An Evaluation of Phase Behaviors of the Oil-Gas-Water System in the Displacement of Crude Oil with CO_(2)

CO_(2)dissolution into an aqueous phase and water evaporation into a gaseous phase takes place during CO_(2)injection into an oil reservoir.This study aims to evaluate the phase behaviors of the oil-gas-water system in the displacement of crude oil by CO_(2).The composition of the JL oilfield in the northeast of China is taken as an example.The flash calculation of the oil-gas-water system was performed,based on the method presented by Li and Nghiem.The research results show that CO_(2)dissolution in the aqueous phase declines as the NaCl concentration in formation water rises.CO_(2)injection is beneficial for the evaporation of formation water.The NaCl concentration in formation water has little effect on water evaporation and dissolved-gas escape.When the injection-gas mole fraction of CO_(2)is 0.5,CO_(2)injection can reverse the phase behavior of the petroleum mixture and the oil-gas system is converted to a pure gas-condensate system.For CO_(2)injection,water vapor has little effect on the miscibility of multiple contacts,but can reduce the miscibility of the first contact.

Phase behavior of TXs/toluene/water microemulsion systems for solubilization absorption of toluene

Triton Xs （TXs） surfactants/cosurfactant/water/oil （toluene） microemulsion systems for enhancing toluene solubilization were proposed and its potential was investigated for toluene removal from gas stream. The results indicated that TX-100 was superior to other TXs surfactants in removing toluene without cosurfactant. The efficiency of cosurfactants for improving toluene solubilization capacity follows the order： amine 〉 alcohol 〉 acid. According to the factor analysis, the linear cosurfactants are better than the branched ones. The effects of hydrophile-lipophile balance （HLB）, salt （NaCl） concentration and temperature on the formation of microemulsion system were also discussed. The results suggested that the optimum value of HLB was 15, the effect of NaCl concentration on the system was inconspicuous and the lower temperature enhanced the solubilization capacity. Nonionic surfactant-based microemulsions had a significant absorption enhancement for toluene, indicated by as much as 82.72% of toluene in phase composition diagram, which will have a great prospect in air pollution treatment.

Phase Behavior of Rare Earth Manganites

Among complex oxides containing rare earth and manganese BaLn_2Mn_2O_7 (Ln=rare earth) with the layered perovskite type and Ln_2(Mn, M)O_7 with pyrochlore-related structure were studied since these compounds show many kinds of phases and unique phase transitions. In BaLn_2Mn_2O_7 there appear many phases, depending on the synthetic conditions for each rare earth. The tetragonal phase of so-called Ruddlesden-Popper type is the fundamental structure and many kinds of deformed modification of this structure are obtained. For BaEu_2Mn_2O_7 at least five phases have been identified from the results of X-ray diffraction analysis with the space group P4_2/mnm, Fmmm, Immm and A2/m in addition to the fundamental tetragonal I4/mmm phase. In the pyrochlore-related type compounds, Ln_2Mn_(2-x)M_xO_7 (M=Ta, Nb, W etc), there also appear several phases with different crystal structures. With regard to every rare earth, Ln_2MnTaO_7 phase is stable only for excess Ta and can be obtained under high oxygen partial pressure process. This group has trigonal structure with zirkelite type (P3_121 space group). On the other hand Ln_2Mn_(2/3)Nb_(4/3)O_7 phase has monoclinic (C2/c space group) and zirconolite type structure. All of these structural models have the fundamental structure based on HTB (hexagonal tungsten bronze) layers formed by the arrangement of oxygen octahedra.

Synthesis and Phase Behavior of ω-(cholesteroxycarbonyloxy)-alkyl 3,3,5,5-tetramethyl-3,5-disila-4-oxa cyclohexyl-carboxylate

Four new organosilane compounds containing cholesteryl group were synthesized by esterification of 3,3,5,5-tetramethyl-3,5-disila-4-oxa-cyclohexane-1-carboxylic acid and ω-hydroxyalkyl, cholesteryl carbonate in the presence of DCC and DMAP. Their structures were characterized by1H-NMR, IR and elemental analysis. Their phase behaviors were investigated by differential scanning calorimetry (DSC) and polarized microscopy. Results showed that these four organosilane compounds were all liquid crystalline and longer spacer was advantageous to orientation of organosilane heterocycle and cholesteryl group.

