双环戊二烯加氢NiMox/γ-Al2O3催化剂耐硫特性的研究  

Study on sulfur tolerance of NiMox/γ-Al2O3 catalyst for dicyclopentadiene hydrogenation

作　　者：史大昕 李爱如 方祝青 李继娟 矫庆泽 吴芹[1] 冯彩虹 赵芸 黎汉生 SHI Daxin;LI Airu;FANG Zhuqing;LI Jijuan;JIAO Qingze;WU Qin;FENG Caihong;ZHAO Yun;LI Hansheng(School of Chemistry and Chemical Engineering,Beijing Institute of Technology,Beijing 102488,China;School of Mechatronical Engineering,Beijing Institute of Technology,Beijing 100081,China;Zhuhai School of Beijing Institute of Technology,Zhuhai 519088,Guangdong,China)

机构地区：[1]北京理工大学化学与化工学院,北京102488 [2]北京理工大学材料学院,北京100081 [3]北京理工大学珠海学院,广东珠海519088

出　　处：《化工学报》2020年第9期4177-4188,共12页CIESC Journal

基　　金：国家自然科学基金项目(21576025)。

摘　　要：研究了钼元素及其添加量对镍基催化剂在双环戊二烯(DCPD)加氢反应中耐硫特性的影响规律。催化剂∶DCPD=1∶10,反应温度150℃,压力3.5 MPa,转速600 r/min,噻吩浓度为:500 mg/L时,Ni/γ-Al2O3催化剂的双环戊二烯8、9位双键的加氢速率显著降低,3、4位双键的加氢活性完全抑制;而NiMo0.2/γ-Al2O3催化剂,在4 h内完成加氢反应,四氢双环戊二烯(endo-THDCPD)收率达到98%,抗硫特性显著提高。不同镍钼比的系列催化剂中,NiMo0.2/γ-Al2O3具有最好的加氢活性与耐硫特性。0~2000 mg/L噻吩浓度内,低浓度条件下,NiMo0.2/γ-Al2O3催化剂对双环戊二烯的加氢活性高,选择性好;随着噻吩浓度增加,催化性能有所下降,2000 mg/L时,加氢反应延长至6 h,endo-THDCPD收率降至95%。The effect of Mo and its addition amount on the sulfur tolerance of Ni catalyst in the hydrogenation of dicyclopentadiene(DCPD)was studied.A series of γ-Al2O3 supported nickel-molybdenum bimetallic catalysts were prepared by the equal volume impregnation method.The performance test of the catalyst was carried out in an autoclave,the feed ratio was the catalyst∶DCPD∶cyclohexane=1∶10∶100.The reaction was carried out at a temperature of 150℃and a pressure of 3.5 MPa,with a stirring speed 600 r/min.Before the reaction starts,a certain amount of thiophene was added in cyclohexane in order to know the sulfur resistance of the catalyst.When the concentration of thiophene cyclohexane solution is 500 mg/L,the hydrogenation rate of the double bond of 8,9 position of dicyclopentadiene is significantly reduced under the catalysis of Ni/γ-Al2O3,and the hydrogenation activity of double bond of 3,4 position is completely suppressed;under NiMo0.2/γ-Al2O3 catalysis,however,the hydrogenation reaction is completed within 4 h,the yield of tetrahydrodicyclopentadiene(endo-THDCPD)reaches 98%,and the sulfur resistance of the catalyst is significantly improved.Among the series of catalysts with different nickel-molybdenum ratios,NiMo0.2/γ-Al2O3 exhibited the best hydrogenation activity and sulfur resistance.Catalyst NiMo0.2/γ-Al2O3 was tested for sulfur resistance with a thiophene concentration range of 0~2000 mg/L.When the concentration of thiophene is low,the NiMo0.2/γ-Al2O3 catalyst has high hydrogenation activity and good selectivity for dicyclopentadiene;as the concentration of thiophene increases,the catalytic performance of the catalyst decreases.When the thiophene concentration is increased to 2000 mg/L,the hydrogenation reaction is extended to 6 hours,and the yield of endo-THDCPD is reduced to 95%.

关 键 词：双环戊二烯 加氢 耐硫特性 钼 镍基催化剂 

分 类 号：TQ517.2[化学工程]