1. Hydrothermal decomposition of virgin and waste polylactic acid with subcritical water under N[sub]2 and air atmospheresMaja Čolnik, Mihael Irgolič, Mojca Škerget, 2025, izvirni znanstveni članek Opis: This study addresses the inherent shortcomings of poly (lactic acid) (PLA), a biodegradable polymer widely used in industries such as packaging and biomedical applications. The principal challenge of PLA resides in its low crystallinity, which detrimentally affects its mechanical properties and thermal stability. Additionally, PLA is prone to water and hydrolysis, which compromises its chemical resistance and can lead to degradation over time. To overcome surmount these limitations, the study focuses on the development of hybrid films through the blending of PLA with poly (l-lactide-co-ethylene adipate) (pLEA) block copolymers. The objective is to augment the crystallinity, mechanical performance, and chemical resistance of the resulting materials. The study employs a range of analytical techniques, including Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), Polarised Light Microscopy (PLM), Differential Scanning Calorimetry (DSC), and Thermogravimetric Analysis (TGA), to thoroughly characterize the copolymers and blend films. By systematically selecting blending ratios and processing methodologies, the study demonstrates enhancements in the properties of the resultant hybrid films compared to neat PLA. Specifically, the structure of films significantly changed from amorphous to crystalline in a short duration - 5 min, of annealing., leading to better tensile strength, modulus and reduced wettability, which are crucial for applications requiring durability and resistance to environmental factors. Films made from 30 wt% of pLEA 97.5/2.5 with 70 % of PLA by fast cooling exhibited outstanding mechanical properties, with a tensile strength 20 MPa higher than that of neat PLA films. Additionally, the chemical resistance may be improved, as evidenced by a decrease in wettability by approximately 15° and a reduction in the polar component of the surface free energy by about 7 mN/m. Hydrophobic, water-repellent materials resist penetration by water and other polar solvents, reducing exposure to corrosive substances and enhancing chemical resistance through barrier protection. Overall, this research addresses the limitations of PLA through innovative copolymerization and blending strategies, offering valuable insights into optimizing the material's properties for various practical applications. Ključne besede: biopolymers recycling, polylactic acid, subcritical water, lactic acid, carboxylic acids, gaseous products Objavljeno v DKUM: 01.04.2025; Ogledov: 0; Prenosov: 1
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2. Hydrolytic decomposition of corncobs to sugars and derivatives using subcritical waterMaja Čolnik, Mihael Irgolič, Amra Perva, Mojca Škerget, 2025, izvirni znanstveni članek Opis: Corncobs are a widespread and renewable by-product of corn cultivation that are typically considered waste or low-value material. Corncobs contain hemicellulose, cellulose, and lignin, which can be converted into valuable products using suitable techniques. Subcritical water is increasingly used as a green medium for the extraction of valuable components from biomass, as it has many advantageous properties (high yield, pure extracts, shorter times) compared to other organic solvents. For this reason, subcritical water was used in this study to extract valuable components from corncobs at different temperatures (150–250 °C) and reaction times (10–60 min). During the decomposition of corncobs, numerous valuable products are formed in the aqueous phase depending on the temperature and reaction time. In addition to sugars and their derivatives, phenolic compounds were also formed, which are of great importance in numerous applications. It was found that at low temperatures (150–170 °C) the hemicellulose in the corncobs begins to decompose and, in particular, the sugars (glucose, xylose, arabinose, and galactose) are initially formed in the aqueous phase. Higher temperatures (200 and 250 °C) are more favorable for the decomposition of corncobs into valuable components. The yield of sugars increases with temperature due to the degradation of the cellulose content of the lignocellulosic biomass. At the same time, several new valuable products (furfural, 5-hydroxymethylfurfural (5-HMF), 1,3-dihydroxyacetone, levulinic acid, and formic acid as well as phenolic components) are formed through the degradation of lignin and the further degradation of sugars. The most important products are certainly the furfurals, which are central platform compounds. The highest furfural content was reached at 200 °C and 60 min and accounted for almost half of all components in the aqueous phase (472.01 ± 5.64 mg/g dry extract). These biomass-derived sugars and derivatives can be used in the production of fuels, pharmaceuticals, biodegradable polymers, and surfactants. Ključne besede: corncobs, subcritical water, biomass, valuable compounds, sugar derivates Objavljeno v DKUM: 07.02.2025; Ogledov: 0; Prenosov: 8
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3. Degradation of waste tetra pak packaging with hydrothermal treatment in sub-/supercritical waterMihael Irgolič, Maja Čolnik, Petra Kotnik, Mojca Škerget, 2024, izvirni znanstveni članek Ključne besede: hydrothermal degradation, waste packing, tetra pak, subcritical water, subcritical waste, chemical recycling, one-stage process, two-stage process, product analysis Objavljeno v DKUM: 16.07.2024; Ogledov: 88; Prenosov: 26
