SORPTION OF PHENOL ONTO GEL—TYPE CROSSLINKED POLYSTYRENEISOCYANURIC ACID RESIN

Spherical crosslinked polystyrene-isocyanuric acid resin was synthesized by reaction of chloromethylated polystryene with isocyanuric acid.The sorption isotherms of phenol from aqueous solution and cyclohexane solution onto the resin were measured.It is of interest to notice that the resin sorbed phenol efficiently though its specific surface area was 0 and did not swell in water,and the sorption capactity from aqueous solution was close to that of phenol onto XAD-4 at the same equilibrium concentration.Sorption enthalpies calculated from the isotherms according to the Clausius-Clapeyron equation were -21-25kJ/mol and -39-41kJ/mol respectively.These values impled that the sorption processes were based on hydrogen bonding.In addition.the details of the hydrogen bonding between the active sites of the resin and phenol were suggested.     

大孔交联聚(对乙烯基苄基苯基醚)树脂对苯酚的吸附机理

由氯甲基化聚苯乙烯合成了大孔交联聚(对乙烯基苄基苯基醚)树脂(简称为苯基醚树脂), 测定了其对正己烷和水中苯酚的吸附等温线, 计算了吸附焓. 同时, 比较了聚(对乙烯基苄甲醚)、苯基醚树脂、聚(对乙烯基苄基对硝基苯基醚)和聚(对乙烯基苄基对甲基苯基醚)对正己烷中苯酚的吸附性能以及氯甲基化聚苯乙烯和苯基醚树脂对水中苯酚、2,3,5-三甲基苯酚和对硝基甲苯的吸附性能. 结果表明, 苯基醚树脂是通过氢键吸附正己烷溶液中苯酚的, 而其对水中苯酚的吸附是基于氢键和疏水作用的协同.     

ADSORPTION OF CAFFEINE BY HYDROGEN DONATING ADSORBENTS BASED ON HYDROGEN BONDING

The adsorption isotherms of caffeine from aqueous solution onto three hydrogen donating adsorbents-hydroxypolystyrene,polystryene-azo-pyrogallol,and D72 resin-were measured.The adsorption enthalpies calculated from the isotherms according to the Clausisu-Clapeyron equation were -24-36kJ/mol,-32-37kJ/mol,and -19-24kJ/mol respectively.These values implied that the adsorption processes were based on hydrogen bonding.Furthermore.the mechanism of the adsorption of caffeine onto D72 resin was studied by IR spectra and the small molecular model experiments,and the results showed that the adsorption of caffeine onto hydrogen donating adsorbents was based on hydrogen bonding.     

ADSORPTION OF CAFFEINE BY HYDROGEN DONATING ADSORBENTS BASED ON HYDROGEN BONDING

1. INTRODUCTIONHydrogen bonding is a useful mechanism for adsorptive separation. The low enemy of thisbond ensures reversibility, while the directionality and the short range of this bond conferselectivity. The adsorption of hydrogen donating solutes onto an adsorbent capable of acceptinghydrogenedmberlite XAD-7, an adsorbent consisted of polycarboxylic ester--based onhydrogen bonding has been examined in detail 11-41. However, the adsorption of hydrogenaccepting solutes onto polymeric a…     

聚(N-对乙烯基苄基二甲胺)树脂对苯酚的吸附性能

采用二甲胺为功能化试剂,化学修饰氯甲基化苯乙烯-二乙烯基苯共聚物合成了大孔交联聚(N-对乙烯基苄基二甲胺)树脂,测得树脂的氯含量由4.2mmol/g降低到0.24mmol/g,树脂的弱碱交换量为4.0mmol/g,说明氯甲基化苯乙烯-二乙烯基苯共聚物发生胺化反应完全。在水溶液中,测定了大孔交联聚(N-对乙烯基苄基二甲胺)树脂对苯酚的吸附等温线,发现吸附平衡数据符合Freundlich等温吸附方程,相关系数大于0.99。计算得到在吸附量为15、20和25mg/g时,等量吸附焓在-20.81~-30.74kJ/mol范围内,吸附自由能和吸附熵均小于0,说明吸附过程中存在氢键作用,吸附是自发、混乱度变小的过程。比较树脂对水溶液中苯酚、对硝基苯酚和对硝基甲苯的吸附性能以及树脂对水、环己烷、乙醇和乙酸乙酯溶液中苯酚的吸附性能,进一步说明大孔交联聚(N-对乙烯基苄基二甲胺)树脂对水溶液中苯酚的吸附是基于疏水作用和氢键作用协同的机理。     

