阳离子交换膜对Cu~（2＋）离子交换的动力学及热力学研究

对阳离子交换膜离子交换Cu2＋的动力学及热力学现象进行了研究,结果表明：温度25℃,溶液pH=6时,干膜对Cu2＋饱和交换容量为0.506 mmol/g;随Cu2＋初始浓度的升高,离子交换速率常数随之增加;随温度升高,离子交换速率常数随之增加;随转速升高,离子交换速率常数随之增加;离子交换过程与一级反应速率方程拟合结果良好;△G0〈0,表明离子交换反应能自发进行;△H0m〉0,表明的交换反应为吸热反应;△S0〉0,表明交换反应是熵变增加的反应。     

活性炭纤维对水中微囊藻毒素的吸附性能

利用活性炭纤维对水中微囊藻毒素MC—LR的吸附，研究了吸附过程的热力学与动力学特性。结果表明，活性炭纤维对MC—LR的平衡吸附量在相同温度下随MC-LR初始浓度的增加而显著增大，并随着温度升高而增加，最大吸附量达246μg／g。不同温度条件下，活性炭纤维对MC-LR的吸附均较好地符合Langmuir等温吸附模型。通过热力学分析发现，△H=15．7kJ／mol、△G〈0、△S〉0，表明该吸附是自发的、吸热的过程，温度升高有利于吸附反应。动力学研究表明，该过程符合一级动力学方程。吸附反应速率受颗粒内扩散和液膜扩散共同影响。活性炭纤维经再生后，平衡吸附量变化较小，具有良好的重复使用性能。     

黄河水中沉积物与锌、镉液-固界面的作用

研究了黄河水中沉积物与重金属污染物Zn^2 、Cd^ 的离子交换吸附作用。结果表明,Zn^2 、Cd^2 在黄河水中主要以M（OH）^ 的形式与沉积物进行－价阳离子交换反应;在天然黄河水pH范围内,Zn^2 、Cd^2 的离子交换率都大于70％;随温度升高,Zn^2 、Cd^2 与沉积物的交换率增加,E-pH曲线向pH值减小的方向位移。     

阳离子交换树脂对NH4+的吸附热力学与动力学研究

采用静态吸附法,研究了NH4+在阳离子交换树脂上的吸附行为,并从热力学和动力学两方面对吸附过程进行了分析.结果表明,NH4+为200～1000 mg/L时,强酸性阳离子交换树脂001×7的NH4+吸附容量大于D001、D113树脂；在实验温度下,采用Langmuir吸咐等温模式能够更好地描述NH4+在001×7树脂上的静态吸附行为,001×7树脂对NH4+的交换吸附属于单分子层吸附；常温(25℃)时,001×7树脂吸附NH4+过程的焓变(△H)大于零,说明NH4+进入树脂后与H+的交换反应为吸热反应,升温有利于反应的进行,此吸附过程的熵变(△S)也大于零,说明该离子交换过程属于熵增的过程,此吸附过程的吉布斯自由能变(△G)小于零,说明该离子交换过程能够自发进行;吸附动力学研究表明,液膜扩散是001×7树脂对NH4+吸附的限速步骤,吸附交换过程符合Lagergren准一级动力学方程；4％(质量分数)NaOH溶液较适合作为001×7树脂的再生液,经过5次再生后,001×7树脂的吸附量只下降了8.8％.     

钻井废液的超临界水氧化处理及动力学分析

在反应温度为500～600℃、压力为25～30 MPa、停留时间为30～600 s的条件下,在连续式反应器中研究了钻井废液的超临界水氧化反应.结果表明:钻井废液的COD去除率可达90.00%以上;在600℃、停留时间为600 s时,钻井废液氧化后,剩余收集液的COD＜120 mg/L,满足《污水综合排放标准》(GB 8978-1996)中的二级标准.用幂函数方程描述了氧化剂过量时钻井废液超临界水氧化的反应动力学规律,反应速率常数与温度的关系符合Arrhenius公式,随停留时间的增加、温度的升高,有机物的去除率显著增加;反应速率常数随压力升高而增加,但反应速率常数的增幅随压力的升高而减小,反应活化体积不是常数.在25 MPa时,反应活化能和频率因子分别为(17 745.430 40±1 114.983 42)kJ/mol和1.152 3×10-4s-1模型计算值与实验值的误差在±15%以内.     

