Sorption of Carbon Dioxide from Wet Gases by K2CO3-in-Porous Matrix: Influence of the Matrix Nature

In a fixed-bed absorber at 40°C, the dynamics of carbon dioxide sorption over composite sorbents prepared by impregnation of potassium carbonate in various porous matrixes is studied. The dynamic capacity of the synthesized sorbents is shown to reach 0.12 g CO₂ per 1 g of the sorbent. The composite dynamic capacity depends on the nature of the host matrix and decreases in the sequence alumina > activated carbon > vermiculite > silica gel. For K₂CO₃-on-alumina, the sorption capacity decreases considerably after the first cycle of «absorption and regeneration under 200–350°C», whereas the sorbents based on active carbons could be reversibly restored. The findings are discussed within the idea on a chemical interaction between the host matrix and the impregnated salt.     

Assessment of the sorption capacity and regeneration of carbon dioxide sorbents using thermogravimetric methods

Adsorption methods using solid sorbents are an alternative to the absorption technology in the processes of purification gases from carbon dioxide. There is a need to rapidly assess the suitability of sorbents for use it in PSA, TSA, or VPSA installations. Important parameters which determine the quality of the sorbent are the sorption capacity of sorbent, selectivity to CO₂ and the possibility of regeneration. This paper presents the results of sorption/desorption of CO₂ study on the impregnated porous materials using thermogravimetric methods. Thermogravimetry allows for rapid assessment of sorption capacity and regeneration of the sorbents. Specially selected temperature program allowed to determine the sorption capacity of sorbents depending on the concentration of CO₂ in the gas mixture and temperature. Degree of sorbent purification was determined in desorption process.     

Sorption of carbon dioxide by the composite sorbent “potassium carbonate in porous matrix”

Sorption of CO₂ in the presence of water vapor by the K₂CO₃—-Al₂O₃ composite sorbent was studied by IR spectroscopy in situ, X-ray diffraction analysis, and the differentiating dissolution method and reasons for a decrease in its dynamic capacity are given. The samples containing K₂CO₃·1.5H₂O in pores are characterized by the maximal dynamic capacity. A mechanism for CO₂ sorption was proposed, which qualitatively explains the obtained dependence of the capacity on the water content in the composite sorbent. A high dynamic capacity can be maintained by regeneration of the sorbents by water vapor at 170 °N. The capacity of the sorbents decreases during the first 10 sorption—regeneration cycles due to the formation of an inactive phase of potassium aluminum carbonate.     

Enthalpies of Dilution of Aqueous Solutions of HCl, MgCl2}, CaCl2, and BaCl2 at 300, 325, and 350°C

Dilution enthalpies, measured using isothermal flow calorimetry, are reported for aqueous solutions of BaCl₂ at 300°C and 11.0 MPa, MgCl₂, CaCl₂, and BaCl₂ at 325°C and 14.8 MPa, and at 350°C and 17.6 MPa. Previously collected dilution enthalpies for aqueous solutions of MgCl₂ and CaCl₂ at 300°C and 10.3 MPa and for aqueous solutions of HCl at 250, 275, and 300°C at 10.3 MPa and 320°C at 12.8 MPa were included with the new data at 300°C and 11.0 MPa and at 350°C and 17.6 MPa when fitting the Pitzer parameters. The concentration range of the chloride solutions was 0.5 to 0.02 molal. Parameters for the Pitzer excess Gibbs ion–interaction equation were determined from the fits of the experimental heat data. Equilibrium constants, enthalpy changes, entropy changes, and heat-capacity changes for the association of alkaline earth metal ions and H⁺ with chloride ion were estimated from the heat data. For all systems, the enthalpy and entropy changes are positive and show accelerating increases with temperature. The resulting equilibrium constants show significant, but smaller, increases with temperature.     

FT-IR study on CO<Subscript>2</Subscript> adsorbed species of CO<Subscript>2</Subscript> sorbents

The stability of amine-functionalized silica sorbents prepared through the incipient wetness technique with primary, secondary, and tertiary amino organosilanes was investigated. The prepared sorbents were exposed to different gaseous streams including CO₂/N₂, dry CO₂/air with varying concentration, and humid CO₂/air mixtures to demonstrate the effect of the gas conditions on the CO₂ adsorption capacity and the stability of the different amine structures. The primary and secondary amine-functionalized adsorbents exhibited CO₂ sorption capacity, while tertiary amine adsorbent hardly adsorbed any CO₂. The secondary amine adsorbent showed better stability than the primary amine sorbent in all the gas conditions, especially dry conditions. Deactivation species were evaluated using FT-IR spectra, and the presence of urea was confirmed to be the main deactivation product of the primary amine adsorbent under dry condition. Furthermore, it was found that the CO₂ concentration can affect the CO₂ sorption capacity as well as the extent of degradation of sorbents.     

