CN109153621A - 烷烃氧化脱氢(odh) - Google Patents
烷烃氧化脱氢(odh) Download PDFInfo
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- CN109153621A CN109153621A CN201780013477.5A CN201780013477A CN109153621A CN 109153621 A CN109153621 A CN 109153621A CN 201780013477 A CN201780013477 A CN 201780013477A CN 109153621 A CN109153621 A CN 109153621A
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- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 44
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 41
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Classifications
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Abstract
本发明提供用于对含有2至6个碳原子的烷烃、优选地乙烷或丙烷、更优选地乙烷氧化脱氢的方法和相关反应***。确切地说,提供一种包含以下的方法:向包含上游和下游催化剂床的反应器容器供应包含所述烷烃和氧气的进气;使所述进气与所述上游催化剂床中的氧化脱氢催化剂接触,接着与所述下游催化剂床中的氧化脱氢/除氧催化剂接触,以产生包含烯烃的反应器流出物;以及从上游冷却剂回路向所述反应器容器的上游壳体空间供应上游冷却剂且从下游冷却剂回路向所述反应器容器的下游壳体空间供应下游冷却剂。
Description
技术领域
本发明涉及用于对含有2至6个碳原子的烷烃、确切地说乙烷或丙烷、更确切地说乙烷氧化脱氢的方法和相关反应***。
背景技术
乙烯为有价值的工业化合物,其广泛用作制造聚合物、苯乙烯、环氧乙烷、氯乙烯和乙酸乙烯酯单体、功能化烃(例如乙苯、二氯乙烷、乙醛、乙醇等)和许多其他化学产品的原料,所述化学产品用于产生如塑料、防冻剂、溶剂等的众多物品。
当前,蒸汽裂解烃(例如石脑油、乙烷、丙烷)为用于工业制造乙烯的最广泛方法。在此方法中,蒸汽稀释的烷烃在裂解炉中加热至足以将烃热裂解为如乙烯和丙烯的烯烃,外加一系列其他烃、氢和焦炭的温度(700-1000℃)。驻留时间极短,通常为0.1-0.5秒,且由于产物的高反应性,产物流必须紧接着淬灭以使所需烯烃的产量最大化且使非所需副产物的产量最小化。
尽管蒸汽裂解当前为乙烯生产的工业标准,但其具有许多缺点。举例来说,蒸汽裂解为高度吸热和高度能源密集的方法,因此使高燃料需求成为必需。类似地,由于方法在极高温下操作,对设备的要求苛刻。另外,在反应器内部形成大量焦炭,因此需要频繁地关闭反应器以进行维护和去除焦炭。
