200906720 九、發明說明 【發明所屬之技術領域】 本發明有關一種以天然氣、丙烷氣體、汽油、石油腦 '燈油'甲醇、生質氣體等之碳化氫系化合物氣體與水以 及氧系氣體作爲原料，而產生一氧化碳氣體之產生一氧化 碳氣體之裝置及方法以及產生滲碳處理用氛圍氣體之產生 滲碳用氛圍氣體之裝置與方法。 【先前技術】 以往，滲碳處理等之金屬表面處理之氛圍氣體或作爲 聚胺基甲酸酯.聚碳酸酯等之製造原料中，一氧化碳氣體 爲必要。 此種一氧化碳氣體，以往係使用碳化氫氣體與氧氣體 作爲原料，利用觸媒並經改質反應而以富含氫氣且一氧化 碳氣體濃度高的混合氣體產生一氧化碳氣體，由此混合氣 體’藉 PSA( Pressure Swing Adsorption:壓力擺動吸附 )法等之方法，藉由分離一氧化碳氣體而獲得（例如下述 專利文獻1及2 )。 又，一般，於氣體滲碳處理中，於滲碳爐內裝入被處 理材料，導入以CO氣體作爲主之氛圍氣體，藉由加熱至 9 3 0〜9 7 0 °C左右而進行。此種滲碳用氛圍氣體，以往是使 碳化氫氣體（丁烷氣體或丙烷氣體）與空氣混合並導入轉 化爐內，利用鎳觸媒進行轉化反應所得之轉化氣體而使用 。如此之一般轉化氣體組成爲C0約20%、H2約40%、N2 200906720 約40%，由於使用空氣作爲原料，故碳電位（ potential )並非如此高，因此有必要一邊進行丙烷 富含氣體之供給並控制氛圍氣一邊進行滲碳。 作爲提高碳勢之滲碳用氣體之製造方法，提案 碳化氫氣體、氧氣體、二氧化碳氣體作爲原料氣體 觸媒引起轉化反應之方法（例如下述專利文獻3 ) 提案有使用碳化氫氣體及氧氣體作爲原料氣體使用 引起轉化反應之方法（例如下列專利文獻4 )。 專利文獻1:特開平11-137942號公報 專利文獻2 :特開2 0 0 1 - 3 3 5 3 0 5號公報 專利文獻3 :特開200 1 - 1 5 23 1 3號公報 專利文獻4 :特開2006-022357號公報 【發明內容】 [發明待解決之課題] 然而，使用碳化氫氣體及氧氣體作爲原料氣體 觸媒加以改質而以富含氫氣且一氧化碳氣體濃度高 氣體產生一氧化碳氣體之方法，若使系統全體之碳 並提高一氧化碳氣體之收率，於反應器的下游析出 包含用以回收在反應器所發生之熱所設之熱交換器 裝置內部因碳析出而受污染之問題。爲此，有必要 一氧化碳收率而不析出碳之條件下運轉或定期地進 碳之維護而運轉。 又，上述專利文獻3之轉化氣體發生裝置，由 carbon 氣體等 有使用 使用鎳 。又， 鈾觸媒 ，利用 的混合 勢提高 碳，而 ，而有 以犧牲 行除去 於設有 -6- 200906720 氧氣導入部及氧氣噴出部而自2系統導入管路導入氧氣， 而有轉化爐本身之構造複雜化之問題。又，由於氧氣自2 系統導入管路導入’故易發生爐內氧濃度凌亂，亦有容易 發生煤或引起觸媒劣化等問題。再者，由於使用二氧化碳 作爲原料’亦有原料成本變高的問題。而且，由於轉化反 應爲吸熱反應，故通常有必要自外部加熱，而有能量成本 亦高的問題。 又’上述專利文獻4之轉化氣體發生裝置，雖然使用 碳化氫氣體及氧氣體作爲原料氣體意圖減低原料成本，但 由於原料氣體之著火（回火）可能性高，爲能夠防止此而 進行設置複數個反應管並因應必要而開關通路，使流速保 持在特定範圍之辦法。然而，裝置本身大幅複雜化，而且 碳化氫與純氧之轉化依然有著火（回火）的可能性。而且 ’反應塔內變成非常高溫亦會引起觸媒或裝置本身過早劣 化。再者，亦有因煤的發生而使裝置閉塞之問題。 本發明係爲解決上述問題而進行者，目的在於提供一 種可使一氧化碳氣體吸收率高且可在減低維護下運轉之產 生一氧化碳氣體之裝置及方法，以及提供一種可以低成本 安全地產生碳勢高之滲碳氣體之產生滲碳用氛圍氣體之裝 置及方法。 [用以解決問題之手段] 爲達上述目的，本發明第一發明之產生一氧化碳氣體 之裝置係具備產生一氧化碳氣體之反應器，該反應器係導 200906720 入碳化氫系氣體與氧系氣體及水蒸氣作爲原料氣體，藉由 使上述原料氣體與觸媒進行催化反應而發生碳化氫系氣體 之燃燒反應以及轉化反應，而使作爲富含氫氣且一氧化碳 氣體濃度高的混合氣體產生一氧化碳氣體，其中以於上述 反應器下游導入含有以H2o爲主之流體爲要旨。 又，爲達上述目的，本發明第一發明之產生一氧化碳 氣體之方法係進行導入碳化氫系氣體與氧系氣體及水蒸氣 作爲原料氣體，藉由使上述原料氣體與觸媒進行催化反應 而發生碳化氫系氣體之燃燒反應以及轉化反應，而使作爲 富含氫氣且一氧化碳氣體濃度高的混合氣體產生一氧化碳 氣體之反應步驟，其中以於上述反應步驟下游導入含有以 H20爲主之流體爲要旨。 爲達上述目的，本發明第二發明之產生一氧化碳氣體 之裝置係具備產生一氧化碳氣體之反應器，該反應器係導 入碳化氫系氣體與氧系氣體及水蒸氣作爲原料氣體，藉由 使上述原料氣體與觸媒進行催化反應而發生碳化氫系氣體 之燃燒反應以及轉化反應，而使作爲富含氫氣且一氧化碳 氣體濃度高的混合氣體產生一氧化碳氣體，其中以於上述 反應器下游導入含有以氫爲主之流體爲要旨。 又，爲達上述目的，本發明第二發明之產生一氧化碳 氣體之方法係進行導入碳化氫系氣體與氧系氣體及水蒸氣 作爲原料氣體，藉由使上述原料氣體與觸媒進行催化反應 而發生碳化氫氣體之燃燒反應以及轉化反應，而使作爲富 含氫氣且一氧化碳氣體濃度高的混合氣體產生一氧化碳氣 200906720 體之反應步驟，其中以於上述反應步驟下游導入含有以氫 爲主之流體爲要旨。 爲達上述目的，本發明之產生滲碳氛圍氣體之裝置係 以具備一反應器爲要旨，該反應器係導入碳化氫系氣體與 氧系氣體及水蒸氣作爲原料氣體，藉由使上述原料氣體與 觸媒進行催化反應而發生碳化氫系氣體之燃燒反應以及轉 化反應，而產生富含氫氣且一氧化碳氣體濃度高的滲碳用 氛圍氣體。 爲達上述目的，本發明之產生滲碳氛圍氣體之方法之 要旨係導入碳化氫系氣體與氧系氣體及水蒸氣作爲原料氣 體，藉由與觸媒進行催化反應而發生碳化氫系氣體之燃燒 反應以及轉化反應，而產生富含氫氣且一氧化碳氣體濃度 高的滲碳用氛圍氣體。 發明效果 本發明第一發明之產生一氧化碳之裝置及方法，藉由 在上述反應器或在反應步驟下游處導入含有以h2o爲主 之流體，可有效地防止碳在反應器下游之配管內部等之金 屬表面上析出。爲此，除了可在一氧化碳氣體之產生勢高 的條件下運轉之外，可大幅減低除去污染物質等之維護。 如此，由於在反應器或反應步驟下游處導入含有以h2o 爲主之流體可抑制碳之析出，故抑制導入反應器或反應步 驟中之水蒸氣量成爲可能，可大幅提高藉由反應器或反應 步驟所得之改質氣體之一氧化碳濃度，可大幅提高一氧化 -9- 200906720 碳收率。 本發明第一發明之產生一氧化碳之裝置 置回收在上述反應器之下游之反應器所發生 器’在上述反應器之出口與熱交換器入口之 h2〇爲主之流體時，爲回收反應器之熱而設 之熱交換器可有效地防止碳析出引起的污染 一氧化碳氣體之發生勢高的條件下運轉以外 低除去污染物質等之維護。 本發明第一發明之產生一氧化碳之裝置 入上述反應器之原料氣體之構成係以水蒸秦 碳化氫系氣體中之C的莫耳比H20/C成爲0 ’設定碳化氫系氣體與氧系氣體與水蒸氣之 產生之混合氣體中一氧化碳氣體濃度變闻。 器中產生高溫，故自反應器排出之混合氣體 用於原料之加熱或對導入反應器下游之含窄 之流體之加熱。 本發明第一發明之產生一氧化碳之裝置 入上述反應器之原料氣體構成爲以氧系氣體 化氫系氣體中之C的莫耳比〇2/C成爲0.3 之方式，設定碳化氫系氣體與氧系氣體與水 時，除了可防止因內部燃燒反應引起之過度 觸媒損傷以外，亦可適當維持所得混合氣體 本發明第一發明之產生一氧化碳之裝置 述反應器藉由使用經Rh改質之（Ni-Ce02) 及方法中，設 之熱的熱交換 間導入含有以 於反應器下游 ，除了可能以 ，亦可大幅減 及方法中’導 ,中之H20與 .5以下之方式 混合比時’所 又，由於反應 所得之熱可利 '以Η 2 Ο爲主 及方法中’導 中之〇2與碳 以上0.5以下 蒸氣之混合比 放熱' 可防止 之組成。 及方法中’上 -Pt觸媒，使 -10 - 200906720 碳化氫系氣體之燃燒反應與轉化反應在相同反應區域內同 時進行時，藉由使放熱反應之燃燒反應與吸熱反應之轉化 反應在相同反應區域內同時進行，由於可利用燃燒反應所 產生之熱能作爲轉化反應之熱源，故極具有能源效率。再 者，於該反應區域同時發生放熱反應及吸熱反應，故可引 起熱中和而可以熱平衡狀態進行運轉。因此，與例如於反 應器內設置單獨進行觸媒燃燒反應之區域的情況相比，頗 能抑制反應區域之溫度上升，反應器所用之耐熱材料之選 定或反應器本身之耐熱構造即使並非如此程度之高溫規格 亦足以使用，故亦可節省設備成本。又，朝觸媒層入口供 給之原料氣體溫度可降低，可抑制因碳化氫熱分解而產生 煤，亦可避免著火危險。 上述含有以H2 0爲主之流體可使用水或水蒸氣。 本發明第二發明之產生一氧化碳之裝置及方法，藉由 在上述反應器或在反應步驟下游處導入含有以氫爲主之氣 體，可有效地防止碳在反應器下游之配管內部等之金屬表 面上析出。爲此，除了可在一氧化碳氣體之產生勢高的條 件下運轉之外，可大幅減低除去污染物質等之維護。如此 ，由於在反應器或反應步驟下游處導入含有以氫爲主之氣 體可抑制碳之析出，故抑制導入反應器或反應步驟中之水 蒸氣量成爲可能，可大幅提高藉由反應器或反應步驟所得 之改質氣體之一氧化碳濃度，可大幅提高一氧化碳收率。 本發明第二發明之產生一氧化碳之裝置及方法中’設 置回收在上述反應器之下游之反應器所發生之熱的熱交換 -11 - 200906720 器，在上述反應器之出口與熱交換器入口之間導 氫爲主之氣體時，爲回收反應器之熱而設於反應 熱交換器可有效地防止碳析出引起的污染’除了 氧化碳氣體之發生勢高的條件下運轉以外，亦可 除去污染物質等之維護。 本發明第二發明之產生一氧化碳之裝置及方 入上述反應器之原料氣體之構成係以水蒸氣中之 碳化氫系氣體中之c的莫耳比H20/C成爲0.5以 ，設定碳化氫系氣體與氧系氣體與水蒸氣之混合 產生之混合氣體中一氧化碳氣體濃度變高。又， 器中產生高溫，故自反應器排出之混合氣體所得 用於原料之加熱。 本發明第二發明之產生一氧化碳之裝置及方 入上述反應器之原料氣體構成爲以氧系氣體中之 化氫系氣體中之C的莫耳比02/C成爲0.3以上 之方式，設定碳化氫系氣體與氧系氣體與水蒸氣 時，除了可防止因內部燃燒反應引起之過度放熱 觸媒損傷以外，亦可適當維持所得混合氣體之組 本發明第二發明之產生一氧化碳之裝置及方 述反應器藉由使用經Rh改質之（Ni-Ce〇2 ) -Pt 碳化氫系氣體之燃燒反應與轉化反應在相同反應 時進行時，藉由使放熱反應之燃燒反應與吸熱反 反應在相同反應區域內同時進行，由於可利用燃 產生之熱能作爲轉化反應之熱源，故極具有能源 入含有以 器下游之 可能以一 大幅減低 法中，導 H20 與 下之方式 比時，所 由於反應 之熱可利 法中，導 〇2與碳 0.5以下 之混合比 、可防止 成。 法中，上 觸媒，使 區域內同 應之轉化 燒反應所 效率。再 -12- 200906720 者’於該反應區域同時發生放熱反應及吸熱反應，故可引 起熱中和而可以熱平衡狀態進行運轉。因此，與例如於反 應器內設置單獨進行觸媒燃燒反應之區域的情況相比，頗 能抑制反應區域之溫度上升，反應器所用之耐熱材料之選 定或反應器本身之耐熱構造即使並非如此程度之高溫規格 亦足以使用，故亦可節省設備成本。又，朝觸媒層入口供 給之原料氣體溫度可降低，可抑制因碳化氫熱分解而產生 煤，亦可避免著火危險。 本發明之產生滲碳用氛圍氣體之裝置及方法，係使碳 化氫系氣體與氧系氣體及水蒸氣與觸媒進行催化反應而發 生碳化氫氣體之燃燒反應以及轉化反應，藉此產生富含氫 氣且一氧化碳氣體濃度高的滲碳用氛圍氣體。如此，由於 使用非空氣之氧系氣體作爲原料，故可獲得碳勢高的滲碳 用氛圍氣體。又，由於使用水蒸氣作爲原料，故與僅以碳 化氫氣體及氧作爲原料之裝置相比，可降低***界限而可 大幅提高安全性。而且，與氧自2系統之導入管路導入之 裝置相比，反應器構造本身亦得以簡化，起因於氧濃度凌 亂之煤發生或觸媒劣化亦得以大幅降低。再者，原料氣體 之成本亦便宜且經濟’可以低成本安全地產生碳勢高之滲 碳氣體。又，可獲得富含H2之氛圍氣體，可抑制滲碳處 理步驟中之未反應碳微粒。 本發明之產生滲碳用氛圍氣體之裝置及方法中，上述 原料氣體係以每次預先使碳化氫氣體與水蒸氣混合’於其 中與氧系氣體合流並導入反應器中之構成時，可縮短使可 -13- 200906720 燃性氣體之碳化氫系氣體與氧系氣體之混合氣體通過之流 路，於安全方面爲有利。 本發明之產生滲碳用氛圍氣體之裝置及方法中’上述 原料氣體係以每次預先使氧系氣體與水蒸氣混合’於其中 與碳化氫系氣體合流並導入反應器中之構成時，由於混合 有可燃性氣體之碳化氫氣體之混合氣體之氧濃度變低’故 ***界限更降低，於安全方面爲有利。 本發明之產生滲碳用氛圍氣體之裝置及方法中’上述 原料氣體構成爲以氧系氣體中之〇2與碳化氫系氣體中之 c的莫耳比02/C成爲0.3以上0.5以下之方式且水蒸氣中 之H20與碳化氫系氣體中之C之莫耳比H20/C成爲0.3 以下之方式，設定碳化氫系氣體與氧系氣體與水蒸氣之混 合比時，所生成之滲碳性氣體中之CO濃度變高，可獲得 碳勢高之氛圍氣體。 本發明之產生滲碳用氛圍氣體之裝置及方法中，上述 原料氣體之供給量以對應於碳化氫系氣體之供給量變動而 自動變動氧系氣體及水的供給量之方式控制時，經常獲得 大致一定C 0濃度之滲碳性氣體，使得滲碳性氣體之生成 量得以變動。 本發明之產生滲碳用氛圍氣體之裝置及方法中，上述 反應器藉由使用經Rh改質之（Ni-Ce02 ) -Pt觸媒，使碳 化氫系氣體之燃燒反應與轉化反應在相同反應區域內同時 進行時，藉由使放熱反應之燃燒反應與吸熱反應之轉化反 應在相同反應區域內同時進行，由於可利用燃燒反應所產 -14- 200906720 生之熱能作爲轉化反應之熱源，故極具有能源效率。再者 ，於該反應區域同時發生放熱反應及吸熱反應，故可引起 熱中和而可以熱平衡狀態進行運轉。因此，與例如於反應 器內設置單獨進行觸媒燃燒反應之區域的情況相比，頗能 抑制反應區域之溫度上升，反應器所用之耐熱材料之選定 或反應器本身之耐熱構造即使並非如此程度之高溫規格亦 足以使用，故亦可節省設備成本。又，可降低朝觸媒層入 口供給之原料氣體溫度，可抑制因碳化氫熱分解而產生煤 ，亦可避免著火危險。 本發明之產生滲碳用氛圍氣體之裝置及方法中，具備 使導入反應器之原料氣體預熱之預熱加熱器，上述預熱加 熱器將上述原料氣體向反應器供給的溫度控制爲 3 00〜45 0 °C時，經常可以效率良好地熱平衡狀態進行運轉 【實施方式】 接者’說明用以實施本發明之最佳形態。 圖1係顯示適用本發明第一發明之產生一氧化碳之裝 置及方法之產生一氧化碳氣體裝置100之一例之構成圖。 該產生一氧化碳裝置100具備產生一氧化碳氣體之反 應器5 1 ’該反應器係以碳化氫系氣體與氧系氣體及水蒸 氣作爲原料氣體，導入該原料氣體，藉由使上述原料氣體 與觸媒進行催化反應而發生碳化氫系氣體之燃燒反應以及 轉化反應，而以富含氫氣且一氧化碳氣體濃度高的混合氣 -15- 200906720 體產生一氧化碳氣體。 於上述反應器5 1，自碳化氫供給管路5 6供給之碳化 氫氣體與自水蒸氣供給管路63供給之水蒸氣加以混合， 並於該混合之氣體供給之混合氣體流路64中與氧供給管 路5 9合流，進而作爲混合有氧氣體之原料氣體自原料氣 體供給管路65導入反應器5 1中。 於上述反應器51反應所生成之富含氫氣且一氧化碳 濃度高之混合氣體的改質氣體，自改質氣體管路72導出 ，經過氣液分離機71，經過第一 PSA裝置73、第二PSA 裝置74，以一氧化碳氣體及氫氣體排出作爲產物氣體。 於上述改質氣體管路72，設有第一熱交換器76、第 二熱交換器77、第三熱交換器78，使得改質氣體之熱被 回收並利用於原料之預熱，並使改質氣體冷卻。 上述碳化氫系氣體自未圖示之高壓筒或導管供給，以 壓縮機5 2壓縮成特定壓力，以流量調節閥5 4調整爲特定 流量，以第一熱交換器76與改質氣體進行熱交換並預熱 ，以碳化氫預熱加熱器5 5預熱至特定溫度爲止，於脫硫 器5 3進行脫硫後以碳化氫供給管路5 6供給。上述脫硫器 5 3亦可採用進行氫化脫硫者，亦可採用充塡有活性碳或 沸石等之吸附劑進行常溫吸附脫硫者。 上述碳化氫系氣體一般以丙烷或作爲都市天然氣等之 社會基礎建設而供給之碳化氫系氣體爲首，可使用例如天 然氣、丁烷氣體、甲烷氣體等之碳化氫系氣體。此例係以 使用天然氣爲例加以說明。 -16- 200906720 上述氧系氣體自未圖示之氧冷蒸發器等供給，以流量 調節閥5 8調整至特定流量並由氧供給管路5 9供給。 至於上述氧系氣體，可適當使用工業用純氧，但若氧 氣濃度係高如2 1 %以上者，則亦可使用多少混入不純物或 其他氣體者作爲氧系氣體。 上述水蒸氣，係以泵60供給純水，以第二熱交換器 77與改質氣體進行熱交換加以預熱，進而以純水加熱器 5 7及蒸氣加熱器62加熱成爲水蒸氣者，以流量調節閥6 1 調整爲特定流量並以水蒸氣供給管路63供給。 上述水蒸氣供給管路63、碳化氫供給管路56及氧供 給管路5 9，首先設有使上述水蒸氣供給管路63與碳化氫 供給管路5 6合流之混合氣體流路64，並設有使該混合氣 體流路64與氧供給管路59合流之原料氣體供給管路65 。藉此，構成爲上述原料氣體每次首先使碳化氫氣體與水 蒸氣混合，於其中合流氧系氣體並導入反應器5 1中。 於混合氣體流路64，設置使碳化氫氣系氣體與水蒸 氣之混合氣體預熱至特定溫度爲止之預熱加熱器66。因 此，將對於以上述預熱加熱器66預熱至特定溫度爲止之 混合氣體添加氧系氣體而成之原料氣體導入反應器5 1中 〇 又，構成爲使上述原料氣體每次預先使氧系氣體與水 蒸氣混合，於其中合流碳化氫系氣體並導入反應器5 1中 。又，亦可構成爲氧系氣體及水蒸氣及碳化氫系氣體同時 合流並導入反應器51中。 -17- 200906720 關於上述原料氣體之碳化氫系氣體、氧系氣體、水蒸 氣之混合比，係以流量調節閥5 4、5 8、61，藉由分別調 整碳化氫系氣體、氧系氣體、水之流量而設定。 亦即’上述原料氣體構成爲以氧系氣體中之〇2與碳 化氫系氣體中之C的莫耳比〇2/c成爲0.3以上0.5以下 之方式且水蒸氣中之H20與碳化氫系氣體中之C之莫耳 比HaO/C成爲0.5以下之方式，設定碳化氫系氣體與氧系 氣體與水蒸氣之混合比。亦即，爲提高C 0收率有必要使 HaO充分低而爲與溫度關係之程度，故h2〇/C較好爲0.5 以下。又’ OWC若超過〇.5，則進入氫燃燒區域之溫度變 筒’故〇2/C較好爲〇.3以上ο·〗以下。又，水蒸氣中之 Ηα〇與碳化氫系氣體中之c之莫耳比HiO/C較好設定爲 〇.〇5以上0.3以下。 例如碳化氫氣體爲甲烷（CH4)時，甲烷中之C爲1 ’故藉下述式（1) (2)決定混合比。〇2/C爲0.3〜0.5即 爲相對於甲烷1莫耳〇2爲〇.3〜0.5莫耳之比混合， H2〇/C = 〇·5以下即爲相對於甲烷1莫耳HaO成爲0.5莫耳 以下而混合。 〇2/C = [02]/ ( ix[ch4] ) =0.3-0.5-----( 1) H2〇/C = [H2〇]/ ( ! x[CH4j ) ^0.5-----(2) [Ο 2 ] : 〇 2之莫耳數 [CH4] : CH4之莫耳數 [H2〇] : H2〇之莫耳數 同樣地’例如，碳化氫氣體爲丙烷（C3H8 )時，丙烷 -18- 200906720 中之C爲3，故藉下述式（3) (4)決定混合比。〇2/C爲 〜0.5即爲相對於丙烷1莫耳〇2爲0· 9〜丨.5莫耳之比混 合，H2〇/C = 0.5以下即爲相對於丙烷1莫耳H2〇成爲i·5 莫耳以下而混合。 〇2/C = [〇2]/ ( 3x[C3H8] ) =0.3-0.5-----( 3 ) H2〇/C = [H2〇]/ ( 3x[C3H8] ) ^〇·5-----(4) [〇 2 ] · Ο 2之莫耳數 [C3H8] : C3H8之莫耳數 [H2〇] : H20之莫耳數 又，此裝置具備流量控制機（未圖示）’該流量控制 機係檢測上述流量調節閥5 4中之碳化氫系氣體之流量變 動，並對應於碳化氫系氣體之供給量變動而保持上述混合 比率之方式，調節氧氣流量調節閥5 8及水流量調節閥6 1 ’且使氧系氣體及水之供給量自動變動之方式控制原料氣 體之供給量。 於上述反應器5 1中塡充經Rh改質之（Ni-Ce02 ) -Pt 觸媒。因此藉由使用上述經Rh改質之（Ni-Ce02) -Pt觸 媒’使碳化氫系氣體之燃燒反應與轉化反應在相同反應區 域內同時進行。 接著，上述反應器5 1具備有溫度控制器6 8，該溫度 控制器6 8係檢測上述原料氣體朝反應器51供給時之溫度 亦即入口側溫度，且使上述預熱加熱器66將原料氣體供 應溫度控制爲250〜450 °C。 又’上述反應器51中設有啓動加熱器69,其係在裝 -19- 200906720 置啓動時，使自未圖示之氮氣高壓筒所供給之氮氣流動同 時使塡充有觸媒之反應區域預熱。藉由上述啓動加熱器 69 ’裝置啓動時內部溫度加熱至原料氣體反應開始所必要 的200〜3 00°C左右爲止，同樣地以上述溫度控制器68加 以控制。 於上述反應器51，利用經Rh改質之（Ni-Ce02 ) -Pt 觸媒，使碳化氫之燃燒反應與轉化反應可在一個反應區域 內同時進行碳化氫之燃燒反應及轉化反應。 亦即，碳化氫之一部份完全燃燒使碳化氫轉變成CO 及H2o之燃燒反應、與藉由此燃燒反應所生成之co2及 H20分別進而與剩餘之碳化氫反應而轉化成H2及CO之 轉化反應，係在上述觸媒上進行，可使碳化氫轉變成h2o 及CO而進行改質。 例如，若以碳化氫爲甲烷之情況加以說明，其反應全 體以如下式（5 )般表示，但實際上如式（6 )〜（8 )，係 以燃燒反應所生成之C02及H20進而與CH4引起轉化反 應，而轉變爲CO與H2之逐步反應。 ch4 + 2〇2 + 4 CO + 8H2 ——( 5 ) ch4 + 2〇2今 C02 + 2H2〇 ……( 6) ch4 + C02 + 2 CO + 2H2 ——( 7 ) 2CH 4 + 2 H2 2 CO + 6H2 _____( 8 ) 上述ch4與02進行催化反應之際，可進而於系統中 供給C02或2H20。此情況下，與C02或2H20之供給量 相抵之〇2供給量可減少。 -20- 200906720 反應溫度可爲3 5 0〜900°C，尤其是宜爲400〜800°C左 右。CH4與02之燃燒反應爲放熱反應，CH4與H20之轉 化反應爲吸熱反應。如上述，裝置啓動時藉由使反應器 51內之反應區域預熱至200〜300 °C，且原料氣體之供給溫 度控制成爲250〜450 °C，藉此使燃燒反應與轉化反應成爲 熱平衡狀態隨後同時進行。又，反應溫度之不足部份亦可 施加外部加熱。又，反應壓力通常採用加壓條件（例如 0.3〜0.4 Μ P a )，但常壓條件亦可。 藉由上述燃燒反應與轉化反應之改質所得之改質氣體 組成，以使用天然氣作爲原料氣體之情況下，以乾重爲基 準大約爲 64%H2 + 26%C0 + 6%C02 + 4%CH4，其餘爲不純物 。上物反應器51之出口部份的改質氣體溫度約爲700〜800 °C左右。 上述經Rh改質之（N i - C e Ο 2 ) - Pt觸媒係例如藉由使 具有適當空隙率之氧化鋁載體表面上擔持Rh ’隨後擔持 Pt，進而同時擔持Ni及Ce02而獲得。其中’載體材質或 形狀之選擇、有無形成被覆物或其材質之選擇’可能有種 種變化。 R h之擔持係藉由含浸R h之水溶性鹽之水溶液後’使 乾燥、燒成、氫還原而進行。又’ Pt之擔持係藉由含浸 Pt之水溶性鹽之水溶液後’使乾燥、燒成、氫還原而進 行。N i及C e Ο 2之同時擔持係藉由含浸N i之水溶性鹽以 及C e之水溶性鹽之混合水溶液後’使乾燥、燒成、氫還 原而進行。 -21 - 200906720 藉由上述列示之順序’獲得成爲目的之經Rh改質之 (N i - C e 0 2 ) - P t觸媒。各成份之組成以重量比計，宜設定 爲 Rh : Ni : Ce02 : Pt= ( 0-05-0.5 ) ： ( 3.0-10.0 ):( 2.0-8.0) : ( 0.3 - 5.0 ) ’ 更好爲 Rh:Ni:Ce02:Pt=( 〇.1-0.4) : ( 4.0-9.0 ) : (2.0-5.0) : (0.3-3.0)。 又，上述中各階段之氫還原處理可省略’而在實際使 用時使觸媒在高溫氫還原後使用。在各階段進行氫還原處 理時，亦可進而在使用之際使觸媒在高溫氫還原後使用。 所以，本實施形態之產生一氧化碳裝置及方法，係在 水蒸氣供給管路63之蒸氣加熱器62更下游側形成份歧管 路，於上述反應器51或反應步驟下游設有導入含有以 H2〇爲主之流體作爲水蒸氣的水蒸氣導入管路67。藉此 ，成爲於自反應器51排出之高溫改質氣體中，導入以蒸 氣加熱器62所加熱之水蒸氣。於上述反應器51或反應步 驟下游所導入之水蒸氣流量，係藉由設於水蒸氣導入管路 67之流量調節閥70加以調節。 水蒸氣導入管路67合流於上述改質氣體管路72之合 流位置’配置於設在改質氣體管路72上之複數個熱交互 器76、77、78中最上游側之第一熱交換器76之入口與反 應器5 1之出口之間。 如上述所得之改質氣體亦即富含氫氣且一氧化碳濃度 高之混合氣體’以冷卻用之第三熱交換器78冷卻，以氣 液分離器71去除水分後’導入第一PSA裝置73中。 上述富含氫氣體且一氧化碳濃度高之混合氣體以第一 -22- 200906720200906720 IX. Description of the Invention [Technical Fields of the Invention] The present invention relates to a hydrocarbon-based compound gas such as natural gas, propane gas, gasoline, petroleum brain 'light oil' methanol, biomass gas, water, and oxygen gas as raw materials. An apparatus and method for generating carbon monoxide gas and a method and method for generating an atmosphere gas for carburizing using an atmosphere gas for carburizing treatment. [Prior Art] Conventionally, carbon monoxide gas is required as an atmosphere gas for metal surface treatment such as carburization treatment or as a raw material for production of polyurethane, polycarbonate, or the like. In the conventional carbon monoxide gas, a hydrocarbon gas and an oxygen gas are used as raw materials, and a carbon monoxide gas is generated by a mixed gas rich in hydrogen gas and having a high concentration of carbon monoxide gas by a catalyst, whereby the mixed gas 'borrows PSA ( A method such as a pressure swing adsorption method is obtained by separating carbon monoxide gas (for example, Patent Documents 1 and 2 below). Further, in the gas carburizing treatment, a material to be treated is placed in a carburizing furnace, and an atmosphere gas containing CO gas as a main gas is introduced and heated to about 930 to 990 °C. Such an atmosphere for carburizing is conventionally used in which a hydrocarbon gas (butane gas or propane gas) is mixed with air and introduced into a reformer, and a conversion gas obtained by a conversion reaction using a nickel catalyst is used. Such a general conversion gas composition is about 20% of C0, about 40% of H2, and about 40% of N2 200906720. Since air is used as a raw material, the carbon potential is not so high, so it is necessary to carry out the supply of propane rich gas. And control the atmosphere while performing carburizing. As a method for producing a carburizing gas for increasing the carbon potential, a method of causing a conversion reaction by using a hydrocarbon gas, an oxygen gas, or a carbon dioxide gas as a raw material gas catalyst (for example, Patent Document 3 below) proposes the use of a hydrocarbon gas and an oxygen gas. A method of causing a conversion reaction is used as a material gas (for example, Patent Document 4 below). Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. H11-137942 (Patent Document 2): JP-A-20001 - 3 3 5 3 0 5 Patent Publication 3: JP-A-200 1 - 1 5 23 1 3 Patent Document 4: JP-A-2006-022357 [Summary of the Invention] [Problems to be Solved by the Invention] However, hydrocarbon gas and oxygen gas are used as a raw material gas catalyst to be reformed, and carbon monoxide gas is generated by a gas rich in hydrogen and having a high concentration of carbon monoxide gas. In the method, if the carbon of the entire system is increased and the yield of carbon monoxide gas is increased, precipitation on the downstream side of the reactor contains a problem of recovering carbon due to carbon deposition in the heat exchanger device provided for the heat generated in the reactor. For this reason, it is necessary to operate under the conditions of carbon monoxide yield without precipitation of carbon or maintenance of regular carbon. Further, in the reformed gas generator of Patent Document 3, nickel is used for carbon gas or the like. In addition, the uranium catalyst uses a mixed potential to increase the carbon, and the sacrificial line is removed from the oxygen introduction portion and the oxygen ejecting portion provided with the -6-200906720, and the oxygen is introduced from the 2 system introduction line, and the reforming furnace itself is provided. The problem of structural complexity. Further, since oxygen is introduced from the introduction line of the system, the oxygen concentration in the furnace is liable to be disordered, and there is a problem that coal or the catalyst is likely to be deteriorated. Further, since carbon dioxide is used as a raw material, there is also a problem that the raw material cost becomes high. Moreover, since the conversion reaction is an endothermic reaction, it is usually necessary to heat from the outside, and there is a problem that the energy cost is also high. In the conversion gas generating device of the above-mentioned Patent Document 4, it is intended to reduce the raw material cost by using the hydrocarbon gas and the oxygen gas as the material gas. However, since the possibility of ignition (tempering) of the material gas is high, it is possible to prevent the occurrence of the plural. The reaction tubes are opened and closed as necessary to maintain the flow rate in a specific range. However, the device itself is greatly complicated, and the conversion of hydrocarbon and pure oxygen still has the possibility of fire (tempering). Moreover, the fact that the inside of the reaction tower becomes very hot can cause premature deterioration of the catalyst or the device itself. Furthermore, there is also the problem of occluding the device due to the occurrence of coal. The present invention has been made to solve the above problems, and an object thereof is to provide an apparatus and method for generating carbon monoxide gas which can absorb carbon monoxide gas and which can be operated under reduced maintenance, and to provide a carbon potential which can be safely produced at low cost. An apparatus and method for producing an atmosphere gas for carburizing of a carburizing gas. [Means for Solving the Problem] In order to achieve the above object, the apparatus for producing carbon monoxide gas according to the first invention of the present invention is provided with a reactor for generating carbon monoxide gas, which is a catalyst for directing hydrocarbon gas and oxygen gas and water. The vapor is used as a raw material gas to cause a combustion reaction and a conversion reaction of a hydrocarbon-based gas by catalytically reacting the raw material gas with a catalyst, thereby generating carbon monoxide gas as a mixed gas rich in hydrogen gas and having a high concentration of carbon monoxide gas. It is the intention to introduce a fluid containing H2o mainly downstream of the above reactor. Further, in order to achieve the above object, the method for producing carbon monoxide gas according to the first aspect of the present invention is to introduce a hydrocarbon gas, an oxygen gas, and steam as a material gas, and to cause a catalytic reaction between the material gas and the catalyst. In the combustion reaction and the conversion reaction of the hydrocarbon-based gas, a reaction step of generating a carbon monoxide gas as a mixed gas rich in hydrogen and having a high concentration of carbon monoxide gas is carried out, and a flow containing a H20-based fluid is introduced downstream of the reaction step. In order to achieve the above object, the apparatus for producing carbon monoxide gas according to the second aspect of the present invention includes a reactor for generating carbon monoxide gas, wherein the reactor introduces a hydrocarbon-based gas, an oxygen-based gas, and steam as a material gas, by using the raw material. The gas and the catalyst are catalytically reacted to generate a combustion reaction and a conversion reaction of the hydrocarbon-based gas, and a carbon monoxide gas is generated as a mixed gas rich in hydrogen and having a high concentration of carbon monoxide gas, wherein the introduction of hydrogen in the downstream of the reactor is performed. The main fluid is the essence. Further, in order to achieve the above object, the method for producing carbon monoxide gas according to the second aspect of the present invention is to introduce a hydrocarbon gas, an oxygen gas, and steam as a material gas, and to cause a catalytic reaction between the material gas and the catalyst. a combustion reaction of a hydrocarbon gas and a conversion reaction, and a reaction step of generating a carbon monoxide gas 200906720 as a mixed gas rich in hydrogen and having a high concentration of carbon monoxide gas, wherein the introduction of a hydrogen-containing fluid downstream of the reaction step is . In order to achieve the above object, the apparatus for producing a carburizing atmosphere according to the present invention is characterized in that a reactor having a hydrocarbon gas, an oxygen-based gas, and steam as a material gas is introduced, and the raw material gas is used. The catalytic reaction with the catalyst generates a combustion reaction and a conversion reaction of the hydrocarbon-based gas, and an atmospheric gas for carburizing rich in hydrogen gas and having a high concentration of carbon monoxide gas is generated. In order to achieve the above object, the method for producing a carburizing atmosphere according to the present invention is to introduce a hydrocarbon gas, an oxygen gas, and a water vapor as a material gas, and to cause combustion of a hydrocarbon gas by catalytic reaction with a catalyst. The reaction and the conversion reaction generate an atmosphere for carburizing rich in hydrogen gas and having a high concentration of carbon monoxide gas. Advantageous Effects of Invention The apparatus and method for producing carbon monoxide according to the first aspect of the present invention can effectively prevent carbon from being inside the piping downstream of the reactor by introducing a fluid containing h2o as a main stream in the reactor or downstream of the reaction step. Precipitated on the metal surface. For this reason, in addition to the operation of the carbon monoxide gas, the maintenance of the removal of pollutants and the like can be greatly reduced. In this way, since introduction of a fluid containing h2o-based fluid downstream of the reactor or the reaction step can suppress precipitation of carbon, it is possible to suppress the amount of water vapor introduced into the reactor or the reaction step, and the reactor or reaction can be greatly improved. The carbon oxide concentration of one of the modified gases obtained in the step can greatly increase the carbon yield of -9-200906720. The apparatus for producing carbon monoxide according to the first invention of the present invention is configured to recover the reactor of the reactor downstream of the reactor, which is the main fluid of the reactor at the outlet of the reactor and the inlet of the heat exchanger. The heat exchanger provided by the heat can effectively prevent the contamination caused by the carbon deposition, and the maintenance of the low-concentration removal of the pollutants and the like under the condition that the carbon monoxide gas has a high potential. The apparatus for producing carbon monoxide according to the first aspect of the present invention is configured such that the composition of the raw material gas in the reactor is such that the molar ratio H20/C of C in the water-hydrogenated Qin hydrocarbon-based gas becomes 0', and the hydrocarbon-based gas and the oxygen-based gas are set. The concentration of carbon monoxide gas in the mixed gas generated with water vapor is changed. The high temperature is generated in the reactor, so that the mixed gas discharged from the reactor is used for heating the raw material or for heating the narrow fluid introduced downstream of the reactor. In the apparatus for generating carbon monoxide according to the first aspect of the present invention, the raw material gas in the reactor is configured such that the molar ratio C2/C of C in the oxygen-based gaseous hydrogen-based gas is 0.3, and the hydrocarbon-based gas and oxygen are set. In the case of gas and water, in addition to preventing excessive catalyst damage due to internal combustion reaction, the resulting mixed gas may be appropriately maintained. The apparatus for producing carbon monoxide according to the first invention of the present invention is modified by using Rh ( In the method of Ni-Ce02) and the method, the heat exchange between the heat exchangers is included in the downstream of the reactor, and may be substantially reduced in the mixing ratio of the H20 and .5 or less in the method. Moreover, the composition of the heat obtained by the reaction is mainly composed of Η 2 Ο and the mixture of the 导 2 in the method and the mixing ratio of the vapor of 0.5 or less to 0.5 or less. And the method of 'up-Pt catalyst, so that the combustion reaction of the hydrocarbon gas and the conversion reaction are simultaneously performed in the same reaction zone when the conversion reaction of the exothermic reaction and the endothermic reaction are the same Simultaneously in the reaction zone, since the heat energy generated by the combustion reaction can be utilized as a heat source for the conversion reaction, it is extremely energy efficient. Further, an exothermic reaction and an endothermic reaction occur simultaneously in the reaction zone, so that heat neutralization can be caused and the operation can be performed in a state of thermal equilibrium. Therefore, compared with the case where, for example, a region in which a catalyst combustion reaction is separately carried out in the reactor is provided, the temperature rise of the reaction zone can be suppressed, the selection of the heat resistant material used in the reactor or the heat resistant structure of the reactor itself is not so. The high temperature specifications are also sufficient to save equipment costs. Further, the temperature of the material gas supplied to the inlet of the catalyst layer can be lowered, and the generation of coal due to thermal decomposition of hydrocarbons can be suppressed, and the risk of fire can be avoided. Water or steam may be used as the above-mentioned fluid containing H2 0 as a main fluid. The apparatus and method for producing carbon monoxide according to the second invention of the present invention can effectively prevent the metal surface of the inside of the piping downstream of the reactor by introducing a gas containing hydrogen in the reactor or downstream of the reaction step. Precipitated. For this reason, in addition to the operation of the carbon monoxide gas, the maintenance of the removal of pollutants and the like can be greatly reduced. In this way, since introduction of a hydrogen-containing gas downstream of the reactor or the reaction step suppresses precipitation of carbon, it is possible to suppress the amount of water vapor introduced into the reactor or the reaction step, and the reactor or reaction can be greatly improved. The carbon monoxide concentration of one of the modified gases obtained in the step can greatly increase the carbon monoxide yield. In the apparatus and method for producing carbon monoxide according to the second invention of the present invention, 'the heat exchange of the heat generated in the reactor downstream of the reactor is set to be -11, 200906720, at the outlet of the reactor and the inlet of the heat exchanger When a hydrogen-conducting gas is used, the heat of the reactor is recovered in the reaction heat exchanger to effectively prevent the contamination caused by carbon deposition. In addition to the operation of the carbon oxide gas, the contamination can be removed. Maintenance of substances, etc. The apparatus for generating carbon monoxide according to the second aspect of the present invention and the raw material gas which is introduced into the reactor are configured such that the molar ratio H20/C of c in the hydrocarbon-based gas in the water vapor is 0.5 to set the hydrocarbon-based gas. The concentration of carbon monoxide gas in the mixed gas produced by mixing with the oxygen gas and the water vapor becomes high. Further, a high temperature is generated in the apparatus, so that the mixed gas discharged from the reactor is used for heating the raw material. The apparatus for generating carbon monoxide according to the second aspect of the present invention and the raw material gas to be introduced into the reactor are configured such that the molar ratio 02/C of C in the hydrogen-based gas in the oxygen-based gas is 0.3 or more, and the hydrocarbon is set. In the case of a gas, an oxygen-based gas, and a water vapor, in addition to preventing excessive exothermic catalyst damage due to internal combustion reaction, the group of the obtained mixed gas can be appropriately maintained, and the apparatus for generating carbon monoxide according to the second invention of the present invention and the reaction are described. By using the Rh-modified (Ni-Ce〇2)-Pt hydrocarbon gas, the combustion reaction and the conversion reaction are carried out in the same reaction, by the exothermic reaction, the combustion reaction and the endothermic reaction are in the same reaction. Simultaneously in the region, since the heat energy generated by the combustion can be used as the heat source for the conversion reaction, it is possible to have a heat source into the downstream of the device, and the heat of the reaction may be caused by a large reduction in the ratio of H20 to the next. In the Kelly method, the mixing ratio of the crucible 2 to the carbon of 0.5 or less can be prevented. In the law, the upper catalyst is used to make the conversion reaction in the region more efficient. Further, in the reaction zone, an exothermic reaction and an endothermic reaction occur simultaneously, so that heat neutralization can be caused and the operation can be performed in a state of thermal equilibrium. Therefore, compared with the case where, for example, a region in which a catalyst combustion reaction is separately carried out in the reactor is provided, the