TWI429588B - Methods and systems for producing silane - Google Patents

Description

Method and system for producing decane

The field of the invention relates to a process for the manufacture of decane, and in particular to a process for the regeneration of reactive components using electrolysis. Some specific embodiments are directed to the manufacture of decane as a substantially "closed-loop" method for halogens and/or alkali or alkaline earth metals.

Decane is a multifunctional compound with many industrial uses. In the semiconductor industry, decane can be used to deposit epitaxial germanium layers on semiconductor wafers and to fabricate polysilicon. Polycrystalline germanium is an important raw material for the manufacture of many commercial products including, for example, integrated circuits and photovoltaic (i.e., solar) cells that can be fabricated by thermal decomposition of decane on ruthenium particles in a fluidized bed reactor.

The decane can be produced by reacting ruthenium tetrafluoride with an alkali metal or alkaline earth metal aluminum hydride such as sodium aluminum hydride, as disclosed in U.S. Patent No. 4,632,816, the disclosure of which is incorporated herein by The manner is incorporated herein. This method is characterized by high energy efficiency; however, the cost of the starting material can negatively impact the economics of the system.

Alternatively, decane can be produced by the so-called "Union Carbide Process" in which metallurgical grade ruthenium is reacted with hydrogen and ruthenium tetrachloride to produce trichloromethane, such as M. Ler et al., "Development and Economic Evaluation of a Reactive Distillation Process for Silane Production", Distillation and Adsorption: Integrated Processes , 2002, which is hereby incorporated by reference in its entirety for all purposes for all purposes for all purposes. The trichloromethane is then processed through a series of disproportionation and distillation steps to produce the final product of decane. This approach requires a large number of large circulating streams, which increases initial equipment costs as well as operating costs.

Therefore, there is a continuing need for an economical process for the manufacture of decane and a closed loop process for the manufacture of certain materials used in the process. There is also a need to implement a system that includes such methods of a substantially closed loop system.

One aspect of the invention is directed to a process for the manufacture of decane from an alkali metal or alkaline earth metal halide salt source. The method comprises electrolyzing an alkali metal or alkaline earth metal halide salt to produce a metallic alkali or alkaline earth metal and a halogen gas. The alkali metal or alkaline earth metal is contacted with hydrogen to produce an alkali metal or alkaline earth metal hydride. A ruthenium halide raw material gas containing at least one halogenated decane selected from the group consisting of ruthenium tetrahalide, trihalo decane, dihalo decane, and monohalo decane is produced by contacting a halogen gas with at least one of: (1) Contacting the manufacture of ruthenium tetrahalide, and (2) contacting hydrogen gas to produce hydrogen halide, wherein the hydrogen halide is further contacted with ruthenium to produce a mixture containing ruthenium tetrahalide and trihalo decane. The halogenated feed gas is contacted with an alkali metal or alkaline earth metal hydride to produce a decane and an alkali metal or alkaline earth metal hydride salt.

Another aspect of the invention is directed to a method of making decane in a substantially closed loop system with respect to alkali or alkaline earth metals. The hafnium halide raw material gas is contacted with an alkali metal or alkaline earth metal halide to produce a decane and an alkali metal or alkaline earth metal halide salt. The halide salt is electrolyzed to produce a metallic alkali metal or alkaline earth metal and a halogen gas. A metallic alkali metal or alkaline earth metal is contacted with hydrogen to produce an alkali metal or alkaline earth metal hydride. The alkali metal or alkaline earth metal hydride produced by contacting a metallic alkali metal or an alkaline earth metal with hydrogen is brought into contact with a ruthenium halide raw material gas to produce a decane and an alkali metal or alkaline earth metal halide salt.

Yet another aspect of the present invention is directed to a method of making decane in a substantially closed loop system with respect to halogen. The ruthenium halide raw material gas containing at least one halogenated decane selected from the group consisting of ruthenium tetrahalide, trihalo decane, dihalo decane and monohalo decane is contacted with an alkali metal or alkaline earth metal hydride to produce decane and an alkali metal or alkaline earth metal. Halide salt. The halide salt is electrolyzed to produce a metallic alkali metal or alkaline earth metal and a halogen gas. A halogenated ruthenium raw material gas containing at least one halogenated decane selected from the group consisting of ruthenium tetrahalide, trihalomethane, dihalodecane and monohalodecane is produced by contacting a halogen gas with at least one of: (1) The ruthenium is contacted to produce ruthenium tetrahalide, and (2) is contacted with hydrogen to produce a hydrogen halide, wherein the hydrogen halide is further contacted with ruthenium to produce a mixture comprising ruthenium tetrahalide and trihalo decane. The hafnium halide raw material gas is contacted with an alkali metal or alkaline earth metal hydride to produce a decane and an alkali metal or alkaline earth metal halide salt.

In another aspect of the present invention, a closed-loop method for producing polycrystalline germanium includes a halogenated ruthenium raw material gas and a base containing at least one halogenated decane selected from the group consisting of ruthenium tetrahalide, trihalo decane, dihalo decane, and monohalo decane. A metal or alkaline earth metal hydride is contacted to produce a decane and an alkali metal or alkaline earth metal halide salt. The decane is thermally decomposed to produce polycrystalline germanium and hydrogen. The halide salt is electrolyzed to produce a metallic alkali metal or alkaline earth metal and a halogen gas. A halogenated ruthenium raw material gas containing at least one halogenated decane selected from the group consisting of ruthenium tetrahalide, trihalo decane, dihalo decane and monohalo decane, by using a halogen gas produced by electrolytic alkali metal or alkaline earth metal halide At least one of the following is produced by contacting: (1) contacting ruthenium to produce ruthenium tetrahalide, and (2) contacting hydrogen to produce hydrogen halide, wherein the hydrogen halide is further contacted with ruthenium to produce ruthenium tetrahalide and trihalo decane. a mixture. The metallic alkali metal or alkaline earth metal is contacted with hydrogen produced by thermal decomposition of decane to produce an alkali metal or alkaline earth metal hydride. Making a ruthenium and an alkali metal or an alkali metal or an alkaline earth metal hydride produced by contacting a halogen gas or a hydrogen halide with ruthenium in contact with an alkali metal or an alkaline earth metal hydride produced by contacting a metallic alkali metal or an alkaline earth metal with hydrogen Alkaline earth metal halide salt.

