Abstract:

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 NiMo_0.2/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, NiMo_0.2/γ-Al₂O₃ exhibited the best hydrogenation activity and sulfur resistance. Catalyst NiMo_0.2/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 NiMo_0.2/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%.

Key words: dicyclopentadiene, hydrogenation, sulfur resistance, molybdenum, nickel-based catalyst

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NiMo_0.2/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，NiMo_0.2/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，NiMo_0.2/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%。

关键词: 双环戊二烯, 加氢, 耐硫特性, 钼, 镍基催化剂