新型吸附树脂对水中苯的吸附行为

研究表明,苯对人的毒性作用表现在中枢神经系统,65g／m^3的苯可引起广泛的出血导致死亡。反复暴露的低浓度苯主要对血液及造血组织产生毒性作用。根据苯吸入致白血病的流行病学研究数据,采用定量外推法计算出饮用水苯质量浓度为0．01mg/L时终身患癌的超额危险度为10^-5,因此饮用水中的苯的限值为0．01mg／L。因此,有效去除饮水中的苯具有重要的意义。     

非苯乙烯型超高交联树脂对空气、溶液及水面浮苯的吸附性能研究

研究了3种非苯乙烯超高交联吸附树脂对空气、溶液及表面浮苯的吸附滤除性能。结果表明,在C0=1722.6mg/L和C0=181.4mg/m3的水溶液或空气体系中,CMB-CMB-XDC(二氯甲基联苯自聚后与二氯甲基苯共聚)树脂对苯的吸附量与穿透吸附量分别可达874.6mg/g和41.59mg/g;对水面浮苯的吸附在3min内可达4360mg/g以上。新型非苯乙烯树脂吸附速度快、容量大,可经再生反复使用,预期在非极性芳烃废气(水)净化及突发污染事故快速处理领域具有很好的应用前景。     

Effects of micropore size and chemical nature of the surface of carbon adsorbents on the adsorption isotherms of water vapor

Adsorption of benzene and water vapors on activated carbons of various microporous structure was studied. The values of the characteristic energy of adsorption of benzene and water vapors were compared and the affinity coefficients β_H2O for carbons with various degrees of activation were calculated. The values of the β_H2O coefficient for carbons with the same degrees of oxidation remain constant. This makes it possible to use the experimental data on benzene adsorption for prediction of the behavior of microporous activated carbons towards adsorption of water vapor. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2636–2639, December, 2005.     

Adsorption of Some Nitrogen-Containing Compounds and Benzene Derivatives from Aqueous Solutions on Active Carbons

The adsorption from aqueous solutions of benzene derivatives (phenol, benzoic acid, and newly synthesized benzoic acid derivatives containing imidazole heterocycles: hydrazide of 4-(1H-imidazole-1-ylmethyl) benzoic acid and methyl ester of 4-(1H-imidazole-1-ylmethyl)benzoic acid), as well as of imidazole and triazole, on active carbons with various microporous structures is studied. The effect of the nature of adsorbate molecules and the pore sizes of active carbons on the sorption character is analyzed. It is shown that the adsorption from aqueous solutions of the organic derivatives of benzene is determined, on the one hand, by the size of a molecule, and, on the other hand, by its hydration energy.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 3, 2005, pp. 416–420.Original Russian Text Copyright © 2005 by Kharitonova, Krasil’nikova, Vartapetyan, Bulanova.     

吸附树脂的修饰官能团设计及其吸附机理研究

利用AM1半经验计算法计算出用不同官能团修饰的聚苯乙烯型吸附树脂的前线轨道能量值.设计筛选出合适的官能团,根据吸附质的分子尺寸,修饰合成出具有匹配孔径、较大比表面积的吸附树脂.在303K下,测定了它们对不同取代基的酚类化合物的吸附等温线.以Amberlite XAD-4作参照,比较了吸附剂的吸附效果,并阐明了吸附机理.     

Adsorption of surfactants onto acrylic ester resins with different pore size distribution

In this study, a series of acrylic ester resins with different pore size distribution were prepared successfully by varying the type and the amount of pore-forming agents. In order to inves-tigate the adsorption behavior and mechanism of surfactants on acrylic ester resins, three kinds of surfactants were utilized as adsorbates that were sodium 6-dodecyl benzenesulfonate (6-NaDBS), sodium 1-dodecyl benzene sulfonate (1-NaDBS) and sodium 1-dodecyl sulfonate, respectively. It was observed that the surface area was available in a particular pore size and an appropriate pore size of resins appeared to be more important for the adsorption of surfactants. As compared to commercial acrylic ester resins XAD-7 and HP2MG, 50# and 38# resins exhibited more excellent adsorption properties toward 1-NaDBS and 6-NaDBS. The experimental equilibrium data were fitted to the Langmuir, and double-Langmuir models. Two models provided very good fittings for all resins over the temperature range studied. The investigation indicated that electrostatic attraction and hydrogen bond between resins and surfactants were the main forces and had an obvious effect on adsorption proc-ess.     

