TW200301160A - Catalytic reactor and process - Google Patents

Catalytic reactor and process Download PDF

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Publication number
TW200301160A
TW200301160A TW091135177A TW91135177A TW200301160A TW 200301160 A TW200301160 A TW 200301160A TW 091135177 A TW091135177 A TW 091135177A TW 91135177 A TW91135177 A TW 91135177A TW 200301160 A TW200301160 A TW 200301160A
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Taiwan
Prior art keywords
steam
methane
hydrogen
patent application
reactor
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TW091135177A
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English (en)
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TW592832B (en
Inventor
Michael Joseph Bowe
Clive Derek Lee Tuffnell
Jason Andrew Maude
Ian Frederick Zimmerman
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Accentus Plc
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Publication of TW592832B publication Critical patent/TW592832B/zh

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/249—Plate-type reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/2495—Net-type reactors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00117—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2219/2491—Other constructional details
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    • B01J2219/32466—Composition or microstructure of the elements comprising catalytically active material
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
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    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1005—Arrangement or shape of catalyst
    • C01B2203/1035—Catalyst coated on equipment surfaces, e.g. reactor walls
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    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
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  • Chemical & Material Sciences (AREA)
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  • Combustion & Propulsion (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

20U30H6U 玖、發明說明 (發明說明應敘明··發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明) (一） 發明所屬之技術領域 本發明關於一種催化方法，及關於一種含有適用於進行 該方法的催化反應器之設備。 (二） 先前技術 W〇01/51194(Accentus pic)中敘述一種方法，其中在第 一催化反應器中甲烷與蒸汽反應而產生一氧化碳和氫；然 後在第二催化反應器中將所得到的氣體混合物用於進行費 雪-闕布希合成。總結果爲將甲烷轉化成較高分子量的烴類 ，其在周圍條件下一般爲液體。此方法的兩階段，即蒸汽/ 甲烷重組和費雪-闕布希合成，係需要不同的觸媒，而且陳 述各階段用的催化反應器。當反·應器分別爲吸熱和放熱時 ’催化反應器能傳遞熱量至反應氣體或來自反應氣體；甲 烷的燃燒提供蒸汽/甲烷重組所需的熱量此方法的潛在問題 爲蒸汽/甲院重組反應器中可能發生其它反應，產生二氧化 碳或產生焦炭。有建議重組器可倂有鈀/铑觸媒，反應在 8 0 0 °C進行。所建議的方法依賴於蒸汽/甲烷比，其接近1 :丄 ，因爲铑觸媒明顯地抗焦化。已經發現一種進行此方法的 改良方式。 (三） 發明內容 本發明提供一種用於進行蒸汽/甲烷重組以產生一氧化碳 和氫之方法’其中使氣體混合物流經金屬片之間的窄流體 - ί 20ύ30Η6ϋ 通道，該金屬片隔開流體通道與熱源，該流體通道含有一 具金屬基材的流體可透過之觸媒結構，以便增加熱傳遞， 通道內的滯留時間係少於0 · 5秒，而且沿著通道的平均溫 度及通道出口溫度皆在7 5 0 t至9 00°C的範圍內，俾形成一 氧化碳的選擇率在85%以上。 較宜地，滯留時間係少於0 . 1秒，但是較佳爲至少0 . 0 2 秒。推測如此短的時間係能讓製程在不平衡條件下操作， 俾僅使有具比較快動力學的反應能發生。亦較宜地，蒸汽 對甲烷的比例爲在1 · 2至2 · 0的範圍內，更佳1 . 3至1 · 6 ’最佳約1 . 4或1 . 5。在這些條件下，進行反應的甲烷之 比例可超過9 0%，且可能超過9 5%。再者，形成一氧化碳而 非二氧化碳的選擇率可超過9 0%(在本文中選擇率係指CO 莫耳數/ (CO莫耳數/ C02莫耳數））。 催化反應器較佳爲包括數個排列用於界定第一和第二流 體通道的金屬片，通道係交替排列著以確保在它們之間流 體有良好的熱接觸。視所需要的反應而定，在各通道中應 提供適合的觸媒。爲了確保所需要的良好熱接觸，第一和 第二流體通道在與片成垂直的方向較佳爲皆少於5毫米深 。第一和第二流體通道更佳爲皆少於3毫米深。波形箔或 具有凹坑的箔、金屬網或波形或皺摺的金屬氈片可在流體 通道內用當作觸媒結構的基材，以增加熱的傳遞及觸媒的 表面積。因爲蒸汽/甲烷重組方法需要良好的熱接觸以在co 的形成中達成高的選擇率，故較佳的結構爲包括一種具有 薄塗層（其含觸媒材料）的金屬箔。 -7-
