200911363 九、發明說明 【發明所屬之技術領域】 本發明係關於含氧碳氫化合物改質用觸媒、使用其製 造氫或合成氣體之方法及燃料電池系統。各詳細而言，本 發明係經由將含銅之具有尖晶石結構之金屬氧化物、與固 體酸的混合物，在含有氧的氣體環境下以特定的溫度燒成 處理的步驟而調製成的含氧碳氫化合物改質用觸媒；使用 此改質用觸媒對含氧碳氫化合物施以各種改質，有效率製 地造氫或合成氣體之方法；以及利用此改質用觸媒之燃料 電池系統。 【先前技術】 合成氣體，係由一氧化碳與氫所形成，使用於作爲甲 醇合成、羰基（0X0 )合成、費-托合成等之原料氣體以 外’廣泛地使用於作爲氨合成或各種化學製品的原料。 此合成氣體，可藉由先前技術之煤經氣化的方法、或 者以天然氣體等作爲原料之碳氫化合物類的水蒸氣改質法 或部份氧化改質法等而製造。惟，碳的氣化方法中，除了 需要複雜且高價的煤氣化爐，亦會有演變成大'規模的設備 等問題。此外，碳氫化合物類的水蒸氣改質法，因爲反應 伴隨著大量吸熱，故除了反應的進行需要700〜1200 °c左 右的高溫’需要特殊的改質爐之外，亦會有所使用的觸媒 被要求高耐熱性等問題。而且’碳氫化合物類的部份氧化 改質中’因爲需要高溫’故會有需要特殊的部份氧化爐， -5- 200911363 此外因爲隨著反應生成大量的煤，故除了此處理成爲問題 之外，亦會有觸媒易劣化等問題。 在此，爲了解決此問題，近年，嘗試使用二甲基醚（ DME)等之含氧碳氫化合物作爲原料，對其施加各種的改 質，製造合成氣體。另一方面，近年，因爲環境問題而使 新能源技術受到注目，焦點集中在作爲此新能源技術之一 的燃料電池。 此燃料電池，係藉由使氫與氧進行電化學反應，使化 學能變換爲電能，具有能源的利用效率高的特徵，作爲民 生用、產業用或汽車用等之實用化硏究正積極地進行。此 外，發電效率高、最近注目度高的固體氧化物形燃料電池 ，除了氫以外亦可利用一氧化碳。作爲此燃料電池的氫源 (固體氧化物形燃料電池中，氫及一氧化碳源），甲醇、 甲烷爲主體之液化天然氣、此天然氣爲主成份之都市天然 瓦斯、以天然氣爲原料之合成液體燃料、而且石油系的石 油腦或燈油等之石油系碳氫化合物的硏究正在進行。 使用此等的石油系碳氫化合物製造氫時，一般而言相 對於該碳氫，觸媒的存在下施以水蒸氣改質處理或自熱改 質處理、部份氧化改質處理等，但此時產生如上述的問題 。所以’即使在氫的製造，使用二甲基醚等的含氧碳氫化 合物作爲原料之方法，進行各種嘗試，關於以二甲基醚等 之含氧碳氫化合物作爲原料，對其施以各種改質而製造氫 或合成氣體時所使用的觸媒，目前爲止亦揭示了各種觸媒 ，其中以使用Cu系的觸媒，作爲改質含氧碳氫化合物之 -6- 200911363 技術，揭示例如使用含Cu觸媒，由含氧碳氫化合物與二 氧化碳製造合成氣體之觸媒及使用其之合成氣體的製造方 法（專利文獻1等）：使用含Cu觸媒，由含氧碳氫化合 物與水蒸氣製造氫之觸媒及使用其之氫的製造方法（專利 文獻2等）：由固體酸上擔載含Cu之金屬者所成的含氧 碳氫化合物改質用觸媒（專利文獻3及4等）：由含Cu 物質與固體酸性物質的混合物所成之含氧碳氫化合物與水 蒸氣製造氫之觸媒及使用其之氫的製造方法（專利文獻5 等）；由.含Cu物質與固體酸性物質的混合物所成之含氧 碳氫化合物與水蒸氣製造合成氣體之觸媒及使用其之合成 氣體的製造方法（專利文獻6等）等。 惟，專利文獻1〜6技術中所使用的Cu系觸媒，皆活 性不足，所以，爲了提昇反應活性而提高反應溫度，則會 有無法避免觸媒劣化之問題。 爲了解決上述問題，提議含有含銅且具有尖晶石結構 之金屬氧化物，或進一步地含有固體酸性物質之含氧碳氫 化合物改質用觸媒（專利文獻7等），但活性尙未謂爲充 足。專利文獻7列舉作爲固體酸性物質之氧化鋁、二氧化 矽•氧化鋁、沸石等，而且記載著以氧化鋁爲佳。此外， 專利文獻8揭示Cu-Zn-Al型甲醇分解型觸媒與混合ZSM-5的觸媒，但與專利文獻7的觸媒比較下，會有易生成觸 媒劣化的原因之焦煤的問題。 另一方面，專利文獻9，以改質用觸媒II的例子的而 言，揭示將 CuMn擔載於氧化鋁後，經過假燒後以 200911363 5 0 0 ~ 1 0 0 0 °C的溫度進行燒成，但此技術在成爲尖晶石前擔 載於氧化鋁，然後藉由以高溫進行燒成而生成尖晶石，與 尖晶石結構者及氧化鋁混合後燒成之技術在本質上爲不同 者。 專利文獻1 :特開平10- 1 74869號公報 專利文獻2 :特開平1 0- 1 7487 1號公報 專利文獻3 :特開200 1 -96 1 5 9號公報 專利文獻4 :特開200 1 -96 1 60號公報 專利文獻5 :特開2003 - 1 0684號公報 專利文獻6 :特開200 3 -3 3 65 6號公報 專利文獻7 :特開2005 -3 42543號公報 專利文獻8 :特開平9- 1 1 8 50 1號公報 專利文獻9: W02004/103555號文獻（8,9頁） 【發明內容】 [發明所欲解決之課題] 本發明因爲是在如此的狀況下形成，故目的在於提供 更進一步地改良含有銅、且具有尖晶石結構之金屬氧化物 作爲含氧碳氫化合物改質用觸媒的性能，二甲基醚等之含 氧碳氫化合物的改質活性優異，而且持久性提高的改質用 觸媒，及使用此改質用觸媒對含氧碳氫化合物施以各種改 質，有效率地製造氫或合成氣體之方法，以及使用該改質 用觸媒之燃料電池系統。 200911363 [用以解決課題之手段] 本發明者等人，爲了達成上述目的，經過精心硏究的 結果’發現將經由將含銅之具有尖晶石結構之金屬氧化物 與固體酸的混合物，在含有氧的氣體環境下以特定的溫度 燒成處理的步驟調製而成觸媒作爲的含氧碳氫化合物改質 用觸媒，適合此目的。本發明係基於該相關見解而完成之 發明。 亦即，本發明係提供 (1) 一種含氧碳氫化合物改質用觸媒，其特徵係經 由將（A )含銅，且具有尖晶石結構之金屬氧化物、與（ B )固體酸的混合物，在至少含有氧的氣體環境下以 3 0 0〜8 5 0 °C燒成處理的步驟所調製而成。 (2 )如上述（1 )所記載之含氧碳氫化合物改質用觸 媒，其中（A )成份的金屬氧化物，爲從Cu-Fe型尖晶石 、Cu-Mn型尖晶石及Cu-Mn-Fe型尖晶石中所選出的至少 一種。 (3 )如上述（2 )所記載之含氧碳氫化合物改質用觸 媒，其中（A )成份的金屬氧化物，係藉由以500〜l〇〇〇°C 的溫度燒成而得到的C u - F e型尖晶石。 (4)如上述（2)或（3)所記載之含氧碳氫化合物 改質用觸媒，其係至少含有Cu-Fe型尖晶石與固體酸之改 質用觸媒，於射入CuK α線的X射線繞射的測量中，至 少在以下的3個位置具有繞射線’ 2 0=24.1。 、33.2。 、49.6。。 -9- 200911363 (5 )如上述（4 )所記載之含氧碳氫化合物改質用觸 媒，其中上述出現在2 61 = 3 3 · 2 °的繞射線強度、與出現在 2 0=36.1。的CuFe2〇4尖晶石的最強線的繞射線強度之比 ，在0.1〜0.9的範圍。 (6) 如上述（1)〜（5)中任一項所記載之含氧碳氫 化合物改質用觸媒，其中（A )成份的金屬氧化物’含有 從鎳、鈷及鉛族元素之中所選出的至少一種的元素。 (7) 如上述（1) ~(6)中任一項所記載之含氧碳氫 化合物改質用觸媒，其中（B )成份的固體酸爲氧化鋁。 (8) 如上述（7)所記載之含氧碳氫化合物改質用觸 媒’其中（B )成份的固體酸，係藉由以300~750 °C的溫 度燒成所得到的7 —氧化鋁。 (9 )如上述（1 )〜（8 )中任一項所記載之含氧碳氫 化合物改質用觸媒，其中燒成處理步驟中之含氧的氣體環 境’爲空氣環境。 (10) —種含氧碳氫化合物改質用觸媒，其特徵係還 原處理上述（丨）〜（9)中任一項所記載之改質用觸媒而 成。 (1 1 )如上述（1 )〜（1 0 )中任一項所記載之含氧碳 氫化合物改質用觸媒，其中含氧之碳氫化合物爲二甲醚。 (12) —種製造氫或合成氣體之方法，其特徵係使用 上述（1)〜（U)中任一項所記載之改質用觸媒，使含氧 之碳氫化合物進行水蒸氣改質。 (13) —種製造氫或合成氣體之方法，其特徵係使用 -10- 200911363 使用上述（1 )〜（11 )中任一項所記載之改質用觸媒，使 含氧之碳氫化合物進行自熱改質。 (14) —種製造氫或合成氣體之方法，其特徵係使用 使用上述（1 ) ~ ( 11 )中任一項所記載之改質用觸媒，使 含氧之碳氫化合物進行部份氧化改質。 (15) —種製造氫或合成氣體之方法，其特徵係使用 使用上述（1 )〜（11 )中任一項所記載之改質用觸媒，使 含氧之碳氫化合物進行二氧化碳改質。 (1 6 ) —種燃料電池系統，其特徵係具有··具備使用 上述（1 ) ~ ( 1 1 )中任一項所記載之改質用觸媒之改質器 、與以藉由該質器所製造的氫作爲燃料之燃料電池。 [發明之效果] 依據本發明，可提供更進一步地改良含有銅、且具有 尖晶石結構之金屬氧化物作爲含氧碳氫化合物改質用觸媒 的性能，二甲基醚等之含氧碳氫化合物的改質活性優異， 而且持久性提高的改質用觸媒，及使用此改質用觸媒對含 氧碳氫化合物改質用觸媒施以各種改質，有效率地製造氫 或合成氣體之方法，以及使用該改質用觸媒的燃料電池系 統。 [實施發明之最佳形態] 首先，說明關於本發明的含氧碳氫化合物改質用觸媒 -11 - 200911363 [含氧碳氫化合物改質用觸媒] 本發明的含氧碳氫化合物改質用觸媒’係經由將（A )含銅，且具有尖晶石結構之金屬氧化物、與（B )固體 酸的混合物，在至少含有氧的氣體環境下燒成處理的步驟 所調製而成的觸媒。 (含銅之尖晶石結構的金屬氧化物） 本發明中，作爲（A )成份使用之具有尖晶石結構的 金屬氧化物之意，係指被視爲AB 2 04型的金屬複氧化物 之代表的結晶結構型之一且具有立方晶系’在上述ab2o4 中，通常A爲二價的金屬，B爲三價的金屬。 本發明中，作爲如使用含銅之尖晶石結構的金屬氧化 物之金屬氧化物，由觸媒活性及耐熱性等之觀點而言，以 Cu-Mn型尖晶石、Cu-Fe型尖晶石、Cu-Mn-Fe型尖晶石 爲佳。作爲上述Cu-Mn型尖晶石，可列舉例如CuMn204 等；作爲Cu-Fe型尖晶石，可列舉例如CuFe204等；作爲 Cu-Mn-Fe型尖晶石，可列舉 Cu(Mn，Fe)204尖晶石之 Cu(Mn 1' 5 Fe 〇. 5) 〇4、Cu(Mn i.〇Fei.〇)04 ' Cu(Mn2/3Fe4/3)〇4 ' Cu(Mn〇.5Fei .5)〇4 尖晶石等。 此外，CuCr2〇4等之Cu-Cr型尖晶石，可再使用 CuA1204 尖晶石 '或 Cu(FeCr)2〇4、Cu(FeAl)204 尖晶石等 〇 該（A)成份的金屬氧化物，可含有由鎳、鈷及鉑元 -12- 200911363 素中所選出的至少1種的元素’此鎳、鈷及鈾元素亦可如 上述與銅一起具有尖晶石結構，亦可爲與含Cu尖晶石混 合的狀態，再者，鈾族元素包括Pt、RU、Rh、Pd、Ir。 作爲上述鎮或鈷與Cu —起具有尖晶石結構者’可列 舉上述尖晶石的一部份被Ni、Co取代之Cu-Ni-Mn型尖 晶石、Cu-Co-Mn型尖晶石、Cu-Ni-Mn-Fe型尖晶石、Cu-Ni-Fe型尖晶石、Cu-Co-Fe型尖晶石、Cu-Co-Mn-Fe型尖 晶石等。 再者，本發明之改質用觸媒中，作爲（A)成份之含 銅之尖晶石結構的金屬氧化物，可使用在無損於本發明的 目的之範圍，依所望含有非尖晶石結構的含有銅之化合物 者。 接著，關於含銅之尖晶石結構之金屬氧化物的調製方 法的其中一例，列舉調製CuMn2〇4尖晶石的情況進行說 明。 首先’作爲銅源，使用硝酸銅等之水溶性銅鹽，作爲 錳源，使用硝酸錳等之水溶性錳鹽，調製使此等以實質上 化學量論的比例，亦即Cu與Μη的莫耳比，實質上以1 :2含有之水溶液’接著，於此水溶液中，加入枸櫞酸等 之螯合劑後，加熱使水蒸發後生成凝膠。接著，加熱處理 此凝膠’將分解凝膠中的硝酸根或枸櫞酸等而得到的氧化 物微粉末’在空氣中以300〜5〇〇。(：左右的溫度進行卜5小 時左右的假燒後，藉由進一步地以500〜1，000 °C左右的溫 度進行5〜1 5小時左右燒成，可得到由CuMn2〇4尖晶石所 -13- 200911363 成的觸媒。此外以700 °C以上的高溫進行燒成時，據說成 爲Μη203與CiM.5Mm.5O4尖晶石的混合物，但此時亦可作 爲（A)成份使用。 此方法中，可使用銅源，使Cu相對於Μη超過化學 量論的比例，此時，所得到的觸媒，成爲銅的氧化物（ Cu20或CuO或者此等的混合物）與尖晶石型氧化物之混 合物，此物亦可作爲（A )成份使用。 此外，調製由CuFe204尖晶石所成的觸媒時，取代上 述錳源，可使用硝酸鐵等之水溶性鐵鹽等之鐵源。而且， 取代上述錳源，藉由使用鐵源與錳源之混合物，可得到 Cu(FeMn)204尖晶石所成的觸媒，此物當然可作爲（A ) 成份使用。 此等的（A )成份，成型爲一般適當大小的顆粒狀後 使用。 本發明中，作爲（A)成份之含有銅的具有尖晶石結 構之金屬氧化物，上述尖晶可單獨使用一種，亦可組合二 種以上使用，但由觸媒活性觀點而言，特別是藉由以 5 0 0〜1 0 0 0 °C的溫度進行燒成所得到的Cu-Fe型尖晶石較適 合0 (固體酸） 本發明的改質用觸媒中，作爲（B )成份使用之固體 酸之意，係指爲雖然爲固體但顯示出布朗斯台德酸或路易 士酸的特性者，具體而言可列舉氧化鋁、二氧化矽•氧化 -14- 200911363 鋁、二氧化矽•二氧化鈦、沸石、脫氧鬼臼素（ Silicicolin )酸鋁（SAPO )等。此等可使用一種，亦可組 合二種以上使用，但此等中所得到的觸媒的活性之觀點而 言，以氧化鋁較適合。 作爲此固體酸使用之氧化鋁，可使用市售的α、召、 r、c 、0、/c、％的任一者的結晶形態者，此外，亦可 使用燒成勃姆石、鎂磷鋁鈣石、三水鋁礦等之氧化鋁水合 物燒成而成者，除此之外，於硝酸鋁加入pH8~10左右的 鹼緩衝液使其生成氫氧化物，亦可使用使其燒成而成者， 亦可燒成氯化鋁。此外，使異丙氧化鋁等之烷氧化物，溶 解於2 -丙醇等之醇，添加作爲水解用的觸媒之鹽酸等之 無機酸，調製氧化鋁凝膠，可使用藉由使其乾燥、燒成之 溶膠•凝膠法而調製者。 本發明中，作爲（B)成份，可單獨使用一種上述固 體酸，亦可組合二種以上使用，但由觸媒活性的觀點而言 ，特別是以3 0 0〜75〇°c左右的溫度進行燒成所得到的r -氧化鋁較適合。 (燒成處理） 本發明的改質用觸媒，係經由將（A )成份之含銅的 尖晶石結構之金屬氧化物、與（B )成份的固體酸的混合 物’在含有氧的氣體環境下燒成處理的步驟所調製而成。 關於上述（A )成份與（B )成份的混合比例，並沒 有特別的限制’由觸媒活性的觀點而言，在混合物中，作 -15- 200911363 爲銅’通常希望含有1〜50質量％，較佳爲2~3〇質量％的 範圍。 上述混合物的調製法並沒有特別的限制，但可採用各 種的物理的混合方法。 此外’作爲燒成時的氣體環境時，可爲含氧氣體，雖 無特別的限制’但由經濟性等的觀點而言，以空氣環境較 適合。 燒成溫度’由觸媒活性的觀點而言，爲3 〇 〇 ~ 8 5 0。〇， 較佳爲350〜800 °C ’更佳爲在700〜800。(：的範圍內選擇。 低於3 0 0 °C則觸媒活性或持久性的提高效果不足，超過 8 5 0 °C則引起固體酸的凝聚或相變化，變得無法發揮作爲 酸的性能，燒成時間受到燒成溫度的左右，無法一槪地決 疋’但通常爲10分鐘〜5〇小時’較佳爲1〜20小時左右。 此外’本發明的改質用觸媒，在射入CuK α線之X 線繞射的測量中，至少在2 0 4.1。 、3 3.2 ° 、4 9 · 6。的 三個位置上持有繞射線強度者較佳，在此位置上具有繞射 強度’則含氧碳氫化合物的改質能力提高。特別佳係在上 述2 0 =3 3.2 °出現的繞射線強度，與在2 0 =3 6 · 1。出現 的CuFe2〇4尖晶石的最強線之繞射線強度之比在〇.1〜0.9 的範圍之改質用觸媒。 本發明者等人，推測藉由以高溫燒成CuFe尖晶石與 氧化鋁的混合物，生成CuFeAl尖晶石，此可能成爲高活 性的要因。此時，推測因爲尖晶石內的Fe與A1交換，所 擠壓出的Fe以Fe2〇3的形態存在，在2 0 =24.1° 、 -16- 200911363 33.2° 、49.6°上出現新的波峰。 亦即，（i )具有CuFe型尖晶石之含氧碳氫化合物改 質用觸媒，而且此觸媒至少在2 0 =24.1。 、33.2° 、 49.6°上持有X線繞射線強度之觸媒，更佳爲（Π )且在 上述2 Θ = 3 3.2。出現的繞射線強度，與在2 0 = 3 6 1°出 現的 CuFe2〇4尖晶石的最強線之繞射線強度之比在 0·1〜0.9的範圍之改質用觸媒，作爲含氧碳氫化合物改質 用觸媒而言爲優異者。 作爲該相關的具有X線繞射線強度之含氧碳氫化合 物改質用觸媒的製造方法，可列舉將（A )成份之Cu-Fe 型尖晶石、與（B )固體酸的混合物，以700〜800 °C燒成 處理之方法。 (還原處理） 本發明中，如上述作法進行燒成處理後所得到的改質 用觸媒，藉由還原處理，可再提高活性；還原處理，有在 含氫的氣流中處理之氣相還原法、以還原劑處理之濕式還 原方法。上述的還原處理係通常在含氫的氣流下，以 15〇〜500 °c程度，較佳爲200〜400。(：的溫度實施30分鐘 ~2 4小時’較佳爲實施}〜丨〇小時，除了氫氣以外，可使 氮、氦、氬等不活性氣體共同存在。 作爲後者的濕式還原法’具有使用液體氨/醇/Na、液 體氨/醇/Li之Birch還原’使用甲基胺/Li等之Benkesei i 原’以 Zn/HCl、Al/Na0H/H20、NaH、LiAlH4 或其取代 -17- 200911363 物、氫矽烷類、氫化硼鈉或其取代物、乙硼烷、甲酸、甲 醛水、肼等之還原劑處理之方法’此時’以室溫〜1〇〇°c， 進行1 0分鐘~24小時左右，較佳爲進行3 0分鐘〜1 〇小時 者。 此外，藉由使反應原料流動，藉由所生成的氫或CO 在反應中觸媒亦可被還原。 本發明中，觸媒因爲還原前處理或藉由所生成的氣體 被還原，而CU或其他元素從尖晶石結構脫離，雖然尖晶 石結構變成一部份或全部未被保持的狀態，但最初使用具 有尖晶石結構的Cu觸媒這一點爲本發明的重要的要點。 作爲適用於本發明的改質用觸媒之含氧碳氫化合物， 較佳可列舉甲醇、乙醇等之醇類，二甲基醚、甲基乙基醚 等之醚類，其中又以二甲基醚爲特別佳。 本發明的氫或合成氣體的製造方法中，使用上述的本 發明的改質用觸媒使二甲基醚等之含氧碳氫化合物，藉由 (1 )水蒸氣改質、（2 )自熱改質、（3 )部份氧化改質 或（4)二氧化碳改質，製造氫或合成氣體。 接著’關於各改質方法，列舉使用二甲基醚時爲例進 行說明。 [水蒸氣改質] 使用本發明的改質用觸媒時，二甲基醚的水蒸氣改質 ’係依照以下所示的反應式，進行反應。 -18- 200911363 CHOCH + HO 2CHOH ---(1) «3 3 2 3 2CH OH + 2H O 2CO + 6H …（2) 3 2 2 2 2CO + 2H — 2CO + 2HO …⑶ Δ 2 2 所以’製造氫時’只要使上述（3)的反應不易進行 ，亦即只要選擇引起 CH OCH + 3Η Ο — 2CO + 6Η . · · (4) 3 3 2 2 2 的反應之反應條件即可。 另一方面’製造合成氣體，只要使上述（1) 、（2) 及（3 )的反應產生，亦即只要選擇引起 CHOCH + ΗΟ — 2CO + 4Η ---(5) 3 3 2 2 / 的反應之反應條件即可。 製造氫時，水蒸氣/二甲基醚莫耳比，理論上爲3, 3〜6左右較佳，另一方面，製造合成氣體時，水蒸氣/二 甲基醚莫耳比，理論上爲1，1〜2左右較佳。 反應溫度通常在200~500°C，較佳爲在25 0~450°C的 範圍內選擇，此溫度若爲200 °C以上，可抑制二甲基酸的 轉化率的降低，若爲5 0 0 °C以下可防止觸媒的熱劣化。 GHSV (氣體時空間速度），以二甲基醚基準而言爲 50〜5,0001^1 ’更佳爲100〜1 6001Γ1的範圍，此GHSV若爲 501Γ1以上，可抑制生產效率的降低，若爲5,00011-1以下 -19- 200911363 ，可降低二甲基醚的轉化率，此外’反應壓力通常爲常壓 〜IMPa程度，藉由使此壓力在此範圍，可防止二甲基醚的 轉化率的降低。 [自熱改質] 自熱改質反應中，二甲基醚的氧化反應與水蒸氣的反 應，在同一反應器內，或在連續的反應器內引起，此時， 氫製造與合成氣體製造，雖然反應條件有若干差異，但一 般而言，氧/二甲基醚莫耳比，較佳爲在〇·1~1的範圍內 選擇，水蒸氣/二甲基醚莫耳比，較佳爲在0.5〜3的範圍 內選擇，氧/二甲基醚莫耳比若爲〇.1以上，可充分地進 行因爲發熱所產生的反應熱的供給，另一方面若爲1以下 ，可防止完全氧化發生後氫濃度降低。此外，水蒸氣/二 甲基醚旲耳比若爲0.5以上，可抑制氣濃度的降低，另一 方面若爲3以下，可防止發熱的供給變不足。 反應溫度通常在200〜800°C，較佳爲在250~500 °C的 範圍內選擇，此外，關於GHSV及反應壓力，與上述水蒸 氣改質的情況相同。 [部份氧化改質] 部份氧化改質反應，係引起二甲基醚的部份氧化反應 ’氫製造與合成氣體製造係反應條件雖然有若干差異，但 一般而言，氧/二甲基醚莫耳比，較佳爲在0.3^.5的範圍 內選擇，此氧/二甲基醚莫耳比若爲0.3以上，二甲基醚 -20- 200911363 的轉化率可充分地提高，另一方面若爲1.5 弓丨起完全氧化發生而氫濃度降低。反應2 200〜900 °C，較佳爲在250〜600 °C的範圍內 關於GHSV及反應壓力，與上述水蒸氣改質 [二氧化碳改質] 二氧化碳改質反應，係引起二甲基醚與 應’氫製造與合成氣體製造係反應條件雖然 但一般而言’ co2/二甲基醚莫耳比，較佳爲 佳爲在0.9〜1.5的範圍內選擇，此C02/二甲 爲以上，二甲基醚的轉化率可充分地提 若爲2以下，可防止生成物中殘留許多c 0: 低。此反應係可導入水蒸氣，藉由此導入可 此外’關於反應濃度、GHSV及反應壓力， 改質的情況相同。 [燃料電池系統] 本發明的燃料電池系統，係具有具備上 之改質器、與以藉由該改質器所製造的氫作 電池爲其特徵之燃料電池系統，藉由圖1說 發明的燃料電池系統之一例的流程圖。 燃料槽21內的燃料（含氧碳氫化合物 器23(圖1未圖示’但含氧碳氫化合物爲 泵導入）。通常’使用作爲含氧碳氫化合物 以下，可防止 昆度度通常在 選擇，此外， 的情況相同。 二氧化碳的反 有若干差異， 在 0.8〜2 ，更 基醚莫耳比若 咼，另一方面 :、氫的分壓降 提高氫濃度， 與上述水蒸氣 述改質用觸媒 爲燃料之燃料 明，圖1係本 )導入至脫硫 液體時，透過 較適合的二甲 -21 - 200911363 基酸或甲醇時’雖然不含硫，但含有作爲著臭劑（ odorant)之含硫化合物等狀況，脫硫器有效。脫硫器23 中可塡充例如活性碳、沸石或金屬系的吸附劑等，以脫硫 器2 3經脫硫的燃料與從水槽經由水泵24的水混合後，被 導入至氣化器1後經氣化，送至改質器3 1中，改質器3 1 中塡充上述的改質用觸媒，由送至改質器31的燃料混合 物（含氧碳氫化合物及水蒸氣），經由上述水蒸氣改質反 應製造氫。 如上述作法所製造的氫，通過CO交換器32、CO選 擇氧化器33而使CO濃度降低至不會影響燃料電池的特 性的程度爲止，作爲此等反應器所使用的觸媒例子，C 0 交換器32中，使用鐵一鉻系、銅—鋅系、貴金屬系觸媒 ，C 0選擇氧化器3 3中，使用釕系、鉑系觸媒或此等的混 合觸媒，經由改質反應所製造的氫中的C 0濃度低時，亦 可不裝CO交換器32。 燃料電池34係負極34A與正極34B之間具備高分子 電解質34C之固體高分子形燃料電池的例子，負極側中由 上述方法所得到的富氫氣體，正極側中由空氣鼓風機35 送來的空氣，必要時各自可適當地進行加濕處理後（加湯 裝置未圖示）被導入。 此時，負極側氫氣成爲質子，進行釋出電子的反應， 正極側係氧氣得到電子與質子而進行變成水的反應，兩極 34A、34B之間發生直流電流，此時，負極使用鉑黑或活 性碳擔載之Pt觸媒或Pt-Ru合金觸媒等，正極使用鉑黑 -22- 200911363 或活性碳擔載之Pt觸媒等。 負極3 4 A側連接改質器3 1的改質器的燃燒器3 1 A而 以剩餘的氫作爲燃料’此外’正極3 4 B側連接氣水分離器 36，藉由使供給至正極34B側之空氣中的氧與氫的鍵結所 生成的水與排氣氣體分離，將水利用於水蒸氣的生成。燃 料電池34因爲伴隨發電而產生熱，可附設排熱回收裝置 3 7回收此熱而有效利用。排熱回收裝置3 7，具備附設於 燃料電池34吸取反應時所產生的熱之熱交換器37A、與 用於以此熱交換器37A吸取到的熱與水進行熱交換之熱 交換器.37B、與冷卻器37C、與此等交換器37A、3：7B及 使冷媒循環於冷卻器37C之泵37D，在熱交換器37B中 所得到的溫水可有效地利用於其他的設備。 【實施方式】 接著，藉由實施例更詳細地說明本發明，但本發明並 不限定於此等例子。 調製例1 CuFe204尖晶石型氧化物 燒杯中放進硝酸銅（和光純藥工業股份有限公司製’ 99.9%Cu(N03)2· 3H20) 24.184g與硝酸鐵（和光純藥工 業股份有限公司製，99.9% Fe(N03)3 . 9H2〇 ) 80.88 lg， 溶解於蒸餾水成3 0 0 m 1，將其加溫至6 0 °C攪拌2小時。 接著，於此溶液中加入枸櫞酸一水合物（和光純藥工 業股份有限公司製，99.5%C6H807 · 3H20) 92.926g’再 -23- 200911363 以60°C攪拌1小時後，昇溫至90°C後使水蒸發。 如此作法所生成的凝膠的硝酸根及枸櫞酸在空氣中以 140〜200 °C分解，得到氧化物微粉末後，於空氣中以900 °C進行10小時燒成，得到CuFe2〇4尖晶石型氧化物。 調製例2 CuMn204尖晶石型氧化物 燒杯中放進硝酸銅（和光純藥工業股份有限公司製， 99.9% Cu(N03)2 · 3H20) 24.184g 與硝酸錳（Aldrich 公司 製，98%Mn(N03)2. 6H20) 58.588g，溶解於蒸餾水成 3 00ml，將其加溫至60°C攪拌2小時。 接著，於此溶液中加入枸櫞酸一水合物（和光純藥工 業股份有限公司製，99.5%C6H807 · 3H20 ) 92_926g，再 以60°C攪拌1小時後，昇溫至90°C後使水蒸發。 如此作法所生成的凝膠的硝酸根及枸櫞酸在空氣中以 140〜200 °C分解，得到氧化物微粉末後，於空氣中以900 °C進行10小時燒成，得到CuMn204尖晶石型氧化物。 調製例3 CuFei.5MnG.504尖晶石型氧化物 燒杯中放進硝酸銅（和光純藥工業股份有限公司製， 99.9% Cu(N03)2 . 3H20 ) 24.1 84g與硝酸鐵（和光純藥工 業股份有限公司製，99.9%Fe(N03)3· 9H20 ) 60.661 g與 硝酸錳（Aldrich 公司製，98%Μη(Ν03)2· 6H20) 14.647g ，溶解於蒸餾水成3 00m卜將其加溫至60°C攪拌2小時。 接著，於此溶液中加入枸櫞酸一水合物（和光純藥工 -24- 200911363 業股份有限公司製，99.5%C6H807. 3 H20) 92.926g，再 以60 °C攪拌1小時後，昇溫至90 °C後使水蒸發。 如此作法所生成的凝膠的硝酸根及枸櫞酸在空氣中以 140〜200 °C分解，得到氧化物微粉末後，於空氣中以900 °C進行10小時燒成，得到CuFei.5Mn〇.504尖晶石型氧化 物。 實施例1 調製例1所得到的CuFe2〇4尖晶石型氧化物1 〇g，與 以700 °C進行30分鐘燒成的r -氧化鋁（住友化學股份有 限公司製「AKP-G015」）5g以硏鉢混合，藉由將其在含 有1 〇體積％的氫之氮氣中，以6 0 (TC進行3小時還原， 然後，在空氣環境下，以3 5 0 °C進行1 〇小時燒成，調製 改質用觸媒。 實施例2 實施例1中，除了將空氣環境下的燒成條件，變更爲 5 00 °C、1 0小時以外’其餘與實施例1同樣作法調製改質 用觸媒。 實施例3 實施例1中’除了將空氣環境下的燒成條件，變更爲 70 0 °C、1 0小時以外’其餘與實施例1同樣作法調製改質 用觸媒。 -25- 200911363 實施例4 實施例1中，除了將空氣環境下的燒成條件，變更爲 8 00°C、1 〇小時以外，其餘與實施例1同樣作法調製改質 用觸媒。 實施例5 實施例1中，除了將含有10體積％的氫之氮氣中的 還原條件，變更爲3 5 (TC、3小時以外，其餘與實施例1 同樣作法調製改質用觸媒。 實施例6 實施例2中，除了將含有10體積％的氫之氮氣中的 還原條件，變更爲3 5 0 °C、3小時以外，其餘與實施例2 同樣作法調製改質用觸媒。 實施例7 實施例3中，除了將含有1〇體積％的氫之氮氣中的 還原條件，變更爲3 5 0 °C、3小時以外，其餘與實施例3 同樣作法調製改質用觸媒。 實施例8 藉由將實施例7所得到的觸媒以1 0〜1 8 · 5網眼加壓成 型後，將所定量塡充於反應器’於含有體積％的氫之 -26- 200911363 氮氣中，以3 5 0 r進行3小時的還原， 實施例9 實施例4中，除了將含有1〇體積 還原條件，變更爲3 5 0。(：、3小時以外 同樣作法調製改質用觸媒。 實施例1 0BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for upgrading an oxygen-containing hydrocarbon, a method for producing hydrogen or a synthesis gas thereof, and a fuel cell system. In each detail, the present invention is prepared by a step of calcining a mixture of a metal oxide having a spinel structure containing copper and a solid acid in a gas atmosphere containing oxygen at a specific temperature. a catalyst for upgrading an oxygen hydrocarbon; a method of applying various modifications to an oxygen-containing hydrocarbon using the catalyst for reforming, efficiently producing hydrogen or synthesizing a gas; and using a catalyst for the modification Fuel cell system. [Prior Art] The synthesis gas is formed by carbon monoxide and hydrogen and is used as a raw material for ammonia synthesis or various chemical products, other than raw material gases such as methanol synthesis, carbonyl (0X0) synthesis, and Fischer-Tropsch synthesis. . This synthesis gas can be produced by a method of vaporizing coal of the prior art, a steam reforming method using a hydrocarbon such as a natural gas or the like, or a partial oxidation reforming method. However, in the gasification method of carbon, in addition to the complicated and expensive coal gasification furnace, there are problems such as the evolution of large-scale equipment. In addition, since the hydrocarbon-based steam reforming method is accompanied by a large amount of heat absorption, it requires a high temperature of about 700 to 1200 °c in addition to the reaction, and it is also used in addition to a special reforming furnace. The catalyst is required to have problems such as high heat resistance. Moreover, in the partial oxidation reform of hydrocarbons, a special partial oxidation furnace is required because of the high temperature required. -5- 200911363 In addition, since a large amount of coal is generated with the reaction, this treatment becomes a problem. In addition, there will be problems such as the catalyst being easily deteriorated. Here, in order to solve this problem, in recent years, an oxygen-containing hydrocarbon such as dimethyl ether (DME) has been used as a raw material, and various modifications have been applied thereto to produce a synthesis gas. On the other hand, in recent years, new energy technologies have attracted attention due to environmental issues, with a focus on fuel cells as one of the new energy technologies. In the fuel cell, the chemical energy is converted into electric energy by electrochemically reacting hydrogen with oxygen, and the energy utilization efficiency is high, and it is actively used as a practical research for people's livelihood, industrial use, and automobiles. get on. In addition, solid oxide fuel cells with high power generation efficiency and recent high visibility have been able to utilize carbon monoxide in addition to hydrogen. As a hydrogen source of the fuel cell (a source of hydrogen and carbon monoxide in a solid oxide fuel cell), a liquefied natural gas mainly composed of methanol and methane, an urban natural gas mainly composed of the natural gas, a synthetic liquid fuel using natural gas as a raw material, Moreover, research on petroleum-based hydrocarbons such as petroleum brains or kerosene is underway. When hydrogen is produced using such petroleum-based hydrocarbons, in general, in the presence of a catalyst, steam reforming, autothermal reforming, partial oxidation reforming, or the like is applied to the hydrocarbon, but At this time, the problem as described above occurs. Therefore, various attempts have been made to use oxygen-containing hydrocarbons such as dimethyl ether as raw materials in the production of hydrogen, and various types of oxygen-containing hydrocarbons such as dimethyl ether have been used as raw materials. Catalysts used in the production of hydrogen or synthesis gas have been disclosed so far, and various catalysts have been disclosed, in which a Cu-based catalyst is used as a modified oxygen-containing hydrocarbon -6-200911363 technique, for example, A catalyst for producing a synthesis gas from an oxygen-containing hydrocarbon and carbon dioxide using a Cu-containing catalyst, and a method for producing a synthesis gas using the same (Patent Document 1 and the like): using a Cu-containing catalyst, an oxygen-containing hydrocarbon and water Catalyst for producing hydrogen by steam and a method for producing hydrogen using the same (Patent Document 2, etc.): an oxygen-containing hydrocarbon reforming catalyst which is obtained by supporting a metal containing Cu on a solid acid (Patent Document 3 and 4, etc.: a catalyst for producing hydrogen from an oxygen-containing hydrocarbon and a vapor of a mixture of a Cu-containing substance and a solid acidic substance, and a method for producing hydrogen using the same (Patent Document 5, etc.); And solid Manufacturing method (Patent Document 6, etc.), a mixture of the acidic substance into the oxygen-containing hydrocarbons and catalyst for producing synthesis gas of water vapor and its use of the synthesis gas. However, the Cu-based catalysts used in the techniques of Patent Documents 1 to 6 are insufficient in activity. Therefore, in order to increase the reaction temperature and increase the reaction temperature, there is a problem that the catalyst is not deteriorated. In order to solve the above problems, a catalyst containing an oxygen-containing hydrocarbon modified with a metal oxide containing a copper or a spinel structure or a solid acidic substance is proposed (Patent Document 7 and the like), but the activity is not described. To be sufficient. Patent Document 7 lists alumina, cerium oxide, alumina, zeolite, etc., which are solid acidic substances, and it is described that alumina is preferred. Further, Patent Document 8 discloses a catalyst of a Cu-Zn-Al type methanolysis type catalyst and a mixed ZSM-5, but in comparison with the catalyst of Patent Document 7, there is a problem of coking coal which is liable to cause deterioration of the catalyst. . On the other hand, in the example of the catalyst II for reforming, Patent Document 9 discloses that CuMn is supported on alumina, and after calcination, it is carried out at a temperature of 200911363 5 0 0 to 100 ° C. Firing, but this technique is carried on alumina before it becomes spinel, and then spin-forming at high temperature to form spinel, which is mixed with spinel structure and alumina and then fired in nature. For different people. