TW482741B - Process for the preparation of hydrogen and/or carbon monoxide rich gas - Google Patents

Process for the preparation of hydrogen and/or carbon monoxide rich gas Download PDF

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TW482741B
TW482741B TW087100593A TW87100593A TW482741B TW 482741 B TW482741 B TW 482741B TW 087100593 A TW087100593 A TW 087100593A TW 87100593 A TW87100593 A TW 87100593A TW 482741 B TW482741 B TW 482741B
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steam reforming
reactor
gas
catalyst
tubular reactor
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Jens Rostrup-Nielsen
Peter Seier Christensen
Viggo Lucassen Hansen
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Haldor Topsoe As
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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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • B01J15/00—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor
    • B01J15/005—Chemical processes in general for reacting gaseous media with non-particulate solids, e.g. sheet material; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • 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
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J19/2415—Tubular reactors
    • B01J19/243—Tubular reactors spirally, concentrically or zigzag wound
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    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Processes with two or more reaction steps, of which at least one is catalytic, e.g. steam reforming and partial oxidation
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts with external heating of the catalyst
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00504—Controlling the temperature by means of a burner
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • 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
    • 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
    • C01B2203/0816—Heating by flames
    • 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
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • 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
    • C01B2203/0866—Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • C01B2203/143—Three or more reforming, decomposition or partial oxidation steps in series
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
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Description

