TWI306081B - Hydrogen generating apparatus and hydrogen generating method using the hydrogen generating apparatus - Google Patents

Hydrogen generating apparatus and hydrogen generating method using the hydrogen generating apparatus Download PDF

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TWI306081B
TWI306081B TW095111879A TW95111879A TWI306081B TW I306081 B TWI306081 B TW I306081B TW 095111879 A TW095111879 A TW 095111879A TW 95111879 A TW95111879 A TW 95111879A TW I306081 B TWI306081 B TW I306081B
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combustion
group
reaction
reaction device
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TW200711989A (en
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Young Chang Byun
Jung Hyun Seo
Jae Hoon Choe
Jung Min Sohn
Jun Yeon Cho
Young Woon Kwon
Kwang Ho Song
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Lg Chemical Ltd
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    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
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Description

1306081 九、發明說明： 【發明所屬之技術領域】 • 本發明係有關於一種氫產生裝置及氫產生方法，特定 、s之，本發明係有關於一種包括含有微通道的單位反應裝 、置之氫產生裝置，以及使用該氫產生裝置之氫產生方法， ♦該微通^係包括經被覆的燃燒觸媒及/或經被覆的重組觸 •媒該氫產生裝置係設計成具有高熱效能以及對氫有高轉 化率以產生氫，其係利用醇類（例如甲醇）做為原料來提供 ♦氫至燃料電池系統等。 " 【先前技術】 ^年來，由於對環境投注愈來愈多的關心，因而使得 使用氫做為燃料的清潔燃料獲得更多的興趣和需求。 因此，對燃料電池從事不斷努力地研究，以期能取代 使用化石原料之傳統的汽油引擊和發電機。 、為、了提高燃料電池的實用性，其應伴隨有具有較佳產 #能，/或供應氫做為原料之其它條件。氫為所有氣體中最輕 的耽體’且易於在空氣中發生爆炸，所以其儲存與處理非 f困難。在現階段之技術，係使用大容量的儲存槽來供應 虱，而’此等氫用儲存槽無法完全地解決上述問題，彳 此等氯的供應方法需要初期大量用於設備的投資，例如發 展大容量的儲存槽及準備較大的儲存空間。因此，氫的^ 應係為國家基礎建設(infra_structure)的目標。 ’、1306081 IX. Description of the Invention: [Technical Field] The present invention relates to a hydrogen generating device and a hydrogen generating method. Specifically, the present invention relates to a unit reaction device including a microchannel. a hydrogen generating device, and a hydrogen generating method using the hydrogen generating device, the micro-passing system comprising a coated combustion catalyst and/or a coated recombination catalyst, the hydrogen generating device is designed to have high thermal efficiency and Hydrogen has a high conversion rate to generate hydrogen, which uses an alcohol (such as methanol) as a raw material to provide hydrogen to a fuel cell system and the like. " [Previous Technology] Over the years, more and more interest in environmental betting has led to increased interest and demand for clean fuels that use hydrogen as a fuel. Therefore, the fuel cell has been continuously researched to replace the conventional gasoline attack and generator using fossil raw materials. In order to improve the practicality of the fuel cell, it should be accompanied by other conditions that have better production energy, and/or supply hydrogen as a raw material. Hydrogen is the lightest carcass of all gases' and is prone to explosion in the air, so it is difficult to store and handle non-f. At this stage of the technology, large-capacity storage tanks are used to supply helium, and 'these hydrogen storage tanks cannot completely solve the above problems. The chlorine supply method requires an initial large amount of investment in equipment, such as development. Large capacity storage tanks and large storage space. Therefore, hydrogen is the target of national infrastructure (infra_structure). ’,

所以，較佳為製造較小的氫產生裝置，降低其重 積以使用作清潔燃料，而不需上述大量㈣設備的投資t 93390 5 1306081 為了將由較小的氫產生裝置所產生的氫直接供應 料電池等，應該使會在燃料電池中降低陽極活性之_氣^ 碳（co)之含量降低。 如同從曱醇產生氫的方法，已經發展並廣泛使用甲_ 流的重組方法（methanol_steam reforming method)。 為了進行該曱醇流重組反應，首先需要用於使液^目> 曱醇和水之混合物氣化的氣化器（gasifier)、用於將熱提供 至重組反應器的燃燒器（combustor)、與使燃燒用的液熊嫁 料氣化的氣化器，以及單獨地需要選擇性氧化反^器' (preferential oxidation reactor)，以降低含於所產生之气 的一氧化碳含量。 該甲醇流重組反應係由下述反應圖式1所示： [反應圖示 l] CH30H + H20 C〇2 + 3H2 △ H = 49.4kJ/mol (1) CH3OH — CO + 2H2 Δ H = 90.5 kJ/mol (2) CO + h2o — • C02 + H2 △ H = -41_lkJ/mol ⑶ 上文所示之甲醇流重組反應係如反應圖式1中的H (1)與反應圖式1中的反應（2)進行，直接使甲醇分解，亦^ 部分係於高溫下進行。反應圖式1中的反應（1)與 反應，所以應該從外面連續地供應熱以進行此等反應。 已知甲醇流重組反應最佳係於300°C進行。偏若溫度 高於此，將發生曱醇的直接分解以及上述反應（3)的逆反 應，而提高產物中一氧化碳的濃度。為了降低一氧化碳的 濃度，需要上述反應（3) ’水媒氣轉化反應（water-gas shift 6 93390 1306081 reaction)。因此，為了降低一氧化碳的濃度，重組器 (reformer)的溫度應精確地維持。 • 韓國專利申請案第0314829號描述甲醇重組裝置係以 ,雙管型式構成，以穩定地維持重組器的溫度。在此裝置中， 係於内管中以相同距離安置蜂巢式燃燒觸媒 combustion catalyst)，且於外管充填重組觸媒，以進行該 重組反應。藉由此結構，避免該重組器的局部溫度升高， 且該溫度係穩定地維持在200至300。(：的範圍内。然而， 畚使用像此結構的反應器並不足以降低重組器的尺寸。Therefore, it is preferred to manufacture a smaller hydrogen generating device, reduce its recombination for use as a cleaning fuel, without the investment of a large number of (4) devices described above. t 93390 5 1306081 In order to directly supply hydrogen generated by a smaller hydrogen generating device The battery, etc. should reduce the amount of carbon (co) which will reduce the anode activity in the fuel cell. Like the method of producing hydrogen from sterol, a methanol_steam reforming method has been developed and widely used. In order to carry out the sterol stream recombination reaction, a gasifier for vaporizing a mixture of liquid and sterol and water, a combustor for supplying heat to the reforming reactor, A gasifier for vaporizing a liquid bear batch for combustion, and a preferentially selective oxidation reactor are separately required to reduce the carbon monoxide content contained in the gas produced. The methanol stream recombination reaction is represented by the following reaction scheme 1: [Reaction diagram 1] CH30H + H20 C〇2 + 3H2 △ H = 49.4 kJ/mol (1) CH3OH - CO + 2H2 Δ H = 90.5 kJ /mol (2) CO + h2o — • C02 + H2 △ H = -41_lkJ/mol (3) The methanol stream recombination reaction shown above is the reaction of H (1) in Reaction Scheme 1 and Reaction Scheme 1 (2) Performing, directly decomposing methanol, and also partially performing at a high temperature. The reaction (1) in Reaction Scheme 1 is reacted with the reaction, so heat should be continuously supplied from the outside to carry out such reactions. It is known that the methanol stream recombination reaction is carried out optimally at 300 °C. If the temperature is higher than this, the direct decomposition of sterol and the reverse reaction of the above reaction (3) will occur, and the concentration of carbon monoxide in the product will be increased. In order to reduce the concentration of carbon monoxide, the above reaction (3) 'water-gas shift 6 93390 1306081 reaction is required. Therefore, in order to reduce the concentration of carbon monoxide, the temperature of the reformer should be accurately maintained. • Korean Patent Application No. 0314829 describes a methanol recombination apparatus which is constructed in a double tube type to stably maintain the temperature of the reformer. In this apparatus, a honeycomb combustion catalyst is placed at the same distance in the inner tube, and a recombination catalyst is filled in the outer tube to carry out the recombination reaction. With this configuration, the local temperature rise of the recombiner is avoided, and the temperature is stably maintained at 200 to 300. Within the range of (:), however, the use of a reactor like this structure is not sufficient to reduce the size of the recombiner.

Pacific North National Laboratory 於 J· 〇f power scnnxe，H)8(2002)2 i_27中揭露一種小尺寸的甲醇流重組裝 置，係使用曱醇做為燃燒用的燃料，並同時做為重組反應 用之原料。然而，由於為維持該反應溫度而饋入燃燒器之 作為燃料的曱醇的量相當大，因此此裝置具有約2〇〇毫瓦 特（mW)的低輸出與5至1 〇〇/0的低總熱效能之缺點。因此， 鲁仍迫切地需要發展一種氫產生裝置，其重量與尺寸為小， 仁具有尚熱效能與對氫有高轉化率，以及其具有產生大量 氫的能力。 【發明内容】 本發明係為了解決上述之習知問題。因此，本發明之 目的係提供一種包括含有微通道的單位反應裝置之氫產生 装置’以及使用該氫產生裝置之氫產生方法，該微通道係 =括、’、二被覆的燃燒觸媒及/或經被覆的重組觸媒，該氫產生 破置係設計成具有高熱效能以及對氫有高轉化率以產生 7 93390 1306081 氫，其係利用醇類（例如曱醇）做為原料來提供氫至燃料電 池系統等。 本發明之氫產生裝置係包括至少一個用於燃燒/重組 .反應的第一單位反應裝置’該第一單位反應裝置係由含有 _燃燒觸媒之燃燒用盤狀物組（plate assembly)與含有重組觸 媒之重組反應用盤狀物組所組成，其中各該盤狀物組含有 一對微通道盤狀物，微通道係形成在該微通道盤狀物的一 面的表面上，且該微通道盤狀物以該微通道彼此相對的方 畚式相互組合；其中該燃燒用盤狀物組在該微通道中包含該 燃燒觸媒；以及其中該重組反應用盤狀物組在該微通道中 包含該重組觸媒。 本發明之氫產生裝置係包括至少一個燃燒/重組反應 用的第一單位反應裝置，至少一個氣化用之第二單位反應 裝置，以及至少一個熱交換用之第主單位反應裝置，其中 該第一單位反應裝置包括含有燃燒觸媒之燃燒用盤狀物組 #與含有重組觸媒之重組反應用盤狀物組；其中該第二單位 反應裝置包括燃燒用盤狀物組與熱交換用盤狀物組；其中 該第三單位反應裝置包括熱交換用盤狀物組；其中該第一 單位反應裝置之燃燒用盤狀物組係連接至該第三單位反應 裝置之一個熱交換用盤狀物組；其令該第三單位反應裝置 之其它熱交換用盤狀物組係連接至該第一單位反應 之 燃燒用盤狀物組;且其中該第二單位反應裝置之熱交換用 盤狀物組係連接至該第一單位反應裝置之重組反應用盤狀 物組。 93390 8 1306081 本發明之氫產生方法包括，（1)第一燃燒步驟，係將氣 相燃料與氧化劑共同饋入/至該第一單位反應裝置之燃燒用 •盤狀物組’使該燃料於燃燒用盤狀物組中燃燒，並利用燃 .燒熱來加熱毗鄰該燃燒用盤狀物組之重組反應用盤狀物組; ‘以及（2)產生氫的重組步驟，係藉由將用於重組反應的原料 (包括甲醇和水的混合物）饋入至經加熱的重組反應用盤狀 物組’使該原料重組，在藉由使用包括至少一個燃燒/重組 反應用之第一單位反應裝置的氫產生裝置來產生氫時，該 畚第一單位反應裝置係包括含有燃燒觸媒之燃燒用盤狀物組 與含有重組觸媒之重組反應用盤狀物組，其中各該盤狀物 組包括一對微通道盤狀物，微通道係形成在該微通道盤狀 物的一面的表面上，且該微通道盤狀物以該微通道彼此相 對的方式相互組合；其中該燃燒用盤狀物組在該微通道中 包含該燃燒觸媒；以及其中該重組反應用盤狀物組在該微 通道中包含該重組觸媒。 _ 本發明之氫產生方法包括，（1)第一燃燒步驟，係將氣 相燃料與氧化劑共同饋入至該第一單位反應裝置之燃燒用 盤狀物組，且使該燃料燃燒；第一預熱步驟，係透過該 第二單位反應裝置之一個熱交換用盤狀物組，利用從該第 一燃燒步驟中的燃燒用盤狀物所釋放的廢氣使該第三單位 反應裝置預熱至80至10(rc;(3)第二燃燒步驟，係透過該 第二單位反應裝置之其它熱交換用盤狀物組，藉由饋入及 氣化液態燃料至該第一單位反應裝置之燃燒用盤狀物組， 並使5亥燃料與饋入的氧化劑同時燃燒，以使該第一單位反 9 93390 1306081 H置加熱i26()至道c;(4)第三燃燒步驟，為藉由將氣 :燃料饋人至該第二單位反㈣置之燃燒用盤狀物組，並 • 2該燃料與氧化劑共同燃燒’以使該第二單位反應裝置加 …、、、至110 S 200 c;(5)氣化步，驟，係藉由使該作為重組反應 1原料的甲醇與水之混合物通過該第二單位反應裝置之燃 :堯用盤狀物組，並將該混合物饋人至該第—單位反應裝置 .之重組反應用盤狀物、组，以使該混合物氣化；以及⑹重組 步驟，為藉由使該經氣化的原料通過該第一單位反應裝置 之重組反應用盤狀物組，以將該經氣化的原料重組成氫， 在藉由使用氫產生農置來產生氣時，該氣產生裝置包括至 少一$用於燃燒/重組反應的第一單位反應裝置，至少一個 用於氣化的第二單位反應裝置，以及至少一個用於熱交換 的第一單位反應裝置，其中該第一單位反應裝置包括含有 燃燒觸媒之燃燒用盤狀物組與含有重組觸媒之重組反應用 盤狀物組；其中該第二單位反應裝置包括燃燒用盤狀^組 鲁與熱交換用盤狀物組；其中該第三單位反應裝置包括熱交 換用盤狀物組；其中該第一單位反應裝置之燃燒用盤狀物 組係連接至該第三單位反應裝置之一個熱交換用盤狀物組； 其中該第三單位反應裝置之其它熱交換用盤狀物組係連接 至5亥第一單位反應裝置之燃繞用盤狀物組；以及其中該第 二單位反應裝置之熱交換用盤狀物組係連接至該第一單位 反應裝置之重組反應用盤狀物組。 【實施方式】 本發明係根據附圖詳細描述如下。 93390 10 1306081 %, 如第1圖所示，本發明之氫產生裝置的特徵在於包括 至少一個燃燒/重組反應用之第一單位反應農置（I〗），該第 • 一單位反應裝置係由含有經被覆的燃燒觸媒之燃燒用盤狀 …物組與含有經被覆的重組觸媒之重組反應用盤狀物組所組 .成，其中各該盤狀物組含有一對微通道盤狀物，微通道係 -形成在該微通道盤狀物的一面的表面上，且該微通道盤狀 .物以該微通道彼此相對的方式相互組合；其中該燃燒用盤 狀物組在該微通道中包含該燃燒觸媒；以及其中該重組反 參應用盤狀物組在該微通道中包含該重組觸媒。因此，本發 明之特徵在於可從燃燒用盤狀物組中獲得用於重組反應^ 熱，該燃燒用盤狀物組係毗鄰於含有重組觸媒之重組反應 用盤狀物組，藉此該重組反應可於理想溫度下進行，以同 時提高熱效能與對氫的轉化率。而且，該特徵亦在於雖然 本發明裝置執行傳統氫產生裝置中燃燒器的功能（其係藉 由組成燃燒用盤狀物組以執行使該燃燒反應在燃燒器中進 ^行的功能），但本發明裝置可製作成較小，且燃燒用盤狀物 組中的燃燒反應是在微通道中執行；以及雖然本發明裝置 執行傳統氫產生裝置中重組器的功能，（其係藉由組成重組 反應用盤狀物組以執行使該重組反應在重組器中進行的功 月b)，但本發明裝置可製作成較小，且重組反應用盤狀物組 中的重組反應是在微通道中執行。再者，根據本發明，如 第2圖所示’藉由組成包括燃燒用盤狀物組（41，）與重組反 應用盤狀物組（41”）之第一單位反應裝置（11)，讓該燃燒用 盤狀物組（41’）與該重組反應用盤狀物組（41，，）相互地堆 93390 11 ，‘13蝴 81 物組（41，，）相互地堆疊，且固定在這兩個蓋子之間（42與 -42’）。在這兩個蓋子（42與42,)中，舉例而言，燃燒器出口 -.(43:與4組器出口（44)係形成於頂蓋（42)，而燃燒器入口 • (^3 )與重組器入口（44，）係形成於底蓋（42，）。然而，一般而 •=通常可理解此等引用標記僅做參考用，對調的蓋子亦 .可起作用。該單位反應裝置之具體實施例的分解照片係顯 不於第3目。於第3圖所示之組成實施例中，該微通道盤 狀物（45)的厚度為約〇.3毫米（mm)，❿該微通道係形成具 有1〇至15〇微米（㈣之深度。通道係形成於平行四邊ς 型式的金屬盤狀物上，且在該金屬盤狀物之各頂點形成允 許流體流動的孔。 如第2圖、第4圖與第5圖所示，組成單位反應裝置 (41)之盤狀物組係包括一對微通道盤狀物（45與45，），一般 於該微通道盤狀物的一面的表面上形成微通道（51與 51’），且該微通道盤狀物以該微通道（51與51,)彼此相對的 Φ方式相互組合；且該燃燒用盤狀物組（41，)在該微通道（51盥 51’）中包含該燃燒觸媒；以及該重組反應用盤狀物組（今广') 在該微通道（51與51，）中包含該重組觸媒。所有蓋子鱼微 通道可以金屬予以鑄型，較佳為以具有良好抗腐钱性與抗 熱性之材料，例如不錄鋼等予以鑄型。如第6圖所示，襯 墊（61)可插入於微通道盤狀物（45與45，）之間。較佳地，該 襯塾（61)可以用銅板予以製作，且由開口⑽與貫穿孔⑹） 所組成，而形成該等開口及貫穿孔係用以在此等微通道盤 狀物（45與45，)之間製做相同的空間。因此，如第2圖之Pacific North National Laboratory, J. 