Mesoporous aluminosilicates as oligomerization catalysts

A catalyst based on the mesoporous molecular sieve MCM-41 aluminosilicate has been used for the oligomerization of propene and butenes[51-53] at low temperatures (between 353 and 473 K). The catalyst shows higher activity and selectivity for the formation of trimers and tetramers as compared with HZSM-5 and HZSM-23. 

Kim and Inui[54] have reported the synthesis of MCM-41 with incorporation of various metal components such as Al, Ga or Fe with different Si/metal ratio. These catalysts were used for the oligomerization of propene, and it was found that the order of activity was Al-MCM-41 Fe-MCM-41 Ga-MCM-41 with the optimum Si/metal ratio being equal to 200. The propene conversion increases with the temperature from 423 up to 523 K. The catalytic activity of mesoporous silicates was lower than zeolitic catalysts, such as MFI metallosilicates. However, 

Chiche et a/.[56] have studied the oligomerization of butene over a series of zeolite (HBeta and HZSM-5), amorphous silica alumina and mesoporous MTS-type aluminosilicates with different pores. The authors found that MTS catalyst converts selectively butenes into a mixture of branched dimers at 423 K and 1.5-2 MPa. Under the same reaction conditions, acid zeolites and amorphous silica alumina are practically inactive due to rapid deactivation caused by the accumulation of hydrocarbon residue on the catalyst surface blocking pores and active sites. The catalytic behaviour observed for the MTS catalyst was attributed to the low density of sites on their surface along with the absence of diffusional limitations due to an open porosity. This would result in a low concentration of reactive species on the surface with short residence times, and favour deprotonation and desorption of the octyl cations, thus preventing secondary reaction of the olefinic products. 

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