CTMAB交联累托石吸附苯胺废水的研究

以十六烷基三甲基溴化铵 (CTMAB) 为交联剂与累托石进行交联反应,制备CTMAB交联累托石,吸附处理CODCr值为910.6mg/L和2806.4mg/L的苯胺废水。结果表明,当CTMAB交联累托石用量为40g/LH2O、pH为7.00和1.00、常温吸附60min时,其CODCr去除率达67%以上。吸附符合Freundlich等温吸附式:?1.338Ct1/n,吸附反应为一级反应:tteCC51019.10--=, 吸附热力学研究表明:ΔH=1.819kJ/mol,ΔG=0.051kJ/mol,ΔS=6.073J/mol稫。     

D406螯合树脂对硫酸锌溶液中氟的吸附和解吸性能及动力学研究

研究了D406螯合树脂对硫酸锌溶液中氟的吸附和解吸性能,考察了影响氟吸附和解吸的因素以及该树脂吸附和解吸氟的动力学参数。结果表明,在25℃、pH=2、硫酸锌浓度为1.50mol/L、氟离子浓度为200mg/L条件下,D406螯合树脂对氟的吸附量为5.55mg/g。D406螯合树脂对氟的吸附符合Freundlich吸附模型。吸附和解吸的动力学符合Boyd液膜扩散方程,吸附反应活化能Ea=12.14kJ/mol,解吸反应活化能Ea=19.54kJ/mol。     

双核铕-苯甲酸-邻菲咯啉三元络合物非等温热分解动力学研究

采用TG-DTG和DTA技术研究了Eu2(BA)6(PHEN)2 (BA苯甲酸根离子;PHEN1,10-邻菲咯啉)在静态空气中的热分解过程,根据TG曲线确定了热分解过程中的中间产物及最终产物,运用Acher法、Madhusudanan-Krishnan-Ninan (MKN)法和Flynn-Wall-Ozawa法对非等温动力学数据进行分析,推断出第一步热分解反应的动力学方程为dα/dt=Aexp(-E/RT)(1-α)2, 第一步热分解反应的活化能为135 kJ/mol, 活化自由能ΔG为149 kJ/mol, 活化焓ΔH为129 kJ/mol, 活化熵ΔS为-33 J/(mol·k), 同时用等温TG法得到失重10%为寿终指标的寿命方程为lnτ=-22.66+1.646×104/T.     

Mg/Al-NO_3 LDH吸附诺氟沙星的热力学和动力学研究

采用平衡吸附实验,研究了诺氟沙星在自制焙烧态镁铝水滑石(Mg/Al-NO_3 LDH)上的吸附热力学和动力学行为。结果表明,在固液比1∶500、p H=5.0、吸附温度25℃、离子强度0.1 mol/L的条件下,吸附1 h对诺氟沙星(20 mg/L)的吸附过程符合Langmuir等温线方程和准二级动力学,理论平衡吸附量达到32.05 mg/g。其热力学参数ΔG0 KJ/mol,ΔH0 KJ/mol,由此推断焙烧态镁铝水滑石对诺氟沙星的吸附是自发放热反应。     

阳离子交换树脂对新奥霉素的吸附性能分析与研究

采用阳离子交换树脂分离提取核苷肽类农用抗生素新奥霉素。实验结果表明,在8种阳离子交换树脂中,7320树脂吸附效果最好,在pH=7时,树脂的交换容量最大;3%氨水可高效地将新奥霉素从7320树脂上解析下来,解析率为95.00%。静态吸附动力学符合Lagergren准二级速率方程,颗粒内扩散为影响吸附速率的主要控速步骤,吸附速率常数为k=0.00738g/(mg·min)。吸附等温线符合Langmuir方程,由热力学平衡方程计算得ΔH=60.93kJ/mol,ΔS0,ΔG0,表明该交换过程是自发的、吸热、熵增加的过程。在动态实验中,发酵液以1BV/h上样、3%氨水以2BV/h进行解吸,解吸液经减压浓缩得到褐色膏状物质,新奥霉素得率为79.96%。     

