CO2-assisted fiber impregnation

Near-critical and supercritical CO₂ is used to facilitate the impregnation of additives, vanillin and l-menthol, into cellulose acetate (CA). SCF technology applied at low pressures is a viable approach for this application since CO₂ only has to dissolve low molecular weight compounds and not the CA fiber. Hence, impregnation operating temperatures are kept under 60 °C and optimum operating pressures are less than 2000 psig and are typically closer to 1250 psig. The optimum operating conditions are intimately linked to the mass transfer and phase behavior characteristics of polymer-CO₂, polymer-additive, and additive-CO₂ mixtures. It is possible to impregnate up to ∼10 wt% vanillin or l-menthol into CA fiber as verified by gravimetric, TGA, and TGA/MS analyses. SEM analysis of the CA fiber shows that the fiber does not undergo structural changes during this impregnation process even when the fiber is rapidly depressurized. At atmospheric conditions, the additives are in solid form in the CA fiber and slowly diffuse from the fiber at a rate fixed by solid diffusion from a semi-crystalline polymer matrix. Hence, a significant amount of additive is still present in the fiber after one month.     

Synthesis and charge/discharge properties of cellulose derivatives carrying free radicals

Ethyl cellulose derivatives [EC-T and EC-P] and cellulose acetate derivatives [CA-T and CA-P] carrying TEMPO or PROXY radicals (TEMPO = 2,2,6,6-tetramethyl-1-piperidinyloxy, PROXY = 2,2,5,5-tetramethyl-1-pyrrolidinyloxy) were synthesized with moderate number-average molecular weights of 62?400-126?000 in 84-88% yield by the reaction of 4-carboxy-TEMPO or 3-carboxy-PROXY with residual hydroxyl group of ethyl cellulose or cellulose acetate. All the free radical-containing cellulose derivatives demonstrated reversible charge/discharge processes, whose discharge capacities were 42.8-61.1 A h/kg. In particular, the CA-T-based cell displayed two-stage discharge process, and the first-stage discharge capacity reached 29.5 A h/kg which corresponds to 74% of its theoretical value, and that of the total capacity was 61.1 A h/kg which approaches up to 153% of the theoretical value for one-electron redox reaction.     

Organic nanoparticles recovery in supercritical antisolvent precipitation

One of the major problems in dry nanoparticles production and handling is their recovery. Indeed, they tend to disperse in all the precipitation chamber and, due to their dimensions, are very difficult to collect.Supercritical antisolvent precipitation (SAS) was frequently used to produce nanoparticles at very mild conditions of pressure and temperature, but the issues of sedimentation mechanisms and nanoparticles recovery as single units, have not been evaluated yet.In this work, SAS nanoparticles were produced for samarium acetate, rifampicin, astemizole, amoxicillin trihydrate, tetracycline hydrochloride, clemastine, cellulose acetate and disperse red 60; the powders were collected as aggregates, due to the specific sedimentation mechanism that characterizes the process. SAS produced nanoparticles of the previously listed materials were precipitated from different organic solvents. Then, they were post-processed by ultrafiltration, ultracentrifugation and ultrasound based techniques, demonstrating that they can be easily separated in single nano-units. Nanoparticles showed mean diameters in the range 50-150 nm.     

Impregnation of vitamin E acetate on silica mesoporous phases using supercritical carbon dioxide

