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Thermodynamic Separation of 1-Butene from 2-Butene in Metal-Organic Frameworks with Open Metal Sites.
J Am Chem Soc 2019; 141(45):18325-18333JA

Abstract

Most C4 hydrocarbons are obtained as byproducts of ethylene production or oil refining, and complex and energy-intensive separation schemes are required for their isolation. Substantial industrial and academic effort has been expended to develop more cost-effective adsorbent- or membrane-based approaches to purify commodity chemicals such as 1,3-butadiene, isobutene, and 1-butene, but the very similar physical properties of these C4 hydrocarbons make this a challenging task. Here, we examine the adsorption behavior of 1-butene, cis-2-butene, and trans-2-butene in the metal-organic frameworks M2(dobdc) (M = Mn, Fe, Co, Ni; dobdc4- = 2,5-dioxidobenzene-1,4-dicarboxylate) and M2(m-dobdc) (m-dobdc4- = 4,6-dioxidobenzene-1,3-dicarboxylate), which all contain a high density of coordinatively unsaturated M2+ sites. We find that both Co2(m-dobdc) and Ni2(m-dobdc) are able to separate 1-butene from the 2-butene isomers, a critical industrial process that relies largely on energetically demanding cryogenic distillation. The origin of 1-butene selectivity is traced to the high charge density retained by the M2+ metal centers exposed within the M2(m-dobdc) structures, which results in a reversal of the cis-2-butene selectivity typically observed at framework open metal sites. Selectivity for 1-butene adsorption under multicomponent conditions is demonstrated for Ni2(m-dobdc) in both the gaseous and the liquid phases via breakthrough and batch adsorption experiments.

Authors+Show Affiliations

Materials Sciences Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States.Materials Sciences Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States.No affiliation info availableNo affiliation info availableMaterials Sciences Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States.No affiliation info availableMaterials Sciences Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31626542

Citation

Barnett, Brandon R., et al. "Thermodynamic Separation of 1-Butene From 2-Butene in Metal-Organic Frameworks With Open Metal Sites." Journal of the American Chemical Society, vol. 141, no. 45, 2019, pp. 18325-18333.
Barnett BR, Parker ST, Paley MV, et al. Thermodynamic Separation of 1-Butene from 2-Butene in Metal-Organic Frameworks with Open Metal Sites. J Am Chem Soc. 2019;141(45):18325-18333.
Barnett, B. R., Parker, S. T., Paley, M. V., Gonzalez, M. I., Biggins, N., Oktawiec, J., & Long, J. R. (2019). Thermodynamic Separation of 1-Butene from 2-Butene in Metal-Organic Frameworks with Open Metal Sites. Journal of the American Chemical Society, 141(45), pp. 18325-18333. doi:10.1021/jacs.9b09942.
Barnett BR, et al. Thermodynamic Separation of 1-Butene From 2-Butene in Metal-Organic Frameworks With Open Metal Sites. J Am Chem Soc. 2019 Nov 13;141(45):18325-18333. PubMed PMID: 31626542.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Thermodynamic Separation of 1-Butene from 2-Butene in Metal-Organic Frameworks with Open Metal Sites. AU - Barnett,Brandon R, AU - Parker,Surya T, AU - Paley,Maria V, AU - Gonzalez,Miguel I, AU - Biggins,Naomi, AU - Oktawiec,Julia, AU - Long,Jeffrey R, Y1 - 2019/10/31/ PY - 2019/10/19/pubmed PY - 2019/10/19/medline PY - 2019/10/19/entrez SP - 18325 EP - 18333 JF - Journal of the American Chemical Society JO - J. Am. Chem. Soc. VL - 141 IS - 45 N2 - Most C4 hydrocarbons are obtained as byproducts of ethylene production or oil refining, and complex and energy-intensive separation schemes are required for their isolation. Substantial industrial and academic effort has been expended to develop more cost-effective adsorbent- or membrane-based approaches to purify commodity chemicals such as 1,3-butadiene, isobutene, and 1-butene, but the very similar physical properties of these C4 hydrocarbons make this a challenging task. Here, we examine the adsorption behavior of 1-butene, cis-2-butene, and trans-2-butene in the metal-organic frameworks M2(dobdc) (M = Mn, Fe, Co, Ni; dobdc4- = 2,5-dioxidobenzene-1,4-dicarboxylate) and M2(m-dobdc) (m-dobdc4- = 4,6-dioxidobenzene-1,3-dicarboxylate), which all contain a high density of coordinatively unsaturated M2+ sites. We find that both Co2(m-dobdc) and Ni2(m-dobdc) are able to separate 1-butene from the 2-butene isomers, a critical industrial process that relies largely on energetically demanding cryogenic distillation. The origin of 1-butene selectivity is traced to the high charge density retained by the M2+ metal centers exposed within the M2(m-dobdc) structures, which results in a reversal of the cis-2-butene selectivity typically observed at framework open metal sites. Selectivity for 1-butene adsorption under multicomponent conditions is demonstrated for Ni2(m-dobdc) in both the gaseous and the liquid phases via breakthrough and batch adsorption experiments. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/31626542/Thermodynamic_Separation_of_1-Butene_from_2-Butene_in_Metal-Organic_Frameworks_with_Open_Metal_Sites L2 - https://dx.doi.org/10.1021/jacs.9b09942 DB - PRIME DP - Unbound Medicine ER -