A Raman investigation on the boron form occurring in salt lake brine during evaporation

Boron resources are abundant in Da Qaidam salt lake of Qaidamu Basin. It has been given great attention for the polyborate species present in brine. In this study, the Raman spectroscopy was applied to investigate the existing-form of boron in brine during evaporation. The prepared solutions of MgO·2B2O3-H2O, MgO·2B2O3-MgCl2 -H2O, and MgO·2B2O3-MgSO4-H2O was also evaporated and recorded to study the influence of boron concentration, pH, and electrolytes on the borate speciation in brine. The mononborates of B(OH)3 and B(OH)4- were found to be the only forms present in the original salt lake brine. Brine evaporation promotes the formation of polyborate anions B3O3(OH)4-, B5O6(OH)4-, and B6O7(OH)62- and also disappearance of the B(OH)4- ion in brine with boron concentration of more than 11 g/L in B2O3. The pentaborate ion of B5O6(OH)4- was sensitive to the solution pH and found to be appeared under the pH value of 8.0. While the hexaborate ion of B6O7(OH)62- was observed more dependent on the electrolyte of magnesium chloride due to its special properties, such as promoting boron accumulation, lowering solution pH, and also the strong af?nity for water molecules, which is beneficial to the polymerization of borate ions in brine. The interaction mechanisms among polyborate anions during evaporation had also been proposed.     

用硫酸分解大柴旦湖低品位硼矿生产硼酸获得成功

大柴旦化工厂硼酸车间是用CO。法分解大柴旦湖底低品位硼矿制取硼酸，由于工艺中结垢问题一直无法解决，该厂硼酸车间自1989年建成后始终未能正常生产。中国科学院青海盐湖研究所有关科技人员在分析了大柴旦湖低品位硼矿的性质和特点后，提出了用硫酸直接分解硼矿制取硼酸的工艺。该工艺用硫酸分解硼矿，可提高硼矿分解率，降低液回比，滤液直接冷却后就可以得到硼酸产品；同原来的CO。分解法相比，酸法工艺中省去了石灰窑、CO2净化及压缩工段，提高了分解液浓度．省去蒸发工段，解决了结垢问题，降低硼酸生产成本。大柴旦化工厂于1995年…     

冻融干湿交替下灰绿板岩矿质元素释放特征及释放模型

针对宁夏中部干旱带压砂地土壤肥力下降、灰绿板岩矿质元素淋溶释放规律不明等问题,通过室内模拟灰绿板岩冻融干湿循环交替试验,采用修正的Elovich方程、抛物线方程、双常数速率方程、一级动力学方程对各矿质元素的累积释放曲线进行拟合,研究不同粒径板岩在冻融干湿循环作用下的释放动力学特征及最优动力学方程。结果表明：两种粒径灰绿板岩淋溶液中矿质元素淋溶总量随循环次数增大而增大,1 cm粒径灰绿板岩矿质元素累积淋溶总量、淋溶速率在不同循环次数下均大于3 cm粒径。灰绿板岩矿质元素淋溶释放是多因素共同控制的物理、化学过程,其释放过程可大致分为快速反应阶段和反应趋于平衡阶段;压砂地土壤中Ca、K、Mg、P元素的供给量运用修正的Elovich方程预测结果较好,抛物线方程更适用于描述S元素的释放规律。研究结果可为宁夏中部干旱带旱作农田土壤肥力调控提供决策参考。     

基于Pitzer模型预测Na-K-Ca-Mg-Cl-H2O溶液的密度

天然水体系的体积性质与压力、温度、组成的相关性(PVTx性质)研究在地球化学、盐湖化工等领域有广泛的应用。密度是卤水最基本的体积性质,不仅可以通过实验测定,还可以用理论模型进行预测。建立富钾卤水密度与组成、温度的关联模型有助于认识钾在复杂卤水中的富集、迁移规律。为了构建基于Pitzer离子相互作用模型的卤水密度预测方法,本文用高精度振荡管密度计测定了常压下KCl、CaCl₂纯盐溶液以及最高离子强度为11.8 mol·kg^-1的混合溶液在283~323 K下的密度,用所测得的密度通过Pitzer离子相互作用模型拟合得到多温下Pitzer单电解质参数和Pitzer混合参数。用Pitzer模型参数计算了Na-K-Ca-Mg-Cl-H₂O体系293~313 K的密度,计算密度值与实验值的相对偏差在±0.25%以内,计算的结果整体上要优于文献值,文献在计算中均未考虑Pitzer混合参数项。结果表明,K、Ca、Cl离子间的相互作用对于Na-K-Ca-Mg-Cl-H₂O溶液的密度有显著的影响,本文获得的Pitzer参数反映了这些离子间的相互作用,可用于计算含有K、Ca、Cl离子的复杂卤水密度的预测。     

Chemical characterization of fractions of dissolved humic substances from a marginal sea—a case from the Southern Yellow Sea

