簇合物(p-H2)N-HCCCN的结构和能量

采用两体作用势模型和遗传算法对簇合物(p-H2)N-HCCCN的极小能量结构和能量进行了理论研究.结果表明,20个para-H2分子形成HCCCN周围的第一个溶剂层,第一个溶剂层包含三个溶剂环,每个溶剂环都有6个para-H2分子,第19和20个para-H2分子分别聚集在HCCCN分子的N、H原子末端.进一步计算了(p-H2)N-HCCCN的化学势,发现化学势随para-H2分子个数的增加呈震荡变化.     

Solvent effect on distribution ratio of Pd(II) in supercritical carbon dioxide extraction and solvent extraction using 2-methyl-8-quinolinol

The distribution ratio (D_M) of Pd(II) by the extraction with 2-methyl-8-quinolinol (HMQ) was determined using the supercritical carbon dioxide medium (SF-CO₂) and organic solvent media such as perfluoro-methylcyclohexane, heptane, cyclohexane, carbon tetrachloride and benzene. From experimental results of the slopes of log D_M versus pH plot and log D_M versus HMQ concentration plot, the extracted species both in the SF-CO₂ extraction (SFE) and the solvent extraction (SE) were determined to be Pd(MQ)₂. The distribution constant of HMQ (K_D,HMQ) in the SFE and SE systems were determined from the dependence of the distribution ratio of HMQ (D_HMQ) on the pH. A linear relationship was observed between log K_D,HMQ and the solubility parameter (δ) of the extraction medium based on the regular solution theory in both the SFE using SF-CO₂ at the pressure of 8.5–40 MPa and the SE systems. The difference in the slope of the log K_D,HMQ versus δ plot between the SFE and the SE systems is attributable to the extent of the specific interaction of the solute HMQ with the solvent molecules, i.e. CO₂ molecules and the organic solvent molecules. The D_M versus δ plot obtained under a given extraction condition using SF-CO₂ (11–40 MPa) and organic solvents showed clear linearity. The D_M obtained using SF-CO₂ at relatively low pressure range from 8.5 to 11 MPa was independent of the pressure and the δ of SF-CO₂, which coincides with the experimental fact that the solubility of Pd(MQ)₂ in the SF-CO₂ at 8.5–11 MPa was practically constant.     

Pathway dependence of the efficiency of calculating free energy and entropy of solute–solute association in water

In this study we investigate two alternative pathways to compute the free energy and the entropy of small molecule association (ΔF_assoc and ΔS_assoc) in water. The first route (direct pathway) uses thermodynamic integration as function of the distance R between the solutes. The mean force and the mean covariance of the force with the energy in solution are calculated from molecular dynamics simulation followed by integration of these quantities with respect to the reaction coordinate R. The alternative approach examined (solvation pathway) would first remove the solutes from the solution using thermodynamic integration as function of a solvation coupling parameter λ, change the solute–solute distance in vacuo and then solvate back the solute pair at the new separation distance. The system studied was a pair of CH₄ molecules in water. We investigate the influence of the CH₄–water interaction strength on the obtained ΔF_assoc and ΔS_assoc values by changing van der Waals and Coulomb interaction and evaluated the accuracy and efficiency for the two pathways. We find that the direct route seems more suitable for the calculation of free energies of hydrophobic solutes while the solvation pathway performs better when calculating entropy changes for solutes that have a stronger interaction with the solvent.     

Resolution studies on counter-current chromatography using supercritical fluid carbon dioxide

Counter-current chromatography (CCC) is a form of liquid–liquid partition chromatography. It requires two immiscible solvent phases; the stationary phase is retained in the separation column, generally by centrifugal force, while the mobile phase is eluted. We recently replaced the mobile phase with supercritical fluid carbon dioxide (SF CO₂). Since the solvent strength of SF CO₂ can be varied by changing the temperature and pressure of the system, separation adjustments are thus more versatile. We investigated the pressure and temperature effects on resolution using water and low-carbon alcohol mixtures as the stationary phases. It was demonstrated that these special properties of SF CO₂ were indeed beneficial to the optimization of separations. In addition, the phase retention ratio was examined in terms of separation resolution. The results appeared very similar to those obtained from conventional traditional CCC. This study should be helpful for the future development of SF applications in CCC.     

