CN104726738A - Crystalline silicon waste treatment method - Google Patents
Crystalline silicon waste treatment method Download PDFInfo
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- CN104726738A CN104726738A CN201510164538.0A CN201510164538A CN104726738A CN 104726738 A CN104726738 A CN 104726738A CN 201510164538 A CN201510164538 A CN 201510164538A CN 104726738 A CN104726738 A CN 104726738A
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- 239000002699 waste material Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 56
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 126
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 62
- 229910052742 iron Inorganic materials 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 29
- 238000003723 Smelting Methods 0.000 claims abstract description 27
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 14
- 239000010959 steel Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 71
- 235000013312 flour Nutrition 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000005261 decarburization Methods 0.000 claims description 15
- 238000005520 cutting process Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910052754 neon Inorganic materials 0.000 claims description 5
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052743 krypton Inorganic materials 0.000 claims description 4
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 29
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 6
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002829 reductive effect Effects 0.000 abstract description 5
- 239000000571 coke Substances 0.000 abstract description 3
- 239000011863 silicon-based powder Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910000640 Fe alloy Inorganic materials 0.000 abstract 2
- 238000007664 blowing Methods 0.000 abstract 2
- 229910052710 silicon Inorganic materials 0.000 description 19
- 239000010703 silicon Substances 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000004321 preservation Methods 0.000 description 9
- 239000005864 Sulphur Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 229910018540 Si C Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910017112 Fe—C Inorganic materials 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- 229910004072 SiFe Inorganic materials 0.000 description 1
- 229910000639 Spring steel Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009865 steel metallurgy Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The invention discloses a crystalline silicon waste treatment method and belongs to the field of crystalline silicon waste treatment. The method includes the steps of A, placing waste steel into a smelting furnace, heating to melt the waste steel into molten iron, and heating the molten iron to reach the temperature above 1570 DEG C; B, continuously blowing waste silicon powder into the molten iron to form molten liquid, and controlling the temperature of the molten liquid to be above 1480 DEG C; C, continuously blowing waste silicon powder, and controlling and keeping the temperature of the molten liquid to be above 1330 DEG C until the silicon-iron alloy liquid reaches the liquid level of a required silicon-iron alloy label product; using protecting gases for protection during the whole working process. The method has the advantages that the carbon in silicon carbide is used to perform silica reduction, energy consumption is reduced, coke adding is not needed, influence of phosphorus and sulfur is reduced, and silicon iron products are low in phosphorus and sulfur and high in value.
Description
Technical field
The invention belongs to crystalline silicon waste disposal field, specifically, relate to a kind of crystalline silicon method for treatment of waste material, more particularly, relate to a kind of intermediate frequency furnace of special shape and utilize the crystalline silicon waste material produced in solar panel production process to carry out the method for smelting duriron.
Background technology
At present, along with the development of clean energy, heliotechnics obtains develop rapidly.In the process of producing solar panel, used a large amount of crystalline silicons, the silicon chip of a diameter 75mm, accessible site several ten thousand, to hundreds of thousands of even millions of elements, defines microtronics, thus has occurred minicomputer, MPU etc.Due to the development of current information engineering, silicon is mainly used in microelectronics.For adapting to the development of large-scale integrated circuit, silicon single crystal forward major diameter, high purity, high uniformity, zero defect future development.A large amount of cutting silica flour waste materials of 6.5 μm to 38 μm is produced in silicon chip of solar cell production process; it is micro-useless that this silica flour belongs to more unmanageable solid, and disposal and utilization silica flour waste material can make silicon resource in the object realizing environment protection that is utilized effectively simultaneously.The silica flour waste material produced in silicon chip of solar cell manufacturing processed belongs to the material without sulphur, phosphorus composition, adopt silica flour waste material to produce ferrosilicon and can produce super low sulfur, phosphorus or the ferro-silicon without sulphur, phosphorus, can be the ferro-silicon raw material that field of steel metallurgy provides high-quality, the quality of steel products can be increased substantially.
