CN1977033B - 催化装置及用于进行费-托合成的方法 - Google Patents
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Abstract
费-托合成在CO/H2原料气中进行,使用多个紧凑的催化反应器模块(12),各模块在两个连续的段中含有催化反应通道和致冷剂通道,各段具有相同数量的反应器模块。第一段的气流速度足够高以使不超过75%的CO被转化。气体在连续段之间被冷却以除去水蒸汽,并且其压力在它们被送入第二段之前被降低(20)。另外第二段的反应温度低于第一段,从而在第二段中也有不超过75%的残余一氧化碳被转化。因此水蒸汽对催化剂的有害作用被抑制,而设备(10)总生产能力可以通过关闭各段中的模块同时保持数量相等得到调节。
Description
本发明涉及一个化工工艺,并涉及适合用于施行本工艺的催化反应器装置。
PCT/GB 03/05198(GTL Microsystems AG)描述了一个工艺,其中费-托合成在两个连续段中进行,所述两段或者出现在单个具有不同数量的通道的反应器模块中,或者两段具有不同数量的模块。现在发现了进行该工艺的改进的方法。
根据本发明,提供了用于施行费-托合成的方法,其所用原料气含有用于生成烃产物的一氧化碳和氢,并使用多个紧凑的催化反应器模块,各自界定了用于费-托合成的流体通道,通道中是透气的催化剂结构,以及邻近的用于传热介质的流体通道,其中费-托合成在至少两个连续段中施行,而且连续段分别具有相同数量的反应器模块,所有反应器模块提供相同的流体通道,在第一段中气流速率足够高而温度足够低,以使不超过75%的一氧化碳被转化,气体在连续段之间被冷却以便冷凝水蒸汽和部分烃产物,然后被送入第二段。
第二段中的温度和压力可以不同于第一段以保持容许水平的对C5+的选择性,以及一氧化碳转化。例如,第二段中的压力可以因为压力损失而更低;这会降低选择性,因此第二段中的温度同第一段相比可以降低,以得到所希望的选择性。因此本工艺还可能包括在连续段之间降低反应气体的压力,且第二段反应温度比第一段反应温度低。工艺的施行可以使得在第二段中有不超过85%的残余一氧化碳被转化。
优选无论在第一段还是第二段中,空间速度大于1000/hr,但是优选不大于15000/hr。显然,第二段中的空间速度低于第一段,因为在第一段中发生了向液体的转化。优选反应器的操作使反应生成的水蒸汽在两段中均不超过26mole%。优选,在第一段中,不超过65%的一氧化碳被转化。
空间速度,在本说明书中,定义为提供给反应器的气体体积流速(在STP下测量),除以反应器的空隙容积。因此,如果反应器处于210℃的温度和2.5MPa压力下,5000/hr的空间速度所对应气流(处于操作条件下)约为每小时空隙容积的354倍,因此对应于约10s的停留时间。
本发明还提供用于施行这样的费-托合成的装置,含有多个紧凑的催化反应器模块,其各自界定了用于费-托合成的流体通道,通道中是透气的催化剂结构,以及邻近的用于传热介质的流体通道,反应器模块的排列使得费-托合成在至少两个连续段中施行,连续段分别具有相同数量的反应器模块,所有反应器模块提供相同的流体通道,装置在连续段之间引入冷却反应气体的设备,从而在连续段之间冷凝水蒸汽和部分烃产物。
连续段间冷凝步骤的目的在于将气体冷却到40至100℃的温度范围内,取决于烃产品的雾点,以避免蜡在传热面上的沉积。
优选在各段合成通道中的温度高于190℃。但是在低于约204℃的温度下具有更大的形成蜡(即长链产物)的趋势,而蜡倾向于附着在催化剂的表面上,这会限制反应物向催化剂的扩散并降低反应速率。相反,温度高于约225℃时反应倾向于生成短链产品由此生成更高比例的甲烷。这些较低分子量的物料在催化剂表面上使得试剂可以更快地扩散至催化剂表面,这促进了反应速率从而产生更多热量和更高的温度。因此连续段的温度可以是不同的,但优选处于约204℃和225℃之间,更优选介于约204℃和210℃之间。
现在本发明将进一步且更详细地描述,仅仅通过实例,并参考附图:
图1显示了用于施行费-托合成装置的流程图。
本发明涉及费-托合成,其可能成为用于将甲烷转化为更长链烃工艺的一部分。费-托合成是一氧化碳和氢之间的反应,且该气体混合物可能通过例如水蒸汽/甲烷重整生成。在费-托合成中气体反应并生成更长的链烃,即:
nCO+2nH2→(CH2)n+nH2O
这是放热反应,在高温,典型地介于190和350℃之间,例如210℃,以及高压,典型地介于2MPa和4MPa之间,例如2.5MPa下,在催化剂如铁,钴或熔融磁铁矿催化剂,以及钾促进剂,存在下进行。反应形成的有机化合物的确切性质取决于温度,压力,和催化剂,以及一氧化碳比氢的比例。
优选催化剂含有在镧稳定的,比面积140-450m2/g的γ氧化铝上涂敷约10-40%(相对于氧化铝重量的重量百分比)的钴,和钌/铂促进剂,促进剂为钴重量的0.01%至10%。还可能有碱性促进剂如氧化钆。催化剂的活性和选择性取决于钴金属在载体上的分散度,钴分散度的最佳值范围典型地为0.1至0.2,从而所存在的10%至20%之间的钴金属原子在表面上。分散度越大,显然钴金属晶粒尺寸必须更小,而其典型的范围为5-15nm。这样尺寸的钴颗粒提供高水平的催化活性,但是可能在水蒸汽存在下氧化,而这导致其催化活性的急剧降低。氧化程度取决于靠近催化剂颗粒处氢与水蒸汽的比例,及其它们的温度,更高的温度和更高的水蒸汽比例均会增加氧化的程度。