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4. Efficient and Green Isolation of Keratin from Poultry Feathers by Subcritical WaterMojca Škerget, Maja Čolnik, Lidija Fras Zemljič, Lidija Gradišnik, Tanja Živković Semren, Blanka Tariba Lovaković, Uroš Maver, 2023, izvirni znanstveni članek Opis: The isolation of keratin from poultry feathers using subcritical water was studied in a batch reactor at temperatures (120–250 °C) and reaction times (5–75 min). The hydrolyzed product was characterized by FTIR and elemental analysis, while the molecular weight of the isolated product was determined by SDS-PAGE electrophoresis. To determine whether disulfide bond cleavage was followed by depolymerization of protein molecules to amino acids, the concentration of 27 amino acids in the hydrolysate was analyzed by GC/MS. The optimal operating parameters for obtaining a high molecular weight protein hydrolysate from poultry feathers were 180 °C and 60 min. The molecular weight of the protein hydrolysate obtained under optimal conditions ranged from 4.5 to 12 kDa, and the content of amino acids in the dried product was low (2.53% w/w). Elemental and FTIR analyses of unprocessed feathers and dried hydrolysate obtained under optimal conditions showed no significant differences in protein content and structure. Obtained hydrolysate is a colloidal solution with a tendency for particle agglomeration. Finally, a positive influence on skin fibroblast viability was observed for the hydrolysate obtained under optimal processing conditions for concentrations below 6.25 mg/mL, which makes the product interesting for various biomedical applications. Ključne besede: poultry feathers, subcritical water hydrolysis, keratin, physico-chemical characterization, cytotoxicity Objavljeno v DKUM: 28.11.2023; Ogledov: 456; Prenosov: 163
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5. Kinetics study of hydrothermal degradation of PET waste into useful productsMaja Čolnik, Darja Pečar, Željko Knez, Andreja Goršek, Mojca Škerget, 2022, izvirni znanstveni članek Opis: Kinetics of hydrothermal degradation of colorless polyethylene terephthalate (PET) waste was studied at two temperatures (300 °C and 350 °C) and reaction times from 1 to 240 min. PET waste was decomposed in subcritical water (SubCW) by hydrolysis to terephthalic acid (TPA) and ethylene glycol (EG) as the main products. This was followed by further degradation of TPA to benzoic acid by decarboxylation and degradation of EG to acetaldehyde by a dehydration reaction. Furthermore, by-products such as isophthalic acid (IPA) and 1,4-dioxane were also detected in the reaction mixture. Taking into account these most represented products, a simplified kinetic model describing the degradation of PET has been developed, considering irreversible consecutive reactions that take place as parallel in reaction mixture. The reaction rate constants (k1–k6) for the individual reactions were calculated and it was observed that all reactions follow first-order kinetics. Ključne besede: PET waste, subcritical water, kinetics, degradation, TPA Objavljeno v DKUM: 18.09.2023; Ogledov: 645; Prenosov: 191
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6. Hydrothermal processes for conversion of lignocellulosic biomass to value-added compounds : doctoral disertationTanja Milovanović, 2020, doktorska disertacija Opis: In this doctorial dissertation subcritical water processes of lignocellulosic biomass to obtain value-added compounds are studied. The doctorial dissertation is divided into four main parts. In the first and second part of dissertation, model compounds (standards of cellulose and sugars and chestnut tannins) were primarly used in order to better understand processes of real biomass material.
The degradation of cellulose and different sugars was performed in batch reactor with subcritical water. The different reaction temperatures and times were used. The main phases, such as water-soluble fraction, acetone-soluble fraction and solid residue were separated and analysed. The analysis of water-soluble phase was done by HPLC equipped with UV and RI detector, while acetone-soluble phase of cellulose was analysed by GC-MS. Total sugar content was determined by the phenol-sulphuric acid colorimetric method. The properties of char, obtained using cellulose as a treated material, such as: specific surface area, pore volume and pore diameter were determined by gas adsorption method. A water-soluble phase mainly consists of sugar monomers and monomer degradation products such as 5-hydroxymethylfurfural (5-HMF), furfural, erythrose, sorbitol, 1,6-anhydroglucose, glycolaldehyde, glycerlaldehyde, 1,3-dihydroxyacetone, pyruvaldehyde, formic, levulinic, lactic, oxalic and succinic acids, while acetone-soluble phase, referred to also as bio-oil, consists of furans, phenols, carboxylic acids, aldehydes, ketones and high molecular compounds. The reaction mechanism of cellulose and sugars in subcritical water has been proposed based on the obtained results. Furthermore, the results from cellulose and sugar hydrothermal degradation were utilized in further work to determine which industrially interesting products could be obtained by hydrothermal processing of paper waste in subcritical water. The optimum conditions ( temperature and reaction time), which gave us the highest yield of base chemicals (furfural, 5-HMF, levulinic acid) were determined.