482741 A7 B7_ 五、發明說明（I ) t發明是關於藉去將碳氫化合物進料與催化硬體接觸 以進行蒸氣重組來生產合成氣體。 (請先閱讀贵面之注意事項再填寫本頁) 術語催化硬體是芾於催化劑系統，其中一層僵化劑被 S定在另一種材料的表面，飼如金屬表靣。其它材料可侥 載體結構用以產生強度給系統。此容許用來設計本身不具 有足夠機械強度的催化劑形狀。此一系統由管子新觀成， 在管子上有一薄層的重組催化劑置於其內璧上。 合成氣體的生產係藉έ反應式（1)至（3)來蒸氣重組碳 氫化合物，該反應式（1)至（3)爲··
CnHm -f η H?0 -► n CO + ( n 4 -)1¾ (_Mfi <〇) (l) CO + H?〇 一 C〇2 十 H2 (△HL = 41 kJ/mole ) (2) CH4 + H?0 =^= CO + 3 1¾ (-δη°298 =-206 kJ/mole ) (3) 經濟部智慧財產局員工消費合作社印製 在蒸氣重組之宄前技藝中，其係利闱各種不同大小及 夥狖之顆粒彤式的重絚催化劑。該催化劑顆粒被置於固定 床反應器中（厘組管中）。該重絕反應是唆熱的。在傳統的 重組器中，反應靳需要的熱通常是藉由詛合輕射及對流以 從管舛面的環境來提供熱至重組器管外側。熱再經自管壁 以熱傳導傳遞至管的內側，並且以對流傳送至氣相。最後， 熱從氣相以對流方式傳送至催化劑顆粒。該催化劑的溫度 可大於loot：、小於在重組器管之同軸位置的內管壁溫度。 傾發現當催化硬體使用於蒸氣重組方法時，熱的傳遞 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 482741 A7 B7 五、發明說明（L ) (請先閱讀嘴面之注意事項再填寫本頁) 比較有效率。傳遞到催化劑的熱是藉由管內壁之熱傳導而 發生的。而此一傳遞機制比經由氣相之對流來傳送要有效 銮。結杲是內管壁與催化劑的溫度是幾乎相同（差別在5t： 以下）。更進一步，可降低管的厚度，如下m示，其使得 重組器管之內及外側之間的溫度差變小。因此有可能具有 較高催化劑濫度及較低管之温度，旦當置於具有催化硬體 管之傳統重組器管時，所有其它條伟均相同。所欲爲較低 之外管壁溫度，因爲可延長管的壽命。高催化劑溫度爲有 利的，因爲反應速率隨溫度增加，並且因爲反應（3)的平銜 會_右手邊移動，而造成較佳的進料利周。 因此，本發明提烘一種製備富含一氧化碳氣體之氫氣 的方法，其係在蒸氣重組催化劑之存在下，將碳氫化合物 莲行蒸氣重組，其中該蒸氣重組催化劑係如薄膜般支撐在 管式反應器上，其包括的步驟爲： U)可選擇性地將預先重組之碳氫化合物進料的製程氣 體通過第一管式反應器，其具有支撐在反應器之壁上的蒸 氣重組催化劑的薄膜，該反應器與來自後續第二管式蒸氣 重組反應器之熱煙道氣具有熱傳導的關係； 經濟部智慧財產局員工消費合作社印製 (b)使來自第一管式反應器之流迅物通至後續第二管式 反應器，其具有蒸氣重組催化劑的薄膜並且以燃燒燃料來 加熱，藉此得到部分蒸氣重組氣體流出物及熱煙道氣； U)使來自第二反應器之流岀物通至固定床蒸氣重組催 •化劑上；並且 (d)從固定床中瑕tB富含一氧化碳及氫氣之產物氣體。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 482741 A7 B7_ 五、發明說明（>) (請先閱讀背面之注意事項再填寫本頁) 在偟化重組器管中的壓力降是比傳統之相同管徑的例 子要低得許多。此使得可利用具有較小直徑的反應器管， 並且仍維持一可接受的壓力降。較小管徑造成管子壽命的 增加、可承受較高溫度及減低管子材料的消耗。 最後，與傳統具有重組催化劑之固定床比較下，當使 用催化硬體重組器管時，可降低催化劑的量。 圖一爲顯示產生合成氣體之裝置的前端，違料2被預 熱、在軍元4中被脫硫、與製程流6混合、並且進一步在 進入一個絕熱預先重組器8之前被加熱。來自預先重組器 8的流tB物流則進一步在置於煙道氣通道12之迴路中被力Π 熱，並且被送至管式重組器14,其中發生宇烷轉化成氫氣、 一氧化碳及二氧化碳。來自管式重組器之下游之流出物氣 體的處理係取決於該產物的使周。 催化硬體可以在圖一所顯示之兩個單元中使用： 1. 在進入管式重組器14之前，用來加熱預先重組之流岀 狡?氣體的預熱器線圈1 〇上。 2. 管式重組器14中。 經濟部智慧財產局員工消費合作社印製 以下將提出當催化硬體用於上述兩個覃元中，圖一裝 置所獲得之結杲。用於催化硬體的催化劑是R-67R鎳蒸氣 重組催化劑，其可得自哈爾德杜薩公司（Haldor Topsoe A/S)。該結果與傳統的情況比較。 該預熱器線圈的目的是使周煙道氣中的熱含量，而能 在製程氣體進入管式重組器之前被用來加熱製程氣體。使 用該煙道氣來預熱該製程氣體，益且羯來預熱管式重組器 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 482741 A7 _B7 _ 五、發明說明（斗） (請先閱讀臂面之注意事項再填寫本頁) 的空氣燃燒（未顯示於圖一）。然而，該煙道氣的熱含量是 大於可.用於這些目的之量，並使所餘的熱可周於蒸氣的產 生。如杲在該煙道氣中較大量的熱含量可被傳送至製程氣 體時，此爲一個優點。這將減少在管式重組器中的燃料需 要量，益且減小該重組器的大小，因爲較小量的熱被傳送 至單元中。 傳統的預熱器因曱烷分解m生成碳的危險而受到限 制。龀設定了可接受之管壁溫度的上限。將催化硬體層固 定在預熱器線圈10的內管壁6上（如圖二所示）會導致管壁 溫度及製程氣體溫度兩者的減低。ife使得在沒有較高之管 溫度下，在線圈中具有較高傳送效率。 