CN108546835B - A kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy - Google Patents

A kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy Download PDF

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CN108546835B
CN108546835B CN201810390048.6A CN201810390048A CN108546835B CN 108546835 B CN108546835 B CN 108546835B CN 201810390048 A CN201810390048 A CN 201810390048A CN 108546835 B CN108546835 B CN 108546835B
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rare earth
agglomerate
reducing agent
carbonaceous reducing
carbothermy
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CN108546835A (en
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王有禄
王有祯
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Wu La Front Banner Three Cai First Ferroalloy Co Ltd
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Wu La Front Banner Three Cai First Ferroalloy Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00

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Abstract

The invention discloses a kind of methods of serialization carbothermy production rare earth ferrosilicon alloy, it prepares problem of the rare earth ferroalloy in terms of the deficiency and product quality promotion in terms of continuous production for existing carbo-thermal process, the core content of the present invention program is a kind of ingredient based on core-shell structure copolymer multilayered structure and ingredient and smelting process method, the case where furnace bottom rising can be effectively avoided in one-step method smelting is carried out by mineral hot furnace, to realize continuous operations, and obtain the rare earth ferrosilicon alloy product of high-quality, smelting operation condition is similar to Antaciron simultaneously, the operating process of working face becomes more easy, energy consumption level is substantially reduced.

Description

A kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy
Technical field
The present invention relates to a kind of methods of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy, belong to pyrogenic process Metallurgy prepares the technical field of rare earth alloy.
Background technique
Rare earth ferrosilicon alloy is the major product of China's rare earth intermediate alloy industry, and the rare earths such as production rare earth ferrosilicomagnesium The critical materials of silicon-base alloy, both extremely important metallurgical industry special alloy.
The production method of rare earth alloy mainly has electro silicothermic process, carbothermic method, fused salt electrolysis process and converts mixed method, for dilute For the industrialized production of unmanufactured iron alloy, only having first two method that can have at present realizes large-scale industrial production condition And industrial value.The most conventional method for producing rare earth ferrosilicon alloy is electro silicothermic process, i.e., ferrosilicon production is first carried out, then again with silicon Iron and rare earth material are raw material, produce rare earth ferrosilicon alloy by slag agent of calcium oxide, commonly known as " two step method ".Due to electric silicon Thermal method haves the shortcomings that preparation cost is high, the quantity of slag is big, and carbo-thermal process develops into a kind of important rare earth ferroalloy successively Production technology, and in recent years in obtained tremendous development.So-called carbothermic method, be with rare earth slag charge, silica, carbonaceous also Former agent, the steel cuttings direct continuous production in mineral hot furnace, commonly known as " one-step method ".Two kinds of production methods compare, (1) carbon heat Reduction method, which prepares rare earth ferroalloy (that is: one-step method), has furnace temperature height, melting loss of elements few, theoretically can be with quantity-produced technique Characteristic has more economic resource efficiency and lower production cost excellent because which save the resource consumptions of ferrosilicon, lime Gesture；(2) carbo-thermal process has better prospect of industrial development by the advantage on its production cost, but carbothermic method The product quality index of prepared rare earth ferroalloy is obvious compared to electric silicon thermal method product differentiation, this also leads to current all Gao Pin Matter rare earth ferrosilicon alloy product must still continue to use electro silicothermic process technique to be manufactured.
