CN105200172B - Store up the cooperative processing method of EAF stainless steel slags and LF refining slag - Google Patents
Store up the cooperative processing method of EAF stainless steel slags and LF refining slag Download PDFInfo
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- CN105200172B CN105200172B CN201510565156.9A CN201510565156A CN105200172B CN 105200172 B CN105200172 B CN 105200172B CN 201510565156 A CN201510565156 A CN 201510565156A CN 105200172 B CN105200172 B CN 105200172B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a kind of cooperative processing method for storing up EAF stainless steel slags and LF refining slag, it will store up EAF stainless steel slags, LF refining slag, be mixed into mixing slag with coke powder and/or coal dust, then mixing slag it is heated, cooling, post processing after, the refining slag after being handled.This method makes to store up Cr in EAF stainless steel slags under high temperature action using the carbon in coke powder or coal dust6+It is reduced to Cr3+；Make full use of the high Al of LF refining slag2O3Content is conducive to the characteristics of spinelle is generated, and makes the Cr of reduction2O3It is cured and seals up for safekeeping into spinelle, the refining slag Cr after processing6+Leaching concentration is a few microgram liters, far below country《Hazardous waste judging standard leaching characteristic identification》（GB5085.3‑2007）In standard limited value, have effectively achieved the harmless treatment for storing up EAF stainless steel slags, realize that the innoxious and cold conditions LF refining slag collaboration for storing up EAF stainless steel slags is handled；Technique is simple, and harmless treatment cost has been saved in the treatment of wastes with processes of wastes against one another；The characteristics of with energy-conserving and environment-protective, high treating effect.
Description
Technical field
The present invention relates to a kind of processing method of slag, especially a kind of association for storing up EAF stainless steel slags and LF refining slag
Same processing method.
Background technology
2014, Chinese stainless steel crude steel yield was 2169.2 ten thousand tons, increases by 14.27% on a year-on-year basis.Produced by every 3 tons of stainless steels
Raw 1 ton of waste containing chromium（Mainly include stainless steel slag, acid-washing stainless steel sludge etc.）Meter, waste containing chromium year yield has exceeded 700
Ten thousand tons.At present, stainless steel main production equipments are electric furnace（Electric Arc Furnace, EAF）And argon oxygen decarburizing furnace
（Argon Oxygen Decarburization, AOD）, therefore stainless steel slag mainly includes EAF slags and AOD slags.Stainless steel slag
Essential element is Ca, Si, Mg, Al, Fe etc., but due in stainless steel slag the content of beary metal such as Cr it is higher, its recycling must
Its pulverability, stability and leaching must be considered.Pulverability is mainly by monoclinic crystal β-C2S is to octahedra γ-C2S nothing
The volumetric expansion that 12% is there are about in hot phase transition process is caused；Stability is 97.8% and 148% in f-CaO and f-MgO hydrolytic processes
Volumetric expansion causes；Leaching refers to that stainless steel slag is stacked or tailings is used as after construction material under the effect of the leaching liquors such as rainwater,
The toxic heavy metals such as Cr enter the ability of water body.Due to the heavy metal leaching such as chromium, the comprehensive Utilization Ways system of stainless steel slag
About, slag cement and construction material are used on a small quantity prepare, and more stainless steel slags can only be to store up processing.
Because the melting later stage is reducing atmosphere, hypoxemia gesture controls the oxidation of metal and metalloid, therefore EAF stainless steels
Cr in slag is main with metallic state and the presence of+trivalent form, and metallic state chromium generally forms alloy with Ni, Fe, passes through fine grinding and magnetic separation
Reclaimed, and trivalent chromium is primarily present in Ca-Mg-Al silicate and spinels mineral.Many scholars think, not only in height
Cr in stainless steel slag when warm3+Cr can be oxidized to6+, the reaction also possesses thermodynamical reaction condition under normal temperature state, especially
Material is absorbed after moisture, and CaO hydrolysis will the generation more Ca in oxygen center (OH)2So that the stronger Cr of oxytropism3+Easily by oxygen
Turn to Cr6+, so as to increase the leaching toxicity of chromium in EAF stainless steel slags.Due to being influenceed by kinetic factor, EAF stainless steel slags
Store up Cr after 1 year3+Oxygenation efficiency 10% or so, greatly strengthen the leaching toxicity of EAF stainless steel slags.Therefore, heap is rationally disposed
Deposit a period of time and contain a certain amount of Cr6+EAF stainless steel slags of storing up be asking of paying close attention to of disposal of waste gas, water and industrial residue field worker
Topic.At present, storing up the harmless treatment of EAF stainless steel slags mainly has three classes：
（1）High temperature reduction method：Pyrocarbon reduction with coke, powdered carbon, wood chip, gangue and eutrophication algae slag etc. as
Reducing agent, carries out high-temperature fusion reaction, by Cr in slag using the excessive C and stainless steel slag wherein contained6+It is reduced to Cr3+, finally
Exist with glassy state or spinelle, can be used as Product recycling., also can be using hydrogen, methane, an oxidation except solid state reduction agent
The gases such as carbon are as reducing agent to Cr3+Reduced.Solid phase high temperature reduction is not often thorough in the presence of reducing, and gas phase high temperature reduction is again
There is reducing agent for fuel gas, technique is relative complex, otherwise easily causes new pollution.
