MMM分子筛的制备与表征

 以碱溶液处理ZSM－5分子筛，得到了含微孔及介孔的MFI结构分子筛（简称MMM），并采用XRD，XRF，SEM，XPS和低温氮吸附等技术对分子筛进行了表征．结果表明，通过改变处理碱的浓度可以得到具有不同物化性能的MMM分子筛，其化学组成、介孔及微孔的大小和多少，及分子筛晶体上n（Al）／n（Si）均随碱浓度的变化而变化，随着碱浓度的增加，分子筛部分微孔结构遭到破坏，介孔的数量增加，孔径增大，n（Al）／n（Si）增大．碱处理脱硅的过程包括脱除晶粒间的无定形物质，脱除分子筛表面的硅及脱除分子筛体相硅等步骤，硅脱除以后形成了介孔．     

低碱度共沉淀法制备苯选择加氢Ru-Zn催化剂

在低碱度下采用共沉淀法成功制备了非负载型Ru-Zn催化剂,用于苯选择加氢制环己烯反应.固定氢氧化钠沉淀剂的量,考察了不同氯化锌加入量对催化剂结构和催化性能的影响,采用N2吸附、X射线衍射和程序升温还原等手段对催化剂进行了表征.同时考察了选用具有最佳锌含量的Ru-Zn催化剂时搅拌速度和硫酸锌添加剂等对催化反应性能的影响,最后考察了催化剂多次使用时的反应性能.研究表明, Zn含量16.7%(质量分数)的Ru-Zn催化剂具有最佳的催化性能;在ZnSO4水溶液(0.45 mol/L)中,优化反应条件(哈氏合金釜,1200 r/min,150oC, H2压5 MPa)下反应45 min,苯转化率57%时环己烯选择性可达80%(收率超过45%).钌催化剂中ZnO晶体对于环己烯选择性达到80%非常重要.催化剂回收循环反应5次时反应性能基本不变,表明低碱度下制备的催化剂具有良好的稳定性,显示了工业化应用前景.     

微量原位水质总碱度在线检测新方法研究

为实现原位水质总碱度快速准确检测的需求,融合顺序注射分析（sequential injection analysis, SIA）与连续光谱检测法,设计了一种小型微量原位水质总碱度在线快速检测仪,系统主要通过设计滴定池将SIA和连续光谱检测法应用于总碱度自动化滴定检测流程,并对连续光谱检测法判断滴定临界值的新方法进行实验研究。基于国标总碱度检测中工业循环冷却水及地表水总碱度的测定标准,设计了原位水质总碱度检测流程,并以顺序注射技术为控制滴定流程基础,在连续光谱扫描测量溶液检测过程的条件下,使用酚酞和甲基橙作为指示剂,对水质总碱度进行滴定分析。通过连续光谱扫描对酚酞碱度及甲基橙碱度滴定过程进行监测,以吸光度曲线552 nm处峰值归零作为酚酞碱度滴定临界值判断条件;以吸光度曲线峰值由465 nm偏移至504 nm处作为甲基橙碱度滴定临界值判断条件;分析通过滴加不同剂量酚酞和甲基橙指示剂所得溶液吸光度曲线得出最佳指示剂用量分别为0.01和0.04 mL。该系统利用最小二乘拟合算法建立总碱度测定的回归模型,并对检测系统及检测流程进行优化,实验结果表明,水质总碱度在0.20~25.00 mmol·L-1范围内与盐酸消耗量线性相关,工作曲线拟合系数≥0.994 2;测定总碱度重复性相对标准偏差（RSD）为0.207%~1.151%;废液量≤16 mL;最低检出限为0.03 mmol·L-1;样品加标回收率在97.2%~102.3%之间;与国标法对比实验结果无明显差别。利用连续光谱检测法判断滴定临界值的新方法对于提升水质总碱度检测仪的技术性能具有重要意义,可适用于系统网格化监控地表水、循环冷却水、养殖循环水等多种监测应用平台。     

透光脉动检测仪研究碱度对絮体形成、破碎及再生的影响

为了解碱度对絮体的形成、破碎及再生过程的影响,采用PDA2000型透光脉动检测仪测定不同碱度下投加硫酸铝时高岭土悬浮液的絮凝指数(FI指数),并以强度因子和再生因子评价絮体的强度和再生能力。结果表明,碱度的高低在很大程度上会影响絮体的形成、破碎及再生过程,所形成絮体的颗粒随碱度的增加而减小。混凝剂投量和碱度高低共同决定了絮体的抗破碎强度,碱度越高,混凝剂投量越大,絮体的强度越高。在电中和作用下形成的絮体在低碱度下经一次破碎后恢复程度接近100%,在网捕卷扫作用下形成的絮体,无论碱度高低,从第2次破碎起,FI指数均以大于10%的幅度逐次下降,絮体不可恢复程度显著增大。     

Interfacial potential difference in electromembrane systems with MA-41 anion-exchange membranes and alkaline solutions of glycine

A method for estimating the interfacial potential difference in electromembrane systems with alkaline solutions of amino acids is developed. Systems with MA-41 anion-exchange membranes and aqueous sodium hydroxide solutions with glycine are investigated. It is found that in solutions with alkali concentrations greater than 0.010 M, the interfacial potential difference decreases logarithmically, i.e., in agreement with the Donnan relationship. At the same time, in weakly alkaline solutions of glycine, in which the amino-acid concentration exceeds that of the alkali, an increase in the interfacial potential difference is observed. This may be due to a disturbance of the equilibrium of the protolytic reaction in the membrane on the side where hydroxide ions form.     

