200909348 九、發明說明： 【發明所屬之技術領域】 本發明係關於-種燃料生產系統及燃料生產程序，尤轉指一種 富氫氣體㈣生產系統及富氫氣體轉生餘序，其係躺於燃料電 池及内燃機之燃料的領域。 【先前技術】 碳氫化合物、甲醇、酒精進料的催化性部分氧化或催化性蒸氣重組程 序以產生富減體已是習知技術。通常這類程序，係將碳氣化合物、甲醇、 酒精進料顧-個兩階段反應ϋ ’催化性部分氧域統重組以產生富氣 氣體。另外的習知技術為在單-反應n中含多個觸航應區时別進行催 化性部分氧化或蒸氣重組反應。已揭示的這類習知技術包括在下列之專 利：US 4522894、US 6849572、US 7715827、us 7144566、us 7153344、 US 7150866、US 6949683 及 US 6936237。 先刖技術程序中在卓反應益中使用的連續多層觸媒區或使用兩階段 反應器均較本發明之單一觸媒區之單一自發熱反應器複雜很多。本發明富 氫氣體燃料生產系統及富氫氣體燃料生產程序不但節省反應器體積及觸媒 單體單價成本，且能降低催化性部分氧化或蒸氣重組反應造成的麗降。同 時經由自發熱重組反應，能以低溫預熱、絕熱反應器設計之方式，達到兼 具部分氧化及蒸氣重組反應的優點（良好的起動及高氫氣產率）。 先前技術中，已知酒精產氫程序之主要目的在產生富氫氣體。包括下 列化學反應： C2H5OH +l/202—2CO +3H2 AH(25t)= :+14 KJ/mol (i) C2H5OH +H20->2C0 +4H2 ΔΗ(25χ)= +256 KJ/mol (2) C〇 +H2O —^C〇2 + H2 ΔΗ(25ΐ)= -41 KJ/mol ⑶ C2H5OH +3H20-^2C02 +6H2 ΔΗ(25Ϊ)= +174 KJ/mol (4) 200909348 C2H5OH +2H20 -H/202-.2C02 +5H2 AH(25C) = -68 KJ/mol (5) 根據熱力子平衡，反應（1 )之酒精的催化性部分氧化反應，可產生3 莫耳的氫；而反應（2)的催化性酒精重組反應，可產生4莫耳的氫，但為 強吸熱反應，反應ϋ躲縣_。(:社溫度找使反應達平雛態，在能 源利用上相當不利。反應⑵與反應⑴的水氣移轉反應(Watergasshift 細km)組合下可產生反應⑷制6莫耳賊，但仍料部熱源以維持 此蒸氣重組反應。本發明的自發熱酒精重組反應為反應（5)，係反應（^ ) 與反應（3)的熱力學組合’為—個放熱反應’其能使反應物進料之預熱溫 度降低，並經觸媒之催化反應放熱在絕熱反應器令維持⑻。C，產生快 速的反應動力。 先前技術已指出，觸媒活性金屬中對酒精重組反應之氫氣產率及酒精 轉化率之活性順序為：Rh〜Ni〜Co > Pd > Pt > Ru〜Zn〜Cu〜Fe。尤其在 含γ-Αΐ2ο3擔體之情形下，更為明顯。但高溫下，c。、Ru、Cu易產生碳沉 積物毒化觸媒，Ni的CO轉換率低易生成高濃度曱烷，pt/Ce〇2下的c〇轉 換率較Rh/Ce02高等’在麟擇下’本發明巾使狀繼金駐少為一種 白金族金屬元素，觸媒氧化物擔體至少為三氧化二鋁、氧化錐、氧化鈽、 氧化銅、氧化鋅之一所組成。 【發明内容】 本發明之主要目的在於提供一種富氫氣體燃料生產系統及富氫氣體燃 料生產程序，其係使用單一觸媒區之單一自發熱反應器，相較於習知技術 使用的連續多層觸媒區或使用兩階段反應器，本發明能節省反應器體積及 觸媒成本，且能降低催化性部分氧化或蒸氣重組反應造成的壓降。 “本發明之次要目的在於提供一種富氫氣體燃料生產系統及富氫氣體燃 料生產程序，其能使反應物進料之預熱溫度降低，並經觸媒之催化反應放 熱，在絕熱反應器中維持500-80(TC，產生快速的反應動力。 本發明之另一目的在於提供一種富氫氣體燃料生產系統及富氫氣體燃 200909348 f生產程序，其所使狀觸媒床相較於f知之觸，具有降低碳沉積物的 毋化、不易生成甲烧及高轉換率之優點。 本發明係關於-種富氫氣體燃料生產系統及富氫氣體燃料生產程序， j統《料生產祕，包括：—錢氣進聽置，其係輸送水蒸氣； ^乳進聽置’，係輸送空氣；_騎蒸氣進料裝置，其係輸送酒精蒸 氣’及-絕熱反應n ’該絕熱反應器之外部具有—絕熱壁，且—重組器置 麟絕熱壁之⑽及-觸媒床置於該重組器之内部；針該水蒸氣、該空 耽及=精統形成之混合氣體輸送至魏熱反之該觸媒床，反應後 產生虱氣。該富氫氣翻料生產程序，包括：將水蒸氣、空氣及酒精蒸氣 形成之混合氣體輸送至-絕熱反應器中之―觸媒床；及進行_產氮重組 反應後，由該絕熱反應器輪出氫氣。 【實施方式】 兹為使貴審查委員對本發明之特徵及方法步驟有更進一步之瞭解與 S忍識，現將詳細設計之原理及本發明之較佳實施例說明如後。 按本發明的程序由-段過程達到。即，反應物中之水蒸發後與空氣混 合，再與蒸發之酒精一起預熱後，直接導入絕熱反應器中重組器的單一觸 媒床上進行酒精重組反應；或反應物中之水與酒精先分別蒸發成氣相後， 進入導官與下游空氣混合預熱後，直接導入絕熱反應器中重組器的單一觸 媒床上進行酒精重組反應；或水與酒精混合後再發發並與空氣混合後，再 直接導入絕熱反應器中重組器的單一觸媒上進行酒精重組反應。反應物最 初接觸到已預熱之觸媒床時，進行催化性部分氧化反應，產生之C〇隨即進 行放熱之水氣移轉反應並提供部分氧化反應所需之吸熱。水與酒精的蒸發 溫度為150°C〜400。(： ’水、酒精及空氣混合氣體之溫度維持在15〇它〜 400°C，觸媒床之溫度維持在500。〇〜8⑻。c。就酒精重組產氫反應的化學動 力學來看’本發明的重組程序涵蓋催化性部分氧化反應與催化性蒸氣重組 反應’但就化學熱力學看來可視為催化性部分氧化反應與催化性水氣轉移 200909348 反應的組合。 ㈣i發明的觸媒床包括—體成型的陶£或不鏽鋼蜂巢結構體，且該蜂巢 :.具有複數個氣孔通道，較佳情形以每平方英忖具有腦_5〇〇個氣體通 ^白金族金屬讀之氧化物擔體覆於該蜂巢結構體之表面及該氣孔通 道之表面。 一該白金族金屬元素係選自歸㈣㈣及姥⑽)所組成之群组之其中之 :者或其組成之群組之混合物。該氧化物擔體之材料係選自三氧化二銘、 2錯、氧⑽、氧化銅及氧化鋅顺狀群組之其巾之—者或其組成之 群，、且之齡物，射三氧化二銘級⑽㈣， 瓜臟，尤其對拙金屬能獲得高產率的氫及高_= :5 -氧化―财又以γ_Α12〇3為較佳材料。本發明於三氧化二辦添加且 =氧化物如氧化錯、氧⑽、氧化銅、氧化辞，目的在維持觸媒床的熱 ^性、減低碳沉積以防止觸媒的毒化，又可作為反應促進劑降低甲燒盘 —乳化碳的產率。上述添加之氧化物巾以氧蝴㈤搞最佳聰。本發明 ，氧化物擔體組成以γ-Α12〇3為主要成份。對拙金屬以卿旗丫為〇:為 最佳’對Pt金屬以Ce02/y-Al203為40斯％/6〇斯％最佳。 ’ 、含白金族金屬元素之氧化物擔體為，為〇3的組合時，在氯的產率 及酒精轉化率上都有良好表現。而代與抑在降低曱燒與一氧化碳產率，及 防止Rh燒結與齡經氧化變大降低觸媒的比表面積上，是良好的觸媒金 屬。因此’本發_觸媒床之白金族金取素之總重量除鱗巢社構體之 體積’每立方英吸含2〇〜働克之白金族金屬元素，較佳為每立方英吸含 8〇〜500克之白金族金屬元素。白金族金屬的重量比為_概=〜 850/〇，〇〇/0 〜30%，15% 〜60%。 〇 产進料反應混合物中水與酒精的莫耳比愈大，氫產率愈高。空氣中 氣與酒精莫耳比愈大，氧化愈完全容易獲得低產率的一氧化碳。但 形有高仏之疑慮’後者摘媒金屬過氧化燒結之疑慮，因此本發明程^ 200909348 中以反應物巾之水無精的莫耳比為1G〜4Q;氧氣與鋪莫耳比為防 1為較佳。 本發明第—較佳實施例之富氫氣體燃料生產系統示意圖如第-圖所 示i括水蒸氟進料裝置1用以輸出水蒸氣，其係包括一水進料裝置u ，接-水»器12，該水蒸發器12用讀液體水蒸發成水統，該水蒸發 器12又和-第—混合器3連接；一空氣進料震置2係提供$氣該空氣進 料裝置2係連接該第—混合器3，該第—混合器3先將水蒸氣與空氣混合， 並輸出水蒸氣及球之混合氣體；―酒精蒸氣進料裝置4㈣輸出酒精蒸 氣’其係包含-酒精進料裝置41連接—;§精蒸發器42，該酒精蒸發器幻 係將液體酒精蒸發成氣體酒精，並和該水蒸氣與空氣之混合氣體混合；一 絕熱反應器5，該絕熱反應器5包含一絕熱壁51、一重組器&及一觸媒床 53々觸媒床53設於触52内，且職_ 52設於魏_ 51内， 該絕熱反應H 5用以触水統、空氣及_統之混合氣體，將該混合 氣體導錢觀床53 ’進行_錢纽反應；-統接《置6和該i 熱反應器5連接，接收產生之氫氣’且該氫氣接收裝置6連接燃料電池或 内燃機、_電域_機_料處理設備，並觀統_料電池或内 燃機的燃料處理設備巾，或錢#伽料電池或内賴_料，其十該燃 料電池係選自固態燃料電池、融溶碳酸鹽燃料電池及質子交換膜燃料 所組成之群組之其巾之—者；助燃機係選自汽油_機及柴 ’ 組成之群組之其巾之—者。 ‘.，、钱所 本發明第一較佳實施例之富氫氣體燃料生產系統之富氫氣體燃 料生產程序之步驟包括(如第二圖所示）： ‘”' S11將該水蒸氣、該空氣混合後，再和該酒精蒸氣混合，將水蒸氣、 空氣及酒精蒸氣形成之混合氣體輸送至一絕熱反應器中之二、=' 床；及 啁媒 S12進行酒精產氫重組反應後，由該絕熱反應器輸出氫氣。 