CN110913986A - 用于将重质重整产物转化成二甲苯的沸石复合催化剂 - Google Patents
用于将重质重整产物转化成二甲苯的沸石复合催化剂 Download PDFInfo
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- CN110913986A CN110913986A CN201880039999.7A CN201880039999A CN110913986A CN 110913986 A CN110913986 A CN 110913986A CN 201880039999 A CN201880039999 A CN 201880039999A CN 110913986 A CN110913986 A CN 110913986A
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- zeolite
- catalyst
- composite catalyst
- zeolite composite
- solution
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Images
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Abstract
提供沸石复合催化剂和生产所述沸石复合催化剂的方法的实施例,其中所述方法包含在加热、搅拌或同时加热和搅拌时将包含至少一种中孔沸石的催化剂前体溶解在碱性溶液中以产生溶解的沸石溶液,其中所述中孔沸石的SiO2/Al2O3摩尔比为至少30,其中所述中孔沸石包含β沸石;调节所述溶解的沸石溶液的pH;使pH调节后的溶解的沸石溶液老化,以由所述溶解的沸石溶液产生固体沸石复合材料;和煅烧所述固体沸石复合材料以生产所述沸石复合催化剂,其中所述沸石复合催化剂具有包含至少一种无序中间相和至少一种有序中间相的介观结构,并且其中所述沸石复合催化剂具有通过Brunauer‑Emmett‑Teller(BET)分析定义的至少600m2/g的表面积。
Description
相关申请的交叉引用
本申请要求于2017年6月15日提交的题为“用于将重质重整产物转化成二甲苯的沸石复合催化剂(ZEOLITE COMPOSITE CATALYSTS FOR CONVERSION OF HEAVY REFORMATETO XYLENES)”的美国专利申请号15/624090(案号SA 6010PA)的优先权,其内容以全文引用的方式并入本文中。
技术领域
本说明书的实施例通常涉及沸石复合催化剂,并且具体地说,涉及沸石复合催化剂以及使用其将重质重整产物转化成二甲苯的方法。
背景技术
衍生自石化来源的芳香族烃化合物,苯(C6H6)、甲苯(甲基苯,C7H8)和二甲苯(二甲基苯,C8H10异构体)可用作多种消费产品的起始材料。二甲苯包括二甲基苯的三种异构体,即:1,2-二甲基苯(邻二甲苯或o-二甲苯)、1,3-二甲基苯(间二甲苯或m-二甲苯)和1,4-二甲基苯(对二甲苯或p-二甲苯)。二甲苯的三种异构体可用于合成许多有用的产品。举例来说,在氧化时,p-二甲苯异构体产生对苯二甲酸,其可用于制造聚酯塑料和合成纺织纤维(如Dacron)、膜(如Mylar)和树脂(如聚对苯二甲酸乙二醇酯,用于制备塑料瓶)。m-二甲苯异构体可用于制造例如增塑剂、偶氮染料和木材防腐剂。o-二甲苯异构体可用作邻苯二甲酸酐生产的原料,所述邻苯二甲酸酐又可用于制备聚酯、烷基树脂和PVC增塑剂。因此,随着聚酯纤维和聚对苯二甲酸乙二醇酯的市场继续表现出高增长率,对于二甲苯的需求仍然强烈。
几个国家的环境法规限制可共混到汽油池中的芳烃的量。汽油中的大多数芳烃都源自石脑油的催化重整。汽油中所含的芳香族烃化合物通常具有较高的辛烷值,并且由于其高热值而作为汽油基底表现优异。其中,甲苯和芳香族烃化合物,尤其是具有八个碳原子的那些芳香族烃化合物,具有较高的辛烷值和驱动性水平,因此,期望增加汽油中的C8芳香族化合物的体积。石脑油的轻质重整产物被共混到汽油中,因为它具有高辛烷值和较低沸点;然而,环境法规排除汽油中大量的重质重整产物,因此使重质重整产物可供用于其它地方。
典型地,重质重整产物含有90重量(wt)%至95wt%C9和5wt%至10wt%C10芳香族化合物。在C9组分中,三甲基苯(TMB)(50wt%至60wt%)和甲基乙基苯(MEB)(30wt%至40wt%)为主要成分。经济上可行的选择中的一个为将重质重整产物中的重质芳烃转化成有价值的产物,如二甲苯。对二甲苯衍生物的需求比对苯衍生物的需求增长得更快。因此,以苯产率为代价提高二甲苯产率为有利的目标。
重质重整产物可单独或与C7(甲苯)一起进行烷基转移以生产二甲苯(C8)和苯(C6)。因为在重质重整产物中可存在许多不同的化合物,所以可发生多个平行和连续的反应。用于将芳香族烃化合物转化成具有不同碳原子数的化合物的烷基转移反应可包括甲苯的歧化反应,即,两个甲苯分子反应以形成一个苯分子和一个二甲苯分子(通过将甲基从一个甲苯分子转移到另一个甲苯分子,烷基转移反应)。然而,烷基转移反应不限于甲苯的歧化。增加二甲苯产率的其它方法通过由将具有九个或更多个碳原子的芳香族烃化合物添加到起始材料中来诱导烷基转移而运作,得到如将一摩尔甲苯添加到一摩尔C9芳香族烃以生产两摩尔二甲苯的反应。这些平行和连续的反应方法还可伴随有多种化学平衡,包括二甲苯、TMB和MEB的异构化。烷基转移和歧化反应为平衡约束的,而脱烷基化反应为动力学控制的。
还已知通过由沸石形成的分子筛分离异构体。沸石通常为水合的硅酸铝和钙(或钠),它们可在受控的孔隙率下制备或选择以用于石油精炼厂的催化裂化,并且可为天然的或合成的。孔可形成发生催化反应的位点,并且还可形成对某些异构体通过而排除其它异构体具有选择性的通道。沸石可通过用酸洗涤而充当用于氢离子交换的布朗斯台德酸,或者通过加热以消除布朗斯台德位点的水而充当路易斯酸。举例来说,ZSM-5沸石(Na3Al3Si93O192.16H2O)的孔尺寸引起形成具有使得其形成二甲苯异构体选择性筛的尺寸和形状的通道。甲醇对甲苯进行的烷化将形成所有三种二甲苯异构体的混合物。p-二甲苯由于其线性构型将穿过ZSM-5中的通道,而o-二甲苯和m-二甲苯将不穿过孔,尽管它们随后可在酸性条件下在孔中重排成p-二甲苯并且然后穿过筛。沸石的催化活性还可通过添加金属催化剂来增加,所述金属催化剂通过在金属表面上将分子氢分解成原子氢来使氢活化,以在烷基转移反应中形成中间体。
无论如何,这些通过重整产物的分馏生产二甲苯的常规手段导致二甲苯产率不足以满足需求,并且其它烃的转化为增加二甲苯产率所必需的。此外,来自催化重整或其它来源的二甲苯异构体流不满足作为化学中间体的需求。对二甲苯尤其是需求迅速增长的主要化学中间体,但是等于典型C8芳烃流的仅20%至25%。
发明内容
因此,一直需要适用于转化重质重整产物以生产二甲苯的催化剂。本公开的实施例涉及沸石复合烷基转移催化剂、它们的制备方法和性能,特别是涉及具有有序/无序介观结构和水热稳定性的这类催化剂的合成。沸石复合催化剂可将重质芳香族化合物的混合物,特别是C9芳香族烃转化成苯、甲苯和二甲苯,并且特别是转化成有商业价值的二甲苯。转化反应包括脱烷基化、烷基转移、歧化和异构化。沸石复合催化剂具有高乙基脱烷基化活性以及高甲基烷基转移活性以改进二甲苯的产率。
根据一个实施例,提供生产沸石复合催化剂的方法。方法包含在加热、搅拌或同时加热和搅拌时将包含中孔沸石的催化剂前体溶解在碱性溶液中以产生溶解的沸石溶液,其中中孔沸石的SiO2/Al2O3摩尔比为至少30,其中中孔沸石包含β沸石;调节溶解的沸石溶液的pH;使pH调节后的溶解的沸石溶液老化,以由溶解的沸石溶液产生固体沸石复合材料;和煅烧固体沸石复合材料以生产沸石复合催化剂,其中沸石复合催化剂具有包含至少一种无序中间相和至少一种有序中间相的介观结构,并且其中沸石复合催化剂具有通过Brunauer-Emmett-Teller(BET)分析定义的至少600m2/g的表面积。
根据另一个实施例,提供沸石复合催化剂。沸石复合催化剂包含介观结构,所述介观结构包含至少一种无序中间相和至少一种有序中间相,其中沸石复合催化剂具有通过Brunauer-Emmett-Teller(BET)分析定义的至少600m2/g的表面积,并且其中沸石复合催化剂包含β沸石。
根据又另一个实施例,提供将C9+烷基芳香族烃转化成包含苯、甲苯和二甲苯的产物流的方法。方法包含还原包含介观结构的沸石复合催化剂,所述介观结构包含至少一种无序中间相和至少一种有序中间相,其中沸石复合催化剂具有在400℃下用氢气通过BET定义的至少600m2/g的表面积,其中沸石复合催化剂包含β沸石。方法另外包含使包含C9+烷基芳香族烃的进料与还原的复合沸石催化剂和氢气在反应器的烷基转移区中接触以生产烷基转移产物;汽提C1-C5和更轻质烃并且从烷基转移产物中汽提未反应的进料;和从烷基转移产物中收集二甲苯产物。