In the technology of the various producing RE ferrosilicon alloy through one-step process researched and developed, with Northeastern University Zhang Chengxiang, appoint It is the most mature to deposit one step production method of rare earth functional materials controlled etc. in ZL92109998.3 patent, fundamentally to change China's rare earth intermediate alloy provided important technical foundation using the situation of single electro silicothermic process production in the past, and was producing It is promoted and applied in practice.Its technical solution is carried out after being fired fluoro-carbon-cerium ore concentrate, with carbonaceous reducing agent, binder Briquetting is mixed, then enters the technique of furnace smelting together with silica, carbonaceous reducing agent.Chen Jingyou et al. is special in application number 03135449.1 One of benefit reduction with carbon method produces rare earth ferrosilicon alloy method, and ingredient is that rare earth ore concentrate, silica and reducing agent is primary Property mixing.Yuan Hongbin et al. is disclosed in the patent application of 01107843.X a kind of produces high rare earth ferroalloy in mineral hot furnace Technique, ingredient and process are to be carried out using the rare earth ore concentrate of content 45~85% with carbon, and mixed carbon comtent is that rare earth oxide turns 2~5 times of carbon amounts needed for changing, then plus adhesive mixing be squeezed into honeycomb, become rare earth agglomerate after coking is handled, then match Enter silica (the ratio between rare earth metal and silicon total amount in silica are 1: 0.50~1.2 in coking rare earth agglomerate)；Make reducing agent with coke (carbon amounts is the 0.85~0.94 of theoretical carbon amounts)；Three is uniformly added into mineral hot furnace and is smelted.It is in the patent No. Disclosed in 02110308.9 patent of invention it is a kind of with the technique of rareearth enriching material rareearth cerium silicon, rareearth lanthanum silicon alloy, Ingredient and process are first to mix rareearth enriching material, fine coal powder, high carbon adhesive, extrusion forming, after agglomerate is made Enter in mineral hot furnace, 300 DEG C~900 DEG C self-baking coking, during mineral hot furnace endosexine and jetsam, self-baking coking is processed into coking Agglomerate；The burnt and blue carbon of silica, bottle coal is incorporated again to be smelted.It is announced in the patent application of application number 201510398475.5 It is a kind of to be with the technique of rareearth enriching material rare-earth silicon alloy, ingredient and process: by rareearth enriching material, powdered carbon, plant Object adhesive mixes, and extrusion forming is made agglomerate, then enters agglomerate in mineral hot furnace, self-baking coking, in mineral hot furnace endosexine and During jetsam, self-baking coking is processed into coking block mass；Silica, bottle coal coke and charcoal are added in coking block mass, in mineral hot furnace It is smelted.
A kind of Mu Donglin furnace suitable for producing RE ferrosilicon alloy through one-step process reported in the ZL01108501.0 patent Expect distribution, according to the patent of invention technology, the furnace charge suitable for producing RE ferrosilicon alloy through one-step process includes rare earths material The block-like silica of pelletizing, grain and charcoal reducing agent, wherein the rare earth ore concentrate containing powdery, charcoal restore described rare earths material pelletizing again Agent, adhesive.A kind of Chen Jingyou et al. high cerium mischmetal Antaciron reported in 201510372708.4 patent applications and its Production method, ingredient and production method are waterglass will to be added in high cerium mischmetal slag first, so that high cerium mischmetal slag depickling, then Carbon dust and alkaline adhesive is added, is pressed into rare earth pelletizing；Silica, carbonaceous reducing agent and above-mentioned rare earth pelletizing will finally be entered together Furnace is smelted.
Theoretically, carbothermic method can carry through to the end reduction in furnace, and be able to achieve no industrial residue Industrialized production.But in practical industrial practice, there are the easy drosses of furnace bottom to go up, and production is difficult to continue for a long time, and the working of a furnace is once disliked Change and the industrial technologies defect such as is not easy to reverse." carbothermic method produces rare earth ferrosilicon alloy furnace bottom dross and goes up " and " technique is not Can long-term continuous production " this two big industry problem always long-standing problem carbo-thermal process rare earth ferroalloy is prepared with one-step method Industry development, become a key restriction of domestic rare earth ferroalloy development.The maximum disadvantage of carbothermy technique is reaction Intermediate product " carbide of rare earth metal ", which is easy to assemble when smelting, forms accretion, so that furnace bottom is escalated, the working of a furnace deteriorates, sternly Important place influences rare earth ferrosilicon continuous production.In actual production technology development process, although domestic rare earth ferroalloy technology Tested with industrial circle by years of researches and industrialization, ingredient, electric operation and in terms of carried out one The improvement adjustment of series, but can only also delay furnace bottom rising, it cannot fundamentally solve the problems, such as continuous production.Another tool The problem of industry general character is carbothermy technique compared to electro silicothermic process technique, and rare earth ferrosilicon alloy product is bright compared to quality discrepancy Aobvious and quality control is often not sufficiently stable.
