Effect of Red Mud Addition on Electrical and Magnetic Properties of Hemp-Derived-Biochar-Containing Epoxy Composites.

Waste stream valorization is a difficult task where the economic and environmental issues must be balanced. The use of complex metal-rich waste such as red mud is challenging due to the wide variety of metal oxides present such as iron, aluminum, and titanium. The simple separation of each metal is not economically feasible, so alternative routes must be implemented. In this study, we investigated the use of red mud mixed with hemp waste to produce biochar with high conductivity and good magnetic properties induced by the reduction of the metal oxides present in the red mud through carbothermal processes occurring during the co-pyrolysis. The resulting biochar enriched with thermally-reduced red mud is used for the preparation of epoxy-based composites that are tested for electric and magnetic properties. The electric properties are investigated under DC (direct current) regime with or without pressure applied and under AC (alternating current) in a frequency range from 0.5 up to 16 GHz. The magnetic measurements show the effective tailoring of hemp-derived biochar with magnetic structures during the co-pyrolytic process.

Production of a bio-magnetic adsorbent via co-pyrolysis of pine wood waste and red mud.

The efficient reduction of accumulated waste biomass and red mud by converting them into a value-added magnetic adsorbent is both difficult and tempting in terms of sustainability. This study focused on investigating the reaction mechanism of co-pyrolysis of different biomasses, including pine wood, cellulose, and lignin, with red mud at 500, 650, and 800 °C, and the comprehensive characterizations of the produced bio-magnetic particles. The performance of biomass and red mud based magnetic adsorbents is also evaluated, and their primary adsorption mechanisms for organic pollutants are revealed by using different organic model compounds. The samples produced at 800 °C showed the best performance. For example, the sample prepared using red mud and pine wood at 800 °C showed the highest adsorption capacity of ibuprofen, which was 21.01 mg/g at ∼pH 4.5, indicating strong π stacking interactions as the dominant adsorption mechanism. When compared to lignin-rich biomass, adsorbents composed of cellulose-rich biomass showed greater adsorption efficacy. The findings show that co-pyrolysis of biomass with red mud can reduce waste while also producing a flexible adsorbent that is magnetically separable and effective at absorbing different organic contaminants from water.

Semi-continuous anaerobic digestion of mixed wastewater sludge with biochar addition.

This work analysed the effects of Biochar (BC) addition to the Anaerobic digestion (AD) of wastewater Mixed sludge (MS) in semi-continuous mode. A 3 L digester was operated at 37 °C for 100 days, feeding MS collected every three weeks in the same wastewater treatment plant, and 10 g L-1 of BC. The average performance of MS digestion (biogas 188 NmL d-1, 68% methane) improved in presence of BC (biogas 244 NmL d-1, 69% methane). According to the results of the multiple linear regression analysis performed on the experimental data, the 79% variation of the soluble COD in the MS was the driving factor for the 38% increase of biogas and methane yields. In conclusion, in the considered experimental conditions, the variability of the substrate's composition was the key factor driving the performances of the AD of MS, independently of the addition of BC.

Pyrolytic Conversion of Plastic Waste to Value-Added Products and Fuels: A Review.

Plastic production has been rapidly growing across the world and, at the end of their use, many of the plastic products become waste disposed of in landfills or dispersed, causing serious environmental and health issues. From a sustainability point of view, the conversion of plastic waste to fuels or, better yet, to individual monomers, leads to a much greener waste management compared to landfill disposal. In this paper, we systematically review the potential of pyrolysis as an effective thermochemical conversion method for the valorization of plastic waste. Different pyrolysis types, along with the influence of operating conditions, e.g., catalyst types, temperature, vapor residence time, and plastic waste types, on yields, quality, and applications of the cracking plastic products are discussed. The quality of pyrolysis plastic oil, before and after upgrading, is compared to conventional diesel fuel. Plastic oil yields as high as 95 wt.% can be achieved through slow pyrolysis. Plastic oil has a heating value approximately equivalent to that of diesel fuel, i.e., 45 MJ/kg, no sulfur, a very low water and ash content, and an almost neutral pH, making it a promising alternative to conventional petroleum-based fuels. This oil, as-is or after minor modifications, can be readily used in conventional diesel engines. Fast pyrolysis mainly produces wax rather than oil. However, in the presence of a suitable catalyst, waxy products further crack into oil. Wax is an intermediate feedstock and can be used in fluid catalytic cracking (FCC) units to produce fuel or other valuable petrochemical products. Flash pyrolysis of plastic waste, performed at high temperatures, i.e., near 1000 °C, and with very short vapor residence times, i.e., less than 250 ms, can recover up to 50 wt.% ethylene monomers from polyethylene waste. Alternatively, pyrolytic conversion of plastic waste to olefins can be performed in two stages, with the conversion of plastic waste to plastic oil, followed by thermal cracking of oil to monomers in a second stage. The conversion of plastic waste to carbon nanotubes, representing a higher-value product than fuel, is also discussed in detail. The results indicate that up to 25 wt.% of waste plastic can be converted into carbon nanotubes.

