PROCESS FOR REMOVING IMPURS FROM OIL CONTAINING TRIACYLGLYCEROL

专利摘要:
process for removing impurities from triacylglycerol containing oil. The present invention is directed to a process for removing impurities from triacylglycerol-containing oil, including mixing the oil and a fluidic agent, by pumping the mixture through a through-flow hydrodynamic cavitation equipment with a pump at a predetermined pressure. hydrodynamic cavitation in the mixture, maintain hydrodynamic cavitation for a predetermined period of time, move the oil impurities with the oil fluid agent. Impurities may include phytosterols, sterol glycosides, acylated sterol glycosides, in which case the fluidic agent is water, an alkali metal hydroxide, an inorganic base, an organic base, phosphoric acid, citric acid, acetic acid or a mixture. of the same. impurities may also include phosphatides, in which case the fluidic agent comprises water and an enzyme such as phospholipase, lipid acyltransferase or a mixture thereof.
公开号:BR112013003542B1
申请号:R112013003542-0
申请日:2010-09-17
公开日:2019-09-24
发明作者:Roman Gordon；Igor Gorodnitsky；Varvara Grichko
申请人:Cavitation Technologies, Inc.；
IPC主号:

专利说明:

PROCESS FOR REMOVING IMPURITIES FROM OIL CONTAINING
TRIACILGLICEROL
Background of the Invention [0001] The invention is generally related to methods of refining triacylglycerol and is based on the use of hydrodynamic cavitation of the through-flow. The invention uses the energy released when imploding cavitation bubbles to purify the oils and improve the commercial value of the collected by-products. More particularly, the present invention relates to the lowering of levels of sterol glycosides (GEs) and of acylated sterol glycosides (GEAs) and enzyme hydrolysable phospholipids that can be followed by the production of biodiesel through transesterification. The residual concentrates obtained from the present invention can be used as food additives for lowering blood cholesterol, in the production of pharmaceutical products, or for other purposes. The invention finds application in biofuels, chemical, food, pharmaceutical and other industries.
[0002] Crude vegetable oils are mainly composed of triacylglycerols (TAG) and contain impurities such as phospholipids (phosphatides), free fatty acids (AGL), unpleasant compounds, carotenes, chlorophyll and other pigments, waxes, aluminum, calcium, copper , iron, magnesium and other metals and phytosterols. Impurities negatively affect the quality of oil and oil products and must be removed before use.
[0003] Crude oil can be produced by using solvents or by pressing the seeds or by heating or
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2/44 without heating. Hot pressing provides the best yield, but results in oil deterioration and the accumulation of non-hydratable phosphatides (FNH), for example, calcium salts and magnesium salts of phosphatidic acid (AF) and phosphatidyl ethanolamine (FE), due to the action of enzymes that are active at 57-85 ° C. FE can be hydrated if it has a liquid charge. The AF has a glycerol structural chain usually with a saturated fatty acid, an unsaturated acid, and a phosphate group attached to carbon 1, 2 and 3, correspondingly. To ensure high oil quality, oil producers avoid exposing seeds to temperatures around 55 ° C-80 ° C and treat them with steam at around 150 ° C to deactivate phospholipases and lower the salt level. of AF by 25-50% (Cmolik Pokorny, 2000; Gunstone et al., 2007).
[0004] The methods of refining the oil depend on the type of oil and usually include degumming, whitening and deodorization. Degumming is the removal of the phosphorus present in the form of hydratable and non-hydratable phosphatides. Degumming provides refined oil with a phosphorus concentration greater than 200 ppm and can be followed by alkaline refining, whitening and deodorization or by acid degumming, dry degumming and physical refining or by enzymatic degumming (Clausen, 2001), whitening and physical refining . There are numerous variations in oil refining methods, depending on the quality of the oil and other conditions. In addition, the oil can be hydrogenated to obtain a stable product.
