生物质与煤流化床催化气化制备燃气

基于单一流化床两步气化法,以煤作为热载体和发热体,水蒸气为气化剂,CaO为催化剂,在自行研制的流化床热态装置上对生物质（锯木）气化制备燃气进行了研究。探讨了温度和水蒸气与锯木比对燃气组分和低位热值的影响。在所研究的操作参数范围内,（H2 + CO）含量为67.58% ~ 74.9%,燃气低位热值为10719.09 kJ/Nm3 ~ 12002.44 kJ/Nm3。实验结果表明,含少量N2的中热值燃气可以被获得,H2和CO是燃气中最主要的两种气体。随着温度的升高,燃气中H2和CO含量增加,而CH4和CO2含量及燃气低位热值则呈现下降趋势。随着水蒸气与锯木比的增加,燃气中H2和CO2含量增加,而CH4和CO含量则相应的减小。     

生物质合成气的化学当量比调整

针对生物质气化气中硫化物少、V（H2／CO）低和V（CO2）高的特点，采用气化炉内铁系高温变换催化剂和气化炉外钛促进的钴钼耐硫催化剂进行水煤气变换调整H2／CO比，添加部分沼气重整过量CO2，对生物质合成气化学当量比调整进行了实验研究。结果表明：气化炉内铁系催化剂调整效果不明显；在高温低硫的生物质气化气中，钛促进的钴钼耐硫催化剂具有较高的变换活性，CO转化率达到80％以上，合成气H2／CO比在1-8范围内可调；在V（CH4，CO2）=1、常压、750℃和镍基催化剂作用下沼气重整过量CO2，制备出宽V（H2／CO）、V（CO2）和V（CH4）均低于5％（摩尔百分比）的合成气；通过水煤气变换过程结合沼气重整过程，可依据目的产物合成的要求，制备合适化学当量比、高碳转化率的生物质合成气。     

木屑高温水蒸气气化制备合成气研究

在常压固定床反应器中进行木屑高温水蒸气气化制取合成气研究。分别在750~1000℃温度和0.32~1.02g/min水蒸气流量下进行实验,反应时间为10 min。主要研究反应温度和水蒸气流量对碳转化率、合成气产率及合成气组分的影响。研究结果表明,木屑水蒸气气化具有很高的反应活性,合成气产率在0.81~1.74 L/g之间;反应温度和水蒸气流量对碳转化率和合成气热值及组分影响显著;在反应温度950℃,水蒸气流量0.67 g/min时,碳转化率达到最高值99.47%;合成气主要由H2、CO、CO2、CH4及少量CnHm组成,其中(H2+CO)比例达到63%~75%,合成气热值在10.5~11.5 MJ/m3之间,H2/CO比在1.0~2.3之间。     

生物质蒸汽气化模拟研究

利用化学热力学软件(GasEQ)模拟了生物质蒸汽气化过程中温度、水蒸气与物料质量比(S/M)以及CO2浓度对H2,CH4和CO的影响;研究了冷合成气低位热值(LHV)和气化能量转化效率(q)随各参数变化的规律,并且考虑了外部能量的消耗。模拟研究得到:随着温度的升高,合成气的LHV总体表现出降低,并且q先增加后微弱下降,认为存在一个最优的气化温度(800⁹00℃);高S/M有利于H2的生成,提高H2的体积浓度,但水蒸气的增加,降低了LHV值,并且q先增加后减少,因为水蒸气会消耗大量外部能量,存在一个最经济的气化S/M;随着反应气中CO2浓度的升高,促进了生物质气化,并使CO浓度升高和H2浓度降低。     

基于活性炭的微波辐射CO_2重整CH_4的研究

以木质活性炭为催化剂,在微波加热实验台上进行了CO2重整CH4的实验研究,考察了活性炭的升温特性,比较了CH4裂解、CH4/CO2重整和CO2气化反应中反应气转化率,分析了反应温度、CH4与CO2物质的量比值和空气流速对重整反应的影响,测试了活性炭的催化活性.结果表明,微波辐射下活性炭床层温度迅速升高;重整反应中CH4转化率高于裂解反应,而CO2转化率低于气化反应;提高反应温度、减小CH4与CO2物质的量比值和降低空气流速均利于提高CH4和CO2转化率,同时降低合成气中H2与CO物质的量比值;初始阶段活性炭表现出较好的催化活性,40 min后活性炭迅速失活.     

