THE ADSORPTION BEHAVIORS OF 2,6-DICHLOROPHENOL ONTO HYPERCROSSLINKED RESINS

Experimental investigations were conducted on the adsorption characteristics of 2,6-dichlorophenol by two hypercrosslinked resin, ZH-01 and XAD-4. The static adsorption was studied. Within temperature range of 288K～313K, the equilibrium adsorption date was fitted to freundlich adsorption isotherm models to evaluate the model parameters. The enthalpies, free energy,entropy were indicative of an exothermic, a spontaneous and disorder decreasing process. The magnitudes for 2,6-dichlorophenol on ZH-01 showed a chemisorption's transitions while on XAD-4shows a physical adsorption process. The results showed that the ZH-01 adsorbents were better than the Amberlite XAD-4 for removing the 2,6-dichlorophenol in aqueous solutions.     

化学修饰的吸附树脂对2,4,6-三氯苯酚的吸附研究

合成了用邻羧基苯甲酰基或苯甲酰基修饰的新型聚苯乙烯-二乙烯苯吸附树脂ZH-01, ZH-02和ZH-03, 利用瓶点法研究了它们和Amberlite XAD-4对288～318 K下水溶液中2,4,6-三氯苯酚的静态吸附和静态脱附特征以证实吸附质与吸附剂之间存在化学吸附, 并利用半经验分子轨道法(AM1)计算的几种吸附剂和2,4,6-三氯苯酚的前线轨道近似能级进行了解释. 结果表明: 经邻羧基苯甲酰基或苯甲酰基化学修饰后的树脂ZH-01, ZH-02和ZH-03对水溶液中2,4,6-三氯苯酚的吸附过程在合适温度时会使酚羟基和吸附剂表面的羰基发生作用, 对吸附剂进行适当的化学修饰后, 对2,4,6-三氯苯酚的穿透吸附容量均为Amberlite XAD-4树脂的150%, 饱和吸附容量是Amberlite XAD-4树脂的114％～128％.     

ADSORPTION OF CHLOROFORM AND TRICHLOROETHYLENE IN WATER WITH A NEW KIND OF HYPERCROSSLINKED RESINS

In this paper two newly developed hypercrosslinked resins were used to treat micropolluted drinking water and their static and kinetic adsorption were investigated at 293 K. The results show that these two adsorbents are superior to Amberlite XAD-4 for removing chloroform and trichloroethylene in aqueous solutions. The breakthrough capacity and the total capacities from mini-column adsorption studies for chloroform and trichloroethylene on XAD-4, ZH-01 and ZH-00 are calculated respectively under experimental conditions     

苯甲酰基修饰的吸附树脂对对甲苯胺的吸附机理研究

合成了用苯甲酰基修饰的新型吸附树脂ZH-03和ZH-04,同时研究了它们和AmberliteXAD-4对不同温度下水溶液中对甲苯胺的静态吸附和脱附性能,并对吸附机理进行了探讨。结果表明,经化学修饰后的树脂ZH-03和ZH-04对水溶液中对甲苯胺的吸附过程在合适温度时存在化学络合吸附作用,对吸附剂进行苯甲酰基修饰可以提高吸附剂对水溶液中对甲苯胺的吸附容量。     

ADSORPTION OF 2,4-DICHLOROPHENOL IN AQUEOUS SOLUTION ONTO ADSORPTION RESIN MODIFIED BY N-ACETYLANILINE

A hypercrosslinked adsorption resin （ZH-05） modified by N-acetylaniline in the post crosslinking process was prepared. The adsorption properties of ZH-05 toward 2,4-dichlorophenol in comparison with granular activated carbon （GAC） and Amberlite XAD-4 were observed. The present study mainly focuses on the static equilibrium adsorption behaviors, desorption profiles and the proof of chemisorption. The results show that the Langmuir equation can give a perfect fitting to experimental data, and high temperature was favorable for adsorption of 2,4-dichlorophenol on ZH-05. A related equation was used to correlate the amount of chemisorption and the suppositionai chemisorption equilibrium concentration of adsorbate in aqueous solution. The adsorption capacities from different ranges of temperature and the static desorption experiment both reveal the same conclusion, i.e., the adsorption of 2,4-dichlorophenol from water on ZH-05 is a coexistent process of physical adsorption and chemical transition as on GAC.     

