CN105803201B - An a kind of step metallurgical Flash Smelting Furnace and metallurgical method - Google Patents
An a kind of step metallurgical Flash Smelting Furnace and metallurgical method Download PDFInfo
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- CN105803201B CN105803201B CN201610283937.3A CN201610283937A CN105803201B CN 105803201 B CN105803201 B CN 105803201B CN 201610283937 A CN201610283937 A CN 201610283937A CN 105803201 B CN105803201 B CN 105803201B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0047—Smelting or converting flash smelting or converting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
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Abstract
The invention provides the Flash Smelting Furnace that an a kind of step is metallurgical, including reaction tower, nozzle is provided with the top of the reaction tower；The one end in the reaction tower bottom connection molten bath, the other end top in the molten bath are provided with uptake flue；The reaction tower lower half is provided with gas leading-in device and is used to import reducibility gas, and reduction air cushion layer is formed in reaction tower lower space.Setting of the invention by reducing air cushion layer, make metal oxide and Fe to be smelted in mineral3O4Metal and FeO are almost completely reduced into, and then contains slag and treats that the amount of metal smelting is extremely low, and improves the property of clinker, reduces its viscosity, beneficial to discharge.
Description
Technical field
The invention belongs to metallurgical technology field, more particularly, to a kind of metallurgical Flash Smelting Furnace of a step and a step metallurgy side
Method.
Background technology
In field of metallurgy, two steps will typically be passed through by sulfide metal concentrate generation crude metal, i.e. melting-blowing,
Traditional method is that melting and blowing are divided among in different device to carry out, as bath smelting+PS bessemerizes, flash smelting+
Flash blowing etc., all there is long flow path, high energy consumption and SO in these traditional handicrafts2The problems such as flue gas low vacancy pollution.Thus someone master
The whole smelting process completed in Zhang Yi metallurgical plant from metal concentrate to crude metal output is a step smelting, and is carried out
The trials of some industrialization:
In copper sulfurized ore field of smelting, Australian Olympic Dam smelteries, Poland Glogow smelteries and
The flash smelting technique that blister copper is exactly directly produced by copper concentrate that the KCM smelteries of Zambia use, the general principle of smelting
It is by adjusting degree of oxidation of the oxygen/material than controlling copper sulfide concentrate, directly producing blister copper, obtained blister copper copper content is about
98.5%.But these methods also have one it is common the characteristics of, be exactly production discharge clinker in, Cu2O content is generally super
Cross 15%, Fe3O4Content is 30%~50%, can then increase investment and production cost to the copper in recovery slag, if do not reclaimed
The significant wastage of resource can be caused again, and slag contains Fe3O4Height, the property deterioration of clinker can be made (slag melting point rise, proportion increase, to glue
Degree increase).To reduce Cu in slag2O and Fe3O4Content, also have tried to the coke charge layer of charcoal of Flash Smelting Furnace molten bath melt upper berth one use
In reduction in flash furnace reaction tower by the Cu oxide of peroxidating, from realizing a step copper metallurgy, but be coke the shortcomings that this method
Substantial amounts of iron can be restored simultaneously, so that iron content is higher in blister copper, subsequently also need to carry out iron removaling refining, meanwhile, the party
Method needs to expend substantial amounts of coke, and energy consumption is higher.
In lead sulphide ore field of smelting, base husband's Saite method is a kind of single step smelting lead method.The big Saite stove of base is by two reaction zones
Composition, stove is interior to be provided with partition wall, and partition wall both sides are respectively oxidation reaction zone and electric furnace reduction area.Fused materials are burnt by weld pool surface
Layer of charcoal realizes the reduction of first stage, and lead skim mixture enters back into the electric furnace reduction area of liquid phase connection, the lead oxides in clinker
By secondary reduction under strong reducing condition.Base husband's Saite furnace gas is mutually separated by partition wall, and oxidation panel flue gas contains SO2Height, reduction section cigarette
Gas mainly contains CO and CO2.Clinker is released with lead bullion by the outlet of reducing zone diverse location.Base husband's Saite stove is substantially Flash Smelting Furnace
Join together to carry out melting with electric furnace, reduction dilution is carried out to the zinc in slag and lead using electric furnace, the technique oxidation panel and reduction
The flue gas of section must be divided into two classes and carry out vent gas treatment respectively, and whole technological process is complicated, and complete equipment investment is big, high energy consumption.
In Ni sulphide mine field of smelting, there are not also a step nickel metallurgy or a step to smelt the industry trial of monel at present.
The content of the invention
In view of this, the present invention is directed to propose a kind of Flash Smelting Furnace of step metallurgy, solves copper sulphur in the method for energy-conserving and environment-protective
Change ore deposit, Ni sulphide mine, clinker present in the step smelting process of lead sulphide ore one containing treating metal smelting and Fe3O4High, slag emission is stranded
In difficult, product the problems such as iron-holder height, high energy consumption, technological process complexity.
To reach above-mentioned purpose, what the technical scheme of the invention was realized in：A kind of metallurgical Flash Smelting Furnace of a step,
Including reaction tower, the one end in the reaction tower bottom connection molten bath, the other end top in the molten bath is provided with uptake flue；It is described
Reaction tower lower half is provided with gas leading-in device and is used to import reducibility gas, and reduction air cushion is formed in reaction tower lower space
Layer.
