Adsorption of nitrogen, methane, carbon monoxide, and their binary mixtures on aluminophosphate molecular sieves

Experimental isotherms describing the adsorption of pure N₂, CH₄ and CO in AlPO₄-11, AlPO₄-17, and AlPO₄-18 were determined using the volumetric method at 40°C and at 23°C (AlPO₄-11 only) over a pressure range up to 123 kPa, and subsequently fitted with the Langmuir or Freundlich equations, as well as the Flory-Huggins Vacancy Solution Theory equation. The capacities for the adsorbates investigated were found to depend on the geometry of the sieve pore size, as well as the molecular dimensions and the polority of the adsorbate involved. At 40°C and over the investigated pressure range, AlPO₄-11 and AlPO₄-17 adsorbed pure CH₄ in the highest amounts, while AlPO₄-18 had a slightly higher capacity for pure CO. The model parameters obtained by fitting the experimental pure-component isotherms permitted the prediction of binary adsorption information for the CO−N₂, CH₄−CO, and CH₄−N₂ gas mixtures at 101.3 kPa total pressure, using the Extended Langmuir Model, the Ideal Adsorbed Solution Theory, and/or the Flory-Huggins Vacancy Solution Theory for mixtures. An explanation of the behaviour predicted by each model for each adsorption system is attempted.     

Catalytic oxidation of methanol on high-dispersity iron oxide in micro- and mesoporous molecular sieves

The catalytic properties of high-dispersity iron oxide deposited on micro-and mesoporous molecular sieves were studied. The deposition was performed by the in situ thermooxidative degradation of various precursors. The atomic catalytic activity of the catalysts in the oxidation of methanol was found to depend on both iron concentration and the accessibility of iron oxide particles.     

Adsorption of hydrogen isotopes on micro- and mesoporous adsorbents with orderly structure

The equilibrium and dynamic adsorption data of H(2) and D(2) on different micro- and mesoporous adsorbents with orderly structure including 3A, 4A, 5A, Y, and 10X zeolites; carbon CMK-3; silica SBA-15; and so forth were collected. Critical effect of the nanodimension of adsorbents on the adsorption behavior of hydrogen and its isotopes is shown. The highest adsorption capacity was observed at pore size 0.7 nm, but equal or even larger isotope difference in the equilibrium adsorption was observed at larger pore sizes, whereas the largest isotope difference in the dynamic adsorption was observed at 0.5 nm. The adsorption rate of D(2) is larger than that of H(2) in microporous adsorbents, but the sequence could be switched over in mesoporous materials. Linear relationship was observed between the adsorption capacity for hydrogen and the specific surface area of adsorbents although the adsorbents are made of different material, which provides a convincing proof of the monolayer mechanism of hydrogen adsorption. The linear plot for microporous adsorbents has a larger slope than that for mesoporous adsorbents, which is attributed to the stronger adsorption potential in micropores.     

Adsorption of molecular hydrogen on ultrafine microporous/mesoporous materials

The comparative processing of H₂ adsorption isotherms obtained at 77 K is demonstrated to be applicable to the investigation of the microtexture of the ultrafine oxide materials MCM-41 and ZSM-5 and their mechanical mixtures. The H₂ sorption method allows the micropore volume to be determined correctly for mixed ultrafine microporous/mesoporous materials.     

Synthesis and characterization of mesoporous molecular sieves

In the synthesis of mesoporous molecular sieves of the type MCM-41, different cationactive surfactants and sources of silicon were used. Moreover, Al-MCM-41 samples with different content of aluminium were synthesized. MCM-41 and Al-MCM-41 were synthesized at elevated temperature in stainless-steel autoclaves. Prepared mesoporous molecular sieves were characterized by powder X-ray diffraction (XRD), physical adsorption of nitrogen at the temperature of −197°C, sorption capacity of benzene, and by infrared spectroscopy (FTIR). Acidity was measured for Al-MCM-41 by temperature programmed desorption of ammonia (TPDA) and by FTIR of adsorbed pyridine. Acid catalytic activity of Al-MCM-41 was tested by isomerization of o-xylene. Influence of the synthesis reproducibility, surfactant used, source of silicon, synthesis time, source of aluminium, and Si to Al mole ratio on the properties of mesoporous molecular sieves were evaluated.     

