Characterization of novel adsorbents for radiostrontium reduction in foods

Distribution coefficients, pH dependence, isotherms, kinetics and breakthrough curves of Sr binding have been measured on several types of adsorbents (carbons modified with titanium silicate, crystalline titanium silicate, mixed titanium-manganese oxide, and synthetic zeolites A4 and P) from different water solutions. It is concluded that acid-base properties of the adsorbent is very important for Sr binding. Titanium silicate based adsorbents had reduced chemical stability in an artificial food fluid below pH 2, the mixed titanium manganese oxide below pH 6, zeolite A4 below pH 5 and zeolite P below pH 7. Consideration is given to the feasibility of the adsorbents for food decontamination.     

Adsorbent filled membranes for gas separation. Part 1. Improvement of the gas separation properties of polymeric membranes by incorporation of microporous adsorbents

The effect of the introduction of specific adsorbents on the gas separation properties of polymeric membranes has been studied. For this purpose both carbon molecular sieves and zeolites are considered. The results show that zeolites such as silicate-1, 13X and KY improve to a large extent the separation properties of poorly selective rubbery polymers towards a mixture of carbon dioxide/methane. Some of the filled rubbery polymers achieve intrinsic separation properties comparable to cellulose acetate, polysulfone or polyethersulfone. However, zeolite 5A leads to a decrease in permeability and an unchanged selectivity. This is due to the impermeable character of these particles, i.e. carbon dioxide molecules cannot diffuse through the porous structure under the conditions applied. Using silicate-1 also results in an improvement of the oxygen/nitrogen separation properties which is mainly due to a kinetic effect. Carbon molecular sieves do not improve the separation performances or only to a very small extent. This is caused by a mainly dead-end (not interconnected) porous structure which is inherent to their manufacturing process.     

Nonlinear gas chromatography as a way of studying inhomogeneous sorbents

A way of organizing and processing the results from gas–chromatographic experiments to obtain chromatographic retention characteristics for a fixed concentration of sorbate in the gas phase or on the surface of the sorbent is proposed and substantiated. The suitability and expediency of such retention characteristics for describing the sorption properties of inhomogenous sorbents is demonstrated using a wide variety of adsorbents of different natures (activated carbons, swelling and nonswelling polymers, silicas and their silver derivatives) as examples.

     

纳米多级孔分子筛：简短的综述

分子筛是一种三维微孔结构的硅铝酸盐晶体,具有灵活多变的骨架和组成、较高的物理和水热稳定性、无毒、高比表面积、离子可交换性以及很低的成本等特点,因而在油品精制、石油化学、农业、水和污水处理等众多领域中用作离子交换剂、催化剂和吸附剂。尽管分子筛的应用是基于其本身的微孔结构,但微孔也导致体积较大的反应物和产物分子的传质阻力高。通过制备纳米尺度和多级孔结构的分子筛等多种手段可克服常规分子筛所具有的传质限制。人们已经开发了多种方法制备了新型的分子筛材料,并考察了它们在各种催化反应和吸附反应中的性能。在反应体系中采用这种多级孔的纳米分子筛,有可能提高催化剂的使用寿命和催化性能,抑制积碳和失活。本综述概述了多级孔分子筛和纳米分子筛的高性能及其合成方法的最新进展,讨论了每个合成方法的优缺点,简述了纳米分子筛和二级孔结构分子筛的催化应用,并与常规分子筛进行了比较。     

Comparison of nutshell granular activated carbons to commercial adsorbents for the purge-and-trap gas chromatographic analysis of volatile organic compounds

Granular activated carbons (GACs) made from agricultural by-products were investigated as adsorbents for short path thermal desorption gas chromatographic analysis of selected polar and nonpolar organic compounds. GACs made from macadamia nut, black walnut and hazelnut shells were compared to four commercially available adsorbents, namely, Tenax TA, Carboxen 569, Carbosieve SIII and coconut charcoal for their properties in purge-and-trap analysis. Adsorption values and breakthrough volumes were calculated for compounds from C3 and C6-C10. GACs derived from macadamia nut shells were found to adsorb and desorb between 80% (benzene) and 277% (ethylbenzene) more acetone (C3), benzene (C6), toluene (C7), ethyl- (C8), n-propyl- (C9), or sec.-butylbenzenes (C10) purged from water at the 100 ppb level than the commercial adsorbents tested.     

Inverse GC Investigation of the Adsorption of Thiophenic Compounds on Zeolites

Inverse gas chromatography (IGC) has been used to examine the adsorption of organo-sulfur compounds on various zeolites. Results obtained were used to explain the behaviour of these materials as adsorbents for ultra-deep desulfurisation of fuels. The model compounds chosen were thiophene and 2,5-dimethylthiophene, with zeolite adsorbents NaX, HX, NaY and HY. Zeolite NaY showed the largest adsorption capacity. Adsorption isotherms in the gas phase are not representative of saturation adsorption in the liquid phase. However, the heat of adsorption and the specific interaction parameter were found to be well correlated to the strength and the selectivity of adsorption in the liquid phase by the different zeolites. The main conclusion of this work is that IGC is a useful tool for preliminary comparison of different adsorbents for the removal of sulfur compounds from fuels.     

