Selective lignin arylation for biomass fractionation and benign bisphenols.

Lignocellulose is mainly composed of hydrophobic lignin and hydrophilic polysaccharide polymers, contributing to an indispensable carbon resource for green biorefineries1,2. When chemically treated, lignin is compromised owing to detrimental intra- and intermolecular crosslinking that hampers downstream process3,4. The current valorization paradigms aim to avoid the formation of new C-C bonds, referred to as condensation, by blocking or stabilizing the vulnerable moieties of lignin5-7. Although there have been efforts to enhance biomass utilization through the incorporation of phenolic additives8,9, exploiting lignin's proclivity towards condensation remains unproven for valorizing both lignin and carbohydrates to high-value products. Here we leverage the proclivity by directing the C-C bond formation in a catalytic arylation pathway using lignin-derived phenols with high nucleophilicity. The selectively condensed lignin, isolated in near-quantitative yields while preserving its prominent cleavable ß-ether units, can be unlocked in a tandem catalytic process involving aryl migration and transfer hydrogenation. Lignin in wood is thereby converted to benign bisphenols (34-48 wt%) that represent performance-advantaged replacements for their fossil-based counterparts. Delignified pulp from cellulose and xylose from xylan are co-produced for textile fibres and renewable chemicals. This condensation-driven strategy represents a key advancement complementary to other promising monophenol-oriented approaches targeting valuable platform chemicals and materials, thereby contributing to holistic biomass valorization.

Kraft Lignin: A Valuable, Sustainable Resource, Opportunities and Challenges.

Kraft lignin, a by-product from the production of pulp, is currently incinerated in the recovery boiler during the chemical recovery cycle, generating valuable bioenergy and recycling inorganic chemicals to the pulping process operation. Removing lignin from the black liquor or its gasification lowers the recovery boiler load enabling increased pulp production. During the past ten years, lignin separation technologies have emerged and the interest of the research community to valorize this underutilized resource has been invigorated. The aim of this Review is to give (1) a dedicated overview of the kraft process with a focus on the lignin, (2) an overview of applications that are being developed, and (3) a techno-economic and life cycle asseeements of value chains from black liquor to different products. Overall, it is anticipated that this effort will inspire further work for developing and using kraft lignin as a commodity raw material for new applications undeniably promoting pivotal global sustainability concerns.

Consequential life cycle assessment of kraft lignin recovery with chemical recycling.

The recovery of kraft lignin from black liquor allows an increasing of the pulp production of a kraft mill (marginal tonnage) and at the same time provide a valuable material that can be used as energy or chemical feedstock. However, because lignin precipitation is an energy- and material-consuming process, the environmental consequences from a life cycle perspective are under discourse. The aim of this study is to investigate, through the application of consequential life cycle assessment, the potential environmental benefits of kraft lignin recovery and its subsequent use as an energy or chemical feedstock. A newly developed chemical recovery strategy was assessed. The results revealed how the use of lignin as energy feedstock is not environmentally advantageous compared to producing energy directly from the pulp mill's recovery boiler. However, the best results were observed when lignin was used as a chemical feedstock in four applications to replace bitumen, carbon black, phenol, and bisphenol-A.

Single-Standard Quantification Strategy for Lignin Dimers by Supercritical Fluid Chromatography with Charged Aerosol Detection.

The increased interest in utilizing lignin as a feedstock to produce various aromatic compounds requires advanced chemical analysis methods to provide qualitative and quantitative characterization of lignin samples along different technology streamlines. However, due to the lack of commercially available chemical standards, routine quantification of industrially relevant lignin oligomers in complex lignin samples remains a challenge. This study presents a novel method for universal quantification of lignin dimers based on supercritical fluid chromatography with charged aerosol detection (CAD). A series of lignin-derived dimeric compounds that have been reported from reductive catalytic fractionation (RCF) were synthesized and used as standards. The applicability of using linear regression instead of quadratic calibration curves was evaluated over a concentration range of 15-125 mg/L, demonstrating that the former calibration method is as appropriate as the latter. The response factors of lignin dimeric compounds were compared to assess the uniformity of the CAD signal, revealing that the CAD response for the tested lignin dimers did not differ substantially. It was also found that the response factors were not dependent on the number of methoxy groups or linkage motifs, ultimately enabling the use of only one calibrant for these compounds. The importance of chromatographic peak resolution in CAD was stressed, and the use of a digital peak sharpening technique was adopted and applied to address this challenge. The developed method was verified and used for the quantification of lignin dimers in an oil obtained by a RCF of birch sawdust.

A New Family of Renewable Thermosets: Kraft Lignin Poly-adipates.

