201127751 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種由矽化合物製造燻矽（fumed silica) 二j 、I. ’ °詳而言之，係關於一種將三氣矽烧製造過程中所 生成之廢氣利用於由矽化合物製造燻矽之燻矽之製造方 法。 【先前技術】 一氣石夕烧（SiHCh)係作為多晶石夕（p〇iySi]icon)之製造原 料之有用的化合物，一般而言，係經由使金屬矽與氣化氫 進行反應來製造。例如，專利文獻丨中，揭示有使用流動 層型反應裝置，使金屬矽與氣化氫在含鐵及鋁之觸媒的存 在下進行反應來製造三氣矽烷之方法。 此種二氣矽烷之製造方法中，係經由下述反應式（1)， 仉金屬矽與氯化氫生成三氣矽烷及氫，就副反應而言，除 了也會進行下述反應式（2)所表示之四氣矽烷（SiCl4)生成反 應之外，也會微量地副生成二氣矽烷（SiH2Cl2)。201127751 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing fumed silica from a bismuth compound. In particular, it relates to a process for producing a three-gas sinter. The waste gas generated in the process is used in a method for producing a smoked smoked smoked product from a bismuth compound. [Prior Art] A useful compound of SiHCh as a raw material for producing polycrystalline stone (p〇iySi) is generally produced by reacting a metal ruthenium with hydrogenated hydrogen. For example, the patent document discloses a method for producing trioxane by reacting a metal ruthenium with a vaporized hydrogen in the presence of a catalyst containing iron and aluminum using a fluidized bed type reaction apparatus. In the method for producing a dioxane, the metal ruthenium and the hydrogen chloride are converted to trioxane and hydrogen via the following reaction formula (1), and the side reaction is carried out in addition to the following reaction formula (2). In addition to the formation reaction of tetraoxane (SiCl4), dioxane (SiH2Cl2) is also slightly produced by-product.
Si + 3HC1— SiHCl3 + H2 ⑴Si + 3HC1 - SiHCl3 + H2 (1)
Si+4HCl-> SiCl4 + 2H2 ⑺ 如上所述，金屬矽與氣化氫之反應中，因為三氣矽烷 以外的虱矽烷會與氫一起生成，目此將反應生成氣體冷卻 至-l〇°C以下，由該氣體冷凝分離出氣矽烷，接著，將所得 之氣石夕烧的冷凝液交付蒸餾以分離回收三氣_ 收之二氣矽烷作為多晶矽製造原料來使用。 另一方面，經過上述冷凝分離而分離出氣矽烷之廢 3 201127751 氣，雖以氫為主成分，t氫以外，除了未被冷凝分離之氣 石夕院等之外’金屬♦中含有矽以外之金屬成分等不可避免 之雜質。s此，此廢氣，除了使用流動層型反應裝置，循 環供給於使金屬珍與氣化氫進行反應時的混合氣體以外， 至目前為止並無有效之真4|丨raid ^ β 上 丹矛j用手段，而是經適切的處理即 廢棄。_ ’隨著三氣錢生產量增大，上述之廢氣的量 亦增加，故期望其有效再利用方法的確立。 又，由金屬石夕與氣化氣來製造三氣石夕烧之方法方面， 專利文獻2中提出下述製程：對於金屬㈣氣化氫反應所 得之反應生成氣體，不進行氣㈣之冷凝分離，而直接作 為氣k多曰B矽之原料氣體來使用，使此原料氣體所含之氣 石夕院與氫進行反應，藉由還原反應來製造多㈣，使此時 所排出之氣體與金屬石夕接觸’藉由該氣體中所含之氣化氫 與金屬矽之反應來製造氣矽烷。 上述專利文獻2之製程中，因為於三氣㈣製造時所 成之虱’會被消耗以作為由氣矽烷製造多晶矽時之還 及ST ’乡晶矽製造時所副生成之氣化氫會在與金屬矽之 製：" 皮消耗，故從不會排出廢氣之觀點來看是良好的 金屬’用於三氣钱之製造的金屬石夕中含有石夕以外之 不Lt，即對於多晶^質造成很大影響之雜質。因此， 不會排出廢氣之專利文獻2的製 體中同時伴隨㈣以外之金屬成^循収製程之氣 品質會造Λ ~ 刀對於所得之多晶矽的 質會w成很大的影響」之觀點來看，仍存在問題。亦即， 4 201127751 將含有由金屬矽與氣化氫之反應所生成之三氣矽烷之反應 生成氣體直接利用於多晶矽製造之製程，因為會導致多晶 矽的品質降低’故還是將反應生成氣體交付冷凝分離以回 收氣矽烷，並從此氣矽烷選擇性地回收三氣矽烷最佳，結 果’現狀為要求三氯矽烷等氣矽烷經濃縮分離，且含有矽 以外之金屬成分等之廢氣的有效利用。 又’三氣矽烷以外之氣矽烷（例如四氯矽烷）亦為使金屬 石夕與氣化氫進行反應所得者’而此種氣矽烷亦具有同樣的 問題。 專利文獻1 :日本專利第3324922號 專利文獻2 :曰本特開昭52 — 1 33〇22號公報 【發明内容】 亦即，本發明之目的係提供一種由金屬矽與氣化氫之 反應來製造氣㈣時’將從反應生成氣體冷凝分離出氯石夕 院後之廢氣加以再利用之方法。 本發明人等著眼於上述廢氣以氮為主成分，針對此廢 ::再利用進行努力研究之結果，獲得以下知識與見解而 ^本”：於使四氯錢^化合物於火焰中進行反岸 =:妙之際，將此廢氣作為氯源與碎化合物一同供給 屬可於不受到該廢氣中所…以外之金屬成 且不需夕之雜f的影響之下，獲得高純度之燦， 亥廢氣交付特別的純化處理，而可直接再利用。 特徵Π:依照本發明，可提供-種㈣之製造方法，其 201127751 使金屬矽與氣化氫進行反應以生成氣矽烷， 從含有上述氣矽烷之反應生成氣體冷凝分離出氣矽 烷， 將氣碎烧經冷凝分離後之廢氣與矽化合物之氣體—起 供給至火焰中，藉此從該矽化合物生成燻矽。 本發明中，較佳為： (1) 使用四氣矽烷作為上述矽化合物， (2) 上述氣石夕烧為三氣石夕烧。 以製造三氣矽烷為例，由金屬矽與氣化氫之反應所生 成之反應生成氣體中，如上所述，含有三氣矽烷，以及氫 及二氣矽烷以外之氣矽烷（例如四氣矽烷、二氣矽烷等），進 而原料金屬矽中亦含有矽以外的金屬成分等不可避免之雜 質。此和使金屬矽與氣化氫進行反應來製造其他氯矽烷的 情況完全相同。 因此，從此反應生成氣體將氣矽烷冷凝分離後之廢 氣，含有氫為主成分，並含有雖為少量但因未被冷凝分離 而殘留下來之氯矽烷及來自金屬矽之不純金屬成分等。本 發明係將此種廢氣再利用於將矽化合物供給至火焰中來製 造燻矽的過程。 然而，若將矽化合物供給至火焰中，則經由與氧反應 之燃燒反應，在火焰中會生成二氧化矽（Si〇2)之細微粒子’ 此細微粒子會熔合而可獲得比表面積大、細微之燻矽，而 此反應因為火焰的形成，而可與氧一起使用氫作為可燃性 氣體。亦即，本發明十係使用上述之廢氣作為此氫。 6 201127751 如上所述’在使用廢氣作為氫源的情況時，因為廢氣 中所含之氯矽烷是可被作為矽化合物（即燻矽之製造原料） 來使用之化合物，故藉由火焰中之反應會生成燻矽。因此， 不會對此爐石夕之生成反應造成不良影響。又，廢氣中所含 之氫及氯矽烷以外之成分（亦即，矽以外之金屬成分等）為極 微量，不會對所生成之燻矽的物性造成不良影響。 如上所述，氣矽烷之製造過程中，從金屬矽與氯化氫 反應生成之反應生成氣體將氣矽烷冷凝分離之後的廢氣， 以往並無適切之再利用方法而將其大部分廢棄，但本發明 可不進行特別之純化處理，而直接將此廢氣有效利用於燻 矽之製造。 因此’不僅可大幅削減廢氣之廢棄處理所花費之成 本，亦可削減燻矽之製造成本，工業上極為有用。 【實施方式】 以下’以製造三氣矽烷為例來說明本發明。 <三氣矽烷之製造> 本發明中，是將於三氣矽烷之製造過程所產生之廢氣 利用於燻矽之製造，而三氣矽烷之製造已如上所述，係經 由金屬矽與氣化氫之反應來進行。 1.金屬石夕： 用於上述反應之金屬矽，可使用冶金製金屬矽、矽鐵、 或夕B曰矽等含有金屬狀態矽元素之固體物質且為習知者， 並無任何限制。又’該等金屬矽所含之鐵化合物等雜質， 其成分、含量方面亦無特別限制。 201127751 2·氣化氫： 用於與金屬矽之反應之氯化氫即使混入有氮、氫等亦 可使用’並無限制。然而’一般而言，三氣石夕院、四氣石夕 烧、二氣錢等氣㈣因為水解性高而會與水分反應。因 此’氣化氫中若含有水分’％會有降低所生成之三氣石夕烧 的產率之虞。因此，此氣化氫較佳為乾燥狀態。 3 ·金屬矽與氯化氫之反應： 金屬矽與氣化氫之反應，從有效率地製造三氣矽烷的 觀點來看’使用觸媒較佳。該觸媒可使用金切與氣化氮 之反應中作為觸媒成分之習知者’並無特別 分具體而言可舉出鐵m”第彻族元素之 金屬或其氣化物等 '鋁、銅、鈦等金屬或氣化物。該等觸 媒可單獨使用、或組合複數之觸媒使用。上述觸媒成分之 使用量只要是能有效率地製& Tcs的量即不特別限制，考 罝製造裝置之能力等適當決定即彳’一般而言，以金屬元 素換算，相對於金屬矽使用0 〇5〜4〇重量％、尤其是〇 5重量％即足夠。 又，上述之觸媒成分可藉由添加至反應系内使之存 =，但當所使用之金屬石夕中含有雜質之鐵化合物等觸媒成 分時，可將此雜質作為觸媒成分來有效利用。當然，即使 是使用含有雜質之觸媒成分的金屬矽的情形，為了提高金 屬石夕與氣化氫之反應性，進—步於反應系内添加觸媒成分 亦無任何問題。 上述金屬石夕與氣化氩之反應中，所使用之反應裝置可 8 201127751 使用習知的及腐壯$ ^ 的反應裝置，並無特別限制。 言’可舉出固定床式反應裝置…“ 置具體而 上述反庫F 或机動床式反應裝置等。 江反應裝置之中，從可連續地供 寺 續地製造三氯石夕烧之觀點 ：氣化乳’連 麻，始gi 乂及從上述反應由於為敌熱 … ……'之除熱效果高之觀點來看，使用流動床1 應裝置較佳。 •·助床式反 關於金屬石夕與氣化氫之反應中之反應溫度亦不 制’考量製造農置之材質、能力等適當決定即可。如上所、 述’金屬矽與氣化氫之反應中，除三氣矽烷以外，還會副 生成四氣钱、二氯錢等氣钱，但—般而t，當反二 溫度咼至必要以上時，則三氣矽烷之選擇率會有降低之傾 向又，上述反應為放熱反應。因此，考量該等觀點，反 應溫度為250〜500°C，較佳為在250〜400。(3之範圍内適當 設定為佳。 4.