ί 20U3〇il6U 如WO 01/51194中所述，該反應器可用於進行甲烷/蒸汽 重組’交替的通道含有甲烷/空氣混合物，故放熱氧化反應 供吸熱重組反應所需要的熱量。氧化反應可以使用數種 不同的觸媒’例如陶瓷載體上的鈀、鉑或銅；例如經鑭、 鈽或鋇所安定的氧化鋁載體上之銅或鉑，或氧化鉻上之鈀 ’或金屬六鋁酸鹽如鎂、鈣、鋸、鋇或鉀的六鋁酸鹽上之 絶’或較佳爲氧化鋁上的鈀或鉑。重組反應亦可以使用數 種不同的觸媒，例如鎳、鉑、鈀、釕或铑，其可用在陶瓷 塗層上；重組反應的較佳觸媒係氧化鋁或經安定的氧化鋁 上之铑或鉑。觸媒塗層較佳爲1〇-50μιη厚。氧化反應可實 質上在大氣壓力下進行，然而反應也可在高壓進行，例如 在高達2 MPa(20大氣壓）的壓力，但在大氣壓力下操作係較 宜的，或可以在稍微高的壓力，例如在大氣壓力以上的〇 至200kPa的範圍內。 將了解的是，反應器的材料在使用時係遭受嚴重的腐蝕 環境，例如溫度可能與900 °C同樣高，但是更典型爲約 8 0 0 °C或8 5 0 °C。反應器可爲金屬製，如帶有鋁的鈀粒鐵鋼 ，尤其已知稱爲費克拉洛尹（Fecral loy)(商標）的類型，其 爲鐵與高達20%鉻、0 · 5-12%鋁及0 ·卜3%釔。例如其可包括 鐵與1 5%鉻、4%鋁及0 · 3%釔。當在空氣中加熱此金屬時， 其形成氧化鋁的黏附氧化物塗層以保護合金防止更進一步 的氧化；此氧化物層亦保護合金在例如甲烷氧化反應器或 蒸汽/甲烷重組反應器的條件下避免被腐蝕。當將此金屬用 作觸媒基材且經一種內混有觸媒材料的陶瓷層所被覆時， ~ 8 -
I： 2QU3〇HBU 茲相信金屬上的氧化鋁層係與氧化物塗層結合，以確保催 化材料黏附於金屬基材。一種替代性的結構金屬係爲 Inconel HT800或另一種高溫合金。 爲了某些目的，可改將觸媒金屬直接沈積在金屬的黏附 氧化物塗層上（沒有任何陶瓷層）。 上述蒸汽/甲烷重組方法所製造的氣體較佳爲接著經歷費 雪-闕布希合成。此可使用具有不同觸媒的第二反應器來進 行。在費雪-闕布希合成後，當過量的氫殘留時，較佳爲由 所欲的產品中分離出氫，及將其送回蒸汽/甲烷重組反應器 的燃燒流體通道。已經發現在此通道內，甲烷與氫的混合 物之燃燒係能產生更均勻的溫度，而且當反應器爲冷時亦 能較容易地引發燃燒反應。 (四）實施方式 現將參考圖式藉由實施例來更進一步且更詳細地說明本 發明。 本發明關於一種用於將甲烷轉化成較長鏈的烴類之化學 方法。第一階段涉及蒸汽/甲烷重組，即以下反應： H20 + CH4 — C〇 + 3H2 此反應係吸熱的，且可在第一氣流通道中被铑或鉑/鍺混 合物所催化。此反應所需要的熱量由甲烷的燃燒所提供， 即： CH4 + 3〇2 — C〇2 + 2H20 其係一種放熱反應，且可在相鄰的第二氣流通道中被鈀 或鉑/鈀混合物所催化。這些反應皆可發生在大氣壓力，但 -9-
I： 2QU30U6U 是重組反應也可能發生在高壓。燃燒反應所產生的熱將被 導引經過用於分隔相鄰通道的金屬片。 蒸汽/甲烷重組所產生的氣體混合物於是可用於進行費雪 -闕布希合成，以產生較長鏈的烴，即 nC〇 + 2nH2 — (CH2)n + nH2〇 其係一種放熱反應，發生在高溫，典型上介於200和 3 5 0 °C之間，例如2 30°C，及在高壓，典型上介於2MPa和4MPa 之間，例如2 . 5MPa，於觸媒如鐵、鈷或熔融磁鐵礦，具有 促進劑如鉀。反應所形成的有機化合物之特性係取決於溫 度、壓力、觸媒以及一氧化碳對氫的比例。較佳的觸媒包 括比表面積1 40 - 230m2/g且具有約10-40%(相對於氧化鋁的 重量）鈷的γ-氧化鋁，且具有釕、鈾或釓促進劑，該促進劑 係爲鈷重量的0 . 