CN1129552C - 自热催化蒸汽转化的方法 - Google Patents
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- CN1129552C CN1129552C CN00106514A CN00106514A CN1129552C CN 1129552 C CN1129552 C CN 1129552C CN 00106514 A CN00106514 A CN 00106514A CN 00106514 A CN00106514 A CN 00106514A CN 1129552 C CN1129552 C CN 1129552C
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- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 title claims description 8
- 238000010438 heat treatment Methods 0.000 title description 6
- 238000000629 steam reforming Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 239000012528 membrane Substances 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- -1 oxonium ion Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Classifications
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0251—Physical processing only by making use of membranes
-
- 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
- C01B2203/80—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0046—Nitrogen
Abstract
一种由烃原料制备氢和/或一氧化碳富气的方法，它包括：采用一种由膜渗透供给的氧化剂对烃原料进行部分氧化，并在一种放置在该膜渗透侧的蒸汽转化催化剂存在下对原料进行蒸汽转化，其中催化剂的蒸汽转化活性在至少一个催化剂床的入口区域是减低的。
Description
技术领域
本发明涉及烃原料的自热催化蒸汽转化。特别地，本发明是关于已知自热催化蒸汽转化工艺的改进，其中的氧化剂是通过一种膜向反应过程气体提供的。
背景技术
采用带有致密可传导氧的陶瓷膜的反应器来生产合成气，对本领域技术人员来说是已知的(例如，WO98/48921)。
合成气在膜反应器中的生产，是通过采用由膜的氧化剂一侧传送的氧气而进行的。合成气的形成可用下列的三个反应式表示：
在上述方法中，气体的入口温度通常在500-800℃之间。在膜的合成气一侧的压力范围为常压-90×105帕，空气一侧的压力范围为常压-26×105帕。
甲烷蒸汽转化和转移反应通常在反应器出口处是接近平衡的。
发明内容
在本发明之前，已知的膜自热催化蒸汽转化方法的改善，是通过控制反应器中的温度梯度，同时在自热反应器的至少一个顶端部位采用一种具有低的蒸汽转化活性或不具有蒸汽转化活性的催化剂而实现的。
因此，本发明是一种由烃原料制备氢和/或一氧化碳富气的方法，它包括：采用一种由膜渗透提供的氧化剂对烃原料进行部分氧化，并在一种放置在该膜渗透侧的蒸汽转化催化剂存在下对原料进行蒸汽转化，其中催化剂的蒸汽转化活性在催化剂床的至少一个入口区域是减活的。
附图说明
自热膜蒸汽转化的原理如图1所示。
具体实施方式
含有烃类物质(在图1和下文中，是以甲烷为例)的原料4在膜6的渗透侧6a处进入反应器2。位于膜这侧的室内装填有蒸汽转化催化剂和/或部分氧化催化剂8。在进料入口处，相对于催化剂床中其它部位的催化剂活性来说，处于顶层8a的催化剂活性是减活的。催化剂除了以固定方式放置外，它也可直接载荷在膜的渗透侧(图中未画出)。
含氧蒸汽10(在图1和下文中，是以空气为例)在膜的另一侧进入反应器。合适的具有传送氧能力的膜材料，对本领域人员来说是公知的。如果氧离子呈可移动的形式，则电子可以相反的方向通过膜，从而可保证电中性。氧流量以一种复杂的方式取决于氧分压的压力差。
假定催化剂在顶层8a不具有蒸汽转化活性，则该催化剂就是作为一种氧化催化剂使用的。
因而，可以获得下列的优点：
·反应器的机械设计变得较简单；
·在较低的物料和/或氧化剂入口温度下的操作成为可能，从而降低热交换面积，减少燃料的消耗；
·所需要的膜面积变小。
对于本领域技术人员来说，用于氢或烃类氧化的催化剂是公知的。具有减低转化活性的蒸汽转化催化剂，可通过采用减低数量的具有催化性能的物质浸渍载体物质和/或添加促进剂以减低具有催化活性物质的活性。这些催化剂的制备方法和具有减低的蒸汽转化活性的催化剂，对本领域的技术人员来说，也是已知的。
还有一个优点是，具有减低活性的催化剂，可在较低的蒸汽/碳比值下进行无碳操作，这是通过向催化剂中添加促进剂以提高抗碳性能和减低催化剂的蒸汽转化活性而实现的。
如果对具有膜供给氧的已知催化自热蒸汽转化炉进行操作，则原料气的蒸汽转化平衡温度，低于原料气通常的反应器入口温度。当原料气与催化剂接触时，蒸汽转化反应立即就会进行。由于蒸汽转化反应是强烈的吸热反应，与气体入口温度相比，可以观察到气体和催化剂温度的降低。
流过膜的氧流量随着温度而增加，在低于某一温度(T0)下，氧流量基本为零。
因此，在带有具有高的蒸汽转化活性催化剂的反应器中，流过单位面积膜的氧流量将要降低。这会出现下列二种后果的一种：
a)反应器内的温度降低到某一水平，当低于这一水平时流过膜的氧流量可忽略。避免这种情形的唯一办法就是提高原料入口温度。
