201231394 六、發明說明： 【發明所屬之技術領域】 本發明之領域係關於用於製造矽烷之方法，且尤其包括 使用電解使反應性組分再生之方法。一些特定實施例係針 , 對矽烷之製造為關於鹵素及/或鹼金屬或鹼土金屬之實質 . 性「閉環（closed-loop)」之方法。 【先前技術】 矽烷為具有許多工業用途之多功能化合物。在半導體工 業中’矽烷可用於在半導體晶圓上沈積磊晶矽層及製造多 晶石夕。多晶矽為用以製造許多商業產品之重要原料，該等 商業產品包括例如可在流體化床反應器中藉由熱分解矽烷 於矽粒子上製造之積體電路及光伏打（亦即太陽）電池。 石夕烧可藉由使四氟化矽與鹼金屬或鹼土金屬鋁氫化物 (諸如四氫化鋁鈉）反應製造，如美國專利第4,632,816號中 所揭示’該文獻出於所有相關及一致之目的以引用之方式 併入本文中。此方法之特徵在於高能效；然而，起始物質 成本可負面影響該系統之經濟效益。 或者’矽烷可藉由所謂「聯合碳化物方法（Union Carbide ' Process) J製造，其中使冶金級矽與氫氣及四氯化矽反應 ’ 製造二氣石夕烧’如Mtiller等人，「Development and201231394 VI. Description of the Invention: Field of the Invention The field of the invention relates to a process for producing decane, and in particular to a process for regenerating a reactive component using electrolysis. Some specific embodiments are needles, and the manufacture of decane is a method of "closed-loop" in relation to the nature of halogens and/or alkali metals or alkaline earth metals. [Prior Art] Oxane is a multifunctional compound having many industrial uses. In the semiconductor industry, decane can be used to deposit epitaxial germanium layers on semiconductor wafers and to make polycrystalline spine. Polycrystalline germanium is an important raw material for the manufacture of a number of commercial products including, for example, integrated circuits and photovoltaic (i.e., solar) cells that can be fabricated by thermally decomposing decane on ruthenium particles in a fluidized bed reactor. The smelting can be produced by reacting lanthanum 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 for This is incorporated herein by reference. 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" J, in which metallurgical grade ruthenium is reacted with hydrogen gas and ruthenium tetrachloride to produce a two-gas stone kiln, such as Mtiller et al., "Development and
Economic Evaluation of a Reactive Distillation Process for Silane Production」，Distillation and Adsorption: /Voceiiei，2002中所述，該文獻出於所有相關 及一致之目的以引用之方式併入本文中。三氯矽烷隨後經 160825.doc 201231394 由 需 本 一系列歧化及蒸館步 要大量大型循環流， 驟處理，製造矽烷終產物。此方法 此舉增加初始設備成本以及操作成 因 此，繼續需要製造矽 況之經濟型方法及關於製造製程 内所用之某些物質之閉環的 展的方法。亦需要執行包括實質 閉環系統之該等方法之系統。 【發明内容】 本發明之一個態樣係斜 ’、^ 種由驗金屬或驗土金屬鹵化 物I來源1^#；^之方法。該方法包括電解驗金屬或驗土 金屬齒化物鹽以製造金屬性驗金屬或驗土金屬及南素氣 體。使金屬性鹼金屬或鹼土金屬與氫氣接觸製造鹼金屬或 驗土金屬氫化物。含有至少一種選自由四齒化石夕、三南石夕 烧 '二齒我及單㈣燒組成之群的㈣烧之函化石夕原料 氣藉由使i素氣體與以τ至少—者接觸來製造：⑴與石夕接 觸製造四鹵化矽，及(2)與氫氣接觸製造函化氫，其中齒化 氫進一步與矽接觸以製造含有四函化矽及三函矽烷之混合 物。使鹵化原料氣與鹼金屬或鹼土金屬氫化物接觸以製造 矽烷及驗金屬或鹼土金屬氫化物鹽。 本發明之另一個態樣係針對一種在關於鹼金屬或鹼土金 屬之實質性閉環系統中製造矽烷之方法。使_化矽原料氣 與鹼金屬或鹼土金屬齒化物接觸以製造矽烷及鹼金屬或鹼 土金屬鹵化物鹽。電解_化物鹽以製造金屬性鹼金屬或鹼 土金層及齒素氣體。使金屬性鹼金屬或鹼土金屬與氫氣接 觸以製造鹼金屬或鹼土金屬氫化物。使藉由使金屬性鹼金 160825.doc 201231394 屬或驗土金屬與氫氣接觸製造之驗金屬或驗土金屬氫化物 與齒化石夕原料氣接觸，製造石夕烧及驗金 屬或驗土金屬鹵化 物鹽。 本發明之又一冑態樣係、針對-種在關於齒素t實質性閉 衣系、’先中製造矽烷之方法。使含有至少一種選自由四鹵化 夕—齒石夕燒、二i石夕烧及單函矽烷組成之群的鹵矽烷之 鹵化矽原料氣與鹼金屬或鹼土金屬氫化物接觸以製造矽烷 及鹼金屬或鹼土金屬鹵化物鹽。電解鹵化物鹽以製造金屬 性鹼金屬或鹼土金屬及鹵素氣體。含有至少一種選自由四 鹵化矽、三齒矽烷、二鹵矽烷及單鹵矽烷組成之群的鹵矽 烧之鹵化矽原料氣係藉由使_素氣體與以下至少一者接觸 來製造：（1)與矽接觸以製造四齒化矽，及（2)與氫氣接觸 以製造ill化氫，其中該齒化氫進一步與碎接觸以製造包含 四鹵化石夕及三函石夕烧之混合物。使鹵化石夕原料氣與驗金屬 或驗土金屬氫化物接觸以製造矽烷及鹼金屬或鹼土金屬_ 化物鹽。 在本發明之另一個態樣中，製造多晶矽之閉環方法包括 使含有至少一種選自由四鹵化矽、三鹵矽烷、二鹵石夕烧及 單鹵矽烧組成之群的鹵矽烧之鹵化矽原料氣與驗金屬或驗 • 土金屬氫化物接觸，以製造矽烷及鹼金屬或鹼土金屬齒化 物鹽。熱分解矽烷以製造多晶矽及氫氣。電解鹵化物鹽以 製造金屬性驗金屬或驗土金屬及_素氣體。含有至少一種 選自由四_化矽、三鹵矽烷、二鹵矽烷及單_石夕烧组成之 群的鹵矽烷之_化矽原料氣係藉由使藉由電解鹼金屬或驗 I60825.doc 201231394 土金屬函化物製造之鹵素氣體與以下至少一者接觸來製 造.（1)與矽接觸以製造四齒化矽，及（2)與氫氣接觸以製 造鹵化氫，其中使鹵化氫進一步與矽接觸以製造含有四鹵 化矽及二鹵矽烷之混合物。使金屬性鹼金屬或鹼土金屬與 由矽烷之熱分解製造之氫氣接觸，以製造鹼金屬或鹼土金 屬氫化物。使藉由使鹵素氣體或鹵化氫與矽接觸製造之鹵 化矽原料氣與藉由使金屬性鹼金屬或鹼土金屬與氫氣接觸 製造之鹼金屬或鹼土金屬氫化物接觸，來製造矽烷及鹼金 屬或驗土金屬函化物鹽。 在本發明之又一個態樣中，用於在實質性閉環方法中製 造矽烷之系統包括用於電解鹼金屬或鹼土金屬鹵化物鹽以 製造金屬性鹼金屬或鹼土金屬及_素氣體之容器。該系統 包括用於製造以下至少-者之函化反應器：⑴四齒化石夕及 (2)三函矽烷，其係藉由使矽與以下至少一者反應來製造： (1)自容器中排出之齒素氣體及（2)使自容器中排出之函素 氣體與氫氣接觸製造之由化氫。該系統包括用於使自容器 中排出之金屬性鹼金屬或鹼土金屬與氫氣反應製造鹼金屬 或鹼土金屬氫化物的氫化物反應器。該系統包括用於使⑴ 四齒切及⑺三㈣烧中之至少—者與驗金屬或酴土金屬 氫化物反應製造矽烷及鹼金屬或鹼土金屬函化物鹽的矽烷 反應器。 關於以上所提及之本發明態樣所指出之特徵存在各種改 進。其他特徵亦可併人以上所提及之本發明態樣中。此等 改進及其料徵可個別地或以任何組合之形式存知舉例 160825.doc 201231394 而言，以下關於任一所說明之本發明實施例所討論之各種 特徵可單獨地或以任何組合之形式併入任一上述本發明態 樣中。 【實施方式】 在所有圖式中，對應參考字符指示對應部件。 本發明實施例之方法在用於製造矽烷之方法_使用電解 使反應性組分再生。電解允許矽烷製造方法視情況為關於 系統中所用之某些化合物（諸如函素（例如氣）及/或鹼金屬 或鹼土金屬（例如鈉））的實質性閉環系統。如本文所用，片 語「實質性閉環方法（SubstantiaUy Cl〇sed l〇〇p pr〇cess)」 或「實質性閉環系統（substantially closed_loop system)」 係才曰具有以下特徵之方法或系統，其中與該系統或方法為 閉環相關之化合物除作為雜質以外不會自系统或方法中抽 出且不會出於除補充在系統中作為雜質損失之化合物量 (例如所補充之化合物量小於系統内總循環之約，下文 將更全面地描述）以外之目的饋入系統或方法中。 在本發明之一或多個實施例中，矽烷藉由電解鹼金屬或 鹼土金屬齒化物鹽以製造金屬性鹼金屬或鹼土金屬及鹵素 氣體來製造。使金屬性鹼金屬或鹼金屬與氫氣反應以製造 虱化物，且使鹵素氣體與矽（且另外在一些實施例中為氫 氣）反應以製造含有四_化石夕且在一些實施例中含有三函 石夕烧之鹵切補氣。使原料氣反應以製造錢及_化物 鹽β在方法為關於鹼金屬或鹼土金屬及鹵素氣體中之至少 者的貫質性閉環之實施例中，鹵化物鹽副產物藉由電解 160825.doc 201231394 ::物鹽以製造金屬性驗金屬或驗土金屬及㈣氣體而再 循環。 使用電解製造矽貌 現在參看圖】，南化物鹽3引入容 齒化物鹽電解以製造齒辛氣 隹…中使 wa > 常體例如α2)及金屬（例如金屬 性鹼金屬或鹼土金屬）。如本文所用「点 ,,.^ 文所用，「鹵化物鹽（halide salt)」含有鹼金屬或鹼土 金屬及南素。鹵化物鹽可具有通 式MXy，其中M為鹼金屬 驗金屬時…，且當Μ為驗土二l X為㈣，且當_ , 為驗土金屬時y為2。函化物鹽之鹼 金屬或驗土金屬(且在如下文所述之某些實施例中兑在 閉環系統内再循環)可選自由以下組成之群：鐘、鈉、 卸、鎮、鎖、鹤及其混合物。函素可選自氣、氣、漠、诚 及其混合物。馨於氣化納之廣泛可用性且#於氯㈣可較 谷易地分離成其組成部分（例如氯氣㈣及金屬 納)，故：為較佳鹼金屬或鹼土金屬且氯為較佳齒素。就 此點而吕，應瞭解’可使用任何驗金屬或驗土金屬且可使 用任何齒素，在如下所述用於製造石夕烧之方法及系統為關 於驗金屬或驗土金屬之閉環的實施例中尤其如此。 一種適合電解齒化物鹽之容器4為唐氏池(D0Wns cell)。 例示性唐氏池顯示於圖2中且參考數字-般為「2〇」。唐 氏池20包括位於其十之一或多種函化物鹽，且含 14及陰極16。陽極14可由例如碳（例如石墨m成且陰極w 可由例如鋼或鐵構成。在陽極14處，氣離子氧化形成齒素 氣體（例如Cl2)。在陰極16處，鹼金屬或驗土金屬離子還原 160825.doc 201231394 形成金屬性鹼金屬或鹼土金屬。就此點而言，應瞭解，如 本文所用，術語「金屬性（metallic)」係指氧化數為〇之^ 金屬或驗土金屬。所形成之_素氣體及金屬性驗金屬或驗 土金屬由分隔物19分開。分隔物19可為由鋼或鐵製成之篩 網或絲網。就此點而言，應瞭解，可使用不為唐氏池之電 解池，諸如美國專利第5,904,821號中所述之電解池，該文 獻出於所有相關及_致之目的以引用之方式併人本文中。 所製造之金屬性驗金屬或驗土金屬之密度小於齒化物 鹽’此使得其在池中上升。齒素氣體亦上升，且齒素氣體 18與金屬性驗金屬或鹼土金屬17均自唐氏池中移除。可向 唐氏池中添加第二鹼金屬或鹼土金屬鹽以形成共晶混合物 且壓低電解之鹵化物鹽之熔點以減少熔融_化物鹽及/或 使鹵化物鹽維持熔融狀態之能量消耗。舉例而言，當氯化 納在唐氏池20中電解時，可添加一定量之氯化鈣、氯化鋁 或碳酸鈉以壓低氣化鈉之熔點。舉例而言，與單獨氣化鈉 之熔點801。(：相比，含有53 2 m〇1%氯化鈣及仏』爪〇1%氣 化鈉之混合物之熔點為的々^，且含有23」酸鈉及 76.9 mol%氯化鈉之例示性混合物之熔點為634。〇。較佳 地第一鹽之鹼金屬或驗土金屬與_化物鹽之驗金屬或驗 土金屬相同，或為比_化物鹽之鹼金屬或鹼土金屬弱之氧 化劑，以便不影響齒化物鹽之鹼金屬或鹼土金屬之還原。 再次參看圖1’ _素氣體18引入鹵化反應器8中，在該鹵 化反應器中其與矽6接觸以製造含有四_化矽（例如siC14) 之鹵化原料氣21。