木质素催化氧化制备芳香醛研究进展

催化氧化技术是实现木质素资源化利用的有效途径之一,可将木质素转化为具有高度官能化的芳香醛(对羟基苯甲醛、香草醛、紫丁香醛等).芳香醛是合成染料、香料及药品的重要中间体,具有较大的工业应用价值.综述了国内外有关木质素在金属催化氧化、有机催化氧化、电化学催化氧化、光催化氧化和离子液体催化氧化方面制备芳香醛的最新研究进展,并...     

木质素氧化解聚制备芳香醛研究进展

木质素作为自然界最丰富的芳香族化合物资源,通过可控的氧化解聚方式得到小分子芳香醛类化合物是实现木质素高附加值利用的重要途径。芳香醛作为重要的食用及日化香料、医药中间体、大宗化学品,目前主要通过石油化工产业链生产,以木质素生产芳香醛是具有重要研究意义和应用潜力的可再生资源利用途径。本文综述了国内外有关木质素制备芳香醛的最新研究进展,包括化学氧化解聚、电化学解聚、光催化解聚和生物催化解聚;对不同方法制备芳香醛的转化率和产率进行了对比,基于不同的解聚工艺与催化体系的特点进行评述与分析,展望未来木质素生产芳香醛的研究方向,以实现木质素的高值化利用。得出多方法耦合催化是可能进一步提高木质素生产芳香醛转化率与选择性的有效策略。     

木质素氧化降解制备酚类化合物研究进展

木质素作为可再生资源被认为是最具有潜力的苯酚替代物用于制备酚醛树脂,作为制浆造纸工业副产品,木质素来源丰富且低毒,但是木质素具有三维空间网状结构,分子量大,反应活性低。到目前为止,很多方法(如热化学转化、热裂解、液化、超临界水处理、氧化、还原和水解等)用于将大分子木质素降解为小分子物质,得到的小分子物质中含有重要的化工中间体可以用来制备多种产品。本论文综述了木质素氧化降解得到酚类物质的研究现状,并展望了木质素工业化的应用前景。     

木质素氧化降解制备酚类化合物研究进展（英文）

木质素作为可再生资源被认为是最具有潜力的苯酚替代物用于制备酚醛树脂,作为制浆造纸工业副产品,木质素来源丰富且低毒,但是木质素具有三维空间网状结构,分子量大,反应活性低。到目前为止,很多方法（如热化学转化、热裂解、液化、超临界水处理、氧化、还原和水解等）用于将大分子木质素降解为小分子物质,得到的小分子物质中含有重要的化工中间体可以用来制备多种产品。本论文综述了木质素氧化降解得到酚类物质的研究现状,并展望了木质素工业化的应用前景。     

催化氧化合成芳香醛的研究进展

综述了近年来几种简单芳香醛的合成研究现状及存在的问题。催化氧化法由于具有操作简单、三废少等优点成为一种芳香醛合成的主要方法。并提出今后该方法的发展建议。     

木质素电氧化降解的研究

研究了电氧化降解过程中木质素磺酸盐的分子结构、功能团、分子量和表面活性的变化。结果表明,电氧化过程中木质素磺酸盐中的芳环被打开,-SO3H含量和表面活性降低,-COOH含量和分子量先增加后降低。     

固体超强酸催化降解木质素的研究

在固体超强酸催化下用过氧化氢氧化降解高沸醇木质素,并利用红外光谱和气相色谱―质谱联用(GC-MS)分析降解产物。结果表明,SO42-/ZrO2固体超强酸催化降解高沸醇木质素可以得到小分子产物。随着固体酸用量增加,羰基和醚键数量明显减少,降解效果较好。GC-MS分析结果显示,FeSO4促催化更有利于木质素的降解。     

微生物降解木质素的研究进展

木质纤维是地球上最丰富的可再生生物质资源,其三大成分之一的纤维素是生产生物基材料、生物燃料及生物基化学品的重要原料,但是木质素复杂的化学结构阻碍了木质纤维的应用.常规木质素的物理、化学及物理-化学等降解方法常需要高温、高压条件,并且易产生抑制物、造成高能耗和环境污染等问题.微生物介导的生物催化过程通常在温和条件下进行,...     

