Cr incorporated MCM-41 type catalysts, which were prepared by direct hydrothermal synthesis and impregnation routes, were tested for dehydrogenation of isobutane. Among the surfactants (C 17 H 38 BrN, C 19 H 42 BrN, and C 32 H 68 BrN) used in the synthesis of MCM-41, C 19 H 42 BrN gave the best structure with ordered mesopores. Characterization results proved that chromium was very well dispersed within the MCM-41 lattice of the synthesized catalysts. In all of the synthesized catalysts, the presence of Cr 6+ (2p 3/2 ) in the form of chromates and Cr 3+ (2p 1/2 ) in the form of CrO x or Cr 2 O 3 was detected. All chromate types (mono, di, and poly) were observed in the catalyst synthesized hydrothermally according to the addition of metal solution simultaneously with silica source (CR_ALS). All characterization methods demonstrated that the highest amount of Cr 6+ was present in this catalyst. Catalytic tests of the synthesized catalysts were carried out at 600 °C and at atmospheric pressure. The maximum conversion value (∼27%) was reached at 15 min on CR_ALS catalyst. No products other than isobutene and hydrogen were encountered at the reactor outlet. Results proved that coke deposition was negligible over the synthesized catalysts in isobutane dehydrogenation. It was shown that the monochromates were the most active phase among all types of chromates for isobutane dehydrogenation. Catalyst deactivation occurred when the tetrahedrally coordinated Cr(VI)O 4 type of chromate was converted to inactive octahedrally coordinated Cr(III)O 6 groups and Cr 2 O 3 crystal phase.

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A chromium incorporated mesoporous silicate structured Cr/MCM-41 type catalyst was synthesized following a one-pot hydrothermal route and tested in dehydrogenation of isobutane to isobutene in a Pd membrane reactor. Characterization results of the catalyst proved that it had ordered pore structure with a narrow pore size distribution. This catalyst showed quite high activity for the dehydrogenation of isobutane. Membrane reactor tests performed at 823 K proved the advantages of in-situ removal of produced hydrogen from the reaction zone through the membrane, on isobutene yield. In fact, much higher isobutane conversions than the conversion values predicted from the equilibrium calculations were achieved at this temperature. However, at a higher temperature of 873 K, the Pd membrane itself also showed catalytic activity for the decomposition of isobutane and isobutene. As a result, lower isobutene selectivity values and quite high methane and propene selectivities were observed at this temperature. Cracking reactions also caused coke formation at 873 K, especially at high pressure differences across the membrane (70 kPa). Increase of pressure difference across the membrane caused fast removal of hydrogen from the reaction zone, which facilitated coke formation due to cracking reactions.

The syntheses of MCM-41 (Mobil Composition of Matter No. 41) supported chromium oxide cat-alysts at different chromium concentrations (4–10 % by mass) were carried out hydrothermally. The aim of this study was to determine the effect of chromium concentration in the catalyst structure on the chro-mate types and chromium oxidation states, as well as the activity of the catalyst in the isobutane dehydro-genation reaction. Inactive α-Cr2O3 crystals for isobutane dehydrogenation were shown to increase in the catalyst structure as the chromium loading increased. The highest amount of Cr6+ on the catalyst surface was detected in the catalyst (H4-MCM-41) with 4 % chromium by mass. Catalytic tests (T = 600 °C, P = atmospheric pressure, WHSV = 26 h–1) were performed under fixed bed reactor conditions. The high-est isobutane conversion (~60 %) and selectivity (~80 %) were observed on the H4-MCM-41 catalyst, which had the highest amount of Cr6+ and monochromate structures. Catalyst deactivation was not due to coke deposition but, rather, was caused by the formation of inactive α-Cr2O3 crystal structures.