生物质催化热解气化热重分析研究

采用热重分析与气相色谱分析(TG-GC)相结合的方法,开展了以麦秸为主要研究对象的生物质催化热解气化实验研究,探讨了以NiO和CaO为催化剂,水蒸气气氛下的麦秸挥发分析出特性、半焦的气化特性、气化反应动力学特性以及催化剂对麦秸气化产物的影响.实验结果表明麦秸水蒸气气氛下的反应活性明显提高,气化反应过程中热解阶段视为一级反应,半焦气化视为缩核反应.非催化条件下麦秸的半焦气化在800℃以上才进行,添加NiO与CaO均促进了麦秸与水蒸气的气化反应,提高了气化过程的碳转化率和反应速率,但二者对半焦气化的促进机理以及气体产物的催化选择性有明显差异.添加NiO时H2产率最大,达到34mol/kg麦秸,且使气化反应温度明显降低.添加CaO不仅促进了H2和CO的生成,而且CH4产率也明显提高,表明CaO更有利于大分子碳氢化合物的裂解.     

生物质加压热重分析研究

对两种生物质木屑和松针进行了不同压力和升温速率下的热重分析试验,通过生物质热重失重率（TG）和失重速率（DTG）曲线,获得了相关热解特性参数,提出了生物质的挥发分综合释放特性指数D．并通过热分析数学方法求取了生物质热解动力学参数．试验结果表明,氮气气氛中,木屑与松针常压和增压下主要热解阶段可认为两段一级反应;热解压力的提高,将延迟生物质挥发分初析温度和DTG峰值温度,降低最大析出率和DTG峰值,生物质的挥发分综合释放特性指数D也减小,增加了生物质挥发分的析出难度,并改变了热解反应活化能和频率因子．同一压力下,提高热解升温速率,生物质综合特性指数D将增加．     

CaO对松木锯末水蒸气气化过程的影响

采用CaO在生物质气化过程中通过吸收CO2促进产氢的方法,对生物质松木锯末进行水蒸气气化实验研究。分析了CaO、水蒸气、温度和停留时间对产气组分的影响。实验结果表明:添加CaO能显著提高产氢量。当Ca/B0.5时,产氢量随着Ca/B的增加而显著增加,当Ca/B0.5后,产氢量略微下降。添加CaO后促进了水煤气反应的进行。当温度高于800℃时,添加CaO后,生物质气化挥发分释放阶段与半焦气化阶段出现了重叠,半焦气化反应提前发生。随着温度和停留时间的延长,H2浓度逐渐升高,且在较长时间内维持在较高的浓度。     

钙钛矿型LaFeO_(3)载氧体生物质化学链气化热力学分析及实验研究北大核心CSCD

文章针对基于LaFeO_(3)载氧体的木屑生物质化学链气化特性,开展了热力学过程模拟与分析,并搭建了固定床实验装置,研究了载氧体添加量(O/B)、气化温度和水蒸气量对合成气品质的影响。热力学分析结果表明:相比传统Fe_(2)O_(3)载氧体,LaFeO_(3)不易与合成气进一步反应,更适合生物质的化学链气化过程,且气化温度升高有利于提升合成气产率,增大LaFeO_(3)添加量也会促进合成气生成,而过多的Fe_(2)O_(3)则会进一步氧化合成气导致产气率下降;添加水蒸气可明显提高合成气中H2占比。实验结果表明,提高反应温度和载氧体添加量能够提高合成气品质,但过量水蒸气反而不利于合成气的转化。在O/B为0.6、气化温度为900℃、水蒸气流量为0.3mL/min的最佳工况下,基于LaFeO_(3)的木屑化学链气化过程的转化效率达到97.09%。研究成果可为生物质固废的能源化利用与推广提供科学依据。     

兰炭生物质复合燃料热解实验分析

采用热重分析方法对生物质复合燃料、无生物质复合燃料、兰炭原料热解行为及其动力学规律进行研究,实验结果发现样品的失重过程分为脱水、脱挥发分,气化反应混合以及气化反应等3个阶段,实验样品的失重率会伴随着温度的变化而变化。对实验样品进行动力学分析,根据3种样品最佳反应温度得出升温速率拟合曲线,3种样品活化能分别为3 562.454、1 042.97、2 904.818 kJ/mol。对比分析得出生物质型炭的活化能大大增加,提高了能量利用率。     