200909348 本發明第二較佳實施例之富氫氣體燃料生產系統示意圖如第三圖所 示’包括：-水蒸氣進料裝置卜其係包括—水進料裝置u連接—水蒸發 器12，該水蒸發器12用以將㈣水蒸發成水蒸氣；—空氣進料裝置^一 酒精蒸氣進料裝置4，其係包含―膽進料裝置41連接—麟蒸發器42， 該酒精蒸發ϋ 42係將液體_蒸發減體贿；—絕熱反應器5，其係包 括一絕熱壁51、一重組器52及一觸媒床53，該觸媒床兄設於該重組器52 内’且該重組器52設於該絕熱壁51内，該絕熱反應器5用以接收水蒸氣、 ，氣及酒精蒸氣之混合氣體，將該混合氣體導入該觸媒床53，進行酒精產 氫重組反應；—氫氣接收裝置6和該絕熱反應器5連接，接收產生之氫氣， 且該氫氣接收裝置6連接顧電池或嶋:機、燃料電池朗燃機的燃料處 理設備，並輸送氫氣到燃料電池或内燃機的燃料處理設備中，或直接當作 燃料電池或内燃機的燃料’其中該燃料電池係選自_、燃料電池、融炼礙 酸鹽燃料電池及質子交換膜燃料電池所組成之群組之其中之一者；該内燃 機係選自汽油内燃機及柴油内燃機所組成之群組之其中之一者。 本發明第二較佳實施例之富氫氣體燃料生產系統之富氫氣體燃料生產 程序之步驟包括（如第四圖所示）： S21將水蒸氣、空氣及酒精蒸氣形成之混合氣體輸送至一絕熱反應器 中之一觸媒床；及 S22進行酒精產氫重組反應後，由該絕熱反應器輸出氫氣。 本發明第二較佳實施例之富氫氣體燃料生產系統示意圖如第五圖所 示，包括：一水進料裝置U及一酒精進料裝置41，分別和一第二混合器7 連接，5亥第一混合器7用以將水與酒精混合；一水及酒精蒸發器8將水與 酒精混合液加熱成蒸氣；一空氣進料裝置2輸送空氣和蒸氣狀的水與酒精 混合後輸送至一絕熱反應器5，該絕熱反應器5，其係包括一絕熱壁51、一 重組器52及一觸媒床53，該觸媒床53設於該重組器52内，且該重組器 52設於該絕熱壁51内，該絕熱反應器5用以接收水蒸氣、空氣及酒精蒸氣 之此5氧體，將該混合氣體導入該觸媒床53，進行酒精產氫重組反應；一 10 200909348 ^氣接收裝置6和該絕熱反應II 5連接’接收產生之氫氣，且該氫氣接收 太連接燃料電池或内燃機、燃料電池或内燃機的燃料處理設備，並輸 达虱氣到㈣電池或_機_料處理設備中，或直接#作祕電池或内 燃2的料，其中該燃料電池麵自嶋燃料電池、融熔碳酸鹽燃料電池 及貝子又換麵料電池所組成之群組之其巾之—者；該嶋機係選自汽油 内燃機及柴油内燃機所組成之群組之其中之一者。 本發明第二較佳實施例之富氫氣體燃料生產系統之富氫氣體燃 料生產程序之步驟包括（如第六圖所示）： S31將酒精及水混合後進行蒸發’再和該空氣混合將水蒸氣、空氣 及酒精瘵氣开 >成之混合氣體輸送至一絕熱反應器中之一觸媒床； 及 、 S32進行酒精產氫重組反應後，由該絕熱反應器輸出氫氣。 例1 本發明的自發熱酒精重組觸媒以下列方式配製，使用每平方英吋2〇〇 個氣流通道(200 channels per square inch)的陶瓷蜂巢結構體(ceramic honeycomb m_lith) ’本例觸媒代號H_41之擔體每立方英呎含忾族金屬 (PGM: Platinum group metal)總量為 300 。其中 pt/pd/Rh 的重量比為 20%/20%/60%，擔體為 γ-Α1203。 觸媒用來自發熱重組酒精，以獲得富氫的合成氣產物。每分鐘1317毫 升(13.17 mL/min.)的水，20.21毫升的酒精(20.21 mL/min.)。水蒸發後與每分 鐘通入15.5〜17公升(15.5〜17 L/min.)的空氣混合。該混合氣流與下游的蒸 發酒精混合進料，經預熱管進入重組器，然後通過代號^[_41之觸煤床。進 料的每小時氣流空間速度(GHSV, Gas Hourly Space Velocity)約為6.0 X 1〇4 hr ’水蒸氣與酒精摩耳比為2.31 ’氧氣與酒精摩耳比在0.406〜0.445。觸 媒床的溫度在500°C〜800°C範圍内。表1指出產物氣體中含富氫、低一氧 化碳、低甲烷、高二氧化碳、且完全的酒精轉化’顯示本發明酒精重組器 的效率及此力。表1中之酒精轉化率以XEt0H表示，其定意為重組反應消耗 200909348 的酒精料數與進射酒精料數_值心代表絲—料酒精產生的 氫摩耳數；s代表產物中各個組成的選擇性，財&為產物中所有氯原 子摩耳數中所含氏中的氫原子料數的分率；&、、、§⑽代表產物 中所有碳原子摩耳數中所含該成份中碳原子摩耳數分率。 表1 H_41觸媒床之各項實驗數據200909348 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a fuel production system and a fuel production program, and particularly to a hydrogen-rich gas (four) production system and a hydrogen-rich gas regenerative residual, which is lie on a fuel The field of fuel for batteries and internal combustion engines. [Prior Art] Catalytic partial oxidation of hydrocarbon, methanol, alcohol feeds or catalytic vapor recombination procedures to produce rich and reduced bodies is a well-known technique. Usually, such a process is to recombine a carbon gas compound, methanol, and alcohol feed into a two-stage reaction 催化 'catalytic partial oxygen system to produce a gas rich gas. Another conventional technique is to carry out a catalytic partial oxidation or vapor recombination reaction when the single-reaction n contains a plurality of contact zones. Such conventional techniques that have been disclosed include the following: US 4,522,894, US 6,849,572, US 7,715,827, US 7,144,566, US 7,153,344, US 7,150,866, US 6,949,683, and US 6,936,237. The continuous multilayer catalyst zone or the two-stage reactor used in the prior art process is much more complicated than the single self-heating reactor of the single catalyst zone of the present invention. The hydrogen-rich gas fuel production system and the hydrogen-rich gas fuel production program of the present invention not only saves the reactor volume and the monovalent cost of the catalyst monomer, but also reduces the drop caused by the catalytic partial oxidation or vapor recombination reaction. At the same time, through the self-heating recombination reaction, the advantages of partial oxidation and vapor recombination reaction (good start-up and high hydrogen yield) can be achieved by means of low-temperature preheating and adiabatic reactor design. In the prior art, it is known that the main purpose of the alcohol hydrogen production process is to produce a hydrogen rich gas. The following chemical reactions are included: C2H5OH +l/202-2CO +3H2 AH(25t)= :+14 KJ/mol (i) C2H5OH +H20->2C0 +4H2 ΔΗ(25χ)= +256 KJ/mol (2) C〇+H2O —^C〇2 + H2 ΔΗ(25ΐ)= -41 KJ/mol (3) C2H5OH +3H20-^2C02 +6H2 ΔΗ(25Ϊ)= +174 KJ/mol (4) 200909348 C2H5OH +2H20 -H/ 202-.2C02 +5H2 AH(25C) = -68 KJ/mol (5) According to the thermodynamic equilibrium, the catalytic partial oxidation of the alcohol of reaction (1) can produce 