CN104671657A - Method for preparing rock wool melt through silicon oxidation and coproducing molten alloy steel - Google Patents

Abstract

The invention discloses a method for preparing rock wool melt through silicon oxidation and coproducing molten alloy steel, belonging to the technical fields of utilization of waste crystal silicon slurry, preparation of rock wool fiber melt and smelting of iron and steel. In the method, a silicon material mixed with silicon carbide is dissolved in the molten iron, an oxidizing agent and a substance at least containing calcium oxide are added, silicon is oxidized into silicon dioxide, the silicon dioxide and the added substance at least containing calcium oxide form liquid slag, the liquid slag is used as rock wool melt for preparing rock wool fiber, the oxidizing agent at least comprises an oxide, the iron oxide is reduced, and thus, liquid metal iron is obtained as a byproduct. According to the method, a silicon material in waste silicon as well as silicon element and carbon element in silicon carbide are used for preparing high-acidity rock wool melt for rock wool fiber, a chemical reducing agent effect and chemical calorific effect of the silicon material as well as the silicon and the carbon in the silicon carbide are fully used, energy consumption is reduced, molten metal, alloy steel mother liquor and stainless steel mother liquor with higher additional value are directly obtained from the metal oxide raw material as coproduced byproducts, and the comprehensive benefits are notable.

Description

Silicon oxidation produces the method for rock wool melt coproduction alloy molten steel

Technical field

The invention belongs to the technical field of comprehensive utilization of silicon and silicon carbide in silicon cutting waste slurry, also belong to and adopt metallurgical hot slag to prepare rock wool fibers lagging material technical field, also belong to smelting iron and steel technical field, particularly produce the method for rock wool melt coproduction alloy molten steel.

Background technology

In order to the thin sheet products obtaining solar cell substrate, unicircuit substrate, electronic chip, sophisticated semiconductor chip adopt, need to carry out Linear cut to highly purified silicon single crystal, polycrystalline silicon rod, ingot.The silicon carbide that Linear cut adopts hardness high is abrasive material, join according to a certain percentage in the aqueous suspensions that polyoxyethylene glycol (PEG) is main raw material and form water-based cutting liquid, wherein, polyoxyethylene glycol plays dissemination, and can take away the huge heat of friction produced in cutting process in time.During silicon wafer cutting, machine guide wheel drives copper-plated steel wire to run up, and steel wire drives silicon carbide abrasive constantly to grind silicon rod, thus cuts into silicon chip.In silicon wafer cutting process, a large amount of silica flour and a small amount of scrap metal enter cutting liquid makes the character of cutting liquid change gradually, and when these solid impurity content are accumulated to a certain degree, final cutting liquid can not meet split requirement and become waste mortar.

While silicon rod is cut into silicon chip, the 40-55% of about silicon rod quality becomes silica flour, the steel wire of cutting machine is by the small part iron powder produced that rubs, the less SiC particle of the damaged particle diameter become is there is in part SiC in cutting process, the moisture in air that PEG absorbs, all enter in the middle of cutting mortar, silicon wafer cutting waste mortar main ingredient and content (massfraction): PEG 40% ~ 50%, SiC 23% ~ 33%, silicon (Si) 20% ~ 24%, iron filings (Fe) 2.5% ~ 3.0%.It is generally acknowledged that polyoxyethylene glycol (PEG) wherein, silicon-carbide particle (SiC), silica flour (Si) have higher recovery or the value of comprehensive utilization.

Waste mortar has following features: (1) cutting fluid is water-soluble, is easy to filtering separation through dilution; (2) silicon carbide stable chemical nature, even if acid of at high temperature also getting along well, alkali react; (3) silica flour purity is high, particle diameter is little, specific surface area is large, has good chemical reactivity.Based on this characteristic of waste mortar, the method that patent application in recent years adopts solid-liquid separation and solid to purify to combine mostly realizes the recycling of cutting waste mortar.

The existing method of publication to the process of polysilicon waste mortar and recovery is roughly divided into four classes: (1) solid-liquid separation, solid purification combined techniques; (2) method of chemical treatment; (3) electrical concentration; (4) electrophoresis (current potential) partition method.

It is comparatively easy to be separated PEG, the SiC in waste mortar.The technique that recovery PEG generally adopts is: first adopt filtration or centrifugation to carry out solid-liquid separation to slip, then is undertaken dewatering or distilling obtaining PEG by being separated the liquid obtained.Reclaiming the technique that generally adopts of SiC is: solid solid-liquid separation obtained carries out pickling deironing, acid-soluble except Si or alkali is molten obtains SiC micro mist except after Si.

Such as, Chinese patent 200710117665 (Zhou Shouzeng) discloses and adopts membrane technique and chemical treatment method, obtains SiC powder.Chinese patent 200610058746.3 (Zhang Jieping), Chinese patent 200810232782.6 (Xi Xifeng) have reclaimed polyoxyethylene glycol (PEG) and silicon carbide (SiC) by process, but do not relate to recovery and the utilization of silica flour.

The technical scheme announced in Chinese patent 200610029378.X (golden Berlin), carried out the recovery of silica flour, the rate of recovery of silica flour is lower, is only the 1-2% of slip.

The purity of the silicon that Chinese patent 200710018636 (Yang Jianfeng) reclaims is higher, reach 98%, concrete technology is: first waste slurry is removed suspension agent and binding agent, again the solid obtained is obtained the mixed powder of Si and SiC by gas flotation, then flotation and gravity treatment is carried out with the liquid of density between Si and SiC, be separated Si and SiC, obtain SiC and Si micro mist, as shown in Fig. 1 (a) finally by iron removal by magnetic separation.Because the Si powder purity reclaimed is greater than 98%, again polysilicon can be prepared as starting material.

