Kinetic parameter estimation for cooling crystallization process based on cell average technique and automatic differentiation

In this paper, a cell average technique(CAT) based parameter estimation method is proposed for cooling crystallization involved with particle growth, aggregation and breakage, by establishing a more efficient and accurate solution in terms of the automatic differentiation(AD) algorithm. To overcome the deficiency of CAT that demands high computation cost for implementation, a set of ordinary differential equations(ODEs) entailed from CAT based discretized population balance equation(PBE) are solved by using the AD based high-order Taylor expansion. Moreover, an AD based trust-region reflective(TRR) algorithm and another interior-point(IP) algorithm are established for estimating the kinetic parameters associated with particle growth, aggregation and breakage. As a result, the estimation accuracy can be further improved while the computation cost can be significantly reduced, compared to the existing algorithms. Benchmark examples from the literature are used to illustrate the accuracy and efficiency of the AD-based CAT, TRR and IP algorithms in comparison with the existing algorithms. Moreover, seeded batch cooling crystallization experiments of β form L-glutamic acid are performed to validate the proposed method.     

High-gravity-assisted green synthesis of rare-earth doped calcium molybdate colloidal nanophosphors

In this work, we report an innovative route for the synthesis of rare-earth doped calcium molybdate (CaMoO₄) nanophosphors by using high gravity rotating packed bed (RPB) technology and paraffin liquid as the solvent. The significant intensified mass transfer and micromixing of reactants in the RPB reactor are benefiting for homogeneous doping of rare-earth ions in the host materials, leading to nanophosphors with high quantum efficiency. The use of liquid paraffin as the solvent eliminates the safety risks associated with volatile organic compounds, increasing the potential for clean production of nanophosphors. Under excitation of deep ultraviolet (DUV) light, the CaMoO₄:Na⁺, Eu³⁺ nanophosphors exhibit red emission at peak wavelength of 615 nm and quantum yield of up to 35.01%. The CaMoO₄:Na⁺,Tb³⁺ nanophosphors exhibit green emission at peak wavelength of 543 nm with quantum yield of up to 30.66%. The morphologies of the nanophosphors are tunable from nanofibers through nanorods to nanodots and the possible mechanism of controlling the formation of different nanostructures is proposed on the basis of experimental results and theoretical analysis of mesoscience. These nanophosphors are highly dispersible in organic solvents and utilized for fabricating fabrication of flexible, freestanding luminescent films based on silicone resin. We also demonstrate the red LEDs consisting of the hybrid films of CaMoO₄:Na⁺,Eu³⁺ nanoparticles as color-converting phosphors and DUV LEDs as illuminators, offering strong potential for future nanophosphors-basedsolid-state lighting systems.     

Research on thermal risk and decomposition behavior of methyl nitrite

The thermal hazards of methyl nitrite(MN) were investigated in the present study. The determination and evaluation of MN decomposition were conducted using a C600 micro thermometer. The thermal runaway reaction characteristics of the compound under different initial pressures were obtained using a VSP2 calorimeter. The kinetic parameters of MN were obtained by regression fitting and calculation of the microthermal experimental data. The experimental and calculated results demonstrated that the potential explosion risk of MN is very high.In addition, there was a high energy barrier in the early stage of the uncontrolled decomposition of MN; however,once the decomposition reaction was initiated, the subsequent decomposition was easily conducted. Under the conditions of adiabatic simulation, the possibility that the reaction was uncontrolled increases with the initial temperature and pressure of the system, and there is a great potential safety risk.     

Thermodynamic modeling and phase diagram prediction of salt lake brine systems. I. Aqueous Mg2+–Ca2+–Cl− binary and ternary systems

Salt lake brine is a complex salt-water system under natural environment. Although many models can express the thermodynamic properties and phase equilibrium of electrolyte aqueous solution, the multi-temperature characteristics and predictability are still the goals of model development. In this study, a comprehensive thermodynamic model system is re-established based on the eNRTL model and some improvements: (1) new expression of long-range electrostatic term with symmetrical reference state is proposed to handle the electrolyte solution covering entire concentration range; (2) the temperature dependence of the binary interaction parameters is formulated with a Gibbs Helmholtz expression containing three temperature coefficients, the liquid parameters, which associated with Gibbs energy, enthalpy, and heat capacity contribution; and (3) liquid parameters and solid species data are regressed from properties and solubility data at full temperature range. Together the activity coefficient model, property models and parameters of liquid and solid offer a comprehensive thermodynamic model system for the typical bittern of MgCl₂–CaCl₂–H₂O binary and ternary systems, and it shows excellent agreement with the literature data for the ternary and binary systems. The successful prediction of complete phase diagram of ternary system shows that the model has the ability to deal with high concentration and high non-ideality system, and the ability to extrapolate the temperature.     

Liquid-solid mass transfer in a rotating packed bed reactor with structured foam packing

A rotating packed bed (RPB) reactor has substantially potential for the process intensification of heterogeneous catalytic reactions. However, the scarce knowledge of the liquid–solid mass transfer in the RPB reactor is a barrier for its design and scale-up. In this work, the liquid–solid mass transfer in a RPB reactor installed with structured foam packing was experimentally studied using copper dissolution by potassium dichromate. Effects of rotational speed, liquid and gas volumetric flow rate on the liquid–solid mass transfer coefficient (k_LS) have been investigated. The correlation for predicting k_LS was proposed, and the deviation between the experimental and predicted values was within ± 12%. The liquid–solid volumetric mass transfer coefficient (k_LSa_LS) ranged from 0.04–0.14 1⁻¹, which was approximately 5 times larger than that in the packed bed reactor. This work lays the foundation for modeling of the RPB reactor packed with structured foam packing for heterogeneous catalytic reaction.     

