饱和多孔介质化学-热-弹性模型及应用

本文基于热局部非平衡(LTNE)条件和加权平均温度概念,并假设孔隙流体由溶质和溶剂两组元组成,对页岩(饱和多孔介质),推导给出了一种LTNE条件下的化学-热-弹性模型,同时讨论了耦合方程组的解耦求解问题.作为模型的应用,考虑无限大平面含一圆形孔的情况,研究了冷/热对流以及溶质摩尔分数突变边界条件下圆孔附近的孔隙压力和化-热应力问题,用Laplace变换得到了平面轴对称情况下有关力学变量的表达式.数值分析了圆孔边界上冷/热对流的Biot数和溶质摩尔分数改变量对圆孔附近孔隙压力和化-热应力的影响.结果表明:在Biot数为中等值(1～5)范围内,LTNE效应是非常明显的;化学作用对孔隙压力和固相应力的影响不可忽视.

Thermodynamics analysis and precipitation behavior of fine carbide in K416B Ni-based superalloy with high W content during creep

The precipitation behavior of carbide in K416 B superalloy was investigated by means of creep measurement and microstructure observation. The results show that nanometer M6 C particles discontinuously precipitate in the γ matrix or along the γ/γ′ interface of the alloy during high temperature tensile creep. Thereinto, the amount of fine M6 C carbide increases as creep goes on, and the coherent interfaces of M6 C phase precipitating from the γ matrix are {100} and {111} planes. The thermodynamics analysis indicates that the solubility of element carbon in the matrix decreases when the alloy is deformed by the axial tensile stress during creep, so as to cause the carbon segregating in the regions of stress concentration and combining with carbide-forming elements M（W, Co）, which promotes the fine M6 C carbide to precipitate from the γ matrix.

Reaction mechanisms of low-grade molybdenum concentrate during calcification roasting process

The effects of Ca-based additives on roasting properties of low-grade molybdenum concentrate were studied. The resultsshow that calcium-based additives can react with molybdenum concentrate to form CaSO4 and CaMoO4. The initial oxidationtemperature of MoS2 is 450℃, while the formation of CaMoO4 and CaSO4 occurs above 500℃. The whole calcification reactionsare nearly completed between 600 and 650℃. However, raising the temperature further helps for the formation of CaMoO4 but isdisadvantageous to sulfur fixing rate and molybdenum retention rate. Calcification efficiency of Ca-based additives follows theorder： Ca（OH）2〉CaO〉CaCO3. With increasing the dosage of Ca（OH）2, the molybdenum retention rate and sulfur-fixing rate rise, butexcessive dosages would consume more acid during leaching process. The appropriate mass ratio of Ca（OH）2 to molybdenumconcentrate is 1：1. When roasted at 650 ℃ for 90 min, the molybdenum retention rate and the sulfur-fixing rate of low-grademolybdenum concentrate reach 100% and 92.92%, respectively, and the dissolution rate of molybdenum achieves 99.12% withcalcines being leached by sulphuric acid.

Thermodynamic modelling and applications of Ce-La-O phase diagram

The Ce-La-O system was investigated via experiments and thermodynamic modeling. A series of CeO2-LaO1.5 mixtures were prepared by co-precipitation technique and examined by X-ray diffraction. Mutual solubilities between LaO1.5 and CeO2 at 1273 K were determined. Using the new experimental data together with literature information, a set of self-consistent thermodynamic parameters for the CeO2-LaO1.5 system were optimized. Combined with thermodynamic descriptions of Ce-O and La-O systems from literature, several property diagrams of Ce-La-O system were calculated and used to explain oxidation process of the Ce-La alloys. The fluorite phase is the unique oxidation products for most of the Ce-La alloys.

Effect of TPB on curing reaction of HTPB-TDI

Catalysis effect of triphenyl bismuth （TPB） on kinetics of hydroxyl terminated polybutadiene-toluene diisocyanate （HTPB-TDI） curing reaction was studied by non-isothermal differential scanning calorimetry （DSC）. The characteristic temperature of curing system was measured for calculating kinetic parameters and establishing curing reaction kinetic equations. The results show that activation energy （Ea） of uncatalyzed HTPB-TDI curing system is 51.29 kJmol-1, and TPB decreases Ea to 46.43 kJ＇mol-1. Catalyst lowers reaction temperature and shortens curing time through decreasing ac- tivation energy of curing reaction and accelerating reaction rate. TPB can increase the reaction rate at 27 ℃ to the value of uncatalyzed system at 80 ℃. The catalytic activity reaches the maximum when concentration is 0.5 %.