temperature rise of the reaction zone can be suppressed, the selection of the heat resistant material used in the reactor or the heat resistant structure of the reactor itself is not so. The high temperature specifications are also sufficient to save equipment costs. Further, the temperature of the material gas supplied to the inlet of the catalyst layer can be lowered, and the generation of coal due to thermal decomposition of hydrocarbons can be suppressed, and the risk of fire can be avoided. An apparatus and method for producing an atmosphere gas for carburizing according to the present invention, wherein a hydrocarbon-based gas and an oxygen-based gas and water vapor are catalytically reacted with a catalyst to generate a combustion reaction and a conversion reaction of a hydrocarbon gas, thereby generating an enrichment An atmospheric gas for carburizing of hydrogen and a high concentration of carbon monoxide gas. As described above, since a non-air oxygen-based gas is used as a raw material, an atmosphere gas for carburizing having a high carbon potential can be obtained. Further, since water vapor is used as a raw material, the explosion limit can be reduced and the safety can be greatly improved as compared with a device using only hydrogen carbide gas and oxygen as a raw material. Further, the reactor structure itself is simplified as compared with the apparatus in which oxygen is introduced from the introduction line of the system, and coal generation due to disordered oxygen concentration or catalyst deterioration is also greatly reduced. Further, the cost of the material gas is also inexpensive and economical, and the carbon gas having a high carbon potential can be safely produced at a low cost. Further, an atmosphere gas rich in H2 can be obtained, and unreacted carbon particles in the carburization treatment step can be suppressed. In the apparatus and method for producing an atmosphere gas for carburizing according to the present invention, the raw material gas system can be shortened by mixing the hydrocarbon gas and the steam in advance, and mixing the oxygen gas into the reactor. It is advantageous in terms of safety to pass a flow path through which a mixed gas of a hydrocarbon gas of a flammable gas and an oxygen-based gas can pass. In the apparatus and method for producing an atmosphere gas for carburizing according to the present invention, the above-mentioned raw material gas system is configured such that the oxygen-based gas and the steam are mixed in advance each time, and the hydrocarbon-based gas is combined and introduced into the reactor. The oxygen concentration of the mixed gas of the hydrocarbon gas in which the combustible gas is mixed becomes low, so that the explosion limit is further lowered, which is advantageous in terms of safety. In the apparatus and method for producing an atmosphere gas for carburizing according to the present invention, the raw material gas is configured such that the molar ratio 02/C of c in the oxygen-based gas and the hydrocarbon-based gas is 0.3 or more and 0.5 or less. Further, when the mixing ratio of the hydrocarbon gas to the oxygen gas to the water vapor is set to be equal to or lower than the molar ratio H20 of the H20 in the hydrogen gas to the gas content of H20/C in the hydrocarbon gas, the carburization property is formed. The concentration of CO in the gas becomes high, and an atmosphere gas having a high carbon potential can be obtained. In the apparatus and method for producing an atmosphere gas for carburizing according to the present invention, the supply amount of the source gas is often controlled so as to automatically change the supply amount of the oxygen-based gas and water in accordance with the fluctuation in the supply amount of the hydrocarbon-based gas. The carburizing gas having a substantially constant C 0 concentration causes the amount of carburizing gas to be generated to vary. In the apparatus and method for producing an atmosphere gas for carburizing according to the present invention, the reactor is subjected to the same reaction by a combustion reaction of a hydrocarbon-based gas and a conversion reaction by using a Rh-modified (Ni-Ce02)-Pt catalyst. When the zones are simultaneously carried out, the conversion reaction between the combustion reaction and the endothermic reaction of the exothermic reaction is simultaneously carried out in the same reaction zone, and since the heat energy produced by the combustion reaction can be used as a heat source for the conversion reaction, Energy efficient. Further, an exothermic reaction and an endothermic reaction occur simultaneously in the reaction zone, so that heat neutralization can be caused and the operation can be performed in a state of thermal equilibrium. Therefore, compared with the case where, for example, a region in which a catalyst combustion reaction is separately carried out in the reactor is provided, the temperature rise of the reaction zone can be suppressed, the selection of the heat resistant material used in the reactor or the heat resistant structure of the reactor itself is not so. The high temperature specifications are also sufficient to save equipment costs. Further, the temperature of the material gas supplied to the inlet of the catalyst layer can be lowered, and coal can be prevented from being thermally decomposed by the decomposition of the hydrocarbon, and the risk of fire can be avoided. The apparatus and method for producing an atmosphere gas for carburizing according to the present invention include a preheating heater that preheats a material gas introduced into the reactor, and the preheating heater controls a temperature at which the raw material gas is supplied to the reactor to 300 00. When it is ~45 0 °C, it is often possible to operate in an efficient thermal equilibrium state. [Embodiment] The best mode for carrying out the invention will be described. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the configuration of an example of a carbon monoxide generating gas apparatus 100 which is applied to a device and method for producing carbon monoxide according to a first invention of the present invention. The carbon monoxide generating apparatus 100 includes a reactor 5 1 for generating carbon monoxide gas. The reactor uses a hydrocarbon-based gas, an oxygen-based gas, and steam as a raw material gas, and introduces the raw material gas by the raw material gas and the catalyst. The combustion reaction and the conversion reaction of the hydrocarbon-based gas occur in the catalytic reaction, and the carbon monoxide gas is produced in the mixture of the hydrogen-rich and carbon monoxide gas-rich gas mixture -15-200906720. The hydrocarbon gas supplied from the hydrocarbon supply line 56 in the reactor 5 1 is mixed with the water vapor supplied from the steam supply line 63, and is mixed with the mixed gas supply mixed gas passage 64. The oxygen supply line 59 is merged, and further, as a material gas for mixing the aerobic gas, is introduced into the reactor 51 from the material gas supply line 65. The reformed gas of the mixed gas rich in hydrogen and having a high concentration of carbon monoxide generated by the reaction of the reactor 51 is led out from the reformed gas line 72, passes through the gas-liquid separator 71, passes through the first PSA unit 73, and the second PSA. The device 74 is discharged as a product gas with carbon monoxide gas and hydrogen gas. The modified gas line 72 is provided with a first heat exchanger 76, a second heat exchanger 77, and a third heat exchanger 78, so that the heat of the reformed gas is recovered and utilized for preheating of the raw materials, and The reformed gas is cooled. The hydrocarbon-based gas is supplied from a high-pressure cylinder or a pipe (not shown), compressed to a specific pressure by the compressor 52, adjusted to a specific flow rate by the flow rate adjusting valve 54, and heated by the first heat exchanger 76 and the reformed gas. The carbon dioxide preheating heater 55 is preheated to a specific temperature, and is desulfurized by the desulfurizer 53 to be supplied to the hydrocarbon supply line 56. The above-mentioned desulfurizer 5 3 may also be used for hydrodesulfurization, or may be adsorbed by activated carbon or zeolite to conduct desulfurization at room temperature. The hydrocarbon-based gas is generally a propene gas or a hydrocarbon-based gas supplied as a social infrastructure such as urban natural gas, and a hydrocarbon-based gas such as natural gas, butane gas or methane gas can be used. This example is illustrated by the use of natural gas. -16-200906720 The oxygen-based gas is supplied from an oxygen-cooled evaporator or the like (not shown), and is adjusted to a specific flow rate by the flow rate adjusting valve 58 and supplied from the oxygen supply line 59. As the oxygen-based gas, industrial pure oxygen can be suitably used. However, if the oxygen concentration is as high as 21% or more, it is also possible to use an oxygen-based gas as much as possible in which impurities or other gases are mixed. The water vapor is supplied with pure water by the pump 60, and is preheated by heat exchange between the second heat exchanger 77 and the reformed gas, and further heated by the pure water heater 57 and the steam heater 62 to become steam. The flow rate adjusting valve 6 1 is adjusted to a specific flow rate and supplied by the water vapor supply line 63. The steam supply line 63, the hydrocarbon supply line 56, and the oxygen supply line 590 are first provided with a mixed gas flow path 64 that joins the water supply line 63 and the hydrocarbon supply line 56, and A material gas supply line 65 that allows the mixed gas flow path 64 to merge with the oxygen supply line 59 is provided. Thereby, the raw material gas is first mixed with water vapor each time, and the oxygen-based gas is combined and introduced into the reactor 51. In the mixed gas flow path 64, a preheating heater 66 for preheating the mixed gas of the carbonized hydrogen gas and the water vapor to a specific temperature is provided. Therefore, the raw material gas obtained by adding the oxygen-based gas to the mixed gas preheated to the specific temperature by the preheating heater 66 is introduced into the reactor 51, and the raw material gas is previously made oxygen-based. The gas is mixed with steam, and a hydrocarbon-based gas is merged therein and introduced into the reactor 51. Further, the oxygen-based gas, the water vapor, and the hydrocarbon-based gas may be simultaneously merged and introduced into the reactor 51. -17- 200906720 The mixing ratio of the hydrocarbon gas, the oxygen gas, and the water vapor of the raw material gas is adjusted by the flow rate adjusting valves 5 4, 5 8 and 61, respectively, by adjusting the hydrocarbon gas and the oxygen gas. Set by the flow of water. In other words, the raw material gas is configured such that the molar ratio C2/c of C in the oxygen-based gas and the hydrocarbon-based gas is 0.3 or more and 0.5 or less, and the H20 and hydrocarbon gas in the water vapor. In the case where the molar ratio of C to HaO/C is 0.5 or less, the mixing ratio of the hydrocarbon-based gas and the oxygen-based gas to the water vapor is set. That is, in order to increase the C 0 yield, it is necessary to make HaO sufficiently low to the extent of temperature, so h2 〇 / C is preferably 0.5 or less. Further, if the OWC exceeds 〇5, it enters the temperature change cylinder of the hydrogen combustion zone. Therefore, the 〇2/C is preferably 〇.3 or more. Further, the molar ratio HiO/C of Ηα〇 in water vapor and c in the hydrocarbon-based gas is preferably set to 〇.5 or more and 0.3 or less. For example, when the hydrocarbon gas is methane (CH4), C in methane is 1', and the mixing ratio is determined by the following formula (1) and (2). 〇2/C is 0.3~0.5, which is a ratio of 33 to 0.5 mol relative to methane 1 Mo〇2, and H2〇/C = 〇·5 or less is 0.5 relative to methane 1 MoH Mole is mixed below. 〇2/C = [02]/ ( ix[ch4] ) =0.3-0.5-----( 1) H2〇/C = [H2〇]/ ( ! x[CH4j ) ^0.5----- (2) [Ο 2 ] : Moir number of 〇2 [CH4] : Moir number of CH4 [H2〇] : The number of moles of H2〇 is similarly 'For example, when the hydrocarbon gas is propane (C3H8), propane C in the -18-200906720 is 3, so the mixing ratio is determined by the following formula (3) (4). 〇 2 / C is ~ 0.5 is the ratio of 0 · 9 ~ 丨. 5 molar relative to propane 1 Mo〇 2, H2 〇 / C = 0.5 or less is relative to propane 1 Mo H2 〇 become i · 5 moles mixed below. 〇2/C = [〇2]/ ( 3x[C3H8] ) =0.3-0.5-----( 3 ) H2〇/C = [H2〇]/ ( 3x[C3H8] ) ^〇·5-- ---(4) [〇2 ] · Ο 2 molars [C3H8] : C3H8 molars [H2〇] : H20 molars, this device has a flow control machine (not shown) The flow rate control device detects a flow rate fluctuation of the hydrocarbon-based gas in the flow rate adjusting valve (54), and adjusts the oxygen flow rate adjusting valve 58 and water in accordance with a change in the supply amount of the hydrocarbon-based gas while maintaining the mixing ratio. The flow rate adjusting valve 6 1 ' controls the supply amount of the material gas so that the supply amount of the oxygen-based gas and water is automatically changed. The Rh-modified (Ni-Ce02)-Pt catalyst was purged in the above reactor 51. Therefore, the combustion reaction of the hydrocarbon-based gas and the conversion reaction are simultaneously carried out in the same reaction zone by using the above-mentioned Rh-modified (Ni-Ce02)-Pt catalyst. Next, the reactor 5 1 is provided with a temperature controller 6 8 that detects the temperature at the time when the raw material gas is supplied to the reactor 51, that is, the inlet side temperature, and causes the preheating heater 66 to feed the raw material. The gas supply temperature is controlled to 250 to 450 °C. Further, the above-mentioned reactor 51 is provided with a starter heater 69 which, when the -19-200906720 is started, allows the nitrogen gas supplied from the nitrogen high pressure cylinder (not shown) to flow while the catalyst is filled with the catalyst reaction area. Preheat. When the starter heater 69' is activated, the internal temperature is heated to about 200 to 300 °C, which is necessary for the start of the reaction of the raw material gas, and is similarly controlled by the temperature controller 68. In the above reactor 51, the combustion reaction and the conversion reaction of the hydrocarbon are carried out by the Rh-modified (Ni-Ce02)-Pt catalyst to simultaneously carry out the combustion reaction and the conversion reaction of the hydrocarbon in one reaction zone. That is, one part of the hydrocarbon is completely burned to convert the hydrocarbon into a combustion reaction of CO and H2o, and the co2 and H20 formed by the combustion reaction are respectively converted into H2 and CO by reacting with the remaining hydrocarbon. The conversion reaction is carried out on the above-mentioned catalyst, and the hydrocarbon can be converted into h2o and CO to be reformed. For example, in the case where hydrocarbon is used as the methane, the reaction is generally represented by the following formula (5), but actually, the formulas (6) to (8) are formed by the combustion reaction to produce C02 and H20. CH4 causes a conversion reaction and is converted into a stepwise reaction of CO and H2. Ch4 + 2〇2 + 4 CO + 8H2 ——( 5 ) ch4 + 2〇2C02 + 2H2〇...