Chrome tannage using high-intensity ultrasonic field

The process time in chrome tannage in leather making, using an elastic compression cycle followed by irradiation by high-intensity ultrasound, is quite short lasting only a few minutes, compared with a process time of several hours in modern chrome tannage. After ultrasonic irradiation, samples were basified in 17 h in chrome liquor at a pH of 4.0 and the shrinkage temperature was measured. The determination of the efficiency for the chrome liquor penetrating into the hides can be based on the steepness of the shrinkage temperature-processing time curve. An approximate value of 20 degrees C min(-1) can be evaluated for the initial slope of the curve when elastic compression and high-intensity ultrasonic irradiation is used, and a processing time of 2 min is required in chrome liquor (plus 17 h basification and 24 h storage time) to obtain leather stable to boiling. Usually, hides are kept in chrome liquor for 2 h.     

Comparison between the use of polyether ether ketone and stainless steel columns for ultrasonic-assisted extraction under various ultrasonic conditions

The ultrasound-assisted extraction (UAE) was conducted using the stainless steel (SS) and polyether ether ketone (PEEK) columns and analyzed with high-performance liquid chromatography (HPLC) to understand the mechanism of ultrasound-assisted chromatography (UAC). Empty SS and PEEK columns were used to extract dyes from a fabric under identical conditions with several parameters including the initial ultrasonic bath temperatures (30 °C and 40 °C), ultrasound power intensities (0, 20, 40, 60, 80, and 100 %), ultrasound operation modes (normal and sweep), and ultrasound frequencies (25 kHz, 40 kHz, and 132 kHz) to compare their extraction capabilities. After 30 min of extraction, the amount of extract was determined by HPLC. The PEEK material was significantly affected by ultrasonic radiation compared to the SS material, especially at a higher temperature (40 °C), power intensity (100 %), and frequency (132 kHz) with sweep mode. At a maximum power density of 45 W/L, the extraction effectiveness ratio of PEEK to SS was in the range of 1.8 - 3.9 depending on the specific frequency, initial temperature, and with or without temperature control. The most optimal ultrasound frequencies, in terms of enhancing extraction effectiveness, are in the order of 132 kHz, 40 kHz, and 25 kHz. Unlike the SS material, the PEEK material was more affected by temperature and acoustic effects under identical conditions, especially at 132 kHz ultrasound frequency. In contrast, at lower frequencies of 40 kHz and 25 kHz, no significant differences in the acoustic effects were observed between the PEEK and SS materials. The findings of this study contribute to elucidating the roles of column materials in UAE and UAC.     

超声场中sol-gel法制备纳米TiO2光催化剂的研究

本文在频率分别为20kHz、30kHz、40kHz(电功率均为500W)的超声场中制备溶胶。用光散射法测得溶胶粒子粒径分别为29．4nm、18．3nm、13．2nm，对无超声场和超声场(40kHz)制备的凝胶进行超临界乙醇干燥。用XRD、BET、TEM、DRS对上述干燥的TiO2粒子进行表征，以光催化降解罗丹明B为模型反应。结果表明，在实验范围内溶胶粒径随超声波频率的升高而减小，加超声场制备的纳米TiO2粒子光催化活性比无超声场下制备的粒子高。     

Ultrasound assisted chrome tanning: Towards a clean leather production technology

Nowadays, there is a growing demand for a cleaner, but still effective alternative for production processes like in the leather industry. Ultrasound (US) assisted processing of leather might be promising in this sense. In the present paper, the use of US in the conventional chrome tanning process has been studied at different pH, temperature, tanning time, chrome dose and US exposure time by exposing the skin before tanning and during tanning operation. Both prior exposure of the skin to US and US during tanning improves the chrome uptake and reduces the shrinkage significantly. Prior exposure of the skin to US increase the chrome uptake by 13.8% or reduces the chrome dose from 8% to 5% (% based on skin weight) and shorten the process time by half while US during tanning increases the chrome uptake by 28.5% or reduces the chrome dose from 8% to 4% (half) and the tanning time to one third compared to the control without US. Concomitantly, the resulting leather quality (measured as skin shrinkage) improved from 5.2% to 3.2% shrinkage in the skin exposed to US prior tanning and to 1.3% in the skin exposed to US during the tanning experiment. This study confirms that US chrome tanning is an effective and eco-friendly tanning process which can produce a better quality leather product in a shorter process time with a lower chromium dose.     