Elemental Composition Method in Thermodynamics of Mul- tireaction Systems (I) Molar Number, Thermodynamic Properties and Partial Properties Relations

When species in the solution undergo multiple chemical reactions, the solution may be treated as a solution of all species actually present or as a hypothetical solution composed of elemental species. Based on the fundamental thermodynamic principle, the relationships of mole numbers, molar fractions, thermodynamic properties, partial molar properties, potential and fugacity between the hypothetical solution of elemental species and the equilibrated solution of actual species were derived. The hypothetical elemental solution provides a way of reducing the dimensionality of problem, simplifying the analysis and visualizing the phase behavior.

Catalytic Pyrolysis of Biodiesel Surrogate over HZSM-5 Zeolite Catalyst

To obtain insight into the catalytic reaction mechanism of biodiesels over ZSM-5 zeolites,the pyrolysis and catalytic pyrolysis of methyl butanoate,a biodiesel surrogate,with H-type ZSM-5(HZSM-5)were performed in a flow rereac tor under atmospheric pressure.The pyrolysis products were identified and quantified using gas chroma to graphy-mass spec trome try(GC-MS).Kine tic modelling and experimental results revealed that H-atom abstraction in the gas phase was the primary pathway for methyl butanoate decomposition during pyrolysis,but dissociating to ketene and methanol over HZSM-5 was the primary pathway for methyl butanoate consumption during catalytic pyrolysis.The initial decomposition temperature of methyl butanoate was reduced by approximately 300 K over HZSM-5 compared to that for the uncatalyzed reaction.In addition,the apparent activation energies of methyl butanoate under catalytic pyrolysis and homogeneous pyrolysis conditions were obtained using the Arrhenius equation.The significantly reduced apparent activation energy confirmed the catalytic performance of HZSM-5 for methyl but anoa te pyrolysis.The act iva tion t empera ture may also affec t some catalytic proper ties of HZSM-5.Overall,this study can be used to guide subsequent catalytic combustion for practical biodiesel fuels.

Solar-heating boosted catalytic reduction of CO_(2） under full-solar spectrum

Catalytic converting CO2 into fuels with the help of solar energy is regarded as‘dream reaction’,as both energy crisis and environmental issue can be mitigated simultaneously.However,it is still suffering from low efficiency due to narrow solar-spectrum utilization and sluggish heterogeneous reaction kinetics.In this work,we demonstrate that catalytic reduction of CO2 can be achieved over Au nanoparticles(NPs)deposited rutile under full solar-spectrum irradiation,boosted by solar-heating effect.We found that UV and visible light can initiate the reaction,and the heat from IR light and local surface-plasmon resonance relaxation of Au NPs can boost the reaction kinetically.The apparent activation energy is determined experimentally and is used to explain the superior catalytic activity of Au/rutile to rutile in a kinetic way.We also find the photo-thermal synergy in the Au/rutile system.We envision that this work may facilitate understanding the kinetics of CO2 reduction and developing feasible catalytic systems with full solar spectrum utilization for practical artificial photosynthesis.

Study of Thermodynamics and Kinetics of CH_4-CaSO_4 and H_2S-Fe_2O_3 Systems

The destruction of hydrocarbon in deep carbonate diagenetic environment is one of problems on the formation of oil and gas. Organic-inorganic reactions in the process of TSR(Thermochemical Sulfate Reduction) are the main reason to make disappearance of the hydrocarbons. The work in this field has often been the subject of much research work in recent years. In this paper, the thermodynamics of CH4-CaSO4 and H2S-Fe2O3 systems is discussed to investigate the possibility of reactions. It is found that these two reactions can proceed spontaneously.Increasing temperature is favorite for CH4-CaSO4 system but disfavorite for H2S-Fe2O3 system. Thermal simulation experiments were carried out using autoclave at high temperature and high pressure. The properties of the products were characterized by microcoulometry, FT-IR and XRD methods. On the basis of the experimental data, a reaction kinetic model is developed and kinetic parameters are determined.

