TW201108498A - Systems and processes of operating fuel cell systems - Google Patents

Systems and processes of operating fuel cell systems Download PDF

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Publication number
TW201108498A
TW201108498A TW099119967A TW99119967A TW201108498A TW 201108498 A TW201108498 A TW 201108498A TW 099119967 A TW099119967 A TW 099119967A TW 99119967 A TW99119967 A TW 99119967A TW 201108498 A TW201108498 A TW 201108498A
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Taiwan
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hydrogen
fuel cell
stream
anode
molten carbonate
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TW099119967A
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Chinese (zh)
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TWI464955B (en
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jing-yu Cui
Erik Edwin Engwall
John William Johnston
Mahendra Ladharam Joshi
Scott Lee Wellington
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Shell Int Research
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Abstract

Processes and systems for operating molten carbonate fuel cell systems are described herein. A process for operating a molten carbonate fuel cell system includes providing a hydrogen-containing stream comprising molecular hydrogen to an anode portion of a molten carbonate fuel cell; controlling a flow rate of the hydrogen-containing stream to the anode such that molecular hydrogen utilization in the anode is less than 50%; mixing anode exhaust comprising molecular hydrogen from the molten carbonate fuel cell with a hydrocarbon stream comprising hydrocarbons, contacting at least a portion of the mixture of anode exhaust and the hydrocarbon stream with a catalyst to produce a steam reforming feed; separating at least a portion of molecular hydrogen from the steam reforming feed; and providing at least a portion of the separated molecular hydrogen to the molten carbonate fuel cell anode.

Description

201108498 六、發明說明： 【發明所屬之技術領域】 本發明係關於燃料電池系統及操作燃料電池之方法。特 疋而α，本發明係關於操作一溶融碳酸鹽燃料電池系統之 糸統及方法。 【先前技術】 熔融碳酸鹽燃料電池將化學能轉化為電能◊熔融碳酸鹽 燃料電池係有用的，乃因其等遞送高品質可靠電功率、操 作清潔且係相對緊凑之發電機。此等特徵使得炼融碳酸鹽 燃料電池作為電源在接達電力供應源受到限制的城市區 域、船舶或偏遠區域中使用頗具吸引力。 炫融碳酸鹽燃料電池由一陽極、一陰極及夾在該陽極與 陰極之間的一電解層形成。該電解質包含可懸浮於一多 孔、絕緣且呈化學惰性之基質中之驗金屬碳酸鹽、驗土金 屬碳酸鹽、熔融鹼金屬碳酸鹽或其混合物。將一可氧化燃 料氣體或可在燃料電池中重組至一可氧化燃料氣體之一氣 體進料至該陽極。進料至該陽極之可氧化燃料氣體通常為 合成氣-可氧化組份、分子氫、二氧化碳及一氧化碳之一 混合物。可將一含氧化劑氣體（通常為空氣及二氧化碳）進 料至陰極以提供產生碳酸根陰離子之化學反應物。在該燃 料電池之操作期間，不斷更新該等碳酸根陰離子。 在问* (通㊉自550 C至700。〔：）下操作熔融碳酸鹽燃料 電池，以使含氧化劑氣體中之氧與二氧化碳反應以產生碳 酸根陰離子。該等碳酸根陰離子跨越電解質以在陽極處與 149088.doc 201108498 來自燃料氣體之氫及/或一氧化碳反應。藉由氧與二氧化 碳在陰極處轉化為碳酸根離子以及碳酸根離子與氫及/或 氧化奴在陽極處之化學反應產生電功率。以下反應闡述 不存在一氧化碳時電池中之電電化學反應： 陰極電荷傳送：CO2+0.5 02+2e.〜C03 = 陽極電荷傳送：C〇3=+H2 —H20+C02 + 2e·及 總反應： H2 + 0.5 〇2 —^H2〇 若一氧化碳存在於該燃料氣體中，則以下化學反應闡述 該電池中之電化學反應。 陰極電荷傳送：C02+02+4e-—2 C03 = 陽極電荷傳送：C03=+H2—H20+C02+2e·及 CO3 +CO —>2 C〇2+2e' 總反應 H2 + CO + 〇2~>H2〇 + C〇2 一電負载或儲存裝置可連接於該陽極與該陰極之間以允 "午電机在β亥陽極與陰極之間流動。該電流給該電負載供電 或將電功率提供至該儲存裝置。 通常藉由一蒸汽重組器將燃料氣體供應至陽極，該重組 益將低分子量烴與蒸汽重組為氫及碳氧化物，舉例而 s，天然氣中之甲烷係用於產生用於該燃料電池之燃料氣 體之車又佳低分子量烴。另一選擇為，該燃料電池陽極可 、星°又计以在内部實現對供應至該燃料電池之陽極之一低分 子量烴(例如甲烷)與蒸汽之一蒸汽重組反應。 曱烷蒸汽重組提供根據以下反應含有氫及一氧化碳之一 燃料氣體：CH4+H2〇?±c〇+3H2。通f，該蒸汽重組反應係 149088.doc 201108498 在對大量κ與蒸汽轉化為氫及—氧化碳有效之溫度下進 行。可在一蒸汽重組器中藉由蒸汽與-氧化碳藉由一水煤 氣轉化反應：h2〇+C(^c〇2+H2轉化為氫及二氧化碳來實 現進一步之氫產生。 然而’在詩將燃料氣體供應至—㈣碳酸鹽燃料電池 之-傳統操作蒸汽重纟以巾，少量氫係由該水職轉化反 ，產生，此乃因該蒸汽重組器係於在能量上有利於藉由蒸 汽重組反應產生—氧化碳及氫之—溫度下操作。在此-溫 度下操作不利於藉由水煤氣轉化反應產生二氧化碳及氯。 由於一氧化碳可在該燃料電池中經氧化以提供電能而二 氧化碳則不能，因此在有利於烴及蒸汽重組至氫及一氧化 碳之溫度下進行該重組反應通常係接受為提供用於該燃料 電池之燃料之-較佳方法。由於該燃料氣體通常係藉由在 外部或内部瘵汽重組而供應至陽極，因此其含有氫、一氧 化奴及少量二氧化碳、未反應之甲烷及作為蒸汽之水。 然而，含有非氫化合物（例如一氧化碳）之燃料氣體對於 在一熔融碳酸鹽燃料電池中產生電功率比較純之氫燃料氣 低效在一給定溫度下’一 '溶融碳酸鹽燃料電池中可產 生之電功率隨氫濃度增加而增加。此乃因分子氫相對於其 他化s物之電化學氧化電位。舉例而言，Watanabe等人在 Applicability 〇f molten carbonate fuel cells to various fuels」（Journal 〇f p〇wer Sources，2006，第 868 至 871 頁） 中聞述在90%燃料利用率及〇 49 Mpa之一壓力下以1500 A/m之一電流密度操作之一 10 kw熔融碳酸鹽燃料電池堆 149088.doc 201108498 疊用一 50%分子氫及5〇0/。水進料產生0.792伏下0.12 W/Cm2 之一電功率密度，而處於相同操作條件下之一 5〇%一氧化 石反及50%水進料僅產生〇 763伏下〇 u w/cm2之一電功率密 度因此，含有大量非氫化合物之燃料氣流在於一溶融碳 酸鹽燃料電池中產生電功率方面不如大部分含有氫之燃料 氣體一樣有效。 然而’炫融碳酸鹽燃料電池通常在商業上以一「氫貧 乏」模式操作，其中選擇燃料氣體（例如）藉由蒸汽重組產 生之條件以限制該燃料氣體中退出該燃料電池之氫之量。 實施此以平衡該燃料氣體t之氫之電能電位與藉由氫退出 該電池而未轉化至電能所損失之電位能（電化學+熱）。 然而，已採取某些措施以重新捕獲退出該燃料電池之氫 之此量’此等氫之能量效率顯著低於氫在該燃料電池中發 生電化學反應之情形。舉例而言，自使該燃料電池中之燃 料氣體發生電化學反應產生之陽極排氣已經燃燒以驅動一 渦輪膨脹機產生電。然而，如此做比捕獲該燃料電池中之 氫之電化學電位顯著低效，此乃因熱能中之許多熱能損失 而非藉由膨脹機轉化至電能。退出該燃料電池之燃料氣體 已經燃燒以提供用於各種熱交換應用之熱能。然而，在燃 燒之後，幾乎5〇%之熱能損失於此等熱交換應用中。氫係 用來點燃低效能量回收系統中所利用之一燃燒器之一種極 為叩貝之氣體，且因此傳統上調整熔融碳酸鹽燃料電池中 所使用之氫之量以利用提供至該燃料電池之氫中之大部分 來產生電功率且最小化在燃料電池排氣中退出該燃料電池 149088.doc 201108498 之氫之量。 已採取其他措施以自存在於該陽極排 生更多氫及/或藉由將該燃料氣體提 想、料氣體產 體分離單元來再循環該陽極氣體中之 組器及/或氣 二氧化碳’存在於胳权山 為回收氫及/或 錢厌μ於陽極中之燃料氣體在 以使陽極氣流中之氫增濃及/或經受 、、且盗中經重組 形成邀及_盖仆山 又水煤氣轉化反應以 形成虱及一氧化杈。熱可由陽極氣流提供。 用於誘發一蒸汽重組器中之甲燒蒸汽 液體燃料轉化為用於墓汽重组器 …及/或將 提供。燃燒-含氧氣體與一燃料(通常為例如天然氣：： 錢料）之燃燒器可用於將所需熱提供至蒸汽重組器。已 利用無焰燃燒來提供用於驅動蒸汽重組反應之熱，其中亦 藉由以避免誘發有焰燃燒之相對量將—烴燃料及氧化劑提 供至—無焰燃燒室來驅動無焰燃燒。用於提供驅動蒸汽重 組反應及/或水煤氣轉化反應所必需之熱之此等方法之能201108498 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a fuel cell system and a method of operating a fuel cell. In particular, the present invention relates to a system and method for operating a molten carbonate fuel cell system. [Prior Art] Molten carbonate fuel cells convert chemical energy into electrical energy. Molten carbonate fuel cells are useful because they deliver high quality, reliable electrical power, clean and relatively compact generators. These features make the use of smelting carbonate fuel cells as power sources in urban areas, ships or remote areas where access to power sources is limited. A dazzling carbonate fuel cell is formed by an anode, a cathode, and an electrolytic layer sandwiched between the anode and the cathode. The electrolyte comprises a metal hydroxide, a soil metal carbonate, a molten alkali metal carbonate, or a mixture thereof, which is suspended in a porous, insulating, chemically inert matrix. An oxidizable fuel gas or a gas recombinable in the fuel cell to an oxidizable fuel gas is fed to the anode. The oxidizable fuel gas fed to the anode is typically a mixture of a syngas-oxidizable component, molecular hydrogen, carbon dioxide, and carbon monoxide. An oxidant-containing gas, typically air and carbon dioxide, can be fed to the cathode to provide a chemical reactant that produces a carbonate anion. The carbonate anions are constantly being updated during operation of the fuel cell. The molten carbonate fuel cell is operated under Q* from 550 C to 700. [:) to react oxygen in the oxidant-containing gas with carbon dioxide to produce a carbonate anion. The carbonate anions cross the electrolyte to react with hydrogen and/or carbon monoxide from the fuel gas at the anode at 149088.doc 201108498. Electrical power is generated by the conversion of oxygen and carbon dioxide at the cathode to carbonate ions and the chemical reaction of carbonate ions with hydrogen and/or oxidized slaves at the anode. The following reaction illustrates the electrochemical reaction in a battery in the absence of carbon monoxide: Cathodic charge transport: CO2+0.5 02+2e.~C03 = Anode charge transfer: C〇3=+H2 —H20+C02 + 2e· and total reaction: H2 + 0.5 〇2 —^H2〇 If carbon monoxide is present in the fuel gas, the following chemical reaction illustrates the electrochemical reaction in the battery. Cathodic charge transfer: C02+02+4e-—2 C03 = Anode charge transfer: C03=+H2—H20+C02+2e· and CO3 +CO —>2 C〇2+2e' Total reaction H2 + CO + 〇 2~>H2〇+ C〇2 An electrical load or storage device can be connected between the anode and the cathode to allow the "noon motor to flow between the anode and the cathode. This current supplies power to the electrical load or provides electrical power to the storage device. The fuel gas is typically supplied to the anode by a steam reformer that recombines the low molecular weight hydrocarbons and steam into hydrogen and carbon oxides. For example, methane in natural gas is used to produce fuel for the fuel cell. Gas vehicles are also good for low molecular weight hydrocarbons. Alternatively, the fuel cell anode can be internally reacted to internally react a low molecular weight hydrocarbon (e.g., methane) supplied to the anode of the fuel cell with steam. The decane vapor recombination provides a fuel gas containing one of hydrogen and carbon monoxide according to the following reaction: CH4+H2〇?±c〇+3H2. The steam recombination reaction system 149088.doc 201108498 is carried out at a temperature effective for converting a large amount of κ with steam to hydrogen and carbon monoxide. Further hydrogen production can be achieved by a steam reforming reaction of steam and carbon monoxide in a steam reformer: h2〇+C (^c〇2+H2 is converted to hydrogen and carbon dioxide to achieve further hydrogen production. Gas is supplied to - (iv) carbonate fuel cell - the traditional operation of steam is repeated with a towel, and a small amount of hydrogen is produced by the conversion of the water, because the steam recombiner is energetically beneficial for recombination by steam Producing - carbon oxide and hydrogen - operating at a temperature. Operation at this temperature is not conducive to the production of carbon dioxide and chlorine by a water gas shift reaction. Since carbon monoxide can be oxidized in the fuel cell to provide electrical energy, carbon dioxide cannot. The recombination reaction which is advantageous for the recombination of hydrocarbons and steam to hydrogen and carbon monoxide is generally accepted as a preferred method for providing fuel for the fuel cell. Since the fuel gas is usually recombined by external or internal combustion. It is supplied to the anode, so it contains hydrogen, oxidized sulphur and a small amount of carbon dioxide, unreacted methane, and water as steam. However, it contains non-hydrogen. The fuel gas of a compound (such as carbon monoxide) is relatively inefficient in producing hydrogen power in a molten carbonate fuel cell. The hydrogen fuel gas is inefficient. The electrical power generated in a 'one' molten carbonate fuel cell at a given temperature depends on the hydrogen concentration. Increase and increase. This is due to the electrochemical oxidation potential of molecular hydrogen relative to other chemical substances. For example, Watanabe et al. in Applicability 〇f molten carbonate fuel cells to various fuels" (Journal 〇fp〇wer Sources, 2006, Pages 868 to 871) A 10 kw molten carbonate fuel cell stack operated at a current density of 1500 A/m at a pressure of 90% fuel utilization and a pressure of 49 Mpa. 149088.doc 201108498 50% molecular hydrogen and 5〇0/. The water feed produces an electrical power density of 0.12 W/cm2 at 0.792 volts, while one of the 5 〇% of the same operating conditions and the 50% water feed produces only 〇 One of the electric power densities of 763uw/cm2 at 763 volts, therefore, the fuel gas stream containing a large amount of non-hydrogen compounds is inferior to most of the hydrogen-containing combustion in the production of electric power in a molten carbonate fuel cell. The gas is just as effective. However, the 'sparkle carbonate fuel cell is usually commercially operated in a "hydrogen-poor" mode in which the fuel gas is selected, for example, by steam recombination to limit the withdrawal of the fuel gas from the fuel cell. The amount of hydrogen is used to balance the electrical potential of the hydrogen of the fuel gas t with the potential energy (electrochemistry + heat) lost by the hydrogen exiting the cell without being converted to electrical energy. However, some measures have been taken to re The amount of hydrogen that is trapped from the fuel cell is 'the energy efficiency of such hydrogen is significantly lower than the situation in which hydrogen reacts electrochemically in the fuel cell. For example, the anode exhaust gas generated by electrochemical reaction of the fuel gas in the fuel cell has been combusted to drive a turboexpander to generate electricity. However, doing so is significantly less efficient than capturing the electrochemical potential of hydrogen in the fuel cell due to the loss of much of the thermal energy in the thermal energy rather than to the electrical energy by the expander. The fuel gas exiting the fuel cell has been combusted to provide thermal energy for various heat exchange applications. However, after combustion, almost 5% of the heat energy is lost in these heat exchange applications. Hydrogen is used to ignite a gas of a very mussel used in one of the burners used in an inefficient energy recovery system, and thus conventionally adjusts the amount of hydrogen used in a molten carbonate fuel cell to utilize the fuel cell provided thereto. Most of the hydrogen is used to generate electrical power and minimize the amount of hydrogen that exits the fuel cell 149088.doc 201108498 in the fuel cell exhaust. Other measures have been taken to recirculate the group of gas and/or carbon dioxide in the anode gas from the presence of more hydrogen at the anode and/or by reclaiming the fuel gas, the gas product separation unit In the case of the recovery of hydrogen and/or money in the anode of the fuel gas in order to make the hydrogen in the anode gas stream enriched and / or withstand, and the reorganization of the formation of the pirates and the conversion of water and gas The reaction is carried out to form cerium and cerium oxide. Heat can be supplied by the anode gas stream. Used to induce a steam-burning vapor in a steam reformer. The liquid fuel is converted to a tomb recombiner... and/or will be provided. A burner of a combustion-oxygen gas and a fuel (typically, for example, natural gas:: money) can be used to provide the required heat to the steam reformer. Flameless combustion has been utilized to provide heat for driving a steam recombination reaction, wherein flameless combustion is also driven by providing a relative amount of flaming combustion to provide a hydrocarbon fuel and an oxidant to the flameless combustion chamber. The ability to provide such heat for driving steam recombination reactions and/or water gas shift reactions

量效率相對低，此乃因藉由燃燒提供之大量熱能未被捕獲 且損失。 X 經重組氣流中之氫及二氧化碳可與陽極排氣分離，例如 藉由使用變壓吸附單元及/或薄膜分離單元。陽極排氣之 溫度通常高於商用氫及/或二氧化碳分離單元所需之溫 度。舉例而言’可透過一熱交換器冷卻該流，然而熱能可 在該冷卻過程中損失。 所分離之氫係進料至該燃料電池之陽極部分。將氫再循 環至陽極可使進入炫融破酸鹽燃料電池之燃料氣體富含 149088.doc • 10- 201108498 氫。將所分離之二氧化碳進料至該燃料電池之陰極部分。 將二氧化碳再循環至陰極可使進入溶融碳酸鹽燃料電池之 空氣富含二氧化碳。 一熔融碳酸鹽燃料電池之電池電位（V)由開路電壓（E)與 才貝失之間的差給出。對於南溫燃料電池，啟動損失極小且 可藉由僅考量歐姆損失而在實際電流密度範圍内獲得電池 電位。因此，電池電位V=E-iR，其中V及E具有伏或毫伏 之單位’ i係電流密度（mA/cm2)且R係將電解質、陰極及陽 極組合在一起之總歐姆電阻（Qcm2)。開路電壓係電池電位 中之主要項。可使用能斯特方程式E=E〇+(RT/2F)ln (Ph2P〇2 /Pl^cO'KRmFWPccnVPcC^a)表示一炼融碳酸鹽燃 料電池之總電壓（電動勢）’其中E係標準電池電位，R係通 用氣體常數8.314472】反-1〇1〇1-1，丁係絕對溫度，且1：'係法拉 第常數9.64853399x104 C mol·1。如圖所顯示，可藉由使 一氧化碳、氫及氧之濃度變化來改變一炫融碳酸鹽燃料電 池之電池電壓。 已採取某些措施以調整提供至該燃料電池之氫、氧及二 氧化碳之濃度以最大化電池電壓。美國專利第7,〇97,925號 Γ925專利）藉由使進料至一熔融碳酸鹽燃料電池之陽極之 流富含氫同時使進料至陰極之流富含氧及二氧化碳來最大 化以下比之分母：The quantity efficiency is relatively low, because the large amount of heat energy provided by combustion is not captured and lost. The hydrogen and carbon dioxide in the reformed gas stream can be separated from the anode gas stream, for example by using a pressure swing adsorption unit and/or a membrane separation unit. The temperature of the anode exhaust is typically higher than the temperature required for commercial hydrogen and/or carbon dioxide separation units. For example, the flow can be cooled by a heat exchanger, but thermal energy can be lost during the cooling process. The separated hydrogen is fed to the anode portion of the fuel cell. Recirculating hydrogen to the anode enriches the fuel gas entering the sulphonate fuel cell with 149088.doc • 10- 201108498 hydrogen. The separated carbon dioxide is fed to the cathode portion of the fuel cell. Recirculating carbon dioxide to the cathode enriches the air entering the molten carbonate fuel cell with carbon dioxide. The battery potential (V) of a molten carbonate fuel cell is given by the difference between the open circuit voltage (E) and the loss of capacitance. For south temperature fuel cells, the startup losses are minimal and the battery potential can be obtained over the actual current density range by considering only ohmic losses. Therefore, the battery potential V=E-iR, where V and E have units of volts or millivolts, i-type current density (mA/cm2) and R is the total ohmic resistance (Qcm2) of the electrolyte, cathode and anode combined together. . The open circuit voltage is the main item in the battery potential. The Nernst standard cell can be expressed using the Nernst equation E=E〇+(RT/2F)ln (Ph2P〇2 /Pl^cO'KRmFWPccnVPcC^a) for the total voltage (electromotive force) of a smelting carbonate fuel cell. Potential, R system general gas constant 8.314472] anti-1〇1〇1-1, butyl absolute temperature, and 1: 'Faraday constant 9.86453399x104 C mol·1. As shown, the cell voltage of a flash carbonate fuel cell can be varied by varying the concentration of carbon monoxide, hydrogen and oxygen. Some measures have been taken to adjust the concentration of hydrogen, oxygen and carbon dioxide supplied to the fuel cell to maximize the battery voltage. U.S. Patent No. 7, 〇97, 925, Γ 925 patent, to maximize the following denominator by enriching the flow of the anode fed to a molten carbonate fuel cell with hydrogen and enriching the feed to the cathode with oxygen and carbon dioxide. :

Ph20 (anode) · ?C02 (anode)Ph20 (anode) · ?C02 (anode)

