基于CPA状态方程计算水的热力学物性参数

虽然储层多孔介质中不可避免的含有大量的地层水,但在通常的相平衡计算过程中往往都忽略了水的存在;常用的状态方程虽然计算简便,但对某些热力学性质的估算仍存在着较大的偏差;已有的状态方程虽然已进行过修正,但其对含有极性物质(烃类、水、醇等)的体系适用性较差。为此,基于同时考虑分子间物理作用和缔合作用的CPA(Cubic-Plus-Association)状态方程,模拟计算了极性物质——水在饱和与非饱和状态下的热力学性质,对比分析了常用状态方程在计算极性物质热力学物性参数时的不足。计算结果表明:(1)常用的状态方程虽然能较好地计算水的饱和蒸汽压值,但在水的密度和焓值的计算时却呈现出不同的差异性,同时焓值的计算不受体积修正的影响;(2)CPA方程计算的水热力学物性参数与实验数据的平均绝对相对偏差在1%左右。结论认为:对含有极性物质的体系而言,CPA方程是首选的热力学状态方程。对水热力学物性参数的准确估算是对含水气藏流体所处状态的基础把握,对该类气藏的开发和生产具有重要的指导意义。

Thermodynamics study on leaching process of gibbsitic bauxite by hydrochloric acid

For the low-grade gibbsitic bauxite,the leaching rate of alumina is very low during the Bayer process.The acid leaching method is attracting more attention,and the hydrochloric acid leaching was developed rapidly.The mineral composition and chemical composition were investigated by X-ray diffraction analysis and semi-quantitative analysis.The thermodynamics of leaching process was analyzed.The results show that the major minerals in the bauxite are gibbsite,secondly goethite and quartz,anatase and so on.The acid leaching reactions of the bauxite would be thermodynamically easy and completed.Under the conditions that ore granularity is less than-55 μm,the L/S ratio is 100：7,and the leaching temperature is 373-383 K,the leaching time is 120 min and the concentration of HCl is 10%,both the leaching rates of Al and Fe are over 95%.The main composition of leaching slag is SiO2 which is easy for comprehensive utilization.

Non-isothermal thermal decomposition kinetics of high iron gibbsite ore based on Popescu method

The thermal decomposition kinetics of high iron gibbsite ore was investigated under non-isothermal conditions.Popescu method was applied to analyzing the thermal decomposition mechanism.The results show that the most probable thermal decomposition mechanism is the three-dimensional diffusion model of Jander equation,and the mechanism code is D3.The activation energy and pre-exponential factor for thermal decomposition of high iron gibbsite ore calculated by the Popescu method are 75.36 kJ/mol and 1.51×10-5 s-（-1）,respectively.The correctness of the obtained mechanism function is validated by the activation energy acquired by the iso-conversional method.Popescu method is a rational and reliable method for the analysis of the thermal decomposition mechanism of high iron gibbsite ore.

Non-isothermal kinetic analysis of thermal dehydration of La_2(CO_3)_3·3.4H_2O in air

The single phase La2（CO3）3·3.4H2 O was synthesized by hydrothermal method. The thermal decomposition and intermediates and final solid products of La2（CO3）3·3.4H2O from 30 to 1000 °C were characterized by XRD, FTIR and DTA-TG. The kinetics of dehydration of La2（CO3）3·3.4H2O in the temperature range of 30-366 °C was investigated under non-isothermal conditions. Flynn-Wall-Ozawa and Friedman isoconversion methods were used to calculate the activation energy and analyze the reaction steps; multivariate non-linear regression program was applied to determine the most probable mechanism and the kinetic parameters. The results show that the thermal dehydration of La2（CO3）3·3.4H2O is a kind of three-step competitive reaction, and controlled by an n-order initial reaction followed by n-order competitive reaction（FnFnFn model）. The activation energy matching with the most probable model is close to value obtained by Friedman method. The fitting curves match the original TG-DTG curves very well.

Statistic characteristics of thermal structure in the southern Yellow Sea in summer

Based on the temperature data along 34°N, 35°N and 36°N sections in August from 1977 to 2003,the structure and formation of the Southern Yellow Sea Cold Water Mass (SYSCWM) and its responses to El Nino events are analyzed. Results show that: (1) There exist double cold cores under the main thermocline along the 35°N and 36°N sections. Also, double warm cores exist above the main thermocline along the 36°N section.(2) Thermocline dome by upwelling separates the upper warm water into two parts, the eastern and western warm waters. Additionally, the circulation structure caused by upwelling along the cold front and northeastward current along the coast in summer is the main reasons of double warm cores along the 36°N section. The intermediate cold water is formed in early spring and moves eastward slowly, which results in the formation of the western one of double cold cores. (3) Position of the thermocline dome and its intensity vary interannually,which is related to El Nino events. However, the deep cold water temperature is hardly affected by El Nino events. In most El Nino years, position of the thermocline dome shifted eastwards and depth of the dome upper limit decreases.

