基于Gibbs自由能最小化原理模拟生物质流化床气化

基于能质平衡和吉布斯(Gibbs)自由能最小化原理,选择松木屑和麦秆两种生物质,利用化工商业化软件ASPEN PLUS模拟生物质流化床气化过程,并结合试验数据验证模拟结果的准确性。在此基础上考察了高温、原料含水率大范围变化等试验中较难实现的操作对气化的影响。模拟结果表明,搭建的气化模型能较好地模拟生物质气化过程,对生物质气化试验与工程放大具有一定的参考价值。     

A two phase model of high temperature steam-only gasification of biomass char in bubbling fluidized bed reactors using nuclear heat

A two phase biomass char steam gasification kinetic model is developed in a bubbling fluidized bed with nuclear heat as source of energy. The model is capable of predicting the temperature and concentration profiles of gases in the bubble, emulsion gas and solid phases. The robust model calculates the dynamic and steady state profiles, as well as the complex parameters of fluidized bed. Three pilot scale gasifiers were simulated in order to see the effect of the H/D ratio and the bed heating dynamics in the gasification kinetics, these parameters are found to be really important in order to enhance the water-gas shift reaction, and consequently, the hydrogen production. For the system modeled, hydrogen is the principal product of the steam-only gasification, as reported in the literature data. The carbon dioxide yield seems to be smaller than the ones in other works, but these differences are due principally to the energy source (no combustion is conducted) and that char (no oxygen in the solids) was used as the carbon source.     

Modeling of biomass gasification in fluidized bed

Modeling of biomass gasification in bubbling and circulating fluidized bed (FB) gasifiers is reviewed. Approaches applied for reactor modeling, from black-box models to computational fluid-dynamic models, are described. Special attention is paid to comprehensive fluidization models, where semi-empirical correlations are used to simplify the fluid-dynamics. The conversion of single fuel particles, char, and gas is examined in detail. The most relevant phenomena to be considered in modeling of FB biomass gasifiers are outlined, and the need for further investigation is identified. An updated survey of published mathematical reactor models for biomass and waste gasification in FB is presented. The overall conclusion is that most of the FB biomass gasification models fit reasonably well experiments selected for validation, despite the various formulations and input data. However, there are few measurements available for comparison with detailed model results. Also, validation of models with data from full-scale FB biomass gasification units remains to be done.     

Hydrogen production via CaO sorption enhanced anaerobic gasification of sawdust in a bubbling fluidized bed

This paper presents the experimental results of CaO sorption enhanced anaerobic gasification of biomass in a self-design bubbling fluidized bed reactor, aiming to investigate the influences of operation variables such as CaO to carbon mole ratio (CaO/C), H₂O to carbon mole ratio (H₂O/C) and reaction temperature (T) on hydrogen (H₂) production. Results showed that, over the ranges examined in this study (CaO/C: 0-2; H₂O/C: 1.2-2.18, T: 489-740 °C), the increase of CaO/C, H₂O/C and T were all favorable for promoting the H₂ production. The investigated operation variables presented different influences on the H₂ production under fluidized bed conditions from those obtained in thermodynamic equilibrium analysis or fixed bed experiments. The comparison with previous studies on fluidized bed biomass gasification reveals that this method has the advantage of being capable to produce a syngas with high H₂ concentration and low CO₂ concentration.     

Research on the characteristics of biomass gasification in a fluidized bed

The depletion of fossil fuels and the increasing environmental problems, make biomass energy a serious alternative resource of energy. Biomass gasification is one of the major biomass utilization technologies to produce high quality gas. In this paper, biomass gasification was performed in a self-designed fluidized bed. The main factors (equivalence ratio, bed temperature, added catalyst, steam) influenced the gasification process were studied in detail. The results showed that the combustible gas content and the heating value increased with the increase of the temperature, while the CO₂ content decreased. The combustible gas content decreased with the increase of the equivalence ratio (ER), but CO₂ content increased. At the same temperature and at different ratios of CaO (from 0 to 20%), H₂ content was increased significantly, CO content was also increased, CH₄ content increased slightly, but CO₂ content was decreased. With the addition of steam at different temperature, the gas in combustible components increased, the content of H₂ increased obviously. The growth rate was 50% increased. As the bed temperature increased, gas reforming reaction increased, the CO and CH₄ content decreased, but CO₂ and H₂ content increased.     

