杂质气体对二氧化碳在废弃气藏咸水层埋存的影响

废弃气藏是埋存二氧化碳的理想场所,但气藏中的杂质气体会影响二氧化碳在水中的溶解过程。针对此问题,建立了考虑逸度-活度的热力学模型,准确捕捉杂质气体-二氧化碳-咸水混合体系的热力学特征。在此基础上,采用基于算子的线性化数值方法,高效准确求解质量守恒方程,研究不同混合物对二氧化碳在咸水中扩散-对流的影响。以荷兰西佩尔尼斯气藏为例,分析并评价了废弃气藏二氧化碳埋存的可行性及潜力。研究结果表明,二氧化碳在咸水中的溶解度随压力的升高而增加,随温度及矿化度的升高而降低,相同压力下,25℃下的溶解度约为90℃下的2倍。不同杂质气体对二氧化碳溶解能力的影响不同,甲烷对二氧化碳溶解度降低程度最大,降低幅度约为12%。二维模拟结果表明,杂质气体会降低二氧化碳羽流指进的速度,延长对流触发的时间,5%的甲烷-二氧化碳混合体系对流触发时间是纯二氧化碳的2.5倍,但杂质气体对总的溶解量影响不大。西佩尔尼斯气藏模拟结果表明,废弃气藏开展二氧化碳埋存潜力巨大;短时间内,二氧化碳主要以游离气及束缚气形式存在,溶解气量较少。关井30 a后,游离气占74.2%,残余气占19.1%,溶解气仅占6.7%。

初中化学疑难实验的改进与创新

对初中化学的3个疑难实验——铜与硝酸银溶液反应实验、铁与硫反应实验、二氧化碳溶解度测定实验进行了改进和创新。

Measurement and Correlation of Solubilities of C.I. Disperse Red 73,C.I. Disperse Blue 183 and Their Mixture in Supercritical Carbon Dioxide

The solubility of disperse dyes and their mixture in supercritical carbon dioxide is an important property in study and development of supercritical fluid dyeing technology.In this study,solubilities of C.I.Disperse Red 73,C.I.Disperse Blue 183 and their mixture in supercritical CO2 are measured at temperatures from 343.2 to 383.2 K and pressures from 12 to 28 MPa with a static recirculation method.Under the experimental conditions for the binary(C.I.Disperse Red 73+CO2 or C.I.Disperse Blue 183+CO2) and ternary(C.I.Disperse Red 73+C.I.Disperse Blue 183+CO2) systems,the solubilities increase with pressure.The solubility of C.I.Disperse Blue 183 decreases with the increase of temperature when the pressure is lower than 16 MPa,and the trend is opposite when the pressure is higher than 16 MPa.However,there is no crossover pressure for C.I.Disperse Red 73.The solubilities are also affected by molecular polarity of dyes.The co-solvent effect exhibited in the dissolving process of mixed dyes promotes their dissolution in supercritical CO2.The experimental data of solubilities of C.I.Disperse Red 73,C.I.Disperse Blue 183,and their mixture are correlated with the Chrastil model and Mendez-Santiago/Teja model. The former is more accurate.

Solubility of Piperine in Supercritical and Near Critical Carbon Dioxide

Piperine is a member of the lipids family commonly found in peppercorn, ginger and other natural sources and is grouped as an alkaloid. The solubility of piperine has been determined in carbon dioxide at near critical and supercritical conditions in a dynamic extraction apparatus. The conditions studied were at pressures ranging from 10 to 20 MPa and temperatures at 293, 300, 313, 323 and 333 K. The results showed that piperine solubility increased with increasing pressure at all temperatures studied. The solubility of plperme in near critical conditions was slightly higher than that at supercritical conditions only at the low-pressure range. Two semi-empirical density dependent correlations, namely the Chrastil model and the Dilute Solution model, were also used to estimate the solubility data. Although both models showed good correlation with the solubility data, the Dilute Solution model performed better prediction than the Chrastil model.