In yet another aspect of the invention, a system for producing decane in a substantially closed loop process includes a vessel for the electrolysis of an alkali or alkaline earth metal halide salt to produce a metallic alkali or alkaline earth metal and a halogen gas. The system comprises a halogenation reactor for the manufacture of at least one of: (1) antimony tetrahalide and (2) trihalomethane, which are produced by reacting rhodium with at least one of: (1) from a container The halogen gas to be discharged and (2) the hydrogen halide produced by bringing the halogen gas discharged from the container into contact with hydrogen. The system includes a hydride reactor for reacting a metallic alkali or alkaline earth metal discharged from a vessel with hydrogen to produce an alkali metal or alkaline earth metal hydride. The system includes a decane reactor for reacting at least one of (1) ruthenium tetrahalide and (2) trihalo decane with an alkali metal or alkaline earth metal hydride to produce a decane and an alkali metal or alkaline earth metal halide salt.

There are various improvements with respect to the features indicated by the above-mentioned aspects of the invention. Other features may also be incorporated into the aspects of the invention mentioned above. Such improvements and other features may exist individually or in any combination. For example, the various features discussed below in relation to any of the illustrated embodiments of the invention may be incorporated into any of the above-described aspects of the invention, either individually or in any combination.

Corresponding reference characters indicate corresponding parts throughout the drawings.

The method of the present invention uses electrolysis to regenerate the reactive components in the process for making decane. Electrolysis allows the decane manufacturing process to be a substantially closed loop system with respect to certain compounds used in the system, such as halogens (e.g., chlorine) and/or alkali or alkaline earth metals (e.g., sodium). As used herein, the phrase "substantially closed-loop process" or "substantially closed-loop system" refers to a method or system having the following characteristics, wherein the system or method is A closed-loop related compound is not extracted from the system or method other than as an impurity and is not derived from the amount of compound that is lost as impurities in the system (eg, the amount of compound added is less than about 5% of the total cycle in the system, below) Feed into a system or method for purposes other than a more comprehensive description.

In one or more embodiments of the invention, the decane is produced by electrolyzing an alkali metal or alkaline earth metal halide salt to produce a metallic alkali or alkaline earth metal and a halogen gas. The metallic alkali metal or alkali metal is reacted with hydrogen to produce a hydride, and the halogen gas is reacted with hydrazine (and in some embodiments hydrogen) to produce a lanthanum halide containing haloxines and in some embodiments The halogenated raw material gas. The feed gas is reacted to produce a decane and a halide salt. In embodiments where the method is substantially closed to at least one of an alkali metal or alkaline earth metal and a halogen gas, the halide salt byproduct is produced by electrolyzing a halide salt to produce a metallic alkali or alkaline earth metal and a halogen gas. Recycling.

Using electrolysis to produce decane

Referring now to FIG. 1, 3 halide salt introduced into the container 4, the manipulation of the container halide salt electrolysis to produce a halogen gas (e.g. Cl ₂₎ and a metal (e.g. alkali metal or alkaline earth metal). As used herein, "halide salt" contains an alkali metal or alkaline earth metal and a halogen. The halide salt may have the formula MX _y wherein M is an alkali metal or alkaline earth metal, X is a halogen, and y is 1 when M is an alkali metal, and y is 2 when M is an alkaline earth metal. The alkali metal or alkaline earth metal of the halide salt (and in some embodiments as described below, which is recycled within the closed loop system) may be selected from the group consisting of lithium, sodium, potassium, magnesium, strontium, calcium. And mixtures thereof. The halogen may be selected from the group consisting of fluorine, chlorine, bromine, iodine, and mixtures thereof. In view of the wide availability of sodium chloride and in view of the ease with which sodium chloride can be separated into its constituent parts (e.g., chloride gas and metallic sodium), sodium is a preferred alkali metal or alkaline earth metal and chlorine is a preferred halogen. In this regard, it is to be understood that any alkali or alkaline earth metal can be used and any halogen can be used, as is the case with the method and system for producing decane as described below with respect to the closed loop of an alkali metal or alkaline earth metal.

A container 4 suitable for electrolyzing a halide salt is a Downs cell. An exemplary Down's cell is shown in Figure 2 and the reference number is generally "20". The Pool 20 includes one or more halide salts 15 therein and contains an anode 14 and a cathode 16. The anode 14 may be composed of, for example, carbon (e.g., graphite) and the cathode 16 may be composed of, for example, steel or iron. At the anode 14, a halogen gas is oxidized to form chlorine ions (e.g., Cl _2). At the cathode 16, an alkali metal or alkaline earth metal ion is reduced to form a metallic alkali metal or alkaline earth metal. In this regard, it is to be understood that the term "metallic" as used herein refers to an alkali or alkaline earth metal having an oxidation number of zero. The formed halogen gas and the metallic alkali metal or alkaline earth metal are separated by the separator 19. The partition 19 may be a screen or wire mesh made of steel or iron. In this regard, it is to be understood that an electrolytic cell other than that of the Down's cell, such as that described in U.S. Patent No. 5,904,821, is incorporated herein by reference.

The metal alkali or alkaline earth metal produced has a lower density than the halide salt, which causes it to rise in the pool. The halogen gas also rises, and the halogen gas 18 and the metallic alkali metal or alkaline earth metal 17 are both removed from the Down's pool. A second alkali metal or alkaline earth metal salt can be added to the Down's pool to form a eutectic mixture and to reduce the melting point of the electrolytic halide salt to reduce the energy consumption of the molten halide salt and/or the halide salt to maintain a molten state. For example, when sodium chloride is electrolyzed in the Down cell 20, a certain amount of calcium chloride, aluminum chloride or sodium carbonate may be added to lower the melting point of the sodium chloride. For example, a mixture containing 53.2 mol% calcium chloride and 46.8 mol% sodium chloride has a melting point of 494 ° C and contains 23.1 mol% sodium carbonate and 76.9 mol% chlorine, compared to the melting point of 801 ° C of sodium chloride alone. An exemplary mixture of sodium is having a melting point of 634 °C. Preferably, the alkali metal or alkaline earth metal of the second salt is the same as the alkali metal or alkaline earth metal of the halide salt, or is an oxidizing agent weaker than the alkali metal or alkaline earth metal of the halide salt so as not to affect the alkali metal of the halide salt. Or reduction of alkaline earth metals.

