CN1148819A - 生产苯酚及其衍生物的催化剂 - Google Patents
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Abstract
一种在例如225-450℃通过一氧化二氮使苯及其衍生物氧化羟基化而产生苯酚及其衍生物的沸石催化剂，由於用含有大约3至100mol％水蒸汽在例如氮气中的气体在大约500至1000℃进行水热处理而具有大为提高的工艺特性，水热处理两小时已被证明是有效的。
Description
这里公开的是用於生产苯酚及其衍生物的经过改进的催化剂，以及制造这类催化剂的方法；所述生产苯酚及其衍生物的方法是用一氧化二氮一步使苯或其它芳香化合物发生氧化羟基化反应。
背景
在多种催化剂上，从硅石上的五氧化二钒到沸石，例如ZSM-5和ZSM-11型沸石催化剂，在高温下，例如300至450℃，用一氧化二氮部分氧化苯来生产苯酚的方法已被公开。当苯被一种苯的衍生物诸如氯苯、氟苯、甲苯或乙苯代替时，可产生相应的取代的苯酚。当苯酚本身作为取代的苯时，反应产物包括二羟基苯诸如氢醌，间苯二酚和邻苯二酚。苯酚及其衍生物，例如二元酚类，氯代苯酚类，硝基苯酚类，甲基苯酚类以及其它含有羟基的芳香化合物是在工业上已找到广泛应用的有价值的产物。这一类当中最普通的化学商品是苯酚，它主要用於生产酚醛树脂，己内酰胺，硝基酚类和氯代苯酚类等。近几十年来，研究者已经寻找到简单和有效的合成苯酚及其衍生物的方法。Iwamoto等人在《物理化学》(J.Physical Chemistry(ACS))第87卷No.6(1983)第903-905页报告芳香化合物的一步羟基化可用一氧化二氮作氧化剂在传统的部份氧化用的催化剂例如钒、钼和钨的载体氧化物存在的条件下来实施。Iwamoto在550℃进行反应，苯转化为10％，对苯酚的选择性为72％。虽然这些结果远优於所有以前的成就，但它们仍然被证明对於这种方法的实际使用是不充分的，这就必然需要寻求更有效的体系。
使用新型的催化剂，例如具有沸石结构的高硅石硅铝酸盐来进行苯的羟基化反应已由Suzuki等人在日本化学协会的Chemistry Letters，(1988)第953-956页、Gubelmann等人在美国专利5,055,623以及Kharitonov等人在美国专利5,110,995中报道过。在这类沸石催化剂存在的条件下苯和其它芳香化合物的羟基化反应在300-400℃发生，对苯酚的选择性为90-100％。然而，催化剂活性仍然完全不适宜这一工艺的商业实用。
研究人员继续去发现改进这种工艺参数和/或增进沸石的效率的新方法，例如引进了各种催化剂预处理。在这方面，Zholobenko在Mendeleev Commun.，(1993)No.1第28-29页报告过一种用沸石催化剂生产苯酚的方法，该催化剂曾通过在空气中高温煅烧来活化。zholobenko的方法的一个缺点是煅烧温度低於700℃时它不能使催化剂活性有任何增加。更具体地说，由於活化作用要在较高温度(750℃以上)才是有意义的，zholobenko的方法难於实际实施。
发明概要
本发明解决了与苯酚及其衍生物的生产中苯及其衍生物经一氧化二氮羟基化过程中所用的沸石催化剂的不完满的性能及效率有关的一些问题。这些问题通过使用一种经简单而有效的活化处理，例如在升高的温度下暴露於水蒸气中的沸石催化剂而令人惊奇地得到解决。
优选实施方案详述
本发明提供一种经改进的沸石催化剂，用於由相应的芳香化合物以一氧化二氮进行氧化羟基化来生产苯酚及其衍生物。这类沸石催化剂的催化性能可用本发明的方法来增进，即在350～950℃的温度范围内用含水蒸气的气相来处理沸石催化剂。在气相中水蒸气的量不是关键性的，可从在一种稀释气体中含有低水平的水蒸气直到基本上纯的水蒸气。例如，气相可以是含有低至3摩尔百分数(mol％)水蒸气在空气中或最好是在一种基本是惰性的稀释气体，包括氮、氩、氦、二氧化碳等或者它们的混合物中所组成的气相。气相中当然应当基本上避免存在会使催化剂中毒的组份。气相中最好能含有较高含量的水蒸气，例如10mol％或更多，直到100mol％。催化剂高温暴露於水蒸气中的时间可依照所需增进活性的程度来变化，并可由通常的实验容易地测定。
