201038479 六、發明說明： 【發明所屬之技術領域】 本發明關於氣相反應裝置。 【先前技術】 二氯砍院（SiHCl3)係半導體、液晶面板、太陽電池等之 製造時所使用的特殊材料氣體。近年來，需求係順利地擴 大’作爲電子領域所廣泛使用的CVD材料，今後亦期待成 長。 〇 三氯矽烷係藉由使氫（H〇附加於四氯矽烷（SiCl4)的以下 反應來生成。201038479 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a gas phase reaction apparatus. [Prior Art] Diclofenac (SiHCl3) is a special material gas used in the manufacture of semiconductors, liquid crystal panels, solar cells, and the like. In recent years, demand has been smoothly expanded. As a CVD material widely used in the field of electronics, it is expected to grow in the future. 〇 Trichloromethane is produced by the following reaction of hydrogen (H 〇 added to tetrachloro decane (SiCl 4 )).
SiCl4 + H2 —SiHCl3 + HC1 (1) 此反應係熱平衡氣相反應，藉由將由已氣化的四氯砂 烷與氫所構成的原料氣體加熱到約700〜1400 °C的高溫而 發生正反應，得到三氯矽烷。 向來，作爲此種氣相反應的反應裝置，例如已知如專 利文獻1中記載的裝置。此裝置具備：周圍被發熱體所包 〇 圍而且由同心配置的管形成外室與內室所構成的反應室， 在反應室的上部所設置之使外室與內室相互連通的轉向器 ，在反應室的下部所設置之進行導入外室的原料氣體與由 內室導出的反應生成氣體之熱交換的熱交換器。原料氣體 係通過熱交換器預熱而供應給外室，在由外室經由轉向器 流到內室之間進行反應’反應生成氣體係經由熱交換器冷 卻而排出。 然而，於如上述的反應裝置中，由於反應室係經由轉 201038479 向器連結的雙重室，成爲氣體依外室與內室的順序而上下 地往返之構造，故有反應室的出口氣體溫度降低之問題。 又，由於不能急速地進行反應生成氣體的冷卻，所生成的 三氯矽烷有逆反應成四氯矽烷之虞，亦有得不到高反應收 率的問題。 [專利文獻1]特開平6-293511號公報 【發明內容】 本發明之一目的在於提供一種氣相反應裝置，其至少 〇 部分地消除習用技術的不良情況。 本發明之另一目的在於提供一種保持高的傳熱效率之 氣相反應裝置。 本發明之再一目的在於提供一種可盡可能地防止逆反 應等而達成高反應收率的氣相反應裝置，尤其是適合於氯 矽烷與氫的高溫氣相反應之反應裝置。 因此，本發明提供一種氣相反應裝置，其具備： 使由流入口以指定的流入流速供給的複數種之原料氣 ο 體進行氣相反應，由流出口當作反應生成氣體排出之反應 容器， 附設於反應容器，加熱反應容器的內部之加熱手段， 及 配設於反應容器的內部，縮小氣體的流路而提高氣體 流速之傳熱構件。 此處’反應谷器只要是由適合於高溫氣相反應的構造 、材料所構成’則可爲任何所成者，較佳爲在容器的一側 201038479 具備流入口，在與該一側遠隔的另一側具備流出口 ’在流 入口與流出口之間留指定的距離之構造者，而且較佳爲藉 由加熱手段來加熱壁面，由傳達熱給反應容器內部的材料 來構成。 加熱手段只要是可加熱反應容器的內部之構造’則可 爲任何所成者，較佳爲將反應容器壁面加熱以使反應容器 內部成爲高溫加熱狀態的構造。於一態樣中，可以爲以傳 熱性優異的材料來形成反應容器，直接加熱反應容器壁的 〇 構造。於另一態樣中，較佳爲以傳熱性優異的材料來形成 反應容器，在反應容器的外部配置加熱器以加熱反應容器 壁面之構造。於任一情況中，反應容器較佳爲將全體收納 在收容容器內，周圍係絕熱，尤其在設置後者的外部加熱 器時，較佳爲在配置有反應容器與加熱器的收容容器內預 先塡充如氬氣的惰性氣體等。 傳熱構件係意味以加熱手段加熱反應容器的內部，結 果反應容器之內部所配設的傳熱構件本身亦被加熱，使該 ϋ 熱傳遞至反應容器內流動的氣流中之構件。因此，上述傳 熱構件係由有關適合於熱傳遞的材料所構成，而且只要是 具有可縮小氣體的流路而提高氣體流速的構造，則可爲任 何的材料、構造。例如，可利用藉由組合具備透孔或凹部 的複數成型塡充物而形成氣體流路者、或具備各種形狀的 貫通孔之擋板等，較佳可利用具備一或複數的貫通孔之碳 製板狀體’尤其多孔板。又，傳熱構件的配置方法係按照 其構造可採取各式各樣的態樣，並沒有特別的限定，可以 201038479 橫斷反應容器的氣體流路’使氣流通過傳熱構件的貫通孔 等之方式來配置。而且’此處所謂的提高氣體流速’就是 意味當比較在氣體接觸傳熱構的部位之氣體流速與氣體邊 接觸傳熱構件邊流動而自傳熱構件離開之際的氣體流速時 ，後者的氣體流速比前者還高。例如’使用多孔板時，與 在孔部入口的氣體流速相比’使在多孔板的孔部出口之氣 體流速上升。其上升比例雖然依賴於開孔率等’但可爲數 倍，例如3倍等。 〇 於該氣相反應裝置中’由於在反應容器的內部配設有 傳熱構件，故若藉由加熱手段來加熱反應容器，可由來自 反應容器的壁體等之輻射傳熱等來加熱傳熱構，藉由從該 傳熱構件往氣流的熱傳遞，可更加熱反應容器中的氣流， 而且藉由傳熱構件而提高在其附近流動的氣流之流速，故 由傳熱構件等到氣流的傳熱效率變高，且由於傳熱構件而 氣流紊亂，亦發生對流傳熱。因此，與在反應容器內未配 設傳熱構件的情況相比，對反應容器內的氣流之傳熱量增 ^ 加，可在反應容器內達成高的傳熱效率，進而高反應收率 〇 於一態樣中，上述的反應容器係由在上下方向延伸， 形成自下部側的流入口到上部側的流出口之氣體流路的筒 狀體所構成，傳熱構件係可由在反應容器的內部，於略水 平方向橫斷筒狀體，在上下方向留間隔配設的複數之多孔 板所構成。特別地，反應容器較佳爲碳製的圓筒狀反應器 ’於一例中’可爲具備在上下方向延伸的圓筒狀部、在圓 201038479 筒狀部的下部所設置的底部、與在圓筒狀部的上 的頂板部，在底部設有流入口，在接近筒狀部的 位置設有流出口之構造。 若使反應容器成爲如此的筒狀體構造，則與 路在上下方向往返的情況相比，裝置的構造係變 由如上述配設的複數之多孔板來構成傳熱構件， 在孔部流動時，流速變高，可達成高的傳熱效率 亦有效地產生對流傳熱。 Ο 本發明者等係如後述實施例中所說明地，對 部等的氣體之流速、多孔板的開孔率、反應容器 孔板的間隙、多孔板的厚度等，爲了實驗地求得 範圍，進行專心致力的檢討。結果，瞭解爲若使 數在如下範圍，則可得到高的傳熱效率。 即，上述中的多孔板較佳爲由具有通過的氣 爲2m/s以上之多孔部所成者，而且較佳爲在與反 內壁之間留指定的間隙配設有具備25%以下的開 ^ 材者。多孔板與反應容器的內壁之間的間隙較佳 方向係略均一，而且較佳爲設計成反應容器的內 6/1 000〜5 0/1000的範圍。較佳爲多孔板的孔部之 應容器的內壁直徑之25/1 000以下，孔數係開孔 以下之數。又，多孔板的厚度t較佳爲10 mm S t 製作加工上若沒有問題則沒有該限定。 此處，多孔板的開孔率係指相於含多孔板的 面視之總面積而言，孔部橫斷面積的總計之比例 部所設置 頂板部之 使氣體流 簡單。若 則當氣流 ，而且可 於通過孔 內壁與多 最合適的 指定的參 體之流速 應容器的 孔率之板 爲在圍周 壁直徑之 孔徑係反 率爲2 5 % $ 60mm 〇 孔部之平 ，間隙係 201038479 指多孔板的外緣端面與內壁面之距離。 而且，在另一態樣中，上述複數的多孔板係在上下方 向留間隔所配設，上下鄰接的各多孔板較佳係孔部形成在 互相偏心的位置所成。多孔板之上下方向的距離間隔係可 爲等間隔或不等間隔。 藉由成爲如此的構成，氣流的流動在由反應容器的下 部之流入口流到上部側的流出口時，被充分混合而促進化 學反應，且由於對流傳熱等而增加傳熱量。 Ο 又，在更一態樣中，上述反應容器與傳熱構件係可爲 表面可經碳化矽被覆的碳製構件製。作爲碳製構件，雖然 相關構件係耐熱性、耐熱衝撃性、耐蝕性等優異，但是如 後述地，由於供應給反應容器內的氫，或由於氫的燃燒所 生成的水，碳製構件係遭受組織的減薄或脆化。因此，對 於長期的使用，較佳爲對表面施予碳化矽被膜處理。碳化 矽被膜處理例如係可藉由CVD法以10〜5 00 μιη的厚度來 進行。 〇 若依照又另一態樣，上述氣相反應裝置較佳爲具備金 屬製的外筒容器與內襯於外筒容器的絕熱層，於內部封入 有惰性氣體的收容容器中，收納反應容器與加熱手段而成 者。 藉由成爲如此的構成，可極力防止由加熱手段所產生 的熱逃到裝置外部’而且可極力均勻地進行反應容器的加 熱。 若依照再另一態樣，本發明的氣相反應裝置特別適用 -10- 201038479 於複數種的原料氣體含有四氯矽烷與氫，反應生成氣體含 有三氯矽烷與氯化氫之反應系統。 此處’原料氣體中可含有四氯矽烷與氫以外的化學物 種’而且亦可使來自其它系統的循環液等蒸發而一倂供給 。又’反應生成氣體中可含有三氯矽烷與氯化氫以外的化 學物種’例如未反應的原料成分或六氯二矽烷等的高沸點 物質、二氯矽烷等的低沸點物質等。 再者’於本發明的氣相反應裝置中，除了上述各種構 Ο 成的任一個以外，爲了更提高反應容器內的傳熱效率，亦 可在反應容器的內部，接近流出口處，設置可使反應生成 氣體的流動向流出口之反射構件。 該反射構件只要是在反應生成氣體的流動撞上時使其 反射，而使反應生成氣體的流動向流出口之構件，則可爲 任何者，但較佳爲加熱手段將反應容器.的內部加熱，結果 反應容器之內部所配設的反射構件本身亦被加熱，使該熱 傳遞至反應容器內的氣流之傳熱構件。因此，反射構件較 〇 佳爲接受反應生成氣體的流動，使所反射的流動朝向流出 口之板材，由適合熱傳遞的材料所構成，例如碳製的板狀 體係可合適地利用。 於該氣相反應裝置中，可藉由反射構件來更提高對反 應容器中的氣流之傳熱效率，可達成高的反應收率。 再者’於本發明的氣相反應裝置中，除了上述各種構 成的任一個以外’較佳爲亦具備將由反應容器所導出的反 應生成氣體急冷的急冷塔。 -11- 201038479 藉由成爲如此的構成，可盡可能地瞬間冷卻反應生成 氣體來凍結平衡，而極力防止逆反應發生。 即，於本發明的一態樣中，提供一種氣相反應裝置， 其具備： 使由流入口以指定的流入流速供給的複數種之原料氣體 進行氣相反應，由流出口當作反應生成氣體排出之反應容 器， 附設於反應容器，加熱反應容器之內部的加熱手段， Ο 配設於反應容器的內部，縮小氣體的流路而提高氣體流 速之傳熱構件，及 連接於反應容器，將由反應容器的流出口所導出的反應 生成氣體急冷之急冷裝置。 【實施方式】 以下，參照圖面來說明本發明的氣相反應裝置之一實 施形態。 於第1圖所示的實施形態中，氣相反應裝置10具備圓 〇 筒狀的收容容器11、收納在收容容器11之內部的反應容 器12、收納在收容容器11之內部且附設於反應容器12而 加熱反應容器12的內部之加熱器（加熱手段）13、與連接於 反應谷器12的急冷:¾•(急冷裝置）14。 收容容器11係在鋼製的外筒容器15之底部及圓周部 的各內面內襯有絕熱磚層16a、在外筒容器15的上部內面 內襯有氧化鋁製絕熱材等的絕熱材層16b之絕熱容器，由 圓筒狀的身軀部11a、在身軀部11a的上端所設置的頂蓋 -12- 201038479 部lib、與在身軀部lla的下端所設置的底板部He所構 成，在身軀部11a的外側面所設置的支持構件lid係在基 礎上被支持，軸心朝向上下而設置。於底板部lie的中心 形成貫通孔1 1 e，在身軀部1 1 a的上緣側之指定位置形成 貫通孔1 1 f。 反應容器12係下部被收容容器11的內部所支持，軸 心朝向上下，於收容容器1 1的身軀部1 1 a內壁與頂蓋部 lib之間留有空間而被收納的碳製略圓筒狀之反應容器， 〇 以使端部彼此對接而略同軸狀地在上下配置指定高度的複 數之略圓筒構件，藉由螺合締結或外嵌合環的締結等締結 手段來氣密地締結對接的端部而成爲圓筒體（筒狀體）17， 以與圓筒構件彼此同樣的締結手段分別地在圓筒體1 7的 下端部氣密地締結碳製的底板構件〗8，在圓筒體17的上 端部氣密地締結碳製的頂蓋構件19而成爲圓筒狀容器。 反應容器12係其底板構件18嵌入收容容器11的底板部 lie之貫通孔ue’被收容容器π所支持，在該底板構件 〇 18形成有貫通孔’以成爲對反應容器12的原料氣體之流 入口 l2a’使在未圖示的蒸發罐所連接的流入管2〇連通該 貫通孔而安裝。頂蓋構件19係由閉塞構件所成，作爲反 應容器12的流出口 12b之貫通孔，係形成在接近頂蓋構 件19的圓筒體17之圓筒構件的側面，反應生成氣體的抽 出管21係安裝於該貫通孔。該抽出管2ι更插通收容容器 1 1的貫通孔1 1 f，略水平地延伸到收容容器n的外部爲止 ，而連接於急冷塔14。 -13- 201038479 加熱器13係前端側電互相連接的二支一組，具備在收 容容器11的身軀部Ua內壁與反應容器12之間的空間， 於反應容器12的圍周方向，留間隔而鉛直配設的長條棒 狀之碳製的複數組發熱體13a，與在發熱體13a的各基端 側所連結的對發熱體13a進行電力的授受之複數組的電極 13b。發熱體13a的基端側係在收容容器11的頂蓋部lib 隔著絕熱材等而被支持，發熱體13a的前端側係垂下到收 容容器11的底板部11c之附近爲止。 〇 於收容容器11的內部塡充有氬氣等的惰性氣體，在反 應容器1 2的周圍和上部有惰性氣體的存在，若施加加熱 器1 3，則發熱體1 3 a被加熱，惰性氣體以及反應容器1 2 係由外周及上方例如被加熱到1 3 00 °C左右而構成。 急冷塔14係將由反應容器12的抽出管21所抽出的以 三氯矽烷和氯化氫的混合物當作主成分的反應生成氣體瞬 間冷卻者，具備鄰接於收容容器11而配設的鋼製圓筒狀 塔本體22、附設於塔本體22的具備將冷卻液噴灑到塔本 ◎ 體22的內部之噴嘴的噴霧裝置23、取出塔本體22的內部 所積存的冷卻液而使循環到噴霧裝置23之泵（省略圖示）、 將冷卻液冷卻的冷卻裝置（省略圖示）、及用於由急冷塔14 的頂部取出急冷後的反應生成氣體之導管（省略圖示）。於 塔本體22的側壁插入有反應容器12的抽出管21之反應 生成氣體導入管24係略水平地設置，抽出管21的前端係 延伸到塔本體22的內部爲止，從噴霧裝置23的噴嘴而來 的冷卻液係對由抽出管21所流出的反應生成氣體，由上 -14- 201038479 往下噴霧而構成。 於本實施形態的氣相反應裝置10中，在反應容器12 的內部，將具有指定開孔率、孔徑、孔數的圓板狀之碳製 多孔板25，以複數片在其圓筒體17的高度方向中留間隔 而配設。此等多孔板25係在圓筒體17的高度方向之略全 長中，基本上略等間隔地且略水平地配置，但是在與反應 容器12的內壁面之間保持指定的間隙，而且各多孔板25 基本上係以一多孔板25的孔部25a與位於其上下的多孔板 〇 25之孔部25a成爲不同軸的方式而製作或配置。 此處，多孔板25的設置方法係任意，例如於圖示例中 ，藉由在底板構件18的上面與最下位的多孔板25之下面 的對應位置，分別形成複數的凹處，在底板構件18的凹 處嵌入複數的棒狀間隔構件26之下端部，在多孔板25的 下面之凹處嵌入該棒狀間隔構件26的上端部，而將多孔 板25配置在底板構件18的上方之指定位置，重複此操作 ，留指定的間隔堆積多孔板25。作爲另一方法，可在反應 Ο 容器12的內壁面，於圓周方向留間隔而形成或安裝複數 的支持緣，於其上載置各多孔板25。