Conversion of carbon dioxide to valuable petrochemicals:An approach to clean development mechanism

The increase of atmospheric carbon dioxide and the global warming due to its greenhouse effect resulted in worldwide concerns. On the other hand, carbon dioxide might be considered as a valuable and renewable carbon source. One approach to reduce carbon dioxide emissions could be its capture and recycle via transformation into chemicals using the technologies in C1 chemistry. Despite its great interest, there are difficulties in CO2 separation on the one hand, and thermodynamic stability of carbon dioxide molecule rendering its chemical activity low on the other hand. Carbon dioxide has been already used in petrochemical industries for production of limited chemicals such as urea. The utilization of carbon dioxide does not necessarily involve development of new processes, and in certain processes such as methanol synthesis and methane steam reforming, addition of CO2 into the feed results in its utilization and increases carbon efficiency. In other cases, modifications in catalyst and/or processes, or even new catalysts and processes, are necessary. In either case, catalysis plays a crucial role in carbon dioxide conversion and effective catalysts are required for commercial realization of the related processes. Technologies for CO2 utilization are emerging after many years of research and development efforts.

Rule of 100:An inherent limitation or performance measure in oxidative coupling of methane?

The oxidative coupling of methane over La203/CaO type-catalyst in a fixed-bed reactor is studied under a wide range of operating conditions （973〈T〈 1103 K, 55〈 Ptotal 〈220 kPa, and 3.7〈 mcat/VTp 〈50 kg.s/m^3）. A ten-step kinetic model incorporating all main products was used to predict the behavior of the system. Methane conversions and C2 selectivities were calculated by varying methane to oxygen ratios in the feed under different operating conditions which were also compared with the rule of 100. The results show that deviation from this rule depends on the operating conditions. Within the range studied, an increase in pressure, temperature and contact time results in smaller deviation from the rule. This rule is best approximated when the catalyst operates near its optimal performance. For negative deviations, common to the most catalysts, it is found that the optimal performance should occur at methane conversion levels lower than 50%. A plot of selectivity versus conversion for high-yield reported performance data of a large variety of catalysts shows that data points concentrated roughly in 20%-50% methane conversion region, confirming the generality and prediction of modeling.

Multi-response optimization of MIL-101 synthesis for selectively adsorbing N-compounds from fuels

In this work,MIL-101,a metal organic framework,has been synthesized and examined in the adsorptive denitrogenation process.Due to the importance of adsorption capacity and selectivity,the effects of synthesis parameters including metal type,reagent ratio,time and temperature on the MIL-101 performance were investigated by measuring quinoline(QUI)separation from iso-octane.The optimum conditions were determined using a Taguchi experimental design and the multiresponse optimization(multivariate statistical)method.Based on the arithmetic mean of normalized QUI adsorption capacity and QUI/dibenzothiophene(DBT)selectivity,as the objective function,the optimum value of synthesis parameters were found to be manganese as metal type in the structure,180°C for synthesis temperature,15h for synthesis time and 1.00 for reagent molar ratio.Under these conditions,QUI adsorption capacity and QUI/DBT selectivity were 19.3 mg-N/g-Ads.and 24.6,respectively.Accordingly,the arithmetic mean between normalized values of these measured parameters was equal to 1.10,which is in good agreement with the predicted value.The MIL-101 produced under optimum conditions was characterized by determining its specific surface area,X-ray powder diffraction patterns and Fourier transform infrared spectroscopy.Finally,isotherm and kinetic studies indicate that the Langmuir isotherm and pseudo-first-order model can successfully describe the experimental data.

Carbon dioxide sequestration in petrochemical industries with the aim of reduction in greenhouse gas emissions

The mitigation of greenhouse gas emissions to acceptable levels is arguably the greatest environmental challenge these days.Vast utilization of fossil fuels and forest destruction are main causes of CO_(2) increase in the atmosphere.Carbon dioxide sequestration that consists of separation,transportation and utilization or storage of CO_(2),is one way for reduction of its emission,in which the most costly section is separation.Different methods can be used for carbon dioxide separation such as absorption,mem-brane separation,adsorption and cryogenic distillation.Economic,technical and environmental issues should be considered in selection of the technology for particular application.Carbon dioxide concentration,temperature,pressure andflow rate are influential operating parameters in the selection of the appropriate separation method.Nowadays,absorption is the worldwide industrial separa-tion method.New researches are focused on developing new stable solvents and efficient column configuration with suitable internals to minimize pressure drop.Membrane separation and adsorption(PSA type)are other long-term alternatives that can increase separation efficiency and decrease separation cost.The level of energy consumption in various separation methods are in the order:chemical absorption>physical absorption>membrane separation.Because of high investment costs,current separation technologies are suitable for large concentrated sources.In the present paper,different processes for carbon dioxide separation are investigated and compared.Available technologies and commercial plants for CO_(2) sequestration are provided.