纤维素热解机理研究进展：以中间态纤维素为核心的纤维素演变

纤维素热解的机理研究对于生物质能的热利用至关重要,能够有效指导工业实际应用。基于著名的Broido-Shafizadeh模型,纤维素热解被分为两步,首先转变为活性的熔融态中间体（中间态纤维素）,然后通过解聚和开环生成左旋葡聚糖、5-羟甲基糠醛、羟基乙醛等重要的化工原料。在这两步转变中,主要涉及低温段氢键网络的断裂、中间态纤维素的生成,以及高温段的解聚和吡喃环开环反应。本文从这3个部分对前人的研究进行了综述,着重介绍了中间态纤维素的生成和表征,综述了纤维素热解几个研究方向：结晶度和结晶形态对热解的影响、纤维素解聚反应方式、吡喃环开环方式等,详细阐述了二次反应对纤维素热解的影响,并提出了部分解决方案。关于纤维素热解依然存在诸多未知和争论,需要进一步的实验研究和理论计算对其进行揭示。     

钾盐对生物质热解特性影响研究进展

为了更好地探究钾盐对生物质催化气化的影响,该论文从钾盐来源和赋存形式出发,对钾盐在生物质热解过程中的化学形式变化和迁移规律、热解过程和产物的影响、添加方式的影响等进行了总结。从钾盐对生物质主要成分纤维素、半纤维素和木质素的热解的影响角度分析了钾盐对生物质热解的影响,对于研究钾盐的热解机理有一定借鉴作用。对钾盐与其他金属盐在生物质热解中催化气化特性作了对比,分析了不同金属盐对生物质热解过程的影响。通过分析比较国内外学者在钾盐催化气化方面的研究,发现由于条件的不同,各研究结论也有所不同,而且在催化气化机理还有待进一步研究。     

生物质快速热解制糠醛的实验研究及理论探讨综述

糠醛是生物质快速热解的重要产物之一,通过对生物质进行定向热解可实现糠醛的选择性制备,从而获得一种新型的糠醛制备方法,实现生物质的高值化利用。概述了国内外对纤维素和半纤维素热解形成糠醛机理的实验研究和密度泛函理论分析,总结了生物质选择性热解制备糠醛的工艺技术,指出了今后的研究需要,明确糠醛的热解形成机理以及优化糠醛选择性制备的技术。     

碳基固体酸催化纤维素热解制备左旋葡聚糖和左旋葡萄糖酮

将纤维素快速热解转化为高价值的左旋葡聚糖和左旋葡萄糖酮是国内外研究热点之一。通过制备及表征碳基固体酸,并优化纤维素催化热解的实验条件,在350℃下,Fe₃O₄/C₇₀₀-H₃PO₄与纤维素以1∶3的比例混合,可以显著提高热解过程中左旋葡聚糖[40.7%（质量）]和左旋葡萄糖酮[13.5%（质量）]的产率,分别比纯纤维素热解提高了2倍和22倍。该研究对纤维素的定向高值化转化具有指导意义。     

预处理促进木质纤维素快速热解生成左旋葡聚糖

将木质纤维素快速热解转化为高价值的左旋葡聚糖是国内外研究的热点之一,而左旋葡聚糖产率低是限制其工艺发展的主要因素。论述了纤维素的结构以及木质纤维素的组分对左旋葡聚糖产率的影响,并归纳总结各种预处理及催化热解促进左旋葡聚糖生成的研究现状,最后对未来的研究方向进行了展望。     

博士毕业论文介绍

木质纤维类生物质定向热解行为研究(摘要)刘军利(1.中国林业科学研究院,北京100091;2.中国林业科学研究院林产化学工业研究所,江苏南京210042)采用居热解-气质联用技术,创新研究生物质定向热解行为,揭示纤维素类生物质热解产物的定向调控机理;通过热重与傅立叶红外联用技术(TG-FTIR),研究生物质热解动力学,并建立热解反应动力学模型;通过高温介质热解技术,     

纤维素快速热解生成左旋葡聚糖的机理研究进展

左旋葡聚糖（LG）是纤维素中温快速热解最重要的产物,其生成机理获得了广泛的关注。本文首先总结了国内外不同学者提出的LG生成机理,将其按照反应类型分为4类,即糖苷键均裂反应、糖苷键异裂反应、生成葡萄糖中间体反应以及协同反应,并指出了实验研究在确定反应机理方面的不足。随后总结了近年来一些学者采用密度泛函理论对LG生成机理的研究,具体比较了研究内容和结果,指出了现有研究的不足。最后提出了今后的研究方向以确定LG的生成途径。     

不同金属离子对生物质热解特性的研究综述

针对生物质内部和外加金属离子对生物质热解特性的作用,分别论述了金属离子对纤维素、半纤维素和木质素等生物质主要组分热解特性及热解动力学的影响。     

国内外生物质热解动力学模型的研究现状

主要介绍了国内外学者对生物质热解动力学模型的研究现状。将生物质热解动力学模型分为单组分全局反应模型和多组分全局反应模型两类,其中多组分全局反应模型主要包括纤维素、半纤维素、木质素热解动力学模型和Miller模型、 Janse模型等其他典型模型。     

