基于PY-GC/MS的生物质组分间相互作用的热解实验

为研究生物质三组分间热裂解过程中的相互作用,利用热裂解-气相色谱/质谱联用仪（PY-GC/MS）联用的方法,对纤维素、木聚糖（半纤维素的模化物）和木质素进行单独热裂解及两两组分混合热裂解实验。单组分实验结果表明,在热解温度600℃、热解时间10s条件下纤维素的热解产物主要以左旋葡聚糖为主,木聚糖以乙酸和糠醛为主,而木质素主要以酚类物质为主。组分混合热裂解实验结果表明,纤维素促进了木聚糖热裂解生成更多的乙酸和糠醛,而木聚糖和木质素对纤维素热解生成左旋葡聚糖具有强烈的抑制作用;纤维素和木聚糖的存在大大促进了木质素热裂解生成酚类物质,而木质素抑制了木聚糖热裂解生成乙酸和糠醛。此外,研究还发现混合组分热解的相互作用受到热解温度和停留时间的影响。     

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.     

纤维素与木质素共热解试验及动力学分析

采用热重分析仪（TGA）对木质素与纤维素单独热解和共热解基本特性及热解动力学进行了研究。热重分析曲线表明,木质素热解过程是由两个位于不同温度段的热解过程组成,纤维素则仅在300～380 ℃的温区内迅速热解,在纤维素含量较低（≤40%）共热解时,二者表现为相互抑制作用,但随着纤维素含量增大,二者关系转变为相互促进作用。热解动力学研究表明,纤维素与木质素单独热解和共热解过程都可用一级反应动力学模型来描述,且随着纤维素含量增加,反应活化能（E）也随之增加,但其值总小于活化能线性加和值（Ec）,据此可推测共热解过程存在着一定的协同作用。     

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。     

Characteristics of hemicellulose,cellulose and lignin pyrolysis

The pyrolysis characteristics of three main components (hemicellulose, cellulose and lignin) of biomass were investigated using, respectively, a thermogravimetric analyzer (TGA) with differential scanning calorimetry (DSC) detector and a pack bed. The releasing of main gas products from biomass pyrolysis in TGA was on-line measured using Fourier transform infrared (FTIR) spectroscopy. In thermal analysis, the pyrolysis of hemicellulose and cellulose occurred quickly, with the weight loss of hemicellulose mainly happened at 220–315 °C and that of cellulose at 315–400 °C. However, lignin was more difficult to decompose, as its weight loss happened in a wide temperature range (from 160 to 900 °C) and the generated solid residue was very high (∼40 wt.%). From the viewpoint of energy consumption in the course of pyrolysis, cellulose behaved differently from hemicellulose and lignin; the pyrolysis of the former was endothermic while that of the latter was exothermic. The main gas products from pyrolyzing the three components were similar, including CO₂, CO, CH₄ and some organics. The releasing behaviors of H₂ and the total gas yield were measured using Micro-GC when pyrolyzing the three components in a packed bed. It was observed that hemicellulose had higher CO₂ yield, cellulose generated higher CO yield, and lignin owned higher H₂ and CH₄ yield. A better understanding to the gas products releasing from biomass pyrolysis could be achieved based on this in-depth investigation on three main biomass components.     

生物质三组分与低密度聚乙烯共催化热解制取轻质芳烃的协同作用机理

生物质与废塑料共催化快速热解是制取轻质芳烃的重要途径。 采用不同种类的分子筛催化剂,首先研究了分子筛种类对杨木、生物质三组分和低密度聚乙烯（LDPE）单独催化快速热解轻质芳烃产率的影响,其次研究了生物质三组分与LDPE在共催化热解过程中的协同作用机理。结果表明：在杨木、生物质三组分和LDPE单独催化快速热解时,HZSM-5（25）催化剂体现出最高的轻质芳烃产率;在杨木和LDPE共催化快速热解时,随着LDPE质量的增加,轻质芳烃的产率呈先升高后降低趋势;在生物质三组分和LDPE共催化快速热解时,纤维素和半纤维素热解的呋喃类中间产物与LDPE热解的轻烯烃中间产物易发生“双烯合成”反应,表现出较强的协同催化作用,促进轻质芳烃的生成,而木质素则抑制轻质芳烃生成。     

Elucidation of the interaction among cellulose,xylan, and lignin in steam gasification of woody biomass

