The effect of temperature on phase equilibria of polyethylene glycol (PEG8000)-K2SO4-H2O at T = (288.15, 298.15, 308.15) K

The phase behavior of potassium sulfate (K₂SO₄) in polyethylene glycol with molecular weight 8000 (PEG8000) and water (H₂O) mixed solvent at 288.15, 298.15, and 308.15 K were determined. According to the results, when the temperature are 288.15 and 298.15 K, there is only a solid–liquid phase equilibrium relationship in the system, and the phase diagrams are both divided into three parts which respectively are the regions of unsaturated homogeneous liquid (L), one liquid and one solid K₂SO₄ (L + S) and one liquid and two solids K₂SO₄ and PEG8000 (L + 2S). The solubility of K₂SO₄ in PEG8000-H₂O mixed solvent decreased with the addition of the PEG8000 in the solution. Comparing the diagrams of 288.15 and 298.15 K, the sizes of regions of (L) and (L + S) increased and that of (L + 2S) decreased with the increase of temperature. While at 308.15 K, solid–liquid and liquid–liquid equilibrium coexist, and there are six parts in the complete phase diagram at 308.15 K, adding the areas of one liquid and one solid K₂SO₄ (L + S), two liquids (2 L), two liquids and one solid K₂SO₄ (2 L + S). The equations developed by Merchuk, Hu, and Jayapal were used to fit the binodal curves data of the system at 308.15 K, meanwhile, the experimental tie-line data of the system at 308.15 K were correlated by Othmer-Tobias equation and Bancroft equation.     

CsCl-PEG8000-H2O三元体系288.2、298.2、308.2K相平衡测定

采用等温溶解法和浊点法研究了288.2、298.2、308.2 K下三元体系CsCl-PEG8000-H₂O的相平衡关系,采用经验方程分别对双液线和结线数据进行了拟合,绘制了完整相图。研究发现CsCl-PEG8000-H₂O体系在288.2、298.2、308.2 K下同时存在固液平衡与液液平衡关系,其完整相图均由不饱和液相区（L）、两个一液一固区（L+S）、双液相区（2L）、两液一固区（2L+S）和两固一液区（2S+L）构成;随着温度升高,不饱和液相区（L）、双液相区（2L）、一液一固区（L+S）、两液一固区（2L+S）均增大,两固一液区（2S+L）减小。对比288.2、298.2、308.2 K下三元体系CsCl-PEG1000/4000/6000/8000-H₂O完整相图,结果表明：288.2、298.2 K时,仅CsCl-PEG1000-H₂O体系存在固液平衡关系,CsCl-PEG4000/6000/8000-H₂O体系同时存在固液和液液平衡关系;308.2 K时,CsCl-PEG1000/4000/6000/8000-H₂O体系同时存在固液和液液平衡关系;双液相区（2L）随聚乙二醇分子量增大而增大。     

四元体系Na+,K+//Br-,SO42——H2O373K相平衡

采用等温溶解平衡法研究了四元体系Na⁺,K⁺//Br^-,SO₄^2--H₂O在373 K条件下的相平衡关系,测定了平衡溶液的溶解度和密度,并根据实验数据绘制相应的相图、水图和密度图。研究发现:交互四元体系Na⁺,K⁺//Br^-,SO₄^2--H₂O在373 K温度下,有复盐钾芒硝Na₂SO₄·3K₂SO₄生成,相图由3个共饱和点、7条单变量曲线和5个结晶区组成。其中,5个结晶区分别对应单盐:K₂SO₄,KBr,NaBr,Na₂SO₄和复盐Na₂SO₄·3K₂SO₄(Gla)。     

