The discovery of new materials for separating ethylene from ethane by adsorption, instead of using cryogenic distillation, is a key milestone for molecular separations because of the multiple and widely extended uses of these molecules in industry. This technique has the potential to provide tremendous energy savings when compared with the currently used cryogenic distillation process for ethylene produced through steam cracking. Here we describe the synthesis and structural determination of a flexible pure silica zeolite (ITQ-55). This material can kinetically separate ethylene from ethane with an unprecedented selectivity of ~100, owing to its distinctive pore topology with large heart-shaped cages and framework flexibility. Control of such properties extends the boundaries for applicability of zeolites to challenging separations.

Control of zeolite framework flexibility and pore topology for separation of ethane and ethylene.

The balance between the market demand and the natural abundance of the rare-earth elements (REEs) in ores, often referred to as the Balance Problem (or the Balancing Problem), is a major issue for REE suppliers. The ideal situation is a perfect match between the market demand for and the production of REEs, so that there are no surpluses of any of the REEs. This means that the rare-earth industry must find new uses for REEs that are available in excess and search for substitutes for REEs that have either limited availability or are high in demand. We present an overview of the trends in the applications for the different REEs and show that the demand for REEs for use in magnets, catalysts, and alloys is still increasing, while the application of REEs in polishing agents, glass, and ceramics are stable. On the other hand, the use of REEs in nickel–metal-hydride (NiMH) batteries and lamp phosphors is decreasing. These changes in the REE market have an influence on the Balance Problem, because the REEs that can be recycled from fluorescent lamps, cathode-ray tubes (CRTs), and NiMH batteries have to be at least partly reused in other applications. Magnesium and aluminum alloys offer an opportunity to mitigate the Balance Problem caused by these changes in the REE market. This is illustrated for REEs that can be recycled from fluorescent-lamp phosphor waste, CRT phosphors, and NiMH batteries. At present, five REEs (Nd, Eu, Tb, Dy, and Y) are being considered as very critical by Europe, the United States, and Japan, but we forecast that in the medium term, only neodymium will remain a critical REE. This paper discusses the relationship between criticality and the Balance Problem and shows how this relationship influences the market for specific REEs.

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Rare Earths and the Balance Problem: How to Deal with Changing Markets?

Metal-organic frameworks (MOFs) with open metal sites (OMSs) have been shown to preferentially adsorb unsaturated hydrocarbons such as C2H4 due to the formation of π-complexation. However, the adsorption capacity and selectivity might well be dampened under humid conditions because OMSs could be easily poisoned in the presence of water vapor. C2H6-selective adsorbents with less hydrophilic environments, on the other hand, not only could effectively minimize the impact of humidity on separation capacity but also could directly produce high-purity C2H4 from C2H6/C2H4 mixtures. Here, we report a C2H6-selective MOF (JNU-2) underlying a rare xae topology. Its cage-like cavities are interconnected through apertures with a limiting diameter of ca. 3.7 A, which is in the domain of kinetic diameters of C2H4 and C2H6 molecules. Molecular modeling studies suggest the four oxygen atoms on aperture are poised to preferentially interact with C2H6 through multiple C-H···O hydrogen bonding, rendering JNU-2 an enhanced C2H6 selectivity. Indeed, experimental results reveal that JNU-2 not only takes up a great amount of C2H6 comparable to other top-performing C2H6-selective MOFs but also displays excellent separation capacity even under humid conditions; moreover, it can be easily regenerated at room temperature owing to its moderate adsorption enthalpy. This work successfully demonstrated a strategy of balancing adsorption capacity and selectivity for C2H6 by designing MOF materials with cavities interconnected through tailored apertures. The apertures function as screening sites for C2H6 selectivity, while the internal cavities provide space for large adsorption.

Cage-Interconnected Metal–Organic Framework with Tailored Apertures for Efficient C2H6/C2H4 Separation under Humid Conditions

Propene is a key building block for the petrochemical industry whose demand is increasing strongly in recent years, even faster than that of ethene. The availability of propene is limited, and therefore, efforts to optimize its production are being pursued. On the occasion of the 75th anniversary of the first FCC unit, we analyze some recent advances that have been achieved in the understanding and development of zeolites aiming to increase the production of light olefins as petrochemical building blocks by means of catalytic cracking. We discuss a selected group of emerging strategies in zeolite engineering that have great prospects for research and that we consider could impact the sector in the near future. These include advances in crystal engineering and hierarchization achieved through bottom-up and top-down approaches, composite materials, tuning of the location of active sites among the different crystallographic positions available, and, importantly, how to characterize these modifications and th...

Engineering Zeolites for Catalytic Cracking to Light Olefins

The separation of ethane (C2H6) from ethylene (C2H4) is of prime importance in the production of polymer-grade C2H4 for industrial manufacturing. It is very challenging and still remains unexploited to fully realize efficient C2H6/C2H4 separation in the emerging hydrogen-bonded organic frameworks (HOFs) due to the weak nature of hydrogen bonds. We herein report the benchmark example of a novel ultrarobust HOF adsorbent (termed as HOF-76a) with a Brunauer-Emmett-Teller surface area exceeding 1100 m2 g-1, exhibiting the preferential binding of C2H6 over C2H4 and thus highly selective separation of C2H6/C2H4. Theoretical calculations indicate the key role of the nonpolar surface and the suitable triangular channel-like pores in HOF-76a to sterically "match" better with the nonplanar C2H6 molecule than the planar C2H4, thus affording overall stronger multipoint van der Waals interactions with C2H6. The exceptional separation performance of HOF-76a for C2H6/C2H4 separation was clearly demonstrated by gas adsorption isotherms, ideal adsorbed solution theory calculations, and simulated and experimental breakthrough curves. Breakthrough experiments on HOF-76a reveal that polymer-grade ethylene gas can be straightforwardly produced from 50/50 (v/v) C2H6/C2H4 mixtures during the first adsorption cycle with a high productivity of 7.2 L/kg at 298 K and 1.01 bar and 18.8 L/kg at 298 K and 5.0 bar, respectively.

Selective Ethane/Ethylene Separation in a Robust Microporous Hydrogen-Bonded Organic Framework.

http://digital.csic.es/bitstream/10261/162147/4/Crudeoil.pdf

E. Corresa

Papers

Crude oil to chemicals: light olefins from crude oil