用於計算的預熱器線圏由8管所組成，其中製程氣體 在該管中流動。煙道氣在外側流動。流動的形式爲交叉流 式/共流式。圖二顯示管的配置圖。具有及沒有催化硬體 的雨種例子被摘述於表一當中。明顯的是將催化硬體之例 與傳統例子比較時，其傳送效率：（熱能量）則是高岀49%。 在催化硬體之㈣中，該催化劑層的厚度是1.〇mm。 經濟部智慧財產局員工消費合作社印製 表1 傳統的例子 ^子的總數目 丨 8 8 ^子的有效總長度 I 51.6 m 1 /0.2 m P道氣進/岀的溫度 ! 1057t/964t I 1057't/912t： 製程氣體進娃的溫度 ! ! 5i2°C/650t： 1 512°c/631°c 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 482741 A7 B7 五、發明說明（5 ) 曱燒轉化率 ! 〇% ! i ί 8.7% 效率 ! 9.69* 106 kcaMir 1 1 1.44*10 kcal/hr 有效的管長度是在煙道氣通道內的管子長度。 傳統的管式重組器由許多管子所組成，其塡充著催化 劑顆粒。製程氣體在管內流動。該管被置於以燃燒燃料來 加熱的熔爐中。 在催化硬體的例子中，塡充在管內的催化劑顆粒被置 於在內管壁上有一層催化硬體的許多管子內。該催化劑層 朽厚度是〇. 2 5 mm。額外的絕熱重組固定尿反應器被置於 管式反應器的下游，因爲甲烷在催化硬體之管式重組器中 的轉化是比傳統的情形差一些。此反應器被稱爲後重組 器。甬於後重組器的催化劑是RKS-2鎳蒸氣重組傕化劑， 其可得自哈爾德杜薩公司（Haldor Topsoe A/S)。 在下表2中摘述該兩種例子。其可見催化劑的消耗是 以11.5的倍數而降低，並且與傳統之例子比較下的催化 硬體之例中，管式重組器中之材質消耗減少了 24%。 -------------------丨訂-------線 (請先閱讀臂面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 表2 1傳統之例子 1 | 催化硬體的重組器 催化硬體之例 +後重組器 管子的數目 276 i 187 管子的長度 13 m 55 m 鐲媒的消耗 31.0 噸 0.63 噸 2.70 噸 ! 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 482741 A7 B7 五、發明說明（b ) 管式重組器的管材 質r無 153.6 0頓 116.0 _ 田 1 /V i 89 % 80.7 % 90.2 % 拫據本發明之方法的流程圖顯示於圖三。三角形裎的 數字代表下列表中的數字，爲方法中所有項目的比較。在 催化硬體的例子中，與傳統的例子進行比較下，燃料的消 耗減少了 7.4%。 表3 (請先閱讀臂面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 位置 傳統之例子 催化硬體的例子 1 聽(°C) 512 512 壓力(kg/cm2 g) 28.5 28.5 總乾燥流量（Nm3/h) 57851 57851 總流量（Nm3/h) 143168 143168 糸且成(乾燥mole%) 氫氣 23.78 23.78 —氧化碳 0.74 0.74 二氧化碳 21.14 21.14 甲烷 54.34 54.34 2 溫度ΓΟ 650 631 壓力(kg/cm2 g) 27.5 27.4 總乾燥流量(Nm3/h) 57851 67397 總流量GW/h) 143168 148720 組成(乾燥mole%) 氫氣 23.78 34.58 一氧化碳 0.74 2.67 二氧化碳 21.14 20.16 甲烷 54.34 42.59 3 溫度rc) 925 1015 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 482741 A7 B7 五、發明說明（） 壓力(kg/cm2 g) ! 24·1 ! 26,0 總乾燥流量(Nm3/h) 141533 132653 總流童(NmVh) 199121 | 194706 組成(乾燥mole%) 1 ! 1 : 氫氣 68.85 66.76 一氧化碳 20.24 20.42 二氧化碳 ! 8.47 I 8.24 甲烷 2.44 ； 4.57 4 1 !’、、觸 ΠΪΠ/Ο广、 i在此飼中沒有後重 930 丨 I 幺口虫 1 ί .'丨猶 ! 壓力(kg/cm2 g) ! ! ! | 24.4 1總乾燥流量(Nm3/h) j 1 142580 總流量(NmiVh) i i j ： ί 1 200003 組成(乾燥mole%) i i | ; j | 氫氣 1 69.08 一氧化碳 20.35 二氧化碳 8.40 曱烷 1 2.17 5 溫度rc) ! 1057 ! 1057 總流量(Nm3/li) ! i ! 244672 ! 234677 6 酿(t) ! 964 ! 912 7 總流量(Nm3/!!) j I | 9524 1 8820 實施例：製備催化硬體 ------------餐--------訂 i,-------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 在製備根據本發明之特定具體實施例中的催化硬體之 方法中，催化劑的製備是藉由在管式重組反應器之表面上 塗钸凝膠塗料（a)(gei coating (a))，並進行退火，再於1000 t：下锻燒表靣上之塗料（a)。接著，藉甴利周前述塗倚步驟 之相同的程序，在經塗覆之表面上另外塗佈上凝謬塗料（b)。 