Search results for: lignocellulosic biochar

Authors: Rajeev Ravindran, Amit K. Jaiswal

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Waste from the food-processing industry is produced in large amount and contains high levels of lignocellulose. Due to continuous accumulation throughout the year in large quantities, it creates a major environmental problem worldwide. The chemical composition of these wastes (up to 75% of its composition is contributed by polysaccharide) makes it inexpensive raw material for the production of value-added products such as biofuel, bio-solvents, nanocrystalline cellulose and enzymes. In order to use lignocellulose as the raw material for the microbial fermentation, the substrate is subjected to enzymatic treatment, which leads to the release of reducing sugars such as glucose and xylose. However, the inherent properties of lignocellulose such as presence of lignin, pectin, acetyl groups and the presence of crystalline cellulose contribute to recalcitrance. This leads to poor sugar yields upon enzymatic hydrolysis of lignocellulose. A pre-treatment method is generally applied before enzymatic treatment of lignocellulose that essentially removes recalcitrant components in biomass through structural breakdown. Present study is carried out to find out the best pre-treatment method for the maximum liberation of reducing sugars from spent coffee waste (SPW). SPW was subjected to a range of physical, chemical and physico-chemical pre-treatment followed by a sequential, combinatorial pre-treatment strategy is also applied on to attain maximum sugar yield by combining two or more pre-treatments. All the pre-treated samples were analysed for total reducing sugar followed by identification and quantification of individual sugar by HPLC coupled with RI detector. Besides, generation of any inhibitory compounds such furfural, hydroxymethyl furfural (HMF) which can hinder microbial growth and enzyme activity is also monitored. Results showed that ultrasound treatment (31.06 mg/L) proved to be the best pre-treatment method based on total reducing content followed by dilute acid hydrolysis (10.03 mg/L) while galactose was found to be the major monosaccharide present in the pre-treated SPW. Finally, the results obtained from the study were used to design a sequential lignocellulose pre-treatment protocol to decrease the formation of enzyme inhibitors and increase sugar yield on enzymatic hydrolysis by employing cellulase-hemicellulase consortium. Sequential, combinatorial treatment was found better in terms of total reducing yield and low content of the inhibitory compounds formation, which could be due to the fact that this mode of pre-treatment combines several mild treatment methods rather than formulating a single one. It eliminates the need for a detoxification step and potential application in the valorisation of lignocellulosic food waste.

Keywords: lignocellulose, enzymatic hydrolysis, pre-treatment, ultrasound

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Authors: A. Kesraoui, M. Seffen

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Applications of adsorption onto activated carbon for water treatment are well known. The process has been demonstrated to be widely effective for removing dissolved organic substances from wastewaters, but this treatment has a major drawback is the high operating cost. The main goal of our research work is to improve the retention capacity of Tunisian biomass for the depollution of industrial wastewater and retention of pollutants considered toxic. The biosorption process is based on the retention of molecules and ions onto a solid surface composed of biological materials. The evaluation of the potential use of these materials is important to propose as an alternative to the adsorption process generally expensive, used to remove organic compounds. Indeed, these materials are very abundant in nature and are low cost. Certainly, the biosorption process is effective to remove the pollutants, but it presents a slow kinetics. The improvement of the biosorption rates is a challenge to make this process competitive with respect to oxidation and adsorption onto lignocellulosic fibers. In this context, the alternating current appears as a new alternative, original and a very interesting phenomenon in the acceleration of chemical reactions. Our main goal is to increase the retention acceleration of dyes (indigo carmine, methylene blue) and phenol by using a new alternative: alternating current. The adsorption experiments have been performed in a batch reactor by adding some of the adsorbents in 150 mL of pollutants solution with the desired concentration and pH. The electrical part of the mounting comprises a current source which delivers an alternating current voltage of 2 to 15 V. It is connected to a voltmeter that allows us to read the voltage. In a 150 mL capacity cell, we plunged two zinc electrodes and the distance between two Zinc electrodes has been 4 cm. Thanks to alternating current, we have succeeded to improve the performance of activated carbon by increasing the speed of the indigo carmine adsorption process and reducing the treatment time. On the other hand, we have studied the influence of the alternating current on the biosorption rate of methylene blue onto Luffa cylindrica fibers and the hybrid material (Luffa cylindrica-ZnO). The results showed that the alternating current accelerated the biosorption rate of methylene blue onto the Luffa cylindrica and the Luffa cylindrica-ZnO hybrid material and increased the adsorbed amount of methylene blue on both adsorbents. In order to improve the removal of phenol, we performed the coupling between the alternating current and the biosorption onto two adsorbents: Luffa cylindrica and the hybrid material (Luffa cylindrica-ZnO). In fact, the alternating current has succeeded to improve the performance of adsorbents by increasing the speed of the adsorption process and the adsorption capacity and reduce the processing time.

Keywords: adsorption, alternating current, dyes, modeling

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Authors: Asfaw Gezae Daful, Mohsen Alimandagari, Kathleen Haigh, Somayeh Farzad, Eugene Van Rensburg, Johann F. Görgens

