Rigid Polyurethane Foams' Development and Optimization from Polyols Based on Depolymerized Suberin and Tall Oil Fatty Acids.

The utilization of polyols derived from renewable sources presents an opportunity to enhance the sustainability of rigid polyurethane (PUR) foams, thereby contributing to the advancement of a circular bioeconomy. This study explores the development of PUR rigid foams exclusively using polyols sourced from second-generation renewable biomass feedstocks, specifically depolymerized birch bark suberin (suberinic acids) and tall oil fatty acids. The polyols achieved a total renewable material content as high as 74%, with a suberinic acid content of 37%. Response surface modeling was employed to determine the optimal bio-polyol, blowing agents, and catalyst content, hence, optimizing the bio-based foam formulations. In addition, response surface modeling was applied to rigid PUR foam formulations based on commercially available petroleum-based polyols for comparison. The results, including apparent density (~40-44 kg/m3), closed cell content (~95%), compression strength (>0.2 MPa, parallel to the foaming direction), and thermal conductivity (~0.019 W/(m·K)), demonstrated that the suberinic acids-based rigid PUR foam exhibited competitive qualities in comparison to petroleum-based polyols. Remarkably, the bio-based rigid PUR foams comprised up to 29% renewable materials. These findings highlight the potential of suberinic acid-tall oil polyols as effective candidates for developing rigid PUR foams, offering promising solutions for sustainable insulation applications.

Catalyzed Hydrothermal Pretreatment of Oat Husks for Integrated Production of Furfural and Lignocellulosic Residue.

This study presents a novel approach for biorefining oat husks into furfural, leveraging a unique pilot-scale setup. Unlike conventional furfural manufacturing processes, which often result in substantial cellulose degradation and environmental concerns associated with sulfuric acid usage, our method utilizes phosphoric acid as a catalyst to achieve high furfural yield while minimizing cellulose destruction. Drawing on our research conducted in a distinctive pilot-scale environment, we successfully developed and implemented a tailored biorefining process for oat husks. Through meticulous experimentation, we attained a remarkable furfural yield of 11.84% from oven-dried mass, accompanied by a 2.64% yield of acetic acid. Importantly, our approach significantly mitigated cellulose degradation, preserving 88.31% of the cellulose content in oat husks. Existing catalytic (H2SO4) furfural manufacturing processes often lead to substantial cellulose degradation (40-50%) in lignocellulosic leftover during the pretreatment stage. As a result of the research, it was also possible to reduce the destruction of cellulose in the lignocellulose leftover to 11.69% of the output (initial) cellulose of oat husks. This research underscores the feasibility and sustainability of utilizing oat husks as a valuable feedstock for furfural production, highlighting the potential of phosphoric acid as a catalyst in biorefining processes. By showcasing our unique pilot-scale methodology, this study contributes to advancing the field of environmentally friendly biorefining technologies.

Innovative Approach to Enhance Bioavailability of Birch Bark Extracts: Novel Method of Oleogel Development Contrasted with Other Dispersed Systems.

Birch outer bark extract (BBE), containing pentacyclic triterpenes such as betulin, lupeol, and betulinic acid, is a widely recognized natural product renowned for its diverse pharmacological effects. However, its limited water solubility restricts its bioavailability. Therefore, the main objective is to enhance the bioavailability of BBE for pharmaceutical use. In this study, we aimed to develop a dispersion system utilizing a unique oleogel-producing method through the recrystallization of BBE from an ethanol solution in the oil phase. We generated an oleogel that demonstrates a notable 42-80-fold improvement in betulin and lupeol peroral bioavailability from BBE in Wistar rats, respectively. A physical paste-like BBE hydrogel developed with antisolvent precipitation showed a 16-56-fold increase in the bioavailability of betulin and lupeol from BBE in rat blood plasma, respectively. We also observed that the repeated administration of the BBE oleogel did not exhibit any toxicity at the tested dose (38.5 mg/kg betulin, 5.2 mg/kg lupeol, 1.5 mg/kg betulinic acid daily for 7 days). Betulin and betulinic acid were not detected in rat heart, liver, kidney, or brain tissues after the peroral administration of the oleogel daily for 7 days. Lupeol was found in rat heart, liver, and kidney tissues.

Evaluation of Oleogels Stabilized by Particles of Birch Outer Bark Extract through a Novel Approach.