〇f power scnnxe, H) 8 (2002) 2 i_27, discloses a small-sized methanol stream recombination device using sterol as a fuel for combustion and simultaneously used as a recombination reaction. raw material. However, since the amount of sterol fuel as a fuel fed to the burner to maintain the reaction temperature is relatively large, the apparatus has a low output of about 2 〇〇 milliwatts (mW) and a low output of 5 to 1 〇〇/0. The shortcomings of total thermal performance. Therefore, there is still an urgent need to develop a hydrogen generating device which is small in weight and size, has a thermal efficiency and a high conversion rate to hydrogen, and has the ability to generate a large amount of hydrogen. SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems. Accordingly, it is an object of the present invention to provide a hydrogen generating apparatus comprising a unit reaction apparatus including a microchannel, and a hydrogen generating method using the hydrogen generating apparatus, the microchannel system comprising, ', and a double coated combustion catalyst and/or Or the coated recombination catalyst, the hydrogen production breaking system is designed to have high thermal efficiency and high conversion to hydrogen to produce 7 93390 1306081 hydrogen, which uses alcohol (such as sterol) as a raw material to provide hydrogen to Fuel cell systems, etc. The hydrogen generating apparatus of the present invention comprises at least one first unit reaction apparatus for combustion/recombination. The first unit reaction apparatus is composed of a plate assembly and a combustion containing a combustion catalyst. The recombination reaction of the recombination catalyst is composed of a disc group, wherein each of the disc groups contains a pair of microchannel discs, and the microchannels are formed on the surface of one side of the microchannel disc, and the micro The channel disc is combined with each other in a square manner in which the microchannels are opposed to each other; wherein the combustion disc group includes the combustion catalyst in the microchannel; and wherein the recombination reaction disc group is in the microchannel The recombination catalyst is included. The hydrogen generating device of the present invention comprises at least one first unit reaction device for combustion/recombination reaction, at least one second unit reaction device for gasification, and at least one first unit reaction device for heat exchange, wherein the first A unit reaction apparatus includes a combustion disk group # containing a combustion catalyst and a disk group for recombination reaction containing a recombination catalyst; wherein the second unit reaction device includes a disk group for combustion and a disk for heat exchange The third unit reaction device includes a heat exchange disk group; wherein the combustion unit of the first unit reaction device is connected to a heat exchange disk of the third unit reaction device a set of other heat exchange discs of the third unit reaction apparatus connected to the combustion unit group for the first unit reaction; and wherein the second unit reaction apparatus is in the form of a disk for heat exchange The object group is connected to the disc group for recombination reaction of the first unit reaction device. 93390 8 1306081 The hydrogen generating method of the present invention comprises: (1) a first combustion step of feeding a gas phase fuel together with an oxidant to/to a combustion disk group of the first unit reaction device to make the fuel Combustion is used in the group of combustion discs, and the heat of combustion is used to heat the group of reconstituted discs adjacent to the group of combustion discs; 'and (2) the step of recombining to generate hydrogen is to be used The raw material (including a mixture of methanol and water) of the recombination reaction is fed to the heated disc group of the recombination reaction to reconstitute the raw material by using a first unit reaction apparatus including at least one combustion/recombination reaction When the hydrogen generating device generates hydrogen, the first unit reaction device includes a combustion disk group containing a combustion catalyst and a disk group for recombination reaction containing a recombination catalyst, wherein each of the disk groups a pair of microchannel discs formed on a surface of one side of the microchannel disc, and the microchannel discs are combined with each other in such a manner that the microchannels are opposed to each other; wherein the burning disc is shaped Object group The combustion channel is contained in the microchannel; and wherein the recombination reaction disk group comprises the recombination catalyst in the microchannel. The hydrogen generating method of the present invention comprises: (1) a first combustion step of feeding a gas phase fuel and an oxidant together to a combustion disk group of the first unit reaction device, and burning the fuel; a preheating step of preheating the third unit reaction apparatus by using a waste heat exchange disc group from the first combustion step through a heat exchange disc group of the second unit reaction unit 80 to 10 (rc; (3) a second combustion step, through the other heat exchange disk group of the second unit reaction device, by feeding and gasifying the liquid fuel to the combustion of the first unit reaction device Using a disc group, and burning the 5 mega fuel with the oxidant fed in so that the first unit counter 9 93390 1306081 H is heated i26 () to the path c; (4) the third combustion step is Feeding the gas: the fuel to the combustion unit of the second unit (four), and • co-combusting the fuel with the oxidant to add the second unit reaction device to, for example, 110 S 200 c (5) gasification step, by using the methanol as the raw material of the recombination reaction 1 The mixture of water is passed through the second unit reaction device: the disk group is used, and the mixture is fed to the first unit reaction device. The reconstitution reaction disk, group is used to vaporize the mixture. And (6) a recombination step of reconstituting the vaporized raw material into hydrogen by passing the vaporized raw material through a recombination reaction disk group of the first unit reaction device, by using hydrogen The gas generating device comprises at least one first unit reaction device for combustion/recombination reaction, at least one second unit reaction device for gasification, and at least one for heat exchange. a unit reaction apparatus, wherein the first unit reaction apparatus comprises a combustion disk group containing a combustion catalyst and a disk group for recombination reaction containing a recombination catalyst; wherein the second unit reaction device comprises a disk plate for combustion a group of heat exchangers for heat exchange; wherein the third unit reaction device comprises a disk group for heat exchange; wherein the combustion disk group of the first unit reaction device is connected to the third a heat exchange disk group of the reaction device; wherein the other heat exchange disk group of the third unit reaction device is connected to the combustion disk group of the 5th first unit reaction device; The heat exchange disc group of the second unit reaction apparatus is connected to the recombination reaction disc group of the first unit reaction apparatus. [Embodiment] The present invention is described in detail below with reference to the drawings. 93390 10 1306081 % As shown in Fig. 1, the hydrogen generating apparatus of the present invention is characterized in that it comprises at least one first unit reaction (I) for combustion/recombination reaction, and the first unit reaction apparatus is coated with a combustion disk-like combustion group and a disk group comprising a recombination reaction containing a coated recombination catalyst, wherein each of the disk groups comprises a pair of microchannel disks, microchannels Formed on a surface of one side of the microchannel disc, and the microchannel discs are combined with each other in such a manner that the microchannels are opposed to each other; wherein the combo disc group includes the microchannel Combustion catalyst And wherein the recombination reaction application disc group comprises the recombination catalyst in the microchannel. Accordingly, the present invention is characterized in that a recombination reaction heat can be obtained from a combustion disk group which is adjacent to a disk group for recombination reaction containing a recombination catalyst, whereby The recombination reaction can be carried out at an ideal temperature to simultaneously increase thermal efficiency and conversion to hydrogen. Moreover, this feature is also characterized in that although the apparatus of the present invention performs the function of the burner in the conventional hydrogen generating apparatus (which is constituted by the group of burning discs to perform the function of causing the combustion reaction to proceed in the combustor), The apparatus of the present invention can be made smaller, and the combustion reaction in the group of combustion discs is performed in the microchannel; and although the apparatus of the present invention performs the function of the recombinator in the conventional hydrogen generating apparatus, The reaction disk group is used to perform the work month b) in which the recombination reaction is carried out in the reformer, but the apparatus of the present invention can be made smaller, and the recombination reaction in the disc group for recombination reaction is in the microchannel carried out. Further, according to the present invention, as shown in Fig. 2, the first unit reaction device (11) consisting of a disk group (41) for combustion and a disk group (41" for recombination reaction, The combustion disk group (41') and the recombination reaction disk group (41,) are stacked on each other 93390 11 , and the '13 butterfly 81 group (41,) are stacked on each other and fixed at Between the two covers (42 and -42'). In the two covers (42 and 42,), for example, the burner outlet - (43: with the 4 sets of outlets (44) formed in The top cover (42), and the burner inlet (^3) and the recombiner inlet (44,) are formed on the bottom cover (42,). However, in general, it is generally understood that the reference marks are for reference only. The inverted lid can also function. The decomposition photograph of the specific embodiment of the unit reaction device is not shown in the third item. In the composition example shown in Fig. 3, the microchannel disc (45) The thickness is about 〇3 mm (mm), and the microchannel is formed to have a depth of 1 〇 to 15 〇 micrometers ((4). The channel system is formed in a parallelogram type. It is on the disc and forms a hole for allowing fluid to flow at each vertex of the metal disc. As shown in Fig. 2, Fig. 4 and Fig. 5, the disc group constituting the unit reaction device (41) A pair of microchannel discs (45 and 45,) are generally formed on the surface of one side of the microchannel disc to form microchannels (51 and 51'), and the microchannel disc is in the microchannel (51 and 51,) Φ modes opposed to each other are combined with each other; and the combustion disk group (41,) contains the combustion catalyst in the microchannel (51盥51'); and the disk for the recombination reaction The object group (Jianguang') contains the recombination catalyst in the microchannels (51 and 51,). All the cover fish microchannels can be metal cast, preferably with good anti-corrosion and heat resistance materials. For example, casting is performed without recording steel, etc. As shown in Fig. 6, the gasket (61) can be inserted between the microchannel discs (45 and 45,). Preferably, the liner (61) can be Made of a copper plate and composed of an opening (10) and a through hole (6), and the openings and through holes are formed for the micropass It was made between the discs (45 and 45) do the same space. Thus, as in FIG. 2 of