CO_2在复合溶液MDEA-AMP中的溶解度

测定了CO2在复合溶液N-甲基二乙醇胺(MDEA)+2-氨基-2-甲基-1-丙醇(AMP)中的溶解度,研究了气相CO2浓度、温度和复合溶液的组分对溶解度的影响。实验获得了温度分别为25℃、30℃和40℃时,CO2在复合溶液MDEA-AMP中的溶解度。实验表明,溶解度随气相中CO2浓度升高或随AMP在复合溶液中的摩尔分数升高而升高,随温度升高而降低。     

Solubility of methane in cellulose acetate — conditioning effect of carbon dioxide

The solubility of CH₄ and CO₂ in cellulose 2.4-acetate membranes was measured at temperatures between —10° and 30°C, and at pressures of up to 40 atm. Pre-exposure of the membrane samples to high-pressure CO₂ caused an increase in the solubility of CH₄, as well as of CO₂ [2]. In contrast, pre-exposure of the samples to high-pressure CH₄ did not alter the solubility of either CH₄ or CO₂. A similar “conditioning effect” by high-pressure CO₂ was also observed with other glassy polymers by Paul et al. [9-11], who reasonably attributed it to the non-equilibrium nature of the glassy state. The solubility isotherms for CH₄ and CO₂ in cellulose 2.4-acetate can be fitted to the “dual-mode” sorption model [1], but a consideration of the heats of solution suggests that a “two Langmuir sites” model [16] may offer a more satisfactory representation of the data. The cellulose acetate samples employed in this study were prepared by drying reverse osmosis membranes and are believed to have contained a large amount of free volume.     

Modified poly(phenylene oxide) membranes for the separation of carbon dioxide from methane

Two types of poly(phenylene oxide) (PPO) membranes were prepared: one by chemical modification through sulfonation using chlorosulfonic acid and another by physical incorporation with a heteropolyacid (HPA), viz., phosphotungstic acid. These membranes were tested for the separation of CO₂/CH₄ mixtures. Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction techniques were used to confirm the modified structure of PPO as well as to understand its interactions with gaseous molecules. Scanning electron microscopy (SEM) was used to investigate the membrane morphology. Thermal stability of the modified polymers was assessed by differential scanning calorimetry (DSC), while the tensile strength was measured to evaluate their mechanical stability. Both chemical and physical modifications did not adversely affect the thermally and mechanical stabilities. Experiments with pure CO₂ and CH₄ gases showed that CO₂ selectivity (27.2) for SPPO increased by a factor of 2.2, while the PPO–HPA membrane exhibited 1.7 times increase in selectivity with a reasonable permeability of 28.2 Barrer. An increase in flux was observed for the binary CO₂/CH₄ mixture permeation with an increasing feed concentration (5–40 mol%) of CO₂. An enhancement in feed pressure from 5 to 40 kg/cm² resulted in reduced CO₂ permeability and selectivity due to the competitive sorption of methane. Both the modified PPO membranes were found to be promising for enrichment of methane despite exhibiting lower permeability values than the pristine PPO membrane.     

六氟化硫中痕量一氧化碳和二氧化碳的气相色谱检测及其在断路器故障分析中的应用

为了准确分析高浓度SF₆中痕量的CO及CO₂,发展了可靠的气相色谱-火焰离子化检测器（GC-FID）方法。通过双Porapak Q色谱柱结合阀切换将SF₆从待测样品中分离并排出检测系统,从而避免SF₆可能造成的在线转化柱中毒现象,同时实现CO和CO₂的完全分离;通过在线镍催化将CO和CO₂的检测转化为对CH₄的检测,极大地提高检测灵敏度。结果显示,该方法对CO和CO₂的检测互不干扰,两者都可在2~500 μL/L范围内呈现良好的线性相应,测定重复性好（RSD小于2%）,准确度高。建立的GC-FID方法可直接用于SF₆高压断路器中痕量CO及CO₂的检测,为SF₆相关电气设备潜伏性故障诊断提供了研究手段。     

Endothermic character of toluene adsorption from supercritical carbon dioxide on activated carbon at low coverage

Recasens, P., Velo, E., Larrayoz, M.A. and Puiggené, J., 1993. Endothermic character of toluene adsorption from supercritical carbon dioxide on activated carbon at low coverage. Fluid Phase Equilibria, 90: 265-287.

Heat effects and volumetric properties are analyzed for the adsorption of toluene from supercritical carbon dioxide onto activated carbon at the limit of zero coverage, based on existing data for the system. Using values of the adsorption equilibrium constant at different temperatures as a function of fluid density, large, negative partial molar volumes for toluene in the fluid were obtained, which were previously unavailable.