热降解木质素制备低分子量木质素及其结构分析

本文以碱木质素为原料,用氢氧化钠溶解、热解和酸化分离处理,得到含有大量低分子量木质素,为后续制备木质素基胶粘剂提供原料。扫描电镜、凝胶渗透色谱、红外光谱和紫外光谱测试结果表明,木质素发生了降解,产物粒径变小,数均分子量降低,木质素酚羟基含量提高,在400℃,0.5h处理后得到的降解木质素酚羟基含量最高2.07mmol/g,比原料木质素的酚羟基含量提高65.6%。本文得到的降解木质素,酚羟基含量提高,相对分子量低,为合成酚醛树脂胶粘剂过程中替代苯酚提供了理论参考。     

木质素催化氧化解聚研究进展

木质素是自然界中唯一能直接提供芳环的可再生资源。然而,受制于其分子中致密的三维网状芳环结构和复杂化学键合方式,超过98%的工业木质素在纸浆和造纸工业中被焚烧,造成极大的资源浪费。木质素氧化解聚转化为香草醛等高度官能化的单体是一个重要且有前景的手段。文章主要介绍了木质素的结构、种类和解聚方法,从催化剂以及催化转化路线方面详细介绍了目前国内外在木质素氧化解聚研究领域的最新进展。在此基础上,对近期热门的非常规活化方法进行了调研与分析。最后总结了当前木质素氧化解聚研究存在的问题,并提出了未来可能的发展方向。     

Immobilized laccase on magnetic nanoparticles for enhanced lignin model compounds degradation

As a natural aromatic polymer, lignin has great potential but limited industrial application due to its complex chemical structure. Among strategies for lignin conversion, biodegradation has attracted promising interest recently in term of efficiency, selectivity and mild condition. In order to overcome the issues of poor stability and non-reusability of enzyme in the biodegradation of lignin, this work explored a protocol of immobilized laccase on magnetic nanoparticles(MNPs) with rough surfaces for enhanced lignin model compounds degradation.Scanning electron microscope with energy dispersive spectrometer(SEM-EDS), flourier transformation infrared spectroscopy(FTIR) and thermal gravimetric analysis(TGA) were utilized to characterize the immobilization of laccase. The results showed a maximum activity recovery of 64.7% towards laccase when it was incubated with MNPs and glutaraldehyde(GA) with concentrations of 6 mg·ml~(-1) and 7.5 mg·ml~(-1) for 5 h, respectively. The immobilized laccase showed improved thermal stability and pH tolerance compared with free laccase, and remained more than 80% of its initial activity after 20 days of storage at 4 ℃. In addition, about 40% residual activity of the laccase remained after 8 times cycles. Gas chromatography–mass spectrometry(GC–MS) was utilized to characterize the products of lignin model compound degradation and activation, and the efficiency of immobilized laccase was calculated to be 1–5 times that of free laccase. It was proposed that the synergistic effect between MNPs and laccase displays an important role in the enhancement of stability and activity in lignin model compound biodegradation.     

New and efficient procedure for the oxidation of dioxybenzylic alcohols into aldehydes with Pt and Pd-based catalysts under flow reactor conditions

Selective and efficient catalysts have been developed for the oxidation benzylic alcohols into the respective commercial aldehydes with air. Catalytically active metals (Pt and Pd) retained their activity when immobilized on the modified carbon carrier. To the best of our knowledge, this is the first example of synthesis of vanillin and piperonal from vanillyl and piperonyl alcohols under flow reactor conditions. Based on our evaluation we estimate that if the catalysts retain their activity for ca. 100 h, the yield of vanillin will be over 120/1 kg of the catalyst. Furthermore, we showed that the catalysts can be regenerated via a feasible treatment with basic water followed by acetone.     

水合肼法还原芳香硝基化合物制备芳胺的技术进展

综述了水合肼法还原芳香硝基化合物制备芳胺及其衍生物的近况,讨论了影响还原反应的主要因素和工艺条件,并展望了水合肼法制备芳胺工艺的应用前景和发展方向。     

Photo-electro catalytic oxidation of aromatic alcohols on visible light-absorbing nitrogen-doped TiO2

Visible light illumination of nitrogen-doped TiO₂ brings about the selective oxidation of benzyl and cinnamyl alcohol to the corresponding aldehydes. The photocatalyst was prepared by a sol-gel method and characterised mainly by XRD, UV-vis diffuse reflectance and Raman spectroscopy. The conditions limiting the observation of visible light photoactivity are the use of dry nitriles as nonaqueous solvents and aromatic alcohols as the substrates. No visible light oxidation takes place in an aqueous medium. The efficiency of benzyl and cinnamyl alcohol photo-oxidation in nitrile solvents follows the order: CH₃CN > CH₃CH₂CN > CH₃(CH₂)₂CN. Conversely, since alcohol photo-oxidation occurs with 100% selectivity on electrodes in O₂ saturated solutions at potentials close to E_fb or under open-circuit conditions, suspensions of the photocatalyst can be advantageously employed. The process involves a relatively weak adsorption of the alcohol substrates which, however, do not readily capture the photogenerated holes. On the basis of the electrochemical and photoluminescence data, it appears that the solvent (e.g. acetonitrile), in addition to O₂ has an active role in the reaction mechanism.     