Current China has become manufacture of solar cells big country, and a large amount of silica flour waste materials how produced in disposal and utilization manufacture of solar cells process, have become extremely important.Existing process silica flour waste material has following several method:
1, crystalline silicon cutting waste material prepares silicon carbide
China Patent No. 201110152492.2, publication date: on December 14th, 2011, patent discloses a kind of method of silicon crystal waste material nitrogenizing reaction sintered silicon carbon, and its method is carried out as follows:
The superfine silicon carbide micro powder produced by crystalline silicon cutting waste material with when producing silicon carbide cutting powder, after accounting for raw material total amount 5-25wt% batching mixing moulding according to free silica, in raw material, add binding agent make green compact, in nitriding furnace, pass into the high pure nitrogen of more than purity 99wt% and nitriding treatment is carried out to green compact heating, obtaining the goods of reactive sintering of silicon nitride silicon carbide.
But this invention directly cannot process crystalline silicon waste material, need to carry out secondary processing, complex procedures.Finished product is sintering silicon carbide products, does not give full play to the feature of crystalline silicon waste material low-sulfur, phosphorus.
2, the method for SiC particles reinforced silicon aluminum alloy matrix material is obtained in crystalline silicon cutting waste material
Chinese Patent Application No.: 201310390694.X, publication date: on March 26th, 2014, disclose a kind of method obtaining SiC particles reinforced silicon aluminum alloy matrix material in crystalline silicon cutting waste material, carry out as follows: first pickling impurity removal is carried out to crystal-cut waste material, ferric oxide in removing cutting waste material, metallic impurity and a small amount of silicon-dioxide etc., through washing, filter, the steps such as oven dry obtain the silicon carbide of size range at 0.5 μm-10 μm and the admixed finepowder of silicon, by the ratio of silicon carbide micro-powder in matrix material total mass mark 4.5-32.5%, free silica presses matrix material total mass per-cent 0.2%-9.8% and aluminum or aluminum alloy proportioning, after adopting high temperature strong stirring dispersed and silica flour dissolving to silicon carbide, matrix material is obtained through rapid solidification process.
But the silicon carbide that this invention uses, silica flour etc. are the waste materials in industrial production, really be make use of waste material, but its product obtained is SiC particles reinforced Al alloy composite, the effect of SiC particles reinforced Al alloy composite is not provided in literary composition, although provide an outlet to crystalline silicon cutting waste material, do not give play to the value at best that the low-sulfur of crystalline silicon cutting waste material is low-phosphorous.
3, mine heat furnace smelting ferro-silicon is adopted
Silica flour waste material adopts mine heat furnace smelting ferro-silicon to be in silica flour, allocate the raw materials such as coke powder, bath of glass and iron scale into make ball material and join smelting duriron in mineral hot furnace, and this smelting process exists following defect:
1), silica flour pellet forming process section adds production cost, directly do not utilize the characteristic of silicon powder particle;
2), the coke powder allocated into brought the material such as sulphur, phosphorus into, adds the sulphur in silicon iron product, phosphorus content, reduces the quality of silicon iron product;
3), in silica flour waste material, major ingredient is elemental silicon and silicon carbide.In mine heat furnace smelting process, mainly fusing and iron are combined into ferro-silicon to silicon, there is not reduction thermo-negative reaction, adopt mineral hot furnace method smelting ferrosilicon that mineral hot furnace throat temperature can be caused high, heats a large amount of in mineral hot furnace is wasted, and effectively can not reduce production cost.
In sum, lacking now one can solve waste problems, also can play the rational method of the process crystalline silicon cutting waste material of himself maximum feature.
Summary of the invention
1. the problem that will solve
Crystalline silicon waste problems can be solved for existing shortage one, also the problem of the rational method of the process crystalline silicon cutting waste material of himself maximum feature can be played, the invention provides a kind of crystalline silicon method for treatment of waste material, it not only solves the process problem of crystalline silicon waste material, and most crucial is the value farthest having played crystalline silicon waste material.
2. technical scheme
In order to solve the problem, the technical solution adopted in the present invention is as follows:
A kind of crystalline silicon method for treatment of waste material, ferrosilicon prepared by molten iron crystalline silicon cutting waste material being put into fusing when there being shielding gas to protect.
