CN1202986C - 以蒸汽重整法制备合成气体 - Google Patents
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- 238000002407 reforming Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
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- 239000012876 carrier material Substances 0.000 claims 4
- 239000002994 raw material Substances 0.000 claims 1
- 238000005476 soldering Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000000629 steam reforming Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
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- 150000001336 alkenes Chemical class 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 238000006057 reforming reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
用于制备富含氢和一氧化碳之气体的方法，其中，使一烃原料在一蒸汽重整催化剂存在条件下进行蒸汽重整反应，所述催化剂具有一多孔载体结构，该结构被粘附到重整反应器的壁上。
Description
技术领域
本发明涉及通过与催化硬件接触来催化地使一烃原料进行蒸汽重整(steam reforming)。
背景技术
此处使用的术语“催化硬件(hard ware)”是指一催化系统，其中一层催化剂被安置在另一材料例如金属的一表面上。术语“多孔结构稳定的催化硬件”指一催化系统，其中一由比催化剂要坚固之材料制成的多孔结构被粘附到其它材料上并且催化剂被沉积在多孔结构的腔穴内。在本说明书的其余部分，多孔结构被认为是由金属制造的。但是，可以使用比催化剂材料坚固的任何多孔材料。
现有技术的蒸汽重整技术利用各种尺寸和形状的粒丸形式的重整催化剂。催化剂粒丸被放置在固定的床式反应器或重整器管内。整个蒸汽重整反应是吸热的。所需的热量是从管外的环境供给的。
使用在一蒸汽重整反应器的内管壁上带有催化硬件蒸汽重整催化剂的重整管被公开在欧洲专利申请第855366号中。在蒸汽重整处理中采用催化硬件的主要优点是：
a.改善了从重整器管外的热源向催化剂的热传输，因为热量可以从内管壁向催化剂直接传导；
b.降低了管温度，从而增大使用寿命和/或减小管材料的消耗；
c.增高了催化剂温度，从而增高催化剂的活性，增强烃的转换和减小催化剂的量；以及
d.减小了压力降。
用于蒸汽重整的催化硬件之一普遍问题是要建立催化剂到反应器壁上之足够的粘附强度，并且与此同时要保持催化剂在催化剂活性、小孔结构和烧结稳定性等方面的必要特性。
发明内容
本发明的目的是提供在蒸汽重整处理中具有改进的粘附稳定性与所需的催化特性的催化硬件。
根据上述目的，本发明是一种在存在一蒸汽重整催化剂时通过蒸汽重整一烃原料来制备富含氢和一氧化碳之气体的处理方法，并且催化剂具有一多孔载体结构以及被粘附到一重整反应器的壁上，其中该蒸汽重整催化剂被沉积在载体多孔结构内。
多孔金属结构对于一金属反应器壁具有改进的粘附性。催化剂被沉积在多孔材料结构内并且被保持在结构内，这就减小了或甚至消除了将催化剂粘附到反应器壁上的要求。
在应用本发明时，可以使用在蒸汽重整处理中能经受实际处理条件的任何类型的金属多孔结构，包括金属泡沫材料，金属网，膨胀金属，烧结金属和金属丝网。催化剂的粘附要求取决于所选择的多孔金属的类型。
泡沫金属具有一结构，其中小孔腔穴大致为球形并且腔穴的开口具有一比球形腔穴的半径小的半径。沉积在腔穴内的催化材料不会从腔穴溢出。因此不要求将催化剂粘附到金属上。
例如可通过将含有一陶瓷母体粒子的泥浆浸入金属泡沫材料内，使之干燥、煅烧，并且浸渍活性催化材料，就可以将催化剂沉积在腔穴内。
如果选择一多孔金属结构，其中不是由结构的物理表面来保持催化剂，则将催化剂粘附到金属上所需的强度仍然会降低。由于增大的催化剂/-金属接触界面的表面面积，每一单位面积的粘附强度低一些就可提供同样的总粘附强度。
催化剂的磨损消耗被有利的降低了，因为当催化剂不可避免地与含有颗粒的沿反应器内表面流动的气体接触时，催化剂受到了金属结构的保护。
催化剂由于例如热应力而从反应器壁剥落的危险显著地降低了。
使用带有一被粘附到一反应器容器壁上之催化剂的金属泡沫材料来从烃原料生产烯烃被公开在日本专利申请JP59-205 332(A)中。该催化剂的目的是当通过对重型物质使用带有一裂解作用的催化剂来内部加热地高温分解重油而生产烯烃时消除形成焦炭的危险。上述专利申请完全没有记载关于含有催化剂的泡沫材料被粘附到反应器容器上的处理工艺。
在本发明处理方法中所用的多孔结构在第一步中被粘附到反应容器的壁上。然后，将催化剂分散到多孔结构内。
对于上述蒸汽重整使用了催化硬件的优点在于特别与一蒸汽重整处理方法有关并且总体上涉及由外部热源加热的吸热性处理方法。
多孔金属可以例如通过焊接或扩散粘接而被粘附到反应器壁上。
将多孔金属被粘附到反应器壁上的制备步骤需要将反应器和多孔金属加热到一高于反应器之最大运作温度的温度。这就要求在反应器的最大运作温度下提供足够的粘附强度。
