水蒸气对高岭土高温吸附铅的影响

使用沉降炉开展了水蒸气对高岭土高温吸附铅影响的实验研究,其中铅的形态为PbO和PbCl₂两种。首先研究了0-20%水蒸气对高岭土吸附PbO(1100-1300℃)和PbCl₂(800-1300℃)的影响规律,然后基于XRD、SEM和残余羟基率等分析,掌握了水蒸气影响高岭土高温吸附的机理。结果表明,水蒸气可以减少高岭土表面羟基的高温脱落,从而阻碍了PbO吸附、促进了PbCl₂吸附。综合高温下惰性莫来石的出现和高岭土孔隙结构的坍塌等因素,PbO和PbCl₂的最佳吸附温度分别为1200和1000℃。     

热处理对憎水硅胶吸附水蒸气的影响

用甲基氯硅烷蒸气或溶液处理硅胶,均可制成憎水硅胶。关于憎水硅胶的吸附性能和热稳定性的研究,文献中时有报道。本文主要探讨以下3个问题:(1)在水蒸气吸附中,硅胶表面自由羟基和缔合羟基究竟哪种起主要作用;(2)从吸附水蒸气等数据讨论硅胶表面有机基团—OSi(CH_3)_3的热稳定性;(3)用二甲基二氯硅烷(DMCS)和三甲基氯硅烷(TMCS)处理的憎水硅胶,哪种硅胶的热稳定性较高。这些基本问题,不仅具有学术意义,对研究氧化物表面改性也有参考价值。     

高岭土吸附稀土元素的实验研究

为更好了解粘土矿物对稀土元素(REE)的吸附及其控制因素,进行了不同溶液介质条件(平衡时间、REE含量、pH＝3～6.5) 1 g·L-1高岭土对REE吸附的系列实验.结果表明: 稀土在较短时间内(24 h)吸附/解吸过程达到平衡;Langmuir吸附等温线能模拟REE在高岭土上的吸附,总的趋势是REE含量越高,分馏越不明显;此外,pH对REE吸附和分馏有很大影响,REE分配系数随pH值增加而增加,且在pH近中性时,出现了明显的重稀土比轻稀土更多的被吸附.     

城市土壤对铅的吸附动力学特征及影响因素

采用批量法对温州景山森林公园5种不同土壤的Ph的吸附动力学行为进行了研究,初步探讨了不同理化性质土壤对重金属吸附的影响。结果表明,在实验条件下,5种土样均在180rain内达到吸附平衡;抛物线扩散方程、双常数速率方程和Elovich方程能很好地描述5种土壤Pb^2＋动力学行为;随着外源Pb^2＋质量浓度的增大,土壤对Pb^2＋的吸附量都相应增大;通过吸附速率与吸附强度与土壤理化性质相关性分析,得出土壤对重金属铅的吸附速率是土壤各理化性质综合作用的结果,而土壤对铅的吸附强度在很大程度上取决于土壤pH。     

碱活化高岭土对亚甲基蓝的吸附研究

本研究通过碱活化的方法对天然高岭土进行改性,制备高岭土基吸附剂,通过静态吸附实验考察了其对亚甲基蓝的吸附行为。实验结果表明:与天然高岭土相比,碱活化高岭土的结构发生了明显改变,进而影响了其吸附亚甲基蓝的性能。该吸附过程可以用伪二级动力学模型和Freundlich等温吸附模型来描述。由吸附热力学可知,该吸附过程可以自发的进行且为吸热过程。     

稀土对变形铅黄铜高温性能的影响

通过高温拉神试验,研究了稀土元素对不同铅含量的变形铅黄铜高温性能的影响。结果表明:添加微量稀土可较显著提高合金的高温延伸率,对最大流动应力无显著影响。采用扫描电镜、定量金相、结构分析等检测手段,研究了稀土对合金微观组织结构的影响。同时,探讨了稀土的作用机理。     

不同金属盐改性对硅胶的水蒸气吸附性能影响

用不同的金属盐溶液对中孔硅胶进行了改性,并进行了吸附水蒸气动力学实验.讨论了改性硅胶的吸湿性与离子半径之间的关系及吸附速率与平均孔径的关系.实验结果表明:(1) CaCl2,LiCl,MgCl2,ZnCl2改性硅胶,可以使硅胶的吸湿性能明显增加.其中用CaCl2改性的硅胶的吸湿量最大,其平衡吸湿量是未改性硅胶的3倍;(2) 用CaCl2溶液改性的中孔硅胶其吸湿量已接近微孔硅胶的吸湿量,但其吸附速率明显大于微孔硅胶的吸附速率;(3) 用CaCl2和ZnCl2的混合溶液改性硅胶对其吸湿量的提高没有明显效果.     

