铝盐沉淀法去除酸性矿井水中SO4^2—的试验研究

在投加铝盐条件下，钙、铝和硫酸根结合成复合物沉淀，使煤矿酸性矿井水中ＳＯ４＾２－得以去除。实验结果表明，本方法处理后出水ＳＯ４＾２－含量低于３００ｍｇ／ｌ；影响ＳＯ４＾２－去除率因素有：ｐＨ值、外加铝盐浓度及原水ＳＯ４＾２－的含量；最佳操作参数为：ｐＨ＝１０．５￣１２．０，ＳＯ４＾２－／Ａｌ＾３＋摩尔比为１．７。     

OH自由基引发光氧化氟氯碳化合物的研究

研究了ＣＦＣ－１１＋Ｈ２Ｏ２，ＣＦＣ－１１＋Ｈ２Ｏ２＋Ｏ２，ＣＦＣ－１２＋Ｈ２Ｏ２和ＣＦＣ－１２＋Ｈ２Ｏ２＋Ｏ２４个体系的光化学反应，这些体系在低压尔照射下，Ｈ２Ｏ２产生了ＯＨ自由基，ＯＨ自由基能引发ＣＦＣ的光氧化反应，其产物在２０ｍ长的漪避用富叶红外光谱仪测量，发现在ＣＦＣ－１１＋Ｈ２Ｏ２和ＣＦＣ－１１＋Ｈ２Ｏ２＋Ｏ２体系中有ＣＯＦＣｌ，ＣＯ２和ＨＣｌ，而在ＣＦＣ－１２＋Ｈ２Ｏ２和ＣＦＣ－１２＋     

光催化氧化法处理染料中间体H酸水溶液

为了去除水中难氧化的有害染料中间体Ｈ酸,研究以ＴＩＯ２、ＺｎＯ、ＣｄＳ和Ｆｅ２Ｏ３为催化剂,采用低压汞灯为光源,对Ｈ酸水溶液进行光催化氧化实验．结果表明：ＴｉＯ２和ＣｄＳ的催化效果最好．采用ＴｉＯ２作催化剂,光催化氧化５ｈ后,Ｈ酸分解率可达９０％,反应速率遵从Ｌａｎｇｍｕｉｒ－Ｈｉｎｓｈｅｌｗｏｏｄ方程,Ｋ＝１２．３Ｌ／ｍｍｏｌ,ｋ＝２５．２×１０－６ｍｏｌ／ｈ．溶液中投加１０ｍｇ／Ｌ的Ｆｅ３＋或Ａｇ＋,可使反应时间缩短２—３ｈ．研究探讨了ｐＨ、ＴｉＯ２投加量和Ｈ酸浓度对催化氧化过程的影响．     

BF4-废水水解法实验

常温下用水解法处理ＢＦ４废水．实验采用铝盐作主水解剂，试剂Ａ作助水解剂，ｐＨ值小于３，在常温条件下实现了对ＢＦ４的高效水解．研究结果表明，ＢＦ４∶Ａｌ３＋∶Ａ的质量比为１∶０．８∶０．１，水解时间６～３ｈ，水解率达到９９．５％以上．使用助水解剂Ａ，缩短了水解时间，减少了铝盐用量，对高浓度的ＢＦ４废水效果尤为显著，水解时间可缩短一半，主水解剂用量可减少１／５，处理后出水中的ＢＦ４含量可降到１０ｍｇ／Ｌ以下．     

UV/H2O2/草酸铁络合物光降解水中氯仿的研究

以４００Ｗ高压汞灯为紫外光源，Ｈ２Ｏ２－草酸铁络合物为光氧化剂，对氯仿水溶液进行了光降解反应实验研究．结果表明，ＵＶ／Ｈ２Ｏ２草酸铁络合物体系能有效地使水溶液中氧仿迅速光解脱氯；在等摩尔系列溶液中,Ｆｅ３＋／草酸根的摩尔比为１：３时，氯仿光解效果最好：溶液ｐＨ值对氯仿光解有显著影响，ｐＨ值在３－４时光解速率最快；随着Ｈ２ｏ２浓度的增加，氯仿大解速率提高，但Ｈ２Ｏ２浓度较大时，Ｈ２Ｏ２的有效利用率降低；温度对氯仿光解反应有一定影响，反应的表观活化能为７．６ｋＪ／ｍｏｌ.     

