WO2012036695A1 - Process to remove impurities from triacylglycerol oil - Google Patents
Process to remove impurities from triacylglycerol oil Download PDFInfo
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- WO2012036695A1 WO2012036695A1 PCT/US2010/049284 US2010049284W WO2012036695A1 WO 2012036695 A1 WO2012036695 A1 WO 2012036695A1 US 2010049284 W US2010049284 W US 2010049284W WO 2012036695 A1 WO2012036695 A1 WO 2012036695A1
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- C11B3/00—Refining fats or fatty oils
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
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- C11B3/00—Refining fats or fatty oils
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- C11B3/00—Refining fats or fatty oils
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
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Definitions
- the invention generally relates to methods of triacylglycerol oil refining and is based on using flow-through hydrodynamic cavitation.
- the invention utilizes energy released upon the implosion of cavitation bubbles to purify oils and improve the commercial value of collected by-products. More particularly, the present invention relates to lowering the levels of sterol glucosides (SGs) and acylated sterol glucosides (ASGs) and enzyme- hydrolyzable phospholipids which can be followed by biodiesel production through transesterification.
- the residual concentrates obtained from the invention can be used as blood cholesterol lowering food additives, in
- Crude vegetable oils are comprised mostly of triacylglycerols (TAG) and contain impurities such as phospholipids (phosphatides), free fatty acids (FFA), off-flavor compounds, carotenes, chlorophyll and other pigments, waxes, aluminum, calcium, copper, iron, magnesium and other metals and
- the crude oil can be produced by solvent extraction or by pressing seeds either with heating or without it. The hot pressing affords the better yield but results in oil deterioration and the accumulation of non-hydratable phosphatides (NHP), for example calcium and magnesium salts of phosphatidic acid (PA) and phosphatidyl ethanolamine (PE) due to the action of enzymes that are active at 57-85 ° C. PE can be hydrated if it has a net charge.
- PA has a glycerol backbone usually with a saturated fatty acid, an unsaturated acid, and a phosphate group attached to carbon 1 , 2 and 3 , correspondingly.
- Oil refining methods depend on the type of oil and usually
- Degumming is the removal of phosphorus present in the form of hydratable and non-hydratable phosphatides.
- Water degumming provides refined oil with a phosphorus concentration greater than 200 ppm and can be followed by alkali refining, bleaching and deodorizing or by acid degumming, dry degum ming and physical refining or by enzymatic degumming (Clausen, 2001 ), bleaching and physical refining.
- oil refining methods depending on the quality of oil and other conditions.
- oil can be hydrogenated to afford a stable product. [ Para 5] Each refining step results in some loss of oil.
- the oil yield can be increased by using enzymes instead of chemical reagents.
- enzymes for example, phospholipase C hydrolyzes phosphatidylcholine (PC), liberating the water- solu ble phosphate ester of choline and diacylglycerol (DAG).
- PC phosphatidylcholine
- DAG diacylglycerol
- the conversion of phospholipids to DAG increases the oil yield due to the accumulation of DAG in the oil phase and minimal entrapment of neutral oil in gu ms comprised of hydrated lecithin.
- PC is converted by phospholipases Al and A2 to
- LPE lysophosphatidylcholine and FFA.
- Lipid acyltransferase (LAT) catalyzes PC breakdown to lysophosphatidylcholine and FFA, which can form esters with the free sterols present in oil. Accordingly, PE is converted by phospholipases Al and A2 and LAT to lysophosphatidylethanolamine (LPE) and FFA or steryl esters. LPE is a plant growth regulator that can be isolated as a valuable by-product.
- Phospholipase C catalyses the hydrolysis of PE to ethanolamine-phosphate and DAG.
- Phosphatidylinositol can be hydrated over a wide pH range and is converted by phospholipases Al and A2 and LAT to lysophosphatidylinositol. However, PI is not hydrolyzed by phospholipase C. Phospholipases Al and A2 and LAT convert alkali salts of PA to lysophosphatidic acid salts. Alkali salts of PA are not affected by phospholipase C.
- SGs are sterol derivatives, in which a carbohydrate unit (arabinose, glucose, etc.) is linked to the hydroxyl group of campesterol, brassicasterol, dihydrositosterol, sitosterol, stigmasterol or other sterols with an ether bond.
- ASGs which are very soluble in vegetable oils, the carbohydrate 6-carbon is esterified with a long chain fatty acid.
- Phytosterols are abundant in plants and can be readily isolated. (Sugawara and Miyazawa, 1 999) They are cellular stress mediators and possess anticancer properties.
- SGs were reported to exhibit a neurotoxic effect and are a potential causal factor in the motor neuron pathology previously associated with cycad consumption and amyotrophic lateral sclerosis-parkinsonism dementia complex.