Sweet chestnut (Castanea Sativa) bark contains high level of tannins and various phenolic compounds which can be utilized in pharmaceutical, cosmetic, nutritional and medical purposes. The sweet chestnut tannins extract and sweet chestnut bark were used as materials highly rich in bioactive compounds for subcritical water processes which are presented in the second part of doctorial dissertation, respectively. The spectrophotometric methods were used to determine total tannins, phenols and carbohydrates content and antioxidant activity. The identified compounds were ellagic and gallic acid, ellagitannins (vescalagin, castalagin, 1-o-galloyl castalagin, vescalin and castalin), sugars (maltose, glucose, fructose and arabinose) and sugar derivatives (5-HMF, furfural and levulinic acid). The results obtained from hydrothermal hydrolysis were compared to results from acid hydrolysis. Finally, the optimization of reaction parameters of subcritical water processes has been done aiming to obtain the product highly rich in ellagic acid.
Subcritical water extraction of horse chestnut (Aesculus hippocastanum) parts such as seeds, seed shell, bark and leaves was described in the third chapter of dissertation. The detected compounds in extracts, such as escins, esculin, fraxin, phenolic compounds (chlorogenic, neochlorogenic and gallic acids) and furfurals (5-hydroxymethyfurfural, furfural, and methylfufrual) are quantified using HPLC.
The last part of dissertation proposes extraction of cocoa shell using green technologies (supercritical CO2 and subcritical water extraction) and also conventional methods (Soxhlet extraction with hexane and extraction with 50 % acetone) to obtain bioactive compounds in order to compare the results. The detected compouns were methylxanthines, phenolic compounds, sugars, fatty acids. Ključne besede: Subcritical water, biomass, biowaste, extraction, hydrothermal degradation, hydrolysis, bioactive compounds. Objavljeno v DKUM: 16.10.2020; Ogledov: 1774; Prenosov: 177
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7. Subcritical water as a green medium for extraction and processing of natural materialsMatej Ravber, 2016, doktorska disertacija Opis: In this doctoral dissertation, the application of subcritical water as a green medium for
the extraction and processing of natural materials is presented. The work is divided into three
main parts. In the first part, subcritical water is proposed as a solvent for the simultaneous
extraction of oil- and water-soluble phase from oily seeds. The extraction parameters, such as
temperature, time and material to solvent ratio that yield the highest amounts of both phases
are examined. The quality of both obtained phases is examined. The characteristics of oils
obtained using subcritical water is compared to that obtained using a conventional method.
The second part of this work proposes subcritical water as an efficient solvent for the
isolation of bioactive phenolic compounds from wood waste, that is produced by the forestry
industry. Different wood fractions are firstly extracted in batch-mode and the fraction with the
highest amounts of bioactive compounds is determined. Next, semi-continuous operation is
applied, where the effects of different extraction parameters are studied on the extraction yield
and quality of the extract. The effect of temperature and ethanol addition to the subcritical
water on the content of single phenolic compounds identified in the extracts is observed.
Lastly, the cost of manufacturing of such a product is estimated by evaluating the economics
of different pilot- and industrial-scale processes operating at optimal conditions determined
on the laboratory scale.
The last part proposes the use of subcritical water as an efficient hydrolytic medium
for glycoside bonded antioxidants, specifically those found in waste agro-industrial sources.
Effect of temperature, treatment time, concentration and the atmosphere used for establishing
the pressure in the reactor are first studied on a model glycoside compound - rutin and the
optimal combination of reaction parameters are established for the batch-mode reactor. The
degradation products of the model compound are identified and the concentration/time profiles
of their degradation are observed. Furthermore, the reaction kinetics explaining the
degradation of the rutin standard are evaluated. In the next step, the method is implemented
on a real glycosides-containing extract. The extract is hydrolyzed at conditions obtained from
the first step and the free aglycone is obtained at the highest yields possible. Lastly, the process
is upgraded to continuous operation and the final hydrolyzed high-purity product is recovered. Ključne besede: Subcritical water, Biowaste, Extraction, Hydrolysis, Antioxidants, Hydrothermal degradation. Objavljeno v DKUM: 16.06.2016; Ogledov: 1904; Prenosov: 232
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