Biomass steam gasification in bubbling fluidized bed for higher-H2 syngas: CFD simulation with coarse grain model

A comprehensive coarse grain model (CGM) is applied to simulation of biomass steam gasification in bubbling fluidized bed reactor. The CGM was evaluated by comparing the hydrodynamic behavior and heat transfer prediction with the results predicted using the discrete element method (DEM) and experimental data in a lab-scale fluidized bed furnace. CGM shows good performance and the computational time is significantly shorter than the DEM approach. The CGM is used to study the effects of different operating temperature and steam/biomass (S/B) ratio on the gasification process and product gas composition. The results show that higher temperature enhances the production of CO, and higher S/B ratio improves the production of H₂, while it suppresses the production of CO. For the main product H₂, the minimum relative error of CGM in comparison with experiment is 1%, the maximum relative error is less than 4%. For the total gas yield and H₂ gas yield, the maximum relative errors are less than 7%. The predicted concentration of different product gases is in good agreement with experimental data. CGM is shown to provide reliable prediction of the gasification process in fluidized bed furnace with considerably reduced computational time.     

Kinetic analysis of catalytic coal gasification process in fixed bed condition using Aspen Plus

Coal is one of the energy resources useful for solving the energy crisis. It has met nearly half of the rise in global energy demand over the last decade, growing even faster than total renewables. Catalytic coal gasification is useful technology in SNG (Substitute Natural Gas) and IGFC (Integrated Gasification Fuel Cell) plants that use coal. The Catalytic Coal Gasification Process developed by Exxon in 1978 was simulated with Aspen Plus in the fixed bed type reactor. The purpose of this study is to derive kinetic parameters from experimental results in literature and compare them using the catalytic coal gasification model in Aspen Plus. Carbon–Steam reaction is an important reaction in catalytic gasification reaction since steam is only an oxidant feeding in the system. Mainly, alkali metal gasification catalysts like potassium carbonate increase the rate of steam gasification. The kinetic values calculated from the experimental data are 0.30126, 0.09204, and 0.076995 (cc mol⁻¹ h⁻¹). Obtained kinetic value k_f determines k_o and E values compared with Arrhenius equation to input Aspen Plus simulation. Another major focus is on low-rank coal because upgrading low-rank coal is very useful for energy efficiency and environmental aspects. Upgrading coal means removing moisture from low-rank coal. Boiler efficiency is decreased because a lot of moisture content and CO₂ emissions are increased. Carbon dioxide and the flue gas emissions for the same energy level can be reduced by about 30%. Low-rank coal will be increased energy requirement for removing carbon dioxide. The investigation of the drying characteristics of low-rank coal is performed in our laboratory. The experimental results based on the drying characteristics are reflected in this simulation process.     

Experimental investigation of the effect of physical pre-treatment on air-blown fluidized bed biomass gasification

The effect of comminution, drying, and densification on bubbling fluidized bed gasification was investigated by fractionating a forestry residue into a feedstock consisting of different particle sizes, moisture levels, and by densifying to pellets. The gasification performance was evaluated at nominal average bed temperatures of 725°, 800° and 875 °C at a constant fluidizing velocity (0.91 m s⁻¹) with feed input rates between 9 and 24 kg h⁻¹.The gas composition was observed to be influenced by both the particle size and form. Smaller particles led to a gas richer in carbon monoxide and depleted in hydrogen. The gasification of pellets led to a gas with the greatest hydrogen to carbon monoxide ratio. The smallest particles tested resulted in the worst gasification performance, as defined by cold gas efficiency, carbon conversion, and tar production. Despite differences in the gas composition among the larger particles and the pellets, similar carbon conversion and cold gas efficiency was observed.Relative to comparable test conditions with dry feed fractions (having a moisture mass fraction of 7–12%), an average 11% increase in carbon conversion was observed for the wetter feed fractions containing a moisture mass fraction of 24–31%. This increase in carbon conversion offset much of the expected decrease in cold gas efficiency by using a wetter feed material. A slight increase in hydrogen production and negligible change in tar production was observed for the wetter feed fractions relative to the dry feed fraction.     

