| 1. |
- Adler, Anneli, et al.
(author)
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Lignin-first biorefining of Nordic poplar to produce cellulose fibers could displace cotton production on agricultural lands
- 2022
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In: Joule. - : Elsevier BV. - 2542-4351. ; 6:8, s. 1845-1858
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Journal article (peer-reviewed)abstract
- Here, we show that lignin-first biorefining of poplar can enable the production of dissolving cellulose pulp that can produce regenerated cellulose, which could substitute cotton. These results in turn indicate that agricultural land dedicated to cotton could be reclaimed for food production by extending poplar plantations to produce textile fibers. Based on climate-adapted poplar clones capable of growth on marginal lands in the Nordic region, we estimate an environmentally sustainable annual biomass production of ∼11 tonnes/ha. At scale, lignin-first biorefining of this poplar could annually generate 2.4 tonnes/ha of dissolving pulp for textiles and 1.1 m3 biofuels. Life cycle assessment indicates that, relative to cotton production, this approach could substantially reduce water consumption and identifies certain areas for further improvement. Overall, this work highlights a new value chain to reduce the environmental footprint of textiles, chemicals, and biofuels while enabling land reclamation and water savings from cotton back to food production.
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| 2. |
- Argyropoulos, Dimitris D. S., et al.
(author)
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Kraft Lignin: A Valuable, Sustainable Resource, Opportunities and Challenges
- 2023
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In: ChemSusChem. - : John Wiley and Sons Inc. - 1864-5631 .- 1864-564X. ; 16:23
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Research review (peer-reviewed)abstract
- 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.
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| 3. |
- Di Francesco, Davide, et al.
(author)
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Ductile Pd-Catalysed Hydrodearomatization of Phenol-Containing Bio-Oils Into Either Ketones or Alcohols using PMHS and H2O as Hydrogen Source
- 2018
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In: Advanced Synthesis and Catalysis. - : Wiley. - 1615-4150 .- 1615-4169. ; 360:20, s. 3924-3929
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Journal article (peer-reviewed)abstract
- A series of phenolic bio-oil components were selectively hydrodearomatized by palladium on carbon into the corresponding ketones or alcohols in excellent yields using polymethylhydrosiloxane and water as reducing agent. The selectivity of the reaction was governed by the water concentration where selectivity to alcohol was favoured at higher water concentrations. As phenolic bio-oil examples cardanol and beech wood tar creosote were studied as substrate to the developed reaction conditions. Cardanol was hydrodearomatized into 3-pentadecylcyclohexanone in excellent yield. From beech wood tar creosote, a mixture of cyclohexanols was produced. No hydrodeoxygenation occurred, suggesting the applicability of the reported method for the production of ketone-alcohol oil from biomass.
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| 4. |
- Galkin, Maxim V., et al.
(author)
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Hydrogen-free catalytic fractionation of woody biomass
- 2016
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In: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 9:23, s. 3280-3287
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Journal article (peer-reviewed)abstract
- The pulping industry could become a biorefinery if the lignin and hemicellulose components of the lignocellulose are valorized. Conversion of lignin into well-defined aromatic chemicals is still a major challenge. Lignin depolymerization reactions often occur in parallel with irreversible condensation reactions of the formed fragments. Here, we describe a strategy that markedly suppresses the undesired condensation pathways and allows to selectively transform lignin into a few aromatic compounds. Notably, applying this strategy to woody biomass at organosolv pulping conditions, the hemicellulose, cellulose, and lignin were separated and in parallel the lignin was transformed into aromatic monomers. In addition, we were able to utilize a part of the lignocellulose as an internal source of hydrogen for the reductive lignin transformations. We hope that the presented methodology will inspire researchers in the field of lignin valorization as well as pulp producers to develop more efficient biomass fractionation processes in the future.
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| 5. |
- Kumaniaev, Ivan, et al.
(author)
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A combination of experimental and computational methods to study the reactions during a Lignin-First approach
- 2020
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In: Pure and Applied Chemistry. - : Walter de Gruyter GmbH. - 0033-4545 .- 1365-3075. ; 92:4, s. 631-639
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Journal article (peer-reviewed)abstract
- Current pulping technologies only valorize the cellulosic fiber giving total yields from biomass below 50 %. Catalytic fractionation enables valorization of both cellulose, lignin, and, optionally, also the hemicellulose. The process consists of two operations occurring in one pot: (1) solvolysis to separate lignin and hemicellulose from cellulose, and (2) transition metal catalyzed reactions to depolymerize lignin and to stabilized monophenolic products. In this article, new insights into the roles of the solvolysis step as well as the operation of the transition metal catalyst are given. By separating the solvolysis and transition metal catalyzed hydrogen transfer reactions in space and time by applying a flow-through set-up, we have been able to study the solvolysis and transition metal catalyzed reactions separately. Interestingly, the solvolysis generates a high amount of monophenolic compounds by pealing off the end groups from the lignin polymer and the main role of the transition metal catalyst is to stabilize these monomers by transfer hydrogenation/hydrogenolysis reactions. The experimental data from the transition metal catalyzed transfer hydrogenation/hydrogenolysis reactions was supported by molecular dynamics simulations using ReaXFF.
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| 6. |
- Kumaniaev, Ivan, et al.
