金属修饰对活性中孔材料(AMC)裂化性能的影响  

Investigation of the Effect of Metal-Modification on the Cracking Performance of Active Mesoporous Material

作　　者：郑金玉[1] 罗一斌[1] 喻辉 王进山 刘宇威 王成强[1] ZHENG Jinyu1 , LUO Yibin1 , YU Hui2 , WANG jinshan3 , LIU Yuwei3 , WANG Chengqiang1(l. Research Institute of Petroleum Processing, SINOPEC, Beijing 100083, China ; 2. SINOPEC Catalyst Company Limited Changling Division, Yueyang 414014, China ; 3. Shandong Yuhuang Chemical Company Limited, Heze 274000, Chin)

机构地区：[1]中国石化石油化工科学研究院,北京100083 [2]中国石化催化剂有限公司长岭分公司,湖南岳阳414014 [3]山东玉皇盛世化工股份有限公司,山东菏泽274000

出　　处：《石油学报（石油加工）》2018年第3期455-464,共10页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：中国石油化工股份有限公司项目(S111024)资助

摘　　要：通过成胶、老化、金属修饰等方法制备得到活性中孔材料(AMC),并采用XRD、XRF、BET、XPS、FT-IR、NH3-TPD等手段以及重油微反装置对材料进行详细结构表征和性能评价。结果表明,AMC材料具有拟薄水铝石结构,金属修饰对物相结构无影响,比表面积和孔体积随金属含量的增加而逐渐降低,但仍可保持明显的中孔特征,平均孔径达到10~11nm,金属修饰导致新Lewis酸中心的形成并具有中强酸的性质,修饰过程引起Br9nsted酸酸量的降低和Lewis酸酸量的提高以及强酸中心比例的降低,有效促进了重油大分子的预裂化,使材料的裂化活性明显增强。基于AMC材料开发了裂化催化剂CRM-100,并在山东玉皇盛世化工股份有限公司的催化裂化装置上进行了工业应用。应用结果表明,在蜡油掺炼比例较高、原油质量变差、装置处理量增加的情况下,CRM-100催化剂仍显示出优异的裂化性能,重油转化能力强,焦炭和干气的选择性佳,价值产品多,产品分布得到改善;装置的操作条件进一步优化,显著提高了经济效益。An active mesoporous material referred to as AMC was prepared by gelling,aging and metal-modification process.It was investigated by XRD,XRF,BET,XPS,FT-IR and NH3-TPD methods and evaluated by MAT.The results indicate that AMC has pseudo-boehmite structures,and the introduction of metal element has no effect on altering structure.The surface area and pore volume decrease with the increase of metal content and the average pore diameter is between10 nm-11 nm.New Lewis acid centers can be formed with the introduction of metal element,resulting in the increase of Lewis acid content.The content of Br9 nsted acid centers,the ratio of B/L and the strength of acid centers decrease by modification,which is beneficial for the precracking of heavy oil and the increase of cracking activity.A FCC catalyst CRM-100 was developed basing on AMC material and it had been employed in Yuhuang Shengshi Chemical Company Limited.The application results reveal CRM-100 possesses excellent cracking performance even at high ratio of wax oil,thus increasing the capacity of equipment.The product distribution and the operational condition are dramatically improved,and much more valuable products are obtained by using CRM-100.

关 键 词：中孔材料 金属修饰 催化裂化(FCC) 重油转化 

分 类 号：TE624[石油与天然气工程—油气加工工程]