CN102241399A - Method for preparing low-boron, low-phosphorus high-purity silicon by electrothermal metallurgy process - Google Patents
Method for preparing low-boron, low-phosphorus high-purity silicon by electrothermal metallurgy process Download PDFInfo
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 63
- 239000011574 phosphorus Substances 0.000 title claims abstract description 63
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 54
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 39
- 239000010703 silicon Substances 0.000 title claims abstract description 39
- 238000005272 metallurgy Methods 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 120
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 59
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 36
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims description 36
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 claims description 33
- 150000007522 mineralic acids Chemical class 0.000 claims description 25
- 229960001866 silicon dioxide Drugs 0.000 claims description 23
- 229910002804 graphite Inorganic materials 0.000 claims description 20
- 239000010439 graphite Substances 0.000 claims description 20
- 238000010306 acid treatment Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 239000000571 coke Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000003610 charcoal Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000006004 Quartz sand Substances 0.000 claims description 4
- 238000005485 electric heating Methods 0.000 claims description 4
- 239000005350 fused silica glass Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 241001062472 Stokellia anisodon Species 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 29
- 238000003723 Smelting Methods 0.000 abstract description 29
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 20
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000003825 pressing Methods 0.000 abstract 1
- 229920005591 polysilicon Polymers 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000004568 cement Substances 0.000 description 7
- 238000009408 flooring Methods 0.000 description 7
- 238000005554 pickling Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 5
- 238000007669 thermal treatment Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- -1 gac Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The invention discloses a method for preparing low-boron, low-phosphorus high-purity silicon by an electrothermal metallurgy process, which belongs to the technical field of metallurgy and is implemented by the following steps: preparing a silicon dioxide basic material containing less than or equal to 10 weight ppm of boron and phosphorus and a carbon reducer; and mixing, adding a binding agent to obtain a binding material, pressing to obtain blocks, placing the blocks in a submerged arc furnace, performing electrothermal smelting and obtaining the low-boron, low-phosphorus high-purity silicon. When the method is used, the rise of furnace bottom in a smelting process can be avoided effectively and the continuous smelting can be ensured. In the invention, the content of boron and phosphorus, which are key impurities, in a silicon product is controlled by controlling the boron and phosphorus content in a raw material; the low-boron, low-phosphorus high-purity silicon prepared by the electrothermal metallurgy process can be further purified to provide high-quality raw material for solar polycrystalline silicon; and thus, the production energy consumption and cost of the polycrystalline silicon are further reduced.
Description
Technical field
The invention belongs to metallurgical technology field, the method for the low boron phosphorus HIGH-PURITY SILICON of particularly a kind of electrothermal metallurgy method preparation.
Background technology
In recent years resource growing tensions such as Quan Qiu oil and coal, renewable energy resources sun power becomes most important new forms of energy of 21 century because of inexhaustible, clean environment firendly, advantage such as safe and reliable.Developed country formulates the policy of encourage growth photovoltaic industry one after another, and the global solar industry has entered high-speed development period, and in recent years, global photovoltaic industry every year is with 40 ~ 50% rate of increase development.The regional sunshine duration of China 2/3 more than 2000h/a, most suitable development sun power, China greatly develops solar energy industry now.
Preparation solar cell used critical material is that purity is 6N(99.9999%) polysilicon.The main method of producing solar-grade polysilicon at present in the world has improvement Siemens Method, silane thermal decomposition process and fluidized bed process, the patented technology of these methods is on top of outside among the national champion, the production of polysilicon technology of kiloton scale for a long time by U.S., moral, move, day etc. state company monopolizing.The active demand that solar-grade polysilicon is prepared gordian technique based on China, at the energy consumption height that exists in the existing solar-grade polysilicon production process, problems such as cost is high and seriously polluted, cleaning procedure and gordian technique that the research and development metallurgy method is produced solar-grade polysilicon, formation has the polysilicon clearer production technology of independent intellectual property right, break international monopoly, realize the low cost of solar-grade polysilicon, less energy-consumption and eco-friendly suitability for industrialized production, this is to the Sustainable development of China's photovoltaic industry, solve energy security and alleviate China's reduction of greenhouse gas discharge pressure and have great strategic importance.
