生物质水蒸气气化制氢模拟研究

利用ASPEN PLUS软件建立了生物质水蒸气气化制氢模型,对各种影响因素进行了深入分析。结果表明:随着碳转化率的增加,H2浓度略有降低,H2产量大幅增加,在碳转化率为1时达到最大值142.54 g/kg;随着水蒸气/生物质质量比的增加,H2浓度和产量大幅增加,而后趋于稳定,水蒸气/生物质质量比取2比较适宜。适当的升温和低压对制备H2有利,在加压条件下,H2浓度与产量达到最大值的温度升高。     

Hydrogen-rich gas production from biomass air and oxygen/steam gasification in a downdraft gasifier

Biomass gasification is an important method to obtain renewable hydrogen. However, this technology still stagnates in a laboratory scale because of its high-energy consumption. In order to get maximum hydrogen yield and decrease energy consumption, this study applies a self-heated downdraft gasifier as the reactor and uses char as the catalyst to study the characteristics of hydrogen production from biomass gasification. Air and oxygen/steam are utilized as the gasifying agents. The experimental results indicate that compared to biomass air gasification, biomass oxygen/steam gasification improves hydrogen yield depending on the volume of downdraft gasifier, and also nearly doubles the heating value of fuel gas. The maximum lower heating value of fuel gas reaches 11.11 MJ/N m³ for biomass oxygen/steam gasification. Over the ranges of operating conditions examined, the maximum hydrogen yield reaches 45.16 g H₂/kg biomass. For biomass oxygen/steam gasification, the content of H₂ and CO reaches 63.27–72.56%, while the content of H₂ and CO gets to 52.19–63.31% for biomass air gasification. The ratio of H₂/CO for biomass oxygen/steam gasification reaches 0.70–0.90, which is lower than that of biomass air gasification, 1.06–1.27. The experimental and comparison results prove that biomass oxygen/steam gasification in a downdraft gasifier is an effective, relatively low energy consumption technology for hydrogen-rich gas production.     

Oxidative catalytic steam gasification of sugarcane bagasse for hydrogen rich syngas production

Reactive Flash Volatilization (RFV) is an emerging thermochemical method to produce tar free hydrogen rich syngas from waste biomass at relatively lower temperature (<900 °C) in a single stage catalytic reactor within a millisecond residence time. Here, we show catalytic RFV of bagasse using Ru, Rh, Pd, or Re promoted Ni/Al₂O₃ catalysts under steam rich and oxygen deficient environment. The optimum reaction conditions were found to be 800 °C, steam to carbon ratio = 1.7 and carbon to oxygen ratio = 0.6. Rh–Ni/Al₂O₃ performed the best, resulting in highest hydrogen concentration in the synthesis gas at 54.8%, with a corresponding yield of 106.4 g-H₂/kg bagasse. A carbon conversion efficiency of 99.96% was achieved using Rh–Ni, followed by Ru–Ni, Pd–Ni, Re–Ni and mono metallic Ni catalyst in that order. Alkali and Alkaline Earth Metal species present in the bagasse ash and char, that deposited on the catalyst, was found to enhance its activity and stability. The hydrogen yield from bagasse was higher than previously reported woody biomass and comparable to the microalgae.     

Catalytic steam reforming of tar for enhancing hydrogen production from biomass gasification: a review

Presently, the global search for alternative renewable energy sources is rising due to the depletion of fossil fuel and rising greenhouse gas (GHG) emissions. Among alternatives, hydrogen (H₂) produced from biomass gasification is considered a green energy sector, due to its environmentally friendly, sustainable, and renewable characteristics. However, tar formation along with syngas is a severe impediment to biomass conversion efficiency, which results in process-related problems. Typically, tar consists of various hydrocarbons (HCs), which are also sources for syngas. Hence, catalytic steam reforming is an effective technique to address tar formation and improve H₂ production from biomass gasification. Of the various classes in existence, supported metal catalysts are considered the most promising. This paper focuses on the current researching status, prospects, and challenges of steam reforming of gasified biomass tar. Besides, it includes recent developments in tar compositional analysis, supported metal catalysts, along with the reactions and process conditions for catalytic steam reforming. Moreover, it discusses alternatives such as dry and autothermal reforming of tar.     