乙烯制备的替代方法为通过乙烷的氧化脱氢(ODH)。在这种方法中,乙烷与氧气在氧化脱氢催化剂存在下反应,产生主要包含乙烯连同未反应的反应物(如乙烷和氧气),和通常其它气体和/或副产物(如一氧化碳、二氧化碳、水)的产物流。通常,氧化脱氢催化剂为含有钼(Mo)、钒(V)、铌(Nb)和优选地碲(Te)作为金属的混合型金属氧化物催化剂。烷烃ODH方法,包括催化剂和其它方法条件的实例例如公开于美国专利第7,091,377号、美国专利公开案第2004/0147393号和第2010/0256432号以及WIPO公开案第WO2003/064035号和第WO2010/096909号中。有利地,相比于常规蒸汽裂解,烷烃ODH方法为热力学上有利的且可以在潜在较低反应温度下进行,不形成焦炭。
鉴于优于常规烯烃生产方法的潜在益处,烷烃ODH方法已成为大量研究的主题。确切地说,当前正研究提高连续操作期间的催化剂性能以延长催化剂使用期限和/或维持或提高催化剂活性和/或选择性的方法。举例来说,EP14194883描述使用包含钼、钒、铌和优选地碲的混合型金属氧化物催化剂的催化剂床的改进的ODH方法,其中通过确保在整个催化剂床中维持足够高的氧分压(例如通过控制ODH反应器出口气体中的氧浓度)而提高催化剂性能(例如选择性、活性和/或稳定性)。
但是,在工业规模ODH方法中,至少部分归因于将与在下游加工中后续去除所述氧相关的增加的成本,一般将ODH反应器出口气体中具有高氧浓度视为非所需的。也就是说,为了实现上文所提到的催化剂性能提高,通常将需要独立且成本高的“除氧”步骤(例如使用位于ODH反应器下游的除氧反应器)以避免下游加工中的可燃性/安全性问题。
因此,本发明人寻求提供用于含有2至6个碳原子的烷烃、确切地说乙烷或丙烷、更确切地说乙烷的氧化脱氢的改进的方法和反应***。确切地说,本发明人寻求提供ODH方法和反应***,其中催化剂性能(例如稳定性、活性和/或选择性)得以提高,同时仍在ODH反应器出口气体中产生低氧浓度。
发明内容
在一个方面中,提供用于将含有2至6个碳原子的烷烃、优选地乙烷或丙烷、更优选地乙烷氧化脱氢为含有2至6个碳原子的烯烃、优选地乙烯或丙烯、更优选地乙烯的方法,所述方法包含:
向反应器容器的入口供应包含烷烃和氧气的进气,反应器容器包含反应器壳体、安置于反应器壳体内部的多个反应管和将反应器容器内部划分为上游区和下游区的穿孔隔板,其中多个反应管包含:
(i)安置于上游区内的上游催化剂床,其包含有包含碲的氧化脱氢催化剂,和
(ii)安置于下游区内的下游催化剂床,其包含氧化脱氢/除氧催化剂;
使进气与上游催化剂床中的氧化脱氢催化剂接触,接着与下游催化剂床中的氧化脱氢/除氧催化剂接触,以产生包含烯烃的反应器流出物;以及
从上游冷却剂回路向反应器容器的上游壳体空间供应上游冷却剂且从下游冷却剂回路向反应器容器的下游壳体空间供应下游冷却剂。
另外,根据另一方面,提供用于将含有2至6个碳原子的烷烃、优选地乙烷或丙烷、更优选地乙烷氧化脱氢为含有2至6个碳原子的烯烃、优选地乙烯或丙烯、更优选地乙烯的反应***,所述反应***包含:
反应器容器,其包含流体连接到烷烃和氧气源的进气入口、反应器壳体、将反应器容器内部划分为上游区和下游区的穿孔隔板和安置于反应器壳体内部的多个反应管,所述多个反应管包含:
(i)安置于上游区内的上游催化剂床,其包含有包含碲的氧化脱氢催化剂,和
(ii)安置于下游区内的下游催化剂床,其包含氧化脱氢/除氧催化剂;
流体连接到反应器容器的上游壳体空间的上游冷却剂回路;和
流体连接到反应器容器的下游壳体空间的下游冷却剂回路。
附图说明
通过部分地参考以下描述以及附图可以理解本发明的一定特定实例实施例。
图1为显示本发明的示例性实施例的示意图。
尽管本发明易有各种修改和替代形式,已在图式中显示特定实例实施例且更详细地描述于本文中。然而,应理解,特定实例实施例的描述不打算将本发明限制于所公开的特定形式,相反,本发明打算涵盖如通过所附权利要求书部分说明的所有修改和等效形式。
