| 1. |
- Abdelaziz, Omar Y., et al.
(författare)
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Conceptual Design of a Kraft Lignin Biorefinery for the Production of Valuable Chemicals via Oxidative Depolymerization
- 2020
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Ingår i: ACS Sustainable Chemistry & Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 8:23, s. 8823-8829
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Tidskriftsartikel (refereegranskat)abstract
- Lignin is the most abundant aromatic biopolymer on Earth, and its aromatic structure makes it a promising platform for the production of biobased chemicals and other valuable building blocks. The valorization of lignin into chemicals currently presents a challenge, and its facilitation is key in the development of viable lignocellulosic biorefinery processes. This study presents a conceptual design for a recently demonstrated process for lignin oxidative depolymerization. Modeling, simulation, and analysis were performed based on experimental data to assess the viability of the process. Mass and energy balances and main design data were determined for a 700 t/y kraft lignin biorefinery. The production capacity of aromatic chemicals, including vanillin, vanillic acid, guaiacol, and acetovanillone, was 0.3 kg aromatics/kg net lignin use. A heat-integrated process design is suggested, and the energy demands and the CO2 emissions are evaluated and compared. Assuming an interest rate of 10% and a plant lifetime of 10 years, the return on investment was calculated to be 14%, indicating that such a biorefinery is viable. A sensitivity analysis was carried out to assess the impact of the vanillin selling price and the cost of lignin on the profitability of the process. A quantitative investigation of process sustainability resulted in an E-factor of ∼1.6 for the entire synthetic route, that is, 38% material efficiency. The findings of this study underline the need for further research to develop efficient lignin conversion technologies with attractive yields in order to increase profitability on an industrial scale.
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| 2. |
- Abdelaziz, Omar Y., et al.
(författare)
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Oxidative Depolymerization of Kraft Lignin for Microbial Conversion
- 2019
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Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 7:13, s. 11640-11652
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Tidskriftsartikel (refereegranskat)abstract
- The valorization of lignin is being increasingly recognized as crucial to improve the economic viability of integrated biorefineries. Because of its inherent heterogeneity and recalcitrance, lignin has been treated as a waste product in the pulp and paper industry, but new technologies are now being explored to transform lignin into a sustainable resource and enhance its value chain. In the present study, alkaline oxidative depolymerization was investigated as a potential form of pretreatment to enable further biological conversion of LignoBoost kraft lignin (LB). LB lignin oxidation reactions were studied at various temperatures (120-200 °C) and O2 partial pressures (3-15 bar) to identify the optimal conditions for obtaining a biocompatible, oxidatively depolymerized lignin (ODLB) stream. The low molecular weight compounds resulting from this treatment consisted mainly of aromatic monomers and carboxylic acids. The highest yield of aromatic monomers, 3 wt %, was obtained at 160 °C and 3 bar O2. The yield of carboxylic acids increased with both increasing temperature and O2 pressure, exceeding 13% under the harshest conditions investigated. The growth of four aromatic-catabolizing bacterial strains was examined on reaction product mixtures, all of which showed growth on agar plates utilizing ODLB as the sole source of carbon and energy. Rhodococcus opacus and Sphingobium sp. SYK-6 were found to consume most of the aromatic monomers present in the ODLB (e.g., vanillin, vanillate, acetovanillone, and guaiacol). The findings of this study indicate that pretreatment by oxidative depolymerization has potential in the biological valorization of technical lignin streams, for the production of valuable chemicals and materials.
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| 3. |
- Adolfsson, Karin H., et al.
