CN104878213A - Method for producing low-carbon ferromanganese from washed iron through decarbonizing and dephosphorizing - Google Patents
Method for producing low-carbon ferromanganese from washed iron through decarbonizing and dephosphorizing Download PDFInfo
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- CN104878213A CN104878213A CN201510308357.0A CN201510308357A CN104878213A CN 104878213 A CN104878213 A CN 104878213A CN 201510308357 A CN201510308357 A CN 201510308357A CN 104878213 A CN104878213 A CN 104878213A
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Abstract
The invention discloses a method for producing low-carbon ferromanganese from Industrial waste residue, i.e., washed iron through recycling. The low-carbon ferromanganese with low cost is obtained through enabling waste slag, obtained after silicomanganese factory production, to be subjected to decarbonizing, dephosphorizing and desiliconizing treatment. The method comprises the specific steps: (a) mixing a certain amount of washed iron, a slag former and a decarbonizer, adding the mixture into a refining furnace, and heating the refining furnace to melt and decarbonize the mixture; (b) adding the decarbonized mixture inside shaking ladles for dephosphorizing treatment, wherein a dephosphorizing agent as well as lime and fluorite are added inside the shaking ladles in advance; (c) returning the dephosphorized mixture into the refining furnace again for desiliconizing treatment, wherein preheated manganese-rich ores and lime are added inside the refining furnace in advance; and (d) carrying out tapping off, and then, casting and conditioning, so as to obtain low-carbon ferrormanganese with relatively low impurity content, i.e., relatively low carbon content and relatively low phosphorus content. Compared with technologies for producing low-carbon ferromanganese through dephosphorizing and decarbonizing in the prior art, the method has the advantages that the used raw material, namely, washed iron is low in price, and the dephosphorizing agent is a novel dephosphorizing agent, is cheaper than commonly-used metal or alloy dephosphorizing agents and can be fully applied to production, so that the production cost can be greatly reduced.
Description
Technical field
The present invention relates to a kind of production method of ferromanganese alloy, particularly relate to a kind of method adopting industrial residue washing iron to produce low carbon ferromanganese.
Background technology
Manganeseirom is the alloy of manganese and iron, wherein also containing carbon, silicon, phosphorus and other elements on a small quantity.Different according to carbon content, ferromanganese is divided into again high carbon ferromanganese, mid-carbon fe-mn and low carbon ferromanganese three kinds.Define the content of carbon impurity and phosphorus in manganeseirom in China's ferromanganese standard (GB/T3795-2006), different with phosphorus content by carbon, be divided three classes: 1, low-carbon (LC) class, namely carbon content is not more than 0.7%, phosphorus content less than 0.3%; 2, middle carbon class, namely carbon content is greater than 0.7% to 2.0%, phosphorus content less than 0.4%; 3, high-carbon class, namely carbon content is greater than 2.0% to 8.0%, phosphorus content less than 0.4%.The content of carbon and phosphorus is the key weighing manganeseirom quality.
At present, the method for production manganese-iron alloy has three kinds: electro-silicothermic process, shaking ladle process and blow oxygen, be batch operation.Often kind of method all has respective merits and demerits.Electro-silicothermic process is that manganese ore, manganese-silicon and lime are added in electric furnace, rely on electric heating to make load melting, then carry out refining desiliconization and obtain medium-low carbon ferromanganese, the charging status just added is different, be divided into again cold charge practice and hot charge practice, the furnace charge added is all that cold burden is called cold charge practice.Manganese ore and lime are warm a little, and manganese-silicon is called hot charge practice at liquid loading.Shaking ladle process is that preheated manganese ore, lime and liquid manganese-silicon are added in shaking ladle, then shakes, and makes load melting and carry out refining desiliconization and obtain medium-low carbon ferromanganese by means of the sensible heat of furnace charge and reaction heat.Widely used both at home and abroad is at present electro-silicothermic process and shaking ladle process.