所描述的实施例的额外的特征和优点将在下面的具体实施方式中予以阐述,并且部分地从那些描述中对本领域技术人员而言将变得显而易见,或者通过实践所描述的实施例(包含下面的具体实施方式、权利要求书以及附图)而被认识。
附图说明
图1为描绘根据本公开的一个或多个实施例的沸石复合催化剂的合成的流程图。
图2为描绘根据本公开的一个或多个实施例的将重质重整产物转化成二甲苯的示意图。
图3为具有有序六方中间相的沸石复合催化剂的X射线衍射(XRD)图,所述沸石复合催化剂在十六烷基三甲基溴化铵(CTAB)存在下,通过使用0.45摩尔浓度(M)NaOH溶液溶解β沸石而生产。
图4为根据本公开的一个或多个实施例的沸石复合催化剂的XRD图,所述沸石复合催化剂具有有序六方中间相和无序六方中间相,所述沸石复合催化剂在CTAB存在下,通过使用0.1M NaOH溶液溶解β沸石而生产。
图5为根据本公开的一个或多个实施例的沸石复合催化剂的XRD图,所述沸石复合催化剂具有有序六方中间相和无序六方中间相,所述沸石复合催化剂在CTAB存在下,通过使用0.2M NaOH溶液溶解β沸石而生产。
图6为说明图3中所描绘的催化剂的孔尺寸分布的图。
图7为说明根据本公开的一个或多个实施例的图4中所描绘的催化剂的孔尺寸分布的图。
图8为说明根据本公开的一个或多个实施例的图5中所描绘的催化剂的孔尺寸分布的图。
图9为示出根据本公开的一个或多个实施例的有序六方相和无序六方相的TEM图像。
具体实施方式
现在将详细参考包含介观结构的沸石复合催化剂的实施例,所述介观结构包含至少一种无序中间相和至少一种有序中间相。在一个实施例中,有序中间相为六方中间相,并且无序中间相包含六方中间相。不受理论束缚,具有有序和无序中间相形成的复合催化剂提供改进的烷基转移催化剂活性,与β沸石和或典型的β沸石/MCM-41复合沸石相比,所述复合催化剂提供改进的二甲苯产率。如所定义的,“有序中间相”意指中孔的结晶沸石均匀排列,其中“中孔”具有在2至50纳米之间的平均孔径。如所定义的,“无序中间相”意指孔的不均匀排列,其中中孔具有在2至50纳米之间的平均孔径。如所定义的,“有序/无序相”意指表面具有至少一种有序中间相和至少一种无序中间相的组合,如图9的透射电子显微镜(TEM)图像中所示。
在一个实施例中,沸石复合催化剂可包含二氧化硅-氧化铝化合物。在另一个实施例中,二氧化硅-氧化铝化合物可包含至少30的SiO2/Al2O3摩尔比。此外,SiO2/Al2O3摩尔比可为30至100、或40至80。
在一个实施例中,沸石复合催化剂可包含β沸石。β沸石为复杂的共生族,其脱硅稳定性低于ZSM-5和丝光沸石的脱硅稳定性。β沸石的商业实施例为可购自日本的东曹株式会社(Tosoh Corporation,Japan)的HSZ-940NHA。另外,催化剂前体的中孔沸石可在沸石催化剂的骨架或基质中包含至少额外的金属或金属氧化物。在沸石复合催化剂的骨架中的额外的金属或金属氧化物可包括锆、锗、锡或其组合。尽管认为各种量为合适的,但是二氧化硅与额外的金属组分(例如,锗、锆、锡或其组合)的摩尔比可为5至100、或20至100。
此外,沸石复合催化剂还可包含至少一种额外的沸石,例如选自由丝光沸石、ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、MFI拓扑结构沸石、NES拓扑结构沸石、EU-1、MAPO-36、SAPO-5、SAPO-11、SAPO-34和SAPO-41组成的组的中孔或大孔沸石。为了本公开的目的,小孔沸石具有3-5埃的孔尺寸、中孔沸石具有5-6的孔尺寸,并且大孔沸石具有6-8的孔尺寸。不受理论的限制,这可允许沸石复合催化剂在继承中孔材料的孔结构质量的同时,维持中孔或大孔沸石的酸度优势。此第二沸石的量可在呈最终干燥和煅烧形式的沸石复合催化剂总量的10至90wt%的范围内。酸度由特定沸石复合催化剂中二氧化硅与氧化铝基团的比率定义。沸石复合催化剂具有中等酸度。为了本公开的目的,小于20的二氧化硅与氧化铝比率被认为是高酸度、在30至100范围内的二氧化硅与氧化铝比率被认为是中等酸度,并且大于100的二氧化硅与氧化铝比率被认为是低酸度。
此外,沸石复合催化剂可用活性金属浸渍用于催化,例如选自由钼、铬、铂、镍、铂、钯、铼或其组合组成的组的活性金属。在一个实施例中,活性金属为钼。金属组分可以化合物,如氧化物、硫化物或卤化物的形式与复合材料的一种或多种其它成分化学组合,或者以元素金属形式存在于最终催化复合材料中。活性金属组分可以催化有效的任何量,通常占基于元素计算的最终催化剂的0.01至5wt%存在于最终沸石复合催化剂中。
如以下在合成讨论中所描述的,沸石复合催化剂可包括由β沸石前体生产的β沸石/MCM-41结构。在至少一个实施例中,沸石复合催化剂包含小于20%的由β沸石前体形成的MCM-41中孔含量。
从特性观点来看,沸石复合催化剂可具有通过Brunauer-Emmett-Teller(BET)分析定义的至少600米2/克(m2/g)的表面积、或至少700m2/g的BET表面积。另外,沸石复合催化剂可具有至少300m2/g的外表面积、或至少350m2/g的外表面积。
在一个或多个实施例中,沸石复合催化剂可具有0.20至3.0cm3/g、或0.30至1.0cm3/g的总孔体积。此外,沸石复合催化剂可具有至少0.30cm3/g、或至少0.40cm3/g、或至少0.50cm3/g的总孔体积。在另一个实施例中,沸石复合催化剂可具有至少30埃(3纳米)的平均孔径。
参考图1,生产沸石复合催化剂的方法可包含以下步骤:提供包含SiO2/Al2O3摩尔比为至少30的中孔沸石的催化剂前体10,并且在加热、搅拌或同时加热和搅拌时将其溶解在碱性溶液中以产生溶解的沸石溶液20。在一个实施例中,催化剂前体包含β沸石,以产生β沸石前体。另外,催化剂前体可包含β沸石和选自由丝光沸石、ZSM-22、ZSM-12以及其组合组成的组的至少一种额外的中孔沸石,以产生替代的β沸石前体。
溶解步骤,也被称为脱硅,可在表面活性剂30存在下进行,其中表面活性剂通常称为用于沸石催化剂的模板剂。虽然图1的实施例示出模板表面活性剂,但是在其它实施例中设想不存在表面活性剂。举例来说但不限于,表面活性剂为阳离子表面活性剂。阳离子表面活性剂可包括季铵化合物。举例来说但不限于,季铵阳离子表面活性剂可为十六烷基三甲基溴化铵(CTAB)。设想将不同量的表面活性剂包括在催化剂前体中。举例来说,催化剂前体可包括1重量%至10重量%的表面活性剂,例如CTAB,或2重量%至8重量%的表面活性剂,例如CTAB。
在常规脱硅期间,使用标准条件通过脱硅生成沸石中的中孔隙。举例来说,脱硅可使用0.2M NaOH在65℃下搅拌30分钟进行。通过此工艺,三分之一的催化剂由于脱硅而损失;然而,本发明方法利用此脱硅源以使用表面活性剂模板生成中孔隙。
另外如图1所示,可在表面活性剂模板存在下通过逐渐加热24小时缓慢发生溶解。通过另一种方法,也可在不存在表面活性剂模板的情况下进行脱硅。在一个实施例中,通过搅拌30分钟,可在不存在表面活性剂模板的情况下发生脱硅。收集滤液并且使用模板介导技术生成中孔。通过这种方式,废弃的脱硅源用于生产中间相。设想各种加热工艺或元件。举例来说,加热可为水热加热。在一个或多个实施例中,可在50至150℃的温度下或90至110℃的温度下发生水热加热。此外,水热加热的持续时间可在30分钟至24小时范围内。
设想各种碱性溶液用于脱硅。在一个实施例中,碱性溶液可包含NaOH。在具体实施例中,碱性溶液可包含0.01至0.2摩尔浓度(M)NaOH、0.05至0.2摩尔浓度(M)NaOH、或0.05至0.1M NaOH。不受理论束缚,出乎意料地发现控制NaOH的摩尔浓度为影响沸石复合催化剂的有序/无序相介观结构的参数。
再次参考图1,方法可包含调节溶解的沸石溶液的pH的步骤40。通过酸性溶液进行pH调节。设想各种酸。在一个实施例中,酸性溶液包含硫酸。在一个实施例中,将pH调节至8至10。
接下来,可利用各种额外步骤50,例如水热老化、过滤、洗涤、干燥、离子交换和煅烧pH调节后的溶解的沸石溶液。水热老化可涉及将pH调节后的溶解的沸石溶液在75至125℃的温度下维持12至48小时的持续时间。在水热老化期间,可溶性铝硅酸盐物质水热冷凝以形成中间相。可在硝酸盐溶液(例如但不限于包含NH4NO3的溶液)存在下发生离子交换。此外,设想可将沸石在600-750℃下汽蒸4小时。在此阶段60,形成具有有序/无序中间相的固体复合沸石。