From dropping process at the top of reaction tower oxidation reaction first occurs for metallic ore to be smelted, and generates the metal oxygen of peroxidating
Compound, then by reaction tower bottom reduce air cushion layer when, metal oxide to be smelted is reduced into metal, Fe3O4It is reduced into
FeO, that is, improve slag and improve the rate of recovery for treating metal smelting again.In reaction tower lower space, by the oxygen of top addition
It is consumed and finishes substantially, reducibility gas, which enters in stove, to be not in vigorous combustion and increases the thermic load of Flash Smelting Furnace, and
Substantial amounts of reducing atmosphere will also absorb heat itself, there is certain cooling effect.
Further, the molten bath upper wall is provided with the barricade goed deep into stove or removable gate close to reaction tower side.Barricade
Set it is possible to prevente effectively from reducibility gas ramps up flue direction quickly spreads, make reaction tower bottom and molten bath side wall and barricade
Between formed one reduction air cushion layer.Barricade is made up of lining refractories outside Copper Water Jacket, and the distance of barricade bottom surface and body of heater bottom surface is
1-3 rice.Preferably, barricade or removable gate are located at the junction of reaction tower and molten bath upper wall, and deep perpendicular to molten bath upper wall
Enter in stove, the reduction air cushion sheaf space so formed is minimum, and reducibility gas is more concentrated, and the utilization rate of effective reducing atmosphere is more
It is high.
Further, molten bath top, side or the flue are provided with some spray guns or air-blast device.Have neither part nor lot in going back for reaction
Originality gas from communicating passage of the reaction tower bottom through molten bath top ramp up flue flowing during, spray gun or drum can be passed through
Wind apparatus sprays into or blasted oxygen-containing gas, is burnt with the reducing gas of surplus, is molten bath additional heat, while eliminate uptake flue
The flue dust being likely to occur bonds.
Further, the reducibility gas contains effective reducing atmosphere, and effective reducing atmosphere is CO, H2Or hydrocarbon
One or more in (such as methane) gas；Preferably, it is the waste gas containing reducing atmosphere of industrial production discharge；It is furthermore preferred that
For blast furnace gas, coal gas of converter, coke-stove gas, electric furnace (mineral hot furnace) tail gas, rotary kiln exhaust gas, rotary hearth furnace tail gas etc.；The present invention
Create using above-mentioned industrial waste gas as gas is smelted, above-mentioned waste gas is passed through tail gas clean-up processing stream again
Journey, substantially reduces the investment of original production process, on the other hand reduces the production cost of metallurgical technology of the present invention, realizes
The circulation comprehensive of resource utilizes, and turns waste into wealth.
Preferably, effective reducing atmosphere (CO and H in the reduction air cushion layer2) content is 35%-70%.According to metallurgical heat
Mechanics principle, under the high temperature of 1100-1450 DEG C of reaction tower space, effective reducing atmosphere (CO+H of above range2) can make
Fe3O4It is easier to be reduced to FeO, and FeO can not almost be reduced into simple substance Fe, meanwhile, copper, nickel and lead oxides are in said temperature
Easily it is reduced with reducing atmosphere concentration.Miberal powder is by reduction air cushion layer, and metal oxide to be smelted therein is substantially all
It is reduced into metal simple-substance.
Another object of the present invention is to provide a kind of method of the step of Flash Smelting Furnace one metallurgy described in utilization, its feature exists
In：It will treat that metal smelting ore deposit, flux, oxygen-containing gas, cold burden are added in reaction tower by the nozzle at the top of Flash Smelting Furnace, pass through gas
Body gatherer imports reducibility gas to reaction tower bottom；Heating, treat that metal smelting ore deposit first passes through reaction tower top and oxygen occurs
Change reaction, generate metal oxide, then the reduction air cushion layer by reaction tower bottom, reduction reaction occurs, generate metal simple-substance,
Crude metal layer is formed in molten bath bottom；After the gangue content in metal smelting ore deposit and flux slag making slag is formed on molten bath top
Layer；Crude metal and slag discharge out of the furnace respectively；The flue gas of reaction generation is discharged by uptake flue.
This method specifically comprises the steps of：
1) stock up：By metallic ore to be smelted dry and dispersion be water content below 0.3%, granularity is less than 0.2mm's
Pulp, the aqueous 1%, granularity that is less than of sludging flux are less than 1mm；Cold burden is aqueous to be less than 1%, and granularity is less than 5mm.
2) middle part aoxidizes on reaction tower：Metal mining powder, flux, oxygen-containing gas, cold burden are passed through into the nozzle at the top of Flash Smelting Furnace
Be injected in red-hot reaction tower, using miberal powder specific surface area it is big, at high temperature with the fireballing characteristic of oxygen reaction, make miberal powder
Oxidation reaction occurs rapidly for middle part on reaction tower with oxygen, generates Multimetal oxide, and release substantial amounts of heat.
3) reaction tower bottom and the reduction of molten bath upper space：Reproducibility is imported to reaction tower bottom by gas leading-in device
Gas, a reduction air cushion layer is formd in reaction tower bottom and molten bath melt upper space, the metal oxide of generation is under
When falling by the reduction air cushion layer, metal oxide to be smelted is reduced into metal simple-substance, is reduced by controlling in air cushion layer
Effective reducing atmosphere (CO+H in reducibility gas2) concentration, control Fe3O4Reducing degree, it is reduced into FeO,
And metal Fe can not be reduced into, the flue gas for reacting generation is discharged by uptake flue.