Structuring liquid oils into oleogels using natural and abundant biomass components as gelling agents is of great significance in fields such as foods, pharmaceuticals, and cosmetics. In this work, a more energy-efficient and technologically simpler approach for directly preparing birch outer bark extract particles containing oleogel was used. This method involves introducing birch outer bark extract particles into the oil phase directly from the extract solution, combining both the evaporation of solution and gel formation. As a result, stable oleogels of various vegetable oils (sunflower, almond, olive, and hemp seed) were obtained with birch outer bark extract particle contents of 4-10%. Infrared spectroscopy and particle size analysis confirmed that when increasing the content of extract particles in the oil, increasing self-assembly of extract particles via hydrogen bonding occurs, leading to the formation of a more structured network. This is consistent with gel strength values from rheological tests of oleogels, which also increased with particle concentration. The obtained oleogels showed important properties such as good tolerance to time-dependent deformation, shear thinning, and thermoreversibility.

Effect of Betulin Colloidal Particles on Proliferation and Cytokine Secretion of Human Skin Fibroblasts.

The aim of the study was to obtain untreated and treated betulin colloidal particles and assess their effect on the viability, morphology, proliferation and cytokine secretion of human dermal fibroblasts. To improve bioavailability, betulin treatment was performed by an antisolvent precipitation technique. The average particle size after treatment in the aqueous dispersion decreased from 552.9 ± 11.3 to 278.2 ± 1.6 nm. Treated betulin colloidal particles showed no cytotoxicity up to a concentration of 400 µg·mL-1 in the colorimetric tetrazolium salt viability test (CCK-8). Moreover, the cell morphology was not changed in the presence of betulin colloidal particles at a concentration range from 0.78 to 400 µg·mL-1. The obtained results also show that betulin particles induce the secretion of the proinflammatory and angiogenesis-stimulating cytokine IL-8. However, further studies would be required to clarify the mechanism of IL-8 secretion induction.

Rigid Polyurethane Foams as Thermal Insulation Material from Novel Suberinic Acid-Based Polyols.

Developing polyols from biomass sources contributes to a more circular economy by replacing petroleum-based polyols in the vast production of polyurethanes (PUR). One such potential biomass source could be leftover birch bark from which suberinic acids (SA) can be obtained. The purpose of this study was to identify the best synthesis routes for novel SA-based polyols, obtain rigid PUR foams, and evaluate their competitiveness and potential suitability as thermal insulation material. Novel polyols were synthesized from depolymerized SA by esterification with various functionality and molecular weight alcohols in several molar ratios. The moisture content, hydroxyl and acid values, and apparent viscosity were tested. Free-rise rigid PUR foams from the most suitable SA-based polyol and tall oil-based polyol were successfully prepared, reaching ~20 wt.% total renewable material content in the foam. The obtained rigid PUR foams' morphological, mechanical, and thermal properties were investigated and compared to present foam materials, including commercial foams. The apparent density (~33 kg/m3), as well as the closed cell content (~94%), compression strength (0.25 MPa, parallel to the foaming direction), and thermal conductivity (~0.019 W/(m·K)), approved the competitiveness and potential ability of SA-based rigid PUR foam production as thermal insulation material.

Analytical Method Cluster Development for Comprehensive Characterisation of Suberinic Acids Derived from Birch Outer Bark.

Suberin is a complex polyester biopolymer, and it is practically impossible to estimate the real content of suberin in suberised plant tissues. This indicates the importance of the development of instrumental analytical methods for the comprehensive characterisation of suberin derived from plant biomass for the successful integration of suberinic products into biorefinery production chains. In this study, we optimised two GC-MS methods-one with direct sylilation, and the second with additional depolymerisation, using GPC methods with RI detector and polystyrene calibration and with a three-angle light scattering detector and an eighteen-angle light scattering detector. We also performed MALDI-Tof analysis for non-degraded suberin structure determination. We characterised suberinic acid (SA) samples obtained from birch outer bark after alkaline depolymerisation. The samples were particularly rich in diols, fatty acids and their esters, hydroxyacids and their corresponding esters, diacids and their corresponding esters, as well as extracts (mainly betulin and lupeol) and carbohydrates. To remove phenolic-type admixtures, treatment with ferric chloride (FeCl3) was used. The SA treatment with FeCl3 allows the possibility to obtain a sample that has a lower content of phenolic-type compounds and a lower molecular weight than an untreated sample. It was possible to identify the main free monomeric units of SA samples by GC-MS system using direct silylation. By performing an additional depolymerisation step before silylation, it was possible to characterise the complete potential monomeric unit composition in the suberin sample. For the molar mass distribution determination, it is important to perform GPC analysis. Even though chromatographic results can be obtained using a three- laser MALS detector, they are not fully correct because of the fluorescence of the SA samples. Therefore an 18-angle MALS detector with filters was more suitable for SA analysis. MALDI-Tof analysis is a great tool for the polymeric compound structural identification, which cannot be done using GC-MS. Using the MALDI data, we discovered that the main monomeric units that makes up the SA macromolecular structure are octadecanedioic acid and 2-(1,3-dihydroxyprop-2-oxy)decanedioic acid. This corresponds with GC-MS results, showing that after depolymerisation hydroxyacids and diacids were the dominant type of compounds found in the sample.

