甲烷自热重整制合成气热力学平衡分析

使用1stOpt2.5计算软件编程计算甲烷自热重整制合成气反应平衡组成,考察温度、原料比对体系组分平衡的影响。通过计算结果指出最适宜的反应条件,为甲烷自热重整制合成气催化剂的研究与开发提供热力学依据。     

催化部分氧化甲烷制合成气的平衡热力学研究

The catalytic partial oxidation of methane to syngas (CO H2) has been simulated thermodynamically with the advanced process simulator PRO/Ⅱ. The influences of temperature,pressure,CH4/O2 ratio and steam addition in feed gas on the conversion of CH4 selectively to syngas and heat duty required were investigated, and their effects on carbon formation were also discussed. The simulation results were in good agreement with the literature data taken from a spouted bed reactor.     

垃圾填埋气的资源化利用

我国城市垃圾中,大约70%采用卫生填埋的方式处理,填埋气数量巨大。有效利用填埋气中的能量,不仅能减少温室效应气体的排放,而且对我国能源安全意义重大。对垃圾填埋气的净化及其资源化利用现状进行了详细综述和分析,对未来发展方向给出了建议。     

化学链重整制合成气过程模拟

基于化学链重整原理,以甲烷为原料,运用Aspen Plus对化学链重整制合成气系统进行了模拟,并研究了燃料反应器温度TF、水甲烷比W/M及NiO甲烷比Ni/M对重整气组成、合成气产率Y、系统效率η影响。结果表明,化学链重整气组成模拟值与实验值吻合较好。提高TF,重整气中CO、H2O含量有升高趋势,H2、CO2含量略微降低;随着W/M增加,重整气中H2、CO2含量升高,CO含量降低,合成气产率Y几乎不变,系统效率η呈现降低趋势;Ni/M增加,重整气中H2、CO含量以及合成气产率Y呈现先升高后降低趋势,效率η下降,且Ni/M=0.8时,合成气产率Y取得最大值。     

二氧化碳重整甲烷制合成气研究进展

由于二氧化碳重整甲烷制合成气具有很多优点,因此引起了广泛的关注。本文综述了二氧化碳重整甲烷制取合成气的研究进展,介绍了二氧化碳重整甲烷热力学、甲烷和二氧化碳的活化、二氧化碳重整甲烷反应过程中的表面积碳和消碳和二氧化碳重整甲烷反应机理的研究现状,并进行了讨论和分析。     

垃圾填埋气的净化技术进展

填埋气是卫生填埋场的降解产物之一，它会引起二次污染、造成温室效应；经净化处理除去惰性组分和有害气体后，其主要成分CH4又是一种清洁能源。本文总结了国内外填埋气净化技术的进展．并从常用的净化单元操作出发．提出用多种联合工艺对填埋气进行净化处理。     

合成气甲烷化制替代天然气热力学分析

根据热力学分析建立了等温条件和绝热条件下的合成气甲烷化的热力学模型,选取CO甲烷化反应、水汽变换反应、CO歧化反应为独立反应,CO、CH4和H2O为关键组分.基于此热力学模型可以得到等温条件下的输出气体组成、CO转化率与CH4选择性和绝热条件下的输出气体温度、组成、CO转化率与CH4选择性.并在绝热条件下讨论了输入温度...     

甲烷重整制合成气用催化剂的研究进展

甲烷重整是制取合成气的重要方法之一,催化剂是重整工艺中的重要组成部分。综合国内外的研究现状,详细论述了甲烷重整反应的几种不同的途径,并针对不同的途径介绍了其反应机理以及催化剂的组成。     

北京首创垃圾填埋气制液化天然气

随着人口的膨胀,北京市面临着生活垃圾处理缺口大、减量化、无害化、资源化处理任务重的困难。近年来,北京市着力提升垃圾资源化利用的比例,加大相关技术研发应用,尤其是北京市环卫集团在全国率先研发出垃圾填埋气制液化天然气,具有环保和节能的双重效应。"一方面要减轻垃圾填埋场的臭味,另一方面要实现资     

