CN101112987A - Method for preparing super metallurgy grade silicon - Google Patents
Method for preparing super metallurgy grade silicon Download PDFInfo
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- CN101112987A CN101112987A CNA2007100660177A CN200710066017A CN101112987A CN 101112987 A CN101112987 A CN 101112987A CN A2007100660177 A CNA2007100660177 A CN A2007100660177A CN 200710066017 A CN200710066017 A CN 200710066017A CN 101112987 A CN101112987 A CN 101112987A
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 56
- 239000010703 silicon Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000005272 metallurgy Methods 0.000 title claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000012535 impurity Substances 0.000 claims abstract description 57
- 238000000605 extraction Methods 0.000 claims abstract description 24
- 238000002386 leaching Methods 0.000 claims abstract description 13
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 106
- 239000000377 silicon dioxide Substances 0.000 claims description 53
- 235000013312 flour Nutrition 0.000 claims description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 39
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000003701 mechanical milling Methods 0.000 claims description 7
- 238000013467 fragmentation Methods 0.000 claims description 5
- 238000006062 fragmentation reaction Methods 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000002525 ultrasonication Methods 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 32
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000011863 silicon-based powder Substances 0.000 abstract description 3
- 238000005728 strengthening Methods 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- 238000011109 contamination Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000004411 aluminium Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 238000003828 vacuum filtration Methods 0.000 description 10
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 9
- 229920005591 polysilicon Polymers 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000011856 silicon-based particle Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 238000009854 hydrometallurgy Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- 239000005052 trichlorosilane Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004484 Briquette Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
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Abstract
The invention provides a method for preparing super metallurgical-grade silicon, relating and pertaining to a method for preparing high purity silicon, in particular to a method for preparing the super metallurgical-grade silicon with purity more than 99.99 percent with metallurgical-grade silicon. The invention is characterized in that: block metallurgical-grade silicon is put into an ultrasonic and microwave field for metallurgical acid leaching after being cleaned, crumbled, ball mill, sieved and preliminary impurity removed, then wet leaching at atmospheric pressure and high-temperature and high-pressure leaching are carried out upon combination to the strengthening treated metallurgical-grade silicon powder so as to leave the metal impurity in the metallurgical-grade silicon powder into the leaching solution as soon as possible, therefore, the leaching solution can be used again upon extraction and the extractant can also be used again after reverse-extraction. The invention jointly uses strengthening technologies in special fields of microwave metallurgy, ultrasonic metallurgy, high-temperature and high-pressure leaching, etc., therefore, the purity of the silicon prepared by the method is 99.99 percent or more, so as to meet the requirements for super metallurgical-grade silicon by solar cell industry. Besides, the invention has the advantages of low investment in equipment, low energy consumption, slight influence on the environment and low cost.
Description
Technical field
The present invention relates to belong to a kind of method for preparing high purity silicon, particularly prepare the method for purity greater than 99.99% super metallurgy grade silicon by metallurgical grade silicon.
Background technology
As everyone knows, traditional fossil energy can not satisfy the human energy demand that increases fast at present.And the photovoltaic industry meets the requirement of the strategy of sustainable development, and all keeps high speed development with the annual growth more than 30% over past ten years.What the photovoltaic industry was relied on is polycrystalline silicon used for solar battery.
Solar cell material mainly comes from the waste material and the substandard products of semi-conductor industry at present.Traditional trichlorosilane (SiHCl
3) hydrogen reduction method is the polycrystalline silicon used for solar battery that the Siemens Method direct production is come out, its investment is big, production cost is high, and poor safety performance, and has occurred problem such as raw material supply shortage.The novel method that the solar energy level silicon that begun one's study is both at home and abroad produced.
The patent of people such as the Wen Rui-Mei of China application relates to the technology that polysilicon is produced in a kind of brand-new hydrogen reduction with the method (patent No. is 02137592.5, and date of declaration is on 03 19th, 2003) of trichlorosilane and silicon tetrachloride producing polysilicon with mixed source, this invention.This invention makes full use of the SiCl that production process produces in polysilicon production process
4, HCl, reach and both guarantee high quality, high yield.Reduce the consumption of material industry silicon, hydrogen and chlorine again, reduced cost.