Mesoporous silicate MCM-48 as an enrichment medium for ambient volatile organic compound analysis

This study investigated the sorption/desorption properties of MCM-48 and its applicability as a sorbent for on-line gas chromatographic analysis of ambient volatile organic compounds (VOCs). To establish a valid comparison, commercially available carbon sorbents were evaluated under similar analytical conditions. Two trapping temperatures of 30 °C and −20 °C, representing ambient and sub-ambient temperatures, were tested by trapping a full range of VOCs from C₂–C₁₂. At ambient temperatures, due to the mesoporosity, the MCM-48 showed considerably limited trapping efficiency compared to microporous carbon sorbents on the highly volatile section of VOCs and only began to show effective trapping for compounds larger than C₇. Cooling to sub-ambient temperatures (e.g., −20 °C) extended the effective trapping down to C₄ VOCs, drastically increasing the applicability of MCM-48 as an in-line enrichment medium for gas chromatographic analysis of VOCs. The mesoporosity of MCM-48 also aided desorption. Much lower desorption temperatures (100–180 °C) were required for full desorption as compared to the temperatures (greater than 200 °C) required for carbon sorbents. Moreover, the easy desorption was accompanied by a low memory effect, as the large pores of MCM-48 can clean up more efficiently after desorption, with little residue left behind.     

Thermoanalytical study of acetylacetonate-modified titanium(IV) isopropoxide as a precursor for TiO<Subscript>2</Subscript> films

Thermal decomposition of dried TiO₂ gel, obtained by hydrolysing acetylacetonate-modified titanium(IV) isopropoxide, was monitored by simultaneous TG/DTA/EGA-FTIR measurements in dynamic air up to 900&deg;C. XRD and FTIR were employed to identify the solid reaction products. Thermal degradation of the TiO₂ gel consists of five distinct mass loss steps, the total mass loss being 43.8&percnt;. EGA by FTIR revealed the release of H₂O below 120&deg;C; followed by acetone, isopropyl acetate and 1-propanol around 200-300&deg;C, and finally CO and CO₂ up to 550&deg;C. Highly exothermic reaction at 410-550&deg;C is caused by the combustion of carbon residues. Crystalline TiO₂-anatase is formed around 500&deg;C and TiO₂-rutile close to 800&deg;C.     

Preparation of Sorbents Containing Straetlingite Phase from Zeolitic By-Product and Their Performance for Ammonium Ion Removal

In this study, straetlingite-based sorbents were used for NH₄⁺ ion removal from a synthetic aqueous solution and from the wastewater of an open recirculation African catfish farming system. This study was performed using column experiments with four different filtration rates (2, 5, 10, and 15 mL/min). It was determined that breakthrough points and sorption capacity could be affected by several parameters such as flow rate and mineral composition of sorption materials. In the synthetic aqueous solution, NH₄⁺ removal reached the highest sorption capacity, i.e., 0.341 mg/g with the S30 sorbent at a filtration rate of 10 mL/min and an initial concentration of 10 mg/L of NH₄⁺ ions. It is important to emphasize that, in this case, the Ce/C0 ratio of 0.9 was not reached after 420 min of sorption. It was also determined that the NH₄⁺ sorption capacity was influenced by phosphorus. In the wastewater, the NH₄⁺ sorption capacity was almost seven times lower than that in the synthetic aqueous solution. However, it should be highlighted that the P sorption capacity reached 0.512 mg/g. According to these results, it can be concluded that straetlingite-based sorbents can be used for NH₄⁺ ion removal from a synthetic aqueous solution, as well as for both NH₄⁺ and P removal from industrial wastewater. In the wastewater, a significantly higher sorption capacity of the investigated sorbents was detected for P than for NH₄⁺.     

