WO2008074072A1 - High energy ultrasound extraction - Google Patents

High energy ultrasound extraction Download PDF

Info

Publication number
WO2008074072A1
WO2008074072A1 PCT/AU2007/001958 AU2007001958W WO2008074072A1 WO 2008074072 A1 WO2008074072 A1 WO 2008074072A1 AU 2007001958 W AU2007001958 W AU 2007001958W WO 2008074072 A1 WO2008074072 A1 WO 2008074072A1
Authority
WO
WIPO (PCT)
Prior art keywords
extraction
liquid phase
sonotrode
oak
liquid
Prior art date
Application number
PCT/AU2007/001958
Other languages
French (fr)
Inventor
Darren Bates
Richard Mcloughlin
Andrew Yap
Original Assignee
Cavitus Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2006907033A external-priority patent/AU2006907033A0/en
Application filed by Cavitus Pty Ltd filed Critical Cavitus Pty Ltd
Priority to EP07845399A priority Critical patent/EP2106278A4/en
Priority to JP2009541691A priority patent/JP2010512998A/en
Priority to CN2007800512116A priority patent/CN101622043B/en
Priority to US12/520,062 priority patent/US8343562B2/en
Priority to BRPI0720541-4A2A priority patent/BRPI0720541A2/en
Priority to AU2007335247A priority patent/AU2007335247B2/en
Publication of WO2008074072A1 publication Critical patent/WO2008074072A1/en

