Continuous production of fatty acid methyl esters from corn oil in a supercritical carbon dioxide bioreactor

Continuous production of fatty acid methyl esters (FAMEs) from corn oil was studied in a supercritical carbon dioxide (SC-CO₂) bioreactor using immobilized lipase (Novozym 435) as catalyst. Response surface methodology (RSM) based on central composite rotatable design (CCRD) was employed to investigate and optimize the reaction conditions: pressure (11-35 MPa), temperature (35-63 °C), substrate mole ratio (methanol:corn oil 1-9) and CO₂ flow rate (0.4-3.6 L/min, measured at ambient conditions). Increasing the substrate mole ratio increased the FAME content, whereas increasing pressure decreased the FAME content. Higher conversions were obtained at higher and lower temperatures and CO₂ flow rates compared to moderate temperatures and CO₂ flow rates. The optimal reaction conditions generated from the predictive model for the maximum FAME content were 19.4 MPa, 62.9 °C, 7.03 substrate mole ratio and 0.72 L/min CO₂ flow rate. The optimum predicted FAME content was 98.9% compared to an actual value of 93.3 ± 1.1% (w/w). The SC-CO₂ bioreactor packed with immobilized lipase shows great potential for biodiesel production.     

An experimental investigation of biodiesel synthesis from waste canola oil using supercritical methanol

Synthesis of biodiesel from waste canola oil using supercritical methanol is investigated under relatively moderate reaction conditions (240–270 °C/10 MPa) with residence time of 15–45 min and methanol to oil weight ratio of 1:1, 1.5:1 or 2:1. The effects of reaction conditions on the biodiesel yield were studied using design of experiments (DOE). The results showed that reaction time, temperature, and their interaction were the most significant factors on the yield. The highest biodiesel yield of 102% was achieved at 270 °C, 10 MPa, and methanol/oil weight ratio of 2 for 45 min reaction time. The GC–MS analysis of the reaction products showed that the by-product, glycerol, further reacted with methanol, generating methyl ethers of glycerol. Further confirmation of this side reaction was obtained by reacting glycerol and methanol at 270 °C/10 MPa for 15, 30, and 45 min. The experimental results showed these reactions could positively affect the overall biodiesel yield by providing oxygenated compounds such as 3-methoxy-1,2-propanediol, dimethoxymethane, and 2,2-dimethoxypropane as well as methyl palmitate and methyl oleate.     

Biodiesel preparation,optimization, and fuel properties from non-edible feedstock,Datura stramonium L.

This is a study on the feasibility of biodiesel preparation from a new and promising non-edible feedstock, Datura stramonium L. oil (DSO). First, important physical–chemical properties, such as oil content of seed (21.4 wt%), acid value (7.93 mg KOH/g) and fatty acid composition of expressed oil, were determined. Second, under the optimal two-step catalyzed reaction conditions, the maximum fatty acid methyl ester (FAME) yield (87%) and FAME content of more than 98 wt% were obtained. Furthermore, the fuel properties of DSO biodiesel were determined and evaluated. Compared with Jatrpha curcas L. (JC) and beef tallow (BT) biodiesel, DSO biodiesel possessed the best kinematic viscosity (4.33 mm²/s) and cold filter plug point (?5 °C). Based on the results, D. stramonium L. was identified as a promising species for biodiesel feedstock.     

Micronization and characterization of squid lecithin/polyethylene glycol composite using particles from gas saturated solutions (PGSS) process

Lecithin was isolated from squid viscera residues after supercritical carbon dioxide (SC-CO₂) extraction at 25 MPa and 45 °C. The particle formation of squid lecithin with biodegradable polymer, polyethylene glycol (PEG) was performed by PGSS using SC-CO₂ in a thermostatted stirred vessel. By applying different temperatures (40 and 50 °C) and pressures (20–30 MPa), conditions were optimized. Two nozzles of different diameters (250 and 300 μm) were used for PGSS and the reaction time was 1 h. The average diameter of the particles obtained by PGSS at different conditions was about 0.74–1.62 μm. The lowest average size of lecithin particle with PEG was found by the highest SC-CO₂ density conditions with the stirring speed of 400 rpm and nozzle size of 250 μm. The inclusion of lecithin in PEG was quantified by HPLC. Acid value and peroxide value was measured after micronization of lecithin.     