（2）Wet reducing method：Stainless steel slag is mixed with acid or alkaline solution, and is added into solution containing sulfuric acid Asia
The reducing substanceses such as iron, alkali metal sulphide, by Cr6+It is reduced to Cr3+, and Precipitation Cr (OH) in alkaline solution3To return
Receive and recycle.It is different according to reaction condition, acidic reduction method, alkaline reduction method and organic phosphorus waste liquid reducing process can be divided into.This
A little methods need to consume acid-base solution, and produce new sewage and need processing.
（3）Cement solidification method：By a certain amount of stainless steel ground-slag with addition of a certain amount of FeSO4、FeCl2Deng adding water after additive
Mud clinker, Cr, with the aquation and condensation hardening process of cement, is sealed in cement hard by the mixing that adds water, stirring, shaping and solidification
Change in vivo without dissolution, reach stable and innoxious purpose.Its shortcoming is after cement solidification due to chromium slag volumetric expansion,
Cause the stability of cement and concrete.
LF refining has the metallurgical characteristics such as equipment is simple, investment cost is low, operation is flexible, refining effect is good, is used as lifting
The effective means of steel metallurgical quality is developed rapidly, it has also become indispensable one in modernization steel production short route
Critical process.In LF refining process, the characteristics of mainly using refining slag high alkalinity, low oxidative and high sulfur capacity is to steel
Liquid is refined, to realize to deoxygenation of liquid steel, desulfurization, adsorbs the metallurgical functions such as the field trash in steel, the form for controlling field trash,
Improve molten steel cleanness.However, also producing a large amount of refining slags after refining, 3% of output of steel or so is accounted for.Produced per year according to 2014
8.23 hundred million tons of steel, 1/2 refines calculating through LF, then will produce 12,350,000 tons of LF refining slags every year.Largely LF refining slags is straight
Run in and put the severe contamination for causing environment and the waste of resource, do not meet green, ecological metallurgical demand for development.
At present, LF refining slag, which is recycled, mainly has hot Returning utilization and cold conditions to handle two kinds of techniques.It is hot to return to profit
With hot refining slag mainly is returned into electric furnace or converter procedure, the lime for reducing steel making working procedure instead of lime desulfurization, dephosphorization disappears
Consumption, while carrying out effective recycling, reduction steel making working procedure energy consumption, pollution of the reduction to environment to the heat of residue；But by
The enrichment of sulphur, phosphorus content in slag so that the number of times of hot refining slag cycling and reutilization is restricted.Cold conditions processing is by cold conditions
The materials such as refining slag and ferrous material, binding agent are mixed, return to blast furnace ironmaking or pneumatic steelmaking after cold moudling；But such a method
It can only be acted on using the flux of refining slag, handling rate is restricted.
The content of the invention
The technical problem to be solved in the present invention is to provide it is a kind of effectively, environmental protection store up EAF stainless steel slags and LF refining slag
Cooperative processing method.
In order to solve the above technical problems, the technical solution used in the present invention is：It will store up EAF stainless steel slags, LF essences
Refine slag, be mixed into mixing slag with coke powder and/or coal dust, then mixing slag it is heated, cooling, post processing after, handled
Refining slag afterwards.
The weight/mass percentage composition of each material is in mixing slag of the present invention：Store up EAF stainless steel slags 3%~10%, LF essences
Refine slag 88%~96%, coke powder and/or coal dust 1%~2%.
The present invention is heated using microwave.The microwave power is 150W~900W, and the heat time is 30~90min.