具体实施方式
现已发现包含碲的氧化脱氢催化剂在还原环境(例如非氧化环境)中尤其易受催化剂失活。此类催化剂失活通常体现为催化剂稳定性、活性和/或选择性的非所需损失。另外,还发现当包含碲的氧化脱氢催化剂在低氧分压和相对高温(例如大于340℃)下操作时,碲可能从催化剂损失,这可能在下游设备和工艺物料流中导致严重问题。
有可能通过限制反应中转化的氧的量且因此确保在整个催化剂床中维持足够高的氧分压而使此类催化剂失活和碲损失最小化。但是,此操作方法导致反应器流出物中的氧浓度增加,归因于潜在的下游可燃性/安全性问题,通常需要在独立且成本高的“除氧”步骤中降低氧浓度。
本发明人已出人意料地发现通过使用本文公开的方法和反应***,有可能最小化或避免上文所提到的问题,同时在反应器流出物中实现足够低的氧浓度而不需要独立且成本高的“除氧”步骤。确切地说,已出人意料地发现,这些优点可以通过向反应器容器供应包含烷烃和氧气的进气来实现,所述反应器容器含有包含有包含碲的氧化脱氢催化剂的上游催化剂床,和包含氧化脱氢/除氧催化剂的下游催化剂床。根据本发明,反应器容器通过穿孔隔板分成上游区和下游区,其中上游催化剂床安置于上游区内且下游催化剂床安置于下游区内。冷却剂独立地在反应器容器的上游和下游壳体空间中循环,因此实现上游和下游区内的温度的独立控制。
一般来说,本发明的方法经操作以使得包含有包含碲的氧化脱氢催化剂的上游催化剂床处于氧化环境中,并且大多数氧气已耗尽的更下游为下游催化剂床,其包含氧化脱氢/除氧催化剂。适当地,下游催化剂床中的氧化脱氢/除氧催化剂为能够在不经历活性损失,或在任何情况下经历少得多的活性损失的情况下在低氧分压下催化烷烃与氧气之间的反应以产生烯烃的催化剂。因此,通过根据本发明方法进行操作,避免反应器流出物中的高氧浓度,但烷烃仍与下游区中剩余的氧气反应,以使其在不经历由下游区中减少的氧浓度所致的催化剂性能的显著下降的情况下转化成烯烃。
本发明的反应***一般包含反应器容器,所述反应器容器包含进气入口、反应器壳体、将反应器容器内部划分为上游区和下游区的穿孔隔板,以及包含上游催化剂床和下游催化剂床的多个反应管。适当地,反应***进一步包含与反应器容器的上游壳体空间和上游冷却剂源流体连通的上游冷却剂回路,和与反应器容器的下游壳体空间和下游冷却剂源流体连通的下游冷却剂回路。
尽管反应器容器内的反应管的尺寸和数目可在反应器之间大幅变化,但用于商业反应器容器的反应管可一般具有1至25米的长度和10至80毫米的内管直径。另外,反应管的数目可变化且可在例如数千至50,000范围内。
在反应器壳体内,反应管的上端通常通过上管板固定在适当的位置且与反应器容器的进气入口流体连通。类似地,反应管的下端通常通过下管板固定在适当的位置且与反应器容器的出口流体连通。优选地,反应管以基本竖直方式布置在反应器壳体内,使得其距竖直不超过5°,且上管板和下管板以基本水平方式安置于反应器壳体内,使得其距水平不超过3°。
穿孔隔板将反应器容器划分为上游区和下游区。一般来说,穿孔隔板为具有多个反应管可穿过的孔的板。穿孔隔板可以是任何合适材料,如金属(例如碳钢)。
每个反应管包含安置于反应器容器的上游区内的上游催化剂床和安置于反应器容器的下游区内的下游催化剂床。任选地,除了上游和下游催化剂床以外,反应管可以进一步包含一个或多个惰性材料床,其可以安置于上游区、下游区或两者中。