b)与处于原料气体温度的氧流量相比，氧流量是降低的。根据本发明的方法，在反应器的入口部位，采用具有减低的或零蒸汽转化活性的催化剂进行操作，温度的降低可以消除或者变得很不显著。因此，由于氧是在较高(平均)温度下流过膜的，所以，其温度可降低到接近T0的水平，或者可降低膜的面积。
Claims (5)
1.一种由烃原料制备氢和/或一氧化碳富气的方法，它包括：采用一种由膜渗透供给的氧化剂对烃原料进行部分氧化，并在一种放置在该膜渗透侧的蒸汽转化催化剂存在下对原料进行蒸汽转化，其中原料和氧化剂以平行流方向供给和至少反应器入口部分的反应温度由催化剂的蒸汽转化活性控制，催化剂床的至少入口区域比催化剂床的其余部分的蒸汽转化活性减低。
2.权利要求1的方法，其中所述入口区域的蒸汽转化的催化活性减低至零。
3.权利要求2的方法，其中所述入口区域催化剂在烃原料的氧化步骤中具有活性。
4.根据权利要求1的方法，其中的催化剂是设置在固定床上的。
5.根据权利要求1的方法，其中的催化剂是由该膜承载的。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12317899P | 1999-03-05 | 1999-03-05 | |
| US60/123178 | 1999-03-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1268481A CN1268481A (zh) | 2000-10-04 |
| CN1129552C true CN1129552C (zh) | 2003-12-03 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00106514A Expired - Fee Related CN1129552C (zh) | 1999-03-05 | 2000-03-05 | 自热催化蒸汽转化的方法 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US6338833B1 (zh) |
| EP (1) | EP1035072B1 (zh) |
| JP (1) | JP4541484B2 (zh) |
| CN (1) | CN1129552C (zh) |
| AT (1) | ATE266601T1 (zh) |
| CA (1) | CA2299940C (zh) |
| DE (1) | DE60010550T2 (zh) |
| ES (1) | ES2218012T3 (zh) |
| NO (1) | NO328246B1 (zh) |
| RU (1) | RU2248931C2 (zh) |
| ZA (1) | ZA200001107B (zh) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3871501B2 (ja) * | 2000-08-07 | 2007-01-24 | 株式会社ノリタケカンパニーリミテド | ゼオライト膜とその製造方法と膜リアクター |
| US6537465B2 (en) * | 2000-12-29 | 2003-03-25 | Praxair Technology, Inc. | Low pressure steam purged chemical reactor including an oxygen transport membrane |
| AU2003212554A1 (en) * | 2002-03-12 | 2003-09-22 | Hy9 Corporation | Steam-reforming catalytic structures |
| US7045231B2 (en) * | 2002-05-22 | 2006-05-16 | Protonetics International, Inc. | Direct hydrocarbon reforming in protonic ceramic fuel cells by electrolyte steam permeation |
| FR2846958B1 (fr) * | 2002-11-13 | 2005-08-26 | N Ghy | Valorisation de l'oxygene pour la production d'hydrogene a partir d'hydrocarbures avec sequestration de co2 |
| US7332237B2 (en) * | 2003-01-27 | 2008-02-19 | Protonetics International, Inc. | Stream reforming of solid carbon in protonic ceramic fuel cells |
| NO20034468D0 (no) * | 2003-10-06 | 2003-10-06 | Statoil Asa | Hydrogenproduksjon fra metanol |
| US7255949B2 (en) | 2004-05-25 | 2007-08-14 | Protonetics International, Inc. | Systems and methods to generate hydrogen and electrical power in a reversible compound fuel cell |
| JP4255941B2 (ja) * | 2005-10-19 | 2009-04-22 | 独立行政法人科学技術振興機構 | 酸素透過膜を用いた炭化水素改質方法及び炭化水素改質装置 |
| DE102005060171A1 (de) * | 2005-12-14 | 2007-06-21 | Uhde Gmbh | Oxidationsreaktor und Oxidationsverfahren |
| US20080260631A1 (en) * | 2007-04-18 | 2008-10-23 | H2Gen Innovations, Inc. | Hydrogen production process |
