串行流化床煤气化试验

针对串行流化床煤气化技术特点,以水蒸气为气化剂,在串行流化床试验装置上进行煤气化特性的试验研究,考察了气化反应器温度、蒸汽煤比对煤气组成、热值、冷煤气效率和碳转化率的影响。结果表明,燃烧反应器内燃烧烟气不会串混至气化反应器,该煤气化技术能够稳定连续地从气化反应器获得不含N₂的高品质合成气。随着气化反应器温度的升高、蒸汽煤比的增加,煤气热值和冷煤气效率均会提高,但对碳转化率影响有所不同。在试验阶段获得的最高煤气热值为6.9 MJ•m^-3,冷煤气效率为68％,碳转化率为92％。     

A mathematical model of fluidized bed biomass gasification

A mathematical model of biomass gasification in a fluidized bed has been developed. It considers axial variations of concentrations and temperature in the bubble and emulsion phases. The mass balance involves instantaneous oxidation and equilibrium devolatilization of the biomass, kinetics of solid-gas gasification reactions as well as of gaseous phase reactions and interphase mass transfer and gas convection. The energy balance is solved locally for each vertical volume element, and globally on the reactor by iteration on the temperature at the bottom of the bed. Three parameters have been adjusted based on the experimental results: the heat transfer coefficient at the wall, the weighting of the kinetics of the water-gas shift reaction and the fraction of biomass carbon remaining as char after devolatilization. The model is used to simulate a pilot scale (50 kg/h) biomass gasifier, and its predictions compared to experimental measurements. The temperature and gaseous concentrations are estimated with good accuracy for the experiments using a wood feedstock, except for the concentration of hydrogen which is overestimated.     

Kinetics of catalytic steam gasification of bitumen coke

The catalytic steam gasification of coke from Athabasca bitumen was investigated by thermogravimetric analysis using K₂CO₃ and Na₂CO₃ as catalysts, both of which reduced the activation energy of the reaction considerably to 1.2 × 10⁵ J mol⁻¹ and 1.3 × 10⁵ J mol⁻¹, respectively, down from 2.1 × 10⁵ J mol⁻¹ for the uncatalyzed reaction. The reaction rates varied with the partial pressure of steam between 60 kPa and 85 kPa consistent with a Langmuir-Hinshelwood model, but a first order equation was also sufficient given the low partial pressures. The initial rate of gasification of the coke particles correlated linearly with the estimated external surface area of the particles, as expected from a surface reaction involving a non-porous solid. The initial reaction rate increased with increasing the catalyst loading up to 2.4 (mol potassium)/kg. A portion of the catalyst penetrated into the coke, as confirmed by secondary ion mass spectroscopy analysis, where it could not promote the reaction with steam. This result was consistent with a small increase observed in the reaction rate at low catalyst loading. The shrinking core model was successful in predicting the rates at higher conversions from the initial rate data, despite increases in BET surface area with conversion.     

Modeling and simulation of biomass air-steam gasification in a fluidized bed

By considering the features of fluidized-bed reactors and the kinetic mechanism of biomass gasification, a steady-state, isothermal, one-dimensional and two-phase mathematical model of biomass gasification kinetics in bubbling fluidized beds was developed. The model assumes the existence of two phases — a bubble and an emulsion phase — with chemical reactions occurring in both phases. The axial gas dispersion in the two phases is accounted for and the pyrolysis of biomass is taken to be instantaneous. The char and gas species CO, CO₂, H₂, H₂O, CH₄ and 8 chemical reactions are included in the model. The mathematical model belongs to a typical boundary value problem of ordinary differential equations and its solution is obtained by a Matlab program. Utilizing wood powder as the feedstock, the calculated data show satisfactory agreement with experimental results and proves the effectiveness and reliability of the model. __________ Translated from Chemical Engineering (China), 2007, 35(10): 23–26 [译自: 化学工程]     

生物质流化床空气-水蒸气气化模型研究

根据流化床反应器特点,结合生物质气化动力学反应机理,建立了生物质在流化床内气化的等温稳态、一维二相动力学模型。该模型所做的主要假定如下:流化床分为气泡相和乳相,在气泡相和乳相内均存在化学反应,考虑二相内的轴向气体扩散,生物质热解过程瞬时完成,主要考虑焦碳以及CO,CO2,H2,H2O,CH4等在流化床内发生的8个主要化学反应。数学模型属于常微分方程组边值问题,利用数值计算软件M atlab7.0进行编程求解。以木粉为原料,将模型结果与实验结果进行了对比,模拟结果与试验数据符合良好,在一定程度上证明了模型的有效性和可靠性。     