[0005] Each refining step results in some oil loss (Racicot and Handel, 1982; Cvengros, 1995; Cmolik and Pokorny, 2000). Oil yield can be increased by using
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3/44 enzymes instead of chemical reagents. For example, phospholipase C hydrolyzes phosphatidylcholine (FC), releasing the water-soluble choline phosphate ester and diacylglycerol (DAG). The conversion of phospholipids to DAG increases the oil yield, due to the accumulation of DAG in the oil phase and minimal capture of neutral oil in the gums consisting of hydrated lecithin. FC is converted by phospholipases A1 and A2 to lysophosphatidylcholine and AGL. Lipid-acetyltransferase (LAT) catalyzes the decomposition of FC to lysophosphatidylcholine and AGL, which can form esters with the free sterols present in the oil. Therefore, EF is converted by phospholipases A1 and A2 and LAT to lysophosphatidylethanolamine (LPE) and AGL or sterile esters. LPE is a plant growth regulator that can be isolated as a valuable by-product. Phospholipase C catalyzes the hydrolysis of EF to ethanolamine-phosphate and DAG. Phosphatidylinositol (PI) can be hydrated over a wide pH range, being converted by phospholipases A1 and A2 and LAT to lysophosphatidylinositol. However, PI is not hydrolyzed by phospholipase C. Phospholipases A1 and A2 and LAT convert the alkaline salts of AF to lysophosphatidic acid salts. Alkaline salts of AF are not influenced by phospholipase C.
[0006] Since phospholipases A1 and A2 and LAT are soluble in water, they act on phosphatides located at the oil / water interface. As a consequence, enzymatic degumming requires long-term, high-shear agitation to sustain the large oil / water surface area and high mass transfer rates and curbs itself with the coalescence of the water-in-oil dispersion. Oil producers do not use emulsifiers to stabilize dispersions in
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4/44 industrial scale due to its high cost.
[0007] GEs are derived from sterol, in which a carbohydrate unit (arabinose, glucose, etc.), is linked to the hydroxyl group of campesterol, brassicasterol, diidrositosterol, sitosterol, stigmasterol, or other sterols with an ether bond. In GEAs, which are very soluble in vegetable oils, the 6-carbon carbohydrate is esterified with a long-chain fatty acid. Phytosterols are abundant in plants and can be easily isolated. (Sugawara and Miyazawa, 1999). They are mediators of cellular stress and have anti-cancer properties. The GEs have been noted for having a neurotoxic effect and are a potential causative factor in neuronomotological pathology previously associated with the consumption of 'cycad' and complex dementia due to amyotrophic lateral sclerosis-parkinsonism. (Khabazian et al, 2002; Ly et al, 2006; Bradford and Awad, 2007; Tabata et al, 2008). GEs are not soluble in biodiesel, or diesel and therefore cannot be forced through a diesel engine filter, which results in a clogged fuel system. GE crystallizes at around 35 ppm at room temperature leading to the formation of turbidity in biodiesel. GEs and GEAs melt at about 240 and 250-300 ° C and promote the crystallization of other compounds present in biodiesel at cold temperatures by becoming the sowing crystals for large agglomerates. Thus, it is necessary to reduce the content of GEA and GE contained in the oil supply before the production of biodiesel.
[0008] The level of GEA and GE in biodiesel drops as a result of the storage of biodiesel due to sedimentation of the agglomerates. GEA can be converted to GE during
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5/44 base-catalyzed transesterification, for example, in an alkali-catalyzed methanolysis. (Lepage, 1964). The acid hydrolysis of both GE and GEA releases the corresponding free sterols, which are not soluble in biodiesel. LAT catalyzes the conversion of free sterols to sterile esters.
[0009] Crude palm, soy, corn and sunflower oils contain up to 2500, 2300, 500 and 300 ppm GEs, respectively. The GE content in palm and soy biodiesel is 55-275 and 0158 ppm, correspondingly. (Van Hoed et al., 2008). To assess the level of contamination and filterability of biodiesel, ASTM D2068-08 “Standard Test Method for Determining Filter Blocking Tendency” and ASTM D6751-09a “Standard Specification for Biodiesel fuel Blend Stock (B100) for Middle Deistillate Fuels” are used . The trend value of
Block of Filter (TBF) of biodiesel in Soy with ~ 70 ppm in GE is from about 15 . The value gives TBF for biodiesel filtered in earth filter diatom with ~ 20 ppm from GE is next in 1. The residue sticky retained with the filters in
biodiesel facilities produced with palm or soy oil contain up to 50 and 25% of GE and GEA, correspondingly. GEs exhibit high adsorption capacity for the fatty acid methyl esters that result in their clogging.
(Van Hoed et al., 2008).
[00010] Purifying the oil before biodiesel production reduces both the concentration of phosphorus and phytosterols in the final product. Although GEs can be removed using filtration, absorption or distillation ((Manjula and Subramanian, 2006; BONDIOLI et al., 2008), biodiesel manufacturers are particularly interested in the development of a low cost, high efficiency and productivity method that reduces the
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6/44 levels of phosphorus, GEs and GEAs in oil supplies and that allows the recovery of valuable residual concentrates.