参考图1,工艺还可包括在粘合剂存在下挤出固体沸石复合材料的步骤70。耐火粘合剂或基质任选地用于促进催化剂的制作、提供强度和降低制作成本。合适的粘合剂包括无机氧化物,如氧化铝、氧化镁、氧化锆、氧化铬、二氧化钛、硼、磷酸盐、氧化锌和二氧化硅中的一种或多种。在一个实施例中,粘合剂为氧化铝基粘合剂。氧化铝粘合剂的一个商业实施例为获自日本的触媒化成工业股份有限公司(Catalysts&Chemicals Industries Co.,Ltd(CCIC),Japan)的Cataloid AP-3。沸石可以干粉形式与含水形式的氧化铝粘合剂混合以产生均匀混合物,从而确保形成的挤出物的均匀组成。在一个或多个实施例中,固体沸石复合材料与粘合剂的重量比为4比1或3比1。与粘合剂一起挤出的步骤70可在100至150℃的温度下进行30分钟至2小时的持续时间。
接下来,工艺可包含在煅烧步骤之前用一种或多种活性金属浸渍固体沸石复合材料的步骤70。一种或多种活性金属选自由钼(Mo)、铂(Pt)、铼(Re)、镍(Ni)以及其组合组成的组。在一个实施例中,活性金属可包含2至6重量%的钼。任选地,沸石复合材料可在湿润浸渍后在100℃下干燥至少2小时。
再次参考图1,另一煅烧步骤90可用于生产沸石复合催化剂,所述沸石复合催化剂作为烷基转移催化剂100为有效的。煅烧步骤可在400至500℃的温度下发生4至8小时、在400℃的温度下发生4小时。
另外如上所述,本发明沸石复合催化剂为适合于将C9+烷基芳香族烃转化成包含苯、甲苯和二甲苯的产物流、特别是转化成有商业价值的二甲苯的烷基转移催化剂。转化工艺的进料流通常包含碳数范围为C9至C11+的烷基芳香族烃,所述烷基芳香族烃可包括例如这类烃,如丙基苯、乙基甲基苯、四甲基苯、乙基二甲基苯、二乙基苯、甲基丙基苯以及其混合物。主要以C9+芳烃为特征的重质芳烃进料流允许轻质芳烃(如苯和甲苯)与更重质C9+芳烃的有效烷基转移,以产生额外的C8芳烃,如二甲苯。重质芳烃流优选地包含至少90wt%C9芳烃,并且可衍生自相同或不同的已知精炼和石化工艺,并且可从来自烷基转移的产物的分离中再循环。
参考图2的实施例,使用沸石复合催化剂作为烷基转移催化剂的方法可任选地包括用加热器单元111加热来自进料源105的包含C9+烷基芳香族烃的进料110。如图所示,加热器单元111可为热交换器,所述热交换器接收加热流108,例如热水流,以在输送至反应器系统113之前加热进料110。设想加热进料的其它方法。
如图2所示,反应器系统可包括具有在烷基转移催化剂区115中使用的沸石复合催化剂的单个反应器113,或者可包括多个反应器或阶段。反应器113被描绘为下流114反应器,但是这是许多可能性中的一个。在图2的实施例中,反应器113具有催化剂固定圆柱形床;然而,可采用利用催化剂移动床或径向流反应器或流化床的其它反应配置。在进料被输送之前,烷基转移催化剂区115中的沸石复合催化剂可被还原,例如用氢气112还原。在一个实施例中,沸石复合催化剂112在350至450℃或400℃的温度下用氢气还原。
再次参考图2,进料流110在反应器113的烷基转移催化剂区115中接触还原的复合沸石催化剂和氢气112。具体地说,进料110在气相中和在氢气112存在下被烷基转移。氢气112可以每摩尔烷基芳烃0.1至10摩尔氢气的量与进料流110一起输送。氢气与烷基芳烃的此比率也称为氢气与烃比率。烷基转移引起生产烷基转移流出物流116,其包含产物烃,具体地说,具有混合二甲苯含量的烃,以及未转化的进料、甲苯和苯。设想各种条件用于反应器113。具体地说,烷基转移催化剂区115可包括在200℃和540℃之间的温度以及1.0MPa至5.0MPa的适度升高的压力。液时空速(LHSV)在1.0小时-1至5.0小时-1范围内。
如图所示,烷基转移流出物流116可使用冷却器117冷却。冷却器117可为热交换器、冷凝器或技术人员熟知的任何其它合适的冷却装置。如图所示,冷却器117为包括冷却流118的热交换器。接下来,可将烷基转移流出物流116进料至汽提柱120,其中将C1-C5和更轻质烃122从烷基转移流出物流116中分离。另外,可从烷基转移流出物流116中汽提未反应的进料。
参考图2,可从汽提柱120底部排出的汽提柱120的产物124可包括包含苯和甲苯的轻质再循环流、混合C8芳烃产物和重质再循环流。所有这些都可随后在一个或多个反应容器125、127、129中被分离。混合C8芳烃产物128可被送去回收p-二甲苯132和其它有价值的异构体134。轻质再循环流126可经历苯和甲苯回收136,其中一部分再循环至烷基转移区或进料源105。重质再循环流130可含有基本上所有C9和更重质芳烃,并且可部分或全部再循环至烷基转移反应区,或输送至进料源105用于再循环,或从工艺中除去用于弃置或其它处理。
实例
通过以下实例将另外阐明所描述的实施例。
为了证明的目的,如下提供复合催化剂的制备。在实例1中描述包括有序六方相的催化剂A的合成。在实例2中描述具有无序六方中间相的复合催化剂B的制备。在实例3中呈现具有有序/无序六方中间相的复合催化剂C的制备。在实例4中将催化剂A的性能与作为催化剂A的成分的两种沸石的物理混合物的性能进行比较。在实例5中将催化剂A的性能与其成分中的一种(β沸石)的性能进行比较。实例6描述β40脱硅沸石(催化剂D)的制备。在实例7中描述负载金属的复合催化剂(A-1、B-1、C-1、E-1、F-1和G-1)的制备。在实例8中比较催化剂A-1、B-1、C-1、D、E-1、F-1和G-1的性能。最后,实例9描述使用脱硅滤液溶液制备β中孔沸石复合催化剂。
在这些实例中描述的催化剂仅为示例性实施例,并不旨在限制覆盖本发明的复合催化剂的一般描述。在每个实例中,β沸石为可购自日本的东曹株式会社的HSZ-940NHA。
实例1:具有有序六方中间相的分级催化剂A的制备
通过在100℃下逐渐加热(在不搅拌的情况下)24小时(h),使用0.45M NaOH溶液崩解两克β沸石(Si/Al摩尔比=40)。加热在CTAB(4.45wt%)存在下进行。将混合物冷却,并且然后通过添加稀硫酸(2当量浓度(N),当量/升)将pH调节至9.0。然后将混合物搅拌24小时(h),并且然后在100℃下老化24小时,以形成β沸石/MCM-41复合材料。过滤固体产物,使用蒸馏水彻底洗涤,在80℃下干燥过夜,然后在550℃下煅烧6小时以除去表面活性剂。将由此获得的复合材料用0.05M NH4NO3溶液在80℃下离子交换三次,持续2小时,然后在550℃下煅烧2小时。所得β沸石/MCM-41复合材料称为催化剂A。
如图3所示,在CTAB存在下使用0.45M NaOH溶液溶解β沸石引起形成催化剂A,所述催化剂A为具有有序六方中间相的典型双孔复合材料。在低X射线衍射角下,观察到对应于MCM-41的在(100)处指示的强峰以及在(110)和(200)处指示的强高阶衍射峰。
实例2:具有有序/无序六方中间相的复合催化剂B的制备。
通过在100℃下逐渐加热(在不搅拌的情况下)24小时,使用0.1M NaOH溶液崩解两克β沸石(Si/Al比率=40)。加热在CTAB(4.45wt%)存在下进行。将混合物冷却,并且然后通过添加稀硫酸(2N)将pH调节至9.0。然后将混合物搅拌24小时,并且然后在100℃下老化24小时,以形成β沸石/MCM-41复合材料。过滤固体产物,使用蒸馏水彻底洗涤,在80℃下干燥过夜,然后在550℃下煅烧6小时以除去表面活性剂。将由此获得的复合材料用0.05M NH4NO3溶液在80℃下离子交换三次,持续2小时,然后在550℃下煅烧2小时。所得β沸石/MCM-41复合材料称为催化剂B。
如图4所示,在CTAB存在下使用0.1M NaOH溶液溶解β沸石引起形成具有无序六方中间相的中孔。XRD图谱表明形成含有高度β沸石特征以及无序六方中间相的β中孔沸石。
实例3:具有有序/无序六方中间相的复合催化剂C的制备。
通过在100℃下逐渐加热(在不搅拌的情况下)24小时,使用0.2M NaOH溶液崩解两克β沸石(Si/Al比率=40)。加热在CTAB(4.45wt%)存在下进行。将混合物冷却,并且然后通过添加稀硫酸(2N)将pH调节至9.0。然后将混合物搅拌24小时,并且然后在100℃下老化24小时,以形成β沸石/MCM-41复合材料。过滤固体产物,使用蒸馏水彻底洗涤,在80℃下干燥过夜,然后在550℃下煅烧6小时以除去表面活性剂。将由此获得的复合材料用0.05M NH4NO3溶液在80℃下离子交换三次,持续2小时,然后在550℃下煅烧2小时。所得β沸石/MCM-41复合材料称为催化剂C。表1包括催化剂C的选定特性。
表1:催化剂C数据
如图5所示,在CTAB存在下使用0.2M NaOH溶液溶解β沸石引起形成含有有序/无序中间相的强度较低的六方相。
