CN109414693A - 包含con型沸石和zsm-5型沸石的催化剂组合物、制备和使用该组合物的方法 - Google Patents

包含con型沸石和zsm-5型沸石的催化剂组合物、制备和使用该组合物的方法 Download PDF

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CN109414693A
CN109414693A CN201780042949.XA CN201780042949A CN109414693A CN 109414693 A CN109414693 A CN 109414693A CN 201780042949 A CN201780042949 A CN 201780042949A CN 109414693 A CN109414693 A CN 109414693A
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E·祖德马
D·W·赞特
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Shell Internationale Research Maatschappij BV
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Abstract

本发明涉及一种催化剂组合物，其包含(a)载体，所述载体包含(i)5到95wt％的CON型沸石，(ii)5到95wt％的ZSM‑5型沸石，和(iii)10到60wt％的无机粘合剂；以及b)0.001到10wt％的一或多种金属，所述金属选自由IUPAC元素周期表第6‑11族组成的组。本发明另外涉及一种制备所述催化剂组合物的方法和使用通过本发明方法所制备的催化剂使含有烷基芳香烃的原料转化的方法。

Description

包含CON型沸石和ZSM-5型沸石的催化剂组合物、制备和使用 该组合物的方法
相关申请的交叉引用
本申请要求2016年7月13日提交的美国临时申请第62/361,767号的优先权，其公开内容通过引用结合在此。
技术领域
本发明涉及一种用于制备催化剂的方法以及使用所述催化剂转化含有芳香族烃的原料的方法。
背景技术
重整油是通过催化转化在70℃到190℃范围内沸腾的直馏烃(例如直馏石脑油)而获得的芳香族产物。重整油原料自身是通过石油原油的分馏或蒸馏获得，其组成视原油来源而变化，但通常具有较低的芳香族含量。在转化成重整油时，芳香烃含量显著增加且所得烃混合物用作有价值的化学中间体来源以及用作汽油组分非常理想。主要组分是一组芳香烃，其通常称作BTX：苯、甲苯和二甲苯，包括乙苯。可能会存在其它组分，例如它们的氢化同系物，例如环己烷。
关于BTX组，最有价值的组分是苯和二甲苯，且因此BTX经常经受以下处理以增加那些两种芳香烃的比例：使甲苯发生加氢脱烷基化而生成苯和使甲苯发生歧化而生成苯和二甲苯。在二甲苯中，对二甲苯是最有用的商品。已开发二甲苯异构化或烷基转移方法以增加对二甲苯的比例。
汽油生产者能够利用的另一种方法是使乙苯发生加氢脱烷基化而生成苯。
通常，汽油生产者从重整油流中分离出含有含至少8个碳原子的芳香烃化合物的馏分，且接着对这个物流进行二甲苯异构化，此旨在使对二甲苯组分最大化。二甲苯异构化是一种催化工艺。正常情况下，接着分离出对二甲苯，留下苯、甲苯(除非已经应用了甲苯转化工艺)、剩余的混合二甲苯(包括乙苯)，以及含有至少9个碳原子的芳香烃化合物。这种烷基芳香烃流能够如下转化：(i)进行脱烷基化以选择性地除去乙苯并增加苯的产率，同时使二甲苯发生异构化直到平衡或(ii)进一步重整以将乙苯转化为二甲苯，同时使二甲苯发生异构化直到平衡或(iii)进行烷基转移，这通过使二甲苯发生异构化直到平衡并使特定的烷基芳香烃化合物发生脱烷基化。后一种方法是本发明的目标。
US5952536描述了借助于催化剂进行的气相芳香烃烷基转移，所述催化剂包含选自SSZ-26、Al-SSZ-33、CIT-1、SSZ-35和SSZ-44的沸石。
在烷基芳香烃处理的这后一阶段的烷基转移反应中，如果催化剂在转化特定的烷基芳香烃化合物(更具体地说，甲基乙基苯)时具有活性，更优选在二甲苯产率相对高和/或总转化率相对高的情况下具有活性，则是有利的。此外，如果催化剂得到的产物中的乙苯与具有8个碳原子的总芳香烃化合物的比率低，则是有利的。此外，如果烷基转移催化剂具有活性、产生二甲苯含量高的产物、产生高纯度的苯、产生高纯度的二甲苯、限制芳香烃损失且/或使二甲苯发生异构化直到平衡，则是有利的。芳香烃典型地因添加氢气而形成例如烯烃或烷烃而可能有损失。
