Adsorption thermodynamics and kinetic investigation of aromatic amphoteric compounds onto different polymeric adsorbents

The adsorption behavior of p-aminobenzoic acid and o-aminobenzoic acid onto the different polymeric adsorbents was systematically investigated as a function of the solution concentration and temperature.Experimental results indicated that the equilibrium adsorption data of the four polymeric adsorbents fitted well in the Freundlich isotherm.The adsorption capacity of multi-functional polymeric adsorbent NJ-99 was the highest,which might be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of aminobenzoic acid.The adsorption capacity of o-aminobenzoic acid onto any adsorbent was higher than p-aminobenzoic acid.Thermodynamic studies suggested the exothermic,spontaneous physical adsorption process.Adsorption kinetics results showed that the adsorption followed the pseudo-second-order kinetics model and the intraparticle mass transfer process was the rate-controlling step.     

吸附树脂对苯甲酸的吸附动力学研究

对比超高交联吸附树脂NJ 8与AmberliteXAD 4对苯甲酸的静态吸附动力学性质 ,并深入讨论温度和起始浓度对平衡时间和吸附速率的影响。NJ 8和XAD 4两种树脂在吸附苯甲酸的过程中 ,膜扩散和颗粒内扩散均为主控步骤 ,但是前者颗粒内扩散占据优势 ,而后者膜扩散占据优势     

Preparation and application of amino functionalized mesoporous nanofiber membrane via electrospinning for adsorption of Cr3+ from aqueous solution

Novel amino (-NH₂) functionalized mesoporous polyvinyl pyrrolidone (PVP)/SiO₂ composite nanofiber membranes were fabricated by a one-step electrospinning method using poly (vinyl alcohol) and tetraethyl orthosilicate (TEOS) mixed with cationic surfactant, cetyltrimethyl ammonium bromide (CTAB) as the structure directing agent. Ureidopropyltriethoxysilane was used for functionalization of the internal pore surfaces. The membranes were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) images, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), element analyzer and N2 adsorption-desorption isotherms. The nanofiber diameters, average pore diameters and surface areas were 100-700 nm, 2.86 nm and 873.62 m²/g, respectively. These mesoporous membranes functionalized with -NH₂ groups exhibited very high adsorptions properties based on the adsorption of Cr³⁺+ from an aqueous solution. Equilibrium adsorption was achieved after approximately 20 min and more than 97% of chromium ions in the solution were removed. The membrane could be regenerated through acidification.     

金属有机骨架HKUST-1对水中微量氨基酸的吸附性能

采用溶剂热法制备金属有机骨架HKUST-1,选取水源水中检出率较高的酪氨酸（Tyr）、苯丙氨酸（Phe）和色氨酸（Trp）为目标物,开展了HKUST-1吸附微量氨基酸性能的研究.利用XRD和FTIR技术对吸附剂HKUST-1进行了表征和分析,通过吸附动力学、吸附等温线和吸附热力学的研究探讨HKUST-1吸附氨基酸的机理.结果表明,HKUST-1具有高结晶度,对酪氨酸、苯丙氨酸和色氨酸有较好的去除效果,饱和吸附容量分别可达248.65,143.67,140.09mg/g;吸附过程符合Langmuir吸附等温线模型和Lagergren准二级动力学模型;吸附热力学结果表明,HKUST-1去除氨基酸的过程为吸热反应;高吸附容量主要归因于静电相互作用、氢键和π-π相互作用.     

Adsorption mechanism of phenolic compounds from aqueous solution on hypercrosslinked polymeric adsorbent

The adsorption of two phenols, namely, phenol and salicylic acid(SA) onto a water-compatible hypercrosslinked polymeric resin (NJ-8) were studied in terms of pseudo-second-order and first order mechanisms for chemical sorption as well as an intraparticle diffusion mechanism process. Kinetic analysis showed that the intraparticle diffusion process was the essential rate-controlling step. The activation energies of sorption have also been evaluated with the pseudo-second-order and intraparticle diffusion constants, respectively. Adsorption equilibrium data were well fitted by the Langmuir, Freundlich and Redlich-Peterson isotherms. Adsorption was exothermic and basically of a type of transition between physical and chemical character. The sorption capacity was higher for SA due to its more hydrophobic. Phenol has a higher adsorption enthalpy since it could form stronger hydrogen bonding on NJ-8.     

