CN1182117A - 在沸石催化的烃类芳构化过程中降低生焦速率的方法 - Google Patents
在沸石催化的烃类芳构化过程中降低生焦速率的方法 Download PDFInfo
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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Abstract
一种芳构化方法,其中通过在烃类进料中加入一定浓度的甲硅烷化剂,可显著降低汽油沸程内的烃类在与沸石催化剂接触的芳构化过程中的生焦速率。
Description
降低生焦速率的方法
本发明涉及一种非芳烃在沸石材料存在下转化成芳烃的方法。更具体地说，本发明涉及在沸石材料存在下、在烃类芳构化过程中降低生焦速率、从而提高沸石材料的稳定性的方法。
非芳族的、汽油沸程的烃类在含有沸石如ZSM-5的催化剂存在下催化裂化成低碳烯烃(如乙烯和丙烯)和芳烃(如苯、甲苯和二甲苯)是大家知道的，如N.Y.Chen等在“工业和工程化学过程设计和开发，第25卷，1986年，第151-155页中描述的。这一催化裂化过程的反应产物含有各种烃类：未转化的C5 +烷烃、低碳烷烃(甲烷、乙烷、丙烷)、低碳烯烃(乙烯和丙烯)、C6-C8芳烃(苯、甲苯、二甲苯和乙苯)以及C9 +芳烃。
在汽油沸程的烃类转化成芳烃和低碳烯烃的过程中，一个与使用沸石催化剂有关的问题是，在转化反应过程中生成过多的焦炭。在沸石催化的烃类芳构化过程中生成的焦炭倾向于沉积在沸石的表面，从而使沸石失活。希望通过减少在这样的芳构化反应过程中生成的焦炭量来改进烃类芳构化法。
本发明的一个目的是，将汽油中的烃类至少部分转化成乙烯、丙烯和BTX(苯、甲苯、二甲苯和乙苯)芳烃。
本发明的另一目的是，提供一种改进的烃类芳构化方法，其中使在这样的烃类芳构化过程中的生焦速率降到低于现有芳构化法中的生焦速率。
本发明的另一目的是，提供一种通过将甲硅烷化剂加到芳构化法的烃类进料中来降低沸石催化的烃类芳构化过程中生焦速率的方法。
本发明的方法用于由烃类进料流生产低碳烯烃和芳烃，其在转化反应过程中生焦速率低于其他类似转化过程的生焦速率。含有汽油沸程烃类的进料物流通过在芳构化反应条件下与酸浸析的沸石材料接触来进行芳构化。条件是，在与酸浸析的沸石材料接触的进料物流中有一定浓度的甲硅烷化剂。
本发明的其他目的和优点由发明详述和附后的权利要求书得以清楚说明。
在非芳烃转化成芳烃的过程中，有效的含沸石的任何催化剂都可用于本发明方法的接触反应步骤。优选的是，催化剂的沸石组分的限制性指数(如在US4097367中规定的)在约0.4至约12范围内、优选约2至9。通常，在沸石的晶体骨架中SiO2/Al2O3摩尔比为至少约5∶1，可一直到无限大。沸石骨架中的SiO2/Al2O3摩尔比优选为约8∶1至约200∶1、更优选约12∶1至约60∶1。优选的沸石包括ZSM-5、ZSM-8、ZSM-11、ZSM-12、ZSM-35、ZSM-38及其混合物。这些沸石中的一些也称为“MFI”或“Pentasil”沸石。使用含有硼和/或至少一种选自Ga、In、Zn、Cr、Ge和Sn的金属的沸石也在本发明的范围内。目前更优选的沸石是ZSM-5。
催化剂通常还含有优选选自氧化铝、氧化硅、氧化铝-氧化硅、磷酸铝、白土(如膨润土)及其混合物的无机粘合剂(也称为基质材料)。任选的是，催化剂中也可含有能提高催化剂的热稳定性的其他金属氧化物，如氧化镁、氧化铈、氧化钍、氧化锆、氧化铪、氧化锌及其混合物。优选的是，催化剂基本上不含加氢助催化剂如Ni、Pt、Pd和其他第VIII族贵金属、Ag、Mo、W等(即这些金属的总量应小于约0.1％(重量))。
通常，沸石组分在催化剂中的含量为约1至99(优选约5至80)％(重量)，而上述无机粘合剂和金属氧化物材料在沸石中的含量为约1至50％(重量)。通常，催化剂的沸石组分与粘合剂一起调制，随后再成型如成球、挤条或压片。通常，催化剂的表面积为约50-700米2/克，而粒度为约1至10毫米。
任何含有其中每一分子有5-16个碳原子的烷烃和/或烯烃和/或环烷烃的适合烃类原料都可在本发明的接触反应步骤中用作进料。这些原料常常还含有芳烃。适合的可得原料的非限制性例子包括催化裂化法(如FCC)得到的汽油、烃类(如乙烷)热裂解法得到的裂解汽油、石脑油、瓦斯油、重整油等。优选的进料为适合用作至少一种汽油调合原料的、通常沸程为约30至210℃的汽油沸程的烃类原料。通常，烷烃的含量超过烯烃、环烷烃和芳烃(如果有的话)的总含量。
