CN104860807B - 一种多相催化芳香烃羰基化制备芳香醛的方法 - Google Patents
一种多相催化芳香烃羰基化制备芳香醛的方法 Download PDFInfo
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Abstract
一种多相催化芳香烃羰基化制备芳香醛的方法,该方法以介孔二氧化硅负载的Pd(II)、Rh(III)为催化剂,一氧化碳为羰基化试剂,使芳香烃羰基化高选择性转化制备芳香醛。该反应体系反应条件温和,不需要强酸性催化剂;制得的芳香醛产品不含卤素和过氧化物等杂质,纯度高;使用的多相催化剂与体系易分离,且可多次重复使用。
Description
技术领域
本发明涉及一种多相催化芳香烃羰基化制备芳香醛的方法,具体地讲,该方法以介孔二氧化硅负载的Pd(II)或者Rh(III)为催化剂,一氧化碳为羰基化试剂,实现了芳香烃羰基化高选择性制备芳香醛。
背景技术
芳香醛是一类重要的化工原料和中间体。其自身在食品,日化,香料等行业中有重要应用。作为中间体,芳香醛经过氧化可以制备相应的羧酸,芳香酸在化工行业中占有极其重要的地位。因此,芳香醛的制备具有非常大的工业应用价值。
芳香烃广泛存在于石油,天然气等化石资源中。通过催化芳香烃直接羰基化可以制备芳香醛。以往的研究主要采用强酸性催化体系催化芳香烃羰基化制备芳香醛,如液体L-B复合酸,酸性离子液体,固体超强酸等。这些方法存在催化剂用量大,催化活性低,环境污染等问题。近年来,研究发现过渡金属有机化合物催化体系可以用于催化芳香烃直接羰基化制备芳香醛。Yuzo Fujiwara等人以醋酸钯为催化剂,一氧化碳为碳源,催化甲苯羰基化制备对甲基苯甲醛,在100℃条件下反应20h,对甲基苯甲醛产率仅为18.0%(J.Chem.Soc.,Chem.Commun.,1980,5,220-221)。而以醋酸钯-三氟乙酸-过硫酸钾为催化剂,一氧化碳为碳源,催化苯羰基化制备苯甲醛时,室温下反应20h后,苯甲醛的产率仅为30.0%(J.Organomet.Chem.1999,580(2),290-294.)。姜玄珍等人在实现苯的羰基化的过程中,使用醋酸钴代替醋酸钯,同时在反应体系中加入吡啶,100℃条件下反应24h,苯甲醛的收率为38.3%(Catal.Lett.2003,87,225.)。上述研究表明,过渡金属有机化合物可以催化芳香烃直接羰基化制备芳香醛,但催化活性较低。并且,过渡金属有机化合物为均相催化剂,存在催化剂分离困难,难以重复使用等问题。因此,实现多相催化芳香烃羰基化高选择性制备芳香醛具有重要意义。
发明内容
本发明的目的在于提供一种多相催化芳香烃羰基化制备芳香醛的方法,该方法以一氧化碳为碳源,以介孔二氧化硅负载的Pd(II)或者Rh(III)为催化剂,实现了芳香烃羰基化高选择性制备芳香醛。
本发明中所用芳香烃为下列结构中的一种或者多种:
该方法中所用催化剂载体为比表面积在500-1000m2/g的SBA-15、SBA-16、MCM-41、MCM-48中的一种或者多种,活性组分为Pd(II)或者Rh(III)。催化剂活性组分按氧化物计与载体的质量比为0.0001-0.15。
催化剂典型制备过程为:按上述比例将活性组分与载体于二氯甲烷中混合,并在氮气保护下,室温搅拌20-40h,然后,过滤得到固体样品,最后用二氯甲烷洗涤1-3h。
上述制备过程中活性组分前体为RhCl(CO)(PPh3)2或者PdCl2(PPh3)2。
该方法中所用催化剂与反应底物的质量比为0.04-3.60。
反应在压力反应器中进行,以一氧化碳为碳源。其中一氧化碳分压为0.01-5.0MPa,最优一氧化碳分压为1.5-3.0MPa。反应温度为40℃-180℃,优化的最佳反应温度为100-140℃。反应时间为0.5-22h,优化的最佳反应时间为6-14h。
催化剂的循环使用采用如下方法进行,反应结束后,采用离心的方法将催化剂分离出来,所得固体用甲醇洗涤,干燥后,即可用于下一轮芳香烃羰基化反应。
与现有技术相比,本发明具有如下优点:
(1)该方法能够在温和条件下实现芳香烃直接羰基化制备芳香醛。催化剂活性高,产物选择性高。