In China, the ground such as Guizhou, Yunnan, Chongqing, Hunan, Guangxi, it is main J. sigillate region, wherein manganese-silicon has a large amount of discarded solid slag after producing, these waste residues form particulate state after cold water fast cooling, also have the ferro-silico-manganese of low levels in waste residue except unwanted impurity.Reduce production cost for improving resource utilization, enterprise adopts cleaning table equipment to carry out washing by inclined-plane flow action to waste residue and is separated, and obtain content higher and be pulverous ferro-silico-manganese, abbreviation washing iron, decreases the wasting of resources.There are a lot of medium-sized and small enterprises using this kind of washing iron as raw material, add Mn-rich slag and lime, adopt electro-silicothermic process or shaking ladle process to produce high, mid-carbon fe-mn alloy.
Application for a patent for invention CN201010186365.X discloses a kind of mid-carbon fe-mn and Mn-rich slag production technique, it comprises following process: washing iron, electrolytic manganese residues are carried out measuring, mixing with lime, add refining furnace to smelt, finishing of testing after going out refining, obtains mid-carbon fe-mn and Mn-rich slag.Remaining solid slag carries out broken screening and separating and obtains ferromanganese slag and return refining furnace and use, and slag is made pad stove and used.Wherein washing iron and electrolytic manganese residues come from the solid slag of silicomanganese, J. sigillate producer.In addition dedusting and recycling are done for the flue dust produced in refining process and byproduct Mn-rich slag.This method can realize recycling economy, reaches the object of energy-saving and emission-reduction.The technology of this patent application can only obtain mid-carbon fe-mn alloy, cannot obtain ferromanganese alloy.
The method of producing low carbon ferromanganese mainly two: one be use intermediate product high silicon manganese-silicon alloy, add ANOMALY IN FINE QUALITY MANGANESE DEPOSITS or Mn-rich slag and appropriate lime, fluorite, smelt in refining furnace and obtain; Another to be added by electrolytic metal Mn in intermediate frequency furnace heavy molten, adds that appropriate scrap iron, mid-carbon fe-mn etc. can obtain.Using maximum is first method.But in the first production method, the producer often use cheap defective in low silicomanganese, the carbon contained and phosphorus higher, need to carry out dephosphorization decarburization, qualified low carbon ferromanganese could be obtained.The method of decarburization adopts to add siliceous reducer and remove with the method improving silicone content, and decarburizer comprises ferrosilicon or industrial silicon.Its principle adds exactly after decarburizer and raises containing Si in manganese-silicon, and after increasing silicon, in manganese-silicon, the content of oxygen reduces greatly, reaches sufficiently high reducing atmosphere, under the reducing conditions can well the dephosphorization of decarburization and postorder.Wherein, Si can combine with Mn, generates and compares Mn
3the MnSi that C is more stable, thus the Mn that will have generated
3c in C extrudes, and achieves decarburization object.In manganese-silicon, removing of phosphorus is very difficult, than carbon remove difficulty many, be also global problem.In manganese-silicon, removing of phosphorus is under reducing atmosphere, adds dephosphorization under reducing atmosphere agent, and dephosphorizing agent is metal or alloy dephosphorizing agent and basic flux dephosphorizing agent two kinds mainly.Basic flux dephosphorizing agent comprises CaO-Na
2o system, CaO-K
2o system, CaO-CaF
2system, CaO-SiO
2system etc.This type of dephosphorizing agent add-on is large, and sometimes up to 40%, dephosphorization effect is also limited.Metal and alloy dephosphorizing agent are often Ca, Mg, Al, Ba, CaSi, Ca
3a1
2, the alloys such as CaBaAI and Ba-Si and slag former CaO-CaF
2mixture, this type of alloy addition is more than 5% of manganese-silicon, and Threshing injury is fast and dephosphorization rate is high, and shortcoming is some metal itself may be that impurity enters in manganese-silicon, and metal or alloy is expensive, and cost is too high, is difficult to be applied in production.The condition that this two classes dephosphorizing agent generally needs is Si content is the 18% even manganese-silicon of more than 25%, does not substantially have dephosphorization effect to Si content less than 18% manganese-silicon, because dephosphorization under reducing atmosphere needs to keep enough low oxygen gesture ability dephosphorization.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method adopting industrial residue washing iron to produce low carbon ferromanganese for above-mentioned defect.The whole percentage compositions related in the application all refer to weight percent.
