CN1759083A - 在碳氢化合物物流中炔烃和二烯烃的选择加氢 - Google Patents
在碳氢化合物物流中炔烃和二烯烃的选择加氢 Download PDFInfo
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Abstract
在下流式沸点反应器中，氢化含氢、甲烷、C2－C6烯烃和烷烃、C2－C6炔烃和二烯烃、苯、甲苯、二甲苯及其他C6+组份物流中的炔烃和二烯烃，其中反应热为产生蒸气的反应器中的液体所吸收。除送到反应器的进料以外，还有以足够速度加入的再循环物流以保证润湿反应器之内的催化剂粒子。加入取自下游蒸馏塔的第三物流，以提供相当于反应器中蒸发质量的补给质量。该第三物流的组成控制流过该反应器的液体的稳态组成。
Description
发明背景
发明领域
本发明涉及一种在碳氢化合物物流中炔烃和二烯烃选择氢化的方法。更特别，本发明涉及一种使用下流式沸点反应器在含氢、烯烃和较少量炔烃和二烯烃的碳氢化合物物流中炔烃和二烯烃的选择加氢。
相关信息
来自碳氢化合物蒸汽裂化装置骤冷系统的蒸气产品流通常由氢、甲烷、C2-C6烯烃和烷烃、C2-C6炔烃和二烯烃、苯、甲苯、二甲苯及其他C6+组份组成。在高压低温室体系中首先将氢与甲烷分离以后，通常在连续的蒸馏装置中实现根据碳数分离和回收产品。由于同样碳数的烯烃、炔烃和二烯烃的相对挥发度差异很小的事实，使生产纯烯烃产品很困难，从而使蒸馏装置的结构复杂化。一种解决该问题的方法是首先分离碳数馏分，然后选择加氢处理每一馏分使乙炔和/或二烯转变为其对应的烯烃或者烷烃。通常所说的“后端”方法需要单独的对于每一碳数馏分的加氢处理体系以及将需要量的氢加入到每一体系中。另外的方法是使用包含的氢作为转化氢源分离之前加氢处理该原料流。该所谓的“前端”方法具有从送入该低温室的原料流中除去大量份额的氢，因此减少了低温室的尺寸和需冷量。
发明内容
本发明提供一种“前端”加氢处理体系，所述的体系可有效控制在催化剂床之内的温度，所述的催化剂用于氢化含氢、甲烷、C2-C6烯烃和烷烃、C2-C6炔烃和二烯烃、苯、甲苯、二甲苯及其他C6+组份物流中的炔烃和二烯烃。本发明利用下流式沸点反应器，其中反应热被生产蒸气的反应器中的液体所吸收。除被送到反应器的进料以外，还有以足够的速度加入的再循环物流以保证润湿反应器之内的催化剂粒子。取自下游蒸馏塔的第三物流被加入提供相当于反应器中蒸发质量的补给质量。第三物流的组成控制流过该反应器的液体的稳态组成。该物流的组成可以通过选择距从其中引出物流的下游蒸馏塔的点进行控制。在塔中引出点越低，在第三物流中该组份的沸点就越高。流过该反应器液体的稳态组成以及压力决定反应器的温度分布图。
在“沸点反应器”中，总是保持液相，即使反应组分由于反应放出的热被蒸发。在任何反应中，反应流可能被蒸发，可能加入惰性较高沸点组分以保持液相。
附图简述
图1是本发明一个实施方式的示意形式的流程图。
图2是图示典型的本发明反应器中的温度分布图。
优选实施方式的详细描述
用于炔烃和二烯烃选择加氢的催化剂包括负载于氧化铝上的氧化钯。一种这样的催化剂包括负载于1/8英寸小球上的0.34wt％的钯，命名为G68C，由Sud-Chemie(以前的United catalyst Inc.)提供。另外的催化剂包括负载于8-12目小球上的0.5wt％的钯，命名为E144SDU，如由Mallinckrodt，Inc的catalyst and Performance Chemicals Division提供的Calcicat。对于最好的结果，催化剂负载于规整填料上，如公开在共同拥有的US5,730,843中。然而该催化剂可简单地装填到反应器中。
现在参考图1，在下流式沸点反应器中进行含比炔烃和二烯烃明显更大量的(摩尔基准)氢和烯烃的碳氢化合物物流中炔烃和二烯烃的选择加氢。显示为塔10的下流式沸点反应器是垂直布置的包含负载于规整填料12上的颗粒催化剂的反应器。气态原料流通过流动管线101加入到塔10的顶端。同样被送到反应器顶端的是在流动管线104中的液体，所述的液体是在流动管线102中的循环物流和来自蒸馏塔40的流动管线103中的物流的混合物，如下更具体的描述。气体和液流同时向下流动通过塔，流动方式是气体连续。气体和液体的并流流动消除了反应失控的可能性。
反应器10绝热操作，以使反应热用于优先蒸发轻的液相组份。来自反应器的流动管线105中的流出物被送到汽液分离器20中，其中分离该蒸气和液体。流动管线106中蒸气的热量包括在反应器10中产生的反应热，而其质量速率等于流动管线101和103中物流的混合流，如下所述更少的滑流107。流动管线102中的液体返回到反应器10的顶部。流动管线102中物流的流速是变化的，要保持至少足够的流速以保证在反应器10中所有位置催化剂粒子被充分润湿。流动管线103中的物流提供相当于反应器中蒸发质量的补给质量，所述蒸发的质量作为流动管线106物流的一部分离开该反应器体系。流动管线103物流的组成控制流过该反应器10液体的稳态组成。这是一个重要的操作参数，它与反应器压力结合决定反应器温度分布图。通过流动管线107取出滑流以控制汽液分离器容器20中的液体容量。
塔40是C5/C6分流器。进入塔的进料是来自分离器20流动管线106中的蒸气。它由在交换器30中与流动管线103中的再循环物流间接热交换而加热。塔40设计为通过流动管线108回收基本上没有C6+组份的蒸气馏出物馏分，和基本上没有C5和轻组份的流动管线109中的塔底液体产物。通过流动管线130取出塔顶馏出物并通过部分冷凝器50，其中冷凝较重组分。在接收器分离器60中收集塔顶馏出物，其中通过流动管线120抽取液态烃并作为回流返回到塔40中。通过流动管线110取出水。如指出的，通过流动管线108除去馏出物产物。