氧化叔胺树脂的合成及其对苯酚的吸附性能研究

将D301树脂的叔胺基氧化，合成了大孔交联氧化叔胺树脂．比较D301树脂与氧化叔胺树脂对正己烷溶液中和水溶液苯酚的吸附性能，发现氧化叔胺树脂对苯酚的吸附量比D301树脂的有明显的增加．为弄清吸附量增加的原因，根据氧化叔胺树脂对正己烷溶液中苯酚的吸附等温线，利用热力学函数关系计算了等量吸附焓、吸附Gibbs自由能和吸附熵，发现叔胺树脂氧化后，与苯酚的相互作用和吸附的自发倾向增强，但吸附过程仍为氢键吸附．     

D301树脂对酚类的吸附热力学研究

测定D301树脂对环己烷溶液中苯酚的吸附等温线，利用热力学函数关系计算了等量吸附焓，吸附自由能和吸附熵，等量吸附焓在30kJ/mol-35kJ/mol之间，推测吸附过程为氢键吸附。比较D301树脂对水溶液和环己烷溶液中苯酚的吸附性能，及D301树脂对环己烷溶液中苯酚和邻硝苯酚的吸附性能，进一步讨论了D301树脂对酚类物质吸附中的氢键作用。     

MODIFICATION OF X-5 RESIN AND ADSORPTION PROPERTY OF THE MODIFIED RESINS

1. INTRODUCTION Adsorption capacity and selectivity are improved when some ion exchange groups or hydrogen bonding acceptor or/and donors are introduced into common polymeric adsorbents [1~5]. R. F. Shi et al have synthesized a series of bifunctional ads…     

MODIFICATION OF X-5 RESIN AND ADSORPTION PROPERTY OF THE MODIFIED RESINS

Three polymeric adsorbents with hydrogen bonding acceptors, methylamine,N-methyl-acetamide and aminotri(hydroxymethyl)methane modified resins are synthesized fromchloromethylated X-5 resin. Adsorption isotherms of phenol and theophylline onto the three modifiedresins and the original X-5 resin from aqueous solution are measured. The results show thatadsorption of compounds with hydrogen bonding donor onto methylamine and N-methylacetamidemodified resins is enhanced as compared with that onto X-5 resin, and adsorption mechanismbetween the adsorbents and the adsorbates is mainly based on hydrogen bonding and hydrophobicinteraction. While adsorption of compounds with hydrogen bonding donor ontoaminotri(hydroxymethyl)methane modified resin is lowered as compared with that onto X-5 resin, andadsorption mechanism between the adsorbent and the adsorbates is mainly based on hydrophobicinteraction.     

Synthesis, characterization, and adsorption behavior of aniline modified polystyrene resin for phenol in hexane and in aqueous solution

Macroporous crosslinked poly(p-vinylbenzylaniline) (PVBA) was synthesized and its adsorption isotherms for phenol in hexane and in aqueous solution were comparatively measured. It was shown that the adsorption isotherms in hexane were straight lines and passed through the origin, whereas those in aqueous solution could be simulated by Freundlich isotherms. Adsorption enthalpies of phenol onto PVBA were calculated, and the results indicated that the adsorption was an exothermic process. Comparison of the adsorption behaviors of PVBA, poly(p-vinylbenzylmethylamine) (PVBMA), and poly(p-vinylbenzyl-p-nitroaniline) (PVBNA) for phenol in hexane suggested that hydrogen bonding and pi-pi stacking were primarily responsible for the adsorption, the nitrogen atom and benzene ring of PVBA acted as hydrogen bonding acceptors and formed hydrogen bonding with the hydrogen atom of hydroxyl group of phenol. Investigation of the adsorption mechanism in aqueous solution revealed that hydrogen bonding and hydrophobic interaction were the main driving forces.     

聚(对乙烯基苄基己内酰胺)树脂对非水体系中苯酚的吸附热力学

测定了聚（对乙烯基苄基己内酰胺）吸附树脂对正庚烷溶液中苯酚的吸附等温线,发现吸附等温线符合Freundlich等温吸附方程,相关系数大于0．99．根据热力学函数关系计算了等量吸附焓、Gibbs吸附自由能和吸附熵,等量吸附焓在30～40kJ／mol之间,推测吸附过程为氢键吸附．通过比较树脂对正庚烷中苯酚和邻硝基苯酚的吸附性能的差别,进一步论证了树脂对非水体系中酚类物质的吸附是基于氢键作用的机理．同时,聚（对乙烯基苄基己内酰胺）树脂对正庚烷溶液中苯酚的吸附相对水溶液中苯酚的吸附有更低的吸附焓变、吸附自由能变和吸附熵变．     