Characterization of wheat bran oil obtained by supercritical carbon dioxide and hexane extraction

Supercritical carbon dioxide (SC-CO₂) and soxhlet extraction using was carried out to extract oil from wheat bran oil. For SC-CO₂, the pressure and temperature were ranging from 10 to 30 MPa and 313.15–333.15 K. The extraction was performed in a semi batch process with a CO₂ flow rate of 26.81 g/min for 2 h. Wheat bran oil was characterized to investigate the quality. Acid value (AV) and peroxide value (POV) were higher in hexane extracted oil compared to SC-CO₂ extracted oil. Induction period was measured by rancimat test. The oil obtained by SC-CO₂ extraction had higher capability to delay the oxidation by surrounding environment. The DPPH radical scavenging activity was also measured. The SC-CO₂ extracted oil showed higher radical scavenging activity compared to hexane extracted oil.     

Response surface optimization of Smyrnium cordifolium Boiss (SCB) oil extraction via supercritical carbon dioxide

In this study, the essential oil of aerial parts of a species of a plant called Smyrnium cordifolium Boiss (SCB) was extracted by supercritical CO₂. The essence was analyzed by the method of GC/MS. Design of experiments was carried out with response surface methodology by Minitab 16 software to optimize four operating variables of supercritical carbon dioxide (SC-CO₂) extraction (pressure, temperature, CO₂ flow rate and extraction dynamic time). This is the first report announcing optimization of the operation of supercritical extraction of SCB in laboratorial conditions. Optimizing process was done to achieve maximum yield extraction. Independent variables were dynamic time (t_d), pressure (P), temperature (T) and flow rate of SC-CO₂ (Q) in the range of 30–150 min, 10–30 MPa, 40–60 °C and 0.5–1.7 ml/min, respectively. The experimental optimal recovery of essential oil (0.8431, w/w%) was obtained at 13.43 MPa, 40 °C, 150 min (dynamic) and 1.7 ml/min (CO₂ flow rate).     

Biodiesel production from waste cooking oil in a microtube reactor

Waste cooking oil (WCO) was used to produce biodiesel in a microtube reactor. First, the acid value of the WCO was reduced from 3.96 mg KOH/g to less than 1 mg KOH/g via acid catalyzed esterification. The effects of the methanol-to-WCO molar ratio (4.5:1–18:1), the H₂SO₄ concentration (0.5–2 wt.%), reaction temperature (55–70 °C), and reaction time (5–20 s) were studied. The optimal conditions were 9:1 methanol-to-WCO molar ratio, 1 wt.% H₂SO₄, 65 °C and 5 s of reaction time. Triglycerides in the product from the first step were transesterified with methanol and alkaline catalyst. Methyl ester content of the biodiesel was 91.76%.     

Supercritical carbon dioxide extraction of microalgae lipid: Process optimization and laboratory scale-up

Supercritical carbon dioxide (SC-CO₂) extraction of lipid from Scenedesmus sp. for biodiesel production was investigated and compared to conventional extraction methods. The effect of biomass pre-treatment prior to extraction and extracting conditions, namely pressure in the range of 200–500 bar, temperatures in the range of 35–65 °C and CO₂ flow rate in the range of 1.38–4.02 g min⁻¹, on SC-CO₂ extraction yield and quality of lipid were investigated. Three levels full factorial design of experiments and response surface methodology was used to model the system. A second order polynomial model was developed and used to predict the optimum conditions. Scaling up to a laboratory larger scale was also tested. The results indicated that SC-CO₂ extraction was superior to other extraction techniques, but exhibited significant variations in yield with changes in operating parameters. In the developed model, it was found that the linear and quadratic terms of the temperature, as well as the interaction with pressure had a significant effect on lipid yield; whereas, their effect on lipid quality was insignificant. The best operating conditions, in the tested range, were 53 °C, 500 bar and 1.9 g min⁻¹, in which lipid extraction yield of 7.41% (dry weight basis) was obtained. Negligible differences were observed when the fatty acid composition of SC-CO₂ extracted lipid was compared to that extracted by the conventional methods. At the optimum conditions, SC-CO₂ extraction was successfully scaled-up by eight-folds and the extracted lipid yield dropped by 16%.     

