CN1281028A - 一种用于烃原料催化蒸汽重整的方法 - Google Patents
一种用于烃原料催化蒸汽重整的方法 Download PDFInfo
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- CN1281028A CN1281028A CN00122293A CN00122293A CN1281028A CN 1281028 A CN1281028 A CN 1281028A CN 00122293 A CN00122293 A CN 00122293A CN 00122293 A CN00122293 A CN 00122293A CN 1281028 A CN1281028 A CN 1281028A
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 16
- 238000001193 catalytic steam reforming Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000000629 steam reforming Methods 0.000 claims abstract description 19
- 238000002407 reforming Methods 0.000 claims abstract description 14
- 239000003546 flue gas Substances 0.000 claims abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 15
- 239000007789 gas Substances 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
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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
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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
- 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)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Fuel Cell (AREA)
Abstract
一种用于烃原料催化蒸汽重整的方法,包括以下步骤:使烃蒸汽混合物与安装在外加热式预重整器内的第一蒸汽重整催化剂接触,外加热式预重整器位于来自燃烧蒸汽重整器的烟道气通道中;并使来自于预重整器的预重整流出物与燃烧蒸汽重整器内的第二蒸汽重整催化剂接触;本方法包括的另一步骤为,使预重整流出物与第三蒸汽重整催化剂接触,第三蒸汽重整催化剂安装在位于外加热式蒸汽重整器上游的烟道气通道的外部。
Description
本发明涉及一种用于烃原料催化蒸汽重整的方法。具体地说,本发明提供一种用于烃原料催化蒸汽重整的改进方法,包括以下步骤:使烃蒸汽混合物与安装在外加热式预重整器壁上并在蒸汽重整中具有活性的催化元件相接触,进行预重整;随后,使来自于预重整器的预重整流出物与燃烧蒸汽重整器内的装载有蒸汽重整催化剂的催化元件整体接触。
在合成气制备中,烃原料预重整是该技术领域公知的。预重整一般用于含有高级烃的烃原料,或者用于提高现有重整炉装置的生产能力。在约为450℃-550℃的温度下,将烃原料工艺气和蒸汽加入预重整器。在预重整器内进行蒸汽重整反应,当以绝热方式进行预重整反应时,工艺气的温度一般是降低的。
在工业合成气制备装置中,预重整后的工艺气随后通过与来自于燃烧重整器的热烟道气进行热交换,再加热到进入燃烧蒸汽重整器所需的入口温度。工业重整器的入口温度通常为600℃-700℃。
EP-855366号欧洲专利公开说明书公开了一种对来自于燃烧蒸汽重整器的烟道气中热能的改进利用方法。在该专利公开的方法中,进入蒸汽重整器的工艺气,在预热器盘管内被部分重整,盘管壁上装有蒸汽重整催化剂薄膜。然后通过在涂有催化剂的壁上进行的吸热蒸汽重整反应,烟道气中的大量有用热能传递给工艺气,并且被其吸收。调整盘管的尺寸和催化剂的量,以增加来自于催化预热器盘管的部分重整工艺气的出口温度,使其达到燃烧蒸汽重整器入口需要的温度。
上述方法的主要缺点是,在催化预热器盘管的长期操作过程中,降低了催化剂的活生,导致盘管的出口温度超过了燃烧蒸汽重整器入口允许的最大气体温度,这是由于工艺气的蒸汽重整量减小,使得对热能的吸收也降低了。因此,盘管壁上的催化剂必须再活化,或用新鲜催化剂来替换。把盘管从烟道气通道中拆下来,更换预热器盘管内的催化剂是困难且昂贵的操作。
本发明的主要目的是通过增加一个易于更换的催化剂设备,补偿预热器盘管内降低的催化剂活性,来提高上述蒸汽重整过程的长期操作性。
根据上述目的,本发明提供一种用于烃原料催化蒸汽重整的方法,包括以下步骤:使烃蒸汽混合物与安装在外加热式预重整器内的第一蒸汽重整催化剂接触,外加热式预重整器位于来自燃烧蒸汽重整器的烟道气通道中;并使来自于预重整器的预重整流出物与燃烧蒸汽重整器内的第二蒸汽重整催化剂接触;本方法包括的另一步骤为,使预重整流出物与第三蒸汽重整催化剂接触,第三蒸汽重整催化剂安装在位于外加热式蒸汽重整器上游的烟道气通道的外部。
依照本发明的方法,在长期操作过程中,预重整器内的活性损失,将由在中间重整设备内进行的预重整流出物的蒸汽重整反应予以补偿,中间重整设备位于烟道气通道内的预重整器的出口与燃烧蒸汽重整器入口之间。中间设备在基本绝热的条件下操作,并补偿加热式预重整器内蒸汽重整催化剂或催化元件的蒸汽重整活性降低,以及由此引起的预重整器流出物的温度升高。
