One-Pot Synthesis Method of MIL-96 Monolith and Its CO2 Adsorption Performance.

A novel preparation method was proposed for a metal-organic framework (MOF) monolith using a simple one-pot synthesis method. A MOF tubular monolith was successfully prepared by the hydrothermal treatment for an α-Al2O3 monolith in an aqueous solution of 1,3,5-benzenetricarboxylic acid and nitric acid without the addition of a metal source. The effects of temperature and the HNO3 concentration in the synthesis solution on the crystallization behavior of MIL-96 were studied. HNO3 enhanced the dissolution of the α-Al2O3 monolith and the growth of MIL-96. The growth rate of MIL-96 was also influenced by the synthesis temperature; a synthesis temperature of over 453 K was required for crystallization. The CO2 adsorption capacity of the prepared MIL-96 monoliths was evaluated and found to be comparable to that of the well-grown MIL-96 powdery crystal. Furthermore, the MIL-96 monoliths demonstrated good stability as their adsorption properties were retained even after 2 months of storage under atmospheric conditions.

Esterification of Acetic Acid by Flow-Type Membrane Reactor with AEI Zeolite Membrane.

AEI-type zeolite membrane for dehydration was prepared, and a flow-type membrane reactor for the esterification of acetic acid and ethanol by AEI membrane was developed. A synthesized AEI membrane had suitable molecular sieving property for gas separation (H2/i-butane and CO2/CH4) and pervaporation (H2O/acetic acid). AEI membrane showed H2O permeance of 6.2 × 10-7 mol m-2 s-1 Pa-1 with a separation factor of 67 at 363 K for the equimolar mixture of H2O/acetic acid. AEI membrane maintained stable performance under acidic conditions. The yield of ethyl acetate at 363 K in a flow-type membrane reactor with AEI membrane successfully exceeded the equilibrium of 69.1%, reaching 89.0%. The flow rate of feed solution strongly affected the conversion of acetic acid and the space-time yield (STY) of ethyl acetate. Due to the more significant proportion of water selectively removed from the reaction system at a lower feed flow rate, the thermodynamic equilibrium shifted significantly, resulting in higher conversions. In contrast, STY increased with increasing feed flow rate. Our flow-type membrane reactor exhibited a relatively large STY of 430 kg m-3 h-1 compared with the batch-type membrane reactor previously reported.

An Experimental Study of a Zeolite Membrane Reactor for Reverse Water Gas Shift.

Reverse water gas shift (RWGS) is attracting attention as one of the promising technologies for CO2 conversion. Selective removal of H2O from the reaction system can improve the CO2 conversion beyond the equilibrium conversion of RWGS in a conventional reactor. In this study, a conventional plug-flow reactor without membrane, and two types of RWGS membrane reactors using ZSM-5 membranes, were developed. The yield of CO without membrane (Case 1) was almost the same as the equilibrium conversion. A membrane reactor (Case 2) showed a CO yield 2-3% above that of a conventional reactor. From the results, the effectiveness of the dehydration membrane reactor for RWGS was verified. In addition, CO yield was further increased in the reactor made up of the combination of conventional reactor and membrane reactor (Case 3). For example, the CO yields in Cases 1, 2, and 3 at 560 K were 21.8, 24.9, and 29.0%, respectively. Although the CO yield increased in Case 2, a large amount of raw materials penetrated through the membrane to the permeation side, and was lost. In Case 3, H2 and CO2 permeation through the membrane were suppressed because of the existence of H2O, resulting in the prevention of the leakage of raw material, and contributing to the high CO yield.

Ultrapermeable 2D-channeled graphene-wrapped zeolite molecular sieving membranes for hydrogen separation.

The efficient separation of hydrogen from methane and light hydrocarbons for clean energy applications remains a technical challenge in membrane science. To address this issue, we prepared a graphene-wrapped MFI (G-MFI) molecular-sieving membrane for the ultrafast separation of hydrogen from methane at a permeability reaching 5.8 × 106 barrers at a single gas selectivity of 245 and a mixed gas selectivity of 50. Our results set an upper bound for hydrogen separation. Efficient molecular sieving comes from the subnanoscale interfacial space between graphene and zeolite crystal faces according to molecular dynamic simulations. The hierarchical pore structure of the G-MFI membrane enabled rapid permeability, indicating a promising route for the ultrafast separation of hydrogen/methane and carbon dioxide/methane in view of energy-efficient industrial gas separation.