Referring again to FIG. 1, the halogen gas 18 introduced into the halogenation reactor 8, the halogenation reactor with a contact 6 to produce silicon-containing silicon tetrahalide (e.g., SiCl ₄₎ of the feed gas 21 halide. This reaction is described below:

Si+2X ₂ →SiX ₄ (1)

The source of 矽6 may be metallurgical grade ruthenium; however, it should be understood that other ruthenium sources such as sand (i.e., SiO ₂ ), quartz, vermiculite, diatomaceous earth, mineral citrate, fluoroantimonate, and mixtures thereof may be used. . In this regard, it is to be understood that as used herein, "contact" of two or more reactive compounds generally causes the reaction of such components, and the terms "contacting" and "reacting" Reacting) is synonymous, as a derivative of these terms, and such terms and derivatives are not to be construed as limiting.

As an alternative to direct reaction with hydrazine and as shown in Figure 3, the halogen gas 18 can be reacted with hydrogen gas 28 in a hydrogen halide burner 25 (synonymous with a hydrogen halide "oven" or "furnace") to form a hydrogen halide 26 (HX). ). According to the reaction shown below, the hydrogen halide 26 can be reacted with ruthenium 6 in the halogenation reactor 8 to form a ruthenium halide feed gas 21' containing a trihalo decane and a ruthenium tetrahalide:

Si+3HX→SiHX ₃ +H ₂ (2)

Si+4HX→SiX ₄ +2H ₂ (3)

The molar ratio of the antimony tetrahalide to the trihalodecane in the hafnium halide feed gas 21' can vary, and in various embodiments, can range from about 1:7 to about 1:2 or from about 1:6 to about 1:3. . In this regard, it will be appreciated that the reaction of hydrazine 6 with hydrogen halide 26 can be made, but not limited to, a certain amount of dihalodecane and/or monohalodecane.

In certain embodiments, it is preferred that the halogen gas 18 reacts with the hydrogen gas 28 to form a hydrogen halide prior to direct halogenation (FIG. 1), and then reacts with hydrazine to form a mixture comprising a trihalodecane and a ruthenium tetrahalide (FIG. 3). This is because decane can be produced from trihalodecane using less hydride than ruthenium tetrahalide, as shown in reaction 5-6ii below. Furthermore, direct halogenation reactions may require higher temperatures and may be more difficult to control relative to the reaction of hydrogen halide with hydrazine.

The source of hydrogen 28 can be selected from the sources described below with respect to hydrogen feedstock 31. The source of the hydrogen gas 28 may be, for example, hydrogen obtained by recycling the halogenated feed gas 21' or hydrogen separated from the halogenated raw material gas 21'. Hydrogen gas can be separated from the hafnium halide raw material gas 21' using a gas-liquid separator (not shown). Examples of such gas-liquid separators include a vessel that lowers the pressure and/or temperature of the intake gas to cause condensation of a low-boiling gas such as ruthenium tetrahalide and/or trihalodecane and separate from a high-boiling gas such as hydrogen. Suitable containers include those commonly referred to in the art as "knock-out drums". The container may optionally be cooled to promote gas separation. Alternatively, hydrogen can be separated by one or more distillation columns.

As an alternative to reacting hydrogen with a halogen in a hydrogen halide burner as shown in FIG. 3, followed by reacting hydrogen halide with hydrazine in a halogenation reactor, hydrogen, a halogen gas, and helium may be reacted in a vessel to produce three a mixture of halodecane and cesium tetrahalide. In this regard, it should be understood that although the preparation of hydrogen halide has been generally described with reference to anhydrous hydrogen halide gas, in some embodiments, an aqueous hydrogen halide solution, and in particular an aqueous HF solution, may be produced, which may be known to those skilled in the art. The method is known to react with hydrazine to produce a mixture comprising a trihalodecane and a ruthenium tetrahalide. Moreover, in this regard, although the reaction product of hydrogen halide and hydrazine has been described as comprising a mixture of a trihalodecane and a ruthenium tetrahalide, it will be appreciated that the reaction parameters can be controlled to produce ruthenium tetrahalide and only traces of trihalo decane (eg, Less than about 5% by volume or less than about 1% by volume) or trihalomethane and a trace amount of ruthenium tetrahalide (e.g., less than about 5% by volume or less than about 1% by volume).

The halogenation reactor 8 can be operated in a fluidized bed format in which helium is suspended in an inlet gas (e.g., halogen 18 (Fig. 1) or hydrogen halide 26 (Fig. 3). The halogenation reactor 8 can be operated at room temperature (e.g., about 20 ° C), especially when fluorine is selected as the halogen. More generally, the reactor can be operated at a temperature of at least about 20 ° C, at least about 75 ° C, at least about 150 ° C, at least about 250 ° C, at least about 500 ° C, at least about 750 ° C, at least about 1000 ° C, or at least about 1150. °C (for example, from about 20 ° C to about 1200 ° C, from about 250 ° C to about 1200 ° C or from about 500 ° C to about 1200 ° C). The operating pressure of reactor 8 can be at least about 1 bar, at least about 3 bar, or even at least about 6 bar (e.g., from about 1 bar to about 8 bar or from about 3 bar to about 8 bar).

In this regard, it should be understood that the hafnium halide feed stream 21 shown in FIG. 1 and the hafnium halide feed stream 21' shown in FIG. 3 may contain a halodecane which is not a hafnium halide or a trihalodecane, such as a certain amount. Monohalodecane and/or dihalodecane. Additionally, the hafnium halide feed stream 21 or the hafnium halide feed stream 21' can be introduced into a disproportionation system (not shown) to produce a quantity of trihalodecane, dihalodecane, and/or monohalodecane. It will be understood that as used herein, "halogentated silicon feed gas" includes any of any amount of one or more halodecanes (ie, hafnium halide, trihalodecane, dihalodecane or monohalodecane). Gas and includes gases that have not been introduced into the disproportionation system and that have been introduced into the disproportionation system.