(författare)
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Microwave Assisted Hydrothermal Carbonization and Solid State Postmodification of Carbonized Polypropylene
- 2018
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Ingår i: ACS Sustainable Chemistry and Engineering. - : AMER CHEMICAL SOC. - 2168-0485. ; 6:8, s. 11105-11114
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Tidskriftsartikel (refereegranskat)abstract
- Functional carbon materials produced through a hydrothermal treatment of waste products have gained interest. Particularly, the method is considered more facile and green compared to conventional decomposition methods. Here, we demonstrated an upcycling of polypropylene (PP) waste to carbon materials by a microwave assisted hydro thermal treatment. The solid product obtained from the hydrothermal treatment was analyzed by multiple techniques to reveal the structure and the influence of processing conditions on PP degradation and hydrothermal carbonization. Chemical analyses showed the presence of carbonaceous material independent of acid amount (20 and 30 mL), temperature (210 and 250 degrees C), and time (20-80 min). A complete transformation of PP content to amorphous carbon required 60 min at 250 degrees C. The mass yield of the solid product decreased as a function of harsher processing conditions. At the same time, thermogravimetric analysis illustrated products with increasing thermal stability and a larger amount of remaining residue at 600 degrees C. The solid products consisted of irregular fragments and sheet-like structures. A solid state microwave process in air atmosphere was performed on a product with incomplete carbonization. The modification resulted in a decreased C/O ratio, and TGA analysis in nitrogen showed high thermal stability and degree of carbonization as indicated by the remaining residue of 86.4% at 600 degrees C. The new insights provided on the hydrothermal carbonization, and postmodification in air atmosphere, can catalyze effective handling of plastic waste by enabling transformation of low quality waste into functional carbon materials.
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| 4. |
- Adolfsson, Karin H., et al.
(författare)
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Zero-Dimensional and Highly Oxygenated Graphene Oxide for Multifunctional Poly(lactic acid) Bionanocomposites
- 2016
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Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 4:10, s. 5618-5631
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Tidskriftsartikel (refereegranskat)abstract
- The unique strengths of 2D graphene oxide nanosheets (GONSs) in polymer composites are thwarted by nanosheet agglomeration due to strong intersheet attractions. Here, we reveal that shrinking the planar size to 0D graphene oxide quantum dots (GOQDs), together with the intercalation of rich oxygen functional groups, reduces filler aggregation and enhances interfacial interactions with the host polymer. With poly(lactic acid) (PLA) as a model matrix, atomic force microscopy colloidal probe measurements illustrated that a triple increase in adhesion force to PLA was achieved for GOQDs (234.8 nN) compared to GONSs (80.4 nN), accounting for the excellent exfoliation and dispersion of GOQDs in PLA, in contrast to the notable agglomeration of GONSs. Although present at trace amount (0.05 wt %), GOQDs made a significant contribution to nucleation activity, mechanical strength and ductility, and gas barrier properties of PLA, which contrasted the inferior efficacy of GONSs, accompanied by clear distinction in film transparency (91% and 50%, respectively). Moreover, the GOQDs with higher hydrophilicity accelerated the degradation of PLA by enhancing water erosion, while the GONSs with large sheet surfaces gave a higher hydrolytic resistance. Our findings provide conceptual insights into the importance of the dimensionality and surface chemistry of GO nanostructures in the promising field of bionanocomposites integrating high strength and multifunction (e.g., enhanced transparency, degradation and gas barrier).
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| 5. |
- Ail, Ujwala, et al.
(författare)
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Effect of Sulfonation Level on Lignin/Carbon Composite Electrodes for Large-Scale Organic Batteries
- 2020
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Ingår i: ACS Sustainable Chemistry and Engineering. - : AMER CHEMICAL SOC. - 2168-0485. ; 8:49, s. 17933-17944
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Tidskriftsartikel (refereegranskat)abstract
- The key figure-of-merit for materials in stationary energy storage applications, such as large-scale energy storage for buildings and grids, is the cost per kilo per electrochemical cycle, rather than the energy density. In this regard, forest-based biopolymers such as lignin, are attractive, as they are abundant on Earth. Here, we explored lignin as an electroactive battery material, able to store two electrons per hydroquinone aromatic ring, with the targeted operation in aqueous electrolytes. The impact of the sulfonation level of lignin on the performance of its composite electrode with carbon was investigated by considering three lignin derivatives: lignosulfonate (LS), partially desulfonated lignosulfonate (DSLS), and fully desulfonated lignin (KL, lignin produced by the kraft process). Partial desulfonation helped in better stability of the composite in aqueous media, simultaneously favoring its water processability. In this way, a route to promote ionic conductivity within the lignin/carbon composite electrodes was developed, facilitating the access to the entire bulk of the volumetric electrodes. Electrochemical performance of DSLS/C showed highly dominant Faradaic contribution (66%) towards the total capacity, indicating an efficient mixed ionic-electronic transport within the lignin-carbon phase, displaying a capacity of 38 mAh/g at 0.25 A/g and 69% of capacity retention after 2200 cycles at a rate of 1 A/g.