Complex process, the investment of methods such as improvement siemens etc. is big, energy consumption is high, makes the holding at high price of polysilicon.And metallurgy method prepares solar-grade polysilicon that cost is low because of having, low, the less investment of power consumption, environment amenable advantage become the domestic and international research focus.Present domestic research prepares solar-grade polysilicon with metallurgy method, the overwhelming majority is to be raw material with the industrial silicon of metallurgical grade or chemical grade or industrial silica fume, adopt methods such as grinding, pickling, external refining, vacuum refinement and directional freeze to purify, but these methods all are difficult to be removed to the scope of requirement to boron in the silicon and phosphorus impurities.In the silicon boron and phosphorus impurities be difficult to remove, become metallurgy method and prepared the technical bottleneck that solar-grade polysilicon is difficult to realize.
Summary of the invention
The problem that boron phosphorus critical impurities is difficult to remove when preparing polysilicon at the prior art metallurgy method, the invention provides the method for the low boron phosphorus HIGH-PURITY SILICON of a kind of electrothermal metallurgy method preparation, silica material that the boron phosphorus content is low and carbonaceous reducing agent and binding agent together are pressed into agglomerate, prepare the HIGH-PURITY SILICON of low boron phosphorus again by the electrothermal metallurgy method.
The present invention carries out according to the following steps:
1. raw material is handled:
Choose SiO
2The silica material of the weight content≤50ppm of weight content 〉=98% and boron and the weight content≤50ppm of phosphorus, the powder that is broken into granularity≤3mm is as silicon dioxide powder; When the weight content of boron in the silicon dioxide powder and phosphorus all≤during 10ppm, directly as silicon-dioxide basis raw material; When the weight content of boron in the silicon dioxide powder or phosphorus＞10ppm, silicon dioxide powder to be mixed with inorganic acid solution, blending ratio is by weight being silicon dioxide powder: inorganic acid solution=1:4 ~ 20, again acid treatment 2 ~ 72h under 20 ~ 90 ℃ of conditions; Water clean to be removed surperficial acid solution after the acid treatment, and the dry again moisture of removing is incubated 0.5 ~ 6h then and carries out vacuum heat treatment under the condition of 300 ~ 1200 ℃ and vacuum tightness≤1000Pa, and the material of acquisition is as the basic raw material of silicon-dioxide;
Choose the carbon raw material of the weight content≤50ppm of the weight content≤50ppm of boron and phosphorus, the powder that is broken into granularity≤3mm is as the carbonaceous powder; In the carbonaceous powder weight content of boron and phosphorus all≤10ppm, directly as carbonaceous reducing agent; When the weight content of boron or phosphorus in the carbonaceous powder＞10ppm, the carbonaceous powder to be mixed with inorganic acid solution, blending ratio is by weight being carbonaceous powder: inorganic acid solution=1:4 ~ 20, again acid treatment 2 ~ 72h under 20 ~ 90 ℃ of conditions; Water clean to be removed surperficial acid solution after the acid treatment, and the dry again moisture of removing is incubated 0.5 ~ 6h then and carries out vacuum heat treatment under the condition of 300 ~ 1200 ℃ and vacuum tightness≤1000Pa, and the material of acquisition is as carbonaceous reducing agent;
2, batching briquetting:
With silicon-dioxide basis raw material and carbonaceous reducing agent mix, the amount of allocating into of C is by reduction SiO
20.9 ~ 1.0 times of batching of required theoretical carbon amount, the reaction equation of charge calculation institute foundation is SiO
2+ 2C=Si+ 2CO, wherein C is a fixation of C in the carbonaceous reducing agent; Add binding agent then in the blended material, the add-on of binding agent is 2 ~ 8% of silicon-dioxide basis raw material and a carbonaceous reducing agent gross weight, mixes and makes binding material;
3, electric heating is smelted:
Binding material is pressed into the agglomerate of particle diameter 10 ~ 50mm, places the hot stove in the ore deposit of adopting Graphite Electrodes to make to carry out electric heating agglomerate and smelt, make the HIGH-PURITY SILICON of low boron phosphorus; Weight content 〉=99.9% of Si in the low boron phosphorus HIGH-PURITY SILICON, the weight content≤10ppm of boron, the weight content≤10ppm of phosphorus.