Marine dissolved organic matter(DOM) is one of the largest dynamic pools of organic carbon in the global carbon cycle, yet DOM is still chemically poorly characterized. To better understand the origin, composition, and cycling of DOM in the China marginal sea, dissolved humic substances(DHS) were isolated from seawaters in two locations in the Southern Yellow Sea. The DHS were subdivided into fulvic acids(FAs), humic acids(HAs) and the XAD-4 fractions. Complementary analytical approaches were used to characterize the isolated DHS samples including stable carbon isotopic composition, Fourier transform infrared spectroscopy(FTIR), ~(13) C cross polarization magic angle spinning(CP/MAS) nuclear magnetic resonance(NMR), and pyrolysis gas chromatography-mass spectrometry(Py-GC/MS). The results demonstrated that both DHS samples encountered the influences from marine source, indicating that algal and microbial-derived materials are the predominant precursors for the studied samples. The three fractions of DHS showed diff erent properties. FAs presented more aromatic features, whereas HAs contained more aliphatic lipids and proteinaceous materials. The XAD-4 fractions were enriched in ~(13) C and contained more carbohydrates but less aromatic compounds. The lower molecular weight and higher heteroatom content and number of carboxyl groups for the XAD-4 fractions may give them considerable geochemical significance for aspects of trace metal species, bioavailability of pollutants, mineral weathering and water acidification in marine environments.     

察尔汗盐湖钾肥生产流程中有机物的组成分析

采用Bond Elute PPL固相萃取小柱对察尔汗1×106t钾肥生产工艺流程中的盐湖卤水有机物进行分离富集,通过元素分析、紫外可见光谱分析、傅里叶红外光谱分析(FTIR)以及高温裂解—气相色谱质谱(Py-GC/MS)对富集得到的有机物进行表征。分析结果表明,察尔汗百万吨钾肥生产工艺流程卤水中,有机物的组成有烷烃烯烃类、醛酮类、含氮类、脂环类、脂肪酸类、芳香类、呋喃及呋喃衍生物类有机物。其中脂环类、脂肪酸类、芳香类、呋喃及呋喃衍生物含量较高。     

大柴旦低品位硼矿的富集研究

在对大柴旦盐湖湖底低品位硼矿的组成、伴生矿物种类、含量等因素进行分析的基础上,依据各矿物物理性质的差异,通过正交试验法,确定采用旋流方法分离低品位硼矿中的石膏和碳酸盐,分别得到以碳酸盐为主要杂质的低品位硼矿和以硫酸盐为主要杂质的低品位硼矿,然后进行分别加工,有效降低大柴旦盐湖低品位硼矿加工过程分解剂的消耗,为大柴旦盐湖低品位硼矿的加工利用提供了一条新的途径。     

固相萃取—热裂解—气相色谱—串联质谱法测定盐湖卤水中溶解性有机质

以青藏高原地区的大柴旦盐湖湖表卤水为研究对象,采用不同的固相萃取(Solid phase extraction,SPE)材料(HLB,PPL,ENVI-18,ENVI-Carb,XAD8和XAD4)对大柴旦盐湖湖表卤水中DOM进行了分离和富集,初步建立了从高盐体系盐湖卤水中高效分离富集出具有代表性的溶解性有机质(Dissolved organic matter,DOM)的方法,系统的考察了pH,上样体积,柱流速和洗脱溶剂对DOM回收率的影响。结合傅里叶变换红外光谱分析(Fourier transform infrared spectroscopy,FTIR)、热裂解—气相色谱—串联质谱分析(Pyrolysis-gas chromatography-mass spectrometry,Py-GC/MS)进一步对盐湖卤水分离物进行了谱学表征。研究结果表明,盐湖卤水在酸性条件下(pH=2),柱流速为0.5 mL/min时有助于吸附剂对DOM的吸附,而随着上样体积的增加,DOM的回收率逐渐下降,而甲醇是比较理想的洗脱剂。大柴旦盐湖湖表卤水中的DOM主要以芳香类,碳水化合物以及部分脂肪族化合物为主,而含氮类化合物含量较少。     

高碳铬铁EDXRF分析中的制样条件优化

利用能量色散X射线荧光光谱分析技术(EDXRF)检测高碳铬铁,能实现对主次组分的同时测量,且无需对铬铁样品进行化学处理.实验以荧光强度和测试精密度为指标,采用单因素试验考察了粉末压片制样过程中称样量、粘结剂种类与用量、研磨时间、压片压力、保压时间等制样条件对测量结果的影响趋势,并将优化后的条件用于对高碳铬铁的检测.结果...     

288.15 K-323.15 K下氯化锂、硫酸锂溶液的密度及摩尔体积研究

用振荡管密度计测定了常压下,温度在288.15-323.15 K范围内不同离子强度的LiCl和 Li₂SO₄溶液的密度,计算了两种锂盐在不同温度下的表观摩尔体积,溶液的浓度范围分别为(0.1~18.9) mol·kg-1及(0.03~3.0)mol·kg-1。用Pitzer离子相互作用模型拟合了LiCl和Li₂SO₄不同温度下的的Pitzer单电解质体积参数,模型的计算值与实验值相吻合良好。