Lomig Hamon

High Uptakes of CO2 and CH4 in Mesoporous Metal—Organic Frameworks MIL-100 and MIL-101

Mesoporous MOFs MIL-100 and MIL-101 adsorb huge amounts of CO2 and CH4. Characterization was performed using both manometry and gravimetry in different laboratories for isotherms coupled with microcalorimetry and FTIR to specify the gas-solid interactions. In particular, the uptake of carbon dioxide in MIL-101 has been shown to occur with a record capacity of 40 mmol g(-1) or 390 cm3STP cm(-3) at 5 MPa and 303 K.

Co-adsorption and Separation of CO2-CH4 Mixtures in the Highly Flexible MIL-53(Cr) MOF

The present study attempts to understand the use of the flexible porous chromium terephthalate Cr(OH)(O(2)C-C(6)H(4)-CO(2)) denoted MIL-53(Cr) (MIL = Material from Institut Lavoisier) for the separation of mixtures of CO(2) and CH(4) at ambient temperature. The coadsorption of CO(2) and CH(4) was studied by a variety of different techniques. In situ synchrotron X-ray Powder Diffraction allowed study of the breathing of the solid upon adsorption of the gas mixtures and simultaneously measured Raman spectra yielded an estimation of the adsorbed quantities of CO(2) and CH(4), as well as a quantification of the fraction of the narrow pore (NP) and the large pore (LP) form of MIL-53. Quantitative coadsorption data were then measured by gravimetry and by breakthrough curves. In addition, computer simulation was performed to calculate the composition of the adsorbed phase in comparison with experimental equilibrium isotherms and breakthrough results. The body of results shows that the coadsorption of CO(2) and CH(4) leads to a similar breathing of MIL-53(Cr) as with pure CO(2). The breathing is mainly controlled by the partial pressure of CO(2), but increasing the CH(4) content progressively decreases the transformation of LP to NP. CH(4) seems to be excluded from the NP form, which is filled exclusively by CO(2) molecules. The consequences in terms of CO(2)/CH(4) selectivity and the possible use of MIL-53(Cr) in a PSA process are discussed.

Comparative Study of Hydrogen Sulfide Adsorption in the MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) Metal−Organic Frameworks at Room Temperature

Hydrogen sulfide gravimetric isotherm adsorption measurements were carried out on MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) metal-organic frameworks (MOFs). A two-step adsorption mechanism related to a breathing effect was observed for MIL-53 terephthalate-based MOFs. Methane adsorption measurements highlighted the regenerability of MIL-53(Al, Cr) and MIL-47(V) MOFs after H(2)S treatment, whereas MIL-100 and MIL-101 CH(4) adsorption capacities were significantly decreased.

A Method for Screening the Potential of MOFs as CO2 Adsorbents in Pressure Swing Adsorption Processes

This work reports the adsorption and coadsorption data of CO(2)/CH(4)/CO mixtures on several metal-organic frameworks [MOFs; MIL-100(Cr), MIL-47(V), MIL-140(Zr)-A, Cu-btc, and MIL-53(Cr)] and compares them with reference adsorbents, that is, zeolite NaX and an activated carbon material, AC35. We also evaluate the effect of H(2)O on CO(2) adsorption and on the stability of the structures. Based on the experimental adsorption data, the performance potential of MOFs in several pressure swing adsorption processes is estimated by making a ranking of working capacities and separation factors. We discuss the separation of biogas, the purification of H(2) produced by steam reforming of methane, and the removal of CO(2) from synthesis gas in IGCC (integrated gasification combined cycle) systems. Some MOFs are very well placed in the ranking of (isothermal) working capacity vs. selectivity. Yet, performance is not the only criterion for the selection of MOFs. Ease and cost of synthesis and long-term stability are other important aspects that have to be taken into account.

Separation of CO2-CH4 mixtures in the mesoporous MIL-100(Cr) MOF: experimental and modelling approaches.