P H2(anode) p0. 02 (cathode) · Pc〇2 (cathode) 149088.doc 201108498 田3氫以及富含氧及二氧化碳之流係自變壓吸附單元提 供。 儘管先前技術在以不同濃度將氫、氧及二氧化碳提供至 燃料電池方面有效，但該方法在產生氫'二氧化碳及氧流 方面相對低效^該方法在氣體之產生及熱過程中亦係相對 地熱低效，此乃因在進入變壓吸附單元之前冷卻陽極氣體 以私除水。另外，重組器亦不將一液體烴原料轉化為用於 蒸汽重組器之一較低分子量進料且可能自該燃料電池提供 不充足之熱來進行此。 可期望在操作用於產生電之熔融碳酸鹽燃料電池系統及 增強該熔融碳酸鹽燃料電池之功率密度之效率方面之進一 步改良。 【發明内容】 本發明係關於一種用於操作一熔融碳酸鹽燃料電池之方 法’其包括： 將一包括分子氫之含氫流提供至一熔融碳酸鹽燃料電池 之一陽極部分； 控制該含氫流至該陽極之一流率以使得該陽極中之分子 氫利用率小於50% ; 將包括來自該熔融碳酸鹽燃料電池之分子氫之陽極排氣 與一包括烴之烴流混合，其中與該烴流混合之該陽極排氣 具有自500t至700°C之一溫度； 使陽極排氣與該烴流之混合物之至少一部分與—觸媒接 觸以產生一包括一種或多種氣態烴、分子氫及至少一 149088.doc 12 201108498 氧化物之蒸汽重組進料； 自及蒸π重組進料分離該分子氫之至少一部分；及 將°亥所分離之分子氫之至少-部Α作為ί亥包括分子氫之 3氫/瓜之至少一部分提供至該熔融碳酸鹽燃料電池陽極。 在另悲樣中，本發明係關於一種熔融碳酸鹽燃料電池 系統，其包括： 熔融兔酸鹽燃料電池，其經組態以以一流率接收一包 括分子氫之含氫流以使得該熔融碳酸鹽燃料電池之一陽極 中之氫利用率小於50% ; 一個或多個重組器，其以操作方式耦合至該熔融碳酸鹽 燃料電池，至少一個重組器經組態以接收來自該熔融碳酸 鹽燃料電池之陽極排氣及烴，且經組態以允許該陽極排氣 與烴充分地混合以至少部分地重組該等烴中之某些烴以產 生一經重組產物流’其中該經重組產物流包括分子氫及至 少一種碳氧化物；及 一高溫氫分離裝置，其係該等重組器中之至少一者之部 分或柄合至該等重組器中之至少一者且以操作方式耗合至 該溶融碳酸鹽燃料電池，其中該高溫氫分離裝置包括一個 或多個高溫氫分離薄膜且經組態以接收一經重組產物流且 將一包括該分子乳之至少一部分之流提供至該'熔融碳酸鹽 燃料電池。 【實施方式】 本文中所闡述之本發明提供用於操作一熔融碳酸鹽燃料 電池以以一高電功率密度產生電之一高效方法及用於執行 149088.doc •13· 201108498 此一方法之一系統。首先，本文中所闡述之方法藉由最小 化而非最大化燃料在該熔融碳酸鹽燃料電池中之每通程之 燃料利用率來最大化該燃料電池系統之電功率密度。最小 化„玄母通転之燃料利用率以減小遍及該燃料電池之陽極路 徑長度之二氧化碳及氧化產物（特定地係水）之濃度，以使 得維持遍及該陽極路徑長度之一高氯濃度。由於沿該燃料 電池之整個陽極路徑長度存在對於陽極電極處電化學反應 為過量之氫，因此該燃料電池提供一高電功率密度。在關 於達成-高每通程之燃料卿率（例如，大於㈣燃料利用 率）之s /去中’氧化產物及二_氧化碳之濃度可在燃料已 行進穿過該燃料電池之甚至一半之前包括大於燃料流之 4〇%:在燃料電池排氣中’氧化產物及二氧化碳之該漠度 可係虱濃度之數倍，使得沿該陽極路徑提供之電功率可隨 提供至該燃料電池之燃料前進穿過該陽極而顯著減少。 在本文中所闡述之方法令，在一炫融碳酸鹽燃料電池之 陽極之整個路徑長度上以氫淹沒該陽極以使得可用於電化 學反叙陽極電極處之氫之濃度在整個陽極路徑長度上維 持在一高位準處。因Jf，u 最大化該燃料電池之電功率密 度。 在該方法中使用主要係氫或較佳幾乎全係氫之-富氫婵 料最大化該燃料電池系統之電功率密度，此乃因氣比通常 用於炼融碳酸鹽燃料電池系統中之其他可氧化化合物（例 如，一氧化碳)具有-顯著較大之電化學電位。 4匕此項技術中已揭不之系統，本文中所閒述之方法藉 149088.doc 201108498 由利用一富氫燃料且最小化而非最大化燃料電池之每通程 之燃料利用率在一熔融碳酸鹽燃料電池系統中產生一更高 電功率密度。該最小化係藉由以下步驟達成：分離且再循 環自該燃料電池之燃料排氣（例如，陽極排氣）捕獲之氫且 以選定速率自一進料及再循環流進料該氫以最小化每通程 之燃料利用率。 與習用系統相比，本文中所闡述之系統允許將一富氫流 提供至該熔融碳酸鹽燃料電池同時最小化提供至該燃料電 池之烃之1。該系統產生可直接引入至該熔融碳酸鹽燃料 電池之陽極部分中之富氫流。 "亥系統不需要直接耦合至該熔融碳酸鹽燃料電池之該陽 極及/或疋位在該陽極中之—重組器來確保作為用於該燃 料電池之„亥陽極之燃料之充足氫產生。纟該、溶融碳酸鹽燃 :找池中移除或消除一重組器或重組區允許以氫淹沒該熔 起酸鹽燃料電池同時將來自該陽極排氣之熱之大部分供 心 第重組态。已裝備有内部重組區之燃料電池可與 本文中所闡述之系統組合使用。此等燃料電池可比此項技 術中已揭示之系統更經濟且更有效地操作。 在本文中所聞述之方4中，纟一炼融碳酸鹽燃料電池之 陰極之i個路;^長度上以二氧化碳淹沒該陰極以使得可用 於電化學反應之陰極電極處之二氧化碳之濃度在整個陰極 路么長度上維持在—高位準處1此，最大化該燃料電池 之電功率达、度及/或電池電壓。 本文中所闡述之方法利S —含富二氧化碳氧化劑氣體之 149088.doc •15· 201108498 流，因此允許該燃料電池之操作以使得該熔融碳酸鹽燃料 電池之該陰極部分之大部分中之二氧化碳分壓高於該熔融 碳酸鹽燃料電池之一陽極部分之大部分中之二氧化碳分 壓。以此方式操作該燃料電池比此項技術中已揭示之系統 產生一更高電功率密度。 利用一富二氧化碳氧化劑氣體升高該熔融碳酸鹽燃料電 池之電壓且抑制該熔融碳酸鹽燃料電池之二氧化碳不足。 「二氧化碳不足」指退出該陰極之二氧化碳之分壓（Pc〇2C) 小於退出該陽極之二氧化碳之分壓（Pco/) ^在一最小氫利 用率下將過量二氧化碳提供至該熔融碳酸鹽燃料電池允許 自該熔融碳酸鹽燃料電池獲得較高電壓及/或電流密度。 與習用系統相比，本文中所闡述之系統允許將一富二氧 化碳流自提供至該熔融碳酸鹽燃料電池之烴提供至該燃料 電池。可將自該系統產生之二氧化碳直接引入至該熔融碳 酸鹽燃料電池之陰極部分中。該系統不需要二氧化碳之一 外部源來確保作為用於該燃料電池之該陰極之進料之充足 二氧化碳。 本文中所闡述之方法亦係高效的，此乃因該燃料電池中 未利用來產生電之氫及二氧化碳連續再循環穿過該燃料電 池系統。此藉由解決與由未轉化至電能即退出該電池之氫 及/或二氧化碳損失能量相關聯之問題來實現相對於燃料 之最低加熱值之一高電功率密度之產生。 該系統允許適當量之空氣或分子氧同時進料至該燃料電 池之陰極，以使得在至該陰極之進料中之二氧化碳對分子 149088.doc -16· 201108498 氧莫耳比最小化該燃料電池之電極處之濃度極化。該系統 不需要富氧空氣。本發明之方法允許以氫淹沒陽極且同時 以二氧化碳淹沒陰極，同時控制分子氧之量以使得至該陰 極之進料中之二氧化碳對分子氧莫耳比為至少2或至少 2.5。 使用本發明中所闡述之燃料電池系統允許在〇1 atm)下以一高功率密度操作該熔融碳酸鹽燃料電池。通 常，熔融碳酸鹽燃料電池係在自大氣壓至約】MPa(1〇atm) 之壓力下操作。在高於大氣壓之壓力下操作可影響在該熔 融碳酸鹽燃料電池之各個部分中之密封之壽命。該溶融碳 酸鹽燃料電池在大氣麼力下或接近大氣麼力操作可延長在 該熔融碳酸鹽燃料電池中之密封之壽+同時針對給定電池 電壓及/或功率密度以高電流密度產生電。 在本文中所闡述之方法中，該方法所產生之每單位電產 =目對少之二氧化碳。一第一重組器、一第二重組器及一 Γ7 m氫刀離裝置與燃料電池之熱積體減少且較佳消除所需 $供以驅動-個或兩個重組器中之吸熱重組反應之額外能 里，其中藉由將熱陽極排氣流自該燃料電池提供至該第一 重組器而將該燃料電池中所產生之熱直接傳送於該第一重 組器。内，且隨後將該第_重組器之產物直接進料於該第二 p n内且然後將該第二重組器之產物直接提供至該高 刀離裝置°此熱積體減少（例如，藉由燃燒）提供額外 牝罝之而求。因此’減少提供能量以驅動重組反應時所產 生之二氧化碳之量。 1490S8.doc •17- 201108498 藉由自經重組氣體產物分離二氧化碳且隨後將含二氧化 碳氣流進料至該燃料電池，使陽極排氣流再循環穿過該系 統且將二氧化碳氣流提供至該燃料電池減少需要由燃燒產 生之一氧化碳之量。此再循環增加該方法之電效率且藉此 減少任何二氧化碳排放。 另外，藉由自經重組氣體產物分離含氫氣流且隨後將該 含氫氣流進料至該燃料電池，使陽極排氣流再循環穿過該 系統且將富含分子氫之一含氫氣流提供至該燃料電池減少 需要由該第二重組器產生之氫之量。陽極排氣之此再循環 增加该方法之電效率。此外，該熔融碳酸鹽燃料電池之功 率在、度传以改良，因此為產生相同量之功率，可使用比習 用燃料電池具有更小尺寸之燃料電池來產生功率。 本文中所闡述之方法比此項技術中已揭示之方法更具熱 及能量效率。來自一燃料電池排氣之熱能直接傳送至一第 一重組器中。在某些實施例中，所傳送之熱能之一部分隨 後自該第一重組器傳送至一第二重組器中。熱能直接自該 燃料電池之陽極排氣至該第一重組器之傳送係高效的，此 乃因該傳送係藉由在該第一重組器中將來自該燃料電池之 一熱陽極排氣流直接與一包括烴之烴流及蒸汽以分子方式 混合而實現。一熱進料自該第一重組器產生且隨後進料至 該第二重組器。熱能自該第一重組器至該第二重組器之傳 这亦係高效的’此乃因該熱能包含在自該第一重組器進料 至a玄第二重組器之進料中。 本文中所闡述之方法比此項技術中已揭示之方法更具熱 149088.doc 201108498 放率此乃因來自陽極排氣之熱用於在低於典型蒸汽重組 方法之溫度下產生氫。在本發明之方法中，可使用一高溫 氫分離裝置自經重组產物氣體分離氫，其中該高溫氮分離 裝置係-薄膜分離裝置。該高溫氫分離裝置可以操作方式 搞合至該第二重組器，以使得可在該第二重組器中發生重 、且反應時自經重組氣體分離氫。氫之分離朝向氫之產生驅 動平衡且降低產生氫所需之溫度。此外，可在較低重組溫 度下產生較夕氫，此乃因水煤氣轉化反應（H2〇 + c〇 # C〇2+H2)之平衡有利於在較低重組溫度下產生氫，而在習 用重組反應溫度下則不利於其。自該第二重組器產生之大 里或所有为子氫及二氧化碳係提供至該熔融碳酸鹽燃料電 池。 本文中所闡述之方法允許利用液體燃料。使用液體燃料 允許一種燃料供多於一個電源使用。舉例而言，可在一船 上使用柴油燃料以給一熔融碳酸鹽燃料電池及引擎供電。 透過陽極排氣與液體進料之混合來將氫添加至該第一重組 器。氫之再循環消除對用於液體進料之熱裂解之一單獨氫 源之一需求。儘管消耗了某些氫，但氫在經裂解烴之重组 之後產生。重組器與高溫氫分離裝置之積體允許該系統產 生該等方法所需之大致所有氫。 液體燃料之重組及/或加氫裂解每莫耳所產生氫產生較 多二氧化碳，此乃因具有大於6之碳數目之燃料（例如，柴 油及石腦油）之氫對碳比低於具有小於6之碳數目之燃料（例 如，甲烷）之氫對碳比。每莫耳所產生氫產生較多二氧化 149088.doc •19- 201108498 碳允許自該液體燃料產生該熔融碳酸鹽燃料電池所需之大 致所有或所有二氧化碳。以此方式產生二氧化碳可消除或 減少將陽極氣體及/或進料氣體之一部分用作用於熱低效 燃燒燃燒器之一燃料來產生二氧化碳之需求。在本文中所 闡述之方法中’產生過量氫及二氧化碳，此允許氫及二氧 化碳再循環穿過該系統。 本發明之方法允許炫融碳酸鹽燃料電池在0 1 atm)或小於o.l MPa(l atm)之壓力下操作且提供至少〇12 W/cm之一功率达、度及/或至少8〇〇 mV之一電池電壓。在某 些實施例中，本發明之方法允許熔融碳酸鹽燃料電池在 〇·1 MPa(l atm)或小於〇.1 MPa(1 atm)之壓力下操作且提供 至少0.12 W/cm2之一功率密度及/或至少8〇〇 mV之一電池 電壓。 如本文中所使用’除非另外指示，否則術語「氫」指分 子氫。 如本文中所使用，術語「氫源」指自其可產生游離氫之 一化合物。舉例而言，氫源可係例如甲烷之烴或此等化合 物之混合物或例如天然氣之含烴混合物。 如本文中所使用，當兩個或更多個元件係闡述為「以操 作方式連接」或「以操作方式耦合」時，該等元件係界定 為直接或間接地連接以允許該等元件之間的直接或間接流 體流動。如本文中所使用，術語「流體流動」指一氣體或 一流體之流動。如在「以操作方式連接」或「以操作方式 耦合」之界定中所使用，術語「間接流體流動」意指可透 149088.doc •20· 201108498 過一個或多個額外元件指引兩個經界定元件之間的一流體 或一氣體之流動以在該流體或氣體在該兩個經界定元件之 間流動時改變該流體或氣體之一個或多個態樣。一流體或 一氣體之可在間接流體流動中改變之態樣包含物理特性 (例如一氣體或一流體之溫度或壓力）及或該氣體或流體之 組成（例如，藉由分離該氣體或流體之一組份或藉由自含 蒸汽之一氣流冷凝水）。如本文中所界定，「間接流體流 動」不包含藉由該流體或氣體之一種或多種元素之化學反 應（例如，氧化）或減少來改變該兩個經界定元件之間的該 氣體或流體之組成。 如本文中所使用，術語「對氫選擇性地可透」係界定為 對分子氫或元素氫可透且對其他元素或化合物不可透，使 得非氫元素或化合物之至多1〇%、或至多5%或至多1%可 滲透對分子氫或元素氫可透之物質。 如本文中所使用，術言吾「高S氫分離裝置」係界定為對 在至少25〇t之一溫度下（例如，在自3〇〇(>(：至65〇1之溫度 下）自一氣流分離呈分子或元素形式之氫有效之一裝置或 設備。 如本文中所使用，指-燃料中之氣在一炼融碳酸鹽燃 電池中之利用率之「每通程之氫利用率」係界定為相對: 針對穿過該㈣碳酸鹽燃料電池之—次通過輸人至該燃: 電池中之—燃料中之氫之總量一燃料中用於在該通過中 電之氫之量。母通耘之氫利用率可藉由以下步驟計算 量測進料至一燃料電池之陽極之一燃料中之氫之量；量: 149088.doc -21 - 201108498 該燃料電池之陽極排氣中之氫之量；自所量測之進料至該 燃料電池之燃料中之氫之量減去所量測之該燃料電池之陽 極排氣中之氫之量以確定該燃料電池中所使用之氫之量； 及將所S十算之該燃料電池中所使用之氫之量除以所量測之 進料至該燃料電池之燃料中之氫之量。每通程之氫利用率 可藉由將所計算之每通程之氫利用率乘以100而表示為一 百分比。 如本文中所使用。「過量二氧化碳」指該熔融碳酸鹽燃 料電池之陽極與陰極之二氧化碳之分壓差之一值（ΔΪ^02)。 「過量二氧化碳」（APco2)係藉由以下步驟計算：分別在陽 極及陰極出口處量測陽極排氣及陰極排氣中之二氧化碳之 分壓’及自所量測之陰極之二氧化碳分壓值減去所量測之 陽極之二氧化碳分壓值（例如，ΔΡε〇2 = (Ρε〇2Κρ⑶對 於至該陽極及陰極之進料之一對流，「過量二氧化碳」係 藉由以下步驟叶异：在陽極出口及陰極入口處量測陽極排 氣及陰極排氣中之二氧化碳之分壓；及自所量測之陰極之 二氧化碳分壓值減去所量測之陽極之二氧化碳分壓值（例 如，△PcofCPco/inletxpco/ounet))。 平均過量二氧化碳藉由以下方程式計算。 APc〇2(aVg)=[{Pc〇2Cin.et+pc〇2C〇utlet}_{pc〇2ainlet+pc〇2a〇utlet^/2 局°卩過里—氧化碳」指在假定沿y方向（寬度）對稱之 一正規化距離上每百分比氫利用率該熔融碳酸鹽燃料電池 之一氧化奴之分壓差之一值^局部過量二氧化 厌藉由計算，其中X係沿陽 149088.doc -22- 201108498 極隔區之長度之一正規化距離。 圖1至圖3繪不用於進行根據本發明之用於操作一溶融碳 酸鹽燃料電池以產生電之方法之本發明之系統之實施例之 不思圖。燃料電池系統10包含溶融碳碳酸鹽燃料電池Η、 第-重組器14、第二重組器16、高溫氫分離裝置18及氧化 單元20。在-較佳實施例中，第二重組器16 '高溫氯分離 裝置職氧化單元2()係—個單元。在—較佳實施例中，氧 化單元20係一催化部分氧化重組器。在—實施例中，高溫 氫分離裝置18係一分子氫薄膜分離裝置。在一實施例中， 第二重組器16包含一重組區、高溫氫分離裝置18、催化部 分氧化重組器20及熱交換器22。熱積體式系統聽融碳酸 鹽燃料電池之繼續操作提供充足氫及二氧化碳以產生電。 熔融碳酸鹽燃料電池12包含陽極24、陰極26及電解質 28。電解質28插入於陽極24與陰極26之間且接觸該陽極及 陰極。熔融碳酸鹽燃料電池12可係一習用熔融碳酸鹽燃料 电池且較佳可具有一管狀或平面組態。熔融碳酸鹽燃料電 池12可包含堆疊在—起之複數個個別燃料電池。該等個別 燃料電池可藉由互連且以操作方式連接而電聯结，使得一 個或夕個氣流可流動穿過經堆疊燃料電池之陽極且一含氧 化劑氣體可流動穿過經堆疊燃料電池之陰極。如本文中所 使用，術語「熔融碳酸鹽燃料電池」係界定為一單個熔融 碳酸鹽燃#電池或複數個以操4乍方式連接或堆疊之溶融碳 酸鹽燃料電池。熔融碳酸鹽燃料電池12之陽極24可由多孔 經燒結鎳化合物、鎳鉻合金、具有鋰鉻氧化物之鎳及/或 J49088.doc •23· 201108498 鎳銅合金或適合用作溶融碳酸鹽燃料電池之陽極之任一材 料形成。熔融碳酸鹽燃料電池i2之陰極26可由多孔經燒結 材料（例如鎳氧化物、鋰-鎳-鐵氧化物）或適合用作熔融碳 酸鹽燃料電池之一陰極之任一材料形成。 將氣流進料至該陽極及陰極以提供在燃料電池12中產生 電所必需之反應物。含氫流進入陽極24且含氧化劑氣流進 入陰極26。電解質區段28定位於該燃料電池中以阻止含氫 氣抓進入陰極且阻止含氧化劑氣流（氧及二氧化碳流）進入 陽極。含氧化劑氣流包含含有氧及/或二氧化碳之一個或 多個流。 電解質區段28將碳酸根離子自陰極引導至陽極以達成與 陽極氣机中之可氧化化合物（例如，氫及（視情況）一氧化 石厌）在一個或多個陽極電極處之電化學反應。電解質區段 可由驗金屬奴&鹽、驗土金屬碳酸鹽或其組合之炼融鹽 形成冑解質材料之實例包含由碳酸鋰鈉、碳酸鋰、碳酸 鈉奴駄鋰鈉鋇、碳酸鋰鈉鈣及碳酸鋰鉀形成之多孔材 料。 Μ料電池12經組態以允許含氫氣流自陽極人口列流動穿 過陽極24且流出陽極排氣出口 &含氫氣流接觸自陽極入 口 30至陽極排氣出σ32之陽極路徑長度上之—個或多個陽 極電極。 , 貫也例中透過管線3 4將含分子氫之一氣流（下文 , έ氫"IL」）或氫源進料至陽極入口 30。節流閥36 可用於選擇並控制該含氫流至陽極入口 30之流率。在一較 149088.doc 24 - 201108498 〇·98莫耳分率氫 =實知例中，1自高溫氫分離裝置以進料至燃料電池Μ之 陽極24’其中該高溫氫分離裝置係，薄膜單元，如下文所 詳細聞述。在-實施例令’該含氫氣流可含有至少0.6、 或至夕0.7、$至少0.8、或至少〇 9、或至少〇 %或至少 「進料至該陰極之-氣體包含氧化劑。如本文中所提及， 「氧化劑」指能夠藉由與分子氫反應而減少之一化合物。 在某些實施例t ’進料至陰極之含氧化劑氣體包含氧、二 氧化石厌、惰性氣體或其混合物。在—實施例中，含氧化劑 氣體係-含氧氣流與-含二氧化碳氣流之—組合或一含氧 ’一氧化碳流。在一較佳實施例中，進料至陰極之含氧氣 體係已與充足之二氧化碳混合之空氣或富氧空氣，使得二 氧化碳對氧之莫耳比為至少2或至少25。 3氧化劑氣體可自陰極入口⑽流動穿過陰極“且隨後 透過陰極排氣出口該含氧化劑氣體接觸自陰極入 口 38至陰極排氣出口 4G之陰極路徑長度上之—個或多個陰 極電極。在—個實施例中，—含氧化劑氣體可相對於流動 至燃料電池12之陽極24之一含氫氣體之流動對流流動。 在-實施例中，含氧化劑氣流透過管線44自含氧化劑氣 體源42進料至陰極人σ38。節流_可用於選擇並控制該 氣流進料至陰極26之速率。在某些實施例中，由一空氣壓 縮機提供該含氧化劑氣體。該含氧化劑氣流可係空氣。在 一個實施例中，該含氧化劑氣體可係純氧。在一實施例 中，該含氧化劑氣流可係含有至少13重量％氧及/或至少％ 149088.doc .25· 201108498 f量氧化碳之§合氧及/或二氧化碳之空氣。在一較佳 實把例中’控制空氣及/二氧化碳之流動以使得^氣中二 氧化碳對分子氧之一莫耳比為至少2或至少2.5。 在個實施例中，藉由—含二氧化碳氣流及一含氧氣流 f供該含氧化劑氣流。二氧化碳流及含氧氣流可來自兩個 單獨之源在-佳實施例中，用於熔融碳酸鹽燃料電池 】2之大部分或大致所有二氧化碳源自提供至第一重組器“ 之匕括m望流。含二氧化碳氣流透過管線料自二氧化碳 源進料至陰極入口 38。提供至燃料電池12之含二氧化碳氣 流可與含氧氣流進料至相同陰極入口 38,或可在進料至陰 極入口 38之月與-含氧氣流混合。另—選擇為，含二氧化 碳氣流可透過單獨之陰極人口提供至陰極2 6。 在較佳貫施例中，該二氧化碳流經由管線48及44自高 溫氫分離裝置18提供至燃料電池12之陰極26，如本文中所 闡述。氧可經由管線44提供至燃料電池Η之陰極％。 在進料至陰極26及/或陽極24之前，進料至陰極及/或陽 極之乳體（無論一個流或多個流）可在一熱交換器22或其他 …、又換器中加熱，較佳藉由與退出陰極排氣口 且透過管 線50連接至熱交換器22之氧耗盡陰極排氣流交換熱。 在本發明之方法中，含氫氣流在熔融碳酸鹽燃料電池12 之陽極電極中之一者或多者處與氧化劑混合以產生電。該 氧化劑較佳係源自流動穿過陰極26之二氧化碳與氧之反應 且經引導跨越該燃料電池之電解質之碳酸根離子。藉由以 選疋獨立速率將含氫氣流及/或含氧化劑氣流進料至燃料 149088.doc -26 - 201108498 電池12來在該燃料電池之—個或多個陽極電極處混合該含 氫氣流與該氧化劑，如下文所進-步詳細論述。該含氫氣 流與該氧化劑較佳在該燃料電池之—個或多個陽極電極處 混合以在1巴下以至少G」w/em2、或至》、G 15 W/W、或 至少0.2 WW、或至少〇 3 w/cm2或至少〇 6 w“2之一電 功率密度產生電。可在較高壓力下及/或藉由使用富含氧 化劑氣流（例如，富氧化劑空氣）獲得較高功率密度。 在對使碳酸根離子能夠自陰極26橫穿電解質部分28至陽 極24有效之一溫度下操作熔融碳酸鹽燃料電池u。可在自 55(TC至7〇(TC或自_。〇至㈣。c之—溫度下操作溶融碳酸 鹽燃料電池12。在—個或多個陽極電池處氫與碳酸根離子 之氧化係-放熱反應。該反應之熱產生操作熔融碳酸鹽燃 料電池12所需之熱。操作熔融碳酸鹽燃料電池時所處之溫 度可受數個因素控制，包含但不限於調節含氫氣體及含氧 氣體之進料溫度及進料流動。由於氫利用率最小化，因此 過量氫進料至該系統且未反應之氫可藉由將過量熱攜載至 垓第—重組器而部分地冷卻該熔融碳豸鹽燃料電池。調節 二氧化碳流及/或含氧化劑流之流動以將二氧化碳對分= 氧之莫耳比維持在約2處需要充足之含氧化劑氣體來^成 約為需要與陽極中所利用之氫之部分反應之量之13至2 〇 倍之分子氧之一過量。因此，於陰極排氣中退出之氧耗盡 之空氣或含氧化劑氣體之過量可自該溶融碳酸鹽燃料電池 攜載大量熱。在將下文所闡述之-含氫流自高溫氫分離裝 置Μ提供至熔融碳酸鹽燃料電池12之陽極24之 、 ’可It由 U9088.doc •27- 201108498 °收（例如，透過熱交換器22)來降低提供至該熔融碳酸 鹽燃料電池陽極之該含氫流之溫度。在將下文所闡述之一 问壓一氧化碳流自高溫氫分離裝置18提供至熔融碳酸鹽燃 料電池12之陰極26之前，可藉由熱回收（例如，透過熱交 換益22)來降低提供至該熔融碳酸鹽燃料電池陰極之該高 壓二氧化碳流之溫度。在將來自催化部分氧化重組器2〇之 一流出物流提供至該熔融碳酸鹽燃料電池陰極之前，可藉 由熱回收（例如，透過熱交換器22)來降低該流出物流之溫 度。來自該燃料電池之廢熱可用於加熱該系統中所利用之 流中之一者或多者。若必須，則此項技術中已知之用於冷 卻熔融碳酸鹽燃料之任何補充系統可用於控制該熔融碳酸 鹽燃料電池之溫度。 在一實施例中，可在進料至陰極26之前將進料至該陰極 之含氧化劑氣流加熱至至少1 50°C或自1 5 01至3 5〇〇c之一 溫度。在一實施例中，當使用一含氧氣體時，將一含氧氣 流之溫度控制至自1 50°C至350°C之一溫度。 為起始燃料電池12之操作，將該燃料電池加熱至其操作 溫度--足以熔融電解質鹽以允許碳酸根離子流動之一溫 度。如圖1中所顯示’可藉由在催化部分氧化重組器2〇中 產生一含氫氣流且透過管線52及34將該含氫氣流進料至溶 融碳酸鹽燃料電池12之陽極24來起始該熔融碳酸鹽燃料電 池之操作。 在存在一習用部分氧化觸媒之情形下，藉由在催化部分 氧化重組器20中燃燒下文所闡述之一包括烴之烴流之—部 149088.doc -28 * 201108498 刀或不同烴流（例如，天然氣中所富含之一燃料流）與一 含氧化劑氣體來在催化部分氧化重組器2〇中產生一含氫氣 机’其中進料至催化部分氧化重組器2〇之含氧化劑氣體令 之氧之一量係相對於烴流中之烴之一量的亞化學計量。含 氫氣流之流動可由閥60控制。 如圖2中所顯不，藉由在氧化單元2()中產生含氫氣流且 透過管線96、104及34將該含氫氣流進料至熔融碳酸鹽燃 料電池之陽極24來將該燃料電池加熱至其操作溫度。藉由 三通閥1G2㈣含氫氣隸由f、_、1()4自氧化單元料 料至陽極24之速率。來自含氫氣流之熱之—部分可經由管 線96穿過熱交換器98以將熱提供至第—重組㈣及/或進 入該第一重組器之包括烴之烴流。 參照圖1及圖2，進料至催化部分氧化重組器汕之燃料可 係-液體或氣態烴或烴混合物，且較佳與提供至第一重組 益14之包括烴之烴流相同。燃料可經由管線。進料至催化 部分氧化重組器20。在一實施例中，使天然氣及/或來自 氫源64之富含氫之進料至催化部分氧化重組請之燃料。 進料至催化部分氧化重組器2〇之氧化劑可係純氧、空氣 或富氧空氣（下文稱為「含氧化劑氣體」）。較佳地，該含 氧化劑氣體係空氣。應將該氧化劑提供至催化部分氧化重 組器20以使得該氧化劑中之氧之—量㈣於進料至該催化 部分氧化重組之烴處於亞化學計量之量中。在—較佳實施 例中，透過管線56將該含氧化劑氣體自氧化#]源42㈣至 催化部分氧化重組器2〇。閥58可控制含氧化劑氣體（空幻 149088.doc •29- 201108498 進料至催化部分氧化重組器20及/或燃料電池12之陰極26 之速率。在一實施例中，可藉由與退出陰極排氣口 40之氧 耗盡陰極排氣流交換熱來加熱進入催化部分氧化重組器Μ 之含氧化劑氣體。 在催化部分氧化重組器2〇中’在存在一習用部分氧化觸 媒之情形下藉由燃燒烴及氧化劑來形成一含氫氣流，其中 相對於烴，該氧化劑處於一亞化學計量之量中。藉由烴與 氧化劑在催化部分氧化重組器2〇中之接觸而形成之含氳氣 流含有藉由與陽極電極中之一者或多者處之碳酸根離子接 觸而可在燃料電池陽極24中氧化之化合物。來自催化部分 氧化重組器20之含氫氣流較佳不含有氧化燃料電池12之陽 極24中之一個或多個陽極電極之化合物。 形成於催化部分氧化重組器2〇中之含氫氣流係熱的且可 具有至少700t、或自700。(：至11〇〇。(：或自別❹它至丨⑽❹它 之-溫度。在本發明之方法中，使用來自催化部分氧化重 組器20之熱氫氣流來起始熔融碳酸鹽燃料電池。之發動為 較佳，此乃因其使該燃料電池之溫度能夠幾乎瞬間升高至 該燃料電池之操作溫度。在一實施例中，當起始該燃料電 池之操作時，熱可在熱交換器22中於來自催化部分氧化重 組器2Ό之熱含氫氣體與進料至陰極26之一含氧化劑氣體之 間交換。. 參照圖1，可使用閥60調整來自催化部分氧化重組器 之熱含氫氣流至燃料電池12中之流動，同時藉由打開閥 來將含氮氣流進料至陽極24中。在起始來自高溫氫分離 149088.doc -30· 201108498 置18之一含氫氣流之流動之後可關閉閥60，同時減少或停 止烴進料透過管線62及氧化劑進料透過管線56至催化部分 氧化重組器20之流動。 參照圖2，可使用三通節流閥102調整熱含氫氣流藉由管 線96自催化部分氧化重組器20至燃料電池12中之流動，同 時藉由打開閥36來將該含氩氣流進料至陽極24中》在自高 溫氫分離裝置18產生一含氫氣流之後可關閉閥1〇2，同時 減少或停止烴進料透過管線62及氧化劑進料透過管線56至 催化部分氧化重組器20之流動。然後，可根據本發明之方 法進行該燃料電池之繼續操作。 二通節流閥102控制流出物自催化部分氧化重組器2〇至 陽極24或陰極26之流動。在發動期間，來自催化部分氧化 重組器20之流出物富含氫，因此在經由管線％穿過熱交換 器98之後將該流出物經由管線1〇4指引至陽極24。在起始 發動^後且若催化部分氧化重組器则於產生用於陰極％ 之一氧化奴，則節流閥1〇2控制流出物經由管線％自催化 部分氧化重組器20至陰極26之流動。 牡乃一貫施例令，在 S咪00肘3虱氣",L VI八王燃ψ\ 电池12中之前，可用可空，网 . 了用了穿過一發動加熱器（未顯示）而將燃 料電池帶至其操作、、田译 电 # mm 、恤度之來自虱源64之氫發動氣流起始該 ^電池之操作’如圖所顯示。氫源以可係能夠接收 分離裝置18之氯之-储存槽。可將該氯源以操 ^ 叶4池以准δ午將虱發動氣流引入至該熔 融奴酸鹽燃料電池 陽極中。該發動加熱器可將氫發動氣 149088.doc -31 · 201108498 流間接加熱至自了切艺至⑺㈧它之一溫度。另一選擇為， 該發動加熱器可藉由自氫源64提供至該加熱器之氫之不完 全燃燒來提供氫。該發動加熱器可係一電加熱器或可係一 燃燒加熱器。在達到該燃料電池之操作溫度之後，可藉由 一閥切斷氫發動氣流至燃料電池中之流動，且可藉由打開 自氫產生至燃料電池之陽極之一閥來將含氫氣流引入至 該燃料電池中以開始該燃料電池之操作。 在一個實施例中，第—重組器14包含一催化部分氧化重 組器’其用於在發動時將氫提供域融碳酸鹽燃料電池。 第-重組器14可包含-個或多個觸媒床，其允許該第一重 組器在該熔融碳酸鹽燃料電池一旦已達到操作溫度時即用 於自熱重組且隨後用於蒸汽重組。 尸一旦燃料電池12已開始操作，陰極26及陽極“即散發才 氣。來自陰極26及陽極24之排氣係熱的且來自該排氣之善 可與其他單元熱積體以產生一熱積體式系統，該熱積體3 系統產生該燃料電池之操作所必需之所有燃料⑷及氧々 劑（碳酸根離子）。 如圚1及圖2中所 十人T尸/T閣述之方法利用一 統’該系統包含熱積體式氫分離分離裝置18、溶融碳酿 燃料電池：12、第一重組器；u及第二重組器16及(在某进 施例中）催化部分氧化重組器20。离、、θ & 回溫虱分離裝置18 & 一個或多個高溫氫分離薄膜68且择 ^方式耦合至熔副 酸鹽燃料電池12。高溫氫分離裝置μ 衣直將主要含有分子f 一含氫氣流提供至燃料電池12之陽;κ 之刼極24，而來自熔融喊 149088.doc -32. 201108498 鹽燃料電池12之陽極之排氣係提供至第一重組器14。第 重組器14及第二重組器16可係一個單元或以操作方式輕人 之兩個單元。第一重組器14及第二重組器16可包含一個或 多個重組區。在一實施例中，第一重組器14及第二重組器 16係包含一第一重組區及一第二重組區之一個單元。 經由管線6 2將包括煙之煙流提供至第一重組器14且將陽 極排氣與烴混合。該方法為熱積體式，其中直接在該第— 重組器内及/或與提供至該第一重組器之烴流中之烴—起 自放熱熔融碳酸鹽燃料電池12之陽極排氣提供驅動第一重 組14中之吸熱重組反應之熱。在一實施例中，來自該陽 極排氣之熱之一部分在一熱交換器令與烴混合，該熱交換 器位於該第一重組器中或以操作方式耦合至該第一重組 器。如圖2中所顯示’ i第一重組器14之額外熱可自來自 催化部分氧化重組H 2G之-熱流出物流提供。在第一重組 益1钟’纟自烴流之烴之至少—部分經裂解及/或經重組 以產生經由管線70提供至第二重組器16之一進料流。 第二重組器16以操作方式耦合至高溫氫分離裝置18且高 ’皿氫刀離裝置產生至少一部分、大部分、至少75體積％或 至/ 90體積％或大致所有進人熔融碳酸鹽燃料電池η之陽 極24之含氫氣體。高溫氫分離裝置可定位在第二重組器μ 之後及熔融碳酸鹽燃料電池12之前。在—較佳實施例中， 向溫氫分離裝置18係一薄膜分離單元，其係第二重組器Μ 之^…皿虱分離裝置18自經重組產物分離氫。所分離 之虱係提供至熔融碳酸鹽燃料電池12之陽極2 4。 149088.doc •33- 201108498 在該方法之一實施例中’烴流含有任何可蒸發烴中之一 者或多者’其在大氣壓（視情況經充氧）下於2(rc下係液 體，在大氣壓下於高達400°C之溫度下可蒸發。此等烴可 包含但不限於具有50°C至36(TC之一沸點範圍之石油分餾 物，例如石腦油、柴油、喷射機燃料、汽油及煤油。在一 貫施例中’該烴流係癸烧。在一較佳實施例中，該烴流係 柴油燃料。在一實施例中，該烴流含有具有自五至二十五 之範圍之碳數目之烴。在一較佳實施例中，該烴流含有至 少0.5、或至少〇.6、或至少〇7或至少0.8莫耳分率之含有至 少五個、或至少六個或至少七個碳原子之烴。 該烴流可視情況含有在25〇c下為氣態之某些烴，例如在 25 C下為氣態之含有自一個至四個碳原子之曱烷、乙烷、 丙烷或其他化合物。該烴流可在進料至第一重組器14之前 經處理及/或在熱交換器72中經加熱以移除可對該第一重 組窃中用於將較高分子量烴轉化至較低分子量烴之任一觸 媒造成有害影響的任何材料。舉例而纟，該烴流可已經歷 一系列處理以移除金屬、硫及/或氮化合物。 方法之貫施例中，該煙流與含有至少2 〇體積0/〇、 或至少50體積％或至少8〇體積％之二氧化碳之天然氣混 合。若必須’則該天錢已經處理以移除硫化氫。在一實 施例中’具有至少20體積之二氧化碳、至少50體積％之 二氧化碳或至少7〇體積％之二氧化碳之—烴流可用作一燃 料源。 在一實施例中 該烴流可在至少、較佳自20〇t至 149088.doc •34· 201108498 重組器14 ’其中該烴流可在 ’如下文所闡述。將該烴流 400°C之一溫度下提供至第一 熱交換器中加熱至一所需溫度 進料至第重組5 14之溫度可選擇為盡可能高以蒸發該等 烴而不產生焦碳。該烴流之溫度可在自i贼至⑽代之範 圍。另-選擇為（但較不佳），倘若該煙流之硫含量為低， 則可在低於例如15G c之—溫度下將該烴流直接進料至第 一重組器14而不加熱該烴流。 如圖1中所顯示，可使該烴流穿過一個或多個熱交換器 、力忒進料。§亥烴流可藉由與自熔融碳酸鹽燃料電池 12之陰極26分離隸由管線74進料至熱交換器以陰極排 氣流交換熱而加熱。可藉由調整節流閥76錢來控制陰極 排氣流進料至熱交換器72及22之速率。 在一較佳實施例中’經由管、_將單獨之陽極排氣流進 料至第一重組14之一個或多個重組區中。可藉由調整節 流閥82來控制陽極排氣流進料至第一重組器"之速率。陽 極排氣之溫度可在自約5〇〇t至約7〇〇t之範圍，且較佳為 約650°C。 … 陽極排氣流包含氫、蒸汽及來自進料至燃料電池12之陽 極24之燃料之氧化的反應產物以及未反應燃料。在一實施 例中，陽極排氣流含有至少〇 5、或至少〇 6或至少〇 7莫耳 分率氫。進料至第—重組器14或該第一重組器之一重組區 之陽極排氣流中之氫可幫助阻止焦碳在該第一重組器中之 形成。在一實施例中，該陽極排氣流含有自〇 〇〇〇】至約 〇·3、或自0.001至約0.25或自〇 〇1至約〇 2莫耳分率水（作為 149088.doc -35- 201108498 蒸汽）。除氫之外，存在於進料至第一重組器14或該第一 重且器之一重組區之陽極排氣流中之蒸汽亦可幫助阻止焦 — 第重組器中之形成。該陽極排氣流可含有充足之 、卩制焦化且含有充足之蒸汽以將烴流中之烴之大部分 重組至甲烷、氫及-氧化碳。因此，該第-重組器及/或 該第二重組器中可需要較少蒸汽來重組烴。 視情況，可經由管線84將蒸汽進料至第一重組器14或安 第重組态之一重組區以與該第—重組器或該第一重組录 之重組區中之烴流混合。可將蒸汽進料至第一重組器⑷ 該第一重組器之—重組區以抑制或阻止焦碳在該第一重每 器中形成且視情況用於該第一重組器中所實現之重組反肩 中。在-實施例中’以一速率將蒸汽進料至第一重組器[ 或㈣-重組器之重組區，其中添加至該第—重組器之鎖 蒸>飞之莫耳比係、添加至該第—重組器之煙流中之碳之莫耳 之至少兩倍或至少三倍。添加至該第-重組器之總蒸汽可 包含士自陽極排氣之蒸汽、來自一外部源之蒸汽(例如， 透過官線84)或其混合物。在第_重組器14或該第_重电 二=組區中提供至少2:1、或至少一至少3"或 ^•5:1之-蒸汽與碳莫耳比可心抑制焦碳在該第一重 =中之形成。節流_可用於控制蒸汽透過管線料進料 -重組器14或該第一重組器之—重組區之速率 該陽極排氣包含大量氣，因此在重組期間往往發生較少隹 :用因：’進料至第-重組器…選蒸汽之量可顯；； 於用於習用重組單元之蒸汽之量。 149088.doc -36 - 201108498 蒸汽可在至少125°C、較佳自15〇°C至300°C之一溫度下 進料至第4組器14，且可具有自〇」至〇 5⑽&之_ 壓力，錢具有等於或低於進料至該第一重組器之陽極排 氣流之壓力之一壓力，如本文中所闡述。可藉由加熱具有 至少1_0 MPa、較佳丨.5 Mpa至2_0 MPa之一壓力之高壓水 (藉由經由管線88傳遞該高壓水穿過熱交換器9〇)來產生蒸 汽。藉由與在陰極排氣進料已經由管線74穿過熱交換器72 之後進料之陰極排氣交換熱來加熱該高壓水以形成高壓蒸 汽。另一選擇為，可將該陰極排氣直接進料至熱交換器 9〇(未顯示）或一個或多個熱交換器。若利用了多於一個熱 交換器，則在退出熱交換器90或最終熱交換器之後，該高 壓蒸汽可隨後經由管線92進料至管線84。可藉由透過一膨 脹機使該高壓蒸汽膨脹來將該高壓蒸汽減壓至所需壓力， 然後將其進料至該第一重組器。另一選擇為，可藉由透過 一個或多個熱交換器90進料低壓水且將所得蒸汽傳遞至第 一重組器14中來產生供該第一重組器中使用之蒸汽。 視情況，第一重組器14或第二重組器16中未利用之高壓 洛汽可透過其他動力裝置（例如，一渦輪機（未顯示與任 一未利用之高壓二氧化碳流一起或視情況不與高壓二氧化 碳流一起膨脹。電源可用於產生電及/或除由燃料電池12 產生之電之外的電。由電源及/或燃料電池產生之功率可 用於給壓縮機94及/或本發明之方法中所使用之任何其他 壓縮機供電。 經流、可選蒸汽及陽極排氣流在對蒸發並非呈蒸氣形式 149088.doc -37· 201108498 之任何烴並裂解該等烴以形成進料有效之一溫度下於第一 重組器14或該第-重組器之一重組區中與一重組觸媒混合 並接觸。 該重組觸媒可係一習用重組觸媒且可係此項技術中已知 之任一觸媒。可使用之典型重組觸媒包含但不限於νιπ族 過渡金屬，特定而言鎳及在高溫反應條件下為惰性之一載 體或基材。用作高溫重組/加氫裂解觸媒之一載體之適合 的惰性化合物包含但不限於α_氧化鋁及氧化錄。 在一較佳實施例中，烴流、陽極排氣及可選蒸汽在自約 5〇〇°C至約65(TC或自約550t：至600。(：之一溫度下與一觸媒 混合並接觸，其中重組反應所必需之所有熱由陽極排氣供 應。在一實施例中，烴流、可選蒸汽及陽極排氣流在至少 4〇〇°C、或自450°C至650°C或自500°C至600°C之一範圍中 之一溫度下與一觸媒混合並接觸。 由自放熱熔融碳酸鹽燃料電池12進料之陽極排氣流供應 至第一重組器14或該第一重組器之一重組區之熱驅動該第 一重組器中之吸熱裂解及重組反應。自熔融碳酸鹽燃料電 池12進料至第一重組器14及/或該第一重組器之—重組區 之陽極排氣流極熱，其具有至少500°C之一溫度，通常具 有自550°C至700t或自600°C至65CTC之一溫度。熱能自熔 融碳酸鹽燃料電池12至第一重組器14或該第一重組器之一 重組區之傳送係相當有效的，此乃因來自該燃料電池之熱 能包含在陽極排氣流中，且藉由直接將該陽極排氣流與烴 流及蒸汽混合而傳送至第一重組器14或該第一重組器之一 149088.doc -38 - 201108498 重組區令之烴流、可選蒸汽及陽極排氣流之混合物。 裎徂白文中所闡述之方法之一較佳實施例中，陽極排氣流 乂供自煙流、可選蒸汽及陽極排氣之混合物產生進料所需 之熱之至少99%或大致所有熱。在_特定較佳實施例中， 除陽極排氣流之外無其他熱源提供至第一重組器14以將烴 流轉化為進料。 在貫細例中，該陽極排氣流、烴流及可選蒸汽在第一 .重組器14中與重組觸媒接觸時所處之壓力可在自0.07 MPa 至3.0 MPa之範圍。若高壓蒸汽未進料至第一重組器"， 則該陽極排氣流、烴流及可職絲汽可在該範圍之低端 處之一壓力（通常自0.07 MPa至〇 5 Mpa或自Μρ^〇 3 MPa)下於該第-重組器中與重組觸媒接觸。若高壓蒸汽進 料至第重組器14，則該陽極排氣流、烴流及蒸汽可在壓 力範圍之較尚端（通常自1〇 MPa至3 〇 Μρ&或自j 5 Mb至 2·〇 MPa)處與該重組觸媒接觸。 參照圖2，第一重組器14可藉由經由管線96與來自催化 部分氧化重組器20之流出物交換熱而加熱至高於63〇<>c、 或自65(TC至90(TC或自700。(：至80(TC之溫度。管線96以操 作方式耦合至熱交換器98。熱交換器98可係管線96之一部 分。熱交換器98可位於第一重組器14中或連接至第一重組 器以使得可與進入該第一重組器之烴流交換熱。可藉由調 整節流閥100及三通節流閥102來控制流出物自催化部分氧 化重組器20進料至第一重組器14之速率。P H2(anode) p0.  02 (cathode) · Pc〇2 (cathode) 149088. Doc 201108498 Field 3 hydrogen and oxygen and carbon dioxide-rich streams are supplied from the pressure swing adsorption unit. Although the prior art is effective in providing hydrogen, oxygen and carbon dioxide to fuel cells at different concentrations, the process is relatively inefficient in producing hydrogen 'carbon dioxide and oxygen flow. ^ The method is relatively hot in the gas generation and heat process. Inefficient, because the anode gas is cooled to enter the water before entering the pressure swing adsorption unit. In addition, the reformer does not convert a liquid hydrocarbon feedstock to a lower molecular weight feed for one of the steam reformers and may provide insufficient heat from the fuel cell to do so. A further improvement in operating the molten carbonate fuel cell system for generating electricity and enhancing the power density of the molten carbonate fuel cell can be expected. SUMMARY OF THE INVENTION The present invention is directed to a method for operating a molten carbonate fuel cell, comprising: providing a hydrogen-containing stream comprising molecular hydrogen to an anode portion of a molten carbonate fuel cell; controlling the hydrogen-containing portion Flow rate to one of the anodes such that the molecular hydrogen utilization in the anode is less than 50%; mixing anode exhaust gas comprising molecular hydrogen from the molten carbonate fuel cell with a hydrocarbon stream comprising hydrocarbons, wherein the hydrocarbon The anode exhaust gas having a flow mixing has a temperature from one of 500t to 700 ° C; contacting at least a portion of the mixture of the anode exhaust gas and the hydrocarbon stream with the catalyst to generate one or more gaseous hydrocarbons, molecular hydrogen, and at least One 149088. Doc 12 201108498 Oxide steam recombination feed; separating at least a portion of the molecular hydrogen from the steamed π recombination feed; and treating at least the partial hydrogen of the molecular hydrogen separated by the ° hai as the MH of the molecular hydrogen At least a portion of the melon is provided to the molten carbonate fuel cell anode. In another sad aspect, the present invention is directed to a molten carbonate fuel cell system comprising: a molten tartrate fuel cell configured to receive a hydrogen-containing stream comprising molecular hydrogen at a first rate to cause the molten carbonic acid Hydrogen utilization in the anode of one of the salt fuel cells is less than 50%; one or more recombiners operatively coupled to the molten carbonate fuel cell, at least one recombinator configured to receive fuel from the molten carbonate The anode of the battery is vented with hydrocarbons and configured to allow the anode exhaust to be thoroughly mixed with hydrocarbons to at least partially recombine certain hydrocarbons of the hydrocarbons to produce a recombined product stream, wherein the reconstituted product stream comprises Molecular hydrogen and at least one carbon oxide; and a high temperature hydrogen separation unit that is at least one of the recombiners or is stalked to at least one of the recombiners and is operatively depleted to the a molten carbonate fuel cell, wherein the high temperature hydrogen separation device comprises one or more high temperature hydrogen separation membranes and is configured to receive a recombinant product stream and one comprising the molecular emulsion To provide at least part of the ilk 'molten carbonate fuel cell. [Embodiment] The invention as set forth herein provides an efficient method for operating a molten carbonate fuel cell to produce electricity at a high electrical power density and for performing 149088. Doc •13· 201108498 One of the methods of this system. First, the methods set forth herein maximize the electrical power density of the fuel cell system by minimizing, rather than maximizing, fuel utilization per fuel path in the molten carbonate fuel cell. The fuel utilization of the mysterious mother is minimized to reduce the concentration of carbon dioxide and oxidation products (specifically water) throughout the length of the anode path of the fuel cell such that a high chlorine concentration throughout one of the lengths of the anode path is maintained. Since there is an excess of hydrogen for the electrochemical reaction at the anode electrode along the entire anode path length of the fuel cell, the fuel cell provides a high electrical power density. In terms of achieving a high-per-pass fuel ratio (eg, greater than (4) The fuel utilization rate s / go to the 'oxidation product and the carbon dioxide concentration can include more than 4% of the fuel flow before the fuel has traveled through even half of the fuel cell: 'oxidation in the fuel cell exhaust The ingress of the product and carbon dioxide can be several times the concentration of the crucible such that the electrical power provided along the anode path can be significantly reduced as the fuel provided to the fuel cell advances through the anode. Submerging the anode with hydrogen over the entire path length of the anode of a molten carbonate fuel cell to enable electrochemical reversal of the anode The concentration of hydrogen at the pole is maintained at a high level throughout the length of the anode path. Jf, u maximizes the electrical power density of the fuel cell. In this method, the main hydrogen or preferably almost all hydrogen is used. The hydroquinone maximizes the electrical power density of the fuel cell system because the gas has a significantly greater electrochemical potential than other oxidizable compounds (e.g., carbon monoxide) typically used in smelting carbonate fuel cell systems.系统The system that has been uncovered in this technology, the method described in this article borrows 149088. Doc 201108498 produces a higher electrical power density in a molten carbonate fuel cell system by utilizing a hydrogen-rich fuel and minimizing, rather than maximizing, the fuel utilization per pass of the fuel cell. The minimization is achieved by separating and recycling hydrogen trapped from the fuel exhaust of the fuel cell (eg, anode exhaust) and feeding the hydrogen from a feed and recycle stream at a selected rate to a minimum. The fuel utilization rate of each pass. The system described herein allows a hydrogen rich stream to be supplied to the molten carbonate fuel cell while minimizing the hydrocarbons supplied to the fuel cell, as compared to conventional systems. The system produces a hydrogen rich stream that can be introduced directly into the anode portion of the molten carbonate fuel cell. The "Hai system does not need to be directly coupled to the anode of the molten carbonate fuel cell and/or the recombiner clamped in the anode to ensure sufficient hydrogen production as a fuel for the fuel cell. 、This, molten carbonate burning: removing or eliminating a recombiner or recombination zone in the pool allows hydrogen to flood the molten acid fuel cell while pre-configuring most of the heat from the anode exhaust. Fuel cells that have been equipped with internal recombination zones can be used in combination with the systems set forth herein. Such fuel cells can operate more economically and efficiently than systems disclosed in the art. In the first step of refining the cathode of the carbonate fuel cell; the length of the cathode is flooded with carbon dioxide so that the concentration of carbon dioxide at the cathode electrode available for electrochemical reaction is maintained throughout the length of the cathode path - The high level is used to maximize the electrical power reach, degree and/or battery voltage of the fuel cell. The method described in this paper is S - 149088 containing carbon dioxide rich oxidant gas. Doc • 15· 201108498 flow, thus allowing operation of the fuel cell such that a partial pressure of carbon dioxide in a majority of the cathode portion of the molten carbonate fuel cell is greater than a majority of an anode portion of the molten carbonate fuel cell The partial pressure of carbon dioxide. Operating the fuel cell in this manner produces a higher electrical power density than the systems disclosed in the prior art. The carbon dioxide oxidant gas is used to raise the voltage of the molten carbonate fuel cell and to suppress the carbon dioxide deficiency of the molten carbonate fuel cell. "Insufficient carbon dioxide" means that the partial pressure of carbon dioxide exiting the cathode (Pc 〇 2C) is less than the partial pressure of carbon dioxide exiting the anode (Pco /) ^ excess carbon dioxide is supplied to the molten carbonate fuel cell at a minimum hydrogen utilization rate Higher voltages and/or current densities are allowed to be obtained from the molten carbonate fuel cell. The system set forth herein allows a hydrocarbon-rich carbon stream to be supplied to the fuel cell from the hydrocarbon supplied to the molten carbonate fuel cell as compared to conventional systems. The carbon dioxide produced from the system can be introduced directly into the cathode portion of the molten carbonate fuel cell. The system does not require an external source of carbon dioxide to ensure sufficient carbon dioxide as a feed to the cathode of the fuel cell. The methods described herein are also highly efficient because hydrogen and carbon dioxide that are not utilized in the fuel cell to produce electricity are continuously recirculated through the fuel cell system. This achieves a high electrical power density relative to one of the lowest heating values of the fuel by solving the problem associated with the loss of hydrogen and/or carbon dioxide energy from the battery that is not converted to electrical energy. The system allows an appropriate amount of air or molecular oxygen to be simultaneously fed to the cathode of the fuel cell such that the carbon dioxide in the feed to the cathode is molecularly 149088. Doc -16· 201108498 Oxygen molar ratio minimizes the concentration polarization at the electrode of the fuel cell. The system does not require oxygen-enriched air. The process of the present invention allows the anode to be flooded with hydrogen while flooding the cathode with carbon dioxide while controlling the amount of molecular oxygen such that the carbon dioxide to molecular oxygen molar ratio in the feed to the cathode is at least 2 or at least 2. 5. The use of the fuel cell system set forth in the present invention allows the molten carbonate fuel cell to be operated at a high power density at 〇1 atm). Typically, molten carbonate fuel cells operate at pressures from atmospheric to about MPa (1 〇 atm). Operating at pressures above atmospheric pressure can affect the life of the seal in various portions of the molten carbonate fuel cell. The molten carbonate fuel cell operates at or near atmospheric pressure to extend the life of the seal in the molten carbonate fuel cell + while generating electricity at a high current density for a given battery voltage and/or power density. In the method described herein, the per unit of electricity produced by the method = less carbon dioxide. A first recombiner, a second recombiner, and a 7 m hydrogen knife-off device and a fuel cell are thermally reduced and preferably eliminated to provide an endothermic recombination reaction in one or both recombiners. In an additional energy, heat generated in the fuel cell is directly transferred to the first recombiner by providing a hot anode exhaust stream from the fuel cell to the first recombiner. And then directly feeding the product of the first recombiner into the second pn and then providing the product of the second recombiner directly to the high knife-off device. The thermal product is reduced (eg, by Burning) provides extra ambiguity. Therefore, the amount of carbon dioxide produced when the energy is supplied to drive the recombination reaction is reduced. 1490S8. Doc • 17-201108498 By recirculating carbon dioxide from the reformed gas product and subsequently feeding a carbon dioxide containing gas stream to the fuel cell, recirculating the anode exhaust stream through the system and providing a carbon dioxide gas stream to the fuel cell is reduced by Combustion produces an amount of carbon monoxide. This recycling increases the electrical efficiency of the process and thereby reduces any carbon dioxide emissions. Additionally, by separating the hydrogen-containing stream from the reformed gas product and subsequently feeding the hydrogen-containing stream to the fuel cell, the anode exhaust stream is recirculated through the system and one of the molecular hydrogen-rich hydrogen-containing streams is provided. To the fuel cell, the amount of hydrogen required by the second recombiner is reduced. This recycling of the anode exhaust increases the electrical efficiency of the process. In addition, the power of the molten carbonate fuel cell is improved by the degree, so that in order to generate the same amount of power, a fuel cell having a smaller size than a conventional fuel cell can be used to generate power. The methods described herein are more thermally and energy efficient than the methods disclosed in the art. Thermal energy from a fuel cell exhaust is delivered directly to a first recombiner. In some embodiments, a portion of the transferred thermal energy is subsequently transferred from the first recombiner to a second recombiner. The transfer of thermal energy directly from the anode of the fuel cell to the first recombiner is efficient because the transfer is performed directly from the hot anode exhaust stream from the fuel cell in the first recombiner This is achieved by a molecular mixing of a hydrocarbon stream comprising hydrocarbons and steam. A hot feed is produced from the first reformer and subsequently fed to the second reformer. The transfer of thermal energy from the first recombiner to the second recombiner is also efficient' because the thermal energy is included in the feed from the first recombiner to the a second recombiner. The methods described herein are more hot than the methods disclosed in the art 149088. Doc 201108498 The rate of release is due to the heat from the anode exhaust used to generate hydrogen at temperatures below the typical steam recombination method. In the process of the present invention, hydrogen can be separated from the reformed product gas using a high temperature hydrogen separation unit, wherein the high temperature nitrogen separation unit is a membrane separation unit. The high temperature hydrogen separation unit can be operatively coupled to the second reformer such that heavy hydrogen can be generated in the second reformer and hydrogen can be separated from the reformed gas during the reaction. The separation of hydrogen drives the equilibrium towards hydrogen and reduces the temperature required to produce hydrogen. In addition, the hydrogen can be produced at a lower recombination temperature, because the balance of the water gas shift reaction (H2〇+c〇# C〇2+H2) is favorable for generating hydrogen at a lower recombination temperature, but in the conventional recombination It is not favorable at the reaction temperature. Most or all of the sub-hydrogen and carbon dioxide systems produced from the second reformer are supplied to the molten carbonate fuel cell. The methods described herein allow for the use of liquid fuels. Using liquid fuel allows one fuel to be used by more than one power source. For example, diesel fuel can be used on a ship to power a molten carbonate fuel cell and engine. Hydrogen is added to the first recombiner by mixing the anode exhaust with the liquid feed. The recycle of hydrogen eliminates the need for one of the individual hydrogen sources for thermal cracking of the liquid feed. Although some hydrogen is consumed, hydrogen is produced after the recombination of the cracked hydrocarbon. The integration of the recombiner with the high temperature hydrogen separation unit allows the system to produce substantially all of the hydrogen required by the methods. The recombination and/or hydrocracking of liquid fuel produces more carbon dioxide per mole of hydrogen produced by the fuel having a carbon number greater than 6 (eg, diesel and naphtha) having a hydrogen to carbon ratio less than less than The hydrogen to carbon ratio of a 6 carbon number fuel (eg, methane). Hydrogen produced by each mole produces more oxidation 149088. Doc •19- 201108498 Carbon allows for the production of all or all of the carbon dioxide required for the molten carbonate fuel cell from the liquid fuel. Producing carbon dioxide in this manner eliminates or reduces the need to use a portion of the anode gas and/or feed gas as a fuel for a thermally inefficient combustion burner to produce carbon dioxide. Excess hydrogen and carbon dioxide are produced in the process set forth herein, which allows hydrogen and carbon dioxide to be recycled through the system. The method of the present invention allows a flash carbonate fuel cell to be at 0 1 atm) or less than o. Operating at a pressure of MPa (l atm) and providing a battery voltage of at least W12 W/cm of power, degrees and/or at least 8 〇〇 mV. In some embodiments, the method of the present invention allows a molten carbonate fuel cell to be at or below 1 MPa (l atm). Operates at a pressure of 1 MPa (1 atm) and provides at least 0. One of 12 W/cm2 power density and / or at least 8 〇〇 mV battery voltage. As used herein, unless otherwise indicated, the term "hydrogen" refers to a molecular hydrogen. As used herein, the term "hydrogen source" refers to a compound from which free hydrogen can be produced. For example, the source of hydrogen can be, for example, a hydrocarbon of methane or a mixture of such compounds or a hydrocarbon-containing mixture such as natural gas. As used herein, when two or more elements are described as "connected operatively" or "operably coupled", the elements are defined as being directly or indirectly connected to allow the Direct or indirect fluid flow. As used herein, the term "fluid flow" refers to the flow of a gas or a fluid. For use in the definition of "operating in connection" or "operating coupling", the term "indirect fluid flow" means permeable 149088. Doc •20· 201108498 One or more additional elements direct the flow of a fluid or a gas between two defined elements to change the fluid or gas as it flows between the two defined elements One or more aspects. A state in which a fluid or a gas can change in an indirect fluid flow includes physical properties (such as the temperature or pressure of a gas or a fluid) and or the composition of the gas or fluid (eg, by isolating the gas or fluid) One part or condensed water by a gas stream containing one of the steam. As defined herein, "indirect fluid flow" does not include the chemical reaction (eg, oxidation) or reduction of one or more elements of the fluid or gas to alter the gas or fluid between the two defined elements. composition. As used herein, the term "selectively permeable to hydrogen" is defined as being permeable to molecular hydrogen or elemental hydrogen and impermeable to other elements or compounds such that at most 1%, or at most, non-hydrogen elements or compounds 5% or at most 1% can penetrate substances that are permeable to molecular hydrogen or elemental hydrogen. As used herein, the term "high S hydrogen separation unit" is defined as being at a temperature of at least 25 〇t (for example, at a temperature of 3 〇〇 (> (: to 65 ° 1) A device or device that is effective in separating hydrogen in the form of molecules or elements from a gas stream. As used herein, the use of a gas in a fuel in a smelting carbonate fuel cell is "utilization of hydrogen per pass". The system is defined as the relative: the amount of hydrogen in the fuel for the passage through the (four) carbonate fuel cell - the second pass to the combustion: the amount of hydrogen in the fuel - the amount of hydrogen used in the pass. The hydrogen utilization rate of the mother overnight can be calculated by measuring the amount of hydrogen fed to one of the anodes of a fuel cell by the following steps; amount: 149088. Doc -21 - 201108498 The amount of hydrogen in the anode exhaust of the fuel cell; from the measured amount of hydrogen fed to the fuel of the fuel cell minus the measured anode exhaust of the fuel cell The amount of hydrogen is used to determine the amount of hydrogen used in the fuel cell; and the amount of hydrogen used in the fuel cell calculated by S is divided by the measured feed into the fuel of the fuel cell The amount of hydrogen. The hydrogen utilization per pass can be expressed as a percentage by multiplying the calculated hydrogen utilization per pass by 100. As used herein. "Excess carbon dioxide" means one of the partial pressure differences (ΔΪ^02) of the carbon dioxide between the anode and the cathode of the molten carbonate fuel cell. "Excess carbon dioxide" (APco2) is calculated by measuring the partial pressure of carbon dioxide in the anode and cathode exhausts at the anode and cathode outlets, respectively, and the partial pressure of carbon dioxide from the measured cathode. The measured partial pressure of carbon dioxide of the anode (for example, ΔΡε〇2 = (Ρε〇2Κρ(3) for one convection of the feed to the anode and cathode, "excess carbon dioxide" is obtained by the following steps: at the anode outlet And measuring the partial pressure of carbon dioxide in the anode exhaust gas and the cathode exhaust gas at the cathode inlet; and subtracting the measured carbon dioxide partial pressure value of the anode from the measured carbon dioxide partial pressure value of the cathode (for example, ΔPcofCPco/ Inletxpco/ounet)) The average excess carbon dioxide is calculated by the following equation: APc〇2(aVg)=[{Pc〇2Cin. Et+pc〇2C〇utlet}_{pc〇2ainlet+pc〇2a〇utlet^/2 卩°卩里—Oxidized carbon refers to each percent hydrogen at a normalized distance assuming symmetry along the y-direction (width) The utilization value of one of the partial pressure differences of the oxidized slave of the molten carbonate fuel cell is calculated by the partial excess of the oxidative anesthesia, wherein the X system is along the yang 149088. Doc -22- 201108498 One of the lengths of the polar zone normalized distance. BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 through 3 illustrate an embodiment of a system of the present invention which is not used in carrying out the method for operating a molten carbonate fuel cell to produce electricity in accordance with the present invention. The fuel cell system 10 includes a molten carbon carbonate fuel cell crucible, a first-recombiner 14, a second recombiner 16, a high-temperature hydrogen separation device 18, and an oxidation unit 20. In a preferred embodiment, the second recombiner 16' high temperature chlorine separation unit Oxidation Unit 2 () is a unit. In the preferred embodiment, oxidation unit 20 is a catalytic partial oxidation recombiner. In the embodiment, the high temperature hydrogen separation unit 18 is a molecular hydrogen membrane separation unit. In one embodiment, the second recombiner 16 includes a recombination zone, a high temperature hydrogen separation unit 18, a catalytic partial oxidation recombiner 20, and a heat exchanger 22. The continued operation of the thermal integrated system to listen to the carbonate fuel cell provides sufficient hydrogen and carbon dioxide to generate electricity. The molten carbonate fuel cell 12 includes an anode 24, a cathode 26, and an electrolyte 28. Electrolyte 28 is interposed between anode 24 and cathode 26 and contacts the anode and cathode. The molten carbonate fuel cell 12 can be a conventional molten carbonate fuel cell and preferably has a tubular or planar configuration. The molten carbonate fuel cell 12 can include a plurality of individual fuel cells stacked in a stack. The individual fuel cells can be electrically coupled by interconnecting and operatively connected such that one or a plurality of gas streams can flow through the anode of the stacked fuel cell and an oxidant-containing gas can flow through the stacked fuel cell cathode. As used herein, the term "molten carbonate fuel cell" is defined as a single molten carbonate fuel cell or a plurality of molten carbonate fuel cells that are connected or stacked in a stack. The anode 24 of the molten carbonate fuel cell 12 may be a porous sintered nickel compound, a nickel-chromium alloy, nickel with lithium chromium oxide, and/or J49088. Doc •23· 201108498 Nickel-copper alloy or any material suitable for use as the anode of a molten carbonate fuel cell. The cathode 26 of the molten carbonate fuel cell i2 can be formed of a porous sintered material such as nickel oxide, lithium-nickel-iron oxide or any material suitable for use as a cathode of a molten carbonate fuel cell. A gas stream is fed to the anode and cathode to provide the reactants necessary to generate electricity in the fuel cell 12. The hydrogen containing stream enters the anode 24 and contains an oxidant stream into the cathode 26. Electrolyte section 28 is positioned in the fuel cell to prevent hydrogen containing gas from entering the cathode and preventing the oxidant containing gas stream (oxygen and carbon dioxide stream) from entering the anode. The oxidant-containing gas stream comprises one or more streams containing oxygen and/or carbon dioxide. Electrolyte section 28 directs carbonate ions from the cathode to the anode to achieve electrochemical reaction at the one or more anode electrodes with oxidizable compounds (eg, hydrogen and, optionally, nitric oxide) in the anode gas engine. . Examples of the electrolyte segment formed by the metal slave salt, the soil metal carbonate or a combination thereof may be formed from lithium carbonate, lithium carbonate, lithium carbonate, sodium strontium carbonate, sodium lithium carbonate. A porous material formed of calcium and lithium potassium carbonate. The dip battery 12 is configured to allow a hydrogen containing stream to flow from the anode population through the anode 24 and out of the anode exhaust outlet & the hydrogen containing stream contacts the anode path length from the anode inlet 30 to the anode exhaust exit σ32 - One or more anode electrodes. Further, a gas stream containing molecular hydrogen (hereinafter, hydrazine "IL) or a hydrogen source is fed to the anode inlet 30 through a line 34. A throttle valve 36 can be used to select and control the flow rate of the hydrogen containing stream to the anode inlet 30. In a comparison 149088. Doc 24 - 201108498 〇·98 mole fraction hydrogen = a known example, 1 from a high temperature hydrogen separation unit to feed to the anode 24' of the fuel cell crucible, wherein the high temperature hydrogen separation unit, thin film unit, as detailed below Speaking. The hydrogen-containing gas stream may contain at least 0. 6, or until the evening 0. 7, $ at least 0. 8. At least 〇 9, or at least 〇 % or at least "the gas fed to the cathode - contains an oxidant. As referred to herein, "oxidant" means a compound that can be reduced by reaction with molecular hydrogen. The oxidant-containing gas fed to the cathode in certain embodiments t' contains oxygen, ruthenium oxide, an inert gas, or a mixture thereof. In the embodiment, the oxidant-containing gas system - the oxygen-containing gas stream is combined with the -carbon dioxide-containing gas stream or an oxygen-containing carbon monoxide stream. In a preferred embodiment, the oxygen-containing system fed to the cathode has been mixed with sufficient carbon dioxide or oxygen-enriched air such that the molar ratio of carbon dioxide to oxygen is at least 2 or at least 25. 3 oxidant gas may flow from the cathode inlet (10) through the cathode "and then through the cathode exhaust outlet, the oxidant-containing gas contacts one or more cathode electrodes over the length of the cathode path from the cathode inlet 38 to the cathode exhaust outlet 4G. In one embodiment, the oxidant-containing gas may flow convectively with respect to the flow of hydrogen-containing gas to one of the anodes 24 of the fuel cell 12. In an embodiment, the oxidant-containing gas stream is passed through line 44 from the oxidant-containing gas source 42. The feed to the cathode σ 38. The throttling _ can be used to select and control the rate at which the gas stream is fed to the cathode 26. In some embodiments, the oxidant-containing gas is provided by an air compressor. The oxidant-containing gas stream can be air. In one embodiment, the oxidant-containing gas may be pure oxygen. In one embodiment, the oxidant-containing gas stream may contain at least 13% by weight of oxygen and / or at least % 149088. Doc . 25· 201108498 f The amount of carbon oxide § oxygen and / or carbon dioxide air. In a preferred embodiment, the flow of air and/or carbon dioxide is controlled such that the molar ratio of carbon dioxide to molecular oxygen in the gas is at least 2 or at least 2. 5. In one embodiment, the oxidant-containing gas stream is supplied by a carbon dioxide-containing gas stream and an oxygen-containing gas stream f. The carbon dioxide stream and the oxygen-containing gas stream can come from two separate sources - in the preferred embodiment, for the majority of the molten carbonate fuel cell 2 or substantially all of the carbon dioxide is supplied to the first recombinator. The carbon dioxide containing gas stream is fed from the carbon dioxide source to the cathode inlet 38 through the line feed. The carbon dioxide containing gas stream provided to the fuel cell 12 can be fed to the same cathode inlet 38 with the oxygen containing stream, or can be fed to the cathode inlet 38. The month is mixed with the oxygen-containing gas stream. Alternatively, the carbon dioxide-containing gas stream can be supplied to the cathode 26 through a separate cathode population. In a preferred embodiment, the carbon dioxide stream is passed from the high temperature hydrogen separation unit 18 via lines 48 and 44. A cathode 26 is provided to the fuel cell 12, as set forth herein. Oxygen can be supplied to the cathode % of the fuel cell via line 44. Feed to the cathode and/or anode prior to feeding to the cathode 26 and/or the anode 24 The milk (whether one stream or streams) can be heated in a heat exchanger 22 or other, in a converter, preferably by being connected to the cathode exhaust port and through the line 50 to the hot junction The oxygen-depleted cathode exhaust stream of the exchanger 22 exchanges heat. In the method of the present invention, the hydrogen-containing stream is mixed with an oxidant at one or more of the anode electrodes of the molten carbonate fuel cell 12 to produce electricity. Preferably, the oxidant is derived from carbonate ions that react with carbon dioxide and oxygen flowing through the cathode 26 and are directed across the electrolyte of the fuel cell. The hydrogen-containing gas stream and/or the oxidant-containing gas stream are fed at an optional rate. To fuel 149088. Doc -26 - 201108498 Battery 12 to mix the hydrogen containing stream with the oxidant at one or more anode electrodes of the fuel cell, as discussed in detail below. Preferably, the hydrogen-containing stream and the oxidant are mixed at one or more anode electrodes of the fuel cell to have at least G"w/em2, or to ", G15W/W, or at least 0. 2 WW, or at least w3 w/cm2 or at least 〇6 w"2 of one electrical power density to generate electricity. Higher at higher pressures and/or by using an oxidant-rich gas stream (eg, oxidant-rich air) Power Density The molten carbonate fuel cell u is operated at a temperature that enables carbonate ions to be effective from the cathode 26 across the electrolyte portion 28 to the anode 24. It can be from 55 (TC to 7 〇 (TC or _ 〇. The molten carbonate fuel cell 12 is operated at a temperature of -4. The oxidation system of hydrogen and carbonate ions is exothermicly reacted at one or more anode cells. The heat of the reaction is produced by operating the molten carbonate fuel cell 12 The heat required to operate a molten carbonate fuel cell can be controlled by several factors, including but not limited to adjusting the feed temperature and feed flow of the hydrogen-containing gas and the oxygen-containing gas. Thus excess hydrogen is fed to the system and unreacted hydrogen can partially cool the molten carbonium salt fuel cell by carrying excess heat to the crucible-recombiner. Adjusting the flow of carbon dioxide and/or the flow of the oxidant-containing stream To The carbon dioxide fraction = oxygen molar ratio maintained at about 2 requires sufficient oxidant-containing gas to be an excess of one to three times the amount of molecular oxygen required to react with the portion of the hydrogen utilized in the anode. Thus, an excess of oxygen-depleted air or oxidant-containing gas exiting the cathode exhaust may carry a significant amount of heat from the molten carbonate fuel cell. The hydrogen-containing stream, as described below, is supplied from a high temperature hydrogen separation unit. To the anode 24 of the molten carbonate fuel cell 12, 'It can be made by U9088. Doc • 27-201108498 ° (eg, through heat exchanger 22) to reduce the temperature of the hydrogen-containing stream supplied to the anode of the molten carbonate fuel cell. The supply to the melt can be reduced by heat recovery (e.g., by heat exchange benefit 22) prior to providing a carbon monoxide stream from the high temperature hydrogen separation unit 18 to the cathode 26 of the molten carbonate fuel cell 12, as explained below. The temperature of the high pressure carbon dioxide stream of the cathode of the carbonate fuel cell. The temperature of the effluent stream can be reduced by heat recovery (e.g., through heat exchanger 22) prior to providing an effluent stream from catalytic partial oxidation reactor 2 to the molten carbonate fuel cell cathode. Waste heat from the fuel cell can be used to heat one or more of the streams utilized in the system. If necessary, any supplemental system known in the art for cooling molten carbonate fuel can be used to control the temperature of the molten carbonate fuel cell. In one embodiment, the oxidant-containing gas stream fed to the cathode may be heated to a temperature of at least 1 50 ° C or from 1 515 to 35 ° C prior to feeding to the cathode 26. In one embodiment, when an oxygen-containing gas is used, the temperature of an oxygen-containing gas stream is controlled to a temperature from 150 ° C to 350 ° C. To initiate operation of the fuel cell 12, the fuel cell is heated to its operating temperature - sufficient to melt the electrolyte salt to allow one of the carbonate ions to flow. 'Starting as shown in FIG. 1 can be initiated by generating a hydrogen-containing stream in the catalytic partial oxidation reformer 2 and feeding the hydrogen-containing stream through the lines 52 and 34 to the anode 24 of the molten carbonate fuel cell 12. The operation of the molten carbonate fuel cell. In the presence of a conventional partial oxidation catalyst, one of the hydrocarbons described below, including the hydrocarbon stream, is combusted in the catalytic partial oxidation reformer 20, 149088. Doc -28 * 201108498 Knife or different hydrocarbon streams (for example, one of the fuel streams enriched in natural gas) and an oxidant-containing gas to produce a hydrogen-containing machine in the catalytic partial oxidation recombiner 2' where the feed to the catalytic portion The oxidant reformer 2 contains an oxidant gas such that one amount of oxygen is substoichiometric relative to one of the hydrocarbons in the hydrocarbon stream. The flow of the hydrogen containing stream can be controlled by valve 60. As shown in FIG. 2, the fuel cell is produced by generating a hydrogen-containing gas stream in oxidation unit 2 () and feeding the hydrogen-containing stream to anodes 24 of the molten carbonate fuel cell through lines 96, 104, and 34. Heat to its operating temperature. The rate at which the three-way valve 1G2 (iv) contains hydrogen from the oxidation unit feed of the f, _, 1 () 4 to the anode 24 is used. The portion from the heat of the hydrogen containing stream may pass through the heat exchanger 98 via line 96 to provide heat to the first recombination (d) and/or to the hydrocarbon stream comprising the hydrocarbon of the first recombiner. Referring to Figures 1 and 2, the fuel fed to the catalytic partial oxidation reformer can be a liquid- or gaseous hydrocarbon or hydrocarbon mixture, and is preferably the same as the hydrocarbon stream comprising the hydrocarbon supplied to the first reform. Fuel can be routed through the pipeline. The feed to the catalytic partial oxidation reformer 20. In one embodiment, the natural gas and/or hydrogen-rich feed from hydrogen source 64 is fed to a catalytically oxidized recombination fuel. The oxidant fed to the catalytic partial oxidation reformer 2 can be pure oxygen, air or oxygen-enriched air (hereinafter referred to as "oxidant-containing gas"). Preferably, the oxidant gas system air. The oxidant should be provided to the catalytic partial oxidation reactor 20 such that the amount of oxygen in the oxidant (four) is in a substoichiometric amount of the hydrocarbon fed to the catalytic partial oxidation. In a preferred embodiment, the oxidant-containing gas is passed through line 56 from source #42 (4) to the catalytic partial oxidation reactor 2〇. Valve 58 controls the oxidant-containing gas (empty illusion 149088. Doc • 29- 201108498 The rate of feed to the catalytic partial oxidation oxidizer 20 and/or the cathode 26 of the fuel cell 12. In one embodiment, the oxidant-containing gas entering the catalytic partial oxidation reformer 加热 can be heated by exchanging heat with the oxygen-depleted cathode exhaust stream exiting the cathode exhaust port 40. In the catalytic partial oxidation reformer 2, a hydrogen-containing stream is formed by burning a hydrocarbon and an oxidant in the presence of a conventional partial oxidation catalyst, wherein the oxidant is in a substoichiometric amount relative to the hydrocarbon. The helium-containing gas stream formed by the contact of the hydrocarbon with the oxidant in the catalytic partial oxidation recombiner 2 is contained in the fuel cell anode 24 by contact with carbonate ions at one or more of the anode electrodes. Compound. The hydrogen-containing stream from the catalytic partial oxidation reformer 20 preferably does not contain a compound which oxidizes one or more anode electrodes of the anode 24 of the fuel cell 12. The hydrogen-containing gas stream formed in the catalytic partial oxidation reformer 2 is hot and may have at least 700t, or from 700. (: to 11 〇〇. (: or self-healing it to 丨 (10) ❹ it-temperature. In the method of the present invention, a hot hydrogen stream from the catalytic partial oxidation recombiner 20 is used to initiate the molten carbonate fuel cell. The activation is preferred because it enables the temperature of the fuel cell to rise almost instantaneously to the operating temperature of the fuel cell. In one embodiment, heat can be exchanged when the operation of the fuel cell is initiated. The heat exchange gas from the catalytic partial oxidation recombiner 2 is exchanged with the feed to the oxidant gas of one of the cathodes 26.  Referring to Figure 1, a valve 60 can be used to adjust the flow of hot hydrogen containing gas from the catalytic partial oxidation recombiner to the fuel cell 12 while feeding the nitrogen containing stream to the anode 24 by opening the valve. At the beginning comes from high temperature hydrogen separation 149088. Doc -30· 201108498 The flow of one of the hydrogen containing streams may be followed by shutting off valve 60 while reducing or stopping the flow of hydrocarbon feed permeate line 62 and oxidant feed permeate line 56 to catalytic partial oxidation reformer 20. Referring to Figure 2, a three-way throttle valve 102 can be used to regulate the flow of hot hydrogen containing gas from the catalytic partial oxidation recombiner 20 to the fuel cell 12 via line 96, while the argon-containing gas stream is fed by opening valve 36. In the anode 24, the valve 1〇2 can be closed after generating a hydrogen-containing gas stream from the high-temperature hydrogen separation unit 18, while reducing or stopping the hydrocarbon feed permeation line 62 and the oxidant feed permeation line 56 to the catalytic partial oxidation recombiner 20. flow. The continued operation of the fuel cell can then be carried out in accordance with the method of the present invention. The two-way throttle valve 102 controls the flow of the effluent from the catalytic partial oxidation recombiner 2 to the anode 24 or cathode 26. During the start-up, the effluent from the catalytic partial oxidation reformer 20 is enriched in hydrogen, so the effluent is directed to the anode 24 via line 1〇4 after passing through the heat exchanger 98 via line %. The throttle valve 1〇2 controls the flow of the effluent via the line % autocatalytic partial oxidation recombiner 20 to cathode 26 after the initial start and if the catalytic partial oxidation recombiner produces one of the oxides for the cathode. . Mu Nai has always applied the order, before the S 00 elbow 3 虱 & 、, L VI 八 王 burning \ battery 12, available null, net.  The operation of the battery is started by using a starting heater (not shown) to bring the fuel cell to its operation, and the translation of the hydrogen from the source 64 of the power source. Shown. The source of hydrogen is a storage tank that can receive chlorine from the separation unit 18. The source of chlorine can be introduced into the anode of the molten sulphonate fuel cell in a milliwatt-hour pool at a quasi-delta. The starting heater can send hydrogen to the gas 149088. Doc -31 · 201108498 The flow is indirectly heated to the temperature from one cut to (7) (eight). Alternatively, the launch heater can provide hydrogen by incomplete combustion of hydrogen supplied from the hydrogen source 64 to the heater. The engine can be an electric heater or can be a combustion heater. After the operating temperature of the fuel cell is reached, the flow of hydrogen to the fuel cell can be shut off by a valve, and the hydrogen-containing stream can be introduced by opening a valve from the hydrogen to the anode of the fuel cell. The fuel cell is used to start the operation of the fuel cell. In one embodiment, the first recombiner 14 includes a catalytic partial oxidation recombiner that is used to provide hydrogen to the domain carbonate fuel cell upon actuation. The first recombiner 14 can include one or more catalyst beds that allow the first recombiner to be used for autothermal recombination once the molten carbonate fuel cell has reached operating temperature and subsequently used for steam recombination. Once the fuel cell 12 has started operating, the cathode 26 and the anode are "dissipated. The exhaust from the cathode 26 and the anode 24 is hot and from the exhaust gas can be thermally integrated with other cells to produce a thermal product. System, the thermal product 3 system generates all the fuels (4) and sputum sputum (carbonate ions) necessary for the operation of the fuel cell. For example, the method of 十1 and the ten-person T-body/T cabinet in FIG. The system comprises a thermal integrated hydrogen separation and separation device 18, a molten carbon brewing fuel cell: 12, a first recombiner; u and a second recombiner 16 and (in a certain embodiment) a catalytic partial oxidation recombiner 20. , θ & 回 虱 separation device 18 & one or more high temperature hydrogen separation membranes 68 and is coupled to the sulphonate fuel cell 12 in a selective manner. The high temperature hydrogen separation device μ clothing will mainly contain molecules f The hydrogen flow is supplied to the anode of the fuel cell 12; the bucker bucker 24, and from the melt shouting 149088. Doc -32.  The exhaust of the anode of the 201108498 salt fuel cell 12 is supplied to the first recombiner 14. The first recombiner 14 and the second recombiner 16 can be one unit or two units that are operationally light. The first recombiner 14 and the second recombiner 16 may comprise one or more recombination zones. In one embodiment, the first recombiner 14 and the second recombiner 16 comprise a unit of a first recombination zone and a second recombination zone. The smoke stream including the smoke is supplied to the first reformer 14 via line 62 and the anode exhaust gas is mixed with the hydrocarbon. The method is a thermal assembly in which the anode exhaust gas from the first recombiner and/or the hydrocarbon stream supplied to the first recombiner is supplied from the anode exhaust of the exothermic molten carbonate fuel cell 12. The heat of the endothermic recombination reaction in a recombination 14. In one embodiment, a portion of the heat from the anode exhaust is mixed with a hydrocarbon in a heat exchanger located in the first reformer or operatively coupled to the first recombiner. The additional heat of the first recombiner 14 as shown in Figure 2 can be provided from the hot effluent stream from the catalytically partially oxidized recombinant H 2G. At least a portion of the first recombination of the hydrocarbons from the hydrocarbon stream is cracked and/or recombined to produce a feed stream provided to a second reformer 16 via line 70. The second recombiner 16 is operatively coupled to the high temperature hydrogen separation unit 18 and the high 'tank hydrogen knife separation unit produces at least a portion, a majority, at least 75% by volume or to /90% by volume or substantially all of the molten carbonate fuel cell. The hydrogen-containing gas of the anode 24 of η. The high temperature hydrogen separation unit can be positioned after the second reformer μ and before the molten carbonate fuel cell 12. In the preferred embodiment, the warm hydrogen separation unit 18 is a membrane separation unit which is a second reformer 分离 虱 虱 separation unit 18 for separating hydrogen from the recombined product. The separated lanthanide is supplied to the anode 24 of the molten carbonate fuel cell 12. 149088. Doc • 33- 201108498 In one embodiment of the method, the 'hydrocarbon stream contains one or more of any evaporable hydrocarbons' at atmospheric pressure (optionally oxygenated) at 2 (rc liquid) at atmospheric pressure Evaporating at temperatures up to 400 ° C. Such hydrocarbons may include, but are not limited to, petroleum fractions having a boiling range of 50 ° C to 36 (TC), such as naphtha, diesel, jet fuel, gasoline, and Kerosene. In a consistent embodiment, the hydrocarbon stream is calcined. In a preferred embodiment, the hydrocarbon stream is a diesel fuel. In one embodiment, the hydrocarbon stream has a range from five to twenty-five. a carbon number of hydrocarbons. In a preferred embodiment, the hydrocarbon stream contains at least zero. 5, or at least 〇. 6, or at least 〇7 or at least 0. 8 mole fraction of hydrocarbons containing at least five, or at least six or at least seven carbon atoms. The hydrocarbon stream may optionally contain certain hydrocarbons which are gaseous at 25 ° C, such as decane, ethane, propane or other compounds containing from one to four carbon atoms which are gaseous at 25 C. The hydrocarbon stream can be treated prior to feeding to the first reformer 14 and/or heated in the heat exchanger 72 to remove the first recombination to convert higher molecular weight hydrocarbons to lower molecular weights. Any material that has a detrimental effect on any of the hydrocarbons. By way of example, the hydrocarbon stream may have undergone a series of treatments to remove metals, sulfur, and/or nitrogen compounds. In a consistent embodiment of the method, the plume is mixed with natural gas containing at least 2 Torr of volume 0/〇, or at least 50% by volume or at least 8% by volume of carbon dioxide. If necessary, then the money has been processed to remove hydrogen sulfide. In one embodiment, a hydrocarbon stream having at least 20 volumes of carbon dioxide, at least 50% by volume of carbon dioxide, or at least 7% by volume of carbon dioxide can be used as a fuel source. In one embodiment, the hydrocarbon stream can be at least, preferably from 20 〇 to 149088. Doc • 34· 201108498 Recombiner 14 'where the hydrocarbon stream can be ' as set forth below. The hydrocarbon stream is supplied to the first heat exchanger at a temperature of 400 ° C to be heated to a desired temperature. The temperature of the feed to the first reactor 54 can be selected to be as high as possible to evaporate the hydrocarbons without generating coke. . The temperature of the hydrocarbon stream can range from i thief to (10). Alternatively - being (but less preferred), if the sulfur content of the stream is low, the hydrocarbon stream can be fed directly to the first reformer 14 at a temperature below, for example, 15 Gc without heating the Hydrocarbon stream. As shown in Figure 1, the hydrocarbon stream can be passed through one or more heat exchangers to feed the feed. The Heterohydrocarbon stream can be heated by being separated from the cathode 26 of the molten carbonate fuel cell 12 by being fed by line 74 to a heat exchanger to exchange heat with the cathode exhaust stream. The rate at which the cathode exhaust stream is fed to the heat exchangers 72 and 22 can be controlled by adjusting the throttle 76. In a preferred embodiment, a separate anode exhaust stream is fed to one or more recombination zones of the first recombination 14 via a tube. The rate at which the anode exhaust stream is fed to the first reformer can be controlled by adjusting the throttle valve 82. The temperature of the anode exhaust gas may range from about 5 Torr to about 7 Torr, and is preferably about 650 °C. The anode exhaust stream contains hydrogen, steam, and reaction products from the oxidation of the fuel fed to the anode 24 of the fuel cell 12, as well as unreacted fuel. In one embodiment, the anode exhaust stream contains at least 〇 5, or at least 〇 6 or at least 莫 7 moles of hydrogen. Hydrogen fed to the anode exhaust stream of the first recombiner 14 or the recombination zone of one of the first reformers can help prevent the formation of coke in the first reformer. In one embodiment, the anode exhaust stream comprises from 〇 至 to about 3 3, or from 0. 001 to about 0. 25 or from 〇1 to about 〇 2 mole fraction of water (as 149088. Doc -35- 201108498 Steam). In addition to hydrogen, the vapor present in the anode exhaust stream fed to the first reformer 14 or a recombination zone of one of the first reactors can also help prevent the formation of a coke-recombiner. The anode exhaust stream may contain sufficient, coked coking and sufficient steam to recombine a majority of the hydrocarbons in the hydrocarbon stream to methane, hydrogen and carbon monoxide. Thus, less steam may be required in the first recombiner and/or the second recombiner to recombine the hydrocarbons. Optionally, steam may be fed via line 84 to the first recombiner 14 or one of the reconfigurable recombination zones for mixing with the hydrocarbon stream in the first recombiner or the recombination zone of the first recombination. Steam may be fed to the first recombiner (4) - the recombination zone of the first recombinator to inhibit or prevent coke formation in the first weight per unit and optionally for recombination achieved in the first recombiner Reverse shoulders. In the embodiment, the steam is fed to the first recombiner [or (4)-recombiner recombination zone at a rate, wherein the lock steaming added to the first recombiner is added to the At least twice or at least three times the amount of carbon in the smoke stream of the first recombiner. The total steam added to the first-recombiner may comprise steam from the anode exhaust, steam from an external source (e.g., through the official line 84), or a mixture thereof. Providing at least 2:1, or at least one at least 3" or ^•5:1 in the first_recombiner 14 or the _re-powered two= group zone, the steam and the carbon molar ratio can suppress coke in the The first weight = the formation of the middle. The throttling_ can be used to control the rate at which the vapor permeates through the line feed-recombiner 14 or the first recombiner - the recombination zone. The anode vent contains a large amount of gas, so less 隹 occurs during recombination: use: ' Feed to the first-recombiner...the amount of steam selected can be;; the amount of steam used in the conventional recombination unit. 149088. Doc -36 - 201108498 Steam can be fed to the fourth group 14 at a temperature of at least 125 ° C, preferably from 15 ° C to 300 ° C, and can have a pressure from 〇 to 〇 5 (10) & The money has a pressure equal to or lower than the pressure of the anode exhaust stream fed to the first reformer, as set forth herein. It can be heated by at least 1_0 MPa, preferably 丨. The high pressure water of one pressure of 5 Mpa to 2_0 MPa (by passing the high pressure water through the heat exchanger 9 via line 88) produces steam. The high pressure water is heated to exchange high pressure steam by exchanging heat with the cathode exhaust gas fed after the cathode exhaust feed has been passed through the heat exchanger 72 through line 74. Alternatively, the cathode exhaust can be fed directly to a heat exchanger 9 (not shown) or one or more heat exchangers. If more than one heat exchanger is utilized, the high pressure steam can then be fed to line 84 via line 92 after exiting heat exchanger 90 or the final heat exchanger. The high pressure steam can be depressurized to a desired pressure by expanding the high pressure steam through an expander and then fed to the first reformer. Alternatively, steam for use in the first reformer can be produced by feeding low pressure water through one or more heat exchangers 90 and passing the resulting vapor to the first reformer 14. Depending on the situation, the high pressure steam that is not utilized in the first or second recombiner 16 may pass through other power devices (eg, a turbine (not shown with any unused high pressure carbon dioxide stream or, as the case may not be, high pressure) The carbon dioxide stream expands together. The power source can be used to generate electricity and/or electricity other than electricity generated by the fuel cell 12. The power generated by the power source and/or fuel cell can be used in the compressor 94 and/or the method of the present invention. Any other compressor used to supply power. The flow, optional steam and anode exhaust flow are not in vapor form in the vaporization 149088. Any hydrocarbon of doc-37·201108498 is lysed and contacted with a recombination catalyst in a recombination zone of the first recombiner 14 or the first recombiner at a temperature effective to form a feed. The recombination catalyst can be a conventional recombination catalyst and can be any of the catalysts known in the art. Typical recombination catalysts that may be used include, but are not limited to, νιπ transition metals, particularly nickel and one of the carriers or substrates that are inert under high temperature reaction conditions. Suitable inert compounds for use as a carrier for the high temperature recombination/hydrocracking catalyst include, but are not limited to, alpha alumina and oxidation. In a preferred embodiment, the hydrocarbon stream, the anode exhaust, and the optional vapor are mixed from about 5 ° C to about 65 (TC or from about 550 t: to 600. (at one temperature, mixed with a catalyst) And contacting, wherein all of the heat necessary for the recombination reaction is supplied by the anode exhaust. In one embodiment, the hydrocarbon stream, the optional vapor and the anode exhaust stream are at least 4 ° C, or from 450 ° C to 650 ° C is mixed with and contacted with a catalyst at a temperature ranging from one of 500 ° C to 600 ° C. The anode exhaust stream fed from the self-heating molten carbonate fuel cell 12 is supplied to the first recombiner 14 or The heat of the recombination zone of one of the first recombiners drives the endothermic cracking and recombination reaction in the first recombiner. The molten carbonate fuel cell 12 is fed to the first recombiner 14 and/or the first recombiner - The anode exhaust stream of the recombination zone is extremely hot, having a temperature of at least 500 ° C, typically having a temperature from 550 ° C to 700 t or from 600 ° C to 65 CTC. Thermal energy from the molten carbonate fuel cell 12 to the first The transfer of the recombiner 14 or the recombination zone of one of the first recombiners is quite effective due to the fuel cell Thermal energy contained in the anode exhaust stream, and by directly mixing the anode exhaust stream and the steam and hydrocarbon stream 14 is transmitted to one of the first or the first recombinant reformer 149,088. Doc -38 - 201108498 Recombination zone for the mixture of hydrocarbon streams, optional steam and anode exhaust streams. In a preferred embodiment of the method set forth in 裎徂白文, the anode exhaust stream is supplied from a mixture of the plume, optional steam and anode exhaust to produce at least 99% or substantially all of the heat required for the feed. . In a particular preferred embodiment, no other heat source other than the anode exhaust stream is provided to the first reformer 14 to convert the hydrocarbon stream to feed. In a detailed example, the anode exhaust stream, hydrocarbon stream, and optional steam are at first. The pressure in the recombiner 14 when in contact with the recombination catalyst can be from 0. 07 MPa to 3. The range of 0 MPa. If the high pressure steam is not fed to the first reformer ", the anode exhaust stream, the hydrocarbon stream, and the combustible wire may be at a pressure at the lower end of the range (usually from 0. 07 MPa to 〇 5 Mpa or Μρ^〇 3 MPa) is contacted with the recombination catalyst in the first-recombiner. If high pressure steam is fed to the first reformer 14, the anode exhaust stream, hydrocarbon stream and steam may be at the more extreme end of the pressure range (typically from 1 MPa to 3 〇Μ ρ & or from j 5 Mb to 2 〇) At MPa), it is in contact with the recombination catalyst. Referring to Figure 2, the first recombiner 14 can be heated to above 63 by exchanging heat with the effluent from the catalytic partial oxidation recombiner 20 via line 96. <>c, or from 65 (TC to 90 (TC or from 700. (: to 80 (TC temperature. Line 96 is operatively coupled to heat exchanger 98. Heat exchanger 98 may be part of line 96) The heat exchanger 98 can be located in the first recombiner 14 or connected to the first recombiner to allow heat exchange with the hydrocarbon stream entering the first recombiner. The throttle valve 100 and the three-way throttle can be adjusted 102 controls the rate at which the effluent is fed to the first reformer 14 from the catalytic partial oxidation reformer 20.

