Synergistic sorbent separation for one-step ethylene purification from a four-component mixture

Chen, Kai‐Jie; Madden, David G.; Mukherjee, Soumya; Pham, Tony; Forrest, Katherine A.; Kumar, Amrit; Space, Brian; Kong, Jie; Zhang, Qiuyu; Zaworotko, Michael J.

doi:10.1126/science.aax8666

Cited by 396 publications

(300 citation statements)

References 41 publications

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“…Retention of structure and porosity despite continued exposure to humidity make the TCuX family a candidate for study under real‐world environments, in which humidity is likely to be present. The C 2 pure‐gas isotherms and the corresponding Q st profiles (Figures S15–S23 in the Supporting Information) indicate unsuitability of the TCuX family for C 2 H 2 /C 2 H n ( n =4 and/or 6) separations, however, it could be utilized as a C 2 H 2 selective bed by a synergistic sorbent approach …”

Section: Methodsmentioning

confidence: 99%

Halogen–C₂H₂ Binding in Ultramicroporous Metal–Organic Frameworks (MOFs) for Benchmark C₂H₂/CO₂ Separation Selectivity

Mukherjee

Franz

et al. 2020

Chemistry A European J

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Acetylene (C 2 H 2 )c apturei sastep in an umber of industrial processes, but it comes with ah igh-energy footprint. Although physisorbents have the potential to reduce this energy footprint, they are handicappedb y generally poor selectivity versusother relevant gases, such as CO 2 and C 2 H 4 .I nt he case of CO 2 ,t he respective physicochemical properties are so similar that traditional physisorbents, such as zeolites, silica, anda ctivated carbons cannot differentiate well between CO 2 and C 2 H 2 .H erein, we report that af amily of three isostructural, ultramicroporous (< 7 )d iamondoidm etal-organic frameworks, [Cu(TMBP)X] (TMBP = 3,3',5,5'-tetramethyl-4,4'-bipyrazole), TCuX (X = Cl, Br,I ), offer new benchmark C 2 H 2 /CO 2 separation selectivity at ambient temperature and pressure.W e attribute this performance to an ew type of strong binding site for C 2 H 2 .S pecifically,h alogen···HC interactions coupledw ith othern oncovalent in at ight binding site is C 2 H 2 specific versus CO 2 .T he binding site is distinct from those found in previous benchmark sorbents, which are based on open metal sites or electrostatic interactionse nabled by inorganic fluoro or oxo anions.That C 2 H 2 poses an immediate fire and explosive hazard at > 2.5 %c oncentrations and features the widest knownf lammability range, [1] 2.5-81 %, underscores the need to develop energy-efficient C 2 H 2 -capture sorbent materials. [2] Further,i ts high reactivity can lead to undesirable chemicalr eactions duringi ndustrial processes, for example, traces of C 2 H 2 can poisonc atalystsb yf orming metal acetylides duringe thylene polymerization, leading to explosions. [3] Removal of C 2 H 2 as a trace contaminant is also important in the productiono fa crylic/vinyl derivatives and acetylenic alcohols. [4] With respect to bulk usage,C 2 H 2 is the most common gas used to fuel cutting torches. C 2 H 2 recovered in high purity can serve as af uel or buildingblock in polymer synthesis for example, polyvinyl chloride, PVC and polyvinylidene fluoride,PVDF. [4] In C 2 H 2 manufacturedb yp artial combustion (oxidative coupling)o fmethane [5] or thermal cracking of hydrocarbons, CO 2 is generated as ab y-product. [6] To enable C 2 H 2 capturef rom C 2 H 2 /CO 2 mixtures, three current methods were employed: 1) bulk extraction by organic solvents, for example, N,N-dimethylformamide, and acetone; [7] b) partial hydrogenation of C 2 H 2 to ethylene, C 2 H 4 using expensive Ag 0 /other noble-metalc atalysts; [8] and c) cryogenic distillation. [9] All three approaches are costly and energy intensive. Althoughp hysisorbentso ffer potentialf or reducing the energyf ootprint of C 2 H 2 capture, zeolites, silica, and activated carbonsc annot effectively separate C 2 H 2 from CO 2[10] because of their similarp hysicochemical properties (size:C 2 H 2 = 3.32 3.34 5.7 3 ;C O 2 = 3.18 3.33 5.36 3 ;k inetic diameter = 3.3 for both;b oilingp oint:C 2 H 2 = 189.3 K, CO 2 = 194.7 K). [11] In this context,a ne merging class of physisorbents, namely, metal-organic m...

