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。     

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％.     

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。     

ADSORPTION CHARACTERISTICS OF CHLOROPHENOLS FROM AQUATIC SYSTEMS BY HYPERCROSSLINKED RESINS MODIFIED WITH BENZOYL GROUP

A hypercrosslinked polymeric adsorbent （ZH-03） for adsorbing and removing chlorophenolic compounds from their aqueous solutions was studied, including the static adsorption. The equilibrium adsorption data were fit to Freundlich adsorption isothermic models to evaluate the model parameters. Thermodynamic studies on the adsorption of chlorophenolic compounds on ZH-03 indicated that there were chemisorption transitions for 2,4,6-trichlorophenol and physical adsorption processes for 2-chlorophenol and 2,6-chlorophenol, and ZH-03 showed the homogeneous nature of the adsorbent surface. Column adsorption for chlorophenols wastewater shows the advantages of the ZH-03 adsorbent for adsorbing the following chlorophenolic compounds as 2-chlorophenol, 2,6-dichlorophenol and 2,4,6-trichlorophenol. Sodium hydroxide was used for desorpting chlorophenols from ZH-03 and showed excellent performance.     

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     

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.     

Adsorption behavior of phenolic compounds onto polymeric adsorbents modified with 2-carboxybenzoyl groups

<正>Two hypercrosslinked polymeric adsorbents(ZH-01 and Amberlite XAD-4 resin) were employed to remove three kinds of phenolic compounds including phenol,4-nitrophenol and 2,4-dinitrophenol from aqueous solutions.The study was focused on the static equilibrium adsorption behavior,the column dynamic adsorption and desorption profiles.The Freundlich model gave a perfect fitting to the isotherm data.The adsorbing capacities for these three compounds on ZH-01 were higher than those on Amberlite XAD-4 within the temperature range 288-318 K,which was attributed to the large micropore area and 2-carboxybenzoyl functional groups on the network of ZH-01 resin.The adsorption for phenol and 4- nitrophenol on ZH-01 was a physical adsorption process,while for 2,4-dinitrophenol it was a coexistence process of physical adsorption and chemisorption's transitions.The column test showed the advantages of ZH-01 in the dynamic adsorption processes of phenolic compounds.Being used as the desorption reagent,sodium hydroxide solution showed an excellent performance.     

巯基树脂对金属离子的吸附性能(Ⅱ)

研究了自合成的巯基树脂对重金属离子Ag 、Hg2 、Cr3 的吸附容量、吸附动力学、等温吸附过程等静态吸附性能,影响吸附的因素和吸附机理.结果表明,该树脂对上述3种离子吸附能力强,吸附量分别达6.56mmol/g、3.25mmol/g、2.10mmol/g.树脂对各重金属离子等温吸附在实验浓度范围内符合Langmuir或Freundlich方程.吸附机理研究表明,巯基与金属离子发生了离子交换和配位反应,化学吸附起支配作用;另外树脂对Ag 、Hg2 吸附过程中存在一定的氧化还原现象.     

乙二胺硅胶材料对铜和锌离子的动态吸附

合成了胺基含量为1.35 mmol/g的乙二胺硅胶材料(EDA/SiO2),研究了EDA/SiO2对Cu2+和Zn2+的动态吸附及动态竞争吸附。结果表明,铜溶液流量和初始浓度对材料动态吸附性能有显著影响,随着溶液初始浓度的增大、流速的加快,穿透时间明显缩短。动态吸附实验结果符合Thomas模型,计算结果显示,铜溶液初始浓度由1.99 mmol/L增大至10.00 mmol/L时,模型平衡吸附容量q0从0.272 mmol/g增大至0.476 mmol/g,影响显著;流量对q0影响不显著。溶液流量和初始浓度对吸附速率常数kTh均有影响,随溶液流量增大、初始浓度的降低,速率常数值增大。在单一体系中,EDA/SiO2对Cu2+和Zn2+的工作吸附量分别为0.340和0.127 mmol/g,混合体系的吸附量均小于单一体系中的吸附量,并且对Zn2+的吸附量下降显著,表明EDA/SiO2对Cu2+的吸附能力强于Zn2+。6次循环实验表明,盐酸和氨水可对EDA/SiO2材料实现再生,再生后材料对铜的吸附容量和穿透时间的下降幅度不大,可重复使用。     