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The sugar industry has to 're-invent' itself to ensure long-term economic survival and opportunities for job creation and enhanced community-level impacts, given increasing pressure from fluctuating and low global sugar prices, increasing energy prices and sustainability demands. We propose biorefineries for re-vitalisation of the sugar industry using low value lignocellulosic biomass (sugarcane bagasse, leaves, and tops) annexed to existing sugar mills, producing a spectrum of high value platform chemicals along with biofuel, bioenergy, and electricity. Opportunity is presented for greener products, to mitigate climate change and overcome economic challenges. Xylose from labile hemicellulose remains largely underutilized and the conversion to value-add products a major challenge. Insight is required on pretreatment and/or extraction to optimize production of cellulosic ethanol together with lactic acid, furfural or biopolymers from sugarcane bagasse, leaves, and tops. Experimental conditions for alkaline and pressurized hot water extraction dilute acid and steam explosion pretreatment of sugarcane bagasse and harvest residues were investigated to serve as a basis for developing various process scenarios under a sugarcane biorefinery scheme. Dilute acid and steam explosion pretreatment were optimized for maximum hemicellulose recovery, combined sugar yield and solids digestibility. An optimal range of conditions for alkaline and liquid hot water extraction of hemicellulosic biopolymers, as well as conditions for acceptable enzymatic digestibility of the solid residue, after such extraction was established. Using data from the above, a series of energy efficient biorefinery scenarios are under development and modeled using Aspen Plus® software, to simulate potential factories to better understand the biorefinery processes and estimate the CAPEX and OPEX, environmental impacts, and overall viability. Rigorous and detailed sustainability assessment methodology was formulated to address all pillars of sustainability. This work is ongoing and to date, models have been developed for some of the processes which can ultimately be combined into biorefinery scenarios. This will allow systematic comparison of a series of biorefinery scenarios to assess the potential to reduce negative impacts on and maximize the benefits of social, economic, and environmental factors on a lifecycle basis.

Keywords: biomass, biorefinery, green economy, sustainability

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Authors: Zoltan Sebestyen, Eszter Barta-Rajnai, Emma Jakab, Zsuzsanna Czegeny

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Extraction of the energy content of lignocellulosic biomass is one of the possible pathways to reduce the greenhouse gas emission derived from the burning of the fossil fuels. The application of the bioenergy can mitigate the energy dependency of a country from the foreign natural gas and the petroleum. The diversity of the plant materials makes difficult the utilization of the raw biomass in power plants. This problem can be overcome by the application of thermochemical techniques. Pyrolysis is the thermal decomposition of the raw materials under inert atmosphere at high temperatures, which produces pyrolysis gas, biooil and charcoal. The energy content of these products can be exploited by further utilization. The differences in the chemical and physical properties of the raw biomass materials can be reduced by the use of torrefaction. Torrefaction is a promising mild thermal pretreatment method performed at temperatures between 200 and 300 °C in an inert atmosphere. The goal of the pretreatment from a chemical point of view is the removal of water and the acidic groups of hemicelluloses or the whole hemicellulose fraction with minor degradation of cellulose and lignin in the biomass. Thus, the stability of biomass against biodegradation increases, while its energy density increases. The volume of the raw materials decreases so the expenses of the transportation and the storage are reduced as well. Biooil is the major product during pyrolysis and an important by-product during torrefaction of biomass. The composition of biooil mostly depends on the quality of the raw materials and the applied temperature. In this work, thermoanalytical techniques have been used to study the qualitative and quantitative composition of the pyrolysis and torrefaction oils of a woody (black locust) and two herbaceous samples (rape straw and wheat straw). The biooil contains C5 and C6 anhydrosugar molecules, as well as aromatic compounds originating from hemicellulose, cellulose, and lignin, respectively. In this study, special emphasis was placed on the formation of the lignin monomeric products. The structure of the lignin fraction is different in the wood and in the herbaceous plants. According to the thermoanalytical studies the decomposition of lignin starts above 200 °C and ends at about 500 °C. The lignin monomers are present among the components of the torrefaction oil even at relatively low temperatures. We established that the concentration and the composition of the lignin products vary significantly with the applied temperature indicating that different decomposition mechanisms dominate at low and high temperatures. The evolutions of decomposition products as well as the thermal stability of the samples were measured by thermogravimetry/mass spectrometry (TG/MS). The differences in the structure of the lignin products of woody and herbaceous samples were characterized by the method of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). As a statistical method, principal component analysis (PCA) has been used to find correlation between the composition of lignin products of the biooil and the applied temperatures.

Keywords: pyrolysis, torrefaction, biooil, lignin

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Authors: Anurag Bhambhani, Jan Peter Van Der Hoek, Zoran Kapelan

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The food system depends on the availability of Phosphorus (P) and Nitrogen (N). Growing population, depleting Phosphorus reserves and energy-intensive industrial nitrogen fixation are threats to their future availability. Recovering P and N from domestic sewage water offers a solution. Recovered P and N can be applied to agricultural land, replacing virgin P and N. Thus, recovery from sewage water offers a solution befitting a circular economy. To ensure minimum waste and maximum resource efficiency a circularity assessment method is crucial to optimize nutrient flows and minimize losses. Material Circularity Indicator (MCI) is a useful method to quantify the circularity of materials. It was developed for materials that remain within the market and recently extended to include biotic materials that may be composted or used for energy recovery after end-of-use. However, MCI has not been used in the context of nutrient recovery. Besides, MCI is time-static, i.e., it cannot account for dynamic systems such as the terrestrial nutrient cycles. Nutrient application to agricultural land is a highly dynamic process wherein flows and stocks change with time. The rate of recycling of nutrients in nature can depend on numerous factors such as prevailing soil conditions, local hydrology, the presence of animals, etc. Therefore, a dynamic model of nutrient flows with indicators is needed for the circularity assessment. A simple substance flow model of P and N will be developed with the help of flow equations and transfer coefficients that incorporate the nutrient recovery step along with the agricultural application, the volatilization and leaching processes, plant uptake and subsequent animal and human uptake. The model is then used for calculating the proportions of linear and restorative flows (coming from reused/recycled sources). The model will simulate the adsorption process based on the quantity of adsorbent and nutrient concentration in the water. Thereafter, the application of the adsorbed nutrients to agricultural land will be simulated based on adsorbate release kinetics, local soil conditions, hydrology, vegetation, etc. Based on the model, the restorative nutrient flow (returning to the sewage plant following human consumption) will be calculated. The developed methodology will be applied to a case study of resource recovery from wastewater. In the aforementioned case study located in Italy, biochar or zeolite is to be used for recovery of P and N from domestic sewage through adsorption and thereafter, used as a slow-release fertilizer in agriculture. Using this model, information regarding the efficiency of nutrient recovery and application can be generated. This can help to optimize the recovery process and application of the nutrients. Consequently, this will help to optimize nutrient recovery and application and reduce the dependence of the food system on the virgin extraction of P and N.