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. 9- 1 1 8 50 No. 1 Patent Document 9: Document No. WO04/103555 (8, 9 pages) [Disclosed] The present invention has been made under such circumstances, and the object is to Provided to further improve the performance of a metal oxide containing copper and having a spinel structure as a catalyst for modifying an oxygen-containing hydrocarbon, and an oxygen-containing hydrocarbon such as dimethyl ether has excellent reforming activity, and a catalyst for improving the durability of the catalyst, a method for applying various modifications to the oxygen-containing hydrocarbon using the catalyst for the modification, a method for efficiently producing hydrogen or a synthesis gas, and a catalyst for using the modifier Fuel cell system. 200911363 [Means for Solving the Problem] The inventors of the present invention, in order to achieve the above object, have found through careful results that a mixture of a metal oxide having a spinel structure containing copper and a solid acid is found. A catalyst for oxygen-containing hydrocarbon reforming, which is prepared by a catalyst at a specific temperature in a gas atmosphere containing oxygen, is suitable for this purpose. The present invention is based on the related findings. That is, the present invention provides (1) an oxygen-containing hydrocarbon upgrading catalyst characterized by (A) a metal oxide containing copper and having a spinel structure, and (B) a solid acid. The mixture is prepared by a step of firing at 300 to 850 ° C in a gas atmosphere containing at least oxygen. (2) The catalyst for modifying an oxygen-containing hydrocarbon according to the above (1), wherein the metal oxide of the component (A) is a Cu-Fe type spinel or a Cu-Mn type spinel. At least one selected from the group consisting of Cu-Mn-Fe type spinels. (3) The catalyst for modifying an oxygen-containing hydrocarbon according to the above (2), wherein the metal oxide of the component (A) is obtained by firing at a temperature of 500 to 1 °C. C u - F e type spinel. (4) The catalyst for modifying an oxygen-containing hydrocarbon according to the above (2) or (3), which contains at least a catalyst for modifying a Cu-Fe type spinel and a solid acid, and is injected therein. In the measurement of the X-ray diffraction of the CuK α line, at least the following three positions have a ray '20 = 24.1. 33.2. 49.6. . -9- 200911363 (5) The catalyst for upgrading oxygen-containing hydrocarbons as described in the above (4), wherein the above-mentioned ray intensity at 2 61 = 3 3 · 2 ° appears at 20 = 36.1 . The ratio of the intensity of the strongest line of the CuFe2〇4 spinel to the ray intensity is in the range of 0.1 to 0.9. (6) The catalyst for modifying an oxygen-containing hydrocarbon according to any one of the above (1) to (5), wherein the metal oxide of the component (A) contains nickel, cobalt and a lead group element. At least one element selected in the middle. (7) The catalyst for modifying an oxygen-containing hydrocarbon according to any one of the above (1), wherein the solid acid of the component (B) is alumina. (8) The solid acid of the (B) component of the catalyst for modifying oxygen-containing hydrocarbons as described in the above (7) is a 7-oxidation obtained by firing at a temperature of 300 to 750 °C. aluminum. (9) The catalyst for modifying an oxygen-containing hydrocarbon according to any one of the above (1) to (8), wherein the oxygen-containing gas atmosphere in the baking treatment step is an air atmosphere. (10) A catalyst for modifying an oxygen-containing hydrocarbon, which is characterized in that the catalyst for reforming according to any one of (1) to (9) above is treated. (1) The catalyst for modifying an oxygen-containing hydrocarbon according to any one of the above (1) to (10), wherein the oxygen-containing hydrocarbon is dimethyl ether. (12) A method for producing hydrogen or a synthesis gas, characterized in that the oxygen-containing hydrocarbon is subjected to steam reforming using the catalyst for reforming according to any one of the above (1) to (U) . (13) A method for producing a hydrogen or a synthesis gas, which is characterized in that the use of the catalyst for reforming according to any one of the above (1) to (11) is carried out to make an oxygen-containing hydrocarbon Perform self-heating modification. (14) A method for producing hydrogen or a synthesis gas, characterized in that the oxygen-containing hydrocarbon is partially oxidized by using the catalyst for reforming according to any one of the above (1) to (11) Upgraded. (15) A method for producing hydrogen or a synthesis gas, characterized in that the oxygen-containing hydrocarbon is subjected to carbon dioxide reforming using the catalyst for reforming according to any one of the above (1) to (11) . (1) A fuel cell system characterized by comprising: a reformer using the catalyst for modifying according to any one of (1) to (1), and The hydrogen produced by the device is used as a fuel cell for fuel. [Effects of the Invention] According to the present invention, it is possible to further improve the performance of a metal oxide containing copper and having a spinel structure as a catalyst for modifying an oxygen-containing hydrocarbon, and oxygen-containing dimethyl ether or the like. The catalyst for reforming which is excellent in the conversion activity of the hydrocarbon, and which has improved durability, and the catalyst for modifying the oxygen-containing hydrocarbon by using the catalyst for reforming, and efficiently producing hydrogen. Or a method of synthesizing a gas, and a fuel cell system using the catalyst for reforming. [Best Mode for Carrying Out the Invention] First, the catalyst for the modification of the oxygen-containing hydrocarbon of the present invention-11-112009363 [catalyst for upgrading an oxygen-containing hydrocarbon] The oxygen-containing hydrocarbon modification of the present invention will be described. The catalytic catalyst is prepared by a step of calcining (A) a metal oxide containing copper and having a spinel structure and a mixture of (B) a solid acid in a gas atmosphere containing at least oxygen. Into the catalyst. (Metal oxide containing a spinel structure of copper) In the present invention, the meaning of the metal oxide having a spinel structure as the component (A) means a metal double oxide which is regarded as an AB 2 04 type. One of the representative crystal structures and has a cubic crystal system. In the above ab2o4, usually A is a divalent metal, and B is a trivalent metal. In the present invention, as a metal oxide of a metal oxide containing a spinel structure containing copper, a Cu-Mn type spinel or a Cu-Fe type tip is used from the viewpoints of catalyst activity and heat resistance. The spar and Cu-Mn-Fe type spinel are preferred. Examples of the Cu-Mn-type spinel include CuMn204 and the like; examples of the Cu-Fe-type spinel include CuFe204; and examples of the Cu-Mn-Fe-type spinel include Cu (Mn, Fe). 204 spinel Cu(Mn 1' 5 Fe 〇. 5) 〇4, Cu(Mn i.〇Fei.