CN1041216C - 合成多层材料它的合成方法及它的用途 - Google Patents

合成多层材料它的合成方法及它的用途 Download PDF

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CN1041216C
CN1041216C CN94192390A CN94192390A CN1041216C CN 1041216 C CN1041216 C CN 1041216C CN 94192390 A CN94192390 A CN 94192390A CN 94192390 A CN94192390 A CN 94192390A CN 1041216 C CN1041216 C CN 1041216C
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S·L·A·冯
S·L·劳顿
W·J·罗思
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Abstract

合成多层材料，它具有包括以下摩尔关系的组成：
X2O3∶(n)YO2
其中n低于约35，X是三价元素，和Y是四价元素，该材料进一步的特征在于，对于1，3，5-三甲基苯的吸着容量为至少约35μl/g煅烧合成材料，初期吸收15mg2，2-二甲基丁烷/g煅烧合成材料的时间短于20秒，和煅烧材料的X-射线衍射图谱在12.4±0.2，9.9±0.3，6.9±0.1，6.2±0.1，3.55±0.07和3.42±0.07埃处有d-间距最大值。

Description

合成多层材料它的合成方法及它的用途
本发明涉及合成多层材料，涉及它的制备方法以及它作为有机化合物转化用的吸着剂或催化剂组分的用途。
多孔无机固体已经用作供工业上使用的催化剂和分离介质。它们的微结构开合程度能让分子进入这些材料的较大的表面区域，以增强它们的催化和吸着活性。当今使用的多孔材料可被分成三大类，使用材料微结构的细节作为分类基础。这些类别是无定形和次晶载体，结晶体分子筛和改性多层材料。在这些材料的微结构中的细节差别，预示着它们本身在材料的催化和吸着性能方面的重大差异，以及在用来表征它们的各种可观察性能中的差异，如它们的表面积、孔隙尺寸和这些尺寸的可变性，存在或不存在X-射线衍射图谱和此类图谱的细节，以及当它们的微结构由透射电子显微技术和电子衍射方法进行研究时材料的外观。
无定形和次晶材料代表了多年来用于工业应用的重要类别的多孔无机固体。这些材料的典型实例是通常用于催化剂配方的无定形氧化硅类和用作固体酸催化剂和石油重整催化剂载体的次晶过渡元素氧化铝类，术语“无定形”本文用来指长程无序的材料，并多少有些被误解，因为几乎所有的材料在某种程度上均有序，至少局部规模上是如此。用来表述这些材料的另一术语是“X-射线无差异”。氧化硅类微结构由100-250埃的致密无定形氧化硅的颗粒组成(kirk-Othmer Encyclopedia of ChemicalTechnology，第三版，20卷，John Wiley & Sons，New York，P.766～781，1982)，具有取决于颗粒间空隙产生的孔隙度。由于在这些材料中长程无序，孔趋向于在相当大的范围内分布。有序性的缺乏还可在X-射线衍射图谱中表现出来，它通常是非特征的。
次晶材料如过渡元素矾土类也具有宽的孔径分布，但较清晰的X-射线衍射图谱通常由几个宽峰组成。这些材料的微结构由凝聚氧化铝相的微晶区组成，材料的孔隙度取决于这些区域之间的不规则空隙(K.Wefers and Chanakya Misra，“Oxides andHydroxides of Aluminum(铝的氧化物和氢氧化物))”，TechnicalPaper(技术论文)No.19修订版，Alcoa Research Laboratories(阿尔科研究实验室)，P.54～59，1987)。由于在每种材料的情况下，没有长程有序地控制材料中的孔径，孔径的可变性一般是相当高的。在这些材料中的孔径落在称作中孔范围的范围内，包括，例如在15～200埃范围内的孔。
与这些在结构上不确定的固体形成强烈对比的是孔径分布非常窄的材料，因为它由精确重复材料微结构的晶体性质所控制。例如沸石是有序的，多孔晶体材料(一般是硅铝酸盐)具有如X-射线衍射方法所测定的一定晶体结构，在其中有大量的小空穴，它们由许多较小的通道或孔互相连通。在特定沸石材料中，这些空穴和孔的尺寸是均匀的。由于这些孔的尺寸能够确保吸附某种尺寸的分子，而同时排斥较大尺寸的分子，这些材料已知是“分子筛”，并以各种方式利用，以充分利用这些性能。
现有技术已经制成了许多种合成沸石。这些沸石中的许多都已经由字母或其它简便符号表示，比如表示方式为沸石A(USP2,882,243)；X(USP 2,882,244)；Y(USP 3,130,007)；ZK-5(USP 3,247,195)；ZK-4(USP 3,314,752)；ZSM-5(USP3,702,886)；ZSM-11(USP 3,709,979)；ZSM-12(USP3,832,449)；ZSM-20(USP 3,972,983)；ZSM-35(USP4,016,245)；ZSM-23(USP 4,076,842)；MCM-22(USP4,954,325)；MCM-35(USP 4,981,663)；MCM-49(WO92/22498)；和PSH-3(USP 4,439,409)。
USP 4,439,409针对命名为PSH-3的物质的晶体分子筛和从一种反应混合物合成它的方法，该反应混合物含有六亚甲基亚胺和一种有机化合物，该化合物用作合成本发明多层MCM-56的导向剂。在EP 293,032中讲述了似乎与USP 4,439,409的PSH-3相同的物质的组合物，但具有附加的结构组分。六亚甲基亚胺也被指出用于合成USP 4,954,325中的晶体分子筛MCM-22；USP4,981,663中的MCM-35；在WO 92/22498中的MCM-49；和在USP 5,021,141中的ZSM-12。在USP 4,826,667和EP 231,860中，讲述了称作沸石SSZ-25的物质的分子筛组合物，该沸石是从含有金刚烷季铵离子的反应混合物合成的。
含有一些能被溶胀剂间隔开的各层的某些多层材料，可被支撑而获得具有较大孔隙度的材料。此类多层材料的例子包括粘土类。这类粘土可用水溶胀，从而粘土的层被水分子间隔开。其它多层材料虽不能用水溶胀，但可以用某些有机溶胀剂如胺类和季铵化合物溶胀。这类水不溶胀的多层材料的例子在USP 4,859,648中有叙述，且包括多层硅酸盐，麦羟硅钠石，水羟硅钠石，三钛酸盐和钙钛矿。水不溶胀但可用某些有机溶胀剂溶胀的多层材料的另一例子，是正如在USP 4,831,006中所描述的含有空位的钛金属酸盐(titanometallate)材料。
