聚合氯化铁-腐殖酸(PFC-HA)冷冻干燥絮体的表面与孔分形研究

采用低温急速冷冻-真空干燥技术制备了PFC-HA絮体的粉末样品,研究了这些样品的物理与分形特征.结果表明,PFC-HA絮体具有晶体结构,SEM图象中有方块状形体;絮体主要组成元素为C、O、Fe,所含的特征官能团保留了絮体组成原料的一些特征;絮体的干燥样品的BET比表面积为51～92 m2·g-1,BJH累积吸附孔体积为0.0638～0.108 cm3·g-1,BJH脱附平均孔径为3.53～4.60nm,PSD峰值对应孔径3.9nm(4#样品还有另外一个PSD峰值53.2nm).PFC-HA絮体的干燥样品具有自相似性的粗糙表面,呈现多尺度分形特征;图象法确定的表面分形维数Ds值远低于N2吸附/脱附等温线法确定的结果,分别为2.14～2.22、2.90～2.96;前者的分形尺度大约处于23～390nm之间,主要属于絮体干燥样品的外表面尺度,后者的分形特征尺度区间的下限大约为0.2nm,属于孔表面尺度,因此,PFC-HA絮体干燥样品的表面粗糙度主要集中于孔表面.另外,对同一絮体,N2吸附法和脱附法确定的孔表面分形维数基本相同.通过热力学模型计算出的4#样品的Ds值接近于FHH理论计算出的结果,但分形尺度的区间变小了.     

聚合氯化铁-腐殖酸(PFC-HA)絮体的粒度和分形维数的动态变化

通过采集PFC-HA絮体的单个样品和拍摄它们的二维图像,研究了在不同混凝条件下絮体的粒度和分形维数的变化.结果表明,原水pH的下降滞后了PFC-HA絮体的出现.原水pH≥7.0时,随着投药量的增加,PFC-HA絮体的分形维数D2(lgA-lgdL)和D3(lgV1-lgdL)随之降低,表明絮体的结构越来越疏松;而原水pH=5.0时,PFC-HA絮体的分形维数存在波动.在PFC的最佳投药量时,水力条件的优化可以提高HA的去除效果,但随着原水pH的下降,HA去除效果的提高程度也随之减小.在最佳水力条件下,PFC-HA絮体的粒度为数百微米,其分形维数值较大,表明絮体的结构较为密实.此外,PFC-HA絮体的粒度分布具有(类)分形特征,最佳水力条件下正的D.值表明絮体的粒度分布趋向平稳.在整个混凝搅拌过程中,PFC-HA絮体的分形维数的变化是与混凝的溶液化学条件、搅拌时间和分形维数类型有关,其D2具有先上升后下降的趋势,这一过程中絮体结构先趋向密实,然后趋向疏松.而且慢速搅拌过程中絮体的尺度也是先增加后下降.     

聚合氯化铁-腐殖酸(PFC-HA)絮体的不同拓扑空间下分形维数的研究

通过对PFC混凝去除水中HA过程中所形成的PFC-HA絮体的研究结果表明,原水pH分另4为9.0、7.0和5.0时,最佳投药量下形成的絮体的平均沉降速度之间的比值为1.17:1.00:0.49,而且所有絮体的水平投影方向的平均直径与垂直投影方向的平均直径的比值均接近0.85.结合Logan公式和有效密度-长轴的双对数关系计算出的絮体三维空间的分形维数Df较为可靠,在本试验中3种pH的原水下形成的PFC-HA絮体的Df均小于2.0.絮体沉降速度的变化是质量分形维数Df、有效密度和粒径等因素的变化综合影响结果,因此,絮体的Df、有效密度各自的变化趋势有可能与沉降速度的不一致.原水pH=7.0时絮体的Df稍大于原水pH=9.0时絮体的Df,但比原水pH=5.0时絮体的Df大11.73%.可见,与原水pH=9.0时形成的絮体相比,原水pH=7.0时形成了稍微密实的小絮体,但原水pH=5.0时却形成了较为疏松的、很小的絮体.在本试验的图像分辨率下,PFC-HA絮体在一维拓扑空间下的分形维数D1比较低,一般都低于1.10.基于投影面积-长轴关系计算的二维拓扑空间的分形维数D2变化趋势为样品3稍大于样品2,样品1最小;然而基于投影面积一周长计算的二维拓扑空间的分形维数D2却呈现不同的变化趋势.另外,尽管PFC-HA絮体的Df小于2,但其与基于投影面积-长轴关系计算的二维拓扑空间的分形维数D2不相等,不符合Meakin的结论,这与本试验中CCD相机的分辨率和絮体样本数量有关.     

