Synthesis of pure aragonite by sonochemical mineral carbonation

The objective of this work was to promote the formation of the aragonite polymorph of calcium carbonate, which has some valuable applications in industry, via the mineral carbonation route. The combination of ultrasound with magnesium ions promoted the formation of pure aragonite crystals at optimum conditions. It was possible to synthesize high purity aragonite precipitates at temperatures ranging from 24 °C to 70 °C, with the resulting powders possessing varying particle size distributions (from sub-micron up to 20 μm) and crystal morphologies (from acicular needles to novel hubbard squash-like particles). Several process parameters were found to influence the produced calcium carbonate polymorph ratios (aragonite over calcite). Higher values of magnesium-to-calcium ratio, intermediate ultrasound amplitude (60%), continuous ultrasound application (100% cycle), introduction of ultrasound pre-breakage, lowering of the CO₂ flow rate, and increase in the relative concentration (g/L Ca(OH)₂), all promoted aragonite formation. A potential route for industrial production of this material has been identified via a fed-batch process, which effectively reutilizes magnesium chloride while maintaining high aragonite yield. The results presented herein are significantly superior to aragonite formation using only single promoting techniques, typically found in literature, and go beyond by focusing on pure (>99%) aragonite formation.     

Optimization of Microwave-Assisted Extraction of Cherry Laurel Fruit

Response surface methodology was used to optimize the influence of microwave power (300–600 W), plant material-to-solvent ratio (0.05–0.2 g/cm³), and extraction time (10–30 min) on the efficiency of microwave-assisted extraction of the cherry laurel (Prunus laurocerasus L.) fruit. From experimental data, a quadratic polynomial mathematical model (R² = 0.9949) was developed to predict the extract yield. All considered factors were statistically significant for extraction efficiency, while the most important factor was extraction time. Microwave power of 550 W, plant material-to-solvent ratio of 0.05 g/cm³, and time of 25 min were determined as optimal conditions with a maximum yield of 9.36 g/100 g fresh plant material, which was confirmed through laboratory experiments (9.12 ± 0.61 g/100 g fresh plant material). An economic condition for simultaneous maximum extract yield (7.58 g/100 g fresh plant material) with minimal energy and solvent consumption was determined by the desirability function method (18.2 min, 300 W, and 0.2 g/cm³). Additionally, the total phenol and flavonoid quantification and antioxidant activity of both extracts were tested. There is no statistically significant difference in the total flavonoid content in the extracts obtained under both proposed conditions, while the total phenolic content and antioxidant activity of the extract obtained under economic conditions were slightly lower.     

Synthesis of single phase aragonite precipitated calcium carbonate in Ca(OH)2-Na2CO3-NaOH reaction system

The formation behavior of precipitated calcium carbonate polymorphs was investigated in three different supersaturation levels. Because the most easily adjustable and influential variable determining supersaturation is the ion concentration of the major reactants — Ca²⁺ and CO3 ₃ ²⁻ — the supersaturation can be adjusted by changing the ion concentration of these two ions. At high supersaturation, free energy is necessary for a decrease in nucleation, promoting the formation of a sphere-shaped vaterite, while aragonite and calcite were seen to co-exist at medium supersaturation. At low supersaturation, aragonite was mainly formed by mixing with some calcite. Hence, we considered that lower supersaturation was necessary to obtain a single phase aragonite. Furthermore, we found that the solubility of Ca(OH)₂ was decreased with the addition of NaOH by a common ion effect. Thus, it is possible to perform an experiment at a lower Ca²⁺ concentration. The aragonite was synthesized by adding the Na₂CO₃ solution to the Ca(OH)₂ slurry containing several concentrations of NaOH solution at 75°C and under the addition rate of Na₂CO₃ at 3 ml/min. The formation yield of calcite decreased when the NaOH concentration was increased. In conclusion, in the case of the reaction of the 2.5 M NaOH solution over 210 minutes, single-phase aragonite with an aspect ratio of 20 was obtained.     

Comparison of Supercritical Fluid Extraction and Liquid Solvent Extraction on Antitumor Diterpenoid from Pteris semipinnata L.

