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WO2008127120A1 - Procédé et équipement permettant la réaction de tétrachlorure de silicium avec du zinc pour produire du chlorure de silicium et de zinc pur - Google Patents

Procédé et équipement permettant la réaction de tétrachlorure de silicium avec du zinc pour produire du chlorure de silicium et de zinc pur Download PDF

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Publication number
WO2008127120A1
WO2008127120A1 PCT/NO2008/000127 NO2008000127W WO2008127120A1 WO 2008127120 A1 WO2008127120 A1 WO 2008127120A1 NO 2008000127 W NO2008000127 W NO 2008000127W WO 2008127120 A1 WO2008127120 A1 WO 2008127120A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
silicon
reaction
molten
reactor
Prior art date
Application number
PCT/NO2008/000127
Other languages
English (en)
Inventor
Per Bakke
Kåre KRISTIANSEN
Original Assignee
Norsk Hydro Asa
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Norsk Hydro Asa filed Critical Norsk Hydro Asa
Publication of WO2008127120A1 publication Critical patent/WO2008127120A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B61/00—Obtaining metals not elsewhere provided for in this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/033—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by reduction of silicon halides or halosilanes with a metal or a metallic alloy as the only reducing agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/04—Halides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/182—Details relating to the spatial orientation of the reactor horizontal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/19—Details relating to the geometry of the reactor
    • B01J2219/192—Details relating to the geometry of the reactor polygonal
    • B01J2219/1923—Details relating to the geometry of the reactor polygonal square or square-derived
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C22B34/1272—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process