In the raw material of the above-mentioned carbonaceous reducing agent after peracid treatment and vacuum heat treatment and silicon-dioxide basis, the weight content of boron and phosphorus all≤10ppm.
Above-mentioned inorganic acid solution is one or more the mixed acid solution in hydrochloric acid, nitric acid and the sulfuric acid, and the weight concentration of inorganic acid solution is 3 ~ 20%.
Above-mentioned carbon raw material is meant the one or more kinds of mixtures in refinery coke, graphite, carbon black, metallurgical coke, gac and the charcoal.
Above-mentioned silica material is one or more the mixture in silica, natural quartz, synthetic quartz, quartz sand, fused quartz and the depleted quartz crucible.
Above-mentioned silica material is bulk, gravel shape, sheet, briquet shape, Powdered or particulate state.
Above-mentioned binding agent is a kind of or several in water glass, alcohol, whiteruss and the polyvinyl alcohol.
Particle diameter 10 ~ 50mm agglomerate of suppressing in the aforesaid method, after oven dry, the requirement of strength of agglomerate highly is free to drop down to the cement flooring from 2m and does not pulverize.
Acid treatment after drying removal moisture is meant under 100 ± 5 ℃ of conditions and dries to moisture weight content≤3% in the aforesaid method.
In the Graphite Electrodes in the hot stove in above-mentioned ore deposit the weight content of phosphorus and boron all≤10ppm.
Method of the present invention is the improvement to preparation HIGH-PURITY SILICON step in the disclosed patent applications such as Xing Pengfei " technology of preparing solar-grade polysilicon by adopting high-temperature metallurgy method ", the technology of preparing solar-grade polysilicon by adopting high-temperature metallurgy method by pre-treatment, arc smelting, external refining and vacuum refinement after, make solar-grade polysilicon through directional freeze again.Mixed carbon comtent in this method employing batching is 1.1 ~ 1.3 times of theoretical amount, and for crossing carbon amount batching, the smelting in the hot stove in ore deposit was the smelting of carbon amount, and this can cause furnace bottom to go up gradually, smelting cycle is short continuously; The weight content of boron in the silicon produced of this method arc smelting and phosphorus causes subsequent step technology complicated all greater than 10ppm simultaneously.Method of the present invention is handled boron and the phosphorus content≤10ppm that controls in advance in silicon-dioxide basis raw material and the carbonaceous reducing agent by pickling and high-temperature vacuum, add binding agent then and be pressed into the good air permeability of agglomerate when guaranteeing the furnace reduction reaction, carry out electric heating then and smelt, prepare the boron phosphorus content all≤the low boron phosphorus HIGH-PURITY SILICON of 10ppm.Mixed carbon comtent in the present invention's batching is 0.9 ~ 1.0 times of theoretical amount, and for losing the carbon batching, the interior smelting of the hot stove in ore deposit is smelted for losing the carbon amount, can effectively avoid the furnace bottom rising in the smelting process, guarantees carrying out continuously of smelting.
The present invention is by the content of boron and phosphorus impurities in the control raw material, control the content of critical impurities boron phosphorus in the silicon product, the low boron phosphorus HIGH-PURITY SILICON of utilizing the electrothermal metallurgy method to prepare, for next step it is purified to solar-grade polysilicon provides high-quality raw material, this has just further reduced the production energy consumption and the cost of solar energy polycrystalline silicon.
Embodiment
SiO in the silica that adopts in the embodiment of the invention, natural quartz, synthetic quartz, quartz sand, fused quartz and the depleted quartz crucible
2Weight content 〉=98%, boron and phosphorus weight content all≤50ppm, the powder that is broken into granularity≤3mm is as silica material.
