活性炭对天然水体中甲基对硫磷和三氯乙烯的吸附特性研究

采用序批式试验研究了3种粉末活性炭(PAC)对天然水体中甲基对硫磷(MP)和三氯乙烯(TCE)的吸附平衡特性,利用均相表面扩散模型(HSDM)对不同投炭量下的吸附动力学进行拟合与预测,并探讨了天然有机物(NOM)对MP、TCE在PAC上的竞争吸附效应.研究结果表明,天然水体条件下,3种PAC对MP和TCE的吸附符合Langmuir模型和Freundlich模型;MP比TCE更易于被PAC吸附;3种PAC对MP、TCE的吸附能力由大到小依次为YK炭、SL炭和JC炭;HSDM模型可以很好地对吸附动力学进行拟合,并能够有效地预测不同投炭量时的吸附动力学;天然水体中的NOM会与MP和TCE在PAC上发生竞争吸附,NOM对MP的竞争吸附作用相对TCE更为显著.     

不同粒径粉末活性炭对水中天然有机物吸附性能的比较研究

以吸附去除微污染水中天然有机物(natural organic matter,NOM)为目标,考察了粉末活性炭(PAC)在10~100μm内的粒径变化对其吸附性能的影响,并探讨了PAC粒径变化对不同相对分子质量NOM组分的分级吸附特性.3种不同粒径的PAC由市售PAC经过研磨筛分获得,按照中值粒径(d50)从小到大依次为:PAC-1(19μm)、PAC-2(46μm)和PAC-3(76μm).吸附实验结果表明,无论对模拟水样还是实际微污染水体中的NOM,随着PAC粒径的减小,PAC对NOM的吸附容量和吸附速率都显著提高.小粒径PAC吸附速率的增加一方面是由于粒径减小导致的有效吸附位点的增加,另一方面粒径减小也使得吸附质分子到达活性炭表面吸附位点的距离减小;而吸附容量的增加主要是由于粒径较小的PAC具有更大的外层比表面积和中孔孔容,有效减弱了相对分子质量大的NOM对活性炭的孔阻塞效应.此外,PAC粒径减小能显著增强其对天然水体中相对分子质量大于2 000的有机物组分的吸附,而对相对分子质量小于800的有机物组分的吸附影响相对较小.     

碳基吸附剂对典型有机防晒剂二苯甲酮-3的吸附性能及热力学研究

针对环境水体中药物及个人护理用品(PPCPs)的污染问题,选择在环境水体中存在的有机紫外防晒剂二苯甲酮-3(BP-3)作为典型污染物,以颗粒活性炭(GAC)、粉末活性炭(PAC)和碳纳米管(CNT)作为吸附剂,考察吸附剂对BP-3的吸附性能、吸附特性和吸附热力学.结果表明:吸附性碳材料对BP-3具有良好的吸附性能,3种碳材料的最大吸附容量排列为:PACGACCNT,其中,PAC的单层最大吸附容量为450.36mg·g-1.Freundlich、Redlich-Peterson和Temkin吸附等温线方程能够较好地拟合吸附数据,Langmuir吸附等温线方程对PAC的吸附拟合效果较好,而对粒径较大的吸附剂(GAC、CNT)的拟合效果不理想.PAC、GAC的吸附过程可以采用一级动力学或者二级动力学模型拟合,而CNT适合采用一级动力学模型来描述.吸附热力学分析表明,PAC、GAC和CNT对BP-3的吸附过程都是自发进行的,其中,PAC和GAC的吸附过程是吸热的,升高温度有利于吸附反应的进行;而CNT的吸附过程是放热的.     

磁性树脂预处理对粉末活性炭吸附水中卡马西平的影响

通过磁性树脂预处理,来提高粉末活性炭(PAC)应对水源水中突发以卡马西平(CBZ)为代表的PPCPs类有机物污染风险的能力.结果显示,Freundlich吸附模型可以更好描述PAC对CBZ的吸附规律;假一级动力学对CBZ吸附动力学过程模拟结果良好,假二级动力学更适合模拟时间大于1h的吸附过程;200~300目PAC具有较大的吸附容量和较快的吸附速率;在模拟配水试验中,磁性树脂与PAC联用相比单独使用PAC时,DOC去除率提高了40.64%,UV254去除率提高了41.27%,CBZ去除率提高了14.72%.在去除水中有机污染物过程中,磁性树脂与PAC间存在协同作用,磁性树脂预处理强化了PAC对CBZ的去除效果.     

