Separation of Hydrocarbons with a Microporous Metal–Organic Framework

Pan, Long; Olson, David H.; Ciemnolonski, Lauren R.; Heddy, Ryan; Li, Jing

doi:10.1002/anie.200503503

Cited by 743 publications

(253 citation statements)

References 37 publications

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“…Contrasting to zeolites, which have pores confined by tetrahedral oxide skeletons, the pores within MOFs can be systematically varied by the judicious choice of the metal-containing and/or organic ligands [19]. Due to their unusual features, MOFs are considered promising materials for gas storage, adsorption separations and catalysis [20][21][22][23][24][25][26][27][28][29][30][31][32].…”

Section: Introductionmentioning

confidence: 99%

Modeling adsorption equilibria of xylene isomers in a microporous metal–organic framework

Bárcia

Nicolau

Gallegos

et al. 2012

Microporous and Mesoporous Materials

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a b s t r a c tSingle and multicomponent adsorption equilibria of xylene isomers: o-xylene (o-x), m-xylene (m-x), pxylene (p-x) and ethylbenzene (eb) was investigated on the three dimensional microporous metal-organic framework Zn(BDC)(Dabco) 0.5 (BDC = 1,4-benzenedicarboxylate, Dabco = 1,4-diazabicyclo[2.2.2]-octane), MOF 1, in the range of temperatures between 398 and 448 K and partial pressures up to 0.1 bar. The equilibrium data show that a significant amount (around 34 g/100g ads at 398 K) of xylene isomers can be adsorbed in MOF 1. The affinity to the adsorbent measured by the Henry's constants to decreases in the order o-x > m-x > eb > p-x for all temperatures. The zero coverage adsorption enthalpies are all similar and range from 77.4 (eb) to 79.8 kJ/mol (o-x). The Dual-Site Langmuir model (DSL) was used for the interpretation and correlation of the experimental data. The parameters obtained from the pure component isotherms fitting were also used to predict the multicomponent equilibrium data by an extended DSL model. A good agreement was obtained between the predictions and the experimental data. It was also demonstrated that the DSL model is also capable to explain the increase in the isosteric heat of sorption with increasing coverage.

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Section: Introductionmentioning

confidence: 99%

Modeling adsorption equilibria of xylene isomers in a microporous metal–organic framework

Bárcia

Nicolau

Gallegos

et al. 2012

Microporous and Mesoporous Materials

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“…[8][9] A porous MOF, copper trimesate ([Cu3(BTC)2(H2O)3]n, denoted as CuBTC hereinafter) known as HKUST-1 10 is one of the first robust metal-organic framework (MOF) materials with a microporous structure that is reminiscent of zeolite frameworks. 11 This material forms face centered-cubic crystals that contain an intersecting three dimensional system of large square-shaped pores (9 × 9 Å). Interestingly, CuBTC obtained from solvothermal synthesis was recently tested for the adsorptive separation of a propanepropylene mixture.…”

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confidence: 99%

Adsorptive Separation of Propylene and Propane on a Porous Metal-Organic Framework, Copper Trimesate

Yoon¹,

Jang²,

Lee³

et al. 2010

Bulletin of the Korean Chemical Society

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The separation of propane and propylene has been commercially performed by an energy-intensive distillation process at about 243 K and 0.3 MPa in a column containing over 100 trays to achieve polymer-grade propylene due to the physicochemical similarities.1 Among several efforts to replace the conventional distillation process, adsorptive separation appears to be one of the promising short-term solutions as an alternative for providing the polymer-grade propylene.2 However, it is still a longcherished desire to develop effective adsorbents with high sorption capacities, high separation ratio and easy regenerability for this process in spite of a plenty of reports on porous adsorbents such as cationic zeolites, Ag-doped silica, etc.3-4 Metal-organic frameworks (MOFs) are currently of great interest and importance 5-7 because they possess extremely high surface area and pore volume, well-ordered porous structures, large amount of metal elements in crystalline frameworks and chemical functionalities. These properties enable to apply for gas purification and separation of gas mixtures. [8][9] A porous MOF, copper trimesate ([Cu3(BTC)2(H2O)3]n, denoted as CuBTC hereinafter) known as HKUST-1 10 is one of the first robust metal-organic framework (MOF) materials with a microporous structure that is reminiscent of zeolite frameworks.11 This material forms face centered-cubic crystals that contain an intersecting three dimensional system of large square-shaped pores (9 × 9 Å). Interestingly, CuBTC obtained from solvothermal synthesis was recently tested for the adsorptive separation of a propanepropylene mixture.12-13 However, the sorption results have shown only a limited separation efficiency in which a separation factor for propylene over propane is 2.0 at 313 K and 5 kPa. Recently, we have reported microwave synthesis of CuBTC as an efficient way to get high crystallinity and high BET surface area.14 The high porosity of the resulting CuBTC encourages us to confirm the possibility to enhance the sorption capacities of C3 hydrocarbons as well as the sorption affinity to propylene. This work aims to explore the adsorptive separation for propylene over propane with CuBTC, obtained by microwave synthesis, through single component adsorption isotherms as well as breakthrough experiments of propane-propylene mixtures. Results and DiscussionSingle component equilibrium adsorption isotherms of propane and propylene on CuBTC(M1) at a temperature range in the range of 303 K and 353 K are compared in Figure 1. For propane adsorption, Langmuir-type isotherms known as type I according to the IUPAC classification are observed at lower adsorption temperatures, but the isotherm shape changes to type V with increasing the sorption temperature ( Figure 1a). Type V isotherms are generally characteristic of weak adsorbentadsorbate interactions, causing small uptakes at low relative pressures. In contrast, for propylene adsorption the adsorbed amount sharply increases with pressure, indicating type I isotherms at all temperatures (Figure ...

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“…Although it is not a trivial task to properly interface these channels to achieve fluid flow through them unless they are designed as membranes with open space on either side of each pore, these porous layers may also be useful for the studies described in this paper, and can actually be designed such that the processes that occur in the pores can be monitored with integrated analysis tools in situ (see below). The latter also holds for any method that can produce layers of an ordered porous material, like zeolites, mesoporous silica [79], or nanoporous metal-organic frameworks (MOFs) [80], in which also very interesting confinement effects have also been observed [81,82].…”

Section: Nanochannel Fabricationmentioning

confidence: 97%

Chemistry in nanochannel confinement

Gardeniers

2009

Anal Bioanal Chem

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This review addresses the questions of whether it makes sense to use lithographically defined nanochannels for chemistry in liquids, and what it is possible to learn from experiments on that topic. The behavior of liquids in different classes of pores (categorized according to their size) is reviewed, with a focus on chemical reactions and protein dynamics. A number of interesting phenomena are discussed for nanochannels with feature sizes that are manufacturable with modern photolithography-based fabrication technology. The use of spectroscopic methods to investigate chemistry in nanochannels, where both spectroscopic method and nanochannels are integrated into a single device, will be evaluated.

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Separation of Hydrocarbons with a Microporous Metal–Organic Framework

Cited by 743 publications

References 37 publications

Modeling adsorption equilibria of xylene isomers in a microporous metal–organic framework

Modeling adsorption equilibria of xylene isomers in a microporous metal–organic framework

Adsorptive Separation of Propylene and Propane on a Porous Metal-Organic Framework, Copper Trimesate

Chemistry in nanochannel confinement

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