A kind of crystalline silicon method for treatment of waste material, the steps include:
(A) steel scrap is put into smelting furnace, scrap melting is become molten iron by body of heater heating, and is continued by molten iron to be heated to more than 1570 DEG C;
(B) blow in molten iron by silica flour waste material continuous spraying, form liquation, the temperature adding silica flour waste material liquation controls more than 1480 DEG C;
(C) continuous winding-up silica flour waste material, control and the temperature maintaining liquation more than 1330 DEG C, until ferro-silicon liquid reaches the liquid level of required ferro-silicon label product; Shielding gas protection is adopted in whole working process.
Preferably, also comprise step (D): the ferro-silicon liquid in stove is sent to vacuum decarburization device and carries out decarburization, carry out composition and finally adjust, obtain qualified ferro-silicon liquid.The adjustment of this composition is the ratio needing to adjust ferrosilicon according to demand.
Preferably, in described step (A), the add-on of steel scrap is determined with the purity of ferrosilicon to be prepared according to becoming to be grouped in silica flour waste material.
Preferably, described shielding gas is the shielding gas beyond nitrogen.Shielding gas mainly prevents composition to be oxidized; why nitrogen is foreclosed; when mainly state modulator is bad; certain silicon nitride may be produced in reaction; find through our great many of experiments; in addition to nitrogen, as long as the shielding gas that discord material reacts can reach this effect.
Preferably, described shielding gas is helium/neon/argon gas/Krypton/xenon.
The present invention mainly considers that ferrosilicon is widely used in Metal smelting, is one of reductor important in steelmaking process, and being one of reductive agent important in light metal smelting industry, is the indispensable raw material of metallurgical industry.Meanwhile, ferrosilicon also can be used as alloying element addition agent, and be widely used among structural low alloy steel, spring steel, bearing steel, high temperature steel and electrical steel, ferrosilicon, in J. sigillate and chemical industry, is commonly used for reductive agent.Because it belongs to high energy consumption product, so the production overwhelming majority of ferrosilicon carries out in developing country and low developed area in the whole world, and the ample supply of electric power, coal and Mineral resources to be had to ensure.
Silica is one of Mineral resources that nature reserves are maximum, is also a kind of ore of the most difficult reduction in the world.Must could realize under the high temperature conditions, its reduction temperature is higher at ambient pressure, the oxygen in such silica could with carbon generation chemical reaction, the carbon monoxide of generation overflows burning, and silicon could generate ferro-silicon with iron generation combination reaction.But in the smelting technology of existing ferrosilicon, all contain the impurity such as a large amount of S, P, want to remove S, P, need to spend a large amount of man power and materials, and precision is not high.
And the present invention recycles solar panel crystalline silicon waste material, reduce landfill to pollute, not only can solve the landfill pollution problem of solar panel crystalline silicon waste material, it can also be made as raw material production ferrosilicon, thus obtaining objective economic benefit, emphasis is the ferrosilicon that can obtain not having S, P.
3. beneficial effect
Compared to prior art, beneficial effect of the present invention is:
(1) of the present inventionly crystalline silicon waste material smelting duriron is utilized, utilize in the method for crystalline silicon waste material smelting duriron, when solar panel crystalline silicon waste material can be used to carry out ferrosilicon smelting, first raw material mainly highly purified silicon and silicon carbide and a small amount of silicon-dioxide, and the smelting technology of crystalline silicon guarantees it containing S, P; The present invention utilizes the carbon in silicon carbide to reduce silicon-dioxide simultaneously, therefore do not need additionally to add coke, so decrease the consumption of the energy, and owing to not needing to add coke, decrease the impact of phosphoric and element sulphur, product ferrosilicon is low-phosphorous, low-sulfur, low-carbon (LC) and ferrosilicon, is worth high; Emphasis is owing to not containing phosphoric and element sulphur in raw material, also not adding phosphoric and element sulphur in production process, and do not worry p and s impurity, without phosphorus and sulphur impurity in its ferrosilicon produced, purity is high;
(2) method of the present invention can while production ferrosilicon, and reduce the discharge of solar cell board waste material, kill two birds with one stone, reduce resource consumption, production technique adopts injection method, shortens the technical process of smelting ferrosilicon;
(3) production process of the present invention is simple, reasonable in design, is easy to realize;
(4) the present invention adopts helium etc. to do protection gas and can not form SiO/SiC, improves the rate of recovery of Si;
(5) can not silicon nitride be produced in production process of the present invention, boost productivity.