- SGs are not soluble in biodiesel or diesel and, therefore, cannot be forced through a diesel engine filter, resulting in a clogged fuel system.
- SG crystallizes at about 35 ppm at room temperature leading to the formation of haze in biodiesel.
- SGs and ASGs melt at approximately 240 and 250-300 ° C and promote the crystallization of other compounds present in biodiesel at cold temperatures by becoming the seed crystals for large agglomerates. Thus, it is necessary to lower the ASG and SG content of oil feedstock prior to the production of biodiesel.
- the Filter Blocking Tendency (FBT) value of soybean biodiesel with -70 ppm SG is approximately fifteen.
- the value for FBT of diatomaceous earth-filtered biodiesel with -20 ppm SG is close to one.
- the sticky residue retained with filters at palm or soybean biodiesel plants contains up to 50 and 25% of SG and ASG, correspondingly. SGs exhibit high adsorption capacity towards fatty acid methyl esters which results in their entrapment. (Van Hoed et a/., 2008)
- the bu bbles collapse in a slow- velocity, high-pressure zone, causing sharp increases in both pressure and temperature, the formation of high-velocity streams and Shock waves, vigorous shearing forces, and the release of a substantial amount of energy.
- This process activates atoms, molecules, ions and/or radicals located in the bubbles and the surrounding liquid, and initiates chemical reactions and processes.
- the bubble implosion can also result in the emission of light favoring
- the invention provides an oil purification method based on generating cavitation in an oil flow within at least one cavitation apparatus' chamber, preferably in a number of the consecutively placed chambers. This goal is achieved through the application of cavitation apparatuses aimed at the express purification of oils.
- the method comprises feeding a fluidic mixture of oil and agent in the flow- through hydrodynamic cavitation device using a preset inlet pressure sustained by a pump and applying selected conditions and additional agents, if required.
- the present invention is directed to the method of processing TAG oil, fat, tallow and grease with a single- or multi-stage flow-through hydrodynamic cavitation apparatus, including a rotor-stator cavitation apparatus and a high-speed (high-energy) jet collision cavitation apparatus.
- Hydrodynamic cavitation significantly lowers the level of impurities in oil, allowing for express, high-efficiency refining. The treatment begins with providing a cavitation apparatus.
- liquid oil is mixed with an agent (for example, the aqueous solution of sodium hydroxide for ASG and SG removal or the solution of phospholipase Al for the removal of phosphatides) and the mixture is pumped at a proper pressure in the device's passage wherein flow pressure alternates in the designed mode, and, therefore, cavitation features are created in the mixture.
- the cavitation temporarily separates the high- boiling constituents of oil from the entrapped gases, water vapor and the vapors of low-boiling compounds that can be found in cavitation bubbles. The implosion of these bubbles thoroughly mixes the oil and water, increasing the contact surface area of the two immiscible liquids.
- ASG and SG are high- boiling compounds, they are likely to play a role as the nuclei of bubbles and, thus, are subjected to the full impact of the implosions.
- the mixture loses cavitation features in the end chamber of the cavitation apparatus, and the purified oil and impurity-enriched layer are separated via gravitational settling, static decantation, centrifugation, filtration, distillation, freezing, absorption or other procedure or combination thereof.
- the purification of oils with the flow-through hydrodynamic cavitation can be carried out by using water with no agent added or be followed by mechanical agitation to complete the enzymatic reactions.
- the separated phytosterol-containing residue varies in appearance and volume, depending on the temperature, agent, the initial levels of SG and ASG in the oil, the water-to-oil ratio, the inlet pressure of the cavitation apparatus, the separation procedure and other conditions.
- sodium hydroxide With sodium hydroxide, the separation via centrifuging may resu lt in the formation of three layers. Diluted phosphoric, citric and other acids split ether bond liberating free sterols.
- the hydrodynamic cavitation-assisted purification of oil from ASG and SG provides vigorous mixing and an extremely large water/oil interface, requires only a relatively small amount of agent and can be easily scaled up to accommodate high throughput.
- the cavitation-assisted purification can be conducted at ambient temperature or at a temperature below the ambient temperature, which prevents unsaturated fatty acid from deterioration and saves energy. Under optimized cavitation conditions no significant degradation or deactivation of phospholipases or LAT is observed, which guarantees the expected outcome of enzymatic refining.
- the present invention is directed to a process to remove impurities from triacylglycerol oil.
- the process begins with mixing the oil and a fluidic agent to form a fluidic mixture having an oil phase and a water phase.
- This fluidic mixture is then pumped through a single- or multi-stage, flow-through hydrodynamic cavitation apparatus.
- hydrodynamic cavitation is created in the fluidic mixture by pumping the fluidic mixture at a pre ⁇ determined inlet pump pressure.
- the hydrodynamic cavitation is maintained in the flu idic mixture for a pre-determined period of time.