〇)04 'Cu(Mn2/3Fe4/3)〇4 'Cu(Mn〇.5Fei .5 ) 〇 4 spinel and so on. In addition, a Cu-Cr type spinel such as CuCr2〇4 may be further oxidized by CuA1204 spinel' or Cu(FeCr)2〇4, Cu(FeAl)204 spinel or the like (A). The material may contain at least one element selected from the group consisting of nickel, cobalt and platinum element-12-200911363. The nickel, cobalt and uranium elements may also have a spinel structure together with copper as described above, or may be In the state in which the Cu-containing spinel is mixed, the uranium element includes Pt, RU, Rh, Pd, and Ir. As the above-mentioned town or cobalt and Cu having a spinel structure, a part of the above spinel may be a Cu-Ni-Mn type spinel substituted with Ni and Co, and a Cu-Co-Mn type spinel. Stone, Cu-Ni-Mn-Fe type spinel, Cu-Ni-Fe type spinel, Cu-Co-Fe type spinel, Cu-Co-Mn-Fe type spinel, and the like. Further, in the catalyst for reforming of the present invention, the metal oxide of the copper-containing spinel structure as the component (A) can be used in the range which does not impair the object of the present invention, and is intended to contain non-spinel. Structure of compounds containing copper. Next, a case where a CuMn2〇4 spinel is prepared as an example of a method of preparing a metal oxide containing a spinel structure containing copper will be described. First, as a copper source, a water-soluble copper salt such as copper nitrate is used, and as a manganese source, a water-soluble manganese salt such as manganese nitrate is used, and the ratio of such a stoichiometric amount, that is, Cu and Μη, is prepared. The ear ratio is substantially an aqueous solution containing 1:2. Then, a chelating agent such as citric acid is added to the aqueous solution, and then heated to evaporate water to form a gel. Next, the gel is subjected to heat treatment to remove the oxide fine powder "obtained by nitrate or citric acid in the gel" by 300 to 5 Torr in the air. (: The left and right temperatures are subjected to a calcination for about 5 hours, and further calcined at a temperature of about 500 to 1,000 °C for about 5 to 15 hours to obtain a spinel from CuMn2〇4. -13- 200911363 The catalyst is formed. When it is fired at a high temperature of 700 °C or higher, it is said to be a mixture of Μη203 and CiM.5Mm.5O4 spinel, but it can also be used as the component (A). In the method, a copper source can be used to make Cu exceed the stoichiometric ratio with respect to Μη. At this time, the obtained catalyst becomes copper oxide (Cu20 or CuO or a mixture thereof) and spinel type oxidation. A mixture of the materials may be used as the component (A). When a catalyst composed of CuFe204 spinel is prepared, an iron source such as a water-soluble iron salt such as iron nitrate may be used instead of the manganese source. Further, instead of the above-mentioned manganese source, a catalyst made of Cu(FeMn)204 spinel can be obtained by using a mixture of an iron source and a manganese source, and this material can of course be used as the component (A). The composition is formed into a pellet of a generally appropriate size and used in the present invention. The metal oxide having a spinel structure containing copper as the component (A) may be used singly or in combination of two or more kinds, but from the viewpoint of catalytic activity, particularly by 5 The Cu-Fe type spinel obtained by firing at a temperature of 0 0 to 1 0 0 ° C is suitable for 0 (solid acid). The solid acid used as the component (B) in the catalyst for reforming of the present invention The term "aluminum, cerium oxide, oxidized-14-200911363 aluminum, cerium oxide, titanium dioxide, etc." Zeolite, Silicicolin Acid Aluminum (SAPO), etc. These may be used alone or in combination of two or more. However, from the viewpoint of the activity of the catalyst obtained in these, alumina is relatively Suitable as the alumina used for the solid acid, a commercially available crystal form of any of α, Z, r, c, 0, /c, and % can be used, and boiled boehmite can also be used. Alumina hydrate sintered by magnesium aluminophosphate, gibbsite, etc. In addition, an alkali buffer having a pH of about 8 to 10 is added to aluminum nitrate to form a hydroxide, which may be used for firing, or may be fired into aluminum chloride. The alkoxide is dissolved in an alcohol such as 2-propanol, and an inorganic acid such as hydrochloric acid as a catalyst for hydrolysis is added to prepare an alumina gel, and a sol/condensation which is dried and fired can be used. In the present invention, as the component (B), one type of the above solid acid may be used alone or two or more types may be used in combination, but from the viewpoint of catalyst activity, in particular, 300 to 75 The r-alumina obtained by firing at a temperature of about 〇 °c is suitable. (Baking treatment) The catalyst for reforming according to the present invention is a gas containing oxygen in a mixture of a metal oxide containing a copper-containing spinel structure of (A) and a solid acid of (B) component. It is prepared by the steps of the firing treatment in the environment. The mixing ratio of the above component (A) to the component (B) is not particularly limited. From the viewpoint of catalyst activity, in the mixture, it is generally desired that the copper is -15-200911363 is 1 to 50% by mass. It is preferably in the range of 2 to 3 % by mass. The preparation method of the above mixture is not particularly limited, but various physical mixing methods can be employed. Further, in the case of a gas atmosphere at the time of firing, the oxygen-containing gas may be used without particular limitation, but it is suitable for an air environment from the viewpoint of economy and the like. The firing temperature is 3 〇 〇 ~ 850 from the viewpoint of catalyst activity. Preferably, it is preferably from 350 to 800 ° C. More preferably from 700 to 800. (: Select within a range of less than 300 °C. The effect of catalyst activity or durability is insufficient. If it exceeds 850 °C, it causes aggregation or phase change of solid acid, and it becomes impossible to exhibit acidity. The firing time is affected by the firing temperature, and it cannot be smashed 'but usually 10 minutes to 5 hours' is preferably about 1 to 20 hours. Further, the catalyst for the modification of the present invention is shot. In the measurement of the X-ray diffraction into the CuK α line, it is preferable to hold the ray intensity at least at the three positions of 2 0 4.1, 3 3.2 °, and 4 9 · 6, and have diffraction at this position. The strength 'increased the ability of oxygen-containing hydrocarbons to improve. Especially the ray intensity of the above 2 0 = 3 3.2 °, and the CuFe2 〇 4 spinel appearing at 20 = 3 6 · 1. The catalyst for the modification of the ratio of the ray intensity of the strongest line in the range of 〇.1 to 0.9. The inventors of the present invention presumed that a CuFeAl spinel was formed by firing a mixture of CuFe spinel and alumina at a high temperature. Stone, this may become the cause of high activity. At this time, it is speculated that the Fe in the spinel exchanges with A1 and is squeezed. Fe exists in the form of Fe2〇3, and new peaks appear at 20 = 24.1°, -16-200911363 33.2°, 49.6°. That is, (i) oxygen-containing hydrocarbons with CuFe-type spinel The catalyst for upgrading is used, and the catalyst has a catalyst for X-ray ray intensity at least at 2 0 = 24.1, 33.2 °, 49.6 °, more preferably (Π) and above 2 Θ = 3 3.2. The intensity of the ray that appears, and the ratio of the ray intensity of the strongest line of the CuFe2〇4 spinel appearing at 20 = 3 6 1° in the range of 0·1 to 0.9, as an oxygen-containing catalyst, as an oxygen-containing catalyst The catalyst for the modification of the hydrocarbon is excellent. As a method for producing the catalyst for modifying an oxygen-containing hydrocarbon having X-ray diffraction intensity, Cu-Fe of the component (A) can be cited. A method of calcining a mixture of a spinel and a solid acid (B) at 700 to 800 ° C. (Reduction treatment) In the present invention, the catalyst for reforming obtained after the calcination treatment as described above is carried out. By reducing treatment, the activity can be further increased; the reduction treatment is carried out by a gas phase reduction method in which a hydrogen-containing gas stream is treated, and a reducing agent is used. The wet reduction method is generally carried out under a hydrogen-containing gas stream at a temperature of from 15 Torr to 500 ° C, preferably from 200 to 400. (The temperature is carried out for 30 minutes to 24 hours) is preferably When it is carried out for ~~ hours, in addition to hydrogen, inactive gases such as nitrogen, helium, and argon may be coexisted. As the latter, the wet reduction method has a use of liquid ammonia/alcohol/Na, liquid ammonia/alcohol/Li, Birch. Reduction of 'Benkesei i original' using methylamine/Li et al. to Zn/HCl, Al/Na0H/H20, NaH, LiAlH4 or its substitution-17-200911363, hydrooxane, sodium borohydride or its substitute, B The method for treating a reducing agent such as borane, formic acid, formalin or hydrazine is carried out at room temperature to 1 〇〇 °c for about 10 minutes to 24 hours, preferably for 30 minutes to 1 hour. By. Further, by flowing the reaction raw material, the catalyst can be reduced by the generated hydrogen or CO in the reaction. In the present invention, the catalyst is detached from the spinel structure due to the pre-reduction treatment or the gas generated by the reduction, although the spinel structure becomes a partially or completely unretained state, The initial use of a Cu catalyst having a spinel structure is an important point of the present invention. The oxygen-containing