93390修正版 13 1306081 實施例所示，二個或大於二個之盤狀物組例如該燃燒用盤 狀物組（41’）與該重組反應用盤狀物組（41，，），可相互地堆 .疊。倘若有需要，亦即根據所欲產生的氫量等，可增加或 •減少所堆疊之燃燒用盤狀物組（41，）與重組反應用盤^狀物 組(41”)的數量。如第7圖所示，在各盤狀物㈣内部形成 -了複數個通道形成空間（71)，而該内壁係當作觸媒被覆部 分（72)，其中所被覆的觸媒為例如燃燒觸媒或重組觸媒。 如第4圖與第5圖所示，此等微通道盤狀物（45與45,) .中，上部微通道盤狀物（45)具有入口（46)、出口（47)、第一 連接孔（48)與第二連接孔（49)，其中該入口與該出口係彼此 地位於對角、線上，i該第一連接孔（48)與該第二連接孔㈣ 係彼此地位於對角線上，其中在該入口⑽與該出口⑼ 間形成溝槽’該溝槽係從包括該入口（46)與該出口⑼之表 面具有一定的深度，且該溝槽壁有截斷壁（53)的作用，以 限制通過此等微料（51)之燃料或原料之流動彳向。在此 ，溝槽甲'藉由分隔壁（52)將此等微通道（51)分隔開，並形成 稷數個。在該入口（46)與該出口（47)的周圍，會聚性凹部⑻ 與會聚性凸部（55)限制燃料或原料之流動，使得來自該入 (46)或該出口（47)之該燃料或原料擴散至該微通道 =’或㈣使_料或原料收集至該人口（46)或該出口 :此等微通道盤狀物(45與45，)中，雖然下部微通道盤 (45 )與上部微通道盤狀物（45)為相同，但其具有鏡像 子稱結構，所以以相同符號表示並僅以符號（，）來做區別。 而且’根據本發明，如第2圖所示，即使在此實例中， 93390 14 '1306081 有兩個或兩個以上之燃燒用盤狀物組（41，）與重組反應用 盤狀物組（41”)相互地堆疊，但該燃料流與原料流並不會彼 .此混雜。參照第2圖，流入燃燒器入口（43)之燃料將透過 .該燃燒用盤狀物組⑷，）的入口（46)流至該燃燒用盤狀物組 • (41’）之内部，使其在通過該微通道中燃燒，然後由燃燒用 盤狀物組（41，）之出口（47)離開，再通過位於上層的該重組 反應用盤狀物組（41，，)之第二連接孔（49)，接著流入位於上 層的該燃燒用盤狀物組（41，）之出口（47)。此亦施用於原料 •以相同方式流入該重組反應用盤狀物組（41，，），所以該燃料 與該原料可彼此分別地流動。 可藉由氣相燃料的饋入與燃燒所產生的燃燒熱使氫產 生，較佳為從氫源（21)與第一氧源（22)將氫與氧化劑（較佳 為氧或空氣）經由燃燒器入口（43)輸入至該燃燒用盤狀物 組（41 )中的第一單位反應裝置（11)中的燃燒用盤狀物組 (4Γ)，供應熱至與其毗鄰的該重組反應用盤狀物組（4ι，，）， 籲並將做為原料的甲醇和水之混合物從原料源（27)饋入至該 重組反應用盤狀物組（41”），使曱醇轉換成氫。除了使用該 燃燒熱外，該重組反應亦可藉由通過該第一單位反應裝置 (11)之該燃燒用盤狀物組（41，)之内部的熱流來進行，熟習 此技藝之人士自然可理解有大規模產生廢熱（exhaust 之處亦可使用此等具有廢熱的熱流。在此實例中，該燃 燒用盤狀物組（41，）中可能不含有該燃燒觸媒。 如第1圖所示，第三單位反應裝置（12)可進—步連接 至該第一單位反應裝置（11)。該第三單位反應裝置（12)包括 93390 15 1306081 含有一對微通道盤狀物之熱交換用盤狀物組，於該微通道 盤狀物的一面的表面上形成微通道，且該微通道盤狀物是 .以忒微通道彼此相對的方式相互組合。可明暸該熱交換用 .盤狀物組具有相同或相似於該燃燒用盤狀物組（41，）或該 •重組反應用盤狀物組（41，，)之結構，只是除了該熱交換用盤 狀物組完全不含有觸媒，例如燃燒腾媒、重組觸媒等，而 且能藉由允許該流體通過該微通道，而使穿過該彼此毗鄰 之盤狀物組的流體間進行熱交換。本文的第三單位反應裝 參置（12)中所;^達的，，第三”係用於區別該既無燃燒觸媒亦無 該重組觸媒之單位反應裝置。該第三單位反應裝置（12)可 連接至該第一單位反應裝置（11)之燃燒用盤狀物組（41，）， 其中該第三單位反應裝置（12)之一個熱交換用盤狀物組的 入口可連接至該第一單位反應裝置（11)之燃燒用盤狀物组 (4Γ)的出口。 因此’來自該第一單位反應裝置（11)之燃燒用盤狀物 鲁組所釋放之廢氣係通過該第三單位反應裝置（12)之一個熱 父換用盤狀物組，並加熱與其毗鄰的其它熱交換用盤狀物 組’藉此可使通過其它熱交換用盤狀物組之内部的流體被 加熱。同時，倘若該第一燃料源（24)連接至其它熱交換用 盤狀物組，且其所供應之液態燃料通過其它熱交換用盤狀 物、、且日守’則會使該液態燃料氣化，且該經氣化之燃料係再 次連接至該第一單位反應裝置（11)之燃燒用盤狀物組 (41’），而使該燃燒反應可繼續 '因此，在初始預熱期間， 利用該氣相燃料使該第一單位反應裝置（11)與該第三單位 93390 1693390 Revision 13 1306081 As shown in the embodiment, two or more disk groups such as the combustion disk group (41') and the recombination reaction disk group (41,) can be mutually Ground pile. Stack. If necessary, that is, according to the amount of hydrogen to be produced, etc., the number of stacked combustion disk groups (41,) and the recombination reaction disk group (41" may be increased or decreased. As shown in Fig. 7, a plurality of passage forming spaces (71) are formed inside each of the discs (four), and the inner wall serves as a catalyst covering portion (72) in which the catalyst to be coated is, for example, a combustion catalyst. Or recombination catalyst. As shown in Figures 4 and 5, in the microchannel discs (45 and 45,), the upper microchannel disc (45) has an inlet (46) and an outlet (47). a first connecting hole (48) and a second connecting hole (49), wherein the inlet and the outlet are located on a diagonal line with each other, i the first connecting hole (48) and the second connecting hole (four) Located on each other on a diagonal line, wherein a groove is formed between the inlet (10) and the outlet (9). The groove has a certain depth from a surface including the inlet (46) and the outlet (9), and the groove wall has a truncation The role of the wall (53) to limit the flow direction of the fuel or material passing through the micro-materials (51). Here, the trench A' is separated by (52) separating the microchannels (51) and forming a plurality of turns. Around the inlet (46) and the outlet (47), the converging recess (8) and the converging convex portion (55) restrict fuel Or the flow of the feedstock such that the fuel or feedstock from the inlet (46) or the outlet (47) diffuses to the microchannel = 'or (d) the feed or feedstock is collected to the population (46) or the outlet: In the microchannel discs (45 and 45,), although the lower microchannel disc (45) is identical to the upper microchannel disc (45), it has a mirror sub-structure, so it is represented by the same symbol and only The symbol (,) is used for the difference. And 'according to the present invention, as shown in Fig. 2, even in this example, 93390 14 '1306081 has two or more combustion disk groups (41,) and The recombination reaction is stacked on each other with the disc group (41"), but the fuel stream and the feed stream are not mixed. Referring to Fig. 2, the fuel flowing into the burner inlet (43) will pass through the inlet (46) of the combustion disc group (4), to the inside of the combustion disc group (41'), so that It is burned through the microchannel, then exits from the outlet (47) of the combustion disc group (41,), and passes through the second connection of the recombination reaction disc group (41,) located in the upper layer. The hole (49) then flows into the outlet (47) of the combustion disk group (41,) located in the upper layer. This is also applied to the raw material. • The reversing reaction disc group (41,) is flowed in the same manner, so that the fuel and the raw material can flow separately from each other. Hydrogen can be generated by the combustion of the gaseous fuel and the combustion heat generated by the combustion, preferably by hydrogen and oxidant (preferably oxygen or air) from the hydrogen source (21) and the first oxygen source (22). The burner inlet (43) is input to the combustion disk group (4Γ) in the first unit reaction device (11) in the combustion disk group (41), and supplies heat to the recombination reaction adjacent thereto. a disc group (4ι,,), and a mixture of methanol and water as a raw material is fed from a raw material source (27) to the reconstituted reaction disc group (41") to convert sterol to hydrogen. In addition to using the heat of combustion, the recombination reaction can also be carried out by the heat flow inside the combustion disk group (41) through the first unit reaction device (11), and those skilled in the art naturally It can be understood that there is a large-scale generation of waste heat (the exhaust heat with waste heat can also be used in the exhaust. In this example, the combustion disk group (41,) may not contain the combustion catalyst. As shown, the third unit reaction device (12) can be further connected to the first unit reaction package (11) The third unit reaction device (12) comprises 93390 15 1306081 a heat exchange disc group comprising a pair of microchannel discs, and microchannels are formed on a surface of one side of the microchannel disc, And the microchannel disk is combined with each other in such a manner that the microchannels are opposite to each other. It is clear that the heat exchange disk group has the same or similar to the combustion disk group (41,) or the Recombination reaction disc group (41,,) is constructed except that the heat exchange disc group contains no catalyst at all, such as combustion medium, recombination catalyst, etc., and can be allowed to pass the fluid a microchannel for exchanging heat between fluids passing through the group of disks adjacent to each other. The third unit of the present invention is provided in the reference device (12); a unit reaction device having neither a combustion catalyst nor a recombination catalyst. The third unit reaction device (12) is connectable to the combustion disk group (41,) of the first unit reaction device (11), wherein a heat exchange disk of the third unit reaction device (12) The inlet can be connected to the outlet of the combustion disk group (4Γ) of the first unit reaction device (11). Therefore, the combustion disk from the first unit reaction device (11) is released by the disk group The exhaust gas is replaced by a heat carrier of the third unit reaction device (12), and the other heat exchange disk group adjacent thereto is heated, thereby allowing the disk group to pass through other heat exchange. The internal fluid is heated. Meanwhile, if the first fuel source (24) is connected to other heat exchange disc groups, and the liquid fuel supplied thereto passes through other heat exchange discs, and The liquid fuel is vaporized, and the vaporized fuel is again connected to the combustion disk group (41') of the first unit reaction device (11), so that the combustion reaction can continue. , during the initial warm-up period, the first unit reaction device (11) and the third unit 93390 16 are utilized by the gas phase fuel

V 1306081 反應裝置（12)預熱至所設定之溫度後，舉例而言，第一單 位反應裝置（11)為260至320°C，而該第三單位反應裝置（12) .為80至l〇〇°C，該重組反應可藉由下述方式繼續··切斷該 .氣相燃料，並且使用藉由第三單位反應裝置（12)所氣化的 .燃料來繼續該燃燒反應。小尺寸的氫產生裝置可使用更便 於操控與儲存的液態燃料，以及使不便於操控與儲存的氣 •相燃料之使用達到最小。關於該液態燃料’較佳為甲醇。 上述所示之組成方式，可藉由氣化液態燃料與使用從該第 參一單位反應裝置（11)所釋出廢氣之廢熱來使燃料有效地使 用。 第二單位反應裝置（13)可連接至該第一單位反應裝置 (11)。該第二單位反應裝置（13)包括燃燒用盤狀物組與熱交 換用盤狀物組。該第二單位反應裝置（13)可連接至該第一 單位反應裝置（11)之重組反應用盤狀物組（41，，），其中該第 二單位反應裝置之熱交換用盤狀物組的出口可連接至該第 _ 一單位反應裝置之重組反應用盤狀物組的入口。可明瞭該 第二單位反應裝置（13)之燃燒用盤狀物組具有相同或相似 於該第一單位反應裝置（11)之燃燒用盤狀物組（41，）的組 成。本文的第二單位反應裝置（13)中所表達的，，第二，，係用 於區別僅包括該燃燒觸媒之單位反應裝置。該第二單位反 應裝置（13)的功能在於藉由加熱與氣化做為供應至該第— 單位反應裝置（11)之燃料的甲醇與水之混合物，以促進該 第一單位反應裝置（11)中之重組反應。意即，供應該氣相 燃料，並措由將風源（21)與第一氧源（25)連接至該第二單杨 93390 17 1306081 反應裝置（13 )之燃燒用盤狀物組而與氧化劑共同燃燒；藉 由利用燃燒熱來加熱毗鄰第二單位反應裝置（13)之燃燒用 .盤狀物組之熱交換用盤狀物組；藉由將原料源（27)連接至 •該熱交換用盤狀物組，而使做為原料之甲醇與水之混合物 ，通過該熱交換用盤狀物組的内部並氣化；以及將該經氣化 的原料係供應至該第一單位反應裝置（11)之重組反應用盤 狀物組（41”）以進行重組。該第二單位反應裝置（13)可維持 於’舉例而言，110至200。(：之範圍。 參第四單位反應裝置（15)可進一步連接於第二單位反應 裝置（13)與第一單位反應裝置（11)之間。第四單位反應裝置 (15)係包括熱交換用盤狀物組。本文的第四單位反應裝置 (15)中所表達的，，第四，，係用於區別既無該燃燒觸媒亦無該 重組觸媒之單位反應裝置。意即，藉由連接該第四單位反 應裝置（15)之熱交換用盤狀物組之任一出口至該第二單位 反應裳置（13 )之燃燒用盤狀物組的入口，同時，連接液態 #燃料源之第二燃料源（26)至該盤狀物組的入口，以及連接 該第四單位反應裝置（15)之其它熱交換用盤狀物組的入口 至該第一單位反應裝置（11)之重組反應用盤狀物組（41”)的 ^ 可使該液態燃料利用其所釋放的產物流的熱而予以 ^化並供應至該第二單位反應裝置（13)之燃燒用盤狀物 二以進行該燃燒反應。藉此，當從該氫源（21)所供應之 氣相燃料被切斷時，可藉由使用由該經第四單位反應裝置 ()所氣化之燃料使該燃燒反應繼續。因此，在操作小尺 寸的風生產裝置中，可使較不便於操控與儲存的氣態燃料 93390 18 1306081 % 之使用減到最小，以及可使用便於操控與儲存的液態燃 料。關於該液態燃料，較佳為曱醇。上述所示之組成'^可 -藉由氣化液態燃料與使用從該第一單位反應裝置（11)所釋 •出之產物流的廢熱來使燃料有效地使用。 選擇性氧化反應器（14)可進一步地連接至該第一單位 .反應裝置（Π)之重組反應用盤狀物組（41，，）的出口。該選擇 性氧化反應器（14)的功能在於進行一氧化碳的氧化作用以 移除包含於做為由第一單位反應裝置（11)所重組與製造之 參產物的氫中的一氧化碳，藉此使從本發明裝置所產生的氫 可直接連接至燃料電池等而予以使用’而不需額外的純化 步驟，因為已移除最大量之可影響燃料電池電極的一氧化 碳。至於該選擇性氧化反應器（14)，可使用如本發明之盤 狀物組。選擇性氧化反應器可具有與該盤狀物組相同與相 似的結構，僅除了進一步包括選擇性氧化觸媒之外，而非 上述之該燃燒觸媒或該重組觸媒。用於供應使一氧化碳氧 籲化用之氧或空氣的第三氧源（28)係連接至該選擇性氧化反 應器（14)。 濾、器可連接於該第一單位反應裝置（11)之重組反應用 盤狀物組（41”)與該選擇性氧化反應器（14)之間。該濾器可 為傳統的機械式濾器。 