烃类进料物料可用任何适合的方式与本发明反应段内的含沸石的固体催化剂接触。接触反应步骤可为间歇工艺步骤，或优选为连续工艺步骤。在后一操作中，可采用固定催化剂床，或移动催化剂床或流化催化剂床。这些操作方式中任一种都有优点和缺点，熟悉本专业的技术人员可根据特定的进料和催化剂选择一种最适合的。不需要大量氢气与进料一起送入接触步骤的反应段，也就是根本没有氢气或只有很微量的对过程没有明显影响的氢气(如小于约1ppm氢气)从外面的来源送入这些反应器。
本方法的一个重要方面是在与本发明芳构化反应段内的沸石催化利接触的烃类进料物流中加入一定浓度的甲硅烷化剂。现已发现，在沸石催化的烃类原料的芳构化过程中，当一定浓度的甲硅烷化剂在原料中存在时，生焦速率明显降低。本发明的关键是，在芳构化反应条件下，烃类原料与沸石催化剂接触时，甲硅烷化剂在烃类原料中的存在。在用作芳构化催化剂以前，预先用甲硅烷化剂改性的沸石的使用不能得到这种生焦速率的降低，这种生焦速率的降低是由在芳构化反应条件下与沸石催化剂接触的烃类进料有一定浓度的甲硅烷化剂的新方法得到。
在本发明方法中使用的甲硅烷化剂可为任何一种在适合于烃类芳构化的反应条件下加到与沸石接触的烃类原料中时能有效降低生焦速率的适合的含硅化合物。更具体地说，甲硅烷化剂是选自有以下分子式的化合物的有机硅化合物：
SiRyX4-y和(RwX3-wSi)2-Z式中，y＝1-4；w＝1-3；R＝烷基、芳基、H、烷氧基、芳烷基，R有1-10个碳原子；X＝卤根；Z＝氧或NH或取代的胺或酰胺。
优选甲硅烷化剂选自原硅酸四烷基酯(Si(OR)4)和聚(烷基)硅氧烷。最优选的甲硅烷化剂为原硅酸四乙酯和聚(苯基甲基)硅氧烷。
甲硅烷化剂在芳构化反应段中与沸石催化剂接触的烃类进料中的浓度应足以使生焦速率降低到当进料中没有甲硅烷化剂时的生焦速率以下。甲硅烷化剂在烃类进料中的有效浓度可是这样的，以致按烃类的总重计，硅存在数量在至多约50％(重量)硅范围内。优选的是，硅的浓度可为约0.1至约80％(重量)、最优选0.1-10％(重量)。
接触步骤在装有沸石催化剂的芳构化反应段中，在适合促进烃类进料中至少一部分烃类芳构化的反应条件下进行。接触步骤的反应温度为约400至约800℃、优选约450至约750℃、最优选500-700℃。接触压力可为常压至约500磅/吋2、优选约20至约450磅/吋2、最优选50-400磅/吋2。
烃类进料送入芳构化反应的流速可为这样的，以致使重时空速(“WHSV”)在0至约1000小时-1。在这里使用的术语“重时空速”指烃类进料送入反应段以磅/小时表示的速率除以烃类送入的反应段中所装催化剂的磅数的数值的比值。进料送入接触段的优选WHSV为约0.25至约250小时-1、最优选0.5-100小时-1。
本发明一个特别优选的实施方案是，使用在与含一定浓度的甲硅烷化剂的烃类进料接触以前先进行了酸处理的沸石催化剂。任何适合的方法都可用来酸处理沸石催化剂，但优选用任何一种本专业中用于沸石与酸溶液接触的已知适合方法，用酸溶液浸泡沸石。酸溶液中的酸可为任何一种适用于从沸石结晶结构中浸析出铝的酸。酸溶液优选为盐酸水溶液。沸石在酸中浸泡约0.25至约10小时。浸泡后，沸石洗至不含酸，然后干燥，任选焙烧。
用以下实施例进一步说明本发明，不应把这些实施例作为对本发明范围的限制。
实施例I
本实施例描述用于实施例II的芳构化反应操作的沸石的两种制品。
用酸浸析法处理商购的ZSM-5催化剂(由联合催化剂有限公司提供，商品名“T-4480”)。为了酸浸析催化剂，将它浸泡在盐酸水溶液中，其浓度为19％(重量)HCl，在约90℃下浸泡2小时。浸泡后，将催化剂从酸溶液中分出，并用水彻底洗涤和干燥。经酸浸泡、洗涤和干燥的催化剂在约500℃下焙烧4小时。将这种经酸浸析的ZSM-5催化剂用于如下文所述的芳构化反应操作中，以测定其生焦速率。
上述经酸浸析的ZSM-5沸石用开始润湿技术，用50％(重量)聚(甲基苯基)硅氧烷的环己烷溶液浸渍的方法，用甲硅烷化剂处理。经浸渍、酸浸析的ZSM-5干燥2小时，随后在530℃下焙烧6小时。将这种经甲硅烷化和焙烧的酸浸析的ZSM-5催化剂用于如下文所述的芳构化反应操作，以测定其生焦速率。
实施例II
该实施例说明由本发明的方法、通过含有一定浓度的甲硅烷化剂的烃类原料与沸石接触的结果使生焦速率降低的好处。实施例I的两种沸石制品用于三个芳构化反应操作，其结果汇于表I。酸浸析的沸石和甲硅烷化的酸浸析的沸石为基准情况的沸石催化剂，本发明方法的结果与它们进行了比较。
