TW201406966A - Method of recovering elemental metal from polycrystalline semiconductor production - Google Patents

Abstract

A method includes the step of introducing hydrogen and a silane-containing feed gas that comprises trichlorosilane into one or more decomposition reactors that contain a polycrystalline silicon seed substrate. The trichlorosilane and hydrogen are reacted to form polycrystalline silicon in the decomposition reactor. A gaseous stream that comprises silicon tetrachloride is exhausted from the one or more decomposition reactors. The gaseous stream and a source of elemental metal that is reactive with the silicon tetrachloride is fed into a recovery reactor. The silicon tetrachloride and the elemental metal are reacted to produce polycrystalline silicon and a first composition that comprises metal chloride. Elemental metal is recovered from the metal chloride in the first composition through at least one of (1) subjecting the first composition comprising the metal chloride to hydrogenation to produce elemental metal and hydrogen chloride, or (2) reacting the metal chloride in the first composition and elemental silicon.

Description

Method for recovering elemental metal from polycrystalline semiconductor process [Cross-quote of related applications]

The present application claims priority to U.S. Provisional Patent Application Serial No. 61/667,145, filed on Jan.

The present invention is basically directed to a method of recovering elemental metals from a semiconductor process. More specifically, the present invention relates to a method of recovering elemental metals from metal chlorides produced during semiconductor processing.

It is known that polycrystalline germanium can be formed by various methods. One method for forming polycrystalline germanium involves the decomposition of decane. In this method, a feed gas comprising a mixture of hydrogen and decane (SiH ₄ ) or a mixture of hydrogen and trichloromethane is fed to a substantially rod (in a Siemens reactor) or pellet (in a stream) In a decomposition reactor of a polycrystalline germanium seed substrate in the form of a chemical bed reactor, the polycrystalline germanium seed substrate is maintained at a temperature above 1000 °C. The ruthenium will deposit on the polycrystalline cerium seed substrate while the byproduct gas mixture will exit with the effluent stream. When a mixture comprising hydrogen and trichloromethane is used, such as in the Siemens process, the exhaust stream may comprise hydrogen, hydrogen chloride, chlorodecane, decane and tantalum powder. For the purposes of this application, the term "chloromethane" means any decane species having one or more chlorine atoms bonded to hydrazine and includes, but is not limited to, monochlorodecane (H ₃ SiCl), dichloromethane ( H ₂ SiCl ₂ ), trichlorodecane (HSiCl ₃ ), ruthenium tetrachloride (SiCl ₄ ), and various dioxane chlorides (such as hexachlorodioxane and pentachlorodioxane). In the effluent stream, hydrogen and chlorodecane (such as ruthenium tetrachloride and trichloromethane) are derived from the unreacted feed gas and the reaction product from the decomposition reaction. The effluent stream typically undergoes a complex recovery process in which condensation, scrubbing, absorption, and adsorption are commonly used to assist in the capture of unit operations for recycle of trichloromethane, hydrogen, and/or dilute (e.g., inert) gases.

Although the Siemens method can be used to form electronic grade polysilicon, the Siemens method has a problem in that it is difficult to achieve high polycrystalline germanium yield from the feed due to the chemical equilibrium and kinetics of the reaction.

Another method for producing polycrystalline germanium is the zinc reduction of ruthenium tetrachloride. In particular, the zinc reduction process of antimony tetrachloride involves feeding hafnium tetrachloride and elemental zinc into a fluidized bed reactor, thereby producing polycrystalline germanium and zinc chloride. Although the zinc reduction method of antimony tetrachloride can also be used to form advanced polycrystalline germanium, this method requires treatment of zinc chloride by-products and recovery of zinc therefrom. However, recent developments in zinc recovery technology have improved the prospects for polycrystalline germanium by zinc reduction of ruthenium tetrachloride.

In view of the above, there is still an opportunity to provide an improved method for recovering elemental metals from the polysilicon process.

The present invention provides a process comprising the steps of introducing hydrogen and a decane-containing feed gas comprising trichloromethane into one or more decomposition reactors comprising a polycrystalline germanium seed substrate. The chlorosilane is reacted with hydrogen in a decomposition reactor to form polycrystalline ruthenium. A gaseous stream comprising ruthenium tetrachloride is withdrawn from one or more decomposition reactors. A gaseous stream and an elemental metal source reactive with ruthenium tetrachloride are fed to the recovery reactor. The antimony tetrachloride reacts with the elemental metal to produce polycrystalline germanium and a first composition comprising the metal chloride. The elemental metal is recovered from the metal chloride in the first composition by at least one of the following: 1) hydrogenating the first composition comprising the metal chloride to produce an elemental metal and hydrogen chloride, or 2) making the first combination The metal chloride in the substance reacts with the element hydrazine.

Produced by reacting polycrystalline germanium by decomposition of trichlorosilane in a decomposition reactor (such as a Siemens reactor) with ruthenium tetrachloride in a gaseous stream discharged from zinc in the presence of a self-decomposing reactor The combination of polycrystalline ruthenium methods increases the yield of polycrystalline germanium from the feed to the decomposition reactor while consuming the components present in the gaseous stream exiting the decomposition reactor. In addition, by recovering the elemental metal from the metal chloride in the first composition, the recovered elemental metal can be recycled into the process to effectively achieve a closed circuit process, thereby minimizing the volume of the waste stream and maximizing the polysilicon as much as possible. Yield.