Combined slow pyrolysis and steam gasification of biomass for hydrogen generation—a review

Hydrogen, the inevitable fuel of the future, can be generated from biomass through promising thermochemical methods. Modern‐day thermochemical methods of hydrogen generation include fast pyrolysis followed by steam reforming of bio‐oil, supercritical water gasification and steam gasification. Apart from the aforementioned methods, a novice technique of employing combined slow pyrolysis and steam gasification can be also engaged to produce hydrogen of improved yield and quality. This review paper discusses in detail about the existing hydrogen generation through thermochemical methods. It elaborates the merits and demerits of each method and gives insight about the combined slow pyrolysis and steam gasification process for hydrogen generation. The paper also elaborates about the various parameters affecting integrated slow pyrolysis and steam gasification process. Copyright © 2014 John Wiley & Sons, Ltd.     

木屑水蒸气气化热重分析及合成气释放特性

试验研究了木屑在水蒸气气氛下的热失重行为及气化过程中合成气释放特性。首先采用TG-DTA对木屑样品进行了水蒸气气氛下的热重行为分析,结果表明,木屑气化过程可以分为挥发分释放和半焦气化两个阶段,分别可由二级反应动力学和三维扩散Ginstling-Broushtein方程描述,对应的表观活化能分别为87.014kJ/mol和103.35 kJ/mol。此外,在自制的固定床气化反应装置上,研究了生物质气化过程中挥发分释放和半焦气化阶段合成气释放特性。另外,半焦水蒸气气化阶段对气体中合成气含量和H2/CO起到决定性作用,通过合理调控半焦气化阶段反应条件,可以得到合适化学当量比的生物质合成气。     

Novel hydrogen‐rich gas production by steam gasification of biomass in a research‐scale rotary tubular helical coil gasifier

The concept of biomass steam gasification offers platform for production (i) of hydrogen, (ii) hydrocarbons and (iii) value added chemicals. Majority of these developments are either in nascent or in pilot/demonstration stage. In this context, there exists potential for hydrogen production via biomass steam gasification. Gaseous products of biomass steam gasification consist of large percentage of CO, CH₄ and other hydrocarbons, which can be converted to hydrogen through water‐gas‐shift reaction, steam reforming and cracking respectively. Although there are many previous research works showing the potential of production of hydrogen from biomass in a two stage process, challenges remain in extended biomass and char gasification so as to reduce the amount of carbon in the residual char as well as improve conversion of heavy hydrocarbon condensates to hydrogen rich gas. In the current work, the characteristics of biomass steam gasification in an in‐house designed rotary tubular helical coil reactor at temperatures less than 850 °C, in the presence of superheated steam, were presented. The objectives were to obtain high carbon conversion in the primary biomass steam gasification step (upstream) and high product gas yield and hydrogen yield in the secondary fixed bed catalytic step (downstream). The influence of temperature, steam‐to‐biomass ratio and residence time on product gas yield in the rotary tubular helical coil gasifier was studied in detail using one of the abundantly available biomass sources in India‐rice husk. Further, enhancement of product gas yield and hydrogen yield in a fixed bed catalytic converter was studied and optimized. In the integrated pathway, a maximum gas yield of 1.92 Nm³/kg moisture‐free biomass was obtained at a carbon conversion efficiency of 92%. The maximum hydrogen purity achieved under steady state conditions was 53% by volume with a hydrogen yield of 91.5 g/kg of moisture‐free biomass. This study substantiates overall feasibility of production of high value hydrogen from locally available biomass by superheated steam gasification followed by catalytic conversion. Copyright © 2016 John Wiley & Sons, Ltd.     

Hydrogen and syngas production from sewage sludge via steam gasification

High temperature steam gasification is an attractive alternative technology which can allow one to obtain high percentage of hydrogen in the syngas from low-grade fuels. Gasification is considered a clean technology for energy conversion without environmental impact using biomass and solid wastes as feedstock. Sewage sludge is considered a renewable fuel because it is sustainable and has good potential for energy recovery. In this investigation, sewage sludge samples were gasified at various temperatures to determine the evolutionary behavior of syngas characteristics and other properties of the syngas produced. The syngas characteristics were evaluated in terms of syngas yield, hydrogen production, syngas chemical analysis, and efficiency of energy conversion. In addition to gasification experiments, pyrolysis experiments were conducted for evaluating the performance of gasification over pyrolysis. The increase in reactor temperature resulted in increased generation of hydrogen. Hydrogen yield at 1000 °C was found to be 0.076 g_gas g_sample⁻¹. Steam as the gasifying agent increased the hydrogen yield three times as compared to air gasification. Sewage sludge gasification results were compared with other samples, such as, paper, food wastes and plastics. The time duration for sewage sludge gasification was longer as compared to other samples. On the other hand sewage sludge yielded more hydrogen than that from paper and food wastes.     