高效液相色谱法测定金属配合物｛Fe［3-(2-吡啶基)-5,6-二苯基-1,2,4-三嗪］3｝2+两种几何异构体的动力学转变

通过高效液相色谱法研究了3-(2-吡啶基)-5,6-二苯基-1,2,4-三嗪(PDT)和Fe(Ⅱ)的配合物［Fe(PDT)3］2+的面式和经式两种几何异构体之间的动力学平衡过程。结果表明:不同温度(30,35,40,45 ℃)下,两种几何异构体含量(x)之间的相互转变均符合动力学一级反应,其xeln［(xe-x0)/(xe-x)］值和反应时间t(min)之间的关系分别为:xeln［(xe-x0)/(xe-x)］=0.082t+0.729 (r2=0.9911,T=45 ℃),xeln［(xe-x0)/(xe-x)］=0.049t+0.598 (r2=0.9987,T=40 ℃),xeln［(xe-x0)/(xe-x)］=0.022t+0.586 (r2=0.9987,T=35 ℃),xeln［(xe-x0)/(xe-x)］=0.012t+0.591(r2=0.9988,T=30 ℃)。两种异构体之间的动力学相互转变过程中的活化焓(ΔH)、活化熵(ΔS)和活化能(ΔEa)分别为:ΔH=103.84 kJ·mol-1,ΔS=271.93 J·mol-1·K-1,ΔEa=86.74 kJ·mol-1 (面式异构体向经式异构体转变);ΔH=106.47 kJ·mol-1,ΔS=257.65 J·mol-1·K-1,ΔEa=94.43 kJ·mol-1 (经式异构体向面式异构体转变)。     

氧化铟改性聚丙烯酰胺复合材料吸附水中铅的研究

环境中铅污染将威胁到生命体安全,因此去除过量的铅显得尤为重要。采用一锅法制备了复合材料吸附剂氧化铟改性的聚丙烯酰胺,通过扫描电子显微镜、N_(2)吸附-脱附仪和热重分析仪对吸附剂进行了表征。结合火焰原子吸收光谱法,研究其对水中的铅吸附性能。优化了溶液pH值及振荡时间对铅吸附的影响,并运用动力学和热力学研究了复合材料对铅的吸附行为。实验结果表明:在初始浓度为10 mg/L,溶液pH值为6.0,振荡时间为100 min时,铅的最大吸附量为9.689 mg/g;吸附行为符合拟二级动力学方程和Freundlich方程;当T=293.15 K时,ΔG=-8.38 kJ/mol,ΔH=23.90 J/mol,证明了复合材料对铅的吸附是自发进行,并且是吸热过程;经过3次吸附—解吸实验,复合材料对铅的解吸率仍大于87%,说明吸附剂的再生性能良好。     

DH-2树脂对镝的吸附及机理

研究了镝离子在HD-2树脂上的吸附行为。在HAc-NaAc体系pH=6.20时吸附最佳,测得静态饱和吸附容量为356mg/g(树脂),用0.1~2.0 mol/L HC l可定量洗脱,表观速率常数k198=1.16×105s-1,表观活化能Ea=16.1kJ/mol。等温吸附服从Freun ilich经验式,吸附热力学参数△H=16.5kJ/mol,△S=58.2 J/(mol.K),△G298=-0.859kJ/mol。用化学和红外光谱等方法讨论了吸附机理。     

大孔丙烯酸树脂对镧元素的静态与动态吸附研究

研究了大孔丙烯酸树脂(MAR)对镧离子的吸附与解吸行为.静态吸附研究pH值、接触时间和温度对吸附的影响.结果表明,大孔丙烯酸树脂可以有效地将镧离子从水溶液中去除.吸附平衡的时间为14 h.在308 K时,缓冲液pH值6.50,由Langmuir等温线模型得出大孔丙烯酸树脂对镧离子的最大吸附量是379 mg·g-1.吸附过程符合液膜扩散动力学(k=4.37×10-5～5.06×10-5s1).与Freundlich等温线相比,吸附过程更符合Langmuir等温线模型.吸附热力学参数分别为:△H=16.7 kJ·mol-1,△S=130 J·(mol·K)-1,△C298K=-22.0 kJ·ml-1.托马斯模型用于确定动态吸附的特征参数以及预测突破曲线.镧离子可以用浓度为0.5 mol·L-1的HCl溶液洗脱.利用红外光谱技术对大孔丙烯酸树脂的表面进行吸附前与吸附后的表征.     