Extraction techniques using Supercritical Fluid Extraction (SFE) and Liquid Solvent Extraction (LSE) were evaluated for the extraction of Ent-11α-hydroxy-15-oxo-kaur-16-en-19-oic-acid (5 F), the antitumor diterpenoid from Pteris semipinnata L. The extracts were analyzed by high performance liquid chromatography (HPLC). SFE experiments showed that many factors had a great impact on the yield and purity of the diterpenoid, such as extraction temperature, pressure, fluid flow rate, extraction time, and modifier. For the SFE process, the optimum operation conditions were as follows: extraction temperature of 328.15 K, extraction pressure of 30 MPa, supercritical CO₂ flow rate of 160 kg/h, extraction time of 4 h, and 10% ethanol as the modifier. Under such a condition, the diterpenoid was almost completely extracted from the material and the yield was approximately 0.504 g/kg dry herb by HPLC analysis. The yield was approximately 3 fold higher than that by liquid solvent extraction. The purity of 5F was 5.148 g/kg dried extract with SFE, it was about 9 fold higher than that by LSE. Mass spectrum data indicated there were two correlative compounds, 5F and its derivative with glycose, in both the extracts, and the ratio of the signal strength of 5F and its derivative was about 3:1 in the SFE extract while that ratio was 1:3 in the LSE extract. The results demonstrated that the supercritical fluid extraction was selective, highly efficient, and with less consumption of organic solvents.     

Arsenite removal from groundwater in a batch electrocoagulation process: Optimization through response surface methodology

In this study, influences of seven process variables such as initial pH (pH_i), applied current (i), operating time (t_EC), initial As(III) concentration (C_o), diameter of Fe ball anode (d_p), column height in the electrocoagulation (EC) reactor (h) and airflow rate (Q_air) for removal of As(III) from groundwater by a new air-fed fixed-bed EC reactor were evaluated with a response surface methodology (RSM). The proposed quadratic model fitted very well with the experimental data for the responses. The removal efficiencies and operating costs were determined to be 99% and 0.01 $/m³ at the optimum operating conditions (a pH_i of 8.5, 0.05 A, 4.94 min, d_p of 9.24 mm, h of 7.49 cm, Q_air of 9.98 L/min for 50 µg/L). This study clearly showed that the RSM in the EC process was a very suitable method to optimize the operating conditions at the target value of effluent As(III) concentration (10 µg/L) while keeping the operating cost to minimal and maximize the removal efficiency.     

OPTIMAL KINETIC PARAMETERS AND BATCH MODELING FOR PECTIN HYDROLYSIS TO GALACTURONIC ACID WITH PECTINEX ULTRA SP-L ENZYME

Galacturonic acid is a monosaccharide obtained by pectin hydrolysis and a suitable substrate to produce bioethanol by fermentation. This article focuses on quantification of citrus pectin hydrolysis to galacturonic acid and provides new, reliable kinetic parameters for the Michaelis-Menten equation when the well-known commercial Pectinex Ultra SP-L is employed as enzyme. They are: r _max  = 1.10 g/(L min), K _m  = 10.42 g/L, and K _IGA  = 10.05 g/L, as obtained with a great accuracy by a nonlinear regression method and confirmed by the three classical linearization procedures (Lineweaver-Burk, Langmuir, and Eadie-Hofstee). The quantification of product inhibition has been achieved, with its inclusion in the rate equation. A batch reactor model yields perfect agreement between predictions and experiments, even under conditions different from those on which the parameters had been determined by regression.     

Response Surface Methodology to Supercritical Carbon Dioxide Extraction of Essential Oil from Amormum krevanh Pierre

Abstract

Response surface methodology was employed to investigate the effects of operating conditions and predict the optimal conditions for supercritical carbon dioxide extraction of essential oil from Amomum krevanh Pierre. The factors investigated were operating temperature (33–67°C), the operating pressure (91–259 bar), and the extraction time (20–70 min). The main effect of the operating pressure and the interaction effect between the operating temperature and the extraction time were found to be significant factors. From the response surface model, an optimal condition for essential oil content within the range of experimental study was found to be at 33°C, 175 bar, and 70 min, which gave the oil yield of 17.3 mg/g dry wt. The essential oil yield obtained at all conditions were higher than that obtained by organic solvent extraction (9.74 mg/g dry wt.) while the composition of the extract was similar, which were 1,8-cineole (70.87%), β-pinene (8.89%), and limonene (4.81%).     