Impregnation of a drug model (α-tocopheryl acetate) into mesoporous host matrices has been carried out using supercritical carbon dioxide (SC CO₂) as impregnation solvent at 15 MPa and 313 K with a flow rate of 500 g h⁻¹. The operating conditions were defined following the solute concentration in the fluid phase as a function of pressure and carbon dioxide flow rate. Solubility measurements of α-tocopheryl acetate were first performed at 313 K for pressures ranging 10-20 MPa. High values of solubility in SC CO₂ were measured: 6 wt% at 10 MPa and 14 wt% at 20 MPa. Measurements of the concentration of the solute in SC CO₂ in the experimental conditions of impregnation in dynamic mode showed than it was ten times lower than the solubility. The variations of this concentration have been studied at 313 K, for a pressure varying from 8 to 15 MPa, and for a carbon dioxide flow rate varying from 120 to 600 g h⁻¹. Two different host matrices were used: a commercial chromatographic silica support and a MCM-41-type mesoporous organized silica synthetized at the laboratory. This latter showed the best drug loading of 1.14 g per gram of adsorbent. The drug loadings obtained in supercritical media were similar to the ones obtained in liquid media using hexane as impregnation solvent. Nevertheless, the maximum loading was obtained after 1 h of impregnation in SC media while 4 h were needed in liquid media.     

Prospects of non-catalytic supercritical methyl acetate process in biodiesel production

Conventional biodiesel production methods utilize alcohol as acyl acceptor and produces glycerol as side product. Hence, with escalating production of biodiesel throughout the world, it leads to oversupply of glycerol and subsequently causes devaluation in the market. In this study, methyl acetate was employed as acyl acceptor in non-catalytic supercritical methyl acetate (SCMA) process to produce fatty acid methyl esters (FAME) and side product of triacetin, a valuable fuel additive instead of glycerol. Consequently, the properties of biodiesel produced (FAME and triacetin) are superior compared to conventional biodiesel method (FAME only). In this research, the effects of reaction temperature, reaction time and molar ratio of methyl acetate to oil on the yield of biodiesel were investigated. Apart from that, the influence of impurities commonly found in waste oils/fats such as free fatty acids and water were studied as well and compared with methanol-based reactions of supercritical and heterogeneous catalysis. Results show that biodiesel yields in SCMA process could achieve 99 wt.% when the operating conditions were fixed at 400 °C/220 bar for reaction temperature, methyl acetate/oil molar ratio of 30:1 and 60 min of reaction time. Furthermore, SCMA did not suffer from adverse effect with the presence of impurities, proving that SCMA has a high tolerance towards contamination which is crucial to allow the utilization of inexpensive waste oils/fats as biodiesel feedstock.     

Antioxidant compounds recovery from grape residues by a supercritical antisolvent assisted process

A process is proposed to selectively extract polyphenols and anthocyanins from lyophilized grape residues. The compounds of interest are first extracted from the vegetable matter, using a tartaric buffer to avoid extract degradation due to polyphenol oxidase, hydrolysis or esterification and to eliminate part of the interfering compounds (mainly sugars). Then, they are selectively adsorbed on a C18 column and desorbed using methanol. The methanolic solution is processed by supercritical antisolvent extraction (SAE) at various process conditions. The optimized result is a powderous, solventless precipitate that, in the case of Cannonau cultivar, contains 33 polyphenols and 7 anthocyanins. The overall content of polyphenols recovered is of 521 mg/kg and the total content of anthocyanins is of 15542 mg/kg of treated material. The most abundant compounds extracted are cathechin (113.9 mg/kg), epicathechin (96.9 mg/kg), epicathechin gallate (101.6 mg/kg) for polyphenols and malvin acetate (1304 mg/kg) and malvin cumarate (9256.9 mg/kg) for anthocyanins. SAE processing confirms to be very effective in producing solventless selective extracts, avoiding their degradation.     

Effects of extraction temperature, extraction pressure and nozzle diameter on micronization of cholesterol by RESS process

Micronized cholesterol particles were produced via the Rapid Expansion of Supercritical CO₂ Solutions (RESS) process. Taguchi design was used for designing the experimental plan to investigate the effects of three parameters including extraction temperature (40-60 °C), extraction pressure (100-160 bar) and nozzle diameter (0.15-0.24 mm) on the size and morphology of the cholesterol particles produced by the RESS process. The characterization of the particles was carried out using scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements to evaluate the performance of RESS process. The average particle size of the original material was 55 μm ± (2.84) while the average particle size of cholesterol after size reduction via the RESS process was between the minimum of 0.62 μm ± (0.03) and the maximum of 4.83 μm ± (0.18) depending upon the experimental conditions used. It was observed that both increasing the temperature from 40 to 60 °C and increasing the nozzle diameter from 0.15 to 0.24 mm result a reducing effect on the average particle size, whereas extraction pressure (100-160 bar) change has slight effect on the average particle size.     