Solubility prediction of disperse dyes in supercritical carbon dioxide and ethanol as co-solvent using neural network

Nowadays artificial neural networkS （ANNs） with strong ability have been applied widely for prediction of non- linear phenomenon. In this work an optimized ANN with 7 inputs that consist of temperature, pressure, critical temperature, critical pressure, density, molecular weight and acentric factor has been used for solubility predic- tion of three disperse dyes in supercritical carbon dioxide （SC-C02） and ethanol as co-solvent. It was shown how a multi-layer perceptron network can be trained to represent the solubility of disperse dyes in SC-C02. Numeric Sensitivity Analysis and Garson equation were utilized to find out the degree of effectiveness of different input variables on the efficiency of the proposed model. Results showed that our proposed ANN model has correlation coefficient, Nash-Sutcliffe model efficiency coefficient and discrepancy ratio about 0.998, 0.992, and 1.053 respectively.

Measurement and Correlation of the Solubility of Ligusticum Chuanxiong oil in Supercritical CO_2

Extraction of the Ligusticum Chuanxiong oil with supercritical CO2 （SC-CO2） was investigated at the temperatures ranging from 55℃ to 70℃ and pressure from 25 MPa to 35 MPa. The mass of Ligusticum Chuanxiong oil extracted increased with pressure at constant temperature. The initial slope of the extraction was considered as the solubility of oil in SC-CO2. Chrastil equation was used to correlate the solubility data of Ligusticum Chuanxiong oil. An improved Chrastil equation was also presented and was employed to correlate the solubility data, The correlation results show that the values of the average absolute relative deviation are 5.94% and 3.33% respectively, indicating the improved version has better correlation accuracy than that of Chrastil equation.

Supercritical Carbon Dioxide Extraction of Andrographolide from Andrographis paniculata： Effect of the Solvent Flow Rate, Pressure, and Temperature

Andrographis paniculata Nees has been extensively used for traditional medicine and help against fever dysentery, diarrhoea, inflammation, and sore throat. In this study, andrographolide, the main component of this plant was extracted from the leaves of A. paniculata using supercritical carbon dioxide. The operating pressures were varied from 7.50 to 20MPa, the temperatures were varied from 30℃ to 60℃, and the flow rates were varied from 0.5 to 4ml.min^-1. The best extraction condition occurred at 10MPa, 40℃, and a flow rate of 2ml.min^-1 for a 3g sample of A. paniculata ground-dried leaves. The measured extraction rate was found to be about 0.0174g of andrographolide per gram of andrographolide present in the leaves per hour of operation. The future studies must focus on the interaction between the various operating parameters such as temperature, pressure, and flow rate of supercritical carbon dioxide.

Solubility of CO2 in Methanol, 1-Octyl-3-methylimidazolium Bis（trifluoromethylsulfonyl）imide, and Their Mixtures

Solubility data of carbon dioxide （CO2） （1） in methanol （2）, 1-octyl-3-methylimidazolium bis（trifluoro- methylsulfonyl）imide （[omim]＋[TfzN]-） （3）, and their mixtures （w3 = 0.2, 0.5, and 0.8） at temperatures 313.2 and 333.2 K and pressures up to 7.0 MPa were measured by a high-pressure view-cell technique. The solubility of CO2 in methanol （w3 = 0）, [omim]＋[Tf2N]- （w3 = 1.0） and their mixtures follows the order of （w3 = 0）〈（w3 = 0.2）〈 （w3 = 0.5）〈（w3 = 0.8）〈（w3 = 1.0） at the same temperature and pressure, while the magnitude of Henry＇s constants follows the reverse order at a given temperature, which is consistent with the COSMO-RS （conductor-like screen- ing for real solvents） calculation. The solubility data of CO2 in methanol and [omim]~[Tf2N]- are correlated with the Peng-Robinson equation of state, and the solubility of CO2 in the mixtures of methanol and [omim]＋[TfzN] can be well predicted based on the mole fraction average of methanol and [omim]＋[Tf2N] over the solubility of CO2 in pure methanol and [omim]＋[Tf2N] . The mixtures of methanol and [omim]＋[Tf2N]- may be used as physical solvents for capturing CO2 with high partial pressures since they combine the advantages of organic solvents and ionic liquids.

