TW200906721A - Process and equipment for reacting silicon tetrachloride with zinc to produce pure silicon and zinc chloride - Google Patents

Abstract

A process and equipment for reacting silicon tetrachloride with liquid zinc to produce silicon and zinc chloride the reaction taking place in a reactor (1). Silicon tetrachloride gas is injected continuously through one or more nozzles (7) into a flow of molten zinc (5) in a reaction zone (2) of the reactor where the temperature is above the melting temperature of zinc ( > 419DEG C ) and below the boiling temperature of zinc chloride at 1 atmosphere pressure (732DEG C ). The reaction products, silicon and zinc chloride are collected in a separation zone (3) from which they may be removed. Silicon with high purity is effectively and cheaply produced by the present inventive process and equipment.

Description

200906721 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method and apparatus for the reaction of ruthenium tetrachloride with rhodium ruthenium to produce ruthenium and chlorination. [Prior Art] As mentioned in International Patent Application No. WO2006/1001, No. 1 101 1925, and No. 1,092,130, the reaction of ^(^ with Ζη can be carried out in a batch reactor involving the injection of gaseous SiC into excess In liquid Zn, the ZnC12 in the gas phase is simultaneously removed, followed by evaporation of Zn, followed by melting/casting of Si. The obvious lack of these methods is that all of them are batch processes, and the injection and evaporation steps are very time consuming. In addition, the large temperature range of 450-1450 C makes a strong demand for the material of such reactors. Furthermore, U.S. Patent Nos. 2773745, 28〇4377, (4) Sichuan and 3041 145 illustrate the gas. The method of reducing (10) 4 in the phase is a method which is more difficult to develop into an industrial scale. SUMMARY OF THE INVENTION The object of the present invention is to overcome the above problems by a known solution in the reaction of tetrachlorinated 7 Manufacture on the basis of the above [Therefore, the novel continuous reactor used to make bismuth in this species, in the separate item of 纟莽^ attached, is bounded by the characteristics of the patent in the scope of patent (1): the device is attached by the independence Patent application The preferred embodiment of the present invention is defined by the following description: 2] 〇 and 12 _ 17 巾. 蜀 甲 6 6 6 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 A method and apparatus for reacting cerium chloride with liquid (melt) zinc to produce cerium and zinc hydride in the form of a continuous reactor 1. The sigma method is preferably at a melting point above Zn (> 4 丨 9. 〇) and lower than the boiling point of ZnCl2 (732. 〇, operating in a constant temperature mode, preferably 450-50 (TC, as shown in Figure 1 (A and B), preferably, reactor The i is composed of the reaction chamber or the generating chamber 2, and the separation zone 3: f, wherein the generating chamber has a reaction zone formed by a groove or a pipe, so that the molten Zn can slowly flow through the reaction product Si4, & ” mouth znc, 6 by

It is separated at Zn 5 and can be removed. The μ gas can be injected into the liquid zinc bath 5 via a jet nozzle 7 located at the bottom or wall of the reaction zone 2. Optionally, an inert carrier gas, such as argon, helium or nitrogen, may be injected with the four gas cut gas to reduce the partial pressure of oxygen inside the reactor. The jet stream 7 disposed along the injector chamber 2 can be well distributed. The spray:: the body has the largest contact area with the metal. Further, in the liquid zinc bath, the direction of the liquid ill is horizontal or slightly downward, so that the residence time of the gas is maximized, thereby contributing to the maximum conversion. However, the fine bubbles of S i C14 言 rupture, and leave zJ: ', then the reaction begins, and the nozzle 7 can also drop to the Si particles. The jet stream is fed into the direction of the melting angle indicated by the direction 8 of the other head, and the reaction product is loaded with two kinds of force to circulate the Zn, and the sides can be detached. towel. In the reaction zone, that is, two = a plurality of .... The jet nozzles can be operated independently, and the system is optimized by the SiCU degree of each nozzle and the gas flow rate of the 200906721 system. In the eight Q & knives away from zone 3 downstream of reaction zone 2, the product - liquid ZnCl2 6 and solid Si 4 can be separated from the excess Zn 5 by the difference in (four) degrees. The density of zinc is 7.lg/em3^si and the density is 23_3, :/ is at the top. The density of ZnCl2 is about 29 cores 3 to constitute an intermediate phase, and it is actually difficult to separate it from the Si fine particles. To overcome this problem, a small amount of fluoride, such as ZnF2, CaF25l KF, may be added to the salt to change the interfacial tension between the molten salt and the Si particles. In order to further modify the properties of the salt, KCl, CaC...aC1 may be added. Salt (; 9 ) can also be added to the surface to minimize contact between the fused Zn and the wire. #based on continuity, or at a particular frequency, by some sort of suction device (not shown), or by moving the particles from the surface (also not shown), and possibly together with other salt ingredients called 2 The scum layer is formed together with the portion of ^, and the Si particles are actually removed/recovered. This step can be carried out under the condition that the program of the money, that is, the sicu program is stopped. The scum contained therein is sent to a separation furnace to be melted and washed. During the heating of the Si-rich scum to the melting temperature of Si, it is effective to evaporate the Zn and Ζαα2 impurities and collect them. After the Si is removed, the remaining 2' and Zncl2 phases can actually be removed from the continuous reactor. After removing the Si-rich scum phase from the separation zone, preferably by Some pumping means (not shown) remove the adjacent ZnCl2 phase and, for example, can be transported to the electrolysis unit to separate it into zinc and chlorine. The zinc prepared by this method can be used in the present invention. The method described is used as the material for the 200906721.