Summary of the invention
The purpose of the present invention is prepare rare earth ferroalloy in terms of continuous production not for existing carbo-thermal process It is enough and product quality promotes the problem of aspect, a kind of method of serialization carbothermy production rare earth ferrosilicon alloy, core is provided Intracardiac appearance is a kind of ingredient based on core-shell structure copolymer multilayered structure and ingredient and smelting process method, passes through mineral hot furnace and carries out a step The case where furnace bottom rising can be effectively avoided in method smelting, to realize continuous operations, and obtains the rare earth ferrosilicon of high-quality Alloy product, while smelting operation condition, similar to Antaciron, the operating process of working face becomes more easy, and energy consumption level is bright It is aobvious to reduce.In summary the advantageous effects of several respects, so as to complete the present invention.
In order to clearly state technical solution of the present invention, it is necessary to also for the domestic many carbon heat having been reported Original process technical solution and its ingredient situation are dissected, and are analyzed general rule therein and are found out and need further to have innovated Kind critical process node.
By reduction reaction process, the current technology of carbon thermal reduction production rare earth ferrosilicon alloy is divided into three key steps, That is: (1) reducing silica is silicon and silicon monoxide and rare earth compound carbonization production carbide；(2) Rare Earth Carbides are by one Silica is reduced to rare earth metal；(3) the iron filings compound that rare earth metal and when silicon and ingredient are added is at rare earth ferrosilicon alloy (" rare earth metallurgy technology ", Science Press, Wu Wen is remote etc. to be write).The intermediate product of silicon and rare earth metal is all carbide, it Can be with SiO and SiO2It interacts and decomposes.The aggregation of carbide easily causes accumulation on furnace hearth if destroying not in time, is formed Accretion.
Under the physical condition of carbothermy reduction process, the quantity ratio of the rare earth metal and silicon that generate and decompose will be by heating power It learns with the summation of kinetic factor and determines.In terms of thermodynamics, the generation of Rare Earth Carbides is quite more held in step (1) Easily (can generally be gone on smoothly at 800 DEG C or more, corresponding to 1 in following reaction equation and 2), and silica be reduced into silicon and The realization difficulty and realization condition of silicon monoxide are more harsh, and (general requirement just can be carried out at 1300 DEG C or more, by following reaction The chemical balance of 3-a~3-e in formula is determined)；In terms of aerodynamic point, based on rare earths material and carbonaceous reducing agent conversion life Reaction speed at Rare Earth Carbides is faster, and restores silica using reducing agents such as coke and be converted into silicon and an oxidation The reaction speed of silicon is quite many slowly, and then is made to Rare Earth Carbides by the reaction process that silicon monoxide is reduced to rare earth metal At retardation (corresponding to 4 in following reaction equation).
By taking rich cerium class rare earths material as an example, when using carbon reducing and smelting rare earth ferrosilicon, from the heating power of Si-O-C-Ce system It learns and dynamics shows key reaction in furnace are as follows:
2CeO2+C=Ce2O3+ CO (1)
Ce2O3+5C=2CeC2+ 3CO (2)
SiO2+ C=SiO+CO (3-a)
2SiO2+ SiC=3SiO+CO (3-b)
SiO2+ Si=2SiO (3-c)
SiO+2C=SiC+CO (3-d)
SiO+SiC=2Si+CO (3-e)
CeC2+2SiO=CeSi2+ 2CO (4)
Industrial technology report of the country in terms of carbothermy produces rare earth ferrosilicon alloy is mostly to have followed Northeastern University The technical thought and technological principle that Research Team is proposed on the basis of ZL92109998.3 patent.Its ingredient and process program Basic ideas are: also by rare earths material (such as: fluoro-carbon-cerium ore concentrate rare earth ore concentrate, high cerium mischmetal slag, rareearth enriching material) and carbonaceous Former agent (such as: carbon dust, coke, powdered carbon, fine coal powder) be mixed into pelletizing (or referred to as agglomerate), then is directed to above-mentioned rare earth ball Group carries out certain pretreatment, then carries out ingredient smelting with silica, carbonaceous reducing agent, and technical thought is: utilizing carbothermy smelting Refining process converts Rare Earth Carbides (REC) for rare earth compound first, and the Rare Earth Carbides are again by silicon monoxide (by titanium dioxide Silicon is generated by carbonaceous reducing agent) it is reduced to rare earth metal, then (restored by silica by carbonaceous with the silicon restored Agent reduction is generated) combine generation RE-Si alloy, i.e. rare earth ferrosilicon alloy.