本发明的目的是提供能够用于这种工艺中的催化剂、使用这种催化剂的方法和制备这种催化剂的方法。
发明内容
本发明涉及一种催化剂组合物，其包含(a)载体，所述载体包含(i)按载体总重量计，含量在5到95重量％(wt％)范围内的CON型沸石，(ii)按载体总重量计，含量为5到95wt％的ZSM-5型沸石，和(iii)按载体总重量计，含量在10到60wt％范围内的无机粘合剂；以及(b)0.001到10wt％的一或多种金属，所述金属选自由IUPAC元素周期表的第6-11族组成的组。
本发明另外涉及一种制备这种催化剂组合物的方法，包含以下步骤：(a)将CON型沸石、ZSM-5型沸石和无机粘合剂混合并且将所得混合物挤出；(b)任选地对步骤(a)中所得的挤出物进行热处理；(c)用包含一或多种金属的溶液浸渍煅烧过的挤出物，所述金属选自由IUPAC元素周期表的第6-11族组成的组；和(d)任选地对步骤(c)中所得的浸渍挤出物进行热处理。
本发明另外涉及一种使用本发明的催化剂或通过本发明的催化剂制备方法所制备的催化剂使含有烷基芳香烃的原料转化的方法。
具体实施方式
CON型沸石在所属领域中众所周知。对于本申请来说，CON沸石如“沸石构架类型图谱(Atlas of Zeolite Framework Types)”Baerlocher等人，第六次修订版(Elsevier2007)中所定义和所描述。本发明中使用的优选CON型沸石是SSZ-26和SSZ-33。最优选的是沸石SSZ-26。沸石SSZ-26可以如US4910006中所述制备。沸石SSZ-33可以如US4963337中所述制备。合成时，沸石SSZ-33倾向于成为硼硅酸盐。硼可以用其它元素取代以产生活性烷基转移催化剂。
ZSM-5沸石也如“沸石构架类型图谱”Baerlocher等人，第六次修订版(Elsevier2007)中所定义和所描述。
本发明的催化剂组合物包含载体，按载体总重量计，所述载体优选包含含量为20到90wt％的CON型沸石。按载体总重量计，CON型沸石的存在量优选在30到70wt％范围内，更优选在40到60wt％范围内。CON型沸石优选具有10到120范围内、优选40到110范围内且更优选50到100范围内的二氧化硅与氧化铝摩尔比。
本发明的催化剂组合物包含载体，按载体材料化合物的总重量计，所述载体包含含量为10到70wt％的ZSM-5型沸石。按载体总重量计，ZSM-5型沸石的存在量优选在15到60wt％范围内，更优选在20到40wt％范围内。本发明催化剂组合物中的CON沸石含量优选高于ZSM-5型沸石。更优选地，本发明催化剂组合物中的CON沸石含量优选比ZSM-5含量高至少5wt％，且更优选高至少10wt％。
ZSM-5型沸石优选具有10到50范围内、优选15到40范围内且更优选18到35范围内的二氧化硅与氧化铝摩尔比。
ZSM-5型沸石优选具有20到500nm范围内的数均粒度。优选地，ZSM-5型沸石具有30到300nm范围内，更优选50到200nm范围内的数均粒度。据观察，根据本发明使用的ZSM-5型沸石的平均颗粒小能够提高苯纯度。
根据本发明使用的适合的ZSM-5型沸石可以根据例如US 3,702,886和US 4,511,547中所述来制备。ZSM-5型沸石的适合实例包括可以从Zeolyst International购得的CBV3014E、CBV 3020E和CBV 8014。
按载体总重量计，本发明的催化剂优选含有含量在10到50wt％范围内的无机粘合剂。优选地，按总载体计，无机粘合剂的存在量在10到40wt％范围内，更优选在15到30wt％范围内。
无机粘合剂宜选自由以下组成的组：γ-氧化铝、二氧化硅、二氧化硅-氧化铝、膨润土、高岭土、二氧化钛、氧化锆、氧化铈、氧化镓、克立莫(climotilolite)、蒙脱石和其任何混合物。优选的无机粘合剂是氧化铝，更具体地说，γ氧化铝。
呈成形形式(例如挤出物)的载体通常具有属于200到600m2/g、优选250到500m2/g、更优选350到450m2/g范围内的BET表面积。表面积宜根据ASTM D3663-03(2015)测量。另外，根据压汞法，挤出物优选具有0.2到1.2ml/g、优选0.4到1.0ml/g、更优选0.5到0.8ml/g范围内的孔隙体积。
本发明的催化剂组合物可以成形为任何特定形式。适合的形状包括三叶形和圆柱形，本发明的催化剂组合物优选三叶形形状。
载体优选由CON型沸石、ZSM-5型沸石和氧化铝组成。