Biomass gasification in supercritical water: Part 1. Effect of the nature of biomass

In this study, biomass feedstocks, including lignocellulosic materials and the tannery wastes, were gasified in supercritical water. Gasification experiments were performed in a batch autoclave at 500 °C. The amount of gases, the gas compositions and the amount of water soluble compounds from gasification were determined. The hydrogen yields ranging between 4.05 and 4.65 mol H₂/kg biomass have been obtained. The results showed that the yields and composition of gases depend also on the organic materials other than cellulose and lignin in lignocellulosic material. In addition to this, it was concluded that the kind of lignin may also have an effect on gasification products. In the case of tannery wastes, the type of tannen agent used in leather production considerably effected the gasification results.     

Influence of pressure, temperature and concentration on the mechanisms of particle precipitation in supercritical antisolvent micronization

In this work, supercritical antisolvent micronization (SAS) is used to produce nanoparticles, microparticles and expanded microparticles of a model compound, gadolinium acetate (GdAc), using dimethylsulfoxide (DMSO) as the liquid solvent with the aim of studying the dependence of particles’ diameter and morphology on some process parameters like pressure, temperature and concentration of the starting solution. Experiments are performed varying the precipitation pressure between 90 and 200 bar, the precipitation temperature between 35 and 60 °C and the concentration of GdAc in the liquid solution in the range from 20 to 300 mg/mL. The experimental evidences show that the formation of particles with specific sizes in the micrometric and nanometric range depends on specific values of each one of these parameters. An explanation of the results is proposed in terms of the competition between two characteristic times of the SAS process that can control the precipitation process. The time of jet break-up of the liquid solution that produces liquid droplet formation, and the dynamic surface tension vanishing time, that induces gas mixing with the precipitation of nanoparticles from the gaseous phase. Indeed, GdAc sub-microparticle, or microparticle (diameter in the range 0.23-1.6 μm with mean diameters in the range 0.28-0.52 μm) formation can be attributed to micro-droplet drying, whereas nanoparticles (mean diameter in the range 90-210 nm) are consistently produced when gas mixing is the possible governing process. In conclusion, the precipitation mechanisms can be modulated varying one SAS parameter a time, thus selecting the range of particle diameters required for the specific application.     

Supercritical fluid-assisted dispersion of C.I. pigment violet 23 in an organic medium

This study investigates the dispersions of 1 wt.% C.I. pigment violet 23 particles in propylene glycol monomethyl ether acetate (PGMEA) using a supercritical fluid-assisted dispersion process (SFAD). The favorable formulation of dispersants is a blend of 40% AJISPER PB821 and 10% FC-4430 in a PGMEA medium. The SFAD processes holding at the supercritical state are good for improving dispersion. Under favorable conditions, 328.2 K and 20 MPa, the mean size of pigment dispersoid with blended dispersants in PGMEA is as small as 175 nm that meets the required range of 100-200 nm in industrial applications. The TGA analyses indicate the adsorbed amount of blended dispersants (40% PB821 and 10% 4430) on the surface of pigment particles in the PGMEA medium is about 1.77 mg/m². Thus, the transmittances, color analyses, and TEM images of pigment dispersoids prove that the SFAD process can disperse pigment particles in PGMEA.     