The previous various realization steps based on the mentioned technical thought of ZL92109998.3 patent are all first by rare earths material Being mixed and being suppressed agglomerating with carbonaceous reducing agent (also includes increasing a certain amount of waterglass etc. containing silicon adhesive, alkalinity bonding Agent), the technical solution that then ingredient is smelted together with silica, carbonaceous reducing agent again.In the actual production process, due in system Rare earths material and carbonaceous reducing agent can be converted into Rare Earth Carbides under lower temperature conditions, and formation speed is too fast, Rare Earth Carbides generated, which fail to restore in time in furnace charge system, is converted into rare earth metal, so causing Rare Earth Carbides rich After collection because its be easy to assemble to caused by furnace bottom rising, thus become influence rare earth ferrosilicon alloy continuous production great disease Where knot.
The object of the present invention is achieved like this: a kind of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy Method, it is characterised in that method includes the following steps:
(1) with rare earths material, siliceous raw material, carbonaceous reducing agent it is that basic raw material distinguishes ingredient, and repressed and be made dilute Mass of soil block；The rare earth agglomerate has core-shell structure copolymer multilayered structure, and wherein rare earth agglomerate kernel is rare earths material, and rare earth agglomerate middle layer is Siliceous raw material, rare earth agglomerate shell are carbonaceous reducing agent；Point of the first kernel of preparation use of rare earth agglomerate, again middle layer, again shell The compacting of step formula；According to the requirement of pressing process and the feature of basic material, can be added in each basic material adhesive come into Row ingredient；
Rare earths material amount is 80~100%wt(of theoretical value with total RE element in rare earth agglomerate in the rare earth agglomerate Meter), siliceous raw material amount is 10~60%wt(of theoretical value in terms of Si element total in rare earth agglomerate, the Si brought into including adhesive Element), carbonaceous reducing agent amount is that siliceous element reduction is the 100%-130%wt(of theoretical value needed for simple substance with dilute in rare earth agglomerate Fixed carbon meter in mass of soil block)；
(2) silica, carbonaceous reducing agent and above-mentioned rare earth agglomerate are entered furnace together to smelt；If dilute in rare earth agglomerate in step (1) The rare earths material of surplus is then entered furnace together with silica, carbonaceous reducing agent and above-mentioned rare earth agglomerate less than 100%wt by native material quantity It smelts；Silica input amount for 100~120%wt of theoretical value deduct surplus corresponding after institute's silicon content in rare earth agglomerate (with SiO in silica2Meter)；Carbonaceous reducing agent is corresponding surplus after contained carbon capacity in theoretical value deduction rare earth agglomerate 0.80~0.96 times (in terms of the fixed carbon in carbonaceous reducing agent)；Burning of coming out of the stove casting, obtains rare earth ferrosilicon alloy.
Invention is described further below:
A kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy of the present invention, it is characterised in that Rare earths material used is the enriched substance of rare-earth wet method metallurgy, polishing powder from rare earth waste material, concentrate, oxide ore, rare-earth smelting furnace The mixture of one or more of slag.
A kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy of the present invention, it is characterised in that Siliceous raw material used in step (1) is silica, SILICA FUME, silicon powder, silicon powder, silicon grain, quartz sand, silicon series ferroalloys smelted furnace cinder One or more of mixture.
A kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy of the present invention, it is characterised in that Carbonaceous reducing agent used is coke, powdered carbon, semi-coke, semi-coke, charcoal, bottle coal coke, bituminous coal, petroleum coke, one kind in fine coal powder Or several mixture；Carbonaceous reducing agent requires the fixed wt of C>=70%, ash<10%wt in step (1)；Carbonaceous in step (2) Reducing agent requires the fixed wt of C>=80%, ash<7%wt.
A kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy of the present invention, it is characterised in that Adhesive used is the mixing of one of waterglass, SILICA FUME, bentonite, paper pulp, syrup waste liquid, plant amylum or concentration Object.
A kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy of the present invention, it is characterised in that Step (1) described substep is compressed to first compacting rare earths material and obtains primary agglomerate, the kernel as rare earth agglomerate；Again by conduct The siliceous raw material of middle layer material is covered in the outer surface of primary agglomerate, and carries out compacting and form second level agglomerate；Further, will make It is covered in the outer surface of second level agglomerate for the carbonaceous reducing agent of outer shell material, and carries out compacting and forms the rare earth with core-shell structure Agglomerate.
A kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy of the present invention, it is characterised in that Contain SiO in silica described in step (2)2> 98%wt, Al2O3< O .4%wt, CaO < 0.2%wt.
A kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy of the present invention, it is characterised in that It is stood 10 minutes or more after coming out of the stove described in step (2) and carries out burning casting again；If there is suspension slag in the alloy molten solution upper layer come out of the stove, Then it is subject to auxiliary device to be excluded, then carries out burning casting again.
Technical principle of the invention is:
1, the enlightenment of technological principle of the invention from electro silicothermic process technique, electro silicothermic process technique are restored using ferrosilicon Rare earth oxide in rare earths material is to obtain the rare earth ferrosilicon alloy of high-quality.The invention proposes use a kind of core-shell structure copolymer The rare earth agglomerate of multilayer is smelted, by rare earths material, siliceous raw material, carbonaceous reducing agent correspond respectively to kernel, middle layer and Shell, since siliceous raw material as middle layer material, send out by the carbonaceous reducing agent of rare earth material and shell to kernel in lumpiness Raw reaction is converted into Rare Earth Carbides and plays the role of barrier property.Based on technical solution of the present invention, carbon reduction method smelting is being used When refining, it is equivalent to and rare earth clinker is added into the charge composition of similar smelting Si-Ca alloy, core reaction is rare earth oxide (6 and 7 in such as following reaction equation) are restored by the silicon monoxide of middle generation under furnace body hot conditions and silicon；In reaction equation 6 and 7 SiO2It is entered in furnace body Si-O-C system again, the chemical balance that Si-O-C system is participated in the hot environment of reproducibility is anti- Answer (main reaction formula such as 5-a~5-c).Main reaction equation are as follows:
SiO2+ Si=2SiO (5-a)
SiO2+ C=SiO+CO (5-b)
SiO+2C=SiC+CO (5-c)
SiO+REO+Si=RE+2SiO2(6)
Si + REO +3SiC=2RESi2+ 3CO (7)
2, in technical solution of the present invention, Si element total amount is theoretical value in siliceous raw material (or containing silicon adhesive) 100~120%, comprehensively considered both sides factor: (1) there are a certain amount of scaling loss for the Si element in smelting process；(2) it comes out of the stove Silicon content present in suspension slag in material (mainly with oxidation state, compound state).
Compared with prior art, the present invention the advantage is that:
1, the present invention is by a kind of new technological means, and being formed to Rare Earth Carbides has effective barriering effect, in root Prevent to make because Rare Earth Carbides form too fast and cannot convert brought " rise of furnace bottom dross " problem in time again on this The silicon process that must be carbonized reducing process being capable of long-term continuous production.
2, the present invention program combines certain process characteristics of electric silicon process, and conventional carbon heat may be implemented in industrial practice also The former unapproachable excellent physical and chemical index of method, obtains the rare earth ferrosilicon alloy product of high-quality.
3, when carrying out industry manufacture according to the present invention program, the technology controlling and process on furnace body upper layer is similar to the smelting of silicon iron product Refining, operating surface are more easily controlled；Carbonaceous reducing agent is largely consumed on furnace body upper layer, in addition using thanks to carbon behaviour in smelting process Make, is easy to electrode and inserts deeply, expand the high-temperature area in furnace.In view of, for the reduction of rare earth oxide, electric silicothermic reduction Temperature requirement will be lower than carbo-thermal process, therefore, using the present invention program, the high conversion rate of rare earths material, rare earth element Burn out rate is low.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Embodiment 1
The technique that rare earth ferrosilicon alloy (12500KVA mineral hot furnace produces Xt30Si) is prepared with rich cerium slag, including following step It is rapid:
(1) the rare earth agglomerate preparation of core-shell structure copolymer multilayered structure
By rich cerium slag, (from the produced waste material of Sichuan bastnaesite hydrometallurgy, wherein TREO is 72%, (La2O3+ CeO2)/TREO=95.47%, CeO2/La2O3=91.12%:8.88%；Average particle size 5mm；BaO≤5%, CaO < 5%, TiO2<1%；Number Amount be the 100% of theoretical value) and it is wet after bentonite (3.0%wt that dosage be rich cerium slag) mix together, extruding pressure forms Agglomerate is made；It is baked to increase its intensity, it is spare as primary agglomerate.