0 1 %至1 0%，並具有鹼性促進劑如Th02。此 合成反應所放出的熱係用來提供蒸汽/甲烷重組反應所需要 的熱之至少一部分，例如可用傳熱流體如氨氣、加壓水或 Syltherm(Dow Corning的商標）傳遞來自發生費雪·闕布希 合成的反應器之熱，該熱用於預熱供應至重組反應器的至 少一個氣流。 現參閱第1圖，以流程圖來顯示全部化學程序。進料氣 1 0係主要由甲烷和小百分率（例如1 〇% )的乙烷和丙烷所構 成。其通經一熱交換器1 1，俾其之溫度約4 0 0 °C，然後經 由流體漩渦式混合器1 2供應第一催化反應器1 4 ;在混合 器1 2中，進料氣係與亦約4 0 0 °C的蒸汽束流作混合，該束 流經由切線入口進入混合器1 2，及沿著螺旋路徑至軸出口 -10-
ί 2QU30iiBU ，俾它們變成徹底混合。二束流可在大氣壓力，或例如在 大氣壓力以上的lOOkPa。流動方式較佳爲使得蒸汽：甲烷 旲耳比（在蒸汽/甲烷重組階段）介於1 . 3和1 . 6之間，較佳 1.4至1.5。反應器14的第一部分係在400 °C具有鉑/铑甲 烷化作用觸媒的預重組器1 5，其中高級烷類與蒸汽反應以 形成甲院（及一氧化碳）；需要額外的蒸汽以確保在此預重 組階段後（此預重組器1 5可能爲一獨立的反應器，若進料 氣1 0實質上不含有高級烷類時則其係不需要的）達成所欲 的蒸汽/甲烷比例。反應器1 4的第二部分係具有鉑/铑觸媒 的重組器1 6，其中甲烷與蒸汽反應以形成一氧化碳和氫。 此反應可在8 5 0 °C進行。 可由相鄰氣流通道內的鈀或鉑上的甲烷之燃燒來提供吸 熱反應所需要的熱。觸媒可倂有當作基材的γ_氧化鋁，經 鈀/鈾2 : 1混合物所塗覆，其充當寬溫度範圍的觸媒，俾溫 度由500增加至800°C或90CTC。可在沿著反應器14的階 段中供應甲烷/氧氣混合物，以確保燃燒係發生在遍及於其 長度。 由重組器1 6所出來的一氧化碳和氫之熱混合物然後通經 熱交換器1 8以被驟冷，俾提供熱蒸汽給漩渦式混合器} 2 ，然後經過熱交換器1 1，其中它失去熱量而送給進料氣。 然後藉由通過一被水冷卻的熱交換器20而將混合物更進一 步冷卻至約100 °C。氣體然後被壓縮機 22壓縮至 2.5MPa(25atm)的壓力。 高壓的一氧化碳和氫之束流然後被送至催化反應器26, -11-
2QU30H6U 於其中氣體發生反應，進行費雪-闕布希合成，而形成烷屬 烴或類似化合物。此反應係放熱的，較佳爲發生於約23 Ot ，且所產生的熱可用預熱要供應至熱交換器18的蒸汽，該 熱交換器使用一種循環於反應器26與蒸汽發生器28的熱 交換通道之間的熱交換流體。在此合成期間，氣體的體積 減少。然後將所產生的氣體通入冷凝器30，於其內與最初 在25°C的水作熱交換。高級烷類（例如C5以上）凝結成液體 ，如同水，此混合物通往重力分離器3 1 ;所分離出的高級 烷類於是可當作所要的產物被移出，而水經由熱交換器28 和1 8回到混合器^ 2。 任何低級烷類或甲烷以及殘存的氫係通經冷凝器3 0及送 往冷凍式冷凝器3 2，於其中被冷卻至約5 °C。殘存的氣體 主要係由氫、二氧化碳、甲烷和乙烷所構成，其通經減壓 渦輪3 3及經由導管3 4被送入儲槽3 5內，然後經由閥3 6 進入第一催化反應器1 4的燃燒通道。被冷凝的蒸氣主要係 由丙烷、丁烷和水所構成’其通往重力分離器3 7，來自其 的水與來自分離器3 1的循環水結合，而烷類被循環至進料 管1 0，俾送入預重組器1 5內。如虛線所示’渦輪3 3所發 出的電力可用於幫助壓縮機2 2的驅動。 當使用此形式時，程序的總結果爲將甲院轉化成較局分 子量的烴類，其在周圍溫度典型上係液體。該程序可用在 油或氣體，良好地將甲烷氣轉化成液態烴’其係較易於運 輸。 根據以上所給的蒸汽/甲烷重組反應’吾人預期蒸汽對甲 - 12- I： 2QU3〇iX6U ? 