IFP连续重整技术的最新进展

论述了ＩＦＰ对连续重整技术发展方向的认识以及ＩＦＰ连续重整技术的最新进展，并对各项技术改进的结果进行了充分对比。     

On-board plasma-assisted conversion of heavy hydrocarbons into synthesis gas

The fuel conversion performance of two gliding arc plasma reformers is investigated with the goal of syn-gas production on-board vehicles. In both systems, n-tetradecane (C₁₄H₃₀) fuel was reformed with plasma under partial oxidation conditions in the absence of metal catalysts and steam. A comparison of the performance of each device is made with regard to the hydrogen yield and energy conversion efficiency. The results show that gliding arc systems are capable of reforming heavy hydrocarbon fuels with high conversion efficiency and are an important piece of technology for on-board vehicular reforming systems that should be further developed and optimized.     

Intensification of steam reforming of natural gas: Choosing combustible fuel and reforming catalyst

The steam reforming of methane in a parallel plate microreactor, consisting of alternating channels carrying out catalytic combustion and reforming on opposite sides of a wall, is modeled with fundamental kinetics and a pseudo-2D reactor model. It is shown that at high fuel conversions, the choice of hydrocarbon combustible fuel is immaterial when suitable compositions are used so that the energy input is kept the same. On the other hand, direct comparison of Rh and Ni indicates that the choice of reforming catalyst is critical. Speed up of heat transfer via miniaturization is insufficient for process intensification; catalyst-intensification is also needed to avoid hot spots and enable compact devices for portable and distributed power generation.     

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.     

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。     

Advances in H2 production from the aqueous-phase reforming of biomass-derived polyols：A review

生物质多元醇水相重整是一项正在发展的、很有前景的制氢技术。本文对近些年来涌现的生物质多元醇水相重整制氢研究进行了综述,讨论了多元醇水相重整反应热力学,介绍了反应动力学特征,并以此为基础对反应机理、催化剂体系以及工艺条件优化进行了总结。通过与蒸汽重整对比,指出了水相重整制氢技术的优缺点：优点是能耗低、工艺步骤较少、后处理简单;缺点是副反应多,收率低。最后,提出开发更为高效稳定的催化材料、降低催化剂制备成本和优化工艺条件将是未来研究工作的重点。     

焦炉煤气制合成气反应器数值模拟

采用CFD软件F luent模拟计算焦炉煤气(COG)非催化局部氧化制合成气反应器,其中湍流模型选择标准k-ε模型,热辐射选择P-1模型,用非预混模型计算化学输运和反应。反应器内组分与温度场的数值模拟结果与实验测定结果基本吻合,说明模拟结果是可信的。通过模拟可预测,当氧气与焦炉煤气进气体积比达到0.14左右时,可以获得最好的焦炉煤气的转化效果。本数值模拟可为COG非催化局部氧化制合成气进一步的工程研究与应用提供可靠的理论参考依据。     

燃料电池用柴油重整制氢技术现状与展望

现有储氢技术在储氢密度、能耗及相应的基础设施建设等方面存在明显短板，难以满足燃料电池技术商业化发展需求，现场制氢技术得到了广泛关注。其中，柴油重整制氢技术以其理论产氢比率高、适用领域广、基础设施完善、安全性好、成本低等优点，可广泛应用于汽车、船舶、分布式发电等民用领域以及潜艇、舰船等军事领域，成为热点研究之一。本文综述了柴油重整制氢的分类，详细介绍了蒸汽重整、部分氧化重整和自热重整制氢的反应机理，并对三种重整反应的优缺点进行了对比分析；在此基础上，概述了三种重整反应国内外研究现状。总体而言，蒸汽重整产物中氢气浓度最高但系统质量较大，比较适用于固定制氢领域；自热重整技术系统结构较为紧凑，产物氢气浓度适中，比较适用于汽车等移动制氢领域；部分氧化重整技术由于产物H₂/CO比率较低，加之反应温度较高，容易发生结焦反应，目前其应用领域还相对有限。     

生物质多元醇水相重整制氢研究进展

生物质多元醇水相重整是一项正在发展的、很有前景的制氢技术。本文对近些年来涌现的生物质多元醇水相重整制氢研究进行了综述,讨论了多元醇水相重整反应热力学,介绍了反应动力学特征,并以此为基础对反应机理、催化剂体系以及工艺条件优化进行了总结。通过与蒸汽重整对比,指出了水相重整制氢技术的优缺点:优点是能耗低、工艺步骤较少、后处理简单;缺点是副反应多,收率低。最后,提出开发更为高效稳定的催化材料、降低催化剂制备成本和优化工艺条件将是未来研究工作的重点。     