Ultrasound-assisted extraction of hesperidin from Penggan (Citrus reticulata) peel

Hesperidin, an abundant and inexpensive bioflavonoid in Penggan (Citrus reticulata) peel, has been reported to possess a wide range of pharmacological properties. Ultrasonic extraction is an effective technique for the isolation of bioactive compounds from vegetable materials. In this study, the application of ultrasonic method was shown to be more efficient in extracting hesperidin from Penggan (C. reticulata) peel than the classical method. The effects of main ultrasonic-assisted extraction conditions on extraction yields of hesperidin from Penggan (C. reticulata) peel were evaluated, including extraction solvents, solvent volume, temperature, extraction time, ultrasonic power, ultrasonic frequency. Results showed that solvent, frequency and processing temperature were the most important factors for improving the extracting yields of hesperidin. When performed at the same temperature under the same time using three frequencies, methanol as the solvent improved the extraction yield evidently compared with ethanol or isopropanol; by comparison of the frequency influence, the yield of hesperidin was higher at 60 kHz than at 20 kHz and 100 kHz. The optimum ultrasonic conditions were determined as: methanol, frequency of 60 kHz, extraction time of 60 min, and temperature of 40 degrees C. In addition, the ultrasonic power had a weak effect on the yields of hesperidin within the experimental range. Extending ultrasonic treatment times did not result in degradation of hesperidin; the rotary beaker for materials can increase the yields of hesperidin.     

Dual-frequency multi-angle ultrasonic processing technology and its real-time monitoring on physicochemical properties of raw soymilk and soybean protein

To improve the soybean protein content (SPC), flavor and quality of soymilk, the effects of dual-frequency ultrasound at different angles (40 + 20 kHz 0°, 40 + 20 kHz 30°, 40 + 20 kHz 45°) on physicochemical properties and soybean protein (SP) structure of raw soymilk were mainly studied and compared with the conventional single-frequency (40 kHz, 20 kHz) ultrasound. Furthermore, the intensity of the ultrasonic field in real-time was monitored via the oscilloscope and spectrum analyzer. The results showed that 40 + 20 kHz 45° treatment significantly increased SPC. The ultrasonic field intensity of 40 + 20 kHz 0° treatment was the largest (8.727 × 10⁴ W/m²) and its distribution was the most uniform. The emulsifying stability of SP reached the peak value (233.80 min), and SP also had the largest particle size and excellent thermal stability. The protein solubility of 40 + 20 kHz 30° treatment attained peak value of 87.09%. 20 kHz treatment significantly affected the flavor of okara. The whiteness and brightness of raw soymilk treated with 40 kHz were the highest and the system was stable. Hence, the action mode of ultrasonic technology can be deeply explored and the feasibility for improving the quality of soymilk can be achieved.     

Sono-leather technology with ultrasound: a boon for unit operations in leather processing - review of our research work at Central Leather Research Institute (CLRI), India

Ultrasound is a sound wave with a frequency above the human audible range of 16Hz to 16kHz. In recent years, numerous unit operations involving physical as well as chemical processes are reported to have been enhanced by ultrasonic irradiation. There have been benefits such as improvement in process efficiency, process time reduction, performing the processes under milder conditions and avoiding the use of some toxic chemicals to achieve cleaner processing. These could be a better way of augmentation for the processes as an advanced technique. The important point here is that ultrasonic irradiation is physical method activation rather than using chemical entities. Detailed studies have been made in the unit operations related to leather such as diffusion rate enhancement through porous leather matrix, cleaning, degreasing, tanning, dyeing, fatliquoring, oil-water emulsification process and solid-liquid tannin extraction from vegetable tanning materials as well as in precipitation reaction in wastewater treatment. The fundamental mechanism involved in these processes is ultrasonic cavitation in liquid media. In addition to this there also exist some process specific mechanisms for the enhancement of the processes. For instance, possible real-time reversible pore-size changes during ultrasound propagation through skin/leather matrix could be a reason for diffusion rate enhancement in leather processing as reported for the first time. Exhaustive scientific research work has been carried out in this area by our group working in Chemical Engineering Division of CLRI and most of these benefits have been proven with publications in valued peer-reviewed international journals. The overall results indicate that about 2-5-fold increase in the process efficiency due to ultrasound under the given process conditions for various unit operations with additional benefits. Scale-up studies are underway for converting these concepts in to a real viable larger scale operation. In the present paper, summary of our research findings from employing this technique in various unit operations such as cleaning, diffusion, emulsification, particle-size reduction, solid-liquid leaching (tannin and natural dye extraction) as well as precipitation has been presented.     