水解聚合铝溶液中形态分布的定量模拟研究

通过Ａｌ－Ｆｅｒｒｏｎ逐时络合比色法和￣（２７）Ａｌ核磁共振（ＮＭＲ）法，并应用“ＭＩＮＥＱＬ”化学平衡模式计算法，对采用不同反应途径制得的聚合铝（ＰＡＣ）溶液中的化学形态分布规律进行了定量模拟研究和对比。模式计算结果与两种实验定量分析结果都较为吻合，结果表明，在水解聚合铝溶液中较稳定的化学形态主要有五种：一种单体形态［ａｌ＿ａ］，即Ａｌ￣（３＋），Ａｌ（ＯＨ）￣（２＋），Ａｌ（ＯＨ）＿２￣＋；３种聚合形态［Ａｌ＿ｂ］，即和以及一种溶胶或凝胶形态［Ａｌ＿ｃ］，即Ａｌ（ＯＨ）＿３（ａｍ）．这些化学形态的分布和转化不仅取决于溶液的化学特征，而且也取决于制备方法的不同。     

绿麦隆在水溶液中光降解动力学研究

以低功率紫外灯和荧光灯为光源对水溶液中的绿麦隆进行光降解，探讨了光解的影响因素．研究表明，绿麦隆在紫外光照下较易降解，其光解符合准一级动力学方程，反应速率常数为２３×１０－２ｍｉｎ－１；在水环境中经长期光照会逐渐矿化为Ｃｌ－、ＣＯ２、ＮＯ－３等无机离子；运用ＧＣ／ＭＳ技术鉴定了绿麦隆的几种光解中间产物，异氰酸（３氯—４甲基）—苯酚酯是主要中间体，并推测了绿麦隆的光解反应历程．     

4-氯苯酚在水溶液中的光化学反应(Ⅰ)单线态氧和自由基的产生

在模拟太阳光照射下，４氯苯酚（４ＣＰ）浓度迅速降低，反应过程对应着产生大量的单线态氧和自由基．金属离子Ｆｅ２＋、Ｆｅ３＋、Ａｌ３＋能够加速这一过程，尤以Ｆｅ２＋、Ｆｅ３＋的影响更明显；在模拟太阳光照射下，向４ＣＰ体系加入的富里酸（ＦＡ），对４ＣＰ浓度降低略起抑制作用，这表明二者之间存在相互作用．但当再加入金属离子Ｆｅ２＋、Ｆｅ３＋、Ａｌ３＋后，能够加速４ＣＰ浓度降低，尤以Ｆｅ２＋、Ｆｅ３＋的影响更显著．     

厦门西海域表层沉积物中甾醇的模糊聚类分析

通过流动法技术研究了ＣｕＯ／γＡｌ２Ｏ３催化剂上添加Ｌａ２Ｏ３对ＣＯ和ＣＨ４的氧化活性．通过Ｏ２ＴＰＤＭＳ等技术研究了催化剂上表面氧脱附与表面氧恢复能力．结果表明，Ｌａ２Ｏ３的添加改善了ＣｕＯ／γＡｌ２Ｏ３催化剂对ＣＯ和ＣＨ４的氧化活性；Ｌａ２Ｏ３的添加促进了ＣｕＯ／γＡｌ２Ｏ３催化剂上表面氧的脱附和表面氧的恢复．     