The refinery coke that adopts in the embodiment of the invention, metallurgical coke, graphite, carbon dust, gac, charcoal and artificial charcoal are technical grade product, the weight content of boron and phosphorus all≤10ppm, the powder that is broken into granularity≤3mm is as carbon raw material.
The hydrochloric acid soln that adopts in the embodiment of the invention, salpeter solution and sulphuric acid soln are prepared by industrial acids respectively.
The water glass that adopts in the embodiment of the invention, alcohol, whiteruss and polyvinyl alcohol are commercial technical grade product.
Dry removal moisture is meant under 100 ± 5 ℃ of conditions and dries to moisture weight content≤3% in the embodiment of the invention.
Embodiment 1
Adopting weight concentration is that 20% sulfuric acid is as inorganic acid solution;
The powder that employing is broken into granularity≤3mm by silica is as silicon dioxide powder, SiO
2Weight content 98.0%, the weight content 20ppm of boron, the weight content 35ppm of phosphorus; Silicon dioxide powder is mixed with inorganic acid solution, and blending ratio is silicon dioxide powder: inorganic acid solution=1:15 by weight, again acid treatment 18h under 60 ℃ of conditions; Water clean to be removed surperficial acid solution after the acid treatment, the dry again moisture of removing, and insulation 2h heat-treats under 1200 ℃ and vacuum condition then, and the material of acquisition is as silicon-dioxide basis raw material; The weight content of boron is 8ppm in the silica material after pickling and thermal treatment, and the weight content of phosphorus is 10ppm;
The refinery coke of employing granularity≤3mm and charcoal are as the carbonaceous powder, and wherein the fixed carbon amount of refinery coke accounts for 80% of total mixed carbon comtent, and the fixed carbon amount of charcoal accounts for 20% of total mixed carbon comtent; Wherein the weight content of the boron in the refinery coke is 4ppm, the weight content 8ppm of phosphorus; The weight content of the boron in the charcoal is 30ppm, and the weight content of phosphorus is 50ppm; The carbonaceous powder is mixed with inorganic acid solution, and blending ratio is carbonaceous powder: inorganic acid solution=1:20 by weight, again acid treatment 36h under 40 ℃ of conditions; Water clean to be removed surperficial acid solution after the acid treatment, the dry again moisture of removing, and insulation 4h carries out vacuum heat treatment under 800 ℃ and vacuum condition then, and the material of acquisition is as carbonaceous reducing agent; The weight content of boron is 8ppm in the carbon raw material after pickling and thermal treatment, and the weight content of phosphorus is 10ppm;
Above-mentioned vacuum condition is meant vacuum tightness≤1000Pa;
Silicon-dioxide basis raw material and carbonaceous reducing agent are mixed and made into mixture, and blending ratio is by reduction SiO
20.90 times of batching of the required C amount of reaction theory; Add the binder liquid paraffin body then in the blended material, the add-on of whiteruss is 4% of a mixture gross weight, makes binding material after mixing;
Binding material is pressed into the agglomerate of particle diameter 10 ~ 50mm, and the requirement of strength of agglomerate highly is free to drop down to the cement flooring from 2m and does not pulverize.Select for use the hot stove in the ore deposit that is provided with Graphite Electrodes as smelting furnace, phosphorus in the Graphite Electrodes of the hot stove in ore deposit and boron weight content all≤10ppm.Place smelting furnace to carry out arc smelting agglomerate, prepare low boron phosphorus HIGH-PURITY SILICON, the weight content 99.90% of Si in the low boron phosphorus HIGH-PURITY SILICON, the weight content 5ppm of boron, the weight content 10ppm of phosphorus.