Supercritical carbon dioxide combined with high power ultrasound: An effective method for the pasteurization of coconut water

Industrially, thermal treatments are extensively used to inactivate microorganisms in foods. However, the demand for new pasteurization methods with reduced impact on the nutritional content and overall food quality is increasing. In this context, this study investigated and compared the effect of supercritical carbon dioxide (SC-CO₂) alone or in combination with high power ultrasound (HPU) on both the natural microbial flora (mesophilic, lactic acid bacteria and yeast and molds) of coconut water and the pathogenic Gram-negative bacteria Salmonella enterica inoculated in the product. Inactivation kinetics were obtained at 12 MPa, by means of batch apparatuses, at different times (from 1 up to 60 min) and temperature conditions (from 25 up to 45 °C). The synergistic effect of SC-CO₂ + HPU was evident and a higher microbial reduction was achieved compared to SC-CO₂ alone: at 12 MPa and 40 °C about 5 log reductions were achieved for natural microbial flora in about 15 min while about 30 min were needed for SC-CO₂ treatment. The storage study highlighted that SC-CO₂ treated coconut water resulted microbiologically unstable and showed heavy regrowth phenomena during the storage, while, a full shelf life of 4 weeks was assured for SC-CO₂ + HPU treated samples.     

Supercritical extraction of carob kibbles (Ceratonia siliqua L.)

Carob pulp kibbles, a by-product of carob been gum production, was studied as a source of bioactive agents. Firstly, the carob kibbles were submitted to an aqueous extraction to extract sugars, and supercritical fluid extraction (SFE) was applied to the solid residue of that aqueous extraction, by using compressed carbon dioxide (SC-CO₂) as the solvent and a mixture of ethanol and water (80:20, v/v) as a co-solvent. Pressure and temperature were studied in the ranges 15–22 MPa, and 40–70 °C. Particle diameter, and co-solvent percentage in ranges of 0.27–1.07 mm, and 0–12.4%, respectively, were also studied, as well as the flow rate of SC-CO₂ between 0.28 and 0.85 kg h⁻¹, corresponding, respectively, to 0.0062 and 0.0210 cm s⁻¹ of superficial velocity. The extracts were characterised in terms of antioxidant capacity by DPPH method, and total phenolics content by the Folin–Ciocalteu method. The central composite non-factorial design was used to optimise the extraction conditions, using the Statistica, version 6 software (Statsoft). The best results, in terms of yield and antioxidant capacity, were found at 22 MPa, 40 °C, 0.27 mm particle size, about 12.4% of co-solvent and a flow rate of 0.29 kg h⁻¹ of SC-CO₂. The phenolics profile of the extracts obtained at these conditions was qualitatively evaluated by HPLC-DAD. The solid residue of the supercritical extraction was also studied showing to be a dietary fiber, which can be compared to Caromax™, a carob fiber commercialised by Nutrinova Inc.     