- the impurities are moved from the oil phase to the water phase. Finally, the water phase containing the impurities is separated from the oil phase.
- the oil can include oil, fat, tallow or grease derived from a wild type, mutated or genetically altered unicellular or
- the oil may be crude, refined, pressed, extracted, filtrated, or dewatered. In addition, the oil may be liquefied prior to performing the mixing step.
- the oil may also be a multi ⁇ phase blend of immiscible liquids, solutes, acids, bases, salts, or gasses comprising a dispersion, an emulsion, a suspension, a melted solid, a gas in a supercritical condition or a mixture thereof.
- the flow-through hydrodynamic cavitation apparatus preferably comprises a high-energy, jet collision hydrodynamic cavitation apparatus or a spinning, rotor-stator hydrodynamic cavitation apparatus.
- P v is the vapor pressure of the fluidic mixture
- p is the density of the fluidic mixture
- V is the velocity of the fluidic mixture at the constriction.
- the separating step may be performed by absorption
- the maintaining step may comprise the step of repeating the pumping and creating steps one or more times in one or more hydrodynamic cavitation apparatuses.
- the mixing step may include diluting the oil with an organic solvent.
- the process may also include cavitating the oil prior to performing the mixing step.
- the fluidic mixture may be heated or cooled prior to performing the pumping step.
- Ammonia gas, nitrogen, carbon dioxide or a mixture thereof may be introduced to the fluidic mixture before or during the pumping, creating and/or maintaining steps.
- the oil is preferably degassed prior to performing the pumping, creating and/or maintaining steps.
- polytetrafluoroethylene, nanodiamonds, nanotubes, or combinations thereof may be immobilized onto inner walls of the hydrodynamic cavitation apparatus or onto a removable insert configured for insertion into the hydrodynamic cavitation apparatus.
- a selective membrane and/or bleaching earth may be placed in an end chamber of the hydrodynamic cavitation apparatus or in a chamber located downstream of the hydrodynamic cavitation apparatus.
- the fluidic mixture may be subjected to acoustic cavitation during the inventive process.
- the fluidic mixture may be subjected to an external electric and/or magnetic field to enhance hydrodynamic cavitation- assisted purification.
- the impurities comprise phytosterols, sterol glucosides and/or acylated sterol glucosides.
- the fluidic agent is water comprising 0.1 -1 0% v/v of the fluidic mixture.
- the water is preferably distilled, de-ionized, reverse osmosis- purified, soft water or otherwise conditioned.
- the fluidic agent may also comprise a solution of an alkali hydroxide comprising sodium hydroxide or potassium hydroxide, an inorganic base, an organic base or a mixture thereof.
- the fluidic agent may comprise a solution of phosphoric acid, citric acid, acetic acid or a mixture thereof.
- the separating step as it relates to phytosterol impurities, may be carried out contemporaneously with the maintaining step.
- the separating step as it relates to sterol glucosides, acylated sterol glucosides and/or derivative- enriched concentrates of the same, may comprise the steps of: liquefying the separated sterol glucosides, acylated sterol glucosides and/or derivative- enriched concentrates thereof by preheating and/or treating the same with solvents and/or liquefying agents; adding enzymes or chemical agents to the liquefied sterol glucosides, acylated sterol glucosides and/or derivative- enriched concentrates thereof; subjecting the liquefied sterol glucosides, acylated sterol glucosides and /or derivative-enriched concentrates thereof combined with enzymes or chemical agents to flow-through hydrodynamic cavitation; and releasing entrapped oil in the liquefie
- the impu rities comprise phosphatides and the fluidic agent comprises water and an enzyme.
- the enzyme may be kosher.
- the enzyme may comprise a phospholipase, a lipid acyltransferase or a mixture thereof.
- the phospholipase may be a wild type, mutated or recombinant bacterial, yeast, plant or animal phospholipase A, phospholipase Al , phospholipase A2 , phospholipase B, lysophospholipase, phospholipase C, phospholipase D, phosphodiesterase, lipid acyltransferase, phosphodiesterase or mixture thereof.
- the oil may be mixed with water and the mixture is subjected to hydrodynamic cavitation followed by the addition of the enzyme comprising phospolipase, lipid acyltransferase or mixture thereof.
- the enzyme is
- the fluidic mixture is preferably heated or cooled to a temperature in the range of 40-60 °C for optimal enzyme activity.
- the process may further comprise the steps of: reacting the phosphatides in the fluidic mixture with the enzyme; agitating the fluidic mixture for a pre-determined period of time to allow completion of the phosphatide reaction; and stopping the phosphatide reaction.
- the phosphatide reaction may be stopped by heating; changing the pH; applying an inhibitor, protease or chelating agent that forms a complex with the enzyme's co-factor; carrying out high-shear mixing; ultrasonic cavitation; and/or subjecting to hydrodynamic cavitation.
