CN1183376A - 蒸汽转化方法 - Google Patents
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- 238000000629 steam reforming Methods 0.000 title description 14
- 239000007789 gas Substances 0.000 claims abstract description 64
- 238000002485 combustion reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 238000002407 reforming Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 241000707825 Argyrosomus regius Species 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
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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
- 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
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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
- C01B2203/08—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
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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
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Abstract
本发明提供氨合成气的制备方法,该方法包括将原料气和烟道气混合,以获得混合气。将混合气供应至少一对重整反应器,每个反应器具有加工及燃料端和燃烧端。每对反应器的加工及燃料端并联布置,而燃烧端串联布置。通过向一对反应器的第一反应器供应过量的燃烧空气,而向第二反应器供应贫氧燃烧空气来控制每对反应器的火焰温度。
Description
本申请要求1996年10月4日申请的美国临时专利No.60/027,639的利益。
本发明涉及氨合成气的制备方法。
本发明提供氨合成气的制备方法。该方法包括,将原料流与烟道气混合,以便获得混合气,然后将分流中的混合气送入至少一对转化反应器中。每个反应器具有一个加工及燃料端和燃烧端。每对反应器的加工及燃料端并联排布,而燃烧端串联排布。每个反应器中的火焰温度保持低于大约1400℃。原料气通常要进行脱硫。
从每对反应器的第二个反应器中取出的烟道气通常主要由CO2、H2O和N2组成。选择烟道气的量,以便获得合成气中预定的H2/N2比。
原料流可以再与蒸汽混合。最好通过供应大量过量的空气,例如大约过量105%,保持第一反应器的温度。每对反应器中第一反应器的烟道气作为燃烧空气供应第二反应器。烟道气的氧气耗尽,这将火焰温度限制到低于大约1400℃。保持总空气过量低至大约5%。
按照优选实施方案,将混合气送入至少两对反应器中。每个反应器的加工气端并联连接。每对反应器的燃烧端与另一对反应器分燃烧端串联连接。
与现有技术相比,本发明的主要优点如下:
来自NH3生产的化学计量合成气在热交换转化反应器中生产,而不用富空气或过量氮气的深冷分离;
在燃烧空气端串联使用两个转化反应器,提供对火焰温度的控制,不必使用总体过量燃烧空气;
由转化过程释放到大气的NOx减至最小;消除了SO2的释放;
通过燃烧形成的CO2和蒸汽部分用作转化炉进料,降低总蒸汽的需求;
过量烟道气的膨胀部分恢复了燃烧空气的压缩动力。
此外,进料气与来自随后热交换蒸汽转化法步骤的含氮气和二氧化碳的烟道气混合进行的蒸汽转化,提供的碳氢化合物原料蒸汽转化的转化率较高,由此提供的反应器流出物中未转化碳氢化合物的浓缩较低。
在蒸汽转化反应器中,通过与加压烟道气进行间接热交换,提供吸热蒸汽转化反应所需的热。
为了提供用于热交换蒸汽转化法的烟道气,燃料与第一热交换蒸汽转化步骤空气中的过量空气一起燃烧,使得反应器中的燃烧温度较低。然后从第一转化步骤中取出含氧烟道气,进行中间冷却,再与随后一个或多个转化步骤中的其它燃料一起燃烧。
参考附图,由本发明的以下描述中将清楚地看出本发明的其它特征和优点。
图1为本发明方法的简图。
图2为本发明方法的另一实施方案的简图。
图1示出了本发明方法的简化形式。原料20通常为脱硫的天然气,分流为两个气流。原料与气流30和预定量的脱氧加压烟道气40(参见下文)混合,获得待生产合成气中所需的正确的H2/N2比。气体混合物用作两个热交换转化反应器60、80(其加工及燃料端并联排布,燃烧空气端串联排布)中的加工气。排布在转化反应器中的每个催化剂床62、82的出口温度很高,以确保CH4泄漏适当低些。
将空气100加压至比热交换器上游加工气的压力稍高的压力。空气首先用作第一热交换燃烧炉64中的燃烧空气,燃烧炉在大量过量(大约过量105%)的空气中进行操作,以保持火焰温度低于1400℃。
与第一反应器中转化炉管进行热交换后,加压烟道气102(于大约600℃)还用作第二反应器80的燃烧空气。该燃烧空气是贫氧的,这将火焰温度限制到低于大约1400℃,同时总空气保持低度过量,大约过量5%。
第二反应器的烟道气104分流为两个气流106、108。气流106膨胀,提供空气压缩所需的部分动力。残留量的烟道气108送入脱氧器中,以除去残留的微量氧气,再如上所述送入进入反应器的进料流中。
图2示出了本发明另一具体实施方案,按照该实施方案,加工气中的甲烷在四个热交换蒸汽转化反应器I、II、III和IV中进行蒸汽转化。
转化炉为常规的插管(bayonet tube)型,其内管同轴放置在外套管中。蒸汽转化催化剂装载在内管和外管限定的环形空间内。
由此,由沿套管壁外部通过的热烟道气提供加工气中进行的吸热蒸汽转化反应所需的热。
在导入加工气2之前,气体与主要由CO2、H2O和N2组成的烟道气4混合。烟道气4向反应器中进行的蒸汽转化反应供应热后,从反应器II中取出。烟道气4与一定量的加工气混合,以获得通过反应器I-IV蒸汽转化制备的合成气所需的H2/N2比。