Numerical simulation of hydrogen production by gasification of large biomass particles in high temperature fluidized bed reactor

Biomass as a renewable fuel compared to fossil fuels usually contains high moisture content and volatile release. Hydrogen production by large particle biomass gasification is a promising technology for utilizing high moisture content biomass particle in the high temperature fluidized bed reactor. In the present work, simulation of large particles biomass gasification investigated at high temperature by using the discrete phase model (DPM). Combustible gases with homogeneous gas phase reactions, drying process with a heterogeneous reaction, primary and secondary pyrolysis with independent parallel-reaction by using two-competing-rate model to control a high and low temperature were used. During the thermochemical process of biomass, gaseous products containing of H₂, H₂O, CH₄, CO and CO₂ was obtained. The effects of concentration, mole and mass fraction and hydrodynamics effects on gaseous production during gasification were studied. The results showed that hydrodynamic effect of hot bed is different from cold bed. Concentration and molar fraction of CO and H₂ production by continually and stably state and small amount of CO₂, H₂O, and CH₄ was obtained. The hydrodynamic of bed plays the significant role on the rate of gaseous products.     

Evaluation of different biomass gasification modeling approaches for fluidized bed gasifiers

To develop a model for biomass gasification in fluidized bed gasifiers with high accuracy and generality that could be used under various operating conditions, the equilibrium model (EM) is chosen as a general and case-independent modeling method. However, EM lacks sufficient accuracy in predicting the content (volume fraction) of four major components (H₂, CO, CO₂ and CH₄) in product gas. In this paper, three approaches—MODEL I, which restricts equilibrium to a specific temperature (QET method); MODEL II, which uses empirical correlations for carbon, CH₄, C₂H₂, C₂H₄, C₂H₆ and NH₃ conversion; and MODEL III, which includes kinetic and hydrodynamic equations—have been studied and compared to map the barriers and complexities involved in developing an accurate and generic model for the gasification of biomass.This study indicates that existing empirical correlations can be further improved by considering more experimental data. The updated model features better accuracy in the prediction of product gas composition in a larger range of operating conditions. Additionally, combining the QET method with a kinetic and hydrodynamic approach results in a model that features less overall error than the original model based on a kinetic and hydrodynamic approach.     

Process analysis of hydrogen production from biomass gasification in fluidized bed reactor with different separation systems

Gasification is one of the most effective and studied methods for producing energy and fuels from biomass as different biomass feedstock can be handled, with the generation of syngas consisting of H₂, CO, and CH₄, which can be used for several applications. In this study, the gasification of hazelnut shells (biomass) within a circulating bubbling fluidized bed gasifier was analyzed for the first time through a quasi-equilibrium approach developed in the Aspen Plus environment and used to validate and improve an existing bubbling fluidized bed gasifier model. The gasification unit was integrated with a water-gas shift (WGS) reactor to increase the hydrogen content in the outlet stream and with a pressure swing adsorption (PSA) unit for hydrogen separation. The amount of dry H₂ obtained out of the gasifier was 31.3 mol%, and this value increased to 47.5 mol% after the WGS reaction. The simulation results were compared and validated against experimental data reported in the literature. The process model was then modified by replacing the PSA unit with a palladium membrane separation module. The final results of the present work allowed comparison of the effects of the two conditioning systems, PSA and palladium membrane, indicating a comparative increase in the hydrogen recovery ratio of 28.9% with the palladium membrane relative to the PSA configuration.     

A model of the dynamics of a fluidized bed combustor burning biomass

A dynamical model of an atmospheric, bubbling, fluidized bed combustor of biomass is presented. The model, based on one previously developed for the steady combustion of high-volatile solids, accounts for the fragmentation and attrition of fuel particles, the segregation and postcombustion of volatile matter above the bed, as well as thermal feedback from the splashing region to the bed. The model was used to assess how the dynamic behavior of the combustor varies with some of the operating parameters. To this end, a bifurcation analysis was first used to study the influence of selected parameters on the number and quality of steady state solutions. Moreover, direct integration of the governing equations provided a simulation of the dynamic behavior of the combustor after perturbing the parameters. Results of the bifurcation analysis indicated that extinction may take place through limit point bifurcations when varying the moisture content of the biomass and the flow rates of feed or air. Dynamic simulations showed that the bed temperature changes slowly when a stepwise change is imposed on one of the parameters. Either a new steady state or extinction eventually results, depending on the stepwise change. While relaxation of the bed temperature occurs rather slowly, the dynamics of the splashing region and of the freeboard are much faster, due to the shorter time-scales associated with homogeneous oxidation reactions. The relaxation time of the bed is determined by the heat capacity of the fluidized solids and by the fraction of the heat released recycling to the bed as thermal feedback.     