氣矽烷之冷凝分離及蒸餾： 經由上述金屬石夕與氣化氫之反應，會產生含有三氣石夕 烷之反應生成氣體，而此氣體中含有為副產物之四氯矽 炫、二氣石夕烧等三氣石夕烧以外之氣♦烧，再者，除了副生 成之氫之外，還含有來自金屬矽之矽以外的金屬成分等。 因此，從上述之反應生成氣體回收三氣矽烷時，首先 供至冷凝分離，從此反應生成氣體中將含有三氯矽烷之氣 矽烷冷凝分離。 此冷凝分離步驟中’反應生成氣體會經過冷卻，此冷 卻溫度只要是各種氣矽烷會冷凝之溫度以下即可，考量冷 201127751 卻裝置之冷卻能力等 烧之除去效果有越高 是-30°C以下即足夠。 除去氣^夕烧者即不特 適當決定即可。冷卻溫度越低，氣矽 的傾向，一般而言，-1 〇。<3以下，尤其 而冷凝分離之壓力也是只要是能充分 別限制，考量冷凝除去裝置之能力等 適當決定即可 以上即足夠。Si+4HCl-> SiCl4 + 2H2 (7) As described above, in the reaction of metal ruthenium with vaporized hydrogen, since decane other than trioxane is formed together with hydrogen, the reaction product gas is cooled to -1 〇 ° C is condensed to separate the gas decane by the gas, and then the condensate of the obtained gas stone is sent to a distillation to separate and recover the trigas, which is used as a raw material for the production of polycrystalline germanium. On the other hand, the waste 3 201127751 gas which separated the gas decane by the above-mentioned condensing separation is mainly composed of hydrogen, and other than t hydrogen, except for the gas shovel which is not condensed and separated, etc. Unavoidable impurities such as metal components. In addition to the use of a fluidized bed type reaction device, the exhaust gas is circulated and supplied to the mixed gas when the metal is reacted with the hydrogenated hydrogen gas. Until now, there is no effective true 4|丨raid ^ β By means of means, it is discarded after appropriate treatment. _ ' As the production of three gas money increases, the amount of exhaust gas mentioned above also increases, so the establishment of an effective recycling method is expected. Further, in the method of manufacturing a three-gas stone by a metal slag and a gasification gas, Patent Document 2 proposes a process for producing a gas for a reaction of a metal (IV) gasification reaction, and does not perform gas (four) condensation separation. And directly used as a raw material gas of gas k 曰 B ,, so that the gas stone contained in the raw material gas reacts with hydrogen, and a plurality of (four) are produced by a reduction reaction, and the gas and metal discharged at this time are made. Shixi contact 'produces gas decane by reacting vaporized hydrogen contained in the gas with metal ruthenium. In the process of the above-mentioned Patent Document 2, since it is produced in the production of three gas (four), it will be consumed as a gasification hydrogen produced by the production of polycrystalline germanium from gas decane and by the production of ST 's With the metal enamel system: " skin consumption, so from the point of view of the exhaust gas is not good, the metal used for the manufacture of three gas money, including the stone eve, not Lt, that is, for polycrystalline The impurities that cause a great influence. Therefore, in the body of the patent document 2 which does not emit the exhaust gas, the gas quality of the metal-made process other than (4) is accompanied by the process of the process, and the knife has a great influence on the quality of the obtained polycrystalline silicon. Look, there are still problems. That is, 4 201127751 The reaction gas containing the trioxane formed by the reaction of the metal ruthenium and the hydrogenation hydrogen is directly used in the process of manufacturing polycrystalline silicon, because the quality of the polycrystalline silicon is lowered, so the reaction gas is delivered to the condensation. Separation is carried out to recover the gas decane, and the trioxane is selectively recovered from the gas decane. As a result, the current situation requires efficient use of the exhaust gas containing a gas component other than ruthenium, such as trichloromethane, which is concentrated and separated. Further, a gas hexane other than trioxane (e.g., tetrachloromethane) is also obtained by reacting a metal with a vaporized hydrogen, and such a gas hexane has the same problem. Patent Document 1: Japanese Patent No. 3,324,922, Patent Document 2: Japanese Patent Application Laid-Open No. SHO-52------------------------------------------------------------------------------------- When the gas (4) is produced, a method of separating and separating the exhaust gas after the chlorite from the reaction gas is used. The inventors of the present invention have focused on the use of nitrogen as a main component of the exhaust gas, and have made the following knowledge and insights for the purpose of this waste: re-use: to make the tetrachloromethane compound in the flame =: When the mist is used, the waste gas is supplied as a chlorine source together with the broken compound, and it can be obtained without being affected by the metal other than the exhaust gas, and the high purity can be obtained. The exhaust gas is delivered to a special purification treatment and can be directly reused. Characteristic Π: According to the present invention, a method for producing the seed (4) can be