CN110072617B - 催化剂组合物 - Google Patents

催化剂组合物 Download PDF

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Publication number
CN110072617B
CN110072617B CN201780075703.2A CN201780075703A CN110072617B CN 110072617 B CN110072617 B CN 110072617B CN 201780075703 A CN201780075703 A CN 201780075703A CN 110072617 B CN110072617 B CN 110072617B
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range
support
type zeolite
zsm
catalyst composition
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CN110072617A (zh
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H-X·李
R·B·莫尔
G·萨巴特·普加达斯
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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Abstract

催化剂组合物，其包含(a)载体，所述载体包含(i)5‑95wt％的丝光沸石型沸石，其平行于12环通道的方向的平均微晶长度为60纳米或更小和中孔容积为至少0.10cc/g，(ii)5‑95wt％的ZSM‑5型沸石；和(iii)10‑60wt％的无机粘合剂；以及(b)0.001‑10wt％的一或多种催化活性金属，其中所述无机粘合剂包括二氧化钛，及其制备和其在烷基芳烃转化中的用途。

Description

催化剂组合物
技术领域
本发明涉及催化剂组合物、其制备及其在烷基芳族转化、更具体地烷基转移中的用途。
发明背景技术
乙苯是可从石脑油裂解或重整油中获得的芳族烃中的一种。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)所获得的芳族产物。用于产生重整油的催化剂通常是氧化铝载铂催化剂。重整油原料自身是通过石油原油的分馏或蒸馏获得，其组成视原油的来源而变化，但通常芳族烃含量较低。在转化成重整油时，芳族烃含量显著增加且所得烃的混合物作为有价值的化学中间物的来源以及作为汽油的组分而变得高度合乎需要。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。可以存在其它组分，例如其的氢化同系物，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个芳族的比例：将甲苯加氢脱烷基化成苯且将甲苯歧化成苯和二甲苯。在二甲苯中，对二甲苯是最有用的商品并且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。
可以应用的另一种方法是将乙苯加氢脱烷化成苯。
通常，优选的是从重整油流中分离BTX，使BTX流进行二甲苯异构化，以使得对二甲苯组分最大化。二甲苯异构化是一种催化工艺。此工艺中所使用的一些催化剂具有不仅使二甲苯异构化且同时使乙苯组分脱烷烃化的能力。通常，接着将对二甲苯分离出来，留下苯、甲苯(除非已经应用了一种或多种甲苯转化工艺)和剩余的混合二甲苯，包括乙苯。这种BTX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。
WO 2009/158233 A2描述了一种所谓的UZM-14聚集材料，其包括微晶的球形聚集体，所述微晶具有MOR骨架类型，平行于12环通道的方向的平均微晶长度为60纳米或更小和中孔容积为至少0.10cc/g。在一个优选的实施方案中，公开了所述聚集材料与选自氧化铝、二氧化硅和二氧化硅-氧化铝中的一种或多种的粘合剂组合。
WO 2009/158233A2的实施例1描述了催化剂，其包括所谓的UZM-14聚集材料结合氧化铝粘合剂和作为掺杂剂的铼，在实施例2中概述了在包含甲苯和各种C9/C9+芳族化合物的原料的烷基转移中对所述催化剂的测试。
WO 2009/158233A2的实施例4描述了催化剂，其包括所谓的UZM-14聚集材料结合MFI沸石和氧化铝粘合剂以及作为金属掺杂剂的镍和钼，在包含甲苯和各种C9/C9+芳族化合物的原料的烷基转移中测试了所述催化剂。
WO2009/158244A2也描述了烷基转移方法，其使用的催化剂包括所谓的UZM-14聚集材料，其包括微晶的球形聚集体，所述微晶具有MOR骨架类型，平行于12环通道的方向的平均微晶长度为60纳米或更小和中孔容积为至少0.10cc/g，其结合选自氧化铝、二氧化硅和二氧化硅-氧化铝的一种或多种的粘合剂。WO2009/158244A2中的实施例与WO2009/158233A2中的实施例大致相似。
发明内容
一个目的是提供一种可以用于烷基芳族转化过程、更具体地烷基转移的改进的催化剂，制备这样的催化剂的方法，以及使用这样的催化剂的方法。
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95wt％范围内的丝光沸石型沸石，其平行于12环通道的方向的平均微晶长度为60纳米或更小和中孔容积为至少0.10cc/g，(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％的一或多种催化活性金属，其中所述无机粘合剂包括二氧化钛。
