Phase equilibrium of CaSO_4Ca(OH)_2-H_2O system

In order to provide the theoretical guidance for applying the neutralization method to treatment of heavy metals wastewater with high concentration of sulfate, and to better understand the mechanism of calcium sulfate scale formation, the equilibrium solubility data of CaSOa-Ca（OH）2-H2O system at 298.15 K were theoretically calculated via the Pitzer semi-empirical ion-interaction theory, and determined experimentally by the optical method combining with X-ray diffractometry, and the calculated and determined phase diagrams of CaSOa-Ca（OH）2-H2O system were plotted and compared. Physical definition of each area was studied, and the physical law of characteristic point and line was explained in detail. Adjusting the pH value of neutralization-hydrolysis solution depended on the SO4z- concentration in the system. And interaction characteristics between the solubilities of CaSO4（s）and Ca（OH）2（s）were found out.

含杂质CO_(2)混合体系的气液相平衡计算模型

对含杂质CO_(2)体系相平衡的准确表征是CCUS(碳捕集、利用与封存)应用中的关键。为探讨针对此类体系相平衡计算的最佳热力学模型,基于CO_(2)/N_(2)、CO_(2)/O_(2)与CO_(2)/H_(2)O等3种二元混合工质的气液相平衡数据,分别使用状态方程(PR、SRK、BWRS、CPA、GERG-2008)和活度系数模型(NRTL、UNIQUAC)进行了气液闪蒸计算。结果表明,针对含杂质CO_(2)二元混合体系,CPA方程具有最高的计算精度,其结果与实验值的平均偏差仅为4.75%。随后,采用CPA方程对CO_(2)/N_(2)、CO_(2)/N_(2)/O_(2)和CO_(2)/N_(2)/O_(2)/H_(2)O等混合物的相包络线进行了预测,其对泡点、露点压力的计算与NIST(美国国家标准与技术研究院)方法计算结果的平均偏差小于3.5%,表明了CPA方程可作为一种简单且准确的含杂质CO_(2)混合体系相平衡计算方法。

Calculation of the Phase Equilibrium of CO2–Hydrocarbon Binary Mixtures by PR-BM EOS and PR EOS

The phase equilibrium data of CO2 hydrocarbon binary mixtures are important for the design and operation of CO 2 ood- ing, coal liquefaction, and supercritical extraction processes. Numerous pieces of binary phase equilibrium data have been obtained. Thus, models for the accurate calculation of binary and multicomponent mixtures must be developed on the basis of existing data. In this work, 3578 vapor liquid phase equilibrium data points for 10 CO 2 hydrocarbon binary mixtures, including CO2 butane, CO 2 pentane, CO 2 isopentane, C O 2 hexane, CO 2 benzene, CO 2 heptane, CO 2 octane, C O 2 non- ane, CO 2 decane, and C O 2 undecane, were collected. The PR and PR-BM equations of state (EOS) in combination with relevant mixing rules were used to calculate the phase equilibrium data of the CO 2 hydrocarbon binary mixtures. The binary interaction parameter k ij in the PR EOS was temperature independent, whereas parameters in the PR-BM EOS were functions of temperature. Thus, the phase equilibrium data and other thermodynamic properties of the binary and multicomponent mixtures at di erent temperatures and pressures can be calculated by using the parameters obtained in this work. The PR-BM EOS performed better than the PR EOS, and the average absolute deviations over the temperature range of 255.98 408.15 K calculated by the PR EOS and PR-BM EOS were less than 5.74% and 3.36%, respectively. The results calculated by the two EOS were compared with those calculated by other models, such as PPR78, PR + LCVM + UNIFAC, KIE + PR EOS + HV, and PSRK. The phase equilibrium data of CO 2 butane decane, CO 2 hexane decane, and C O 2 octane decane ternary mixtures were calculated by the two EOS. The average overall deviations for the CO 2 mole fractions calculated by the two EOS were less than 7.66%.