Adsorption and diffusion of nitrogen, methane and carbon dioxide in aluminophosphate molecular sieve AlPO4-11

The knowledge about the adsorption and diffusion properties (specially about diffusion) of aluminophosphate molecular sieves is very scarce in the literature. These materials offer interesting properties as adsorbents as they have a polar framework and do not contain charge-balancing cations. In this work, the adsorption isotherms of nitrogen, methane and carbon dioxide over an AlPO₄-11 sample synthesized in our laboratories have been measured with a volumetric method at 25, 35, 50 and 65 °C over a pressure range up to 110 kPa. The adsorption capacities of each gas are determined by the strength of interaction with the pore surface (carbon dioxide > methane > nitrogen). The equilibrium selectivity to carbon dioxide is quite high with respect to other adsorbents without cations due to the polarity of the aluminophosphate framework. The adsorption Henry’s law constants and diffusion time constants of nitrogen, methane and carbon dioxide in the synthesized AlPO₄-11 material have been measured from pulse experiments. A pressure swing adsorption (PSA) process for recovering methane from a carbon dioxide/methane mixture (resembling biogas) has been designed using a dynamic model where the measured adsorption equilibrium and kinetic information has been incorporated. The simulation results show that the proposed process could be simpler than other PSA processes for biogas upgrading based on cation-containing molecular sieves such as 13X zeolite, as it can treat the biogas at atmospheric pressure, and it requires a lower pressure ratio, to produce high purity methane with high recovery.     

Adsorption separation of carbon dioxide,methane, and nitrogen on Hβ and Na-exchanged β-zeolite

Adsorption isotherms of carbon dioxide （CO2）, methane （CH4）, and nitrogen （N2） on Hβand sodium exchanged β-zeolite （Naβ） were volumetrically measured at 273 and 303 K. The results show that all isotherms were of Brunauer type I and well correlated with Langmuir-Freundlich model. After sodium ions exchange, the adsorption amounts of three adsorbates increased, while the increase magnitude of CO2 adsorption capacity was much higher than that of CH4 and N2. The selectivities of CO2 over CH4 and CO2 over N2 enhanced after sodium exchange. Also, the initial heat of adsorption data implied a stronger interaction of CO2 molecules with Na＋ ions in Naβ . These results can be attributed to the larger electrostatic interaction of CO2 with extraframework cations in zeolites. However, Naβ showed a decrease in the selectivity of CH4 over N2, which can be ascribed to the moderate affinity of N2 with Naβ. The variation of isosteric heats of adsorption as a function of loading indicates that the adsorption of CO2 in Naβ presents an energetically heterogeneous profile. On the contrary, the adsorption of CH4 was found to be essentially homogeneous, which suggests the dispersion interaction between CH4 and lattice oxygen atoms, and such interaction does not depend on the exchangeable cations of zeolite.     

Adsorption separation of carbon dioxide, methane and nitrogen on monoethanol amine modified B-zeolite

A new type of composite adsorbents was synthesized by incorporating monoethanol amine (MEA) into β-zeolite. The parent and MEA-functionalized β-zeolites were characterized by X-ray diffraction (XRD), N₂ adsorption, and thermogravimetric analysis (TGA). The adsorption behavior of carbon dioxide (CO₂), methane (CH₄), and nitrogen (N₂) on these adsorbents was investigated at 303 K. The results show that the structure of zeolite was well preserved after MEA modification. In comparison with CH₄ and N₂, CO₂ was preferentially adsorbed on the adsorbents investigated. The introduction of MEA significantly improved the selectivity of both CO₂/CH₄ and CO₂/N₂, the optimal selectivity of CO₂/CH₄ can reach 7.70 on 40 wt% of MEA-functionalized β-zeolite (MEA(40)-β) at 1 atm. It is worth noticing that a very high selectivity of CO₂/N₂ of 25.67 was obtained on MEA(40)-β. Steric effect and chemical adsorbate-adsorbent interaction were responsible for such high adsorption selectivity of CO₂. The present MEA-functionalized β-zeolite adsorbents may be a good candidate for applications in flue gas separation, as well as natural gas and landfill gas purifications.     

Effect of the nature of quaternary ammonium surfactants on the structure and properties of mesoporous molecular sieves

The influence of the nature of surfactant cations (dodecyltrimethylammonium bromide and tosylate and ethonium chloride) on the structure and adsorbent properties of mesoporous molecular sieves has been studied. The possibility of spatial self-organization of silica-surfactant systems without hydrothermal treatment has been observed. The influence of the surfactant counterions on the structure formation process has also been noted. L. V. Pisarzhevskii Institute of Physical Chemistry, Ukrainian Academy of Sciences, Ukraine, 252039 Kiev, Science Prosp., 31. Translated from Teoreticheskiya i éksperimental’naya Khimii, Vol. 33, No. 1, pp. 53–57, January–February, 1997.     