- the separating step comprises the step of removing the reacted phosphatides.
- the reacted phosphatides may be removed by absorption, centrifugation, decantation, extraction, filtration, freezing, membrane filtration, or sedimentation.
- the separating step as it relates to the removed
- phosphatides may further comprise the steps of: liquefying the removed phosphatides by preheating the removed phosphatides, and/or adding solvents and liquefying agents to the removed phosphatides; subjecting the liquefied phosphatides to flow-through hydrodynamic cavitation; and releasing entrapped neutral oils and liberating diacylglycerols and fatty acids in the liquefied phosphatides.
- the separating step may further comprise the steps of: liquefying the removed phosphatides by preheating the removed phosphatides, and /or adding solvents and liquefying agents to the removed phosphatides; adding releasing agents and/or lipid acyltransferase, lipase, phospholipase or a mixture thereof to the liquefied phosphatides; releasing entrapped oils in the liquefied phosphatides.
- the present invention is also directed to a method of generating cavitation in a flow mixture of oil and agent resulting in the production of oil refined of ASG, SG and phosphorus. This goal is achieved through the design of the cavitation apparatuses aimed to expedite purification followed by
- the method comprises feeding liquid oil and agent solution or a mixture thereof into the flow-through hydrodynamic single- or multistage cavitation apparatus with a pump and controlling cavitation by varying the inlet pump pressure, and continuing the application of such treatment for a period of time sufficient to obtain the refined oil.
- oil includes, but is not limited to homogeneous or heterogeneous triacylglycerol oil, fat, tallow and grease existing in a liquid phase prior to cavitation, produced by wild type, mutated or genetically engineered bacteria, yeast, algae, plant(s), animals, bird, fish and other prokaryotes or eukaryotes, a two-phase or a multi-phase system comprised of oil, water and/or other immiscible liquids, solution of salts, acids, bases, enzymes, gases and/or other solutes, dispersions, emulsions,
- the objects of the present invention are achieved by feeding a mixture of oil and agent into a hydrodynamic cavitation apparatus to carry out the conversion of impurities and the extraction of the corresponding products with a water phase.
- Hydrodynamic cavitation involves the formation of vapor bubbles of volatile compounds within the mixture's flow accelerated to a proper velocity with a pump. The phenomenon is called cavitation, because cavities form when the flow pressure is reduced to the vapor pressure of volatile compou nds in the fluid. The bubbles expand and collapse, reaching a region of higher pressure. The implosion causes a localized increase in the pressure and temperature and intense shearing forces, resulting in thorough mixing and the acceleration of reaction rates.
- FIGURE 1 is a perspective view a preferred embodiment of the present multi-stage cavitation device.
- FIGURE 2 is a cross-sectional view taken along line 2-2 of FIG. 1 .
- FIGURE 3 is a cross-sectional view of the turbulizer disk taken along line 3-3 of FIG. 2.
- FIGURE 4 is a cross-sectional view of the radial mu lti-jet nozzle taken along lines 4-4 of FIG. 2.
- FIGURE 5 is a cross-sectional view of the cylindrical body taken along lines 5-5 of FIG. 2.
- FIGURE 6 is a side view of the cylindrical body.
- FIGURE 7 is a close-up view of the front interior working chamber and toroidal vortex chamber illustrating fluid flow.
- FIGURE 8 is a close-up view of the back interior working chamber and toroidal vortex chamber illustrating fluid flow.
- FIGURE 9 is a cross-sectional view of various forms of the hemi ⁇ spherical body.
- FIGURE 1 0 is a cross-sectional view of another preferred embodiment
- FIGURE 1 1 is a cross-sectional view taken along line 1 1 - 1 1 of FIG. 1 0.
- a method for the creation of cavitation in an oil-water flow resulting in localized spots of increased pressure, heat and vigorous mixing to refine oil uses a flow-through hydrodynamic cavitation apparatus to carry out ASG, SG and /or phospholipid removal from oil.
- a preferred flow-through cavitation apparatus should be fabricated of inert material, for example stainless steel.
- the inner surface can be coated with oxides, nitrides, ceramics, plastics, polytetrafluoroethylene (PTFE), nanodiamonds, nanotubes, and other suitable compounds, materials, composites, particles, nanoparticles and combination thereof.
- PTFE polytetrafluoroethylene
- the apparatus can be optimized via hardening, anodizing and other technologies.
- agents are
- the cavitation apparatus can be provided with a filter, selective membrane or absorbant to afford even better removal of impurities.
- the flow-through cavitation device depicted in FIGS.l and 2 is comprised of a steel housing 22, which is attached to inlet 24 and outlet 26 pipes for direct connection to an industrial pipeline (not shown).