凝胶型交联聚苯乙烯—异氰尿酸树酯对酚类物质的吸附机理研究

由氯甲基化低交联聚苯乙烯和异氰尿酸在三乙胺作用下反应,制得了凝胶型交联聚苯乙烯－异氰尿酸树脂,测定了该树脂对苯酚和间苯二酚在不同温度下的吸附等温线,依据Clapeyron0Clausius方程从吸附等温线计算出了吸附热,从热力学的角度论证了树脂是基于氢键键合的疏水作用而吸附苯酚和间苯二酚的。     

大孔交联聚(对乙烯基苄基苯胺)树脂对苯酚的吸附

由氯甲基化聚苯乙烯合成了大孔交联聚(对乙烯基苄基苯胺)树脂, 测定了其对正己烷和水中苯酚的吸附等温线, 计算了吸附焓. 结果表明, 苯胺基树脂主要是通过氢键吸附正己烷中苯酚的, 树脂负载的功能基氮原子和苯环都作为氢键受体与苯酚的羟基氢原子形成氢键, 而其对水中苯酚的吸附是基于氢键和疏水作用.     

ADSORPTION OF TANNIN FROM AQUEOUS SOLUTION ONTO MACROPOROUS CROSSLINKED POLY（N—VINYL—ACETAMIDE）VIA HYDROGEN BONDING

A Strongly hydrophilic hydrogen-bonding adsorbent-macroporous crosslinked Poly(Nvinyl-acetamide),which contain both hydrogen bond acceptor and donator,was synthesized.Adsorption mechanism and dynamic adsorption of tannin from aqueous solution onto the adsorbent were investigated.Most of the differntial adsorption heats for various adsorption capacities calculated from the adsorption isotherms according to Clapeyron-Clausius equation lay in the range of hydrogen bond energy(8-50J/mol).Adsorption properties of the adsorbent were studied in detail.These results revealed a hydrogen bonding mechanism of the adsorption of tannin from aqueous solution onto the adsorbent.The result of the dynamic adsorption of tanning with the initial concentration under 600mg/L showed that the adsorption rate of tannin exceeded 90% when the flow rate was 3BV/h and the effluent volume reached 100BV.Therefore,the developed hydrogen-bonding adsorbent-macroporous crosslinked poly(N-vinyl-acetamide)-is an excellent adsorbent to remove tannin from extract of natural products,and has great value in application.     

Isotherm analysis of phenol adsorption on polymeric adsorbents from nonaqueous solution

Macroporous poly(methyl methacrylate-co-divinylbenzene) (PMMA), interpenetrating polymer adsorbent based on poly(styrene-co-divinylbenzene) (PS) and poly(methyl methacrylate-co-divinylbenzene) (PMMA/PS), and macroporous cross-linked poly(N-p-vinylbenzyl acetylamide) (PVBA) were prepared for the adsorption of phenol from cyclohexane. The sorption isotherms of phenol on the three polymeric adsorbents were measured and fitted to Langmuir and Freundlich isotherms. It is shown that the Langmuir isotherm, which is based on a homogeneous surface model, is unsuitable to describe the sorption of phenol on the adsorbents from nonaqueous solution and the Freundlich equation fits the tested three adsorption systems well. The isosteric enthalpy was quantitatively correlated with the fractional loading for the sorption of phenol onto the three polymeric adsorbents. The surface energetic heterogeneity patterns of the adsorbents were described with functions of isosteric enthalpy. The results showed that the tested three polymeric adsorbents exhibited different surface energetic heterogeneity patterns. The initial isosteric enthalpy of phenol sorption on polymeric adsorbent has to do with the surface chemical composition and is free from the pore structure of the polymeric adsorbent matrix. Forming hydrogen bonds between phenol molecules and adsorbent is the main driving force of phenol sorption onto PVBA and PMMA adsorbent from nonaqueous solution. When phenol is adsorbed on PMMA/PS, pi-pi interaction resulting from the stacking of the benzene rings of the adsorbed phenol molecules and the pendant benzene ring of adsorbent is involved.     

