ZSM-5硅烷化改性对临氢降凝催化剂的影响
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摘要
采用液相沉积法对ZSM-5分子筛进行硅烷化改性,以改性后的分子筛为原料制备了变压器油临氢降凝催化剂,通过N_2-BET、NH_3-TPD和By-IR等方法对催化剂进行表征。以环烷基原油加氢改质柴油为原料油,在固定床反应器上对催化剂进行性能评价。结果表明,通过控制SiO_2的沉积位置和沉积量,可以降低外表面酸性、修饰孔口尺寸,阻止非择形裂解反应,提高反应的择形性能。在反应温度280℃、压力8 MPa、空速1.0 h~(-1)和氢油体积比500∶1的条件下,使用自制的催化剂,可得到倾点小于-50℃的40~#变压器油馏分。
Silanization of ZSM-5 molecular were prepared by liquid deposition method.Then hydrodewaxing catalyst for transformer oil was prepared from the modified zeolite,and characterized by N_2-BET,NH_3-TPD and By-IR.The performance of catalyst was evaluated in a fixed-bed reactor using naphthenic hydro-upgrading diesel as raw material.The results show that by controlling the deposition position and deposition amount of SiO_2,outer surface acidity can be reduced,pore size can be modified,and the non-shape selective pyrolysis reaction can be prevented so as to improve shape-selectivity.Using this catalyst,the 40# transformer oil with pour point less than-50 ℃can be obtained under the conditions of reaction temperature 280 ℃,pressure 8 MPa,space velocity 1.0 h~(-1),and hydrogen to oil volume ratio 500∶1.
Silanization of ZSM-5 molecular were prepared by liquid deposition method.Then hydrodewaxing catalyst for transformer oil was prepared from the modified zeolite,and characterized by N_2-BET,NH_3-TPD and By-IR.The performance of catalyst was evaluated in a fixed-bed reactor using naphthenic hydro-upgrading diesel as raw material.The results show that by controlling the deposition position and deposition amount of SiO_2,outer surface acidity can be reduced,pore size can be modified,and the non-shape selective pyrolysis reaction can be prevented so as to improve shape-selectivity.Using this catalyst,the 40# transformer oil with pour point less than-50 ℃can be obtained under the conditions of reaction temperature 280 ℃,pressure 8 MPa,space velocity 1.0 h~(-1),and hydrogen to oil volume ratio 500∶1.
引文
[1]李大东,聂红,孙丽丽,等.加氢处理工艺与工程[M].北京:中国石化出版社,2004.
[2]徐如人,庞文琴,霍启升,等.分子筛与多孔材料化学[M]. 北京:科学出版社,2004.
[3]王桂茹,韩翠英,于桂燕,等.ZSM-5沸石催化剂外表面的化学修饰[J].催化学报,1993,14(1):65-68.Wang Guiru,Han Cuiying,Yu Guiyan,et al.Chemical modification of external surface of ZSM-5 zeolite catalysts[J]. Chinese Journal of Catalysis,1993,14(1):65-68.
[4]兰权,刘丽芝,黎元生.ZSM-5分子筛孔口修饰的分子模拟研究[C]//2003年石油化工学术年会论文集.北京:中国化工学会,2003.
[5]刘丽芝,郭洪臣.硅烷化改性ZSM-5分子筛用于催化脱蜡催化剂[J].石化技术与应用,2009,27(3):242-245.Liu Lizhi,Guo Hongchen.Silanizing- modified zeolite catalyst ZSM -5 for catalytic dewaxing[J].Petrochemical Technology & Application,2009,27(3):242-245.
[2]徐如人,庞文琴,霍启升,等.分子筛与多孔材料化学[M]. 北京:科学出版社,2004.
[3]王桂茹,韩翠英,于桂燕,等.ZSM-5沸石催化剂外表面的化学修饰[J].催化学报,1993,14(1):65-68.Wang Guiru,Han Cuiying,Yu Guiyan,et al.Chemical modification of external surface of ZSM-5 zeolite catalysts[J]. Chinese Journal of Catalysis,1993,14(1):65-68.
[4]兰权,刘丽芝,黎元生.ZSM-5分子筛孔口修饰的分子模拟研究[C]//2003年石油化工学术年会论文集.北京:中国化工学会,2003.
[5]刘丽芝,郭洪臣.硅烷化改性ZSM-5分子筛用于催化脱蜡催化剂[J].石化技术与应用,2009,27(3):242-245.Liu Lizhi,Guo Hongchen.Silanizing- modified zeolite catalyst ZSM -5 for catalytic dewaxing[J].Petrochemical Technology & Application,2009,27(3):242-245.