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| 6. |
- Almenara Perez, Naroa, et al.
(författare)
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Lignin–Chitosan Gel Polymer Electrolytes for Stable Zn Electrodeposition
- 2023
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Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 11:6, s. 2283-2294
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Tidskriftsartikel (refereegranskat)abstract
- Electrochemical energy storage technologies offer means to transition toward a decarbonized society and carbon neutrality by 2050. Compared to conventional lithium-ion batteries, aqueous zinc-ion chemistries do not require scarce materials or toxic and flammable organic-based electrolytes to function, making them favorable contenders in the scenario of intensifying climate change and supply chain crisis. However, environmentally benign and bio-based materials are needed to substitute fossil-based battery materials. Accordingly, this work taps into the possibilities of lignin together with chitosan to form gel polymer electrolytes (GPEs) for zinc-ion chemistries. A simple fabrication process enabling free-standing sodium lignosulfonate–chitosan and micellar lignosulfonate–kraft lignin–chitosan GPEs with diameters exceeding 80 mm is developed. The GPEs combine tensile strength with ductility, reaching Young’s moduli of 55 ± 4 to 940 ± 63 MPa and elongations at break of 14.1 ± 0.2 to 43.9 ± 21.1%. Competitive ionic conductivities ranging from 3.8 to 18.6 mS cm–1 and electrochemical stability windows of up to +2.2 V vs Zn2+/Zn were observed. Given the improved interfacial adhesion of the GPEs with metallic Zn promoted by the anionic groups of the lignosulfonate, a stable cycling of the Zn anode is obtained. As a result, GPEs can operate at 5000 μA cm–2 with no short-circuit and Coulombic efficiencies above 99.7%, outperforming conventional separator–liquid electrolyte configurations such as the glass microfiber separator soaked into 2 M ZnSO4 aqueous electrolyte, which short-circuits after 100 μA cm–2. This work demonstrates the potential of underutilized biorefinery side-streams and marine waste as electrolytes in the battery field, opening new alternatives in the sustainable energy storage landscape beyond LIBs.
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| 7. |
- Almqvist, Henrik, et al.
(författare)
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Muconic Acid Production Using Engineered Pseudomonas putida KT2440 and a Guaiacol-Rich Fraction Derived from Kraft Lignin
- 2021
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Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 9:24, s. 8097-8106
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Tidskriftsartikel (refereegranskat)abstract
- Industrial lignin such as kraft lignin is an abundant feedstock for renewable chemicals and materials. In this study, a process was developed for depolymerization of kraft lignin followed by an upgrading separation step and further bioconversion of the obtained monoaromatic compounds to muconic acid. First, industrial kraft lignin, Indulin AT, was processed into a guaiacol-rich stream using base-catalyzed depolymerization. This stream was subsequently upgraded using liquid-liquid extraction and evaporation to yield a more concentrated and less inhibitory stream, adapted for bioconversion. Finally, guaiacol was quantitatively converted to muconic acid through bioconversion using an engineered Pseudomonas putida strain containing cytochrome P450 and ferredoxin reductase for guaiacol assimilation and deletion of the native catBC genes for muconic acid production. Isomerization of muconic acid in a fermentation medium depending on pH was also studied.
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| 8. |
- Antonio, Capezza, et al.
