氧化生物质制备甲酸过程中木质素结构变化的表征

表征生物质酸性氧化制备甲酸过程中木质素结构变化是木质素高值化利用的关键之一。以O₂为氧化剂,对松木粉在NaVO₃-DMSO-H₂SO₄体系中氧化生成甲酸进行研究,考察反应时间、催化剂和固液比对木质素结构变化的影响。采用高效液相色谱（HPLC）、傅里叶变换红外光谱（FT-IR）、凝胶渗透色谱（GPC）、气相色谱（GC）和二维异核单量子相干核磁光谱（2D-HSQC）对固体残渣和已溶解的木质素碎片进行分析。结果显示,在H₂SO₄浓度为0.7wt.%的NaVO₃-DMSO-H₂SO₄体系中,当固液比为1∶50时,甲酸的碳摩尔收率为75.1%。在氧化解聚过程中,木质素通过断裂C—O键被降解形成125 ~ 900 g/mol之间的碎片,而且木质素碎片中的芳环结构被氧化成醌类结构。     

Lignin Interaction with Cellulase during Enzymatic Hydrolysis

The conversion of lignocellulosic biomass into biofuels or biochemicals typically involves a pretreatment process followed by the enzyme-catalyzed hydrolysis of cellulose and hemicellulose components to fermentable sugars. Many factors can contribute to the recalcitrance of biomass, e.g., the lignin content and structure, crystallinity of cellulose, degree of fiber polymerization, and hemicellulose content, among others. However, nonproductive binding between cellulase and lignin is the factor with the greatest impact on enzymatic hydrolysis. To reduce the nonproductive adsorption of enzymes on lignin and improve the efficiency of enzymatic hydrolysis, this review comprehensively summarized the progress that has been made in understanding the interactions between lignin and enzymes. Firstly, the effects of pretreatment techniques on lignin content and enzymatic hydrolysis were reviewed. The effects of lignin content and functional groups on enzymatic hydrolysis were then summarized. Methods for the preparation and characterization of lignin films were assessed. Finally, the methods applied to characterize the interactions between lignin and cellulase were reviewed, and methods for decreasing the nonproductive binding of enzymes to lignin were discussed. This review provides an overview of the current understanding of how lignin hinders the enzymatic hydrolysis of lignocellulosic biomass, and provides a theoretical basis for the development of more economical and effective methods and additives to reduce the interaction of lignin and enzymes to improve the efficiency of enzymatic hydrolysis.     

制备活性炭负载K2CO3用于催化餐饮废油合成生物柴油

以K₂CO₃为催化剂,工业碱木质素(KL)为活性炭(AC)前体,在管式电阻炉中经一步共混活化(K₂CO₃/KL质量比为0.6、活化温度800℃、N₂流量100cm³/min、活化时间2h)制备K₂CO₃/AC固体碱催化剂,用于餐饮废油与甲醇的酯交换反应合成生物柴油。对制备的固体碱催化剂进行了X-射线衍射(XRD)、BET表面积及扫描电镜(SEM)表征。考察了反应温度、催化剂用量、反应时间、醇油摩尔比等因素对餐饮废油转化为生物柴油产率的影响。结果表明当反应时间2h、反应温度60℃、醇油摩尔比15:1、催化剂为原料油质量的3.0%时,生物柴油最大产率为87.5%。考查了催化剂的循环利用效果,结果表明催化剂能循环利用3次,第3次利用时生物柴油的产率仍达到80.7%。     

木质素基二氧化硅复合纳米颗粒的制备及在高密度聚乙烯中的应用

针对目前木质素基SiO₂复合纳米颗粒聚集严重及木质素负载量低,难以应用的现状,以碱木质素为主要原料,先通过磷酸化改性制备磷酸化碱木质素,再利用酸析共沉法将1.2份磷酸化碱木质素与1份纳米SiO₂(均为质量份)复合制备了木质素-SiO₂复合纳米颗粒,并探究复合颗粒对高密度聚乙烯(HDPE)力学性能的影响。FT-IR、XPS、TEM、TG和静态接触角测试结果表明,木质素主要以氢键作用与SiO₂结合;与原料二氧化硅相比,复合颗粒的粒径从25 nm增加到40 nm,聚集程度明显减弱;复合纳米颗粒中木质素占47%(质量分数);表面的疏水性增强,有利于复合颗粒在高密度聚乙烯中均匀分散,显著提高了HDPE的拉伸强度。与碱木质素/HDPE复合材料相比,木质素-SiO₂复合纳米颗粒/HDPE复合材料的拉伸强度和断裂拉伸率分别提高了48.68%和73.57%。     