如第1圖至第7圖所示，本發明之氫產生裝置之特徵 在於包括至少一個燃燒/重組反應用之第一單位反應裝置 (11)、至少一個氣化用之第二單位反應裝置(13)，以及至少 個熱父換用之第三單位反應裝置（12)，其中該第一單位 19 93390 1306081 反應裝置（Π)包括含有燃燒觸媒之燃燒用盤狀物組（4Γ)與 含有重組觸媒之重組反應用盤狀物組（41”）；其中該第二單 位反應裝置（13)包括燃燒用盤狀物組與熱交換用盤狀物組; •其中該第三單位反應裝置（12)包括熱交換用盤狀物組；其 .中該第一單位反應裝置（11)之燃燒用盤狀物組（41，）係連接 至該第三單位反應裝置（12)之一個熱交換用盤狀物；其中 該第三單位反應裝置（12)之其它熱交換用盤狀物係連接至 該第一單位反應裝置（11)之燃燒用盤狀物組（41，）；以及其 #中該第二單位反應裝置（13)之熱交換用盤狀物組係連接至 該第一單位反應裝置（11)之重組反應用盤狀物組（41，，）。 用於改變流動方向之閥（23)係連接至該第一單位反應 裝置（11)之燃燒用盤狀物組(4 Γ)。而且，氫源（21)係連接至 此用於改變流動方向的閥（23)。用於改變流動方向的閥（23) 較佳可為四向閥，以使從與其相連之該氫源所供應的氫可 依序地先饋入至用於還原之該第一單位反應裝置（n)之燃 籲燒用盤狀物組（4Γ)中，然後饋入至用於還原之重組反應用 盤狀物組（41”）中，最後饋入至該第二單位反應裝置（13)之 燃燒用盤狀物組中。藉此，偏若藉由利用氮做為燃料，使 第一單位反應裝置（11)以及與其相連之第三單位反應裝置 (12)之溫度升高至高於做為燃料之甲醇的沸點時，則該燃 料從氫換成甲醇。而且，藉由甲醢从、由 稭田T転的連續燃燒反應使該第 「單位反應裝置（U)之溫度升高至該還原溫度（約· 後^該重組反應用盤狀物組（41，，）中之該重組觸媒可藉由 93390 20 1306081 藉由如上述之組成，本發明係提供如下之優點：在包 含微通道之單位反應裝置之燃燒用盤狀物組中進行辦声反 應、，並堆疊與放置與其毗鄰之重組反應用盤狀物組，' =而 .使進彳丁該重組反應之重組反應用盤狀物組能維持穩定的操 ，作溫度’而可提升甲醇的轉化率與產物中氫的組成，並且 •可藉由降低一氧化碳的含量來顯現高的熱效能與氫產率； 以及可使該裝置較小，且直接附接於燃料電池等，以藉由 降低一氧化碳的含量來供應氫。而且，本發明係藉由^一 步L括k擇性氧化反應器以盡可能移除一氧化碳而提供可 操作燃料電池而不使燃料電池電極去活化（deactive)之好 處。 本發明之氫產生方法係包括（丨）第一燃燒步驟，係將氣 相燃料與氧化劑共同饋入至該第一單位反應裝置(11)之燃 燒用盤狀物組（41，），使該燃料在該燃燒用盤狀物組(41，）中 燃燒’並利用燃燒熱來加熱毗鄰該燃燒用盤狀物組（41，）之 #，組反應甩盤狀物組(41，，)；以及（2)產生氫的重組步驟，係 藉由將用於重組反應的原料（包括曱醇和水的混合物）饋入 至經加熱的重組反應用盤狀物組（41，，），使該原料重組，在 藉由使用包括至少一個燃燒/重組反應用之第一單位反應 裝置（11)的氫產生裝置中，該第一單位反應裝置係包括含 有燃燒觸媒之燃燒用盤狀物組與含有重組觸媒之重組反應 用盤狀物組，其中各盤狀物組含有一對微通道盤狀物，微 通道係形成在該微通道盤狀物的一面的表面上，且該微通 道盤狀物以該微通道彼此相對的方式相互組合；其中該燃 93390 21 1306081 燒用盤狀物組在該微通道中包含該燃燒觸媒；以及其中該 重組反應用盤狀物組在該微通道中包含該重組觸媒。藉由 •供應從該第一燃燒步驟所產生的燃燒熱使該重組反應用盤 .狀物組加熱，並使用該熱來進行該重組反應。因此，本發 .明之特徵在於藉由在包含微通道之單位反應裝置之燃燒用 盤狀物組（41，）中進行燃燒反應，並堆疊與放置與其毗鄰之 重組反應用盤狀物組（41，，），藉此使進行該重組反應之重組 反應用盤狀物組（41，，）能維持260至32〇t的穩定操作溫 參度，而可提升曱醇的轉化率與產物中氫的組成，並且可藉 由降低一氧化碳的含量來顯現高的熱效能與氫產率。本文 中，倘若該第一單位反應裝置（11)的溫度低於26〇t：，則對 氫的轉化率可能因為重組反應溫度太低而降低，相反地， 倘若鬲於320 C，則產物中一氧化碳的含量會升得太多， 而接下來的優選氧化反應仍無法使一氧化碳的濃度充分降 低’以致該氳產率可能減少。倘若該一氧化碳的濃度變得 鲁相對地高，則可能有一問題，即做為產物的氫無法直接地 納入以做為燃斜電池用之燃料。 本發明之氫產生方法可在該第一燃燒步驟（丨）與該重 組步驟（2)之間，進一步包括：第一連接步驟，係將含有熱 父換用盤狀物組之第三單位反應裝置（12)連接至該第一單 位反應裝置（11)之燃燒用盤狀物組（41，），該熱交換用盤狀 物組之各該盤狀物組包括一對微通道盤狀物，微通道係形 成在該Μ通道盤狀物的一面的表面上，且該微通道盤狀物 以該微通道彼此相對的方式相互組合，其中該第三單位反 93390 22 ' 1306081 應裝置（12)之熱交換用盤狀物的任何入口係連接至該第一 單位反應裝置（11)之燃燒用盤狀物組（41，）之出口；以及第 • 一氣化步驟’係將從該第一單位反應裝置（11)之燃燒用盤 •狀物組（4Γ)所釋放之廢氣連接至該第三單位反應裝置（12) 之一個熱交換用盤狀物組’並將液態燃料饋入至該第三單 位反應裝置（12)之其它熱交換用盤狀物組，以使該液態燃 .料氣化。該特徵在於藉由該第一連接步驟，將該第三單位 反應裝置（12)連接至該第一單位反應裝置（11)，並藉由使用 參從該第一單位反應裝置（11)之燃燒用盤狀物組（41，）所釋放 之廢軋使該液態燃料氣化並再一次藉由供應經氣化之燃料 至第一單位反應裝置（11)以作為燃料用’倘若使該反應開 始進行，而加熱該第三單位反應裝置（12)至所給定的溫 度，較佳為80至1 〇〇。〇，則進一步停止該氣相燃料的使用， 並使用液態燃料，藉此可能使不便於操控與儲存的氣相燃 料之使用達到最小’而使用較便於操控與儲存的液態燃 馨料。倘若該第三單位反應裝置之溫度低於8〇它，將使該液 態燃料無法充分地氣化，.而在實際製程操作中’沒有溫度 尚於100°c的實例。 本發明之風產生方法可在該第一燃燒步驟（1)與該重 組步驟（2)之間，進一步包括：第二連接步驟，係將含有燃 燒用盤狀物組與熱交換用盤狀物組之第二單位反應裝置 (13)連接至該第一單位反應裝置（11)之重組反應用盤狀物 組（41”）’其中該第二單位反應裝置（13)之熱交換用盤狀物 勺出係連接至该第一單位反應裝置（11)之重組反應用盤 93390 23 1306081 狀物組（4Γ，)之入口；第二燃燒步驟，係將氣相燃料與氧化劑 共同饋入至該第二單位反應裝置（13)之燃燒用盤狀物組， *使s亥燃料在燃燒用盤狀物組中燃料’並藉由利用該燃燒熱 .來加熱毗鄰該燃燒用盤狀物組之熱交換用盤狀物組；第I 氣化步驟，係將重組反應用的原料（包括甲醇和水的混合物） .饋入至該第二單位反應裝置（13)之熱交換用盤狀物組，以 .使該原料氣化；以及第一進料步驟，係將在第二氣化步驟中 經氣化之重組反應用的原料饋入至該第一單位反應裝置 參（11)之重組反應用盤狀物組（41”）。藉由第二連接步驟，使 該第二單位反應裝置（13)連接至該第一單位反應裝置 (11)’藉由使用來自第二單位反應裝置（13)之燃燒用盤狀物 組中的燃燒反應之燃燒熱而使先被導入至該第一單位反應 裝置（11)之原料氣化與重組’使得該重組反應可順利地進 行’藉此可提高該熱效能與該對氫的轉換率。 本發明之氫產生方法可在該第一燃燒步驟G)與該重 _組步驟（2)之間，進一步包括：第三連接步驟，係將含有熱 父換用盤狀物組之第四單位反應裝置（15)連接至該第二單 位反應裝置（13)之燃燒用盤狀物组，其中該第四單位反應 裝置（15)之熱交換用盤狀物的任何一個出口係連接至該第 一單位反應裝置（13 )之燃燒用盤狀物組之入口；且該熱交 換用盤狀物組之入口係連接至液態燃料源；第四連接步 驟，係將第四單位反應裝置（15)之其它入口連接至該第一 單位反應裝置（11)之重組反應用盤狀物組之出口，並將熱 交換用盤狀物的出口連接至產物收集器；以及第三氣化步 93390 24 1306081 Γ物Γ藉由料從第—單位反應裝置（n)之重組反應用盤 ’且所釋放出的產物流的熱’使饋人至該第二單位反應 ，裝置(13)的液態燃料氣化。因此，該特徵在於在該第二单: 位反應裝置（I3)升高至所給訂的溫度（較佳為⑽至·。〇 .之前’該第四單位反應裝置（15)係藉由從第—單位反 =1)所釋放的產物流予以充分地加熱，這樣的製程係藉 乳相燃料（即氫）來操作，而在該第二單位反應裝置 (13)升馬至所給訂的溫度（較佳為11 〇至2001)之後，則供 ㈤態燃料(即甲醇)至該第四單位反應袋置〇5)，並使之： 該第四單位反應裝置中氣化，且藉由將經氣化之燃料供應 至該第二單位反應裝置（13)使之作做為燃料用，而可能使 不便於操控與儲存的氣相燃料之使用達到最小，並使用更 便於操控與錯存的液態燃料。倘若該第三單位反應裝置之 温度低於1HTC ’可能使液態燃料無法充分地氣^，而實 際製程操作中，沒有溫度高於20(TC的實例。 本發明之氫產生方法之特徵在於包括：⑴第一燃燒步 驟，係將氣相燃料與氧化劑共同饋入至該第一單位反應裝 置之燃燒用盤狀物組，且使該燃料燃燒；（2)第一預熱步 驟，係透過該第三單位反應裝置之熱交換用盤狀物組，利 用從該第一燃燒步驟中的燃燒用盤狀物所釋放的廢氣使該 第三單位反應裝置預熱至8〇至1〇〇(5(：;(3)第二燃燒步驟， 係透過該第二單位反應裴置之其它熱交換用盤狀物組，藉 由饋入及氣化液態燃料至該第一單位反應裝置之燃燒用盤 狀物組，並使該燃料與饋入的氧化劑同時燃燒，以使該第 93390 25 1306081 一單位反應裝置加熱至260至32(TC;(4)第三燃燒步驟，係 藉由將氣相燃料饋入至該第二單位反應裝置之燃燒用盤狀 •物組，並使該燃料與氧化劑共同燃燒，以使該第二單位反 •應裝置加熱至110至200°c;(5)氣化步驟，係藉由使該作為 重組反應之原料的甲醇與水之混合物通過該第二單位反應 裝置之燃燒用盤狀物組，並將該混合物饋入至該第一單位 .反應裝置之重組反應用盤狀物組，以使該混合物氣化；以及 (6)重組步驟，係藉由通過該第一單位反應裝置之重組反應 參用盤狀物組，使該經氣化的原料重組成氫，藉由使用本發 明之氫產生裝置來產生氫，該裝置包括至少一個燃燒/重組 反應用之第一單位反應裝置、至少一個氣化用之第二單位 反應裝置，以及至少一個熱交換用之第三單位反應裝置， 其中該第一單位反應裝置包括含有燃燒觸媒之燃燒用盤狀 物組與含有重組觸媒之重組反應用盤狀物組；其中該第二 單位反應裝置包括燃燒用盤狀物組與熱交換用盤狀物組； 鲁其中該第二單位反應裝置包括熱交換用盤狀物組；其中該 第一單位反應裝置之燃燒用盤狀物組係連接至該第三單位 反應裝置之一個熱交換用盤狀物；其中該第三單位反應裝 置之其它熱交換用盤狀物係連接至該第一單位反應裝置之 燃燒用盤狀物組；且其中該第二單位反應裝置之熱交換用 盤狀物組係連接至該第一單位反應裝置之重組反應用盤狀 物組。 在藉由使用如上述之本發明的氫產生裝置產生氫中， 上述方法可使用做為理想的實施例。意即，為了啟動該重 93390 26 1306081 組反應，首先，供應氫與空氣或氧的氣體混合物至該第一 單位反應裝置（11)’並在燃燒用盤狀物組（41，）中燃燒；此時 •所產生的熱與廢氣經由該第三單位反應裝置（12)被排放 .出，而在將做為液態燃料的甲醇供應至第三單位反應裝置 (12)並氣化之後，再將經氣化的曱醇供應至該第一單位反 應裝置（11)以繼續燃燒反應。本文中，倘若該燃燒反應藉 一由甲醇予以啟動，則停止做為氣相燃料的氫之供應，而使 該氫與空氣或氧的氣相混合物供應第二單位反應農置 鲁（13)。換句話說，藉由調整曱醇的饋入比例使該燃燒反應 繼續’直到該第一單位反應裝置（11)之溫度達到26〇至32〇 C，倘若達到’則藉由供應做為原料之曱醇與水的混合物至 該第一單位反應裝置（11)之重組反應用盤狀物組（41，，），以 進行該燃燒反應，並將做為產物流的氫流供應至該第四單 位反應裝置（15)。在該第四單位反應裝置（15)中，亦可使做 為液態燃料的甲醇氣化，並供應至該第二單位反應裝置 籲（13)。在該第二單位反應裝置（丨3)中，亦可進行該燃燒反 應，並倘若該溫度達到11〇至20(rc，係完成本發明之氫 產生裝置的操作起始步驟，且藉由連續地使用僅做為液態 燃料的甲醇使該燃燒反應在該第一單位反應裝置（丨1 )與第 二單位反應裝置（13)中繼續，並藉由在第一單位反應裝置 (11)之重組反應用盤狀物組（41，，）中重組做為原料之甲醇與 水的混合物而連續地產生氫。 本發明可藉由下述之實施例更具體地說明。然而，應 暸解該實施例並不以任何方式來侷限本發明。 93390 27 1306081 « 實施例l 重組反應用盤狀物組係藉由下述方式所組成：使用藉 由共沉殿方法以4/4/2之重量比所合成之銅/鋅/紹氧化物 •做為重組觸媒，並在第一單位反應裝置之重組反應用盤狀 .物、'且的每個微通道盤狀物以〇 6克的重組觸媒量被覆。燃 .^用盤狀物組藉由下述方式所組成：首先在微通道盤狀物 -組上被覆^_氧化鋁做為燃燒觸媒，並將具有鉑量約；3重量 /。之鉑的水溶液添加至該α _氧化鋁，使該盤狀物組乾燥及 锻燒。該第一單位反應裝置係藉由下述方式所組成：如上 述所構成，使六個重組反應用盤狀物組與五個燃燒用盤狀 物組彼此交替地堆疊，且藉由啟動該操作以及調整第一單 位反應裝置之溫度至約300。(：來進行該重組反應，而未附 接選擇性氧化反應器。同時，做為重組反應用之原料之甲 醇：水的混合比例係為50 : 50，而供應至該第一單位反應 裝置之重組反應用之原料之流動速率經調整為3 cc/分 _鐘，且該做為燃料之甲醇的流動速率經調整為hl ec/分 鐘。在此等操作條件下，約90分鐘後該第一單位反應裝置 即達到該上述之温度。當該第一單位反應裝置於3它操 作時’重組反應後該產物的組成比例，係以移除澄氣之乾 重為基準計’經分析為74.8%的氫、24.4%的二氧化碳與 0.84%的一氧化碳。 根據參與該重組反應的甲醇量，甲醇的轉化率為 99.5%。使用下述方程式（1)計算出指示該操作效能之熱效 能’根據 the Pacific North Laboratory 之 J. 〇f p〇Wer s〇urce 93390 28 1306081 ⑽（2002)中第21至27頁，其描述做為本發明之前案所 述及之甲醇的水蒸氣重組裝置供客觀的比較： -[方程式（1)] •操作效能=(AHcH2)/(AHc 總 ch3oh) CH3OH(液態）+1.5 〇2=c〇2+2H20(液態）千焦耳/ 莫耳 « H2+0.5 02=H20(氣態）^11=-242 千焦耳/莫耳 上述方程式中，△ Hc H2為所產生之氫的總焓 ♦ (entity)，而肌總⑶观為參與該重組反應與該燃燒 反應之總甲醇的總焓。 因為根據上述方程式之計算，本發明之氫產生裝置的 熱效能為59.5°/。。而且，連接選擇性氧化裝置之後，該氫 產物中的一氧化碳含量降低至70ppm。同時該熱效能亦降 低至56.7。/。，因為在該選擇性氧化反應期間有些氫一起發 生反應。 ·(產業利用性） 根據包括含有微通道(該微通道係包括燃燒觸媒及/或 重組觸媒的被覆）的單位反應裝置之氫產生裝置，以及使用 本發明之氫產生裝置的氫產生方法;藉由使用包括在微通 道上含有燃燒觸媒之燃燒用盤狀物組與在微通道上含有重 組觸媒之重組反應用盤狀物組（其彼此毗鄰地堆疊）之單位 反應裝置，使該燃燒反應與該重組反應進行，以維持該重 組反應在一穩定的溫度範圍，由於該組成中發生重組$應 處與發生燃燒反應處相近’因此使該燃燒反應所產生的熱 93390 29 1306081 迅速地轉移至該重組反應，並且在該微通道中在保持高反 應溫度下進行該燃燒反應與該重組反應；可達到以曱醇的 轉換率為99%或大於99%及高熱效能為59.5%或大於 • 59.5%產生氫。而且，設計為具有高熱效能且對氫有高轉 化率之本發明之氳產生裝置以及使用該氫產生裝置之氳產 生方法’係藉由使用醇類（例如曱醇）做為燃料而有效地供 應氫至燃料電池系統，因為所有該燃燒反應與該重組反應 可藉由使用微通道來進行，並且該氫產生裝置藉由熱交換 參之氣化作用使本身可非常小。再者’氫的產量可視需要僅 藉由調整以組成該燃燒用盤狀物組與該重組反應用之盤狀 物組為單位之此等盤狀物組的堆疊數來控制。 【圖式簡單說明】 弟1圖係說明本發a月之氫產生裝置之整個結構的示意 圖。 第2圖係說明用於第丨圖之氫產生裝置的單位反應裝 g置之分解圖。 第3圖為本發明之氫產生裝置之具體實施例的分解照 片。 第4圖為組成第2圖之單位反應裝置之僅盤狀物組的 分解圖。 第5圖為組成第4圖之盤狀物組之微通道盤狀物之平 面圖。 第6圖為組成本發明之單位反應裝置之盤狀物組中所 使用的襯塾的平面圖。 30 93390 1306081 第7圖為組成第2圖之單位反應裝置之盤狀物組的截 面圖 0 【主要元件符號說明】 11 第一單位反應裝置 12 第三單位反應裝置 13 第二單位反應裝置 14 選擇性氧化反應器 15 第四單位反應裝置 21 氫源 22 第一氧源 23 用於改變流動方向的閥 24 第一燃料源 25 第二氧源 26 第二燃料源 27 原料源 28 第三氧源 31 濾器 41 單位反應裝置 41， 燃燒用盤狀物組 41” 重組反應用盤狀物組 42與42’頂蓋與底蓋 43, 燃燒器入口 43 燃燒器出口 44? 重組器入口 44 重組器出口 45與45’ 微通道盤狀物 46與46’ 入口 47與47’ 出口 48與48’ 第一連接孔 49與49’ 第二連接孔 51與 5 Γ 微通道 52與52’ 分隔壁 53與 53’截斷壁 54與54’ 會聚性凹部 55與55’ 會聚性凸部 61 襯墊 62 開口 63 貫穿孔 71 通道形成空間 72 觸媒被覆部分 31 93390修正版V 1306081 After the reactor (12) is preheated to the set temperature, for example, the first unit reaction unit (11) is 260 to 320 ° C, and the third unit reaction unit (12) is 80 to 1 At 〇〇 ° C, the recombination reaction can be continued by cutting off the gas phase fuel and continuing the combustion reaction using the fuel vaporized by the third unit reaction unit (12). Small-sized hydrogen generators use liquid fuels that are easier to handle and store, as well as minimize the use of gas fuels that are difficult to handle and store. The liquid fuel ' is preferably methanol. The composition shown above can be effectively utilized by vaporizing the liquid fuel and using waste heat from the exhaust gas discharged from the first unit reaction unit (11). A second unit reaction unit (13) is connectable to the first unit reaction unit (11). The second unit reaction device (13) includes a disk group for combustion and a disk group for heat exchange. The second unit reaction device (13) is connectable to the recombination reaction disk group (41,) of the first unit reaction device (11), wherein the second unit reaction device heat exchange disk group The outlet can be connected to the inlet of the disc group for the recombination reaction of the first unit reaction unit. It is apparent that the combustion disk group of the second unit reaction device (13) has the same or similar composition of the combustion disk group (41) of the first unit reaction device (11). The second unit reaction device (13) herein, as expressed in the second unit, is used to distinguish unit reaction devices comprising only the combustion catalyst. The function of the second unit reaction device (13) is to promote the first unit reaction device by heating and gasification as a mixture of methanol and water supplied to the fuel of the first unit reaction device (11). Recombination reaction in ). That is, the gas phase fuel is supplied, and the wind source (21) and the first oxygen source (25) are connected to the combustion disk group of the second single Yang 93390 17 1306081 reaction device (13). The oxidant is co-combusted; the heat exchange disc group adjacent to the combustion disc group of the second unit reaction device (13) is heated by utilizing the heat of combustion; by connecting the raw material source (27) to the heat Exchanging a disc group, and using a mixture of methanol and water as a raw material, passing through the inside of the heat exchange disc group and vaporizing; and supplying the vaporized raw material system to the first unit reaction The reconstitution reaction device (11) of the device (11) is used for recombination. The second unit reaction device (13) can be maintained, for example, from 110 to 200. (: range: reference to the fourth unit The reaction device (15) may be further connected between the second unit reaction device (13) and the first unit reaction device (11). The fourth unit reaction device (15) includes a disk group for heat exchange. The four unit reaction device (15), fourth, is used to distinguish neither The combustion catalyst is also free of the unit reaction device of the recombination catalyst, that is, by any one of the outlets of the heat exchange disc group connected to the fourth unit reaction device (15) to the second unit reaction (13) an inlet for the group of combustion discs, at the same time, a second fuel source (26) connecting the liquid #fuel source to the inlet of the disc group, and the other connecting the fourth unit reaction device (15) The