CN1182071A - 乙苯脱氢为苯乙烯的方法 - Google Patents
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000006356 dehydrogenation reaction Methods 0.000 title claims description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title abstract description 17
- 239000003054 catalyst Substances 0.000 claims description 14
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- 229910052768 actinide Inorganic materials 0.000 description 1
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- 238000002485 combustion reaction Methods 0.000 description 1
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- B01J8/067—Heating or cooling the reactor
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- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
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Abstract
本发明揭示了一种将乙苯脱氢成为苯乙烯的方法和装置,该方法和装置不需多个反应器和预热器,而是使用紧凑的单个反应器,反应器中具有气体加热器或电气元件之类的内部热源,并利用热量递增热反应器的原理。
Description
本发明涉及苯乙烯的制造，尤其是揭示了乙苯脱氢成为苯乙烯单体的方法和设备，包括反应容器。
在苯乙烯制造领域内，在1000-1230°F的高温和约4-20PSIA压力下，在诸如氧化铁之类的脱氢催化剂存在下使乙苯的苯环上的乙基脱氢形成苯乙烯分子的方法是众所周知的。这通常在一系列辐射形的绝热的苯乙烯反应器内完成的，这些反应器一般被称为乙苯脱氢反应器，这种脱氢反应器通常是直径约为5-30英尺或更大、长约为10-1000英尺或更大的伸长的、圆筒形的、很大尺寸的垂直结构。这种反应器的常规结构是在位于垂直反应器的中心的入口使乙苯气体输入，由此气体径向向外流动通过一个环形区域，通过一个环形的氧化铁或其它适当的脱氢催化剂的多孔催化剂床，然后通过一个外部的环形区域输出反应器壳体。由于穿过催化剂床的乙苯的流动是径向的，这些反应器有时就称为“径向”反应器。
苯乙烯制造行业的技术人员目前认为多重的、带有典型的脱氢催化剂床的径向床乙苯反应器的最佳配置是使用三个或更多个径向绝热反应器，这些反应器在流动方向串联配置，并在这些反应器之间配有再加热装置为该吸热反应提供热量。每一个反应器可以具有选择性与其它反应器的催化剂不同的催化剂。在这些情况下，“选择性”被本领域技术人员认为是指催化剂选择性产生高含量的所需的苯乙烯和低含量的不希望有的甲苯和苯的能力。“活性”是指催化剂将凡是通过催化剂的原料的一定百分比的乙苯转化为芳香族化合物的能力。上面提到的这种常规的径向反应器的例子在Butler等人的美国专利5,358,698中可以找到。
由于传统的乙苯反应器绝热设计及脱氢反应的吸热性，传统的乙苯方法需要在过程中加入热量以维持脱氢反应。这本身又需要使用多重反应器以提供机会在过程中加入热量，这是通过使用处于串联反应器之间的加热器或过热器来完成的。这也是每一个串联反应器使用不同催化剂，使各个串联反应器的催化剂选择性不同的一个原因。由于串联反应器中的乙苯反应的吸热性，通过系统的液体时空速(LHSV)要严格限定。乙苯原料必须足够缓慢地流动通过各反应器以使脱氢基本上完成，脱氢由于反应中的热量吸收而被减缓。
因此，需要一种不需庞大的多重反应器、加热器、热交换器，或多重催化剂，并且也不受低LHSV限制的乙苯脱氢方法。
本发明揭示了一种使用单个小型催化反应器的乙苯脱氢方法和设备，它既不是绝热的，也不是等温的，而事实上是一个热量递增反应器。
附图是反应器的横截面视图和实施本发明的方法流程图。
参看附图，该附图是显示本发明构思的横截面示意图，揭示了热量递增的乙苯反应器10，乙苯反应器10具有被外壳11所限定的反应室，它带有入口集管12和出口集管13。供应管线14与入口集管12相联接而产品流送管15从出口集管13通出。
乙苯反应器10的中心截面包含炉子11，其中放置一系列的产品流动管16，产品流动管16与入口集管12相连。管16的开孔暴露于入口集管12，使乙苯原料通过管道14进入到入口集管12并穿越管道16进入出口集管13。虽然，在此示意图中仅仅揭示了三条这样的管道，但实际上在反应器内可以有很多这样的管道。在管道16上面是许多在炉箱顶部的加热器18。加热器管道18有一个诸如天然气，氢或其它可燃气体之类的燃料源，这些可燃气体是利用燃料入口管道17来提供的，而燃料入口管道17与加热器单元18连通。燃烧产物废料管道19通过室11的壁，并带走来自喷咀24的火焰的燃烧产物。氧气源也可以利用单独的氧气供应管道或空气供应管道来提供，该氧气供应管道或空气供应管道可以单独地与燃烧器管道18相连接，或者可以在进入管道17之前通过一个混合器箱，空气或氧气可以在该处与气体燃料混合。
在典型的操作中，乙苯原料是通过入口管道14输入，并通过反应器管道16。反应管道16的内部可以完全或部分地填有操作者希望用于该方法的乙苯脱氢催化剂。本领域的技术人员会知道可有利地用于本发明的合适的脱氢催化剂。
如前所述，反应器管道16可能完全或部分地填有所需的乙苯脱氢催化剂，使来自人集管12的乙苯原料通过管道16，流经选定的催化剂，并在出口集管13收集。
当乙苯流动通过反应器管道16时，燃料与进入管道17的氧气源的气态混合物通入加热器喷嘴24并喷出。在反应器启动时要提供一个点火源，而气体连续地通过喷嘴24，并在从喷嘴喷出时燃烧。通过少量的实验就可以确定为了得到热量递增热反应器所需使用的特定喷嘴尺寸。因此，当乙苯进入管道14，通过反应室入口集管12进入反应器管道16时，它穿过包含在反应器管道16内的乙苯脱氢催化剂，并由于所消耗的气体燃料而受到数量逐渐加大的热量输入。虽然最好使用气态燃料，但当然也可使用液态燃料，在其进入管道17之前用氧源气体使其雾化。也可用其它常规的喷嘴-加热器装置以消耗不同的燃料源。此外，也可以使用电气加热元件来代替化学驱动的热量供应，这些电气加热元件所产生的热量从反应器入口端至反应器出口端是变化的，以使反应器得到递增的热量供应。因此，本领域的技术人员可用电气加热元件来代替加热管18，这些电气加热元件的热量输出随着接近其末端(与反应器管道16的输出端相关联)而逐渐增大。