磁性树脂预处理对粉末活性炭吸附水中卡马西平的影响

通过磁性树脂预处理,来提高粉末活性炭(PAC)应对水源水中突发以卡马西平(CBZ)为代表的PPCPs类有机物污染风险的能力.结果显示,Freundlich吸附模型可以更好描述PAC对CBZ的吸附规律;假一级动力学对CBZ吸附动力学过程模拟结果良好,假二级动力学更适合模拟时间大于1h的吸附过程;200~300目PAC具有较大的吸附容量和较快的吸附速率;在模拟配水试验中,磁性树脂与PAC联用相比单独使用PAC时,DOC去除率提高了40.64%,UV254去除率提高了41.27%,CBZ去除率提高了14.72%.在去除水中有机污染物过程中,磁性树脂与PAC间存在协同作用,磁性树脂预处理强化了PAC对CBZ的去除效果.     

腐殖酸对粉末活性炭吸附微囊藻毒素的影响研究

在测定粉末活性炭(PAC)比表面性质和对微囊藻毒素(MCLR)吸附动力学的基础上,通过改变腐殖酸(HA)浓度、天然有机物(NOM)浓度和溶液pH值,研究HA对PAC吸附MCLR的影响及在NOM影响吸附过程中的作用。结果表明,PAC吸附MCLR的有效孔径容积约占16.7%,对MCLR的吸附在24h后可达平衡。当溶液中含有10.0mg/LHA时,PAC对MCLR的理论单层饱和吸附量qm从64.06μg/g降低至48.16μg/g。溶液中HA和NOM浓度为5mg/L时,平衡吸附量qe从38.47μg/g降至28.14μg/g和33.78μg/g,天然水体中,与其它结构的有机物相比,HA很可能是削弱PAC吸附MCLR能力的主要因素,且随HA和NOM浓度增大,qe降低较缓慢。当pH≥9时,HA对PAC吸附MCLR的影响开始逐渐减小。     

碘化活性炭吸附和预富集水体汞的方法

化学处理活性炭对汞等重金属离子具有良好的吸附特性。通过一系列测试获得了碘化和氯化活性炭预富集水体汞的优化方案。对实验室配制汞标准样品的测试表明,碘化和氯化活性炭对汞具有良好的吸附特性,而采样管的内径、活性炭的填充量以及过滤流速均影响活性炭预富集水体汞的效率。采用600mg的碘化活性炭采样管(内径:0.35cm),在水体过滤流速为10r/min(7mL/min)~25r/min(17mL/min)的条件下,碘化活性炭对水体汞的吸附效率可达到95%以上。增加流速和采样管内径以及减少活性炭填充量均会降低活性炭对水体汞的吸附效率。同时进一步测试了碘化活性炭对高汞(万山汞矿区渗滤水,含量范围:37.68~321.57ng/L)和低汞(贵阳市降水,含量范围:2.76~9.98ng/L)等天然水体汞的预富集效率,其预富集效率的平均值分别为96.74%(n=8)和96.09%(n=8)。该研究为采用化学处理活性炭技术预富集天然水体汞以及开展水体汞同位素测试提供了一种全新方法。     

基于EEMs和PARAFAC分析典型碳材料吸附水中DOM特征研究

水中溶解性有机物(DOM)对全球污染物迁移和水处理工艺效能具有重要影响。采用3种典型碳材料,包括碳纳米管(CNTs)、颗粒活性炭(GAC)、粉末活性炭(PAC)分别吸附微污染源水中的DOM。基于荧光发射-激发光谱(EEMs)和平行因子(PARAFAC)分析,解析DOM中的有效荧光组分,评估3种材料对不同组分吸附去除的效果和吸附特征。研究表明:PARAFAC分析方法提取4种荧光组分C1和C2(腐殖酸类)、C3和C4(类蛋白类)。以TOC为基础的吸附等温线模型表明,PAC的KF值大于GAC和CNTs,PAC有丰富的中孔和较大的比表面积,吸附容量比GAC和CNTs更大。C3和C4 2个荧光组分在吸附过程中更容易被吸附,PAC对两者吸附容量最大。研究结果揭示了不同碳吸附材料对水中不同类型有机物的吸附特征,可为吸附工艺应用提供技术参考。     

