Characterization and Energy Densification of Mayhaw Jelly Production Wastes Using Hydrothermal Carbonization.

Research background: Mayhaw jelly, made from mayhaw berries from the southern United States, is a popular food product that on processing produces a berry pomace waste. Little information is available in the literature about this waste or how to valorize it. This study investigated this food production waste and its possibilities for conversion to a biofuel. Experimental approach: Dried mayhaw berry wastes were characterized with fiber analysis using the US National Renewable Energy Laboratory methods. After drying and grinding, hydrothermal carbonization was applied to the mayhaw berry wastes, the mayhaw waste without seeds, and mayhaw waste seeds. Fourier transform infrared spectroscopy (FTIR) was performed on mayhaw berry wastes, mayhaw waste without seeds, and mayhaw waste seeds. Calorimetry revealed the fuel value of each component of the waste and of the dried mayhaw berry wastes without any component separated. Friability testing on pellets of the biomass investigated their durability. Results and conclusions: Fiber analysis indicated a high proportion of lignin compared to cellulose in the dried mayhaw waste. Hydrothermal carbonization did not enhance the fuel value of the seeds due to their tough outer coat that inhibited hydrothermal carbonization's high ionic-product water penetration. Other mayhaw berry waste samples had enhanced fuel value after treatment at 180 or 250 °C for 5 min, with a higher fuel value attained for 250 °C treatment. After hydrothermal carbonization, the wastes were easily pelletized into durable pellets. Fourier transform infrared spectroscopy characterization indicated raw seeds had high lignin content, as did the hydrothermal carbonization-treated mayhaw berry wastes. Novelty and scientific contribution: Hydrothermal carbonization is a process not previously applied to mayhaw berry wastes. This study fills in the gaps of this waste biomass' potential to become a biofuel.

Ionic Liquids Separating Rubber Latex from Guayule.

Danger to rubber trees (Hevea brasiliensis) from South American leaf blight fungus imperils the world's source of natural latex for essential rubber products. Avoiding latex allergies also requires a non-Hevea latex source. The present methods for removing latex entrapped in the individual cells of guayule plants require environmentally hazardous chemicals. This study proposes a new method for latex extraction from guayule using various ionic liquids (ILs) to dissolve cell walls and release latex, as substantiated by Fourier transform infrared spectroscopy (FTIR) data.

Synergistic utilization of diverse industrial wastes for reutilization in steel production and their geopolymerization potential.

Recycling wastes back into a manufacturing process, or into a separate product, is an important challenge. The primary aim of this work was to combine wastes from the steel industry, the galvanizing industry and the pulp and paper industry to form two new useful products. The steel industry generates the wastes red dust, mill scale, blast oxygen furnace slag and iron ore fines. Galvanizing industrial facilities dispose of sulfuric acid contaminated with iron. The pulp and paper industry produces the byproduct black liquor, which is high in lignin. Inserting these wastes as resources into the steel industry, or as stand-alone products, could reduce the need for virgin materials. The main methodology of the work was three-fold. First, spent sulfuric acid was used to precipitate the lignin from black liquor. Second, this lignin was combined with steel industry wastes and geopolymeric materials to make briquettes, a sustainable reducing material for steelmaking furnaces. Briquettes contained red dust, mill scale, blast oxygen furnace slag, iron ore fines and lignin precipitated from black liquor with spent sulfuric acid. Key research findings of compressive strength and weight loss testing showed the briquettes to be feasible for steel-making furnace use. Third, these steel industry wastes were investigated as a partial fly ash replacement in geopolymers. Main research findings were that compared to the control geopolymer, these geopolymer samples improved compressive strength and gave similar workability. Thus, the investigated wastes have the potential to both increase recycling in the steel industry and to improve geopolymeric products.

Hydrothermal Liquefaction of Loblolly Pine: Effects of Various Wastes on Produced Biocrude.

In this study, feedstock interaction of cow manure and digested sewage sludge on hydrothermal liquefaction (HTL) of loblolly pine (LP) was evaluated. Noncatalytic HTL experiments were performed at reaction temperatures of 250, 275, and 300 °C at a constant reaction time of 30 min. Cyclohexane and acetone were used for biocrude extraction separately. The study focuses on the characteristics of the produced biocrude, and thus, physicochemical properties of biocrudes were examined by gas chromatography-mass spectrometry, Fourier-transform infrared spectroscopy, density, and viscosity measurements, in addition to comparing mass and energy yields. On a LP basis, the biocrude yield reached as high as 30 and 17% for acetone and cyclohexane extraction, respectively, at the highest reaction temperature. Elemental carbon and energy contents increased with increasing HTL temperature for all cases. Alkalinity of the HTL process liquid (aqueous phase) increases from the HTL of sludge, and thus, it favored the formation of nonpolar compounds in biocrude. On the other hand, acidity of the reaction medium increases with the HTL of manure and pine, and thus, phenolic compounds in biocrude were increasing. Cyclohexane was more effective for sludge/LP biocrude extraction, whereas acetone was effective for manure/LP. Density of cyclohexane extracted sludge/LP biocrudes at 300 °C was less than 1000 kg m-3, whereas acetone-extracted biocrudes had densities greater than 1000 kg m-3. For all the biocrudes, viscosity was reduced considerably for the mixtures when compared to biocrudes from LP alone.