provided, which has a reaction of the metal ruthenium with a gasification hydrogen to form a gas decane, and the gas oxime is contained. The reaction gas is condensed to separate the gas decane, and the gas which is condensed and separated by the condensed gas is supplied to the flame together with the gas of the hydrazine compound, thereby generating smoldering from the hydrazine compound. In the present invention, it is preferred that: 1) using tetrakisane as the above-mentioned ruthenium compound, (2) the above-mentioned gas-stone sinter is a three-gas sinter. In the case of producing trioxane, a reaction gas formed by the reaction of a metal ruthenium and a vaporized hydrogen gas is produced. In the above, as described above, trioxane, and hydrogen gas and gas hexane other than dioxane (for example, tetraoxane, dioxane, etc.) are contained, and the metal ruthenium other than ruthenium is inevitably contained in the raw material ruthenium. This is the same as the case where the metal ruthenium is reacted with the vaporized hydrogen to produce another chlorodecane. Therefore, the exhaust gas obtained by condensing and separating the gas oxime from the reaction product gas contains hydrogen as a main component and contains a small amount of The chlorodecane remaining from the condensed separation and the impure metal component derived from the metal ruthenium, etc. The present invention re-uses the exhaust gas to supply the cerium compound to the flame to produce a smoldering process. When the compound is supplied to the flame, fine particles of cerium oxide (Si〇2) are generated in the flame by a combustion reaction with oxygen, and the fine particles are fused to obtain a large specific surface area and a fine smoked sputum. This reaction can use hydrogen as a combustible gas together with oxygen because of the formation of a flame. That is, the present invention uses the above-mentioned exhaust gas as the hydrogen. 6 201127751 As described above, when using exhaust gas as a hydrogen source, since the chlorosilane contained in the exhaust gas is a compound which can be used as a ruthenium compound (i.e., a raw material for the production of smoked mash), the reaction in the flame is used. It will produce smoked sputum. Therefore, it will not adversely affect the reaction of the furnace, and the components other than hydrogen and chlorinated in the exhaust gas (that is, metal components other than strontium) are extremely small. It does not adversely affect the physical properties of the smoked oysters produced. As described above, in the production process of gas decane, the reaction gas generated by the reaction of metal ruthenium and hydrogen chloride condenses and separates the gas after the gas condensed and separated, which is not suitable in the past. Most of the waste is discarded by the recycling method. However, the present invention can be effectively utilized for the manufacture of smoked tobacco without special purification treatment. Therefore, the cost of waste gas disposal can be greatly reduced. It is extremely useful in the industry to reduce the manufacturing cost of smoked oysters. [Embodiment] Hereinafter, the present invention will be described by taking trioxane as an example. <Production of Trioxane> In the present invention, the exhaust gas generated in the production process of trioxane is used for the manufacture of smoked sputum, and the production of trioxane is as described above, via metal ruthenium and gas. The reaction of hydrogen is carried out. 1. Metallic stone: The metal ruthenium used for the above reaction may be a solid material containing a metal-containing lanthanum element such as metal lanthanum, lanthanum iron, or yttrium B. and is not limited. Further, impurities such as iron compounds contained in the metal ruthenium are not particularly limited in terms of their components and contents. 201127751 2. Hydrogenation of hydrogen: Hydrogen chloride used for the reaction with metal ruthenium can be used even if nitrogen, hydrogen or the like is mixed in. However, in general, the three gas stone courts, the four gas stone burning, the second gas and other gas (four) will react with water because of high hydrolyzability. Therefore, if the amount of water contained in the vaporized hydrogen is reduced by %, the yield of the generated triphosite is reduced. Therefore, this vaporized hydrogen is preferably in a dry state. 3. Reaction of metal ruthenium with hydrogen chloride: The reaction of metal ruthenium with vaporized hydrogen is preferred from the viewpoint of efficiently producing trioxane. The catalyst can be used as a catalyst component in the reaction between gold-cut and vaporized nitrogen. 