CN1177780C - 从合成气制备烃类的方法 - Google Patents

从合成气制备烃类的方法 Download PDF

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CN1177780C
CN1177780C CNB991075579A CN99107557A CN1177780C CN 1177780 C CN1177780 C CN 1177780C CN B991075579 A CNB991075579 A CN B991075579A CN 99107557 A CN99107557 A CN 99107557A CN 1177780 C CN1177780 C CN 1177780C
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G·克莱里西
V·皮克科洛
P·布劳丁
J-C·维尔埃德
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Abstract

从合成气制备烃类的方法,该方法包括a)向用于费-托反应的反应器底部加入H2/CO摩尔比范围为1-3的合成气;b)从反应器顶部排放含有悬浮状态的催化剂的液态烃;c)将悬浮液加入到至少一个一级旋液分离器中,以得到部分分离了的、含0.5-15%体积的固体颗粒的产物;d)将部分分离了的产物加入到至少一个二级旋液分离器中,以得到基本上不含固体颗粒的液体物流。

Description

从合成气制备烃类的方法
本发明涉及一种从合成气制备烃类的方法。
更具体地说,本发明涉及一种利用费-托法从合成气制备在室温和大气下为液体的烃类的方法。
从传统已知的合成气、即以氢和一氧化碳为基础的气体混合物来制备烃类的费-托技术在科学文献中是已知的。有关费-托合成反应的主要著作的总结见Bureau of Mines Bulletin,544(1955)中的题为“费-托合成及相关过程的参考书目”H.C.Anderson,J.L.Wiley and A.Newell。
大体上,费-托技术是以使用一种用于化学反应的反应器为基础的,其中化学反应是在三相体系中进行的,气相鼓泡进入固体在液体中的悬浮液。气相由合成气组成,其中H2/CO的摩尔比的变化范围为1-3,分散的液相代表反应产物,即主要是带有多个碳原子的直链烃,固相则为催化剂。
因此,由反应器释放出来的反应产物由悬浮液组成,该悬浮液需要进行处理,从液相中分离出固体(催化剂)。而催化剂则循环回到合成反应器中,液体进行后续处理,如氢化裂解和/或氢化异构化处理,以获得具有工业意义的烃类组分。
已公开的欧洲专利申请609.079描述了一种用于费-托反应的反应器,该反应器由一个气体鼓泡塔构成,塔内装有由悬浮在液态烃中的催化剂颗粒所形成的悬浮液。合成气从反应器的底部加入,而合成的烃则在顶部回收。
为了避免催化剂颗粒的夹带,反应器设有安置在该反应器内上部的圆筒形的过滤装置。
已公开的国际专利申请WO97/31693描述了一种从固体颗粒悬浮液中分离液体的方法,该方法包括:在第一阶段中脱去悬浮液中的气体,在第二阶段中通过一个切向流过滤器过滤悬浮液。尤其是,悬浮液来自费-托反应器并且是由合成的、夹带催化剂颗粒的重烃所形成的。
用于分离离开费-托反应器的悬浮液中所含催化剂的方法的其它例子在已公开的欧洲专利申请592.176、已公开的国际专利申请WO94/16807、英国专利2.281.224、美国专利4.605.678和5.324.335以及德国专利3.245.318中均有所描述。
本申请人现在发现了一种利用费-托法来制备液态烃类的更进一步的方法,这一方法可以从制得的悬浮液中将液相回收,简单并且不需要借助于合成反应器内部或外部的专门的过滤系统。
因此,本发明涉及一种从合成气制备烃类的方法,该方法包括:
a)连续向用于费-托反应的反应器底部加入合成气,该反应器中装有分散在液相中的催化剂,合成气主要由氢和一氧化碳组成,其中H2/CO的摩尔比范围为1-3;
b)连续从反应器的顶部排出费-托反应产物,该产物主要由处于悬浮状态的、含有催化剂的烃液相组成;
c)将悬浮液加入到至少一个一级旋液分离器中,以得到浓缩了的底部产物,该底部产物循环回到合成反应器中,并得到部分分离了的、含0.5-15%体积的固体颗粒的产物;
d)将部分分离了的产物加入到至少一个二级旋液分离器中,以得到第二个浓缩了的底部产物,该底部产物循环回到反应器中,并得到基本上不含固体颗粒的液体物流。
按照本发明的方法,用于费-托类反应的反应器为一个容器构成的鼓泡反应器,通常是立式的,比如塔,在反应器内部化学反应被激活,这些化学反应在三相体系中发生,其中气相鼓泡进入到液体中的固体悬浮液中。在这种情况下,气相由合成气组成,其中H2/CO的摩尔比变化范围为1-3,分散的液相代表反应产物,即主要是带有多个碳原子的直链烃,固相则为催化剂。
以在美国专利5.645.613中所描述的反应为基础,合成气优选来自于蒸气转化或天然气的部分氧化。另外合成气也可以来自于其它的制备技术,比如来自于“自热式转化”或者来自于碳与水蒸气在高温下的气化作用,正如在“催化科学与技术”Vol.1,Springer-Verlag,纽约,1981中所描述的。
从费-托反应制得的主要有两相,较轻的一相是主要由轻质烃类、水蒸气、惰性产物等组成的气相,该气相与未反应的气体一起在顶部排放出来,另一较重的相则主要由在反应温度下处于液态的、含有饱和的高碳原子数直链烃混合物的石蜡组成。通常这些烃类混合物的沸点高于150℃。
费-托反应在150-400℃、优选为200-300℃的温度范围内,并维持反应器内部的压力为0.5-20MPa的条件下进行。有关费-托反应的更为具体的细节可以在上面提到的“催化科学与技术”中得到。
最后,催化剂存在于反应器内部,悬浮在烃液相中。
在费-托反应中具有活性的任何催化剂都可以用在本发明的方法中。优选的催化剂是以钻为基础的,钴处于金属状态或者氧化物状态或者有机(无机)盐状态,并且分散在固体载体上,而固体载体由下列元素Si,Ti,Al,Zn,Mg中的一种或多种中选出的至少一种氧化物组成。优选的载体是二氧化硅、氧化铝或二氧化钛。