下文說明此反應： 160825.doc 201231394 • ,Economic Evaluation of a Reactive Distillation Process for Silane Production", Distillation and Adsorption: /Voceiiei, 2002, which is hereby incorporated by reference in its entirety for all purposes for all of the same purposes. The chloroformane is then subjected to a series of disproportionation and steaming steps, and a large number of large circulating streams are processed to prepare the final product of decane by 160825.doc 201231394. This approach adds to the initial equipment cost and operation as a result of the continuing need for an economical method of manufacturing and a closed-loop approach to the manufacture of certain materials used in the process. It is also necessary to implement a system comprising such methods of a substantially closed loop system. SUMMARY OF THE INVENTION One aspect of the present invention is a method of detecting metal or soil metal halide I from a source. The method includes electrolytically examining a metal or a soil metallized salt to produce a metallic metal or a soil metal and a gas. The alkali metal or alkaline earth metal is contacted with hydrogen to produce an alkali metal or soil metal hydride. a (four) burning functional fossil-containing raw material gas containing at least one group selected from the group consisting of four-tooth fossil eve, Sannan Shixi-burning 'two-toothed me and one (four)-burning by making the elemental gas and at least τ contact (1) making contact with Shixia to produce ruthenium tetrahalide, and (2) contacting hydrogen gas to produce a functional hydrogen, wherein the hydrogenated hydrogen is further contacted with ruthenium to produce a mixture containing tetradide and trioxane. The halogenated feed gas is contacted with an alkali metal or alkaline earth metal hydride to produce a decane and a 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 cerium raw material gas is contacted with an alkali metal or alkaline earth metal tooth to produce a decane and an alkali metal or alkaline earth metal halide salt. The electrolytic salt is used to produce a metallic alkali metal or alkaline earth gold layer and a dentate gas. A metallic alkali metal or alkaline earth metal is contacted with hydrogen to produce an alkali metal or alkaline earth metal hydride. The metal or soil metal hydride produced by contacting the metallic alkali gold 160825.doc 201231394 or the soil of the soil and hydrogen is contacted with the tooth fossil raw material gas to produce the stone and the metal or soil metal halide. Salt. Another aspect of the present invention is a method for producing a decane in the context of a substantial closure of the dentate t. Contacting a halogenated ruthenium raw material gas containing at least one halogenated decane selected from the group consisting of tetrahalogenated sulphate, sulphide, and monodecane with an alkali metal or alkaline earth metal hydride to produce decane and an alkali metal Or an 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 lanthanum halide raw material gas containing at least one selected from the group consisting of ruthenium tetrahalide, tridentane, dihalodecane and monohalodecane is produced by contacting a gas with at least one of: (1) Contacting the crucible to produce a tetradentate crucible, and (2) contacting hydrogen gas to produce ill hydrogen, wherein the hydrogenated hydrogen is further contacted with the crumb to produce a mixture comprising a tetrahalogenated fossil and a trigeminite. The halogenated fossil feed gas is contacted with a metal or soil metal hydride to produce a decane and an alkali metal or alkaline earth metal salt. In another aspect of the present invention, a closed-loop method for producing polycrystalline germanium includes subjecting a halogenated antimony halide containing at least one selected from the group consisting of antimony tetrahalide, trihalodecane, dihalite, and monohalogenated antimony. The feed gas is contacted with a metal or a metal hydride to produce a decane and an alkali or alkaline earth metal tooth salt. The decane is thermally decomposed to produce polycrystalline germanium and hydrogen. Electrolytic halide salts are used to make metal or metal and soil gases. The ruthenium-containing raw material gas containing at least one group selected from the group consisting of tetrahydropallium, trihalodecane, dihalodecane and mono-stone sulphate is made by electrolyzing an alkali metal or by I60825.doc 201231394 The halogen gas produced by the earth metal complex is manufactured by contacting at least one of (1) contact with ruthenium to produce a tetradentate ruthenium, and (2) contact with hydrogen to produce hydrogen halide, wherein the hydrogen halide is further contacted with ruthenium. To produce a mixture containing ruthenium tetrahalide and dihalo decane. 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 Earth test metal salt. In still another aspect of the invention, a system for making decane in a substantially closed loop process includes a vessel for electrolyzing an alkali or alkaline earth metal halide salt to produce a metallic alkali or alkaline earth metal and a gas. The system comprises at least one of the following functional reactors: (1) tetradentate fossil and (2) trioxane, which are produced by reacting hydrazine with at least one of the following: (1) from a container The discharged dentate gas and (2) the hydrogen produced by contacting the funnel gas discharged from the container 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) tetradentate cutting and (7) tri (four) firing with a metal or alumina metal hydride to produce decane and an alkali metal or alkaline earth metal complex salt. There are various improvements in the features indicated in the above-mentioned aspects of the invention. Other features may also be incorporated in the aspect of the invention as mentioned above. Such improvements and their identities may be known individually or in any combination. For example, 160825.doc 201231394, the various features discussed below with respect to any of the illustrated embodiments of the invention may be used individually or in any combination. Incorporating into any of the above aspects of the invention. [Embodiment] In all the drawings, corresponding reference characters indicate corresponding components. The method of the embodiments of the present invention is used in the process for producing decane to regenerate reactive components using electrolysis. Electrolysis allows the decane manufacturing process to be a substantially closed loop system with respect to certain compounds used in the system, such as a gas (e.g., gas) and/or an alkali metal or alkaline earth metal (e.g., sodium). As used herein, the phrase "SubstantiaUy Cl〇sed l〇〇p pr〇cess" or "substantially closed_loop system" is a method or system having the following characteristics, The system or method is a closed-loop related compound that is not extracted from the system or method other than as an impurity and does not deplete the amount of compound that is lost as impurities in the system (eg, the amount of compound added is less than the total cycle in the system) Feeds into the system or method for purposes other than that described below more fully. In one or more embodiments of the invention, the decane