焦炉气非催化部分氧化与催化部分氧化制合成气工艺比较

提出了一种可用于焦炉气转化的非催化部分氧化工艺,并进行了研究;同时对焦炉气非催化部分氧化和催化部分氧化制合成气工艺进行了比较,结果表明,催化部分氧化需要大量的外加蒸汽,其总体能耗并不比非催化部分氧化法低。     

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%。     

Hydrogen production via dry reforming of butanol: Thermodynamic analysis

Dry reforming of butanol for hydrogen production has been studied by Gibbs free energy minimization method. The calculation results showed that the formation of hydrogen and carbon monoxide was through a multi-step pathway via the dehydrogenation, dehydration, decomposition and carbon dioxide reforming of butanol. The optimum conditions for hydrogen production are identified: reaction temperatures between 1150 and 1200 K and carbon dioxide-to-butanol molar ratios between 3.5 and 4.0 at 1 atm. Under the above conditions, 100% conversion of butanol, 34.91-37.98% concentration of hydrogen and 57.34−57.87% concentration of carbon monoxide could be achieved in the absence of coke formation. The butanol dry reforming with carbon dioxide is suitable for providing fuels for Solid Oxide Fuel Cell (SOFC). The coke-formed and coke-free regions are found, which are useful in guiding the search for suitable catalysts for the reaction.     

Thermodynamic analysis of glycerol dry reforming for hydrogen and synthesis gas production

A thermodynamic analysis of glycerol dry reforming has been performed by the Gibbs free energy minimization method as a function of CO₂ to glycerol ratio, temperature, and pressure. Hydrogen and synthesis gas can be produced by the glycerol dry reforming. The carbon neutral glycerol reforming with greenhouse gas CO₂ could convert CO₂ into synthesis gas or high value-added inner carbon. Atmospheric pressure is preferable for this system and glycerol conversion keeps 100%. Various of H₂/CO ratios can be generated from a flexible operational range. Optimized conditions for hydrogen production are temperatures over 975 K and CO₂ to glycerol ratios of 0-1. With a temperature of 1000 K and CO₂ to glycerol ratio of 1, the production of synthesis gas reaches a maximum, e.g., 6.4 mol of synthesis gas (H₂/CO = 1:1) can be produced per mole of glycerol with CO₂ conversion of 33%.     

煤基合成气甲烷化反应过程的热力学计算与分析

建立了煤基合成气甲烷化反应过程基于吉布斯自由能最小法的热力学计算模型。考察了温度、压力对CO,CO_2单独及同时甲烷化反应的影响,探讨了原料气脱碳处理后,CO_2摩尔分数对CO转化率、CH_4选择性、CH_4产率及积炭的影响。结果表明,低温高压有利于甲烷化反应。在多数情况下CO转化率要高于CO_2,尤其是温度低于600℃时,CO甲烷反应比CO_2更容易发生;随着温度进一步升高,CO_2转化率明显上升,而CO转化率迅速下降。另外,当原料气中CO_2摩尔分数低于2.44%时对积炭无影响,对CH_4的选择性和产率降幅小于10%,在脱碳工艺中可以不予脱除。     

天然气换热式转化制合成气催化剂的选用

论述了制合成气过程催化剂的选择及重要性,转化催化剂要求有较好的低温活性和抗积炭性能,中变催化剂考虑催化剂本体含硫量,低变催化剂要从活性、热稳定性、堆积密度、还原后体积收缩率、烧失重和自由水含量等方面衡量,甲烷化催化剂的选用要根据设备状况满足工艺要求方面考虑。催化剂的使用寿命既与合理选用催化剂有重要关系,也与工业应用过程中的正确使用和维护有关。     

Thermodynamic analysis of glycerol partial oxidation for hydrogen production

Thermodynamics of glycerol partial oxidation for hydrogen production has been studied by Gibbs free energy minimization method. The optimum conditions for hydrogen production are identified: reaction temperatures between 1000 and 1100 K and oxygen-to-glycerol molar ratios of 0.4-0.6 at 1 atm. Under the optimal conditions, complete conversion of glycerol, 78.93%-87.31% yield of hydrogen and 75.12%-87.97% yield of carbon monoxide could be achieved in the absence of carbon formation. The glycerol partial oxidation with O₂ is suitable for providing hydrogen-rich fuels for Molten Carbonate Fuel Cell and Solid Oxide Fuel Cell. The carbon-formed and carbon-free regions are found, which are useful in guiding the search for suitable catalysts for the reaction. Inert gases have a positive effect on the hydrogen and carbon monoxide yields.     