一旦多层材料溶胀，该材料通过在间隔开的各层之间***热稳定性物质如氧化硅而被支撑。例如，前述USP 4,831,006和USP 4,859,648描述了将其中所述的水不溶胀的多层材料支撑的方法。有关将多层材料支撑的方法和支撑的产品的其它专利包括USP 4,216,188；4,248,739；4,176,090；和4,367,163；和EP205,711。
支撑的多层材料的X-射线衍射图谱可以显著地变化，这取决于对通常本已非常有序的多层微结构的溶胀和支撑破坏程度。在某些支撑的多层材料中微结构的规则性被如此糟糕地破坏，以致于在X-射线衍射图谱上在低角度区域中仅观察到一个峰，该峰位于与在支撑材料中层间重复相对应的d-间距处。轻度破坏的材料在这一区域中显示有几个峰，它们一般是这一基本重复的有序性体现。有时还能观察从这些层的晶体结构的X-射线反射现象。在这些支撑的多层材料中的孔径分布，比在无定形和次晶材料中的孔径分布窄，但比在晶体骨架材料中的孔径分布宽。
本发明针对一种合成多层材料，本文称作MCM-56，它具有包括以下摩尔关系的组成：
X2O3∶(n)YO2其中n低于约35，X是三价元素，和Y是四价元素，该材料的进一步特征在于对于1，3，5-三甲苯的吸着容量是至少约35μl/g煅烧合成材料，初期吸着15mg 2，2-二甲基丁烷/g煅烧合成材料的时间短于20秒，以及煅烧材料的X-射线衍射图谱在12.4±0.2，9.9±0.3，6.9±0.1，6.2±0.1，3.55±0.07，和3.42±0.07埃处有d-间距最大值。
本发明的MCM-56与许多晶体骨架材料，主要是MCM-22，和MCM-49，和与某些其它多层材料有区别，但表现出某些相似性。MCM-56的平均晶胞c-参数为约25.5埃，而不形成层间桥。当所合成的MCM-56在例如540℃下煅烧时，结构没有压缩，但保持多层形式。煅烧MCM-56吸附至少约35μl/g的1，3，5-三甲基苯，例如至少为煅烧MCM-22或MCM-49所吸附1，3，5-三甲基苯的4倍。在由2，2-二甲基丁烷的初期快速吸着量表示的吸着数据方面，煅烧MCM-56与煅烧MCM-22和MCM-49也不一样。当与MCM-22和MCM-49相比较时，MCM-56表现出独特的吸着率和催化利用率。
具体地说来，本发明的MCM-56材料基本上是纯净的，很少有或没有可检测到的杂质晶体或层相，且具有一种如下X-射线衍射图谱，它与下表I(合成的)和下表II(煅烧的)中所示的其它已知的合成材料或热处理材料的区别在于线条位置和强度的结合。在这些表中，强度由相对于在12.4埃处的d-间隔线来确定。
                         表I
                                             最接近的3-维材料
MCM-56             最接近的多层材料
                                             Material MCM-49晶面间的               晶面间的                  晶面间的d-间距    相对强度     d-间距     相对强度       d-间距    相对强度(A)                    (A)                       (A)--         --         10.5         m             --         --12.4±2      vs         12.4         m-vs          12.5       vs--         --         11.1         m             11.2       m-s9.9±0.3     m          --           --            --         ----         --         9.2          m             9.0        m6.9±0.1     w          6.9          w             6.9        w6.4±0.3     w          6.7          w             6.4        w6.2±0.1     w          6.2          w             6.2        m3.57±0.07   m-s        3.56         w-m           3.55       w-m3.44±0.07   vs         3.43         s-vs          3.44       vs
                      表IIMCM-56                 MCM-22                 MCM-49晶面间的                晶面间的               晶面间的d-间距    相对强度      d-间距     相对强度    d-间距      相对强度(A)                     (A)                    (A)12.4±0.2    vs           12.4       m-vs        12.4        vs--         --           11.0       m-s         11.1        s9.9±0.3     m-s          --         --           --         ----         --           8.8        m-vs        8.9         m-s6.9±0.1     w            6.9        w-m         6.9         w6.2±0.1     s            6.2        m-vs        6.2         m3.55±0.07   m-s          3.56       w-m         3.57        w3.42±0.07   vs           3.42       vs          3.43        s-vs