左旋葡聚糖溶剂热转化为高值化学品的研究进展

木质纤维素热解是一种高效生物质利用途径,其衍生产物左旋葡聚糖(LGA)是纤维素热解产物中最主要的初级产物,其产率可高达80%,将LGA高效转化为其他平台化学品可实现其高值化利用。首先综述了纤维素热解制备LGA的研究进展,对比反应器类型和反应条件对LGA产率的影响,生物质预处理工艺将进一步提升工业化规模制备LGA。然后概述了LGA在不同条件下转化为左旋葡萄糖酮、葡萄糖和呋喃类化合物的最新研究进展。发现在LGA溶剂热催化转化为左旋葡萄糖酮的过程中,催化剂Br?nsted酸性位点及原位移除反应生成的水分有助于提升左旋葡萄糖酮的产率,最优条件下左旋葡萄糖酮的最大产率可接近60%,开发合适的催化剂及溶剂体系有助于进一步提高左旋葡萄糖酮产率。通过酸水解作用,LGA转化为葡萄糖的产率及选择性均可达近100%,且催化剂能够长时间稳定运行,该方法提供了一个由纤维素间接生产葡萄糖的方法。最后,总结了催化剂理化特性及溶剂条件对LGA生成呋喃类和酸酯类化合物的影响规律,发现葡萄糖间接转化机制可促进LGA高效转化为此类化学品。     

热解温度对纤维素和木质素成炭结构的影响

从纤维素、木质素和半纤维素热解转化特征及分子重构建行为着手，利用TG、TEM、Raman、XRD、FT-IR等分析手段探究这3种物质的热解炭化机理。实验结果表明：半纤维素在炭化过程中几乎完全分解；链状结构的纤维素热分解脱除氢氧后，形成的碳自由基发生芳构化重排，大部分构成生物质热解炭中的结晶区；木质素分子结构复杂，呈交联态，在热解过程中同时发生软化熔融，大部分构成了生物质热解炭中的无定形区。在炭化过程中，纤维素在200 ℃之前主要发生脱水反应，200~400 ℃是热解的主要阶段；木质素在研究温度范围（200~500 ℃）内结构相对稳定，在软化熔融的同时仅发生部分结构转变。     

Effect of cellulose, lignin, alkali and alkaline earth metallic species on biomass pyrolysis and gasification

Fundamental pyrolysis/gasification characteristics of natural biomass and acid-washed biomass without alkali and alkaline earth metals (AAEM) were investigated by a thermogravimetric analyzer (TGA) and a fixed-bed reactor. In these experiments, six types of biomass were used and the contents of cellulose, lignin and AAEM species in the biomass were measured. It was observed that the characteristic of biomass pyrolysis and gasification was dependent on its components and AAEM species on the basis of TGA experiments. During biomass pyrolysis, the tar and gas yields increased with the growth of cellulose content, but the char yield decreased. There were two reactions indicating two major decomposition mechanisms. The first stage of decomposition showed rapid mass decrease due to the volatilization of cellulose, while the second stage became slow attributed to the lignin decomposition. The higher the cellulose content, the faster the pyrolysis rate. In contrast, the pyrolysis rate of biomass with higher lignin content became slower. In addition, the rises of cellulose content elevated the peak temperature of gasification and prolonged the gasification time. Meanwhile, the effect of AAEM species on gasification behavior was studied by comparing unwashed and acid-washed biomass. AAEM species increased the peak gasification value, whereas decreased initial gasification temperature. It revealed that the activity of biomass gasification was attributed to the interaction between AAEM-cellulose/lignin.     

生物质与废塑料催化热解制芳烃(Ⅰ):协同作用的强化

采用两段式固定床对比研究了纤维素与高密度聚乙烯（HDPE）的单独物料催化热解、混合物催化热解和分段催化热解,对热解产物分布、目标产物产率及选择性以及催化剂积炭量等参数进行考察,拟从模型化合物水平探索生物质与塑料催化热解制芳烃过程强化协同作用的可能性。结果表明,纤维素与HDPE的共催化热解（混合和分段催化热解）对芳烃的形成具有协同作用,且分段催化热解较混合催化热解表现出更显著的协同作用,可获得更高的芳烃产率及选择性,提高纤维素热解转化率并降低催化剂的积炭,其协同作用符合"双烯合成"反应理论。并结合HDPE催化热解验证实验对分段催化热解制芳烃过程协同作用的强化机理进行阐述。     