可以通过使载体成形且随后对所述载体进行热处理来制备载体。热处理优选包含煅烧成形的载体，煅烧之前任选地进行干燥。干燥温度宜在50℃到200℃的范围内。干燥时间宜在0.5到24小时范围内。煅烧温度宜在200℃到800℃范围内，优选在300℃到600℃范围内。煅烧载体材料时，宜应用相对短的时间，例如0.5到5小时范围内。煅烧宜在400到700℃范围内，优选450到600℃范围内的温度下进行。
本发明的催化剂组合物包含一或多种金属，所述金属选自由2013年5月1日的IUPAC元素周期表第6-11族组成的群组。所述催化剂组合物优选包含一或多种选自由以下组成的组的金属：钨、钒、钼、铼、镍、钴、铬、锰、铂和钯。所述金属最优选钼。
金属含量优选在0.001到10wt％金属范围内(按催化剂总重量计)，更优选在0.1到10wt％范围内、更优选在2到9wt％、更优选2到8wt％、更优选2到6wt％金属范围内(按催化剂总重量计)。所述金属可以借助于金属盐溶液并入载体中。所述金属优选通过孔隙体积浸渍法来并入。
金属的量是作为独立于实际存在的化合物的金属来计算。
本发明的催化剂组合物的形状宜使得装填催化剂颗粒的反应器具有至少10体积％、优选在20到70％范围内、更优选在35到55体积％范围内的平均空隙分率。
将金属并入载体中之后，优选对浸渍过的载体进行热处理。此热处理优选100到最高500℃，优选200到最高450℃。
使用催化剂组合物之前，优选的是使催化剂组合物上的金属呈金属化(而非氧化)形式。因此，催化剂组合物优选经历还原条件，例如在还原气氛(例如在氢气中，任选地用惰性气体(例如氮气或二氧化碳)稀释)中，在150到600℃范围内的温度下加热0.5到5小时范围内的时间。
本发明催化剂优选用于含有烷基芳香烃的原料的转化(更具体地说，烷基转移)工艺中。
烷基芳香烃原料宜包含至少70wt％，更具体地说，至少80wt％，更具体地说，至少90wt％的甲苯和含有至少9个碳原子的烷基芳香烃。可以存在的其它化合物是乙苯和乙基-二甲苯。原料优选包含重量比为10:90到90:10的甲苯和含有至少9个碳原子的烷基芳香烃化合物。烷基芳香烃原料最优选地包含35到75wt％的甲苯和25到65wt％的含有至少9个碳原子的烷基芳香烃化合物。
原料宜在氢气存在下与催化剂组合物接触。这可以在固定床系统、移动床系统或流化床系统中进行。这种系统可以连续地或以分批方式操作。优选在固定床系统中进行连续操作。催化剂可以在一个反应器中使用或在若干个单独反应器串联使用，或在回转系统中操作，以确保在催化剂更换期间连续操作。
本发明的烷基转移方法优选在200到600℃范围内，优选在250到500℃范围内并且更优选在300到400℃范围内的温度下进行。
所述方法优选在1到30巴范围内的压力下、优选在2到20巴范围内的压力下且更优选在2到10巴范围内的压力下进行。
所述方法中应用的重量空速宜在0.2到30hr-1，优选2到20hr-1范围内，并且更优选在3到6hr-1范围内。
进料与氢气比率mol.mol-1是在0.5到100范围内，优选在1到10范围内。
优选回收反应排出物并且进行蒸馏处理以移出所期望的产物，更具体地说，二甲苯和苯。未反应的反应物(例如甲苯)宜进行再循环以供进一步反应。
现将通过以下实例说明本发明。
实例
实例1
二氧化硅与氧化铝摩尔比为23并且数均晶体尺寸为100nm的ZSM-5沸石获自Zeolyst International。二氧化硅与氧化铝摩尔比为79的CON沸石根据如US7648694中所述的方法制备。
通过挤出80wt％沸石和20wt％氧化铝(Pural SB1，可购自Sasol)的混合物来制备载体。将所得挤出物干燥且在约550℃下煅烧1小时。使用过铼酸溶液，通过孔隙体积浸渍法而在煅烧过的挤出物中并入0.3wt％铼。将浸渍过的挤出物在140℃下干燥两小时，且接着在480℃下煅烧1小时。将所得催化剂组合物研磨至30-80目颗粒，且按不同比率混合以获得如表2中所述的各种烷基转移催化剂系统。
使用线上GC分析，评估催化剂系统在中试工厂中对具有表1中所概述的组成的典型烷基转移进料进行的烷基转移作用。在整个实验中维持30巴的总压力和5的氢气:烃摩尔比。测试之前，催化剂在氢气流中、在室温和大气压下干燥1小时，接着加热到400℃维持1小时，加压到30巴，在这些条件下再维持1小时，并且最后冷却到310℃。烃进料按照4h-1的WHSV引入，并且所述系统操作24小时以使性能稳定。表1比较了24小时后该温度下的关键性能参数。
表1.进料组成
表2.催化剂综述和烷基转移性能
表2表明本发明催化剂组合物在烷基转移方面引起的MEB转化率高于仅含有CON沸石的催化剂，同时二甲苯产率和/总转化率相对较高。另外，在二甲苯产率相对高和/总转化率相对高的情况下，本发明催化剂组合物产生的产物中的乙苯与具有8个碳原子的总芳香烃化合物比率低。

