CN1090993C - 具有高表面积和可控制的多孔性分布的一种微－中孔材料的制备方法 - Google Patents

具有高表面积和可控制的多孔性分布的一种微－中孔材料的制备方法 Download PDF

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CN1090993C
CN1090993C CN97113214A CN97113214A CN1090993C CN 1090993 C CN1090993 C CN 1090993C CN 97113214 A CN97113214 A CN 97113214A CN 97113214 A CN97113214 A CN 97113214A CN 1090993 C CN1090993 C CN 1090993C
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C·普里格
A·卡拉逖
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Abstract

本发明涉及一种微-中孔材料的一种制备方法，包括：a)从一种四烷基原硅酸盐、一种C3-C6烷醇或二醇，一种具有如式R1(R2)3N-OH四烷基氢氧化物，选择性地在一种或几种金属化合物存在下制备一种混合物；b)将该混合物进行水解作用和随后在20℃至接近存在的醇或醇的混合物的沸点温度的温度下进行胶凝作用；c)将得到的凝胶体干燥和锻烧。所述的材料能够很方便地用作一种非均相催化剂，一种吸附剂或一种催化剂载体用于工业方法中，精炼，石油化学，基础化学和精细化学领域中。

Description

具有高表面积和可控制的多孔性 分布的一种微-中孔材料的制备方法
本发明涉及具有高表面积和可控制的多孔性分布的一种微-中孔材料的一种制备方法。
更详细地说该方法包括：a)从一种四烷基原硅酸盐、一种C3-C6烷醇或二醇、一种具有如式R1(R2)3N-OH其中R1是一个C3-C7烷基和R2是一个C1或C3-C7烷基的四烷基铵氢氧化物，选择性地在一种或几种金属化合物存在下制备一种混合物，其中的摩尔此在下列范围中：-醇/SiO2＜或等于20；-R1(R2)3N-OH/SiO2＝0.05-0.4；-H2O/SiO2＝1-40；-金属氧化物/SiO2＝0-0.02；b)将该混合物进行水解作用和随后在20℃至接近存在的醇或醇混合物的沸点混度的温度下进行胶凝作用；c)将得到的凝胶体干燥和锻烧。
M.R.Manton和J.C.Davidtz在催化学报(Journal ofCatalysis)(1979)，第60卷，第156-166页中叙述了具有高表面积和窄的中孔性分布(孔的尺寸范围在37至150)特征的一种无定形氧化硅铝合成的可能性；但是这些材料还未发现可行的应用。
专利申请书WO 91/11390叙述了具有平均孔径在20至100间并且按六方形或立方形结构在材料中规则地组织的一组新的硅铝酸盐(叫做MCM-41)的制备可能性。
这些材料能够以一种混合物中制得，该混合物含有至少一种二氧化硅源、一种氧化铝源、具有式R1R2R3R4N-OH的一种有机化合物，其中R1、R2、R3和R4中至少一个选自氢和一个具有短链的烷基知，选择性地，具有上式R1R2R3R4N-OH的一种第二种季铵碱，但是其中R1、R2、R3和R4是选自氢和一种C1-C5烷基，烷基中有两个可以认为是共同形成一种环形化合物。
该混合物用水热法在25℃至250℃温度范围内处理5分钟至14天。
得到的产物用X-射线衍射光谱(XRD)测基特征，以其粉末中得到具有一种双尺寸次序的一种六角形结构或一种具有立方对称性的结构。
利用高共振透射电子显微镜法(HREM)实施的测试表明，对具有一种六方形对称性的MCM-41来说，存在的单尺寸中孔性按照一种蜂窝六方形结构规则地组织。
在这些材料中，铝是以四面体配位使材料呈酸性，此外这些材料对热处理极稳定。
美国专利5,434,118和5,049,536和意大利专利申请书MI 93A02696公开了制备无定形的金属硅酸盐，称为MSA(Bellussi G，等人，表面科学催化研究，(Stud.Surf.sci.Catal.)(1994)第84卷，第85页)的另一种可能性，MSA具有一个非常窄的孔尺寸分布(平均直径在20至40，基本没有直径大于40的孔，表面积7500米3/克)，孔体积0.4-0.8毫升/克。