基于铁矿石载氧体的生物质化学链气化机理研究

在单批次进料小型流化床上,以稻壳为生物质燃料,研究了床料、气化温度、水蒸气体积分数以及载氧体载氧量与生物质含碳量的摩尔比(O/C)对生物质化学链气化反应特性的影响,并考察了铁矿石的长期交替氧化还原过程中的反应特性,分析了在小型流化床,水蒸气气氛气化条件下,铁矿石载氧体在反应过程中主要的反应以及反应后的铁矿石的床料变化。研究表明:在载氧体条件下,生物质的碳转化率显著增大,随着反应温度的升高,合成气中的H_2和CO的体积分数也相应升高。在温度不变情况下,随着水蒸气比例的升高,CO_2和H_2的体积分数显著上升。伴随着O/C摩尔比的升高,CO和H_2均显著下降。因此,在不同的反应条件下,铁矿石在生物质化学链气化过程中对反应速度、合成气比例等均有明显的作用,对研究生物质的综合利用具有一定的意义。     

不同气化剂下海藻粉在气流床下气化特性试验研究

为考察O2/水蒸气和O2/CO2作为气化剂对海藻粉气化特性的影响,在自制的小型生物质气流床气化炉上开展海藻粉在气流床下气化特性试验研究。当氧气/生物质比（O/B）为0.3、气化温度为1200℃时,不同水蒸气/生物质比（S/B=0～1.2）对合成气组成有较大影响,其中H2产量的上升趋势最为明显,S/B=1.2时比单纯氧气气化提高了81.4%。而在O2/CO2气化条件下,由生物质产生的CO2随二氧化碳/生物质比（CO2/B）的增加而下降,当CO2/B=0.9时,H2、CO的产量分别比单纯氧气气化提高了33.9%和75.8%,热值由5521 kJ/m3上升至8576 kJ/m3。结果表明,如果以提高热值为制取合成气的目标时,添加CO2在一定范围内可以达到水蒸气的效果,同时降低了系统能耗及简化了气化设备。     

利用分布活化能模型研究木材的热解和燃烧机理

在热天平上考察了三种木材在不同气氛和升温速率下的热解行为,并利用分布活化能模型研究了三种木材的热解动力学.结果表明:在空气气氛下,热失重分为三个阶段,失重率为500/~6000/时,三种木材的活化能值都在110~250 kJ/mol,且非单调增加;在氮气气氛下,热失重分两个阶段,失重率在1000/~8500/时,三种木材的活化能值都在165~230 kJ/mol,且呈“W”形变化.活化能的分布函数,反映了木材在热解、气化、燃烧过程中不同阶段的反应活性变化规律,有助于了解木材的热解和燃烧机理.     

生物质高温气化重整制氢实验研究

在自行设计的固定床气化炉实验台上开展序批式进料模式的生物质(白松木屑)高温气化实验研究,重点考察反应温度、水蒸气流率以及物料粒径等不同工况条件对生物质气化产气特性的影响,实验结果表明,在800~950℃的范围内,每千克白松木屑的氢产率为21.91~71.63g H2。不同水蒸气流率下H2平均浓度变化不大,CO平均浓度随水蒸气流率的增加略有增大,气体平均热值在11.87~12.04kJ/m3内变化。实验条件下水蒸气流率为20.2g/min时的氢气产率最大。随着生物质给料粒径的减小,气体产率和气化效率均减小。     

松木屑水蒸气催化气化制氢及其大物料量气化动力学研究

利用松木屑在自制固定床气化系统上进行水蒸气催化气化实验研究.考察反应温度、水蒸气/生物质比(S/B)以及催化剂加入量对气体成分、产氢率和潜在产氢率的影响.结果表明:反应温度为850℃、S/B为3.27、催化剂量,木屑进料量比为2%时合成气品质较优,氢气浓度可达40.13%,产气率为0.718m3·kg-1.该文也进行大物料量松木屑催化气化等温热重实验研究,加入催化剂使木屑气化反应活化能降低,加快了反应进程.     

Thermogravimetric kinetic analysis of Nannochloropsis oculata combustion in air atmosphere

The thermal behavior of Nannochloropsis oculata combustion in air atmosphere were investigated by performing experiments on STA PT1600 Thermal Analyzer at heating rates of 10°C/min, 40°C/min and 70°C/min and range of temperatures from room temperature to 1200°C. The kinetic parameters were evaluated by using Kissinger and Ozawa methods. The result showed that Nannochloropsis oculata combustion occurred in five stages. Started with initial devolatilization, the main thermal decomposition and combustion process, transition stage, the combustion of char and the last stage was the slow burning reaction of residual char. In line with increasing heating rate, the mass loss rate increased as well, but it delayed the thermal decomposition processes toward higher temperatures. The average activation energy at the main thermal decomposition stage and the stage of char combustion were approximately 251 kJ/mol and 178 kJ/mol, respectively.     