Hydrogen and syngas production from biomass gasification for fuel cell application

Gasification process is being developed to produce a clean and efficient gas flue from fuels such as coal, biomass, and solid/liquid wastes for power generation. In this work, a biomass gasification kinetic model that can predict reaction temperature, gasification performance, and gas composition has been developed for a circulating fluidized bed (CFB). Experimental data from a CFB power plant have been used to validate the model. It is confirmed that the addition of steam is important for increasing the hydrogen concentration and syngas caloric value. Based on the predicted results, an optimal condition is suggested for air and steam gasification in the CFB gasifier.     

Development of a high‐temperature two‐stage entrained flow gasifier model for the process of biomass gasification and syngas formation

This paper presents development of the Mitsubishi Heavy Industries (MHI) gasifier utilizing an analogy between a model with coal feedstock and the model with torrefied woody biomass. A computational fluid dynamics (CFD) model was primarily developed for coal gasification, and the simulation results were validated with similar published work and experimental measurements. The model was extended for the woody biomass to predict the gasifier performance under the gasification process. The results were used to compare the effect of fuel type on the gasifier performance and gaseous product compositions. The second‐level injection nozzles were modified tangentially, and the flow characteristics, species yields, and temperature were evaluated. The possibility of reducing the gasifier length from 13 to 8 m is also evaluated for different total length. The results revealed that using woody biomass leads to a decrease in the mole fraction of CO and H₂ at the gasifier outlet compared with coal. An opposite trend was observed for CO₂ and CH₄ compositions. The contributions of modified second‐level nozzles to the total gas composition and exit temperature only account for less than 3%. Reducing the gasifier length from 13 to 8 m increased the exit temperature from 1289 to 1340 K, but the changes in the exit gas composition were less than 2%. The new design of the MHI gasifier can reduce the investment costs by reducing the gasifier length as well as using biomass instead of coal.     

Valorizing petroleum coke into hydrogen-rich syngas through K-promoted catalytic steam gasification

Hydrogen-rich syngas was successfully produced from catalytic steam gasification of petroleum coke. This work studied the steam gasification of petroleum coke over KOH, K₂CO₃, KNO₃, CaO, Fe₂O₃, K₂CO₃–CaO and K₂CO₃–Fe₂O₃ in a pressurized fixed bed. KOH and K₂CO₃ demonstrated good catalytic activity compared with other catalysts. The carbon conversion efficiency (CCE) increased from 14.7 wt% to 61.4 wt% and 87.9 wt% after adding 10 wt% K₂CO₃ and 10 wt% KOH, respectively, and H₂ content increased from 60.9 vol% to 66.7 vol% and 64.2 vol%. The increase of gasification temperature and pressure resulted in the increase of CCE. However, raising temperature was beneficial to the increase of H₂ and CO contents, while the elevated pressure was in favor of the formation of CH₄. In addition, the K-catalytic steam gasification of petroleum coke accorded with the oxygen transfer and intermediate hybrid mechanism.     

Neural network modeling of biomass gasification for hydrogen production

Hydrogen plays a significant role as an alternative feedstock in the production of several industrial chemicals such as methanol and ammonia; it can also be used as a clean fuel for power generation in the Internal Combustion (IC) engines and Proton Exchange Membrane (PEM) fuel cells. The main objective of this work is to develop a computer-based model based on the experimental data to predict the gasification behavior of biomass particles for hydrogen and syngas production. The results showed that an increase in gasification temperature significantly increased the hydrogen yield and CGE. The maximum CGE also found to be increased by about 230% when the reaction temperature increases from 700 to 900 ^?C.     