The reaction mechanism for gas and tar evolution in the steam gasification of cellulose, lignin, xylan, and real biomass (pulverized eucalyptus) was investigated with a continuous cross‐flow moving bed type differential reactor, in which tar and gases can be fractionated according to reaction time. In the steam gasification of real biomass, the evolution rates of water‐soluble tar (derived from cellulose and hemicelluloses) and water‐insoluble tar (derived from lignin) decrease with increasing reaction time. It was found that the evolution of water‐soluble tar occurs earlier than in the gasification of pure cellulose, indicating an interaction of the three components. The predicted yield of water‐insoluble tar is substantially less than that of real biomass. This implies that the evolution of tar from the lignin component of biomass is enhanced, compared with pure lignin gasification, by other components. The gas evolution rate from real biomass is similar to that predicted by the superposition of cellulose, lignin, and xylan. © 2008 American Institute of Chemical Engineers AIChE J, 2009     

TGA and macro-TGA characterisation of biomass fuels and fuel mixtures

The thermal behaviour of selected biomass fuels and mixtures as wood, demolition wood, coffee waste and glossy paper was investigated using a thermogravimetric analyzer (TGA) and a macro-thermobalance (macro-TGA). A kinetic model, involving first-order independent parallel reactions, was applied to results obtained from pyrolysis TGA experiments. The pyrolysis rate was considered as the sum of the main biomass pseudo-components, namely cellulose, hemicellulose and lignin. Additionally, the thermal behaviour of the same fuels was investigated at combustion conditions in the TGA, including ignition behaviour. The thermogravimetric analysis showed that each single fuel had pyrolysis and combustion characteristics based on its own main pseudo-components (hemicellulose, cellulose and lignin). The pyrolysis and combustion characteristics of selected fuel mixtures and the gas composition analysis from macro-TGA experiments showed respectively quantitative and qualitative summative behaviour based on the single fuels.     

TG study on pyrolysis of biomass and its three components under syngas

Pyrolysis of sawdust and its three components (cellulose, hemicellulose and lignin) were performed in a thermogravimetric analyzer (TGA92) under syngas and hydrogen. The effect of different heating rates (5, 10, 15 and 20 °C/min) on the pyrolysis of these samples were examined. The pyrolysis tests of the synthesized samples (a mixture of the three components with different ratios) were also done under syngas. The distributed activation energy model (DAEM) was used to study the pyrolysis kinetics. It is found that syngas could replace hydrogen in hydropyrolysis process of biomass. Among the three components, hemicellulose would be the easiest one to be pyrolyzed and then would be cellulose, while lignin would be the most difficult one. Heating rate could not only affect the temperature at which the highest weight loss rate reached, but also affect the maximum value of weight loss rate. Both lignin and hemicellulose used in the experiments could affect the pyrolysis characteristic of cellulose while they could not affect each other obviously in the pyrolysis process. Values of k₀ (frequency factor) change very greatly with different E (activation energy) values. The E values of sawdust range from 161.9 to 202.3 kJ/mol, which is within the range of activation energy values for cellulose, hemicellulose and lignin.     

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...     

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.     

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.     

生物质和煤共热解特性及催化剂对热解的影响

为研究生物质和煤程序升温共热解特性及相互作用,利用热天平和管式炉反应器对白松木屑和五彩湾烟煤的共热解特性及催化剂对生物质和煤共热解的影响进行了研究,并考察了共热解半焦的孔结构特性。结果表明：不同比例的生物质和煤在共热解过程中,两者基本保持了各自的热解特性,由于生物质和煤的主要热解阶段温度相差较大,共热解过程中没有发生明显的协同作用。生物质和煤共热解半焦产率实验值大于计算值,当生物质质量分数从75%减少至25%时,半焦产率实验值与计算值之间的差值从0.81个百分点增加到1.07个百分点。橄榄石和载镍橄榄石（NiO/olivine）的添加促进了共热解反应发生的深度。载镍橄榄石催化剂添加（原料和催化剂质量比1：1）的条件下,共热解碳转化率提高了0.5%~5.1%,随着混合物中生物质比例的增加,催化剂的催化效果更加明显。     

固定床反应器中生物质/废塑料共热解制备燃料油

通过热重分析不同生物质（木屑和秸秆）单独热解以及与塑料（PP和dcPVC）共热解时的热解行为,研究了生物质与塑料共热解过程中的协同作用。在固定床反应器中考察了塑料的含量对生物质/塑料共热解的影响,最后通过元素分析和GC-MS对所得生物油进行了分析。研究结果表明：生物质和塑料共热解过程中存在明显的协同作用。木屑和PP共热解过程中的协同作用最为显著,当PP含量为80%时,所得生物油的产率最高,明显高于两者单独热解得到的生物油。元素分析和GC-MS分析结果表明：木屑和PP所得生物油的含氢量较高,所得到生物油的热值与石化燃油的相近。     

