Vapor compression CuCl heat pump integrated with a thermochemical water splitting cycle

In this paper, the feasibility of using cuprous chloride (CuCl) as a working fluid in a new high temperature heat pump with vapor compression is analyzed. The heat pump is integrated with a copper–chlorine (Cu–Cl) thermochemical water splitting cycle for internal heat recovery, temperature upgrades and hydrogen production. The minimum temperature of heat supply necessary for driving the water splitting cycle can be lowered because the heat pump increases the working fluid temperature from 755 K up to ～950 K, at a high COP of ～6.5. Based on measured data available in past literature, the authors have determined the T–s diagram of CuCl, which is then used for the thermodynamic modeling of the cycle. In the heat pump cycle, molten CuCl is flashed in a vacuum where the vapor quality reaches ～2.5%, and then it is boiled to produce saturated vapor. The vapor is then compressed in stages (with inter-cooling and heat recovery), and condensed in a direct contact heat exchanger to transfer heat at a higher temperature. The heat pump is then integrated with a copper–chlorine water splitting plant. The heat pump evaporator is connected thermally with the hydrogen production reactor of the water splitting plant, which performs an exothermic reaction that generates heat at 760 K. Additional source heat is obtained from heat recovery from the hot reaction products of the oxy-decomposer. The heat pump transfers heat at ～950 K to the oxy-decomposer to drive its endothermic chemical reaction. It is shown that the heat required at the heat pump source can be obtained completely from internal heat recovery within the plant. First and second law analyses and a parametric study are performed for the proposed system to study the influence of the compressor's isentropic efficiency and temperature levels on the heat pump's COP. Two new indicators are presented: one represents the heat recovery ratio (the ratio between the thermal energy obtained by internal heat recovery, and the energy needed at the heat pump evaporator), and the other is the specific heat pump work per mole of hydrogen produced. This new heat pump with CuCl as a working fluid can be attractive in other industrial contexts where high temperature heat is needed. One may replace a common heating technology (combustion or electric heating) with the present sustainable method that uses heat recovery and high efficiency temperature upgrading for heating applications.     

Analysis of the heat generation of lithium-ion battery during charging and discharging considering different influencing factors

Operating temperature of lithium-ion battery is an important factor influencing the performance of electric vehicles. During charging and discharging process, battery temperature varies due to internal heat generation, calling for analysis of battery heat generation rate. The generated heat consists of Joule heat and reaction heat, and both are affected by various factors, including temperature, battery aging effect, state of charge (SOC), and operation current. In this article, a series of experiments based on a power-type lithium manganese oxide/graphite battery was implemented under different conditions. The parameters for Joule heat and reaction heat are determined, and the Joule heat, reaction heat as well as total heat generation rate is detailed and analyzed considering the influence of temperature, aging, SOC, and current. In order to validate the accuracy of heat generation rate, a lumped battery heat transfer model is applied to calculate the temperature variation, and the estimated temperature variation shows good correspondence with experimental results under different currents and aging conditions. Due to its simplicity, the temperature variation estimation method is suitable for real time applications.     

差示扫描量热仪对物质相变潜热的精确量度

差示扫描量热仪(DSC)在测量物质相变潜热方面有着十分广泛的应用。当相变前后试样的比热发生较大的变化,亦即相变前后DSC的基线不在同一直线上时,导致在实际测量样品的相变潜热过程中,出现各种经验处理方法共存的局面[1-3]。对于同一实验曲线,不同的经验处理方法会得到不同的潜     

Modulated temperature DSC measurements relating to the cold crystallization process of poly(ethylene terephtalate)

The modulated temperature differential scanning calorimetric method (MT-DSC) yields three temperature dependent signals, an underlying heat capacity curve from the underlying heat flow rate (corresponding to the conventional DSC signal), and a complex heat capacity curve with a real part (storage heat capacity) and an imaginary part (loss heat capacity). These curves have been measured in the cold crystallization region for poly(ethylene terephtalate) with a modified Perkin-Elmer DSC-7. The underlying curve shows the well known large exothermic crystallization peak. The storage heat capacity shows a step change which reproduces the change in heat capacity during crystallization. This curve may be used as baseline, to separate the crystallization heat flow rate from the underlying heat flow rate curve. The loss heat capacity curve exhibits a small exothermic peak at the temperature of the step change of the storage curve. It could be caused by changes of the molecular mobility during crystallization.Dedicated to Professor Wunderlich on the occasion of his 65th birthday     

