运城盐池开发利用的新进展

运城盐池是我国著名的内陆盐池,也是山西省重要的无机盐生产基地,盐池中含有储量丰富的白钠镁矾,开发历史悠久。过去运城盐化局只从盐气中提取十水芒硝及用卤水与芒硝反应制取食盐。而后将十水芒硝加热脱水生产元明粉或含80～90% Na_2SO_4的水硝。再将一部分硫酸钠,经转炉煅烧生产硫化碱。上述产品国内畅销并远销国外,受到用户好评。但盐池中的大量镁盐从未开发利用,     

35℃时Na_2SO_4-MgSO_4-(NH_4)_2SO_4-H_2O体系相图及其应用

针对白钠镁矾矿产资源的加工开发,提出以硫酸铵做盐析剂分离白钠镁矾制备镁氮复肥和硫酸钠的设想,采用等温法测定了35℃时Na2SO4-Mg SO4-(NH4)2SO4-H2O四元体系的溶解度,并依据相平衡数据绘制了相图。该相图存在4个共饱点和6个结晶区,6个结晶区分别是Mg SO4·7H2O结晶区,Mg SO4·Na2SO4·4H2O复盐结晶区,Na2SO4结晶区,Na2SO4·(NH4)2SO4·4H2O复盐结晶区,(NH4)2SO4结晶区,以及Mg SO4·(NH4)2SO4·6H2O复盐结晶区,其中Mg SO4·(NH4)2SO4·6H2O的结晶区最大,表明该复盐Mg SO4·(NH4)2SO4·6H2O易于结晶析出。依据相图分析和计算,设计了白钠镁矾矿和(NH4)2SO4为原料制备氮镁复肥和十水硫酸钠的新工艺,新工艺具有生产母液不需蒸发水分,显著节能的优点。     

黑北凹地富钾地下卤水自然蒸发实验研究

黑北凹地位于阿尔金山山前,其富钾地下卤水储量巨大,该卤水以钠、氯含量占绝对优势。富钾地下卤水化学组成简单,易于提取,具有很好的开发利用价值。以该富钾卤水为研究对象,在现场进行了自然蒸发实验。通过实验发现,卤水经过较长的石盐（NaCl）析出阶段后,分别达到光卤石（KCl·MgCl₂·6H₂O）和水氯镁石（MgCl₂·6H₂O）析出阶段,最后蒸干于南极石阶段,其析盐顺序为石盐—光卤石—水氯镁石—南极石;其中钾只以光卤石矿物析出,且析出阶段比较集中,在整个蒸发过程中氧化硼（B₂O₃）和锂则都在卤水中浓缩富集,没有析出。根据卤水蒸发过程中的析盐规律,其与K ⁺,Na ⁺,Mg ²⁺//Cl ^--H₂O（25 ℃）介稳相图相符,蒸发过程中的体系变化趋势为液相体系点在石盐相区逐渐向远离石盐相点的方向移动,到达石盐与钾石盐共饱线后沿此线向石盐、钾石盐、光卤石共饱点移动,后沿石盐、光卤石共饱线移动,最终蒸干于石盐、光卤石、水氯镁石共饱点。经过对整个蒸发过程中卤水pH及密度的变化规律进行分析,指出可以通过pH及密度的变化来控制卤水的制卤过程。通过该蒸发实验研究,将为黑北凹地地下卤水的提钾工艺实验和后期开发提供科学依据。     

白钠镁矾盐湖矿制取芒硝和泻利盐冷却结晶工艺研究

介绍了一种以白钠镁矾为原料制取芒硝和泻利盐的工艺,该工艺克服了传统工艺的缺陷,减少了工艺中析白钠镁矾的过程,工艺流程能耗低、操作简便、生产成本低、经济效益好,可以充分利用硫酸钠、硫酸镁资源。讨论了对该工艺的各种影响因素,确立了适宜的工艺条件,并制得合格的芒硝和泻利盐产品。     