Experimental study on biomass steam gasification for hydrogen-rich gas in double-bed reactor

Based on Response Surface Methodology, the experiments of biomass catalytic gasification designed by Design-Expert software were carried out in steam atmosphere and double-bed reactor. The response surface was set up with three parameters (gasification temperature, the content of K-based catalyst in gasification bed and the content of Ni-based catalyst in reforming bed) for biomass gasification performance of carbon conversion efficiency and hydrogen yield to make analysis and optimization about the reaction characteristics and gasification conditions. Results showed that gasification temperature and the content of K-based catalyst in gasification bed had significant influence on carbon conversion efficiency and hydrogen yield, whilst the content of Ni-based catalyst in reforming bed affected the gasification reactions to a large extent. Furthermore, appropriate conditions of biomass steam gasification were 800 °C for gasification temperature, 82% for the content of K-based catalyst in gasification bed and 74% for the content of Ni-based catalyst in reforming bed by the optimization model. In these conditions, the steam gasification experiments using wheat straw showed that carbon conversion efficiency was 96.9% while hydrogen yield reached 64.5 mol/kg, which was in good agreement with the model prediction. The role of the reforming bed was also analyzed and evaluated, which provided important insight that the employment of reforming bed made carbon conversion efficiency raised by 4.8%, while hydrogen yield achieved a relative growth of 50.5%.     

Modeling of fixed bed downdraft biomass gasification: Application on lab‐scale and industrial reactors

This study aimed at presenting a model to simulate downdraft biomass gasification under steady‐state or unsteady‐state conditions. The model takes into account several processes that are relevant to the transformation of solid biomass into fuel gas, such as drying; devolatilization; oxidation; CO₂, H₂O, and H₂ reduction with char, pressure losses, solid and gas temperature, particle diameter, and bed void fraction evolution; and heat transfer by several mechanisms such as solid–gas convection, bed–wall convection, and radiation in the solid phase. Model validation is carried out by performing experiments in two lab‐scale downdraft fixed bed reactors (unsteady‐state conditions) and in a novel industrial pilot plant of 400 kW_th–100 kW_e (steady‐state conditions). The capability of the model to predict the effect of several factors (reactor diameter, air superficial velocity, and particle size and biomass moisture) on key response variables (temperature field, maximum temperature inside the bed, flame front velocity, biomass consumption rate, and composition and calorific value of the producer gas) is evaluated. For most response variables, a good agreement between experimental and estimated values is attained, and the model is able to reproduce the trend of variation of the experimental results. In general terms, the process performance improves with higher reactor diameter and lesser air superficial velocity, particle size, and moisture content of biomass. The steady‐state simulation appears to be a versatile tool for simulating different reactor configurations (preheating systems, variable geometry, and different materials). Copyright © 2013 John Wiley & Sons, Ltd.     

Experimental investigation of a multi‐stage air‐steam gasification process for hydrogen enriched gas production

To achieve hydrogen‐rich and low‐tar producer gas, multi‐stage air‐blown and air‐steam gasification processes were studied in this research. Results showed that the tar content from multi‐stage air‐blown and air‐steam gasification were lower, compared to the average value of that from downdraft gasification. In the cases of air supplies of 80, 100 l min^?1 and 100, 100 l min^?1 with steam, hydrogen yields were increased by 40.71 and 41.62%, respectively, compared to that without steam. These were about 1.6 times of hydrogen flow rate of the base case (S/B = 0). However, it was found that too much steam added to the process was disadvantageous. The equilibrium model was also applied to predict the hydrogen production and the composition of producer gas obtained from the multi‐stage air‐blown and air‐steam gasification processes. The predicted result showed a better match for the case of multi‐stage air‐blown gasification process. Copyright © 2010 John Wiley & Sons, Ltd.     

Modelling of a downdraft biomass gasifier with finite rate kinetics in the reduction zone

A model of a downdraft gasifier has been developed based on chemical equilibrium in the pyro‐oxidation zone and finite rate kinetic‐controlled chemical reactions in the reduction zone. The char reactivity factor (C_RF) in the reduction zone, representing the number of active sites on the char and its degree of burn out, has been optimized by comparing the model predictions against the experimental results from the literature. The model predictions agree well with the temperature distribution and exit gas composition obtained from the experiments at C_RF=100. A detailed parametric study has been performed at different equivalence ratios (between 2 and 3.4) and moisture content (in the range of 0–40%) in the fuel to obtain the composition of the producer gas as well as its heating value. It is observed that the heating value of the producer gas increases with the increase in the equivalence ratio and decrease in the biomass moisture content. The effect of divergence angle of the reduction zone geometry (in the range of 30–150°) on the temperature and species concentration distributions in the gasifier has been studied. An optimum divergence angle, giving the best quality of the producer gas, has been identified for a particular height of the reduction zone. Copyright © 2009 John Wiley & Sons, Ltd.     

