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Pd-Al 负载黏土催化剂在水相体系中催化 4-氯苯酚的加氢脱氯反应。

Pd-Al pillared clays as catalysts for the hydrodechlorination of 4-chlorophenol in aqueous phase.

机构信息

Area de Ingeniería Química, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain.

出版信息

J Hazard Mater. 2009 Dec 15;172(1):214-23. doi: 10.1016/j.jhazmat.2009.06.161. Epub 2009 Jul 5.

Abstract

Catalysts based on pillared clays with Pd-Al were synthesized from a commercial bentonite and tested for catalytic hydrodechlorination (HDC) using 4-chlorophenol (4-CPhOH) as target compound and formic acid as hydrogen source. Stable Pd-Al pillared clays, with a strong fixation of the active phase to the solid support were obtained since no Pd was detected in the reaction media. The incorporation of Pd to the pillared clay structure yielded catalysts with high activity in the reaction studied reaching a complete removal of the 4-CPhOH under mild conditions of temperature (50-70 degrees C). Phenol was not the only reaction product formed, since a more hydrogenated product such as cyclohexanone was detected in the effluent, which indicates additional hydrogenation of phenol. The influence of the method of introduction of Pd in the pillared clay (ion-exchange or impregnation) and Pd concentration in the catalytic activity were studied as well as other important operating variables such as reaction temperature, catalyst concentration, 4-CPhOH initial concentration and formic acid to 4-CPhOH molar ratio. The catalysts prepared suffered deactivation after three consecutive runs, probably due to carboneous deposits formation since no appreciable Pd leaching was observed.

摘要

基于 Pd-Al 的层柱粘土催化剂是由商业膨润土合成的,并用于催化氢解(HDC),以 4-氯苯酚(4-CPhOH)为目标化合物,甲酸为氢源。由于反应介质中未检测到 Pd,因此获得了稳定的 Pd-Al 层柱粘土,活性相与固体载体之间具有很强的固定性。将 Pd 掺入层柱粘土结构中,得到了在研究反应中具有高活性的催化剂,在温和的温度条件(50-70°C)下完全去除了 4-CPhOH。苯酚不是唯一形成的反应产物,因为在流出物中检测到更氢化的产物,如环己酮,这表明苯酚的进一步氢化。还研究了 Pd 在层柱粘土中的引入方法(离子交换或浸渍)和 Pd 浓度对催化活性的影响,以及其他重要的操作变量,如反应温度、催化剂浓度、4-CPhOH 初始浓度和甲酸与 4-CPhOH 的摩尔比。催化剂在连续运行三次后失活,可能是由于形成了碳沉积物,因为没有观察到明显的 Pd 浸出。

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