In
this work, a new aluminum fumarate MOF was investigated regarding
its water stability and CO2 adsorption in the presence
and absence of water. The adsorption equilibrium isotherms were measured
at 303, 323, and 348 K for CO2 and at 288 and 313 K for
water vapor. Water vapor adsorption isotherms are type IV and were
fit using the Langmuir-Ising model. The adsorption capacity of CO2 at 303 K and 1.0 bar was 2.1 mmol/g and remained constant
after exposure to humidity and regeneration. The isosteric heats of
adsorption were 21 and 44 kJ/mol for CO2 and H2O, respectively. Fixed bed experiments were performed at 303 K to
determine breakthrough curves of CO2, water vapor, and
the CO2/water vapor mixture. Binary breakthrough indicated
a reduction of only 17% in CO2 adsorption capacity for
a stream with 14% RH. The remarkable stability of this MOF suits it
for such applications as CO2 capture and thermal storage
with water.
Growing concern about climate change has been driving the search for solutions to mitigate greenhouse gas emissions. In this context, carbon capture and utilization (CCU) technologies have been proposed and developed as a way of giving CO2 a sustainable and economically viable destination. An interesting approach is the conversion of CO2 into valuable chemicals, such as methanol (MeOH) and dimethyl ether (DME), by means of catalytic hydrogenation on Cu-, Zn-, and Al-based catalysts. In this work, three catalysts were tested for the synthesis of MeOH and DME from CO2 using a single fixed-bed reactor. The first one was a commercial CuO/γ-Al2O3; the second one was CuO-ZnO/γ-Al2O3, obtained via incipient wetness impregnation of the first catalyst with an aqueous solution of zinc acetate; and the third one was a CZA catalyst obtained by the coprecipitation method. The samples were characterized by XRD, XRF, and N2 adsorption isotherms. The hydrogenation of CO2 was performed at 25 bar, 230°C, with a H2:CO2 ratio of 3 and space velocity of 1,200 ml (g cat · h)−1 in order to assess the potential of these catalysts in the conversion of CO2 to methanol and dimethyl ether. The catalyst activity was correlated to the adsorption isotherms of each reactant. The main results show that the highest CO2 conversion and the best yield of methanol are obtained with the CZACP catalyst, very likely due to its higher adsorption capacity of H2. In addition, although the presence of zinc oxide reduces the textural properties of the porous catalyst, CZAWI showed higher CO2 conversion than commercial catalyst CuO/γ-Al2O3.
A headspace technique, that consists in analyzing the composition of the vapor phase in equilibrium with the condensed phase of a mixture in a sealed vial containing the adsorbent sample, has been recently applied to acquire equilibrium data for adsorption of xylenes in liquid phase. In this study, we used this technique to measure experimental binary equilibrium data for C 8 aromatics in Y and mordenite zeolitic molecular sieves. For the Y zeolite, we also measured C 8 aromatics quaternary equilibrium data. Measurements were made at temperatures between C 40-80°C. A more tedious, but traditional, chromatographic pulses method was also used to validate some of the results.
Metal-impregnated carbons (Cu--AC; Ag--AC and Pd--AC) were studied as adsorbents for the desulphurization of liquid fuels. A real gasoline was examined for sulphur compounds. Textural characteristics of adsorbents were determined by nitrogen adsorption/desorption isotherms at 77 K. The adsorption isotherms were obtained by frontal analysis in a single fixed bed at 30 degrees C and 45 degrees C. Breakthrough curves were simulated according to a mathematical model that assumed axially dispersed flow and mass transfer described by a linear driving force approximation and nonlinear adsorption equilibrium reached instantaneously on the external surface of the adsorbents particles. The model was solved numerically by orthogonal collocation in finite elements, using the commercial solver gPROMS. The proposed model matched experimental data reasonably well. Resistance to mass transfer was significant and thought to be due to intraparticle diffusion kinetics. The results confirmed the efficiency of the use of activated carbon (AC) in the adsorption of sulphur compounds, especially when its surface is modified with metals. Comparing adsorption capacities of sulphur compounds from real gasoline, AC-Pd material appeared more selective than other materials, even presenting a behaviour of rapid saturation explained by the presence of other components competing for adsorption sites, reducing their effectiveness in removing sulphur compounds. Both pristine AC and Pd--AC showed good regenerability. The regenerated Pd--AC sorbent can recover about 85% of the desulphurization capacity.
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