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)将丝光沸石型沸石、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)用包含一或多种催化活性金属的溶液浸渍煅烧过的挤出物，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根据本发明的催化剂或通过根据本发明的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
在烷基芳烃转化中，更具体地说，通过使二甲苯异构化至平衡并使特定烷基芳族化合物脱烷基化的烷基转移，如果催化剂在生产二甲苯中具有高活性，则可能是有利的。此外，如果产物含有高纯度的苯，则在这种烷基转移反应中可能是有利的。苯的纯度是在产物中苯沸腾范围中沸腾的部分中苯的量。本发明的方法可以生产高纯度的苯。此外，当催化剂用于烷基芳族化合物转化时，观察到有限的芳烃损失。
丝光沸石型沸石和ZSM-5型沸石在本领域中是众所周知的。对于本申请，这些沸石如在“Atlas of Zeolite Framework Types”，Baerlocher等人编辑，第六修订版(Elsevier2007)中定义和描述。
在WO2009/158244A2中描述了用于本发明的优选的丝光沸石型沸石。
本文所述的沸石的平均粒度通过计算通过使用X射线衍射(线加宽)和Scherrer方程测量的样品的数均粒径来确定。该技术在用于确定微晶粒度的本领域中是众所周知的(参见，例如，“Catalysis:An Integrated Approach to Homogeneous,Heterogeneous andIndustrial Catalysis”,J.A.Moulijn,P.W.N.M.van Leeuwen,R.A.van Santen(Eds.),Elsevier,1993,pp.365-367,WO 2009/158244A2)。
具体而言，本发明的丝光沸石优选具有10至60，更优选为20～40的平均微晶长度。平行于12环通道方向的平均微晶长度通过将Scherrer方程应用于x射线衍射数据来测量。在分析之前，通过在氮气中将NH4交换的形式加热至540℃2小时，然后在空气中加热5小时，将丝光沸石转化为氢形式。具体地，对于CuKα辐射，在23.8°2θ处测量(002)衍射峰的半峰全宽(FWHM)，然后从Scherrer方程计算平行于12环通道方向的平均微晶长度L0002。假设峰的形状是部分高斯的并且部分Cauchy的。
此外，丝光沸石型沸石的中孔体积至少为0.10cc/g。优选地，丝光沸石型沸石的中孔体积为至多0.23cc/g。中孔体积由氮吸附等温线如下确定。在分析之前，通过在空气中将NH4交换的形式加热至550℃5小时，将丝光沸石转化为氢形式。然后测量吸附等温线，并从最高P/P0值(约0.98)的氮吸收确定总孔体积。使用t-图估计微孔体积。从解吸等温线获得数据，中孔体积由沸石上吸附的气体总和计算，其孔径范围如下：600-260径向埃(大孔)、260-100径向埃(中孔)、100-50径向埃(微孔)和50-20径向埃。
本发明的催化剂组合物包含载体，以载体的总重量计，其优选地包含20到90wt％的量的丝光沸石型沸石。按载体总重量计，丝光沸石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。
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。
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25到300nm范围内，更优选25到200nm范围内和甚至更优选30到200nm范围内的数均粒度。如上所述通过使用X射线衍射(谱线加宽)和Scherrer方程确定平均粒度。
在本发明的特别优选的实施方案中，ZSM-5型沸石具有25到100nm范围内，更优选30到100nm范围内和甚至更优选30到70nm范围内的数均粒度。令人惊讶地观察到，将ZSM-5型沸石的小平均颗粒与本催化剂组合物的其它特征组合使用可以进一步提高苯纯度。
可以制备根据本发明使用的合适的ZSM-5型沸石，例如，如在US 3702886 A和US4511547A中描述的。ZSM-5型沸石的合适实例包括CBV 3014E、CBV 3020E和CBV 8014，可从Zeolyst International商购获得。
在本发明的一个优选实施方案中，如上所述的催化剂组合物包含(a)载体，所述载体包含(i)按载体总重量计，含量在5到95wt％范围内的丝光沸石型沸石，其平行于12环通道的方向的平均微晶长度为60纳米或更小和中孔容积为至少0.10cc/g，(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至10wt％的一种或多种催化活性金属，
其中无机粘合剂由二氧化钛组成。
按载体总重量计，根据本发明的催化剂组合物优选含有含量在10到50wt％范围内的二氧化碳作为无机粘合剂。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。
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0.3到1.0ml/g、更优选0.4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。合适的形状包括三叶形和圆柱形。
优选地，本发明的催化剂组合物为三叶形形状。
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750℃范围内，优选450到700℃范围内，更优选500到700℃范围内的温度下进行。