Definitions

  • the present invention relates to a process and equipment for reacting silicon tetrachloride with zinc to produce silicon and zinc chloride.
  • the present invention aims to overcome the problems with the known solutions to produce silicon on the basis of reacting silicon tetrachloride with zinc.
  • the present invention is concerned with a novel continuous reactor for producing silicon where the process is characterized by the features as defined in the attached independent claim 1. Further the equipment is characterized by the features as defined in the attached independent claim 11. Preferred embodiments of the invention are defined in the dependent claims 2 - 10 and 12 - 17.
  • Fig. 1 A), B) shows a principal sketch of an equipment according to the invention seen in cross sectional side view A), and seen from the top, B).
  • Fig. 2 is a diagram showing the velocity as a function of the distance from a nozzle as is used according to the invention.
  • the present invention relates, as stated above, to a process and equipment in the form of a continuous reactor 1 for reacting silicon tetrachloride with liquid (molten) zinc to produce silicon and zinc chloride.
  • the process preferably operates at a constant temperature above the melting temperature of Zn (>419°C) and below the boiling temperature of ZnCI 2 (732 0 C), preferably 450-500 0 C,
  • the reactor 1 preferably consists, as is shown in Fig. 1 (A and B), a reaction or production chamber 2 with gutter or channel forming the reaction zone through which molten Zn flows slowly and a separation zone 3 where the reaction products Si, 4, Zn, 5, and ZnCI 2 , 6 are separated from Zn, 5 and may be removed.
  • SiCI 4 gas is injected into the liquid zinc bath 5.
  • an inert carrier gas such as argon, helium or nitrogen may be injected with the silicon tetrachloride gas to reduce the partial pressure of oxygen inside the reactor.
  • the jets 7 provided along the injection chamber 2 ensure a fine distribution of SiCI 4 , maximizing the gas metal contact area.
  • the jet nozzles are directed horizontally or slightly downwards in the liquid zinc bath to maximize the residence time of the SiCI 4 gas in the liquid thereby facilitating maximum conversion.
  • the fine bubbles of SiCI 4 are exposed to Zn the reaction occurs and the bubbles collapse, leaving fine droplets Of ZnCI 2 and Si particles behind.
  • the jet nozzles 7 may also be directed in the flow direction with an angle, ⁇ relative to the molten Zn indicated by the flow direction arrows 8, thereby providing a force to circulate the Zn and to bring the reaction products into the separation zone 3 of the reactor.
  • Several nozzles 7 can be located on each side of the reaction zone.
  • the jet nozzles can be operated independently which means that SiCI 4 concentrations and gas velocities through each nozzle can be adjusted for optimization of the system.
  • Zinc has a density of 7,1 g/cm 3 and Si with a density of 2,3 g/cm 3 floats on top.
  • ZnCI 2 has a density of approx. 2,9 g/cm 3 and constitutes a middle phase, which in practice may be difficult to separate from the fine Si particles.
  • a small amount of fluorides for example ZnF 2 , CaF 2 or KF can be added to the salt to change the interfacial tension between the molten salt and the Si particles.
  • KCI, CaCI 2 and NaCl can be added.
  • Salt (layer 9) may also be added to the surface to minimize contact between molten Zn and air.
  • the Si particles may be removed/recovered in a practical manner by some kind of sucking means (not shown) or mechanically by scraping the particles (neither not shown) off from the surface as a dross phase, possibly alongside fractions of ZnCI 2 other salt components and Zn. This can be done without stopping the process i.e. the injection of SiCI 4 .
  • the Si-enriched dross is transported to a separate furnace for melting and casting. During heating of the Si-enriched dross to above the melting temperature of Si, Zn and ZnCI 2 contaminants are efficiently evaporated and collected. The remaining fractions of Zn and ZnCI 2 phase can practically be removed from the continuous reactor after the removal of Si.
  • the adjacent ZnCI 2 phase may preferably be removed by some kind of pumping means (not shown) and for example transported to an electrolysis unit for separation into zinc and chlorine gas.
  • Zinc prepared from this process can be used as feed material in the process described in this invention.
  • Zn is circulated back to the inlet of the reactor (reaction zone). This can be achieved by introducing a partition wall 10 separating the reaction zone from the separation zone.
  • the partition wall 10 retains the phases floating on top while the heavier Zn phase flows under the partition wall.
  • Adition of molten Zn to replace the Zn consumed in the reaction and to maintain the metal level within an optimum window of operation can be done right after the partition walls as indicated by the arrow 11.
  • the size of respectively the production chamber 3 and reaction zone 2 is governed by the desired production rate, with the gas injection rate as a limiting factor. If the velocity of the gas is so large that it produces a turbulent jet, the jet grows at approximately 13 degrees half angle, regardless of velocity. Assuming a flat velocity profile in the jet the velocity as a function of the distance from the nozzle is shown in Fig. 2. It is seen that at approximately 60 nozzle diameters the average velocity is reduced to 0.001 of the nozzle velocity. With 5 mm nozzle diameter and a gas velocity of 330 m/s in the nozzle the average velocity is reduced by a factor of 1000 to 0,33 m/s at a distance of only 30 cm from the nozzle.
  • reaction products ZnCI 2 and Si are liquid and solid, respectively, and not gases. Hence the flow far away from the nozzle will be significantly less turbulent than if only inert gas is used, or if gaseous products had been formed during the reaction.
  • a SiCI 4 bubble with diameter of 1 cm (0.4 cm 3 ) will generate a ZnCI 2 droplet with a diameter of just 1.3 mm (0.9 mm 3 ) and a Si particle with diameter of only 0.6 mm (0.09 mm 3 ).
  • nozzles With a distance of 15 cm between the nozzles, 20 nozzles may be placed in the reaction zone 2 as indicated in Figure 1. Operating at for example 48O 0 C, it means that in a reaction zone with 4 m length, 50 cm width and 30-60 cm height of the molten Zn, corresponding to 4260-8520 kg Zn in the reaction zone, then 230 kg Si (0.1 m 3 ) and 2250 kg molten ZnCI 2 (0,77 m 3 ) will be produced per hour consuming 1080 kg Zn (0,15m 3 ). With 80% uptime the annual production of Si may be in the order of 1620 tonnes.
  • the separation zone 3 downstream of the reaction zone should provide a sufficient volume to allow separation of the reaction products by the action of gravity.
  • the volume of the separation zone should hold between 2 and 3 m 3 of salt and metal. With these volumes a suitable frequency for removal of SiVZnCI 2 and addition of Zn/salt can be once per hour.
  • the reduction of SiCI 4 with liquid Zn producing liquid ZnCI 2 is an exothermal reaction in which the reaction enthalpy ⁇ H is 72500 J/mol. This means that it may be necessary to remove heat to maintain a constant temperature during operation.
  • the reactor Before starting the process the reactor can be heated by electrical resistance from the outside (not shown in the figures), or by a heat exchanger medium (nether not shown) that can be used for heating while melting Zn, and removal of heat during operation.
  • the latter requires that the heat exchanger medium is heated externally to temperatures up to around 500 0 C, and then circulated in channels or in a cooling jacket in the walls of the reactor to give away the heat. Examples of such a heat exchanger medium can be a multi-component salt or molten gallium. If heating is done in a different way, water can be used for cooling. Induction heating should not be necessary.
  • the practical solution related to the heating and cooling is not shown in Fig. 1 , but is assumed to be none-inventive design matter for person skilled in
  • the reactor is preferably equipped with covers (not shown) to control the atmosphere inside the reactor. Off-gases can be sucked out through a channel over the reaction zone and any traces of SiCI 4 can in principle be condensed before the remaining off- gases are led to a scrubber. Inert gas can be injected through the nozzles or otherwise to reduce the partial pressure of oxygen. This may be used when the cover in the separation zone is opened for removal of Si and ZnC ⁇ .
  • the reaction zone 2 as shown in Fig. 1 A), B) is designed like a shallow U-shaped gutter or channel where the injection nozzles are provided along the length of the gutter from the partition wall 10 at one end 12 to the separation zone 3 at the other end 13.
  • the invention as defined in the claims is not limited to such design.
  • the reaction chamber may just be a straight, longitudinal gutter or channel, or it may be provided as part or section of a common chamber with the separation zone with a partition wall between.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne un procédé et un équipement permettant la réaction de tétrachlorure de silicium avec du zinc pour produire du chlorure de silicium et de zinc pur, la réaction s'effectuant dans un réacteur. Du gaz de tétrachlorure de silicium est injecté en continu à travers une ou des buses (7) dans un flux de zinc en fusion (5) dans une zone de réaction (2) du réacteur où la température est supérieure à la température de fusion du zinc (>419°C) et inférieure au la température d'ébullition du chlorure de zinc à une pression d'atmosphère 1 (732°C). Les produits réactionnels, du chlorure de silicium et de zinc sont recueillis dans une zone de séparation (3) à partir de laquelle ils peuvent être retirés. Le procédé et l'équipement selon la présente invention permet de produire efficacement et économiquement du silicium de haute pureté.
PCT/NO2008/000127 2007-04-11 2008-04-04 Procédé et équipement permettant la réaction de tétrachlorure de silicium avec du zinc pour produire du chlorure de silicium et de zinc pur WO2008127120A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO20071852 2007-04-11
NO20071852A NO20071852L (no) 2007-04-11 2007-04-11 Prosess og utstyr for reduksjon av silisium tetraklorid i sink for fremstilling av silisium med hoy renhet samt sinkklorid

