电催化木质素升级转化成高附加值化学品和燃料的研究进展

为节能减排和能源结构调整以快速实现"碳中和",发展可再生、清洁与绿色的能源以替代传统化石能源已成为当今世界高质量发展的重要共识.生物质能作为一种典型的可再生能源,具有储量丰富、分布广泛、可有效转化成各种化工原料和燃料等特点逐步受到广泛关注并成为科研热点.木质素是生物质的重要组成部分,其含氧量低、热值高,可转化成高热值燃料;同时,木质素富含芳香结构单元,可以转化成各类高附加值化工原料及医药中间体.木质素解聚及其对应单体升级转化是木质素高效转化利用的关键技术.当前,传统热催化是其主要应用技术手段.然而,该类方法常在高温高压下进行,需消耗大量能源及众多繁琐操作步骤,不易规模化生产.相对而言,电催化技术能实现常温常压的木质素解聚及对应单体的升级转化,采用由可再生能源(例如风能、太阳能等)获得的清洁电力,则能实现完全绿色可持续生产,对未来经济社会的发展及"碳中和"的目标具有重大意义.本文综述了近年来电催化技术在木质素升级转化成高附加值燃料和化学品方面的应用,尤其是在木质素解聚及其对应单体于水溶液相关电解质中升级转化方面的应用.(1)针对总体研究背景进行了概述,总结了木质素研究的重要意义并概括了当前木质素研究的主要思路,并简单介绍了木质素结构单元及连接键等基本性质;(2)针对电催化技术在木质素应用方面进行了总结,包括反应类型和反应路径等;(3)总结了木质素常用的几种典型表征技术手段,如GC-MS、NMR、IR等;(4)总结了电催化木质素解聚及其单体升级转化研究现状,对电催化木质素解聚应用中木质素前体类型、电解质种类和电还原/氧化催化剂进行了详细介绍及客观评价,并对几种代表性单体的电催化加氢反应及氧化反应做了详细评述.在此基础上展望了电催化技术在木质素升级转化中的应用前景,指出了当前电催化技术在木质素升级转化应用中存在的实际问题,提出了电催化技术在木质素升级转化中的发展方向.     

Structure and Action Mechanism of Ligninolytic Enzymes

Lignin is the most abundant renewable source of aromatic polymer in nature, and its decomposition is indispensable for carbon recycling. It is chemically recalcitrant to breakdown by most organisms because of the complex, heterogeneous structure. The white-rot fungi produce an array of extracellular oxidative enzymes that synergistically and efficiently degrade lignin. The major groups of ligninolytic enzymes include lignin peroxidases, manganese peroxidases, versatile peroxidases, and laccases. The peroxidases are heme-containing enzymes with catalytic cycles that involve the activation by H₂O₂ and substrate reduction of compound I and compound II intermediates. Lignin peroxidases have the unique ability to catalyze oxidative cleavage of C–C bonds and ether (C–O–C) bonds in non-phenolic aromatic substrates of high redox potential. Manganese peroxidases oxidize Mn(II) to Mn(III), which facilitates the degradation of phenolic compounds or, in turn, oxidizes a second mediator for the breakdown of non-phenolic compounds. Versatile peroxidases are hybrids of lignin peroxidase and manganese peroxidase with a bifunctional characteristic. Laccases are multi-copper-containing proteins that catalyze the oxidation of phenolic substrates with concomitant reduction of molecular oxygen to water. This review covers the chemical nature of lignin substrates and focuses on the biochemical properties, molecular structures, reaction mechanisms, and related structures/functions of these enzymes. Reference to a company and/or products is only for purposes of information and does not imply approval of recommendation of the product to the exclusion of others that may also be suitable. All programs and services of the US Department of Agriculture are offered on a nondiscriminatory basis without regard to race, color, national origin, religion, sex, age, marital status, or handicap.     

木质素在高分子材料中的应用

本文简要介绍了木质素的结构及其在衙种高分子材料的应用和开发前景。     

Capillary electrophoretic determination of lignin degradation products obtained by permanganate oxidation

A new capillary electrophoretic (CE) technique was developed for the separation of lignin degradation products after permanganate oxidation, yielding information about quality and quantity of various linkages in the lignin molecule. This CE method is a promising alternative to existing gas chromatographic (GC) methods. An advantage in comparison with GC is the short separation time and the fact that the oxidation products (aromatic acids) can be analyzed without derivatization. The selectivity and sensitivity of CE combined with UV detection is adequate and makes it suited for fast routine characterization of lignins. If necessary, the CE method can be coupled with electrospray ionization mass spectrometry in order to make a clear assignment of the peaks.     