Links

Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/40—Colouring or decolouring of foods
    • A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
    • A23L5/43—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives
    • A23L5/44—Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives using carotenoids or xanthophylls
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23F—COFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
    • A23F3/00—Tea; Tea substitutes; Preparations thereof
    • A23F3/16—Tea extraction; Tea extracts; Treating tea extract; Making instant tea
    • A23F3/18—Extraction of water soluble tea constituents
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23F—COFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
    • A23F5/00—Coffee; Coffee substitutes; Preparations thereof
    • A23F5/24—Extraction of coffee; Coffee extracts; Making instant coffee
    • A23F5/26—Extraction of water-soluble constituents
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/10—Natural spices, flavouring agents or condiments; Extracts thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/10—Natural spices, flavouring agents or condiments; Extracts thereof
    • A23L27/11—Natural spices, flavouring agents or condiments; Extracts thereof obtained by solvent extraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0203—Solvent extraction of solids with a supercritical fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0261—Solvent extraction of solids comprising vibrating mechanisms, e.g. mechanical, acoustical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0261—Solvent extraction of solids comprising vibrating mechanisms, e.g. mechanical, acoustical
    • B01D11/0265—Applying ultrasound
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/02—Recovery or refining of essential oils from raw materials
    • C11B9/025—Recovery by solvent extraction
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12G—WINE; PREPARATION THEREOF; ALCOHOLIC BEVERAGES; PREPARATION OF ALCOHOLIC BEVERAGES NOT PROVIDED FOR IN SUBCLASSES C12C OR C12H
    • C12G3/00—Preparation of other alcoholic beverages
    • C12G3/04—Preparation of other alcoholic beverages by mixing, e.g. for preparation of liqueurs
    • C12G3/06—Preparation of other alcoholic beverages by mixing, e.g. for preparation of liqueurs with flavouring ingredients
    • C12G3/07—Flavouring with wood extracts, e.g. generated by contact with wood; Wood pretreatment therefor
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • This invention relates to improvements in the liquid phase extraction of valuable chemical components from material by using preferentially immersed ultrasonic sonotrodes.
  • Oakwood comprises cellulose, hemicellulose, tannins and lignins - the fast 3 influencing wine during contact in wood.
  • Hemicellulose non-odorous
  • Tannins non-volatile liberated from wood are hydrolysable and composed of polymers of ellagic and gallic acids. Amounts in wine after storage in barrels can be up to 100 mg/L.
  • Important compounds entering wine by simple diffusion are cis and trans-b-methyl octalactoned which have a coconut-like aroma - by far the most important organoleptically (oak lactones can be modified to a more caramel-like note by furfural); aldehydes (particularly vanillin); phenolics ketones which augment the vanillin aroma; other volatile phenolics ketones; volatile phenols, such as eugenol (spicy, clove and carnation aromas); guaiacol and its derivatives (smoky and medicinal); furanic derivatives derived from toasting, and a range of other compounds; and Nor-isoprenoids (about 30, including B-ionone)
  • Toasting increases (i) the amounts of guaiacol (smoky and medicinal), 4-methyl guaiacol (smoky and clove-like), vanillin (vanilla), syringaldehyde, coniferaldehyde, sinapaldehyde and oak lactones (woody and coconut-like) in wine, and (ii) polysaccharides in oak (about 50%) give rise to furfural, maltol and cyclotene, which impart a sweet and toasty aroma.
  • American oak contains more oak lactones and nor-isoprenoid constituents than French oak.
  • a new 225 L barrel can contribute 3.8 g of wood extraction at a depth of penetration of 0.5 mm in about 2 months. Based on tasting results this is about 3 to 10 times the amount needed to produce a testable difference in wine. Over a lengthy period of time, penetration of up to 6 mm may occur.
  • European patent 583200 discloses a method of extracting evening primrose oil in an extraction column attached to which are ultrasonic transducers. [020] In USA .patent 5859236 there is disclosed an extraction process for microcrystalline cellulose in which the extracted liquor is subjected to ultrasonic agitation.
  • the high-energy waves create high energy cavitation, mechanical shock waves, micro streaming, high energy vibration and high energy pressure waves in the processed medium.
  • the present invention uses low frequency ultrasound (16kHz — 10OkHz) for the extraction of substances from material with the preferred frequency being between 20 and 30kHz.
  • a wide range of substances can be extracted using the method of the present invention including, but not limited to, colouring, f avourings and neutraceutical compounds existing within the material.
  • the ultrasonic frequency and the sonotrode design and the flow through cell design needs to be adapted for the material to be extracted.
  • the extent of the organic load and type of structure of the material will determine the type of sonotrode design.
  • the design of a specific sonotrode will allow for greater penetration of the ultrasonic wave/cavitational energy, better coupling of energy to the product and improved energy efficiency resulting in greater extraction of components, aqueous penetration and dislodgment of components from the material being extracted.
  • the present invention can be applied to include the extraction of colour and flavour compounds from grape skin, extraction of anthracyanins from grape skin, anti oxidants from grape seed using aqueous solvent, organic solvent or a combination of the two.
  • an oak process with low organic loading or products with a strong absorption factor of ultrasonic energy would use a cascade design radial sonotrode.
  • a process with a high organic load or a low ultrasonic absorption coefficient would use a radial sonotrode having an increased diameter to length (wavelength) factor /ratio producing ultrasonic waves which have a greater distance of propagation and have a greater capacity to penetrate through a product stream with a high organic loading or a product with a low ultrasonic absorption coefficient.
  • Prior art devices using transducers welded/bolted to the outside of vessels/chambers/tubes were not designed for specific types of organic load or products with different ultrasonic absorption characteristics.
  • Increased performance of aqueous penetration and extraction of components is achieved by using an automatic frequency scanning system for different types of product.
  • an automatic frequency scanning system for different types of product. For example, in extracting compounds from oak, the greater the organic ioad (concentration, viscosity), the more the type of oak surface/tissue/structure will determine the resonance frequency of that system/oak product.
  • the ultrasonic resonance frequency is the frequency at which the ultrasonic unit will deliver the greatest energy efficiency.
  • the resonance frequency of lettuce is 20,350 Hz where as carrot will have a resonance frequency of 20,210 Hz.
  • Prior art devices using transducers welded/bolted to the outside of vessels/chambers/tubes were not designed with an automatic resonance frequency tracking system for specific types of oak products so products could not be processed at the correct resonance frequency and maximum power efficiency.
  • the present invention is particularly useful in enhancing water as a solvent for the extraction of components from oak products.
  • the use of high power, energy efficient focused and radial systems producing high velocity microstreaming, high-energy cavitation enables the penetration of water through a hydrophobic surface and into the tissue/structure of the oak material to remove/dislodge components.
  • this invention could also be applied to the use of ultrasonics in combination with a mixture of water and organic solvent (e.g. water and ethanol) or an organic solvent alone (e.g. alcohol, hexane, acetone) for the extraction of compounds from products such as oak products.
  • a mixture of water and organic solvent e.g. water and ethanol
  • an organic solvent alone e.g. alcohol, hexane, acetone
  • the use of low frequency ultrasound could also be combined with supercritical fluids (e.g. liquid CO2) under high pressure for the extraction of components and compounds from oak materials.
  • the ultrasonic transducer could be attached to an existing high pressure vessel containing super critical liquid.
  • Another aspect of this invention is to use low frequency/high intensity ultrasound in combination with mild heat (0 0 C - 6O 0 C) to extract components, compounds from oak products.
  • the synergistic effect between ultrasonic energy and thermal energy enhances extraction kinetics and extraction yield.
  • Another aspect of this invention is to use low frequency/high intensity ultrasound in combination with pressure (0.5 to 10 bar pressure but preferentially between 2 and 4bar) to extract components, compounds from oak products.
  • pressure 0.5 to 10 bar pressure but preferentially between 2 and 4bar
  • This synergistic effect between ultrasonic energy and pressure greatly enhances the coupling and impedance matching of the ultrasonic waves to the medium particularly when the fluid contains high solids content.
  • the improved coupling of the waves to the product improves extraction kinetics and extraction yield
  • this present invention relates to the use of radial sonotrodes, which emit high-energy ultrasonic waves.
  • other sonotrodes could be used such as high amplitude focused sonotrodes, which produce high concentration of localized cavitation bubbles around the so ⁇ otrode surface.
  • the sonotrode and flow cell arrangements in accordance with the present invention are based on using radial sonotrodes immersed in a liquid phase and capable of being tuned to frequencies in the range of 16kHz - 100kHz and produce energy intensities of between 0.01 to 1000 W/cm 3 .
  • One arrangement includes Radial sonotrodes fitted longitudinally or laterally within an open tank, trough or flume. Reflector shields are arranged at the base to reflect and or focus ultrasonic energy into the product flow path.
  • Another suitable arrangement utilizes focused or radial sonotrodes fitted in a flow through cell where the water/oak product flows either directly into the face or across the face of the sonotrode. Residence time can be controlled by regulating the micro-streaming flow from the sonotrode, the flow rate, the power and size of a transducer/sonotrode, the number of transducer sonotrodes in series and parallel and vessel geometry.
  • the invention includes super critical fluids/extraction technology (such as liquid CO 2 ) to enhance yield and process kinetics.
  • super critical fluids/extraction technology such as liquid CO 2
  • Figure 1 shows a radial sonotrodes of the present invention fitted longitudinally in a channel
  • Figure 2 is shows a lateral sonotrode of the present invention for closed flow through cells
  • Figure 3 shows a focused sonotrode of the present invention in a rotating drum extractor
  • Figure 4 shows a radial sonotrode of the present invention in a closed flow through cell
  • Figure £ shows the results of the present invention on extraction of compounds from oak material, 10 seconds in water
  • Figure 8 shows the colour spectra of the extracted table grapes with different sonication times at 100% and 30% amplitude, focused;
  • Figure 9 shows the colour spectra of the extracted table grapes with different sonication times at 100% amplitude, radial;
  • Figure 10 shows the control gro ⁇ p; colour spectra of the extracted table grapes which were stirred for different time periods;
  • FIG. 11a and 11b Colour absorbance at the two standard wavelengths used for colour analysis for quality control in the wine industry. 11b represents the colour intensity, the summation of the absorbance at each wavelength. Data extracted from Figures 8-10;
  • Figure 12 shows pH of the extractions of figures 8-10 after different sonication times
  • Figure 13 shows Extraction from lemons for different experimental conditions
  • Figure 14 shows the extractable solids from tea as a wt%.
  • the systems of this invention include a power source, a transducer converting electric energy into mechanical vibrational energy, which is transmitted into the liquid extraction phase system by a sonotrode 5.
  • the sonotrode 5 can provide either radial wave, stationary wave or focused emission, depending on the application.
  • the sonotrode material may be made of titanium or ceramic, steel, cast alloy, or glass.
  • the transducer system could be PZT (piezo ceramic transducer), Terfenol-D magnetostrictive transducer or a Nickel-Iron-Vanadium magnetostrictive material.
  • the immersed sonotrodes 5 of the current invention could be used when conveyers are used to transport produce.
  • the current invention could also be a cascade sonotrode for use in low organic liquids and a radial sonotrode with a greater diameter to length ration for improved penetration in high organic loaded liquids.
  • the transducers/power supply can have an individual power ranging from 100 Watts - 16000 Watts.
  • the power supplies preferably include automatic resonance frequency tracking so that when the equipment is running during the extraction process, the unit is also always scanning the new resonance frequency (relates to maximum power output) due to changes in the liquid stream 12.
  • the sonotrodes/transducers can be mounted or retrofitted to tanks, vessels (round, square, oval), troughs, pipes, flow-cells 10 containing the solid materia! entrained in the flow 12 of the liquid extraction phase.
  • Figure 1 shows the sonotrode 5 immersed in the liquid extraction phase 7, with a reflector 9 in a channel 11.
  • the invention as described can also be combined with super critical fluids/extraction technology to enhance yield and process kinetics - such as liquid CO2.
  • a transducer could be incorporated on the outer shell of the extraction tube so that the extraction tube becomes the sonotrode.
  • the ultrasonic waves are then produced inside the super critical extraction tube where the super critical solvent and solid substrate is located.
  • the ultrasonic sonotrode could be connected via a flange internally inside the super critical extraction tube where it is exposed directly to the solid substrate and the super critical fluid.
  • the ultrasonic waves and cavitation produced aid solvent mass transfer of the super critical fluid into the solid substrate.
  • Examples of this application are the extraction of gingerol from ginger.
  • the sonicated samples were of the same time periods (10, 60 and 120 seconds) at 100% amplitude and one sample at 30% amplitude for 60
  • the sonicator was operated in either focused or radial modes. See Table 1 for the different experimental combinations.
  • the control samples were
  • Figure 12 shows the pH of the samples.
  • the pH slightly decreased with increased sonication time, probably as a result of the release of acids from the fruit and skins.
  • the absorbance without modifying the pH of the controls did not make a significant difference, probably as the amount of the anthocynin present was at the limit of detection of the instrument.
  • a batch of carrots was blended in a food mixer. 3Og of the blend was suspended in 150mt of 20% ethanol water solution either by sonication with a 400W bench too instrument or by mixing by hand (control samples). Variables considered were extraction time: 10, 20 and 30 seconds, focussed versus radial sonicatio ⁇ mode, and 100% versus 25% amplitude in radial mode. After the extraction the liquid component was immediately removed by sieving with a 0.8mm pore size stainless steel sieve. An aliquot of the sieved liquid was then filtered using a syringe filter with a pore size of 0.45 ⁇ m. This was then diluted 6 times with a 20% ethanol water mix and analysed on a VU-vis spectrometer. The background sample was an aliquot of pure extraction solvent (20% etha ⁇ ol water mix).
  • Peelings of each fruit were blended in a food mixer.
  • 30g of the blend was suspended in 150ml of water either by sonication with a 400W bench top instrument (manufacturer) or by mixing by hand (control samples).
  • Variables considered were extraction time: 5, 10 and 30 seconds, focussed versus radial sonication mode, and 100% versus 25% amplitude in radial mode.
  • For lime 15g of the blend was suspended in 75ml of water either by sonication with a 400W bench top instrument or by mixing by hand (control samples).
  • Variables considered were extraction time: 10 and 30 seconds, focused versus radial sonication mode, and 100% versus 25% amplitude in radial mode.
  • the liquid component was immediately removed by sieving with a 0.8mm pore size stainless steel sieve. 10ml of hexane was added to each liquid sample and vigorously mixed, by hand, for 30 seconds after which they were left to stand until the end of the day. The aqueous component was removed by freezing over night at approx - 15°C and decanting the liquid hexane.
  • Extractions were performed each using 200ml of tap water (at 80 0 C, 2 data points were also done at 5O 0 C for coffee) and 40g of tea or coffee.
  • the samples were stirred (control samples) or sonicated for 10, 20 and 30 seconds after which a liquid sample was taken for sieving (ca. 0.8mm mesh) followed by filtration at 0.45 ⁇ m for coffee and 0.2 ⁇ m pore size for tea.
  • a sub- sample of filtrate was immediately taken and diluted 10x with 1 :1 wt. mix of ethanol/water for tea; and 5Ox with water for coffee prior to measurements with a UV-visible spectrometer.
  • the remaining filtered sample was weighed and left to dry at 80 0 C. All extracted samples were weighed before and after drying to allow calculation of extractable solids as a % of extracted liquid/solution.
  • Figure 1 and 2 shows the extractable solids (% solids of the solution after filtration) and the UV-vis absorbance at 320nm wavelength for tea.
  • Figures 3 and 4 are for coffee showing the same detail as tea but the spectroscopy was at 350nm. The oak extraction only shows the UV-vis absorbance at 270nm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Acoustics & Sound (AREA)
  • Nutrition Science (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Biochemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Zoology (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Cosmetics (AREA)

