Beneficiation of the tailings from Iron Oxide Apatite (IOA) ore has become an important topic in the field of mineral processing as phosphate rock is considered as critical raw material by the European Union. Driven by the strong call for sustainability and green technology, this paper introduces the application of novel and bio-based organosolv lignin particles (OLP) as a reagent for apatite flotation. In the artificial mineral mixture flotation tests, OLP addition or replacement to tall oil fatty acid-based collector (TOFA) was shown to improve flotation kinetics and recovery. In this study, it was demonstrated that one of the widely used commercial TOFA collectors could be replaced with OLP by 70 %. The replacement led to an increase in recovery (+2%) and only a minimal decrease in P grade (−0.3 %) for the rougher-cleaner flotation tests in one of the two feed types tested. The influence of OLP and other reagents on apatite floatability has been investigated through Hallimond tube tests and laboratory scale batch flotation tests as well as zeta potential measurements and spectroscopy tests to further understand the possible mechanism and synergism of reagents in the apatite flotation system.

The green transition is driving a steep increase in the demand for minerals, which has put the focus on more responsible and sustainable mining practices as there is a growing pressure on mining operations to minimise their environmental footprint, mitigate risks in neighbouring communities, and decrease the consumption of natural resources. In 2022, mineral froth flotation was used to recover 18 million tonnes of copper from copper ore, accounting for 80% of total copper mine output. The mineral froth flotation process can be made more sustainable through the use of bio-based and biodegradable flotation reagents. Currently, xanthates are used as collectors for the recovery of copper-bearing sulfide minerals from sulfide ores. However, xanthates are fossil-based and pose significant risks, particularly to aquatic life and ecosystems. Additionally, a significant part of xanthates is currently obtained from production sites in Asia, which can lead to supply dependency and delays, as evident during the global pandemic.

The aim of this thesis was to develop an efficient, sustainable, and environmentally friendly mineral froth flotation process based on total or partial replacement of xanthates with bio-based, biodegradable, and low-carbon footprint organosolv lignin particles (OLP). The lignin was obtained through organosolv fractionation of residual forest biomass, i.e. spruce and birch. The particles were produced via solvent exchange method from the homogenized lignin solution. As a result, 4 different particle types were produced: birch nanoparticles (BN), birch microparticles (BM), spruce nanoparticles (SN), and spruce microparticles (SM). At first, the characterization and surface chemistry study of the OLP was carried out to deepen the understanding of interaction mechanism between the OLP and mineral surfaces. The lignin was characterized by gel permeation chromatography and nuclear magnetic resonance for its molecular size and content of functional groups. While morphology, surface charge and stability in dispersion of the particles was determined using scanning electron microscopy, ζ-potential, and Turbiscan. All 4 particles were spherical with the diameter around 100 nm for nanoparticles and 1μm for microparticles. The ζ-potential measurement showed the surface variation caused by the difference in size and content of functional groups. Spruce particles, SN and SM, had higher negative charge due to higher content of carboxylic and total phenolic groups. Under alkali conditions, the ζ-potential below -20mV for all particles, with the lowest at −55.1 mV for SM. Finaly, the interaction of OLP with mineral surfaces was examined using quartz crystal microbalance. While the attachment of all OLP was very rigid for both, chalcopyrite and pyrite surfaces, the affinity for attachment was notably greater in the case of pyrite compared to chalcopyrite.