Thermosetting polymeric materials have advantageous properties and are therefore used in numerous applications. In this study, it was hypothesized and ultimately shown that thermosets could be derived from comparably sustainable sub-components. A two-step procedure to produce a thermoset comprising of Kraft lignin (KL) and the cross-linker adipic acid (AdA) was developed. The cross-linking was activated by means of an acetylating agent comprising isopropenyl acetate (IPA) to form a cross-linking mixture (CLM). The cross-linking was confirmed by FTIR and solid-state NMR spectroscopy, and the esterification reactions were further studied using model compounds. When the KL lignin was mixed with the CLM, partial esterification occurred to yield a homogeneous viscous liquid that could easily be poured into a mold, as the first step in the procedure. Without any additions, the mold was heated and the material transformed into a thermoset by reaction of the two carboxylic acid-derivatives of AdA and KL in the second step.

Oxidative cleavage of C-C bonds in lignin.

Lignin is an aromatic polymer that constitutes up to 30 wt% of woody biomass and is considered the largest source of renewable aromatics. Valorization of the lignin stream is pivotal for making biorefining sustainable. Monomeric units in lignin are bound via C-O and C-C bonds. The majority of existing methods for the production of valuable compounds from lignin are based on the depolymerization of lignin via cleavage of relatively labile C-O bonds within lignin structure, which leads to yields of only 36-40 wt%. The remaining fraction (60 wt%) is a complex mixture of high-molecular-weight lignin, generally left unvalorized. Here we present a method to produce additional valuable monomers from the high-molecular-weight lignin fraction through oxidative C-C bond cleavage. This oxidation reaction proceeds with a high selectivity to give 2,6-dimethoxybenzoquinone (DMBQ) from high-molecular-weight lignin in 18 wt% yield, thus increasing the yield of monomers by 32%. This is an important step to make biorefining competitive with petroleum-based refineries.

Thermal and Mechanical Properties of Esterified Lignin in Various Polymer Blends.

Lignin is an abundant polymeric renewable material and thus a promising candidate for incorporation in various commercial thermoplastic polymers. One challenge is to increase the dispersibility of amphiphilic lignin in lipophilic thermoplastic polymers We altered Kraft lignin using widely available and renewable fatty acids, such as oleic acid, yielding more than 8 kg of lignin ester as a light brown powder. SEC showed a molecular weight of 5.8 kDa with a PDI = 3.80, while the Tg of the lignin ester was concluded to 70 °C. Furthermore, the lignin ester was incorporated (20%) into PLA, HDPE, and PP to establish the thermal and mechanical behavior of the blends. DSC and rheological measurements suggest that the lignin ester blends consist of a phase-separated system. The results demonstrate how esterification of lignin allows dispersion in all the evaluated thermoplastic polymers maintaining, to a large extent, the tensile properties of the original material. The impact strength of HDPE and PLA blends show substantial loss upon the addition of the lignin ester. Reconverting the acetic acid side stream into acetic anhydride and reusing the catalyst, the presented methodology can be scaled up to produce a lignin-based substitute to fossil materials.

Debottlenecking a Pulp Mill by Producing Biofuels from Black Liquor in Three Steps.

By extracting lignin, pulp production can be increased without heavy investments in a new recovery boiler, the typical bottleneck of a pulp mill. The extraction is performed by using 0.20 and 0.15 weight equivalents of CO2 and H2 SO4 respectively. Herein, we describe lignin esterification with fatty acids using benign reagents to generate a lignin ester mixable with gas oils. The esterification is accomplished by activating the fatty acid and lignin with acetic anhydride which can be regenerated from the acetic acid recycled in this reaction. The resulting mass balance ratio is fatty acid/lignin/acetic acid (2 : 1 : 0.1). This lignin ester can be hydroprocessed to generate hydrocarbons in gasoline, aviation, and diesel range. A 300-hour continuous production of fuel was accomplished. By recirculating reagents from both the esterification step and applying a water gas shift reaction on off-gases from the hydroprocessing, a favorable overall mass balance is realized.

Holistic Valorization of Hemp through Reductive Catalytic Fractionation.

Despite the increased use of hemp fiber, negligible attention has been given to upgrade the hemp hurd, which constitutes up to 70 wt % of the hemp stalk and is currently considered a low-value byproduct. In this work, valorization of hemp hurd was performed by reductive catalytic fractionation (RCF) in the presence of a metal catalyst. We found an unexpectedly high yield of monophenolic compounds (38.3 wt %) corresponding to above 95% of the theoretical maximum yield. The high yield is explained by both a thin cell wall and high S-lignin content. In addition, organosolv pulping was performed to generate a pulp that was bleached to produce dissolving-grade pulp suitable for textile fiber production (viscosity, 898 mL/g; ISO-brightness, 90.2%) and nanocellulose. Thus, we have demonstrated a novel value chain from a low-value side stream of hemp fiber manufacture that has the potential to increase textile fiber production with 100% yield and also give bio-oil for green chemicals.

