Olefin-paraffin separation is a critical yet energy-intensive process in the chemical industry, accounting for over 250 trillion BTU/year of global energy consumption. This work explores the use of redox-active nickel maleonitriledithiolate complex for olefin-paraffin separations. Key performance factors, namely the electrochemical oxidation of the complex and the olefin capture utilization fraction, were systematically quantified. Electrochemical studies revealed near-complete oxidation of Ni(II) to Ni(IV) species, suggesting that the electrochemical oxidation step is not a limiting factor in olefin capture. The utilization fraction was found to be strongly dependent on the complexation equilibrium behavior between olefin-bound and unbound state of the complex. Time-resolved kinetic measurements unveiled a sluggish complexation rate, requiring over 36 hours to approach equilibrium. These insights highlight the importance of driving the complexation equilibrium and improving the kinetics to enhance the performance of Ni-based electrochemical swing absorbers for energy-efficient olefin-paraffin separations. The findings lay the groundwork for future optimization strategies and industrial implementation of this sustainable separation technology.
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http://dx.doi.org/10.1039/d4re00145a | DOI Listing |
React Chem Eng
August 2024
Department of Chemical and Biomolecular Engineering, New York University, Brooklyn, NY, 11201, USA.
Olefin-paraffin separation is a critical yet energy-intensive process in the chemical industry, accounting for over 250 trillion BTU/year of global energy consumption. This work explores the use of redox-active nickel maleonitriledithiolate complex for olefin-paraffin separations. Key performance factors, namely the electrochemical oxidation of the complex and the olefin capture utilization fraction, were systematically quantified.
View Article and Find Full Text PDFAnal Chem
November 2024
Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States.
Silver(I) ions (Ag) undergo selective π-complexation with olefins and have been employed as separation media for the isolation of olefins from structurally similar paraffins. Ionic liquids (ILs) possess minimal vapor pressures, exceptional thermal stabilities, low melting points, as well as provide a favorable environment for π-complexation between Ag ions and olefins. The development of molecular drivers capable of highly selective olefin/paraffin separation systems with Ag-containing ILs necessitates a comprehensive understanding of all factors that affect olefin solubility and selectivity.
View Article and Find Full Text PDFChemistry
June 2024
State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement of Science and Technology, Chinese Academy of Sciences, Wuhan, 430071, China.
Direct determination of the equilibrium adsorption and spectroscopic observation of adsorbent-adsorbate interaction is crucial to evaluate the olefin/paraffin separation performance of porous adsorbents. However, the experimental characterization of competitive adsorption of various adsorbates at atomic-molecular level in the purification of multicomponent gas mixtures is challenging and rarely conducted. Herein, solid-state NMR spectroscopy is employed to examine the effect of co-adsorbed guest adsorbates on the separation of ethylene/ethane mixtures on Mg-MOF-74, Zn-MOF-74 and UTSA-74.
View Article and Find Full Text PDFACS Appl Mater Interfaces
February 2024
Chemical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India.
Cryogenic distillation, a currently employed method for CH/CH and CH/CH mixture separation, is energy-intensive, prompting the research toward alternative technologies, including adsorbent-based separation. In this work, we combine machine learning (ML) technique with high-throughput screening to screen ∼23,000 hypothetical metal-organic frameworks (MOFs) for paraffin (CH and CH) selective adsorbent separation. First, structure-based prescreening was employed to remove MOFs with undesired geometric properties.
View Article and Find Full Text PDFNat Commun
January 2024
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, Jiangxi, 330031, China.
Olefin/paraffin separations are among the most energy-intensive processes in the petrochemical industry, with ethylene being the most widely consumed chemical feedstock. Adsorptive separation utilizing molecular sieving adsorbents can optimize energy efficiency, whereas the size-exclusive mechanism alone cannot achieve multiple olefin/paraffin sieving in a single adsorbent. Herein, an unprecedented sieving adsorbent, BFFOUR-Cu-dpds (BFFOUR = BF, dpds = 4,4'-bipyridinedisulfide), is reported for simultaneous sieving of C-C olefins from their corresponding paraffins.
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