Japan has developed a kind of novel method thick silicon of purifying and has been used for solar cell.The used raw material of this technology is that purity is about 95% thick silicon.At first, under 1500 ℃ and vacuum condition,, and the phosphorus in the thick silicon is gasified with the 750kW electron beam with its fusing.Adopt directional solidification technique, silicon crystal is arranged in one direction, metallic impurity such as iron, aluminium are separated, boron and carbon then remove with plasma fusing and oxidizing process.Adopt directional solidification technique for the second time then, remove trace-metal.Become ingot highly purified silicon fusing and by the electromagnetic casting technical cure at last, so just avoid silicon to contact with the melting tank wall.
The Ji Chuan of Tokyo Univ Japan is strong to wait the people to utilize Si-Al alloy liquation characteristics to propose to prepare the solar energy level silicon novel process with the metallurgical grade silicon for raw material low temperature, and the physical and chemical process of this process carried out more deep research, but aluminum content is higher in the silicon that obtains at present, also need further be optimized research.
The patent that Marvin's can wait the people to apply for is a kind of to prepare that (patent No. is 200610010654.8 in the method for solar-grade polysilicon, the bulletin time is on 07 19th, 2006), this invention relates to a kind of method for preparing solar-grade polysilicon, adopt metallurgical grade silicon as raw material, after preliminary acidleach processing, carrying out vacuum refinement again in vacuum oven handles, vacuum refinement divides two stages, it is vor refining stage, vacuum distilling refining and vacuum outgas stage,, obtain the solar-grade polysilicon product after directional freeze and crop are handled.The purity of its silicon is more than 99.9999%, satisfies the requirement of the required silicon raw material of solar cell industry.
Super metallurgy grade silicon is intermediates in the solar-grade polysilicon production process, and its purity is mainly produced by the acidleach preprocessing process greater than 99.99%.Because the ununiformity of impurity in the metallurgical grade silicon, for the purification process of metallurgical grade silicon has increased very big difficulty.Can remove most of metallic impurity by preprocessing process, reduce the difficulty of follow-up vacuum melting process; To be ground into the process of silica flour itself be exactly the process of a mixing to the metallurgical grade silico briquette in addition, and it has vital role to the post-processed stability of ensuring the quality of products.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method for preparing super metallurgy grade silicon, its production efficiency height, and facility investment is few, energy consumption is low, influence to environment is smaller, cost is low, and the silicon purity height of output can satisfy the requirement of solar cell industry to super metallurgy grade silicon.
Solving the technical scheme that technical problem of the present invention adopts is: block metallurgical grade silicon is through cleanings, fragmentation, ball milling, screening, tentatively after the operations such as removal of impurities, putting into ultrasonic wave, microwave field carries out metallurgical acidleach and handles, adopt the normal pressure wet method to leach again and High Temperature High Pressure leaching combination through the metallurgical grade silica flour after the intensive treatment, make the metallic impurity in the metallurgical grade silica flour to enter as soon as possible in the leach liquor, leach liquor is through extraction back recycle, and extraction agent is also through the back recycle of stripping.
Major technology condition of the present invention is:
(1) concentration of leach liquor: sulfuric acid concentration is 2mol/L～6mol/L, and concentration of hydrochloric acid is 0.5mol/L～8mol/L, and concentration of nitric acid is 1mol/L～8mol/L;
(2) the weight liquid-solid ratio when microwave treatment, ultrasonication is 1: 1～5: 1, and temperature is 40 ℃～90 ℃, and the treatment time is 0.5 hour～3 hours;
Weight liquid-solid ratio when (3) normal pressure leaches is 1: 1～10: 1, and temperature is 40 ℃～90 ℃, and the treatment time is 1 day～5 days;
Weight liquid-solid ratio when (4) High Temperature High Pressure leaches is 1: 1～8: 1, and pressure is 0.3MPa～2.5MPa, and temperature is 110 ℃～190 ℃, and the treatment time is 0.5 hour～12 hours.
(5) isolated silica flour was the hydrofluoric acid leaching of 1mol/L～5mol/L with concentration at last after High Temperature High Pressure leached, and the concentration of reaction solution is 1mol/L～5mol/L, 40 ℃～80 ℃ of temperature of reaction, and the reaction times is 1 hour～8 hours;
Clean: the block metallurgical grade silicon with commercially available purity 98%～99.5% is a raw material, with clean-out system and ultrasonic equipment its lip-deep foreign material are cleaned 30min～60min, to reduce the increase that causes total impurities in the metallurgical grade silicon because of the increase of these foreign material.
Pulverize: after the metallurgical grade silicon process crusher fragmentation for several times after will cleaning up, drop in the ball mill and grind, obtain 50 orders～300 purpose silica flour materials, be for further processing.
