In this work, ZSM-5 type chromosilicate samples as K[Cr]ZSM-5(KCS) and Na[Cr]ZSM-5(NCS) were prepared by hydrothermal method and their catalytic properties were investigated for the oxidative dehydrogenation of ethylb...In this work, ZSM-5 type chromosilicate samples as K[Cr]ZSM-5(KCS) and Na[Cr]ZSM-5(NCS) were prepared by hydrothermal method and their catalytic properties were investigated for the oxidative dehydrogenation of ethylbenzene in the presence of CO<sub>2</sub> as an oxidant using a fixed-bed stainless steel reactor. The prepared samples were characterized by their morphology (SEM), structural parameters (XRD), and textural parameters (BET). The performance of these catalysts was evaluated in terms of conversion, styrene yield, and selectivity. The KCS<sub>BW</sub> catalyst (potassium chromosilicate before washing with distilled water) afforded the highest styrene yield, 56.19%, with the selectivity of 96.05% in the presence of CO<sub>2</sub> because of the coexistence of potassium ion and Cr<sub>2</sub>O<sub>3</sub> in its structure and their synergistic effect. The influence of the presence of Cr<sub>2</sub>O<sub>3</sub> and sodium or potassium ion on the catalytic activity of the chromosilicate samples in the catalytic EB dehydrogenation process was discussed in detail. Moreover, according to the results, the catalytic activity of the chromosilicate samples (CS) in EB dehydrogenation was increased by decreasing the surface area.展开更多
Dehydrogenation of ethylbenzene （EB） to styrene （ST） in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift （RWGS）, was investigated extensively through both theoretical ...Dehydrogenation of ethylbenzene （EB） to styrene （ST） in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift （RWGS）, was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.展开更多
文摘In this work, ZSM-5 type chromosilicate samples as K[Cr]ZSM-5(KCS) and Na[Cr]ZSM-5(NCS) were prepared by hydrothermal method and their catalytic properties were investigated for the oxidative dehydrogenation of ethylbenzene in the presence of CO<sub>2</sub> as an oxidant using a fixed-bed stainless steel reactor. The prepared samples were characterized by their morphology (SEM), structural parameters (XRD), and textural parameters (BET). The performance of these catalysts was evaluated in terms of conversion, styrene yield, and selectivity. The KCS<sub>BW</sub> catalyst (potassium chromosilicate before washing with distilled water) afforded the highest styrene yield, 56.19%, with the selectivity of 96.05% in the presence of CO<sub>2</sub> because of the coexistence of potassium ion and Cr<sub>2</sub>O<sub>3</sub> in its structure and their synergistic effect. The influence of the presence of Cr<sub>2</sub>O<sub>3</sub> and sodium or potassium ion on the catalytic activity of the chromosilicate samples in the catalytic EB dehydrogenation process was discussed in detail. Moreover, according to the results, the catalytic activity of the chromosilicate samples (CS) in EB dehydrogenation was increased by decreasing the surface area.
基金The authors are grateful for the financial support of The Sate Key Fundamental Research Project and the Natural Science Foundation of China.
文摘Dehydrogenation of ethylbenzene （EB） to styrene （ST） in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift （RWGS）, was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.
