CN102050450A - Device for purifying polysilicon by shell melting method, and method - Google Patents
Device for purifying polysilicon by shell melting method, and method Download PDFInfo
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Abstract
The invention discloses a device for purifying polysilicon by adopting shell melting technology, which comprises a water cooling vacuum hearth, annularly arranged water cooling copper pipes, a water cooling base plate with a lifting device, a plasma torch, a feeder and ultrahigh frequency induction heating coils. The invention also discloses a method for manufacturing solar-grade polysilicon, which comprises the following steps of: forming a solid silicon shell-melting crucible, performing ultrahigh frequency and ultrahigh temperature vacuum melting and plasma atmosphere refining on silicon raw materials in the shell-melting crucible, and performing directional solidification.
Description
Technical field
The present invention relates to the purification techniques of polysilicon, particularly a kind of device and manufacture method thereof that adopts the shell melting technology to make solar level 6N polysilicon.
Technical background
At present, propose in the new forms of energy policy in countries in the world, solar electrical energy generation all occupies an important position.Its most basic material is exactly highly purified solar-grade polysilicon.The development prospect of this industry in the quality of solar-grade polysilicon and cost determination.Most of in the world now manufacturers adopt the improvement Siemens Method to produce electronic-grade polycrystalline silicon, mainly supply the IC industry and use, and small portion is supplied with photovoltaic industry simultaneously.Production cost is higher, and purity (9N-10N) far above the actual needs of solar energy level silicon (6N-7N) generating, is a kind of waste also.In fact, in June, 2008, Suzhou A Site company (CSI) declares publicly: having produced commercial photoelectric transformation efficiency with the polysilicon (UMG) of 100% purity lower (5N) is 13.3% solar cell.At the beginning of 2009, German Wa Ke company has estimated then in the formation of global source polysilicon that the polysilicon that this purity is lower (UMG silicon) will account for 17%.Therefore, for many years, people are seeking the polysilicon novel method of the suitable solar electrical energy generation needs of a kind of low cost production always and are seeing successful hope.
The earliest as the Chinese patent ZL 96198989.0 of Kawasaki, Japan system iron Co., Ltd. (open day: on January 6th, 1999), disclosing a kind of is starting raw material with low-purity industrial silicon (2N), pass through electronic beam vacuum smelting, plasma oxidation refining and directional freeze series of process are produced solar-grade polysilicon.But technology is various, apparatus expensive, and cost is still very high.
On July 19th, 2006) and the Chinese patent CN 200610046525.4 of Dalian University of Technology (open day: on December 6th, 2006) respectively foregoing invention has been done improvement, the Chinese patent ZL 200610010654.8 of Kunming University of Science and Technology (open day: to simplify technology and to raise the efficiency; People such as C.Alemany (the C.Alemany et al.Solar Energy Materials ﹠amp of France; Solar Cells, 72 (2002) 41-48) then induction plasma atmosphere purifying polycrystalline silicon has been done more deep research, their experimental result shows and adopts hydrogeneous and argon plasma atmosphere oxygen can make the content of B in the silicon, P, C and other impurity reduce greatly.
The Chinese patent CN 200710175384.0 of the BJ University of Aeronautics ﹠ Astronautics of China (open day on July 16th, 2008) then discloses a kind of improved device, can be with vacuum melting, electron beam melting, plasma melting and directional freeze are incorporated in the equipment and finish in turn, have simplified technical process.
But great majority have adopted the crucible material incomplete same with bath composition in the above patented technology, under high temperature and plasma body reactive atmosphere, new pollution can be produced unavoidably, and quartzy softening temperature (should be lower than 1600 ℃) can not be surpassed as the temperature that quartz crucible has also limited silicon melt.Electron beam and plasma body can only act on bath surface in addition, thereby under the condition of resistive heating that adopts usually or graphite induction heating, the effect of melting is not fine.
Recently, also the someone has proposed to adopt the higher frequency electromagnetic field to make silicon melt suspend purification to avoid the scheme of crucible pollution, as the Chinese patent CN200710045392.3 of Shanghai Solar Energy Engineering Technology Research Center Ltd (open day on March 4th, 2009), but to make the silicon melt inevitable volume or the quality that limit melt greatly of melting that suspend.