除在长期操作中,对工艺气提供需要的温度调节,使之以低于燃烧蒸汽重整器的最大入口温度进入其内之外,中间重整器设备的另一个优点是位于烟道气通道的外部。如上所述,为了补偿预重整器内的活性损失,需要更换或再活化燃烧重整器上游失活的催化剂。在前面已经提到,更换位于烟道气通道中的设备内的催化剂,既耗费时间,操作费用又高。而根据本发明,通过在烟道气外部安装中间催化剂设备,失活的催化剂在中间重整器设备内被更换,更换操作被显著地简化。
中间催化剂设备优选安装于连接预重整器与燃烧蒸汽重整器的管中,并位于烟道气通道的外部。中间设备内的催化剂可以是常用于烃蒸汽重整中的任何形状。为了减小中间设备的压降,催化剂的形状优选采用直管形。
中间催化剂设备内催化剂的尺寸和活性取决于实际工艺布置。
Claims (3)
1.一种用于烃原料催化蒸汽重整的方法,包括以下步骤:使烃蒸汽混合物与安装在外加热式预重整器内的第一蒸汽重整催化剂接触,外加热式预重整器位于来自燃烧蒸汽重整器的烟道气通道中;并使来自于预重整器的预重整流出物与燃烧蒸汽重整器内的第二蒸汽重整催化剂接触;本方法包括的另一步骤为,使预重整流出物与第三蒸汽重整催化剂接触,第三蒸汽重整催化剂安装在位于外加热式蒸汽重整器上游的烟道气通道的外部。
2.如权利要求1所述的方法,其中,第一蒸汽重整催化剂是薄膜催化剂,安装在外加热式预重整器的壁上。
3.如权利要求1所述的方法,其中,第三蒸汽重整催化剂是一种整体结构催化剂。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14395399P | 1999-07-15 | 1999-07-15 | |
US60/143953 | 1999-07-15 | ||
US60/143,953 | 1999-07-15 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1281028A true CN1281028A (zh) | 2001-01-24 |
CN100379842C CN100379842C (zh) | 2008-04-09 |
Family
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB001222937A Expired - Fee Related CN100379842C (zh) | 1999-07-15 | 2000-07-15 | 一种用于烃原料催化蒸汽重整的方法 |
Country Status (11)
Country | Link |
---|---|
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) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1307086C (zh) * | 2002-09-26 | 2007-03-28 | 赫多特普索化工设备公司 | 制备合成气的方法和装置 |
CN100471788C (zh) * | 2005-06-14 | 2009-03-25 | 气体产品与化学公司 | 轴向对流重整装置及在其中产生合成气的蒸汽重整方法 |
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 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1403215B1 (en) * | 2002-09-26 | 2013-03-13 | Haldor Topsoe A/S | Process and apparatus for the preparation of synthesis gas |
EP1413547A1 (en) | 2002-09-26 | 2004-04-28 | Haldor Topsoe A/S | Process for the production of synthesis gas |
US7919057B2 (en) | 2005-09-06 | 2011-04-05 | Air Products And Chemicals, Inc. | Method and apparatus for producing a hydrogen-containing gas |
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 |
Family Cites Families (15)
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JPS60122702A (ja) * | 1983-12-01 | 1985-07-01 | Jgc Corp | 炭化水素の水蒸気改質法 |
GB8530272D0 (en) * | 1985-12-09 | 1986-01-22 | Shell Int Research | Producing liquid hydrocarbons |
GB8728882D0 (en) * | 1987-12-10 | 1988-01-27 | Ici Plc | Hydrogen |
JP2607644B2 (ja) * | 1988-10-27 | 1997-05-07 | 三菱重工業株式会社 | メタノール改質方法 |
DE3991744T (zh) * | 1989-09-20 | 1991-10-10 | ||
EP0522744B1 (en) * | 1991-07-09 | 1997-08-13 | Imperial Chemical Industries Plc | Synthesis gas production |
JPH05186203A (ja) * | 1992-01-07 | 1993-07-27 | Toshiba Corp | 水蒸気改質用触媒エレメント |
JPH06219705A (ja) * | 1993-01-22 | 1994-08-09 | Mitsubishi Electric Corp | 燃料改質装置 |
KR0131529B1 (ko) * | 1994-11-24 | 1998-04-09 | 안덕기 | 탄화수소부터의 옥소 가스(Oxo-gas)의 제조방법 |