| DE102009060489A1 (de) | 2009-12-29 | 2011-06-30 | Uhde GmbH, 44141 | Vorrichtung und Verfahren zur Regelung der Sauerstoffpermeation durch nicht-poröse Sauerstoffanionen leitende keramische Membranen und deren Verwendung |
| RU2725983C2 (ru) * | 2017-01-17 | 2020-07-08 | Андрей Владиславович Курочкин | Автотермический реактор |
| US11492255B2 (en) | 2020-04-03 | 2022-11-08 | Saudi Arabian Oil Company | Steam methane reforming with steam regeneration |
| US11322766B2 (en) | 2020-05-28 | 2022-05-03 | Saudi Arabian Oil Company | Direct hydrocarbon metal supported solid oxide fuel cell |
| US11639290B2 (en) | 2020-06-04 | 2023-05-02 | Saudi Arabian Oil Company | Dry reforming of methane with carbon dioxide at elevated pressure |
| US11492254B2 (en) | 2020-06-18 | 2022-11-08 | Saudi Arabian Oil Company | Hydrogen production with membrane reformer |
| US11583824B2 (en) | 2020-06-18 | 2023-02-21 | Saudi Arabian Oil Company | Hydrogen production with membrane reformer |
| RU2755470C1 (ru) * | 2020-08-04 | 2021-09-16 | Федеральное государственное автономное образовательное учреждение высшего образования "Сибирский федеральный университет" | Способ получения газа, обогащенного водородом, из газообразного углеводородного сырья |
| US11718575B2 (en) | 2021-08-12 | 2023-08-08 | Saudi Arabian Oil Company | Methanol production via dry reforming and methanol synthesis in a vessel |
| US11787759B2 (en) | 2021-08-12 | 2023-10-17 | Saudi Arabian Oil Company | Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel |
| US11578016B1 (en) | 2021-08-12 | 2023-02-14 | Saudi Arabian Oil Company | Olefin production via dry reforming and olefin synthesis in a vessel |
| US11617981B1 (en) | 2022-01-03 | 2023-04-04 | Saudi Arabian Oil Company | Method for capturing CO2 with assisted vapor compression |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5879089A (ja) * | 1981-11-05 | 1983-05-12 | Matsushita Electric Ind Co Ltd | 炭化水素燃料改質装置 |
| JPS61161133A (ja) * | 1985-01-08 | 1986-07-21 | Mitsubishi Heavy Ind Ltd | 吸熱反応装置 |
| US5160713A (en) * | 1990-10-09 | 1992-11-03 | The Standard Oil Company | Process for separating oxygen from an oxygen-containing gas by using a bi-containing mixed metal oxide membrane |
| JP2998217B2 (ja) * | 1991-01-24 | 2000-01-11 | 富士電機株式会社 | 燃料改質器 |
| JPH04313339A (ja) * | 1991-04-12 | 1992-11-05 | Toyo Eng Corp | 触媒燃焼を利用した部分酸化改質反応器 |
| US5276237A (en) * | 1991-12-20 | 1994-01-04 | Amoco Corporation | Membrane and use thereof in oxidative conversion |
| ES2120538T3 (es) * | 1993-05-17 | 1998-11-01 | Haldor Topsoe As | Reformacion por vapor a alta temperatura. |
