Adsorption of water on zeolites of different types

We have investigated the interaction of water with Na⁺-ion exchanged zeolites of different structures (LTA, FAU, ERI, MOR and MFI) by means of temperature-programmed desorption (TPD). The non-isothermal desorption of water shows, depending on the zeolite type, differently structured desorption profiles. In every case the profiles have, however, two main ranges. Using a regularization method, desorption energy distribution functions have been calculated. The desorption energy distributions between 42–60 kJ mol^?1, which can be attributed to a non-specific interaction of water, show two clearly distinguished energy ranges. The water desorption behaviour of this range correlates with the electronegativity of the zeolites and the average charge of the lattice oxygen atoms calculated by means of the electronegativity equalization method (EEM). The part of the desorption energy distributions in the range of 60–90 kJ mol^?1, reflecting interactions of water with Na⁺ cations, shows two more or less pronounced maxima. In agreement with vibrational spectroscopic studies in the far infrared region, it may be concluded that all samples under study possess at least two different cation sites.     

Synthesis and application of colloidal nanocrystals of the MFI-type zeolites

The colloidal dispersion containing the nanosized zeolites with the MFI topology has been successfully prepared. A pre-aging process of the mother gel at 80°C for 24 h before the crystallization was important for the formation of the nanosized zeolites. We have also found that silicalite-1 nanocrystals av. 62 nm in size were formed by the addition of acidic amino acids into the mother gel. The particle size of the zeolites can be controlled ranging from 62 to 530 nm by changing the amount of water, aging process, crystallization time and temperature and the addition of organic molecules. Furthermore, nanosized titanium silicalite-1 (TS-1) with the size of 50-130 nm has been successfully synthesized by the addition of a Ti source into the synthesis gel of the silicalite-1 nanocrystals. The nanosized TS-1 exhibits a higher catalytic activity in the epoxidation of cyclohexene than the microsized ones. Finally, we demonstrate the preparation of thin films of the silicalite-1 and TS-1 nanocrystals onto a silicon substrate by a dip-coating technique.     

In situ monitoring of desilication of MFI-type zeolites in alkaline medium

In situ pH and Attenuated Total Reflection (ATR) infrared techniques have been successfully applied in order to gain insights into the dissolution process connected to mesopore formation occurring upon alkaline treatment of ZSM-5 zeolites. Online pH measurements reveal a similar consumption of OH(-) ions in the initial stage of the reaction independent of the Si/Al ratio of the zeolite. In view of the greatly different mesoporosity development, the extraction of polymeric silica entities is anticipated, its structure depending on the framework Si/Al ratio. In agreement, ATR-IR experiments have confirmed dissolution of polymeric silicon-containing species that in the course of the alkaline treatment disintegrate into smaller entities. A direct relation between the type of porosity developed and the process of silicon extraction as measured in the liquid phase cannot be drawn.     

Molecular screening of alcohol and polyol adsorption onto MFI-type zeolites

Configurational-bias grand canonical Monte Carlo (CB-GCMC) simulations and expanded ensemble (EE)-CB-GCMC simulations were performed to obtain adsorption isotherms of alcohols and polyols onto MFI-type zeolites from the gas phase and aqueous solution. In adsorption from both phases, Henry's constants and heats of adsorption at infinite dilution for straight-chain alcohols, diols, and triols in silicalite-1 are found to increase, and the saturation loadings decrease with increasing carbon number. Adsorption of straight-chain alcohols is more favorable than that of branched-chain alcohols. Henry's constants increase with increasing number of hydroxyl groups for gas-phase adsorption but decrease for adsorption from aqueous solution due to the strong hydrophilic solvent effect of water. The location of the hydroxyls does not affect significantly the adsorption from aqueous solution but does so in gas-phase adsorption. The saturation pressures for gas-phase adsorption decrease by orders of magnitude from the alcohols to the triols. Nonframework cations increase the adsorption of the small alcohols by an order magnitude at low concentrations (<1 mg/mL), but result in only a factor of 2 increase for larger alcohols like butanol at low concentrations (<0.03 mg/mL), and then decrease the adsorption at higher concentrations. Overall, the simulated results are in reasonable agreement with available experimental data.     

