流动反应器流量调节式量热方法模拟

面向连续流动条件下化学反应放热的测量需求,针对其量热方法开展研究。首先,根据流体流动状态及管路传热原理建立连续流动反应系统模型。其次,设计一种应用于流动状态下的量热方法,通过热平衡理论推导出温度信息与质量流量之间的线性函数关系,其斜率与截距中包含反应热力学信息,利用不同流量下多组实验的温度数据进行线性拟合,求取反应焓,针对管路内存在温度分布的情形,引入温度分布分段的计算方式。最后,模拟研究流量调节步长和分段计算步长对量热结果的影响。结果表明:面对多种放热工况,反应焓计算结果的误差在5%以内,随着流量调节步长和计算步长值的增加,计算结果误差增大。综合研究结果,在方法应用时,流量调节步长的建议值应在1—2 mL/min之间,计算步长的建议值应在0.005—0.01 m之间。

煤发热量测定方法的研究

本文采用差示扫描量热DSC方法,通过对环境温度、升温速率、面积积分方式、取值方法、峰形、器皿形态以及煤灰对基线的影响等方面的研究,探索出了另一种测量煤的发热量的方法,取得了良好的测试结果。

燃烧热测定实验中三条直线校正温度法的探究

燃烧热测定实验是物理化学实验教学中十分经典的实验内容,该文通过建立数学模型将计算法应用于量热分析中的数据处理,采用三条直线法对温差进行校正,并与作图法进行比较,得到比较满意的结果。

生物质和高硫劣质煤混烧灰熔融特性研究

对生物质和煤混烧特性的研究受到国内外学者的广泛重视。对生物质与高硫劣质煤混烧灰的熔融特性进行研究,测量了灰熔点,并利用热重–差示扫描量热(thermo-gravimetry-differential scanning calorimetry,TG-DSC)方法对灰的熔融过程进行研究。实验结果表明,混烧生物质能降低灰熔点,生物质混烧比例越高,灰熔点下降幅度越大。由于生物质中灰分含量远小于高硫劣质煤,混烧灰的灰熔点温度主要受煤灰的影响。由于灰的组成成分及其含量的差异,煤灰、生物质灰在实验温度范围,TG-DSC曲线有较大差异。在低混烧比时,混烧灰的TG-DSC曲线基本体现煤灰的熔融特性。随着混烧比例的提高,TG-DSC曲线上生物质的影响变得明显。

Synthesis and characterization of triclinic structural LiVPO_4F as possible 4.2 V cathode materials for lithium ion batteries

A potential 4.2 V cathode material LiVPO4F for lithium batteries was prepared by two-step reaction method based on a carbon-thermal reduction （CTR） process. Firstly, V2O5, NH4H2PO4 and acetylene black are reacted under an Ar atmosphere to yield VPO4. The transition-metal reduction is facilitated by the CTR based on C→CO transition. These CTR conditions favor stabilization of the vanadium as V^3＋ as well as leaving residual carbon, which is useful in the subsequent electrode processing. Secondly, VPO4 reacts with ElF to yield LiVPO4F product. The property of the LiVPO4F was investigated by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement. XRD studies show that LiVPO4F synthesized has triclinic structure（space group p I ）, isostructural with the naturally occurring mineral tavorite, EiFePO4-OH. SEM image exhibits that the particle size is about 2μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of LiVPO4F powder is 119 mA·h/g at the rate of 0.2C with an average discharge voltage of 4.2V （vs Ei/Li^＋）, and the capacity retains 89 mA·h/g after 30 cycles.

Lie Symmetrical Perturbation and Adiabatic Invariants of Generalized Hojman Type for Relativistic Birkhoffian Systems

For a relativistic Birkhoffian system, the Lie symmetrical perturbation and adiabatic invariants of generalized Bojman type are studied under general infinitesimal transformations. On the basis of the invariance of relativistic Birkhotfian equations under general infinitesimal transformations,Lie symmetrical transformations of the system are constructed, which only depend on the Birkhoffian variables. The exact invariants in the form of generalized Hojman conserved quantities led by the Lie symmetries of relativistic Birkhoffian system without perturbations are given. Based on the definition of higher-order adiabatic invariants of a mechanical system, the perturbation of Lie symmetries for relativistic Birkhoffian system with the action of small disturbance is investigated, and a new type of adiabatic invariants of the system is obtained. In the end of the paper, an example is given to illustrate the application of the results.

