FR2571353A1 - Process for the production of silicon - Google Patents
Process for the production of silicon Download PDFInfo
- Publication number
- FR2571353A1 FR2571353A1 FR8415506A FR8415506A FR2571353A1 FR 2571353 A1 FR2571353 A1 FR 2571353A1 FR 8415506 A FR8415506 A FR 8415506A FR 8415506 A FR8415506 A FR 8415506A FR 2571353 A1 FR2571353 A1 FR 2571353A1
- Authority
- FR
- France
- Prior art keywords
- calcium
- silicon
- bath
- electrolysis
- molten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 25
- 239000010703 silicon Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000011575 calcium Substances 0.000 claims abstract description 23
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- -1 calcium halides Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 150000001669 calcium Chemical class 0.000 claims 1
- 230000005496 eutectics Effects 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 5
- 239000000374 eutectic mixture Substances 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 229910000882 Ca alloy Inorganic materials 0.000 description 3
- 229910004706 CaSi2 Inorganic materials 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 3
- 235000011148 calcium chloride Nutrition 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910021346 calcium silicide Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
LE PROCEDE CONSISTE A PROVOQUER LE DEPOT DU SILICIUM SUR L'ANODE PAR ELECTROLYSE DANS UN BAIN DE SELS FONDUS A BASE D'HALOGENURES DE CALCIUM, DE PREFERENCE EN MELANGE EUTECTIQUE, DANS LEQUEL LE SILICIUM EST DISSOUS SOUS FORME DE DERIVES AVEC LE CALCIUM. LE SILICIUM AINSI OBTENU SE CARACTERISE PAR UNE TRES HAUTE PURETE, NOTAMMENT EN CE QU'IL EST PRATIQUEMENT EXEMPT DES METAUX QUI LE CONTAMINENT HABITUELLEMENT.THE PROCESS CONSISTS OF CAUSING THE DEPOSIT OF THE SILICON ON THE ANODE BY ELECTROLYSIS IN A BATH OF MELT SALT BASED ON CALCIUM HALOGENIDES, PREFERABLY IN A EUTECTIC MIXTURE, IN WHICH THE SILICON IS DISSOLVED IN THE FORM OF DERIVATIVES WITH THE CALCIUM. THE SILICON SO OBTAINED IS CHARACTERIZED BY A VERY HIGH PURITY, ESPECIALLY IN THAT IT IS PRACTICALLY FREE OF METALS WHICH USUALLY CONTAMINATE IT.
Description
PROCEDE DE PRODUCTION DE SILICIUM
La présente invention se rapporte à un procédé de production de silicium de très haute pureté, par électrolyse dans un bain de sels fondus. Le silicium se dépose sur l'anode, en sorte qu'il est pratiquement exempt des métaux qui le contaminent habituellement.PROCESS FOR PRODUCING SILICON
The present invention relates to a process for producing very high purity silicon, by electrolysis in a bath of molten salts. The silicon is deposited on the anode, so that it is practically free from the metals which usually contaminate it.
On connaît des procédés de production de silicium par électrolyse ou par électro-raffinage, un bon exemple de ces procédés étant décrit dans l'exposé d'invention français nO 2 480 796. Dans ce procédé, qui s'applique au raffinage du silicium, du silicium est dissous dans un bain de sels fondus à base d'halogénures et de nitrures d'alcalins et/ou d'alcalino-terreux à partir d'une anode de silicium. Le silicium ainsi dissous se dépose sur la cathode en sorte que, même si cette opération de raffinage conduit à du silicium de haute pureté, on ne peut garantir qu'il soit exempt de traces de métaux, oui eux aussi se déposent à la cathode. Processes for the production of silicon by electrolysis or by electro-refining are known, a good example of these processes being described in the description of French invention No. 2,480,796. In this process, which applies to the refining of silicon, silicon is dissolved in a bath of molten salts based on halides and nitrides of alkali and / or alkaline-earth from a silicon anode. The silicon thus dissolved is deposited on the cathode so that, even if this refining operation leads to high purity silicon, it cannot be guaranteed that it is free of traces of metals, yes they too are deposited on the cathode.
I1 n'est pas besoin d'insister sur l'intérêt d'obtenir du silicium de très haute pureté, exempt de métaux, quand on sait que cet élément est un des constituants principaux de certaines mémoires et circuits électroniques. There is no need to insist on the advantage of obtaining silicon of very high purity, free of metals, when it is known that this element is one of the main constituents of certain memories and electronic circuits.
L'invention vise précisément à obtenir de très hautes puretés, sans métaux, en provoquant le dépôt du silicium sur l'anode.Le procédé se caractérise donc en ce qu' il consiste à provoquer le dépôt du silicium sur l'anode par électrolyse d'un bain de sels fondus à base d'haloaénures de calcium, dans lequel le silicium est dissous sous forme de dérivé avec le calcium. The invention aims precisely to obtain very high purities, without metals, by causing the deposition of silicon on the anode. The method is therefore characterized in that it consists in causing the deposition of silicon on the anode by electrolysis of 'a bath of molten salts based on calcium haloides, in which the silicon is dissolved in the form of a derivative with calcium.