Referring again to Figure 1, hafnium halide feed stream 21 (or hafnium halide feed stream 21' as in Figure 3) is introduced into decane reactor 30 to produce decane 35. Prior to introduction into the decane reactor 30, the ruthenium halide feed gas 21 (or the feed gas 21' containing ruthenium tetrahalide and trihalomethane) may be purified to remove such as an aluminum halide or an iron halide (for example, when the halogen is chlorine) Impurities of AlCl ₃ and/or FeCl ₃ ) and/or ruthenium polymer (Si _n Cl _m polymer when halogen is chlorine). These impurities can be removed by cooling the gas to precipitate impurities from the system. The precipitated impurities can be removed by introducing the gas into a particle separator such as a bag filter or a cyclone separator. To precipitate impurities (such as metal halides and/or ruthenium polymers), the ruthenium halide feed gas 21 (or a mixture of ruthenium tetrahalide and/or trihalomethane 21') can be cooled to a temperature of less than about 200 ° C, or As in other embodiments, less than about 175 ° C, less than about 150 ° C, or even less than about 125 ° C (eg, from about 100 ° C to about 200 ° C or from about 125 ° C to about 175 ° C). The gas can be cooled by exchanging heat with cooling water or cooling oil in the heat exchange device and/or the cooler device. The hafnium halide feed gas 21 (or the mixture of tetrahalide ruthenium and/or trihalodecane 21') may contain less than 10% by volume of impurities (i.e., compounds which are not halodecane) or even less than about 5 volumes after impurity removal. %, less than about 1% by volume, less than about 0.1% by volume, or even less than about 0.01% by volume of impurities (eg, from 0.001% to about 10% by volume or from about 0.001% to about 1% by volume).

A metallic alkali metal or alkaline earth metal 17 produced as an electrolytic product is introduced into the hydride reactor 9. A certain amount of hydrogen 31 is also introduced into the hydride reactor 9. As shown in the following reaction, the reaction between the metallic alkali metal or alkaline earth metal and hydrogen produces an alkali metal or alkaline earth metal hydride 32:

(2/y)M+H ₂ →(2/y)MH _y (4)

Wherein y is 1 when M is an alkali metal, and y is 2 when M is an alkaline earth metal. For example, when M is Na, the reaction proceeds as follows.

2Na+H ₂ →2NaH (4i).

When M is Ca, the reaction proceeds as follows.

Ca + H ₂ → CaH ₂ (4ii).

Reaction (4) can occur in hydride reactor 9 in the presence of a solvent. Suitable solvents include the various hydrocarbon compounds, such as toluene, diethyl ether, diethylene glycol dimethyl ether, and ionic liquids, such as NaAlCl _4. In an embodiment using NaAlCl ₄ , the hydride reactor 9 can include an electrode. Once the supply of alkali metal or alkaline earth metal hydride is exhausted, the electrode can be excited to cause sodium (including a certain amount of sodium from NaAlCl ₄ ) to react with H ₂ and regenerate the hydride compound. In an embodiment using NaAlCl ₄ as a solvent, other ionic compounds may be added to form a eutectic mixture as disclosed in U.S. Patent No. 6,482,381, hereby incorporated hereinby .

The hydride reactor 9 may be a stirred tank reactor in which a certain amount of a solvent (not shown) and a metallic alkali metal or alkaline earth metal 17 are added. Hydrogen 31 can be bubbled through the reaction mixture to form an alkali metal or alkaline earth metal hydride 32 in a batch mode or in a semi-continuous or continuous process. Suitable sources of hydrogen 31 include commercially available hydrogen or hydrogen obtained from other process streams. For example, in an embodiment where a hydrogen halide is reacted with hydrazine, hydrogen can be separated from the trihalomethane and the ruthenium tetrahalide mixture 21' (e.g., a gas-liquid separator as described above). Alternatively or additionally, hydrogen released from the decane during the manufacture of the downstream polysilicon can be used. The amount of solvent, hydrogen 31, and metallic alkali metal or alkaline earth metal 17 added to reactor 9 can be selected such that the weight ratio of hydride to solvent in reactor 9 can be at least about 1:20, and in other In embodiments, at least about 1:10, at least about 1:5, at least about 1:3, at least about 2:3, or even at least about 1:1 (eg, from about 1:20 to about 1:1 or about 1: 10 to about 2:3).

In one or more embodiments, the reaction mixture in reactor 9 is thoroughly mixed using, for example, one or more mixers having relatively high agitation of one or more impellers. The relatively high agitation allows the hydrogen to be sufficiently dispersed throughout the reaction mixture to maximize the rate of hydrogen dissolution and to shear any solid alkali or alkaline earth metal hydride from the metallic alkali or alkaline earth metal to make the liquid alkali metal or The alkaline earth metal can be continuously used to react with dissolved hydrogen. In this regard, and without wishing to be bound by any particular theory, the mass transfer in the hydride reactor is dependent on the liquid side resistance and is expected to be between about 100 s ^-1 to about 100,0000 s ^-1 and more typically between about The volumetric gas-liquid mass transfer coefficient (K _L a _G ) between 1,000 s ^-1 and about 10,000 s ^-1 is determined. It should be noted that the specific volumetric gas-liquid mass transfer coefficient (K _L a _G ) may vary depending on the particular hydride and solvent selected for use in reactor 9. Such values can be readily determined by those skilled in the art in accordance with known methods (e.g., measuring hydrogen evolution over time).

In several embodiments of the invention, the hydride reactor 9 is operated under high pressure conditions such as at least about 50 bar, at least about 125 bar, at least about 200 bar, at least about 275 bar, or at least about 350 bar (eg, From about 50 bar to about 350 bar or from about 50 bar to about 200 bar). The hydride reactor 9 can be operated at a temperature less than the thermal decomposition of an alkali metal or alkaline earth metal halide, such as less than about 160 ° C, less than about 145 ° C, or less than about 130 ° C (eg, from about 120 ° C to about 160 ° C). ).