A new measurement method of crack propagation rate for brittle rock under THMC coupling condition

A new electrical method of conductive carbon-film(with waterproof and anticorrosion ability)was proposed to continuously measure crack propagation rate of brittle rock under THMC coupling condition.A self-designed coupling testing system was used to conduct THMC coupling fracture tests of the pre-cracked red sandstone specimens(where the temperature is only changed)by this new electrical method of conductive carbon-film.Calculation results obtained by the energy method coincide well with the test results.And the higher the temperature is,the earlier the crack is initiated and the larger the crack propagation rate and accelerated velocity are,which can prove the validity of the new electrical method.This new electrical method has advantages of continuously measuring crack propagation rate over the conventional electrical,optical and acoustic methods,and can provide important basis for safety assessment and cracking-arrest design of deep rock mass engineering.

Thermodynamic analysis of simplified dual-pressure ammonia-water absorption power cycle

A simplified dual-pressure ammonia-water absorption power cycle(DPAPC-a) using low grade energy resources is presented and analyzed.This cycle uses turbine exhaust heat to distill the basic solution for desorption.The structure of the cycle is simple which comprises evaporator,turbine,regenerator(desorber),absorber,pump and throttle valves for both diluted solution and vapor.And it is of high efficiency,because the working medium has large temperature difference in evaporation and small temperature difference in absorptive condensation,which can match the sensible exothermal heat resource and the cooling water simultaneously.Orthogonal calculation was made to investigate the influence of the working concentration,the basic concentration and the circulation multiple on the cycle performance,with 85-110 ℃ heat resource and 20-32 ℃ cooling water.An optimum scheme was given in the condition of 110 ℃ sensitive heat resource and 20 ℃ cooling water,with the working concentration of 0.6,basic concentration of 0.385,and circulation multiple of 5.The thermal efficiency and the power recovery efficiency are 8.06 % and 6.66%,respectively.The power recovery efficiency of the DPAPC-a is 28.8% higher than that of the steam Rankine cycle(SRC) and 12.7% higher than that of ORC(R134a) under the optimized situation.

The Swelling Equilibria of N-isopropylacrylamide Based Hydrogel in Aqueous Solution of Ethanol

N-isopropylacrylamide (NIPAAm) was used to synthesize NIPAAm homopolymer (nonionized) and NIPAAm-sodium methacrylate copolymer (ionized). The swelling equilibria for both gels were obtained in aqueous solution of ethanol with concentration ranging from 0 to 100%(by mass) at 25℃. The swollen gel in water shrank first with the addition of a small amount of ethanol and then reswelled with further addition of ethanol showing not only a discontinuous volume phase transition but also a typical reentrant phenomenon. A thermodynamic model based on the UNIQUAC with the 'free-volume' contribution was applied to correlate and predict the swelling behavior of the poly(NIPAAM)-gels in ethanol-water mixture.

Effects of H_3PO_4 and Ca(H_2PO_4)_2 on mechanical properties and water resistance of thermally decomposed magnesium oxychloride cement

The effects of H3PO4 and Ca（H2PO4）2 on compressive strength, water resistance, hydration process of thermally decomposed magnesium oxychloride cement （TDMOC） pastes were studied. The mineral composition, hydration products and hydration heat release were analyzed by XRD, FT-IR, SEM and TAM air isothermal calorimeter, etc. After being modified by H3PO4 and Ca（HzPO4）2, the properties of the TDMOC are improved obviously. The compressive strength increases from 14.8 MPa to 48.1 MPa and 37.1 MPa, respectively. The strength retention coefficient （Kn） increases from 0.38 to 0.99 and 0.94, respectively. The 24 h hydration heat release decreases by 10% and 4% and the time of hydration peak appearing is delayed from 1 h to about 10 h. The XRD, FT-IR and SEM results show that the main composition is 5Mg（OH）z＇MgCIz＇8H20 in the modified TDMOC pastes. The possible mechanism for the strength enhancement was discussed. The purposes are to extend the potential applications of the salt lake magnesium resources and to improve the mechanical properties of TDMOC.