hydrocarbon to be used in the catalyst for reforming of the present invention is preferably an alcohol such as methanol or ethanol, or an ether such as dimethyl ether or methyl ethyl ether. The base ether is particularly preferred. In the method for producing hydrogen or a synthesis gas of the present invention, the oxygen-containing hydrocarbon such as dimethyl ether is used to modify (1) water vapor by using the catalyst for reforming according to the present invention described above, and (2) Thermal modification, (3) partial oxidation modification or (4) carbon dioxide modification to produce hydrogen or synthesis gas. Next, the description will be made by taking an example of the use of dimethyl ether for each modification method. [Steam reforming] When the catalyst for reforming according to the present invention is used, the steam reforming of dimethyl ether is carried out in accordance with the reaction formula shown below. -18- 200911363 CHOCH + HO 2CHOH ---(1) «3 3 2 3 2CH OH + 2H O 2CO + 6H ... (2) 3 2 2 2 2CO + 2H — 2CO + 2HO ... (3) Δ 2 2 So 'manufacturing In the case of hydrogen, the reaction of the above (3) is not easily carried out, that is, the reaction conditions for the reaction of CH OCH + 3Η Ο 2CO + 6 Η · · · (4) 3 3 2 2 2 may be selected. On the other hand, 'the synthesis gas is produced by the reaction of the above (1), (2) and (3), that is, as long as CHOCH + CO 2CO + 4 Η ---(5) 3 3 2 2 / is selected. The reaction conditions of the reaction may be sufficient. When hydrogen is produced, the water vapor/dimethyl ether molar ratio is theoretically about 3, 3 to 6 or so. On the other hand, when producing a synthesis gas, the steam/dimethyl ether molar ratio is theoretically 1,1~2 or so is preferred. The reaction temperature is usually selected from 200 to 500 ° C, preferably in the range of from 25 to 450 ° C. If the temperature is above 200 ° C, the conversion of dimethyl acid can be suppressed, and if it is 50 Below 0 °C, the thermal deterioration of the catalyst can be prevented. GHSV (gas space velocity) is 50 to 50001^1', more preferably 100 to 16001Γ1, based on dimethyl ether. If the GHSV is 501Γ1 or more, the production efficiency can be suppressed. It is 5,00011-1 or less -19-200911363, which can reduce the conversion rate of dimethyl ether. In addition, the reaction pressure is usually from atmospheric pressure to IMPa. By making this pressure within this range, dimethyl ether can be prevented. Reduced conversion rate. [self-heating modification] In the self-heating reforming reaction, the oxidation reaction of dimethyl ether with water vapor is caused in the same reactor or in a continuous reactor. At this time, hydrogen production and synthesis gas production Although there are some differences in the reaction conditions, in general, the oxygen/dimethyl ether molar ratio is preferably selected within the range of 〇·1 to 1, and the water vapor/dimethyl ether molar ratio is preferably. When it is selected in the range of 0.5 to 3, if the oxygen/dimethyl ether molar ratio is 〇.1 or more, the supply of reaction heat due to heat generation can be sufficiently performed, and if it is 1 or less, it can be prevented. The hydrogen concentration decreases after complete oxidation occurs. Further, when the water vapor/dimethyl ether oxime ratio is 0.5 or more, the gas concentration can be suppressed from decreasing, and if it is 3 or less, the supply of heat can be prevented from becoming insufficient. The reaction temperature is usually selected from the range of 200 to 800 ° C, preferably 250 to 500 ° C, and the GHSV and the reaction pressure are the same as those of the above-described water vapor reforming. [Partial oxidative upgrading] Partial oxidative upgrading reaction, which causes partial oxidation of dimethyl ether. 'Hydrogen production and synthesis gas production system. Although there are some differences in reaction conditions, in general, oxygen/dimethyl The ether molar ratio is preferably selected within the range of 0.3^.5. If the oxygen/dimethyl ether molar ratio is 0.3 or more, the conversion of dimethyl ether-20-200911363 can be sufficiently improved. On the one hand, if the 1.5 yoke is completely oxidized, the hydrogen concentration is lowered. The reaction 2200~900 °C, preferably in the range of 250~600 °C, regarding the GHSV and the reaction pressure, and the above-mentioned steam reforming [carbon dioxide upgrading] carbon dioxide upgrading reaction, causing dimethyl ether and 'Hydrogen production and synthesis gas production system reaction conditions, although generally 'co2 / dimethyl ether molar ratio, preferably preferably selected in the range of 0.9 to 1.5, this CO 2 / dimethyl is above, dimethyl The conversion ratio of the ether can be sufficiently 2 or less to prevent a large amount of c 0 : low remaining in the product. In this reaction, water vapor can be introduced, and the introduction can be carried out in the same manner as in the case of the reaction concentration, GHSV and reaction pressure. [Fuel Cell System] The fuel cell system of the present invention has a fuel cell system including a reformer and a hydrogen battery produced by the reformer, and is invented by FIG. A flow chart of an example of a fuel cell system. The fuel in the fuel tank 21 (oxygen-containing hydrocarbon device 23 (not shown in Fig. 1 but the oxygen-containing hydrocarbon is introduced as a pump). Usually used as an oxygen-containing hydrocarbon, it is possible to prevent the degree of the degree of the The choice, in addition, is the same. There are several differences in the carbon dioxide reaction, at 0.8~2, the more ether ether molar ratio, on the other hand: the hydrogen partial pressure drop increases the hydrogen concentration, and the above water vapor reform The catalyst-fueled fuel is shown in Fig. 1 when it is introduced into the desulfurization liquid. When it is passed through a suitable dimethyl-21 - 200911363 acid or methanol, it contains sulfur as a odorant. The desulfurizer is effective in the case of sulfur compounds. The desulfurizer 23 may be filled with, for example, activated carbon, zeolite or a metal-based adsorbent, etc., and the desulfurized fuel of the desulfurizer 23 is mixed with water from the water tank via the water pump 24, and then introduced into the gasifier 1 After being gasified, it is sent to the reformer 31, and the reformer 3 1 is charged with the above-mentioned catalyst for reforming, and the fuel mixture (oxygen-containing hydrocarbon and water vapor) sent to the reformer 31 is used. Hydrogen is produced via the above steam reforming reaction. The hydrogen produced by the above method is controlled by the CO exchanger 32 and the CO selective oxidizer 33 to reduce the CO concentration to such an extent that the characteristics of the fuel cell are not affected. As an example of the catalyst used in the reactors, C 0 In the exchanger 32, an iron-chromium-based, copper-zinc-based, or noble-metal catalyst is used, and in the C 0 selective oxidizer 33, a lanthanide, a platinum-based catalyst, or a mixed catalyst thereof is used, and a reforming reaction is carried out. When the concentration of C 0 in the produced hydrogen is low, the CO exchanger 32 may not be installed. The fuel cell 34 is an example of a solid polymer fuel cell including a polymer electrolyte 34C between the negative electrode 34A and the positive electrode 34B, the hydrogen-rich gas obtained by the above method on the negative electrode side, and the air sent from the air blower 35 on the positive electrode side. If necessary, each of them can be appropriately subjected to humidification treatment (the soup addition device is not shown). At this time, the hydrogen gas on the negative electrode side becomes a proton, and a reaction for releasing electrons is performed. On the positive electrode side, oxygen is obtained by electrons and protons, and a reaction becomes water. A direct current flows between the two electrodes 34A and 34B. In this case, platinum black or active is used for the negative electrode. Carbon-supported Pt catalyst or Pt-Ru alloy catalyst, etc., and the positive electrode uses platinum black-22-200911363 or activated carbon-supported Pt catalyst. The negative electrode 3 4 A side is connected to the burner 3 1 A of the reformer of the reformer 3 1 and the remaining hydrogen is used as the fuel 'further' the positive electrode 3 4 B side is connected to the gas-water separator 36, and is supplied to the positive electrode 34B. The water generated by the bonding of oxygen and hydrogen in the air on the side is separated from the exhaust gas, and the water is used for the generation of water vapor. The fuel cell 34 generates heat due to power generation, and the exhaust heat recovery device 37 can be used to recover the heat and use it efficiently. The exhaust heat recovery device 3 7 includes a heat exchanger 37A attached to the heat generated during the reaction of the fuel cell 34, and a heat exchanger for heat exchange with the heat and water sucked by the heat exchanger 37A. 37B The warm water obtained in the heat exchanger 37B can be effectively utilized in other equipment, together with the cooler 37C, the exchangers 37A, 3:7B, and the pump 37D that circulates the refrigerant to the cooler 37C. [Embodiment] Next, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. Preparation Example 1 Copper nitrate was placed in a CuFe204 spinel oxide beaker (99.9% Cu(N03)2·3H20 manufactured by Wako Pure Chemical Industries, Ltd.) 24.184g and ferric nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) 99.9% Fe(N03)3 . 