CMC-Na/DETA-B62型蛇笼树脂对金属离子的吸附性能

本文研究了自合成的蛇笼型螯合树脂-二乙烯三胺交联甘油环氧树脂/羰甲基纤维素体系对Cd^2 ,Pb^2 ,Fe^2 的吸附量，吸附动力学，等温吸附过程等静态吸附性能，同时研究了pH值等因素对吸附性能的影响。实验结果表明，该树脂对Cd^2 具有较强的吸附选择性，能在Cd^2 ,Pb^2 ,Fe^2 3种离子共存时选择吸附Cd^2 ，其选择性系数分别为Kcd^2 /pb^2 =3.77,Kcd^2 /Fe^2 =9.61。该树脂对上述3种离子的吸附量可分别达4.00,1.06,0.42mmol/g。该类树脂可用于含重金属离子污水的处理和金属离子的分离等方面。     

螯合树脂研究 ⅩⅩⅤ．环硫（氧）氯丙烷与三（二）乙醇胺钠盐反应合成硫氮杂冠醚型树脂

环硫（氧）氯丙烷，不经过预先聚合，直接与三（二）乙醇胶的钠盐进行反应，制得交联的硫、氮杂冠醚型螫合树脂．提出了可能的反应机理．还研究了这类树脂对一些贵金属和非贵金属离子的吸附性能．比较了相应的含硫、氮和氧氮树脂吸附性能的差别．总的说来合硫氮的树脂对贵金属的吸附性能优于含氧、氮树脂．     

聚乙烯醇接枝微粒对黄酮类物质的吸附特性

以硅胶表面接枝有聚乙烯醇(PVA)的接枝微粒PVA/SiO₂为固体吸附剂, 对槲皮素和芦丁2种黄酮类化合物进行了吸附研究, 结果表明, 由于接枝微粒PVA/SiO₂表面含有高密度的羟基, 使得该接枝微粒与黄酮类化合物分子之间可形成多位点的常规氢键和π型氢键, 溶剂的竞争吸附对黄酮化合物的吸附容量产生很大的影响. 以弱极性的1,2-二氯乙烷(DCE)为溶剂时, 几乎不存在溶剂的竞争吸附, 槲皮素和芦丁具有最高的吸附容量, 分别为0.32 mmol/g(96 mg/g)和0.23 mmol/g(140 mg/g); 而在质子溶剂乙醇中, 强烈的溶剂竞争吸附使两者的吸附容量降至0.22 mmol/g(65 mg/g)和0.14 mmol/g(87 mg/g). 升高温度会减弱氢键作用, 甚至使氢键断裂, 导致吸附容量减小. 质子溶剂中电解质的存在, 对吸附作用产生负性影响. 功能微粒PVA/SiO₂对黄酮类化合物的吸附为放热过程, 且为焓驱动的吸附过程.     

新型含氮、硫纤维素螯合树脂的合成及其吸附性能

将稻壳纤维素的氯化产物(CDC)分别与水合肼、乙二胺、二乙烯三胺、三乙烯四胺、丁二胺和己二胺反应,合成了6种含氮纤维素螯合树脂(ADC-1～ADC-6);在碱性条件下用环硫氯丙烷交联ADC合成了6种新型含氮、硫纤维素螯合树脂(TADC-1～TADC-6),研究了合成条件和ADC,TADC树脂对金属离子的吸附性能.结果表明,ADC树脂对Cu²⁺,Cr³⁺,Ni²⁺,Hg²⁺,Zn²⁺等离子有较好的吸附性,对Hg²⁺吸附容量可达0.5mmol/g左右;TADC树脂对Ag⁺,Cu²⁺,Hg²⁺等离子有较好的吸附性,对Hg²⁺和Ag⁺吸附容量可达1.1mmol/g和1.9mmol/g左右;强酸性条件下,ADC和TADC树脂的吸附容量都降低,它们对金属离子的吸附顺序分别为Hg²⁺>Cu²⁺>Ni²⁺和Ag⁺>Hg²⁺>Cu²⁺,树脂用10%的氨水解吸附可重复使用.     

Preparation of activated carbons and their adsorption properties for greenhouse gases: CH4 and CO2

Three kinds of activated carbons were prepared using coconut-shells as carbon precursors and characterized by XRD, FT-IR and texture property test. The results indicate that the prepared activated carbons were mainly amorphous and only a few impurity groups were adsorbed on their surfaces. The texture property test reveals that the activated carbons displayed different texture properties, especially the micropore size distribution. The adsorption capacities of the activated carbons were investigated by adsorbing CH4, CO2, N2 and O2 at 25 ?C in the pressure range of 0-200 kPa. The results reveal that all the activated carbons had high CO2 adsorption capacity, one of which had the highest CO2 adsorption value of 2.55 mmol/g at 200 kPa. And the highest adsorption capacity for CH4 of the activated carbons can reach 1.93 mmol/g at 200 kPa. In the pressure range of 0-200 kPa, the adsorption capacities for N2 and O2 were increased linearly with the change of pressure and K-AC is an excellent adsorbent towards the adsorption separation of greenhouse gases.     