在至少 500°C、或自 550°C 至 950。(：、或自 600。(：至 80CTC 149088.doc •39· 201108498 或自65(TC至75(TC之一溫度下於第一重組器i4中接_ 流、洛汽 '觸媒及陽極排氣流可裂解及/或重組該等煙之 至少-部分且形成進料。裂解及/或重組烴流中之烴減少 烴流中之烴化合物中之碳原子之數目，藉此產生具有❹ 之分子量之烴化合物。在-實施例中，烴流可包括含有至 少5個、或至少6個或$ /丨少7 山rc 飞至v 7個奴原子之烴，其等轉化為可 用作至第二重組器16之進料之含有至多4個、或至多3個或 至多2個碳原子之烴。在—實施例中，該煙流中之煙可在 第一重組器14或該第一重組器之一重組區中反應以使得自 該第-重組器產生之進料可由不多於、或不多於〇〇5或 不夕於0.01莫耳分率之具有四個碳原子或更多碳原子之煙 組成。在一實施例中，柄、、* 士 > ___ J r 垤仙·中之烴可經裂解及/或重组以 使得自烴流中之烴產生之進料中之至少〇 7、或至少“、 或至少0.9或至少〇.95莫耳分率的所得烴係甲烧。在一實施 例中，裂解及/或重组烴流中之煙產生進料中之煙具有至 多1.3、至多1.2或至多L1之—平均碳數目之一進料。 如上所述，來自陽極排氣流之氫及蒸汽及添加至第一重 組器14之額外蒸汽在裂解烴以形成進料時抑制焦炭在第一 重’”且益中之形成。在一較佳實施例中，選擇陽極排氣流、 烴流及蒸汽進料至第一重組器14之相對速率因此陽極排 ，流中之氫及蒸汽以及經由管線84添加至該第一重組器之 蒸汽阻止焦炭在該第一重組器中之形成。 在一實施例中，在至少„ 仕主V 500 C、或自550°C至70(TC或自 喊至65吖之一溫度下於第-重組器“中使烴流、蒸汽 149088.doc 201108498 及陽極排氣與重組觸媒接觸亦可實現烴流令之烴與第一重 組器:u内所產生之進料之至少某些重組而產生氣及碳氧化 物（特定而言，—氧化碳）。重組之量可係大量，其中在第 一重組器14或該第—重組器之重組區中自裂解及重租 導致之進料可含有至少⑽、或至少Q1或至少⑶莫耳分 率一氧化碳。 ” 可選擇第-重組器14或該第一重組器之一重組區中之溫 度及魔力條件，因此該第一重組器中所產生之進料包括在 2〇°C下為氣態、通常含有⑴個碳原子之輕烴。在—較佳 實施例中，由該第-重組器產生之進料（下文稱為「 重組進料」）甲之烴由至少〇.6、或至少0.7、或至少"或 至少0.9莫耳分率甲烧組成。蒸汽重組進料亦包：來自陽 極排氣流之氫，且若在第一重組器中實現進一步之重組， 則，括來自經重組烴之氫。蒸汽重組進料亦包括來自:極 排氣流且視情況來自重組器蒸汽進料之蒸 “、U 右弟—重衾且 器14或該第一重組器之一重組區中實現大量重組，則提供 至第二重組器16之自該第一重組器產生之進料可包括除I 氧化碳之外的一氧化碳。 在本發明之方法中，蒸汽重組進料係自第-重組器14提 供至透過管線70以操作方式連接至該第一重組器之第二 組器16。退出第一重組器14之蒸汽重組進料可具^ ^ 5〇〇t至65〇t或自5贼至之—溫度。在將退:第一 重組器14之蒸汽重組進料進料至第二重組器16之前，可 由在進料至第二重組器16之前於—個或多個熱交換㈣中曰 149088.doc -41 · 201108498 父換”.、來降低退出第一重組器之該蒸汽重組進料之溫度。 視隋况，不在進入該第二重組器之前冷卻該蒸汽重組進 料。在第一重組器14藉由其他源（例如，如圖2中所顯示， 來自催化部分氧化重組器2〇之蒸汽及/或熱）加熱之實施例 中退出第—重組器之進料可具有自650。(：至950°C、或自 700°C至90〇t或自75〇t至8〇〇t：之一溫度。 可藉由與進料至該系統中之水交換熱、冷卻進料且產生 可進料至第一重組器14之蒸汽來冷卻該蒸汽重組進料，如 上文所闡述。若利用多於一個熱交換器9〇 ,則該蒸汽重組 進料及水/蒸汽可逐次進料至熱交換器中之每一者，較佳 以對流方式以冷卻該進料且加熱該水/蒸汽。可將該蒸 汽重組進料冷卻至自150。(：至65〇。(：、或自15〇<>(：至3〇〇<>(：、 或自400。(：至650。(：或自450。(：至550t之一溫度。 經冷卻蒸汽重組進料可自熱交換器9〇進料至壓縮機94， 或在另一實施例中可直接進料至第二重組器16。另一選擇 為（但較不佳），退出第一重組器14或該第一重組器之—重 組區之蒸汽重組進料可不經冷卻即進料至壓縮機94或第二 重組器16。壓縮機94係能夠在高溫下操作之一壓縮機，且 較佳係一可自市場購得之StarR〇t〇r壓縮機。蒸汽重組進料 可具有至少0.5 MPa之一壓力及自4〇〇。(：至800。(：、較佳自 400 C至650 C之一溫度。該蒸汽重組進料可由壓縮機94壓 縮至至少0.5 MPa、或至少10 MPa、或至少1.5 MPa、或至 少2 MPa、或至少2.5 MPa或至少3 MPa之一壓力以維持第 二重組器16之重組區108中之充足壓力。在一實施例中， 149088.doc • 42- 201108498 在將進料流提供至第二重組器之前，將該蒸汽重組進料壓 縮至自0.5 MPa至6.0 MPa之一壓力。 包括氫、輕烴、蒸汽及（視情況）一氧化碳之視情況壓 縮、視情況冷卻之蒸汽重組進料係進料至第二重組器j 6。 该蒸汽重組進料可具有至少0.5 MPa之一壓力及自400°C至 8〇0 C '較佳自4〇〇它至65〇。(：之一溫度。在一實施例中， 若必須，則可在自第一重組器14產生之蒸汽重組進料退出 壓縮機94之後藉由使該進料之一部分循環穿過熱交換器9〇 及/或72來增加自該第一重組器產生之蒸汽重組進料之溫 度。 視情況，若對於重組該進料而言為必須，則可將額外蒸 汽添加至第二重組器16之重組區1〇8中以用於與由該第一 重組器產生之蒸汽重組進料混合。在一較佳實施例十，可 藉由透過管線ι10將高壓水自水入口管線88注射至壓縮機 94中來添加額外蒸汽以用於在該壓縮機中壓縮該進料時與 該進料混合。在一實施例(未顯示)令，可藉由在熱交換器 90中將高壓水與進料混合來將該高壓水注射至該進料中。 在另-實施例(未顯示)中，可在將該進料傳遞至熱交換器 9〇之前或之後抑或在將該進料傳遞至盤縮機“之前或之 於管線110中將高壓水注射至進料中。在-實施例中，可 將高壓水注射至管線70中或注射至墨縮機94中或注射於敎 ^換益90中，其中該壓縮機或該熱交換器不包含於該系統 該高壓水藉由與蒸汽重組進料 混合而經加熱 以形成蒸 149088.doc -43- 201108498 汽’且該蒸汽重組進料藉由與該水混合而經冷卻。藉由注 射於蒸汽重組進料中之水提供至其中之冷卻可消除或減少 對熱交換器90之需求，較佳將用於冷卻蒸汽重組進料之熱 交換器之數目限制至至多一個。 另一選擇為(但較不佳），可將高壓蒸汽注射至第二重电 器之重組區1()8中或注射至至該第二重組器之管線川中 以與H重組進料混合。高壓蒸汽可係藉由在熱交換器％ 中加熱透過水人口管線88注射至該系統中之高壓水（藉由 與退出第-重組器14之進料交換熱）而產生之蒸汽。高壓 蒸汽可透過管線112進料至第二重組器16。節流閥ιΐ4可用 於控制洛汽至該第二重組器之流動。該高壓蒸汽可具有類 似於正進料至該第二重組器之進料之壓力之一麼力。另 選擇為’肖高壓蒸汽可進料至管線7G以在該進料進料至碑 縮機94之前與料料混合，因此蒸汽與進料线合物可二 起屋縮至―敎壓力。豸高麼蒸汽可具#自200X^ 5001 之一溫度。 可選擇並控制向壓水或高壓蒸汽進料至該系統中之速率 以將對最佳化重組器中之反應以產生—含氫氣流有效之一 蒸汽量提供至第-重組器;u及/或第：重組器16。可心 調整節流閥116及118(其等控制水進料至該系统之速率曰)或 藉由調整節流閥8 6、i 2 0及；L i 4 (其等控制蒸汽進料至第一 重組器14、第二重組器16之速率)來控制將除陽極排氣流 中之瘵 >飞之外的蒸汽提供至第一重組器14之速率。可將蒸 汽供應至該系統中之額外組件（例如，一渦輪機）。 149088.doc -44 - 201108498 若將南壓水注射至第二重組器16中，則可調整節流閥 114及120以控制水透過管線112注射至第二重組器中之速 率。若將咼壓蒸汽注射至第二重組器16中或注射至管線7〇 中’則可调整節流閥114、116及118以控制蒸汽注射至第 二重組器16中或注射至管線70中之速率。可調整蒸汽之流 動以提供蒸汽與碳之至少2:1、或至少2.5d、或至少3:1或 至少3·5:1之一莫耳比。 藉由第一重組器產生之蒸汽重組進料及（視情況）額外蒸 汽係進料至第二重組器16之重組區1〇8中。該重組區可且 較佳確實在其中含有一重組觸媒。該重組觸媒可係一習用 蒸汽重組觸媒且可係在此項技術中已知。可使用之典型蒸 汽重組觸媒包含但不限於νιπ族過渡金屬，特定而言鎳。 通*可期望將該等重組觸媒承载於一耐火基材（或載體） 上。該載體（若使用）較佳係一惰性化合物。用作一載體之 適合惰性化合物含有週期表之ΠΙ及IV族元素，例如A1、At least 500 ° C, or from 550 ° C to 950. (:, or from 600. (: to 80CTC 149088.doc •39·201108498 or from 65 (TC to 75 (TC at one temperature in the first recombiner i4 in the _ stream, Luoqi 'catalyst and anode row The gas stream can cleave and/or recombine at least a portion of the smoke and form a feed. The hydrocarbons in the cracked and/or reformed hydrocarbon stream reduce the number of carbon atoms in the hydrocarbon compound in the hydrocarbon stream, thereby producing a a hydrocarbon compound of a molecular weight. In an embodiment, the hydrocarbon stream may comprise a hydrocarbon containing at least 5, or at least 6 or at least 7 rc to v 7 slave atoms, which are converted to The feed of the second reformer 16 contains hydrocarbons of up to 4, or up to 3 or up to 2 carbon atoms. In an embodiment, the smoke in the stream may be at the first recombiner 14 or the first Recombining in one of the recombiners to react such that the feed produced from the first-recombiner can have no more than, or no more than, or no more than 0.01 moles of four carbon atoms or more The composition of the smoke of a carbon atom. In one embodiment, the hydrocarbon of the stalk, * 士 > ___ J r 垤 · can be cracked and/or recombined to be from the hydrocarbon stream The resulting hydrocarbon-derived toluene of at least 、7, or at least ", or at least 0.9 or at least 〇.95 mole fraction of the hydrocarbon-derived feed. In one embodiment, in the cracked and/or recombined hydrocarbon stream The smoke in the feed produces a feed having up to 1.3, at most 1.2, or at most L1 - one of the average carbon numbers. As described above, hydrogen and steam from the anode exhaust stream and additional steam added to the first reformer 14 The formation of coke in the first weight is avoided when the hydrocarbon is cracked to form a feed. In a preferred embodiment, the relative anode exhaust stream, hydrocarbon stream, and vapor feed to the first recombiner 14 are selected. The rate thus the anode row, the hydrogen and vapor in the stream, and the steam added to the first reformer via line 84 prevents the formation of coke in the first reformer. In one embodiment, at least „V. V 500 C Hydrocarbon flow can also be achieved by contacting the hydrocarbon stream, steam 149088.doc 201108498 and the anode exhaust gas with the recombination catalyst from 550 ° C to 70 (TC or from one to 65 ° at a temperature of 65 ° in the first reactor) Having the hydrocarbon and the first recombiner: at least some of the feeds produced in u recombined Anger and carbon oxides (specifically, carbon monoxide). The amount of recombination can be large, wherein the feed caused by self-cracking and re-leasing in the recombination zone of the first recombiner 14 or the first recombiner can contain At least (10), or at least Q1 or at least (3) molar fraction of carbon monoxide. "The temperature and magic conditions in the recombination zone of the first recombiner 14 or the first recombiner may be selected, thus resulting in the first recombiner The feed comprises a light hydrocarbon which is gaseous at 2 ° C and usually contains (1) carbon atoms. In a preferred embodiment, the feed produced by the first recombiner (hereinafter referred to as "recombinant feed") The hydrocarbon of Form A consists of at least 6.6, or at least 0.7, or at least " or at least 0.9 moles of A. The steam recombination feed also includes hydrogen from the anode exhaust stream and, if further recombination is achieved in the first reformer, hydrogen from the recombined hydrocarbon. The steam recombination feed also includes a large amount of recombination from the extreme exhaust stream and, as the case may be, the steam from the recombiner steam feed, the U right brother, the heavy reactor, or the recombination zone of one of the first reformers. The feed from the first reformer provided to the second reformer 16 may include carbon monoxide other than carbon monoxide. In the process of the present invention, the steam recombination feed is supplied from the first-recombiner 14 to Line 70 is operatively coupled to the second set of first recombiners 16. The steam recombination feed exiting the first recombiner 14 can be from ^^5〇〇t to 65〇t or from 5 thieves to temperature Before retreating: the steam recombination feed of the first reformer 14 is fed to the second recombiner 16, it may be in one or more heat exchanges (four) before being fed to the second recombiner 16 曰149088.doc -41 · 201108498 The parent changed "." to reduce the temperature of the steam recombination feed exiting the first recombiner. The steam recombination feed is not cooled prior to entering the second reformer, as appropriate. In the embodiment where the first recombiner 14 is heated by other sources (e.g., as shown in Figure 2, steam and/or heat from the catalytic partial oxidation recombiner 2), the feed to the first recombiner may have Since 650. (: to 950 ° C, or from 700 ° C to 90 ° t or from 75 ° t to 8 〇〇 t: one of the temperatures. The heat can be exchanged with the water fed to the system, cooling the feed and Producing steam that can be fed to the first reformer 14 to cool the steam recombination feed, as set forth above. If more than one heat exchanger 9 is utilized, the steam recombination feed and water/steam can be fed sequentially To each of the heat exchangers, preferably in a convection manner to cool the feed and heat the water/steam. The steam recombination feed can be cooled to from 150. (: to 65 〇. (:, or from 15〇<>(: to 3〇〇<>(:, or from 400. (: to 650. (: or from 450. (: to 550t one temperature. Recombination feed through cooling steam can be The heat exchanger 9 is fed to the compressor 94, or in another embodiment can be fed directly to the second recombiner 16. Another option is (but less preferred) exiting the first recombiner 14 or the first A recombination zone steam recombination feed can be fed to compressor 94 or second recombiner 16 without cooling. Compressor 94 is capable of operating a compressor at elevated temperatures, and A StarR〇t〇r compressor commercially available from the market. The steam recombination feed can have a pressure of at least 0.5 MPa and from 4 〇〇 (: to 800. (:, preferably from 400 C to 650 C) One of the temperatures. The steam recombination feed may be compressed by compressor 94 to a pressure of at least 0.5 MPa, or at least 10 MPa, or at least 1.5 MPa, or at least 2 MPa, or at least 2.5 MPa or at least 3 MPa to maintain a second recombination Sufficient pressure in the recombination zone 108 of the vessel 16. In one embodiment, 149088.doc • 42-201108498 compresses the steam recombination feed to from 0.5 MPa to 6.0 before providing the feed stream to the second reformer. One pressure of MPa. The hydrogen recombination feed comprising hydrogen, light hydrocarbons, steam and, as the case may be, carbon monoxide, optionally cooled, is fed to a second reformer j 6. The steam recombination feed may have at least One pressure of 0.5 MPa and from 400 ° C to 8 〇 0 C ' is preferably from 4 〇〇 to 65 〇. (: one temperature. In one embodiment, if necessary, from the first recombiner 14 generated steam recombination feed exiting compressor 94 by partially passing the feed Passing through heat exchangers 9 and/or 72 to increase the temperature of the steam recombination feed produced from the first reformer. Optionally, additional steam may be added to the second if necessary to recombine the feed. The recombination zone 1 8 of the recombiner 16 is for mixing with the steam recombination feed produced by the first recombiner. In a preferred embodiment 10, high pressure water can be supplied from the water inlet line 88 via line ι10. Injection into compressor 94 adds additional steam for mixing with the feed as it is compressed in the compressor. In an embodiment (not shown), the high pressure water can be injected into the feed by mixing high pressure water with the feed in heat exchanger 90. In another embodiment (not shown), the high pressure water may be injected before or after the feed is transferred to the heat exchanger 9 or before the feed is transferred to the coiler. In the feed, in the embodiment, high pressure water may be injected into the line 70 or injected into the melter 94 or injected into the smelting machine 90, wherein the compressor or the heat exchanger is not included in The high pressure water of the system is heated by mixing with a steam recombination feed to form a steam 149088.doc -43 - 201108498 steam and the steam recombination feed is cooled by mixing with the water. Recombined by injection in steam The cooling provided to the water in the feed eliminates or reduces the need for heat exchanger 90. Preferably, the number of heat exchangers used to cool the steam recombination feed is limited to at most one. Poor), high pressure steam may be injected into the recombination zone 1 () 8 of the second heavy appliance or injected into the pipeline of the second recombiner to mix with the H recombination feed. The high pressure steam may be by heat The exchanger % is heated to the system through the water population line 88 The high pressure water (the steam generated by exchanging heat with the feed exiting the first-recombiner 14). The high pressure steam can be fed through line 112 to the second reformer 16. The throttle valve ι4 can be used to control the steam to the The flow of the second reformer. The high pressure steam may have a force similar to the pressure of the feed being fed to the second reformer. Alternatively, 'Xiao high pressure steam may be fed to line 7G to The material is mixed with the material before the feed to the indenter 94, so the steam and the feed compound can be contracted to the pressure of 敎. The high steam can have a temperature of one from 200X^5001. Controlling the rate at which pressurized water or high pressure steam is fed to the system to provide a quantity of steam effective to the reaction in the optimized reformer to produce a hydrogen-containing stream to the first-recombiner; u and/or: Recombiner 16. The throttle valves 116 and 118 can be adjusted (such as controlling the rate at which water is fed to the system) or by adjusting the throttle valves 86, i 2 0 and L i 4 (their control steam) The rate of feeding to the first recombiner 14 and the second recombiner 16 is controlled to control the enthalpy in the anode exhaust stream> The steam outside is supplied to the rate of the first recombiner 14. The steam can be supplied to additional components in the system (eg, a turbine). 149088.doc -44 - 201108498 If the South pressurized water is injected into the second recombiner In step 16, the throttle valves 114 and 120 can be adjusted to control the rate at which water is injected into the second recombiner through the line 112. If helium vapor is injected into the second recombiner 16 or injected into the line 7' The throttle valves 114, 116, and 118 can be adjusted to control the rate at which steam is injected into the second recombiner 16 or injected into the line 70. The flow of steam can be adjusted to provide at least 2:1, or at least 2.5d of steam and carbon. , or at least 3:1 or at least 3·5:1 one molar ratio. The steam recombination feed produced by the first reformer and, as the case may be, additional steam is fed to the recombination zone 1〇8 of the second reformer 16. The recombination zone may, and preferably does, contain a recombination catalyst therein. The recombination catalyst can be a conventional steam recombination catalyst and can be known in the art. Typical vapor recombination catalysts that may be used include, but are not limited to, νιπ transition metals, specifically nickel. It is contemplated that the recombination catalysts are carried on a refractory substrate (or carrier). The carrier, if used, is preferably an inert compound. Suitable inert compounds for use as a carrier contain elements of the Periodic Table and Group IV elements, such as A1.