对于每一芳构化试验来说，5克特定沸石催化剂样与约5毫升10-20目氧化铝混合，放入不锈钢管式反应器中(长约18吋；内径约0.5吋)。炼油厂催化裂化操作得到的汽油在约600℃和常压下，以约14毫升/小时的流速通过反应器。生成的反应产物流出反应器，并通过几个冰冷却阱。液体部分留在这些冷阱中，并称重，而用湿式流量计测量流出冷阱的气体部分的体积。定期收集液体和气体产物样，并用气相色谱法分析。反应操作完成后，通过测量沉积在催化剂表面上的焦炭数量来测定生焦速率。
在本发明的操作中，使用经酸浸析的沸石催化剂。送入反应器的初始进料中，每2体积份原硅酸四甲酯(TEOS)含5体积份汽油进料，并以约12毫升/小时的速率进料2小时。随后，将不含TEOS的汽油进料以14毫升/小时的速率给反应器进料6小时。
表I
| 催化剂 | 生焦速率，％(重量)/小时 |
| 酸浸析的沸石 | 1.74 |
| 甲硅烷化的酸浸析的沸石 | 0.46 |
| TEOS加到与酸浸析的沸石接触的进料中 | 0.17 |
正如可从表I所列生焦速率数据看出的那样，甲硅烷化的酸浸析沸石在烃类芳构化中的应用比酸浸析的沸石得到更低的生焦速率。而且，甲硅烷化剂加到在芳构化过程中与酸浸析的沸石接触的进料中，与甲硅烷化的酸浸析的沸石相比，生焦速率甚至有更加显著的降低。
在不违背本发明的范围的条件下，可在本发明的公开内容和附后的权利要求书范围内，作出各种变通方案、改进和对各种操作和条件的修改。
Claims (14)
1.一种使含有在汽油沸程内的烃类进料中的烃类芳构化的方法，所述的方法包括，
将一定浓度的甲硅烷化剂加到所述的进料物流中；以及
使含有所述浓度的所述甲硅烷化剂的所述的进料流与经酸浸析的沸石在芳构化反应条件下接触。
2.根据权利要求1的方法，其中所述进料物流中烃类的沸程为约30至约210℃。
3.根据权利要求2的方法，其中所述甲硅烷化剂在所述进料物流中的所述浓度能有效降低在所述进料流中的烃类芳构化过程中的生焦速率。
4.根据权利要求2的方法，其中所述甲硅烷化剂在所述进料流中的所述浓度是这样的，以致硅的数量为所述进料流的烃类的至多约50％(重量)。
5.根据权利要求4的方法，其中所述的甲硅烷化剂为有机硅化合物。
6.根据权利要求5的方法，其中所述的接触反应步骤得到含有芳烃的产物流。
7.根据权利要求6的方法，其中所述的有机硅化合物选自原硅酸四烷基酯和聚(烷基)硅氧烷。
8.根据权利要求7的方法，其中所述的原硅酸四烷基酯为原硅酸四乙基酯，而所述的聚(烷基)硅氧烷是聚(苯基甲基)硅氧烷。
9.一种降低在烃类芳构化中的生焦速率的方法，所述的方法包括：
在芳构化反应条件下，使烃类进料流与经酸浸析的沸石接触；以及
将在所述烃类进料的芳构化过程中能有效降低生焦速率的甲硅烷化剂的有效量加到烃类进料流中。
10.根据权利要求9的方法，其中所述烃类进料流的沸程为约30至210℃。
11.根据权利要求10的方法，其中甲硅烷化剂在所述烃类进料流中的数量是这样的，以致按烃类进料流中的烃类重量计，硅的浓度为至多50％(重量)。
12.根据权利要求11的方法，其中甲硅烷化剂为有机硅化合物。
13.根据权利要求12的方法，其中所述的有机硅化合物选自原硅酸四烷基酯和聚(烷基)硅氧烷。
14.根据权利要求13的方法，其中所述的原硅酸四烷基酯化合物为原硅酸四乙基酯，而所述的聚(烷基)硅氧烷为聚(苯基甲基)硅氧烷。
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| US5942443A (en) | 1996-06-28 | 1999-08-24 | Caliper Technologies Corporation | High throughput screening assay systems in microscale fluidic devices |
| US5945364A (en) * | 1996-06-26 | 1999-08-31 | Phillips Petroleum Company | Catalyst composition comprising acid-base leached zeolites |
| US5800696A (en) * | 1996-11-12 | 1998-09-01 | Phillips Petroleum Company | Method for inhibiting the rate of coke formation during the zeolite catalyzed aromatization of hydrocarbons |