Optimization of fish-oil-based biodiesel synthesis

In this study, the optimum conditions (methanol/oil mole ratio, temperature, and so on) for producing biodiesel with fish oil (menhaden oil) were established. The length of the carbon chain of fish oil is frequently greater than that of general vegetable oils. Therefore, the use of fish-oil based biodiesel with larger cetane number may improve diesel engine performance and result in a reduction of pollutant emissions. The optimum conditions of the manufacture of biodiesel with menhaden oil were reaction time of 120 min, reaction temperature of 55 °C, methanol/fish oil molar ratio of 12, and alkaline catalyst content of 2.0 wt%. In the performance evaluation of the biodiesel produced, the acid value (0.20 mg KOH/g), kinematic viscosity (4.60 cSt at 40 °C), and higher heating value (42.1 MJ/k) biodiesel quality standards were suitable.     

Macauba oil as an alternative feedstock for biodiesel: Characterization and ester conversion by the supercritical method

In this work different samples of Brazilian macauba oil obtained from mechanical pressing were characterized and production of esters of fatty acids using a catalyst-free continuous process under supercritical alcohols was assessed. Analysis of oil samples showed that the major fatty acid on pulp oil was oleic acid (mean value 62.8%), the amount of free fatty acid (FFA) was very high (37.4–65.4%), samples contained glycerides (7.4–16.5% TAG, 14.2–16.8% DAG and 1.0–3.4% MAG) and moisture was around 1.0%. Oil was processed in a continuous reactor using supercritical methanol or ethanol and the effects of temperature (573, 598, 623 and 648 K), pressure (10, 15 and 20 MPa), oil to alcohol molar ratio (1:20, 1:30 and 1:40), water concentration (0, 5 and 10 wt% added) and the flow rate of reaction mixture (1.0, 1.5, 2.0, 2.5 and 3.0 mL/min) on process efficiency were evaluated. The highest ester content achieved in reactions with supercritical methanol was 78.5% (648 K, 15 MPa, 1:30 oil:methanol molar ratio, 5 wt% water and 2.5 mL/min flow rate), while with supercritical ethanol was 69.6% (598 K, 15 MPa, 1:30 oil:ethanol molar ratio, 5 wt% water and 2.0 mL/min flow rate). The extent of the reaction was explored using a novel parameter, convertibility, which corresponds to the maximum ester content attainable from the feedstock. According to the convertibility of macauba pulp oil, the highest ester content corresponded to efficiencies of 98.0% and 86.9%, respectively. Results demonstrate that macauba oil might be a potential alternative for biodiesel production, though purification steps should be taken into account to achieve biodiesel specifications.     

Water and ethanol as co-solvent in supercritical fluid extraction of proanthocyanidins from grape marc: A comparison and a proposal

Supercritical carbon dioxide (SC-CO₂) extraction of grape marc was studied using water (W) and ethanol (EtOH) as co-solvent at 15% (w/w), 100 and 200 MPa, and 313.15, 323.15 and 333.15 K to analyze their influence upon total phenols of the extracts. The overall extraction curves were determined and suggested 10 MPa and 313.15 K as the best operating conditions for SC-CO₂ + 15%W extraction, and 10 MPa and 333.15 K for SC-CO₂ + 15% EtOH. The phenolic yields obtained were 63.4 g/kg of extract for SC-CO₂ + 15% W and 38.8 g/kg of extract for SC-CO₂ + 15% EtOH. An alternative method combining Sc-CO₂ + 15% W extraction, followed by SC-CO₂ + 15% EtOH was tested. This procedure provided the best results allowing to obtain the highest phenolic yield (68.0 g/kg of extract), phenol content (733.6 mg GAE/100 g DM), proanthocyanidins concentration (572.8 mg catechin/100 g DM) and antioxidant activity (2649.6 mg α-tocopherol/100 g DM). SC-CO₂ methods were compared with methanol extraction.     