is produced by electrolyzing an alkali metal or alkaline earth metal tooth salt to produce a metallic alkali or alkaline earth metal and a halogen gas. The metal alkali metal or alkali metal is reacted with hydrogen to produce a telluride, and the halogen gas is reacted with hydrazine (and, in some embodiments, hydrogen) to produce a tetra-synthesis and in some embodiments a three-letter Shi Xi burned the halogen to cut the qi. The reaction of the feed gas to produce the money and the salt of the salt is in the embodiment of the process of being a closed loop of at least the alkali metal or alkaline earth metal and the halogen gas, the halide salt by-product by electrolysis 160825.doc 201231394 :: Salt is recycled by making metal or metal and (4) gases. The use of electrolysis to produce a ruthenium Referring now to the figure, the hydride salt 3 is introduced into the dentate salt electrolysis to produce a dentate gas such as wa > a normal body such as α2) and a metal (e.g., a metallic alkali metal or an alkaline earth metal). As used herein, "halide salt" is used to mean alkali metal or alkaline earth metal and sulphate. The halide salt may have the general formula MXy, where M is an alkali metal metallurgy... and when Μ is the soil test 2 l X is (4), and when _ is the soil test metal, y is 2. Alkali metal or soil test metal of the salt (and in some embodiments as described below, recycled in a closed loop system) may be selected from the group consisting of: clock, sodium, unloading, town, lock, crane And mixtures thereof. The element can be selected from the group consisting of gas, gas, desert, sincerity and mixtures thereof. The versatile availability of scented gasification and the separation of chloro (4) into its constituents (such as chlorine (4) and metal nanoparticles) is preferred. It is a preferred alkali or alkaline earth metal and chlorine is the preferred dentate. At this point, Lu should understand that 'any metal or soil test metal can be used and any fangs can be used. The method and system for manufacturing the stone shovel as described below is the implementation of the closed loop of the metal or soil test. This is especially true in the case. A container 4 suitable for electrolytic tooth salt is a D0Wns cell. An exemplary Down's pool is shown in Figure 2 and the reference number is generally "2". The Pool 20 includes one or more of its tenth salt and contains 14 and a cathode 16. The anode 14 may be composed of, for example, carbon (e.g., graphite m and the cathode w may be composed of, for example, steel or iron. At the anode 14, gas ions are oxidized to form a dentate gas (e.g., Cl2). At the cathode 16, alkali metal or soil metallization is reduced. 160825.doc 201231394 Forming a metallic alkali metal or alkaline earth metal. In this regard, it should be understood that, as used herein, the term "metallic" refers to a metal or earth-measuring metal having an oxidation number of 〇. The gas and metallurgical metal or soil test metal are separated by a partition 19. The partition 19 may be a screen or a wire mesh made of steel or iron. In this regard, it should be understood that the use may not be Down's. The electrolytic cell of the pool, such as the electrolytic cell described in U.S. Patent No. 5,904,821, the disclosure of which is hereby incorporated by reference in its entirety for all purposes for all purposes. Less than the toothed salt' this causes it to rise in the pool. The dentate gas also rises, and the dentate gas 18 and the metallic metal or alkaline earth metal 17 are removed from the Down's pool. Diabasic metal The alkaline earth metal salt forms a eutectic mixture and depresses the melting point of the electrolytic halide salt to reduce the energy consumption of the molten salt and/or maintains the halide salt in a molten state. For example, when the sodium chloride is in the Down cell 20 In the middle electrolysis, a certain amount of calcium chloride, aluminum chloride or sodium carbonate may be added to lower the melting point of the vaporized sodium. For example, it has a melting point of 801 with sodium vaporization alone (:: 53 2 m〇) The melting point of a mixture of 1% calcium chloride and 1% sodium sulphate is 々^, and the exemplary mixture containing sodium 23" and 76.9 mol% sodium chloride has a melting point of 634. The alkali metal or soil test metal of the first salt is the same as the metal or soil test metal of the salt, or is an oxidant weaker than the alkali metal or alkaline earth metal of the salt, so as not to affect the alkali metal of the tooth salt or Reduction of the alkaline earth metal. Referring again to Figure 1 'the gas 18 is introduced into a halogenation reactor 8 where it is contacted with ruthenium 6 to produce a halogenated feed gas 21 containing tetrahydroanthracene (e.g., siC14). Explain this reaction: 160825.doc 201231394 • ,
Si + 2X2 —► SiX4 (1) 矽6之來源可為冶金級矽；然而，應瞭解，可使用其他矽 來源諸如（亦即Si〇2)、石英、縫石、矽藻土、礦物矽 鷇鹽、氟矽酸鹽及其混合物。就此點而言，應瞭解，如本 文所用兩種或兩種以上反應性化合物之「接觸 (contact)」一般會引起該等組分之反應，且術語「接觸 (contacting)」及「反應（reacting)」為同義詞，如同此等術 語之派生詞一般，且此等術語及其派生詞不應被視為具有 限制意義。 作為與矽直接反應之替代且如圖3中所示，_素氣體18 可與氫氣28在鹵化氫燃燒器25(與鹵化氫「烘箱」或 「爐」同義）中反應以形成齒化氫26(HXp根據如下所示 反應’齒化氫26可在鹵化反應器8中與矽6反應形成含有三 鹵矽烷及四鹵化矽之齒化矽原料氣2 i，：Si + 2X2 — ► SiX4 (1) The source of 矽6 can be metallurgical grade 矽; however, it should be understood that other 矽 sources such as (ie Si〇2), quartz, scutellite, diatomaceous earth, mineral 矽鷇 can be used. Salt, fluoroantimonate and mixtures thereof. In this regard, it is to be understood that "contacts" of two or more reactive compounds as used herein generally cause the reaction of such components, and the terms "contacting" and "reacting". Is a synonym, 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, _ gas 18 can be reacted with hydrogen 28 in a hydrogen halide burner 25 (synonymous with a hydrogen halide "oven" or "furnace") to form hydrogenated hydrogen 26 (HXp reacts as described below. 'Tooth hydrogenation 26 can be reacted with ruthenium 6 in the halogenation reactor 8 to form a dentate ruthenium feed gas 2 i containing trihalo decane and ruthenium tetrahalide:
Si + 3HX — SiHX3 + H2 (2)Si + 3HX — SiHX3 + H2 (2)
