CO2气氛下生物质气化制氢的数值分析

生物质气化制氢有重要的工业应用价值,本文采用ASPEN PLUS软件数值模拟了稻壳在流化床中的气化过程。本次模拟运用吉布斯自由能最小化原理,选择RGibbs和RYield模块,采用CO2作为气化剂,计算获得了气化温度、CO2质量流量、CO2和稻壳质量比和碳转化率对产氢率的影响规律。结果表明：在CO2质量流量为200kg/h时,H2的生成率高达43%。随着CO2/B增加,CO和CO2体积分数逐渐升高,CH4体积分数下降,H2体积分数在不同的气化温度下趋于平稳（600~700℃）或下降（800~1000℃）。随着气化温度升高,碳转化率增加;随着CO2和稻壳质量比的升高,碳转化率下降。     

锡林浩特褐煤气化特性研究

利用同步热分析仪研究了制焦温度、气化温度以及升温速率等因素对煤焦气化特性的影响。研究结果表明:随着制焦温度的升高,煤焦的气化失重量减少,气化反应的时间延长,气化反应性略有降低。随着气化温度的提高,锡林浩特褐煤煤焦在相同时间内的碳转化率增加,煤焦的气化时间缩短,气化温度对煤焦的气化反应性有较大的影响。随着升温速率的增大,TG曲线、DTG曲线均向高温侧偏移。升温速率越大,相同温度时煤焦的碳转化率越低,气化反应速率达到峰值对应的气化温度随升温速率的增大而升高。随着升温速率的增大,煤焦气化反应活性变好,气化反应进行的更加剧烈。     

基于等转化率法的生物焦CO_2气化反应动力学参数研究

利用热重分析仪在800~950℃对稻秆焦和木屑焦CO2等温气化过程进行了研究。分别采用等转化率法和随机孔模型求解了稻秆焦和木屑焦气化反应的动力学参数。通过等转化率法发现,随着碳转化率的增加,反应活化能随着碳转化率的升高而增大,稻秆焦和木屑焦在碳转化率为0.02时刻(即接近初始时刻)的活化能分别为157.2 k J/mol和166.4 k J/mol;采用随机孔模型计算得到稻秆焦和木屑焦的活化能分别为155.1 k J/mol和165.5 k J/mol,与等转化率法求得的碳转化率为0.02时刻的活化能接近,表明随机孔模型可以准确地描述稻秆焦和木屑焦的气化特性。同时发现,同一气化温度下,稻秆焦的结构参数大于木屑焦的结构参数;不同温度下的同一焦炭的结构参数f与对应的气化温度存在良好的指数关系。最后结合结构参数f与气化温度的指数关系表达式,得出稻秆焦和木屑焦的等温气化反应动力学随机孔模型速率表达式。     

石油焦的气化反应特性

针对3种不同的石油焦，在热天平上考察了不同的化学反应条件，包括温度、压力和气氛等因素对气化反应的影响．研究结果发现，在水蒸气气氛下石油焦具有良好的气化反应活性，而在二氧化碳气氛下石油焦气化反应进行得相当缓慢，相同条件下的C-H2O反应速率是C-CO2反应速率的十几倍，在60％水蒸气的实验温度条件下，每升高50℃，平均气化反应速率提高1倍；1000℃时，水蒸气分压对平均气化反应速率的影响不均匀，分压增加，影响减小．随着反应的不断进行，气化反应速率存在最大值，而出现最大值时的转化率不受反应温度和压力的影响，而与气化介质有关．根据实验结果，分析得到了3种石油焦在水蒸气条件下反应速率与温度、水蒸气分压和转化率的关系式，并得到了3种石油焦气化反应的活化能。     

几种因素对天然焦-H_2O气化反应活性的影响

在Thermax500型加压热重分析仪上进行了天然焦-H2O气化反应试验,分析了常压下气化温度、水流量、氧气分压、反应气氛和灰分等因素的影响.结果表明,气化温度升高,天然焦-H2O气化反应明显加快;随着水流量加大,碳转化率有所增大,但水流量达到0.07 mL/min后,碳转化率不再随水流量的进一步增加而变化;在气化剂中加入少量纯氧能有效促进气化反应;天然焦-H2O的气化速率明显大于天然焦-CO2的气化速率;天然焦脱灰后碳转化率略有降低.     