(author)
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Lignin depolymerization to monophenolic compounds in a flow-through system
- 2017
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In: Green Chemistry. - : Royal Society of Chemistry (RSC). - 1463-9262 .- 1463-9270. ; 19:24, s. 5767-5771
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Journal article (peer-reviewed)abstract
- A reductive lignocellulose fractionation in a flow-through system in which pulping and transfer hydrogenolysis steps were separated in time and space has been developed. Without the hydrogenolysis step or addition of trapping agents to the pulping, it is possible to obtain partially depolymerized lignin (21 wt% monophenolic compounds) that is prone to further processing. By applying a transfer hydrogenolysis step 37 wt% yield of lignin derived monophenolic compounds was obtained. Pulp generated in the process was enzymatically hydrolyzed to glucose in 87 wt% yield without prior purification.
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| 7. |
- Lebedeva, Daria, 1994-, et al.
(author)
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Sustainable aviation fuel from prehydrolysis liquors
- 2024
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In: Green Chemistry. - 1463-9262 .- 1463-9270. ; 26:12, s. 7258-7267
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Journal article (peer-reviewed)abstract
- Maximizing products of high value and minimizing incineration of side-streams is key to realize future biorefineries. In current textile production from forestry, hemicellulose is removed by prehydrolysis before delignification. The resulting prehydrolysis liquor is incinerated in the recovery boiler at low efficiency. This additional burden on the limiting recovery boiler reduces the pulp production. In this study, we demonstrate that prehydrolysis liquor can be upgraded, in 5 steps, to yield aviation fuels. Prehydrolysis liquors were dehydrated to furfural by zeolite catalysis. Furfural was selectively reduced to furfuryl alcohol by Au@NC. Rhenium-catalysed Achmatowicz rearrangement gave a C5 intermediate susceptible to self [2 + 2] cycloaddition to give the C10 oxygenated precursor. By using a combination of Ru/C and zeolites, full hydrodeoxygenation was achieved. The overall transformation from furfural to hydrocarbons resulted in a 48% carbon yield. The resulting hydrocarbons, containing an anticipated strained four-membered ring, are preferred aviation fuel components. This is an important step to show that aviation fuels can be produced sustainably from existing industrial side-streams. A comparative life cycle assessment was applied to evaluate the environmental impact of the proposed valorization approach, demonstrating benefits in the climate change impact category when implementing this technology in a pulp mill compared to the incineration of pre-hydrolysis liquor scenario.
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| 8. |
- Lebedeva, Daria, 1994-, et al.
(author)
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Waste-to-Fuel Approach : Valorization of Lignin from Coconut Coir Pith
- 2022
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In: ACS Agricultural Science and Technology. - : American Chemical Society (ACS). - 2692-1952. ; 2:2, s. 349-358
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Journal article (peer-reviewed)abstract
- Coconut Coir Pith (CCP) is a relatively unexplored type of lignocellulosic waste from the coconut industry. As a feedstock that is highly enriched in lignin (Klason lignin content of 40.9 wt % found in this study), CCP is a potential source for renewable lignin-derived materials. We have performed a systematic study on the characterization and valorization of lignin from CCP. We have investigated two different valorization approaches: reductive catalytic fractionation (RCF) and soda pulping followed by catalytic hydrodeoxygenation. During RCF, the lignin was converted into monomeric products in 7.6 wt %. Using soda pulping conditions, we were able to isolate lignin from CCP in 74% yield. Subsequent hydrotreatment of the lignin over a Pt/MoO3/TiO2catalyst resulted in the formation of hydrogenated oil in 43 wt % yield, suitable for the production of biobased diesel fuels and lubricant base oils.
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| 9. |
- Li, Hongji, et al.
(author)
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Functionalized spirolactones by photoinduced dearomatization of biaryl compounds
- 2019
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In: Chemical Science. - : Royal Society of Chemistry (RSC). - 2041-6520 .- 2041-6539. ; 10:12, s. 3681-3686
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Journal article (peer-reviewed)abstract
- 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.
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| 10. |
- Subbotina, Elena, et al.
(author)
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Aqueous synthesis of highly functional, hydrophobic, and chemically recyclable cellulose nanomaterials through oxime ligation
- 2022
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In: Nature Communications. - : Springer Nature. - 2041-1723. ; 13:1
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Journal article (peer-reviewed)abstract
- Cellulose nanofibril (CNF) materials are candidates for the sustainable development of high mechanical performance nanomaterials. Due to inherent hydrophilicity and limited functionality range, most applications require chemical modification of CNF. However, targeted transformations directly on CNF are cumbersome due to the propensity of CNF to aggregate in non-aqueous solvents at high concentrations, complicating the choice of suitable reagents and requiring tedious separations of the final product. This work addresses this challenge by developing a general, entirely water-based, and experimentally simple methodology for functionalizing CNF, providing aliphatic, allylic, propargylic, azobenzylic, and substituted benzylic functional groups. The first step is NaIO4 oxidation to dialdehyde-CNF in the wet cake state, followed by oxime ligation with O-substituted hydroxylamines. The increased hydrolytic stability of oximes removes the need for reductive stabilization as often required for the analogous imines where aldehyde groups react with amines in water. Overall, the process provides a tailored degree of nanofibril functionalization (2-4.5 mmol/g) with the possible reversible detachment of the functionality under mildly acidic conditions, resulting in the reformation of dialdehyde CNF. The modified CNF materials were assessed for potential applications in green electronics and triboelectric nanogenerators. Water is a standing challenge in the chemical modification of cellulose nanofibrils. Here, authors employ oxime-ligation to solve this by direct covalent chemistry on dialdehyde-CNF in water and assess the material for potential applications in green electronics and triboelectric nanogenerators.
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