It is using the beneficial effect produced by above-mentioned technical proposal：The present invention utilizes coke powder or coal dust under high temperature action
In carbon make to store up Cr in EAF stainless steel slags6+It is reduced to Cr3+；Make full use of the high Al of LF refining slag2O3Content is conducive to sharp crystalline substance
The characteristics of stone is generated, makes the Cr of reduction2O3It is cured and seals up for safekeeping into spinelle, the refining slag Cr after processing6+Leaching concentration is
A few microgram liters, far below country《Hazardous waste judging standard leaching characteristic identification》（GB5085.3-2007）In standard limit
Value, have effectively achieved the harmless treatment for storing up EAF stainless steel slags, realize the innoxious and cold conditions for storing up EAF stainless steel slags
The collaboration of LF refining slag is handled.Therefore, present invention process is simple, and harmless treatment cost has been saved in the treatment of wastes with processes of wastes against one another；With energy-saving ring
The characteristics of guarantor, high treating effect.
When the present invention is using microwave heating, the features such as making full use of fast microwave method heating, small heat consumption, homogeneous heating can have
Effect ground lifting treatment effect, reduction processing energy consumption.
Embodiment
Originally the cooperative processing method for storing up EAF stainless steel slags and LF refining slag uses following processing steps：EAF will be stored up not
Rust slag, LF refining slag, coke powder and/or coal dust are respectively placed in drying box to be cooled to after 3~6h is dried at 100~120 DEG C
Normal temperature；According to the quality hundred for storing up EAF stainless steel slags 3%~10%, LF refining slag 88%~96%, coke powder and/or coal dust 1%~2%
Distribution ratio, mixing slag is mixed into by material.Mixing slag loads ceramic crucible, and then ceramic crucible is put into micro-wave oven,
It is incubated, is heated under 150W~900W microwave powers after 30~90min with mineral wool around crucible, close micro-wave oven, opens stove
Door takes out material and is cooled to normal temperature.Mixing slag after cooling is post-processed using the method for conventional slag processing, you can obtained
Refining slag innoxious, after processing.
With reference to specific embodiment, the present invention is further detailed explanation, the material component in following embodiments with
And course of reaction is as described below.
（1）Described to store up the iron and steel enterprise stockyard that EAF stainless steel slags derive from EAF technique productions stainless steels, it is mainly changed
Study point and content is as shown in table 1.
Table 1：Store up the main chemical compositions and content of EAF stainless steel slags（Quality %）
（2）The main chemical compositions and content of the LF refining slag are as shown in table 2.
Table 2：The chemical composition and content of LF refining slag（Quality %）
（3）Carbon in the coke powder and fine coal can make to store up the Cr that EAF stainless steel slags store up process oxidation generation6+Reduction
For Cr3+, the key reaction in microwave heating process is shown in formula（1）To formula（3）：
2C+O2→2CO （1）
3CO+2CrO3→Cr2O3+3CO2（2）
CO2+C→2CO （3）.
Embodiment 1：The EAF stainless steel slags of more than 1 year are stored up in collection, and this stores up the main chemical compositions of EAF stainless steel slags
And content is：CaO 40%、MgO 8%、SiO2 20%、Al2O3 5%、FeO 8%、MnO 2%、Cr2O32%, above-mentioned content is attached most importance to
Amount proportioning.Cold conditions LF refining slag is gathered, the main chemical compositions and content of the LF refining slag are：CaO 30%、MgO 7%、SiO2
6%、Al2O310%th, FeO 0.3%, Fe 0.3%, above-mentioned content is weight proportion.Store up EAF stainless steel slags, LF refining slag and
Coke powder is respectively placed in drying box is cooled to normal temperature after 6h is dried at 100 DEG C, according to storing up EAF stainless steel slags:LF refining slag:
Coke powder=3:96:1 mass ratio, after material is well mixed, loads ceramic crucible, then ceramic crucible is put into micro-wave oven,
It is incubated, is heated under 150W microwave powers after 90min with mineral wool around crucible, close micro-wave oven, is opened fire door and take out material