Chinese patent 200910187695.8 (Xing Pengfei) has related to the recovery of silica flour: first carry out physics sedimentation to waste slurry and obtain SiC enrichment material and Si enrichment material respectively, after silicon enrichment material is carried out pickling deironing, metal silicon ingot is obtained 1500-1600 degree Celsius of lower founding, SiC and Si is separated, then directional freeze is carried out to Si ingot and obtain solar-grade polysilicon.Carry out pickling deironing to SiC enrichment material, pickling alkali cleaning removes Si, drying obtains SiC micro mist, technological process is as shown in Fig. 1 (b).

The technical scheme of above-mentioned patent application, to cutting the recovery of waste mortar from single recovery silicon carbide, to the synthetical recovery of silicon carbide, silicon and polyoxyethylene glycol, and the purity of the rate of recovery, product improves gradually, major part application is based on identical principle, just repetition or combination are carried out to different operations, and the silicon major part obtained is tended to return be applied to photovoltaic crystal silicon again.

In current industrial practice, waste mortar, through centrifugation, solid-liquid separation and a series of refining, purification, finally obtains three class product (1) liquid based on PEG; (2) based on SiC, the heavy mixture containing other impurity such as Si, Fe; (3) based on Si powder, mixture that proportion containing impurity such as SiC is little.The recycling of first two is comparatively ripe, only has the third useless silicon material being mixed with SiC not utilize well.

The main technique of commercial recovery is: most polysilicon waste slurry is after centrifugation, silicon carbide is due to than great, be separated preferably with suspension, after removal of impurities is purified, silicon carbide is better reclaimed, also easily abrasive applications is re-used as, the matrix of suspension is PEG, pressed powder is wherein silica flour and tiny silicon carbide, solid-liquid separation is carried out in suspension press filtration, fluent meterial is based on PEG, cutting link can be returned after good purifying treatment, being separated in the solid matter obtained is the silica flour having mixed silicon carbide and a small amount of iron, and containing certain liquid component, as shown in Fig. 1 (c), the lower right corner based on Si powder, useless silicon material containing SiC is not well utilized.This is because the utilization the most easily of Si powder is exactly return the high-purity crystal silicon material of preparation.But the value of HIGH-PURITY SILICON in fact and do not lie in silicon material itself, and is that the technical difficulty of purifying is large, complex process, cost are high.Such as, the silicon content of industrial silicon reaches 97-99%, and high-purity crystal silicon material is exactly by this small amount of Impurity removal, its cost is higher than the value of silicon material itself 15-28 times, in some cases, can reach 70-233 times by the value promotion of the unit silicon of purification removal of impurities, what so the increase in value of many times relied on is the remarkable lifting of purity, instead of silicon materials itself.So, although may not necessarily containing the boron being difficult to remove in useless Si material, the impurity such as phosphorus, but owing to being mixed with silicon carbide, iron, add the easy surface oxidation of very thin silica flour and form silicon-dioxide, particularly because the ratio of silicon in waste silicon powder and silicon carbide has very wide fluctuation range, in fact contaminated silica flour revert to photovoltaic industry without any practical significance, because purchase the industrial silicon of 99% from the market, Pure Silicon Metal does the words of raw material, material cost shared in high-purity crystal silicon is also very little, and raw-material quality, supply, price is more stable.

The present invention and do not lie in crystal silicon cutting waste slurry be separated, but the Si powder being mixed with SiC obtained is separated for waste slurry, a kind of more rational utilization ways is provided, make full use of the feature of wherein element silicon, for the preparation of the rock wool melt needed for the multi-purpose rock wool fibers such as building heat preservation and other thermal insulation, sound insulation, vibration damping.

Rock wool fibers is as the one of inorganic mineral fiber, there is excellent physical and chemical performance, heat preserving and insulating material as building is its purposes the most widely, not only light specific gravity, good heat-insulation effect, and stable chemical nature, under outdoor adverse weather condition, life-time service undergoes no deterioration, what is more important, compared with organic lagging material, its refractoriness is high, can not burn, also can not discharge toxic gas in situation on fire, be safe, healthy, fire-retardant, fire-resistant, nontoxic external-wall heat-insulation material.In addition it also has other purposes a series of, the such as gobo of motorway, high-speed railway, the vibration damping of subway tunnel, noise reduction, sound-proof material, the sound insulation filler of theater, music hall, family, meeting room, office building, applied fireproofing, and industrial heat preservation etc.In agricultural, rock wool fibers can as the matrix of supporting without earth culture.

The preparation process of rock wool fibers is divided into two links, and first is preparation rock wool melt, and second is fibroblast link.Second link roughly all comparing class seemingly, utilizes centrifugal drying silk or gas-blown to become fiber by possessing the multivariant oxide of certain ingredients with the high-temperature fusion of viscosity exactly, and then subsequent disposal in addition.Emphasis of the present invention provides a kind of method and apparatus obtaining rock wool melt with silica flour, silicon carbide blend.

Industrial in order to obtain rock wool melt, general employing is based on basalt raw material, be equipped with other mineralogical composition, being heated to 1200-1500 degrees Celsius makes it be melted into rock wool melt, main type of heating has two kinds, and a kind of is the cupola furnace technique of chemical heat source adopting coke, hot blast, and another kind is the eaf process adopting electric power heating, no matter any, all need to consume a large amount of energy.By the heating raw materials of normal temperature to suitable temperature of fusion, typical heat-processed, general melt per ton needs to consume about 1000-1600kwh, and the rock wool melt of attaching most importance to energy consumption heating link occupies about 40% of rock wool fibers manufacturing processed total cost.

