Percorrer por autor "Maurin, Guillaume"
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- Adsorption and dynamics of linear and mono-branched hexane isomers in MIL-140 metal-organic frameworksPublication . Zhao, Hengli; Silva, José A.C.; Henrique, Adriano; Nouar, Farid; Serre, Christian; Maurin, Guillaume; Ghoufi, AzizRecent breakthrough experiments revealed the iso-reticular Zr-MOFs, MIL-140B and MIL-140C, as promising sorbents for the separation of C6 isomers. Interestingly while the ultra-small pore MIL-140B exhibited hexane isomer sorption hierarchy according to the normal boiling point order (n-C6 > 3MP (3-methyl pentane)), an uncommon shift in the elution order was observed in the larger pore MIL-140C. It was only speculated that the flexibility of the MOFs might be the origin of this intriguing behavior. Herein, flexible force field hybrid osmotic Monte Carlo combined with molecular dynamics simulations were carried out to unravel the microscopic mechanism of the adsorption and dynamics of both C6 isomers in MIL140B and MIL140C. Thermodynamically preferred adsorption of n-C6 over 3MP was predicted for MIL-140B and to a slightly less extent for MIL-140C. Interestingly while the mobility of n-C6 was found to remain higher than that of 3MP in the whole range of loading for MIL-140B, 3MP becomes more mobile than n-C6 at saturation in MIL-140C. This suggests that this kinetics order is most probably the origin of the inversion of the elution order observed experimentally for MIL-140C. The translational and rotational dynamics of the two guests in MIL-140B and MIL-140C was further understood in-depth.
- A complete separation of hexane isomers by a functionalized flexible metal organic frameworkPublication . Mendes, Patrícia A.P.; Horcajada, Patricia; Rives, Sébastien; Ren, Hong; Rodrigues, Alírio; Devic, Thomas; Magnier, Emmanuel; Trens, Philippe; Jobic, Hervé; Ollivier, Jacques; Maurin, Guillaume; Serre, Christian; Silva, José A.C.The separation ability of branched alkane isomers (nHEX, 3MP, 22DMB) of the flexible and functionalized microporous iron(III) dicarboxylate MIL-53(Fe)-(CF3)2 solid is evaluated through a combination of breakthrough experiments (binary or ternary mixtures), adsorption isotherms, X-ray diffraction temperature analysis, quasi-elastic neutron scattering measurements and molecular dynamics simulations. A kinetically controlled molecular sieve separation between the di-branched isomer of hexane 22DMB from a mixture of paraffins is achieved. The reported total separation between mono- and di-branched alkanes which was neither predicted nor observed so far in any class of porous solids is spectacular and paves the way towards a potential unprecedented upgrading of the RON of gasoline.
- Hexane isomers separation on an isoreticular series of microporous Zr carboxylate metal organic frameworksPublication . Henrique, Adriano; Maity, Tanmoy; Zhao, Hengli; Brântuas, Pedro; Rodrigues, Alírio; Nouar, Farid; Ghoufi, Aziz; Maurin, Guillaume; Silva, José A.C.; Serre, ChristianA series of isoreticular Zr carboxylate MOFs, MIL-140A, B and C, exhibiting 1D microporous triangular shaped channels and based on different aromatic dicarboxylate ligands (1,4-BDC, 2,6-NDC and 4,4′-BPDC, respectively), were investigated by chromatographic breakthrough experiments regarding their ability to separate hexane isomers (nC6/2MP/3MP/23DMB/22DMB). Both single and equimolar multicomponent experiments were performed at the temperatures 343, 373, and 423 K and a total hydrocarbon pressure up to 50.0 kPa using the MIL-140B form. The elution order is similar to that of the normal boiling point of the compounds nC6 > 2MP > 3MP > 23DMB > 22DMB. It is noteworthy that this material enables separation of the hexane isomers by class, linear > mono-branched > di-branched, with a selectivity (linear + mono-branched isomers/di-branched isomers) up to 10 at 343 K, decreasing, however, as the temperature increases. Grand canonical Monte Carlo simulations were further performed to gain insight into the adsorption/separation mechanisms, highlighting the crucial need to consider a tiny tilting of the organic linkers for capturing the experimental observations. The impact of the pore size was finally assessed through the comparison with MIL-140A and MIL-140C, respectively, based on multicomponent experiments at 343 K. We evidenced a significant decrease of the selectivity (about 2) in both cases while the loadings were decreased or increased for MIL-140A and MIL-140C, respectively. Additionally, MIL-140C was demonstrated to exhibit an uncommon shift in the elution order occurring between nC6 and 3MP, 3MP being the last compound to saturate in the column.
