CN1596150A - 含有负载于中孔载体上微孔分子筛的催化剂及其制备方法 - Google Patents

含有负载于中孔载体上微孔分子筛的催化剂及其制备方法 Download PDF

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CN1596150A
CN1596150A CNA028235576A CN02823557A CN1596150A CN 1596150 A CN1596150 A CN 1596150A CN A028235576 A CNA028235576 A CN A028235576A CN 02823557 A CN02823557 A CN 02823557A CN 1596150 A CN1596150 A CN 1596150A
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molecular sieve
described method
mesopore
inorganic oxide
mixture
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Inventor
单志平
雅各布斯·格尼留斯·扬森
叶春渊
约翰尼斯·亨德里克·克格尔
托马斯·马施迈尔
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CB&I Technology Inc
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ABB Lummus Global Inc
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Abstract

一种包括负载在中孔无机氧化物载体上的微孔分子筛的催化材料。微孔分子筛包括β分子筛、Y分子筛或ZSM－5分子筛。中孔无机氧化物可为如氧化硅或氧化铝，以及任选包括其它金属。本发明描述了制备和使用该催化材料的方法。

Description

含有负载于中孔载体上微孔分子筛的催化剂及其制备方法
相关申请的相互参考
本申请为1999年9月7日提交的系列号为09/390,276的美国专利申请的部分继续，并要求其优先权，在此全部引入作为参考。
背景
1.发明领域
本公开内容涉及包含嵌入催化剂载体的分子筛的催化材料，具体地说，涉及嵌入中孔载体的微孔分子筛。
2.技术背景
大多数现有烃加工技术都基于分子筛催化剂。分子筛催化剂在此领域里是众所周知的，它具有排列很好的孔大小均匀的孔体系。但是，这些材料不是只有微孔就是只有中孔。微孔定义为直径小于约2am的孔。中孔定义为直径约2-约50am的孔。
由于这种烃加工反应是传质控制的，因此具有理想孔大小的分子筛将有助于反应物向催化剂活性位扩散以及产物从催化剂中扩散出来。
发明概述
这里提供一种用于烃催化加工的材料。该材料包括分子筛和多孔无机氧化物，其中在无机氧化物的微孔和中孔中包括至少97vol.％的中孔。分子筛优选为微孔分子筛例如β分子筛、Y分子筛或ZSM-5分子筛。这里描述了制备和使用这种材料的方法。
这里所述的催化材料有利于促进反应物向催化剂活性位扩散，比只用分子筛时活泼大约5倍。
附图简述
下面参照附图对各实施方案进行描述，其中：
图1是纯β分子筛、含β分子筛的中孔无机氧化物载体(样品1)的X射线衍射图和样品1的延伸扫描时间图；
图2是含β分子筛的中孔无机氧化物载体(样品1)的高分辨透射电子显微扫描图，插图显示分子筛部分的电子衍射图；
