Effects of metal cation on the skeletal isomerization of n-Butene over ZSM-5 and ferrierite

Abstract

The effects of metal cation on the skeletal isomerization of 1-butene to isobutene was investigated. H-ZSM-5 was sythesized with the initial SiO2/Al2O3 ratio of 30. MFI-50, MFI-90 and Ferrrierite zeolite catalysts were commercially supplied. The zeolites were ion exchanged with cobalt, nickel, zinc, cupper (magnesium and manganese only for synthesized ZSM-5) salts, impregnated with cobalt, in order to change their acidity.The H-ZSM-5 zeolite was additionally ion exchanged with cobalt using different metal loading amounts. Then, the catalysts were tested for their activity in a fixed bed tubular quartz reactor at 375°C at weight hourly space velocity (WHSV) of 22 h-1.Scanning Electron Microscopy images and X-Ray Powder Diffraction patterns of the zeolites showed that their crystallinity was not affected with ion exchange, even with the increase in the loading amount (2.68 w%). But with the impregnation method, the intensity of the characteristic peaks for zeolites were decreased. Impregnating the zeolite also resulted in a decrease in the surface area.The acidity measurements of the catalysts were made by IR spectroscopy with pyridine adsorption method. The tests showed that acidities of the catalysts were changed with ion exchange and impregnation of metal ions.The catalytic tests for H-ZSM-5 showed that different metal loadings with ion exchange lowered the yield for isobutene. H-ZSM-5 showed a conversion of 59 % and 33.2 % yield for isobutene. The lowest yield was obtained from magnesium and manganese with 12.2 % and 9.6 %, respectively. The H-ZSM-5 zeolite catalysts were also tested for Co ion exchanged with different amounts (2.68, 1.45, 0.63 and 0.23 w%).1.45 w% loaded catalyst showed the best activity for the reaction with a conversion of 59.1 %, and yield for isobutene 24.5 %. Both increased and decreased loading decreased yield 17.8 %, 2.5 % and 0.48 %, respectively. H-MFI-50 and its modified forms showed high conversions compared to H-ZSM-5. But low yields and selectivities were obtained. H-MFI-50 showed the highest conversion with 82.7 % and yield of 21.5 %. Co-MFI-50 showed similar conversion as the parent zeolite with 82.7 %, and yield of 17.9 %. The lowest conversion is obtained by Cu-MFI-50 with 76.5 % and yield for isobutene was 21 %. H-MFI-90 and its modified samples showed alike conversions around 76.1 %, but Cu loading decreased conversion as low as 65.9 %. Like MFI-50, the yield of isobutene was also affected by the metal ion exchanging. H-MFI-90 showed 24.8 % yield of isobutene. However, Co-MFI-90 had a yield of 27.6 %. The worst yield was obtained from cupper loaded catalyst with 20.4 %. As would be expected, changing the metal ion loaded to ferrierite also changed the activity of the catalyst. The highest conversion was obtained by H-FER with 57 % and a yield of 39 %. Co-FER and Ni-FER showed similar conversions 52 % and 53 %, respectively. Zn-FER and Cu-FER showed the lowest conversions with 47 % and 45 %, respectively. Yields for the metal loaded catalysts lowered to 27 %.Impregnation with Co, severely decreased the activity of the catalysts both compared to H form and ion exchanged form of the catalysts. Impregnated H-ZSM-5, H-MFI-50, H-MFI-90 and ferrierite showed conversions of 48.1 %, 66.8 %, 60.7 % and 45.4 %, respectively. The yields for isobutene were 11 %, 13.8 %, 15.5 % and 13.7 %, respectively.