适当地,上游催化剂床包含有包含碲的氧化脱氢催化剂。适合的包含碲的氧化脱氢催化剂的实例包括但不一定限于具有下式的一种或多种混合型金属氧化物催化剂:
Mo1VaTebNbcOn
其中:
a、b、c和n表示所讨论的元素的摩尔量与钼(Mo)的摩尔量的比率,
a(对于V)是0.01到1,优选是0.05到0.60,更优选是0.10到0.40,更优选是0.20到0.35,最优选是0.25到0.30;
b(对于Te)是>0到1,优选是0.01到0.40,更优选是0.05到0.30,更优选是0.05到0.20,最优选是0.09到0.15;
c(对于Nb)是>0到1,优选是0.01到0.40,更优选是0.05到0.30,更优选是0.10到0.25,最优选是0.14到0.20;并且
n(对于O)是由除氧以外的元素的价数和出现频率确定的数值。
任选地,上游催化剂床可包含超过一种包含碲的氧化脱氢催化剂。举例来说,在一个实施例中,上游催化剂床可包含具有改变的活性水平的多种氧化脱氢催化剂(例如以沿上游区中的反应管的长度改变活性水平)。另外,必要时,上游催化剂床可以进一步包含惰性材料(例如以稀释和/或降低上游催化剂床的活性)。
通常,在相同基础上,上游催化剂床的催化剂床高度为反应管长度的至少50%、或至少60%、或至少65%、或至少70%。另外,在相同基础上,上游催化剂床的催化剂床高度通常为反应管长度的至多99%、或至多95%、或至多90%、或至多85%。另外,在相同基础上,上游催化剂床的催化剂床高度可以是反应管长度的约50%至99%、或约50%至95%、或约70%至95%。
适当地,下游催化剂床包含氧化脱氢/除氧催化剂。一般来说,适合的氧化脱氢/除氧催化剂为能够在低氧分压下催化烷烃与氧气之间的反应以产生烯烃的那些催化剂和/或用于驱动除氧的催化剂。
适合的氧化脱氢/除氧催化剂包括但不一定限于具有下式的一种或多种混合型金属氧化物催化剂:
a)Mo1VaTebNbcAdOn;
b)Mo1VaSbbNbcAdOn;
c)Mo1VaSbbNbcOn;
d)Mo1VaSbbAdOn;或
e)Mo1VaSbbOn;
其中:
A为选自由Pt、Pd、Cu、Ag和Fe组成的群组的至少一种金属;
a、b、c、d和n表示所讨论的元素的摩尔量与钼(Mo)的摩尔量的比率;
a(对于V)是0.01到1,优选是0.05到0.60,更优选是0.10到0.40,更优选是0.20到0.35,最优选是0.25到0.30;
b(对于Te或Sb)是>0到1,优选是0.01到0.40,更优选是0.05到0.30,更优选是0.05到0.20,最优选是0.09到0.15;
c(对于Nb)是>0到1,优选是0.01到0.40,更优选是0.05到0.30,更优选是0.10到0.25,最优选是0.14到0.20;
d(对于A)是>0到0.3;并且
n(对于O)是由除氧以外的元素的价数和出现频率确定的数值。
另外,适合的氧化脱氢/除氧催化剂还可以包括用于驱动除氧的任何已知催化剂(例如氧化催化剂、水煤气变换催化剂)。举例来说,此类催化剂可以包括所属领域的技术人员已知的负载的铂、钯、银、铜和/或铁催化剂。
任选地,下游催化剂床可以包含超过一种氧化脱氢/除氧催化剂。举例来说,在一个实施例中,下游催化剂床可以包含具有改变的活性水平的多个氧化脱氢/除氧催化剂(例如以沿下游区中的反应管的长度改变活性水平)。另外,必要时,下游催化剂床可以进一步包含惰性材料(例如以稀释和/或降低下游催化剂床的活性)。
