CN207347178U - A kind of device of silicon melt external refining - Google Patents

A kind of device of silicon melt external refining Download PDF

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CN207347178U
CN207347178U CN201720788265.1U CN201720788265U CN207347178U CN 207347178 U CN207347178 U CN 207347178U CN 201720788265 U CN201720788265 U CN 201720788265U CN 207347178 U CN207347178 U CN 207347178U
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silicon melt
silicon
maing ladle
refining
circle
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魏奎先
王杰
马文会
李绍元
谢克强
伍继君
于洁
雷云
吕国强
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

A kind of device of silicon melt external refining is the utility model is related to, belongs to purifying industrial silicon technology field.Bottom of two-maing ladle in the device sets two gas nozzles, and the angle theta of two nozzle centers of circle and bottom center of circle presentation of two-maing ladle meets:90°≤θ≤180°;Relation between the distance in two nozzle centers of circle and the bottom center of circle of two-maing ladle, spout radius r and the bottom radius R that two-mans ladle is:WhereinSet to bottom of two-maing ladle in two gas nozzles and be continually fed into compressed air or refinery gas, the silicon melt that mine heat furnace smelting goes out is put into in two-maing ladle, with the increase for interior release silicon melt of two-maing ladle, adds refining agent, and adjust and be passed through refinery gas component and flow, carry out air blowing, slag refining outside stove;Push the scum silica frost of silicon melt surface aside, carry out the cast of silicon melt, obtain high-purity industrial silicon product.The dynamic conditions of special interior silicon melt of two-maing ladle is ensure that in the utility model, is eliminated stirring dead angle, is effectively raised silicon product quality.