'Specifically, the metal of the metal element or its vapor, such as aluminum, may be mentioned. a metal or a vapor such as copper or titanium. These catalysts may be used singly or in combination with a plurality of catalysts. The amount of the above-mentioned catalyst components is not particularly limited as long as it can efficiently produce & Tcs. In general, it is sufficient to use 0 〇 5 to 4% by weight, especially 〇 5% by weight, based on the metal element, in terms of the ability to manufacture the device. In addition, the above-mentioned catalyst component is sufficient. It can be added to the reaction system to store it. However, when a metal component such as an iron compound containing impurities is used in the metal stone used, the impurity can be effectively used as a catalyst component. Of course, even if it is used In the case of a metal ruthenium containing a catalyst component of an impurity, in order to improve the reactivity of the metal slag and the vaporized hydrogen, there is no problem in adding a catalyst component to the reaction system. In the reaction, used The reaction apparatus used 8201127751 device may be a conventional strong $ ^ rot and is not particularly limited. Introduction 'may include a fixed bed type reaction apparatus ... "counter and said counter-specific libraries F motorized bed reaction apparatus or the like. Among the river reaction devices, from the point of view that it can continuously manufacture triclosan in the temple: the gasified milk 'Lian Ma, the first gi 乂 and the above reaction due to the enemy heat... ...... From the standpoint of view, it is preferred to use a fluidized bed 1 device. • The bed-side reaction is not related to the reaction temperature in the reaction between the metal and the hydrogenation of hydrogen. As mentioned above, in the reaction of 'metal ruthenium and hydrogenated hydrogen, in addition to the three gas decane, it also generates gas money such as four gas money and dichloro money, but generally, when the temperature is reversed, it is necessary. At the same time, the selectivity of trioxane tends to decrease, and the above reaction is an exothermic reaction. Therefore, considering these points, the reaction temperature is 250 to 500 ° C, preferably 250 to 400. (It is preferable to set it appropriately within the range of 3. 4. Condensation separation and distillation of gas decane: The reaction product gas containing triphosate is generated by the reaction of the above metal sulphate with hydrogenation gas, and this gas contains In addition to the by-products such as tetrachloroguanidine or the second gas, the gas is burned in addition to the gas generated by the third gas, and the metal component other than the metal ruthenium. Therefore, when the trioxane is recovered from the reaction gas generated by the above reaction, it is first supplied to the condensation separation, and the gas decane containing trichloromethane is condensed and separated from the reaction gas. In the condensation separation step, the reaction gas is cooled. As long as the cooling temperature is below the temperature at which various gas condensates will condense, considering the cooling capacity of 201127751, the cooling effect of the device is higher than -30 ° C. The removal of gas is not appropriate. The decision is made. The lower the cooling temperature, the tendency of gas enthalpy, generally, -1 〇. <3 or less, especially the pressure of condensing separation is as long as it can be fully limited, consider condensation Means the ability to be appropriately determined above is sufficient.
般而言，300kPaG以上，尤其是500kPaG 用以進行冷凝之冷卻手段，只要是可將反應生成 氣體冷卻至上述冷卻溫度者即不特別限制，可使用習知的 冷部手奴來進仃。該冷卻手段具體而t，可舉出使反應生 成氣體通過已冷卻之熱交換器使之冷卻之冷卻手段、或以 經冷凝冷卻之冷凝物來將反應生成氣體冷卻之冷卻手段 等。該等方法可分別單獨採用或併用。 再者，為了使氣體之壓力上升，在氯矽烷之冷凝除去 則’亦可設置加壓機。χ，為了 ^呆護該加壓機，預備的氣 矽烷冷凝、過濾器等亦可設置於較加壓機更上流側。該等 方法，可採用作為工業之製程設計的通常手段。 經由上述之冷凝分離從反應生成氣體所得之冷凝液， 為各種氣矽烷的混合物，藉由蒸餾將三氣矽烷單離，所回 收之三氣我係作為製造多晶石夕之步驟中之才斤出原料來使 用。 又，氣矽烷經冷凝分離後之廢氣，含有氫氣為主成分， 進而，未經冷凝分離而殘存之氣矽烷含量雖依冷凝程度而 異，但通常含有2體積％以下的量，且含有雖為微量之來自 金屬矽之不純金屬成分等，該廢氣被再利用於以下所述之 10 201127751 燦矽製造步驟。 <燻矽之製造> 此製造步驟中，孫w功#人& 1 ,、 σ物為原料，將此與氧氣（或 空氣）及可燃性氣體一起供仏至*吟士吐 咚伢，，。至火焰中使之燃燒，藉此，在 火焰中會生成二氧化石々偶_ # ? π 乳化矽彳政粒子且藉由粒子彼此之熔合而獲 得細微且比表面積大之燻石夕。 本發明中’係將前述之三氣石夕燒製造步驟中所生成之 氣撕凝分離後的廢氣作為可燃性氣體，與上述石夕化合 物之氣體一起供給至火焰中 主人焰中。亦即，此廢氣因為是以氫 主體，故藉由作為可揪性翁俨φ q』·.·'注轧體來使用，而有助於火焰之形 成。且’此廢氣中所含之負石々p 〃办丨丄 a <虱矽烷（例如三氣矽烷、四氣矽烷、 二氣石夕烧等）因為是可祐你& λ 破作為矽化合物（即燻矽之製造原料） 來使用之化合物，故經由在火焰中之燃燒而會轉換成燦 夕又I氣中所含之來自金屬矽之矽以外的金屬成分 因為是極微量，故不會對所 響 a對所付之燻矽的物性等產生不良影 由上述之說明可明瞭，极友 瞭廢軋中所含之氫以外的成分不 會對燻石夕之特性產生不良影#，因此，本發明中可於不將 冷凝分離後之廢氣供至特別的精製處理等之下，直 用於燻矽之製造步驟’此為本發明之最大優點。 又，上述之廢氣中的氣石夕烧含量最多為2體積％左右， 當然，即使當此含量超過2舯 (迫2體積/〇時，因為此種氣矽烷 會反應而生成燒紗，故可做 文了將该廢氣直接供給至燻矽之劁1 步驟。 、表坆 201127751 本發明中，原料之矽化合物係使用常溫下為氣體狀或 液狀者。其具體例可例示以下之矽化合物。 妙氧烷類： 例如六甲基環三矽氧烷、八甲基環四矽氧烷、十甲基 ί哀五石夕氧烷、六甲基二矽氧烷、八甲基三矽氧烷等。 院氧基矽烷類： 例如四甲氧基矽烷、四乙氧基矽烷、甲基三甲氧基石夕 烧、二甲基二甲氧基矽烷、甲基三乙氧基矽烷等。 院氧基矽烷以外之有機矽烷： 例如四甲基矽烷、二乙基矽烷、六曱基二矽氮等。 無機矽烷化合物： 例如單氣;5 夕烧、二氣石夕烧、三氣石夕院、四氣石夕烧等氣 矽烷、單矽烷、二矽烷等。 本發明中’上述所例示之矽化合物之中，較佳為氣石夕 烷等函化矽，最佳係使用四氣矽烷。 