Screening: the silica flour material after will pulverizing drops in the sieve apparatus and carries out the silicon powder particle classification, obtains 50 orders～300 purpose silica flour materials, is for further processing, and also can be used as product and sells; Then put into again less than 50 purpose silica flours and to carry out ball milling repeatedly in the ball mill.
Preliminary removal of impurities: the metallurgical grade silicon after the screening is put into and is carried out repeatedly magnetic separation in the electromagnetic separator, to reduce iron and the iron oxide content of bringing in fragmentation, the mechanical milling process.
Microwave, ultrasonication: will be through the metallurgical grade silica flour after the preliminary removal of impurities, add acid solution according to the weight liquid-solid ratio, in power is reacting by heating 30min～120min, acidleach 5min～180min under 500W～800W ultrasonic wave effect again in the microwave equipment of 300W～1000W.This process mainly is to improve the acidleach temperature, shortens the reaction times, removes the metallic impurity in most metallurgical grade silicon.
Hydrometallurgical process under the normal pressure: continuing with concentration in 40 ℃～90 ℃ of bath temperatures through the metallurgical grade silica flour after the above-mentioned processing is the hydrochloric acid of 0.5mol/L～7mol/L or the leaching of chloroazotic acid secondary 1 day～5 days.This process main purpose is to make the metallurgical grade silica flour fully contact, to react with leach liquor.Make impurity can access better removal.
Hydrometallurgical process in the autoclave: be the sulfuric acid of 2mol/L～6mol/L and hydrochloric acid soln according to liquid-solid ratio through the silica flour after the normal pressure acidleach and concentration be to put in the high pressure reactor after mixing in 1: 1～8: 1, the maintenance reaction pressure is 0.3MPa～2.5MPa, temperature of reaction is 110～190 ℃, and stirring velocity is to react 0.5～12 hour under 300 rev/mins～700 rev/mins the condition.Adopt decompression separation methods such as vacuum filtration that liquid-solid phase is separated then.Silica flour after the separation is the hydrofluoric acid of 1～5mol/L at last with concentration, and 40 ℃～80 ℃ of temperature were soaked 1～8 hour; Remove the silicon-dioxide and some impurity on silica flour material surface, use filtration under diminished pressure after three grades of washed with de-ionized water 3～5 times then, drying.Can sell after the product packing.The inner lining material of autoclave is metal titanium or resin.
The recycle of leaching agent: the leach liquor after adopting extraction liquid to decompression separation carries out extracting and separating.Leach liquor after the separation is put in the above-mentioned preprocessing process again, has realized the recycle of leach liquor; Reacted extraction liquid then adopts soda ash solution or sodium hydroxide solution to strip, and extraction liquid is equally also realized recycle.The metallic impurity elements that produces is nontoxic, can be used as waste and handles.
The invention has the beneficial effects as follows:
1. production efficiency height.Adopted the associating leaching-out technique of microwave metallurgical, ultrasonic wave metallurgy and high pressure-temperature hydrometallurgy, better solved the difficult problem of metallurgical grade silicon purification, made refining effect and production efficiency that the variation of matter arranged;
2. initial cost is less.Present method has mainly adopted full hydrometallurgical technology, and its initial cost can reduce 70% with respect to its initial cost of identical production-scale pyrogenic process manufacturer;
3. equipment is simple, security good.Because this technology all is hydrometallurgy process, its equipment is fairly simple, and subsystem is few, and safe;
4. less energy consumption, production cost is low.Its power consumption can reduce more than 60% in the production process, and production cost can reduce by 50%;
5. low in the pollution of the environment.Because what the leaching agent of this process adopted recycles, and do not need to discharge a large amount of acid solutions in the production process, so this novel process is little to environmental stress, can realize cleaner production, meets the requirement of green metallurgical.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment one
Use silicone content to be raw material, major impurity composition Al content 1100ppmw wherein, Fe content 1620ppmw, Ca content 420ppmw as the metallurgical grade silicon of 98.5wt%.
Raw material is carried out crusher in crushing, ball mill ball milling, and adopt sieve apparatus that the metallurgical grade silica flour is sieved, obtaining silicon particle size is 150 purpose silica flour materials, adopts electromagnetic separator to remove with the iron contamination of bringing in the broken mechanical milling process then.