四乙烯五胺功能化纳米高分子材料对Cr(VI)与磷酸盐共存体系的吸附机理

合成了四乙烯五胺功能化纳米高分子材料(TEPA-NP),采用傅里叶变换红外光谱分析(FTIR)、有机元素分析(EA)、X射线光电子能谱分析(XPS)等手段对其进行了表征,重点考察了其对水中Cr(VI)与磷酸根离子共存时的吸附机理.结果表明,溶液p H对TEPA-NP的吸附性能影响较大.对于Cr(VI)或磷酸盐单一体系,p H 2.5时TEPA-NP的吸附效果最佳;吸附热力学均符合Langmuir模型,吸附动力学均符合准二级速率方程.TEPA-NP对Cr(VI)的饱和吸附量为123.5 mg/g;吸附过程为吸热熵增的自发过程,ΔH为16.06 k J/mol,ΔS为59.02 J/(mol K),308 K时ΔG为-2.10 k J/mol;吸附活化能为30.28 k J/mol.TEPA-NP对磷酸盐的饱和吸附量为149.2 mg/g;吸附过程为放热熵增的自发过程,ΔH为-1.74 k J/mol,ΔS为1.91J/(mol K),308 K时ΔG为-2.32 k J/mol;吸附活化能为18.85 k J/mol.当磷酸盐的共存浓度小于100 mg/L时,磷酸盐对TEPA-NP吸附Cr(VI)几乎没有影响;而当Cr(VI)的共存浓度大于5 mg/L时,Cr(VI)对TEPA-NP吸附磷酸盐的影响已较为明显,可使TEPA-NP吸附磷酸盐的饱和吸附量减小17.3%;结合红外和XPS表征可以推测TEPA-NP对Cr(VI)的吸附涉及静电与配位相互作用,而对磷酸盐以静电吸附为主;Cr(VI)与磷酸盐共存时,TEPA-NP优先吸附Cr(VI).Cr(VI)可以通过竞争取代吸附在TEPA-NP上的磷酸根,且随着Cr(VI)初始浓度增大,TEPA-NP上吸附的总磷脱附的比例增大;而磷酸根对Cr(VI)的竞争吸附较难实现.     

ADSORPTION OF MACROPOROUS PHOSPHONIC ACID RESIN FOR INDIUM

The adsorption kinetics and mechanism of a nrovel chelate resin, macroporous phosphonic acid resin (PAR) for In(Ill) were investigated Tile statically saturated adsorption capacity is 216mg·g^-1resin at 298K in HAc-NaAc medium. Tire apparent adsorption rate constant is k298=4.84×10^-5 s^-1. Tile adsorption behavior of PAR for In(Ill) obeys the Freundlich isotherm. The thermodynamic adsorption parameters, enthalpy change △H, free energy change △G and entropychange △S of PAR for In(Ⅲ) are 11.5kmol, -12.6kJmol and 80.8Jmol.K, respectively. The apparent activation energy is Ea=3.5k.l/mol. Tire molar coordination ratio of the functional group of PAR to In(Ⅲ) is about 3:1.     

