200922870 rj^uuuooi w 25947twf.doc/n 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種氫氣產生器系統（hydr〇g妨 generation system) ’且特別是有關於一種可以作為高分子 電解貝燃料電池(Polymer Electrolyte Fuel Cell，PEFC)發電 系統所需之燃料的氫氣產生器系統。 【先前技術】 ) 同分子電解質燃料電池（Polymer Electrolyte Fuel200922870 rj^uuuooi w 25947twf.doc/n IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a hydrogen generator system (and hydr〇g generation system) and particularly relates to one that can be used as a high A hydrogen generator system for fuels required for a Polymer Electrolyte Fuel Cell (PEFC) power generation system. [Prior Art] ) Polymer Electrolyte Fuel Cell (Polymer Electrolyte Fuel)
Cell ’ PEFC)應用於分散式定置型發電系統、可攜式發電系 統、或電動汽車動力系統，已是明確的產業趨勢。無論是 於分散式定置型發電系統或可攜式發電系統，都會運用既 有之燃料供應網，藉由燃料重組器(Ref〇rmer)將化石燃料 ，換成一氧化碳(CO)濃度低於2〇ppm之富氫重組氣，供應 高分子電解質燃料電池發電系統所需之燃料。 一般设s十之燃料重組器系統包括：燃料轉換成重組氣 之重組反應、水移轉反應(Water gas-shift，WGS)、選擇性 氧化(Preferential oxidation，Pr〇X)反應以及陽極廢氫氣氧 化與反應進料水汽化等單元，其反應後氣體溫度分別約為 250〜6〇〇°C(視燃料種類而定）、2〇〇〜3〇(rc、1〇〇〜2〇〇<t以及 400°C以上。最終產生之重組氣再經由冷卻至適當溫度，通 往燃料電池發電機組。 有關燃料重組器系統的專利，多是偏向於如何改善其 各單元反應的排列、如何提昇熱回收效益、以及如何提昇 燃料轉換成重組氣的效率、以及如何研發反應性更佳之各 200922870 rjH^owuooiw 25947twf.doc/n 單元反應觸媒。 然而’當前的系統仍存在重組氣中的C〇濃度不穩定 及CO濃度超過警戒值的問題，亟待解決。 【發明内容】 本發明提供一種氫氣產生器系統，可簡化整體燃料重 組器系統設計與操作’以不影響系統整體熱能轉換為原 則，又可同步提昇水移轉反應(water gas_shift，WGS)及選 〇 擇性氧化(preferential oxidation，PrOX)反應對於 CO 的轉 化率。 本Ίχ月^出種虱氣產生器系統，包括一個重組反應 單元、一個水移轉反應(WGS)單元、一個降溫除水且能自 我升溫之裝置和一個選擇性氧化(Pr〇x)反應單元。其中， ^組反應單元是用以將燃料轉換成重組氣，而水移轉反應 單元則對來自重組反應單元的重組氣進行水移轉反應。至 於降溫除水且能自我升溫之裝置則是用以降低來自:述水 移轉反應單元之重組氣的水蒸氣濃度。選擇性氧化反應單 元則對來自降溫除水且能自我升溫之裝置的重組進 CO選擇性氧化反應。 在本發明之一實施例中，經上述選擇性氧化反應單元 所輸出的重組氣為CO漠度低於20 ppm以下之富氫氣體， 可以作為燃料電池(Fuel Cel】)發電系統所需之燃才、， 在本發明之一實施例中，上述燃料包括化石辦料 生能源。·其中，化石燃料譬如城氣、甲醇、酒精、液化 石油氣(liquefied petroleum gas，LPG)、煤油或柴油。再生 200922870 I w 25947twf.doc/n 能源則例如魏反應產生之甲⑥或生質能發酵產生之酒 精。 — 在本發明之-實施例中，上述降溫除水且能自我升、、θ 之裝置包括-個冷凝裝置，其中冷凝裝置與水移轉反應= 兀相連，用以將來自水移轉反應單元之重組氣冷凝至 〜80〇C。 在本發明之一實施例中，上述降溫除水且能自我升溫 之裝置包括一個含内管與外管的雙套管以及一個冷凝蛇7皿 管。其中，冷凝蛇管位於雙套管之内管内，以使來自水移 轉反應單元之重組氣由上述内管進入而被冷凝蛇管冷凝至 60°C〜80°C ’再經上述外管回溫至1〇〇。〇〜15〇〇c。 在本發明之一實施例中，上述降溫除水且能自我升溫 之裝置包括一個含内管與外管的雙套管以及一個熱導管。 其中，熱‘管位於雙套管之内管内，以使來自水移轉反應 單元之重組氣由上述内管進入而被熱導管冷凝至6(Π：〜8〇 °c ’再經上述外管回溫至100°c〜150°c。 在本發明之一實施例中，上述水移轉反應單元包括一 段式反應單元或兩段式反應單元。其中，兩段式反應單元 包括一個馬溫水移轉反應單元和一個低溫水移轉反應單 元0 在本發明之一實施例中，上述重組反應單元包括蒸氣 重組反應單元或自熱式重纟且反應單元。 在本發明之一實施例中，上述氫氣產生器系統更包括 一個陽極廢氫氣氧化單元，用以將廢氫氣提供給上述重組 200922870 r^^owooiw 25947twf.doc/n 反應單元作為能源。其中，陽極廢氫氣氧化單元例如單獨 存在或置於重組反應單元之内管。 在本發明之一實施例中，上述氫氣產生器系統更包括 一個反應進料燃料預熱暨水汽化單元’用以將預熱之燃料 暨水蒸氟提供給上述重組反應單元。 在本發明之一實施例中，上述氫氣產生器系統更包括 一個重組氣溫度調節控制單元，以調節來自選擇性氧化反 應單元的重組氣之溫度。 本發明因為於氫氣產生器系統的水移轉反應(WGS)單 元與選擇性氧化(PrOX)反應單元之間，加入一個降溫除水 且能自我升溫之裝置，因此可使經WGS反應後之重組氣 的水蒸氣濃度降低，而提昇選擇性氧化反應對於c〇的反 應選擇性及轉化率，降低選擇性氧化反應的負荷，並使氫 氣產生系統更穩定，使富氫重組氣中的c〇濃度可以穩定 低於20 ppm以下。 為讓本發明之上述特徵和優點能更明顯易懂，下文特 舉較佳實施例，並配合所附圖式，作詳細說明如下。 【實施方式】 圖1疋依照本發明之第一實施例之一種氫氣產生器 統之方塊圖。 請參照圖卜第-實施例的氫氣產生器系統1〇〇至少 包括一個重組反應單元11〇、一個水移轉反應(WGS)單元 |20、一個降溫除水且能自我升溫之裝置13〇和一個選擇性 氧化(PrOX)反應單tl ho。在圖！巾，重組反應單元 200922870 rjH^uwuooj. w 25947twf.doc/n 例如疋蒸氣重組反應單元或自熱式重組反應單元，用以將 燃料轉換成重組氣，其中燃料例如化石燃料或再生能源。 舉例來說，化石燃料包括天然氣、甲醇、酒精、液化石油 氣(liquefied petroleum gas ’ LPG)、煤油或柴油；再生能源 則包括例如厭氧反應產生之甲烷或生質能發酵產生之酒 精。