本催化剂组合物包含一种或多种催化活性金属。优选地，这些金属选自由2013年5月1日的IUPAC元素周期表第2-14族。所述催化剂组合物优选包含一或多种选自由以下的金属：锡、钨、钒、钼、铼、镍、钴、铬、锰、铂和钯。
载体可以通过混合丝光沸石、ZSM-5型沸石和无机粘合剂，使混合物成型并使成型混合物在200至800℃的温度下进行煅烧来制备。可在煅烧之前干燥成型混合物。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。
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。
根据本发明的催化剂组合物可合适地具有这类形状，使得填充有催化剂粒子的反应器的平均空隙分数为至少10体积％，优选地在20体积％到70体积％的范围内，更优选地在35体积％到55体积％的范围内。
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600℃，优选200到最高550℃。
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。
本发明还涉及用于使用根据本发明的催化剂进行的含有芳香族烃的原料的转化(更具体地说，烷基转移)的方法。
烷基芳香烃原料宜包含至少30wt％，更具体地说，至少40wt％，更具体地说，至少50wt％，最具体地说，至少90wt％的甲苯和含有至少9个碳原子的烷基芳香烃的总量。可以存在的其它化合物是乙苯和二甲苯。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。这可在固定床系统、移动床系统或流体化床系统中进行。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。催化剂可在一个反应器中或串联的数个独立的反应器中使用或在摆动系统中操作，以确保在催化剂更换期间连续的操作。
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50巴范围内的压力下、优选在10到40巴范围内的压力下且更优选在25到35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。
本公开不限于如上所述的实施方案和所附权利要求。可以想到许多修改，并且可以组合各个实施方案的特征。
为便于更好地理解本发明，提供一些实施方案的某些方面的以下实施例。这些实施例决不应被理解为限制或限定本发明的范围。
实施例
实施例1催化剂制备
制备一系列催化剂，其包括两种沸石(丝光沸石和ZSM-5，以它们的铵形式(可从Zeolyst International获得))、无机粘合剂以及作为催化活性金属的铂和第14族金属掺杂剂的混合物。制备的每种催化剂含有类似量的铂和第14族金属掺杂剂作为催化活性金属。所述催化活性金属按US 6867340 B2加入。
按照相同的通用程序制备催化剂，其中例如通过混合18克丝光沸石(无论是丝光沸石-A或丝光沸石-B，参见下面的表2)(以铵形式)、12克ZSM-5(ZSM-5A或ZSM-5B，参见下表2)(以铵形式)与粘合剂(氧化铝(可获得自例如Sasol)、氧化锆(可获得自Exchi)或二氧化钛(可获得自Evonik Industries))。
将粉末与包含铂和第14族金属掺杂剂的金属盐溶液胶溶在一起。挤压胶溶的混合物以获得具有1.6mm直径的颗粒。这些挤压物在120℃下干燥2小时，接着在样品的空气中，在500℃下煅烧2小时。
制备的催化剂的完整概述在下面的表2中给出。
实施例2催化剂测试
实施例1中制备的催化剂在通过脱烷基化和烷基转移从含有C9+芳香族烃的原料生产苯和混合二甲苯中进行了测试。
在芳烃烷基转移试验中并且使用以下表1中总结的原料对这些样品中的每一个进行性能测试。
表1
Figure BDA0002086699580000071
Figure BDA0002086699580000081
一旦被测试的10克催化剂组合物已装入固定床反应器中并首先在氢气氛(>99％纯度)中在400℃下进行还原步骤一小时，进行性能测试。然后，在30巴的总系统压力，3.5g进料/g催化剂/小时的重时空速和4.5mol.mol-1的氢气与进料比下，在固定床反应器中测量催化剂性能。改变温度以达到45％的所需转化率，性能结果示于下表2中。
表2.催化剂综述和烷基转移性能
Figure BDA0002086699580000082
*丝光沸石A(SAR＝20；晶体尺寸>60nm，中孔体积≥0.10cc/克)。
**丝光沸石B(SAR＝18；晶体尺寸<45nm，中孔体积≥0.10cc/克)。
***ZSM-5A(SAR＝25；晶体尺寸>100nm，具体地在100-115nm之间的范围内)。
****ZSM-5B(SAR＝30；晶体尺寸<100nm，具体地在25-40nm之间的范围内)。
苯的纯度可以看作是产物中在苯的大约沸点附近沸腾的馏分中苯的量。关于这一点，技术人员会明白，苯本身不具有沸点范围，而是具有沸点。然而，通过蒸馏获得的苯通常含有C6和C7非芳族烃杂质，难以与苯通过蒸馏分离，因为它们的沸点接近苯的沸点。因此，在产物中在大约苯的沸点沸腾的馏分将包含含有6个碳原子的化合物例如苯、含有5个碳的甲基取代的环状化合物和含有6个碳原子的环状化合物。因此，在表2中，在苯沸点馏分中的共沸物％是苯的纯度的量度，并且当使用参考催化剂1时相对于所述苯沸点馏分中共沸物％给出。
芳香族损失是进料中的芳香族化合物mol％减去产物中的芳香族化合物mol％，再除以进料中的芳香族化合物mol％。当使用参考催化剂(催化剂1)时，此量相对于芳香族化合物损失给出。
在表2中的上述实验结果显示，根据本发明的催化剂令人惊奇地导致产品具有增加的苯纯度和减少的芳族化合物的损失。
因此，使用如前文所述的特定的丝光沸石结合ZSM-5和作为粘合剂的二氧化钛的惊人益处在表2中显而易见。