Normal temperature is cooled to, the mixing slag after cooling is post-processed using the method for conventional slag processing, you can the essence after being handled
Refine slag.Cr in refining slag after being handled using GB5085.3-2007 measure6+Leaching concentration, as a result shows：Cr6+Leaching concentration ＜
5μg/L。
Embodiment 2：The EAF stainless steel slags of more than 1 year are stored up in collection, and this stores up the main chemical compositions of EAF stainless steel slags
And content is：CaO 50%、MgO 10%、SiO2 30%、Al2O3 10%、FeO 22%、MnO 3%、Cr2O310%, above-mentioned content is equal
For weight proportion.Cold conditions LF refining slag is gathered, the main chemical compositions and content of the LF refining slag are：CaO 70%、MgO 16%、
SiO2 30%、Al2O345%th, FeO 2.5%, Fe 2.5%, above-mentioned content is weight proportion.Store up EAF stainless steel slags, LF essences
Refining slag and coal dust are respectively placed in drying box is cooled to normal temperature after 5.5h is dried at 105 DEG C, according to storing up EAF stainless steel slags:
LF refining slag:Coal dust=5:94:1 mass ratio, after material is well mixed, loads ceramic crucible, is then put into ceramic crucible
In micro-wave oven, it is incubated, is heated under 300W microwave powers after 70min with mineral wool around crucible, close micro-wave oven, opens fire door
Take out material and be cooled to normal temperature, the mixing slag of cooling is post-processed using the method for conventional slag processing, you can handled
Refining slag afterwards.Cr in refining slag after being handled using GB5085.3-2007 measure6+Leaching concentration, as a result shows：Cr6+Leach
The μ g/L of concentration ＜ 5.
Embodiment 3：The EAF stainless steel slags of more than 1 year are stored up in collection, and this stores up the main chemical compositions of EAF stainless steel slags
And content is：CaO 45%、MgO 9%、SiO2 25%、Al2O3 7.5%、FeO 15%、MnO 2.5%、Cr2O36%, above-mentioned content
It is weight proportion.Cold conditions LF refining slag is gathered, the main chemical compositions and content of the LF refining slag are：CaO 50%、MgO
12%、SiO2 18%、Al2O323%th, FeO 1.4%, Fe 1.4%, above-mentioned content is weight proportion.Store up EAF stainless steel slags,
LF refining slag and coke powder are respectively placed in drying box is cooled to normal temperature after 4.5h is dried at 110 DEG C, according to storing up EAF stainless steels
Slag:LF refining slag:Coke powder=7:91:2 mass ratio, after material is well mixed, loads ceramic crucible, then by ceramic crucible
It is put into micro-wave oven, is incubated around crucible with mineral wool, heated under 450W microwave powers after 50min, close micro-wave oven, opens
Fire door takes out material and is cooled to normal temperature, and the mixing slag of cooling is post-processed using the method for conventional slag processing, you can obtained
Refining slag after processing.Cr in refining slag after being handled using GB5085.3-2007 measure6+Leaching concentration, as a result shows：Cr6+
The μ g/L of leaching concentration ＜ 5.
Embodiment 4：The EAF stainless steel slags of more than 1 year are stored up in collection, and this stores up the main chemical compositions of EAF stainless steel slags
And content is：CaO 43%、MgO 8.7%、SiO2 27%、Al2O3 7.5 %、FeO 15.8%、MnO 2.8%、Cr2O37.5%, on
It is weight proportion to state content.Cold conditions LF refining slag is gathered, the main chemical compositions and content of the LF refining slag are：CaO 46%、
MgO 11%、SiO2 16%、Al2O321%th, FeO 0.9%, Fe 0.8%, above-mentioned content is weight proportion.Store up EAF stainless steels
Slag, LF refining slag and coal dust are respectively placed in drying box and are cooled to normal temperature after 3h is dried at 115 DEG C, according to EAF stainless steel slags:
LF refining slag:Coal dust=8:90:2 mass ratio, after material is well mixed, loads ceramic crucible, is then put into ceramic crucible
In micro-wave oven, it is incubated, is heated under 900W microwave powers after 40min with mineral wool around crucible, close micro-wave oven, opens fire door
Take out material and be cooled to normal temperature, the mixing slag of cooling is post-processed using the method for conventional slag processing, you can handled
Refining slag afterwards.Cr in refining slag after being handled using GB5085.3-2007 measure6+Leaching concentration, as a result shows：Cr6+Leach
The μ g/L of concentration ＜ 5.