Sl、Τι、Mg、ce及Zr之氧化物或碳化物。 /亥蒸汽重組進料及（視情況）額外蒸汽在對形成含氫及二 氧化碳之—經重组產物氣體有效之一溫度下於重組區108 中〃重組觸媒混合並接觸。該經重組產物氣體可藉由蒸汽 f組進料中之烴而形成。該經重組產物氣體亦可藉由使蒸 ^與進料中之一氧化碳發生水煤氣轉化反應而形成及/或 藉由蒸π重組該進料而產生。在一實施例中，若第一重組 ㈣或該第一重組器之一重組區中實現了大量重組且該蒸 汽重組進料含有大量一氧化碳’則第二重組器16可更充當 I49088.doc -45· 201108498 一水煤氣轉化反應器。該經重組產物氣體包括氫及至少一 種碳氧化物。在一實施例中，該經重組產物氣體包括氣態 烴、氫及至少一種碳氧化物。可處於該經重組產物氣體中 之碳氧化物包含一氧化碳及二氧化碳。 在一實施例中，來自催化部分氧化重組器2〇之流出物之 熱可與正提供至及/或處於重組區108中之蒸汽重組進料流 進行熱交換。來自催化部分氧化重組器2〇之流出物之一溫 度可在自750°C至1050t、或自800eC至1000t或自850°c 至900。(：之範圍。來自該流出物之熱可將第二重組器“之 重組區108加熱至自約50(rc至約85〇ΐ：或自約55〇c>c至 700 C之一溫度。第二重組器16之重組區1〇8中之一溫度可 足以重組來自第-重組器14之大致所有或所有進料以產生 包括氫及至少一種碳氧化物之經重組產物氣體。 該經重組產物氣體可 逸入以i是/Mr七-V 人^ .Oxides or carbides of Sl, Τι, Mg, ce and Zr. /Hai steam recombination feed and, as the case may be, additional steam is combined and contacted in the recombination zone 108 in a recombination zone 108 at a temperature effective to form a hydrogen-containing and carbon dioxide-reacted product gas. The recombined product gas can be formed by the hydrocarbons in the steam f group feed. The reformed product gas may also be formed by subjecting the vapor to a water gas shift reaction of one of the carbon oxides in the feed and/or by steaming the π to recombine the feed. In one embodiment, the second recombiner 16 can act more as I49088.doc-45 if the first recombination (four) or a recombination zone in one of the first recombiners achieves substantial recombination and the vapor recombination feed contains a significant amount of carbon monoxide. · 201108498 One water gas conversion reactor. The reformed product gas comprises hydrogen and at least one carbon oxide. In one embodiment, the reformed product gas comprises a gaseous hydrocarbon, hydrogen, and at least one carbon oxide. The carbon oxides that may be present in the reformed product gas comprise carbon monoxide and carbon dioxide. In one embodiment, the heat from the effluent from the catalytic partial oxidation reformer 2 can be heat exchanged with the steam reforming feed stream being provided to and/or in the reforming zone 108. The temperature of one of the effluents from the catalytic partial oxidation reformer 2 can range from 750 ° C to 1050 t, or from 800 eC to 1000 t or from 850 ° C to 900. (The range of: The heat from the effluent may heat the recombination zone 108 of the second recombiner to a temperature from about 50 (rc to about 85 Torr: or from about 55 〇 c > c to 700 C). The temperature of one of the recombination zones 1 〇 8 of the second recombiner 16 may be sufficient to recombine substantially all or all of the feed from the first recombiner 14 to produce a recombined product gas comprising hydrogen and at least one carbon oxide. The product gas can escape to i is /Mr seven-V human ^.