9H2〇) 80.88 lg, dissolved in distilled water to 300 m 1, and heated to 60 ° C for 2 hours. Next, citric acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., 99.5% C6H807 · 3H20) was added to the solution. 92.926g 're-23-200911363 After stirring at 60 ° C for 1 hour, the temperature was raised to 90 °. After C, the water is evaporated. The nitrate and tannic acid of the gel produced in this manner are decomposed in air at 140 to 200 ° C to obtain an oxide fine powder, which is then fired at 900 ° C for 10 hours in the air to obtain a CuFe 2 〇 4 tip. Spar oxide. Preparation Example 2 Copper nitrate was placed in a CuMn204 spinel oxide beaker (manufactured by Wako Pure Chemical Industries, Ltd., 99.9% Cu(N03)2 · 3H20) 24.184 g with manganese nitrate (manufactured by Aldrich Co., Ltd., 98% Mn ( N03) 2. 6H20) 58.588 g, dissolved in distilled water to make 300 ml, and warmed to 60 ° C and stirred for 2 hours. Then, 92-926 g of citric acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., 99.5% C6H807 · 3H20) was added to the solution, and the mixture was stirred at 60 ° C for 1 hour, and then heated to 90 ° C to evaporate water. . The nitrate and tannic acid of the gel produced in this manner are decomposed in air at 140 to 200 ° C to obtain an oxide fine powder, and then fired at 900 ° C for 10 hours in the air to obtain CuMn204 spinel. Type oxide. Preparation Example 3 CuFei.5MnG.504 Spinel-type oxide beaker was placed with copper nitrate (manufactured by Wako Pure Chemical Industries, Ltd., 99.9% Cu(N03)2. 3H20) 24.1 84g and ferric nitrate (Wako Pure Chemical Industries, Ltd.) Co., Ltd., 99.9% Fe(N03)3·9H20) 60.661 g and manganese nitrate (98% Μη(Ν03)2·6H20, manufactured by Aldrich Co., Ltd.) 14.647g, dissolved in distilled water to 300 00m and heated to Stir at 60 ° C for 2 hours. Next, 92.926 g of citric acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., 99.5% C6H807. 3 H20) was added to the solution, and the mixture was further stirred at 60 ° C for 1 hour, and then the temperature was raised to The water was evaporated after 90 °C. The nitrate and tannic acid of the gel produced in this manner are decomposed in air at 140 to 200 ° C to obtain an oxide fine powder, which is then fired at 900 ° C for 10 hours in the air to obtain CuFei.5Mn〇. .504 spinel oxide. Example 1 The CuFe2〇4 spinel oxide 1 〇g obtained in the preparation example 1 and the r-alumina ("AKP-G015" manufactured by Sumitomo Chemical Co., Ltd.) which was fired at 700 ° C for 30 minutes were prepared. 5g was mixed with hydrazine, and it was reduced by 6 0 (TC for 3 hours) in nitrogen gas containing 1 〇 vol% of hydrogen, and then burned at 350 ° C for 1 hour in an air atmosphere. In the first embodiment, the firing conditions in the air environment were changed to 500 ° C and 10 hours, and the rest were modified and modified in the same manner as in the first embodiment. (Example 3) In the first embodiment, except that the firing conditions in an air atmosphere were changed to 70 ° C and 10 hours, the catalyst for the modification was prepared in the same manner as in Example 1. -25- 200911363 Example 4 In the first embodiment, the catalyst for reforming was prepared in the same manner as in Example 1 except that the firing conditions in the air atmosphere were changed to 800 ° C for 1 hour. In 1 , the reduction conditions in nitrogen gas containing 10% by volume of hydrogen were changed to 3 5 (TC, 3) The catalyst for reforming was prepared in the same manner as in Example 1 except for the hour. Example 6 In Example 2, the reduction conditions in nitrogen gas containing 10% by volume of hydrogen were changed to 350 ° C for 3 hours. The catalyst for reforming was prepared in the same manner as in Example 2. Example 7 In Example 3, the reduction conditions in nitrogen gas containing 1% by volume of hydrogen were changed to 350 ° C for 3 hours. The catalyst for the modification was prepared in the same manner as in Example 3. Example 8 After the catalyst obtained in Example 7 was pressure-molded by 10 0 to 1 8 · 5 mesh, the amount of the catalyst was quantitatively charged. The reactor was subjected to a reduction of 35% in a nitrogen gas containing -26% by volume of hydrogen in -26-200911363, and Example 9 was changed to 3 5 in addition to the reduction condition of 1 〇 volume. 0. (:, 3 hours other than the same method of modulation and modification of the catalyst. Example 1 0
調製例1所得到的CuFe204尖晶石 以7 00°C進行30分鐘燒成的r -氧化鋁 限公司製「AKP-G015」）5g以硏鉢混 境下，以3 5 0 °C進行1 0小時燒成，丨 SCFAc35，燒成溫度：3 5 0 °C )。使用 述的測量條件進行X線繞射，將此圖表 裝置：Rigaku-RINT-2200，線源： 40mA 階段（s t e p ) : 0 · 〇 2 °，掃描速度： 再者，圖2中’ SCFAclOO係除了 成條件變更爲1〇〇〇 °C以外，其餘與實拥 得到的改質用觸媒的X線繞射圖，但 判定性能比SCFAc90差，未進行〇ΜΕ 實施例11 製改質用觸媒。 %的氫之氮氣中的 ，其餘與實施例4 ί型氧化物l〇g，與 (住友化學股份有 合，藉由在空氣環 調製改質用觸媒（ 所得到的觸媒以下 列示於圖2。 CuK α 線、40kV、 IV分鐘 將空氣環境下的燒 i例1 〇同樣作法所 X線繞射的結果， 的改質反應性評估 -27- 200911363 實施例1 〇中，除了將空氣環境下的燒成條件，變更 爲5 〇〇°C、10小時以外’其餘與實施例10同樣作法調製 改質用觸媒（SCFAc50，燒成溫度·· 50(TC )，使用所得 到的觸媒以實施例1 〇所示的測量條件進行X線繞射，其 圖表列示圖2。 實施例1 2 實施例1〇中，除了將空氣環境下的燒成條件，變更 爲7 0 0 °C、1 〇小時以外，其餘與實施例1 〇同樣作法調製 改質用觸媒（SCFAC70 ’燒成溫度：700 °C )。 使用所得到的觸媒以實施例1 〇所示的測量條件進行 X線繞射，其圖表列示圖2。其結果係在2 0 =3 3.2°出現 的繞射線強度、與在2 0 =3 6. 1 °出現的CuFe〇4尖晶石的 最強線之繞射線強度之比在〇 . 2 3。 實施例1 3 藉由將實施例12所得到的觸媒以1〇~18·5網眼加壓 成型後，將所定量塡充於反應器’於含有10體積％的氫 之氮氣中，以3 5 0。(：進行3小時的還原’調製改質用觸媒 實施例1 4 實施例1 0中，除了將空氣環境下的燒成條件’變更 爲8 0 01：、1 〇小時以外，其餘與實施例1 0同樣作法調製 -28- 200911363 改質用觸媒（SCFAc80，燒成溫度：800°C)。 使用所得到的觸媒以實施例丨〇所示的測量條件進行 X線繞射，其圖表列示圖2。其結果係在2 β = 3 3 · 2。出現 的繞射線強度、與在2 0 = 3 6.1。出現的C u F e Ο 4尖晶石的 最強線之繞射線強度之比在0.6 8。 實施例1 5 實施例10中’除了將空氣環境下的燒成條件，變更 爲7 0 0°C、1小時以外’其餘與實施例丨〇同樣作法調製改 質用觸媒。 實施例1 6 實施例1 〇中’除了將空氣環境下的燒成條件，變更 爲70 0°C、5小時以外，其餘與實施例1 〇同樣作法調製改 質用觸媒。 實施例17 實施例1 〇中，除了將空氣環境下的燒成條件，變更 爲7 0 0 °C、2 0小時以外，其餘與實施例1 〇同樣作法調製 改質用觸媒。 比較例1 調製例1所得到的CuFe2〇4尖晶石型氧化物10g，與 以7 〇 〇 °C進行3 0分鐘燒成的r -氧化鋁（住友化學股份有 -29- 200911363 限公司製「AKP-G015」）5g以硏鉢混合，藉由將其在含 有10體積％的氫之氮氣中，以600。(：進行3小時還原， 調製改質用觸媒。 比較例2 比較例〗中，除了將空氣環境下的燒成條件，變更爲 900 °C、1〇小時以外，其餘與實施例丨同樣作法調製改質 用觸媒。 比較例3 比較例〗中，除了將含有10體積％的氫之氮氣中的 還原條件，變更爲3 50它、3小時以外，其餘與比較例1 同樣作法調製改質用觸媒。 比較例4 比較例2中，除了將含有1 0體積％的氫之氮氣中的 還原條件，變更爲35(TC、3小時以外，其餘與比較例2 同樣作法調製改質用觸媒。 比較例5 調製例1所得到的CuFe2〇4尖晶石型氧化物10g，與 以700C進彳7 30分鐘燒成的7-氧化銘（住友化學股份有 限公司製「AKP-G015」）5g以硏鉢混合，調製改質用觸 媒（SCFA )，使用所得到的觸媒以實施例1 〇所示的測量 -30- 200911363 條件進行X線繞射，將此圖表列示於圖2。 比較例6 實施例1 0中，除了將空氣環境下的燒成條件，變更 爲9 0 〇 °C、1 0小時以外，其餘與實施例1 0同樣作法調製 改質用觸媒（SCFAc90，燒成溫度：900 °C )。使用所得 到的觸媒以實施例1 0所示的測量條件進行X線繞射，其 圖表列示圖2。 實施例1 8 調製例2所得到的CuMn204尖晶石型氧化物l〇g，與 以7〇〇 °C進行30分鐘燒成的r -氧化鋁（住友化學股份有 限公司製「AKP-G015」）5g以硏鉢混合，然後，在空氣 環境下’以7 00 °C進行10小時燒成，調製改質用觸媒。 比較例7 調製例2所得到的CuMn2〇4尖晶石型氧化物l〇g，與 以70(TC進行30分鐘燒成的7 —氧化鋁（住友化學股份有 限公司製「AKP-G015」）5g以硏鉢混合，調製改質用觸 媒。 實施例1 9 調製例3所得到的CuFei 5Mn〇.5〇4尖晶石型氧化物 l〇g，與以7〇〇°C進行30分鐘燒成的7 -氧化鋁（住友化 -31 - 200911363 學股份有限公司製「AKP-G015」）5g以硏鉢 ，在空氣環境下’以7 00 °C進行1 〇小時燒成 用觸媒。 比較例8 調製例3所得到的CuFei.5MnG.504尖晶 l〇g，與以700 °C進行30分鐘燒成的7 -氧化 學股份有限公司製「AKP-G015」）5g以硏鉢 改質用觸媒。 比較例9 將調製例1所得到的CuFe204尖晶石型氧 在空氣環境下，以70 (TC進行1〇小時燒成者， 進行1 〇小時燒成的r -氧化鋁（住友化學股份 「AKP-G015」）5g以硏鉢混合，調製改質用頻 參考例15 g of the CuFe204 spinel obtained in Preparation Example 1 and "AKP-G015" manufactured by r-alumina Co., Ltd., which was fired at 70 ° C for 30 minutes, in a mixed atmosphere, at 305 ° C. 0 hour firing, 丨SCFAc35, firing temperature: 3 50 °C). X-ray diffraction using the measurement conditions described, this chart device: Rigaku-RINT-2200, line source: 40mA stage (step): 0 · 〇2 °, scanning speed: Again, in Figure 2 'SCFAclOO system except The condition was changed to X-ray diffraction pattern of the catalyst for modification which was obtained in addition to 1 〇〇〇 °C, but the determination performance was worse than that of SCFAc 90, and the catalyst was not modified. . % of the hydrogen in the nitrogen, the rest with the example 4 ί type oxide l〇g, with (Sumitomo Chemical Co., Ltd., by modifying the catalyst in the air ring modulation (the resulting catalyst is shown below) Figure 2. CuK α line, 40kV, IV minutes, the results of the X-ray diffraction of the same method in the air environment, the conversion reactivity evaluation -27- 200911363 Example 1 In addition to the air The firing conditions in the environment were changed to 5 〇〇 ° C for 10 hours. The rest of the catalyst was prepared in the same manner as in Example 10 (SCFAc 50, firing temperature · 50 (TC ), and the obtained touch was used. The medium was subjected to X-ray diffraction under the measurement conditions shown in Example 1 and the graph is shown in Fig. 2. Example 1 2 In Example 1, the firing conditions in the air environment were changed to 70 °. The catalyst for the modification (SCFAC70 'sintering temperature: 700 ° C) was prepared in the same manner as in Example 1 except that C and 1 hour were used. The obtained catalyst was used under the measurement conditions shown in Example 1 X-ray diffraction, the chart is shown in Figure 2. The result is a ray around 20 = 3 3.2 ° The ratio of the radiant intensity to the strongest line of the CuFe〇4 spinel appearing at 20 = 3 6. 