生物质三组分热解特性研究

在可再生能源的利用过程中,生物质因其储量巨大和"碳中性"而获得国内外学者的广泛关注。生物质热解是一种将生物质能转化为高附加值的烃和燃料的热化学转换技术。讨论了木质纤维素生物质的热解,主要集中在其三组分的不同热解特性。进一步讨论了生物质热解所面临的挑战以及提出未来的研究方向。     

生物质三组分二元混合热解特性研究

采用TG-FTIR-MS研究了生物质三组分二元混合热解过程的失重特性和小分子气体逸出规律。结果表明二元混合组分热解过程降低了热解反应开始温度。纤维素与半纤维素混合热解过程热解反应受到抑制,热解失重率降低,H₂、CH₄和H₂O产量减小,CO和CO₂产量增加。木质素和半纤维素在混合热解过程中存在协同效应,促进热解反应进行,H₂产量增加,然而其他小分子气体产物的生成被抑制,协同效应的效果更有利于可冷凝挥发分产物生成,这种效应随着半纤维素比例增大而减弱。半纤维素和纤维素在整个热解过程表现出相互抑制的效果,其小分子气体产物产量减小,但随着纤维素比例增大,影响减弱。     

生物质及生物质组分的慢速热解热效应研究

利用绝热加速量热仪(ARC)进行多种生物质及生物质组分的慢速热解,检测热解过程的吸放热情况,结果显示在缓慢升温过程中,纤维素的放热峰在256.2~279.2℃之间,放热量约为673.9J/g,质量分数为51.8%固体炭产物;而木聚糖在219.8~253.7℃之间有一尖锐的放热峰,放出热量约为873.3J/g,得到质量分数为68.7%的残余固体;木质素的热流曲线却在133.3~292.2℃有吸热趋势,吸收热量为340.1J/g,得到质量分数为80.4%的固体炭。各生物质的热流曲线中均有两个相连的放热峰出现,分别来源于半纤维素和纤维素。各生物质热流曲线特征值各异,但起始放热温度在190℃前后,第1个峰值温度在220℃左右,第2个放热峰峰值集中在255℃前后。     

N2/CO2气氛下木屑生物质热解特性的实验研究

本研究利用固定床管式炉开展了不同N2/CO₂比例气氛下的木屑生物质热解实验,考察了CO₂浓度、载气流速和停留时间对热解油和焦炭产率的影响。结果表明：热解油和焦炭的产率随反应温度和停留时间的增加而降低,热解油产率随反应气氛中CO₂浓度的升高而增加。在N₂和CO₂气氛下,载气流速升高均使热解油产率下降,而焦炭产率则在15%左右保持不变。添加HZSM-5和ZIF-67两种催化剂,发现ZIF-67在CO₂气氛下的热解油产率可以达到72.3%,相比其在N₂气氛下的热解油产率提升了近1.5倍;而HZSM-5由于其微孔孔道对生物质大分子传质的限制,产生最多焦炭(24.1%)。     

氧分级对药渣O2/CO2燃烧NOx生成规律与反应机理的影响

在我国目前能源结构中,化石能源尤其是煤炭资源占比很高,造成了极大的环境压力。抗生素发酵药渣为近年来产量迅速升高的固体废弃物,也是一种生物质燃料资源,但目前对药渣的能源化利用研究较少。以CH4等气体来模拟药渣可燃成分,利用Chemkin模拟软件中的PFR反应器构建了药渣在O₂/CO₂气氛下氧气分级燃烧及非分级燃烧模型,对2种情况下NO_x生成特性进行了模拟研究,探求了氧气分级及非分级燃烧时各种因素的影响,并利用生成速率分析法和敏感性分析法对结果进行了反应机理分析。研究结果表明,在氧气非分级条件下,NO_x转化率随燃烧温度升高先升高后降低,在1500℃左右达到峰值;NO_x转化率随过量氧气系数增加而升高,在过量氧气系数由0.9增至1.1时,增幅显著。在氧气分级条件下,主燃区燃烧温度对NO_x转化率的影响较为复杂;NO_x转化率随燃尽风率增加先降低后升高,随燃尽风位置推后降低。氧气分级条件下,还原气氛促进了NO_x中N向其他组分转化,能够明显降低NO_x生成。当燃烧温度低于1500℃,燃尽风率为0.35左右时,NO_x转化率最低。首次对药渣在O₂/CO₂气氛下的燃烧进行了反应动力学模拟研究,探求了各种因素的影响,为实现药渣能源化利用提供了指导。     