在催化剂中,钴的重量含量范围为总重量的1-50%,通常为5-35%。
用于本发明的方法中的催化剂也可以含有其它元素。例如,它可以含有重量含量占总重量0.05-5%、优选为0.1-3%的钌以及重量含量占总重量0.05-5%、优选为0.1-3%的至少一种选自于第IIIB族的第三种元素。这种类型的催化剂在文献中是已知的,在已公开的欧洲专利申请756.895中描述了这种催化剂及其制备方法。
另外的催化剂的例子也是以钴为基础,但还含有重量含量占催化剂总重量0.05-5%、优选为0.1-3%的钽作为助催化剂元素。这些催化剂在制备时,首先将钴盐沉积在惰性载体(二氧化硅或氧化铝)上,比如利用干法浸渍技术,然后进行煅烧步骤,并有选择地对煅烧产物进行还原和钝化。
将钽的衍生物(特别是钽的醇化物)沉积在如此得到的催化剂前体上,优选采用湿法浸渍技术,然后进行煅烧和选择性地进行还原和钝化。
无论催化剂的化学组成如何,都是以极细分散的粉末形式使用,其平均粒径范围为10-700微米。
由烃相和催化剂共同组成的费-托反应产物连续地从合成反应器的顶部排放出来。该产物为悬浮液,其中固体相的体积浓度范围通常为20-40%。
可以在反应器的内部和外部对悬浮液进行脱气。比如可以将悬浮液加入到立式的搅拌容器中进行脱气,并将从液相中释放出来的气体输送到外部与从反应器顶部排放出来的气相汇合。
将选择性脱气后的悬浮液加入到一个一级旋液分离器(或旋液分离器组)中进行初步定量分离。旋液分离器是一种固液分离装置,其分离作用是靠离心作用发生的,而离心运动则是通过保持装置平稳并沿切向加入悬浮液而形成的旋转运动来保证的。有关旋液分离器的详细描述可以在“Ullmann’s工业化学百科全书”第五版,1988,B2卷或“旋液分离器”,L.Svarovsky Holt,Rinehart andWinston,1984中找到。
在旋转运动过程中,颗粒被推向装置的器壁、损耗能量、沉积并富集在旋液分离器的底部。这样就可以从旋液分离器得到两股物流,一股从底部得到、由浓缩了的悬浮液组成,另一股从顶部得到、由含有约0.5-15%、通常为2-7%体积的固体颗粒的稀悬浮液组成。
浓缩了的悬浮液循环回到合成反应器中,而更稀的悬浮液则被加入到一个二级旋液分离器(或旋液分离器组)中,从该分离器得到基本上不含固体颗粒(固体颗粒少于0.5%体积)的物流,该物流被送入到费-托过程所要求的后续操作阶段中。
从二级旋液分离器的底部回收另一相对于其进料更为浓缩的物流,它可以循环回到合成反应器中。
对于本发明的从合成气制备烃类的方法,可以参照附图中的工艺流程图更好地加以理解。该工艺流程图代表的是两种举例性的而不是限制性的实施方案。
具体地,图1的工艺流程表示的是一种方法,其中悬浮液在反应器和一级旋液分离器之间的循环是靠一种称为“气升”的效应来保证的。在处理具有不同密度的悬浮液时(象此情形中那样),就会产生“气升”效应,利用了在具有较低密度的鼓泡悬浮液(在反应器内部)与具有较高密度的脱气后的悬浮液(在旋液分离器内部)之间形成的流体静力学的液封。有关“气升”效应的信息可以在“工业与工程化学研究”,1988,37,41-48,240-246或“化工科学”,1977,52,2527-2540中找到。
另一方面,图2的工艺流程表示的是另一种方法,其中反应器和一级旋液分离器基本上处于相同的压力下,悬浮液在两个设备之间的循环靠液压泵来保证。
参照附图,工艺流程图包括:一台费-托反应器(FT),一台脱气器(D),两台泵(P1)和(P2),两台旋液分离器(IC1)和(IC2)。
从附图及前面的描述可知本方法的作用是很明显的。合成气(1)被加入到鼓泡式反应器(FT)的底部。由液相和催化剂组成的悬浮液(2)从反应器的顶部排放出来,并被加入到容器(D)中进行脱气。从容器(D)中释放出来的气体(3)汇入到离开反应器(FT)的气相(4)中,该气相将在未画出的操作单元中进行处理,以回收被夹带的烃类。
靠泵(P1)有选择地移出的悬浮液(5)被加入到一级旋液分离器(IC1)中,从中回收得到两股物流。一股是浓缩了的物流(6),循环回到反应器(FT)中,另一股是部分分离了的物流(7),由泵(P2)移出以物流(8)加入到二级旋液分离器(IC2)中。
基本上不含颗粒的液体物流(9)从(IC2)的顶部排放出来,而第二个浓缩的物流(10)则从其底部排放出来并循环回到反应器(FT)中。
为了更好地理解本发明及其实施方案,下面给出两个举例性的而不是限制性的实施例。
实施例1
粒度范围为20-150μm的催化剂由表面积为175m2/g的氧化铝载体和分布在载体上的14%重量的钴及0.5%重量的钽组成,该催化剂被加入到连接在图1流程中的用于费-托反应的反应器/反应塔(FT)中。
在激活反应以后,H2/CO摩尔比为2的合成气物流在平稳状态下被加入到反应器的底部。反应在225℃及3MPa的压力下进行。
1m3/h的含28%体积的催化剂的烃悬浮液被连续移出反应器。在(D)中脱气后的悬浮液被加入到一级旋液分离器(IC1)中,从一级旋液分离器(IC1)的底部回收得到约0.83m3/h的、浓度为32%重量的悬浮液,该悬浮液被循环回到反应器(FT)中,而大约为0.12m3/h的部分分离了的、含6.5%体积的催化剂的悬浮液则从一级旋液分离器(IC1)的顶部回收。
部分分离了的悬浮液被加入到二级旋液分离器(IC2)中,在二级旋液分离器(IC2)的顶部得到0.1m3/h的、净化的液体物流(催化剂的浓度低于0.5%体积),在其底部则得到约0.02m3/h的、增稠了的、含32%体积的固体的悬浮液,该悬浮液被循环回到合成反应过程中。
实施例2
进行与实施例1相同的方法,只是所参照的是图2中的工艺流程。
1m3/h的含25%体积的固体的悬浮液连续从反应器(FT)中移出,脱气完成后,由泵(P1)输送到一级旋液分离器中。0.88m3/h的、固体浓度为28%体积的悬浮液被回收并循环回到反应器(FT)中,还回收得到0.1m3/h的、部分分离了的含5%体积的催化剂的悬浮液。
部分分离了的悬浮液被加入到二级旋液分离器(IC2)中,在二级旋液分离器(IC2)的顶部得到0.08m3/h的、净化的液体物流(催化剂的浓度低于0.5%体积),在其底部则得到0.02m3/h的、含约23%体积的固体的悬浮液,该悬浮液被循环回到合成反应过程中。