Description

A kind of device of silicon melt external refining
Technical field
A kind of device of silicon melt external refining is the utility model is related to, belongs to purifying industrial silicon technology field.
Background technology
Industrial silicon industry is source and the basic industry of whole silicon industrial chain.Polysilicon and photovoltaic industry are to develop in recent years Most fast, most promising industry.Industrial silicon industry and polysilicon and photovoltaic industry be belong to silicon industrial chain up and down Product industry is swum, is restricted between quality and quantity close.China is the big producer of industrial silicon, China's industrial silicon yield in 2016 For 225.20 ten thousand tons, increase by 4.74% on a year-on-year basis.
Photovoltaic industry develops rapidly, and the demand of polysilicon solar cell is growing, alusil alloy, organosilicon compared with Fast development, these all drive the fast development of industrial silicon, its market demand increase is also increasingly notable.Scientific and technological production development it is same When, market is also higher and higher to the quality requirement of industrial silicon, and existing industrial silicon production technology gradually can not meet market will Ask.Therefore, more impurity in industrial silicon how are removed, high-purity industrial silicon is prepared and is asked as what each production production man paid close attention to Topic.In the industrial production, the most common impurity-removing method of industrial silicon plant is to carry out stove to the silicon melt that mineral hot furnace comes out in two-maing ladle Outer refining.Zhang Anfu et al. (number of patent application:201110127717) bottom blowing compressed air and oxygen and additional refinements are passed through Desulfurizing agent calcium stone, makes the aluminium accelerated oxidation in silicon liquid, forms oxidizing slag, effectively removes impurity A l contents, improve industrial silicon Product quality.Jihong ZHOU et al. (number of patent application:201510654085) refined by first oxygen blast, then add certain proportion in due course Magnesium salts and sodium salt be mixed into combination wadding agent, effectively by metallurgical grade silicon lifted to chemical grade silicon grade.As can be seen that blow Refining and slag refining can effectively remove partial impurities in industrial silicon, improve silicon product quality.
In fact, the bottom of two-maing ladle used in the furnace outer refining technology of invention only has a nozzle.In actual production, one The bottom blowing refining of a nozzle can both make silicon melt stir insufficient, uneven components in silicon melt, so as to influence product quality, again Cause refining time longer, thermal loss is more, finally influences yield, increases energy consumption.Lifted using the twin-jet nozzle of rational position arrangement Bag carries out external refining, can effectively solve the above problems in the case where excessively not increasing capital expenditure.
The content of the invention
For the above-mentioned problems of the prior art and deficiency, the utility model provides a kind of dress of silicon melt external refining Put.The device of the utility model strengthens external refining in refining using special two-man ladle of bottom twin-jet nozzle, and the utility model leads to Cross following technical scheme realization.
A kind of device of silicon melt external refining, the bottom 2 of two-maing ladle set two gas nozzles 3, two 3 centers of circle of nozzle and The angle theta that the bottom center of circle is presented of two-maing ladle meets:90°≤θ≤180°;The distance 1 in two 3 centers of circle of nozzle and the bottom center of circle of two-maing ladle, Relation between 3 radius r of nozzle and the 2 radius R of bottom that two-mans ladle is:Wherein
A kind of application process of the device of silicon melt external refining, it is comprised the following steps that:
Step 1, set in two gas nozzles 3 to bottom 2 of two-maing ladle and be continually fed into compressed air or refinery gas, to two-maing ladle In be put into the silicon melt that mine heat furnace smelting goes out, with two-man ladle it is interior release silicon melt increase, add refining agent, and adjust be passed through essence Gas componant and flow are refined, carries out air blowing, slag refining outside stove;
After step 2, silicon melt external refining, the scum silica frost of silicon melt surface is pushed aside, after realizing the separation of slag silicon, carry out silicon The cast of melt, obtains high-purity industrial silicon product.
It is 0.5~15m that the step 1, which is passed through refinery gas flow,3/ h, pressure are 1~15MPa, duration of ventilation for 0.3~ 8h.Above-mentioned refinery gas includes but not limited to:One or more of gas arbitrary proportions in air, oxygen-enriched air, vapor etc. Mixed gas.
The step 1 refining agent addition is 20 with silicon melt mass ratio:1~1:20.The feed postition of refining agent includes: Disposable addition, in batches addition etc.;Refining agent refines general refining agent for silicon melt, includes but not limited to:CaO、CaF2、 SiO2, the Ith and II one or more refining agent arbitrary proportions in main group alkali metal compound etc. admixture refining agent.
The utility model aim to solve the problem that using it is existing two-man ladle carry out external refining when, interior silicon melt stirring of two-maing ladle is insufficient, In the presence of stirring dead angle, cause to wrap interior melt quality uneven;Refining time is grown, and silicon melt thermal loss is more, so as to influence yield Realistic problem.After the fully process characteristic and actual condition of research industrial silicon external refining, the utility model is directly right Two-man ladle and transformed, by setting two nozzles in bottom appropriate location of two-maing ladle, the scavenger system of each self-configuring independence, is made Slag, joint of blowing refining, utilize the heat of silicon melt, improve product quality, wherein Al, Ca, Ti, C impurity content well Significantly reduce than before.