Sample evaporation in conventional GC split/splitless injectors. Part 1: Some quantitative estimates concerning heat consumption during evaporation

During sample evaporation in conventional vaporizing injection, the supply of heat to the evaporating liquid is a problem, first because the amounts of heat consumed are relatively large and, secondly, because the heat must be transferred to the sample within a very short time. Times available for evaporation, required amounts of heat, possible sources of heat, and the time required to transfer the heat to the sample liquid are discussed. It is shown that mixing with carrier gas contributes little heat to the evaporation process, but also that packings with glass wool have too low a heat capacity to deliver the required amount of heat to the evaporating sample. Transfer of heat from the insert wall to the sample easily requires several seconds, even if cooling of the vaporizing zone by 20° is accepted. Thus “flash evaporation” is usually impossible and most liquids must be held in the vaporizing chamber to allow full evaporation.     

Temperature modulated differential scanning calorimetry (TMDSC) in the region of phase transitions. Part 1: theoretical considerations

For temperature modulated differential scanning calorimetry (TMDSC) a simple model, the low pass filter, is presented which allows to see and calculate the influence of heat transfer into the sample on magnitude and phase shift of the modulated part of the measured heat flow rate and the heat capacity determined from it. A formula is given which enables to correct the measured magnitude of the periodic heat flow rate function and the calculated heat capacity in dependence on the thermal resistance and heat capacity of the sample. The correction becomes very important in regions where the heat capacity changes considerably as in the melting region. The approach is successfully tested with model substances with well-known excess heat capacity in the transition region.     

热解过程中生物质半焦比热容的测定

采用热重-差示量热扫描法(TG-DSC)测量了生物质和一次热解焦炭及不同转化率下半焦的比热容,建立了计算半焦比热容的数学模型并与实验测量结果进行了对比。结果表明,生物质样品和热解焦炭的比热容在60~200℃随温度升高而线性增大。生物质焦炭的比热容低于生物质样品的比热容,从60℃时的1.2 J/(g·K)增大到200℃附近的1.8~2.0 J/(g·K)。生物质半焦比热容随热解转化率的提高而降低。由半焦比热容数学模型计算得到的结果在接近150~200℃时与实验测定的半焦比热容数值基本一致。     

A New Theoretical Approach to Steady State of Temperature Modulated Heat Flux DSC

The steady state of temperature modulated heat flux DSC, in which the sample temperature is controlled at a fixed frequency, a fixed amplitude and a constant underlying heating rate, is theoretically investigated for complex heat capacity of the sample, taking accounts of heat capacities of heat paths, heat loss to the environment and mutual heat exchange between the sample and the reference material. Rigorous and general solutions for the temperature difference oscillation are obtained in relation to the sample temperature as a reference oscillation. The results are quite different from those obtained in functions of the heat source temperature as a reference oscillation. From these solutions, application of the technique to heat capacity measurements is discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Heat capacity of superfine oxides of iron under applied magnetic fields

Heat capacity is one of the most characteristic and important properties when the peculiarities of magnetic nanosystems are studied. In these systems the magnetic ordering becomes obvious due to the thermal effects such as heat capacity anomalies. It was considered earlier that heat capacity change under magnetic fields applied is slight and it cannot be taken into account in thermodynamic calculations. However the experimental heat capacity data for ferrofluids under magnetic fields applied show that field and temperature heat capacity dependences have a complicated behavior and in magnetic fields an essential heat capacity change takes place. On the other hand in the literature the contradictory data about heat capacity of nanoparticles appear. According to some papers nanoparticles heat capacity can exceed heat capacity of a bulk material a few times.     

Study on radiative heat transfer property of fiber assemblies using FTIR

Radiative heat transfer could be a significant contribution to the total heat transfer within the highly porous materials. This article reports on the use of a conventional instrument, viz. Fourier transform infrared (FTIR) spectroscopy, for the characterization of radiative heat properties of fiber assemblies with low bulk densities. Experimental measurements on spectral transmission with FTIR were performed on five types of fiber assemblies commonly used for insulating materials. From the measurements, radiative heat conductivity was determined by calculating extinction coefficient using Beer’s Law and applying the diffusion approximation approach. Bulk density, fiber arrangement, and temperature influences to radiative heat transfer were discussed. Results show that radiative heat conductivity decreases with bulk density and that of the random arranged fiber assemblies shows lower radiative heat conductivity than the random ball and parallel arranged fiber assemblies. Radiative heat conductivity is proportional to the cubic temperature. The existing theoretical model was modified by comparing theoretical and experimental radiative heat conductivity results.     