Direct Furfural Production from Deciduous Wood Pentosans Using Different Phosphorus-Containing Catalysts in the Context of Biorefining.

This study seeks to improve the effectiveness of the pretreatment stage when direct furfural production is integrated into the concept of a lignocellulosic biomass biorefinery. First of all, the catalytic effects of different phosphorus-containing salts (AlPO4, Ca3(PO4)2, FePO4, H3PO4, NaH2PO4) were analysed in hydrolysis for their ability to convert birch wood C-5 carbohydrates into furfural. The hydrolysis process was performed with three different amounts of catalyst (2, 3 and 4 wt.%) at a constant temperature (175 °C) and treatment time (90 min). It was found that the highest amount of furfural (63-72%, calculated based on the theoretically possible yield (% t.p.y.)) was obtained when H3PO4 was used as a catalyst. The best furfural yield among the used phosphorus-containing salts was obtained with NaH2PO4: 40 ± 2%. The greatest impact on cellulose degradation during the hydrolysis process was observed using H3PO4 at 12-20% of the initial amount, while the lowest degradation was observed using NaH2PO4 as a catalyst. The yield of furfural was 60.5-62.7% t.p.y. when H3PO4 and NaH2PO4 were combined (1:2, 1:1, or 2:1 at a catalyst amount of 3 wt.%); however, the amount of cellulose that was degraded did not exceed 5.2-0.3% of the starting amount. Enzymatic hydrolysis showed that such pretreated biomass could be directly used as a substrate to produce glucose. The highest conversion ratio of cellulose into glucose (83.1%) was obtained at an enzyme load of 1000 and treatment time of 48 h.

Thermomechanical and Alkaline Peroxide Mechanical Pulping of Lignocellulose Residue Obtained from the 2-Furaldehyde Production Process.

The necessity for the reduction in greenhouse gas emissions, the growing demand for the improvement of biorefinery technologies, and the development of new biorefining concepts oblige us as a society, and particularly us, as scientists, to develop novel biorefinery approaches. The purpose of this study is to thoroughly evaluate the leftover lignocellulosic (LC) biomass obtained after the manufacture of 2-furaldehyde, with the intention of further valorizing this resource. This study demonstrates that by using thermomechanical and alkaline peroxide mechanical pulping techniques, birch wood chips can be used in the new biorefinery processing chain for the production of 2-furaraldehyde, acetic acid, and cellulose pulp. In addition, the obtained lignocellulosic residue is also characterized. To produce a lignocellulosic material without pentoses and with the greatest amount of cellulose fiber preserved for future use, a novel bench-scale reactor technology is used. Studies were conducted utilizing orthophosphoric acid as a catalyst to deacetylate and dehydrate pentose monosaccharides found in birch wood, converting them to 2-furaldehyde and acetic acid. The results showed that, with the least amount of admixtures, the yields of the initial feedstock's oven-dried mass (o.d.m.) of 2-furaldehyde, acetic acid, and lignocellulose residue ranged from 0.04 to 10.84%, 0.51 to 6.50%, and 68.13 to 98.07%, respectively, depending on the pretreatment conditions utilized. The ideal 2-furaldehyde production conditions with reference to the purity and usability of cellulose in residual lignocellulosic material were also discovered through experimental testing. The experiment that produced the best results in terms of 2-furaldehyde yield and purity of residual lignocellulose used a catalyst concentration of 70%, a catalyst quantity of 4%, a reaction temperature of 175 °C, and a treatment period of 60 min. It was possible to create pulp with a tensile index similar to standard printing paper by mechanically pulping the necessary LC residue with alkaline peroxide, proving that stepwise 2-furaldehyde production may be carried out with subsequent pulping to provide a variety of value-added goods.

Qualitative Differences and Emission Persistence of Volatile Organic Compounds from Bio-Based Particleboards.