4) molten bath slag making separates：Molten bath is being fallen into by the reacted melt in above-mentioned space, gangue content therein is with melting
Slag making reaction occurs for agent, generates the slag of low melting point, due to the difference of density, metal and the slag of the liquid for being reduced out sink
Form sediment and be layered, from top to bottom formation slag blanket and crude metal layer, the noble metal removal in raw material is in the crude metal layer of melting, then passes through
Metal discharge mouth and slag-drip opening respectively discharge out of the furnace crude metal and metallurgical slag.
Preferably, during being somebody's turn to do, the temperature control in reaction tower is at 1100-1450 DEG C.
Preferably, in oxygen-containing gas oxygen volumetric concentration >=50%.
Preferably, it is described treat metal smelting ore deposit for copper sulfurized ore (or doped portion copper sulphur or copper scap), Ni sulphide mine (or
Doped portion nickel sulphur), one kind in lead sulphide ore (or doped portion lead containing sludge or flue dust).The Flash Smelting Furnace of the proposition of the present invention
It is wide to adaptability to raw material with a step smelting process, the Ni sulphide mine and low lead of copper sulfurized ore, the high MgO of low nickel for low copper high ferro
The lead sulphide ore of high ferro is all suitable for, and can produce certain economic benefit.
In order to solve to complete metallic sulfide oxidation and metal oxide also in same reacting furnace in currently available technology
Former two kinds of courses of reaction, are aoxidized using in space, while are set coke layer on molten bath melt top layer or set in molten bath
The mode of electrode realizes the reduction task of metal oxide, and its essence is to be aoxidized by the use of carbon as reducing agent to be reduced directly metal
Thing, thus inevitably make metal Fe simple substance be reduced out, cause to contain a certain amount of iron in last crude metal, subsequently
Also need to individually refine iron removal step, added investment and energy consumption, while in this process, the consumption of coke or electrode material
Amount is also very big, and production cost is high.And the technical scheme that the invention proposes is in flash furnace reaction tower space structure from top to bottom
Two kinds of metallurgical atmosphere of oxidation and reduction have been built, CO and H is used in air cushion layer is reduced2Etc. effective reducing atmosphere as reducing agent,
By controlling the method for the temperature and effective reducing atmosphere concentration partial pressure that reduce in air cushion layer to enable metal oxide to be smelted
It is completely reduced into metal simple-substance, and Fe3O4FeO can only be reduced into, fe can not be restored, this is relative to existing skill
One important technical of art improves.
Further, the cold burden is that the raw ore containing valuable metal, flue dust, pyrometallurgical smelting slag, hydrometallurgy slag are (including floating
Slag) in one or more.Preferably, the valuable metal is the one or more in gold, silver, indium, copper, bismuth, cobalt.Cold burden one
Aspect absorbs the thermic load that with furnace heat, can reduce Flash Smelting Furnace, and metal bath (Cu or Ni on the other hand can be used in molten bath
Or Pb) trapping cold burden in valuable metal (valuable metal finally dissolving is enriched in crude metal, subsequently can be with separation and Extraction), do
To turning waste into wealth.
Further, Fe in the metallurgical slag slag blanket3O4Content be less than 0.5%.The method that the invention proposes, passes through
Control imported into the flow velocity of reducibility gas in flash furnace reaction tower, you can adjusts the thickness of flash furnace reduction air cushion layer and goes back
The concentration partial pressure of effective reducing atmosphere in Primordial Qi bed course, so that metal oxide (Cu to be smelted2O or NiO or PbO) can quilt
It is reduced into metal simple-substance completely, and Fe3O4FeO can only be reduced into, the Fe in the metallurgical slag for ensureing finally to discharge out of the furnace3O4Contain
While amount is less than 0.5%, effective reducing atmosphere in reducibility gas is consumed as far as possible again, improve the utilization of effective reducing atmosphere
Rate, reduce energy consumption.
Relative to prior art, the metallurgical Flash Smelting Furnace of a step that the invention proposes and a step metallurgical method have following
Advantage：
The metallurgical Flash Smelting Furnace of a step of the present invention and a step metallurgical method pass through reducing atmosphere (CO/H2) can be to iron
Oxide carries out the characteristic of selective reduction, metal oxide to be smelted is completely reduced into metal simple-substance, and Fe3O4
FeO can only be reduced into, fe can not be restored, so as to ensure that the rate of recovery for treating metal smelting, reduces thick gold again
Iron-holder in category, improve the performance of slag.
The reducibility gas wide material sources that the metallurgical Flash Smelting Furnace of a step of the present invention is imported, can be directly using industry
On the one hand the waste gas containing reducing atmosphere with heat of production discharge makes waste gas net by tail gas again as gas is smelted
Change handling process, substantially reduce the investment of original production process, on the other hand reduce the production of metallurgical technology of the present invention
Cost, meanwhile, without sharp using a large amount of coke and expensive electrode material, more energy efficient environmental protection, the synthetical recovery for realizing resource
With.
The metallurgical Flash Smelting Furnace structure of a step of the present invention is simple, is not required to additionally use electric furnace or adds coke disposal to melt
Slag, investment is small, production cost is low.
Brief description of the drawings
The accompanying drawing for forming the part of the invention is used for providing further understanding the invention, present invention wound
The schematic description and description made is used to explain the invention, does not form the improper restriction to the invention.