西藏朋彦错盐湖碳酸盐型卤水15℃等温蒸发实验研究

通过开展朋彦错盐湖夏季卤水15℃等温蒸发实验,参考Na~+,K~+∥Cl~-,SO_4~(2-),CO_3~(2-)-H_2O五元体系25℃介稳相图,获得了卤水在蒸发过程中Li、K、B、Na等元素的浓缩富集规律及各盐类矿物的析出顺序。结果表明,朋彦错盐湖卤水在15℃等温蒸发过程中,先后析出菱镁矿和芒硝矿物,最后析出少量含K和B矿物。K和B分别以钾芒硝和硼砂的形式少量沉淀析出,氯化钠在整个过程中持续析出。Li在整个蒸发过程中未见析出,处于持续富集状态。     

硝板采溶原理及方法

运城盐湖地表固体矿以白钠镁矾(俗称“硝板”,其分子式为Na_2SO_4·MgSO_4·4H_2O)为主体。硝板易溶于水的性质有利于强化芒硝生产的制卤工序,加快成卤速度,提高卤水质量。因此掌握溶采硝板的原理和方法是相当重要的。     

硫酸镁亚型卤水制取硫酸钾完成中间试验

新疆罗布泊钾盐科技开发有限责任公司近日完成了现场变温条件下兑卤蒸发路线试验 ,进行制取高质量钾盐镁矾型钾混盐和光卤石型钾混盐的研究 ;钾盐镁矾型钾混盐转化、富集制取优质软钾镁矾中间试验 ;光卤石型钾混盐分解浮选生产氯化钾中间试验 ;由软钾镁矾、氯化钾经盐田法制取硫酸钾 (ＬＢＰ - 0 1工艺 )和装置法生产硫酸钾 (ＬＢＰ - 0 2工艺 )的产品化研究。通过中间试验 ,搞清了罗布泊卤水在自然条件下的蒸发路线 ,确定了制取高质量钾混盐较佳的工艺方法 ;解决了罗布泊卤水生产氯化钾的难题 ,从而解决了其氯化钾原料供应的难题 ;以罗布泊…     

察尔汗盐湖盐田工艺相图分析及计算

以察尔汗盐湖卤水滩晒含钠光卤石的盐田工艺为研究对象,以Na+、K+、Mg2+∥Cl-—H2O四元水盐体系相图理论为依据,对察尔汗盐田工艺分别做了25 ℃等温相图和多温相图分析。结果表明：察尔汗盐湖卤水在15~ 25 ℃时的结晶路线为NaCl→NaCl+Car→NaCl+Car+Bis,-5~15 ℃时的结晶路线为NaCl→NaCl+KCl→NaCl+Car→ NaCl+Car+Bis。物料衡算结果表明：分段蒸发使原矿的钠质量分数由37.046%降至12.353%,钾质量分数由16.899%提升至23.525%,分段蒸发可有效降低光卤石矿中杂质氯化钠的含量,提高含钠光卤石的品位,KCl收率高达97.90%。该研究可为盐田生产和工艺计算提供理论指导。     

298K下Na~+,K~+//Cl~ˉ,SO_4~(2ˉ),NO_3~ˉ-H_2O五元体系液固介稳相平衡

研究了298 K下,五元体系Na+,K+//Clˉ,SO42ˉ,NO3ˉ-H2O的液固介稳相平衡。采用等温蒸发法确定了溶液的介稳平衡溶解度。根据实验数据,绘制出了该体系介稳相图中氯化钠介稳饱和区以及氯化钠饱和条件下的介稳相平衡投影相图。相图中,有四个四盐共饱的零变量点、九个三盐共饱的单变量线和六个两盐结晶区:Na2SO4·Na NO3·H2O+Na Cl,3K2SO4·Na2SO4+Na Cl,Na NO3+Na Cl,KNO3+Na Cl,Na2SO4+Na Cl和KCl+Na Cl。该体系在298 K下的介稳相图和稳定平衡相图存在一定的差别,复盐3K2SO4·Na2SO4的结晶区明显缩小。     

