Catalytic conversion of guaiacol to alcohols for bio-oil upgrading

Guaiacol was chosen to represent O-containing chemicals with lower effective hydrogen carbon ratio(H/Ceff factor) in bio-oil,and the hydrodeoxygenation of guaiacol was investigated over non-precious and nonsulfided catalysts. Effects of metal composition,reaction temperature,and hydrogen pressure on conversion and selectivity were investigated systematically. Among various compositions of catalysts,Ni Co/CNT exhibited best performance of guaiacol conversion with higher selectivity towards desired alcohols with higher H/Cefffactor. The reaction pathways of guaiacol in aqueous were proposed based on the product analyzed.Results show that metal composition and temperature have great effects on the conversion of guaiacol and the yields of desired products.     

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.     

限域NiCo合金纳米颗粒高效催化生物质衍生物水相加氢脱氧

将储量丰富的生物质及其衍生物转化为具有高附加值的燃料和化学品被认为是一种有前景的绿色途径,可以极大地减少人们对传统化石资源的依赖.作为木质纤维素热解的直接产物和生物油升级的模型化合物,香草醛可以通过加氢脱氧(HDO)过程选择性地转化为2-甲氧基-4-甲基苯酚(MMP).MMP是一种有价值的化学品,常用于香料和药物等重要中间体的合成.在过去十年里,大量的金属催化剂被用来催化香草醛HDO转化为MMP.其中,贵金属(Pt,Pd,Ru和Au)虽然活性高,但是其储量低、价格昂贵,不利于工业化应用;而非贵金属(Fe,Co,Ni和Cu)的催化活性普遍较低,需要苛刻的反应条件来提高转化效率和选择性.此外,这类HDO反应大都在有机溶剂中进行,容易造成环境污染.因此,开发高效、稳定的非贵金属催化剂用于水相HDO反应是一个巨大的挑战.一般来说,合金纳米颗粒(NPs)具有强烈的协同效应,能产生良好的配位结构和电子环境,从而显著提升催化活性和选择性.基于此,本文首次采用了一种简单可控的合成方法来制备三聚氰胺海绵负载的氮掺杂碳纳米管(N-CNTs)限域的Ni-Co合金NPs(NiCo@N-CNTs/CMF)催化剂.该催化剂具有优异的HDO性能,在2 MPa H2,120oC反应6 h条件下,能在水相中将生物质衍生的香草醛高效转化为MMP,转化率和选择性均达到100％.相比于单金属的Ni@N-CNTs/CMF和Co@N-CNTs/CMF催化剂,香草醛转化率和MMP选择性都有大幅度的提高.而且,在温和的反应条件下,该催化剂对香草醛衍生物和其他芳香醛类化合物同样表现出优异的HDO性能,拥有100％的转化率以及较高的MMP选择性(91.5％～100％).XPS结果表明,Ni-Co形成合金后发生了电子结构的偏移,即Co原子可以从邻近的Ni原子处得到电子,提高Co电子云密度,从而促进对香草醛中C=O键的吸附.DFT计算结果表明,相比于单金属的Ni和Co,Ni-Co合金化后能显著提高对C=O键的选择性吸附和活化.同时,H2解离后形成的活性H*物种在Ni-Co合金NPs表面更容易脱附并参与催化反应.因此,Ni-Co@N-CNTs/CMF催化剂优异的HDO性能主要是由于Ni-Co合金NPs的协同作用大大促进了其对C=O键的选择性吸附和活化,以及活化氢物种的脱附.本文为设计和制备高效的非贵金属催化剂应用于水相的HDO反应提供了一个新策略.     

Controlled depolymerization of lignin in an electrochemical membrane reactor

The electrochemical oxidative cleavage of lignin is a promising approach to valorize lignin's monomeric subunits as bulk and fine chemicals. It is attractive since it does not require toxic solvents or expensive catalysts. However, due to the rather unselective nature of the electrochemical depolymerization, overoxidation of the generated products occurs. In order to prevent the degradation of the aromatic monomeric compounds into acids and CO₂, a selective product removal strategy from the reaction environment is necessary. We report the use of an electrochemical membrane reactor for the continuous electrochemical cleavage of lignin integrated with an in-situ nanoporous filtration process. The generated cleavage products are removed through the nanofiltration membrane from the oxidative environment and product degradation is prevented. The reaction/separation unit comprises an unprecedented electrode configuration: electrode rods integrated into a 3D-printed turbulence-promoting mixer minimizing fouling and polarization phenomena at membrane and electrodes.     