ATE200884T1 (de) * | 1997-01-22 | 2001-05-15 | Haldor Topsoe As | Erzeugung eines synthesegases durch dampfreformierung unter verwendung eines katalysierten hardware |
US5980596A (en) * | 1997-04-25 | 1999-11-09 | Exxon Research And Engineering Co. | Multi-injector autothermal reforming process and apparatus for producing synthesis gas (law 565). |
DK173052B1 (da) * | 1997-05-05 | 1999-12-06 | Topsoe Haldor As | Fremgangsmåde til fremstilling af ammoniak syntesegas |
JPH111302A (ja) * | 1997-06-10 | 1999-01-06 | Toyota Motor Corp | 燃料改質方法と燃料改質装置ならびに該燃料改質装置を備えた燃料電池装置 |
DE19754013C2 (de) * | 1997-12-05 | 2000-10-26 | Dbb Fuel Cell Engines Gmbh | Vorrichtung und Verfahren zur Wasserdampfreformierung eines Kohlenwasserstoffs |
BR9815937A (pt) * | 1998-07-21 | 2001-02-28 | Haldor Topsoe As | Produção de gás de sìntese por reforma a vapor |
-
2000
- 2000-06-29 EP EP00113766A patent/EP1069070B1/en not_active Expired - Lifetime
- 2000-06-29 ES ES00113766T patent/ES2375102T3/es not_active Expired - Lifetime
- 2000-06-29 AT AT00113766T patent/ATE535495T1/de active
- 2000-07-03 TW TW089113126A patent/TWI223643B/zh not_active IP Right Cessation
- 2000-07-12 CA CA002313762A patent/CA2313762C/en not_active Expired - Lifetime
- 2000-07-13 KR KR10-2000-0040066A patent/KR100444428B1/ko active IP Right Grant
- 2000-07-14 AU AU48635/00A patent/AU769747B2/en not_active Ceased
- 2000-07-14 JP JP2000214618A patent/JP2001064001A/ja active Pending
- 2000-07-14 RU RU2000118561/04A patent/RU2263627C2/ru not_active IP Right Cessation
- 2000-07-15 CN CNB001222937A patent/CN100379842C/zh not_active Expired - Fee Related
- 2000-07-17 NZ NZ505785A patent/NZ505785A/en not_active IP Right Cessation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1307086C (zh) * | 2002-09-26 | 2007-03-28 | 赫多特普索化工设备公司 | 制备合成气的方法和装置 |
CN100471788C (zh) * | 2005-06-14 | 2009-03-25 | 气体产品与化学公司 | 轴向对流重整装置及在其中产生合成气的蒸汽重整方法 |
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 |
Also Published As
Publication number | Publication date |
---|---|
ATE535495T1 (de) | 2011-12-15 |
EP1069070B1 (en) | 2011-11-30 |
AU769747B2 (en) | 2004-02-05 |
CA2313762A1 (en) | 2001-01-15 |
AU4863500A (en) | 2001-01-18 |
CA2313762C (en) | 2009-09-01 |
KR100444428B1 (ko) | 2004-08-16 |
KR20010061919A (ko) | 2001-07-07 |
ES2375102T3 (es) | 2012-02-24 |
TWI223643B (en) | 2004-11-11 |
RU2263627C2 (ru) | 2005-11-10 |
CN100379842C (zh) | 2008-04-09 |
EP1069070A3 (en) | 2003-01-29 |
NZ505785A (en) | 2001-12-21 |
EP1069070A2 (en) | 2001-01-17 |
JP2001064001A (ja) | 2001-03-13 |
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