流化床在甲烷临氧CO2重整反应中的作用研究

在流化床反应器中进行甲烷临氧CO₂重整制合成气反应。通过计算分析了催化剂颗粒在床层内的流化特性。对比实验表明,流化床反应器在催化剂活性、稳定性、自热过程以及催化剂积炭等方面均体现出比固定床反应器的优越性。在流化床反应器中进行的甲烷自热重整反应,甲烷的转化率接近热力学平衡值,床层温度梯度小于10 ℃, 反应20 h后,催化剂表面无积炭。     

甲烷自热重整催化剂的研究进展

简要介绍了甲烷自热制合成气的研究进展,重点从催化剂活性组分、载体、助剂方面介绍了自热重整反应常用的负载型金属催化剂,指出了联合活性组分和功能型载体是大规模自热重整制氢的发展热点。     

甲烷二氧化碳重整制合成气 催化剂抗积碳稳定性研究取得重大进展

<正>近日,甲烷二氧化碳自热重整制合成气装置在山西潞安集团煤制油基地实现稳定运行。目前该装置已稳定运行了1000小时以上。甲烷二氧化碳重整制合成气技术源于中国科学院上海高等研究院、山西潞安矿业(集团)有限责任公司和荷兰壳牌     

甲烷二氧化碳制合成气万方级装置实现稳定运行

<正>近日,甲烷二氧化碳自热重整制合成气装置在山西潞安集团煤制油基地实现稳定运行,即在前期试运行和系统优化的基础上,6月21日该装置启动全系统运行,7月10日实现满负荷生产,8月2日完成了中国石油和化学工业联合会组织的现场标定。甲烷二氧化碳重整制合成气技术源于中国科学院上海高等研究院、山西潞安矿业(集团)有限责任公司和荷兰壳牌石油     

甲烷二氧化碳催化重整制合成气研究进展

催化剂研究是实现甲烷二氧化碳重整制合成气工业化的关键。对近年来甲烷二氧化碳重整制合成气的催化剂研究进行综述。介绍了贵金属催化剂、非贵金属催化剂及碳化物催化剂在甲烷二氧化碳重整反应中的应用及反应机理,并对催化剂体系研究方向进行展望。     

膜催化技术用于甲烷转化反应的研究进展

介绍了膜催化技术在甲烷转化反应中的应用,这些过程包括甲烷氧化偶联反应制乙烯,甲烷部分氧化制甲醇,甲烷水蒸气重整制合成气等,通过膜催化反应与传统催化反应的比较,揭示了膜催化技术的优点。     

甲烷临氧催化转化制合成气研究进展

介绍了国内外甲烷临氧催化转化制合成气的研究进展,结合本课题组的研究结果及文献报道,对甲烷部分氧化、甲烷临氧二氧化碳重整、甲烷临氧水蒸气重整及甲烷-二氧化碳-水-氧气耦合三重整反应进行了阐述和分析,综述了在催化剂体系、反应机理和工艺条件等方面取得的近期研究成果.最后对甲烷临氧催化转化制合成气技术今后的研究重点及应用领域作了展望.     

天然气转化制备合成气研究进展

综述了目前转化利用天然气制备合成气的主要方法,包括甲烷水蒸气重整、甲烷部分氧化、甲烷二氧化碳重整、甲烷水蒸气重整与部分氧化耦合反应、甲烷部分氧化与二氧化碳重整耦合反应、甲烷水蒸气重整与二氧化碳重整耦合反应以及甲烷的三重整反应,重点介绍了前3种典型反应所用的催化剂,最后提出将这3种典型反应耦合使用,并辅以晶格氧工艺、等离子体技术、微波技术是未来甲烷转化制备合成气的发展趋势。     

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。     

甲烷部分氧化及重整反应多相催化剂的研究进展

介绍国内外甲烷制合成气技术中多相催化剂的研究进展,包括催化剂在水蒸气重整、甲烷部分氧化和二氧化碳重整制合成气技术中的研究情况,重点评述了催化剂的活性组分、助剂和载体方面的研究进展及存在的问题。     

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%。     

Thermodynamic analysis of dry autothermal reforming of glycerol

Dry autothermal reforming of glycerol uses a combination of dry (CO₂) reforming and partial oxidation reactions to produce syngas rich product stream. Thermodynamic equilibrium data for dry autothermal reforming of glycerol was generated for temperature range 600-1000 K, 1 bar pressure, OCGR [feed O₂/C (C of glycerol only) ratio] 0.1 to 0.5 and CGR [feed CO₂/glycerol ratio] 1 to 5 and analyzed. The objective of the paper is to identify the thermodynamic domain of the process operation, study the variation of product distribution pattern and describe the optimum conditions to maximize yield of the desired product and minimize the undesired product formation. Higher OCGR and higher CGR yielded a syngas ratio (∼ 1), with lower carbon and methane formation, while lower CGR and lower OCGR yielded good hydrogen and total hydrogen, with low water and CO₂ production. The best thermoneutral condition for DATR of glycerol operation was seen at a temperature of 926.31 K at 1 bar pressure, OCGR = 0.3 and CGR = 1 that gave 2.67 mol of hydrogen, 4.8 mol of total hydrogen with negligible methane and carbon formations.     