A technical review of bioenergy and resource recovery from municipal solid waste.

Population growth, rapid urbanization, industrialization and economic development have led to the magnified municipal solid waste generation at an alarming rate on a global scale. Municipal solid waste seems to be an economically viable and attractive resource to produce green fuels through different waste-to-energy conversion routes. This paper reviews the different waste-to-energy technologies as well as thermochemical and biological conversion technologies for the valorization of municipal solid waste and diversion for recycling. The key waste-to-energy technologies discussed in this review include conventional thermal incineration and the modern hydrothermal incineration. The thermochemical treatments (e.g. pyrolysis, liquefaction and gasification) and biological treatments (e.g. anaerobic digestion and composting) are also elaborated for the transformation of solid wastes to biofuel products. The current status of municipal solid waste management for effective disposal and diversion along with the opportunities and challenges has been comprehensively reviewed. The merits and technical challenges of the waste-to-energy technologies are systematically discussed to promote the diversion of solid wastes from landfill disposal to biorefineries.

Feasibility of anaerobic digestion as a treatment for the aqueous pyrolysis condensate (APC) of birch bark.

Biooil produced via biomass pyrolysis includes an aqueous-acidic phase and a dense and rich organic phase. The aqueous phase has a low heating value and is considered a waste stream. In this study fractional condensation was employed to separate the liquid product of birch bark pyrolysis into an aqueous pyrolysis condensate (APC) and a dense biooil fraction. The APC contained high amounts (~100 g/kg) of acidic acid (AA) and was investigated for anaerobic digestion (AD). The AA in the APC could be converted to biogas, however, it contained elevated concentrations of microbial inhibitors (24 g/kg total phenolics). The inhibiting effect could be mitigated by acclimatization of the microbial population, which in turn converted some of the additional organics. The production of methane further improved with the addition of biochar to adsorb some of the inhibitors. The results imply that a waste product can be converted into a potential energy carrier.

Antioxidant Activity of the Lignins Derived from Fluidized-Bed Fast Pyrolysis.

A challenge in recent years has been the rational use of forest and agriculture residues for the production of bio-fuel, biochemical, and other bioproducts. In this study, potentially useful compounds from pyrolytic lignins were identified by HPLC-MS/MS and untargeted metabolomics. The metabolites identified were 2-(4-allyl-2-methoxyphenoxy)-1-(4-hydroxy-3-methoxyphenyl)-1-propanol, benzyl benzoate, fisetinidol, phenyllactic acid, 2-phenylpropionic acid, 6,3'-dimethoxyflavone, and vanillin. The 2,2-diphenyl-1-picrylhydrazyl radical scavenging activity (DPPH), trolox equivalent antioxidant capacity (TEAC), and total phenolics content (TPC) per gram of pyrolytic lignin ranged from 14 to 503 mg ascorbic acid equivalents, 35 to 277 mg trolox equivalents, and 0.42 to 50 mg gallic acid equivalents, respectively. A very significant correlation was observed between the DPPH and TPC (r = 0.8663, p ≤ 0.0001), TEAC and TPC (r = 0.8044, p ≤ 0.0001), and DPPH and TEAC (r = 0.8851, p ≤ 0.0001). The polyphenolic compounds in the pyrolytic lignins which are responsible for radical scavenging activity and antioxidant properties can be readily profiled with HPLC-MS/MS combined with untargeted metabolomics. The results also suggest that DPPH, TEAC, and TPC assays are suitable methods for the measurement of antioxidant activity in a variety of pyrolytic lignins. These data show that the pyrolytic lignins can be considered as promising sources of natural antioxidants and value-added chemicals.

Application of 1D and 2D MFR reactor technology for the isolation of insecticidal and anti-microbial properties from pyrolysis bio-oils.

