CN108642231A - A kind of converter slag modifier and the method using its obtained low alkalinity slag system - Google Patents
A kind of converter slag modifier and the method using its obtained low alkalinity slag system Download PDFInfo
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- CN108642231A CN108642231A CN201810462306.7A CN201810462306A CN108642231A CN 108642231 A CN108642231 A CN 108642231A CN 201810462306 A CN201810462306 A CN 201810462306A CN 108642231 A CN108642231 A CN 108642231A
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/36—Processes yielding slags of special composition
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/36—Processes yielding slags of special composition
- C21C2005/363—Slag cements
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Abstract
The present invention provides a kind of converter slag modifier and using the method that low alkalinity slag system is made in it, the modification agent ingredient is as follows by weight percentage：The sum of blast furnace dedusting ash, iron tailings are 90% 100%, and mass ratio=0.7~6.0 of blast furnace dedusting ash/iron tailings, discard Al2O3C Bricks mass percentage 0~10%.The method that low alkalinity slag system is made using above-mentioned converter slag modifier, by the modification agent and vessel slag according to mass ratio be 0.5~1.3 it is full and uniform mix, and mixed mixture satisfaction：Mc0.27 × M of ＞Fe2O3+0.2×MFeO；MCaO2.8 × M of ＜SiO2+0.941×MAl2O3+1.4×MMgO；By mixture, calcination temperature is not less than 1450 DEG C under the conditions of nonoxidizing atmosphere, and the time is not less than 20 minutes, obtains 0.5 1.3 slag system of basicity.The present invention solves to reduce waste discharge while vessel slag recycles and obtains the low alkalinity slag system of high value added product.
Description
Technical field
The invention belongs to convertor steelmaking process solid waste resources to recycle field more particularly to a kind of modification of vessel slag
The method of agent and its obtained low alkalinity slag system.
Background technology
Vessel slag is the industrial solid wastes generated during a kind of pneumatic steelmaking.Often produce 1 ton of steel want by-product 0.1~
0.13 ton of slag, 1350 DEG C~1450 DEG C or so of temperature.Wherein also contain 10~30% full iron (TFe) and a large amount of beneficial elements
Therefore calcium, magnesium and silicon etc. increase the recycling to vessel slag resource, becoming reduces steel mill's smelting cost, realize waste zero
The main means of discharge.Currently, for the existing main methods of vessel slag be by cold conditions vessel slag by broken, screening,
Magnetic separation and etc., it is used again after extracting metal oxide therein, usually handles rear converter slag for ground backfill, road
Making, cement raw material, water purification agent and slag fertilizer etc..Two kinds of products that this processing method obtains are respectively ferriferous oxide and height
Basicity slag system, added value of product are relatively low.
《A method of it is recycled using gas reduction vessel slag and clinker》(105624359 A of CN) is disclosed
A method of it is recycled using gas reduction vessel slag and clinker comprising following steps：Converter steelmaking process is divided into
Pneumatic steelmaking and vessel slag are heat-treated two flows, in the pneumatic steelmaking flow, the oxidized reaction of impurity element in molten iron
Enter vessel slag in the form of the oxide, forms the hot vessel slag of high content of phosphorus；The vessel slag is poured into processing slag and fills single
Member is heat-treated flow into the vessel slag, and the slag filling unit for filling the vessel slag is transferred to vessel slag treating stations, described
The vessel slag occurs using coal gas as the hot reduction of reducing medium in vessel slag treating stations, wherein the reduction ratio ＞ of FeO
80%, the reduction ratio ＞ 80% of P2O5, hot reduction treatment process are carried out at the same time waste heat recovery and the gaseous state of the vessel slag
Phosphorus recovery operation, the vessel slag after processing finishes are re-applied as pre-melted slag and iron content cooling material return converter.This method institute
It is generally higher to obtain slag system dual alkalinity, and there are free calcium oxide in slag, the slag system can not in urban road laying, prepare cement etc.
Sector application.