能经受本发明方法增进活性处理的沸石包括ZSM-5和ZSM-11型沸石，它们最好是酸型并含有铁。这类沸石在本领域内是众所周知的，它们用於种种商业方法中并可容易地由催化剂出售商，诸如UOP、Mobil及它处购得。商品沸石催化剂典型地是铝或硅石的多孔基质以便提供能够耐受填充式或流化床反应器中磨损的耐用的丸型。已经发现本发明的方法能有利地适用于粉状的或丸型的沸石。
用本发明的方法制备的经增进了性能的沸石催化剂在芳香化合物诸如苯和苯的衍生物，例如氯苯、氟苯、甲苯、乙苯等以及苯酚的氧化反应中特别有用。这种氧化是通过把酚、一氧化二氮以及，任选地，稀释气体诸如氮、氩、二氧化碳等所组成的进料气体混合物在225～450℃或更高的温度，例如500℃以上，通过沸石催化剂床。工艺条件，包括进料组成、反应温度、流速等可依照所需的工艺参数，例如酚生产的选择性、一氧化二氮的转化、产物气体中的酚浓度、催化剂效率等，由本领域的技术人员来改变。例如，在进料气体混合物中一氧化二氮对苯的摩尔比率可从100∶1变化到1∶100。在一些经优选的实施方案中，使芳香化合物处於摩尔过量来操作这种工艺是有益的。
在本发明的一个方面，经过水热处理过的沸石催化剂的特征是在所需的催化转化中具有稳定的性能，即在350℃用一氧化二氮氧化苯以生产苯酚的过程中苯转化只有很低的下降。本发明的经优选的催化剂，例如ZSM-5或ZSM-11型沸石催化剂，经3小时连续操作后所呈现的苯转化对初始苯转化的比率为至少40％。对更优选的催化剂这一比率为至少50％。以下的实例说明对有些催化剂这一比率为大约70％。
已经过水热处理的本发明的催化剂可通过对水热处理的耐受性来鉴定。例如，本发明的一种含铁的、经酸化的沸石催化剂可以具有如下特征：该催化剂用由50mol％空气和50mol％水组成的气体在600℃的温度下水热处理两小时以后，当在350℃，在由75mol％氦，5mol％苯和20mol％一氧化二氮组成的气流中用於苯的催化羟基化反应以形成苯酚时，催化剂的苯转化性能的增加不会超过10％。
本发明的优点可通过以下的实例来说明，其中沸石的增强了的性能可通过用一氧化二氮氧化苯来证实。
实例1
一种每摩尔SiO2中含有4.3×10-4摩尔Fe2O3和2.3X10-2摩尔Al2o3的基於SiO2的沸石催化剂可按照在美国专利5,110,995中Kharitonov公开的方法来制备。在有机模板材料被烧除以后，沸石用酸处理使它转化成H型并在550℃干燥的空气流中煅烧两小时。为进行催化剂性质试验，可通过把大约2毫升0.5-1.0毫米部份的沸石填充进内径为0.7厘米的石英管中来制备一个管状反应器。把填充了沸石的管状反应器加热到350℃并进料含有5mol％苯和20mol％一氧化二氮在氦气中的反应气体混合物。从反应器出来的产物气流用气相色谱定期进行分析。气体分析数据被用来计算苯转化(X)和对酚的选择性(S)，结果被报告於表1中。可以看出在反应过程中催化剂由於焦沉积而明显失活。开始往反应器中进料气流20分钟以后，进行测量以决定初始的苯转化Xo为8.5％以及初始的选择性So为92.5％。连续操作3小时后，苯转化经测定为3.0％，表明催化剂活性的下降。苯转化对初始的苯转化的比率(X/Xo)为35％表征了操作中的催化剂稳定性。在任何一次操作中均未观察到选择性的降低。
实例2
基本上按实例1中的方法来制备催化剂，不过另外进行水热处理两小时，即在含有50mol％水的空气存在的条件下在500℃暴露於含有50mol％水的空气中两小时。经水热处理过的催化剂的催化性质报告於表1中，它表明初始的苯转化大为增加，达18.5％。
实施3-8
这些实例说明了本发明的一些方面，其中对水热处理的温度进行了变动。在这些实例中催化剂试样基本上是按实例2中的方法来制备的，只是水热处理的温度是在550-1000℃进行。观察到的催化性质被报告於表1中，它表明最优化的水热处理温度可由通常的试验很容易地测定，以使催化剂具有所需的初始的或长期的转化特性。更令人惊奇的是，当苯转化随着水热处理增加时，例如由8.5％增至37％，催化剂稳定性也增长了系数2，即X/Xo由35％增至70％。在很高温度，例如1000℃附近进行这样的处理是不可取的，因为它明显地导致活性的降低。