(författare)
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Advances in the use of protein-based materials: towards sustainable naturally sourced absorbent materials
- 2019
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Ingår i: American Chemical Society Symposium Series (ACS). - : American Chemical Society (ACS). - 0097-6156 .- 1947-5918. ; 7:5
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Tidskriftsartikel (refereegranskat)abstract
- Superabsorbent polymers (SAPs) are important in the health-care and personal care industries. Products like bed pads and diapers improve the comfort and sanitary conditions for people all over the world, with SAPs reaching yearly production volumes of ca. 2 million tons. However, recent sustainability issues have questioned the high negative footprint of polymers from nonrenewable resources. Biomacromolecules, especially when functionalized, have properties that make them an attractive alternative for the production of biobased SAPs. Proteins are a particularly interesting alternative due to their high variability and because of their relatively low price, being available as side streams from the agricultural industries. Due to the harsh extraction conditions, these side stream proteins are not competing with the food industry and alternative source-effective uses are advantageous in a circular bioeconomy. As the properties of a SAP material come from a combination of neutralized functional groups to promote polar liquid uptake and intermolecular cross-links to prevent dissolution, proteins offer unique opportunities due to their variability in polymerization. An increased understanding of the protein characteristics and how these can be tuned through functionalization is therefore a prerequisite for the successful development of a commercial biobased SAP that utilizes industrial and nontoxic wastes toward more sustainable products. This review focuses on proteins as biomacromolecules with relevant characteristics for superabsorbent functions, and discusses the opportunities that they may offer toward sustainable SAPs utilizing nontoxic chemicals and following the green chemistry principles.
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| 9. |
- Arias, Veluska, et al.
(författare)
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Homocomposites of Polylactide (PLA) with Induced Interfacial Stereocomplex Crystallites
- 2015
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Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 3:9, s. 2220-2231
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Tidskriftsartikel (refereegranskat)abstract
- The demand for “green” degradable composite materials increases with growing environmental awareness. The key challenge is achieving the preferred physical properties and maintaining their eco-attributes in terms of the degradability of the matrix and the filler. Herein, we have designed a series of “green” homocomposites materials based purely on polylactide (PLA) polymers with different structures. Film-extruded homocomposites were prepared by melt-blending PLA matrixes (which had different degrees of crystallinity) with PLLA and PLA stereocomplex (SC) particles. The PLLA and SC particles were spherical and with 300–500 nm size. Interfacial crystalline structures in the form of stereocomplexes were obtained for certain particulate-homocomposite formulations. These SC crystallites were found at the particle/matrix interface when adding PLLA particles to a PLA matrix with d-lactide units, as confirmed by XRD and DSC data analyses. For all homocomposites, the PLLA and SC particles acted as nucleating agents and enhanced the crystallization of the PLA matrixes. The SC particles were more rigid and had a higher Young’s modulus compared with the PLLA particles. The mechanical properties of the homocomposites varied with particle size, rigidity, and the interfacial adhesion between the particles and the matrix. An improved tensile strength in the homocomposites was achieved from the interfacial stereocomplex formation. Hereafter, homocomposites with tunable crystalline arrangements and subsequently physical properties, are promising alternatives in strive for eco-composites and by this, creating materials that are completely degradable and sustainable.
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| 10. |
- Arias, Veluska, et al.
(författare)
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Toward "Green" Hybrid Materials : Core-Shell Particles with Enhanced Impact Energy Absorbing Ability
- 2016
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Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 4:7, s. 3757-3765
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Tidskriftsartikel (refereegranskat)abstract
- Restrained properties of "green" degradable products drive the creation of materials with innovative structures and retained eco-attributes. Herein, we introduce the creation of impact modifiers in the form of core-shell (CS) particles toward the creation of "green" composite materials. Particles with CS structure constituted of PLA stereocomplex (PLASC) and a rubbery phase of poly(epsilon-caprolactone-co-D,L-lactide) (P[CL-co-LA]) were successfully achieved by spray droplet atomization. A synergistic association of the soft P[CL-co-LA] and hard PLASC domains in the core-shell structure induced unique thermo-mechanical effects on the PLA-based composites. The core-shell particles enhanced the crystallization of PLA matrices by acting as nucleating agents. The core-shell particles functioned efficiently as impact modifiers with minimal effect on the composites stiffness and strength. These findings provide a new platform for scalable design of polymeric-based structures to be used in the creation of advanced degradable materials.
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