Thermodynamic modeling of CO2 and H2S solubilities in aqueous DIPA solution, aqueous sulfolane-DIPA solution, and aqueous sulfolane-MDEA solution with electrolyte NRTL model

A thermodynamic model developed for CO₂ and H₂S solubilities in aqueous MDEA solution is extended to cover CO₂ and H₂S solubilities in aqueous DIPA solution, aqueous sulfolane-DIPA solution, and aqueous sulfolane-MDEA solution. The model makes use of the 2009 version of the electrolyte NRTL model for liquid phase activity coefficient calculations and the PC-SAFT equation of state for vapor phase fugacity coefficient calculations. The NRTL binary parameters for the molecule-electrolyte pairs required for the H₂O-DIPA-CO₂ ternary and the H₂O-sulfolane-DIPA-CO₂ quaternary are regressed against the solubility data of CO₂ in aqueous DIPA solution and aqueous sulfolane-DIPA solution, respectively. The NRTL binary parameters for the molecule-electrolyte pairs required for the H₂O-DIPA-H₂S ternary and the H₂O-sulfolane-DIPA-H₂S quaternary are regressed against the solubility data of H₂S in aqueous DIPA solution and aqueous sulfolane-DIPA solution simultaneously. The NRTL binary parameters for the electrolyte-electrolyte pairs involved in the H₂O-DIPA-CO₂-H₂S quaternary are regressed against the solubility data of the acid gas mixtures in aqueous DIPA solution. Likewise, the NRTL binary parameters for the sulfolane-electrolyte pairs required for the H₂O-sulfolane-MDEA-CO₂ quaternary and the H₂O-sulfolane-MDEA-H₂S quaternary are regressed against the solubility data of the acid gases in aqueous sulfolane-MDEA solution. The predicted enthalpies of acid gas absorption are compared favorably with the literature data available for the H₂O-DIPA-CO₂ system, the H₂O-DIPA-H₂S system, and the H₂O-sulfolane-MDEA-CO₂ system.     

Enthalpies of absorption and solubility of CO2 in aqueous solutions of methyldiethanolamine

A flow mixing unit using a SETARAM C-80 calorimeter, developed for measuring the enthalpy of solution of two fluids, has been used to measure enthalpies of absorption of carbon dioxide in a 30 wt.% aqueous solution of methyldiethanolamine (MDEA) at three temperatures 313.15, 353.15, 393.15 K and three pressures 2.0, 5.0, 10.0 MPa. We have established that the effect measured by calorimetry corresponds not only to the absorption of CO₂ in the aqueous solution but also to the vaporisation of water into the carbon dioxide depending on the temperature and the pressure of the experiment. The enthalpies measured by calorimetry were compared with those calculated from solubility measurements and a reasonable agreement within the accuracy of measurement and calculation was found.     

CO2/H2 separation by facilitated transport membranes immobilized with aqueous single and mixed amine solutions: Experimental and modeling study

An experimental and theoretical analysis to separate CO₂ using facilitated transport membranes immobilized with different aqueous single and mixed amine solutions have been performed. The membranes containing monoethanolamine (MEA), diethanolamine (DEA), monoprotonated ethylenediamine (EDAH⁺) and piperazine (PZ), as well as aqueous blends of PZ with MEA, DEA or EDAH⁺ were considered. The aqueous solution of PZ showed the highest CO₂ permeation rate with respect to other single amine solutions. Therefore blends of PZ with MEA, DEA and EDAH⁺ increased the permeance of carbon dioxide through mixed amine membranes.     

Synthesis of oxazolidinones in supercritical CO2 under heterogeneous catalysis

Basic alumina efficiently promotes the reaction of propargylamines with scCO₂ for the synthesis of variously substituted oxazolidinones that, after catalyst filtration, are easily isolated by methanol crystallization.     