New methods of heterogeneous catalysis for lignocellulosic biomass conversion to chemicals

This review deals with the use of solid catalysts for the enhancement of the efficiency and the development of a new generation of environmentally friendly, energy and resource efficient processes for the deep processing of lignocellulosic biomass to desired chemicals. The oxidative delignification of wood with hydrogen peroxide in the presence of the suspended TiO₂ catalyst, the oxidation of wood with molecular oxygen in the presence of copper catalysts, the acidcatalyzed conversion of cellulose to glucose and levulinic acid, and the thermal conversion of lignin to fuel additives on solid acid catalysts are analyzed. New integrated processes based on the heterogeneous catalytic oxidation are suitable for the complex processing of lignocellulosic biomass to produce valuable chemicals and engine fuel components without the use of toxic and corrosion-active reagents.     

Hydrodeoxygenation of Oxygen-Containing Aromatic Plastic Wastes to Liquid Organic Hydrogen Carriers

To address the global plastic pollution issues and the challenges of hydrogen storage and transportation, we report a system, based on the hydrodeoxygenation (HDO) of oxygen-containing aromatic plastic wastes, from which organic hydrogen carriers (LOHCs) can be derived. We developed a catalytic system comprised of Ru-ReO_x/SiO₂+HZSM-5 for direct HDO of polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene oxide (PPO), and their mixtures, to cycloalkanes as LOHCs, with high yields up to 99 %, under mild reaction conditions. The theoretical hydrogen storage capacity reaches ca. 5.74 wt%. The reaction pathway involves depolymerization of PC into C₁₅ aromatics and C₁₅ monophenols by direct hydrogenolysis of the C−O bond between the benzene ring and ester group, and subsequent parallel hydrogenation of C₁₅ aromatics and HDO of C₁₅ monophenols. HDO of cyclic alcohol is the rate-determining step. The active site is Ru metallic nanoparticles with partially covered ReO_x species. The excellent performance is attributed to the synergetic effect of oxophilic ReO_x species and Ru metallic sites for C−O hydrogenolysis and hydrogenation, and the promotion effect of HZSM-5 for dehydration of cyclic alcohol. The highly efficient and stable dehydrogenation of cycloalkanes over Pt/γ-Al₂O₃ confirms that HDO products can act as LOHCs.     

Fast screening of Depolymerized Lignin Samples Through 2D-Liquid Chromatography Mapping

Lignin valorization and particularly its depolymerization into bio-aromatics, has emerged as an important research topic within green chemistry. However, screening of catalysts and reaction conditions within this field is strongly constrained by the lack of analytical techniques that allow for fast and detailed mapping of the product pools. This analytical gap results from the inherent product pool complexity and the focus of the state-of-the-art on monomers and dimers, overlooking the larger oligomers. In this work, this gap is bridged through the development of a quasi-orthogonal GPC-HPLC-UV/VIS method that is able to separate the bio-aromatics according to molecular weight (hydrodynamic volume) and polarity. The method is evaluated using model compounds and real lignin depolymerization samples. The resulting color plots provide a powerful graphical tool to rapidly assess differences in reaction selectivity towards monomers and dimers as well as to identify differences in the oligomers.     

Catalytic Platinum Nanoparticles Decorated with Subnanometer Molybdenum Clusters for Biomass Processing

The development of improved technologies for biomass processing into transportation fuels and industrial chemicals is hindered due to a lack of efficient catalysts for selective oxygen removal. Here we report that platinum nanoparticles decorated with subnanometer molybdenum clusters can efficiently catalyze hydrodeoxygenation of acetic acid, which serves as a model biomass compound. In contrast with monometallic Mo catalysts that are inactive and monometallic Pt catalysts that have low activities and selectivities, bimetallic Pt–Mo catalysts exhibit synergistic effects with high activities and selectivities. The maximum activity occurs at a Pt to Mo molar ratio of three. Although Mo atoms themselves are catalytically inactive, they serve as preferential binding anchors for oxygen atoms while a catalytic transformation proceeds on neighboring surface Pt atoms. Beyond biomass processing, Pt–Mo nanoparticles are promising catalysts for a wide variety of reactions that require a transformation of molecules with an oxygen atom and, more broadly, in other fields of science and technology that require tuning of surface–oxygen interactions.     

