氨化松香基交联聚合树脂对水中诺氟沙星的吸附性能

将松香基功能高分子进行胺基化得到氨化松香基交联聚合树脂(aminated rosin-based resin,ARBR),采用扫描电镜(SEM)、红外光谱(FTIR)和比表面分析(BET)对ARBR进行了表征.利用ARBR树脂对水中诺氟沙星(NOR)吸附去除,系统研究了树脂投加量、pH值、接触时间、离子强度和温度等因素对NOR吸附性能的影响.结果表明,pH在2.0~6.0范围内,ABRA对NOR的去除效果随着溶液pH值的增加而升高,在8~10之间则呈现下降趋势;共存离子溶液的存在对ARBR去除NOR的行为总体上表现为促进作用.ARBR对水中诺氟沙星的吸附动力学过程符合准二级动力学模型.Langmuir等温吸附模型可较好地描述ARBR对水中NOR的吸附过程,理论最大吸附量为30.29 mg·g~(-1)(pH 6.0、20℃).吸附热力学分析表明,ARBR对水中诺氟沙星的吸附是自发吸热的过程,属于物理吸附,其吸附机制主要为氢键与静电作用.脱附再生实验发现,0.1 mol·L~(-1)HCl溶液效果明显优于其它脱附液,进一步确证了氢键在吸附中的主导作用;经过5次吸附-脱附循环后,对NOR仍具有稳定的吸附性能,可再生循环使用.对比了不同类型商品化树脂,ARBR具有较好的吸附效果.该研究结果拓展了松香高值化的应用研究领域,对开发松香在环境微污染控制中的应用具有理论指导意义.     

Removal of perfluorinated surfactants from wastewater by adsorption and ion exchange——Influence of material properties,sorption mechanism and modeling

Perfluorooctane sulfonate(PFOS) has attracted increasing concern in recent years due to its world-wide distribution, persistence, bioaccumulation and potential toxicity. The influence of sorbent properties on the adsorptive elimination of PFOS from wastewater by activated carbons, polymer adsorbents and anion exchange resins was investigated with regard to their isotherms and kinetics. The batch and column tests were combined with physicochemical characterization methods, e.g., N_2 physisorption, mercury porosimetry, infrared spectroscopy, differential scanning calorimetry, titrations, as well as modeling. Sorption kinetics was successfully modelled applying the linear driving force(LDF) approach for surface diffusion after introducing a load dependency of the mass transfer coefficient βs.The big difference in the initial mass transfer coefficient βs,0, when non-functionalized adsorbents and ion-exchange resins are compared, suggests that the presence of functional groups impedes the intraparticle mass transport. The more functional groups a resin possesses and the longer the alkyl moieties are the bigger is the decrease in sorption rate.But the selectivity for PFOS sorption is increasing when the character of the functional groups becomes more hydrophobic. Accordingly, ion exchange and hydrophobic interaction were found to be involved in the sorption processes on resins, while PFOS is only physisorptively bound to activated carbons and polymer adsorbents. In agreement with the different adsorption mechanisms, resins possess higher total sorption capacities than adsorbents. Hence, the latter ones are rendered more effective in PFOS elimination at concentrations in the low μg/L range, due to a less pronounced convex curvature of the sorption isotherm in this concentration range.     

Capability of cation exchange technology to remove proven N-nitrosodimethylamine precursors

N-nitrosodimethylamine(NDMA) precursors consist of a positively charged dimethylamine group and a non-polar moiety, which inspired us to develop a targeted cation exchange technology to remove NDMA precursors. In this study, we tested the removal of two representative NDMA precursors, dimethylamine(DMA) and ranitidine(RNTD), by strong acidic cation exchange resin. The results showed that pH greatly affected the exchange efficiency, with high removal(DMA 78% and RNTD 94%) observed at pH pk_a-1 when the molar ratio of exchange capacity to precursor was 4. The exchange order was obtained as follows: Ca~(2+) Mg~(2+) RNTD~+ K~+ DMA~+ NH_4~+ Na~+. The partition coefficient of DMA~+to Na~+was 1.41 ± 0.26, while that of RNTD~+to Na~+was 12.1 ± 1.9. The pseudo second-order equation fitted the cation exchange kinetics well. Bivalent inorganic cations such as Ca~(2+)were found to have a notable effect on NA precursor removal in softening column test. Besides DMA and RNTD, cation exchange process also worked well for removing other 7 model NDMA precursors. Overall, NDMA precursor removal can be an added benefit of making use of cation exchange water softening processes.     

氯化磁性凹土树脂的制备与表征研究

利用表面负载的方法将有机化磁性凹土与苯乙烯、二乙烯苯等制备磁性凹土树脂;对磁性凹土树脂进行氯甲基化改性,制备出氯化磁性凹土树脂.表征了样品的形貌、结构以及表面积,研究了树脂对天然有机物(腐殖酸)的吸附性能.结果表明:氯化后的磁性凹土树脂的比表面积是原有的1.9倍,对附腐殖酸的饱和吸附能力也从原有的41.84 mg/g提高到了51.02 mg/g,这表明改性后的树脂增强了其对腐殖酸的去除能力.     