Claims (6)

1.一种用于从合成气制备烃类的方法,该方法包括:
a)连续向用于费-托反应的反应器底部加入合成气,该反应器中装有分散在液相中的催化剂,合成气主要由氢和一氧化碳组成,其中H2/CO的摩尔比的范围为1-3;
b)连续从反应器的顶部排出费-托反应产物,该产物主要由处于悬浮状态的、含有催化剂的烃液相组成;
c)将悬浮液加入到至少一个一级旋液分离器中,以得到浓缩了的底部产物,该底部产物被循环回到合成反应器中,并得到部分分离了的、含0.5-15%体积的固体颗粒的产物;
d)将部分分离了的产物加入到至少一个二级旋液分离器中,以得到第二个浓缩了的底部产物,该底部产物至少部分循环回到一级旋液分离器中,并得到基本上不含固体颗粒的液体物流。
2.按照权利要求1的方法,其中用于费-托反应的反应器是立式的鼓泡反应器。
3.按照权利要求1或2的方法,其中液相中的费-托反应产物主要由沸点高于150℃的石蜡组成。
4.按照前述任何一项权利要求的方法,其中费-托反应在150-400℃的温度范围及0.5-20MPa的压力范围内进行。
5.按照前述任何一项权利要求的方法,其中对在费-托反应器中制备的悬浮液进行脱气。
6.按照前述任何一项权利要求的方法,其中悬浮液在第一次过滤之后,固体的浓度为2-7%体积。
CNB991075579A 1998-04-23 1999-04-23 从合成气制备烃类的方法 Expired - Fee Related CN1177780C (zh)

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