再者，此處的間隔構 件2 6當然亦爲碳製構件。 對於如上述地在反應容器12的內部所設置的多孔板25 ’本發明者等驗證多孔板的開孔率、與內壁的間隙、多孔 板的厚度等對其設置效果之影響。結果，知道若設置多孔 板25，則可大幅提高反應容器12的傳熱效率，所使用的 多孔板25較佳爲具備如下的特性。 -15- 201038479 •具有通過的氣體之流速爲2m/s以上的多孔部25a •具有25%以下的開孔率。 •與反應容器1 2的內壁之間的間隙係在反應容器1 2的 內壁直徑之6/1000〜50/1 000的範圍。 •孔部的孔徑爲反應容器12的內壁直徑之2 5/1 000以下 ，孔數係開孔率爲25 %以下之數。 •多孔板的厚度t較佳爲10mmStS60mm，製作加工上 若沒有問題則沒有該限定。 〇 此處，多孔板的開孔率係指相對於含多孔板的孔部之 平面視的總面積而言，孔部橫斷面積的總計之比例，間隙 係指多孔板的外緣端面與反應容器的內壁面之距離。 於上述中，作爲構成碳製構件的材質，較佳爲氣密性 優異的石墨材，特別地從由於微粒子構造而強度高、熱膨 脹等特性對於任一方向皆相同來看，較佳爲使用耐熱性及 耐蝕性亦優異的等方向性高純度石墨。 再者，由於供應給反應容器內的氫，或由於氫的燃燒 ο 所生成的水，碳係如以下地遭受組織的減薄或脆化。 C + 2H2-> CH4 c+h2o— h2 + co C + 2H2〇— 2H2 + C〇2 爲了防止它，較佳在上述碳製構件的表面上形成碳化 矽被膜。 碳化矽被膜的形成方法係沒有特別的限制，典型地可 藉由CVD法來蒸鍍而形成。爲了藉由CVD法在指定構件 -16- 201038479 的表面上形成碳化矽被膜，例如可使用：用如四氯矽烷或 三氯矽烷的鹵化矽化合物與甲烷或丙烷等的烴化合物之混 合氣體的方法，或邊以氫將如甲基三氯矽烷、三苯基氯矽 烷、甲基二氯矽烷、二甲基二氯矽烷、三甲基氯矽烷之具 有烴基的鹵化矽化合物熱分解，邊在經加熱的碳製構件之 表面上沈積碳化矽的方法。碳化矽被膜的厚度較佳爲10〜 5 00μιη，更佳爲30〜3 00μπι。碳化矽被膜的厚度若爲ΙΟμιη 以上，則可充分抑制反應容器內存在的氫、水、甲烷等所 Ο 致的碳製構件之腐蝕，而若爲500μιη以下，則亦不會助長 碳化矽被膜的龜裂或碳製構件之組織的破裂。 接著，一邊適宜地參照第1圖以及第2圖的模型圖， 一邊說明本實施形態的氣相反應裝置1 〇之作用。 經蒸發罐所氣化的四氯矽烷與氫之混合氣體係由流入 口 12a以指定的導入流速被導入到反應容器12中。反應容 器1 2係被加熱器1 3由外部來加熱，加熱器1 3係在圓周 方向以等間隔配設於反應容器1 2的外部，由於在收容容 0 器11內塡充有氬氣等的惰性氣體，故反應容器12的外周 面被比較均勻地加熱。藉由來自加熱器13的輻射傳熱， 熱係到達反應容器12的外面（參照第2圖（a))，若加熱反 應容器12全體，由於反應容器12係碳製，故在反應容器 12的壁體，藉由從其外表面向內表面的傳導傳熱，熱係有 效率地對反應容器12內壁表面的傳導，圓筒體17的內壁 表面變成高溫（參照第2圖（b))，反應容器12的內部藉由 輻射傳熱等而加熱到約700〜1 400 °C的高溫。然後，對反 -17- 201038479 應容器12內所流動的氣流’藉由對流傳熱來傳導其熱 而加熱氣流，同時由反應容器12的圓筒體17之內壁表 向多孔板25發生輻射傳熱，而加熱多孔板25(參照第2 (<0)，同時來自多孔板25的熱係傳導至碰撞多孔板25 在多孔板25的孔部25a中流通的氣流。又’原料氣體與 應生成氣體混雜流動，在多孔板25的孔部25a周邊發生 流傳熱，藉此亦加熱氣體（参照第2圖（d))。由於如此被 熱的多孔板25係配置在反應容器12內’故反應容器 〇 內的傳熱面積增加，亦發生對流傳熱’結果對氣流的傳 量升高，而且於氣流通過多孔板25的孔部25a之際，氣 的流速升高，故在多孔板25的孔部25 a附近的傳熱效率 高。如此地，以高效率加熱反應容器12內所流動的氣 ，式（1)的熱平衡反應在正方向進行’所導入的原料氣體 化成以三氯矽烷與氯化氫當作主成分的反應生成氣體， 流出口 12b經由抽出管21導引至急冷塔14。 如此地，於本實施形態的氣相反應裝置10中，由於 Ο 以加熱器13所加熱的反應容器12之內部設有多孔板25 故發生氣流的混合，同時反應容器12內的傳熱效率係 多孔板2 5的輻射傳熱和對流傳熱所提高。 又，由於在反應容器12的流出口 12b設置抽出管21 連接於急冷塔14，多孔板25的效果亦相輔，反應生成 體係在由抽出管21抽出的狀態下成爲經充分加熱的狀 ，由於在該狀態下於急冷塔14中將反應生成氣體瞬間 卻，故凍結平衡反應，有效地防止逆反應。 面 圖 或 反 對 加 12 熱 流 升 流 轉 由 在 * 被 氣 態 冷 -18- 201038479 以上說明本發明的一實施形態，惟本發明當然不受該 實施形態所限定。例如，除了多孔板25以外，於反應容 器12的內部在接近流出口 12b處，亦可設置若反應生成 氣體的流動撞上時能使其反射，使反應生成氣體的流動朝 向流出口之由碳等的傳熱性材料所成的反射板。藉由該反 射構件，可更提高對反應容器中的氣流之傳熱效率，可達 成高的反應收率。又，亦可爲使多孔板2 5組合擋板或其 它成型塡充物的構造。再者，反應容器12在圖示例中雖 〇 然是上下方向同徑的圓筒狀，但亦可爲將流出口 12b的附 近或流入口 1 2 a的附近設爲縮徑部。 以下，記載對於多孔板的設置效果進行驗證的實施例 。再者，此實施例係多孔板的典型例’用於確認設置效果 ，但是多孔板的構成係不受該實施例所限定。 實施例 實施例1 <多孔板的厚度對傳熱量之影響> Θ 於以下的反應裝置中’驗證多孔板的厚度對多孔板的 設置效果之影響。 收容容器： 外筒容器：SUS304製’ 19mm厚 絕熱材層：氧化鋁製絕熱材’ 29〇1111厚 絕熱碍層：氧化鋁製磚’ 50〇111111厚 惰性氣體層：氬氣’ 163mm層 反應容器： -19- 201038479 碳製圓筒狀反應器，100mm厚 圓筒部內徑：750mm 分別製作複數片的厚度爲20mm、40mm、60mm之圓 板狀多孔板（依順序爲多孔板1、基準多孔板、多孔板2)。 各多孔板係以同一圖案形成孔徑5mm的多數孔部，爲碳製 的直徑74cm者，其具備用於將支持棒固定在指定位置的 複數之固定孔。 首先在反應容器內的圓筒體內部於上下留間隔，使用 〇 間隔構件來水平地配置40mm的厚度之基準多孔板。又， 在反應裝置的氣體入口、氣體出口、身軀部中央部等適宜 地設置熱電偶。 於此狀態下，施加加熱器而將反應容器加熱到1 300 °C 爲止後，對反應裝置以1513kg/h的流速供應四氯矽烷與氫 (莫耳=1:2)的混合氣體，在O.IMPaG進行反應而生成三氯 矽烷。而且，反應過程中的氣體溫度：1124.9 °C，測定出 口氣體溫度等的各溫度測定點之溫度，計算反應容器全體 ◎ 的傳熱量，結果爲8760kcal/h。 同樣地，對於20mm的厚度之多孔板1及60mm的厚度 之多孔板2，重複操作，由測定溫度來計算傳熱量。 結果得到如下表所示的結果。 -20- 201038479 [表i] 多孔板1 基準多孔板 多孔板2 多孔板厚度(mm) 20 40 60 傳面積(m2) 2.33 3.08 3.83 出口氣溫度(°C) 1173 1175 1178 傳熱量(kcal/h) 8390 8760 9100 每傳面積的傳熱量 (kcal/m2-h) 3602 2845 2377 傳熱量對基準多孔板的比(％) 95.8 100 103.9 Ο 此結果亦在第3圖中以曲線圖的形式來顯示。 如由此等結果可知，於相對於基準多孔板而言，厚度 爲1.5倍的多孔板2中，傳面積上升25°/。，於相對於基準 多孔板而言’厚度爲1/2的多孔板1中，每傳面積的傳熱 量上升26%。由此等結果可知，若多孔板變薄而增加片數 ，則可期待傳熱量增加。 實施例2 <多孔板的間隙對傳熱量之影響> 〇 除了代替所用的多孔板以外，使用與實施例1記載者 相同的反應裝置、操作條件，驗證多孔板與反應容器的內 壁之間的間隙對多孔板的設置效果之影響。 分別製作複數片的外徑爲 746 mm、740 mm、736〜 710mm的各種之厚度爲40mm的圓板狀多孔板（依順序爲多 孔板3、基準多孔板、多孔板4〜7)。各多孔板係以同一圖 案形成孔徑5mm的多數孔部，具備用於在指定位置固定於 間隔構件的複數之凹處的碳製者。 -21- 201038479 首先在反應容器內的圓筒體內部於上下留間隔而配置 外徑爲740mm的基準多孔板。此時的多孔板與反應容器內 壁間之間隙爲5mm。於此狀態下進行三氯矽烷的生成反應 ，在反應過程中測定入口氣體溫度、出口氣體溫度等的各 溫度測定點之溫度’計算反應容器全體的傳熱量，結果爲 8 760 k cal/h。 同樣地，分別設置外徑爲746mm、736mm、730mm、 720mm、710mm(間隙爲 2、7、10、15、20mm)的多孔板 3 〇 〜7，重複操作，由測定溫度來計算傳熱量。 結果得到如下表所示的結果。 [表2] 多孔板3 基準多 孔板 多孔板4 多孔板5 多孔板6 多孔板7 間隙(mm) 2 5 7 10 15 20 出口氣體溫度(°c) 1171 1175 1177 1178 1177 1176 傳熱量 (kcal/h) 8110 8760 9050 9220 9190 9020 傳熱量對基準多 孔板的比(％) 92.5 100.0 103.3 105.2 104.9 102.9 此結果亦在第3圖中以曲線圖的形式來顯示。 如由此等結果可知，多孔板的間隙之最合適値爲1 0mm ，此時傳熱量變成最大。藉此，由於傳熱係數、來自反應 容器外表面的傳熱量之增加，傳熱量上升5%。 實施例3 <多孔板的孔徑·孔數對傳熱量之影響> -22- 201038479 除了代替所用的多孔板以外，使用與實施例1記載者 相同的反應裝置、操作條件，驗證孔徑·孔數對多孔板的 設置效果之影響。 製作已變更孔徑、孔數、開孔率的3種類之多孔板。 首先，第1多孔板係基準多孔板，孔徑15πιιηφ、孔數504 個、開孔率20.7%，第2多孔板（多孔板8)係孔徑15πιιηφ、 孔數1 024個、開孔率42.1%，第3多孔板（多孔板9)係孔 徑 10·5ηιιηφ、孑L 數 1024 個、開孔率 20·7%。 Ο 於反應容器內的圓筒體內部在上下留間隔而配置各多 孔板，於此狀態下進行三氯矽烷的生成反應，在反應過程 中測定入口氣體溫度、出口氣體溫度等的各溫度測定點之 溫度，計算反應容器全體的傳熱量。 表3中顯示所得之結果。 [表3] 多孔板1 基準多孔板 多孔板2 多孔板厚度(Him) 20 40 60 傳面積(m2) 2.33 3.08 3.83 出口氣體溫度(°C) 1173 1175 1178 傳熱量(kcal/h) 8390 8760 9100 每傳面積的傳熱量 (kcal/m2-h) 3602 2845 2377 傳熱量對基準多孔板的比(％) 95.8 100 103.9 如由此等結果可知，單純地增加多孔板的孔數亦不會 增加傳熱量。茲認此係因爲流速降低，結果傳熱係數減少 。然而，可知若使開孔率爲20.7%，使孔部小徑化，且增 -23- 201038479 加孔數，則傳熱量增加（表的例中，傳熱量上升 【圖式簡單說明】 第1圖係本發明的實施形態之反應裝置的 圖。 第2圖係用於說明第1圖的反應裝置中由 流的傳熱程序之模型圖，第2圖（a)表示由加熱 器的輻射傳熱，第2圖（b)表示反應容器壁體中 ，第2圖（c)表示由反應容器內面對多孔板的輻 〇 2圖（d)表示由反應容器內表面與多孔板對氣體 〇 第3圖係顯示實施例1的結果之曲線圖。 第4圖係顯示實施例2的結果之曲線圖。 【主要元件符號說明】 • 9%) 0 意縱剖面 丨熱器對氣 m反應容 傳導傳熱 傳熱，第 對流傳熱 10 氣相反應裝置 11 收容容器 11a 身軀部 lib 頂蓋部 11c 底板部 lid 支持構件 lie、 1 1 f 貫通孔 12 反應容器 12a 流入口 12b 流出口 13 加熱器（加熱手段） 24- 201038479SiCl4 + H2 - SiHCl3 + HC1 (1) This reaction is a heat equilibrium gas phase reaction in which a positive reaction occurs by heating a raw material gas composed of vaporized tetrachlorosilane and hydrogen to a high temperature of about 700 to 1400 °C. , to obtain trichlorodecane. As a reaction apparatus for such a gas phase reaction, for example, the apparatus described in Patent Document 1 is known. The device includes a reaction chamber surrounded by a heating element and a chamber formed by a concentrically arranged tube forming an outer chamber and an inner chamber, and a diverter provided at an upper portion of the reaction chamber to allow the outer chamber and the inner chamber to communicate with each other. A heat exchanger provided at a lower portion of the reaction chamber for exchanging heat between the material gas introduced into the outer chamber and the reaction product gas derived from the inner chamber. The raw material gas is supplied to the outer chamber by preheating by the heat exchanger, and the reaction is carried out between the outer chamber and the inner chamber via the diverter. The reaction-generating gas system is cooled by the heat exchanger and discharged. However, in the above-described reaction apparatus, since the reaction chamber is connected to the double chamber connected to the device by the transfer of 201038479, the gas is connected to the upper and lower chambers in the order of the outer chamber and the inner chamber, so that the temperature of the outlet gas in the reaction chamber