烷的適當莫耳比應爲1 : 1。然而，在該比値時有焦化的重 大危險，且有大比例的甲烷將不會進行反應之危險。增加 蒸汽的比例會增加甲烷反應的比例，及減少焦化的危險， 但是若蒸汽的比例太高則會同樣地增加二氧化碳的形成。 過量的蒸汽係能量的浪費，而且會稀釋反應物氣體。已發 現，在1 . 3至1 . 6間的蒸汽/甲烷比操作時，較佳爲在1 . 4 或1 . 5的蒸汽/甲烷比，結合短的滯留時間，較佳爲l〇〇ms ，則能對一氧化碳的形成有高選擇率，而且有非常高比例 的甲烷進行反應。經過重組器1 6的流速較佳爲使得滯留時 間在20至100ms的範圍內，更佳約50ms。 該短的滯留時間使得反應器1 6能在非平衡的條件下操作 。一氧化碳與蒸汽之間的競爭反應（會形成不想要產物二氧 化碳和氫）之動力學係慢於形成一氧化碳和氫的蒸汽/甲院 重組反應；且在重組反應中，逆向程序之動力學係慢於順 向程序。短的滯留時間使得較慢的反應沒有足夠的時間抵 達平衡。在這些條件下，甲烷進行反應的比率可能超過90% ’而且對一氧化碳的選擇率可超過90%。 表中顯示此蒸汽/甲烷重組階段的實驗測量。在各情況中 ’蒸汽/甲烷比係1 . 5 ’氣體混合物係被預熱至4 5 0或 5 5 0 C ’且重組益內的滯留時間係5 0 m s。重組器具有二層， 其內具有全部1 5個通道以供蒸汽甲烷重組反應，各通道的 覓型爲1〇_’長度爲1〇〇_，深度爲1.5_，含有一具鉑/ 鍺觸媒的薄氧化鋁塗層之相同尺寸的波形箔。這些通道與 燃燒通道之四層交替著，以達成所需的熱輸入。 -13-
20U30U6U 在沿著中央通道的四個位置處（在其長度的10%、40%、60% 和9 0% )測量溫度，這些測量値的第一個和最後一個在表中 列爲入口和出口溫度，且亦將所有四個溫度的平均値列表 入口溫度/ °c 出口溫度/°C 平均溫度厂 C CO選擇率/% ch4轉化率/% 656 736 712 80.1 80.7 717 851 805 88.6 91.3 727 869 810 90.3 93.7 726 853 810 92.5 93.8 731 866 815 93.0 94.2 當平均溫度和出口溫度高於7 5 0°C時，CO選擇率爲85%以 上。當出口溫度在8 3 (TC以上，較佳8 5 (TC以上時，得到更 佳的CO選擇率。於氫的存在下將反應器的溫度上升至約 8 5 0°C以進行預處理亦可改善反應器的性能，因爲其改善後 續的觸媒活性。 如上述，進料至費雪-闕布托合成反應器的理想之氫/ 一 氧化碳化學計量比例係2莫耳的氫對1莫耳的一氧化碳。 如上討論的’藉由蒸汽/重組反應係不容易獲得此比例，在 蒸汽/甲烷比爲1 . 0時，所得到的氣體混合物具有3 : 1之氫 對一氧化碳比，而在必須採用高蒸汽/甲烷比以避免焦化時 ，氫對一氧化碳比係約3 ’且可能高達4比1。因此，在費 雪-闕布托合成反應已經發生後，將有過量的氫殘存著。己 經發現’將此氣體送入反應器1 4的燃燒通道會產生更均勻 的溫度分佈，而使得在反應器冷時能更容易地引發燃燒反 -14-
^ 2QU3〇U6U 應（因此催化燃燒可在與1 5或20t同樣低的溫度發生）。製 程的總熱效率係被改善了，直接送入燃燒通道的甲烷量係 減少了，而且一氧化碳排放至環境的量亦減少了。 現參閱第2圖，反應器4 0 (適合於蒸汽/甲烷重組的例子） 包括一堆板4 2，各屬費克拉洛尹鋼，各爲側邊2 5 Omm且厚 度3mm之六角形。應了解的是，所給予的反應器4〇係僅爲 例子而已’而且其它催化反應器設計可代替地使用。在各 板中切削出寬2 0 m m且深2 · 5 m m的溝槽4 4，其從各板之一 邊橫過至另一邊，被寬3mm的陸面45所隔開（爲了簡明起 見，圖中僅顯示四條溝槽44和三個陸面45 )。