使用IUPAC符号和术语手册所建议的术语，附录2，第I集表面化学纯应用化学(1972)第31卷578其中微孔被定义为具有直径大于20的孔和中孔被定义为具有直径在20至500的孔，这些材料可以被分类为微-中孔。
这些材料具有优异的催化性质，该性质是由所用的制备方法使金属以均匀分布这一事实形成的；当该金属是铝时，在27Al-MAS-NMR谱中(Bellussi G.等人，表面科学催化研究(Stud.Surf.Sci.Catal)(1994)等84卷，第85页)观察到一种四面体配位，并且这使得上述MSA被分类为沸石状材料。
上述材料的合成方法包括一种二氧化硅源(优选自四烷基原硅酸盐)和一种可溶性过渡金属盐或一种可溶性的属于元素周期表中的IIIA、IVA或VA族的金属盐与一种四烷基铵氢氧化物(R4N-OH，其中R＝乙基、正丙基、正-丁基，正-戊基)的水溶性相混合。
然后通过将得到的溶液加热至50℃至110℃使共凝胶化；再将得到的凝胶干燥和锻烧以产生最终产物。
水解和胶凝作用相很方便地在装有一个回流冷凝器的反应器中或在一个由自动压力操作的封闭的耐压反应器中实施，以避免存在的醇逸出。
专利申请书EP 95 200093.3和EP 96 104 680.2也叙述了制备叫做ERS-8的微-中孔金属硅酸盐的可能性，ERS-8的特点是具有一个平均直径小大40的窄的孔尺寸分布，孔体积为0.3-1.3毫升/克，表面积为500-1200米2/克。
鉴于MSA完全是无定形的，用X射线衍射光谱(XRD)从ERS-8的粉末中测其特性。它在角度很低时具有一个广布的反射，表明微-孔中孔结构是一个“近程”有序结构。
更特别地，用装有一个比例脉冲计数器，1/6°的发散和接受载片的Philips垂直衍射计用CuKα发射(λ＝1.54178)记录的XRD谱，其特征是存在一个单一放大的衍射线，或虽然有一个广布的“散射”，角度值不会大于2θ＝5°，因为没有观察到更高的角度值下的其它相干“散射”现象。这可以用微-中孔结构中存在的“近程”有序来解释，结构相关性基本上只限于瞬间邻基。
这些材料中包括一个二氧化硅基体，其中一种或多种金属氧化物可能是均匀分散了的，其中金属选自过渡金属或属于元素周期表的IIIA、IVA或VA族的金属。
现已惊人地发现选择上述化合物的制备方法和适当改进一些操作条件能获得具有类似特性的材料但具有改进了的催化性能。
因此本发明涉及具有高表面积和可控制的多孔性分布的一种微-中孔材料的制备方法，该方法基本上包括进行水解作用，胶凝作用和随后锻烧，一种四烷基原硅酸盐溶液，一种醇，一种四烷基铵氢氧化物，可能存在有一种或多种金属化合物。
更详细地说，根据本发明的方法包括：a)从一种四烷基原硅酸盐，一种C3-C6烷醇或二醇，具有式R1(R2)3N -OH其中R1是一个C3-C7烷基和R2是一个C1或C3-C7烷基的一种四烷基铵氢氧化物，选择性地存在一种或多种金属化合物，开始制备一种混合物，其中摩尔比在下列范围中：-醇/SiO2＜或等于20；-R1(R2)3N-OH/SiO2＝0.05-0.4；-H2O/SiO2＝1-40；-金属氧化物/SiO2＝0-0.02；b)将该混合物水解和然后在20℃至接近于存在的醇或醇混合物的沸点温度的温度下进行胶凝作用；c)将得到的凝胶干燥和锻烧。
更详细地说，优选使用一种带有一个C6-C7烷基的四烷基铵氢氧化物；当氢氧化物是烷基三甲基铵时，烷基是C4-C7烷基。
醇优选地是选自丙醇和丁醇，而水解和胶凝处理优选是在25至50℃的温度下实施。
涉及该方法的优点是：1)使用3-5碳原子的醇可以使表面积和孔体积值最大化而基本上不改变分布；使用这些醇也使操作在一个均相体系中实施，使得试剂的混合不很严格；2)更快的水解和胶凝时间，可以减小至数分种，通常在5分钟至1小时间变化；3)在开放体系中的操作保证了在硅醇盐水解作用中产生的醇和所添加的相同或不同的醇在反应环境中的碱性守恒。将温度保持在室温至低于存在的醇或醇混合物的沸点湿度是必需的。
如此得到的材料其特征为表面积大于500米2/克，孔体积在0.3-1.3毫升/克，平均孔直径大小40，和它的XRD谱不具有晶体结构，但是可能具有角度值不大于2θ＝5°的广布的“散射”。
这材料能够方便地用作一种非均相催化剂，一种吸附剂或一种催化剂的载体用于工业方法中、用于精制，石油化学，基础化学和精细化学领域中。
所提供的下列实施例用于更好地说明本发明及其实施例，而不应认为是对本发明范围自身的限制。