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Section: Methodsmentioning

confidence: 99%

Halogen–C₂H₂ Binding in Ultramicroporous Metal–Organic Frameworks (MOFs) for Benchmark C₂H₂/CO₂ Separation Selectivity

Mukherjee

Franz

et al. 2020

Chemistry A European J

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“…And partial hydrogenation of acetylene into ethylene over catalyst 10 or solvent extraction of cracked olefins 11 are also involved with the purification of ethylene from acetylene. Adsorptive separation by porous materials is an alternative technology, especially, some metal-organic frameworks (MOFs) [12][13][14][15][16][17][18][19][20][21] with high volume, designable pore characteristics, and countless structural possibilities, can be employed into the gas separation processes, the adsorption selectivity and capacity are higher than the results of conventional adsorbents [22][23][24] such as zeolites and carbon-based, especially the adsorption and separation for C 2 H 6 /C 2 H 4 8,22,[25][26][27][28][29][30][31][32][33][34][35][36][37][38][39] .…”

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A robust Th-azole framework for highly efficient purification of C2H4 from a C2H4/C2H2/C2H6 mixture

et al. 2020

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Separation of C 2 H 4 from C 2 H 4 /C 2 H 2 /C 2 H 6 mixture with high working capacity is still a challenging task. Herein, we deliberately design a Th-metal-organic framework (MOF) for highly efficient separation of C 2 H 4 from a binary C 2 H 6 /C 2 H 4 and ternary C 2 H 4 /C 2 H 2 /C 2 H 6 mixture. The synthesized MOF Azole-Th-1 shows a UiO-66-type structure with fcu topology built on a Th 6 secondary building unit and a tetrazole-based linker. Such noticeable structure, is connected by a N,O-donor ligand with high chemical stability. At 100 kPa and 298 K Azole-Th-1 performs excellent separation of C 2 H 4 (purity > 99.9%) from not only a binary C 2 H 6 / C 2 H 4 (1:9, v/v) mixture but also a ternary mixture of C 2 H 6 /C 2 H 2 /C 2 H 4 (9:1:90, v/v/v), and the corresponding working capacity can reach up to 1.13 and 1.34 mmol g −1 , respectively. The separation mechanism, as unveiled by the density functional theory calculation, is due to a stronger van der Waals interaction between ethane and the MOF skeleton.

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“…[4] Methanolc ould be directly produced from methane by using H 2 O 2 as an oxidant; however,abatch reactor was typicallyu sed, and H 2 O 2 is more expensive than methanol, making its practical applicationi mprobable.E thylene could be produced by using O 2 in ac ontinuous reactor,b ut the reaction temperature was typicallyh ighert han 700 8C, andv ariouss ide products were formed together owing to its radical-derived chemistry, [5] causing higherc ost for separation. [6] Methanol was produced from ac ontinuous-flow reactor by using O 2 ,b ut the productivity was very low at 0.02 mmol g cat À1 h À1 . [4a,c] The nonoxidative conversion uses methane only but typicallyr equires very high temperature (> 1000 8C).…”

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Oxidative Methane Conversion to Ethane on Highly Oxidized Pd/CeO₂ Catalysts Below 400 °C

et al. 2020

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Methane upgrading into more valuable chemicals has received much attention. Herein, we report oxidative methane conversion to ethane using gaseous O2 at low temperatures (<400 °C) and atmospheric pressure in a continuous reactor. A highly oxidized Pd deposited on ceria could produce ethane with a productivity as high as 0.84 mmol gcat−1 h−1. The Pd−O−Pd sites, not Pd−O−Ce, were the active sites for the selective ethane production at low temperatures. Density functional theory calculations confirmed that the Pd−O−Pd site is energetically more advantageous for C−C coupling, whereas Pd−O−Ce promotes CH4 dehydrogenation. The ceria helped Pd maintain a highly oxidic state despite reductive CH4 flow. This work can provide new insight for methane upgrading into C2 species.

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Synergistic sorbent separation for one-step ethylene purification from a four-component mixture

Cited by 396 publications

References 41 publications

Halogen–C₂H₂ Binding in Ultramicroporous Metal–Organic Frameworks (MOFs) for Benchmark C₂H₂/CO₂ Separation Selectivity

Halogen–C₂H₂ Binding in Ultramicroporous Metal–Organic Frameworks (MOFs) for Benchmark C₂H₂/CO₂ Separation Selectivity

A robust Th-azole framework for highly efficient purification of C2H4 from a C2H4/C2H2/C2H6 mixture

Oxidative Methane Conversion to Ethane on Highly Oxidized Pd/CeO₂ Catalysts Below 400 °C

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Synergistic sorbent separation for one-step ethylene purification from a four-component mixture

Cited by 396 publications

References 41 publications

Halogen–C2H2 Binding in Ultramicroporous Metal–Organic Frameworks (MOFs) for Benchmark C2H2/CO2 Separation Selectivity

Halogen–C2H2 Binding in Ultramicroporous Metal–Organic Frameworks (MOFs) for Benchmark C2H2/CO2 Separation Selectivity

A robust Th-azole framework for highly efficient purification of C2H4 from a C2H4/C2H2/C2H6 mixture

Oxidative Methane Conversion to Ethane on Highly Oxidized Pd/CeO2 Catalysts Below 400 °C

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Product

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Halogen–C₂H₂ Binding in Ultramicroporous Metal–Organic Frameworks (MOFs) for Benchmark C₂H₂/CO₂ Separation Selectivity

Halogen–C₂H₂ Binding in Ultramicroporous Metal–Organic Frameworks (MOFs) for Benchmark C₂H₂/CO₂ Separation Selectivity

Oxidative Methane Conversion to Ethane on Highly Oxidized Pd/CeO₂ Catalysts Below 400 °C