Claims (8)

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5-95wt％范围内的丝光沸石型沸石，其平行于12环通道的方向的平均微晶长度为60纳米或更小和中孔容积为至少0.10cc/g，(ii)按载体总重量计，含量为5-95wt％的ZSM-5型沸石；其中所述ZSM-5型沸石具有25到100nm范围内的数均晶体尺寸，其通过X射线衍射测定，和(iii)按载体总重量计，含量在10-60wt％范围内的无机粘合剂；其中，按载体总重量计，载体中(i)、(ii)和(iii)的总和等于100％；以及
(b)0.001-10wt％的一种或多种催化活性金属，
其中所述无机粘合剂包括二氧化钛。
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20-90wt％范围内的丝光沸石型沸石。
3.根据权利要求1或2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10-70wt％的ZSM-5型沸石。
4.根据权利要求1-3中任一项所述的催化剂组合物，其中所述ZSM-5型沸石具有15到40范围内的二氧化硅与氧化铝摩尔比。
5.一种用于制备根据权利要求1到4中任一项所述的催化剂组合物的方法，包含以下步骤：
(a)将丝光沸石型沸石、ZSM-5型沸石和无机粘合剂混合，并挤出得到的混合物，
(b)任选地对步骤(a)中得到的挤出物进行热处理，
(c)用含有一种或多种催化活性金属的溶液浸渍任选地热处理的挤出物，和(d)将步骤(c)中获得的浸渍的挤出物进行热处理。
6.一种使用根据权利要求1到4中任一项所述或通过根据权利要求5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。
7.根据权利要求6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。
8.根据权利要求6所述的方法，其中所述原料包含范围为35-75wt％的甲苯和范围为25-65wt％的含有至少9个碳原子的烷基芳香烃化合物。
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