WO3/SiO2催化剂上2-丁烯与乙烯歧化制丙烯

Metathesis of ethylene and 2-butylene to propylene over WO3/SiO2 catalysts

  • 摘要:  采用浸渍法制备了WO3/SiO2催化剂,对其进行了UV-Vis DRS和NH3-TPD表征。将WO3/SiO2作为催化剂,以乙烯和2-丁烯为原料制备丙烯,考察了反应温度、质量空速等因素对歧化反应的影响。实验结果表明,催化剂的最佳WO3担载量为8 %;以8%WO3/SiO2 为催化剂,在反应温度473K~573K、压力3.0MPa、质量空速1.6h-1下,2-丁烯的转化率可保持在80%以上,丙烯的选择性大于89.2%。经过140h的稳定性实验,2-丁烯的转化率和丙烯的选择性略有下降,适当的提高反应温度(由473K增加到513K)可以恢复催化剂的活性。新鲜催化剂表面存在四面体、八面体六价钨物种和体相WO3,适当还原的W物种是歧化活性物种;W负载在催化剂表面引入了新的强酸中心,同时明显增加了总酸量。

     

    Abstract: The WO3/SiO2 catalysts were prepared by impregnation (NH4)2WO4 onto SiO2 supports and their physicochemical properties were characterized by means of UV-Vis DRS and NH3-TPD. Effects of reaction conditions on the catalytic performance of WO3/SiO2 for metathesis of ethylene and 2-butylene to produce propylene were investigated. The optimal amount of WO3 loading was ~8%. Under the conditions of 473K~573K, 3.0MPa and 1.6h-1, the initial 2-butene conversion was higher than 80% with an exceeding 89.2% selectivity to  propylene, using 8%WO3/SiO2 as the catalyst. It was shown that the 2-butene conversion and propylene selectivity decreased slightly during 140h continuous operation, and the metathesis activity of catalyst can be recovered through increasing the reaction temperature from 473K to 513K. The characterization revealed that three types of W+6 species (tetrahedral tungsten oxide species, octahedral polytungstate species and WO3 crystallites) were present in fresh WO3/SiO2 catalysts and the reduced form of tungsten oxide species (W+4, W+5 and W+(6-y) (0<y<1)) may be the suitable state of W species acting as metathesis active centers. NH3-TPD results demonstrated that new acid sites were introduced into the catalysts and the total amount of acidity was increased when SiO2 supports were loaded with WO3.

     

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