Phase Equilibrium and Phase Diagram of the Ternary System（MgCl2 + MgB2O4 + H2O） at 288 and 298 K

1 Introduction The brines with high concentrations of magnesium and boron resources are widely distributed in the Qaidam Basin of the Qinghai-Tibet plateau,China(Zheng&Tang,1988).Although some works on the ternary system

5-氯-2-戊酮与环丙基甲基酮物性及汽液相平衡

测定5-氯-2戊酮和环丙基甲基酮的物化性质:密度、黏度、摩尔体积、热膨胀系数和表面张力。测定5-氯-2-戊酮(1)+环丙基甲基酮(2)二元体系的汽液相平衡(VLE),并应用Aspen Plus V11中Van Laar方程、Wilson方程和NRTL方程对实验数据进行关联,回归得到二元交互参数。实验结果通过热力学一致性检查。该研究不仅补充了汽液相平衡数据库,也为5-氯-2-戊酮与环丙基甲基酮的分离提供热力学数据。

NaF-Na_(3)PO_(4)-H_(2)O体系相图与热力学模型

NaF–Na_(3)PO_(4)–H_(2)O体系是稀土矿物加工的典型盐水体系,开发氟、磷回收工艺需要该体系的相图和热力学模型支持。利用等温溶解平衡法测定了273.15 K、298.15 K、323.15 K和348.15 K的固液相平衡数据,并基于eNRTL模型框架构建了该体系从最低共熔点到348.15 K的热力学模型。实验结果表明:NaF–Na_(3)PO_(4)–H_(2)O体系存在NaF、Na_(3)PO_(4)·12H_(2)O、Na_(3)PO_(4)·8H_(2)O和复盐NaF·2Na_(3)PO_(4)·19H_(2)O 4个固相物种;其中复盐在各温度均占据三元体系的主要相区,磷酸钠水合物的相区极窄,很难单独成盐,NaF相区相对较大并随温度升高而增大。热力学模型研究较好地表达了NaF–H_(2)O、Na_(3)PO_(4)–H_(2)O体系的多温离子活度系数、溶液渗透系数、二元体系相图,获得了盐水作用参数和6个固相的热力学数据;通过对三元体系多温相图数据的有效表达,获得了盐-盐作用参数和复盐的热力学数据,在此基础上推测了NaF–Na_(3)PO_(4)–H_(2)O体系相图结构,获得了难以实验测定的9个零变量点和9条单变量共饱和线,从而得到了全部固相的平衡相区,并给出了NaF–Na_(3)PO_(4)–H_(2)O体系完整相图,为更复杂体系的热力学表达以及工业应用提供了参考依据。

Relationship between CO_2 Sensor Voltage Response and Phase Equilibrium of Solid Electrolyte Na,K-β/β″-Al_2O_3

A type of CO2 sensor based on oxygen concentration cell was designed as following: Cell I: Pt | Au, O2, CO2| Na2CO3(Au)|NKBA(Au)|YSZ|O2, CO2|Pt or Cell lI: Pt|Au, O2, CO2|K2CO3(Au)|NKBA(Au)|YSZ|O2, CO2|Pt. (Na,K-β/β'-AI2O3 is named by NKBA). The sensor signal is consistent with the Nernstian slope within the region of phase equilibrium for Na, K-β/β'-AI2O3 material. The relationship between CO2 sensor voltage response and phase equilibrium of solid electrolyte Na, K-β/β-AI2O3 is discussed in this paper.