is lowered. The problem. Further, since the reaction product gas cannot be rapidly cooled, the produced trichloromethane has a problem of reverse reaction to tetrachloromethane, and a high reaction yield is not obtained. [Patent Document 1] JP-A-6-293511 SUMMARY OF THE INVENTION An object of the present invention is to provide a gas phase reaction apparatus which at least partially eliminates the problems of the conventional technique. Another object of the present invention is to provide a gas phase reaction apparatus which maintains high heat transfer efficiency. Still another object of the present invention is to provide a gas phase reaction apparatus which can prevent a reverse reaction or the like as much as possible and achieve a high reaction yield, and is particularly suitable for a reaction apparatus for high-temperature gas phase reaction of chlorosilane with hydrogen. Accordingly, the present invention provides a gas phase reaction apparatus comprising: a reaction vessel in which a plurality of kinds of raw material gases supplied from a flow inlet at a predetermined inflow flow rate are subjected to a gas phase reaction, and the outlet is discharged as a reaction product gas; A heating means attached to the reaction vessel, heating the inside of the reaction vessel, and a heat transfer member disposed inside the reaction vessel to reduce the flow path of the gas to increase the gas flow rate. Here, the 'reaction grain device may be any one as long as it is composed of a structure or a material suitable for a high-temperature gas phase reaction, and it is preferable to have an inflow port on one side of the container 201038479, which is spaced apart from the side. On the other side, there is a structure in which the outflow port is disposed at a predetermined distance between the inflow port and the outflow port, and it is preferable that the wall surface is heated by a heating means and the material is conveyed by heat to the inside of the reaction container. The heating means may be any one as long as it can heat the inside of the reaction container, and it is preferable to heat the wall surface of the reaction container so that the inside of the reaction container becomes a high-temperature heating state. In one aspect, the reaction vessel may be formed of a material having excellent heat transfer properties to directly heat the crucible structure of the reaction vessel wall. In another aspect, it is preferred that the reaction vessel is formed of a material having excellent heat conductivity, and a heater is disposed outside the reaction vessel to heat the structure of the wall surface of the reaction vessel. In either case, it is preferable that the reaction container is housed in the storage container, and the periphery is insulated, and in particular, when the latter external heater is provided, it is preferable to preliminarily circulate in the storage container in which the reaction container and the heater are disposed. An inert gas such as argon. The heat transfer member means that the inside of the reaction vessel is heated by heating means, and as a result, the heat transfer member disposed inside the reaction vessel itself is heated to transfer the heat to the member in the gas flow flowing in the reaction vessel. Therefore, the heat transfer member is composed of a material suitable for heat transfer, and may be any material or structure as long as it has a structure capable of reducing the flow path of the gas and increasing the gas flow rate. For example, a gas flow path may be formed by combining a plurality of shaped entanglements having through holes or recesses, or a baffle having a through hole having various shapes, and the like, and carbon having one or a plurality of through holes may preferably be used. The plate-shaped body is especially porous. Further, the method of arranging the heat transfer member is not limited to a wide variety of aspects depending on the configuration thereof, and the gas flow path of the reaction vessel may be passed through the through hole of the heat transfer member in 201038479. Way to configure. Further, 'the so-called increase in the gas flow rate' means that the gas flow rate of the latter is compared when the gas flow rate at the portion where the gas contacts the heat transfer structure is compared with the flow rate of the gas while the gas is in contact with the heat transfer member while leaving the heat transfer member. Higher than the former. For example, when a perforated plate is used, the gas flow rate at the outlet of the perforated plate is increased as compared with the flow rate of the gas at the inlet of the hole. Although the rising ratio depends on the opening ratio or the like, it may be several times, for example, three times or the like. In the gas phase reaction apparatus, since a heat transfer member is disposed inside the reaction vessel, if the reaction vessel is heated by a heating means, heat transfer can be performed by radiation heat transfer or the like from a wall of the reaction vessel. By heat transfer from the heat transfer member to the gas stream, the gas flow in the reaction vessel can be heated more, and the flow velocity of the gas flow flowing in the vicinity thereof is increased by the heat transfer member, so that the heat transfer member or the like is transmitted to the gas flow. The thermal efficiency becomes high, and the airflow is turbulent due to the heat transfer member, and convective heat transfer also occurs. Therefore, compared with the case where the heat transfer member is not disposed in the reaction vessel, the amount of heat transfer to the gas flow in the reaction vessel is increased, and high heat transfer efficiency can be achieved in the reaction vessel, and the high reaction yield is lowered. In one aspect, the reaction container is formed of a cylindrical body extending in the vertical direction and forming a gas flow path from the inlet port on the lower side to the outlet port on the upper side, and the heat transfer member may be inside the reaction container. The tubular body is transversely cut in a horizontal direction, and a plurality of porous plates are disposed at intervals in the vertical direction. In particular, the reaction vessel preferably has a cylindrical reactor made of carbon 'in one example', and may have a cylindrical portion extending in the vertical direction, a bottom portion provided at a lower portion of the cylindrical portion of the circle 201038479, and a circle. The top plate portion on the upper portion of the tubular portion is provided with an inflow port at the bottom portion and a structure of an outflow port at a