Method described in the utility model be using bottom twin-jet nozzle it is special two-man ladle blown, slag refining.Herein During external refining, can according to special interior silicon melt amount of two-maing ladle number, the spraying state of silicon melt, rationally adjustment is each Gas flow, gas pressure and the gas ingredients of nozzle so that it is special two-man ladle interior silicon melt without flowing " dead band ", realize refining when Between shorter, refining process that refining efficiency is higher.This discovery is with refining effect is good, production efficiency is high, capital expenditure is few, environment It is pollution-free, it is easy to the features such as heavy industrialization is applied.
The utility model has the advantage that:
(1) refining effect is good:The utility model twin-jet nozzle it is special two-man ladle in carry out external refining, ensure that special lift The dynamic conditions of silicon melt in bag, eliminates stirring dead angle, effectively raises silicon product quality.
(2) production efficiency is high;External refining using the utility model it is special two-man ladle blown, slag refining, pass through Gas flow, the gas pressure of each nozzle, two nozzle interruptions or the operation such as injection at the same time are adjusted, industrial silicon melt is realized High efficiency purifies.
(3) capital expenditure is few;The utility model only need to carry out reasonable reformation to two-maing ladle, and the specific location in bottom of two-maing ladle is pacified Two nozzles are filled, increase an independent scavenger system, equipment is simple, facilitates feasible.
(4) environmental nonpollution;It is small to environmental pressure since this process will not produce secondary pollution, therefore can realize green It is metallurgical.
Brief description of the drawings
Fig. 1 is 1 structure drawing of device of the utility model embodiment;
Fig. 2 is the specific dimensional structure figure of 1 device of the utility model embodiment;
Fig. 3 is the specific dimensional structure figure of 2 device of the utility model embodiment;
Fig. 4 is the specific dimensional structure figure of 3 device of the utility model embodiment.
In figure:1- two-mans ladle mouth, and 2- two-mans ladle bottom, 3- nozzles.
Embodiment
With reference to the accompanying drawings and detailed description, the utility model is described in further detail.
Embodiment 1
As illustrated in fig. 1 and 2, the device of the silicon melt external refining, two gas nozzles 3 of the setting of bottom 2 of two-maing ladle, two The angle theta of 3 center of circle of nozzle and bottom center of circle presentation of two-maing ladle (meets for 120 °:90°≤θ≤180°);Two 3 centers of circle of nozzle and lift The distance 1 for wrapping the bottom center of circle is that 0.5R, 3 radius r of nozzle are 0.2R, is metWherein
The application process of the device of the silicon melt external refining, it is comprised the following steps that:
Step 1, set to bottom 2 of two-maing ladle and compressed air be continually fed into two gas nozzles 3 (flow of compressed air is 8m3/ h), silicon melt that mine heat furnace smelting goes out is put into in two-maing ladle (mainly including following mass percent component:96%Si, 0.8%Al, 3%Ca), with the increase for interior release silicon melt of two-maing ladle, it is 10 to add mass ratio:1:10 SiO2、CaF2With Al2O3(refining agent addition is 20 with silicon melt mass ratio to refining agent:1), and by two gas nozzles 3 logical oxygen-enriched air (oxygen is changed Gas is 9 with volume of air ratio:1, the oxygen-enriched air pressure being passed through is 5MPa, flow 10m3/ h), carry out air blowing, slag making outside stove Refine 0.3h (i.e. duration of ventilation is 0.3h);
After step 2, silicon melt external refining, the scum silica frost of silicon melt surface is pushed aside, after realizing the separation of slag silicon, carry out silicon The cast of melt, obtains high-purity industrial silicon product.
Al content in the industrial silicon product that the present embodiment is prepared<0.1wt%, Ca content<0.02wt%, silicone content are 99.6%.The equipment (nozzle 1 only is set in bottom centre position of two-maing ladle) of existing conventional silicon melt external refining purification with Al content in the silicon product being prepared under the identical Parameter Conditions of the present embodiment<0.3wt%, Ca content<0.04wt%, silicon contain Measure as 99.3%, hence it is evident that it can be seen that the impurity such as device A l, Ca, Ti, C of industrial silicon melt external refining purification of the application contains Amount is efficiently removed, and improves refining effect.
Embodiment 2
As shown in figure 3, the device of the silicon melt external refining, the bottom 2 of two-maing ladle sets two gas nozzles 3, two sprays The angle theta of 3 center of circle of mouth and bottom center of circle presentation of two-maing ladle (meets for 90 °:90°≤θ≤180°);Two 3 centers of circle of nozzle are with two-maing ladle The distance 1 in the bottom center of circle is that 0.3R, 3 radius r of nozzle are 0.2R, is metWherein
The application process of the device of the silicon melt external refining, it is comprised the following steps that:
Step 1, set to bottom 2 of two-maing ladle and compressed air be continually fed into two gas nozzles 3 (flow of compressed air is 8m3/ h), silicon melt that mine heat furnace smelting goes out is put into in two-maing ladle (mainly including following mass percent component:96%Si, 0.8%Al, 3%Ca), with the increase for interior release silicon melt of two-maing ladle, it is 10 to add mass ratio:1:2 NaO, CaF2And Al2O3 (refining agent addition is 1 with silicon melt mass ratio to refining agent:20), and by two gas nozzles 3 the water flowing steam (water being passed through is changed Steam pressure is 15MPa, flow 0.5m3/ h), carry out air blowing, slag refining 2h outside stove (i.e. duration of ventilation is 2h);
After step 2, silicon melt external refining, the scum silica frost of silicon melt surface is pushed aside, after realizing the separation of slag silicon, carry out silicon The cast of melt, obtains high-purity industrial silicon product.
Al content in the industrial silicon product that the present embodiment is prepared<0.1wt%, Ca content<0.01wt%, B<10ppm, Silicone content is 99.6%.The equipment of existing conventional silicon melt external refining purification (only sets spray in bottom centre position of two-maing ladle Mouth 1) Al content in the silicon product that is prepared under the Parameter Conditions identical with the present embodiment<0.2wt%, Ca content< 0.04wt%, silicone content 99.3%, hence it is evident that it can be seen that the device A l of the industrial silicon melt external refining purification of the application, The impurity contents such as Ca, Ti, C are efficiently removed, and improve refining effect.