Abstract

The present invention describes a method and apparatus for aqueous extraction of chemical compounds from solid material in which the solid material is entrained in an extraction liquid phase that flowed around immersed sonotrodes emitting radial or focused high energy ultrasonic waves. A significant increase in extracted material and decreases in extraction time is observed.

Description

[001] HIGH ENERGY ULTRASOUND EXTRACTION
[002] FIELD OF THE INVENTION
[003] This invention relates to improvements in the liquid phase extraction of valuable chemical components from material by using preferentially immersed ultrasonic sonotrodes.
[004] DESCRIPTION OF THE PRIOR ART
[005] The wooden barrel has historically occupied an important place as a general container for liquids and foodstuffs. However, the development of methods of materials handling, and of other construction materials more practical under modern conditions, has replaced the barrel almost completely, except for wine and spirit aging.
[006] Wines and spirits stored in oak barrels acquire attractive and desirable sensory characteristics, complexity and sensory qualities. Because of this, the production of many fine red and white table wines involves the use of oak barrels. Most barrels used for wine maturation around the world are between 190 and 500 lit-es in capacity. For table wine, a size of about 225 litres is the most common.
[007] Oakwood comprises cellulose, hemicellulose, tannins and lignins - the fast 3 influencing wine during contact in wood. Hemicellulose (non-odorous) do so indirectly - heating staves transform them chemically, thus becoming a base for other odor compounds. Tannins (non-volatile) liberated from wood are hydrolysable and composed of polymers of ellagic and gallic acids. Amounts in wine after storage in barrels can be up to 100 mg/L. The soluble lignins are partially degraded into aromatic aldehydes, which can form the corresponding phenolics acids by oxidation The contribution of new oak barrels depends mainly on the extraction of the volatile phenolics (over 200 identified) fraction of the wood components.
[008] Important compounds entering wine by simple diffusion are cis and trans-b-methyl octalactoned which have a coconut-like aroma - by far the most important organoleptically (oak lactones can be modified to a more caramel-like note by furfural); aldehydes (particularly vanillin); phenolics ketones which augment the vanillin aroma; other volatile phenolics ketones; volatile phenols, such as eugenol (spicy, clove and carnation aromas); guaiacol and its derivatives (smoky and medicinal); furanic derivatives derived from toasting, and a range of other compounds; and Nor-isoprenoids (about 30, including B-ionone)
[009] Toasting increases (i) the amounts of guaiacol (smoky and medicinal), 4-methyl guaiacol (smoky and clove-like), vanillin (vanilla), syringaldehyde, coniferaldehyde, sinapaldehyde and oak lactones (woody and coconut-like) in wine, and (ii) polysaccharides in oak (about 50%) give rise to furfural, maltol and cyclotene, which impart a sweet and toasty aroma.
[010] American oak contains more oak lactones and nor-isoprenoid constituents than French oak.
[011] In a new hogshead (300L) about 11 g of oak is extracted per mm of wine penetration into the wood. The first mm is penetrated in about 1 week. Based on barrel surface area per litre of wine, for each mm that wine penetrates into the barrel it extracts about 7.6 g of wood extract for a 200L barrel and 5.6 g for a 500L barrel.
[012] A new 225 L barrel can contribute 3.8 g of wood extraction at a depth of penetration of 0.5 mm in about 2 months. Based on tasting results this is about 3 to 10 times the amount needed to produce a testable difference in wine. Over a lengthy period of time, penetration of up to 6 mm may occur.
[013] This represents extraction of up to 46 g of wood in a 225L barrel. This gives about 100 times the min detectable level of flavouring for most wines, or the barrel could be filled and emptied 100 times and detectably flavour all of that wine.
[014] Diffusion of oak components into wine will change somewhat as the surface becomes exhausted, as large molecules will take longer to diffuse. However, a molecule capable of diffusing through the semi-permeable wood system will eventually be extracted, and it is not surprising that even after long and continual use of a barrel it may still contribute detectable oak flavours to wine stored in it for sufficient time.
[015] Traditionally the only way a wine would ever pick up wood character was through contact in an oak barrel or tank. But the increasing cost associated with the purchase of an oak barrel in past 10 years, economically minded winemakers, wishing to maintain the oak advantage, are switching to oak alternatives, oak replacements or oak options. Oak alternatives are practically anything in oak, which is not coopered. The terminology for the various options depends on the supplier, but the basic choices include staves and inserts of many lengths and toast levels, blocks, cubes, "dominoes," chips, shavings, chains of oak bars and oak powder. The quality of oak is the same as for oak barrels, but the cost is not.
[016] Aqueous and chemical extraction of valuable components such as oils, flavourings, pigments, pharmaceutical or nutritional compounds from materials is widely practiced. The speed and yields of such processes have an important influence on the cost of production.
[017] Agricultural production releases a large amount of waste that is found to contain a significant amount of high value components and dietary fibre, which are valuable substances. Extraction of high value components from food products could provide an additional income for producers. Conventional extraction has a number of problems including high organic chemical consumption, long operating time and low yield.
[018] There have been some attempts to improve the extraction process for some materials by utilizing ultrasonic vibrations to facilitate the contact between the material and the extraction agent.
[019] European patent 583200 discloses a method of extracting evening primrose oil in an extraction column attached to which are ultrasonic transducers. [020] In USA .patent 5859236 there is disclosed an extraction process for microcrystalline cellulose in which the extracted liquor is subjected to ultrasonic agitation.
[021] These prior patents demonstrate that low power ultrasonic technology producing wave vibrations assisted extraction in a small batch environment. However, the low power ultrasonic technology could not be used in a continuous flow process. In this case, the ultrasonic energy density is to low, the ultrasonic -esidence time is short and the volume/production speed is high.
[022] Also, the technology used in existing patents could not be used without breakdown, overheating, power overload, on a mobile fluid or medium because the electrical/electronic design specification of the generator and transducers were not designed to treat mobile fluids with changing physical and chemical conditions (flow rate, pressure, temperature, gas entrainment, vapour pressure of liquid, surface tension are examples)-. Low power ultrasound was designed only for small batch volumes, which were static (none mobile). The experience of using low power ultrasound has been that the cost effectiveness has not been commercially attractive or technically/economically viable.
[023] OBJECT OF THE INVENTION
[024] It is an object of the present invention to provide a method of extracting chemical components from material with greater efficiency than has otherwise been possible.
[025] It is an object Df the present invention to overcome, or at least substantially ameliorate, the disadvantages and shortcomings of the prior art.
[026] Other objects and advantages of the present invention will become apparent from the following description, taking in connection with the accompanying drawings, wherein, by way of illustration and example, an embodiment of the present invention is disclosed. [027] SUMMARY OF THE INVENTION
[028] According to the present invention, although this should not be seen as limiting the invention in any way, there is provided a method of aqueous extraction of chemical compounds from material in which the material entrained in an extraction liquid phase is flowed around immersed sonotrodes emitting radial or focused ultrasonic waves into the oak fluid medium at energy intensities in the range of 0.01 to 1000 WYcm3 (or 0.01 to 1000 W/cm2) but most preferentially the process will work effectively between 0.1 and 100 VWctn3 or 0.1 to 100 W/cm2.
{029] The high-energy waves create high energy cavitation, mechanical shock waves, micro streaming, high energy vibration and high energy pressure waves in the processed medium.
[030] The use of sonotrodes immersed in the liquid phase increases the penetration of the ultrasonic waves into the interior of the material. This contrasts with ttie prior art where transducers were clamped/bolted/welded to the outside of steel vessels/chambers. This effect creates low energy, low efficiency standing/stationary waves in the liquid allowing for only outer surface extraction and only if the residence time is very long (> 1 hour). The energy intensity associated with standing/stationary vibration waves is only in the region 0.0001 Watt/ cm3.
[031] Further the prior art was often limited to batch treatment and not continuous flow through extraction.
[032] The use of high intensity ultrasonic radial waves or focused energy produces microstreaming effects/cavitational effects on the surface and into the structure of the oak material to remove/dislodge components and to enhance aqueous penetration. In contrast prior ultrasonic methods which use the concept of transducers clamped/bolted/welded to the outside of steel vessels/chambers created low energy, low efficiency standing/stationary waves in the material which does not produce microstreaming effects to enhance aqueous penetration and component removal. In contrast, the introduction of high intensity sonotrodes into the liquid stream produces intensities of between 0.01 - 1000 W/cm3 allowing for high velocity microstreaming effects (780 km/hr), enhanced aqueous penetration and component removal.
[033] The present invention uses low frequency ultrasound (16kHz — 10OkHz) for the extraction of substances from material with the preferred frequency being between 20 and 30kHz. A wide range of substances can be extracted using the method of the present invention including, but not limited to, colouring, f avourings and neutraceutical compounds existing within the material.
[034] The ultrasonic frequency and the sonotrode design and the flow through cell design needs to be adapted for the material to be extracted. The extent of the organic load and type of structure of the material will determine the type of sonotrode design. The design of a specific sonotrode will allow for greater penetration of the ultrasonic wave/cavitational energy, better coupling of energy to the product and improved energy efficiency resulting in greater extraction of components, aqueous penetration and dislodgment of components from the material being extracted.
[035] In preference, the present invention can be applied to include the extraction of colour and flavour compounds from grape skin, extraction of anthracyanins from grape skin, anti oxidants from grape seed using aqueous solvent, organic solvent or a combination of the two.