Bench-scale bubbling fluidized bed systems around the world - Bed agglomeration and collapse: A comprehensive review

Thermochemical conversion by gasification process is one of the most relevant technologies for energy recovery from solid fuel, with an energy conversion efficiency better than other alternatives like combustion and pyrolysis. Nevertheless, the most common technology used in the last decades for thermochemical conversion of solid fuel through gasification process, such as coal, agriculture residues or biomass residues are the fluidized bed or bubbling fluidized bed system. For these gasification technologies, an inert bed material is fed into reactor to improve the homogenization of the particles mixture and increase the heat transfer between solid fuel particles and the bed material. The fluidized bed reactors usually operate at isothermal bed temperatures in the range of 700–1000 °C, providing a suitable contact between solid and gas phases. In this way, chemical reactions with high conversion yield, as well as an intense circulation and mixing of the solid particles are encouraged. Moreover, a high gasification temperature favours carbon conversion efficiency, increasing the syngas production and energy performance of the gasifier. However, the risk of eutectic mixtures formation and its subsequent melting process are increased, and hence the probability of bed agglomeration and the system collapse could be increased, mainly when alkali and alkaline earth metals-rich biomasses are considered. Generally, bed agglomeration occurs when biomass-derived ash reacts with bed material, and the lower melting temperature of ash components promotes the formation of highly viscous layers, which encourages the progressive agglomerates creation, and consequently, the bed collapse and system de-fluidization. Taking into account the relevance of this topic to ensure the normal gasification process operating, this paper provides several aspects about bed agglomeration, mostly for biomass gasification systems. In this way, chemistry and mechanism of bed agglomeration, as well as, some methods for in-situ detection and prediction of the bed agglomeration phenomenon are reviewed and discussed.     

Gasification of biomass to hydrogen-rich gas in fluidized beds using porous medium as bed material

Experiments were carried out to study the characteristics of biomass gasification in a fluidized bed using industrial sand and porous medium as bed materials. Analysis was conducted to investigate the effects of different operation parameters, including bed material, gasification temperature (600 °C–900 °C), oxygen enrichment in the gasifying agent (21 vol.% to 50 vol.%), and steam flow rate (1.08 kg/h to 2.10 kg/h), on product yields and gas composition. The results of gas chromatography show that the main generated gas species were H₂, CO, CO₂, CH₄, and C₂H₄. Compared with industrial sand as bed material, porous medium as bed material was more suitable for gasifying biomass to hydrogen-rich gas. The physical characteristics of porous structure are more favorable to heat transfer, producing the secondary crack of heavy hydrocarbons and generating more hydrogen and other permanent gases. The product yields of hydrogen-rich gas increased with increasing gasification temperature. The hydrogen concentration improved from 22.52 vol.% to 36.06 vol.%, but the CO concentration decreased from 37.53 vol.% to 28.37 vol.% with increasing temperature from 600 °C to 900 °C under the operation parameters of porous bed material at a steam flow rate of 1.56 kg/h. With increasing oxygen concentration, H₂ concentration increased from 12.36% to 20.21%. Over the ranges of the examined experimental conditions, the actual steam flux value (e.g., 1.56 kg/h) was found to be the optimum value for gasification.     

Influences of equivalence ratio,oxygen concentration and fluidization velocity on the characteristics of oxygen-enriched gasification products from biomass in a pilot-scale fluidized bed

The influences of equivalence ratio (ER), oxygen concentration (OC) and fluidization velocity (FV) on the gasification performance in a pilot-scale fluidized bed with capacity of 1 ton biomass (the mixture of agricultural residue) per day were investigated using oxygen-enriched air as gasification agent and high-alumina bauxite as bed material. The characteristics of syngas (lower heating value (LHV), gas yield (Y), carbon conversion (CC) and cold gas efficiency (CGE)), bio-char (LHV and Proximate analysis) and tar (tar yield and LHV) were used to evaluate the gasification performance in this study. The results showed that 0.161 was the optimal ER due to the high quality of syngas produced and relatively lower tar generation with ER changing from 0.115 to 0.243 at OC ≈ 40% and FV ≈ 1.20.29.7% was the optimal OC due to the highest Y and CC and relatively low tar generation when OC varied from 21% to 44.7% at ER ≈ 1.40 and FV ≈ 1.15. Although higher FV could improve syngas quality, it also resulted in the higher tar yield and heavier wear, therefore, the optimal gasification performance was achieved at moderate FV (FV = 1.13). This study proved that oxygen-enriched gasification in a large-scale fluidized bed was an effective option to produce gaseous biofuels with high quality.     