Comparative analysis of methods for determination of structural characteristics of carbon adsorbents

Experimental data on the equilibrium adsorption of sulfur hexafluoride, methane, carbon dioxide, and benzene on carbon adsorbents of different porosity obtained in a wide pressure range at 298–408 K were analyzed. The adsorption volumes, surface areas, and sizes of slit-shaped pores of the carbons were determined using several independent methods. A method for determination of the adsorption volume from the experimental isotherm of excessive adsorption of gases and the total content equation was proposed. The resulting values are similar to the adsorption volumes calculated from the data for vapors. A new method for the calculation of the adsorbent surface area is described. The method is based on the dependence of the adsorption volume of adsorbent pores on the effective size of adsorbate molecules. A possibility to determine the average size of narrow slit-shaped carbon pores from the difference of the initial heats of adsorption of the gas under study on the carbon black and porous carbon adsorbent is considered. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2219–2227, October, 2005.     

大孔树脂吸附苯和甲苯的平衡及动力学研究

研究并比较了四种大孔吸附树脂对正庆烷中低浓度苯、甲苯的吸附平衡及动力学。Langmuir方程能够良好地描述吸附等温线,由单组分吸附平衡得到的参数;可以很好地预测双组分吸附平衡。动力学研究表明,内扩散过程是决速步,并估算出粒内扩散系数。     

Petroleum resins adsorption onto quartz sand: near infrared (NIR) spectroscopy study

In this paper we have tried to evaluate adsorption parameters of petroleum resins. Near infrared (NIR) spectroscopy is applied for resins bulk concentration evaluation during adsorption process. NIR experimental scheme and parameters are provided. NIR spectra range of 9000-13,000 cm(-1) is chosen. Quartz sand (0.2-0.8 mm fraction) is used as adsorbent; benzene is used as solvent. Different approaches of "NIR spectra-resins concentration" calibration model building are discussed. Partial least squares (PLS) regression method is used. Langmuir model is chosen for experimental data fitting. Combined usage of kinetic and isothermic data gives us ability to evaluate the maximal adsorbed mass density, the equilibrium constant of adsorption, and the rate constants of adsorption (and desorption). The rate constants of resins adsorption and desorption are found to be concentration independent.     

Oscillatory character of deactivation of zeolite catalysts in carbonium ion conversions of hydrocarbons

We have observed damped oscillations of increasing frequency in alkylation of benzene by 1-decene, which we interpret based on surface competition between the benzene and the coke being formed according to a mechanism of alternating inversions of the adsorption layer. We propose a scheme for the inversions in terms of chemical potentials of the adsorbed components. The change in the character of the oscillations is connected with a qualitative change in the coke over time.__________Translated from Teoreticheskaya i Éksperimentalnaya Khimiya, Vol. 41, No. 1, pp. 40–44, January–February, 2005.     

漆酚醛树脂多孔微球对有机物的吸附性能

研究了由悬浮缩聚法制备的多孔漆酚醛树脂微球对乙二胺、二乙烯三胺和茶碱,以及苯、二甲苯、氯仿和四氯化碳等气体的吸附性能,并研究了吸附时间对乙二胺、二乙烯三胺和茶碱吸附性能的影响。结果表明,树脂中的酚羟基因能与胺基产生酸碱之间的作用而吸附乙二胺和二乙烯三胺,其吸附量分别为320.9mg/g、222.2mg/g;该多孔微球亦能吸附有机物气体,尤其对氯仿、四氯化碳的吸附性能较佳,其吸附量分别为248.1mg/g和119.7mg/g。     

Adsorption of benzene from benzene/n-C6 and n-C7 mixture by nano Beta zeolite with different Si/Al ratios