表1
| 实例编号 | 处理温度，℃ | 最初的催化性质 | 气流中3小时后的活性 | ||
| Xo(％) | So(％) | X(％) | X/Xo(％) | ||
| 12345678 | 未处理5005506006507007501000 | 8.518.533.637.036.531.527.56.6 | 92.593.593.095.093.595.696.095.0 | 3.04.512.015.518.022.018.52.7 | 3524344249706749 |
实例9-12
这些实例说明了本发明的一些方面，其中对水热处理气体中的水含量进行了改动。在这些实例中催化剂试样基本上是按实例2的方法来制备的，只是水热处理是用600℃的处理气体来进行并且其中水蒸气的含量为2.5～100mol％。催化数据被报告於表2中，它表明增加水热处理气体中水蒸气的浓度可使催化剂具有大为增加的工艺效率。例如，苯转化由8.6％增加到38.5％的同时，还使稳定性增加并使选择性也有某种程度的增加。
在实例9中水热处理是在可能相似於催化剂在空气中煅烧的条件下进行的，即只含2.5mol％水蒸气。将实例9与实例1比较表明这样低的水浓度对於催化剂的显著活化是不够的。
表2
| 实例编号 | CH2O(mol％) | 最初的催化性质 | 操作3小时后活性 | ||
| Xo(％) | So(％) | X(％) | X/Xo(％) | ||
| 9101112 | 2.51060100 | 8.615.535.038.5 | 92.593.094.095.0 | 3.05.015.519.0 | 35334550 |
实例14-16
这些实例说明了本发明的方法对许多用一氧化二氮羟基化苯以生产苯酚的反应中有用的催化剂的有益效果。具有在表3中所报告的组份的沸石都被评估以测定初始的苯转化和苯酚选择性。这些沸石然后通过在500℃的含有50mol％水的气体中暴露两小时进行水热处理。可以看到这样的水热处理大大增进了这类改变了的沸石组份的工艺特性。
表3
| 实例编号 | 化学组成 | 催化性质 | |||
| 处理前 | 处理后 | ||||
| Xo(％) | So(％) | Xo(％) | So(％) | ||
| 141516 | 1.1×10-2的Al2O3SiO23.4×10-3的Fe2O38.6×10-3Al2O3SiO25.7×10-3的Fe2O3SiO2 | 8.021.515.0 | 97.083.591.0 | 30.046.531.5 | 98.087.590.0 |
这些实例表明了本发明的本质，但决不是全部内容，意味着水热活化的最佳条件(温度，时间，水蒸气浓度等)对於不同类型的催化剂以及想要使用这种催化剂的反应可以是不相同的。具体地说，经活化的催化剂的高效率不仅使得在过量一氧化二氮的条件下能够实施这种方法，而且在过量芳香类存在的条件下，例如芳香类对一氧化二氮的摩尔比率高达100∶1的条件下也能实施这种方法。在过量芳香化合物的条件下实施这种方法的优点是在这种条件下可达到完全的一氧化二氮转化。这可导致有意义的工艺简化，因为在这种情况下没有必要去分离未反应的一氧化二氮并将它返回到反应中。
虽然在这里描述了具体的实施方案，但对於本领域的技术人员显然还可进行各种改变而不偏离本发明的真正精神和范围。按此，打算用下面的权利要求来涵盖所有这类改变在完全的发明概念之内。
Claims (7)
1.一种用于增强用一氧化二氮氧化苯的反应的沸石催化剂的制备方法，所述方法包括在350～950℃用含3-100mol％水的气体水热(hydrothermally)处理沸石催化剂。
2.按照权利要求1的方法，其中所说的沸石催化剂是ZSM-5和ZSM-11型沸石催化剂。
3.按照权利要求2的方法，其中所说的催化剂是一种酸化的含铁沸石。
4.按照权利要求3的方法，其中所说的气体含有至少10mol％的水。
5.按照权利要求4的方法，其中所说的气体温度至少为500℃。