10‧‧‧ Equipment

12‧‧‧heating area

14‧‧‧temperature control zone

16‧‧‧Cooling area

18‧‧‧Tray

20‧‧‧ side wall

22‧‧‧Perforation

24‧‧‧ collection room

Other advantages of the present invention will be readily understood and better understood by reference to the following detailed description in which <RTIgt; Step: producing trichlorosilane, decomposing trichloromethane, reacting antimony tetrachloride with elemental metal (for example, zinc), recovering elemental metal from metal chloride, and recycling elemental metal and antimony tetrachloride to tetrachlorinate Figure 2 is a schematic flow diagram showing an embodiment of the process of the present invention, the process comprising the steps of: producing trichlorodecane, decomposing trichloromethane, and causing antimony tetrachloride and elemental metal (for example, zinc) reaction, recovery of elemental metal from metal chloride, recycling of elemental metal to the step of reacting antimony tetrachloride with elemental metal; and recycling of HCl to the step of producing trichloromethane; 3 is a schematic diagram of a reactor that can be used to recover elemental metals in accordance with one embodiment of the process of the present invention.

The present invention provides a method for producing polycrystalline germanium substantially by combining: 1) reacting hydrogen with trichloromethane in one or more decomposition reactors, and 2) discharging one or more decomposition reactors The ruthenium tetrachloride in the gaseous stream is reacted with the elemental metal in one or more recovery reactors. By providing a gaseous stream that is discharged from one or more decomposition reactions In the case of ruthenium tetrachloride, the yield of polycrystalline germanium (basically, high quality (such as solar grade 矽) can be increased.

The process of the present invention comprises the step of producing a decane-containing feed gas comprising trichloromethane intended for use in the manufacture of polycrystalline germanium, as indicated by numeral 30 in Figures 1 and 2. A known technique in the art for producing trichloromethane is a direct process involving the reaction of hydrogen chloride with a source of helium to form a chlorodecane such as trichloromethane and ruthenium tetrachloride. The direct process involves the use of a fluidized bed reactor and can be a continuous process. The ruthenium tetrachloride produced by the direct process, the unreacted feed gas such as HCl, the particles entrained in the product stream, and other reaction product gases other than trichloromethane may be separated from the product stream to produce decane-containing gas. The gas is fed to one or more decomposition reactors. Alternatively, the decane-containing feed gas obtained and intended to be fed to one or more decomposition reactors may still contain some unseparated gaseous products, such as ruthenium tetrachloride.

As mentioned above, the method comprises the steps of introducing hydrogen and a decane-containing feed gas comprising trichloromethane into one or more decomposition reactors, as indicated by numeral 32 in Figures 1 and 2. The decomposition reactor contains a polycrystalline germanium seed substrate. For example, a Siemens reactor is typically used as a decomposition reactor containing a polycrystalline germanium seed substrate in the form of a polycrystalline twin seed. Alternatively, a fluidized bed reactor is used as the decomposition reactor, in which case the polycrystalline seed crystal substrate is in the form of polycrystalline seed particles.

The Siemens reactor used herein is a conventional Siemens reactor. For example, the Siemens reactor can be operated as follows. The polycrystalline twin seed rods were placed vertically and parallel to each other in a Siemens reactor. Two or more of the seed rods may be joined to each other by a bridge, thereby forming a U-shaped rod. The U-shaped rod is heated until it reaches a temperature ranging from about 700 ° C to about 1,400 ° C, from about 1,000 ° C to about 1,200 ° C or from about 1,100 ° C to about 1,150 ° C. The Siemens reactor can be operated at a pressure ranging from about 13 kPa (2 psig) to about 3450 kPa (500 psig), from about 6 kPa (1 psig) to about 1380 kPa (200 psig), or from about 100 kPa (1 bar) to about 690 kPa (100 psig).

The decane-containing feed gas is typically fed to the Siemens reaction via an inlet in the base Device. As noted above, the decane-containing feed gas comprises hydrogen and trichloromethane, and typically comprises from about 5% to about 75% trichlorodecane. The decane-containing feed gas may comprise from about 0.015 moles of trichloro decane/mole hydrogen to about 0.3 moles of trichloro decane/mole hydrogen. Alternatively, the decane-containing feed gas may comprise from about 0.03 moles of trichlorodecane/mole hydrogen to about 0.15 moles of trichlorodecane/mole hydrogen. As also noted above, the decane-containing feed gas may further comprise ruthenium tetrachloride as desired.

The process of the present invention further comprises the step of reacting trichloromethane with hydrogen in a decomposition reactor to produce polycrystalline hydrazine. When the one or more decomposition reactors are Siemens reactors, under the above temperature and pressure conditions, helium will be deposited on the U-shaped rod from the decane-containing feed gas, thereby increasing the diameter of the U-shaped rod. Without wishing to be bound by theory, it is believed that from about 5% to about 50%, or from about 20% to about 50%, of polycrystalline germanium product from the Siemens reactor based on the total amount of rhodium contained in the decane-containing feed gas. the amount.