In order to save energy, the hot slag of people's trial pyrometallurgy industry uses as rock wool melt, but both acidity difference are larger.Rock wool melt wishes higher SiO ₂content, carry out quantitatively characterizing by acidity quotient Mk value, Mk is defined as

$M_k=\frac{\mathrm{wt}\%{\mathrm{SiO}}_2+\mathrm{wt}\%{\mathrm{Al}}_2{O}_3}{\mathrm{wt}\%\mathrm{CaO}+\mathrm{wt}\%\mathrm{MgO}}---\left(1\right)$

Acidity quotient Mk indicates SiO in melt ₂and Al ₂o ₃deng the ratio of the basic oxide such as acidic oxide and CaO, MgO content, Mk value is greater than 1.6 or 1.8 for high-quality inorganic fibre, and be referred to as rock wool fibers, Mk value will reduce an obvious class between 1.2-1.6 quality, be referred to as mineral wool fibre.Lower acidity value makes the water tolerance of mineral wool fibre, weathering resistance all can not meet conventional building materials requirement, and acidity value lower in addition also brings high temperature viscosity, fibre-forming performance, fusibility aspect to be difficult to meet the fine processing requirement of system.

In general, rock wool adopts basalt to be main raw material, and mineral wool then adopts blast-furnace slag, and the performance of the two, application aspect have larger difference.Be used in the fiber on exterior wall, acidity quotient Mk must more than 1.6, the Mk of rock wool is more than 1.8, and the Mk of mineral wool between 0.8 to 1.2, can only only have 1.2-1.6 at most, acidity quotient directly determines its work-ing life, the Mk of mineral wool is very low, 2 to 5 years will efflorescence, for the words of exterior wall, after several years, exterior wall will play drum, and then cracking comes off.And rock wool can with building the same longevity, due to the significant difference of Mk, their ultimate compression strength and pull strength have very big-difference, this is because its fibre array is different, rock wool is interspersed, and presents wavy, this enhances interfibrous adhesive fastness, and mineral wool fibre is parallel distribution, bond between fiber insecure.Thus, rock wool and mineral wool are except identical in fire-protection rating, and be all A level, the performance of other each side all has essential distinction.

The hot slag of general pyrometallurgical process, acidity quotient is all on the low side, is often less than 1 even lower, directly can not manufactures the rock wool fibers of highly acidity, even if manufacture qualified mineral wool product, also need the SiO allocating a large amount of cold conditions into ₂etc. acid mineral, so, energy-conservation effect is also not obvious, constrains rock wool melt and reduces costs.

Chinese patent CN201210230153.6 adopts basalt to produce rock wool melt with addition of other materials exactly.Chinese patent CN91101900.6 proposes the rock wool fibers preparation method of highly acidity.Chinese patent CN01135221.3 proposes to adopt coal gangue to produce mineral fibre, and seeming raw material self can provide part fusing institute heat requirement, but still needs the external world to provide a large amount of heat energy to melt.Chinese patent CN201110362291.5 adopts industrial tailings preparation raw material.Technical scheme disclosed in above-mentioned patent all needs to fire link in the fusing of cupola furnace or tank furnace provides mass energy.

Chinese patent ZL88108024 proposes to adopt hot-melt yellow phosphorous dreg, directly produce mineral wool fibre, but its acidity quotient is less than 1, and gained mineral wool fibre cannot match in excellence or beauty rock wool fibers.Chinese patent application 201310055394.6 adopts blast furnace hot slag to be main body, and preparation mineral wool fibre is not still the rock wool fibers of peracid angle value.

Chinese patent CN200780034126 proposes a kind of mineral wool composition, and acidity quotient is wherein higher, can produce high-quality rock wool fibers, but does not propose the more energy-conservation method producing melt.

Chinese patent CN200480024490.3 proposes a kind of glass fibre can degraded in physiological liquid, and object is to reduce the risk to harm, but and not mentionedly how to realize energy-conservation in fusing link.

U.S. Patent application US20030181306 proposes the chemical composition of mineral wool fibre, is conducive to physiologic degradation, but does not propose different Technology Ways with regard to the heat energy supply of melting materials capable.

US Patent No. 4971615 describes the method producing mineral wool fibre from cinder, drawn by hot melt cinder in coal-fired boiler in power plant, making mineral wool fibre, is the method for relative energy-saving, but its composition and acidity quotient are limited by the kind of coal, be thus difficult to be adjusted to desirable composition and acidity.

US Patent No. 4822388 proposes the technological measure of improvementization slag hearth, improves fuel source, but wherein carbonaceous fuel remains main chemical heat source, needs to supply more extra power.

US Patent No. 4365984 proposes the chemical composition of suitable mineral wool fibre and the processing step of melting, needs to consume larger extra power and makes load meltingly to produce fiber.

In general, the drawback of prior art or deficiency are mainly:

1, after polysilicon cutting waste slurry separation and Extraction, polyoxyethylene glycol (PEG) and silicon carbide (SiC) are recycled preferably in industry member at present, but the thin Si powder being mixed with the impurity such as SiC is not yet utilized effectively;

Even if 2 mix and have the Si powder of SiC to obtain purification, often need the SiC removed wherein, because the rate fluctuations scope of SiC in Si powder is very large, this means that a large amount of SiC is wasted;

3, existing rock wool fibers is when producing rock wool melt, wants the rock wool fibers obtaining high quality, peracid angle value, adopts the SiO such as natural basalt ₂the mineral that content is high, make it fusing by inputting a large amount of heat energy, heat rejection is very large, and cost is very high;

If 4 adopt the hot slag of the high temperature industries such as metallurgy, chemical industry to prepare insulation fibre as melt, because the acidity value of of hot slag itself is too low, high-quality rock wool fibers cannot be prepared.

Summary of the invention

The technical problem to be solved in the present invention is: for drawback and the deficiency of public technology scheme in prior art and forefathers' patent, produced the method for rock wool melt coproduction alloy molten steel, make full use of the silicon raw material in useless silicon by silicon oxidation;

Another object of the present invention is to make full use of the element silicon in the silicon carbide in useless silicon material;

Another object of the present invention is to make full use of the carbon in useless silicon material contained by silicon carbide;

Another object of the present invention is can also under not relying on the external world and providing the prerequisite of the energy, and the high-grade rock wool fibers rock wool melt of obtained peracid angle value, reduces energy consumption;

A further object of the invention is the chemical reducing agent effect making full use of silicon, carbon in silicon, silicon carbide, directly obtains metal, alloy mother liquor goods compared with high added value, as the byproduct of coproduction, increase economic efficiency further from the raw material of metal oxide.

