CN101351527B - 由一种或多种气相反应物生产凝相产物的方法 - Google Patents

由一种或多种气相反应物生产凝相产物的方法 Download PDF

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CN101351527B
CN101351527B CN2006800477442A CN200680047744A CN101351527B CN 101351527 B CN101351527 B CN 101351527B CN 2006800477442 A CN2006800477442 A CN 2006800477442A CN 200680047744 A CN200680047744 A CN 200680047744A CN 101351527 B CN101351527 B CN 101351527B
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Abstract

在含有一种或多种催化剂组分的固体催化剂的存在下由一种或多种气相反应物生产至少一种凝相产物的方法,其中所述固体催化剂具有两个或多个区域,在所述区域中,一种或多种气相反应物与一种或多种催化剂组分的接触时间不同。

Description

由一种或多种气相反应物生产凝相产物的方法
本发明涉及非均相催化领域,更具体地涉及在固体催化剂存在下将一种或多种气相反应物转变成凝相(condensed phase)产物的改进方法。
费-托合成是用于由合成气(一氧化碳和氢气的混合物)生产烃的已知反应,其中将合成气与非均相催化剂接触来生产烃的混合物。合成气通常通过比如煤或天然气的蒸汽重整这样的方法制得,或者由天然气的部分氧化制得,并且其还可由生物质制得。费-托合成的一种应用是在于可用作燃料的烃液体和/或蜡的生产,或者在于通过例如加氢裂化的处理生产燃料。
在用于烃的费-托合成的非均相催化过程中,液体或固体的产物烃在反应条件下会冷凝在催化剂表面上,这抑制合成气反应物与催化剂表面的接触从而导致反应物转化率的降低。
迄今已描述了可变直径反应器用于控制过程中的反应温度,所述过程涉及在反应条件下在气相中的反应物和产物。因此,WO 03/011449描述了一个装置,其中固体催化剂床的横截面积沿其纵轴增加,该增加是通过使用载送热传递材料的成型插件,以及DE 2929300描述了用于控制吸热或放热反应中催化剂温度的可变直径反应器,其中载送热传递材料的插件的形状沿它们的长度是变化的。然而,其中描述的这些方法在反应条件下不产生在凝相中的产物,因此没有应对固体催化剂覆盖有凝相产物的问题。
根据本发明,提供了由一种或多种气相反应物生产凝相产物的方法,该方法包括将一种或多种反应物加入反应器中,在该反应器中,气相中的一种或多种反应物在具有一种或多种催化剂组分的固体催化剂存在下反应,产生至少一种凝相产物,其特征在于所述固体催化剂具有两个或多个区域,在所述区域中一种或多种气相反应物与一种或多种催化剂组分的接触时间是不同的。
在本发明中,一种或多种气相反应物与固体催化剂的一种或多种催化剂组分的接触时间在所述固体催化剂的两个或多个区域中是不同的。通过在各个区域中具有不同接触时间,一种或多种气相反应物到凝相产物的转化率可通过维持每个区域中至少一种凝相产物与一种或多种催化剂组分之比(以下称为凝相产物与催化剂组分之比)在预定范围的值内而得以优化。
例如,凝相产物与催化剂组分之比的预定值范围可以基于实验观测的结果或者基于理论模型。通常可对所述范围进行选择以优化工艺效率,例如通过在具有低的反应物转化率的区域维持低的凝相产物与催化剂组分之比,或者通过在需要降低转化率时维持高的产物与催化剂组分之比。比值范围将取决于催化剂各区域内凝相产物浓度的变化。