Cellulose-based aerogels

New organic aerogels were prepared using cellulose derivatives as precursors. The elaboration process and the structural characterisations of these porous cellulose-based materials are described in the present study. Series of monolithic gels were synthesised in acetone by crosslinking cellulose acetate with a non-toxic isocyanate via sol-gel route, using tin-based catalyst. Gelation times (ranging from 15 to 150 min) were significantly dependent on reagents' nature and concentration. Low-density materials (from 0.25 cm³/g to 0.85 cm³/g) were obtained after supercritical carbon dioxide drying. These newly developed nanostructured materials were characterised using mercury porosimetry, nitrogen adsorption and scanning electron microscopy. All the prepared materials have shown both a nanostructured solid network (specific surface areas between 140 and 250 m²/g) and a nanoporous network (characteristic pore sizes between 13 and 25 nm) together with specific porous volumes as large as 3.30 cm³/g.Influence of sol-gel synthesis parameters as crosslinker content and cellulose degree of polymerisation or concentration was investigated. First empirical correlations between synthesis parameters and final material properties were obtained. A special attention was dedicated to the different shrinkages occurring during the elaboration process. In particular, the important shrinkage occurring during the supercritical drying step was studied in terms of affinity between the crosslinked polymeric network and carbon dioxide. In parallel, first thermo-mechanical properties were presented in terms of bulk modulus and effective thermal conductivity.     

Recovery of triglycerides from used frying oil by extraction with liquid and supercritical ethane

The extraction of triglycerides from used frying oil with liquid and supercritical ethane has been studied in a semibatch system at different temperatures (25-80 °C) and pressures (150-250 kg/cm²). It has been found that isobaric decreases of temperature and isothermal increases of pressure lead to both increasing extraction yields and decreasing separation efficiencies. Lipid fractions recovered in the high density region had acceptable concentrations of polar compounds.Results with ethane have been compared to those reported for CO₂ in earlier works. At similar reduced densities of the solvents, oil solubility in ethane was higher than in CO₂, being the separation efficiency of polar fractions slightly better when using ethane.The extraction process was further analyzed in a packed countercurrent column. At optimum conditions (250 kg/cm², 25 °C, and solvent-to-oil ratio 45 g:g) about 85% of the triglycerides were recovered, being 11.2% the polar content of the triglyceride fraction recovered.     

Particle size design of digitoxin in supercritical fluids

Bioavailability of the pharmaceutical substances is very important for their activity. In case of necessity, bioavailability can be improved by reducing the particle size of the drugs. In this study, particle size of digitoxin was reduced by the Rapid Expansion of Supercritical Solutions (RESS). The effects of pre-expansion temperature (90-110 °C), flow rate (2.5-7.5 ml/min), spray distance (3-7 cm) on the size and size distribution of the precipitated digitoxin particles were carried out. The particles were characterized by dynamic light scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and LC-MS analysis.While the particle size range of the original digitoxin was 0.2-8 μm, it was decreased to 68-458 nm and determined that 97% of the particles were below 200 nm depending on the different experimental conditions.Response surface method (RSM) was used to optimize the process parameters. The flow rate, 7 ml/min; spray distance, 7 cm; pre-expansion temperature, 95 °C were found to be the optimum conditions to achieve the minimum particle size of digitoxin.     

Radical-scavenging activity of extracts from Cordia verbenacea DC obtained by different methods