In accompanying drawing：
Fig. 1 is the metallurgical Flash Smelting Furnace of the step described in the invention embodiment 1-3.
Description of reference numerals：
1- reaction towers, 2- nozzles, 3- gas leading-in devices, 4- reduction air cushion layers, 5- molten baths, 6- barricades, 7- slag blankets, 8- are thick
Metal level, 9- spray guns；10- uptake flues.
Embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the invention can
To be mutually combined.
The metallurgical Flash Smelting Furnace of the step of embodiment 1 one
A kind of metallurgical Flash Smelting Furnace of a step, including reaction tower 1, the top of reaction tower 1 are provided with nozzle 2；The bottom of reaction tower 1 connects
The one end in molten bath 5, the other end top in molten bath 5 are provided with uptake flue 10；Used provided with gas leading-in device 3 lower half of reaction tower 1
In importing reducibility gas, contain CO and H in reducibility gas2.Reducibility gas is empty in the bottom of reaction tower 1 and the top of molten bath 5
Between formed reduction air cushion layer 4.Molten bath 5 and the junction of reaction tower 1 are provided with barricade 6.On the top of molten bath 5, side and uptake flue 10
Provided with some spray guns 9.
The method that embodiment 2 utilizes the step copper metallurgy of Flash Smelting Furnace one of embodiment 1
1st, raw material and auxiliary material prepare
Raw material is used in the present embodiment as a kind of import copper concentrate, main component such as following table：
| Composition | Cu | S | Fe | SiO2 | CaO+MgO |
| % | 29.5 | 31 | 26 | 6 | 1 |
By raw material drying and dispersion be water content below 0.3%, granularity accounted for below 200 mesh 80% dry concentrate.
Flux is SiO2Silica flour of the content more than 90%, the aqueous 1%, granularity that is less than of silica flour account for less than 60 purposes
90%, herein silica flour as flux participate in flash smelting slagging process.
Cold burden be containing one kind in valuable metal such as gold, silver, indium, copper, the flue dust of bismuth, clinker, raw ore, wet-leaching slag or
It is a variety of, dry to aqueous and be less than 1%, granularity is less than 5mm.On the one hand cold burden absorbs heat excessive in stove, reduce Flash Smelting Furnace
Thermic load, (valuable metal finally dissolves for the copper liquid trapping that the valuable metal on the other hand wherein contained can be melted in molten bath 5
It is enriched in blister copper, subsequently can be with separation and Extraction), so that secondary resource is recycled utilization, kill two birds with one stone, turn waste into wealth.
Oxygen-containing gas is generally oxygen-air mixture, and generally use air and the mixing of industrial oxygen are made into, oxygen-containing gas
Volumetric concentration >=50% of middle oxygen.
2nd, smelting process
Raw material, flux, oxygen-containing gas, cold burden are added to flash furnace reaction tower 1 by Flash Smelting Furnace top jet nozzle 2, dodged
In fast furnace reaction tower 1, Cu2S generates Cu by direct oxidation2O, also there is the Cu of part peroxidating2O and Fe3O4With under-oxidized Cu2S
Cross reaction generation copper, part copper is oxidized to Cu once more2O.The mass ratio for controlling oxygen and copper concentrate to add is 43%-
47%, on the one hand make finally all to be oxidized into the sulphur in the copper concentrate of reaction tower 1 and sulfide, finally fall into molten bath 5
S content is less than 0.05% in material, meanwhile, also make the oxidation reaction of sulphur in copper concentrate, sulfide and iron by reaction tower 1
The oxygen depletion of central space, it is in weak oxide environment to make the lower space of reaction tower 1.
Substantial amounts of Cu is generated after the oxidation reaction at the upper middle part of reaction tower 12O、Fe3O4With a small amount of copper, to avoid
Cu2O and Fe3O4Into clinker, the present invention imports reducibility gas in the bottom of reaction tower 1, and reducibility gas contains CO, H2Or carbon
One or more in hydrogen compound gas (such as methane) effectively reducing atmosphere, preferably industrial production discharge contain also Primordial Qi
The waste gas of atmosphere such as blast furnace gas, coal gas of converter, coke-stove gas, electric furnace (mineral hot furnace) tail gas, rotary kiln exhaust gas, rotary hearth furnace tail gas
Deng.Barricade is set in the junction in reaction tower 1 Yu molten bath 5, is full of formation between the bottom of reaction tower 1 and the top of molten bath 5 and barricade
The reduction air cushion layer 4 of reducing atmosphere.
In the lower space of reaction tower 1, it is consumed and is finished substantially by the oxygen of top addition, reducibility gas enters in stove
Be not in vigorous combustion and increase the thermic load of Flash Smelting Furnace, and substantial amounts of reducibility gas will absorb heat itself,
There is certain cooling effect to body of heater.Work as Cu2O and Fe3O4It is dropped through and contains effective reducing atmosphere (CO+H2) concentration is 35%-
During 70% reduction air cushion layer 4, Cu2O is reduced into simple substance Cu, Fe3O4FeO is reduced into, that is, the rate of recovery for improving copper changes again
It has been apt to slag.