Electroanalytical Applications of Microporous Zeolites and Mesoporous (Organo)Silicas: Recent Trends

Microporous zeolites and ordered mesoporous (organo)silicas have been widely used as electrode modifiers because of their attractive properties (ion exchange and size selectivity of zeolites, well ordered nanoreactors containing a high number of widely accessible active centers in mesoporous (organo)silicas). These properties have been intelligently combined to selected redox processes to improve the response of the resulting modified electrodes or to design novel electrochemical detection schemes. This up‐to‐date review provides the recent advances made in the electroanalytical applications of zeolite modified electrodes and discusses the interest of ordered mesoporous (organo)silica materials in electroanalysis.     

Fixed bed adsorption of benzothiophene over zeolites with faujasite structure

This work addresses the adsorption of benzothiophene (BT), as a model heterocyclic and aromatic sulphur compound present in road fuels, over agglomerated zeolites with faujasite structure. Several adsorbents based on zeolites with FAU structure have been prepared with different Si/Al molar ratios and exchange cations and then agglomerated. The influence of the zeolite basicity has been studied, both in equilibrium and dynamic liquid phase adsorption experiments. Basicity of the adsorbent increased as the Si/Al molar ratio and the electronegativity of the exchange cation decreased. In equilibrium experiments, the affinity towards the adsorbent increased as the Si/Al molar ratio decreased, showing the highest affinity for exchanged low silica X zeolites with medium basicity (A-KLSX-02). Dynamic experiments showed that the less zeolite basicity, the higher fractional bed utilization and adsorption capacity at breakthrough time. Besides, zeolites with high basicity did not reach the equilibrium capacity due to the low diffusivity of BT into the micropores. Thermogravimetric analyses of the spent adsorbents showed a stronger BT adsorption onto the more basic zeolites. As main conclusion, adsorbents with medium basicity could present the best performance in fuel desulphurization due to their high affinity with sulphur compounds, although diffusion problems should be taken into account.     

Specific features of the separation of inorganic and organic compounds on alumina modified with fluorinated polyimide

Highly fluorinated thermally stable polyimide is synthesized and used to modify alumina. The effects of polyimide concentration (10 and 15 wt %) and thermal treatment conditions on the adsorption and chromatographic properties of the prepared adsorbents are studied by the low-temperature adsorption of nitrogen and gas chromatography on packed columns. The adsorbents prepared possess mesoporous structures and ensure the selective separation of permanent gases and hydrocarbons on their simultaneous presence.     

Gas chromatography on carbon adsorbents: Characterization, systematization, and practical applications to catalytic studies

The results of the characterization of graphite-like carbon materials by X-ray diffraction, electron microscopy, and adsorption and gas chromatography are discussed. All carbon-containing adsorbents are systematized in accordance with their structure and adsorption characteristics, chemical nature, and chromatographic surface properties. The adsorption and gas-chromatographic properties of carbons and other adsorbents are compared. The purposeful regulation of the chemical nature of carbon adsorbent surfaces is considered; it significantly extended the gas-chromatographic capabilities of carbon-containing materials, in particular, in studies of the product composition of catalytic reactions.     