inlet of the heat exchange disc group to the reconstitution reaction disc group (41" of the first unit reaction device (11) allows the liquid fuel to be utilized by the heat of the product stream it releases. And supplying the combustion disk 2 to the second unit reaction device (13) to perform the combustion reaction, whereby when the gas phase fuel supplied from the hydrogen source (21) is cut off, The combustion reaction is continued by using the fuel vaporized by the fourth unit reaction device. Therefore, in operating the small-sized wind production device, the gaseous fuel 33390 18 1306081% which is less convenient to handle and store can be made. Minimize the use and ease of use and storage The liquid fuel. Preferably, the liquid fuel is decyl alcohol. The composition shown above can be obtained by gasifying the liquid fuel and using the product stream released from the first unit reaction unit (11). Waste heat is used to effectively use the fuel. The selective oxidation reactor (14) can be further connected to the outlet of the first unit. reaction apparatus (Π) for the reaction reaction disc group (41,,). The function of the oxidation reactor (14) is to carry out the oxidation of carbon monoxide to remove carbon monoxide contained in the hydrogen as a reference product reconstituted and manufactured by the first unit reaction unit (11), thereby making the apparatus of the present invention The hydrogen produced can be used directly to the fuel cell or the like for use without additional purification steps since the maximum amount of carbon monoxide that can affect the fuel cell electrode has been removed. As for the selective oxidation reactor (14), a disk group such as the present invention can be used. The selective oxidation reactor may have the same structure as the disc group, except that it further includes a selective oxidation catalyst, rather than the combustion catalyst or the recombination catalyst described above. A third oxygen source (28) for supplying oxygen or air for carbon monoxide oxygenation is connected to the selective oxidation reactor (14). The filter may be connected between the reconstituted reaction disk group (41") of the first unit reaction device (11) and the selective oxidation reactor (14). The filter may be a conventional mechanical filter. As shown in Figures 1 to 7, the hydrogen generating apparatus of the present invention is characterized by comprising at least one first unit reaction unit (11) for combustion/recombination reaction and at least one second unit reaction unit for gasification ( 13), and at least one third unit reaction device (12) replaced by a hot parent, wherein the first unit 19 93390 1306081 reaction device (Π) comprises a combustion disk group (4Γ) containing a combustion catalyst and contains a recombination catalyst recombination reaction disk group (41"); wherein the second unit reaction device (13) comprises a combustion disk group and a heat exchange disk group; wherein the third unit reaction device (12) comprising a disk group for heat exchange; wherein the combustion disk group (41,) of the first unit reaction device (11) is connected to a heat of the third unit reaction device (12) a disk for exchange; wherein the third unit reaction device (12) a heat exchange disc is connected to the combustion disc group (41,) of the first unit reaction device (11); and a heat exchange disc of the second unit reaction device (13) The group is connected to the disc group (41,) for recombination reaction of the first unit reaction device (11). A valve (23) for changing the flow direction is connected to the combustion disk group (4 Γ) of the first unit reaction device (11). Moreover, a hydrogen source (21) is connected to the valve (23) for changing the flow direction. The valve (23) for changing the flow direction is preferably a four-way valve such that hydrogen supplied from the hydrogen source connected thereto can be sequentially fed first to the first unit reaction device for reduction ( n) is burned into a disk group (4Γ), then fed into a disk group (41" for recombination reaction for reduction, and finally fed to the second unit reaction device (13) In the combustion disk group, the temperature of the first unit reaction device (11) and the third unit reaction device (12) connected thereto is raised to be higher than by using nitrogen as a fuel. When the boiling point of the fuel is methanol, the fuel is exchanged from hydrogen to methanol. Moreover, the temperature of the first unit reaction unit (U) is raised to the temperature by the continuous combustion reaction of the formazan from the straw field T転. The reduction temperature (about </ RTI> after the recombination reaction disc group (41,,) the recombination catalyst can be composed of 93390 20 1306081 by the above composition, the present invention provides the following advantages: Acoustic reaction in the combustion disk group of the unit reaction device of the channel, and stacking Place the disc group with the recombination reaction adjacent to it, '=. The recombination reaction of the recombination reaction can maintain a stable operation with the disc group, and the temperature can be increased to increase the methanol conversion rate and the product. The composition of hydrogen, and • can exhibit high thermal efficiency and hydrogen yield by reducing the content of carbon monoxide; and can make the device smaller and directly attached to a fuel cell or the like to supply by reducing the content of carbon monoxide Hydrogen. Moreover, the present invention provides the benefit of operating a fuel cell without deactivating the fuel cell electrode by removing the carbon monoxide as much as possible by removing the carbon monoxide oxidation reactor as much as possible. The method includes a first combustion step of feeding a gas phase fuel and an oxidant to a combustion disk group (41,) of the first unit reaction device (11) to cause the fuel to be used in the combustion. Burning in the disc group (41,) and using combustion heat to heat the # adjacent to the combustion disc group (41,), the group reaction disc group (41,,); and (2) generating Hydrogen recombination step The raw material (including a mixture of decyl alcohol and water) to be used in the recombination reaction is fed to the heated reconstituted reaction disk group (41,) to reconstitute the raw material, including at least one combustion/recombination by use. In the hydrogen generator of the first unit reaction device (11) for reaction, the first unit reaction device includes a combustion disk group containing a combustion catalyst and a disk group for recombination reaction containing a recombination catalyst. Wherein each disc group comprises a pair of microchannel discs, the microchannels are formed on a surface of one side of the microchannel disc, and the microchannel discs are combined with each other in such a manner that the microchannels face each other; Wherein the burning 93390 21 1306081 burning disc group comprises the combustion catalyst in the microchannel; and wherein the recombination reaction disc group comprises the recombination catalyst in the microchannel. The recombination reaction is heated by a disk group by supplying the heat of combustion generated from the first combustion step, and the heat is used to carry out the recombination reaction. Therefore, the present invention is characterized in that a combustion reaction is carried out in a combustion disk group (41,) in a unit reaction apparatus including a microchannel, and a disk group for recombination reaction adjacent thereto is stacked and placed (41). ,,), whereby the reconstitution reaction disc group (41,) capable of carrying out the recombination reaction can maintain a stable operating temperature parameter of 260 to 32 〇t, and can improve the conversion of sterol and hydrogen in the product. The composition, and can exhibit high thermal efficiency and hydrogen yield by reducing the content of carbon monoxide. Herein, if the temperature of the first unit reaction unit (11) is lower than 26〇t:, the conversion rate to hydrogen may be lowered because the recombination reaction temperature is too low, and conversely, if it is at 320 C, the product is in the product. The content of carbon monoxide will rise too much, and the next preferred oxidation reaction will still not sufficiently reduce the concentration of carbon monoxide so that the yield of tantalum may be reduced. If the concentration of carbon monoxide becomes relatively high, there may be a problem that hydrogen as a product cannot be directly incorporated as a fuel for a slanting battery. The hydrogen generating method of the present invention may be between the first burning step (丨) and the recombining step (2), further comprising: a first joining step of reacting the third unit containing the hot parent with the disc group The device (12) is connected to the combustion disk group (41,) of the first unit reaction device (11), and each of the disk groups of the heat exchange disk group includes a pair of microchannel disks a microchannel is formed on a surface of one side of the meandering channel disk, and the microchannel disk is combined with each other in such a manner that the microchannels are opposite to each other, wherein the third unit is inverted 93390 22 '1306081 device (12 Any inlet of the heat exchange disk is connected to the outlet of the combustion disk group (41,) of the first unit reaction device (11); and the first gasification step is from the first The exhaust gas released by the combustion disk unit (4Γ) of the unit reaction device (11) is connected to a heat exchange disk group ' of the third unit reaction device (12) and feeds the liquid fuel thereto. Other heat exchange discs for the third unit reaction unit (12) , So that the liquid fuel. Vaporized material. The feature is that the third unit reaction device (12) is connected to the first unit reaction device (11) by the first connecting step, and by using the combustion of the first unit reaction device (11) The liquid fuel is vaporized by the waste rolling released by the disc group (41,) and once again by supplying the vaporized fuel to the first unit reaction unit (11) for use as a fuel 'if the reaction is started The third unit reaction unit (12) is heated to a given temperature, preferably 80 to 1 Torr. 