By Cab-O-sil (SiO after crushing2>=98%wt, Al2O3The .2%wt of≤0 .5%wt, CaO≤0, average particle size 3mm；Quantity is the 30% of theoretical value) and waterglass (wherein SiO2>=25%, modulus is 3.5 scholars 0.30；Dosage is Cab-O-sil 4.0%) it mixes together, material rolling is spread on to the surface of primary agglomerate, densification operation is carried out while rolling is applied, passes through machinery Device automatic cycle for several times, until silica powder material has all been covered on the outer surface of primary agglomerate；It is baked to increase its intensity Add, it is spare as second level agglomerate.
By semi-coke powder (fixed carbon>70%, ash content<10%, moisture<5%, granularity≤5mm；Quantity is to be by siliceous element reduction 120% of theoretical value needed for simple substance) with waterglass and plant amylum (the two weight ratio is 1:1, and total dosage is the 5.0% of semi-coke powder) It mixes together, material rolling is spread on to the surface of second level agglomerate, densification and operations for forming are carried out while rolling is applied, passes through machinery Device automatic cycle for several times, until semi-coke powder material has all been covered on the outer surface of second level agglomerate；It is baked to increase its intensity Add, it is spare (it is with core-shell structure copolymer multilayered structure) as rare earth agglomerate.
(2) by silica (SiO2> 98%wt, Al2O3< O .4%wt, CaO < 0.2%wt；Quantity is that the 108%wt of theoretical value is deducted Surplus corresponding after institute's silicon content in rare earth agglomerate, with the SiO in silica2Meter), coke (wt of C>=80%, ash<7% wt；Quantity is 0.91 times that theoretical value deducts in rare earth agglomerate corresponding surplus after contained carbon capacity, in carbonaceous reducing agent Fixed carbon meter) and above-mentioned rare earth agglomerate enter together furnace smelting.
The process conditions smelted in mineral hot furnace specifically include that mineral hot furnace power supply system condition is electrode diameter 900mm, current potential 1.00~1.15V/cm of gradient, 140~190A of primary side current, 120~140V of secondary side voltage.
It is primary to go out alloy within average 50 minutes 2 hours；Alloy molten solution stands 12 minutes, excludes alloy molten solution by skimmer device A small amount of suspension slag that upper layer occurs, then carries out burning casting again.Through analyzing, the main component of suspension slag is CaOAl2O3· SiO2Double salt.
The heat statistical conditions in continuous production in two days are taken, concrete outcome is as follows:
1, add up 85.01 tons of rare earth ferrosilicon alloy product of production, the horizontal 7127KWh/t of average current drain in two days.
2, product physico-chemical analysis index (taking the aggregate sample of whole day product, unit: Wt%):
Detail RE Ce/TREO Si Al Ba+Ca P Fe
First day 30.24 86.12 49.97 0.42 1.53 <0.01 Surplus
Second day 30.34 86.08 50.56 0.41 1.63 <0.01 Surplus
Compared with the 30# rare earth ferrosilicon alloy prepared by the traditional handicraft, the impurity nocuousness Al element of 1 products obtained therefrom of embodiment Content reduces 70% or more, and Ba+Ca content reduces 55% or more, and quality is evident as excellent.
3, the RE rate of recovery is that 96.78%(refers to the RE total amount in the total amount of the RE in alloy/rare earths material).
4, suspension slag total amount 1084.8Kg, the weight ratio of opposite rare earth ferrosilicon alloy product are 1.28%.