308.2 K三元体系KCl+PEG10000/20000+H2O相平衡及热力学计算

采用等温溶解平衡法和浊点法分别测定了308.2 K时三元体系KCl+PEG10000/20000+H₂O的固液平衡组成和液液平衡组成,同时测定了固液平衡时体系的密度和折射率。根据实验数据,绘制了两个三元体系308.2 K时的完整相图、双液线对比图和结线-组成图。研究发现：三元体系KCl+PEG10000/20000+H₂O 308.2 K时的完整相图均包含6个区域：不饱和液相区（L）,2个一固一液区（L+S）,双液相区（2L）,两液一固区（2L+S）,两固一液区（L+2S）;其中,一液两固区（L+2S）中的两种固相分别为KCl和PEG10000/20000。在完整相图中,一固一液区面积最大,双液相区面积最小。对比308.2 K时聚乙二醇分子量为1000、4000、6000、10000和20000的KCl+PEG+H₂O体系可知：分子量为1000、4000和6000时,体系中仅存在固液相平衡关系;分子量为10000和20000时,体系中同时存在固液和液液相平衡关系,且随着聚乙二醇分子量的增加,双液线向原点移动,双液相区（2L）和两液一固区（2L+S）增大,不饱和液相区（L）和一固一液区（L+S）均减小。采用Chen-NRTL-PDH热力学模型进行了液液相平衡计算,计算结果与实验数据吻合较好。     

三元体系K +,Cs +//SO4 2——H2O 298.2 K稳定相平衡研究

采用等温溶解法开展了三元体系K ⁺,Cs ⁺//SO₄ ^2--H₂O 298.2 K稳定相平衡研究,测定了该体系溶解度、密度及折光率。结果表明,该三元体系在298.2 K下属于复杂体系,有固溶体（K,Cs）₂SO₄产生,且固溶体相区最大;其稳定相图包含3条单变量曲线、3个析出相区和2个共饱点;共饱点处对应的液相组成分别为w（K₂SO₄）=11.69%、w（Cs₂SO₄）=4.02%和w（K₂SO₄）=3.39%、w（Cs₂SO₄）=60.84%。平衡液相的密度和折光率随Cs₂SO₄含量的增大呈现递增的趋势。采用经验公式对平衡液相的折光率进行理论计算,计算值和实验值具有良好的一致性。     

333.15 K K+,NH4+//Cl-,SO42——H2O和K+,NH4+//Cl-,SO42——(CH2OH)2-H2O体系固液相平衡

采用等温溶解法研究333.15 K体系（K⁺,NH₄⁺//Cl^-,SO₄^2--H₂O）和（K⁺,NH₄⁺//Cl^-,SO₄^2--（CH₂OH）₂-H₂O）[w（（CH₂OH）₂）=30%]的固液相平衡关系。测定了平衡溶液的溶解度数据及物化性质,包括密度、黏度、折射率、pH。根据实验数据,绘制了相应的干盐相图、水图及物化性质-组成图。实验中的物化性质（黏度、密度、折射率、pH）随J（2NH₄⁺）的变化呈现相似性规律。实验结果表明：在333.15 K下,体系（K⁺,NH₄⁺//Cl^-,SO₄^2--H₂O）和（K⁺,NH₄⁺//Cl^-,SO₄^2--（CH₂OH）₂-H₂O）[w（（CH₂OH）₂）=30%]的相图相似,均含有一个四元共饱和点,四条单变曲线及四个固相结晶区域。这两个体系均为复杂体系,存在（K,NH₄）Cl、（NH₄,K）Cl、（K,NH₄）₂SO₄、（NH₄,K）₂SO₄四种固溶体。实验所获数据和结论,可优化以硫酸盐型固体废弃物为硫酸根来源,转化法生产硫酸钾工艺。     

四元体系LiCl-LiBO2-Li2SO4-H2O在298.15K时的相平衡

采用等温溶解平衡法开展了四元体系LiCl-LiBO₂-Li₂SO₄-H₂O在298.15 K时相平衡实验研究,测定体系溶解度和平衡溶液的折光率、密度、pH和电导率。根据实验数据,分别绘制该四元体系的干基图、水图以及相对应的物化性质-组成图。研究结果表明:在该四元体系298.15 K相图中,有2个无变度共饱点分别为相称共饱点(Li₂SO₄·H₂O + LiCl·H₂O + LiBO₂·2H₂O)和不相称共饱点(Li₂SO₄·H₂O + LiBO₂·2H₂O + LiBO₂·8H₂O)、5条溶解度曲线和4个单盐结晶相区(Li₂SO₄·H₂O、LiCl·H₂O、LiBO₂·8H₂O和LiBO₂·2H₂O),无复盐和固溶体产生,属于简单四元体系水合物Ⅱ型相图。实验研究中,发现2种偏硼酸锂水合矿物存在(LiBO₂·8H₂O和LiBO₂·2H₂O),LiCl对Li₂SO₄的盐析效应显著;四元体系平衡溶液物化性质随着溶液中氯化锂浓度的变化呈现规律性的变化。     

