Thermodynamic analysis of carbon dioxide reforming of methane in view of solid carbon formation

A thermodynamic equilibrium analysis on the multi-reaction system for carbon dioxide reforming of methane in view of carbon formation was performed with Aspen plus based on direct minimization of Gibbs free energy method. The effects of CO₂/CH₄ ratio (0.5-3), reaction temperature (573-1473 K) and pressure (1-25 atm) on equilibrium conversions, product compositions and solid carbon were studied. Numerical analysis revealed that the optimal working conditions for syngas production in Fischer-Tropsch synthesis were at temperatures higher than 1173 K for CO₂/CH₄ ratio being 1 at which about 4 mol of syngas (H₂/CO = 1) could be produced from 2 mol of reactants with negligible amount of carbon formation. Although temperatures above 973 K had suppressed the carbon formation, the moles of water formed increased especially at higher CO₂/CH₄ ratios (being 2 and 3). The increment could be attributed to RWGS reaction attested by the enhanced number of CO moles, declined H₂ moles and gradual increment of CO₂ conversion. The simulated reactant conversions and product distribution were compared with experimental results in the literatures to study the differences between the real behavior and thermodynamic equilibrium profile of CO₂ reforming of methane. The potential of producing decent yields of ethylene, ethane, methanol and dimethyl ether seemed to depend on active and selective catalysts. Higher pressures suppressed the effect of temperature on reactant conversion, augmented carbon deposition and decreased CO and H₂ production due to methane decomposition and CO disproportionation reactions. Analysis of oxidative CO₂ reforming of methane with equal amount of CH₄ and CO₂ revealed reactant conversions and syngas yields above 90% corresponded to the optimal operating temperature and feed ratio of 1073 K and CO₂:CH₄:O₂ = 1:1:0.1, respectively. The H₂/CO ratio was maintained at unity while water formation was minimized and solid carbon eliminated.     

二氧化碳加氢直接合成二甲醚的研究进展

综述了二氧化碳直接加氢合成二甲醚的研究进展及二氧化碳加氢合成二甲醚催化剂的研究现状。     

An Ru-based catalytic membrane reactor for dry reforming of methane—its catalytic performance compared with tubular packed bed reactors

The methane reforming with CO₂ seems to be a promising reaction system useful to reduce the greenhouse contribution of both gases into the atmosphere. On this basis, and considering the potentiality of this reaction system, the dry reforming reaction has been carried out in an Ru-based ceramic tubular membrane reactor, in which two Ru depositions have been performed using the co-condensation technique. Experimental results in terms of CH₄ and CO₂ conversion versus temperature during time are presented, as well as product selectivity and carbon deposition. These experiments have also been carried out using a traditional reactor. A comparison with literature data regarding dry reforming reaction is also provided. Experimental evidence points out a good catalyst activity for the methane dry reforming reaction, confirming the potentiality of a catalytic membrane applied to the reaction system.     

Thermodynamic Equilibrium Analysis of Propane Dehydrogenation with Carbon Dioxide and Side Reactions

A thermodynamic analysis of propane dehydrogenation with carbon dioxide was performed using constrained Gibbs free energy minimization method. Different reaction networks corresponding to different catalytic systems, including non-redox and redox oxide catalysts, were simulated. The influences of CO₂/C₃H₈ molar ratio (1–10), temperature (700–1000 K), and pressure (0.5–5 bar) on equilibrium conversion and product composition were studied. In the presence of CO₂ with a molar ratio of CO₂/C₃H₈ = 1, the temperature of dehydrogenation can be 30 K lower than that of dehydrogenation in the presence of steam (H₂O/C₃H₈ = 1) and about 50 K lower than that of simple dehydrogenation without dilution to achieve 60% propane conversion. It was found that the occurrence of dry reforming of propane and coke-forming side reactions could strongly impact the equilibrium product composition of the multireaction system and, therefore, these reactions should be kinetically controlled. Comparison of the simulated reactant conversions with those reported in the literatures revealed that the experimental conversion levels of propane are far below the corresponding equilibrium values due to rapid catalyst deactivation by coke, implying that research efforts should be directed toward formulation of more active and selective catalysts.     

