TWI223643B - Process for the catalytic steam reforming of a hydrocarbon feedstock - Google Patents

Process for the catalytic steam reforming of a hydrocarbon feedstock Download PDF

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Publication number
TWI223643B
TWI223643B TW089113126A TW89113126A TWI223643B TW I223643 B TWI223643 B TW I223643B TW 089113126 A TW089113126 A TW 089113126A TW 89113126 A TW89113126 A TW 89113126A TW I223643 B TWI223643 B TW I223643B
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Taiwan
Prior art keywords
reformer
catalyst
steam
flue gas
steam reforming
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Application number
TW089113126A
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English (en)
Inventor
Thomas Rostrup-Nielsen
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Haldor Topsoe As
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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
    • 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
    • C01B3/382—Multi-step processes
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
    • 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
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Fuel Cell (AREA)

Description

1223643 A7
經濟部智慧財產局員工消費合作社印製 五、發明說明（） 本發明是關於一種催化蒸氣重組烴原料之方法。特別 的是，本發明提供上述類型之改良方法，其包括的步驟爲 :將烴蒸氣混合物在與催化硬體接觸下預重組，該催化硬 體具有蒸氣重組之活性並被置於外部經加熱之預重組器之 壁上’且接著，將來自預重組器之經預重組流出物與置於 燃燒蒸氣重組器中之催化硬體單石上之蒸氣重組觸媒接觸 Ο 在製備合成氣體時，預重組烴原料爲本技藝中所習知 。預重組一般是利用含較高烴類之烴原料或是用於增加現 存重組工廠的能力。烴原料與蒸氣之製程氣體於約450到 55〇°C之溫度下被導入預重組器中。藉由在預重組器中進行 蒸氣重組反應，當以絕熱模式進行預重組製程時，製程氣 體的溫度通常會降低。 在工業合成氣體製備工廠中，藉由與來自燃燒重組器 中之熱煙道氣熱交換，可使預重組的製程氣體隨後被再加 熱到燃燒蒸氣重組器所須之入口溫度。到工業重組器之通 常的入口溫度在600〜700°C之間。 在EP專利公告號855,366中揭示，改良利用字來自燃 燒蒸氣重組器之熱煙道氣中的熱。在該專利案中揭示，蒸 氣重組器之製程氣體會部分在預加熱器旋管上重組，該旋 管之壁上設有蒸氣重組處媒之薄膜。在煙道氣中大量可貴 之熱會然後經由塗覆於壁上之觸媒所進行之吸熱蒸氣預重 組反應而被傳送並被製程氣體吸收。 上述方法之主要缺點爲在催化預加熱器旋管之長時間 3 (請先閱讀背面之注意事項再填寫本頁) 裝 訂·· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1223643 A7 B7 五、發明說明（） 操作下，會降低觸媒活性，導致因爲減少了在氣體中重組 之蒸氣熱吸收，旋管出口溫度會大於燃燒重組器入口之最 大允許的氣體溫度。在旋管壁上之觸媒必須被再活化或是 更換爲新的觸媒。更換在預熱器旋管中之處媒爲困難的且 當要從煙道氣通道中卸下旋管時爲昂貴之操作。 本發明的主要目的是要改良前述類型之蒸氣重組製程 中長期的可操作性，其係藉易更換的額外觸媒單位以補償 在預加熱器旋管中降低之觸媒活性。 根據前述之目的，本發明提供一種催化蒸氣重組烴原 料之方法，其包括的步驟爲：將烴蒸氣混合物在與第一蒸 氣重組接觸接觸，該觸媒是置於燃燒蒸氣重組器之煙道氣 通道上之外部加熱預重組器，且在燃燒蒸氣重組器中將預 重組器之經預重組流出物與第二蒸氣重組觸媒接觸，該方 法包括進一步之步驟爲:將預重組流出物與置於外部加熱蒸 氣重組器下游之煙道氣通道外的第三蒸氣重組觸媒接觸。 藉由本發明之方法，在長時間操作期間之預重組器的 活性損失將由位在煙道氣通道上之預重組器出口與燃燒蒸 氣重組器入口之間的中間重組單元之經預重組流出物之蒸 氣重組反應以補償。中間單元將在大致上絕熱條件下操作 ，並補償在加熱預重組器中蒸氣重組觸媒或催化硬體之所 降低之蒸氣重組活性及補償預重組器之流出物中所得溫度 增加。 除了提供製程氣體在長期操作下所需溫度調整低於燃 燒蒸氣重組器之最大入口溫度，中間重組器單元之進一步 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)
T 經濟部智慧財產局員工消費合作社印製 1223643 A7 B7 五、發明說明（） 優點爲使單元置於煙道氣管到外。爲了補償前述預重組器 中之所降低之活性，有必要使燃燒蒸氣婁組器上游之失效 觸媒被取代或產生活性。如此處所述地，在煙道氣通道內 之單元上取代失效觸媒之前爲耗費時間並昂貴難以處理。 根據本發明，藉由在煙道氣通道外安置中間觸媒單元 ，失效觸媒然後在中間重組單元上被取代，而取代操作因 此簡化。 中間觸媒單元因此較佳被安置在與預重組器連接煙道 氣通道外之燃燒蒸氣重組器之管線上。在中間單元上之觸 媒可爲適用於烴類蒸氣重組中之任何形狀。爲了降低在單 元中之壓降，觸媒較佳爲直通道之整塊石料。 在中間觸媒單元上之觸媒之大小與活性將取決於真實 製程工廠佈置。 (請先閱讀背面之注意事項再填寫本頁) 裝
I H ϋ· I n ϋ I 經濟部智慧財產局員工消費合作社印製 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）