For solving the problem, the raw water washed metal that the present invention uses is the waste residue after silicomanganese factory produces, the shaking table equipment of ore dressing is adopted to carry out separation washing by the effect of inclined-plane current to waste residue, obtain content higher and for pulverous washing iron, it contains manganese more than 50%, silicon more than 12%, carbon less than 3%, phosphorus less than 0.4%, also has a small amount of iron.This ferromanganese producing and manufacturing technique cost of material is cheap, resource reclaim, and technique is simple, and less investment, benefit is fast.First, add in refining furnace after washing iron, lime and decarburizer are mixed and heat decarburization, obtain low carbon and high silicon manganese-silicon, again manganese-silicon is poured into dephosphorization in shaking ladle, the dephosphorizing agent of existing preheating in shaking ladle, after concussion mixing dephosphorization, joins desiliconization in refining furnace again Purified Mnsi Alloy, there are the rich manganese ore of preheating or middle manganese slag in refining furnace, after desiliconization, obtain low phosphorus and low carbon manganeseirom.Finally carry out casting, finishing and warehouse-in, obtain qualified product.The present invention's decarburizer used increases silicea (comprising ferro-silicon or industrial crystallization silicon), the content of silicon in the very low washing iron of silicon content (silicone content <18%) is made to reach more than 28% by the content increasing silicon, carbon in washing iron and phosphorus content are reduced greatly, especially the content of carbon can reach 0.7% even less than 0.4%, add cheap dephosphorizing agent dephosphorization again, phosphorus content in further reduction manganese-silicon, obtain low-carbon low-phosphor manganese-silicon, finally add Mn-rich slag and obtain ferromanganese alloy.
The present invention achieves the above object by the following technical solutions, comprises the following steps:
1) raw material prepares and major equipment
Comprise washing iron, decarburizer, dephosphorizing agent, unslaked lime and fluorite, rich manganese ore, if these raw material oversize material, need to carry out fragmentation, particle size after cracking≤10mm, major equipment is refining furnace.
2) batching and decarburization
According to the needs of each refining furnace, weigh washing iron, decarburizer, unslaked lime and fluorite, then the washing iron of certain proportioning, decarburizer, unslaked lime and fluorite are mixed, join in refining furnace and carry out heating smelting, calm for some time after washing iron melting, skim and remove the superiors' mixture, this mixture is high carbon-coating, silicate, fluorite and lime etc. mainly.Final acquisition low carbon and high silicon manganese-silicon.
3) dephosphorization
In order to further dephosphorization, need to add dephosphorizing agent.First determine the consumption of best dephosphorizing agent, then join in shaking ladle rapidly, then the silicomanganese in refining furnace is joined in shaking ladle, calm for some time after melting, upper strata mixture is removed in deslagging.
4) desiliconization
Rich manganese ore and lime is added in refining furnace, then qualified low phosphorus and low carbon high silicon manganese-silicon alloy is poured in refining furnace, carry out desiliconization heat with rich manganese ore and lime to convert, if sample examination is defective supplement a part of rich manganese ore and lime again, up to the qualified rear tapping casting of sample examination alloy, finishing, end product is put in storage.
5) waste gas and Solid state fermentation
The three wastes refer to waste gas, waste residue and waste water in the industrial production, and in manganeseirom is produced mainly waste gas and waste residue.Owing to being opened type refining furnace, produce so have large quantity of exhaust gas, need to use disposal box and cooling tower to carry out cooling dust removal process.Waste residue can carry out fragmentation screening, and Mn-rich slag directly returns heat in stove and converts manganese-silicon.Poor manganese slag can produce the adulterant, fertilizer, slag brick etc. of cement.Calcium phosphide (Ca can be produced in dephosphorizing process
3p
2), meet water vigorous reaction and generate phosphuret-(t)ed hydrogen (PH
3), method of disposal adds dry sand, dry powder or stone flour.