( 6) ch4 + C02 + 2 CO + 2H2 ——( 7 ) 2CH 4 + 2 H2 2 CO + 6H2 _____( 8 ) When the above ch4 and 02 are subjected to a catalytic reaction, CO 2 or 2H 20 may be further supplied to the system. In this case, the supply amount of 〇2 which is offset by the supply amount of C02 or 2H20 can be reduced. -20- 200906720 The reaction temperature can be 3 5 0 to 900 ° C, especially about 400 to 800 ° C. The combustion reaction between CH4 and 02 is an exothermic reaction, and the conversion reaction between CH4 and H20 is an endothermic reaction. As described above, when the apparatus is started up, the reaction zone in the reactor 51 is preheated to 200 to 300 ° C, and the supply temperature of the raw material gas is controlled to 250 to 450 ° C, thereby making the combustion reaction and the conversion reaction into a thermal equilibrium state. Then proceed simultaneously. Further, external heating may be applied to the insufficient portion of the reaction temperature. Further, the reaction pressure is usually under a pressurized condition (for example, 0.3 to 0.4 Μ P a ), but it may be a normal pressure condition. In the case of using natural gas as a raw material gas by using the modified gas composition obtained by the above-mentioned combustion reaction and conversion reaction, it is about 64% H2 + 26% C0 + 6% C02 + 4% CH4 on a dry weight basis. The rest are not pure. The temperature of the reforming gas at the outlet portion of the upper reactor 51 is about 700 to 800 °C. The Rh-modified (N i -C e Ο 2 ) - Pt catalyst is supported by, for example, a substrate carrying an appropriate porosity to support Rh, and then supporting Ni and Ce02. And get. Among them, the choice of the material or shape of the carrier, the choice of whether or not to form the coating or the material thereof may vary. The support of R h is carried out by impregnating an aqueous solution of a water-soluble salt of Rh, followed by drying, firing, and hydrogen reduction. Further, the support of Pt is carried out by impregnating an aqueous solution of a water-soluble salt of Pt, followed by drying, firing, and hydrogen reduction. The simultaneous holding of N i and C e Ο 2 is carried out by impregnating a water-soluble salt of N i and a mixed aqueous solution of a water-soluble salt of C e, followed by drying, firing, and hydrogen reduction. -21 - 200906720 By the order listed above, the (N i - C e 0 2 ) - P t catalyst which is the target of Rh modification is obtained. The composition of each component should be set to Rh: Ni : Ce02 : Pt = ( 0-05-0.5 ) : ( 3.0-10.0 ): ( 2.0 - 8.0 ) : ( 0.3 - 5.0 ) ' More preferably Rh : Ni: Ce02: Pt = (〇.1-0.4) : (4.0-9.0) : (2.0-5.0) : (0.3-3.0). Further, the hydrogen reduction treatment in each of the above stages may be omitted, and the catalyst may be used after high-temperature hydrogen reduction in actual use. When the hydrogen reduction treatment is carried out at each stage, the catalyst can be further used after high-temperature hydrogen reduction at the time of use. Therefore, the carbon monoxide generating apparatus and method of the present embodiment form a portion-distributing line on the downstream side of the steam heater 62 of the steam supply line 63, and is provided with H2 in the downstream of the reactor 51 or the reaction step. The main fluid is introduced into the line 67 as steam of water vapor. Thereby, the water vapor heated by the steam heater 62 is introduced into the high-temperature reforming gas discharged from the reactor 51. The flow rate of water vapor introduced in the reactor 51 or the downstream of the reaction step is adjusted by a flow rate adjusting valve 70 provided in the steam introduction line 67. The water vapor introduction line 67 merges with the merged gas line 72 at the junction position 'the first heat exchange disposed on the most upstream side of the plurality of thermal exchangers 76, 77, 78 provided on the reformed gas line 72. The inlet of the vessel 76 is between the outlet of the reactor 51. The modified gas obtained as described above, i.e., the mixed gas having a high hydrogen monoxide and a high concentration of carbon monoxide, is cooled by the third heat exchanger 78 for cooling, and is removed by the gas-liquid separator 71, and then introduced into the first PSA unit 73. The above-mentioned mixed gas rich in hydrogen gas and having a high concentration of carbon monoxide is first -22-200906720
PSA裝置73去除H20' C02、CH4等之後，以第二PSA 裝置74分離爲製品一氧化碳及氫氣。 上述第一 PSA裝置73爲並列配置有複數根（例如此 例中爲4根）吸附塔7 9之構成。於上述各吸附塔7 9內部 ，充塡活性碳、分子篩、沸石等之吸附劑，以上述反應器 51生成之富含氫氣且一氧化碳濃度高之混合氣體藉由通 過吸附劑層，而將H20、C02、CH4等吸附於吸附劑上並 去除。使上述H20、C02、CH4等吸附於吸附劑之吸附塔 79藉由以真空泵80吸引吸附塔79內，使H20、C02、 CH4等自吸附劑脫附並以廢氣排出。 上述混合氣體藉由第一 PSA裝置73將H20、C02、 CH4等吸附去除成以一氧化碳氣體及氫氣作主之混合氣體 ，並導入第二PSA裝置74。 上述第二PSA裝置74爲並列配置有複數根（例如此 例中爲4根）吸附塔8 1之構成。於上述各吸附塔8 1內部 ’充塡活性碳、分子篩、沸石等之吸附劑，自上述第一 PSA裝置73排出之一氧化碳氣體與氫氣之混合氣體藉由 通過吸附劑層，而將一氧化碳氣體吸附於吸附劑上並分離 ° 一氧化碳氣體之吸附分離係將自吸附塔81排出之氣體 以循環壓縮機8 6再度導入吸附塔8 1並重複複數次操作循 環而進行，且將一氧化碳濃度充分低之氫氣作爲製品氫氣 而回收。 於上述各吸附塔81所吸附分離之一氧化碳氣體藉由 以真空泵82吸引吸附塔8 1內，使一氧化碳自吸附劑脫附 -23- 200906720 ，經過緩衝槽83、壓縮機84 ’而作爲製品一氧化碳儲存 於製品槽85中。 如上述，本實施形態之產生一氧化碳氣體之裝置及方 法，藉由在上述反應器51或反應步驟下游導入水蒸氣， 可有效防止在反應器51下游的配管內部等之金屬表面上 析出碳。因此，除了可在一氧化碳發生勢高的條件下運轉 以外，可大幅降低去除污染物質等之維護。如此，由於可 抑制於反應器5 1或反應步驟下游導入水蒸氣引起之碳析 出，故抑制於反應器51或反應步驟中導入之水蒸氣量成 爲可能，藉由反應器51或反應步驟所得之改質氣體之一 氧化碳濃度可大幅提高且大幅提高一氧化碳之收率。 於上述反應器51下游設置可回收由反應器51所產生 之熱的熱交換器76、77、78，且在上述反應器51之出口 與最上游側之第一熱交換器76入口之間導入水蒸氣時， 可有效防止用以回收反應器51之熱而設在反應器51下游 之熱交換器76、77、78被碳析出所污染，除了可在一氧 化碳氣體之產生勢高的條件下運轉以外，可大幅降低去除 污染物質等之維護。 導入上述反應器51之原料氣體構成爲以水蒸氣中之 H2〇與碳化氫系氣體中之C的莫耳比H20/C成爲0.5以下 之方式’設定碳化氫系氣體與氧系氣體與水蒸氣之混合比 時’所產生之混合氣體中一氧化碳氣體濃度變高。又，由 於反應器5 1中產生高溫，故自反應器5 1排出之混合氣體 所得之熱可利用於使原料加熱或利用於使導入反應器下游 -24- 200906720 之水蒸氣加熱。 導入上述反應器51之原料氣體構成爲以氧系氣體中 之〇2與碳化氫系氣體中之C的莫耳比02/C成爲0.3以上 〇-5以下之方式，設定碳化氫系氣體與氧系氣體與水蒸氣 之混合比時，除了可防止因內部燃燒反應引起之過度放熱 、可防止觸媒損傷以外，亦可適當維持所得混合氣體之組 成。 上述反應器51藉由使用經Rh改質之（Ni-Ce02) -Pt 觸媒，使碳化氫系氣體之燃燒反應與轉化反應在相同反應 區域內同時進行時，藉由使放熱反應之燃燒反應與吸熱反 應之轉化反應在相同反應區域內同時進行，由於可利用反 應燃燒所產生之熱能作爲轉化反應之熱源’故極具有能源 效率。再者，於該反應區域同時發生放熱反應及吸熱反應 ，故可引起熱中和而可以熱平衡狀態進行運轉。因此’與 例如於反應器51內設置單獨進行觸媒燃燒反應之區域的 情況相比，頗能抑制反應區域之溫度上升’反應器5 1所 用之耐熱材料之選定或反應器51本身之耐熱構造即使並 非如此程度之高溫規格亦足以使用’故亦可節省設備成本 。又，可降低朝觸媒層入口供給之原料氣體溫度，可抑制 因碳化氫熱分解而產生煤’亦可避免著火危險。 上述原料氣體係以每次預先使碳化氫氣體與水蒸氣混 合，於其中與氧系氣體合流並導入反應器51中之構成時 ，可縮短使可燃性氣體之碳化氫氣體與氧系氣體之混合氣 體通過之流路’於安全方面爲有利。 -25- 200906720 上述原料氣體係以每次預先使氧系氣體與水蒸氣混合 ，於其中與碳化氫系氣體合流並導入反應器51中之構成 時，由於混合有可燃性氣體之碳化氫系氣體之混合氣體之 氧濃度變低，故***界限更降低’於安全方面爲有利。 上述原料氣體之供給量以對應於碳化氫系氣體之供給 量變動而自動變動氧系氣體及水的供給量之方式控制時’ 經常獲得大致一定C◦濃度氣體，而可變動生成量。 具備使導入反應器51之原料氣體預熱之預熱加熱器 66，以上述預熱加熱器66使上述原料氣體向反應器51供 給之溫度控制爲25 0〜45(TC時，成爲可經常以效率良好地 熱平衡狀態運轉。 又，由於可抑制於反應器5 1或反應步驟下游導入之 水蒸氣引起之碳析出，故可抑制導入反應器5 1或反應步 驟之水蒸氣量，隨運轉條件而定，成爲亦可省略配置在第 一 PSA裝置73上游處之氣液分離器71。 圖2爲g兌明本發明第一實施形態之產生一·氧化碳裝置 及方法之圖。 此例中，於上述反應器5 1或反應步驟下游設有導入 純水作爲以含有H2 0爲主之流體之純水導入管路8 8及純 水吹入器8 7。藉此，成爲於自反應器5 1排出之高溫改質 氣體中導入純水。其以外，與上述實施例同樣，同樣的部 份附以同樣符號。此例亦發揮與上述實施形態同樣的作用 效果。 圖3爲說明本發明第三實施形態之產生一氧化碳裝置 -26- 200906720 及方法之圖。 於是，以本實施形態之產生一氧化碳之裝置及方 於上述反應器51或反應步驟下游設有導入氫氣作爲 有氫氣爲主之氣體之氫氣導入管路90 °藉此，成爲 反應器51排出之高溫改質氣體中導入主要爲氫氣之 。於上述反應器51或反應步驟下游所導入之氫氣流 由設於氫氣導入管路90上之流量調節閥9 1加以調節 於上述反應器51或反應步驟下游導入之以氫氣 之氣體亦可使用例如自氫高壓筒之氫源供給之氫氣， 導入以上述一氧化碳與氫之分離裝置的第二”八裝㊂ 所分離並回收之氫氣。此等氫氣亦可就此導入反應^ 或反應步驟下游，亦可與氮氣或水蒸氣等其他氣體混 導入。 氫氣導入管路90合流於上述改質氣體管路72之 位置，係配置於設在改質氣體管路7 2上之複數個熱 器76、77、78中最上游側之第一熱交換器76之入口 應器5 1之出口之間。 除此之外，與上述各實施形態同樣’於同樣部份 相同符號。 本實施形態之產生一氧化碳氣體之裝置及方法’ 在上述反應器51或反應步驟下游導入含有以氫氣爲 氣體，可有效防止在反應器51下游的配管內部等之 表面上析出碳。因此’除了可在一氧化碳氣體發生勢 條件下運轉以外，可大幅降低去除污染物質等之維護 法， 以含 於自 體 量藉 0 爲主 亦可 | 74 I 51 合並 合流 交互 與反 附以 藉由 主之 金屬 高的 。如 -27- 200906720 此，由於可抑制於反應器51或反應步驟下游導入含有以 氫氣爲主之氣體引起之碳析出，故抑制於反應器51或反 應步驟中導入之水蒸氣量成爲可能，藉由反應器51或反 應步驟所得之改質氣體之一氧化碳濃度可大幅提高且大幅 提高一氧化碳之收率。 於上述反應器51下游設置可回收由反應器51所產生 之熱的熱交換器76、77、78，且在上述反應器51之出口 與最上游側之第一熱交換器76入口之間導入含有以氫氣 爲主之氣體時，可有效防止用以回收反應器51之熱而設 在反應器51下游之熱交換器76、77、78被碳析出所污染 ，除了可在一氧化碳氣體之產生勢高的條件下運轉以外， 可大幅降低去除污染物質等之維護。 導入上述反應器51之原料氣體構成爲以水蒸氣中之 H2〇與碳化氫系氣體中之C的莫耳比H20/C成爲0.5以下 之方式，設定碳化氫系氣體與氧系氣體與水蒸氣之混合比 時，所產生之混合氣體中一氧化碳氣體濃度變高。又，由 於反應器51中產生高溫，故自反應器51排出之混合氣體 所得之熱可利用於使原料加熱。 導入上述反應器51之原料氣體構成爲以氧系氣體中 之〇2與碳化氫系氣體中之C的莫耳比〇2/C成爲〇·3以上 0.5以下之方式，設定碳化氫系氣體與氧系氣體與水蒸氣 之混合比時，除了可防止因內部燃燒反應引起之過度放熱 、可防止觸媒損傷以外，亦可適當維持所得混合氣體之組 成。 -28- 200906720 上述反應器51藉由使用經Rh改質之（Ni-Ce02) -Pt 觸媒，使碳化氫系氣體之燃燒反應與轉化反應在相同反應 區域內同時進行時’藉由使放熱反應之燃燒反應與吸熱反 應之轉化反應在相同反應區域內同時進行’由於可利用反 應燃燒所產生之熱能作爲轉化反應之熱源，故極具有能源 效率。再者，於該反應區域同時發生放熱反應及吸熱反應 ，故可引起熱中和而可以熱平衡狀態進行運轉。因此’與 例如於反應器5 1內設置單獨進行觸媒燃燒反應之區域的 情況相比，頗能抑制反應區域之溫度上升，反應器51所 用之耐熱材料之選定或反應器51本身之耐熱構造即使並 非如此程度之高溫規格亦足以使用，故亦可節省設備成本 。又，可降低朝觸媒層入口供給之原料氣體溫度，可抑制 因碳化氫熱分解而產生煤，亦可避免著火危險。 上述原料氣體係以每次預先使碳化氫氣體與水蒸氣混 合，於其中與氧系氣體合流並導入反應器51中之構成時 ，可縮短使可燃性氣體之碳化氫氣體與氧系氣體之混合氣 體通過之流路，於安全方面爲有利。 上述原料氣體係以每次預先使氧系氣體與水蒸氣混合 ，於其中與碳化氫系氣體合流並導入反應器51中之構成 時，由於混合有可燃性氣體之碳化氫系氣體之混合氣體之 氧濃度變低，故***界限更降低，於安全方面爲有利。 上述原料氣體之供給量以對應於碳化氫系氣體之供給 量變動而自動變動氧系氣體及水的供給量之方式控制時， 經常獲得大致一定C 0濃度之氣體，而可變動生成量。 -29- 200906720 具備使導入反應器51之原料氣體預熱之預熱加熱器 66’以上述預熱加熱器使上述原料氣體向反應益51供糸η 之溫度控制爲2 5 0〜4 5 0 °C時，成爲可經常以效率良好地熱 平衡狀態運轉。 實施例1 圖4係顯示上述產生一氧化碳裝置100中，以丙烷氣 體作爲原料，使水蒸氣中之H20與碳化氫系氣體中之C 之莫耳比H20/C變化而產生一氧化碳之結果。又，此時 之〇2/C設定爲〇_〇4，原料氣體之供給溫度設定爲400 °c ’改質壓力設定爲〇.3MPa。 由圖中可了解，於H20/C設爲0.5以下時，所產生之 改質氣體中之CO濃度變高，可提高CO收率。 圖5係顯示上述產生一氧化碳裝置100中，以丙烷氣 體作爲原料’使上述原料氣體中氧系氣體之〇2與碳化氫 系氣體中之C之莫耳比〇2/c變化而產生一氧化碳之結果 。又’此時之H2〇/C設定爲0.5，原料氣體之供給溫度設 定爲400°C ’改質壓力設定爲〇.3MPa。 由圖中可了解，於〇2/C設爲〇_3以上0.5以下時， 所產生之改質氣體中之C0濃度變高，可提高CO收率。 圖6係顯示上述產生一氧化碳裝置100中，以天然氣 作爲原料，使水蒸氣中之H2〇與碳化氫系氣體中之c之 莫耳比H2〇/C變化而產生一氧化碳之結果。又，此時之 〇2/c設定爲0.04 ’原料氣體之供給溫度設定爲4()(rc，改 -30- 200906720 質壓力設定爲〇.3MPa。 由圖中可了解，於H20/C設爲0.5以下時，所產生之 改質氣體中之CO濃度變高，可提高CO收率。 圖7係顯示上述產生一氧化碳裝置100中，以天然氣 作爲原料’使上述原料氣體中氧系氣體之〇2與碳化氫系 氣體中之C之莫耳比o2/c變化而產生一氧化碳之結果。 又’此時之H20/C設定爲0.5 ’原料氣體之供給溫度設定 爲400 °C，改質壓力設定爲0.3MPa。 由圖中可了解，於02/C設爲0.3以上0.5以下時， 所產生之改質氣體中之CO濃度變高，可提高C〇收率。 圖8係顯示本發明適用之產生滲碳氛圍氣體裝置3〇 之一構成圖。 該產生渗碳氛圍氣體裝置30具備一'反應器1，該反 應器1係導入碳化氫系氣體與氧系氣體及水蒸氣作爲原料 氣體’導入上述原料氣體，使上述原料氣體與觸媒進行催 化反應而發生碳化氫氣體之燃燒反應以及轉化反應，藉此 產生富含氫氣且一氧化碳氣體濃度高的滲碳用氛圍氣體。 上述碳化氫系氣體，在此例中，係自氣體高壓筒2供 給’在脫硫器3進行脫硫，以流量調節器4調節於特定流 量，以碳化氫預熱加熱器5預熱至特定溫度後以碳化氫供 給管路6供給。上述脫硫器3可採用進行氫化脫硫者，亦 可採用充塡有活性碳或沸石等之吸附劑進行常溫吸附脫硫 者。 上述碳化氫系氣體一般以丙烷或作爲都市天然氣等之 -31 - 200906720 社會基礎建設而供給之碳化氫系氣體爲首，可使用例如天 然氣、丁烷氣體、甲烷氣體等之碳化氫系氣體。 上述氧系氣體自未氧高壓筒7供給，以流量調節器8 調整至特定流量並由氧供給管路9供給。 至於上述氧系氣體，可適當使用工業用純氧，但若氧 氣濃度係高如2 1 %以上者，則亦可使用多少混入不純物或 其他氣體者作爲氧系氣體。 上述水蒸氣，係以泵1 〇供給純水，以流量調節器1 1 調整爲特定流量並以蒸氣加熱器1 2加熱成水蒸氣以水蒸 氣供給管路1 3供給。 上述水蒸氣供給管路1 3、碳化氫供給管路6及氧供 給管路9，首先設有使上述水蒸氣供給管路1 3與碳化氫 供給管路6合流之混合氣體流路1 4，並設有使該混合氣 體流路1 4與氧供給管路9合流之原料氣體供給管路1 5。 藉此，構成爲上述原料氣體每次首先使碳化氫氣體與水蒸 氣混合，於其中合流氧系氣體並導入反應器1中。 上述原料氣體亦可構成爲每次預先使氧系氣體與水蒸 氣混合，於其中合流碳化氫系氣體並導入反應器1中。又 ，亦可構成爲氧系氣體及水蒸氣及碳化氫系氣體同時合流 並導入反應器1中。 關於上述原料氣體之碳化氫系氣體、氧系氣體、水蒸 氣之混合比，係以流量調節器4、8、1 1，藉由分別調整 碳化氫系氣體、氧系氣體、水之流量而設定。 亦即，上述原料氣體構成爲以氧系氣體中之〇2與碳 -32 - 200906720 化氫系氣體中之c的莫耳比〇 2/C成爲0.3以上0.5以下 之方式且水蒸氣中之Η2〇與碳化氫系氣體中之C之莫耳 比H20/C成爲0.3以下之方式’設定碳化氫系氣體與氧系 氣體與水蒸氣之混合比。又’水蒸氣中之Ηβ與碳化氫 系氣體中之c之莫耳比H2〇/C較好設定爲0.05以上0.3 以下。 例如碳化氫氣體爲甲烷（CH4 )時，甲烷中之c爲1 ，故02/1=0.3-0.5，即爲相對於甲院1莫耳〇2爲ο」〜〇.5 莫耳之比混合，H2〇/l=〇.3以下’即相對於甲烷！莫耳 H20成爲0.3莫耳以下而混合。 同樣地，例如，碳化氫氣體爲丙烷（C3H8 )時，丙院 中之C爲3，故〇2Π爲0.3〜0.5，即相對於丙院i莫耳〇2 爲〇_9〜1 .5莫耳之比混合，Η2〇/3 = 0·3以下，即相對於丙 院1莫耳Η2〇成爲0.9莫耳以下而混合。 又’此裝置具備流量控制機1 7，該流量控制機丨7係 檢測上述流量調節器4中之碳化氫系氣體之流量變動，並 對應於碳化氫系氣體之供給量變動而保持上述混合比率之 方式，調節氧氣流量調節器8及水流量調節器丨丨，且使 氧系氣體及水之供給量自動變動之方式控制原料氣體之供 給量。 於原料氣體流路1 4與氧供給管路9之合流點附近， 氧供給管路9、混合氣體流路丨4以及原料氣體供給路線 1 5上設有將碳化氫系氣體與水蒸氣之混合氣體、氧系氣 體、上述混合氣體與氧系氣體混合之原料氣體預熱至特定 -33- 200906720 預熱溫度爲止之預熱加熱器16。因此，以上述預熱加熱 器16預熱至特定溫度之經預熱原料氣體被導入反應器1 中〇 上述反應器1中塡充經Rh改質之（Ni-Ce02 ) -Pt觸 媒。因此藉由使用上述經Rh改質之（Ni-Ce02 ) -Pt觸媒 ，使碳化氫系氣體之燃燒反應與轉化反應在相同反應區域 內同時進行。 接著，上述反應器1具備有溫度控制器1 8，該溫度 控制器1 8係檢測上述原料氣體朝反應器1供給時之溫度 亦即入口側溫度，且使上述預熱加熱器1 6將原料氣體供 應溫度控制爲3 0 0〜4 5 0 °C。 又，上述反應器1中設有啓動加熱器19，其係在裝 置啓動時，使自未圖示之氮氣高壓筒所供給之氮氣流動同 時使塡充有觸媒之反應區域預熱。藉由上述啓動加熱器 1 9，裝置啓動時內部溫度加熱至原料氣體反應開始所必要 的200〜3 00 °C左右爲止，同樣地以上述溫度控制器18加 以控制。 於上述反應器1，利用經Rh改質之（Ni-Ce02 ) -Pt 觸媒，使碳化氫之燃燒反應與轉化反應可在一個反應區域 內同時進行碳化氫之燃燒反應及轉化反應。 亦即，碳化氫之一部份完全燃燒使碳化氫轉變成CO 及H20之燃燒反應、與藉由此燃燒反應所生成之c〇2及 H2〇分別進而與剩餘之碳化氫反應而轉化成H2及CO之 轉化反應，係在上述觸媒上進行，可使碳化氫轉變成H2 -34- 200906720 及CO。 例如，若以碳化氫爲甲烷之情況加以說明，其反應全 體以如下式（9)般表示，但實際上如式（10)〜（12) ’ 係以燃燒反應所生成之C02及H20進而與CH4引起轉化 反應，而轉變爲CO與H2之逐步反應。 CH4 + 2〇2^ 4 CO + 8H2 -----(9) CH4 + 2〇2^ C02 + 2H2〇 .....(10) CH4 + C02 今 2 CO + 2H2 .....(11) 2CH4 + 2 H20+ 2 CO + 6H2 .....(12) 上述CH4與02進行催化反應之際，可進而於系統中 供給C〇2或2H20。此情況下，與C02或2H20之供給量 相抵之02供給量可減少。 反應溫度可爲 3 5 0〜900 °C，尤其是宜爲400~800 °c左 右。CH4與〇2之燃燒反應爲放熱反應，CH4與H20之轉 化反應爲吸熱反應。如上述，裝置啓動時藉由使反應器1 內之反應區域預熱至200〜3 00 °C，且原料氣體之供給溫度 控制成爲3 00〜45 0 °C，藉此使燃燒反應與轉化反應成爲熱 平衡狀態隨後同時進行。又，反應溫度之不足部份亦可施 加外部加熱。又，反應壓力通常採用加壓條件，但常壓條 件亦可。 藉由上述轉化反應所得之轉化氣體組成，以乾重計大 約爲 5 8 % Η 2 + 3 9 % C 0+ 1 % C Ο 2 + 2 % C Η 4，其餘爲不純物。上 物反應器1之出口部份的轉化氣體溫度約爲700~800 °C左 右。 -35- 200906720 上述經Rh改質之（Ni-Ce02 ) -Pt觸媒係例如藉由使 具有®當空隙率之氧化鋁載體表面上擔持Rh，隨後擔持 Pt ’進而同時擔持Ni及Ce02而獲得。其中，載體材質或 形狀之選擇、有無形成被覆物或其材質之選擇，可能有種 種變化。