Adsorption of catechol from aqueous solution by aminated hypercrosslinked polymers

Adsorption of catechol from aqueous solution with the hypercrosslinked polymeric adsorbent NDA-100 and its derivatives AH-1,AH-2 and AH-3 aminated by dimethylamine, the commercial resin Amberlite XAD-4 and weakly basic anion exchanger resin D301 was compared. It was found that the aminated hypercrosslinked resins had the highest adsorption capacities among the tested polymers. The empirical Freundlich equation was successfully employed to describe the adsorption process. Specific surface area and micropore structure of the adsorbent, in company with tertiary amino groups on matrix affected the adsorption performance towards catechol. In addition, thermodynamic study was carried out to interpret the adsorption mechanism. Kinetic study testified that the tertiary amino groups on the polymer matrix could decrease the adsorption rate and increase the adsorption apparent activation energy.     

环丙沙星在黄土中的吸附机制及影响因素

为了解兽药抗生素在西北黄土中的吸附行为及机制,以环丙沙星（Ciprfloxacin,CIP）为目标污染物,采用批平衡实验法研究其在黄土中的吸附动力学、吸附热力学、pH值和粒径等影响因素.结果表明：环丙沙星在黄土中的吸附可分为两个阶段,6h内表现为快速吸附,6~10h表现为慢速吸附,10h后吸附达到平衡;环丙沙星在黄土中的吸附动力学过程较符合准二级吸附动力学模型,吸附速率受颗粒内部扩散和外部液膜扩散共同影响;吸附热力学过程较符合Freundlich等温吸附模型,且吸附等温线符合L-型,表明黄土对环丙沙星的吸附受溶液中溶质和水分子共同作用影响;焓变ΔH^θ、熵变ΔS^θ和吉布斯自由能ΔG^θ均<0,表明黄土对环丙沙星的吸附是混乱度减少的自发进行的放热反应;pH=5时黄土对环丙沙星的吸附量最大,pH值为2~5时,黄土对环丙沙星的吸附量随pH值升高呈上升趋势,pH>5时,黄土对环丙沙星的吸附量随pH值升高呈下降趋势,表明强酸和碱性环境均不利于吸附;吸附量与黄土粒径呈反比,与初始浓度呈正比.由实验结果推断黄土对环丙沙星的吸附主要与有机质含量有关,主要吸附机制为环丙沙星分子中氨基的阳离子交换作用.     

季铵化改性稻草吸附去除水中SO42-的特性研究

采用NaOH、环氧氯丙烷和三甲胺改性稻草秸秆,制备出含季铵基的吸附剂,用以去除水中的硫酸根离子(SO2-4).通过SEM、元素分析、13C-NMR表征发现,稻草改性后表面纤维结构暴露,含氮量增加,引入了大量的季铵基,吸附潜力显著提高.吸附实验结果表明,改性稻草吸附去除SO42-平衡时间约20min,pH为3～8范围内吸附效果较好.采用Langmuir吸附模型可较好地描述改性稻草对SO2-4的吸附等温线,其最大单分子层吸附量Qmax为74.76mg·g-1,吸附能力远大于原稻草(11.68mg·g-1).     

Kinetics of enhanced adsorption by polarization for organic pollutants on activated carbon fiber

The adsorption kinetics for model pollutants on activated carbon fiber (ACF) by polarization was investigated in this work. Kinetics data obtained for the adsorption of these model pollutants at open-circuit, 400 mV, and −400 mV polarization were applied to the Lagergren equation, and adsorption rate constants (K _a) were determined. With the anodic polarization of 400 mV, the capacity of sodium phenoxide was increased from 0.0083 mmol/g at open-circuit to 0.18 mmol/g, and a 17-fold enhancement was achieved; however, the capacity of p-nitrophenol was decreased from 2.93 mmol/g at open-circuit to 2.65 mmol/g. With the cathodal polarization of −400 mV, the capacity of aniline was improved from 3.60 mmol/g at open-circuit to 3.88 mmol/g; however, the capacity of sodium dodecylbenzene sulfonate was reduced from 2.20 mmol/g at open-circuit to 1.59 mmol/g. The enhancement for electrosorption changed with different groups substituting. Anodic polarization enhances the adsorption of benzene with the electron-donating group. But whether anodic or not, cathodal polarization had less effect on the adsorption of electron-accepting aromatic compounds, and decreased the adsorption capacity of benzene-bearing donor-conjugate bridge-acceptor, while increasing its adsorption rate. Electrostatic interaction played a very important role in the electrosorption of ion-pollutants. Translated from Environmental Science, 2006, 27(6): 1111–1116 [译自: 环境科学]     