〇, the use of the gas phase fuel is further stopped, and liquid fuel is used, thereby making it possible to minimize the use of gas fuels that are inconvenient to handle and store, while using liquid fuels that are easier to handle and store. If the temperature of the third unit reaction unit is lower than 8 Torr, the liquid fuel will not be sufficiently vaporized, and in the actual process operation, there is no example where the temperature is still at 100 ° C. The wind generating method of the present invention may be between the first burning step (1) and the recombining step (2), further comprising: a second joining step of containing the disc group for combustion and the disc for heat exchange The second unit reaction device (13) of the group is connected to the disc group (41") of the recombination reaction of the first unit reaction device (11), wherein the second unit reaction device (13) has a disk shape for heat exchange The scoop is connected to the inlet of the reconstitution reaction disk 93390 23 1306081 (4Γ,) of the first unit reaction device (11); the second combustion step is to feed the gas phase fuel and the oxidant together a group of combustion discs of the second unit reaction device (13), *heating the fuel in the group of combustion discs and heating the adjacent disc group by using the heat of combustion a heat exchange disc group; a first gasification step, which is a raw material for recombination reaction (including a mixture of methanol and water) fed to the second unit reaction unit (13) for heat exchange disc group To vaporize the feedstock; and the first feed step, which will be in the second The raw material for the gasification recombination reaction in the gasification step is fed to the recombination reaction disk group (41") of the first unit reaction device (11). Connecting the second unit reaction device (13) to the first unit reaction device (11)' by using a second connection step by using the combustion disk group from the second unit reaction device (13) Combustion heat of the combustion reaction causes vaporization and recombination of the raw material introduced into the first unit reaction device (11) so that the recombination reaction can be smoothly performed, thereby increasing the thermal efficiency and the conversion rate of the hydrogen . The hydrogen generating method of the present invention may be between the first burning step G) and the heavy group step (2), further comprising: a third connecting step of replacing the fourth unit containing the hot parent with the disc group a reaction device (15) connected to the combustion disk group of the second unit reaction device (13), wherein any one of the outlet ports of the heat exchange disk of the fourth unit reaction device (15) is connected to the first An inlet of the combustion disk group of one unit reaction device (13); and the inlet of the heat exchange disk group is connected to the liquid fuel source; and the fourth connection step is a fourth unit reaction device (15) The other inlet is connected to the outlet of the disc reaction set for the first unit reaction unit (11), and the outlet of the heat exchange disc is connected to the product collector; and the third gasification step 93390 24 1306081 The liquid material is vaporized by the liquid fuel of the device (13) by feeding the liquid to the second unit by the recombination reaction of the first unit reaction device (n) and the heat of the product stream released. . Therefore, the feature is that the fourth unit reaction device (15) is raised from the second unit: position reaction device (I3) to a given temperature (preferably (10) to 〇. The product stream released by the first unit inverse = 1) is sufficiently heated, such that the process is operated by the milk phase fuel (i.e., hydrogen), and the second unit reaction unit (13) is upgraded to the given order. After the temperature (preferably 11 〇 to 2001), the (five) state fuel (ie, methanol) is placed in the fourth unit reaction bag (5), and is: gasified in the fourth unit reaction device, and by Supplying the vaporized fuel to the second unit reaction unit (13) for use as a fuel, may minimize the use of gas phase fuels that are inconvenient to handle and store, and use more convenient handling and misplacement Liquid fuel. If the temperature of the third unit reaction device is lower than 1 HTC', the liquid fuel may not be sufficiently vaporized, and in the actual process operation, there is no temperature higher than 20 (the example of TC. The hydrogen generation method of the present invention is characterized by including: (1) a first combustion step of feeding a gas phase fuel and an oxidant together to a combustion disk group of the first unit reaction device and burning the fuel; (2) a first preheating step of transmitting the first The heat exchange disc group of the three-unit reaction apparatus preheats the third unit reaction apparatus to 8 〇 to 1 利用 by using the exhaust gas released from the combustion disk in the first combustion step (5 (5 ( (3) a second combustion step of passing through the other heat exchange disk group of the second unit reaction device, by feeding and vaporizing the liquid fuel to the combustion disk of the first unit reaction device And combusting the fuel with the fed oxidant to heat the unit 93390 25 1306081 unit reaction unit to 260 to 32 (TC; (4) third combustion step by feeding the gas phase fuel Into the combustion of the second unit reaction device a disk-like object group, and co-combusting the fuel with an oxidant to heat the second unit reaction device to 110 to 200 ° C; (5) a gasification step by using the material as a recombination reaction a mixture of methanol and water is passed through the combustion disk group of the second unit reaction device, and the mixture is fed to the first unit. Reconstitution device for the reaction reaction disk group to vaporize the mixture And (6) a recombination step of reconstituting the vaporized raw material into hydrogen by passing through a recombination reaction of the first unit reaction device, by using the hydrogen generating device of the present invention Hydrogen, the apparatus comprising at least one first unit reaction unit for combustion/recombination reaction, at least one second unit reaction unit for gasification, and at least one third unit reaction unit for heat exchange, wherein the first unit reaction The apparatus includes a combustion disk group containing a combustion catalyst and a recombination reaction disk group containing a recombination catalyst; wherein the second unit reaction device includes a combustion disk group and a heat exchange disk group The second unit reaction device includes a heat exchange disk group; wherein the combustion unit of the first unit reaction device is connected to a heat exchange disk of the third unit reaction device; Wherein the other heat exchange disk of the third unit reaction device is connected to the combustion disk group of the first unit reaction device; and wherein the heat exchange disk group of the second unit reaction device is connected a disc group for recombination reaction to the first unit reaction apparatus. In the production of hydrogen by using the hydrogen generator of the present invention as described above, the above method can be used as a preferred embodiment. Heavy 93390 26 1306081 group reaction, first, supply a mixture of hydrogen and air or oxygen to the first unit reaction device (11)' and burn in the combustion disk group (41,); The heat and exhaust gas are discharged through the third unit reaction device (12), and after the methanol as a liquid fuel is supplied to the third unit reaction device (12) and gasified, the vaporized sterol is further for To the first reaction unit means (11) to continue the combustion reaction. Herein, if the combustion reaction is initiated by methanol, the supply of hydrogen as a gas phase fuel is stopped, and the gas phase mixture of the hydrogen and air or oxygen is supplied to the second unit reaction (13). In other words, the combustion reaction is continued by adjusting the feed ratio of the sterol until the temperature of the first unit reaction device (11) reaches 26 〇 to 32 〇 C, and if it is reached, it is supplied as a raw material. a mixture of decyl alcohol and water to the disc reaction group (41,) of the first unit reaction apparatus (11) to carry out the combustion reaction, and supply a hydrogen stream as a product stream to the fourth Unit reaction unit (15). In the fourth unit reaction unit (15), methanol as a liquid fuel may also be vaporized and supplied to the second unit reaction unit (13). In the second unit reaction apparatus (丨3), the combustion reaction can also be carried out, and if the temperature reaches 11 〇 to 20 (rc, the operation starting step of the hydrogen generating apparatus of the present invention is completed, and by continuous The combustion reaction is continued in the first unit reaction unit (丨1) and the second unit reaction unit (13) using methanol as only a liquid fuel, and is recombined by the first unit reaction unit (11). The reaction is continuously produced by mixing a mixture of methanol and water as a raw material in the disk group (41,.). The present invention can be more specifically illustrated by the following examples. However, it should be understood that this embodiment The invention is not limited in any way. 93390 27 1306081 « Example 1 The disc group for recombination reaction consists of the following method: using a weight ratio of 4/4/2 by the common sinking method Synthetic copper/zinc/salt oxide • as a recombination catalyst, and in the first unit reaction unit, the recombination reaction is carried out with a disk-like substance, and each microchannel disk is 〇6 g of recombinant catalyst. The amount of coating. The burning of the disk group consists of the following First, the microchannel disc-group is coated with ^_alumina as a combustion catalyst, and an aqueous solution having a platinum amount of about 3 wt% of platinum is added to the α-alumina to make the disc group Drying and calcining. The first unit reaction apparatus is composed of the following steps: as described above, the six recombination reaction disc groups and the five combustion disc groups are alternately stacked with each other, and By starting the operation and adjusting the temperature of the first unit reaction device to about 300. (: to carry out the recombination reaction without attaching the selective oxidation reactor. At the same time, as a raw material for the recombination reaction, methanol: water The mixing ratio is 50:50, and the flow rate of the raw material for the recombination reaction supplied to the first unit reaction apparatus is adjusted to 3 cc/min., and the flow rate of the methanol as the fuel is adjusted to hl. Ec/min. Under these operating conditions, the first unit reaction device reaches the above temperature after about 90 minutes. When the first unit reaction device is operated at 3, the composition ratio of the product after the recombination reaction, To remove the scent The weight is calculated as '74.8% hydrogen, 24.4% carbon dioxide and 0.84% carbon monoxide. According to the amount of methanol involved in the recombination reaction, the methanol conversion rate is 99.5%. The following equation (1) is used to calculate the indication. The thermal performance of this operational efficiency is described in pages 21 to 27 of J. 