枯竭气藏CO_(2)封存中的相平衡规律研究

在枯竭气藏CO_(2)注入及封存过程中,注入的CO_(2)引起气、水、固三相之间的再平衡,伴随出现CO_(2)溶解、水蒸发和盐析现象,影响近井带地层物性。以川西的枯竭气藏为例,采用SRK-HV方程和盐析模型分析了枯竭气藏CO_(2)注入过程中的三相变化规律。研究表明:在定容体系中的CO_(2)注入过程中,随着CO_(2)物质的量增加,气相压力增大,CO_(2)溶解度逐渐增大,H2O在气相中的摩尔分数逐渐降低,但H2O在气相中的物质的量不断增加,说明水的总蒸发量加大。此外,水蒸发引起的水相体积减小量相对于初始水相体积较小。因此,地层水矿化度增加幅度较小。CO_(2)的溶解加快了CaCO_(3)的析出,同时抑制了CaSO_(4)、CaSO_(4)·2H2O的析出。在氯化钙型地层水中,随着矿化度增加,地层水中会析出CaCO_(3)和CaSO_(4)两种盐成分。该研究成果对枯竭气藏CO_(2)注入过程中水蒸发及盐析规律研究具有一定的借鉴意义。

Deep insight of unique phase transition behaviors and mechanism in Zr_(2)Co-H isotope system with ultra-low equilibrium pressure

Efficient capture,safe storage and release of tritium from the international thermonuclear experimental reactor(ITER) reaction exhaust gas is a perplexing problem,and the development of an efficient tritium-getter material with ultra-low hydrogenation equilibrium pressure is considered as a reliable way.In this work,Zr_(2)Co alloy was selected as a tritium-getter material and prepared through induction levitation melting.Fundamental performance test results show that Zr_(2)Co exhibits an ultra-low hydrogenation equilibrium pressure of 3.22 × 10^(-6) Pa at 25℃ and excellent hydriding kinetics under a low hydrogen pressure of 0.005 MPa.Interestingly,unique phase transition behaviors were presented in Zr_(2)Co-H system.Specifically,Zr_(2)CoH_(5) formed by Zr_(2)Co hydrogenated at room temperature is initially decomposed into ZrH_(2) and ZrCoH_(3) at200 ℃.With the temperature increasing to 350 ℃,ZrCoH_(3)is dehydrogenated to ZrCo,and then ZrCo further reacts with ZrH_(2) at 650 ℃ to reform Zr_(2)Co and hydrogen.Among the staged phase transition pathways during dehydrogenation,the decomposition of Zr_(2)CoH_(5) occurs preferentially,which is well accordance with both the smallest reaction energy barrier and the maximum reaction spontaneity that are determined respectively from kinetics activation energy and thermodynamics Gibbs free energy.Furthermore,first principles calculation results indicate that the stronger binding of hydrogen in interstitial environments of ZrCoH_(3)and ZrH_(2) triggers the hydrogen-stabilized phase transformation of Zr_(2)CoH_(5).The unique phase transition mechanisms in Zr_(2)Co-H system can shed light on the further exploration and regulation of analogous staged phase transition of hydrogen storage materials.

Progress in the Study on the Phase Equilibria of the CO2·H2O and CO2-HeO-NaCI Systems

To study the feasibility of CO2 geological sequestration,it is needed to understand the complicated mul- tiple-phase equilibrium and the densities of aqueous solution with CO2 and multi-ions under wide geological condi- tions(273.15—473.15K,0—60MPa),which are also essential for designing separation equipments in chemical or oil-related industries.For this purpose,studies on the relevant phase equilibria and densities are reviewed and ana- lyzed and the method to improve or modify the existing model is suggested in order to obtain more reliable pre- dictions in a wide temperature and pressure range.Besides,three different models(the electrolyte non random two-liquid(ELECNRTL),the electrolyte NRTL combining with Helgeson model(ENRTL-HG),Pitzer activity co- efficient model combining with Helgeson model(PITZ-HG))are used to calculate the vapor-liquid phase equilib- rium of CO2-H2O and CO2-H2O-NaCl systems.For CO2-H2O system,the calculation results agree with the experi- mental data very well at low and medium pressure(0—20MPa),but there are great discrepancies above 20MPa.For the water content at 473.15K,the calculated results agree with the experimental data quite well.For the CO2-H2O-NaCl system,the PITZ-HG model show better results than ELECNRTL and ENRTL-HG models at the NaCl concentration of 0.52mol·L -1 .Bur for the NaCl concentration of 3.997mol·L -1 ,using the ELECNRTL and ENRTL-HG models gives better results than using the PITZ-HG model.It is shown that available experimental data and the thermodynamic calculations can satisfy the needs of the calculation of the sequestration capacity in the temperature and pressure range for disposal of CO2 in deep saline aquifers.More experimental data and more accu- rate thermodynamic calculations are needed in high temperature and pressure ranges(above 398.15K and 31.5MPa).