Techno-economic analysis and life cycle assessment of a biorefinery utilizing reductive catalytic fractionation.

Reductive catalytic fractionation (RCF) is a promising approach to fractionate lignocellulose and convert lignin to a narrow product slate. To guide research towards commercialization, cost and sustainability must be considered. Here we report a techno-economic analysis (TEA), life cycle assessment (LCA), and air emission analysis of the RCF process, wherein biomass carbohydrates are converted to ethanol and the RCF oil is the lignin-derived product. The base-case process, using a feedstock supply of 2000 dry metric tons per day, methanol as a solvent, and H2 gas as a hydrogen source, predicts a minimum selling price (MSP) of crude RCF oil of $1.13 per kg when ethanol is sold at $2.50 per gallon of gasoline-equivalent ($0.66 per liter of gasoline-equivalent). We estimate that the RCF process accounts for 57% of biorefinery installed capital costs, 77% of positive life cycle global warming potential (GWP) (excluding carbon uptake), and 43% of positive cumulative energy demand (CED). Of $563.7 MM total installed capital costs, the RCF area accounts for $323.5 MM, driven by high-pressure reactors. Solvent recycle and water removal via distillation incur a process heat demand equivalent to 73% of the biomass energy content, and accounts for 35% of total operating costs. In contrast, H2 cost and catalyst recycle are relatively minor contributors to operating costs and environmental impacts. In the carbohydrate-rich pulps, polysaccharide retention is predicted not to substantially affect the RCF oil MSP. Analysis of cases using different solvents and hemicellulose as an in situ hydrogen donor reveals that reducing reactor pressure and the use of low vapor pressure solvents could reduce both capital costs and environmental impacts. Processes that reduce the energy demand for solvent separation also improve GWP, CED, and air emissions. Additionally, despite requiring natural gas imports, converting lignin as a biorefinery co-product could significantly reduce non-greenhouse gas air emissions compared to burning lignin. Overall, this study suggests that research should prioritize ways to lower RCF operating pressure to reduce capital expenses associated with high-pressure reactors, minimize solvent loading to reduce reactor size and energy required for solvent recovery, implement condensed-phase separations for solvent recovery, and utilize the entirety of RCF oil to maximize value-added product revenues.

Assessing Methodologies to Synthesize α-Sulfenylated Carbonyl Compounds by Green Chemistry Metrics.

α-Sulfenylated carbonyl compounds are important both as active pharmaceutical ingredients and as intermediates in organic synthesis. Owing to their relevance in synthetic organic chemistry, this Minireview focuses on assessing the most relevant synthetic procedures based on green chemistry metrics. The Minireview starts with the traditional routes and then focuses on more recently developed methodologies. These routes include sulfenylating reagents using organocatalysis, cross-dehydrogenative couplings using in situ halogenations to prevent reactive intermediates in high concentrations, oxidative couplings using terminal oxidants such as DDQ or TEMPO, and redox-neutral couplings using transition metal catalysis. These methodologies have been evaluated on the basis of atom economy, E factor, and the safety and toxicity of the transformations and the solvents used. Besides using green metrics to evaluate these novel methodologies, the synthetic utility is also assessed with regard to the availability of starting materials and the generality of the reactions. This Minireview aims to inspire researchers to apply green assessments to other methodologies and also for them to take measures to increase the greenness of their developed transformations.

Preface to Special Issue of ChemSusChem on Lignin Valorization: From Theory to Practice.

In this Editorial, Guest Editors Run-Cang Sun, Joseph S. M. Samec, and Arthur J. Ragauskas introduce the Special Issue of ChemSusChem on Lignin Valorization: From Theory to Practice. The significance of and enormous challenges for the utilization of lignin are reviewed, and the contents of the Special Issue with highly interesting contributions from scientists around the world are outlined.

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

Organosolv pulping releases reactive monomers from both lignin and hemicellulose by the cleavage of weak C-O bonds. These monomers recombine to form undesired polymers through the formation of recalcitrant C-C bonds. Different strategies have been developed to prevent this process by stabilizing the reactive monomers (i.e., lignin-first approaches). To date, all reported approaches rely on the addition of capping agents or metal-catalyzed stabilization reactions, which usually require high pressures of hydrogen gas. Herein, a metal- and additive-free approach is reported that uses zeolites as acid catalysts to convert the reactive monomers into more stable derivatives under organosolv pulping conditions. Experiments with model lignin compounds showed that the recondensation of aldehydes and allylic alcohols produced by the cleavage of ß-O-4' bonds was efficiently inhibited by the use of protonic ß zeolite. By applying a zeolite with a preferred pore size, the bimolecular reactions of reactive monomers were effectively inhibited, resulting in stable and valuable monophenolics. The developed methodology was further extended to birch wood to yield monophenolic compounds and value-added products from carbohydrates.

