An improved model for the kinetics of non-oxidative hydrothermal process.

Hydrothermal processing as a post-treatment technology for sludge has attracted great interest globally as it could reduce the amount of sludge considerably. This experimental study developed a comprehensive kinetic model of cellulose degradation via non-oxidative hydrothermal processing at various temperatures (ranges 180-260 °C). Values of activation energies and pre-exponential factors were determined using chemical oxygen demand (COD)-based lumped concentrations. In this study, a new reaction pathway between solid, soluble matter and gaseous products was proposed which not only enables prediction of solid phase degradation but also can predict the formation of various types of products (in liquid and gas phase) during the reaction time. The results show that the reaction rate of cellulose to liquid products (k1=2.7×109exp(-102810RT)) were fast compared to that of for liquid products to gaseous products (k2=4.4×103exp(-64629RT)). Moreover, the model infers that the major part of solid degradation leads to the formation of the gaseous product with the reaction rate constant of k3=5.7exp(-12905RT). The proposed model can provide an opportunity to predict the performance of the non-oxidative hydrothermal processing of organic solid waste.

Fundamental mechanisms and reactions in non-catalytic subcritical hydrothermal processes: A review.

The management and disposal of solid waste is of increasing concern across the globe. Hydrothermal processing of sludge has been suggested as a promising solution to deal with the considerable amounts of sludge produced worldwide. Such a process not only degrades organic compounds and reduces waste volume, but also provides an opportunity to recover valuable substances. Hydrothermal processing comprises two main sub-processes: wet oxidation (WO) and thermal hydrolysis (TH), in which the formation of various free radicals results in the production of different intermediates. Volatile fatty acids (VFAs), especially acetic acid, are usually the main intermediates which remain as a by-product of the process. This paper aims to review the fundamental mechanism for hydrothermal processing of sludge, and the formation of different free radicals and intermediates therein. In addition, the proposed kinetic models for the two processes (WO and TH) from the literature are reviewed and the advantages and disadvantages of each model are outlined. The effect of mass transfer as a critical component of the design and development of the processes, which has been neglected in most of these proposed models, is also reviewed, and the effect of influencing parameters on the processes' controlling step (reaction or mass transfer) is discussed.

Changes in the myosin secondary structure and shrimp surimi gel strength induced by dense phase carbon dioxide.

Dense phase carbon dioxide (DPCD) could induce protein conformation changes. Myosin and shrimp surimi from Litopenaeus vannamei were treated with DPCD at 5-25MPa and 40-60°C for 20min. Myosin secondary structure was investigated by circular dichroism and shrimp surimi gel strength was determined using textural analysis to develop correlations between them. DPCD had a greater effect on secondary structure and gel strength than heating. With increasing pressure and temperature, the α-helix content of DPCD-treated myosin decreased, while the ß-sheet, ß-turn and random coil contents increased, and the shrimp surimi gel strength increased. The α-helix content was negatively correlated with gel strength, while the ß-sheet, ß-turn and random coil contents were positively correlated with gel strength. Therefore, when DPCD induced myosin to form a gel, the α-helix of myosin was unfolded and gradually converted to a ß-sheet. Such transformations led to protein-protein interactions and cross-linking, which formed a three-dimensional network to enhance the gel strength.

Wastewater treatment high rate algal pond biomass for bio-crude oil production.

This study investigates the production potential of bio-crude from wastewater treatment high rate algal pond (WWT HRAP) biomass in terms of yield, elemental/chemical composition and higher heating value (HHV). Hydrothermal liquefaction (HTL) of the biomass slurry (2.2wt% solid content, 19.7kJ/g HHV) was conducted at a range of temperatures (150-300°C) for one hour. The bio-crude yield and HHV varied in range of 3.1-24.9wt% and 37.5-38.9kJ/g, respectively. The bio-crudes were comprised of 71-72.4wt% carbon, 0.9-4.8wt% nitrogen, 8.7-9.8wt% hydrogen and 12-15.7wt% oxygen. GC-MS analysis indicated that pyrroles, indoles, amides and fatty acids were the most abundant bio-crude compounds. HTL of WWT HRAP biomass resulted, also, in production of 10.5-26wt% water-soluble compounds (containing up to 293mg/L ammonia), 1.0-9.3wt% gas and 44.8-85.5wt% solid residue (12.2-18.1kJ/g). The aqueous phase has a great potential to be used as an ammonia source for further algal cultivation and the solid residue could be used as a process fuel source.

