多组分生物油吸附强化重整制氢的热力学分析

文章采用HSC Chemistry软件进行多组分生物油重整制氢(包括普通重整和吸附强化重整)过程的热力学分析,研究反应温度、S/C和Ca/C对氢气浓度和氢气产率等指标的影响。研究结果表明:两种重整制氢过程的氢气产率和氢气浓度均随着S/C的增大而增大,但在S/C3后增幅不再明显;当S/C=3时,普通重整制氢过程的氢气产率和氢气浓度均仅为70%左右,最佳重整反应温度高达830℃;加入吸附剂CaO后,吸附强化重整过程的氢气产率和氢气浓度较普通重整制氢过程有大幅提升,且最佳重整反应温度显著下降,当S/C=3时,最佳重整反应温度为480℃,氢气产率和氢气浓度分别为97.2%和99.7%。     

生物质油应用技术

介绍了国外生物质油的各种应用技术研究成果。作为燃料，与煤混合用于锅炉可以减少SO2排放，与矿物柴油共同乳化可驱动柴油机，也可直接用于燃气轮机中，但是生物质油有一定的腐蚀性。生物质油可以用于制氢，但目前成本较高，必须结合高附加值的副产品联合生产。生物质油还可以成为一种纤维素气化工艺的中间产品，生产合成气；作为脱硫脱硝剂使用也很有前途。     

乙醇重整制氢催化剂的国内研究进展

制氢技术是发展燃料电池的关键技术之一,而目前研究较多且具有良好应用前景的制氢技术是乙醇水蒸气重整制氢法制氢。综述了国内水蒸气重整法、部分氧化法、氧化重整法等乙醇重整制氢法的研究进展,同时综述了乙醇水蒸气重整制氢催化剂助剂、载体的研究进展。指出了在较低温度下以高转化率、低C0选择性、高氢气选择性制氢是乙醇制氢技术研究的方向。     

生物质气化制氢研究现状

重点讨论生物质催化气化制氢的基本原理和基本过程，阐述生物质催化气化制氢、超临界水中生物质催化气化制氢、等离子体热解气化制氢的研究现状，指出生物质气化制氢的广阔前景。     

制氢技术和工艺

氢能是最具希望的能源之一，氢能的获得在于制氢原料和制氢途径两大因素。文章详细介绍了目前制氢技术和工艺的发展现状，并根据我国国情提出了利用生物质制氢的能源利用新方式。     

生物质一步制氢的热力学分析及实验研究

根据最小吉布斯自由能理论,采用ASPEN模拟软件,计算分析了生物质一步制氢过程中,温度、压力、汽碳比以及钙碳比对气化过程的影响,并对该制氢过程进行了实验研究。研究结果表明,随气化温度的升高,气体产物中氢的含量增加;生物质一步制氢比较适宜的气化压力约为2.0MPa;在最佳的压力范围内,钙碳比合适的比例为2.0;高的汽碳比可以抑制甲烷的生成,但其值大于5后其影响明显减弱。对不同种类的生物质的实验研究表明:种类广泛的生物质,均能在该文确定的条件下实现一步制氢和二氧化碳等的同步脱除。     

生物质热化学转化制氢技术

生物质是一种重要的可再生能源，是氢的载体，与矿物燃料相比，具有挥发分高，硫、氮含量低等优点。无论是从能源角度还是从环境角度，发展生物质制氢技术都具有重要的意义。目前有关生物质制氢方面的研究主要集中在热化学转换法和生物法，文章从热化学转换的角度，进行了几种生物质制氢路线的技术经济分析预测。     

二甲醚水蒸气重整制氢的模型和数值模拟

为研究二甲醚的水蒸气重整制氢过程,设计了一种带有隔热套、瓦片式加热通道和催化反应床的重整反应器.建立了反应器的数学模型,并利用COMSOL软件对其仿真.试验研究了反应气体温度、水蒸气与二甲醚的物质的量比和反应器结构参数对二甲醚转化率、氢产率的影响.模拟结果显示了二甲醚水蒸气重整制氢过程中的各组分质量分布及不同温度、不同...     