Numerical integration of the differential equation that expresses the isobaric temperature dependence of the equilibrium constant, coupled with parameter optimization, enabled us to estimate the differential enthalpy of toluene adsorption onto the surface from the ideal gas at the same pressure and temperature, in addition to the enthalpy of transfer from the fluid to the surface. This is found to be large and positive near the critical conditions. Using the thermodynamic analysis of Kelley and Chimowitz, our results show that in terms of the enthalpy of transfer, the isothermal adsorption from a supercritical fluid is an endothermic process, thus explaining the retrograde behavior experimentally observed for the regeneration of carbon with supercritical CO₂ at conditions not far from the solvent's critical point.     

Investigation of carbon dioxide modified supercritical and near supercritical carrier streams for flow injection systems

Since flow injection (FI) is a dilution technique, efforts have been undertaken to minimize online dilution or dispersion. Solutes in supercritical fluids exhibit increased diffusion coefficients which have been shown to decrease dispersion of the sample zone. This work investigates the use of supercritical fluids (or CO₂ modified fluids) as carrier streams for FI. Both a non-reacting tracer and an online chemical reaction were employed to investigate the behavior of solutes in supercritical and near critical systems. Further, these results are compared to those obtained in the system studied with a conventional carrier stream. Plots of peak response vs% CO₂ modifier increase with a sharp break at moderate modifier composition (20–30%). Plots of peak variance vs% CO₂ modifier show decreased variance with increasing % modifier. The system was also optimized with regards to temperature and pressure. The optimized system displayed improved limits of detection and decreased variance relative to 0% CO₂ modifier carrier streams.     

Solvation of the tautomeric forms of 2-oxopyrimidine in carbon tetrachloride solution: A Monte Carlo simulation

Solvation of both tautomeric forms of 2-oxopyrimidine by carbon tetrachloride has been investigated using the Monte Carlo method for a cluster consisting of 50 molecules at T=300 K. The results indicate that, in oposition to hydration, this solvation shifts the tautomeric equilibrium a little towards the lactim form, in agreement with experiment. The structure of the solvation shell in both tautomers closely resembles that of the pure solvent. Local minima of the interaction energy between n = 1, 2, 3, 4, 6 and 8 CCl₄ molecules and 2-oxopyrimidine have been examined. The results shed some light on the nature of the poor solubility of purines and pyrimidines in carbon tetrachloride.     

CO2在非质子溶剂与铁基离子液体复合体系中的吸收

选用非质子型有机溶剂聚乙二醇二甲醚(NHD)与N, N-二甲基乙酰胺(DMAC), 分别与BmimFeCl₄复配, 构建了BmimFeCl₄/NHD和BmimFeCl₄/DMAC复合铁基离子液体体系. 考察了温度、 BmimFeCl₄/溶剂的质量 比以及压力对CO₂在复合铁基离子液体体系中溶解行为的影响. 结果表明, 高压低温的吸收条件更利于CO₂ 的溶解, 当BmimFeCl₄/DMAC质量比为7∶3时, CO₂在BmimFeCl₄/DMAC复合体系中的亨利系数为0.9181 MPa·L·mol^-1, 低于同等条件下BmimFeCl₄/NHD体系的亨利系数. 在常压、 363.2 K条件下进行再生, 经5次循环后, CO₂在BmimFeCl₄/NHD和BmimFeCl₄/DMAC中的溶解度分别为初次吸收量的92.53%和99.04%. 傅里叶变换红外光谱(FTIR)结果表明, 铁基离子液体复配体系吸收CO₂为物理吸收过程. 密度泛函理论(DFT)计算与IRI分析的结果表明, 在复配DMAC的体系中, CO₂更倾向与阳离子和溶剂分子作用, 而在复配NHD的体系中, CO₂则更容易与阴离子和溶剂分子作用.     

Capacity ratios and diffusion coefficients of low-volatile organic compounds in supercritical carbon dioxide from supercritical fluid chromatography (SFC)

Capacity ratios k have been determined for phenyl myristate, phenyl palmitate and phenyl stearate from supercritical fluid chromatography (SFC) at 35 to 56°C and 85 to 190 bar using supercritical CO₂ as mobile phase and Perisorb A and Perisorb RP8 as stationary phases. For the esters used a rise in pressure from 90 to 190 bar produces a drop of k by about two orders of magnitude giving evidence of the rapidly increasing solvent power of supercritical CO₂ with increasing density. At a constant CO₂ density, k decreases with increasing temperature. The separation of the esters was found to be the better the lower the pressure was.