耐高温强化泡沫体系提高超稠油油藏采收率研究

超稠油油藏经多轮次蒸汽吞吐工艺后, 易出现注汽压力过高、 热损失大、 蒸汽波及范围小、 汽窜等问题, 严重影响油藏的有效动用。针对超稠油油藏这一开采难题, 采用一维、 三维物理模拟手段研究了分别添加栲胶、碱木素的强化泡沫体系在油藏温度、 地层水矿化度、 注入方式等影响因素下的封堵性能。结果表明, 泡沫与两种凝胶体系均产生协同效应, 体现为凝胶强化了泡沫的稳定性, 而泡沫可携带凝胶更多的进入高渗层, 进而实现泡沫体系的高效调剖; 三维物理模拟实验表明,伴随蒸汽分别注入两种体系均可提高稠油油藏采收率,同时大幅降低含水率, 栲胶泡沫体系的伴注蒸汽驱开采方式可比单纯注入蒸汽提高采收率2 0%左右, 碱木素泡沫体系可提高1 1%。     

木质素催化解聚的研究进展

木质素是一种芳环结构来源丰富且价格低廉的可再生资源。从木质素出发催化解聚制备单酚类高附加值精细化学品和芳香烃烷烃等高品位生物燃料,可以部分替代以化石燃料为原料的生产过程,是生物质资源全组分高效综合利用的重要组成部分。在木质素催化解聚方法中,催化氢解可以直接将木质素转化为低氧含量的液体燃料,在生物燃料利用方面展现出巨大的潜力。本文详细总结了木质素的催化解聚方法,从催化剂类型、溶剂种类、反应机理及催化剂循环使用性等方面介绍了国内外的主要研究进展,着重阐述了木质素催化氢解方法。最后总结了当前木质素催化解聚过程中存在的难题,并对未来的技术发展提出了建议和展望。     

A direct synthesis of adsorbable hydrochar by hydrothermal conversion of lignin

Hydrothermal conversion of lignosulfonate with or without formaldehyde as polymerization agent was conducted at 320°C. Compared with the hydrochar produced without formaldehyde addition (WF-hydrochar), the yield and surface area of the hydrochar produced with formaldehyde addition (F-hydrochar) increased 33.8 and 46.4%, respectively. The F-hydrochar showed much higher adsorption ability of Cu²⁺ than that of WF-hydrochar, while its adsorption ability of methyl orange was a little lower than that of WF-hydrochar. These discoveries explored a high yield of hydrochar production and a potential new application of hydrochar.     

木质素/LDPE-EVA共混材料的力学性能及热性能

以天然热塑材料木质素和LDPE-EVA为原料,研究了不同木质素以及增容剂含量对木质素/LDPE-EVA共混材料的力学及热性能影响。结果表明,20份木质素与LDPE-EVA共混效果较好,拉伸强度达到最大（25.88 MPa）,较LDPE-EVA聚合物提高了9%,且共混物在100 ℃附近的吸热峰出现一定左移（3.6 ℃）,降解性能增加;10份增容剂LDPE-g-MAH的加入使体系拉伸强度达到35.66 MPa,较未加增容剂时提高了26.6%,100℃附近的吸热峰进一步左移（2 ℃）,降解性能小幅降低,显著提高了共混物的相容性。     

Thermogravimetric analysis as a new method to determine the lignocellulosic composition of biomass

Biomass energy uses organic matter such as wood or plants - lignocellulosic biomass - for creating heat, generating electricity and producing green oil for cars. Modern biomass energy recycles organic leftovers from forestry and agriculture, like corn stovers, rice husks, wood waste and pressed sugar cane, or uses special, fast-growing “energy crops” like willow and switchgrass, as fuel. Biomass is composed of three major components: cellulose, hemicelluloses, and lignin. Their differences in chemical structures lead to different chemical reactivities, making the relative composition in cellulose, hemicelluloses and lignin in the biomass a crucial factor for process design. In this paper thermogravimetric analysis is investigated as a new method to obtain lignin, hemicellulose and ??-cellulose contents in biomass. It is shown that this alternative method lead to comparable results than common methods used for the determination of the ??-cellulose content, with an enhancement of the accuracy in the determination of the hemicellulose content. Unfortunately, this method cannot be adopted for the determination of the lignin amount.     

碱预处理糠醛渣性质及其纤维素酶解研究

以糠醛渣为原料进行碱法预处理,对比了处理前后的样品成分、结晶度、表面特性、红外谱图的变化以及对纤维素酶解的影响。研究结果表明:经NaOH处理样品,木质素脱除量随着温度升高而增加,120 ℃ 处理后的样品木质素脱除了 10.22 %,而碱性过氧化氢处理样品木质素脱除率达到 12.6 %。NaOH预处理后的样品酶解糖化率随处理温度的升高而降低。每克纤维素加入纤维素酶 12 FPU、纤维二糖酶 15 IU,120 ℃ 经NaOH预处理样品,酶解 72 h 后糖化率为38.6%,比原料糠醛渣低21.0个百分点,而经 60 ℃,6 h 碱性过氧化氢处理后的样品,酶解 72 h 糖化率可达到 86.6 %,比原料糠醛渣高27.0个百分点。NaOH预处理后样品红外谱图检测,证明生成了新的醚键。碱法预处理后的样品结晶度要比未处理的样品的稍高,且表面更加光滑。