用AGMP-1M阴离子交换树脂直接分离Zn的实验方法改进

针对原有用于铜、铁、锌同位素分析的提纯步骤方法,我们专门对锌的提纯进行了改进,即在1mol/LHCl的介质条件下,采用200~400目AGMP-1M树脂提纯锌,大大简化了锌的提纯方法。在改进的实验条件下,地质样品的回收率接近100%;标准溶液在离子交换分离前后同位素组成一致,表明分离前后无Zn同位素分馏;全流程Zn的空白小于0.7ng/mL。此法可作为用于高精度Zn同位素分析的前处理方法。     

树脂基固态胺吸附剂室温下对低浓度CO2的吸附性能研究

以大孔甲基丙烯酸酯吸附树脂为载体,聚乙烯亚胺(PEI)为有机胺,采用液相浸渍法制备出固态胺吸附剂,并研究了其在室温下对低浓度CO2的吸附行为.同时,利用氮气吸附、热重分析和扫描电镜表征了材料的物理化学性质,并采用热重法和固定床吸附法考察了材料的CO2吸附性能.结果表明,大孔树脂担载50%PEI(质量分数)时吸附性能最佳,对纯CO2的最大吸附量为175 mg·g-1;CO2的吸附行为由扩散动力学与吸附热力学共同决定,低温有利于提高吸附容量;吸附剂对400 ppm~15%浓度的CO2都具有优异的动态吸附性能,其中对400 ppm CO2的吸附量达到86 mg·g-1,对15%CO2的吸附量达到150 mg·g-1;湿度对吸附起促进作用,相对湿度为10%时,对400 ppm CO2的吸附量提高至139mg·g-1;吸附剂具有优异的循环性能,具有直接空气捕集CO2的潜力.     

同源地人工湖水体和底泥中有机物组成及有机结构的分析研究

采用XAD-8大孔吸附树脂对水体和底泥中的有机物进行组分分离,并通过傅里叶变换红外光谱(FTIR)、紫外-可见光谱(UV-Vis)和三维荧光光谱(3DEEMs)对自然水体和底泥中的疏水酸(腐殖酸、富里酸)、疏水碱、疏水中性物质和亲水物质进行表征和对比.结果表明,水体中有机物含量:亲水物质富里酸腐殖酸疏水碱疏水中性物质,底泥中有机物的含量为:腐殖酸富里酸亲水物质疏水碱疏水中性物质.根据红外、紫外、三维荧光光谱可知底泥中有机物的芳香程度、不饱和程度及分子量大小略高于水体有机物.根据荧光指数(FI)和自生源指标(BIX)可知,底泥和水体的腐殖酸和富里酸主要来源于陆生动植物和土壤有机质,而其余物质主要源于细菌和藻类活动.     

混凝-生物强化联合处理环氧树脂高盐废水

环氧树脂高盐废水是目前较难处理的工业废水之一.采用混凝联合生物强化工艺:通过混凝过程进行预处理后,投加嗜盐菌进行生物强化考察盐度变化对系统降解有机物的影响以及污泥性状的变化情况.结果表明,当废水中氯离子浓度达到驯化目标10 g/L时,系统对COD的去除率仍稳定在85％左右;以没有投加嗜盐菌的反应器为对照组,在进水COD平均浓度为550 mg/L左右,氯离子浓度由12 g/L增至21 g/L时,对照组COD平均去除率由82％降至60％以下,而投加了嗜盐菌的反应器(投加组)则仍保持在85％以上;此外,盐度的变化同时影响污泥的活性及其沉降性能,随着盐度增大,两组中的污泥活性均有所降低,但投加组的污泥活性相对较高,其污泥的沉降时间和污泥体积指数(sludge volume in-dex,SVI)值也较低.采用本工艺处理环氧树脂高盐废水,使得生物处理过程能够长期稳定运行,且能够保持较高的耐盐度和COD去除率.     

洗相废水中银回收技术研究

采用电解法和离子交换法回收洗相废水中的银.结果表明,电解法对高浓度含银洗相废水的银回收处理是一种行之有效的方法.对于中低浓度洗相废水中的银的回收,采用4%硫酸再生IRA-68离子交换树脂,树脂的交换能力可以增加4倍,再生时由于已交换的银被直接固定在树脂上,结果使得再生剂处置和银回收过程更加简单方便.IRA-68离子交换树脂回收中低浓度洗相废水中银的技术具有银回收效率更高、离子交换运行时间更长和操作更为简便等优点,使得传统的离子交换技术得到极大的改进和提高.     

滦河水体溶解性有机物的综合分级表征及其混凝去除过程

天然水体溶解性有机物(DOM)是微污染物的潜在载体,是消毒副产物的主要前驱物,自身又可能成为微污染物,因此研究其内在特性和去除机理有着重要的基础性科学意义.本研究综合利用化学、物理分级方法(即树脂和超滤分级法),对中国北方典型饮用水源--滦河水体的DOM进行全面分级表征.此水体DOM基本化学分级特征是憎水酸(HoA)、亲水性物质(HiM)含量较高,且具有季节稳定性;其物理分级特征是分子量＜1 kDa及3 kDa～10 kDa的组分含量较高,也表现出一定的时间稳定性.选用工业聚合铝(PAC)研究此DOM的基本混凝特征和内在混凝机理,结果表明,强憎水部分HoA及3 kDa～10 kDa间的有机物较易被去除,而较大分子量范围10 kDa～30 kDa间的有机物去除率较低,说明混凝过程中此DOM的物理性质不起主要作用,而化学性质更为重要.特别对DOM各组分作进一步(结合)分级研究,发现HoA主要在＞10 kDa范围.＜1 kDa的有机物中主要为HiM,但其中还含有HoA和弱憎水酸(WHoA),这使特定条件下部分＜1 kDa有机物被混凝去除成为可能.另外,HoA中按分子量大小仍可分为易去除和难去除部分,但分布不连续,易去除部分在3 kDa～10 kDa和＞30 kDa区间,而其10 kDa～30 kDa部分较难去除,说明可能存在其他结构性影响因素,值得深入研究.