Accompanying drawing explanation
Fig. 1 is the structural representation of the intermediate frequency furnace adopted in embodiments of the invention 1;
Fig. 2 is the structural representation of the intermediate frequency furnace adopted in embodiments of the invention 2.
In figure: 1, body of heater hypomere; 2, body of heater stage casing; 3, body of heater epimere; 4, nozzle; 5, winding-up rifle.
Embodiment
A kind of crystalline silicon method for treatment of waste material, ferrosilicon prepared by molten iron crystalline silicon cutting waste material being put into fusing when there being shielding gas to protect.
A kind of crystalline silicon method for treatment of waste material, the steps include:
(A) steel scrap is put into smelting furnace, scrap melting is become molten iron by body of heater heating, and is continued by molten iron to be heated to more than 1570 DEG C;
(B) blow in molten iron by silica flour waste material continuous spraying, form liquation, the temperature adding silica flour waste material liquation controls more than 1480 DEG C;
(C) continuous winding-up silica flour waste material, control and the temperature maintaining liquation more than 1330 DEG C, until ferro-silicon liquid reaches the liquid level of required ferro-silicon label product; Shielding gas protection is adopted in whole working process.
Preferably, also comprise step (D): the ferro-silicon liquid in stove is sent to vacuum decarburization device and carries out decarburization, carry out composition and finally adjust, obtain qualified ferro-silicon liquid.The adjustment of this composition is the ratio needing to adjust ferrosilicon according to demand.Now can reach the standard of ferro-silicon, but the too high problem of carbon content may be there is in partial picture, now for this situation, only the ferro-silicon liquid in intermediate frequency furnace need be sent to vacuum decarburization device carries out decarburization, according to the difference of carbon containing, select to add iron scale, carry out composition and finally adjust, generate qualified ferro-silicon liquid, smelting process terminates.Vacuum decarburization adopts common decarbonization process, and those skilled in the art can realize, and place does not repeat them here.
Preferably, in described step (A), the add-on of steel scrap is determined with the purity of ferrosilicon to be prepared according to becoming to be grouped in silica flour waste material.
Preferably, described shielding gas is the shielding gas beyond nitrogen.Shielding gas mainly prevents composition to be oxidized; why nitrogen is foreclosed; when mainly state modulator is bad; certain silicon nitride may be produced in reaction; find through our great many of experiments; in addition to nitrogen, as long as the shielding gas that discord material reacts can reach this effect.
Preferably, described shielding gas is helium/neon/argon gas/Krypton/xenon.
Below in conjunction with specific embodiment, the present invention is described further.
Present invention utilizes silicon carbide and melt reaction mechanism
Silicon carbide melts
Silicon carbide fusing point is 2700 DEG C, proportion 3200kg/m
3.In silica flour waste material, silicon-carbide particle is blown in molten iron or ferro-silicon liquid, silicon-carbide particle and molten iron or ferro-silicon liquid carry out sufficient thermodynamics and kinetics exchange, make carbon be combined with iron and be liquefied silicon carbide, silicon and molten iron or ferro-silicon liquid are further combined with forming ferro-silicon liquid.