Adsorption of catechol from aqueous solution by aminated hypercrosslinked polymers

Adsorption of catechol from aqueous solution with the hypercrosslinked polymeric adsorbent NDA-100 and its derivatives AH-1, AH-2 and AH-3 aminated by dimethylamine, the commercial resin Amberlite XAD-4 and weakly basic anion exchanger resin D301 was compared. It was found that the aminated hypercrosslinked resins had the highest adsorption capacities among the tested polymers. The empirical Freundlich equation was successfully employed to describe the adsorption process. Specific surface area and micropore structure of the adsorbent, in company with tertiary amino groups on matrix affected the adsorption performance towards catechol. In addition, thermodynamic study was carried out to interpret the adsorption mechanism. Kinetic study testified that the tertiary amino groups on the polymer matrix could decrease the adsorption rate and increase the adsorption apparent activation energy.

Analysis of seasonal variation of water masses in East China Sea

Seasonal variations of water masses in the East China Sea(ECS) and adjacent areas are investigated, based on historical data of temperature and salinity( T-S). Dynamic and thermodynamic mechanisms that affect seasonal variations of some dominant water masses are discussed, with reference to meteorological data. In the ECS above depth 600 m, there are eight water masses in summer but only five in winter. Among these, Kuroshio Surface Water(KSW), Kuroshio Intermediate Water(KIW), ECS Surface Water(ECSSW), Continental Coastal Water(CCW), and Yellow Sea Surface Water(YSSW) exist throughout the year. Kuroshio Subsurface Water(KSSW), ECS Deep Water(ECSDW), and Yellow Sea Bottom Water(YSBW) are all seasonal water masses, occurring from May through October. The CCW, ECSSW and KSW all have significant seasonal variations, both in their horizontal and vertical extents and their T-S properties. Wind stress, the Kuroshio and its branch currents, and coastal currents are dynamic factors for seasonal variation in spatial extent of the CCW, KSW, and ECSSW, whereas sea surface heat and freshwater fl uxes are thermodynamic factors for seasonal variations of T-S properties and thickness of these water masses. In addition, the CCW is affected by river runoff and ECSSW by the CCW and KSW.

Kinetic Study of Hydrothermal Stripping from Iron-Loaded Organic Phase

The iron-loaded organic phase of naphthenic acid-isooctyl alcohol-kerosene was prepared, and the process kinetics of hydrothermal stripping of iron from the phase was studied. Several factors affecting hydrothermal stripping, such as the polymer of naphthenic acid, initial concentrations of iron and naphthenic acid, temperature and agitation time, were investigated, and based on experimental results and theoretical analysis, two kinetic models were established.The stripping rate equation suggests that the hydrothermal stripping process activation energy is 96.4 kJ·mol-1 and the stripping is controlled by hydrolysis of naphthenic complex of iron. The values calculated by the stripping fraction equation comparatively accord with the experimental data.

A Fourteen-Year Climatology of the Southwest Vortex in Summer

Statistical studies were conducted on the southwest vortex(SWV) during the summers of 2000–13 using high-resolution reanalysis data with a horizontal resolution of 0.5°× 0.5°. A total of 578 SWVs were detected, with a maximum interannual frequency of 55. The variation of the interannual frequency featured a period of around six years. The most active period of SWVs was early July and the maximum occurrence of SWVs appeared in early morning(0200–0800 Beijing Standard Time(BST)). Most of the SWVs were short-lived, with only 66 cases(11.4%) lasting for more than 24 h. In addition, the moving tracks and three-dimensional shape of long-lived(≥ 36 h) SWVs are also presented. For those SWVs that lasted for more than 12 h, four types of SWVs(Types I–IV) were identified using a new method, and the results indicated that the dynamical and thermodynamical conditions before the formation of SWVs are effective indicators of the subsequent evolution of the vortex and associated severe weathers. Moreover, a further level of classification was also constructed for Type II SWVs, which accounted for the largest proportion out of Types I–IV, and the results indicated that the lifespan, radius and maximum 6-h precipitation were all closely related to the intensity of precipitation before the formation of SWVs.

Prediction of Structure-H Gas Hydrate Formation Conditions for Reservoir Fluids

In this work, a thermodynamic model is developed for prediction of structure H hydrate formation. The model combines the Peng-Robinson equation of state for the vapor, liquid and aqueous phases with the extended Ng-Robinson hydrate model for gas hydrate formation of all three structures. The parameters of 14 structure- H hydrate formers are determined based on the experimental data of structure-H hydrates in the literature. The expression of fugacity of water in the empty hydrate phase is correlated for calculating structure-H hydrate formation conditions in the absence of free water. The model is tested by predicting hydrate formation conditions of a number of structure-H hydrate forming systems which are in good agreement with the experimental data. The proposed model is also applied to the prediction of hydrate formation conditions for various reservoir fluids such as natural gas and gas condensate.