當燃料為化石燃料時，在重組反應單元u〇中發生的 反應如下： ^ 2HC+02+H20->2H2+CO+C〇2 然後，請繼續參照圖1，來自重組反應單元丨的重 組氣會在水移轉反應單元120中進行水移轉反應，以進一 步將CO移轉為氫氣。在第一實施例中，水移轉反應單元 120疋一段式反應單元。此外，水移轉反應單元I]。還可 以疋兩段式反應單兀，譬如包括高溫水移轉反應（high tempe論re water gas-shift，HTS)單元以及緊接於後之低溫 水移轉反應(low temperature water gas-shift，LTS)單元。而 在水移轉反應單元120發生的反應如下： CO+H2〇~^" H2+CO2 已知提高水蒸氣(Steam’s)與C0莫耳比有利於埶力學 =衡，提高CO轉化率使重組氣的c〇濃度下降，但是於 向S/CO莫耳比(>3〜4)狀況時，進入選擇性氧化(pr〇x)反應 皁元140之重組氣的水蒸氣濃度會高達5〇%、甚至最高 時，會超過PrOX觸媒可承受的臨界點，不但重組氣中的 水蒸氣會與CO競爭吸附，且水蒸氣濃度高也會稀釋總體 氧化放熱溫昇，導致PK)X _對於c〇反應選擇率及轉 200922870 l W 25947twf,doc/n 化率明顯下降’如圖2所不。圖2是選擇性氧化(pj*〇x)反 應單元140中的水蒸氣濃度與CO轉化率之關係曲線圖。 從圖2可知，水蒸氣濃度愈高，則CO轉化率愈低。而c〇 轉化率變低’將使得系統產生之重組氣的C〇濃度不穩定 且容易超過lOOppm的警戒值。因此，第一實施例於選擇 性氧化反應單元140之前，設有降溫除水且能自我升溫之 裝置130 ’用以降低來自水移轉反應單元丨2〇之重組氣的 水蒸氣(S)濃度。 在圖1中，降溫除水且能自我升溫之裝置13〇包括一 個冷凝裝置132,其中冷凝裝置132與水移轉反應單元12〇 相連，用以將來自水移轉反應單元12〇之重組氣冷凝至大 約6(TC〜8(rC，以使重組氣中的水蒸氣凝結，此時重組氣 ，，祭氣浪度譬如約降低至30%以下。然後，已經降低水 二氣/辰度之重組氣會進入一個加熱回溫部位1，期間能 藉由氫氣產生器系統100中原有的熱能，使經冷凝裝置132 =重組氣回溫至大約1〇〇它〜15〇。〇，並通往選擇性氧化反 應單元140。 ^之後，來自降溫除水且能自我升溫之裝置130的重組 二會在選擇性氧化反應單元_進行c〇選擇性氧化反 ‘边乂使剩餘的c〇激度被盡可能地減小，其反應如下： CO+0.5O 广 C02 ’、 體•來1就能夠獲得co濃度低於20ppm以下之富氮氣 兩少！·、組氣，其可作為燃料電池(fUd Cdl，FC)發電系統所 200922870 r-ίΗ^υυυοο i w 25947twf.d〇c/n 另外，第一實施例的氫氣產生器系統1〇〇還可包括一 個陽極廢氫氣氧化單元15〇，作為熱回收的單元，可將來 自燃料電池的廢氫氣與未達c〇濃度標準的重組氣(例如 CO濃度高於2G ppm的重喊)經或織放熱，提供給 上述重組反應單兀110作為能源，亦可配合外加燃料經姆 燒所釋出之熱值將反應進料加熱至適當可反應之溫度，再 進入重組反應單元110。而且，陽極廢氮氣氧化單元⑼ 〇 除了單獨f在外，也可置於重組反應單元110之内管。在 圖1中’還有—個反應進料燃料預熱暨水汽化單元16〇邀 -個重組氣溫度調節控鮮元m，分別歧重組反應單 =110以及選擇性氧化反應單元M〇。其中，反應進料燃 料預熱暨水汽化單元160是用來將預熱之燃料暨 供=反應單ί110。尤其是在圖1中以虛線加箭頭ί 不的U卩為魏之熱氣體可供應重組反應單it 110和 反應進料_賴暨水汽化單元⑽雜所需之孰量。至 (度=控制單元170則是用以調節來自選擇性 = 重組氣之溫度，使其配合燃料電池的 宜=明=氫氣產生器系統除第-實施例之外，還可對 ί::溫除水且能自我升溫之她計上的變更，如 個人盘11'里除水且能自我升溫之裝置300包括-20 冷相官32G位於雙套管310之内管302内， 11 200922870 rjHy\}\j\j〇〇 L yv 25947twf.doc/n 以使來自水移轉反應單元之重組氣，由上述内管3〇2進入 而被冷凝蛇管320冷凝至60Ό〜8〇。(：，再經上述外管3〇4 回溫至100。(：〜15(TC，再通往選擇性氧化反應單元。此外， 上述冷凝蛇管320也可用熱導管來取代，同樣可收降低水 蒸氣濃度之效。 ^以下列舉一個實驗例和一個比較例，來證實本發明之 氳氣產生器系統比習知氫氣產生器系統具有更優異的功 效。 【實驗例】 提供一個第一 々 貝施例所述的氧氣產生器系統，亚於氫 氣產生器系統_的重組反應單元中通入空氣、水蒸氣(Kg) 和天然氣(NG)，其中天然氣主成份是甲烷(CH4)，流量έ勺為 Π L/min。此外，空氣所含氧氣(a)與天然氣的流量/匕 CVNG約0.15〜0.18，而水蒸氣與天然氣的流量比Η2〇_ 則約為3.5〜3.7。然後，於氣體溫度約4〇(rc〜7〇(rc進行重 組反應，以將通入的燃料轉換成重組氣。接著，重級 ，入水移轉反應單元中，並於氣體溫度約25(rc〜3〇〇^& 行水移轉反應。之後，重組氣會進入降溫除水且能自 ，之裝置，並於其中先冷凝至大約听〜贼，以使 氣中的水条氣凝結’然後重組氣會回溫至大約漏 ^ =並通往選擇性氧化反應單元。最後，重組氣會 j約HKTC〜2〇(TC進行co選擇性氧化反應，以使= 氣成為CO濃度低於20 ppm以下之富氫氣體。 圖4為上述實驗例所得到的c〇濃度隨使 (elapsed time)變化的曲線圖。從圖*可知，本發明之氫^ 12 200922870 „ 25947twf.doc/n f生器系統隨使用時間增加，其c〇濃度極 度則達60%。 乳乳/辰 【比較例】 使用與上述實驗例相同的條件進行實驗，但 產生益系統中沒有降溫除水且能自我升溫之裝置，而= 水移轉反料讀轉性氧化反鮮元錢相連。 圖5為比較騎制的⑺濃度隨使㈣ 線圖。從圖5可知’ C0濃度變化極大，且圖5的縱轴的 百分比是以0.20為一格，比圖4以〇 01為一格要大得多， 因此與上-實驗例相較’比較例的系統所得到的重叙于^之 CO濃度超出標準，祕致氫氣產生難統不穩定。 ，上所述，本發明之氫氣產生器系統，因為在水移轉 反應單元與選擇性氧化反應單元之間加入一個降溫除水且 忐自我升溫之裝置，所以可藉由降低進入ΡΓ〇χ反應單元 之重組氣中的水蒸氣濃度，達到提昇PrOX反應對於C〇 的反，選擇性及轉化率之效果，使得系統產生之重組氣的 C0濃度可以穩定地低於20ppm，且使氫氣產生器系統具 有易操作的特性，以利於供應高分子電解質燃料電池發電 系統所需之燃料。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明’任何所屬技術領域中具有通常知識者，在不 脫離本發明之精神和範圍内’當可作些許之更動與潤飾， 因此本發明之保護範圍當視後附之申請專利範圍所界定者 為準。 【圖式簡單說明】 13 200922870 wr 〜25947tw£doc/n 圖1是依照本發明之第一實施例之一種氫氣 統之方塊圖。 