Keywords: circular economy, dynamic substance flow, nutrient cycles, resource recovery from water

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Authors: M. Zielinski, M. Debowski, P. Rusanowska, A. Glowacka-Gil, M. Zielinska, A. Cydzik-Kwiatkowska, J. Kazimierowicz

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Technologies for the micro-biogas plant with heating and mixing systems are presented as a part of the Research Coordination for a Low-Cost Biomethane Production at Small and Medium Scale Applications (Record Biomap). The main objective of the Record Biomap project is to build a network of operators and scientific institutions interested in cooperation and the development of promising technologies in the sector of small and medium-sized biogas plants. The activities carried out in the project will bridge the gap between research and market and reduce the time of implementation of new, efficient technological and technical solutions. Reactor with simultaneously mixing and heating system is a concrete tank with a rectangular cross-section. In the reactor, heating is integrated with the mixing of substrate and anaerobic sludge. This reactor is solution dedicated for substrates with high solids content, which cannot be introduced to the reactor with pumps, even with positive displacement pumps. Substrates are poured to the reactor and then with a screw pump, they are mixed with anaerobic sludge. The pumped sludge, flowing through the screw pump, is simultaneously heated by a heat exchanger. The level of the fermentation sludge inside the reactor chamber is above the bottom edge of the cover. Cover of the reactor is equipped with the screw pump driver. Inside the reactor, an electric motor is installed that is driving a screw pump. The heated sludge circulates in the digester. The post-fermented sludge is collected using a drain well. The inlet to the drain well is below the level of the sludge in the digester. The biogas is discharged from the reactor by the biogas intake valve located on the cover. The technology is very useful for fermentation of lignocellulosic biomass and substrates with high content of dry mass (organic wastes). The other technology is a reactor for micro-biogas plant with a pressure mixing system. The reactor has a form of plastic or concrete tank with a circular cross-section. The effective mixing of sludge is ensured by profiled at 90° bottom of the tank. Substrates for fermentation are supplied by an inlet well. The inlet well is equipped with a cover that eliminates odour release. The introduction of a new portion of substrates is preceded by pumping of digestate to the disposal well. Optionally, digestate can gravitationally flow to digestate storage tank. The obtained biogas is discharged into the separator. The valve supplies biogas to the blower. The blower presses the biogas from the fermentation chamber in such a way as to facilitate the introduction of a new portion of substrates. Biogas is discharged from the reactor by valve that enables biogas removal but prevents suction from outside the reactor.

Keywords: biogas, digestion, heating system, mixing system

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Authors: Marcin Zielinski, Marcin Debowski, Paulina Rusanowska, Magda Dudek

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As a result of sonification, the destruction of complex biomass structures results in an increase in the biogas yield from the conditioned material. First, the amount of organic matter released into the solution due to disintegration was determined. This parameter was determined by changes in the carbon content in liquid phase of the conditioned substrate. The amount of carbon in the liquid phase increased with the prolongation of the sonication time to 16 min. Further increase in the duration of sonication did not cause a statistically significant increase in the amount of organic carbon in the liquid phase. The disintegrated material was then used for respirometric measurements for determination of the impact of the conditioning process used on methane fermentation effectiveness. The relationship between the amount of energy introduced into the lignocellulosic substrate and the amount of biogas produced has been demonstrated. Statistically significant increase in the amount of biogas was observed until sonication of 16 min. Further increase in energy in the conditioning process did not significantly increase the production of biogas from the treated substrate. The biogas production from the conditioned substrate was 17% higher than from the reference biomass at that time. The ultrasonic disintegration method did not significantly affect the observed biogas composition. In all series, the methane content in the produced biogas from the conditioned substrate was similar to that obtained with the raw substrate sample (51.1%). Another method of substrate conditioning was hydrothermal depolymerization. This method consists in application of increased temperature and pressure to substrate. These phenomena destroy the structure of the processed material, the release of organic compounds to the solution, which should lead to increase the amount of produced biogas from such treated biomass. The hydrothermal depolymerization was conducted using an innovative microwave heating method. Control measurements were performed using conventional heating. The obtained results indicate the relationship between depolymerization temperature and the amount of biogas. Statistically significant value of the biogas production coefficients increased as the depolymerization temperature increased to 150°C. Further raising the depolymerization temperature to 180°C did not significantly increase the amount of produced biogas in the respirometric tests. As a result of the hydrothermal depolymerization obtained using microwave at 150°C for 20 min, the rate of biogas production from the Sida silage was 780 L/kg VS, which accounted for nearly 50% increase compared to 370 L/kg VS obtained from the same silage but not depolymerised. The study showed that by microwave heating it is possible to effectively depolymerized substrate. Significant differences occurred especially in the temperature range of 130-150ºC. The pre-treatment of Sida hermaphrodita silage (biogas substrate) did not significantly affect the quality of the biogas produced. The methane concentration was about 51.5% on average. The study was carried out in the framework of the project under program BIOSTRATEG funded by the National Centre for Research and Development No. 1/270745/2/NCBR/2015 'Dietary, power, and economic potential of Sida hermaphrodita cultivation on fallow land'.