适合用于费托装置的反应器模块含有大量界定与反应通道交替的致冷剂通道的塔盘,并且在反应通道中具有透气的催化剂结构(如波状的箔,毡或筛)。塔盘可以是平板状的,而通道由凹槽界定;或者,一些塔盘可以是波状的或齿形的以界定通道。塔盘典型地通过扩散焊接或铜焊结合在一起,并为反应气体和冷却剂提供了适合的联管箱。例如,用陶瓷涂层涂敷,用催化剂材料浸渍的50μm厚的波状的Fecralloy合金箔可以在连接联管箱之前被插入反应通道中,并且可以在催化剂失效时被更换。在实际的装置中希望所有反应器模块具有相同的结构和尺寸,这样它们就是相同的。实际上,标准化的一个好处是可以降低装置的投资费用。
现在参考图1,费托装置10接收通过压缩机11在2.1MPa压力下提供的一氧化碳和氢的气流。该装置包括十个相同的反应器模块:通过五个模块12a的气流是平行的,这些组成第一段,通过另五个模块12b的气流是平行的并且组成第二段。阀14使得操作者可以打开或关闭通过各模块12a或12b的流体,而且模块12a或12b可以被分离。
在第一段和第二段之间,气体混合物穿过热交换器16,其目的在于冷凝水蒸汽和较长的链烃,从而将它们从气流中除去。然后冷却的气体混合物穿过分离器,如旋风分离器18,继之以分离室19,其中将三相的水,烃,和未反应的气体分离。气体通过减压阀20进入至装置10的第二段中,因此第二段中的反应压力可以典型地被降低至1.6-2.0MPa范围内。
通过在各模块12内部的致冷剂通道中提供冷却剂可以实现对反应温度的控制,各情况下冷却剂通过相应的热交换器15再循环。冷却剂流速调节至可以保证通过模块12过程中冷却剂温度的变化不超过10℃。第二段中反应温度可以控制到低于第一段中的温度。这可以通过对模块12a或12b使用不同的冷却剂回路15而实现,如图所示。或者,可以同时为两段连续地提供相同的冷却剂,但是使其温度在一段和下一段之间降低。优选第二段中的反应温度较第一段低约5℃或10℃。
第二段之后气流通过另一个热交换器16,其目的在于冷凝水蒸汽和较长的链烃。然后冷却的气体混合物穿过分离器,例如第二旋风分离器18,继之以第二分离室19,其中将三相的水,烃,和未反应的气体分离。所得尾气典型地是富氢的,并且可以放空燃烧,或用于为催化燃烧工艺提供燃料,或为燃气轮机(未示出)提供燃料。
使用装置10时一氧化碳与氢的混合物在例如2.1MPa的压力下提供给第一段反应器模块12a,在其中进行费-托合成。冷却剂以并流方式通过各模块12中的致冷剂通道,并将各反应器模块12a内部的温度值保持在205至220℃之间,沿反应器通道长度方向的温度变化不超过+/-5℃。(实际上冷却剂可以沿蛇行轨迹流过一系列横向的管道,所述蛇行轨迹近似于并流)。其目的在于使整个反应器10内部达到等温条件;其优点在于可将从反应通道流向出口方向的流体通道被任何蜡(即很长的链烃)阻断的风险减到最小。反应器模块12a中反应气体的流速(空间速度)范围为4000-7000/hr,例如约6500/hr,可以保证气体离开第一段时一氧化碳的转化率范围为35%到70%。
水蒸汽(以及一些较长的链烃)在通过热交换器16通道时冷凝,而且任何液滴通过分离器18和室19的管路从气相中被除去。这显著地降低了流入第二段的气体混合物中水蒸汽的分压。
残余气体的压力可以通过阀20,在被送入第二段的反应器模块12b之前被降低。模块12b中气体再一次进行费-托合成,但是冷却剂温度被安排为可以将各模块12b内部的温度保持在低于第一段几度,例如约5至10℃的温度下。应当理解因为显著比例的气体在通过第一段模块12a过程中转变为烃类,第二段中的空间速度不可避免地会更小,通常范围为2000-4000/hr。尽管如此,通过降低模块12b中压力并降低反应温度(同第一段相比),一氧化碳在通过模块12b过程中的转化率以及对C5+的选择性得以保持,使得总一氧化碳转化率超过85%(在两段内)而C5+总选择性保持在75-95%范围内。例如第一段的转化率可以是40%,生成约11%的水蒸汽;第二段中的转化率可以是82%(对于残余CO),得到约25%水蒸汽。
在到达第二段模块12b之前,通过分离器18和室19的通道除去水蒸汽和较低沸点烃类,不仅降低了水蒸汽的分压,并从而抑制了催化剂的氧化,还具有另外的好处,即至少除去了一部分会在催化剂结构上形成液层的那些烃类。任何这样的液层会抑制气体混合物与催化剂颗粒的接触并抑制烃类产物离开所述催化剂颗粒的扩散,因此除去所述液态烃使这些扩散阻力最小化。
如果原料气流速降低,通过使用阀14在各段中关闭相同数量的模块12a和12b,实质上可以使各段中反应条件(即空间速度,温度和压力)保持恒定。第一段中使用中的反应器模块12a的数目应该始终等于第二段中使用中的反应器模块12b的数目。因此装置10的生产能力可以减少至其设计能力的20%而操作条件没有任何显著的变化。这使得所述工艺能够适应天然气供应随时间的变化而变化,而不需要干扰费-托模块内部的操作条件;这样的干扰会导致催化剂中毒,因为过低的空间速度会导致CO的过度转化并从而引发高的水蒸汽分压,并且催化剂会受到氧化或在水蒸汽存在下与陶瓷载体发生不可逆反应。