The method further includes the step of discharging a gaseous stream comprising ruthenium tetrachloride from one or more decomposition reactors. In particular, ruthenium tetrachloride is the product of the decomposition reaction and is therefore produced in one or more decomposition reactors. Cerium tetrachloride may also be present in the decane-containing feed gas introduced into one or more decomposition reactors. The gaseous stream exiting one or more decomposition reactors can be fed directly to one or more recovery reactors to recover the ruthenium from the ruthenium tetrachloride, as shown by numeral 34 in Figures 1 and 2, and can be fed directly to One or more recovery reactors are not subjected to an intermediate treatment step (there is no unit operation between one or more decomposition reactors and one or more recovery reactors). Alternatively, the gaseous stream exiting one or more of the decomposition reactors can be treated to remove certain materials and then fed to one or more recovery reactors. For example, the fine gas powder, dioxane or may be removed by feeding the discharged gaseous stream through a dedusting device cooled by a fluid such as industrial water to treat the gaseous stream exiting the one or more decomposition reactors. Its combination.

The ruthenium tetrachloride is reacted with the elemental metal in one or more recovery reactors to produce polycrystalline ruthenium and a first composition comprising the metal chloride. More specifically, the ruthenium tetrachloride in the discharged gaseous stream is reacted with elemental metals to produce high purity ruthenium. Elemental metal optional A group consisting of zinc, copper, aluminum, magnesium, sodium, and the like. The reaction can be carried out by gas phase reaction of a hafnium tetrachloride gas with an elemental metal gas as is known in the art. Specifically, the reaction of ruthenium tetrachloride with an elemental metal can be carried out by reacting a ruthenium tetrachloride gas with a zinc gas in a recovery reactor having a temperature of from about 800 to about 1200 ° C or from about 900 to about 1000 ° C. Under these conditions, the ruthenium tetrachloride gas easily reacts with the zinc gas. The pressure within the recovery reactor is, for example, from about 0 to about 1723 kPa. As described above, the polycrystalline ruthenium is produced by the reaction of ruthenium tetrachloride with an elemental metal. The polycrystalline germanium is generally of high purity and is considered a solar grade germanium by those skilled in the art. Another result is a first composition comprising a metal chloride which is a by-product of the reaction. When zinc is used as the elemental metal, the by-product is zinc chloride as shown in the following reaction formula.

SiCl ₄ +2Zn→Si+2ZnCl ₂

After the polycrystalline germanium is produced, the first composition remaining in one or more of the recovery reactors contains metal chlorides and may also contain elemental metals, antimony tetrachloride, and the like. The metal chloride can be separated and recovered in liquid form by lowering the temperature to the boiling point of the metal chloride or lower. The elemental metal may be recovered in the form of a powder or liquid metal and may be recycled to one or more recovery reactors. The residual ruthenium tetrachloride can also be recycled to one or more recovery reactors.

The method of the present invention further comprises the step of recovering the elemental metal from the metal chloride in the first composition by at least one of the following, as indicated by numerals 36 and 38 in Figures 1 and 2: 1) comprising metal chloride The first composition of the compound is hydrogenated to produce an elemental metal and hydrogen chloride; or 2) the metal chloride in the first composition is reacted with elemental hydrazine.

Recovering elemental metals from metal chlorides in the first composition by hydrogenation to produce elemental metals and hydrogen chloride

According to the process of the present invention, and as shown in Fig. 2, the metal chloride present in the first composition is hydrogenated. As shown in the following reaction formula, when the metal chloride is zinc chloride, hydrogen chloride and zinc are produced.

ZnCl ₂ +H ₂ →Zn+2HCl

The reduction of zinc chloride with hydrogen is generally carried out at a temperature of from about 700 to about 1500 ° C, from about 800 to about 1400 ° C, or from about 900 to about 1300 ° C. The reduction reaction hydrogen to molar ratio of zinc chloride is from about 2:1 to about 200:1, or from about 5:1 to about 100:1. The reaction residence time is generally from about 0.01 to about 1 second, or from about 0.03 to about 0.1 second. The hydrogenation reaction is a reversible reaction, and thus the temperature is lowered to the boiling point or lower of the elemental metal zinc immediately after completion of the reaction. Under the above reaction conditions, zinc chloride can be reduced by hydrogen to obtain fine zinc powder.

As shown in Figure 2 and the above formula, the hydrogenation reaction produces elemental metals such as zinc and HCl. The elemental metal can be recycled to one or more recovery reactors while HCl can be recycled to the direct process for producing a decane-containing feed gas comprising trichloromethane. In this regard, by the present invention, the yield of polycrystalline germanium can be increased as much as possible and the waste stream can be reduced.

Recovering elemental metal from the metal chloride in the first composition by reacting the metal chloride in the first composition with elemental hydrazine

According to the process of the invention and as shown in Figure 1, the elemental metal is recovered from the metal chloride in the first composition by reacting the metal chloride in the first composition with elemental hydrazine, which reacts in equilibrium. In particular, the equilibrium reaction involves the reaction of a metal chloride with an elemental ruthenium (ie, a ruthenium atom present in the ruthenium source and available for the reaction) to produce ruthenium tetrachloride and elemental metals (ie, chlorine atoms from the metal chloride) The separated metal atom can be used to drive the equilibrium reaction in one direction or the other to achieve the purpose of recovering the elemental metal. The element 矽 may exist in a relatively impure ruthenium containing impurities and element 矽, and the element 矽 may be effectively separated from some impurities in the element 矽 source by reaction of the element 矽 with the metal chloride, and then the obtained tetrachloride may be further processed. Plutonium is used to separate hafnium tetrachloride from impurities.