The OLP was tested in proof-of-concept study on three different ore samples, and improvements in the flotation performance was observed, including better selectivity and increased recovery. The further evaluation of the OLP as flotation reagent was conducted with copper ore samples. The flotation trials were carried out with 600 g of ore sample in laboratory flotation cell. Starting with the dosage study, the results were confirmed in rougher-cleaner flotation tests. However, the OLP could not be used as a sole collector, it was shown that significant part of xanthate in the flotation mix could be replaced by OLP resulting in improved copper recovery and selectivity. Additionally, a synergy was observed when the OLP and xanthate mixture was used as combined reagents performed better than each of them separately at the same dosage. The copper recovery was increased from 82.2% to 88.7% in a semi-pilot rougher flotation when 50% of xanthate was replaced by OLP compared to the xanthate alone. Significant depression of iron recovery was observed when the OLP was utilized, even in absence of lime. Thus, the OLP reagents eliminated the need for lime, which is required on an industrial scale. Further positive effect of OLP application was indicated recovery of other valuable elements in the concentrates, such as cobalt and molybdenum, while there was no increase in penalty elements. The amount of OLP needed was up to 10 g/ton of ore, which is very small amount, and it is roughly 10 times less compared to any other modifier used in such a process. Therefore, this thesis demonstrates the potential of OLP as flotation reagent. If implemented, the proposed flotation system would lead to better resource efficiency and lower environmental impact.

Organosolv lignin nanoparticles have been recently evaluated for their use in mineral froth flotation as a flotation reagent, and as a result, the recovery of the target minerals was improved and the selectivity of the process was increased. However, the mechanism of lignin activity in mineral froth flotation is not known. Therefore, this study is the first step in understanding the interaction of organosolv lignin with the mineral surface. As such, the organosolv lignin was characterized by GPC and 31P NMR, where the structural differences between the birch and spruce lignins were determined. The molecular size and lignol unit composition were evaluated. Subsequently, the morphology and size of the organosolv lignin particles were examined for all 4 produced types: BN, BM, SN, and SM. The ? potential was measured in the pH range of 2-11. All particles had a high negative charge, which indicated good stability of the dispersion in the alkali range. The stability of their colloidal dispersion was observed under increasing concentrations of mono- and divalent cations, and electrostatic repulsion was identified as the main stabilization mechanism. Finally, QCM-D was used to study the interaction of the lignin particles with the mineral surfaces of chalcopyrite, pyrite, and galena, which gave insight into the possible mechanism during the flotation process.

Flotation is a key step during mineral separation. Xanthates are the most commonly used collectors for recovering Cu, Ni, and Zn from sulphide ores. However, xanthates are fossil-based and toxic for the environment. The aim of this study was to evaluate the use of lignin nanoparticles and microparticles as sustainable and environmentally friendly collectors. Lignin particles demonstrated good selectivity toward Cu (chalcopyrite), with total recoveries exceeding 80% and grades of up to 8.6% w/w from a Cu-Ni ore in rougher flotation tests. When floating Zn-Pb-Cu ore, lignin nanoparticles could reduce the use of xanthates by 50%. Moreover, they outperformed xanthates alone, achieving total recoveries of up to 91%, 85%, and 98% for Cu, Pb, and Zn, respectively. These results prove the potential of lignin as a flotation collector.

The rising demand for surfactants by the pharmaceuticals and cosmetic industries has generated vast amounts of petroleum-based synthetic surfactants, which are often toxic and non-degradable. Owing to their low toxicity, stability in extreme conditions, and biodegradability, biosurfactants could represent a sustainable alternative. The present study aimed to maximize the production of rhamnolipids (RL) from Pseudomonas aeruginosa by optimizing glucose concentration, temperature, and C/N and C/P ratios. After 96 h of cultivation at 37 °C, the final RL concentration was 4.18 ± 0.19 g/L with a final yield of 0.214 ± 0.010 g/gglucose when pure glucose was used as a carbon source. At present, the main obstacle towards commercialization of RL production is economic sustainability, due to the high cost of downstream processes and media components. For this reason, a renewable source such as wood hydrolysates (from birch and spruce woodchips) was examined here as a possible source of glucose for RL production. Both hydrolysates proved to be adequate, resulting in 2.34 ± 0.17 and 2.31 ± 0.10 g/L of RL, respectively, and corresponding yields of 0.081 ± 0.006 and 0.089 ± 0.004 g/gsugar after 96 h. These results demonstrate the potential of using renewable biomass for the production of biosurfactants and, to the best of our knowledge, they constitute the first report on the use of wood hydrolysates for RL production.

