☆ 4.8 Review

Reductive catalytic fractionation as a novel pretreatment/lignin-first approach for lignocellulosic biomass valorization: A review

BIORESOURCE TECHNOLOGY (2023)

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Reductive catalytic cracking of industrial phenolics mixture to selective cyclohexanols

Meenu Jindal et al.

Summary: Cyclohexanols can be efficiently produced from industrial phenolics through liquid-phase hydrodeoxygenation reaction. The mixture of IPA and water as the solvent is beneficial for improving the conversion and selectivity, achieving a conversion of over 99% and a selectivity of 87.4% for cyclohexanols under optimal reaction conditions.

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Article Agricultural Engineering

Valorization of lignin through reductive catalytic fractionation of fermented corn stover residues

Wen-Zheng Yin et al.

Summary: A novel strategy using a commercial Pd/C catalyst was proposed to produce monophenolic compounds from fermented corn stover. By controlling the reaction temperature, the highest monomer yield of 28.5 wt% was achieved at 220 degrees C, compared to 22.8 wt% for pristine corn stover. The enhanced monophenol yield was attributed to higher lignin content and lower recalcitrance in the fermented stover. The results demonstrated a potential avenue for the valorization of lignin through reductive catalytic fractionation of agricultural waste.

BIORESOURCE TECHNOLOGY (2023)

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Article Agricultural Engineering

Characterization of slow pyrolysis products from three different cashew wastes

Ramandeep Kaur et al.

Summary: This study aims to utilize cashew wastes generated during cashew nut processing. Slow pyrolysis of cashew skin, cashew shell, and cashew shell de-oiled cake was conducted at different temperatures. The bio-oil yield varied for different feedstocks and temperatures, with cashew shell waste having the highest yield at 500 degrees C. The bio-oil was analyzed and phenolics were found to be the predominant component. Cashew skin resulted in the highest biochar yield, while the characterization of biochar revealed its carbonaceous and amorphous nature.

BIORESOURCE TECHNOLOGY (2023)

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Article Agricultural Engineering

Effect of zeolite structure and Si/Al ratio on cotton stalks hydropyrolysis

Meenu Jindal et al.

Summary: Two different zeolites, HY and HZSM-5, with different Si/Al ratios, were used to investigate the effect of zeolite structure on aromatic hydrocarbons (AHs) production during flash hydropyrolysis of cotton stalks. Both zeolites enhanced AHs production, but the pore structure and pore size of HZSM-5 had a more pronounced effect on the reduction of oxygenated compounds. Ni/zeolite catalysts were also studied, and they promoted the conversion of phenolics and other oxygenated compounds, resulting in increased production of aromatic and aliphatic hydrocarbons through direct deoxygenation, decarbonylation, and decarboxylation reactions.

BIORESOURCE TECHNOLOGY (2023)

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Review Energy & Fuels

Lignin-First Biorefinery for Converting Lignocellulosic Biomass into Fuels and Chemicals

Zhongyang Luo et al.

Summary: Driven by concerns over excessive consumption of fossil resources and environmental pollution, researchers have focused on converting lignocellulosic biomass into fuels and chemicals through biorefinery processes. One promising strategy is lignin-first, which enables the production of high-yield and high-selectivity aromatic monomers. This review highlights recent advancements in lignin-first biorefinery, covering the processing steps from raw lignocellulose to downstream pathways for intermediate compounds. Key topics include catalytic conversion of lignin and its derivatives, as well as cascade utilization of carbohydrate residues. The review concludes with an overview of current challenges, potential solutions, and future perspectives for lignin-first biorefinery, offering insights for efficient utilization of lignocellulosic biomass.

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Promoted Production of Phenolic Monomers from Lignin-First Depolymerization of Lignocellulose over Ru Supported on Biochar by N,P-co-Doping

Tao Ding et al.

Summary: The codoping of N,P into the support of metal-supported catalysts significantly improves catalytic performance by promoting the production of phenolic monomers and increasing lignin yield, achieving full delignification during the depolymerization process.

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Lignin-First Depolymerization of Lignocellulose into Monophenols over Carbon Nanotube-Supported Ruthenium: Impact of Lignin Sources

Shihao Su et al.

Summary: Ru/CNT catalyst exhibits high selectivity and yield towards lignin hydrogenolysis. The yields of aromatic monomers are related to lignin sources and decrease in the order: hardwoods > herbaceous plants > softwoods. The scission of C-O bonds and the high selectivity to monomeric aromatic compounds over the Ru/CNT catalyst are enhanced by avoiding side condensation. The fabricated Ru/CNT shows good reusability and recyclability, applicability, and biomass feedstock compatibility.

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Multi-pass flow-through reductive catalytic fractionation

Jun Hee Jang et al.

Summary: Reductive catalytic fractionation (RCF) is an effective method for selectively extracting and depolymerizing lignin from biomass. Multi-pass flow-through RCF reduces solvent demand without compromising delignification and monomer yield.