The alkali metal or alkaline earth metal hydride 32 is typically a solid in an organic solvent. A slurry containing an alkali metal or alkaline earth metal hydride 32 suspended in a solvent can be introduced into the decane reactor 30 to produce decane 35. In this regard, it will be appreciated that in certain other embodiments of the invention, the alkali metal or alkaline earth metal hydride 32 may be introduced into the decane reactor 30 in the form of a solid or agglomerated solid containing a relatively small amount of solvent. The alkali or alkaline earth metal can be separated from the solvent by centrifugation or filtration or by any other suitable method known to those skilled in the art. In this regard, it is understood, may be used but are not limited to, a solvent of an organic solvent (e.g. NaAlCl _4).

As described above, the antimony tetrahalide and the alkali metal or alkaline earth metal hydride 32 from the antimony halide raw material gas 21 (or the mixture 21' containing tetrahalide and trihalomethane as shown in FIG. 3) are introduced into the decane reactor 30. The decane 35 and the halide salt 37 were produced according to the reaction shown below:

(4/y)MH _y +SiX ₄ →(4/y)MX _y +SiH ₄ (5)

3MH _y +ySiHX ₃ →3MX _y +ySiH ₄ (6)

Wherein y is 1 when M is an alkali metal, and y is 2 when M is an alkaline earth metal. For example, when M is Na and X is Cl, the reaction proceeds as follows.

4NaH+SiCl ₄ →4NaCl+SiH ₄ (5i)

3NaH+SiHCl ₃ →3NaCl+SiH ₄ (6i).

When M is Ba and X is Cl, the reaction proceeds as follows.

2BaH ₂ +SiCl ₄ →2BaCl ₂ +SiH ₄ (5ii)

3BaH ₂ + 2SiHCl ₃ → 3BaCl ₂ + 2SiH ₄ (6ii).

The decane reactor 30 can be a stirred tank reactor (e.g., impeller agitation). The alkali metal or alkaline earth metal hydride 32 added to the reactor 30 can be suspended in a solvent (e.g., toluene) in which it is produced (e.g., by reacting an alkali metal or alkaline earth metal with hydrogen). The hafnium halide and/or trihalodecane 31 can be bubbled through the hydride slurry and preferably bubbled in a countercurrent relationship. The weight ratio of the amount of hydride 32 added to reactor 30 to the amount of solvent added to the reactor can be at least about 1:20, and in other embodiments at least about 1:10 or at least about 1:5 ( For example, it is from about 1:20 to about 1:5 or from about 1:20 to about 2:10). The tetrahalide ruthenium added from the ruthenium halide feed gas 21 (Fig. 1) or the tetrahalide ruthenium and trihalomethane from the ruthenium halide feed gas 21' (Fig. 3) may be substantially stoichiometric with respect to the hydride 32. Wherein the molar ratio is shown in the above reactions (5) to (6ii).

A quantity of a catalyst such as triethylaluminum, various Lewis acids or traces of an alkali metal such as an impurity Lewis acid such as a metal chloride may be added to the reactor 30. The catalysts lower the temperature at which reactions (5) and (6) achieve sufficient conversion and reduce heat in the input system. In embodiments where no catalyst is used, the operating temperature of reactor 30 can be at least about 120 ° C (eg, from about 120 ° C to about 225 ° C or from about 140 ° C to about 200 ° C); however, in embodiments using a catalyst The operating temperature of reactor 30 can be relatively cold, at least about 30 ° C (eg, from about 30 ° C to about 125 ° C, from about 40 ° C to about 100 ° C, or from about 40 ° C to about 80 ° C). The average residence time of the materials added to reactor 30 can range from about 5 minutes to about 60 minutes.

The decane gas 35 can be relatively pure (e.g., containing less than about 5% by volume or even less than about 2% by volume of a compound that is not decane). After the decane gas 35 is removed from the reactor 30, the decane gas 35 can be further processed. For example, decane 35 can be removed by the introduction of one or more distillation columns and/or molecular sieves, as disclosed in U.S. Patent No. 5,211,931, U.S. Patent No. 4,554,141, or U.S. Patent No. 5,206,004. All related and consistent objects are incorporated herein by reference or by any other known method available to those skilled in the art (e.g., removal of a compound such as a boron halide or a phosphorus halide).

The decane gas 35 can be used to prepare polycrystalline germanium (eg, granular or bulk polycrystalline germanium) or can be used to prepare one or more epitaxial layers on a germanium wafer. As is known to those skilled in the art, the decane gas can be stored and/or transported prior to use.

The alkali metal or alkaline earth metal hydride is reacted with ruthenium tetrahalide in the ruthenium halide feed gas 21 (or a mixture of trihalomethane and ruthenium tetrahalide 21') to produce an alkali metal or alkaline earth metal halide salt 37 as a by-product. In embodiments where a solvent is used, the halide salt 37 is soluble and more typically suspended in a solvent such as toluene. The halide salt 37 can be separated from the solvent and used commercially or recycled as described further below.

Substantial closed-loop method for the manufacture of decane

The methods described above can be incorporated into a substantial closed loop process for the manufacture of decane. The above process may be a ring closure with respect to alkali or alkaline earth metals and/or with respect to halogens. Referring now to Figure 4, the halide salt 37 can be separated from the solvent by use of a separator 40. The separator 40 can be an evaporator, or in addition to or instead of the evaporator, other suitable equipment can be used, including crystallizers, filtration and/or gravity based separators (e.g., centrifuges). Suitable evaporators include wiped film evaporators. After separation, the dried halide salt can be heated (eg, to 500 ° C) to remove traces of solvent.

Solvent 43 can be condensed and reintroduced into hydride reactor 9 and/or decane reactor 30. The separated halide salt 3 can be used as a raw material 3 for electrolysis so that the alkali metal or alkaline earth metal and/or halide is substantially recycled throughout the system.

In this regard, it will be appreciated that the substantial closed loop process illustrated in FIG. 4 can be modified to include a hydrogen halide burner 25 to produce a gas 21' comprising a hafnium halide and a trihalodecane as in FIG.