聚合氯化铝-腐殖酸(PACl-HA)絮体的物理与分形特征研究

采用低温急速冷冻-真空干燥技术制备了PACl-HA絮体的粉末样品,研究了这些样品的物理与分形特征.结果表明,PACl-HA絮体具有无定形结构,主要组成元素为C、O、Al,所含特征官能团保留了絮体组成原料的一些特征;絮体的BET比表面积为130～161 m²·g^-1,BJH累积吸附孔体积为0.38～0.52 cm³·g^-1,BJH脱附平均孔径为7.7～9.6nm,PSD峰值对应孔径8.4～11.2nm.PACl-HA絮体具有自相似性的粗糙表面,呈现多尺度分形特征;图象法和N₂吸附/脱附等温线法确定的表面分形维数Ds分别为2.03～2.26、2.24～2.37,前者的分形尺度大约处于23～390nm之间,主要属于絮体外表面尺度,而后者的分形特征尺度区间的下限大约为0.2nm,属于孔表面尺度;另外,对同一絮体,N₂吸附法和脱附法确定的孔表面分形维数不同.热力学模型计算出的D_s远大于3,与Sahouli等的研究不符.     

微涡旋絮凝-逆流气浮-纳滤集成工艺去除水中腐殖酸的研究之二——以聚合氯化铁(PFC)为絮凝剂

试验研究了微涡旋絮凝-逆流气浮-纳滤集成工艺去除水中腐殖酸的工艺特征和效果.试验结果表明,微涡旋絮凝-逆流气浮工艺去除水中腐殖酸时,在聚合氯化铁(PFC)的最佳投药点0.62 mmol·L-1(Fe3 )下,出水水质符合纳滤膜系统预处理单元的要求,而且该工艺需要PFC絮凝剂的量较低.该预处理系统与纳滤系统组合的集成工艺可以使水中的腐殖酸有机物浓度大大降低,且含TQ56-36FC型纳滤膜的流程1比含M-N1812A型纳滤膜的流程2效果好.前者出水的TOC值可达0.48 mg·L-1,CODMn值为0.64～0.69mg·L-1,UV254值为0,且有95%以上的脱盐率.后者出水的TOC值为0.61～1.00mg·L-1,CODMn值为0.72～0.97mg·L-1,UV254值为0～0.0109,脱盐率很低.另外,尽管保安过滤/活性炭预处理有利于纳滤膜出水水质的提高,但活性炭柱的存在也降低了纳滤膜对有机物的去除率.动态实验结果表明,该集成工艺在本试验中运行周期为72h.水中颗粒物粒度分布表明,原水、絮凝后和气浮出水中颗粒物粒度分布的中位直径(d50)分别为2～5 μm、21 μm和16μm;经过保安过滤器或保安过滤器/活性炭柱,水样中的颗粒物的d50为0到几个μm;经过纳滤膜后,出水基本无颗粒物.初步研究表明,微涡旋絮凝过程中投药量对絮体的分形维数有着显著影响.     