Le dérivé du silicium avec le calcium, qu'on dissout dans le bain d'électrolyse, peut être du siliciure de calcium ou silicocalciumaSi2, qui est un produit métallurgique relativement courant. The derivative of silicon with calcium, which is dissolved in the electrolysis bath, can be calcium silicide or silicocalciumaSi2, which is a relatively common metallurgical product.
En ce qui concerne le bain d'électrolyse, on choisit les halogénures de calcium dans le groupe comprenant le chlorure, le fluorure de calcium et leurs mélanges De préférence, les mélanges sont des mélanges eutectiques. As regards the electrolysis bath, the calcium halides are chosen from the group comprising chloride, calcium fluoride and mixtures thereof. Preferably, the mixtures are eutectic mixtures.
On travaille à des températures de bain de sels fondus comprises entre 650 et 10000C, oû CaSi2 est soluble. We work at bath temperatures of molten salts between 650 and 10000C, where CaSi2 is soluble.
La concentration de ce dérivé dans le bain est généralement comprise entre 1 et 2% en poids.The concentration of this derivative in the bath is generally between 1 and 2% by weight.
On notera que le procédé selon l'invention permet également la production, à la cathode, de calcium de haute pureté. Le calcium étant soluble dans le bain d'électrolyse, ce bain se sature progressivement en calcium métal, ce qui -peut conduire à l'arrêt de l'électrolyse. It will be noted that the method according to the invention also allows the production, at the cathode, of high purity calcium. Since calcium is soluble in the electrolysis bath, this bath gradually becomes saturated with calcium metal, which can lead to the cessation of electrolysis.
Pour éviter ce processus, on travaille en continu selon le principe de la cathode liquide, c'est-à-dire que le calcium est déposé cathodiauement dans un métal fondu, par exemple du cuivre ou de l'étain. On évite ainsi que le calcium métal ne se dissolve dans le bain et n'arrête l'électrolyse. To avoid this process, one works continuously according to the principle of the liquid cathode, that is to say that the calcium is deposited cathodiauously in a molten metal, for example copper or tin. This prevents the calcium metal from dissolving in the bath and stopping the electrolysis.
Mentionnons encore que, aux températures de-travail indiquées ci-dessus et pour des bains consistant en des mélanges de chlorure et fluorure de calcium, les tensions à appliquer sont comprises entre 0,5 et 5 V. It should also be noted that, at the working temperatures indicated above and for baths consisting of mixtures of calcium chloride and fluoride, the voltages to be applied are between 0.5 and 5 V.
Le silicium obtenu, de façon anodique, se caractérise par un très haut degré de pureté et il e-st impossible d'y déceler, par les voies analytiques les plus sensibles utilisées à ce jour, de traces de contaminants métalliques classiques, tels que Fe, Al, Ca, Cu, Mg. The silicon obtained, in an anodic manner, is characterized by a very high degree of purity and it is impossible to detect there, by the most sensitive analytical methods used to date, traces of conventional metallic contaminants, such as Fe , Al, Ca, Cu, Mg.
L'invention sera illustrée dans les exemples ci-dessous, donnés à titre d'exemple. The invention will be illustrated in the examples below, given by way of example.
Exemple 1
On fond dans un creuset graphite d'un- diamètre de 10 cm et de hauteur de 30 cm, 2 kg d'un mélange de CaCl2 anhydre et CaF2 à 18 % de CaF2. Le mélange après fusion est porté à 7000C, et on ajoute de l'étain qui constitue une cathode fondue dans la partie inférieure du creuset. On ajoute ensuite en agitant du CaSi2 à raison de 2 % en poids. Puis on polarise le creuset négativement et on place une autre électrode en graphite à 3 cm environ de la cathode d'étain liquide. La différence de potentiel entre les électrodes est maintenue à 2,5 V pour une intensité totale de 200 A.Example 1
2 kg of a mixture of anhydrous CaCl2 and CaF2 containing 18% CaF2 are melted in a graphite crucible with a diameter of 10 cm and a height of 30 cm. The mixture after fusion is brought to 7000C, and tin is added which constitutes a molten cathode in the lower part of the crucible. CaSi2 is then added with stirring in an amount of 2% by weight. Then the crucible is polarized negatively and another graphite electrode is placed about 3 cm from the cathode of liquid tin. The potential difference between the electrodes is maintained at 2.5 V for a total intensity of 200 A.
Au cours de l'électrolyse, on ajoute environ 360 g de
CaSi2 à l'heure à raison de 30 g toutes les5 minutes. La masse d'étain liquide était au départ de 1200 q et à la fin de l'opération on a retiré un alliage de calcium et d'étain à 10,3 % de calcium.During electrolysis, approximately 360 g of
CaSi2 per hour at a rate of 30 g every 5 minutes. The mass of liquid tin was initially 1200 q and at the end of the operation, an alloy of calcium and tin containing 10.3% calcium was removed.