应当理解该发明不局限于两段工艺,因为所述工艺的安排可以提供三个或更多的费-托反应段,同时相应增多级间冷却和分离单元的数量。例如可能有四个连续段,其中每个具有五个反应器模块12;因为具有更多段,任一段中的转化率可以限制为更低的值,如20%,而仍然由该装置得到良好的总体转化率。这样的更低的转化率数值进一步降低了催化剂所接触的水蒸汽的浓度,并因此可以应用活性更高的催化剂(其更容易受到提高的水蒸气压力的损害),并且可以使用更高的空间速度。此外,可以提高连续段之间的压力(而不是如上所述进行降低)。
Claims (6)
1.一种对原料气施行费-托合成的方法,所用原料气含有一氧化碳和氢以生成烃产物,使用多个紧凑的催化反应器模块,该催化反应器模块各自含有许多塔盘,所述塔盘界定用于费-托合成的反应通道以及与之交替的致冷剂通道,其中用于费-托合成的反应通道中是透气的催化剂结构,其中所述催化剂结构插入反应通道中并在催化剂失效时被更换,其中费-托合成在至少两个连续段中施行,各段在多个催化反应器模块中进行,催化反应器模块中反应气体平行流动,而且连续段分别具有相同数量的催化反应器模块,所有催化反应器模块提供相同的流体通道,其中各催化反应器模块装备有阀从而可以打开或关闭通过各催化反应器模块的流体,在第一段中气流速率足够地高而温度足够低,以使不超过75%的一氧化碳被转化,气体在连续段之间被冷却以便冷凝水蒸汽和部分烃产物,然后被送入第二段,其中在原料气流速降低时,通过使用所述阀在各段中关闭相同数量的模块。
2.权利要求1的方法,其中第一段与第二段温度均处于204℃-225℃范围内。
3.权利要求1或2的方法,其中水蒸汽不超过26mol%。
4.权利要求1或2的方法,其中至少在第一段中,不超过65%的一氧化碳被转化。
5.用于对原料气施行费-托合成的装置,所述原料气含有用于生成烃产物的一氧化碳和氢,所述装置包括多个紧凑的催化反应器模块,各自含有许多塔盘,所述塔盘界定用于费-托合成的反应通道以及与之交替的致冷剂通道,其中用于费-托合成的反应通道中是透气的催化剂结构,其中所述催化剂结构插入反应通道中并在催化剂失效时被更换,催化反应器模块被布置使得费-托合成在至少两个连续段中施行,各段具有多个所述催化反应器模块,在所述催化反应器模块中反应气体是平行流动的,连续段分别具有相同数量的催化反应器模块,所有催化反应器模块提供相同的流体通道,各催化反应器模块装备有阀从而可以打开或关闭通过各催化反应器模块的流体,其中在原料气流速降低时,通过使用所述阀在各段中关闭相同数量的模块,装置在连续段之间引入冷却反应气体的设备,从而冷凝水蒸汽和部分烃产物。
6.权利要求5的装置,其中各段有5个催化反应器模块。
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Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8034436B2 (en) * | 2002-04-30 | 2011-10-11 | Avery Dennison Corporation | Fluorescent article having multiple layers |
GB0314790D0 (en) * | 2003-06-25 | 2003-07-30 | Accentus Plc | Catalytic reactor and process |
US7084180B2 (en) * | 2004-01-28 | 2006-08-01 | Velocys, Inc. | Fischer-tropsch synthesis using microchannel technology and novel catalyst and microchannel reactor |
DE102007023759A1 (de) * | 2006-08-10 | 2008-02-14 | Evonik Degussa Gmbh | Anlage und Verfahren zur kontinuierlichen industriellen Herstellung von Fluoralkylchlorsilan |
DE102007023764A1 (de) * | 2006-08-10 | 2008-02-14 | Evonik Degussa Gmbh | Anlage und Vorrichtung zur kontinuierlichen industriellen Herstellung von 3-Chlorpropylchlorsilanen |
DE102007023757A1 (de) * | 2006-08-10 | 2008-02-14 | Evonik Degussa Gmbh | Anlage und Verfahen zur kontinuierlichen industriellen Herstellung von Organosilanen |
DE102007023760A1 (de) * | 2006-08-10 | 2008-02-14 | Evonik Degussa Gmbh | Anlage, Reaktor und Verfahren zur kontinuierlichen industriellen Herstellung von 3-Methacryloxypropylalkoxysilanen |