亦即’經由矽化合物之燃燒來生成埭矽之反應，若以 八曱基環四矽氧烷為例，係以下述式所表示。In general, a cooling means for condensing 300 kPaG or more, particularly 500 kPaG, is not particularly limited as long as it can cool the reaction product gas to the above-described cooling temperature, and a conventional cold hand slave can be used. Specifically, the cooling means may be a cooling means for cooling the reaction-generating gas through the cooled heat exchanger, or a cooling means for cooling the reaction-forming gas by condensate-cooled condensate. These methods can be used individually or in combination. Further, in order to increase the pressure of the gas, a pressurizing machine may be provided to remove the condensation of the chlorosilane. χ, in order to maintain the press, the prepared gas condensate, filter, etc. may be placed on the upstream side of the presser. These methods can be used as a general means of industrial process design. The condensate obtained from the reaction gas is separated by condensation as described above, and the mixture of various gas decanes is separated by trituration by distillation, and the recovered three gas is used as a step in the process of manufacturing polycrystalline stone. Use raw materials to use. Further, the exhaust gas obtained by the condensation separation of the gas decane contains hydrogen as a main component, and the content of the gas decane remaining without being separated by condensation varies depending on the degree of condensation, but usually contains 2% by volume or less, and the content is A trace amount of impure metal components derived from metal ruthenium, etc., and the exhaust gas is reused in the following 10 201127751 矽 矽 manufacturing step. <Manufacturing of smoked oysters> In this manufacturing step, Sun Wong#人& 1 , σ is a raw material, and this is supplied with oxygen (or air) and flammable gas to *gentle spit ,,. It is burned in the flame, whereby in the flame, a sulphur dioxide _ _ _ _ emulsified ruthenium particles are formed, and the particles are fused to each other to obtain a fine and large surface area. In the present invention, the exhaust gas obtained by the aerobic separation of the gas generated in the above-described three-gas sinter firing step is supplied as a combustible gas, and is supplied to the flame master flame together with the gas of the above-mentioned stone compound. That is, since this exhaust gas is mainly composed of hydrogen, it is used as a squeezing body, and contributes to the formation of a flame. And 'the negative stone contained in this exhaust gas 〃 a 虱矽 a < decane (such as trioxane, four gas decane, two gas stagnation, etc.) because it is bless you & λ broken as a bismuth compound (i.e., the raw material for the production of smoked sputum), the compound used in the flame is converted into a metal component other than the metal lanthanum contained in the ceremonial ceremonial gas, which is contained in the gas. It is clear from the above description about the physical properties of the smoked abundance, etc., and it is clear that the components other than the hydrogen contained in the waste rolling do not adversely affect the characteristics of the smoked stone. In the present invention, the exhaust gas after the condensation separation is not supplied to a special refining treatment or the like, and is directly used in the manufacturing step of the smoked smoke. This is the greatest advantage of the present invention. Further, the content of the gas-fired gas in the exhaust gas is at most about 2% by volume. Of course, even when the content exceeds 2 Torr (for 2 volumes/〇, since the gas oxime reacts to form a calcined yarn, it can be In the present invention, the ruthenium compound of the raw material is a gas or a liquid at a normal temperature. Specific examples thereof include the following ruthenium compounds. Amyoxanes such as hexamethylcyclotrioxane, octamethylcyclotetraoxane, decamethyl pentoxide, hexamethyldioxane, octamethyltrioxane Ethenyloxyalkylenes: for example, tetramethoxydecane, tetraethoxydecane, methyltrimethoxycarbazide, dimethyldimethoxydecane, methyltriethoxydecane, etc. Organic decane other than decane: for example, tetramethyl decane, diethyl decane, hexamethylene diazide, etc. Inorganic decane compound: for example, single gas; 5 shochu, two gas stone shochu, three gas stone garden, four a gas decane, a monodecane, a dioxane, etc., such as a gas stone, etc. Among the ruthenium compounds, a ruthenium or the like is preferably used, and tetrakisane is preferably used. That is, a reaction of ruthenium by combustion of a ruthenium compound is carried out. The alkane is exemplified by the following formula.