Experimental investigations on ultrasound mediated particle breakage

This paper investigates the effect of high-intensity ultrasound on the breakage characteristics of particles suspended in water. A continuous sonicated flow experimental apparatus is used involving a 24 kHz horn type transducer and continuous in-line particle chord length measurement. The effects of sonication power (150-350 W) and temperature (10-50 degrees C) on the breakage characteristics are investigated. Higher breakage is favored at higher sonication power. An optimum temperature in the range tested is observed to exist between 25 degrees C and 37 degrees C. The acoustic cavitation field is influenced by temperature through a complex interplay of vapor pressure, surface tension and viscosity leading to the optimum observed in particle breakage. The efficiency of ultrasound energy conversion to particle breakage is calculated using calorimetry and found along with the net breakage efficiency to initially increase with temperature followed by a decrease after the optimum. It is found to be independent of input ultrasonic power. The effects of contact time is also investigated.     

Dosimetry in sonochemistry: the use of aqueous terephthalate ion as a fluorescence monitor

The generation of HO radicals by acoustic cavitation in water was monitored by their reaction with terephthalic acid (TA) anion to produce fluorescent hydroxyterephthalate ions using a cleaning bath (38kHz) and a probe system (20, 40 and 60 kHz) as different sources of ultrasound. When using the ultrasonic bath as a source of energy for sonochemical studies, the shape of the reaction vessel is important. In the case of HO production from water (50 cm³), reaction in a conical flask (100 cm³) produces 2.75 times more radicals than a round-bottomed flask of the same capacity. The fluorescence yield (fluorescence intensity/ultrasound dosage) obtained using the conical flask and ultrasonic bath was similar to that for a probe operating at 40 kHz on the same volume of solution. For a probe system operating at 20, 40 and 60 kHz the greatest sonochemical efficiency was attained at the highest of these frequencies (60 kHz). For the probe system the fluorescence yield is directly proportional to power input and the concentration of TA. The fluorescence yield decreases as the temperature is increased.     

Ultrasound assisted supercritical fluid extraction of oil and coixenolide from adlay seed

Oil and coixenolide are important components of adlay seed (Coix lachrymal-jobi L. var. Adlay) with many beneficial functions to human health. In this work, a novel extraction technique--ultrasound assisted supercritical fluid extraction (USFE)--was studied. Effects of operating conditions on the extraction, including extraction temperature (T), pressure (P), time (t), CO(2) flow rate (F) and ultrasonic power (I) were investigated. There are optimum temperatures which gives the maximum extraction yields (EYs) for the supercritical fluid extractions with and without ultrasound. The effect of pressure on EYs for is similar to that of pressure on CO(2) density. Based on the yield of extraction, the favorable conditions for supercritical fluid extraction (SFE) were: T at 45 degrees C, P at 25 MPa, t at 4.0 h and F at 3.5L/h. While ultrasound was applied as in USFE, the following parameters were preferred: T at 40 degrees C, P at 20 MPa, t at 3.5h and F at 3.0 L/h, respectively. The results show that supercritical fluid extraction with the assistance of ultrasound could reduce the temperature, pressure, CO(2) flow rate, as well as time used in the process. Compared with SFE, USFE could give a 14% increase in the yield for extracting oil and coixenolide from adlay seed with less severe operating conditions.     

Intensification of alkaline delignification of sugarcane bagasse using ultrasound assisted approach

Ultrasound-assisted approach has been investigated for delignification so as to develop green and sustainable technology. Combination of NaOH with ultrasound has been applied with detailed study into effect of various parameters such as time (operating range of 15–90 min), alkali concentration (0.25 M−2.5 M), solvent loading (1:15–1:30 w/v), temperature (50–90 ˚C), power (40–140 W) and duty cycle (40–70 %) at fixed frequency of 20 kHz. The optimized operating conditions established for the ultrasonic horn were 1 M as the NaOH concentration, 1 h as treatment time, 70˚C as the operating temperature, 1:20 as the biomass loading ratio, 100 W as the ultrasonic power and 70% duty cycle yielding 67.30% as the delignification extent. Comparative study performed using conventional and ultrasonic bath assisted alkaline treatment revealed lower delignification as 48.09% and 61.55% respectively. The biomass samples were characterized by SEM, XRD, FTIR and BET techniques to establish the role of ultrasound during the treatment. The morphological changes based on the ultrasound treatment demonstrated by SEM were favorable for enhanced delignification and also the crystallinity index was more in the case of ultrasound treated material than that obtained by conventional method. Specific surface area and pore size determinations based on BET analysis also confirmed beneficial role of ultrasound. The overall results clearly demonstrated the intensification obtained due to the use of ultrasonic reactors.     