但是，本发明最好是使用与围绕乙苯脱氢系统的提纯操作相容的热源，而最易得到的燃料通常是氢或一种压缩天然气，因此本发明是按燃气加热系统来说明的。当乙苯原料穿过反应器16的长度，通过包含在其中的催化剂时，就发生显著的脱氢反应，排出至出口集管的产品主要含有苯乙烯，这产品通过产品流送管15送出，以便进一步纯化，并去除乙苯、苯、甲苯和氢等非苯乙烯产品。如前面所述，由喷嘴24排出的燃烧气体通过加热器箱体底部的废气导管19流出。这里所说明的就是称为热量递增反应器的一种将乙苯脱氢成为苯乙烯的反应器，它可为吸热的乙苯脱氢反应提供热量输入，而且提供的热量随着乙苯脱氢反应趋向结束，反应的组分将用完，反应更难驱动时而逐步增加。
虽然以上说明了本发明的一些较佳实施例，以便理解本发明的一般原理，但应理解，可在不背离这些原理的条件下对所述的脱氢反应器系统作各种变化和改革。也可以使反应器管道的直径沿其长度变化而使通过管道的流率(LHSV)变化。例如，反应器管道可以在入口端较小而在出口端较大，从而使每一反应器管道中的LHSV沿其长度逐渐减小。这可使乙苯反应在管道内的较高温度下有较长的停留时间。另外，也可在相反方向改变管道的直径，使管道在起始端较大而在终了端较小，从而使LHSV沿管道的长度逐渐增大。其它变化对本领域技术人员来说将是显而易见的，因此本发明包括在不背离本发明的实质和范围的条件下，对为了说明目的而揭示的各具体实施例所作的全部变化和改变。
Claims (3)
1.一种将乙苯脱氢成为苯乙烯的方法，它包括：
将乙苯原料通过至少一个含有脱氢催化剂的脱氢反应器管道，并在该管道长度的主要部分加热；以及
在该管上沿着所述原料流动的方向增加热量，使施加于该管的热量改变。
2.如权利要求1所述的方法，其特征还在于所述管道沿其长度具有基本恒定的截面积，热量级别的变化是依靠改变燃烧器的操作来实现的。
3.如权利要求1所述的方法，其特征还在于所述管道的截面积是沿其长度递增或是递减的。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74535696A | 1996-11-08 | 1996-11-08 | |
| US08/745,356 | 1996-11-08 | ||
| US08/745356 | 1996-11-08 |
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| CN1087281C CN1087281C (zh) | 2002-07-10 |
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| EP (1) | EP0841317B1 (zh) |
| JP (1) | JP4215846B2 (zh) |
| CN (1) | CN1087281C (zh) |
| AT (1) | ATE211722T1 (zh) |
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| US6762335B1 (en) * | 2000-02-29 | 2004-07-13 | Fina Technology, Inc. | Apparatus for dehydrogenation of ethylbenzene to styrene |
| US6570905B1 (en) | 2000-11-02 | 2003-05-27 | U-L-M Photonics Gmbh | Vertical cavity surface emitting laser with reduced parasitic capacitance |
| US6380449B1 (en) | 2000-11-22 | 2002-04-30 | Fina Technology, Inc. | Dehydrogenation process |
| US6781024B2 (en) * | 2000-11-22 | 2004-08-24 | Fina Technology, Inc. | Dehydrogenation process |
| US7169960B2 (en) * | 2004-12-22 | 2007-01-30 | Fina Technology, Inc. | Dehydrogenation process |
| CA2645218C (en) | 2006-03-23 | 2014-10-07 | Anna Lee Tonkovich | Process for making styrene using microchannel process technology |
| US7981377B2 (en) * | 2007-11-06 | 2011-07-19 | Fina Technology, Inc. | Dehydrogenation of alkyl aromatics |
| EP2065355A1 (en) | 2007-11-29 | 2009-06-03 | Total Petrochemicals France | Process for cooling the stream leaving an ethylbenzene dehydrogenation reactor |
| DE102008023042A1 (de) | 2008-05-09 | 2009-11-12 | Süd-Chemie AG | Verfahren zur semi-adiabatischen, semi-isothermen Durchführung einer endothermen Reaktion unter Einsatz eines katalytischen Reaktors und Ausbildung dieses Reaktors |
| US7901640B2 (en) * | 2008-05-13 | 2011-03-08 | Uop Llc | Optimized counter-current flow baffle |
| US7906081B2 (en) | 2008-05-13 | 2011-03-15 | Uop Llc | Internal grids for adsorbent chambers and reactors |
| US7718146B2 (en) * | 2008-05-13 | 2010-05-18 | Uop Llc | Enhanced bed separation in a styrene monomer reactor using milled plates |
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| US3288871A (en) * | 1963-08-07 | 1966-11-29 | Dow Chemical Co | Catalytic dehydrogenation of hydrocarbons |