For achieving the above object, the invention provides following technical scheme: silicon oxidation produces the method for rock wool melt coproduction alloy molten steel, it is characterized in that, comprises the steps:

To the silicon material dissolution of silicon carbide be mixed with in molten pig liquid, the quality of described molten pig liquid for described in be mixed with the 3-20 of element silicon quality in the silicon raw material of silicon carbide doubly, forms at least siliceous molten iron and bathes molten bath;

Oxygenant and the material at least containing calcium oxide is added in described at least siliceous molten iron bath molten bath, silicon is oxidized to silicon-dioxide, described silicon-dioxide and the material at least containing calcium oxide added, form the molten slag at least containing silicon-dioxide, calcium oxide, the acidity quotient Mk of described molten slag is 1.6-8.0, described acidity quotient $M_k=\frac{\mathrm{wt}\%{\mathrm{SiO}}_2+\mathrm{wt}\%{\mathrm{Al}}_2{O}_3}{\mathrm{wt}\%\mathrm{CaO}+\mathrm{wt}\%\mathrm{MgO}};$

The described molten slag at least containing silicon-dioxide, calcium oxide is as the rock wool melt producing rock wool fibers, and at least comprise ferriferous oxide in described oxygenant, it is byproduct that ferriferous oxide is reduced the liquid metal iron obtained.

The described silicon raw material being mixed with silicon carbide is polysilicon cutting waste slurry or is extracted product after polyoxyethylene glycol, silicon carbide for polysilicon cuts waste slurry.

The described silicon raw material being mixed with silicon carbide for polysilicon cutting waste slurry be extracted polyoxyethylene glycol, silicon carbide after as the resistates of reductive agent for discharging after Pidgeon process technique vacuum silicon heat refining magnesium, containing magnesium raw material in described Pidgeon process technique vacuum silicon heat refining magnesium process is calcined dolomite, reduction refining reactive magnesium temperature is 1000-1400 DEG C, and pressure is 0.1-200Pa.

The described silicon raw material containing silicon carbide is by being blown into using rare gas element as carrier gas in iron liquid molten bath.

Described oxygenant also comprises oxygen and/or air, and described oxygen and/or air are blown into described molten iron bath molten bath in the mode of gas top blast jet, or bottom blowing, side-blown mode are blown into described molten iron bath molten bath.

Described oxygenant also comprises one or more in Mn oxide, tungsten oxide, molybdenum oxide, barium oxide, after one or more in described Mn oxide, tungsten oxide, molybdenum oxide, barium oxide are reduced, one or more obtaining in manganese, tungsten, molybdenum, v element enter described molten iron bath molten bath, obtain containing the alloy molten steel of one or more in manganese, tungsten, molybdenum, v element.

The described Material Source containing calcium oxide with the addition of the reducing slag of calcium oxide when chromated oxide and Si reduction react and obtain chromium metal, and adds in the mode of hot charging; Electric power is adopted to heat furnace charge, chromated oxide be reduced the chromium metal obtained be dissolved in described molten iron bath molten bath beyond iron liquid in, formed containing the mother liquor of stainless steel of chromium as byproduct, the described chromium stainless steel mother liquor as byproduct be 10-30% containing chromium mass percent.

In described chromated oxide and iron liquid during pasc reaction, bottom blown gas is adopted to stir iron liquid.

The reducing slag containing Dicalcium Phosphate (Feed Grade) of the described material containing calcium oxide for discharging after Pidgeon process technique vacuum silicon heat refining magnesium, and add in the mode of hot charging; Containing magnesium raw material in described Pidgeon process technique vacuum silicon heat refining magnesium process is calcined dolomite, and reduction refining reactive magnesium temperature is 1000-1400 DEG C, and pressure is 0.1-200Pa.

Ferriferous oxide containing 5-15% in described rock wool melt.

In described rock wool melt, the mass percent of silicon-dioxide is 35-70%, and calcium oxide mass percent is 15-35%, and quality of alumina percentage ratio is 5-20%.

In described ferriferous oxide and iron liquid during pasc reaction, bottom blown gas is adopted to stir iron liquid.

The present invention utilizes the useless silicon material containing Si, SiC to make raw material, adopts the technique means such as molten iron bath, oxidation style to produce highly acidity rock wool melt, the aluminium alloy of by-product iron content, chromium etc., achieves following Multiple techniques effect.

1, silicon is the strong reductant of metal, is used for the metal oxide such as reduced iron, chromium, and coproduction obtains iron liquid, containing ferrochrome liquid, and the high added value metal product such as chromium stainless steel mother liquor, as byproduct.

2, silicon is also chemical heat source, can not only supply the intensification of self, can also melt certain external auxiliary agent, the material mainly containing CaO, is used for adjusting slag acidity, obtains the rock wool melt of good properties, and then produce rock wool fibers and goods thereof.

3, the rock wool melt of very highly acidity coefficient can be obtained, the rock wool fibers of obtained highly acidity.Because the oxidation that have employed Si is produced, the basic oxide content such as CaO, MgO wherein can be fallen too low, in rock wool fibers, require SiO ₂content is very high, and such silicon is after completing the heat-generating agent as reductive agent and chemical heat source, and resultant product act as the main component of rock wool melt.

4, silicon carbide can be dissolved in iron liquid, obtains ferrosilicon liquid and carbon, and in silicon carbide, silicon and carbon are also played as the double effects of reductive agent, thermal source.

5, molten iron bath molten bath is adopted to absorb silicon, silicon carbide, obtain siliceous and carbon containing iron liquid, there is multiple advantage, can either as the thermophore of heat energy, snubber, reaction medium, heat-transfer medium, homogeneous phase, produce the dynamic conditions of good high-temperature fusant, newly-increased metallic iron, chromium metal etc. can also be absorbed and form aluminium alloy, as byproduct, further improve effects.