Production of synthesis gas

The state-of-the-art for the production of synthesis gas from the steam reforming of methane is reviewed and discussed. Particular attention is given to the design of the tubular reformer and carbon formation on the nickel catalyst. Improvements in syngas technology are discussed, including: CO₂ reforming, autothermal reforming and heat exchange reforming, and the energy efficiencies of direct and indirect methane conversion are compared and contrasted.     

用低质煤层气(CMM)制氨的探讨

本文叙述了一种利用低质矿井区煤层气(CMM)[甲烷含量30%(φ)左右]制氨合成气的工艺及有关工艺条件的影响。低质煤层气通过自热转化制气,经变换,变压吸附脱氮,脱碳,制得氢氮体积分数之比为3的氨合成气。对于含30%(φ)甲烷的煤层气,脱氮成本112元/吨氨,由于低质煤层气价格较低,以折纯甲烷0.60元/Nm3计,脱氮后相当于纯甲烷价格为0.714元/Nm3,故具有较好的经济效益、环境效益和社会效益。氨可进一步加工为硝酸、或硝酸铵、或磷酸铵等,则可获得更大的经济效益。     

Autothermal CO2 reforming of methane over NiO–MgO solid solution catalysts under pressurized condition: Effect of fluidized bed reactor and its promoting mechanism

The effect of fluidized bed reactor in autothermal CO₂ reforming of methane over NiO–MgO solid solution catalysts was investigated by comparing with fixed bed reactor. Methane conversion to syngas was drastically enhanced by using a fluidized bed reactor. The catalyst was reduced and oxidized repeatedly in fluidized bed reactor during the reaction. The enhancement of methane conversion is related to the catalyst reducibility.     

Synthesis gas production by steam reforming of ethanol

A two-layer fixed-bed catalytic reactor for syngas production by steam reforming of ethanol has been proposed. In the reactor, ethanol is first converted to a mixture of methane, carbon oxides and hydrogen over a Pd-based catalyst and then this mixture is converted to syngas over a Ni-based catalyst for methane steam reforming. It has been shown that the use of the two-layer fixed-bed reactor prevents coke formation and provides the syngas yield closed to equilibrium.     

Mathematical Modeling and Optimization of Combined Steam and Dry Reforming of Methane Process in Catalytic Fluidized Bed Membrane Reactor

Mathematical modeling of the methane-combined reforming process (steam methane reforming–dry reforming methane) was performed in a fluidized bed membrane reactor. The model characterizes multiple phases and regions considering low-density phase, high-density phase, membrane, and free board regions that allow study of reactor performance. It is demonstrated that the combined effect of membrane and reaction coupling provides opportunities to overcome equilibrium limits and helps to achieve higher conversion. Additionally, the influence of key parameters on reactor performance including reactor temperature, reactor pressure, steam to methane feed ratio (S/C), and carbon dioxide to methane feed ratio (CO₂/C) were investigated in the multi-objective genetic algorithm to find the optimal operating conditions. Finally, the process of steam reforming was simulated in selected optimal conditions and the results are compared to those of the combined reforming process. Comparison reveals the superiority of the combined reforming process in terms of methane conversion, catalyst activity, and outlet H₂/CO ratio in the syngas product in being close to unity.     

High-Throughput Screening for the Promoters of Alumina Supported Ni Catalysts in Autothermal Reforming of Methane

The conversion of natural gas(methane) to syngas (reforming reaction) is regarded as alternative routes for production of great value compounds, such as synthetic liquid fuels and oxygenated compounds. The aim of this work is to investigate the highest activity catalyst among 30 catalyst candidates which consists of Ni-M [M (promoter) = Co, Fe, Ce] on γ-Al₂O₃, by combinatorial method for autothermal reforming. The catalyst candidates with different M/Ni molar ratio were prepared by the impregnation method. The consistent results were found between 32 channel reactors and single fixed bed reactor. It was found that the best catalyst is 5.54 wt%Ni-13.3wt% Ce/γ-Al₂O₃.     

Analysis of hydrogen production from methane autothermal reformer with a dual catalyst-bed configuration

This paper presents a performance analysis of a dual-bed autothermal reformer for hydrogen production from methane using a non-isothermal, one dimensional reactor model. The first section of Pt/Al₂O₃ catalyst is designed for oxidation reaction, whereas the second one based on Ni/MgAl₂O₄ catalyst involves steam reforming reaction. The simulation results show that the dual-bed autothermal reactor provides higher reactor temperature and methane conversion compared with a conventional fixed-bed reformer. The H₂O/CH₄ and O₂/CH₄ feed ratios affect the methane conversion and the H₂/CO product ratio. The addition of steam at lower temperatures to the steam reforming section of the dual-bed reactor can produce the synthesis gas with a higher H₂/CO product ratio.     

Autothermal reforming of methane over Ni catalysts supported over CaO–CeO2–ZrO2 solid solution

Ni catalysts supported on various solid solutions of ZrO₂ with alkaline earth oxide and/or rare earth oxide were synthesized. The catalytic activities were compared for partial oxidation of methane and autothermal reforming of methane. For partial oxidation of methane, the Ni catalyst supported on a CaO–ZrO₂ solid solution showed a high activity. Incorporation of CaO in the ZrO₂ matrix was effective for increasing the reduction rate of the NiO particles and for decreasing the coke formation. On the other hand, the Ni particles supported on the CaO–CeO₂–ZrO₂ solid solution had a strong interaction with the support, and the Ni particles showed high activity and stability for autothermal reforming of methane.