Improvement of the oxidation stability of biodiesel as prepared by supercritical methanol method with lignin

An antioxidation effect of lignin‐derived products in biodiesel prepared using supercritical methanol (300°C/20 MPa) with molar ratio between rapeseed oil and methanol of 1:42 was studied. It was found that lignin could be decomposed to low molecular compounds that have a free radical‐trapping effect after supercritical methanol treatment. However, longer treatment time decreased the antioxidation effect of the lignin‐derived compounds. Rapeseed biodiesel prepared by supercritical methanol method at 300°C/20 MPa for 20 min with a small amount of added lignin showed an induction period longer than 6 h at 110°C in a Rancimat test. In addition, it was found that lignin had a catalytic effect in biodiesel production using the supercritical methanol method without significantly affecting other fuel properties of the prepared biodiesel. Thus, the study proved that lignin addition provides an inexpensive and technically acceptable way to improve the oxidation stability of biodiesel prepared by the supercritical methanol method with satisfactory fuel properties.     

Decolorization and aromatic ring degradation of colored textile wastewater using indirect electrochemical oxidation method

In this research, decolorization and aromatic ring degradation of colored textile wastewater was investigated by indirect electrochemical process in a batch reactor. The graphite and sodium chloride were used as electrode and supporting electrolyte, respectively. Reactive Yellow 3 (RY3) was used as model compound. The effects of influential variables governing the efficiency of the process such as initial dye concentration, pH, current density, and electrolyte concentration were studied. The decrease of absorbance at UV region in UV-Vis spectra was indicative of the aromatic ring degradation. Kinetic analysis indicates that the electrochemical decolorization rates might be obeyed as a first order model. The UV-Vis data supported the decolorization and degradation of aromatic intermediates of RY3.     

Study on the catalytic degradation of sodium lignosulfonate to aromatic aldehydes over nano-CuO: Process optimization and reaction kinetics

As one of the few renewable aromatic resources, the research of depolymerization of lignin into high-value chemicals has attracted extensive attention in recent years. Catalytic wet aerobic oxidation (CWAO) is an effective technology to convert lignin like sodium lignosulfonate (SL), a lignin derivative, into aromatic aldehydes such as vanillin and syringaldehyde. However, how to improve the yield of aromatic aldehyde and conversion efficiency is still a challenge, and many operating conditions that significantly affect the yield of these aromatic compounds have rarely been investigated systematically. In this work, we adopted the stirred tank reactor (STR) for the CWAO process with nano-CuO as catalyst to achieve the conversion of SL into vanillin and syringaldehyde. The effect of operating conditions including reaction time, oxygen partial pressure, reaction temperature, SL concentration, rotational speed, catalyst amount, and NaOH concentration on the yield of single phenolic compound was systematically investigated. The results revealed that all these operating conditions exhibit a significant effect on the aromatic aldehyde yield. Therefore, they should be regulated in an optimal value to obtain high yield of these aldehydes. More importantly, the reaction kinetics of the lignin oxidation was explored. This work could provide basic data for the optimization and design of industrial operation of lignin oxidation.     

甲苯的复合氧化反应动力学及其降解的研究

在停止流动光谱仪反应器中研究了污水中的甲苯在3种氧化剂H2O2、O3和O3/H2O2、温度298K及pH=3~11时的氧化反应动力学及其降解过程。实验结果表明,甲苯在H2O2中氧化速率很慢,在O3中的氧化速率较快,当两种强氧化剂H2O2与O3耦合,构成高级氧化过程(AOP),甲苯的氧化速率最快。随着pH值增加,甲苯在O3和O3/H2O2中的氧化速率进一步加快。通过理论分析,初步探讨了有机污染物降解过程的机理;通过对实验数据的回归分析,获得了反应动力学常数。     

Preparation and characterization of nanoscale aromatic polyamide particles

Aromatic polyamide particles were prepared by reacting m-phthalyl chloride and 4,4′-diaminodiphenyl ether in a dioxane solution with high water content using a precipitation polymerization method. These nanoscale particles were spherical with a narrow size distribution. The morphologies and characteristic features of the polyamide products obtained depended strongly on the water content of this polymerization system. The characteristic features of the polyamide products were correlated with the amount of HCl (generated during polycondensation) complexed with polyamide products. Water was essential for the formation of spherical particles and played an important role in determining the polarity of the reaction solution. Further, water removed HCl from this condensation reaction system and played an important role as a reaction accelerator.