重組區108中之經重組產物氣體、 系氫導管124自與第二重組器16之 物氣體、進料及蒸汽中之非氫化 149088.doc •46· 201108498 合物之氣體連通㈣。“壁對氫（元素及/或分子）選擇性 地可透4吏传重組區1〇8中之氣可穿過薄膜Μ之薄膜壁至 氫導“24 @重組區中之其他氣體則藉由該薄膜壁被阻 止傳遞至氫導管β可藉由調整第二重組器“中之壓力來增 加或減少跨越高溫氫分離裝置18之氫通量。第二重組器Μ 中之壓力可由陽極排氣流進料至第—重組器14之速率控 制。 > 圖3，來自第二重組器16之進料經由管線進料至 同'瓜氫刀離裝置18。高溫氫分離裝置18可包括對氫（呈分 子或元素形式）選擇性地可透之一構件。在一較佳實施例 中’該高溫氫分離裝置包括對氫選擇性地可透之一薄膜。 在一實施例中，高溫氫分離裝置包括一管狀薄膜，其塗佈 有對氫選擇性地可透之鈀或鈀合金。 經由官線122進入高溫氫分離裝置18之氣流可包含氫、 碳氧化物及烴。該氣流可接觸管狀氫分離薄膜68且氫可穿 過一薄膜壁至位於薄膜68内之氫導管124。該薄膜壁將氫 導官124自與非氫化合物之氣體連通分離且對氫（元素及/或 刀子）選擇性地可透，使得所進入氣體中之氫可穿過該薄 膜壁至氫導管124，而其他氣體則藉由該薄膜壁被阻止傳 遞至該氫導管。 圖1及圖2中之高溫管狀氫分離薄膜68可包含一載體，其 塗佈有對氫選擇性地可透之一金屬或合金之一薄層β該載 體可由滲透氫之一陶瓷或金屬材料形成。多孔不銹鋼或多 孔氧化銘係用於薄膜68之載體之較佳材料。塗佈於該載體 149088.doc •47· 201108498 上之氫選擇金屬或合金可係選自以下VIII族金屬，包含但 不限於Pd、Pt、Ni、Ag、Ta、V、Y、Nb、Ce、ln、Ho、 La、Au及RU(特定而言呈合金形式）。鈀及鈀合金為較佳。 本方法中所使用之一特定較佳薄膜68具有一極薄鈀合金 膜，該膜具有塗佈一多孔不銹鋼載體之一高表面積。使用 美國專利第6,1 52,987號中所揭示之方法可準備此類型之薄 膜。具有一高表面積之鉑或鉑合金之薄膜將亦適合於作為 氫選擇材料》 將第二重組器16之重組區1〇8内之壓力維持在顯著高於 管狀薄膜68之氫導管124内之壓力之一位準處，以使得強 迫氫自第二重組器10之重組區1〇8穿過薄膜壁至氫導管η* 中。在一實施例中，將氫導管124維持在大氣壓下或接近 大氣壓，且將重組區108維持在至少〇 5 Mpa、或至少1〇 MPa、或至少2 MPa或至少3 Mpa之一壓力下。如上所述， :藉由用壓縮機94壓縮來自第一重組器14之進料且將處於 高壓之進料混合物注射至重組區1〇8中來將重組區1〇8維持 在此等經提高之壓力下。另一選擇為，可藉由如上文所闡 述使高壓蒸汽與進料混合且將高壓混合物注射至第二重組 器16之重組區1〇8令來將重組區1〇8維持在此等高壓下。另 一選擇為，可藉由在第一重組器14或該第一重組器之一重 :區中將高壓蒸汽與烴流混合且直接或透過一個或多個熱 交換器90將該第一重組器中所產生之一高壓進料注射至第 二重組器16中來將重組區1〇8維持在此等高壓下。可將第 二重組器16之重組區108維持在至少〇5 Μρ&、或至少^〇 149088.doc • 48 - 201108498 MPa、或至少2.0 MPa或至少3.0 MPa之一壓力下。 蒸汽重組進料及（視情況）額外蒸汽在第二重組器16之重 組區108中與重組觸媒混合並接觸時所處之溫度為至少 4〇〇 C，且較佳可在自4〇〇〇c至65〇<Jc之範圍，最佳在自 450 C至550 C之一範圍中。典型蒸汽重組器係在750°C或 更高之溫度下運行以獲得足夠高之平衡轉化。在本方法 中，藉由將氫自重組區1〇8連續移除至薄膜68之氫導管124 中（且因此自第二重組器16移除）來在40CTC至050°C之重組 器操作溫度範圍中朝向氫之產生驅動重組反應。以此方 式，本方法可在無平衡限制之情形下獲得反應物至氫之近 乎το全之轉化。400°C至650。(：之一操作溫度亦有利於變換 反應，從而將一氧化碳及蒸汽轉化為更多氫，然後穿過薄 膜之薄膜壁將該氫自重組區1〇8移除至氫導管124中。可在 第二重組器16中達成藉由重組及水煤氣轉化反應之烴及一 氧化碳至氫及二氧化碳之近乎完全轉化，此乃因由於自該 第二重組器連續移除氫而決不會達到平衡。 在一實施例中，自第一重組器14及/或該第一重組器之 一重組區提供至第二重組器16之蒸汽重組進料供應熱以驅 動該第二重組器中之反應。至第二重組器16之自第一重組 态14及/或該第一重組器之一重組區產生之蒸汽重組進料 可含有充足之熱能以驅動該第二重組器中之反應，且可具 有自400 C至950 C之一溫度。自第一重組器14及/或該第 一重組器之一重組區產生之蒸汽重組進料之熱能可超出驅 動第二重組器16中之反應所需之熱能，且如上文所闡述， 149088.doc •49· 201108498 在將該進料進料至第二會έ 矛一窒、‘且克16之前可於熱交換器90中及/ 或猎由將水〉主射至兮玄；隹：* 豕進枓中來將該進料冷卻至自400°C至 J於600 C之一溫度。具有處於或接近第二重組器所需 之’皿度之進料可係較佳，使得丨）可調整第二重組器“内 之溫度以有利於氫在水煤氣轉化反應中之產生；2)可延長 薄膜68筹命’且3)改良壓縮機94之效能。熱能自第一重組 器14至第一重組器16之傳送係相當有效的此乃因來自第 一重組器之熱能包含於該進料中，該進料密切地涉及該第 二重組器内之反應。 在尚溫氫分離裝置18中藉由選擇性地使氫穿過氫分離薄 膜68之薄膜壁至氫導管124中以自經重組產物氣體分離含 氫氣流來由經重組產物氣體形成含氫流。含氫氣流可含有 一極高之氫濃度，且可含有至少0.9、或至少〇 95或至少 0.98莫耳分率氫。 由方；氮穿過風分離薄膜68之南通量，因此可以一相對高 速率自經重組產物氣體分離含氫氣流》在一實施例中，透 過氫分離薄膜68自經重組產物氣體分離氫時所處之溫度為 至少300°C、或自約35(TC至約600°C或自400。(：至500。(：。 由於氫以一高分壓存在於第二重組器16中，因此氫以_高 通量速率穿過氫分離薄膜68。第二重組器16中之氫之高分 壓係由於1)進料至第一重組器14且在進料中傳遞至第二重 組器之陽極排氣流中之大量氫；2)在第一重組器中產生且 進料至第二重組器之氫；及3)在第二重組器中藉由重組及 變換反應產生之氫。由於氫自經重組產物分離之高速率， 149088.doc -50- 201108498The recombined product gas in the reforming zone 108, the hydrogen conduit 124, is in gas communication with the non-hydrogenated 149088.doc • 46· 201108498 compound of the second reformer 16 gas, feed and steam (4). "The wall is selectively permeable to hydrogen (elements and / or molecules). The gas in the recombination zone 1 〇 8 can pass through the membrane wall of the membrane 至 to the hydrogen conduction" 24 @ @ @ @ @ @ @ @ @ @ @ @ @ @ @ The membrane wall is prevented from being transferred to the hydrogen conduit β. The pressure in the second reformer can be adjusted to increase or decrease the hydrogen flux across the high temperature hydrogen separation unit 18. The pressure in the second reformer 可由 can be flowed from the anode exhaust stream. Feed rate control to the first-recombiner 14. > Figure 3, the feed from the second reformer 16 is fed via line to the same 'guana hydrogen knife-off device 18. The high temperature hydrogen separation unit 18 may include hydrogen ( Optionally in a molecular or elemental form, a member is permeable. In a preferred embodiment, the high temperature hydrogen separation unit comprises a membrane that is selectively permeable to hydrogen. In one embodiment, the high temperature hydrogen separation unit A tubular film is coated which is coated with a palladium or palladium alloy which is selectively permeable to hydrogen. The gas stream entering the high temperature hydrogen separation unit 18 via the official line 122 may comprise hydrogen, carbon oxides and hydrocarbons. The gas stream may contact tubular hydrogen. Separating film 68 and hydrogen can pass through a film wall in place a hydrogen conduit 124 in the membrane 68. The membrane wall separates the hydrogen conductor 124 from the gas communication with the non-hydrogen compound and is selectively permeable to hydrogen (element and/or knife) such that the hydrogen in the incoming gas is permeable. The film wall is passed to the hydrogen conduit 124, and other gases are prevented from being transferred to the hydrogen conduit by the film wall. The high temperature tubular hydrogen separation membrane 68 of Figures 1 and 2 may comprise a carrier coated with hydrogen. Optionally, a thin layer of one of the metals or alloys may be formed. The support may be formed of a ceramic or a metal material that is permeable to hydrogen. Porous stainless steel or porous oxide is a preferred material for the carrier of the film 68. The hydrogen-selective metal or alloy on the carrier 149088.doc •47· 201108498 may be selected from the following Group VIII metals, including but not limited to Pd, Pt, Ni, Ag, Ta, V, Y, Nb, Ce, ln, Ho, La, Au and RU (specifically in alloy form). Palladium and palladium alloys are preferred. One of the preferred films 68 used in the process has a very thin palladium alloy film having a porous coating High surface area of one of the stainless steel carriers. U.S. Patent No. 6,1 A film of this type can be prepared by the method disclosed in No. 52,987. A film having a high surface area of platinum or a platinum alloy will also be suitable as a hydrogen selective material. The pressure in the recombination zone 1 〇 8 of the second recombiner 16 is maintained. At a level significantly above the pressure within the hydrogen conduit 124 of the tubular membrane 68, such that forced hydrogen is forced from the recombination zone 1〇8 of the second recombinator 10 through the membrane wall into the hydrogen conduit η*. In one example, the hydrogen conduit 124 is maintained at or near atmospheric pressure and the recombination zone 108 is maintained at a pressure of at least M5 Mpa, or at least 1 MPa, or at least 2 MPa, or at least 3 MPa. As noted above, Recombination zone 1 8 is maintained at such elevated pressure by compressing the feed from first recombiner 14 with compressor 94 and injecting the high pressure feed mixture into recombination zone 1〇8. Alternatively, the recombination zone 1〇8 can be maintained at such high pressures by mixing the high pressure steam with the feed as described above and injecting the high pressure mixture into the recombination zone 1 of the second recombiner 16. . Alternatively, the first recombiner can be mixed with the hydrocarbon stream by a high pressure vapor in the first recombiner 14 or one of the first recombiners and directly or through one or more heat exchangers 90. One of the high pressure feeds produced in the second reformer 16 is injected to maintain the recombination zone 1 〇 8 at such high pressures. The recombination zone 108 of the second recombiner 16 can be maintained at a pressure of at least 〇5 Μρ&, or at least ^149088.doc • 48 - 201108498 MPa, or at least 2.0 MPa or at least 3.0 MPa. The steam recombination feed and (as appropriate) additional steam are mixed and contacted with the recombination catalyst in the recombination zone 108 of the second reformer 16 at a temperature of at least 4 ° C, and preferably at 4 〇〇. The range of 〇c to 65〇<Jc is preferably in the range from 450 C to 550 C. A typical steam reformer operates at a temperature of 750 ° C or higher to achieve a sufficiently high equilibrium conversion. In the present method, the recombiner operating temperature is 40 CTC to 050 ° C by continuously removing hydrogen from the recombination zone 1 〇 8 into the hydrogen conduit 124 of the membrane 68 (and thus removed from the second recombiner 16). The generation of hydrogen in the range drives the recombination reaction. In this way, the process can achieve a near-to-total conversion of the reactants to hydrogen without equilibrium limitations. 400 ° C to 650. (: One of the operating temperatures is also advantageous for shifting the reaction to convert carbon monoxide and steam to more hydrogen, and then removing the hydrogen from the recombination zone 1〇8 into the hydrogen conduit 124 through the membrane wall of the membrane. The second reformer 16 achieves near complete conversion of hydrocarbons and carbon monoxide to hydrogen and carbon dioxide by recombination and water gas shift reaction, because equilibrium is never reached due to continuous removal of hydrogen from the second reformer. In the example, the steam recombination feed supplied to the second recombiner 16 from the first recombiner 14 and/or one of the first recombiners is supplied with heat to drive the reaction in the second recombiner. The steam recombination feed from the first reconfiguration 14 and/or one of the first recombiner recombination zones may contain sufficient thermal energy to drive the reaction in the second recombiner and may have from 400 C to a temperature of 950 C. The thermal energy of the steam recombination feed produced from the first recombiner 14 and/or the recombination zone of one of the first recombiners may exceed the thermal energy required to drive the reaction in the second recombiner 16, and As stated in the article, 149088.doc • 49· 201108498 Injecting the feed to the second meeting, before the squirrel 16 and in the heat exchanger 90 and/or hunting by water, the main shot to the 兮 隹; 隹: * 豕The feed is cooled to a temperature from 400 ° C to J at 600 C. The feed having a 'dish degree at or near the second recombiner can be preferred so that 丨 can be adjusted The second recombinator "temperature to facilitate the production of hydrogen in the water gas shift reaction; 2) can extend the film 68 and improve the performance of the compressor 94. Thermal energy from the first recombiner 14 to the first reorganization The transfer of the device 16 is quite effective because the thermal energy from the first recombiner is contained in the feed, which is closely related to the reaction in the second recombiner. Hydrogen is selectively passed through the membrane wall of the hydrogen separation membrane 68 to the hydrogen conduit 124 to separate the hydrogen-containing stream from the reformed product gas to form a hydrogen-containing stream from the reformed product gas. The hydrogen-containing stream may contain a very high hydrogen. Concentration, and may contain at least 0.9, or at least 〇95 or at least 0.98 mole fraction of hydrogen. Passing through the south flux of the wind separation membrane 68, the hydrogen containing stream can be separated from the recombined product gas at a relatively high rate. In one embodiment, the temperature at which hydrogen is separated from the recombined product gas by the hydrogen separation membrane 68 is At least 300 ° C, or from about 35 (TC to about 600 ° C or from 400. (: to 500. (: Since hydrogen is present in the second recombiner 16 at a high partial pressure, hydrogen is _ Qualcomm The rate of rate passes through the hydrogen separation membrane 68. The high partial pressure of hydrogen in the second reformer 16 is due to 1) feeding to the first reformer 14 and passing in the feed to the anode exhaust stream of the second reformer. a large amount of hydrogen; 2) hydrogen produced in the first reformer and fed to the second reformer; and 3) hydrogen produced by the recombination and shift reaction in the second reformer. Due to the high rate of separation of hydrogen from the recombinant product, 149088.doc -50- 201108498