度王态糸 圖2是選擇性氧化(ρΓ〇χ)反應單元中的水 c〇轉化率之關係曲線圖。 蒸氣濃度與 圖3是圖1之降溫除水且能自我升溫之裝置的變更示 圖4為實驗例所得到的c〇濃度隨使用時間變化的曲 線圖。 圖5為比較例所得到的c〇濃度隨使用時間變化的曲 線圖。 【主要元件符號說明】 100 :氫氣產生器系統 110 :重組反應單元 120 :水移轉反應單元 130、 132 134 140 150 160 170 302 304 310 320 300 :降溫除水且能自我升溫之裝置 冷凝裝置 加熱回溫部位 選擇性氧化反應單元 陽極廢氫氣氧化單元 反應進料燃料預熱暨水汽化單元 重組氣溫度調節控制單元 内管 外管 雙套管 冷凝蛇管 14Cell ’ PEFC is a definite fixed-type power generation system, portable power generation system, or electric vehicle power system, which is a clear industry trend. Whether it is a decentralized fixed-type power generation system or a portable power generation system, the existing fuel supply network will be used, and the fossil fuel will be replaced by a fuel recombiner (Ref〇rmer) with a carbon monoxide (CO) concentration of less than 2〇. A hydrogen-rich recombination gas that supplies the fuel needed for a polymer electrolyte fuel cell power generation system. Generally, the fuel recombiner system includes: recombination reaction of fuel into reformed gas, water gas shift (WGS), selective oxidation (Pr〇X) reaction, and oxidation of anode waste hydrogen. And the reaction feed water vaporization and other units, the gas temperature after the reaction is about 250~6 〇〇 ° C (depending on the type of fuel), 2 〇〇 ~ 3 〇 (rc, 1 〇〇 ~ 2 〇〇 < t and above 400 ° C. The resulting recombination gas is then cooled to the appropriate temperature to the fuel cell generator set. The patents on the fuel recombiner system tend to improve the arrangement of the reaction of each unit and how to improve the heat. Recycling benefits, and how to improve the efficiency of fuel conversion to recombination gas, and how to develop better reactivity. 200922870 rjH^owuooiw 25947twf.doc/n unit reaction catalyst. However, 'the current system still has C〇 concentration in the reformed gas. The problem of instability and CO concentration exceeding the warning value needs to be solved. SUMMARY OF THE INVENTION The present invention provides a hydrogen generator system that simplifies the design of an overall fuel recombiner system and As a principle of not affecting the overall thermal energy conversion of the system, it can simultaneously increase the water transfer rate (WGS) and the selective oxidation (PrOX) reaction for the conversion rate of CO. a helium gas generator system comprising a recombination reaction unit, a water shift reaction (WGS) unit, a device for cooling and water removal and self-heating, and a selective oxidation (Pr〇x) reaction unit. The reaction unit is used to convert the fuel into a reformed gas, and the water transfer reaction unit performs a water transfer reaction on the reformed gas from the recombination reaction unit. The device for lowering the temperature and removing the water and capable of self-heating is used to reduce the: The water vapor concentration of the reformed gas of the water transfer reaction unit. The selective oxidation reaction unit selectively recombines the CO into a device capable of self-heating by cooling and dehydrating. In one embodiment of the