α(α2)/γ PHASE EQUILIBRIA IN Ti-Al-C AND Ti-Al-B TERNARY SYSTEMS

α（α２）／γＰＨＡＳＥＥＱＵＩＬＩＢＲＩＡＩＮＴｉＡｌＣＡＮＤＴｉＡｌＢＴＥＲＮＡＲＹＳＹＳＴＥＭＳ①ＬｉＪｕｎｔａｏ，ＨａｏＳｈｉｍｉｎｇＤｅｐａｒｔｍｅｎｔｏｆＭａｔｅｒｉａｌｓＳｃｉｅｎｃｅａｎｄＥｎｇｉｎｅｒｉｎｇ，Ｎｏｒｔｈｅａｓ...

考虑微纳米限域效应对相平衡影响的CO_(2)驱油机理研究

注二氧化碳能够有效提高致密油藏采收率。然而,致密储层低孔、低渗,微纳米孔喉发育,孔隙中流体受到吸附、流体分子与孔壁相互作用等限域效应的影响,传统相态理论难以对微纳米孔隙中二氧化碳同烃类的相互作用进行准确描述。为此,本文首先提出一种考虑微纳米限域效应的相平衡理论模型。通过引入吸附效应和流体分子-孔壁相互作用参数,对Peng-Robinson状态方程(PR-EOS)进行修正。分别计算了流体组分的无因次临界温度和临界压力的相对偏差值,计算值同实验值符合良好,验证了算法的准确性。然后进行了储层温度压力下的流体相平衡计算。结果表明,微纳米限域效应使流体泡点压力降低,溶解气油比和地层油体积系数增大,原油黏度和界面张力降低。此外,对于CO_(2)驱油过程中轻烃抽提作用和CO_(2)扩散作用研究表明,微纳米限域效应使轻烃的抽提系数降低,CO_(2)扩散作用增强,有利于CO_(2)与原油充分接触,提高原油采收率。该模型能够准确预测致密储层CO_(2)-原油多组分混合物的相行为,为致密储层CO驱油提高采收率技术的应用提供理论支持。

High-pressure Phase Equilibria for Binary Ethanol System Containing Supercritical CO_2

High-pressure phase behavior of supercritical (SC) CO2+ethanol system was investigated at 333.2 K,348.2K, 353.2K, 368.2K, 413.2K and 453.2K and pressure from 2.0MPa to 14.3MPa. The measurement was carried out in a cylindrical autoclave with a moveable piston and a window for adjustment and observation of phase equilibria at given T and p. The samples were taken from two coexisting phases and were analyzed to obtain their compositions. It is shown that the solubility of SC CO2 in ethanol increases drastically with pressures at the given temperature, but the content of ethanol in CO2-rich phase increase faintly.