生物质半焦CO2气化反应动力学研究

采用热天平研究生物质半焦CO2气化反应动力学特性。考察半焦粒径、热解制焦温度以及热解制焦气氛对气化反应碳转化率的影响。采用随机孔模型、未反应芯缩核模型和混合模型对生物质半焦气化反应速率随碳转化率变化的趋势进行拟合,并求出半焦气化的动力学参数,结果表明随机孔模型的拟合效果最好。     

准东煤气化动力学模型研究

混合准东煤原煤与催化剂K_2CO_3、Ca(OH)_2并制成煤样,在化学反应动力学控制条件下研究其气化反应特性,分析了煤样质量、CO_2体积流量和颗粒直径对气化过程中内、外扩散阻力的影响,获得不同反应温度下均相模型、未反应芯收缩核模型和修正体积模型的拟合曲线,利用等转化率法计算气化反应活化能,并通过催化活性指数验证了该方法计算活化能的准确性.结果表明:在转化率为0.2、0.4、0.6和0.8时对应的活化能为100.1~130.2kJ/mol,3种模型计算所得活化能分别为128.97kJ/mol、140.33kJ/mol和139.43kJ/mol;均相模型为较合适的气化反应动力学模型.     

煤焦气化反应动力学研究

气流床气化技术是煤炭清洁、高效转化的重要途径和发展方向之一。利用热天平,采用等温热重法对抽样选出的煤种在800℃～1 400℃温度范围内进行了煤焦CO2气化反应动力学特性研究。研究结果表明:高温下煤焦的气化反应特性不同于低温时的反应特性,在900℃～1 000℃时气化反应逐步由化学反应控制过渡到过渡区控制,在1 100℃～1 300℃时气化从反应过渡区控制逐步到扩散区控制;不同粒径的煤粉气化反应,在相同的时间内,1 000℃时的碳转化率、气化反应速率比950℃时的碳转化率、气化反应速率高很多,950℃时的碳转化率、气化反应速率比900℃时的碳转化率、气化反应速率高。     

中药渣水蒸气气化制备合成气研究

以中药渣为原料进行水蒸气气化实验,研究气化温度、水蒸气与生物质质量之比(S/B)对产气流量、气体产率、产气组分、碳转化率、燃气热值以及气化效率的影响。研究结果表明:气化温度的升高能够促进气化反应的进行,提高产气品质和气化效率;一定量的气化剂水蒸气可提高气化效率,但是过量的水蒸气会影响气化效果;气化温度为800℃,S/B为1.0时,气化效果最佳,气化效率高达72.91%;中药渣具备良好的水蒸气气化特性。研究结果可为中药渣资源利用提供理论参考。     

两段式水煤浆气化炉气化参数对IGCC系统性能的影响

采用Thermo Flex软件建立了基于两段式水煤浆气化技术的200MW级IGCC系统模型,研究了气化温度、水煤浆浓度、气化压力、氧气纯度等气化参数对系统性能的影响.结果表明：提高反应温度和气化压力,系统的供电效率和发电效率降低;氧气纯度增加,供电效率上升;在相同气化温度（或气化压力、氧气纯度）的情况下,提高二段给煤比γsc,系统性能可以得到有效改善;当水煤浆浓度变化时,氧煤质量比随γsc改变进行调整才能达到设计值碳转化率的要求.     

Kinetics of rice husk char gasification in an H2O or a CO2 atmosphere

Rice husk gasification has been attracting increasing attention in rice-producing countries, but the technology has not yet achieved optimal efficiency. Only a few studies have reported on the gasification kinetics of rice husk char, and the influence of some important parameters has not yet been investigated. This paper provides an experimental database and kinetic models of gasification of a rice husk char particle in an H₂O or a CO₂ atmosphere. A complete parametric study of rice husk char gasification was performed in a wide range of operating conditions, relevant to those that exist in industrial gasifiers. Two kinetic models were developed to predict the conversion of a particle, taking into account changes in the reactive surface. Results of this study could help researchers and engineers in the design, modeling or optimization of a new efficient rice husk gasifier.     