高浓度聚合氯化铁(PFC)中铁的形态分布与转化研究

以氯化铁和无水碳酸钠为原料,加入稳定剂W,采用共聚工艺,制备了稳定高浓度的聚合氯化铁(PFC)混凝剂.采用Fe-Ferron逐时络合比色法研究了PFC中铁的形态分布情况,考察了熟化时间、碱化度(B)及n(W)/n(Fe)(W/Fe摩尔比)对PFC中铁的形态分布的影响.研究结果表明,在PFC中,由于稳定剂W与铁的水解产物间的相互作用,使得铁的水解聚合形态分布及转化情况发生了变化.碱化度(B)、n(W)/n(Fe)和熟化时间均对铁的形态分布有重要的影响.      

贵阳市PM_(2.5)微观特征的季节变化分析

大气颗粒物的污染特性与其理化性质有密切关系.本文利用高分辨率场发射扫描电镜(FESEM)和图像分析技术(IA)对贵阳市PM2.5进行研究,分析其微观形貌、数量贡献、体积贡献和粒度分布特征.结果表明:贵阳市PM2.5中颗粒物类型以烟尘及其集合体为主,其次是不规则矿物颗粒、规则矿物颗粒、燃煤飞灰和未知颗粒;4个季节PM2.5样品中烟尘及其集合体占多数,较多分布在0.1~0.2μm的粒径范围内,冬季数量比达到88.24%,体积比为60.45%;研究区PM2.5样品中含有较多的规则矿物颗粒,春季数量比、体积比分别为13.49%、33.58%,春、夏、秋季数量集中分布在0.5~0.6μm粒径范围,冬季主要分布在1.0~2.5μm粒径范围.     

颗粒物微界面吸附模型的分形修正--朗格缪尔(Langmuir)、弗伦德利希(Freundlich)和表面络合模型

运用分形理论修正了颗粒物微界面吸附模型,建立了朗格缪尔(Langmuir)、弗伦德利希(Freundlich)和表面络合模型的分形吸附等温线方程式．其中,朗格缪尔(Langmuir)吸附等温线的分形表达式为：Γ=ΓmCc^1/m／(b^m Cc^1/m),指数m与颗粒物表面分维Ds的关系如下：m∝ac^D/2-1∝ro^Do-2;表面络合模型的分形表达式为：Γ=ΓmCs^(n/x)/(b^(n/x) Cs^(n/x)),而且lgb=lg(ks／kb) pH,指数x／n与颗粒物表面分维Ds的关系如下：x／n∝0^D/2-1∝r0^D-2;相应的弗伦德利希(Freundlich)吸附等温线的分形形式分别为：Γ=(Γm／bm)Cs^1/n,Γ=(Γm／b^(x/n))Cr^(n/x),通过对献中的数据的模拟初步讨论了分形模型的适用性,结果表明,它们具有更接近于实际的描述微界面吸附过程的能力,通过lg(x／n)=lgk’ (Dn-2)lgro计算出土壤颗粒和尾矿砂颗粒的表面分形维数分别为2．42和2．72。     

旅游景区(点)系统空间分布的分形发育及演化特征——以四川省为例

论文以四川省为例,借用分形理论中的网格维测算方法分析旅游景区(点)系统的空间分形特征,用位序-规模双对数拟合方法研究旅游流的规模分布规律,得到以下结论:①旅游景区(点)系统分形是演化的分形,分形结构是逐步进化而来的。1980年以前,四川省旅游景区(点)的空间分布尚未发育分形结构,直至1990年,分形结构才逐渐形成;②旅游景区(点)空间分布的分形发育与旅游流流量规模分布的分形演化在总体趋势上是一致的,但具体过程有不同步性;③旅游景区(点)空间分布的分形发育为旅游业发展提供了良好的载体平台,但并不意味着旅游流的规模分布就一定会发育成理想的分形结构,还需要对相关要素进行调控,才能使旅游流的规模分布也具有分形特征。     