Keywords: disintegration, biogas, methane fermentation, Virginia fanpetals, biomass

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Authors: Trevor Malambo Simbayi, Diane Hildebrandt, Tonderayi Matambo

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The rapid growth of population in recent decades has resulted in an increased need for energy to meet human activities. As energy demands increase, the need for other sources of energy other than fossil fuels, increases in turn. Furthermore, environmental concerns such as global warming due to the use of fossil fuels, depleting fossil fuel reserves and the rising cost of oil have contributed to an increased interest in renewables sources of energy. Biogas is a renewable source of energy produced through the process of anaerobic digestion (AD) and it offers a two-fold solution; it provides an environmentally friendly source of energy and its production helps to reduce the amount of organic waste taken to landfills. This research seeks to address the waste management problem caused by an aquatic weed called water hyacinth (Eichhornia crassipes) at the Hartbeespoort (Harties) Dam in the North West Province of South Africa, through biogas production of the weed. Water hyacinth is a category 1 invasive species and it is deemed to be the most problematic aquatic weed. This weed is said to double its size in the space of five days. Eutrophication in the Hartbeespoort Dam has manifested itself through the excessive algae bloom and water hyacinth infestation. A large amount of biomass from water hyacinth and algae are generated per annum from the two hundred hectare surface area of the dam exposed to the sun. This biomass creates a waste management problem. Water hyacinth when in full bloom can cover nearly half of the surface of Hartbeespoort Dam. The presence of water hyacinth in the dam has caused economic and environmental problems. Economic activities such as fishing, boating, and recreation, are hampered by the water hyacinth’s prolific growth. This research proposes the use of water hyacinth as a feedstock or substrate for biogas production in order to find an economic and environmentally friendly means of waste management for the communities living around the Hartbeespoort Dam. In order to achieve this objective, water hyacinth will be collected from the dam and it will be mechanically pretreated before anaerobic digestion. Pretreatment is required for lignocellulosic materials like water hyacinth because such materials are called recalcitrant solid materials. Cow manure will be employed as a source of microorganisms needed for biogas production to occur. Once the water hyacinth and the cow dung are mixed, they will be placed in laboratory anaerobic reactors. Biogas production will be monitored daily through the downward displacement of water. Characterization of the substrates (cow manure and water hyacinth) to determine the nitrogen, sulfur, carbon and hydrogen, total solids (TS) and volatile solids (VS). Liquid samples from the anaerobic digesters will be collected and analyzed for volatile fatty acids (VFAs) composition by means of a liquid gas chromatography machine.

Keywords: anaerobic digestion, biogas, waste management, water hyacinth

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Authors: Iris Vural Gursel, Andrea Ramirez

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Effective utilization of lignin is an important mean for developing economically profitable biorefineries. Current literature suggests that large amounts of lignin will become available in second generation biorefineries. New conversion technologies will, therefore, be needed to carry lignin transformation well beyond combustion to produce energy, but towards high-value products such as chemicals and transportation fuels. In recent years, significant progress on catalysis has been made to improve transformation of lignin, and new catalytic processes are emerging. In this work, a techno-economic assessment of two of these novel conversion routes and comparison with more established lignin pyrolysis route were made. The aim is to provide insights into the potential performance and potential hotspots in order to guide the experimental research and ease the commercialization by early identifying cost drivers, strengths, and challenges. The lignin conversion routes selected for detailed assessment were: (non-catalytic) lignin pyrolysis as the benchmark, direct hydrodeoxygenation (HDO) of lignin and hydrothermal lignin depolymerisation. Products generated were mixed oxygenated aromatic monomers (MOAMON), light organics, heavy organics, and char. For the technical assessment, a basis design followed by process modelling in Aspen was done using experimental yields. A design capacity of 200 kt/year lignin feed was chosen that is equivalent to a 1 Mt/y scale lignocellulosic biorefinery. The downstream equipment was modelled to achieve the separation of the product streams defined. For determining external utility requirement, heat integration was considered and when possible gasses were combusted to cover heating demand. The models made were used in generating necessary data on material and energy flows. Next, an economic assessment was carried out by estimating operating and capital costs. Return on investment (ROI) and payback period (PBP) were used as indicators. The results of the process modelling indicate that series of separation steps are required. The downstream processing was found especially demanding in the hydrothermal upgrading process due to the presence of significant amount of unconverted lignin (34%) and water. Also, external utility requirements were found to be high. Due to the complex separations, hydrothermal upgrading process showed the highest capital cost (50 M€ more than benchmark). Whereas operating costs were found the highest for the direct HDO process (20 M€/year more than benchmark) due to the use of hydrogen. Because of high yields to valuable heavy organics (32%) and MOAMON (24%), direct HDO process showed the highest ROI (12%) and the shortest PBP (5 years). This process is found feasible with a positive net present value. However, it is very sensitive to the prices used in the calculation. The assessments at this stage are associated with large uncertainties. Nevertheless, they are useful for comparing alternatives and identifying whether a certain process should be given further consideration. Among the three processes investigated here, the direct HDO process was seen to be the most promising.

Keywords: biorefinery, economic assessment, lignin conversion, process design

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Authors: Razieh Karimi Aghcheh, Christian Kubicek, Joseph Strauss, Gerhard Braus

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Filamentous fungi are of considerable economic and social significance for human health, nutrition and in white biotechnology. These organisms are dominant producers of a range of primary metabolites such as citric acid, microbial lipids (biodiesel) and higher unsaturated fatty acids (HUFAs). In particular, they produce also important but structurally complex secondary metabolites with enormous therapeutic applications in pharmaceutical industry, for example: cephalosporin, penicillin, taxol, zeranol and ergot alkaloids. Several fungal secondary metabolites, which are significantly relevant to human health do not only include antibiotics, but also e.g. lovastatin, a well-known antihypercholesterolemic agent produced by Aspergillus. terreus, or aflatoxin, a carcinogen produced by A. flavus. In addition to their roles for human health and agriculture, some fungi are industrially and commercially important: Species of the ascomycete genus Hypocrea spp. (teleomorph of Trichoderma) have been demonstrated as efficient producer of highly active cellulolytic enzymes. This trait makes them effective in disrupting and depolymerization of lignocellulosic materials and thus applicable tools in number of biotechnological areas as diverse as clothes-washing detergent, animal feed, and pulp and fuel productions. Fungal LaeA/LAE1 (Loss of aflR Expression A) homologs their gene products act at the interphase between secondary metabolisms, cellulase production and development. Lack of the corresponding genes results in significant physiological changes including loss of secondary metabolite and lignocellulose degrading enzymes production. At the molecular level, the encoded proteins are presumably methyltransferases or demethylases which act directly or indirectly at heterochromatin and interact with velvet domain proteins. Velvet proteins bind to DNA and affect expression of secondary metabolites (SMs) genes and cellulases. The dynamic interplay between LaeA/LAE1, velvet proteins and additional interaction partners is the key for an understanding of the coordination of metabolic and morphological functions of fungi and is required for a biotechnological control of the formation of desired bioactive products. Aspergilli and Trichoderma represent different biotechnologically significant species with significant differences in the LaeA/LAE1-Velvet protein machinery and their target proteins. We, therefore, performed a comparative study of the interaction partners of this machinery and the dynamics of the various protein-protein interactions using our robust proteomic and mass spectrometry techniques. This enhances our knowledge about the fungal coordination of secondary metabolism, cellulase production and development and thereby will certainly improve recombinant fungal strain construction for the production of industrial secondary metabolite or lignocellulose hydrolytic enzymes.