It will be appreciated that the process of the invention can be applied to any equilibrium reaction involving the reaction of a metal halide (e.g., a metal chloride) with an elemental cerium to produce a cerium tetrahalide (e.g., cerium tetrachloride) and an elemental metal. For example, a suitable elemental metal may be selected from the group consisting of zinc, copper, aluminum, magnesium, sodium, and the like. In a specific embodiment of the invention, the equilibrium reaction involves chlorine Zinc is reacted with elemental cerium to produce cerium tetrachloride and elemental zinc. In another embodiment of the invention, the equilibrium reaction involves the reaction of copper chloride with elemental cerium to produce cerium tetrachloride and elemental copper. In another embodiment of the process of the invention, the equilibrium reaction involves the reaction of aluminum chloride with elemental cerium to produce cerium tetrachloride and elemental aluminum. Of course, each of the above reactions is an equilibrium reaction, so the reverse reaction and the forward reaction will reach at least some degree of equilibrium, and all compounds on the reactant side and the product side are referred to as "reaction materials".

As shown in Fig. 3, in the apparatus 10 generally isolated from the atmosphere, the step of recovering the elemental metal is carried out by reacting the metal chloride in the first composition with the elemental cerium. It will be appreciated that the apparatus 10 may be unsealed for the purpose of feeding or removing the reaction mass, however, during the reaction, the apparatus 10 is typically sealed to prevent contaminants from entering the apparatus 10, to avoid toxic environmental effects on the reaction, and to control balance. The thermal dynamics of the reaction. A suitable device 10 is described in the TW co-pending application _______, which claims the priority of the US application 61/667,134 filed on July 2, 2012, and entitled "APPARATUS FOR FACILITATING AN EQUILIBRIUM REACTION AND SELECTIVELY SEPARATING REACTIVE SPECIES" (Archive No. DC11194PSP1), filed on the same day, is incorporated herein by reference in its entirety.

In general, as shown in FIG. 3, apparatus 10 includes a heating zone 12, an overhead temperature regulating zone 14 in fluid communication with heating zone 12, and an overhead cooling zone 16 in fluid communication with overhead temperature regulating zone 14. In particular, "fluid communication" means that liquids and/or gases from one zone can flow directly between zones without the need to deblock the apparatus 10 (but valves, gates or other intermediate structures or devices can be placed between the zones) To control the flow of the contents of the device 10 between the zones). The temperature of each zone is independently controlled relative to other zones of equipment 10 to balance the thermal dynamics of the equilibrium reactions in the various zones of the mobile device 10, thereby controlling the physical state of the reactants in each zone (eg, solid state, The liquid and/or gaseous state and the separation of the reaction materials based on the physical state under ambient conditions in each zone. By separating the reaction mass based on the physical state, the equilibrium reaction can be driven to move in one or the other direction as described in more detail below. Although the districts The temperatures are independently controlled, however it should be understood that the zones need not be isolated from each other and that the conditions of one zone may affect the conditions in the other zones, and the process steps of the methods described in more detail below may still be performed in each zone. To illustrate, apparatus 10 can be a reactor having an integrated zone housed therein, such as the reactor shown in Figure 3, wherein the temperature in one zone can affect conditions in adjacent zones. However, it will be appreciated that the various zones may be represented by separate reactors, vessels or devices while joining the zones by feed lines, which provides advantages in the industrial scale implementation of the process of the invention.

In accordance with an embodiment of the present invention, a first composition comprising a metal chloride, such as zinc chloride, is introduced into apparatus 10 when apparatus 10 having various zones is used to carry out the process of the present invention. The first composition can be introduced into the heating zone 12 of the apparatus 10 in gaseous form for the purpose of reacting the metal chloride with the elemental enthalpy therein. The first composition is provided from one or more recovery reactors and may comprise components other than metal chlorides. However, it is to be understood that the first composition generally comprises substantially purified, i.e., at least about 90%, at least about 92.5%, at least about 95%, at least about 98%, at least about 99%, at least about 99.5%, at least about 99.9%. Or at least about 99.99% by weight metal chloride.

In certain embodiments, a carrier (dilution) gas is introduced into the heating zone 12 of the reactor 10 to lift one or more components from the first composition. The gas is generally inert but can also react with another compound. Examples of such gases include rare gases such as argon, and/or process gases such as ruthenium tetrachloride (STC) gas, hydrogen (H ₂ ), and the like. For example, the gas can be passed (eg, by blowing) a first composition that is molten/liquid in order to remove undesirable materials, such as volatile materials. This process may be referred to in the art as stripping of the first composition.

As mentioned above, according to an embodiment, an elemental cerium source reactive with metal chloride can also be introduced into the apparatus 10. In other words, the element 矽 is present in the elemental ruthenium in the form of being reactive with the metal chloride to form ruthenium tetrachloride. In order to utilize the advantages of the invention in the purification of elemental oxime and as mentioned above, the element may be provided in a relatively impure elemental source In addition to elemental germanium, the elemental source contains impurities. It is advantageous to use a relatively impure elemental source, which is therefore much cheaper than a purified element. For example, a relatively impure element source can be readily obtained in a waste stream of some processes, such that the process of the present invention can be used in combination with other methods of producing a waste stream containing elemental sources.