D152树脂对铜(Ⅱ)的吸附性能

The sorption behavior and mechanism of D152 resin for Cu~(2+) is investigated.D152 resin has a good adsorptivity for Cu~(2+) in the HAc-NaAc medium at pH=4.73.The statically saturated sorption capacity is 309mg/g·(resin).Cu~(2+)adsorbed on D152 resin can be eluted quantitatively by using 0.1-2.0mol/L hydrochloric acid as an eluant.The apparent rate constant and activation energy are k_(298)=1.86×10~(-5) sec~(-1) and Ea=12.3kJ/mol.The sorption behavior of D152 resin for Cu~(2+) obeys the Freundlich isotherm.The sorption thermodynamic parameters of D152 resin for Cu~(2+)are enthalpy change ΔH=14.6 kJ/mol,free energy change ΔG=-0.72kJ/mol,entropy change ΔS=51.4J/(mol·K).respectively.     

纳米γ-Al_2O_3吸附Ge(Ⅳ)的机理及性能

研究了纳米γ-Al2O3吸附剂对Ge(Ⅳ)的吸附行为,考察了吸附平衡时间、温度和溶液的pH值等因素对吸附过程的影响.结果表明,纳米Al2O3对Ge(Ⅳ)的吸附在2min时基本达到平衡,在pH=4～11范围内,Ge(Ⅳ)可以被纳米Al2O3定量富集,吸附率大于95%;吸附于纳米Al2O3上的Ge(Ⅳ)可以用0.3mol/LK3PO4和1mol/LH2SO4混合溶液洗脱,5min后基本达到解析平衡,解析率能达到97%;该吸附过程符合准二级反应动力学模型,计算了不同温度下的吸附速率常数,并求得纳米Al2O3对Ge(Ⅳ)的吸附活化能(Ea)为11.63kJ/mol;该体系的吸附过程符合Freundlich等温式,由D-R等温式求得常温下纳米Al2O3对Ge(Ⅳ)的平均吸附能为10.87kJ/mol.Ge(Ⅳ)吸附反应的ΔG0为负值,焓变ΔH0为正值,说明该吸附过程是自发的吸热反应.     

717型阴离子交换树脂吸附水溶性芳香族有机污染物研究

研究了717型阴离子交换树脂对苯酚、苯甲酸和十二烷基苯磺酸钠(SDBS)等水溶性芳香族污染物吸附过程的基本化学问题.研究结果表明:717型树脂对苯酚、苯甲酸和SDBS的吸附过程均符合Lagergren二级吸附动力学方程,吸附速率均随着温度的升高而加快,吸附表观活化能Ea分别为13.2kJ/mol、59.5kJ/mol和48.1kJ/mol,吸附过程△H0和△S0均为正值,△G0均为负值,吸附能够自发进行;吸附等温模型符合Langmuir等温式;318K时,717型树脂在pH=9.1对SDBS的饱和吸附容量为360mg/g;在pH=10.2,对苯酚和苯甲酸的饱和吸附容量分别为194mg/g和286mg/g.用浓度均为0.5mol/L,体积比为5∶1的NaCl-NaOH混合溶液可快速洗脱树脂上吸附的污染物,洗脱率达98％以上.该树脂对水溶性芳香族污染物吸附容量大,易于再生和循环利用,可用于环境水体中水溶性芳香族有机污染物的吸附治理.     

果糖催化合成四氢苯并[b]吡喃衍生物:动力学和机理研究(英文)

Fructose was used as an efficient catalyst for three-component condensation reactions of aryl aldehydes,malononitrile,and dimedone in a mixture of EtOH and H_2O as green solvents.The advantages of this method are a short reaction time,high yields,low cost,easy accesses,and simple work-up.The mechanism of the synthesis of a derivative of 4H-tetrahydrobenzo[b]pyran was clarified using spectroscopic kinetic methods.The activation energy(Ea=65.34 kJ/mol)and related kinetic parameters(ΔG=69.14 kJ/mol,ΔS=20.99 J/(mol·K),andΔH=62.89 kJ/mol)were calculated,based on the effects of temperature,concentration,and solvent.The first step in the proposed mechanism was identified as the rate-determining step(k1),based on the steady-state approximation.     