Synthesis of binaphthols over mesoporous molecular sieves

Mesoporous aluminosilicates (Al-containing NaMCM-41) were applied as catalyst supports for oxidative coupling of β-naphthol and substituted β-naphthols due to their remarkable features such as surface area, ordered mesopores and high thermal stability. The NaMCM-41 supported copper catalysts prepared by impregnation method, and Cu-NaMCM-41 was prepared by incorporating copper during synthesis. Oxidative coupling of β-naphthol reaction was studied using molecular oxygen as oxidant. The copper supported NaMCM-41 catalysts were prepared with different Si/Al ratios and calcined from 120 to 420 °C were observed to show varied product selectivity. The NaMCM-41 supported copper catalysts and Cu-NaMCM-41 were more active than the corresponding Cu/Fe supported on NaY zeolite. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), UV–DRS, ICPMS and BET surface area techniques and the reaction products were confirmed by ¹H-NMR, FTIR and HRMS. An attempt has been made to explain the product selectivity of the catalysts discussed with the above techniques. The high dispersion of Cu⁺² species observed in the catalysts having high Si/Al ratios in NaMCM-41 support and catalysts that are calcined at low temperatures, i.e. less than 420 °C, yielded an unexpected product perylene diol. A comparatively low dispersion of Cu⁺² species, noticed in catalysts having low Si/Al ratios and calcined at high temperatures, yielded binapthol as the coupled product. The effect of the variation of catalyst and the solvent are also studied.     

Hysteresis and scanning behavior of mesoporous molecular sieves

Sorption hysteresis is a widely studied phenomenon whose predicted behavior is well documented and researched. On the other hand, there is much less known about the region that lies between sorption isotherms, believed to be a metastable region. Scanning curves are a way of understanding the mechanism of hysteresis and a tool for hysteresis model validation. Scanning curves were produced for mesoporous materials: SBA-15 and MCM-41 for N(2) sorption at 77 K and Ar sorption at 87 K. A limited set of different scanning behaviors is identified. Like most hysteresis theories, it was found that a single model for scanning behavior cannot be extended to all materials under the same or different experimental conditions. Two behaviors are consistent with recent theories and simulations; however, several are not. The implications as to the characterization of pore dimensions and structure are discussed.     

Synthesis of micro- and mesoporous molecular sieves at room temperature and neutral pH catalyzed by functional analogues of silicatein

By using functional mimics of the protein silicatein alpha together with organic structure directing agents, it was possible to produce different mesoporous and microporous molecular sieves at room temperature and neutral pH.     

Adsorption hysteresis of nitrogen and argon in pore networks and characterization of novel micro- and mesoporous silicas

We report results of nitrogen and argon adsorption experiments performed at 77.4 and 87.3 K on novel micro/mesoporous silica materials with morphologically different networks of mesopores embedded into microporous matrixes: SE3030 silica with worm-like cylindrical channels of mode diameter of approximately 95 angstroms, KLE silica with cage-like spheroidal pores of ca. 140 angstroms, KLE/IL silica with spheroidal pores of approximately 140 angstroms connected by cylindrical channels of approximately 26 angstroms, and, also for a comparison, on Vycor glass with a disordered network of pores of mode diameter of approximately 70 angstroms. We show that the type of hysteresis loop formed by adsorption/desorption isotherms is determined by different mechanisms of condensation and evaporation and depends upon the shape and size of pores. We demonstrate that adsorption experiments performed with different adsorptives allow for detecting and separating the effects of pore blocking/percolation and cavitation in the course of evaporation. The results confirm that cavitation-controlled evaporation occurs in ink-bottle pores with the neck size smaller than a certain critical value. In this case, the pressure of evaporation does not depend upon the neck size. In pores with larger necks, percolation-controlled evaporation occurs, as observed for nitrogen (at 77.4 K) and argon (at 87.3 K) on porous Vycor glass. We elaborate a novel hybrid nonlocal density functional theory (NLDFT) method for calculations of pore size distributions from adsorption isotherms in the entire range of micro- and mesopores. The NLDFT method, applied to the adsorption branch of the isotherm, takes into account the effect of delayed capillary condensation in pores of different geometries. The pore size data obtained by the NLDFT method for SE3030, KLE, and KLE/IL silicas agree with the data of SANS/SAXS techniques.     

Influence of nitrogen oxides on hydrogen values in the microdetermination of carbon and hydrogen,with an external absorbent

Summary By using an external absorbent for removal of nitrogen oxides it is possible to obtain correct hydrogen values if the whole anhydrone filling of the water-absorption tube is heated at 80–90°C during the combustion. Heating is simply done by providing a normal carbon-hydrogen combustion apparatus with a special glass mortar. The effect of the temperature of the anhydrone filling has been studied as well as the effect of the type of compound.

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Zusammenfassung Mit einem Außenabsorptionsmittel für die Entfernung der Stickoxide ist es möglich, richtige Wasserstoffwerte zu bekommen, wenn die ganze Anhydronfüllung des Wasserabsorptionsrührchens auf 80 bis 90° C erwärmt wird. Es ist nur notwendig, die normale Kohlenstoff-Wasserstoff-Verbrennungsapparatur mit einer speziellen Heizgranate zu versehen. Der Einfluß der Temperatur auf die Adsorption an der Anhydronfüllung wurde studiert; ebenso auch der Einfluß des Stickstoffgehalts verschiedener Substanztypen.