甲烷三重整制合成气热力学分析

甲烷三重整反应(TRM,Tri-reforming of methane)具有过程能效高、合成气H2/CO适宜和较低催化剂积炭的优点。采用平衡常数法对TRM反应制合成气进行了热力学分析,研究了反应温度、压力及反应原料进气组分对重整特性的影响。结果表明:温度在1073K以上时TRM反应表现出很好的效果,温度升高有利于转化率的提高;但是压力的升高不利于反应正向进行。氧气含量增加,将使甲烷和二氧化碳转化率分别升至95%以上和降至10%以下,但是H2/CO值维持在1.5附近;水蒸气和二氧化碳含量增加,甲烷转化率升高,二氧化碳转化率降低,而且H2/CO值在1.4～2.1之间变化,前者使之升高,后者使之降低。     

串联交替式炉膛高热值生物质气化炉数值模拟及试验研究

对串联交替式炉膛高热值燃气生物质气化炉进行了研究,气化炉以木质颗粒为燃料、空气-水蒸气为气化剂,采用Fluent软件数值模拟了气化炉内水蒸气入口距离炉栅位置高度h、水蒸气入口流量Vs与空气入口流量V03个参数对燃气组分CO,H2和CH4体积浓度的影响。采用正交试验优化了上述3个参数,并试验测试了3个参数下燃气组分CO,H2和CH4体积浓度及燃气热值。数值模拟与试验结果表明,当h为175 mm,V0为0.92 m3/h,Vs为1.33 m3/h时,生物质燃气热值Q最大值为10.46 MJ/m3,比单一空气气化剂作用下提高了107.95%。     

木屑炭水蒸气催化气化制取合成气研究

以木屑炭为原料,K2CO3作为催化剂,以固定床气化炉为实验设备,进行水蒸气催化气化木屑炭的探究。考察木屑炭水蒸气气化的炭转化率、产氢率、气体组成体积分数和H2/CO比值随K2CO3催化剂质量分数(0~8%)、水蒸气流量(0.15~0.35 g/(min·g))、气化温度(800~950℃)变化的规律。实验结果表明:K2CO3催化剂可显著提升碳转化率及产氢率,K2CO3质量分数为8%时,碳转化率和产氢率分别达到86.3%和125.6 g/kg,同时合成气中CO体积分数显著增加,H2/CO比值降至2.43。增加水蒸气流量,合成气中H2含量显著增大,H2/CO比值随之增大。温度可有效促进炭气化过程,950℃时碳转化率和产氢率分别达到84.3%和127.1 g/kg,但合成气中CO体积分数增大,H2/CO比值降至2.48。实验得到H2/CO比值在2.43~5.16范围的合成气。气化反应温度在900℃、水蒸气0.2 g/(min·g)、K2CO3质量分数3%时,碳转化率可达80.4%,产氢率109.6 g/kg,合成气中(H2+CO)体积分数82.4%,同时H2/CO比值高达3.05。     

稻壳热解气化特性的试验研究

以稻壳为试验原料,DHC-32为催化剂.高纯N2为载气,在管式炉中研究了热解温度和DHC-32催化剂对稻壳热解气化特性的影响.试验结果表明:稻壳热解气中H2,CO含量随热解温度升高而增加,CH4CO2含量随热解温度升高而呈下降趋势;添加DHC-32催化剂后,未改变H2,CO,CH4,CO2含量随热解温度的变化趋势,但对4种气体的相对含量有一定的影响;在试验温度范围内,添加10%DHC-32催化剂比3%DHC-32催化剂对稻壳热解气影响更大一些.     

掺混比例对生物质和煤流化床共气化特性影响的试验研究

采用新型床料在鼓泡流化床中进行了2种典型的木本和草本生物质与烟煤的空气-水蒸气气化试验,研究了生物质掺混比例对燃气组分和热值、气化效率及碳转化率等参数的影响规律.结果表明:当松木屑的掺混比例从0%增大到100%时,H2和CO的体积含量分别增加了4.6%和4.4%,CO2的体积含量减少了3%,CH4和CnHm的含量也有所增加;当稻秸的掺混比例从0%增大到100%时,CO的体积含量先从25.8%上升至27.5%,再下降至25.3%,其他燃气组分的变化趋势与松木屑和煤气化的相类似;随着生物质掺混比例的增加,2种生物质和煤共气化的气化效率和碳转化率均有所提高,且在共气化过程中存在协同效应.     