Determination of soluble lignin and proteins in the presence of each other

Several methods for the differential determination of lignin and of proteins solubilized together in the same solution are compared. It is shown that lignin is best determined by spectrophotometry at 280 nm, the absorptivity of the polymer being an order of magnitude greater than those of proteins. In contrast, a turbidimetric method applied to acid-precipitated lignin is strongly influenced by both the nature and the amounts of the proteins present in the mixture. Ninhydrin reagents permits the determination of proteins without interference from soluble lignin. Phenol and Coomassie Blue reagents react strongly with lignin, thus masking their interaction with proteins. The soluble lignin preparations used were solubilized from stake lignin in buffers adjusted to different pH values. They were analysed by exclusion chromatography and the results suggest that the lignin fragments obtained at higher pH are larger than those solubilized at lower pH. Turbidimetry showed that these larger soluble fragments form larger aggregates after acid precipitation.     

钛酸酯偶联剂的结构对PVC/木质素复合材料性能的影响

本文采用钛酸酯系列偶联剂对造纸工业废渣──木质素磺酸盐进行处理，然后填充聚氯乙烯（PVC）制成复合材料．结果发现用钛酸酯类偶联剂处理的木质素磺酸盐，填充PVC体系，其拉伸强度随使用钛酸酯偶联剂不同，拉伸强度下降幅度不同，而冲击强度和伸长率都不同程度上升，尤以冲击强度的提高最为明显．     

PREPARATION AND PROPERTIES OF CHITOSAN/LIGNIN COMPOSITE FILMS

Biodegradable composite films based on chitosan and lignin with various composition were prepared via the solution-casting technique.FT-IR results indicate the existence of hydrogen bonding between chitosan and lignin,and SEM images show that lignin could be well dispersed in chitosan when the content of lignin is below 20 wt%due to the strong interfacial interaction.As a result of strong interaction and good dispersion,the tensile strength,storage modulus,thermal degradation temperature and glass transi...     

木质素模型化合物的裂解工艺及机理的研究进展

化石资源的有限性、不可再生性及其利用所造成的环境污染,使木质生物质资源生产高附加值化学品和燃料受到广泛关注。因木质素是结构复杂的高分子聚合物,其综合有效利用受到极大限制,通常被作为燃料直接燃烧,同时给木质素解聚研究带来了巨大的困难。因此,围绕木质素模型化合物裂解工艺及机理的研究发展迅速。为梳理木质素模型化合物的裂解研究的现状和预测未来发展方向,本文综述了其裂解工艺和机理的研究进展。着重介绍木质素单体、二聚体和多聚体不同裂解工艺的特点、优势、应用前景以及相关的机理,最后预测了木质素模型化合物裂解研究未来的发展方向。     

Synthesis ofa trimeric lignin model compound composed ofol-O-4 and β-O-4 linkages under microwave irradiation

A trimeric lignin model compound composed of α-O-4 and β-O-4 linkages was prepared by the microwave-assisted synthesis, which consisted of three steps： （a） the synthesis of 3-methoxy-4- benzyloxyacetophenone （2） from acetovanillone （1）, （b） the bromination of compound 2 to produce 3- methoxy-4-benzyloxy-α-bromoacetophenone （3）, and （c） followed by a nucleophilic substitution of compound （3） to obtain 3-methoxy-4-benzyloxy-α-（3-methoxy-4-（1-propenyl）phenol）-acetophenone （4）. The target product was characterized by MS, 1H NMR and 13C NMR spectroscopy. It was found that the trimeric compound synthesized can be used as a preferable lignin model compound because it contains guaiacyl structural unit （3-methoxy-4-hydroxy phenyl propane） linked by α-O-4 and β-O-4 linkages. In addition, under the conditions of microwave irradiation, the reaction time of each step is significantly reduced, and the selectivity of target product is greatly improved. The yields of each step and the overall sequence are 95.31%. 87.3%. 90.6% and 75.4% （95.31%× 87.3% × 90.6%）. respectively.     

木质素对酚醛/木质素嵌段共聚树脂制备的影响及反应机理

以工业木糖生产残渣为原料, 用不同条件下碱提取得到的碱木质素液与苯酚和甲醛原位反应制备酚醛/木质素嵌段共聚树脂. 以所制备树脂中甲醛释放量最小为原则, 得到木质素的最佳提取条件: 碱浓度5%(质量分数), 固液体积比1:12, 反应时间3 h. 在此条件下树脂中甲醛释放量为0.115%, 相应的胶合强度为1.197 MPa, 均远优于GB/T14074-2006中对于一类胶合板用酚醛胶的要求(甲醛释放量≤0.3%, 胶合强度≥0.7 MPa). 实验结果表明, 碱木质素液能参与到反应中, 提高酚醛/木质素嵌段共聚树脂的热稳定性及胶合强度, 降低甲醛释放量, 有利于树脂的储存及应用. 同时讨论了碱木质素与苯酚和甲醛的可能反应机理.     