重整制氢技术及其研究进展

燃料电池技术的发展使得氢能利用也在快速发展，目前利用重整技术进行制氢是十分重要的一种手段。本文介绍了重整制氢技术的现状及其研究动态，指出了蒸汽重整是目前比较成熟的制氢方法，并正在由常规型设备向紧凑型、微通道型方向发展。另外介绍了部分氧化重整、催化部分氧化重整和自热重整技术的优缺点以及它们目前所遇到的技术困难。最后预测了今后重整制氢技术的研究重点是等离子体重整。     

中低温废热与甲醇重整结合的氢电联产系统

提出了烧结机烟气中低温废热与甲醇蒸汽重整制氢整合的新方法,模拟建立了中低温废热结合甲醇重整制氢的系统.基于能的品位概念,采用EUD图像火用分析方法,揭示低品位的中低温废热转化为高品位化学能的能量转换特性;研究了中低温废热品位的提升随甲醇重整反应温度的变化规律.研究结果表明:新型制氢系统的火用效率有望达到82 8%,比传统甲醇制氢系统约高12个百分点,甲醇燃料节能率23.7%.另外,初步静态经济性分析表明:新系统可使氢气生产成本约为1.5元/m3,远低于电解水制氢成本(5.5元/m3).当甲醇原料成本价格保持在一定的价格范围内,其制氢成本可以与传统天然气制氢成本1.2元/m3相竞争.本研究为冶金工业同时解决中低温废热利用和制氢能耗高的难题提供了一个新途径.     

Economic analysis of hydrogen production from steam reforming process: A literature review

The interest in steam reforming process as an efficient method for hydrogen production has been greatly increasing, due to its efficiency during hydrogen production and low environmental problems compared to other techniques. The main objective of this review was to present a comprehensive study of environmental, economic aspects of hydrogen production from steam reforming of raw materials such as biomass, bio-gas, ethanol, and natural gas. From literature review, it was found that among methods for hydrogen production, steam reforming of natural gas has lower installed capital due to the precence of high amounts of unconverted hydrocarbons in the produced gas (so-called tar) during other methods such as steam reforming of bio-gas.     

Modeling the effect of non-linear process parameters on the prediction of hydrogen production by steam reforming of bio-oil and glycerol using artificial neural network

Biomass-derived substrates such as bio-oil and glycerol are gaining wide acceptability as feedstocks to produce hydrogen using a steam reforming process. The wide acceptability can be attributed to a huge amount of glycerol and bio-oil obtained as by-products of biodiesel production and pyrolysis processes. Several parameters have been reported to affect the production of hydrogen by biomass steam reforming. This study investigates the effect of non-linear process parameters on the prediction of hydrogen production by biomass (bio-oil and glycerol) steam reforming using artificial neural network (ANN) modeling technique. Twenty different multilayer ANN model architectures were tested using datasets obtained from the bio-oil and glycerol steam reforming. Two algorithms namely Levenberg-Marquardt and Bayesian regularization were employed for the training of the ANNs. An optimized network configuration consisting of 3 input layer 14 hidden neurons, 1 output layer, and 3 input layer, 5 hidden neurons, and 1 output layer were obtained for the Levenberg-Marquardt and Bayesian regularization trained network, respectively for hydrogen production by bio-oil steam reforming. While an optimized network configuration consisting of 5 input nodes, 9 hidden neurons, 1 output node, and 5 input nodes, 8 hidden neurons, and 1 output node were obtained for Levenberg-Marquardt and Bayesian regularization trained network, respectively for hydrogen production by glycerol steam reforming. Based on the optimized network, the predicted hydrogen production from the bio-oil and glycerol steam agreed with the actual values with the coefficient of determination (R²) > 0.9. A low mean square error of 3.024 × 10⁻²⁴ and 6.22 × 10⁻¹⁵ for the optimized for Levenberg-Marquardt and Bayesian regularization-trained ANN, respectively. The neural network analyses of the two processes showed that reaction temperature and glycerol-to-water molar ratio were the most relevant factors that influenced the production of hydrogen by bio-oil and glycerol steam reforming, respectively. This study has demonstrated the robustness of the ANN as a technique for investigating the effect of non-linear process parameters on hydrogen production by bio-oil and glycerol steam reforming.     