JOULE (2022)

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Reductive Catalytic Fractionation of Lignocellulosic Biomass: A New Promissing Method for Its Complex Processing

A. Miroshnikova et al.

Summary: This article focuses on recent research in the complex processing of lignocellulosic biomass, specifically the reductive catalytic fractionation (RCF) technique. It discusses the impact of catalysts, co-catalysts, solvents, hydrogen sources, and raw materials on the selectivity in producing monomeric lignin products. The study finds that catalysts containing palladium, platinum, ruthenium, and nickel exhibit the highest activity. Bifunctional catalysts with both acidic and metallic active sites are the most efficient in RCF processes.

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Metal-Organic-Framework-Derived Copper Catalysts for the Hydrogenolysis of Lignin into Monomeric Phenols

Qiang Wang et al.

Summary: In this study, a copper-based catalyst derived from a metal-organic backbone is presented for the reductive catalytic fractionation of woody sawdust, which offers high yields of propyl and propanol end-chain monomeric phenols. The catalyst is found to effectively cleave aryl ether linkages, promoting the conversion of lignin into valuable compounds.

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Catalyst choice impacts aromatic monomer yields and selectivity in hydrogen-free reductive catalytic fractionation

Jacob K. Kenny et al.

Summary: Hydrogen-free reductive catalytic fractionation (RCF) is a promising method to extract and depolymerize lignin from native biomass. Pt/C and Pd/C achieve comparable monomer yields regardless of hydrogen pressure, while Ru/C and Ni/C show lower yields under H-2-free conditions. Pt/C and Pd/C can form ethyl and propanol products through dehydrogenation and hydrogenation reactions. Adding water increases the selectivity of propyl products. Similar trends in yield and selectivity are observed for poplar RCF and reactions with coniferyl alcohol, indicating the importance of stabilization rate of reactive monomer intermediates in H-2-free RCF.

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Tailored one-pot lignocellulose fractionation to maximize biorefinery toward versatile xylochemicals and nanomaterials

Yanyan Yu et al.

Summary: The use of diol-tailored deep eutectic solvents allows for efficient fractionation of lignocellulose and maximizes the efficiency of refinery. This method achieves near-quantitative extraction of cellulose from lignocellulose, while simultaneously solubilizing lignin and hemicellulose. Additionally, the hemicellulose can be selectively converted to useful products and the lignin can be recovered for synthesis of other chemicals. This work demonstrates the importance of tailored deep eutectic solvent fractionation in lignocellulose refinery.

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Hydrolysis-dehydration of cellulose to glucose and 5-hydroxymethylfurfural over Sibunit solid acid carbon catalysts under semi-flow conditions

Cyril Aymonier et al.

Summary: This study demonstrates the possibility of producing glucose and 5-HMF from inedible cellulose using solid acid catalysts based on Sibunit carbon material; the acidity of the catalyst and the nature and amount of surface acid groups affect the formation of glucose and 5-HMF; through proper processing, yields of up to 75% and 10% for glucose and 5-HMF, respectively, can be obtained from polysaccharides.

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Highly efficient fractionation of corn stover into lignin monomers and cellulose-rich pulp over H2WO4

Zewei Ma et al.

Summary: This study investigates the fractionation of raw biomass based on a lignin-first biorefinery strategy, aiming to achieve efficient fractionation of corn stover. Results show that temperature and reaction time have an impact on lignin removal efficiency, as well as cellulose retention and lignin monomer yield.

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Advances in Versatile Nanoscale Catalyst for the Reductive Catalytic Fractionation of Lignin

Haichuan Zhang et al.

Summary: This review discusses the latest advances in biomass-derived biofuels and biochemicals as alternatives to petroleum, focusing on the synthesis and fabrication of porous nanocatalysts for hydrogenolysis of lignin. The emphasis is on catalyst design, the effects of different supports, and the challenges and opportunities for lignin hydrogenolysis over nanomaterial-supported catalysts.

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A review on trends in lignin extraction and valorization of lignocellulosic biomass for energy applications

Diego Ramon Lobato-Peralta et al.

Summary: This review summarizes various lignin extraction methods, pre-treatments, and their influence on yield and properties, as well as investigates thermochemical conversion of lignin-based biomass and its application in supercapacitors and hydrogen storage. The study highlights the importance of chemical extraction via the organosolv process in preserving lignin structure and purity compared to sulfur processes. Moreover, parameters such as extraction method, temperature, pH, resident time, and pressure significantly affect the Kappa value and yield of lignin.

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Article Agricultural Engineering

Molybdenum-catalyzed hydrogenolysis of herbaceous biomass: A procedure integrated lignin fragmentation and components fractionation

Xue Gong et al.

