生物炭对向日葵秸秆热解特性及气体产物影响

为了研究生物炭对向日葵秸秆热解的影响,以向日葵秸秆为原料,基于TG-FTIR研究生物炭添加前后向日葵秸秆热解特性与气体产物的变化。结果表明,与向日葵秸秆相比,混合样品主热解区间由276~349℃变得更长,并且发生不同程度的偏移,热解活化能不同程度降低,由60.21降到38.07~50.35 kJ/mol,呋喃类、酸类、含羰基类化合物、芳香醛类、CO、CH4等产物吸光度值存在差异。随着添加500℃制备生物炭比例增加,混合样品热解的活化能减小,释放气体产物中芳香醛类释放量增量减少,CO与CH4释放量降低。添加不同制备温度的生物炭,混合样品热解产生呋喃类、酸类、含羰基类化合物释放量均有所降低;添加500和700℃制备的生物炭,混合样品热解气体产物中芳香醛类增加。添加900℃制备的生物炭,向日葵秸秆热解气体产物中CO产量增加。该研究为向日葵秸秆的有效利用提供理论基础和技术支撑。     

小麦秸秆热解过程中碳和微量元素迁移转化规律

为研究小麦秸秆热解过程中碳元素和微量元素的迁移转化规律,依托连续式作物秸秆分段均匀炭化联产系统,基于热解炭化生产工艺,测算及分析碳元素在秸秆热解过程中的存在形式及迁移转化量,利用HSC Chemistry软件模拟微量元素在秸秆热解炭化过程中的组分变化,分析了8种微量元素的迁移转化规律,为生物质热解机理的进一步研究提供支撑,为提高秸秆热解炭品质提供强有力保证。结果表明:经测试及测算得到的碳元素迁移足迹图符合碳元素质量守恒定律,碳元素迁移到热解炭中41.12%,以固定碳存在;22.83%迁移到焦油中,以大分子长链烃和环链烃存在;26.62%的碳元素以六碳内的短链烃存在于热解气;4.71%迁移到木醋液中为醛、酮、酸等。小麦秸秆中含量在100μg/L以上的8种高富集微量元素里,K、Na、Ca、Mg主要以硫酸盐、磷酸盐及氯化物形式存在于热解炭中,Al、Fe多以氧化物、硫化物以及硅、氧共融物形态被大量保留在热解炭中,而P、S元素在热解炭化过程中的析出主要是有机结合物的分解。     

木质原料热解及活性炭结构的研究

以椰壳为代表原料进行热解研究，用热重分析法分析了椰壳热分解的机理。与一般木质原料一样，椰壳也是由半纤维素、纤维素和木质素构成，椰壳中的半纤维素的分解温度在200～260℃，纤维素的分解温度在260～295℃，木质素的分解温度在295～320℃。本研究还探讨了椰壳炭的孔结构参数，炭化温度425～720℃，其微孔容积为0．124～O．222mL／g，并用扫描电子显微镜观察了椰壳炭的表面形貌，椰壳在热分解时，细胞壁分解形成了微米级的大孔，并保留了椰壳的纤维状结构。采用离子发射光谱，分析了椰壳炭的微量元素组成，主要有铝、钡、铁、镁、钙、硅等。     

生物质热解液化技术研究现状及展望

生物质热解液化技术是把低能量密度生物质转化为高能量密度液体产物的一种新型生物质能利用技术。该技术很大程度上能缓解当今社会的能源危机以及环境污染，是人类开发可再生资源的一种非常有效的途径。本文简要介绍了国内外对这一技术的研究及其进展。     

转锥式生物质闪速热解液化反应器生产能力的计算

转锥式生物质闪速热解液化装置是当今研究的一个热点,也是一种很有前途的生物能利用技术,其反应器的生产能力是该装置设计和推广的一个重要参数和指标。本文着重研究了转锥式反应器生产能力的计算方法,为转锥式反应器的设计提供理论支持。     

Characteristics and decomposition rates of pruning residues from a shaded coffee system in Southeastern Brazil

In the Zona da Mata Mineira of Southeastern Brazil the development of sustainable land requires the integration of crops with trees. The objectives of this study then were to (i) characterize prunings from the main tree species in an agroforestry system; (ii) determine the effects of the physical and chemical characteristics of the prunings on their decomposition patterns in the laboratory; (iii) assess the effect of mixing leaves of different species on decomposition rates; and (iv) propose a decomposition index for the residues studied. The study was carried out with pruning residues from Cajanus cajan, Solanum variable, Cassia ferruginea, Piptadenia gonoacantha, Croton urucurana, and Melinis multiflora. The materials were characterized for total C, N, P, Ca, Mg and K contents; lignin, cellulose, hemicellulose and soluble polyphenols contents. The pruning residues had high polyphenols and lignin contents, high C:N and C:P ratios, and low contents of Ca, Mg, and K. The low decomposition rates of the prunings were related to the P, K, hemicellulose and polyphenol contents. The rates of N mineralization from most of the residues indicate that there is a potential to supply the needs of a crop of maize. The residues of some species, if decomposed alone, would not supply sufficient nutrients, and need to be mixed with leaves of other species.This revised version was published online in November 2005 with corrections to the Cover Date.     