Potassium catalysis in the pyrolysis behaviour of short rotation willow coppice

Short rotation willow coppice (SRC) and a synthetic biomass, a mixture of the basic biomass components (cellulose, hemicellulose and lignin), have been investigated for the influence of potassium on their pyrolysis behaviours. The willow sample was pre-treated to remove salts and metals by hydrochloric acid, and this demineralised sample was impregnated with potassium. The same type of pre-treatment was applied to components of the synthetic biomass. Characterisation was performed using thermogravimetric analysis with measurement of products by means of Fourier transform infrared spectroscopy (TGA-FTIR) and pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS). A comparison of product distributions and kinetics are reported. While the general features of decomposition of SRC are described well by an additive behaviour of the individual components, there are some differences in the magnitude of the influence of potassium, and on the products produced. For both SRC and the synthetic biomass, TGA traces indicate catalytic promotion of both of the two-stages of biomass decomposition, and potassium can lower the average apparent first-order activation energy for pyrolysis by up to 50 kJ/mol. For both SRC and synthetic biomass the yields and distribution of pyrolysis products have been influenced by the presence of the catalyst. Potassium catalysed pyrolysis increases the char yields markedly and this is more pronounced for synthetic biomass than SRC. Gas evolution profiles during pyrolysis show the same general features for both SRC and synthetic biomass. Relative methane yields increase during the char formation stage of pyrolysis of the potassium doped samples. The evolution profiles of acetic acid and formaldehyde change, and these products are seen in lower relative amounts for both the demineralised samples. A greater variation in pyrolysis products is observed from the treated SRC samples compared to the different synthetic biomass samples. Furthermore, substituted phenols from lignin pyrolysis are more dominant in the pyrolysis profiles of the synthetic biomass than of the SRC, implying that the extracted lignins used in the synthetic biomass yield a greater fraction of monomeric type species than the lignocellulosic cell wall material of SRC. For both types of samples, PY-GS-MS analyses show that potassium has a significant influence on cellulose decomposition markers, not just on the formation of levoglucosan, but also other species from the non-catalysed mechanism, such as 3,4-dihydroxy-3-cyclobutene-1,2-dione.     

Effects of organic and inorganic metal salts on thermogravimetric pyrolysis of biomass components

Thermogravimetric analyzer (TGA) was employed to elucidate the catalytic effects of organic and inorganic metal salts (K₂CO₃, KAc, Na₂CO₃ and NaAc) on the pyrolysis of three biomass components (cellulose, hemicellulose and lignin). In case of cellulose, TG analysis results showed that all the four metal salts increased the yield of char products and decreased the weight loss rates of cellulose pyrolysis, which followed the order of Na₂CO₃>K₂CO₃>NaAc>KAc. In contrast to cellulose, the four organic and inorganic salts employed had no significant effects on the remaining two biomass components:, hemicellulose and lignin. However, the four metal salts led to the devolatilization reaction of hemicellulose to occur at lower temperature region, and the dehydration reaction of lignin was promoted more or less. An increase in the heating rate might augment the maximum degradation rate. Different mixing ratios had little influence on the progress of catalytic pyrolysis. Based on the observations, the potential mechanism of the catalytic pyrolysis of biomass components with metal salts was discussed.     

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。     

Detailed CFD modelling of fast pyrolysis of different biomass types in fluidized bed reactors

In the present study, an Eulerian‐Eulerian computational fluid dynamics (CFD) model, combined with a comprehensive biomass reaction scheme, was used to simulate fast pyrolysis of four different biomass types in the fluidized bed reactors. The study focuses on the influence of biomass components of different biomass types on the yields, formations, and contents of compositions of pyrolysis products. The result showed that the bio‐oil yield of cellulose‐rich biomass was higher than other biomass types, and char was mainly produced by the fast pyrolysis of LIG‐C of biomass. Moreover, the contents of bio‐oil components were affected by the fast pyrolysis of biomass components. Further, the energy recovery coefficient (ERC) of bio‐oil obtained from pyrolysis of different biomass types was also calculated and analyzed in this paper.

     

Co-pyrolysis of pine cone with synthetic polymers

Biomass from pine cone (Pinus pinea L.) was co-pyrolyzed with synthetic polymers (PE, PP and PS) in order to investigate the effect of biomass and plastic nature on the product yields and quality of pyrolysis oils and chars. The pyrolysis temperature was of 500 °C and it was selected based on results from thermogravimetric analysis of the studied samples. Co-pyrolysis products namely gases, aqueous and tar fraction coming from biomass, oils from synthetic polymers and residual char were collected and analyzed. Due to the synergistic effect in the pyrolysis of the biomass/polymer mixtures, higher amounts of liquid products were obtained compared to theoretical ones. To investigate the effect of biomass content on the co-pyrolysis, the co-pyrolysis of pure cellulose as model natural polymer for biomass with polymer mixture was also carried out. In the presence of cellulose, degradation reaction leading to more gas formation and less char yield was more advanced than in the case of co-pyrolysis with pine cone. Co-pyrolysis gave polar oxygenated compounds distributed between tar and aqueous phase and hydrocarbon oils with composition depending on the type of synthetic polyolefin. Co-pyrolysis chars had higher calorific values compared to pyrolysis of biomass alone.