Embodiment 2
Being mixed with rare earth ferrosilicon alloy with rich cerium slag and polishing powder from rare earth waste residue, (12500KVA mineral hot furnace is produced Xt35Si technique), comprising the following steps:
(1) the rare earth agglomerate preparation of core-shell structure copolymer multilayered structure
By rich cerium slag, (from the produced waste material of Sichuan bastnaesite hydrometallurgy, wherein TREO is 72%, (La2O3+ CeO)/ TREO=95.47%, CeO/La2O3=91.12%:8.88%；Average particle size 5mm；BaO≤5%, CaO < 5%, TiO2<1%；Quantity is reason By the 70% of value), polishing powder from rare earth waste residue (from polishing powder from rare earth using failure after produced waste material, wherein TREO be 84%, (La2O3+CeO2)/TREO=89.11%, CeO2/La2O3=93.44%:8.88%；Average particle size 3mm；BaO≤5%, CaO < 5%, TiO2<1%；Quantity is the 30% of theoretical value) and it is wet after (3.2%wt that dosage be rare earths material inventory) mix together, it is crowded Pressure is made type and agglomerate is made；It is baked to increase its intensity, it is spare as primary agglomerate.
By Cab-O-sil (SiO after crushing2>=98%wt, Al2O3The .2%wt of≤0 .5%wt, CaO≤0, average particle size≤ 3mm；Quantity is the 35% of theoretical value) and waterglass (wherein SiO2>=25%, modulus is 3.5 scholars 0.30；Dosage is Cab-O-sil 4.0%) it mixes together, material rolling is spread on to the surface of primary agglomerate, densification operation is carried out while rolling is applied, passes through machinery Device automatic cycle for several times, until silica powder material has all been covered on the outer surface of primary agglomerate；It is baked to increase its intensity Add, it is spare as second level agglomerate.
By semi-coke powder (fixed carbon>70%, ash content<10%, moisture<5%, granularity≤5mm；Quantity is to be by siliceous element reduction 120% of theoretical value needed for simple substance) with waterglass and plant amylum (the two weight ratio is 1:1, and total dosage is the 5.0% of semi-coke powder) It mixes together, material rolling is spread on to the surface of second level agglomerate, densification and operations for forming are carried out while rolling is applied, passes through machinery Device automatic cycle for several times, until semi-coke powder material has all been covered on the outer surface of second level agglomerate；It is baked to increase its intensity Add, it is spare (it is with core-shell structure copolymer multilayered structure) as rare earth agglomerate.
(2) by silica (SiO2> 98%wt, Al2O3< O .4%wt, CaO < 0.2%wt；Quantity is that the 112%wt of theoretical value is deducted Surplus corresponding after institute's silicon content in rare earth agglomerate, with the SiO in silica2Meter), coke (wt of C>=80%, ash<7% wt；Quantity is 0.92 times that theoretical value deducts in rare earth agglomerate corresponding surplus after contained carbon capacity, in carbonaceous reducing agent Fixed carbon meter) and above-mentioned rare earth agglomerate enter together furnace smelting.
The process conditions smelted in mineral hot furnace specifically include that mineral hot furnace power supply system condition is electrode diameter 900mm, current potential 1.00~1.15V/cm of gradient, 150~210A of primary side current, 126~148V of secondary side voltage.
It is primary to separate alloy within average 3 hours 10；Alloy molten solution stands 12 minutes, is excluded on alloy molten solution by skimmer device A small amount of suspension slag that layer occurs, then carries out burning casting again.Through analyzing, the main component of suspension slag is CaOAl2O3·SiO2 Double salt.
The heat statistical conditions in continuous production in two days are taken, concrete outcome is as follows:
1, add up 82.53 tons of rare earth ferrosilicon alloy product of production, the horizontal 7440KWh/t of average current drain in two days.
2, product physico-chemical analysis index (taking the aggregate sample of whole day product, unit: Wt%):
Detail RE Ce/TREO Si Al Ba+Ca P Fe
First day 35.61 86.12 46.40 0.47 1.69 <0.01 Surplus
Second day 35.57 86.08 46.44 0.49 1.77 <0.01 Surplus
Compared with the rare earth ferrosilicon alloy prepared by the traditional handicraft, the impurity nocuousness Al element of 2 products obtained therefrom of embodiment contains Amount reduces 72% or more, and Ba+Ca content reduces 60% or more, and quality is evident as excellent.
3, the RE rate of recovery is that 96.55%(refers to the RE total amount in the total amount of the RE in alloy/rare earths material).
4, suspension slag total amount 1113.6Kg, the weight ratio of opposite rare earth ferrosilicon alloy product are 1.35%.
Applicant carries out carrying out serialization life in two 12500KWA mineral hot furnaces respectively according to embodiment 1 and embodiment 2 It produces, continuous production 30 months or more, product with stable quality.