当施加焊接时，焊接温度必须比最大运作温度高至少100～150℃。
催化剂可通过例如喷散、涂刷或浸渍到一含有一陶瓷母体粒子的泥浆中而配置到多孔结构内。此后，使泥浆干燥和煅烧。最后，将使这样获得的陶瓷层浸渍有催化活性材料。或者，将催化活性材料与陶瓷母体粒子同时施加。
附图说明和具体实施方式
在本发明的一具体实施例中，多孔结构通过下列步骤被粘附到一重整反应器的壁上：
在对载体材料与管件进行适当的预处理后，将一多孔金属结构与焊接材料一起安置在一反应器管内。该管件被安装在一感应炉内，从而将管件的一部分加热到焊接温度以上。在焊接区域内使用一冲头或球体来将多孔金属压靠到管壁上，以确保多孔金属与管壁接触，如附图1中所示意表示的。该加热区域与冲头则沿管件长度移动，以获得沿管件整个长度的载体材料的焊接。
通过使用一合适形状的冲头，本发明也可用于圆形管件以外的其它形状。
将多孔金属粘附到一重整反应器壁上的另一方法所用的一装置示意地表示在图2a与2b中。图2a表示从端部观看的装置。图2b表示一分解的视图。多孔金属结构4在对载体材料与管件进行适当的预处理后，与焊接材料5一起被安置在管件6内。在管件内侧安装一第二较小的管件或杆1。在内、外管件之间的环形空间内安置一材料2，该材料在高温下膨胀。安置一隔件3，以避免材料2与结构4之间的接触。该管件被放置在一炉内并且被加热到焊接温度。膨胀的材料则迫使多孔金属结构抵靠到管件壁上，以确保与管壁接触。一有用的膨胀材料2为可从3M公司获得的一产品，其品名为Interam。
在两种方法中催化剂接着都被分散到多孔结构内。对于上述蒸汽重整使用了催化硬件之优点在于特别与一蒸汽重整处理方法有关，并且总体上与由外部热源加热的吸热性处理方法有关。
Claims (8)
1.一种用于制备富含氢和一氧化碳的气体的方法，其包括：
将一多孔金属结构放置在重整反应器的壁上；
将该多孔金属结构粘附在重整反应器的壁上；
在该多孔金属结构中提供一陶瓷载体材料；
将一蒸汽重整催化活性材料结合到陶瓷载体材料中；以及
通过以下步骤使一烃原料在蒸汽重整催化活性材料存在的情况下进行蒸汽重整，即，使该原料通过重整反应器，该重整反应器具有多孔金属结构和设置于其中的陶瓷载体材料以及充入陶瓷载体材料中的蒸汽重整催化活性材料。
2.如权利要求1所述的方法，其特征是，金属结构为一泡沫金属、金属网、膨胀金属或烧结金属。
3.如权利要求1所述的方法，其特征是，多孔金属结构通过焊接或扩散粘接而被粘附到重整反应器的壁上。
4.如权利要求3所述的方法，其特征是，焊接是通过一感应炉来进行的。
5.如权利要求4所述的方法，其特征是，多孔金属结构为泡沫金属。
6.如权利要求3所述的方法，其特征是，多孔金属结构在通过一膨胀材料来进行焊接处理的过程中被固定。
7.如前述权利要求中任一项所述的方法，其特征是，重整反应器为一管件。
8.如权利要求2所述的方法，其特征是，金属结构为金属丝网。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13639899P | 1999-05-27 | 1999-05-27 | |
| US60/136398 | 1999-05-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1275524A CN1275524A (zh) | 2000-12-06 |
| CN1202986C true CN1202986C (zh) | 2005-05-25 |
Family
ID=22472681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001087215A Expired - Fee Related CN1202986C (zh) | 1999-05-27 | 2000-05-26 | 以蒸汽重整法制备合成气体 |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US6576158B1 (zh) |
| EP (1) | EP1055637B1 (zh) |
| JP (1) | JP2001019404A (zh) |
| KR (1) | KR100395002B1 (zh) |
| CN (1) | CN1202986C (zh) |
| AT (1) | ATE308482T1 (zh) |
| CA (1) | CA2310481A1 (zh) |
| DE (1) | DE60023591T2 (zh) |
| ES (1) | ES2250044T3 (zh) |
| NO (1) | NO20002714L (zh) |
| RU (1) | RU2264350C2 (zh) |
| ZA (1) | ZA200002649B (zh) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0507741A (pt) * | 2004-02-17 | 2007-07-10 | Modine Mfg Co | trocador de calor recuperativo e sistema de processamento de combustìvel |
| US7939046B2 (en) * | 2004-06-21 | 2011-05-10 | Raytheon Company | Microporous graphite foam and process for producing same |