市售茶叶对水中镉铅锶的吸附

本文探讨了国产茶叶(市售安徽产绿茶)对水中Cd~(2+)、Pb~(2+)、Sr~(2+)的吸附特性。考察了抗坏血酸、柠檬酸、草酸等存在下,茶叶对水中Cd~(2+)、Pb~(2+)吸附能力的影响。于一定pH时及相同操作条件下,用60℃烘干碎成80目的茶,对Pb~(2+)、Cd~(2+)分别进行了11及7次测定,其吸附率均值Pb~(2+)86.9％,Cd~(2+)为41.3％,相对标准偏差是2.3％及2.7％。用未烘干粉碎的市售茶,对Pb~(2+)、Cd~(2+)分别进行7及6次测定,吸附率均值为96.4％及62.3％,相对标准偏差为1.8％及1.9％。     

电厂废气中饱和水蒸气对活性炭变压吸附捕集CO2的影响

由于热电厂废气中含有高湿饱和水蒸气,选用疏水材料活性炭为吸附剂,利用真空变压吸附技术研究了活性炭分离电厂废气中水蒸气和二氧化碳的可行性和优越性,研究了水对CO₂捕集的影响。实验分析表明,水在活性炭上的“S”型等温吸附曲线有利于真空条件下被解吸。同时,圆锥模型描述了水蒸气在吸附床内的浓度分布。结果表明,即使水蒸气可以被活性炭吸附,但它的存在不影响CO₂的捕集。每个循环操作可在相对较短的解吸时间和较高的解吸压力下完成。实验中单床三步变压吸附工艺可以使CO₂回收率高达80%,CO₂纯度达43%。     

有机分子偶氮苯在高岭石表面吸附研究

利用Gaussian 98软件,采用量子化学从头算计算方法,研究有机分子偶氮苯在高岭石表面的吸附作用.不同位置的吸附结果比较表明,吸附后体系稳定性强弱及电子发生转移的可能性大小依次是平行于硅氧烷表面、平行(010)面、平行[AlO4]八面体表面.芳香环上的π键和硅氧烷表面的O原子均相互作用,电子从偶氮苯上的C和N原子流向高岭石表面的O原子.对吸附复合物进行了X射线粉末衍射(XRD)、红外光谱(FTIR)测试及结构分析,结果表明,偶氮苯吸附到高岭石的硅氧烷表面.     

Influences of acid and heat treatments on the structure and water vapor adsorption property of natural zeolite

Natural zeolite was first acid treated and then heat treated. The influences of acid and heat treatments on the structure and water vapor adsorption property of natural zeolite were investigated. X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction (XRD), thermogravimetric analysis (TG), and Brunauer‐Emmett‐Teller (BET) surface areas were employed to investigate the structure changes of the zeolite samples. Water vapor adsorption property of the samples was investigated in order to determine wettability of the samples. The results showed that nitric acid treatment could remove Al from the structure, decrease relative crystallinity, and significantly increase specific surface area of the zeolite samples. Heat treatment could change or even destroy the structure, effectively remove water molecules from the surface/structure, and decrease the specific surface area of the zeolite samples. Water vapor adsorptions on the acid‐treated zeolite samples were significantly lower than that for the zeolite sample, and the adsorptions further reduced for the heat‐treated zeolite samples. The increase of Si/Al ratio, decreases of silanol groups, and specific surface area of the samples were major reasons related to the reductions of water vapor adsorptions on the zeolite samples.     

Flash calcination of kaolinite studied by DSC,TG and MAS NMR

The structural changes occurring during the dehydroxylation of kaolinite have been followed using flash calcination to produce kinetically frozen calcines. The percentage of dehydroxylation was varied by changing the furnace residence time or temperature and/or heating speed. These calcination conditions affected the reaction kinetics, but the products depended only on the extent of dehydroxylation.Changes in the position and enthalpy of the endothermic transformation to metakaolinite and the high temperature exothermic reaction of metakaolinite have been followed using Differential Scanning Calorimetry of the flash calcines and related to Thermogravimetry. ²⁷Al magic-angle-spinning NMR spectra, at high magnetic fields and spin rates, enabled the reaction of kaolinite to be monitored and provides new information on the nature of the species formed in the course of dehydration.We thank the Science and Engineering Council for supporting our studies of mineral transformations and. R. Meinhold thanks N.Z. D.S.I.R. chemistry, and H Atakul thanks Istanbul Technical University, for leave to undertake these studies. We thank Bruker Analytische for access to NMR spectrometers in their Karlsruhe laboratory.     

Thermodynamics of sodium chloride solutions at high temperatures

Osmotic coefficients are reported from vapor-pressure-lowering measurements on sodium chloride solutions at concentrations from approximately 4m to saturation and at temperatures from 75° C to 300° C. In combination with previously reported measurements at lower concentrations, these results allow a correlation of free energies for the system NaCl–H₂O over a range of concentrations and temperatures that is unprecedented for any aqueous electrolyte. Activity coefficients and other thermodynamic quantities for both salt and water have been calculated for the complete range of concentrations and temperatures. Calculated heats of solution and standard partial molal entropies agree well with calorimetric determinations where comparison is possible. The excess partial molal entropy of the salt is informative concerning structural effects and their changes with temperature and concentration.Presented in part at the 160th National Meeting of the American Chemical Society, Chicago, Illinois, September 1970.     

