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Publications (5 of 5) Show all publications
Jogi, R., Samikannu, A., Mäki-Arvela, P., Virtanen, P., Hemming, J., Smeds, A., . . . Mikkola, J.-P. (2024). Liquefaction of lignocellulosic biomass into phenolic monomers and dimers over multifunctional Pd/NbOPO4 catalyst. Renewable energy, 233, Article ID 121148.
Open this publication in new window or tab >>Liquefaction of lignocellulosic biomass into phenolic monomers and dimers over multifunctional Pd/NbOPO4 catalyst
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2024 (English)In: Renewable energy, ISSN 0960-1481, E-ISSN 1879-0682, Vol. 233, article id 121148Article in journal (Refereed) Published
Abstract [en]

For the first time, a tandem catalytic material, 5 wt. % Pd/NbOPO4, was utilized in the depolymerization of wood in supercritical ethanol under hydrogen atmosphere. The experiments were conducted under various conditions, with fresh, and acetone extracted birch. A comprehensive analysis was performed to elucidate the dissolution efficiency and achieved product distribution. The results indicated that with fresh birch, 34 wt. % of lignin monomer yield with 84 wt. % delignification efficiency were obtained while with extracted wood, 35 wt. % of lignin monomer yield with 78 wt. % delignification efficiency were achieved. The total lignin monomer content extracted from the fresh birch is composed of 76.9 wt. % of dimethoxyphenols and 16.5 wt. % with the guaiacol structure. Major lignin monomer product was homosyringaldehyde (61.9 wt. %). With extracted wood, 93.2 wt. % of dimethoxyphenols (63.6 wt. % homosyringaldehyde) and 6.8 wt. % of guaiacol-monomers were achieved. It was concluded that the depolymerization occurred via breaking of the ether bonds in lignin, including ether hydrolysis by Lewis acid sites over the solid acid catalyst and with subsequent deoxygenation of monophenols over Pd. In addition, an extraction process was proposed to extract the aromatic fraction from the obtained biocrude.

Place, publisher, year, edition, pages
Elsevier, 2024
Keywords
liquefaction, wood biomass, tandem catalyst, bio-aromatics, aromatic extraction, deep eutectic solvents
National Category
Organic Chemistry Analytical Chemistry Bioprocess Technology
Identifiers
urn:nbn:se:umu:diva-228224 (URN)10.1016/j.renene.2024.121148 (DOI)001295524400001 ()2-s2.0-85201073446 (Scopus ID)
Funder
Bio4Energy
Available from: 2024-08-07 Created: 2024-08-07 Last updated: 2025-04-24Bibliographically approved
Jogi, R., Samikannu, A., Mäki-Arvela, P., Virtanen, P., Hemming, J., Smeds, A., . . . Mikkola, J.-P. (2022). Liquefaction of Lignocellulosic Biomass into Phenolic Monomers and Dimers Over Multifunctional Pd/Nbopo4 Catalyst.
Open this publication in new window or tab >>Liquefaction of Lignocellulosic Biomass into Phenolic Monomers and Dimers Over Multifunctional Pd/Nbopo4 Catalyst
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2022 (English)Manuscript (preprint) (Other academic)
Abstract [en]

For the first time, a tandem catalytic material namely 5 wt. % Pd/NbOPO 4 was utilized in the depolymerization of wood in supercritical-ethanol under low initial-hydrogen pressure. The experiments were conducted under various experimental conditions, wood fractionation was executed with fresh, and acetone extracted birch. A comprehensive analysis was performed to elucidate the dissolution efficiency and achieved product distribution. The results indicated fresh birch, 34 wt. % of lignin monomer yield with 84 wt. % delignification efficiency were obtained while extracted wood, 35 wt. % of lignin monomer yield with 78 wt. % delignification efficiency was achieved. The total lignin monomer content extracted from the fresh birch is composed of 76.9 wt. % of dimethoxyphenols and 16.5 wt. % of monomers with the guaiacol structure. Among the dimethoxyphenols, major homosyringaldehyde (61.9 wt. %). Where extracted wood, 93.2 wt. % of dimethoxyphenols (63.6 wt. % homosyringaldehyde) and guaiacol-monomers (6.8 wt. %). It was concluded that the depolymerization occurred via breaking of the ether bonds in lignin, including ether hydrolysis by Lewis acid sites over the solid acid catalyst and with subsequent deoxygenation of monophenols over Pd. In addition, an extraction process was proposed to extract the aromatic fraction from the obtained biocrude.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-198313 (URN)10.2139/ssrn.4093291 (DOI)
Available from: 2022-07-28 Created: 2022-07-28 Last updated: 2022-07-29
Mukesh, C., Sarmad, S., Samikannu, A., Nikjoo, D., Siljebo, W. & Mikkola, J.-P. (2022). Pore size-excluded low viscous porous liquids for CO2 sorption at room temperature and thermodynamic modeling study. Journal of Molecular Liquids, 356, Article ID 119046.
Open this publication in new window or tab >>Pore size-excluded low viscous porous liquids for CO2 sorption at room temperature and thermodynamic modeling study
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2022 (English)In: Journal of Molecular Liquids, ISSN 0167-7322, E-ISSN 1873-3166, Vol. 356, article id 119046Article in journal (Refereed) Published
Abstract [en]