Using continuous and pulse experiments to compare two promising nickel-based oxygen carriers for use in chemical-looping technologies

Chemical-looping technologies have obtained widespread recognition as power or hydrogen production units with inherent carbon capture in a future scenario where CO₂ capture and storage (CCS) is reality. In this paper three different techniques are described; chemical-looping combustion and two categories of chemical-looping reforming. The three techniques are all based on oxygen carriers that are circulating between an air- and a fuel reactor, providing the fuel with undiluted oxygen. Two different oxygen carriers; NiO/NiAl₂O₄ (40/60 wt/wt) and NiO/MgAl₂O₄ (60/40 wt/wt) are compared. Both continuous and pulse experiments were performed in a batch laboratory fluidized bed working at 950 °C using methane as fuel. It was found that pulse experiments offer advantages in comparison to continuous experiments, particularly when evaluating suitable particles for autothermal chemical-looping reforming. Firstly, smaller conversion ranges can be investigated in more detail, and secondly, the onset and extent of carbon formation can be determined more accurately. Of the two oxygen carriers, NiO/MgAl₂O₄ offers several advantages at elevated temperatures, i.e. higher methane conversion, higher selectivity to reforming and lesser tendency for carbon formation.     

入口气体组成对天然气重整工作温度的影响

重整催化剂是影响重整制氢系统造价和寿命的重要因素。由于在所需重整温度下容易烧结积炭,廉价的Ni系催化剂在分布式中小型重整反应器中的应用受到了限制。为了使Ni系催化剂在不易发生烧结积炭的温度下工作,分析了在一定原料CH4空速和转化率下入口气体组成对重整工作温度的影响,并探讨了在原料气中导入循环气来改变重整入口气体组成的方法。结果表明：Ni系催化剂在导入一定组成和流量比的循环气与不导入循环气时相比,一定原料CH4空速和转化率下的重整工作温度大幅降低。据此,提出了一种用于燃料电池电站氢源系统的重整制氢工艺流程,其特征是将部分燃料电池阳极出口气作为循环气与原料气混合后导入重整反应器,使天然气重整工作温度大幅降低。     

生物质炭化热解气催化重整制取费-托合成气研究进展

生物质热解气是一种高热值的可燃气体,具有重要的开发利用价值,但由于其复杂的组分,多焦油和CO₂、CH₄等成分对热解气化过程以及相关的设备都有较大的危害,而冷凝下来形成的黏稠液体易造成管道堵塞,直接燃用产生的炭黑会造成环境污染,成为制约热解气进一步开发利用的主要因素。本文分析了热解气催化重整制取费-托合成气的可行性,分别介绍了连续和分段式热解-催化重整设备,镍基、钙基、铁基、碱金属类、生物炭等催化剂,以及热解气分离提纯技术等方面的研究现状,分析了目前热解气制取费-托合成气研究中存在的催化重整设备规格不统一、缺乏相关的行业标准、不同催化剂与催化剂助剂的催化重整效果、机理尚不明确等问题,并提出了采用分段式热解-催化重整设备,并以炭化产品生物炭作为催化重整催化剂的未来研究方向,开辟了生物质炭化热解气开发利用的新途径。     

UOP公司催化重整催化剂专利技术分析

对UOP公司催化重整催化剂领域相关专利进行了检索,从专利申请趋势、技术区域分布、专利技术布局和在中国专利申请情况等方面对其专利技术进行分析。UOP公司在催化重整催化剂领域进行了大量的研究工作,自1943年开始在该领域申请专利,并不断加强其在世界主要国家的专利布局,在美国和中国等10 余个国家申请了相关专利,专利技术主要涉及含分子筛催化剂、含贵金属催化剂和分子筛催化剂等制备技术。UOP公司催化重整催化剂专利技术的研发主要集中在铂基多金属催化剂的优化、催化剂载体性能的进一步提高以及新助剂的研究,目前主要是通过对不同类型和含量的助金属进行研究,研发高活性、高产率、高选择性、低生焦、抗磨性能好的催化重整催化剂,其催化剂呈现系列化发展。     

以天然气为介质还原蒸汽转化催化剂

介绍了在中国石化荆门分公司制氢装置采用天然气还原Z417/Z418型转化催化剂工业应用的成功经验,并对使用天然气作为还原介质的操作要点进行说明。结果表明,使用天然气作为还原Z417/Z418型转化催化剂介质,必须在建立系统循环的基础上进行,通过系统循环,保证转化催化剂还原所需要的氢气,使转化催化剂得到完全还原。     