Characterization of ignition and combustion characteristics of phenolic fiber-reinforced plastic with different thicknesses

The present study focuses on ignition and combustion characteristics of phenolic fiber-reinforced plastic (FRP) with different thicknesses under different external heat fluxes using cone calorimeter, which receives little attention to date. A series of parameters including ignition time, thermal thickness, mass loss factor, mass loss rate (MLR), heat release rate (HRR), total heat release (THR), fire performance index (FPI) and fire growth index (FGI) are measured or calculated. Results indicate that the ignition time increases with the thickness, but decreases with the external heat flux. Phenolic FRP with thickness of 3 mm may be considered as thermally thin material. However, phenolic FRP with thickness of 5 and 8 mm is prone to be thermally thick material. The critical heat flux, minimum heat flux and ignition temperature are deduced and validated. The thermal thickness increases with the external heat flux. Linear correlations of the thermal thickness with the ratio of specimen density and external heat flux are demonstrated and presented. The mass loss factor decreases with the thickness. Three and two peak MLRs occur in the cases of low and high external heat fluxes, respectively. The average MLR increases with the external heat flux and thickness. The average and maximum HRR increases with the external heat flux. The FGI for the maximum HRR increases with the external heat flux. Linear correlations of the average MLR, the average and maximum HRR and the FGI for the maximum HRR with the external heat flux are demonstrated and presented.

     

Theoretical investigations into heat transfer in laser-welded steel sheets

This study contains mathematical modelling and numerical analysis of heat transfer in laser beam welding process. The temperature field was obtained on the basis of numerical solution into unsteady heat transfer equation with convective term and volumetric heat sources taken into account. Volumetric heat source model describing laser beam power distribution in combined truncated cone?Ccylinder volume was developed. Due to the wide range of temperatures appearing in the process latent heat of fusion, evaporation as well as latent heat of phase transformations in solid state were taken into account in the solution algorithm. On the basis of developed numerical algorithms an analysis of heat transfer in laser butt-welded steel sheets as a three-dimensional initial-boundary problem was performed.     

A Theoretical Approach to Temperature Modulated Power Compensation DSC

The steady state of temperature modulated power compensation DSC has been theoretically investigated for measurements of complex heat capacity, taking accounts of heat capacities of heat paths, heat loss to the environment, and mutual heat exchange between the sample and the reference material. Thermal contact between the sample cell and the cell holder is also taken into accounts. Rigorous and general solutions are obtained. From these solutions application of the technique to heat capacity measurements is discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

凝结热对低阶煤低温氧化过程的影响

选用Pulse Calorimeter仪器，研究了低阶煤在干燥氧气下低温氧化过程的反应热和相对湿度为80％的氮气下凝结热与温度的变化，以研究凝结热对低阶煤低温氧化过程的影响。结果表明,随着温度的上升体系的反应热增加，而凝结热减少。在26℃~60℃的低温下，体系的凝结热明显高于反应热。因此，低温下凝结热是影响低阶煤的低温氧化过程的重要因素。研究还得到了低阶煤在干燥氧气下低温氧化过程的动力学方程及活化能。     

对MDTA中测样品热容量的准恒温法的评述

对用调制差热分析（ＭＤＴＡ）准恒温法测样品热容量的情形进行了讨论。通过结合最基本的热传导定律和ＭＤＴＡ模型，指出了目前国际上测量样品热容量的准恒温法只能得到在所测温度范围内的物质热容量平均值，调制温度的幅度越大或调制频率越高，所得到的热容量数据越平滑。在所测温度范围内样品热容量基本不变时，用ＭＤＴＡ准恒温法较好；但当样品热容量在所测温度范围内有明显变化时，用传统差热分析法（ＤＴＡ）更好一些。     

Deuterium isotope effect on molar heat capacities and apparent molar heat capacities in dilute aqueous solutions: A multi-channel heat-flow microcalorimeter study