Herein, we report porous ionic liquids (type-III) designed to utilize microporous ZIF-8 moieties with functional ionic liquids such as 8-(2-methoxyethyl)-1,8-Diazabicyclo[5.4.0]undec-7-en-8-ium, Bis(trifluoromethane)sulfonamide ([MEDBU][TFSI] and Trioctylammonium 4-para-tert-butylbenzoiate [TOAH][PTBBA]). The prepared materials were thoroughly characterized by means of XRD, FT-IR, SEM, TEM, BET, TGA, DSC and viscometry techniques. The idea of combining the intrinsic properties of ionic liquids with microporous architecture to prepare porous ionic liquids yields promising fluidic materials that have received attention in industrial applications such as gas sorption and separation etc. The prepared porous ionic liquids possess unique physico-chemical properties such as low viscosity, high thermal stability, low vapor pressure, reusability and their fluidic nature renders the materials suitable for CO2 capture. Herein introduced porous ionic liquids (ILs) showed enhanced CO2 uptake (0.92 mmol/g in [TOAH][PTBBA]-Z100 and 1.16 mmol/g in [MEDBU][TFSI]-Z200), or in other words, 15–47% higher sorption capacity compared to neat ionic liquids. This concept overcomes the drawbacks of highly viscous ILs and their limited CO2 sorption capacity. Thermodynamic modeling further demonstrated that the enthalpy of sorption is only −9.99 kJ mol−1, indicating that significantly less energy is required for regeneration. This is promising for the potential use of these fluidic materials in continuous separation processes on an industrial scale, as a better alternative to the existing hazardous amine scrubbing.

Place, publisher, year, edition, pages
Elsevier, 2022
National Category
Physical Chemistry Materials Chemistry
Identifiers
urn:nbn:se:umu:diva-194108 (URN)10.1016/j.molliq.2022.119046 (DOI)000799182800017 ()2-s2.0-85128835880 (Scopus ID)
Funder
Bio4EnergyThe Kempe FoundationsKnut and Alice Wallenberg Foundation
Available from: 2022-04-25 Created: 2022-04-25 Last updated: 2023-09-05Bibliographically approved
Mukesh, C., Nikjoo, D. & Mikkola, J.-P. (2020). Production of C-14 Levulinate Ester from Glucose Fermentation Liquors Catalyzed by Acidic Ionic Liquids in a Solvent-Free Self-Biphasic System. ACS Omega, 5(10), 4828-4835
Open this publication in new window or tab >>Production of C-14 Levulinate Ester from Glucose Fermentation Liquors Catalyzed by Acidic Ionic Liquids in a Solvent-Free Self-Biphasic System
2020 (English)In: ACS Omega, E-ISSN 2470-1343, Vol. 5, no 10, p. 4828-4835Article in journal (Refereed) Published
Abstract [en]