Embodiment 2
Adopting weight concentration is that 8% hydrochloric acid is as inorganic acid solution;
Employing by natural quartz be broken into granularity for the silica powder of≤3mm as silicon dioxide powder, SiO
2Weight content 99.0%, the weight content 6ppm of boron, the weight content 12ppm of phosphorus; Silicon dioxide powder is mixed with inorganic acid solution, and blending ratio is silicon dioxide powder: inorganic acid solution=1:4 by weight, again acid treatment 0.5h under 90 ℃ of conditions; Water clean to be removed surperficial acid solution after the acid treatment, the dry again moisture of removing, and insulation 0.5h heat-treats under 1000 ℃ and vacuum condition then, and the material of acquisition is as silicon-dioxide basis raw material; The weight content of boron is 4ppm in the silica material after pickling and thermal treatment, and the weight content of phosphorus is 8ppm;
The metallurgical coke of employing granularity≤3mm and gac are as the carbonaceous powder, and wherein the fixed carbon amount of metallurgical coke accounts for 85% of total mixed carbon comtent, and the fixed carbon amount of gac accounts for 15% of total mixed carbon comtent; Wherein the weight content of the boron in the metallurgical coke is 15ppm, the weight content 26ppm of phosphorus; The weight content of the boron in the gac is 28ppm, and the weight content of phosphorus is 45ppm; The carbonaceous powder is mixed with inorganic acid solution, and blending ratio is carbonaceous powder: inorganic acid solution=1:15 by weight, again acid treatment 36h under 50 ℃ of conditions; Water clean to be removed surperficial acid solution after the acid treatment, the dry again moisture of removing, and insulation 6h carries out vacuum heat treatment under 300 ℃ and vacuum condition then, and the material of acquisition is as carbonaceous reducing agent; The weight content of boron is 5ppm in the carbon raw material after pickling and thermal treatment, and the weight content of phosphorus is 10ppm;
Above-mentioned vacuum condition is meant vacuum tightness≤1000Pa;
Silicon-dioxide basis raw material and carbonaceous reducing agent are mixed and made into mixture, and blending ratio is by reduction SiO
20.9 times of batching of the required C amount of reaction theory; Add water glass of binder then in the blended material, the add-on of water glass is 8% of a mixture gross weight, makes binding material after mixing;
Binding material is pressed into the agglomerate of particle diameter 10 ~ 50mm, and the requirement of strength of agglomerate highly is free to drop down to the cement flooring from 2m and does not pulverize.Select for use the hot stove in the ore deposit that is provided with Graphite Electrodes as smelting furnace, require phosphorus in the Graphite Electrodes of the hot stove in ore deposit and boron weight content all≤10ppm.Place smelting furnace to carry out arc smelting agglomerate, prepare low boron phosphorus HIGH-PURITY SILICON, the weight content 99.90% of Si in the low boron phosphorus HIGH-PURITY SILICON, the weight content 3ppm of boron, the weight content 8ppm of phosphorus.
Embodiment 3
Adopting weight concentration is that 5% nitric acid is as inorganic acid solution;
The powder that employing is broken into granularity≤3mm by synthetic quartz is as silicon dioxide powder, SiO
2Weight content 99.5%, the weight content 5ppm of boron, the weight content 10ppm of phosphorus, with silicon dioxide powder directly as silicon-dioxide basis raw material;
Adopting the metallurgical coke of granularity≤3mm is the carbonaceous powder, and the weight content of the boron in the metallurgical coke is 15ppm, the weight content 26ppm of phosphorus; The carbonaceous powder is mixed with inorganic acid solution, and blending ratio is carbonaceous powder: inorganic acid solution=1:10 by weight, again acid treatment 72h under 40 ℃ of conditions; Water clean to be removed surperficial acid solution after the acid treatment, the dry again moisture of removing, and insulation 4h carries out vacuum heat treatment under 500 ℃ and vacuum condition then, and the material of acquisition is as carbonaceous reducing agent; The weight content of boron is 5ppm in the carbon raw material after pickling and thermal treatment, and the weight content of phosphorus is 9ppm;
Above-mentioned vacuum condition is meant vacuum tightness≤1000Pa;
Silicon-dioxide basis raw material and carbonaceous reducing agent are mixed and made into mixture, and blending ratio is by reduction SiO
21.0 times of batchings of the required C amount of reaction theory; Add binding agent alcohol then in the blended material, the add-on of alcohol is 6% of a mixture gross weight, makes binding material after mixing;
Binding material is pressed into the agglomerate of particle diameter 10 ~ 50mm, and the requirement of strength of agglomerate highly is free to drop down to the cement flooring from 2m and does not pulverize.Select for use the hot stove in the ore deposit that is provided with Graphite Electrodes as smelting furnace, require phosphorus in the Graphite Electrodes of the hot stove in ore deposit and boron weight content all≤10ppm.Place smelting furnace to carry out arc smelting agglomerate, prepare low boron phosphorus HIGH-PURITY SILICON, the weight content 99.92% of Si in the low boron phosphorus HIGH-PURITY SILICON, the weight content 3ppm of boron, the weight content 8ppm of phosphorus.