- A microporous multi‐cage metal–organic framework for an effective one‐step separation of branched alkanes feedsPublication . Zhou, Lin; Brântuas, Pedro; Henrique, Adriano; Reinsch, Helge; Wahiduzzaman, Mohammad; Grenèche, Jean‐Marc; Rodrigues, Alírio; Silva, José A.C.; Maurin, Guillaume; Serre, ChristianThe improvement of the Total Isomerization Process (TIP) for the production of high-quality gasoline with the ultimate goal of reaching a Research Octane Number (RON) higher than 92 requires the use of specific sorbents to separate pentane and hexane isomers into classes of linear, mono- and di-branched isomers. Herein we report the design of a new multi-cage microporous Fe(III)-MOF (referred to as MIP-214, MIP stands for materials of the Institute of Porous Materials of Paris) with a flu-e topology, incorporating an asymmetric heterofunctional ditopic ligand, 4-pyrazolecarboxylic acid, that exhibits an appropriate microporous structure for a thermodynamic-controlled separation of hydrocarbon isomers. This MOF produced via a direct, scalable, and mild synthesis route was proven to encompass a unique separation of C5/C6 isomers by classes of low RON over high RON alkanes with a sorption hierarchy: (n-hexane >> n-pentane approximate to 2-methylpentane>3-methylpentane)(low RON)>>(2,3-dimethylbutane approximate to i-pentane approximate to 2,2-dimethylbutane)(high RON) following the adsorption enthalpy sequence. We reveal for the first time that a single sorbent can efficiently separate such a complex mixture of high RON di-branched hexane and mono-branched pentane isomers from their low RON counterparts, which is a major achievement reported so far.
- Separation of Branched Alkane Feeds with Metal-Organic FrameworksPublication . Henrique, Adriano; Brântuas, Pedro; Zafanelli, Lucas F.A.S.; Aly, Ezzeldin; Rodrigues, Alírio; Maurin, Guillaume; Serre, Christian; Silva, José A.C.The production of high-quality gasoline is currently achieved through the Total Isomerization Process that separates n/iso-paraffins in the pentane (C5) and hexane (C6) range while not reaching the ultimate goal of a research octane number (RON) higher than 92. This work demonstrates two promising alternatives/strategies using metal-organic frameworks (MOF) that lead to a novel adsorptive separation process to overcome this limitation. Here, the efficient discrimination of C5/C6 alkane isomers into valuable fractions of high RON (HRON – 2,3-dimethylbutane (23DMB; RON 105), 2,2-dimethylbutane (22DMB; RON 94), and isopentane (iC5; RON 93.5)) and low RON (LRON – n-pentane (nC5; RON 61.7), (nC6; RON 30), 2-methylpentane (2MP; RON 74.5), and 3-methylpentane (3MP; RON 75.5)) compounds is achieved.
- Separation of Branched Alkane Feeds with Metal-Organic FrameworksPublication . Henrique, Adriano; Brântuas, Pedro; Zafanelli, Lucas F.A.S.; Aly, Ezzeldin; Rodrigues, Alírio; Maurin, Guillaume; Serre, Christian; Silva, José A.C.The production of high-quality gasoline is currently achieved through the Total Isomerization Process that separates n/iso-paraffins in the pentane (C5) and hexane (C6) range while not reaching the ultimate goal of a research octane number (RON) higher than 92. This work demonstrates two promising alternatives/strategies using metal-organic frameworks (MOF) that lead to a novel adsorptive separation process to overcome this limitation. Here, the efficient discrimination of C5/C6 alkane isomers into valuable fractions of high RON (HRON – 2,3-dimethylbutane (23DMB; RON 105), 2,2-dimethylbutane (22DMB; RON 94), and isopentane (iC5; RON 93.5)) and low RON (LRON – n-pentane (nC5; RON 61.7), (nC6; RON 30), 2-methylpentane (2MP; RON 74.5), and 3-methylpentane (3MP; RON 75.5)) compounds is achieved.