不同温度下CO2对管线钢母材/焊缝腐蚀行为研究

通过腐蚀实验和电化学实验研究了温度和CO₂协同作用对集输管道的腐蚀行为。结果表明：温度越高,时间越长,全面腐蚀速率和最大蚀坑深度越大,腐蚀形貌由全面腐蚀向点蚀转变。温度升高,开路电位和腐蚀电位负移,腐蚀电流密度增大,电荷转移电阻减小,最大相位角减小,表明腐蚀加剧,同时母材的耐蚀性优于焊缝。在温度为40℃时,焊缝试样在低频出现第二个相位角峰值,说明在较高的温度条件下,焊缝腐蚀产物的扩散速率是关键影响因素。     

高浓度CO2气氛下白云石强化煅烧工艺研究

CO₂循环煅烧白云石是具有前景的低碳炼镁新工艺。为研究新工艺下高浓度(摩尔分数)CO₂氛围中白云石强化煅烧措施,文中根据煅烧理论,建立了基于双环缩核的白云石煅烧反应动力学模型;计算分析了白云石分解过程传热传质和化学反应动力学的耦合特征,剖析了CO₂分压、温度和炉内总压等因素对单个白云石矿料分解动力学特征的影响;进一步考虑竖窑煅烧过程矿料粒径分布和矿料温度均匀性,研究不同炉内总压、温度、颗粒粒径等因素对竖炉容积利用系数的影响规律。结果表明：温度一定时,总压提高可强化热气流与矿料间的传热,促进白云石煅烧。通过合理调控煅烧过程温度和压力可有效提高新工艺的容积利用系数,最高可达0.967 1 t/(m³·h)。     

松木焦CO2气氛催化气化特性研究

生物质焦CO2气化主要是通过气化剂CO2和焦中的碳发生反应,从而制取得到高纯度可燃气CO.采用热重分析法研究不同过渡金属催化剂(Ni,Ce,Fe和Cr)以及不同气化温度下松木焦在30%CO2气氛下的气化特性,采用n级反应模型并利用ABSW微分法,计算出高温段710℃～990℃松木焦催化气化动力学参数.结果表明,随着气化温度的升高,反应完成的时间缩短,气化温度达到850℃以上,才能有较高的反应速率,添加4种过渡金属对气化均有明显的促进作用.其催化效果由高到低依次为:Ni,Ce,Fe和Cr.采用n级反应模型可以很好地拟合高温段的实验数据.     

生物质多孔炭吸附CO2的研究进展

本文对生物质多孔炭吸附CO₂的研究进展进行了综述,介绍了不同的生物质作为前驱体制备的吸附材料,着重对生物质多孔炭材料的结构与性能的构效关系进行了分析,总结了影响CO₂吸附的主要因素,并对生物质多孔炭材料目前存在的问题和发展方向进行了分析和展望。     

Calcination and sintering characteristics of limestone under O2/CO2 combustion atmosphere