Modeling of IT-SOFC with indirect internal reforming operation fueled by methane: Effect of oxygen adding as autothermal reforming

Mathematical models of an Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC) with indirect internal reforming operation (IIR-SOFC) fueled by methane were developed. The models were based on a steady-state heterogeneous two-dimensional tubular-design SOFC. The benefit in adding oxygen to methane and steam as the feed for autothermal reforming reaction on the thermal behavior and SOFC performance was simulated. The results indicated that smoother temperature gradient with lower local cooling at the entrance of the reformer channel can be achieved by adding a small amount of oxygen. However, the electrical efficiency noticeably decreased when too high oxygen content was added due to the loss of hydrogen generation from the oxidation reaction; hence, the inlet oxygen to carbon (O/C) molar ratio must be carefully controlled. Another benefit of adding oxygen is the reduction of excess steam requirement, which could reduce the quantity of heat required to generate the steam and eventually increases the overall system performance. It was also found that the operating temperature strongly affects the electrical efficiency achievement and temperature distribution along the SOFC system. By increasing the operating temperature, the system efficiency increases but a significant temperature gradient is also detected. The system with a counter-flow pattern was compared to that with a co-flow pattern. The co-flow pattern provided smoother temperature gradient along the system due to better matching between the heat supplied from the electrochemical reaction and the heat required for the steam reforming reaction. However, the electrical efficiency of the co-flow pattern is lower due to the higher cell polarization at a lower system temperature.     

A comparative assessment of homogeneous propane reforming at intermediate temperatures

The study compares the performance of different pathways for gas-phase (non-catalytic) fuel reforming between 600 and 1000 °C. Specifically, the conversion of propane to hydrogen-rich syngas was investigated numerically and experimentally for pyrolysis (Py), steam reforming (SR), partial oxidation (POx), and autothermal reforming (ATR). Experiments were conducted in a tubular quartz reactor, where temperatures were imposed externally; reactants were diluted with nitrogen to reduce the impact of endothermic/exothermic reactions on the variation of gas-phase temperatures. In experiments, product concentrations of hydrogen, carbon monoxide, carbon dioxide, methane, and a range of hydrocarbon species were measured at predetermined operating conditions. The performance of each homogeneous reforming process was evaluated and compared by assessing propane conversion and production efficiencies for hydrogen and other species of interest. At 600 °C, propane conversion was low, but increased substantially with temperature; complete conversion was achieved at 1000 °C. Furthermore, findings show improved hydrogen production efficiencies of POx/ATR when compared to Py/SR. Experimental results are substantiated by numerical simulations with detailed chemical kinetics; numerical results are in good agreement with experiments at identical operating conditions. Experimental and numerical results for non-catalytic propane reforming at all tested temperatures (600–1000 °C) imply a negligible impact of steam addition to the process, as results for SR resemble Py results, and ATR closely follows POx characteristics. As such, results clearly show that steam does not play an active role in gas-phase reforming of propane at intermediate temperatures.     

On-board LPG reforming system for an LPG · hydrogen mixed combustion engine

In this study, we evaluated the properties of a reforming catalyst system for generating hydrogen from liquified petroleum gas (LPG) fuel and supplying hydrogen to an LPG engine. The fuel supply system of the LPG engine was modified in order to supply LPG to a reforming catalyst prior to combustion. A test apparatus was also built to evaluate the performance of a reforming catalyst system. Gas chromatography was used to measure H₂, N₂, O₂, CH₄, and CO emissions, while CO₂ emissions were measured using an exhaust gas analyzer. The products concentration of the reforming reactions according to reforming fuel quantity and air flow was analyzed. In actual engine operating conditions, H₂ yield and air flow were proportional, whereas H₂ yield and fuel reforming fuel quantity were inversely proportional. The experimental results of the reforming reaction under various conditions will be used as the basic data for integrating the reforming catalyst system into an actual operating engine.     

Economic assessment of membrane-assisted autothermal reforming for cost effective hydrogen production with CO2 capture