Carbon dioxide is the main undesirable compound present in raw natural gas and biogas. Physisorption based adsorption processes such as pressure swing adsorption (PSA) are one of the solutions to selectively adsorb CO(2) from CH(4). Some hybrid crystalline porous materials that belong to the family of metal-organic frameworks (MOFs) show larger CO(2) adsorption capacity compared to the usual industrial adsorbents, such as zeolites and most activated carbons, which makes them potentially promising for such applications. However, their selectivity values have been most often determined using only single gas adsorption measurements combined with simple macroscopic thermodynamic models or by means of molecular simulations based on generic forcefields. The transfer of this systematic approach to all MOFs, whatever their complex physico-chemical features, needs to be considered with caution. In contrast, direct co-adsorption measurements collected on these new materials are still scarce. The aim of this study is to perform a complete analysis of the CO(2)-CH(4) co-adsorption in the mesoporous MIL-100(Cr) MOF (MIL stands for Materials from Institut Lavoisier) by means of a synergic combination of outstanding experimental and modelling tools. This solid has been chosen both for its fundamental interests, given its very large CO(2) adsorption capacities and its complexity with a combination of micropores and mesopores and the existence of unsaturated accessible metal sites. The predictions obtained by means of Grand Canonical Monte Carlo simulations based on generic forcefields as well as macroscopic thermodynamic (IAST, RAST) models will be compared to direct the co-adsorption experimental data (breakthrough curve and volumetric measurements).

Aerial pollutants in swine buildings: a review of their characterization and methods to reduce them.

The swine industry follows a large increase of meat production since the 1950s causing the development of bigger swine buildings which involves a raise of pollutants emissions. Due to recent anthropological pressures concerning the animal welfare, the limitation of neighborhood disturbances and atmospheric pollutions limitations, the livestock farming has to adapt their management methods to reduce or treat the aerial pollutants emissions. Through the diversity of livestock barns configurations, their climatic location, their size, and their management, we thus propose hereafter a critical review of the characterizations of these aerial pollutants. This is realized by distinguishing both solids and gaseous emissions and by referencing the measurements methods mainly used to analyze and quantify airborne particles, odorants, and gaseous compounds in the atmosphere of swine buildings. The origins of these pollutants are focused and the sturdiest techniques for concentration measurements are highlighted. Finally, we discuss pollutants abatement techniques criticizing their implementation in swine buildings and emphasizing the use of biological ways such as biofiltration for gases and odors treatment.

Quantification of the NH3 Adsorption on Dusts and its Consequences on the Design of Systems for the Removal of Aerial Pollutants in Piggeries

Through the framework of the aerial pollutants removal from the atmosphere of piggeries using a biofilter, this paper focuses on the effect of the presence of dust on the design of the biofilter. Simultaneous measurements (dust size distribution, dust concentration and NH3 concentrations) are carried out in the casing of the piggery air extraction.

Global statistical predictor model for characteristic adsorption energy of organic vapors–solid interaction: Use in dynamic process simulation

Adsorption of Volatile Organic Compounds (VOCs) is one of the best remediation techniques for controlling industrial air pollution. In this paper, a quantitative predictor model for the characteristic adsorption energy (E) of the Dubinin-Radushkevich (DR) isotherm model has been established with R(2) value of 0.94. A predictor model for characteristic adsorption energy (E) has been established by using Multiple Linear Regression (MLR) analysis in a statistical package MINITAB. The experimental value of characteristic adsorption energy was computed by modeling the isotherm equilibrium data (which contain 120 isotherms involving five VOCs and eight activated carbons at 293, 313, 333, and 353 K) with the Gauss-Newton method in a statistical package R-STAT. The MLR model has been validated with the experimental equilibrium isotherm data points, and it will be implemented in the dynamic adsorption simulation model PROSIM. By implementing this model, it predicts an enormous range of 1200 isotherm equilibrium coefficients of DR model at different temperatures such as 293, 313, 333, and 353K (each isotherm has 10 equilibrium points by changing the concentration) just by a simple MLR characteristic energy model without any experiments.