Biofuels are essential for transitioning to a sustainable society. This switch can be achieved by introducing novel feedstocks and technologies for efficient and economically feasible biofuel production. Second-generation biofuels are particularly advantageous, as they are produced from nonedible lignocellulosic biomass derived primarily from agricultural byproducts. Ciona intestinalis, a marine filter feeder, is cultivated to produce fish feed from the invertebrate’s inner tissue body. This process generates also vast amounts of a renewable side stream, namely the tunicate’s external cellulose-rich tunic. The aim of the present study was to evaluate the potential of the C. intestinalis tunic as a novel feedstock for bioethanol production. For this purpose, organosolv fractionation of the tunic was optimized to increase cellulose content. Enzymatic saccharification of the pretreated biomass was assessed to identify the most promising materials, which were subsequently utilized as carbon source in fermentation trials. Under optimal conditions, a titer of 38.7 g/L of ethanol, with a yield of 78.3% of the maximum theoretical, was achieved. To the best of our knowledge, this is the first report whereby organosolv pretreated tunic biomass is valorized toward bioethanol production; the current work paves the way for incorporating tunicates in bioconversion processes for the generation of biofuels and other biobased chemicals.

Background

One of the sustainable development goals focuses on the biomass-based production as a replacement for fossil-based commodities. A novel feedstock with vast potentials is tunicate biomass, which can be pretreated and fermented in a similar way to lignocellulose. Ciona intestinalis is a marine filter feeder that is cultivated to produce fish feed. While the inner tissue body is used for feed production, the surrounding tunic remains as a cellulose-rich by-product, which can be further separated into outer and inner tunic. Ethanol production from organosolv-pretreated whole-tunic biomass was recently validated. The aim of the present study was to evaluate the potential of organosolv pretreated outer-tunic biomass for the production of biofuels and cellobiose that is a disaccharide with prebiotic potential.

Results

As a result, 41.4 g/L of ethanol by Saccharomyces cerevisiae, corresponding to a 90.2% theoretical yield, was achieved under the optimal conditions when the tunicate biomass was pretreated at 195 °C for 60 min at a liquid-to-solid ratio of 50. In addition, cellobiose production by enzymatic hydrolysis of the pretreated tunicate biomass was demonstrated with a maximum conversion yield of 49.7 wt. %.

Conclusions

The utilisation of tunicate biomass offers an eco-friendly and sustainable alternative for value-added biofuels and chemicals. The cultivation of tunicate biomass in shallow coastal sea improves the quality of the water and ensures sustainable production of fish feed. Moreover, there is no competition for arable land, which leaves the latter available for food and feed production.

The aim of this study was to assess the effect of hot water extraction followed by organosolv pretreatment on the enzymatic hydrolysability of spruce bark biomass. To this end, samples were pretreated at five different temperatures in the presence or not of acid catalyst. The cellulose content of pre-treated biomass reached 49.6% w/w. During the enzymatic hydrolysis trials with 3% w/w dry solids, the final hydrolysis yield reached up to 70.1%, which corresponded to the release of 7.8 g/L of glucose. Whereas, the final hydrolysis yield obtained during the high-gravity enzymatic hydrolysis reached up to 43.5%. The concentration of released glucose was in range of 33.3 – 40.0 g/L with a hemicellulose sugars in a range of 5.5 – 6.6 g/L. These values are suitable for downstream bioconversion processes and represent a significant improvement over existing steam pretreatment methods.