Syngas production by chemical looping gasification of rice husk using Fe-based oxygen carrier

The chemical looping gasification (CLG) of rice husk was conducted in a fixed bed reactor to analyze the effects of the ratio of oxygen carrier to rice husk (O/C), temperature, residence time and preparation methods of Fe-based oxygen carriers. The yield of gas, H₂/CO, lower heating value of syngas (LHV), conversion efficiency and performance parameters were analyzed to obtain CLG reaction characterization and optimal reaction conditions. Results showed that when O/C increased from 0.5 to 3.0, the gas production, H₂/CO, CO₂ yield and carbon conversion efficiency gradually increased, while the yield of H₂, CO and CH₄ and LHV gradually decreased. At the same time, a highest gasification efficiency was obtained when O/C was 1.5. As increasing temperature, the gas production, CO yield, carbon conversion efficiency and gasification efficiency gradually increased, while the yield of H₂, CH₄ and CO₂, H₂/CO and LHV gradually decreased. Sintering and agglomeration was obvious when the temperature was higher than 850 °C. When the reaction time increased from 10 min to 60 min, the gas production, CO yield, carbon conversion efficiency and gasification efficiency gradually increased, but the yield of H₂, H₂/CO and LHV decreased, among which 30 min was the best reaction residence time. In addition, coprecipitation was the best preparation method among several preparation methods of oxygen carrier. Finally, O/C of 1.5, 800 °C, 30 min and coprecipitation preparation method of oxygen carrier were the optimal parameters to obtain a gasification efficiency of 26.88%, H₂ content of 35.64%, syngas content of 56.40%, H₂/CO ratio of 1.72 and LHV of 12.25 MJ/Nm³.     

Experimental investigation on gasification characteristics of polycarbonate (PC) microplastics in supercritical water

In order to solve the problem of marine microplastics and realize the harmless resource utilization of plastics, the gasification experiments of polycarbonate (PC) microplastics were carried out in supercritical water and a novel seawater gasification of microplastic experiment was investigated. In this paper, the effects of different operating conditions (temperature, time, feedstock concentration, pressure) on gasification performance were discussed. The gasification kinetic of microplastics in supercritical water was calculated. The experimental results showed that the increase in gasification temperature and time enhanced the cracking reaction and free radical reaction of the microplastics to increase the gasification efficiency, while the reduction in feedstock concentration improved the gasification efficiency by increasing the gasification level of unit feedstock. The change in pressure had no significant effect on gasification due to the fact that the properties of the supercritical water were not significantly changed. It was found that the valuable results that all alkali metal salts in seawater promote hydrogen conversion, while in terms of carbon conversion, only KCl, CaCl₂, NaHCO₃ and seawater had a significant catalytic effect on the gasification. Seawater gasification of microplastics was a potential resource utilization method. Finally, it was considered that the PC plastic gasification conformed to the random nucleation and subsequent growth model (n = 3), and the reaction activation energy was 230.45 kJ/mol, which was smaller than that of traditional pyrolysis.     

生物质流化床热裂解参数对产物分布的影响研究

以稻壳为原料,在自制的小型流化床上,研究了生物质快速热解反应温度、物料尺寸、惰性气体(N2)流量对生物油产率的影响。结果表明稻壳在反应温度500℃、氮气流量2 m3/h、颗粒为0.64 mm时,生物油产率最高52.87%。同时对玉米芯、龙须菜和绿菜在稻壳产油率最高的工况下进行了热解试验,结果表明稻壳和玉米芯生物油产率高于龙须菜和绿菜,就产炭率来说则龙须菜和绿菜明显高于稻壳和玉米芯。     

Kinetics of rice husk char gasification

The gasification of rice husk char in carbon dioxide and steam was investigated for determining the kinetic parameters. Experiments were conducted with rice husk char in its original grain form in a silica tube reactor with steam at temperatures of 750°C, 800°C, 850°C and 900°C and experiments were conducted with rice husk char powder in a thermogravimetric balance in a carbon dioxide medium at temperatures of 750°C, 800°C, 850°C and 900°C. The data was analysed based on the volume reaction and shrinking core models. The activation energies obtained for the rice husk grain sample were 200 kJ/mol and for the rice husk powder, about 180 kJ/mol respectively. The results obtained are in good agreement with literature values of different char gasification reactions.     