Accompanying drawing explanation

Fig. 1 (a), (b), (c) existing three kinds of polysilicon waste slurry separation-extraction technology technology

Fig. 2 silicon oxidation produces rock wool melt coproduction iron liquid artwork

Fig. 3 silicon oxidation produces rock wool melt coproduction iron liquid schematic diagram

Fig. 4 silicon oxidation produces rock wool melt coproduction mother liquor of stainless steel artwork

Fig. 5 (a), (b) silicon oxidation produce rock wool melt coproduction mother liquor of stainless steel schematic diagram

Fig. 6 acidity quotient is the rock wool melt viscosity-thetagram of 2.4

Fig. 7 silicon produces rock wool melt coproduction iron liquid artwork after production of magnesium by pidgeonprocess

Fig. 8 (a), (b) silicon produce rock wool melt coproduction iron liquid schematic diagram after production of magnesium by pidgeonprocess

Fig. 9 acidity quotient is the rock wool melt viscosity-thetagram of 2.9

In figure, 101 iron bath smelting furnace, 102 useless silicon feed pots, 103 oxygen rifles, 104 iron ore feed pots, 105 high-temperature flue gas outlets, 106 rock wool melts, 107 molten iron baths, 108, iron liquid exports, 109 hot metal ladle, 110 for nitrogen device, 111 rock wool melt outlet, 112 for argon device, 113 Argon pipes, 114 newly-generated iron liquid, 201 holding furnaces, 203 4 roller centrifugal drying silks, 204 fibroblast collection are cotton, 205 rock wool fibers solidifications, 206 asbestos product cuttings, 207 asbestos product aftertreatments, 301 refining chromium stoves, 302 refining chromium give up silicon feed pot, 303 heating electrodes, 304 chrome ore feed pots, 305 iron liquid entrances, 306 refining chromium reducing slags, 307 chromium molten iron baths, 308 ferrochrome liquid outlets, 309 ferrochrome liquid bags, 310 refining chromium stoves are for nitrogen device, 311 slag notches, 312 refining chromium stoves are for argon device, 313 refining chromium stove Argon pipes, 314 containing ferrochrome liquid, 316 refining chromium slag pot, 317 refining chromium reducing slags, 401 magnesium smelting reduction pots

Embodiment

Below in conjunction with accompanying drawing 1-Fig. 9, the specific embodiment of the present invention is described in detail, but the present invention is not limited to specific embodiment.

Embodiment 1

In the present embodiment, utilize the useless silicon material being mixed with SiC, while obtaining the rock wool melt of highly acidity, coproduction iron liquid.As shown in Figure 2, as shown in Figure 3, concrete technology step is as follows for technical scheme and principle in technical process:

Molten silicon bathed by A, iron

Get the useless silicon material being mixed with SiC of 2000kg drying, be wherein 58% containing Si, be 40% containing SiC, all the other are iron, are placed in useless silicon feed pot 102.

The iron liquid 20 tons of 1600 DEG C that have melted is filled in iron bath smelting furnace 101.Open for nitrogen device 110, the silicon material nitrogen that will give up, as carrier gas, is blown in iron bath smelting furnace 101, the combination reaction of silica flour and iron occurs, and release of heat, reaction is easy to carry out, and speed, as shown in formula (2), (3).

Fe+Si＝FeSi (2)

ΔG ^Θ＝-80332-4.18*T(J) (3)

When the silicon content of iron bath is less than 33wt%, in useless silicon material, SiC also reacts with iron liquid, and iron destroys SiC, generates FeSi, and this reaction is easy to occur, as shown in formula (4), (5).

SiC+Fe＝FeSi+C (4)

ΔG ^Θ＝-26777-11.21*T(J) (5)

After tens seconds, just define the ferrosilicon liquid of low silicon.The siliceous mass percent of ferrosilicon liquid in this example only has 7.8%, carbon containing 1.2%.Silicon and silicon carbide all can be dissolved in iron liquid, and form FeSi, due in FeSi siliceous 33%, so the quality of Fe liquid must be greater than more than 2 times of silicon, owing to also having the carbon dissolution of SiC release in iron liquid, so, iron liquid is greater than siliceous amount more than 3 times, can obtain the effect of good dissolves silicon.

B, oxidation slagging, make rock wool melt

Silicon is excellent metallic reducing agent, and most metal oxide by Si reduction time, can also release of heat, as shown in table 1, when silicon is oxidized, have larger heat energy release.

The exothermic effect of the every 1000kg silicon oxidation process of table 1

Produce rock wool melt to need multivariant oxide is heated up and melts, the liquid mean heat capacity of the slag of the composition such as multivariant oxide is 1.248kJ/ (kgK), latent heat of fusion average out to 209kJ/kg, so average oxide compound per ton is from room temperature to 1600 DEG C, the heat absorbed is needed to be roughly 2200MJ/t, amount to electric power and be about 600-620kwh, thermal equilibrium can be estimated roughly with this.According to dissimilar fusing reactor, the heat radiation ratio of its water coolant, furnace wall, flue gas etc. is not approximately 5-30% not etc.

Utilize the intensification of silicon oxidation heat release and rock wool melt feed in table 1 to melt heat absorption and carry out EQUILIBRIUM CALCULATION FOR PROCESS, rock wool melt can obtained without the need to the external world under heat condition.