Summary: The study demonstrated the successful utilization of a low-cost MoO2/C catalyst for reductive catalytic fractionation of various herbaceous biomass feedstocks, resulting in high yields and selectivity of phenolic monomers, along with the production of solid carbohydrate pulps suitable for enzymatic hydrolysis.

BIORESOURCE TECHNOLOGY (2021)

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β-Zeolite-Assisted Lignin-First Fractionation in a Flow-Through Reactor**

Alexei Kramarenko et al.

Summary: This study conducted hydrogen-free one-step catalytic fractionation of woody biomass using commercial beta-zeolite as catalyst in a flow-through reactor. The results showed that beta-Zeolite acted as a bifunctional catalyst, playing a significant role in the reaction process.

CHEMSUSCHEM (2021)

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Article Agricultural Engineering

Effect of metal triflates on the microwave-assisted catalytic hydrogenolysis of birch wood lignin to monophenolic compounds

Xudong Liu et al.

Summary: By utilizing Fe(OTf)(3) as a Lewis acid and combining it with microwave heating, efficient delignification and depolymerization of lignin in birch sawdust were achieved, resulting in a high yield of monophenolic compounds.

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Article Chemistry, Physical

The Impact of Biomass and Acid Loading on Methanolysis during Two-Step Lignin-First Processing of Birchwood

Panos D. Kouris et al.

Summary: This study optimized the solvolysis step in methanol for the two-step lignin-first upgrading of woody biomass. The impact of reaction conditions on delignification and sugar release was investigated, revealing that high pressure and optimized ratios can enhance delignification while preserving key chemical bonds. The high reactivity of extracted lignin fragments was confirmed through a second hydrogenolysis step, facilitating ether linkage disappearance and molecular weight reduction in hydrotreated lignin oil.

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Progress in plant-based bioelectrochemical systems and their connection with sustainable development goals

Enas Taha Sayed et al.

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Effects of metal sites and acid sites on the hydrogenolysis of cornstalks in supercritical ethanol during lignin-first fractionation

Bowen Luo et al.

Summary: Utilizing a lignin-first strategy, the hydrogenolysis of cornstalk lignin in supercritical ethanol was investigated with a focus on the effects of metal and acid sites. The acid pretreatment of Ru/C catalysts significantly improved the hydrogenolysis process, with Ru/C-acid (10) achieving the highest monomer yield of 42.9 wt%. Characterizations of catalysts and products demonstrated the importance of active metal and acid sites for efficient lignin hydrogenolysis.

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Lignin First: Confirming the Role of the Metal Catalyst in Reductive Fractionation

Lu Chen et al.

Summary: The study confirms the precise role of metal catalysts in the reductive catalytic fractionation of lignin by using rhodium nanoparticles embedded in hollow porous carbon nanospheres to hydrogenate monomeric lignin fragments into more stable forms following a solvent-based fractionation and fragmentation of lignin.

JACS AU (2021)

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Flow-through solvolysis enables production of native-like lignin from biomass

David G. Brandner et al.

Summary: In this study, flow-through solvolysis with methanol at 225 degrees C was used to produce native-like lignin from poplar, enabling the study of intrinsic lignin properties and evaluation of steady-state lignin depolymerization processes.

GREEN CHEMISTRY (2021)

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Low molecular weight and highly functional RCF lignin products as a full bisphenol a replacer in bio-based epoxy resins

Korneel Van Aelst et al.

Summary: This study introduces a complete valorization chain for converting lignocellulose to chemicals, where lignin oligomers derived from pine wood through reductive catalytic fractionation are used to fully replace BPA in the synthesis of bio-based epoxy resins.

CHEMICAL COMMUNICATIONS (2021)

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Highly selective reductive catalytic fractionation at atmospheric pressure without hydrogen

Tianyu Ren et al.

Summary: By conducting reductive catalytic fractionation of lignin at or near atmospheric pressure using Ru/C catalyst in ethylene glycol, propylguaiacol and propylsyringyl can be efficiently produced, making the operation easier and more convenient.

GREEN CHEMISTRY (2021)

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Yi Liu et al.

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Effect of cobalt on titania, ceria and zirconia oxide supported catalysts on the oxidative depolymerization of prot and alkali lignin

Avnish Kumar et al.

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Yuhe Liao et al.

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Zeolite-Assisted Lignin-First Fractionation of Lignocellulose: Overcoming Lignin Recondensation through Shape-Selective Catalysis

Elena Subbotina et al.

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Enhanced Acid-Catalyzed Lignin Depolymerization in a Continuous Reactor with Stable Activity

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Highly Efficient Reductive Catalytic Fractionation of Lignocellulosic Biomass over Extremely Low-Loaded Pd Catalysts

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Osamudiamhen Elvis Ebikade et al.

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Reductive catalytic fractionation of lignin in birch sawdust to monophenolic compounds with high selectivity

Xudong Liu et al.

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Solvent assisted catalytic conversion of beech wood and organosolv lignin over NiMo/γ-Al2O3

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