《A kind of process for treating steel slag and its device》The process for treating steel slag that (103757152 B of CN) is disclosed includes will
Sial acidic oxide and slag feed intake, wherein mole of total sial acidic oxide and basic anhydride in mixture
Than 1:2.5-2.9；Kiln temperature is 1350-1450 DEG C, and in the presence of reducing agent, mixture heats mixing in rotary kiln；Production
Object is granulated into particle, carries out water quenching and cooling, falls into the water later, then through dehydration；Particle carries out magnetic separation separation after dehydration,
Steel grit is detached with series silicate particle.Reducing agent is carbon monoxide and coal dust intermixture in this method, and cost of material is higher.And
Rotary kiln process of coal combustion necessarily introduces the oxygen in air, complicated compared to reducing agent direct-reduction flow, reduction efficiency compared with
It is low.
《A method of recycling iron and phosphorus from copper smelter slag》Method is by including disclosed in (102264919 A of CN)
Following process, can recycle phosphorus and iron with low cost from the copper smelter slag, and can be using the phosphorus of recycling and iron as resource
It is efficiently used：The first step in the process, carries out the phosphorous copper smelter slag such as dephosphorization clinker with the reducing agents such as carbon, Si, Al
Reduction treatment, by the clinker ferriferous oxide and phosphorous oxides restored and recycle in the form of phosphorous molten iron；Second work
Sequence in the process, is used the copper smelter slag for eliminating ferriferous oxide and phosphorous oxides as the sources CaO in sintering circuit, will
Sinter obtained is recycled to blast furnace；The third step, in the process, to the phosphorous molten iron recycled by the reduction treatment
Dephosphorization treatment is carried out, until the phosphorus concentration in phosphorous molten iron reaches 0.1 mass % hereinafter, phosphorus is made to be concentrated in CaO class flux；
In the process, which is mixed as source of iron to blast-melted in 0.1 mass % phosphorous molten irons below for the fourth step
In.CaO mass percentages are higher in obtained slag in this method, therefore can only substitute the CaO in sintering circuit, nothing on a small quantity
Method obtains the slag with gelling property, and added value of product is relatively low, limits its recycle value.
Taeyoung Kim et al.《Recovery of Fe and P from CaO-SiO2-FetO-P2O5 Slag by
Microwave Treatment》A kind of laboratory research of microwave heating graphitic carbon reduction treatment vessel slag is described in paper.
Wherein the equilibrium constant of carbon is 1.69, is heated 15 minutes, the reduction rate of iron reaches 0.97, phosphorus 0.89.Liu Chun is big et al.
《Valorization of BOF Steel Slag by Reduction and Phase Modification:Metal
Recovery and Slag Valorization》Describe iron phosphate oxide in carbon thermal reduction slag in paper, and by with addition of
Aluminium oxide and silica adjustment basicity prepare the laboratory research of different slag system products.Reaction restores 1 hour at 1600 DEG C, iron oxygen
The removal rate of compound is more than 0.9, and describes the cutting mechanisms of iron phosphate oxide.Reducing agent used is graphite in two articles
Matter carbon is difficult to obtain economic benefit in heavy industrialization.
The method that the existing converter Slag treatment of the above invention and paper recycles, is mostly carbon thermal reduction ferriferous oxide
Or magnetic separation go slagging-off in iron compound method, in order to make full use of iron and steel enterprise generate waste, set forth herein one kind by
Converter slag modifier prepared by the difficult tailing of blast furnace dedusting ash and mine, which is waste, and to converter
It is iron and low alkalinity slag system that product is obtained after Slag treatment, is high value added product.
According to background above data, patent of the present invention proposes the side of a kind of converter slag modifier and its obtained low alkalinity slag system
Method.
Invention content
It a kind of converter slag modifier is provided and is made using it is an object of the invention to overcome the above problem and deficiency
The method of low alkalinity slag system, the waste blast furnace dedusting ash generated using three kinds of iron and steel enterprises, mine iron tailings, discarded alumina carbon brick
Vessel slag Pignus pignoris agent is prepared, the oxide for restoring the elements such as iron in vessel slag, manganese, phosphorus and the free oxidation of reduction even removal
Calcium realizes the recycling of vessel slag iron resource while producing the products such as cement admixture, geo-polymer.
What the object of the invention was realized in：
A kind of converter slag modifier, including blast furnace dedusting ash, iron tailings, discarded Al2O3C Bricks；The modification agent ingredient is by weight
Percentages are as follows：The sum of blast furnace dedusting ash, iron tailings are 90%-100%, and the mass ratio of blast furnace dedusting ash/iron tailings=
0.7~6.0, discard Al2O3C Bricks mass percentage 0~10%.
