3744-02-3Relevant articles and documents
Acetone condensation over CaO—SnO2 catalyst
Koklin,Hasyanova,Glukhov,Bogdan
, p. 488 - 490 (2017/09/15)
Aldol condensation of acetone was studied over solid base CaO—SnO2 catalyst in the 300—450 °C temperature range and at 15—75 atm pressure in a fixed-bed reactor. The main products are mesityl oxide and isophorone. The high stability of CaO—SnO2 catalyst performance was observed at pressure of 75 atm giving the acetone conversion of 36—41%. Increase in the temperature and pressure led to a simultaneous raise in acetone conversion. The maximum conversion of 41% was achieved at 400 °C, 75 atm and a flow rate of acetone of 8.1 g h–1 (g catalyst)–1.
Condensation and esterification reactions of alkanals, alkanones, and alkanols on TiO2: Elementary steps, site requirements, and synergistic effects of bifunctional strategies
Wang, Shuai,Goulas, Konstantinos,Iglesia, Enrique
, p. 302 - 320 (2016/07/06)
Rates and selectivity of TiO2-catalyzed condensation of C3 oxygenates (propanal, acetone) are limited by ubiquitous effects of side reactions, deactivation, and thermodynamic bottlenecks. H2 together with a Cu function, present as physical mixtures with TiO2, circumvents such hurdles by scavenging unsaturated intermediates. They also render alkanols and alkanals/alkanones equivalent as reactants through rapid interconversion, while allowing esterification turnovers by dehydrogenating unstable hemiacetals. Oxygenates form molecules with new C-C and C-O bonds and fewer O-atoms at nearly complete conversions with stable rates and selectivities. Kinetic, isotopic, and theoretical methods showed that rates are limited by α-C-H cleavage from carbonyl reactants to form enolate intermediates, which undergo C-C coupling with another carbonyl species to form α,β-unsaturated oxygenates or with alkanols to form hemiacetals with new C-O bonds, via an intervening H-shift that forms alkoxide-alkanal pairs. Titrations with 2,6-di-tert-butylpyridine, pyridine, CO2, and propanoic acid during catalysis showed that Lewis acid-base site pairs of moderate strength mediate enolate formation steps via concerted interactions with the α-H atom and the enolate moiety at transition states. The resulting site-counts allow rigorous comparisons between theory and experiments and among catalysts on the basis of turnover rates and activation free energies. Theoretical treatments give barriers, kinetic isotope effects, and esterification/condensation ratios in excellent agreement with experiments and confirm the strong effects of reactant substituents at the α-C-atom and of surface structure on reactivity. Surfaces with Ti-O-Ti sites exhibiting intermediate acid-base strength and Ti-O distances, prevalent on anatase but not rutile TiO2, are required for facile α-C-H activation in reactants and reprotonation of the adsorbed intermediates that mediate condensation and esterification turnovers.
Cr, Zr-incorporated hydrotalcites and their application in the synthesis of isophorone
Liu, Yanxia,Sun, Kunpeng,Ma, Haowen,Xu, Xianlun,Wang, Xiaolai
experimental part, p. 880 - 883 (2010/11/04)
Cr3+ and Zr4+ cation-incorporated hydrotalcites (HTs) were prepared by coprecipitation method. Corresponding mixed oxide were obtained by the thermal decomposition of HTs at 773 K for 8 h and applied in the synthesis of isophorone (IP) from acetone. From the characteristic results, both Cr3+ and Zr4+ were introduced into the lattice of hydrotalcite producing the more disordered HT structures. Compared with Mg-Al mixed oxide, Cr and Zr modified mixed oxide demonstrated more amount of basic sites and stronger base strength, which were responsible for the improvement of catalytic activity. As a result, both of the modified mixed oxide exhibited IP selectivity of more than 70% under atmospheric pressure.