The possibility of using the leaves of Cordia verbenacea as a new source of natural antioxidant compounds was investigated. In the present work, extracts from C. verbenacea were obtained using different extraction methods: supercritical fluid extraction (SFE), Soxhlet (SE), hydrodistillation and maceration, with the objective to evaluate the methods in terms of yield and antioxidant potential. The high-pressure technique was applied using pure CO₂ and CO₂ with co-solvent at different temperatures and pressures (30, 40 and 50 °C and 100, 200, and 300 bar). Organic solvents with different polarities were used to obtain extracts by low-pressure extraction processes. The extracts were evaluated according to their antioxidant activity using total phenolic content, scavenging abilities on DPPH radical, total antioxidant activities (ABTS^•+), superoxide anion radical-scavenging (O₂^•) and protection against lipid peroxidation in vitro (LPO). Ethyl acetate fraction obtained by maceration and extract isolated by SE using 25% aqueous mixture of ethanol possessed the highest scavenger activity against DPPH radical (IC₅₀ = 9.2 ± 0.4 μg/ml, IC₅₀ = 27.4 ± 0.1 μg/ml, respectively). The SFE with 8% ethanol as a co-solvent produced extracts with distinguished increase in the antioxidant activity. The Soxhlet extract with ethyl acetate exhibited a strong reduction of lipid peroxidation (IC₅₀ = 209 ± 3 μg/ml) value comparable to the standard rutin (IC₅₀ = 203 ± 2 μg/ml). The results indicate that extracts of C. verbenacea have important potential as a source of bioactive compounds with antioxidant activity.     

Continuous synthesis of castor oil ethyl esters under supercritical ethanol

The transesterification of castor oil under supercritical ethanol using a catalyst-free continuous process was investigated. The effect of water concentration on the reaction medium, reaction temperature, pressure, and substrates flow rate were studied. A maximum ester content of 74.2% was achieved when the reactor was operated at 573 K, 20 MPa, substrates flow rate of 0.8 ml min⁻¹, and 5 wt% water concentration in the alcohol. The ester content of the product increased with the operation temperature, but after certain temperature level the converse effect was observed. This adverse effect was attributed to oil degradation, which increased to 88.7% at 648 K (at the flow rate of 0.8 ml min⁻¹). A favorable effect on ester content was observed when the water concentration was increased, unlike the effect of water on the conventional alkali-catalyzed process.     

Preparation of porous carbons from thermoplastic precursors and their performance for electric double layer capacitors

Porous carbons with high surface area were successfully prepared from thermoplastic precursors, such as poly(vinyl alcohol) (PVA), hydroxyl propyl cellulose and poly(ethylene terephthalate), by the carbonization of a mixture with MgO at 900 °C in an inert atmosphere. After carbonization the MgO was dissolved out using a diluted sulfuric acid and the carbons formed were isolated. The mixing of the PVA carbon precursor with the MgO precursors (reagent grade MgO, magnesium acetate or citrate) was done either in powder form or in an aqueous solution. The BET surface area of the carbons obtained via solution mixing could reach a very high value, such as 2000 m²/g, without any activation process. The pore structure of the resultant carbons was found to depend strongly on the mixing method; the carbons prepared via solution mixing were rich in mesopores, but those produced via powder mixing were rich in micropores. The size of mesopores was found to be almost the same as that of the MgO particles, suggesting a way of controlling the mesopore size in the resultant carbons. Measurement of capacitance was carried out in 1 mol/L H₂SO₄ electrolyte. The porous carbon with a BET surface area of 1900 m²/g prepared at 900 °C through solution mixing of Mg acetate with PVA showed a fairly high EDLC capacitance, about 250 F/g with a current density of 20 mA/g and 210 F/g with 1000 mA/g. The rate performance was closely related to the mesoporous surface area.     

Generation of chitosan nanoporous structures for tissue engineering applications using a supercritical fluid assisted process

In recent years, considerable attention has been given to chitosan-based materials and their applications in the field of tissue engineering. However, the techniques proposed until now for the formation of chitosan scaffolds present some limitations such as: they are very time-consuming, use organic solvents, have difficulties in the obtainment and preservation of various levels of porosity and the 3-D structure. In this work, a new SC-CO₂ assisted process for the production of chitosan scaffolds is proposed; it consists of three steps: formation of a chitosan hydrogel by thermally induced phase separation; substitution of water with a suitable solvent; drying of the gel using SC-CO₂. Using this process, we produced chitosan nanostructured networks with filaments diameters around 50 nm, without any collapse of the gel nanostructure, characterized by a high porosity (>91%) and high compressive modulus (150 kPa).     