沸石分子筛材料在消除挥发性有机化合物反应中的吸附与催化性能

作为空气污染物的主要成分之一,挥发性有机化合物(VOCs)会极大地破坏生态环境并损害人体健康。在众多消除 VOCs的方法中,吸附法由于操作简单、成本低廉的优势而在工业上得以广泛应用。催化燃烧法则因去除效率高,适用范围广且无二次污染等优点被认为是 VOCs消除最有效的手段之一。
　　目前,活性炭是最常用的 VOCs吸附剂,但存在再生困难、抗湿性差、易燃等诸多问题。与活性炭等常规吸附剂相比,沸石分子筛作为 VOCs吸附剂其主要优势在于：(1)沸石分子筛的疏水性可调,通过调控分子筛骨架的硅铝比可以调节分子筛的亲疏水性,高硅铝比的沸石分子筛有着优异的疏水性能,从而可以有效降低在一定湿度条件下水对 VOCs分子的竞争吸附;(2)均一的孔径分布可以有效地进行分子识别,从而使吸附剂对VOCs的选择性吸附性大大提高;(3)沸石分子筛一般由硅铝构成,本身不可燃且水热稳定性好,因此能够与微波加热等其他手段相结合以降低吸附剂重生能耗,提高操作安全性;(4)沸石分子筛比表面积大,吸附容量高,是作为蜂窝转轮吸附技术中吸附剂的理想材料,而该技术是目前工业大规模消除VOCs的研究热点。因此,沸石分子筛由于其独特的性质,被视为一种简单高效、选择性好的VOCs吸附剂。现阶段,催化燃烧VOCs所使用的催化剂常用金属氧化物作为载体,但是金属氧化物比表面积相对较小且孔道结构不均一,因此严重影响了催化剂对VOCs的催化燃烧效率,限制了催化燃烧活性的提高。而与金属氧化物载体相比,沸石分子筛材料具有均一的孔道结构以及相对较大的比表面积等优点,而将具有较好吸附选择性和吸附容量的沸石分子筛作为载体,负载活性组分后可以实现催化剂催化燃烧性能的显著提高,从而成为VOCs催化燃烧的理想催化剂。
　　本文综述了目前沸石分子筛材料作为吸附剂和催化剂载体的负载型催化剂消除各类VOCs的研究进展。对于沸石分子筛作为VOCs吸附剂,我们小结了影响其吸附容量和吸附选择性的因素,发现分子筛的孔道大小和阳离子类型与VOCs的吸附情况密切相关。在此基础上,进一步简单介绍了分子筛蜂窝吸附转轮技术的研究现状。对于沸石分子筛作为催化剂载体,我们总结了其用于各类VOCs催化燃烧的研究情况,如烷烃类、芳烃类和醛类等。探究了催化性能的影响因素及相应的催化机理,发现分子筛的孔道结构、阳离子类型、硅铝比等都会显著影响沸石分子筛负载型催化剂的催化活性。最后,探讨了沸石分子筛应用于VOCs消除目前所存在的问题,同时展望了该领域未来的研究和发展方向。     

Adsorption of organic pollutants over microporous solids investigated by microcalorimetry techniques

This work is focused on the gas and liquid-phase adsorption of pollutants: propanol, 2-butanone, phenol and nicotine onto zeolites (H-BETA, H-ZSM-5, H-MCM-22, and clinoptilolite). Textural properties and origin of zeolites were taken into account as criteria of adsorbents selection. The aldehyde and the ketone were adsorbed in the gas phase using microcalorimetry linked to a volumetric line to evaluate adsorption. Adsorptions in water were carried out for phenol and nicotine and the evolved heats during adsorption were measured by a differential heat flow reaction calorimeter with stirring. Results are discussed in relation with the pore sizes and various interactions which could occur between the adsorbent and the adsorbate.     

分子筛材料在小分子吸附分离中的应用

吸附分离技术与工艺在工业上具有重要意义. 常见的吸附剂包括沸石分子筛、 金属有机框架材料、 活性炭等材料. 分子筛具有比表面积大、 稳定性高、 生产成本低等优势, 可以满足吸附分离技术中高效、 节能和环保的需求, 是一种非常有应用前景的小分子混合物分离吸附剂. 本文综合评述了吸附分离领域中常用的吸附剂材料的特点和吸附分离机理与评价方法, 总结了分子筛在空气分离、 烃类分离、 二氧化碳吸附、 芳香硫化物脱除、 一氧化碳吸附、 氮氧化物吸附、 氢气储存吸附及氢同位素分离等领域的应用, 并对基于分子筛膜的小分子混合物分离现状进行了介绍. 此外, 本文还系统分析了分子筛对不同混合物的吸附分离性能与其拓扑结构、 骨架组成及改性方法之间的关系, 并对未来的研究前景进行了展望.     

Gas chromatographic analysis of the products of catalytic reduction of nitric oxide by ammonia

The behavior of small amounts of nitric oxide in the presence of ammonia and excess oxygen on adsorbents of different textures was studied by gas chromatography. A scheme for the gas chromatographic analyses of the products of catalytic reduction of nitric oxide by ammonia and the catalytic oxidation of ammonia by oxygen was suggested. The scheme makes it possible to prevent chemical reactions between components of the gas mixture analyzed during the accumulation of the products and their analysis, to exclude the partial or complete adsorption of NO on microporous adsorbents, and to monitor the content of components at a level of 500 ppm and lower.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2508–2513, October, 1996.     