图3是含β分子筛的中孔无机氧化物载体(样品1)和不含β分子筛的对比样品的NH3程序升温脱附分析图；
图4是实施例3、4和5产生的材料以及纯β分子筛的中孔大小分布图；
图5是实施例2-5产生的材料以及纯β分子筛的X射线衍射谱图。
优选实施方案详述
这里所述催化剂包括嵌入中孔载体的微孔分子筛。微孔分子筛可以是任何一种微孔分子筛，包括但不限于β分子筛、Y分子筛和ZSM-5分子筛。这种分子筛在此领域里是众所周知的，而且在商业上流通。分子筛可被嵌入中孔载体或者可被原位合成于催化剂载体中。
催化剂载体优选为三维的中孔无机氧化物材料，以无机氧化物材料的微孔和中孔计算(即没有嵌入任何分子筛)，含有中孔至少97vol.％(即微孔不大于3vol.％)，一般至少含有98vol.％中孔。制备优选的多孔含硅催化剂载体的方法在序列号为09/390,276的美国专利申请中做了描述。N2孔度法测得，优选催化剂的平均中孔大小为约2-约25nm。一般地，中孔无机氧化物的制备通过加热(1)无机氧化物在水中的前体和(2)有机模板剂的混合物而实现，后者与前体产生的氧化物前体或者氧化物物种很好地混合，优选地与之形成氢键。
原料一般是无定形材料，可由一种或多种无机氧化物组成，例如氧化硅或氧化铝，再加入或不加其它金属氧化物。硅原子可部分地被金属原子例如Al、Ti、V、Zr、Ga、Mn、Zn、Cr、Mo、Ni、Co和Fe等替代。任选地，可在开始进行产生含中孔的结构的过程之前将这些另加的金属嵌入材料中。也可任选地在材料制成后，将体系中阳离子用其它离子如碱金属离子(如Na、K、Li等)替代。
有机模板剂优选为二醇(一种包括两个或多个羟基的化合物)，例如丙三醇、二甘醇、三甘醇、四甘醇、丙二醇等，或者三乙醇胺、环丁砜、四亚乙基五胺和二苯甲酸二乙二醇酯中的一种或多种。
中孔催化剂载体为假结晶材料(即用现有有效的X射线衍射技术没有观察到结晶度)。中孔的壁厚约为3nm-约25nm。BET(N2)法测得的催化剂载体的表面积优选为约400m2/g-约1200m2/g。催化剂孔体积为约0.3cm3/g-约2.2cm3/g。
催化剂中分子筛的含量范围从小于约1wt.％到大于约99wt.％，优选为约5-约90wt.％，更优选为约20-约80wt.％。含分子筛的催化剂优选包括不大于约5vol.％的微孔。
更具体地说，制备催化剂的方法包括将分子筛悬浮于水中。然后将无机氧化物前体加入水中并混合。无机氧化物前体可为硅酸盐，如四乙基原硅酸盐(TEOS)或铝原如异丙基氧化铝。TEOS和异丙基氧化铝可从已知供应商处购得。
溶液的pH值优选保持在7.0以上。任选地，水溶液可包含其它金属离子例如所述离子。搅拌之后，加入与氧化硅(或其它无机氧化物)物种以氢键连接的有机模板剂，与水溶液混合。有机模板剂有助于在成孔期间形成中孔，如下所讨论。有机模板剂不应当疏水，以免在水溶液中形成分离相。有机模板剂可为上面列出的一种或多种化合物。优选地，通过滴加并搅拌的方式将有机模板剂加入无机氧化物水溶液中。一段时间后(如大约1-2小时)，混合物形成浓胶。优选地，在这期间，对混合物进行搅拌，有助于组分的混合。溶液优选包括醇类，可将它加入混合物和/或通过无机氧化物前体的分解而原位产生。例如，一旦加热，TEOS就产生乙醇。异丙基氧化铝分解产生丙醇。
然后胶体在约5℃-约45℃的温度下老化，优选为室温，完成水解和无机氧化物原的缩聚。老化时间优选为高达约48h，一般为约2-约30h，更优选为约10-约20h。老化后，在约98℃-100℃下将胶体在空气中加热足够的一段时间(例如约6-约24h)，通过赶走水份而使其干燥。优选地，帮助形成中孔的有机模板剂在老化阶段应当留在胶体中。因此，优选有机模板剂的沸点至少约150℃。