参考图6-8,催化剂A表现出窄的中孔尺寸分布(图6)。然而,与典型的双孔复合材料相比,含有无序中间相的催化剂B(图7)和有序/无序中间相催化剂C的孔尺寸分布示出孔不是均匀分布的(图8)。
实例4:催化剂A与其成分的物理混合物的比较
在台式反应系统中使用含有摩尔比为1:1的1,2,4-三甲基苯和甲苯的原料,测试催化剂A的烷基转移反应活性。还测试通过以等比例物理混合β沸石和MCM-41制备的催化剂(催化剂PMBM),以便证明复合催化剂对C9转化率和二甲苯产率的有效性。催化测试包括在竖直反应器中在反应器中部负载2.0毫升(ml)的催化剂,以及在反应器的下部和上部装入惰性氧化铝球。反应器的总体积为5ml。在400℃下于50毫升/分钟纯氢气流量下活化和还原催化剂,并且在此温度下保持2小时。然后,将反应器的压力增加至20巴,并且原料的流动以4.8毫升/小时开始。在收集产物样品之前,使反应在此温度下运行3小时。
将反应产物直接注入配备有火焰离子化检测器的在线气相色谱仪中。在程序升温条件下,在50米(m)长和0.15毫米(mm)直径的色谱柱上进行烃分离。各组分根据它们的沸点进行分离。使用校准来鉴定组分,所述校准使用具有已知组成的组分的标准烃混合物样品来完成。通过配备有火焰离子化检测器和热导检测器的气相色谱仪离线分析气态产物的组成。通过50m长的毛细管柱分析气态烃和氢气。
从如下的表2中所示的数据来看,与在相同工艺条件下β沸石和MCM-41的物理混合物(催化剂PMBM)相比,催化剂A示出明显更高的二甲苯产率。这些结果表明,含有β沸石和MCM-41的复合催化剂具有独特的结构,其性能与仅其成分的混合物的性能不同。
表2:催化剂A与其成分的物理混合物的性能比较
实例5:催化剂A与β沸石的比较
在台式反应器中使用工业重质重整产物原料测试催化剂A的烷基转移反应活性。还测试β沸石样品以便证明复合催化剂对C9转化率和二甲苯产率的有效性。用于确定催化活性的程序与实例4中所述的程序相同,期望原料为工业重质重整产物原料。重质重整产物的组成在表3中呈现。
表3:重质重整产物组成
从表4所示的产物组成数据来看,与β沸石相比,催化剂A提供更高的二甲苯产率。数据还示出单个C9烃的转化百分比更高,尤其是表3中列出的主要烃。
表4催化剂A与β沸石的性能比较
实例6-β40脱硅沸石(催化剂D)的制备。
通过在65℃下搅拌30分钟,使用0.2M NaOH溶液将两克β沸石(Si/Al摩尔比=40)脱硅。将混合物冷却,并且过滤固体产物,使用蒸馏水彻底洗涤,并且在80℃下干燥过夜。将由此获得的材料用0.05M NH4NO3溶液在80℃下离子交换三次,持续2小时,然后在550℃下煅烧2小时。所得脱硅沸石称为催化剂D。
实例7-负载金属(Pt、Mo)的复合催化剂的制备
从实例1-3中,发现复合催化剂A对于烷基转移具有活性。为了改进性能,制备具有六方有序和无序孔结构的催化剂,并且将一种或多种活性金属负载在复合催化剂A、B和C上。
这类负载钼的复合催化剂的实例称为催化剂A-1(4.0wt%Mo)、B-1(4.0wt%Mo)和C-1(4.0wt%Mo)。将活性与常规的β40脱硅沸石(催化剂D)的活性进行比较。在催化剂A上负载有铂的催化剂称为催化剂E-1(2.0wt%Pt)。在催化剂A上负载有钼的催化剂称为催化剂F-1(2.0wt%Mo)。在催化剂A上负载有铂和钼的催化剂称为催化剂G-1(1.5wt%Mo+0.5wt%Pt)。初始润湿浸渍方法被应用于负载金属,并且其程序总结如下:
步骤1:将一克催化剂A浸入1.72克(g)去离子水中,以使孔体积饱和;步骤2:将0.0397g四氨合硝酸铂溶解在1.72g去离子水中;步骤3:然后添加一克催化剂A,并且与溶解的铂或钼溶液均匀混合;和步骤4:将样品在100℃下干燥过夜,接着在400℃下煅烧四小时(加热速率为5摄氏度/分钟)。
在双金属浸渍的情况下,首先浸渍1.5wt%Mo、干燥并且然后浸渍0.5wt%Pt。然后将样品在400℃下煅烧四小时。加热速率为5摄氏度/分钟。
实例8-负载金属的催化剂A-1、B-1、C-1、E-1、F-1和G-1与脱硅催化剂D的性能比较
在台式反应系统中使用工业重质重整产物原料测试催化剂的烷基转移反应活性。用于确定催化活性的程序与实例4中所述的程序相同。
从表5中所示的产物组成数据可以看出,一种或多种活性金属的浸渍引起显著改进,特别是对二甲苯的选择率。获得的超过2%Mo的产物组成(催化剂F-1)示出轻质烃产率的显著降低。它还示出更高的TMB转化率,并且因此改进二甲苯产率(29.5wt%)。
表5:负载金属的催化剂A-1、B-1、C-1、E-1、F-1和G-1与脱硅催化剂D的性能比较
实例9:使用脱硅滤液溶液制备β中孔沸石复合催化剂。
通过在65℃下搅拌30分钟,使用60mL的0.2M NaOH溶液将β沸石脱硅。过滤固体产物、使用蒸馏水彻底洗涤、干燥并且进行离子交换,并且在500℃下煅烧2小时。
收集滤液,并且在CTAB(2-8wt%)存在下用于介观结构转化。将混合物冷却,并且然后通过添加稀硫酸(2N)将混合物的pH调节至9.0。然后将混合物搅拌24小时,并且然后在100℃下老化24小时,以形成分级β沸石。过滤固体产物,使用蒸馏水彻底洗涤,在80℃下干燥过夜,然后在550℃下煅烧6小时以除去表面活性剂。将由此获得的复合材料用0.05MNH4NO3溶液在80℃下离子交换三次,持续2小时,然后在550℃下煅烧2小时。
现在应理解,描述沸石复合催化剂、生产沸石复合催化剂的方法、以及使用这些方法将C9+烷基芳香族烃转化成包含苯、甲苯和二甲苯的产物流的方法的各个方面,并且这类方面可与各种其它方面结合使用。
在第一方面中,本公开提供一种生产沸石复合催化剂的方法。所述方法包含在加热、搅拌或同时加热和搅拌时将包含至少一种中孔沸石的催化剂前体溶解在碱性溶液中以产生溶解的沸石溶液,其中所述中孔沸石的SiO2/Al2O3摩尔比为至少30,其中所述中孔沸石包含β沸石;调节所述溶解的沸石溶液的pH;使pH调节后的溶解的沸石溶液老化,以由所述溶解的沸石溶液产生固体沸石复合材料;和煅烧所述固体沸石复合材料以生产所述沸石复合催化剂,其中所述沸石复合催化剂具有包含至少一种无序中间相和至少一种有序中间相的介观结构,并且其中所述沸石复合催化剂具有通过Brunauer-Emmett-Teller(BET)分析定义的至少600m2/g的表面积。
在第二方面中,本公开提供根据第一方面所述的方法,其中所述方法另外包括将所述固体沸石复合材料与粘合剂一起挤出。
在第三方面中,本公开提供根据第二方面所述的方法,其中所述粘合剂为氧化铝基粘合剂。
在第四方面中,本公开提供根据第二或第三方面中任一项所述的方法,其中所述固体沸石复合材料与粘合剂的重量比为4比1。
在第五方面中,本公开提供根据第一至第四方面中任一项所述的方法,其中所述有序中间相为六方中间相。
在第六方面中,本公开提供根据第一至第五方面中任一项所述的方法,其中所述催化剂前体的所述中孔沸石包含至少一种额外的金属或金属氧化物。
在第七方面中,本公开提供根据第六方面所述的方法,其中所述至少一种额外的金属或金属氧化物选自由锆、锗、锡以及其组合组成的组。
在第八方面中,本公开提供根据第一至第七方面中任一项所述的方法,其中所述加热为水热加热。
在第九方面中,本公开提供根据第一至第八方面中任一项所述的方法,其中所述老化涉及将所述pH调节后的溶解的沸石溶液在75至125℃的温度下维持12至48小时的持续时间。
在第十方面中,本公开提供根据第一至第九方面中任一项所述的方法,其中所述方法另外包含对所述固体沸石复合材料进行离子交换。
在第十一方面中,本公开提供根据第一至第十方面中任一项所述的方法,其中所述溶解在不存在表面活性剂的情况下进行。
在第十二方面中,本公开提供根据第一至第十方面中任一项所述的方法,其中所述溶解在表面活性剂存在下进行。
在第十三方面中,本公开提供根据第十二方面所述的方法,其中所述表面活性剂为十六烷基三甲基溴化铵。
在第十四方面中,本公开提供根据第一至第十三方面中任一项所述的方法,其中所述催化剂前体另外包含选自由丝光沸石、ZSM-22、ZSM-12以及其组合组成的组的至少一种额外的中孔沸石。
在第十五方面中,本公开提供根据第一至第十四方面中任一项所述的方法,其中所述pH的所述调节为通过酸性溶液进行的。
在第十六方面中,本公开提供根据第一至第十五方面中任一项所述的方法,其中所述沸石复合催化剂具有在0.2至3.0cc/g范围内的孔体积。
在第十七方面中,本公开提供根据第一至第十六方面中任一项所述的方法,其中所述沸石复合催化剂中二氧化硅与铝的摩尔比为30至100。
在第十八方面中,本公开提供根据第一至第十七方面中任一项所述的方法,其中二氧化硅与锗、锆和锡的摩尔比为5至100。
在第十九方面中,本公开提供根据第一至第十八方面中任一项所述的方法,其中所述方法另外包含在煅烧步骤之前用一种或多种活性金属浸渍固体沸石复合材料,其中所述一种或多种活性金属选自由钼、铂、铼、镍以及其组合组成的组。