3 moles of hydrogen; and the reaction (2) The catalytic alcohol recombination reaction can produce 4 moles of hydrogen, but for a strong endothermic reaction, the reaction ϋ 县县. (: The temperature of the company is expected to make the reaction reach a flat state, which is quite unfavorable in energy utilization. The reaction (2) and the water vapor shift reaction (Watergasshift fine km) of the reaction (1) can produce a reaction (4) to produce 6 moles, but still a heat source to maintain the vapor recombination reaction. The self-heating alcohol recombination reaction of the present invention is a reaction (5), and the thermodynamic combination of the reaction (^) and the reaction (3) is an exothermic reaction, which enables the reactant to be fed. The preheating temperature is lowered and the catalytic reaction of the catalyst is exothermic in the adiabatic reactor to maintain (8) C, which produces a rapid reaction power. The prior art has indicated that the hydrogen yield and alcohol in the catalytically active metal for the alcohol recombination reaction The order of activity of the conversion is: Rh~Ni~Co > Pd > Pt > Ru~Zn~Cu~Fe. Especially in the case of the γ-Αΐ2ο3 support, it is more obvious, but at high temperature, c. , Ru, Cu are prone to carbon deposit poisoning catalyst, Ni has a low CO conversion rate and is easy to generate high concentration of decane, and the conversion rate of c〇 under pt/Ce〇2 is higher than that of Rh/Ce02. The towel is shaped as a metal element of the platinum group, and the catalyst is oxidized. The carrier is composed of at least one of aluminum oxide, oxidized cone, cerium oxide, copper oxide and zinc oxide. SUMMARY OF THE INVENTION The main object of the present invention is to provide a hydrogen-rich gas fuel production system and a hydrogen-rich gas fuel production program. It is a single self-heating reactor using a single catalyst zone. Compared with the continuous multilayer catalyst zone used in the prior art or using a two-stage reactor, the invention can save reactor volume and catalyst cost, and can reduce Pressure drop caused by catalytic partial oxidation or vapor recombination reaction. "The secondary objective of the present invention is to provide a hydrogen-rich gaseous fuel production system and a hydrogen-rich gaseous fuel production process that can reduce the preheating temperature of the reactant feed, And exothermic by catalytic reaction of the catalyst, maintaining 500-80 (TC, generating rapid reaction power in the adiabatic reactor. Another object of the present invention is to provide a hydrogen-rich gas fuel production system and hydrogen-rich gas combustion 200909348 f production The program has the advantages of reducing the carbon deposits, preventing the formation of a burnt carbon and high conversion rate, compared to the touch of the contact medium. The invention relates to a hydrogen-rich gas fuel production system and a hydrogen-rich gas fuel production program, and the following are: "Production secrets, including: - money gas into the listening, which is to transport water vapor; ^ milk into the listener', Conveying air; _ riding steam feeding device, which is conveying alcohol vapor 'and - adiabatic reaction n 'the outside of the adiabatic reactor has a heat insulating wall, and - the recombiner is placed on the insulating wall (10) and - the catalyst bed is placed The inside of the recombiner; the mixed gas formed by the water vapor, the open space and the fine system is sent to Weier and vice versa, and the reaction generates helium gas. The hydrogen-rich turning production process includes: The mixed gas formed by the vapor, air and alcohol vapor is sent to the "catalyst bed" in the adiabatic reactor; and after the nitrogen recombination reaction is carried out, the hydrogen is taken out from the adiabatic reactor. [Embodiment] The principles of the detailed design and the preferred embodiments of the present invention are described below in order to provide a further understanding of the features and method steps of the present invention. The