An attempt to reduce, replace, or even eliminate the synthetic resins from wood-based panels alongside broadening the array of raw lignocellulosics is still essential and attractive. Many pretreatments of lignocellulosics have been studied, among which steam explosion (SE) resulted in superior physical-mechanical properties of the obtained binder-less boards. However, the SE pretreatment leads to a relatively strong odor, which is even emitted from the obtained binder-less boards independent of the raw lignocellulosic, raising concern about the use of the boards. Emissions of volatile organic compounds (VOCs) were investigated in the framework of the study from binder-less boards obtained from different SE raw lignocellulosics and SE-untreated suberinic acids-bonded particleboard. VOCs were collected by headspace solid-phase microextraction (HS-SPME) and analyzed by gas chromatography-mass spectrometry (GC-MS) for 28 days with an interval of 2 weeks. The results showed that the number of detected VOCs and their chromatographic peak area varied significantly depending on the raw lignocellulosic, board density, and post-treatment (overlayering), decreasing over time. The lowest area of detected VOCs was demonstrated by the suberinic acids-bonded particleboard, while the highest area was detected from the high-density binder-less board obtained from SE hemp shives with the main compound of furfural (up to 70%) in all board types.

Utilization of Suberinic Acids Containing Residue as an Adhesive for Particle Boards.

The birch (Betula spp.) outer bark is a valuable product rich in betulin. After removal of betulin extractives, suberin containing tissues are left. Suberin is a biopolyester built from α,ω-bifunctional fatty acids (suberinic acids), which after depolymerization together with lignocarbohydrate complex is a potential adhesive as a side-stream product (residue) from obtaining suberinic acids for polyol synthesis. In this work, we studied the utilization possibilities in particleboards of the said residue obtained by depolymerization in four different solvents (methanol, ethanol, isopropanol and 1-butanol). The adhesives were characterised by chemical (acid number, solubility in tetrahydrofuran, epoxy and ash content) and instrumental analytical methods (SEC-RID, DSC, TGA and FTIR). Based on the results of mechanical characteristics, ethanol was chosen as the most suitable depolymerization medium. The optimal hot-pressing parameters for particleboards were determined using the design of experiments approach: adhesive content 20 wt%; hot-pressing temperature 248 °C, and hot-pressing time 6.55 min.

Polyurethane Foam Composites Reinforced with Renewable Fillers for Cryogenic Insulation.

Sawdust, microcellulose and nanocellulose and their silanized forms were used to reinforce rigid polyurethane (PU) foam composites. The concentration of fillers was varied in the range of 0.5-1.5%. For rigid PU foam formulations, three polyols from recycled and renewable materials were used, among other components. Polyols were obtained from rapeseed oil, tall oil fatty acids and recycled polyethylene terephthalate. As rigid PU foam composites in literature have been described as appropriate thermal insulation material, the appliance of obtained composites for cryogenic insulation was investigated by determining the various physical-mechanical properties of composites. The physical-mechanical properties, such as the modulus of elasticity, compressive and tensile strength in both 293 K and 77 K, adhesion measurements with and without cryo-shock, apparent density, thermal conductivity coefficient, and safety coefficient were measured. The results showed that the addition of fillers did not give a significant improvement of characteristics.

Characterization of Birch Wood Residue after 2-Furaldehyde Obtaining, for Further Integration in Biorefinery Processing.

Latvia is a large manufacturer of plywood in Eastern Europe, with an annual production of 250,000 m3. In Latvia's climatic conditions, birch (Betula pendula) is the main tree species that is mainly used for plywood production. A significant part of the processed wood makes up residues like veneer shorts, cores, and cut-offs (up to 30%), which have a high potential for value-added products. The aim of this research was to comprehensively characterize lignocellulosic (LC) biomass that was obtained after 2-furaldehyde production in terms of further valorization of this resource. The polymeric cellulose-enriched material can be used in the new biorefinery concept for the production of 2-furaldehyde, acetic acid, cellulose pulp, thermomechanical (TMP) and an alkaline peroxide mechanical (APMP) pulping process. In addition, we experimentally developed the best 2-furaldehyde production conditions to optimize the purity and usability of cellulose in the leftovers of the LC material. The best experimental results in terms of both 2-furaldehyde yield and the purity of residual lignocellulose were obtained if the catalyst concentration was 70%, the catalyst amount was 4 wt.%, the reaction temperature was 175 °C,and the treatment time was 60 min. After process optimization with DesignExpert11, we concluded that the best conditions for maximal glucose content (as cellulose fibers) was a catalyst concentration of 85%, a catalyst amount of 5 wt.%, a temperature of 164 °C, and a treatment time of 52 min.