Effects of alumina phases on CO2 sorption and regeneration properties of potassium-based alumina sorbents

A range of potassium-based alumina sorbents were fabricated by impregnation of alumina with K₂CO₃ to examine the effects of the structural and textural properties of alumina on the CO₂ sorption and regeneration properties. Alumina materials, which were used as supports, were prepared by calcining alumina at various temperatures (300, 600, 950, and 1,200 °C). The CO₂ sorption and regeneration properties of these sorbents were examined during multiple tests in a fixed-bed reactor in the presence of 1 vol% CO₂ and 9 vol% H₂O. The regeneration capacities of the potassium-based alumina sorbents increased with increasing calcination temperature of alumina. The formation of KHCO₃ increased with increasing calcination temperature during CO₂ sorption, whereas the formation of KAl(CO₃)(OH)₂, which is an inactive material, decreased. These results is due to the fact that the structure of alumina by the calcination temperature is related directly to the formation of the by-product [KAl(CO₃)(OH)₂]. The structure of alumina plays an important role in enhancing the regeneration capacity of the potassium-based alumina sorbent. Based on these results, a new potassium-based sorbent using δ-Al₂O₃ as a support was developed for post-combustion CO₂ capture. This sorbent maintained a high CO₂ capture capacity of 88 mg CO₂/g sorbent after two cycles. In particular, it showed a faster sorption rate than the other potassium-based alumina sorbents examined.     

Effect exerted by texture of calcined calcium oxide on its sorption capacity in the CO2 sorption-regeneration cycles

The dynamic capacity of a set of sorbents prepared by calcination of different precursors was studied in multiple CO₂ sorption-regeneration cycles. The effect exerted by type of a precursor and calcination temperature on the steady state value of the dynamic capacity attained after several tens of cycles was determined. A model was suggested for estimate of the sorption capacity of CaO sintered above the Tammann temperature from data on the mercury porosimetry.     

Effect of antimony dopants on the sorption properties of SnO2

The effects of antimony modifying additive (0.15—0.50 at.% Sb) on the electrophysical and sorption properties of SnO₂ powders with a well developed specific surface were studied in the temperature range of 25—250 °C. Small amounts of antimony (0.15 at.%) increase the conductivity of SnO₂ containing SO₂ and CO chemisorbed in the temperature range of 25—100 °C. This makes this composition promising as a sensitive element of gas sensors.     

The Effect of the Modification of Carbon Spheres with ZnCl2 on the Adsorption Properties towards CO2

Zinc chloride and potassium oxalate are often applied as activating agents for carbon materials. In this work, we present the preparation of ZnO/carbon spheres composites using resorcinol-formaldehyde resin as a carbon source in a solvothermal reactor heated with microwaves. Zinc chloride as a zinc oxide source and potassium oxalate as an activating agent were applied. The effect of their addition and preparation conditions on the adsorption properties towards carbon dioxide at 0 °C and 25 °C were investigated. Additionally, for all tested sorbents, the CO₂ sorption tests at 40 °C, carried out utilizing a thermobalance, confirmed the trend of sorption capacity measured at 0 and 25 °C. Furthermore, the sample activated using potassium oxalate and modified using zinc chloride (a carbon-to-zinc ratio equal to 10:1) displayed not only a high CO₂ adsorption capacity (2.69 mmol CO₂/g at 40 °C) but also exhibited a stable performance during the consecutive multicycle adsorption–desorption process.     

Application of a carbonized apricot stone for the treatment of some radioactive nuclei

Apricot stone shells were carbonized under certain chemical and thermal conditions to produce sorbents having a quantitative affinity to retain some radioactive nuclei. The sorbent shows a thermal stability upto 500 °C. The diffraction patterns clarify that the sorbent is mainly amorphous in structure. Carbon in these shells was elementally analyzed and the data reveal a predominant content of acidic surface centers with hydrophilic properties. The isoelectric point (pH_PZC) was determined and found to be 4.2 implying the acidic nature of the sorbent surface. The sorption of Cs⁺, Co²⁺ and Eu³⁺ on the prepared sorbent was studied from aqueous solution under different variables and the sorption capacity had values from 0.23-1.15 meq/g.     

Solubility of nonpolar gases in tetrahydrofuran at 0 to 30°C and 101.33 kPa partial pressure of gas

Solubility measurements of several nonpolar gases (He, Ne, Ar, Kr, Xe, H₂, D₂, N₂, CH₄, C₂H₄, C₂H₆, CF₄ and SF₆) in tetrahydrofuran from 0 to 30°C and 101.33 kPa partial pressure of gas are reported. Thermodynamic functions for the solution process (Gibbs energy, enthalpy, and entropies) at 25°C are evaluated from experimental values of gas solubility as mole fractions and their variation with temperature. Lennard-Jones 6–12 pair potential parameters for tetrahydrofuran are estimated using the scale particle theory; experimental solubilities as mole fraction are compared with values calculated using this theory.     