Si4(CH3)8〇4+ 16〇2— 4Si02 + 8C02+12H20 從此反應式可理解’從非齒系之石夕化合物製造燻石夕 時’矽化合物之燃燒反應中氫不會被消耗，被供給作為可 燃性氣體之氫僅會被消耗於火焰之形成。 另一方面，經由四氣矽烷之燃燒來生成燦矽之反應係 以下述式所表示。Si4(CH3)8〇4+ 16〇2—4Si02 + 8C02+12H20 From this reaction formula, it can be understood that hydrogen is not consumed in the combustion reaction of the bismuth compound from the non-dentate stone compound. Hydrogen supplied as a flammable gas is only consumed by the formation of a flame. On the other hand, the reaction for generating the saponin by the combustion of tetrakisane is represented by the following formula.
SiCl4 + 2H2 + 〇广 Si02 + 4HCl + 〇2 12 201127751 從此反應式可理解’從鹵化矽來製造燻矽時，此燃燒 反應中氫會被消岸毛，尤其四氣錢與其他的氯石夕烧相比氮 被消耗得最多。㈣，此燃燒反應，與前述之㈣系矽化 合物之燃燒反應相t匕’因為火焰的形成以外亦消耗了大量 的氫’故依循本發明’ #由供給前述之廢氣，可大幅減低 氫所需要之成本，可將本發明之優點活用至最大限度。 又’亦可將用於上述之矽化合物的燃燒之氫氣的總量 :為前述之廢氣’亦可將氫氣的—部分作為廢氣，將此廢 氣與初生（virgin)之氫氣混合來供給。 又，將各種氣體供給至火焰中之反應，可使用單管之 燃燒器來進行，亦可使用多管之燃燒器來進行。 例如當使用單管之燃燒器時，—般而言，係採用將石夕 化合物之氣體、可燃性氣體及氧氣等預先加以混合之後， 經過單管之燃燒器再於反應室内使之燃燒之方法，上述之 廢氣可單獨或與初生之氫氣一起作為可燃性氣體來使用\ 又’當使用多管之燃燒器時’―般而言，係採用將石夕 化合物之氣體及氧氣供給至中心冑，再將可燃性氣體供給 至外周部使之在反應室内燃燒之方法，此情況時，供給: 外周部之可燃性氣體可使用初生之氫氣，上述之廢氣^從 中〜#供給。亦即，因為若從外周部供給廢氣時，廢氣中 的氯石夕燒會在管的出口附近反應，而反應物（二氧化石幻會附 著於管壁，會使管閉塞而有造成連續運轉之障礙之虞 ， 又’關於火焰之溫度亦不特別限制，考量所使用之燃 燒器能力等適當決定即可。it常，在使用四氯矽烷來製造 13 201127751 燻矽之際，將燃燒器的溫度設定為1000〜220(TC的範圍即 可又，供給之氣體量、氣體的流速、火焰的長度等，設 疋成使所生成之燻矽具有適當之平均粒徑、比表面積即可。 例如，因為火焰中之二氧化矽（Si〇2)濃度越高，所得之 燻矽越有平均粒徑變大，且比表面積變小之傾向，故因應 所要之燒石夕的物性來設定矽化合物的氣體供給量即可。 又’氧氣（空氣）的供給量至少設定為矽化合物及火焰形 成所’肖耗之氫可完全燃燒的量，通常係使用大過剩量之氧 氣。 再者，火焰的溫度越高，則燻矽越有平均粒子徑變大， 比表面積變小之傾向，火焰溫度係取決於火焰形成所消耗 之虱量，此氫量越多則火焰溫度會變得越高，故含有廢氣 之氫氣的供給量亦因應所要之壎石夕的物性適當設定即可。 再者，火焰的長度越長則燻矽的平均粒子徑會變得越 大比表面積變得越小，故考量此來設定各種氣體之供@ 速度。 此種方式所得之燻石夕，具有其本身習知的物性，例如 BET比表面積在45〜5GQmVg左右的範圍。該燻料適當 進行表面處理，供應於其本身習知的㈣例如各種樹脂 的充填劑、電子照片用色劑（t_r)之外添劑等。 又，上述之本發明中，可將在三氣石夕烧製造過程中所 生成之冷凝分離後的廢氣直接再利用於㈣之製造，尤直 當製造高純度之爐石夕時，亦可將此廢氣加以純化處理(例如 以活性碳進行之吸附處理）以除丰 )除去虱矽烷，使廢氣中所含之 14 201127751 氯石夕烧的置成為〇.01體積％以下再供給至造步^ 中 〇 亦可與氫氣（廢氣）一起併用碳化氫氣作為可燃性氣 體。 、 雖以使用製造二氣矽烷時所產生之廢氣的情況 為例來犮明本發明，但本發明所屬技術領域中具有通常知 識者自可明瞭製造其他氯⑪院時所產生之廢氣（例如使金 屬矽與氣化氩進行反應來製造四氣矽烷時所產生之廢氣)亦 可同樣地適用於本發明。 實施例 以下以實施例更進一步說明本發明，但本發明並不限 疋於違專貫施例。 又廢氣之組成及所得之二氧化矽的分析，係以以下 方法來進行。 廢氣之組成分析； 廢氣之組成分析係以氣相層析來進行。 ： 二氧化>5夕之組成分析： 所得之二氧化矽係以比表面積、體積密度、鐵濃度、 崔呂濃度來評價。 比表面積係以氣體吸附BET單點法來測定。 體積密度，係將約1L之燻矽靜置3 0分鐘後，進行重 量測定來算出。 鐵濃度及紹濃度係對燻石夕2 g進行適當之前處理後，以 ICP發光分光分析法來測定。 15 201127751 (實施例1) 以内徑50mm之不鏽鋼製流動層型反應器製造三氣矽 烷。 亦即，將500g之金屬矽（鐵含量：〇15重量％、鋁含量· 〇_25重量％)裝填至反應器’接著，將氯化氫幻％ (O.HnmoD/mm 與氫 〇.214g (0.107m〇丨）/min 加以混合， 再供給至反應器。 將此反應器保持在35(TC之溫度，於大氣壓下以6〇g (2.14mol)/hr之速度供給金屬矽。 從上述反應器所排出之反應生成氣體，以熱交換器冷 卻後，再以壓縮機加壓至600kPaG，再冷卻至_5(rc以將^ 矽烷冷凝除去。氣矽烷經冷凝除去後之廢氣的組成如下。 廢氣組成： 氫：99.62體積％ 氣矽烷：0.38體積％ 二氣石夕烧（DSC) 0.05體積％ 三氣矽烷（TCS) 0.29體積％ 四氯矽烷（STC) 0.04體積％ 將四氣矽烷、上述所回收之廢氣及空氣加以預先混合 後，使用^ S燃燒器從圓筒狀反應器的上端連續地供給來 進行燃燒反應。 又，氣體之混合比，調整為四氣矽烷與廢氣中之氫與 空氣之體積比為2 : 5 : 14，已預先混合之氣體係從多管燃 燒器之中心部（内管）供給。又，從外管供給空氣及從其内側 16 201127751 供給氫與空氣之混合氣體來作為密封氣體，以製造燻石夕。 此燻矽之BET比表面積、體積密度、鐵濃度、鋁濃度 係如下所述。 BET比表面積：220m2/ g 體積密度：25g/L 鐵濃度：未滿lppm 在呂濃度：未滿1 ppm (實施例2) 除了將從反應生成氣體冷凝分離氣矽烷時之深冷壓力 及深冷溫度分別變更為650kPaG、-30°C以外’係以與實施 例1完全相同的方式獲得下述組成之廢氣。 廢氣組成： 氫：98·98體積％ 氯矽烷：1.02體積％ 二氣矽烷（DSC) 0_09體積％ 三氣矽烷（TCS) 0.84體積％ 四氣矽烷（STC) 0.09體積％ 使用上述之廢氣，以與實施例1相同之方式製造燒石夕， 獲得下述性質之燻矽。 BET比表面積：220m2/g 體積密度：25g/L 鐵濃度：未滿lppm 在呂濃度：未滿lppm (實施例3) 17 201127751 除了將從反應生成氣體冷凝分離氣矽烧時之深冷壓力 及深冷溫度分別變更為i3〇kPaG、-30°C以外，係以與實施 例1完全相同的方式獲得下述組成之廢氣。 廢氣組成： 氫：97.30體積％ 氣矽烷：2.70體積％ 二氣矽烷（DSC) 0.3體積％ 三氣矽烷（TCS) 2.2體積°/〇 四氣矽烷（STC) 0.2體積％ 使用上述之廢氣，以與實施例1相同的方式製造壤石夕 獲得下述性質之燻矽。 BET比表面積：220m2/ g 體積密度：25g/L 鐵濃度：未滿Ippm 鋁濃度：未滿Ippm 以上實施例1〜3中’燻矽之製造中所使用之廢氣的組 成係如下述表1所示。 [表1] 實施例1 實施例2 DSC 0.05% 0.09% TCS 0.29% 0.84% STC 0.04% 0.09%SiCl4 + 2H2 + 〇广SiO2 + 4HCl + 〇2 12 201127751 From this reaction formula, it can be understood that when the sputum is produced from bismuth halide, the hydrogen in this combustion reaction will be eliminated, especially the four gas and other chlorite eves. Burning is most consumed compared to nitrogen. (4) The combustion reaction is in contact with the combustion reaction of the above-mentioned (4) ruthenium compound, because a large amount of hydrogen is consumed in addition to the formation of the flame, so that the present invention can be greatly reduced by supplying the aforementioned exhaust gas. The cost of the present invention can be maximized. Further, the total amount of hydrogen used for the combustion of the above-mentioned ruthenium compound may be the same as that of the above-mentioned waste gas, and the hydrogen gas may be supplied as an exhaust gas, and this waste gas may be mixed with virgin hydrogen. Further, the reaction of supplying various gases to the flame can be carried out using a single-tube burner or a multi-tube burner. For example, when a single-tube burner is used, in general, a method in which a gas of a compound of a scorpion compound, a combustible gas, and oxygen are mixed in advance, and then burned through a burner of a single tube and then burned in the reaction chamber The above-mentioned exhaust gas can be used as a combustible gas alone or in combination with nascent hydrogen gas. Also, when a multi-tube burner is used, "the gas and oxygen of the Shixia compound are supplied