After the PSA device 73 removes H20' C02, CH4, etc., it is separated into carbon monoxide and hydrogen by the second PSA unit 74. The first PSA device 73 has a configuration in which a plurality of (for example, four in this example) adsorption towers 7 are arranged in parallel. In the inside of each of the adsorption towers 7 9 , an adsorbent such as activated carbon, molecular sieve or zeolite is charged, and a mixed gas rich in hydrogen and having a high concentration of carbon monoxide generated by the reactor 51 is passed through the adsorbent layer to pass H20, C02, CH4, etc. are adsorbed on the adsorbent and removed. The adsorption tower 79 which adsorbs the H20, CO2, CH4 or the like to the adsorbent is sucked into the adsorption tower 79 by the vacuum pump 80, and H20, CO2, CH4 and the like are desorbed from the adsorbent and discharged as exhaust gas. The mixed gas is adsorbed and removed by the first PSA unit 73 into a mixed gas mainly composed of carbon monoxide gas and hydrogen, and introduced into the second PSA unit 74. The second PSA unit 74 has a configuration in which a plurality of (e.g., four in this example) adsorption towers 8 1 are arranged in parallel. The adsorbent of activated carbon, molecular sieve, zeolite or the like is filled in the inside of each of the adsorption towers 81, and a mixed gas of carbon oxide gas and hydrogen is discharged from the first PSA unit 73 to adsorb carbon monoxide gas through the adsorbent layer. The adsorption separation of the carbon monoxide gas on the adsorbent is carried out by introducing the gas discharged from the adsorption tower 81 into the adsorption tower 81 by the recycle compressor 86 and repeating the plurality of operation cycles, and the hydrogen gas having a sufficiently low carbon monoxide concentration. It is recovered as hydrogen of the product. One of the carbon monoxide gases adsorbed and separated by the adsorption towers 81 is sucked into the adsorption tower 81 by the vacuum pump 82, and the carbon monoxide is desorbed from the adsorbent -23-200906720, and is stored as a carbon monoxide product through the buffer tank 83 and the compressor 84'. In the product tank 85. As described above, in the apparatus and method for generating carbon monoxide gas in the present embodiment, by introducing water vapor downstream of the reactor 51 or the reaction step, it is possible to effectively prevent carbon from being deposited on the metal surface inside the piping downstream of the reactor 51. Therefore, in addition to the operation of carbon monoxide, the maintenance of decontaminants and the like can be greatly reduced. In this way, since it is possible to suppress precipitation of carbon caused by introduction of water vapor downstream of the reactor 51 or the reaction step, it is possible to suppress the amount of water vapor introduced in the reactor 51 or the reaction step, which is obtained by the reactor 51 or the reaction step. The concentration of carbon oxide in one of the reformed gases can be greatly increased and the yield of carbon monoxide can be greatly increased. A heat exchanger 76, 77, 78 capable of recovering heat generated by the reactor 51 is disposed downstream of the reactor 51, and is introduced between the outlet of the reactor 51 and the inlet of the first heat exchanger 76 on the most upstream side. In the case of water vapor, the heat exchangers 76, 77, 78 disposed downstream of the reactor 51 for recovering the heat of the reactor 51 can be effectively prevented from being contaminated by carbon deposition, except that the carbon monoxide gas can be operated under high conditions. In addition, maintenance of decontaminants and the like can be greatly reduced. The raw material gas introduced into the reactor 51 is configured such that the hydrocarbon gas and the oxygen gas and the water vapor are set such that the H 2 水 in the water vapor and the molar ratio H20/C of C in the hydrocarbon gas are 0.5 or less. At the mixing ratio, the concentration of carbon monoxide gas in the mixed gas produced becomes high. Further, since the high temperature is generated in the reactor 51, the heat of the mixed gas discharged from the reactor 51 can be utilized to heat the raw material or to heat the water vapor introduced into the downstream of the reactor -24-200906720. The raw material gas introduced into the reactor 51 is configured such that the hydrocarbon gas and oxygen are set such that the molar ratio 02/C of C in the oxygen-based gas and the hydrocarbon-based gas is 0.3 or more and 〇-5 or less. When the mixing ratio of the gas to the water vapor is used, the composition of the obtained mixed gas can be appropriately maintained in addition to preventing excessive heat generation due to the internal combustion reaction and preventing damage to the catalyst. The above reactor 51 uses a Rh-modified (Ni-Ce02)-Pt catalyst to simultaneously react a combustion reaction of a hydrocarbon-based gas with a conversion reaction in the same reaction zone by a combustion reaction of an exothermic reaction The conversion reaction with the endothermic reaction proceeds simultaneously in the same reaction zone, and since the heat energy generated by the reaction combustion can be utilized as a heat source for the conversion reaction, it is extremely energy-efficient. Further, an exothermic reaction and an endothermic reaction occur simultaneously in the reaction zone, so that heat neutralization can be caused and the operation can be performed in a state of thermal equilibrium. Therefore, it is possible to suppress the temperature rise of the reaction zone as compared with the case where the catalyst combustion reaction is separately performed in the reactor 51, for example, the selection of the heat resistant material used for the reactor 51 or the heat resistant structure of the reactor 51 itself. Even if it is not such a high temperature specification, it is enough to use it, so it can also save equipment costs. Further, the temperature of the material gas supplied to the inlet of the catalyst layer can be lowered, and the generation of coal by thermal decomposition of hydrocarbon can be suppressed, and the risk of fire can be avoided. When the raw material gas system is mixed with water vapor in advance, and the oxygen gas is combined with the oxygen gas and introduced into the reactor 51, the mixing of the hydrocarbon gas of the combustible gas with the oxygen gas can be shortened. The flow path through which the gas passes is advantageous in terms of safety. -25-200906720 The above-mentioned raw material gas system is a mixture of an oxygen-based gas and steam, and a hydrocarbon-hydrogen gas mixed with a flammable gas when it is combined with a hydrocarbon-based gas and introduced into the reactor 51. The oxygen concentration of the mixed gas is lowered, so that the explosion limit is further lowered, which is advantageous in terms of safety. When the supply amount of the raw material gas is controlled so as to automatically change the supply amount of the oxygen-based gas and water in accordance with the fluctuation in the supply amount of the hydrocarbon-based gas, a gas having a substantially constant C◦ concentration is often obtained, and the amount of production can be varied. The preheating heater 66 for preheating the material gas introduced into the reactor 51 is controlled so that the temperature of the raw material gas supplied to the reactor 51 by the preheating heater 66 is controlled to 25 0 to 45 (TC), Further, since the carbon is prevented from being precipitated by the water vapor introduced downstream of the reactor 51 or the reaction step, the amount of water vapor introduced into the reactor 51 or the reaction step can be suppressed, depending on the operating conditions. The gas-liquid separator 71 disposed upstream of the first PSA unit 73 may be omitted. Fig. 2 is a view showing the apparatus and method for generating a carbon monoxide according to the first embodiment of the present invention. In the above reactor 5 1 or downstream of the reaction step, pure water is introduced as a pure water introduction line 8 8 and a pure water insufflator 8 7 containing a H 2 0-based fluid, thereby forming the self-reactor 5 . In the same manner as in the above-described embodiment, the same portions are denoted by the same reference numerals, and the same effects as those of the above-described embodiment are also exhibited. Three implementation The carbon monoxide generating device -26-200906720 and the method of the method. Thus, the apparatus for generating carbon monoxide according to the embodiment and the hydrogen introducing tube for introducing hydrogen into the reactor 51 or the reaction step are provided downstream of the reactor 51 or the reaction step. The passage of 90 ° thereby introduces mainly hydrogen into the high-temperature reforming gas discharged from the reactor 51. The hydrogen flow introduced downstream of the reactor 51 or the reaction step is provided by a flow regulating valve provided on the hydrogen introduction line 90. 9 1 is adjusted to the above reactor 51 or the gas introduced downstream of the reaction step by using hydrogen gas, for example, hydrogen gas supplied from a hydrogen source of the hydrogen high pressure cylinder, and introduced into the second "eight pack three" of the above-mentioned separation device of carbon monoxide and hydrogen. The separated and recovered hydrogen gas may be introduced into the reaction or downstream of the reaction step, or may be introduced in combination with other gases such as nitrogen or water vapor. The hydrogen introduction line 90 merges with the modified gas line 72. The inlet device of the first heat exchanger 76 disposed on the most upstream side of the plurality of heaters 76, 77, 78 disposed on the reformed gas line 72 In the same manner as in the above embodiments, the same reference numerals are given to the same portions as in the above embodiments. The apparatus and method for generating carbon monoxide gas in the present embodiment are introduced in the reactor 51 or the downstream of the reaction step. Hydrogen is a gas, and it is possible to effectively prevent carbon from being deposited on the surface of the inside of the piping downstream of the reactor 51. Therefore, in addition to being operated under the condition that the carbon monoxide gas is generated, the maintenance method for removing pollutants and the like can be greatly reduced. The self-body volume can be dominated by 0. 74 I 51 The merged merge interaction and the anti-attachment are higher by the metal of the main. For example, -27-200906720, since it can be suppressed from being introduced into the reactor 51 or downstream of the reaction step containing hydrogen Since the carbon caused by the main gas is precipitated, it is possible to suppress the amount of water vapor introduced in the reactor 51 or the reaction step, and the concentration of carbon oxide in the reformed gas obtained by the reactor 51 or the reaction step can be greatly increased and the carbon monoxide can be greatly increased. The yield. A heat exchanger 76, 77, 78 capable of recovering heat generated by the reactor 51 is disposed downstream of the reactor 51, and is introduced between the outlet of the reactor 51 and the inlet of the first heat exchanger 76 on the most upstream side. When the gas containing hydrogen is contained, the heat exchangers 76, 77, 78 disposed downstream of the reactor 51 for recovering the heat of the reactor 51 can be effectively prevented from being contaminated by carbon deposition, except for the generation of carbon monoxide gas. In addition to operation under high conditions, maintenance of decontaminants and the like can be greatly reduced. The raw material gas introduced into the reactor 51 is configured such that the hydrocarbon gas and the oxygen gas and the water vapor are set such that the H 2 水 in the water vapor and the molar ratio H20/C of C in the hydrocarbon gas are 0.5 or less. At the mixing ratio, the concentration of carbon monoxide gas in the mixed gas produced becomes high. Further, since the high temperature is generated in the reactor 51, the heat of the mixed gas discharged from the reactor 51 can be utilized to heat the raw material. The raw material gas to be introduced into the reactor 51 is configured such that the hydrocarbon gas is set to be 〇·3 or more and 0.5 or less in the 〇 2 of the oxygen-based gas and the molar ratio C 2 / C of C in the hydrocarbon-based gas. When the mixing ratio of the oxygen-based gas and the water vapor is prevented, excessive heat generation due to the internal combustion reaction can be prevented, and the catalyst can be prevented from being damaged, and the composition of the obtained mixed gas can be appropriately maintained. -28- 200906720 The above reactor 51 uses a Rh-modified (Ni-Ce02)-Pt catalyst to simultaneously react the combustion reaction of the hydrocarbon-based gas with the conversion reaction in the same reaction zone. The conversion reaction between the combustion reaction of the reaction and the endothermic reaction is carried out simultaneously in the same reaction zone. The thermal energy generated by the combustion of the available reaction is used as a heat source for the conversion reaction, so that it is extremely energy-efficient. Further, an exothermic reaction and an endothermic reaction occur simultaneously in the reaction zone, so that heat neutralization can be caused and the operation can be performed in a state of thermal equilibrium. Therefore, it is possible to suppress the temperature rise of the reaction zone, the selection of the heat resistant material used for the reactor 51, or the heat resistant structure of the reactor 51 itself, as compared with the case where, for example, a region where the catalyst combustion reaction is separately performed in the reactor 51 is provided. Even if it is not such a high temperature specification, it is enough to save equipment costs. Further, the temperature of the material gas supplied to the inlet of the catalyst layer can be lowered, and coal can be prevented from being thermally decomposed by the decomposition of the hydrocarbon, and the risk of ignition can be avoided. When the raw material gas system is mixed with water vapor in advance, and the oxygen gas is combined with the oxygen gas and introduced into the reactor 51, the mixing of the hydrocarbon gas of the combustible gas with the oxygen gas can be shortened. The flow path through which the gas passes is advantageous in terms of safety. In the above-mentioned raw material gas system, a mixture of a hydrocarbon-based gas and a water vapor is mixed in advance, and when it is combined with a hydrocarbon-based gas and introduced into the reactor 51, a mixed gas of a hydrocarbon-based gas in which a combustible gas is mixed is used. As the