present invention, The recombination gas output by the above selective oxidation reaction unit is a hydrogen-rich gas having a CO intrinsicity of less than 20 ppm, and can be used as a fuel cell (Fuel Cel) power generation system. In one embodiment of the present invention, the fuel includes a fossil energy source. Among them, fossil fuels such as city gas, methanol, alcohol, liquefied petroleum gas (LPG), kerosene or diesel fuel. Regeneration 200922870 I w 25947twf.doc/n Energy is, for example, A6 produced by the Wei reaction or alcohol produced by the fermentation of biomass. - In the embodiment of the present invention, the above-mentioned cooling and water removal can self-lift, θ The apparatus includes a condensing unit, wherein the condensing unit is connected to the water transfer reaction = 兀 to condense the reformed gas from the water transfer reaction unit to ~80 〇C. In one embodiment of the invention, the means for lowering the temperature and removing water and capable of self-heating comprises a double casing comprising an inner tube and an outer tube and a condensing snake 7 tube. Wherein, the condensing coil is located in the inner tube of the double casing, so that the recombination gas from the water transfer reaction unit enters from the inner tube and is condensed by the condensing coil to 60 ° C to 80 ° C and then returned to the temperature through the outer tube to 1〇〇. 〇~15〇〇c. In one embodiment of the invention, the means for lowering the temperature and removing water and capable of self-heating comprises a double casing comprising an inner tube and an outer tube and a heat pipe. Wherein the hot 'tube is located in the inner tube of the double casing, so that the reformed gas from the water transfer reaction unit enters by the inner tube and is condensed by the heat pipe to 6 (Π:~8〇°c' and then through the outer tube The temperature is returned to 100 ° c to 150 ° C. In one embodiment of the invention, the water transfer reaction unit comprises a one-stage reaction unit or a two-stage reaction unit, wherein the two-stage reaction unit comprises a horse warm water Transferring Reaction Unit and a Low Temperature Water Transfer Reaction Unit 0 In one embodiment of the invention, the above recombination reaction unit comprises a vapor reforming reaction unit or an autothermal reforming unit and a reaction unit. In one embodiment of the invention, The hydrogen generator system further includes an anode waste hydrogen oxidation unit for supplying waste hydrogen to the above-mentioned recombination 200922870 r^^owooiw 25947twf.doc/n reaction unit as an energy source, wherein the anode waste hydrogen oxidation unit is separately present or placed. In an embodiment of the present invention, the hydrogen generator system further includes a reaction feed fuel preheating and water vaporization unit for preheating The feed water vapor is supplied to the above-mentioned recombination reaction unit. In one embodiment of the invention, the hydrogen generator system further