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。     

Thermodynamic analysis and optimization of RWGS processes for solar syngas production from CO2

Process systems were investigated for syngas production from CO₂ and renewable energy (solar) by the reverse water‐gas shift (RWGS) and the reverse water‐gas shift chemical looping (RWGS‐CL) process. Thermodynamic analysis and optimization was performed to maximize the solar‐to‐syngas (StS) efficiency η_StS. Special emphasis was laid on product gas separation. For RWGS‐CL, maximum StS efficiencies of 14.2 and 14.4% were achieved without and with heat integration, respectively. The StS efficiency is dictated by the low overall efficiency of H₂ production. RWGS‐CL is most beneficial for the production of pure CO, where the StS efficiency is one percent point higher compared to that of the RWGS process with heat integration. Heat integration leads to significant reductions in external heat demand since most of the gas phase process heat can be integrated. The StS efficiencies for RWGS and RWGS‐CL achieve the same level as the reported values for solar thermochemical syngas production. © 2016 American Institute of Chemical Engineers AIChE J, 63: 15–22, 2017     

Thermodynamic analysis of steam reforming of glycerol for hydrogen production at atmospheric pressure

Thermodynamic chemical equilibrium analysis of steam reforming of glycerol(SRG)for selective hydrogen production was performed based on the Gibbs free energy minimisation method.The ideal SRG reaction(C₃H₈O₃+3H₂O→3CO₂+7H₂)and a comprehensive set of side reactions during SRG are considered for the formation of a wide range of products.Specifically,this work focused on the analysis of formation of H₂,CO₂,CO and CH4 in the gas phase and determination of the carbon free region in SRG under the conditions at atmospheric pressure,600 K–1100 K and 1.013×10⁵–1.013×10⁶ Pa with the steam-to-glycerol feed ratios(SGFR)of 1:5–10.The reaction conditions which favoured SRG for H₂ production with minimum coke formation were identifies as:atmospheric pressure,temperatures of 900 K–1050 K and SGFR of 10:1.The influence of using the inert carrier gas(i.e.,N₂)in SRG was studied as well at atmospheric pressure.Although the presence of N₂ in the stream decreased the partial pressure of reactants,it was beneficial to improve the equilibrium yield of H₂.Under both conditions of SRG(with/without inert gas),the CH4 production is minimised,and carbon formation was thermodynamically unfavoured at steam rich conditions of SGFR>5:1.     

Fuel processor based on syngas production via short contact time catalytic partial oxidation reactors

Short contact time catalytic partial oxidation (SCT-CPO) of natural gas is a promising technology for syngas production, representing an appealing alternative to existing processes. The high conversion and selectivity observed since the earlier works in this field can make this process attractive. Moreover, the SCT-CPO reactors can be autothermally operated and the possibility to use air as oxidant appears a feasible route to reduce syngas production costs: these two issues make possible the use of a SCT-CPO reactor as the reformer of a fuel processor for H₂ production for fuel cells.

The present work refers to an experimental study of syngas production from CH₄ and O₂ via a SCT-CPO reactor made of a fixed bed of Rh/-Al₂O₃ spheres. The main obtained results are: (i) an increase in GHSV produces an enhancement of transport rates and this in turn determines an improvement in CH₄ conversion, despite the reduction in residence time; (ii) the catalyst pellets get hotter than the gas phase thus favouring the H₂ and CO production; syngas formation is in fact both thermodynamically and kinetically promoted at high temperatures; (iii) a similar improvement of conversion was obtained with a reduction of the catalyst particle size, thanks once again to an increase in the heat transport and a higher geometrical surface area of the catalyst itself. By a slight increase of the O₂ fed to the reactor, H₂ and CO yields can be maximised and a complete CH₄ conversion achieved.