Efficient kinetic separation of propene and propane using two microporous metal organic frameworks

Peng, Junjie; Wang, Hao; Olson, David H.; Li, Zhong; Li, Jing

doi:10.1039/c7cc03529b

Cited by 97 publications

(60 citation statements)

References 33 publications

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“…[2] Thes eparation of C 3 H 6 /C 3 H 8 mixtures is performed by distillation at high pressure (20 bar). Due to the close-lying boiling points of C 3 H 6 (226 K) and C 3 H 8 (231 K), [3] their relative volatility is very small (1.09-1.15) [4] and the distillation column should have av ery large number of theoretical trays (180 +) [5] and be operated at very high reflux ratios (12)(13)(14)(15)(16)(17)(18)(19)(20), [6] resulting in huge energy consumption. [1] Without phase change,the energy requirement of adsorptive separation is much lower than distillation.…”

Section: Asoneofthemostimportantchemicalsinchemicalindustrymentioning

confidence: 99%

Selective Aerobic Oxidation of a Metal–Organic Framework Boosts Thermodynamic and Kinetic Propylene/Propane Selectivity

et al. 2019

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Efficient adsorptive separation of propylene/propane (C 3 H 6 /C 3 H 8 )i sh ighly desired and challenging.K nown strategies focus on either the thermodynamic or the kinetic mechanism. Here,w er eport an interesting reactivity of am etal-organic framework that improves thermodynamic and kinetic adsorption selectivity simultaneously.W hen the metal-organic framework is heated under oxygen flow, half of the soft methylene bridges of the organic ligands are selectively oxidized to form the more polar and rigid carbonyl bridges. Mixture breakthrough experiments showed drastic increase of C 3 H 6 /C 3 H 8 selectivity from 1.5 to 15. Forc omparison, the C 3 H 6 /C 3 H 8 selectivities of the best-performing metal-organic frameworks Co-MOF-74 and KAUST-7 were experimentally determined to be 6.5 and 12, respectively.G as adsorption isotherms/kinetics,s ingle-crystal X-ray diffraction, and computational simulations revealed that the oxidation gives additional guest recognition sites,w hich improve thermodynamic selectivity,a nd reduces the framework flexibility,w hich generate kinetic selectivity.

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Section: Asoneofthemostimportantchemicalsinchemicalindustrymentioning

confidence: 99%

Selective Aerobic Oxidation of a Metal–Organic Framework Boosts Thermodynamic and Kinetic Propylene/Propane Selectivity

et al. 2019

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“…[5] Af ew other MOFs with appropriate pore aperture sizes were considered as promising candidates for the kinetic separation of the two hydrocarbon species.T hey showed equally great interest for achieving high permeation selectivity when incorporated in membranes. [8][9][10] In particular, the zeolitic imidazolate framework-8 (ZIF-8) was revealed as ap romising MOF for such ak inetic control of the separation. [11][12][13][14] Many approaches have recently been considered, such as linker exchange,metal substitution, and configuration optimization, to enhance the C 3 H 6 /C 3 H 8 diffusion selectivity achieved by ZIF-8 derivatives.…”

Section: Bin Zheng and Guillaume Maurin*mentioning

confidence: 99%

Mechanical Control of the Kinetic Propylene/Propane Separation by Zeolitic Imidazolate Framework‐8

Zheng

Maurin

2019

Angew Chem Int Ed

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One intriguing feature of many porous MOFs is their stimulus-induced flexibility,w hichm akes them unique compared to standarda dsorbents.H ere we propose an innovative concept to achieve an efficient kinetic separation of species with similar properties by the mechanical fine-tuning of the pore architecture of the flexible zeolitic imidazolate framework ZIF-8. This unprecedented approach was applied to one of the most challenging societally relevant separations: the separation of propylene and propane,w hich is of vital importance in the petrochemical industry.Itwas demonstrated that the application of an external pressure creates ag radual enhancement in the propylene/propane diffusion selectivity to more than one order of magnitude at 1GPa pressure.A detailed analysis of the molecular simulations was further able to unravel the origin of this unusual behavior at the atomistic level.

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“…On the other hand, in the case of propane/propylene separation, where the removal of a single olefin from its corresponding paraffin is needed, kinetically driven separation often proves to be more suitable and efficient . A number of adsorbents have been reported to undergo kinetic separation toward propane and propylene . Compared to conventional adsorbents, the MOF pore size can be tuned much more readily to achieve significantly improved performance for kinetic separation of the two C3 molecules, as demonstrated in several recent studies .…”

mentioning

confidence: 99%

Tailor‐Made Microporous Metal–Organic Frameworks for the Full Separation of Propane from Propylene Through Selective Size Exclusion

et al. 2018

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in the production of polypropylene, the world's second-most widely produced synthetic plastic. The global demand for polypropylene has been rising continuously and its annual growth rate is expected to be 4-5% before 2020, resulting in increasing need for polymer-grade (>99.5%) propylene. [3] Nevertheless, the production of highly pure propylene represents a challenging and complicated process, which involves the separation of propylene from a propane/propylene mixture. Propane/ propylene mixtures are typically obtained by steam cracking of naphtha or during fluid catalytic cracking of gas oils in refineries, with a propylene purity of 50-60% for the former and 80-87% for the latter. Conventional separation of propane and propylene relies on cryogenic distillation, which is carried out at about 243 K and 0.3 MPa in a column containing over 100 trays. [4] Undoubtedly, this heat-driven process is highly energy-intensive.To lower the energy and operational cost and to suppress the carbon emissions associated with the propylene purification process through cryogenic distillation, several alternative technologies have been proposed and among them adsorptive separation, such as pressure/temperature swing adsorption, Adsorptive separation of olefin/paraffin mixtures by porous solids can greatly reduce the energy consumption associated with the currently employed cryogenic distillation technique. Here, the complete separation of propane and propylene by a designer microporous metal-organic framework material is reported. The compound, Y 6 (OH) 8 (abtc) 3 (H 2 O) 6 (DMA) 2 (Y-abtc, abtc = 3,3′,5,5′-azobenzene-tetracarboxylates; DMA = dimethylammonium), is rationally designed through topology-guided replacement of inorganic building units. Y-abtc is both thermally and hydrothermally robust, and possesses optimal pore window size for propane/propylene separation. It adsorbs propylene with fast kinetics under ambient temperature and pressure, but fully excludes propane, as a result of selective size exclusion. Multicomponent column breakthrough experiments confirm that polymer-grade propylene (99.5%) can be obtained by this process, demonstrating its true potential as an alternative sorbent for efficient separation of propane/propylene mixtures.

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Efficient kinetic separation of propene and propane using two microporous metal organic frameworks

Cited by 97 publications

References 33 publications

Selective Aerobic Oxidation of a Metal–Organic Framework Boosts Thermodynamic and Kinetic Propylene/Propane Selectivity

Selective Aerobic Oxidation of a Metal–Organic Framework Boosts Thermodynamic and Kinetic Propylene/Propane Selectivity

Mechanical Control of the Kinetic Propylene/Propane Separation by Zeolitic Imidazolate Framework‐8

Tailor‐Made Microporous Metal–Organic Frameworks for the Full Separation of Propane from Propylene Through Selective Size Exclusion

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