Experimental measurement and correlation of solubility of β-carotene in pure and ethanol-modified subcritical water

For the first time, the solubility of β-carotene in pure and ethanol-modified subcritical water (SW) using the static method was determined. The experimental runs were performed at a temperature ranging from 298.15 to 403.15 K and 0–10% (w/w) of ethanol as a modifier at a constant pressure of 5 MPa. Samples were analyzed by UV–vis spectrophotometer. The solubility of β-carotene was found to range from 1.084 × 10⁻⁸ to 227.1 × 10⁻⁸ mol fractions in the subcritical water in above mentioned conditions. The obtained β-carotene solubility data were correlated using the linear model and modified Apelblat model. The obtained results showed the modified Apelblat model was better for estimating the solubility of β-carotene in SW. The values of the root-mean-square deviation (RMSD) between experimental and correlated data were calculated and used as the index of validity and accuracy for the model. Also, thermodynamic properties of the solution such as the Gibbs free energy of solution, enthalpy, and entropy of solution were estimated.     

Fabrication,structural and dielectric property of lead-free perovskite silver niobate ceramics

Dielectric capacitors with high recoverable energy density are in high demand for their application in electrical and electronic systems. Among lead-free dielectric materials, silver niobate (AgNbO₃) has attracted growing interest due to its superior energy storage density at room temperature. The field-induced phase transition from antiferroelectric (AFE) phase to ferroelectric (FE) phase contributes to its large energy density. In this work, pure perovskite silver niobate ceramics were fabricated in an oxygen atmosphere by the solid-state reaction technique. The Pbcm orthorhombic phase of AgNbO₃ was closely observed using the Rietveld refinement method to provide explanation for the origin of high spontaneous polarization within a unit cell. Local structural analysis via piezoelectric force microscopy revealed the existence of ferroelectric nano domains, which may contribute to the high energy storage efficiency (η = 99.9926%) in AgNbO₃ at low electric fields. The phase transitions of AgNbO₃ were also investigated via the dependence of the dielectric permittivity (ε′ and ε″) and loss angle tangent (tanδ) on temperatures, providing insights into the further modification of AgNbO₃.     

Phase transition and interface evolution of Al2O3/ZrO2 particles in plasma-sprayed coatings

Alumina and zirconia ceramic particles exhibit high hardness and excellent wear resistance at high temperature, and hence are used as ceramic reinforcement phases in some plasma sprayed coatings. In this study, the interface evolution of a zirconia/alumina eutectic ceramic and the phase transition of zirconia in a plasma-sprayed coating were investigated. Scanning electron microscopy and transmission electron microscopy combined with focused-ion beam and energy dispersive X-ray were used to analyze the microstructure and composition of the ceramic interface. The results showed that the eutectic ceramic particles consisted of alumina (outer) and columnar zirconia (inner) before and after the plasma spraying process. The inner zirconia part showed the martensitic transformation of t-type zirconia to stripe-like m-type zirconia. After the plasma spraying, the interface between alumina and zirconia changed significantly, which formed a new oxide layer. The phase transition mechanism in the ceramic particle and oxide layer formation mechanism at the alumina/zirconia interface were investigated.     

基于多时间尺度和多源储能的综合能源系统能量协调优化调度

考虑源荷不确定性及储能设备配置对综合能源系统IES(integrated energy system)优化调度的影响,提出基于多时间尺度和多源储能的IES能量协调优化调度策略。该策略以系统运行经济最优、滚动控制时域内购能成本与储能惩罚成本之和最低以及设备输出功率调整量最小为目标,分别建立了日前、日内滚动和实时反馈3个时间尺度的优化调度模型。在日前考虑多种储能模式对IES经济性的影响;日内利用场景分析法描述滚动预测的不确定性来提高系统经济运行稳定性;再基于模型预测控制方法,构建日内与实时的反馈闭环优化,平抑由预测误差导致的系统功率波动。仿真结果表明:多源储能模式有助于提高IES的经济性;多时间尺度调度既可以保证IES运行的经济性,又能有效降低不确定性对系统实际运行的影响,减轻电网平抑功率波动负担。     

黄陵矿区主要含水层特征对煤矿采掘的影响

黄陵矿区位于黄陇侏罗纪煤田北部,主要开采2#煤层,矿井生产中对各含水层特征认识不一,严重影响了煤矿的安全生产。针对此问题,收集整理黄陵矿区历年来的勘查数据,对各地层含水性特征进行客观分析与研究,并对主要含水层的富水性进行详细论述。研究结果表明,影响矿区煤层采掘的主要含水层为白垩系下统洛河组含水层和侏罗系中统直罗组含水层,其中,洛河组含水层对矿井采掘的影响较为突出。洛河组含水层富水性属于弱-中等,弱富水性区域位于矿区的东部,中等富水性区域位于矿区的中西部。今后矿井防治水工作中需高度重视矿区中西部洛河组含水层对煤矿采掘的影响。