In one embodiment, the elemental germanium source contains less than or equal to about 90.00% by weight enthalpy, which is typical of the "relatively impure" elemental source of the present application. However, it should be understood that any source of germanium, regardless of purity, can be used with the present invention. Examples of relatively impure sources include, but are not limited to, low-grade helium sources, such as metallurgical grades; waste streams containing crushed materials, direct process residues, and forged ceria; and any combination of the above-described elemental sources.

As with the first composition comprising a metal chloride, the elemental germanium source is typically introduced into the heating zone 12 of the apparatus 10. Unlike the first composition, the elemental lanthanum source is typically introduced into the apparatus 10 in solid form. In this regard, the heating zone 12 of the apparatus 10 generally includes a suspended tray or butterfly 18 disposed therein to retain a source of solid element germanium. The suspended tray or butterfly 18 can be supported by the side wall 20 of the device 10 in the heating zone 12 or, in other cases, can be hovered in the heating zone 12 by other features of the apparatus 10. To facilitate contact between the first composition and the elemental source, the suspended tray or butterfly 18 generally has perforations 22 therethrough for allowing the first composition to flow upward through the suspended tray or butterfly 18 and the contact element source. Logically, the first composition is typically introduced into the heating zone 12 below the suspended tray or butterfly 18 to facilitate the flow of the first composition to the elemental source.

The metal chloride from the first composition reacts with the elemental cerium from the elemental cerium source in apparatus 10 to produce a gaseous stream comprising ruthenium tetrachloride, unreacted metal chloride, and optionally elemental metals. The reaction leaves impurities in solid form which are present in the source of the ruthenium, thereby effectively separating the ruthenium from the impurities present in the ruthenium source.

In general, the reaction of the metal chloride with the elemental ruthenium occurs in the heating zone 12 of the apparatus 10, and the reaction is generally carried out in accordance with a gas phase/solid phase reaction in which the first composition is in a gaseous form and the elemental lanthanum is in a solid state. form. More specifically, in the heating zone 12 of the device 10 During the middle reaction, the metal chloride is generally in a gaseous form and the elemental oxime is generally in a solid form. The reaction is carried out under conditions sufficient to drive the reaction, and in this regard, the temperature and pressure within the heating zone 12 of the apparatus 10 is controlled to drive the reaction of the metal chloride with the elemental ruthenium. The physical state of the reaction material is also contemplated in order to establish environmental conditions in the heating zone 12, thereby controlling the temperature and pressure of the heating zone 12 to avoid melting of the helium source and to avoid condensation of the antimony tetrachloride and unreacted metal chloride.

In one embodiment, the elemental metal may have a boiling point above ambient conditions (i.e., temperature and pressure) of the heating zone 12 such that the elemental metal may condense in the heating zone 12 after the metal chloride reacts with the elemental cerium. In this regard, the temperature and pressure in the heating zone 12 are controlled to promote the condensation of elemental metal within the heating zone 12 ( thereby preventing the elemental metal from becoming only due to the condensation of elemental metals during the reaction of the metal chloride with the elemental cerium). An optional component of the gaseous stream produced by the reaction of the metal chloride with the elemental ruthenium). Alternatively, the elemental metal may have a boiling point lower than the environmental conditions of the heating zone 12 such that the gaseous stream produced by the reaction of the metal chloride with the elemental semiconductor comprises elemental metal. The temperature and pressure conditions in the heating zone 12 are generally optimized to achieve maximum conversion between ruthenium and ruthenium tetrachloride.

As mentioned above, after the metal chloride is reacted with the elemental cerium, the elemental metal may condense in the heating zone 12 in a liquid form. For this embodiment, when the ambient conditions in the heating zone 12 are below the boiling point of the elemental metal, a collector (not shown) may be provided in the heating zone 12 to collect the condensed elemental metal separated from the elemental cerium source. For example, when a suspended tray or butterfly 18 is present in the heating zone 12 and has perforations 22, the collector can be placed under the suspended tray or butterfly 18 and the liquid elemental metal flowing down through the perforations 22 can be collected. It will be appreciated that in some cases, the features within the heating zone 12 may have a higher temperature than the environment within the heating zone 12 such that features may not be present in the heating zone 12 even under ambient conditions sufficient to cause the elemental metal to condense. The higher temperature at which the elemental metal is allowed to condense. During or after the parallel reaction, elemental metal may be condensed and collected in the heating zone 12 and the elemental metal in the collector may be transported out of the apparatus 10. As shown in Figure 1, elemental metals can be shown (shown in these figures as The zinc) is recycled to one or more recovery reactors whereby a closed circuit process is formed between one or more recovery reactors and equipment for recovering elemental metals from the metal chloride. Alternatively, elemental metals can be used in apparatus 10 to further react with ruthenium tetrachloride, as described in more detail below.

In one embodiment in which the elemental metal is condensed in a liquid form in the heating zone 12, the metal chloride is zinc chloride and the elemental metal is zinc. In this embodiment, the ruthenium is typically reacted with zinc chloride in the heating zone 12 at a temperature of from about 756 to about 910 ° C, which is sufficient to cause the zinc to condense in the liquid zone in the heated zone 12 while maintaining the heated zone. The temperature in 12 is higher than the boiling point of zinc chloride.