Keywords: cellulases, LaeA/1, proteomics, secondary metabolites

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Authors: Anitha Muralidhara, Victor Engelen, Christophe Len, Pascal Pandard, Guy Marlair

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Production of bio-based chemicals and materials from lignocellulosic biomass is gaining tremendous importance in advanced bio-refineries while aiming towards progressive replacement of petroleum based chemicals in transportation fuels and commodity polymers. One such attempt has resulted in the production of key furan derivatives (FD) such as furfural, HMF, MMF etc., via acid catalyzed dehydration (ACD) of C6 and C5 sugars, which are further converted into key chemicals or intermediates (such as Furandicarboxylic acid, Furfuryl alcohol etc.,). In subsequent processes, many high potential FD are produced, that can be converted into high added value polymers or high energy density biofuels. During ACD, an unavoidable polyfuranic byproduct is generated which is called humins. The family of FD is very large with varying chemical structures and diverse physicochemical properties. Accordingly, the associated risk profiles may largely vary. Hazardous Material (Haz-mat) classification systems such as GHS (CLP in the EU) and the UN TDG Model Regulations for transport of dangerous goods are one of the preliminary requirements for all chemicals for their appropriate classification, labelling, packaging, safe storage, and transportation. Considering the growing application routes of FD, it becomes important to notice the limited access to safety related information (safety data sheets available only for famous compounds such as HMF, furfural etc.,) in these internationally recognized haz-mat classification systems. However, these classifications do not necessarily provide information about the extent of risk involved when the chemical is used in any specific application. Factors such as thermal stability, speed of combustion, chemical incompatibilities, etc., can equally influence the safety profile of a compound, that are clearly out of the scope of any haz-mat classification system. Irrespective of the bio-based origin, FD has so far received inconsistent remarks concerning their toxicity profiles. With such inconsistencies, there is a fear that, a large family of FD may also follow extreme judgmental scenarios like ionic liquids, by ranking some compounds as extremely thermally stable, non-flammable, etc., Unless clarified, these messages could lead to misleading judgements while ranking the chemical based on its hazard rating. Safety is a key aspect in any sustainable biorefinery operation/facility, which is often underscored or neglected. To fill up these existing data gaps and to address ambiguities and discrepancies, the current study focuses on giving preliminary insights on safety assessment of FD and their potential targeted by-products. With the available information in the literature and obtained experimental results, physicochemical safety, environmental safety as well as (a scenario based) fire safety profiles of key FD, as well as side streams such as humins and levulinic acid, will be considered. With this, the study focuses on defining patterns and trends that gives coherent safety related information for existing and newly synthesized FD in the market for better functionality and sustainable applications.

Keywords: furanics, humins, safety, thermal and fire hazard, toxicity

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Authors: A. Volperts, G. Dobele, A. Zhurinsh, I. Kruusenberg, A. Plavniece, J. Locs

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Nowadays energy consumption constantly increases and development of effective and cheap electrochemical sources of power, such as fuel cells and electrochemical capacitors, is topical. Due to their high specific power, charge and discharge rates, working lifetime supercapacitor based energy accumulation systems are more and more extensively being used in mobile and stationary devices. Lignocellulosic materials are widely used as precursors and account for around 45% of the total raw materials used for the manufacture of activated carbon which is the most suitable material for supercapacitors. First part of our research is devoted to study of influence of main stages of wood thermochemical activation parameters on activated carbons porous structure formation. It was found that the main factors governing the properties of carbon materials are specific surface area, volume and pore size distribution, particles dispersity, ash content and oxygen containing groups content. Influence of activated carbons attributes on capacitance and working properties of supercapacitor are demonstrated. The correlation between activated carbons porous structure indices and electrochemical specifications of supercapacitors with electrodes made from these materials has been determined. It is shown that if synthesized activated carbons are used in supercapacitors then high specific capacitances can be reached – more than 380 F/g in 4.9M sulfuric acid based electrolytes and more than 170 F/g in 1 M tetraethylammonium tetrafluoroborate in acetonitrile electrolyte. Power specifications and minimal price of H₂-O₂ fuel cells are limited by the expensive platinum-based catalysts. The main direction in development of non-platinum catalysts for the oxygen reduction is the study of cheap porous carbonaceous materials which can be obtained by the pyrolysis of polymers including renewable biomass. It is known that nitrogen atoms in carbon materials to a high degree determine properties of the doped activated carbons, such as high electrochemical stability, hardness, electric resistance, etc. The lack of sufficient knowledge on the doping of the carbon materials calls for the ongoing researches of properties and structure of modified carbon matrix. In the second part of this study, highly porous activated carbons were synthesized using alkali thermochemical activation from wood, cellulose and cellulose production residues – craft lignin and sewage sludge. Activated carbon samples were doped with dicyandiamide and melamine for the application as fuel cell cathodes. Conditions of nitrogen introduction (solvent, treatment temperature) and its content in the carbonaceous material, as well as porous structure characteristics, such as specific surface and pore size distribution, were studied. It was found that efficiency of doping reaction depends on the elemental oxygen content in the activated carbon. Relationships between nitrogen content, porous structure characteristics and electrodes electrochemical properties are demonstrated.