〇fp〇Wer s〇urce 93390 28 1306081 (10) (2002) of the Pacific North Laboratory, which is described as the methanol described in the previous paragraph of the present invention. Water vapor recombination unit for objective comparison: - [Equation (1)] • Operational efficiency = (AHcH2) / (AHc total ch3oh) CH3OH (liquid) + 1.5 〇 2 = c 〇 2+ 2H20 (liquid) kJ / Mo Ear « H2+0.5 02=H20 (gaseous) ^11=-242 kJ/mole In the above equation, △ Hc H2 is the total enthalpy of the hydrogen produced, and the total muscle (3) is involved in the reorganization The total enthalpy of total methanol reacted with the combustion reaction. Since the hydrogen generating apparatus of the present invention has a thermal efficiency of 59.5 ° / according to the calculation of the above equation. . Moreover, after the selective oxidation device was connected, the carbon monoxide content in the hydrogen product was lowered to 70 ppm. At the same time, the thermal efficiency is also reduced to 56.7. /. Because some hydrogen reacts together during this selective oxidation reaction. (Industrial Applicability) According to a hydrogen generating device including a unit reaction device including a microchannel including a coating of a combustion catalyst and/or a recombination catalyst, and a hydrogen generating method using the hydrogen generating device of the present invention By using a unit reaction apparatus comprising a group of combustion discs containing a combustion catalyst on a microchannel and a disc group of recombination reactions containing a recombination catalyst on a microchannel, which are stacked adjacent to each other, The combustion reaction is carried out in conjunction with the recombination reaction to maintain the recombination reaction in a stable temperature range, since the recombination in the composition should be similar to the occurrence of the combustion reaction, thus causing the heat generated by the combustion reaction to be 93390 29 1306081 quickly Transferring to the recombination reaction, and performing the combustion reaction and the recombination reaction in the microchannel while maintaining a high reaction temperature; achieving a conversion ratio of 99% or more of sterol and a high thermal efficiency of 59.5% or More than • 59.5% produces hydrogen. Moreover, the crucible generating device of the present invention which is designed to have high thermal efficiency and has high conversion to hydrogen and the crucible generating method using the hydrogen generating device are efficiently supplied by using an alcohol (for example, decyl alcohol) as a fuel. Hydrogen to the fuel cell system, since all of the combustion reaction and the recombination reaction can be carried out by using microchannels, and the hydrogen generating device itself can be very small by the gasification of the heat exchange. Further, the production of hydrogen can be controlled by merely adjusting the number of stacks of such disc groups in units of the disc group for the combustion and the disc group for the recombination reaction. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the entire structure of a hydrogen generating apparatus of the present month. Fig. 2 is an exploded view showing the unit reaction device for the hydrogen generator of the second drawing. Fig. 3 is an exploded photograph of a specific embodiment of the hydrogen generating apparatus of the present invention. Fig. 4 is an exploded view of the disc-only group constituting the unit reaction apparatus of Fig. 2. Fig. 5 is a plan view showing a microchannel disk constituting the disk group of Fig. 4. Fig. 6 is a plan view showing the lining used in the disk group constituting the unit reaction apparatus of the present invention. 30 93390 1306081 Figure 7 is a cross-sectional view of a disk group constituting the unit reaction device of Fig. 2 [Description of main components] 11 First unit reaction device 12 Third unit reaction device 13 Second unit reaction device 14 Selection Oxidation reactor 15 fourth unit reaction unit 21 hydrogen source 22 first oxygen source 23 valve 24 for changing the flow direction first fuel source 25 second oxygen source 26 second fuel source 27 raw material source 28 third oxygen source 31 Filter 41 unit reaction unit 41, combustion disc group 41" Recombination reaction disc group 42 and 42' top and bottom cover 43, burner inlet 43 burner outlet 44? Recombiner inlet 44 recombiner outlet 45 And 45' microchannel discs 46 and 46' inlets 47 and 47' outlets 48 and 48' first connecting holes 49 and 49' second connecting holes 51 and 5 Γ microchannels 52 and 52' partition walls 53 and 53' Truncated walls 54 and 54' Converging recesses 55 and 55' Converging projections 61 Pad 62 Opening 63 Through-hole 71 Channel forming space 72 Catalyst-covered portion 31 93390 Revision

Claims (1)

1306081 丨 1 _ 1 丨_丨_. Ml·..， 第95111879號專利申請案 申請專利範圍修正本 (95年11月21日） ..二種氫產生裝置，係包括至少一個燃燒/重組反應用之 '第一單位反應裝置，該第一單位反應裝置係由含有燃燒 -觸媒之燃燒用盤狀物組與含有重組觸媒之重組反應用 盤狀物組所組成，其中各盤狀物組含有一對微通道盤狀 _ 物，微通道係形成在該微通道盤狀物的一面的表面上， 且該微通道盤狀物以該微通道彼此相對的方式相互組 曰，/、中D亥燃燒用盤狀物組在該微通道中含有該燃燒觸 媒，以及其中該重組反應用盤狀物組在該微通道中含有 該重組觸媒。 2.如申請專利範圍第〗項之氫產生裝置，其中該第一單位 反應裝置係包括燃燒用盤狀物組與重組反應用盤狀物 、、且其兩者係相互地堆疊。 •,申&quot;月專利範圍第1項之氫產生裝置，其中該燃燒觸媒 係選自鉑族元素，例如鉑、鍺、釕、锇、銥與鈀；金； 銀’銅及其混合物所組成之群組。 •如申請專利範圍第3項之氫產生裝置，其中該燃燒觸媒 ，藉由下述方式形成··被覆觸媒撐體，添加0.1至5重 之量的燃燒觸媒至該觸媒撐體，並乾燥，鍛燒，以 及支撐該燃燒觸媒。 5 由—士 ,叫專利範圍第4項之氫產生裝置，其中該觸媒撐體 係選自氧化鋁、《 _氧化鋁、氧化錯（Zr02)、二氧化矽 c S 93390修正版 1306081 (Si〇2)或其混合物所組成之群組。 6. 如申凊專利範圍第1項之氫產生裝置，其中該重組觸媒 係選自銅/氧化鈽/氧化鍅（Cu/Ce〇2/Zr02)之合成產物、 銅/氧化辞/氧化鋁（Cu/Zn〇2/Al2〇3)之合成產物、銅/氧化 鈽/氧化鋁（Cu/CeCVAlsO3)之合成產物、銅/氧化錯/氧化 鋁（Cu/Zr02/ Al2〇3)之合成產物以及銅_辞_銘（CuZnA1) 氧化物的固溶體所組成之群組。 7. 如申請專利範圍第6項之氫產生裝置，其中該重組觸媒 係為藉由共沉澱方法以銅氧化物：鋅氧化物：鋁氧化物 之重1比為3至5:3至5: 1至3所合成的產物。 8. 如申請專利範圍第1項之氫產生裝置，其中該第一單位 反應裝置所包含之單位反應裝置係包括由兩個金屬塊 所組成的蓋子，其中該燃燒用盤狀物組與該重組反應用 盤狀物組係在這兩個蓋子間相互堆疊。 9. 如申請專利範圍第8項之氫產生裝置，其中組成該單位 反應裝置之各盤狀物組係包括一對微通道盤狀物，微通 道係形成於該微通道盤狀物的一面的表面上，且該微通 道盤狀物以該微通道彼此相對的方式相互組合。 10. 如申請專利範圍帛8項之氫產生裝置，進一 ^包括由銅 板所製成之襯墊。 U.如申請專利範圍第9項之氫產生裝置，其中該微通道盤 狀物具有入口、出口、第一連接孔與第二連接孔，其中 °亥入口與該出口係彼此位於對角線上，且該第一連接孔 與該第二連接孔係彼此位於對角線上，其中在該入口與 93390修正版 2 1306081 該出口間形成溝槽，該溝槽係從包括該入口 主工曰-、琢出口之 表面具有一定的深度。 12.如申請專利範圍第n項之氫產生裝 六' τ用以m制 燃料或原料之流動，而使得來自該入口或 人必出口之群r嫩 料或原料擴散至該微通道，或使該燃料或原料收集=該 入口或出口的會聚性凹部與會聚性凸部係形成於該2 口或該出口周圍。 、'^ 13. 如申請專利範圍第〗項之氫產生裝置，其中第三單位 應裝置（12)係連接至該第一單位反應裝置。 反 14. 如申請專利範圍第13項之氫產生裝置，其中該第三單 位反應裝置係包括含有一對微通道盤狀物之熱交換= 盤狀物組，微通道係形成於該微通道盤狀物的一面的表 面上，且該微通道盤狀物以該微通道彼此相對的方式相 互組合；其中該熱交換用盤狀物組不包含觸媒例如燃 燒觸媒或重組觸媒。 • 15.如申請專利範圍第1項之氫產生裝置，其中第二單位反 應裝置係連接至該第一單位反應裝置。 16·如申請專利範圍* 15項之氳產生裝置，其中該第二單 位反應裝置係包括燃燒用盤狀物組與熱交換用盤狀物 組。 17·如申請專利範圍第15項之氫產生裝置，其中第四單位 反應裝置係連接於該第二單位反應裝置與該第一單位 反應裝置之間。 18·如申請專利範圍第17項之氫產生裝置，其中該第四單 3 93390修正版 1306081 位反應裝置係包括熱交換用盤狀物組。 ❹Μ專利範㈣！項之氫產生裝置，其中選擇性 ⑽_氧化反應器進一步連接至該第一單位反應 裝置。 20. 如申請專利範圍第19項之氣產生裳置，其中滤器係連 接於，第-單位反應t置與該選擇性氧化反應器之間。 21. -種氫產生裝置，係包括至少一個燃燒/重組反應用之 第一單位反應裝置、至少-個氣化用之第二單位反應裝 置$至少一個熱交換用之第三單位反應裝置，其中該第 -單位反應裝置包括含有燃燒觸媒之燃燒用盤狀物組 與3有重組觸媒之重組反應用盤狀物組；其中該第二單 位反應裝置包括燃燒用盤狀物組與熱交換用盤狀^且. 其中該第三單位反應裝置包括熱交換用盤狀物組；其中 該第一單位反應裝置之燃燒用盤狀物組係連接至該第 三單位反應裝置之一個熱交換用盤狀物；其令該第三單 位反應裝置之其它熱交換用盤狀物係連接至該第:單 位反應裝置之燃燒用盤狀物組；以及其中該第二單位反 應裝置之熱交換用盤狀物組係連接至該第一單位反應 裝置之重組反應用盤狀物組。 &quot; 22.—種使用如申請專利範圍第！項之氫產生裝置之氫產 生方法，係包括： (1)第一燃燒步驟，係將氣相燃料與氧化劑共同饋入至 該第一單位反應裝置之燃燒用盤狀物組，使該燃料 於該燃燒用盤狀物組中燃燒，並利用燃燒熱來加熱 93390修正版 4 1306081 田比鄰4燃燒㈣狀物組之重組反應用盤狀物电.以 及 ， (2)產生氫的重組步，驟，係藉由將用於重組反應的原料 (包括曱醇和水的混合物）饋人至經加熱的重組反應 用盤狀物組，使該原料重組。 23.如申請專利範圍第22項之氫產生方法，其中該第一單 位反應裝置之溫度係持續地維持在26〇至32〇乞之範圍 内。 从如申請專利範圍第22項之氫產生方法，在該第一燃燒 步驟（1)與該重組步驟（2)間，進一步包括： 第一連接步驟，係將含有熱交換用盤狀物組（各該 盤狀物組包括一對微通道盤狀物，微通道係形成在該微 通道盤狀物的一面的表面上，且該微通道盤狀物以該微 通道彼此相對的方式相互組合）之第三單位反應裝置連 接至該第一單位反應裝置之燃燒用盤狀物組；其中該第 三單位反應裝置之熱交換用盤狀物組的任何入口係連 接至該第一單位反應裝置之燃燒用盤狀物組之出口；以 及 第一氣化步驟，係將由該第一單位反應裝置之燃燒 用盤狀物組所釋放之廢氣連接至該第三單位反應裝置 之一個熱交換用盤狀物組，並將液態燃料饋入至該第三 單位反應裝置之其它熱交換用盤狀物組，以使該液態燃 料氣化。 25.如申睛專利範圍第24項之氫產生方法，其中該第三單 5 93390修正版 1306081 位反應裝置之溫度係持續地維持在80至1 〇〇乞之範圍 -内。 • - 26.如申請專利範圍第22項之氳產生方法，在該第一燃燒 . 步驟（1)與該重組步驟（2)間，進一步包括： 第二連接步驟，係將含有燃燒用盤狀物組與熱交換 • 用盤狀物組之第二單位反應裝置連接至該第一單位反 應裝置之重組反應用盤狀物組，其中該第二單位反應裝 置之熱交換用盤狀物組的出口係連接至該第一單位反 • 應裝置之重組反應用盤狀物組之入口； 第二燃燒步驟’係將氣相燃料與氧化劑共同饋入至 該第二單位反應装置之燃燒用盤狀物組，使該燃料在該 燃燒用盤狀物組中燃燒，並藉由利用燃燒熱來加熱毗鄰 該燃燒用盤狀物組之熱交換用盤狀物組； 第二氣化步驟，係將重組反應用的原料（包括曱醇 和水的混合物）饋入至該第二單位反應裝置之熱交換用 • 盤狀物組，以使該原料氣化；以及 第一進料步驟，係將在第二氣化步驟中該經氣化之 重組反應用的原料饋入至該第一單位反應裝置之重組 反應用盤狀物组。 27.如申請專利範圍第22項之氫產生方法’在該第一燃燒 步驟（1)與該重組步驟（2)間，進一步包括： 弟二連接步驟’係將含有熱交換用盤狀物組之第四 單位反應裂置連接至該第二單位反應裝置之燃燒用盤 狀物組，其中該第四單位反應裝置之熱交換用盤狀物組 6 93390修正版 1306081 的任何一個出口係連接至該第二單位反應裝置之燃燒 用盤狀物組之入口；且該熱交換用盤狀物組之入口係連 接至液態燃料源； 第四連接步驟’係將第四單位反應裝置之其它入口 連接至該第一單位反應裝置之重組反應用盤狀物組之 _ 出口，並將熱交換用盤狀物的出口連接至產物收集器； 以及 /、’ 第三氣化步驟，係藉由利用從該第一單位反應裝置 之重組反應用盤狀物組所釋放出的產物流的熱，使饋入 至該第二單位反應裝置的液態燃料氣化。 况如申請專利範圍第27項之氫產生方法，其中該第二單 位反應裝置之溫度係持續地維持在i 1〇至2〇〇它之範圍 内。 29.-種使用如申請專利範圍第21項之氫產生裝置之氯產 生方法，係包括： ⑴第:燃燒步驟’係將氣相燃料與氧化劑共同饋入至 該第-單位反應裝置之燃燒用盤狀物組，且使該辦 料燃燒； ⑺第-預熱步驟，係透過該第三單位反應裝置之一個 熱交換用餘物組，利用從該第—燃燒步驟中的辦 燒用盤狀物組所釋放的廢氣使該第三單位反應裝置 預熱至80至1〇〇。〇，· ⑺第：燃燒步驟’係透過該第三單位反應裝置之其它 熱交換用盤狀物組，藉由於 稭由饋入及氣化液態燃料至該 7 ( 93390修正版 •1306081 第一單位反應裝置之燃燒用盤狀物組，並使該燃料 與饋入的氧化劑同時燃燒，以使該第一單位反應裝 置加熱至260至320°C; (4) 第三燃燒步驟，為藉由將氣相燃料饋入至該第二單 位反應裝置之燃燒用盤狀物組，並使該燃料與氧化 劑共同燃燒，以使該第二單位反應裝置加熱至11〇 至 200°C ; (5) 氣化步驟，係藉由使該作為重組反應之原料的甲醇 與水之混合物通過該第二單位反應裝置之燃燒用盤 狀物組，並將該混合物饋入至該第一單位反應裝置 之重組反應用盤狀物組，以使該混合物氣化丨以及 (6) 重組步驟，為藉由使該經氣化的原料通過該第一單 位反應裝置之重組反應用盤狀物組，以將該經氣化 的原料重組成氫。 8 93390修正版1306081 丨1 _ 1 丨_丨_. Ml·.., Patent Application No. 95111879 (Amended November 21, 1995). Two hydrogen generation devices including at least one combustion/recombination reaction The first unit reaction device is composed of a combustion disk group containing a combustion-catalyst and a disk group for recombination reaction containing a recombination catalyst, wherein each disk is composed of a disk group The group contains a pair of microchannel disc-shaped bodies, and the microchannels are formed on the surface of one side of the microchannel disc, and the microchannel discs are grouped with each other in such a manner that the microchannels face each other, /, medium The D-combustion disk group contains the combustion catalyst in the microchannel, and wherein the recombination reaction disk group contains the recombination catalyst in the microchannel. 2. The hydrogen generator of claim 1, wherein the first unit reaction apparatus comprises a disc group for combustion and a disc for recombination, and the two are stacked on each other. The hydrogen generating device of the first aspect of the patent, wherein the combustion catalyst is selected from the group consisting of platinum group elements such as platinum, rhodium, ruthenium, osmium, iridium and palladium; gold; silver 'copper and mixtures thereof The group that makes up. The hydrogen generating device according to claim 3, wherein the combustion catalyst is formed by coating the catalyst support by adding 0.1 to 5 weights of the combustion catalyst to the catalyst support. And drying, calcining, and supporting the combustion catalyst. 5 The hydrogen generating device of the fourth aspect of the patent, wherein the catalyst supporting system is selected from the group consisting of alumina, _alumina, oxidized (Zr02), ceria c S 93390 modified version 1306081 (Si〇 2) A group consisting of or a mixture thereof. 6. The hydrogen generating device according to claim 1, wherein the recombination catalyst is selected from the group consisting of copper/cerium oxide/cerium oxide (Cu/Ce〇2/Zr02), copper/oxidized/alumina Synthesis of (Cu/Zn〇2/Al2〇3), synthesis of copper/yttria/alumina (Cu/CeCVAlsO3), synthesis of copper/oxidized/alumina (Cu/Zr02/Al2〇3) And a group consisting of solid solutions of copper _ _ _ _ (CuZnA1) oxide. 