在第二十方面中,本公开提供根据第十九方面所述的方法,其中所述活性金属包含钼。
在第二十一方面中,本公开提供根据第一至第二十方面中任一项所述的方法,其中所述碱性溶液为0.1至0.2M NaOH溶液。
在第二十二方面中,本公开提供一种沸石复合催化剂。所述沸石复合催化剂包含介观结构,所述介观结构包含至少一种无序中间相和至少一种有序中间相,其中所述沸石复合催化剂具有通过Brunauer-Emmett-Teller(BET)分析定义的至少600m2/g的表面积,并且其中所述沸石复合催化剂包含β沸石。
在第二十三方面中,本公开提供根据第二十二方面所述的沸石复合催化剂,其中如通过BET定义的所述表面积为至少700m2/g。
在第二十四方面中,本公开提供根据第二十二或第二十三方面中任一项所述的沸石复合催化剂,其中所述沸石复合催化剂具有至少300m2/g的外表面积。
在第二十五方面中,本公开提供根据第二十二至第二十四方面中任一项所述的沸石复合催化剂,其中所述沸石复合催化剂包含至少0.50cm3/g的总孔体积。
在第二十六方面中,本公开提供根据第二十二至第二十五方面中任一项所述的沸石复合催化剂,其中所述沸石复合催化剂包含β沸石/MCM-41。
在第二十七方面中,本公开提供一种将C9+烷基芳香族烃转化成包含苯、甲苯和二甲苯的产物流的方法。所述方法包含还原包含介观结构的沸石复合催化剂,所述介观结构包含至少一种无序中间相和至少一种有序中间相,其中所述沸石复合催化剂具有在400℃下用氢气通过BET定义的至少600m2/g的表面积,其中所述沸石复合催化剂包含β沸石;使包含C9+烷基芳香族烃的进料与还原的复合沸石催化剂和氢气在反应器的烷基转移区中接触以生产烷基转移产物;汽提C1-C5和更轻质烃并且从所述烷基转移产物中汽提未反应的进料;和从所述烷基转移产物中收集二甲苯产物。
在第二十八方面中,本公开提供根据第二十七方面所述的方法,其中所述烷基转移区处于1.0至3.0MPa之间的压力、200℃至500℃的温度、1.0至5.0小时-1的空速,和1比4的氢气与烃比率。
对于本领域技术人员显而易见的是,可在不偏离所要求保护的主题的精神和范围的情况下对所描述的实施例进行各种修改和变化。因此,旨在本说明书覆盖所描述的各种实施例的修改和变化,其条件是,这类修改和变化落在所附权利要求书以及其等效物的范围内。
Claims (15)
1.一种生产沸石复合催化剂的方法,其包含:
在加热、搅拌或同时加热和搅拌时将包含至少一种中孔沸石的催化剂前体溶解在碱性溶液中以产生溶解的沸石溶液,其中所述中孔沸石的SiO2/Al2O3摩尔比为至少30,其中所述中孔沸石包含β沸石;
调节所述溶解的沸石溶液的pH;
使pH调节后的溶解的沸石溶液老化,以由所述溶解的沸石溶液产生固体沸石复合材料;和
煅烧所述固体沸石复合材料以生产所述沸石复合催化剂,其中所述沸石复合催化剂具有包含至少一种无序中间相和至少一种有序中间相的介观结构,并且其中所述沸石复合催化剂具有通过Brunauer-Emmett-Teller(BET)分析定义的至少600m2/g的表面积。
2.根据权利要求1所述的方法,其另外包含将所述固体沸石复合材料与氧化铝基粘合剂以4比1的所述固体沸石复合材料与粘合剂的重量比一起挤出。
3.根据权利要求1所述的方法,其中所述有序中间相为六方中间相。
4.根据权利要求1所述的方法,其中所述催化剂前体的所述中孔沸石包含选自由锆、锗、锡以及其组合组成的组的至少一种额外的金属或金属氧化物。
5.根据权利要求1所述的方法,其中所述老化涉及将所述pH调节后的溶解的沸石溶液在75至125℃的温度下维持12至48小时的持续时间。
6.根据权利要求1所述的方法,其另外包含对所述固体沸石复合材料进行离子交换。
7.根据权利要求1所述的方法,其中所述催化剂前体另外包含选自由丝光沸石、ZSM-22、ZSM-12以及其组合组成的组的至少一种额外的中孔沸石。
8.根据权利要求1所述的方法,其中所述沸石复合催化剂具有在0.2至3.0cc/g范围内的孔体积。
9.根据权利要求1所述的方法,其中所述沸石复合催化剂中二氧化硅与铝的摩尔比为30至100。
10.根据权利要求1所述的方法,其中二氧化硅与锗、锆和锡的摩尔比为5至100。
11.根据权利要求1所述的方法,其另外包含在煅烧步骤之前用一种或多种活性金属浸渍固体沸石复合材料,其中所述一种或多种活性金属选自由钼、铂、铼、镍以及其组合组成的组。
12.根据权利要求1所述的方法,其中所述碱性溶液为0.1至0.2M NaOH溶液。
13.一种沸石复合催化剂,其包含介观结构,所述介观结构包含至少一种无序中间相和至少一种有序中间相,其中所述沸石复合催化剂具有通过Brunauer-Emmett-Teller(BET)分析定义的至少600m2/g的表面积,并且其中所述沸石复合催化剂包含β沸石。
14.一种将C9+烷基芳香族烃转化成包含苯、甲苯和二甲苯的产物流的方法,所述方法包含:
还原包含介观结构的沸石复合催化剂,所述介观结构包含至少一种无序中间相和至少一种有序中间相,其中所述沸石复合催化剂具有在400℃下用氢气通过BET定义的至少600m2/g的表面积,其中所述沸石复合催化剂包含β沸石;
使包含C9+烷基芳香族烃的进料与还原的复合沸石催化剂和氢气在反应器的烷基转移区中接触以生产烷基转移产物;
汽提C1-C5和更轻质烃并且从所述烷基转移产物中汽提未反应的进料;和
从所述烷基转移产物中收集二甲苯产物。
15.根据权利要求14所述的方法,其中所述烷基转移区处于1.0至3.0MPa之间的压力、200℃至500℃的温度、1.0至5.0小时-1的空速,和1比4的氢气与烃比率。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI814099B (zh) * | 2020-11-06 | 2023-09-01 | 美商艾克頌美孚化學專利股份有限公司 | 烷基芳族化合物之製造 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10661260B2 (en) | 2017-06-15 | 2020-05-26 | King Fahd University Of Petroleum And Minerals | Zeolite composite catalysts for conversion of heavy reformate to xylenes |
US11261098B2 (en) * | 2019-11-06 | 2022-03-01 | Saudi Arabian Oil Company | Systems and methods for preparing nano-sized crystals of BEA zeolite with metal oxide for hydrocarbon conversions |
US10981160B1 (en) | 2019-12-19 | 2021-04-20 | Saudi Arabian Oil Company | Composite hierarchical zeolite catalyst for heavy reformate conversion to xylenes |
US20240124317A1 (en) * | 2022-10-12 | 2024-04-18 | Saudi Arabian Oil Company | Processes of producing mesoporous beta zeolites |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130165315A1 (en) * | 2011-12-27 | 2013-06-27 | King Fahd University Of Petroleum And Minerals | Method of forming a hydrocarbon cracking catalyst |
CN104603087A (zh) * | 2012-04-02 | 2015-05-06 | 沙特阿拉伯石油公司 | 从重质芳烃生产二甲苯和轻质烯烃的方法 |
Family Cites Families (65)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4341622A (en) | 1980-12-04 | 1982-07-27 | Mobil Oil Corporation | Manufacture of benzene, toluene and xylene |