A WATER-COMPATIBLE PHENOLIC HYDROXYL MODIFIED POLYSTYRENE AS AN ADSORBENT FOR ADSORBING PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTIONS

1. INTRUDUCTION As most phenolic compounds are extremely toxic at the concentrations discharged into accepting effluents, the removal or destruction of phenolic compounds from such streams has become a significant environmental task [1]. Increasing concern for public health and environmental quality has led to the establishment of limits on the acceptable environmental levels of specific pollutants [2]. Consequently there has been a growing interest in developing and implementing various …     

A WATER—COMPATIBLE PHENOLIC HYDROXYL ODIFIED POLYSTYRENE AS AN ADSORBENT FOR ADSORBING PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTIONS

A water-compatible phenolic hydroxyl modified polystyrene adsorbent (AM-1) for adsorbing and removing phenolic compounds from aqueous solutions was prepared by covalent bonding of phenolic hydroxyl groups to the surface of porous polystyrene-divinylbenzene beads,this resin can be used directly without wetting process.A comparison of the sorption properites of the new resin and Amberlite XAD-4 toward four phenolic compounds,phenol,p-cresol,p-chlorophenol,and p-nitrophenol was made.The capacities of equilibrium adsorption of AM-1 for all four phenolic compounds increased around 20% over that of Amberlite XAD-4,which may be contributed to pheonl hydroxyl group on the surface and the unusual poe distribution.At their dilute solution,the equilibrium adsorption capacities of AM-1 for phenol increased aout 62% over that of Amberlite XAD-4,while equilibrium adsorption capacities of the other three phenolic compounds increased 4-35%,suggesting an advantage of AM-1 over Amberlite XAD-4 in the collection of phenol.Freundlich isotherm equations and isosteric adsorption enthalpies for the four phenolic compunds indicate a physical adsorption process on the Amberlite XAD-4 and AM-1 resins,Column studies for phenol show that AM-1 resin has excellent adsorption and desorption performance.     

A WATER-COMPATIBLE PHENOLIC HYDROXYL MODIFIED POLYSTYRENE AS AN ADSORBENT FOR ADSORBING PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTIONS

A water-compatible phenolic hydroxyl modified polystyrene adsorbent (AM-1) foradsorbing and removing phenolic compounds from aqueous solutions was prepared by covalent bonding of phenolic hydroxyl groups to the surface of porous polystyrene-divinylbenzene beads, this resin can be used directly without wetting process. A comparison of the sorption properties of the new resin and Amberlite XAD-4 toward four phenolic compounds, phenol, p-cresol, p-chlorophenol,and p-nitrophenol was made. The capacities of equilibrium adsorption of AM-l for all four phenolic compounds increased around 20% over that of Amberlite XAD-4, which may be contributed to phenol hydroxyl group on the surface and the unusual pore distributior. At their dilute solution, the equilibrium adsorption capacities of AM-1 for phenol increased about 62% over that of Amberlite X4D-4, while equilibrium adsorption capacities of the other three phenolic compounds increased 4-35%, suggesting an advantage of AM-I over Amberlite XAD-4 in the collection of phenol.Freundlich isotherm equations and isosteric adsorption enthalpies for the four phenolic compounds indicate a physical adsorption process on the Amberlite XAD-4 and AM-I resins. Column studies for phenol show that AM-1 resin has excellent adsorption and desorption performance.     

一种亲水的酚羟基修饰聚苯乙烯树脂对酚类化合物的吸附热力学

在283-323K和研究的浓度范围内,苯酚、对甲苯酚、对氯苯酚和对硝基苯酚在亲水性的酚羟基修饰聚苯乙烯树脂（AM-1）与大孔吸附树脂（Amberlite XAD-4)上平衡吸附数据符合Freundlich吸附等温方程。酚类化合物在AM-1上的吸附容量比在Amberlite XAD-4上的吸附容量增加20%以上,这主要得益于AM-1表面的酚羟基入树脂的微孔结构。在较稀的溶液中AM-1对苯酚的吸附量比AmberliteXAD-4对苯酚的吸附量增加60%,表明AM-1对苯酚有特殊的选择性。Freundlich吸附等温线、相对吸附容量以及等量吸附焓表明,四种酚在两种树脂上的吸附是物理吸附过程。对酚类化合物被两种树脂吸附的吸附焓、自由能、吸附熵也作了测试,并对吸附行为作了合理的解释。     

THERMODYNAMIC STUDY OF ADSORPTION OF PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTION BY A WATER-COMPATIBLE HYPERCROSSLINKED POLYMERIC ADSORBENT