快速热解炭负载Cu-Zn对碱木质素热裂解生成单酚类化合物的催化性能

以具备丰富中孔和大孔结构的快速热解炭(FPC)为载体,采用共浸渍法制备了不同Cu/Zn摩尔比的CuxZny/FPC负载型催化剂.采用X射线衍射仪(XRD)、高分辨场发射扫描电子显微镜(FE-SEM)及电子能谱仪(EDX)对催化剂进行了表征,采用热重分析仪(TG)和热解气质联用仪(Py-GC/MS)评价了催化剂对碱木质素热裂解生成单酚类化合物的催化性能.结果表明,催化剂活性组分Cu O和Zn O晶相结构均一,很好地嵌入到FPC中孔和大孔结构中,未发生聚集状态或生成Cu Zn合金;随着Cu或Zn金属负载量的增大,相应的Cu或Zn金属氧化物衍射峰强度逐渐增强,平均晶粒尺寸逐渐增大.热重分析结果表明,催化剂降低了碱木质素热裂解残炭率和反应活化能,提高了热裂解反应效率.热解气质联用分析表明,CuxZny/FPC催化剂大幅度简化了碱木质素热裂解单酚类化合物种类(从23种减少到了10种),Cu0.67Zn0.33/FPC对单酚类化合物表现出最大的选择性(52.99%),与Cu/FPC相比选择性增加49.7%.     

Oxidative cracking of precipitated hardwood lignin by hydrogen peroxide

Precipitated hardwood lignin (PHL) is a major byproduct in the biomassto-ethanol process. Oxidativecracking of PHL by hydrogen peroxide in aqueous medium was investigated as a means to produce potentially useful chemicals. The cracking reaction takes place at moderate temperatures (80–160°C), giving mono-and dicarboxylic acids as the main products. The yields of these products are in the range of 30–50% of initial lignin. The reaction mechanism and the product distribution are dependent upon the reaction conditions, especially the pH. The reaction under strong alkaline condition proceeds well even at low reaction temperatures (80–90°C). Under acidic conditions, higher temperatures (130–160°C) are required to attain the same degrees of cracking. The reaction patterns of the oxidative cracking reaction involve the cleavage of lignin ring, aryl ether bond, or other linkages within lignin. By using the findings of this investigation and those of previous work, we have illustrated the reaction pathways for degradation of PHL under alkaline and acidic conditions. Aldehydes and aromatic acids are interm ediate products in the oxidative degradation of lignin. However, they were produced only in trace amounts owing to rapid degradation induced by hydrogen peroxide. Presented at the 21st Symposium on Biotechnology for Fuels and Chemicals, Fort Collins, CO, May 1999.     

Catalytic Conversion of Macroalgae-derived Alginate to Useful Chemicals

Alginate, a main carbohydrate compound of macroalgae, can be hydrothermally converted to valuable organic products, such as furfural and organic acids, over various types of catalysts. In this review, alginate is evaluated as a renewable biomass feedstock for the production of the useful chemicals, based on the structural differences between alginate and conventional lignocellulosic biomass feedstocks. The influence of different catalysts and reaction conditions on the alginate depolymerization and the product distribution is discussed. Finally, future research direction for the catalytic conversion of alginate is suggested.     

Ru/Co-Al-O负载型催化剂的制备及其加氢脱氧性能研究

先采用共沉淀法制备出Co-Al类水滑石,其经煅烧后形成的复合氧化物用作载体制备出一系列Ru/Co-Al-O负载型催化剂,并采用XRD、BET、FT-IR等方法对其结构性能进行表征分析,最后以木质素生物质油的典型含氧化合物对甲基苯酚为模型,测试所制催化剂的加氢脱氧性能。主要研究了载体中Co/Al物质的量比、催化剂还原温度等因素对催化剂加氢脱氧活性的影响,并优化了HDO反应温度。结果表明,当Co/Al物质的量比为3∶1,催化剂还原温度为350℃,反应温度为275℃时,催化剂的加氢脱氧活性最高,催化对甲基苯酚加氢脱氧反应的转化率和脱氧率都达到了100%。     

Lignin-Derived Syringol and Acetosyringone from Palm Bunch Using Heterogeneous Oxidative Depolymerization over Mixed Metal Oxide Catalysts under Microwave Heating