Coal pyrolysis and gasification in a fluidized bed thermogravimetric analyzer

The kinetics and modelling of coal gasification were studied in the newly developed fluidized bed thermogravimetric analyzer. The total weight loss obtained from the fluidized bed reactor and the total gas product are in general agreement. The presented model for the micro‐fluidized bed reactor encompasses the kinetics of coal pyrolysis as well as the gasification reactions. For coal pyrolysis, the resulting activation energies for the individual gases were 34.7 to 59.8 kcal/mol. These values are 19 to 21 % lower than those found in the literature for similar coals. This decrease of the activation energies of the endothermic pyrolysis reactions is attributed to a gradient of temperature of 185 to 209 °C. The obtained activation energy for the CO shift reaction is 46.6 kcal/mol, increasing by 20 % from the one used in the literature. This increase of the activation energy of such a mildly exothermic reaction represents an equivalent of 170 °C gradient of temperature. The effects of temperature on the yield and the composition of the gas product are studied. Experimental results and equilibrium data are also compared. The model shows reasonably good agreement with the experimental results, except for the water gas shift reaction.

     

Modelling and simulation of a coal gasification process in pressurized fluidized bed

A coal gasification mathematical model that can predict temperature, converted fraction and particle size distribution for solids have been developed for a high pressure fluidized bed. For gases in both emulsion and bubble phase, it can predict temperature profiles, gas composition, velocities and other fluid-dynamic parameters. In the feed zone, it could be considered a Gaussian distribution or any other distribution for the solid particle size. Experimental data from literature have been used to validate the model. Finally, the model can be used to optimize the gasification process changing several parameters, such as excess of air, particle size distribution, coal type and reactor geometry.     

福建无烟粉煤-纸浆黑液小型流化床水蒸汽催化气化表观动力学研究

在内径为26mm的实验室小型流化床反应器中进行福建尤溪无烟粉煤与纸浆黑液(BL)浸渍混合后的水蒸气催化气化实验.考察了4g/min水蒸汽流量下,不同催化剂加载浓度及不同温度对碳转化率的影响,并对催化气化表观动力学参数进行拟合与计算.研究结果表明:气化温度的升高和催化剂加载浓度的增大能显著提高碳转化率和产气速率,催化剂加载浓度从0%到8%的增加明显降低了催化气化反应的活化能,而从8%到10%的增加又令活化能有增加的趋势.在本实验条件下,BL作为催化剂的饱和加或浓度为8%.     

感冒清热颗粒中药渣中试规模循环流化床气化实验

以感冒清热颗粒中药渣为原料,在双回路循环流化床中试设备中进行热解气化实验,研究原料含水率、原料粒径以及空气当量比ER对其气化特性的影响。结果表明：①随着原料含水率的提高,炉内平均温度降低,产生的燃气中焦油含量、CO2含量明显提高;CO含量、气体产率、碳转化率显著降低;H2含量、燃气热值以及气化效率均呈现先增大后减小的趋势。②原料粒径越小,反应炉内平均温度越高,燃气中焦油含量越低,燃气热值和气体产率越高,气化效率以及碳转化率越高;H2、CH4、CO、CnHm含量增加,CO2含量减少。③随着ER的增大,可燃气体尤其是CO的浓度不断降低,CO2含量不断增加;炉内平均温度、气体产率以及碳转化率均逐渐增大;燃气热值和燃气中焦油质量浓度逐渐减小;气化效率则呈现先增大后减小的变化趋势。④当原料含水量<9%、原料粒径<4mm以及ER在0.25~0.27时,气化效率较高,具有较好气化特性。     

鼓泡流化床垃圾衍生燃料富氧气化

在鼓泡流化床上进行两种垃圾衍生燃料(RDF)的富氧气化试验,考察了RDF的热重特性并分析了气化温度、当量比及富氧浓度对气化特性的影响.结果表明:两种RDF均由纤维素及塑料类组分构成.随着温度由650℃升高至800℃,两种RDF产气的H₂、CO及CH₄浓度均逐渐增加,产气热值和气化效率同时提高.当量比增大时可燃组分浓度先略有增大后逐渐减小,但气体产率不断增大.RDF1及RDF2分别在当量比为0.22及0.27处达到最佳气化效率.富氧气化可有效改善气化品质,提升合成气热值,富氧浓度为45%时RDF1及RDF2合成气热值均达到最大,分别为8.6 MJ·m^-3及9.2 MJ·m^-3.     