化学沉淀法去除垃圾渗滤液中的氨氮

为了有效地去除垃圾渗滤液中高浓度的ＮＨ＾＋４－Ｎ而避免传统吹脱法造成吹脱塔内碳酸盐结垢问题,探讨了采用化学药剂诸加ＭｇＣｌ２·６Ｈ２Ｏ和Ｎａ２ＨＰＯ４·１２Ｈ２Ｏ或ＭｇＯ和Ｈ３ＰＯ４使ＮＨ＾＋４－Ｎ生成磷酸铵镁的化学沉淀去除法。小试研究结果表明,当垃圾渗滤液中投加ＭｇＣｌ２·６Ｈ２Ｏ和Ｎａ２ＨＰＯ４·１２Ｈ２Ｏ而使Ｍｇ＾２＋：ＮＨ＾＋４：ＰＯ＾３－４的比例为１：１：１时,在最佳ｐＨ为８．５～９．０     

初始pH值对连续投加铝盐混凝去除小分子有机物的影响机制

以污水厂二级出水中小分子有机物强化混凝去除为目的,提出了连续投加混凝工艺(CDC),并以水杨酸为模型小分子有机物,研究了初始pH值对CDC工艺去除效果的影响以及铝离子与水杨酸的络合特性.结果表明,初始pH值6时CDC工艺的去除率最高,比常规混凝工艺提升了13.8%.但是初始pH值5和7时CDC工艺的提升效果较小.三维荧光结果表明,不同pH值下水杨酸和铝离子的络合特性不同.X射线光电子能谱和电喷雾质谱结果表明,pH值5时CDC工艺前期主要生成1:1络合物Al(OH)(C₇H₄O₃)(H₂O)₂.其络合作用强烈,稳定性较高,难以从水中去除.pH值6时前期主要生成中等聚合铝(如原位Al₁₃),其与水杨酸形成的络合物可以参与到铝离子的生长过程,最终生成表面崎岖形态松散的珊瑚礁状絮体,强化了水杨酸的去除.pH值7时,主要生成不定形氢氧化铝,通过絮体表面吸附小分子有机物.     

Al与F的络合作用对土壤吸附Al和F的影响

研究了Al-F络合作用对土壤吸附Al和F的影响以及吸附前的溶液中铝化学形态的差异。提高Al或F的加入量将人别使分配在土壤溶液中的F或Al的数量增加，即Al-F络合作用地使Al和F在土壤固-液间的分配平衡向液相移动，土壤对Al-F络合物吸附程度很小，吸附前，3种不同F/Al比溶液中Al^3 ，AlF^2 的浓度随着F/Al比的增加逐渐降低，AlF2^ ,AlF3^0的浓度则逐渐升高，与土壤作用后，溶液中Al主要与AlF^2 ,AlF2^ 的形式存在，以AlF^2 的数量居多。     

pH和有机酸对氟溶出砖红壤中铝离子的影响

研究砖红壤对F-的吸附反应尤其是随后Al3+的释放过程,有助于增进对土壤酸化过程及其环境影响的理解. 在初步揭示出F-吸附反应以及Al3+释放反应的动力学特征基础上,重点考察了pH和有机酸对上述反应的影响. 结果表明:土壤对F-的吸附反应十分迅速,2 min内吸附量即可达到24 h内总吸附量95%,而土壤中不同含铝矿物的溶解度差异使Al3+的释放过程在前15 min十分迅速,释放量可达24 h内总释放量的80%,随后则逐渐减缓. 降低反应体系pH可促进Al3+释放,但会使F-吸附量减少,这是因为伴随Al3+的释放,部分F-又可以AlF络合物的形态重新进入溶液,尽管在低pH条件下,土壤表面以带正电荷为主而有利于F-吸附. 草酸和抗坏血酸对土壤吸附F-均有抑制作用,但对F-溶出土壤Al3+有促进作用. 此外,草酸对土壤铁氧化物的选择性溶解作用,可使更多F-吸附在土壤铝氧化物位点,并导致Al3+释放量增加.      

