Johan van den Bergh

Ethane/Ethene Separation Turned on Its Head: Selective Ethane Adsorption on the Metal−Organic Framework ZIF-7 through a Gate-Opening Mechanism

Ethane is selectively adsorbed over ethylene in their mixtures on the zeolite imidazolate framework ZIF-7. In packed columns, this results in the direct production of pure ethylene. This gas-phase separation is attributed to a gate-opening effect in which specific threshold pressures control the uptake and release of individual molecules. These threshold pressures differ for the different molecules, leaving a window of selective uptake operation. This phenomenon makes ZIF-7 a perfect candidate for the separation of olefins from paraffins, since in contrast to most microporous materials, the paraffin is selectively adsorbed. Mixture adsorption, as studied by breakthrough experiments, demonstrates that gate-opening effects can be effectively used to separate molecules of very similar size.

Understanding the anomalous alkane selectivity of ZIF-7 in the separation of light alkane/alkene mixtures.

C2 and C3 alkanes are selectively adsorbed from mixtures over the corresponding alkenes on the zeolite imidazolate framework ZIF-7 through a gate-opening mechanism. As a result, the direct production of the pure alkene upon adsorption and the pure alkane upon desorption in packed columns is possible. Herein, a detailed investigation of the step-wise adsorption and separation of alkanes and alkenes is presented, together with a rigorous performance assessment. A molecular picture of the gate-opening mechanism underlying the unprecedented selectivity towards alkane adsorption is proposed based on DFT calculations and a thermodynamic analysis of the adsorption-desorption isotherms.

Natural gas purification with a DDR zeolite membrane; permeation modelling with maxwell-stefan equations

Abstract The permeation of CO 2 , N 2 and CH 4 and their mixtures through a DDR membrane has been investigated over a wide range of temperatures and pressures. The synthesized DDR membrane exhibits a very high selectivity for CO 2 and a moderate selectivity for N 2 over CH 4 with good permeances. At a total pressure of 101 kPa and temperature of 225 K, the selectivity for CO 2 was found to be over 3000 and 40 for N 2 in a 50/50 feed mixture with CH 4 , both decrease with temperature. The N 2 /CH 4 selectivity remains constant with pressure, while that for CO 2 /CH 4 decreases. An engineering model, based on the generalized Maxwell-Stefan equations, has been used to interpret the transport phenomena in the membrane. The diffusivity of these permanent gases is strongly dependent on the loading in the membrane, severely complicating modelling work. A model developed by Reed and Ehrlich [ 1 ] could describe this phenomenon well for both the unary as the binary permeances. The feasibility of DDR membranes as applied to CO 2 and N 2 removal from natural gas is anticipated.

Separation of CO2 and CH4 by a DDR membrane

The permeation of CO2 and CH4 and their binary mixtures through a DDR membrane has been investigated over a wide range of temperatures and pressures. The synthesized DDR membrane exhibits a high permeance and maintains a very high selectivity for CO2. At a total pressure of 101 kPa, the highest selectivity for CO2 in a 50∶50 feed mixture was found to be over 4000 at 225 K. This is ascribed to the higher adsorption affinity, as well as to the higher mobility for the smaller CO2 molecules in the zeolite, preventing the bypassing of the CH4 through the membrane. An engineering model, based on the generalized Maxwell-Stefan equations, has been used to interpret the transport phenomena in the membrane. The feasibility of DDR membranes as applied to CO2 removal from natural gas or biogas is anticipated.

Facile synthesis of the DD3R zeolite: performance in the adsorptive separation of buta-1,3-diene and but-2-ene isomers

Small pore size and hydrophobic nature of DD3R make this material a unique zeolite with high potential in industrial separation applications. However, the reproducible rapid synthesis of this zeolite is still a problem. In this work, a thorough assessment of different synthetic methods revealed that synthesis reproducibility relies on two main pillars: the use of properly cleaned autoclave liners and the synthesis composition. High quality DD3R crystals are obtained when KOH is used as a cleaning agent, eliminating memory effects, and when KF is used in the synthesis as a mineralizing agent. The effect of fluoride addition is investigated by use of several characterization techniques (13C, 19F and 29Si MAS-NMR and (2D) 29Si–1H correlation spectra), while monitoring the temporal crystallization of DDR. 29Si–1H NMR reveals that template molecules accommodated within the cages are sticking to these 8-ring windows through their amine group. High quality DD3R crystals are applied in the adsorptive separation of buta-1,3-diene and but-2-ene isomers, one of the most energy intensive separations in chemical industry. Mixture separation experiments revealed that the 8-ring apertures of the DD3R cages are only accessible to trans-but-2-ene and buta-1,3-diene, while excluding but-1-ene and cis-but-2-ene molecules, resulting in shape-selective separation in the presence of C4 mixtures.

Production of Monosugars from Lignocellulosic Biomass in Molten Salt Hydrates: Process Design and Techno-Economic Analysis

ZnCl2 hydrate, the main molten salt used in biomass conversion, combined with low concentration HCl is an excellent solvent for the dissolution and hydrolysis of the carbohydrates present in lignocellulosic biomass. The most recalcitrant carbohydrate, cellulose, is dissolved in a residence time less than 1 h under mild conditions without significant degradation. This technology is referred to as BIOeCON-solvent technology. Separation of the sugars from the solution is the main challenge. The earlier conclusion regarding the potential of zeolite beta for selective adsorption has been used as the basis of a scale-up study. The technology of choice is continuous chromatographic separation (e.g., simulated moving bed, SMB). The sugar monomers are separated from the sugar oligomers, allowing the production of monosugars at high yield, using water as an eluent. Results of a pilot plant study are presented showing a stable operation at high selectivity. Several process designs are discussed, and the techno-economic performance of the BIOeCON-solvent technology is demonstrated by comparison with the state-of-the-art technology of NREL (National Renewable Energy Laboratory), which is based on enzymatic conversion of cellulose. It is concluded that the BIOeCON-solvent technology is technically and economically viable and is competitive to the NREL process. Because the BIOeCON-solvent process is in an early stage of development and far from fully optimized, it has the potential to outperform the existing processes.