Representation of Phase Behavior of Ionic Liquids Using the Equation of State for Square-well Chain Fluids with Variable Range

An equation of state （EOS） for square-well chain fluids with variable range （SWCF-VR） developed based on statistical mechanics for chemical association was employed for the calculations of pressure-volume-temperature （pVT） and phase equilibrium of pure ionic liquids （ILs） and their mixtures. The new molecular parameters for 23 ILs were obtained by fitting their experimental density data over a wide temperature and pressure ranges. The mo- lecular parameters of ILs composed of homologous organic cation and an identical anion such as [Cxmim][NTf2] are good linear with respect to their molecular weight, indicating that the molecular parameters of homologous substances, subsequently p VT and vapor-liquid equilibria vapor-liquid equilibria （VLE） can be predicted using the generalized parameter when no experimental data were available. The new set of parameters were satisfactorily used for calculations of the property of solvent and ILs mixture and the solubility of gas in various ILs at low pressure only using one temperature-independent binary interaction parameter.

Effect of thermodynamic parameters on prediction of phase behavior and process design of extractive distillation

Extractive distillation was investigated for separation of the minimum azeotrope of n-propanol/water, via the Aspen Plus simulation platform. Experimental data of n-propanol/water, which could pass the thermodynamic consistency test, were regressed to get suitable binary interaction parameters(BIPs) by the UNIQUAC thermodynamic model. The azeotrope system was heterogeneous in the simulation with built-in BIPs, which was contrary to the experimental data. The study focused on the effect of thermodynamic parameters on the prediction of phase behavior, and process design of extractive distillation. N-methyl-2-pyrrolidone(NMP) and ethylene glycol were used as solvents to implement the separation. Processes with built-in and regressed BIPs were explored,based on the minimum total annual cost(TAC). There were significant differences in the phase behavior simulation using different thermodynamic parameters, which showed the importance of BIPs in the design and optimization of extractive distillation.

Phase Behavior, Thermal Stability and Rheological Properties of PPEK/PC Blends

Phase behavior, thermal stability and rheological properties of the blends of poly(phthalazinone ether ketone) (PPEK) with bisphenol-A polycarbonate (PC) prepared by solution coprecipitation were studied using differential scanning calorimetry (DSC), Frourier-Transform IR spectroscopy (FT-IR), thermogravimetric analysis (TGA) and capillary rheometer. The DSC results indicated that PPEK/PC blends are almost immiscible in full compositions. FT-IR investigation showed that there were no apparent specific interactions between the constituent polymers. The blends keep excellent thermal stability and the addition of PC degrades the thermal stability of blends to some degree. The thermal degradation processes of the blends are much similar to that of PC. The studies on rheological properties of blends show that blending PPEK with PC is beneficial to reducing the melt viscosity and improving the appearance of PPEK.

STUDIES ON STRUCTURE AND PHASE BEHAVIOR OF MULTICOMPONENT POLYMERS THROUGH RHEOLOGICAL TESTS

Rheological measurement has been a preferred approach to the characterization of the structure and phase behaviors for multi-component/multi-phase polymer systems, due to its sensitive response to the changes of structure for these heterogeneous polymers. In the present article, recent progresses in the studies on rheology for heterogeneous polymer systems including phase-separated polymeric blends and block copolymers are reviewed, mainly depending on the results by the authors＇ research group. By means of rheological measurements, not only some new fingerprints responsible for the evolution of morphology and structure concerning these polymer systems are obtained, also the corresponding results are significant for design and preparation of novel polymeric structural materials and functional materials.

Study on the Phase Behavior of Coating Matrix in Supercritical or Sub-critical Carbon Dioxide

The high-pressure phase behavior of coating-solvent-supercritical or sub-critical carbon dioxide system was investigated experimentally. The coating matrix used was 108-acrylic resin at concentration ranging from 10% to 50% (by mass) in mixtures with n-butyl acetate. The experiments were conducted in a high-pressure view cell for temperatures from 35℃ to 65℃ and for pressures from 3.0MPa to 8.0MPa. The effect of temperature, pressure and content of every component on the phase behavior of the systems was observed. Finally, the ternary phase diagram for resin-solvent-CO2 was plotted.

Phase behaviors in a binary mixture of diblock copolymers confined between two parallel walls

The phase behaviors in a binary mixture of diblock copolymers confined between two parallel walls are investigated by using a cell dynamics simulation of the time-dependent Ginzburg-Landau theory.The morphological dependence of the wall-block interaction and the distance between walls（confinement degree） has been systematically studied,and the effect of repulsive interactions between different monomers is also discussed.It is interesting that multiple novel morphological transitions are observed by changing these factors,and various multilayered sandwich structures are formed in the mixture.Furthermore,the parametric dependence and physical reasons for the microdomain growth and orientational order transitions are discussed.From the simulation,we find that much richer morphologies can form in a binary mixture of diblock copolymers than those in a pure diblock copolymer.Our results provide an insight into the phase behaviors under parallel wall confinement and may provide guidance for experimentalists.This model system can also give a simple way to realize orientational order transition in soft materials through confinement.