The foregoing is a specific embodiment of the present invention, it is noted that for those skilled in the art For.Various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as Protection scope of the present invention.

Claims (8)

1. a kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy, it is characterised in that this method include with Lower step:
(1) with rare earths material, siliceous raw material, carbonaceous reducing agent it is that basic raw material distinguishes ingredient, and repressed and rare earth group is made Block；The rare earth agglomerate has core-shell structure copolymer multilayered structure, and wherein rare earth agglomerate kernel is rare earths material, and rare earth agglomerate middle layer is siliceous Raw material, rare earth agglomerate shell are carbonaceous reducing agent；The multiple step format of the first kernel of preparation use of rare earth agglomerate, again middle layer, again shell Compacting；According to the requirement of pressing process and the feature of basic material, adhesive is added in each basic material to carry out ingredient；
Rare earths material amount is 80~100%wt of theoretical value in the rare earth agglomerate, and rare earths material amount is with total in rare earth agglomerate RE element meter；Siliceous raw material amount be theoretical value 10~60%wt, siliceous raw material amount in terms of Si element total in rare earth agglomerate, including The Si element that adhesive is brought into；Carbonaceous reducing agent amount is that siliceous element reduction is theoretical value needed for simple substance in rare earth agglomerate 100%-130%wt, carbonaceous reducing agent amount is in terms of the fixed carbon in rare earth agglomerate；
(2) silica, carbonaceous reducing agent and above-mentioned rare earth agglomerate are entered furnace together to smelt；If rare earth is former in rare earth agglomerate in step (1) The rare earths material of surplus is entered furnace smelting less than 100%wt, then by doses together with silica, carbonaceous reducing agent and above-mentioned rare earth agglomerate； Silica input amount deducts surplus corresponding after institute's silicon content in rare earth agglomerate for 100~120%wt of theoretical value, and silica is thrown Enter amount with the SiO in silica2Meter；Carbonaceous reducing agent is corresponding surplus after contained carbon capacity in theoretical value deduction rare earth agglomerate 0.80~0.96 times, carbonaceous reducing agent is in terms of the fixed carbon in carbonaceous reducing agent；Burning of coming out of the stove casting, obtains rare earth ferrosilicon alloy.
2. a kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy according to claim 1, special Sign is that rare earths material used is the enriched substance of rare-earth wet method metallurgy, polishing powder from rare earth waste material, concentrate, oxide ore, rare earth The mixture of one or more of smelted furnace cinder.
3. a kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy according to claim 1, special Sign is that siliceous raw material used in step (1) is silica, SILICA FUME, silicon powder, silicon powder, silicon grain, quartz sand, silicon series ferroalloys smelting The mixture of one or more of furnace slag.
4. a kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy according to claim 1, special Sign is that carbonaceous reducing agent used is coke, powdered carbon, semi-coke, semi-coke, charcoal, bottle coal coke, bituminous coal, petroleum coke, fine coal powder The mixture of middle one or more；Carbonaceous reducing agent requires fixed C>=70%wt, ash<10%wt in step (1)；In step (2) Carbonaceous reducing agent requires fixed C>=80%wt, ash<7%wt.
5. a kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy according to claim 1, special Sign is that adhesive used is one or more of waterglass, SILICA FUME, bentonite, paper pulp, syrup waste liquid, plant amylum Mixture.
6. a kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy according to claim 1, special Sign is that step (1) described substep is compressed to first compacting rare earths material and obtains primary agglomerate, the kernel as rare earth agglomerate；Again Siliceous raw material as middle layer material is covered in the outer surface of primary agglomerate, and carries out compacting and forms second level agglomerate；Further Carbonaceous reducing agent as outer shell material is covered in the outer surface of second level agglomerate by ground, and is carried out compacting and formed with nucleocapsid knot The rare earth agglomerate of structure.
7. a kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy according to claim 1, special Sign is to contain SiO in silica described in step (2)2> 98%wt, Al2O3< 0.4%wt, CaO < 0.2%wt.
8. a kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy according to claim 1, special Sign is to stand 10 minutes or more after coming out of the stove described in step (2) carries out burning casting again；If the alloy molten solution upper layer come out of the stove occurs Suspension slag is then subject to auxiliary device and is excluded, then carries out burning casting again.
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