| US3326996A (en) * | 1964-05-06 | 1967-06-20 | Union Carbide Corp | Dehydrogenation of ethylbenzene to styrene |
| US3330878A (en) * | 1964-06-15 | 1967-07-11 | Halcon International Inc | Process for producing styrene |
| US3417156A (en) * | 1966-09-23 | 1968-12-17 | Universal Oil Prod Co | Endothermic catalytic conversion of ethylbenzene to styrene |
| BE789153A (fr) * | 1971-09-23 | 1973-03-22 | Aquitaine Petrole | Perfectionnement a la fabrication du styrene |
| US3755482A (en) * | 1972-03-24 | 1973-08-28 | Dow Chemical Co | Multistage production of styrene |
| US3868428A (en) * | 1973-04-12 | 1975-02-25 | Lummus Co | Process and apparatus for the dehydrogenation of alkylated aromatic hydrocarbons |
| US4229603A (en) * | 1977-04-26 | 1980-10-21 | The Dow Chemical Company | Method of dehydrogenation of alkyl aromatics to alkenyl aromatics |
| DE2909763C2 (de) * | 1979-03-13 | 1982-09-09 | Deggendorfer Werft Und Eisenbau Gmbh, 8360 Deggendorf | Verfahren zur katalytischen einstufigen, isothermen Dehydrierung von Äthylbenzol zu Styrol |
| DE3319024A1 (de) * | 1983-05-26 | 1984-11-29 | Deggendorfer Werft Und Eisenbau Gmbh, 8360 Deggendorf | Verfahren zur herstellung von styrol durch dehydrieren von aethylbenzol |
| US5053572A (en) * | 1989-05-11 | 1991-10-01 | Amoco Corporation | Multistage ethylbenzene dehydrogenation process with split-flow hydrocarbon feed |
| FR2648145B1 (fr) * | 1989-06-08 | 1991-10-04 | Inst Francais Du Petrole | Utilisation d'alliages a base de nickel dans un procede de craquage thermique d'une charge petroliere et reacteur pour la mise en oeuvre du procede |
| US5710356A (en) * | 1994-11-22 | 1998-01-20 | The University Of Kansas | Method of conducting an endothermic reaction in a packed-bed reactor with external energy addition |
-
1997
- 1997-10-24 EP EP97203305A patent/EP0841317B1/en not_active Expired - Lifetime
- 1997-10-24 DK DK97203305T patent/DK0841317T3/da active
- 1997-10-24 AT AT97203305T patent/ATE211722T1/de active
- 1997-10-24 ES ES97203305T patent/ES2169837T3/es not_active Expired - Lifetime
- 1997-10-24 DE DE69709528T patent/DE69709528T2/de not_active Expired - Lifetime
- 1997-11-04 JP JP31771297A patent/JP4215846B2/ja not_active Expired - Lifetime
- 1997-11-07 CN CN97122483A patent/CN1087281C/zh not_active Expired - Fee Related
- 1997-11-10 TW TW086116775A patent/TW448151B/zh not_active IP Right Cessation
-
1999
- 1999-02-08 US US09/195,179 patent/US6096937A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1087281C (zh) | 2002-07-10 |
| JP4215846B2 (ja) | 2009-01-28 |
| DE69709528D1 (de) | 2002-02-14 |
| JPH10175889A (ja) | 1998-06-30 |
| EP0841317A1 (en) | 1998-05-13 |
| US6096937A (en) | 2000-08-01 |
| EP0841317B1 (en) | 2002-01-09 |
| ATE211722T1 (de) | 2002-01-15 |
| DK0841317T3 (da) | 2002-04-29 |
| DE69709528T2 (de) | 2002-08-08 |
| ES2169837T3 (es) | 2002-07-16 |
| TW448151B (en) | 2001-08-01 |
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