生物油水蒸气催化重整制氢研究进展

生物油催化重整制氢是生物质转化为高品位能源的主要发展方向之一,引起了国内外的广泛关注。本文主要介绍了国内外生物油制取氢气的工艺、催化剂制备等技术。作者建议开发生物油流化床催化重整制氢技术和开发高效耐磨催化剂等,从而降低生物油制氢的成本。     

液体碳氢燃料蒸汽重整制氢催化剂研究进展

液体碳氢燃料具有能量密度高、氢含量大及便于储存和运输的特点,以其为原料经重整制氢并应用到移动式的燃料电池/加氢站对民用设备及国防武器等具有现实意义。本文首先对液体碳氢燃料蒸汽重整机理进行概述,明确当前催化剂面临的积炭、硫中毒等主要问题,从而指导高性能催化剂的设计和开发;其次,总结了几种典型液体碳氢燃料（汽油、煤油、柴油、焦油、含硫碳氢燃料等）蒸汽重整催化剂的相关进展,对比了不同催化剂在相应工艺条件下的活性及稳定性;最后,归纳了几类蒸汽重整过程强化技术包括等离子体重整、化学链重整、吸附增强重整及反应与分离耦合重整,说明了各类强化技术的优点及存在的不足,提出通过构建高效催化剂与蒸汽重整强化技术耦合有望实现液体碳氢燃料的高效转化制氢。希望本综述能为进一步研究液体碳氢燃料重整制氢提供相关指导。     

甘油催化重整制氢/合成气的研究进展

随着生物柴油的大规模化发展,副产物甘油的合理利用成为生物柴油产业发展的关键问题之一。对甘油蒸汽重整、水相重整和超临界重整制氢气和合成气的研究进行了综述和评价,对未来甘油重整制氢气/合成气的研究提出了不足和展望。     

Reaction mechanism of partial oxidation of methane to synthesis gas over supported ni catalysts

A mechanistic study on the partial oxidation of methane to synthesis gas (H₂ and CO) was conducted with supported nickel catalysts. To investigate the reaction mechanism, pulse experiments, O₂-TPD, and a comparison of the moles of reactants and products were carried out. From the O₂-TPD experiment, it was observed that the active catalyst in the synthesis gas production desorbed oxygen at a lower temperature. In the pulse experiment, the temperature of the top of the catalyst bed increased with the pulses, whereas the temperature of the bottom decreased. This suggests that there are two kinds of reactions, that is, the total oxidation of methane (exothermic) at the top and reforming reactions (endothermic) at the bottom. From the comparison of the moles of reactants and products, it was found that the moles of CO₂, CH₄ and H₂O decreased as the moles of H₂ and CO increased. The results support the mechanism that synthesis gas is produced through a two-step reaction mechanism: the total oxidation of methane to CO₂ and H₂O takes place first, followed by the reforming reaction of the produced CO₂ and H₂O with residual CH₄ to form synthesis gas. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

A novel power generation system based on moderate conversion of chemical energy of coal and natural gas

This paper proposes a novel power generation system that implements mutually beneficial use of natural gas and coal. In conventional power plants fossil fuels are usually directly burned with air to convert the chemical energy to thermal energy for power generation. In combustion processes, about 30% of exergy of fuels is destructed, and the decrease in the irreversibility of combustion processes has large potential to improve the performance of power plants. The new system attempts to use chemical exergy of fuels before combustion through coordinated use of coal and natural gas. First approximate 60% of coal is gasified in a gasifier with air and steam as oxidant, then, the unconverted residuals (char) and natural gas are utilized synthetically based on the method of char-fired reforming to generate syngas, in which the combustion of char will drive the methane/steam-reforming reaction. The fuel gas from the partial gasification of coal and syngas from char-fired reforming are mixed together and fed into a combined cycle for power generation. As a result, the overall thermal efficiency of the new system is about 51.5% based on the current turbine technologies and the net thermal efficiency of coal to electricity of the new system can reach near 48.6%. The results obtained here may provide a new way of using coal and natural gas more efficiently and economically.     

催化重整研究进展

介绍了国内外催化重整工艺以及半再生重整与连续重整催化剂的研究进展,综述了美国UOP公司、法国IFP公司、中国RIPP和中国FRIPP在催化重整催化剂方面的研究进展。设计新型催化重整反应途径,开发出新型催化反应所需的工艺和催化剂将成为未来发展的方向。