Zn2+改性丝光沸石对甲基橙的吸附性能研究

采用盐熔融法,将Zn2+交换丝光沸石分子筛制备Zn2+改性丝光沸石吸附材料。通过该材料对甲基橙的吸附动力学和吸附热力学研究,了解其吸附机理。研究结果表明:Zn2+改性丝光沸石对甲基橙的吸附动力学可用拟二级动力学方程来描述,计算值与试验值吻合较好,相关系数达到0.99;Zn2+改性丝光沸石对甲基橙的吸附等温线均符合Langmuir和Freundlich方程,室温下相关系数均大于0.9。根据不同温度下的热力学平衡常数,推算出Zn2+改性丝光沸石对甲基橙的吸附吉布斯自由能变ΔG0<0,吸附焓变ΔH0>0,表明吸附为自发的吸附过程,升温有利于吸附的进行,且吸附过程主要是物理吸附。     

13X沸石分子筛对饮用水中NH_4~+-N吸附性能的实验研究

研究了 13X沸石分子筛对饮用水中低浓度NH+4 N的吸附性能 ,包括影响吸附的主要因素、沸石对NH+4 N的吸附效果、沸石的再生效果及沸石对NH+4 N的吸附机理。实验表明用NaOH处理的沸石比未处理的沸石对NH+4 N的吸附效果要好。在 pH值为 6 5～ 7 5、吸附时间为 2 0min、吸附温度为 2 0～ 30℃的条件下 ,沸石对NH+4 N的吸附率接近 10 0 % ,沸石对NH+4 N的吸附量可达 16 32mg/g。用直接焙烧法进行再生活化处理后的沸石对NH+4 N的吸附率仍接近 10 0 % ,沸石对NH+4 N的吸附机理是以离子交换吸附作用为主。 13X沸石吸附NH+4 N的过程符合Langmuir吸附等温模式。实验证明 ,利用 13X沸石净化含低浓度NH+4 N的饮用水具有良好的工业化应用前景。     

河北省赤城县独石口沸石岩矿物学特征及其性能研究

独石口沸石岩共生矿物组合为斜发沸石、蒙脱石、α-方石英和少量丝光沸石。斜发沸石呈微晶产于玻璃质岩屑和火山尘中,也呈板状产于玻屑和珍珠岩溶解形成的孔洞中,沸石总量大于70％;化学成分显示高Si、高Al、富K、富Ca、贫Na的特征;阳离子交换容量高,交换性阳离子以Ca为主,其次为K,Na,Mg;阳离子选择交换顺序为NH_4~+>K~+>Ca~(2+)>Na~+>Mg~(2+);不同阳离子类型的沸石岩其热稳定性和吸附性有差异,K型和Na型沸石岩可稳定至700℃,而Ca型沸石岩在500℃时结构被破坏;Ca型沸石岩吸附性好,而K型差。     

阳离子对斜发沸石物理化学性能的影响

利用离子交换方法可以制备出K-型、Na-型和Ca-型斜发沸石。斜发沸石所含的阳离子类型不同,其物理化学性能有明显的差异。本文就不同类型的阳离子对斜发沸石的某些物理化学性能的影响进行了研究。     

沸石的热分析

沸石类矿物因具有阳离子交换作用、催化作用及分子筛作用.它作为工业原料、农业原料、以及公害处理材料有多方面利用价值,很值得注意,还有这种矿物在比较低温条件下脱水,产生“沸石水”,这种热的特性也使人深感兴趣.本研究是想通过用差热分析,研究日本国内产斜发涕石(Clinop-tilotite)的热特性,作为探索天然沸石生成状态的一个线索.实验方法将日本岛根县产斜发沸石选纯.在IN、KCI、NaCI、CaCI_2水溶液中进行离子交换,作成K型、Na型、Ca型沸石,然后通过加热使结构发生变化,经化学分析确认已成为所要求的沸石.然后使用“岛津制作所的A30型热分析装置”以至少33毫升/分钟的N_2进行热矢量分析、差热分析,从沸石中存在的U~+、Na~+”、Ca~(2+)的离子比率中求出     

碱处理对河北围场天然沸石结构和性能的影响及其机理研究

采用NaOH对围场地区天然沸石进行处理,采用X射线衍射仪、红外光谱仪、N2吸附-脱附技术、扫描电子显微镜等对材料进行表征分析,采用水蒸气吸附法评价材料的亲水性,采用Cr3+和Mn2+评价材料的离子交换性能,探讨了碱处理对天然沸石的结构、亲水性和离子交换性能的影响及其机理.实验结果表明,围场地区天然沸石中主要含有斜发沸石...     