Phase equilibrium studies of titanomagnetite and ilmenite smelting slags

The phase equilibrium information of slag plays an important role in pyrometallurgical processes to obtain optimum fluxing conditions and operating temperatures.The smelting reduction of titanomagnetite and ilmenite ores in an iron blast furnace(BF)can form Ti(C,N)particles,causing the increased viscosities of slag and hot metal.HIsmelt has been developed in recent years for ironmaking and does not need coke and sinter.The formation of Ti(C,N)in the HIsmelt process is avoided because the oxygen partial pressure in the process is higher than that in the BF.The smelting of TiO_(2)-containing ores in the HIsmelt process results in Al_(2)O_(3)-MgO-SiO_(2)-CaO-TiO_(2)slag.Phase equilibrium in this slag system has been investigated using equilibration,quenching,and electron probe microanalysis techniques.The experimental results were presented in two pseudo-binary sections,which represent the process of HIsmelt for the treatment of 100%titanomagnetite ore and mixed titanomagnetite+ilmenite ore(mass ratio of 2:1),respectively.The primary phases observed in the composition range investigated include pseudo-brookite M_(3)O_(5)(MgO·2TiO_(2)-Al_(2)O_(3)·TiO_(2)),spinel(MgO·Al_(2)O_(3)),perovskite CaTiO_(3),and rutile TiO_(2).The results show that the liquidus temperatures decrease in the TiO_(2)and M_(3)O_(5) primary phase fields and increase in the spinel and CaTiO_(3)primary phase fields with the increase in CaO concentration.The calculation of solid-phase fractions from the experimental data has been demonstrated.The effect of basicity on the liquidus temperatures of the slag has been discussed.The smelting of titanomagnetite plus ilmenite ores has significant advantages to obtain low-sulfur hot metal and high-TiO_(2)slag.Experimentally determined liquidus temperatures were compared with the FactSage predictions to evaluate the existing thermodynamic databases.

Subsolidus Phase Relations in the System MgO-SiO_2-Cr-O and Thermodynamic Properties of Related Cr^(2+)-Containing End-members

Subsolidus phase relations have been determined in the systems SiO2-Cr-O and MgO-SiO2-Cr-O in equilibrium with metallic Cr, at 1100 to 1500℃ and 0 to 2.88 GPa. The results show that there are no ternary phases in the SiO2-Cr-O system at these conditions, i.e., only the assemblage eskolaite-Cr-metal-quartz (or tridymite) is found. In the MgO-containing system, however, extensive substitution of Cr2+ for Mg is observed in (Mg, Cr2+)2SiO4 olivine, (Mg, Cr2+)2Si2O6 pyroxene, and (Mg, Cr2+)Cr2O4 spinel. Cr3+ levels in olivine and pyroxene are below detection limits. The pyroxene is orthohombic at XCrPx2+ < 0.2, monoclinic at higher XCrPx2+ . Thestructure of the spinels becomes tetragonally distorted at XCr2+Sp >0.2. The experimental datahave been fitted to a thermodynamic model, and the authors obtained the mixing parameter (W) of Mg-Cr2+ in olivine, pyroxene and spinel, and the relation between temperatures and free energies of formation for the end-members: Cr2+-olivine (Cr2SiO4), Cr2+-pyroxene (Cr2Si2O6) and Cr2+-spinel (Cr3O4).

Liquidus and phase equilibria in CaO-SiO2-5%MgO-20%Al2O3-TiO2 system

The single hot thermocouple technique （SHTT） and high temperature equilibrium technique were combined to investigate the phase diagram of the CaO-SiO2-5%MgO-20%AlzO3-TiO2 system. The 1300 ℃ to 1500 ℃ liquidus lines are calculated according to the thermodynamic equations based on the pseudo-melting temperatures measured by the single hot thermocouple technique. The phase equilibria relationships are experimentally determined at 1400 ℃ using the high temperature equilibria technique followed by X-ray fluorescence （XRF）, X-ray diffraction（XRD）, scanning electron microscopy （SEM） and energy dispersive X-ray spectroscopy （EDX） analysis. The liquid phase（L）, melilite solid solution phase （（C2MSz,C2AS）ss）, diopside phase（CMS2） and perovskite phase （CaO·TiO2） are found. Coupled with the liquidus lines and equilibria results, the phase diagram is constructed for the specified region of the CaO-SiO2-5%MgO-20%Al2O3-TiO2 system.