(2)反应结束后,催化剂易于分离,且可回收利用,有很好的应用前景。
附图说明
图1为RhCl(CO)(PPh3)2/SBA-15催化甲苯羰基化反应的甲苯转化率随温度变化图;
图2为RhCl(CO)(PPh3)2/SBA-15催化甲苯羰基化反应的对甲基苯甲醛选择性随温度变化图;
图3为PdCl2(PPh3)2/SBA-15催化甲苯羰基化反应的甲苯转化率随温度变化图;
图4为PdCl2(PPh3)2/SBA-15催化甲苯羰基化反应的对甲基苯甲醛选择性随温度变化图;
图5为RhCl(CO)(PPh3)2/SBA-15催化甲苯羰基化反应的甲苯转化率随时间变化图;
图6为RhCl(CO)(PPh3)2/SBA-15催化甲苯羰基化反应的对甲基苯甲醛选择性随时间变化图;
图7为PdCl2(PPh3)2/SBA-15催化甲苯羰基化反应的甲苯转化率随时间变化图;
图8为PdCl2(PPh3)2/SBA-15催化甲苯羰基化反应的对甲基苯甲醛选择性随时间变化图;
图9为RhCl(CO)(PPh3)2和PdCl2(PPh3)2在无载体负载时催化甲苯羰基化制备对甲基苯甲醛反应时的甲苯转化率图;
图10为RhCl(CO)(PPh3)2和PdCl2(PPh3)2在无载体负载时催化甲苯羰基化制备对甲基苯甲醛反应时的对甲基苯甲醛选择性图;
图11为载体在无活性组分负载时催化甲苯羰基化制备对甲基苯甲醛反应时的甲苯转化率图;
图12为载体在无活性组分负载时催化甲苯羰基化制备对甲基苯甲醛反应时的对甲基苯甲醛选择性图;
图13为不同载体负载的催化剂催化甲苯羰基化反应的甲苯转化率图;
图14为不同载体负载的催化剂催化甲苯羰基化反应的对甲基苯甲醛选择性图。
下面以实施例详述本发明。
具体实施方式
实施例1-16:不同温度下,RhCl(CO)(PPh3)2/SBA-15或者PdCl2(PPh3)2/SBA-15催化甲苯羰基化制备对甲基苯甲醛反应结果如图1-4所示。具体实验过程描述如下:
将0.92g甲苯,0.92g催化剂,2mL甲醇加入10mL反应釜中,充入一氧化碳至2MPa,不断搅拌下,在不同温度下保持8h。如果一氧化碳分压下降,补充一氧化碳至2MPa。反应结束后,冷却至室温。产物分析采用气相色谱法。反应结束后,反应液离心,取上层清液进行气相色谱分析。
从图中可以看到,使用两种催化剂催化甲苯羰基化反应时,甲苯转化率随反应温度升高不断提高,而对甲基苯甲醛选择性在反应温度大于100℃时开始降低。温度过高,副反应增多使得对甲基苯甲醛收率降低。因此,最佳反应温度设定为100-140℃。
实施例17-32:不同反应时间,RhCl(CO)(PPh3)2/SBA-15或者PdCl2(PPh3)2/SBA-15催化甲苯羰基化制备对甲基苯甲醛反应结果如图5-8所示。具体实验过程描述如下:
将0.92g甲苯,0.92g催化剂,2mL甲醇加入10mL反应釜中,充入一氧化碳至2MPa,不断搅拌下升温至120℃,并分别保持不同反应时间。如果一氧化碳分压下降,补充一氧化碳至2MPa。反应结束后,冷却至室温。反应液离心,取上层清液进行气相色谱分析。
实施例33-34:RhCl(CO)(PPh3)2或者PdCl2(PPh3)2在无载体负载时催化甲苯羰基化制备对甲基苯甲醛反应结果如图9-10所示。具体实验过程描述如下:
将0.92g甲苯,0.09g催化剂,2mL甲醇加入10mL反应釜中,充入一氧化碳至2MPa,不断搅拌下,在120℃下保持10h。如果一氧化碳分压下降,补充一氧化碳至2MPa。反应结束后,冷却至室温。反应液离心,取上层清液进行气相色谱分析。
从图中可以看到,无载体负载的活性组分催化甲苯羰基化反应时,甲苯转化率均高于相应的均相催化剂。但对甲基苯甲醛的选择性均低于相应的均相催化剂,这是因为活性组分分布在介孔二氧化硅载体的特殊孔道结构中,由于择形效应使得产物选择性提高。
实施例35-38:无活性组分负载的载体对甲苯羰基化制备对甲基苯甲醛反应的作用结果如图11-14所示。具体实验过程描述如下:
将0.92g甲苯,0.92g载体,2mL甲醇加入10mL反应釜中,充入一氧化碳至2MPa,不断搅拌下,在120℃下保持10h。如果一氧化碳分压下降,补充一氧化碳至2MPa。反应结束后,冷却至室温。反应液离心,取上层清液进行气相色谱分析。