一經含觸媒 材料的厚10-20μπι陶瓷塗層所被覆且具有高2 . 5mm波紋的 厚5 Ομηι費克拉洛尹鋼之載體箔46可滑入各溝槽44(圖中 僅顯示一個）內。一疊板4 2被組裝，在相繼的板4 2中溝槽 4 4的方向差異係6 0 °，且係被費克拉洛尹鋼的扁平頂板所 覆蓋；該堆疊體於是擴散地結合一起。然後將波形箔46插 入。接著使頭部4 8附著於所組裝的堆疊體的面。因此，溝 槽44界定氣流通道；且板42的方向爲使得任一個板42之 上或下板42中的流向爲互相成丨2〇。（這些構槽係分別由虛 線和鏈線所示）。 蒸汽/甲烷混合物係供應至頭部48 a，而所得到的氫與一 氧化碳之混合物係經由頭部48d流出。甲烷/空氣混合物係 供應經過頭部4 8 c及4 8 e (即頭部4 8 a之任一側的頭部，俾 來自燃燒程序的廢氣係經由頭部48b及48 f流出，因此氣 流係至少部分逆流的，俾燃燒通道中最熱的區域（其最靠近 -15-
I 20U3〇ilbU 這些通道的入口）係最接近蒸汽/甲烷重組反應的出口。另 外，在某些情況中，可爲部分並流。 頭部4 8各包括一簡單矩形帽，其周緣密封於堆疊體外側 ，俾蓋住堆疊體的一面。它們可焊接到堆疊體的外側。將 了解的是，在使用一段時間後，若通道兩者或之一中的觸 媒已經被耗盡，則可移除或分離頭部4 8，及移除並替換對 應的帶有觸媒之箔46。然後，再裝上頭部48。 將了解的是，氣流通道內的波形箔46上所沈積的陶瓷之 類型可能不同於堆疊體中的連續板42，而且觸媒材料亦可 能不同。例如，陶瓷可包括在氣流通道之一中的氧化鋁及 在其它氣流通道中的氧化锆。板42所形成的反應器40亦 可適用於進行費雪-闕布希合成。因爲形成堆疊體的板42 係接合在一起，故氣流通道係氣密的（除了各端與頭部48 連通外），且板42和溝槽44的尺寸係爲使得交替的氣流通 道內之壓力可能相當不同。波形箔46的間距或樣式可沿著 反應器通道44而變化，以便調整催化活性，因此在反應器 40的不同點提供對溫度或反應速率的控制。可有超過一層 的波形箔配置成爲通道44中的堆疊體。波形箔46亦可爲 具有穿孔者，以便促進通道44內流體的混合。再者，箔46 的部分可沒有觸媒。 在反應器40的一修飾例中，箔46係再度爲費克拉洛尹 材料製，但是觸媒材料係直接沈積在費克拉洛尹的氧化物 層上。作爲另一替代例，箔4 6可金屬線網或波形或打摺的 纖維板所替換。將了解的是，反應器40可爲其它材料製， -1 6 -
20U30H6U 例如，費雪-闕布希合成用的反應器40可爲鈦或不銹鋼製 〇 特別地，當反應器40將用於費雪-闕布希合成時，反應 器的氣流通道44可減少寬度，及可能的話以及沿著其長度 之深度，俾改變流體流動條件，及熱傳或質傳係數。在合 成反應期間，氣體體積減少，且藉由適當地使通道4 4逐漸 變細，則在反應進行時可維持氣體速度。再者，波形箔46 的間距或樣式可沿著反應通道4 4而變化，俾調整催化活性 ，而因此在反應器40的不同點提供對溫度或反應速率的控 制。反應器亦可爲不同形狀者，例如由具有溝槽界定流體 通道的一疊矩形板，在連續板中溝槽係爲不同方向，例如 在相對於板之縱軸分別成0°、+45。、0。、-45。角度。沿著 堆疊體側面的頭部係能使得氣體由一組通道流向下一組。 當反應器如反應器4 0係用於氣體之間的反應以產生氣態 產物時，則通道的方向係不重要的。然而，若產物爲液體 ，則較佳安排反應器40以使得反應的流動途徑係向下傾斜 ，以確保所形成的任何液體將由通道44排出。矩形反應器 ，其中頭部提供連續通道之間的連通，係意味該頭部可增 進所夾帶的液滴由氣液中分離，或凝結一些的蒸氣。 將了解的是，相關於第1圖所述的全部程序可被不同方 式所修改。例如，來自分離器3 7的短鏈烷類可被送入燃燒 通道1 4內。若在費雪-闕布希反應器2 6中發現長鏈鱲狀產 物時，則冷凝器30可僅將此產物冷到到例如60或80°C。 將了解的是，可由相鄰通道中的催化燃燒來提供蒸汽/甲 -17-