Si + 4HX —>· SiX4 + 2H2 (3) 鹵化矽原料氣2 Γ中四_化矽與三鹵矽烷之莫耳比可變化， 且在多個實施例中，可為約1:7至約1:2或約1:6至約1:3。 就此點而言，應瞭解’矽6與鹵化氫26之反應亦可製造但 不限於一定量之二鹵矽烧及/或單鹵石夕烧。 在某些實施例中’與矽直接鹵化（圖1)相比，較佳為鹵 素氣體18與氫氣28反應形成鹵化氫，之後與石夕反應形成包 含三齒石夕烧及四_化石夕之混合物（圖3 )，此係因為與四鹵化 石夕相比’由三齒石夕院使用較少氫化物即可製造石夕烧，如以 160825.doc •10· 201231394 下反應5-6ii中所示。此外，相對於鹵化氫與矽之反應，直 接齒化反應可能需要較南溫度且可能更難#制。 氫氣2 8之來源可選自下文關於氫氣原料3丨所述之來源。 氫氣28之來源視情況可為由鹵化原料氣21，再循環得到之氣 氣或自函化石夕原料氣21中分離之氫氣。氫氣可使用氣液分 • 離器（未圖示）自鹵化矽原料氣21，中分離。該等氣液分離器 之實例包括使進氣之壓力及/或溫度降低而引起低沸點氣 體（例如四鹵化石夕及/或三_石夕院）冷凝並與高沸點氣體（例 如氫氣）分離的容器。適合之容器包括在此項技術中通常 稱為「分液罐（knock-out drum)」之容器。該容器可視情 況經冷卻以促進氣體分離。或者，氫氣可藉由一或多個蒸 餾塔分離。 作為如圖3所示在鹵化氫燃燒器中使氫氣與鹵素反應， 之後在鹵化反應中使画化氮與秒反應之替代，可使氯 氣、鹵素氣體及矽在一個容器中反應以製造包含三鹵石夕烧 及四鹵化石夕之混合物。就此點而言’應瞭解儘管鹵化氫之 製備已參考無水鹵化氫氣體一般化地描述，但在一些實施 例中’可製造鹵化氫水溶液且尤其HF水溶液，其可藉由熟 習此項技術者已知之方法與矽反應以製造包含三鹵石夕院及 四鹵化石夕之混合物。此外’就此點而言，儘管鹵化氫及石夕 之反應產物已經描述為包含三鹵矽烷及四_化石夕之混合 物，但應瞭解，可控制反應參數以製造四齒化石夕及僅微量 三鹵矽烷（例如小於約5體積°/。或小於約1體積％)或製造三 鹵矽烷及微量四鹵化矽（例如小於約5體積％或小於約1體積 160825.doc • 11 · 201231394 〇/〇)。 鹵化反應器8可以流體化床形式操作，其中使石夕懸浮於 進氣（例如鹵素18(圖1)或鹵化氫26(圖3))中。鹵化反應器8 可在室溫（例如約20°C)下操作，尤其當選擇氟作為鹵素 時。更一般而5 ’反應器之操作溫度可為至少約2 〇 °c、至 少約75°C、至少約150°C、至少約25〇°c、至少約5〇〇〇c、 至少約750°C、至少約100(TC或至少約U5〇〇c(例如為約 20°C 至約 1200°C 、約 250。(：至約 12〇〇。(：或約 500。(：至約 1200C)。反應器8之操作壓力可為至少約1巴、至少約3巴 或甚至至少約6巴（例如為約1巴至約8巴或約3巴至約8巴）。 就此點而s，應瞭解，圖1中所示之鹵化石夕原料流21及 圖3中所示之函化石夕原料流21’可含有不為四齒化矽或三_ 矽烷之齒矽烷，諸如一定量之單_矽烷及/或二齒矽烷。 此外，鹵化矽原料流21或鹵化矽原料流21，可引入歧化系統 (未圖示）中，以製造一定量之三鹵矽烷、二函矽烷及/或單 鹵石夕烧。應瞭解’如本文所用，「_化矽原料氣 (halogentated silicon feed gas)」包括含有任何量之一或多 種i矽烷（亦即四_化矽、三_矽烷、二齒矽烷或單齒矽 烧）之任何氣體且包括尚未引入歧化系統中與已引入歧化 系統中之氣體。 再次參看圖1，鹵化矽原料流21(或如圖3中之鹵化矽原 料流21’）引入矽烷反應器30中以製造矽烷35。在引入矽烷 反應器30中之前，鹵化矽原料氣21(或含有四鹵化矽與三 齒石夕烧之原料氣2Γ)可經純化以移除諸如_化鋁或函化鐵 160825.doc 12 201231394 (例如當鹵素為氣時為AlCh及/或FeCh)及/或碎聚人物（卷 鹵素為氯時為SinClm聚合物）之雜質。此等雜質可藉由冷^ 氣體以自系統中沈澱出雜質來移除。所沈澱之雜質可藉由 將氣體引入諸如袋濾器或氣旋分離器之顆粒分離器中來移 除。為沈澱出雜質（例如金屬_化物及/或矽聚合物），可使 鹵化矽原料氣2 1 (或四鹵化矽及/或三鹵矽烷之混合物21，） 冷卻至小於約200。(：之溫度’或如在其他實施例中，小於 約175°C、小於約150t或甚至小於約125°C (例如為約 l〇〇°C至約200°C或約125°C至約175eC )。氣體可藉由在熱 交換裝置及/或冷卻器裝置中與冷卻水或冷卻油交換熱來 冷卻。在雜質移除之後’函化矽原料氣21 (或四函化矽及/ 或三鹵矽烷之混合物2Γ)可含有小於1〇體積。/。雜質（亦即不 為鹵矽烷之化合物）或甚至小於約5體積％、小於約1體積 %、小於約0.1體積。/。或甚至小於約〇 〇1體積％雜質（例如 0.001體積％至約10體積％或約0.001體積％至約1體積。/〇)。 製造作為電解產物之金屬性鹼金屬或鹼土金屬I7引入氫 化物反應器9中。一定量之氫氣3 1亦引入氫化物反應器9 中。如以下反應中所示，金屬性鹼金屬或鹼土金屬與氫氣 之間的反應製造鹼金屬或鹼土金屬氫化物32 : (2/y)M + H2 — (2/y)MHy (4) 其中當Μ為鹼金屬時y為1，且當μ為鹼土金屬時y為2。舉 例而言，當Μ為Na時，反應如下進行， 2Na + H2 2NaH (4i)。 當M為Ca時，反應如下進行， I60825.doc 201231394 (4ii) 0Si + 4HX —>· SiX4 + 2H2 (3) bismuth halide raw material gas 2 The molar ratio of _ _ 矽 to trihalo decane may vary, and in various embodiments, may be about 1:7 to About 1:2 or about 1:6 to about 1:3. In this regard, it should be understood that the reaction of '6 with hydrogen halide 26 can also be made, but is not limited to a certain amount of dihalogenated and/or monohalite. In some embodiments, it is preferred that the halogen gas 18 reacts with the hydrogen gas 28 to form a hydrogen halide, and then reacts with the stone to form a tridentate stone and a four-fossil eve. Mixture (Fig. 3), this is because compared with the tetrahalide fossils, 'the use of less hydrides from the tridentate stone courtyard can be used to make the stone shochu, as in the reaction of 160825.doc •10·201231394 5-6ii Shown. In addition, the direct toothing reaction may require a relatively south temperature and may be more difficult than the reaction of hydrogen halide with hydrazine. The source of hydrogen 28 can be selected from the sources described below with respect to the hydrogen feedstock. The source of the hydrogen gas 28 may be, for example, a halogenated feed gas 21, a gas obtained by recycling, or a hydrogen gas separated from the fossil feed gas 21 . Hydrogen gas can be separated from the halogenated raw material gas 21 by using a gas-liquid separator (not shown). Examples of such gas-liquid separators include lowering the pressure and/or temperature of the intake air to cause condensation of low-boiling gases (such as tetrahalide fossils and/or tri-stones) and separation from high-boiling gases such as hydrogen. Container. Suitable containers include those commonly referred to in the art as "knock-out drums". The vessel may be cooled as appropriate 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, and then reacting the drawn nitrogen with a second in the halogenation reaction, the chlorine gas, the halogen gas, and the ruthenium can be reacted in one vessel to produce three A mixture of brine stone and tetrahalogenated fossils. 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 especially an aqueous HF solution can be produced, which can be obtained by those skilled in the art. The method is known to react with hydrazine to produce a mixture comprising a trihalite stone garden and a tetrahalide fossil. In addition, in this regard, although the reaction products of hydrogen halide and Shixi have been described as comprising a mixture of trihalodecane and tetra-phosphorus, it is understood that the reaction parameters can be controlled to produce tetradentate fossils and only trace amounts of trihalides. a decane (e.g., less than about 5 vol/or less than about 1 vol%) or a trihalomethane and a trace amount of ruthenium tetrahalide (e.g., less than about 5% by volume or less than about 1 volume of 160825.doc • 11 · 201231394 〇/〇) . The halogenation reactor 8 can be operated in the form of a fluidized bed in which the diarrhea is suspended in an inlet (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 5' reactor can be operated at a temperature of at least about 2 ° C, at least about 75 ° C, at least about 150 ° C, at least about 25 ° C, at least about 5 ° C, at least about 750 °. C, at least about 100 (TC or at least about U5〇〇c (for example, from about 20 ° C to about 1200 ° C, about 250. (: to about 12 〇〇. (: or about 500. (: 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). It is understood that the halogenated fossil feed stream 21 shown in Figure 1 and the fossilized feed stream 21' shown in Figure 3 may contain a dentate that is not tetradentate or trioxane, such as a certain amount of _ In addition, 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 certain amount of trihalodecane, dioxane and/or monohalide. "_____________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________ Any gas of bidentane or monodentate) 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, the hafnium halide feed stream 21 (or hafnium halide feed stream 21 as shown in Figure 3) ') is introduced into the decane reactor 30 to produce decane 35. Prior to introduction into the decane reactor 30, the ruthenium halide feed gas 21 (or the ruthenium tetrahalide and the tridentate raw material gas 2 Γ) can be purified to remove Impurities such as _ aluminized or functionalized iron 160825.doc 12 201231394 (for example AlCh and/or FeCh when halogen is gas) and/or fragmented people (SinClm polymer when halogen is chlorine). It can be removed by precipitating impurities