Further, the aqueous mass percent of the blast furnace dedusting ash is less than 2%, and grade accounts for mass percent less than 100 mesh
90% or more, carbon is not less than 0.7 with full weight of iron ratio.
Further, the aqueous mass percent of the iron tailings is less than 1%, and grade accounts for mass percent 90% less than 100 mesh
More than, silica is not less than 5.0 with full weight of iron ratio.
Further, the aqueous mass percent of discarded alumina carbon brick is less than 2%, and grade accounts for mass percent less than 100 mesh
90% or more, MgO mass percentage are less than 5%.
Technical solution provided by the invention second is that a kind of side that low alkalinity slag system being made using above-mentioned converter slag modifier
Method, by the modification agent and vessel slag according to mass ratio be 0.5~1.3 it is full and uniform mix, and mixed mixture meets such as
Lower formula：
Mc0.27 × M of ＞Fe2O3+0.2×MFeO
MCaO2.8 × M of ＜SiO2+0.941×MAl2O3+1.4×MMgO
Wherein：McCarbonaceous amount, M in-mixtureFe2O3Fe in-mixture2O3Quality, MFeOFeO mass in-mixture,
MCaOCalcium oxide quality, M in-mixtureSiO2Silica quality, M in-mixtureAl2O3Quality of alumina in-mixture,
MMgOMagnesia quality in-mixture；
Described later by mixture, calcination temperature is not less than 1450 DEG C under the conditions of nonoxidizing atmosphere, and the time is not less than 20 points
Clock obtains the low alkalinity slag system that basicity R2 is 0.5-1.3.
The beneficial effects of the present invention are：Modification agent raw material blast furnace dedusting ash, iron tailings, the waste aluminium charcoal that the present invention introduces
Brick is waste material, while solving vessel slag recycling, reduces waste discharge.Product is obtained to be iron and can be used for preparing
The low alkalinity slag system of the high value added products such as cement, geo-polymer.
Specific implementation mode
Below by embodiment, the present invention is further illustrated.
A kind of converter slag modifier, including blast furnace dedusting ash, iron tailings, discarded Al2O3C Bricks；The modification agent ingredient is by weight
Percentages are as follows：The sum of blast furnace dedusting ash, iron tailings are 90%-100%, and the mass ratio of blast furnace dedusting ash/iron tailings=
0.7~6.0, discard Al2O3C Bricks mass percentage 0~10%.
The aqueous mass percent of blast furnace dedusting ash be less than 2%, grade less than 100 mesh account for mass percent 90% with
On, carbon is not less than 0.7 with full weight of iron ratio.
The aqueous mass percent of iron tailings is less than 1%, and grade accounts for 90% or more mass percent, oxygen less than 100 mesh
SiClx is not less than 5.0 with full weight of iron ratio.
The aqueous mass percent of discarded alumina carbon brick be less than 2%, grade less than 100 mesh account for mass percent 90% with
On, MgO mass percentages are less than 5%.
A method of low alkalinity slag system being made using above-mentioned converter slag modifier, by the modification agent and vessel slag according to matter
Amount is than for 0.5~1.3 full and uniform mixing, and mixed mixture meets following formula：
Mc0.27 × M of ＞Fe2O3+0.2×MFeO
MCaO2.8 × M of ＜SiO2+0.941×MAl2O3+1.4×MMgO
Wherein：McCarbonaceous amount, M in-mixtureFe2O3Fe in-mixture2O3Quality, MFeOFeO mass in-mixture,
MCaOCalcium oxide quality, M in-mixtureSiO2Silica quality, M in-mixtureAl2O3Quality of alumina in-mixture,
MMgOMagnesia quality in-mixture；
The mixture is calcination temperature is not less than 1450 DEG C under the conditions of nonoxidizing atmosphere later, and the time is not less than 20 points
Clock obtains the low alkalinity slag system that basicity R2 is 0.5-1.3.