Reactional equation: SiC+Fe---→ SiFe+C
Silicon dioxde reaction mechanism
Silica melting point 1650 DEG C, proportion 2200kg/m
3.In silica flour waste material, silica dioxide granule is blown in molten iron or ferro-silicon liquid, silica dioxide granule and molten iron or ferro-silicon liquid carry out sufficient thermodynamics and kinetics exchange, the carbon generation chemical reaction that part of silica particle and molten iron or ferro-silicon liquid rush, makes silicon-dioxide be reduced into silicon.Chemical reaction is as follows:
C+SiO
2——→SiO+CO↑
In the process that silicon carbide melts, produce a certain amount of C element sometimes, cannot discharge.In atmospheric conditions, the SiO produced in the process that silicon-dioxide melts is dissolved in ferro-silicon liquid simultaneously, cannot continue reaction and generate Si and CO.Therefore after ferro-silicon liquid is come out of the stove through vacuum decarburization device, namely move can remove SiO by molecular balance, if still containing C element, add appropriate iron scale, reach the object removing C element, produce qualified ferrosilicon.
Vacuum decarburization reaction formula is as follows:
C+SiO——→Si+CO↑
Fe-C+Fe
3O
4——→FeO+CO↑
Fe-C+FeO——→Fe+CO↑
The present invention is explained further below in conjunction with specific embodiment.
Embodiment 1
Adopt a kind of intermediate frequency furnace as shown in Figure 1 during the present embodiment heating, comprise body of heater, body of heater is divided into body of heater hypomere 1, body of heater stage casing 2 and body of heater epimere 3 three sections from bottom to top; The diameter of body of heater hypomere 1 is 764mm, is highly 700mm, and the shape of the vertical section in body of heater stage casing 2 is the reverse frustoconic of inner hollow, and the diameter of lower end, body of heater stage casing 2 equals the diameter of body of heater hypomere 1; The height in body of heater stage casing 2 is 700mm, and the angle of side and horizontal plane is 60 °, and the height of body of heater epimere 3 is 1462mm, and the diameter of upper end, body of heater stage casing 2 equals the diameter of body of heater epimere 3, and this intermediate frequency furnace is 10 tons of ferrosilicon intermediate frequency furnaces.The sidewall bottom in body of heater stage casing 2 is provided with 2 nozzles 4, and the bottom of body of heater hypomere 1 is provided with a nozzle 4, and nozzle 4 adopts gas permeable brick; Body of heater epimere 3 is provided with Heat preservation coil; Body of heater hypomere 1 and body of heater stage casing 2 are provided with heater coil.The Heat preservation coil of body of heater epimere 3 works alone; The heater coil in body of heater hypomere 1 and body of heater stage casing 2 is by same control circui.Heat preservation coil is positioned at the bottom of body of heater epimere 3.
During use, the steps include:
(A) by the 2500kg low-carbon waste steel shove charge needed for smelting ferrosilicon, scrap melting is become molten iron with body of heater stage casing 2 heater coil energising work by body of heater hypomere 1, and is continued by molten iron to be heated to 1570 DEG C within the scope of 1610 DEG C; The composition of silica flour waste material is: Si:72%, Si-C:16%, Fe:2%, and all the other are SiO
2, granularity: 6.5 μm-10 μm;
(B) by the nozzle 4 of body of heater hypomere 1, silica flour waste material continuous spraying is blown in molten iron, forms liquation, the power of adjustment heater coil, control and maintain add liquation after silica flour waste material temperature at 1480 DEG C within the scope of 1520 DEG C; Winding-up adopts argon gas winding-up, and winding-up argon carrier amount is 310Nm
3/ h, silica flour waste material winding-up amount is 300kg/min;
(C) after being blown into silica flour waste material, the liquid level of liquation rises and after filling body of heater stage casing 2, to be jetted silica flour waste material by the nozzle 4 in body of heater stage casing 2, the Heat preservation coil of body of heater epimere 3 is started working, continuous winding-up silica flour waste material, final control the temperature maintaining liquation at 1330 DEG C within the scope of 1380 DEG C, until ferro-silicon liquid is full of body of heater working zone.
(E) ferro-silicon liquid is sent into vacuum decarburization device, regulate vacuum tightness to-5, add iron scale 252.4kg, produce qualified ferro-silicon liquid, smelting process terminates simultaneously.
Come out of the stove ferro-silicon amount: 10283kg, silicon content 72.9%.