实施例1
在一个开放体系中制备催化剂1
在室温下于一个400毫升的实验室烧杯中将7.4克四己基铵氢氧化物(40％重量的水溶液)，248克正丁醇和31克水进行混合。
分别将1.2克第二丁醇铝和52克四乙基原硅酸盐混合，然后加入到前述制备好的溶液中。
混合物的组成，按摩尔比表示，如下：-Al2O3/SiO2＝0.01；-四己基铵氢氧化物/SiO2＝0.032；-H2O/SiO2＝8；-正丁醇/SiO2＝13。
搅拌大约30分钟后，形成一个透明的凝胶，将其陈化大约20小时，然后在烘箱中于120℃真空下干燥和最后在空气中于550℃锻烧8小时，得到催化剂1。
XRD光谱在低角度进未显示出存在有大量的“散射”现象。
比表面积证明是等于1111米2/克，比孔体积是1.02毫升/克，平均孔径为40。
实施例2
在一个开放体系中制备催化剂2。
在室温下于400毫升实验室烧杯中，将17.5克正庚基三甲基铵氢氧化物(27.6％重量水溶液)，33克水和1克异丙醇铝进行混合。
将混合物在大约60℃加热直到铝盐完全溶解，然后冷却至室温。
分别将52克四乙基原硅酸盐和126克正丙醇混合，然后加入到前述制备好的溶液中。
混合物的组成，按摩尔比表示，如下：-Al2O3/SiO2＝0.01；-正己基三甲基铵氢氧化物/SiO2＝0.11；-H2O/SiO2＝9；-正丙醇/SiO2＝8；
搅拌大约30分钟后，形成一个透明的凝胶，将其陈化大约20小时，然后在烘箱中于120℃真空下干燥和最后在空气中于550℃下锻烧8小时，得到催化剂2。
XRD光谱在低角度进未显示出存在有大量的“散射”现象。
比表面积证明是等于87.2米2/克，比孔体积是0.85毫升/克，平均孔径是40。实例3(对比)
在一个封闭体系中制备催化剂3
在该实施例中反应混合物的组分采用如下摩尔比：-Al2O3/SiO2＝0.01；-四丙基铵氢氧化钠/SiO2＝0.09；-H2O/SiO2＝15。
将4.727千克水和3.922千克四丙基铵氢氧化物(以14％重量水溶液的形式使用)，装入一个20升耐压反应器中。
溶液在反应器中加热，当温度达到60℃时，加入0.120千克Al(OiPr)3(异丙醇铝-Fluka)。
混合物在封闭的反应器中保持于此温度下并搅拌使铝化合物完全溶解所必需的时间(大约40分钟)。
在铝化合物完全溶解时将反应器温度升高至90℃并用适当的阀门加入6.250千克的TEOS(四乙基原硅酸盐)。
添加完后，将阀门关闭，将温度固定在88℃和将反应器在这些条件下保持3小时。
压力达到最大值1.5巴。
如此得到一个粘稠的液体产物，将其陈化大约12小时后，在一台旋转蒸发器上于大约60乇的真空下干燥，然后在空气中于550℃锻烧大约8小时，得到催化剂3。
XRD光谱在低角度时未显示出存在有大量的“散射”现象。
相同固体的比表面积是656米2/克，孔体积是0.473毫米/克，平均孔径40。
实施例4
催化评价。
在该实施例中评价了根据前述实施例合成的材料在丙烯低聚反应中的催化活性，使用下列操作条件：-WHSV(重时空速)＝4小时-1；-压力＝35巴-温度＝150℃
转化％根据丙烯进料反应63小时后来计算。
催化剂1提供转化等于87％，催化剂2等于79％而催化剂3等于67％。

Claims (5)

1.一种制备具有高表面积和可控制的多孔性分布的一种微-中孔材料的方法，该方法包括：a)从一种四烷基原硅酸盐、具有3-5个碳原子的醇或醇混合物、一种具有式R1(R2)3N-OH其中R1是一个C3-C7烷基和R2是一个C1或C3-C7烷基的四烷基铵氢氧化物，选择性地在有一种或多种金属化合物存在下，在开放体系中制备一种混合物，其中的摩尔比在下列范围中：-醇/SiO2＝0.01-20；-R1(R2)3N-OH/SiO2＝0.05-0.4；-H2O/SiO2＝1-40；-金属氧化物/SiO2＝0-0.02；b)将该混合物进行水解作用和随后在20℃至接近存在的醇或醇混合物的沸点温度的温度下进行胶凝作用；c)将得到的凝胶体干燥和煅烧。
2.根据权利要求1的方法，其中四烷基铵氢氧化物具有一个C6-C7烷基。
3.根据权利要求1和2的方法，其中烷基三甲基铵氢氧化物具有一个C4-C7烷基。
4.根据权利要求1的方法，其中醇选自丙醇或丁醇。
5.根据权利要求1的方法，其中水解和胶凝处理在25至50℃温度下实施。
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