The hydrochloric acid that with concentration is 4mol/L is that 1: 1 amount is to react 5min under the ultrasonic wave effect of 800W at power to the silica flour material according to liquid-solid ratio, be to carry out acidleach under the 300W microwave action to handle 60min then at power, being placed on bath temperature then leached 5 days down for 50 ℃, in autoclave, reacted 2 hours at last, temperature of reaction is 110 ℃ in the autoclave, pressure is 2.5MPa, and stirring velocity is 300 rev/mins.Reacted material adopts vacuum filtration that acid solution and silica flour material are separated, and uses distilled water to clean 4 times, adopts extraction liquid to carry out extractive reaction reacted acid solution, to separate the metal ion in the acid solution.The acid solution that has extracted drops into after replenishing a certain amount of eo-acid in the acidleach experiment of a new round again; And add a spot of soda ash solution in the extraction liquid or sodium hydroxide solution is stripped, make that extraction liquid has also obtained recycling.Reduced by 96% through the iron contamination content after handling under three different conditions, the aluminium foreign matter content has reduced by 95%, impurity nickel content has reduced by 87%, the impurity titanium has removed 83%, it is that the hydrofluoric acid of 5mol/L is handled that silica flour material after treatment re-uses concentration, treatment time is 5 hours, can be with silicon-dioxide and some Impurity removal of particle surface, and use three grades of washed with de-ionized water 6 times.
Result of implementation: metallurgical grade silicon after treatment, its purity is 99.991%, wherein the content of iron contamination is 18ppmw, the content of aluminium impurity is 14ppmw, the content of calcium impurities is 8ppmw, and the content of titanium impurity is 15ppmw, and the total impurities of other metals is less than 15ppmw.
Embodiment two
Use silicone content to be raw material as the metallurgical grade silicon of 99.5wt%, its major impurity composition Al content is 540ppmw, and Fe content is 850ppmw, Ca content 200ppmw.
Raw material is carried out crusher in crushing, ball mill ball milling, and adopt sieve apparatus that the metallurgical grade silica flour is sieved, obtaining silicon particle size is 200 purpose silica flour materials, adopts electromagnetic separator to remove the iron contamination of bringing in the broken mechanical milling process then.
The nitric acid that with concentration is 8mol/L is that 5: 1 amount is carried out acidleach to the silica flour material and handled according to liquid-solid ratio.Be to handle 30min under the 600W ultrasonic wave condition at power earlier, under microwave condition, handle 40min then, microwave power is 600W, in 60 ℃ water-bath, leached 3 days then, adopt vacuum filtration that acid solution and material are separated then, and use distilled water to clean 4 times, be that the sulphuric acid soln of 4mol/L leaches under High Temperature High Pressure the silica flour material according to 5: 1 liquid-solid ratio with concentration then, after 10 hours, temperature of reaction is 190 ℃ in the autoclave, pressure is 0.3MPa, stirring velocity is 500 rev/mins, with vacuum filtration acid solution and silica flour material is separated, and uses three grades of washed with de-ionized water 4 times, adopt extraction liquid to carry out extractive reaction reacted acid solution, to separate the metal ion in the acid solution.The acid solution that has extracted drops into after replenishing a certain amount of eo-acid in the acidleach experiment of a new round again; And add a spot of soda ash solution in the extraction liquid or sodium hydroxide solution is stripped, make that extraction liquid has also obtained recycling.Reduced by 97% through the iron contamination content after handling under three different conditions, the aluminium foreign matter content has reduced by 93%, nickel impurity content has reduced by 85%, titanium impurity has removed 87%, it is that the hydrofluoric acid of 1mol/L is handled that silica flour material after treatment re-uses concentration, treatment time is 1 hour, can be with silicon-dioxide and some Impurity removal of particle surface, and use three grades of washed with de-ionized water 6 times.
Result of implementation: metallurgical grade silicon after treatment, its purity has reached 99.995%, wherein, the content of iron contamination is 10ppmw, and the content of aluminium impurity is 7ppmw, and the content of calcium impurities is 8ppmw, the content of titanium impurity is 3ppmw, and the total impurities of other metals is less than 5ppmw.
Embodiment three
Use silicone content to be raw material as the metallurgical grade silicon of 99.3wt%, its major impurity composition Al content is 930ppmw, and Fe content is 1320ppmw, Ca content 420ppmw.
Raw material is carried out crusher in crushing, ball mill ball milling, and adopt sieve apparatus that the metallurgical grade silica flour is sieved, obtaining silicon particle size is 100 purpose silica flour materials, adopts electromagnetic separator to remove the iron contamination of bringing in the broken mechanical milling process then.