Equilibrium data for the adsorption of phenolic compounds, i.e., phenol, p-cresol, p-chlorophenol and p-nitrophenol from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent (NJ-8) within temperature range of 283-323 K were obtained and correlated with a Freundlich-type of isotherm equation, so that equilibrium constants KF and n were obtained. The capacities of equilibrium adsorption for all the four phenolic compounds on the NJ-8 from aqueous solutions are around 2 times as high as those of Amberlite XAD-4, which may be attributed to the unusual micropore structure and the partial polarity on the network. The values of the enthalpy (always negative) are indicative of an exothermic process, which manifests the adsorption of all the four phenolic compounds on the two polymeric adsorbents to be a process of physical adsorption. The negative values of free energy change show that the solute is more concentrated on the adsorbent than in the bulk solution. The absolute free energy values of adsorption for NJ-8 are always higher than those for Amberlite XAD-4, which indicates that phenolic compounds are preferentially adsorbed on NJ-8. The negative values of the adsorption entropy are consistent with the restricted mobilities of adsorbed molecules of phenolic compounds as compared with the molecules in solution. The adsorption entropy values of phenolic compounds for NJ-8 are lower than those for Amberlite XAD-4, which means the micropores of NJ-8 require more orderly arranged adsorbate.     

ADSORPTION OF BENZOIC ACID AND P-NITROBENZOIC ACID ON A NEW HYPERCROSSLINKED PHENOL GROUP PST ADSORBENT

1.INTRODUCTIONThepolymericadsorbentAmberliteXAD-4isconsideredoneofthemostsuitablepolymericadsorbentsforremovingphenoliccompoundsfromwaterstreams[1,2]becauseitischemicallystable,notsolubleinsolventsandmoreselectiveforaromaticringsduetoitshydrophobicproperties.However,methanol,acetoneoracetonitrile,hastobeusedtoenhancethesurfacecontactbetweenadsorbentandthesolute.DavankovandTsyurupadescribedanewseriesofadsorbents[3,4].Thistechniqueyieldedpolystyrenesorbentsofunusualhypercrosslinkedstructu…     

ADSORPTION OF BENZOIC ACID AND P-NITROBENZOIC ACID ON A NEW HYPERCROSSLINKED PHENOL GROUP PST ADSORBENT

A comparison of the adsorption of benzoic acid and p-nitrobenzoic acid on the new hypercrosslinked polymeric adsorbent AM-I, with that by macroporous Amberlite XAD-4, including the equilibrium adsorption isotherms, the dynamic adsorption behaviors through column and the adsorption thermodynamics were studied. Results show that Freundlich equation gives a fitting adsorption isotherm. The specific surface of AM-l is only 67% of that of Amberlite XAD-4, but the adsorption capacities on AM-1 are much higher about 125%～166% than that on Amberlite XAD-4,which is contributed to the micropore mechanism and polarity. The negative values of the adsorption enthalpy are indicative of an exothermic process. Enthalpy and free energy changes of adsorption both manifest a physic-sorption process. The negative values of the adsorption entropy indicate that the adsorption is well consistent with the restricted mobilities and the configurations of the adsorbed benzoic acid molecules on the surface of studied adsorbents with superficial heterogeneity. Both adsorbents were used in mini-column experiments for adsorbing benzoic acid expecting to elucidate the higher breakthrough adsorption capacity of the new hypercrosslinked polymeric adsorbent AM-1 as compared with that of Amberlite XAD-4.     

ADSORPTION OF 4-METHYLANILINE IN AQUEOUS SOLUTION BY BENZOYL-CONTAINING POLYMERIC ADSORBENTS

New polymeric adsorbents (ZH-02, ZH-03) containing benzoyl group for adsorbing and removing 4-methylaniline from its aqueous solutions were prepared. Studies on the isotherms and the comparison of desorption conditions evidenced through the adsorption of 4-methylaniline in water onto ZH-02 and ZH-03, namely that there are chemisorption‘s transitions at a proper higher temperature. Mini-colunm adsorption studies of 4-methylaniline on XAD-4, ZH-02 and ZH-03 at 288 K show that the breakthrough capacities are 2.39, 2.99 and 3.19 mmol/g and the total capacities are 3.45, 3.92 and 4.35 mmol/g, respectively.     