过渡金属催化不饱和烃与二氧化碳的羧化反应研究与进展

CO₂是一种无毒、廉价易得、储量丰富的可再生资源,通过化学方法将其转化为具有高附加值的化学品已成为实现可持续发展的战略性课题。其中,以CO₂作为羧化试剂合成羧酸及其衍生物的研究已成为CO₂催化活化领域的研究热点。本文按照不同过渡金属催化的不饱和烃与CO₂的羧化反应,分类归纳了近些年来的羧化反应研究进展。     

CO2还原反应二维电催化剂研究进展

二氧化碳(CO₂)电化学还原为高附加值化学品在解决CO₂过量排放上具有极好的应用前景,但这需要开发先进的电催化剂来降低CO₂活化能并提高还原产物的选择性。受益于独特的几何结构,二维材料在电催化CO₂还原反应中得到了广泛研究。本综述将系统介绍应用于CO₂还原反应的二维电催化剂上的最新进展。我们也将揭示特征结构与电催化性能之间的构效关系。我们希望本文可以为开发CO₂还原电催化剂提供有益的指导。     

Electrochemical reduction of CO2 with high current density in a CO2 + methanol medium II. CO formation promoted by tetrabutylammonium cation

The cation of the supporting electrolyte was found to play an important role in the electrochemical reduction of highly concentrated CO₂ in a CO₂ + methanol medium. Electroreduction of CO₂ with tetrabutylammonium (TBA) salts yielded CO as the main product, while methyl formate was predominantly formed when lithium salts were used as supporting electrolytes. The latter supporting electrolytes showed a higher overvoltage than the former. When TBA salt was used, the reduction of CO₂ was catalysed by TBA ion to yield CO^−.₂. This intermediate may be stabilized by forming an ion pair, {TBA⁺---CO^−.₂}, or by being adsorbed on the electrode surface as CO^−._2ad. Then CO^−.₂ reacts with CO₂ to produce CO. The hydrophobic atmosphere at the electrode provided by TBA ion may be adequate for CO production. Lithium ion, on the other hand, suppressed the reduction of CO₂.     

乙二醇溶剂热合成的CeO2的可逆氧化还原性及CO2捕获性能

利用乙二醇的还原性,采用乙二醇溶剂热法制备了表面具有丰富氧空穴的CeO₂-GST纳米晶,对其进行了X射线衍射、透射电镜、X射线光电子能谱、原位H₂还原-O₂氧化循环和CO₂原位红外漫反射表征,并研究了其可逆氧化还原性及CO₂捕获性能. 结果表明,与CeO₂-nanorod和柠檬酸溶胶法合成的CeO₂-CA样品相比,CeO₂-GST纳米晶具有最好的可逆氧化还原性能和循环稳定性,同时在50 ℃下具有最好的CO₂吸附性能（149 μmol/g）. 利用原位红外漫反射光谱研究了CO₂在还原CeO₂表面的吸附情况,发现CO₂主要以双齿碳酸盐和桥连碳酸盐两种形式吸附在CeO₂表面,其中桥连碳酸盐物种不稳定,He吹扫可脱附. 此外,CO₂在CeO₂-nanorod上还会生成稳定的甲酸盐和单齿碳酸盐物种.     

Experimental study of high pressure phase equilibrium of (CO2 + NO2/N2O4) mixtures

Experimental bubble pressure, as well as liquid density of (CO₂ + NO₂/N₂O₄) mixtures are reported at temperatures ranging from (298 to 328.45) K. Experiments were carried out using a SITEC high-pressure variable volume cell. Transition pressures were obtained by the synthetic method and liquid density was deduced from measurement of the cell volume. Correlation of experimental results was carried out without considering chemical equilibrium of NO₂/N₂O₄ system. (Liquid + vapour) equilibrium was found to be accurately modelled using the Peng–Robinson equation of state with classical quadratic mixing rules and with a binary interaction coefficient k_ij equal to zero. Nevertheless, modelling of liquid density values was unsatisfactory with this approach.     