procedure according to the invention is achieved by a -stage process. That is, the water in the reactant is evaporated and mixed with air, and then preheated with the evaporated alcohol, and then directly introduced into the single catalyst bed of the recombiner in the adiabatic reactor for alcohol recombination reaction; or the water and alcohol in the reactant first After evaporating into a gas phase separately, after entering the preheating of the guide and the downstream air, the mixture is directly introduced into the single catalyst bed of the recombiner in the adiabatic reactor for alcohol recombination reaction; or the water is mixed with the alcohol and then mixed and mixed with the air. And then directly introduced into the single catalyst of the recombiner in the adiabatic reactor for alcohol recombination reaction. When the reactant is initially exposed to the preheated catalyst bed, a catalytic partial oxidation reaction is carried out, and the resulting C 〇 is then subjected to an exothermic water gas shift reaction and provides the endothermic heat required for the partial oxidation reaction. The evaporation temperature of water and alcohol is 150 ° C ~ 400. (: 'The temperature of the water, alcohol and air mixture is maintained at 15 ° ~ 400 ° C, the temperature of the catalyst bed is maintained at 500. 〇 ~ 8 (8). c. On the chemical kinetics of alcohol recombination hydrogen production reaction' The recombination procedure of the present invention encompasses a combination of a catalytic partial oxidation reaction and a catalytic vapor recombination reaction 'but chemical hydrogenation may be considered a combination of a catalytic partial oxidation reaction and a catalytic water vapor transfer 200909348. (iv) The catalyst bed of the invention includes: a body-formed ceramic or stainless steel honeycomb structure, and the honeycomb: has a plurality of stomatal channels, preferably with a brain per square inch of cerebral enthalpy And the surface of the honeycomb structure and the surface of the pore channel. The platinum group metal element is selected from the group consisting of (4) (4) and 姥 (10)): a mixture of the group or a group thereof. The material of the oxide support is selected from the group consisting of bismuth trioxide, 2 volt, oxygen (10), copper oxide and zinc oxide, or a group thereof, and the age of the object, shot three Oxidation two grades (10) (four), melons, especially for base metals can obtain high yield of hydrogen and high _ = : 5 - oxidation - and γ_Α12〇3 is the preferred material. The invention is added to the third oxidation and = oxides such as oxidation, oxygen (10), copper oxide and oxidation, in order to maintain the thermal properties of the catalyst bed, reduce carbon deposition to prevent poisoning of the catalyst, and act as a reaction. The accelerator reduces the yield of the A-burning-emulsified carbon. The above-mentioned added oxide towel is best for Conghua (5). In the present invention, the oxide support has a composition of γ-Α12〇3 as a main component. For the base metal, the flag is 〇: the best is the best for the Pt metal with Ce02/y-Al203 of 40 s%/6 〇. The oxide support containing a platinum group metal element is a combination of ruthenium 3 and has a good performance in terms of chlorine yield and alcohol conversion rate. It is a good catalyst metal in order to reduce the yield of smoldering and carbon monoxide, and to prevent Rh sintering and age oxidation to reduce the specific surface area of the catalyst. Therefore, 'the total weight of the platinum-golden gold extract of the hair-receiving bed is divided by the volume of the scale nest body'. Each cubic inch contains 2〇~働克的白金族金属元素, preferably 8 per cubic inch. 