In the present embodiment, the fine iron breeze of 3.5 tons of iron content 60%, iron scale is good as oxidant preparing, get out 3.8 tons again and mainly contain calcium oxide, aluminum oxide, magnesian slag as additive, oxygenant and additive are mixed, be placed in iron ore feed pot 104, join in iron bath smelting furnace 101 in batches, utilize oxygen rifle 103 injecting oxygen or oxygen-rich air to enter stove simultaneously, oxidation process, and realize fully stirring, the C dissolved in iron liquid is oxidized, generates CO gas, from high-temperature flue gas outlet 105 effusion stove.Meanwhile, bottom blowing stirring is carried out by Argon pipe 113 to molten bath in stove for argon device 112.The chemical equation (6) of silicon oxidation, (7), (8) are as follows:

3[Si]+2(Fe ₂O ₃)＝3(SiO ₂)+4[Fe] (6)

[Si]+2(FeO)＝(SiO ₂)+2[Fe] (7)

[Si]+O ₂＝(SiO ₂) (8)

In addition, also can there is oxidizing reaction in a small amount of carbon of dissolving, and release of heat, as shown in chemical equation (9), (10), (11).

3[C]+(Fe ₂O ₃)＝3CO+2[Fe] (9)

[C]+(FeO)＝CO+[Fe] (10)

2[C]+O ₂＝2CO (11)

All oxygenants, additive add complete, continue argon bottom-blowing stir and weaken the flow of Argon pipe 113, leave standstill, make hot slag and the layering of iron liquid, upper strata is rock wool melt 106, and lower floor is molten iron bath 107, rock wool melt 106 flows out from rock wool melt outlet 111, flow into holding furnace 201, through four roller centrifugal drying silks 203, fibroblast collection cotton 204, rock wool fibers solidification 205, asbestos product cutting 206, asbestos product aftertreatment 207, become qualified rock wool fibers finished product.

Amount to obtained rock wool melt 7.6 tons, record the main component of the rock wool melt of this composition: SiO ₂be 47%, CaO be 18%, Al ₂o ₃be 13%, MgO be 7%, FeO be 12%, acidity quotient is 2.4, is the high-quality rock wool melt that acidity is higher.

C, coproduction molten steel

After above-mentioned steps, iron liquid weight is 21.8 tons, increases weight 1.8 tons, is newly-generated iron liquid 114, is flowed out by 1.8 tons of iron liquid, enter into hot metal ladle 109 from iron liquid outlet 108, for steel-making or direct ingot casting after outflow, is the byproduct of rock wool melt producing process.Remain 20 tons of iron liquid again as the new a collection of waste silicon powder of dissolution with solvents, repeat above-mentioned A, B process.

Embodiment 2

In the present embodiment, utilize the useless silicon material being mixed with SiC, while obtaining the rock wool melt of highly acidity, coproduction chromium stainless steel mother liquor.As shown in Figure 4, technical scheme and principle are as shown in (a), (b) of Fig. 5, and concrete technology step is as follows in technical process:

Molten silicon bathed by A, iron

Identical with embodiment one: in 20 tons of iron liquid, to dissolve the useless silicon material that 2000kg is mixed with SiC, obtain the low silicon ferrosilicon liquid of silicone content 7.8%, carbon content 1.2%.

B, oxidation slagging, be blended into refining chromium reducing slag, make rock wool melt

The fine iron breeze of 6.5 tons of iron content 60%, iron scale is good as oxidant preparing, get hot refining chromium reducing slag 317 in 3.6 tons of step C in addition ready as additive, all mark with #1 slag in figure at (a), (b) two of Fig. 5, and be equipped with the bauxite of 1 ton, jointly join in ferrosilicon liquid by iron ore feed pot 104, argon bottom-blowing fully stirs, then argon flow amount is reduced, make hot slag and the layering of iron liquid, upper strata rock wool melt flows out produces rock wool fibers, and lower floor's iron liquid includes newly-generated iron liquid.

Amount to obtained rock wool melt 8.3 tons, the main component recording this rock wool melt is as follows:

The chemical composition of table 2 rock wool melt

Main component	SiO 2	CaO	Al 2O 3	MgO	FexOy
						Mass percent %	45	20	17	6	10

The acidity quotient Mk value of rock wool melt is 2.4, meets the component requirements of preparation highly acidity rock wool fibers.As shown in Figure 6, during temperature variation, the change of viscosity comparatively slowly evenly, is the viscosity of good rock wool melt to the temperature-viscosity curve of this rock wool melt.

Iron liquid quality is for being 23 tons, and increase by 3 tons, 3 tons of iron liquid are byproduct, in the present embodiment, utilizes iron liquid to continue to smelt chromium stainless steel mother liquor.All increase iron liquid newly with #3 at (a), (b) two of Fig. 5 in figure and represent that the iron liquid that Si reduction of iron ore obtains, #4 increase iron liquid newly and represents the iron liquid that C element reduction of iron ore obtains.

C, coproduction molten stainless steel

By iron liquid 3.2 tons outflow, be injected in refining chromium stove 301 by iron liquid entrance 305, the nitrogen utilizing refining chromium stove to provide for nitrogen device 310 is carrier gas, stove is entered from the give up 550kg silicon material that gives up of jetting silicon feed pot 302 of refining chromium, wherein element silicon total amount is 473kg, after being dissolved into iron liquid, obtain the ferrosilicon liquid 3.7 tons of siliceous 12.6%.