Hydrothermal processing of cellulose: A comparison between oxidative and non-oxidative processes.

This study investigates oxidative and non-oxidative hydrothermal processing of cellulose at five different temperatures (180-260°C). Volatile fatty acids (VFAs) concentration, total suspended solid (TSS) degradation, dissolved organic carbon (DOC) and chemical oxygen demand (COD) were measured and compared in both processes. Moreover, the existence of hydrogen peroxide in both oxidative and non-oxidative processes was confirmed experimentally for the first time in literature. At temperatures ⩽220°C the amount of H2O2 produced in the oxidative process was higher (50 fold) than that of in the non-oxidative while at higher temperatures (⩾240°C) it was more for non-oxidative (3.5-5 fold). The concentration of VFAs in the non-oxidative process was lower than 10% of that in oxidative process. In both processes soluble COD increased with time and temperature, however at 260°C after reaching a maximum, it decreased with time due to conversion of some soluble intermediates to CO2 and water.

Biodiesel production potential of wastewater treatment high rate algal pond biomass.

This study investigates the year-round production potential and quality of biodiesel from wastewater treatment high rate algal pond (WWT HRAP) biomass and how it is affected by CO2 addition to the culture. The mean monthly pond biomass and lipid productivities varied between 2.0±0.3 and 11.1±2.5gVSS/m2/d, and between 0.5±0.1 and 2.6±1.1g/m2/d, respectively. The biomass fatty acid methyl esters were highly complex which led to produce low-quality biodiesel so that it cannot be used directly as a transportation fuel. Overall, 0.9±0.1g/m2/d (3.2±0.5ton/ha/year) low-quality biodiesel could be produced from WWT HRAP biomass which could be further increased to 1.1±0.1g/m2/d (4.0ton/ha/year) by lowering culture pH to 6-7 during warm summer months. CO2 addition, had little effect on both the biomass lipid content and profile and consequently did not change the quality of biodiesel.

Formation and degradation of valuable intermediate products during wet oxidation of municipal sludge.

The current study investigated the formation of organic acids and alcohols as major intermediate products of wet oxidation of municipal sludge. Municipal sludge was subjected to 60-min wet oxidation at temperatures ranging from 220 to 240°C, with 20bar oxygen partial pressure. Acetic acid was the main intermediate compound produced in this study, followed by propionic, n-butyric, iso-butyric and pentanoic acids and methanol. It was found that the process severity has a significant influence on the formation and degradation of these intermediate products.

Wastewater treatment high rate algal ponds (WWT HRAP) for low-cost biofuel production.

Growing energy demand and water consumption have increased concerns about energy security and efficient wastewater treatment and reuse. Wastewater treatment high rate algal ponds (WWT HRAPs) are a promising technology that could help solve these challenges concurrently where climate is favorable. WWT HRAPs have great potential for biofuel production as a by-product of WWT, since the costs of algal cultivation and harvest for biofuel production are covered by the wastewater treatment function. Generally, 800-1400 GJ/ha/year energy (average biomass energy content: 20 GJ/ton; HRAP biomass productivity: 40-70 tons/ha/year) can be produced in the form of harvestable biomass from WWT HRAP which can be used to provide community-level energy supply. In this paper the benefits of WWT HRAPs are compared with conventional mass algal culture systems. Moreover, parameters to effectively increase algal energy content and overall energy production from WWT HRAP are discussed including selection of appropriate algal biomass biofuel conversion pathways.

Preparation and Characterization of Microencapsulated Phase Change Materials for Use in Building Applications.

A method for preparing and characterizing microencapsulated phase change materials (MPCM) was developed. A comparison with a commercial MPCM is also presented. Both MPCM contained paraffin wax as PCM with acrylic shell. The melting temperature of the PCM was around 21 °C, suitable for building applications. The M-2 (our laboratory made sample) and Micronal® DS 5008 X (BASF) samples were characterized using SEM, DSC, nano-indentation technique, and Gas Chromatography/Mass spectrometry (GC-MS). Both samples presented a 6 µm average size and a spherical shape. Thermal energy storage (TES) capacities were 111.73 J·g-1 and 99.3 J·g-1 for M-2 and Micronal® DS 5008 X, respectively. Mechanical characterization of the samples was performed by nano-indentation technique in order to determine the elastic modulus (E), load at maximum displacement (Pm), and displacement at maximum load (hm), concluding that M-2 presented slightly better mechanical properties. Finally, an important parameter for considering use in buildings is the release of volatile organic compounds (VOC's). This characteristic was studied at 65 °C by CG-MS. Both samples showed VOC's emission after 10 min of heating, however peaks intensity of VOC's generated from M-2 microcapsules showed a lower concentration than Micronal® DS 5008 X.