KCl-PEG4000-H2O三元体系288、298、308 K相平衡测定及计算

采用等温溶解平衡法研究了288、298、308 K下三元体系KCl-PEG4000-H₂O的相平衡关系，绘制了相应的相图、密度-组成图和折射率-组成图。研究发现：288、298、308 K下，三元体系KCl-PEG4000-H₂O无分层现象，只存在固液相平衡关系，其平衡相图由不饱和液相区(L)、一固一液区(S+L)和两固一液区(2S+L)构成，且两固一液区随温度升高减小。KCl溶解度随着溶液中PEG4000含量不断增加而减小。溶液中PEG4000含量小于0.50时，盐析率受温度影响较小；含量大于0.50时，盐析率随着温度升高呈减小趋势。采用修正后的Pitzer方程进行了三元体系KCl-PEG4000-H₂O (288、298、308 K)溶解度计算，对比发现，理论计算值与实验值吻合较好。     

四元体系硼酸锂-硼酸钾-硼酸镁-水在308.15 K时固液相平衡研究

采用等温溶解平衡法研究四元体系硼酸锂-硼酸钾-硼酸镁-水在308.15 K时固液相平衡,测定了体系溶解度和平衡液相的密度、折光率和pH。研究发现：该体系308.15 K时的稳定相图中包含一个共饱点（L+Li₂B₄O₇·3H₂O+K₂B₄O₇·4H₂O+Mg₂B₆O₁₁·15H₂O）,其液相组成：w（Li₂B₄O₇）=3.112%、w（K₂B₄O₇）=16.64%、w（Mg₂B₆O₁₁）=0.101 8%;3个固相结晶区：Li₂B₄O₇·3H₂O、K₂B₄O₇·4H₂O、Mg₂B₆O₁₁·15H₂O,体系无复盐或固溶体生成。溶液中硼酸锂、硼酸钾对多水硼镁石有很强的盐析效应,液相的密度、折光率和pH随溶液中硼酸盐浓度的增加呈规律性变化。     

四元体系NaCl+NaBO2+Na2CO3+H2O 298.15 K 相平衡研究

柴达木盐湖中具有丰富的盐湖离子,对其中的一个四元体系水盐相图开展研究,采用等温溶解平衡法开展了298.15 K时四元体系NaCl+NaBO₂+Na₂CO₃+H₂O相平衡研究,测定了体系平衡液相组成及密度和折光率,绘制了四元体系NaCl+NaBO₂+Na₂CO₃+H₂O 298.15 K的相图及相应的物化性质图。研究发现NaCl+NaBO₂+Na₂CO₃+H₂O四元体系298.15 K 时包含2个共饱点（E₁、E₂）、5条溶解度曲线（AE₁、BE₁、CE₂、DE₂、E₁E₂）、4个结晶区（NaCl、NaBO₂·4H₂O、Na₂CO₃·7H₂O、NaCl·NaBO₂·2H₂O）。其中三元体系NaCl+NaBO₂+H₂O在298.15 K下产生了复盐NaCl·NaBO₂·2H₂O,通过研究发现该四元体系NaCl+NaBO₂+Na₂CO₃+H₂O在298.15 K下也具有NaCl·NaBO₂·2H₂O复盐区。     

Selective oxidation of toluene on V2O5/TiO2/SiO2 catalysts modified with Te, Al, Mg, and K2SO4

The effect of the modification of vanadia catalysts supported on TiO₂/SiO₂ by the oxides of Al, Mg and Te, and K₂SO₄on the selective oxidation of toluene in the vapor phase has been studied. The catalysts were prepared by successive impregnation and characterized by BET surface measurements, XRD, XPS, and TPR. Addition of the second component decreased specific activity in all cases, except Al, mainly due to the decrease of surface area. Intrinsic activity was increased with addition of Te and Al, and decreased by that of Mg, while K₂SO₄ had little effect. These differences could be explained by the observed changes in either vanadium surface dispersion or reducibility. Selectivity to benzaldehyde increased markedly with addition of Te or K₂SO₄, that caused the formation of new oxide phases, V₃Ti₆O₁₇ and TiV₂O₆, in which vanadium is in a partially reduced state.     