position close to the tubular portion. When the reaction container has such a tubular structure, the structure of the apparatus is changed from the plurality of porous plates arranged as described above to the heat transfer member as compared with the case where the road is reciprocated in the vertical direction, and the hole portion flows. The flow rate becomes high, high heat transfer efficiency can be achieved, and convective heat transfer is effectively generated. In the present inventors, the flow rate of the gas such as the portion, the opening ratio of the porous plate, the gap of the reaction vessel orifice plate, the thickness of the porous plate, and the like are determined experimentally, as described in the examples below. Conduct a dedicated review. As a result, it is understood that if the number is in the following range, high heat transfer efficiency can be obtained. In other words, the porous plate in the above-described porous plate is preferably made of a porous portion having a passing gas of 2 m/s or more, and preferably has a predetermined gap between the counter inner wall and 25% or less. Open the material. The gap between the perforated plate and the inner wall of the reaction vessel is preferably uniformly uniform, and is preferably designed to be in the range of 6/1 000 to 5 0/1000 of the reaction vessel. Preferably, the diameter of the inner wall of the container of the hole portion of the perforated plate is 25/1000 or less, and the number of holes is the number below the opening. Further, the thickness t of the perforated plate is preferably 10 mm S t , and there is no such limitation if there is no problem in the production process. Here, the opening ratio of the perforated plate means the ratio of the total area of the cross-sectional area of the perforated plate to the total area of the perforated plate, and the ratio of the cross-sectional area of the perforated portion is set to be simple. If the airflow, and the flow rate through the inner wall of the hole and the most suitable designated reference body, the porosity of the container should be the diameter of the aperture wall of the peripheral wall diameter of 2 5 % $ 60mm. Flat, gap system 201038479 refers to the distance between the outer edge of the perforated plate and the inner wall surface. Further, in another aspect, the plurality of perforated plates are disposed at an upper and lower intervals, and the perforated plates adjacent to each other are preferably formed at positions which are eccentric to each other. The distance between the upper and lower sides of the perforated plate may be equally spaced or unequal. With such a configuration, the flow of the gas stream is sufficiently mixed when flowing from the lower inlet port of the reaction vessel to the outlet port on the upper side to promote the chemical reaction, and the amount of heat transfer is increased by convection heat transfer or the like. Further, in a further aspect, the reaction vessel and the heat transfer member may be made of a carbon member whose surface may be coated with tantalum carbide. As a carbon member, although the relevant member is excellent in heat resistance, heat resistance, corrosion resistance, and the like, as will be described later, the carbon member is subjected to hydrogen supplied to the reaction vessel or water generated by combustion of hydrogen. Thinning or embrittlement of the tissue. Therefore, for long-term use, it is preferred to apply a ruthenium carbide film to the surface. The tantalum carbide film treatment can be carried out, for example, by a CVD method at a thickness of 10 to 500 μm. According to still another aspect, the gas phase reaction apparatus preferably includes a metal outer cylinder container and a heat insulating layer lining the outer cylinder container, and is housed in a storage container in which an inert gas is sealed, and the reaction container is housed. Heating means. With such a configuration, it is possible to prevent the heat generated by the heating means from escaping to the outside of the apparatus as much as possible, and the heating of the reaction container can be performed as evenly as possible. According to still another aspect, the gas phase reaction apparatus of the present invention is particularly suitable for use in a reaction system in which a plurality of raw material gases contain tetrachloromethane and hydrogen, and a reaction gas contains trichloromethane and hydrogen chloride. Here, the raw material gas may contain a chemical species other than hydrogen tetrachloride and hydrogen, and the circulating liquid or the like from another system may be evaporated and supplied as it is. Further, the reaction product gas may contain a chemical species other than trichloromethane and hydrogen chloride, for example, an unreacted raw material component, a high-boiling substance such as hexachlorodioxane, or a low-boiling substance such as dichloromethane. Further, in the gas phase reaction device of the present invention, in addition to any of the above various configurations, in order to further improve the heat transfer efficiency in the reaction vessel, it may be provided in the interior of the reaction vessel near the outflow port. A reflecting member that causes the flow of the reaction product gas to flow to the outflow port. The reflecting member may be any member that reflects the flow of the reaction product gas when the reaction product gas collides with the flow of the reaction product gas, but it is preferable that the heating means heats the inside of the reaction container. As a result, the reflecting member disposed inside the reaction vessel itself is also heated to transfer the heat to the heat transfer member of the gas flow in the reaction vessel. Therefore, it is preferable that the reflecting member receives the flow of the reaction-forming gas so that the reflected flow faces the plate of the outflow port and is made of a material suitable for heat transfer, and a plate-like system made of carbon, for example, can be suitably used. In the gas phase reaction apparatus, the heat transfer efficiency to the gas flow in the reaction vessel can be further improved by the reflecting member, and a high reaction yield can be achieved. Further, in the gas phase reaction apparatus of the present invention, in addition to any of the above various configurations, it is preferable to provide a quenching tower which rapidly quenches the reaction product gas derived from the reaction vessel. -11- 201038479 By such a configuration, the reaction product gas can be cooled as quickly as possible to freeze the equilibrium, and the reverse reaction is prevented