用于获得表I中数据的材料是湿饼形式的多层材料MCM-56，用同样的有机导向剂(它在煅烧时转移到MCM-22中)合成的湿饼式多层材料，和湿饼式晶体MCM-49。用于获得表II的材料是用于表I的材料的煅烧产物。每种材料的煅烧是在540℃的空气中进行2～20小时。允许在MCM-56和这一家族的其它成员(MCM-22和MCM-49型材料)之间存在初始差异的最有效鉴别特征可以在8.8～11.2埃的d-间距的区域内观察到。后一类别在约8.8～9.2埃和10.8～11.2埃处显示出两个可分辨的最大峰，在它们之间有明显的凹陷。MCM-56的特征在于以d-间距9.9埃附近为中心的宽带。尽管该带可具有不对称轮廓，例如带有拐点，但凹陷的出现表明开始形成MCM-49和损失MCM-56。
用使用铜K-α辐射的、装有锗固体检测器的Scintag衍射***收集这些X-射线衍射数据。衍射数据由0.02度的2θ角步进扫描来记录，其中θ角是布喇格角，每一步的计数时间为10秒。晶面间距d(按埃单位(_)计算)和谱线的相对强度，I/I0，是本底以上最强谱线强度的百分之一，是通过使用外形拟合程序(二次导数算法)得到的。该等强度对于洛伦兹和极化效应是未校正的。相对强度以符号表示：VS＝极强(60-100)，S＝强(40-60)，m＝中等(20～40)和w＝弱(0～20)。应该明白，这一样品的按单线形式列举的衍射数据可由多根重叠的谱线组成，它们在某些条件，如结晶变化方面的差异，可以表现为可分辨的或部分分辨的谱线。典型地，结晶变化可包括晶胞参数和/或晶体对称性方面的次要变化，而无结构方面的变化。作为在阳离子含量，骨架组成，孔填充的性质和程度，及热和/或水热历史方面的有差异的结果，也可发生这些次要的影响，包括相对强度方面的变化。在衍射图中的其它变化可以显示这些材料之间的重要差异，这是将MCM-56与类似材料例如MCM-49，MCM-22和PSH-3相比较的情况。
这些材料在X-射线衍射图上的差异的重要性可从材料结构方面的知识来解释。MCM-22和PSH-3是不平常材料家族中的成员，因为经过煅烧后，在X-射线衍射图上的变化可通过在一个轴向尺寸的显著变化来解释。这表明在材料内部键结方式有深层次变化，并不是用于合成的有机物质的简单损失。这一家族的前体成员与煅烧成员(例如，对比表I和表II中的中栏)在X-射线衍射方面明显不同。对前体和煅烧形式的X-射线衍射图的考察，揭示出具有非常相似位置和强度的多个反射峰，而其它峰则不同。这些差异中的一些与轴向尺寸和键接方式的变化有直接关系。
晶体MCM-49具有与该家族的煅烧成员的轴向尺寸相类似的轴向尺寸，因此，在它们的X-射线衍射图谱上有相似性。然而，MCM-49轴向尺寸不同于在煅烧过的材料中所观察到的轴向尺寸。例如，在MCM-22中轴向尺寸的变化可以从对这些变化特别敏感的峰位置来检测。两个这种峰出现在～13.5埃和～6.75埃(前体MCM-22)，在～12.8埃和～6.4埃(合成MCM-49)以及在～12.6埃和～6.30埃(煅烧MCM-22)，MCM-49的～12.8埃峰非常靠近所有这三种材料都能观察到的强12.4埃峰，且经常无法与它完全地分开。同时，已煅烧MCM-22材料的～12.6埃峰通常只能看作是强～12.4埃峰上的肩峰。
MCM-56与上述类似材料在其它特征方面的区别总结于下表III。
                   表  III
   特  征         MCM-22      MCM-49      MCM-56合成的：结       构         多层        3维         多层可 溶 胀 性         是          不是        是煅烧后的收缩        是          是          不是煅烧的：
对于1，3，5-三甲  低          低          高
基苯的吸着容量1
2，2-二甲基丁烷   慢          幔          快
的初期吸着速率2注：1  低吸着容量被定义为低于约8～10μl/g。高容量至少是低
 容量的约4倍。煅烧过的MCM-56吸着至少约35μl/g。2  初期吸着速率被定义为吸着第一批15mg 2，2-二甲基丁烷/
 g吸着剂所需要的时间。快吸着速率是短于20秒；慢吸着时
 间至少是快吸着的5倍。
 1克煅烧过的MCM-56在短于约20秒，例如短于约15秒的时
 间内吸着15mg 2，2-二甲基丁烷。
 本发明的独特多层材料具有包含以下摩尔关系的组成：
 X2O3∶(n)YO2其中X是三价元素，如铝、硼、铁和/或镓，优选铝；Y是四价元素，如硅和/或锗，优选硅；和n低于约35，例如，5～25，通常入程度是使III A族元素，例如铝在结构中被浸渍或与其以物理方式紧密地混合。此类组分可被浸渍入组合物中或浸渍到组合物上，例如，在铂的情况下，通过用含有铂金属离子的溶液处理该硅酸盐。所以，用于此目的的合适铂化合物包括氯铂酸，氯化亚铂和含有铂胺配合物的各种化合物。
MCM-56可进行热处理，而不会影响其多层结构，其中在热处理后它仍可以被溶胀。热处理一般是通过在至少约370℃的温度下加热至少1分钟和一般不长于20小时来进行的。尽管热处理可使用低于大气压，为方便起见，希望使用常压。可在至多约925℃的温度下进行热处理。热处理产品，尤其以它的金属、氢和铵形式，特别可用来催化某些有机物，例如烃的转化反应。此类反应的非限制性实例包括在
U.S.P.4,954,325；4,973,784；
4,992,611；4,956,514；4,962,250；4,982,033；4,962,257；
4,962,256；4,992,606；4,954,663；4,992,615；4,983,276；
4,962,040；4,962,229；4,968,402；5,000,839；5,001,296；
4,986,894；5,001,295；5,001,283；5,012,033；5,019,670；
5,019,665；5,019,664；and 5,013,422。中所描述的那些反应。
当本发明的多层MCM-56材料用作吸着剂或用作有机化合转化工艺中的催化剂时，应该脱水，至少部分地脱水。这可在200-370℃范围内的温度下，在诸如空气、氮气等的气氛中及在常压、低于大气压或正压下加热30～48小时来完成。还可以仅仅将MCM-56置于真空中，在室温下进行脱水，但是，为了获得足够的脱水量需要较长的时间。
可以从含有碱金属或碱土金属(M)，例如钠或钾源，阳离子，三价元素X，例如铝的氧化物，四价元素Y，例如硅的氧化10～20，更常见13～18。在合成的形式中，该材料具有以无水形式为基础的和按照每n摩尔YO2的氧化物摩尔数关系的结构式，如下：
(0-2)M2O∶(1-2)R∶X2O3∶(n)YO2其中M是碱金属或碱土金属，和R是有机部分。M和R组分与该材料相结合，是它们在合成过程中存在的结果，并可通过下文更具体描述的后合成方法而被轻易地除去。