Modelling of the inactivation kinetics of Escherichia coli,Saccharomyces cerevisiae and pectin methylesterase in orange juice treated with ultrasonic-assisted supercritical carbon dioxide

The combined effect of supercritical carbon dioxide (SC-CO₂) and high power ultrasound (HPU) on the inactivation kinetics of Escherichia coli, Saccharomyces cerevisiae and pectin-methyl esterase (PME) in orange juice was studied in order to select models that can predict their inactivation behaviour based on process parameters. Experiments were performed at different temperatures (31–41 °C, 225 bar) and pressures (100–350 bar, 36 °C). The inactivation rate of E. coli, S. cerevisiae and PME increased with pressure and temperature during SC-CO₂ + HPU treatments. The SC-CO₂ + HPU inactivation kinetics of E. coli, S. cerevisiae and PME were represented by models that included temperature, pressure and treatment time as variables, based on the Biphasic, the Peleg Type B, and the fractional models, respectively. The HPU-assisted SC-CO₂ batch system permits the use of mild process conditions and treatment times that can be even shorter than those of continuous SC-CO₂ systems.     

Supercritical CO2 extraction of omega-3 rich oil from Sacha inchi (Plukenetia volubilis L.) seeds

Supercritical carbon dioxide (SC-CO₂) was employed to extract omega-3 rich oil from Sacha inchi (Plukenetia volubilis L.) seeds and partially defatted cake. For ground seeds, the supercritical extraction was carried out at temperatures of 40, 50 and 60 °C and pressures of 300 and 400 bar, and for the cold pressed partially defatted cake, the extraction was carried out with 300 bar at 40 °C and with 400 bar at 60 °C. The global extraction yields (X₀), oil solubility, fatty acid composition of the oil and tocopherol content were determined. The seed samples used in this work contained 54.3% oil, of which 50.5% was linoleinc acid (ω-3). The maximum extraction recovery for the seeds as 92% at 400 bar and 60 °C, but on one occasion a recovery of 99.1% oil was obtained when cold pressed extraction was employed, followed by supercritical extraction at 400 bar and 60 °C. A high tocopherol content of about 2–3 g/kg of oil was obtained.     

Biodiesel production over Ca-based solid catalysts derived from industrial wastes

The solid oxide catalysts derived from the industrial waste shells of egg, golden apple snail, and meretrix venus were used as biodiesel production catalysts. Their catalytic activity in transesterification of palm olein oils and their physicochemical properties (by TG/DTA, EDX, SEM, N₂ sorption, CO₂-TPD, and XRD) were systematically investigated. The waste materials calcined in air with optimum conditions (temperature of 800 °C, time of 2–4 h) transformed calcium species in the shells into active CaO catalysts. The activity of the catalysts was in line with the basic amount of the strong base sites, surface area, and crystalline phase in the catalysts. All catalysts derived from egg and mollusk shells at 800 °C provided high activity (>90% fatty acid methyl ester (FAME) in 2 h). These abundant wastes showed good potential to be used as biodiesel production catalysts.     

Heterogeneous transesterification processes by using CaO supported on zinc oxide as basic catalysts

Zinc oxide, obtained by thermal decomposition of zinc oxalate, has been impregnated with different amounts of calcium oxide, and used as solid catalyst for transesterification processes. Catalysts have been characterized by chemical analysis, XRD, XPS, FT-IR, SEM, N₂ adsorption–desorption at 77 K and CO₂-TPD. The catalytic behaviour has been evaluated by choosing two transesterification processes: a simple model such as the reaction between ethyl butyrate and methanol and the production of biodiesel from sunflower oil and methanol. Calcium oxide is stabilized by filling the mesoporous network of ZnO, as reveal the corresponding pore size distributions, thus avoiding the lixiviation of the active phase in the reaction medium. These supported CaO catalysts, thermally activated at 1073 K, can give rise to FAME (fatty acid methyl esters) yield higher than 90%, after 2 h of reaction, when a methanol:oil molar ratio of 12 and 1.3 wt% of the catalyst with a 16 wt% CaO were employed.     