as much as possible. That is, in one aspect of the invention, there is provided a gas phase reaction apparatus comprising: performing a gas phase reaction on a plurality of material gases supplied from a flow inlet at a specified inflow flow rate, and using the outlet as a reaction gas The discharged reaction vessel is attached to the reaction vessel, heating means for heating the inside of the reaction vessel, Ο disposed inside the reaction vessel, narrowing the flow path of the gas to increase the gas flow rate of the heat transfer member, and connecting to the reaction vessel, and reacting The reaction derived from the outlet of the vessel produces a quenching device that quenches the gas. [Embodiment] Hereinafter, an embodiment of a gas phase reaction apparatus of the present invention will be described with reference to the drawings. In the embodiment shown in Fig. 1, the gas phase reaction device 10 includes a cylindrical storage container 11 and a reaction container 12 housed inside the storage container 11, and is housed inside the storage container 11 and attached to the reaction container. 12, a heater (heating means) 13 for heating the inside of the reaction vessel 12, and a quenching: 3⁄4 (quick cooling device) 14 connected to the reaction vessel 12. The storage container 11 is lined with a heat insulating brick layer 16a on the inner surface of the bottom portion and the circumferential portion of the steel outer cylinder container 15, and a heat insulating material layer such as an alumina heat insulating material is lined on the inner surface of the upper portion of the outer cylinder container 15. The heat insulating container of 16b is composed of a cylindrical body portion 11a, a top cover -12-201038479 portion lib provided at the upper end of the body portion 11a, and a bottom plate portion He provided at the lower end of the body portion 11a. The support member lid provided on the outer side surface of the portion 11a is supported on the basis of the support, and the axial center is provided to face up and down. A through hole 1 1 e is formed in the center of the bottom plate portion lie, and a through hole 1 1 f is formed at a predetermined position on the upper edge side of the body portion 1 1 a. The lower portion of the reaction container 12 is supported by the inside of the storage container 11, and the axis is oriented upward and downward, and a space slightly left between the inner wall of the body portion 1 1 a of the storage container 1 1 and the top cover portion lib is stored. The cylindrical reaction container is configured such that the end portions are butted to each other and a plurality of substantially cylindrical members of a predetermined height are disposed on the upper and lower sides in a substantially coaxial manner, and are tightly sealed by means of a screwing or an outer fitting ring. The abutting end portion is formed into a cylindrical body (cylindrical body) 17, and the carbon bottom plate member 8 is airtightly joined to the lower end portion of the cylindrical body 17 by the same joining means as the cylindrical members. A carbon top cover member 19 is airtightly joined to the upper end portion of the cylindrical body 17 to form a cylindrical container. The reaction container 12 is supported by a storage container π in which the bottom plate member 18 is fitted into the bottom plate portion lie of the storage container 11, and a through hole ' is formed in the bottom plate member 〇18 to be a raw material gas flow to the reaction container 12. The inlet l2a' is attached to the inflow pipe 2 connected to the evaporation can (not shown) so as to communicate with the through hole. The top cover member 19 is formed of a closing member, and a through hole as the outflow port 12b of the reaction container 12 is formed on the side surface of the cylindrical member close to the cylindrical body 17 of the top cover member 19, and the extraction tube 21 for generating a gas is formed. It is attached to the through hole. The extraction tube 2i is further inserted into the through hole 1 1 f of the storage container 1 1 and extends to the outside of the storage container n horizontally, and is connected to the quenching tower 14 . -13- 201038479 Two sets of the heater 13 are electrically connected to each other at the front end side, and have a space between the inner wall of the body Ua of the storage container 11 and the reaction container 12, and are spaced apart in the circumferential direction of the reaction container 12. On the other hand, the plurality of rod-shaped carbon composite array heating elements 13a are vertically disposed, and the electrodes 13b are electrically connected to the heating element 13a connected to the respective base ends of the heating element 13a. The base end side of the heat generating body 13a is supported by the top cover portion lib of the storage container 11 via a heat insulating material or the like, and the front end side of the heat generating body 13a is suspended to the vicinity of the bottom plate portion 11c of the container 11. The inside of the storage container 11 is filled with an inert gas such as argon gas, and an inert gas is present around the upper portion and the upper portion of the reaction container 12. When the heater 13 is applied, the heating element 1 3 a is heated, and the inert gas is heated. Further, the reaction container 12 is configured by heating the outer circumference and the upper portion to, for example, about 1 300 °C. In the quenching tower 14 , the reaction product gas which is a main component of the mixture of trichlorosilane and hydrogen chloride extracted from the extraction pipe 21 of the reaction vessel 12 is instantaneously cooled, and is provided with a steel cylindrical shape which is disposed adjacent to the storage container 11 . The tower main body 22, the spray device 23 provided with the nozzle for spraying the coolant to the inside of the tower body 22, and the pump which is discharged from the inside of the tower main body 22 and is circulated to the spray device 23 (not shown), a cooling device (not shown) that cools the coolant, and a conduit (not shown) for taking out the reaction-generated gas after the quenching from the top of the quenching tower 14. The reaction product gas introduction pipe 24 in which the extraction pipe 21 of the reaction container 12 is inserted into the side wall of the column main body 22 is disposed horizontally, and the front end of the extraction pipe 21 extends to the inside of the column main body 22, from the nozzle of the spray device 23. The resulting coolant is formed by reacting a gas generated by the extraction