Reaction behavior of lignin in supercritical methanol as studied with lignin model compounds

 The reaction behavior and kinetics of lignin model compounds were studied in supercritical methanol with a batch-type supercritical biomass conversion system. Guaiacol, veratrole, 2,6-dimethoxyphenol, and 1,2,3-trimethoxybenzene were used as model compounds for aromatic rings in lignin. In addition, 5-5, β-1, β-O-4, and α-O-4 types of dimeric lignin model compounds were used as representatives of linkages in lignin. As a result, aromatic rings and 5-5 (biphenyl)-type structures were stable in supercritical methanol, and the β-1 linkage was not cleaved in the β-1-type structure but converted rapidly to stilbene. On the other hand, β-ether and α-ether linkages of β-O-4 and α-O-4 lignin model compounds were cleaved rapidly, and these compounds decomposed to some monomeric compounds. Phenolic compounds were found to be more reactive than nonphenolic compounds. These results indicate that cleavages of ether linkages mainly contribute to the depolymerization of lignin, whereas condensed linkages such as the 5-5 and β-1 types are not cleaved in supercritical methanol. Therefore, it is suggested that the supercritical methanol treatment effectively depolymerizes lignin into the lower-molecular-weight products as a methanol-soluble portion mainly by cleavage of the β-ether structure, which is the dominant linkage in lignin. Received: December 19, 2001 / Accepted: April 30, 2002 Acknowledgments This research has been done under the research program for the development of technologies for establishing an ecosystem based on recycling in rural villages for the twenty-first century from the Ministry of Agriculture, Forestry and Fisheries, Japan; by a Grant-in-Aid for Scientific Research (B)(2) (no.12460144, 2001.4–2003.3) from the Ministry of Education, Culture, Sports, Science and Technology, Japan; and under the research program from Kansai Research Foundation for Technology Promotion, Japan. The authors thank them for their financial support. This study was presented in part at the 45th Lignin Symposium, Ehime, Japan, October 2000 and the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, Japan, April 2002 Correspondence to:S. Saka     

Reactivity of secondary hydroxyl groups in methylβ-d-xylopyranoside toward aβ-o-4-type quinone methide

Methyl-d-xylopyranoside was allowed to react with-O-4-type quinone methide without a catalyst to elucidate the reactivities of secondary hydroxyl groups at the C2, C3, and C4 positions. Benzyl ether-type lignin-carbohydrate complex (LCC) compounds linked at the C2 and C4 positions were predominant, at a ratio of 23. However, the reactivity of the hydroxyl group at the C3 position was quite low. These results strongly suggest that the reactivity of the C2 hydroxyl group in xylan toward quinone methide intermediate is higher than that of the C3 hydroxyl group during biosynthesis of LCCs.     

Determination of nitrobenzene oxidation products by GC and1H-NMR spectroscopy using 5-iodovanillin as a new internal standard

The nitrobenzene oxidation method was modified to obtain more reproducible data and more structural information about lignin, not only by gas chromatography (GC) but also by proton nuclear magnetic resonance (¹H-NMR) spectroscopy for quantitative determination of the oxidation products and to simplify the procedures. The nitrobenzene oxidation mixture was directly extracted after acidification without preextraction of by-products. The direct extraction made the extractive step easy and gave reproducible data. 5-Iodovanillin was selected as a new internal standard. The reason for this selection was that 5-iodovanillin did not exist in the nitrobenzene oxidation products from any plant species and had an aldehyde group whose peak did not overlap with the other aldehyde peaks on an¹H-NMR spectrum. Thus, the use of 5-iodovanillin enabled us to quantifyp-hydroxybenzaldehyde, vanillin, and syringaldehyde in oxidation products on the basis of¹H-NMR analysis as well as GC. Furthermore, more information about the condensed structure of lignin was derived by comparing the¹H-NMR and GC analyses.Part of this work was presented at the 42nd Annual Meeting of the Lignin Symposium, Sapporo, October 1997