生物油水蒸气催化重整制氢研究进展

氢气作为一种环境友好的清洁能源,人们对它的关注度越来越高。生物油水蒸气催化重整制氢是未来制氢的一种可行性方案。本文综述了近年来生物油水蒸气重整制氢的研究进展。主要从重整制氢反应机理、热力学分析、催化重整催化剂、代表性的重整反应器方面进行讨论,指出催化重整中的主要问题是碳沉积导致催化剂失活。研制高活性、高稳定性、高选择性的催化剂是生物油催化重整制氢的关键。     

Hydrogen production from glycerol steam reforming for low- and high-temperature PEMFCs

This paper presents a thermodynamic study of a glycerol steam reforming process, with the aim of determining the optimal hydrogen production conditions for low- and high-temperature proton exchange membrane fuel cells (LT-PEMFCs and HT-PEMFCs). The results show that for LT-PEMFCs, the optimal temperature and steam to glycerol molar ratio of the glycerol reforming process (consisting of a steam reformer and a water gas shift reactor) are 1000 K and 6, respectively; under these conditions, the maximum hydrogen yield was obtained. Increasing the steam to glycerol ratio over its optimal value insignificantly enhanced the performance of the fuel processor. For HT-PEMFCs, to keep the CO content of the reformate gas within a desired range, the steam reformer can be operated at lower temperatures; however, a high steam to glycerol ratio is required. This requirement results in an increase in the energy consumption for steam generation. To determine the optimal conditions of glycerol steam reforming for HT-PEMFC, both the hydrogen yield and energy requirements were taken into consideration. The operational boundary of the glycerol steam reformer was also explored as a basic tool to design the reforming process for HT-PEMFC.     

Comparative exergy analysis of sorption enhanced and conventional methane steam reforming

Exergy efficiency analysis tool is used to evaluate sorption enhanced steam reforming in comparison with the industrial hydrogen production route, steam reforming. The study focuses on hydrogen production for use in high pressure processes. Thermodynamic sensitivity analysis (effect of reforming temperature on hydrogen yield and reforming enthalpy) was performed to indicate the optimum temperature (650 °C) for the sorption enhanced reforming. The pressure was selected to be, for both cases, 25 bar, a typical pressure used in the industrial (conventional) process. Atmospheric pressure, 1000 °C and CO₂ as inert gas were specified as the optimum operating parameters for the regeneration of the sorbent after performing exergy efficiency analysis of three realistic case scenarios. Aspen Plus simulation process schemes were built for conventional and sorption enhanced steam reforming processes to attain the mass and energy balances required to assess comparatively exergy analysis. Simulation results showed that sorption enhanced reforming can lead to a hydrogen purity increase by 17.3%, along with the recovery of pure and sequestration-ready carbon dioxide. The exergy benefit of sorption enhanced reforming was calculated equal to 3.2%. Analysis was extended by adding a CO₂ separation stage in conventional reforming to reach the hydrogen purity of sorption enhanced reforming and enable a more effective exergy efficiency comparison. Following that analysis, sorption enhanced reforming gained 10.8% in exergy efficiency.     

Thermodynamic study of hydrogen production from crude glycerol autothermal reforming for fuel cell applications

This study presents a thermodynamic analysis of hydrogen production from an autothermal reforming of crude glycerol derived from a biodiesel production process. As a composition of crude glycerol depends on feedstock and processes used in biodiesel production, a mixture of glycerol and methanol, major components in crude glycerol, at different ratios was used to investigate its effect on the autothermal reforming process. Equilibrium compositions of reforming gas obtained were determined as a function of temperature, steam to crude glycerol ratio, and oxygen to crude glycerol ratio. The results showed that at isothermal condition, raising operating temperature increases hydrogen yield, whereas increasing steam to crude glycerol and oxygen to crude glycerol ratios causes a reduction of hydrogen concentration. However, high temperature operation also promotes CO formation which would hinder the performance of low-temperature fuel cells. The steam to crude glycerol ratio is a key factor to reduce the extent of CO but a dilution effect of steam should be considered if reforming gas is fed to fuel cells. An increase in the ratio of glycerol to methanol in crude glycerol can increase the amount of hydrogen produced. In addition, an optimal operating condition of glycerol autothermal reforming at a thermoneutral condition that no external heat to sustain the reformer operation is required, was investigated.     