The molar heat capacities of chloroform, dichloromethane, methanol, acetonitrile, acetone, dimethyl sulfoxide, benzene, dimethylformamide, toluene, and cyclohexane, as well as their deuterated isotopologues, were measured using a multi-channel heat conduction TAM (Thermal Activity Monitor) III microcalorimeter. In addition, the apparent molar heat capacities of some of the associated dilute aqueous solutions (0.0039 < solute mole fraction, x_i < 0.0210) were also measured. A temperature drop method from (298.15 to 297.15) K at 0.1 MPa was employed. The corresponding heat capacities were determined from the integration of the measured heat flow. The heat capacity results are shown to be in good to very good agreement with the available literature values. In addition, good correlations were obtained for the effect of isotopic substitution on both molar heat capacity and apparent molar heat capacity in aqueous solutions. These correlations should be useful in the prediction of the molar heat capacities or the apparent molar heat capacities of other deuterated compounds. Since these measurements were conducted with ampoules, the effects of heat of condensation and/or vapor space on the accuracy of the heat capacity determinations are discussed. The overall results from this study demonstrate the utility of a multi-channel heat conduction microcalorimeter in obtaining good reproducibility and good accuracy for molar heat capacities as well as apparent molar heat capacities from simultaneous samples.     

热辐射通量对沥青改性PMMA燃烧特性的影响

采用本体聚合法制备沥青改性聚甲基丙烯酸甲酯(PMMA)块体,研究了热辐射通量对其热释放速率平均值、质量损失速率平均值、点燃时间、CO及CO_2产率的影响。结果表明,添加沥青的PMMA点燃后300 s内平均热释放速率由569 kW/m~2降低到了525 kW/m~2,沥青使其燃烧更加平稳;沥青改性PMMA的平均热释放速率、质量损失速率和CO产率与热辐射通量成线性递增关系;点燃时间随着辐射通量的增加而呈指数衰减趋势;CO_2产率在热辐射通量低于40 kW/m~2时基本不变,高于40 kW/m~2时呈线性递增。添加沥青之后PMMA能够平稳燃烧使其可以作为锥形量热仪标准物质候选物,得到的燃烧特性与热辐射通量的函数关系式为其不确定度评估提供了依据。     

The heat generation rate of nickel-metal hydride battery during charging/discharging

The heat generation rate of nickel-metal hydride battery is investigated during charging/discharging in this study. The heat capacity of 8 Ah cylindrical Ni-MH battery is measured using a large-scale calorimeter. An accelerating rate calorimeter is employed to provide an adiabatic environment for the battery. The generation rates of reaction heat, polarization heat, and combination heat are calculated through curve fitting. Results show that there exits a linear relationship between each generation rate of the three heat items and the charging/discharging currents. It is suggested that the ohm internal resistance of the battery needs to be as low as possible for reducing the ohm heat. In addition, it is better to avoid overcharging in the higher rate of 5 C for battery safety.     

Some elements in specific heat capacity measurement and numerical simulation of temperature modulated DSC (TMDSC) with R/C network

One important application of temperature modulated DSC (TMDSC) is the measurement of specific heat of materials. In this paper, a thermal resistance/capacitance (R/C) numerical model is used to analyze the effects of experimental parameters and calibration on the measurement of specific heat in TMDSC under isothermal conditions. The actual TMDSC experiments were conducted with sapphire and pure copper samples, respectively. Both simulation and experiments showed that in TMDSC, the measured sample specific heat is a non-linear function of many factors such as sample mass, the heat transfer properties of the TMDSC instrument, temperature modulation period, the heat capacity difference between calibration material and the test material, but modulation amplitude has very little effect on the results. The typical behavior of a heat flux type TMDSC can be described as a low pass filter in terms of specific heat capacity measurement when the instrument heat transfer properties are taken into account. At least for metallic materials, where the temperature gradient inside the sample can normally be ignored, the sample should be chosen in such a way that its total heat capacity (mass times specific heat) is close to that of the calibration material in order to get a more accurate result. Also, a large modulation period is beneficial to improving the test accuracy.     

热处理对煤焦反应性及微观结构的影响

用热天平和XRD考察了热处理对二种煤(河北蔚县褐煤、四川湔江烟煤)镜质组半焦微观结构和反应活性的影响。TGA结果表明，热处理温度增加，蔚县煤镜质组(YXV)与湔江煤镜质组(JJV)焦炭的反应性降低；YXV焦炭的反应性随着热处理时间的增加而急剧下降，但一定热处理时间(60 min)后，其下降趋势变缓；热处理时间对JJV焦炭的影响较小。XRD结果表明，在热处理温度为900 ℃，初焦热处理时间为60 min时，YXV焦炭晶格结构发生明显改变，900 ℃以上，YXV焦炭芳香堆垛高度Lc随着热处理时间的增加而增加；热处理时间对JJV焦炭的影响不如YXV显著，而只有在较高的热处理温度(1 200 ℃)下，碳的微观结构才出现明显的有序化。热处理导致的焦炭微观碳结构趋于有序化是焦炭反应性下降的主要原因。