Studies on the use of power ultrasound in leather dyeing

Uses of power ultrasound for acceleration/performing the chemical as well as physical processes are gaining importance. In conventional leather processing, the diffusion of chemicals through the pores of the skin/hide is achieved by the mechanical agitation caused by the paddle or drumming action. In this work, the use of power ultrasound in the dyeing of leather has been studied with the aim to improve the exhaustion of dye for a given processing time, to reduce the dyeing time and to improve the quality of dyed leather. The effect of power ultrasound in the dyeing of full chrome cow crust leather in a stationary condition is compared with dyeing in the absence of ultrasound as a control experiment both in a stationary as well as conventional drumming condition. An ultrasonic cleaner (150 W and 33 kHz) was used for the experiments. Actual power dissipated into the system was calculated from the calorimetric measurement. Experiments were carried out with variation in type of dye, amount of dye offer, temperature and time. The results show that there is a significant improvement in the percentage exhaustion of dye due to the presence of ultrasound, when compared to dyeing in absence of ultrasound. Experiments on equilibrium dye uptake carried out with or without ultrasound suggest that ultrasound help to improve the kinetics of leather dyeing. The results indicate that leathers dyed in presence of ultrasound have higher colour values, better dye penetration and fastness properties compared to control leathers. The physical testing results show that strength properties of the dyed leathers are not affected due to the application of ultrasound under the given process conditions. Apparent diffusion coefficient during the initial stage of dyeing process, both in presence and in absence of ultrasound was calculated. The values show that ultrasound helps in improving the apparent diffusion coefficient more for the difficult dyeing conditions such as in the case of metal-complex dyes having bigger aggregate size compared to less difficult dyeing conditions.     

Baeyer-Villiger oxidation of cyclohexanone to epsilon-caprolactone in airlift sonochemical reactor

Baeyer-Villiger oxidation of cyclohexanone to epsilon-caprolactone was studied in a new type reactor--the airlift loop sonochemical reactor. The reactor plays a synergistic effect of sonochemsity and higher oxygen transfer rate. The influences of ultrasound intensity, reaction temperature, the molar ratio of benzaldehyde to cyclohexanone and oxygen gas flow rate on the conversion and selectivity of cyclohexanone were investigated and discussed. Under ultrasound, the amount of benzaldehyde can be reduced from 75% to 67%. Ultrasound not only intensified the rates of reactions but also increased the yield of product. The optimized operation conditions are listed as follows: the reaction temperature is 30 degrees C, the molar ratio of cyclohexanone to benzaldehyde is 1:2, the oxygen gas flow rate is 1.15 cm s(-1), and ultrasonic irradiations 2h at 40 kHz, 2.25 W cm(-2). Under the optimum operation conditions, the average molar yield of epsilon-caprolactone comes up to 87.7%.     

Sonophotocatalytic oxidation of elemental sulphur on titanium dioxide

The effect of ultrasound on the photocatalytic oxidation kinetics of elemental sulphur particles catalyzed by titanium dioxide was studied using a conductivity method to follow the reaction. The simultaneous use of photocatalyst and ultrasound have a positive effect on the reaction. The zero-order oxidation rate constant of sulphur, reached after an activation period of approximately 150 min, was about 20 times higher when the reactor was sonicated, using an ultrasonic processor of 30 kHz, compared to the rate found in its absence. Finally, when the amount of sulphur is changed in the reactor, saturation kinetics seems to be the most appropriate model to describe the oxidation process in the presence of ultrasound and, in the other hand, when titanium dioxide was increased, a maximum rate was achieved when 0.56 g/L TiO2 were used.     

Process intensification and kinetic studies of ultrasound-assisted extraction of flavonoids from peanut shells

In this work, extraction of flavonoids from peanut shells has been studied in the presence of ultrasound and the results are compared with Soxhlet and heat reflux extraction for establishing the process intensification benefits. The process optimization for understanding the effects of operating parameters, such as ethanol concentration, particle size, solvent to solid ratio, extraction temperature, ultrasonic power and ultrasonic frequency, on the extraction of flavonoids has been investigated in details. The highest extraction yield (9.263 mg/g) of flavonoids was achieved in 80 min at optimum operating parameters of particle size of 0.285 mm, solvent to solid ratio of 40 ml/g, extraction temperature of 55 °C, ultrasonic power of 120 W and ultrasonic frequency of 45 kHz with 70% ethanol as the solvent. Two kinetic models (i.e. phenomenological model and Peleg’s model) have been introduced to describe the extraction kinetic of flavonoids by fitting experimental data and predict kinetic parameters. Good performance with slight loss of goodness of fit of two models was found by comparing their coefficient of determination (R²), root mean square error (RMSE) and/or mean percentage error (MPE) values. This work would provide the reduction of degradation and the economic evaluation for the extraction processes of flavonoids from peanut shells, as well as give a better explanation for the mechanism of ultrasound.     