The production of high added-value chemicals from renewable resources is a necessity inour attempts to switch to a more sustainable society. 3-Hydroxypropionic acid (3HP) is a promisingmolecule that can be used for the production of an important array of high added-value chemicals,such as 1,3-propanediol, acrylic acid, acrylamide, and bioplastics. Biological production of 3HP hasbeen studied extensively, mainly from glycerol and glucose, which are both renewable resources.To enable conversion of these carbon sources to 3HP, extensive work has been performed to identifyappropriate biochemical pathways and the enzymes that are involved in them. Novel enzymeshave also been identified and expressed in host microorganisms to improve the production yieldsof 3HP. Various process configurations have also been proposed, resulting in improved conversionyields. The intense research efforts have resulted in the production of as much as 83.8 g/L 3HP fromrenewable carbon resources, and a system whereby 3-hydroxypropionitrile was converted to 3HPthrough whole-cell catalysis which resulted in 184.7 g/L 3HP. Although there are still challengesand difficulties that need to be addressed, the research results from the past four years have been animportant step towards biological production of 3HP at the industrial level.

Lignocellulosic biomass represents an excellent alternative to fossil fuels in terms of both energy production and raw material usage for a plethora of daily-use products. Organosolv pretreatment is a fractionation technique able to separate lignocellulosic biomass into individual streams of cellulose, hemicellulose, and lignin under controlled conditions. Sawdust, the by-product of sawmill processing of Picea abies wood, was the subject of our investigation in this work. The aim was to evaluate the effects of different parameters of the organosolv process of spruce sawdust on the yield of components and how this affects the enzymatic saccharification of cellulose. Sixteen distinct pretreatments were performed with ethanol concentrations of 50 and 60% v/v at 180 and 200 °C for 15 and 30 min. Half of the pretreatments contained 1% sulfuric acid as a catalyst, while the other half were acid-free. Thereafter, the effects of different variables on the yield of products were assessed and compared to determine the ideal pretreatment condition. The results showed that cellulose-rich pulps, with cellulose content as high as 55% were generated from an initial mass of 37.7% spruce sawdust with the reactor operating at 180 °C for 30 min using 60% ethanol and 1% sulfuric acid. With the pretreatments performed with the catalyst at 200 °C, hemicellulose was almost entirely removed from the pulps obtained. The recovered hemicellulose fraction was composed mainly of monomers achieving up to 10 g/100 g of biomass. Delignification values of up to 65.7% were achieved with this pretreatment technique. Fractionated lignin presented low levels of sugar and ashes contamination, with values as low as 1.29% w/w. Enzymatic saccharification of the pretreated pulps yielded 78% cellulose hydrolysis, with glucose release higher than 0.54 g/g of biomass, indicating the potential of the pulps to be applied in a fermentation process.

The use of residual biomass for bioconversions makes it possible to decrease the output of fossil-based chemicals and pursue a greener economy. While the use of lignocellulosic material as sustainable feedstock has been tried at pilot scale, industrial production is not yet economically feasible, requiring further technology and feedstock optimization. The aim of this study was to examine the feasibility of replacing woodchips with residual sawdust in biorefinery applications. Woodchips can be used in value-added processes such as paper pulp production, whereas sawdust is currently used mainly for combustion. The main advantages of sawdust are its large supply and a particle size sufficiently small for the pretreatment process. Whereas, the main challenge is the higher complexity of the lignocellulosic biomass, as it can contain small amounts of bark and cambium. Here, we studied the fractionation of birch sawdust by organosolv pretreatment at two different temperatures and for two different durations. We evaluated the efficiency of fractionation into the three main fractions: lignin, cellulose, and hemicellulose. The cellulose content in pretreated biomass was as high as 69.2%, which was nearly double the amount in untreated biomass. The obtained lignin was of high purity, with a maximum 4.5% of contaminating sugars. Subsequent evaluation of the susceptibility of pretreated solids to enzymatic saccharification revealed glucose yields ranging from 75% to 90% after 48 h but reaching 100.0% under the best conditions. In summary, birch sawdust can be successfully utilized as a feedstock for organosolv fractionation and replace woodchips to simplify and lower the costs of biorefinery processes.