pipe 21 and spraying it downward from the upper-14-201038479. In the gas phase reactor 10 of the present embodiment, a disk-shaped carbon porous plate 25 having a predetermined opening ratio, a pore diameter, and a number of holes is provided in the inside of the reaction vessel 12 in a plurality of sheets in the cylindrical body 17 thereof. The height direction is set to be spaced apart. These perforated plates 25 are arranged substantially slightly at equal intervals and slightly horizontally in the longitudinal direction of the cylindrical body 17, but maintain a prescribed gap between the inner wall faces of the reaction vessel 12, and each of the perforations The plate 25 is basically formed or arranged such that the hole portion 25a of the perforated plate 25 and the hole portion 25a of the perforated plate 25 located above and below are different from each other. Here, the method of arranging the perforated plate 25 is arbitrary. For example, in the illustrated example, a plurality of recesses are respectively formed by corresponding positions on the upper surface of the bottom plate member 18 and the lowermost perforated plate 25, in the bottom plate member. The recess of 18 is embedded in the lower end portion of the plurality of rod-shaped spacer members 26, and the upper end portion of the rod-shaped spacer member 26 is fitted in the recess in the lower surface of the perforated plate 25, and the perforated plate 25 is disposed above the bottom plate member 18. Position, repeat this operation, leaving the perforated plate 25 at the specified interval. As another method, a plurality of support edges may be formed or mounted on the inner wall surface of the reaction crucible container 12 at intervals in the circumferential direction, and the perforated plates 25 may be placed thereon. Further, the spacer member 26 herein is of course also a carbon member. The inventors of the present invention have verified the influence of the opening ratio of the perforated plate, the gap with the inner wall, the thickness of the perforated plate, and the like on the effect of the perforated plate 25' provided in the inside of the reaction container 12. As a result, it is known that the heat transfer efficiency of the reaction container 12 can be greatly improved by providing the porous plate 25, and the porous plate 25 to be used preferably has the following characteristics. -15- 201038479 • The porous portion 25a having a flow rate of the passing gas of 2 m/s or more • having an opening ratio of 25% or less. The gap with the inner wall of the reaction vessel 12 is in the range of 6/1000 to 50/1 000 of the inner wall diameter of the reaction vessel 12. • The pore diameter of the pore portion is 2 5/1 000 or less of the diameter of the inner wall of the reaction vessel 12, and the number of pores is 25% or less. The thickness t of the perforated plate is preferably 10 mmStS 60 mm, and there is no such limitation if there is no problem in the production process. Here, the opening ratio of the perforated plate means the ratio of the total area of the cross-sectional area of the perforated portion with respect to the total area of the plane of the hole portion including the perforated plate, and the gap means the outer end surface of the perforated plate and the reaction The distance from the inner wall of the container. In the above, as the material constituting the carbon member, a graphite material having excellent airtightness is preferable, and in particular, from the viewpoint of high strength and thermal expansion due to the fine particle structure, it is preferable to use heat resistance in any direction. Isotropic high-purity graphite excellent in properties and corrosion resistance. Further, the carbon is subjected to thinning or embrittlement of the structure as follows due to hydrogen supplied to the reaction vessel or water generated by the combustion of hydrogen. C + 2H2-> CH4 c + h2o - h2 + co C + 2H2 〇 - 2H2 + C 〇 2 In order to prevent it, it is preferred to form a ruthenium carbide film on the surface of the above carbon member. The method for forming the tantalum carbide film is not particularly limited, and is typically formed by vapor deposition by a CVD method. In order to form a tantalum carbide film on the surface of the specified member-16-201038479 by a CVD method, for example, a method of using a mixed gas of a phosphonium compound such as tetrachlorosilane or trichloromethane with a hydrocarbon compound such as methane or propane may be used. Or thermally decomposing a halogenated ruthenium compound having a hydrocarbon group such as methyltrichloromethane, triphenylchlorodecane, methyldichlorodecane, dimethyldichlorodecane or trimethylchloromethane by hydrogen, while A method of depositing tantalum carbide on the surface of a heated carbon member. The thickness of the tantalum carbide film is preferably from 10 to 500 μm, more preferably from 30 to 300 μm. When the thickness of the tantalum carbide film is ΙΟμηη or more, corrosion of the carbon member such as hydrogen, water, methane, or the like existing in the reaction container can be sufficiently suppressed, and if it is 500 μm or less, the tantalum carbide film is not promoted. Cracking of the structure of a crack or carbon component. Next, the action of the gas phase reaction apparatus 1 of the present embodiment will be described with reference to the model diagrams of Figs. 1 and 2 as appropriate. The mixed gas system of tetrachloromethane and hydrogen vaporized by the evaporation can is introduced into the reaction vessel 12 by the inflow port 12a at a prescribed introduction flow rate. The reaction vessel 12 is heated by the heater 13 from the outside, and the heaters 13 are disposed outside the reaction vessel 12 at equal intervals in the circumferential direction, and the argon gas is filled in the accommodating container 11. The inert gas is such that the outer peripheral surface of the reaction vessel 12 is heated relatively uniformly. The heat is radiated by the radiation from the heater 13, and the heat reaches the outside of the reaction container 12 (see Fig. 2(a)). When the entire reaction container 12 is heated, since the reaction container 12 is made of carbon, it is in the reaction container 12. The wall body is heat-transferred from the outer surface to the inner surface, and the heat is efficiently conducted to the inner wall surface of the reaction container 12, and the inner wall surface of the cylindrical body 17 becomes high temperature (refer to Fig. 2(b)). The inside of the reaction vessel 12 is heated to a high temperature of about 700 to 1 400 ° C by radiation heat transfer or the