Keywords: activated carbons, low-temperature fuel cells, nitrogen doping, porous structure, supercapacitors

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Authors: Kimberly Samaha

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The Bio-Hub Ecosystem model was developed to address a critical area of concern within the global energy market regarding biomass as a feedstock for power plants. Yet the lack of an economically-viable business model for bioenergy facilities has resulted in the continuation of idled and decommissioned plants. This study analyzed data and submittals to the Born Global Maine Innovation Challenge. The Innovation Challenge was a global innovation challenge to identify process innovations that could address a ‘whole-tree’ approach of maximizing the products, byproducts, energy value and process slip-streams into a circular zero-waste design. Participating companies were at various stages of developing bioproducts and included biofuels, lignin-based products, carbon capture platforms and biochar used as both a filtration medium and as a soil amendment product. This case study shows the QCA (Qualitative Comparative Analysis) methodology of the prequalification process and the resulting techno-economic model that was developed for the maximizing profitability of the Bio-Hub Ecosystem through continuous expansion of system waste streams into valuable process inputs for co-hosts. A full site plan for the integration of co-hosts (biorefinery, land-based shrimp and salmon aquaculture farms, a tomato green-house and a hops farm) at an operating forestry-based biomass to energy plant in West Enfield, Maine USA. This model and process for evaluating the profitability not only proposes models for integration of forestry, aquaculture and agriculture in cradle-to-cradle linkages of what have typically been linear systems, but the proposal also allows for the early measurement of the circularity and impact of resource use and investment risk mitigation, for these systems. In this particular study, profitability is assessed at two levels CAPEX (Capital Expenditures) and in OPEX (Operating Expenditures). Given that these projects start with repurposing facilities where the industrial level infrastructure is already built, permitted and interconnected to the grid, the addition of co-hosts first realizes a dramatic reduction in permitting, development times and costs. In addition, using the biomass energy plant’s waste streams such as heat, hot water, CO₂ and fly ash as valuable inputs to their operations and a significant decrease in the OPEX costs, increasing overall profitability to each of the co-hosts bottom line. This case study utilizes a proprietary techno-economic model to demonstrate how utilizing waste streams of a biomass energy plant and/or biorefinery, results in significant reduction in OPEX for both the biomass plants and the agriculture and aquaculture co-hosts. Economically viable Bio-Hubs with favorable environmental and community impacts may prove critical in garnering local and federal government support for pilot programs and more wide-scale adoption, especially for those living in severely economically depressed rural areas where aging industrial sites have been shuttered and local economies devastated.

Keywords: bio-economy, biomass energy, financing, zero-waste

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Authors: Sara Scolari, Davide Mombelli, Gianluca Dall'Osto, Jasna Kastivnik, Gašper Tavčar, Carlo Mapelli

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The EIT Raw Materials RIS-DustRec-II project aims to transform Electric Arc Furnace Dust (EAFD) into a valuable resource by overcoming the challenges associated with traditional recycling approaches. EAFD, a zinc-rich industrial by-product typically recycled by the Waelz process, contains complex oxides such as franklinite (ZnFe₂O₄), which hinder the efficient extraction of zinc, by also introducing other valuable elements (Fe, Ni, Cr, Cu, …) in the slag. The project aims to develop a multistage multidisciplinary approach to separate EAFD into two streams: a magnetic and non-magnetic one. In this paper the production of self-reducing briquettes from the magnetic stream of EAFD with a reducing agent, aiming to drive carbothermic reduction and recover iron as a usable alloy, was investigated. Research was focused on optimizing the magnetic and subsequent gravimetric separation (MGS) processes, followed by high-temperature smelting to evaluate reduction efficiency and phase separation. The characterization of selected two different raw EAFD samples and their magnetic-gravitational separation to isolate zinc- and iron-rich fractions was performed by X-ray diffraction and scanning electron microscope. The iron-enriched concentrates were then agglomerated into self-reducing briquettes by mixing them with either biochar (olive pomace pyrolyzed at 350 and 750°C and wood chips pyrolyzed at 750 °C) and a Cupola Furnace dust as reducing agents, combined with gelatinized corn starch as a binder. Cylindrical briquettes were produced and cured for 14 days to ensure structural integrity during subsequent thermal treatments. Smelting tests were carried out at 1400 °C in an inert argon atmosphere to assess the metallization efficiency and the separation between metal and slag phases. A carbon/oxides mass ratio of 0.262 (C/(ZnO+Fe₂O₃)) was used in these tests to maintain continuity with previous studies and to standardize reduction conditions. The magnetic and gravimetric separations effectively isolated zinc- and iron-enriched fractions, particularly for one of the two EAFD, where the concentration of Zn in the concentration fraction was reduced by 8 wt.% while Fe reached 45 wt.%. The reduction tests conducted at 1400 °C showed that the chosen carbon/oxides ratio was sufficient for the smelting of the reducible oxides within the briquettes. However, an important limitation became apparent: the amount of carbon, exceeding the stochiometric value, proved to be excessive for the effective coalescence of metal droplets, preventing clear metal-slag separation. To address this, further smelting tests were carried out in an air atmosphere rather than inert conditions to burn off excess carbon. This paper demonstrates the potential of controlled carbothermic reduction for EAFD recycling. By carefully optimizing the C/(ZnO+Fe₂O₃) ratio, the process can maximize metal recovery while achieving better separation of the metal and slag phases. This approach offers a promising alternative to traditional EAFD recycling methods, with further studies recommended to refine the parameters for industrial application.