干燥后的材料仍然含有有机模板剂，将它加热到基本形成中孔的温度。孔形成步骤进行的温度高于水的沸点，大约达到有机模板剂的沸点。一般地，形成中孔的温度为约100℃-约250℃，优选为约150℃-约200℃。孔形成步骤任选地在密封容器的本身压力及水热条件下进行。水热步骤的长短和温度影响最终产品的中孔大小和体积。一般地，提高处理温度和延长处理时间将提高最终产品的中孔体积百分含量。
孔形成步骤后，在约300℃-约1000℃下焙烧催化材料，优选为约400℃-约700℃，更优选为约500℃-约600℃，保持焙烧温度足够长的时间以使材料的焙烧有效。焙烧步骤的时间典型为约2h-约40h，优选为5h-15h，部分依赖于焙烧温度。
为避免热点，应当逐渐升温。优选地，催化材料的温度应当缓慢地升到焙烧温度，速率为约0.1-约25℃/min，更优选为约0.5-约15℃/min，最优选为约1-约5℃/min。
在焙烧期间，催化材料的结构最终形成，有机分子被赶走并分解。
脱除有机模板剂的焙烧过程可用有机溶剂如乙醇抽提的方式替代。这样，模板剂可被回收再用。
本发明的催化剂粉末也可预先与粘合剂如氧化硅和/或氧化铝混合，然后通过挤条或者其它合适方法形成期望的形状(如片、环等)。
金属离子如Ti、V、Zr、Ga、Mn、Zn、Ni、Fe、Co、Cr和Mo可以通过浸渍、离子交换或者部分取代晶格原子的方式加入催化剂，正如G.W.Skeels和E.M.Flanigen在M.Occelli等编辑的A.C.S.Symposium Series，Butterworth，第398卷，420-435页(1989)中所述。
这里所述的催化剂用于烃加工过程如加氢裂化、加氢异构化、脱蜡、烷基化等。
例如，采用所述催化剂的烃与烯烃进行烷基化的温度为约90℃-约250℃，压力为约10-约500psig，空速为约1-约20WHSV。
采用所述催化剂的烃加氢裂化的反应条件包括约200℃-约400℃的温度、约150-约1000psig的压力，以及约1-约50WHSV的空速。
采用所述催化剂的烃加氢异构化的反应条件包括约150℃-约500℃的温度、约15-约3500psig的压力，以及约0.1-约20WHSV的空速。
采用所述催化剂的烃脱蜡的反应条件包括约150℃-约500℃的温度、约100-约1500psig的压力，以及约0.1-约20WHSV的空速。
下面通过实施例1-5说明制备本发明的催化剂组合物的方法。实施例6对催化剂在烷基化过程中的使用进行了说明。对比实施例A不依照本发明，使用不含所述中孔载体的纯β分子筛。组分含量以重量份数形式给出。
实施例1
首先，将1.48份Si/Al比为24.9、平均颗粒大小为1μm的已焙烧的β分子筛悬浮于16.32份水中并搅拌30min。然后一边搅拌，一边加入20.32份四乙基原硅酸盐(TEOS)。再连续搅拌30min后，加入9.33份三乙醇胺。再搅拌30min后，将4.02份四乙基氢氧化胺水溶液(从Aldrich购得的35％溶液)滴加进混合物以提高pH值。搅拌大约2h后，混合形成浓的不流动的胶体。在室温静态条件下将胶体老化17h。再将胶体在100℃下空气中干燥28h。将干燥的胶体转移到压力釜，在170℃进行水热处理17.5h。最后，在空气中600℃下焙烧10h，升温速率为1℃/min。
最终产品标为样品1。样品1中β分子筛的理论含量为20wt.％。用X射线衍射(XRD)、透射电子显微镜(TEM)、氮孔度法、氩孔度法和NH3程序升温脱附法(TPD)对样品进行表征。为对比起见，也对纯β分子筛进行XRD表征。