| US7320778B2 (en) * | 2004-07-21 | 2008-01-22 | Catacel Corp. | High-performance catalyst support |
| WO2006045744A1 (en) * | 2004-10-20 | 2006-05-04 | Shell Internationale Research Maatschappij B.V. | Process for steam and/or co2 reforming of a hydrocarbonaceous feedstock |
| US7472936B2 (en) * | 2005-04-14 | 2009-01-06 | Catacel Corp. | Tool for insertion and removal of a catalytic reactor cartridge |
| US20060230613A1 (en) * | 2005-04-14 | 2006-10-19 | Catacel Corporation | Catalytic reactor cartridge |
| US7565743B2 (en) * | 2005-04-14 | 2009-07-28 | Catacel Corp. | Method for insertion and removal of a catalytic reactor cartridge |
| US7682580B2 (en) * | 2005-05-19 | 2010-03-23 | Catacel Corp. | Catalytic reactor having radial leaves |
| US7501102B2 (en) * | 2005-07-28 | 2009-03-10 | Catacel Corp. | Reactor having improved heat transfer |
| US20070175094A1 (en) * | 2006-01-30 | 2007-08-02 | Reinke Michael J | Integrated autothermal reformer recuperator |
| DK3814273T3 (da) | 2018-06-26 | 2022-10-24 | Thyssenkrupp Ind Solutions Ag | Fremgangsmåde til tilvejebringelse af syntesegas ved hjælp af en yderligere elektrisk opvarmning |
| DE102018210409A1 (de) | 2018-06-26 | 2020-01-02 | Thyssenkrupp Ag | Verfahren zur Bereitstellung von Synthesegas mit Hilfe einer zusätzlichen induktiven Heizung |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2333571A1 (fr) * | 1975-12-05 | 1977-07-01 | Inst Nawozow Sztucznych | Procede de fabrication d'un catalyseur pour le reformage a la vapeur d'hydrocarbures et pour la methanisation |
| US5039510A (en) * | 1983-03-25 | 1991-08-13 | Imperial Chemical Industries Plc | Steam reforming |
| JPS59205332A (ja) * | 1983-05-10 | 1984-11-20 | Mitsubishi Heavy Ind Ltd | 炭化水素よりオレフインを製造する方法 |
| GB8501526D0 (en) * | 1985-01-22 | 1985-02-20 | Ici Plc | Catalyst |
| KR930004068B1 (ko) * | 1990-11-14 | 1993-05-20 | 오옥수 | 함인 브레이크슈 재료를 용제하기 위한 모합금 |
| JP3328845B2 (ja) * | 1992-10-12 | 2002-09-30 | 三菱瓦斯化学株式会社 | 水素製造法とそれに用いる触媒 |
| DE4333293A1 (de) * | 1993-09-30 | 1995-04-06 | Basf Ag | Verfahren zur selektiven Hydrierung von Butindiol-1,4 zu Buten-2-diol-1,4 und dafür geeigneter Katalysator |
| KR100271387B1 (en) * | 1994-06-06 | 2000-11-15 | Praxair Technology Inc | Method for the endothermic generation of carbon monoxide and hydrogen atmospheres for the heat traeting |