Composite hollow fiber membranes for CO2 capture

Composite hollow fibers membranes were prepared by coating poly(phenylene oxide) (PPO) and polysulfone (PSf) hollow fibers with high molecular polyvinylamine (PVAm). Two procedures of coating hollow fibers outside and respective inside were investigated with respect to intrinsic PVAm solution properties and hollow fibers geometry and material.The influence of operating mode (sweep or vacuum) on the performances of membranes was investigated. Vacuum operating mode gave better results than using sweep because part of the sweep gas permeated into feed and induced an extra resistance to the most permeable gas the CO₂. The composite PVAm/PSf HF membranes having a 0.7–1.5 μm PVAm selective layer, showed CO₂/N₂ selectivity between 100 and 230. The selectivity was attributed to the CO₂ facilitated transport imposed by PVAm selective layer. The CO₂ permeance changed from 0.006 to 0.022 m³(STP)/(m² bar h) in direct correlation with CO₂ permeance and separation mechanism of the individual porous supports used for membrane fabrication. The multilayer PVAm/PPO membrane using as support PPO hollow fibers with a 40 nm PPO dense skin layer, surprisingly presented an increase in selectivity with the increase in CO₂ partial pressure. This trend was opposite to the facilitated transport characteristic behaviour of PVAm/porous PSf. This indicated that PVAm/PPO membrane represents a new membrane, with new properties and a hybrid mechanism, extremely stable at high pressure ratios. The CO₂/N₂ selectivity ranged between 20 and 500 and the CO₂ permeance from 0.11 to 2.3 m³(STP)/(m² bar h) depending on the operating conditions.For both PVAm/PSf and PVAm/PPO membranes, the CO₂ permeance was similar with the CO₂ permeance of uncoated hollow fiber supports, confirming that the CO₂ diffusion rate limiting step resides in the properties of the relatively thick support, not at the level of 1.2 μm thin and water swollen PVAm selective layer. A dynamic transfer of the CO₂ diffusion rate limiting step between PVAm top layer and PPO support was observed by changing the feed relative humidity (RH%). The CO₂ diffusion rate was controlled by the PPO support when using humid feed. At low feed humidity the 1.2 μm PVAm top layer becomes the CO₂ diffusion rate limiting step.     

Absolute absorption cross section measurements of CO2 in the wavelength region 163–200 nm and the temperature dependence

Laboratory measurements of the absorption cross section of CO₂ at the temperatures 195 and 295 K have been made throughout the wavelength region 163–200 nm by using a high resolution grating spectrometer. Cross sections at 195 K are smaller than those at 295 K, and the band structures are more emphasized as expected. In combining with our previous measurements [J. Quant. Spectrosc. Radiat. Transfer, 55 (1996) 53], the absorption cross sections of CO₂ are available in the wavelength region 117.8–200.0 nm at 295 K and 117.8–192.5 nm at 195 K.     

CO2/NIR light dual-controlled nanoparticles for dsDNA unzipping

Both of carbon dioxide(CO2)and near-infrared(NIR)light as triggers for non-invasive remotely control are attracting wide attentions due to their good biocompatibility and easy operation.Here,CO2/NIR light dual controlled nanoparticles are proposed to remotely regulate the unzipping of dsDNA by using imidazole functionalized conjugated polymer nanoparticles(imidazole-CPNs).The dsDNA successfully coats on the shell of imidazole-CPNs to form imidazole-CPNs/dsDNA assembly due to intensively electrostatic interaction triggered by CO2.Furthermore,the unzipping process of dsDNA is remotely controlled by NIR light based on the photothermal effect,and it can be readily monitored by the fluorescence intensity of ethidium bromide(EB)and CD spectra of dsDNA.Thus,dual stimulation responsive imidazole-CPNs effectively control dsDNA unzipping under CO2 stimulus and NIR light,promising a new direction in the biological applications of DNA,such as the treatments of diseases caused by gene duplication abnormality.     

Synthesis of Dimethyl Carbonate from CO2 , Methanol, and Epoxides Using Re（CO） 5 Cl/K2 CO3 as Catalyst System

IntroductionOver the past few years, dimethyl carbonate(DMC) has been proven to be an efficientmethylating,methoxylating, and methoxycarbonylating agent inorganic syntheses, in which DMC is used to replace thetoxic methyl halides, dimethyl sulfate or carb     

CO2在纳米SiO2/TiO2悬浮体系中的光催化还原

用水热法合成了氧化硅改性的具有高比表面积、高催化活性的锐钛型二氧化钛, 并在其悬浮体系中将CO₂光催化还原合成甲醇. 采用XRD, TEM, 物理吸附, UV-Vis吸收光谱和FTIR等表征手段对催化剂结构特征进行了研究. 结果表明: 添加氧化硅后, 氧化硅和二氧化钛之间形成Si—O—Ti键, 抑制了TiO₂晶粒生长, 提高了锐钛型TiO₂的比表面积, 且随着含硅量的增加, SiO₂/TiO₂的UV吸收逐步蓝移, 禁带宽度增加. 还原反应结果表明: SiO₂/TiO₂具有光催化还原活性, 且随着含硅量的增加先增加后减小, 当SiO₂质量分数为3.5%时, SiO₂/TiO₂复合催化剂反应活性最强, 5 h内甲醇产量可达到21.0 mg/L, 并有少量甲醛生成.     