Experimental study on syngas production by co-gasification of coal and biomass in a fluidized bed

The main results of an experimental work on co-gasification of a Chinese bituminous coal and two types of biomass in a bench-scale fluidized bed are reported in the present study. Experiments were performed at different oxygen equivalence ratio, steam/carbon ratio and biomass/coal ratio. In addition, stabilization of co-gasification process was investigated. It was found that a relatively low oxygen equivalence ratio favors the increase of syngas yield (CO + H₂). There is a maximum value in the curve of syngas yield versus steam/carbon ratio. Moreover, the content of H₂ in gas increases with the increase of biomass ratio while that of CO and syngas yield decrease. A continuous stable operation can be gained.     

Techno-economic analysis and life cycle assessment of hydrogen production from different biomass gasification processes

The paper presents techno-economic analyses and life cycle assessments (LCA) of the two major gasification processes for producing hydrogen from biomass: fluidized bed (FB) gasification, and entrained flow (EF) gasification. Results indicate that the thermal efficiency of the EF-based option (56%, LHV) is 11% higher than that of the FB-based option (45%), and the minimum hydrogen selling price of the FB-based option is $0.3 per kg H₂ lower than that of the EF-based option. When a carbon capture and liquefaction system is incorporated, the efficiencies of the EF- and FB-based processes decrease to 50% and 41%, respectively. The techno-economic analysis shows that at a biomass price of $100 per tonne, either a minimum price of $115/tonne CO_2e or a minimum natural gas price of $5/GJ is required to make the minimum hydrogen selling price of biomass-based plants equivalent to that of commercial natural gas-based steam methane reforming plants. Furthermore, the LCA shows that, biomass as a carbon-neutral feedstock, negative life cycle GHG emissions are achievable in all biomass-based options.     

Theoretical and experimental investigation of biomass gasification process in a fixed bed gasifier

This investigation concerns the process of air biomass gasification in a fixed bed gasifier. Theoretical equilibrium calculations and experimental investigation of the composition of syngas were carried out and compared with findings of other researchers. The influence of excess air ratio (λ) and parameters of biomass on the composition of syngas were investigated. A theoretical model is proposed, based on the equilibrium and thermodynamic balance of the gasification zone.The experimental investigation was carried out at a setup that consists of a gasifier connected by a pipe with a water boiler fired with coal (50 kWth). Syngas obtained in the gasifier is supplied into the coal firing zone of the boiler, and co-combusted with coal. The moisture content in biomass and excess air ratio of the gasification process are crucial parameters, determining the composition of syngas. Another important parameter is the kind of applied biomass. Despite similar compositions and dimensions of the two investigated feedstocks (wood pellets and oats husk pellets), compositions of syngas obtained in the case of these fuels were different. On the basis of tests it may be stated that oats husk pellets are not a suitable fuel for the purpose of gasification.     

Modeling the effects of the operational parameters on H2 composition in a biomass fluidized bed gasifier

In this study, effects of the operational parameters such as gasifier temperature, bed operational velocity, equivalence ratio, biomass particle size and biomass-to-steam ratio on hydrogen production from an atmospheric biomass FB gasifier is simulated by presently developed model. The model is one-dimensional, isothermal and steady state, and the fluid-dynamics are based on the two-phase theory of fluidization. Tar conversion is taken into account in the model. The model simulation results are also compared with and validated against experimental data given in the literature. As a result of this study, it is observed that H₂ composition increased remarkably with the rise of the gasifier temperature. Small biomass particles improves H₂ composition. It is unfeasible to apply too small or too large ER in biomass air-steam gasification. The increases in the mole fractions of H₂ with increases in the steam flow rate indicated that the gas shift reaction has a substantial effect in air-steam gasification.     

Chemical looping dry reforming of benzene as a gasification tar model compound with Ni- and Fe-based oxygen carriers in a fluidized bed reactor

Gasification tar during a fluidized bed operation impedes syngas utilization in downstream applications. Among tar constituents sampled during biomass gasification, benzene was the most abundant species. Thus, benzene was used as a model compound for chemical looping dry reforming (CLDR) over iron (Fe) and nickel (Ni) metals impregnated on silicon carbide (SiC) in a lab-scale fluidized bed reactor to convert it into hydrogen and carbon monoxide (H₂ and CO). A high benzene conversion rate (>90%) was observed at a higher experimental temperature (above 730 °C). Catalytic conversion of benzene using NiFe/SiC catalyst resulted in higher H₂ production whereas higher levels of CO were produced with Fe/SiC catalyst at an elevated temperature. Control experiments using an empty bed and SiC bed showed the formation of both the biphenyls and excessive carbon deposits. Air oxidation was also performed for the regeneration of oxygen carrier during the chemical looping operation.