Preparation of a Chemical Polyblend Sizing Agent via Polymerization of Acrylic Acid with Polyvinyl Alcohol

A polyblend sizing agent was prepared by free radical polymerization of partially neutralized acrylic acid (AA) in the presence of polyvinyl alcohol, (PVOH) (Vinarol®DV of Clariant), using ammonium persulfate (AP) initiator. Polymerization was conducted under different conditions including AP concentration (0.025–0.125 mol/L), degree of neutralization (3–50%), time (0–60 min), temperature (50–80°C), AA/PVOH ratio (0.2:1.2), type of neutralizing agent (NaOH or NH₄OH), and PVOH concentration (50–150 g/L). At optimum polymerization conditions, 100 g/L PVOH, 75 g/L AA (3% neutralized using NH₄OH), 0.1 mol/L AP, at 70°C for 25 min, a polyblend was prepared with a percent total conversion of 94%. It was then neutralized with NaOH to a pH of 7. Rheological properties of 10% aqueous solution of the polyblend or PVOH at 80°C revealed that the first was of a non-Newtonian pseudoplastic flow and the latter is of a non-Newtonian thixotropic flow. Solubility time of the polyblend film was shorter than that of PVOH, either after thermal treatment (120°C/15 min)or without thermal treatment. Sized gauzy fabric samples using the polyblend were of higher tensile strength and extent of size removal than those sized with PVOH.     

A sequential separation of linderane and norisoboldine using supercritical fluid and ionic liquid-based ultrasonic-assisted extraction from Lindera aggregate

ABSTRACT

Linderane (LDR) and norisoboldine (NOR) are two typical active compounds in Lindera aggregate (Sims.) Kosterm. In this study, a new method of sequential extraction of LDR and NOR from L. aggregate was developed by supercritical fluid extraction (SFE) and ionic liquid-based ultrasonic-assisted extraction (IL-UAE) for the first time. The suitable SFE with CO₂ conditions for LDR were 60 min dynamic extraction time, 40°C temperature and 30 MPa pressure. And the optimal IL-UAE factors for NOR were 2.06 mol/L 1-butyl-3-methylimidazolium bromide ([Bmim] Br) aqueous solution, 44 mL/g liquid–solid ratio, and 67 min ultrasonic time. Compared with the traditional extraction process, the sequential methods not only can obtain higher extraction efficiency, but also can realize the selective extraction for two different kinds of constituents with less consumption of traditional organic solvent. In addition, this environmentally friendly method could be used in a large-scale industry.     

Sorption of Silver Cations by Natural and Na-Exchanged Mordenite

Sorption of Ag⁺ by natural mordenite and its Na-exchanged form was investigated by the batch method. Maximum Ag⁺ uptake was observed at initial pH > 3.0 and contact time 90 min. The kinetic data fitted very well to the pseudo-second-order rate model with values of k ₂ from 37.31 to 0.487 and 48.32 to 0.491 g/meq min for the natural and Na-exchanged mordenite, respectively. The Langmuir model is in good correlation with the isotherm data up to initial concentration of 500 mg Ag⁺/L (q _m = 57.41 (natural sample) and 87.72 mg/g (Na-exchanged sample). The obtained data are promising for clean-up of polluted water.     

Optimization of formic acid hydrolysis of corn cob in xylose production

Dilute acid pretreatment of lignocellulosic material is one of the significant steps in a biorefinery. We used response surface methodology to determine the important factors of formic acid concentration (2%–6% wt%), treatment time (30–150 min), reaction temperature (120–160 °C), and liquid to solid ratio (3–11 mL/g) on dilute acid hydrolysis of corn cob to produce xylose. A xylose yield of 81.6% and selectivity of 15.1 g/g were achieved under the optimal conditions (5% acid concentration, 150 min, 135 °C, and 7 mL/g liquid to solid ratio). The addition of trivalent salts (FeCl₃, Fe(NO₃)3, and Fe₂(SO₄)₃) to the reaction system enhanced the xylose yield but decreased selectivity. The FeCl₃ concentration over 0.75 mol/L had a negative effect on xylose production.     