粉末活性炭粒径对水中菲吸附动力学的影响效应研究

以菲为目标污染物,研究了粉末活性炭(PAC)在微尺度(1～ 100.Μm)下的粒径效应对多环芳烃吸附性能的影响.实验中按照中值粒径将研磨后得到的粉末活性炭划分为:PAC-1 (19 μm)、PAC-2(46μm)、PAC-3(76 μm).通过比表面积及孔隙度自动分析仪、原位拉曼光谱、扫描电镜等手段对PAC物化性质进行表征,发现粒径减小使PAC的BET比表面积和总孔容增加了10％ ～20％左右,而对PAC表面化学性质的影响较小.PAC的粒径分布对其吸附性能有显著影响,这种影响主要体现为吸附速率成倍的增加,其次是吸附容量有30％ ～36％的增幅.分别用3种动力学模型对吸附过程进行拟合,结果表明,伪二级动力学方程的拟合程度最高,PAC-1有最大的吸附速率常数k,并且随着粒径的减小,k值逐渐增大.     

PAC对再生水中典型有机物吸附动力学和热力学研究

通过粉末活性炭(PAC)吸附再生水中3类典型有机物(腐殖酸、多糖和蛋白质)进行等温线吸附、动力学吸附及吸附前后其粒径变化试验,研究PAC吸附不同有机物的热力学和动力学特性。结果表明,吸附等温线中Freundlich方程拟合结果最好,吸附过程为单分子层吸附,PAC对腐殖酸的吸附效果最好,对多糖的吸附效果最差;热力学研究发现,PAC对3类有机物的吸附过程为自发放热过程。吸附动力学研究发现,PAC吸附3种有机物的最佳接触时间均为12 h;准二级动力学方程更适合描述PAC的吸附过程,其对有机物的吸附由液膜扩散和颗粒内扩散联合作用;PAC吸附腐殖酸的扩散速率最快,吸附量也最大。PAC吸附有机物后的粒径均不同程度地增大,吸附多糖时增加最多,吸附腐殖酸时增加最小。     

Powdered activated carbon adsorption of two fishy odorants in water: Trans,trans-2,4-heptadienal and trans,trans-2,4-decadienal

Powdered activated carbon (PAC) adsorption of two fishy odorants, trans,trans-2,4-heptadienal (HDE) and trans,trans-2,4-decadienal (DDE), was investigated. Both the pseudo first-order and the pseudo second-order kinetic models well described the kinetics curves, and DDE was more readily removed by PAC. In isotherm tests, both Freundlich and Modified Freundlich isotherms fitted the experimental data well. PAC exhibited a higher adsorption capacity for DDE than for HDE, which could be ascribed to the difference in their hydrophobicity. The calculated thermodynamic parameters (ΔG⁰, ΔH⁰, and ΔS⁰) indicated an exothermic and spontaneous adsorption process. PAC dosage, pH, and natural organic matter (NOM) presence were found to influence the adsorption process. With increasing PAC dosage, the pseudo first-order and pseudo second-order rate constants both increased. The value of pH had little influence on HDE or DDE molecules but altered the surface charge of PAC, and the maximum adsorption capacity occurred at pH 9. The presence of NOM, especially the fraction with molecular weight less than 1 k Dalton, hindered the adsorption. The study showed that preloaded NOM impaired the adsorption capacity of HDE or DDE more severely than simultaneously fed NOM did.     

Competitive effects of humic acid and wastewater on adsorption of Methylene Blue dye by activated carbon and non-imprinted polymers

