Rodrigo Navia

Biotechnological processes for biodiesel production using alternative oils

As biodiesel (fatty acid methyl ester (FAME)) is mainly produced from edible vegetable oils, crop soils are used for its production, increasing deforestation and producing a fuel more expensive than diesel. The use of waste lipids such as waste frying oils, waste fats, and soapstock has been proposed as low-cost alternative feedstocks. Non-edible oils such as jatropha, pongamia, and rubber seed oil are also economically attractive. In addition, microalgae, bacteria, yeast, and fungi with 20% or higher lipid content are oleaginous microorganisms known as single cell oil and have been proposed as feedstocks for FAME production. Alternative feedstocks are characterized by their elevated acid value due to the high level of free fatty acid (FFA) content, causing undesirable saponification reactions when an alkaline catalyst is used in the transesterification reaction. The production of soap consumes the conventional catalyst, diminishing FAME production yield and simultaneously preventing the effective separation of the produced FAME from the glycerin phase. These problems could be solved using biological catalysts, such as lipases or whole-cell catalysts, avoiding soap production as the FFAs are esterified to FAME. In addition, by-product glycerol can be easily recovered, and the purification of FAME is simplified using biological catalysts.

Adsorption studies of the herbicide simazine in agricultural soils of the Aconcagua valley, central Chile.

Simazine is a s-triazine herbicide that has been applied worldwide for agriculture. This herbicide is the second most commonly detected pesticide in surface and groundwater in the United States, Europe and Australia. In this study, simazine adsorption behaviour was studied in two agricultural soils of the Aconcagua valley, central Chile. The two studied soils were soil A (loam, 8.5% organic matter content) and soil B (clay-loam, 3.5% organic matter content). Three times higher simazine adsorption capacity was observed in soil A (68.03 mg kg(-1)) compared to soil B (22.03 mg kg(-1)). The simazine adsorption distribution coefficients (K(d)) were 9.32 L kg(-1) for soil A and 7.74 L kg(-1) for soil B. The simazine adsorption enthalpy in soil A was -21.0 kJ mol(-1) while in soil B the adsorption enthalpy value was -11.5 kJ mol(-1). These results indicate that simazine adsorption process in these soils is exothermic, governing H bonds the adsorption process of simazine in both the loam and clay-loam soils. These results and the potentiometric profiles of both soils, suggest that simazine adsorption in soil A is mainly governed by simazine-organic matter interactions and in soil B by simazine-clay interactions. The understanding of simazine sorption-desorption processes is essential to determine the pesticide fate and availability in soil for pest control, biodegradation, runoff and leaching.

Heavy metals retention capacity of a non-conventional sorbent developed from a mixture of industrial and agricultural wastes.

Zinc and copper removal from aqueous solutions using brine sediments (industrial residue), sawdust (agricultural residue) and the mixture of both materials has been researched through batch and column tests. Brine sediments were found to be mainly constituted by halite and calcite, while its main cations exchangeable were sodium, calcium, magnesium and potassium. In sawdust the main exchangeable cations detected were calcium, magnesium, sodium and potassium. FT-IR spectra of sawdust and brine sediment-sawdust mixture showed that brine sediments produced important changes in carboxylic, alcoholic and phenolic groups present in the sawdust. The maximum zinc adsorption capacity was found to be 4.85, 2.58 and 5.59 mg/g using an adsorbent/solution ratio of 1/40, for brine sediments, sawdust and the mixture, respectively. For copper, the maximum adsorption capacity was found to be 4.69, 2.31 and 4.33 mg/g, using adsorbent/solution ratios of 1/40, for brine sediments, sawdust and the mixture, respectively. Maximum copper adsorption capacity of the mixture, on the contrary to zinc adsorption, was lightly inferior to maximum adsorption capacity obtained in brine sediments. Adsorption isotherms data adjusted better to the Langmuir model. Additionally, columns reached the saturation point at 690 min for zinc and 360 min for copper. The main mechanism involved in the removal of both metals may be the ionic exchange between sodium and calcium ions present in brine sediments and H(+) present in functional groups of sawdust. The use of brine sediments, sawdust and their mixture, presents an interesting option both, for wastewater decontamination (as a possible non-conventional sorbent for the removal of heavy metals) and as a waste recycling option.