黑龙江省穆棱沸石矿田矿石矿物特征及物化性能分析

综合应用显微观测、化学分析和物化检测手段，对黑龙江省穆棱沸石矿床沸石岩进行了系统研究，确定其矿物组成主要为斜发沸石和丝光沸石，二可单独产出，也可形成混合型矿石。该矿石在成分上属高硅型沸石，SiO2／Al2O3比值均大于8，有富元素As、Pb等较低。物化性能测试表明，穆棱沸石矿为高品级沸石矿，矿石平均热失重值达12．8％，NH4^ 交换容量为146．10meq/100g^,K^ 交换容量平均9．58mmol/100g，丝光沸石热稳定性可稳定至800℃-900℃，具有良好的开发应用前景。     

斜发沸石对模拟核素Sr2+的吸附/解吸动力学研究

以Sr（NO3）2为核素源、新疆富蕴县所产斜发沸石为吸附剂,研究斜发沸石对Sr2＋的动力吸附/解吸效果。探讨吸附时间、Sr2＋初始浓度与吸附量的关系以及吸附机理。用pH=6的水溶液对饱和吸附了Sr2＋的斜发沸石进行解吸。结果表明：斜发沸石对Sr2＋的吸附在4 h能达到最大吸附率的99%,Freundlich吸附等温式能对吸附曲线进行很好的描述,单位质量沸石对Sr2＋的最大吸附量为38.34 mg/g,以阳离子交换吸附为主。4.5 h后解吸率为1.78%,解吸速率远小于吸附速率,解吸量与解吸时间的自然对数呈现明显的线性关系,用Elovich方程对解吸曲线进行拟合,R=0.9994,拟合方程为：qt=0.03375＋0.11916lnt。理论上将5%的Sr2＋解吸出来约需5044 d。该斜发沸石固Sr2＋能力很强,对于处理含Sr2＋放射性废液具有重要的意义。     

斜发沸石岩的阳离子交换性能——对钾离子选择吸附的研究

斜发沸石是天然沸石中较常见和具有实际应用价值的一种。其化学分子式为:Ca（Na·K）₄Al₆Si₃₀O₇₂·24H₂O。关于斜发沸石的吸附、阳离子交换等性能,国外已有很多研究,并已将天然的斜发沸石、丝光沸石应用于从空气中富集氧、石油化工、原子能放射性废水和工业污水的处理、干燥剂,土壤改良剂、造纸充填剂等许多方面。     

天然斜发沸石吸附去除水中氨氮机理研究

采用天然斜发沸石吸附去除水中氨氮,利用X射线衍射(XRD)和X荧光光谱(XRF)分析沸石的物相组成和化学成分。通过批试验考察p H、氨氮初始浓度和温度对沸石吸附氨氮的影响,通过吸附等温线、吸附热力学和吸附动力学的研究探讨天然斜发沸石吸附氨氮的机理。溶液p H=8时沸石对氨氮的吸附效果最佳。Freundlich吸附等温线较Langmuir能更准确描述天然斜发沸石吸附氨氮的过程,该吸附过程属优惠吸附。对吸附热力学参数计算得到吉布斯自由能变ΔG~00,熵变ΔH~00,说明天然斜发沸石吸附氨氮是自发的吸热过程;熵变ΔS~00说明氨氮在沸石上的分布较在水溶液中的分布倾向无序。吸附动力学符合准二级动力学方程,且随着氨氮初始浓度的增大,吸附反应的优惠程度降低。运用颗粒内扩散模型对实验数据的拟合结果表明吸附过程分为两个阶段:前30分钟主要是外表面吸附,30分钟后主要是颗粒内扩散。     

The reaction chlorite+dolomite=spinel+forsterite+calcite+carbon dioxide+water

The reaction chlorite+dolomite=spinel+ forsterite+calcite+CO₂+H₂O has been studied with hydrothermal equipment technique in a C-O-H fluid at P _fluid=1,000, 2,000 and 3,000 bars and fo₂ controlled by NB or QFM buffer. The equilibrium conditions for the reaction has been determined as log K=–57,119/T+95.77+0.9860(P-1)/T(bar,°K). The mineral mixtures had an excess of dolomite. The composition of the chlorite among the reaction products has been analysed and found to have a higher Al/Si ratio than clinochlore.     