Embodiment 5：The EAF stainless steel slags of more than 1 year are stored up in collection, and this stores up the main chemical compositions of EAF stainless steel slags
And content is：CaO 47%、MgO 9.2%、SiO2 23%、Al2O3 6.3%、FeO 12.9%、MnO 2.12%、Cr2O33.8%, on
It is weight proportion to state content.Cold conditions LF refining slag is gathered, the main chemical compositions and content of the LF refining slag are：CaO 54%、
MgO 13%、SiO2 20%、Al2O325%th, FeO 1.5%, Fe 1.6%, above-mentioned content is weight proportion.Store up EAF stainless steels
Slag, LF refining slag, coke powder and coal dust（Weight compares 1:1）It is respectively placed in drying box and is cooled to often in after dry 3.5h at 120 DEG C
Temperature, according to EAF stainless steel slags:LF refining slag:Coke powder and coal dust=10:88:2 mass ratio, after material is well mixed, loads
Ceramic crucible, is then put into micro-wave oven by ceramic crucible, is incubated around crucible with mineral wool, is heated under 600W microwave powers
After 30min, micro-wave oven is closed, fire door taking-up material is opened and is cooled to normal temperature, the mixing slag of cooling is using conventional slag processing
Method is post-processed, you can the refining slag after being handled.In refining slag after being handled using GB5085.3-2007 measure
Cr6+Leaching concentration, as a result shows：Cr6+The μ g/L of leaching concentration ＜ 5.
Claims (3)
1. a kind of cooperative processing method for storing up EAF stainless steel slags and LF refining slag, it is characterised in that：It is stainless that it will store up EAF
Slag, LF refining slag, mixing slag is mixed into coke powder and/or coal dust, then mixing slag it is heated, cooling, post processing after,
Refining slag after being handled, the main chemical compositions and content of the EAF stainless steel slags are：CaO 40%、MgO 8%、SiO2
20%、Al2O3 5%、FeO 8%、MnO 2%、Cr2O32%, above-mentioned content is weight proportion；Mainization of the LF refining slag
Study point and content is：CaO 30%、MgO 7%、SiO2 6%、Al2O310%th, FeO 0.3%, Fe 0.3%, above-mentioned content is
The weight/mass percentage composition of each material is in weight proportion, the mixing slag：Store up EAF stainless steel slags 3%, LF refining slag 96%, Jiao
Powder and/or coal dust 1%, after testing, final Cr6+The μ g/L of leaching concentration ＜ 5.
2. the cooperative processing method according to claim 1 for storing up EAF stainless steel slags and LF refining slag, it is characterised in that：
Heated using microwave.
3. the cooperative processing method according to claim 1 or 2 for storing up EAF stainless steel slags and LF refining slag, its feature exists
In：The microwave power is 150W~900W, and the heat time is 30~90min.
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| JP2002053351A (en) * | 2000-08-07 | 2002-02-19 | Sumitomo Metal Ind Ltd | Pollution-free stainless steel slag and method for manufacturing the same |
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| CN101569784A (en) * | 2009-06-08 | 2009-11-04 | 昆明理工大学 | Method for detoxicating chromium residue by utilizing coal refuse through microwave |
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| CN1212901C (en) * | 2003-10-10 | 2005-08-03 | 匡少平 | Method for harmless treating chromium slag into resource and use thereof |
| CN101138670A (en) * | 2006-09-08 | 2008-03-12 | 隋智通 | Novel process of the high temperature reduction and detoxication of industrial chromic slag |
| CN101264481A (en) * | 2008-04-30 | 2008-09-17 | 钢铁研究总院 | Cr6+ furnace cinder containing gas reduction curing method |
| CN101942571B (en) * | 2010-09-06 | 2014-10-22 | 重庆瑞帆再生资源开发有限公司 | Method for innocently treating and recycling chromium residues and metallurgical waste material |
| CN103638629B (en) * | 2013-12-10 | 2015-11-04 | 西南科技大学 | The technique of integration reduction curing chromium slag |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053351A (en) * | 2000-08-07 | 2002-02-19 | Sumitomo Metal Ind Ltd | Pollution-free stainless steel slag and method for manufacturing the same |
| CN101549894A (en) * | 2009-05-21 | 2009-10-07 | 昆明理工大学 | Method of using lake sediment in microwave detoxification of chromium slags |
| CN101569783A (en) * | 2009-06-08 | 2009-11-04 | 昆明理工大学 | Method for detoxicating chromium residue by utilizing high sulfur petroleum coke through microwave |
| CN101569784A (en) * | 2009-06-08 | 2009-11-04 | 昆明理工大学 | Method for detoxicating chromium residue by utilizing coal refuse through microwave |
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