四元体系Li~+,K~+//CO_3~(2-),B_4O_7~(2-)-H_2O273K介稳相平衡研究

针对西藏扎布耶盐湖卤水组成,用等温蒸发平衡法研究了四元体系Li+,K+//CO23-,B4O27--H2O 273 K的相平衡,测定了平衡时各组分的溶解度及平衡液相的密度。四元体系Li+,K+//CO32-,B4O72--H2O273 K时的相图由5条溶解度单变量线、4个结晶区及2个共饱点组成。4个结晶区分别为对应于盐Li2CO3,K2CO3.1.5H2O,K2B4O7.4H2O及Li2B2O4.16H2O。2个共饱点中,一个为Li2CO3,K2CO3.1.5H2O及K2B4O7.4H2O三盐相称共饱点,另一个为Li2CO3,K2B4O7.4H2O和Li2B2O4.16H2O的三盐不相称共饱点。体系属四元水合物相图Ⅰ型,4种原始组分间未形成复盐或固溶体。对于该四元体系273 K和288 K下的介稳相图发现,碳酸锂盐的溶解度呈现较明显的负温度效应,它在273 K下的结晶相区比在288 K下的要小,且析出固相为偏硼酸锂;而碳酸钾、硼酸钾及硼酸锂结晶区则比288 K下的大。     

四元体系Rb+, Cs+, Mg2+ // SO42- - H2O 298.2 K相平衡研究

采用等温溶解平衡法研究了298.2 K下四元体系Rb⁺, Cs⁺, Mg²⁺ // SO₄^2- - H₂O的相平衡关系，测定了该体系的溶解度、密度以及折射率，并绘制了相应的稳定相图、水图、密度-组成图和折射率-组成图。研究表明：298.2 K下，该四元体系为复杂四元体系，有复盐Cs₂SO₄·MgSO₄·6H₂O和Rb₂SO₄·MgSO₄·6H₂O以及固溶体[(Rb, Cs）₂SO₄]生成。其稳定相图由4个四元共饱点、9条单变量曲线以及6个结晶区组成。四元共饱点中E₁、E₂、E₃为相称共饱点，E₄为不相称共饱点。6个结晶相区分别对应3种单盐Rb₂SO₄、MgSO₄·7H₂O、Cs₂SO₄，2种复盐Cs₂SO₄·MgSO₄·6H₂O、Rb₂SO₄·MgSO₄·6H₂O和1种固溶体[(Rb,Cs）₂SO₄]。其中，复盐Rb₂SO₄·MgSO₄·6H₂O结晶区最大，表明其在该体系中最易结晶析出；Cs₂SO₄结晶区最小。平衡液相的密度和折射率随着溶液中Cs₂SO₄含量变化呈规律性变化。该体系稳定相图将为硫酸镁亚型盐湖卤水中的铷、铯等资源开发利用提供理论依据。     

-15℃下Na+， K+， Mg2+//Cl-， NO3-， SO42——H2O体系相平衡研究

新疆卤水硝酸盐矿主要含有Na⁺、K⁺、Mg²⁺、Cl^-、NO₃^-、SO₄^2-六种离子，属于高元复杂体系，其合理利用和开发需要不同温度下的相平衡研究作为理论支撑。采用等温溶解平衡法，对Na⁺， K⁺， Mg²⁺//Cl^-， NO₃^-， SO₄^2--H₂O体系在-15℃、NaCl·2H₂O饱和条件下的相平衡进行了研究，并构建了相图。相图中有六个零变量点和八个两盐结晶区，只存在一种复盐KCl·MgCl₂·6H₂O。八个两盐结晶区，分别对应于NaCl·2H₂O+Na₂SO₄·10H₂O、NaCl·2H₂O+NaNO₃、NaCl·2H₂O+KCl、NaCl·2H₂O+KNO₃、NaCl·2H₂O+MgSO₄·7H₂O、NaCl·2H₂O+MgCl₂·8H₂O、NaCl·2H₂O+Mg(NO₃)₂·6H₂O和NaCl·2H₂O+KCl·MgCl₂·6H₂O，其中NaCl·2H₂O+Na₂SO₄·10H₂O共晶区最大，在低温时，硫酸钠的溶解度最小，降温过程中较易结晶析出。与该体系在25℃下的相图相比，复盐种类减少5种，零变量点减少19个，相关系得以极大简化。     