例如,在凝相产物量高的固体催化剂区域中,则至少一种凝相产物对催化剂的覆盖度也将是高的,导致低的反应物转化率。因此通过提高固体催化剂区域内一种或多种气相反应物与一种或多种催化剂组分之间的接触时间可提高反应物转化率。相反地,在凝相产物量低的固体催化剂区域中,凝相产物与催化剂组分之比将是低的,因此催化剂覆盖度将是低的,并且转化率可以是高的。因此,通过降低接触时间,可获得降低的转化率。
在本发明的优选实施方案中,通过具有不同浓度的催化剂组分的固体催化剂区域和/或具有不同横截面积及体积的固体催化剂区域,各个固体催化剂区域内一种或多种气相反应物与一种或多种催化剂组分之间的接触时间可以是变化的。
因此,在本发明的一个实施方案中,固体催化剂包含具有不同浓度的一种或多种催化剂组分的区域。固体催化剂横截面积和/或体积在固体催化剂不同区域中可以是相同的,以便在其中获得一种或多种气相反应物与一种或多种催化剂组分之间的不同接触时间。因此,具有两个或多个有相同的横截面积和体积而具有不同浓度的一种或多种催化剂组分的区域的固体催化剂,将具有一种或多种气相反应物与一种或多种催化组分的不同接触时间。因此,具有两个或多个有不同浓度的一种或多种催化剂组分的区域的固体催化剂可用于独立地维持各个区域中至少一种凝相产物与一种或多种催化剂组分之比在预定值范围内。
另外,或者,固体催化剂的两个或多个区域具有不同的横截面积和体积,这导致在固体催化剂的不同区域内不同的气相反应物空速。固体催化剂各区域内一种或多种催化剂组分的浓度可以是相同或不同的,使得固体催化剂的两个或多个区域中一种或多种气相反应物与一种或多种催化剂组分的接触时间是不同的。优选地,在整个固体催化剂中固体催化剂每个区域内一种或多种催化剂组分的浓度是相同的,这可降低将催化剂装入反应器的复杂性。
通过在反应物转化率低的区域中提高固体催化剂的横截面积和体积,就必然降低凝相产物与催化剂组分之比,导致降低的催化剂覆盖度和改善的反应物转化率。相反地,通过具有降低的横截面积和体积,可获得提高的凝相产物对一种或多种催化剂组分的覆盖度,这可降低该区域中的反应物转化率。后种情形可能是有利的,例如,对于优选降低固体催化剂区域内放热程度以避免催化剂损伤或失活的放热反应。通过这些方法,具有两个或多个不同横截面积和体积的区域的固体催化剂可用于独立地维持各个区域中至少一种凝相产物与一种或多种气相反应物之比在预定值范围内。
本发明的该实施方案的另外优点是,固体催化剂可分布在反应器中,从而使需要降低的至少一种凝相产物与一种或多种催化剂组分之比的区域中可存在较高体积的催化剂,而要求较高比的区域中可存在较低体积的催化剂,这便改善固体催化剂的利用率。固体催化剂的横截面积可在不同横截面积和体积的区域之间连续地变化,或者可以按不连续、梯级方式变化,这样催化剂床的各区域便由横截面积的不同梯级改变所限定。
固体催化剂可以包括例如成型插件如一种整料、纤维材料或网状物的床、或者固体颗粒如球、珠、粒或挤出物的床。优选地,固体催化剂包括填充催化剂颗粒,因为颗粒可容易地嵌入反应器中从而使它们适于其中直径的变化。
固体催化剂包含一种或多种催化剂组分,这些组分催化一种或多种气相反应物转化成至少一种凝相产物。可存在单一催化剂组分,例如过渡金属或过渡金属化合物,或者可存在多于一种的催化剂组分,例如另外的共催化剂或催化剂助剂。所述一种或多种催化剂组分可加以支承或未加以支承。
固体催化剂区域内一种或多种催化剂组分的浓度可加以改变,例如,通过将催化惰性颗粒与包含一种或多种催化剂组分的颗粒混合。或者,如一种或多种催化剂组分附在载体上,则固体催化剂的不同区域可包括附在该载体上具有不同载量的一种或多种催化剂组分的区域。