Natural organic matter(NOM), present in natural waters and wastewater, decreases adsorption of micropollutants, increasing treatment costs. This research investigated mechanisms of competition for non-imprinted polymers(NIPs) and activated carbon with humic acid and wastewater. Three different types of activated carbons(Norit PAC 200,Darco KB-M, and Darco S-51) were used for comparison with the NIP. The lower surface area and micropore to mesopore ratio of the NIP led to decreased adsorption capacity in comparison to the activated carbons. In addition, experiments were conducted for single-solute adsorption of Methylene Blue(MB) dye, simultaneous adsorption with humic acid and wastewater, and pre-loading with humic acid and wastewater followed by adsorption of MB dye using NIP and Norit PAC 200. Both the NIP and PAC 200 showed significant decreases of 27% for NIP(p = 0.087) and 29% for PAC 200(p = 0.096) during simultaneous exposure to humic acid and MB dye. There was no corresponding decrease for NIP or PAC 200 pre-loaded with humic acid and then exposed to MB. In fact, for PAC 200, the adsorption capacity of the activated carbon increased when it was pre-loaded with humic acid by 39%(p = 0.0005). For wastewater, the NIP showed no significant increase or decrease in adsorption capacity during either simultaneous exposure or pre-loading. The adsorption capacity of PAC 200 increased by 40%(p = 0.001) for simultaneous exposure to wastewater and MB. Pre-loading with wastewater had no effect on MB adsorption by PAC 200.     

固定床生物活性炭吸附天然有机物及其模型化研究

以日本长良川原水为研究对象,提高水处理出水水质为目标,研究了生物活性炭(BAC)小柱对原水中天然有机物(NOM)的去除效果。比较了不同NOM进水浓度时BAC小柱对其的去除率,研究了小柱层内及出水中NOM的相对分子量分布随着通水时间增加的变化情况,并利用结合了理想吸附溶液理论(IAST)的平推流表面扩散模型对出水中NOM的浓度进行模拟。结果表明,BAC小柱对不同浓度原水中NOM的去除率均高于相同试验条件下的粒状活性炭(GAC)小柱;BAC小柱对相对分子量分布为1000~5200g/mol内各分子量区间的有机物均可去除;平推流表面扩散模型对试验数据拟合结果较好。     

Comparison of different combined treatment processes to address the source water with high concentration of natural organic matter during snowmelt period

The source water in one forest region of the Northeast China had very high natural organic matter (NOM) concentration and heavy color during snowmelt period. The efficiency of five combined treatment processes was compared to address the high concentration of NOM and the mechanisms were also analyzed. Conventional treatment can hardly remove dissolved organic carbon (DOC) in the source water. KMnO₄ pre-oxidization could improve the DOC removal to 22.0%. Post activated carbon adsorption improved the DOC removal of conventional treatment to 28.8%. The non-sufficient NOM removal could be attributed to the dominance of large molecular weight organic matters in raw water, which cannot be adsorbed by the micropore upon activated carbon. O₃ + activated carbon treatment are another available technology for eliminating the color and UV₂₅₄ in water. However, its performance of DOC removal was only 36.4%, which could not satisfy the requirement for organicmatter. The limited ozone dosage is not sufficient to mineralize the high concentration of NOM. Magnetic ion-exchange resin combined with conventional treatment could remove 96.2% of color, 96.0% of UV₂₅₄ and 87.1% of DOC, enabling effluents to meet the drinking water quality standard. The high removal efficiency could be explained by the negative charge on the surface of NOM which benefits the static adsorption of NOM on the anion exchange resin. The results indicated that magnetic ion-exchange resin combined with conventional treatment is the best available technology to remove high concentration of NOM.     

Comparison of different combined treatment processes to address the source water with high concentration of natural organic matter during snowmelt period

The source water in one forest region of the Northeast China had very high natural organic matter(NOM) concentration and heavy color during snowmelt period. The efficiency of five combined treatment processes was compared to address the high concentration of NOM and the mechanisms were also analyzed. Conventional treatment can hardly remove dissolved organic carbon(DOC) in the source water. KMn O4pre-oxidization could improve the DOC removal to 22.0%. Post activated carbon adsorption improved the DOC removal of conventional treatment to 28.8%. The non-sufficient NOM removal could be attributed to the dominance of large molecular weight organic matters in raw water, which cannot be adsorbed by the micropore upon activated carbon. O3+ activated carbon treatment are another available technology for eliminating the color and UV254 in water. However, its performance of DOC removal was only 36.4%, which could not satisfy the requirement for organic matter. The limited ozone dosage is not sufficient to mineralize the high concentration of NOM. Magnetic ion-exchange resin combined with conventional treatment could remove 96.2%of color, 96.0% of UV254 and 87.1% of DOC, enabling effluents to meet the drinking water quality standard. The high removal efficiency could be explained by the negative charge on the surface of NOM which benefits the static adsorption of NOM on the anion exchange resin. The results indicated that magnetic ion-exchange resin combined with conventional treatment is the best available technology to remove high concentration of NOM.     