i 2QU30H6U 烷重組反應的熱（如上述），但是作爲替代例，燃燒可發生 在外部燃燒器（如層流燃燒器）中，約900或lOOOt之非常 熱的廢氣係通經反應器1 4的第二氣流通道，與甲烷的流動 方向成反向；此使得重組器1 6內的反應氣體能抵達與 900°C同樣高的最終溫度。在此情況中，未必要在具有陶瓷 塗層或觸媒的燃燒通道中提供箔，但是藉由傳遞熱量給分 離板42，該箔應能增進帶有熱廢氣的第二氣流通道與預重 組器和重組器通道中的反應物之間的熱傳遞。在催化反應 器1 4的燃燒通道中，若使用催化燃燒來產生熱（如所不）時 ，則燃燒觸媒本身可被薄的多孔惰性陶瓷層所塗覆，俾限 制氣體混合物與觸媒的接觸，及因此限制反應速率，尤其 在通道的開始處。 特別地，當無法取得氫時，可使電流直接通過形成反應 器用的板，而提供電熱。此可在最初使用以提高溫度，例 如在供應氣體之前將重組反應器1 4的溫度提高到例如400 °C，以確保催化燃燒的發生。在操作期間亦可使用該電熱 來調整反應器溫度。在反應器1 4出口附近亦可使用該電熱 ，以確保進行重組反應的氣體能達到例如90 (TC的溫度。 (五）圖式簡單說明 第1圖係本發明的化學方法之流程圖；及 第2圖係一適用於進行第1圖中所示方法之步驟的反應 器之平面圖。 符號說明= 10
進料氣 - 1 8 -
2QU3〇ilbU ) 11 熱交換器 12 混合器 14 反應器 15 預重組器 16 重組器 18 熱交換器 20 熱交換器 22 壓縮機 26 反應器 28 蒸汽發生器、熱交換器 30 冷凝器 3 1 重力分離器 32 冷凍式冷凝器 33 減壓渦輪 34 導管 35 儲槽 36 閥 37 重力分離器 40 反應器 42 板 44 溝槽 45 陸面 46 箔 48a - f 頭部
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Claims (1)

  1. 2QU30H6U 拾、申請專利範圍 第9 1 1 3 5 1 77號「催化反應器及方法㈠」專利案 (9 2年3月修正） 1 · 一種用於進行蒸汽/甲烷重組以產生一氧化碳和氫之方法 ，其中使氣體混合物流經金屬片（4 2 )之間的窄流體通道 (44)，該金屬片（42)隔開流體通道與熱源，該流體通道（44) 含有一具金屬基材的流體可透過之觸媒結構，以便增加 熱傳遞，其特徵爲：通道內的滯留時間係少於0 . 5秒， 而且沿著通道的平均溫度及通道出口溫度皆在7 50 t至 9 0 0 °C的範圍內，俾形成一氧化碳的選擇率在8 5 %以上。 2 ·如申請專利範圍第1項之方法，其中滯留時間係少於〇 . 1 秒且至少0 . 0 2秒。 3 ·如申請專利範圍第1項之方法，其中重組反應係在大氣 壓力進行。 4 ·如申請專利範圍第1項之方法，其中蒸氣對甲烷的比例 係在1 . 2至2 . 0的範圍內。 5 ·如申請專利範圍第4項之方法，其中該比例係在1 . 4至 1 . 6的範圍內。 6 ·如申請專利範圍第1項之方法，其之進行係使用一種催 化反應器，此催化反應器界定數個交替排列著的相鄰通 道，以用於蒸汽/甲烷重組反應及用於放熱反應。 7 ·如申請專利範圍第6項之方法，其中放熱反應係含氫的 氣體之燃燒。 8 ·如申請專利範圍第7項之方法，其中至少部分的氫係由 -1- 20U3〇H6U 蒸汽/甲烷重組程序所產生者。 9 ·如申請專利範圍第7項之方法，其中進行燃燒的氫係爲 在使來自蒸汽/甲烷重組程序的一氧化碳和氫接受後續的 費雪-闕布希合成之後所留存的氫。 1 0 . —種用於進行如申請專利範圍第1至9項中任一項之方 法的設備。
    -2-
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