Summary of the invention
Adopt non-silicon materials crucible to bring the secondary pollution problem in order to solve prior art, the purpose of this invention is to provide a kind of device of making solar-grade polysilicon, adopt the shell melting technology, with the fusion crust of high-purity or solar-grade high-purity silicon crucible, eliminate in the previous technology crucible material to the pollution problem of high temperature silicon melt as the splendid attire silicon melt.Adopt the shell melting technology, the temperature of silicon melt can also be brought up to 2000-2500 ℃, in addition higher, thus accelerate removal of impurities chemical reaction rate and impurity rate of volatilization, improve the efficient of purifying greatly.
The silicon melt flow stream velocity is slow when adopting graphite resistance or graphite induction heating mode in order to solve prior art, therefore main high-temperature vacuum melting and the also slow problem of plasma atmosphere purified removal of impurities speed that relies on surface volatilization and reaction, another object of the present invention just provides a kind of technique means, utilize the powerful electromagnetic stirring action of ultra-high frequency electromagnetic field to silicon melt, the silicon melt each several part is improved significantly by the speed that convection current is exposed to the surface, mainly depend on surface reaction and melting of evaporable high-temperature vacuum and plasma atmosphere purified removal of impurities speed thereby strengthen greatly.
Because the development of shell melting technology, the weight of shell melting technology initial refining material can reach the hundreds of kilogram even go up metric ton now, so a further object of the present invention provides the method that a kind of technical scale is made solar-grade polysilicon.Utilize principle of the present invention, suitably improve technology, the silicon materials of the hundreds of of can purifying once, last metric ton, even can purify continuously.
Need repeatedly fusing and coagulation problem in order to solve existing polysilicon physical purification technology, a further object of the invention is to realize high-temperature vacuum melting removal of impurities by stages with the shell melting technology in same equipment, plasma atmosphere refining removal of impurities, with the directional freeze removal of impurities, produce satisfactory solar-grade polysilicon high efficiency, low cost.
In order to realize the foregoing invention purpose, the technical scheme that the present invention at first adopts provides a kind of device (referring to accompanying drawing) of making solar-grade polysilicon, this device comprises: water-cooled vacuum hearth 1, its top is equipped with plasma torch 2, with feeder 3, water-cooled vacuum hearth 1 central authorities are equipped with by the water-cooled copper 6 of annular array and water-cooled chassis 7 (container of forming charge, water-cooled chassis 7 is separable with water-cooled copper 6), and water-cooled copper is around with load coil 10; Water-cooled chassis links to each other with hoisting appliance 16; Vacuum unit 15, steam line 5 link to each other with water-cooled vacuum hearth 1, are used for the water-cooled vacuum hearth and vacuumize and inflate, and can make water-cooled vacuum hearth 1 inside present needed atmosphere state; The silico briquette raw material melts a little molten bath with induction plasma flame earlier, again with the heating that directly is coupled of the ultra-high frequency electromagnetic field of load coil and melted silicon, all melt up to the silicon material, the solid-state silcrete that the part that silicon melt and water-cooled copper contact with water-cooled chassis forms is formed " the fusion crust crucible " 11 of actual splendid attire silicon melt, therefore, silicon melt melting in siliceous " fusion crust crucible " does not directly contact with the chassis with water-cooled copper; The frequency 1-3MHz of load coil, power 100-500KW; Induction plasma also is used for the refining purification phase except that being used for igniting, its induction ionization frequency is 3-5MHz, power 60-200KW.
Second scheme of the present invention provides a kind of method of purifying polycrystalline silicon, and the step that comprises is as follows:
1, form the fusion crust crucible, and melted silicon raw material therein:
2, melting under the ultra-high frequency ultra-high temperature plasma atmosphere;
3, the vacuum melting of ultra-high frequency ultrahigh-temperature;
4, directional freeze;
5, obtain solar-grade polysilicon.
Description of drawings
Accompanying drawing is a shell melting fado crystal silicon purifying plant synoptic diagram of the present invention.
Among the figure, the 1st, water-cooled vacuum hearth, the 2nd, induction plasma spray gun body, the 3rd, feeder, the 4th, silico briquette material, the 5th, inlet mouth, the 6th, annular array water-cooled copper, water-cooled chassis in 7, the 8th, water-in, the 9th, water outlet, the 10th, high-frequency induction heating coil, the 11st, siliceous fusion crust, the 12nd, silicon melt, the 13rd, silicon crystal, the 14th, silicon seed layer, the 15th, vacuum unit, the 16th, lifting device.