After above-mentioned reactant melt falls into molten bath 5, FeO and flux SiO therein2Slag making, the slag of liquid and the copper of melting
Liquid is due to the different precipitated and separateds of proportion, and it is blister copper layer to form slag blanket 6 and crude metal layer 7, and generation contains SO2Flue gas pass through
Uptake flue 10 discharges out of the furnace, then can introduce sulfuric acid plant's relieving haperacidity after cooling, dedusting.In the top of Flash Smelting Furnace molten bath 5, side
And some spray guns 9 on uptake flue 10, having neither part nor lot in effective reducing atmosphere (CO or the H of reaction2) connection through the top of molten bath 5
During space ramps up the flowing of flue 10, oxygen-containing gas can be sprayed into or blasted, is on the one hand the additional heat of molten bath 5, simultaneously
The flue dust that uptake flue 10 is likely to occur is eliminated to bond.
The method of one step copper metallurgy of the proposition of the present invention has wide applicability to raw material, is applicable not only to the low Fe of high Cu
Copper concentrate, it can also be used to the smelting of the low Cu of high Fe copper concentrate, meanwhile, doped portion copper sulphur or copper scap are also in concentrate
Feasible.
3rd, the main chemical reactions occurred in smelting process
1) main chemical reactions that central space occurs on reaction tower：
A. decomposition reaction
4CuFeS2=2Cu2S+4FeS+S2
2FeS2=2FeS+S2
4CuS=2Cu2S+S2
B. oxidation reaction
2Cu2S+3O2=2Cu2O+2SO2
2FeS+3O2=2FeO+2SO2
6FeO+O2=2Fe3O4
S+O2=SO2
C. cross reaction
3Fe3O4+ FeS=10FeO+SO2
Cu2O+FeS=Cu2S+FeO
Cu2S+2Cu2O=6Cu+SO2
2) main chemical reactions (reduction reaction) that reaction tower lower space and molten bath upper space occur
Cu2O+CO=2Cu+CO2 Cu2O+H2=2Cu+H2O
Fe3O4+ CO=3FeO+CO2 Fe3O4+H2=3FeO+H2O
3) esoteric main chemical reactions (slag making reaction) are melted in molten bath
2FeO+SiO2=2FeOSiO2
CaO+SiO2=CaOSiO2
The method that embodiment 3 utilizes the thick alloy of step nickel metallurgy copper of Flash Smelting Furnace one of embodiment 1
1st, raw material, fuel and auxiliary material prepare
Raw material is nickel ore concentrate, and main nickeliferous, two kinds of metals of copper in nickel ore concentrate, the mass ratio of ambrose alloy content is generally in 1.5-
Between 2.5, additionally containing cobalt and a small amount of gold, silver and platinum group metal.The composition for the nickel ore concentrate that the present embodiment uses is as follows：
| Composition | Ni | Cu | Co | Fe | S | SiO2 | CaO | MgO |
| % | 6.6 | 2.8 | 0.3 | 39.5 | 27.3 | 8.2 | 1.2 | 6 |
By raw material drying and dispersion be water content below 0.3%, granularity accounted for below 200 mesh 80% dry concentrate.
Flux is SiO2Silica flour of the content more than 90%, the aqueous 1%, granularity that is less than of silica flour account for less than 60 purposes
90%.Silica flour participates in the slagging process of flash smelting as flux herein.
Coal must carry out coal-grinding and drying process as fuel, its water content is accounted for 85% less than 200 mesh less than 1%, granularity；
Fine coal provides required heat for flash smelting by burning.
Oxygen-containing gas directly uses technique oxygen (O2>=70%)
2nd, smelting process
Raw material, flux, technique oxygen, fine coal are added in flash furnace reaction tower 1 by Flash Smelting Furnace top jet nozzle 2,
At a temperature of 1100-1450 DEG C, (NiFe) in nickel ore concentrate9S8、CuFeS2Sulfides are decomposed reaction, generate Ni3S2、
Cu2S, the metal sulfide such as FeS, CoS, this several sulfide are largely oxidized to rapidly NiO, Cu2O、Fe3O4, CoO, peroxide
NiO, Cu of change2O, CoO and Fe3O4Cross reaction occurs in an impact with under-oxidized FeS (centre of particle), generates
Metal and sulfide can be oxidized again again, in the process, oxygen is gradually depleted.What control oxygen and nickel ore concentrate added
Mass ratio is 42%-47.5%, on the one hand makes the Ni into reaction tower 13S2、Cu2S, FeS, CoS sulfides and sulphur are finally complete
Portion is oxidized, and the content for making finally to fall into S in the material in molten bath 5 is less than 0.05%, meanwhile, also make sulphur in nickel ore concentrate, vulcanization
For the oxidation reaction of thing and iron by the oxygen depletion of central space on reaction tower 1, it is in weak oxide environment to make in the lower space of reaction tower 1.
To avoid NiO, Cu in the oxidized reaction generation in the upper middle part of reaction tower 12O, CoO and Fe3O4Into clinker, sheet
Invention imports reducibility gas in the bottom of reaction tower 1, and reducibility gas contains CO, H2Or hydrocarbon gas (such as methane)
One or more in effective reducing atmosphere, the preferably such as blast furnace gas of the waste gas containing reducing atmosphere of industrial production discharge, turn
Producer gas, coke-stove gas, electric furnace (mineral hot furnace) tail gas, rotary kiln exhaust gas, rotary hearth furnace tail gas etc..Company in reaction tower 1 Yu molten bath 5
Meet place and barricade is set, make to form the reduction air cushion layer 4 full of reducing atmosphere between the bottom of reaction tower 1 and the top of molten bath 5 and barricade.