Deep eutectic solvents' ability to solubilize lignin, cellulose, and hemicellulose; thermal stability; and density.

An environmentally-friendly method to separate cellulose and hemicelluloses from lignin in recalcitrant biomass for subsequent conversion is desirable to reduce greenhouse gas generation. Easily-prepared, deep eutectic solvents (DESs) have low volatility, wide liquid range, non-flammability, nontoxicity, biocompatibility, and biodegradability. This study shows the DESs (formic acid:choline chloride, lactic acid:choline chloride, acetic acid:choline chloride, lactic acid:betaine, and lactic acid:proline) to be capable of preferentially dissolving lignin at 60°C. Thermogravimetric analysis show DES to be stable at typical biomass processing temperatures. Pretreating loblolly pine in one DES increased glucose yield after enzymatic hydrolysis to more than seven times that of raw or glycerol-pretreated pine. The density of DES-pretreated biomass was found to be 40% higher than the untreated pine's density.

Glycerol as an ionic liquid co-solvent for pretreatment of rice hulls to enhance glucose and xylose yield.

Rice hulls, a widely-available secondary agricultural residue, can be pretreated with ionic liquids (IL) prior to enzymatic hydrolysis to enhance glucose and xylose yields. The high cost of ILs is a deterrent to commercial deployment at present. ILs 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate, 1,3-dimethylimidazolium dimethylphosphate, and 1-ethyl-3-methylimidazolium diethylphosphate were investigated for rice hull pretreatment. Effects of diluting ILs with glycerol were investigated for biomass pretreatment efficacy, and for solvent recovery. When diluted with 50% glycerol, rice hulls treated in 1-ethyl-3-methylimidazolium formate was found to give glucose and xylose yields after enzymatic hydrolysis better than rice hulls treated in pure 1-ethyl-3-methylimidazolium formate. Dilution in glycerol resulted in an increased rate of solvent recovery after pretreatment, as much as six times that when pure 1-ethyl-3-methylimidazolium formate was used. Diluting 1-ethyl-3-methylimidazolium formate with 50% glycerol was found to decrease solvent viscosity at the pretreatment temperature (110 °C) helping explain improved biomass pretreatment.

Reaction kinetics of hydrothermal carbonization of loblolly pine.

Hydrothermal carbonization (HTC) is a pretreatment process to convert diverse feedstocks to homogeneous energy-dense solid fuels. Understanding of reaction kinetics is necessary for reactor design and optimization. In this study, the reaction kinetics and effects of particle size on HTC were investigated. Experiments were conducted in a novel two-chamber reactor maintaining isothermal conditions for 15s to 30 min reaction times. Loblolly pine was treated at 200, 230, and 260°C. During the first few minutes of reaction, the solid-product mass yield decreases rapidly while the calorific value increases rapidly. A simple reaction mechanism is proposed and validated, in which both hemicellulose and cellulose degrade in parallel first-order reactions. Activation energy of hemicellulose and cellulose degradation were determined to be 30 and 73 kJ/mol, respectively. For short HTC times, both reaction and diffusion effects were observed.

Pretreatment of rice hulls by ionic liquid dissolution.

As a highly available waste product, rice hulls could be a starting block in replacing liquid fossil fuels. However, their silica covering can make further use difficult. This preliminary study investigates effects of dissolving rice hulls in the ionic liquids 1-ethyl-3-methylimidazolium acetate (EMIM Ac), 1-hexyl-3-methylimidazolium chloride, (HMIM Cl), and 1-allyl-3-methylimidazolium chloride (AMIM Cl), and what lignocellulosic components can be precipitated from the used ionic liquid with water and ethanol. EMIM Ac dissolution at 110 °C for 8 h was found to completely remove lignin from rice hulls, while ethanol was capable of precipitating lignin out of the used EMIM Ac. With 8h dissolution at 110 °C using HMIM Cl, approximately 20% of the cellulose in the rice hull sample can be precipitated out using water as co-solvent, while more than 60% of the hemicellulose can be precipitated with ethanol.

Acetic acid and lithium chloride effects on hydrothermal carbonization of lignocellulosic biomass.

As a renewable non-food resource, lignocellulosic biomass has great potential as an energy source or feedstock for further conversion. However, challenges exist with supply logistics of this geographically scattered and perishable resource. Hydrothermal carbonization treats any kind of biomass in 200 to 260°C compressed water under an inert atmosphere to produce a hydrophobic solid of reduced mass and increased fuel value. A maximum in higher heating value (HHV) was found when 0.4 g of acetic acid was added per g of biomass. If 1g of LiCl and 0.4 g of acetic acid were added per g of biomass to the initial reaction solution, a 30% increase in HHV was found compared to the pretreatment with no additives, along with greater mass reduction. LiCl addition also reduces reaction pressure. Addition of acetic acid and/or LiCl to hydrothermal carbonization each contribute to increased HHV and reduced mass yield of the solid product.