木质素及其模型化合物氧化裂解催化剂的研究进展

木质素是绿色可持续的再生资源,但结构复杂,是通过C-O和C-C键交织相连的大分子化合物,通过化学转化可以得到系列的高附加值的化学品。通过将转化中的催化剂类型分类,对木质素及其模型化合物氧化裂解催化剂的研究进展进行综述。     

木质素及其模型化合物生产愈创木酚的研究进展

总结了目前使用木质素及其模型化合物香草酸、香草醛和阿魏酸生产愈创木酚的方法,并进一步阐明了生物发酵法生产愈创木酚的基本代谢途径,以期为相关研究提供参考.     

基于氢化断裂木质素及其模型化合物C-O键的研究进展

基于不同氢化断键模式,从催化剂类型综述了目前木质素及其模型化合物的氢化断裂C-O键研究的进展。为木质素及其模型化合物的研究提供相关的理论和实践基础。     

木质素催化热解用催化剂的研究进展

木质素是一种结构复杂、产量丰富但利用率较低的生物质资源,可通过催化热解解聚为高附加值产物,具有广阔的应用前景。本文介绍了催化剂机理研究方法和催化剂作用方式,比较了催化木质素热解常用的分子筛类催化剂、金属氧化物类催化剂和金属盐类催化剂的催化性能、产物收率、产品分布、催化机理及优缺点。文中指出：分子筛类催化剂的脱氧能力强、酸度高,但液体产物收率较低;金属氧化物类催化剂具有液体产物收率较高、热稳定性强等优点,但依赖于催化剂酸碱性的调控;金属盐类催化剂虽高效、价格低廉,但热稳定性差、易失活。同时,本文对木质素催化热解领域提出了展望,未来热解催化剂的研究有待深入和系统化,根据木质素种类和目标产物设计复合型催化剂、核壳型催化剂和多催化剂协同催化是未来热解催化剂发展的趋势。     

木质素慢速热解机理

利用热重考察了不同升温速率下木质素的热解特性,结合红外光谱对木质素热解的不同阶段生成的半焦的表征结果,分析了木质素在慢速升温条件下的热裂解机理,表明:木质素的热解是一个旧键断裂挥发、新键重组的过程。热解过程随着反应时间的推移依次分为水分挥发、支链断裂重组或挥发和芳环缩聚成碳3个阶段。采用Flynn-Wall-Ozawa方法,根据不同升温速率下测得的失重速率变化求算后两个阶段的活化能,结果分别为64 kJ·mol^-1和132 kJ·mol^-1,进一步证明了木质素热解的分段特征,并表明芳环缩聚成碳所需活化能远大于与苯环相连的支链断裂所需的能量。     

木质素结构及热解特性

为研究结构类型和提取方法对木质素热解特性的影响,本研究采用Klason方法预处理得到的棉杆、核桃壳Klason木质素和贝克曼方法预处理得到的核桃壳磨木木质素(MWL),并结合傅里叶红外光谱仪(FT-IR)和快速热解仪-气相色谱/质谱联用(Py-GC/MS)对其化学结构和热解特性进行分析。FT-IR表明碱木质素为G型木质素,棉杆木质素属于GS类型木质素,而核桃壳木质素具有HGS木质素的特征;Py-GC/MS分析发现原料的变化以及提取方法对木质素热解产物的组成有明显的影响,在棉杆Klason木质素中邻苯二酚类产物含量为28.18%,而在核桃壳Klason和磨木木质素的含量分别为18.12%和35.11%。同时研究表明经两种方法处理的木质素结构有明显的不同,其中Klason木质素结构中苯丙酸侧链上的α-和β-醚键明显断裂,而贝克曼处理主要体现在苯基芳基醚键的断裂。     

云南松热解及其热解产物的研究

采用自制固定床反应器对云南松木粉进行热解,探讨了热解温度、原料颗粒尺寸和氮气流速对云南松热解特性的影响,并采用GC-MS对生物油的组分含量进行分析。结果表明:在热解温度为500 ℃,原料颗粒尺寸为0.250~0.420 mm,氮气流速为150 mL/min条件下,生物油的产率最高为50%,液体组分主要以2,6-二叔丁基对甲酚、2-甲氧基-4-甲基苯酚、异丁香酚、愈创木酚为主,占液体总量的39.24%。     