The O₂/CO₂ coal combustion technology is an innovative combustion technology that can control CO₂, SO₂ and NO_x emissions simultaneously. Calcination and sintering characteristics of limestone under O₂/CO₂ atmosphere were investigated in this paper. The pore size, the specific pore volume and the specific surface area of CaO calcined were measured by N₂ adsorption method. The grain size of CaO calcined was determined by XRD analysis. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere are less than that of CaO calcined in air at the same temperature. And the pore diameter of CaO calcined in O₂/CO₂ atmosphere is larger than that in air. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere increase initially with temperature, and then decline as temperature exceeds 1000 °C. The peaks of the specific pore volume and the specific surface area appear at 1000 °C. The specific surface area decreases with increase in the grain size of CaO calcined. The correlations of the grain size with the specific surface area and the specific pore volume can be expressed as L = 744.67 + 464.64 lg(1 / S) and L = − 608.5 + 1342.42 lg(1 / ε), respectively. Sintering has influence on the pore structure of CaO calcined by means of influencing the grain size of CaO.     

Study on coal chars combustion under O2/CO2 atmosphere with fractal random pore model

When predicting the variation of pore structure during O₂/CO₂ combustion of coal chars using the random pore model (RPM), it is impossible to calculate exactly the structure parameter ψ from the pore characteristics. The values of structure parameter ψ, which were calculated based on its fractal feature at various carbon conversions, should be almost constant. However, this investigation exhibited a drastic increase of ψ at the end of combustion reaction. In this work, structure parameter ψ of the RPM was modified according to the experimental analysis and a new model, fractal random pore model (FRPM), was constructed. Compared with other models such as RPM, discrete random pore model (DRPM), the Struis model (Model I) and the Liu model (Model II), it was found that fractal random pore model was more accurate to describe coal chars combustion, especially at higher conversions. Using the FRPM, O₂/CO₂ isotherm combustion of coal chars were analyzed at different temperatures.     

Properties of char particles obtained under O2/N2 and O2/CO2 combustion environments

Pulverized coal combustion in O₂/N₂ and O₂/CO₂ environments was investigated with a drop tube furnace. Results present that the reaction rate and burn-out degree of O₂/CO₂ chars (obtained in O₂/CO₂ environments) are lower than that of O₂/N₂ chars (obtained in O₂/N₂ environments) under the same experimental condition. It indicates that a higher O₂ concentration in O₂/CO₂ environment is needed to achieve the similar combustion characteristic to that in O₂/N₂ environment. The main differences between O₂/N₂ and O₂/CO₂ chars rely on the pore structure determined by N₂ adsorption and chemical structure measured by FT-IR. For O₂/CO₂ char, the surface is thick and the pores are compact which contribute to the fragmentation reduction of particles burning in O₂/CO₂ environment. The organic functional group elimination rate from the surface of O₂/CO₂ chars is slower or delayed. The present research results might have important implications for further understanding the intrinsic kinetics of pulverized coal combustion in O₂/CO₂ environment.     

浅析CO_2汽提法尿素装置合成系统的NH_3/CO_2

介绍CO2汽提法尿素装置合成系统的NH3/CO2的控制方法,合成系统NH3/CO2异常的症状,判断方法,偏离正常时的处理和防范措施。     

NO reduction by CH4 in the presence of O2 over La2O3 supported on Al2O3

Dispersing La₂O₃ on δ- or γ-Al₂O₃ significantly enhances the rate of NO reduction by CH₄ in 1% O₂, compared to unsupported La₂O₃. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La₂O₃ precursor used, the pretreatment, and the La₂O₃ loading. The most active family of catalysts consisted of La₂O₃ on γ-Al₂O₃ prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m²) occurred between the addition of one and two theoretical monolayers of La₂O₃ on the γ-Al₂O₃ surface. The best catalyst, 40% La₂O₃/γ-Al₂O₃, had a turnover frequency at 700°C of 0.05 s⁻¹, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La₂O₃/Al₂O₃ catalysts exhibited stable activity under high conversion conditions as well as high CH₄ selectivity (CH₄ + NO vs. CH₄ + O₂). The addition of Sr to a 20% La₂O₃/γ-Al₂O₃ sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO⁼₄ to the latter Sr-promoted La₂O₃/Al₂O₃ catalyst decreased activity although sulfate increased the activity of Sr-promoted La₂O₃. Dispersing La₂O₃ on SiO₂ produced catalysts with extremely low specific activities, and rates were even lower than with pure La₂O₃. This is presumably due to water sensitivity and silicate formation. The La₂O₃/Al₂O₃ catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.     