Phase Behavior and Structural Transitions in Sodium Dodecyl Sulfonate Microemulsions

The forming mechanism of microemulsion of sodium dodecyl sulfonate, alcohols,water and isooctane was studied, with particular emphasis on the effect of molecular weight andconcentration of alcohols. Phase diagram of the four components, alcohol, sodium dodecyl sulfonate,water and isooctane, was used as a means of study, through which the microemulsion regions weredetermined. Phase diagram of sodium dodecyl sulfonate/n-pentanol/isooctane/water system at κ_m = 2(κ_m = W_(n-pentanol)/W_(SDS)) is presented. The variation of conductivities of differentmicroemulsion samples with water was measured. From the conductivities we investigated a change instructure from water droplets in oil (W/O) at low water content to liquid crystal at intermediatewater content and a stricture of oil droplets in water (O/W) at high water content.

Phase behavior of heavy oil-solvent mixture systems under reservoir conditions

A novel experimental procedure was proposed to investigate the phase behavior of a solvent mixture(SM)(64 mol%CH4,8 mol%CO2,and 28 mol%C3 H8)with heavy oil.Then,a theoretical methodology was employed to estimate the phase behavior of the heavy oil-solvent mixture(HO-SM)systems with various mole fractions of SM.The experimental results show that as the mole fraction of SM increases,the saturation pressures and swelling factors of the HO-SM systems considerably increase,and the viscosities and densities of the HO-SM systems decrease.The heavy oil is upgraded in situ via asphaltene precipitation and SM dissolution.Therefore,the solvent-enriched oil phase at the top layer of reservoirs can easily be produced from the reservoir.The aforementioned results indicate that the SM has promising application potential for enhanced heavy oil recovery via solvent-based processes.The theoretical methodology can accurately predict the saturation pressures,swelling factors,and densities of HO-SM systems with various mole fractions of SM,with average error percentages of1.77%for saturation pressures,0.07%for swelling factors,and 0.07%for densities.

Study on the Miscibility and Phase Behavior of Polyoxymethylene with Novolak

The miscibility and phase behavior of the blends of polyoxymethylene (POM)/Novolak were investigated by the cloud point method, which showed that the POM/Novolak blends exhibited a lower critical solution temperature. The melting point of POM decreased when diluted with Novolak. From the melting temperature depression of POM, a negative interaction parameter (x) between POM and Novolak was obtained. The IR spectrum revealed that the miscibility between POM and Novolak was caused by the specific interaction between the OH groups of Novolak and the ether oxygen atoms of POM. The morphology of the blends investigated by polarized light microscopy showed that the size of spherulites of POM was sharply decreased by its mixing with Novolak. This suggests that Novolak be used as a compatibilizer for POM.

COMPATIBILITY AND PHASE BEHAVIOR OF PS/SBR BLENDS H. TORSIONAL BRAID ANALYSIS

The compatibility and phase behavior of PS/SBR blends was studied with torsional braid analysis technique. The technique used in this study for preparation of braids was first developed by one of the authors, which gives more precise phase diagram as compared to other conventional methods. The results obtained are in good agreement with those obtained in our previous work.

COMPATIBILITY AND PHASE BEHAVIOR OF PS/SBR BLEND Ⅰ. EFFECT OF MOLECULAR WEIGHT OF PS

The results of this study reveals not only the sensitivity of the compatibility of PS with SBR to the molecular weight (MW) of PS and temperature, but also some other interesting characteristics, i. e., unusual morphology change during the process of mixing with increase in temperature of specimen preparation observed under optical microscope and double-peak UCST curves for three blends with PS of low MW from DSC data. Acording to the amount of inward shift of the component T_g's and the broadening of the transition regions, it may be said that this polymer pair is compatible only when the MW of PS is low, and even then there still exists micro-heterogeneity.

Phase behavior of rotationally asymmetric Brownian kites containing 90°internal angles

Previous Monte Carlo simulations have shown that ordered tetratic phases can emerge in a dense two-dimensional Brownian system of rotationally asymmetric hard kites having 90°internal angles.However,there have been no experimental investigations yet to compare with these simulation results.Here,we have fabricated two types of micron-sized kites having internal angles of 72°-90°-108°-90°and 72°-99°-90°-99°,respectively,and we have experimentally studied their phase behavior in two-dimensional systems.Interestingly and in contrast to the Monte Carlo simulations,the experimental results show a phase sequence of isotropic fluid-hexagonal rotator crystal-square crystal as the area fractionφA increases for both types of kites.The observed square crystal displays not only a quasi-long-range translational order but also(quasi-)long-range 4-fold bond-and molecular-orientational order;these characteristics confirm that tetratic order can emerge even in dense Brownian systems of rotationally asymmetric particles.A model based on local polymorphic configurations(LPCs)is proposed to understand the origin of the square lattice order in these dense kite systems.The results in this study provide a new route to realize custom-designed self-assembly of colloids by controlling LPCs.