低分子量有机酸对几种可变电荷土壤吸附氟的影响

用一次平衡法研究了四种低分子量有机酸对几种可变电荷土壤吸附氟的影响，结果表明，低分子量有机酸可以通过竞争吸附作用抑制土壤对氟的吸附，化学结构相对简单的草酸和丙二酸对氟吸附的抑制作用大于柠檬酸和苹果酸。有机酸对氟吸附的抑制作用随土壤氧化铁含量的增加而增加，并随体系pH的增加而增强。在低pH和氟加入量较高的情况下，有机酸通过与氟竞争可溶性铝而增加土壤对氟的吸附量，这在对铝溶解度较高的酸性土壤中尤为明显。     

Two-dimensional correlation spectroscopic analysis on the interaction between humic acids and aluminum coagulant

In this study, two-dimensional correlation spectroscopy integrated with synchronous fluorescence and infrared absorption spectroscopy was employed to investigate the interaction between humic acids and aluminum coagulant at slightly acidic and neutral p H. Higher fluorescence quenching was produced for fulvic-like and humic-like fractions at p H 5. At p H 5, the humic-like fractions originating from the carboxylic acid, carboxyl and polysaccharide compounds were bound to aluminum first, followed by the fulvic-like fractions originating from the carboxyl and polysaccharide compounds. This finding also demonstrated that the activated functional groups of HA were involved in forming the Al-HA complex, which was accompanied by the removal of other groups by co-precipitation.Meanwhile, at p H 7, almost no fluorescence quenching occurred, and surface complexation was observed to occur, in which the activated functional groups were absorbed on the amorphous Al(OH)3. Two-dimensional FT-IR correlation spectroscopy indicated the sequence of HA structural change during coagulation with aluminum, with IR bands affected in the order of COOH COO-NH deformation of amide Ⅱ aliphatic hydroxyl C\OH at p H 5, and COO-aliphatic hydroxyl C\OH at p H 7. This study provides a promising pathway for analysis and insight into the priority of functional groups in the interaction between organic matters and metal coagulants.     

铜绿微囊藻对混凝除氟的促进作用及机理分析

以铜绿微囊藻、氯化铝（AlCl₃·6H₂O）为研究对象,通过三维荧光、场发射扫描电镜等表征,探究了藻类对氟化物混凝去除机制的影响.结果表明,在pH值为7.0,8.0,9.0,Al投加量在20.0~80.0mg/L的条件下,铜绿微囊藻对混凝除氟有明显的促进作用,其促进作用主要在于藻絮体对氟的表面吸附.铜绿微囊藻与氯化铝水解产物通过吸附架桥和网捕卷扫作用,聚集成较大较多的絮体.絮体粒径越大,除氟率越高.pH值为7.0,Al投加量为40.0mg/L时,絮体粒径达到最大值500μm,此时氟去除率最高,为77.37%;当Al投加量为80.0mg/L时,藻细胞破损严重,有机物过多释放,对混凝除氟起阻碍作用.絮体破碎吸附实验结果表明,对絮体进行一定强度破碎可以增加吸附位点,从而提高氟的去除率;但破碎强度过大,絮体粒径过小,对氟的吸附效率亦会降低.     

Effects of low temperature on aluminum(Ⅲ) hydrolysis: theoretical and experimental studies

In this study, the effects of low temperature on aluminum(III) (Al) hydrolysis were examined both theoretically and experimentally by constructing a solubility diagram for amorphous aluminum hydroxide (Al(OH)3(am)) and a distribution diagram of hydrolyzed Al species. Firstly, thermodynamic data of Al species at 4℃ were calculated from that at 25℃. A well confirmed polymeric Al species, AlO4Al12(OH)247 (Al13), was involved in building the diagrams and, correspondingly, the non-linear simultaneous equations with 13 degrees were resolved. Secondly, polarized Zeeman atomic absorption spectrophotometry (AAS), 27Al nuclear magnetic resonance (NMR) spectroscopy, and ferron-based spectrophotometry were applied for constructing the practical diagrams. The results show that a decrease of temperature from 25 to 4℃ caused the Al(OH)3(am) boundary on the solubility diagram to shift toward the alkaline side by about 1.0 pH unit and the minimum solubility of Al(OH)3(am) to reduce by 1.0 log unit. The distribution diagram indicates that the monomeric Al, Al13, and solid-phase Al(OH)3 were alternately the predominant species with the increase of pH value during Al hydrolysis. At 25℃, Al13 was the dominant species in a pH range of 4.0 to 4.5, whereas at 4℃, Al13 was the leading species in a pH range spaced from 4.5 to 6.3. The predominant species changed from the monomeric Al to the solid-phase Al(OH)3 over the range of 1.8 pH units at 4℃ in comparison with the range of 0.5 pH unit at 25℃.     