通常,在相同基础上,下游催化剂床的催化剂床高度为反应管长度的至少1%、或至少5%、或至少10%、或至少15%。另外,在相同基础上,下游催化剂床的催化剂床高度通常为反应管长度的至多50%、或至多40%、或至多35%、或至多30%。另外,在相同基础上,下游催化剂床的催化剂床高度可以是反应管长度的约1%至50%、或约5%至50%、或约5%至30%。
优选地,氧化脱氢催化剂、氧化脱氢/除氧催化剂或两者为非均相的且呈粒子形式。另外,优选地,所述非均相催化剂为多孔的,尤其为多孔、微粒催化剂。
任选地,本发明的反应***可以进一步包含除氧区,其包含位于上游以及下游催化剂床下游的除氧催化剂。当包括时,除氧区可以安置于反应器容器的底部部分内(即反应管以下的反应器壳体的底部部分中)和/或独立的除氧容器中。有利地,除氧区可以用于进一步减少反应器流出物的氧浓度。适合的除氧催化剂可以包括用于驱动除氧的任何已知催化剂(例如氧化催化剂、水煤气变换催化剂)。举例来说,适合的除氧催化剂可以包括所属领域的技术人员已知的负载的铂、钯、银、铜和/或铁催化剂。
本发明的反应***进一步包含上游冷却剂回路和下游冷却剂回路。如先前所提及,关于反应器容器的结构,反应器容器通过穿孔隔板分成上游区和下游区,其相对应地允许分别通过上游和下游冷却剂回路独立地控制上游壳体空间和下游壳体空间中循环的冷却剂的温度。一般来说,上游和下游冷却剂回路分别向反应器容器的上游和下游壳体空间供应冷却剂且从其去除冷却剂。
优选地,上游和下游冷却剂回路各自包含冷却设备(例如热交换器、汽包等)和循环泵。冷却剂可以任何合适方式供应至反应器容器的上游和下游壳体空间和从其去除。举例来说,冷却剂可以通过上游和下游冷却剂入口分别在上游和下游区的底部处或附近供应至反应器容器的上游和下游壳体空间。类似地,冷却剂可以通过上游和下游冷却剂出口分别在上游和下游区的顶部处或附近从反应器容器的上游和下游壳体空间去除。冷却剂可以是适合于热传递的任何流体,例如适合于热交换的熔融盐或有机材料(例如油、煤油等)。
任选地,使用上游和/或下游冷却剂回路从反应器容器去除的热量可以用于加热供应至反应器容器的进气和/或冷却剂。另外,必要时,去除的热量还可以用于蒸汽产生(或锅炉给水预热)以用作能量来源,包括以蒸汽自身形式或另外转化成电力。
一般来说,独立地选择供应至反应器容器的上游和下游壳体空间的冷却剂的对应温度,以这种方式使得相关上游或下游催化剂床具有所需活性。另外,如所属领域的技术人员应了解,如分别在上游和下游冷却剂入口处所测量的上游和下游冷却剂温度可以用于提供上游和下游催化剂床的对应温度的近似值。举例来说,取决于冷却剂的特定热容量、方法条件和反应器规格,上游和下游催化剂床的温度可能通常超过对应上游和下游冷却剂温度1-30℃。
适当地,如在上游冷却剂入口处所测量的冷却剂温度通常为至少250℃、或至少275℃、或至少300℃、或至少325℃、或至少350℃,且通常为至多400℃、或至多375℃、或至多370℃、或至多360℃、或至多350℃,或250℃至400℃、或275℃至375℃、或300℃至350℃。
适当地,如在下游冷却剂入口处所测量的冷却剂温度通常为至少120℃、至少150℃、至少200℃、至少250℃、或至少275℃、或至少300℃、或至少310℃、或至少320℃,且通常为至多500℃、或至多450℃、或至多425℃、或至多400℃、或至多380℃,或120℃至500℃、或200℃至500℃、或250℃至500℃、或250℃至400℃、或300℃至400℃、或320℃至380℃。
