of device, and temperature is down to 100 DEG C about, enters feeding device.
5. the side of a kind of step-by-step reduction recovery ferrum and coal gasification recovery waste heat from molten copper slag according to claim 4
Method is it is characterised in that it is limestone or dolomite or quick lime that described step-by-step reduction carries ferrum and the flux of coal-gas recovering process.
6. the side of a kind of step-by-step reduction recovery ferrum and coal gasification recovery waste heat from molten copper slag according to claim 4
Method is it is characterised in that it is coal dust or coke or graphite that described step-by-step reduction carries ferrum and the reducing agent of coal-gas recovering process.
7. the side of a kind of step-by-step reduction recovery ferrum and coal gasification recovery waste heat from molten copper slag according to claim 4
Method is it is characterised in that the solution assembling in described gas separation dust arrester is NaOH solution or Ca (OH)2Solution.
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| CN105838839B (en) * | 2016-05-24 | 2018-08-21 | 江苏省冶金设计院有限公司 | It prepares the method for granulated iron and prepares the system of granulated iron |
| CN106086276B (en) * | 2016-09-09 | 2018-05-29 | 东北大学 | It is a kind of to recycle copper ashes waste heat and be reduced directly the system and method for carrying iron |
| CN108588440A (en) * | 2017-05-03 | 2018-09-28 | 昆明理工大学 | The method that iron resource effectively recycles in slag cleaning furnace copper ashes is realized in a kind of oxidation of carbon dioxide |
| CN107365914A (en) * | 2017-07-11 | 2017-11-21 | 重庆大学 | The method that magnetic separation carries iron in the copper ashes particle prepared from dry method centrifugal granulation method |
| CN107641717A (en) * | 2017-10-10 | 2018-01-30 | 东北大学 | A kind of method produced by cupric slag |
| CN107604118A (en) * | 2017-10-26 | 2018-01-19 | 江苏省冶金设计院有限公司 | Handle the equipment that molten state copper ashes produces high-quality iron |
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| CN112853012B (en) * | 2021-02-05 | 2022-09-09 | 山东迪尔节能科技有限公司 | High-temperature furnace slag air quenching humidifying granulation waste heat recovery system |
| CN113174492A (en) * | 2021-04-28 | 2021-07-27 | 东北大学 | Side-top composite blowing smelting reduction furnace for treating molten copper slag |
| CN113151691A (en) * | 2021-04-28 | 2021-07-23 | 东北大学 | Bottom-top composite blowing smelting reduction furnace for treating molten copper slag |
| CN114686632B (en) * | 2022-04-08 | 2024-03-22 | 瀜矿环保科技(上海)有限公司 | Copper slag recycling and CO based on industrial solid waste 2 Mineralization coupling method and mineralization coupling system |
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| CN101724726B (en) * | 2008-10-29 | 2011-06-15 | 贾会平 | Method and device for ironmaking by smelting |
| CN101597658B (en) * | 2009-07-10 | 2010-12-08 | 东北大学 | Coal gasification system and method of blast furnace slags |
| CN102952952B (en) * | 2012-09-26 | 2014-08-20 | 东北大学 | Method for directly restoring and recovering copper iron from smelting copper slag |
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