流动管线103中的再循环物流的抽出位置或者塔盘是操作变量。将取出点移动到塔下游更远的位置可增加物流中的高沸组分。当从塔40底部段抽出时，可实现在固定温度曲线下反应器10最低的工作压力。
实施例
加入到图1描述体系中的进料是来自生产烯烃的蒸汽裂化装置骤冷塔的，在压缩和去除酸性气(CO2和H2S)之后的蒸气产物。该反应器装填有大约14,000英尺3的负载氢化催化剂的规整填料。床尺寸大约为15英尺直径×70英尺长。反应器的操作条件是：反应器顶部底部压力为250/240psia；液体循环速率(流动管线102中的物流)为4,000,000Lbs/hr；流动管线107中的滑流为2243Lbs/hr。蒸馏塔40是配置为16.4英尺直径20段(理论上的)顶部部分和10.5英尺20段(理论上的)底部部分。蒸馏塔40的设计条件是：回流比0.18；回流温度136°F；凝汽器压力238psia；柱压降2psi；底部段侧线馏分；倾析器温度84°F。表1中列出热量和物料平衡结果。图2中给出了整个反应器之间的温度变化曲线。
表1
热量和物料平衡
| 101 | 102 | 103 | 104 | 105 | 106 | 107 | 108 | 109 | 110 | |
| 温度F压力psi蒸气馏分摩尔流量lbmol/hr质量流量lb/hr体积流量cuft/hr焓 MMBtu/hr质量流量lb/hrH2Co甲烷乙炔乙烯乙烷甲基乙炔丙二烯丙烯丙烷丁二烯叔丁烯1-丁烯顺2-丁烯异丁烯异丁烷丁烷1-戊烯己烯辛烷苯甲苯间二甲苯邻二甲苯对二甲苯乙苯苯乙烯水PD异戊二烯己二烯庚烯戊烷 | 132250129,994.6808,116.0718,016.6-37.89,260.11,540,9118,468.54,280.8242.593.752743.45,139.05,197.5141,595.44006.440,018.215317.015672.915148.415705.26571.86,368.837318.510179.21895.827,486.77,304.754.941.558.972534.04,266.78,127.77,499.24,147.50.00.0 | 221.4250052453.14,000,00094,069-34.511958928620349,95214,7056662,58387,2813,9966,17223,50369,51125,18020.5257,59110,212140,912471,367230,3871,826,330782.0279,3527,6189,86011,6036,29311,29971562285,00056,10718,965 | 241.425003,537.9290,0006,677-1.4000000000000010002.35664,8316,998167,10029,107157112170215907262911,0447,337419 | 222.8250055,991.04,290,000100,746-35.9119589,28620349,95214,7056662,58387,2813,9966,17223,50369,51125,18120,5257,59110,212143,268536,198237,3861,993,430811,1339,5097,72910,02911,8186.38311,30674265196,04463,44419,384 | 221.42400.37984,546.95,098,120995,976-73.76,4791,599127,755978293,90070,0451,4105,743233,19610,55610,55738,820121,64140,33036,23014,16317,104190,449546,377239,2812,020,920818,4379,5657,77110,08911,8926,41715,57396680898,17265,51225,388 | 221.4240132,064.41,095,870901,853-39.26,3601,541118,463775243,92055,3327443,158145,8666,5584,38215,30452,09115,136156946,5888,88649,45774,7468,764193,56035,9712071492232821214,26825018513,1249,3746,412 | 221.4240029.42,243530.000502880149231339141246792641291,02443954674600483111 | 83.723827,809.5757,208615,020-115.66,3601,541118,468775243,94855,3407443,160145,9156,5604,38515,31752,13015,14915,7056,5726,89246,9781,66902270000001,2442221546571,1305,967 | 405.92400578.647,8851,3236.0000000000000000002038,5091,89527,2587,30355425973341331,47293937 | 83.72380167.83,02249-20.600000000000000000000000000003,02200000 |
