0000000000019153
AUTHOR
Marie-hélène Simonot-grange
Adsorption of gaseous p-xylene and m-xylene on NaY, KY, and BaY zeolites: Part 1. Adsorption equilibria of pure xylenes
Abstract Isothermal and isobaric adsorptions of p -xylene and m -xylene on NaY, KY, and BaY are studied by thermogravimetry between 25°C and 400°C, and 10 Pa and 1014 Pa. At low filling BaY shows a stronger affinity for xylenes than the other zeolites. At high temperature and low pressure its adsorption capacity is greater than those of NaY and KY. These two zeolites have a similar behavior and adsorb more m -xylene than p -xylene. At low temperature and high pressure KY adsorbs p -xylene like NaY and m -xylene like BaY, and, unlike NaY, the adsorption capacities of KY and BaY are higher for p -xylene than for m -xylene. The substitution of K + or Ba 2+ for Na + decreases the adsorption cap…
Microporous volume and external surface of Y zeolites accessible to p-xylene and m-xylene
Abstract Isothermal adsorption of p-xylene and m-xylene on NaY, KY and BaY zeolites was studied by thermogravimetry at 25°C. Adsorption isotherms showed type H4 hysteresis associated with a xylenes adsorption process activated by the pressure. Experimental data were analysed with the t-method to distinguish the amounts of xylene adsorbed in the α-cages and on the external surface of crystallites. Results were compared with those previously achieved by calorimetry. Whatever may be the isomer and the Y zeolite, the adsorption capacity of α-cages at 25 °C is equal to 3.5 molecule α−1. At saturation, the amount of xylenes adsorbed on the external surface represents 13% of the total amount adsor…
Données expérimentales et modélisation d’adsorption des systèmes N2(g)/montmorillonite potassique de Camp-Berteau et N2(g)/hydrotalcite carbonatée
Resume In this paper capacities of adsorption of nitrogen onto two clays at 77 K are compared and analyzed. One system is a montmorillonite of Camp-Berteau saturated by potassium cation and the second one is an hydrotalcite saturated by carbonate anion. Adsorbed amounts have been obtained using a volumetric technique. So it is shown that the smectite adsorbed more than the hydrotalcite at the same relative pressure of nitrogen. The modelling of experimental data by various theories of adsorption as de Brunauer, Emmett et Teller (BET) and t-method are used to calculate the specific surface and to have access to the porosity of these materials at 77 K. Then it is shown that the adsorption of …
Water vapour adsorption onto Ca2+ Camp–Berteau montmorillonite and comparison with properties of Na+ sample
Abstract In this paper, we present an analysis of the adsorbed amounts and adsorption heats of water vapour of Ca2+ Camp–Berteau montmorillonite. Measurements were obtained at 298 K using thermogravimetry and calorimetry as a function of relative pressure and the study was completed by the adsorption of nitrogen at 77 K. Experimental data were analysed with BET and t-method theories and compared with those of the Na+ sample. A correlation was shown between models and two domains observed on the calorimetric curves. These domains have been attributed to a multilayer equivalent adsorption. However, the determination of the surface area of clays remains a difficulty. So, the areas of interlaye…
Adsorption Properties of Nax and Bax Zeolites: Correlation between Structural and Thermodynamic Results on Para- and Meta-xylene Adsorption
A comparison is made between NaX and BaX adsorption properties starting from crystallographic data and thermodynamic measurements. Adsorption isotherms and differential adsorption heats of pure para- and meta-xylenes in NaX and BaX zeolites are interpreted in the light of crystallographic results.
Adsorption of m-Xylene on Prehydrated Zeolite BaX: Correlation between Temperature-Programmed Desorption and Low-Temperature Neutron Powder Diffraction Studies
Adsorption of m-xylene on partially hydrated zeolite BaX is studied by thermogravimetry, mass spectrometry, temperature-programmed desorption and neutron diffraction for different m-xylene loadings of the zeolite. Macroscopic and microscopic measurements, for both molecules, were correlated and relationships were found between the crystallographic positions of the adsorbed molecules on the zeolite and macroscopic properties such as the number and the area of the peaks in the desorption spectra for m-xylene or water. The influence of water molecules on the adsorption phenomenon of m-xylene on BaX zeolite was characterized. In particular, it was shown that the increase of the filling of the p…
Contribution to the study of framework modification of SAPO-34 and SAPO-37 upon water adsorption by thermogravimetry
Abstract The adsorption–desorption of water vapor in SAPO-34 and SAPO-37 is followed in isobar conditions ( P H 2 O =17.6 mbar ) by thermogravimetry at temperatures from 20°C to 400°C. The phenomenon is reversible in SAPO-34 but not in SAPO-37. The rise in water uptake is the highest at around 60–70°C, i.e. in range where an attack of the frameworks was previously reported. The reversibility (or not) of water adsorption–desorption uptake is linked to this reversible (or not) framework modification. The kinetics of desorption in SAPO-34 is strongly slowed down between 40°C and 60°C. This suggests that the full restructuration of the framework requires some time (700 min in the experimental c…
Co-adsorption of 1,2-dichloroethane and 1-bromo,2-chloroethane on zeolite ZSM-5 from the liquid and vapour phases, using the Myers-Prausnitz-Dubinin model