[036] By way of example, an oak process with low organic loading or products with a strong absorption factor of ultrasonic energy would use a cascade design radial sonotrode. In contrast, a process with a high organic load or a low ultrasonic absorption coefficient would use a radial sonotrode having an increased diameter to length (wavelength) factor /ratio producing ultrasonic waves which have a greater distance of propagation and have a greater capacity to penetrate through a product stream with a high organic loading or a product with a low ultrasonic absorption coefficient. Prior art devices using transducers welded/bolted to the outside of vessels/chambers/tubes were not designed for specific types of organic load or products with different ultrasonic absorption characteristics.
[037] Increased performance of aqueous penetration and extraction of components is achieved by using an automatic frequency scanning system for different types of product. For example, in extracting compounds from oak, the greater the organic ioad (concentration, viscosity), the more the type of oak surface/tissue/structure will determine the resonance frequency of that system/oak product. The ultrasonic resonance frequency is the frequency at which the ultrasonic unit will deliver the greatest energy efficiency.
[038] This invention also provides an ultrasonic system, which locks onto the resonance frequency of a specific product and then re-scans for the new resonance frequency every 0.001 second throughout the treatment process. Without resonance frequency tracking a variation as little as 10Hz from the resonance frequency would result in a drop in energy efficiency in the order of 10 - 40%. This would have a significant reduced effect on the aqueous penetration, extraction of components and dislodgment of components.
[039] By way of example, the resonance frequency of lettuce is 20,350 Hz where as carrot will have a resonance frequency of 20,210 Hz. Prior art devices using transducers welded/bolted to the outside of vessels/chambers/tubes were not designed with an automatic resonance frequency tracking system for specific types of oak products so products could not be processed at the correct resonance frequency and maximum power efficiency.
[040] It is preferred to use high power and high amplitude ultrasound (O.OOlW/cm2 — 1000VWcm2) and 1-micron displacement - 500-micron displacement (the preferred amplitude range would be 20 - 60 microns) for the extraction. Prior art devices were unable to produce this kind of energy and amplitude level.
[041] The present invention is particularly useful in enhancing water as a solvent for the extraction of components from oak products. The use of high power, energy efficient focused and radial systems producing high velocity microstreaming, high-energy cavitation enables the penetration of water through a hydrophobic surface and into the tissue/structure of the oak material to remove/dislodge components.
[042] Thus using the system of the present invention organic solvents can be replaced wholly or partly with water and reduce the safety concerns that arise from the use of solvents such as hexane.
[043] However, this invention could also be applied to the use of ultrasonics in combination with a mixture of water and organic solvent (e.g. water and ethanol) or an organic solvent alone (e.g. alcohol, hexane, acetone) for the extraction of compounds from products such as oak products. The use of low frequency ultrasound could also be combined with supercritical fluids (e.g. liquid CO2) under high pressure for the extraction of components and compounds from oak materials.
[044] The ultrasonic transducer could be attached to an existing high pressure vessel containing super critical liquid.
[045] Another aspect of this invention is to use low frequency/high intensity ultrasound in combination with mild heat (00C - 6O0C) to extract components, compounds from oak products. The synergistic effect between ultrasonic energy and thermal energy enhances extraction kinetics and extraction yield.
[046] Another aspect of this invention is to use low frequency/high intensity ultrasound in combination with pressure (0.5 to 10 bar pressure but preferentially between 2 and 4bar) to extract components, compounds from oak products. This synergistic effect between ultrasonic energy and pressure greatly enhances the coupling and impedance matching of the ultrasonic waves to the medium particularly when the fluid contains high solids content. The improved coupling of the waves to the product improves extraction kinetics and extraction yield
[047] In the preferred equipment design, this present invention relates to the use of radial sonotrodes, which emit high-energy ultrasonic waves. However, other sonotrodes could be used such as high amplitude focused sonotrodes, which produce high concentration of localized cavitation bubbles around the soπotrode surface.
[048] The sonotrode and flow cell arrangements in accordance with the present invention are based on using radial sonotrodes immersed in a liquid phase and capable of being tuned to frequencies in the range of 16kHz - 100kHz and produce energy intensities of between 0.01 to 1000 W/cm3.
[049] One arrangement includes Radial sonotrodes fitted longitudinally or laterally within an open tank, trough or flume. Reflector shields are arranged at the base to reflect and or focus ultrasonic energy into the product flow path.
[050] Another suitable arrangement utilizes focused or radial sonotrodes fitted in a flow through cell where the water/oak product flows either directly into the face or across the face of the sonotrode. Residence time can be controlled by regulating the micro-streaming flow from the sonotrode, the flow rate, the power and size of a transducer/sonotrode, the number of transducer sonotrodes in series and parallel and vessel geometry.
[051] The invention relates to high power ultrasonic extraction of compounds from oak based materials, however the technology as described above could also be applied to other horticultural/agricultural based materials (fruit, vegetables, cereals, grass, seeds by way of example) for the extraction of neutraceutical, anti-oxidant, oils, flavourings, colorants, bio-active compounds, food materials.
[052] In preference, the invention includes super critical fluids/extraction technology (such as liquid CO2) to enhance yield and process kinetics.
[053] BRIEF DESCRIPTION OF THE DRAWINGS
[054] By way of example, an employment of the invention is described more fully hereinafter with reference to the accompanying drawings, in which:
[055] Figure 1 shows a radial sonotrodes of the present invention fitted longitudinally in a channel; [056] Figure 2 is shows a lateral sonotrode of the present invention for closed flow through cells;
[057] Figure 3 shows a focused sonotrode of the present invention in a rotating drum extractor;
[058] Figure 4 shows a radial sonotrode of the present invention in a closed flow through cell; . .
[059] Figure £ shows the results of the present invention on extraction of compounds from oak material, 10 seconds in water;
[060] Figure 6 shows the results of the present invention on extraction of compounds from oak material, 30 seconds in water;
[061] Figure 7 shows the results of the present invention on extraction of compounds from oak material, 10 seconds in 12% ethanol/water;
[062] Figure 8 shows the colour spectra of the extracted table grapes with different sonication times at 100% and 30% amplitude, focused;
[063] Figure 9 shows the colour spectra of the extracted table grapes with different sonication times at 100% amplitude, radial;
[064] Figure 10 shows the control groμp; colour spectra of the extracted table grapes which were stirred for different time periods;
[065] Figure 11a and 11b, Colour absorbance at the two standard wavelengths used for colour analysis for quality control in the wine industry. 11b represents the colour intensity, the summation of the absorbance at each wavelength. Data extracted from Figures 8-10;
[066] Figure 12 shows pH of the extractions of figures 8-10 after different sonication times;
[067] Figure 13 shows Extraction from lemons for different experimental conditions; [068] Figure 14 shows the extractable solids from tea as a wt%. [F = focυssed, R = radial, 100% and 25% = amplitude];
[069] Figure 15 shows the UV-vis absorbaπce from extracted tea. [F = focussed, R = radial, 100% and 25% = amplitude];
[070] Figure "• 6, shows the UV-vis absorbance from extracted coffee. [F = focussed, R = radial, 100% and 25% = amplitude];
[071] Figure 17 shows the extraction from oak chips into water and 12% ethanol/water. [F = focussed, R = radial, 100% and 25% = amplitude].
[072] DETAILED DESCRIPTION OF THE INVENTION
[073] The systems of this invention include a power source, a transducer converting electric energy into mechanical vibrational energy, which is transmitted into the liquid extraction phase system by a sonotrode 5. The sonotrode 5 can provide either radial wave, stationary wave or focused emission, depending on the application. The sonotrode material may be made of titanium or ceramic, steel, cast alloy, or glass.
[074] The transducer system could be PZT (piezo ceramic transducer), Terfenol-D magnetostrictive transducer or a Nickel-Iron-Vanadium magnetostrictive material.
[075] As could now well be appreciated, the immersed sonotrodes 5 of the current invention could be used when conveyers are used to transport produce. In addition the current invention could also be a cascade sonotrode for use in low organic liquids and a radial sonotrode with a greater diameter to length ration for improved penetration in high organic loaded liquids.
[076] Application of ultrasonics range (10kHz to 100kHz), intensity (0.01 W/cm3 - 1000 W/cm3) and amplitude (1 micron displacement — 500 micron displacement). The transducers/power supply can have an individual power ranging from 100 Watts - 16000 Watts. The power supplies preferably include automatic resonance frequency tracking so that when the equipment is running during the extraction process, the unit is also always scanning the new resonance frequency (relates to maximum power output) due to changes in the liquid stream 12. The sonotrodes/transducers can be mounted or retrofitted to tanks, vessels (round, square, oval), troughs, pipes, flow-cells 10 containing the solid materia! entrained in the flow 12 of the liquid extraction phase. Figure 1 shows the sonotrode 5 immersed in the liquid extraction phase 7, with a reflector 9 in a channel 11.
[077] Moreover, the invention as described can also be combined with super critical fluids/extraction technology to enhance yield and process kinetics - such as liquid CO2. A transducer could be incorporated on the outer shell of the extraction tube so that the extraction tube becomes the sonotrode. The ultrasonic waves are then produced inside the super critical extraction tube where the super critical solvent and solid substrate is located. Alternatively, the ultrasonic sonotrode could be connected via a flange internally inside the super critical extraction tube where it is exposed directly to the solid substrate and the super critical fluid.
[078] The ultrasonic waves and cavitation produced aid solvent mass transfer of the super critical fluid into the solid substrate. Examples of this application are the extraction of gingerol from ginger.