参看图1，标为图“b”的纯β分子筛的XRD谱图在2θ约7.7°和22.2°处(扫描时间为33min)显示明显的特征反射。负载β分子筛晶体的中孔无机氧化物载体(样品1)的XRD谱图标为图“a”。在低角度观察到强峰，表明样品1为中间结构型材料。β分子筛的峰相对较小，这是因为最终产品的最大理论分子筛含量只有约20wt.％。当样品1的扫描时间延长到45h时，β分子筛的特征峰清晰可见，标为图“c”。
参看图2，它是样品1的高分辨透射电子显微图“TEM”，在中孔基底12上显示出黑灰区域11。插图“ED”为电子衍射谱图，证实黑灰区域11是β分子筛晶体。
氮吸附法表明，样品1具有窄的中孔大小分布，主要集中于约9.0nm处，具有710m2/g的高比表面积和1.01cm3/g的高总孔容。氩吸附法显示在约0.64nm处的微孔大小分布峰，对应于β分子筛的微孔。直径小于0.7nm的孔的微孔体积为0.04cm3。这约是纯β分子筛的微孔体积的16％。根据最终的复合物，开始加入的未焙烧的β分子筛量为20wt.％。由于焙烧时模板剂的脱除，已用的β分子筛损失约20wt.％。考虑到焙烧时分子筛的损失量，最终产品中β分子筛的预期含量大约16wt.％，这和从微孔体积得到的值一致。
参看图3，样品1的NH3-TPD测试显示有两个脱附峰，表明存在类似于分子筛的强酸位。
实施例2
首先，将3.40份Si/Al比为150、平均颗粒大小为0.2μm的已焙烧的β分子筛悬浮于84.98份水中并搅拌30min。然后一边搅拌，一边加入105.80份TEOS。再连续搅拌30min后，加入38.27份三乙醇胺。再搅拌30 min后，将20.93份四乙基氢氧化胺水溶液(35％)滴加进混合物。搅拌大约2h后，混合变成浓的不流动的胶体。在室温静态条件下将胶体老化24h。再将胶体在98-100℃下空气中干燥24h。将干燥的胶体转移到四个50ml高压釜中，在180℃进行水热处理4h。最后，在空气中600℃下焙烧10h，升温速率为1℃/min。形成的产物为样品2，其XRD谱图示于图5。最终复合物中大约有10wt.％的β分子筛。
实施例3
首先，将4.59份Si/Al比为150、平均颗粒大小为0.2μm的已焙烧的β分子筛悬浮于51.02份水中并搅拌30min。然后一边搅拌，一边加入22.97份三乙醇胺。再连续搅拌30min后，加入63.50份TEOS。再搅拌另外30min后，将12.58份四乙基氢氧化胺水溶液(35％)滴加进混合物。搅拌大约2h后，混合形成浓的不流动胶体。在室温静态条件下将胶体老化24h。再将胶体在100℃下空气中干燥24h。将干燥的胶体转移到三个50ml高压釜中，在180℃进行水热处理4h。最后，在空气中600℃下焙烧10h，升温速率为1℃/min。形成的产物为样品3，其XRD谱图示于图5，清晰地显示出两个β分子筛的特征峰。最终复合物中大约有20wt.％的β分子筛。氮吸附法测得其表面积约为730m2/g，孔体积约为1.08cm3/g。其中孔体积大小分布示于图4。
实施例4
首先，将12.23份Si/Al比为150、平均颗粒大小为0.2μm的已焙烧的β分子筛悬浮于50.99份水中并搅拌30min。然后在悬浮液一边搅拌，一边加入22.96份三乙醇胺。再连续搅拌30min后，加入63.48份TEOS。再搅拌另外30min后，将12.68份四乙基氢氧化胺水溶液(35％)滴加进混合物。搅拌大约2h后，混合形成浓的不流动胶体。在室温静态条件下将胶体老化24h。再将胶体在100℃下空气中干燥24h。将干燥的胶体转移到三个50ml高压釜中，在180℃进行水热处理4h。最后，在空气中600℃下焙烧10h，升温速率为1℃/min。形成的产物为样品4，其XRD谱图示于图5，清晰地显示出两个β分子筛的特征峰。最终复合物中大约有20wt.％的β分子筛。氮吸附法测得其表面积约为637m2/g，孔体积约为1.07cm3/g。其中孔体积大小分布示于图4。