Ethanol modified supercritical carbon dioxide extraction of flavonoids from Momordica charantia L. and its antioxidant activity

Ethanol modified supercritical carbon dioxide (SC-CO₂) extraction of flavonoids from Momordica charantia L. fruits and its antioxidant activity were performed. The influences of parameters such as temperature, extraction time and pressure on the yield of flavonoids were investigated. The antioxidant activities of flavonoids were assessed by means of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging assay and β-carotene bleaching test. The experimental data obtained indicated that pressure, temperature and time had significant effect on the extraction yield. The optimum extraction conditions, determined by the 3D response surface and contour plots derived from the mathematical models, were as follows: extraction temperature 46 °C, pressure 33.4 MPa, and extraction time 53.2 min. Under these conditions, the experimental value was 15.47 mg/g, which was well matched with value predicted by the model. The antioxidant activity of flavonoids obtained by ethanol modified SC-CO₂ extraction method had higher antioxidant activity than the flavonoids extracted by conventional solvent extraction (CSE) method. The DPPH radical-scavenging ability of flavonoids obtained by ethanol modified SC-CO₂ extraction method reached to 96.14 ± 1.02%, equivalent to the clearance rate of ascorbic acid at 1.2 mg/mL. Results indicated that ethanol modified SC-CO₂ extraction was a suitable approach for the selective extraction of flavonoids from M. charantia L.     

The effect of flux and residence time in the production of biodiesel from various feedstocks using a membrane reactor

Biodiesel produced from lipid sources is a clean-burning, biodegradable, nontoxic fuel that is free of aromatic hydrocarbons. Current biodiesel production processes are tedious and involve two to three reaction steps each followed by separation and purification. Process integration of reaction and separation in a single step within a membrane reactor (MR) offers several advantages over conventional reactors.This investigation is aimed at studying the effect of membrane flux and residence time on the performance of a membrane reactor in treating a variety of raw and used feedstocks. A membrane reactor having three selectable reactor volumes was designed to decouple the effect of residence time in the reactor from membrane flux on the performance of the reactor. Low free fatty acid (FFA) oils (FFA < 1%), i.e. canola, corn, sunflower and un-refined soy oils, and high FFA waste cooking oil (FFA = 5%) were base transesterified and the quality of the biodiesel produced was determined in terms of free glycerine, mono-glyceride, di-glyceride and tri-glyceride content. All oils were base transesterified without pretreatment.Based on the composition of the final product, the MR could be operated at the upper limit of the flux tested (70 L/m²/h) and a residence time of 60 min. The ASTM D6751 and EN 14214 standards for glycerin and glycerides were reached in the washed biodiesel product for all feedstocks and run conditions. The operating pressure in the reactor was exceeded at 70 L/m²/h in treating waste oils and pre-treated corn oil. For these oils, reasonable operating pressures in the reactor were reached at a membrane flux of 30–40 L/m²/h. The quality of the washed biodiesel always met ASTM and EN standards. The FAME produced from WCO at intermediate fluxes and high residence times met the ASTM and EN standards without water washing.     

Modeling the inactivation of Staphylococcus aureus and Serratia marcescens in clinical solid waste using supercritical fluid carbon dioxide

The aim of the present study was to determine an effective sterilization method for safe handling and recycle-reuse of clinical solid waste materials. Supercritical fluid carbon dioxide (SC-CO₂) was applied in the inactivation of gram positive Staphylococcus aureus (S. aureus) and gram negative Serratia marcencens (S. marcescens) in clinical solid waste. The colony forming activity of the bacteria was completely lost at pressures 10–40 MPa, temperatures 35–80 °C and treatment period between 5 and 120 min. An increase in pressure at constant temperature and vice versa with the increasing treatment time enhanced the SC-CO₂ inactivation efficiency. The inactivation process was illustrated by the modified Gompertz equation. The SC-CO₂ inactivation of bacteria was compared with the steam autoclaved bacteria. Regrowth of the bacteria was observed in the autoclaved sample while no re-growth was detected in the SC-CO₂ treated clinical solid waste. Results from SEM image analysis, cellular protein and enzymatic activity of untreated, autoclaved and SC-CO₂ treated S. marcescens and S. aureus cells confirmed that SC-CO₂ is an effective sterilization method.