In Situ Measurement of the Undisturbed Ground Temperature for Ground Source Heat Pump System

The undisturbed ground temperatures are important for design of the ground heat exchangers in ground source heat pump （GSHP） systems. In this paper, the undisturbed ground temperatures measured in two different methods are presented. The investigation was carried out in two cases. The temperature measured with the direct method is assumed to give the correct undisturbed ground temperature profile. The temperature measured with indirect method overestimates the undisturbed ground temperature by 2.1℃ and 1.7~C. This difference is mainly caused by the circulation pump and ambient air to the fluid. Therefore, the results that are decreased about 2℃ as compared with the indirect measured are recommended to estimate the undisturbed ground temperature in situ measuring. A smaller pump or deeper borehole or mild weather would result in a more correct temperature. Because the undisturbed ground temperature is affected by many factors. Whether or not these conclusions are correct to other areas, this would need further investigation.

Understanding the influence of microwave on the relative volatility used in the pyrolysis of Indonesia oil sands

In this paper, pyrolysis of Indonesian oil sands （lOS） was investigated by two different heating methods to develop a better understanding of the microwave-assisted pyrolysis. Thermogravimetric analysis was conducted to study the thermal decomposition behaviors of lOS, showing that 550 ℃ might be the pyrolysis final temperature. A explanation of the heat-mass transfer process was presented to demonstrate the influence of mi- crowave-assisted pyrolysis on the liquid product distribution. The heat-mass transfer model was also useful to explain the increase of liquid product yield and heavy component content at the same heating rate by two differ- ent heating methods. Experiments were carried out using a fixed bed reactor with and without the microwave irradiation. The results showed that liquid product yield was increased during microwave induced pyrolysis, while the formation of gas and solid residue was reduced in comparison with the conventional pyrolysis. Moreover, the liquid product characterization by elemental analysis and GC-MS indicated the significant effect on the liquid chemical composition by microwave irradiation. High polarity substances （ε 〉 10 at 25 ℃）, such as oxy- organics were increased, while relatively low polarity substances （ε 〈 2 at 25℃）, such as aliphatic hydrocarbons were decreased, suggesting that microwave enhanced the relative volatility of high polarity substances. The yield improvement and compositional variations in the liquid product promoted by the microwave-assisted pyrolysis deserve the further exploitation in the future,

Developments in the understanding of gas–solid contact efficiency in the circulating fluidized bed riser reactor:A review

In the last several decades, circulating fluidized bed reactors have been studied in many aspects including hydrodynamics, heat and mass transfer and gas–solid two phase contacting. However, despite the abundance of review papers on hydrodynamics, there is no summary paper on gas–solid contact efficiency to date, especially on high density circulating fluidized beds(CFBs). This paper gives an introduction to, and a review of the measurement of contact efficiency in circulating fluidized bed riser. Firstly, the popular testing method of contact efficiency including the method of heating transfer experiment and hot model reaction are discussed, then previous published papers are reviewed based on the discussed methods. Some key results of the experimental work are described and discussed. Gas–solid contact efficiency is affected by the operating conditions as well as the particle size distribution. The result of the contact efficiency shows that the CFB riser is far away from an ideal plug flow reactor due to the characteristics of hydrodynamics in the riser. Lacunae in the available literature have been delineated and recommendations have been made for further work.

Theories and Applications of Mixed Quantum-Classical Non-adiabatic Dynamics

Electronically non-adiabatic processes are essential parts of photochemical process, collisions of excited species, electron transfer processes, and quantum information processing. Various non-adiabatic dynamics methods and their numerical implementation have been developed in the last decades. This review summarizes the most significant development of mixed quantum-classical methods and their applications which mainly include the Liouville equa- tion, Ehrenfest mean-field, trajectory surface hopping, and multiple spawning methods. The recently developed quantum trajectory mean-field method that accounts for the decoherence corrections in a parameter-free fashion is discussed in more detail.