〇 ~ 500 grams of platinum metal elements. The weight ratio of the platinum group metal is _ abbreviation = 850 / 〇, 〇〇 / 0 ~ 30%, 15% ~ 60%. The greater the molar ratio of water to alcohol in the feed reaction mixture, the higher the hydrogen yield. The greater the molar ratio of air to alcohol in the air, the more complete the oxidation is easy to obtain low yields of carbon monoxide. However, there is a suspicion of sorghum's doubts about the latter's oxidative sintering of the metal. Therefore, in the process of the invention, the water molar ratio of the reaction towel is 1G~4Q; the oxygen and the paving ratio are 1 It is better. A schematic diagram of a hydrogen-rich gas fuel production system according to a first preferred embodiment of the present invention, as shown in the first drawing, includes a water-steamed fluorine feeding device 1 for outputting water vapor, which comprises a water feeding device u, and a water-feeding device. The water vaporizer 12 is evaporated into a water system by reading liquid water, and the water vaporizer 12 is connected to the first-mixer 3; an air feed is provided to provide a gas supply device 2 Is connected to the first mixer 3, the first mixer 3 first mixes water vapor with air, and outputs a mixed gas of water vapor and ball; - alcohol vapor feeding device 4 (four) outputs alcohol vapor 'the system contains - alcohol into The material device 41 is connected to a fine evaporator 42 which evaporates liquid alcohol into gaseous alcohol and is mixed with the mixed gas of water vapor and air; an adiabatic reactor 5, the adiabatic reactor 5 comprises An insulating wall 51, a recombiner & and a catalyst bed 53 々 catalyst bed 53 are disposed in the contact 52, and the _ 52 is located in the Wei _ 51, the adiabatic reaction H 5 is used to touch the water system, the air And the mixed gas of the system, the mixed gas is guided to the bed to carry out the 53' _ Qianxin reaction; 6 is connected to the i-thermal reactor 5 to receive the generated hydrogen 'and the hydrogen receiving device 6 is connected to the fuel cell or the internal combustion engine, the electric field_machine-processing device, and the fuel processing device of the battery or the internal combustion engine Towel, or money, the fuel cell is selected from the group consisting of a solid fuel cell, a melted carbonate fuel cell, and a proton exchange membrane fuel; The machine is selected from the group consisting of gasoline, machine and firewood. The steps of the hydrogen-rich gaseous fuel production process of the hydrogen-rich gaseous fuel production system of the first preferred embodiment of the present invention include (as shown in the second figure): '''S11 the water vapor, the After the air is mixed, it is mixed with the alcohol vapor, and the mixed gas formed by water vapor, air and alcohol vapor is sent to the second, =' bed of the adiabatic reactor; and the S12 is subjected to the alcohol hydrogen production recombination reaction. The adiabatic reactor outputs hydrogen gas. 200909348 A schematic diagram of a hydrogen-rich gaseous fuel production system according to a second preferred embodiment of the present invention is as shown in the third figure 'including: - a steam feed device comprising a water feed device u connection a water evaporator 12 for evaporating (iv) water into water vapor; an air feed device, an alcohol vapor feed device 4, comprising a "bare feed device 41" - a lining evaporator 42 The alcohol evaporating crucible 42 is a liquid evaporating body brittle; the adiabatic reactor 5 includes a heat insulating wall 51, a recombiner 52 and a catalyst bed 53, and the catalyst bed is set in the recombiner 52 inside 'and the reorganizer 52 is set in the In the wall 51, the adiabatic reactor 5 is configured to receive a mixed gas of water vapor, gas and alcohol vapor, and introduce the mixed gas into the catalyst bed 53 to perform an alcohol hydrogen recombination reaction; the hydrogen receiving device 6 and the heat insulating device The reactor 5 is connected to receive the generated hydrogen gas, and the hydrogen receiving device 6 is connected to the fuel processing device of the battery or the fuel cell burner, and delivers hydrogen to the fuel processing device of the fuel cell or the internal combustion engine, or directly As a fuel for a fuel cell or an internal combustion engine, wherein the fuel cell is selected from the group