The hydrochloric acid that with concentration is 3mol/L under ultrasonic wave condition is handled 5min earlier according to 8: 1 liquid-solid ratio to the silica flour material, its power is 500W, under microwave condition, handle 120min then, microwave power is 1000W, in 90 ℃ water-bath, leached 2 days then, adopt vacuum filtration that acid solution and material are separated then, be that the sulphuric acid soln of 2mol/L is to silica flour material acidleach 0.5h under High Temperature High Pressure with concentration then, temperature of reaction is 190 ℃ in the autoclave, pressure is 1.5MPa, stirring velocity is 700 rev/mins, then acid solution and silica flour material are separated with vacuum filtration, and use three grades of washed with de-ionized water 4 times, adopt extraction liquid to carry out extractive reaction reacted acid solution, to separate the metal ion in the acid solution.The acid solution that has extracted drops into after replenishing a certain amount of eo-acid in the acidleach experiment of a new round again; And add a spot of soda ash solution in the extraction liquid or sodium hydroxide solution is stripped, make that extraction liquid has also obtained recycling.Reduced by 98% through the iron contamination content after handling under three different conditions, the aluminium foreign matter content has reduced by 97%, nickel impurity content has reduced by 83%, titanium impurity has removed 85%, it is that the hydrofluoric acid of 3mol/L is handled that silica flour material after treatment re-uses concentration, treatment time is 8 hours, can be with silicon-dioxide and some Impurity removal of particle surface, and use three grades of washed with de-ionized water 6 times.
Result of implementation: metallurgical grade silicon after treatment, its purity has reached 99.991%, wherein, the content of iron contamination is 17ppmw, and the content of aluminium impurity is 13ppmw, and the content of calcium impurities is 10ppmw, the content of titanium impurity is 15ppmw, and the total impurities of other metals is less than 8ppmw.
Embodiment four
Use silicone content to be raw material as the metallurgical grade silicon of 99.0wt%, its major impurity composition Al content is 1030ppmw, and Fe content is 1430ppmw, Ca content 400ppmw.
Raw material is carried out crusher in crushing, ball mill ball milling, and adopt sieve apparatus that the metallurgical grade silica flour is sieved, obtaining silicon particle size is 300 purpose silica flour materials, adopts electromagnetic separator to remove the iron contamination of bringing in the broken mechanical milling process then.
The hydrochloric acid that with concentration is 1mol/L under ultrasonic wave condition is handled 180min earlier according to 10: 1 liquid-solid ratio to the silica flour material, its power is 800W, under microwave condition, handle 80min then, microwave power is 800W, in 70 ℃ water-bath, leached 4 days then, adopt vacuum filtration that acid solution and material are separated then, and use distilled water to clean 3 times, be that the sulphuric acid soln of 6mol/L is to silica flour material acidleach 12h under High Temperature High Pressure with concentration then, temperature of reaction is 150 ℃ in the autoclave, pressure is 1.0MPa, and stirring velocity is 600 rev/mins.The back separates acid solution and silica flour material with vacuum filtration, and uses three grades of washed with de-ionized water 4 times, adopts extraction liquid to carry out extractive reaction reacted acid solution, to separate the metal ion in the acid solution.The acid solution that has extracted drops into after replenishing a certain amount of eo-acid in the acidleach experiment of a new round again; And add a spot of soda ash solution in the extraction liquid or sodium hydroxide solution is stripped, make that extraction liquid has also obtained recycling.Reduced by 95% through the iron contamination content after handling under three different conditions, the aluminium foreign matter content has reduced by 98%, nickel impurity content has reduced by 87%, titanium impurity has removed 93%, it is that the hydrofluoric acid of 4mol/L is handled that silica flour material after treatment re-uses concentration, treatment time is 8 hours, can be with silicon-dioxide and some Impurity removal of particle surface, and use three grades of washed with de-ionized water 6 times.
Result of implementation: metallurgical grade silicon after treatment, its purity has reached 99.992%, wherein, the content of iron contamination is 12ppmw, and the content of aluminium impurity is 14ppmw, and the content of calcium impurities is 6ppmw, the content of titanium impurity is 17ppmw, and the total impurities of other metals is less than 11ppmw.
Embodiment five
Use silicone content to be raw material as the metallurgical grade silicon of 99.4wt%, its major impurity composition Al content is 850ppmw, and Fe content is 1220ppmw, Ca content 320ppmw.
Raw material is carried out crusher in crushing, ball mill ball milling, and adopt sieve apparatus that the metallurgical grade silica flour is sieved, obtaining silicon particle size is 250 purpose silica flour materials, adopts electromagnetic separator to remove the iron contamination of bringing in the broken mechanical milling process then.