从二氧化碳和环氧丙烷及异氰酸酯合成聚亚氨碳酸酯

研究了二氧化碳，环氧丙烷和异氰酸酯的共聚合反应．并考察了反应条件，异氰酸酯加入量对共聚产率及共聚物的特性粘数、分子量分布及热稳定性的影响．实验发现，引入异氰酸酯具有扩链作用，而引入二异氨酸酯则具有明显的文化交联作用．由共聚物水解试验和光谱研究结果表明，共聚反应生成的是聚亚氨碳酸酯，而不是聚氨基甲酸酯．这种聚亚氨碳酸酯比聚碳酸亚丙酯具有较高的热稳定性．     

高压下CO2-乙醇二元系统的气液平衡

在带有可视石英窗的可变体积高压釜内,在60－180 ℃温度范围、 4.0－14.5 MPa压力范围下测定了CO2和乙醇二元系统的相平衡数据.根据实验结果预测了pc,Tc,xc.用Peng Robinson方程和Wong Sandler混合规则进行了拟合,所得结果与实验数据基本相符.     

Synthesis of carbonates directly from 1 atm CO2 and alcohols using CH2Cl2

We introduced here a new one-pot, general procedure for the preparation of dialkyl carbonates from alcohols in a straightforward fashion under 1 atm pressure of CO₂ using Cs₂CO₃ and CH₂Cl₂ as key reagents.     

Solubility of CO2 in CO2-philic oligomers; COSMOtherm predictions and experimental results

We report the solubility of carbon dioxide in four physical solvents and compare our data to predicted phase behavior using the conductor-like screening model for real solvents (COSMO-RS) formalism. The solubility data are presented in pressure-composition (Px) diagrams as well as Henry's law coefficients on a wt% basis at 298.15 K. The oligomers presented in this study are poly ethylene glycol di-methyl ether (PEGDME), perfluoro polyether (PFPE), poly di-methyl siloxane (PDMS), and poly propylene glycol di-methyl ether (PPGDME), which is a new solvent designed for this application by our group. These oligomers had 2–5 repeat units. We assess these four oligomers for capturing CO₂ from high-pressure streams. The COSMO-RS formalism is able to qualitatively and to some extent quantitatively describe solubilities of CO₂ in each of the oligomers.     

Experimental analysis and modeling of CO2 solubility in AMP (2-amino-2-methyl-1-propanol) at low CO2 partial pressure using the models of Deshmukh–Mather and the artificial neural network

The equilibrium solubility data for CO₂ in aqueous solution of AMP have been determined at temperatures from 293 K to 323 K, partial pressures from 17.47 kPa to 69.87 kPa and concentrations of AMP from 1 M to 4 M. The experimental results show that the solubility of CO₂ in AMP increases with partial pressure and decreases with temperature and concentration of solvent. Two different mathematical models have been used to analyze the solubility of CO₂ in AMP including those of Deshmukh–Mather and the artificial neural network. The modeling results indicate that the neural network modeling provides a better prediction of experimental CO₂ loadings than the Deshmukh–Mather model when compared with experimental results in this work. Therefore, this new modeling method can be useful in predicting the results of CO₂ absorption and its accuracy is comparable with those of thermodynamic models which are used widely.     

新型双子表面活性剂在H2S和CO2盐水溶液中对碳钢的缓蚀性能

合成了一系列含有羟基的双子表面活性剂:1,3-双(十二烷基二甲基氯化铵)-2-丙醇(12-3OH-12),1,3-双(十四烷基二甲基氯化铵)-2-丙醇(14-3OH-14),1,3-双(十六烷基二甲基氯化铵)-2-丙醇(16-3OH-16)和1,3-双(十八烷基二甲基氯化铵)-2-丙醇(18-3OH-18).采用静态失重法、极化曲线和交流阻抗技术研究了其在H2S/CO2腐蚀环境中对L360钢的缓蚀作用.结果表明,三种研究方法取得的结论是一致的,缓蚀效果为14-3OH-14>12-3OH-12>16-3OH-16>18-3OH-18.其中,12-3OH-12和14-3OH-14都表现出很好的缓蚀效果,在35mg·L-1的较低浓度下缓蚀率就达95%以上.极化曲线测试结果表明n-3OH-n(n=12,14,16,18)型双子表面活性剂是一种以阳极抑制为主的混合型缓蚀剂.除n=18外,其它三种双子表面活性剂n-3OH-n(n=12,14,16)在L360钢表面的吸附服从朗缪尔等温线,并且属于物理和化学混合吸附.提出了一个用来解释双子表面活性剂在H2S/CO2溶液中缓蚀机理的吸附模型.