Specific embodiments
To first part of the present invention, a kind of preferred embodiment of shell melting technology purifying polycrystalline silicon device that adopts is described below in conjunction with accompanying drawing.This device comprises: water-cooled vacuum hearth 1, its top is equipped with plasma torch 2, with feeder 3, burner hearth central authorities are equipped with water-cooled copper 6 and water-cooled chassis 7 (water-cooled copper 6 and the water-cooled chassis 7 composition charge casks of annular array, the two is separable), water-cooled copper 6 is around with ultra-high frequency load coil 10; Water-cooled chassis 7 links to each other with hoisting appliance 16, but free lifting; Vacuum unit 15, steam line 5 link to each other with water-cooled vacuum hearth 1, are used for burner hearth and vacuumize and inflate, and can make water-cooled vacuum hearth inside present needed atmosphere state; Silicon material piece 4 draws molten with induction plasma spray gun body 2 earlier, again with the heating that directly is coupled of ultra-high frequency ruhmkorff coil 10 and melted silicon 12, all melt up to the silicon material, and silicon melt forms solid-state fusion crust 11 with the part that water-cooled copper contacts with water-cooled chassis, form the fusion crust crucible of splendid attire silicon melt; The frequency 1-3MHz of described ultra-high frequency load coil; The induction plasma spray gun body also is used for the refining purification phase, its ionization coil frequency 3-5MHz.
Concrete purification process is as follows:
1, form the fusion crust crucible, and melting polycrystalline silicon raw material therein:
Water-cooled chassis is risen to annular water-cooled copper lower edge, is that the silica flour slurry of 4N one 6N is applied in container of formation on annular water-cooled copper and the water-cooled chassis then with purity, and the 4N polysilicon block of packing into is to the copper pipe upper edge.
Water-cooled furnace is evacuated to 10
-3Behind the Pa, charge into argon gas and flowed 10-30 minute; Start the argon plasma spray gun body then, ionization frequency 3-5MHz, power 60-200KW, melt a molten bath on polysilicon block top, when the molten bath diameter reaches 20mm when above, start the ultra-high frequency induction heating make it with the silicon molten bath directly coupling and progressively add high-power, induction heating frequency 1-3MHz, power 100-500KW progressively enlarges the silicon molten bath.Constantly feed in raw material by feeder, melt fully with melt liquid level up to silicon and reach predetermined height.Between silicon melt and water-cooled copper and water-cooled chassis, then formed complete " a fusion crust crucible " that constitutes by the fusion crust of solid state si.
2, melting under the ultra-high frequency ultra-high temperature plasma atmosphere:
Add water vapor in the argon plasma, content is 1-10wt.%, reaction gas flow 1-15 liter/minute.The air pressure of vacuum hearth is adjusted to 0.5-1.1atm., and the silicon melt temperature is adjusted to 1450-2500 ℃, constant temperature melting 0.5-5 hour.
3, the vacuum melting of ultra-high frequency ultrahigh-temperature:
Close plasma torch, the vacuum tightness of vacuum hearth adjusts to 10
3-10
-3Pa, melt temperature remain on 1450-2500 ℃, and acutely stir down vacuum melting 0.5-5 hour in the ultra-high frequency high-intensity magnetic field.
4, directional freeze:
Be evacuated down to 10
-3Pa adjusts silicon melt temperature to 1450 ℃ simultaneously, is incubated and leaves standstill silicon melt 30 minutes, all shifts out below the induction coil with 20-200mm/ speed at one hour rating decline water-cooled chassis to melt then.Be cooled to room temperature with 50-200 ℃/h then.
5, obtain solar-grade polysilicon:
The silicon ingot that is chilled to room temperature is cut part about 10% end to end.
The polysilicon that obtains so after testing, its purity is more than 6N, wherein boron content is lower than 0.3ppm, phosphorus content is lower than 0.1ppm, meets the specification of quality of solar-grade polysilicon.
Wherein, step 2 and 3 order can be exchanged.
Below in conjunction with embodiment, further the working process to apparatus of the present invention specifically describes, but does not limit interest field of the present invention.