Keywords: biochars, electrical arc furnace dust, metallization, smelting

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Authors: Álvaro Ramírez Vidal, Martín Muñoz Morales, Francisco Jesús Fernández Morales, Luis Rodríguez Romero, José Villaseñor Camacho, Javier Llanos López

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In recent times, environmental problems have led to the extensive use of biological systems to solve them. Among the different types of biological systems, the use of plants such as aquatic macrophytes in constructed wetlands and terrestrial plant species for treating polluted soils and sludge has gained importance. Though the use of constructed wetlands for wastewater treatment is a well-researched domain, the slowness of pollutant degradation and high biomass production pose some challenges. Plants used in CW participate in different mechanisms for the capture and degradation of pollutants that also can retain some pharmaceutical and personal care products (PPCPs) that are very persistent in the environment. Thus, these systems present advantages in line with the guidelines published for the transition towards friendly and ecological procedures as they are environmentally friendly systems, consume low energy, or capture atmospheric CO₂. However, the use of CW presents some drawbacks, as the slowness of pollutant degradation or the production of important amounts of plant biomass, which need to be harvested and managed periodically. Taking this opportunity in mind, it is important to highlight that this residual biomass (of lignocellulosic nature) could be used as the feedstock for the generation of carbonaceous materials using thermochemical transformations such as slow pyrolysis or hydrothermal carbonization to produce high-value biomass-derived carbons through sustainable processes as adsorbents, catalysts…, thereby improving the circular carbon economy. Thus, this work carried out the analysis of some PPCPs commonly found in urban wastewater, as salicylic acid or ibuprofen, to evaluate the remediation carried out for the Phragmites Australis. Then, after the harvesting, this biomass can be used to synthesize electrodes through hydrothermal carbonization (HTC) and produce high-value biomass-derived carbons with electrocatalytic activity to remove heavy metals and persistent pollutants, promoting circular economy concepts. To do this, it was chosen biomass derived from the natural environment in high environmental risk as the Daimiel Wetlands National Park in the center of Spain, and the rest of the biomass developed in a CW specifically designed to remove pollutants. The research emphasizes the impact of the composition of the biomass waste and the synthetic parameters applied during HTC on the electrocatalytic activity. Additionally, this parameter can be related to the physicochemical properties, as porosity, surface functionalization, conductivity, and mass transfer of the electrodes lytic inks. Data revealed that carbon materials synthesized have good surface properties (good conductivities and high specific surface area) that enhance the electro-oxidants generated and promote the removal of PPCPs and the chemical oxygen demand of polluted waters.

Keywords: constructed wetlands, carbon materials, heavy metals, pharmaceutical and personal care products, hydrothermal carbonization

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Authors: Rouzbeh Jafari, Joe Nava

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This study includes learnings from an engineering practice normally performed on large scale biohydrogen processes. If properly scale-up is done, biohydrogen can be a reliable pathway for biowaste valorization. Most of the studies on biohydrogen process development have used model feedstock to investigate process key performance indicators (KPIs). This study does not intend to compare different technologies with model feedstock. However, it reports economic drivers and technical challenges which help in developing a road map for expanding biohydrogen economy deployment in Canada. BBA is a consulting firm responsible for the design of hydrogen production projects. Through executing these projects, activity has been performed to identify, register and mitigate technical drawbacks of large-scale hydrogen production. Those learnings, in this study, have been applied to the biohydrogen process. Through data collected by a comprehensive literature review, a base case has been considered as a reference, and several case studies have been performed. Critical parameters of the process were identified and through common engineering practice (process design, simulation, cost estimate, and life cycle assessment) impact of these parameters on the commercialization risk matrix and class 5 cost estimations were reported. The process considered in this study is food waste and woody biomass dark fermentation. To propose a reliable road map to develop a sustainable biohydrogen production process impact of critical parameters was studied on the end-to-end process. These parameters were 1) feedstock composition, 2) feedstock pre-treatment, 3) unit operation selection, and 4) multi-product concept. A couple of emerging technologies also were assessed such as photo-fermentation, integrated dark fermentation, and using ultrasound and microwave to break-down feedstock`s complex matrix and increase overall hydrogen yield. To properly report the impact of each parameter KPIs were identified as 1) Hydrogen yield, 2) energy consumption, 3) secondary waste generated, 4) CO2 footprint, 5) Product profile, 6) $/kg-H2 and 5) environmental impact. The feedstock is the main parameter defining the economic viability of biohydrogen production. Through parametric studies, it was found that biohydrogen production favors feedstock with higher carbohydrates. The feedstock composition was varied, by increasing one critical element (such as carbohydrate) and monitoring KPIs evolution. Different cases were studied with diverse feedstock, such as energy crops, wastewater slug, and lignocellulosic waste. The base case process was applied to have reference KPIs values and modifications such as pretreatment and feedstock mix-and-match were implemented to investigate KPIs changes. The complexity of the feedstock is the main bottleneck in the successful commercial deployment of the biohydrogen process as a reliable pathway for waste valorization. Hydrogen yield, reaction kinetics, and performance of key unit operations highly impacted as feedstock composition fluctuates during the lifetime of the process or from one case to another. In this case, concept of multi-product becomes more reliable. In this concept, the process is not designed to produce only one target product such as biohydrogen but will have two or multiple products (biohydrogen and biomethane or biochemicals). This new approach is being investigated by the BBA team and the results will be shared in another scientific contribution.