By 3.3 tons of chrome ores and 2.2 tons of lime mixing, joined in refining chromium stove 301 by chrome ore feed pot 304.Ratio containing chromic oxide 40%, Cr and Fe element in chrome ore is 2.5, and also have certain aluminum oxide, magnesium oxide in addition, calcium oxide, silicon oxide are less.In heating electrode 303, electric-arc heating is carried out in energising, and provides argon gas by refining chromium stove for argon device 312, carries out argon bottom-blowing stirring, following chemical reaction occurs from refining chromium stove Argon pipe 313

3[Si]+2Cr ₂O ₃+6CaO＝3{2CaO·SiO ₂}+4[Cr] (8)

And the reduction reaction of iron ore:

3[Si]+2(Fe ₂O ₃)＝3(SiO ₂)+4[Fe] (6)

[Si]+2(FeO)＝(SiO ₂)+2[Fe] (7)

Produce the alkaline reduction slag 3.6 tons based on calcium oxide, basicity 1.8, namely refines chromium reducing slag 317, all marks with #1 slag in figure at (a), (b) two of Fig. 5, be transported to iron ore feed pot 104, hot charging to B link as the additive producing rock wool melt.Produce the mother liquor of stainless steel 4.7 tons containing chromium 19% simultaneously, the #3 that wherein original ferro element derives from step B increases iron liquid newly, #4 increases iron liquid newly, and the newly-increased chromium of this step C is that #7 increases chromium metal newly, is obtained by Si reducing chrome ore, #6 is also had to increase iron liquid newly, also being that the preferential reduction of iron ore of Si obtains, also having #5 to increase iron liquid newly, is that the carbon reduction of iron ore dissolved obtains, mother liquor of stainless steel flows out from ferrochrome liquid outlet 308, entering into ferrochrome liquid bag 309, become containing ferrochrome liquid 314, is the byproduct of coproduction.

Embodiment 3

In the present embodiment, utilize the useless silicon material being mixed with SiC, be first applied to production of magnesium by pidgeonprocess as reductive agent, be subsequently dissolved in iron liquid, while oxidation obtains the rock wool melt of highly acidity, coproduction chromium stainless steel mother liquor.As shown in Figure 7, technical scheme and principle are as shown in (a), (b) of Fig. 8, and concrete technology step is as follows in technical process:

A, production of magnesium by pidgeonprocess

By levigate to 300 orders for the rhombspar after calcining, fully mix with useless silicon material.The ratio of useless silicon material and the rhombspar after calcining, according to the proportions of 20:80, adds a small amount of Fluorspar Powder in addition as additive.Ball processed after abundant mixing, sends into after ball processed in the magnesium smelting reduction pot 401 of Pidgeon process vacuum silicon reduction, and carry out vacuum refining reactive magnesium, temperature 1200 DEG C, pressure 10Pa, following chemical reaction occurs:

2{CaO·MgO}+Si＝2CaO·SiO ₂+2Mg(g) (9)

Because silicon carbide does not participate in the reaction of refining magnesium, pretend Si and the SiC mixture that the quantity added for reductive agent is x, the silicon that quantity is y is consumed through refining reactive magnesium, in residuum except the oxide compounds such as Dicalcium Phosphate (Feed Grade), quantity is also had to be the Si of (x-y) and the SiC added, therefore the xSi+SiC allocated into before refining magnesium, residue (x-y) Si+SiC after refining magnesium, the magnesium-smelting reduction slags such as Dicalcium Phosphate (Feed Grade) are labeled as #2 slag at (a), (b) two of Fig. 8 in figure.

Every canned material 240kg, through the refining magnesium process of 12 hours, obtains 40kg metal raw magnesium, output 200kg refines magnesium resistates simultaneously, wherein reducing slag 175.2kg, remaining silicon and silicon carbide 24.8kg altogether, wherein excessive unreacted silica flour 4.6kg, has neither part nor lot in the silicon carbide 19.2kg of reaction.

B, iron bathe molten silicon, byproduct iron liquid

The 10 tank refining magnesium resistatess of 1150-1200 DEG C are amounted to 2000kg enter iron bath smelting furnace 101 from iron ore feed pot 104 hot charging, mix with 20 tons of iron liquid.Wherein 248kg silicon and silicon carbide dissolve and enter iron liquid, and magnesium-smelting reduction slag is based on Dicalcium Phosphate (Feed Grade), i.e. #2 slag, forms slag phase 1752kg.Abundant stirring makes after Si, C fully dissolve, to continue to add useless silicon material 750kg, add the ferriferous oxide of 3.8 tons of iron content 60% as oxygenant simultaneously, finally obtain rock wool melt 3.5 tons, acidity quotient 2.3, byproduct iron liquid 2.1 tons.

Embodiment 4

In the present embodiment, using the fine iron breeze of 6.5 tons of iron content 60% as oxygenant, 2 tons mainly contain calcium oxide, aluminum oxide, magnesian slag as additive.

Amount to obtained rock wool melt 5.8 tons, record the main component of the rock wool melt of this composition: SiO ₂be 65%, CaO be 20%, Al ₂o ₃be 7%, MgO be 5%, FeO be 2%, acidity quotient is 2.9, is the high-quality rock wool melt that acidity is higher.The temperature-viscosity curve of this rock wool melt as shown in Figure 9, has higher viscosity number, but along with temperature rising, viscous consistency declines, and is conducive to manufacturing excellent rock wool fibers.

Other NM techniques are identical with embodiment 1.

Embodiment 5

In the present embodiment, using the fine iron breeze of 6.5 tons of iron content 60% as oxygenant, 800kg mainly contains calcium oxide, aluminum oxide, magnesian slag as additive.

Amount to obtained rock wool melt 4.3 tons, record the main component of the rock wool melt of this composition: SiO ₂be 80%, CaO be 12%, Al ₂o ₃be 3%, MgO be 2%, acidity quotient is 5.5, is the rock wool melt that acidity is higher.

Other NM techniques are identical with embodiment 1.

Embodiment 6

In the present embodiment, using the fine iron breeze of 6.5 tons of iron content 60% as oxygenant, 400kg mainly contains calcium oxide, aluminum oxide, magnesian slag as additive.

Amount to obtained rock wool melt 3.9 tons, record the main component of the rock wool melt of this composition: SiO ₂be 85%, CaO be 10%, Al ₂o ₃be 3%, MgO be 1%, acidity quotient is 8.0, is the rock wool melt that acidity is very high.

Other NM techniques are identical with embodiment 1.

Embodiment 7

In the present embodiment, using the fine iron breeze of 2 tons of iron content 60% as oxygenant, 5 tons mainly contain calcium oxide, aluminum oxide, magnesian slag as additive, are blown into oxygen make silicon oxidation additionally by oxygen rifle 103.

