CN1203186A - 制备氨合成气的方法和生产装置 - Google Patents
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 230000009466 transformation Effects 0.000 claims description 27
- 238000000629 steam reforming Methods 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 238000001193 catalytic steam reforming Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 36
- 239000000446 fuel Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
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- 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
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- 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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- 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
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
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Abstract
从烃原料制备氨合成气的方法和装置,包括在热交换初次蒸汽转化装置和其后的二次转化装置里顺序地初次蒸汽转化和二次蒸汽转化原料,其中将流出的初次蒸汽转化气体流用在初次蒸汽转化气体输入二次转化装置之前的二次转化气体的热产物流采用间接热交换加热。
Description
本申请针对氨合成气的制备。更具体地说，本发明涉及制备这种气体的方法和生产装置，包括在热交换式初次蒸汽转化装置和其后的绝热转化装置里把烃原料顺序地进行初次蒸汽转化和二次蒸汽转化。
传统的氨合成气的制备采用在燃烧管式蒸汽转化装置里将天然气或高级烃的烃原料通过与蒸汽转化催化剂接触进行吸热蒸汽转化反应进行。然后将初次转化气体送进二次绝热转化装置里，在二次绝热转化装置里，在气体里的部分氢和剩余的烃在二次转化催化剂存在下用空气或富含氧的气体部分氧化。在上述蒸汽转化反应里，原料与在二次转化阶段中通过加入的空气加到气体里的氮气反应中形成含有氢、一氧化碳和二氧化碳的粗氨合成气从二次转化装置里出来。
用于初次绝热蒸汽转化反应所必须的热量通常由燃料在初次蒸汽转化装置烟道气侧壁内燃烧提供，其中催化剂设置在穿过该转化装置垂直延伸的管子里。在初次转化装置里为了降低燃烧负荷和燃料消耗，也曾经提议通过利用流出来的蒸汽转化气流作为热源提供一部分热量。这样的方法和反应器在美国专利US 5429809里提出，其中，热量一部分由来自燃料燃烧的热烟道气流提供，一部分由在插管式热交换反应器的热产物流提供。
本发明的总目的是在用于从烃原料制备氨合成气的顺序地初次热交换蒸汽转化和二次转化中进一步降低燃烧负荷和燃料消耗。
根据这个总目的，本发明的一个目的是提供从烃原料制备氨合成气的方法，包括在初次热交换蒸汽转化装置里和在随后的二次转化装置里顺序地进行初次和二次催化蒸汽转化原料的阶段，其中将流出的初次蒸汽转化气体流在初次蒸汽转化气体输入二次转化装置之前由二次转化气体的热产物流采用间接热交换加热。
本发明的另一个目的是提供一种用于上述蒸汽转化方法中的生产装置。因此这个生产装置包括，一个连接到二次蒸汽转化装置的初次热交换蒸汽转化装置和设置在二次蒸汽转化装置上游的进料/流出物热交换器，以便将来自初次热交换蒸汽转化装置的蒸汽转化烃原料的流出气流由来自二次蒸汽转化装置的产物流采用间接热交换加热。
本文中前文和下文所述的术语“热交换蒸汽转化装置”是指一种蒸汽转化装置，其在初次蒸汽转化催化剂的固定床上发生的初次蒸汽转化反应所需要的热量一部分是通过热燃烧气体提供，一部分由通过转化装置的二种与催化床有热交换关系的气体在一次转化气体里所含的热量提供。在这种类型的转化装置里，在转化气体里的热量从一般约800℃的转化温度降至低水平的一般约600℃的出口温度而回收。
在二次蒸汽转化阶段进口的平衡温度是在初次蒸汽转化催化床出口处初次转化气体的温度，一般高于800℃。
然而，在使用没有预热的初次转化气体顺序地进行初次和二次蒸汽转化中的热交换初次蒸汽转化装置时，在二次转化装置进口处的初次转化气体的温度却因为与在初次转化装置里的生成气体的间接热交换而比较低。这导致在二次蒸汽转化阶段原料转化率降低。
为了得到要求的化学计算量的二次转化粗氨合成气的组成和在随后氨合成工艺里所要求的在气体里低的氢含量，在顺序的初次热交换和不预热初次转化气体的二次转化中的初次转化气体的平衡温度必须提高用以补偿在二次转化阶段低的氢原料转化率。
通过把二次转化装置和进料/流出物热交换器创造性地相结合，在热交换转化装置里已经降低于平衡温度的初次蒸汽转化气体的温度通过与来自二次转化装置的热产物流的间接热交换被升高至二次转化装置里所要求的反应温度。这样，通过在进料/流出物热交换器里回收在二次蒸汽转化气体里多余的热量，在初次转化装置里的燃料消耗有利地降低了。与传统的初次-二次蒸汽转化相比，这种方式导致来自蒸汽转化区生成的粗氨合成气出口温度相应较低。
来自转化区的较低的出口温度和在初次转化装置中降低的燃料消耗，导致在转化装置区消耗曲线全面改善。
在以下的说明中将参照附图更详细地说明本发明，其中唯一的附图表示根据本发明一个特定实施例的工艺的简化的流程图。
当根据本发明的一个特定实施例的工艺操作时，例如天然气和蒸汽之类的进料2在温度为450℃下被送入初次热交换转化反应器4内。反应器4是一种传统设计的插管式反应器，包括在抗压壳6内的由薄板制的外管8(其出口端封闭并且同心地围绕着一个端部开口的热交换插接内管10)构成的一个或多个反应器管道。
在管8和10之间的空间用初次转化催化剂12填充。
输入的进料2经过外管8和催化剂12，通过和催化剂12接触被初次蒸汽转化。在催化剂12上进行的吸热蒸汽转化反应所需要的热量由热烟道气供给，热烟道气由在底部燃烧器14内燃烧燃料获得，在热烟道气沿着外管8的壁经过时，和在管8内的反应进料呈热传导关系。