to the center 胄, Further, the flammable gas is supplied to the outer peripheral portion to be combusted in the reaction chamber. In this case, the flammable gas in the outer peripheral portion can be supplied with nascent hydrogen gas, and the exhaust gas can be supplied from the middle to the #. That is, if the exhaust gas is supplied from the outer peripheral portion, the chlorine gas in the exhaust gas will react near the outlet of the tube, and the reactant (the oxidized stone will adhere to the tube wall, causing the tube to be closed and causing continuous operation). The obstacles are different, and the temperature of the flame is not particularly limited. It is appropriate to consider the burner capacity used. It is often used in the manufacture of 13 201127751 smoked sputum using tetrachloro decane. The temperature is set to 1000 to 220 (the range of TC may be, the amount of gas supplied, the flow rate of the gas, the length of the flame, etc., so that the generated smoked sputum has an appropriate average particle diameter and specific surface area. Because the higher the concentration of cerium oxide (Si〇2) in the flame, the larger the average particle size of the obtained sputum is, and the specific surface area becomes smaller. Therefore, the bismuth compound is set according to the physical properties of the desired smoldering stone. The amount of gas supplied is sufficient. The amount of oxygen (air) supplied is at least set to the amount at which the hydrogen consumed by the ruthenium compound and the flame is completely burned. Usually, a large excess of oxygen is used. The higher the temperature, the more the smoked sputum has a larger average particle diameter and the smaller the specific surface area. The flame temperature depends on the amount of enthalpy consumed by the flame formation. The more the amount of hydrogen, the higher the flame temperature becomes. Therefore, the supply amount of the hydrogen gas containing the exhaust gas may be appropriately set according to the physical properties of the desired ruthenium. Further, the longer the length of the flame, the larger the average particle diameter of the smoked sputum, and the smaller the surface area becomes, the smaller the surface area becomes. Considering the supply of various gases at the @speed. The smoked ash obtained in this way has its own customary properties, such as a BET specific surface area in the range of about 45 to 5 GQmVg. The smoked material is suitably surface-treated and supplied. (4) For example, a filler of various resins, a toner other than an electrophotographic toner (t_r), etc. Further, in the above invention, the condensation generated in the manufacturing process of the three-gas stone can be produced. The separated exhaust gas is directly reused in the manufacture of (4), and when the high-purity furnace is produced, the exhaust gas may be purified (for example, adsorbed by activated carbon) to remove decane. The amount of 14 201127751 chlorite contained in the exhaust gas is set to 0.01% by volume or less and is supplied to the step ^. The hydrogen gas (exhaust gas) can also be used together with carbonized hydrogen as a combustible gas. The present invention will be exemplified by the case of the exhaust gas generated in the case of dioxane, but those having ordinary knowledge in the technical field of the present invention can clarify the exhaust gas generated when other chlorine 11 yards are manufactured (for example, metal crucible and gasification). The exhaust gas produced by the reaction of argon to produce tetraoxane can also be suitably applied to the present invention. EXAMPLES Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited to the specific examples. The composition of the exhaust gas and the analysis of the obtained cerium oxide were carried out by the following methods: Composition analysis of the exhaust gas; Composition analysis of the exhaust gas was carried out by gas chromatography. : Dioxide > 5 composition analysis: The obtained cerium oxide was evaluated by specific surface area, bulk density, iron concentration, and Cui Lu concentration. The specific surface area was measured by a gas adsorption BET single point method. In the bulk density, about 1 L of the smoked cockroach was allowed to stand for 30 minutes, and then the weight was measured and calculated. The iron concentration and the concentration were determined by ICP emission spectrometry after appropriate treatment of 2 g of the extract. 