当与前述材料如煅烧的PSH-3，SSZ-25，MCM-22，和MCM-49相比较时，发现本发明的MCM-56材料可以进行热处理，并以煅烧形式表现出高表面积(大于300m2/gm)和对于某些较大的分子通常有高的吸着容量。MCM-56湿饼，即所合成的MCM-56，可被溶胀，表明不存在层间桥，与不可溶胀的MCM-49相反。
所合成材料最初的碱金属或碱土金属阳离子(如钠离子)，可以根据本领域中众所周知的技术，通过与其它阳离子进行离子交换，至少部分交换，被置换到所需要的程度。优选的置换用阳离子包括金属离子，氢离子，氢前体(例如铵)离子及它们的混合物。特别优选的阳离子是能提高某些烃转化反应的催化活性的那些阳离子。这些包括氢，稀土金属和元素周期表中II A、III A、IV A、I B、II B、III B、IV B和VIII族的金属。
当用作为催化剂时，本发明的多层MCM-56材料可以经受处理，一般加以煅烧，以除去部分或所有的任何有机成分。该晶体材料还可用作与加氢组分如钨、钒、钼、铼、镍、钴、铬、锰，或贵金属如铂或钯紧密结合的催化剂，用于加氢—脱氢工艺。此类组分可以通过共结晶方式进入组合物，交换进入组合物，其进物，导向剂(R)和水的反应混合物制取本发明的多层MCM-56材料，该反应混合物具有在以下范围内的、按氧化物摩尔比的组成：
反应物         有用        优选
YO2/X2O3  5 to 35     10 to 25
H2O/YO2   10 to 70     16 to 40
OH-/YO20.05 to 0.5  0.06 to 0.3
M/YO2   0.05 to 3.0  0.06 to 1.0
R/YO2    0.1 to 1.0   0.3 to 0.5
在本合成方法中，为了获得本发明的结晶产品，YO2源应该包括占主要地位的固体YO2，例如至少约30wt％固体YO2。当YO2是氧化硅时，使用含有至少约30wt％固体氧化硅的氧化硅源，例如Ultrasil(一种沉淀的、喷雾干燥的含90wt％氧化硅的氧化硅)或Hisil(一种沉淀的、水合的SiO2，它含有约87wt％氧化硅，约6wt％游离水和约4.5wt％水合键合H2O，且它的粒径为约0.02微米)，有利于在所需合成条件下从以上反应混合物制备晶体MCM-56。所以，优选地，YO2例如氧化硅源含有至少约30wt％固体YO2例如氧化硅和更优选含有至少约40wt％固体YO2例如氧化硅。
导向剂R选自环烷基胺，氮杂环烷，二氮杂环烷，和它们的混合物，烷基包括5～6个碳原子。R的非限制性实例包括环戊基胺，环己基胺，环庚基胺，六亚甲基亚胺，七亚甲基亚胺，高哌嗪及它们的混合物。
本发明多层材料的结晶，可以在合适的反应器，比如聚丙烯大口瓶或特氟隆衬里的高压釜或不锈钢压力釜中，在静态或搅拌条件下进行。结晶优选在80～225℃之间的温度下进行。然而，对于从上述反应混合物合成MCM-56来说，关键的是在开始形成MCM-49(损失MCM-56)之前停止和骤冷该反应。之后，从液体中分离出并回收MCM-56。合成MCM-56且随后不转化为MCM-49所需要的时间取决于所使用的反应温度。然而，通过鉴别在9～11埃d-间距范围内的X-射线衍射图谱随合成进程而发生的变化，而得以方便地控制反应，使在MCM-49形成之前骤冷反应。因此，从表I中可清楚地看出，MCM-56在d-间距9.9±0.3处显示出一单峰，而MCM-49显示出两个中心位于d-间距9.0和11.2埃的峰。
本发明的多层MCM-56材料可用作吸着剂，比如用来在气相或液相中从多种组分(对于MCM-56各自有不同的吸着特性)的混合物中分离至少一种组分。所以，至少一种组分可以部分地或基本上全部地从各种组分(对于MCM-56各自有不同的吸着特性)的混合物分离出来，方式是让混合物与MCM-56相接触，有选择地吸着这一种组分。
本发明的多层材料MCM-56可用来催化各种各样的化学转化工艺过程，包括目前许多商业/工业上的重要化学工艺。可由MCM-56有效地催化的化学转化工艺的实例，由MCM-56本身或与一种或多种其它催化活性物质包括其它晶体催化剂相结合，包括需要具有酸活性的催化剂的那些工艺。具体实例包括：
(1)芳烃例如苯与长链烯烃例如C14烯烃的烷基化反应，反应条件包括温度340～500℃，压力100-20,000KPa(常压-200大气压)，重时空速为2hr-1～2000hr-1和芳烃/烯烃摩尔比为1/1～20/1，反应后得到长链烷基芳烃，它随后被磺化得到合成洗涤剂；
(2)可得到短链烷基芳族化合物的、芳烃与气态烯烃的烷基化反应，例如苯与丙烯的烷基化反应得到枯烯，反应条件包括温度10～125℃，压力100～3,000KPa (1～30大气压)，和芳烃的重时空速(WHSV)为5～50hr-1
(3)含大量苯和甲苯的重整产品与含C5烯烃的燃料气的烷基化反应，这一反应尤其可得到单和二烷基化物，反应条件包括温度315℃～455℃，压力2860～5620KPa(400～800磅/英寸2)，烯烃的WHSV为0.4hr-1～0.8hr-1，重整产品的WHSV为1hr-1～2hr-1，和气体循环量为1.5～2.5v/v燃料气原料；
(4)芳烃例如苯、甲苯、二甲苯和萘与长链烯烃例如C14烯烃的烷基化反应，得到烷基化芳族润滑油基料，反应条件包括温度160～260℃和压力2510～3200KPa(350～450磅/英寸2)；
(5)酚类与烯烃或等当量的醇类的烷基化反应，得到长链烷基酚类，反应条件包括温度200～250℃，压力1480～2170KPa(200～300磅/英寸2)和总WHSV为2hr-1～10hr-1；和
(6)异链烷烃例如异丁烷与烯烃例如2-丁烯的烷基化反应，反应条件包括温度-25℃至400℃，例如75℃至200℃，压力为低于常压～35000KPa(5000磅/英寸2)，例如100～7000KPa(1～1000磅/英寸2)，基于烯烃的重时空速为0.01hr-1～100hr-1，例如0.1hr-1～20hr-1，总异链烷烃/总烯烃的摩尔比为1∶2～100∶1，例如3∶1～30∶1。
在许多催化剂的情况下，希望在MCM-56中引入耐受有机转化工艺中所使用的温度和其它条件的另一种材料。此类材料包括活性和非活性材料，合成或天然沸石，以及无机材料如粘土、氧化硅和/或金属氧化物如氧化铝。后者可以是天然的或者是凝胶沉淀物或凝胶形式，包括氧化硅和金属氧化物的混合物。活性材料与MCM-56一起使用，即与其结合或在MCM-56合成过程中就存在，趋向于改变某些有机转化工艺中催化剂的转化效率和/或选择性。非活性材料适合用作稀释剂，以控制在所给定工艺中的转化量，这样，可以经济和正常地获得产品，无需采用其它控制反应速度的措施。可将这些材料引入天然粘土中，例如膨润土和高岭土，以改进催化剂在工业操作条件下的抗破碎强度。这些材料即粘土、氧化物等用作催化剂的粘结剂。希望提供具有良好抗破碎强度的催化剂，因为在工业应用上希望能够防止催化剂破碎成粉末状物质。这些粘土和/或氧化物粘结剂一般仅用来改进催化剂的抗破碎强度。