DE102007023762A1 (de) * | 2006-08-10 | 2008-02-14 | Evonik Degussa Gmbh | Anlage und Verfahren zur kontinuierlichen industriellen Herstellung von 3-Glycidyloxypropylalkoxysilanen |
DE102007023763A1 (de) * | 2006-08-10 | 2008-02-14 | Evonik Degussa Gmbh | Anlage, Reaktor und Verfahren zur kontinuierlichen industriellen Herstellung von Polyetheralkylalkoxysilanen |
DE102007023756A1 (de) * | 2006-08-10 | 2008-02-14 | Evonik Degussa Gmbh | Anlage und Verfahren zur kontinuierlichen industriellen Herstellung von Alkylalkoxysilanen |
RU2461603C2 (ru) | 2007-01-19 | 2012-09-20 | Вилосис Инк. | Способ, установка и композиция для превращения природного газа в высокомолекулярные углеводороды посредством микроканальной технологии |
US20080260631A1 (en) | 2007-04-18 | 2008-10-23 | H2Gen Innovations, Inc. | Hydrogen production process |
WO2009044198A1 (en) * | 2007-10-02 | 2009-04-09 | Compact Gtl Plc | Gas-to-liquid plant using parallel units |
GB0725140D0 (en) * | 2007-12-24 | 2008-01-30 | Compactgtl Plc | Catalytic Reactor |
BRPI0908113A2 (pt) * | 2008-02-14 | 2015-10-06 | Compactgtl Plc | módulo de reação catalítica, método de realizar uma reação endotérmica, e, sistema de controle para um módulo de reação catalítica para realizar uma reação endotérmica |
US8100996B2 (en) | 2008-04-09 | 2012-01-24 | Velocys, Inc. | Process for upgrading a carbonaceous material using microchannel process technology |
CN102056657A (zh) | 2008-04-09 | 2011-05-11 | 万罗赛斯公司 | 使用微通道工艺技术将碳质材料转化为甲烷、甲醇和/或二甲醚的方法 |
US8293805B2 (en) * | 2008-05-29 | 2012-10-23 | Schlumberger Technology Corporation | Tracking feedstock production with micro scale gas-to-liquid units |
JP5715568B2 (ja) | 2008-10-10 | 2015-05-07 | ヴェロシス,インク. | マイクロチャネルプロセス技術を使用するプロセスおよび装置 |
GB0822544D0 (en) * | 2008-12-11 | 2009-01-14 | Compactgtl Plc | Chemical reactor operation |
CA2755881C (en) * | 2009-03-20 | 2015-08-04 | Bharat Petroleum Corporation Limited | Counter-current multistage fischer tropsch reactor systems |
EP2486107A1 (en) * | 2009-10-09 | 2012-08-15 | Velocys Inc. | Process for treating heavy oil |
CN102373065B (zh) * | 2010-08-19 | 2014-03-26 | 中国石油化工股份有限公司 | 一种固定床费托合成方法 |