Intermolecular Stereospecific Substitution of Underivatized Enantioenriched Secondary Alcohols by Organocatalysis.

The stereospecific substitution of non-derivatized and non-allylic enantioenriched alcohols with only water as a by-product would enable the use of readily available alcohols as substrates for green and sustainable transformations. However, the poor leaving group ability of the OH group has hampered the development of such a process. Denton and co-workers recently described the use of (2-hydroxybenzyl)diphenylphosphine oxide as a catalyst of a redox-neutral and zero-waste-generating Mitsunobu reaction. This innovative process constitutes the first intermolecular stereospecific substitution of non-allylic alcohols, and might find industrial applications.

Intramolecular substitutions of secondary and tertiary alcohols with chirality transfer by an iron(III) catalyst.

Optically pure alcohols are abundant in nature and attractive as feedstock for organic synthesis but challenging for further transformation using atom efficient and sustainable methodologies, particularly when there is a desire to conserve the chirality. Usually, substitution of the OH group of stereogenic alcohols with conservation of chirality requires derivatization as part of a complex, stoichiometric procedure. We herein demonstrate that a simple, inexpensive, and environmentally benign iron(III) catalyst promotes the direct intramolecular substitution of enantiomerically enriched secondary and tertiary alcohols with O-, N-, and S-centered nucleophiles to generate valuable 5-membered, 6-membered and aryl-fused 6-membered heterocyclic compounds with chirality transfer and water as the only byproduct. The power of the methodology is demonstrated in the total synthesis of (+)-lentiginosine from D-glucose where iron-catalysis is used in a key step. Adoption of this methodology will contribute towards the transition to sustainable and bio-based processes in the pharmaceutical and agrochemical industries.

High-Atom Economic Approach To Prepare Chiral α-Sulfenylated Ketones.

Chiral α-sulfenylated ketones are versatile building blocks, although there are still several limitations with their preparation. Here we report a new two-step procedure, consisting of Pd-catalyzed hydrothiolation of propargylic alcohols followed by an enantioselective Rh isomerization of allylic alcohols. The isomerization reaction is the key step for obtaining the ketones in their enantioenriched form. The new methodology has a high atom economy and induces good to high levels of enantioselectivity; no waste is produced. A mechanism involving a Rh-hydride-enone intermediate is proposed for the isomerization reaction.

Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling Reaction of Naphthyl and Quinolyl Alcohols with Boronic Acids.

A nickel-catalyzed C(sp3)-C(sp2) Suzuki cross-coupling of arylboronic acids and (hetero)naphthyl alcohols has been developed. A Ni(dppp)Cl2 complex showed the highest efficiency and broadest substrate scope. High functional group tolerance has been achieved where 35  compounds could be generated in good to excellent yields, including both primary and secondary benzylic alcohols. Mechanistic studies using multiple NMR techniques as well as ESI-HRMS showed that the C-O cleavage is facilitated by an activation of the benzylic alcohol through formation of a boronic ester intermediate.

Functionalized spirolactones by photoinduced dearomatization of biaryl compounds.

The idea of using biaryl structures to generate synthetic building blocks such as spirolactones is attractive because biaryl structures are abundant in biomass waste streams. However, the inertness of aromatic rings of biaryls makes it challenging to transform them into functionalized structures. In this work, we developed photoinduced dearomatization of nonphenolic biaryl compounds to generate spirolactones. We demonstrate that dearomatization can be performed via either aerobic photocatalysis or anaerobic photooxidation to tolerate specific synthetic conditions. In both pathways, dearomatization is induced by electrophilic attack of the carboxyl radical. The resulting spirodiene radical is captured by either oxygen or water in aerobic and anaerobic systems, respectively, to generate the spirodienone. These methods represent novel routes to synthesize spirolactones from the biaryl motif.

Lignin Valorization by Cobalt-Catalyzed Fractionation of Lignocellulose to Yield Monophenolic Compounds.

Herein, a catalytic reductive fractionation of lignocellulose is presented using a heterogeneous cobalt catalyst and formic acid or formate as a hydrogen donor. The catalytic reductive fractionation of untreated birch wood yields monophenolic compounds in up to 34 wt % yield of total lignin, which corresponds to 76 % of the theoretical maximum yield. Model compound studies revealed that the main role of the cobalt catalyst is to stabilize the reactive intermediates formed during the organosolv pulping by transfer hydrogenation and hydrogenolysis reactions. Additionally, the cobalt catalyst is responsible for depolymerization reactions of lignin fragments through transfer hydrogenolysis reactions, which target the ß-O-4' bond. The catalyst could be recycled three times with only negligible decrease in efficiency, showing the robustness of the system.