from the system by cold gas. The precipitated impurities can be removed by introducing the gas into a particle separator such as a bag filter or a cyclone separator. _ and/or ruthenium polymer), which can be used to cool the ruthenium halide feed gas 2 1 (or a mixture of ruthenium tetrahalide and/or trihalo decane 21) to less than about 200. (: temperature ' or as in other implementations In an example, less than about 175 ° C, less than about 150 t or even To less than about 125 ° C (eg, from about 10 ° C to about 200 ° C or from about 125 ° C to about 175 ° C). The gas can be cooled or cooled by cooling in a heat exchange device and / or cooler device The oil is exchanged for heat to cool. After the impurities are removed, the functional material 21 (or the mixture of tetradoxon and / or trihalodecane 2) may contain less than 1 volume. /. Impurity (ie, not halogen) The compound of decane) or even less than about 5% by volume, less than about 1% by volume, less than about 0.1 volume. /. Or even less than about 1% by volume of impurities (e.g., 0.001% to about 10% by volume or about 0.001% by volume to about 1% by volume). A metallic alkali metal or alkaline earth metal I7, which is an electrolytic product, is introduced into the hydrogenation reactor 9. A certain amount of hydrogen 3 1 is also introduced into the hydride reactor 9. As shown in the following reaction, the reaction between a metallic alkali metal or alkaline earth metal and hydrogen produces an alkali metal or alkaline earth metal hydride 32: (2/y) M + H2 — (2/y) MHy (4) When Μ is an alkali metal, y is 1, and when μ is an alkaline earth metal, y is 2. For example, when hydrazine is Na, the reaction proceeds as follows, 2Na + H 2 2NaH (4i). When M is Ca, the reaction proceeds as follows, I60825.doc 201231394 (4ii) 0
Ca + H2 —> CaH 反應（4)可在虱化物反應器9内在溶劑存在下發生。適合 之溶劑包括各種烴化合物’諸如甲苯、二曱醚、二乙二醇 二曱醚及離子液體，諸如NaAlCU。在使用NaAlCl4之實施 例申，氫化物反應器9可包括電極。一旦鹼金屬或鹼土金 屬氫化物之供應耗盡，則電極可激發而引起鈉（包括一定 量來自NaAlCU之鈉）與H2反應並使氫化物化合物再生。在 使用NaAlCU作為容劑之實施例中，可添加其他離子化合 物以形成如美國專利第6,482,38 1號中所揭示之共晶混合 物，a亥文獻出於所有相關及一致之目的以引用之方式併入 本文中。 氫化物反應器9可為攪拌槽反應器，其中添加有一定量 之溶劑（未圖示）及金屬性鹼金屬或鹼土金屬17。氫氣31可 鼓泡穿過反應混合物以分批模式或在半連續或連續製程中 形成鹼金屬或鹼土金屬氫化物Μ。適合的氩氣31來源包括 市售氫氣或獲自其他製程流之氫氣。舉例而言，在鹵化氫 與石夕反應之實施例中’ |氣可自三㈣燒及四画化石夕混合 物21’中分離（例如如上所述之氣液分離器）。或者或另外， 可使用在下游多晶秒製造期間自⑦烧釋放之氫氣。添加至 反應器9中之溶劑、氫氣31及金屬性鹼金屬或鹼土金屬17 之量可經選擇以便反應器9中氫化物與溶劑之量的重量比 可為至少約1:20 ’且在其他實施例中為至少約1:1〇、至少 約1:5、i少約1:3、至少約2:3或甚至至少約1:1(例如為約 1:20至約1:1或約1:10至約2:3)。 I60825.doc 201231394 在-或多個實施例中，使用例如一或多個具有一或多個 葉輪之相對較高軸之混合器充分混合反應H9中之反應 此口物才目對較向之授動使氣氣充分分散於整個反應混合 物中以便使氫氣之溶解速率達到最大，以及自金屬性驗金 屬或驗土金屬中前a α d刀任何固體鹼金屬或鹼土金屬氫化物以 便使液體鹼金屬或鹼土金屬可連續用於與溶解之氫氣反 應”尤此點而§且不希望受任何特定理論束缚，氫化物反 應益中之質里轉移視液體側阻力及預期介於約100 s-丨至約 1〇〇,〇綱S之間且更通常介於約l，〇〇G s.i與約10，GG0 s·1之 間的租積氣液質量轉移係數而定。應注意，特定體 積氣液質里轉移係數（KLaG)可視選擇用於反應器9中之特 定就化物及溶劑而不同。該等數值可由熟習此項技術者根 據已知方法容易地測定（例如量測隨時間變化之氫氣吸 收）。Ca + H2 -> The CaH reaction (4) can occur in the telluride reactor 9 in the presence of a solvent. Suitable solvents include various hydrocarbon compounds such as toluene, dioxane, diethylene glycol dioxime ether and ionic liquids such as NaAlCU. In the embodiment using NaAlCl4, the hydride reactor 9 may 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 NaAlCU) to react with H2 and regenerate the hydride compound. In embodiments in which NaAlCU is used as the bulking agent, other ionic compounds may be added to form a eutectic mixture as disclosed in U.S. Patent No. 6,482,38, the disclosure of which is incorporated herein by reference in its entirety for Incorporated herein. 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 in a batch mode or in a semi-continuous or continuous process. Suitable sources of argon 31 include commercially available hydrogen or hydrogen from other process streams. For example, in the embodiment in which the hydrogen halide reacts with the Shixia reaction, the gas can be separated from the three (four) firing and the four-painted fossil mixture 21' (e.g., a gas-liquid separator as described above). Alternatively or additionally, hydrogen gas released from the 7-burn during the downstream polycrystalline seconds manufacturing may 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 1:1 Å, at least about 1:5, less than 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). I60825.doc 201231394 In one or more embodiments, the reaction in the reaction H9 is thoroughly mixed using a mixer such as one or more relatively high axes of one or more impellers. The gas is sufficiently dispersed throughout the reaction mixture to maximize the rate of hydrogen dissolution, and any solid alkali or alkaline earth metal hydride from the metal or metal test metal in the metal or soil test metal to make the liquid alkali metal Or an alkaline earth metal can be continuously used to react with dissolved hydrogen. In particular, and without wishing to be bound by any particular theory, the hydride reaction benefits are transferred to the liquid side resistance and are expected to be between about 100 s-丨 to Approximately 1 〇〇, between the S and more usually between about 1, 〇〇G si and about 10, GG0 s·1, depending on the mass transfer coefficient of the gas-liquid mass. It should be noted that a specific volume of gas and liquid The mass transfer coefficient (KLaG) may vary depending on the particular compound and solvent selected for use in reactor 9. These values can be readily determined by those skilled in the art according to known methods (e.g., measuring hydrogen evolution over time) ).
在本發明之若干實施例中，氫化物反應器9在高壓條件 下操作’壓力為諸如至少約5 〇巴、至少約12 5巴、至少約 200巴、至少約275巴或至少約350巴（例如為約50巴至約 350巴或約50巴至約2〇〇巴）。氫化物反應器9可在小於鹼金 屬或鹼土金屬鹵化物之熱分解之溫度下操作，溫度為諸如 小於約160°C、小於約i45°C或小於約130°C (例如為約 120°C 至約 160°C 驗金屬或鹼土金屬氫化物32在有機溶劑中通常為固體。 含有懸浮於溶劑中之鹼金屬或鹼土金屬氫化物32之毁料可 引入矽烷反應器30中以製造矽烷35。就此點而言，應瞭 160825.doc 15 201231394 解，在本發明之某些其他貫施例中，鹼金屬或鹼土金屬氫 化物3 2可以含有較少量洛劑之固體或結塊固體形式引入矽 烧反應器30中。驗金屬或驗土金屬可藉由離心或過濾或藉 由熟習此項技術者可用之任何其他適合之方法與溶劑分 離。就此點而言，應瞭解’可使用但不限於不為有機溶劑 之溶劑（例如NaAlCU)。 如上所述，來自鹵化矽原料氣21(或如圖3中之包含四鹵 化矽及三產矽烷之混合物21，）之四函化矽及鹼金屬或驗土 金屬氫化物3 2引入矽烷反應器3 〇中以根據如下所示反應製 造矽烷35及函化物鹽37 : (4/y)MHy + SiX4 — (4/y)MXy + SiH4 (5) 3MHy + ySiHX3 — 3MXy + ySiH4 ⑹ 其中當M為鹼金屬時y為1，且當M為鹼土金屬時y為2。舉 例而言’當Μ為Na且X為C1時，反應如下進行， (5i) (6i)。 4NaH + SiCl4 4NaCl + SiH4 3NaH + SiHCl3 — 3NaCl + SiH4 當M為Ba且X為Cl時，反應如下進行， 2BaH2 + SiCl4 2BaCl2 + SiH4 (5“） 3BaH2 + 2SiHCl3 一 3BaCl2 + 2SiH4 (6U)。 矽炫反應器30可為攪拌槽反應器（例如葉輪攪動）。添加 至反應器30中之驗金屬或驗土金屬氫化物32可懸浮於一定 量製造其（例如藉由使鹼金屬或鹼土金屬與氫氣反應）之溶 劑（例如甲笨）中。四鹵化矽及/或三鹵矽燒3丨可鼓泡穿過氫 化物聚料’且較佳以逆流關係鼓泡。