- the device 20 preferably has a mirrored symmetry such that from the inlet 24 to a mid-point 27 is repeated in reverse from the mid-point 27 to an outlet 26. The following description will follow the mirrored symmetry and describe from both the inlet 24 and outlet 26 toward the mid-point 27 simultaneously.
- front and end disk multi-jet nozzles 28, 30 serve as the front and back walls of exterior working chambers 32 , 34 and are located behind the inlet pipe 24 and in front of the outlet pipe 26.
- the multi-jet nozzles 28, 30 are equipped with constricting and expanding channels 36 that are distributed uniformly over the su rfaces of the disks that are the multi-jet nozzles 28, 30.
- the working chambers 32 , 34 are comprised of radial cones 38, 44 and central guide cones 42, 43, which are attached to radial multi-jet nozzles 44, 46.
- the radial multi-jet nozzles 44, 46 feature both constricting and expanding channels 48.
- the channels 48 are spread evenly over the radial perimeter surface of the nozzles 44, 46, which direct the flow to interior working chambers 50, 52.
- the cross-section of the flow guides 54, 56 generally has a S-shape configuration.
- a hemi-spherical body 58, 60 with a top niche 62 is mounted in the working chambers 50, 52 against the multi-jet nozzle 44, 46.
- the turbulizer disk 64, 66 (FIG. 3) with cu rved guides 68 and central hole 69 is located behind the guides 54, 56 in vortex chamber 70.
- the vortex chamber 70 is formed of the inner wall of the housing 22 and a cylindrical body disposed in the center. The vortex chamber 70 directs the flow from the hole 69 of the front disk 64.
- FIGURE 3 is a diagram that shows disks 64, 66 with cu rved gu ides 68 and central holes 69.
- An interior side of the radial multi-jet nozzles 44, 46 is depicted in FIG. 4.
- the channels 48 let out into the working chambers 50, 52 housing the hemi-spherical body 58, 60 with the top niche 62.
- FIG. 5 shows a cross-sectional view of the cylindrical body 72, which is provided with the superficial perimeter guides 74 that serve as the channels for fluid flow.
- FIG. 6 is a drawing of a preferred embodiment for the guides 74 of the cylindrical body 72.
- FIGS. 7 and 8 depict the junction between the working chambers 50, 52 and the disks 64, 66 and illustrate fluid flow.
- At the junction between the guides 54, 56 and the disks 64, 66 are toroidal vortex chambers 76 which are connected to the holes 69 and working chambers 50, 52.
- FIG. 9 is a simplified schematic illustration showing various embodiments for the niche 62 : a hemi ⁇ sphere, a toroid, and a parabola.
- the present flow-through cavitation device (FIG. 2) operates as follows. Fluid, for example, a rough disperse emulsion, is pumped in the inlet pipe 24. The fluid moves to the multi-jet nozzle 28 and passes through its channels 36, which have both constrictions and expansions. Flowing through the channels 36 causes the formation of vortices, detached flows and
- cavitation Particles of the emulsion become subjected to shear forces, and emulsion quality improves.
- cavitation bubbles reach the working chamber 32 they pulsate and collapse.
- the bubble implosion resu lts in increased pressure and temperature and formation of local jets that act on the emulsion particles, further improving the emulsion homogeny.
- the flow moves in a converging cone formed by the radial cone 38 and the central cone 42 that is mounted on the radial multi-jet nozzle 44. The flow is accelerated as it passes through the converging cone and then enters the channels 48, which possess both constrictions and expansions to generate vortices, detached flows and cavitation in the fluid flow.
- the end of the flow guide 54 is shaped as a constricting nozzle.
- the hole 69 in the disk 64 is shaped as an expanding nozzle in the beginning and a toroidal resonator 76 is positioned in the constrict location. [Para 61 ] When the fluid flows along the place of the attachment of the flow guide 54 to the disk 64 it enters the ring grooves or toroidal resonator 76.
- the working principle of the toroidal resonator 76 is based on a high sensitivity of an symmetric flow to a side pressure.
- the fluid is forced off the toroidal resonator 76 by discrete portions, which generates dynamic pulsations, vortices and cavitation.
- the frequency of a toroidal resonator depends on its diameter (Agranat et a/., 1 987). [ Para 62 ]
- the flow moves out of the working chamber 50, accelerating due to passing through the hole 69 in the front disk 64 and then enters channels located between the guides 68 on the front disk 64 in the vortex chamber 70.
- the guides 74 are provided on the cylinder 72 surface to direct the flow into channels 78 and sustain the spiral flow state (FIG. 5).
- the vortex chamber 70 cavitation bubbles are acted upon by centrifugal and Coriolis forces. As a result, the fluidic pressure rises and the bubbles collapse.
- the number of guides 74 that may be intersected by one line is limited due to the requirement that the total area of the guide channels 78 be equal to the area of the central hole 69 of the disks 64, 66.
