硫改性镍催化剂丁烯-1双键临氢异构性能

Performance of Sulfur Modified Catalysts for Hydroisomerization of 1-Butene

将Ni/Al_2O_3催化剂浸渍于有机多硫化物(TPS-37)中制备得到硫改性Ni/Al_2O_3催化剂。采用X射线荧光光谱(XRF)、热重-质谱(TG-MS)联用、X射线光电子能谱仪(XPS)和程序升温还原(TPR)等方法对催化剂进行表征,并考察了硫改性Ni/Al_2O_3催化剂上丁烯-1双键临氢异构性能。结果表明,硫改性Ni/Al_2O_3催化剂经高温氢气活化及甲苯萃取后,催化剂上硫含量基本不变。硫与催化剂之间存在较强的相互作用,使氧化镍在相对较低的温度下被H2还原;硫改变了Ni金属周围电子环境,从而显著改善催化剂的双键临氢异构性能。在反应温度60℃,氢压1.6 MPa,氢气和碳四烃物质的量之比(氢烃比)为0.013的条件下,硫改性Ni/Al_2O_3催化剂催化丁烯-1双键临氢异构反应,丁烯-1转化率可达92.6%,丁烯-2选择性为97.5%。催化剂稳定性实验结果表明,硫改性催化剂催化性能好,稳定性优良。

The sulfur-modified Ni-based catalysts were prepared by the incipient wetness impregnation technique with the Ni/Al2O3in solution of organic polysulfide.The catalysts were characterized by X-ray fluorescence(XRF),thermogravimetry-mass spectrometry(TG-MS),X-ray photoelectron spectroscopy(XPS)and temperature-programmed reduction(TPR).The performance of sulfur-modified Ni/Al2O3catalyst on hydrogen isomerization of1-butene double bond was investigated.The results showed that the sulfur content of the sulfur-modified Ni/Al2O3catalyst was almost unchanged after the activation of high temperature hydrogen and extraction with toluene.Since there was a strong interaction between the sulfur and the catalyst,nickel oxide was reduced by hydrogen at relatively low temperature.Sulfur changed the electronic environment around the Ni metal,thereby significantly improved the hydroisomerization of the catalyst at the double bond.The conversion up to92.6%,selectivity of2-butene97.5%were obtained when sulfur modified Ni/Al2O3catalyst was used to catalyze the hydroisomerization of1-butene under the operation conditions of temperature60℃,hydrogen pressure1.6MPa and the molar ratio of H2to C40.013.The catalyst stability tests demonstrated that the sulfur-modified Ni/Al2O3performed excellent with good stability.