The purifying plant that adopts among the following embodiment, the charge cask of forming by annular array water-cooled copper and water-cooled chassis wherein, its internal diameter 200mm, high 250mm; But also can expand to, for example, at least to internal diameter 400-500mm, high 300-450mm.
Embodiment one
1, form the fusion crust crucible, and melting polycrystalline silicon raw material therein:
Water-cooled chassis is risen to annular water-cooled copper lower edge, is that the silica flour slurry of 4N is applied in container of formation on annular water-cooled copper and the water-cooled chassis then with purity, and the 4N polysilicon block of packing into is to the copper pipe upper edge.
Burner hearth is evacuated to 10
-3Behind the Pa, charge into argon gas and flowed 10 minutes; Start the argon plasma spray gun body then, ionization frequency 3MHz, power 60KW melts a molten bath in the polysilicon block center upper portion, when the molten bath diameter reaches 20mm when above, starting the ultra-high frequency load coil makes it directly to be coupled with the silicon molten bath and progressively to add high-power, induction heating frequency 1.3MHz, power 200KW progressively enlarges the silicon molten bath, constantly feed in raw material by feeder simultaneously, melt fully with melt liquid level up to silicon and reach predetermined height.Between silicon melt and water-cooled copper and chassis, then formed complete " a fusion crust crucible " that constitutes by the fusion crust of solid state si.
2, melting under the ultra-high frequency ultra-high temperature plasma atmosphere:
Add water vapor in the argon plasma spray gun body, water-content is 1.5wt.%, and reaction gas flow is 5 liters/minute.The vacuum tightness 0.7atm. of burner hearth, 1800 ℃ of silicon melt temperature, melting 1 hour.
3, the vacuum melting of ultra-high frequency ultrahigh-temperature:
Close plasma torch, burner hearth vacuum tightness adjusts to 10
-1Pa, melt temperature continue to remain on 1800 ℃, and acutely stir down vacuum melting 1 hour in the ultra-high frequency high-intensity magnetic field.
4, directional freeze:
Be evacuated down to 10
-3Pa adjusts silicon melt temperature to 1450 ℃, is incubated and leaves standstill melted silicon 30 minutes, all solidifies with 20mm/ speed at one hour rating decline water-cooled chassis to melt then.Be cooled to room temperature with 100 ℃/h then.
5, obtain solar-grade polysilicon:
The silicon ingot that is chilled to room temperature is cut part about 10% end to end.
The polysilicon that obtains so after testing, its purity is more than 6N, wherein boron content is lower than 0.3ppm, phosphorus content is lower than 0.1ppm, meets the specification of quality of solar-grade polysilicon.
Embodiment two
1, form the fusion crust crucible, and melting polycrystalline silicon raw material therein:
Water-cooled chassis is risen to annular water-cooled copper lower edge, is that the silica flour slurry of 6N is applied in container of formation on annular water-cooled copper and the water-cooled chassis then with purity, and the 4N polysilicon block of packing into is to the copper pipe upper edge.
Burner hearth is evacuated to 10
-3Behind the Pa, charge into argon gas and flowed 20 minutes; Start the argon plasma spray gun body then, ionization frequency 3.5MHz, power 100KW melts a molten bath in the polysilicon block center upper portion, when the molten bath diameter reaches 20mm when above, starting the ultra-high frequency load coil makes it directly to be coupled with the silicon molten bath and progressively to add high-power, induction heating frequency 1.8MHz, power 200KW progressively enlarges the silicon molten bath, constantly feed in raw material by feeder, melt fully with melt liquid level up to silicon and reach predetermined height.Between silicon melt and water-cooled copper and chassis, then formed complete " a fusion crust crucible " that constitutes by the fusion crust of solid state si.
2, melting under the ultra-high frequency ultra-high temperature plasma atmosphere:
Add water vapor in the argon plasma spray gun body, vapour content is 3wt.%, and reaction gas flow is 3 liters/minute.The vacuum tightness 0.8atm. of burner hearth, the silicon melt temperature is adjusted to 2000 ℃ of following meltings 0.5 hour.
3, the vacuum melting of ultra-high frequency ultrahigh-temperature:
Close plasma torch, burner hearth vacuum tightness is adjusted to 100Pa, and melt temperature continues to remain on 2000 ℃, and acutely stirs down vacuum melting 1 hour in the ultra-high frequency high-intensity magnetic field.