An apparatus for the chromatographic determination of binary diffusion coefficients in supercritical gases is described. D₁₂ values for some organic compounds in carbon dioxide at 40°C and in the pressure range from 80 to 160 bar are presented. With an improved electronic flow regulator an overall precision of the D₁₂ values of ±3% is obtained.     

Solvent effects on non-resonant vibrational deactivation: N2(ν = 1) deactivated by CH4 in liquid Ar/liquid N2 mixtures

New measurements have been made of rate constants for the vibrational deactivation of N₂(ν = 1) by CH₄ in liquid Ar/liquid N₂ mixtures. The ratio of the liquid phase rate constants, k_L,M for the liquid mixture over k_L,Ar for liquid argon solution, varies non-linearly with composition. The results imply a saturation effect which occurs when one solvent N₂ molecule is present in the first solvation shell of the excited molecule. It is proposed that this is due to the formation of a N₂(ν = 1) … N₂ collision complex.     

A new experimental technique for validating exchange models of carbon dioxide between the atmosphere and sea-water

The mechanism of CO₂-exchange between the atmosphere and sea-water was re-examined by simultaneously measuring pH and pO₂ in artificial sea-water exposed to CO₂ and air atmospheres. The data were fitted to an exchange model by using both the differential and integral forms of the diffusion equation. It was found that the pH and pO₂ data support the assumption that the exchange for these gases is driven by the gradient of the partial pressure of the gas across the imaginary solution-gas boundary layer (the z layer) and is not affected by chemical reaction or hydration rate under the experimental conditions used, viz. 1–100 meq/l., alkalinity, pH 4.5–8.3 and z-layer thickness 2–500 μm. It is concluded that the rate of hydration of CO₂ plays an insignificant role in the exchange mechanisms between the atmosphere and the oceans.     

Fluid phase equilibria of binary and ternary mixtures of supercritical carbon dioxide with tetradecanoic acid and docosane up to 43 MPa and 393 K: cosolvency effect and miscibility windows

Isothermal pressure (p)-mass fraction (w) phase diagrams were measured for CO₂ + tetradecanoic acid at six temperatures from 328.2 K to 373.2 K and for CO₂ + docosane at four temperatures from 343.2 K to 393.2 K as well as isobaric temperature (T)-mass fraction (w) phase diagrams for both systems at 34.5 MPa. In addition the isothermal and isobaric Gibbs phase prisms at 373.2 K and 34.5 MPa respectively were determined for the ternary system CO₂ + tetradecanoic acid + docosane, and and isobaric miscibility window was found between 333 K and 385 K at 34.5 MPa.     

A novel channel-wall engineering strategy for two-dimensional cationic covalent organic frameworks: Microwave-assisted anion exchange and enhanced carbon dioxide capture

A novel channel-wall engineering strategy of the porous materials cationic covalent organic frameworks(COFs)is established based on rapid microwave-assisted anion exchange reaction and utilized to prepare a set of new COFs.Due to the interaction between the carbon dioxide(C02)and the acetate anion,the resulting SJTU-COF-AcO shows greatly enhanced carbon dioxide capacity up to 1.7 times of the pristine COF.The effect of the counteranions to CO2 capacity in the cationic COFs is investigated for the first time,which demonstrates that our channel-wall engineering strategy is a promising way to tailor the property of COFs for high CO2 capacity.     

低碳烷烃与二氧化碳催化转化研究进展

页岩气革命为低碳经济发展提供了重要契机.在低碳烷烃(甲烷和乙烷)催化转化过程中,以二氧化碳作为氧化剂参与反应,通过C-H键的选择性活化可将页岩气转化为优质化工原料——合成气和乙烯,是一种低碳烷烃转化与二氧化碳资源化利用的工艺路线.本文总结了近年来甲烷干重整与乙烷和二氧化碳反应中与C-H键活化相关的研究进展,分析了甲烷干...     

反应气中活化后的镍酸镧用于二氧化碳加氢生成甲烷

采用柠檬酸法制备了钙钛矿镍酸镧,并将其作为催化剂的前躯体用于二氧化碳甲烷化反应中。催化剂在400℃~700℃温度下反应气中进行活化处理。活化过程中生成了金属镍颗粒和碳酸氧化镧。金属镍呈高度分散状并被碳酸氧化镧包裹,这种现象有助于反应在400℃和500℃的高温下仍保持高活性和稳定性。XRD、XPS、TEM和H₂-TPD等表征测试表明,在活化过程中生成的碳酸氧化镧对反应起到了至关重要的作用。