- the total cross-sectional area of the channels 78 can be calculated by multiplying the number of channels by the height and width. [ Para 64] After passing through the channels 78 the fluid flow moves over the surface of the vortex guides 68 and enters the hole 69 in the rear disk 66. This directs the flow along the central axis of the device 20.
- the pulsation frequency and the cavitation zone shape depend on the fluid properties, flow rate and the niche shape. The preferred embodiments for the niche 62 are described above.
- the fluidic flow passes through the region of the toroidal resonator 76 and niche 62 and enters the working chamber 52 bou nded by the rear guide 56 inner wall and the rear semi-spherical body 60, which direct the flow from the center to the perimeter.
- the cavities detached from the toroidal flow region implode in the working chamber 52.
- the fluid flow After passing the working chamber 52 , the fluid flow enters channels 48 of the rear radial multi-jet nozzle 46 provided with the constrictions and the expansions. This generates vortices, detached flow jets and cavitation.
- the fluid flow moves in the working chamber 34, the flow velocity decreases, the pressure goes up, and pulsation and implosion of the bubbles take place.
- the flow passes through the constrictions and the expansions 36 of the rear multi-jet nozzle 30 followed by generation of vortices, detached flow jets and cavitation.
- the particles of emulsion that undergo the cavitation process are reduced in size and their surfaces are modified.
- the cavitation bubbles pulse and implode within the working chamber 34, leading to shear force and local jet formation. Then the fluid flow exits the cavitation device through the outlet pipe 26.
- This preferred embodiment of the device provides at least eleven cavitation zones: (1 ) the front multi-jet nozzle 28; (2) the front, radial multi-jet nozzle 44; (3) the top niche 62 in the front hemi-spherical body 58; (4) the front toroidal vortex chamber 76; (5) the hole 69 and curved guides 68 of the front disk 64; (6) the vortex chamber 70; (7) the hole 69 and curved guides 68 of the rear disk 66; (8) the rear toroidal vortex chamber 76; (9) the top niche 62 in the rear hemi-spherical body 60; (1 0) the rear, radial multi-jet nozzle 46; and (1 1 ) the rear-end multi-jet nozzle 30.
- the device design allows for two, four, six or even more mirror-symmetric cavitation regions. The plane of mirror symmetry goes through the mid-point 27 of the vortex chamber 70 located between the disks 64, 66.
- the device 20 can be connected to a pump at either end and is especially suitable for technological applications with a demand for reversing flow direction.
- the device 20 can be incorporated in a pipeline without any risk of confusing inlet with outlet.
- the main benefit of the present flow-through cavitation device 1 0 is the interface of the vortex and cavitation generating zones with the higher-pressure working chambers for the cavitation bubbles' implosion.
- FIGURE 1 0 is a drawing that shows an alternate embodiment for a flow-through multi-stage cavitation system 80 that provides as many as ten zones 82 for generation and collapse of cavitation bubbles and is comprised of ten identical working chambers 84 and ten multi-jet nozzles 86 that differ in respect to the cross-sectional passage areas created by their channels 88.
- the flow rate is the same within the identical, sequentially located multi-jet nozzle channels 88.
- the cavities implode and the fluid's temperature rises.
- the increased temperature and amplification of the nuclei facilitate the onset of cavitation events in downstream cavitation zones. Therefore, the same cavitation number and the same cavitation bubble concentration can be achieved within downstream zones with the lower flow velocity inside the nozzle channels 88.
- Du ring multi-stage fluid processing the hydraulic resistance is reduced by meeting the following condition:
- This helps save energy required for pumping a fluid flow through the multi-zone cavitation system.
- the multi-jet nozzle 86 it is necessary to place the channels 88 for fluid passage as close as possible.
- the number of the channels 88 of the multi-jet nozzle 86 is limited by the ratio of the total area of the largest cross-sectional openings of the channels (Sd) to the surface area of k
- the composition of the cavitation bubble vapors is not uniform.
- the cavities are enriched with the vapors of the compound(s) that are most volatile under the given conditions.
- the bubble implosion releases energy that drives chemical reactions and/or warms up the fluid.
- the processed matter contains the products of these reactions, the newly formed chemical compounds.
- the size of the cavities depends on the nature of the fluid under the treatment, the engineering design of the cavitation device and other conditions, such as the velocity of a flow sustained by a pump. In practice, the pump pressure is increased until a proper intensity of the cavitation field is achieved.
- the inlet pressure governs the outcome of the chemical reactions.
- a lower cavitation nu mber implies a high degree of cavitation.