木质素结构及热解特性

为研究结构类型和提取方法对木质素热解特性的影响,本研究采用Klason方法预处理得到的棉杆、核桃壳Klason木质素和贝克曼方法预处理得到的核桃壳磨木木质素（MWL）,并结合傅里叶红外光谱仪（FT-IR）和快速热解仪-气相色谱/质谱联用（Py-GC/MS）对其化学结构和热解特性进行分析。FT-IR表明碱木质素为G型木质素,棉杆木质素属于GS类型木质素,而核桃壳木质素具有 HGS木质素的特征;Py-GC/MS分析发现原料的变化以及提取方法对木质素热解产物的组成有明显的影响,在棉杆Klason木质素中邻苯二酚类产物含量为28.18%,而在核桃壳Klason和磨木木质素的含量分别为18.12%和35.11%。同时研究表明经两种方法处理的木质素结构有明显的不同,其中Klason木质素结构中苯丙酸侧链上的α-和β-醚键明显断裂,而贝克曼处理主要体现在苯基芳基醚键的断裂。     

赤泥/木质素共热解制备复合吸附材料及其性能

炼铝工业产生的赤泥废渣以不合理的方式处置,会造成严重的环境污染和资源浪费。赤泥中富含的铁元素以Fe₂O₃的形式存在,不利于铁资源回收,可通过还原方式制取磁性材料用于重金属离子的去除。基于此,本研究采用碳热还原法耦合赤泥与木质素制备一种复合吸附材料。系统探究还原温度、还原时间、还原剂用量对还原效果的影响,并开展铅离子吸附实验。研究表明,通过与烟煤还原赤泥对比得出木质素还原赤泥最佳工艺参数：还原温度625℃、还原时间30min、木质素与赤泥质量比为1∶1;GC对共热解气体产物进行分析得出赤泥的引入能够提高氢气产量;GC-MS对共热解液体产物进行分析得出木质素/赤泥共热解能够提升芳烃类化合物产量;吸附实验得出制备的复合材料能够有效去除水溶液中的铅离子。通过耦合赤泥、木质素残渣两种废弃物制备复合吸附材料,能够响应国家环保政策,具备潜在的经济、能源、环境效益。     

The condensation of lignin model compounds with hexamethylene diisocyanate

Analysis by infrared and nuclear magnetic resonance spectroscopy, differential scanning calorimetry and thermogravimetric estimation of the condensation products of hexamethylene diisocyanate and certain lignin model compounds bearing a free phenolic hydroxyl (prepared both in the melt at 100°C and in refluxing methylene chloride solution) shows that stoichiometric proportions give high yields of bisurethanes. These products decompose below 160°C to regenerate the starting materials.     

木质素及其模化物催化加氢脱氧研究进展

木质纤维素类生物质是重要的可再生原料,可通过多种转化途径转化为燃料或精细化工品。木质素作为木质纤维素物质的重要成分之一,因其结构复杂,其利用一直没有得到很大突破。笔者以木质素及其模化物催化加氢脱氧制取化工品为着眼点,按催化剂种类综述了国内外木质素及其模化物催化加氢脱氧研究进展情况,并对其进行了分析评价,指出了木质素催化加氢脱氧的研究重点。     

Effect of bed material,lignin content,and origin on the processability of biomass in fast pyrolysis reactors

Lignin has great potential for the production of valuable aromatic compounds and has attracted considerable attention. The development of high value applications for Kraft lignin would boost the profitability of pulp and paper operations. A potential solution is the pyrolytic conversion of lignin to valuable liquids and solids. However, Kraft lignin is a thermally sensitive powder which tends to agglomerate under pyrolysis conditions. A mechanically fluidized reactor (MFR) can be used to monitor both the generation of vapours and gas during pyrolysis and how cohesive a feedstock becomes when pyrolyzed. The MFR was, therefore, used to evaluate alternative solutions to improve Kraft lignin behaviour by mixing it with non‐problematic feedstocks or by modifying its bed material. Finally, Kraft lignin behaviour and products were compared to those of hydrolysis lignins from different origins.     