Thermal Dehydration Kinetics of Gypsum and Borogypsum under Non-isothermal Conditions

Thermal dehydration of gypsum and borogypsum was investigated under nonisothermal conditions in air by using simultaneous thermogravimetric-differential thermal analyzer. Nonisothermal experiments were carried out at various linear heating rates. Kinetics of dehydration in the temperature range of 373-503 K were evaluated from the DTA (differential thermal analysis)-TGA (thermogravimetric analysis) data by means of Coats-Redfern,Kissinger and Doyle Equations. Values of the activation energy and the pre-exponential factor of the dehydration were calculated. The results of thermal experiments and kinetic parameters indicated that borogypsum is similar to gypsum from dehydration mechanism point of view although it consists of boron and small amount of alkali metal oxides.

Determination of Hydrogen Production from Rich Filtration Combustion with Detailed Kinetics Based CFD Method

Computational fluid dynamics （CFD） combined with detailed chemical kinetics was employed to model the filtration combustion of a mixture of methane/air in a packed bed of uniform 3 mm diameter alumina spherical particles. The standard k-ε turbulence model and a methane oxidation mechanism with 23 species and 39 elemental reactions were used. Various equivalence ratios （1.47, 1.88, 2.12 and 2.35） were studied. The numerical results showed good agreement with the experimental data. For ultra-rich mixtures, the combustion temperature exceeds the adiabatic value by hundreds of centigrade degrees. Syngas （hydrogen and carbon monoxide） can be obtained up to a mole fraction of 23%. The numerical results also showed that the combination of CFD with detailed chemical kinetics gives good performance for modeling the pseudo-homogeneous flames of methane in porous media.

Thermodynamic behaviors of Cu in interaction with chlorine, sulfur, phosphorus and minerals during sewage sludge co-incineration

Thermodynamic equilibrium calculations were performed to reveal effects of interactions among Cl, S, P and other minerals on Cu migration. Our results showed that HCl（g）, SO2（g） and （P2O5）2（g） were released from the sewage sludge co-incineration. Cl was found to weaken adsorption of Cu by Al2O3, CaO and Fe2O3, while S de- layed reactions of Fe2O3 and Al2O3 with Cu, with P having no effect on reactions between the minerals and Cu. Among the coupled systems ofCl, S and P, the co-existences of Cl and S, and Cl, S and P were determined to inhibit Cu volatilization, and the co-existence of Cl and P had an enhancing effect Cu migration was affected only by S in the S and P system. With the SiO2, CaO and Al2O3 system, both Cl alone and Cl and P led to failed reactions be- tween the minerals and Cu. In the systems of S, S and Cl, S and P, and S, Cl and P, the migration behavior of Cu was mainly affected by S at low temperatures and by Cl at high temperatures, whereas P had no effect on Cu mi- gration during the entire nrocess.

Correlation of ^1H NMR Chemical Shift for Aqueous Solutions by Statistical Associating Fluid Theory Association Model

1H NMR chemical shifts of binary aqueous mixtures of acylamide, alcohol, dimethyl sulphoxide (DMSO), and acetone are correlated by statistical associating fluid theory (SAFT) association model. The comparison between SAPT association model and Wilson equation shows that the former is better for dealing with aqueous solutions. Finally, the specialties of both models are discussed.

A Molecular Thermodynamic Model for Interfacial Tension in Surfactant-Oil-Water System

An interfacial equation of state based on perturbation theory for surfactant-oil-water system has been developed. By combining the interfacial equation of state with Boudh-Hir and Mansoori's model, a molecular ther-modynamic model has been proposed. The interfacial tension of surfactant-oil-water systems can be calculated from the surface tensions of pure oil and water by this model. The interfacial tension data for sodium dodecyl sulphate-heptane-water system, polyoxyethylene n-octylphenol-heptane-water system and hexadecyl trimethyl ammonium bromide-heptane-water system have been correlated. By using the adjustable parameters obtained, the interfacial tensions of these systems at other temperatures have been predicted. Both the correlated and the predicted values are satisfactory.

Rheological numerical simulation for thermo-hydro-mechanical coupling analysis for rock mass

Under the environment of seepage field, stress field and temperature field interaction and influence, the three fields will not only produce coupling effect, but also have deformation with time due to the rheological behavior of rock mass. In the paper, based on the fundamental theories of rock mass coupling theory and rheological mechanics, the rheological model for fully coupled thermo-hydro-mechanical analysis for rock mass was set up, and the corresponding constitutive relationship, the conservation equation of mass and the conservation equation of energy were given, and the finite element formulas were derived for coupling analysis of rock mass. During establishing governing equations, rock mass was assumed approximately as macro-equivalent continuum medium. The obtained rheological numerical model for fully coupled thermo-hydro-mechanical analysis can be used for analyzing and predicting the long-term stability of underground caverns and slope engineering under the condition of thermo-hydro-mechanical coupling with rheological deformation.