改性荞麦壳对水溶液中Cu~(2+)离子吸附效果及机理

以柠檬酸对荞麦壳进行化学改性,改性后荞麦壳吸附剂对Cu2+的吸附量增加。研究了不同pH、吸附剂投入量、浓度和时间对吸附效果的影响。在pH值为5.5,Cu2+初始浓度50 mg/L,吸附剂投入量为1 g,吸附时间为120 min的条件下,Cu2+的吸附量达到较大值。通过用改性荞麦壳吸附剂对Cu2+的热力学吸附过程的分析,结果表明,改性荞麦壳吸附剂符合Langmuir吸附等温模式,改性荞麦壳吸附剂对Cu2+的吸附存在化学吸附,改性荞麦壳的最大吸附量可以达2.26 mg/g。研究改性荞麦壳吸附剂吸附Cu2+的动力学特性,吸附动力学行为可用准二级速率方程进行很好的描述,准二级吸附速率常数随温度升高而增大。准一级速率方程和颗粒扩散模型可以较好地描述吸附初始阶段,Cu2+浓度较高,颗粒内扩散;吸附后期,Cu2+浓度较低,受到颗粒外扩散的控制。总之,整个吸附过程可能是多种动力学机理共同作用的结果。     

水溶液中甲基橙的超声化学降解动力学研究

研究了水溶液中甲基橙的超声化学降解动力学。结果表明 ,水溶液中甲基橙可通过超声化学方法降解 ,降解动力学为一级反应 ,降解速率常数为 -2 .2 5× 10 - 3m in- 1。甲基橙降解速率随初始浓度的升高而降低 ,随介质温度的下降而升高 ,随介质酸度的变化而变化。 H2 O2 、F e2 +和 I- 等自由基促进剂可有效加速甲基橙的降解     

印染废水催化湿式氧化法处理中水质酸碱度的变化

以初始质量浓度为1088 mg/L、色度为30万倍的亚甲蓝溶液模拟印染废水进行实验,系统考察了印染废水催化湿式氧化(CWAO)法处理中水质酸碱度的变化.结果表明,处理后出水pH呈先降低后升高的趋势,而且反应前期pH降低的幅度大,反应后期pH升高的幅度小;出水中pH最低点随CulFel催化剂(Cu2+、Fe2+质量比为1:1)投加量的增加、氧分压的升高、进水pH的降低而降低;反应温度越高,出水pH越先达到最低点;反应终点出水pH随CulFel催化剂投加量的增加、氧分压的升高、反应温度的升高、进水pH的升高而升高.     

制备条件对Ni-Y分子筛的性质及其吸附二苯并噻吩性能的影响

采用液相离子交换法制备Ni-Y分子筛,考察制备条件对它的性质及其吸附燃料油中二苯并噻吩(DBT)性能的影响。结果表明:(1)采用液相离子交换法制备Ni-Y分子筛适宜使用0.1mol/L的Ni(NO3)2溶液作为离子交换液,交换温度提高有利于Ni-Y分子筛的含Ni量增大。(2)当活化温度为300～450℃时,脱硫率随活化温度提高而增大,原因是温度升高有利于除去分子筛的吸附水和结晶水,增加其与有机物质的亲和力。活化温度高于450℃后,Ni-Y分子筛的脱硫率大幅下降,可能是因为高温下分子筛表面的Ni2+反应生成NiO化合物,同时使Ni2+由超笼向稳定的SI位置迁移。(3)在甲苯等干扰物质存在的条件下,Ni-Y分子筛的吸附性能优于其他分子筛,其对DBT为500mg/L、甲苯体积分数为5%的模拟燃油中DBT吸附量分别是Na-Y、Mg-Y及Cu(Ⅱ)-Y分子筛的2.57、2.32、4.24倍,因而更具有实际应用价值。     

水体系中正癸烯的光催化降解

以中压汞灯为光源 ,研究了水体系中正癸烯 (n C10 H2 0 )在TiO2 光催化氧化作用下的降解。结果表明 ,降解反应符合一级动力学方程 ;n C10 H2 0 在不同粒径TiO2 下的反应速率常数k为 6 .80— 9.90× 10 -3 min-1(在 30 0W中压汞灯下 ) ,其值随粒径的增加而降低 ;在相同粒径下 ,k值随光强增加而增大。同时测定了在水体中掺杂 1wt% (即过渡金属质量占Ti原子质量的百分数 )的过渡金属离子时 ,n C10 H2 0 的光降解速率常数k为 11.4— 15 .9× 10 -3 min-1,因而其对光降解的影响顺序是 :Ag+ >Fe3 + >Pb2 + >Fe2 + >Zn2 + >Mn2 + 。产物经GC/MS分析表明 ,水体中n C10 H2 0 光催化降解生成辛醛、壬醛、癸醛和 2 癸酮。     

