CN102325742A - 丙烯制备方法 - Google Patents

丙烯制备方法 Download PDF

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CN102325742A
CN102325742A CN2009801533439A CN200980153343A CN102325742A CN 102325742 A CN102325742 A CN 102325742A CN 2009801533439 A CN2009801533439 A CN 2009801533439A CN 200980153343 A CN200980153343 A CN 200980153343A CN 102325742 A CN102325742 A CN 102325742A
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CN102325742B (zh
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G·A·索耶
M·G·阿克塞尔罗
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Abstract

公开了丙烯生产方法。该方法包括(a)在骨架异构化催化剂的存在下使含有异丁烯的进料流反应,得到包含C4烯烃的异构化料流;以及(b)在复分解催化剂的存在下使所述异构化料流与乙烯反应,形成包含丙烯、C4烯烃、和C5+烯烃的复分解产物流。所述复分解反应压力等于或低于骨架异构化的压力。

Description

丙烯制备方法
技术领域
本发明涉及由C4烯烃和乙烯制备丙烯的方法。
背景技术
烃的蒸汽裂解是石油化学加工过程,广泛用于生产烯烃,例如乙烯、丙烯、C4烯烃(1-丁烯、2-丁烯、异丁烯)、丁二烯和芳族烃如苯、甲苯和二甲苯。2-丁烯包括顺式-2-丁烯和/或反式-2-丁烯。在烯烃设备(plant)中,烃类进料如萘、汽油、或全原油的其他馏分与蒸汽混合。所述混合物在预热后,在热解炉中在高温下进行重度热裂解。来自热解炉的裂解流出物包含很多种的气态烃(每分子碳原子数为1-35)。该流出物包括脂肪族、芳香族、饱和及不饱和烃,也可包括大量分子氢。然后热解炉的裂解产物在烯烃设备中进一步加工来制备作为该设备的产品的各种单独的产物流,例如氢气、乙烯、丙烯、每分子具有4或5个碳原子的混合烃、以及裂解汽油。
粗制C4烃可能含有不同数量的正丁烷、异丁烷、C4烯烃、乙炔(乙基乙炔和乙烯基乙炔)、以及丁二烯。参见Kirk-Othmer Encyclopedia of Chemical  Technology,在线版本(2008)。通常将粗制C4烃进行丁二烯萃取或丁二烯选择氢化以除去大部分,如果不能基本上全部的话,存在的丁二烯和乙炔。然后C4残液(称为残液-1)进行化学反应(如醚化、水合、或二聚化),其中异丁烯转化为其他化合物(如甲基叔丁基醚、叔丁醇、或二异丁烯)(参见,如美国专利6,586,649和4,242,530)。主要包括正丁烷、异丁烷、1-丁烯和2-丁烯的剩余C4料流称为残液-2。然而,市场有时对甲基叔丁基醚、叔丁醇、或二异丁烯的需要是有限的,需要将异丁烯转化为其他有价值的产品,例如丙烯。
已知通过异丁烯骨架异构化及复分解反应制备丙烯的方法。参见,如美国专利6,743,958、6,872,862、6,977,318、7,074,976。骨架异构化反应在相对较低的压力下进行以限制不需要的副反应。然而,迄今公开的方法要求复分解步骤在相对较高的压力下进行。因此需要将来自骨架异构化反应的异构化料流冷却至更低的温度以对所述料流加压,然后在该料流进料到复分解反应前加热该料流至高温。在美国专利6,743,958的一个实施例中,复分解反应器在3.5Mpa(514psig)下进行。美国专利6,872,862、6,977,318,和7,074,976教导复分解反应在300至800F的温度以及200至600psig压力下进行。
需要开发能够使热交换需要以及能量和设备成本最小化的方法。
发明概述
本发明为丙烯生产方法。所述方法包括(a)在骨架异构化催化剂的存在下包含异丁烯的进料流反应得到包括C4烯烃的异构化料流;以及(b)在复分解催化剂的存在下所述异构化料流与乙烯反应,以形成包括丙烯、C4烯烃和C5以及更高级烯烃的复分解产物流。复分解反应压力等于或低于骨架异构化反应的压力。
附图说明
图1为本发明一种实施方式的示意图。
图1A显示图1的分离区的细节。
图2为制备丙烯的对比方法的示意图。
图2A显示图2的分离区的细节。
发明详述