臭氧氧化对天然有机物在氧化铝表面吸附行为的影响

为进一步明确臭氧预氧化对颗粒的脱稳作用,选用氧化铝（α-Al₂O₃）作为悬浮颗粒,考察了臭氧氧化后天然有机物（natural organic matters,NOM）特性及吸附行为的变化.结果表明,臭氧氧化能够破坏NOM的芳香结构,SUVA值降低25%～35%,氧化后酸性官能团含量增多,总酸度增加0.3～1.4 mmol·g^-1,分子量和极性的变化与NOM的性质有关;有机物初始浓度相对于臭氧投量较低时,NOM的溶解性增强,与其酸性官能团增加产生的吸附促进作用相抵消,因而吸附性能出现不变甚至降低的现象;有机物初始浓度较高时,臭氧能够起到强化NOM吸附的作用.采用2.5　mg·L^-1臭氧进行氧化后,以商用腐殖酸为代表的NOM的吸附形貌,由密集分布的球形对称聚集结构向网状结构过渡,分子之间的交联作用十分明显,吸附高度低于其氧化处理前,云母的表面覆盖率较氧化前略有提高.     

Membrane flux dynamics in the submerged ultrafiltration hybrid treatment process during particle and natural organic matter removal

Exponential relationship was developed to quantify the normalized membrane flux dynamics during the filtration period and fitted the results well.     

Effects of chemical modification on physicochemical properties and adsorption behavior of sludge-based activated carbon

This study aimed to explore the adsorption performance of sludge-based activated carbon (SBC) towards dissolved organic matters (DOMs) removal from sewage, and investigated the modification effect of different types of chemicals on the structure of synthesized SBC. Waste activated sludge (WAS) was used as a carbon source, and HCl, HNO₃, and NaOH were used as different types of chemicals to modify the SBC. With the aid of chemical activation, the modified SBC showed higher adsorption performances on DOMs removal with maximum adsorption of 29.05 mg/g and second-order constant (k) of 0.1367 (L/mol/sec) due to the surface elution of ash and minerals by chemicals. The surface elemental composition of MSBC suggested that the content of C-C and C-O functional groups on the surface of modified sludge-based activated carbon (MSBC) played an important role on the adsorption capacities of MSBC towards DOMs removal in sewage. Additionally, the residual molecular weight of DOMs in sewage was investigated using a 3-dimension fluorescence excitation-emission matrix (3D-EEM) and high-performance size exclusion chromatography (HP-SEC). Results showed that the chemical modification significantly improved the adsorption capacity of MSBC on humic acids (HA) and aromatic proteins (APN), and both of NaOH-MSBC and HCl-MSBC were effective for a wide range of different AMW DOMs removal from sewage, while the HNO₃-MSBC exhibited poorly on AMW organics of 2,617 Da and 409 Da due to the reducing content of macropore. In brief, this study provides reference values for the impact of the chemicals of the activation stage before the SBCs application.     

Effect of water matrices on removal of veterinary pharmaceuticals by nanofiltration and reverse osmosis membranes

This study explored the removal of five veterinary pharmaceuticals (VPs) (sulfamethoxazole (SMETOX), trimethoprim (TMP), ciprofloxacin (CIPRO), dexamethasone (DEXA) and febantel (FEBA)) from different water matrices (Milli-Q water, model water, tap water and real pharmaceutical wastewater using four types of nanofiltration (NF) membranes (NF90, NF270, NF and HL) and two reverse osmosis (RO) membranes (LFC-1 and XLE). All VPs were added to different water matrices at a concentration of 10 mg/L. Rejections of VPs and water flux were measured. The rejection increased with increase of molecular weight. The highest rejections were obtained with RO membranes (LFC-1, XLE) and tight NF (NF90) membrane. In general, the rejection of VPs was higher in model water and tap water than in Milli-Q water, but the water flux was lower. This was mainly explained by ion adsorption inside the membranes pores. Narrower pore size counteracted the effect of presence of low concentration of natural organic matter (NOM) in tap water. The NOM was assumed to enhance the adsorption of VPs onto membrane surface, increased the size exclusion and electrostatic repulsion also appeared during the transport. Investigated water matrices had influence on water flux decline due to their complexity.