An improvement to the simulation of phase-change heat-transfer during soil freezing and thawing

A new variable time step method,which is called the backwards calculating time step method,is presented in this paper.It allows numerical simulation of soil freezing and thawing while avoiding "phase change missing and overflowing".A sensitive heat capacity model is introduced through which the calculation errors are analyzed.Then the equation using the self-adjusted time step is presented and solved using finite differences.Through this equation,the time needed for a space cell to reach the phase change point temperature is calculated.Using this time allows the time step to be adjusted so that errors caused by "phase change missing and overflowing" are successfully eliminated.Above all,the obvious features of this method are an accelerated rate for adjusting the time step and simplifing the computations.An actual example proves that this method can accurately calculate the temperature fields during soil freezing and thawing.It is an improvement over traditional methods and can be widely used on complicated multi-dimensional phase change problems.

Adiabatic correction for the esterification of acetic anhydride by methanol via accurate kinetics

In the field of adiabatic correction for complex reactions,a simple one-stage kinetic model was used to estimate the real reaction kinetics.However,this assumption simplified the real process,inevitably generated inaccurate or even unsafe results.Therefore,it was necessary to find a new correction method for complex reactions.In this work,esterification of acetic anhydride by methanol was chosen as an object reaction of study.The reaction was studied under different conditions by Reaction Calorimeter(RC1).Then,Thermal Safety Software(TSS)was used to establish the kinetic model and estimate the parameters,where,activation energies for three stages were67.09,81.02,73.77 kJ?mol^(-1)respectively,and corresponding frequency factors in logarithmic form were 16.05,19.59,15.72 s^(-1).In addition,two adiabatic tests were performed by Vent Sizing Package2(VSP2).For accurate correction of VSP2 tests,a new correction method based on Enhanced Fisher method was proposed.Combined with kinetics,adiabatic correction of esterification reaction was achieved.Through this research,accurate kinetic parameters for a three-step kinetic model of the esterification reaction were acquired.Furthermore,the correlation coefficients between simulated curves and corrected curves were 0.976 and 0.968,which proved the accuracy of proposed new adiabatic correction method.Based on this new method,conservative corrected results were able to be acquired and be applied in safety assessment.

Geostrophic meridional transport in tropical Northwest Pacific based on Argo profiles

Absolute geostrophic currents in the North Pacific Ocean were calculated using P-vector method from newly gridded Argo profiling float data collected during 2004-2009. The meridional volume transport of geostrophic currents differed significantly from the classical Sverdrup balance, with differences of 10×106 -20×106 m3 /s in the interior tropical Northwest Pacific Ocean. Analyses showed that errors of wind stress estimation could not explain all of the differences. The largest differences were found in the areas immediately north and south of the bifurcation latitude of the North Equatorial Current west of the dateline, and in the recirculation area of the Kuroshio and its extension, where nonlinear eddy activities were robust. Comparison of the geostrophic meridional transport and the wind-driven Sverdrup meridional transport in a high-resolution OFES simulation showed that nonlinear effects of the ocean circulation were the most likely reason for the differences. It is therefore suggested that the linear, steady wind-driven dynamics of the Sverdrup theory cannot completely explain the meridional transport of the interior circulation of the tropical Northwest Pacific Ocean.

Measurement of Thermal Resistance of Heat-resistant Fabrics with a Guarded-hot-box

A novel analytical method with the guarded-hot-box （GHB） in investigating the thermal resistance of heat-resistant fabrics is described and the analytical method is also presented in this paper. The new apparatus is capable of measure thermal resistance of the fabrics in high temperature up to an average applied temperature of 250~C. The maximum measurement error of the apparatus is 6.5% and relative error is less than 2.8% between the introduced method and standard given value. In the G/-IB method, air layer thickness is the most important factor that influences measurement value of thermal resistance of heat-resistant fabrics. Results show that the method is more accurate and efficient than GBl1048-89 one in measuring thermal resistance of heat-resistant fabrics.