The present invention adopts washing iron as raw material; due to the waste residue that washing iron is manganese-silicon producer; with low cost; valuable element wherein reclaims the requirement that can meet present national energy-saving and reduce discharging; protection of the environment is stopped to pollute; by decarburization and dephosphorization, obtain Purified Mnsi Alloy, then desiliconization obtains low carbon ferromanganese.Compared with other dephosphorization decarburization production ferromanganese alloy technology, raw materials used washing iron is cheap, and dephosphorizing agent uses novel dephosphorizing agent, and its price is compared very cheap with common metal or alloy dephosphorizing agent, can be applied in the middle of production completely, production cost is reduced greatly.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
The major equipment that the present invention uses is a refining furnace and a shaking ladle.The main raw material used is washing iron, and wherein Fe content is more than 60%, and silicone content is about 14%, and carbon content is 2.31%, and phosphorus content is 0.18%, and all the other are iron and aluminum silicate impurity.Decarburizer is ferrosilicon powder FeSi75, and wherein Si content is 74-80%, carbon content 0.1%, phosphorus content 0.035%, below granularity 10mm, also can be that FeSi65 or industrial silicon, silicon metal etc. increase silicea.Dephosphorizing agent is novel silicon calcium powder, and calcium contents is more than 35-36%, and silicone content is more than 18-20%, and phosphorus content is less than 0.04%, and carbon content is less than 0.1%, and granularity is 0-5mm.Rich manganese ore, wherein Fe content is 43%, iron level 3.2%, and all the other are the impurity such as aluminosilicate, below granularity 10mm.Lime and fluorite all require carbon and phosphorus content low.
First, join in electric furnace after the mixing of raw water washed metal, decarburizer and slag former, wherein slag former is the mixture of lime and fluorite, ratio is 60:40, add-on is the 8-10% of washing iron weight, be as the criterion with the quantity of slag in the washing iron detected, decarburizer add-on is more than 28% to be as the criterion, and temperature is about 1500 DEG C.Calm for some time after washing iron melts, the time is 30 minutes.Finally skim and remove the 2-3mm mixture of the superiors, this mixture comprises high carbon-coating, slag, fluorite, lime etc.Acquisition be carbon containing 0.28%, phosphorous 0.17% high silicon manganese-silicon alloy.
Poured into from refining furnace in hot metal ladle by liquation after decarburization, add dephosphorizing agent in advance in hot metal ladle, dephosphorizing agent add-on is the 7-10% of manganese-silicon, can combined lime and fluorite in dephosphorizing agent, and add-on is the 8-10% of liquation amount, and ratio is 60:40.To sling shaking ladle with crane, the reaction of shake shaking ladle, after 8-10 minute, outwells rapidly the slag on upper strata to avoid occurring returning phosphorus phenomenon.Can obtain after dephosphorization carbon containing 0.15%, phosphorous 0.075% high silicon manganese-silicon alloy.
After decarburization dephosphorization, the manganese-silicon in shaking ladle is poured in refining furnace, in refining furnace, added rich manganese ore and the lime of preheating.Adding rich manganese ore is in order to desiliconization.And the effect of lime is slag making and the reduction helping manganese.The add-on of lime is 1.0 ~ 1.2 to be advisable with basicity in liquation.After the furnace charge in refining furnace all dissolves, sample examination alloy silicon content, qualifiedly can come out of the stove, and can add a part of rich manganese ore and lime again if defective.
Obtaining product is low phosphorus and low carbon manganeseirom, and wherein Fe content is 80.0% ~ 88.0%, and silicone content is 1.3%, carbon content 0.5%, phosphorus content 0.16%.