Thin-Layer Chromatography of Metal Ions in Formic Acid Medium on Impregnated and Unimpregnated Silica Gel G: Semiquantitative Determination of Fe3+, Cd2+, Th4+, Al3+, Zn2+, UO2+ 2, VO2+, Ce4+, and Ni2+

Abstract

The adsorption behavior of metal ions in the formic acid-sodium formate system using unimpregnated as well as impregnated silica gel G as thin layers has been studied. A remarkable result of this study is the dramatic selectivity of impregnated silica gel G thin layers when compared to the corresponding unimpregnated silica gel G thin layers. This impregnation effect provides us with a new adsorbent phase which is sufficiently stable in the formic acid-sodium formate medium. Some important ternary separations have been achieved on silica gel G thin layers. Al³⁺, Ni²⁺, Fe³⁺, and Pb²⁺ have been qualitatively separated from mixtures of other ions. Cu²⁺ has been selectively separated on impregnated silica gel G thin layers. The semi-quantitative determination of nine metal ions on impregnated silica gel G layers has also been attempted.     

K+,Na+//Cl-,SO2-4 ,NO-3-H2O体系热力学研究

通过引入表达离子缔合或离子间的短程静电作用项,提高了局部组成模型关联单一电解质水溶液体系热力学性质的精度,并通过建立新的计算多元混合体系作用参数的方法,将其推广应用到多离子电解质溶液体系.在此基础上,预测了Na+//Cl-,SO2-4,NO-3,H2O、K+//Cl-,SO2-4,NO-3,H2O、K+ ,Na+//Cl-,SO2-4,H2O、K+ ,Na+//Cl-,NO-3,H2O、K+,Na+// SO2-4,NO-3,H2O 5个四元体系及K+,Na+//Cl-,SO2-4,NO-3,H2O 五元体系的溶解度,模型参数均通过上述体系所包含的二元、三元体系的溶解度数据获得,计算结果满意.     

298．16K下K^＋，Mg^2＋／／NO3^-，SO4^2- -H2O和Na^＋，K^＋，Mg^2＋／／NO3^- -H2O体系的液固相平衡

采用等温溶解平衡法研究了298.16 K下四元体系K , Mg2 //NO3-, SO42--H2O和Na , K , Mg2 //NO3--H2O的液固相平衡,并根据获得的溶解度数据分别绘制出了平衡相图及投影图.结果表明:在298.16 K下,四元交互体系K , Mg2 //NO3-, SO42--H2O相图中有五个单盐结晶区,七条单变量溶解度曲线和三个零变量点.五个单盐结晶区分别对应于KNO3、K2SO4、Mg(NO3)2·6H2O、MgSO4·7H2O和复盐K2SO4·MgSO4·6H2O;具有同离子的四元体系Na , K , Mg2 //NO3--H2O相图中有三个单盐结晶区,三条单变量溶解度曲线和一个零变量点.三个结晶区分别对应于NaNO3、KNO3、Mg(NO3)2·6H2O.K2SO4和KNO3的结晶区比较大,Mg(NO3)2·6H2O的结晶区最小.     

Effect of Co2+, Ni2+, Cu2+, or Zn2+ on properties of polyaniline nanoparticles

Uniform polyaniline (PANI) nanoparticles with typical sizes of about 50 nm were electropolymerized on indium tin oxide surfaces in the presence of Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺. According to shaping theory, we first suggest the reason forming PANI spherical particles. Their conductivity, UV‐vis spectra, FTIR spectra, X‐ray diffraction, and thermogravimetric analysis were investigated. The conductivities and crystallinity of PANI doped with these ions are higher than those of PANI doped with HCl (PANI/HCl). Both UV‐vis absorption spectra and FTIR spectra indicate the interactions between Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ and PANI chains. TG analysis also shows that the thermal stability of PANI doped by Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺ is lower than that of PANI/HCl. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Competitive Adsorption of Ag+, Pb2+, Ni2+, and Cd2+ Ions on Vermiculite