Removal of cibacron blue 3G-A (CB) dye from aqueous solution using chemo-physically activated biochar from oil palm empty fruit bunch fiber

A novel biodegradable adsorbent called pyrolysed empty fruit bunch fibres (PEF) was prepared by chemo-physical activation of empty fruit bunch fibres (EFB) biochar for removal of cibacron blue 3G-A (CB) dye from aqueous solution. PEF was characterized using FTIR, SEM-EDX, XRD and BET techniques. The N₂ adsorption-desorption isotherms indicated PEF’s surface area to be 362.84 m²g⁻¹ and XRD attributed amorphous nature to PEF. After adsorption process, PEF has smoother surface morphology, increase in carbon by weight and shift in functional groups. The established adsorption optimum conditions were pH 10, 45 min contact time and 0.10 g/100 mL adsorbent dosage with 99.05% CB dye removal capacity at 343 K and initial dye concentration 100 mg/L. Desorption ratio >90% after seventh cycle of adsorption-desorption experiments confirmed high reusability (regeneration) of PEF. Pseudo second order kinetic and Freundlich were better fitted with kinetic and isotherm model respectively, while mechanism of adsorption was controlled by film diffusion (external mass transfer). Thermodynamic studied revealed ΔG, ΔS and ΔH to be −3.12 MJ/mol K, 9.11 kJ/mol K, 6.83 kJ/mol respectively at 343 K. The negative value of ΔG, positive values of ΔS and ΔH indicated spontaneity, feasibility and endothermic nature of CB dye adsorption from aqueous solution onto PEF.     

Cooperative spin transition in the two-dimensional coordination polymer [Fe(4,4'-bipyridine)2(NCX)2]·4CHCl3 (X = S, Se)

Two new isostructural two-dimensional (2D) coordination polymers exhibiting spin crossover (SCO) behavior of formulation [Fe(4,4'-bipy)(2)(NCX)(2)]·4CHCl(3) (4,4'-bipy = 4,4'-bipyridine; X = S [1·4CHCl(3)], Se [2·4CHCl(3)]) have been synthesized and characterized, and both undergo cooperative spin transitions (ST). For 1·4CHCl(3) the ST takes place in two steps with critical temperatures of T(c1)(down) = 143.1 K, T(c2)(down) = 91.2 K, T(c1)(up) = 150.7 K, and T(c2)(up) = 112.2 K. 2·4CHCl(3) displays half ST characterized by T(c)(down) = 161.7 K and T(c)(up) = 168.3 K. The average enthalpy and entropy variations and cooperativity parameters associated with the ST have been estimated to be ΔH(1)(av) = 5.18 kJ mol(-1), ΔS(1)(av) = 35 J K(-1) mol(-1), and Γ(1) = 2.8 kJ mol(-1) and ΔH(2)(av) = 3.55 kJ mol(-1), ΔS(2)(av) = 35 J K(-1) mol(-1), and Γ(2) = 2.6 kJ mol(-1) for 1·4CHCl(3), and ΔH(av) = 6.25 kJ mol(-1), ΔS(av) = 38.1 J K(-1) mol(-1), and Γ = 3.2 kJ mol(-1) for 2·4CHCl(3). At T > [T(c1) (1·4CHCl(3)); T(c) (2·4CHCl(3))], both compounds are in the space group P2/c while at T < [T(c1) (1·4CHCl(3)); T(c) (2·4CHCl(3))] they change to the C2/c space group and display an ordered checkerboard-like arrangement of iron(II) sites where the high- and low-spin states coexist at 50%.     