Adsorption phenomena at high pressures and temperatures 5. Heats of excess and total adsorption of krypton on zeolite NaA

Thermodynamic principles for the calculation of differential heats of excess and absolute adsorption were considered. A set of isosteres of excess adsorption of krypton on zeolite NaA are presented, from which the coverage and temperature dependences of the heats of excess adsorption are calculated and analyzed. The reasons for infinitely high values of the excess heats at finite values of adsorption are discussed. The problems of recalculation of the excess adsorption to absolute adsorption are considered.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1946–1950, August, 1996.     

水蒸气对甲烷在金属铁表面还原NO行为的影响

采用程序控温电加热水平陶瓷管反应器,在N2气氛和模拟烟气气氛中、300~1100℃下,研究了水蒸气对甲烷在金属铁表面还原NO行为的影响,并对反应前、后铁样品进行了X光衍射(XRD)、扫描电子显微镜(SEM)及X光电子能谱(XPS)等表征。结果表明,水蒸气对甲烷在金属铁表面还原NO行为的影响较小。在N2气氛中,水蒸气参与了金属铁的氧化;与无水蒸气时相比,水蒸气存在时NO还原效率有所下降。当水蒸气含量从2.5%增加到7%时,由于水蒸气对金属铁的氧化导致其表面形成疏松的微观孔隙,使得NO的还原效率随水蒸气含量的增加而提高。甲烷则参与了铁氧化物的还原,使铁样品表面形成相对致密的Fe3O4和FeO氧化层,不利于NO与金属铁的接触,使得NO的还原效率低于无甲烷时的结果。在模拟烟气条件下,水蒸气使得甲烷在金属铁表面还原NO的效率增加;在1050℃下,反应段过量空气系数SR1=0.7和燃尽段过量空气系数SR2=1.2时,含7%的H2O和无H2O条件下脱硝效率分别为96.7%和90.6%。而在湿烟气中SO2使NO还原效率略有下降。持久性脱硝实验结果表明,当反应温度为1050℃时,在含7%的H2O、0.02%的SO2的模拟烟气中,1.14%的甲烷在金属铁表面持续50h都能保持90%以上的脱硝效率。     

Determination of cadmium and lead in river water by sequential metal vapor elution analysis using a step-heated column

Determination of cadmium and lead in river water by sequential metal vapor elution analysis (SMVEA, column temperature; >1210 K) with argon carrier gas and an atomic absorption detector (AA) is reported. The column was a molybdenum tube inserted a tungsten coil. The flow rate of carrier gas was 1.8 ml min^–1. Cadmium and lead were separated from Ca, Fe, K, Na, and Zn metal vapours by SMVEA with the step-heated column (1210–1520 K) at an atomization temperature of 1830 K. Under the optimal experimental conditions, the recoveries of spiked-cadmium and lead in river waters were in the range of 91 to 106%. It is to determine cadmium and lead in river water without the interferences by matrix elements observed by electrothermal AAS, after only the addition of hydrochloric acid to the sample.     

卟啉钒在改性高岭土上的吸附行为及机理研究

利用酸改性和负载钼的酸改性高岭土作为吸附剂研究了环己烷中的卟啉钒(钒氧-2,3,7,8,12,13,17,18-八乙基卟啉,VO-OEP)在这两种吸附剂上的吸附行为,从热力学角度探讨了吸附机理。结果表明,两种吸附剂对卟啉钒的吸附符合Langmuir吸附等温线,卟啉钒单层吸附在改性高岭土上;吸附表现为自发热过程,吸附热均大于40 kJ/mol,说明吸附形成了化学键。     

Adsorption of water vapor on modified methacrylate polymeric sorbents

Adsorption of water vapor on methacrylate copolymers and terpolymers was studied. An increase in the content of the cross-linking agent gives rise to increase in the limiting adsorption of water vapor at the saturation pressure (a _s) and to decrease in the concentration of primary adsorption centers. Modification of the initial copolymer containing 60 % of 2,3-epoxypropyl methacrylate (EPMA) monomer and 40 % of cross-linking agent, ethylene dimethacrylate, with diethylenetriamine (DETA) results in an increase in thea _s value, while modification with C₁₂ and C₁₈ alkyl, benzyl, and phenyl groups gives rise to decrease in thea _s values for the copolymeric sorbents. The concentration of primary adsorption centers (a _m) increases considerably on modification of the copolymer with DETA and C₁₂ groups and decreases markedly on modification with benzyl and phenyl groups. For terpolymers, containing EPMA and styrene, an increase in the styrene/EPMA ratio reduces thea _s anda _m values. The copolymer modified with DETA groups possesses the most hydrophilic properties, while the copolymer modified with benzyl group exhibits the most hydrophobic properties. The mechanism of adsorption of water molecules on the polymers is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2163–2167, November, 1995.The work was financially supported by the Russian Foundation for Basic Research (Project No. 94-03-09550).