所述方法的进料流包含异丁烯。优选地,进料包含多于95wt%C4烯烃。一种合适的进料流可由残液-1得到,该残液-1由来自精制或蒸汽裂解工艺的粗制C4流获得。残液-1主要包括C4烯烃、正丁烷和异丁烷。优选地,使用合适的萃取溶剂(例如二甲基甲酰胺、N-甲基吡咯烷酮、或N-甲酰基吗啉)通过萃取蒸馏或选择吸附从残液-1中除去链烷烃(正丁烷和异丁烷)。一种合适的进料是由叔丁基醇脱水得到的。
所述方法包括在骨架异构化催化剂的存在下进料流反应得到包含C4烯烃的异构化料流。骨架异构化催化剂为任何可催化异丁烯至直链C4烯烃(1-丁烯,2-丁烯)的异构化的固体。另外,它们也可催化1-丁烯和2-丁烯之间的转化反应。这些催化剂在所属领域中已知。合适的骨架异构化催化剂包括沸石、金属氧化物和混合金属氧化物。
可使用包含沸石的骨架异构化催化剂。除氧以外,沸石一般包括Si、Ge、Al、B、P等的一种或多种。通常孔隙大小在大于约0.4nm至小于约0.7nm范围内的具有一维孔结构的沸石可用于本发明的方法。适用于骨架异构化的沸石实例包括镁碱沸石(ferrierite)的氢形式、SAPO-11、SAPO-31、SAPO-41、FU-9、NU-23、NU-10、ZSM-12、ZSM-22、ZSM-23、ZSM-35、ZSM-48、ZSM-50、MeAPO-11、MeAPO-31、MeAPO-41、MeAPSO-11、MeAPSO-31、MeAPSO-41、ELAPO-11、ELAPO-31、ELAPO-41、ELAPSO-11、ELAPSO-31、ELAPSO-41、浊沸石、斜发沸石、钙霞石、菱钾沸石、片沸石(heulindite)的氢形式、辉沸石的氢形式、以及丝光沸石的镁或钙形式,如美国专利6,111,160中所述。美国专利5,817,907、申请公开号为2002/0019307的美国专利以及EP050157公开了其他合适的沸石。
可使用包含金属氧化物或混合氧化物的骨架异构化催化剂。合适的金属氧化物或混合氧化物包括氧化铝、氧化硅-氧化铝、氧化锆、氧化硅-氧化锆等。其实例可参见美国专利2,471,647、3,558,733、5,321,195和5,659,104。
尽管骨架异构化反应可在任何反应器类型中进行,但优选固定床反应器。所述催化剂优选为挤出物、珠、颗粒、片等形式。
骨架异构化优选在500至850F下,更优选在600至750F,和在15至100psig压力下、更优选在20至60psig压力下进行。气体时空速适于在50至200/小时范围内。
由骨架异构化反应可产生异构化料流。所述异构化料流包括C4烯烃,以及可能少量的C5及更高级的烯烃。
该方法包括在复分解催化剂存在下使异构化料流与乙烯反应。复分解催化剂在本领域中是公知的(如参见美国专利4,513,099,5,120,894)。通常,复分解催化剂包含过渡金属氧化物。合适的过渡金属氧化物包括钴、钼、铼、钨的氧化物及其混合物。合宜地,催化剂负载于载体上。合适的载体包括氧化硅、氧化铝、氧化钛、氧化锆、沸石、粘土及其混合物。氧化硅和氧化铝为优选的载体。催化剂可以任何合适的方式负载于载体上,尤其是通过吸附、离子交换、浸渍或升华作用。催化剂的过渡金属氧化物成分的量为全部催化剂的1至30wt%,优选5至20wt%。
除复分解催化剂之外,所述复分解步骤还优选使用双键异构化催化剂。双键异构化催化剂可在复分解反应过程中将1-丁烯转化为2-丁烯,由此提高复分解反应的丙烯产率。
可以使用许多双键异构化催化剂,包括酸性催化剂和碱性催化剂。合适的酸性催化剂包括金属氧化物(例如氧化铝、氧化锆、硫酸化氧化锆),混合氧化物(例如氧化硅-氧化铝、氧化锆-氧化硅)、酸性沸石、酸性粘土(参见如美国专利US4,992,613、公开号为2004/0249229和2006/0084831的美国专利申请)。碱性双键异构化催化剂优选为金属氧化物,如镁氧化物(氧化镁)、氧化钙、氧化钡、及氧化锂。可使用负载于载体上的金属氧化物。合适的载体包括氧化硅、氧化铝、氧化钛、氧化硅-氧化铝等,及其混合物(参见如美国专利5,153,165、5,300,718、5,120,894、4,992,612,公开号为2003/0004385的美国专利申请)。尤其优选的碱性异构化催化剂为氧化镁。适用的氧化镁具有至少1平方米每克(m2/g)的表面积,优选至少5m2/g。
异构化料流与乙烯在复分解催化剂存在下的反应是在等于或低于骨架异构化反应的压力下进行的。通常,复分解反应压力为15至100psig,更优选在20至60psig下。本发明的优点在于不需要冷却异构化料流、对其加压、然后再加热至适于复分解反应的温度。因此本发明节省了能量和设备。下述的实施例1和2进一步证明了本发明的优点。
所述复分解反应制备得到包含乙烯、丙烯、C4烯烃、及C5和更高级烯烃(C5+烯烃)的复分解产物流。
优选地,所述方法进一步包括将分离复分解产物流为乙烯流、丙烯产物流、C4流(主要包含C4烯烃)、和C5+烯烃流。所述C5+烯烃流主要包含具有5个或更多碳的烯烃,可用作汽油调和组分。分离如复分解产物流的混合物对本领域人员是公知的。参见美国专利7,214,841。通常,这种分离利用串联的三个蒸馏塔进行:脱乙烯塔、脱丙烯塔、和脱丁烯塔。