Insight into the adsorption of tetracycline onto amino and amino–Fe functionalized mesoporous silica: Effect of functionalized groups

In order to study the influences of functionalized groups onto the adsorption of tetracycline (TC), we prepared a series of amino and amino–Fe^3 + complex mesoporous silica adsorbents with diverse content of amino and Fe^3 + groups (named N,N-SBA15 and Fe-N,N-SBA15). The resulting mesoporous silica adsorbents were fully characterized by X-ray powder diffraction, Fourier transform infrared spectrometer and N₂ adsorption/desorption isotherms. Furthermore, the effects of functionalized groups on the removal of TC were investigated. The results showed that the periodic ordered structure of SBA-15 was maintained after modification of amino/Fe^3 + groups. The functionalized amino groups decreased the adsorption capacity while the coordinated Fe^3 + increased the adsorption capacity. The adsorption kinetics of TC fitted pseudo-second-order model well and the equilibrium was achieved quickly. The adsorption isotherms fitted the Langmuir model well and with the Fe^3 + content increased from 3.93% to 8.26%, the Q_max of the adsorbents increased from 102 to 188 mmol/kg. The solution pH affected the adsorption of TC onto amino complex adsorbents slightly while influenced the adsorption onto Fe-amine complex adsorbents greatly. The adsorption of TC on SBA15 and N,N-SBA15 may be related to the formation of outer-sphere surface complexes, while the adsorption of TC onto Fe-N,N-SBA15 was mainly attributed to the inner-sphere surface complexes. This study could offer potential materials that have excellent adsorption behavior for environmental remediation and suggested useful information for the preparing other adsorbents in environmental applications.     

胺基树脂吸附去除水中的壬基酚聚氧乙烯醚

使用氯球作为前驱体与二乙烯三胺在回流条件下反应合成一种胺基树脂,对胺基树脂的特征进行了表征,并研究了胺基树脂对水中的壬基酚聚氧乙烯醚(NP₁₀EO)的吸附行为.树脂的红外、元素分析及比表面积与平均孔径分析结果表明,胺基官能团成功地嫁接到树脂表面,胺基浓度为5.6 mmol/g,且胺基树脂的比表面积较氯球有较大增加.胺基树脂对NP₁₀EO的吸附等温线表明,温度的升高有利于吸附,在35 ℃下胺基树脂对NP₁₀EO的最高平衡吸附量达58.36 mg/g.采用Langmuir方程和Freundlich方程用于吸附等温线的解释,结果表明,吸附等温线更加符合Langmuir模型,相关系数(R2)均大于0.98. NP₁₀EO在胺基树脂上的吸附符合准二级动力学方程,初始ρ(NP_10EO)越低达到吸附平衡所需时间越短,初始ρ(NP_10EO)为9.41 mg/L的溶液能在2 h内达到吸附平衡.      

聚合铝与有机高分子复合絮凝剂的絮凝性能及其吸附特性

为探讨聚合铝与有机高分子在复合絮凝作用过程中的相互作用,选取４种典型有机高分子絮凝剂,研究聚合铝与阳离子型有机高分子和阴离子型有机高分子复合后的凝聚絮凝特征及其吸附特性．结果表明,聚合铝与阳离子型有机高分子复合能够使其絮凝效能相互促进,而聚合铝与阴离子型有机高分子的复合只有在药剂投加量达到一定值时才能对絮凝效能起促进作用．阳离子型有机高分子引入聚合铝后,使聚合铝的吸附量降低,而阴离子型有机高分子的引入使聚合铝的吸附能力大大增强,吸附量显著提高     

复合功能树脂吸附对苯二酚的热力学研究

研究了复合功能超高交联树脂对水溶液中对苯二酚的静态吸附热力学特征,结果表明:超高交联树脂上引入适量的胺基,可明显地提高树脂的吸附容量。该类树脂对对苯二酚的吸附为自发的放热过程,属于物理吸附过程。     