补充热量由来自催化剂12的热的初次转化气流16供给，气流16以800℃的出口温度离开催化剂并且通过内管10，在催化剂12内与反应进料气体呈热传导关系。
初次转化的气体16的温度因此下降至600℃。
然后气体16被输送至进料/流出物热交换器18，在这里气体16的温度通过与以975℃的温度的正从二次转化装置22排出的热的二次转化的气体20的间接热交换被升至800℃。二次转化装置22是一个传统设计的绝热转化装置，在这里预热的初次转化气体16在该反应器的顶部用空气24部分氧化，然后通过与在二次转化反应器22底部设置成固定床26的二次转化催化剂相接触而被二次转化。二次转化气体20从反应器的底部以975℃的温度排出，并且通过如上所述的间接热交换被冷却至825℃。
Claims (2)
1、从烃原料制备氨合成气的方法，包括在初次热交换蒸汽转化装置里和在随后的二次转化装置里顺序地进行初次和二次催化蒸汽转化原料的阶段，其中将流出的初次蒸汽转化气体流由在初次蒸汽转化气体输入二次转化装置之前的二次转化气体的热产物流采用间接热交换加热。
2、提供用于上述蒸汽转化方法中的处理装置，该处理装置包括，一个连接到二次蒸汽转化装置的初次热交换蒸汽转化装置和设置在二次蒸汽转化装置上游的进料/流出物热交换器，以便将来自初次热交换蒸汽转化装置的蒸汽转化烃原料的流出气流用来自二次蒸汽转化装置的产物流采用间接热交换加热。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK0510/1997 | 1997-05-05 | ||
| DK0510/97 | 1997-05-05 | ||
| DK199700510A DK173052B1 (da) | 1997-05-05 | 1997-05-05 | Fremgangsmåde til fremstilling af ammoniak syntesegas |
Publications (2)
| Publication Number | Publication Date |
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| CN1203186A true CN1203186A (zh) | 1998-12-30 |
| CN1105080C CN1105080C (zh) | 2003-04-09 |
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| CN98109785A Expired - Fee Related CN1105080C (zh) | 1997-05-05 | 1998-05-04 | 制备氨合成气的方法和生产装置 |
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| Country | Link |
|---|---|
| US (1) | US6077459A (zh) |
| EP (1) | EP0876993B1 (zh) |
| JP (1) | JPH111303A (zh) |
| KR (1) | KR19980086722A (zh) |
| CN (1) | CN1105080C (zh) |
| AT (1) | ATE400527T1 (zh) |
| DE (1) | DE69839685D1 (zh) |
| DK (1) | DK173052B1 (zh) |
| EA (1) | EA000777B1 (zh) |
| TW (1) | TW513385B (zh) |
| UA (1) | UA53630C2 (zh) |
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| CN100379842C (zh) * | 1999-07-15 | 2008-04-09 | 赫多特普索化工设备公司 | 一种用于烃原料催化蒸汽重整的方法 |
| CN105858603A (zh) * | 2007-08-08 | 2016-08-17 | 阿梅尼亚·卡萨莱股份有限公司 | 制备氨合成气的方法 |
| CN107812499A (zh) * | 2016-09-14 | 2018-03-20 | 乔治·克劳德方法的研究开发空气股份有限公司 | 具有结构化催化剂和改善的热平衡的重整器管 |
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| DK173742B1 (da) * | 1998-09-01 | 2001-08-27 | Topsoe Haldor As | Fremgangsmåde og reaktorsystem til fremstilling af syntesegas |
| PT1106570E (pt) * | 1999-12-02 | 2013-10-15 | Haldor Topsoe As | Processo e reactor para realizar reacções catalíticas não adiabáticas |
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| US6647930B2 (en) * | 2002-02-11 | 2003-11-18 | L'Air Liquide-Societe Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des Procedes Georges Claude | Ammonia vapor generation |
| US7435401B2 (en) * | 2004-07-02 | 2008-10-14 | Kellogg Brown & Root Llc | Pseudoisothermal ammonia process |
| US7892511B2 (en) * | 2004-07-02 | 2011-02-22 | Kellogg Brown & Root Llc | Pseudoisothermal ammonia process |
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| EP1698590A1 (en) * | 2005-03-04 | 2006-09-06 | Ammonia Casale S.A. | Reforming process for synthesis gas production and related plant |
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| US7682580B2 (en) * | 2005-05-19 | 2010-03-23 | Catacel Corp. | Catalytic reactor having radial leaves |