US4861739A (en) * | 1987-06-04 | 1989-08-29 | Uop | Microporous crystalline composite compositions |
TW504501B (en) | 1995-02-10 | 2002-10-01 | Mobil Oil Corp | Process for converting feedstock comprising C9+ aromatic hydrocarbons to lighter aromatic products |
US5942651A (en) | 1997-06-13 | 1999-08-24 | Mobile Oil Corporation | Process for converting C9 + aromatic hydrocarbons to lighter aromatic products by transalkylation in the prescence of two zeolite-containing catalysts |
WO2000038834A1 (en) * | 1998-12-24 | 2000-07-06 | Sk Corporation | Catalyst for the disproportionation/transalkylation of aromatic hydrocarbons and method for preparing the same |
US7084087B2 (en) * | 1999-09-07 | 2006-08-01 | Abb Lummus Global Inc. | Zeolite composite, method for making and catalytic application thereof |
FR2802120B1 (fr) | 1999-12-14 | 2002-02-01 | Inst Francais Du Petrole | Solide silicoaluminate micro et mesoporeux, procede de preparation, utilisation comme catalyseur et en conversion d'hydrocarbures |
US6746659B2 (en) | 2000-05-25 | 2004-06-08 | Board Of Trustees Of Michigan State University | Ultrastable porous aluminosilicate structures |
WO2003004444A1 (en) * | 2001-07-02 | 2003-01-16 | Exxonmobil Chemical Patents Inc. | Inhibiting catalyst coke formation in the manufacture of an olefin |
US6793911B2 (en) | 2002-02-05 | 2004-09-21 | Abb Lummus Global Inc. | Nanocrystalline inorganic based zeolite and method for making same |
US6815570B1 (en) | 2002-05-07 | 2004-11-09 | Uop Llc | Shaped catalysts for transalkylation of aromatics for enhanced xylenes production |
WO2004000768A1 (en) | 2002-06-19 | 2003-12-31 | Exxonmobil Chemical Patents Inc. | Manufacture of xylenes by reactive distillation of reformate |
US6972348B2 (en) | 2004-03-24 | 2005-12-06 | Uop Llc | Catalytic conversion of polycyclic aromatics into xylenes |
ATE435068T1 (de) | 2004-04-14 | 2009-07-15 | Inst Francais Du Petrole | Katalysator enthaltend einen 10mr zeolith und einen 12mr zeolith und seine verwendung zur transalkylierung von alkylaromatischen kohlenwasserstoffen |
US20130292300A1 (en) | 2004-04-23 | 2013-11-07 | Massachusetts Institute Of Technology | Mesostructured zeolitic materials suitable for use in hydrocracking catalyst compositions and methods of making and using the same |
US7589041B2 (en) | 2004-04-23 | 2009-09-15 | Massachusetts Institute Of Technology | Mesostructured zeolitic materials, and methods of making and using the same |
US7154041B2 (en) | 2004-05-05 | 2006-12-26 | Itron, Inc. | Double wall isolated remote electronic enclosure apparatus |
US7220885B2 (en) | 2004-05-27 | 2007-05-22 | Uop Llc | Catalyst treatment useful for aromatics conversion process |
ES2936719T3 (es) | 2004-12-28 | 2023-03-21 | Neste Oyj | Método para la preparación de materiales catalíticos |
WO2006107452A1 (en) | 2005-03-31 | 2006-10-12 | Exxonmobil Chemical Patents Inc. | A process of using a high activity catalyst for the transalkylation of aromatics |
EP1866271B1 (en) | 2005-03-31 | 2016-09-21 | ExxonMobil Chemical Patents Inc. | Process and catalyst for the transalkylation of aromatics |
FR2909012B1 (fr) | 2006-11-23 | 2009-05-08 | Inst Francais Du Petrole | Catalyseur a base d'un materiau a porosite hierarchisee comprenant du silicium et procede d'hydrocraquage/ hydroconversion et d'hydrotraitement de charges hydrocarbonees. |
ES2319007B1 (es) | 2006-12-07 | 2010-02-16 | Rive Technology, Inc. | Metodos para fabricar materiales zeoliticos mesoestructurados. |
US7919421B2 (en) | 2006-12-21 | 2011-04-05 | Exxonmobil Chemical Patents Inc. | Catalyst composition, the method of manufacturing and the process of use thereof in aromatics alkylation |