可以与这种新型晶体物复合的天然粘土包括蒙脱土和高岭土族，这一族包括变膨润土类，和高岭土类，一般已知为Dixie、McNamee、Georgia和Florida粘土或其中主要矿物成分是多水高岭土、高岭石、地开石、珍珠石或富硅高岭石的其它物质。这些粘土可以在最初开采出来的原始状态下使用或在最初进行煅烧、酸处理或化学改性之后使用。用来与本发明的MCM-56多层材料复合的粘结剂还包括无机氧化物，尤其氧化铝。
除了上述材料之外，MCM-56可与多孔母体材料复合，比如氧化硅—氧化铝，氧化硅—氧化镁，氧化硅—氧化锆，氧化硅—氧化钍，氧化硅—氧化铍，氧化硅—氧化钛以及三元组合物如氧化硅—氧化铝—氧化钍，氧化硅—氧化铝—氧化锆，氧化硅—氧化铝—氧化镁和氧化硅—氧化镁—氧化锆。
细碎的MCM-56材料与无机氧化物母体的相对比例可以在大范围内变化，其中MCM-56的含量在1-90wt％范围内，以及更常见(尤其当复合物以微珠形式制得时)在占复合物的2～80wt％范围内。
现参考实施例和附图更具体地描述本发明，其中：
图1示出了实施例1的干燥产品MCM-56的X-射线衍射图。
图2示出了实施例2的煅烧产品MCM-56的X-射线衍射图。
图3示出了实施例9的干燥产品MCM-56的X-射线衍射图。
图4示出了实施例10的煅烧产品MCM-56的X-射线衍射图。
图5(a)示出了实施例2产品的X-射线衍射图。
图5(b)示出了实施例3产品的X-射线衍射图。
图5(c)示出了实施例4产品的X-射线衍射图。
图5(d)示出了实施例5产品的X-射线衍射图。
在实施例中，当测试α值时，应当注意，α值大致表示了该催化剂相对于标准催化剂的催化裂化活性，它给出相对速率常数(正常己烷转化速率/每体积催化剂·每单位时间)。它以取α值为1(速率常数＝0.016秒-1)的氧化硅—氧化铝裂化催化剂的活性为基准。α测试在USP 3,354,078中；在the Journal ofCatalysis，Vol.4，P527(1965)；Vol.6，P.278(1966)；和Vol.61，P.395(1980)中均有叙述。这里所使用试验的实验条件包括恒温于538℃和可变流速，这在the Journal of Catalvsis，Vol.61，P.395中有详细叙述。
                    实施例1
258克水、6克50％氢氧化钠溶液，13.4克铝酸钠溶液(25.5％Al2O3和19.5％Na2O)，51.4克Ultrasil(VN3)，和27.1克六亚甲基亚胺(HMI)在143℃下在600ml搅拌的(400rpm)压力釜中进行反应。
反应混合物具有以下组成，按摩尔比：
    SiO2/Al2O3 ＝    23
    OH-/SiO2    ＝    0.21
    Na/SiO2      ＝    0.21
    HMI/SiO2     ＝    0.35
    H2O/SiO2    ＝    20
在34小时的时候停止反应。过滤产物，用水洗涤形成湿饼，取一部分在110℃的烘箱中干燥。
一部分产物湿饼和干燥部分进行X-射线分析并证实为MCM-56。干燥MCM-56的X-射线衍射图在下表IV中给出分析数据并在图1中示出。
                    表IV2θ                       d(A)          I/Io       注解a4.1           21.6          10          B6.94          12.74         34          B，sh7.15          12.36         100         S8.9           9.9           32          VVB12.84         6.89          12          B13.89         6.38          7           VB，sh14.32         6.18          15          S15.92         5.57          8           VVB19.94         4.45          30          VVB21.98         4.04          43          B22.51         3.95          59          VB23.44         3.80          28          VVB24.97         3.57          43          S25.93         3.44          100         S26.61         3.35          51          B31.52         2.838         5           S33.40         2.683         10          VVB34.71         2.584         3           VVB36.26         2.477         3           S37.00         2.429         3           S37.75         2.383         9           S
a S＝尖峰，B＝宽峰，VB＝很宽峰，VVB＝极宽峰
      ，sh＝肩峰
实施例1产品的化学组成是(按wt％)：
N       ＝    1.61
Na      ＝    1.1
Al2O3 ＝    6.6
SiO2   ＝    70.5
灰芬    ＝    78.2
这一产品的SiO2/Al2O3摩尔比是18。
                   实施例2
一部分实施例1的产品通过与1M硝酸铵接触三次进行铵交换，然后在540℃下在空气中煅烧6小时。这一实施例煅烧产品的x-射线衍射图证明，它是MCM-56，在下表V中给出分析数据并在图2中示出。
                  表V
2θ                    d(A)         I/Io      注解a
4.1         21.6          37          B
7.14        12.38         97          S
8.9         9.9           33          VVB
12.80       6.92          12          B
14.42       6.14          59          S