includes a reforming gas temperature adjustment control unit for regulating the temperature of the reformed gas from the selective oxidation reaction unit. The present invention is capable of recombining after WGS reaction by adding a device for cooling and water removal and self-heating between the water transfer reaction (WGS) unit and the selective oxidation (PrOX) reaction unit of the hydrogen generator system. The water vapor concentration of the gas is lowered, and the selectivity and conversion rate of the selective oxidation reaction for c〇 is increased, the load of the selective oxidation reaction is lowered, and the hydrogen generation system is more stable, so that the concentration of c〇 in the hydrogen-rich reformed gas is made. The above features and advantages of the present invention can be more clearly understood. The above-described features and advantages of the present invention will become more apparent and understood. A block diagram of a hydrogen generator system in accordance with a first embodiment of the present invention. Referring to the hydrogen generator system of FIG. Including a recombination reaction unit 11〇, a water transfer reaction (WGS) unit|20, a device for cooling and water removal and self-heating, 13〇 and a selective oxidation (PrOX) reaction, single tl ho. Recombination reaction unit 200922870 rjH^uwuooj.w 25947twf.doc/n For example, a helium vapor recombination reaction unit or an autothermal recombination reaction unit for converting fuel into a reformed gas, such as a fossil fuel or a renewable energy source. Fossil fuels include natural gas, methanol, alcohol, liquefied petroleum gas (LPG), kerosene or diesel; renewable energy sources include, for example, methane produced by anaerobic reactions or alcohol produced by fermentation of biomass. When the fuel is fossil fuel, the reaction occurring in the recombination reaction unit u〇 is as follows: ^ 2HC+02+H20->2H2+CO+C〇2 Then, please continue to refer to Figure 1, the recombination from the recombination reaction unit The gas undergoes a water transfer reaction in the water shift reaction unit 120 to further shift the CO to hydrogen. In the first embodiment, the water transfer reaction unit 120 is a one-stage reaction unit. Further, the water is transferred to the reaction unit I]. It is also possible to use a two-stage reaction unit such as a high tempe rewater gas-shift (HTS) unit and a low temperature water gas shift (LTS). )unit. The reaction occurring in the water transfer reaction unit 120 is as follows: CO+H2〇~^" H2+CO2 It is known that increasing steam (Steam's) and C0 molar ratio is beneficial to the 埶 mechanics = balance, increasing CO conversion rate for reorganization The concentration of c〇 in the gas decreases, but in the case of the S/CO molar ratio (> 3 to 4), the concentration of the reformed gas entering the selective oxidation (pr〇x) reaction soap 140 can be as high as 5 〇. %, even the highest, will exceed the critical point that the PrOX catalyst can withstand. Not