4, directional freeze:
Be evacuated down to 10
-3Pa adjusts silicon melt temperature to 1450 ℃ simultaneously, is incubated and leaves standstill silicon melt 30 minutes, all solidifies with 100mm/ speed at one hour rating decline water-cooled chassis to melt then.Be cooled to room temperature with 200 ℃/h then.
5, obtain solar-grade polysilicon:
The silicon ingot that is chilled to room temperature is cut part about 10% end to end.
The polysilicon that obtains so after testing, its purity is more than 6N, wherein boron content is lower than 0.3ppm, phosphorus content is lower than 0.1ppm, meets the specification of quality of solar-grade polysilicon.
Embodiment three
1, form the fusion crust crucible, and melting polycrystalline silicon raw material therein:
Water-cooled chassis is risen to annular water-cooled copper lower edge, is that the silica flour slurry of 6N is applied in container of formation on annular water-cooled copper and the water-cooled chassis then with purity, and the AN polysilicon block of packing into is to the copper pipe upper edge.
Burner hearth is evacuated to 10
-3Behind the Pa, charge into argon gas and flowed 30 minutes; Start the argon plasma spray gun body then, ionization frequency 4.5MHz, power 100KW melts a molten bath in the polysilicon block center upper portion, when the molten bath diameter reaches 20mm when above, starting the ultra-high frequency load coil makes it directly to be coupled with the silicon molten bath and progressively to add high-power, induction heating frequency 2.5MHz, power 300KW progressively enlarges the silicon molten bath, constantly feed in raw material by feeder simultaneously, melt fully with melt liquid level up to silicon and reach predetermined height.Between silicon melt and water-cooled copper and chassis, then formed complete " a fusion crust crucible " that constitutes by the fusion crust of solid state si.
3, melting under the ultra-high frequency ultra-high temperature plasma atmosphere:
Add water vapor in the argon plasma spray gun body, water-content is 7wt.%, and reaction gas flow is 10 liters/minute.The vacuum tightness 1.0atm. of burner hearth, 2300 ℃ of silicon melt temperature, melting 0.5 hour.
3, the vacuum melting of ultra-high frequency ultrahigh-temperature:
Close plasma torch, burner hearth vacuum tightness is adjusted to 1000Pa, and melt temperature continues to remain on 2300 ℃, and acutely stirs down vacuum melting 0.5 hour in the ultra-high frequency high-intensity magnetic field.
4, directional freeze:
Be evacuated down to 10
-3Pa adjusts silicon melt temperature to 1450 ℃, is incubated and leaves standstill melted silicon 30 minutes, all solidifies with 150mm/ speed at one hour rating decline water-cooled chassis to melt then.Have a power failure then from being chilled to room temperature.
5, obtain solar-grade polysilicon:
The silicon ingot that is chilled to room temperature is cut part about 10% end to end.
The polysilicon that obtains so after testing, its purity is more than 6N, wherein boron content is lower than 0.3ppm, phosphorus content is lower than 0.1ppm, meets the specification of quality of solar-grade polysilicon.
Obviously, those skilled in the art can carry out various changes and distortion to the present invention and not break away from essential scope of the present invention.If these modifications of the present invention and distortion are belonged within the scope of claim of the present invention and equivalent technology thereof, then the present invention also comprises these changes and is out of shape interior.
Claims (9)
1. the device of a purifying polycrystalline silicon; it is characterized in that; this device comprises: water-cooled vacuum hearth [1]; induction plasma spray gun body [2] and feeding device [3]; the inlet mouth of shielding gas [5]; circular permutation water-cooled copper [6], water-cooled chassis [7] and load coil [10] are installed in the water-cooled vacuum hearth [1], and water-cooled chassis [7] links to each other with jacking system [16], and the water-cooled vacuum hearth links to each other with vacuum unit [15].
2. the device of purifying polycrystalline silicon according to claim 1 is characterized in that, water-cooled copper [6] is isolating with water-cooled chassis [7].
3. the device of purifying polycrystalline silicon according to claim 1 is characterized in that, the output frequency of load coil [10] is 1-3MHz, output rating 100-500KW; The plasma torch ionization frequency is 3-5MHz, power 60-200KW.