Die Reaktion Phlogopit + Calcit + Quarz = Tremolit + Kalifeldspat + H2O + C2O

Hydrothermal experiments with mixtures of synthetic minerals have shown the reversibility of the reaction 5 phlogopite + 6 calcite + 24 quartz = 3 tremolite + 5 K-feldspar + 2 H₂O + 6 CO₂. In an isobaric T – diagram the equilibrium curve reaches a maximum at = 0,75. The P, T-values for this maximum are: 2 kb-523°; 4 kb-585°; 6 kb-625°; P±5%, T±10° C. These results give a first approximation of the P, T conditions responsible for a similar mineral reaction which has been recorded from natural metamorphic assemblages.

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Herrn Prof. H. G. F. Winkler danke ich für anregende Diskussionen, desgleichen Herrn Dr. D. Puhan für wichtige Hinweise und Mitteilung seiner exp. Daten. Herrn Prof. V. Trommsdorff und Herrn P. H. Thompson bin ich für petrographische Angaben zu Dank verpflichtet. Der Aufbau der Hydrothermalanlage und die Finanzierung der laufenden Untersuchungen wurde aus den Mitteln des Fonds zur Förderung der wissenschaftlichen Forschung ermöglicht. Für diese Unterstützung gilt daher mein besonderer Dank.     

Empirical calibration of six geobarometers for the mineral assemblage quartz+muscovite+biotite+plagioclase+garnet

Six equilibria among quartz, plagioclase, biotite, muscovite, and garnet were empirically calibrated using mineral composition data from 43 samples having the assemblage quartz+muscovite+biotite+garnet+plagioclase+Al₂SiO₅ (sillimanite or kyanite). Pressures and temperatures in the data set used for calibration were determined through the simultaneous application of garnet-biotite geothermometry and garnet-quartz-plagioclase-Al₂SiO₅ geobarometry. Thermodynamic expressions for four of the six equilibria incorporate interaction parameters that model non-ideality in the mixing of cations in the octahedral sites of both muscovite and biotite. With pressure chosen as the dependent variable, multiple regression was used to solve for unknowns in the equilibrium thermodynamic expressions. The regressions yielded multiple correlation coefficients ranging from 0.983 to 0.999, with corresponding standard deviations of 338 and 92 bars in the residuals. The standard deviations in the residuals may be explained largely or entirely by the propagation of errors associated with electron microprobe analysis. These equilibria enable the determination of pressures from equilibrium assemblages of quartz+garnet+plagioclase+muscovite+biotite, and give results closely comparable to the experimentally calibrated garnet-quartz-plagioclase-Al₂SiO₅ geobarometer. Geobarometric applications should be restricted to rocks in which equilibrium constants and compositional variables fall within the same ranges as those used for calibration.     

Experiments on the phase transition calcite+wollastonite+ +epidote=grossular-andraditess+CO2+H2O

The reaction 2 epidote+2 calcite+3 wollastonite3 grossular-andradite_ss+ 2 CO₂+1 H₂O has been explored by hydrothermal experiments at a total fluid pressure of 1000 bars. For a grossular-andradite_ss of andradite ₂₅ composition, the isobaric univariant curve passes through the points 458°C: X_CO2=0.00; 521°C: X_CO2=0.026; 523°C: X_CO2=0.052; 526°C: 0.088; 528°C: X_CO2=0.104. This curve intersects the isobaric univariant curve of the reaction calcite+quartz+[H₂O] wollastonite+CO₂+[H₂O] at the isobaric invariant point around 528°C and X_CO2=0.12. At higher values of X_CO2, this reaction is replaced by another one, namely: 2 epidote+5 calcite+3 quartz3 grossular-andradite_ss+5 CO₂+ 1 H₂O. It is demonstrated that both the reactions do actually take place during the metamorphism of calcareous rocks. The petrologic significance of contrasted sequence of reactions within this system observed by various workers is also discussed.     