A recent techno-economic study (Spallina et al., Energy Conversion and Management 120: p. 257–273) showed that the membrane assisted chemical looping reforming (MA-CLR) technology can produce H₂ with integrated CO₂ capture at costs below that of conventional steam methane reforming. A key technical challenge related to MA-CLR is the achievement of reliable solids circulation between the air and fuel reactors at large scale under the high (>50 bar) operating pressures required for optimal performance. This work therefore presents process modelling and economic assessments of a simplified alternative; membrane assisted autothermal reforming (MA-ATR), that inherently avoids this technical challenge. The novelty of MA-ATR lies in replacing the MA-CLR air reactor with an air separation unit (ASU), thus avoiding the need for oxygen carrier circulation. The economic assessment found that H₂ production from MA-ATR is only 1.5% more expensive than MA-CLR in the base case. The calculated cost of hydrogen (compressed to 150 bar) in the base case was 1.55 €/kg with a natural gas price of €6/GJ and an electricity price of €60/MWh. Both concepts show continued performance improvements with an increase in reactor pressure and temperature, while an optimum cost is achieved at about 2 bar H₂ permeate pressure. Sensitivities to other variables such as financing costs, membrane costs, fuel and electricity prices are similar between MA-ATR and MA-CLR. Natural gas prices represent the most important sensitivity, while the sensitivity to membrane costs is relatively small at high reactor pressures. MA-ATR therefore appears to be a promising alternative to achieve competitive H₂ production with CO₂ capture if technical challenges significantly delay scale-up and deployment of MA-CLR technology. The key technical demonstration required before further MA-ATR scale-up is membrane longevity under the high reactor pressures and temperatures required to minimize the cost of hydrogen.     

An alternative process for gasoline fuel processors

The article explores the thermodynamics of an alternate hydrogen generation process - dry autothermal reforming and its comparison to autothermal reforming process of isooctane for use in gasoline fuel processors for SOFC. A thermodynamic analysis of isooctane as feed hydrocarbon for autothermal reforming and dry autothermal reforming processes for feed OCIR (oxygen to carbon in isooctane ratio) from 0.5 to 0.7 at 1 bar pressure under analogous thermoneutral operating conditions was done using Gibbs free energy minimization algorithm in HSC Chemistry. The trends in thermoneutral points (TNP), important product gas compositions at TNPs and fuel processor energy requirements were compared and analyzed. Dry autothermal reforming was identified as a less energy consuming alternative to autothermal reforming as the syngas can be produced with lower energy requirements at thermoneutral temperatures, making it a promising candidate for use in gasoline fuel processors to power the solid oxide fuel cells. The dry autothermal reforming process for syngas production can also be used for different fuels.     

Autothermal reforming over a Pt/Gd-doped ceria catalyst: Heat and mass transport limitations in the steam reforming section

Autothermal reforming (ATR) has several advantages for fuel cell applications, such as a compact reactor structure and fast response. Using oxidation reactions inside the reactor, ATR does not have the external heat transfer limitations associated with steam reforming. However, mass and heat transfer limitations inside and outside the catalyst particles are still anticipated. In this study, transport limitations in the steam reforming section of ATR over a Pt/Gd-doped ceria catalyst are analyzed by numerical simulations based on a reaction rate equation in which parameters are adjusted to measured kinetic data. The simulation results show that significant transport limitations characterize the steam reforming section of packed-bed ATR reactors. The activity per catalyst bed volume is highly dependent on the particle size, and only the thin exterior layer of the particles is involved in catalyzing the reactions. Based on the results, it is shown that an eggshell type catalyst particle could reduce catalyst material significantly without a considerable decline in the activity per catalyst bed volume.     

Externally reformed solid oxide fuel cell–micro-gas turbine (SOFC–MGT) hybrid systems fueled by methanol and di-methyl-ether (DME)

Solid oxide fuel cell–micro-gas turbine (SOFC–MGT) hybrid power plants integrate a solid oxide fuel cell and a micro-gas turbine and can achieve efficiencies of over 60% even for small power outputs (200–500 kW). The SOFC–MGT systems currently developed are fueled with natural gas, which is reformed inside the same stack, but the use of alternative fuels can be an interesting option. In particular, as the reforming temperature of methanol and di-methyl-ether (DME) (200–350 °C) is significantly lower than that of natural gas (700–900 °C), the reformer can be sited outside the stack. External reforming in SOFC–MGT plants fueled by methanol and DME enhances efficiency due to improved exhaust heat recovery and higher voltage produced by the greater hydrogen partial pressure at the anode inlet. The study carried out in this paper shows that the main operating parameters of the fuel reforming section (temperature and steam-to-carbon ratio (SCR)) must be carefully chosen to optimise the hybrid plant performance. For the stoichiometric SCR values, the optimum reforming temperature for the methanol fueled hybrid plant is approximately 240 °C, giving efficiencies of about 67–68% with a SOFC temperature of 900 °C (the efficiency is about 72–73% at 1000 °C). Similarly, for DME the optimum reforming temperature is approximately 280 °C with efficiencies of 65% at 900 °C (69% at 1000 °C). Higher SCRs impair stack performance. As too small SCRs can lead to carbon formation, practical SCR values are around one for methanol and 1.5–2 for DME.     