consisting of a fuel cell, a smelting acid fuel cell, and a proton exchange membrane fuel cell; the internal combustion engine is selected from the group consisting of One of a group consisting of a gasoline internal combustion engine and a diesel internal combustion engine. The steps of the hydrogen-rich gaseous fuel production process of the hydrogen-rich gas fuel production system of the second preferred embodiment of the present invention include (as shown in the fourth figure): S21 transports a mixed gas formed by water vapor, air and alcohol vapor to one of the catalyst beds in an adiabatic reactor; and S22 performs a hydrogen recombination reaction after alcohol production Hydrogen is output from the adiabatic reactor. A schematic diagram of a hydrogen-rich gaseous fuel production system according to a second preferred embodiment of the present invention, as shown in FIG. 5, includes: a water feed device U and an alcohol feed device 41, respectively The second mixer 7 is connected, the first mixer 7 is used to mix water and alcohol; the water and alcohol evaporator 8 is used to heat the water and alcohol mixture into a vapor; and the air feeding device 2 is to deliver air and vapor. The water is mixed with the alcohol and then sent to an adiabatic reactor 5, which includes a heat insulating wall 51, a recombiner 52, and a catalyst bed 53. The catalyst bed 53 is disposed in the recombiner 52. The regenerative reactor 52 is disposed in the heat insulating wall 51 for receiving the 5 oxygen body of water vapor, air and alcohol vapor, and introducing the mixed gas into the catalyst bed 53 for alcohol production. Hydrogen recombination reaction; a 10 200909348 ^ gas receiving device 6 and the adiabatic reaction II 5 are connected to 'receive the generated hydrogen gas, and the hydrogen gas receives the fuel processing device that is too connected to the fuel cell or the internal combustion engine, the fuel cell or the internal combustion engine, and delivers helium gas To (four) battery or _ machine _ In the material processing equipment, or directly #秘秘电池 or internal combustion 2 material, wherein the fuel cell surface is self-tanning fuel cell, molten carbonate fuel cell and shellfish and fabric battery group The downtime machine is selected from the group consisting of a gasoline internal combustion engine and a diesel internal combustion engine. The steps of the hydrogen-rich gaseous fuel production process of the hydrogen-rich gas fuel production system of the second preferred embodiment of the present invention include (as shown in FIG. 6): S31 combines alcohol and water to evaporate 'and then mix with the air The water vapor, air and alcohol helium gas are mixed into a catalyst bed in an adiabatic reactor; and, after S32 is subjected to an alcohol hydrogenation recombination reaction, hydrogen is output from the adiabatic reactor. Example 1 The self-heating alcohol recombination catalyst of the present invention was prepared in the following manner, using a ceramic honeycomb structure (ceramic honeycomb m_lith) of 200 channels per square inch per square inch. The total amount of PGM: Platinum group metal per cubic metre of H_41 is 300. The weight ratio of pt/pd/Rh is 20%/20%/60%, and the support is γ-Α1203. The catalyst is derived from a heat-recombinant alcohol to obtain a hydrogen-rich synthesis gas product. 1317 ml (13.17 mL/min.) of water per minute, 20.21 ml of alcohol (20.21 mL/min.). After the water has evaporated, it is mixed with air of 15.5 to 17 liters (15.5 to 17 L/min.) per minute. The mixed gas stream is mixed with the downstream evaporated alcohol feed, passed through a preheating tube into the reformer, and then passed through a coal bed codenamed [[41]. The gas hourly space velocity (GHSV, Gas Hourly Space Velocity) of the feed is about 6.0 X 1 〇 4 hr ‘the water vapor to alcohol molar ratio is 2.31 ’. The oxygen to alcohol molar ratio is 0.406 to 0.445. The temperature of the catalyst bed is in the range of 500 ° C to 800 ° C. Table 1 indicates that the product gas contains hydrogen rich, low carbon