Steam and Dry Reforming Processes Coupled with Partial Oxidation of Methane for CO2 Emission Reduction

CO₂ is thought to contribute to global climate change. A novel integrated process of steam methane reforming (SMR) and dry methane reforming (DMR) coupled to partial oxidation of methane (POX) has been developed that utilizes the compensating heat effects of DMR and POX and recycles a large amount of CO₂ to the DMR+POX section. Both SMR and the integrated process were simulated using Aspen Plus and were optimized to operate under their respective optimum operating conditions. Modified mitigation cost (MMC) was implemented as the evaluation method. The results demonstrate that the combined process is more efficient than the SMR process due to its reutilization of CO₂ and lower requirement of raw materials.     

生物质粗燃气自热重整调变的热力学分析

运用吉布斯自由能最小化方法对生物质粗燃气自热重整过程进行了热力学分析,研究了重整反应过程中的温度,O2/CH4摩尔比及焦油摩尔分数等因素对平衡产物组成的影响规律。研究结果表明:低温有利于CO歧化与加氢反应,而高温促进了CH4和CO2的转化,提高合成气H2+CO摩尔分数,降低H2/CO摩尔比。O2/CH4摩尔比的增加有利于生物质燃气从部分氧化反应向完全氧化反应转变,促进了CH4的重整反应而抑制了CO2的转化;O2/CH4摩尔比的增加降低了合成气H2+CO摩尔分数,降低了H2/CO摩尔比,在重整后的生物质粗燃气中,n(H2)/n(CO)≈1。积碳量随温度升高和O2/CH4摩尔比的增加逐渐减少,随着焦油(C10H8)物质的量的增加而增加。焦油物质的量增加提高了合成气中H2与CO摩尔分数,是重整反应的重要原料。优化的生物质燃气自热重整反应条件为温度1 023 K,O2/CH4摩尔比0.7,焦油摩尔分数<1%。     

二氧化碳和水蒸气重整制甲醇的热力学分析

二氧化碳和水蒸气重整制甲醇是有效利用二氧化碳资源的重要途径,具有重要的经济和环保意义。从热力学角度进行分析,找出合理的反应条件,以提高甲醇的选择性和收率,对指导CO2和H2O反应具有重要意义。文中基于Gibbs最小自由能原理对该体系的热力学平衡进行了相关计算,分析了温度、压力、原料配比H2O/CO2等条件对该反应体系平衡组成的影响。结果表明:改变温度对体系的平衡组成影响不大,而体系的平衡组成随着压力和原料配比H2O/CO2的增大而增大。得到优化反应条件为初始原料摩尔比n(H2O)/n(CO2)为7∶3,温度约为500 K,压力为8 MPa。这对二氧化碳水蒸气重整制甲醇反应条件的优化具有一定的指导价值。     

Redeposition in CO2 textile dry cleaning

Perchloroethylene (PER) is commonly used as cleaning solvent in the textile dry-cleaning industry but this chemical is toxic by nature. One of the potential PER replacements is carbon dioxide (CO₂), which is non-toxic, cheap, and widely available. Previous studies have indicated that the particulate soil removal with CO₂ is lower compared to that of PER. While the particulate soil removal of the CO₂ dry-cleaning was studied, it was found that redeposition of particulate soil occurs. Several experiments have been carried out to study and reduce this problem. In these experiments, textiles stained with different kinds of particulate soils were cleaned using a 25 L CO₂ dry-cleaning set-up. It was found that the redeposition level increases along with washing time, while rinsing has little influence. Modifying the filtration system by using scavenger textile, or adding a cellulose compound to the cleaning vessel as anti redeposition agent can significantly reduce redeposition.     

Mechanical action in CO2 dry cleaning

High-pressure carbon dioxide (CO₂) is a potential alternative for perchloroethylene (PER), a common but harmful textile dry cleaning solvent. Previous studies have indicated that the particulate soil removal with CO₂ is lower compared to that with PER, because of the low amount of mechanical action in CO₂. It is the objective of this study to get more insight in the influence of various types of mechanical action on the cleaning results in CO₂ dry cleaning. In the experiments, various mechanisms of mechanical action, such as rotating drum, CO₂ spray, and ultrasound were investigated. Several types of textiles stained with different kinds of particulate soils were cleaned using 25 L and 90 L CO₂ dry cleaning set-ups. The washing results show that liquid CO₂ spray may be a suitable additional mechanism to provide textile movement. The average CPI of CO₂ over all soils using the best combination of commercial machine and process was still 25% lower than the results with PER and 18% lower than the results with water, but 11% higher than K4 solvent while the average redeposition level was significantly lower, showing that CO₂ has a good prospect as an alternative solvent to replace PER. An endoscopic camera has been installed in the 25 L set-up to get an insight in the textile movement inside the rotating drum. The results show that no plug formation occurs and the textile movement in CO₂ is sluggish, which means that the mechanical movement of textile in CO₂ dry cleaning does not follow the simplified tumbling-movement model which was developed in a previous study, and the mechanical action is much less than predicted.     