因此不需要掃掠氣體來協助氣自氯導管124移除且移出高 溫氫分離裝置18。 D 如圖1至圖2中所顯示，含氫氣流退出高溫氫分離裝置18 且經由氫導管124透過管線126及34至陽極人㈣中而# 溶融碳酸鹽燃料電池12之陽極24β另—選擇為，該含氯氣 體係經由官線12 6直接進料至塔托 、 伐逛枓至％極入口 3〇。該氫氣流將氫 提供至陽極24以達成在沿燃料電㈣中之陽極路徑長度之 -個或多個陽極電極處與氧化劑之電化學反應。進入=二 重組器16之分子氫之一分壓高於退出高溫氫分離裝置18之 含氫氣流中之分子氫之-分a。第二重組器16與退出高溫 氫分離裝㈣之含氫氣流中之分子氫之分壓之間的分壓差 驅動重組反應及/或水煤氣轉化反應以製成更多氫。在某 些實施例中’可將一掃掠氣體（例如，蒸汽）注射至氫導管 十以將氫自薄膜壁構件之内部部分掃掠至氫導管中，藉此 增加可藉由氫分離薄膜自該重組區分離氫之速率。 在將含氫氣流進料至陽極24之前，可經由管線128將該 ，氫氣流或其-部分進料至熱交換器72以加熱煙流且冷卻 氫氣流。在退出高溫氫分離裝置18之後，該含氫氣流可具 有自400 C至650 C之-溫度（通常為自45〇〇c至55〇。〇之一 溫度）。退出高溫氫分離驻罢 轧刀離裝置18之含氫氣體之壓力可具有 約0.1 MPa、或自0.01服至〇 5 Mpa、或自〇 〇2跑至〇 4 MPa或自0.3至0.1 MPa之一颅上 上 vira之壓力。在一較佳實施例中，退 出南溫風分離裝置18之一含氫氣流具有約45〇。匸之一溫度 及約0.1 MPa之一屙六。山·- — 11 退出南溫虱分離裝置is之含氫氣 149088.doc 201108498 流之壓力及溫度可適合於直接將該含氫氣流直接進料至熔 融碳酸鹽燃料電池12之陽極入口 30〇 可視情況藉由在熱交換器72中與氫氣流交換熱且視情況 藉由與一氧化碳氣流交換熱來加熱烴流，如下文所闡述。 與選擇並控制進料至熔融碳酸鹽燃料電池12之陰極26之含 氧化劑氣流之溫度組合，可將進料至熔融碳酸鹽燃料電池 12之陽極24之氫氣流冷卻至至多4〇(rc、或至多3〇(Γ(：、或 至多200°C、或至多15〇。(：之一溫度、或自20。(：至400。(：或 自25°C至250°C之溫度以將熔融碳酸鹽燃料電池之操作溫 度控制在自600°C至700。(：之一範圍内。通常可藉由在熱交 換器72中與烴流交換熱來將含氫氣流或其一部分冷卻至自 200°C至400°C之一溫度。視情況，可藉由將氫氣流或其— 4为自熱父換器72傳遞至一個或多個額外熱交換器（未顯 示）以在該一個或多個額外熱交換器中之每一者中進一步 與煙流或與一水流交換熱來進一步冷卻該氫氣流或其—部 分。若s玄系統中採用額外熱交換器，則該氫氣流或其—部 分可係冷卻至自20。(：至200。(：、較佳自25。(：至100°C之一溫 度。在一實施例中，氫氣流之一部分可在熱交換器72及 (視情况）一個或多個額外熱交換器中經冷卻’且該氫氣流 之一部分可不在一熱交換器中經冷卻即進料至熔融碳酸鹽 燃料電池12之陽極24，其中該氫氣流之經組合部分可在至 多400°C、或至多30(rC、或至多2〇〇τ：、或至多15〇t>c之一 溫度、或自20°C至4〇〇。(：或自25充至1〇〇。(：之溫度下進料至 該燃料電池之陽極。 149088.doc •52- 201108498 可選擇並控制該氫氣流或其一部分至熱交換器72、22及 (視情況）至一個或多個額外熱交換器之流率以控制進料至 溶融碳酸鹽燃料電池12之陽極24之氫氣流之溫度。可藉由 調整節流閥36、130及132來選擇並控制氫氣流或其一部分 至熱父換器22及可選額外熱父換器之流率。可調整節流閥 36及130以控制氫氣流或其一部分透過管線126至熔融碳酸 鹽燃料電池12之陽極24之流動而不冷卻該氫氣流或其一部 分。節流閥130亦可控制氫氣流或其一部分至熱交換器η 之流動。可調整節流閥132以控制氫氣流或其一部分透過 管線128至熱交換器72及任一可選額外熱交換器之流動。 可協調地調整節流閥130及132以在將氫氣流進料至熔融碳 酸鹽燃料電池12之陽極24之前將所需之冷卻度提供至該氫 氣机。在一貫施例中，可回應於退出燃料電池12之陽極排 氣流及/或陰極排氣流之溫度之回饋量測而自動協調地調 整節流閥m及；m。該氫氣流將氫提供至陽極24以達成在 沿燃料電池u中之陽極路徑長度之一個或多個陽極電極處 與氧化劑之電化學反應。可藉由選擇將進料進料至第二重 組益16之速率來選擇氫氣流進料至炫融碳酸鹽燃料電池！ 2 之陽極24之速率，而將進料進料至第二重組器⑽速率又 可藉由烴流進料至第一重組器14之速率來選擇，而烴流進 料至第-重組器14之速率又可藉由調整烴流入口閥ι〇6來 控制。 進料至熱交換器72及（視情況）額外熱交換器之含氨氣流 之任—部分可自該熱交換器或透過用於冷卻該含氯氣流之 J49088.doc -53- 201108498 最後一個額外熱交換器進料，其中該氫氣流之任一部分環 繞β亥等熱交換器路由至熔融碳酸鹽燃料電池之陽極。在一 實施例中’可在一壓縮機（未顯示）中壓縮該含氫氣流之經 組合部分或退出高溫氫分離裝置18之含氫氣流以增加氫氣 流之壓力，且隨後可將該氫氣流進料至該陽極。在一實施 例中’可將該氫氣流壓縮至自〇.15 MPa至〇·5 MPa、或自 0_2 MPa至0.3 MPa、或高達〇·7 MPa或高達丄MPa之一壓 力。可藉由如下文所闡述而形成之一高壓二氧化碳流之膨 脹及/或穿過一個或多個渦輪機之高壓蒸汽來提供驅動該 麼縮機所需之所有能量或該能量之部分。 另一選擇為，可藉由以一協調方式控制節流閥36及134 來選擇氫氣流進料至熔融碳酸鹽燃料電池12之陽極24之速 率。可調整節流閥36以增加或減少氫氣流至陽極24中之流 動可調整節流閥134以增加或減少氫氣流至氫源64之流 動。可以一協調方式控制節流閥36及134，以使得一選定 速率之氫氣流可透過管線3 4進料至熔融碳酸鹽燃料電池工2 之陽極24,而超出提供該選定速率所需之氫氣流之量之氫 氣流之一部分可透過管線136進料至氫源64。 可經由管線48自高溫氫分離裝置18移除一氫耗盡經重組 產物氣流，其中該氫耗盡經重組產物氣流可包含未反應之 進料及該經重組產物氣體中之氣態非氫經重組產物^ ^等 非氫經重組產物及未反應之進料可包含二氧化碳、水（作 為洛汽）及少量一氧化碳及未反應之烴。氫耗盡經重組產 物氣流中亦可含有少量氫。 149088.doc -54- 201108498 在一實施例中’退出高溫氩分離裝置18之氫耗盡經重組 產物氣流可係在一乾燥基礎上含有至少0 8 '或至少0.9、 或至少0.95或至少0.98莫耳分率二氧化碳之二氧化碳氣 流。該二氧化碳氣流係具有至少0.5 MPa、或至少1 MPa、 或至少2 MPa或至少2.5 MPa之一壓力之一高壓氣流。在下 文中，氫耗盡經重組產物氣體將係稱為高壓二氧化碳氣 流。退出氫分離裝置18之高壓二氧化碳氣流之溫度為至少 400°C或通常介於425°C與600。(：之間或45〇t與55(TC之 間。 高壓二氧化碳氣流可退出高溫氫分離裝置18且經由管線 48及44進料至燃料電池12之陰極26。如圖所顯示，高壓二 氧化碳氣流穿過熱交換器22且可用於加熱氧化劍氣流。在 -實施例中’將該二氧化碳流之一部分直接與經由管線44 進入陰極26之氧化劑氣流混合。 在-較佳實施例中，經由管線48將高壓二氧化碳氣流進 料至催化部分氧化重組㈣。在催化部分氧化重組器2〇 中’二氧化碳流中之剩餘烴（例如，曱炫、乙院及丙烧）於 存在經由管㈣自氧化劑源42進料之氧或空氣之情形下燃 燒’以形成經由管線138穿過熱交換器22且經由管線㈣ 料至陰極26之一熱流出物燃燒流。在—實施例中，姆燒流 經由管線138及44直接進料至陰極26。進料至催化部分氧 化重組器20之含氧化劑流中之分子氧之一量係二氧化碳流 中之挺之完全燃燒所需之化學計量量之至少〇·9倍作不多 於1.1倍。 149088.doc -55- 201108498 熱燃燒流可包含大量二氧化碳，但亦可包含氮氣及水。 退出催化部分氧化重組器20之熱燃燒流可具有在自至少 75 0°C 至 1050°C、或自 800°C 至 l〇〇〇°C 或自 850。〇 至 900。<：之 範圍之一溫度。來自熱燃燒氣體之熱可在熱交換器22中與 含氫氣流交換及/或在該熱交換器中與含氧化劑氣流交 換。如圖2中所顯示，來自退出催化部分氧化重組2〇之燃 燒流之熱之至少一部分可經由管線96在熱交換器98中與第 一重組器14交換。 在一實施例中’熱燃燒氣體可直接進料至陰極排氣入口 38。可調整含氧化劑氣體之一溫度以使得退出該燃料電池 之陰極排氣流之一溫度在自550艽至了㈧它之範圍。可透過 在熱乂換器22中冷卻及/或加熱來將含氧化劑氣體溫度調 整至自150 C至450°C之一溫度。可藉由調整節流閥46、58 及140來控制含氧化劑氣流自高溫氫分離裝置“至熱交換 器22及/或催化部分氧化重組器2〇之流動。 在熱燃燒氧流退出催化部分氧化重組2 〇時，其可含有大 篁作為蒸汽之水。在一實施例中，可藉由在熱交換器22中 及/或在熱交換器72及（若需要）一個或多個額外熱交換器 (未顯示）中冷卻熱燃燒氣流且自蒸汽冷凝水來自該熱燃燒 氣流移除蒸汽。 糟由使含二氧化碳氣流穿過管線142至熱交換器72同時 透過烴流管線62將烴流進料至熱交換器72中來利用來自高 皿氫分離裝置18之.高壓二氧化碳氣流加熱該烴流。可藉由 調整節流閥144來控制高壓熱氧化碳流自高溫氫分離裝置 149088.doc • 56 - 201108498 18至熱交換器72之流動。可調整節流閥144以控制二氧化 碳流至熱交換器72之流動以將該烴流加熱至一選定溫度。 可將该fe流加熱至一溫度以使得在將該烴流進料至第一重 組器14時該烴流具有至少15〇它或自2〇〇。〇至5CKTC之一溫 度。 可藉由一回饋機制自動調整節流閥46、58及14〇，其中 該回饋機制可量測退出燃料電池12之陰極排氣流之溫度及/ 或進入第一重組器14之烴流之溫度且調整節流閥46、58及 140以將該陰極排氣流及/或進入第一重組器14之烴流之溫 度維持在所設定限制内，同時將第二重組器16及/或高溫 氫分離裝置18内之内部壓力維持在一所需位準處。 猎由乳與二氧化碳在陰極處之反應產生之氫氣流及氧化 劑（碳酸根離子）較佳在燃料電池12之一個或多個陽極電極 處混合（如上文所閣述）以以至少〇·1 W/cm2、更佳地至少 〇·15 W/Cm2、或至少0.2 W/cm2或至少0.3 w/cm2之一電功 率氹f產生電。可藉由選擇並控制氫氣流進料至燃料電池 12之陽極24之速率及含氧化劑氣流進料至燃料電池^之陰 ㈣之速率以此等電功率密度產生電。可藉由調整氧化劑 氣，體入口閥46來選擇並控制至燃料電池之陰極“之含氧 化劑氣流之流率。 士上文所闡4，可藉由選擇並控制將進料進料至第二重 巧之速率來選擇並控制氫氣流至燃料電池12之陽極24 之=率，而將進料進料至第二重組器16之速率又可藉由將 U科至第—重組器14之速率來選擇並控制，而將烴流 149088.doc -57- 201108498 進料至第一重組器14之速率又可藉由調整烴流入口閥1〇6 來選擇並控制。另一選擇為，如上文所闡述，可藉由以一 協調方式控制節流閥36、130、132及134來選擇並控制氫 氣机進料至燃料電池之陽極24之速率。在一實施例中， 可藉由一回饋機制來自動調整節流閥36、i3〇、132及Η# 以維持氫氣流至陽極24之-選定料，其中該回饋機制可 f於對陽極排氣流中之氫含量、或陽極排氣流中之水含 量、或該燃料電池中所形成之水相對於該陽極排氣流中之 氫之比之量測而操作。 在本發月之方法中’使氫氣流與氧化劑在一個或多個陽 極電極處混合藉由存在於進料至_電池12之該氫氣流中 ，氫之-部分與該氧化劑之氧化而產生水（作為蒸汽卜由 氫與氧化劑之氧化產生之水藉由氫氣流之未反應部分掃掠 穿過燃料電池12之陽極24以作為陽極排氣流之部分退出陽 . 。必俘亚衩制氫氣流: 料至陽極2 4之流率，因此备置 此母早位時間燃料電池12中所带 之水之量對每單位時間陽極排 ‘ 虱之量之比為至 1.0、或至多0.75、或至多0.67 4 rΛ 兄主夕0.43、或至多〇 : 或至多0.11。在一實施例中， 了 乂莫耳置測燃料電池12 所形成之水之量及陽極排氣中 τI虱之I，以使得每單位Ε 該燃料，所形成之水之量對每單位時間該二 之虱之里之比在每單位時間以莫耳計為There is therefore no need to sweep the gas to assist in the removal of gas from the chloride conduit 124 and removal of the high temperature hydrogen separation unit 18. D, as shown in Figures 1 to 2, the hydrogen-containing stream exits the high temperature hydrogen separation unit 18 and passes through the hydrogen conduit 124 through lines 126 and 34 to the anode (4). # The molten anode of the carbonate fuel cell 12 is further selected as The chlorine-containing gas system is directly fed to the Tato via the official line 12 6 , and is cut to the % pole inlet 3〇. The hydrogen stream provides hydrogen to the anode 24 to effect an electrochemical reaction with the oxidant at one or more anode electrodes along the length of the anode path in the fuel cell (4). The partial pressure of one of the molecular hydrogens entering the second reactor 16 is higher than the molecular weight of the molecular hydrogen in the hydrogen-containing gas flowing out of the high-temperature hydrogen separation unit 18. The partial pressure difference between the second reformer 16 and the partial pressure of the molecular hydrogen in the hydrogen-containing gas stream exiting the high temperature hydrogen separation unit (4) drives the recombination reaction and/or the water gas shift reaction to produce more hydrogen. In some embodiments, a sweep gas (eg, steam) can be injected into the hydrogen conduit 10 to sweep hydrogen from the interior portion of the membrane wall member into the hydrogen conduit, thereby increasing the separation of the membrane by hydrogen. The rate at which the recombination zone separates hydrogen. The hydrogen stream or a portion thereof may be fed to heat exchanger 72 via line 128 to heat the flue gas and cool the hydrogen stream prior to feeding the hydrogen containing stream to anode 24. After exiting the high temperature hydrogen separation unit 18, the hydrogen containing stream may have a temperature from 400 C to 650 C (typically from 45 ° C to 55 Torr.). The pressure of the hydrogen-containing gas exiting the high-temperature hydrogen separation station may be about 0.1 MPa, or from 0.01 to M5 Mpa, or from 〇〇2 to 〇4 MPa or from 0.3 to 0.1 MPa. The pressure of the vira on the skull. In a preferred embodiment, one of the exiting southerly wind separation devices 18 has a hydrogen containing stream of about 45 Torr. One of the temperatures and one of about 0.1 MPa. Mountain·- 11 Exiting the South Wenyu Separation Unit is containing hydrogen 149088.doc 201108498 The pressure and temperature of the stream can be adapted to directly feed the hydrogen-containing stream directly to the anode inlet 30 of the molten carbonate fuel cell 12. The hydrocarbon stream is heated by exchanging heat with the hydrogen stream in heat exchanger 72 and optionally by exchanging heat with the carbon monoxide gas stream, as set forth below. The hydrogen stream fed to the anode 24 of the molten carbonate fuel cell 12 can be cooled to at most 4 Torr, in combination with the temperature of the oxidant-containing gas stream selected and controlled to feed to the cathode 26 of the molten carbonate fuel cell 12. Up to 3 〇 (Γ, or at most 200 ° C, or up to 15 〇. (: one temperature, or from 20 (: to 400. (or or from 25 ° C to 250 ° C to melt The operating temperature of the carbonate fuel cell is controlled in a range from 600 ° C to 700 °. Typically, the hydrogen containing stream or a portion thereof can be cooled to 200 by exchanging heat with the hydrocarbon stream in heat exchanger 72. a temperature of from ° C to 400 ° C. Optionally, by transferring the hydrogen stream or its heat exchanger 72 to one or more additional heat exchangers (not shown) at the one or more Each of the additional heat exchangers further exchanges heat with the plume or with a stream of water to further cool the stream or portion thereof. If an additional heat exchanger is employed in the smectic system, the hydrogen stream or its The portion may be cooled to from 20. (: to 200. (:, preferably from 25 (...) to a temperature of 100 ° C. In one embodiment, a portion of the hydrogen stream may be cooled in heat exchanger 72 and (as appropriate) one or more additional heat exchangers and one portion of the hydrogen stream may be cooled or fed in a heat exchanger. Up to the anode 24 of the molten carbonate fuel cell 12, wherein the combined portion of the hydrogen stream can be at a temperature of at most 400 ° C, or at most 30 (rC, or at most 2 〇〇 τ:, or at most 15 〇 t > c) Or from 20 ° C to 4 〇〇 (: or from 25 to 1 〇〇. (: at the temperature of the anode to the fuel cell. 149088.doc • 52- 201108498 can choose and control the hydrogen flow The flow rate of or a portion thereof to the heat exchangers 72, 22 and (as appropriate) to one or more additional heat exchangers controls the temperature of the hydrogen stream fed to the anode 24 of the molten carbonate fuel cell 12. The throttle valves 36, 130, and 132 are adjusted to select and control the flow rate of the hydrogen stream or a portion thereof to the hot parent exchanger 22 and the optional additional hot parent exchanger. The throttle valves 36 and 130 can be adjusted to control the hydrogen flow or A portion of the flow through line 126 to the anode 24 of the molten carbonate fuel cell 12 is not The hydrogen stream or a portion thereof. The throttle valve 130 can also control the flow of the hydrogen stream or a portion thereof to the heat exchanger η. The throttle valve 132 can be adjusted to control the flow of hydrogen or a portion thereof through the line 128 to the heat exchanger 72 and Flow of any of the optional additional heat exchangers. The throttle valves 130 and 132 can be coordinated to provide the desired degree of cooling to the hydrogen machine prior to feeding the hydrogen stream to the anode 24 of the molten carbonate fuel cell 12. In a consistent embodiment, the throttle valves m and m can be automatically coordinated in response to feedback measurements of the temperature of the anode exhaust stream and/or the cathode exhaust stream exiting the fuel cell 12. The hydrogen stream provides hydrogen to the anode 24 to effect an electrochemical reaction with the oxidant at one or more anode electrodes along the length of the anode path in the fuel cell u. The hydrogen stream feed can be selected to the smelting carbonate fuel cell by selecting the rate at which the feed is fed to the second replenishment benefit 16! The rate of the anode 24 of 2, while the feed to the second reformer (10) rate can in turn be selected by the rate at which the hydrocarbon stream is fed to the first reformer 14, and the hydrocarbon stream is fed to the first-recombiner 14. The rate can in turn be controlled by adjusting the hydrocarbon flow inlet valve ι〇6. Any portion of the ammonia-containing gas stream fed to the heat exchanger 72 and, where appropriate, the additional heat exchanger may be from the heat exchanger or through the last additional J49088.doc -53-201108498 for cooling the chlorine-containing gas stream. The heat exchanger feeds wherein any portion of the hydrogen stream is routed to the anode of the molten carbonate fuel cell around a heat exchanger such as a beta. In one embodiment, the combined portion of the hydrogen-containing stream or the hydrogen-containing stream exiting the high temperature hydrogen separation unit 18 may be compressed in a compressor (not shown) to increase the pressure of the hydrogen stream, and then the hydrogen stream may be subsequently flowed. Feed to the anode. In one embodiment, the hydrogen stream can be compressed to a pressure from 〇15 MPa to 〇·5 MPa, or from 0_2 MPa to 0.3 MPa, or up to 〇7 MPa or up to 丄MPa. The expansion of the high pressure carbon dioxide stream and/or the high pressure steam passing through one or more turbines can be used to provide all of the energy or portion of the energy required to drive the compressor. Alternatively, the rate at which the hydrogen stream is fed to the anode 24 of the molten carbonate fuel cell 12 can be selected by controlling the throttle valves 36 and 134 in a coordinated manner. The throttle valve 36 can be adjusted to increase or decrease the flow of hydrogen to the flow adjustable throttle 134 in the anode 24 to increase or decrease the flow of hydrogen to the hydrogen source 64. The throttle valves 36 and 134 can be controlled in a coordinated manner such that a selected rate of hydrogen flow can be fed through line 34 to the anode 24 of the molten carbonate fuel cell 2 beyond the hydrogen flow required to provide the selected rate. A portion of the amount of hydrogen stream can be fed to hydrogen source 64 via line 136. A hydrogen depleted recombined product gas stream can be removed from high temperature hydrogen separation unit 18 via line 48, wherein the hydrogen depleted recombined product gas stream can comprise unreacted feed and gaseous non-hydrogen recombination in the reformed product gas. The non-hydrogen recombined product, such as the product, and the unreacted feed may comprise carbon dioxide, water (as Luoqi), and a small amount of carbon monoxide and unreacted hydrocarbons. The hydrogen depleted reconstituted product stream may also contain a small amount of hydrogen. 149088.doc -54- 201108498 In one embodiment, the hydrogen depleted recombined product gas stream exiting the high temperature argon separation unit 18 can contain at least 0 8 ' or at least 0.9, or at least 0.95 or at least 0.98 on a dry basis. The ear fraction is the carbon dioxide gas flow of carbon dioxide. The carbon dioxide gas stream is a high pressure gas stream having a pressure of at least 0.5 MPa, or at least 1 MPa, or at least 2 MPa or at least 2.5 MPa. In the following, the hydrogen depleted recombined product gas will be referred to as a high pressure carbon dioxide gas stream. The temperature of the high pressure carbon dioxide gas stream exiting the hydrogen separation unit 18 is at least 400 ° C or typically between 425 ° C and 600. (between or between 45 〇t and 55 (TC.) The high pressure carbon dioxide gas stream can exit the high temperature hydrogen separation unit 18 and be fed via line 48 and 44 to the cathode 26 of the fuel cell 12. As shown, high pressure carbon dioxide gas flow The heat exchanger 22 is passed through and can be used to heat the oxidant stream. In an embodiment, a portion of the carbon dioxide stream is directly mixed with the oxidant stream entering the cathode 26 via line 44. In the preferred embodiment, the high pressure is via line 48. The carbon dioxide gas stream is fed to the catalytic partial oxidation recombination (IV). The remaining hydrocarbons in the carbon dioxide stream in the catalytic partial oxidation reformer 2 (eg, Xingxuan, Yiyuan, and Propylene) are present in the presence of the tube (4) from the oxidant source 42. Combustion in the presence of oxygen or air to form a hot effluent combustion stream through line 138 through heat exchanger 22 and via line (iv) to cathode 26. In an embodiment, the m-burn stream is directly via lines 138 and 44 Feeding to the cathode 26. The amount of molecular oxygen fed to the oxidant-containing stream of the catalytic partial oxidation reformer 20 is the stoichiometric amount required for complete combustion in the carbon dioxide stream. At least 〇·9 times for no more than 1.1 times. 149088.doc -55- 201108498 The hot combustion stream may contain a large amount of carbon dioxide, but may also contain nitrogen and water. The hot combustion stream exiting the catalytic partial oxidation reformer 20 may have From at least 75 0 ° C to 1050 ° C, or from 800 ° C to l ° ° C or from 850 ° 〇 to 900. <: one of the ranges of temperature. Heat from hot combustion gases can be exchanged in heat The exchanger 22 is exchanged with a hydrogen-containing gas stream and/or exchanged with the oxidant-containing gas stream in the heat exchanger. As shown in Figure 2, at least a portion of the heat from the combustion stream exiting the catalytically partially oxidized recombination unit 2 can be via line 96. In the heat exchanger 98, it is exchanged with the first recombiner 14. In one embodiment, 'hot combustion gases can be fed directly to the cathode exhaust inlet 38. The temperature of one of the oxidant-containing gases can be adjusted to exit the cathode of the fuel cell. The temperature of one of the exhaust streams is in the range from 550 Torr to (eight). The temperature of the oxidant-containing gas can be adjusted to a temperature from 150 C to 450 ° C by cooling and/or heating in the heat exchanger 22. By adjusting the throttle valves 46, 58 and 140 Controlling the flow of the oxidant-containing gas stream from the high temperature hydrogen separation unit "to the heat exchanger 22 and/or the catalytic partial oxidation reformer 2". When the hot combustion oxygen stream exits the catalytic partial oxidation recombination 2 〇, it may contain large ruthenium as steam Water. In one embodiment, the hot combustion gas stream may be cooled and steamed by heat exchanger 22 and/or in heat exchanger 72 and, if desired, one or more additional heat exchangers (not shown). Condensed water is removed from the hot combustion gas stream. The waste is passed from a high water vapor stream by passing a carbon dioxide containing gas stream through line 142 to heat exchanger 72 while passing hydrocarbon stream 62 through hydrocarbon stream line 62 to heat exchanger 72. The high pressure carbon dioxide gas stream of unit 18 heats the hydrocarbon stream. The flow of the high pressure thermal oxidizing carbon stream from the high temperature hydrogen separation unit 149088.doc • 56 - 201108498 18 to the heat exchanger 72 can be controlled by adjusting the throttle valve 144. The throttle valve 144 can be adjusted to control the flow of carbon dioxide to the heat exchanger 72 to heat the hydrocarbon stream to a selected temperature. The fe stream can be heated to a temperature such that the hydrocarbon stream has at least 15 Torrs or 2 Torr when the hydrocarbon stream is fed to the first reformer 14. 〇 to a temperature of 5CKTC. The throttle valves 46, 58 and 14〇 can be automatically adjusted by a feedback mechanism that measures the temperature of the cathode exhaust stream exiting the fuel cell 12 and/or the temperature of the hydrocarbon stream entering the first reformer 14. And adjusting the throttle valves 46, 58 and 140 to maintain the temperature of the cathode exhaust stream and/or the hydrocarbon stream entering the first reformer 14 within a set limit while the second recombiner 16 and/or high temperature hydrogen The internal pressure within the separation device 18 is maintained at a desired level. The hydrogen stream and the oxidant (carbonate ion) produced by the reaction of the milk with carbon dioxide at the cathode are preferably mixed at one or more anode electrodes of the fuel cell 12 (as described above) to at least 〇·1 W. More preferably /cm2, at least W15 W/cm2, or at least 0.2 W/cm2 or at least 0.3 w/cm2 of electrical power 凼f produces electricity. Electricity can be generated at such electrical power densities by selecting and controlling the rate at which the hydrogen stream is fed to the anode 24 of the fuel cell 12 and the rate at which the oxidant-containing gas stream is fed to the cathode (4) of the fuel cell. The flow rate of the oxidant-containing gas stream to the cathode of the fuel cell can be selected and controlled by adjusting the oxidant gas, body inlet valve 46. As explained above, the feed can be fed to the second by selecting and controlling. The rate of repetition to select and control the rate of hydrogen flow to the anode 24 of the fuel cell 12, while the rate at which the feed is fed to the second recombiner 16 can be increased by the rate of U to the first recombiner 14. To select and control, the rate at which the hydrocarbon stream 149088.doc -57- 201108498 is fed to the first reformer 14 can in turn be selected and controlled by adjusting the hydrocarbon stream inlet valve 1〇6. Another option is as above As illustrated, the rate at which the hydrogen machine is fed to the anode 24 of the fuel cell can be selected and controlled by controlling the throttle valves 36, 130, 132, and 134 in a coordinated manner. In one embodiment, a feedback mechanism can be utilized To automatically adjust the throttle valves 36, i3, 132, and Η# to maintain the flow of hydrogen to the anode 24, wherein the feedback mechanism can be used in the hydrogen content of the anode exhaust stream, or in the anode exhaust stream. Water content, or water formed in the fuel cell relative to the anode exhaust Operating in the ratio of hydrogen in the process. In the method of the present month, 'mixing the hydrogen stream with the oxidant at one or more anode electrodes is present in the hydrogen stream fed to the battery 12, hydrogen Part of the oxidation of the oxidant to produce water (as a vapor, water produced by oxidation of hydrogen and oxidant is swept through the unreacted portion of the hydrogen stream through the anode 24 of the fuel cell 12 as part of the anode exhaust stream Exiting from the yang. The hydrogen flow from the Aachen process: the flow rate to the anode 24, so the amount of water carried in the fuel cell 12 at the mother's early time is set to the amount of the anode row per unit time. The ratio is up to 1.0, or at most 0.75, or at most 0.67 4 rΛ, 0.43, or at most 〇: or at most 0.11. In one embodiment, the amount of water formed by the fuel cell 12 and the anode are measured. The ratio of τI虱 in the exhaust gas so that the ratio of the amount of water formed per unit time to the fuel is expressed in moles per unit time.