| US7504048B2 (en) * | 2005-06-14 | 2009-03-17 | Air Products And Chemicals, Inc. | Axial convective reformer |
| US7501102B2 (en) * | 2005-07-28 | 2009-03-10 | Catacel Corp. | Reactor having improved heat transfer |
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| GB8609099D0 (en) * | 1986-04-15 | 1986-05-21 | British Petroleum Co Plc | Production of synthesis gas |
| GB8728882D0 (en) * | 1987-12-10 | 1988-01-27 | Ici Plc | Hydrogen |
| US5011625A (en) * | 1989-12-11 | 1991-04-30 | The M. W. Kellogg Company | Autothermal steam reforming process |
| DK167864B1 (da) * | 1990-02-02 | 1993-12-27 | Topsoe Haldor As | Fremgangsmaade og reaktorsystem til reforming af carbonhydrider under varmeveksling |
| US5429809A (en) * | 1991-09-23 | 1995-07-04 | Haldor Topsoe A/S | Process and reactor for carrying out non-adiabatic catalytic reactions |
| DK162891A (da) * | 1991-09-23 | 1993-03-24 | Haldor Topsoe As | Fremgangsmaade og reaktor til gennemfoerelse af ikke-adiabatiske reaktioner. |
-
1997
- 1997-05-05 DK DK199700510A patent/DK173052B1/da not_active IP Right Cessation
-
1998
- 1998-04-24 TW TW087106411A patent/TW513385B/zh not_active IP Right Cessation
- 1998-04-28 AT AT98107704T patent/ATE400527T1/de not_active IP Right Cessation
- 1998-04-28 EP EP98107704A patent/EP0876993B1/en not_active Expired - Lifetime
- 1998-04-28 DE DE69839685T patent/DE69839685D1/de not_active Expired - Fee Related
- 1998-04-30 EA EA199800356A patent/EA000777B1/ru not_active IP Right Cessation
- 1998-05-01 JP JP10122406A patent/JPH111303A/ja active Pending
- 1998-05-02 KR KR1019980015837A patent/KR19980086722A/ko not_active Application Discontinuation
- 1998-05-04 UA UA98052260A patent/UA53630C2/uk unknown
- 1998-05-04 CN CN98109785A patent/CN1105080C/zh not_active Expired - Fee Related
- 1998-05-05 US US09/072,966 patent/US6077459A/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100379842C (zh) * | 1999-07-15 | 2008-04-09 | 赫多特普索化工设备公司 | 一种用于烃原料催化蒸汽重整的方法 |
| CN105858603A (zh) * | 2007-08-08 | 2016-08-17 | 阿梅尼亚·卡萨莱股份有限公司 | 制备氨合成气的方法 |
| CN107812499A (zh) * | 2016-09-14 | 2018-03-20 | 乔治·克劳德方法的研究开发空气股份有限公司 | 具有结构化催化剂和改善的热平衡的重整器管 |
| CN107812499B (zh) * | 2016-09-14 | 2021-12-28 | 乔治·克劳德方法的研究开发空气股份有限公司 | 具有结构化催化剂和改善的热平衡的重整器管 |
Also Published As
| Publication number | Publication date |
|---|---|
| DK173052B1 (da) | 1999-12-06 |
| CN1105080C (zh) | 2003-04-09 |
| ATE400527T1 (de) | 2008-07-15 |
| EA000777B1 (ru) | 2000-04-24 |
| DE69839685D1 (de) | 2008-08-21 |
| US6077459A (en) | 2000-06-20 |
| DK51097A (da) | 1998-11-06 |
| KR19980086722A (ko) | 1998-12-05 |
| EA199800356A1 (ru) | 1998-12-24 |
| TW513385B (en) | 2002-12-11 |
| UA53630C2 (uk) | 2003-02-17 |
| EP0876993B1 (en) | 2008-07-09 |
| JPH111303A (ja) | 1999-01-06 |
| EP0876993A1 (en) | 1998-11-11 |
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