| DK175723B1 (da) * | 1995-03-20 | 2005-02-07 | Topsoe Haldor As | Fremgangsmåde til fremstilling af elektrisk energi i en höjtemperaturbrændselscelle |
| JPH09315801A (ja) * | 1996-03-26 | 1997-12-09 | 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システム |
| US5980840A (en) * | 1997-04-25 | 1999-11-09 | Bp Amoco Corporation | Autothermic reactor and process using oxygen ion--conducting dense ceramic membrane |
| ID20211A (id) * | 1997-04-29 | 1998-10-29 | Praxair Technology Inc | Metoda produksi hidrogen dengan menggunakan membran elektrolit padat |
| US5865878A (en) * | 1997-04-29 | 1999-02-02 | Praxair Technology, Inc. | Method for producing oxidized product and generating power using a solid electrolyte membrane integrated with a gas turbine |
| US6077323A (en) * | 1997-06-06 | 2000-06-20 | Air Products And Chemicals, Inc. | Synthesis gas production by ion transport membranes |
| US6139810A (en) * | 1998-06-03 | 2000-10-31 | Praxair Technology, Inc. | Tube and shell reactor with oxygen selective ion transport ceramic reaction tubes |
-
2000
- 2000-02-16 DE DE60010550T patent/DE60010550T2/de not_active Expired - Lifetime
- 2000-02-16 AT AT00103158T patent/ATE266601T1/de not_active IP Right Cessation
- 2000-02-16 EP EP00103158A patent/EP1035072B1/en not_active Expired - Lifetime
- 2000-02-16 ES ES00103158T patent/ES2218012T3/es not_active Expired - Lifetime
- 2000-02-23 US US09/511,236 patent/US6338833B1/en not_active Expired - Lifetime
- 2000-03-02 CA CA2299940A patent/CA2299940C/en not_active Expired - Fee Related
- 2000-03-03 ZA ZA200001107A patent/ZA200001107B/xx unknown
- 2000-03-03 JP JP2000058716A patent/JP4541484B2/ja not_active Expired - Fee Related
- 2000-03-03 NO NO20001114A patent/NO328246B1/no not_active IP Right Cessation
- 2000-03-05 CN CN00106514A patent/CN1129552C/zh not_active Expired - Fee Related
- 2000-03-06 RU RU2000105295/15A patent/RU2248931C2/ru not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CA2299940C (en) | 2010-05-25 |
| CA2299940A1 (en) | 2000-09-05 |
| ZA200001107B (en) | 2000-09-06 |
| JP4541484B2 (ja) | 2010-09-08 |
| NO20001114D0 (no) | 2000-03-03 |
| NO20001114L (no) | 2000-09-06 |
| EP1035072B1 (en) | 2004-05-12 |
| CN1268481A (zh) | 2000-10-04 |
| DE60010550D1 (de) | 2004-06-17 |
| DE60010550T2 (de) | 2005-05-12 |
| NO328246B1 (no) | 2010-01-18 |
| JP2000256001A (ja) | 2000-09-19 |
| ATE266601T1 (de) | 2004-05-15 |
| ES2218012T3 (es) | 2004-11-16 |
| EP1035072A1 (en) | 2000-09-13 |
| US6338833B1 (en) | 2002-01-15 |
| RU2248931C2 (ru) | 2005-03-27 |
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