like. Then, the anti--17-201038479 airflow flowing in the container 12 is heated by the convective heat transfer to heat the gas stream while being radiated from the inner wall of the cylindrical body 17 of the reaction vessel 12 toward the perforated plate 25. The heat transfer is performed to heat the perforated plate 25 (refer to the second (<0), and the heat from the perforated plate 25 is conducted to the gas flow which flows through the hole portion 25a of the perforated plate 25 in the perforated plate 25. A gas mixed flow is generated, and heat transfer occurs around the hole portion 25a of the perforated plate 25, thereby heating the gas (see Fig. 2(d)). The porous plate 25 thus heated is disposed in the reaction vessel 12' Therefore, the heat transfer area in the crucible of the reaction vessel increases, and convective heat transfer also occurs. As a result, the flow rate of the gas flow rises, and as the gas flows through the pore portion 25a of the perforated plate 25, the flow velocity of the gas rises, so the perforated plate The heat transfer efficiency in the vicinity of the hole portion 25a of 25 is high. Thus, the gas flowing in the reaction vessel 12 is heated with high efficiency, and the heat balance reaction of the formula (1) is carried out in the forward direction. Reaction of decane with hydrogen chloride as a main component The gas is introduced into the quenching tower 14 via the extraction pipe 21. Thus, in the gas phase reaction apparatus 10 of the present embodiment, the inside of the reaction vessel 12 heated by the heater 13 is provided with a perforated plate. 25, the mixing of the gas stream occurs, and the heat transfer efficiency in the reaction vessel 12 is improved by the radiant heat transfer and the convective heat transfer of the perforated plate 25. Further, since the extraction pipe 21 is provided at the outflow port 12b of the reaction vessel 12, the extraction pipe 21 is connected to the quenching. In the column 14, the effect of the perforated plate 25 is also complementary, and the reaction product system is sufficiently heated in a state of being withdrawn by the extraction pipe 21, and in this state, the reaction gas is generated in the quenching tower 14 instantaneously, so that it is frozen. Balancing the reaction, effectively preventing the reverse reaction. The surface pattern or the anti-addition 12 heat flow upflow is described by an embodiment of the present invention in the above-described state of the present invention. However, the present invention is of course not limited to the embodiment. In addition to the perforated plate 25, in the inside of the reaction vessel 12, near the outflow port 12b, it is also possible to provide a reflection of the flow of the reaction product gas when it collides with it. A reflecting plate made of a heat-transfer material such as carbon, which flows toward the outlet of the reaction product gas. The reflecting member can further improve the heat transfer efficiency to the gas flow in the reaction vessel, thereby achieving high reaction yield. Further, the porous plate 25 may have a structure in which a baffle or another formed entangled material is combined. Further, the reaction container 12 may be a cylindrical shape having the same diameter in the vertical direction in the illustrated example, but may be In the vicinity of the outflow port 12b or the vicinity of the inflow port 12 a, the reduced diameter portion is used. Hereinafter, an example in which the effect of the installation of the perforated plate is verified will be described. Further, this embodiment is a typical example of a perforated plate. The effect of the setting is confirmed, but the configuration of the perforated plate is not limited to this embodiment. EXAMPLES Example 1 <Effect of thickness of porous plate on heat transfer amount> Θ In the following reaction apparatus, the effect of the thickness of the porous plate on the effect of setting the porous plate was verified. Storage container: Outer tube container: SUS304 system '19mm thick insulation material layer: alumina insulation material' 29〇1111 thick insulation layer: alumina brick '50〇111111 thick inert gas layer: argon' 163mm layer reaction container : -19- 201038479 Carbon cylindrical reactor, 100 mm thick cylindrical inner diameter: 750 mm A disk-shaped porous plate having a thickness of 20 mm, 40 mm, and 60 mm in a plurality of sheets (in the order of perforated plate 1 and reference porous plate) , multi-well plate 2). Each of the perforated plates was formed into a plurality of holes having a hole diameter of 5 mm in the same pattern, and was made of carbon having a diameter of 74 cm, and provided with a plurality of fixing holes for fixing the support bars at specified positions. First, the inside of the cylindrical body in the reaction container was left and left at intervals, and a reference porous plate having a thickness of 40 mm was horizontally arranged using a 间隔 spacer member. Further, a thermocouple is suitably provided at the gas inlet, the gas outlet, the central portion of the body portion, and the like of the reaction apparatus. In this state, after the heater was applied and the reaction vessel was heated to 1,300 ° C, a mixed gas of tetrachlorosilane and hydrogen (mole = 1:2) was supplied to the reaction apparatus at a flow rate of 1513 kg/h. .IMPaG reacts to form triclosan. Further, the gas temperature during the reaction was 1124.9 ° C, and the temperature at each temperature measurement point such as the outlet gas temperature was measured, and the heat transfer amount of the entire reaction vessel was calculated. As a result, it was 8760 kcal/h. Similarly, for the perforated plate 1 having a thickness of 20 mm and the perforated plate 2 having a thickness of 60 mm, the operation was repeated, and the amount of heat transfer was calculated from the measured temperature. As a result, the results shown in the following table were obtained. -20- 201038479 [Table i] Perforated plate 1 Reference porous plate perforated plate 2 Thickness of perforated plate (mm) 20 40 60 Transmission area (m2) 2.33 3.08 3.83 Outlet gas temperature (°C) 1173 1175 1178 Heat transfer capacity (kcal/h 8390 8760 9100 Heat transfer per area (kcal/m2-h) 3602 2845 2377 Ratio of heat transfer to reference multi-well plate (%) 95.8 100 103.9 Ο This result is also shown in the form of a graph in Figure 3. . As can be seen from the results, in the porous plate 2 having a thickness of 1.5 times with respect to the reference porous plate, the transfer area was increased by 25 ° /. In the perforated plate 1 having a thickness of 1/2 with respect to the reference porous plate, the