only will the water vapor in the reformed gas compete with the CO for adsorption, but the high water vapor concentration will also dilute the overall oxidative exothermic temperature rise, resulting in PK)X _ C〇 reaction selectivity and transfer to 200922870 l W 25947twf, doc / n rate significantly decreased 'Figure 2 does not. Fig. 2 is a graph showing the relationship between the water vapor concentration and the CO conversion rate in the selective oxidation (pj*〇x) reaction unit 140. As can be seen from Fig. 2, the higher the water vapor concentration, the lower the CO conversion rate. However, the conversion rate of c〇 becomes low, which will make the concentration of C〇 of the reformed gas produced by the system unstable and easily exceed the warning value of 100 ppm. Therefore, before the selective oxidation reaction unit 140, the first embodiment is provided with a device 130' for reducing the temperature and removing water and capable of self-heating to reduce the concentration of water vapor (S) of the reformed gas from the water transfer reaction unit. . In Fig. 1, the device 13 for cooling and de-watering and capable of self-heating includes a condensing device 132, wherein the condensing device 132 is connected to the water transfer reaction unit 12A for recombining gas from the water transfer reaction unit 12 Condensate to about 6 (TC~8 (rC, so that the water vapor in the reformed gas is condensed, at this time, the gas is recombined, and the degree of turbulence is reduced to less than 30%. Then, the water gas/time is reduced. The recombination gas enters a heated rewarming zone 1 during which the heat energy from the hydrogen generator system 100 can be used to reheat the condensing unit 132 = recombination gas to about 1 〇〇 it 〇 15 〇. After the selective oxidation reaction unit 140. ^, the recombination of the device 130 from the temperature-removing and water-removing device will be carried out in the selective oxidation reaction unit _ to perform selective oxidation of the side 乂 to make the remaining c〇 被Reduce as much as possible, the reaction is as follows: CO + 0.5O wide C02 ', body · 1 can get less than 20ppm of nitrogen concentration less than the rich nitrogen! ·, group gas, which can be used as a fuel cell (fUd Cdl , FC) power generation system 200922870 r-ίΗ^υυυοο iw 25947twf.d〇c/n In addition, the hydrogen generator system 1 of the first embodiment may further include an anode waste hydrogen oxidation unit 15〇, as a heat recovery unit, the waste hydrogen from the fuel cell may be The recombination gas of the c〇 concentration standard (for example, the CO concentration is higher than 2G ppm), or the woven heat is supplied to the above-mentioned recombination reaction unit 110 as an energy source, and may also be combined with the calorific value released by the external fuel. The reaction feed is heated to a suitably reactable temperature and then to the recombination reaction unit 110. Further, the anode waste nitrogen oxidation unit (9) may be