Publications (1)

Publication Number Publication Date
WO2008127120A1 true WO2008127120A1 (fr) 2008-10-23

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Application Number Title Priority Date Filing Date
PCT/NO2008/000127 WO2008127120A1 (fr) 2007-04-11 2008-04-04 Procédé et équipement permettant la réaction de tétrachlorure de silicium avec du zinc pour produire du chlorure de silicium et de zinc pur

Country Status (3)

Country Link
NO (1) NO20071852L (fr)
TW (1) TW200906721A (fr)
WO (1) WO2008127120A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2415711A1 (fr) 2010-08-05 2012-02-08 Hycore ANS Procédé et appareil pour la préparation et la récupération de silicium à pureté élevée

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI471267B (zh) * 2011-10-12 2015-02-01 C S Lab In Technology Ltd Manufacture of high purity silicon fine particles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3743500A (en) * 1968-01-10 1973-07-03 Air Liquide Non-polluting method and apparatus for purifying aluminum and aluminum-containing alloys
GB2013248A (en) * 1978-01-30 1979-08-08 Kloeckner Humboldt Deutz Ag Refining molten metal
JPH1192130A (ja) * 1997-09-11 1999-04-06 Sumitomo Sitix Amagasaki:Kk 高純度シリコンの製造方法
WO2006100114A1 (fr) * 2005-03-24 2006-09-28 Umicore Procede de fabrication de si par reduction de sicu a l’aide de zn liquide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3743500A (en) * 1968-01-10 1973-07-03 Air Liquide Non-polluting method and apparatus for purifying aluminum and aluminum-containing alloys
GB2013248A (en) * 1978-01-30 1979-08-08 Kloeckner Humboldt Deutz Ag Refining molten metal
JPH1192130A (ja) * 1997-09-11 1999-04-06 Sumitomo Sitix Amagasaki:Kk 高純度シリコンの製造方法
WO2006100114A1 (fr) * 2005-03-24 2006-09-28 Umicore Procede de fabrication de si par reduction de sicu a l’aide de zn liquide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2415711A1 (fr) 2010-08-05 2012-02-08 Hycore ANS Procédé et appareil pour la préparation et la récupération de silicium à pureté élevée

Also Published As

Publication number Publication date
NO20071852L (no) 2008-10-13
TW200906721A (en) 2009-02-16

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