[079] As could not be readily appreciated to those skilled in the art, the above invention could also be readily applied to extraction of tea solids, colour, flavour and polyphenols from tea leaves - aqueous extraction, extraction of caffeine from coffee, extraction of coffee, flavour, colour from whole and ground roasted coffee beans - aqueous extraction, extraction of antioxidants, neutraceuticals, bio actives and carotenoids from agricultural products such as fruit, fruit pulp, fruit skin,
[080] Extraction from vegetables, vegetable pulp, vegetable skins and nuts - example of this would be lycopene from tomato pulp or skin, alpha and beta carroteine from carrot pulp and skin, citrus oil from the peel of citrus fruit such as orange, grapefruit, lime, lemon. This could be aqueous or solvent such as ethanol or a combination of aqueous and solvent, extraction of oils from agricultural products such as fruit, fruit pulp, fruit skin. [081] Extraction of corn oil from corn or corn germ, soya beans, olives, canola seeds, palm plants and palm fruit/fibre, rose oil from plant/petal materials. This could be aqueous or solvent such as ethanol, hexane, butane or a combination of aqueous and solvent.
[082] Extraction of flavours from agricultural products including fruit, vegetable and nuts such as chocolate from cocoa beans, extraction of protein from meat, extraction of renin from dairy products, extraction of sugar from sugar beat or sugar cane, extraction of starch from com, soya, wheat, (and other agricultural materials) and from the fibres of those materials, extraction of juice from fruit and vegetable based materials.
[083] Examples
[084] Oak Flavour Extraction
[085] 40g of oak was extracted using 150ml of either tap water or 12% ethanol/water or 100% ethanol. The samples were stirred (control samples) or sonicated for 10 and 30 seconds after which a liquid sample was taken for sieving (ca. 0.8mm mesh) followed by filtration with number 1 Whatman filter paper. A sub-sample of filtrate was diluted 3.5x with water and sent for oak flavour analysis by GC-MS at The Australian Wine Research Institute.
[086] Results
[087] The limit of quantification (μg/L in the diluted extract) for the identified chemicals by GC-MS were: guaiacol 3.5, eugenol 35, oak lactone 35, vanillin 35 and furfural 35. Other chemicals which were analysed but were below the limit of quantification were: 4-methylguaiacol, 4-ethylphenoi, 4-ethylguaiacol and 5-methylguaiacol.
[088] The extraction data shows that sonication using the above methodology increases the extraction of desired compounds compared to the control samples for the same extraction time.
[089] In radial mode 12% ethanol (Figure 5) was most effective, whereas in focussed mode water (Figure 6 and 7) was most effective. [090] From the above results sonication significantly increased the extraction of oak flavours as measured by GC-MS of the oak flavours. In focussed mode water was most effective, whereas in 12% ethaπo! radial and focussed were similar in effectiveness. Reducing the amplitude to 25% also did not make a significant reduction in the extraction of the flavour chemicals.
[091] Extraction of colour (anthocyanin) from red table grapes using different sonication methods and durations.
[092] Ten extractions were performed; each used 150ml of deionised water and peeled skins from 20 red table grapes. The control samples were stirred for 10, 60 and 120 seconds after which a liquid sample was taken for pH analysis followed by colour measurements with a UV-visible spectrometer.
The sonicated samples were of the same time periods (10, 60 and 120 seconds) at 100% amplitude and one sample at 30% amplitude for 60
. seconds. The sonicator was operated in either focused or radial modes. See Table 1 for the different experimental combinations. The control samples were
* 'ladjtfsTeTrϊb pH 4.3 to be inline with the sonicated samples which varied from
4.3 to 4.5. All samples were measured for colour without filtration and after filtration with 0.2μm syringe filters.
[093] Results
[094] Colour intensity increases with increased extraction time, measured by the absorbance of light at a specific wavelength, see Table 1 , Figures 8-10 and 11 of both the controls (stirred) and sonicated samples. Figures 8and 9 are on the same x- and y-axis scale and it is clear from the comparison that the focused mode extracts more colour than the radial mode. The summation of the absorbance at the wavelengths 420 and 520nm is defined as the colour intensity of the extract, as is typically measured in the wine industry. This is shown in Figure 11b, whereas the individual absorbances at each wavelength are shown in Figure 11a. It is clear that sonication greatly increases the extraction of anthocyanins and therefore the colour intensity.
Extraction time: 10 60 120
RadiaM00% 420nm 0.0196 0.0942 0.1832
RadiaM00% 520nm 0.0148 0.0884 0.198 Focused 100% 420nrn 0.033 0.1356 0.3368
Focused 100% 520nrn 0.0264 0.1254 0.376
Control 420nm 0.004 0.0076 0.0152
Control 520nm 0.002 0.002 0.002
Focused 30% 420nm 0.0296
Focused 30% 520nm 0.0224
[095] Table 1
[096] Increasing the duration of sonication from 60 to 120 seconds resulted in a greater than 2-fold increase in absorbance.
[097] Figure 12 shows the pH of the samples. The pH slightly decreased with increased sonication time, probably as a result of the release of acids from the fruit and skins. The absorbance without modifying the pH of the controls did not make a significant difference, probably as the amount of the anthocynin present was at the limit of detection of the instrument.
[098] Conclusion
[099] Sonication using the methodology described increases the release of the red colouring chemical, anthocyanins, found in the skins of grapes. Increasing the duration of sonication had a positive effect on the colour intensity (Figure 11) as did the use of the focused mode. Reduction of the amplitude to 30% had an expected reduction in the extraction.
[0100] Extraction of carotene from carrots and limonene from lemon and limes
[0101] Methodology for the extraction and analysis of carotene
[0102] A batch of carrots was blended in a food mixer. 3Og of the blend was suspended in 150mt of 20% ethanol water solution either by sonication with a 400W bench too instrument or by mixing by hand (control samples). Variables considered were extraction time: 10, 20 and 30 seconds, focussed versus radial sonicatioα mode, and 100% versus 25% amplitude in radial mode. After the extraction the liquid component was immediately removed by sieving with a 0.8mm pore size stainless steel sieve. An aliquot of the sieved liquid was then filtered using a syringe filter with a pore size of 0.45μm. This was then diluted 6 times with a 20% ethanol water mix and analysed on a VU-vis spectrometer. The background sample was an aliquot of pure extraction solvent (20% ethaπol water mix).
[0103] Methodology for the extraction and analysis of limonene from lemon and lime
[0104] Peelings of each fruit were blended in a food mixer. For lemon, 30g of the blend was suspended in 150ml of water either by sonication with a 400W bench top instrument (manufacturer) or by mixing by hand (control samples). Variables considered were extraction time: 5, 10 and 30 seconds, focussed versus radial sonication mode, and 100% versus 25% amplitude in radial mode. For lime 15g of the blend was suspended in 75ml of water either by sonication with a 400W bench top instrument or by mixing by hand (control samples). Variables considered were extraction time: 10 and 30 seconds, focused versus radial sonication mode, and 100% versus 25% amplitude in radial mode. After the extraction of the lemon and lime the liquid component was immediately removed by sieving with a 0.8mm pore size stainless steel sieve. 10ml of hexane was added to each liquid sample and vigorously mixed, by hand, for 30 seconds after which they were left to stand until the end of the day. The aqueous component was removed by freezing over night at approx - 15°C and decanting the liquid hexane.
[0105] An aliquot of each sample was analysed on a VU-vis spectrometer with the background sample as hexane.
[0106] Results
[0107J An increased absorption at a specific wavelength indicates the presence of increased analyte. For each wavelength represented in each chart in figure one, each variable (time, sonication mode and amplitude) is depicted. Figure 13 is a representative example showing the effects of the variables (time, sonication mode and amplitude) upon the extraction from lemon and lime.
[0108] The data shows that sonication using the described methodology increases the extraction compared to the control samples for the same extraction time. Increasing the extraction time increases the measured extract for carrot, lemon and lime.
[0109] Extraction of tea, coffee and oak.
[0110] Methodology for tea and coffee
[0111] Extractions were performed each using 200ml of tap water (at 800C, 2 data points were also done at 5O0C for coffee) and 40g of tea or coffee. The samples were stirred (control samples) or sonicated for 10, 20 and 30 seconds after which a liquid sample was taken for sieving (ca. 0.8mm mesh) followed by filtration at 0.45μm for coffee and 0.2 μm pore size for tea. A sub- sample of filtrate was immediately taken and diluted 10x with 1 :1 wt. mix of ethanol/water for tea; and 5Ox with water for coffee prior to measurements with a UV-visible spectrometer. The remaining filtered sample was weighed and left to dry at 80 0C. All extracted samples were weighed before and after drying to allow calculation of extractable solids as a % of extracted liquid/solution.
[0112] Methodology for oak
[0113] 4Og of oak was extracted using 150ml of either tap water or 12% ethanol/water. For oak chips only one extraction time was used for the 12% ethanol mix. The samples were stirred (control samples) or sonicated for 10, 20 and 30 seconds after which a liquid sample was taken for sieving (ca. 0.8mm mesh) followed by filtration with number 1 Whatman filter paper. A sub- sample of filtrate was immediately taken and diluted 5x with either extraction solvents; prior to measurements with a UV-visible spectrometer. A second filtrate sub-sample was diluted 3.5x with water and sent for oak flavour analysis by GC-MS.
[0114] Oak powder used: Medium toast, ca. 1mm particle size
[0115] Oak chips used: Heinrich Cooperage, American Oak Medium. Particle size approx 10- 18mm long, 2-7mm wide, 1-2mm thick.
[0116] Results and discussion [0117] Figure 1 and 2 shows the extractable solids (% solids of the solution after filtration) and the UV-vis absorbance at 320nm wavelength for tea. Figures 3 and 4 are for coffee showing the same detail as tea but the spectroscopy was at 350nm. The oak extraction only shows the UV-vis absorbance at 270nm.
[0118] Results
[0119] All the data shows that sonication increases the extraction compared to the control samples for the same extraction time.
[0120] Any improvement may be made in part or all of the method steps and systems components. All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended to illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. Any statement herein as to the nature or benefits of the invention or of the preferred embodiments is not intended to be limiting, and the appended claims should not be deemed to be limited by such statements. More generally, no language in the specification should be construed as indicating any non-claimed element as being essential to the practice of the invention. This invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contraindicated by context.