Keywords: biohydrogen, process scale-up, economic evaluation, commercialization uncertainties, hydrogen economy

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Authors: Yetti Marlida, Syukri Arif, Nadirman Haska

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Recently, alcohol fuels have been produced on industrial scales by fermentation of sugars derived from wheat, corn, sugar beets, sugar cane etc. The enzymatic hydrolysis of cellulosic materials to produce fermentable sugars has an enormous potential in meeting global bioenergy demand through the biorefinery concept, since agri-food processes generate millions of tones of waste each year (Xeros and Christakopoulos 2009) such as sugar cane baggase , wheat straw, rice straw, corn cob, and oil palm trunk. In fact oil palm trunk is one of the most abundant lignocellulosic wastes by-products worldwide especially come from Malaysia, Indonesia and Nigeria and provides an alternative substrate to produce useful chemicals such as bioethanol. Usually, from the ages 3 years to 25 years, is the economical life of oil palm and after that, it is cut for replantation. The size of trunk usually is 15-18 meters in length and 46-60 centimeters in diameter. The trunk after cutting is agricultural waste causing problem in elimination but due to the trunk contains about 42% cellulose, 34.4%hemicellulose, 17.1% lignin and 7.3% other compounds,these agricultural wastes could make value added products (Pumiput, 2006).This research was production of bioethanol from oil palm trunk via saccharafication by cocktail carbohydrases enzymes. Enzymatic saccharification of acid treated oil palm trunk was carried out in reaction mixture containing 40 g treated oil palm trunk in 200 ml 0.1 M citrate buffer pH 4.8 with 500 unit/kg amylase for treatment A: Treatment B: Treatment A + 500 unit/kg cellulose; C: treatment B + 500 unit/kgg xylanase: D: treatment D + 500 unit/kg ligninase and E: OPT without treated + 500 unit/kg amylase + 500 unit/kg cellulose + 500 unit/kg xylanase + 500 unit/kg ligninase. The reaction mixture was incubated on a water bath rotary shaker adjusted to 600C and 75 rpm. The samples were withdraw at intervals 12 and 24, 36, 48,60, and 72 hr. For bioethanol production in biofermentor of 5L the hydrolysis product were inoculated a loop of Saccharomyces cerevisiae and then incubated at 34 0C under static conditions. Samples are withdraw after 12, 24, 36, 48 and 72 hr for bioethanol and residual glucose. The results of the enzymatic hidrolysis (Figure1) showed that the treatment B (OPT hydrolyzed with amylase and cellulase) have optimum condition for glucose production, where was both of enzymes can be degraded OPT perfectly. The same results also reported by Primarini et al., (2012) reported the optimum conditions the hydrolysis of OPT was at concentration of 25% (w /v) with 0.3% (w/v) amylase, 0.6% (w /v) glucoamylase and 4% (w/v) cellulase. In the Figure 2 showed that optimum bioethanol produced at 48 hr after incubation,if time increased the biothanol decreased. According Roukas (1996), a decrease in the concentration of ethanol occur at excess glucose as substrate and product inhibition effects. Substrate concentration is too high reduces the amount of dissolved oxygen, although in very small amounts, oxygen is still needed in the fermentation by Saccaromyces cerevisiae to keep life in high cell concentrations (Nowak 2000, Tao et al. 2005). The results of the research can be conluded that the optimum enzymatic hydrolysis occured when the OPT added with amylase and cellulase and optimum bioethanol produced at 48 hr incubation using Saccharomyses cerevicea whereas 18.08 % bioethanol produced from glucose conversion. This work was funded by Directorate General of Higher Education (DGHE), Ministry of Education and Culture, contract no.245/SP2H/DIT.LimtabMas/II/2013

Keywords: oil palm trunk, enzymatic hydrolysis, saccharification

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Authors: Pejman Salimi, Sebastiano Tieuli, Somayeh Taghavi, Michela Signoretto, Remo Proietti Zaccaria

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Increasing the growth of industrial waste due to the large quantities of production leads to numerous environmental and economic challenges, such as climate change, soil and water contamination, human disease, etc. Energy recovery of waste can be applied to produce heat or electricity. This strategy allows for the reduction of energy produced using coal or other fuels and directly reduces greenhouse gas emissions. Among different factories, leather manufacturing plays a very important role in the whole world from the socio-economic point of view. The leather industry plays a very important role in our society from a socio-economic point of view. Even though the leather industry uses a by-product from the meat industry as raw material, it is considered as an activity demanding integrated prevention and control of pollution. Along the entire process from raw skins/hides to finished leather, a huge amount of solid and water waste is generated. Solid wastes include fleshings, raw trimmings, shavings, buffing dust, etc. One of the most abundant solid wastes generated throughout leather tanning is shaving waste. Leather shaving is a mechanical process that aims at reducing the tanned skin to a specific thickness before tanning and finishing. This product consists mainly of collagen and tanning agent. At present, most of the world's leather processing is chrome-tanned based. Consequently, large amounts of chromium-containing shaving wastes need to be treated. The major concern about the management of this kind of solid waste is ascribed to chrome content, which makes the conventional disposal methods, such as landfilling and incineration, not practicable. Therefore, many efforts have been developed in recent decades to promote eco-friendly/alternative leather production and more effective waste management. Herein, shaving waste resulting from metal-free tanning technology is proposed as low-cost precursors for the preparation of carbon material as anodes for lithium-ion batteries (LIBs). In line with the philosophy of a reduced environmental impact, for preparing fully sustainable and environmentally friendly LIBs anodes, deionized water and carboxymethyl cellulose (CMC) have been used as alternatives to toxic/teratogen N-methyl-2- pyrrolidone (NMP) and to biologically hazardous Polyvinylidene fluoride (PVdF), respectively. Furthermore, going towards the reduced cost, we employed water solvent and fluoride-free bio-derived CMC binder (as an alternative to NMP and PVdF, respectively) together with LiFePO₄ (LFP) when a full cell was considered. These actions make closer to the 2030 goal of having green LIBs at 100 $ kW h⁻¹. Besides, the preparation of the water-based electrodes does not need a controlled environment and due to the higher vapour pressure of water in comparison with NMP, the water-based electrode drying is much faster. This aspect determines an important consequence, namely a reduced energy consumption for the electrode preparation. The electrode derived from leather waste demonstrated a discharge capacity of 735 mAh g⁻¹ after 1000 charge and discharge cycles at 0.5 A g⁻¹. This promising performance is ascribed to the synergistic effect of defects, interlayer spacing, heteroatoms-doped (N, O, and S), high specific surface area, and hierarchical micro/mesopore structure of the biochar. Interestingly, these features of activated biochars derived from the leather industry open the way for possible applications in other EESDs as well.

Keywords: biowaste, lithium-ion batteries, physical activation, waste management, leather industry

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