Experimental study on the key factors affecting the gasification performance between different biomass: Compare citrus peel with pine sawdust

This work aims to reveal the advantages of citrus peel gasification and investigate the key factors affecting gasification performance. The gasification performance of citrus peel and pine sawdust are compared in a fixed bed reactor, and the reactivity and properties of biochar were investigated. The results showed that the H₂ yield and carbon conversion efficiency of citrus peel gasification were 34.35 mol/kg_biomass and 66.30%, respectively, which were higher than those of pine sawdust. Due to the high reactivity of citrus peel char, it only takes 100 min for the citrus peel to complete the gasification reaction, which is significantly faster than pine sawdust. Although the specific surface area of citrus peel char is lower than that of pine sawdust char, both the low degree of graphitization and the high catalytic index (2426.96) are favorable for the conversion of char, which ultimately lead to the high reactivity of citrus peel char.     

Hydrogen enriched syngas production via gasification of biofuels pellets/powders blended from olive mill solid wastes and pine sawdust under different water steam/nitrogen atmospheres

In this work, we study the gasification of pellets produced, after densification, by blending olive mill solid wastes, impregnated or not by olive mill waste water, and pine sawdust under different steam/nitrogen atmospheres. The charcoals necessary for the gasification tests were prepared by pyrolysis using a fixed bed reactor. The gasification technique using steam was chosen in order to produce a hydrogen-enriched syngas. Gasification tests were performed using macro-thermogravimetric equipment. Tests were carried out at different temperatures (750 °C, 800 °C, 820 °C, 850 °C and 900 °C), and at different atmospheres composed by nitrogen and steam at different percentages (10%, 20% and 30%). Results show that the mass variation profiles is similar to the usual lingo-cellulosic gasification process. Moreover, the increase of temperatures or water steam partial pressures affects positively the rate of conversion and the char reactivity by accelerating the gasification process. The increase of the gasification yields demonstrates the promise of using olive mill by-products as alternative biofuels (H₂ enriched syngas).     

The development of a real-time thermogravimetric analyzer on the gasification of pine sawdust in a simulated fluidized bed gasifier

In this study, a real-time thermogravimetric analyzer was developed for providing insight into the reactivity and gasification process of pine sawdust. The mass loss rate of pine sawdust, syngas composition, and tar compounds in the gasification process were analyzed at different gasification conditions. According to the real-time thermogravimetric analysis, 800°C of the gasification temperature, 0.25 of the equivalence ratio, and 600 kg/(m²·h) of the gasification throughput were regarded as an optimum conditions for the gasification of pine sawdust in a fluidized bed gasifier.     

Kinetic characteristics of in-situ char-steam gasification following pyrolysis of a demineralized coal

This study aims to examine the char-steam reactions in-situ, following the pyrolysis process of a demineralized coal in a micro fluidized bed reactor, with particular focuses on gas release and its kinetics characteristics. The main experimental variables were temperatures (925 °C?1075 °C) and steam concentrations (15%–35% H₂O), and the combination of pyrolysis and subsequent gasification in one experiment was achieved switching the atmosphere from pure argon to steam and argon mixture. The results indicate that when temperature was higher than 975 °C, the absolute carbon conversion rate during the char gasification could easily reach 100%. When temperature was 1025 °C and 1075 °C, the carbon conversion rate changed little with steam concentration increasing from 25% to 35%. The activation energy calculated from shrinking core model and random pore model was all between 186 and 194 kJ/mol, and the fitting accuracy of shrinking core model was higher than that of the random pore model in this study. The char reactivity from demineralized coal pyrolysis gradually worsened with decreasing temperature and steam partial pressure. The range of reaction order of steam gasification was 0.49–0.61. Compared to raw coal, the progress of water gas shift reaction (CO + H₂O ? CO₂ + H₂) was hindered during the steam gasification of char obtained from the demineralized coal pyrolysis. Meanwhile, the gas content from the char gasification after the demineralized coal pyrolysis showed a low sensitivity to the change in temperature.     