由木质素制备高品位运输燃料初探

木质素是一种绿色可再生的资源,是制备液体运输燃料的理想原料。本文研究了一种由木质素制备液体运输燃料的方法。首先,选用K-OMS-2催化剂进行氧化反应,通过氧化木质素单体模型物获得芳香醛,木质素二聚体模型物(α-O-4结构木质素二聚体)氧化解聚后获得了65%产率的芳香醛;同时尝试氧化碱木素,产物中检测到香草醛、对羟基苯甲醛等化合物;其次,通过芳香醛和丙酮发生Claisen-Schmidt缩合反应增加碳链长度;最后,通过芳烃加氢获得高品位的饱和烷烃燃料。     

Production of oxychemicals from precipitated hardwood lignin

Lignin is a major byproduct in the biomass-to-ethanol process. The lignin produced from acid treatment of biomass has characteristics suitable for further conversion to organic chemicals. It is free of contaminants and has a relatively low molecular weight. In this study, catalytic oxidative conversion of the acid-soluble lignin precipitated from acid hydrolysates of hardwood was investigated. The process is based on aqueous alkaline oxidation of lignin with dissolved O₂ in the presence of Fe³⁺ and Cu²⁺ catalysts at moderate reaction temperatures (160–180°C). Aromatic aldehydes, ketones, and organic acids are found to be the primary products identifiable on extraction with ether. The combined weight yield of the total ether extractable products is about 20–25% of the initial lignin. The yield of the aldehydes (vanillin + syringaldehyde) is in the vicinity of 15% with an additional 3 to 4% of aromatic ketones. The yields of aldehydes plus ketones observed in this work far exceeded those obtainable from the conventional alkaline air oxidation of spent sulfite liquors. This article also provides comprehensive batch reaction data on conversion and product distribution.     

微波辅助高效降解木质素转化酚类化合物的研究进展

木质素作为自然界中丰富的可再生芳香族聚合物,可用于生产高附价值的酚类化合物,木质素降解已引起了各界越来越广泛的兴趣,为了高效降解木质素以获得酚类化合物更高得率,各种技术被广泛运用在木质素降解的研究中,其中微波辅助高效降解技术因更具优势而备受关注,微波降解木质素具有环境友好、高效快速、节能省电、易控制、安全、选择性强等特点。为了解微波辅助高效降解木质素转化酚类化合物的现状,并预测未来发展方向,本文在综述其研究进展的基础上,着重回顾了微波辅助高效降解技术的机理、特点及优势,考察了微波辅助条件下不同催化剂高效降解木质素的效果,介绍了微波辅助高效降解与其他物质偶联降解木质素的方法以及效果,同时综述了降解产物的分离检测方法、特点以及优势与应用前景,最后以此为依据,展望微波辅助高效降解木质素转化绿色化学品研究的未来发展方向。     

Preparation and Characterization of a Lignin Modified Electrode

Alkali lignin undergoes strong adsorption on polycrystalline gold electrodes. Subsequent oxidation in a sulfuric acid solution leads to a restructured redox‐active polymer that shows features characteristic for surface confined species. Surface coverage of up to 4.40×10^?10 mol cm^?2 may be obtained depending on the adsorption time or lignin concentration in the adsorption solution. Using Laviron's approach the electron‐transfer rate constant and the transfer coefficient were found to be 8.9 s^?1 and 0.35, respectively. The formal potential of the redox couple shifted negatively with pH at a rate of ca. 60 mV/pH unit, suggesting a 2 e/2 H⁺ reaction. The redox couple was also found to be a good mediator for electrochemical ascorbic acid oxidation in neutral phosphate buffer with ca. 250 mV reduction of the oxidation overpotential.     

木质素基环氧丙烯酸酯的合成及紫外光固化

正木质素是地球上一种储量十分丰富的可再生资源,可生物降解[1,2].木质素结构中含有大量羟基,主要以酚羟基和醇羟基形式存在,可与许多化合物发生化学反应制得木质素基环保材料,是最有前途的生物质资源之一[3].但工业木质素纯度较低,对其利用多为直接混合,如水泥减水剂等低端领域.环氧丙烯酸酯(EA)作为紫外光固化的预聚体,在紫外光照射下可快速固化,其黏接性高,耐化学药品性能优异,应用广泛[4,5].因此降低EA的成本,对其进行改性是近年来该领域的研究热点[6].本文以工     

木质素在橡胶中的应用研究进展

木质素是地球上最丰富的生物材料之一,其基本单元为9-碳苯酚丙烷(香豆醇、松柏醇和芥子醇),这些单元通过不同类型的键连接在一起形成一个多酚类芳香族聚合物。作为造纸工业的主要废弃物,木质素成本低廉,目前主要用作低附加值的燃料,其开发价值还没有得到充分利用。将木质素用于填充改性橡胶既经济又环保,其不仅有补强的效果,还有偶联、抗氧防老、阻燃的作用,可部分代替炭黑。本文将对木质素的改性、橡胶/木质素复合材料的制备方法及研究进展进行综述,并对橡胶/木质素复合材料研究的挑战和机遇进行了展望。     