A thermodynamic study of propanol reforming in presence of hydrazine for hydrogen production

Thermodynamic analysis of hydrogen production from propanol reforming reactions, by decomposition and steam reforming, in presence of hydrazine was evaluated as a function of temperature (300–900 K) at a constant pressure of 1 atm. The molar ratio of reactants were varied to identify the conditions leading to hydrogen rich product stream with low carbon formation. Steam reforming of propanol displayed higher hydrogen production and a gradual decrease in carbon content with an increase in the steam/propanol ratio. Addition of hydrazine leads to a further enhancement in hydrogen amount along with a suppression in coking. A similar trend was observed in case of propanol decomposition reaction. Addition of hydrazine leads to a favorable condition for hydrogen production along with a decrease in carbon formation. In both, steam reforming and decomposition, methane and water seem to be the stable products at low temperature, which react together at elevated temperatures following steam reforming of methane to generate CO and hydrogen. Hydrazine, on the other hand diminishes carbon at low temperature and produces ammonia, which decomposes at higher temperature to generate hydrogen and nitrogen. It is clear that steam assists in eliminating carbon at higher temperature whereas hydrazine is helpful in removing carbon formation at lower temperature. Also, a considerably high ratio of H₂/CO can be maintained in both the reactions, propanol steam reforming and propanol decomposition, by introducing a hydrazine stream in the feed.     

Technological aspects of an auxiliary power unit with internal reforming methanol fuel cell

Increasing source runtime, speeding up the transient response, while minimizing weight, volume and cost of the power supply system are key requirements for portable, mobile and off-grid applications of fuel cells. In this respect, Internal Reforming Methanol Fuel Cell (IRMFC) modules were designed, constructed and tested based on an innovative double reformer (DRef) configuration and metallic bipolar plates (BPPs) with unique arrangement. Recently developed cross-linked Advent TPS^® high-temperature membrane electrode assemblies (MEAs) were employed for fuel cell operation at 210 °C. Taking into account the requirement for a light-weight and low-volume stack, Cu-based methanol reforming catalyst were supported on carbon papers, resulting in ultra-thin reformers. The proposed configuration offered a significant decrease in the weight and volume of the whole power system, as compared with previous voluminous foam-based modules. Moreover, specifically designed bipolar plates were made of coated Al-metal alloys, which proved to be stable in the strong acidic environment at elevated temperatures. The prototype 32MEAs-32DRef IRMFC stack of 100 W including home-made insulation casing, was integrated for operation at 200–210 °C and at 0.2 A cm⁻², demonstrating the functionality of the unit. A power output of 100.7 W (3.14 W per cell; 0.114 W cm⁻²) was achieved in the last run following several on-off cycles. The volumetric power density of the IRMFC stack including insulation and casing is around 30 W per lt, being among the highest reported either in the case of portable or stationary applications. Overall, the observed stability of reformers and bipolar plates was satisfactory within the timeframe of the work undertaken. Specific targets for improvement of the efficiency were identified, and the main drawback had to do with low thermal and mechanical stability of the membranes under start-up/shut-down transient operation.     

A review on reforming bio-ethanol for hydrogen production

Bio-ethanol is a prosperous renewable energy carrier mainly produced from biomass fermentation. Reforming of bio-ethanol provides a promising method for hydrogen production from renewable resources. Besides operating conditions, the use of catalysts plays a crucial role in hydrogen production through ethanol reforming. Rh and Ni are so far the best and the most commonly used catalysts for ethanol steam reforming towards hydrogen production. The selection of proper support for catalyst and the methods of catalyst preparation significantly affect the activity of catalysts. In terms of hydrogen production and long-term stability, MgO, ZnO, _CeO2${\mathrm{CeO}}_2$, and _La2O3${\mathrm{La}}_2{\mathrm{O}}_3$ are suitable supports for Rh and Ni due to their basic characteristics, which favor ethanol dehydrogenation but inhibit dehydration. As Rh and Ni are inactive for water gas shift reaction (WGSR), the development of bimetallic catalysts, alloy catalysts, and double-bed reactors is promising to enhance hydrogen production and long-term catalyst stability. Autothermal reforming of bio-ethanol has the advantages of lesser external heat input and long-term stability. Its overall efficiency needs to be further enhanced, as part of the ethanol feedstock is used to provide low-grade thermal energy. Development of millisecond-contact time reactor provides a low-cost and effective way to reform bio-ethanol and hydrocarbons for fuel upgrading. Despite its early R&D stage, bio-ethanol reforming for hydrogen production shows promises for its future fuel cell applications.