OH-/SiO2比对合成β沸石晶粒粒度分布及结构的影响

具有十二元环的三维高硅大孔β沸石是1967年由Wadlinger[1]首先合成的,其结构模型于1988年由Newsam等[2]确定,近十年来,许多文献报道了不同模板剂、不同铝源和硅源以及不同碱金属对β沸石合成的影响及杂原子β沸石的合成[3-5],但均存在晶化时间较长等缺点,关于晶化混合物的OH-/SiO2比(以下简称碱度)对在较短晶化时间下所合成的β沸石的影响未见报道.     

Thin‐Layer Chemical Modulations by a Combined Selective Proton Pump and pH Probe for Direct Alkalinity Detection

We report a general concept based on a selective electrochemical ion pump used for creating concentration perturbations in thin layer samples (～40 μL). As a first example, hydrogen ions are released from a selective polymeric membrane (proton pump) and the resulting pH is assessed potentiometrically with a second membrane placed directly opposite. By applying a constant potential modulation for 30 s, an induced proton concentration of up to 350 mM may be realized. This concept may become an attractive tool for in situ titrations without the need for sampling, because the thin layer eventually re‐equilibrates with the contacting bulk sample. Acid–base titrations of NaOH and Na₂CO₃ are demonstrated. The determination of total alkalinity in a river water sample is carried out, giving levels (23.1 mM ) comparable to that obtained by standard methods (23.6 mM ). The concept may be easily extended to other ions (cations, anions, polyions) and may become attractive for environmental and clinical applications.     

同时测定无机离子的改良离子色谱法在河水和废水质量监控中的应用（英文）

In this study,our recent work on advanced ion chromatographic methods for the simultaneous determination of inorganic ionic species such as common anions(SO2-4,Cl-and NO-3) and cations(Na+,NH+4,K+,Mg2+,and Ca2+),nutrients(phosphate and silicate) and hydrogen ion/alkalinity are summarized first.Then,the applications using these methods for monitoring environmental water quality are also presented.For the determination of common anions and cations with nutrients,the separation was successfully performed by a polymethacrylate-based weakly acidic cation-exchange column of TSKgel Super IC-A/C(Tosoh,150 mm×6.0 mm i.d.) and a mixture solution of 100 mmol/L ascorbic acid and 4 mmol/L 18-crown-6 as acidic eluent with dual detection of conductivity and spectrophotometry.For the determination of hydrogen ion/alkalinity,the separation was conducted by TSKgel ODS-100Z column(Tosoh,150 mm×4.5 mm i.d.) modified with lithium dodecylsulfate and an eluent of 40 mmol/L LiCl/0.1 mmol/L lithium dodecylsulfate/0.05 mmol/L H2SO4 with conductivity detector.The differences of ion concentration between untreated and treated wastewater showed the variation of ionic species during biological treatment process in a sewage treatment plant.Occurrence and distribution of water-quality conditions were related to the bioavailability and human activity in watershed.From these results,our advanced ion chromatographic methods have contributed significantly for water quality monitoring of environmental waters.     

碱性离子液体催化的Claisen-Schmidt缩合反应

合成了6种以N-甲基咪唑为基体的碱性离子液体, 以其作为催化剂, 在无溶剂条件下, 成功催化了Claisen-Schmidt缩合反应. 采用Hammett指示剂法对碱性离子液体的碱性强度和碱量进行表征. 实验结果表明, 此系列碱性离子液体对Claisen-Schmidt缩合反应具有较高的催化活性, 反应条件温和, 产物产率较高, 离子液体经简单处理后可多次循环使用, 催化活性未见明显降低.     

海洋沉积物孔隙水总碱度的现场分析方法

海洋沉积物孔隙水总碱度及其分布对海洋天然气水合物的调查研究具有重要意义.孔隙水总碱度异常对于判断天然气水合物的存在具有重要的指示作用.建立了利用微量水样品测试总碱度的方法,将2.00 mL孔隙水样品加入10.00 mL已知总碱度的海水样品中,使用盐酸标准溶液滴定、pH计监控法测定混合溶液的总碱度,然后计算出加入孔隙水样品的总碱度.方法所需样品量少,测定结果的相对标准偏差小于2％(n=12),方法简便可行,可用于船上海洋沉积物孔隙水总碱度的现场测定.