Claims (1)

  1. 1223643 六、申請專利範SI \ ….......—1 1. 一種催化蒸氣重組烴i料ϋϋ，_其包括的步驟爲 :將烴蒸氣混合物與第一蒸氣重組觸媒接觸使其預重組之 ，該觸媒是置於燃燒蒸氣重組器之煙道氣通道上之外部加 熱預重組器中，且在燃燒蒸氣重組器中將來自預重組器之 經預重組流出物與第二蒸氣重組觸媒接觸，該方法包括進 一步之步驟爲：將經預重組流出物與置於煙道氣通道外面 及在煙道氣通道中之預重組器出口和燃燒蒸氣重組器入口 之間的中間催化重組單元接觸。 2. 根據申請專利範圍第1項之方法，其中第一蒸氣重 組觸媒爲置於外部加熱預重組器之壁上的薄層觸媒。 3. 根據申請專利範圍第1項之方法，其中中間重組催 化單位包含一單石結構觸媒。 (請先閲讀背面之注意事項再塡寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公釐)
TW089113126A 1999-07-15 2000-07-03 Process for the catalytic steam reforming of a hydrocarbon feedstock TWI223643B (en)

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EP (1) EP1069070B1 (zh)
JP (1) JP2001064001A (zh)
KR (1) KR100444428B1 (zh)
CN (1) CN100379842C (zh)
AT (1) ATE535495T1 (zh)
AU (1) AU769747B2 (zh)
CA (1) CA2313762C (zh)
ES (1) ES2375102T3 (zh)
NZ (1) NZ505785A (zh)
RU (1) RU2263627C2 (zh)
TW (1) TWI223643B (zh)

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Publication number Priority date Publication date Assignee Title
EP1413547A1 (en) 2002-09-26 2004-04-28 Haldor Topsoe A/S Process for the production of synthesis gas
ES2405587T3 (es) * 2002-09-26 2013-05-31 Haldor Topsoe A/S Procedimiento y aparato para la preparación de gas de síntesis
EP1403217A1 (en) 2002-09-26 2004-03-31 Haldor Topsoe A/S Process and apparatus for the preparation of synthesis gas
US7504048B2 (en) * 2005-06-14 2009-03-17 Air Products And Chemicals, Inc. Axial convective reformer
US7919057B2 (en) 2005-09-06 2011-04-05 Air Products And Chemicals, Inc. Method and apparatus for producing a hydrogen-containing gas
CN101134160B (zh) * 2006-08-30 2010-06-30 中国石油天然气股份有限公司 一种催化裂解生产低碳烯烃的反应装置
US7501078B2 (en) 2007-01-10 2009-03-10 Air Products And Chemicals, Inc. Process for generating synthesis gas using catalyzed structured packing
US8187369B2 (en) * 2009-09-18 2012-05-29 General Electric Company Sorbent activation plate

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CA2313762C (en) 2009-09-01
CN100379842C (zh) 2008-04-09
KR100444428B1 (ko) 2004-08-16
CN1281028A (zh) 2001-01-24
EP1069070A2 (en) 2001-01-17
AU769747B2 (en) 2004-02-05
RU2263627C2 (ru) 2005-11-10
AU4863500A (en) 2001-01-18
ATE535495T1 (de) 2011-12-15
CA2313762A1 (en) 2001-01-15
KR20010061919A (ko) 2001-07-07
EP1069070A3 (en) 2003-01-29
NZ505785A (en) 2001-12-21
EP1069070B1 (en) 2011-11-30
JP2001064001A (ja) 2001-03-13
ES2375102T3 (es) 2012-02-24

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