Herein, we present the C-14 levulinate ester of 2,3-butanediol as the product of sugar fermentation liquors. The designed Brønsted acidic ionic liquid (BAIL) catalysts enable self-induced phase separation with ester products, and the role of anions has been investigated. Esterification reactions were carried out by 2,3-butanediol (2,3-BDO) and levulinic acid in solvent-free media and low temperatures (60–105 °C). For comparison, sulfuric acid, amberlite IR-120, and sulfonic acid-functionalized pyridinium ionic liquids with different anions were utilized as a catalyst upon esterification reaction. The diester product, namely, butane-2,3-diyl bis(4-oxopentanoate), was formed with a good yield (85%) and selectivity (85%) after complete conversion of 2,3-BDO in 24 h at 80 °C. The low yield (8%) of the monoester was observed. The monoester and diester were separated by a liquid–liquid extraction method. The ester products were characterized by various instrumental techniques such as 1H and 13C NMR, GC–FID, LC–MS, and FT-IR spectroscopy. The Hammett acidity functions of BAILs were determined from UV–vis spectroscopy. The catalyst was successfully recycled and reused in the processes. The spent BAILs were reused in six consecutive cycles with only a ∼7% diminished diester yield and selectivity. The produced levulinate ester will be useful as biofuel additives, solvents, plasticizers, and other applications.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2020
National Category
Chemical Engineering Organic Chemistry Polymer Technologies Other Chemical Engineering
Identifiers
urn:nbn:se:umu:diva-168744 (URN)10.1021/acsomega.9b03517 (DOI)000520853400014 ()2-s2.0-85081219571 (Scopus ID)
Projects
Bio4Energy
Funder
Bio4Energy
Available from: 2020-03-09 Created: 2020-03-09 Last updated: 2025-02-18Bibliographically approved
Mukesh, C., Khokarale, S. G., Virtanen, P. & Mikkola, J.-P. (2019). Rapid desorption of CO2 from deep eutectic solvents based on polyamines at lower temperatures: an alternative technology with industrial potential. Sustainable Energy & Fuels, 3(8), 2125-2134
Open this publication in new window or tab >>Rapid desorption of CO2 from deep eutectic solvents based on polyamines at lower temperatures: an alternative technology with industrial potential
2019 (English)In: Sustainable Energy & Fuels, E-ISSN 2398-4902, Vol. 3, no 8, p. 2125-2134Article in journal (Refereed) Published
Abstract [en]

Herein we developed a new family of polyamine-based deep eutectic solvents (DESs) dedicated to reduce the energy consumption, avoiding the formation of hazardous molecules, aiming at low solvent losses and robust desorption efficiency for carbon dioxide (CO 2) capture technology. The strategy developed for economical, thermally stable and low viscous absorbents for CO 2 capture by functionalized neoteric media of azolide anion and secondary amine is presented. The prepared anion functionalized ionic liquids (ILs) and the derived DESs with ethylene glycol (EG) have a low viscosity which promotes high uptake of CO 2 (17-22% w/w) at 298.15 K and 1 atm. The absorption capacity of DESs was determined by a gravimetric technique. 13 C NMR was used for examine the desorption efficiency (DE) of CO 2. It was found that rapid desorption of CO 2 in TEPA polyamine based DESs occurs compared to monoethanolamine at 80 °C. However, the desorption rate of CO 2 was observed to be higher at higher temperatures and, as a result, under nitrogen flow complete desorption of CO 2 took place at 100 and 110 °C after 30 and 20 minutes, respectively. Consequently, comparative regeneration of CO 2 was studied in the absence of nitrogen flow at different temperatures. Excellent reversible uptake of CO 2 was observed without significant loss of absorption capacity under four consecutive cycles at 100 °C. The chemisorption of CO 2 was verified by 13 C NMR, 2D-NMR and FT-IR spectroscopy. The solvent loss study demonstrated the low volatility of polyamines based DESs at 100 °C and 120 °C after 50 hrs. The proposed DESs are thermally stable, cheap and give rise to negligible amounts of hazardous degradation components. Further, they exhibit low solvent losses, low viscosities and rapid CO 2 desorption capability. Therefore they are promising candidates when aiming at improving amine based conventional CO 2 capture technology.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
National Category
Organic Chemistry
Identifiers
urn:nbn:se:umu:diva-161789 (URN)10.1039/C9SE00112C (DOI)000476912900021 ()2-s2.0-85069772826 (Scopus ID)
Projects
Bio4Energy
Funder
Bio4Energy
Available from: 2019-08-05 Created: 2019-08-05 Last updated: 2020-12-17Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0003-4097-3504

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