Optimization of total alkannin yields of Alkanna tinctoria by using sub- and supercritical carbon dioxide extraction

The effects of supercritical carbondioxide extraction was investigated to compare previously validated extraction methods on total alkannin yield with Alkanna tinctoria collected form Antalya, Turkey. A two-step process was used; extraction of alkannin derivatives with supercritical CO₂ followed by alkaline hydrolysis of alkannin derivatives. A Box-Behnken exprerimental design was used to evaluate the effect of three variables, pressure (50-350 bar), temperature (30-80 °C) and CO₂ flow (5-20 g min⁻¹) at 1:30 ratio of alkanna root:CO₂ amount. Response surface analysis revealed that the data were adequately fitted to a second-order polynomial model with R² 0.9665 and the most effective variable was pressure (P ≤ 0.05). Optimum conditions were determined as 80 °C, 175 bar, 5 g min⁻¹ CO₂ flow yielding the highest total alkannins (1.47%) which was higher than conventional hexane extraction (1.24%) providing a solvent-free alternative for industrial production.     

Continuous countercurrent deterpenation of lemon essential oil by means of supercritical carbon dioxide: Experimental data and process modelling

A thermodynamic model based on the Peng-Robinson equation of state was developed in order to perform high-pressure phase equilibria calculations for the system carbon dioxide-lemon essential oil. The multicomponent natural oil was simulated by a mixture of three key components, one for each relevant class of compounds (monoterpenes, monoterpene oxygenated derivatives and sesquiterpenes). Firstly the proposed model was validated on semi-batch experimental data and then it was used to simulate the behaviour of a continuously operated countercurrent column. Experiments on deterpenation process on a packed column, operating as a stripping section, were carried out in the temperature range 50-70 °C and pressure range 8.7-11.2 MPa. The comparison between experimental results and process simulation demonstrated that the proposed model is capable of reliable predictions on the behaviour of the countercurrent continuous deterpenation process. Furthermore, an average height equivalent to a theoretical plate of about 40 cm was estimated, for the stated packing and operating conditions. A case study for the production of 10-fold high quality oil, with strict specifications for the recovery of oxygenated compounds (99%), was investigated by simulations of a continuous countercurrent process with an external reflux. The linkage between the number of theoretical stages, the reflux ratio and the solvent to feed ratio was investigated throughout the above-mentioned pressure and temperature ranges. Operating conditions at higher pressure and temperature proved to be more favourable. As an example, operating a 20 theoretical stage column at 70 °C and 11.2 MPa, it is possible to attain process specifications with a solvent to feed ratio of about 63.     

Continuous extraction of glycerol acetates from their mixture using supercritical carbon dioxide

Supercritical carbon dioxide was used for partially selective extraction of triacetin from a mixture of triacetin, diacetin, and monoacetin with a molar ratio of 1:2:1. The extraction was carried out in two stages. In the first stage, a central composite design was used to optimize the four variables of pressure, temperature, liquid CO₂ flow rate, and extraction time at three levels using a semi-continuous, supercritical carbon dioxide extraction setup. The composition of the extract under the predicted optimum conditions (i.e., 109 bar, 56 °C, 0.86 mL min⁻¹, and 61 min) was about 69% triacetin accompanied by only 30% diacetin and no detectable monoacetin. In the second stage, the effect of the two factors, pressure (100, 109, and 140 bar) and liquid CO₂ flow rates of 0.86 and 1.5 mL min⁻¹ measured at average laboratory temperature (27 °C) and pressure (0.89 bar), were studied using a continuous, supercritical carbon dioxide fractionation setup equipped with a glass-bead packed column kept under a thermal gradient of 56-70 °C. The experimental design was organized as a 3 × 2 general factorial design. Under the best conditions (i.e., 140 bar and 1.5 mL min⁻¹), the extraction yield of triacetin and diacetin were 41.8 and 3.0%, respectively, without any detectable monoacetin as verified by GC-FID.