从图中可以看到,无活性组分负载的载体对甲苯羰基化反应活性很小。可以判断此多相催化体系中起催化作用的主要是Pd(II)或者Rh(III)。
实施例39-44:不同载体负载的催化剂RhCl(CO)(PPh3)2/SBA-16、RhCl(CO)(PPh3)2/MCM-41、RhCl(CO)(PPh3)2/MCM-48、PdCl2(PPh3)2/SBA-16、PdCl2(PPh3)2/MCM-41、PdCl2(PPh3)2/MCM-48催化甲苯羰基化反应结果如图9-10所示。具体实验过程描述如下:
将0.92g甲苯,0.92g催化剂,2mL甲醇加入10mL反应釜中,充入一氧化碳至2MPa,不断搅拌下,在120℃下保持10h。如果一氧化碳分压下降,补充一氧化碳至2MPa。反应结束后,冷却至室温。产物分析采用气相色谱法。反应结束后,反应液离心,取上层清液进行气相色谱分析。
从图中可以看到,使用不同载体负载的催化剂均能催化甲苯羰基化反应。
实施例45-54:各种芳烃催化羰基化反应结果如表1所示。具体实验过程描述如下:
将0.01mol芳香烃(苯,乙苯,正丙苯,异丙苯,正丁苯,叔丁苯,正戊苯,正己苯,正庚苯,正辛苯),0.92g的RhCl(CO)(PPh3)2/SBA-15,2mL甲醇加入10mL反应釜中,充入一氧化碳至2MPa,不断搅拌下升温至120℃,并保持10h。如果一氧化碳分压下降,补充一氧化碳至2MPa。反应结束后,冷却至室温。反应液离心,取上层清液进行气相色谱分析。
从表中可以看出,各类芳香烃在该催化体系下,均能实现高效的催化羰基化。
表1
实施例55-60:催化剂重复使用情况如表2所示。具体实验过程描述如下:
将0.92g甲苯,0.92g RhCl(CO)(PPh3)2/SBA-15,2mL甲醇加入10mL反应釜中,充入一氧化碳至2MPa,不断搅拌下升温至120℃,并保持10h。如果一氧化碳分压下降,补充一氧化碳。反应结束后,冷却至室温。反应液离心,取上层清液进行气相色谱分析。
反应结束后,采用离心的方法将催化剂分离出来,所得固体用甲醇洗涤、干燥后,即可用于下一轮芳香烃羰基化反应。
从表中可以看出,催化剂经过6次重复使用,仍有较高催化活性,说明该催化剂具有良好的稳定性。
表2
以上所述,仅为本发明部分具体实施例,但是本发明的保护范围并不仅限于此,也不因各实施例的先后次序对本发明造成任何限制,任何熟悉本发明技术领域的技术人员在本发明报道的技术范围内,可轻易进行变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围不仅限于以上实施例,应该以权利要求的保护范围为准。
Claims (6)
1.一种多相催化芳香烃羰基化制备芳香醛的方法,其特征在于:以一氧化碳为羰基化试剂,以载体负载活性组分作为催化剂,所述活性组分为RhCl(CO)(PPh3)2或者PdCl2(PPh3)2中的一种或者二种;芳香烃羰基化制备芳香醛;
所述催化剂载体为SBA-15、SBA-16、MCM-41、MCM-48中的一种或者多种;所述催化剂载体的比表面积为500-1000 m2/g。
2.按照权利要求1所述的方法,其特征在于:芳香烃为下列结构中的一种或者多种:
。
3.按照权利要求1所述的方法,其特征在于:活性组分按氧化物计与载体的质量比为0.002-0.150。
4.按照权利要求1或2所述的方法,其特征在于:所述催化剂的制备过程为: 按所需比例将活性组分前体与载体于二氯甲烷中混合,并在氮气保护下,室温搅拌20-40 h,然后,过滤得到固体样品,最后用二氯甲烷洗涤固体1-3 h。
5.按照权利要求1所述的方法,其特征在于:该方法中所用催化剂与反应底物的质量比为0.04-3.60。
6.按照权利要求1所述的方法,其特征在于:该方法中羰基化反应的一氧化碳分压为1.5-3.0 MPa;反应温度为100-140 ℃;反应时间为6-14 h。
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