四元体系LiB5O8+NaB5O8+KB5O8+H2O在298.15K实验与理论预测相平衡研究

采用等温溶解平衡法研究了四元体系LiB₅O₈ + NaB₅O₈ + KB₅O₈ + H₂O在298.15 K下的相平衡。实验测定了该体系在298.15 K下的固液相平衡溶解度和物理性质（密度和折射率）,基于实验溶解度绘制了四元体系的干盐相图、水图和物理性质组成图。在该四元体系的干基图中,有一个共饱点（LiB₅O₈·5H₂O + NaB₅O₈·5H₂O + KB₅O₈·4H₂O）、3条单变量溶解度曲线和3个单盐结晶区（LiB₅O₈·5H₂O、NaB₅O₈·5H₂O和KB₅O₈·4H₂O）。该体系在298.15 K下没有复盐和固溶体生成,属于简单四元水溶液体系。结合三元体系溶解度,拟合获得了3种碱金属五硼酸盐的单盐参数和三离子混合作用参数;应用Pitzer及其扩展的HW模型对溶解度进行预测,预测值与实验值吻合较好,表明获得的Pitzer参数可靠。研究结果可为碱金属五硼酸盐分离纯化提供理论基础。     

Phase transition in K2SO4 AT 56 K

Specific heat and dielectric constant of K₂SO₄ were measured below room temperature down to liquid helium temperature. A phase transition was detected at 56 K, which is accompanied with a slight λ-type anomaly in specific heat and a break on dielectric constant vs. temperature curve. Evidence for the incommensurate or super structure was not confirmed by neutron diffraction.     

Fluxing reactions of sulphate and carbonates in cement clinkering. I. Systems CaSO4-K2SO4 and K2SO4-CaCO3

Phase equilibria and thermodynamics have been used to determine compatabilities in the systems CaSO₄-K₂SO₄ and K₂SO₄-CaCO₃. In the CaSO₄-K₂SO₄ system, a polymorphic inversion at 200°C is encountered in K₂Ca₂(SO₄)₃. Thermodynamic calculation of the reciprocal salt system K₂SO₄-CaCO₃-CaSO₄-K₂CO₃ discloses that the join K₂SO₄-CaCO₃ constitutes a stable binary: experiments in flowing CO₂ at 1 bar pressure confirm this. A noteworthy feature of the system is the solid solution of CaCO₃ in K₂SO₄, reaching 20% mol % CaCO₃. The eutectic, located at 880°C and 43 mol % CaCO₃, is attainable without significant decomposition. The possible consequences to clinkering reactions are discussed.     

锅炉受热面复合陶瓷涂层抗高温SO2腐蚀性能

针对燃煤锅炉受热面存在的高温腐蚀问题,采用料浆法在20G钢材表面制备复合陶瓷涂层,烧结后的复合陶瓷涂层表面较为致密,涂层与基材具有良好的结合状态。对喷涂及未喷涂陶瓷涂层钢片在SO₂腐蚀气氛环境下的抗高温腐蚀性能进行试验,并采用热分析动力学方法对试验数据进行处理,结果表明,在400~500℃温度范围内,两种试样的腐蚀过程均符合一维扩散反应动力学模式,计算求得喷涂涂层钢片腐蚀反应活化能低于未喷涂涂层钢片,涂层具有较好的抗高温腐蚀性能。对腐蚀试验后试样的形貌、成分和物相分析结果显示,涂层在SO₂气氛下腐蚀后,表面生成K₂SO₄晶粒,但由于涂层较为致密,阻止了S的扩散,内部基本没有检测到K₂SO₄的存在。     

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。     

Effect of alkalies on portland cement hydration II. Alkalies present in form of sulphates

Alkalies present in cement in the form of Na₂SO₄ and/or K₂SO₄ do not alter the progress of C₃S and C₃A hydration. The setting time becomes accelerated especially with K₂SO₄ due to the formation of syngenite CaSO₄·K₂SO₄·H₂O. The compressive strength is lowered significantly.     