15.80       5.61          14          VVB
19.76       4.49          27          VVB
22.45       3.96          73          VVB
23.75       3.75          26          VVB
25.10       3.55          37          S
26.05       3.42         100          S
26.79       3.33          35          B
31.75       2.818          6          S
33.52       2.673         10          VVB
34.82       2.576          4          VVB
36.44       2.466          3          S
37.96       2.370          6          S
a s=尖峰，B=宽峰，VVB=极宽峰
                    实施例3
为了对比，重复USP 4,954,325的实施例1。该实施例的合成晶体材料，在这里称作MCM-22前体或MCM-22的前体形式，由X-射线衍射分析来测试。它的X-射线衍射图谱在下表VI中给出分析数据并在图5(b)中示出。
                        表VI
2θ                           d(A)           I/Io
3.1             28.5          14
3.9             22.7          ＜1
6.53            13.53          36
7.14            12.38          100
7.94            11.13          34
9.67            9.15           20
12.85           6.89           6
13.26           6.68           4
14.36           6.17           2
14.70           6.03           5
15.85           5.59           4
19.00           4.67           2
19.85           4.47           22
21.56           4.12           10
21.94           4.05           19
22.53           3.95           21
23.59           3.77           13
24.98           3.56           20
25.98           3.43           55
26.56           3.36           23
29.15           3.06           4
31.58           2.833          3
32.34           2.768          2
33.48           2.676          5
34.87           2.573          1
36.34           2.472          2
37.18           2.418          1
37.82           2.379          5
                    实施例4
实施例3的产品在538℃下煅烧20小时。这一煅烧产品的X-射线衍射图的分析数据示于表VII并在图5(c)中示出该图谱。
              表VII
2θ                     d(A)        I/Io
2.80         31.55       25
4.02         21.98       10
7.10         12.45       96
7.95         11.12       47
10.00        8.85        51
12.90        6.86        11
14.34        6.18        42
14.72        6.02        15
15.90        5.57        20
17.81        4.98        5
19.08        4.65        2
20.20        4.40        20
20.91        4.25        5
21.59        4.12        20
21.92        4.06        13
22.67        3.92        30
23.70        3.75        13
25.01        3.56        20
26.00        3.43        100
26.95        3.31        14
27.75        3.21        15
28.52        3.13        10
29.01        3.08        5
29.71        3.01        5
31.61        2.830       5
32.21        2.779       5
33.35        2.687       5
34.61        2.592       5
                   实施例5
向压力釜中含有1.0份50％NaOH溶液和43.0份H2O的溶液中，添加2.24份量的45％铝酸钠。在搅拌下添加8.57份量的Ultrasil沉淀氧化硅，随后添加4.51份HMI。
反应混合物具有以下组成，按摩尔比：
SiO2/Al2O3   ＝    23
OH-/SiO2      ＝    0.21
Na/SiO2        ＝    0.21
HMI/SiO2       ＝    0.35
H2O/SiO2      ＝    19.3
混合物在搅拌下、在150℃下结晶84小时。产品被确认为MCM-49，它的X-射线衍射图在表VIII中给出分析数据并在图5(d)中示出该图谱。