多0.75、或至多0.67、或 ，或J ^或至多〇_25或至」 I49088.doc •58· 201108498 0.11。在-實施例中，可選擇並控制氫氣流進料至陽極24 之流率，因此燃料電池12中之每通程之氫利用率為小於 50%、或至多45%、或至多·、或至多鄕、或至多篇 或至多10%。 在本發明之方法之另一實施例中，可選擇並控制氫氣流 進料至陽極24之流率，因此陽極排氣流含有至少〇 6、或 至少0.7、或至少〇·8或至少〇 9莫耳分率氫在一另一實施 例中，可選擇並控制進料至陽極24之氫氣流之流率，因此 該陽極排氣流含有進料至陽極24之氫氣流中之氫之大於 50%、或至少60%、或至少70%、或至少8〇%、或至少 90%。 在某些實施例中，可選擇並控制二氧化碳流進料至陰極 26之流率以使得該熔融碳酸鹽燃料電池之陰極部分之大部 刀中之一氧化奴之分壓咼於該炫融碳酸鹽燃料電池之一陽 極部分之一大部分中之二氧化碳之一分壓。在一實施例 中可選擇並控制二氧化碳流進料至陰極26之流率以使得 退出該燃料電池之陰極排氣流中之二氧化碳之分壓大於退 出該燃料電池之陽極排氣流中之二氧化碳之分壓。選擇並 控制一氧化奴之流率以使得溶融碳酸鹽燃料電池之至少 75%、或至少95%或大致所有陰極部分中之二氧化碳之分 壓高於該熔融碳酸鹽燃料電池之至少75%、95%或大致所 有陽極部分之二氧化碳之一分壓。 操作該熔融碳酸鹽燃料電池以在任一空氣濃度及/或任 風利用率下將APco2控制在高於〇處之壓力下，可抑制溶 149088.doc •59- 201108498 融碳酸鹽燃料電池之二氧化碳不足且增強該熔融碳酸鹽燃 料電池之電池電位。可選擇並控制二氧化碳流進料至熔融 碳酸鹽燃料電池12之陰極26之流率以使得在氩利用率為至 多60%、至多50%或至多40%、至多30%、至多2〇。/0或至多 1 0%時如由方程式（ΔΡςοΟΚΡα/χΡα/)碟定之二氧化碳 分壓之德爾塔為約0巴或高於0巴，自0.01至〇 2巴或自〇 〇5 至0.15巴，及/或控制空流動以使得二氧化碳對分子氧之一 莫耳比為約2。 下文陳述非約束性實例。 與對電池電位之計算組合之一 UniSim⑰模擬程式 (Honey well)用於構造本發明之熔融碳酸鹽燃料電池系統之 -詳細過程模擬。UniSim程式用於獲得物質均衡及能量均 衡資料。針對不同之氫利用率值及其他相關系統參數重複 地解該詳細過程模擬κ細過程模擬輸出包含進入及退 出該炼融碳酸鹽燃料電池之所有過程流之詳細έ且成資料。 對於高溫燃料電池，啟動損失小且可藉由僅考量歐姆及 電極損失而在實際電流密度範圍内獲得電池電位。如此， 一熔融碳酸鹽燃料電池之電池 .^ 电1 (V)係開路電壓（Ε)與損 失（iR)之間的差，如方程式（1)中所顯示。More than 0.75, or at most 0.67, or , or J ^ or at most 〇 _25 or to " I49088.doc • 58 · 201108498 0.11. In an embodiment, the flow rate of the hydrogen stream feed to the anode 24 can be selected and controlled such that the hydrogen utilization rate per pass in the fuel cell 12 is less than 50%, or at most 45%, or at most, or at most, Or up to 10% or up to 10%. In another embodiment of the method of the present invention, the flow rate of the hydrogen stream feed to the anode 24 can be selected and controlled, such that the anode exhaust stream contains at least 〇6, or at least 0.7, or at least 〇8 or at least 〇9 Mohr Fraction Hydrogen In another embodiment, the flow rate of the hydrogen stream fed to the anode 24 can be selected and controlled so that the anode exhaust stream contains more than 50 hydrogen in the hydrogen stream fed to the anode 24. %, or at least 60%, or at least 70%, or at least 8%, or at least 90%. In certain embodiments, the flow rate of the carbon dioxide stream feed to the cathode 26 can be selected and controlled such that one of the majority of the knives of the cathode portion of the molten carbonate fuel cell is crushed by the sulphuric carbonic acid. One of the carbon dioxide portions of one of the anode portions of the salt fuel cell is divided. In one embodiment, the flow rate of the carbon dioxide stream feed to the cathode 26 can be selected and controlled such that the partial pressure of carbon dioxide in the cathode exhaust stream exiting the fuel cell is greater than the carbon dioxide exiting the anode exhaust stream exiting the fuel cell. Partial pressure. Selecting and controlling the flow rate of monoxide to cause at least 75%, or at least 95% or substantially all of the partial pressure of carbon dioxide in the cathode portion of the molten carbonate fuel cell to be higher than at least 75%, 95 of the molten carbonate fuel cell % or approximately one of the carbon dioxide partial pressures of the anode portion. Operating the molten carbonate fuel cell to control APco2 at a pressure above the helium at any air concentration and/or any wind utilization rate, thereby inhibiting the carbon dioxide deficiency of the melted carbonate fuel cell by 149088.doc • 59-201108498 And enhancing the battery potential of the molten carbonate fuel cell. The flow rate of the carbon dioxide stream feed to the cathode 26 of the molten carbonate fuel cell 12 can be selected and controlled such that the argon utilization rate is at most 60%, at most 50% or at most 40%, at most 30%, at most 2 Torr. At /0 or at most 10%, the delta of the carbon dioxide partial pressure determined by the equation (ΔΡςοΟΚΡα/χΡα/) is about 0 bar or higher than 0 bar, from 0.01 to 2 bar or from 5 to 0.15 bar. And/or controlling the empty flow such that the molar ratio of carbon dioxide to molecular oxygen is about 2. Non-binding examples are set forth below. One of the combinations of calculations for battery potential, the UniSim17 Simulator (Honey Well) was used to construct a detailed process simulation of the molten carbonate fuel cell system of the present invention. The UniSim program is used to obtain material balance and energy balance data. Repeatedly resolving the detailed process simulation for different hydrogen utilization values and other relevant system parameters. The simulated process output contains detailed information on all process flows entering and exiting the smelting carbonate fuel cell. For high temperature fuel cells, the startup loss is small and the battery potential can be obtained over the actual current density range by considering only ohmic and electrode losses. Thus, the battery of a molten carbonate fuel cell. ^1 (V) is the difference between the open circuit voltage (Ε) and the loss (iR), as shown in equation (1).

V=E-iR 其中V及E具有伏及毫伏之置办,〆 且 2…“ 早位’ 1係電流密度(mA/cm2) 且RWcm)係將電解質、陰極 队一、陰極⑷與陽極ω電… 一起之歐姆 心.·且U ，如方程式（2)中所 149088.doc 201108498 顯示。 R-Rohm + nc + na (2) E係自能斯特方程式獲得： E一E "KRT/^FWPj^Po’VPj^oXrtqF) ln(PC02c/pC02a) (3) 實例1使用上文所闡述之詳細過程模擬來針對本文_所 闡述之’熔融奴酸鹽燃料電池系統模擬電池電壓對電流密度 及功率密度形成，其中藉由陽極排氣加熱第一重組器，無 其他加熱。舉例而言，圖1所繪示之系統。藉由與來自催 化部分氧化重組器之熱流出物交換來加熱用於第二重組器 之熱。藉由使用陰極排氣以預熱催化氧化重組器空氣進料 來增加來自該催化部分氧化重組器之流出物之輸出溫度。 實例2使用上文所闡述之模擬來針對本文中所闡述之炫 融碳酸鹽燃料電池系統模擬電池電壓對電流密度及功率密 度形成，其中藉由陽極排氣及來自一催化部分氧化重組器 之熱來加熱第一重組器。舉例而言，圖2中所繪示之系 統。 對於實例1及2 ,在1巴（約oj MPa或約i atm)之一壓力及 650 C之一溫度下操作該熔融碳酸鹽燃料電池。至該熔融 碳酸鹽燃料電池之陰極之進料之流動與至陽極之進料之流 動係對流。使用空氣作為氧源。使用空氣之值來在各種氫 利用率下產生二氧化碳對分子氧之為2之一莫耳比。在表t 中列出了貫例1及2模擬之該熔融碳酸鹽燃料電池之百分比 氫利用率、該第一及第二重組器之操作條件、蒸汽對碳比 及本至虱之百为比轉化。自j. p〇wer S〇urces 2002，112， 149088.doc 201108498 第5 09-5 18頁獲得方程式2中之R且假定為等於0.75 Qcm2。 將來自用於實例1及2模擬之資料與由Larmine等人在 「Fuel Cell Systems Explained」（2003，Wiley & Sons，第 199頁）中闡述之目前技術水平的熔融碳酸鹽燃料電池之電 池電壓、電流密度及功率密度之文獻值進行比較。 表1 h2利用 率，％ 溫度，第 一重組 器，t 溫度，第 二重組 器，。C 壓力，第 二重組 器，巴 蒸汽/破比，第 一重組器 蒸汽/碳比，第 二重組器 苯至氫之 轉化％ 20 619 500 15 2.5 3 94 30 591 500 15 2.5 3 95 40 569 500 15 2.5 3 96 50 551 500 15 2.5 3 96 60 536 500 15 2.5 3 97 圖4針對實例1及2中所模擬之熔融碳酸鹽燃料電池系統 繪示電池電壓（mV)對電流密度（mA/cm2)及具有作為一進料 之重組油之一熔融碳酸鹽燃料電池之文獻值。以20。/〇及 30〇/〇之氫利用率操作該等熔融碳酸鹽燃料電池。資料線 160針對實例】及2之一熔融碳酸鹽燃料電池系統繪示在 20。/。之氫利用率下之電池電壓（mV)對電流密度…八化爪2)。 資料線162針對實例i及2繪示在30%之氫利用率下之電池 電壓（mV)對電流密度（mA/cm2)。資料線164針對如由V=E-iR where V and E have volts and millivolts, and 2... "early position 1 system current density (mA/cm2) and RWcm) is the electrolyte, cathode team, cathode (4) and anode ω Electricity... Together with ohms. and U, as shown in equation (2), 149088.doc 201108498. R-Rohm + nc + na (2) E is a self-energy equation: E-E "KRT/ ^FWPj^Po'VPj^oXrtqF) ln(PC02c/pC02a) (3) Example 1 uses the detailed process simulation described above to simulate battery voltage versus current density for a molten sulphate fuel cell system as described herein. And power density formation, wherein the first recombinator is heated by the anode exhaust without any other heating. For example, the system illustrated in Figure 1 is heated by exchange with hot effluent from the catalytic partial oxidation recombiner. The heat of the second recombiner increases the output temperature of the effluent from the catalytic partial oxidation recombiner by using a cathode exhaust to preheat the catalytic oxidation recombiner air feed. Example 2 uses the simulation described above. Simulation of the flash carbonate fuel cell system described in this paper The cell voltage is formed for current density and power density, wherein the first recombiner is heated by anode venting and heat from a catalytic partial oxidation recombiner. For example, the system depicted in Figure 2. For Example 1 and 2, operating the molten carbonate fuel cell at a pressure of 1 bar (about oj MPa or about i atm) and a temperature of 650 C. The flow of the feed to the cathode of the molten carbonate fuel cell is to the anode The flow of the feed is convection. Air is used as the oxygen source. The value of air is used to produce a molar ratio of carbon dioxide to molecular oxygen at various hydrogen utilization rates. Tables 1 and 2 are listed in Table t. Simulating the percentage hydrogen utilization of the molten carbonate fuel cell, the operating conditions of the first and second reformers, the steam to carbon ratio, and the ratio of the present to the enthalpy. From j. p〇wer S〇urces 2002 , 112, 149088.doc 201108498 Page 5 09-5 Page 18 Obtain the R in Equation 2 and assume that it is equal to 0.75 Qcm 2. The data from the simulations used in Examples 1 and 2 will be from the "Fuel Cell Systems Explained" by Larmine et al. 2003, Wiley & Sons, No. The literature values for the battery voltage, current density and power density of the current state of the art molten metal carbonate fuels described in page 199 are compared. Table 1 h2 utilization rate, % temperature, first recombiner, t temperature, second recombiner. C pressure, second recombiner, bar steam/break ratio, first reformer steam/carbon ratio, second reformer benzene to hydrogen conversion % 20 619 500 15 2.5 3 94 30 591 500 15 2.5 3 95 40 569 500 15 2.5 3 96 50 551 500 15 2.5 3 96 60 536 500 15 2.5 3 97 Figure 4 shows the battery voltage (mV) vs. current density (mA/cm2) for the molten carbonate fuel cell system simulated in Examples 1 and 2. And literature values for a molten carbonate fuel cell having one of the reconstituted oils as a feed. Take 20. The hydrogen utilization rate of /〇 and 30〇/〇 operates the molten carbonate fuel cells. The data line 160 is shown at 20 for one example and one of the molten carbonate fuel cell systems. /. The battery voltage (mV) under the hydrogen utilization rate is the current density...eight claws 2). Data line 162 plots battery voltage (mV) versus current density (mA/cm2) at 30% hydrogen utilization for Examples i and 2. The data line 164 is directed to

Larmine 專人在「Fuel Cell Systems Explained」（2003，Larmine is at "Fuel Cell Systems Explained" (2003,