placed in the inner tube of the recombination reaction unit 110 in addition to the separate f. In Fig. 1, ' There is a reaction feed fuel preheating and water vaporization unit 16 invites a recombination gas temperature regulation control element m, respectively, a recombination reaction unit = 110 and a selective oxidation reaction unit M〇. Among them, the reaction feed fuel pre- The hot hydration vaporization unit 160 is used to supply the preheated fuel cum to the reaction unit ί110. In particular, in Fig. 1, the U 卩 is a dotted line plus an arrow ί, and the hot gas can supply the recombination reaction unit it 110 and the reaction. Feeding_Lai cum water The unit (10) is required for the amount of impurities. (degree = control unit 170 is used to adjust the temperature from the selectivity = recombination gas, so that it can be combined with the fuel cell = hydrogen generator system in addition to the first embodiment In addition, it can also be changed to ί:: warm water removal and self-heating, such as the device 300 that removes water and can self-heat in the personal disk 11' includes -20 cold phase official 32G located in the double casing 310 In the inner tube 302, 11 200922870 rjHy\}\j\j〇〇L yv 25947twf.doc/n to allow the reformed gas from the water transfer reaction unit to enter the inner tube 3〇2 and be condensed by the condensation coil 320 to 60Ό~8〇. (:, and then warmed to 100 by the above outer tube 3〇4. (: ~15 (TC, then to the selective oxidation reaction unit. In addition, the above condensation coil 320 can also be replaced by a heat pipe, the same can be reduced Effect of vapor concentration. ^ An experimental example and a comparative example are listed below to demonstrate that the helium gas generator system of the present invention has superior efficacy than the conventional hydrogen generator system. [Experimental Example] Providing a first mussel The oxygen generator system described in the example, the recombination reaction unit of the hydrogen generator system _ is ventilated with air, water vapor (Kg) and natural gas (NG), wherein the main component of the natural gas is methane (CH4), and the flow rate is Π L / min. In addition, the oxygen contained in the air (a) and the flow rate of natural gas / 匕 CVNG is about 0.15 ~ 0.18, and the flow ratio of water vapor to natural gas Η 2 〇 _ is about 3.5 ~ 3.7. Then, at the gas temperature about 4〇(rc~7〇(rc performs a recombination reaction to convert the incoming fuel into a reformed gas. Then, the heavy stage is transferred to the reaction unit in water, and the gas temperature is about 25 (rc~3〇〇^& ; water transfer reaction. After that, the recombination gas will enter the drop The device that removes water and can be self-contained, and first condenses to about ~ thief, so that the water in the gas condenses 'then the recombination gas will warm back to about leaking ^ = and lead to the selective oxidation reaction unit. Finally, the recombination gas will be about HKTC~2〇 (TC undergoes co selective