Adsorption energy of water vapor on high-silica and pure-silica zeolites

The high heats of water adsorption on silicalite with the adsorption of 0.4 mmole/g result from an additional interaction with the silicalite OH groups, while the high heats of water adsorption on NaZSM-5 with the adsorption of 0.5 mmole/g result from an additional strong interaction with 0.5 mmole/g sodium cations. Tetraaqua complexes are formed about these sodium cations at the channel intersection sites in NaZSM-5. The first water molecule adds with an energy of about 100 kJ/mole, while the other three molecules add with the same energy of 56 ± 2 kJ/mole. The water adsorption isotherms on silicalite and NaZSM-5 are completely and satisfactorily described by two- and three-term VMOT equations.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2862–2864, December, 1989.     

同晶外延生长法合成MFI型核壳复合分子筛

采用二次热液结晶法,以四丙基氢氧化铵水溶液预处理过的低硅ZSM-5分子筛为晶核,通过调控p H值、水量和晶化时间等二次结晶条件,在晶核上外延生长了高硅ZSM-5壳,制备了MFI/MFI核壳型复合分子筛。通过X射线衍射、扫描电镜、能量色散谱仪、透射电子显微镜、N2吸附-脱附和NH3-程序升温脱附等手段表征了所合成的核壳分子筛的晶体结构、表面形态及核/壳界面,并对它们的结构参数以及酸性进行了初步评估。结果表明,核壳复合分子筛的壳层由多层200 nm的MFI沸石晶粒组成;高硅ZSM-5分子筛壳层的生成,引入了介孔结构,显著增大了外比表面积;同时,核壳结构的形成降低了复合分子筛酸性和外表面的酸密度,但增加了弱酸量。当二次晶化母液p H值为8.5,H2O/SO2物质的量比为30,晶化时间为24 h时,高硅分子筛壳层更易可控生长。     

Elastic behavior of MFI-type zeolites: Compressibility of H-ZSM-5 in penetrating and non-penetrating media

The elastic behavior of H-ZSM-5 was investigated by in-situ synchrotron X-ray powder diffraction, using both silicone oil (s.o.) and (16:3:1) methanol:ethanol:water (m.e.w.) as “non-penetrating” and “penetrating” pressure transmitting media, respectively. From P_amb to 6.2 GPa the volume reduction observed in s.o. is 16.6%. This testifies that H-ZSM-5 is one of the most flexible microporous materials up to now compressed in s.o. Volume reduction observed in m.e.w. up to 7.6 GPa is 14.6%. A strong increase in the total electron number of the extraframework system, due to the penetration of water/alcohol molecules in the pores, is observed in m.e.w. This effect is the largest up to now observed in zeolites undergoing this phenomenon without cell volume expansion. The higher compressibility in s.o. than in m.e.w. can be ascribed to the penetration of the extra-water/alcohol molecules, which stiffen the structure and contrast the channel deformations.     

Adsorption characteristics of some zeolites

Attempts have been made to correlate the Si/Al atom ratio, the degree of crystallinity, crystallite dimensions and the mean diameter of crystalline particles with the relative adsorption affinity index (RAI). Differences in molecular sieving effect and in some diffusional aspects between traditional zeolites and the new shape-selective ZSM are revealed by the adsorption characteristics of cyclohexane, benzene, toluene, neopentane and xylenes.

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Si/Al , , , (RAI). - ZSM , , , .

     

Adsorption tests of water vapor on synthetic zeolites for an atmospheric detritiation dryer

Tritiated hydrogen and hydrocarbon are usually oxidized to a tritiated water vapor to make the tritium adsorbable and easy to treat. The adsorption system as a subsequent process plays an important role in a tritium recovery and its performance affects the overall detritiation efficiency significantly. In order to quantify an adsorbent's utilization and its dynamic capacity against an inlet humidity and a flow rate, a series of quantitative tests based on the breakthrough behavior were carried out in an isothermal fixed bed of synthetic zeolites such as molecular sieve 4A, 5A, 13X and mordenite. The amount of water vapor breaking during the adsorption was estimated to provide a breakthrough capacity at the various inlet flow rates and humidity conditions. The molecular sieve 13X exhibited a better adsorption performance at a given bed height. The existence of CO₂ in a humid atmosphere had a minor effect on the net adsorption capacity and the hydrogen isotopic water (HDO) in the elution stream showed a delayed behavior during a thermal desorption.     

Adsorption study of dealuminated HY zeolites

Pyridine (py) and acetic acid (Ac) adsorption on dealuminated HY zeolites with Al content in the range of 3.9–58 per unit cell (U.C.) was studied at 553 K by a flow-gravimetric technique. The ratio of the number of adsorbed py and Ac molecules to the number of Al atoms was plotted as a function of the Al content. The plot passes through a maximum for py and a minimum for Ac. The extrema are at about 30 Al/U.C.