| US5873994A (en) * | 1997-07-15 | 1999-02-23 | Phillips Petroleum Company | Process for aromatization of a cracked gasoline feedstock using a catalyst containing an acid leached zeolite and tin |
| WO2000015338A1 (en) * | 1998-09-16 | 2000-03-23 | Phillips Petroleum Company | An improved zeolite |
| WO2000024509A1 (en) * | 1998-10-27 | 2000-05-04 | Phillips Petroleum Company | Method of making a zeolite catalyst and using the catalyst in a hydrocarbon conversion process |
| US6066770A (en) * | 1998-11-05 | 2000-05-23 | Phillips Petroleum Company | Selectivated zeolitic hydrocarbon conversion catalyst |
| CN1298425C (zh) * | 2004-12-01 | 2007-02-07 | 中国石油化工集团公司 | 一种芳构化催化剂及其制备方法和应用 |
| US20060219598A1 (en) * | 2005-01-10 | 2006-10-05 | Cody Ian A | Low energy surfaces for reduced corrosion and fouling |
| US20130237734A1 (en) * | 2012-03-07 | 2013-09-12 | Chevron Phillips Chemical Company Lp | Aromatization Catalyst and Methods of Preparing Same |
| JP7239100B2 (ja) * | 2018-09-03 | 2023-03-14 | Ｅｎｅｏｓ株式会社 | 炭素数６～８の単環芳香族炭化水素の製造方法 |
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| US4097367A (en) * | 1977-07-25 | 1978-06-27 | Mobil Oil Corporation | Conversion of olefinic naphtha |
| US4390414A (en) * | 1981-12-16 | 1983-06-28 | Exxon Research And Engineering Co. | Selective dewaxing of hydrocarbon oil using surface-modified zeolites |
| US4548914A (en) * | 1983-08-26 | 1985-10-22 | Mobil Oil Corporation | Zeolite catalysts of improved activity and para-selectivity |
| US4677094A (en) * | 1986-09-22 | 1987-06-30 | Uop Inc. | Trimetallic reforming catalyst |
| US4983274A (en) * | 1986-12-04 | 1991-01-08 | Mobil Oil Corp. | Shape selective crystalline silicate zeolite containing intermetallic component and use as catalyst in hydrocarbon conversions |
| US4849386A (en) * | 1987-04-08 | 1989-07-18 | Taiwan Styrene Monomer Corporation | Novel silicon-modified catalyst Si/HZSM-5 preparation |