     

Partially graphitic micro- and mesoporous carbon microspheres for supercapacitors

Partially graphitic micro-and mesoporous carbon microspheres(GMMCMs)were synthesized using hydrothermal emulsion polymerization followed by KOH activation and catalytic graphitization.The resulting GMMCMs show micro-and mesopores with a specifc surface area of 1113 m2/g,regular spherical shape with diameters of 0.5–1.0 mm and a partially graphitic structure with a low internal resistance of 0.34 V.The graphitic carbons as electrode for supercapacitor exhibit a fast ion-transport and rapid charge–discharge feature,and a high-rate electrochemical performance.The typical GMMCM electrode shows a specifc capacitance of 220 F/g at 1.0 A/g,and 185 F/g under a high current density of20.0 A/g in a 6 mol/L KOH electrolyte.     

Adsorption of proteins on mesoporous carbon adsorbents

A study of the sorption of bull serum albumin (BSA) on carbon adsorbents with different porous structures has shown that, for adsorbents with globular structures, sorption depends on the size of the adsorbent particles. An assumption has been made concerning the nonequilibrium nature of BSA sorption on mesoporous adsorbents associated with irreversible adsorption of the protein and the nonuniform distribution of the adsorbed protein within the adsorbent particles.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1737–1740, August, 1991.     

原位合成负载型MSU系列分子筛

采用原位合成法,使用壬基酚聚氧乙烯醚(Tx-15)和脂肪醇聚氧乙烯醚(AEO-19)做为模板剂,在中性条件下合成W.MSU-1和W-MSU-2介孔分子筛,合成中使用乙酰丙酮(HAcac)作为助剂,考察其对介孔结构的影响,通过X射线衍射仪(XRD)、傅里叶红外光谱仪(FT-IR)、扫描电镜(SEM)、低温N2吸附对样品进行表征.结果表明,加入过渡金属氧化物有助于介孔的形成,助剂的使用提高了孔的结构参数.     

Synthesis of micro- and mesoporous carbon spheres for supercapacitor electrode

Micro- and mesoporous carbon spheres (MMCSs) are synthesized by the polymerization of colloidal silica-entrapped resorcinol/formaldehyde in the presence of ammonia as catalyst, followed by carbonization, sodium hydroxide (NaOH) etching to remove silica template, and potassium hydroxide (KOH) activation. The morphology and microstructure are characterized by scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption–desorption. The results show that a typical sample (denoted as MMCS-3) unites the characteristics of regular spherical shape (uniform diameters of 500 nm), high specific surface area (1,620 m² g^?1), large pore volume (1.037 cm³ g^?1), and combined micropores and mesopores (11.0 nm), which endows MMCS-3 good electrochemical performance. MMCS-3 as supercapacitor electrode shows a specific capacitance of 314 F g^?1 under a current density of 0.5 A g^?1 and low internal resistance of 0.2 Ω in 6 M KOH aqueous solution. The electrochemical capacitance still retains 198 F g^?1 at a high current density of 10 A g^?1. After 500 cycle numbers of galvanostatic charge/discharge at 0.5 A g^?1, MMCS-3 electrode still remains the specific capacitance of 301 F g^?1 with the retention of 96 %. This study highlights the potential of well-designed MMCSs as electrodes for widespread supercapacitor applications.     

Characteristics of molecular sorption on template containing mesoporous molecular sieves of type MCM-41

Template containing materials of type MCM-41 have properties of microporous substances. On absorption into the micropores of such materials the dependence of the characteristic absorption energies on the molecular mass of the sorptive is extreme, and the specific absorption volume decreases with increased molar volume of the sorptive. A model is proposed to explain the peculiarities of the absorption properties of the template containing materials. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine 31 Prospekt Nauki, Kiev 252039, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 35, No. 6, 367–372, November–December, 1999.     

Adsorption and diffusion of molecular nitrogen in single wall carbon nanotubes

Using molecular simulation, the adsorption and self-diffusion of diatomic nitrogen molecules inside a single wall carbon nanotube have been studied over a range of nanotube diameters (8.61-15.66 A) and loadings at temperatures of 100 and 298 K. Nitrogen adsorption energy is found to increase as the nanotube diameter is reduced toward the molecular diameter of nitrogen. A discrete organization of the nitrogen into adsorbed layers is observed at high loadings that follows a regular progression determined primarily by geometric considerations. The formation of an adsorbate core at the center of the nanotube is found to increase the self-diffusion of nitrogen. A "wormlike" phase is found for the adsorbed nitrogen in the (15, 0) carbon nanotube at high loadings and at 100 K.