Embodiment 3
As shown in figure 4, the device of the silicon melt external refining, the bottom 2 of two-maing ladle sets two gas nozzles 3, two sprays The angle theta of 3 center of circle of mouth and bottom center of circle presentation of two-maing ladle (meets for 180 °:90°≤θ≤180°);Two 3 centers of circle of nozzle are with two-maing ladle The distance 1 in the bottom center of circle is that 0.7R, 3 radius r of nozzle are 0.2R, is metWherein
The application process of the device of the silicon melt external refining, it is comprised the following steps that:
Step 1, set to bottom 2 of two-maing ladle and compressed air be continually fed into two gas nozzles 3 (flow of compressed air is 12m3/ h), silicon melt that mine heat furnace smelting goes out is put into in two-maing ladle (mainly including following mass percent component:96%Si, 0.8%Al, 3%Ca), with the increase for interior release silicon melt of two-maing ladle, addition mass ratio is CaO:MgO:CaF2=6:3:1 refining (refining agent addition is 10 with silicon melt mass ratio for agent:1), and by two gas nozzles 3 logical volume ratio is changed as 1:1 hydrogen and (mixture pressure being passed through is 1MPa, flow 15m to nitrogen mixed gas3/ h), carry out air blowing, slag refining 8h outside stove (i.e. duration of ventilation is 8h);
After step 2, silicon melt external refining, the scum silica frost of silicon melt surface is pushed aside, after realizing the separation of slag silicon, carry out silicon The cast of melt, obtains high-purity industrial silicon product.
Al content in the industrial silicon product that the present embodiment is prepared<0.08wt%, Ca content<0.005wt%, B< 8ppm, silicone content 99.7%.The equipment of existing conventional silicon melt external refining purification (is only installed in bottom interposition of two-maing ladle Put nozzle 1) Al content in the silicon product that is prepared under the Parameter Conditions identical with the present embodiment<0.2wt%, Ca content< 0.02wt%, silicone content 99.4%, hence it is evident that it can be seen that the device A l of the industrial silicon melt external refining purification of the application, The impurity contents such as Ca, Ti, C are efficiently removed, and improve refining effect.
Embodiment 4
The device of the silicon melt external refining, the bottom 2 of two-maing ladle set two gas nozzles 3, two 3 centers of circle of nozzle and lift The angle theta that the bottom center of circle is presented is wrapped for 150 ° (to meet:90°≤θ≤180°);Two 3 centers of circle of nozzle and the bottom center of circle of two-maing ladle Distance 1 is3 radius r of nozzle isMeetWherein
The application process of the device of the silicon melt external refining, it is comprised the following steps that:
Step 1, set to bottom 2 of two-maing ladle and compressed air be continually fed into two gas nozzles 3 (flow of compressed air is 15m3/ h unit), silicon melt that mine heat furnace smelting goes out is put into in two-maing ladle (mainly including following mass percent component:96% Si, 0.8%Al, 3%Ca), with the increase for interior release silicon melt of two-maing ladle, add CaO:MgO:CaF2=6:3:1 refining agent (essence It is 1 that agent addition, which is refined, with silicon melt mass ratio:10), and by two gas nozzles 3 logical volume ratio is changed as 1:1:1 hydrogen gas and water is steamed (mixture pressure being passed through is 5MPa, flow 10m for vapour and nitrogen mixed gas3/ h), carry out air blowing, slag refining outside stove 2h (i.e. duration of ventilation is 2h);
After step 2, silicon melt external refining, the scum silica frost of silicon melt surface is pushed aside, after realizing the separation of slag silicon, carry out silicon The cast of melt, obtains high-purity industrial silicon product.
Al content in the industrial silicon product that the present embodiment is prepared<0.06wt%, Ca content<0.005wt%, B< 8ppm, silicone content 99.7%.The equipment of existing conventional silicon melt external refining purification (is only installed in bottom interposition of two-maing ladle Put nozzle 1) Al content in the silicon product that is prepared under the Parameter Conditions identical with the present embodiment<0.2wt%, Ca content< 0.015wt%, silicone content 99.5%, hence it is evident that it can be seen that the device A l of the industrial silicon melt external refining purification of the application, The impurity contents such as Ca, Ti, C are efficiently removed, and improve refining effect.
Specific embodiment of the present utility model is explained in detail above in association with attached drawing, but the utility model is not It is limited to the above embodiment, within the knowledge of a person skilled in the art, this practicality can also be not being departed from Various changes can be made on the premise of new objective.

Claims (1)

  1. A kind of 1. device of silicon melt external refining, it is characterised in that:Two-man ladle bottom (2) set two gas nozzles (3), two spray The angle theta of mouth (3) center of circle and bottom center of circle presentation of two-maing ladle meets:90°≤θ≤180°;Two nozzle (3) centers of circle and bottom of two-maing ladle Relation between the distance 1 in the center of circle, nozzle (3) radius r and bottom of two-maing ladle (2) radius R is:Wherein
CN201720788265.1U 2017-06-30 2017-06-30 A kind of device of silicon melt external refining Active CN207347178U (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107352546A (en) * 2017-06-30 2017-11-17 昆明理工大学 A kind of devices and methods therefor of silicon melt external refining
CN113661258A (en) * 2019-04-05 2021-11-16 杰富意钢铁株式会社 Vessel for refining high temperature melt

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107352546A (en) * 2017-06-30 2017-11-17 昆明理工大学 A kind of devices and methods therefor of silicon melt external refining
CN113661258A (en) * 2019-04-05 2021-11-16 杰富意钢铁株式会社 Vessel for refining high temperature melt
US11976340B2 (en) 2019-04-05 2024-05-07 Jfe Steel Corporation Refining vessel for high-temperature melt

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