The adsorption of benzene from benzene/n-alkane mixtures was studied by two types of nano Beta zeolite with Si/Al ratios of 11.5 and 24.5. Benzene was adsorbed into benzene/n-hexane and n-heptane mixtures which had 0.5% up to 10% mole fraction of benzene using batch technique in the ambient temperature. The nano Beta zeolite has active sites on its surface, which have interaction with π electron in benzene, and this can increase the heat of adsorption. The Si/Al ratio defines the number of active sites in the zeolite surface and the heat of adsorption. However, an increase in the active sites of Beta zeolite declines the entropy of adsorption. Therefore, free energy of mixing specifies the potential of adsorption in Beta zeolite.As the results indicated in all mixtures, benzene is adsorbed more than n-hexane and n-heptane into the Beta zeolite surface, which suggests that this type of zeolite has a high separation factor (∼50) for benzene in Beta zeolite (Si/Al = 24.5). Also, Beta zeolite with Si/Al = 24.5 had a greater separation factor than Beta zeolite with Si/Al = 11.5 in similar mixtures.     

Comparison of adsorption equilibrium of fructose, glucose and sucrose on potassium gel-type and macroporous sodium ion-exchange resins

Adsorption equilibrium of fructose, glucose and sucrose was evaluated on sulfonated poly(styrene-co-divinylbenzene) cation-exchange resins. Two types of resins were used: potassium (K⁺) gel-type and sodium (Na⁺) macroporous resins. Influence of the cation and effect of the resin structure on adsorption were studied. The adsorption isotherms were determined by the static method in batch mode for mono-component and multi-component sugar mixtures, at 25 and 40 °C, in a range of concentrations between 5 and 250 g L⁻¹. All adsorption isotherms were fitted by a linear model in this range of concentrations. Sugars were adsorbed in both resins by the following order: fructose > glucose > sucrose. Sucrose was more adsorbed in the Na⁺ macroporous resin, glucose was identically adsorbed, and fructose was more adsorbed in the K⁺ gel-type resin. Data obtained from the adsorption of multi-component mixtures as compared to the mono-component ones showed a competitive effect on the adsorption at 25 °C, and a synergetic effect at 40 °C. The temperature increase conducted to a decrease on the adsorption capacity for mono-component sugar mixtures, and to an increase for the multi-component mixtures. Based on the selectivity results, K⁺ gel-type resin seems to be the best choice for the separation of fructose, glucose and sucrose, at 25 °C.     

Benzene and toluene adsorption at low concentration on activated carbon fibres

The present study analyses the preparation of activated carbon fibres (ACFs) by the so-called “physical” activation method with steam or carbon dioxide and their application for benzene and toluene adsorption at low concentration (200 ppmv). ACFs have been scarcely studied for the adsorption of these pollutants at low concentration in gaseous phase, despite their interesting features regarding adsorption kinetics, bed pressure drop, possibility of conformation and others. Our results have shown that the preparation method used is suitable to produce ACFs with high adsorption capacities for benzene and toluene at the low concentration used. The fibre morphology of the ACFs does not enhance their performance, which results to be similar to other non-fibrous activated carbons such as granular, pellets and powders. Such good performance of the ACFs, leading to benzene and toluene adsorption capacities as large as 31 g benzene/100 g ACF or 53 g toluene/100 g ACF, can be explained due to their large volume of narrow micropores (<0.7 nm) developed upon activation and their low content in surface oxygen groups. Our results have also shown very good agreement between the adsorption results derived from dynamic adsorption experiments and from adsorption isotherms. As the relative pressure of the organic compound increases the corresponding fraction of narrow micropore volumes filled by benzene and toluene increases. For a given low and comparable relative pressure, toluene always occupies a larger fraction of narrow micropores than benzene.     

Adsorption of benzene and perfluorobenzene vapor from a flow of moist air by a layer of equilibrium moistened active carbon

The equilibrium adsorption of benzene and perfluorobenzene vapor from a flow of moist air by a layer of active carbon (AC) hydrated to equilibrium were considered. It was ascertained that these organic substances partly displace the water from the adsorptive micropore volume of AC. The equilibrium adsorption values of benzene, perfluorobenzene, and water vapors on AC were calculated. The adsorption of benzene and perfluorobenzene from a flow of moist air by a layer of AC is characterized by volume filling of the micropore adsorption space. This work is part of the research devoted to the study of the dynamics of the adsorption of organic substances from a flow of moist air by a layer of AC hydrated to equilibrium.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1398–1401, August, 1994.     