反应器可包括一个或多个插件。在本发明的优选实施方案中,反应器包括一个或多个纵向布置的插件,该插件有两个或多个具有可变横截面积和体积的区域。固体催化剂可以在一个插件内或在多个插件内,或者在一个或多个插件与反应器内壁之间的反应器空间中。取决于催化剂所处的位置,插件或者插件与反应器内壁之间的无催化剂区域可用于载送热交换介质,以便控制反应器内的温度。相对于一种或多种气态反应物的流动来说,热交换介质可并流流动,或者可反向流动。
在反应期间,形成一种或多种产物,其至少一种在反应条件下处在凝相中。本发明特别适合于其中产物在反应条件下处在液相中的工艺,因为液体产物相比于蜡状产物或其它固体产物更易于与固体催化剂分离。
在本发明的一个实施方案中,将两种气相反应物并流加入反应器,并且穿过具有相同浓度的催化剂组分的固定催化剂床,其中气相反应物反应产生液相产物。在两种气相反应物与固体催化剂床接触的初始位置,液相产物的浓度低。液相产物的浓度随反应进行而增加,并且随着气相反应物沿着固体催化剂床穿过变得更浓。这可导致在固体催化剂的下游区域(相对于气相产物的流动方向)中液相产物对固体催化剂的覆盖程度更大。通过在下游区域增加固体催化剂横截面积和体积,便降低液体产物与一种或多种催化剂组分之比,导致在那些区域对催化剂的覆盖的减少并且还导致气相反应物与固体催化剂的接触时间增加。该结果是具有较高横截面积和体积的区域中反应物转化率的改善。
在本发明的备选实施方案中,在与一种或多种气相反应物接触的初始位置接邻的区域中降低固体催化剂的横截面积和体积。该实施方案可以是有利的,例如在一种或多种反应物与固体催化剂的最初接触和放热反应的开始之间存在延迟的反应中。因此在初始,在固体催化剂上具有缓慢的反应物流动速率有利,以便提高反应物与一种或多种催化剂组分的接触时间,并且促进反应的引发。一旦反应被引发,反应速率增加,放热所产生的热量可能会导致催化剂的损害或失活,并且可导致对所需产物的选择性降低和催化剂寿命降低。因此通过减小固体催化剂的接邻下游区域的横截面积和体积,使反应物在催化剂上的流动速率增加,这减少反应物与固体催化剂的接触时间,其可导致反应物转化率和反应速率降低。另外,通过减小横截面积和体积,会使凝相产物与一种或多种催化剂组分之比增加,其进一步起到降低一种或多种气相反应物的转化率的作用。任选地,在更加下游的固体催化剂区域可具有增加的横截面积和体积,以便改善转化率,否则,其中液体产物对固体催化剂的覆盖率增加便可能出现。备选地,在更加下游的固体催化剂区域可具有甚至更低的横截面积和体积。
固体催化剂可以包括间隙或无催化剂的部分。例如,在本发明的实施方案中,其中固体催化剂包含颗粒并且固体催化剂的不同区域具有不同浓度的催化剂组分,不同催化剂区域可由栅格隔开以便防止不同区域中的颗粒的交叉混合。在这些实施方案中,栅格之间的体积不可能用催化剂和惰性颗粒完全填满,例如由于颗粒下沉(settling)的结果。
在存在多于一种气态反应物时,可将反应物分开地或预混合地加入到反应器中。它们可一开始全都接触在固体催化剂同一区段的固体催化剂,或者它们可在固体催化剂的不同位置加入。一种或多种反应物与固体催化剂的初始接触位置是这样的位置,在该位置,所有反应物最初在气相中和在固体催化剂的存在下互相接触。优选地,一种或多种气态反应物并流地流过固体催化剂。
可将一种或多种气相反应物以气相或者作为凝相加入到反应器中,所述凝相在反应器内汽化,从而使其以气相与固体催化剂接触。