The nitric acid that with concentration is 1mol/L under ultrasonic wave condition is handled 150min earlier according to 5: 1 liquid-solid ratio to the silica flour material, its power is 500W, under microwave condition, handle 50min then, microwave power is 1000W, in 60 ℃ water-bath, leached 5 days then, adopt vacuum filtration that acid solution and material are separated then, and use distilled water to clean 3 times, be that the hydrochloric acid soln of 6mol/L is to silica flour material acidleach 6h under High Temperature High Pressure with concentration then, temperature of reaction is 170 ℃ in the autoclave, pressure is 2.0MPa, and stirring velocity is 690 rev/mins.The back separates acid solution and silica flour material with vacuum filtration, and uses three grades of washed with de-ionized water 4 times, adopts extraction liquid to carry out extractive reaction reacted acid solution, to separate the metal ion in the acid solution.The acid solution that has extracted drops into after replenishing a certain amount of eo-acid in the acidleach experiment of a new round again; And add a spot of soda ash solution in the extraction liquid or sodium hydroxide solution is stripped, make that extraction liquid has also obtained recycling.Reduced by 98% through the iron contamination content after handling under three different conditions, the aluminium foreign matter content has reduced by 94%, nickel impurity content has reduced by 89%, titanium impurity has removed 85%, it is that the hydrofluoric acid of 2mol/L is handled that silica flour material after treatment re-uses concentration, treatment time is 6 hours, can be with silicon-dioxide and some Impurity removal of particle surface, and use three grades of washed with de-ionized water 6 times.
Result of implementation: metallurgical grade silicon after treatment, its purity has reached 99.993%, wherein, the content of iron contamination is 10ppmw, and the content of aluminium impurity is 8ppmw, and the content of calcium impurities is 10ppmw, the content of titanium impurity is 17ppmw, and the total impurities of other metals is less than 9ppmw.
Claims (5)
1. method for preparing super metallurgy grade silicon, it is characterized in that: after the operations such as the cleaning of block metallurgical grade silicon process, fragmentation, ball milling, screening, preliminary removal of impurities, putting into ultrasonic wave, microwave field carries out metallurgical acidleach and handles, adopt the normal pressure wet method to leach again and High Temperature High Pressure leaching combination through the metallurgical grade silica flour after the intensive treatment, make the metallic impurity in the metallurgical grade silica flour to enter as soon as possible in the leach liquor, leach liquor is through extraction back recycle, and extraction agent is also through the back recycle of stripping.
2. the method for preparing super metallurgy grade silicon according to claim 1 is characterized in that the major technology condition is:
(1) concentration of leach liquor: sulfuric acid concentration is 2mol/L～6mol/L, and concentration of hydrochloric acid is 0.5mol/L～8mol/L, and concentration of nitric acid is 1mol/L～8mol/L;
(2) the weight liquid-solid ratio when microwave treatment, ultrasonication is 1: 1～5: 1, and temperature is 40 ℃～90 ℃, and the treatment time is 0.5 hour～3 hours;
Weight liquid-solid ratio when (3) normal pressure leaches is 1: 1～10: 1, and temperature is 40 ℃～90 ℃, and the treatment time is 1 day～5 days;
Weight liquid-solid ratio when (4) High Temperature High Pressure leaches is 1: 1～8: 1, and pressure is 0.3MPa～2.5MPa, and temperature is 110 ℃～190 ℃, and the treatment time is 0.5 hour～12 hours;
(5) isolated silica flour was the hydrofluoric acid leaching of 1mol/L～5mol/L with concentration at last after High Temperature High Pressure leached, and the concentration of reaction solution is 1mol/L～5mol/L, 40 ℃～80 ℃ of temperature of reaction, and the reaction times is 1 hour～8 hours.
3. the method for preparing super metallurgy grade silicon according to claim 2 is characterized in that: described raw material is the metallurgical grade silicon of purity 98%～99.5%.
4. according to claim 2 or the 3 described methods that prepare super metallurgy grade silicon, it is characterized in that: described raw material is through after cleaning, being crushed to granularity is 50 orders～300 orders, preliminary removal of impurities is that the metallurgical grade silica flour after the screening is carried out magnetic separation, and iron and the iron oxide content brought in fragmentation, the mechanical milling process are reduced.
5. according to claim 2,3,4 described a kind of methods that prepare super metallurgy grade silicon, it is characterized in that: the inner lining material of the autoclave of using when High Temperature High Pressure leaches is metal titanium or resin.
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