Claims (9)
1.一种氢化含氢、甲烷、C2-C6烯烃和烷烃、C2-C6炔烃和二烯烃、苯、甲苯、二甲苯及其他C6+组份物流中炔烃和二烯烃的方法，包括将所述的物流通过包含于下流式沸点反应器中的氢化催化剂，其中反应器在反应器中混合物的沸点下操作，反应热被煮沸液体所吸收，其中炔烃和二烯烃的一部分转变为它们对应的同样碳数的烯烃和烷烃。
2.根据权利要求1的方法，其中分离来自所述下流式沸点反应器流出物中的液体和蒸气，一部分液体循环回到所述下流式沸点反应器的顶部。
3.根据权利要求2的方法，其中保持足够的循环液体量以保证在所述下流式沸点反应器之内所有位置的催化剂被充分润湿。
4.根据权利要求2的方法，其中所述流出物中的蒸气被送到C5/C6分流器中，其中C5及轻物料作为塔顶馏出物移出，C6及重物料作为塔底产物引出。
5.根据权利要求4的方法，其中侧线馏分取自所述的C5/C6分流器，并被送到所述下流式沸点反应器的顶部。
6.根据权利要求5的方法，其中在所述下流式沸点反应器中，流动液体的稳态组成由沿所述C5/C6分流器高度的所述侧线馏分的引出点的位置控制。
7.根据权利要求6的方法，其中所述的侧线馏分由所述的C5/C6分流器底部段引出。
8.一种氢化含氢、甲烷、C2-C6烯烃和烷烃、C2-C6炔烃和二烯烃、苯、甲苯、二甲苯及其他C6+组份物流中炔烃和二烯烃的方法，包括如下步骤：
(a)将所述的物流通过包含于下流式沸点反应器中的氢化催化剂，其中反应器在反应器中混合物的沸点下操作，反应热被煮沸液体所吸收，其中炔烃和二烯烃的一部分转变为它们对应的同样碳数的烯烃和烷烃；
(b)分离包含于来自所述下流式沸点反应器流出物中的液体和蒸气；
(c)将一部分分离的液体返回到所述的下流式沸点反应器的顶部；
(d)保持返回液体的量以保证在所述下流式沸点反应器之内的催化剂在所有位置处被充分润湿；
(e)将所述流出物中的蒸气加入C5/C6分流器，其中C5及轻物料作为塔顶馏出物引出，及C6和重物料作为塔底产物引出；
(f)从所述的C5/C6分流器引出侧线馏分，并将所述侧线馏分加入到所述下流式沸点反应器的顶部；和
(g)通过选择沿所述C5/C6分流器高度的所述侧线馏分的位置，从而控制所述下流式沸点反应器中流动液体的稳态组成。
9.根据权利要求8的方法，其中所述侧线馏分由所述的C5/C6分流器底部段引出。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/385,677 | 2003-03-12 | ||
| US10/385,677 US6867338B2 (en) | 2002-03-15 | 2003-03-12 | Selective hydrogenation of acetylenes and dienes in a hydrocarbon stream |
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| Publication Number | Publication Date |
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| CN1759083A true CN1759083A (zh) | 2006-04-12 |
| CN100371305C CN100371305C (zh) | 2008-02-27 |
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| US (2) | US6867338B2 (zh) |
| EP (1) | EP1618082A2 (zh) |
| JP (1) | JP2006522120A (zh) |
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| PL (1) | PL378808A1 (zh) |
| RU (1) | RU2325429C2 (zh) |
| WO (1) | WO2004081149A2 (zh) |
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| US20040030207A1 (en) * | 2002-08-08 | 2004-02-12 | Catalytic Distillation Technologies | Selective hydrogenation of acetylenes |
| US7022645B2 (en) * | 2003-08-04 | 2006-04-04 | Catalytic Distillation Technologies | Ni hydrogenation catalysts, manufacture and use |
| US20060173224A1 (en) * | 2005-02-01 | 2006-08-03 | Catalytic Distillation Technologies | Process and catalyst for selective hydrogenation of dienes and acetylenes |
| JP4845172B2 (ja) * | 2005-03-30 | 2011-12-28 | 月島機械株式会社 | 有機化合物の断熱冷却式晶析方法及び装置 |