As shown in Figure 4, the process is substantially ring closed with respect to alkali or alkaline earth metals and with respect to halogens, wherein the system includes alkali or alkaline earth metals or halogens in any of the feed streams 6, 31 (i.e., alone or The alkali metal or alkaline earth metal and halogen are not removed in the output stream 35 in the form of an alkali metal or alkaline earth metal or halogen compound. In this regard, it will be appreciated that alkali or alkaline earth metals and/or halogens may be removed from the system as impurities or may be included in the purge stream and may be fed into the system or process as a supplemental stream. Any supplementation of an alkali metal or alkaline earth metal and/or halogen can be achieved by addition to a compound system containing individual elements, and in certain embodiments, by the respective hydride salt itself. In various embodiments, the amount of alkali metal or alkaline earth metal and/or halogen gas (which may be added as an alkali metal or alkaline earth metal salt) added to the system is less than about 5% of the total cycle in the system, and in other In embodiments, it is less than about 2% of the total cycle in the system (e.g., from about 0.5% to about 5%).

In some embodiments of the invention, the system and method may be a substantial closed loop with respect to hydrogen. For example, as shown in FIG. 5, the decane 35 exiting the decane reactor 30 can be introduced into the polycrystalline reactor 50, preferably to remove traces of decane, carbon compounds, trace metals, and any boron doped, preferably. After the phosphorus or aluminum compound (for example by a low temperature activated carbon adsorber). The polycrystalline reactor 50 can be a fluidized bed (e.g., a granular polycrystalline germanium) or a Siemens reactor (e.g., a bulk polycrystalline germanium) or can be incorporated with any other reactor design suitable for making polycrystalline germanium. The decane is thermally decomposed according to the following reaction to produce polycrystalline germanium:

SiH ₄ →Si+2H ₂ (7)

The decane may be subjected to further processing prior to addition to the polycrystalline reactor 50, such as various purification steps as described above. The reaction product of reactor 50 includes polycrystalline germanium 52 and hydrogen 31. As shown in FIG. 5, hydrogen gas 31 is introduced into the hydride reactor 9. Hydrogen 31 can be further processed by separation of the dust and by purification (e.g., distillation) prior to introduction into the hydride reactor 9. As shown in FIG. 5, only 矽6 in the input system and only the polysilicon 52 is output. The system is a substantial closed loop with respect to hydrogen where hydrogen is only removed as an impurity or as a purge stream (not shown) and only added as a makeup stream (not shown).

Substantial closed-loop system for the manufacture of decane

The process of the present invention can be carried out in a system for making decane, such as any of the systems illustrated in Figures 1-5. The system can be a substantial closed loop with respect to one or more of a halogen, an alkali or alkaline earth metal, and hydrogen.

Referring to Figure 1, the system can include a vessel 4 (e.g., Down's tank) for electrolyzing a halide salt to produce a metallic alkali or alkaline earth metal and a halogen gas. The halogen gas is delivered to at least one of: (1) a hydrogen halide burner 25 to react with hydrogen and produce hydrogen halide (FIG. 3), and (2) a halogenation reactor 8 to The reaction is carried out from the helium storage device to the halogenation reactor 8 by means of a transport device to react and produce ruthenium tetrahalide. In the embodiment in which the halogen gas reacts to produce hydrogen halide, the hydrogen halide can then be transported to the halogenation reactor 8 by a transfer device to produce a mixture comprising ruthenium tetrahalide and trihalomethane. Any ruthenium tetrahalide and/or trihalo decane gas produced is delivered to the decane reactor 30 by a transfer device.

The system also includes a hydride reactor 9 (e.g., a stirred tank reactor). The metallic alkali metal or alkaline earth metal is transported from the vessel to the hydride reactor 9 by means of a conveying device. Hydrogen is also transported to the hydride reactor 9 by means of a transport unit to react with a metallic alkali or alkaline earth metal to produce an alkali metal or alkaline earth metal hydride. The system includes a decane reactor 30 (e.g., a stirred tank reactor) to which a hydride (any solvent, as the case may be) is delivered by a delivery device. In the decane reactor 30, the hydride is reacted with a ruthenium tetrahalide and/or a trihalo decane gas to form a halide salt, optionally in the presence of a solvent.

In various embodiments and as shown in Figure 4, the solvent and halide salts can be delivered by a delivery device to a separator 40 for separating any solvent and halide salts. The solvent can be delivered to the hydride reactor 9 by means of a transport unit, and the halide salt can be transported by means of a transport device to a vessel 4 (for example a Downs cell) for recycling and completion of the substance relating to halogens and alkali or alkaline earth metals. Closed loop system.

In several other embodiments, the system also includes a polycrystalline reactor 50, which may be a Siemens-type reactor or a fluidized bed reactor. The decane is transported from the decane reactor 30 to the polycrystalline reactor 50 by a transport unit to produce hydrogen and polycrystalline germanium. Hydrogen can be delivered from the polycrystalline reactor 50 to the hydride reactor 9 by a transfer unit to recycle the hydrogen and complete a substantially closed loop system with respect to hydrogen.

Suitable delivery devices are well known and well known in the art. Conveying devices suitable for transferring gases include, for example, compressors or blowers, and conveying devices suitable for transferring solids include, for example, towed, spiral, belt, and pneumatic conveyors. In this regard, it should be understood that the phrase "conveying apparatus" is used herein to mean that a unit of the system is transferred directly to another unit, and only the substance is transferred between the parts by any number and/or Or an organization moves from one unit to another. For example, a substance can be delivered from one unit to another processing unit (eg, a purification or storage unit for providing buffering between continuous or batch processes) and subsequently delivered to the second unit. In this example, each of the transport units including the intermediate processing equipment itself can be considered a "conveying device" and the phrase "conveying device" should not be considered limiting.

Preferably, all of the equipment used in the system for making decane is resistant to environmental corrosion (including exposure to the compounds used in the system and manufactured in the system). Suitable materials for construction are well known and well known in the art and include, for example, carbon steel, stainless steel, MONEW alloys, INCONEL alloys, HASTELLOY alloys, nickel and non-metallic materials such as quartz (i.e., glass) and fluorinated polymerization. (such as TEFLON, KEL-F, VITON, KALREZ and AFLAS).