Embodiment 4
The quartz sand that adopts granularity≤3mm is as silicon dioxide powder, SiO
2Weight content 99.6%, the weight content 4ppm of boron, the weight content 9ppm of phosphorus, with silicon dioxide powder directly as silicon-dioxide basis raw material;
The carbon black that adopts granularity≤3mm is as the carbonaceous powder, the weight content 5ppm of boron, the weight content 8ppm of phosphorus; With the carbonaceous powder directly as carbonaceous reducing agent;
Silicon-dioxide basis raw material and carbonaceous reducing agent are mixed and made into mixture, and blending ratio is by reduction SiO
20.98 times of batching of the required C amount of reaction theory; Add the binding agent polyvinyl alcohol then in the blended material, the add-on of polyvinyl alcohol is 2% of a mixture gross weight, makes binding material after mixing;
Binding material is pressed into the agglomerate of particle diameter 10 ~ 50mm, and the requirement of strength of agglomerate highly is free to drop down to the cement flooring from 2m and does not pulverize.Select for use the hot stove in the ore deposit that is provided with Graphite Electrodes as smelting furnace, phosphorus in the Graphite Electrodes of the hot stove in ore deposit and boron weight content all≤10ppm.Place smelting furnace to carry out arc smelting agglomerate, prepare low boron phosphorus HIGH-PURITY SILICON, the weight content 99.92% of Si in the low boron phosphorus HIGH-PURITY SILICON, the weight content 3ppm of boron, the weight content 5ppm of phosphorus.
Embodiment 5
The powder that employing is broken into granularity≤3mm by fused quartz is as silicon dioxide powder, SiO
2Weight content 99.8%, the weight content 3ppm of boron, the weight content 5ppm of phosphorus; With silicon dioxide powder as silicon-dioxide basis raw material;
The refinery coke that adopts granularity≤3mm is as the carbonaceous powder, the weight content 4ppm of boron, the weight content 8ppm of phosphorus; With the carbonaceous powder directly as carbonaceous reducing agent;
Silicon-dioxide basis raw material and carbonaceous reducing agent are mixed and made into mixture, and blending ratio is by reduction SiO
20.95 times of batching of the required C amount of reaction theory; Add water glass of binder and alcohol then in the blended material, 4% of each mixture gross weight of the add-on of water glass and alcohol is made binding material after mixing;
Binding material is pressed into the agglomerate of particle diameter 10 ~ 50mm, and the requirement of strength of agglomerate highly is free to drop down to the cement flooring from 2m and does not pulverize.Select for use the hot stove in the ore deposit that is provided with Graphite Electrodes as smelting furnace, phosphorus in the Graphite Electrodes of the hot stove in ore deposit and boron weight content all≤10ppm.Place smelting furnace to carry out arc smelting agglomerate, prepare low boron phosphorus HIGH-PURITY SILICON, the weight content 99.96% of Si in the low boron phosphorus HIGH-PURITY SILICON, the weight content 2ppm of boron, the weight content 4ppm of phosphorus.