乙烯流通过脱乙烯塔作为塔顶馏出物分离。典型所述脱乙烯塔在冷凝器中在-5至40F温度下和350至650psig的压力下进行。优选地,所述乙烯流循环至该方法的复分解反应。
丙烯以及任意更轻的化合物在脱丙烯塔的塔顶馏出物中去除。典型脱丙烯塔在冷凝器中在为50至140F温度下和100至350psig压力下进行。
C4烯烃以及任意更轻的化合物从脱丁烯塔作为塔顶馏出物去除。典型脱丁烯塔在冷凝器中在100至160F温度下和50至140psig压力下进行。优选地,所述C4烯烃流循环至该方法的骨架异构化反应。C5及更重的产物作为脱丁烯塔的塔底产物分离。
实施例1
图1和1A显示了该方法。管道1中的新鲜异丁烯进料(100,000lb/h)与来自管道2的循环C4流混合,形成管道3中的混合C4流。该混合C4流在加热区101加热至700F。该加热的混合C4流,通过管道3a,进入骨架异构化反应器102形成异构化产物流。反应器102中使用美国专利6,111,160实施例1中描述的H-Ferrierite催化剂。异构化反应在700F和30psig下进行。异构化料流在656F温度下经管道4离开反应器102,并与管道5中的新鲜乙烯进料及管道6中的循环乙烯流混合。该混合进料通过加热区103加热然后经管道8a进入复分解反应器104。所述复分解反应器104包括美国专利5,120,894中公开的氧化镁和负载于氧化硅上的WO3的混合物。复分解反应在650F和30psig下进行。复分解产物流经管道9离开反应器104,然后经冷却区105冷却至140F,经压缩机106加压,然后经管道9b进料至分离区107。
分离区107的细节在图1A中显示。它包括脱丁烯塔107a、脱丙烯塔107b、和脱乙烯塔107c。蒸馏顺序,由较低压力到较高压力,非常适合管道9b中的低压蒸汽进料。复分解产物流经管道9b进入脱丁烯塔107a。C5+烯烃流经管道11作为脱丁烯塔107a的塔底产物流来回收。包含丁烯和更轻烯烃的塔顶馏出物经管道12进料至脱丙烯塔107b。丁烯流作为脱丁烯塔107b的塔底产物得到并经管道2循环至异构化反应。塔顶馏出物经管道13进入脱乙烯塔107c。乙烯流在管道6中在脱乙烯塔107c中作为塔顶馏出物分离。丙烯产物流经管道10由塔底产物流得到。各种料流的预期组分列于表1。该方法的总传热交换示于表2。
对比实施例2
图2和2A显示了该方法。管道1中的新鲜异丁烯进料与来自管道2的循环C4流混合形成管道3中的混合C4进料。该混合C4流经加热区201加热至700F。该加热的C4进料经管道3a进入异构化反应器202。反应器202中使用美国专利6,111,160实施例1中描述的H-Ferrierite催化剂。异构化产物流经管道4离开反应器202然后进入冷却区203冷却至80F。管道4a中冷凝的料流经泵204抽吸至450psig,然后与管道5中新鲜乙烯进料和管道6中循环乙烯流混合。该混合进料在205区加热至605F,然后进入复分解反应器206。所述复分解反应器206包含美国专利5,120,894中公开的氧化镁和负载于氧化硅上的WO3的混合物。该复分解反应器在650F和450psig下进行。管道9中的复分解产物流经冷却区207冷却然后进入分离区208。
分离区208的细节在图2A中显示。它包括脱乙烯塔208a、脱丙烯塔208b、和脱丁烯塔208c。复分解产物流经管道9a进入脱乙烯塔208a。蒸馏顺序,由较高压力到较低压力,非常适合管道9a中的高压进料。未反应的乙烯在脱乙烯塔208a中作为塔顶馏出物回收并经管道6循环。包含丙烯和C4-C6烯烃的脱乙烯塔塔底产物流进料至脱丙烯塔208b,其中丙烯产物流作为塔顶馏出物经管道10回收。来自脱丙烯塔208b塔底产物的丁烯、C5烯烃、及更高级烯烃经管道13进料至脱丁烯塔208c,在那里丁烯作为塔顶馏出物分离并经管道2循环。C5+烯烃料流作为塔底产物流从脱丁烯塔208c经管道11回收。各料流的预期组成列于表1。该方法的总传热示于表2。
表2比较了2个实施例中的加热和冷却需求,包括分离区所需要的那些。能量节省可由热工艺料流和冷工艺料流的热集成(heat integrating)认识到;然而,热集成设备的大小和成本随着热集成量的增大而增加。通过应用本发明(实施例1),热集成可减少一半,由398MMBTU/h至194MMBTU/h。热集成的节省来自工艺前端的改变。进一步地,利用设备如蒸汽或火焰加热器的加热由218MMBTU/h减至158MMBTU/h。利用设备例如冷却水、空气或冷冻的冷却也减少了。加热及冷却设备的节省来自蒸馏顺序的改变,这有助于其匹配复分解的较低压力。
表2 总传热
  MMBTU/h   实施例1   对比例2
  集成的热   194   398
  加热设备   158   218
  冷却设备   198   225