硫酸钠/氧化硅复合定形相变材料的溶胶凝胶法制备和表征简

A sodium sulfate （NaeSO4）/silica （SiO2） composite was prepared as a shape-stabilized solid-liquid phase change material by a sol-gel procedure using Na2SiO3 as the silica source. Na2SO4 in the composite acts as a latent heat storage substance for solid-liquid phase change, while SiO2 acts as a support material to provide structural strength and prevent leakage of melted NazSO4. The microstructure and composition of the prepared composite were characterized by the N2 adsorption, transmission electron microscope （TEM）, scanning electron microscope （SEM）, Fourier transform infrared spectroscopy （FTIR） and X-ray diffraction. The results show that the prepared Na2SOJSiO2 composite is a nanostructured hybrid of NazSO4 and SiO2 without new substances produced during the phase change. The macroscopic shape of the NazSO4/SiO2 composite after the melting and freezing cycles does not change and there is no leakage of Na2SO4. Determined by differential scanning calorimeter （DSC） analysis, the values of phase change latent heat of melting and freezing of the prepared NazSO4/SiO2 （50%, by mass） composite are 82.3 kJ.kg i and 83.7 kJ.kg-1, and temperatures of melting and freezing are 886.0 ℃ and 880.6 ℃, respectively. Furthermore, the Na2SOJSiO2 composite maintains good thermal energy storage and release ability even after 100 cycles of melting and freezing. The satisfactory thermal storage performance renders this composite a versatile tool for high-temperature thermal energy storage.     

-15℃下Na+, K+, Mg2+// Cl-, SO4-2-H2O体系相平衡

采用等温溶解平衡法,研究了Na⁺, K⁺, Mg²⁺//Cl^-, SO₄^-2-H₂O, 五元水盐体系在-15℃下NaCl·2H₂O饱和时的相平衡关系,测定了溶解度和密度,并绘制出相应的相图。研究结果表明:该五元体系平衡相图中有3个四盐共饱点,7条单变量溶解度曲线及5个两盐结晶区,5个两盐结晶区分别对应于KCl+NaCl·2H₂O、Na₂SO₄·10H₂O+ NaCl·2H₂O、MgSO₄·7H₂O+NaCl·2H₂O、MgCl₂·8H₂O+NaCl·2H₂O、KCl·MgCl₂·6H₂O+ NaCl·2H₂O;所 得-15℃相图和25℃下相图相比,相图结构大为简化:K₂SO₄·MgSO₄·4H₂O、KCl·MgSO₄·3H₂O、Na₂SO₄·3K₂SO₄、Na₂SO₄·MgSO₄·4H₂O、MgSO₄·(4～6)H₂O、K₂SO₄·MgSO₄·6H₂O结晶区均消失,Na₂SO₄结晶区转变为Na₂SO₄·10H₂O且结晶区扩大,KCl、MgSO₄·7H₂O、KCl·MgCl₂·6H₂O结晶区缩小,MgCl₂·6H₂O结晶区转变为MgCl₂·8H₂O。在此基础上研究了不同组成的盐湖卤水在降温过程中的结晶规律,为低温盐田工艺的开发提供了理论依据。     

府谷煤CO2催化气化反应性的研究

加入适宜的催化剂可以提高气化反应速率,降低起始气化温度。为了研究不同阴离子（SO₄^2-、CO₃^2-、Cl^-）盐对府谷煤热失重过程的影响,利用热重分析仪对负载了8种催化剂（K₂CO₃、K₂SO₄、KCl;Na₂CO₃、Na₂SO₄、NaCl;FeSO₄、FeCl₂）的煤样进行了CO₂气化实验,其中每克府谷煤的K⁺、Na⁺、Fe²⁺负载量分别为0.001mol。同时采用升温动力学模型进行了数据拟合。实验结果表明：催化剂对煤与CO₂的低温热解并无明显的催化作用,而在高温气化阶段催化效果显著。对于钾盐和钠盐催化剂,当阳离子相同时,其催化活性顺序为：CO₃^2->SO₄^2->Cl^-。对于铁盐催化剂,FeSO₄的催化活性优于FeCl₂。动力学结果发现：负载催化剂煤样的活化能大小符合上述实验规律,分布在169～232.6kJ/mol之间,相比原煤（267.9kJ/mol）都有一定程度的降低。