Detailed kinetic analysis and modelling of the dry gasification reaction of olive kernel and lignite coal chars

The dry gasification process of solid fuels is a promising pathway to mitigate and utilize captured CO₂ emissions toward syngas generation with tailored composition for several downstream energy conversion and chemical production processes. In the present work, comprehensive kinetic analysis and reaction modelling studies were carried out for olive kernel and lignite coal chars gasification reaction using pure CO₂ as gasifying agent. Chars reactivity and kinetics of the gasification reactions were thoroughly examined by thermogravimetric analysis at three different heating rates and correlated with their physicochemical properties. The reactivity of olive kernel char, as determined by the mean gasification reactivity and the comprehensive gasification characteristic index, S, was almost three times higher compared to that of the lignite coal char. It was disclosed that the fixed carbon content and alkali index (AI) have a major impact on the reactivity of chars. The activation energy, E_a, estimated by three different model-free kinetic methods was ranged between 140 and 170 kJ/mol and 250–350 kJ/mol for the olive kernel and lignite coal chars, respectively. The activation energy values for the lignite coal char significantly varied with carbon conversion degree, whereas this was not the case for olive kernel char, where the activation energy remained essentially unmodified throughout the whole carbon conversion range. Finally, the combined Malek and Coats-Rendfrem method was applied to unravel the mechanism of chars-CO₂ gasification reaction. It was found that the olive kernel char-CO₂ gasification can be described with a 2D-diffusion mechanism function (D2) whereas the lignite coal char-CO₂ gasification follows a second order chemical reaction mechanism function (F2).     

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.     

高温空气气化数学模型的建立与分析

建立了一种基于物料平衡、能量平衡和化学平衡分析的气化数学模型。利用该模型分别对松木屑、秸秆、稻壳和棉柴进行气化计算,获得不同水蒸气添加率的合成燃气成分、热值、气化效率及干燃气产率等气化指标,分析水蒸气添加率对高温空气气化的影响,为高温气化操作优化奠定基础。     

Syngas yield during pyrolysis and steam gasification of paper

Main characteristics of gaseous yield from steam gasification have been investigated experimentally. Results of steam gasification have been compared to that of pyrolysis. The temperature range investigated were 600–1000 °C in steps of 100 °C. Results have been obtained under pyrolysis conditions at same temperatures. For steam gasification runs, steam flow rate was kept constant at 8.0 g/min. Investigated characteristics were evolution of syngas flow rate with time, hydrogen flow rate and chemical composition of syngas, energy yield and apparent thermal efficiency. Residuals from both processes were quantified and compared as well. Material destruction, hydrogen yield and energy yield is better with gasification as compared to pyrolysis. This advantage of the gasification process is attributed mainly to char gasification process. Char gasification is found to be more sensitive to the reactor temperature than pyrolysis. Pyrolysis can start at low temperatures of 400 °C; however char gasification starts at 700 °C. A partial overlap between gasification and pyrolysis exists and is presented here. This partial overlap increases with increase in temperature. As an example, at reactor temperature 800 °C this overlap represents around 27% of the char gasification process and almost 95% at reactor temperature 1000 °C.     

Characteristics of cardboard and paper gasification with CO2

Evolutionary behavior of syngas chemical composition and yield have been examined for paper and cardboard at three different temperatures of 800, 900 and 1000 °C using CO₂ as the gasifying agent at constant flow rate. Specifically the evolution of syngas chemical composition with time has been investigated. Pyrolysis of the sample was dominant at the beginning of the gasification process as observed from the high initial devolatilization of the sample followed by char gasification of material to form syngas for a long period of time. Results provided the role of gasification temperature on kinetics of the CO₂ gasification process. Increase in gasification temperature provided increased conversion of the sample material to syngas. Thus the sample conversion to syngas was low at the low temperature of 800 °C while at elevated temperatures of 900 and 1000 °C substantial enhancement of the kinetics process occurred. The evolution of extensive reaction rate of carbon-monoxide was calculated. Results show that increase in temperature increased the extensive reaction rate of carbon-monoxide. The global behavior of syngas chemical composition examined at three different temperatures revealed a peak in concentration of H₂ to exhibit after few minutes into the gasification that changed with gasification temperature. At 800 °C gasification temperature peak in H₂ was displayed at 3 min into gasification while it decreased to only 2 min, approximately, at gasification temperatures of 900 and 1000 °C. The effect of reactor temperature on CO mole fraction has also been examined. Increase in the gasification temperature enhances the mole fraction of CO yields. This is attributed to the increase in forward reaction rate of the Boudouard reaction (C+CO₂2CO). The results show important role of CO₂ gas for the gasification of wastes and low grade fuels to clean syngas.