Biomass valorization to building block chemicals in food and pharmaceutical industries has tremendously gained attention. To produce monophenolic compounds from palm empty fruit bunch (EFB), EFB was subjected to alkaline hydrothermal extraction using NaOH or K₂CO₃ as a promotor. Subsequently, EFB-derived lignin was subjected to an oxidative depolymerization using Cu(II) and Fe(III) mixed metal oxides catalyst supported on γ-Al₂O₃ or SiO₂ as the catalyst in the presence of hydrogen peroxide. The highest percentage of total phenolic compounds of 63.87 wt% was obtained from microwave-induced oxidative degradation of K₂CO₃ extracted lignin catalyzed by Cu-Fe/SiO₂ catalyst. Main products from the aforementioned condition included 27.29 wt% of 2,4-di-tert-butylphenol, 19.21 wt% of syringol, 9.36 wt% of acetosyringone, 3.69 wt% of acetovanillone, 2.16 wt% of syringaldehyde, and 2.16 wt% of vanillin. Although the total phenolic compound from Cu-Fe/Al₂O₃ catalyst was lower (49.52 wt%) compared with that from Cu-Fe/SiO₂ catalyst (63.87 wt%), Cu-Fe/Al₂O₃ catalyst provided the greater selectivity of main two value-added products, syringol and acetosyrigone, at 54.64% and 23.65%, respectively (78.29% total selectivity of two products) from the NaOH extracted lignin. The findings suggested a promising method for syringol and acetosyringone production from the oxidative heterogeneous lignin depolymerization under low power intensity microwave heating within a short reaction time of 30 min.     

Production of Benzene from Lignin through Current Enhanced Catalytic Conversion

The directional production of benzene is achieved by the current-enhanced catalytic conversion of lignin. The synergistic effect between catalyst and current promotes the depolymerization of lignin and the selective recombinant of the functional groups in the aromatic monomers. A high benzene yield of 175 g_benzene/kg_lignin was obtained with an excellent selectivity of 92.9 C-mol%. The process potentially provides a promising route for the production of basic petrochemical materials or high value-added chemicals using renewable biomass.     

催化一步转化木质素单体为苯酚:建立木质素到高附加值化学品的通道（英文）

木质素是地球上产量最大的芳香类有机高分子,其有效转化利用在近年来备受关注.催化降解木质素制备酚类单体在过去十年取得了长足进步,目前已开发出氢解、水解、热解、氧化、光解等一系列方法.通过加氢脱氧法可以将木质素的降解产物转化为烃类燃料,但该过程耗氢量大,并且芳香环在加氢气氛下被破坏.另一个可能的应用是将木质素衍生物进一步转化为高附加值的芳香族化合物,但解聚产物成分复杂,成为木质素高效转化为单一高附加值化学品的瓶颈.在加氢条件下,木质素解聚产物主要为酚类混合物,多在羟基临位带有一至两个甲氧基,并在对位带有C2或C3的取代基(多为烷基).针对这一结构特点,我们设计了新反应路径,通过分别去除甲氧基和烷基得到苯酚.该过程保留了苯酚的基本结构而将其他取代基去除,原理上可以有效的将木质素降解的混合物转化为单一产物苯酚.通过催化剂的筛选和优化,Pt/C催化剂对脱甲氧基显示出最好的活性和选择性,在400°C,常压下脱除效率80%.在流动气氛下连续工作4 h,Pt/C催化剂无失活迹象.H-ZSM-5为最有效的脱烷基催化剂,最优效率83%左右.H-ZSM-5在反应过程中逐渐失活.通过热重差热及红外光谱分析,失活主要原因为积碳.在400°C空气中煅烧后,催化剂可以再生.通过简单的物理混合,Pt/C和H-ZSM-5一步将木质素单体转化为60%的苯酚,显示了该方法直接转化木质素到高附加值苯酚的巨大潜力.这是同时将木质素中甲氧基、烷基选择性脱除的首例报道.经过估算,从原生木质素出发,通过加氢解聚,耦合本文开发的一步脱甲氧基、烷基路径,可将木质素转化为约25%的苯酚.木质素中的甲氧基、烷基将分别转化为甲醇和烯烃,提高了木质素碳资源的利用效率.     

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.     