4. a device according to claim 1 is made the method for solar-grade polysilicon, it is characterized in that, this method comprises the steps: that (1) forms the fusion crust crucible, and melted silicon raw material therein: the refining of (2) ultra-high frequency ultrahigh-temperature induction plasma atmosphere; (3) ultra-high frequency ultrahigh-temperature vacuum melting; (4) directional freeze; (5) obtain solar level 6N polysilicon.
5. the method for manufacturing solar-grade polysilicon according to claim 4 is characterized in that, the material of described fusion crust crucible is the polysilicon of will be purified, the preferably polycrystalline silicon material of the above purity of 6N.
6. the method for manufacturing solar-grade polysilicon according to claim 4 is characterized in that, described ultra-high frequency ultra-high temperature plasma melting condition is induction heating frequency 1-3MHz, heating power 100-500KW, melt temperature 1450-2500 ℃; The carrier of plasma body is argon, moisture 1-10wt.%, ionization frequency 3-5MHz, and power 60-200KW, reaction gas flow 1-15 liter/minute, smelting time 0.5-5 hour.
7. the method for manufacturing solar-grade polysilicon according to claim 4 is characterized in that, the condition of described ultra-high frequency ultrahigh-temperature vacuum melting is induction heating frequency 1-3MHz, heating power 100-500KW, melt temperature 1450-2500 ℃; Vacuum tightness in the water-cooled vacuum hearth is 10
3Pa-10
-3Pa, smelting time 0.5-5 hour.
8. the method for purifying polycrystalline silicon according to claim 4 is characterized in that, directional freeze speed 20-200mm/ hour.
9. the method for manufacturing solar-grade polysilicon according to claim 4 is characterized in that, the resulting polycrystal silicon ingot of directional freeze need remove crust and portion end to end, accounts for the 5-10% of polycrystal silicon ingot weight, and inner gained is solar level 6N polysilicon.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106756073A (en) * | 2016-12-28 | 2017-05-31 | 哈尔滨工业大学 | A kind of multi-functional melt casting machine for being applied to high-melting-point high activity metal material |
| CN107084620A (en) * | 2017-04-09 | 2017-08-22 | 王红 | A kind of band large-scale metal or nonmetallic sintered crucible |
| CN107084621A (en) * | 2017-04-09 | 2017-08-22 | 王红 | A kind of metal or nonmetallic sintered crucible with shielding body of heater |
| CN107606946A (en) * | 2017-10-25 | 2018-01-19 | 睿为电子材料（天津）有限公司 | The apparatus and method that a kind of high-frequency plasma starts fusing in cold crucible |
| CN114111347A (en) * | 2021-11-15 | 2022-03-01 | 中广核研究院有限公司 | Melting furnace and radioactive waste melting treatment equipment |
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2009
- 2009-11-06 CN CN2009102161543A patent/CN102050450A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106756073A (en) * | 2016-12-28 | 2017-05-31 | 哈尔滨工业大学 | A kind of multi-functional melt casting machine for being applied to high-melting-point high activity metal material |
| CN107084620A (en) * | 2017-04-09 | 2017-08-22 | 王红 | A kind of band large-scale metal or nonmetallic sintered crucible |
| CN107084621A (en) * | 2017-04-09 | 2017-08-22 | 王红 | A kind of metal or nonmetallic sintered crucible with shielding body of heater |
| CN107084620B (en) * | 2017-04-09 | 2019-09-17 | 王红 | A kind of band large-scale metal or nonmetallic sintered crucible |
| CN107084621B (en) * | 2017-04-09 | 2019-09-17 | 王红 | A kind of metal or nonmetallic sintered crucible with shielding furnace body |
| CN107606946A (en) * | 2017-10-25 | 2018-01-19 | 睿为电子材料（天津）有限公司 | The apparatus and method that a kind of high-frequency plasma starts fusing in cold crucible |
| CN114111347A (en) * | 2021-11-15 | 2022-03-01 | 中广核研究院有限公司 | Melting furnace and radioactive waste melting treatment equipment |
| CN114111347B (en) * | 2021-11-15 | 2024-04-26 | 中广核研究院有限公司 | Melting furnace and radioactive waste melting treatment equipment |
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Application publication date: 20110511 |