Claims

1. A method of extraction of chemical compounds from a solid material in which the solid material is entrained in a liquid extraction phase that is flowed around a sonotrode immersed in the liquid phase, the sonotrode emitting ultrasonic waves into the liquid phase at energy intensities between approximately 0.1 and 100 W/cm2.
2. The method of claim 2, wherein the emitted ultrasonic waves are radial or focused.
3. The method of claim 3, wherein the method further includes degassing the liquid phase.
4. The method of claim 4, wherein the material is a food product.
5. The method of anyone of claims 1 to 5, wherein the method further includes tuning the sonotrode to lock onto a resonate frequency of the material entrained in the extraction liquid phase.
6. The method of claim 6, wherein the liquid phase is an aqueous liquid.
7. The method of claim 7, wherein the aqueous liquid is water.
8. The method of claim 6 wherein the liquid phase is a supercritical liquid.
9. The method of any one of claims 1-5, wherein the liquid phase is heated to between 00C and 600C.
10. The method of anyone of claims 1-10, wherein the liquid phase is held under a pressure.
11. The method of claim 11, wherein the pressure is between 0.5 bar to 10 bar.
12. The method of claim 12, wherein the pressure is between 2 bar and 4 bar.
13. The method of claim 5, wherein the food material is selected from the group consisting of fruit, vegetables, cereals, grasses, seeds, and mixtures thereof.
14. An apparatus for extracting chemical compounds from a solid material including an extractor body;
i. a conduit for directing a flow of liquid extraction phase around the material such that the materia! is entrained therein;
ii. at least one ultrasonic generator operatively connected to at least one sonotrode, the at least one sonotrode being in contact with the liquid phase;
iii. such that operation of the ultrasonic generator results in ultrasonic energy being applied to the solid material entrained in the liquid phase.
15. The apparatus of claim 14, wherein the ultrasonic generator operates at energy intensities between approximately 0.1 and 100 W/cm2.
16. The apparatus of claim 15, wherein the sonotrode operatively connected to the ultrasonic generator is tuneable to lock onto a resonate frequency of the material entrained in the extraction liquid phase.
17. The apparatus for extracting chemical compounds from solid material as substantially described herein.
PCT/AU2007/001958 2006-12-18 2007-12-18 High energy ultrasound extraction WO2008074072A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP07845399A EP2106278A4 (en) 2006-12-18 2007-12-18 High energy ultrasound extraction
JP2009541691A JP2010512998A (en) 2006-12-18 2007-12-18 High energy ultrasonic extraction
CN2007800512116A CN101622043B (en) 2006-12-18 2007-12-18 High energy ultrasound extraction
US12/520,062 US8343562B2 (en) 2006-12-18 2007-12-18 High energy ultrasound extraction method and apparatus
BRPI0720541-4A2A BRPI0720541A2 (en) 2006-12-18 2007-12-18 HIGH ENERGY EXTRACTION
AU2007335247A AU2007335247B2 (en) 2006-12-18 2007-12-18 High energy ultrasound extraction