In the lower space of reaction tower 1, it is consumed and is finished substantially by the oxygen of top addition, reducibility gas enters in stove
Be not in vigorous combustion and increase the thermic load of Flash Smelting Furnace, and substantial amounts of reducing atmosphere will absorb heat itself, it is right
Body of heater has certain cooling effect.As NiO, Cu2O, CoO and Fe3O4It is dropped through and contains effective reducing atmosphere (CO+H2) concentration is
During 35%-70% reduction air cushion layer 4, NiO, Cu2O, CoO is reduced into metal simple-substance Ni, Cu and Co, Fe3O4It is reduced into
FeO, that is, improve the rate of recovery that slag improves Ni, Cu and Co again.
After above-mentioned reactant falls into molten bath 5, MgO, FeO and flux SiO therein2Slag making, the slag of liquid and the copper of melting
Nickel is due to the different precipitated and separateds of proportion, and it is the thick alloy-layer of ambrose alloy to form slag blanket 6 and crude metal layer 7, due to NiO, Cu2O、CoO
And Fe3O4All almost it is reduced completely, slag contains Ni, Cu, Co and Fe3O4It is all very low.The thick alloy of cupro-nickel can extract it in refining
In noble metal after be made into a certain proportion of corronil and sell, such as monel metal, or post-cure is after grinding floating separation
To secondary copper ore concentrate and secondary nickel ore concentrate, then smelt obtain copper metal and nickel metal respectively.
Reaction generation contains SO2Flue gas discharged out of the furnace by uptake flue 10, then by cooling, can introduce after dedusting
To sulfuric acid plant's relieving haperacidity.Some spray guns 9 on the top of Flash Smelting Furnace molten bath 5, side and uptake flue 10, having neither part nor lot in going back for reaction
Primordial Qi atmosphere (CO or H2) connected space through the top of molten bath 5 ramp up flue 10 flow during, can spray into or blast and be oxygen-containing
Gas, it is on the one hand the additional heat of molten bath 5, while eliminates the flue dust that uptake flue 10 is likely to occur and bond.
The method of one step copper metallurgy of the proposition of the present invention has wide applicability to raw material, and it is low to be applicable not only to high Ni
MgO nickel ore concentrate, it can also be used to the smelting of the low Ni of high MgO low-quality nickel ore concentrate, and certain economic benefit can be produced.In essence
Doped portion nickel sulphur or nickeliferous cupric or waste residue containing cobalt are also feasible in ore deposit.In addition, if heat surplus in Flash Smelting Furnace, can also add
Enter containing one or more cold in valuable metal such as gold, silver, indium, copper, bismuth, the flue dust of cobalt, clinker, raw ore, wet-leaching slag
Material, these valuable metals can finally be enriched in blister copper nickel alloy, accomplish twice laid, kill two birds with one stone.
3rd, the main chemical reactions occurred in smelting process
1) main chemical reactions that central space occurs on reaction tower：
A. decomposition reaction
2(NiFe)9S8=4Ni3S2+6FeS+S2
4CuFeS2=2Cu2S+4FeS+S2
2Fe7S8=14FeS+S2
2FeS2=2FeS+S2
B. oxidation reaction
2Ni3S2+7O2=6NiO+4SO2
2Cu2S+3O2=2Cu2O+2SO2
2CoS+3O2=2CoO+2SO2
2FeS+3O2=2FeO+2SO2
6FeO+O2=2Fe3O4
S+O2=SO2
C. cross reaction
6NiO+6FeS=2Ni3S2+6FeO+S2
3Fe3O4+ FeS=10FeO+SO2
Cu2O+FeS=Cu2S+FeO
CoO+FeS=CoS+FeO
Cu2S+2Cu2O=6Cu+SO2
2) main chemical reactions (reduction reaction) that reaction tower lower space and molten bath upper space occur
NiO+CO=Ni+CO2 NiO+H2=Ni+H2O
Cu2O+CO=2Cu+CO2 Cu2O+H2=2Cu+H2O
CoO+CO=Co+CO2 CoO+H2=Co+H2O
Fe3O4+ CO=3FeO+CO2 Fe3O4+H2=3FeO+H2O
3) esoteric main chemical reactions (slag making reaction) are melted in molten bath
2FeO+SiO2=2FeOSiO2
MgO+SiO2=MgOSiO2
CaO+SiO2=CaOSiO2
The method that embodiment 4 utilizes the Flash Smelting Furnace single step smelting lead of embodiment 1
1st, raw material and auxiliary material prepare
Raw material is a kind of lead concentrate, and main component is：
By raw material drying, simultaneously dispersion is water content below 0.3%, dry concentrate of the granularity less than 0.2mm.
Flux is quartz sand and lime stone.Quartz sand contains SiO2More than 80%, quartz sand drying to it is aqueous be less than 1%,
Granularity is less than 1mm；Lime stone contains CaCO3More than 90%, granularity is less than 1mm, aqueous to be less than 1%.Quartz sand and lime herein
Masonry is the slagging process that flux participates in flash smelting.
Coal must carry out coal-grinding and drying process as fuel, its water content is less than 0.2mm less than 1%, granularity, fine coal leads to
Cross burning and required heat is provided for flash smelting.