改性Y型分子筛对FCC汽油脱硫性能的研究

采用液相离子交换法制备了Cu(I)Y、NiY、CeY分子筛,利用XRD、ICP/MS、N₂吸附脱附等技术对其物化性质进行了表征,使用固定床技术和色谱-硫化学发光检测(SCD)偶联技术系统考查了改性Y分子筛对FCC汽油的选择性吸附脱硫性能,着重探讨了FCC汽油选择性吸附脱硫过程中硫化物的脱除规律。结果表明,不同金属阳离子改性的Y分子筛对FCC汽油中不同硫化物选择性有所不同,对CeY分子筛:2-甲基-5-乙基噻吩<噻吩3硫醇< C₂噻吩<2或3-甲基噻吩<苯并噻吩<3,4-二甲基噻吩≈2,3,4-三甲基噻吩<四氢噻吩,而NiY与Cu(I)Y选择性相同:C₃硫醇<2-甲基-5-乙基噻吩2噻吩<2或3-甲基噻吩<噻吩<苯并噻吩<3,4-二甲基噻吩≈2,3,4-三甲基噻吩<四氢噻吩,改性Y分子筛对噻吩及小分子烷基取代噻吩类硫化物的选择性较差。     

Specific features of the absorption of divalent manganese ions from aqueous solutions by zeolites

Sorption properties of natural zeolites from various Russia’s deposits for the Mn²⁺ ion were studied in comparison with various industrial adsorbents and some minerals. It was demonstrated that the equilibrium sorption capacity of these materials can be raised by their Na⁺-modification. The natural zeolites are advantageous at low Mn²⁺ ion concentrations over synthetic cation exchangers and activated carbons. The sorption capacity of the natural zeolites grows with increasing temperature.     

Gas chromatography study of the adsorption of refrigerating fluids on microporous solid adsorbents

Adsorption isotherms for microporous solids have been determined by elution gas chromatography. Adsorbents are of ;molecular sieves' type; their utilization in affinity thermal machines is envisaged. These machines work in a relatively high domain of pressure for the adsorbate, so the chromatographic technique is generally inadequate for their study. The possibility of increasing the maximal pressures reached by chromatography has been investigated in relation with: the carrier gas flow rate, the length and width of columns, the injected adsorbate mass. This study has been made for different solid adsorbents (zeolite 4A and 13X, silica gel), in different shapes (small stick, pellet, powder), and with different adsorbates (water, methanol, ethanol). In the most favorable conditions that have been derived, the qualities of the chromatographic method, rapidity, simplicity and large range of measures, appear well fitted to the search of this kind of isotherms which does not require a great accuracy.     

Characterization of synthetic adsorbents with fine particle sizes for preparative-scale chromatographic separation

Synthetic adsorbents with fine particle sizes (15-30 microm) were manufactured. These adsorbents are made of poly(styrenedivinylbenzene) and polymethacrylate, and have the same chemical structure as analytical- (5-10 microm) or industrial- (200-600 microm) grade synthetic adsorbents. Both of them have very similar porous structure to those of analytical or industrial sizes, so that they can adsorb compounds of various molecular masses. Chromatographic separation characteristics of newly manufactured fine-particle grades of synthetic adsorbents were evaluated and compared to those of analytical or industrial adsorbents. Reasonable dependency of separation performance on particle size of synthetic adsorbents was obtained. Hydraulic properties of fine-grade adsorbents had also been measured in view of column operations. Furthermore, scalability and applicability of these adsorbents for preparative-scale chromatographic separation of bioactive compounds was evaluated. Separation of soybean isoflavones and tea catechin derivatives had revealed that fine-grade synthetic adsorbents could be well applied with scalability under the same elution conditions used for analytical use. Scalability up to a 22400-fold loading amount was achieved from a small column packed with analytical-grade adsorbent used for method development to a scale-up preparative column packed with fine-grade adsorbent used for preparative purification. These results showed the usefulness of the fine-grade synthetic adsorbents for more precise purification of bioactive compounds, including pharmaceuticals and functional food additives with higher recovery.     

Modification of glass capillary gas chromatographic columns by alkylation of the glass surface with pentafluorobenzyl bromide

Summary Glass surface alkylation with pentafluorobenzyl (PFB) bromide yields glass capillary gas chromatographic columns with modified retention characteristics. Glass-alkylated OV-225 columns have been tested in the analysis of PFB fluoroacetate, and the substantial increase in retention time of this highly volatile compound was found to improve the precision of analysis. PFB-alkylated columns should prove generally useful in gas chromatographic analysis of small relative molecular mass compounds.     

Needs and trends in rational synthesis of zeolitic materials

Zeolites are an important class of materials which are widely used in industry as catalysts, adsorbents and ion-exchangers. Their superior properties are closely related to their unique porous framework structure, as well as composition and morphology. The ever-growing needs for zeolitic materials in applications inspire us to think of the rational synthesis of zeolites with desired structures and properties. However, rationalization of zeolitic materials remains one of the most challenging issues in the zeolite research field due to their unclear formation mechanism. Despite this, many efforts have been devoted to synthesize zeolites in a more rational way. In this tutorial review, first, we demonstrate how the geometrical characteristics of zeolite frameworks affect the catalytic performances of the resulting materials; then, we present recent advances in synthetic innovations to target materials, and we further highlight the developments in computer simulations toward ab initio design and synthesis; finally, the future perspective on the rational synthesis of zeolitic materials with desired functions and structures will be described.