oxidation reaction so that the = gas becomes a hydrogen-rich gas with a CO concentration below 20 ppm. Figure 4 shows the concentration of c〇 obtained in the above experimental example. A graph showing changes in elapsed time. It can be seen from the figure that the hydrogen system of the present invention has an increase in c〇 concentration of 60% as the use time increases with the use time. [Comparative Example] The experiment was carried out under the same conditions as those in the above experimental example, but the device in which the temperature system was not cooled and dehydrated and which was capable of self-heating was produced, and the water-shifting reaction-reading oxidation-removing anti-fresh money was connected. To compare the riding (7) concentration with the (four) line graph. It can be seen from Fig. 5 that the 'C0 concentration varies greatly, and the percentage of the vertical axis of Fig. 5 is 0.20, which is larger than the figure 401. More, so compared with the upper-experimental example, the re-synopsis of the system of the comparative example The CO concentration exceeds the standard, and the hydrogen generation is unstable. According to the above, the hydrogen generator system of the present invention has a cooling water removal between the water transfer reaction unit and the selective oxidation reaction unit.忐 Self-heating device, so by reducing the concentration of water vapor in the reforming gas entering the helium reaction unit, the effect of increasing the reverse, selectivity and conversion rate of the PrOX reaction on C〇 can be achieved, so that the recombination gas generated by the system The C0 concentration can be stably below 20 ppm, and the hydrogen generator system has an easy-to-operate property to facilitate the supply of fuel required for the polymer electrolyte fuel cell power generation system. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS 13 200922870 wr 〜25947 tw £1/ Figure 1 is a block diagram of a hydrogen gas system according to a first embodiment of the present invention. Figure 2 is a graph showing the relationship between water c〇 conversion rate in a selective oxidation (ρΓ〇χ) reaction unit. Fig. 3 is a diagram showing the change of the apparatus for cooling and dehydrating and self-heating of Fig. 1. Fig. 4 is a graph showing changes in the concentration of c〇 obtained in the experimental example as a function of use time. Fig. 5 is a graph showing changes in c〇 concentration as a function of use time in the comparative example. [Description of main component symbols] 100: Hydrogen generator system 110: Recombination reaction unit 120: Water transfer reaction unit 130, 132 134 140 150 160 170 302 304 310 320 300: Heating device capable of self-heating by cooling and heating Reheating part selective oxidation reaction unit anode waste hydrogen oxidation unit reaction feed fuel preheating water vaporization unit recombination gas temperature adjustment control unit inner tube outer tube double casing condensation coil 14