凝謬塗料U)的製備係藉由混合60g軟化水，25g乙醇， 3 5g甘油，2g PEG(聚乙烯）20,000混末及lg分散劑（Surfynol 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 482741 A7 B7 五、發明說明（y) 104?〇1*11^1:〇141126〇2，2,4,7,9-四甲基-5-癸炔-4,7-二醇）。 在上述經攪拌之混合物中添加80g經安定之氧化鉻及20g 氧化鋁。最後將所得混合物於球磨機中.研磨至小於20微米 约粒徑。 凝膠塗料（b)的製備係藉由混合30g軟化水，25g乙醇，-25§官涵，1£卩£0 20,000 及1莒分散齊!|(31^)^11〇1104卩〇1*111€1: (：14112602,2,4,7,9-四甲基-5-癸炔-4,7-二醇）。在上述挢得經 攪拌之混合物中添加40g經安定之氧化鉻及60g氧化鋁。 最後將所得混合物於球磨機中硏磨至小於20微米的粒徑。 在上述之管式反應器之內壁被塗覆完成之後，獲得0.25 mm厚度之陶瓷載體層。再以作爲活性蒸氣重組催化劑之Ni 來浸漬載體，其係藉由將SOg之60%熱硝酸鎳通過管來進 行的。最後，將管加熱至45〇t。 圖式簡單說明 在圖1及3之簡單槪要形式中顯示生產合成氣體之裝 置的流程圖；且 _ 2爲預熱器線圏之放大圖式，在線圏之內壁上具有 薄膜催化劑。 圖式主要元件符號說明 7 進料 4 脫硫軍元 6 製程流 8 斧B熱預先重組器 10 預熱器線圏 11 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------------- -7 訂---------線 (請先閱讀背面之注意事項再填寫本頁) 482741 A7 _B7 五、發明說明（3 ) 12 煙道氣通道 14 管式重組器 16 預熱器線圈之內壁 --------------------;訂·—-------線 1^· (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製
2 IX 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）

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  1. 丄 i一. i 女^申讀專利範圍 ：;丨宅酿U2l丨：^ ._ν h； 〜'.〜….—…一： (請先閲讀背面之注意事項再填寫本頁) 1. 一種製備富含一氧化碳氣體之氫氣的方法，其係在 蒸氣重組催化劑存在下，將碳氫化合物進料進行蒸氣重 組，其中該蒸氣重組催化劑如薄膜般支撐在管式反應器 上，其包括的步驟爲： (a) 可選擇性地將預先重組之碳氫化合物進料的製程氣 體通過第一管式反應器，其具有支撐在反應器之壁上的蒸 氣重絚催化劑的薄膜，該反應器與來自後續第二管式蒸氣 重組反應器之熱煙道氣具有熱傳導的關係； (b) 使來自第一管式反應器之流出物通至後續第二管式 反應器，其具有蒸氣重組催化劑的薄膜並且以燃燒燃料來 加熱，藉此得到部分蒸氣重組氣體流出物及熱煙道氣； (c) 使來自第二反應器之流出物通至固定床蒸氣重組催 化劑上；並且 (d) 從固定床中取出富含一氧化碳及氫氣之產物氣體。 2. 如申請專利範圍第1項的方法，其中該固定床蒸氣 重詛催化劑是在絕熱的條件下操作。 3 .如申請專利範圍第1項的方法，.其中該固定床蒸氣 重組催化劑是被安置在第二管式反應器內。 經濟部智慧財產局員工消費合作社印製 4.如申請專利範圔第1項的方法，其中該蒸氣重組催 化劑包括鎳及/或釕。 _ 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）
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EP0855366A1 (en) 1998-07-29
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AU728728B2 (en) 2001-01-18
NO980274D0 (no) 1998-01-21
CA2227598C (en) 2007-09-11
KR19980070692A (ko) 1998-10-26
DE69800734T2 (de) 2001-08-09
JP4521735B2 (ja) 2010-08-11
AU5215898A (en) 1998-07-30
CA2227598A1 (en) 1998-07-22
AU728728C (en) 2001-08-30
UA61888C2 (uk) 2003-12-15
CN1269724C (zh) 2006-08-16
ATE200884T1 (de) 2001-05-15
KR100547540B1 (ko) 2006-03-23
RU2218301C2 (ru) 2003-12-10
US5932141A (en) 1999-08-03
DE69800734D1 (de) 2001-06-07
NO318107B1 (no) 2005-01-31
EP0855366B1 (en) 2001-05-02
DK0855366T3 (da) 2001-08-13
NZ329613A (en) 1998-11-25
CN1196330A (zh) 1998-10-21
ES2158621T3 (es) 2001-09-01

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