添加至反應器3 〇中之 160825.doc 16 201231394 氳化物3 2與添加至反應器中之溶劑之量的重量比可為至少 約1:20 ’且在其他實施例中為至少約1:丨〇或至少約丨：5(例 如為約1:20至約1:5或約1:20至約2:10) »添加之來自鹵化矽 原料氣21 (圖1)之四鹵化矽或來自鹵化矽原料氣2丨，（圖3)之 四函化物矽及三鹵矽烷可相對於氫化物32成實質上化學計 量之比率，其中莫耳比顯示於以上反應（5)至（61丨）中。 一定量之催化劑（諸如三乙基鋁）、各種路易斯酸（lewis acid)或痕量鹼金屬（例如雜質路易斯酸，諸如金屬氯化物） 可添加至反應器3 0中。該等催化劑使溫度降低，在此溫度 下反應（5)及（6)實現充分轉化且可減少輸入系統中之熱 量。在不使用催化劑之實施例中，反應器3〇之操作溫度可 為至少約12(TC (例如為約12〇。(：至約225。(：或約140。(：至約 2〇〇°C );然而，在使用催化劑之實施例中，反應器3〇之操 作溫度可相對較冷，為至少約3〇〇c (例如為約3〇它至約 125 C、約40°C至約l〇〇°C或約4(rc至約8〇°c )。添加至反 應器30中之物質的平均滞留時間可為約5分鐘至約6〇分 鐘0 矽烷氣體35可相對較純（例如含有小於約5體積％或甚至 小於約2體積。/〇之不為矽烷之化合物）。在自反應器％中移 除矽烷氣體35之後，可對矽烷氣體35進行進一步加工。舉 例而5 ，矽烷3 5可藉由引入一或多個蒸餾塔及/或分子篩 中移除雜質，如美國專利第5,211，931號、美國專利第 4,554，141號或美國專利第5,2〇6,〇〇4號中所揭示，各文獻出 所有相關及一致之目的以引用之方式併入本文中，或藉由 160825.doc 17 201231394 熟習此項技術者可用之任何其他已知方法來純化(例如移 除諸如函化硼或齒化磷之化合物）。 石夕烧氣體35可用以製備多晶石夕（例如粒狀或塊狀多晶石夕） 或可用以製備石夕晶圓上之一或多個蟲晶層。如熟習此項技 術者所瞭解，矽烷氣體可在使用之前儲存及/或運輸。 鹼金屬或鹼土金屬氫化物與鹵化矽原料氣21(或包含三 i矽烷及四鹵化矽之混合物21，）中之四鹵化矽之反應製造 鹼金屬或鹼土金屬鹵化物鹽37作為副產物。在使用溶劑之 實施例中，i化物鹽37可溶解且更通常懸浮於溶劑（例如 甲笨）中。_化物鹽37可與溶劑分離且進行市售或如下文 所進一步描述再循環使用。 用於製造矽烷之實質性閉環方法 上文所述之方法可併入製造矽烷之實質性閉環方法中。 上文方法可為關於鹼金屬或鹼土金屬及/或關於鹵素之閉 環。現在參看圖4，鹵化物鹽37可藉由使用分離器4〇與溶 劑分離。分離器40可為蒸發器，或除蒸發器以外或替^蒸 發器，可使用其他適合之設備，包括結晶器、基於過遽及/ 或重力之分離器（例如離心機）。適合之蒸發器包括刮膜式 蒸發器。在分離之後，乾燥之鹵化物鹽可加熱（例如1 5〇〇°C)以移除痕量溶劑。 洛劑43可冷凝並再引入氫化物反應器9及/或矽烷反應器 中。分離之鹵化物鹽3可用作電解之原料3，以便鹼金屬 或鹼土金屬及/或齒化物在整個系統中實質上再循環。 就此點而言，應瞭解，圖4中所示之實質性閉環方法可 160825.doc -18· 201231394 經修改以包括鹵化氫燃燒器25以製造如圖3中 丫 I S有四 化矽及三ifi矽烷之氣體2 1，。 如圖4中所示’該方法為關於鹼金屬或鹼土金屬及關於 鹵素之實質性閉環，其中該系統在任何進料流6、3 1 j比 包括鹼金屬或驗土金屬或鹵素（亦即單獨或以在含鹼金^ 或鹼土金屬或鹵素化合物内之形式）且其中在出料节Μ中 不移除鹼金屬或鹼土金屬及齒素。就此點而言，應瞭解 鹼金屬或鹼土金屬及/或鹵素可自系統中作為雜質移除或 可包括在淨化流中且可作為補充流饋入系統或方法中[鹼 金屬或鹼土金屬及/或鹵素之任何補充可藉由添加至含有 各別元素之化合物系統中達成，且在某些實施例中，藉由 各別氫化物鹽本身達成。在多個實施例中，補充至系統中 之鹼金屬或鹼土金屬及/或齒素氣體（其可以鹼金屬或鹼土 金屬鹽形式添加）之量小於系統内之總循環之約5%，且在 其他實施例中，小於系統内之總循環之約2%(例如為約 0.5%至約 5%)。 在本發明之一些實施例中，該系統及方法可為關於氫氣 之實質性閉環。舉例而t•’如圖5中所示，退出矽烷反應 器30之石夕烧35可引入多晶反應器5〇中，較佳在純化移除痕 量矽烷、碳化合物、痕量金屬及任何摻雜硼、磷或鋁化合 物(例如藉由低溫活性炭吸附器)之後。多晶反應器5〇可為 抓體化床（例如製造粒狀多晶矽）或西門子反應器 reaCt〇r)(例如製造塊狀多晶矽）或可合併有適合製造多晶矽 之任何其他反應器設計。矽烷根據以下反應熱分解以製造 160825.doc -19- 201231394 多晶碎： (7) 矽烷在添加至多晶反應器50中之前可進行進—步加工， 諸如如上所述之各種純化步驟。反應器5〇之反應I物包括 多晶矽52及氫氣31。如圖5中所示，氫氣以引入氫化物反 應益9中。氫氣31在引入氫化物反應器9中之前可藉由分離 出矽塵及藉由純化（例如蒸餾）進一步加工。如圖5中所示， 輸入系統中的僅為矽6且輸出的僅為多晶矽5 2。該系統為 關於氫氣之實質性閉環，其中氫氣僅移除作為雜質或作為 淨化流（未圖示）且僅添加作為補充流（未圖示）。 用於製造矽烷之實質性閉環系統 本發明之方法可在用於製造矽烷之系統中進行，諸如圖 1至5中所說明之任一系統。該系統可為關於函素、鹼金屬 或鹼土金屬及氫氣中之一或多者之實質性閉環。 參看圖1，系統可包括用於電解鹵化物鹽以製造金屬性 鹼金屬或鹼土金屬及_素氣體之容器4(例如唐氏池）。豳素 氣體藉由輸送裝置輸送至以下至少—者中：⑴自化氫燃燒 器25，以與氫氣反應且製造#化氫（圖”，及（2)_化反應 盗8,以與矽（其藉由輸送裝置自矽儲存裝置輸送至_化反 應益8中）反應且製造四齒化矽。在鹵素氣體反應製造鹵化 虱之實施例中，鹵化氫可隨後藉由輸送裝置輸送至鹵化反 應态8中以製造包含四鹵化矽及三_矽烷之混合物。所製 造之任何四_化矽及/或三鹵矽烷氣體藉由輸送裝置輸送 至石夕院反應器30中。 160825.doc •20· 201231394 系統亦包括氫化物反應器9(例如攪拌槽反應器）。金屬 性鹼金屬或鹼土金屬藉由輸送裝置自容器輸送至氫化物反 應器9中。氫氣亦藉由輸送裝置輸送至氫化物反應器9中， 與金屬性鹼金屬或鹼土金屬反應，製造鹼金屬或鹼土金屬 虱化物。系統包括矽烷反應器3〇(例如攪拌槽反應器），氫 化物（視情況存在之任何溶劑）藉由輸送裝置輸送至其中。 在石夕烧反應器3G中’視情況在溶劑存在下，氫化物與四齒 化矽及/或三齒矽烷氣體反應形成齒化物鹽。 在多個實施例t且如圖4中所示，溶劑及函化物鹽可藉 由輸送裝置輸送至用於分離任何溶劑與鹵化物鹽之分離器 中'合剑可藉由輸送裝置輸送至氫化物反應器9中，且 齒化物I可藉由輸送裝置輸送至容器4(例如唐氏池）中以再 循環且完成關於南素及鹼金屬或鹼土金屬之實質性閉環系 統。 乂 、 在若干其他實施例中’系統亦包括多晶反應器50,其可 ，西門子型反應器(Siemens_type react〇r)或流體化床反應 益、。石夕烧藉由輸送裝置自石夕烧反應器3〇輸送至多晶反應器 ^以製造氫氣及多晶石夕。氫氣可藉由輸送裝置自多晶反應 Γ輸送至氫化物反應益9中以再循環氫氣且完成關於氫 氣之實質性閉環系統。 適，之輸送裝置在此項技術中為習知且熟知的。適用於 轉移氣體之輸送裝置包括例如壓縮機或吹風機，且適用於 轉移固體之輸送裝置包括例如拖良式、螺旋式、帶式及氣 動輸送機。就此點而言，應瞭解，本文中使用二 160825.doc •21 - 201231394 裝置（conveying apparatus)」不意謂暗示自系統之—個。。- 直接轉移至另-個單元，而僅為物質藉由任何數 ^ 轉移部件及/或機構自一個單元轉移至另_ _ 矣 U平兀。舉例 而言，物質可自一個單元輸送至其他加工 干及^例如用於 提供連續或分批製程之間的緩衝之純化或儲存單元），/ 後輸送至第二單元。在此實例中，包括中間加工設備本身 之各輸送單元可被視為「輸送裝置」，且片語「輸送裝 置」不應被視為具有限制意義。 、 較佳地，用於製造矽烷之系統中所用之所有設備皆抗環 境腐蝕（包括曝露於所用及系統内製造之化合物卜適合構 造用物質在本發明領域中為習知且熟知的，且包括例如碳 鋼、不鏽鋼、MONEL合金、INCONEL合金 ' Hastell〇y 合金、鎳及非金屬物質，諸如石英（亦即玻璃）及氟化聚合 物（諸如 TEFLON、KEL-F、VITON、KALREZ及 AFLAS)。 應瞭解’上文所述方法及系統可包括一個以上任何所述 單元（例如反應器及/或分離單元），且在不背離本發明範疇 之情況下，多個單元可連續及/或並行操作。此外，就此 點而言，應瞭解’所述方法及系統為例示性的，且該等方 法及系統可包括帶有但不限於其他功能之其他單元。 當介紹本發明要素或其較佳實施例時，冠詞「一（a)」、 「一（an)」、「該（等）(the)」及「該（等）（said)」意欲意謂 存在一或多個要素。術語「包含（comprising)」、「包括 (including)」及「具有（having)」意欲為包括性的且意謂可 存在除列舉要素以外之其他要素。 160825.doc •22· 201231394 =不以本發明範缚之情況下可對上述裝置及方法 進二種改變，所以意欲以上說明書中所μ關中所示 之所有事項應被視為例示性的且不具有限制意義。 【圖式簡單說明】 圖1為用於製造矽烧之系絲沾-土 一 ^ Μ之域的不意圖，其涉及根據本發 明實施例之函化物鹽之電解； 圖2為適用於電解齒化物鹽之唐氏池(D〇wn.s ceu)之橫截 面； 圖3為用於製造含有四鹵化石夕及三㈣烧之鹵化石夕原料 氣之系統的示意圖； 圖4為根據本發明實施例之用於製造矽烷之實質性閉環 系統的示意圖；及 圖5為根據本發明實施例之用於製造多晶矽之實質性閉 環系統之示意圖。 【主要元件符號說明】 3 鹵化物鹽/原料 4 容器 6 矽 8 鹵化反應器 9 氫化物反應器 14 陽極 15 鹵化物鹽 16 陰極 17 金屬性驗金屬或驗土金屬 160825.doc -23- 201231394 18 19 20 21 21' 25 26 28 30 31 32 35 37 40 43 50 52 鹵素氣體 分隔物 唐氏池 鹵化原料氣/鹵化矽原料氣/鹵化矽原料流 鹵化原料氣/鹵化矽原料氣/鹵化矽原料流/含 有四鹵化矽及/或三_矽烧之原料氣/四鹵化矽 及/或三鹵矽烷之混合物 鹵化氫燃燒器 鹵化氫 氫氣 矽烷反應器 氫氣 驗金屬或驗土金屬氫化物 矽烷 驗金屬或驗土金屬ii化物鹽 分離器 溶劑 多晶反應裔 多晶矽 160825.doc -24-In several embodiments of the invention, the hydride reactor 9 is operated under high pressure conditions such as at least about 5 Torr, at least about 125 bar, at least about 200 bar, at least about 275 bar, or at least about 350 bar ( For example, from about 50 bar to about 350 bar or from about 50 bar to about 2 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 i45 ° C, or less than about 130 ° C (eg, about 120 ° C). The metal or alkaline earth metal hydride 32 is typically solid in an organic solvent to about 160 C. A slag 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, reference is made to 160825.doc 15 201231394, in certain other embodiments of the invention, the alkali metal or alkaline earth metal hydride 3 2 may be introduced in the form of a solid or agglomerated solid containing less amount of the agent. In the calcining reactor 30, the metal or soil test metal can be separated from the solvent by centrifugation or filtration or by any other suitable method available to those skilled in the art. In this regard, it should be understood that 'it can be used but not It is limited to a solvent which is not an organic solvent (for example, NaAlCU). As described above, a tetragonal ruthenium and an alkali metal derived from a ruthenium halide raw material gas 21 (or a mixture 21 containing ruthenium tetrahalide and decane as shown in FIG. 3) Or soil test The hydride 3 2 is introduced into the decane reactor 3 to produce decane 35 and a functional salt 37 according to the reaction shown below: (4/y)MHy + SiX4 — (4/y)MXy + SiH4 (5) 3MHy + ySiHX3 — 3MXy + ySiH4 (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 Μ is Na and X is C1, the reaction proceeds as follows, (5i) (6i 4NaH + SiCl4 4NaCl + SiH4 3NaH + SiHCl3 - 3NaCl + SiH4 When M is Ba and X is Cl, the reaction proceeds as follows, 2BaH2 + SiCl4 2BaCl2 + SiH4 (5") 3BaH2 + 2SiHCl3 - 3BaCl2 + 2SiH4 (6U). The enthalpy reactor 30 can be a stirred tank reactor (e.g., impeller agitation). The metal or soil metal hydride 32 added to the reactor 30 can be suspended in an amount to produce it (e.g., by making an alkali or alkaline earth metal) In a solvent (for example, a stupid) which reacts with hydrogen, tetrahalium halide and/or trihalide may be bubbled through the hydride polymer 'and preferably bubbling in a countercurrent relationship. Add to the reactor 3 〇 160820.doc 16 201231394 The weight ratio of telluride 3 2 to the amount of solvent added to the reactor can be at least about 1:20 'and in other embodiments at least about 1: 丨〇 or at least about 丨: 5 (eg, from about 1:20 to about 1:5 or from about 1:20 to about 2:10) »added from the bismuth halide raw material The tetrahalide ruthenium of gas 21 (Fig. 1) or the ruthenium halide feedstock 2 丨, (tetrazide ruthenium and trihalo decane of (Fig. 3) may be in a substantially stoichiometric ratio relative to hydride 32, wherein molar ratio It is shown in the above reactions (5) to (61丨). 