Embodiment 6
The powder that employing is broken into granularity≤3mm by the depleted quartz crucible is as silicon dioxide powder, SiO
2Weight content 99.9%, the weight content 2ppm of boron, the weight content 4ppm of phosphorus; With silicon dioxide powder directly as silicon-dioxide basis raw material;
The graphite that adopts granularity≤3mm is as the carbonaceous powder, the weight content 2ppm of boron, the weight content 4ppm of phosphorus; With the carbonaceous powder directly as carbonaceous reducing agent;
Silicon-dioxide basis raw material and carbonaceous reducing agent are mixed and made into mixture, and blending ratio is by reduction SiO
20.93 times of batching of the required C amount of reaction theory; Add binder liquid paraffin body and polyvinyl alcohol then in the blended material, the add-on of whiteruss and polyvinyl alcohol is 3% of a mixture gross weight respectively, makes binding material after mixing;
Binding material is pressed into the agglomerate of particle diameter 10 ~ 50mm, and the requirement of strength of agglomerate highly is free to drop down to the cement flooring from 2m and does not pulverize.Select for use the hot stove in the ore deposit that is provided with Graphite Electrodes as smelting furnace, phosphorus in the Graphite Electrodes of the hot stove in ore deposit and boron weight content all≤10ppm.Place smelting furnace to carry out arc smelting agglomerate, prepare low boron phosphorus HIGH-PURITY SILICON, the weight content 99.99% of Si in the low boron phosphorus HIGH-PURITY SILICON, the weight content 1ppm of boron, the weight content 3ppm of phosphorus.
Claims (7)
1. an electrothermal metallurgy method prepares the method for hanging down boron phosphorus HIGH-PURITY SILICON, it is characterized in that carrying out according to the following steps:
(1) chooses SiO
2The silica material of the weight content≤50ppm of weight content 〉=98% and boron and the weight content≤50ppm of phosphorus, the powder that is broken into granularity≤3mm is as silicon dioxide powder; In silicon dioxide powder the weight content of boron and phosphorus all≤10ppm, directly as silicon-dioxide basis raw material; When the weight content of boron in the silicon dioxide powder or phosphorus＞10ppm, silicon dioxide powder to be mixed with inorganic acid solution, blending ratio is by weight being silicon dioxide powder: inorganic acid solution=1:4 ~ 20, again acid treatment 2 ~ 72h under 20 ~ 90 ℃ of conditions; Water clean to be removed surperficial acid solution after the acid treatment, and the dry again moisture of removing is incubated 0.5 ~ 6h then and carries out vacuum heat treatment under the condition of 300 ~ 1200 ℃ and vacuum tightness≤100Pa, and the material of acquisition is as the basic raw material of silicon-dioxide;
Choose the carbon raw material of the weight content≤50ppm of the weight content≤50ppm of boron and phosphorus, the powder that is broken into granularity≤3mm is as the carbonaceous powder; In the carbonaceous powder weight content of boron and phosphorus all≤10ppm, directly as carbonaceous reducing agent; When the weight content of boron or phosphorus in the carbonaceous powder＞10ppm, the carbonaceous powder to be mixed with inorganic acid solution, blending ratio is by weight being carbonaceous powder: inorganic acid solution=1:4 ~ 20, again acid treatment 2 ~ 72h under 20 ~ 90 ℃ of conditions; Water clean to be removed surperficial acid solution after the acid treatment, and the dry again moisture of removing is incubated 0.5 ~ 6h then and carries out vacuum heat treatment under the condition of 300 ~ 1200 ℃ and vacuum tightness≤1000Pa, and the material of acquisition is as carbonaceous reducing agent;
(2) with silicon-dioxide basis raw material and carbonaceous reducing agent mix, the amount of allocating into of C is by reduction SiO
20.9 ~ 1.0 times of batching of required theoretical carbon amount, the reaction equation of charge calculation institute foundation is SiO
2+ 2C=Si+ 2CO, wherein C is a fixation of C in the carbonaceous reducing agent; Add binding agent then in the blended material, the add-on of binding agent is 2 ~ 8% of silicon-dioxide basis raw material and a carbonaceous reducing agent gross weight, mixes and makes binding material;
(3) binding material is pressed into the agglomerate of particle diameter 10 ~ 50mm, place the hot stove in ore deposit that adopts Graphite Electrodes to carry out electric heating agglomerate and smelt, make low boron phosphorus HIGH-PURITY SILICON, weight content 〉=99.9% of Si in the low boron phosphorus HIGH-PURITY SILICON, weight content≤the 10ppm of boron, the weight content≤10ppm of phosphorus.