Effect of high pressure processing on the conversion of dihydroxyacetone to methylglyoxal in New Zealand manuka (Leptospermum scoparium) honey and models thereof.

The effect of high pressure processing (HPP) on the conversion of dihydroxyacetone (DHA) to methylglyoxal (MGO) was examined in New Zealand manuka honey and models thereof. The objective was to confirm that previously reported increases of MGO with HPP treatment originated from conversion of DHA. RP-HPLC was used to quantify DHA, MGO and hydroxymethylfurfural (HMF) after derivatisation with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) or (in the case of MGO) separately with o-phenylenediamine (OPD). Fresh and stored manuka honey, clover honey with DHA added and artificial 26 honey with DHA added were subjected to nine different pressures and holding times and compared to untreated samples. There was no consistent trend of decrease in DHA or increase in MGO for any of the samples with any treatment. Samples showed random change generally within 5-10% of an untreated sample for MGO, DHA and HMF. HPP does not accelerate the conversion of DHA to MGO in honey.

A review of enzymatic transesterification of microalgal oil-based biodiesel using supercritical technology.

Biodiesel is considered a promising replacement to petroleum-derived diesel. Using oils extracted from agricultural crops competes with their use as food and cannot realistically satisfy the global demand of diesel-fuel requirements. On the other hand, microalgae, which have a much higher oil yield per hectare, compared to oil crops, appear to be a source that has the potential to completely replace fossil diesel. Microalgae oil extraction is a major step in the overall biodiesel production process. Recently, supercritical carbon dioxide (SC-CO(2)) has been proposed to replace conventional solvent extraction techniques because it is nontoxic, nonhazardous, chemically stable, and inexpensive. It uses environmentally acceptable solvent, which can easily be separated from the products. In addition, the use of SC-CO(2) as a reaction media has also been proposed to eliminate the inhibition limitations that encounter biodiesel production reaction using immobilized enzyme as a catalyst. Furthermore, using SC-CO(2) allows easy separation of the product. In this paper, conventional biodiesel production with first generation feedstock, using chemical catalysts and solvent-extraction, is compared to new technologies with an emphasis on using microalgae, immobilized lipase, and SC-CO(2) as an extraction solvent and reaction media.

Production of biodiesel using a continuous gas-liquid reactor.

A novel continuous reactor process has been developed for the production of biodiesel from fats and oils. The key feature of the process is its ability to operate continuously with a high reaction rate, potentially requiring less post reaction cleaning and product/reactant separation than currently established processes. This was achieved by atomising the heated oil/fat and then spraying it into a reaction chamber filled with methanol vapor in a counter current flow arrangement. This allows the continuous separation of product and the excess methanol stream in the reactor. The overall conversion based on a single cycle of this process has been between 50% and 96% of the feed stock materials. Conversions of 94-96% were achieved while operating with 5-7 g of sodium methoxide/L of methanol at methanol flow rate of 17.2 L/h and oil flow rate of 10 L/h. Additional variations in the reactant stoichiometry (i.e. reactant flow rates), catalyst type/concentration, and reaction temperature on the overall product conversion were investigated.

Seaweed processing using industrial single-mode cavity microwave heating: a preliminary investigation.

A single-cavity microwave heating system has been designed and fabricated for microwave-assisted extraction of carrageenans from seaweed. The system comprises a single mode (TE101) waveguide fitted with power and temperature controls, together with a continuous-flow-recycle reactor operating at atmospheric pressure. The system has been tested by extraction of E. cottonii and E. spinosum in aqueous organic solvents. Even without purification, the extraction products were found to have virtually identical FTIR and 13C and 1H NMR spectra to the reference samples of kappa- and iota-carrageenan, respectively. The principal advantages of the microwave system are substantial reduction of extraction time and low consumption of organic solvents.