Reaction kinetics and phase behavior in the chemoselective hydrogenation of 3‐nitrostyrene over Co‐N‐C single‐atom catalyst in compressed CO_(2)

Single‐atom catalysts(SACs)have demonstrated excellent performances in chemoselective hydrogenation reactions.However,the employment of precious metals and/or organic solvents compromises their sustainability.Herein,we for the first time report the chemoselective hydrogenation of 3‐nitrostyrene over noble‐metal‐free Co‐N‐C SAC in green solvent—compressed CO2.An interesting inverted V‐curve relation is observed between the catalytic activity and CO2 pressure,where the conversion of 3‐nitrostyrene reaches the maximum of 100%at 5.0 MPa CO2(total pressure of 8.1 MPa).Meanwhile,the selectivities to 3‐vinylaniline at all pressures remain high(>99%).Phase behavior studies reveal that,in sharp contrast with the single phase which is formed at total pressure above 10.8 MPa,bi‐phase composed of CO2/H_(2)gas‐rich phase and CO2‐expanded substrate liquid phase forms at total pressure of 8.1 MPa,which dramatically changes the reaction kinetics of the catalytic system.The reaction order with respect to H_(2)pressure decreases from~0.5 to zero at total pressure of 8.1 MPa,suggesting the dissolved CO2 in 3‐nitrostyrene greatly promotes the dissolution of H_(2)in the substrate,which is responsible for the high catalytic activity at the peak of the inverted V‐curve.

Simulation of petroleum phase behavior in injection and production process of underground gas storage in a gas reservoir

On the basis of analyzing the fluid phase behavior during the transformation from gas reservoir to gas storage,a mathematical model and an experimental simulation method are established to describe the oil-gas phase behavior during the whole injection-production process of gas storage.The underground gas storage in the Liaohe Shuang 6 gas reservoir with oil rim is taken as a typical example to verify the reliability and accuracy of the mathematical model and reveal characteristics and mechanisms of fluid phase behavior.In the gas injection stage of the gas storage,the phase behavior is characterized by mainly evaporation and extraction and secondarily dissolution and diffusion of gas in the cap to oil in the oil rim of the reservoir;the gas in gas cap increases in light component content,decreases in contents of intermediate and heavy components,and increases in density and viscosity.The oil of the ring decreases in content of heavy components,increases in contents of light and intermediate components,decreases in density and viscosity,and increases in volume factor and solution gas oil ratio.In the stable operation stage of periodic injection-production of gas storage,the phase behavior shows that the evaporation and extraction capacity of injection gas in the cap to oil rim is weakened step by step,the phase behavior gradually changes into dissolution and diffusion.The gas in gas cap decreases in content of intermediate components,increases in content of light components slowly,and becomes lighter;but changes hardly in density and viscosity.The oil in the oil rim increases in content of heavy components,decreases in content of intermediate components,rises in density and viscosity,and drops in volume factor and solution gas oil ratio.

Studies on the Phase Behavior of Lyotropic Liquid Crystal in DAD/C_4OH/n-C_8H_(18)/D_2O System

The lytropic liquid crystals in dodecanic acid diethanolamine (DAD) /n-butanol (C4OH) /octane (n-C8H18) /deuteron (D2O) system were studied to determine the phase regions and were investigated by 2H-NMR spectroscopy,optical polarizing microscope and small-angle X-ray diffraction (SAXD) methods.The results indicate that the lamellar,hexagonal and cubic liquid crystals all exist in the above system.Keeping the weight ratio of DAD and C4OH constant,the microphase Structure,2H quadruple splitting and the interlayer spacing are all changed with the addition of deuteron.

SYNTHESIS AND PHASE BEHAVIOR OF LIQUID CRYSTALLINE 4'-ALKYLOXY-4-HYDROXYBIPHENYLS

The synthesis and phase behavior of a series of 4'-alkyloxy -4-hydroxy biphenyls were discribed.The effects of reaction conditions on the yields of products were investigated.The characterizations of thermotropic liquid crystalline products for the type and thermal properties are discussed through the use of differential scanning calorimetry,polarizing microscopy.