2. the method for the low boron phosphorus HIGH-PURITY SILICON of a kind of electrothermal metallurgy method preparation according to claim 1 is characterized in that in the carbonaceous reducing agent and silicon-dioxide basis raw material after peracid treatment and vacuum heat treatment, the weight content of boron and phosphorus all≤10ppm.
3. the method for the low boron phosphorus HIGH-PURITY SILICON of a kind of electrothermal metallurgy method preparation according to claim 1, it is characterized in that described inorganic acid solution is one or more the mixed acid solution in hydrochloric acid, nitric acid and the sulfuric acid, the weight concentration of inorganic acid solution is 3 ~ 20%.
4. the method for the low boron phosphorus HIGH-PURITY SILICON of a kind of electrothermal metallurgy method preparation according to claim 1 is characterized in that described carbon raw material is meant the one or more kinds of mixtures in refinery coke, graphite, carbon black, metallurgical coke, gac and the charcoal.
5. the method for the low boron phosphorus HIGH-PURITY SILICON of a kind of electrothermal metallurgy method preparation according to claim 1 is characterized in that described silica material is one or more the mixture in silica, natural quartz, synthetic quartz, quartz sand, fused quartz and the depleted quartz crucible.
6. the method for the low boron phosphorus HIGH-PURITY SILICON of a kind of electrothermal metallurgy method preparation according to claim 1 is characterized in that described binding agent is a kind of or two or more mixture in water glass, alcohol, whiteruss and the polyvinyl alcohol.
7. the method for the low boron phosphorus HIGH-PURITY SILICON of a kind of electrothermal metallurgy method preparation according to claim 1, the weight content that it is characterized in that phosphorus and boron in the Graphite Electrodes of the hot stove in ore deposit all≤10ppm.
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| CN102976329A (en) * | 2012-12-11 | 2013-03-20 | 安徽科技学院 | Method for preparing high-purity silicon from white carbon black |
| CN104140102A (en) * | 2014-06-25 | 2014-11-12 | 中国科学院过程工程研究所 | Adhesive for preparing silicon smelting waste carbon-containing pellet and preparation method of pellet |
| CN106672976A (en) * | 2017-02-16 | 2017-05-17 | 石兵兵 | Low-boron polycrystalline silicon and preparation method thereof |
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| CN1219504A (en) * | 1998-11-11 | 1999-06-16 | 重庆市渝西硅化工有限公司 | Production technique for smelting crystalline silicon with complete quartz sand |
| CN101724902A (en) * | 2009-12-16 | 2010-06-09 | 东北大学 | Process for preparing solar-grade polysilicon by adopting high-temperature metallurgy method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219504A (en) * | 1998-11-11 | 1999-06-16 | 重庆市渝西硅化工有限公司 | Production technique for smelting crystalline silicon with complete quartz sand |
| CN101724902A (en) * | 2009-12-16 | 2010-06-09 | 东北大学 | Process for preparing solar-grade polysilicon by adopting high-temperature metallurgy method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976329A (en) * | 2012-12-11 | 2013-03-20 | 安徽科技学院 | Method for preparing high-purity silicon from white carbon black |
| CN104140102A (en) * | 2014-06-25 | 2014-11-12 | 中国科学院过程工程研究所 | Adhesive for preparing silicon smelting waste carbon-containing pellet and preparation method of pellet |
| CN104140102B (en) * | 2014-06-25 | 2016-08-17 | 中国科学院过程工程研究所 | For preparing binding agent and the preparation method of pelletizing of refining silicon garbage carbonaceous pelletizing |
| CN106672976A (en) * | 2017-02-16 | 2017-05-17 | 石兵兵 | Low-boron polycrystalline silicon and preparation method thereof |
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