oxygen concentration becomes lower, the explosion limit is further reduced, which is advantageous in terms of safety. When the supply amount of the raw material gas is controlled so as to automatically change the supply amount of the oxygen-based gas and the water in accordance with the fluctuation in the supply amount of the hydrocarbon-based gas, the gas having a substantially constant C 0 concentration is often obtained, and the amount of production can be varied. -29-200906720 The preheating heater 66' for preheating the raw material gas introduced into the reactor 51 is controlled by the preheating heater to supply the raw material gas to the reaction mass 51 to a temperature of 2,500 to 4,500. At °C, it is possible to operate in an efficient thermal equilibrium state. [Embodiment 1] Fig. 4 shows the results of the production of carbon monoxide in the carbon monoxide generating apparatus 100 described above, using propane gas as a raw material to change the molar ratio of H20 in the water vapor to the molar ratio H20/C of C in the hydrocarbon-based gas. Further, at this time, 〇2/C was set to 〇_〇4, and the supply temperature of the material gas was set to 400 °c. The reforming pressure was set to 〇3 MPa. As can be seen from the figure, when H20/C is 0.5 or less, the CO concentration in the reformed gas generated becomes high, and the CO yield can be improved. Fig. 5 is a view showing the result of generating carbon monoxide by changing the molar ratio 〇2/c of the oxygen-based gas in the raw material gas and the molar ratio C2/c of C in the hydrocarbon-based gas in the carbon monoxide generating apparatus 100 described above. . Further, H2〇/C at this time was set to 0.5, the supply temperature of the material gas was set to 400 °C, and the reforming pressure was set to 〇3 MPa. As can be seen from the figure, when 〇2/C is set to 〇_3 or more and 0.5 or less, the C0 concentration in the reformed gas generated becomes high, and the CO yield can be improved. Fig. 6 is a view showing the result of generating carbon monoxide in the carbon monoxide generating apparatus 100 by using natural gas as a raw material to change the molar ratio of H2〇 in the steam to the molar ratio H2〇/C of c in the hydrocarbon-based gas. In addition, at this time, 〇2/c is set to 0.04'. The supply temperature of the material gas is set to 4 () (rc, change -30-200906720, the mass pressure is set to 〇.3 MPa. As can be seen from the figure, it is set at H20/C. When the ratio is 0.5 or less, the CO concentration in the reformed gas generated is increased, and the CO yield can be increased. Fig. 7 is a view showing that the carbon monoxide generating device 100 uses natural gas as a raw material to make the oxygen gas in the raw material gas 2 The result of carbon monoxide ratio o2/c in the hydrocarbon gas is changed by carbon monoxide. The H20/C is set to 0.5 at this time. The supply temperature of the raw material gas is set to 400 °C, and the reforming pressure is set. It is 0.3 MPa. As can be seen from the figure, when 02/C is set to 0.3 or more and 0.5 or less, the CO concentration in the generated reformed gas becomes high, and the C 〇 yield can be improved. Fig. 8 shows the application of the present invention. A configuration of one of the carburizing atmosphere gas devices 3 is provided. The carburizing atmosphere gas device 30 includes a 'reactor 1 that introduces a hydrocarbon gas, an oxygen gas, and water vapor as a raw material gas. The raw material gas is used to carry out the raw material gas and the catalyst The combustion reaction of the hydrocarbon gas and the conversion reaction occur to generate a carburizing atmosphere gas rich in hydrogen gas and having a high concentration of carbon monoxide gas. The hydrocarbon gas is supplied from the gas high pressure cylinder 2 in this example. 'Desulfurization is carried out in the desulfurizer 3, adjusted to a specific flow rate by the flow regulator 4, and preheated to a specific temperature by the hydrocarbon preheating heater 5, and then supplied to the hydrocarbon supply line 6. The desulfurizer 3 can be used. For hydrodesulfurization, it is also possible to carry out desulfurization at room temperature by using an adsorbent such as activated carbon or zeolite. The above hydrocarbon gas is generally supplied by propane or as a social infrastructure such as urban natural gas. The hydrocarbon-based gas is used, and a hydrocarbon-based gas such as natural gas, butane gas, or methane gas can be used. The oxygen-based gas is supplied from the unoxygenated high pressure cylinder 7, and is adjusted to a specific flow rate by the flow rate regulator 8 and is made of oxygen. The supply line 9 is supplied. For the oxygen-based gas, industrial pure oxygen can be suitably used. However, if the oxygen concentration is as high as 21% or more, how much can be used. An impurity or other gas is used as the oxygen-based gas. The water vapor is supplied to the pure water by the pump 1 , adjusted to a specific flow rate by the flow regulator 1 1 , and heated to a steam by the steam heater 12 to supply the water vapor. The water vapor supply line 13 , the hydrocarbon supply line 6 , and the oxygen supply line 9 are first provided with a mixed gas flow that joins the water vapor supply line 13 and the hydrocarbon supply line 6 . The path 14 is provided with a material gas supply line 15 that allows the mixed gas flow path 14 to merge with the oxygen supply line 9. Thereby, the raw material gas is first mixed with the water vapor first. The oxygen-based gas is combined and introduced into the reactor 1. The material gas may be configured such that the oxygen-based gas is mixed with the water vapor in advance, and the hydrocarbon-based gas is combined and introduced into the reactor 1. Further, the oxygen-based gas, the water vapor, and the hydrocarbon-based gas may be simultaneously merged and introduced into the reactor 1. The mixing ratio of the hydrocarbon gas, the oxygen gas, and the water vapor of the source gas is set by adjusting the flow rates of the hydrocarbon gas, the oxygen gas, and the water by the flow rate regulators 4, 8, and 1 respectively. . In other words, the raw material gas is configured such that the molar ratio 〇2/C of c in the oxygen-based gas and the carbon-32 - 200906720 hydrogen-based gas is 0.3 or more and 0.5 or less and Η 2 in the water vapor. The mixing ratio of the hydrocarbon-based gas to the oxygen-based gas and the water vapor is set such that the molar ratio of C to the molar ratio H20/C in the hydrocarbon gas is 0.3 or less. Further, the molar ratio H2〇/C of Ηβ in the steam and c in the hydrocarbon gas is preferably set to 0.05 or more and 0.3 or less. For example, when the hydrocarbon gas is methane (CH4), c in methane is 1, so 02/1=0.3-0.5, which is a ratio of ο"~〇.5 molar ratio with respect to 1 〇2 , H2 〇 / l = 〇. 3 below 'that is relative to methane! The Mo H20 is mixed below 0.3 mol. Similarly, for example, when the hydrocarbon gas is propane (C3H8), C in the courtyard is 3, so 〇2Π is 0.3 to 0.5, that is, 〇_9~1. The ratio of the ear is mixed, Η2〇/3 = 0·3 or less, that is, mixed with less than 0.9 moles in the case of the 1st Η2〇. Further, the apparatus includes a flow rate control unit 7 for detecting a flow rate fluctuation of the hydrocarbon-based gas in the flow rate adjuster 4, and maintaining the mixing ratio in accordance with a variation in the supply amount of the hydrocarbon-based gas. In this manner, the oxygen flow rate regulator 8 and the water flow rate regulator 调节 are adjusted, and the supply amount of the material gas is controlled such that the supply amount of the oxygen-based gas and the water is automatically changed. In the vicinity of the junction point of the raw material gas flow path 14 and the oxygen supply line 9, the oxygen supply line 9, the mixed gas flow path 4, and the raw material gas supply path 15 are provided with a mixture of a hydrocarbon-based gas and water vapor. The gas, the oxygen-based gas, and the raw material gas in which the mixed gas and the oxygen-based gas are mixed are preheated to the preheating heater 16 at a preheating temperature of -33 to 200906720. Therefore, the preheated raw material gas preheated to the specific temperature by the preheating heater 16 described above is introduced into the reactor 1. The above reactor 1 is filled with Rh-modified (Ni-Ce02)-Pt catalyst. Therefore, by using the above Rh-modified (Ni-Ce02)-Pt catalyst, the combustion reaction of the hydrocarbon-based gas and the conversion reaction are simultaneously carried out in the same reaction zone. Next, the reactor 1 is provided with a temperature controller 18 for detecting the temperature at the time when the raw material gas is supplied to the reactor 1, that is, the inlet side temperature, and the preheating heater 16 is used as a raw material. The gas supply temperature is controlled to be 300 to 4 50 °C. Further, the reactor 1 is provided with a starter heater 19 for preheating a reaction zone which is filled with a catalyst while flowing nitrogen gas supplied from a nitrogen high pressure cylinder (not shown) while the apparatus is being started. By the start of the heater 1, the internal temperature is heated up to about 200 to 300 °C necessary for the start of the reaction of the raw material gas, and the temperature controller 18 is controlled in the same manner. In the above reactor 1, the combustion reaction and the conversion reaction of the hydrocarbon are carried out by the Rh-modified (Ni-Ce02)-Pt catalyst to simultaneously carry out the combustion reaction and the conversion reaction of the hydrocarbon in one reaction zone. That is, one part of the hydrocarbon is completely burned to convert the hydrocarbon into a combustion reaction of CO and H20, and the c〇2 and H2〇 generated by the combustion reaction are respectively converted into H2 by reacting with the remaining hydrocarbon. The CO conversion reaction is carried out on the above catalyst to convert the hydrocarbon into H2 - 34 - 200906720 and CO. For example, when carbon dioxide is used as the methane, the reaction is generally represented by the following formula (9), but actually, the formula (10) to (12) ' is formed by the combustion reaction to produce C02 and H20. CH4 causes a conversion reaction and is converted into a stepwise reaction of CO and H2. CH4 + 2〇2^ 4 CO + 8H2 -----(9) CH4 + 2〇2^ C02 + 2H2〇.....(10) CH4 + C02 Today 2 CO + 2H2 .....( 11) 2CH4 + 2 H20+ 2 CO + 6H2 (12) When the above CH4 and 02 are subjected to a catalytic reaction, C〇2 or 2H20 may be further supplied to the system. In this case, the supply amount of 02 which is offset by the supply amount of C02 or 2H20 can be reduced. The reaction temperature may be from 3,500 to 900 °C, particularly preferably from about 400 to about 800 °C. The combustion reaction between CH4 and 〇2 is an exothermic reaction, and the conversion reaction between CH4 and H20 is an endothermic reaction. As described above, when the apparatus is started up, the reaction zone in the reactor 1 is preheated to 200 to 300 ° C, and the supply temperature of the raw material gas is controlled to be 300 to 45 ° C, thereby causing the combustion reaction and the conversion reaction. It becomes a state of thermal equilibrium and then proceeds simultaneously. Further, external heating may be applied to the insufficient portion of the reaction temperature. Further, the reaction pressure is usually under pressurized conditions, but it is also possible under normal pressure conditions. The conversion gas composition obtained by the above conversion reaction is about 58 % by dry weight, Η 2 + 3 9 % C 0 + 1 % C Ο 2 + 2 % C Η 4, and the balance is impurities. The temperature of the reforming gas at the outlet of the reactor 1 is about 700 to 800 °C. -35- 200906720 The Rh-modified (Ni-Ce02)-Pt catalyst is supported by, for example, supporting Rh by the surface of an alumina carrier having a void ratio, and then carrying Pt' Obtained by Ce02. Among them, there may be various changes in the choice of the material or shape of the carrier, the presence or absence of the formation of the coating or the material thereof.