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 in which no catalyst is used, the operating temperature of the reactor 3 can be at least about 12 (TC (e.g., about 12 Torr. (: to about 225. (: or about 140. (: to about 2 〇〇 °) C); however, in embodiments in which the catalyst is used, the operating temperature of the reactor 3 can be relatively cold, at least about 3 〇〇c (e.g., from about 3 Torr to about 125 C, from about 40 ° C to about l 〇〇 ° C or about 4 (rc to about 8 ° ° C). The average residence time of the material added to reactor 30 can range from about 5 minutes to about 6 minutes. 0 The decane gas 35 can be relatively pure (eg, Containing less than about 5% by volume or even less than about 2 vol./〇 which is not a decane compound. After the decane gas 35 is removed from the reactor %, the decane gas 35 can be further processed. For example, 5, decane 3 5 can be removed by introducing one or more distillation columns and/or molecular sieves, such as U.S. Patent No. 5,211,931, U.S. Patent No. 4,554,141, or U.S. Patent No. 5,2,6, 〇〇4 All relevant and consistent objects in the literature are incorporated herein by reference, or by reference to 160825.doc 17 2012313 94 Any other known method available to those skilled in the art for purification (eg, removal of a compound such as a functionalized boron or a toothed phosphorus). The sulphur gas 35 can be used to prepare a polycrystalline stone (eg, granular or lumpy) Polycrystalline stellite may be used to prepare one or more layers of smectic crystals on a Shi Xi wafer. As is known to those skilled in the art, decane gas may be stored and/or transported prior to use. Alkali or alkaline earth metal hydrogenation The alkali metal or alkaline earth metal halide salt 37 is produced as a by-product by reacting the ruthenium tetrahalide in the ruthenium halide raw material gas 21 (or a mixture 21 containing trioxane and ruthenium tetrahalide). In the embodiment using a solvent i salt 37 is soluble and more typically suspended in a solvent such as methyl. The salt 37 can be separated from the solvent and commercially available or recycled as described further below. Methods The methods described above can be incorporated into a substantially closed ring process for the manufacture of decane. The above process can be a ring closure with respect to alkali or alkaline earth metals and/or with respect to halogen. Referring now to Figure 4, the halide salt 37 can be borrowed. The separator 4 is separated from the solvent using a separator 4. The separator 40 may be an evaporator, or in addition to or in addition to the evaporator, other suitable equipment may be used, including a crystallizer, a separator based on helium and/or gravity ( For example, a centrifuge. Suitable evaporators include wiped film evaporators. After separation, the dried halide salt can be heated (eg, 15 ° C) to remove traces of solvent. It is introduced into the hydride reactor 9 and/or the decane reactor. The separated halide salt 3 can be used as the raw material 3 for electrolysis so that the alkali metal or alkaline earth metal and/or the dentate is substantially recycled throughout the system. In this regard, it should be understood that the substantial closed-loop method illustrated in FIG. 4 can be modified to include a hydrogen halide burner 25 to produce a tetrahydrogen halide and a trifibrane as shown in FIG. Gas 2 1, 1. As shown in Figure 4, the method is directed to an alkali metal or alkaline earth metal and a substantially closed ring with respect to halogen, wherein the system comprises an alkali metal or a soil metal or halogen in any feed stream 6, 3 1 j ratio (ie Alkali metal or alkaline earth metal and dentate are not removed, either alone or in the form of an alkali metal or alkaline earth metal or halogen compound, and in which the knot is removed. In this regard, it should be understood 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 [alkali or alkaline earth metals and/or Or any supplementation of halogen can be achieved by addition to a system of compounds 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 dentate 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 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 substantially closed loop with respect to hydrogen. By way of example, as shown in FIG. 5, the sulphide 35 exiting the decane reactor 30 can be introduced into the polycrystalline reactor 5, preferably in the purification to remove traces of decane, carbon compounds, trace metals and any After doping with boron, phosphorus or aluminum compounds (for example by means of a low temperature activated carbon adsorber). The polycrystalline reactor 5 can be a grabbed bed (e.g., a granular polycrystalline germanium) or a Siemens reactor reaCt(R) (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 160825.doc -19-201231394 polycrystalline cullet: (7) 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 the reactor 5 includes polycrystalline germanium 52 and hydrogen gas 31. As shown in Figure 5, hydrogen is introduced into the hydride reaction 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 Figure 5, only 矽6 in the input system and only the polysilicon 矽5 2 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). Substantially closed loop system for the manufacture of decane The process of the invention can be carried out in a system for the manufacture of decane, such as any of the systems illustrated in Figures 1 to 5. The system can be a substantial closed loop of one or more of the elements, alkali or alkaline earth metals and hydrogen. Referring to Figure 1, the system can include a vessel 4 (e.g., Down's pool) for electrolyzing a halide salt to produce a metallic alkali or alkaline earth metal and a gas. The halogen gas is transported to at least one of the following by means of a conveying device: (1) a hydrogenating burner 25 for reacting with hydrogen and producing #hydrogen (Figure), and (2) _ reaction thief 8 to It is transported by the transport device from the helium storage device to the reaction to produce tetradentate ruthenium. In the embodiment in which the halogen gas reacts to produce lanthanum halide, the hydrogen halide can then be transported to the halogenation reaction by the transport device. A mixture comprising ruthenium tetrahalide and trioxane is produced in State 8. Any tetrahydroquinone and/or trihalo decane gas produced is delivered to the Shixiayuan reactor 30 by means of a conveyor. 