本发明的方法可任选地包括串联布置的多个反应器,使得从第一反应器取出的任何组合物被加入第二反应器中,并且从第二反应器取出的组合物被加入第三反应器中,等等。在该实施方案中,从各反应器取出的组合物包括凝相产物和未反应的反应物。任选地,在反应器之间的位置将至少部分凝相产物取出,并加至例如纯化工段。在该实施方案中,各反应器包含固体催化剂,并且至少第一反应器将有固体催化剂,该固体催化剂具有两个或多个区域,这些区域中一种或多种气相反应物与一种或多种催化剂组分的接触时间是不同的,如前所述。
通常将取自一个或多个反应器的含有一种或多种产物的料流加入到纯化区,其中将未反应的反应物和不期望的副产物除去并且任选循环至反应器,或反应器中的任一个或多个。
本发明适合用于由合成气通过费-托合成非均相催化生产烃,例如在柴油或航空燃料或其前体的生产中。由合成气费-托合成烃可由方程式1表示:
mCO+(2m+1)H2→mH2O+CmH2m+2    方程式1
该方法通常会产生包含具有一系列碳数的烃的产物,所述碳数将特别取决于合成气的CO∶H2比、工艺条件和催化剂。烃或其混合物优选在反应条件下是液体。优选地,烃数主要在方程式1的“m”值大于5的范围内。
合成气反应物中氢与一氧化碳(H2∶CO)体积比优选为0.5∶1至5∶1,更优选1∶1至3∶1,和最优选1.8∶1至2.2∶1。一种或多种气态反应物还可包含其它气态组分,例如氮、二氧化碳、水、甲烷和其它饱和和/或不饱和轻质烃,各优选地以小于30体积%的浓度存在。
费-托反应的温度优选为100-400℃、更优选150-350℃和最优选150-250℃。压力优选为1-100巴(0.1-10MPa)、更优选5-75巴(0.5-7.5MPa)和最优选10-40巴(1.0-4.0MPa)。
一种或多种气态反应物还可包括提取自工艺中其它位置的再循环材料,例如纯化期间从烃产物分离的未反应的反应物。
合成气通常以100-10000h-1(转换成标准温度和压力的气体体积)、优选250-5000h-1例如250-3000h-1和更优选250-2000h-1的气时空速(GHSV)穿过催化剂床。
催化剂通常为颗粒状固定床催化剂,并且包含对费-托催化具有活性的金属。优选的金属选自钴、铁、钌、镍、钼、钨和铼中的一种或多种,优选钴和/或铁,甚至更优选钴。优选地,该金属要加以支承,例如支承在载体上,载体包括二氧化硅、氧化铝、二氧化硅/氧化铝、二氧化钛、氧化锆、二氧化铈或氧化锌中的一种或多种。优选地,载体是氧化铝和/或氧化锌,更优选氧化锌。最优选地,该催化剂包含在氧化锌载体上的钴。本发明中适合于费-托方法的催化剂组合物例如描述于EP-A-0261870和EP-A-0209980中。
现将参考附图对本发明进行说明,其中:
图1是两个反应器的纵截面示意图,其突出了在含有相同固体催化剂的两个不同反应器的三个不同区域中凝相产物的浓度;
图2是有催化剂填充插件的根据本发明的反应器的纵截面示意图;
图3显示了贯穿图2所描述反应器的一系列横截面;
图1说明了反应器A和反应器B的三个区域中凝相产物浓度的差异,所述反应器A具有有恒定横截面积和体积区域的固体催化剂和均匀浓度的一种或多种催化剂组分,所述反应器B具有相同的固体催化剂,但却具有不同横截面积和体积的区域。反应器A的固体催化剂因此没有根据本发明,而反应器B的固体催化剂则与本发明一致。将两种反应物1和2并流且向下加入到各个反应器中,并且在气相中于固体催化剂(未示出)的存在下反应产生凝相产物4。反应器内凝相产物3的浓度由阴影程度表示,其中疏阴影表示低浓度的凝相产物,而浓阴影表示高浓度的凝相产物。在反应器A中,固体催化剂各区域的体积是相同的。当产物浓度从区域1增加到区域3时,结果是在相应的区域中逐渐增加的凝相产物与一种或多种催化剂组分之比。在反应器B中,通过增加接连区域内的横截面积和体积,而使固体催化剂全部三个区域内的该比率保持不变。因此反应器B中固体催化剂的三个区域内的反应物转化率通过降低凝相产物对催化剂的覆盖程度而得以最优化,所述覆盖程度的降低是通过降低凝相产物与一种或多种催化剂组分之比。