Lysinoalanine formation and conformational characteristics of rice dreg protein isolates by multi-frequency countercurrent S-type sonochemical action

The influences of multi-frequency countercurrent S-type ultrasound (MFSU), with various frequency modes, on lysinoalanine (LAL) formation and conformational characteristics of rice dreg protein isolates (RDPI) were investigated. The ultrasonic operating mode with dual-frequency combination (20/40 kHz) indicated lower LAL content and higher protein dissolution rate of RDPI compared with that of other ultrasound operating modes. Under the dual-frequency ultrasound mode of 20/40 kHz, acoustic power density of 60 W/L, time of 20 min, and temperature of 35 °C, the relative reduction rate of LAL of RDPI reached the highest with its value of 26.95%, and the protein dissolution rate was 71.87%. The changes in chemical interactions between protein molecules indicated that hydrophobic interactions and disulfide bonds played a considerable role in the formation of LAL of RDPI, especially the reduction of g-g-g and g-g-t disulfide bond. Alterations in microstructure showed that ultrasonication loosened the protein structure and created more uniform protein fragments of RDPI. In conclusion, using MFSU in treating RDPI was an efficacious avenue for minimizing LAL content and modifying the conformational characteristics of RDPI.     

Ultrasonically enhanced corrosion of 304L stainless steel I: the effect of temperature and hydrostatic pressure

A systematic study of the effect exerted by various parameters on the corrosion of 304L stainless steel in an ultrasonic field has been carried out. Ultrasound increased the corrosion rate under all the investigated conditions. In this paper, attention is focused on the effect of temperature and hydrostatic pressure. At ambient pressure, increase in temperature, T, was found to increase the ultrasonically enhanced corrosion rate up to a maximum of 40 degrees C; at 50 degrees C a marked decrease in the effect of ultrasound was observed. At constant temperature, increase in hydrostatic pressure caused a strong increase in corrosion rate to values in excess of 2500 mm yr(-1) at 4 bar.     

Ultrasound-assisted extraction of capsaicinoids from Capsicum frutescens on a lab- and pilot-plant scale

The influence of operating parameters (solvent type, powder to solvent ratio and temperature) on the ultrasonically assisted extraction of capsaicinoids from dried Capsicum frutescens (fruit) was studied. From the economic perspective, the suitable condition for capsaicinoid extraction by indirect sonication in an ultrasonic bath with a working frequency of 35 kHz was at a ratio of 1g of solid material: 5 ml of 95% (v/v) ethanol, 45 degrees C, where 85% of the capsaicinoids were removed from the raw material in 3h. In an experimental pilot study in 20-l extraction tank at the fixed ultrasonic frequency of 26 kHz and 70 kHz, the recovery of capsaicinoids was 76% and 70%, respectively. It was shown that the ultrasonic extraction produced a significant reduction in extraction time at a lower operational temperature than under a conventional industrial hot maceration process.     

Ultrasonic drying of foodstuff in a fluidized bed: Parametric study

The application of high power ultrasound for dehydration of porous materials may be very effective in processes in which heat-sensitive materials such as foodstuffs have to be treated. In fact, high-intensity ultrasonic vibrations are capable of increasing heat and mass transfer processes in materials. The application of ultrasonic energy can be made alone or in combination with other kind of energy such as hot-air. In this case, ultrasound helps in reducing temperature or treatment time. The aim of this work is to study the effect of air flow rate, ultrasonic power and mass loading on hot-air drying assisted by a new power ultrasonic system. The drying chamber is an aluminium vibrating cylinder, which is able to create a high intensity ultrasonic field in the gas medium. To that purpose the chamber is driven at its centre by a power ultrasonic vibrator at 21.8 kHz. Drying kinetics of carrot cubes and lemon peel cylinders were carried out at 40 degrees C for different air velocities, with and without ultrasound. The results show that the effect of ultrasound on drying rate is affected by air flow rate, ultrasonic power and mass loading. In fact, at high air velocities the acoustic field inside the chamber is disturbed and the effect of ultrasound on drying kinetics diminishes.     

Ultrasonic acceleration of ester hydrolyses

Kinetics of acid-catalyzed hydrolysis of ethyl acetate in 1M HCl solution was investigated without sonication and under ultrasound at 22 kHz. An average 6.2-fold ultrasonic rate enhancement for the temperature range of 10-28 degrees C was found. This is a considerably greater acceleration than previously reported for ester hydrolyses. It was suggested that a significant part of the sonochemical effect on polar reactions may be due to temperature gradients in the cavitating medium.