产品的化学组成(按wt％)是：
    N               1.70
    Na              0.70
    Al2O3         7.3
    SiO2          74.5
    灰分            84.2
产品的氧化硅/氧化铝摩尔比是17.3。
在538℃下煅烧9小时后的吸着容量(按wt％)是：
环己烷，40托10.0
正己烷，40托13.1
H2O， 12托15.4
一部分样品在538℃下在空气中煅烧3小时。这一材料的X-射线衍射图的分析数据示于表IX。
      表VIII2θ                 d(A)        I/Io3.1         28.5       183.9         22.8       7+6.81       12.99       61 sh7.04       12.55       977.89       11.21       419.80        9.03       4012.76        6.94       1713.42        6.60       4*13.92        6.36       1714.22        6.23       1114.63        6.05        215.81        5.61       1517.71        5.01        418.86        4.71        419.23        4.62        620.09        4.42       2720.93        4.24        821.44        4.14       1721.74        4.09       3722.16        4.01       1722.56        3.94       5823.53        3.78       2624.83        3.59       2225.08        3.55       1025.86        3.45      10026.80        3.33       2827.53        3.24       2128.33        3.15       1528.98        3.08        429.47        3.03        231.46       2.843        432.08       2.790        633.19       2.699        934.05       2.633        534.77       2.580        436.21       2.481        236.90       2.436        337.68       2.387        8sh＝肩峰+＝非结晶MCM-49峰*＝杂质峰
          表IX
2θ              d(A)      I/Io
3.2       28.0     9+
3.9       22.8     7+
6.90     12.81     48 sh
7.13     12.39    100
7.98     11.08     46
9.95      8.89     5312.87      6.88     1014.32      6.18     3614.74      6.01     1115.94      5.56     1717.87      4.96      219.00      4.67      519.35      4.59      320.24      4.39     1421.06      4.22      521.56      4.12     1521.87      4.06     2522.32      3.98     1222.69      3.92     4123.69      3.76     2324.95      3.57     1925.22      3.53      425.99      3.43     9026.94      3.31     2027.73      3.22     1728.55      3.13     1129.11      3.07      329.63      3.01      231.59     2.833      632.23     2.777      433.34     2.687      934.35     2.611      434.92     2.570      336.35     2.471      237.07     2.425      237.82     2.379      6sh＝肩峰+＝非结晶MCM-49峰
                     实施例6
实施例2的产品进行α测试，显示出的α值是106。
                  实施例7
为了对比在MCM-56、MCM-22和MCM-49之间的微孔率和有效开孔率，按照E.L.Wu，G.R.Landolt，和A.W.Chester在“New Development in Zeolite Science and Technology(沸石科技中的新进展)”，Studies in Surface Science and Catalysis(表面科学和催化研究)，28，547(1986)中所描述的操作过程，将具有递增分子尺寸的烃化合物按顺序吸着到这些实施例的各部分煅烧的MCM-56、MCM-22和MCM-49产品上。这一研究的动态吸着结果示于下表X。
                 表X吸着物       MCM-56        MCM-22       MCM-49
       μl/c   秒    μl/c    秒    μl/c    秒正己烷       79    17    120      12     114     102.2-二甲基-丁烷      60    12    72       252    85      2331，3，5-三甲基苯         41    24    8        550    未检测到