Rh之擔持係藉由含浸Rh之水溶性鹽之水溶液後，使 乾燥、燒成、氫還原而進行。又，Pt之擔持係藉由含浸 Pt之水溶性鹽之水溶液後，使乾燥、燒成、氫還原而進 行。N i及C e Ο 2之同時擔持係藉由含浸N i之水溶性鹽以 及Ce之水溶性鹽之混合水溶液後，使乾燥、燒成、氫還 原而進行。 藉由上述列示之順序，獲得成爲目的之經Rh改質之 (Ni-Ce〇2 ) -Pt觸媒。各成份之組成以重量比計，宜設定 爲 Rh : Ni : Ce02 : Pt= ( 0.05-0.5 ) : ( 3.0-10.0)：( 2.0-8.0 ) ： ( 0.3-5.0 )，更好爲 Rh:Ni:Ce02:Pt=( 0.1-0.4 ) ： ( 4.0-9.0 ) ： ( 2.0-5.0 ) ： ( 0.3-3.0 )。 又，上述中各階段之氫還原處理可省略，而在實際使 用時使觸媒在高溫氫還原後使用。在各階段進行氫還原處 理時，亦可進而在使用之際使觸媒在高溫氫還原後使用。 如上述所得之滲碳用氛圍氣體以冷卻器2 0冷卻，以 氣液分離器21去除水分後，導入滲碳爐中。 圖9係顯示上述產生滲碳用氛圍氣體之裝置30之氣 體滲碳裝置50 —例之圖。 此氣體滲碳裝置50具備使碳化氫系氣體與氧系氣體 -36- 200906720 及水蒸氣與觸媒進行催化反應而發生碳化氫系氣體之燃燒 反應以及轉化反應’藉此產生富含氫氣且一氧化碳氣體濃 度高的滲碳用氛圍氣體之反應器1，以及導入有上述反應 器1所得之滲碳用氛圍氣體之氛圍氣體爐31。 於是，構成爲於上述氛圍氣體爐31具備導入氟系氣 體之氟系氣體導入機構，被處理物在氟系氣體氛圍下加熱 進行形成氟化物皮膜之氟化處理後，導入在上述反應器1 所得之滲碳用氛圍氣體並加熱進行滲碳處理。 於此氣體滲碳裝置50中，被處理物40在氟系氣體氛 圍下加熱進行形成氟化物皮膜之氟化處理後，導入藉由使 碳化氫系氣體與氧系氣體及水蒸氣與觸媒進行催化反應而 發生碳化氫氣體之燃燒反應以及轉化反應所得之富含氫氣 且一氧化碳氣體濃度高的滲碳用氛圍氣體並加熱而進行滲 碳處理。 若更詳細加以說明’於圖中，31爲氛圍器爐，具備 有外殼32、內部形成爲處理室之內容器34、設於上述內 容器34與外殼32之間之加熱器33。於上述內容器34內 ’連通氣體導入管35及排氣管36。上述氣體導入管35 連通上述產生滲碳用氛圍氣體之裝置30以及充塡有氟化 處理氣體之N2 + NF3之高壓筒46。47爲流量計，48爲閥 。此例中’上述高壓筒46與流量計47此等藉由連接於氣 體導入管35之流路等，構成上述氟氣體導入機構。 又’上述排氣管36上連接有排氣處理裝置44以及真 空栗43。藉此’於內容器34內之處理室內導入處理氣體 -37- 200906720 並排出。上述處理室內’設有附加可攪拌處理氣體之馬達 37的風扇38。41爲裝入運轉的被處理物40之籠41。 於此氛圍氣爐3 1內’例如裝入被處理物40 ’導入與 高壓筒46以流路連接之NF3等之氟系氣體導入氛圍氣爐 3 1內並加熱同時進行氟化處理’隨後自排氣管3 6以真空 泵43之作用引出其氣體，在排氣處理裝置44內無毒化並 排放至外部。隨後，導入以上述產生滲碳用氛圍氣體裝置 3 0所產生之滲碳用氣體進行滲碳處理，隨後，經由排氣 管3 6、排氣處理裝置44將氣體排放至外部。藉此一連串 作業，於該氣體滲碳裝置50進行氟化處理及滲碳處理。 構成上述被處理物40之材質，可使用各種金屬材料 ，但尤其較好使用鐵系金屬材料。尤其好的是，使用以奧 氏體系不鏽鋼爲代表之奧氏體系金屬。 上述奧氏體系不鏽鋼舉例有例如含有鐵成份5 0重量 %以上、鉻成份含有1 2重量％以上含有鎳之奧氏體系不鏽 鋼。具體而言，舉例有SUS304、SUS316、SUS303S等之 1 8 - 8系不鏽鋼鋼材或含有鉻2 5重量％、鎳2 0重量％之奧 氏體系不鏽鋼之US310S或309，進而舉例有鉻含量23重 量％、鉬含有2重量％之奧氏體-純粒鐵2相系不鏽鋼鋼材 等。 又，含有鎳爲19〜22重量％、鉻爲20〜27重量％、碳 爲0.25〜0.45重量％之SCH21或SCH22等之耐熱鋼鑄鋼亦 可適合用於作爲本發明之奧氏體系不鏽鋼。再者，含有鉻 爲20〜22重量％、鎳爲3.2 5〜4.5重量％、錳爲8〜1 0重量％ -38- 200906720 '碳爲〇_48〜0.58重量％之SUH35、或含有鉻13.5〜16重 量％、鎳爲24~27重量％、鉬爲1〜1.5重量％之SUH660等 之耐熱鋼亦可適合用於作爲本發明之奧氏體系不鏽鋼。 如此，藉由使用含鎳及鉻之低碳亦可適合用於作爲本 發明之奧氏體系不鏽鋼’可製得耐蝕性優異且不析出鉻化 合物、在保有非磁性之奧氏體系不鏽鋼的表層部形成碳固 溶硬化層、耐磨耗性或耐鈾性優異之非磁性金屬製品。 如此，作爲被處理物4〇使用母材爲由奧氏體系不鏽 鋼所構成者，藉由對其進行上述氟化處理及滲碳處理，可 至少在表層部形成於母材之奧氏體固熔有碳之比母材硬度 更高之碳固熔硬化層。 此處，對上述氟化處理詳細加以說明。 上述氟化處理中所用之氟系氣體舉例爲由nf3、bf3 、CF4、HF、SF6、C2F6、WF6、CHF3、SiF4、C1F3 等所構 成之氟系化合物氣體。該等可單獨使用或以兩種以上合倂 使用。 又’該等氣體以外’於分子內含有氟之氟系氣體亦可 使用作爲本發明之氟系氣體。又’此等氣系氣化合物氣體 以熱分解裝置熱分解所生成之F2氣體或預先作成之|：2氣 體亦可使用作爲上述氛系氣體。此等氟化合物氣體與f2 氣體隨情況可混合使用。 其中尤其作爲本發明中使用之氟系氣體中最具備實用 性者爲NF3。系由於上述NF3於常溫成氣體狀、化學安定 性高且操作性容易之故。此等NF3氣體通常如後述，係與 -39- 200906720 %氣體組合在特定濃度範圍內稀釋使用。 上述中所例示之各種氟系氣體，可僅其單獨使用，但 通常以N2氣體等之惰性氣體稀釋後使用。此等經稀釋之 氣體中，氟氣體本身濃度爲例如以體積爲基準，爲 10000〜100000 ppm ’ 較好爲 20000〜70000 ppm，更好爲 30000〜50000 ppm。 使用上述氟系氣體作爲氛圍氣體之氟化處理，係使用 馬弗爐般之氛圍氣爐31，於爐內裝入未處理之被處理物 40，在上述濃度之氟系氣體氛圍氣之下，保持加熱狀態藉 此而進行。 此時之保持加熱係藉由使由奧氏體系不鏽鋼所構成之 被處理物40本身例如保持在1 80〜600 °C，較好保持在 200-450 °C而進行。上述氟系氣體氛圍中之被處理物40之 保持時間通常設定爲1 〇數分鐘~數小時。藉由使被處理物 40在此種氟系氣體氛圍下加熱處理，在奧氏體系不鏽鋼 表面形成之含有Cr204之不作用態皮膜變化成氟化膜。上 述不作用態皮膜在以往不可能滲碳，但藉由進行氟化處理 ，上述不作用態皮膜變化成氟化膜。認爲係此氟化膜比不 作用態皮膜更容易被滲碳中使用之碳原子所滲透，奧氏體 系不鏽鋼表面藉由上述氟化處理成爲碳原子容易滲透之表 面狀態之故。 其次，與上述氟化處理同時期及/或在其後，對上述 奧氏體系不鏽鋼表面進行滲碳處理。 滲碳處理係使上述奧氏體系不鏽鋼本身在680 °C以下 -40- 200906720 之滲碳處理溫度下加熱，使用上述滲碳用氣體，於爐內於 滲碳用氣體氛圍氣體中進行。於此滲碳用氣體氛圍氣體中 ’因應必要亦可富含有丙烷氣體等之碳源氣體。 因此’與以往已知之滲碳處理相比，本發明之滲碳處 理可在極低溫度領域進行。 上述滲碳處理時之溫度亦即滲碳處理溫度爲680 °C以 下，亦即較好在400~68(TC之溫度。滲碳處理溫度若超過 680 °C，由於奧氏體系不鏽鋼的母材本身產生軟化，經滲 碳之碳原子於母材上與固熔之鉻結合產生鉻碳化物，母材 本身所含之鉻量減少使表層部耐鈾性大幅降低，以侵入固 熔於滲碳層之狀態存在的碳量減少，母材強度或耐蝕性降 低，且成爲帶有磁性。 依據同樣理由，作爲上述滲碳處理溫度更好爲400〜600 t：之溫度範圍，進而較好爲400〜5 50 °C，最好爲45 0~500 °C之溫度範圍。於本發明中，藉由進行上述氟化處理，在 如此極爲低溫中之滲碳處理成爲可能，於滲碳處理中幾乎 不生成鉻碳化物粒子，碳侵入固熔於母材中，使晶格尺寸 增大而在表面層形成碳固熔硬化層。 藉由如此處理，碳於奧氏體系不鏽鋼表層部擴散滲透 並深且均一地形成碳固熔硬化層。此碳擴散層於基相的奧 氏體相中，成爲多量C原子侵入固熔引起晶格擴張之狀態 ，可實現與母材相比硬度顯著提高。且，上述碳原子幾乎 不與母材中之鉻形成Cr7C3或Cr23C6等碳化物且由於侵入 固熔於結晶晶格中，故上述碳固熔硬化層中實質上不存在 -41 - 200906720 鉻碳化物粒子’且母材中固熔之鉻量不會減少，故可維持 與母材相同程度之耐蝕性。 又’如上述般進行滲碳處理之奧氏體系不鏽鋼表面粗 度亦幾乎不惡化，不會因膨脹產生尺寸變化且亦不產生磁 性。因此，表面粗度降低或尺寸變化亦少，可以更良好精 度進行表面改質。又’奧氏體系不鏽鋼中，尤其是含多量 鎳之安定型奧氏體系不鏽鋼或含鉬之安定型奧氏體系不鏽 鋼，碳擴散層之耐蝕性更爲良好。 上述滲碳處理可自氟化處理結束後開始，亦可與氟化 處理開始同時開始進行滲碳處理，亦可在氟化處理開始後 不等渗碳處理結束而開始滲碳處理。 藉由氟化處理結束後進行滲碳處理，相對於藉由氟化 處理使表面活性化之被處理物，可比純粹滲碳氛圍氣體擴 散滲透更多碳原子，於表面強度變高且硬化深度變大時有 利，係由於有效提高表面硬度之故。 藉由上述滲碳處理不等氟化處理結束即開始，可一邊 進行藉由氟化之表面活性化一般進行碳之擴散滲透，於表 面強度變高且硬化深度變大時有利。 如上述，本實施形態之產生滲碳用氛圍氣體之裝置及 方法，藉由使碳化氫系氣體及氧系氣體及水蒸氣與觸媒進 行催化反應，藉由同時發生碳化氫系氣體之燃燒反應及轉 化反應，而發生富含氫氣且一氧化碳氣體濃度高之滲碳用 氛圍氣體。如此，由於作爲原料不使用空氣而使用氧系氣 體，故可獲得碳勢高的滲碳用氛圍氣體。又，使用水蒸氣 -42- 200906720 作爲原料，故與僅以碳化氫氣體與氧氣作爲原料之裝置相 較，***界限可降低而可大幅提高安全性。因此，與氧由 2系統之導入管路而導入之裝置相比，反應器構造本身亦 可簡化，起因於氧濃度凌亂之媒發生或觸媒的劣化亦可大 幅減少。再者，原料氣體成本亦較便宜，可以低成本且安 全地發生碳勢高之滲碳氣體。又，可獲得富含H2之氛圍 氣體，可抑制滲碳處理步驟之未反應碳微粒。 上述原料氣體係以每次預先使碳化氫氣體與水蒸氣混 合，於其中與氧系氣體合流並導入反應器1中之構成時， 可縮短使可燃性氣體之碳化氫氣體與氧系氣體之混合氣體 通過之流路，於安全方面爲有利。 上述原料氣體係以每次預先使氧系氣體與水蒸氣混合 ，於其中與碳化氫系氣體合流並導入反應器1中之構成時 ，由於合流有可燃性氣體之碳化氫系氣體之混合氣體之氧 濃度變低，故***界限更降低，於安全方面爲有利。 上述原料氣體構成爲以氧系氣體中之〇2與碳化氫系 氣體中之C的莫耳比02/C成爲0.3以上0.5以下之方式 且水蒸氣中之 H20與碳化氫系氣體中之 C之莫耳比 H20/C成爲0.3以下之方式，設定碳化氫系氣體與氧系氣 體與水蒸氣之混合比時，所生成之滲碳性氣體中之C 0濃 度變高，可獲得碳勢高之氛圍氣體。 上述原料氣體之供給量以對應於碳化氫系氣體之供給 量變動而自動變動氧系氣體及水的供給量之方式控制時， 經常獲得大致一定CO濃度之滲碳性氣體，使得滲碳性氣 -43- 200906720 體之生成量得以變動。 上述反應器1藉由使用經Rh改質之（Ni-Ce〇2) -Pt 觸媒，使碳化氫系氣體之燃燒反應與轉化反應在相同反應 區域內同時進行時，藉由使放熱反應之燃燒反應與吸熱反 應之轉化反應在相同反應區域內同時進行，由於可利用燃 燒反應所產生之熱能作爲轉化反應之熱源，故極具有能源 效率。再者，於該反應區域同時發生放熱反應及吸熱反應 ，故可引起熱中和而可以熱平衡狀態進行運轉。因此’與 例如於反應器1內設置單獨進行觸媒燃燒反應之區域的情 況相比，頗能抑制反應區域之溫度上升，反應器1所用之 耐熱材料之選定或反應器1本身之耐熱構造即使並非如此 程度之高溫規格亦足以使用’故亦可節省設備成本。又’ 可降低朝觸媒層入口洪給之原料氣體溫度，可抑制因碳化 氫熱分解而產生煤’亦可避免著火危險。 具備使導入反應器1之原料氣體預熱之預熱加熱器 1 6，上述預熱加熱器1 6將上述原料氣體向反應器1供給 的溫度控制爲3 00〜45 0 °C時，經常可以效率良好地熱平衡 狀態進行運轉。 實施例2 圖10係顯示上述產生滲碳用氛圍氣體之裝置30中， 上述原料中之氧系氣體之〇2與碳化氫系氣體中之C之莫 耳比02/C變化而產生滲碳用氣體之結果。又，此時之 H20/C設定爲0.20’原料氣體之供給溫度設定爲450 °C。 -44 - 200906720 由圖中可了解，於〇2/C設爲0.3以上〇·5以下時， 所產生之轉化氣體中之CO濃度變高’可獲得碳勢高之滲 碳氣體。 圖11係顯示上述產生滲碳用氛圍氣體之裝置30中， 上述原料中之水蒸氣中之Η2Ο與碳化氨系氣體中之c之 莫耳比H2〇/C變化而產生滲碳用氣體之結果。又，此時 之〇2/C設定爲0.40，原料氣體之供給溫度設定爲45〇〇c 0 由圖中可了解’於H2〇/C設爲0·3以下時，所產生之 轉化氣體中之CO濃度變高，可獲得碳勢高之滲碳氣體。 【圖式簡單說明】 圖1係顯示本發明之產生一氧化碳氣體裝置之一實施 形態圖。 圖2係顯示本發明之產生一氧化碳氣體裝置之第二實 施形態圖。 圖3係顯不本發明之產生一氧化碳氣體裝置之一實施 形態圖。 圖4係顯示以丙烷作爲原料，使H2〇/c變化而產生 一氧化碳氣體之結果圖。 圖5係顯示以丙焼作爲原料，使〇2/c變化而產生一 氧化碳氣體之結果圖。 圖6係顯示以天然氣作爲原料，使H2〇/c變化而產 生一氧化碳氣體之結果圖。 ' 45 - 200906720 圖7係顯示以天然氣作爲原料，使owe變化而產生 一氧化碳氣體之結果圖。 圖8係顯示本發明之產生滲碳氛圍氣體裝置之一實施 形態圖。 圖9係顯示本發明之滲碳裝置之一實施形態圖。 圖1 〇係顯示〇2/C經變化而產生滲碳用氣體之結果圖 〇 圖1 1係顯示H20/C經變化而產生滲碳用氣體之結果 圖。 【主要元件符號說明】 1 :反應器 2 :高壓筒 3 :脫硫器 4 :流量調節器 5 :碳化氫預熱加熱器 6 :碳化氫供給管路 7 :氧高壓筒 8 :流量調節器 9 :氧供給管路 10 :泵 11 :流量調節器 1 2 :蒸氣加熱器 1 3 :水蒸氣供給管路 -46 - 200906720 1 4 :混合氣體流路 1 5 :原料氣體供應管路 1 6 :預熱加熱器 1 7 :流量控制機 1 8 :溫度控制機 1 9 :啓動加熱器 20 :冷卻器 2 1 =氣液分離器 30:產生滲碳用氛圍氣體之裝置 3 1 :氛圍氣爐 3 2 :外殼 3 3 :加熱器 34 :內容器 3 5 :氣體導入管 3 6 ‘·排氣管 3 7 :馬達 38 :風扇 4 0 :被處理物 41 :籠 43 :真空泵 44 :排氣處理裝置 46 :高壓筒 47 :流量計 48 :閥 -47 - 200906720 5 0 :氣體滲碳裝置 51 :反應器 5 2 :壓縮機 5 3 :脫硫器 54 :流量調節閥 5 5 :碳化氫預熱加熱器 5 6 :碳化氫供給管路 5 7 :純水加熱器 5 8 :流量調節閥 5 9 :氧供給管路 6 0 ··泵 6 1 :流量調節閥 62 =蒸氣加熱器 6 3 :水蒸氣供給管路 64 :混合氣體流路 6 5 :原料氣體供給管路 66 =預熱加熱器 67 :水蒸氣導入管路 68 =溫度控制器 6 9 :啓動馬達 70 :流量調節閥 7 1 :氣液分離器 72 :改質氣體管路 73 :第一 PSA裝置 200906720 74 :第二PSA裝置 76 :第一熱交換器 7 7 :第二熱交換器 7 8 :第三熱交換器 7 9 :吸附塔 80 :真空泵 8 1 :吸附塔 8 2 :真空泵 83 :緩衝槽 8 4 :壓縮機 8 5 :製品槽 8 6 :循環壓縮機 8 7 :純水吹入器 8 8 :純水導入管路 90 :氫導入管路 9 1 :流量調節閥 1〇〇:產生一氧化碳氣體之裝置 -49 -The Rh is carried out by impregnating an aqueous solution of a water-soluble salt of Rh, followed by drying, firing, and hydrogen reduction. Further, the Pt is carried out by impregnating an aqueous solution of a water-soluble salt of Pt, followed by drying, firing, and hydrogen reduction. The simultaneous storage of N i and C e Ο 2 is carried out by impregnating a mixed aqueous solution of a water-soluble salt of N i and a water-soluble salt of Ce, followed by drying, firing, and hydrogen reduction. By the order listed above, the target-modified Rh-modified (Ni-Ce〇2)-Pt catalyst is obtained. The composition of each component should be set to Rh: Ni : Ce02 : Pt = ( 0.05 - 0.5 ) : ( 3.0-10.0 ) : ( 2.0 - 8.0 ) : ( 0.3 - 5.0 ) , more preferably Rh : Ni :Ce02:Pt=( 0.1-0.4 ) : ( 4.0-9.0 ) : ( 2.0-5.0 ) : ( 0.3-3.0 ). Further, the hydrogen reduction treatment in each of the above stages may be omitted, and the catalyst may be used after high-temperature hydrogen reduction in actual use. When the hydrogen reduction treatment is carried out at each stage, the catalyst can be further used after high-temperature hydrogen reduction at the time of use. The carburizing atmosphere gas obtained as described above is cooled by the cooler 20, and the water is removed by the gas-liquid separator 21, and then introduced into a carburizing furnace. Fig. 9 is a view showing an example of a gas carburizing device 50 of the apparatus 30 for generating an atmosphere gas for carburizing. The gas carburizing apparatus 50 is provided with a hydrocarbon gas-oxygen gas-36-200906720 and a steam-catalyst reaction to generate a combustion reaction and a conversion reaction of a hydrocarbon-based gas, thereby generating hydrogen-rich carbon monoxide. The reactor 1 for the atmospheric gas for carburizing having a high gas concentration, and the atmosphere gas furnace 31 for introducing the atmospheric gas for carburization obtained by the reactor 1 described above. Then, the atmosphere gas furnace 31 is provided with a fluorine-based gas introduction mechanism that introduces a fluorine-based gas, and the object to be treated is heated in a fluorine-based gas atmosphere to form a fluoride film, and then introduced into the reactor 1 and then introduced into the reactor 1. The carburizing is performed by carburizing with an atmosphere gas and heating. In the gas carburizing apparatus 50, the workpiece 40 is heated in a fluorine-based atmosphere to perform a fluorination treatment to form a fluoride film, and then introduced into the hydrocarbon-based gas, the oxygen-based gas, the water vapor, and the catalyst. The catalytic reaction generates a combustion reaction of a hydrocarbon gas and a carburizing atmosphere gas rich in hydrogen gas and having a high concentration of carbon monoxide gas obtained by the conversion reaction, and is heated to perform carburization treatment. More specifically, in the drawings, reference numeral 31 denotes an atmosphere furnace, comprising a casing 32, an inner container 34 formed inside as a processing chamber, and a heater 33 provided between the inner container 34 and the outer casing 32. The gas introduction pipe 35 and the exhaust pipe 36 are connected to the inner container 34. The gas introduction pipe 35 communicates with the device 30 for generating the carburizing atmosphere gas and the high pressure cylinder 46 of the N2 + NF3 charged with the fluorination gas. 47 is a flow meter, and 48 is a valve. In this example, the high-pressure cylinder 46 and the flow meter 47 are connected to the flow path of the gas introduction pipe 35, etc., to constitute the fluorine gas introduction means. Further, an exhaust gas treatment device 44 and a vacuum pump 43 are connected to the exhaust pipe 36. Thereby, the processing gas -37-200906720 is introduced into the processing chamber in the inner container 34 and discharged. In the above-mentioned processing chamber, a fan 38 to which a motor 37 capable of stirring a process gas is attached is provided. 41 is a cage 41 in which the workpiece 40 to be processed is loaded. In the atmosphere gas furnace 31, for example, the fluorine-based gas such as NF3 connected to the high-pressure cylinder 46 and introduced into the high-pressure cylinder 46 is introduced into the atmosphere gas furnace 3 1 and heated while being subjected to fluorination treatment. The exhaust pipe 36 draws out its gas by the action of the vacuum pump 43, and is non-toxic in the exhaust gas treatment device 44 and discharged to the outside. Subsequently, the carburizing treatment is performed by the carburizing gas generated by the above-described carburizing atmosphere gas device 30, and then the gas is discharged to the outside via the exhaust pipe 36 and the exhaust gas treatment device 44. By this series of operations, the gas carburizing apparatus 50 performs fluorination treatment and carburization treatment. Although various metal materials can be used as the material of the material 40 to be processed, an iron-based metal material is particularly preferably used. It is particularly preferable to use an austenitic metal typified by an austenitic stainless steel. The austenitic stainless steel is exemplified by, for example, an austenitic stainless steel containing 50% by weight or more of an iron component and 12% by weight or more of a chromium component containing nickel. Specific examples include a 1 8 - 8 series stainless steel material such as SUS304, SUS316, and SUS303S, or US 310S or 309 containing a chromium oxide of 25 wt% and a nickel content of 20 wt%, and further exemplified by a chromium content of 23 The weight% and molybdenum contain 2% by weight of austenite-pure iron 2-phase stainless steel or the like. Further, a heat-resistant steel cast steel containing SCH21 or SCH22 having a nickel content of 19 to 22% by weight, a chromium content of 20 to 27% by weight, and a carbon content of 0.25 to 0.45 wt% may also be suitably used as the austenitic stainless steel of the present invention. . Further, it contains 20 to 22% by weight of chromium, 3.2 to 4.5% by weight of nickel, and 8 to 10% by weight of manganese -38 to 200906720 'SUH35 of carbon 〇48 to 0.58% by weight, or contains chromium 13.5. A heat resistant steel such as ~16% by weight, a nickel of 24 to 27% by weight, and a molybdenum of 1 to 1.5% by weight of SUH660 or the like can also be suitably used as the austenitic stainless steel of the present invention. Thus, by using a low carbon containing nickel and chromium, it is also suitable for use as the austenitic stainless steel of the present invention, which can provide excellent corrosion resistance and does not precipitate a chromium compound, and retains a non-magnetic austenitic stainless steel. The surface layer portion forms a carbon solid solution hardened layer, and is a non-magnetic metal product excellent in abrasion resistance or uranium resistance. As described above, the base material used as the workpiece 4 is made of austenitic stainless steel, and by performing the above-described fluorination treatment and carburization treatment, the austenite solid formed on the base material at least in the surface layer portion can be formed. A carbon solid hardening layer having a carbon hardness higher than that of the base material. Here, the above fluorination treatment will be described in detail. The fluorine-based gas used in the above fluorination treatment is exemplified by a fluorine-based compound gas composed of nf3, bf3, CF4, HF, SF6, C2F6, WF6, CHF3, SiF4, C1F3 or the like. These may be used singly or in combination of two or more. Further, a fluorine-based gas containing fluorine in the molecule other than the above-mentioned gases can also be used as the fluorine-based gas of the present invention. Further, these gas-based gas compounds may be used as the above-mentioned atmosphere gas by F2 gas generated by thermal decomposition of a thermal decomposition apparatus or a previously prepared gas of :2. These fluorine compound gases and f2 gases may be used in combination. Among them, NF3 is the most practical among the fluorine-based gases used in the present invention. The NF3 is gas-formed at room temperature, has high chemical stability, and is easy to handle. These NF3 gases are generally used in a specific concentration range in combination with the -39-200906720% gas combination as described later. The various fluorine-based gases exemplified above may be used alone or in combination with an inert gas such as N2 gas. The concentration of the fluorine gas itself in the diluted gas is, for example, 10,000 to 100,000 ppm', preferably 20,000 to 70,000 ppm, more preferably 30,000 to 50,000 ppm, based on the volume. The fluorination treatment using the fluorine-based gas as the atmosphere gas is carried out by using an atmosphere gas furnace 31 like a muffle furnace, and the untreated processed material 40 is placed in the furnace under the fluorine gas atmosphere of the above concentration. The heating is maintained by this. In this case, the heating is carried out by, for example, maintaining the object to be treated 40 composed of austenitic stainless steel at 1,800 to 600 ° C, preferably at 200 to 450 ° C. The holding time of the workpiece 40 in the fluorine-based gas atmosphere is usually set to 1 minute to several hours. By subjecting the workpiece 40 to heat treatment in such a fluorine-based