磷(P)对老冲积黄壤微团聚体表面砷(As(Ⅴ))吸附-解吸的研究

本文以名山河流域老冲积黄壤为研究对象,采用批培养法研究了原土及不同粒径微团聚体(2~0.25 mm,0.25~0.053 mm,0.053~0.002mm,0.002 mm)对As(Ⅴ)、P的吸附-解吸特性和P对As(Ⅴ)吸附-解吸特性的影响.结果表明:原土及不同粒径微团聚体对As(Ⅴ)与P的吸附-解吸特性相似,等温吸附均符合Langmuir和Freundlich方程,但Langmuir方程拟合效果最佳;动力学吸附均符合Elovich和双常数方程,而Elovich方程拟合效果最好,表明原土及各粒径微团聚体对As(Ⅴ)、P的吸附均以专性吸附为主,非专性吸附为辅.原土及不同粒径微团聚体对As(Ⅴ)的最大吸附量从大到小的排序为:(0.002 mm)原土(0.053~0.002 mm)(0.25~0.053 mm)(2~0.25 mm),对P的最大吸附量的顺序为:(0.002 mm)(0.053~0.002 mm)(0.25~0.053 mm)原土(2~0.25 mm),即粒径越小其最大吸附量越高.As、P在各粒径微团聚体上解吸量与其吸附量呈指数关系.As(Ⅴ)与P共存时,原土及不同粒径微团聚体对As(Ⅴ)的吸附量随P浓度的增加而减少,As(Ⅴ)的解吸量随P浓度的增加而增加,表明P能抑制土壤对As(Ⅴ)的吸附,而促进土壤对As(Ⅴ)的解吸,且0.002 mm粒径的土壤对As(Ⅴ)的吸附-解吸受P浓度的影响最小.     

Fractal analysis of polyferric chloride-humic acid （PFC-HA） flocs in different topological spaces

The fractal dimensions in different topological spaces of polyferric chloride-humic acid (PFC-HA) flocs, formed in flocculating different kinds of humic acids (HA) water with different initial pH (9.00, 7.00, 5.00) and PFC dosages, were calculated by effective density-maximum diameter, image analysis, and N2 absorption-desorption methods, respectively. The mass fractal dimensions (Df) of PFC-HA flocs, being more than 2.0, calculated by bi-logarithm relation of effective density-maximum diameter and Logan empirical formula at initial pH of 7.00 had 11-13 percentage greater than those at pH 9.00 and 5.00, indicating the most compact flocs formed in flocculated HA water at initial pH of 7.00. The image analysis for those flocs indicates that after flocculating the HA water at initial pH greater than 7.00 with PFC flocculant, the fractal dimensions of D2 (logA vs. logdL) and D3 (logVsphere vs. logdL) of PFC-HA flocs decreased with the increase of PFC dosages, and PFC-HA flocs showed a gradually looser structure. At the optimum dosage of PFC, the D2 (logA vs. logdL) values of the flocs show 14%--43% difference with their corresponding Df, and they even had different tendency as the change of initial pH values. However, the D2 values of the flocs formed at three different initial pH in HA solution, calculated from the horizontal projected images with magnification about 9, had a same tendency with the corresponding Df. Based on fractal Frenkel-Halsey-Hill (FHH) adsorption and desorption equations, the pore surface fractal dimensions (Ds) for dried powders of PFC-HA flocs formed in HA water with initial pH 9.00 and 7.00 were all close to 2.9421, and the Ds values of flocs formed at initial pH 5.00 were less than 2.3746. It indicated that the pore surface fractal dimensions of PFC-HA flocs dried powder mainly show the irregularity from the mesopore-size distribution and some marcopore-size distribution.     