| US4835336A (en) * | 1987-12-31 | 1989-05-30 | Mobil Oil Corporation | Method for suppressing hydrogenolysis of noble metal/low acidity zeolites |
| US4985135A (en) * | 1988-12-30 | 1991-01-15 | Exxon Research And Engineering Company | Surface silylated zeolite cataysts, and processes for the preparation, and use of said catalysts in the production of high octane gasoline |
| US4950835A (en) * | 1989-10-24 | 1990-08-21 | Taiwan Styrene Monomer Corporation | Novel silicon-modified catalyst Si/HZSM-5, it's preparation, and a process for synthesizing high purity p-dialkyl benzene from monoalkyl benzene by using said catalyst |
| GB8924410D0 (en) * | 1989-10-30 | 1989-12-20 | Exxon Chemical Patents Inc | Zeolite l |
| US5382696A (en) * | 1992-10-16 | 1995-01-17 | Mitsui Toatsu Chemicals, Incorporated | Method for preparing methylamines |
| US5300469A (en) * | 1992-12-08 | 1994-04-05 | Engelhard Corporation | Composition for passivating vanadium in catalytic cracking and preparation thereof |
| US5349113A (en) * | 1993-02-25 | 1994-09-20 | Mobil Oil Corp. | Shape selective hydrocarbon conversion over pre-selectivated, activated catalyst |
| US5476823A (en) * | 1993-05-28 | 1995-12-19 | Mobil Oil Corp. | Method of preparation of ex situ selectivated zeolite catalysts for enhanced shape selective applications and method to increase the activity thereof |
| US5800696A (en) * | 1996-11-12 | 1998-09-01 | Phillips Petroleum Company | Method for inhibiting the rate of coke formation during the zeolite catalyzed aromatization of hydrocarbons |
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| CA2218763A1 (en) | 1998-05-12 |
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| US5925237A (en) | 1999-07-20 |
| KR19980042252A (ko) | 1998-08-17 |
| EP0841387A3 (en) | 1998-07-29 |
| TW396151B (en) | 2000-07-01 |
| EP0841387B1 (en) | 2003-10-08 |
| EP0841387A2 (en) | 1998-05-13 |
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