amount of heat transfer per transfer area was increased by 26%. From these results, it can be seen that when the number of sheets is increased and the number of sheets is increased, the amount of heat transfer can be expected to increase. Example 2 <Influence of the gap of the perforated plate on the amount of heat transfer> In addition to the porous plate used, the same reaction apparatus and operating conditions as those described in Example 1 were used to verify the inner wall of the porous plate and the reaction vessel. The effect of the gap between the holes on the setting effect of the perforated plate. Each of the plurality of disk-shaped porous plates having a thickness of 746 mm, 740 mm, and 736 to 710 mm and having a thickness of 40 mm (in the order of the multi-hole plate 3, the reference perforated plate, and the perforated plates 4 to 7) was produced. Each of the perforated plates was formed into a plurality of holes having a hole diameter of 5 mm in the same pattern, and was provided with carbon for fixing at a predetermined position to a plurality of recesses of the spacer member. -21- 201038479 First, a reference porous plate having an outer diameter of 740 mm was placed in the inside of the cylindrical body in the reaction vessel with a space therebetween. The gap between the porous plate and the inner wall of the reaction vessel at this time was 5 mm. In this state, the formation reaction of trichlorosilane was carried out, and the temperature of each temperature measurement point such as the inlet gas temperature and the outlet gas temperature was measured during the reaction. The heat transfer amount of the entire reaction vessel was calculated and found to be 8 760 kcal/h. Similarly, perforated plates 3 〇 to 7 having outer diameters of 746 mm, 736 mm, 730 mm, 720 mm, and 710 mm (gaps of 2, 7, 10, 15, and 20 mm) were respectively set, and the heat transfer amount was calculated from the measured temperature by repeating the operation. As a result, the results shown in the following table were obtained. [Table 2] Multiwell plate 3 Reference porous plate perforated plate 4 Porous plate 5 Multiwell plate 6 Multiwell plate 7 Gap (mm) 2 5 7 10 15 20 Outlet gas temperature (°c) 1171 1175 1177 1178 1177 1176 Heat transfer amount (kcal/ h) 8110 8760 9050 9220 9190 9020 Ratio of heat transfer to reference porous plate (%) 92.5 100.0 103.3 105.2 104.9 102.9 This result is also shown in the form of a graph in Figure 3. As can be seen from the results, the most suitable enthalpy of the gap of the perforated plate is 10 mm, at which time the amount of heat transfer becomes maximum. Thereby, the heat transfer amount is increased by 5% due to an increase in the heat transfer coefficient and the amount of heat transfer from the outer surface of the reaction vessel. Example 3 <Effect of the pore diameter and the number of pores of the perforated plate on the amount of heat transfer> -22- 201038479 The same reaction apparatus and operating conditions as those described in Example 1 were used instead of the porous plate used, and the pore diameter was verified. The effect of the number of pairs of porous plates on the setting effect. Three kinds of perforated plates having changed pore diameter, number of holes, and opening ratio were produced. First, the first porous plate-based reference porous plate has a pore diameter of 15 π ιηηφ, a number of pores of 504, and an open cell ratio of 20.7%. The second porous plate (porous plate 8) has a pore diameter of 15 π ιηηφ, a number of pores of 1,024, and an open cell ratio of 42.1%. The third porous plate (porous plate 9) has a pore diameter of 10·5 ηιηηφ, a number of 孑L of 1024, and an opening ratio of 20.7%.各 Each of the perforated plates is placed in the inside of the cylindrical body in the reaction vessel with a space therebetween. In this state, the formation reaction of chlorosilane is carried out, and each temperature measurement point such as the inlet gas temperature and the outlet gas temperature is measured during the reaction. At the temperature, the amount of heat transfer in the entire reaction vessel was calculated. The results obtained are shown in Table 3. [Table 3] Multiwell plate 1 Reference porous plate perforated plate 2 Perforated plate thickness (Him) 20 40 60 Transmission area (m2) 2.33 3.08 3.83 Outlet gas temperature (°C) 1173 1175 1178 Heat transfer amount (kcal/h) 8390 8760 9100 The amount of heat transfer per area (kcal/m2-h) 3602 2845 2377 The ratio of heat transfer to the reference porous plate (%) 95.8 100 103.9 As can be seen from this result, simply increasing the number of holes in the perforated plate does not increase the number of passes. Heat. I believe this is because the flow rate is reduced and the heat transfer coefficient is reduced. However, when the opening ratio is 20.7%, the diameter of the hole portion is reduced, and the number of holes is increased by -23-201038479, the heat transfer amount is increased (in the example of the table, the heat transfer amount is increased [Simplified description] First BRIEF DESCRIPTION OF THE DRAWINGS Fig. 2 is a diagram for explaining a heat transfer procedure of a flow in a reaction apparatus of Fig. 1, and Fig. 2(a) shows radiation transmission by a heater. Heat, Fig. 2(b) shows the reaction vessel wall, Fig. 2(c) shows the convergence of the porous plate facing the inside of the reaction vessel. Fig. 2(d) shows the gas enthalpy from the inner surface of the reaction vessel and the perforated plate. Fig. 3 is a graph showing the results of Example 1. Fig. 4 is a graph showing the results of Example 2. [Explanation of main component symbols] • 9%) 0 Intentional profile heat exchanger for gas m reaction capacity Conduction heat transfer and heat transfer, convection heat transfer 10 Gas phase reaction device 11 Storage container 11a Body portion lib Top cover portion 11c Base plate portion lid Support member lie, 1 1 f Through hole 12 Reaction container 12a Flow inlet 12b Flow outlet 13 Heater (heating means) 24-201038479
13a 發熱體 13b 電極 14 急冷培·（急冷裝置） 15 外筒容器 16a、 16b 絕熱磚層，絕熱材層（絕熱層） 17 圓筒體（筒狀體） 18 底板構件（底部） 19 頂蓋構件（頂板部） 20 流入管 2 1 抽出管 22 塔本體 23 噴霧裝置 24 反應生成氣體導入管 25 多孔板（傳熱構件） 25a 孔部 26 間隔構件 -25-13a Heating element 13b Electrode 14 Quenching culture (quick cooling device) 15 Outer tube container 16a, 16b Insulating brick layer, insulation layer (insulation layer) 17 Cylindrical body (cylindrical body) 18 Base plate member (bottom) 19 Top cover member (top plate portion) 20 Inflow pipe 2 1 Extraction pipe 22 Tower body 23 Spray device 24 Reaction to generate gas introduction pipe 25 Perforated plate (heat transfer member) 25a Hole portion 26 Spacer member - 25 -