超高交联吸附树脂对苯甲酸的吸附研究

用新合成的NJ－8超高交联吸附树脂吸附苯甲酸，并与Amberlite XAD-4进行比较。从静态平衡吸附行为及其热力学性质讨论吸附机理。动态穿透吸附实验进一步验证了NJ－8提高交联吸附树脂对苯甲酸的吸附能力约为Amberlite XAD-4的1.6倍。     

Frontal analysis of aqueous phenol solutions in amberlite XAD-4 columns Implications on the operation and design of solid phase extraction systems

Frontal analysis of aqueous phenol solutions in Amberlite XAD-4 columns was carried out at different experimental conditions. Operating variables such as the concentration, pH and ionic strength of the influent, the presence of competitor solutes, the fluid flow-rate and the column length were considered and their effects on the front profile, the phenol breakthrough volume and the equilibrium parameters were determined. The obtained results may explain some contradictory reported data concerning the recovery of hydrophilic compounds in solid phase extraction (SPE) systems using Amberlite XAD-2 or XAD-4 columns. Furthermore, it is demonstrated that the adsorption parameters derived from a frontal analysis in an XAD-4 column are directly transposable to columns of different sizes (at the analytical level). Therefore, the results of this study may also be used for prediction and/or design of a phenol SPE system adapted to a particular problem.     

超高交联吸附树脂吸附对硝基苯乙酮的热力学研究

比较两种超高交联聚苯乙烯吸附树脂NJ-8、AM-1与Amberlite XAD-4(以下简称XAD-4)对对硝基苯乙酮的静态吸附行为，根据吸附等温线研究了吸附热力学性质．在298～318K和研究的浓度范围内，NJ-8，AM-1、XAD-4对对硝基苯乙酮的吸附平衡数据符合Freundlich吸附等温方程．结果表明：吸附为放热过程，适当降低温度有利于吸附．计算了对硝基苯乙酮在NJ-8，AM-1、XAD-4树脂上的吸附焓变、自由能变，吸附熵变．对吸附行为作了合理的解释。     

乙酰苯胺修饰的吸附树脂对苯酚和对氯苯酚的吸附研究

通过Friedel-Crafts后交联及化学修饰反应,合成了乙酰苯胺基修饰的超高交联吸附树脂ZH-05,通过红外光谱(IR)和比表面及孔径分析(BET)对其结构进行表征.以Amberlite XAD-4树脂作为参照,通过等温吸附实验和吸附动力学实验探讨了ZH-05树脂对水溶液中苯酚和对氯苯酚的吸附性能和机理.结果表明,与XAD-4树脂相比,ZH-05树脂对苯酚和对氯苯酚均具有更佳的吸附性能.Langmuir和Freundlich方程均能较好拟合ZH-05树脂对苯酚和对氯苯酚的吸附等温线.ZH-05树脂对苯酚和对氯苯酚的吸附以焓推动的自发物理吸附过程为主,吸附过程放热;吸附符合准一级动力学吸附方程,颗粒内扩散是吸附过程的主要控制步骤.     

Untersuchungen zur adsorptiven anreicherung von elementspuren an adsorberharzen

Summary The mechanisms of the adsorption of neutral compounds, ion associates and metal halogeno-complexes from aqueous solutions on Amberlite XAD-2, XAD-4, XAD-7 and XAD-8 resins are studied in the light of adsorption isotherms and of the pH-dependence of the adsorption. The similarity in the behaviour of adsorption systems to corresponding solvent extraction processes and the regularities of the sorption from aqueous solution on a solid surface are discussed by use of a simple model.

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Herrn Prof. Dr. G. Tölg zum 60. Geburtstag gewidmet

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Teil IV: Fresenius Z Anal Chem (1989) 335:483–488     

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.     

Extraction of Organic Compounds from Aqueous Media by Amberlite XAD Resins

Abstract

Three Amberlite polymeric resins, XAD-2, XAD-4 and XAD-7, were evaluated for extraction efficiency from aqueous media of several organic compounds representing pesticides, polyaromatic hydrocarbons, phenols and phthalate esters. The three resins exhibited different extraction characteristics. The extraction efficiency of the resins was found to be dependent on pH conditions and, on the average, was best at pH7. At this pH the XAD-2 and XAD-4 resins yielded quantitative recoveries in the 90–100% range for most compounds at the 20–200ppb level. Recoveries by XAD-7 resins were lower for several compounds. The recovery of aldrin and o, p DDT under all conditions was relatively low (>68%) and showed a higher degree of variability than that obtained for the other compounds. Alkaline pH conditions were generally unfavourable for the extraction of phenolic compounds but acidification to pH2 was not found to be a necessary step for the quantitative extraction of the phenolic compounds. Acidification to pH2 further led to a decrease in the recovery of most compounds for XAD-4 resins. A combined resin column yielded extraction efficiencies comparable to the XAD-2 column at pH 7, but since the three resins possess different extraction characteristics, a mixture comprising all three is recommended for the preconcentration of organic compounds from environmental water samples containing a wide range of compounds.