Overview of combustion and gasification of rice husk in fluidized bed reactors

Rice is cultivated in more than 75 countries in the world. The rice husk is the outer cover of the rice and on average it accounts for 20% of the paddy produced, on weight basis. The worldwide annual husk output is about 80 million tonnes with an annual energy potential of 1.2 × 10⁹ GJ corresponding to a heating value of 15 MJ/kg. India alone generates about 22 million tonnes of rice husk per year. If an efficient method is available, the husk can be converted to a useful form of energy to meet the thermal and mechanical energy requirements of the rice mills themselves. This paper provides an overview of previous works on combustion and gasification of rice husk in atmospheric bubbling fluidized bed reactors and summarizes the state of the art knowledge. As the high ash content, low bulk density, poor flow characteristics and low ash melting point makes the other types of reactors like grate furnaces and downdraft gasifiers either inefficient or unsuitable for rice husk conversion to energy, the fluidized bed reactor seems to be the promising choice. The overview shows that the reported results are from only small bench or lab scale units. Although a combustion efficiency of about 80% can normally be attained; the reported values in the literature, which are more than 95%, seem to be in higher order. Combustion intensity of about 530 kg/h/m² is reported. It is also technically feasible to gasify rice husk in a fluidized bed reactor to yield combustible producer gas, even with sufficient heating value for application in internal combustion engines. A combustible gas with heating value of 4-6 MJ/Nm³ at a rate of 2.8-4.6 MW_th/m² seems to be possible. Only very little information is available on the pollutant emissions in combustion and tar emissions from gasification. The major conclusion is that the results reported in the literature are limited and vary widely, emphasizing the need for further research to establish suitable and optimum operating conditions for commercial implementations.     

石灰石直接硫化实验研究

进行了在高CO2浓度下石灰石直接硫化实验研究。实验研究了温度、CO2分压、O2分压及SO2浓度对石灰石直接硫化的影响。结果表明,温度对直接硫化反应速率影响很大,随温度的升高直接硫化速率增大,在所试验的时间内,当温度为1173K时,Ca转化率可以达到87%,当转化率≈0时,测得表观活化能为93.5kJ/mol,且表观活化能随Ca转化率的升高而增加;与温度相比,CO2分压对石灰石直接硫化几乎没有影响,增加CO2分压只是延缓石灰石的分解,提高石灰石的分解温度;在5%以下随O2分压的增加,直接硫化速率随之增加,O2分压超过5%以后,O2分压对石灰石直接硫化就没有什么影响;随SO2浓度的增加,直接硫化速率升高。     

Biomass and low-density polyethylene waste composites gasification: Orthogonal array design of Taguchi technique for analysis and optimization

This modeling study explores and optimizes the performance of the gasification of a rice husk and low-density polyethylene waste composite utilizing an orthogonal array design of a Taguchi technique. This modeling study uses a signal to noise ratio analysis to optimize the gasification of rice husk and low-density polyethylene waste composite and utilizes an analysis of variance approach to identify the most important factors contributing to the process. It is shown that the composition ratio of rice husk and polyethylene waste contributes significantly to the gasification performance. Increasing composition ratio of rice husk and polyethylene waste improves hydrogen concentration, decreases carbon dioxide concentration and enhances carbon monoxide concentration. Energy efficiency is enhanced and normalized carbon dioxide emission is improved by increasing composition ratio of rice husk and polyethylene waste. The gasification of rice husk and low-density polyethylene waste composite is efficient (total energy efficiency of 77.6%) and clean (normalized carbon dioxide emission of 2.1 g/mol, based on the composite entering the system) at its multi-objective optimum conditions. The research results support the development of a system for gasification of biomass and plastic waste composites utilizing orthogonal array design of a Taguchi approach.     

Design and experimental study of pilot scale throat-less downdraft gasifier fed by rice husk and wood sawdust

In this work, pilot scale throat-less downdraft gasifier is fabricated and tested on rice husk and blend of rice husk-sawdust. The test aims to investigate effect of equivalence ratio on temperature profile, propagation front (flame propagation rate, bed movement rate, and effective propagation rate), and performance of the gasifier (composition of producer gas, heating value of producer gas, and thermal efficiency of the gasifier). Equivalence ratio investigated are 0.15, 0.20, and 0.25, while the blend ratio is 1:1 by mass. The results show that axial temperatures in the reactor surge faster with increasing equivalence ratio during the rice husk gasification and the blend gasification. Typically, flame propagation rate, bed movement rate, and effective propagation rate improve with rising equivalence ratio from 0.15 to 0.25. The best higher heating values and thermal efficiencies are obtained at equivalence ratio of 0.2 and 0.15 for the rice husk gasification and the blend gasification, respectively.