Non-adiabatic Couplings Induced Complex-Forming Mechanism in H+MgH^(+)→Mg^(+)+H_(2) Reaction

A chemical process may involve multiple adiabatic electronic states, and non-adiabatic couplings play an important role in the reaction mechanism. In this work, the effect of non-adiabatic couplings in the H+MgH;→Mg;+H;reaction are studied using the time-dependent wave packet method and trajectory surface hopping method. The calculated results show that the reaction follows a direct abstraction process when the non-adiabatic couplings are neglected. However, when non-adiabatic couplings are included in the calculations, a longlived excited state complex(MgH_(2)+)*can be formed during the reaction. These direct and complex-forming reaction pathways are revealed by trajectory surface hopping calculations.The non-adiabatic couplings induced complex-forming mechanism not only increases the reactivity but also has significant effect on the product vibrational state distribution.

A New Approach to Measurement of Heating Rate of Trapped Ions

We propose a new scheme to estimate the heating rate of trapped ions in thermal states. By applying a controlled-U gate between the internal and the motional states of one of the trapped ions, we could obtain the mean phonon number from the population of the internal state of the ion. The imperfection due to fluctuations of the relevant parameters in real experiments is considered and we anaiyze the experimental feasibility of our scheme with sophisticated ion trap techniques.

New method for analyzing recrystallization kinetics of deformed metal by differential scanning calorimeter

The drawn copper wires have been analyzed by differential scanning calorimeter(DSC) and a new method, which uses DSC measurements to determine the Johnson-Mehl-Avrami-Kolmogorov(JMAK) exponent via introducing Arrhenius behavior and modifying the baseline of DSC curves, has been proposed. The results show that JMAK exponent and recrystallization activation energy of the drawn copper wires with a strain of 2.77 are about 2.39 and 125 k J/mol, respectively. The line linking the tangency points of DSC curve hypotenuse can be used as the baseline when calculating recrystallization fraction. The JMAK exponent obtained by the DSC method is in a good agreement with that obtained by microhardness measurements. Compared to traditional methods to measure the exponent, the proposed method is faster and less labor intensive.

Thermophysical Properties of Channel Catfish at Freezing Temperatures

Freezing is the most common method used to preserve and minimize loss in quality of catfish during storage. Since freezing is a heat transfer process, the design and selection of freezing equipment require knowledge of thermophysical properties such as freezing temperature, enthalpy of freezing, unfreezable water and specific heat. Channel catfish thermophysical properties at freezing temperature were determined using differential scanning calorimetry. Using the combination of Raoult＇s law and Classius-Clapeyron equations, the amount of unfreezable （bound water） was estimated to be 0.129 g H20 g^-1 During freezing （or melting）, the specific heat increased from about 1.5 J g^-1 ℃^-1 to about 30.6 J g^-1 ℃^-1 It was found that freezing of catfish occur over a wide temperature range with the peak and incident freezing temperatures occurring at temperatures of-1.88 ℃ and -6.10 ℃, respectively. About 250 J g^-1 of heat have to be removed from catfish when it is to be frozen to -40 ℃. The implication is that any system that will be designed to freeze catfish must be able to remove 250 J g^-1 of heat.

Laboratory and field experiment on measurement of soil thermal conductivity by probe method

The authors presented a new measuring method of the soil thermal conductivity,the probe method,which is designed and made based on the theory of line heat source. This method is used to measure thermal conductivity of coarse sand,fine sand and silty clay in different water contents. The results that measured by the probe method are well consistent with those of QTM-D_2. The soil thermal conductivity increases in different levels with the increase of the water content. Compared the soil thermal conductivity measured by the probe method in laboratory with in-situ experiment,it shows that the measuring gap gradually increases with the increase of the depth. The reason is that the in-situ measuring thermal conductivity can reflect the actual situation of the soil mass.

Condensing Heat Exchanger

The paper shows a method of designing a heat exchanger recovering heat from the condensation of water vapour contained in flue gases. A heat exchanger condenses water vapour and SO2 （sulphur dioxide） in the presence of inert gases （CO2, CO, N2, O2） contained in flue gases. A mathematical model and a sample design of a heat exchanger were presented. The heat exchange is capable of recovering from a dozen or so to several dozen percent of heat from flue gases escaping into the atmosphere. A second advantage of the heat exchanger is the possibility to reduce the emissions of SO2 considerably. Depending on the parameters, it can be even a sevenfold reduction in the emissions. The main mathematical tool used for designing the condensing heat exchanger is the Colburn-Hougen method. The authors omitted that part of the method which requires iterative calculations. The Mollier diagram was used instead.