6.一种ZSM-5或ZSM-11型沸石催化剂，其特征在于350℃用一氧化二氮使苯氧化而产生苯酚的过程中具有稳定的苯转化，其中经3小时连续操作后苯的转化对初始苯的转化的比率至少为40％。
7.一种含铁的、经酸化的沸石催化剂，其特征在于该催化剂用由50mol％空气和50mol％水组成的气体在600℃的温度下水热处理2小时后，当在350℃，在由75mol％氦、5mol％苯、20mol％一氧化二氮的气流中用於苯的催化羟基化以生成苯酚的反应中时，不会使催化剂的苯转化性能增加大於10％。
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| Application Number | Priority Date | Filing Date | Title |
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| RU9494013071A RU2074164C1 (ru) | 1994-04-12 | 1994-04-12 | Способ получения фенола или его производных |
| RU94013071 | 1994-04-12 |
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| CN101747155B (zh) * | 2008-12-08 | 2013-04-24 | 中国石油天然气股份有限公司 | 一种n2o为氧化剂苯一步氧化合成苯酚的方法 |
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| US4429176A (en) * | 1982-02-08 | 1984-01-31 | Mobil Oil Corporation | Active zeolite catalysts of improved stability |
| FR2648810B1 (fr) * | 1989-06-22 | 1992-02-28 | Rhone Poulenc Chimie | Procede de preparation de phenols |
| US5110995A (en) * | 1991-03-12 | 1992-05-05 | Institute Of Catalysis | Preparation of phenol or phenol derivatives |
| DE4117511A1 (de) * | 1991-05-29 | 1992-12-03 | Vaw Ver Aluminium Werke Ag | Verfahren zur modifizierung eines rein-anorganisch synthetisierten zeoliths vom pentasil-typ |
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| CN101747155B (zh) * | 2008-12-08 | 2013-04-24 | 中国石油天然气股份有限公司 | 一种n2o为氧化剂苯一步氧化合成苯酚的方法 |
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| AU2376795A (en) | 1995-10-30 |
| KR100231372B1 (ko) | 1999-11-15 |
| CN1102074C (zh) | 2003-02-26 |
| JP3507500B2 (ja) | 2004-03-15 |
| AU694967B2 (en) | 1998-08-06 |
| MX9604787A (es) | 1998-05-31 |
| JPH09511445A (ja) | 1997-11-18 |
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