Embodiment 2
Adopt a kind of intermediate frequency furnace as shown in Figure 2 during the present embodiment heating, with embodiment 1, the height not being both body of heater hypomere 1 is 600mm, and the volume of body of heater hypomere 1 accounts for 40% of body of heater working zone; Also comprise winding-up rifle 5, charging is by winding-up rifle 5, and winding-up rifle 5 is inserted into the bottom of body of heater hypomere 1 downwards through the top of body of heater.Winding-up rifle 5 is adopted to add silica flour waste material.
(A) by the 2500kg low-carbon waste steel shove charge needed for smelting ferrosilicon, scrap melting is become molten iron with body of heater stage casing 2 heater coil energising work by body of heater hypomere 1, and is continued by molten iron to be heated to 1590 DEG C within the scope of 1630 DEG C; The composition of silica flour waste material is: Si:72%, Si-C:16%, Fe:2%, and all the other are SiO
2, granularity: 6.5 μm-10 μm;
(B) by the nozzle 4 of body of heater hypomere 1, silica flour waste material continuous spraying is blown in molten iron, forms liquation, the power of adjustment heater coil, control and maintain add liquation after silica flour waste material temperature at 1450 DEG C within the scope of 1560 DEG C; Winding-up adopts helium winding-up, and winding-up helium load volume is 345Nm
3/ h, silica flour waste material winding-up amount is 390kg/min;
(C) after being blown into silica flour waste material, the liquid level of liquation rises and after filling body of heater stage casing 2, to be jetted silica flour waste material by the nozzle 4 in body of heater stage casing 2, the Heat preservation coil of body of heater epimere 3 is started working, continuous winding-up silica flour waste material, final control the temperature maintaining liquation at 1340 DEG C within the scope of 1365 DEG C, until ferro-silicon liquid is full of body of heater working zone.
(E) ferro-silicon liquid is sent into vacuum decarburization device, regulate vacuum tightness to-5, add iron scale 227.9kg, produce qualified ferro-silicon liquid, smelting process terminates simultaneously.
Come out of the stove ferro-silicon amount: 10265kg, silicon content 73.1%.
Embodiment 3
Adopt a kind of intermediate frequency furnace as shown in Figure 2 during the present embodiment heating, comprise body of heater, body of heater is divided into body of heater hypomere 1, body of heater stage casing 2 and body of heater epimere 3 three sections from bottom to top; The diameter of body of heater hypomere 1 is 874mm, is highly 800mm, and the shape of the vertical section in body of heater stage casing 2 is the reverse frustoconic of inner hollow, and the diameter of lower end, body of heater stage casing 2 equals the diameter of body of heater hypomere 1; The height in body of heater stage casing 2 is 700mm, and the angle of side and horizontal plane is 60 °, and the height of body of heater epimere 3 is 2024mm, and the diameter of upper end, body of heater stage casing 2 equals the diameter of body of heater epimere 3, and this intermediate frequency furnace is 15 tons of ferrosilicon intermediate frequency furnaces.The sidewall bottom in body of heater stage casing 2 is provided with 2 nozzles 4, and the bottom of body of heater hypomere 1 is provided with a nozzle 4, and nozzle 4 adopts gas permeable brick; Body of heater epimere 3 is provided with Heat preservation coil; Body of heater hypomere 1 and body of heater stage casing 2 are provided with heater coil.The Heat preservation coil of body of heater epimere 3 works alone; The heater coil in body of heater hypomere 1 and body of heater stage casing 2 is by same control circui.Heat preservation coil is positioned at the bottom of body of heater epimere 3.