monoxide, low methane, high carbon dioxide, and complete alcohol conversion' showing the efficiency and strength of the alcohol recombiner of the present invention. The alcohol conversion rate in Table 1 is expressed by XEt0H, which is defined as the number of alcohols and the amount of incoming alcohol in the reaction reaction consumption 200909348. The value represents the number of hydrogen moles produced by the silk alcohol; s represents the composition of the product. The selectivity, the sum of money is the fraction of the number of hydrogen atoms in the moles of all chlorine atoms in the product; &,,, §(10) represents the number of moles of all carbon atoms in the product. The fraction of carbon atoms in the composition. Table 1 Experimental data of H_41 catalyst bed
Air (LP M) O/C (mol/ mol) Reside nee time( msec) h2 (Vol. %) ch4 (Vol. %) CO (Vol. %) C〇2 (Vol. %) n2 (Vol. %) Yh2 (mol/ mol) Sco (%) Sc〇2 (%) ScH4 (%) SH2 (%) XEtOH (%) 17 0.448 59.43 44.12 h 1.04 7.70 13.81 卜 33.31— 卜2.227 34.23 Γ61.19 4.58 95.53 100 16.5 0.433 60.12 ^45.20 1.13 7.63 13.72 32.20 2.245 34.07 60.99 4.95 95.31 100 16 0.420 60.80 45.03 1.57 7.74 13.88 31.76 2.248 32.28 60.85 6 RR cn oc 100 100 15.5 0.408 61.54 45.33 1.86 7.14 14.70 30.95 2.245 30.11 62.04 7 85 〇〇 ΛΊ 例2 本發明的自發細精重_媒訂财植製，個每平方英时· 個氣流通道(2〇〇 channels per SqUare inch)的陶瓷蜂巢結構體(_响 honeycomb monolith)，本例觸媒代號H_10〜Η·13之載體每立方英吸含丹 族金屬(PGM:Platinumgroupmetal)總量為 200g/ft3。其中 Pt/Pd/Rh 重量比 為 60%/20%/20% ’ 擔體中之 〇〇2/γ-Α12〇3 重量比為 〇_8〇%/1〇〇_2〇%。 觸媒用來自發熱重組酒精，以獲得富氫的合成氣產物。每分鐘13 口毫 升(13.17mL/min‘)的水’ 20.21毫升的酒精(20.21 mL/min·)。水蒸發後與每分 鐘通入15.5公升的空氣(15.5L/min·)混合。該混合氣流與下游的蒸發酒精二 合進料，經預熱管進人重組器，然後通過代號H_1〇〜H_13觸煤床。以獲得 富氫的合成氣產物。進料的每小時氣流空間速度為5 85 χ，水蒸氣 與酒精摩耳比為2.2卜氧氣無精料tb為請8,媒床的溫度在霄 800°C範圍内。表2指出產物氣體中含富氫、低一氧化碳、低甲烧、高二氧 化碳、且完全的酒精轉化，顯示本發明酒精重組器的效率及能力。且顯現 觸媒支撐物中含Ce〇2時能使曱烷產率降低。表2中之χ Q" ttDli 1 H2 N OJ-J2 、Air (LP M) O/C (mol/ mol) Reside nee time( msec) h2 (Vol. %) ch4 (Vol. %) CO (Vol. %) C〇2 (Vol. %) n2 (Vol. %) Yh2 (mol/ mol) Sco (%) Sc〇2 (%) ScH4 (%) SH2 (%) XEtOH (%) 17 0.448 59.43 44.12 h 1.04 7.70 13.81 Bu 33.31 - Bu 2.227 34.23 Γ61.19 4.58 95.53 100 16.5 0.433 60.12 ^45.20 1.13 7.63 13.72 32.20 2.245 34.07 60.99 4.95 95.31 100 16 0.420 60.80 45.03 1.57 7.74 13.88 31.76 2.248 32.28 60.85 6 RR cn oc 100 100 15.5 0.408 61.54 45.33 1.86 7.14 14.70 30.95 2.245 30.11 62.04 7 85 〇〇ΛΊ Example 2 The invention of the spontaneous fine and fine _ media-made financial system, a square channel per square inch per channel (2 〇〇 channels per SqUare inch) ceramic honeycomb structure (_ ring honeycomb monolith), this example of the catalyst code H_10 ~ The carrier of Η·13 has a total amount of 200 g/ft3 of metal (PGM: Platinum groupmetal) per cubic inch. The weight ratio of Pt/Pd/Rh is 60%/20%/20%' 〇〇2/γ-Α12〇3 in the support is 〇_8〇%/1〇〇_2〇%. The catalyst is derived from a heat-recombinant alcohol to obtain a hydrogen-rich synthesis gas product. 13 milliliters per minute (13.17 mL/min ') of water ' 20.21 ml of alcohol (20.21 mL/min·). After the water evaporates, it is mixed with 15.5 liters of air (15.5 L/min·) per minute. The mixed gas stream is combined with the downstream evaporated alcohol, fed into the recombiner through a preheating tube, and then contacted the coal bed by code H_1〇~H_13. A hydrogen rich synthesis gas product is obtained. The hourly airflow velocity of the feed is 5 85 χ, the water vapor to alcohol molar ratio is 2.2, the oxygen-free concentrate tb is 8, and the temperature of the media bed is 霄 800 °C. Table 2 indicates that the product gas contains hydrogen-rich, low carbon monoxide, low-combustion, high carbon dioxide, and complete alcohol conversion, indicating the efficiency and ability of the alcohol recombiner of the present invention. It also shows that when the catalyst support contains Ce〇2, the yield of decane can be lowered. In Table 2, Q" ttDli 1 H2 N OJ-J2,
Sc〇、SCH4、SC02之定義與例1相同。 12 200909348 表2 H-10〜H-13觸媒床之各項實驗數據The definitions of Sc〇, SCH4, and SC02 are the same as in Example 1. 12 200909348 Table 2 Experimental data of H-10~H-13 catalyst bed