Investigation of the benefits of diabatic microreactors for process intensification of the water-gas shift reaction within the steam reforming process

Currently, the steam reforming process is the largest industrial source of hydrogen. Improving its efficiency can help to reduce associated carbon emissions and hydrogen production costs. Intensifying the water-gas shift reaction using microreactors with integrated cooling is one way of achieving this. In this study, a 2-D computational model of one of these microreactors is developed, validated with experimental data, and then used to demonstrate how microreactors can enhance the conversion of the water-gas shift reaction beyond what can be achieved using conventional packed bed reactors. These results are then generalized into a full system model of the steam reforming process to demonstrate how microreactors can reduce hydrogen production costs. The results suggest that microreactors can significantly reduce the required reactor volume and catalyst loading for the water-gas shift reaction and can similarly reduce the hydrogen production costs associated with the steam reforming process.     

Thermochemical waste-heat recuperation as on-board hydrogen production technology

Thermochemical waste-heat recuperation (TCR) as an on-board hydrogen production technology is considered. To determine the effectiveness of using TCR systems as an on-board hydrogen production technology and to assess the possibility of hydrogen production in TCR systems, a thermodynamic analysis of various hydrocarbon reforming reactions was carried out. The thermodynamic analysis has been realized via Aspen HYSYS software. Three steam reforming reactions with methane, methanol, and ethanol were investigated. It was established that the composition of the initial reaction mixture and the process temperature has a significant effect on the efficiency of the thermochemical heat recuperation system. The maximum efficiency of thermochemical heat recuperation systems due to steam reforming is achieved at 600 K for methanol; 700 K for ethanol and 900 K for methane.     

Techno-economic analysis of H2 production processes using fluidized bed heat exchangers with steam reforming – Part 1: Oxygen carrier aided combustion

This work presents the techno-economic assessment for a new process where a fluidized bed heat exchanger (FBHE) is used as heat source for steam reforming in a hydrogen production plant. This suggested process configuration is compared with a reference case representing a conventional steam methane reforming (SMR) large-scale hydrogen production plant. The use of a FBHE as a heat source for the endothermic reforming is an advantage because of the high heat transfer coefficient to the reformer tubes. The suggested process configuration utilizes oxygen carrier particles as bed material and a bubbling fluidized bed reactor with immersed reformer tubes to ensure sufficient heat production for the reforming and improved heat transfer to the reformer tubes compared a conventional plant. The results include a comparison of hydrogen production efficiency and levelized production costs (LCOH) of the two plants where the production efficiency is more than 11% higher and the LCOH is more than 7% lower for the suggested process configuration.     

A comparative study on hydrogen production from steam-glycerol reforming: thermodynamics and experimental

A detailed comparative study on thermodynamic and experimental analyses of glycerol reforming for hydrogen production has been conducted in terms of the effects of temperature, pressure, water to glycerol feed ratio, feeding reactants to inert gas ratio and feeding gas flow rate (residence time). The thermodynamic analysis was conducted by using a non-stoichiometric methodology based on the minimisation of Gibbs free energy. And the experiments were carried out with a pilot scale set-up. The results show that the thermodynamic and experimental data agree fairly well with each other. The measured hydrogen production is slightly lower than that predicted by the thermodynamic analysis, which is mainly because the conversion of steam is incomplete. High temperature, low pressure, low feeding reactants to inert gas ratio and low gas flow rate are favourable for steam reforming of glycerol for hydrogen production. There is an optimal water to glycerol feed ratio for steam reforming of glycerol for hydrogen production which is about 9.0. The glycerol conversion is a strong function of water to glycerol ratio, whereas a weak function of other parameters over the conditions of this work. A novel adsorption enhanced reaction process incorporating water and heat recovery is proposed for further optimisation of hydrogen production from steam reforming of glycerol.