7. The hydrogen generating apparatus according to claim 6, wherein the recombination catalyst is a ratio of copper oxide: zinc oxide: aluminum oxide by coprecipitation to 3 to 5:3 to 5 : 1 to 3 synthesized product. 8. The hydrogen generating apparatus of claim 1, wherein the unit reaction apparatus included in the first unit reaction apparatus comprises a lid composed of two metal blocks, wherein the burning disc group and the recombination A reaction disc group is stacked on each other between the two covers. 9. The hydrogen generating apparatus of claim 8, wherein each of the disc groups constituting the unit reaction apparatus comprises a pair of microchannel discs, and the microchannels are formed on one side of the microchannel disc. On the surface, and the microchannel discs are combined with each other in such a manner that the microchannels face each other. 10. If the hydrogen generating device of the patent application 帛8 is applied, the gasket comprising the copper plate is further included. The hydrogen generating device of claim 9, wherein the microchannel disk has an inlet, an outlet, a first connecting hole and a second connecting hole, wherein the inlet and the outlet are on a diagonal line with each other, And the first connecting hole and the second connecting hole are located on a diagonal line with each other, wherein a groove is formed between the inlet and the 93390 modified version 2 1306081, the groove is from the inlet main work-- The surface of the exit has a certain depth. 12. The hydrogen generating device of the nth item of the patent application scope is used for the flow of fuel or raw materials, so that the group of raw materials or raw materials that must be exported from the inlet or the person are diffused to the microchannel, or The fuel or material collection = the converging recess and the converging projection of the inlet or outlet are formed around the 2 port or the outlet. , '^ 13. The hydrogen generating device of claim 1, wherein the third unit (12) is connected to the first unit reaction device. The hydrogen generating device of claim 13, wherein the third unit reaction device comprises a heat exchange=disc group containing a pair of microchannel discs, and the microchannel is formed in the microchannel disc On the surface of one side of the object, and the microchannel discs are combined with each other in such a manner that the microchannels are opposed to each other; wherein the heat exchange disc group does not contain a catalyst such as a combustion catalyst or a recombination catalyst. 15. The hydrogen generating device of claim 1, wherein the second unit reaction device is coupled to the first unit reaction device. 16. The device for producing a ninth aspect of the invention, wherein the second unit reaction device comprises a disk group for combustion and a disk group for heat exchange. The hydrogen generating device of claim 15, wherein the fourth unit reaction device is connected between the second unit reaction device and the first unit reaction device. 18. The hydrogen generator of claim 17, wherein the fourth unit 3 93390 revision 1306081 reaction device comprises a heat exchange disk group. ❹Μ Patent Fan (4)! A hydrogen generating unit wherein the selective (10) oxidation reactor is further connected to the first unit reaction unit. 20. The gas generating device according to claim 19, wherein the filter is connected, the first unit reaction t is placed between the selective oxidation reactor. 21. A hydrogen generating apparatus comprising: at least one first unit reaction unit for combustion/recombination reaction, at least one second unit reaction unit for gasification, and at least one third unit reaction unit for heat exchange, wherein The first unit reaction apparatus includes a combustion disk group containing a combustion catalyst and a recombination reaction disk group having a recombination catalyst; wherein the second unit reaction device includes a combustion disk group and heat exchange The third unit reaction device includes a heat exchange disk group; wherein the combustion unit of the first unit reaction device is connected to a heat exchange of the third unit reaction device a disk; the other heat exchange disk of the third unit reaction device is connected to the combustion disk group of the first unit reaction device; and the heat exchange disk of the second unit reaction device The group is connected to the disc group of the recombination reaction of the first unit reaction device. &quot; 22. - Use as for the scope of patent application! The hydrogen generating method of the hydrogen generating device of the present invention includes: (1) a first combustion step of feeding a gas phase fuel and an oxidant together to a combustion disk group of the first unit reaction device, so that the fuel is The combustion is burned in a disk group, and the heat of combustion is used to heat the disk reaction of the regenerative reaction of the 93390 modified version 4 1306081, the Tiebi 4 combustion (four) group, and (2) the recombination step of generating hydrogen. The raw material is reconstituted by feeding the raw material for the recombination reaction (including a mixture of decyl alcohol and water) to the heated disc group for the recombination reaction. 23. The hydrogen generating method according to claim 22, wherein the temperature of the first unit reaction apparatus is continuously maintained in the range of 26 Torr to 32 Torr. The hydrogen generating method of claim 22, wherein the first burning step (1) and the recombining step (2) further comprises: a first joining step of containing a heat exchange disc group ( Each of the disc sets includes a pair of microchannel discs formed on a surface of one side of the microchannel disc, and the microchannel discs are combined with each other in such a manner that the microchannels face each other) a third unit reaction device connected to the combustion disk group of the first unit reaction device; wherein any inlet of the heat exchange disk group of the third unit reaction device is connected to the first unit reaction device An outlet for the combustion disk group; and a first gasification step of connecting the exhaust gas released by the combustion disk group of the first unit reaction device to a heat exchange disk of the third unit reaction device And the liquid fuel is fed to the other heat exchange disc group of the third unit reaction device to vaporize the liquid fuel. 25. The hydrogen generating method according to claim 24, wherein the temperature of the third unit 5 93390 revision 1306081 reaction device is continuously maintained within a range of 80 to 1 Torr. • - 26. The method for producing the enthalpy of claim 22, between the first combustion step (1) and the recombination step (2), further comprising: a second joining step comprising a disk for combustion Object group and heat exchange; a second unit reaction device of the disk group is connected to the disk group for recombination reaction of the first unit reaction device, wherein the heat exchange disk group of the second unit reaction device The outlet is connected to the inlet of the disc group for recombination reaction of the first unit counter device; the second combustion step is to feed the vapor phase fuel and the oxidant together to the combustion disc of the second unit reaction device And combusting the fuel in the combustion disk group and heating the heat exchange disk group adjacent to the combustion disk group by using combustion heat; the second gasification step is a raw material for recombination reaction (including a mixture of decyl alcohol and water) fed to the heat exchange disk group of the second unit reaction device to vaporize the raw material; and a first feeding step, which is to be In the second gasification step Recombinant gasification reaction feedstock is fed to the first reactor unit of the recombination reaction disk device group was used. 27. The method for producing hydrogen according to claim 22, wherein between the first combustion step (1) and the recombination step (2), the method further comprises: the second connection step is to include a disk group for heat exchange The fourth unit reaction split is connected to the combustion disk group of the second unit reaction device, wherein any one of the outlets of the heat exchange disk group 6 93390 revision 1306081 of the fourth unit reaction device is connected to An inlet of the combustion disk group of the second unit reaction device; and the inlet of the heat exchange disk group is connected to the liquid fuel source; and the fourth connection step is to connect the other inlets of the fourth unit reaction device Up to the outlet of the disc reaction group of the first unit reaction apparatus, and connecting the outlet of the heat exchange disc to the product collector; and /, 'the third gasification step is utilized by The recombination reaction of the first unit reaction unit vaporizes the liquid fuel fed to the second unit reaction unit by the heat of the product stream released from the disc group. The hydrogen generating method of claim 27, wherein the temperature of the second unit reaction device is continuously maintained within a range of i 1 〇 to 2 。. 29. A chlorine production method using a hydrogen generator according to claim 21, wherein: (1) a combustion step of feeding a gas phase fuel together with an oxidant to the combustion of the first unit reaction device a disk group, and burning the material; (7) a preheating step of passing through a heat exchange waste group of the third unit reaction device, using a disk shape for burning from the first combustion step The exhaust gas released by the object group preheats the third unit reaction unit to 80 to 1 Torr. 〇, (7) The: combustion step 'is through the other heat exchange disc group of the third unit reaction device, by feeding and gasifying the liquid fuel to the 7 (93390 revision version • 1306081 first unit) a combustion disk set of the reaction device, and the fuel is simultaneously combusted with the fed oxidant to heat the first unit reaction device to 260 to 320 ° C; (4) the third combustion step is performed by The gas phase fuel is fed to the combustion disk group of the second unit reaction device, and the fuel and the oxidant are co-combusted to heat the second unit reaction device to 11 〇 to 200 ° C; (5) gas The step of passing the mixture of methanol and water as a raw material for the recombination reaction through the combustion disk group of the second unit reaction device, and feeding the mixture to the recombination reaction of the first unit reaction device Using a disk group to vaporize the mixture and (6) a recombination step, the disk group is subjected to a recombination reaction by passing the vaporized material through the first unit reaction device Gasified raw material weight To hydrogen. Revision 893390 第2圖Figure 2
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