在下游催化剂床包含具有氧化脱氢功能性(即催化烷烃与氧气之间的反应以产生烯烃)的催化剂的那些实施例中,如在下游冷却剂入口处所测量的冷却剂的温度优选地为300℃至500℃,或300℃至400℃。
另外,在下游催化剂床包含具有氧化功能性(即催化烯烃和/或未反应的烷烃的燃烧反应以产生二氧化碳和水)和/或水煤气变换功能性(即催化一氧化碳和水的反应以产生二氧化碳和氢气)的催化剂的那些实施例中,如在下游冷却剂入口处所测量的冷却剂的温度优选地为120℃至400℃,或150℃至400℃,自200℃至400℃。
优选地,反应器容器内的多个反应管中的压力为约1至20绝对巴(bara/“barabsolute”)、优选地1至15绝对巴、更优选地2至10绝对巴、并且甚至更优选地3至8绝对巴。
根据本发明的氧化脱氢方法,将包含烷烃和氧气的进气供应至反应器容器的入口。如本文所用,术语“进气”理解为是指反应器容器的入口处的全部气态物料流。因此,如所属领域的技术人员应了解,进气通常由一种或多种气态物料流,如乙烷物料流、氧气物料流、再循环气体流等的组合构成。任选地,除烷烃(例如乙烷)和氧气以外,进气可以进一步包含其它烷烃、一氧化碳、二氧化碳、氢气、蒸汽、惰性气体(如氮气、氦气和/或氩气),和/或ODH反应的各种副产物(例如乙炔、乙酸)。
含有2至6个碳原子的适合的烷烃一般包括含有2至6个碳原子的直链烷烃(即,乙烷、丙烷、丁烷、戊烷和己烷)。优选地,烷烃为含有2至4个碳原子的直链烷烃(即,乙烷、丙烷和丁烷)。更优选地,烷烃为乙烷或丙烷,最优选为乙烷。一般来说,进气中的烷烃(例如乙烷)可以来自任何适合的来源,包括天然气,其条件是从其充分地去除杂质且可以包括新的烷烃和任选地从反应器流出物再循环的未反应的烷烃。类似地,氧气可以来源于任何适合的来源,如空气。
一般来说,反应器容器入口处的进气中的分子氧与烃(例如烷烃,如乙烷)的摩尔比可以在0.01至1、更适当地0.05至0.5的范围内。优选地,相对于进气的总体积,进气包含5至35体积%的氧气、更适当地20至30体积%的氧气,和40至80体积%的烷烃,更适当地50至70体积%烷烃,和小于80(0至80)体积%的惰性气体,更适当地小于50(0至50)体积%的惰性气体,更适当地5至35体积%的惰性气体,最适当地10至20体积%的惰性气体。
进气的组分供应至反应器容器入口的次序和方式不受特定限制,且因此,组分可以同时或依序组合。另外,进气的组分可以任选地在供应至反应器容器入口之前使用所属领域的技术人员已知的方法汽化、预热和混合(必要时)。举例来说,预热技术可以包括例如从蒸汽、热传递流体(例如冷却剂)、反应器流出物和/或炉的热交换。
反应器流出物将通常包含烷烃的脱氢等效物(也就是说,对应烯烃)。举例来说,在乙烷的情况下,反应器流出物包含乙烯,在丙烷的情况下,反应器流出物包含丙烯,诸如此类。除烯烃以外,反应器流出物可以进一步包含添加的水(如果使用的话),和由ODH反应形成的额外水、一氧化碳、二氧化碳、羧酸、和少量的其它杂质,外加残余量的未反应的烷烃和氧气。
优选地,按反应器流出物的总体积计,反应器流出物中的氧气的量为至多500体积百万分率(ppmv),或至多300ppmv,或至多200ppmv,或至多100ppmv,或至多50ppmv。
在一些实施例中,烯烃可以在相同条件下进一步氧化为对应羧酸,其可或可不含有一个或多个不饱和碳-碳双键。举例来说,在乙烷的情况下,反应器流出物可以包含乙烯和/或乙酸。另外,在丙烷的情况下,反应器流出物可以包含丙烯和/或丙烯酸。