改性天然沸石去除水中氨氮的研究

分别采用NaCl、KCl和CaCl2对黑龙江省某市天然沸石进行改性，考察了pH值、氨氮初始浓度以及温度对改性沸石交换性能的影响，并对改性沸石的交换动力学进行了研究。结果表明，NaCl和KCl改性对沸石原矿交换容量有不同程度提高，而KCl改性后容量有所降低。pH、NH4初始浓度以及温度对交换性能有明显影响，pH6．0附近沸石交换容量最大；NH4初始浓度越高，反应速度越快，相同初始浓度下，钾型沸石交换速度较快，而沸石原矿交换速度最慢。采用Langmuir型离子交换等温线进行非线性回归的结果显示，低温有利于交换反应的进行。溶液中NH4^＋在改性沸石上的离子交换反应可采用Vermeulen模型描述，沸石原矿拟合相关系数较差。改性沸石多次再生后，其交换容量均有所降低。     

天然和CPB改性沸石对Hg^2＋的吸附特征

通过静态实验研究溴代十六烷基吡啶（CPB）改性沸石和天然沸石对废水中Hg^2＋的吸附特性，探讨了吸附动力学、吸附平衡和吸附热力学机制。研究表明：Langmuir方程能较好地描述2种沸石对Hg^2＋的吸附，CPB改性沸石对Hg^2＋的吸附率得到显著提高。实验条件下，改性沸石对Hg^2＋的吸附率从67．5％提高到98．9％，吸附容量从0．521mg／g提高到3．07mg／g。利用准一级动力学方程、假二级动力学方程、颗粒内扩散模型和Elovich方程分别对动力学过程进行拟合，发现2种沸石对Hg^2＋的吸附均满足假二级动力学方程，且离子的颗粒内扩散对整个吸附过程有影响。动力学拟合、D-R方程拟合和热力学研究综合表明：2种沸石对Hg^2＋的吸附既存在化学吸附又存在物理吸附，吸附吉布斯自由能变（△G^0）、焓变（△H^0）、熵变（△S^0）均小于0，反应为自发的放热反应，低温有利于吸附的进行。     

改性天然沸石去除水中氨氮的研究

分别采用NaCl、KCl和CaCl2对黑龙江省某市天然沸石进行改性,考察了pH值、氨氮初始浓度以及温度对改性沸石交换性能的影响,并对改性沸石的交换动力学进行了研究.结果表明,NaCl和KCl改性对沸石原矿交换容量有不同程度提高,而KCl改性后容量有所降低.pH、NH4 初始浓度以及温度对交换性能有明显影响,pH 6.0附近沸石交换容量最大;NH4 初始浓度越高,反应速度越快,相同初始浓度下,钾型沸石交换速度较快,而沸石原矿交换速度最慢.采用Langmuir型离子交换等温线进行非线性回归的结果显示,低温有利于交换反应的进行.溶液中NH4 在改性沸石上的离子交换反应可采用Vermeulen模型描述,沸石原矿拟合相关系数较差.改性沸石多次再生后,其交换容量均有所降低.     

Degradation of aqueous carbon tetrachloride by nanoscale zerovalent copper on a cation resin

Nanoscale zerovalent copper supported on a cation resin was successfully synthesized to enhance the removal of carbon tetrachloride (CCl(4)) from contaminated water. The use of the cation resin as a support prevents the reduction of surface area due to agglomeration of nanoscale zerovalent copper particles. Moreover, the cation resin recycles the copper ions resulting from the reaction between CCl(4) and Cu(0) by simultaneous ion exchange. The decline in the amount of CCl(4) in aqueous solution results from the combined effects of degradation by nanoscale zerovalent copper and sorption by the cation resin; thus the amount of CCl(4) both in aqueous solution and sorbed onto the resin were measured. The pseudo-first-order rate constant normalized by the surface-area and the mass concentration of nanoscale zerovalent copper (k(SA)) was 2.1+/-0.1 x 10(-2)lh(-1)m(-2), approximately twenty times that of commercial powdered zerovalent copper (0.04 mm). Due to the exchange between Cu(2+) and the strongly acidic ions (H(+) or Na(+)), the pH was between 3 and 4 in unbuffered solution and Cu(2+) at the concentration of less than 0.1 mg l(-1) was measured after the dechlorination reaction. In the above-ground application, resin as a support would facilitate the development of a process that could be designed for convenient emplacement and regeneration of porous reductive medium.     