160825.doc • 20 · The 201231394 system also includes a hydride reactor 9 (eg, a stirred tank reactor). The metallic alkali or alkaline earth metal is transported from the vessel to the hydride reactor 9 by means of a transfer device. The hydrogen is also transported to the hydride by the transport device. In the reactor 9, reacting with a metallic alkali metal or an alkaline earth metal to produce an alkali metal or alkaline earth metal telluride. The system includes a decane reactor 3 (for example, a stirred tank reactor), a hydride (any dissolved as the case may be) The hydride is reacted with the tetradentate ruthenium and/or the tridentate decane gas to form a dentate salt in the presence of a solvent, as the case may be, in the case of a gas-fired reactor 3G. In various embodiments And as shown in FIG. 4, the solvent and the functional salt can be transported by means of a transport device to a separator for separating any solvent and halide salt. The sword can be transported to the hydride reactor 9 by means of a transport device. And the dentate I can be delivered to the vessel 4 (e.g., Down's tank) by a conveyor to recycle and complete a substantially closed loop system with respect to the south and alkali or alkaline earth metals. 乂, in several other embodiments The system also includes a polycrystalline reactor 50, which can be a Siemens type reactor (Siemens_type react〇r) or a fluidized bed reaction, which is transported from the smelting reactor 3〇 to the polycrystalline reactor by a transport device. To produce hydrogen and polycrystalline stone. Hydrogen can be transported from the polycrystalline reaction enthalpy to the hydride reaction benefit 9 by a transport unit to recycle the hydrogen and complete a substantial closed loop system with respect to hydrogen. Technology It is well known and well known. Conveying devices suitable for transferring gases include, for example, compressors or blowers, and conveying devices suitable for transferring solids include, for example, towed, screw, belt, and pneumatic conveyors. It should be understood that the use of the two 160825.doc •21 - 201231394 "conveying apparatus" in this article does not imply that the system is directly transferred to another unit, but only the substance is transferred by any number ^ And/or the mechanism is transferred from one unit to another _ 矣 兀 兀. For example, the substance can be transported from one unit to the other, and for example to provide purification or storage between buffers in a continuous or batch process. Unit), / after delivery to the second unit. In this example, each of the conveying units including the intermediate processing equipment itself can be regarded as a "conveying device", and the phrase "conveying device" should not be considered to have a limiting meaning. Preferably, all of the equipment used in the system for making decane is resistant to environmental corrosion (including exposure to materials used in the systems and systems suitable for construction) and is well known and well known in the art, and includes For example, carbon steel, stainless steel, MONEW alloy, INCONEL alloy 'Hastell〇y alloy, nickel and non-metallic materials such as quartz (ie, glass) and fluorinated polymers (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. In addition, in this regard, it should be understood that the described methods and systems are illustrative, and that the methods and systems may include other elements with other functions, but not limited to other functions. For example, the articles "a", "an", "the" and "said" are intended to mean the presence of one or more elements. "including", "including" and "having" are intended to be inclusive and mean that there may be other elements than enumerated elements. 160825.doc •22·201231394=Not bound by the present invention In the case where the above apparatus and method can be changed in two ways, it is intended that all matters shown in the above description in the above description should be regarded as illustrative and not limiting. [Simplified Schematic] FIG. 1 is for The intention of producing a simmered silk-sand-soil field is related to the electrolysis of a functional salt according to an embodiment of the present invention; and FIG. 2 is a Down's pool suitable for electrolytic toothed salt (D〇wn. s ceu) cross-section; FIG. 3 is a schematic diagram of a system for producing a halogenated fossil fuel gas containing tetrahalogenated fossils and three (four) sinter; FIG. 4 is a substantial closed loop for the manufacture of decane according to an embodiment of the present invention. Schematic diagram of the system; and Figure 5 is a schematic diagram of a substantially closed-loop system for producing polycrystalline germanium according to an embodiment of the present invention. [Explanation of main components] 3 Halide salt/raw material 4 Container 6 矽8 Halogenation reactor 9 Hydrogenation Reactor 14 Anode 15 Halide salt 16 Cathode 17 Metallurgical metal or soil test metal 160825.doc -23- 201231394 18 19 20 21 21' 25 26 28 30 31 32 35 37 40 43 50 52 Halogen gas separator Down Pool halogenated feed gas/halogenated germanium raw material gas/halogenated germanium raw material stream halogenated raw material gas/halogenated germanium raw material gas/halogenated germanium raw material flow/containing tetrahalogenated antimony and/or tri-sulfonated raw material gas/tetrahalide antimony and/or three Halogen mixture hydrogen halide burner hydrogen halide hydrogen decane reactor hydrogen metal or soil test metal hydride decane metal or soil test metal ii salt separator solvent polycrystalline reactive polycrystalline 矽 160825.doc -24-