1 ° is 〇. 2 3. Example 1 3 The catalyst obtained by Example 12 After press molding with a mesh of 1〇~18·5, the quantified solution was charged to the reactor 'in a nitrogen gas containing 10% by volume of hydrogen, and was changed to 305. (: 3 hours of reduction' modulation was modified. Catalyst Example 1 4 In Example 10, except that the firing condition in the air environment was changed to 801:1, 1 hr, the same procedure as in Example 10 was carried out. -28-200911363 Modification Using a catalyst (SCFAc80, firing temperature: 800 ° C.) X-ray diffraction was performed using the obtained catalyst under the measurement conditions shown in Example ,, and the graph is shown in Fig. 2. The result is in 2 β = 3 3 · 2. The ratio of the intensity of the ray that appears to the ray intensity of the strongest line of the C u F e Ο 4 spinel appearing at 20 = 3 6.1 is 0.68. Example 1 5 In the case of "in the case of the firing conditions in the air environment, the temperature was changed to 700 ° C for 1 hour," and the catalyst for the modification was modified in the same manner as in the example. 1 6 Example 1 The catalyst for reforming was prepared in the same manner as in Example 1 except that the firing conditions in the air atmosphere were changed to 70 ° C for 5 hours. Example 17 Example 1 In the crucible, the catalyst for reforming was prepared in the same manner as in Example 1 except that the firing conditions in the air atmosphere were changed to 70 ° C for 20 hours. Comparative Example 1 10 g of CuFe 2 〇 4 spinel oxide obtained in Preparation Example 1 and r-alumina sintered at 70 ° C for 30 minutes (Sumitomo Chemical Co., Ltd. -29-200911363 limited company) "AKP-G015") 5 g was mixed with hydrazine by using 600 in nitrogen gas containing 10% by volume of hydrogen. (: Three-hour reduction was carried out to prepare a catalyst for reforming. In Comparative Example 2, the firing conditions in the air atmosphere were changed to 900 ° C for 1 hour, and the same procedure as in Example 丨 was carried out. In the comparative example, the reduction conditions in the nitrogen gas containing 10% by volume of hydrogen were changed to 3 50, and 3 hours, and the same modification as in Comparative Example 1 was carried out. Comparative Example 4 In Comparative Example 2, the reduction conditions in nitrogen gas containing 10% by volume of hydrogen were changed to 35 (TC, 3 hours, and the same procedure as in Comparative Example 2 was used. Comparative Example 5 10 g of CuFe 2 〇 4 spinel oxide obtained in Preparation Example 1 and 7-Oxide (76-made by Sumitomo Chemical Co., Ltd.) made by firing at 700 C for 30 minutes. 5g was mixed with yttrium, modulated with a catalytic converter (SCFA), and X-ray diffraction was performed using the obtained catalyst under the measurement of -30-200911363 shown in Example 1 and the graph is shown in Fig. 2 Comparative Example 6 In Example 10, except for firing in an air environment The catalyst for the modification (SCFAc90, firing temperature: 900 ° C) was prepared in the same manner as in Example 10 except that the temperature was changed to 90 ° C for 10 hours. The obtained catalyst was used as an example. X-ray diffraction was performed under the measurement conditions shown in 10, and the graph is shown in Fig. 2. Example 1 8 The CuMn204 spinel-type oxide l〇g obtained in Preparation Example 2 was carried out at 30 °C. 5 g of r-alumina ("AKP-G015" manufactured by Sumitomo Chemical Co., Ltd.) which was fired in a minute was mixed with ruthenium, and then fired at 700 ° C for 10 hours in an air atmosphere to prepare a touch for modification. Comparative Example 7 The CuMn2〇4 spinel oxide l〇g obtained in Preparation Example 2 and the 7-alumina sintered at 70 (TC for 30 minutes (AKP-G015, manufactured by Sumitomo Chemical Co., Ltd.) 5g mixed with yttrium to modulate the catalyst for modification. Example 1 9 CuFei 5Mn〇.5〇4 spinel-type oxide l〇g obtained in Preparation Example 3, and 7 〇〇 ° C 7-alumina fired in 30 minutes ("Supplier-31 - 200911363" Co., Ltd. "AKP-G015") 5g 硏钵, in the air environment 'to 7 The catalyst for firing was burned at 00 ° C for 1 hour. Comparative Example 8 CuFei.5MnG.504 spinel l〇g obtained in Preparation Example 3 was limited to 7-oxidation shares which were fired at 700 ° C for 30 minutes. 5 g of the company's "AKP-G015") was used to modify the catalyst for ruthenium. Comparative Example 9 The CuFe204 spinel oxygen obtained in Preparation Example 1 was fired at 70 (TC for 1 hour) in an air atmosphere. , 5 g of r-alumina (Sumitomo Chemical Co., Ltd. "AKP-G015") which was fired in 1 hour, mixed with yttrium, and used for frequency modulation reference example 1
CuZnAl ( SUD-CHEMIE 公司製「MDC-3」 以700 °c進行30分鐘燒成的7 -氧化鋁（住友 限公司製「AKP-G015」）5g以硏鉢混合，調 媒。 參考例2CuZnAl ("MDC-3" manufactured by SUD-CHEMIE Co., Ltd. 5 g of 7-alumina ("AKP-G015" manufactured by Sumitomo Co., Ltd.) which was fired at 700 °C for 30 minutes was mixed with ruthenium to adjust the medium. Reference Example 2
CuZnAl ( SUD-CHEMIE 公司製「MDC-3」 混合，然後 ，調製改質 石型氧化物 鋁（住友化 混合，調製 化物1 0 g， 與以7 0 0 °C 有限公司製 i媒。 )l〇g ，與 化學股份有 製改質用觸 )1〇g ，與 -32- 200911363 以7〇(TC進行30分鐘燒成的r -氧化鋁（住友化學股份有 限公司製「AKP-G015」）5g以硏鉢混合，然後，在空氣 環境下’以7〇〇°C進行1〇小時燒成，調製改質用觸媒。 試驗例 關於實施例1 ~ 1 9、比較例1〜9及參考例1、2所得到 的改質用觸媒’進行下述所示的性能評估試驗，其結果列 不表1。 <前處理條件> .將於1 〇~ 1 8.5網眼成型的觸媒，塡充於反應器。 (關於實施例8、1 3，如下述於反應器中在反應前進行氫 還原） <反應條件：DME水蒸氣改質反應> • GHSV = 9 1 001Γ1 ( DME + H20 基準）（（DME 基準爲 15 171Γ1 )，蒸氣/碳莫耳比=2.5，反應溫度=3 75 °C，反應 時間=5 0小時 • DME 轉化率（％ ) = ( A/B ) xl 〇〇 Α:出口 CO莫耳濃度+出口 C02莫耳濃度+出口 CH4莫耳濃度 B:出口 CO莫耳濃度+出口 C〇2莫耳濃度+出口 CH4 莫耳濃度+出口 DME莫耳濃度x2 •劣化率（％ ) =[ ( C-D ) /C]xl〇〇 -33- 200911363 c :反應開始7小時 D :反應開始5 0小時 (惟，比較例8、實 據作爲D ) t的DME轉化率 後的DME轉化率 例1 9，係使用3 5小時後的數 -34- 200911363 例編號 mm tl還原 燒成 燒成後還原 溫度 時間 溫度 時間 溫度 時間 (°C) (h) ΓΟ (h) CC) (h) 實1 600 3 350 10 - _ 實2 600 3 500 10 - . 實3 600 3 700 10 _ _ 實4 600 3 800 10 - - 實5 350 3 350 10 . _ 實6 350 3 500 10 - _ 實7 350 3 700 10 _ - 實8 350 3 700 10 350 3 實9 350 3 800 10 - _ 實10 - 350 10 - - CuFe 型 尖晶石 實η - - 500 10 - _ 氧化銘 實12 一 700 10 _ 實13 - - 700 10 350 3 實14 • 800 10 _ 實15 - 700 1 • . 實16 - 700 5 - _ 實Π - - 700 20 嗎 比1 600 3 - _ _ 比2 600 3 900 10 _ 比3 350 3 - • 比4 350 3 900 10 比5 _ 一 - _ _ _ 比6 - 900 10 - - CuMn 型 尖晶石 實18 - - 700 10 - _ 尖晶石 比7 - - - . _ CuFeMn 尖晶石 實19 - - 700 10 - 型尖晶 石 比8 - - - - - - CuFe型尖晶石 比9 - - 700 10 - - 尖晶石 - - 700 10 - - CuZnAl 尖晶石 參1 - - _ _ - . 市售品 參2 - - 700 10 - (實：實施例、比：比較例、參：參考例） -35- 200911363CuZnAl ("MDC-3" manufactured by SUD-CHEMIE Co., Ltd. was mixed, and then modified stone-type oxide aluminum (Sumitomo Mix, 10 g of the compound, and the medium made by 700 °C). 〇g, and the chemical stocks have been modified to use 1)g, and -32- 200911363 to 7〇 (TC-fired r-alumina for 30 minutes ("AKP-G015" by Sumitomo Chemical Co., Ltd.) 5 g was mixed with hydrazine, and then fired at 7 ° C for 1 hour in an air atmosphere to prepare a catalyst for reforming. Test Examples About Examples 1 to 19, Comparative Examples 1 to 9 and Reference The performance-testing tests shown in Examples 1 and 2 performed the performance evaluation tests shown below, and the results are shown in Table 1. <Pre-treatment conditions>. Touches to be formed in 1 〇~1 8.5 mesh The medium was charged to the reactor. (About Examples 8, 13, hydrogen reduction was carried out before the reaction in the reactor as follows) <Reaction conditions: DME steam reforming reaction> • GHSV = 9 1 001 Γ 1 ( DME + H20 benchmark) ((DME benchmark is 15 171Γ1), steam/carbon molar ratio = 2.5, reaction temperature = 3 75 °C, reaction time = 50 hours • DME conversion rate (%) = (A/B) xl 〇〇Α: outlet CO molar concentration + outlet C02 molar concentration + outlet CH4 molar concentration B: outlet CO molar concentration + outlet C 〇 2 molar concentration + Export CH4 molar concentration + outlet DME molar concentration x2 • Deterioration rate (%) = [ ( CD ) /C]xl〇〇-33- 200911363 c : 7 hours after the start of the reaction D: 50 hours after the start of the reaction (only, comparison Example 8, the DME conversion rate after DME conversion as D) t Example 169, using the number after 34 hours -34-200911363 Example number mm tl reduction after firing, reduction temperature time temperature time temperature time (°C) (h) ΓΟ (h) CC) (h) Real 1 600 3 350 10 - _ Real 2 600 3 500 10 - . Real 3 600 3 700 10 _ _ Real 4 600 3 800 10 - - Real 5 350 3 350 10 . _ Real 6 350 3 500 10 - _ Real 7 350 3 700 10 _ - Real 8 350 3 700 10 350 3 Real 9 350 3 800 10 - _ Real 10 - 350 10 - - CuFe type spinel Real η - - 500 10 - _ Oxidization Ming 12 - 700 10 _ Real 13 - - 700 10 350 3 Real 14 • 800 10 _ Real 15 - 700 1 • . Real 16 - 700 5 - _ Real Π - - 700 20 than 1 600 3 - _ _ than 2 600 3 900 10 _ than 3 350 3 - • than 4 350 3 900 10 to 5 _ one - _ _ _ than 6 - 900 10 - - CuMn type spinel real 18 - - 700 10 - _ spinel ratio 7 - - - . _ CuFeMn spinel solid 19 - - 700 10 - type spinel than 8 - - - - - - CuFe type spinel ratio 9 - - 700 10 - - Spinel - - 700 10 - - CuZnAl Spinel ginseng 1 - - _ _ - . Commercial product ginseng 2 - - 700 10 - (Real: Example, ratio: comparative example, reference: reference example) - 35- 200911363