A Comparative Study of Hydroxyapatite- and Alumina-Based Catalysts in Dry Reforming of Methane

The dry reforming of methane over hydroxyapatite- and alumina/magnesia (commercial Pural MG 30)-supported nickel catalysts was investigated. The catalytic performance of the catalysts prepared with fresh supports highly depended on the basicity, the metal-support interaction, and the metal particle size. Calcination of the supports at 1200 °C for 5 h made the catalysts less active because of specific surface area reduction and basicity destruction. However, this treatment allowed avoiding any further catalyst deactivation by thermal sintering and maintained excellent catalytic stability over 300 h of time-on-stream. These tests under simulated industrial conditions (high contact time and long time-on-stream) showed the competitiveness of the prepared catalysts in this important catalytic process.     

聚甲醛二甲醚反应热力学分析

聚甲醛二甲醚(DMM2—8)是一种有潜在应用价值的绿色柴油添加剂,可以采用三聚甲醛和甲醇为原料合成。用基团贡献法对聚甲醛二甲醚合成反应体系中主要反应的反应焓变、反应Gibbs自由能变和反应平衡常数以及多种基础热力学数据进行了估算。结果表明:在298.15—473.15 K,反应体系中三聚甲醛分解为甲醛单体的反应为吸热反应,升高温度有利于反应的进行,而甲醛与甲醇反应生成DMM2—8的反应为放热反应,随温度升高反应逐渐向不可自发进行转变;以上两步反应耦合后,在整个温度范围内为放热反应,升高温度使反应平衡常数减小,但反应均可自发进行。     

Structure and Catalytic Performance of Mg‐SBA‐15‐Supported Nickel Catalysts for CO2 Reforming of Methane to Syngas

A series of Mg‐modified SBA‐15 mesoporous silicas with different MgO contents were successfully synthesized by a simple one‐pot synthesis method and further impregnated with Ni. The Mg‐modified SBA‐15 materials and supported Ni catalysts were characterized by N₂ physisorption (BET), X‐ray diffraction (XRD), temperature‐programmed desorption of CO₂ (CO₂‐TPD), temperature‐programmed H₂ reduction (H₂‐TPR), and temperature‐programmed hydrogenation (TPH) techniques and used for methane dry reforming with CO₂. CO₂‐TPD results proved that the addition of Mg increased the total amount of basic sites which was responsible for the enhanced catalytic activity over the Mg‐modified Ni catalyst. The excellent catalytic stability of Ni/8Mg‐SBA‐15 was ascribed to less coking and higher stability of the Ni particle size due to the introduction of Mg.     

Thermodynamic equilibrium analysis on the dehydration of glycerol with monohydric alcohols to alkyl glyceryl ethers

Under the conditions of the feed of 400 moles of alcohol + 100 moles of glycerol, 313–573 K and 0.1 MPa, based on Gibbs free energy global minimization, an improved genetic algorithm was used for the thermodynamic equilibrium analysis on the synthesis processes of alkyl glyceryl ethers, respectively, from methanol + glycerol, ethanol + glycerol, isobutanol + glycerol, and tert-butanol + glycerol. The columnar stacking charts and three-dimensional contour graphs were used to compare the effects of temperature, pressure, and the feed ratio to the equilibrium conversion, product selectivity, and equilibrium composition. The basic laws of the synthesis processes of alkyl glycerol ethers in homogeneous and heterogeneous states were investigated in a wide temperature range. Through comparison, it was found that the isopropanol + glycerol system is easier to convert into alkyl glycerol ethers, followed by the ethanol + glycerol system. The methanol + glycerol system and tert-butanol + glycerol system are greatly affected by pressure and temperature, and their conversions and selectivities are relatively low.     