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2006907033 2006-12-18
AU2006907033A AU2006907033A0 (en) 2006-12-18 High energy ultrasound extraction

Publications (1)

Publication Number Publication Date
WO2008074072A1 true WO2008074072A1 (en) 2008-06-26

Family

ID=39535880

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2007/001958 WO2008074072A1 (en) 2006-12-18 2007-12-18 High energy ultrasound extraction

Country Status (7)

Country Link
US (1) US8343562B2 (en)
EP (1) EP2106278A4 (en)
JP (1) JP2010512998A (en)
CN (1) CN101622043B (en)
AU (1) AU2007335247B2 (en)
BR (1) BRPI0720541A2 (en)
WO (1) WO2008074072A1 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008138324A1 (en) * 2007-05-15 2008-11-20 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Phenol extracts from oil seeds
WO2010077171A2 (en) 2008-12-29 2010-07-08 Limited Liability Company "Prof Business" Process and system for extraction of bioactive compounds from plant material
WO2010129985A1 (en) * 2009-05-14 2010-11-18 Cavitus Pty Ltd Density modification
WO2010138254A1 (en) * 2009-05-28 2010-12-02 Cargill, Incorporated Improving oil recovery and reducing the oxygen demand of palm oil mill effluent
US20110189353A1 (en) * 2009-01-27 2011-08-04 Frito-Lay North America, Inc. Methods of Flavor Encapsulation and Matrix-Assisted Concentration of Aqueous Foods and Products Produced Therefrom
DE102010052052A1 (en) * 2010-11-23 2012-05-24 Abel und Schäfer GmbH & Co. KG Treating poppy seeds, preferably opium poppy seeds comprises washing poppy seeds with water for reducing alkaloid content and drying
WO2012106768A1 (en) * 2011-02-09 2012-08-16 Cavitus Pty Ltd Methods for isolating oil from plant material and for improving separation efficiency
EP2334424A4 (en) * 2008-07-29 2013-04-10 Cavitus Pty Ltd Viscosity reduction
WO2015136130A1 (en) 2014-03-13 2015-09-17 Productos Agrovin, S.A. Use of ultrasound in wine-making processes
WO2016046481A1 (en) * 2014-09-25 2016-03-31 Seguin Moreau & C° Method for the treatment of pieces of wood and use thereof in the manufacture of wines and spirits, or of wood extracts or of wooden containers
WO2017182552A1 (en) 2016-04-20 2017-10-26 Gcr - Global Commodity Resources Ug (Haftungsbeschränkt) Method for obtaining etheric oils and/or constituents of etheric oils from moist extraction material
WO2019209127A1 (en) * 2018-04-27 2019-10-31 Bicafé - Torrefecção E Comércio De Café, Lda. System for extracting a caffeine-rich powder

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2645323A1 (en) * 2006-03-16 2007-09-27 Matthew Gardner Meat brines
US20100272870A1 (en) * 2009-04-24 2010-10-28 Far East University Preparation method for caffeine control and device thereof
IT1399668B1 (en) * 2010-04-09 2013-04-26 Gambardella PROCESS AND PLANT OF EXTRACTION OF OILS AND ESSENCES FROM ORGANIC SUBSTANCES AND THEIR POSSIBLE DEODORIZATION
US10334870B2 (en) 2010-10-07 2019-07-02 Tropicana Products, Inc. Processing of whole fruits and vegetables, processing of side-stream ingredients of fruits and vegetables, and use of the processed fruits and vegetables in beverage and food products
RU2605352C1 (en) 2013-02-15 2016-12-20 Пепсико, Инк. Obtaining and including by-products in beverages to increase nutritional value and improve organoleptic properties
US9388363B2 (en) 2013-03-15 2016-07-12 Megasonic Sweeping, Incorporated Ultrasonic and megasonic method for extracting palm oil
CN108604882A (en) * 2014-03-20 2018-09-28 彼得·哈格尔施泰因 The conversion of vibrational energy
CN106998769A (en) * 2014-11-28 2017-08-01 高砂香料工业株式会社 Flavor improving agent
US10633620B2 (en) * 2016-11-10 2020-04-28 Mark DeCaro Accelerated spirit/beverage aging and flavor loading methods and systems
US10332252B2 (en) * 2016-12-29 2019-06-25 General Electric Company Slope constrained cubic interpolation
US11582987B2 (en) * 2017-06-07 2023-02-21 Whitewave Services, Inc. Systems and methods using physical energy technology to produce non-dairy protein base and value-added utilization of the co-product

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4416785A1 (en) * 1994-05-09 1995-11-16 Guenther Dr Kannert Appts. for extraction of solids with compressed gas
RU2104733C1 (en) * 1996-11-06 1998-02-20 Сульман Михаил Геннадьевич Method of extraction from solid vegetable raw material
US5859236A (en) * 1996-02-29 1999-01-12 Burkart; Leonard Process for preparation of lignin and microcellulose
DE19842998A1 (en) * 1998-09-21 2000-04-13 Maria Uphoff Process for testing soil samples comprises using a container having a flat resonating base
DE10164274A1 (en) * 2001-12-27 2003-07-17 Energietechnik Leipzig Gmbh Continuous extraction of fatty acid from native oils and transesterification of such oils, involves extraction with alcohol, phase separation and reaction with alcohol in presence of catalyst, all with ultrasound assistance
US7101691B2 (en) * 2003-08-29 2006-09-05 Ultraforce Technology Llc Alcohol production using sonication
US20060204624A1 (en) * 2005-03-14 2006-09-14 Cargill, Inc. Process and apparatus for enhancing peel oil extraction

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4603115A (en) * 1983-01-17 1986-07-29 International Coal Refining Company Automated process for solvent separation of organic/inorganic substance
JPS59169505A (en) * 1983-03-15 1984-09-25 Gunma Daigaku Liquid-liquid extractive separation apparatus by ultrasonic emulsification
AU578313B2 (en) * 1984-09-26 1988-10-20 Werner Alex Julius Greve Extracting fragrant oil extracts using high frequency acoustic energy
JPH01139103A (en) * 1987-11-25 1989-05-31 Mitsubishi Heavy Ind Ltd Extractive separation using supercritical gas as gaseous solvent
JPH04221318A (en) * 1990-12-20 1992-08-11 Toyotama Koryo Kk Method for extracting citrus limonoid
FR2694705B1 (en) 1992-08-12 1994-09-23 Commissariat Energie Atomique Continuous solvent extraction process with ultrasound treatment and column for carrying out this process.
US5829345A (en) * 1996-10-30 1998-11-03 Inter-Nevet Ltd. Devices and methods for isolating seeds of vegetables and fruits and for releasing and separating same from coats
US7439654B2 (en) * 2004-02-24 2008-10-21 Air Products And Chemicals, Inc. Transmission of ultrasonic energy into pressurized fluids
US7604126B2 (en) * 2004-10-22 2009-10-20 Cargill, Incorporated Treatment of phosphate material using directly supplied, high power ultrasonic energy
JP4705691B2 (en) * 2006-10-11 2011-06-22 クリティテック・インコーポレイテッド Method for precipitating small pharmaceutical particles in a container for use