- Separation of Branched Alkanes Feeds by a Synergistic Action of Zeolite 5A and Metal-Organic Framework MIL-160(Al)Publication . Henrique, Adriano; Brântuas, Pedro; Zafanelli, Lucas F.A.S.; Aly, Ezzeldin; Rodrigues, Alírio; Maurin, Guillaume; Serre, Christian; Silva, José A.C.The total isomerisation process (TIP) developed by the universal oil products (UOP) for upgrading the octane rating of light hydrocarbon fractions, especially mixed feedstocks containing pentane (C5) and hexane (C6) isomers, is among the first and most successful adsorption processes applied in the industry. Typically, the light naphtha, characterised by a low research octane number (RON, ≈70), undergoes an incomplete catalytic isomerisation that generates an effluent containing unconverted linear paraffins, mostly n-pentane (nC5; RON 61.7) and n-hexane (nC6; RON 30), mixed with their respective branched isomers, i.e., isopentane (iC5; RON 93.5), 2-methylpentane (2MP; RON 74.5), 3-methylpentane (3MP; RON 75.5), 2,2-dimethylbutane (22DMB; RON 94), and 2,3-dimethylbutane (23DMB; RON 105). After that, the output of the isomerisation reactor is fed into an adsorber packed with zeolite (LTA type) that behaves as a molecular sieve, adsorbing only the linear paraffins (which are then recycled to the catalytic reactor for further processing). This results in a final branched isomerate product with an average RON ≈87–90. However, with the actual TIP process, the monobranched hexanes 2MP and 3MP represent up to 30% of the final product composition, which is detrimental to the octane improvement of gasoline for RON values higher than 90. Accordingly, this work shows a novel adsorptive separation process, based on the synergistic action of the zeolite 5A and the MIL-160(Al) metal-organic framework (MOF), to efficiently fractionate C5/C6 alkane isomers according to classes of high RON (HRON – 22DMB, 23DMB, and iC5) and low RON (LRON – nC5, nC6, 2MP, and 3MP) compounds.
- Separation of branched alkanes feeds by a synergistic action of zeolite 5A and metal-organic framework MIL-160(Al)Publication . Henrique, Adriano; Brântuas, Pedro; Zafanelli, Lucas F.A.S.; Aly, Ezzeldin; Rodrigues, Alírio; Maurin, Guillaume; Serre, Christian; Silva, José A.C.The total isomerisation process (TIP) developed by the universal oil products (UOP) for upgrading the octane rating of light hydrocarbon fractions, especially mixed feedstocks containing pentane (C5) and hexane (C6) isomers, is among the first and most successful adsorption processes applied in the industry. Typically, the light naphtha, characterised by a low research octane number (RON, ≈70), undergoes an incomplete catalytic isomerisation that generates an effluent containing unconverted linear paraffins, mostly n-pentane (nC5; RON 61.7) and n-hexane (nC6; RON 30), mixed with their respective branched isomers, i.e., isopentane (iC5; RON 93.5), 2-methylpentane (2MP; RON 74.5), 3-methylpentane (3MP; RON 75.5), 2,2-dimethylbutane (22DMB; RON 94), and 2,3-dimethylbutane (23DMB; RON 105). After that, the output of the isomerisation reactor is fed into an adsorber packed with zeolite (LTA type) that behaves as a molecular sieve, adsorbing only the linear paraffins (which are then recycled to the catalytic reactor for further processing). This results in a final branched isomerate product with an average RON ≈87–90. However, with the actual TIP process, the monobranched hexanes 2MP and 3MP represent up to 30% of the final product composition, which is detrimental to the octane improvement of gasoline for RON values higher than 90. Accordingly, this work shows a novel adsorptive separation process, based on the synergistic action of the zeolite 5A and the MIL-160(Al) metal-organic framework (MOF), to efficiently fractionate C5/C6 alkane isomers according to classes of high RON (HRON – 22DMB, 23DMB, and iC5) and low RON (LRON – nC5, nC6, 2MP, and 3MP) compounds.
- Separation of branched alkanes feeds by a synergistic action of zeolite and metal-organic frameworkPublication . Brântuas, Pedro; Henrique, Adriano; Wahiduzzaman, Mohammad; Wedelstedt, Alexander von; Maity, Tanmoy; Rodrigues, Alírio; Nouar, Farid; Lee, U-Hwang; Cho, Kyung Ho; Silva, José A.C.; Serre, Christian; Maurin, GuillaumeZeolites and metal-organic frameworks (MOFs) are considered as “competitors” for new separation processes. The production of high-quality gasoline is currently achieved through the total isomerization process that separates pentane and hexane isomers while not reaching the ultimate goal of a research octane number (RON) higher than 92. This work demonstrates how a synergistic action of the zeolite 5A and the MIL-160(Al) MOF leads to a novel adsorptive process for octane upgrading of gasoline through an efficient separation of isomers. This innovative mixed-bed adsorbent strategy encompasses a thermodynamically driven separation of hexane isomers according to the degree of branching by MIL-160(Al) coupled to a steric rejection of linear isomers by the molecular sieve zeolite 5A. Their adsorptive separation ability is further evaluated under real conditions by sorption breakthrough and continuous cyclic experiments with a mixed bed of shaped adsorbents. Remarkably, at the industrially relevant temperature of 423 K, an ideal sorption hierarchy of low RON over high RON alkanes is achieved, i.e., n-hexane ≫n-pentane ≫2-methylpentane > 3-methylpentane⋙ 2,3-dimethylbutane > isopentane ≈ 2,2-dimethylbutane, together with a productivity of 1.14 mol dm−3 and a high RON of 92, which is a leap-forward compared with existing processes.