The aim of this study was to utilize the whole food waste in two stages. In the first stage, the carbohydrate and protein fractions of food waste recovered after enzymatic hydrolysis was used to cultivate heterotrophic microalgae, resulting in biomass yield of 0.346 ± 0.09 g/g_sugars and lipid yield of 0.216 ± 0.06 g/g_sugars. In the second stage, oil (14.15% w/w) was extracted from food waste after hydrolysis and converted to biodiesel by a two-step transesterification reaction that generated 135.8 g/kg_{food waste} of fatty acid methyl esters and 13.8 g/kg_{food waste} of crude glycerol. Finally, crude glycerol obtained from both processes was used at 20 g/L to cultivate heterotrophic microalgae, resulting in a cell dry weight and total lipid concentration of 6.23 g/L and 2.91 g/L, respectively. A total 248.21 g of fatty acid methyl esters were obtained from the 1 kg of food waste through this integrated process.

Polyunsaturated fatty acids (PUFAs) are essential for human function, however they have to be provided through the diet. As their production from fish oil is environmentally unsustainable, there is demand for new sources of PUFAs. The aim of the present work was to establish the microalgal platform to produce nutraceutical-value PUFAs from forest biomass. To this end, the growth of Phaeodactylum tricornutum on birch and spruce hydrolysates was compared to autotrophic cultivation and glucose synthetic media. Total lipid generated by P. tricornutum grown mixotrophically on glucose, birch, and spruce hydrolysates was 1.21, 1.26, and 1.29 g/L, respectively. The highest eicosapentaenoic acid (EPA) production (256 mg/L) and productivity (19.69 mg/L/d) were observed on spruce hydrolysates. These values were considerably higher than those obtained from the cultivation without glucose (79.80 mg/L and 6.14 mg/L/d, respectively) and also from the photoautotrophic cultivation (26.86 mg/L and 2.44 mg/L/d, respectively). To the best of our knowledge, this is the first report describing the use of forest biomass as raw material for EPA and docosapentaenoic acid (DHA) production.

Textile production has doubled in the last 20 years, but only 1% is recycled into new fibers. It is the third largest contributor to water pollution and land use, accounting for 10% of global carbon emissions and 20% of clean water pollution. A key challenge in textile recycling is blended yarns, such as polycotton blends, which consist of polyester and cotton. Chemical recycling offers a solution, in particular, alkali treatment, which hydrolyzes polyester (PET) into its components while preserving cotton fibers. However, conventional methods require high temperatures, long durations, or catalysts. Our study presents, for the first time, the heated high-ethanol alkaline aqueous (HHeAA) process that efficiently hydrolyzes PET from polycotton at lower temperatures and without a catalyst. A near-complete PET hydrolysis was achieved in 20 min at 90 °C, while similar results were obtained at 70 °C and 80 °C with longer reaction times. The process was successfully scaled at 90 °C for 20 min, and complete PET hydrolysis was achieved, with a significantly reduced liquid-to-solid ratio, from 40 to 7 (L per kg), signifying its potential to be implemented in an industrial context. Additionally, the cotton maintained most of its properties after the treatment. This method provides a more sustainable and efficient approach to polycotton recycling.

Mineral separation relies heavily on the process of flotation. This study explored the feasibility of using organosolv lignin nanoparticles and microparticles (OLP) as a greener alternative to xanthates in the flotation process for mineral separation. Xanthates are widely used but pose environmental and health risks. The efficiency of OLP as collectors was compared to collectorless flotation, resulting in approximately 50% copper recovery, indicating that OLP may not be a suitable replacement for xanthates. Further tests were conducted using a mixture of xanthates and OLP (birch nano and spruce micro) with varying substitution levels (20%, 30%, and 40%). The results demonstrated that increasing the dosage of OLP led to a decrease in flotation efficiency for copper. TOC analysis of the products revealed that high dosages (160 g/t) of birch nano and spruce micro as sole collectors showed beneficiation and selective recovery against copper. While OLPs did not prove effective as collectors, the study highlights their potential as substitutes for maltodextrin in selective flotation of the final concentrate. Two out of four tested OLPs were recommended for pilot scale testing.