Fly ashes from coal and petroleum coke combustion: current and innovative potential applications

Coal fly ashes (CFA) are generated in large amounts worldwide. Current combustion technologies allow the burning of fuels with high sulfur content such as petroleum coke, generating non-CFA, such as petroleum coke fly ash (PCFA), mainly from fluidized bed combustion processes. The disposal of CFA and PCFA fly ashes can have severe impacts in the environment such as a potential groundwater contamination by the leaching of heavy metals and/or particulate matter emissions; making it necessary to treat or reuse them. At present CFA are utilized in several applications fields such as cement and concrete production, agriculture and soil stabilization. However, their reuse is restricted by the quality parameters of the end-product or requirements defined by the production process. Therefore, secondary material markets can use a limited amount of CFA, which implies the necessity of new markets for the unused CFA. Some potential future utilization options reviewed herein are zeolite synthesis and valuable metals extraction. In comparison to CFA, PCFA are characterized by a high Ca content, suggesting a possible use as neutralizers of acid wastewaters from mining operations, opening a new potential application area for PCFA that could solve contamination problems in emergent and mining countries such as Chile. However, this potential application may be limited by PCFA heavy metals leaching, mainly V and Ni, which are present in PCFA in high concentrations.

Improving fatty acid methyl ester production yield in a lipase-catalyzed process using waste frying oils as feedstock

The application of waste frying oil (WFO) mixed with rapeseed oil as a feedstock for the effective production of fatty acid methyl esters (FAME) in a lipase-catalyzed process was investigated. The response surface methodology (RSM) was used to optimize the interaction of four variables: the percentage of WFO in the mixed feedstock, the methanol-to-oil ratio, the dosage of Novozym 435 as a catalyst and the temperature. Furthermore, the addition of methanol to the reaction mixture in a second step after 8 h was shown to effectively diminish enzyme inhibition. Using this technique, the model predicted the optimal conditions that would reach 100% FAME, including a methanol-to-oil molar ratio of 3.8:1, 100% (wt) WFO, 15% (wt) Novozym 435 and incubation at 44.5 degrees C for 12 h with agitation at 200 rpm, and verification experiments confirmed the validity of the model. According to the model, the addition of WFO increased FAME production yield, which is largely due to its higher contents of monoacylglycerols, diacylglycerols and free fatty acids (in comparison to rapeseed oil), which are more available substrates for the enzymatic catalysis. Therefore, the replacement of rapeseed oil with WFO in Novozym 435-catalyzed processes could diminish biodiesel production costs since it is a less expensive feedstock that increases the production yield and could be a potential alternative for FAME production on an industrial scale.

Lipase-catalyzed process in an anhydrous medium with enzyme reutilization to produce biodiesel with low acid value.

One major problem in the lipase-catalyzed production of biodiesel or fatty acid methyl esters (FAME) is the high acidity of the product, mainly caused by water presence, which produces parallel hydrolysis and esterification reactions instead of transesterification to FAME. Therefore, the use of reaction medium in absence of water (anhydrous medium) was investigated in a lipase-catalyzed process to improve FAME yield and final product quality. FAME production catalyzed by Novozym 435 was carried out using waste frying oil (WFO) as raw material, methanol as acyl acceptor, and 3Å molecular sieves to extract the water. The anhydrous conditions allowed the esterification of free fatty acids (FFA) from feedstock at the initial reaction time. However, after the initial esterification process, water absence avoided the consecutives reactions of hydrolysis and esterification, producing FAME mainly by transesterification. Using this anhydrous medium, a decreasing in both the acid value and the diglycerides content in the product were observed, simultaneously improving FAME yield. Enzyme reuse in the anhydrous medium was also studied. The use of the moderate polar solvent tert-butanol as a co-solvent led to a stable catalysis using Novozym 435 even after 17 successive cycles of FAME production under anhydrous conditions. These results indicate that a lipase-catalyzed process in an anhydrous medium coupled with enzyme reuse would be suitable for biodiesel production, promoting the use of oils of different origin as raw materials.