基于CPFD方法的流化床生物质气化数值模拟

基于计算颗粒流体动力学(CPFD)建立了三维鼓泡流化床水蒸气-空气混合气化的数值模型,并进行了模型验证,结果表明模拟和实验具有良好的一致性。在该模型的基础上,研究了气化炉内气体分布以及温度分布;同时探究了生物质属性(颗粒粒径、含水率、种类)以及操作条件(气化温度、床料高度)对气化特性的影响。结果表明,生物质颗粒粒径对气化性能的影响存在一个最优值,平均粒径为0.6 mm是最佳的;较高的含水率会降低可燃气体产量,不利于气化反应的进行;四种生物质中,锯末气化的效率最高、可燃气体产量最大、气体热值最高,稻壳仅次于锯末但其碳转化率高于锯末;提高气化温度可以增加可燃气体的比例、提高气化效率;而初始床层高度的变化可以改变H₂/CO的比例。本实验为生物质水蒸气/空气气化提供了理论参考,有助于生物质原料的选取和处理,也有助于气化炉的放大和优化。     

Experimental study of droplet vaporization in a fluidized bed

The injection of liquid in a hot fluidized bed is used in many industrial processes. The larger droplets are likely to engulf particles and create agglomerates that should be avoided when a fast vaporization is expected. A new model is proposed to estimate the chances of agglomeration based on a critical bed temperature below which agglomerates form. This critical temperature for safe operating conditions is based on heat transfer between the particles and the liquid and takes the porosity of the solid into account. The model could be applied to pure and multi‐component mixtures and has been validated experimentally.     

Numerical study of biomass gasification combined with CO2 absorption in a bubbling fluidized bed

Biomass gasification combined with CO₂ absorption-enhanced reforming (AER) in a bubbling fluidized bed (BFB) reactor is numerically studied via the multiphase particle-in-cell (MP-PIC) method featuring thermochemical and polydispersity sub-models. A novel bubble detection algorithm is proposed for efficiently characterizing bubble morphology. The effects of several crucial operating parameters on the microscale particle behaviors, mesoscale bubble dynamics, and macroscale reactor performance of the AER gasification process are analyzed. Compared with conventional gasification, AER gasification reduces the CO₂ concentration by 33.58% but elevates the H₂ concentration by 32.13%. Higher operating temperature and steam-to-biomass (S/B) ratio promote H₂ generation but deteriorate gasification performance. A lower operating pressure improves gas–solid contact efficiency and gasification performance as the increased operating pressure inhibits bubble dynamics and particle kinematics. Compared with pure sand as bed material, the mixed bed material (CaO:sand = 1:1) significantly improves gasification performance by enhancing H₂ generation and CO₂ removal.     

Numerical simulation of 3D fluidized bed biomass gasification based on CPFD

Based on computational particle fluid dynamics (CPFD), a three-dimensional bubbling fluidized bed steam-air mixed gasification numerical model was established, and it was verified with experiment trials. The results show that the simulation and experiment have good consistency. Based on the model, the gas distribution and temperature distribution in the gasifier were studied; meanwhile, the biomass properties (particle size, water content, types) and operating conditions (gasification temperature, bed height) were investigated. The results show that there is an optimal value for the impact of biomass particle size on gasification performance, with an average particle size of 0.6 mm being the best; a higher water content will reduce the output of combustible gas and is not conducive to the gasification reaction. Among the four types of biomass, sawdust gasification has the highest efficiency, the largest combustible gas production, and the highest gas calorific value. Rice husk is second only to sawdust but its carbon conversion rate is higher than that of sawdust; increasing the gasification temperature can increase the proportion of combustible gas and increase gasification efficiency; while the change of initial bed height can change the ratio of H₂/CO. This experiment provides a theoretical reference for biomass steam/air gasification, which is helpful for the selection and processing of biomass raw materials, and also facilitates the amplification and optimization of the gasifier.     

灰熔聚粉煤气化技术运行中出现的问题及措施

灰熔聚循环流化床粉煤气化技术是我国具有自主知识产权的新型煤气化技术。介绍了该技术的特点、工艺流程,总结了在应用中出现的问题及一些整改措施。     

Potential approaches to improve gasification of high water content biomass rich in cellulose in dual fluidized bed

Biomass containing water of 30-65 wt.% and rich in cellulose, such as various grounds of drinking materials and the lees of spirit and vinegar, is not suitable for biological digestion, and the thermal conversion approach has to be applied to its conversion into bioenergy. The authors have recently worked on converting such biomass into middle heating-value gas via dual fluidized bed gasification (DFBG) integrated with various process intensification technologies. This article is devoted to highlighting those technical ways, including the choice of the superior technical deployment for a DFBG system, the impregnation of Ca onto fuel in fuel drying, the integration of gas cleaning with fuel gasification via two-stage DFBG (T-DFBG), and the decoupling of fuel drying/pyrolysis and char gasification via the decoupled DFBG (D-DFBG). The attained results demonstrated that the superior deployment of bed combination for the DFBG should be a bubbling/turbulent fluidized bed gasifier integrated with a pneumatic riser combustor. In terms of improving efficiency of fuel conversion into combustible gas and suppressing tar generation during gasification, the impregnation of Ca onto fuel exhibited distinctively high upgrading effect, while both the T-DFBG and D-DFBG were also demonstrated to be effective to a certain degree.     