Beech Lignin—Proposal of a Constitutional Scheme

The high molecular weight material lignin consists of phenylpropane units linked together by a variety of bond types. During the past eight years, two newly developed degradation procedures have permitted the first direct determinations of the nature of these bonds. The first procedure affords a very mild partial hydrolysis of benzyl ether bonds. Eleven dimeric, trimeric, and tetrameric degradation products were obtained in this way from spruce and beech lignin: they exhibited three different kinds of bonds between the C₉ structural units, and their structures have all been elucidated. In the second procedure, the most important kind of bond in lignin, i. e. the arylglycerol-β-aryl ether bond, can be subjected to directed cleavage under mild conditions after introduction of a suitable neighboring group. On application to beech lignin, 91 % of the material was degraded giving monomeric to tetrameric phenols. Complete structural elucidation of the twenty dimeric phenols isolated and a knowledge of their relative yields and the yields of the other fractions obtained by gel filtration permitted a structural scheme to be set up for beech lignin in which the C₉ structural units are linked together by no less then ten different kinds of bonds. The structural scheme, which can be readily explained biogenetically, has the same elemental composition as natural beech lignin. Further support for the structural scheme comes from a comparison of the ¹³C-NMR spectrum of natural beech lignin and a ¹³C-NMR spectrum calculated for the proposed structure on the basis of about fifty lignin model substances.     

Abrasive Stripping Voltammetric Studies of Lignin and Lignin Model Compounds

Lignin is potentially a major renewable, nonfossil source of aromatic and cyclohexyl compounds. In this study, we have investigated the abrasive stripping voltammetry of lignin and four lignin model compounds in the room temperature ionic liquids (RTILs) [C₄mim][NTf₂], [N_6,2,2,2][NTf₂] and [C₄mim][OTf] (where [C₄mim]⁺=1‐butyl‐3‐methylimidazolium, [N_6,2,2,2]⁺=n‐hexyltriethylammonium, [NTf₂]^?=bis(trifluoromethanesulfonyl)imide and [OTf]^? =trifluoromethanesulfonate) on a gold macrodisk and in 0.1 M H₂SO₄ and 0.1 M NaOH on a boron‐doped diamond (BDD) macroelectrode, with the hope of using the voltammetry to fingerprint the functional groups within the lignin molecule. The use of RTILs on metal electrodes, or either acidic or basic media in combination with BDD electrodes allows solvent systems with wide electrochemical potential windows, useful for studying voltammetry which may be difficult to observe in systems where early breakdown of the solvent occurs.     

Steric effects of bulky tethered arylpiperazines on the reactivity of Co-Schiff base oxidation catalysts—a synthetic and computational study

New C2-symmetric and C2-asymmetric Co-Schiff base catalysts tethered to arylpiperazine units were synthesized and used to oxidize phenolic lignin models to para-benzoquinones. Synthetic approaches to these catalysts were optimized to include fewer steps and broaden the types of catalyst structures available. In contrast to conventional Co-Schiff base catalysts, these systems induce phenolic oxidation in the absence of an external axial base, simplifying the process. Asymmetric catalysts bearing a phenylethylene or diphenylmethyl piperazine substituent display the highest catalytic activity observed to date for the conversion of S-models to 2,6-dimethoxybenzoquinone (DMBQ). Computational analysis shows that more reactive catalysts populate conformations that favor oxidation in preference to non-productive decomposition routes. This balance between catalyst reactivity and catalyst deactivation is optimized by inclusion of sufficient steric bulk around the periphery of the Schiff base ligand, reducing catalyst deactivation and allowing oxidations to proceed in the absence of an added axial ligand.     

低成本木质素吸附剂对废水中Pb2+吸附性能的研究

首次尝试以马尾松为原料的木质素制备低成本重金属吸附剂,采用N2物理吸附和红外漫反射技术对其结构和表面化学进行了表征,研究了pH值,温度对其吸附水溶液中Pb2 的影响,并与麦草木质素和商业活性炭进行了对比,探讨了它吸附重金属离子的吸附机理以及结构和表面化学对重金属离子吸附的影响。结果表明,马尾松木质素吸附剂对水溶液中Pb2 的吸附机理主要是化学吸附,其表面的功能基有利于吸附水溶液中Pb2 ,尽管商业活性炭的比表面积是马尾松碱木素的200多倍,在相同的实验条件下,所制备的马尾松碱木素对Pb2 的单位比表面积平衡吸附量却是商业活性炭的1000多倍。