Claims (12)

1.制备丙烯的方法,包括:
(a)在骨架异构化催化剂的存在下使含有异丁烯的进料流反应,得到包含C4烯烃的异构化料流;和
(b)在复分解催化剂的存在下使所述异构化料流与乙烯反应,形成包含丙烯、C4烯烃、和C5及更高级烯烃的复分解产物流;其中步骤(b)在等于或小于步骤(a)的压力下进行。
2.权利要求1的方法,其中步骤(a)在20至60psig下进行。
3.权利要求2的方法,其中步骤(b)在20至60psig下进行。
4.权利要求1的方法,其中所述进料流含有高于95wt%的C4烯烃。
5.权利要求1的方法,其中所述进料流由叔丁醇的脱氢制得。
6.权利要求1的方法,进一步包括将复分解产物流分离为乙烯流、丙烯产物流、C4烯烃流、以及C5及更高级烯烃流。
7.权利要求6的方法,其中步骤(a)在20至60psig下进行。
8.权利要求7的方法,其中步骤(b)在20至60psig下进行。
9.权利要求6的方法,其中所述乙烯流循环至步骤(b)。
10.权利要求6的方法,其中所述C4烯烃流循环至步骤(a)。
11.权利要求6的方法,其中所述进料流含有高于95wt%的C4烯烃。
12.权利要求6的方法,其中所述进料流由叔丁醇的脱氢制得。
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