生物质化学组分及其液化残渣的热重行为

分别对木粉主要组分（纤维素、半纤维素和木质素）及其在相同液化条件下的液化残渣的热重行为进行了研究。热重实验结果表明,木粉主要组分的热稳定性为：木质素 > 纤维素 > 半纤维素。木粉的热解过程可以认为是这3种主要组分热解行为的综合：木质素的热解比较缓慢,热解温度区间最宽,主要失重温度为250～630 ℃;而纤维素和半纤维素的主要热解温度分别为332～383 ℃和236～333 ℃。在液化反应过程中,木粉主要组分发生降解从易到难的顺序为：木质素 > 半纤维素 > 纤维素。在木粉的液化过程中,快速液化阶段主要与半纤维素和木质素有关,而液化残渣率的高低主要与纤维素液化程度有关。     

Kinetic Model of Biomass Pyrolysis Based on Three-component Independent Parallel First-order Reactions

The pyrolysis behavior of two kinds of typical biomass (pine wood and cotton stalk) was studied in nitrogen atmosphere at various heating rates by thermogravimetric analysis (TGA). The pyrolysis process can be divided into three stages: evolution of moisture (<200℃), devolatilization (200~400℃) and carbonization (>400℃). The comparison of DTG curves of two biomass materials show that the higher the hemicellulose content of biomass, the more evident the shoulder peak of DTG curve. The weight loss process of two materials was simulated by the kinetic model assuming cellulose, hemicellulose and lignin pyrolyzing independently and in parallel, obeying first-order reactions. The pyrolysis kinetic parameters corresponding to the three components were estimated by the nonlinear least square algorithm. The results show that their fitting curves are in good agreement with the experimental data. Their activation energy values for pine wood and cotton stalk are in the range of 188~215, 90~102, 29~49 and 187~214, 95~101, 30~38 kJ/mol, respectively. The corresponding pre-exponential factors are in the range of 1.8′1015~2.0′1016, 1.6′107~7.1′108, 9.3′101~1.5′103 and 1.2′1015~6.7′1017, 1.2′108~1.4′109, 1.4′102~4.6′102 min-1, respectively. In addition, the activation energy of cellulose and lignin increased and their contributions to volatile tended to fall, whereas the activation energy of hemicellulose decreased and its contribution to volatile tended to rise with increasing of heating rate.     

Comparison of the thermal reactivities of isolated lignin and holocellulose during pyrolysis

Woody shells of Turkish hazelnuts which are rich in lignin content offer an important potential as a renewable energy source. Hence, this study focuses on the investigation of the thermal reactivities of the real macromolecular ingredients of this biomass species. Hazelnut shells were treated with chemicals to isolate its holocellulose (hemicelluloses + cellulose) and lignin. Scanning Electron Microscopy (SEM) images revealed the significant differences between the physical features of the untreated biomass and its isolated ingredients. Thermal properties of the biomass and these ingredients were examined by Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) techniques under non-isothermal pyrolysis conditions from ambient to 900 °C. It was found that unlike holocellulose, lignin slowly decomposes in a wider temperature range, and its decomposition is associated with exothermic heat flow. It was also concluded that the hemicellulosics in holocellulose have very important effects with respect to the char yield and the exothermicity of the process. Besides, inorganics in biomass play a catalytic role during pyrolysis. The activation energies calculated according to Borchardt-Daniels' kinetic model were 64.8 and 51.8 kJ/mol for the pyrolysis of holocellulose and lignin, respectively, and each of them is higher than that for the untreated biomass.     

Preparation of artificial wood films with controlled biodegradability

Artificial wood films containing cellulose, xylan, and lignin were easily prepared by the dissolution of wood components in 1‐ethyl‐3‐methylimidazolium acetate followed by reconstitution with distilled water. The composition and characteristics of wood films were highly controllable and predictable through the variation of the concentration of each component in the wood solution. The water vapor solubility of the wood films was increased when the xylan content was increased and the content of lignin was decreased. The biodegradability of the artificial wood films was investigated with cellulase from Trichoderma viride. The relative degradability of the wood film prepared with 5% cellulose and 5% lignin was 42%, whereas that of the wood film made with 5% cellulose and 5% xylan was 189%. The biodegradability of cellulose in the wood films correlated well with the content of xylan and lignin, and it was enhanced when the xylan content was increased and the content of lignin was decreased. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42109.     

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.