| DE19534433C1 (de) * | 1995-09-16 | 1996-10-10 | Daimler Benz Ag | Katalysatorschichtstruktur für einen Methanolreformierungsreaktor und Verfahren zu ihrer Herstellung |
| KR100240563B1 (ko) * | 1995-12-30 | 2000-01-15 | 김덕중 | 전기 방전을 이용한 탄화수소계 원료의 개질에 의한 수소 제조방법 및 이에 사용되는 장치 |
| US5718881A (en) * | 1996-06-24 | 1998-02-17 | International Fuel Cells, Inc. | Catalytic reactor designed to reduce catalyst slumping and crushing |
| EP0855366B1 (en) * | 1997-01-22 | 2001-05-02 | Haldor Topsoe A/S | Synthesis gas production by steam reforming using catalyzed hardware |
| KR100246079B1 (ko) * | 1997-12-15 | 2000-03-15 | 한갑수 | 합성가스 제조용 반응기 및 이를 이용한 합성가스의 제조방법 |
| EP0931762B1 (en) * | 1998-01-21 | 2005-05-04 | Haldor Topsoe A/S | Process for the preparation of hydrogen-rich gas |
| US6197365B1 (en) * | 1999-03-30 | 2001-03-06 | Xcellsis Gmbh | Process for manufacturing a catalytic material |
-
2000
- 2000-04-17 AT AT00108369T patent/ATE308482T1/de not_active IP Right Cessation
- 2000-04-17 DE DE60023591T patent/DE60023591T2/de not_active Expired - Lifetime
- 2000-04-17 EP EP00108369A patent/EP1055637B1/en not_active Expired - Lifetime
- 2000-04-17 ES ES00108369T patent/ES2250044T3/es not_active Expired - Lifetime
- 2000-05-25 JP JP2000155123A patent/JP2001019404A/ja active Pending
- 2000-05-25 US US09/577,600 patent/US6576158B1/en not_active Expired - Fee Related
- 2000-05-26 CN CNB001087215A patent/CN1202986C/zh not_active Expired - Fee Related
- 2000-05-26 ZA ZA200002649A patent/ZA200002649B/xx unknown
- 2000-05-26 RU RU2000113107/15A patent/RU2264350C2/ru not_active IP Right Cessation
- 2000-05-26 CA CA002310481A patent/CA2310481A1/en not_active Abandoned
- 2000-05-26 NO NO20002714A patent/NO20002714L/no not_active Application Discontinuation
- 2000-05-26 KR KR10-2000-0028553A patent/KR100395002B1/ko not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CA2310481A1 (en) | 2000-11-27 |
| DE60023591T2 (de) | 2006-06-01 |
| NO20002714L (no) | 2000-11-28 |
| EP1055637A1 (en) | 2000-11-29 |
| ATE308482T1 (de) | 2005-11-15 |
| US6576158B1 (en) | 2003-06-10 |
| NO20002714D0 (no) | 2000-05-26 |
| JP2001019404A (ja) | 2001-01-23 |
| KR100395002B1 (ko) | 2003-08-19 |
| RU2264350C2 (ru) | 2005-11-20 |
| ZA200002649B (en) | 2000-11-30 |
| KR20010049413A (ko) | 2001-06-15 |
| EP1055637B1 (en) | 2005-11-02 |
| DE60023591D1 (de) | 2005-12-08 |
| ES2250044T3 (es) | 2006-04-16 |
| CN1275524A (zh) | 2000-12-06 |
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