2nd, smelting process
Raw material, flux, technique oxygen, fine coal are added to flash furnace reaction tower 1 by Flash Smelting Furnace top jet nozzle 2, in 1100-
At a temperature of 1450 DEG C, raw material quickly reacts after entering reaction tower 1 with hot oxygen, and lead, zinc, the sulfide of copper and iron are rapid
PbO, ZnO, Cu are generated by direct oxidation2O and Fe3O4, in the process, oxygen is gradually depleted.Control oxygen and lead concentrate add
The mass ratio entered is 28.5%-30%, sulfide and sulphur into reaction tower 1 is finally all oxidized, makes last
The content for falling into S in the material in molten bath 5 is less than 0.05%, meanwhile, also make the oxidation reaction of sulphur in lead concentrate, sulfide and iron
By the oxygen depletion of central space on reaction tower 1, it is in weak oxide environment to make in the lower space of reaction tower 1.
To avoid PbO, Cu in the oxidized reaction generation in the top of reaction tower 12O and Fe3O4Into clinker, the present invention exists
The bottom of reaction tower 1 imports reducibility gas, and reducibility gas contains CO, H2Or hydrocarbon gas (such as methane) are effectively also
One or more in Primordial Qi atmosphere, preferably industrial production discharge the waste gas containing reducing atmosphere for example blast furnace gas, coal gas of converter,
Coke-stove gas, electric furnace (mineral hot furnace) tail gas, rotary kiln exhaust gas, rotary hearth furnace tail gas etc..Set in reaction tower 1 and the junction in molten bath 5
Barricade is put, makes to form the reduction air cushion layer 4 full of reducing atmosphere between the bottom of reaction tower 1 and the top of molten bath 5 and barricade.
In the lower space of reaction tower 1, it is consumed and is finished substantially by the oxygen of top addition, reducibility gas enters in stove
Be not in vigorous combustion and increase the thermic load of Flash Smelting Furnace, and substantial amounts of reducing atmosphere will absorb heat itself, have
Certain cooling effect.As PbO, Cu2O and Fe3O4It is dropped through and contains effective reducing atmosphere (CO+H2) concentration be 35%-70%
Reduction air cushion layer 4 when, PbO, Cu2O is reduced into elemental metals Pb and Cu, Fe3O4FeO is reduced into, that is, improves slag again
Improve Pb and the Cu rate of recovery.
After above-mentioned reactant melt falls into molten bath 5, MgO, FeO and flux SiO therein2Slag making, the slag of liquid and melting
Lead liquid due to the different precipitated and separateds of proportion, it is that (a small amount of Cu also enters lead bullion to lead bullion layer to form slag blanket 6 and crude metal layer 7
In), due to PbO, Cu2O and Fe3O4All it has been reduced, slag contains Pb, Cu and Fe3O4It is all very low.
Reaction generation contains SO2Flue gas discharged out of the furnace by uptake flue 10, then by cooling, can introduce after dedusting
To sulfuric acid plant's relieving haperacidity.Some spray guns 9 on the top of Flash Smelting Furnace molten bath 5, side and uptake flue 10, having neither part nor lot in going back for reaction
Primordial Qi atmosphere (CO or H2) connected space through the top of molten bath 5 ramp up flue 10 flow during, can spray into or blast and be oxygen-containing
Gas, oxygen can be the additional heat of molten bath 5 with reducing atmosphere burning, can also eliminate the bonding that uptake flue 10 is likely to occur.
The method of the single step smelting lead of the proposition of the present invention has wide applicability to raw material, is applicable not only to the low iron of high lead
Lead concentrate, it can also be used to the smelting of the lead ore of low lead high ferro.In addition, the leaded waste residue of doped portion such as lead is residual in concentrate
Slag, lead sulfate Ni, Copper scum silica frost, refining oxidizing slag etc., and it is feasible.
3rd, the main chemical reactions occurred in smelting process
1) main chemical reactions that central space occurs on reaction tower：
A. decomposition reaction
4CuFeS2=2Cu2S+4FeS+S2
2Fe7S8=14FeS+S2
2FeS2=2FeS+S2
CaCO3=CaO+CO2
B. oxidation reaction
2PbS+3O2=2PbO+2SO2
2PbS+4O2=2PbSO4
2ZnS+3O2=2ZnO+2SO2
2Cu2S+3O2=2Cu2O+2SO2
2FeS+3O2=2FeO+2SO2
6FeO+O2=2Fe3O4
S+O2=SO2
C. cross reaction
PbS+2PbO=3Pb+SO2
PbS+PbSO4=2Pb+2SO2
3Fe3O4+ FeS=10FeO+SO2
Cu2O+FeS=Cu2S+FeO
2) main chemical reactions (reduction reaction) that reaction tower lower space and molten bath upper space occur
PbO+CO=Pb+CO2 PbO+H2=Pb+H2O
Cu2O+CO=2Cu+CO2 Cu2O+H2=2Cu+H2O
Fe3O4+ CO=3FeO+CO2 Fe3O4+H2=3FeO+H2O
3) esoteric main chemical reactions (slag making reaction) are melted in molten bath
2FeO+SiO2=2FeOSiO2
CaO+SiO2=CaOSiO2
Effect experimental examples
The product and byproduct of the production of embodiment 2-4 methods are detected and the energy consumption of whole technological process is divided
Analysis calculates, and compared with the state-of-the-art metallurgical technology of industrialization in the prior art, in resulting clinker tenor and
Comprehensive energy consumption result is as shown in the table：
The metallurgical method of the invention proposition is understood by upper table, clinker is reduced and contains amount of metal and Fe to be smelted3O4
Content, both improved the rate of recovery for treating metal smelting, and improved the property of clinker again, and reduced its viscosity, beneficial to discharge, together
When, due to without using electric furnace, it is not required that add coke, one-time investment is small, and comprehensive energy consumption is low, and the production cost of product is low.