Wiley & Sons ’第199頁）中所闡述之目前技術水平的熔融 碳酸鹽燃料電池系統繪示電池電壓（mV)對電流密度 149088.doc -62- 201108498 (mA/cm2)。如圖4中所顯示’對於一給定電流密度，本文 中所闡述之熔融碳酸鹽燃料電池系統之電池電壓·高於具有 作為一進料之重組油氣體之目前技術水平的溶融碳酸鹽燃 料電池之電池電壓。 圖5針對在20%及30%之氫利用率下操作之實例1及2_所 模擬之熔融碳酸鹽燃料電池系統繪示功率密度（w/cm2)對 電流密度（mA/cm2)及具有作為一進料之一重組油氣體之一 熔融碳酸鹽燃料電池之文獻值。資料線166針對實例i及2 繪示在20%之氫利用率下之功率密度（w/cm2)對電流密度 (mA/cm2)。資料線168針對實例！及2繪示在3〇%之氫利用 率下之功率密度（W/Cm2)對電流密度（mA/cm2)。資料線17〇 針對如由 Larmine 等人在「Fuei Cell Systems Expiained」 (2003, Wiley & Sons，第199頁）中所闡述之目前技術水平 的熔融碳酸鹽燃料電池系統繪示功率密度（w/cm2)對電流 在、度（mA/cm2)。如圖5中所顯示，對於一給定電流密度， 本文中所闡述之熔融碳酸鹽燃料電池系統之功率密度高於 具有作為一進料之重組油氣體之熔融碳酸鹽燃料電池之功 率密度。 圖6針對貫例1緣示過量二氧化碳（Δρ⑽（巴）)及總燃料電 池電位（mV)對氫利用率。資料線172表示過量二氧化碳值 (在給定氫利用率及2〇〇 mA/cm2之一電流密度下）。資料 I74表不在一給定氫利用率下之平均過量二氧化碳值。資 料線176表示該燃料電池之如自能斯特方程式確定之在給 定氫利用率下之總電池電位(吟如圖6中所顯示，隨著 149088.doc -63 - 201108498 氫利用率增加，ΔΡ£：02減小且電池電位增加，因此在小於 5〇0/。之氫利用率下且二氧化碳淹沒之情形下操作該熔融碳 酸鹽燃料系統導致該熔融碳酸鹽燃料電池之增強之電池電 位。 圖7繪示圖6之燃料電池電位（mV)之二氧化碳部分。資料 線178表示燃料電池之電池電位（mV)之二氧化破部分（例 如’能斯特方程式之（RT/2F)ln(Pc〇2C/Pc〇2a)部分）。如圖7 中所顯示’當以二氧化碳淹沒該燃料電池之陰極部分時， 該燃料電池之一電池電壓升高。舉例而言，在一 20%之氫 利用率下且以約〇. 10 5之一過量二氧化碳值操作該燃料電 池，30 mV之總燃料電池電位便是由該過量二氧化碳造成 的0 如圖6及圖7中所顯示，當提供至燃料電池之二氧化碳之 量過量（ΔΡ〇〇2 >〇)且百分比氫利用率為低（例如，小於 35%、小於30%或小於2〇%)時，電池電位最大化。因此， 在小於50 /。之氫利用率下操作該炼融礙酸鹽燃料系統且將 過量二氧化碳提供至該熔融碳酸鹽燃料電池之一陰極部 分，使得該熔融碳酸鹽燃料電池之陰極部分之大部分中之 二氧化碳之-分壓高於該炫融碳酸鹽燃料電池之—陽極部 分之大部分中之二氧化碳之—八廠 刀/1 ’且精此增強該熔融碳 酸鹽燃料電池之電池電壓。 實例3針對包含藉由陽極排氣加熱之第—重組哭之一熔 融碳酸燃料電池系統（例如，，中所繪示之系統）使用上文 所關述之模擬來確定在7巴⑽.7咖或約7 _)下操作之 149088.doc • 64 * 201108498 一熔融碳酸鹽燃料電池之電流密度、電池電壓及功率密 度。在7巴之力及65G〇C2 —溫度下以2〇%或3〇%之氮 利用率操作該熔融碳酸鹽燃料電池。該第一重組器具有 2.5之-蒸汽對碳比。允許該第—重組器之溫度變化。盘 高溫氫分離裝置組合之第二重組器具有5〇(rc之一溫度及 巴之G力使用空軋作為氧源。使用空氣之值以使得 陰極進料巾之二氧化碳對分子氧之比係化學計量的，因此 最小化陰極側濃度極化。在所有情形中，使用苯作為進料 之系統之經組合碳轉化值介於93%與95%之間。由該系統 内之熱積體供應用於第二重組器之反應熱。藉由以CY. Yuh^J.R. Selman^J. Electrochem. Soc.(Vol. 138 . No. 12，1991年12月）中所闡述之方法單獨地計算以上方程式2 中之個別項來計算r。對於實例3，計算尺為〇 57 Ω cm2。 圖8針對如圖1中所繪示之一熔融碳酸鹽燃料電池繪示電 池電壓（mV)對電流密度（mA/cm2)。資料線18〇繪示在2〇% 之氫利用率下之電池電壓（mV)對電流密度（mA/em2)。資料 線182繪示在30%之氫利用率下之電池電壓（mV)對電流密 度（mA/cm2)。將圖4與圖8進行比較’在一給定電流密度 下’與在1巴下操作之熔融碳酸鹽燃料電池系統之電池電 壓相比，在約7巴之壓力下操作之熔融碳酸鹽燃料電池系 統觀察到一較高電池電壓。 圖9針對如圖1中所繪示之一熔融碳酸鹽燃料電池系統繪 示功率密度（W/cm2)對電流密度及該熔融碳酸鹽燃料電池 之一狀態。資料線184繪示在20%之氫利用率下之功率密 149088.doc -65- 201108498 度（W/cm2)對電流密度（mA/cni2)。資料線186繪示在30%之 氫利用率下之功率密度（W/cm2)對電流密度（mA/cm2)。資 料點 188 針對如由 j. r §eiman 在 j〇urnai p〇werThe state of the art molten carbonate fuel cell system set forth in Wiley & Sons 'p. 199 shows battery voltage (mV) versus current density 149088.doc -62 - 201108498 (mA/cm2). As shown in Figure 4, for a given current density, the battery voltage of the molten carbonate fuel cell system set forth herein is higher than the current state of the art molten carbonate fuel cell with a reconstituted oil gas as a feed. Battery voltage. Figure 5 shows the power density (w/cm2) vs. current density (mA/cm2) and the behavior for the molten carbonate fuel cell system simulated in Examples 1 and 2_ operating at 20% and 30% hydrogen utilization. A literature value for one of the molten oil fuels of one of the reconstituted oil gases. Data line 166 plots power density (w/cm2) versus current density (mA/cm2) at 20% hydrogen utilization for Examples i and 2. Data line 168 is for the instance! And 2 shows the power density (W/Cm2) versus current density (mA/cm2) at a hydrogen utilization rate of 3%. The data line 17 is for power density (w/) for a state of the art molten carbonate fuel cell system as described by Larmine et al., "Fuei Cell Systems Expiained" (2003, Wiley & Sons, page 199). Cm2) The current is in the degree (mA/cm2). As shown in Figure 5, for a given current density, the power density of the molten carbonate fuel cell system set forth herein is higher than the power density of a molten carbonate fuel cell having a reconstituted oil gas as a feed. Figure 6 shows the hydrogen utilization rate for excess carbon dioxide (?ρ(10)(bar)) and total fuel cell potential (mV) for Example 1. Data line 172 represents the excess carbon dioxide value (at a given hydrogen utilization rate and a current density of 2 mA/cm2). Data I74 shows the average excess carbon dioxide value at a given hydrogen utilization rate. Data line 176 represents the total cell potential of the fuel cell as determined by the Nernst equation at a given hydrogen utilization rate (as shown in Figure 6, with the increase in hydrogen utilization rate of 149088.doc -63 - 201108498, ΔΡ£:02 decreases and the battery potential increases, so operating the molten carbonate fuel system at a hydrogen utilization rate of less than 5 〇0/min and carbon dioxide flooding results in an enhanced battery potential of the molten carbonate fuel cell. Figure 7 is a diagram showing the carbon dioxide portion of the fuel cell potential (mV) of Figure 6. The data line 178 represents the dioxide breakdown of the battery potential (mV) of the fuel cell (e.g., 'NT/2F) ln (Pc) 〇2C/Pc〇2a)). As shown in Figure 7, 'when the cathode portion of the fuel cell is flooded with carbon dioxide, one of the fuel cells has an increased battery voltage. For example, a 20% hydrogen utilization The fuel cell is operated at a rate of about one of the excess carbon dioxide values of about 10 5 , and the total fuel cell potential of 30 mV is caused by the excess carbon dioxide as shown in FIG. 6 and FIG. 7 when supplied to the fuel cell. Dioxane When the amount of carbon is excessive (ΔΡ〇〇2 > 〇) and the percentage hydrogen utilization is low (for example, less than 35%, less than 30%, or less than 2%), the battery potential is maximized. Therefore, at less than 50 /. Operating the smelting acid fuel system under hydrogen utilization and supplying excess carbon dioxide to a cathode portion of the molten carbonate fuel cell such that a portion of the cathode portion of the molten carbonate fuel cell is divided by carbon dioxide The pressure is higher than the carbon dioxide in the majority of the anode portion of the smelting carbonate fuel cell - eight factory knife / 1 ' and this enhances the battery voltage of the molten carbonate fuel cell. Example 3 is directed to the anode row Gas Heating - Recombination Cry One of the molten carbonic acid fuel cell systems (eg, the system depicted in the above) uses the simulations described above to determine operation at 7 bar (10).7 coffee or about 7 _) 149088.doc • 64 * 201108498 Current density, battery voltage and power density of a molten carbonate fuel cell. The molten carbonate fuel cell was operated at a nitrogen utilization rate of 2% or 3% at a force of 7 bar and 65 G C2. The first recombiner has a vapor-to-carbon ratio of 2.5. Allow the temperature of the first-recombiner to change. The second recombiner of the combination of the high-temperature hydrogen separation device has a temperature of 5 〇 (the temperature of one of the rc and the G force of the bar are used as the oxygen source. The value of the air is used to make the ratio of the carbon dioxide to the molecular oxygen of the cathode feed towel. Metered, thus minimizing the concentration of the cathode side. In all cases, the combined carbon conversion value of the system using benzene as the feed is between 93% and 95%. The supply of heat in the system is used. The heat of reaction of the second recombiner. The above equation 2 is separately calculated by the method described in CY. Yuh^JR Selman^J. Electrochem. Soc. (Vol. 138. No. 12, December 1991). The individual term is used to calculate r. For Example 3, the ruler is 〇57 Ω cm2. Figure 8 shows the cell voltage (mV) versus current density (mA/cm2 for one molten carbonate fuel cell as shown in Figure 1). The data line 18〇 shows the battery voltage (mV) versus current density (mA/em2) at 2% hydrogen utilization. The data line 182 shows the battery voltage at 30% hydrogen utilization (mV). ) vs. current density (mA/cm2). Compare Figure 4 with Figure 8 'at a given current density' with A higher battery voltage was observed for the molten carbonate fuel cell system operating at a pressure of about 7 bar compared to the cell voltage of a molten carbonate fuel cell system operating at 1 bar. Figure 9 is for Figure 1 A molten carbonate fuel cell system is shown with power density (W/cm2) versus current density and one state of the molten carbonate fuel cell. Data line 184 shows power density 149088 at 20% hydrogen utilization. Doc -65- 201108498 degrees (W/cm2) versus current density (mA/cni2). Data line 186 shows power density (W/cm2) versus current density (mA/cm2) at 30% hydrogen utilization. Information point 188 is targeted by j. r §eiman at j〇urnai p〇wer

Sources(2006，第852至857頁）中所闡述之一目前技術水平 的熔融碳酸鹽燃料電池系統繪示功率密度（w/cm2)對電流 密度（mA/cm2)。如圖9中所顯示，在約3〇〇 mA/cm2之一電 流密度下’本文中所闡述之熔融碳酸鹽燃料電池系統之功 率密度咼於該目前技術水平的熔融碳酸鹽燃料電池之功率 密度。 實例4使用上文所闡述之模擬將作為用於熔融碳酸鹽燃 料電池系統之燃料源之甲烷與苯之使用進行比較，其中第 一重組器由陽極排氣加熱，無其他加熱。舉例而言，圖1 中所繪示之系統。藉由該系統内之熱積體供應用於第二重 組器之反應熱。對於此等模擬，在i巴（約〇1 Mpa或約i atm)之一壓力及65(rc之一溫度下操作該熔融碳酸鹽燃料 電池。使S氣作為氧源。使用空氣之值來在各種氮利用 率下產生二氧化碳對分子氧之為2之一莫耳比。進料至第 一重組器之燃料進料之量對於苯係1〇() kgm〇i/hr且對於甲 烷係600 kgmol/hr。在表2中針對苯且在表3中針對甲烷列 出該熔融碳酸鹽燃料電池之百分比氫利用率、第一及第二 重組器之操作條件及蒸汽對碳比。 士自 J. Power Sources 2002，112 ’ 第 509 至 518 頁所獲 得，假定方程式2中之R等於0.75 D.cm2。 149088.doc • 66 - 201108498 表2 h2利用率，％ 溫度，第 一重組 器，0C 溫度，第二 重組器， °C 壓力，第二 重組器，巴 蒸汽/破比， 第一重組器 蒸汽/破比，第二 重組器 20 605 500 15 3.0 3 30 574 500 15 3.2 3 40 549 500 15 3.3 3 50 527 500 15 3.3 3 表3 H2利用率，％ 溫度，第 一重組 器，0C 溫度，第 二重組 器，0C 壓力，第 二重組 器，巴 蒸汽/破比， 第一重組器 蒸汽/破比，第二 重組器 20 624 500 15 1.9 3 30 596 500 15 2.0 3 40 574 500 15 2.1 3 50 555 500 15 2.1 3 圖1 〇針對使用苯或曱烷作為一燃料源之熔融碳酸鹽燃料 電池系統繪示電池電壓（mV)對電流密度（mA/cm2)。資料線 190繪示使用苯作為一進料源在2〇%之氫利用率下之電池 電壓（mV)對電流密度（mA/cm2)。資料線192繪示使用曱烷 作為一進料源在20%之氫利用率下之電池電壓（mV)對電流 抢度（mA/cm2)。如圖10中所顯示，將苯用作第一重組器之 一燃料源時該熔融碳酸鹽燃料電池系統觀察到一較高電池 電壓。 149088.doc •67· 201108498 圖11針對在200 mA/cm2之一電流密度下使用苯或甲燒作 為一燃料源之一炼融碳酸鹽燃料電池系統之平均過量二氧 化碳（△〜㈣）對百分比農利用率。資料線194表示針對苯 在一給定氫利用率下之平均過量二氧化碳值。資料線196 表示針對甲燒之平均過量二氧化碳值。如圖u中所顯示， 在J於50%之氫利用率下，在一給定氣利用率下苯比尹院 提'更多過量二氧化碳。因此，當使用苯作為-燃料源 時每莫耳氫產生更多莫耳之二氧化碳。 如貫例1至4中所顯示，本文中所閣述之炫融碳酸鹽燃料 電池系統及方法藉由以下步驟提供增強之電流密度、電流 電壓^力㈣度且抑制該燃料電池之二氧化碳不足：將一 i括刀子氫之含氫流提供至一炼融碳酸鹽燃料電池之一陽 。八"控制該含氫流至該陽極之-流率以使得該陽極中 ，子氫利用率小於5〇% :將包括來自溶融碳酸鹽燃料電 刀子氫之陽極排氣與一包括烴之烴流混合，其中斑哕 烴流混合之該陽極排氣具有自戰至戰之一溫度:、使 氣㈣㈣之該混合物之至少一部分與一觸媒接觸 、“匕括種或多種氣態烴、分子氫及至少一種碳氧 + :'飞重組進料；自該蒸汽重組進料分離該分子氫之 卩刀’及將所分離之分子氫之至少-部分作為該包 括分子藍 電池陽極。卜部分提供至該炼融石炭酸鹽燃料 【圖式簡單說明】 圖1係用於實踐本文中所闡述之-方法之包含-第一重 149088.doc • 68 · 201108498 組器及與一第二重組器組合之一高溫氫分離裝置之—系統 之一實施例之一示意圖。 圖2係用於實踐本文中所闡述之一方法之包含具有一熱 父換器之一第一重組器及與一第二重組器組合之一高溫氫 分離裝置之一系統之一實施例之一示意圖。 圖3係其中高溫氫分離裝置位於第二重組器外部之系統 之一部分之一實施例之一示意圖。 圖4針對在1巴下操作之熔融碳酸鹽燃料電池系統之實施 例繪示電池電壓（mV)對電流密度（mA/cm2)。 圖5針對在1巴下操作之熔融碳酸鹽燃料電池系統之實施 例繪示功率密度（W/cm2)對電流密度。 圖6針對在7巴下操作之熔融碳酸鹽燃料電池系統之各種 實施例繪示電池電壓（mV)對電流密度（mA/cm2)。 圖7針對在7巴下操作之熔融碳酸鹽燃料電池系統之實施 例繪示功率密度（W/cm2)對電流密度⑻八化爪2)。 圖8針對在一給定氫利用率下使用各種量之過量空氣操 作熔融碳酸鹽燃料電池之實施例繪示百分比氫利用率對 △Pc〇2(巴）。 圖9針對使用曱院或苯作為一進料源操作熔融碳酸鹽燃 料電池之實施例繪示百分比氫利用率對ΔΡ(：〇2(巴）。 圖1 〇針對使用各種燃料源之熔融碳酸鹽燃料電池系統之 實施例繪示電池電壓（mV)對電流密度（mA/cm2)。 圖11針對使用各種燃料源之熔融碳酸鹽燃料電池系統之 實施例繪示平均過量二氧化碳（△PcOVavg))對百分比氫利用 149088.doc •69· 201108498 率 【主要元件符號說明】 10 燃料電池系統 12 熔融碳碳酸鹽燃 14 第一重組器 16 第二重組器 18 南溫氮分離裝置 20 氧化單元 22 熱交換器 24 陽極 26 陰極 28 電解質 30 陽極入口 32 陽極排氣出口 34 管線 36 節流閥 38 陰極入口 40 陰極排氣出口 42 含氧化劑氣體源 44 管線 46 節流閥 48 管線 50 管線 52 管線 149088.doc 70- 201108498 56 管線 58 閥 60 閥 62 管線 64 氫源 66 管線 68 南溫氫分離薄膜 70 管線 72 熱交換器 74 管線 76 節流閥 78 節流閥 80 管線 82 節流閥 84 管線 86 節流閥 88 管線 90 熱交換器 92 管線 94 壓縮機 96 管線 98 熱交換器 100 節流閥 102 三通節流閥 149088.doc •71 - 201108498 104 106 108 110 112 114 116 118 120 122 124 126 128 130 132 134 136 138 140 142 144 管線 烴流入口閥 重組區 管線 管線 節流閥 節流閥 節流閥 節流閥 管線 氫導管 管線 管線 節流閥 節流閥 節流閥 管線 管線 節流閥 管線 節流閥 149088.doc -72One of the state of the art molten carbonate fuel cell systems set forth in Sources (2006, pages 852-857) shows power density (w/cm2) versus current density (mA/cm2). As shown in Figure 9, at a current density of about 3 mA/cm2, the power density of the molten carbonate fuel cell system set forth herein is less than the power density of the state of the art molten carbonate fuel cell. . Example 4 compares the use of methane as a fuel source for a molten carbonate fuel cell system with benzene using the simulations set forth above, where the first recombiner is heated by the anode exhaust without additional heating. For example, the system depicted in Figure 1. The heat of reaction for the second recombiner is supplied by the thermal product in the system. For these simulations, the molten carbonate fuel cell is operated at one of the pressures of i bar (about 1 Mpa or about i atm) and 65 (rc). The S gas is used as the oxygen source. The value of the air is used. The nitrogen ratio of carbon dioxide to molecular oxygen is 2 under various nitrogen utilization rates. The amount of fuel feed to the first reformer is 1 〇() kgm〇i/hr for benzene and 600 kgmol for methane /hr. The percentage hydrogen utilization of the molten carbonate fuel cell, the operating conditions of the first and second recombiners, and the steam to carbon ratio are listed for benzene in Table 2 and in Table 3 for methane. Power Sources 2002, 112 ' Obtained on pages 509 to 518, assuming R in Equation 2 is equal to 0.75 D.cm2. 149088.doc • 66 - 201108498 Table 2 h2 Utilization, % Temperature, First Recombiner, 0C Temperature, Second recombinator, °C pressure, second recombiner, Ba steam/break ratio, first recombiner steam/break ratio, second recombiner 20 605 500 15 3.0 3 30 574 500 15 3.2 3 40 549 500 15 3.3 3 50 527 500 15 3.3 3 Table 3 H2 utilization, % temperature, first recombinator, 0C Temperature, second reformer, 0C pressure, second reformer, bar steam/break ratio, first reformer steam/break ratio, second reformer 20 624 500 15 1.9 3 30 596 500 15 2.0 3 40 574 500 15 2.1 3 50 555 500 15 2.1 3 Figure 1 电池 Battery voltage (mV) versus current density (mA/cm2) for molten carbonate fuel cell systems using benzene or decane as a fuel source. Data line 190 shows use Battery voltage (mV) vs. current density (mA/cm2) for benzene as a feed source at 2% hydrogen utilization. Data line 192 shows the use of decane as a feed source at 20% hydrogen utilization. Battery voltage (mV) versus current rush (mA/cm2). As shown in Figure 10, a higher battery was observed in the molten carbonate fuel cell system when benzene was used as a fuel source for the first recombiner. Voltage 149088.doc •67· 201108498 Figure 11 shows the average excess carbon dioxide (△~(d)) for a smelting carbonate fuel cell system using benzene or formazan as a fuel source at a current density of 200 mA/cm2. Percentage agricultural utilization. Data line 194 indicates for benzene in a given Average excess carbon dioxide value under utilization. Data line 196 indicates the average excess carbon dioxide value for the A-burn. As shown in Figure u, at a hydrogen utilization rate of 50%, the benzene ratio at a given gas utilization rate. Yin Yuan mentions 'more excess carbon dioxide. Therefore, when benzene is used as a fuel source, more moles of carbon dioxide are generated per mole of hydrogen. As shown in Examples 1 through 4, the dazzling carbonate fuel cell system and method described herein provides enhanced current density, current and voltage (four degrees) and inhibits carbon dioxide deficiency of the fuel cell by the following steps: A hydrogen-containing hydrogen stream of the knife is supplied to one of the smelting carbonate fuel cells. Eight " controlling the flow rate of the hydrogen-containing stream to the anode such that the sub-hydrogen utilization rate in the anode is less than 5% by weight: an anode exhaust gas comprising hydrogen from a molten carbonate fuel electro-knives and a hydrocarbon including hydrocarbons Flow mixing, wherein the anode exhaust gas mixed with the hydrocarbon hydrocarbon stream has a temperature from the war to the battle: at least a portion of the mixture of the gas (d) (d) is contacted with a catalyst, "including a plurality of gaseous hydrocarbons, molecular hydrogen And at least one carbon oxygen +: 'flying recombination feed; separating the molecular hydrogen from the steam recombination feed' and at least a portion of the separated molecular hydrogen as the anode comprising the molecular blue battery. The smelting carbonate fuel (simplified illustration) Figure 1 is used to practice the method described in this article - the first weight 149088.doc • 68 · 201108498 group and combined with a second recombiner A schematic diagram of one embodiment of a system of high temperature hydrogen separation apparatus. Figure 2 is a method for practicing one of the methods described herein, comprising a first recombiner having a hot parent converter and a second recombiner Combination of high temperature hydrogen Schematic diagram of one of the embodiments of one of the systems. Figure 3 is a schematic illustration of one embodiment of a system in which the high temperature hydrogen separation unit is located outside of the second reformer. Figure 4 is directed to molten carbonate operating at 1 bar. An embodiment of a fuel cell system depicts battery voltage (mV) versus current density (mA/cm2). Figure 5 illustrates power density (W/cm2) pairs for an embodiment of a molten carbonate fuel cell system operating at 1 bar. Current Density Figure 6 shows cell voltage (mV) versus current density (mA/cm2) for various embodiments of a molten carbonate fuel cell system operating at 7 bar. Figure 7 for molten carbonate operating at 7 bar An embodiment of a fuel cell system illustrates power density (W/cm2) versus current density (8) eight jaws 2). Figure 8 illustrates the implementation of operating a molten carbonate fuel cell using various amounts of excess air at a given hydrogen utilization rate. The example shows the percentage hydrogen utilization versus ΔPc 〇 2 (bar). Figure 9 shows the percentage hydrogen utilization versus ΔΡ (: 〇 2 for an example of operating a molten carbonate fuel cell using a brothel or benzene as a feed source. (巴). 1 电池 Battery voltage (mV) versus current density (mA/cm 2 ) for an embodiment of a molten carbonate fuel cell system using various fuel sources. Figure 11 is an embodiment of a molten carbonate fuel cell system using various fuel sources The average excess carbon dioxide (ΔPcOVavg) is shown as a percentage of hydrogen utilization 149088.doc •69· 201108498 rate [main component symbol description] 10 fuel cell system 12 molten carbon carbonate burning 14 first recombiner 16 second recombiner 18 south Warm Nitrogen Separation Unit 20 Oxidation Unit 22 Heat Exchanger 24 Anode 26 Cathode 28 Electrolyte 30 Anode Inlet 32 Anode Exhaust Outlet 34 Line 36 Throttle Valve 38 Cathode Inlet 40 Cathode Exhaust Outlet 42 Oxidizer Gas Source 44 Line 46 Throttle 48 Line 50 Line 52 Line 149088.doc 70- 201108498 56 Line 58 Valve 60 Valve 62 Line 64 Hydrogen Source 66 Line 68 South Temperature Hydrogen Separation Membrane 70 Line 72 Heat Exchanger 74 Line 76 Throttle Valve 78 Throttle 80 Line 82 Throttle valve 84 line 86 throttle valve 88 line 90 heat exchanger 92 line 94 compressor 96 Line 98 Heat exchanger 100 Throttle valve 103 Three-way throttle valve 149088.doc • 71 - 201108498 104 106 108 110 112 114 116 118 120 122 124 126 128 130 132 134 136 138 140 142 144 Pipeline hydrocarbon inlet valve reorganization Zone pipeline pipeline throttle valve throttle valve throttle valve throttle valve pipeline hydrogen pipeline pipeline pipeline throttle valve throttle valve throttle valve pipeline pipeline throttle valve throttle valve 149088.doc -72

Claims (1)

201108498 七、申請專利範園： 1· 一種操作一熔融碳酸鹽燃料電池之方法，其包括： 將—包括分子氫之含氫流提供至一熔融碳酸鹽燃料電 池之一陽極部分； 控制该含氫流至該陽極之一流率以使得該陽極中之分 子氫利用率小於50% ; 將包括來自該熔融碳酸鹽燃料電池之分子氫之陽極排 氣與包括煙之烴流混合，其中與該烴流混合之該陽極 排氣具有自500eC至700t之一溫度； 使％極排氣與该煙流之該混合物之至少一部分與一觸 媒接觸以產生一包括一種或多種氣態烴、分子氫及至少 一種碳氧化物之蒸汽重組進料； 自該蒸汽重組進料分離該分子氫之至少一部分；及 將该所分離之分子氫之至少一部分作為該包括分子氫 之含氫流之至少一部分提供至該熔融碳酸鹽燃料電池陽 極〇 2. 如請求項1之方法，其中該含氫流包括至少〇6或至少約 〇·95莫耳分率分子氫。 3. 如請求項1之方法，其中該烴流之該等烴中之至少某些 烴包括具有至少為4之碳數目之一種或兩種可蒸發烴。 4. 如請求項1之方法，其進一步包括以一量將二氧化碳進 料至該熔融碳酸鹽燃料電池之一陰極部分以使得該熔融 碳酸鹽燃料電池之大部分陰極部分中之二氧化碳分壓高 於該熔融碳酸鹽燃料電池之大部分陽極部分中之二氧化 I49088.doc 201108498 碳分壓。 5. 如請求項4之方法’其中該熔融碳酸鹽燃料電池之該陰 極部分之入口或排氣出口處之二氧化碳分壓與該熔融碳 酸鹽燃料電池之該陽極部分之該排氣出口處之二氧化碳 为壓之間的差值為至少〇 〇5巴、或至少〇丨巴或至少 巴。 6. 如μ求項4之方法，其中藉由高溫氫分離裝置提供被提 供至該熔融碳酸鹽燃料電池之該陰極部分之該二氧化碳 之至少一部分。 7. 如請求項1之方法，其進一步包括以下步驟：自該蒸汽 重組進料分離一包括該等碳氧化物中之至少一者及該等 氣.vl U中之至少一者之氫耗盡氣流之至少一部分，使該 所分離之氫耗盡流之至少一部分與氧化劑接觸以產生一 經加熱流，及將來自該經加熱流之熱之至少一部分提供 至S亥陽極排氣及/或提供至該包括烴之烴流。 8. 如请求項1之方法，其進一步包括：將空氣及二氧化碳 提供至該熔融碳酸鹽燃料電池之—陰極，其中該空氣包 括分子氧；及控制該空氣及/或二氧化碳之一流率以使得 二氧化碳對分子氧之一莫耳比為至少2。 9. 如請求们之方法，其進一步包括：使提供至該熔融碳 酉义I陽極之忒分子氫之至少一部分在該熔融碳酸鹽燃料 電池之一陽極中之一個或多個陽極電極處與氧化劑混 口及以至少0.1 w/cm2之-電功率密度自該溶融碳酸鹽 燃料電池產生電。 149088.doc •2- 201108498 ίο. —種熔融碳酸鹽系統，其包括： 一熔融碳酸鹽燃料電池，其經組態以於一流率接收一 包括分子氫之含氫流以使得該熔融碳酸鹽燃料電池之一 陽極中之氫利用率小於5〇〇/0 ; 一個或多個重組器，其以操作方式耦合至該熔融碳酸 鹽燃料電池，至少一個重組器經組態以接收來自該熔融 碳酸鹽燃料電池之陽極排氣及烴，且經組態以允許該陽 極排氣與烴充分地混合以至少部分地重組該等烴中之某 些烴以產生一經重組產物流，其中該經重組產物流包括 分子氫及至少一種碳氧化物；及 一高溫氫分離裝置，其係該等重組器中之至少一者之 部分或輕合至該等重組器中之至少一 一者且以操作方式耦201108498 VII. Patent Application: 1. A method of operating a molten carbonate fuel cell, comprising: providing a hydrogen-containing stream comprising molecular hydrogen to an anode portion of a molten carbonate fuel cell; controlling the hydrogen-containing Flow rate to one of the anodes such that the molecular hydrogen utilization in the anode is less than 50%; mixing anode exhaust gas comprising molecular hydrogen from the molten carbonate fuel cell with a hydrocarbon stream comprising smoke, wherein the hydrocarbon stream Mixing the anode exhaust gas with a temperature from 500 eC to 700 t; contacting at least a portion of the mixture of the % polar exhaust gas and the flue gas with a catalyst to produce a gas comprising one or more gaseous hydrocarbons, molecular hydrogen, and at least one a vaporous recombination feed of carbon oxide; separating at least a portion of the molecular hydrogen from the vapor reformed feed; and providing at least a portion of the separated molecular hydrogen to the melt as at least a portion of the hydrogen-containing hydrogen stream comprising the molecular hydrogen The method of claim 1, wherein the hydrogen-containing stream comprises at least 〇6 or at least about 〇·95 mole fraction molecular hydrogen . 3. The method of claim 1 wherein at least some of the hydrocarbons of the hydrocarbon stream comprise one or two vaporizable hydrocarbons having a carbon number of at least four. 4. The method of claim 1, further comprising feeding carbon dioxide to a cathode portion of the molten carbonate fuel cell in an amount such that a partial pressure of carbon dioxide in a majority of the cathode portion of the molten carbonate fuel cell is higher than The carbon dioxide partial pressure in the majority of the anode portion of the molten carbonate fuel cell is I49088.doc 201108498. 5. The method of claim 4, wherein the partial pressure of carbon dioxide at the inlet or exhaust outlet of the cathode portion of the molten carbonate fuel cell and the carbon dioxide at the exhaust outlet of the anode portion of the molten carbonate fuel cell The difference between the pressures is at least 巴5 bar, or at least 〇丨 bar or at least bar. 6. The method of claim 4, wherein at least a portion of the carbon dioxide supplied to the cathode portion of the molten carbonate fuel cell is provided by a high temperature hydrogen separation unit. 7. The method of claim 1, further comprising the step of separating from the vapor recombination feed a hydrogen depletion comprising at least one of the carbon oxides and at least one of the gases vl U At least a portion of the gas stream contacting at least a portion of the separated hydrogen depleted stream with an oxidant to produce a heated stream, and providing at least a portion of the heat from the heated stream to the Shai anode exhaust and/or to The hydrocarbon stream comprising hydrocarbons. 8. The method of claim 1, further comprising: providing air and carbon dioxide to the cathode of the molten carbonate fuel cell, wherein the air comprises molecular oxygen; and controlling a flow rate of the air and/or carbon dioxide to cause carbon dioxide One molar ratio to molecular oxygen is at least 2. 9. The method of claimant, further comprising: causing at least a portion of the hydrazine molecular hydrogen supplied to the molten carbon I anode to be at one or more anode electrodes in the anode of the molten carbonate fuel cell and the oxidant Mixing and generating electricity from the molten carbonate fuel cell at an electrical power density of at least 0.1 w/cm2. 149088.doc • 2 201108498 ίο. A molten carbonate system comprising: a molten carbonate fuel cell configured to receive a hydrogen-containing stream comprising molecular hydrogen at a first rate to cause the molten carbonate fuel The hydrogen utilization rate in one of the anodes of the battery is less than 5 〇〇 / 0; one or more recombiners operatively coupled to the molten carbonate fuel cell, at least one recombinator configured to receive from the molten carbonate An anode exhaust of a fuel cell and a hydrocarbon, and configured to allow the anode exhaust to be thoroughly mixed with hydrocarbons to at least partially recombine certain hydrocarbons of the hydrocarbons to produce a recombined product stream, wherein the reconstituted product stream Including molecular hydrogen and at least one carbon oxide; and a high temperature hydrogen separation device that is at least one of the recombiners or is lightly coupled to at least one of the recombiners and is operatively coupled 熔融碳酸鹽燃料電池。 149088.docMolten carbonate fuel cells. 149088.doc
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