吸着结果表明，在这些试验材料之间有明显的区别。对于1，3，5-三甲基苯(在这一研究中使用的最受阻的烃分子)，MCM-56有至少4倍于MCM-22和MCM-49的容量。MCM-56还比MCM-22或MCM-49表现出更快的2，2-二甲基丁烷初期吸着速率(在373°K下，在流动氦气中有80托2，2-二甲基丁烷的条件下，吸着最初15mg 2，2-二甲基丁烷/g吸着剂所需要的时间)。代表性材料MCM-56、MCM-22和MCM-49的相应时间分别是12，252和233秒。正己烷的初期吸着速率是吸着最初40mg正己烷/g吸着剂所需要的时间，对于1，3，5-三甲基苯，是吸着最初7mg 1，3，5-三甲基苯/g吸着剂所需要的时间。
                     实施例8
重复实施例1，只是在第40小时时停止反应。X-射线分析证明产品是MCM-56。
                 实施例9
258g水、20.5g铝酸钠溶液(25.5％Al2O3和19.5％Na2O)、51.4g Ultrasil(VN3)和50g六亚甲基亚胺(HMI)的混合物，在154℃下在600ml搅拌(400rpm)压力釜中进行反应。
反应混合物具有下述组成，按摩尔比：
SiO2/Al2O3   ＝    15
OH-/SiO2      ＝    0.17
Na/SiO2        ＝    0.17
HMI/SiO2       ＝    0.66
H2O/SiO2      ＝    19
在第130小时时停止反应。过滤产物，用水洗涤形成湿饼，一部分在110℃的烘箱中干燥2小时。
一部分产物湿饼和干燥部分进行X-射线分析并被证明是MCM-56。干燥材料的X-射线衍射图的分析数据示于表XI并在图3中示出。
             表XI
2θ            d(A)    I/Io   注解a
4.1     21.6     30      B
6.67    13.25    23      B，shb
6.96    12.70    24      B
7.16    12.35    80      S
8.9     9.9      21      VVB
12.86   6.88     14      B
13.98   6.33     7       VB，sh
14.33   6.18     15      S
15.85   5.59     7       VVB
19.93   4.45     25      VVB
21.95   4.05     42      VB
22.56   3.94     38      B
23.46   3.79     26      VVB
24.94   3.57     39      S
25.94   3.43     100     S
26.64   3.35     33      Ba S＝尖峰，B＝宽峰  VB＝很宽峰，VVB＝极宽峰
sh＝肩峰b 可能是痕量MCM-22前体
实施例9产品的化学组成(按wt％)是：
N       ＝    1.42
Na      ＝    2.3
Al2O3 ＝    9.3
SiO2   ＝    70.7
灰分    ＝    82.3
这一产品的SiO2/Al2O3摩尔比是13。
                   实施例10
一部分实施例9的干燥样品用1M硝酸铵溶液进行三次交换。固体物在482℃氮气中加热3小时，冷却至大约130℃，然后在538℃的空气中煅烧5小时。这一材料的X-射线图谱示于表XII和图4。
            表XII2θ         d(A)    I/Io   注解a4.3    20.5    69       B7.13   12.40   100      S8.1    10.9    33       VVB9.8    9.0     37       VVB12.79  6.92    12       B14.38  6.16    48       S15.78  5.62    17       VVB19.74  4.50    24       VVB22.45  3.96    69       VVB23.70  3.75    23       VVB25.10  3.55    36       S26.05  3.42    88       S26.86  3.32    27       B31.71  2.822   5        S33.34  2.687   9        B34.30  2.614   6        VVB36.40  2.468   5        S37.92  2.373   5        Sas＝尖峰，B＝宽峰，VVB＝极宽峰
实施例2-5的产品材料的X-射线衍射图示于图5。图5(a)示出了实施例2的MCM-56产品的图谱；图5(b)示出了实施例3的产品的图谱。实施例4的MCM-22产品的图谱示于图5(c)，实施例5的MCM-49产品的图谱示于图5(d)。这些图谱在这一图5中给出的方式是为了方便对比。图5(b)和(c)分别来自合成多层材料(它经煅烧后转变成晶体MCM-22)和晶体MCM-22。

Claims (8)

1.一种合成的多层材料，其特征在于，所述材料的组成包括以下摩尔关系的组成：
      X2O3∶(n)YO2式中，
n小于约35，
X是三价元素，
Y是四价元素，
所述材料对1，3，5-三甲基苯的吸着容量为至少约35μl/g煅烧合成材料，
所述材料初期吸收15mg 2，2-二甲基丁烷/g煅烧合成材料的时间约小于20秒，
所述已煅烧的合成材料的X-射线衍射图谱在12.4±0.2，9.9±0.3，6.9±0.1，6.2±0.1，3.55±0.07和3.42±0.07埃处有d一间距的最大值。
2.根据权利要求1所述的合成材料，其中，X选自铝、硼、铁和镓，而Y选自硅和锗。
3.根据权利要求1所述的材料，其中，X包括铝，Y包括硅。
4.根据权利要求1所述的材料，其中，n是5～25。
5.根据权利要求4所述的材料，其中，n是10～20。
6.根据权利要求1所述的材料，其中，所述材料的组成，以已合成的、无水的形式为基础，且按照氧化物摩尔数/每n摩尔YO2表示时，其通式为：
(0-2)M2O∶(1-2)R∶X2O3∶(n)YO2式中
M是碱金属或碱土金属，
R是有机部分。
7.根据权利要求6所述的材料，其中，R选自环烷基胺、氮杂环链烷烃、二氮杂环链烷烃和它们的混合物，烷基包含5～8个碳原子。
8.权利要求1-7中任何一项所述合成多层材料作为有机化合物转化用的吸附剂或催化剂组分的应用。
CN94192390A 1993-04-26 1994-04-19 合成多层材料它的合成方法及它的用途 Expired - Lifetime CN1041216C (zh)

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