胶原纤维固化杨梅单宁对UO22+的吸附

以胶原纤维为基质，通过交联剂将杨梅单宁固化在胶原纤维上制备吸附材料．实验结果表明，所制备的吸附材料对UO2^2 具有很强的吸附能力，当溶液中UO2^2 的浓度为7．5mmol/L、pH为5．0时，吸附容量达到1．19mmol UO2^2 /g(283．3mgU／g)．UO2^2 在固化杨梅单宁上的吸附平衡符合Freurldlich方程，升高温度，平衡吸附量增大。吸附动力学可用拟二级速度方程来描述，由动力学方程计算得到的平衡吸附量与实测的平衡吸附量基本相同，误差在4％以内．pH值对吸附过程有较大影响，适宜的pH在5-8之间。所制备的吸附材料具有优良的柱动力学特性，床层的有效利用率高；经解吸后的吸附柱其吸附性能基本不变。     

ADSORPTION BEHAVIORS OF Pt（IV） AND Pd（II） ON POLYMERIC ESTER THIOUREA RESIN

Polymeric ester thiourea resin （PDTU-I） is a new kind of chelating resin with functional atoms S, N and O, so it is an excellent adsorbent for noble metal ions. In batch testes, the adsorption capacities of PDTU-I for Pt（IV） and Pd（II） increase with the increase of contact time, temperature and initial concentration of metal ions. The adsorption data fit Boyd＇s diffusion equation of liquid film, Langmuir adsorption isotherm and Freundlich adsorption isotherm. The maximum adsorption capacities calculated by Langmuir equation are 2.54mmol/g for Pt（IV） and 4.88mmol/g for Pd（II）. According to FTIR and XPS results, functional groups of PDTU-I coordinate with noble metal ions in the adsorption process.     

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.     

二乙烯三胺接枝壳聚糖的合成与表征

以壳聚糖为基体,与环氧氯丙烷反应,然后与二乙烯三胺反应,制得二乙烯三胺接枝壳聚糖(CTSN)。经红外光谱FTIR分析和X-射线衍射分析表征了结构,在活化及接枝过程中未破坏壳聚糖中的吡喃苷六元环结构,其结构与预期结构吻合。初步研究了它对Pd2 、Ag 、Ni2 、Cu2 、Co2 、Cd2 金属离子的静态吸附性能,试验结果表明,CTSN对金属离子有较大的吸附容量,对Pd2 、Ag 离子的吸附容量分别为1.29mmol/g和1.15mmol/g。     

笼形聚偕胺肟树脂的研究──酸处理树脂吸附H_2PdCl_4

考查了无机酸、羧酸和酚类化合物处理的笼形聚偕胺肟树脂吸附酸性溶液中H_2PdCl_4的能力，其中H_3BO_3/ACAO、HSCH_2CO_2H/ACAO和p－NH_2C_6H_4H/ACAO树脂对H_2PdCl_4的吸附容量分别是2．023、2．368和2．083mmol/g-R或215、252和222mgPd／g－R。优于相同条件下的碱处理树脂（BCAO吸附容量为1．828mmol/g-R）。研究了吸附动力学，讨论了吸附机理。     

酚醛基质苯并咪唑螯合树脂的合成及配位性能

通过1,4-对苯二酚二缩水甘油醚和2,2′-二苯并咪唑二乙胺反应合成四苯并咪唑单体(TBMZ),经甲醛等缩合生成酚醛聚合物为基质的苯并咪唑螯合树脂(PTBMZs)。 新型螯合树脂配基含量达2.1~3.02 mmol/g。新树脂及其单体结构经13C核磁共振谱、FT-IR红外光谱、元素分析和DSC分析确证。 测定了Cu2+、Ni2+、Zn2+、Cd2+和Co2+氯化物在pH值为1.0~6.0的缓冲溶液中的配位容量。 实验结果表明,该类螯合树脂对Cu2+有高度的选择性,KCuX≥4.3非竞争条件下,PTBMZ-1的最大配位容量为1.15 mmol/g(pH=5.0,Cu2+),PTBMZ-2的最大配位容量为0.97 mmol/g(pH=5.0,Cu2+),配基占有率分别为35.9%,33.4%。 PTBMZ-1树脂对Cu2+吸附较快,t1/2=21 min。 电子顺磁共振谱和FT-IR光谱分析结果表明,形成n(金属离子)∶n(配基)=1∶2的螯合物为主。