Allophanic Soil Adsorption System as a Bleached Kraft Mill Aerobic Effluent Post-Treatment

Bleached Kraft mill effluent was treated in an activated sludgereactor followed by an allophanic soil adsorption system (ASAS). Under aerobic conditions, removal efficiencies of biological oxygen demand (BOD5) and chemical oxygen demand (COD) varied between 57.7–96.5% and 30.3–57.0%, respectively, depending on the hydraulic retention time (HRT). On the other hand, tannin-lignin and phenolic compounds removal efficiencies attained values between 13.2–51.2 and 3.6–33.5%,respectively. An allophanic soil adsorption system was designed for color and phenolic compounds removal. Three different types of soils were used: Natural allophanic soil as the control compared, with calcinated and acidified allophanic soil. The initial removal efficiencies for phenolic compounds varied between 72 an 87% for activated soils, while color initial removal efficiencies were between 95 and 99%. Moreover, COD and tannin-lignin initial removal efficiencies reached maximum values of 74 and 87%, respectively, for calcinated soil. Design parameters show that there is an enhancement factor in adsorption capacities for both activated soils. In fact, phenolic compounds breakpoint adsorption capacity increased 5.3 times for calcinated soil and 17.6 times for acidified soil, while saturation capacity increased between 2.2 and 3.2 times. In addition, color breakpoint adsorption capacity increased 2.8 times for calcinated soil and 10.4 times for acidified soil, while saturation capacity increased between 3.2 and 5.5 times.

Evaluation of biodegradable polymers as encapsulating agents for the development of a urea controlled-release fertilizer using biochar as support material.

Biochar constitutes a promising support material for the formulation of controlled-release fertilizers (CRFs). In this study we evaluated the effect of different polymeric materials as encapsulating agents to control nitrogen (N) leaching from biochar based CRFs. Nitrogen impregnation onto biochar was performed in a batch reactor using urea as N source. The resulting product was encapsulated by using sodium alginate (SA), cellulose acetate (CA) and ethyl cellulose (EC). Leaching potential was studied in planted and unplanted soil columns, monitoring nitrate, nitrite, ammonium and urea concentrations. After 90 days, plants were removed from the soil columns and plant yield was evaluated. It was observed that the ammonium concentration in leachates presented a maximum concentration for all treatments at day 22. The highest concentration of N in the leachates was the nitrate form. The crop yield was negatively affected by all developed CRFs using biochar compared with the traditional fertilization.

In situ biodiesel production from greasy sewage sludge using acid and enzymatic catalysts.

This study proposes to select the most appropriate sewage sludge (greasy, primary and secondary) for in situ transesterification and to compare the technical, economic and energetic performance of an enzymatic catalyst (Novozym®435) with sulfuric acid. Greasy sludge was selected as feedstock for biodiesel production due to its high lipid content (44.4%) and low unsaponifiable matter. Maximum methyl esters yield (61%) was reached when processing the wet sludge using sulfuric acid as catalyst and n-hexane, followed by dried-greasy sludge catalyzed by Novozym®435 (57% methyl esters). Considering the economic point of view, the process using acid catalyst was more favorable compared to Novozym®435 catalyst due to the high cost of lipase. In general, greasy sludge (wet or dried) showed high potential to produce biodiesel. However, further technical adjustments are needed to make biodiesel production by in situ transesterification using acid and enzymatic catalyst feasible.

Enzymatic biodiesel production kinetics using co-solvent and an anhydrous medium: a strategy to improve lipase performance in a semi-continuous reactor

Enzymatic biodiesel production kinetics under previously optimized conditions were investigated. Waste frying oil (WFO) was used as the raw material, Novozym 435 as catalyst, methanol as acyl acceptor and tert-butanol as co-solvent. To investigate pure transesterification kinetics improving product properties, 3Å molecular sieves were incorporated into the reaction to provide an anhydrous medium avoiding the side reactions of hydrolysis and esterification. The effects of either WFO or methanol on the reaction rate were analyzed separately. The reaction was described by a Ping Pong mechanism and competitive inhibition by methanol. The results obtained in the kinetics study were applied in the operation of a semi-continuous reactor for biodiesel production. The operational conditions of each reaction cycle were: methanol-to-oil ratio 8/1 (mol/mol), 15% (wt) Novozym 435, 0.75% (v/v) of tert-butanol, 44.5°C, 200 rpm and 4h of reaction time. The enzymes were successively reused by remaining in the reactor during all the cycles. Under these conditions, biodiesel production yields higher than 80% over 7 reaction cycles were observed. Both the kinetics study and the reactor operation showed that Novozym 435 was not inhibited at high methanol concentrations and that the kinetics of the proposed enzymatic process could be comparable to the conventional chemical process.