实施例5
首先，将9.17份Si/Al比为150、平均颗粒大小为0.2μm的已焙烧的β分子筛悬浮于16.99份水中并搅拌30min。然后在所述悬浮液中一边搅拌，一边加入7.65份三乙醇胺。再连续搅拌另外30min后，加入21.16份TEOS。再搅拌另外30min后，将4.19份四乙基氢氧化胺水溶液(35％)滴加进混合物。搅拌大约2h后，混合形成浓的不流动胶体。在室温静态条件下将胶体老化24h。再将胶体在100℃下空气中干燥24h。将干燥的胶体转移到三个50ml高压釜中，在180℃进行水热处理4h。最后，在空气中600℃下焙烧10h，升温速率为1℃/min。形成的产物为样品5，其XRD谱图示于图5，清晰地显示出两个β分子筛的特征峰。最终复合物中大约有60wt.％的β分子筛。氮吸附法测得其表面积约为639m2/g，孔体积约为0.97cm3/g。其中孔体积大小分布示于图4。
实施例6
将8份样品1与2份Nyacol型氧化铝混合以产生催化剂。混合物干燥后，以5℃/min的升温速率升到120℃进行焙烧，120℃温度恒温一小时后，以5℃/min的升温速率升到500℃，恒温5小时，最后以5℃/min的速率降温至150℃，然后在干燥器中冷却至室温。再将催化剂手工压碎，筛分为-12/+20mesh，测试其活性。该催化剂在中孔载体中含有16wt.％的β分子筛。将1.000g催化剂装入循环微分固定床反应器。循环速率(200gm/min)约为进料速率(6.1gm/min)的33倍。刚开始用苯充满已装填的反应器，然后当反应器温度到190℃，用计量泵计量进料(含0.35wt.％乙烯的苯)。一次试验进行7h。反应条件包括190℃的温度、350psig的压力和6WHSV的空速。在试验开始、中间和最后取原料样。每3min，取一次产品样，用气相色谱分析。根据速率平衡，得到在含16wt.％β分子筛的催化剂上苯和乙烯烷基化反应形成苯乙烯的速率常数为0.30cm3/g-sec。可选地，该值等价于含80wt.％β分子筛的催化剂上1.50cm3/g-sec的速率常数值。
对比实施例A
根据实施例l描述的方法，不加入分子筛，制备全硅中孔载体。形成的载体标为对比样A。在对比样A上进行NH3-TPD测试，其结果示于图3。
对比实施例B
从供应商获得β分子筛样品，它含有80wt.％β分子筛和20wt.％粘合剂(Si/Al比为4.9)，将其大小调整为-12/+20mesh。β分子筛的孔大小分布示于图4。采用与所述实施例6相同的方法和设备，在相同的烷基化条件下，对本对比实施例中纯β分子筛的活性进行测试。得到速率常数为0.29cm3/g-sec。
比较实施例6和对比实施例B的结果，根据本发明的实施例6中催化剂的苯与乙烯烷基化活性大于相同量的纯β分子筛约5倍。这些结果表明，在样品1的合成过程中，中孔分子筛载体中分子筛晶体的完整性得到保持。结果也说明，在样品1的中孔载体上的微孔β分子筛在合成催化剂后，仍然容易进入，而载体的中孔促进芳烃烷基化反应中的传质。
虽然所述描述包含许多细节，但是这些细节不应当被看作是对本发明范畴的限制，仅作为优选实施方案的范例。本领域的普通技术人员在本发明权利要求所定义的范畴和精神范围内，将预见到其它许多可能性。

Claims (31)

1.一种材料，包括：
一种分子筛；和
多孔无机氧化物，它包括基于无机氧化物微孔和中孔至少97vol.％的中孔。
2.按权利要求1所述材料，其中分子筛为微孔分子筛。