Ni/Al_2O_3催化剂的CO_2-TPD表征

Ni/Al_2O_3催化剂是甲烷二氧化碳重整反应制取合成气研究最多、最具应用潜力的一种催化剂。通过对催化剂进行CO_2-TPD研究,考察还原态Ni/Al_2O_3催化剂的CO_2脱附特性。结果表明,浸渍法制备的Ni/Al_2O_3催化剂CO_2脱附曲线呈现双峰,分别在(60~65)℃和(350~380)℃出现高低温两个活性位;高温CO_2吸附量为3.0 cm~3·g~(-1),低温CO_2吸附量为24.0 cm~3·g~(-1)。催化剂的CO_2吸附量与其Ni含量无关。考察选用不同载体的CO_2脱附行为,发现以Al_2O_3为载体的催化剂CO_2吸附量是MgO和SiO_2为载体催化剂的2~4倍,以TiO_2为载体的催化剂几乎不吸附CO_2。     

ZrO2/SiO2- and La2O3/Al2O3-supported platinum catalysts for CH4/CO2 reforming

Surface-phase ZrO₂ on SiO₂ (SZrOs) and surface-phase La₂O₃ on Al₂O₃ (SLaOs) were prepared with various loadings of ZrO₂ and La₂O₃, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH₄/CO₂ reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al₂O₃ and Pt/SiO₂ catalysts. CO₂ or CH₄ pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO₂ to form a stable surface-phase oxide. The lanthana cannot be spread well on Al₂O₃, but it forms a stable amorphous oxide with Al₂O₃. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO₂ and Pt/Al₂O₃ by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO₂ and Pt/Al₂O₃ catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO₂ adsorbed on the basic sites of SZrOs and SLaOs.     

Thermodynamic performance of O2/CO2 gas turbine cycle with chemical recuperation by CO2-reforming of methane

This paper proposes a novel power cycle system composed of chemical recuperative cycle with CO₂–NG (natural gas) reforming and an ammonia absorption refrigeration cycle. In which, the heat is recovered from the turbine exhaust to drive CO₂–NG reformer firstly, and then lower temperature heat from the turbine exhaust is provided with the ammonia absorption refrigeration system to generate chilled media, which is used to cool the turbine inlet gas except export. In this paper, a detailed thermodynamic analysis is carried out to reveal the performance of the proposed cycle and the influence of key parameters on performance is discussed. Based on 1 kg s⁻¹ of methane feedstock and the turbine inlet temperature of 1573 K, the simulation results shown that the optimized net power generation efficiency of the cycle rises up to 49.6% on the low-heating value and the exergy efficiency 47.9%, the new cycle system reached the net electric-power production 24.799 MW, the export chilled load 0.609 MW and 2.743 kg s⁻¹ liquid CO₂ was captured, achieved the goal of CO₂ and NO_x zero-emission.     

Experimental study of ash formation during pulverized coal combustion in O2/CO2 mixtures

The present paper was addressed to mineral transformations and ash formation during O₂/CO₂ combustion of pulverized coal. Four Chinese thermal coals were burned in a drop tube furnace to generate ashes under various combustion conditions. The ash samples were characterized with XRD analysis and ⁵⁷Fe Mössbauer spectroscopy. The impacts of O₂/CO₂ combustion on mineral transformation and ash formation were explored through comparisons between O₂/CO₂ combustion and O₂/N₂ combustion. It was found that, O₂/CO₂ combustion did not significantly change the mineral phases formed in the residue ashes, but did affect the relative amounts of the mineral phases. The differences observed in the ashes formed in two atmospheres were attributed to the impact of the gas atmosphere on the combustion temperatures of coal char particles, which consequently influenced the ash formation behaviors of included minerals.