The material chemical component analysis of modification agent of the embodiment of the present invention is shown in Table 1, modification agent composition design of the embodiment of the present invention
Table part table 2, vessel slag chemical composition analysis of the embodiment of the present invention are shown in Table 3, and modification agent of the embodiment of the present invention is mixed with vessel slag matches
Material table is shown in Table 4, and the embodiment of the present invention is made low alkalinity slag system experimental evaluation and the results are shown in Table 5.
The material chemical component analysis (wt%) of 1 modification agent of the embodiment of the present invention of table
2 modification agent composition design table of the embodiment of the present invention (wt/%) of table
Table 1-3 vessel slag of embodiment of the present invention chemical composition analysis (wt%)
| Vessel slag | FeO | Fe2O3 | SiO2 | CaO | MgO | Al2O3 |
| 1 | 0.72 | 23.14 | 12.89 | 38.38 | 10.76 | 9.18 |
| 2 | 0.66 | 22.56 | 13.22 | 39.1 | 9.86 | 9.57 |
| 3 | 0.66 | 22.56 | 13.22 | 39.1 | 9.86 | 9.57 |
| 4 | 0.72 | 23.14 | 12.89 | 38.38 | 10.76 | 9.18 |
4 modification agent of the embodiment of the present invention of table and vessel slag mixed ingredients table
Low alkalinity slag system experimental evaluation result is made in 5 embodiment of the present invention of table
In order to state the present invention, explanation appropriately and is being sufficiently carried out to the present invention by embodiment among the above, it is above
Embodiment is merely to illustrate the present invention, and not limitation of the present invention, those of ordinary skill in technical field, not
In the case of being detached from the spirit and scope of the present invention, can also make a variety of changes and modification, made by any modification, equally replace
It changes, improve, should all be included in the protection scope of the present invention, scope of patent protection of the invention should be limited by claim
It is fixed.
Claims (5)
1. a kind of converter slag modifier, which is characterized in that including blast furnace dedusting ash, iron tailings, discarded Al2O3C Bricks；The modification agent at
Divide as follows by weight percentage：The sum of blast furnace dedusting ash, iron tailings are 90%-100%, and blast furnace dedusting ash/iron tailings
Al2O3C Bricks mass percentage 0~10% is discarded in mass ratio=0.7~6.0.
2. a kind of converter slag modifier according to claim 1, which is characterized in that the blast furnace dedusting ash contains water quality hundred
Divide than being less than 2%, grade accounts for 90% or more mass percent less than 100 mesh, and carbon is not less than 0.7 with full weight of iron ratio.
3. a kind of converter slag modifier according to claim 1, which is characterized in that the aqueous mass percent of iron tailings
Less than 1%, grade accounts for 90% or more mass percent less than 100 mesh, and silica is not less than 5.0 with full weight of iron ratio.
4. a kind of converter slag modifier according to claim 1, which is characterized in that the aqueous quality of the discarded alumina carbon brick hundred
Divide than being less than 2%, grade accounts for 90% or more mass percent less than 100 mesh, and MgO mass percentages are less than 5%.
5. a kind of method that low alkalinity slag system is made in converter slag modifier using described in claim 1-4, which is characterized in that will
The modification agent and vessel slag according to mass ratio be 0.5~1.3 it is full and uniform mix, and mixed mixture meet it is following public
Formula：
Mc0.27 × M of ＞Fe2O3+0.2×MFeO
MCaO2.8 × M of ＜SiO2+0.941×MAl2O3+1.4×MMgO
Wherein：McCarbonaceous amount, M in-mixtureFe2O3Fe in-mixture2O3Quality, MFeOFeO mass, M in-mixtureCaO—
Calcium oxide quality in mixture, MSiO2Silica quality, M in-mixtureAl2O3Quality of alumina in-mixture, MMgO—
Magnesia quality in mixture；
By the mixture, calcination temperature is not less than 1450 DEG C under the conditions of nonoxidizing atmosphere later, and the time is not less than 20 minutes,
Obtain the low alkalinity slag system that basicity R2 is 0.5-1.3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114790502A (en) * | 2022-04-13 | 2022-07-26 | 山东莱钢永锋钢铁有限公司 | Method for reducing content of free calcium oxide in converter steel slag |
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| CN101413043A (en) * | 2008-12-05 | 2009-04-22 | 攀枝花钢城集团有限公司 | Steel-smelting regulator and preparation thereof |
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