KNO3和KF改性Pd-Pb／Al2O3催化剂用于混合C4选择加氢除炔-学兔兔 www.xuetutu.com.pdfVIP

学兔兔 石 油 化 工 · 1094· PETROCHEMICAL TECHNOL0GY 2010年第39卷第10期 KNO3和KF改性Pd—Pb／AI2 03催化剂 用于混合C4选择加氢除炔 杨 栋，朱云仙，乐 毅，徐立英 (中国石油化工股份有限公司 北京化工研究院，北京 100013) [摘要]用KNO3和KF助剂对Pd—Pb／A12O 催化剂进行改性，采用XPS，TEM，H2一TPD等方法对改性前后的催化剂进行了表 征，并考察了催化剂对混合C 选择加氢除炔反应的选择性。实验结果表明，KF改性对Pd—Pb／AI2O3催化剂的选择性有明显的 改善作用，而KNO 改性的效果甚微。在保证剩余炔烃质量分数小于1．5×10I5的情况下，KF改性后催化剂的1，3一丁二烯损失 为2．6％，较未改性的Pd—Pb／AI2O3催化剂降低了0．6个百分点。XPS表征显示，KF改性的催化剂中F主要以K3A1F6物种形 式存在，富电子的F对Pd的3 电子状态的影响可能是造成KF改性效果优于KNO 的主要原因。 [关键词]硝酸钾；氟化钾；钯一铅／氧化铝催化剂；混合碳四；选择加氢；除炔 [文章编号 1000—8144(2010)10—1094—05 [中图分类号：TQ 221．223 [文献标识码]A Pd-Pb／AI2 03 Catalyst Modified by KNO3 and KF for Selective Hydr0genatiOn 0f Crude C4 to Remove Alkynes Yang Dong，Zhu Yunxian，Yue Yi，Xu Liying (Beijing Research Institute of Chemical Industry，SINOPEC，Beijing 100013，China) l Abstract l The modification of Pd—Pb／A1．O catalyst with KNO，and KF was studied and used in hydrogenation of alkynes in crude C4． The catalysts before and after the modification were characterized by means of XPS，TEM and H2-TPD．The selectivities of these catalysts in the selective hydrogenation were investigated．Results showed that KF could significantly improve the selectivity of Pd．Pb／A1，O catalyst．while the effect of KNO was little．With the premises of less than 1．5×10 (mass fraction)of residual C4 alkynes in the hydrogenated crude C4，butadiene losses over KF modified Pd—Pb／A12 O3 catalyst achieved 2．6％ ，which was 0．6 percentage point lower than that over the