TY - JOUR

T1 - Fluid phase equilibria of the reaction mixture during the selective hydrogenation of 2-butenal in dense carbon dioxide

A1 - Musko,Nikolai

A1 - Jensen,Anker Degn

A1 - Baiker,Alfons

A1 - Kontogeorgis,Georgios

A1 - Grunwaldt,Jan-Dierk

AU - Musko,Nikolai

AU - Jensen,Anker Degn

AU - Baiker,Alfons

AU - Kontogeorgis,Georgios

AU - Grunwaldt,Jan-Dierk

PB - Elsevier BV

PY - 2012

Y1 - 2012

N2 - Knowledge of the phase behaviour and composition is of paramount importance for understanding multiphase reactions. We have investigated the effect of the phase behaviour in the palladium-catalysed selective hydrogenation of 2-butenal to saturated butanal in dense carbon dioxide. The reactions were performed using a 5wt% Pd on activated carbon in custom-designed high pressure autoclaves at 323K. The Cubic-Plus-Association (CPA) equation of state was employed to model the phase behaviour of the experimentally studied systems. CPA binary interaction parameters were estimated based on the experimental vapour–liquid or liquid–liquid equilibria data available in the literature. No experimental data for the CO2–2-butenal binary system were available in the literature; therefore, the bubble points of this mixture of varying composition at three different temperatures were measured in a high-pressure view cell. The results of the catalytic experiments showed that small amounts of carbon dioxide added to the system significantly decrease the conversion, whereas at higher loadings of CO2 the reaction rate gradually increases reaching a maximum. The CPA calculations revealed that this maximum is achieved in the so-called “expanded liquid” region, which is located near the critical point of the reacting mixture. It was also found that in this point the hydrogen concentration achieved its maximum in the CO2-expanded phase. Furthermore, the pressure – temperature regions where the multicomponent reaction system exists in one single phase and in multiphase were calculated.

AB - Knowledge of the phase behaviour and composition is of paramount importance for understanding multiphase reactions. We have investigated the effect of the phase behaviour in the palladium-catalysed selective hydrogenation of 2-butenal to saturated butanal in dense carbon dioxide. The reactions were performed using a 5wt% Pd on activated carbon in custom-designed high pressure autoclaves at 323K. The Cubic-Plus-Association (CPA) equation of state was employed to model the phase behaviour of the experimentally studied systems. CPA binary interaction parameters were estimated based on the experimental vapour–liquid or liquid–liquid equilibria data available in the literature. No experimental data for the CO2–2-butenal binary system were available in the literature; therefore, the bubble points of this mixture of varying composition at three different temperatures were measured in a high-pressure view cell. The results of the catalytic experiments showed that small amounts of carbon dioxide added to the system significantly decrease the conversion, whereas at higher loadings of CO2 the reaction rate gradually increases reaching a maximum. The CPA calculations revealed that this maximum is achieved in the so-called “expanded liquid” region, which is located near the critical point of the reacting mixture. It was also found that in this point the hydrogen concentration achieved its maximum in the CO2-expanded phase. Furthermore, the pressure – temperature regions where the multicomponent reaction system exists in one single phase and in multiphase were calculated.

KW - CO2–2-butenal VLE

KW - Supercritical CO2

KW - Selective hydrogenation

KW - Equations of state

KW - CPA

U2 - 10.1016/j.apcata.2012.07.027

DO - 10.1016/j.apcata.2012.07.027

JO - Applied Catalysis A: General

JF - Applied Catalysis A: General

SN - 0926-860X

VL - 443-444

SP - 67

EP - 75

ER -