乙醇-二氧化碳重整制氢研究现状

乙醇-二氧化碳重整技术可以有效利用及转化大气中的温室气体二氧化碳,同时又可制取低碳氢比的合成气,为F-T合成等提供理想原料。乙醇-二氧化碳重整反应过程复杂,通过调节反应条件、选择合适的催化剂可以控制反应的产物。重点分析反应热力学,概述贵金属和非贵金属催化剂的催化作用,并探讨工艺条件对目标产物选择性的影响,展望乙醇-二氧化碳重整制氢的发展趋势和面临的挑战。

Carbon dioxide-expanded ethanol-assisted synthesis of carbon-based metal composites and their catalytic and electrochemical performance in lithium-ion batteries

Highly dispersed metals,metal oxides and their composites on substrates have received considerable interest in catalysis and lithium-ion batteries,because of their superior properties compared with their single-component counterparts.In this review,we introduce the properties of supercritical carbon dioxide（scCO2） expanded ethanol,such as low viscosity,near-zero surface tension and high diffusivity.We discuss the deposition procedure and formation mechanism of carbon-based composites in scCO2-expanded ethanol.This method has been used to fabricate several carbon-based composites,such as metal and metal oxide composites deposited on zero-dimensional colloidal carbon,one-dimensional carbon nanotubes,two-dimensional graphene,and three-dimensional hierarchical porous carbon.These materials and their performance as anodic materials for lithium-ion batteries will also be reviewed.

High-pressure Phase Equilibria for Binary Ethanol System Containing Supercritical CO_2

High-pressure phase behavior of supercritical (SC) CO2+ethanol system was investigated at 333.2 K,348.2K, 353.2K, 368.2K, 413.2K and 453.2K and pressure from 2.0MPa to 14.3MPa. The measurement was carried out in a cylindrical autoclave with a moveable piston and a window for adjustment and observation of phase equilibria at given T and p. The samples were taken from two coexisting phases and were analyzed to obtain their compositions. It is shown that the solubility of SC CO2 in ethanol increases drastically with pressures at the given temperature, but the content of ethanol in CO2-rich phase increase faintly.

Modeling and Kinetic Study on Absorption of CO2 by Aqueous Solutions of N-methyldiethanolamine in a Modified Wetted Wall Column

To get more accurate kinetic data of the absorption of CO2 into aqueous solution of N-methyldiethanolamine,a wetted wall column was modified to more uniformly distribute the liquid on the column surface and gas in the absorbing chamber and change the length of the column.The average liquid film thickness and the liquid-phase mass transfer coefficient were measured,and a correlation for the Sherwood number,Reynolds number and Schmidt number was obtained for the modified wetted wall column.The equilibrium concentrations in chemical reactions were calculated with a minor absolute error for calculating the rate constant more accurately.A mathe-matical model for the CO2 absorption was established based on the diffusional mass transfer accompanied with parallel reversible reactions,and the partial differential equation was solved by Laplace transform.An analytical ex-pression for the concentration of carbon dioxide as a function of time and penetration depth in liquid film and the average interphase mass transfer rate was obtained.This model was also used to calculate the rate constant for a second-order reaction,which was in good agreement with reported data.

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.

CO_2-甲醇和CO_2-乙醇体系的交叉缔合模型

在统计缔合流体理论(statistical associating fluid theory,SAFT)的基础上,将二氧化碳(CO2)处理为似缔合分子,考虑醇羟基之间的自缔合作用,以及CO2分子与醇羟基之间的交叉缔合作用,提出了适用于CO2-醇类体系的交叉缔合模型.应用该模型研究了CO2-甲醇和CO2-乙醇体系从低温低压到高温高压的相平衡性质.p-x和p-ρ相图的计算值与实验值吻合良好.研究表明,考虑CO2与甲醇和乙醇分子之间的交叉缔合对Helmholtz自由能的贡献,可显著改善相平衡性质的计算结果,并避免模型对低温区间中三相平衡和三相点的错误预测.

Study on Critical Properties for CO_2+Cosolvent Binary System and Ternary System

The performance of supercritical fluid (SCF) as a solvent can be greatly affected by addition of anentrainer to the system. In this study, a constant volume visual method is used to measure the critical point ofCO2+n-butyraldehyde, CO2+ i-butyraldehyde and CO2+alcohol binary systems and CO2+entrainer+trisodiumsalt of tri-(m-sulfonphenyl)phosphine (TPPTS) ternary systems, which provides us good theoretical basis for super-critical extraction and chemical reaction. The relationship between critical point and concentration of the entrainerare discussed. The phase behavior of binary system and that of ternary system are compared. The relationshipbetween the concentration of TPPTS and critical point of binary systems are also discussed.

