MgO焙烧-碳热氯化法提取包钢选矿厂尾矿中的稀土

包钢选矿厂尾矿中含有大量稀土,可以回收利用.提出MgO焙烧-碳热氯化提取包钢选矿厂尾矿中稀士的新工艺.在该工艺中首先将尾矿与MgO混合焙烧脱氟,然后使用氯气作为氯化剂,碳作为还原剂,碳热氯化该脱氟后的尾矿中的稀土,水浸取回收稀土.考察了MgO的用量、碳热氯化时间、碳热氯化温度对稀土提取率的影响.结果表明:尾矿与Mgo焙烧后,700℃氯化反应0.5 h,氯化率高达83%.利用X射线衍射探讨了脱氟过程可能发生的反应.     

HCl-H_2O_2溶液浸出氟碳铈矿的研究

以混合型稀土精矿为研究对象,采用HCl-H2O2溶液浸出氟碳铈矿,达到独居石与氟碳铈矿分离的目的。考察了焙烧温度、盐酸浓度、液固比、双氧水用量、浸出温度、浸出时间等对稀土精矿浸出率的影响规律,并得出最佳浸出工艺条件为:焙烧温度:600℃,焙烧时间:2 h,盐酸浓度:6 mol·L-1,液固比:30∶1,双氧水用量:10 m L,浸出温度:90℃,浸出时间:90 min。通过此实验条件,稀土精矿中氟碳铈矿的浸出率达到了98.69%,使稀土精矿中的氟碳铈矿大部分进入溶液中,达到与独居石分离的目的,为浸出氟碳铈矿的工艺提供新思路。     

HNO3-Al（NO3）3溶液分离包头混合稀土精矿的研究

根据Al3+与F-能形成稳定的络合离子[AlF6]3-,采用HNO3-Al(NO3)3溶液络合浸出包头混合稀土精矿中的氟碳铈矿。热力学分析结果表明:HNO3-Al(NO3)3体系对稀土精矿浸出反应为自发过程。考察了HNO3浓度、Al(NO3)3浓度、液固比、搅拌速度、温度、搅拌时间这些因素对稀土精矿浸出的影响。实验结果表明:在HNO3浓度3 mol·L-1,Al(NO3)3浓度1.5 mol·L-1,液固比30∶1,搅拌速度300 r·min-1,温度100℃,搅拌时间90 min的条件下,稀土精矿中氟碳铈矿的浸出率达到92.18%,氟碳铈矿与独居石基本分离。通过产物层受界面交换和扩散混合控制的新缩小核模型可用来描述浸出过程的动力学,计算推导出了反应的宏观动力学方程。     

包头混合稀土精矿络合浸出的研究

根据Al3+或Fe3+与F-能形成稳定的络合离子[AlF6]3-或[FeF6]3-,分别用HCl-AlCl3和HCl-FeCl3溶液络合浸出包头混合稀土精矿中的氟碳铈矿,并对两者进行了对比.结果表明,用HCl-AlCl3体系的精矿浸出率和稀土浸出率比用HCl-FeCl3体系的都高30％;在HCl浓度4.0 mol·L-1,Al3+浓度2.0 mol ·L-1,温度85℃,浸出时间120 min,液固比为30:1的条件下,稀土精矿中氟碳铈矿的浸出率达到了97.69％,氟碳铈矿中稀土浸出率达到了92.23％,进而使稀土精矿中的氟碳铈矿基本完全进入溶液中,达到与独居石分离的目的.     

MgCl_2焙烧分解白云鄂博氟碳铈矿的研究

针对氟碳铈矿高温焙烧产生含氟废气治理难度大,采用MgCl_2焙烧分解白云鄂博氟碳铈矿精矿。研究了焙烧温度、焙烧时间、盐矿比等工艺参数对稀土提取率的影响,得到最佳工艺条件:焙烧温度460℃,焙烧时间90 min,矿盐质量比1∶1.3,氟碳铈矿中的稀土提取率达到98.9%。通过热重分析(TGA-TG)、X射线衍射(XRD)、扫描电镜(SEM)和能谱分析(EDS)等方法,研究了MgCl_2分解氟碳铈矿氯化焙烧过程的反应机制:氟碳铈矿与MgCl_2分解产物反应生成氯氧化稀土,氯氧化稀土进一步分解得到氧化稀土,氟以MgF_2的形式存在。此工艺节能环保,有效解决了含氟废气问题。     