AlCl_(3)·6H_(2)O在FeCl_(3)、CaCl_(2)、KCl及KCl–FeCl_(3)溶液中溶解度的实验及预测

如何将AlCl_(3)·6H_(2)O从众多组分中选择性地结晶分离是从煤矸石中提Al的关键,而AlCl_(3)·6H_(2)O在煤矸石酸浸体系中的热力学平衡数据对于结晶过程的控制至关重要。在25~85℃的温度范围内,测定了不同温度和溶液浓度下AlCl_(3)·6H_(2)O在FeCl_(3)、CaCl_(2)、KCl及KCl-FeCl_(3)溶液中的溶解度。实验发现温度对AlCl_(3)·6H_(2)O在所有溶液体系中溶解度的影响均不明显,溶解度只随温度的升高略有增加;溶液浓度是影响溶解度的主要因素,AlCl_(3)·6H_(2)O在所有溶液体系中的溶解度均随溶液浓度的升高而明显下降,分析其原因是由于溶液浓度的增大使得Cl^(–)同离子效应增强。为了提高OLI软件预测结果的准确性,对其嵌入Bromley-Zemaitis模型中“Al^(3+)–Cl^(-)”离子对的交互参数进行了修正。随后验证了修正模型的实用性,结果表明它可应用于AlCl_(3)·6H_(2)O在FeCl_(3)、CaCl_(2)及KCl的任意单、混溶液中溶解度的预测。

不同温度下三元体系NH_(4)H_(2)PO4-NH_(4)Cl-H_(2)O的相平衡测定与关联

采用等温溶解平衡法研究了三元体系NH_(4)H_(2)PO4-NH_(4)Cl-H_(2)O在303.15、323.15、333.15和343.15 K下的固液相平衡关系。通过湿渣法与X射线衍射法相结合鉴定了平衡固相组成,绘制了该三元体系在不同温度下的平衡相图。结果表明:该体系在各温度下的相图中都包含1个共饱和点,2条单变量曲线,3个结晶区。采用Pitzer-Harvie-Weare模型对实验数据关联计算,计算值与实验值的平均相对偏差(RAD)和均方根差(RMSD)最大分别为3.18和0.98,实验值与计算值吻合。实验结果可为该体系的共结晶研究提供必要的热力学数据。

UO_(2)在碳酸盐熔盐中的反应行为研究

为获得UO_(2)在碱金属碳酸盐熔盐体系中的基础反应数据,本文分析了UO_(2)在不同组分碳酸盐熔盐中的平衡浓度和反应产物。本文借助电感耦合等离子体质谱、X射线衍射、红外光谱等表征方法,研究反应产物及铀的形态。结果表明:在本文条件下,铀元素在不同组分碳酸盐熔盐中平衡浓度(500~700℃)呈“V”型分布,其平衡浓度在20~220μg/g,最小值在二元和三元熔盐体系中分别低于30μg/g和60μg/g(600℃)。另外UO_(2)在碳酸盐熔盐中的反应产物结构均以重铀酸盐为主(<700℃)。在碳酸盐熔盐体系中系统的分析了UO_(2)的反应行为,验证了碳酸盐盐熔盐氧化技术对UO_(2)进行氧化处理的可行性,为该技术的发展提供了一定基础数据的支撑。

CO_(2)埋存中的状态方程研究进展与展望

在废弃油气藏中进行CO_(2)埋存,能够减少温室气体在大气中的直接排放量,是减缓温室效应的有效途径之一。改进常规的气液相平衡理论,应用热力学状态方程研究CO_(2)-烃-地层水体系,对揭示CO_(2)地下埋存的溶解机理具有十分重要的意义。总结了热力学状态方程对CO_(2)-烃-地层水体系相平衡计算方面的国内外研究进展,指出其实际应用中的不足,分析了其发展趋势,包括:应进一步研究适用于非理想体系的状态方程和混合规则,准确预测该体系热力学性质变化规律;拓展研究体系的地层水离子差异,使之与真实CO_(2)埋存条件相符合;将CO_(2)中相态变化的物理过程与地层水中矿物溶解析出的化学过程耦合。