Contribution of Pore-Connectivity to Permeation Performance of Silicalite-1 Membrane; Part II, Diffusivity of C6 Hydrocarbon in Micropore.

This study investigated the permeation behaviors of n-hexane and 2-methylpentane through two-types of silicalite-1 membranes that have different pore-connectivity. The permeation mechanisms of these hydrocarbons were able to be explained by the adsorption-diffusion model. In addition, the fluxes through silicalite-1 membranes could be expressed by the modified Fick's first law. The hydrocarbon fluxes through S-1S with better pore-connectivity were ca. 3-20 times larger than those through S-1M with poor pore-connectivity. For these membranes with different pore-connectivity, the activation energy of diffusion of n-hexane was 17.5 kJ mol-1 for the membrane with better pore-connectivity and 18.0 kJ mol-1 for the membrane with poorer pore-connectivity, whereas for 2-methylpentane it was 17.9 and 33.0 kJ mol-1, respectively. We concluded that the pore-connectivity in silicalite-1 membrane significantly influences the molecular diffusivities.

Contribution of Pore-Connectivity to Permeation Performance of Silicalite-1 Membrane; Part I, Pore Volume and Effective Pore Size.

The micropore volumes and effective pore sizes of two types of silicalite-1 membranes were compared with those of a typical silicalite-1 powder. The silicalite-1 membrane with fewer grain boundaries in the membrane layer showed similar micropore volume and effective pores size to those of the silicalite-1 powder. In contrast, when the silicalite-1 membrane contained many grain boundaries, relatively small micropore volume and effective pore size were observed, suggesting that narrowing and obstruction of the micropore would occur along grain boundaries due to the disconnection of the zeolite pore. The silicalite-1 membrane with fewer grain boundaries exhibited relatively high permeation properties for C6-C8 hydrocarbons. There was an over 50-fold difference in benzene permeance between these two types of membranes. We concluded that it is important to reduce grain boundaries and improve pore-connectivity to develop an effective preparation method for obtaining a highly permeable membrane.

Synthesis of FAU-Zeolite Membrane by a Secondary Growth Method: Influence of Seeding on Membrane Growth and Its Performance in the Dehydration of Isopropyl Alcohol-Water Mixture.

Y-type zeolite membranes were prepared on a porous tubular α-alumina support by a secondary growth process. Various experimental conditions such as seed size, pH of seed solution, and degassing of support were examined for understanding their influence on the membrane deposition process. The experimental results showed that the potential of alumina support surface and the USY seed slurry plays a significant role in controlling the electrostatic interaction between seed particles and support surface and also the aggregation of USY seed particles in the slurry. In addition, we also noted the significance of the capillary forces working at the three-phase interface on the support surface and is a key factor that governs the seeding behavior onto the tubular support surface. Optimization of these parameters resulted in crack-free compact membranes that were able to effectively separate a mixture of isopropyl alcohol and water in a vapor-phase separation process.

Olefin Recovery by *BEA-Type Zeolite Membrane: Affinity-Based Separation with Olefin-Ag+ Interaction.

Ag+ was introduced into *BEA-type zeolite membrane by an ion-exchange method to enhance olefin selectivity. Ag-*BEA membrane exhibited superior olefin separation performance for both ethylene/ethane and propylene/propane mixtures. Particularly, the separation factor for ethylene at 373 K reached 57 with the ethylene permeance of 1.6×10-7  mol m-2 s-1 Pa-1 . Adsorption properties of olefin and paraffin were evaluated to discuss contribution of Ag+ to separation performance enhancement. A strong interaction between olefin and Ag+ in the membrane caused preferential adsorption of olefin against paraffin, leading to selective permeation of olefin. Ag-*BEA membrane also exhibited high olefin selectivities from olefin/N2 mixtures. The affinity-based separation through Ag-*BEA membrane showed a high potential for olefin recovery and purification from various gas mixtures.