Sorbents based on calix[4]arenes for extraction of technetium(vii) from acidic and alkaline media

Sorption of Tc^VII from solutions of various compositions with new sorbents prepared by the noncovalent immobilization of (thia)calix[4]arenes on the Amberlite XAD-7™ support was studied. The sorbents studied efficiently extract technetium(vii) from both acidic and alkaline media. The sorption capacity of the sorbent with thiacalix[4]arene groups is superior to that of the sorbents with calix[4]arene groups and several times higher than that of the sorbents previously proposed for the sorption of Tc^VII. Technetium(vii) is sorbed by this sorbent as 1: 1 and 1: 2 thiacalix[4]arene—NH₄TcO₄ and 1: 1 and 1: 2 thiacalix[4]arene—NaTcO₄ complexes.     

Modified Raoult's law including the solvent structural constant and solute solvation; Aqueous sodium chloride solutions, 25 to 300°C; Other electrolytes and urea, 25°C

The form of Raoult's law is modified to express the activity of water [a(H₂O)] for aqueous electrolyte solutions by the mole fraction of a free (nonsolvating) solvent structural unit raised to the reciprocal power of the solvent structural constant. Relatively close agreement with experiment, is obtained for a(H₂O) of aqueous sodium chloride solutions up to 300°C and nearly saturated concentrations, and of other aqueous electrolyte solutions at 25°C. In an example for aqueous-organic systems, a(H₂O) for urea solutions at 25°C is described with an average deviation of 0.09% for molalities from 0 to 20m (54.6 wt%) by using the necessary (universal) structural constant and a single solvation parameter.     

The solvent dependence of the sorptive abilities of tetracyanocomplexes

The two different types of tetracyanocomplexes [ZnNi(CN)₄·nH₂O] and [Cd(en)Pd(CN)₄·2C₆H₆] have been examined as sorptive materials in a simple contact with benzene, after their modification with auxiliary solvents and their use in gas chromatographic experiments. All forms of sorption experiments show identical characteristics from the view of the sorption of aromatic compounds as exemplified by benzene. The tetracyanocomplexes exhibit a permanent capability of sorption, even when heated to a temperature of 260°C and show a separation ability towards sorbed materials depending on the solvent used and on the degree of thermal degradation of the tetracyanocomplex. The prducts of the modification and sorption (in static and dynamic) experiments have been characterized by IR spectroscopy, X-ray patterns and by thermal analysis.     

Partial molal enthalpies,excess partial molal heat capacities,and structural effects ofn-Am4NBr in the water-dioxane system

Integral heats of solution of tetra-n-pentylammonium bromide, n-Am₄NBr, in aqueous binary mixtures of dioxane are reported at 25° and 35°C from 0.0 to 0.3 mole fraction of dioxane. The excess partial molal heat capacity c _p ^° at 30°C is derived from the integral heats of solution at infinite dilution at 25° and 35°C. The partial molal enthalpies of n-Am₄NBr exhibit a rather flat maxima at 0.2 mole fraction dioxane. The c _p ^° values suggest a structure-breaking role for dioxane. The results obtained in this study are compared with those obtained with n-Bu₄NBr in the same system in an earlier study.     

Selective water sorbents for multiple applications, 8. sorption properties of CaCl2?SiO2 sol-gel composites

This paper presents sorption properties of CaCl₂/SiO₂ composites synthesized by a sol-gel approach. Desorption isobars measured at T=30–140°C and vapor pressure 12.8–81.0 mbar clearly show a correlation between the sorbents pore structure and their sorption properties. The sample adsorptivities are found to exceed 1.2 kg H₂O/kg adsorbent (or 20–25 mol H₂O/mol of the salt). That is markedly higher than any reported before for silica-based materials. This results in a high energy storage capacity reaching 3,400 kJ/kg of dry sorbent, as confirmed by direct calorimetric measurements. The isosteric desorption heat is found to decrease from 67±5 kJ/mol to 46±5 kJ/mol with increase in the surface coverage.     

Adsorption of benzene on dispersed polycrystalline fullerites

The sorption properties of dispersed polycrystalline C₆₀ and C_Σ (a mixture of fullerenes) fullerites were studied. The isotherms of adsorption of benzene on these sorbents were measured. Some data on the sorption of ethanol from gas and liquid phases, KOH from solutions in ethanol, and naphthalene in the solid and molten states and from its solutions in ethanol were obtained. The sorbability of the C_Σ samples with respect to benzene is as high as that of commercial activated carbons, while C₆₀ fullerites were found to be less efficient sorbents. It was concluded that dispersed polycrystalline fullerites are porous sorbents. Through porosity arises due to the presence of defects in the crystal structure; i.e., the less perfect the lattice, the higher its adsorption capacity.