Le calcium est ensuite extrait par distillation sous vide de l'alliage calcium/étain. The calcium is then extracted by vacuum distillation of the calcium / tin alloy.
Le silicium a formé un dépôt compact sur l'anode. A 1' interface entre l'anode et le dépôt, on peut détecter la présence de carbure de silicium. The silicon formed a compact deposit on the anode. At the interface between the anode and the deposit, the presence of silicon carbide can be detected.
On récupère le dépôt de silicium sur l'anode et on constate que ce métal se trouve dans un état de pureté très élevé. The silicon deposit is recovered on the anode and it is found that this metal is in a very high state of purity.
En effet, aucune impureté métallique n'est décelable avec les moyens d'analyse à disposition ce jour. Indeed, no metallic impurity is detectable with the analytical means available today.
Dans les conditions indiquées ci-dessus, le rendement faradique est de 81 %
Exemple 2
Cn procède comme décrit à l'exemple 1, mais en utilisant du CaCl2 pur à 8000C. Under the conditions indicated above, the faradic yield is 81%
Example 2
Cn proceeds as described in Example 1, but using pure CaCl2 at 8000C.
On obtient ainsi du silicium de très haute pureté, comme précédemment, et un alliage de calcium et d'étain à 12,45 % de calcium, d'où le calcium peut être extrait par distillation sous vide. Very high purity silicon is thus obtained, as above, and an alloy of calcium and tin containing 12.45% calcium, from which the calcium can be extracted by vacuum distillation.
Claims (8)
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8415506A FR2571353B1 (en) | 1984-10-05 | 1984-10-05 | PROCESS FOR PRODUCING SILICON |
| BR8507254A BR8507254A (en) | 1984-10-05 | 1985-09-27 | PROCESS OF PRODUCTION OF CALCIUM OR HIGH PURITY CALCIUM ALLOYS |
| PCT/FR1985/000266 WO1986002108A1 (en) | 1984-10-05 | 1985-09-27 | Method for producing calcium or calcium alloys with high purity |
| EP85904824A EP0230411A1 (en) | 1984-10-05 | 1985-09-27 | Method for producing calcium or calcium alloys with high purity |
| US06/876,857 US4738759A (en) | 1984-10-05 | 1985-09-27 | Method for producing calcium or calcium alloys and silicon of high purity |
| FI871421A FI871421A0 (en) | 1984-10-05 | 1985-09-27 | FOERFARANDE FOER FRAMSTAELLNING AV SYNNERLIGEN REN KALCIUM ELLER KALCIUMLEJERINGAR. |
| AU50110/85A AU5011085A (en) | 1984-10-05 | 1985-09-27 | Method for producing calcium or calcium alloys with high purity |
| JP60504380A JPS62500527A (en) | 1984-10-05 | 1985-09-27 | Method for producing high-purity calcium or calcium alloy |
| PT81241A PT81241B (en) | 1984-10-05 | 1985-10-02 | PROCESS FOR PRODUCING CALCIUM OR ITS ALLOYS AND HIGH-PURITY SILICON OR GRAPHITE |
| ES547525A ES8608449A1 (en) | 1984-10-05 | 1985-10-03 | HIGH PURITY CALCIUM OR CALCIUM ALLOY MANUFACTURING PROCEDURE |
| NO862234A NO862234L (en) | 1984-10-05 | 1986-06-04 | PROCEDURE FOR PREPARING CALCIUM AND HIGH-PURITY Alloys. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8415506A FR2571353B1 (en) | 1984-10-05 | 1984-10-05 | PROCESS FOR PRODUCING SILICON |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2571353A1 true FR2571353A1 (en) | 1986-04-11 |
| FR2571353B1 FR2571353B1 (en) | 1987-02-13 |
Family
ID=9308504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8415506A Expired FR2571353B1 (en) | 1984-10-05 | 1984-10-05 | PROCESS FOR PRODUCING SILICON |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS62500527A (en) |
| FR (1) | FR2571353B1 (en) |
-
1984
- 1984-10-05 FR FR8415506A patent/FR2571353B1/en not_active Expired
-
1985
- 1985-09-27 JP JP60504380A patent/JPS62500527A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 99, no. 4, juillet 1983, page 463, no. 29947u, Columbus, Ohio, US; G.M.RAO et al.: "Electrolytic production of silicon" * |
| EXTENDED ABSTRACTS, vol. 81-2, octobre 1981, pages 1130-1131, no. 468, Pennington, New Jersey, US; J.M.OLSON et al.: "Electrowinning of silicon using a molten tin cathode" * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62500527A (en) | 1987-03-05 |
| FR2571353B1 (en) | 1987-02-13 |
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| ST | Notification of lapse |