Adsorption separation of heavier isotope gases in subnanometer carbon pores.

Isotopes of heavier gases including carbon (13C/14C), nitrogen (13N), and oxygen (18O) are highly important because they can be substituted for naturally occurring atoms without significantly perturbing the biochemical properties of the radiolabelled parent molecules. These labelled molecules are employed in clinical radiopharmaceuticals, in studies of brain disease and as imaging probes for advanced medical imaging techniques such as positron-emission tomography (PET). Established distillation-based isotope gas separation methods have a separation factor (S) below 1.05 and incur very high operating costs due to high energy consumption and long processing times, highlighting the need for new separation technologies. Here, we show a rapid and highly selective adsorption-based separation of 18O2 from 16O2 with S above 60 using nanoporous adsorbents operating near the boiling point of methane (112 K), which is accessible through cryogenic liquefied-natural-gas technology. A collective-nuclear-quantum effect difference between the ordered 18O2 and 16O2 molecular assemblies confined in subnanometer pores can explain the observed equilibrium separation and is applicable to other isotopic gases.

Preferential Adsorption of Propylene over Propane on a Ag-Exchanged X-Type Zeolite Membrane.

We investigated the adsorption properties of propylene and propane on an olefin-selective Ag-X membrane and discussed the contribution of adsorption selectivity to propylene/propane separation performance through this membrane. The isotherms of propylene and propane on Ag-X membranes were measured in unary systems at 313 K. The amount of propylene adsorbed on the Ag-X membrane at a lower pressure increased remarkably compared with that on the Na-X membrane. Such a change of adsorption property could induce excellent separation property for the Ag-X membrane. We compared the adsorption properties in a binary system calculated based on the Markham-Benton approach with the results of a permeation test. The molar fractions of propylene in the adsorbed phase in the binary system provided good agreement with propylene purity on the permeation side of the Ag-X membrane. These results clearly show that permeation selectivity of the Ag-X membrane for the propylene/propane mixture is mainly governed by adsorption selectivity.

Organic Structure-directing Agent-free Synthesis for *BEA-type Zeolite Membrane.

Membrane separation has drawn attention as a novel-energy saving separation process. Zeolite membranes have great potential for hydrocarbon separation in petroleum and petrochemical fields because of their high thermal, chemical, and mechanical strength. A *BEA-type zeolite is an interesting membrane material because of its large pore size and wide Si/Al range. This manuscript presents a protocol for *BEA membrane preparation by a secondary growth method that does not use an organic structure-directing agent (OSDA). The preparation protocol consists of four steps: pretreatment of support, seed preparation, dip-coating, and membrane crystallization. First, the *BEA seed crystal is prepared by conventional hydrothermal synthesis using OSDA. The synthesized seed crystal is loaded on the outer surface of a 3 cm long tubular α-Al2O3 support by a dip-coating method. The loaded seed layer is prepared with the secondary growth method using a hydrothermal treatment at 393 K for 7 days without using OSDA. A *BEA membrane having very few defects is successfully obtained. The seed preparation and dip-coating steps strongly affect the membrane quality.

Olefin Selective Ag-Exchanged X-Type Zeolite Membrane for Propylene/Propane and Ethylene/Ethane Separation.

Propylene/propane and ethylene/ethane separation was examined with Ag-exchanged X-type zeolite membrane (Ag-X membrane). The Na-X membrane was prepared on a porous tubular α-alumina support by a secondary growth method. The resulting Na-X membrane was ion-exchanged by using AgNO3 aq. Olefin selectivities in both mixtures were markedly improved after the ion exchange from Na to Ag cation. The Ag-X membrane exhibited a maximum propylene selectivity of 55.4 with a permeance of 4.13 × 10-8 mol m-2 s-1 Pa-1 at 353 K for a propylene/propane (50:50) mixture. This membrane also exhibited a maximum ethylene selectivity of 15.9 with a permeance of 9.04 × 10-8 mol m-2 s-1 Pa-1 at 303 K for an ethylene/ethane (50:50) mixture. We consider that the strong interaction between olefin and Ag cation plays an important role for the appearance of such high selectivity of olefin.