Numerical study on solar spouted bed reactor for conversion of biomass into hydrogen-rich gas by steam gasification

A solar-powered biomass steam gasification system was developed, in which heat transfer model, flow model and chemical model were constructed to predict the distributions of temperature, pressure, mole fraction of syngas, and solar incident flux. Several key parameters of gasifier were designed to ensure the fluidization stability. Based on the model validation, gasifier performance simulations in the design working conditions were obtained. The effects of the key variable parameters, including the rim angle of the dish collector, steam-to-biomass mass flow ratio, biomass feeding rate and the solar irradiance in the different operation working conditions on the composition of syngas, lower heating value, and efficiencies were investigated. The results reveal that the coupled system implements the best gasification performance in the design conditions which the rim angle, steam-to-biomass mass flow ratio, and biomass feeding rate are set at 60°, 0.4, and 2.5 g/min, while the LHV, carbon conversion, and gasification energy efficiencies are 11.51 MJ/m³, 78.17%, and 93.01%, respectively. The overall energy efficiency considering solar energy is 30.79%.     

Transient gasification and syngas formation from coal particles in a fixed‐bed reactor

An experimental investigation on gasification and syngas formation from coal particles in a fixed‐bed reactor is conducted; particular attention is paid to the transient reaction dynamics. Three different coals, including two high‐volatile coals and a low‐volatile coal, are taken into consideration. In the initial reaction period, a two‐stage reaction is clearly observed; specifically, an exothermic reaction followed by an endothermic reaction is exhibited. Meanwhile, seeing that the devolatilization and pyrolysis reactions are pronounced, the initial concentrations of H₂ and CH₄ are relatively high, especially for the former. With increasing time, the interaction between coal and char particles is dominated by the latter, the concentrations of CO and CO₂ thus become higher. From the observation of syngas combustion, the entire gasification intensity proceeds from intensified growth, rapid decay, and then to progressive decay with increasing reaction time. For the two high‐volatile coals, the mass depletion is enhanced markedly once the reaction temperature is as high as 1000°C, whereas it is insensitive to the temperature for the low‐volatile coal. Nevertheless, it is found that, based on the weights of moisture and volatile matter, their relative release ratio from the low‐volatile coal is better than that from the high‐volatile coals. This implies that the final devolatilization and pyrolysis extent is not determined by coal grade. Copyright © 2006 John Wiley & Sons, Ltd.     

Comparison between isothermal and microwave gasification of lignite char for high syngas production

Using the water of lignite as gasification agent, this paper mainly studies the influence of microwave and isothermal gasification on the syngas production and H₂/CO ratio to obtain the maximum possible amount of high-quality syngas. The results show that microwave heating produced syngas had an immensely superior performance over conventional heating. The total gas yields of 1,000 W microwave gasification is 1.75 times more than that of the 1,000°C isothermal gasification. Moreover, the values of H₂/CO ratio obtained from microwave gasification was higher than 1,000°C isothermal gasification.     

Absorption-enhanced steam gasification of biomass for hydrogen production: Effect of calcium oxide addition on steam gasification of pyrolytic volatiles

The effect mechanism of calcium oxide (CaO) addition on gasification of pyrolytic volatiles as a key sub-process in the absorption-enhanced steam gasification of biomass (AESGB) for H₂ production at different conditions was investigated using a two-stage fixed-bed pyrolysis–gasification system. The results indicate that CaO functions as a CO₂ absorbent and a catalyst in the volatiles gasification process. CaO triggers the chemical equilibrium shift to produce more H₂ and accelerates volatile cracking and gasification reactions to obtain high volatile conversion rates. Increasing the gasification temperature could improve the reaction rate of cracking and gasification of volatiles as well as the catalytic effect of CaO, which continuously increase H₂ yield. When the gasification temperature exceeds 700 °C, the sharp decrease in CO₂ absorption capability of CaO drastically increases the CO₂ concentration and yield, which significantly decrease H₂ concentration. The appropriate temperature for the absorption-enhanced gasification process should be selected between 600 °C and 700 °C in atmospheric pressure. Increasing the water injection rate (represented as the mass ratio of steam to biomass) could also improve H₂ yield. The type of biomasses is closely associated with H₂ yield, which is closely related to the volatile content of biomass materials.