- the preferred embodiment of the present invention optimizes the cavitation to perform uniform alteration of fluids by applying the most su itable pump pressure. If too much energy is applied or the treatment time is too long, then the processing cost goes up. By applying hydrodynamic cavitation at a pump pressure designed to generate cavitation and chemical conversion evenly throughout the fluid, the change in physical and chemical properties takes place and the desirable outcome is obtained.
- the devices depicted in the FIGs. 1 - 1 1 are used for carrying into effect the method, according to the present invention.
- the fluid can be treated either continuously or periodically, by passing through the multi-stage devices 20, 80 comprised of the vortices and bubbles' generating zones, as well as the higher-pressu re working chambers.
- the systems can be placed anywhere around a production site, oil refining colu mn or any other facility.
- the device may be fixed in position or movable. Placement of one device may be combined with the placement of another device in series or parallel. In practice, it is necessary to consider the cost of the device, its production capacity and operation and maintenance expenses.
- an operator of the cavitation device is not required to wear the high performance safety products for hearing protection, such as earmuffs or earplugs, as it would be in a case of a high frequency acoustic cavitation.
- embodiment of the present invention is achieved with a pump pressure selected from the range of approximately 50-5,000 psi.
- the optimal pressure produces a sufficient amount of cavities to achieve a high degree of treatment.
- different fluids require different energies achieved through cavitation in order for their alteration to proceed. Therefore, the range of 50-5,000 psi is in no way limited for using the present invention. Energy released because of bubble implosion during a flow-through
- hydrodynamic cavitation activates molecules forcing them to react and form new compounds.
- the result is an upgraded product of higher commercial value whose components are easier to handle.
- the oil purification from phosphorus catalyzed by lipid acyltransferase can be coincidental or conducted after the acid hydrolysis of ASGs and SGs to liberate steryl esters of fatty acids.
- the bubbles generated during such treatment are comprised of the vapors of the compounds that are volatile under the set conditions, including those to be removed during downstream purification steps. Energy released due to the implosion of cavitation bubbles disrupts the structure of water and oil mixing them
- the ultrafine dispersions produced by using a flow-through cavitation apparatus are relatively stable and do not coalesce rapidly. They provide very large oil/water contact surface area which can be preserved through the subsequent conventional mechanical agitation.
- a hydrodynamic cavitation apparatus can be placed at the oil production site, storage facility or biodiesel plant. Yet another possibility exists, in which the apparatus is movable.
- the size of the cavitatation bubbles depends on the fluidic mixture properties, design of the cavitation device, the flow velocity sustained by a pump, temperature and other conditions. In practice, the pump pressure is increased until the required level of cavitation is achieved. Inlet pressure affects the size, concentration and composition of the bubbles and, thus, the
- composition of the processed oil Preferably the cavitation is optimized to efficiently purify oil by applying the most suitable pressure.
- the desirable outcome is obtained by generating hydrodynamic cavitation with an optimal cavitation number and density consistent throughout the flow.
- the flow-through hydrodynamic apparatuses are designed for the express purification of large volumes of oil.
- the apparatuses can be placed sequentially or assembled in skid systems to scale up the capacity.
- the placement of one device may be combined with the placement of another one.
- the hydrodynamic cavitation-assisted treatment of oil can be repeated as many times as needed to achieve the desired result.
- the implosion of cavities results in the formation of deformed micro bubbles, which become nuclei after moving into the reduced pressure zone, enhancing the cavitation field density and lowering the cavitation threshold.
- This makes the multi-stage cavitation apparatus especially suitable for high-quality oil refining.
- the apparatuses can be easily mounted and transported, making them suitable for field and remote locations.
- the mixture was matured at 80°C for twenty minutes, cooled to 50-55°C and 1 00 ppm phosphorylase Al Lecitase Ultra in 1 % v/v water was added followed by a second single-pass flow-through hydrodynamic cavitation treatment of the resultant mixture by using three 1 1 -stage apparatuses placed in series and operated at an inlet pump pressure of 800 psi.
- the mixture was centrifuged after a fast mechanical agitation at 50-55°C for one hour.
- hydrodynamic cavitation-assisted enzymatic degumming contained 2.99 ppm P, 1 .49 ppm Ca, 0.76 ppm Mg and 1 .06% FFA confirming the higher efficiency of the combined treatment even with the citric acid and NaOH addition steps being omitted.
- the refined oil that was subjected to the cavitation after the addition of 1 00 ppm phospholipase contained 1 .06% FFA, which is substantially higher when compared to 0.70% FFA obtained by conventional processing with 1 00 ppm enzyme. It should be noted that neither citric acid nor NaOH was used in the last treatment.
- the hydrodynamic cavitation not only significantly increases the oil yield but eliminates the need for using harsh chemicals.
- the invention provides a novel method for removing phospholipase- and LAT- hydrolyzable phosphatides from oil and increases the yield without making major changes to the conventional processing conditions.