US20080214882A1 (en) | 2007-02-16 | 2008-09-04 | Board Of Trustees Of Michigan State University | Acidic mesostructured aluminosilicates assembled from surfactant-mediated zeolite hydrolysis products |
US7803977B2 (en) | 2007-03-16 | 2010-09-28 | Uop Llc | Transalkylation of heavy alkylate using a layered catalyst |
US20100029467A1 (en) | 2008-07-30 | 2010-02-04 | Tomoyuki Inui | Multiple zeolite catalyst |
US8653315B2 (en) | 2008-07-30 | 2014-02-18 | King Fahd University Of Petroleum And Minerals | Multiple zeolite catalyst and method of using the same for toluene disproportionation |
US8252337B2 (en) * | 2008-10-23 | 2012-08-28 | National Health Research Institutes | Charged mesoporous silica nanoparticle-based drug delivery system for controlled release and enhanced bioavailability |
US8685875B2 (en) * | 2009-10-20 | 2014-04-01 | Rive Technology, Inc. | Methods for enhancing the mesoporosity of zeolite-containing materials |
CN102039201A (zh) * | 2009-10-22 | 2011-05-04 | 中国石油天然气股份有限公司 | 一种双微孔-介孔复合分子筛及其制备方法 |
CN102039200B (zh) | 2009-10-22 | 2012-07-18 | 中国石油天然气股份有限公司 | 一种Y-Beta/MCM-41双微孔-介孔复合分子筛及制备方法 |
US20110171121A1 (en) | 2010-01-08 | 2011-07-14 | Rive Technology, Inc. | Compositions and methods for making stabilized mesoporous materials |
US8071828B2 (en) | 2010-02-03 | 2011-12-06 | Exxonmobil Chemical Patents Inc. | Transalkylation of heavy aromatic hydrocarbon feedstocks |
US8435909B2 (en) | 2010-02-18 | 2013-05-07 | King Fahd University Of Petroleum And Minerals | Dual-zeolite catalyst for production of ethylbenzene |
US20110201860A1 (en) | 2010-02-18 | 2011-08-18 | Muhammad Naseem Akhtar | Process for conversion of alkanes to aromatics |
CA2830370A1 (en) | 2011-04-08 | 2012-10-11 | Rive Technology, Inc. | Mesoporous framework-modified zeolites |
FR2984759B1 (fr) | 2011-12-22 | 2013-12-20 | IFP Energies Nouvelles | Catalyseur comprenant au moins une zeolithe nu-86, au moins une zeolithe usy et une matrice minerale poreuse et procede d'hydroconversion de charges hydrocarbonees utilisant ce catalyseur |
CN103205271B (zh) * | 2012-01-12 | 2016-03-09 | 易高环保能源研究院有限公司 | 高温煤焦油加氢生产中间相沥青的方法 |
US9376324B2 (en) | 2012-01-13 | 2016-06-28 | Rive Technology, Inc. | Introduction of mesoporosity into zeolite materials with sequential acid, surfactant, and base treatment |
US20160017238A1 (en) | 2012-02-17 | 2016-01-21 | Kior, Inc. | Mesoporous Zeolite-Containing Catalysts For The Thermoconversion Of Biomass And For Upgrading Bio-Oils |
US8697593B2 (en) | 2012-03-12 | 2014-04-15 | King Fahd University Of Petroleum And Minerals | Zeolite catalyst for the alkylation of toluene with methanol |
JP2015516878A (ja) | 2012-04-02 | 2015-06-18 | サウジ アラビアン オイル カンパニー | キシレン類および石油化学品原料を生成するために重質改質油をトランスアルキル化するための多金属ゼオライト系触媒 |
JP6034224B2 (ja) * | 2012-04-10 | 2016-11-30 | ユニゼオ株式会社 | ベータ型ゼオライト及びその製造方法 |
CN104334515A (zh) | 2012-04-19 | 2015-02-04 | 沙特阿拉伯石油公司 | 从重质重整产物最大化生产二甲苯的脱烷基-烷基转移联合工艺 |
KR101384479B1 (ko) | 2012-08-24 | 2014-04-10 | 한국화학연구원 | 중형 세공을 갖는 제올라이트의 제조방법 |
US9573121B2 (en) | 2012-11-08 | 2017-02-21 | Rive Technology, Inc. | Mesoporous zeolite catalyst supports |
US9724680B2 (en) * | 2012-12-07 | 2017-08-08 | Exxonmobil Research And Engineering Company | Fiber reinforced zeolite extrudates with enhanced physical properties |
JP6436495B2 (ja) | 2013-07-04 | 2018-12-12 | トタル リサーチ アンド テクノロジー フエリユイ | 多孔質材料上に堆積させた寸法の小さい分子篩結晶を含む触媒組成物 |
EP3016741B1 (en) | 2013-07-05 | 2020-07-01 | Danmarks Tekniske Universitet | Method for producing zeolites and zeotypes |
CN103626655B (zh) * | 2013-11-27 | 2017-01-04 | 安徽大学 | 一种暴露晶面可控的金属有机骨架材料制备方法 |
US9662640B2 (en) * | 2013-12-27 | 2017-05-30 | Rive Technology, Inc. | Introducing mesoporosity into zeolite materials with a modified acid pre-treatment step |
JP6626103B2 (ja) | 2014-07-11 | 2019-12-25 | トタル リサーチ アンド テクノロジー フエリユイ | 回収可能かつリサイクル可能なメソポア−鋳型剤を含むメソポーラス・ミクロポーラス結晶質材料の製造方法 |