反应器I-IV就混合加工气6的导入而言为并联连接的。在燃烧/烟道气端,反应器以反应器I和II为一组、反应器III和IV为一组来排布。两个反应器组串联连接。
反应器I和II通过燃烧燃料和加压空气8进行加热。反应器I中用过量空气进行燃烧,以达到适当的燃烧温度并提供从反应器I中取出的烟道气中必需的氧气量,然后导入反应器II中,再与燃料一起燃烧。从反应器II中取出的烟道气12循环到具有常规氧化催化剂床的脱氧器14中,以除去气体中残留量的氧气。来自脱氧器14、基本上由氮气、二氧化碳和水组成的烟道气4循环到进料气2中并进行混合。
烟道气端串联连接的反应器III和IV通过在大气压下燃烧燃料进行加热。离开反应器III的烟道气16送入反应器IV进行燃烧。烟道气向反应器IV供应热后,送去进行废热回收。
尽管本发明联系特殊实施方案进行描述,但许多其它变化和修改对本领域技术人员是很明显的。因此,本发明不受具体说明书的限制,而仅受所附的权利要求限制。
Claims (10)
1.氨合成气的制备方法,包括以下步骤:
可选地将原料气与烟道气混合,以便获得混合气;
将可选地与烟道气混合的原料气送入至少一对重整反应器中,每个反应器具有加工及燃料端和燃烧端,每对反应器的加工及燃料端并联排布,而燃烧端串联排布;
其中通过向一对反应器的第一反应器供应过量的燃烧空气,而向第二反应器供应贫氧燃烧空气来控制每对反应器的火焰温度。
2.权利要求1的方法,其中火焰温度保持低于大约1400℃。
3.权利要求1的方法,还包括向第一反应器供应过量大约105%的空气。
4.权利要求1的方法,其中来自每对反应器中第一反应器的贫氧烟道气作为燃烧空气供应第二反应器,以便限制第二反应器的火焰温度,在第二反应器中保持总空气过量大约5%。
5.权利要求1的方法,其中供应第一反应器的燃烧空气被压缩至比位于反应器上游的原料气的压力稍高的压力。
6.权利要求6的方法,其中来自第二反应器的烟道气膨胀,以提供至少一部分空气压缩所需的动力。
7.权利要求1的方法,其中从各对反应器的第二反应器中取出与原料气混合的烟道气。
8.权利要求1的方法,其中混合气送入至少两对反应器中,每对反应器的燃烧端与另一对反应器的燃烧端串联连接。
9.权利要求1的方法,其中选择与原料气混合的烟道气的量,以便获得合成气中预定的H2/N2比。
10.权利要求1的方法,其中原料是经过脱硫的。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US2763996P | 1996-10-04 | 1996-10-04 | |
US027639 | 1996-10-04 | ||
US027,639 | 1996-10-04 |
Publications (2)
Publication Number | Publication Date |
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CN1183376A true CN1183376A (zh) | 1998-06-03 |
CN1100721C CN1100721C (zh) | 2003-02-05 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN97120064A Expired - Fee Related CN1100721C (zh) | 1996-10-04 | 1997-10-05 | 制备氨合成气的蒸汽重整方法 |
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Country | Link |
---|---|
US (1) | US5925328A (zh) |
EP (1) | EP0834465B1 (zh) |
JP (1) | JP4105786B2 (zh) |
CN (1) | CN1100721C (zh) |
AT (1) | ATE194816T1 (zh) |
DE (1) | DE69702581T2 (zh) |
RU (1) | RU2211798C2 (zh) |
Cited By (2)
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CN101049908B (zh) * | 2006-04-05 | 2011-05-25 | 气体产品与化学公司 | 重整装置和合成气产生方法 |
CN102471707A (zh) * | 2010-03-01 | 2012-05-23 | 普拉斯科能源Ip控股集团毕尔巴鄂沙夫豪森分公司 | 具有集成处理区的碳转化系统 |
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DK173496B1 (da) * | 1998-07-16 | 2001-01-02 | Topsoe Haldor As | Fremgangsmåde til fremstilling af syntesegas ved vanddampreformering under anvendelse af en katalyseret metaloverflade |
PT1106570E (pt) * | 1999-12-02 | 2013-10-15 | Haldor Topsoe As | Processo e reactor para realizar reacções catalíticas não adiabáticas |
US20040161381A1 (en) * | 1999-12-02 | 2004-08-19 | Thomsen Soren Gyde | Process and reactor for carrying out non-adiabatic catalytic reactions |
US6962492B2 (en) | 2001-10-05 | 2005-11-08 | Mold-Masters Limited | Gap seal between nozzle components |
US7967878B2 (en) * | 2002-01-04 | 2011-06-28 | Meggitt (Uk) Limited | Reformer apparatus and method |
US7138001B2 (en) * | 2003-03-16 | 2006-11-21 | Kellogg Brown & Root Llc | Partial oxidation reformer-reforming exchanger arrangement for hydrogen production |