氧化石墨烯改性污泥基生物炭对培氟沙星的去除机理研究

为获得培氟沙星废水高效去除的环境友好型吸附剂,以城市剩余污泥为原料制备了SBC（污泥基生物炭）,并采用氧化石墨烯（GO）对其改性得到GO-SBC（氧化石墨烯改性生物炭）,利用SEM和FTIR对其进行表征,通过静态吸附试验探讨了生物炭对培氟沙星的去除效果,并通过吸附模型和FTIR、XPS表征技术进一步探究了GO-SBC对培氟沙星的吸附机理.结果表明:①改性后的GO-SBC表面更加粗糙,生物炭表面含氧官能团数量增加.②动力学吸附研究表明,GO-SBC对培氟沙星的最大吸附容量为137.51 mg/g,比SBC对培氟沙星的吸附容量提高了40.32%,且GO-SBC对培氟沙星的吸附更符合伪二级动力学模型,表明吸附过程主要以化学吸附为主.③GO-SBC对培氟沙星的吸附符合Freundlich等温吸附模型,表明该吸附过程为多层吸附.④热力学研究表明,吸附过程为自发吸热反应.⑤GO-SBC对培氟沙星的吸附机制主要有两种作用,一种是π-π相互作用,另一种是GO-SBC的N—H与培氟沙星的C—H相互作用.研究显示,GO-SBC是一种高效去除培氟沙星的吸附剂,这为城市剩余污泥的资源化利用提供了出路,也为抗生素废水治理提供了方法.      

氨基修饰氧化石墨烯-羧甲基纤维素复合吸附剂的制备及其对Cr (VI)的吸附性能研究

为获得价格低廉、吸附性能优良的石墨烯基吸附剂,以氧化石墨烯（GO）、羧甲基纤维素（CMC）为基材,以聚乙烯亚胺（PEI）为改性试剂,通过化学修饰的方法制备了氨基修饰氧化石墨烯-羧甲基纤维素复合吸附剂（GO-PEI-CMC）.采用扫描电镜（SEM）、傅里叶红外光谱（FT-IR）及X射线光电子能谱（XPS）等表征手段证实了CMC、氧化石墨烯与PEI已成功复合.静态吸附实验表明GO-PEI-CMC对Cr （VI）表现出良好的吸附性能,由Langmuir等温吸附模型所得最大吸附量值为243.92 mg·g^-1.吸附动力学、吸附等温线研究表明GO-PEI-CMC对Cr （VI）的吸附为单分子层、化学吸附过程.GO-PEI-CMC对Cr （VI）吸附性能优良,且具有绿色环保、可生物降解的优点,是一种极具潜力的Cr （VI）吸附剂.     

甲基化MCM-41吸附水中硝基苯类化合物的研究

利用三甲基氯硅烷对MCM-41进行表面修饰制得甲基化MCM-41,采用X-射线衍射分析仪（XRD）、透射电镜（TEM）、N2吸附-脱附和红外光谱（FTIR）对样品进行表征,并考察其对水中硝基苯类化合物（NACs）的吸附性能.结果表明,甲基化MCM-41对NACs的吸附速率较快,吸附为放热过程,吸附等温线可以用线性模型拟...     

DOM不同相对分子质量组分在无机矿物上的吸附及其对卡马西平吸附的影响实验

为探究溶解性有机质(DOM)不同相对分子质量组分在矿物质上的吸附特征及其与药物和个人护理品(PPCPs)类污染物的结合作用对两者吸附过程的影响,以卡马西平作为目标污染物,用商用腐殖酸制备DOM,以石英砂代表无机矿物,开展吸附实验,并采用透析实验和红外光谱表征等手段,探讨了不同相对分子质量腐殖酸(HA)的结构特征及其与卡马西平(CBZ)的结合作用对HA或CBZ在固相介质上吸附作用的差异及产生机制.结果表明,大分子量HA有更多的羟基、芳香烃和脂肪烃,以疏水物质为主;而小分子量HA有更多的醇和羧基,以亲水物质为主.HA与CBZ的结合主要通过CBZ的氨基与小分子量HA中极性官能团的结合,以及CBZ疏水基团与大分子量HA中脂肪族与芳香族的疏水作用.CBZ与HA之间的相互作用对腐殖酸或卡马西平的吸附产生明显差异.当CBZ不存在时,石英砂主要通过疏水作用结合HA中疏水性大分子或与HA的羟基、羧基等发生交换配位反应,且石英砂更倾向于吸附HA中的脂肪性及疏水性大分子组分.当CBZ存在时,石英砂转而吸附HA中的小分子量部分,且HA在石英砂上的最大吸附量减小.当HA不存在时,CBZ可通过疏水作用,范德华力和极性相互作用使其在石英砂上有一定量的吸附.加入HA后,石英砂吸附增加的CBZ归因于部分HA分子与CBZ结合后共吸附或累积吸附于石英砂上.     