| US7408090B2 (en) * | 2005-04-07 | 2008-08-05 | Catalytic Distillation Technologies | Method of operating downflow boiling point reactors in the selective hydrogenation of acetylenes and dienes |
| US8471082B2 (en) * | 2008-03-14 | 2013-06-25 | Catalytic Distillation Technologies | Process for converting methane to ethylene |
| EP2223987A1 (en) * | 2009-02-17 | 2010-09-01 | ISP Marl GmbH | Purification of an aromatic fraction containing acetylenes by selective hydrogenation of the acetylenes |
| US20120209042A1 (en) | 2011-02-10 | 2012-08-16 | Saudi Basic Industries Corporation | Liquid Phase Hydrogenation of Alkynes |
| US9695096B2 (en) * | 2012-07-12 | 2017-07-04 | Lummus Technology Inc. | More energy efficient C5 hydrogenation process |
| JP6298438B2 (ja) * | 2014-11-28 | 2018-03-20 | 旭化成株式会社 | 炭化水素の製造方法 |
| FR3045651B1 (fr) * | 2015-12-22 | 2018-01-19 | IFP Energies Nouvelles | Procede d'hydrogenation selective de charges olefiniques avec un seuil reacteur principalet un reacteur de garde de taille reduite |
| RU2673550C1 (ru) * | 2018-05-15 | 2018-11-28 | Публичное Акционерное Общество "Нижнекамскнефтехим" | Способ совместного получения циклогексана и гексанового растворителя |
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| US4283271A (en) | 1980-06-12 | 1981-08-11 | Mobil Oil Corporation | Manufacture of hydrocracked low pour lubricating oils |
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| US5011593A (en) | 1989-11-20 | 1991-04-30 | Mobil Oil Corporation | Catalytic hydrodesulfurization |
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- 2004-03-04 CN CNB2004800064972A patent/CN100371305C/zh not_active Expired - Fee Related
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| WO2004081149A3 (en) | 2005-01-13 |
| EG23539A (en) | 2006-04-26 |
| RU2325429C2 (ru) | 2008-05-27 |
| CA2518260A1 (en) | 2004-09-23 |
| AU2004219723A1 (en) | 2004-09-23 |
| US20030233017A1 (en) | 2003-12-18 |
| US7368617B2 (en) | 2008-05-06 |
| KR20050106112A (ko) | 2005-11-08 |
| RU2005131579A (ru) | 2006-02-10 |
| EP1618082A2 (en) | 2006-01-25 |
| JP2006522120A (ja) | 2006-09-28 |
| CN100371305C (zh) | 2008-02-27 |
| PL378808A1 (pl) | 2006-05-15 |
| US20050090701A1 (en) | 2005-04-28 |
| MXPA05009270A (es) | 2005-10-19 |
| BRPI0400329A (pt) | 2005-01-04 |
| AR043554A1 (es) | 2005-08-03 |
| US6867338B2 (en) | 2005-03-15 |
| WO2004081149A2 (en) | 2004-09-23 |
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