Conversion of teak wood waste into microwave-irradiated activated carbon for cationic methylene blue dye removal: Optimization and batch studies

The objective of this study is to find optimum preparation conditions in converting teak wood waste into activated carbon (TWAC) and to evaluate its performance in adsorbing cationic dye of methylene blue (MB). TWAC was produced via physiochemical activation (potassium hydroxide, KOH chemical treatment, and carbon dioxide, CO₂ gasification) and heated through microwave irradiation technique. With the aid of response surface methodology (RSM), optimized TWAC was successfully synthesized at radiation power, radiation time, and impregnation ratio (IR) of 366 W, 5.30 min, and 1.15 g/g, respectively. These preparation conditions produced TWAC with MB adsorption uptakes of 66.69 mg/g and a yield of 38.23%. Characteristics of TWAC in terms of BET surface area, mesopores surface area, total pore volume, and average pore diameter were determined to be 1345.25 m²/g, 878.63 m²/g, 0.6140 cm³/g, and 2.85 nm, respectively. Isotherm studies divulged that the MB-TWAC adsorption system followed the Langmuir model with a maximum monolayer adsorption capacity of 567.52 mg/g. In terms of kinetic studies, this adsorption system fit pseudo-second order model the best whereas Boyd plot confirmed that the adsorption process was controlled by the film diffusion mechanism. Thermodynamic parameters of enthalpy change, ΔH°, entropy change, ΔS°, Gibbs free energy, ΔG° and Arrhenius activation energy, E_a were calculated to be ?4.06 kJ/mol, 0.06 kJ/mol.K, –22.69 kJ/mol and 16.03 kJ/mol, respectively. The activation and microwave heating methods employed succeeded to produce TWAC with excellent adsorption performance in removing MB dye. TWAC was also successfully regenerated for 5 cycles via microwave heating technique.     

Adsorption of methyl orange on nanoparticles of a synthetic zeolite NaA/CuO

CuO supported on an NaA zeolite (CuO/NaA) was prepared with an NaA zeolite through the ion-exchange (CuO/NaA) method. The morphology and the physicochemical properties of the prepared samples were investigated by XRD, MEB, and EDS. The various parameters, such as contact time, catalyst dose, initial dye concentration, initial pH, and temperature, influencing the adsorption of methyl orange (MO) were optimized. The MO adsorption equilibrium was reached after 240 min of contact time. Removal of MO is better at neutral pH than in acidic and alkaline solutions. Among the tested models, the equilibrium adsorption data are well fitted by the Langmuir isotherm. The adsorption kinetics is best described by the pseudo-second-order model. The evaluation of the thermodynamic parameters, i.e. ΔG^o, ΔH^o, and ΔS^o, revealed that MO adsorption was spontaneous, while the activation energy (20.98 kJ/mol) indicates a physical adsorption. The photodegradation of MO decreased from 100 mg/L down to 2 mg/L when the solution is exposed to visible light.     

Kinetic study of the thermal inactivation of glucose oxidase in the presence of denaturant and stabilizer by means of bioelectrocatalysis method

The thermal inactivation of glucose oxidase (GOD) in aqueous solution has been studied by the electrochemical method to follow the bioelectrocatalytic current due to the oxidation of glucose by GOD. Exponential time-dependent decrease in bioelectrocatalytic current, that is, the decrease in the enzymatic activity of GOD, was observed at given temperatures to determine the rate constant (k) of a simple inactivation process: GOD (active) → GOD (inactive). The ln[k] vs. T(-1) plots gave straight lines with all solution conditions tested, so that the resulting Arrhenius activation parameters including ΔH(?) and ΔS(?) can be compared with each other. In the 50 mmol/L phosphate buffer at 70°C, k was determined to be (6.6 ± 1.6)× 10(-4) s(-1), and ΔH(?) and ΔS(?) were calculated to be 202 ± 13 kJ mol(-1) and 282 ± 39 J K(-1) mol(-1), respectively. By addition of 3 mol/L guanidine hydrochloride, the k was increased to (4.7 ± 0.6)× 10(-3) s(-1), indicating that the denaturant accelerates the thermal inactivation. In this case, ΔH(?) was significantly reduced. By addition of 1 g/L ε-poly-L-lysine, which may adsorb onto the GOD surface to reduce the local disorder, k was decreased to (1.8 ± 0.6)× 10(-4) s(-1). In this case, ΔS(?) was reduced but ΔH(?) was not decreased much. This can be used as an important indication for selection of the enzyme stabilizer in solution.