木质素降解模型化合物愈创木酚及苯酚原位加氢制备环己醇

以Raney Ni为催化剂,研究了甲醇水相重整制氢与木质素降解模型化合物愈创木酚／苯酚加氢的耦合反应.考察了反应前冷压、反应温度、反应时间、物料配比等条件对木质素降解模型化合物原位加氢反应性能的影响,并对影响机制进行了讨论.结果表明,在反应温度为220 ℃、反应前冷压0 MPa(表压)、物料比水／甲醇／模型化合物为20∶5∶0.8的条件下,反应7 h后愈创木酚转化率与环己醇选择性分别达99.00％和93.74％,反应12 h后苯酚的转化率与环己醇选择性分别达90.50％和99.29％.采用原位加氢反应,木质素降解的酚类模型化合物转化率和选择性明显优于外部供氢反应的转化率和选择性,同时,避免了外部供氢反应存在的氢气制备、储存、传输及加氢条件苛刻等问题,为木质素解聚产物制备化工品提供了新思路与实验基础.     

Synthesis of Cyclopentadiene and Methylcyclopentadiene with Xylose or Extracted Hemicellulose

Cyclopentadiene (CPD) and methylcyclopentadiene (MCPD) are important intermediates that have been widely used in the production of high-energy-density rocket fuels, polymers and valuable chemicals. Currently, CPD and MCPD are produced from fossil energies at very low yields, which greatly limits their application. As a solution to this problem, we disclose an alternative two-step bio-route to access CPD and MCPD using xylose or extracted hemicellulose as the feedstock. In the first step, cyclopentanone (CPO) was directly produced by the selective hydrogenolysis of xylose or extracted hemicellulose over a commercial Ru/C catalyst in an acid-free toluene/NaCl aqueous solution biphasic system. In the second step, CPO was selectively converted to CPD by a cascade hydrodeoxygenation/dehydrogenation reaction over zinc molybdate catalysts. When methanol was introduced with CPO and hydrogen, MCPD was selectively obtained by a cascade dehydrogenation/aldol condensation/selective hydrodeoxygenation reaction over zinc molybdate catalysts.     

Kinetics of thermal depolymerization of trimethylsiloxy end-blocked polydimethylsiloxane and polydimethylsiloxane-N-phenylsilazane copolymer

The thermal degradation of Me₃SiO end-blocked polydimethylsiloxane (eb-PDMS) and polydimethylsiloxane-N-phenylsilazane (eb-PDMS–NPhSz) copolymer was studied. For both polymers relative degree of polymerization (DP /DP ₀) as a function of conversion (1 – W/W₀) data were obtained. For eb-PDMS the results were consistent with a mechanism involving a rate determining random siloxane bond cleavage initiation step followed by a rapid and complete depropagation of the active fragments evolving volatile cyclic oligomers. Rate constants (k) for initiation were obtained at four temperatures from plots of DP ^?1 vs. time. An Arrhenius activation energy of approximately 80 kcal/mol was determined and is consistent with a SiOSi scission transition state. The degradation of eb-PDMS–NPhSz appears to follow the same depolymerization process evolving cyclic oligomers. Although DP /DP ₀ vs. C data suggest a random cleavage–complete depolymerization mechanism, an Arrhenius plot suggests a more complex degradation mechanism. The role of impurities as degradation catalysts is discussed.     

Recent advances of use of the supercritical carbon dioxide for the biomass pre-treatment and extraction: A mini-review

Biomass is considered as the most sustainable and renewable resource for the synthesis of value added potential platform chemicals. Various techniques are utilized to extract or to pre-treat or to isolate various value added chemicals from biomass. Pre-treatment of the biomass is a very essential aspect to enhance the biomass processing yield which is attributed to reduced lignin content/delignification, cellulose crystallinity and hemi-cellulose hydration. In search of efficient extraction and processing for biomass treatment, supercritical fluid (SCF) has been considered as the green technique to obtain the value added chemicals with higher efficiency than conventional technique. The use of the supercritical carbon dioxide (SC–CO₂) pre-treatment on biomass not only enhances glucose yield effectively but also delignify, hydrolyse hemi-cellulose component and allows extraction of various compounds from the biomass. However, very limited research articles are available for the use of SC-CO₂ for biomass processing to obtain value-added chemicals. In view of this, the present review article focus on the recent advances of applications of SC-CO₂ in (i) extraction of value added chemicals from biomass processing, (ii) biomass pre-treatment, (iii) factors affecting SC-CO₂ processing efficiency, (iv) scale-up scenario (v) challenges and opportunities in this field.