应用VC+ +对MAPGIS进行二次开发

本介绍了用VC＋＋对MAPGIS进行二次开发的方法和基本函数以及软件开发实例。     

Experimentelle Untersuchung der Reaktion Dolomit + Kalifeldspat + H2O ⇌ Phlogopit + Calcit + CO2

The equilibrium curve for the reaction 3 dolomite + 1 K-feldspar + 1 H₂O=1 phlogopite + 3 calcite + 3 CO₂ was determined experimentally at a total gas pressure of 2000 bars using two different methods.

1. In the first case water alone was added to the reactants. The CO₂ component of the gas phase was producted solely by the reaction under favourable P-T conditions. This manner of carrying out the reaction is called the “water method”. With this method sufficient time must be allowed for the gas phase to attain a constant composition (see Fig. 1). Reverse reactions were carried out using reaction products of the forward reaction.
2. In the second case silver oxalate + water were added to the reactants. Breakdown of the silver oxalate leads to formation of a CO₂-H₂O gasphase of definite composition. At constant temperature and gas pressure the \(X_{{\text{CO}}_{\text{2}} } \) determines whether the reaction products will be phlogopite + calcite or dolomite + K-feldspar. In this case it is not necessary to wait for equilibrium to be attained. This method is abbreviated the “oxalate method”. Reactants for reverse reactions are not identical with the products of the forward reaction.

At high temperatures the results of the two different methods agree well (see Tables 1 and 2). Equilibrium was attained in one case at 490° C and \(X_{{\text{CO}}_{\text{2}} } \) of approximately 0.77, and in the other case at 520° C and \(X_{{\text{CO}}_{\text{2}} } \) of 0.90. At lower temperatures there are considerable differences in the results. With the water method an \(X_{{\text{CO}}_{\text{2}} } \) of about 0.25 was reached at 450° C. With the oxalate method dolomite K-feldspar and water still react with each other at even higher \(X_{{\text{CO}}_{\text{2}} } \) values. Phlogopite, calcite and CO₂ are formed together with metastable talc. There are no criteria to indicate which of the methods is the correct one at lower temperatures and in Fig. 2, therefore, both equilibrium curves are plotted.     

Stability of the assemblage cordierite +K feldspar+quartz

Under hydrous conditions the stability field of the assemblage Mg-cordierite+K feldspar+quartz is limited on its low-temperature side by the breakdown of cordierite+K feldspar into muscovite, phlogopite and quartz, whereas the high-temperature limit is given by eutectic melting. The compatibility field of the assemblage ranges from 530° C to 745° C at 1 kbar , from 635 to 725° C at 3 kbars , from 695 to 725° C at 5 kbars and terminates at 5.5 kbars . Most components not considered in the model system will tend to restrict this field even more. However, the condition < P _total will increase the range of stable coexistence drastically, making the assemblage common at elevated temperatures from contact metamorphic rocks up to intermediate pressure granulites of appropriate bulk composition.     

EPR of V4+ and Fe3+ in titanites

EPR investigations of yellow-green titanites from four localities showed presence of V⁴⁺ and Fe³⁺. They were investigated at X-band and room temperature. For V⁴⁺ the principal values of the g matrix and ⁵¹V hyperfine splitting and the directions of their principal axes indicate presence of a VO²⁺ ion substituting for Ti. Due to a high zero-field splitting only approximate values of the fine structure parameters of Fe³⁺ could be determined. With directions of their principal axes very similar to those of V⁴⁺ this ion must also substitute for Ti. Unusually large linewidths for both ions with little variation for samples from different localities are ascribed to the reported domain structure of titanites and accumulation of impurities in the domain boundaries. While for Fe³⁺ a small variation of the fine structure parameters explains this broadening, for V⁴⁺ a distribution of g-factors equal to its total anisotropy must be responsible whereas the V=0 bond length is remarkably constant. Due to preferential incorporation of impurities in the grain boundaries a contribution of dipolar broadening cannot be excluded.