The step of Zn being separated from the separation zone by the separation zone and passing back to the reactor (reaction zone) can be achieved by introducing the partition wall 1n to receive α = 10 to separate the reaction zone from the separation zone. The partition 10 retains the phase which is floating on the buttocks & 1 reversed on page 4, while the heavier twisted phase is moved in the next wall. As indicated by the arrow ", the addition of 炫ηΖ to replace the Ζη′ consumed in the reaction and maintaining the optimum metal level in the operating window can be completed after the partition. In the case where the gas injection rate is used as a limiting factor, the magnitude of t 3 and the reaction zone 2 can be separately controlled by the desired production rate. If the flow rate of the gas is too large to generate a spoiler jet, the jet μ grows at a half angle of about 13 degrees regardless of the speed. Assuming a flat velocity profile in the jet, the velocity is a function of the distance from the nozzle tip as shown in Figure 2. It can be seen from the figure that the average speed is reduced to 〇 〇〇 1 of the original nozzle speed with a nozzle diameter of about 6 〇. When the nozzle has a diameter of 5 mm and the gas flow rate in the nozzle is 330 m/s, the average speed is reduced by 1000 times to 0.33 m/s at a distance of only 3 距 from the nozzle. It should also be noted that the reaction products ZnC 2 and Si are liquids and solids, respectively, rather than gases. Therefore, if only an inert gas is used, or if a gaseous product has been produced during the reaction, the fluid far from the nozzle is clearly less disordered. At 4 8 〇X: and the pressure is equivalent to 30 cm Ζη, the Sicm4 bubble (〇.4 cm3) with a diameter of i cm will produce ZnCl2 droplets (0,9 mm3) with a diameter of only 1.3 cm and diameter only It is a 0.6 mm Si particle (〇.〇9 mm3). As shown in Fig. 1, when the distance between the nozzles is 15 cm, 20 nozzles can be provided in the reaction zone 2. When operated at, for example, 480 ° C, 8 200906721 曰 is in the reaction zone of molten Zn having a length of 4 m, a width of 50 em and a height of 30-60 cm, which corresponds to 4260 in the reaction zone. 8520 kg of Zn, then 230 kg of Sl (0.1 m3) and 2250 kg of molten ZnCl2 (0.77 at 8 〇/°) with an hourly consumption of 1080 kg zn ( 015 m3) Under normal operating time, the annual production of Si can reach the volume of 1620. The common pg* + good knife away & 3 downstream of the reaction zone should have sufficient volume to allow the reaction product to be 3 by gravity. Separation. The volume of the separation zone should be maintained between 2 ^ ι and the metal. Under such a volume, the appropriate frequency for removing Si/ZnCl2 and adding Zn/salt is once per hour. The reduction of SiCl4 produces liquid ZnCl2 as an exothermic reaction, and the second reaction heat; t3 H is 725GG "m. This means that it may be necessary to keep the heat in the process of maintaining the normal temperature. Before the start of the program, The borrower uses thermoelectric p from the outside and (not shown in the figure), or by using::heat' at the same time The heat exchange of the Zn and the heat removal of the Zn is carried out. The latter is heated to a temperature of up to about 5 Torr. Circulation in the scoop or cooling jacket in the reactor wall to remove heat. An example of such a heat exchanger medium can be multi-component salt or smelting. If it is to be heated in different ways 'The water can be used for cooling. Inductive heating should not be required. The actual solution for heating and cooling is not shown in Figure 1. For the heat technician, it should be assumed to be a non-inventive design. The car 乂 佳 and δ 'reactor should be equipped with a casing (not shown) to control the anti-2009 200906721 internal g-γ-, -, Qiaoqi. The exhaust can be sucked through the pipe above the reaction zone. In addition to, and in principle, any traces of SlCl4 can be condensed before directing the residual exhaust to the scrubber. The inert gas can be injected via a nozzle or other means to reduce the partial pressure of oxygen. When the casing in the separation zone is opened For removing Si and Znci2 This method can be used. As shown in Figures 1 A) and B), the reaction zone 2 is designed as a shallow u-shaped groove or in the pipe. The main injection nozzle is located along the partition 10 at the end point 12 to the other end. The groove length of the separation zone 3 of the point 13 is set. However, the invention as defined in the scope of the claims is not limited to such a design. Thus, the reaction chamber can be exactly a straight, longitudinal groove or conduit, or it can be, in general, a portion or region of the chamber having a separation zone with a partition therebetween. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be further illustrated by the following examples and with reference to the following drawings in which: Figure 1 A), B) shows a schematic view of a device according to the invention, the cross-sectional side view of which is A) The top view is b). Figure 2 is a graph showing the speed as a function of the distance of the nozzle used in accordance with the present invention. [Main component symbol description] Figure 1 A) 1 Reactor 2 Reaction zone or chamber or reaction chamber or production chamber 3 Separation zone or production chamber 200906721 4 Si 5 Zn or liquid bath or molten zinc 6 ZnCl2 7 Jet nozzle or nozzle Or Jet 8 Directional Arrow 9 Salt 10 Partition Figure 1 B) 1 Reactor 2 Reaction zone or chamber or reaction chamber or chamber or trench or pipe 3 Separation zone or chamber 4 Si 5 Zn or liquid zinc bath or molten zinc 6 ZnCl2 7 jet nozzle or nozzle or jet 8 direction arrow 9 inlet 10 partition 11 arrow or inlet 12 upper end or end point 13 downstream end or end point 11