RU2489207C1 (ru) * | 2012-05-04 | 2013-08-10 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Катализатор и способ получения алифатических углеводородов из оксида углерода и водорода в его присутствии |
US9676623B2 (en) | 2013-03-14 | 2017-06-13 | Velocys, Inc. | Process and apparatus for conducting simultaneous endothermic and exothermic reactions |
AR110129A1 (es) | 2016-11-16 | 2019-02-27 | Dow Global Technologies Llc | Procesos y sistemas para obtener alta conversión de carbono a productos deseados en un sistema de catalizador híbrido |
RU2638217C1 (ru) * | 2016-12-15 | 2017-12-12 | Публичное акционерное общество "Нефтяная компания "Роснефть" | Компактный реактор для получения синтетических углеводородов в процессе Фишера-Тропша, способ активации катализатора Фишера-Тропша и способ осуществления синтеза Фишера-Тропша в компактном варианте с его использованием |
FR3073152B1 (fr) * | 2017-11-09 | 2022-03-11 | Aer | Unite d'hydrogenation d'oxydes de carbone a taux de conversion accru, dont la performance depend faiblement du vieillissement du catalyseur |
DE102019201172A1 (de) * | 2019-01-30 | 2020-07-30 | Siemens Aktiengesellschaft | Reaktorkaskade und Verfahren zum Betreiben einer Reaktorkaskade |
GB202208492D0 (en) * | 2022-06-10 | 2022-07-27 | Johnson Matthey Davy Technologies Ltd | System for producing a hydrocarbon product from a syngas |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6211255B1 (en) * | 1997-02-28 | 2001-04-03 | Den Norske Stats Oljeselskap A.S. | Fischer-tropsch synthesis |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8400608A (nl) * | 1984-02-28 | 1985-09-16 | Shell Int Research | Werkwijze voor de bereiding van koolwaterstoffen. |
US20020143075A1 (en) * | 2001-03-27 | 2002-10-03 | Agee Kenneth L. | Low-profile moving bed reactor |
GB0116894D0 (en) * | 2001-07-11 | 2001-09-05 | Accentus Plc | Catalytic reactor |
DE60203018T2 (de) * | 2001-10-12 | 2005-07-07 | Gtl Microsystems Ag | Katalytischer reaktor |
GB0129054D0 (en) * | 2001-12-05 | 2002-01-23 | Accentus Plc | Catalytic reactor and process |
JP4446388B2 (ja) * | 2002-12-02 | 2010-04-07 | コンパクトジーティーエル パブリック リミテッド カンパニー | 触媒反応器及び方法 |
-
2004
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2005
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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