Competitive adsorption of Ag⁺, Pb²⁺, Ni²⁺, and Cd² ions on vermiuculite in a binary, ternary, and quaternary mixture was investigated in batch experiments. The effects of the presence of Ag⁺, Ni²⁺, and Cd²⁺ ions on the adsorption of Pb²⁺ ions were investigated in terms of the equilibrium isotherm. Experimental results indicated that Pb²⁺ ions always favorably adsorbed on vermiculite over Ag⁺, Ni²⁺, and Cd²⁺ ions. The adsorption equilibrium data of Pb²⁺ ions better fitted the Langmuir model than the Freundlich model. The results showed that the pseudo-second-order kinetics model was in good agreement with the experimental results for all metal ions, and the adsorption rate among the metal ions followed Ag⁺ > Pb²⁺ > Ni²⁺ > Cd²⁺. The desorption and regenration study indicated that vermiculite can be used repeatedly and be suitable for the design of a continuous process.     

KINETICS AND MECHANISM OF THE INTERFACIAL MASS TRANSFER OF Zn2+, Co2+, Ni2+ IN THE SYSTEM: BIS(2-ETHYLHEXYL)PHOSPHORIC ACID,n-DODECANE - KNO3, WATER

ABSTRACT

The mass transfer rate of Zn(II), Co(II) and Ni(II) between aqueous nitrate solutions and n-dodecane solutions of the organic soluble ligand HDEHP has been investigated using a forced convection, constant interfacial area stirred cell. The distribution ratios necessary to evaluate the kinetic experiments have been determined and the equilibrium constants which describe the heterogeneous complex formation reaction between Zn²⁺, Co²⁺, Ni²⁺ and HDEHP have been evaluated. The results have been interpreted according to two limiting models: 1) the mass transfer rate is controlled by slow reversible interfacial reactions, 2) the mass transfer is controlled by interfacial film diffusion. Both models are adequate to Interpret the experimental data. The conclusion Is reached that, if interfacial chemical reactions are rate controlling, rate constants of interfacial complex formation reactions independent of the nature of the cation are obtained. This result supports a reaction mechanism which is rate controlled by the microscopic diffusion of the cation through a viscous and structured layer of interfacial water adjacent to the liquid interface     

Fe3+、Co2+、Ni2+、Cu2+参与UV/类Fenton反应动力学研究

以活性艳红X-3B为研究对象,用4种3d轨道过渡金属离子协同UV作催化剂,以H2O2为氧化剂,探讨不同pH值、不同催化剂和氧化剂投入量对色度、COD去除效果的影响;通过改变温度研究4种过渡金属离子进行催化反应的活化能。结果表明,4种过渡金属离子都能发生类Fenton反应,且对活性艳红X-3B的降解速率模型符合二级反应速率模型,通过对反应速率、体系活化能和指前因子的量化研究,得知催化能力的大小顺序为Fe^3＋〉Cu^2＋〉Ni^2＋〉Co^2＋;受温度影响的大小程度排序为：Ni^2＋〉Co^2＋〉Cu^2＋〉Fe^3＋。     

SORPTION PROCESSES OF NATURAL IRANIAN BENTONITE EXCHANGED WITH CD2+, CU2+, NI2+, AND PB2+ CATIONS

Experimental studies on the retention of cadmium (Cd²⁺), copper (Cu²⁺), nickel (Ni²⁺), and lead (Pb²⁺) by bentonite samples from Iran were conducted using single- and multiple-component solutions. Based on the sorption capacity of bentonite the following order was obtained for single- and multiple-component solutions: Pb²⁺ > Cd²⁺ > Ni²⁺ > Cu²⁺. The maximum adsorption capacities of bentonite with metals in single- and multiple-component solutions were 29.5%, 22.5%, 19.2%, and 17.1% and 13.5%, 13.4%, 12.1%, and 9.1% for Pb²⁺, Cd²⁺, Ni²⁺, and Cu²⁺, respectively. Desorption isotherms of Cd²⁺, Cu²⁺, Ni²⁺, and Pb²⁺ deviated significantly from the sorption isotherms, thereby indicating irreversible or very slowly reversible sorption. Finally, soil solution saturation indices and metal speciation were assessed using the Visual MINTEQ 2.6 program and the probability of mineral precipitation was supported by scanning electron microscopy.