Sorption of traces of silver ions onto polyurethane foam from acidic solution

The sorption of traces of silver ions onto polyurethane foam (PUF) has been investigated in detail. Maximum sorption of silver (K(d)=6109 cm(3) g(-1), %sorption>97.5%) has been achieved from 1 M nitric acid solution after equilibrating silver ions with approximately 29 mg PUF for 20 min. The kinetics and thermodynamics of the sorption of silver ions onto PUF have also been studied. The sorption of silver ions onto PUF follows a first-order rate equation, which results as 0.177 min(-1). The variation of sorption with temperature yields the values of DeltaH=-56.1+/-3.2 kJ mol(-1), DeltaS=-159.7+/-10.5 J mol(-1) K(-1) and DeltaG=-8.68+/-0.09 kJ mol(-1) at 298 K with a correlation factor gamma=0.9919. The sorption data were subjected to different sorption isotherms. The sorption follows Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The values of Langmuir isotherms Q=65.4+/-1.5 mumol g(-1) and b=(4.79+/-1.16)x10(4) dm(3) mol(-1) have been evaluated for Langmuir sorption constants, whereas the Freundlich sorption isotherm gives the value 1/n=0.12+/-0.02 and A=0.15+/-0.03 mmol g(-1). The D-R parameters computed were beta=-0.000817+/-0.000206 mol(2) kJ(-2), X(m)=76.8+/-8.7 mumol g(-1) and E=24.7+/-3.2 kJ mol(-1). The influence of common ions on the sorption was also examined. It is observed that Hg(II), thiourea, Al(III), thiocyanate and thiosulphate reduce the sorption, whereas Cu(II), citrate and acetate ions enhance the sorption significantly. It can be concluded that PUF may be used to remove traces of silver ions from its very dilute solutions or for its preconcentration from aqueous acidic solutions.     

ADSORPTION OF PHENOL IN NON—AQUEOUS SYSTEM BASED ON HYDROGEN—BONDING

Two hydrogen-bonding adsorbents-macroporous crosslinked poly(P-nitrostyrene)and poly(p-vinylbenzyl amide)-were synthesized,and the adsorption property of phenol from cyclohexane solution onto the adsorbents was studied,The differential adsorption heasts for varied adsorption capacities calculated from the adsorption isotherms according to the Claperyron-Clausius equation lay in the range of hydrogen bond energy (8-50kJ/mol),The adsorption capaccity of o-nitrophenol in cyclohexane was moch less than that of phenol under the same condition.The adsorption capacity of phenol from cyclohexane onto polyacrylonitrile was much less than that onto poly(p-nitrostyrene)or poly(p-vinylbenzyl amide),All these results revealed that adsorption of phenol from cyclohexane by poly(p-nitrostyrene) or poly(p-vinylbenzyl amide)is based on hydrogen-bonding.     

ADSORPTION OF PHENOL IN NON-AQUEOUS SYSTEM BASED ON HYDROGEN-BONDING

1 INTRODUCTIONHydrogen-bonding adsorbents are functional polymers for adsorption and separation via theformation of hydrogen bond between the adsorbentS and adsorbates. Because hydrogen bond is astrong intermolecular (or intramolecular) force, hydrogen-bonding adsorbents have strong potentto adsorbing adsorbates with which can form hydrogen bond. In our previous work, three seriesof hydrogen-bonding adsorbents have been studied, which were adsorbents with hydrogendonator, adsorbentS with …     

SORPTION OF PHENOL AND P-NITROPHENOL ONTO A WEAKLY ANION EXCHANGER： XPS ANALYSIS AND MECHANISM

X-ray photoelectron spectroscopy (XPS ) was adopted to elucidate sorption mechanism of phenol and p-nitrophenol onto a weakly anion exchanger D301. The distribution of specific forms of tertiary amino group on D301 was obtained and effect of free tertiary amino group on phenol sorption onto D301 was discussed. The result indicated that the percent of the protonated tertiary amine group on polymeric matrix was much lower than the reference compound N,N-dimethylbenzylamine at an identical pH value in solution due to the much lower activity degree of hydrogen ion in inner resin phase than in the external solution. Less free amino group on D301 results in less sorption capacity of phenol and p-nitrophenol in an acidic solution. Under the experimental conditions both phenol sorption onto D301 can be explained as solid extraction and the distribution coefficient varies linearly with the content of free amino group on D301.     

SORPTION OF PHENOL AND P-NITROPHENOL ONTO A WEAKLY ANION EXCHANGER: XPS ANALYSIS AND MECHANISM

1. INTRODUCTION Phenolic compounds are pollutants encountered frequently in water system. Some of them, such as phenol and p-nitrophenol, have been listed as priority pollutants in many countries. How to remove them completely from the polluted water is of significant concern to environmental scientists. Up to now many technologies such as biodegradation, oxidation and adsorption are available to remove phenolic compounds from the receiving water [1~4]. In the past two decadesphenol sorpt…