Roles of Surface and Bulk Lattice Oxygen in Forming CO2 and CO During Methane Reaction over Gadolinia-Doped Ceria

Temperature-programmed reaction of methane and temperature-programmed reduction were performed over gadolinia-doped ceria (GDC). It was found that CO₂ formation can occur at very much lower temperature than CO formation. The surface lattice oxygen acts as the active site for CH₄ adsorption. This active site has a dynamic characteristic due to the mobility of the lattice oxygen. The rates of CO and CO₂ formations can be controlled by the supply rate of the lattice oxygen from the GDC bulk; this supply rate depends on the mobility and the concentration of the bulk lattice oxygen. CO₂ formation is associated with the existing surface lattice oxygen while CO formation depends on the oxygen species coming from the bulk lattice during methane reaction.     

化学热力学分析中短缺组分概念的应用问题

本文从吉布斯自由概念的定义出发，指出了ΔＧ、ΔＧＴ在热力学分析中的使用条件。本着准确，直观，便利的应用原则，提出了应用于化学热力学分析中的短缺组分概念，并给出了这一概念的应用实例。     

Optimal design and operation of a natural gas tri-reforming reactor for DME synthesis

Korea Gas Corporation (KOGAS) is developing a new di-methyl-ether (DME) plant. Syngas is provided by natural gas tri-reforming, in a reactor consisting of a homogenous part where oxidation leads to a temperature increase required for the reforming reactions and a catalytic part where the reforming reactions take place. A first principle model for the tri-reforming reactor is developed. A kinetic mechanism is proposed combining homogeneous gas-phase reactions and heterogeneous catalytic reactions. The proposed model is systematically calibrated and validated with global sensitivity analysis followed by global parameter estimation against concentration measurements of a lab-scale prototype reactor and comparisons of the sensitivity of the outlet as a function of inlet composition and design parameters with experimental results. The validated model is finally used for the optimization of design variables such as length ratio of homogeneous and heterogeneous section and operational variables such as the feed composition.     

NiBa catalysts for CO2-reforming of methane

Ni–Ba catalysts supported on γ-Al₂O₃ for the dry reforming of methane were prepared, characterized and studied under reaction conditions. Ba incorporation inhibits the formation of Ni spinel. All the Ni–Ba catalysts studied are highly active for the CO₂-reforming of methane. However, the Ni–Ba catalyst with high Ba and Ni content was the most active and stable catalyst, due to the presence of accessible Ni particles stabilized by the formation of BaAl₂O₄.     

High-Performance Bimetallic Catalysts for Low-Temperature Carbon Dioxide Reforming of Methane

Catalytic dry reforming of methane (DRM) is a promising way for renewable syngas production due to the utilization of both CO₂ and CH₄ greenhouse gases. Current approaches were made to improve the catalytic activity and coke resistance by introducing a second metal into the Ni-based catalytic system. This bimetallic catalytic system showed a significant improvement in coke resistance due to the synergistic effect of both metals towards the reaction. This review summarizes recent developments in bimetallic catalysts in DRM which focused on the evaluation of catalysts, deactivation studies, and reaction mechanisms of developed bimetallic catalysts.     

Structure and reactivity of plasma treated Ni/Al2O3 catalyst for CO2 reforming of methane

The glow discharge plasma treated Ni/Al₂O₃ catalyst showed an excellent anti-coke property for CO₂ reforming of methane. Characterizations using X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (TPR), transmission electron microscopy (TEM), and CO adsorbed infrared spectroscopy (IR) were conducted to investigate the structure and reactivity of the plasma treated Ni/Al₂O₃ catalyst for CO₂ reforming of methane. It confirms that the plasma treatment of Ni precursor at room temperature followed by calcination thermally has a significant influence on the surface characteristics of the active phase. The plasma treated catalyst contains high concentration of close packed plane with improved Ni dispersion and enhanced Ni-alumina interaction, which lead to high catalytic activity and excellent resistance to formations of filamentous carbon and encapsulating carbon.     

Molecular Simulation Study for CO2 Clathrate Hydrate

The present work has concentrated on the structure of CO₂ hydrate in the NPT ensemble using SPC (simple point charge) intermolecular potential model of water by the Monte Carlo (MC) molecular simulation. A mixture of water and CO₂ placed arbitrarily in a cubic cell has been used as a model system to simulate the CO₂ clathrate hydrate at temperatures ranging from 150–280 K and pressure up to 10 MPa. The result shows that the obtained MC simulation agrees well with the results obtained by molecular dynamic (MD) simulation. The present work is also directed to the study of structure with TIP4P potential model of water.