Unless otherwise stated, all temperatures referred to herein are the internal temperatures of the designated zone (rather than the temperature of the walls, heating elements or other features of the device 10). For example, the jacket disposed about the heating zone 12 can be set to a temperature of about 1000 °C, which will impart a temperature of about 756 to about 910 °C to the heating zone 12. It is expected that at least some of the heat is lost between the heating element and the heating zone 12. This logic applies to other zones of the reactor, such as the cooling zone 16, where the temperature of the cooling components is lower than the cooling zone 16 itself. It will be appreciated that some zinc may still be present in the gaseous stream under these conditions, while some zinc will condense in the heating zone 12. It should also be understood that the features in the heated zone 12 will overheat without causing the elemental zinc to condense thereon, so that the elemental zinc can remain in the gaseous stream.

The gaseous stream produced by the reaction of elemental ruthenium with a metal chloride condenses any unreacted metal chloride and elemental metal (when present), wherein the unreacted metal chloride and any elemental metal condense, the ruthenium tetrachloride remains in the gaseous stream in. More specifically, when the metal chloride and the elemental ruthenium are reacted under ambient conditions sufficient to maintain the elemental metal in a gaseous stream, both the elemental and unreacted metal chlorides in the gaseous stream condense from the gaseous stream while maintaining Antimony tetrachloride is in a gaseous form. Alternatively, when the metal chloride and the elemental ruthenium are reacted under ambient conditions insufficient to maintain the elemental metal in the gaseous stream, only the unreacted metal chloride will condense from the gaseous stream. Ultimately, the goal is to condense most of the reaction materials from the gaseous stream and

The ruthenium tetrachloride is maintained in a gaseous stream to separate the ruthenium tetrachloride from the other reaction materials. It is theoretically possible to influence the yield of each reaction mass and the dynamics of the equilibrium reaction by removing certain reaction materials from the system shown in FIG.

In view of the fact that the unreacted metal chloride does not condense under the desired environmental conditions in which the metal chloride reacts with the elemental ruthenium, in the apparatus 10 including various zones, it is possible to carry out the zone in which the metal chloride is separated from the elemental ruthenium. Condensation of reactive metal chlorides and elemental metals (when present). More specifically, a gaseous stream comprising unreacted metal chloride and optionally elemental metal may be fed to the overhead temperature control zone 14 and may be condensed in the overhead temperature control zone 14 in fluid communication with the heating zone 12. Unreacted metal chloride and any elemental metal in the gaseous stream. Since the environmental conditions in the overhead temperature control zone 14 are independently controlled relative to the heating zone 12, environmental conditions in the overhead temperature control zone 14 can be established to selectively condense unreacted metal chlorides and elemental metals (when When present, the ruthenium tetrachloride is simultaneously maintained in the gaseous stream. Since elemental metals and metal chlorides generally have different melting points, elemental metals and metal chlorides can be further separated by operating the environmental conditions of the overhead temperature control zone 14. For example, the elemental metal can be solidified while the metal chloride is condensed into a liquid form (the liquid is not viscous compared to the elemental metal). The condensed metal chloride can be returned from the overhead temperature control zone 14 to the heating zone 12 to participate in the reaction with the element yttrium therein, thereby effectively recovering the unreacted metal chloride and enhancing the conversion between the metal chloride and the elemental metal. effectiveness. Theoretically, the unreacted metal chloride can be recovered by the above mechanism until the gaseous stream contains no unreacted metal chloride. In this regard, the equilibrium reaction is generally carried out under excess helium so that this cycle is repeated until the metal chloride is consumed.

In a specific embodiment, the metal chloride is zinc chloride and the elemental metal is zinc. The ruthenium and zinc chloride can be reacted in the heating zone 12 at a temperature of at least about 910 ° C under atmospheric pressure, under which conditions the zinc will be present in the gaseous stream. Zinc is condensed in the liquid or solid form in the overhead temperature control zone 14. In order for the zinc to condense at atmospheric pressure, the temperature in the overhead temperature control zone 14 should be less than about 910 °C. Although it should be understood that zinc and unreacted zinc chloride can be condensed from the gaseous stream. In the different zones, unreacted zinc chloride may also condense with the zinc in the overhead temperature control zone 14. In such cases, unreacted zinc chloride and zinc may condense from the gaseous stream in the overhead temperature control zone 14 at a temperature of from about 275 to about 756 ° C at atmospheric pressure, such conditions being lower than the boiling point of zinc chloride. And support its condensation. Alternatively, unreacted zinc chloride and zinc may be condensed from a gaseous stream at a temperature of from about 275 to about 420 ° C at atmospheric pressure. Under these conditions, zinc is solid and zinc chloride is liquid, which allows for easier separation of chlorine. Zinc and zinc. Alternatively, unreacted zinc chloride and zinc may condense from the gaseous stream at a temperature of from about 420 to about 756 ° C at atmospheric pressure.