Claims (1)

200906721 X. Application for Patent Park: 1 · ~ A method for the reaction of tetragassing hydrazine with liquid zinc to produce bismuth and zinc chloride 'The reaction is carried out in reactor (1), characterized by one or more The nozzle (7) continuously injects helium tetrachloride gas into the molten zinc stream (5) in the reaction zone (2) of the reactor, wherein the temperature in the reactor is higher than the melting point of the word (&gt;419 ° C) It is lower than the point of vaporization of zinc oxide at i atmosphere (732 ° C), wherein the reaction product strontium and zinc chloride are collected in the separation zone (3). 2. The separation zone (3) prepared according to the method of claim i is directly connected to the reaction zone. 3. The method according to the scope of the patent application, characterized in that the reaction product monofilament particles and molten zinc chloride are removed from excess zinc in the separation zone located downstream of the reaction zone in a continuous or semi-continuous manner. 4. The method according to any one of clauses 1-5 to 3 of the patent application, characterized in that the unreacted zinc is accompanied by an additional addition to replace the molten zinc which is consumed in the reaction of the four gas fossils. A method of recycling back to the reaction zone into the -β τ I process, which is characterized by a fine gas interception injected by a nozzle (7) on the bottom or wall of the equipment (1). ~~(2) Μ艮射请专利范(四)丨 to 3 is characterized by injecting tetrachloride into a turbulent jet at a high speed. 7. According to the patent application, any feature of items 3 to 3 is through melting and melting. The method of zinc flow 7 item, the door angled (α) nozzle will be four 12 200906721 ' thus providing a force to circulate the molten zinc and carry the reaction product - 矽 particles and vaporized zinc to the separation zone of the reactor in. The method according to any one of claims 1 to 3, characterized in that, by being disposed on the wall of the reaction zone and at an angle to the flow direction of the molten remarks (〇〇# nozzle injects tetrachloride, thereby providing A force to circulate the melt and carry the reaction product into the separation zone of the reactor. 9. The method according to claims 1 to 3, characterized in that the temperature of the molten zinc is preferably in the range of 450 to 500. The method according to any one of claims 1 to 3, characterized in that zinc, potassium, or sodium I compounds or a mixture of two or more of these compounds is added to zinc chloride to improve Separating from vaporized zinc and material. U. According to the method of any one of items 1 to 3 of the special (4), characterized by adding zinc, #, unloading or nano-chloride or two or more of these vapors. The mixture prevents oxidation of the molten zinc and improves the separation of the salt phase from the salt phase. 12. A device for reacting tetragassing hydrazine with liquid zinc to produce hydrazine and zinc chloride, the reaction being carried out in a reactor, characterized in that The reactor 〇) is a continuous type 4 comprising a reaction or production chamber (2) having compartments through which the molten enthalpy flows slowly while simultaneously injecting four gasified ruthenium into the molten ruthenium and the reaction product Si Separation zone (4) in which Ζη and ZnCl2 are separated and can be removed. 13. The device according to item 2 of the patent application is characterized in that the reaction zone (2) is in the form of a pipe or a groove. 14. The device according to any one of the patents of the present invention, which is characterized in that it is characterized by a jet nozzle (7) equipped with a full length of the s-channel or the groove (2). Gas cutting injection. ^ The device according to any one of the items 12 to 13 of the patent application is characterized in that the pipe biting groove is separated from the zone, and the upper end (12) is connected to the branch with a partition wall (also associated with the separation zone). (3) 磕, 丹卜游螭 C 13) by the groove or pipe (2 to make ^ ΖΠ together with the generated dream into the separation zone (3). The upper end (12) flows to the downstream end (13) and enters 1M Any of the 12th to 13th patents is characterized in that it is provided with a nozzle (7) such that J is placed, or the pipe (7) is angled (α) to promote the jet flow and the groove β < α) to promote melting &amp; The flow of the dip, and the flow into the separation zone (3). (13) 17. According to the scope of claims 12 to 13 of the patent application, the upper end of the pipe or the groove is provided with a device of "9", respectively supplying salt and Ζη. 1 1 ) by A according to the scope of patent application 12 Any of the 13 items that are characterized by a reactor, the Japaneses are sealed by a casing and separated from the cat by the casing, and there is a suction device to remove any waste or particles. Page 14