第1表-2 例 編號 反應結果 備註 DME轉化率(％) 劣化率 (%) 7h後 5〇h後 CuFe 型 尖晶石 氧化鋁 實1 65.0 42.6 34.5 觸媒名稱:SCFAc35 觸媒名稱:SCFAc50 實2 66.3 56.0 15.6 實3 77.8 75.7 2.8 實4 81.3 81.6 -0.4 實5 65.1 68.4 -5.1 實6 83.0 76.2 8.2 實7 82.3 80.3 2.4 貝8 80.1 75.7 5.5 實9 80.4 81.8 -1.7 實10 66.3 68.4 -3.2 實11 67.1 66.1 1.5 實12 83.6 84.9 -1.5 觸媒名稱:SCFAc70 實13 80.0 76.0 5.0 觸媒名稱:SCFAc80 實14 79.5 83.8 -5.4 實15 71.3 69.9 2.0 實16 81.9 81.5 0.4 實17 82.3 81.6 0.9 比1 70.1 7.4 89.4 比2 0.2 - - 比3 67.6 59.8 11.5 觸媒名稱:SCFA 觸媒名稱:SCFAc90 比4 3.4 - - 比5 66.9 59.7 10.9 比6 2.7 - _ CuMn 型 尖晶石 尖晶石 實18 72.6 72.6 0.0 比7 55.8 56.1 -0.4 CuFeMn 型尖晶石 尖晶石 實19 71.1 56.6 20.4 35小時後的轉化率、劣化率 比8 65.6 33.2 49.4 35小時後的轉化率、劣化率 CuFe型尖晶石 比9 61.4 58.4 4.8 將尖晶石與氧化鋁各自以700 t：燒成後混合(與實12的比較） 尖晶石 CuZnAl 市售品 尖晶石 參1 14.2 15.3 -7.4 參2 46.7 49.7 -6.3 (實：實施例、比：比較例、參：參考例） -36- 200911363 從表1可得知下述內容。 •比較例1與實施例1〜4的比較： 藉由加入3 50°C、500°C的燒成步驟（實施例1、2) ，比未燒成（比較例1 )更能大量地抑制劣化，50小時後 的活性係實施例變得較高。 藉由加入7 0 0 °C、8 0 0 °C的燒成步驟（實施例3、4 ) ，比未燒成（比較例1 )更能大量地提高初期活性及持久 性，此外，900 °C的燒成（比較例2 )則初期活性顯著地 低。 •比較例3、4與實施例5〜9的比較： 藉由加入3 5 0 °C的燒成步驟（實施例5 )，雖然初期 性能比未燒成（比較例3 )少許降低，但活性劣化受到抑 制，50小時後的活性係實施例5變得較高。藉由加入5〇〇 °C、7 0 0 °C、8 0 0 °C的燒成步驟（實施例6、7、8、9 ) ’ 比未燒成（比較例3 )更能大量地提高初期活性及持久性 ，此外，90(TC的燒成（比較例4 )則初期活性顯著地低 〇 此外，反應前還原與否的影響小（實施例7與8的比 較） •比較例5、6與實施例1 0〜1 4的比較： 藉由加入3 5 0 °C、50〇t的燒成步驟（實施例10、1 1 -37- 200911363 )，即使初期性能約與未燒成（比較例4 )同等，但活性 劣化受到抑制，50小時後的活性變高。藉由加入700°C、 8 0 0 °C的燒成步驟（實施例1 2、1 3、1 4 )，比未燒成（比 較例5 )更能大量地提高初期活性及持久性，此外，900 t的燒成（比較例6)則初期活性顯著地低。 此外，反應前是否有還原的影響並不大（實施例12 、1 3的比較） •比較例5與實施例1 2、1 5、1 6、1 7的比較（7 0 0 °C燒成 時間的比較）： 7 00 °C燒成的時間即使爲1小時（實施例15 )亦有效 果，但5小時以上（實施例1 6、12、1 7 )具有更大的效 果。 •比較例7與實施例1 8的比較： 在CuMn尖晶石中，亦確認藉由與氧化鋁的混合後的 7〇〇 °C燒成，具有初期活性提高效果。 •比較例8與實施例1 9的比較： 在CuFeMn尖晶石中，亦確認藉由與氧化鋁的混合後 的7 00 °c燒成，具有初期活性提高、持久性提高的效果。 •比較例9與實施例1 2的比較：Table 1-2 Example No. Reaction Results Remarks DME Conversion Rate (%) Deterioration Rate (%) CuFe-type spinel alumina after 5 h after 7 h 6 6 4 42.6 34.5 Catalyst name: SCFAc35 Catalyst name: SCFAc50 2 66.3 56.0 15.6 Real 3 77.8 75.7 2.8 Real 4 81.3 81.6 -0.4 Real 5 65.1 68.4 -5.1 Real 6 83.0 76.2 8.2 Real 7 82.3 80.3 2.4 Shell 8 80.1 75.7 5.5 Real 9 80.4 81.8 -1.7 Real 10 66.3 68.4 -3.2 Real 11 67.1 66.1 1.5 Real 12 83.6 84.9 -1.5 Catalyst name: SCFAc70 Real 13 80.0 76.0 5.0 Catalyst name: SCFAc80 Real 14 79.5 83.8 -5.4 Real 15 71.3 69.9 2.0 Real 16 81.9 81.5 0.4 Real 17 82.3 81.6 0.9 Ratio 1 70.1 7.4 89.4 Ratio 2 0.2 - - to 3 67.6 59.8 11.5 Catalyst Name: SCFA Catalyst Name: SCFAc90 Ratio 4 3.4 - - Ratio 5 66.9 59.7 10.9 Ratio 6 2.7 - _ CuMn Type Spinel Spinel Real 18 72.6 72.6 0.0 Ratio 7 55.8 56.1 -0.4 CuFeMn type spinel spinel 19 171.1 56.6 20.4 Conversion rate and deterioration rate after 35 hours 8 65.6 33.2 49.4 Conversion rate after 35 hours, deterioration rate CuFe type spinel ratio 9 61.4 58.4 4.8 Put spinel and alumina at 700 t each Mix after firing (compared with real 12) Spinel CuZnAl Commercial product spinel ginseng 1 14.2 15.3 -7.4 Reference 2 46.7 49.7 -6.3 (Real: Example, ratio: Comparative example, reference: Reference example) - 36- 200911363 The following can be seen from Table 1. • Comparison of Comparative Example 1 and Examples 1 to 4: By adding a firing step of 3 50 ° C and 500 ° C (Examples 1 and 2), it was more suppressed than that of unfired (Comparative Example 1). Deterioration, the activity system after 50 hours became higher. By adding the firing step of 700 ° C and 800 ° C (Examples 3 and 4), the initial activity and durability can be greatly improved compared with the unfired (Comparative Example 1), in addition, 900 ° The firing of C (Comparative Example 2) showed that the initial activity was remarkably low. • Comparison of Comparative Examples 3 and 4 with Examples 5 to 9: By adding a baking step of 350 ° C (Example 5), although the initial performance was slightly lower than that of the unfired (Comparative Example 3), the activity was The deterioration was suppressed, and the activity of Example 5 after 50 hours became higher. The firing step (Examples 6, 7, 8, and 9) ' by adding 5 ° C, 700 ° C, and 800 ° C can be greatly improved compared with the unfired (Comparative Example 3) Initial activity and durability, in addition, 90 (combustion of TC (Comparative Example 4) showed that the initial activity was remarkably low, and the effect of reduction before the reaction was small (comparison of Examples 7 and 8). 6Comparative with Example 1 0 to 1 4: By adding a firing step of 350 ° C and 50 〇t (Example 10, 1 1 -37 to 200911363), even if the initial performance is about or not ( Comparative Example 4) Equivalent, but the activity deterioration was suppressed, and the activity after 50 hours became high. By adding a firing step of 700 ° C and 80 ° C (Examples 1, 2, 13, 3), the ratio was In the unfired (Comparative Example 5), the initial activity and the durability were further improved in a large amount, and the initial activity was remarkably low in the calcination at 900 t (Comparative Example 6). Moreover, whether or not the reduction was affected before the reaction was not large. (Comparison of Examples 12 and 13) • Comparison of Comparative Example 5 with Examples 1 2, 1 5, 16 and 17 (comparison of firing time at 700 ° C): firing at 700 ° C Even time 1 hour (Example 15) also had an effect, but more than 5 hours (Examples 16, 6 and 12) had a greater effect. • Comparison of Comparative Example 7 with Example 18: In CuMn spinel It was also confirmed that the initial activity was improved by firing at 7 ° C after mixing with alumina. • Comparison of Comparative Example 8 and Example 19: In CuFeMn spinel, it was also confirmed by When the alumina was mixed at 700 ° C, the initial activity was improved and the durability was improved. Comparison of Comparative Example 9 and Example 1 2
CuFe尖晶石與氧化鋁即使各自700t：燒成後混合（比 -38- 200911363 較例9)，未出現如實施例1 2之混合後的燒成效果，此 外，初期活性稍微低於各自未燒成下混合且混合後亦無燒 成的狀況（比較例5)。 •參考例1、2的比較 混合CuZnAl (非尖晶石）與氧化鋁後進行700 °C燒 成時，具有初期活性提高的效果，但活性的絕對値低。 [產業上的可利用性] 本發明的含氧碳氫化合物改質用觸媒，可有以高轉化 率且有效率地由含氧碳氫化合物製造氫或合成氣體，可應 用於效率高的燃料電池系統。 【圖式簡單說明】 [圖1 ]本發明的燃料電池系統其中一例之流程圖。 [圖2 ]實施例1 0 ~ 1 2及1 4、比較例5及6所得到的改 質用觸媒的X線繞射圖。再者，SCAFclOO係除了變更爲 空氣環境下的燒成條件1 0 0 0。(：以外，與實施例1 〇同樣作 法而得到的改質用觸媒的X線繞射圖。 【主要元件符號說明】 I :氣化器 II :水供給管 1 2 :燃料導入管 -39- 200911363 1 5 :連接管 2 1 :燃料槽 23 :脫硫器 2 4 :水泵 3 1 :改質器 31A:改質器的燃燒器 32 : CO交換器 33 : CO選擇氧化器 3 4 :燃料電池 34A :燃料電池負極 34B :燃料電池正極 34C :燃料電池高分子電解質 3 5 :空氣鼓風機 3 6 :氣水分離器 3 7 :排熱回收裝置 37A :熱交換器 37B :熱交換器 3 7 C :冷卻器 3 7D :冷媒循環泵 -40-CuFe spinel and alumina were mixed at 700 t: after firing (compared with -38-200911363 to Example 9), and the firing effect after mixing as in Example 12 did not occur, and the initial activity was slightly lower than that of each. The mixture was mixed under firing and did not burn after mixing (Comparative Example 5). • Comparison of Reference Examples 1 and 2 When CuZnAl (non-spinel) and alumina were mixed and fired at 700 °C, the initial activity was improved, but the activity was absolutely low. [Industrial Applicability] The catalyst for oxidizing hydrocarbon-containing reforming of the present invention can produce hydrogen or a synthesis gas from an oxygen-containing hydrocarbon at a high conversion rate and efficiently, and can be applied to high efficiency. Fuel cell system. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A flow chart of an example of a fuel cell system of the present invention. Fig. 2 is an X-ray diffraction pattern of a catalyst for modification obtained in Examples 1 0 to 1 2 and 14 and Comparative Examples 5 and 6. Further, SCAFclOO was changed to the firing condition 1 0 0 0 in the air environment. (X-ray diffraction pattern of the catalyst for reforming obtained in the same manner as in Example 1 except for (1). [Explanation of main component symbols] I: Gasifier II: Water supply pipe 1 2: Fuel introduction pipe - 39 - 200911363 1 5 : Connecting pipe 2 1 : Fuel tank 23 : Desulfurizer 2 4 : Water pump 3 1 : Reformer 31A: Reformer burner 32 : CO exchanger 33 : CO selective oxidizer 3 4 : Fuel Battery 34A: Fuel cell negative electrode 34B: Fuel cell positive electrode 34C: Fuel cell polymer electrolyte 3 5 : Air blower 3 6 : Gas water separator 3 7 : Exhaust heat recovery device 37A: Heat exchanger 37B: Heat exchanger 3 7 C : Cooler 3 7D : Refrigerant Circulation Pump - 40-