Valuable chemicals can be separated from agricultural residues by chemical or thermochemical processes. The application of pyrolysis has already been demonstrated as an efficient means to produce a liquid with a high concentration of desired product. The objective of this study was to apply an insect and microorganism bioassay-guided approach to separate and isolate pesticidal compounds from bio-oil produced through biomass pyrolysis. Tobacco leaf (Nicotianata bacum), tomato plant (Solanum lycopersicum), and spent coffee (Coffea arabica) grounds were pyrolyzed at 10°C/min from ambient to 565°C using the mechanically fluidized reactor (MFR). With one-dimensional (1D) MFR pyrolysis, the composition of the product vapors varied as the reactor temperature was raised allowing for the selection of the temperature range that corresponds to vapors with a high concentration of pesticidal properties. Further product separation was performed in a fractional condensation train, or 2D MFR pyrolysis, thus allowing for the separation of vapor components according to their condensation temperature. The 300-400°C tobacco and tomato bio-oil cuts from the 1D MFR showed the highest insecticidal and anti-microbial activity compared to the other bio-oil cuts. The 300-350 and 350-400°C bio-oil cuts produced by 2D MFR had the highest insecticidal activity when the bio-oil was collected from the 210°C condenser. The tobacco and tomato bio-oil had similar insecticidal activity (LC50 of 2.1 and 2.2 mg/mL) when the bio-oil was collected in the 210°C condenser from the 300-350°C reactor temperature gases. The 2D MFR does concentrate the pesticidal products compared to the 1D MFR and thus can reduce the need for further separation steps such as solvent extraction.

Lipid accumulation from pinewood pyrolysates by Rhodosporidium diobovatum and Chlorella vulgaris for biodiesel production.

This study evaluated the suitability of pinewood pyrolysates as a carbon source for lipid production and cultivation of the oleaginous yeast Rhodosporidium diobovatum and the microalgae Chlorella vulgaris. Thermal decomposition of pinewood and fractional condensation were used to obtain an oil rich in levoglucosan which was upgraded to glucose by acid hydrolysis. Blending of pyrolytic sugars with pure glucose in both nitrogen rich and nitrogen limited conditions was studied for R. diobovatum, and under nitrogen limited conditions for C. vulgaris. Glucose consumption rate decreased with increasing proportions of pyrolytic sugars increasing cultivation time. While R. diobovatum was capable of growth in 100% (v/v) pyrolytic sugars, C. vulgaris growth declined rapidly in blends greater than 20% (v/v) until no growth was detected in blends >40%. Finally, the effects of pyrolysis sugars on lipid composition was evaluated and biodiesel fuel properties were estimated based on the lipid profiles.

Comparison of ethanol production from corn cobs and switchgrass following a pyrolysis-based biorefinery approach.

BACKGROUND: One of the main obstacles in lignocellulosic ethanol production is the necessity of pretreatment and fractionation of the biomass feedstocks to produce sufficiently pure fermentable carbohydrates. In addition, the by-products (hemicellulose and lignin fraction) are of low value, when compared to dried distillers grains (DDG), the main by-product of corn ethanol. Fast pyrolysis is an alternative thermal conversion technology for processing biomass. It has recently been optimized to produce a stream rich in levoglucosan, a fermentable glucose precursor for biofuel production. Additional product streams might be of value to the petrochemical industry. However, biomass heterogeneity is known to impact the composition of pyrolytic product streams, as a complex mixture of aromatic compounds is recovered with the sugars, interfering with subsequent fermentation. The present study investigates the feasibility of fast pyrolysis to produce fermentable pyrolytic glucose from two abundant lignocellulosic biomass sources in Ontario, switchgrass (potential energy crop) and corn cobs (by-product of corn industry). RESULTS: Demineralization of biomass removes catalytic centers and increases the levoglucosan yield during pyrolysis. The ash content of biomass was significantly decreased by 82-90% in corn cobs when demineralized with acetic or nitric acid, respectively. In switchgrass, a reduction of only 50% for both acids could be achieved. Conversely, levoglucosan production increased 9- and 14-fold in corn cobs when rinsed with acetic and nitric acid, respectively, and increased 11-fold in switchgrass regardless of the acid used. After pyrolysis, different configurations for upgrading the pyrolytic sugars were assessed and the presence of potentially inhibitory compounds was approximated at each step as double integral of the UV spectrum signal of an HPLC assay. The results showed that water extraction followed by acid hydrolysis and solvent extraction was the best upgrading strategy. Ethanol yields achieved based on initial cellulose fraction were 27.8% in switchgrass and 27.0% in corn cobs. CONCLUSIONS: This study demonstrates that ethanol production from switchgrass and corn cobs is possible following a combined thermochemical and fermentative biorefinery approach, with ethanol yields comparable to results in conventional pretreatments and fermentation processes. The feedstock-independent fermentation ability can easily be assessed with a simple assay.