Two-stage dual fluidized bed gasification: Its conception and application to biomass

The quoted two-stage dual fluidized bed gasification (T-DFBG) devises the use of a two-stage fluidized bed (TFB) to replace the single-stage bubbling fluidized bed gasifier involved in the normally encountered dual fluidized bed gasification (N-DFBG) systems. By feeding fuel into the lower stage of the TFB, this lower stage functions as a fuel gasifier similar to that in the N-DFBG so that the upper stage of the TFB works to upgrade the produced gas in the lower stage and meanwhile to suppress the possible elutriation of fuel particles fed into the freeboard of the lower-stage bed. The heat carrier particles (HCPs) circulated from the char combustor enter first the upper stage of the TFB to facilitate the gas upgrading reactions occurring therein, and the particles are in turn forwarded into the lower stage to provide endothermic heat for fuel pyrolysis and gasification reactions. Consequently, with T-DFBG it is hopeful to increase gasification efficiency and decrease tar content in the produced gas. This anticipation was corroborated through gasifying dry coffee grounds in two 5.0kg/h experimental setups configured according to the principles of T-DFBG and N-DFBG, respectively. In comparison with the N-DFBG case, the test according to T-DFBG increased, the fuel C conversion and cold gas efficiency by about 7% and decreased tar content in the produced gas by up to 25% under similar reaction conditions. Test results demonstrated also that all these upgrading effects via adopting T-DFBG were more pronounced when a Ca-based additive was blended into the fuel.     

过热蒸汽流化床流化特性的实验研究

在底部直径为120 mm的锥型流化床中,以玻璃珠为流化颗粒,过热蒸汽为流化介质,研究了固体颗粒在过热蒸汽流化床中的流化特性,考察了操作温度和压力对临界流化速度(umf)的影响.结果表明,过热蒸汽流化床的流化行为与热空气相似,临界流化速度(umf)随床层温度的升高而减小,随床内压力的增大而减小;在相同温度条件下,过热蒸汽流化床的临界流化速度比热空气大.     

城市污泥流化床中低温空气气化及重金属迁移特性

利用自行搭建的流化床热态实验装置，系统研究了污泥的中低温气化及重金属迁移特性。研究表明，对冷煤气效率和碳转化率影响最大的是气化温度，其次是空气当量比，而一二次风配比和流化数影响较弱。污泥中低温气化的焦油产率较之高温气化明显增加。随着二次风占比和空气当量比的提高，焦油产率单调下降。气化温度由600℃升至850℃，冷煤气效率和碳转化率均呈升高趋势；空气当量比由0.2升至0.4，冷煤气效率呈先升高后下降的趋势，在0.3时达到最大值，而碳转化率则呈单调升高趋势。随着气化温度的升高，污泥中重金属转移至产气、焦油及飞灰的迁移率升高。随着空气当量比的升高，Ni、Cu的迁移率降低，Cr升高，Cd、Zn、As和Pb等其他重金属的迁移率几乎不变。     

玉米秸秆循环流化床气化中试试验

玉米秸秆是农业生产过程中产生的剩余物,其热解气化是秸秆类生物质处理应用的重要选择方向。为此,采用循环流化床气化中试装置对玉米秸秆进行了气化试验,研究空气当量比ER、原料含水率对反应温度、气化燃气组分与热值、气化效率及燃气中的焦油含量等气化特性影响规律,并通过改变进料量试验得到了在不同负荷运行条件下的优化工作参数。结果表明：①随着ER的增大,循环流化床气化炉内的反应温度升高,气化燃气中的CO₂含量增加,焦油与CO含量及燃气热值降低,气化效率随ER的增大呈现先增大后减小趋势,较理想的ER为0.26,此时的气化效率达到70.2%、燃气热值为5.1MJ/m³;②原料含水率的增大降低了气化炉内的反应温度,当原料含水率在5%～15%之间逐渐增大时,燃气中的H₂含量、燃气热值及气化效率均有提升,当含水率由15%继续增大到25%过程中,燃气热值与气化效率均出现了快速下降;③根据气化炉额定进料量设计值,改变进料负荷在66%～120%范围内,调节ER在0.26～0.3时均可得到较好的运行工况,对应得到的燃气热值为4.8～5.1MJ/m³、气化效率为69%～72%。