FED-BATCH SIMULTANEOUS SACCHARIFICATION AND FERMENTATION OF MICROWAVE/ACID/ALKALI/H2O2 PRETREATED RICE STRAW FOR PRODUCTION OF ETHANOL

The batch simultaneous saccharification and fermentation (SSF) of microwave/acid/alkali/H₂O₂ pretreated rice straw to ethanol was optimized using cellulase from Trichoderma reesei and Saccharomyces cerevisiae YC-097 cells prior to the fed-batch SSF studies. The batch SSF optima were 10% w/v substrate, 40°C, 15 mg cellulase/g substrate, initial pH 5.3, and 72 hours. Under the optimum conditions the ethanol concentration and its yield were 29.1 g/L and 61.3% respectively. Based on the optimal batch SSF, the fed-batch SSF was investigated and its operation parameters were optimized. Under its optimal conditions the ethanol concentration reached 57.3 g/L, while its productivity and yield were only slightly less than those in the batch SSF. This suggests that fed-batch SSF is a potential operation mode for effective ethanol production from microwave/acid/alkali/H₂O₂ pretreated rice straw.     

Optimization of Microwave‐Assisted Extraction of Flavonoid from Radix Astragali using Response Surface Methodology

Abstract

Response surface methodology (RSM) was applied to predict optimum conditions for microwave‐assisted extraction (MAE) of flavonoid from Radix Astragali. A central composite design was used to monitor the effect of temperature, extraction time, solvent‐to‐material ratio, and the ethanol concentration on yield of total flavanoid (TFA). Optimum extraction conditions were predicted as 108.2°C, 26.7 min, 23.1 ml/g solvent‐to‐material ratio and 86.2% ethanol. The maximum yield 1.234±0.031 mg/g was close to the yield of Soxhlet and higher than that of ultrasound assisted extraction and heat reflux extraction. MAE was an effective alternative to conventional extraction methods.     

Optimization of Ultrasound-Assisted Extraction of Single Cell Oil from Mortierella isabellina

In this paper, ultrasound-assisted extraction of single cell oil (SCO) from Mortierella isabellina (MI) was investigated using mathematical statistics, such as Plackett–Burman (PB) design, steepest ascent (SA) design, and Box–Behnken (BB) design. The results from response surface methodology (RSM) indicated the hydrochloric acid concentration, ultrasound time, ultrasound temperature, and extraction time are the most significant parameters. The optimum extraction conditions were as follows: ultrasound power 300 W, ultrasound time 12.20 min, ultrasound temperature 53.42°c, hydrochloric acid 30 mmol in each gram of wet fungal mycelia, extraction time 19.45 min, extraction solvent (CH₃Cl-CH₃OH) ratio 2:1. Under the conditions, the extraction rate of SCO from MI was up to 90.63 ± 1.35%, and the yield of SCO was 109.88 ± 0.02 mg/g (P < 0.05) that was 1.23-fold and 1.35-fold the yield of acid-heating method and ultrasound method, respectively.     

Optimization of Spray-Drying Process Conditions for the Production of Maximally Viable Microencapsulated L. acidophilus NCIMB 701748