Improved lignin pyrolysis for phenolics production in a bubbling bed reactor--Effect of bed materials.

Lignin pyrolysis was studied in a bubbling fluidized bed reactor equipped with a fractional condensation train, using nitrogen as the fluidization gas. The effect of different bed materials (silica sand, lignin char, activated lignin char, birch bark char, and foamed glass beads) on bio-oil yield and quality was investigated for a pyrolysis temperature of 550 °C. Results how that a bed of activated lignin char is preferable to the commonly used silica sand: pyrolysis of Kraft lignin with a bed of activated lignin char not only provides a pure char product, but also a higher dry bio-oil yield (with a relative increase of 43%), lower pyrolytic water production, and better bio-oil quality. The bio-oil obtained from Kraft lignin pyrolysis with a bed of activated lignin char has a lower average molecular weight, less tar, more phenolics, and less acidity than when sand is used as bed material.

Insecticidal activity of bio-oil from the pyrolysis of straw from Brassica spp.

Agricultural crop residues can be converted through thermochemical pyrolysis to bio-oil, a sustainable source of biofuel and biochemicals. The pyrolysis bio-oil is known to contain many chemicals, some of which have insecticidal activity and can be a potential source of value-added pest control products. Brassicacae crops, cabbage, broccoli, and mustards, contain glucosinolates and isocyanates, compounds with recognized anti-herbivore activity. In Canada, canola Brassica napus straw is available from over 6 000 000 ha and mustard Brassica carinata and Brassica juncea straw is available from 200 000 ha. The straw can be converted by microbial lignocellulosic enzymes as a substrate for bioethanol production but can also be converted to bio-oil by thermochemical means. Straw from all three species was pyrolyzed, and the insecticidal components in the bio-oil were isolated by bioassay-guided solvent fractionation. Of particular interest were the mustard straw bio-oil aqueous fractions with insecticidal and feeding repellent activity to Colorado potato beetle larvae. Aqueous fractions further analyzed for active compounds were found not to contain many of the undesirable phenol compounds, which were previously found in other bio-oils seen in the dichloromethane (DCM) and ethyl acetate (EA) solvent phases of the present study. Identified within the most polar fractions were hexadecanoic and octadecanoic fatty acids, indicating that separation of these compounds during bio-oil production may provide a source of effective insecticidal compounds.

Pyrolysis based bio-refinery for the production of bioethanol from demineralized ligno-cellulosic biomass.

This paper evaluates a novel biorefinery approach for the conversion of lignocellulosic biomass from pinewood. A combination of thermochemical and biochemical conversion was chosen with the main product being ethanol. Fast pyrolysis of lignocellulosic biomasss with fractional condensation of the products was used as the thermochemical process to obtain a pyrolysis-oil rich in anhydro-sugars (levoglucosan) and low in inhibitors. After hydrolysis of these anhydro-sugars, glucose was obtained which was successfully fermented, after detoxification, to obtain bioethanol. Ethanol yields comparable to traditional biochemical processing were achieved (41.3% of theoretical yield based on cellulose fraction). Additional benefits of the proposed biorefinery concept comprise valuable by-products of the thermochemical conversion like bio-char, mono-phenols (production of BTX) and pyrolytic lignin as a source of aromatic rich fuel additive. The inhibitory effect of thermochemically derived fermentation substrates was quantified numerically to compare the effects of different process configurations and upgrading steps within the biorefinery approach.

Detection of the breakage of pharmaceutical tablets in pneumatic transport.

Pneumatic transport of pharmaceutical tablets is very convenient, compact and greatly reduces contamination. A potential problem, however, is the breakage of a significant fraction of the transported tablets, causing serious product quality problems. Since the flowrate of tablets transported through a given pneumatic transport line increases with gas velocity, lines are often operated at gas velocities slightly below the velocity at which tablets break. Minor changes in operating conditions can have a large effect on the impact resistance of tablets and on the observed tablet breakage rate. Therefore, maintaining a constant gas velocity is not sufficient to keep the tablet breakage rate below an acceptable level. The objective of the present study was to develop a reliable and non-invasive on-line method for the detection of tablet breakage. Pharmaceutical acetaminophen tablets were transported pneumatically in a 0.1 m diameter pipeline consisting of a 5 m vertical and a 4.0 m horizontal section made of either re-enforced PVC or steel. The pipeline flow regime was determined by visual observation through clear pipeline sections. Tablet breakage was quantified by screening tablet samples. Acoustic measurements were recorded at different locations along the pipeline. Analysis of the signals from microphones attached to the wall of the elbow and horizontal section provided a reliable detection of conditions leading to tablet breakage.