15 201127751 (Example 1) Trioxane was produced by a flow layer type reactor made of stainless steel having an inner diameter of 50 mm. That is, 500 g of metal ruthenium (iron content: 〇15% by weight, aluminum content 〇255% by weight) was charged to the reactor'. Next, the hydrogen chloride phantom % (O.HnmoD/mm and hydroquinone.214g (0.107) M〇丨)/min was mixed and supplied to the reactor. The reactor was maintained at a temperature of 35 (TC) and supplied to the metal crucible at a rate of 6 〇g (2.14 mol)/hr at atmospheric pressure. The discharged reaction product gas is cooled by a heat exchanger, and then pressurized to 600 kPaG by a compressor, and then cooled to _5 (rc to condense and remove the decane. The composition of the exhaust gas after the condensed gas is removed by condensation is as follows. Composition: Hydrogen: 99.62 vol% Gas decane: 0.38 vol% Digas calcite (DSC) 0.05 vol% Trioxane (TCS) 0.29 vol% Tetrachloro decane (STC) 0.04 vol% Tetrahydrofurane, recovered as described above After the exhaust gas and the air are premixed, the combustion reaction is continuously supplied from the upper end of the cylindrical reactor using a burner, and the mixing ratio of the gas is adjusted to hydrogen and air in the four gas decane and the exhaust gas. Volume ratio is 2: 5 : 14, pre-mixed The gas system is supplied from the center portion (inner tube) of the multi-tube burner. Further, air is supplied from the outer tube and a mixed gas of hydrogen and air is supplied from the inner side 16 201127751 as a sealing gas to produce a smoked stone. The BET specific surface area, bulk density, iron concentration, and aluminum concentration are as follows. BET specific surface area: 220 m 2 / g Bulk density: 25 g / L Iron concentration: less than 1 ppm Lu concentration: less than 1 ppm (Example 2) Except that the cryogenic pressure and the cryogenic temperature at the time of condensing and separating the gas decane from the reaction product gas were changed to 650 kPaG and -30 ° C, respectively, the exhaust gas of the following composition was obtained in exactly the same manner as in Example 1. Exhaust gas composition: Hydrogen: 98.98 vol% chlorodecane: 1.02 vol% Dioxane (DSC) 0_09 vol% Trioxane (TCS) 0.84 vol% Tetrahydrodecane (STC) 0.09 vol% Using the above-mentioned exhaust gas, and Example 1 In the same manner, in the same manner, the sputum was obtained, and the following characteristics were obtained: BET specific surface area: 220 m 2 /g Bulk density: 25 g / L Iron concentration: less than 1 ppm Lv concentration: less than 1 ppm (Example 3) 17 201127751 Will be counter Exhaust gas of the following composition was obtained in the same manner as in Example 1 except that the cryogenic pressure and the cryogenic temperature at the time of the formation of the gas condensed separation gas were changed to i3 〇 kPaG and -30 ° C, respectively. : 97.30 vol% gas decane: 2.70 vol% dioxane (DSC) 0.3 vol% trioxane (TCS) 2.2 volume ° / 〇 four gas decane (STC) 0.2 vol% using the above-mentioned exhaust gas, in the same manner as in Example 1. The way to make the soil stone to obtain the following characteristics of smoked cockroaches. BET specific surface area: 220 m 2 / g Bulk density: 25 g / L Iron concentration: less than 1 ppm Aluminum concentration: less than 1 ppm The composition of the exhaust gas used in the manufacture of 'smoked smoke in Examples 1 to 3 is as shown in Table 1 below. Show. [Table 1] Example 1 Example 2 DSC 0.05% 0.09% TCS 0.29% 0.84% STC 0.04% 0.09%
(參考例1) 18 201127751 當製造燻矽時，除了使用初生的氮氣取代廢氣以外 係以與實施例1完全相同之條件來製造燻石夕。 所得之燻石夕的各種物性等係如下所述。 BET比表面積：220m2/ g 體積密度：25g/ L 鐵濃度：未滿1 p p m 在呂濃度：未滿1 p p m 從以上之實驗結果可理解 之製造過程中所得之氣矽烷冷 使用，藉此可獲得具有與使用 積及體積密度且高純度之燻石夕 ’依照本發明，將三氣矽烷 凝分離後之廢氣作為氫源來 子刀生之氫氣時相等之比表面 又確認到，即使藉由變更用以 條件而使廢氣之組成變動，亦不會二二離氣矽烷之深冷 生不良影響，可獲得與使用Μ之^斤得之壎石夕的物性產 及，來自起始原料之金屬矽之微量二虱時相等之燻矽’以 會對燻矽之物性造成影響。 、金屬雜質，亦完全不 【圖式簡單說明】 無 【主要元件符號說明】 無 19(Reference Example 1) 18 201127751 When the smoked smoke was produced, the smoked stone was produced under the same conditions as in Example 1 except that the primary nitrogen was used instead of the exhaust gas. The various physical properties and the like of the obtained smoked stone are as follows. BET specific surface area: 220m2 / g Bulk density: 25g / L Iron concentration: less than 1 ppm Lv concentration: less than 1 ppm From the above experimental results, it can be understood that the gas decane obtained in the manufacturing process is used coldly. According to the present invention, the surface of the gas obtained by coagulation and separation of the trioxane as a hydrogen source is equal to the surface, even if it is changed by the surface. In order to change the composition of the exhaust gas under the conditions, and not to affect the adverse effects of the deep-cold chilling of the two-way decane, it is possible to obtain the physical properties of the stagnation of the sputum, and the metal 来自 from the starting materials. The amount of smoke in the second sputum is equivalent to the influence of the physical properties of the smoked cockroach. Metal impurities, not at all [Simple description of the diagram] None [Main component symbol description] None 19