Inrecent years, the use of spray drying for the production of anhydrobiotics has gained the interest of functional food manufacturers, mainly due to cost efficiencies and enhanced product and process flexibility (e.g., enhanced shelf life). In the present work, spray-drying conditions (air inlet temperature and feed flow rate) were optimized for the microencapsulation of the thermo sensitive probiotic lactobacilli strains Lactobacillus acidophilus stabilized in a 60:20:20 (w/w) maltodextrin: whey protein concentrate: D-glucose carrier. A 2³ full-factorial experimental design was constructed with air inlet temperature (120, 140, and 160°C) and feed flow rate (6, 7.5, and 9.0 mL/min) as the independent variables and total viable counts (TVC), water activity (a _w ), and cyclone recovery (CR) defined as the dependent variables. The increase in air inlet temperature from 120 to 160°C induced a significant (p < 0.001) reduction in the TVC from 9.02 to 7.20 log cfu/g, which corresponds to a97.5% loss of the L. acidophilus viable counts. On the other hand, the increase in the feed flow rate from 6 to 7.5 mL/min significantly reduced (p < 0.001) the heat-induced viability loss. A further increase in the feeding rate did not further modify the achieved thermo protection, and a detrimental impact of cyclone recovery (reduction) and water activity (increase) of the powder was observed. Using pruned quadratic mathematical models, the optimum spray-drying conditions for the production of maximally viable microencapsulated L. acidophilus were 133.34°C and 7.14 mL/min. The physicochemical and structural characteristics of the powders produced were acceptable for application with regards to residual water content, particles mean size, and thermo physical properties to ensure appropriate storage stability under room temperature conditions, with a low inactivation rate of L. acidophilus. Microcapsules appeared partially collapsed by scanning electron microscope with a spherical shape with surface concavities.     

Extraction of Caffeine with Annular Centrifugal Contactors

Abstract

An extraction process for caffeine has been developed with annular centrifugal contactors. The caffeine distribution ratio in the mother solution effluent‐chloroform system was measured to be about 18.6. Both the pilot tests and the plant tests have been completed with Φ20 mm and Φ230 mm annular centrifugal contactors, respectively. The extraction rate higher than 99% was achieved in the pilot tests, when the rotor speed was 3000‐4500 r/min, the total flow was 20‐80 mL/min, and the flow ratio (A/O) was 2/1. When the rotor speed was 1800 r/min, the mother solution flow was 2000 L/h, and the chloroform flow was 1000 L/h; the extraction rate was also more than 99% in the plant tests.     

Antioxidant Activity and Total Polyphenols Content of Camellia Oil Extracted by Optimized Supercritical Carbon Dioxide

In this study, Camellia oil is co-extracted from Camellia oleifera seeds and green tea scraps by supercritical carbon dioxide (SC-CO₂), which is optimized on the extraction yield, ABTS-scavenging activity, and total polyphenols content (TPC) of oil by single-factor experiments combined with response surface methodology (RSM). The extraction temperature, pressure, dynamic time, carbon dioxide (CO₂) flow rate, and seed mass ratio were investigated with single-factor experiments. The results indicated the optimum CO₂ flow rate and dynamic extraction time were 15 L hour⁻¹ and 60 min (i.e., 2.382 kg CO₂/100 g sample). Furthermore, the complicated effects of extraction temperature (40–50 °C), pressure (20–30 MPa), and seed mass ratio (0.25–0.75) were optimized by RSM based on the Box–Behnken design (BBD). The models with high R-squared values were obtained and used to predict the optimum operating conditions of the process. Under the optimum operating conditions (i.e., temperature of 46 °C, pressure of 30 MPa, and seed mass ratio of 0.35), the extraction yield, ABTS-scavenging activity, and TPC of oil were 14.43 ± 0.17 g/100 g sample, 73.70 ± 0.34%, and 2.18 ± 0.05 mg GAE/g oil, which were in good agreement with the predicted values. In addition, the experiments indicated that the Camellia oil obtained was rich in polyphenols, resulting in better oxidation stability and antioxidant activity than the original oil.     

Adsorption of Cr(VI) on Stipa tenacissima L (Alfa): Characteristics,kinetics and thermodynamic studies

This study aims to remove ionic Cr(IV) from aqueous solution using Stipa tenacissima L as a biomass source. The Arabic name for the plant Stipa tenacissima L is HALFA (ALFA) ; it belongs to the category of biosorbents agro-industrial origin. Stipa tenacissima L is from the center of the province of Djelfa Algeria. This biomass was characterized by various analytical techniques such as scanning electron microscopy, energy dispersive spectroscopy and Fourier-transform infrared spectroscopy. In order to optimize the operating conditions for the determination of ions of Cr(VI), the initial concentration of Cr(VI) ions, temperature, pH of the solution and the solid/liquid ratio were individually studied. According to the results, a fix rate of about 90% was recorded. Optimum biosorption conditions were found to be pH ~1, C_o = 50 mg/L, R = 5 g/L and T = 296 K. It was found that biosorption of Cr(VI) ions onto biomass of Stipa tenacissima L was better suitable to Langmuir model. The correlation coefficients for the second-order kinetic model obtained were found to be 0.996 for all concentrations. These indicate that the biosorption system studied belongs to the second-order kinetic model. Thermodynamics parameters as enthalpy, entropy of system and free energy were evaluated, which confirms the feasibility of the process. An empirical modeling was performed by using a 2⁴ full factorial design, and the regression equation for adsorption chromium (VI) was determined from the data. The initial metal ion concentration has the most positive pronounced effect in increasing the chromium (VI) adsorption, whereas the pH and adsorbent dosage have the most negative effect on the process.     