氟碳铈矿焙烧过程中脱氟机制的研究

测定了La F3和La OF在饱和水蒸气气氛下1000℃焙烧3 h后的脱氟率,采用X射线衍射技术对焙烧产物进行了物相分析。测定了氟碳铈矿在饱和水蒸气气氛下700~1000℃焙烧3 h后的焙烧产物中的氟含量,并对焙烧产物进行了物相分析,对焙烧前后的氟碳铈矿进行了SEM扫描对比分析。结果表明:氟碳铈矿发生脱氟反应的过程为:REF3·RE2(CO3)3首先分解生成REF3和RE2O3,同时伴随REOF的生成,然后在有水分子的条件下,REF3,REOF相继发生脱氟反应生成RE2O3和HF。     

氟碳铈矿精矿的分步氯化—化学气相传输反应

以气态配合物LnAlnCl3n 3(Ln=镧系元素）为载体,研究了从氟碳铈矿精矿中提取分离稀土元素的分步氯化－化学气相传输反应,精矿加热至800K,然后在800－1300K氯化,生成氯化物在1300K与配件反应生成气态配合物,并化学传输分离6h,CaCl2和BaCl2留在残渣中,研究结果表明,递减温度场和波浪形温度场中的化学传输反应呈现明显不同的特性。     

微波氯化分解氟碳铈矿的研究

采用微波加热技术氯化分解四川冕宁60%品位的氟碳铈精矿(含氟碳铈矿57.78%，氟碳钙铈矿33.86%)，利用无水MgCl₂作为氯化剂，活性炭作为辅助剂，实现了微波场中空气气氛下氟碳铈精矿的无氧化焙烧分解。通过热重-差热分析(TG-DSC)、 X射线衍射(XRD)、扫描电镜(SEM)和能谱(EDS)分析等检测手段，阐明了微波氯化分解氟碳铈精矿的无氧化反应机理，得到了主要以氯氧化稀土(REOCl)和氟化镁(MgF₂)为主的微波焙烧矿。通过实验，确定了微波氯化分解工艺的最佳参数：微波功率1200 W，焙烧温度800℃，焙烧时间30 min，矿盐比(氟碳铈精矿∶无水氯化镁∶活性碳)为1∶0.25∶0.18。在此条件下，氟碳铈精矿的分解率为96.23%，酸浸液中氟的浸出率只有23.35%，铈的氧化率小于0.6%。     

氟碳铈矿测氟样品处理新方法研究

用国标GB7483-87《水质氟化物的测定氟试剂分光光度法》不能准确测定氟碳铈矿中的氟量.原因在于该氟碳铈矿中的氟量比较高,一般达到9%～11%,易形成REF3沉淀,用一般的酸消解法很难将氟从矿样中全部蒸馏出来.本文采用加入Ca（OH）2,使氟转化CaF2,矿中的氟能完全被蒸出.并做了矿中氟测定的精密度实验,矿中的氟质量分数为9.02%,CV=0.4424.经加标矿中氟量的0.5、1和2倍等3个水平,其回收率在97.83%～99.44%范围,方法是对国标测氟法的重要补充.     

氟碳铈矿精矿焙烧稀土浸出新工艺研究

以四川冕宁氟碳铈矿精矿为研究对象,提出了一种减少氟碳铈矿中Ce(Ⅲ)的氧化来提高稀土浸出率的新工艺。通过控制焙烧温度和焙烧助剂NaHCO_3用量,利用焙烧助剂分解产物Na_2CO_3熔融包覆矿物以减少Ce(Ⅲ)的氧化,经水洗、酸浸过程,促使氟碳铈矿中铈进入酸浸液而减少留在酸浸渣,从而实现铈的浸出回收,提高总的稀土浸出率。得到的优化工艺条件为:NaHCO_3与氟碳铈矿质量比为40%,于900℃焙烧2 h,水洗温度50℃,水洗液固比10∶1,盐酸浓度为2 mol·L~(-1),酸浸液固比为15∶1,温度75℃酸浸2 h。在此条件下,总稀土浸出率达93.23%,铈的浸出率为87.43%。     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。