Characterization of Cr ion exchange with hydrotalcite

Experiments were performed to characterize the removal of chromium from water with uncalcined hydrotalcite, a clay mineral ion exchange media. The process was characterized as a function of pH, temperature, contact time, and both Cr and hydrotalcite concentrations. A Freundlich isotherm, used to describe adsorption equilibria, was used as a model and Freundlich constants were determined. The kinetics of the ion exchange reaction were also modeled using a pseudo-first order reaction rate. Finally, an equilibrium stage process was modeled with sequential batch separations to determine if hydrotalcite ion exchange could reduce aqueous Cr levels to below the EPA limit of 0.1mgl(-1). It was shown that the process is highly pH dependent, only yielding significant removals at pH levels between 2.0 and 2.1. While hydrotalcite concentration, Cr concentration, and time did effect the ion exchange, temperature was not found to be a factor. Under optimal conditions, maximum removals of greater than 95% were achieved. Finally, sequential batch tests performed on initial Cr solutions ranging from 5mgl(-1) to 40mgl(-1), demonstrated that the water could be purified to a level that was not statistically different than the EPA limit, thus demonstrating the applicability of hydrotalcite ion exchange.     

Effects of copper and palladium on the reduction of bromate by Fe(0)

Bromate reduction by Fe(0) with incorporation of copper or palladium was investigated in batch tests. The incorporation of copper led to an increase in the rate of bromate reduction, while incorporation of palladium did not show any effect on bromate reduction by Fe(0), regardless of the bimetal application techniques (either simultaneous addition of Cu(II) or Pd(IV) into the Fe-BrO3- reaction system or using copper or palladium amended iron for bromate removal). Surface analyses by X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) techniques indicated that aqueous Cu(II) was reduced and incorporated into the iron surface to form Cu2O and Cu(0). Among these two species, pure Cu(0) is not an active electron donor to the bromate reduction reaction, as shown by there being no reduction from using Cu(0) powders alone and no enhancement by Fe(0) when physically mixed with Cu(0). Although it has been proposed in the literature that the enhancement of adsorption also contributes to the enhancement of chemical reduction, this is not the case here because adsorption decreased when Cu increased. The enhanced bromate reduction rate in the presence of copper observed here is most likely the result of the newly formed active Cu(I). The presence of PdO was evidenced by XPS but yielded no enhancement in bromate reduction. Finally, the Cu2O present on the iron surface because of copper impurities in commercially available iron was found to be involved in the bromate reduction and to accelerate the reduction rate.     

Nitrate reduction by fluoride green rust modified with copper

Nitrate reduction by the fluoride form of green rust modified with copper (GR-F(Cu)) was investigated using a batch reactor system. The extent of nitrate reduction was measured by measuring the increase in concentration of ammonia, which is the final product of nitrate reduction by GR. This approach was required, because nitrate could be removed from solution by ion exchange without reduction. The rate of ammonium production was investigated over the range of pH 7.8-11. The fastest reaction was achieved at pH 9 when GR was present at a concentration of 0.083M as Fe(II) and 1mM of Cu(II) was added. The rate at pH 9 was enhanced by a factor of 2.5 compared to that at pH 7.8 by comparing the time elapsed to transform all nitrate to ammonium. Kinetics of nitrate reduction by GR-F at pH 7.8 were affected by the concentration of Cu(II) added. The rate constants for ammonium production increased from 0.012 to 1.52h(-1) as Cu(II) additions increased from 0 to 2.5mM, but the reaction rate at 5mM was slightly decreased to 1.25h(-1). The mechanism of enhanced rates of nitrate reduction by addition of Cu(II) could not be fully determined in this study. However, XRD results showed that magnetite was produced in the reaction of Cu(II) and GR-F and SEM shows the production of nano-size particles which were not fully identified in this study. In addition, the concentration of Fe(II) in GR was observed to linearly decrease with concentration of Cu(II) added.     

Intra-particle migration of mercury in granular polysulfide-rubber-coated activated carbon (PSR-AC)

The depth profile of mercuric ion after the reaction with polysulfide-rubber-coated activated carbon (PSR-AC) was investigated using micro-X-ray fluorescence (μ-XRF) imaging techniques and mathematical modeling. The μ-XRF results revealed that mercury was concentrated at 0-100 μm from the exterior of the particle after 3 months of treatment with PSR-AC in 10 ppm HgCl₂ aqueous solution. The μ-X-ray absorption near edge spectroscopic (μ-XANES) analyses indicated HgS as a major mercury species, and suggested that the intra-particle mercury transport involved a chemical reaction with PSR polymer. An intra-particle mass transfer model was developed based on either a Langmuir sorption isotherm with liquid phase diffusion (Langmuir model) or a kinetic sorption with surface diffusion (kinetic sorption model). The Langmuir model predicted the general trend of mercury diffusion, although at a slower rate than observed from the μ-XRF map. A kinetic sorption model suggested faster mercury transport, which overestimated the movement of mercuric ions through an exchange reaction between the fast and slow reaction sites. Both μ-XRF and mathematical modeling results suggest mercury removal occurs not only at the outer surface of the PSR-AC particle but also at some interior regions due to a large PSR surface area within an AC particle.