Thermodynamic design of a cascade refrigeration system of liquefied natural gas by applying mixed integer non-linear programming

Liquefied natural gas(LNG) is the most economical way of transporting natural gas(NG) over long distances. Liquefaction of NG using vapor compression refrigeration system requires high operating and capital cost. Due to lack of systematic design methods for multistage refrigeration cycles, conventional approaches to determine optimal cycle are largely trial-and-error. In this paper a novel mixed integer non-linear programming(MINLP)model is introduced to select optimal synthesis of refrigeration systems to reduce both operating and capital costs of an LNG plant. Better conceptual understanding of design improvement is illustrated on composite curve(CC) and exergetic grand composite curve(EGCC) of pinch analysis diagrams. In this method a superstructure representation of complex refrigeration system is developed to select and optimize key decision variables in refrigeration cycles(i.e. partition temperature, compression configuration, refrigeration features, refrigerant flow rate and economic trade-off). Based on this method a program(LNG-Pro) is developed which integrates VBA,Refprop and Excel MINLP Solver to automate the methodology. Design procedure is applied on a sample LNG plant to illustrate advantages of using this method which shows a 3.3% reduction in total shaft work consumption.

Effect of hydrogen combustion reaction on the dehydrogenation of ethane in a fixed-bed catalytic membrane reactor

A two-dimensional non-isothermal mathematical model has been developed for the ethane dehydrogenation reaction in a fixed-bed catalytic membrane reactor. Since ethane dehydrogenation is an equilibrium reaction,removal of produced hydrogen by the membrane shifts the thermodynamic equilibrium to ethylene production.For further displacement of the dehydrogenation reaction, oxidative dehydrogenation method has been used.Since ethane dehydrogenation is an endothermic reaction, the energy produced by the oxidative dehydrogenation method is consumed by the dehydrogenation reaction. The results show that the oxidative dehydrogenation method generated a substantial improvement in the reactor performance in terms of high conversions and signi ficant energy saving. It was also established that the sweep gas velocity in the shell side of the reactor is one of the most important factors in the effectiveness of the reactor.

Thermodynamic Analysis of Formation of Low-carbon Olefins via Coal Gasification Coupling C_1 Reaction

The complex reaction system of the coal gasification coupling C1 reaction was analyzed based on the principles of thermodynamics. The results show that an increase in the temperature is beneficial to the generation of hydrocarbons with high carbon-atom contents, in which the alkane yield is higher than the alkene yield. The complex reaction system consisting of C, H20, CO, CO2, H2, C2H4, C3H6 and C4Hs was studied, and the obtained results indicated that when the maximum mole fraction content of C2-C4 olefins was regarded as the optimized objective function, the optimum temperature was approximately 648 K, the pressure was 0.1 MPa, the feed ratio was approximately 0.6, and the maximum mole fraction content of C2-C4 olefins was approximately 28.24%. The thermodynamic simulation and calculation of the complex reaction system can provide a basis for the determination and optimization of actual process conditions and are therefore of great theoretical and practical significance.

A comprehensive comparison on vibration and heat transfer of two elastic heat transfer tube bundles

Elastic heat transfer tube bundles are widely used in the field of flow-induced vibration heat transfer enhancement. Two types of mainly used tube bundles, the planar elastic tube bundle and the conical spiral tube bundle were comprehensively compared in the condition of the same shell side diameter. The natural mode characteristics, the effect of fluid-structure interaction, the stress distribution, the comprehensive heat transfer performance and the secondary fluid flow of the two elastic tube bundles were all concluded and compared. The results show that the natural frequency and the critical velocity of vibration buckling of the planar elastic tube bundle are larger than those of the conical spiral tube bundle, while the stress distribution and the comprehensive heat transfer performance of the conical spiral tube bundle are relatively better.

Kinetics of the Chlorination of Copper （I） Sulphide by Calcium Chloride in the Presence of Oxygen

The chemism of the chlorination of copper （I） sulphide by calcium chloride in the presence of oxygen has been determined based on the thermodynamic analysis in the Cu2S-CaCl2-O2 system as well as characterization of used raw materials and obtained products. The influence of temperature （from 473 to 773 K）, time （from 2 to 120 min）, oxygen flow （from 20 to 100 L/h） and calcium chloride quantity （from 5 to 40%） on the chlorination degree has been investigated. Kinetic analysis and the activation energy values of 20.89 kJ/mol showed that the chlorination of copper （I） sulphide by calcium chloride in the presence of oxygen is diffusion controlled.