gas atmosphere, the non-acting film containing Cr204 formed on the surface of the austenitic stainless steel is changed into a fluorinated film. The above-mentioned inactive film is not likely to be carburized in the past, but by performing the fluorination treatment, the above-mentioned inactive film changes to a fluoride film. It is considered that the fluorinated film is more likely to be infiltrated by carbon atoms used in carburization than the non-active film, and the surface of the austenitic stainless steel is subjected to the above-mentioned fluorination treatment to become a surface state in which carbon atoms are easily permeable. Next, the surface of the above austenitic stainless steel is carburized at the same time as and/or after the above fluorination treatment. In the carburizing treatment, the austenitic stainless steel itself is heated at a carburizing temperature of 680 ° C or lower -40 to 200906720, and the above-mentioned carburizing gas is used in a furnace gas in a gas atmosphere for carburizing. In the gas atmosphere for carburizing, the carbon source gas such as propane gas may be rich as needed. Therefore, the carburization treatment of the present invention can be carried out in an extremely low temperature range as compared with the previously known carburization treatment. The temperature during the carburizing treatment, that is, the carburizing temperature is 680 ° C or less, that is, preferably 400 to 68 (TC temperature. If the carburizing temperature exceeds 680 ° C, due to the mother of the austenitic stainless steel The material itself softens, and the carburized carbon atoms are combined with the solid-melting chromium to produce chromium carbides. The amount of chromium contained in the base material itself reduces the uranium resistance of the surface layer to a large extent to invade the solid solution. In the state of the carbon layer, the amount of carbon is reduced, the strength of the base material or the corrosion resistance is lowered, and the magnetic properties are increased. For the same reason, the temperature of the carburization treatment is preferably in the range of 400 to 600 t: The temperature range of 400 to 5 50 ° C, preferably 45 0 to 500 ° C. In the present invention, by performing the above-mentioned fluorination treatment, carburization treatment in such an extremely low temperature is possible in the carburization treatment. Almost no chromium carbide particles are formed, and carbon invades and solidifies in the base material to increase the crystal lattice size and form a carbon solid hardening layer on the surface layer. By doing so, the carbon diffuses and penetrates in the surface portion of the austenitic stainless steel. Deep and uniform formation of carbon solid hardening In the austenite phase of the base phase, the carbon diffusion layer is in a state in which a large amount of C atoms invade and solidify to cause lattice expansion, and the hardness is remarkably improved as compared with the base material, and the carbon atoms are hardly related to the base material. The chromium in the form forms a carbide such as Cr7C3 or Cr23C6 and is intrinsically solidified in the crystal lattice, so that the carbon solid solution layer is substantially free of -41 - 200906720 chromium carbide particles and the molten chromium in the base material The amount does not decrease, so it can maintain the same degree of corrosion resistance as the base material. In addition, the surface roughness of the austenitic stainless steel subjected to carburization as described above hardly deteriorates, and there is no dimensional change due to expansion. Produces magnetism. Therefore, the surface roughness is reduced or the dimensional change is small, and the surface modification can be performed with better precision. In the 'austenitic stainless steel, especially the stable austenitic stainless steel containing a large amount of nickel or containing molybdenum The stability of the austenitic stainless steel, the corrosion resistance of the carbon diffusion layer is better. The carburizing treatment can be started after the fluorination treatment, and the carburization treatment can be started simultaneously with the start of the fluorination treatment. After the fluorination treatment is started, the carburization treatment is started after the completion of the carburization treatment. After the fluorination treatment is completed, the carburization treatment is performed, and the surface treated with the fluorination treatment can be compared with pure carburization. The atmospheric gas diffuses and permeates more carbon atoms, and is advantageous when the surface strength is high and the hardening depth is increased, because the surface hardness is effectively increased. The boring treatment is started, and the fluorination treatment is started. The surface diffusion of fluorination generally proceeds to diffuse carbon, and is advantageous when the surface strength is high and the depth of hardening is increased. As described above, the apparatus and method for generating an atmosphere for carburizing in the present embodiment, by using hydrogen carbide The gas, the oxygen gas, and the water vapor are catalytically reacted with the catalyst, and a combustion reaction and a conversion reaction of the hydrocarbon gas are simultaneously generated to generate a carburizing atmosphere gas rich in hydrogen gas and having a high concentration of carbon monoxide gas. As described above, since the oxygen-based gas is used as the raw material without using air, an atmosphere for carburizing having a high carbon potential can be obtained. Further, since steam-42-200906720 is used as a raw material, the explosion limit can be lowered and the safety can be greatly improved as compared with a device using only hydrocarbon gas and oxygen as a raw material. Therefore, the reactor structure itself can be simplified as compared with a device in which oxygen is introduced from the introduction line of the system, and the occurrence of a medium having a disordered oxygen concentration or deterioration of a catalyst can be greatly reduced. Further, the cost of the raw material gas is also relatively low, and the carburizing gas having a high carbon potential can be generated at a low cost and safely. Further, an atmosphere rich in H2 gas can be obtained, and unreacted carbon particles in the carburization treatment step can be suppressed. When the raw material gas system is mixed with water vapor in advance, and the oxygen gas is combined with the oxygen gas and introduced into the reactor 1, the mixing of the hydrocarbon gas of the combustible gas with the oxygen gas can be shortened. The flow path through which the gas passes is advantageous in terms of safety. In the above-mentioned raw material gas system, when the oxygen-based gas and the steam are mixed in advance, and the hydrocarbon gas is combined with the hydrocarbon gas and introduced into the reactor 1, the mixed gas of the hydrocarbon-based gas in which the combustible gas is combined is used. As the oxygen concentration becomes lower, the explosion limit is further reduced, which is advantageous in terms of safety. The raw material gas is configured such that the molar ratio 02/C of C in the oxygen-based gas and the hydrocarbon-based gas is 0.3 or more and 0.5 or less, and H20 in the steam and C in the hydrocarbon-based gas. When the ratio of the hydrocarbon gas to the oxygen gas and the water vapor is set to be a ratio of the molar ratio of H20/C to 0.3 or less, the concentration of C 0 in the carburized gas formed is high, and the carbon potential is high. Atmosphere gas. When the supply amount of the raw material gas is controlled so as to automatically change the supply amount of the oxygen-based gas and the water in accordance with the fluctuation in the supply amount of the hydrocarbon-based gas, a carburizing gas having a substantially constant CO concentration is often obtained, so that the carburizing gas is obtained. -43- 200906720 The amount of volume generated can be changed. In the reactor 1 described above, by using a Rh-modified (Ni-Ce〇2)-Pt catalyst, the combustion reaction of the hydrocarbon-based gas and the conversion reaction are simultaneously carried out in the same reaction zone, by allowing an exothermic reaction. The conversion reaction between the combustion reaction and the endothermic reaction proceeds simultaneously in the same reaction zone, and since the heat energy generated by the combustion reaction can be utilized as a heat source for the conversion reaction, it is extremely energy-efficient. Further, an exothermic reaction and an endothermic reaction occur simultaneously in the reaction zone, so that heat neutralization can be caused and the operation can be performed in a state of thermal equilibrium. Therefore, it is possible to suppress the temperature rise of the reaction zone as compared with the case where the catalyst combustion reaction is separately performed in the reactor 1, for example, the selection of the heat resistant material used in the reactor 1 or the heat resistant structure of the reactor 1 itself is Not so high temperature specifications are sufficient to use 'and therefore can save equipment costs. In addition, the temperature of the material gas supplied to the inlet of the catalyst layer can be lowered, and coal can be suppressed from being thermally decomposed by the decomposition of hydrocarbon, and the risk of fire can be avoided. The preheating heater 16 for preheating the raw material gas introduced into the reactor 1 is controlled by the preheating heater 16 when the temperature of the raw material gas supplied to the reactor 1 is controlled to 300 to 45 ° C. Operate efficiently in a state of thermal equilibrium. [Embodiment 2] FIG. 10 is a view showing the apparatus 30 for generating an atmosphere gas for carburizing, wherein the enthalpy of the oxygen-based gas in the raw material and the molar ratio of C to 02/C in the hydrocarbon-based gas are used for carburization. The result of the gas. Further, at this time, H20/C was set to 0.20', and the supply temperature of the material gas was set to 450 °C. -44 - 200906720 As can be seen from the figure, when 〇2/C is set to 0.3 or more and 〇·5 or less, the concentration of CO in the generated reform gas becomes high, and a carbonized gas having a high carbon potential can be obtained. Fig. 11 shows the result of the carburization gas generated by the change of the molar ratio H2〇/C of c in the water vapor in the raw material and the molar ratio H2〇/C of c in the carbonized ammonia-based gas in the apparatus 30 for generating the carburizing atmosphere gas. . Further, at this time, 〇2/C is set to 0.40, and the supply temperature of the material gas is set to 45 〇〇c 0. From the figure, it can be understood that 'the conversion gas generated when H2〇/C is set to 0·3 or less The CO concentration becomes high, and a carburizing gas having a high carbon potential can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an embodiment of a device for producing carbon monoxide gas of the present invention. Fig. 2 is a view showing a second embodiment of the apparatus for producing carbon monoxide gas of the present invention. Fig. 3 is a view showing an embodiment of the apparatus for producing carbon monoxide gas of the present invention. Fig. 4 is a graph showing the results of producing carbon monoxide gas by changing H2〇/c using propane as a raw material. Fig. 5 is a graph showing the results of producing carbon monoxide gas by changing 〇2/c using propylene carbonate as a raw material. Fig. 6 is a graph showing the results of producing carbon monoxide gas by using natural gas as a raw material to change H2〇/c. ' 45 - 200906720 Figure 7 shows the results of using natural gas as a raw material to change the owe to produce carbon monoxide gas. Fig. 8 is a view showing an embodiment of the apparatus for producing a carburizing atmosphere of the present invention. Fig. 9 is a view showing an embodiment of a carburizing device of the present invention. Fig. 1 shows the results of the carburizing gas produced by the change of 〇2/C. 〇 Figure 1 1 shows the result of the carburization gas produced by the change of H20/C. [Explanation of main components] 1 : Reactor 2 : High pressure cylinder 3 : Desulfurizer 4 : Flow regulator 5 : Hydrocarbon preheating heater 6 : Hydrocarbon supply line 7 : Oxygen high pressure cylinder 8 : Flow regulator 9 : Oxygen supply line 10 : Pump 11 : Flow regulator 1 2 : Steam heater 1 3 : Water vapor supply line - 46 - 200906720 1 4 : Mixed gas flow path 1 5 : Raw material gas supply line 1 6 : Pre Heater 1 7 : Flow controller 1 8 : Temperature controller 1 9 : Starter heater 20 : Cooler 2 1 = Gas-liquid separator 30 : Device for generating atmospheric gas for carburizing 3 1 : Atmosphere gas furnace 3 2 : Housing 3 3 : Heater 34 : Inner container 3 5 : Gas introduction pipe 3 6 '·Exhaust pipe 3 7 : Motor 38 : Fan 4 0 : Object 41 : Cage 43 : Vacuum pump 44 : Exhaust treatment device 46 : High pressure cylinder 47: Flow meter 48: Valve - 47 - 200906720 5 0 : Gas carburizing device 51 : Reactor 5 2 : Compressor 5 3 : Desulfurizer 54 : Flow regulating valve 5 5 : Hydrocarbon preheating heater 5 6 : Hydrocarbon supply line 5 7 : Pure water heater 5 8 : Flow regulating valve 5 9 : Oxygen supply line 6 0 · · Pump 6 1 : Flow regulating valve 62 = Steam heater 6 3: Water vapor supply line 64: Mixed gas flow path 6 5: Raw material gas supply line 66 = Preheating heater 67: Water vapor introduction line 68 = Temperature controller 6 9 : Starter motor 70: Flow regulating valve 7 1 : gas-liquid separator 72 : reforming gas line 73 : first PSA unit 200906720 74 : second PSA unit 76 : first heat exchanger 7 7 : second heat exchanger 7 8 : third heat exchanger 7 9 : adsorption tower 80 : vacuum pump 8 1 : adsorption tower 8 2 : vacuum pump 83 : buffer tank 8 4 : compressor 8 5 : product tank 8 6 : recycle compressor 8 7 : pure water blower 8 8 : pure water introduction Line 90: Hydrogen introduction line 9 1 : Flow regulating valve 1〇〇: Device for generating carbon monoxide gas -49 -