It will be appreciated that the methods and systems described above may include more than one of any of the described units (e.g., reactors and/or separation units), and that multiple units may be operated continuously and/or in parallel without departing from the scope of the invention. . Moreover, in this regard, it should be appreciated that the methods and systems are illustrative, and that the methods and systems can include other elements with, but not limited to, other functions.

The articles "a", "an", "the", "said" and "said" are intended to mean the elements of the present invention or the preferred embodiments thereof. There are one or more elements. The terms "comprising", "including" and "having" are intended to be inclusive and mean that there are other elements than those listed.

All the matters contained in the above description and the accompanying drawings are to be considered as illustrative and not restrictive.

3. . . Halide salt / raw material

4. . . container

6. . .矽

8. . . Halogenation reactor

9. . . Hydride reactor

14. . . anode

15. . . Halide salt

16. . . cathode

17. . . Metallic alkali or alkaline earth metal

18. . . Halogen gas

19. . . Separator

20. . . Down Pool

twenty one. . . Halogenated feed gas/halogenated germanium feedstock/halogenated germanium feedstock

twenty one'. . . Halogenated feed gas/halogenated ruthenium feed gas/halogenated ruthenium raw material stream/feedstock gas containing tetrahalide ruthenium and/or trihalo decane/mixture of ruthenium tetrahalide and/or trihalo decane

25. . . Hydrogen halide burner

26. . . Hydrogen halide

28. . . hydrogen

30. . . Decane reactor

31. . . hydrogen

32. . . Alkali metal or alkaline earth metal hydride

35. . . Decane

37. . . Alkali metal or alkaline earth metal halide salt

40. . . Splitter

43. . . Solvent

50. . . Polycrystalline reactor

52. . . Polycrystalline germanium

1 is a schematic diagram of a system for producing decane, which relates to electrolysis of a halide salt according to an embodiment of the present invention;

Figure 2 is a cross section of a Down's cell suitable for electrolytic halide salts;

3 is a schematic view of a system for producing a ruthenium halide raw material gas containing ruthenium tetrahalide and trihalo decane;

4 is a schematic diagram of a substantial closed loop system for making decane in accordance with an embodiment of the present invention;

Figure 5 is a schematic illustration of a substantially closed loop system for making polysilicon in accordance with an embodiment of the present invention.

3. . . Halide salt

4. . . container

6. . .矽

8. . . Halogenation reactor

9. . . Hydride reactor

17. . . Metallic alkali or alkaline earth metal

18. . . Halogen gas

twenty one. . . Halogenated feed gas/halogenated germanium feedstock/halogenated germanium feedstock

30. . . Decane reactor

31. . . hydrogen

32. . . Alkali metal or alkaline earth metal hydride

35. . . Decane

37. . . Alkali metal or alkaline earth metal halide salt

Claims (46)