Separate versus Simultaneous Saccharification and Fermentation of Two‐Step Steam Pretreated Softwood for Ethanol Production

Abstract

In two previous studies, optimal conditions were identified for two‐step steam pretreatment of SO₂‐ and H₂SO₄‐impregnated softwood. In the present study the yield of sugar and ethanol was determined in a process development unit where pretreatment was performed in a 10‐L reactor and simultaneous saccharification and fermentation (SSF) or enzymatic hydrolysis (EH) were performed in 30‐L reactors. The study showed that a steam pretreatment reactor should be larger than 2 L to yield acceptable results. Two pretreatment combinations were studied. In the H₂SO₄ case, the first pretreatment step was at 180°C for 10 min with 0.5% H₂SO₄ and the second step at 210°C for 2 min with 1% H₂SO₄. In the SO₂ case, first step was at 190°C for 2 min followed by a second step at 210°C for 5 min. The concentration of SO₂ was 3% in both steps. EH and SSF were performed on the whole slurry after the second pretreatment step to determine the yield of sugars and ethanol. The liquid after the first pretreatment step was also analyzed and fermented. When SSF and EH were performed at the same dry matter content and enzymatic activity, the ethanol yield in SSF exceeded the yield obtained with EH in both pretreatment cases, even when 100% yield in the fermentation step was assumed. Thus SSF is a better process if yield is the main priority. Comparison of the yields with the two acid catalysts showed higher yields with SO₂ in both SSF and EH. The overall ethanol yield following SSF of SO₂‐impregnated and pretreated wood reached 81% of the theoretical, that is, 357 liters per metric ton of dry raw material.     

Removal of Copper and Lead from Aqueous Solution by Adsorption onto Cross-Linked Chitosan/Montmorillonite Nanocomposites in the Presence of Hydroxyl–Aluminum Oligomeric Cations: Equilibrium,Kinetic, and Thermodynamic Studies

Adsorption removal of Cu (II) and Pb (II) on cross-linked chitosan/Al₁₃-pillared montmorillonite (CCPM) was examined in solutions. The chitosan dosage was drastically reduced in the new nanocomposite, which is made from the treated clay (Al₁₃-pillared montmorillonite). Several important parameters that influenced the adsorption of Cu (II) and Pb (II) ions, such as cross-linked chitosan-to-clay ratio, pH, temperature, initial concentration, dosage, and contact time effect, were systematically investigated. Result showed that in the nanocomposite with cross-linked chitosan-to-clay ratio of 0.45:1, the maximum removal efficiencies of Cu (II) [pH 6.5, dosage 10 g/L, initial Cu (II) concentration 100 mg/L, contact time 2 h, 298 K] and Pb (II) [pH 6.0, dosage 5 g/L, initial Pb (II) concentration 100 mg/L, contact time 2 h, 298 K] were 96.0% and 99.5%, respectively. Kinetic and isotherm studies have indicated that the adsorption process of Cu (II) or Pb (II) nanocomposites was better fitted by the pseudo-second-order equation and the Freundlich equation, with chemical adsorptions as the rate-limiting step. The metal–ion affinity to the functional groups of CCPM followed the order Pb (II) > Cu (II). The thermodynamic parameters ΔH and ΔS values showed that the sorption process of Cu (II) or Pb (II) was spontaneous (ΔG < 0), was endothermic (ΔH < 0), and had decreased entropy (ΔS < 0). HNO₃ (0.1 M) could be a good desorbent in the recovery of metal ions after adsorption and regeneration of the adsorbent.