现在参看图1,其为根据本发明的实施例,将烷烃(例如乙烷)氧化脱氢为对应烯烃(例如乙烯)的反应***的示意图。技术人员应清楚,作为示意图,此图不显示可存在于反应***中的所有所需输入、输出、再循环流等。此外,在图中,如应了解,可以添加、更换和/或消除元件以提供任何数目的其它实施例。另外,如应了解,图中提供的元件的比例和相对标度打算说明本发明的实施例,且不应以限制性含义采用。
如图1中所示出,反应器容器(1)为壳管式热交换器反应器容器,气包含进气入口(2)、反应器壳体(3)、将反应器容器(1)的内部划分为上游区(10)和下游区(20)的穿孔隔板(5),和基本上平行于反应器容器(1)的中心纵向轴线(7)安置的多个开口反应管(6)。一般来说,穿孔隔板(5)为具有多个反应管(6)可穿过的孔的板。反应管(6)的上端(8)连接至基本上水平的上管板(9)且反应管(6)的下端(18)连接至基本上水平的下管板(19)。上管板(9)和下管板(19)通过反应器容器(1)的内壁负载。
如图1中所示出,反应管(6)穿过存在于穿孔隔板(5)中的孔,使得每个反应管的一部分安置于上游区(10)内且每个反应管的一部分安置于下游区(20)中。反应管(6)含有安置于上游区(10)中的上游催化剂床(11)和安置于下游区(20)中的下游催化剂床(21)。除上游和下游催化剂床以外,反应管(6)可以任选地进一步包含惰性材料床,如惰性床(13)。上游催化剂床(11)含有包含碲的氧化脱氢催化剂(12)。下游催化剂床(21)含有氧化脱氢/除氧催化剂(22)。通常,下游催化剂床(21)通过布置于反应管(6)的下端(18)中的催化剂载体构件(未示出)负载于反应管(6)中。
冷却剂以基本独立方式循环穿过上游壳体空间(14)和下游壳体空间(24),因此实现上游区(10)和下游区(20)内的温度的独立控制。任选地,上游壳体空间(14)和/或下游壳体空间(24)可以配备有引导冷却剂的挡板(未示出)。
在上游区(10)中,冷却剂通过一个或多个上游冷却剂入口,如上游冷却剂入口(16)从上游冷却剂回路(15)供应至上游壳体空间(14),且通过一个或多个上游冷却剂出口,如上游冷却剂出口(17)从上游壳体空间(14)去除。类似地,在下游区(20)中,冷却剂通过一个或多个下游冷却剂入口,如下游冷却剂入口(26)从下游冷却剂回路(25)供应至下游壳体空间(24),且通过一个或多个下游冷却剂出口,如下游冷却剂出口(27)从下游壳体空间(24)去除。
在上游和下游壳体空间两者中,循环冷却剂将通过与反应管(6)接触而吸收热,使得冷却剂在从上游或下游冷却剂出口排出时将通常比其供应至对应上游或下游冷却剂入口时略微更热。适当地,在上游和下游冷却剂回路两者中,冷却设备(未示出)可用于在将冷却剂分别再供应至上游和下游壳体空间之前从其去除热量。
根据本发明方法,包含乙烷和氧气的进气(4)通过与反应管(6)的上端(8)流体连通的一个或多个进气入口,如进气入口(3)供应至反应器容器(1)。在反应管(6)中,进气(4)首先接触上游催化剂床(11),接着接触下游催化剂床(21)。在催化剂存在下在如上文所述的适当反应条件下接触进气将至少一部分乙烷转化为乙烯、水和反应副产物(如果存在)。反应器流出物(29)通过与反应管(6)的下端(18)流体连通的一个或多个出口,如出口(28)离开反应器容器(1)。
Claims (9)
1.一种用于将含有2至6个碳原子的烷烃、优选地乙烷或丙烷、更优选地乙烷氧化脱氢为含有2至6个碳原子的烯烃、优选地乙烯或丙烯、更优选地乙烯的方法,其包含:
向反应器容器的入口供应包含所述烷烃和氧气的进气,所述反应器容器包含反应器壳体、安置于所述反应器壳体内部的多个反应管和将所述反应器容器内部划分为上游区和下游区的穿孔隔板,其中所述多个反应管包含:
(i)安置于所述上游区内的上游催化剂床,其包含有包含碲的氧化脱氢催化剂,和
(ii)安置于所述下游区内的下游催化剂床,其包含氧化脱氢/除氧催化剂;
使所述进气与所述上游催化剂床中的所述氧化脱氢催化剂接触,接着与所述下游催化剂床中的所述氧化脱氢/除氧催化剂接触,以产生包含所述烯烃的反应器流出物;和
从上游冷却剂回路向所述反应器容器的上游壳体空间供应上游冷却剂且从下游冷却剂回路向所述反应器容器的下游壳体空间供应下游冷却剂。
2.根据权利要求1所述的方法,其中所述上游催化剂床的催化剂床高度为反应管长度的50%到99%且所述下游催化剂床的催化剂床高度为反应管长度的1%至50%。
3.根据权利要求1或权利要求2所述的方法,其中所述上游冷却剂在250℃至400℃的温度下供应至所述反应器容器的所述上游壳体空间。
4.根据权利要求1到3中任一项所述的方法,其中所述下游冷却剂在120℃至500℃的温度下供应至所述反应器容器的所述下游壳体空间。
5.根据权利要求1到4中任一项所述的方法,其中所述反应器流出物包含不超过500ppmv的氧气。
6.根据权利要求1到5中任一项所述的方法,其中所述上游催化剂床中的所述包含碲的氧化脱氢催化剂具有下式:
Mo1VaTebNbcOn
其中:
a、b、c和n表示所讨论的元素的摩尔量与钼的摩尔量的比率;
a为0.01至1;
b为>0至1;
c为>0至1;且
n是由除氧以外的元素的价数和出现频率确定的数值。
7.根据权利要求1到6中任一项所述的方法,其中所述下游催化剂床中的所述氧化脱氢/除氧催化剂具有下式中的一个:
a)Mo1VaSbbNbcAdOn;
b)Mo1VaSbbNbcOn;
c)Mo1VaSbbAdOn;或
d)Mo1VaSbbOn;
其中:
A为选自由Pt、Pd、Cu、Ag和Fe组成的群组的至少一种金属;
a、b、c、d和n表示所讨论的元素的摩尔量与钼的摩尔量的比率;
a为0.01至1;
b为>0至1;
c为>0至1;
d为>0至0.3;且
n(对于O)是由除氧以外的元素的价数和出现频率确定的数值。
8.根据权利要求1到6中任一项所述的方法,其中所述下游催化剂床中的所述氧化脱氢/除氧催化剂具有下式:
Mo1VaTebNbcAdOn
其中:
A为选自由Pt、Pd、Cu、Ag和Fe组成的群组的至少一种金属;
a、b、c、d和n表示所讨论的元素的摩尔量与钼的摩尔量的比率;
a为0.01至1;
b为>0至1;
c为>0至1;
d为>0至0.3;且
n是由除氧以外的元素的价数和出现频率确定的数值。
9.一种用于将含有2至6个碳原子的烷烃、优选地乙烷或丙烷、更优选地乙烷氧化脱氢为含有2至6个碳原子的烯烃、优选地乙烯或丙烯、更优选地乙烯的反应***,其包含:
反应器容器,其包含流体连接到烷烃和氧气源的进气入口、反应器壳体、将所述反应器容器内部划分为上游区和下游区的穿孔隔板和安置于所述反应器壳体内部的多个反应管,所述多个反应管包含:
(i)安置于所述上游区内的上游催化剂床,其包含有包含碲的氧化脱氢催化剂,和
(ii)安置于所述下游区内的下游催化剂床,其包含氧化脱氢/除氧催化剂;
流体连接到所述反应器容器的上游壳体空间的上游冷却剂回路;和
流体连接到所述反应器容器的下游壳体空间的下游冷却剂回路。
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