For the purpose of driving the equilibrium reaction to produce ruthenium tetrachloride and elemental metal, at least a portion of the gaseous phase comprising ruthenium tetrachloride is allowed to flow after the metal chloride and the elemental metal (when present) are condensed from the gaseous stream. Condensed metal chloride and elemental metal are separated. By separating at least a portion of the gaseous stream comprising ruthenium tetrachloride after the coagulation step, at least a portion of the ruthenium tetrachloride self-equilibrium reaction can be effectively removed, thereby driving the equilibrium reaction to produce ruthenium tetrachloride and elemental metal movement. Ultimately, this singulation can shift the equilibrium reaction to much higher yields, such as at least about 90 mole percent conversion and even up to 100 mole percent conversion.

In order to condense the metal chloride and the elemental metal (when present) from the gaseous stream, at least a portion of the gaseous stream comprising ruthenium tetrachloride is separated from the condensed metal chloride and the elemental metal, and may remain in the overhead after coagulation. The gaseous stream in the temperature regulation zone 14 is fed to the overhead cooling zone 16 such that at least a portion of the gaseous stream condenses in the overhead cooling zone 16. More specifically, the conditions in the overhead cooling zone 16 allow the ruthenium tetrachloride to condense therein while preserving the conditions in the temperature control zone 14 to maintain the ruthenium tetrachloride in a gaseous form. A baffle is present in the apparatus 10 to separate or separate the condensate in the overhead cooling zone 16 from the overhead temperature regulating zone 14. As illustrated in FIG. 3, the overhead cooling zone 16 can be configured to prevent condensation of ruthenium tetrachloride from flowing back into the overhead temperature regulation zone 14, wherein the baffles are in the device 10 relative to the top by the overhead cooling zone 16. The angle at which the temperature regulation zone 14 extends is established. However, it should be understood that valves or other features (not shown) may also be used as baffles to prevent such flow. In any case, the overhead cooling zone 16 is designed to prevent condensate generated therein from other condensate, gaseous state in other zones where the reactor is present. The stream or other reactive materials are mixed whereby the condensate produced in the overhead cooling zone 16 is effectively separated from the reactants in other zones of the apparatus 10. The condensate produced in the overhead cooling zone 16 can be collected in the collection chamber 24, as shown in Figure 3, and recycled to the recovery reactor for use in the steps indicated by numeral 34. In this regard, the step of separating at least a portion of the gaseous stream comprising hafnium tetrachloride may include withdrawing at least a portion of the gaseous stream from the apparatus 10 for another process or disposal.

As mentioned above, in addition to separating at least a portion of the gaseous stream comprising ruthenium tetrachloride from the condensed metal chloride and the elemental metal, the ruthenium tetrachloride can be reacted with the elemental metal from the reaction of the metal chloride with the elemental ruthenium. A high-purity element lanthanum is formed at a position separate from the reaction of the element lanthanum with the metal chloride. For example, as described above, the elemental metal and ruthenium tetrachloride can be recycled to one or more of the recovery reactors used in the steps indicated by numeral 34. The ruthenium tetrachloride which can be recycled to the one or more recovery reactors is the ruthenium tetrachloride which is isolated. As referred to herein, "high purity" element cerium generally refers to a cerium composition having a purity greater than about 90.00% by weight or at least about 99.00% by weight, whereby the "high purity" element is typically included in the heating zone 12 Used to distinguish between the reaction with metal chlorides.

In view of the above teachings, many modifications and variations of the present invention are possible, and the invention can be practiced in a manner that is specifically described in the scope of the appended claims. It is to be understood that the scope of the appended claims is not limited to the particular embodiments of the inventions and This document clearly covers the subject matter of all combinations of independent and affiliated (including single and multiple affiliated) technical solutions. For any Markush group on which the specific features or aspects of the various embodiments described herein are dependent, it should be understood that each of the members of the Markus group who are independent of all other members of the Markusi group Get different, special and/or unexpected results. Each member of the Markusi group may individually and/or combine and suitably support specific embodiments within the scope of the appended claims.

It should also be understood that any scope and sub-dependency upon which the various embodiments of the present invention are relied upon The accompanying claims are intended to be inclusive and in the scope of the appended claims. Those skilled in the art can readily appreciate that the scope and sub-ranges recited are sufficient to describe and support the various embodiments of the present invention, and such ranges and sub-ranges can be further described as related one-half, one-third, four One, one fifth, and the like. As an example, the range "0.1 to 0.9" can be further described as one third of the previous paragraph (ie 0.1 to 0.3), one third of the middle section (ie 0.4 to 0.6), and one third of the latter paragraph (ie , and the specific embodiments within the scope of the appended claims are individually and/or combined and appropriately supported. In addition, terms used to define or modify the scope (such as "at least", "greater than", "less than", "not greater than" and the like are understood to include sub-ranges and/or upper or lower limits. As another example, the range "at least 10" essentially includes sub-ranges of at least 10 to 35, sub-ranges of at least 10 to 25, sub-ranges of 25 to 35, and the like, and each sub-range may be separately and/or combined. The specified embodiments are within the scope of the appended claims. Finally, individual numbers within the scope of the disclosure can be relied upon and appropriately supported with respect to the specified embodiments within the scope of the appended claims. For example, the range "1 to 9" includes each individual integer (such as 3), and an individual number (or fraction) including a decimal point (such as 4.1), which may depend on and appropriately support the scope of the additional patent application. Designated embodiments.