During use, the steps include:
(A) by the 3750kg low-carbon waste steel shove charge needed for smelting ferrosilicon, scrap melting is become molten iron with body of heater stage casing 2 heater coil energising work by body of heater hypomere 1, and is continued by molten iron to be heated to 1570 DEG C within the scope of 1600 DEG C; The composition of silica flour waste material is: Si:72%, Si-C:16%, Fe:2%, and all the other are SiO
2, granularity: 10 μm-38 μm;
(B) by the nozzle 4 of body of heater hypomere 1, silica flour waste material continuous spraying is blown in molten iron, forms liquation, the power of adjustment heater coil, control and maintain add liquation after silica flour waste material temperature at 1480 DEG C within the scope of 1510 DEG C; Winding-up adopts neon winding-up, and winding-up neon load volume is 300Nm
3/ h, silica flour waste material winding-up amount is 300kg/min;
(C) after being blown into silica flour waste material, the liquid level of liquation rises and after filling body of heater stage casing 2, to be jetted silica flour waste material by the nozzle 4 in body of heater stage casing 2, the Heat preservation coil of body of heater epimere 3 is started working, control and the temperature maintaining liquation at 1480 DEG C within the scope of 1510 DEG C;
(D) continuous winding-up silica flour waste material, finally control and the temperature maintaining liquation at 1350 DEG C within the scope of 1400 DEG C, until ferro-silicon liquid is full of body of heater working zone.
(E) ferro-silicon liquid is sent into vacuum decarburization device, regulate vacuum tightness to-5, add iron scale 378.6kg, produce qualified ferro-silicon liquid, smelting process terminates simultaneously.
Come out of the stove ferro-silicon amount: 15424kg, silicon content 73%.
Embodiment 4
With embodiment 1, difference is described shielding gas is Krypton.
Embodiment 5
With embodiment 1, difference is described shielding gas is xenon.
Schematic above the present invention and embodiment thereof to be described, those of ordinary skill in the art are according to the description in present specification and accompanying drawing, can know principle of work of the present invention and completely can realize technical scheme of the present invention and reach the effect that the present invention will reach, so repeat no more, this schematic description is not restricted, shown in accompanying drawing is also one of embodiments of the present invention, method is not limited thereto, and common intermediate frequency stove direct heating can be adopted, but silicone content is lower like this, need first to refine a stove, then half is poured out to another stove, and then add silica flour, some is complicated for program, vacuum oven is directly adopted to smelt in other words or winding-up charging smelting+vacuum decarburization below, these are also all can according to the method in claims of the present invention, those skilled in the art can expect and the technical scheme easily realized naturally, so, if those of ordinary skill in the art enlightens by it, when not departing from the invention aim, the frame mode identical or similar with this technical scheme and embodiment is designed without creationary, based on the legislative spirit of patent law, protection scope of the present invention all should be belonged to.
Claims (6)
1. a crystalline silicon method for treatment of waste material, ferrosilicon prepared by molten iron crystalline silicon cutting waste material being put into fusing when there being shielding gas to protect.
2. a crystalline silicon method for treatment of waste material, the steps include:
(A) steel scrap is put into smelting furnace, scrap melting is become molten iron by body of heater heating, and is continued by molten iron to be heated to more than 1570 DEG C;
(B) blow in molten iron by silica flour waste material continuous spraying, form liquation, the temperature adding silica flour waste material liquation controls more than 1480 DEG C;
(C) continuous winding-up silica flour waste material, control and the temperature maintaining liquation more than 1330 DEG C, until ferro-silicon liquid reaches the liquid level of required ferro-silicon label product; Shielding gas protection is adopted in whole working process.
3. a kind of crystalline silicon method for treatment of waste material according to claim 2, it is characterized in that, also comprise step (D): the ferro-silicon liquid in stove is sent to vacuum decarburization device and carries out decarburization, carry out composition and finally adjust, obtain qualified ferro-silicon liquid.
4. a kind of crystalline silicon method for treatment of waste material according to claim 2, is characterized in that, in described step (A), the add-on of steel scrap is determined with the purity of ferrosilicon to be prepared according to becoming to be grouped in silica flour waste material.
5. a kind of crystalline silicon method for treatment of waste material according to claim 1 and 2, is characterized in that, described shielding gas is the shielding gas beyond nitrogen.
6. a kind of crystalline silicon method for treatment of waste material according to claim 5, is characterized in that, described shielding gas is helium/neon/argon gas/Krypton/xenon.
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| CN115704061A (en) * | 2021-08-16 | 2023-02-17 | 中国科学院过程工程研究所 | Rare earth silicon-iron alloy prepared based on neodymium-iron-boron oil sludge and cutting waste silicon powder and preparation method thereof |
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