Produce the waste gas mainly flue dust in manganeseirom.The common feature of these flue dust is that dust is comparatively thin, and granularity is generally below 1 ~ 2 μm.Gas is N mainly
2, CO
2, H
2o and SO
2mixture.Dust is mainly containing CaO, SiO
2, MgO, Fe
2o
3, Al
2o
3, the impurity such as MnO, C, and the valuable metal such as V, In, Tl, Pb, Sn, Au, Ag.The comprehensive reutilization of flue dust, is related to the saving of environment protection, metal recovery and the energy.It is good that comprehensive utilization work is done, and not only can improve working conditions, and reducing environmental pollution, and can promote production technique, reclaim useful metal, is a great riches.To these flue dust, on the one hand enclosed workshop is adopted to body of heater, synthetical recovery can be carried out to flue dust on the other hand.The method reclaimed is that first flue dust enters in disposal box, and the dust of the larger heavier-weight of particle diameter is deposited in disposal box with its deadweight.Remaining gas enters in counterflow cooling tower through upcast, downtake again, puts into sodium carbonate or sodium hydroxide solution in shower, and flue gas can be lowered the temperature dedusting by shower, can also absorb the sulfurous gas in flue gas.
Also can produce a large amount of waste residues in production, these waste residues are Mn, Fe, CaO, SiO
2, Al
2o
3, the mixture such as MgO.If when the content of Mn reaches more than 30% in these waste residues, directly can to return in stove heat together with rich manganese ore and convert manganese-silicon.If Mn content is lower in these waste residues, then can as the adulterant, fertilizer, slag brick etc. producing cement.
Because calcium and phosphorus combination can produce calcium phosphide (Ca in dephosphorizing process
3p
2), this material has severe toxicity and extremely unstable, meets water vigorous reaction and generates phosphuret-(t)ed hydrogen (PH
3), the waste residue therefore after dephosphorization needs process, and treatment process adds dry sand, dry powder or stone flour.
Claims (3)
1. industrial residue washing iron recycles a method of producing low carbon ferromanganese, it is characterized in that described method steps is as follows:
A, a certain amount of washing iron, slag former, decarburizer to be mixed, add heating in refining furnace and melt decarburization;
Join after b, decarburization inside shaking ladle and carry out dephosphorization treatment, inside shaking ladle, add dephosphorizing agent and lime and fluorite in advance;
Turn back to again in refining furnace after c, dephosphorization and carry out desiliconization process, inside refining furnace, add rich manganese ore and the lime of preheating in advance;
D, come out of the stove after carry out casting, finishing, obtain carbon impurity and the lower ferromanganese alloy of phosphorus content.
2. the method for production low carbon ferromanganese according to claim 1, it is characterized in that: described washing iron is the waste residue after silicomanganese factory produces, the shaking table equipment of ore dressing is adopted to carry out separation washing by the effect of inclined-plane current to waste residue, obtain content higher and for pulverous washing iron, it contains manganese more than 50%, silicon more than 12%, carbon less than 3%, phosphorus less than 0.4%, also has a small amount of iron.
3. the method for production low carbon ferromanganese according to claim 1 and 2, is characterized in that: slag former be lime and fluorite with the mixture of 60:40 weight ratio, amount of the mixture is the 8-10% of washing iron weight, is as the criterion with the quantity of slag in the washing iron detected; Decarburizer is ferrosilicon powder FeSi75, and wherein silicone content is 74-80%, carbon content 0.1%, phosphorus content 0.035%, below granularity 10mm, decarburizer add-on is 28% of washing iron weight, be as the criterion with the silicone content in the washing iron detected, decarburization Heating temperature is 1500 DEG C; Dephosphorizing agent is the compound dephosphorization agent of alloy dephosphorizing agent and basic flux dephosphorizing agent, and its composition sees the following form:
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Cited By (1)
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| CN110669944A (en) * | 2019-09-30 | 2020-01-10 | 曾世林 | Method for preparing pure ferromanganese alloy and active silicate particles from inferior alloy powder |
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| CN1876857A (en) * | 2005-06-11 | 2006-12-13 | 太原钢铁(集团)有限公司 | Method for smelting stainless steel using molten iron as raw material |
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2015
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| CN110669944A (en) * | 2019-09-30 | 2020-01-10 | 曾世林 | Method for preparing pure ferromanganese alloy and active silicate particles from inferior alloy powder |
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