A system for producing decane in a substantially closed-loop process, the system comprising: a vessel for electrolyzing an alkali metal or alkaline earth metal halide salt to produce a metallic alkali or alkaline earth metal and a halogen gas; for producing at least one of the following Halogenation reactor: (1) ruthenium tetrahalide, and (2) trihalomethane; which is produced by reacting ruthenium with at least one of: (1) a halogen gas discharged from the vessel; 2) a hydrogen halide obtained by contacting a halogen gas discharged from the vessel with hydrogen; for reacting a metallic alkali metal or alkaline earth metal discharged from the vessel with hydrogen to produce an alkali metal or alkaline earth metal hydrogenation a hydride reactor for reacting at least one of (1) ruthenium tetrahalide and (2) trihalomethane with the alkali metal or alkaline earth metal hydride to produce decane and an alkali metal or alkaline earth metal halide salt a decane reactor, wherein the decane reactor is a stirred tank reactor, wherein a halogenated ruthenium raw material gas containing at least one halogenated decane selected from the group consisting of ruthenium tetrahalide and trihalo decane is bubbled through a solvent containing and dispersed therein Solvent a reaction mixture of an alkali metal or an alkaline earth metal hydride, and wherein the alkali metal or alkaline earth metal halide salt obtained therein is dissolved or suspended in the solvent; and is used for isolating the solvent and halogenating the alkali metal or alkaline earth metal Salt of matter Off the device. The system of claim 1, wherein the container is an electrolytic cell. The system of claim 1 wherein the system comprises a delivery device for delivering an alkali metal or alkaline earth metal halide salt discharged from the decane reactor to the vessel for electrolyzing an alkali metal or alkaline earth metal halide salt. The system of claim 1 comprising a transport device for delivering the solvent and the alkali metal or alkaline earth metal halide salt discharged from the decane reactor to the separator and for separating the alkali metal Or an alkaline earth metal halide salt is delivered to the delivery device for the vessel for the electrolysis of an alkali metal or alkaline earth metal halide salt. The system of claim 1 comprising a delivery device for delivering the separated solvent to the hydride reactor. The system of claim 1 wherein the halogenation reactor is a fluidized bed reactor wherein the lanthanide is suspended in a halodecane comprising at least one selected from the group consisting of ruthenium tetrahalide, trihalodecane, dihalodecane and monohalodecane. In the raw material gas of the antimony halide. The system of claim 1, wherein the hydride reactor is a stirred tank reactor, wherein hydrogen gas is bubbled through a reaction mixture containing a solvent and a metallic alkali metal or alkaline earth metal to produce an alkali metal suspended in the solvent. Or alkaline earth metal hydride. A system according to claim 7 which comprises a transport means for transporting an alkali metal or alkaline earth metal hydride and a solvent from the hydride reactor to the decane reactor. The system of claim 1, wherein the system comprises a method for decomposing decane A polycrystalline germanium reactor for hydrogen and polycrystalline germanium. The system of claim 9, wherein the polycrystalline germanium reactor is a fluidized bed reactor, wherein the decane fluidizes the polycrystalline germanium particles. The system of claim 9, wherein the system comprises a delivery device for delivering hydrogen from the polycrystalline ruthenium reactor to the hydride reactor. The system of claim 9, wherein the system comprises a delivery device for delivering decane from the decane reactor to the polycrystalline ruthenium reactor. A system according to claim 1, which comprises a conveying means for conveying a metallic alkali metal or alkaline earth metal discharged from the vessel for electrolyzing an alkali metal or alkaline earth metal halide salt to the hydride reactor. A system according to claim 1, which comprises a conveying means for conveying a halogen gas discharged from the vessel for electrolyzing an alkali metal or alkaline earth metal salt to the halogenation reactor. The system of claim 1 comprising a transport apparatus for transporting at least one of (1) ruthenium tetrahalide and (2) trihalo decane from the halogenation reactor to the decane reactor. A system according to claim 1, which comprises a hydrogen halide burner which reacts hydrogen with a halogen gas to produce a hydrogen halide. The system of claim 16 comprising a delivery device for delivering hydrogen halide to the halogenation reactor. A system according to claim 16, which comprises a conveying means for conveying a halogen gas discharged from the vessel for electrolyzing an alkali metal or alkaline earth metal salt to the hydrogen halide burner. The system of claim 1, comprising a helium storage device and for transporting helium To the delivery device of the halogenation reactor. The system of claim 1, wherein the system is a substantially closed loop with respect to hydrogen. A system as claimed in claim 1, wherein the system is a substantially closed loop with respect to halogen. The system of claim 1 wherein the system is a substantially closed loop with respect to an alkali metal or alkaline earth metal. A system according to claim 1, which comprises a disproportionation system for producing a monohalodecane or a dihalodecane from at least one of (1) ruthenium tetrahalide and (2) trihalomethane. A system for the manufacture of decane in a substantially closed-loop process, the system being a substantially closed ring of hydrogen, the system comprising: for the electrolysis of an alkali or alkaline earth metal halide salt to produce a metallic alkali or alkaline earth metal and a halogen a gas container; a halogenation reactor for producing at least one of: (1) antimony tetrahalide, and (2) trihalodecane; which are produced by reacting rhodium with at least one of: (1) a halogen gas discharged from the container; and (2) a hydrogen halide obtained by contacting a halogen gas discharged from the container with hydrogen; a metal alkali metal or alkaline earth metal for discharging the container a hydrogenation reactor for the production of an alkali metal or alkaline earth metal hydride; A decane reactor for reacting at least one of (1) ruthenium tetrahalide and (2) trihalomethane with the alkali metal or alkaline earth metal hydride to produce decane and an alkali metal or alkaline earth metal halide salt. The system of claim 24, wherein the container is an electrolytic cell. The system of claim 24, wherein the system comprises a delivery device for delivering an alkali metal or alkaline earth metal halide salt discharged from the decane reactor to the vessel for electrolyzing an alkali metal or alkaline earth metal halide salt. The system of claim 24, wherein the decane reactor is a stirred tank reactor, wherein a halogenated ruthenium halide material comprising at least one halogenated decane selected from the group consisting of ruthenium tetrahalide, trihalo decane, dihalo decane, and monohalo decane is used. The gas is bubbled through a reaction mixture containing a solvent and an alkali metal or alkaline earth metal hydride dispersed in the solvent, and the alkali metal or alkaline earth metal halide salt obtained therein is dissolved or suspended in the solvent. The system of claim 27, comprising: a separator for separating the solvent from the alkali metal or alkaline earth metal halide salt; and the solvent and the alkali metal or alkaline earth metal for discharging the decane reactor A delivery device for delivering a halide salt to the separator, and a delivery device for delivering the separated alkali metal or alkaline earth metal halide salt to the vessel for electrolyzing an alkali metal or alkaline earth metal halide salt. The system of claim 27, comprising: a separator for separating the solvent from the alkali metal or alkaline earth metal halide salt; and a transport device for transporting the separated solvent to the hydride reactor Set. The system of claim 24, wherein the halogenation reactor is a fluidized bed reactor, wherein the lanthanide is suspended in a halodecane comprising at least one selected from the group consisting of ruthenium tetrahalide, trihalo decane, dihalo decane, and monohalo decane. In the raw material gas of the antimony halide. The system of claim 24, wherein the hydride reactor is a stirred tank reactor in which hydrogen gas is bubbled through a reaction mixture containing a solvent and a metallic alkali metal or alkaline earth metal to produce an alkali metal suspended in the solvent. Or alkaline earth metal hydride. The system of claim 31, comprising a delivery device for delivering an alkali metal or alkaline earth metal hydride and a solvent from the hydride reactor to the decane reactor. The system of claim 24, wherein the system comprises a polycrystalline germanium reactor for decomposing decane to produce hydrogen and polycrystalline germanium. The system of claim 33, wherein the polycrystalline germanium reactor is a fluidized bed reactor, wherein the decane fluidizes the polycrystalline germanium particles. The system of claim 33, wherein the system comprises a delivery device for delivering hydrogen from the polycrystalline ruthenium reactor to the hydride reactor. The system of claim 33, wherein the system comprises a delivery device for delivering decane from the decane reactor to the polycrystalline ruthenium reactor. The system of claim 24, comprising a delivery device for delivering a metallic alkali or alkaline earth metal discharged from the vessel for electrolyzing an alkali metal or alkaline earth metal halide salt to the hydride reactor. The system of claim 24, comprising: for use in electrolyzing an alkali metal The halogen gas discharged from the container of the alkaline earth metal salt is supplied to the conveying device of the halogenation reactor. The system of claim 24, comprising a transport device for transporting at least one of (1) ruthenium tetrahalide and (2) trihalodecane from the halogenation reactor to the decane reactor. The system of claim 24, comprising a hydrogen halide burner that reacts hydrogen with a halogen gas to produce a hydrogen halide. A system of claim 40, comprising a delivery device for delivering hydrogen halide to the halogenation reactor. The system of claim 40, comprising a delivery device for delivering a halogen gas discharged from the vessel for electrolyzing an alkali metal or alkaline earth metal salt to the hydrogen halide burner. The system of claim 24, comprising a helium storage device and a transport device for transporting helium to the halogenation reactor. The system of claim 24, wherein the system is a substantially closed loop with respect to halogen. The system of claim 24, wherein the system is a substantially closed loop with respect to an alkali metal or alkaline earth metal. The system of claim 24, comprising a disproportionation system for producing a monohalodecane or a dihalodecane from at least one of (1) ruthenium tetrahalide and (2) trihalodecane.