Catalyst Ce〇2 (wt%) γ-Α1203 (wt%) η2 (Vol. %) CH4 (Vol. %) CO (Vol. %) C02 (Vol. %) n2 (Vol. %) ------ Yh2 (mol/ mol) Sco (%) Sc〇2 (%) S〇H4 (%) Sh2 (%) XEtOH (%) H13 0 100 40.31 1.92 9.12 16.18 32.44 1.905 33.44 59.48 7.07 91.30 100~ H10 40 60 ^〇J〇0_ 0.71 8.8 15.90 34.50 1.779 34.78 62.50 2.72 96.67 100 H11 60 40 0.97 8.47 16.50 33.84 1.822 ^2.64 63.71 ^ 66 95.50 ion H12 80 20 38.50 0.91 8.17 16.50 35.60 1.656 32.03 64.35 3.62 95.41 100 ”’不上所述本發明之§氫氣體燃料生產纟、統及富氫氣體燃料生產程序具有 下列之優點： 1. f發明使用單-觸媒區之單—自發熱反應器，相較於習知技術使用的連 續多層觸舰或使用兩階段反鮮，本發明能節省反應碰積及觸媒成 本’且能降低催化性部分氧化或蒸氣重組反應造成的壓降。 2. 本發明能使反應物進料之麵溫度降低，並經之催化反應放熱，在 絕熱反應器中維持500姻。c，產生快速的反應動力。 3. 本發明使用之觸媒床相較於習知之觸媒，具有降低礙沉積物的毒化、不 易生成甲烷及高轉換率之優點。 准以上所述者’僅為本發明之較佳實施例而已，並非用來限定本發明 實施之範圍’舉凡依本發明巾請專纖_述之構造、賴及精神所為之 均等變化與料’均應包括於本發明之㈣專職圍内。 【圖式簡單說明】 第-圖為本發明第—較佳實施例之f氫氣體燃料生產紐示意圖。 第二圖為本發明第-較佳實施例之富氫氣體燃料生產系統之富氣氣 體燃料生產程序之步驟流程圖。 第二圖為本發明第二較佳實施例之富氫氣麵料生產线示意圖。 第四圖為本發明第二較佳實施例之富氫氣體燃料生產系統之富氣氣 體燃料生產程序之步驟流程圖。 第五圖為本發明第三較佳實施例之富氫氣體燃料生產系統示意圖。 200909348 第六圖為本發明第三較佳實施例之富氫氣體燃料生產系統之富氫氣 體燃料生產程序之步驟流程圖。 【主要元件符號說明】 1水蒸氣進料裝置 11水進料裝置 12水蒸發器 2空氣進料裝置 3第一混合器 4酒精蒸氣進料裝置 41酒精進料裝置 42酒精蒸發器 5該絕熱反應器 51絕熱壁 52重組器 53觸媒床 6氫氣接收裝置 7第二混合器 8 水及酒精蒸發器 14Catalyst Ce〇2 (wt%) γ-Α1203 (wt%) η2 (Vol. %) CH4 (Vol. %) CO (Vol. %) C02 (Vol. %) n2 (Vol. %) ----- - Yh2 (mol/ mol) Sco (%) Sc〇2 (%) S〇H4 (%) Sh2 (%) XEtOH (%) H13 0 100 40.31 1.92 9.12 16.18 32.44 1.905 33.44 59.48 7.07 91.30 100~ H10 40 60 ^ 〇J〇0_ 0.71 8.8 15.90 34.50 1.779 34.78 62.50 2.72 96.67 100 H11 60 40 0.97 8.47 16.50 33.84 1.822 ^2.64 63.71 ^ 66 95.50 ion H12 80 20 38.50 0.91 8.17 16.50 35.60 1.656 32.03 64.35 3.62 95.41 100 ” § Hydrogen gas fuel production 纟, system and hydrogen-rich gas fuel production process has the following advantages: 1. f invention single-catalyst zone single-self-heating reactor, continuous multilayer compared to conventional techniques The invention can save the reaction and the catalyst cost by using the two-stage reverse freshness, and can reduce the pressure drop caused by the catalytic partial oxidation or the vapor recombination reaction. 2. The invention can make the surface temperature of the reactant feed Decreased, and exothermic by the catalytic reaction, maintaining 500 cc in the adiabatic reactor, producing rapid reaction power. The catalyst bed used in the present invention has the advantages of reducing the poisoning of the deposit, the difficulty in generating methane and the high conversion rate compared with the conventional catalyst. The above is merely a preferred embodiment of the present invention. It is not intended to limit the scope of the practice of the present invention. The structure and the equivalent of the structure and the spirit of the invention shall be included in the (4) full-time enclosure of the present invention. The first drawing is a schematic diagram of the production process of the hydrogen gas fuel of the first preferred embodiment of the present invention. The second drawing is a step of the gas-rich gas fuel production process of the hydrogen-rich gas fuel production system of the first preferred embodiment of the present invention. The second figure is a schematic diagram of a hydrogen-rich gas production line according to a second preferred embodiment of the present invention. The fourth figure is a gas-rich gas fuel production process of a hydrogen-rich gas fuel production system according to a second preferred embodiment of the present invention. The fifth embodiment is a schematic diagram of a hydrogen-rich gas fuel production system according to a third preferred embodiment of the present invention. 200909348 FIG. 6 is a hydrogen-rich gas fuel production system according to a third preferred embodiment of the present invention. A step of producing a hydrogen rich gas fuel flow chart of the program. [Main component symbol description] 1 water vapor feeding device 11 water feeding device 12 water evaporator 2 air feeding device 3 first mixer 4 alcohol vapor feeding device 41 alcohol feeding device 42 alcohol evaporator 5 the adiabatic reaction Heater wall 52 recombiner 53 catalytic bed 6 hydrogen receiving device 7 second mixer 8 water and alcohol evaporator 14