Fractal analysis of polyferric chloride-humic acid (PFC-HA) flocs in di erent topological spaces

The fractal dimensions in di erent topological spaces of polyferric chloride-humic acid (PFC-HA) flocs, formed in flocculating di erent kinds of humic acids (HA) water at di erent initial pH (9.0, 7.0, 5.0) and PFC dosages, were calculated by e ective densitymaximum diameter, image analysis, and N2 absorption-desorption methods, respectively. The mass fractal dimensions (Df) of PFC-HA flocs were calculated by bi-logarithm relation of e ective density with maximum diameter and Logan empirical equation. The Df value was more than 2.0 at initial pH of 7.0, which was 11% and 13% higher than those at pH 9.0 and 5.0, respecively, indicating the most compact flocs formed in flocculated HA water at initial pH of 7.0. The image analysis for those flocs indicates that after flocculating the HA water at initial pH greater than 7.0 with PFC flocculant, the fractal dimensions of D2 (logA vs. logdL) and D3 (logVsphere vs. logdL) of PFC-HA flocs decreased with the increase of PFC dosages, and PFC-HA flocs showed a gradually looser structure. At the optimum dosage of PFC, the D2 (logA vs. logdL) values of the flocs show 14%–43% di erence with their corresponding Df, and they even had di erent tendency with the change of initial pH values. However, the D2 values of the flocs formed at three di erent initial pH in HA solution had a same tendency with the corresponding Df. Based on fractal Frenkel-Halsey-Hill (FHH) adsorption and desorption equations, the pore surface fractal dimensions (Ds) for dried powders of PFC-HA flocs formed in HA water with initial pH 9.0 and 7.0 were all close to 2.9421, and the Ds values of flocs formed at initial pH 5.0 were less than 2.3746. It indicated that the pore surface fractal dimensions of PFC-HA flocs dried powder mainly show the irregularity from the mesopore-size distribution and marcopore-size distribution.     

颗粒物表面酸碱特性与孔表面分形的研究

通过电位滴定试验,证明了5种颗粒物的表面存在着一定量的OH-受体,其表面位浓度(Hs)在0.1219～0.3134 mmo.·L-1之间,表面位密度(DoH)在0.8586～2.1305个·nm-2之间,且不同采样点的颗粒物,其表面位浓度和表面位密度差别很大.所采集的5种颗粒物的孔结构接近平行板狭缝,孔尺寸分布不是均一的,平均孔径分布范围较宽(1.8～76nm);BET比表面积为9.5669～34.5605 m2·g-1,累积脱附孔体积为0.01729～0.06711 cm3·g-1,BJH脱附平均孔径为5.6768～7.7388nm,处于中孔范围,且平均孔径均大于其PSD峰值对应的孔径.通过分形FHH方程模拟N2吸附和脱附等温线数据计算出这些颗粒物的孔表面分形维数Ds比较接近(2.68～2.82之间),但它们的分形标度区间不同.另外,采用热力学模型和分形FHH理论计算出的表面分形维数的差异主要归因于这些样品孔尺寸分布的不均一性.     

Effects of humic acid on recoverability and fractal structure of alum-kaolin flocs

Particle surface characteristics, floc recoverability and fractal structure of alum-kaolin flocs were investigated using in situ particle image velocimetry (PIV) and microbalance with or without humic acid. Experimental results indicated that the zeta potential of kaolin particle surface after adsorption of humic acid was related with humic acid concentration and its acid-base bu ering capacity. Adsorption of humic acid resulted in more negative electrophoresis on the particle surface. Coagulant dosages for particles to form flocs would increase with increasing humic concentration. PIV was used to evaluate floc structural fragmentation, floc surface erosion as well as recoverability after high shear. It was found that the floc size during the steady phase of growth was small, while the regrowing capability decreased in the presence of humic acid. The recoverability was closely related with floc breakage modes including floc structural fragmentation and floc surface erosion. The fractal dimensions of alum-kaolin flocs by mass-size method based on microbalance would decrease with increasing humic concentration. This study proved that humic acid had adverse influences on the performance of coagulation process.