Suberinic Acids as a Potential Feedstock for Polyol Synthesis: Separation and Characterization.

Global sustainability challenges prompt the world to modify its strategies and shift from a fossil-fuel-based economy to a bio-resources-based one and to the production of renewable biomass chemicals. Depolymerized suberinic acids (SA) were considered as an alternative resource to develop bio-polyols that can be further used in polyurethane (PU) material production. Birch (Betula pendula) outer bark was used as a raw material to obtain the SA, extracted with ethanol, and depolymerized with potassium hydroxide ethanol solution. By acidifying the filtrate to pH 5.0, 3.0, and 1.0 and drying it at 50 °C and 130 °C, 12 different SA potential feedstocks were obtained and characterized using chemical (total phenolics content, solubility in DMSO, acid, hydroxyl, and saponification number) and instrumental analytical methods (GC-MS, SEC-RID, DSC, and FTIR). Several bio-polyols were synthesized from the SA sample acidified to pH 1 and dried at 130 °C. Acid number and hydroxyl number values, the apparent viscosity and moisture content were measured. It was concluded that SA have a high enough saponification and acid value to investigate the polyol synthesis route via the esterification reaction. Moreover, SA had OH groups in their structure, which can be exploited for PU material development. The majority of SA compounds had relatively low molecular weight with <1300 Da that are suited for bio-polyol synthesis applied for rigid PU foam development. The synthesized bio-polyols had high hydroxyl number values necessary for bio-polyols to be used for rigid PU foam production.

Residual Birch Wood Lignocellulose after 2-Furaldehyde Production as a Potential Feedstock for Obtaining Fiber.

From birch wood, it is possible to obtain both acetic acid and 2-furaldehyde as valuable value-added products. The main objective of this study was to develop a new wasteless technology for obtaining 2-furaldehyde, acetic acid, and lignocellulose (LC) residue usable as feedstock in further processing such as thermomechanical (TMP), alkaline peroxide mechanical (APMP), and sulfate pulping processes. To achieve this objective several screening tests were performed, and a further experimental plan was developed using DesignExpert11. Process yields were analyzed both in terms of total yield and at individual time increments. In addition, the obtained LC residue was also characterized. A unique bench-scale reactor system was used to obtain an LC material without pentoses and with maximum preservation of cellulose fiber for further research. Studies on the deacetylation and dehydration of birch wood hemicelluloses of pentose monosaccharides to 2-furaldehyde and acetic acid using orthophosphoric acid as a catalyst were carried out. Results showed that, depending on the used pre-treatment conditions, the 2-furaldehyde yield was from 0.04% to 10.84% oven dry mass (o.d.m.), the acetic acid yield was from 0.51% to 6.50% o.d.m., and the LC residue yield was from 68.13% to 98.07% o.d.m. with minimal content of admixtures. Process optimization using DesignExpert11 revealed that the main pre-treatment process parameters that influenced the yield of 2-furaldehyde in the pre-treatment process were process temperature (53.3%) and process duration (29.8%).

Obtaining lignocellulosic biomass-based catalysts and their catalytic activity in cellobiose hydrolysis and acetic acid esterification reactions.

Global challenges prompt the world to modify its strategies and shift from a fossil-fuel-based economy to a bio-resource-based one with the production of renewable biomass chemicals. Different processes exist that allow the transformation of raw biomass into desirable bio-based products and/or energy. In this work different biochars that were obtained as a by-product from birch chip fast pyrolysis and carbonization were used as is or chemically/physically treated. These sulfonated carbon catalysts were compared to a commercially available sulfonated styrene-divinylbenzene macroreticular resin (Dowex 50W X8). Characterisation (water content and pH value, FTIR, base titration, element analysis and N2 desorption) was done to evaluate the obtained sulfonated biocarbon catalysts. Catalytic activity was tested using cellobiose (CB) hydrolysis and acetic acid esterification. For the catalytic CB hydrolysis, we tested the reaction temperature, time and CB and catalyst mass ratios. The determined optimal conditions were 120 °C and 24 h, with CB and catalyst mass ratio 1 : 5. The highest glucose yield was observed for biochar obtained from the birch chip fast pyrolysis process (BC_Py-H2SO4) - 92% within 24 h for 120 °C. Comparably high glucose yield was observed for biochar that was obtained in birch chip carbonization (BC_Carbon-H2SO4) - 86% within 24 h for 120 °C.