Abstract The adsorption/co-adsorption of 1,2-dichloroethane (DCA) and 1-bromo,2-chloroethane (BCA) from the vapour and the liquid phases by zeolite ZSM-5 at ambient temperature is reported, using Dubinin's theory and the recent Myers-Prausnitz-Dubinin (MPD) theory. For adsorption from the liquid phase, the activity coefficients in the adsorbed and the liquid states are the same and no selectivity is observed. This is confirmed by the absence of an excess enthalpy of immersion of ZSM-5 into the mixtures. Adsorption from the vapour phase proceeds in two stages, as indicated by double Dubinin-Astakhov (DA) plots. If one considers only the domain of high relative pressure, co-adsorption is desc…
Location of Water and Xylene Molecules Adsorbed on Prehydrated Zeolite BaX. A Low-Temperature Neutron Powder Diffraction Study
Differential calorimetric enthalpies of adsorption ofp-xylene andm-xylene on y faujasites at 25°C
The differential enthalpies of adsorption ofp-xylene andm-xylene on NaY, KY and BaY zeolites were measured by isothermal calorimetry coupled with isothermal volumetry at 25‡C. Whatever the zeolite, the enthalpies of adsorption ofp-xylene andm-xylene at low filling were of the same order of magnitude. They did not show significantly the effect of the dipolar moment ofm-xylene. Their absolute values varied in the sequence
Adsorption of chlorinated volatile organic compounds on hydrophobic faujasite: correlation between the thermodynamic and kinetic properties and the prediction of air cleaning
This work deals with a thermodynamic and kinetic study of the adsorption of single volatile organic compounds (VOCs) (dichloromethane (DCM), 1,2-dichloroethane (DCA), trichloroethene (TCE) and tetrachloroethene (PCE)) on a dealuminated faujasite Y by simultaneous measurements of the adsorbed amounts, adsorption heats and diffusivities. The type V isotherms and the weak values of derivative enthalpies allowed us to predict that the competitive adsorption of their mixture would be similar to a distillation. This prediction was verified experimentally: the breakthrough curves of VOC mixtures showed that the adsorbate with the higher boiling point displaced the adsorbate with the lower boiling …
t-Curves for n-Hexane
The adsorption and desorption isotherms of n-hexane on powdered alumina and silica have been studied at 25°C over a wide range of relative pressures. Two t-curves for pore structure analysis are proposed, one for alumina (C = 12) and the second for silica (3 ≤ C ≤ 9). The statistical thickness t of the adsorbed n-hexane layer has been drawn as a function of the relative pressure assuming a maximal thickness of 0.55 nm and a mean thickness of 0.42 nm for the monolayer. The results are discussed in relation to previous published data.
Adsorption of gaseous p-xylene and m-xylene on NaY, KY, and BaY zeolites. Part 2: Modeling. Enthalpies and entropies of adsorption
Abstract The adsorption isotherms of xylenes are described by Henry's law and Langmuir's model on NaY and KY and the Dubinin-Radushkevich model on BaY. The isoteric enthalpies of adsorption show on each zeolite that the adsorbate-adsorbent interactions are nearly the same with both isomers. They are stronger on BaY than on NaY and KY. The adsorbate-adsorbate interactions are stronger with m-xylene than with p-xylene and especially outstanding on KY. The entropies of adsorption show that the mobility of the adsorbate is lower with m-xylene than with p-xylene. The isosteric free enthalpies of adsorption are related to the acidity of each zeolite. BaY has a stronger acidity and a greater abili…
Adsorption of p-Xylene/m-Xylene Gas Mixtures on BaY and NaY Zeolites. Coadsorption Equilibria and Selectivities
Coadsorption of the gases p-xylene and m-xylene on BaY and NaY was studied at 150 °C in the range of pressure 10-2-3 hPa. For BaY coadsorption isotherms and single-component adsorption isotherms are perfectly superimposed in the whole range of investigated pressure. The capacity of adsorption of BaY is 3 molecules α-1 for each single component as well as for each mixture under 3 hPa. For NaY coadsorption isotherms lie between those of single p-xylene and m-xylene. The capacity of adsorption of NaY for mixtures is in proportion to the composition of the initial adsorptive mixture and varies from the capacity of adsorption for single p-xylene (3.3 molecules α-1) to that for single m-xylene (3…
Study of the Pore Network of Dealuminated Faujasites by Water Vapor Adsorption
Summary The adsorption and desorption isotherms of water vapor are drawn at 25°C for dealuminated HY zeolites upon framework Si/Al ratio. The isotherms are compared to that of the parent NaY zeolite. The isotherm changes in shape from the type I to the type IV with an hysteresis loop changing from the type H 4 to the type H 2 , as increases the Si/Al ratio. The POLANYI-DUBININ theory is used to determine the micropore volume accessible to water. It decreases with increasing Si/Al ratios, down to zero at a Si/Al ratio of 35. Such a result is accounted by the adsorption on the hydrophilic centers which are the cations (H + ) associated with the structural aluminium ions, each cation being coo…
Valorisation de machines frigorifiques a adsorption sur zeolithes
Abstract The regeneration stage using intermittent thermodynamical cycles based on zeolite adsorption (zeolite 13X-H2O) has been studied. This point is of particular interest for understanding of systems of energy storage and cooling. This paper examines the use of microwave energy sources for analysing the regeneration problem. The method proposed allows a considerable decrease in the regeneration time without an increase of the temperature of the material. The energy yields are high and the adsorption-desorption time cycles are short if the microwave field is well tuned. This last is a function of time and of the filling coefficient. The results obtained using microwave irradiation are co…