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(Py) (Ac) HY Al 3,9–58 (U.C.) 553 . Py Ac Al Al. Py Ac. 30 Al/U.C..

     

Adsorption of mixtures of vapors on zeolites

Conclusions The adsorption of a binary mixture of vapors[CHCl₃-(C₂H₅)₂O]on zeolite NaX was studied at 60 and 72°. The thermodynamic properties of the adsorption solutions formed were described.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1309–1311, July, 1964     

Adsorption of radioactive iodide by natural zeolites

The vacancy transfer probabilities of K to L₁, L₂ and L₃ shell were measured with a new method. The L X-ray yields of targets excited by 59.5 keV incident photons, i.e., above the K edge of elements, were detected with a high-resolution Si(Li) detector. For comparison with the experimental results, theoretical calculations were made using data available on radiative and radiationless transitions. The radiative transition values of these elements were taken from the relativistic Hartree-Slater model, those of the radiationless transitions from the Dirac-Hartree-Slater model. The measured values were found to be in good agreement with theoretical ones. The h_KLi (i = 1, 2, 3) values were calculated by measuring the L_1x, L_2x and L_3x X-ray production cross-sections.     

乙炔、丙烯在多种分子筛上的吸附和脱附性质

在80℃下研究了ZSM5、13X、Y、MOR、5A、SAPO34等多种分子筛和常见载体上乙炔和丙烯的吸附和脱附性能。结果表明,乙炔和丙烯在SiO2、γ-Al2O3上不吸附,而与分子筛存在较强的相互作用。对于同类型的分子筛,两者的饱和吸附量均随分子筛硅铝比的增大而减小。在同一种分子筛上,以摩尔计的丙烯吸附量均明显高于乙炔。在80℃改性β分子筛上乙炔和丙烯饱和吸附量可分别达到0.11mmol/g和4.89mmol/g,该结果明显高于文献报道的结果。     

Adsorption behavior of organic halides on zeolites

The adsorption behavior and the differential heat of adsorption of chloroform were measured on various types of zeolite (faujasite, ZSM-5 and mordenite) with different Si/Al ratios. The results reveal that saturated adsorption is almost proportional to the micropore volume and is independent of the micropore structure or the Si/Al ratio. However, initial heat of adsorption was the highest (90 kJ mol⁻¹) on the mordenite with low Si/Al ratio, while low on the faujasite with high Si/Al ratio or ZSM-5 (50 kJ mol⁻¹). Change in initial heat of adsorption with Si/Al ratio is small for faujasite or mordenite and large for ZSM-5. For the comparison, trichloroethylene adsorption behavior of zeolite was also investigated. Saturated adsorption of trichloroethylene was almost constant for all types of zeolite, while the faujasite with high Si/Al ratio exhibited an adsorption isotherm of type V in BDDT (Brunauer, Deming, Deming and Teller) classification. The tendencies of heat of immersion are similar to the results of the initial heat of adsorption.     

沸石的碱性催化:乙醇双分子缩合反应

本文首次发现在碱性沸石上乙醇参数发生以正丁醇为主产物的双分子缩合反应。在所研究的催化剂中, 含铷的LiX沸石表现出最高的反应选择性。研究表明, 这一碱化反应的活性与催化剂的酸碱性质密切相关。催化剂的碱性对反应起决定作用,但催化剂的碱性太强则不利于反应。     

Adsorption and inhibition effects of tribenzylamine in ethanol+water mixtures on a mercury electrode

The adsorption properties of tribenzylamine on mercury were studied using electrocapillary and C-E curves measurements in ethanol+water mixtures in various supporting electrolytes. With the increase of ethanol content a sudden decrease of the differential capacity to a minimum value was observed followed at negative potentials by an abrupt increase of the capacity to the value of the supporting electrolyte. These transition potentials were dependent on the percentage of ethanol and on the concentration of tribenzylamine.The observed behaviour was attributed to a two-dimensional association of the adsorbate in the double layer. The quantitative evaluation of the results fulfilled the theoretical relations for association in the film. Another support for this idea was obtained from the inhibition effect of tribenzylamine on several fast charge transfer reactions at the DME. The potential of the sudden decrease of the limiting diffusion controlled current was very near to the positive transition potential at the C-E curves. The inhibition effect decreased with ethanol content.