Absorption Rate of CO_2 into MDEA Aqueous Solution Blended with Piperazine and Diethanolanline

Absorption rate of CO2 into aqueous solution of N-methyldiethanolamine (MDEA) blended with diethanolamine (DEA) and piperazine (PZ) was studied and a kinetic model was established. It is shown that homogeneous activation mechanism could explain this absorption process. The absorption rate coefficients of carbon dioxide into MDEA aqueous solution blended with DEA, PZ or DEA+PZ were compared with each other. The results demonstrated that the different activation effect of DEA, PZ and DEA+PZ on the carbon dioxide absorption comes from the difference in CO2 combination rate, transport of PZ and DEA to MDEA and the regeneration rate of PZ and DEA.

Process simulation and analysis of carbon capture with an aqueous mixture of ionic liquid and monoethanolamine solvent

This study investigated the prospect of using aqueous mixture of 1-butylpyridinium tetrafluoroborate （[Bpy][BF4]） ionic liquid （IL） and monoethanolamine （MEA） as solvent in post-combustion CO2 capture （PCC） process. This is done by analysis of the process through modelling and simulation. In literature, reported PCC models with a mixture of IL and MEA solvent were developed using equilibrium-based mass transfer approach. In contrast, the model in this study is developed using rate-based mass transfer approach in Aspen Plus. From the results, the mixed aqueous solvent with 5-30 wt% IL and 30 wt% MEA showed 7%-9% and 12%-27% less specific regeneration energy and solvent circulation rate respectively compared to commonly used 30 wt% MEA solvent. It is concluded that the ｜L concentration （wt%） in the solvent blend have significant impact on specific regeneration energy and solvent circulation rate. This study is a starting point for further research on technical and economic analysis of PCC process with aqueous blend of IL and MEA as solvent.

Microalgae for Renewable Energy： Is it a Solution for Global Warming？

Microalgae could be a new sustainable energy source substituted for petroleum. They can produce high value biodiesel, bioethanol, bio-hydrogen, biogas, and that they are able to use waste water and nutrients, allowing for integration of such processes with waste treatment. Open ponds in hectares of area, could remove excess CO2 in atmosphere with photosynthesis. Large scale microalgal production in fields which are not suitable for agriculture could be a solution for CO： capturing from the atmosphere. Sea water could be used for the culture medium not to consume the fresh water. However microalgae reduce the atmospheric CO： while producing the organic material, using the biomass for either fuel production or food, feed, fertilizer, come out with CO2 release to the atmosphere, when burned by the engine, body and/or bacterial activities. So, microalgal growth can＇t reduce the CO2 however makes an important contribution to keep the atmospheric CO2 level stable. Long term solution for removing the CO2, could be possible with making durable biomaterials with microalgal biomass and capture the atmospheric CO2 by fixing into the materials and interrupt the carbon cycle for a long while.

Adsorption equilibrium of citric acid from supercritical carbon dioxide/ethanol on cyano column

Supercritical adsorption equilibrium has a significant role in defining supercritical adsorption behavior. In this paper, the adsorption equilibrium of citric acid from supercritical CO2/ethanol on a cyano column was systematically investigated with the elution by characteristic point method. Equilibrium loading was obtained at 313.15 K and 321.15 K with supercritical CO2/ethanol densities varying from 0.7068 g·cm-3to 0.8019 g·cm-3. The experimental results showed that the adsorption capacity of citric acid decreased with increasing temperature and increasing density of the supercritical CO2/ethanol mobile phase. The adsorption equilibrium data were fitted well by the Quadratic Hill isotherm model and the isotherms showed anti-Langmuir behavior. The monolayer saturation adsorption capacity of citric acid is in the range of 44.54 mg·cm-3to 64.66 mg·cm-3with an average value of 56.86 mg·cm-3.

Investigation of the interfacial properties for CO_2-methanol and CO_2-ethanol mixtures

An equation of state (EOS) applicable for the interfacial properties of CO2-methanol and CO2-ethanol mixtures was established by combining the cross-association EOS and the density gradient theory (DGT). The correlated surface tensions of CO2-ethanol mixtures agreed well with the experimental data. The results illustrated the temperature and pressure dependence of the cross-association between CO2 and alcohol hydroxyls in the whole vapor-liquid surface,and the influence of the cross-association on the calculation of the surface tensions of binary mixtures.