3.按权利要求2所述材料，其中微孔分子筛选自β分子筛、Y分子筛和ZSM-5分子筛。
4.按权利要求1所述材料，其中多孔无机氧化物包含至少98vol.％的中孔。
5.按权利要求1所述材料，其中中孔的大小为约2nm～约25nm。
6.按权利要求1所述材料，其中多孔无机氧化物是氧化硅。
7.按权利要求1所述材料，其中多孔无机氧化物是氧化铝。
8.按权利要求1所述材料，包括选自Al、Ti、V、Zr、Ga、Mn、Zn、Cr、Mo、Ni、Co和Fe的金属原子。
9.按权利要求1所述材料，其中分子筛的重量百分含量组成为约5％～约90％。
10.按权利要求1所述材料，其中分子筛的重量百分组成含量为约20％～约80％。
11.一种制备催化材料的方法，其包括如下步骤：
a)将分子筛与水、无机氧化物或无机氧化物的前体结合，至少一种形成中孔的有机化合物通过氢键与无机氧化物或无机氧化物的前体连接，形成混合物；
b)干燥混合物；
c)加热干燥的混合物到一定温度，经过一段足够的时间，形成中孔氧化物结构。
12.按权利要求11所述方法，其中所述形成中孔的有机化合物选自丙三醇、二甘醇、三甘醇、四甘醇、丙二醇、三乙醇胺、环丁砜、四亚乙基五胺和二甘醇二苯甲酸酯。
13.按权利要求11所述方法，其中所述形成中孔的有机化合物的沸点至少约为150℃。
14.按权利要求11所述方法，其中无机氧化物通过无机氧化物前体与水反应而形成。
15.按权利要求14所述方法，其中无机氧化物前体选自四乙基原硅酸盐和异丙基氧化铝。
16.按权利要求11所述方法，其中混合物的pH值维持在约7.0以上。
17.按权利要求11所述方法，其中化合物通过滴加同时搅拌的方式加入混合物中，混合物形成胶体。
18.按权利要求11所述方法，其中混合物包括烷醇。
19.按权利要求11所述方法，其中混合物在空气中一定温度下干燥足够的一段时间，以赶走水份和挥发性有机化合物。
20.按权利要求11所述方法，其中加热步骤(c)包括将干燥的混合物加热到约100℃～约250℃的温度。
21.按权利要求11所述方法，其中加热步骤(c)包括将干燥的物料加热到约150℃～约200℃的温度。
22.按权利要求11所述的方法，进一步包括在约300℃～约1000℃的温度下焙烧已加热干燥混合物的步骤。
23.按权利要求11所述的方法，进一步包括在约400℃～约700℃的温度下焙烧已加热干燥的混合物约2～约40小时的步骤。
24.按权利要求11所述的方法，进一步包括将金属离子与混合物结合，所述的金属选自Ti、V、Zr、Ga、Mn、Zn、Ni、Fe、Co、Cr和Mo。
25.按权利要求11所述的方法，进一步包括将粘合剂与催化材料掺合，使催化材料形成预定形状的步骤。
26.一种处理烃原料的方法，包括：
在充分的反应条件下，将含有至少一种烃组分的原料与催化有效量的催化剂接触，使所述烃组分转化，所述的催化剂包括负载于多孔无机氧化物上的分子筛，所述的多孔无机氧化物基于其微孔和中孔有至少97vol.％的中孔。
27.按权利要求26所述方法，其中烃组分的转化通过加氢裂化反应、加氢异构化反应、脱蜡反应或烷基化反应实现。
28.按权利要求26所述方法，其中所述的原料包括芳香族化合物和烯烃，反应条件要足以实现芳香族化合物与烯烃的烷基化。
29.按权利要求28所述方法，其中反应条件包括温度为约90℃～约250℃、压力为约10～约500psig和空速为约1～约20WHSV。
30.按权利要求26所述方法，其中分子筛为微孔分子筛。
31.按权利要求30所述方法，其中微孔分子筛为β分子筛。
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