Mathematical modelling of lignin pyrolysis

Seven lignins from different sources were pyrolysed (i) isothermally in vacuum over the temperature range 300–1300 °C and (ii) at a constant heating rate of 30 °C min^?1 and a pressure of 0.1 MPa over the temperature range 150–900 °C. The mass fraction of each product—char, tar and gas species—and the elemental composition of the char and the tar were determined for the flash pyrolysis experiments. The evolution rates of the gas species and the tar versus the dynamic temperature of pyrolysis were determined for the constant heating rate pyrolysis experiments. Although the amount of each product species varied from lignin to lignin, the evolution rates were insensitive to the lignin source and the extraction process. To model the data, modifications were made to a recently developed model of coal pyrolysis. The model proved to be successful in simulating both the data from vacuum flash pyrolysis and constant heating rate pyrolysis of Iotech lignin.     

Low-temperature pyrolysis of Texas lignite,basic extracts and some related model compounds

Low-temperature (400 °C) pyrolysis of Texas lignite produced volatile products typical of coal tars, with tar evolution beginning at about 300 °C. n-Alkanes up to about C₃₀ were observed among the products and these were accompanied by smaller but significant amounts of 1 -alkenes. Similar pyrolyses were performed on pyridine extracts and sodium hydroxide extracts of lignite. The alkanes and alkenes were seen among the pyrolysis products from the pyridine extracts and from the residual lignite from both types of extractions, but they were not seen among the pyrolysis products from the sodium hydroxide extracts. Pyrolyses of some model compounds suggested that dealkylation of alkyl-substituted arenes can be significant at 400 °C and can account for the production of the alkanes and alkenes from the lignite.     

添加木质素对污泥热解过程氮转化的影响

利用热重-质谱联用仪（TG-MS（在线检测添加不同比例木质素的污泥热解和主要含氮气体释放特性,并利用傅里叶红外光谱仪（FTIR（在线检测热解过程固体残焦表面官能团的变化规律,分析木质素对污泥热解过程氮转化的影响,从而揭示氮的迁移机理。结果表明：污泥热解过程NH₃的生成主要来自蛋白质的脱氨作用,加入木质素后热解过程中产生了大量羰基,抑制了氨基酸的分子内环化和分子间缩聚反应,而促进了直链酰胺的生成,最终在OH自由基攻击下转化成HNCO和HCN;NH₃的增加并非来自HCN和OH的反应,而是由未缩合的氨基脱除生成;另外,添加40%左右的木质素对于减少污泥热解过程中NO_x前驱物的排放有积极意义。     

Formation and destruction of H2S in the short residence time pyrolysis of pulverized coal and model compounds

The evolution of sulphur as H₂S from three US bituminous coals, L-cystine, and thianthrene has been studied in the reflected shock region of a chemical shock tube. With heating rates of approximately 3 × 10⁶Ks^?1, to temperatures in the range 1000–2000K, ultimate yields of sulphur from 7 to 70% as H₂S are observed in as little as 1.5 ms. The most important influence on ultimate yields may be the H/S molar ratio in the fuel which corresponds in the hydrocarbons studied with the H₂S yields. Inherent mineral matter may also influence the evolution, as H₂S formation precedes light hydrocarbon formation from the two model compounds, but occurs nearly simultaneously from the coals. The overall rate of H₂S formation for the three coals is adequately described by a reaction, first order with respect to remaining sulphur, with a rate constant $\text{k=8.1 × 10}{}^7\text{exp}\text{(?}\text{15 960}\text{T}\text{) s}{}^{\mathrm{?1}}$. In the pyrolysis of all five solids, the H₂S yields are decreased to below detectable limits at temperatures >1500K. The path for destruction of the H₂S appears to be by reaction with hydrocarbons such as C₂H₂, the concentration of which becomes similar to the H₂S concentration in the temperature range 1500–1600K.