Theoretical Studies on Dehydrogenation Reactions in Mg2（BH4）2（NH2）2 Compounds

Borohydrides have been recently hightlighted as prospective new materials due to their high gravimetric capacities for hydrogen storage. It is, therefore, important to under- stand the underlying dehydrogenation mechanisms for further development of these ma- terials. We present a systematic theoretical investigation on the dehydrogenation mecha- nisms of the Mg2（BH4）2（NH2）2 compounds. We found that dehydrogenation takes place most likely via the intermolecular process, which is favorable both kinetically and thermo- dynamically in comparison with that of the intramolecular process. The dehydrogenation of Mg2（BH4）2（NH2）2 initially takes place via the direct combination of the hydridie H in BH4 and the protie H in NH2-, followed by the formation of Mg-H and subsequent ionic recombination of Mg-Hδ-…Hδ＋-N.

Simulation of Continuous Esterification Process of Polyester Polyols

Based on the kinetic and thermodynamic equations, a comprehensive mathematical model for the con- tinuous esterification process of polyester polyols was developed, which was carried out in an innovational bub- bling reactive distillation tower （BRDT） at atmospheric pressure. In this new type of reactor, direct esterification between ethylene glycol and adipic acid was accomplished efficiently and rapidly. A bench BRDT with the height of 2 m was applied for the esteriflcation process of l^oly （ethylene adlpate） （P＇EA）. In the continuous operation, Hn- ear oligomers were discharged from the bottom of the column, while water passed a few column trays and a pack- ing section as a condensation byproduct. The influence of major operating conditions on reactor performance was also simulated. Simulation results were in good agreement with experimental data, providing a strategy for devel- oping and optimizing this process.

Magnetic Effects in the Thermodynamics of the Process of Thinking

The authors have shown that the process of information and thinking can be modeled on the basis of chemical thermodynamics. The authors offer general equations to calculate the thinking of the work of judgment the L and of entropy solutions G in the presence of a magnetic field. As a result, studies have shown that the magnetic effects strongly influence the thermodynamics of the process of thinking.

Magnetic Effects in the Thermodynamics of Information

The authors have shown that the process data can be modeled on the basis of chemical thermodynamics. The authors offer general information of the equation in the presence of a magnetic field. As a result, studies have shown that the magnetic effects strongly influence the thermodynamics of information.

Thermal Analysis of Composite Cements

The hydration of cement compounds gives hydrated compounds, which allow linking together, the different particles and aggregate of cement, and gives the concrete the required qualities. The dynamics of hydration reactions will depend on many factors, such as the fineness of cement, the ratio w/c during hydration, temperature, mixing technique, and the presence of additives in blended cement, as pozzolan, tuff and slag from blast furnaces. We studied the thermal and kinetic reactions of Portland cement hydration, and its variants with different additions using a differential scanning calorimetric analysis. The parameters from these models of curves allow us to evaluate the enthalpies, and the degree of progression of this blended cement, and finally determine their activation energies. We can say that the hydration of Portland cement is due to a series of reactions as （ C3S,C2S,C3A and C4AF reactions with water） and each of them, has its own kinetic, the experimental measurement of the heat of hydration, allows us to represent the overall kinetics of these reactions values of activation energy, they are therefore apparent and global energy. In our experiments, significant differences in these physicochemical parameters were observed, depending on the additive used.

Effects of Heat Softening on Initiation of Landslides

Effects of heat softening on the initiation of slide surface(shear banding) in clayey slopes during fast deformation were discussed.Controlling equations considering heat,pore pressure and mechanical movement were presented.By perturbation method,the instability condition of localized zone(i.e.criterion for initiation of shear banding) for thermal related soils,such as clayey slope,was obtained.It is shown that slide surface initiates once the thermal-softening effects overcome the strain-hardening effects whether it is adiabatic or not.Without strain hardening effects,strain rate hardening obviously plays a role in initiation of shear band.During initiating process,heat is trapped inside the shear band,which leads rapidly to a pore pressure increase and fast loss of strength.The localized shear strain is concentrated in a narrow zone with a width of several centimeters at most and increases fast.This zone forms the sliding surface.Temperature can increase more than 2?C,pore pressure can increase 160% in about 0.1s inside this zone.These changes cause the fast decrease in friction-coefficient by about 36% over the initial value.That is how shear band initiated and developed in clayey slopes.