Adsorption of Cr(Ⅲ) from acidic solutions by crop straw derived biochars

Cr（Ⅲ） adsorption by biochars generated from peanut, soybean, canola and rice straws is investigated with batch methods. Adsorption of Cr（Ⅲ） increased as pH rose from 2.5 to 5.0. Adsorption of Cr（Ⅲ） led to peak position shifts in the FFIR-PAS spectra of the biochars and made zeta potential values less negative, suggesting the formation of surface complexes between Cr^3＋ and functional groups on the biochars. The adsorption capacity of Cr（Ⅲ） followed the order： peanut straw char 〉 soybean straw char 〉 canola straw char 〉 rice straw char, which was consistent with the content of acidic functional groups on the biochars. The increase in Cr^3＋ hydrolysis as the pH rose was one of the main reasons for the increased adsorption of Cr（Ⅲ） by the biochars at higher pH values. Cr（llI） can be adsorbed by the biochars through electrostatic attraction between negative surfaces and Cr^3＋, but the relative contribution of electrostatic adsorption was less than 5%. Therefore, Cr（Ⅲ） was mainly adsorbed by the biochars through specific adsorption. The Langumir and Freundlich equations fitted the adsorption isotherms well and can therefore be used to describe the adsorption behavior of Cr（Ⅲ） by the crop straw biochars. The crop straw biochars have great adsorption capacities for Cr（Ⅲ） under acidic conditions and can be used as adsorbents to remove Cr（Ⅲ） from acidic wastewaters.     

PDMS基涂层活性炭对甲苯、苯和丙酮吸附研究

活性炭疏水性改性是提高其对含水VOCs选择性吸附的重要手段,然而这种改性方法对活性炭吸附不同VOCs的效果研究较少.采用聚二甲基硅氧烷(polydimethylsiloxane,PDMS)对活性炭进行改性处理,并利用BET、Boehm滴定等方法对活性炭进行表征.采用动态吸附法,利用Yoon-Neslon吸附理论模型研究了不同相对湿度条件下,PDMS改性活性炭对VOCs(甲苯、苯、丙酮)吸附穿透曲线、饱和吸附量的影响及关键影响因素.结果表明:PDMS改性活性炭BET比表面积、微孔容积和表面酸碱官能团含量均有减少;经PDMS改性后,活性炭表面疏水性增大.动态吸附实验结果表明:PDMS改性前后活性炭吸附甲苯、苯、丙酮穿透曲线均符合Y-N模型;随着相对湿度增大,未经改性的活性炭(Bare-AC)对甲苯、苯和丙酮吸附速率降低、平衡吸附量减少,PDMS改性活性炭对甲苯、苯分子吸附速率和选择吸附能力提高,其中PDMS改性的活性炭(PDMS/AC-250)对甲苯、苯吸附量为相同条件下Bare-AC的1.86(甲苯)、1.92(苯)倍,但对丙酮分子提高不明显;结合表征结果分析,PDMS改性活性炭对VOCs分子吸附主要依靠化学吸附,同时与VOCs分子极性有关.     

胞外聚合物对活性污泥吸附去除全氟辛烷磺酸（PFOS）的影响

采用活性污泥和去除胞外聚合物(EPS)污泥作为吸附剂,探讨污泥吸附PFOS的机制和EPS在吸附过程中的作用.结果表明,活性污泥和去除EPS污泥吸附PFOS均符合准二级动力学方程,平衡吸附量(q_e)分别为0.46 mg·g~(-1)和0.38 mg·g~(-1),化学吸附占主要作用.吸附等温线可以用Freundlich、Langmuir及Temkin方程拟合.Ca~(2+)和Cu~(2+)通过离子架桥作用促进PFOS在污泥上的吸附.活性污泥吸附去除PFOS的效果明显优于去除EPS后的污泥.傅里叶红外光谱(FTIR)和X射线光电发射光谱(XPS)分析吸附前后的污泥官能团变化,发现去除了EPS的污泥中羟基、羧基和氨基活性基团减少,而这些基团是PFOS吸附过程中参与反应的主要成分.由此可见污泥EPS中蛋白质含有的羧基和氨基活性基团为PFOS提供了吸附反应位点,EPS在吸附过程中起到至关重要的作用.