Solubility of red palm oil in supercritical carbon dioxide： Measurement and modelling

The solubility of red palm oil （RPO） in supercritical carbon dioxide （scCO2） was determined using a dynamic method at 8.5-25 MPa and, 313.15-333.15 K and at a fixed scCO2 flow rate of 2.9 g. mn -1 using a full factorial design. The solubility was determined under low pressures and temperatures as a preliminary study for RPO par- ticle formation using scCO2. The solubility of RPO was 0.5-11.3 mg. （g CO2） -1 and was significantly affected by the pressure and temperature. RPO solubility increased with pressure and decreased with temperature. The Adachi-Lu model showed the best-fit for RPO solubility data with an average relative deviation of 14% with a high coefficient of determination, R2 of 0.9667, whereas the Peng-Robinson equation of state thermodynamic model recorded deviations of 17%-30%.

Measurement and calculation of solubility of quinine in supercritical carbon dioxide

Solubility of quinine in supercritical carbon dioxide(SCCO_2) was experimentally measured in the pressure range of 8 to 24 MPa, at three constant temperatures: 308.15 K, 318.15 K and 328.15 K. Measurement was carried out in a semi-dynamic system. Experimental data were correlated by iso-fugacity model(based on cubic equations of state, CEOS), Modified Mendez–Santiago–Teja(MST) and Modified Bartle semi-empirical models. Two cubic equations of state: Peng–Robinson(PR) and Dashtizadeh–Pazuki–Ghotbi–Taghikhani(DPTG) were adopted for calculation of equilibrium parameters in CEOS modeling. Interaction coefficients(k_(ij)& l_(ij)) of van der Waals(vdW) mixing rules were considered as the correlation parameters in CEOS-based modeling and their contribution to the accuracy of model was investigated. Average Absolute Relative Deviation(AARD) between correlated and experimental data was calculated and compared as the index of validity and accuracy for different modeling systems. In this basis it was realized that the semi-empirical equations especially Modified MST can accurately support the theoretical studies on phase equilibrium behavior of quinine–SCCO_2 media. Among the cubic equations of state DPGT within two-parametric vd W mixing rules provided the best data fitting and PR within one-parametric vd W mixing rules demonstrated the highest deviation respecting to the experimental data. Overall, in each individual modeling system the best fitting was observed on the data points attained at 318 K, which could be perhaps due to the moderate thermodynamic state of supercritical phase.

Determination of Paclitaxel Solubility in Carbon Dioxide Using Quartz Crystal Microbalance

A quartz crystal microbalance （QCM） is used to determine the phase equilibrium of paclitaxel-carbon dioxide system in the pressure range of 0-11 MPa and at temperatures of 35 °C,40 °C and 45 °C.The experimental results indicated that gaseous CO2 could be absorbed poorly into paclitaxel.The swelling of paclitaxel film in CO2 was observed before paclitaxel dissolved into supercritical carbon dioxide （ScCO2） with the increase of pressure.It was found that ScCO2 was not a good solvent for paclitaxel.The mole fraction of paclitaxel in ScCO2 was in the range of （4.5×10-9）-（7.8×10-9） under all our experimental conditions.Therefore,a much higher pressure than the CO2 supercritical point and/or a cosolvent must be used in any processes wherever paclitaxel dissolution in ScCO2 is required.

Solubilities of Cimaterol and Mabuterol in SF-CO_2

The solubilities of two β-agonists, cimaterol and mabuterol, in supercritical carbon dioxide (SF-CO2) were measured by a recirculating method at temperatures of 40℃ and 60℃ and pressures between 9 MPa to 49 MPa.The compounds exhibit very limited solubilities in the range of 10^-5 to 10^-7 (mole fraction). Cimaterol has a higher solubility than that of mabuterol. The experimental data of solubility were correlated by four density-based models.The correlation accuracy highly depends on the system investigated, which is mainly determined by the density ranges and temperature.