The preferred embodiment of the invention is the foregoing is only, is not intended to limit the invention creation, it is all at this
Within the spirit and principle of innovation and creation, any modification, equivalent substitution and improvements made etc., the invention should be included in
Protection domain within.
Claims (8)
- A kind of 1. metallurgical Flash Smelting Furnace of a step, it is characterised in that：Including reaction tower, nozzle is provided with the top of the reaction tower；It is described Reaction tower bottom connects the one end in molten bath, and uptake flue is provided with above the other end in the molten bath；The reaction tower lower half is set There is gas leading-in device to be used to import reducibility gas, reduction air cushion layer is formed in reaction tower lower space；The reproducibility gas Body contains effective reducing atmosphere, and effective reducing atmosphere is CO, H2In one or more；Primordial Qi is effectively gone back in the reduction air cushion layer The content of atmosphere is 35%-70%；Temperature control in reaction tower is at 1100-1450 DEG C.
- 2. Flash Smelting Furnace according to claim 1, it is characterised in that：The molten bath upper wall is provided with close to reaction tower side gos deep into stove Interior barricade or removable gate.
- 3. Flash Smelting Furnace according to claim 1, it is characterised in that：Molten bath top, side or the flue are provided with some Spray gun or air-blast device.
- A kind of 4. method metallurgical using the step of Flash Smelting Furnace one described in claim 1, it is characterised in that：To treat metal smelting ore deposit, Flux, oxygen-containing gas, cold burden are added in reaction tower by Flash Smelting Furnace top jet nozzle, by gas leading-in device under reaction tower Portion imports reducibility gas；Heating, treat that metal smelting ore deposit first passes through reaction tower top and oxidation reaction, generation metal oxidation occurs Thing, then the reduction air cushion layer by reaction tower bottom, reduction reaction occurs, generate metal simple-substance, thick gold is formed in molten bath bottom Belong to layer；After the gangue content in metal smelting ore deposit and flux slag making slag blanket is formed on molten bath top；Crude metal and slag are arranged respectively Come out of the stove outer；The flue gas of reaction generation is discharged by uptake flue.
- 5. the metallurgical method of a step according to claim 4, it is characterised in that：It is described to treat that metal smelting ore deposit vulcanizes for copper One kind in ore deposit, Ni sulphide mine, lead sulphide ore.
- 6. the metallurgical method of a step according to claim 4, it is characterised in that：The cold burden is the original containing valuable metal One or more in ore deposit, flue dust, pyrometallurgical smelting slag, hydrometallurgy slag.
- 7. the metallurgical method of a step according to claim 6, it is characterised in that：The valuable metal be gold, silver, indium, copper, One or more in bismuth, cobalt.
- 8. the metallurgical method of a step according to claim 4, it is characterised in that：Fe in the slag blanket3O4Content be less than 0.5%.
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| CN106521181B (en) * | 2016-11-02 | 2019-05-21 | 阳谷祥光铜业有限公司 | It is a kind of to revolve floating lead smelting process and revolve floating lead smelting device |
| CN109504812B (en) * | 2018-10-22 | 2020-09-01 | 江西理工大学 | Double-flash comprehensive recovery method for neodymium iron boron waste |
| CN109576431B (en) * | 2018-10-22 | 2020-09-08 | 江西理工大学 | One-step comprehensive recovery method for flash roasting of neodymium iron boron waste |
| CN109517934B (en) * | 2019-01-07 | 2021-02-23 | 山西赛思普科技有限公司 | Method for smelting pure metal by accurately controlling heat loss value |
| CN110317955B (en) * | 2019-08-19 | 2021-04-06 | 中南大学 | Process for efficiently separating and recovering blister copper from lead matte |
| CN110396606A (en) * | 2019-09-05 | 2019-11-01 | 天津闪速炼铁技术有限公司 | A kind of flash metallurgy gas package integral supply system and method for mixing |
| CN111101001B (en) * | 2020-01-16 | 2023-06-16 | 中国恩菲工程技术有限公司 | One-step nickel smelting system and one-step nickel smelting method |
| CN111733332A (en) * | 2020-06-11 | 2020-10-02 | 中铜东南铜业有限公司 | Process and device for reducing smoke dust rate of suspension smelting furnace and suspension converting furnace |
| CN112961953B (en) * | 2021-01-29 | 2023-01-06 | 天津闪速炼铁技术有限公司 | Production method and production system for hydrogen and metal products |
| CN114854995B (en) * | 2022-03-17 | 2024-03-19 | 中国恩菲工程技术有限公司 | Method for smelting lead-containing concentrate by hydrogen base and treating lead-based solid waste |
| CN115491491B (en) * | 2022-09-07 | 2023-11-17 | 金川集团股份有限公司 | Mixed flux batching method for metallurgical furnace |
| CN115852166B (en) * | 2022-12-28 | 2023-11-21 | 金川集团股份有限公司 | Method for smelting metallized nickel matte through nickel concentrate oxygen enrichment |
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