图2显示了具有多个装有费-托催化剂颗粒18的插件12的反应器11。将冷却剂通过入口14加入插件之间的反应器空间13并通过出口15取出。将合成气16通过入口17加入含催化剂插件中,并与插件内的固体催化剂18接触。将凝相烃产物和未反应的反应物通过出口19从含催化剂插件中取出。插件的直径从固体催化剂床的顶部(其中反应物气体首先与催化剂接触)到固体催化剂床的底部逐渐增加,形成具有不同横截面积的固体催化剂床的不连续区域。固体催化剂床的体积随横截面积的增加而增加。
图3通过面A-A′、B-B′、C-C和D-D′说明了图1反应器11的四个横截面。插件12,和其中固体催化剂床18的横截面积,在不同深度具有不同的直径Z。插件间的空间13填充有冷却剂。

Claims (12)

1.由一种或多种气相反应物生产凝相产物的方法,该方法包括将一种或多种反应物供入反应器中,在该反应器中,一种或多种反应物在具有一种或多种催化剂组分的固体催化剂存在下于气相中反应,产生至少一种在反应条件下处于凝相中的产物,其特征在于所述固体催化剂具有两个或多个区域,在所述区域中,一种或多种气相反应物与一种或多种催化剂组分的接触时间是不同的。
2.如权利要求1所要求的方法,其中固体催化剂的各个区域具有不同浓度的一种或多种催化剂组分。
3.如权利要求1所要求的方法,其中固体催化剂的两个或多个区域具有不同的横截面积和体积。
4.如权利要求1所要求的方法,其中固体催化剂包含颗粒。
5.如权利要求4所要求的方法,其中所述固体催化剂包含球、珠、粒或挤出物。
6.如权利要求1所要求的方法,其中固体催化剂包含选自二氧化硅、氧化铝、二氧化硅/氧化铝、二氧化钛、氧化锆、二氧化铈或氧化锌中的-种或多种的载体。
7.如权利要求1所要求的方法,其中至少一种催化剂组分是对费-托合成具有活性的金属,该金属选自钴、铁、钌、镍、钼、钨和铼中的一种或多种。
8.如权利要求1-7中任一项所要求的方法,其中合成气是反应物,并且至少一种凝相产物包含在反应条件下为液体的烃的混合物。
9.如权利要求8中所要求的方法,其中由烃的混合物生产柴油或航空燃料。
10.如权利要求1所要求的方法,其中反应器包括一个或多个插件。
11.如权利要求8所要求的方法,其中反应器包括一个或多个插件。
12.如权利要求10或11所要求的方法,其中一个或多个插件包含固体催化剂并且插件之间的空间被热传递介质包围。
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AU2006328677A1 (en) 2007-06-28
EP1966348A1 (en) 2008-09-10
KR101328784B1 (ko) 2013-11-13
MX2008007936A (es) 2008-09-24
EG25356A (en) 2011-12-18
EA014084B1 (ru) 2010-08-30
ES2344752T3 (es) 2010-09-06
US7977391B2 (en) 2011-07-12
PL1966348T3 (pl) 2010-10-29
ATE466063T1 (de) 2010-05-15
CO6141475A2 (es) 2010-03-19
DE602006014025D1 (de) 2010-06-10
KR20080078673A (ko) 2008-08-27
AU2006328677A2 (en) 2008-07-31

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