Claims (24)

A method comprising the steps of: introducing hydrogen and a decane-containing feed gas comprising trichloromethane into one or more decomposition reactors comprising a polycrystalline germanium seed substrate; reacting the trichlorosilane with hydrogen at Forming a polycrystalline ruthenium in the decomposition reactor; discharging a gaseous stream comprising ruthenium tetrachloride from the one or more decomposition reactors; feeding the gaseous stream and the elemental metal source reactive toward the ruthenium tetrachloride to one or a plurality of recovery reactors; reacting the antimony tetrachloride with the elemental metal to form a polycrystalline germanium and a first composition comprising the metal chloride; and at least one of the following from the first composition The metal chloride recovers the elemental metal: 1) hydrogenating the first composition comprising the metal chloride to produce an elemental metal and hydrogen chloride, or 2) reacting the metal chloride in the first composition with elemental hydrazine. The method of claim 1, wherein the step of recovering the elemental metal from the metal chloride is further defined as subjecting the first composition comprising the metal chloride to hydrogenation to produce an elemental metal and hydrogen chloride. The method of claim 1, further comprising the steps of: introducing the first composition comprising the metal chloride into an apparatus isolated from an atmospheric environment; and introducing an elemental cerium source reactive to the metal chloride to In the apparatus, reacting the metal chloride with the element lanthanum in the apparatus to produce a gaseous stream comprising ruthenium tetrachloride, unreacted metal chloride and optionally elemental metal, wherein the reaction is an equilibrium reaction; The unreacted metal chloride and elemental metal (when present) are condensed from the gaseous stream to retain the ruthenium tetrachloride in the gaseous stream; and the metal chloride and elemental metal (when present) After the gaseous stream comprising the ruthenium tetrachloride is condensed, at least a portion of the gaseous stream is separated from the condensed metal chloride and the elemental metal. The method of claim 1, wherein the elemental metal is selected from the group consisting of zinc, copper, aluminum, magnesium, sodium, and the like. The method of claim 3, wherein the apparatus comprises a heating zone, an overhead temperature regulating zone in fluid communication with the heating zone, and an overhead cooling zone in fluid communication with the overhead temperature regulating zone, wherein the temperature of each zone is Independent control. The method of claim 5, wherein the elemental helium source is introduced into the heating zone of the apparatus and wherein the metal chloride is reacted with the elemental helium in the heating zone of the apparatus. The method of claim 6 wherein during the reaction of the heating zone of the apparatus, the metal chloride is in gaseous form and the elemental lanthanide is in solid form. The method of claim 5, further comprising the step of feeding the gaseous stream to the overhead temperature control zone and allowing unreacted metal chloride to condense in the overhead temperature control zone. The method of claim 8, further comprising the step of returning the condensed metal chloride from the overhead temperature control zone to the heating zone. The method of claim 8, wherein the gaseous stream remaining in the overhead temperature control zone after condensing is fed to the overhead cooling zone and wherein at least a portion of the gaseous stream condenses in the overhead cooling zone. The method of claim 8 wherein the baffle in the apparatus separates the condensate in the overhead cooling zone from the overhead temperature regulating zone. The method of claim 8, wherein the gaseous stream comprises the elemental metal, and wherein the The elemental metal condenses in the overhead temperature control zone in liquid or solid form. The method of claim 12, wherein the metal chloride is zinc chloride and the elemental metal is zinc, and wherein zinc and zinc chloride are reacted in the heating zone at a temperature of at least 910 ° C at atmospheric pressure to cause zinc Condensation in the overhead temperature control zone in liquid or solid form. The method of claim 13, wherein the unreacted zinc chloride and zinc are condensed and/or solidified from the gaseous stream in the overhead temperature control zone at a temperature of 275 to a temperature of 756 ° C at atmospheric pressure. The method of claim 14, wherein the unreacted zinc chloride is condensed from the gaseous stream at a temperature of from about 275 to about 420 ° C at atmospheric pressure, and the unreacted zinc is solidified from the gaseous stream. The method of claim 14, wherein the unreacted zinc chloride and zinc are condensed from the gaseous stream at a temperature of from about 420 to about 756 ° C at atmospheric pressure. The method of claim 8, wherein the elemental metal is condensed in the heating zone in a liquid form after the metal chloride is reacted with the elemental cerium. The method of claim 17, wherein the metal chloride is zinc chloride and the elemental metal is zinc, and wherein the cerium is reacted with zinc chloride at a temperature of from about 756 to about 910 ° C in the heated zone. The method of claim 3, further comprising the step of reacting the antimony tetrachloride with a metal from the reaction of the metal chloride with the elemental cerium to form a high position at a position separate from the reaction of the element cerium with the metal chloride Purity element 矽. The method of claim 19, wherein the high purity element cerium has a purity greater than about 90.00% by weight. The method of claim 1, wherein the step of separating at least a portion of the gaseous stream comprising the antimony tetrachloride is further defined as extracting at least a portion of the gaseous stream from the apparatus. The method of claim 3, wherein the ruthenium tetrachloride is recirculated from the gaseous stream To the one or more recovery reactors. The method of claim 3, wherein the elemental source comprises less than or equal to about 90.00% by weight. The method of any one of claims 1 to 23, wherein the elemental metal recovered from the metal chloride in the first composition is recycled to the one or more recovery reactors.