NiY分子筛表面酸性影响其选择性吸附脱硫性能的机理研究

采用原位红外光谱技术,以噻吩、环己烯和苯为模型探针分子,分别考察单一烃分子在NiY分子筛上的吸附与反应行为以及噻吩与烯烃、芳烃间的竞争吸附和催化反应行为。单一探针分子吸附研究发现,NiY分子筛中与Ni物种相关的Lewis(L)酸位是噻吩的选择性吸附活性位;噻吩和环己烯在NiY分子筛中Brnsted(B)酸位上发生的质子化和低聚反应明显弱于HY分子筛。双探针分子竞争吸附研究发现,环己烯二聚体在NiY中强B酸位上的强化学吸附与噻吩存在显著的竞争吸附行为。另外,苯和噻吩在NiY上的竞争吸附现象在373K时明显减弱。由此,在选择性吸附脱硫过程中,减少吸附剂表面B酸中心可降低烯烃对噻吩的竞争吸附,另外适当提高吸附体系的温度可以有效避免芳烃对噻吩的竞争吸附。     

大孔树脂对磺酸类化合物吸附行为的研究

用4种大孔树脂ND-022，ND-900，NDA-99和NDA-100作为吸附剂，分别对水溶液中甲基磺酸钠、苯磺酸钠、对甲基苯磺酸钠和2-萘磺酸钠等磺酸盐进行吸附．探讨了溶液的初始pH值对不同类型树脂吸附磺酸类物质的影响，并通过动态吸附实验研究了SO4^2-对树脂吸附磺酸盐的影响．实验结果表明，复合功能树脂NDA-99对磺酸类化合物具有良好的吸附性能，且其选择性优于弱碱树脂ND-900，这为进一步研究大孔树脂对磺酸类物质的吸附机理和实际工业应用提供了一定的理论依据。     

Description of the adsorption equilibrium of organic substances absorbed from a flow of moist air by a fixed bed of active carbon moistened to equilibrium

Isotherms of the adsorption of benzene vapor from moist air on active carbon (AC) moistened to equilibrium are obtained from dynamic experiments. The experimental data on the adsorption equilibrium of some organic substances from a flow of moist air by a fixed bed of AC moistened to equilibrium are obtained. The data on the equilibrium adsorption of benzene vapor is analyzed using the Dubinin-Radushkevich equation (the theory of volume filling of micropores). It is revealed that the characteristic adsorption energy of benzene vapor decreases as the filling of the microporous volume with water molecules increases. The characteristic adsorption energy depends on the following factors: polarizability of a substance in the adsorption field created by micropores, the number of carbon atoms in the adsorbate molecules, and parameters of the porous structure. The equation for the calculation of the parameters of equilibrium adsorption of organic substances from moist air on AC moistened to equilibrium are obtained.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 434–438, March, 1995.     

Decreasing the Content of Free Formaldehyde in Urea-Formaldehyde Resins

The possibility of decreasing the content of free formaldehyde in urea-formaldehyde resins by varying the pH and urea-formaldehyde ratio in various synthesis steps was examined. Urea-formaldehyde resins containing no free formaldehyde were prepared.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 4, 2005, pp. 692–694.Original Russian Text Copyright © 2005 by V. Maslosh, Kotova, O. Maslosh.     

Effect of the Structure of Benzo- and Dibenzocrown Ethers on Their Reaction with the Aerosil Surface

The adsorption of 4-substituted benzo- and 5,5′-disubstituted dibenzocrown ethers from benzene by aerosil A-300 was studied. The ethers included a total of 45 compounds with diphenyl oxide, diphenyl, and diphenyl sulfide fragments. Analysis of the Henry coefficients (K_H) and the extent of desorption, the IR spectra of the adsorbed compounds, and the relationship between their structure and adsorption capacity indicated that all structural fragments of the crown ethers studied interact to some extent with aerosil surface fragments. The number of oxygen atoms in the polyether fragment and the size of the macrocycle are the predominant factors. A large, nonadditive increase in K_H is observed in going from pentadentate to hexadentate crown ethers. __________ Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 41, No. 4, pp. 247–251, July–August, 2005.