US7220505B2 (en) * | 2003-03-18 | 2007-05-22 | Kellogg Brown & Root Llc | Autothermal reformer-reforming exchanger arrangement for hydrogen production |
US7320778B2 (en) * | 2004-07-21 | 2008-01-22 | Catacel Corp. | High-performance catalyst support |
WO2006027175A1 (en) * | 2004-09-09 | 2006-03-16 | Haldor Topsøe A/S | Process for production of hydrogen and/or carbon monoxide |
US7565743B2 (en) * | 2005-04-14 | 2009-07-28 | Catacel Corp. | Method for insertion and removal of a catalytic reactor cartridge |
US20060230613A1 (en) * | 2005-04-14 | 2006-10-19 | Catacel Corporation | Catalytic reactor cartridge |
US7472936B2 (en) * | 2005-04-14 | 2009-01-06 | Catacel Corp. | Tool for insertion and removal of a catalytic reactor cartridge |
US7682580B2 (en) * | 2005-05-19 | 2010-03-23 | Catacel Corp. | Catalytic reactor having radial leaves |
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US7501102B2 (en) * | 2005-07-28 | 2009-03-10 | Catacel Corp. | Reactor having improved heat transfer |
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CN102319555A (zh) * | 2011-06-27 | 2012-01-18 | 吴焕松 | 一种利用空气除氧去杂制备无氧保护气体的方法及装置 |
US8545775B2 (en) * | 2011-10-20 | 2013-10-01 | Kellogg Brown & Root Llc | Reforming exchanger system with intermediate shift conversion |
WO2016004955A1 (en) | 2014-07-09 | 2016-01-14 | Haldor Topsøe A/S | Process for producing hydrogen |
FR3040167B1 (fr) | 2015-08-18 | 2020-12-25 | Air Liquide | Procede de production de gaz de synthese au moyen de reacteurs de vaporeformage |
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1997
- 1997-09-17 AT AT97116134T patent/ATE194816T1/de not_active IP Right Cessation
- 1997-09-17 DE DE69702581T patent/DE69702581T2/de not_active Expired - Lifetime
- 1997-09-17 EP EP97116134A patent/EP0834465B1/en not_active Expired - Lifetime
- 1997-10-02 US US08/943,066 patent/US5925328A/en not_active Expired - Lifetime
- 1997-10-03 JP JP27152797A patent/JP4105786B2/ja not_active Expired - Fee Related
- 1997-10-03 RU RU97116511/12A patent/RU2211798C2/ru not_active IP Right Cessation
- 1997-10-05 CN CN97120064A patent/CN1100721C/zh not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101049908B (zh) * | 2006-04-05 | 2011-05-25 | 气体产品与化学公司 | 重整装置和合成气产生方法 |
CN102471707A (zh) * | 2010-03-01 | 2012-05-23 | 普拉斯科能源Ip控股集团毕尔巴鄂沙夫豪森分公司 | 具有集成处理区的碳转化系统 |
Also Published As
Publication number | Publication date |
---|---|
EP0834465A3 (en) | 1998-04-15 |
EP0834465B1 (en) | 2000-07-19 |
RU2211798C2 (ru) | 2003-09-10 |
JPH10231102A (ja) | 1998-09-02 |
CN1100721C (zh) | 2003-02-05 |
JP4105786B2 (ja) | 2008-06-25 |
EP0834465A2 (en) | 1998-04-08 |
US5925328A (en) | 1999-07-20 |
DE69702581D1 (de) | 2000-08-24 |
ATE194816T1 (de) | 2000-08-15 |
DE69702581T2 (de) | 2000-11-23 |
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