Effects of low temperature on aluminum(III) hydrolysis: Theoretical and experimental studies

In this study, the effects of low temperature on aluminum(III) (Al) hydrolysis were examined both theoretically and experimentally by constructing a solubility diagram for amorphous aluminum hydroxide (Al(OH)3(am)) and a distribution diagram of hydrolyzed Al species. First, thermodynamic data of Al species at 4 degrees C were calculated from that at 25 degrees C. A well confirmed polymeric Al species, AlO4Al12(OH)24(7+)(Al13), was involved in building the diagrams and, correspondingly, the non-linear simultaneous equations with 13 degrees were resolved. Secondly, polarized Zeeman atomic absorption spectrophotometry (AAS), 27Al nuclear magnetic resonance (NMR) spectroscopy, and ferron-based spectrophotometry were applied for constructing the practical diagrams. The results show that a decrease of temperature from 25 to 4 degrees C caused the Al(OH)3(am) boundary on the solubility diagram to shift toward the alkaline side by about 1.0 pH unit and the minimum solubility of Al(OH)3(am) to reduce by 1.0 log unit. The distribution diagram indicates that the monomeric Al, Al13, and solid-phase Al(OH)3 were alternately the predominant species with the increase of pH value during Al hydrolysis. At 25 degrees C, Al13 was the dominant species in a pH range of 4.0 to 4.5, whereas at 4 degrees C, All3 was the leading species in a pH range spaced from 4.5 to 6.3. The predominant species changed from the monomeric Al to the solid-phase Al(OH)3 over the range of 1.8 pH units at 4 degrees C in comparison with the range of 0.5 pH unit at 25 degrees C.     

铁盐和铝盐混凝微滤工艺除As(V)的比较研究

选择FeCl₃和Al₂(SO₄)₃作混凝剂,采用小试规模的混凝微滤膜反应器比较了铁盐和铝盐混凝微滤工艺的除As(V)效果、相关性能指标及适用范围.结果发现,Fe³⁺投加量为4 mg/L、Al₂(SO₄)₃投加量为50 mg/L时,铁盐和铝盐工艺的除As(V)效果大致相当,均可使水中As(V)的浓度从100 μg/L左右降低到10 μg/L以下,最低为1.68 μg/L.出水浊度均小于0.1 NTU,出水中铁、铝和SO^2-₄浓度均符合饮用水标准.铁盐工艺出水pH值比原水大约高0.5,铝盐工艺处理前后水的pH值基本不变.反应器运行结束静沉24 h后,铁盐工艺浓缩比为1 791,是铝盐工艺的2.54倍,污泥中As(V)的含量也大大高于铝盐工艺,去除同等重量的As(V)所产生的污泥量较铝盐工艺少得多.因此,对于仅有砷超标的饮用水,应优先考虑铁盐工艺.按除氟所需混凝剂数量投加Al₂(SO₄)₃,铝盐工艺即可在去除As(V)的同时去除氟,铁盐工艺则不能去除氟.因此,对于砷和氟均超标的饮用水,可采用铝盐工艺同时去除砷和氟.     

从阳极泥中提取结晶形Al（OH）3的绿色化研究

采用碱中和阳极泥中的Al2O3和无定形Al(OH)₃,再通入CO₂,从铝型材生产线阳极沉积下来的废泥中成功制备出结晶形Al(OH)₃,研究了温度,pH及CO₂气流速率对形成结晶形Al(OH)3产量的影响。结果表明,在强烈搅拌下,当温度为70~80℃,pH为8~9,CO₂气流速率为50~60mL/min时,Al(OH)3产量最高。该研究实现了回收铝资源,净化环境,且副产品Na₂CO₃可回收利用的目的,从而达到综合利用资源,变废为宝的绿色目标。