Amount to obtained rock wool melt 8.5 tons, record the main component of the rock wool melt of this composition: SiO ₂be 41%, CaO be 32%, Al ₂o ₃be 17%, MgO be 9%, acidity quotient is 1.6, is the rock wool melt that acidity is qualified.

Byproduct iron liquid 1.1 tons.

Other NM techniques are identical with embodiment 1.

Claims (12)

1. silicon oxidation produces the method for rock wool melt coproduction alloy molten steel, it is characterized in that, comprises the steps:

To the silicon material dissolution of silicon carbide be mixed with in molten pig liquid, the quality of described molten pig liquid for described in be mixed with the 3-20 of element silicon quality in the silicon raw material of silicon carbide doubly, forms at least siliceous molten iron and bathes molten bath;

Oxygenant and the material at least containing calcium oxide is added in described at least siliceous molten iron bath molten bath, silicon is oxidized to silicon-dioxide, described silicon-dioxide and the material at least containing calcium oxide added, form the molten slag at least containing silicon-dioxide, calcium oxide, the acidity quotient M of described molten slag _kfor 1.6-8.0, described acidity quotient $M_k=\frac{\mathrm{wt}\%\mathrm{Si}{O}_2+\mathrm{wt}\%{\mathrm{Al}}_2{O}_3}{\mathrm{wt}\%\mathrm{CaO}+\mathrm{wt}\%\mathrm{MgO}};$

The described molten slag at least containing silicon-dioxide, calcium oxide is as the rock wool melt producing rock wool fibers, and at least comprise ferriferous oxide in described oxygenant, it is byproduct that ferriferous oxide is reduced the liquid metal iron obtained.

2. silicon oxidation as claimed in claim 1 produces the method for rock wool melt coproduction alloy molten steel, it is characterized in that, described in be mixed with silicon carbide silicon raw material be polysilicon cutting waste slurry or be extracted product after polyoxyethylene glycol, silicon carbide for polysilicon cuts waste slurry.

3. silicon oxidation as claimed in claim 1 produces the method for rock wool melt coproduction alloy molten steel, it is characterized in that, the described silicon raw material being mixed with silicon carbide for polysilicon cutting waste slurry be extracted polyoxyethylene glycol, silicon carbide after as the resistates of reductive agent for discharging after Pidgeon process technique vacuum silicon heat refining magnesium, containing magnesium raw material in described Pidgeon process technique vacuum silicon heat refining magnesium process is calcined dolomite, reduction refining reactive magnesium temperature is 1000-1400 DEG C, and pressure is 0.1-200Pa.

4. as claim 1,2 or 3 arbitrary as described in silicon oxidation produce the method for rock wool melt coproduction alloy molten steel, it is characterized in that, the described silicon raw material containing silicon carbide is blown into using rare gas element as carrier gas in iron liquid molten bath.

5. silicon oxidation as claimed in claim 1 produces the method for rock wool melt coproduction alloy molten steel, it is characterized in that, described oxygenant also comprises oxygen and/or air, described oxygen and/or air are blown into described molten iron bath molten bath in the mode of gas top blast jet, or bottom blowing, side-blown mode are blown into described molten iron bath molten bath.

6. silicon oxidation as claimed in claim 1 produces the method for rock wool melt coproduction alloy molten steel, it is characterized in that, described oxygenant also comprises one or more in Mn oxide, tungsten oxide, molybdenum oxide, barium oxide, after one or more in described Mn oxide, tungsten oxide, molybdenum oxide, barium oxide are reduced, one or more obtaining in manganese, tungsten, molybdenum, v element enter described molten iron bath molten bath, obtain containing the alloy molten steel of one or more in manganese, tungsten, molybdenum, v element.

7. silicon oxidation as claimed in claim 1 produces the method for rock wool melt coproduction alloy molten steel, it is characterized in that, the described Material Source containing calcium oxide with the addition of the reducing slag of calcium oxide when chromated oxide and Si reduction react and obtain chromium metal, and adds in the mode of hot charging; Electric power is adopted to heat furnace charge, chromated oxide be reduced the chromium metal obtained be dissolved in described molten iron bath molten bath beyond iron liquid in, formed containing the mother liquor of stainless steel of chromium as byproduct, the described chromium stainless steel mother liquor as byproduct be 10-30% containing chromium mass percent.

8. silicon oxidation as claimed in claim 7 produces the method for rock wool melt coproduction alloy molten steel, it is characterized in that, described chromated oxide is with in iron liquid during pasc reaction, and employing bottom blown gas stirs iron liquid.

9. silicon oxidation as claimed in claim 1 produces the method for rock wool melt coproduction alloy molten steel, it is characterized in that, the reducing slag containing Dicalcium Phosphate (Feed Grade) of the described material containing calcium oxide for discharging after Pidgeon process technique vacuum silicon heat refining magnesium, and add in the mode of hot charging; Containing magnesium raw material in described Pidgeon process technique vacuum silicon heat refining magnesium process is calcined dolomite, and reduction refining reactive magnesium temperature is 1000-1400 DEG C, and pressure is 0.1-200Pa.

10. silicon oxidation as claimed in claim 1 produces the method for rock wool melt coproduction alloy molten steel, it is characterized in that, the ferriferous oxide containing 5-15% in described rock wool melt.

11. as arbitrary in claim 1 or 10 as described in silicon oxidation produce the method for rock wool melt coproduction alloy molten steel, it is characterized in that, in described rock wool melt, the mass percent of silicon-dioxide is 35-70%, and calcium oxide mass percent is 15-35%, and quality of alumina percentage ratio is 5-20%.

12. as claim 1,2,3,5,6,7,8,9 or 10 arbitrary as described in silicon oxidation produce the method for rock wool melt coproduction alloy molten steel, it is characterized in that, in described ferriferous oxide and iron liquid during pasc reaction, adopt bottom blown gas to stir iron liquid.