- the oil refined by this method contained 3.1 5 ppm P, 0.38 ppm Ca, 0.26 ppm Mg and only 0.51 % FFA.
- soybean oil contained 650.00 ppm P, 46.40 ppm Ca, 64.70 ppm Mg and 0.80% FFA and the mixture was subjected to a single-pass flow-through hydrodynamic cavitation treatment using three 1 1 -stage apparatuses that were placed in series and operated at an inlet pump pressure of 800 psi followed by agitation at 80°C for thirty minutes and the addition of 1 .56% v/v water.
- the mixture was subjected again to a single-pass flow-through hydrodynamic cavitation treatment by using three 1 1 -stage apparatuses placed in series and operated at an inlet pump pressure of 800 psi and centrifuged after maturation at 80°C for twenty minutes.
- the oil refined by this method contained 6.80 ppm P, 0.73 ppm Ca, 0.56 ppm Mg and 0.53% FFA. Thus, no increase in yield was observed and the phosphorus concentrations were higher than those obtained with the cavitation and enzyme combined treatment.
- the preferred embodiment the cavitation system that is especially suitable for the removal of ASGs and SGs from triacylglycerol oil using the process described herein is three 1 1 -stage devices that are placed in series and operated at a pump pressure of 800- 1 ,200 psi.
- the temperature of the oil and agent solution is in the range of 1 0-90 ° C and the fluidic agent comprises a 0.1 -5% v/v percentage solution.
- triacylglycerol oil using the process described herein is three 1 1 -stage devices that are placed in series and operated at an inlet pump pressure of 800- 1 ,200 psi.
- the temperature of oil and enzyme solution is in the range of 40-60 ° C and the enzyme containing water phase comprises 0.1 - 5% v/v percentage solution.
- Hydrodynamic cavitation is the formation of vapor-filled bubbles in the flow of fluid followed by the collapse of these bubbles in a high-pressure zone.
- the process is performed as follows: the fluid is fed into the inlet passage cavitation apparatus with a pump. In localized zones, the flow velocity increases, causing the fluid pressure to drop in accordance with Bernoulli's law. This pressure drop leads to the formation of bubbles filled with the vapors of compounds that boil under the given conditions, i.e., the fluid pressure drops below the vapor pressure.
- cavitation field is controlled by using a properly designed device, inlet pressure, temperature and composition of the fluid medium.
- the high viscosity of oil can be lowered by adding solvents or surfactants or mixtures thereof, by heating, applying external electric or magnetic fields or any combination thereof.
- the preferred embodiments of the present invention apply optimized levels of both pressure and heat via a controlled hydrodynamic cavitation.
- the process is independent of external conditions and provides a highly effective method of oil purification through the removal of phosphorus-containing compounds, ASG and SG.
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Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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CA2809236A CA2809236C (en) | 2010-09-16 | 2010-09-17 | Process to remove impurities from triacylglycerol oil |
SG2013006986A SG187241A1 (en) | 2010-09-16 | 2010-09-17 | Process to remove impurities from triacylglycerol oil |
MX2013002287A MX343518B (en) | 2010-09-16 | 2010-09-17 | Process to remove impurities from triacylglycerol oil. |
BR112013003542-0A BR112013003542B1 (en) | 2010-09-16 | 2010-09-17 | PROCESS FOR REMOVING IMPURS FROM OIL CONTAINING TRIACYLGLYCEROL |
EP10857392.4A EP2616156B1 (en) | 2010-09-16 | 2010-09-17 | Process to remove impurities from triacylglycerol oil |
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US12/883,328 | 2010-09-16 | ||
US12/883,328 US8945644B2 (en) | 2009-06-15 | 2010-09-16 | Process to remove impurities from triacylglycerol oil |
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WO2012036695A1 true WO2012036695A1 (en) | 2012-03-22 |
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PCT/US2010/049284 WO2012036695A1 (en) | 2010-09-16 | 2010-09-17 | Process to remove impurities from triacylglycerol oil |
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EP (1) | EP2616156B1 (en) |
AR (1) | AR083000A1 (en) |
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Also Published As
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CA2809236C (en) | 2017-02-07 |
AR083000A1 (en) | 2013-01-23 |
EP2616156B1 (en) | 2018-10-10 |
MY164311A (en) | 2017-12-15 |
MX2013002287A (en) | 2013-10-28 |
EP2616156A1 (en) | 2013-07-24 |
EP2616156A4 (en) | 2014-03-05 |
MX343518B (en) | 2016-11-07 |
CA2809236A1 (en) | 2012-03-22 |
US8945644B2 (en) | 2015-02-03 |
US20110003370A1 (en) | 2011-01-06 |
BR112013003542B1 (en) | 2019-09-24 |
BR112013003542A2 (en) | 2016-06-28 |
SG187241A1 (en) | 2013-03-28 |
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