US9708233B2 (en) | 2014-08-15 | 2017-07-18 | Exxonmobil Chemical Patents Inc. | Aromatics production process |
US9963349B2 (en) | 2014-12-11 | 2018-05-08 | Rive Technology, Inc. | Preparation of mesoporous zeolites with reduced processing |
US10626019B2 (en) | 2014-12-30 | 2020-04-21 | W. R. Grace & Co.-Conn. | Methods for preparing zeolites with surfactant-templated mesoporosity and tunable aluminum content |
US10118165B2 (en) | 2015-02-04 | 2018-11-06 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and use in heavy aromatics conversion processes |
US20160221897A1 (en) | 2015-02-04 | 2016-08-04 | Exxonmobil Chemical Patents Inc. | Transalkylation of Heavy Aromatic Hydrocarbon Feedstocks |
WO2017005715A1 (en) | 2015-07-09 | 2017-01-12 | Total Research & Technology Feluy | Mesoporous zeolitic material, method for making the same and use |
ITUB20154284A1 (it) | 2015-10-09 | 2017-04-09 | Eme International Ltd | Pyrolysis process and plasma pyrolysis reactor for carrying out said process |
US10391480B2 (en) | 2017-05-01 | 2019-08-27 | Saudi Arabian Oil Company | Methods of producing hierarchical beta zeolites with tunable mesoporosity through pore directing agent assisted base leaching |
US10661260B2 (en) | 2017-06-15 | 2020-05-26 | King Fahd University Of Petroleum And Minerals | Zeolite composite catalysts for conversion of heavy reformate to xylenes |
US11097262B2 (en) | 2017-06-15 | 2021-08-24 | Saudi Arabian Oil Company | Composite hierarchical zeolite catalyst for heavy reformate conversion to xylenes |
US10118163B1 (en) | 2017-07-28 | 2018-11-06 | Saudi Arabian Oil Company | Methods for producing hierarchical mesoporous zeolite beta |
US10350585B1 (en) | 2018-08-14 | 2019-07-16 | Saudi Arabian Oil Company | Methods for synthesizing hierarchical zeolites for catalytic cracking |
-
2017
- 2017-06-15 US US15/624,090 patent/US10661260B2/en active Active
-
2018
- 2018-06-06 JP JP2019568698A patent/JP2020524072A/ja active Pending
- 2018-06-06 EP EP18735043.4A patent/EP3638416A1/en active Pending
- 2018-06-06 WO PCT/US2018/036269 patent/WO2018231602A1/en unknown
- 2018-06-06 CN CN201880039999.7A patent/CN110913986A/zh active Pending
- 2018-06-06 SG SG11201911918YA patent/SG11201911918YA/en unknown
- 2018-06-06 KR KR1020207001305A patent/KR20200027506A/ko not_active IP Right Cessation
-
2019
- 2019-12-15 SA SA519410814A patent/SA519410814B1/ar unknown
-
2020
- 2020-04-15 US US16/849,038 patent/US11351527B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130165315A1 (en) * | 2011-12-27 | 2013-06-27 | King Fahd University Of Petroleum And Minerals | Method of forming a hydrocarbon cracking catalyst |
CN104603087A (zh) * | 2012-04-02 | 2015-05-06 | 沙特阿拉伯石油公司 | 从重质芳烃生产二甲苯和轻质烯烃的方法 |
Non-Patent Citations (2)
Title |
---|
HAIJUAN ZHANG ETC.: "Preparation and characterization of Beta/MCM-41composite zeolite with a stepwise-distributed pore structure", <POWDER TECHNOLOGY> * |
HAIYAN XU ETC.: "Synthesis of Beta/MCM-41 composite molecular sieve with high hydrothermal stability in static and stirred condition", <JOURNAL OF COLLOID AND INTERFACE SCIENCE> * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI814099B (zh) * | 2020-11-06 | 2023-09-01 | 美商艾克頌美孚化學專利股份有限公司 | 烷基芳族化合物之製造 |
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US20180361365A1 (en) | 2018-12-20 |
EP3638416A1 (en) | 2020-04-22 |
SA519410814B1 (ar) | 2022-08-30 |
SG11201911918YA (en) | 2020-01-30 |
KR20200027506A (ko) | 2020-03-12 |
JP2020524072A (ja) | 2020-08-13 |
US11351527B2 (en) | 2022-06-07 |
WO2018231602A1 (en) | 2018-12-20 |
US20200254428A1 (en) | 2020-08-13 |
US10661260B2 (en) | 2020-05-26 |
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