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4416785A1 (en) * 1994-05-09 1995-11-16 Guenther Dr Kannert Appts. for extraction of solids with compressed gas
US5859236A (en) * 1996-02-29 1999-01-12 Burkart; Leonard Process for preparation of lignin and microcellulose
RU2104733C1 (en) * 1996-11-06 1998-02-20 Сульман Михаил Геннадьевич Method of extraction from solid vegetable raw material
DE19842998A1 (en) * 1998-09-21 2000-04-13 Maria Uphoff Process for testing soil samples comprises using a container having a flat resonating base
DE10164274A1 (en) * 2001-12-27 2003-07-17 Energietechnik Leipzig Gmbh Continuous extraction of fatty acid from native oils and transesterification of such oils, involves extraction with alcohol, phase separation and reaction with alcohol in presence of catalyst, all with ultrasound assistance
US7101691B2 (en) * 2003-08-29 2006-09-05 Ultraforce Technology Llc Alcohol production using sonication
US20060204624A1 (en) * 2005-03-14 2006-09-14 Cargill, Inc. Process and apparatus for enhancing peel oil extraction

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200341, Derwent World Patents Index; Class J01, AN 2003-437497, XP008109419 *
See also references of EP2106278A1 *

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008138324A1 (en) * 2007-05-15 2008-11-20 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Phenol extracts from oil seeds
EP2334424A4 (en) * 2008-07-29 2013-04-10 Cavitus Pty Ltd Viscosity reduction
WO2010077171A2 (en) 2008-12-29 2010-07-08 Limited Liability Company "Prof Business" Process and system for extraction of bioactive compounds from plant material
US9504274B2 (en) * 2009-01-27 2016-11-29 Frito-Lay North America, Inc. Methods of flavor encapsulation and matrix-assisted concentration of aqueous foods and products produced therefrom
US20110189353A1 (en) * 2009-01-27 2011-08-04 Frito-Lay North America, Inc. Methods of Flavor Encapsulation and Matrix-Assisted Concentration of Aqueous Foods and Products Produced Therefrom
WO2010129985A1 (en) * 2009-05-14 2010-11-18 Cavitus Pty Ltd Density modification
US9005686B2 (en) 2009-05-14 2015-04-14 Cavitus Pty Ltd Density modification
AU2010246892B2 (en) * 2009-05-14 2016-01-21 Cavitus Pty Ltd Density modification
WO2010138254A1 (en) * 2009-05-28 2010-12-02 Cargill, Incorporated Improving oil recovery and reducing the oxygen demand of palm oil mill effluent
US20120083618A1 (en) * 2009-05-28 2012-04-05 Cargill, Incorporated method of improving oil recovery and reducing the biochemical oxygen demand and chemical oxygen demand of palm oil mill effluent
DE102010052052A1 (en) * 2010-11-23 2012-05-24 Abel und Schäfer GmbH & Co. KG Treating poppy seeds, preferably opium poppy seeds comprises washing poppy seeds with water for reducing alkaloid content and drying
WO2012106768A1 (en) * 2011-02-09 2012-08-16 Cavitus Pty Ltd Methods for isolating oil from plant material and for improving separation efficiency
WO2015136130A1 (en) 2014-03-13 2015-09-17 Productos Agrovin, S.A. Use of ultrasound in wine-making processes
US11045782B2 (en) 2014-03-13 2021-06-29 Productos Agrovin, S.A. Application of ultrasound in vinification processes
US11052371B2 (en) 2014-03-13 2021-07-06 Productos Agrovin, S.A. Application of ultrasound in vinification processes
FR3026337A1 (en) * 2014-09-25 2016-04-01 Seguin Moreau & C PROCESS FOR TREATING WOODEN PIECES AND THEIR USE IN THE MANUFACTURE OF WINES AND SPIRITS, OR EXTRACTS OF WOOD OR WOOD CONTAINERS
WO2016046481A1 (en) * 2014-09-25 2016-03-31 Seguin Moreau & C° Method for the treatment of pieces of wood and use thereof in the manufacture of wines and spirits, or of wood extracts or of wooden containers
WO2017182552A1 (en) 2016-04-20 2017-10-26 Gcr - Global Commodity Resources Ug (Haftungsbeschränkt) Method for obtaining etheric oils and/or constituents of etheric oils from moist extraction material
DE102016206677A1 (en) 2016-04-20 2017-10-26 Gcr Global Commodity Resources Ug (Haftungsbeschränkt) Process for obtaining essential oils and / or constituents of essential oils from moist extraction material
WO2019209127A1 (en) * 2018-04-27 2019-10-31 Bicafé - Torrefecção E Comércio De Café, Lda. System for extracting a caffeine-rich powder

Also Published As

Publication number Publication date
JP2010512998A (en) 2010-04-30
US8343562B2 (en) 2013-01-01
AU2007335247B2 (en) 2011-11-17
BRPI0720541A2 (en) 2014-02-18
EP2106278A1 (en) 2009-10-07
AU2007335247A1 (en) 2008-06-26
CN101622043B (en) 2013-10-16
US20100015302A1 (en) 2010-01-21
EP2106278A4 (en) 2011-02-02
CN101622043A (en) 2010-01-06

Similar Documents

Publication Publication Date Title
AU2007335247B2 (en) High energy ultrasound extraction
Clodoveo et al. Emerging technology to develop novel red winemaking practices: An overview
Kovačević et al. Innovative technologies for the recovery of phytochemicals from Stevia rebaudiana Bertoni leaves: A review
US11326137B2 (en) Method of infusing beer with hops flavoring using controlled mechanically induced cavitation
Selvamuthukumaran et al. Recent advances in extraction of antioxidants from plant by-products processing industries
Bobinaitė et al. Application of pulsed electric field in the production of juice and extraction of bioactive compounds from blueberry fruits and their by-products
El Darra et al. Pulsed electric field, ultrasound, and thermal pretreatments for better phenolic extraction during red fermentation
Rodrigues et al. Extraction processes assisted by ultrasound
US11045782B2 (en) Application of ultrasound in vinification processes
Cisneros-Yupanqui et al. Ultrasound-assisted extraction of antioxidant bioactive compounds from wastes of rapeseed industry and their application in delaying rapeseed oil oxidation
US20160222333A1 (en) System and methods for the completion of chemical reactions in bottled products
Gupta et al. Orange
Mason et al. Ultrasonically assisted extraction in food processing and the challenges of integrating ultrasound into the food industry
Mazumder et al. Sonication microwave synergistic extraction of bioactive compounds from plant source
US11781097B2 (en) Preparations including extracts of natural products such as wood and use thereof as flavorings for food and alcoholic and non-alcoholic beverages
Goswami et al. Ultrasound-Assisted Extraction for Food, Pharmacy, and Biotech Industries
Nolan ULTRASOUND FOR ACCELERATING THE WINE AGEING PROCESS: AWINETASTER’S VIEW
US20230384660A1 (en) Preparations including extracts of natural products such as wood and use thereof as flavorings for food and alcoholic and non-alcoholic beverages
Neftullayeva et al. Investigation of the yield of biologically active substances during the ultrasound and electro-discharge extraction of medicinal herbs of the foothills of the North Caucasus.
Qomarudin Extraction of Pandanus amaryllifiolus Roxb.: A review of methods and the influencing factors
Türkmen Effect of Sonication Treatments on Freshly Squeezed Mandarin Juice Quality Parameters
Sangeeta et al. New Food Product Development from Citrus Fruits
Comandini Development of instrumental and sensory analytical methods of food obtained by traditional and emerging technologies
NZ761407B2 (en) Passive care control method and associated systems
NZ761407A (en) Monoclonal antibodies against her2 epitope

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200780051211.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07845399

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2009541691

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2007335247

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 4627/DELNP/2009

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 2007845399

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2007335247

Country of ref document: AU

Date of ref document: 20071218

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 12520062

Country of ref document: US

REG Reference to national code

Ref country code: BR

Ref legal event code: B01E

Ref document number: PI0720541

Country of ref document: BR

Free format text: APRESENTE DOCUMENTOS COMPROBATORIOS QUE EXPLIQUEM A DIVERGENCIA NO NOME DE TRES INVENTORES QUE CONSTAM NA PUBLICACAO INTERNACIONAL WO 2008/074072 DE 26/06/2008, "DARREN BATES", "RICHARD MCLOUGHLIN" E "ANDREW YAP", E O CONSTANTE DA PETICAO INICIAL NO 020090060180 DE 18/06/2009, "DARREN M. BATES", 'ARTHUR R. MCLOUGHLIN" E "ANDREW SIN JU YAP", RESPECTIVAMENTE.

ENP Entry into the national phase

Ref document number: PI0720541

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20090618