Claims (10)

1.一种催化剂组合物，其包含
(a)载体，所述载体包含(i)按载体总重量计，含量在5到95wt％范围内的CON型沸石，(ii)按载体总重量计，含量为5到95wt％的ZSM-5型沸石，和(iii)按载体总重量计，含量在10到60wt％范围内的无机粘合剂；以及
(b)0.001到10wt％的一或多种金属，所述金属选自由IUPAC元素周期表第6-11族组成的组。
2.根据权利要求1所述的催化剂组合物，其中按载体总重量计，所述载体包含含量在20到90wt％范围内的CON型沸石。
3.根据权利要求1所述的催化剂组合物，其中按载体总重量计，所述载体包含含量为10到70wt％的ZSM-5型沸石。
4.根据权利要求1所述的催化剂组合物，其中按催化剂总重量计，所述催化剂组合物包含含量在1到10wt％范围内的钼作为金属。
5.根据权利要求1所述的催化剂组合物，其中所述ZSM-5型沸石具有15到35范围内的二氧化硅与氧化铝摩尔比。
6.根据权利要求1所述的催化剂组合物，其中所述ZSM-5型沸石具有50到200nm范围内的数均晶体尺寸。
7.一种用于制备根据权利要求1到6中任一项所述的催化剂组合物的方法，其包含以下步骤：
(a)将CON型沸石、ZSM-5型沸石和无机粘合剂混合并且将所得混合物挤出；
(b)任选地对步骤(a)中所得的挤出物进行热处理；
(c)用包含一或多种金属的溶液浸渍所述煅烧过的挤出物，所述金属选自由IUPAC元素周期表第6-11族组成的组；以及
(d)任选地对步骤(c)中所得的所述浸渍过的挤出物进行热处理。
8.一种使用根据权利要求1到6中任一项所述或通过根据权利要求7所述的方法制备的催化剂使含有烷基芳香烃的原料转化的方法。
9.根据权利要求8所述的方法，其中所述原料包含重量比率为10:90到90:10的甲苯和含有至少9个碳原子的烷基芳香烃化合物。
10.根据权利要求8所述的方法，其中所述原料包含35到75wt％的甲苯和25到65wt％的含有至少9个碳原子的烷基芳香烃化合物。
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