[00011] Most vegetable oils can be purified in accordance with the present invention, including oils of açaí, almond, peanut, avocado, hawthorn, camelina, walnut, canola, cashew, castor, citrus, cocoa butter, coconut, corn , cottonseed, primrose, grape seed, peanut, hazelnut, hemp, jojoba, flax seed, macadamia, Meadowfoam seed, mongongo, mustard, ojon, olive, palm, papaya, peanut, nuts, pine nut, pistachio, seed of poppy, radish, rapeseed, rice bran, saffron, soy, sesame, sunflower, tung and nut oil. The invention is also applicable to algae oil, animal fat, poultry fat, fish fat, tallow and fatty material.
[00012] It is known that the increase in both pressure and tem and the vigorous agitation provided by the cavitation can initiate and / or accelerate chemical reactions and processes. Although extreme conditions can be disadvantageous, the response of an optimized controlled cavitation treatment is always beneficial. Therefore, the improvement in reaction yield through the energy released when the generated cavitation bubbles collapse has a number of applications.
[00013] Cavitation can be by hydrodynamics, acoustics, ultrasound, induced by light irradiation, generated by steam injection, etc. The simultaneous application of the cavitation generating methods improves efficiency (Moulton and Montagens, 1999; Young, 1999; Gogate, 2008; Mahulkar et al., 2008).
[00014] If the fluid flow is directed in a flow-through hydrodynamic cavitation equipment, bubbles filled with
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7/44 vapor will form within the flow due to the drop in hydrolytic pressure. The collapse of the bubbles in a zone of high pressure and low speed causes sharp increases in both pressure and temperature, formation of high speed currents and shock waves and shock waves, vigorous shear forces, and the release of substantial amounts of energy . This process activates atoms, molecules, ions and / or radicals located in the bubbles and in the surrounding liquid, and initiates chemical reactions and processes. The implosion of the bubbles can also result in the emission of light favoring photoreactions and radical generation.
[00015] The cavitation phenomenon is categorized by the cavitation number C _v , defined as: C _v = (P - P _v ) / 0.5 pV2, where P is the pressure downstream of a constriction, Pv is the pressure of fluid vapor, p is the density of the fluid, and V is the velocity of the fluid in the bore. Cavitation starts at Cv = 1, and Cv <1 indicates a high degree of cavitation. The number of cavitation events in a flow unit is another important parameter. (Suslick, 1989; Didenko et al., 1999; Suslick et al, 1999 ;. Young, 1999; Gogate, 2008; Passandideh-Fard and Roohi, 2008 ;. Zhang et al., 2008). Numerous through-flow hydrodynamic equipment is known. See, for example, US Patent. No. 6705396 to Ivannikov et al., U.S. Patent. No. 7338551 to Kozyuk and U.S. Patent No. 7762715 to Gordon et al.
[00016] With energy costs and human health concerns rising rapidly, it is highly desirable to develop low cost and environmentally friendly technology for removing phospholipids, GEs and GEAs from oils. To achieve the highest possible profit margin, it is necessary to decrease energy consumption time and loss of energy.
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8/44 oil during refining. The methods already known do not offer the most efficient technologies for purifying oils in the shortest possible time. As a result, there is a need for an advanced method for the rapid removal of phytosterols and phospholipids from oil, with low energy consumption and cost agents, which results in products with advanced qualities, preferably using through-flow cavitation. The present invention provides such a method while delivering purified oil within a very short processing time. There is no accumulation of waste material harmful to the environment, and the produced waste concentrates are suitable for further processing.
[00017] The invention provides an oil purification method based on the generation of cavitation in a flow of oil contained in at least one chamber of a cavitation equipment, preferably in a number of chambers positioned consecutively. This objective is achieved through the application of cavitation equipment aimed at the rapid purification of oils. According to the present invention, the method comprises feeding a fluid mixture of oil and the agent into the hydrodynamic cavitation device by passing flow using a predefined inlet pressure supported by a pump and applying selected conditions and additional agents, if necessary.
Summary of the Invention [00018] The present invention is directed to the method of processing TAG oil, fat, tallow and fatty material with a single-stage or multistage through-flow hydrodynamic cavitation equipment, including
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9/44 rotor-stator cavitation and high speed (high energy) collision cavitation equipment.
[00019] Hydrodynamic cavitation, including rotor-stator cavitation equipment and high speed (high energy) equipment.
[00020] Hydrodynamic cavitation significantly reduces the level of impurities in the oil, allowing to express high efficiency refining. Treatment begins with the provision of cavitation equipment. Then, the liquid oil is mixed with an agent (for example, the aqueous sodium hydroxide solution for the removal of GEA and GE removal or the phospholipase A1 solution for the removal of phosphatides) and the mixture is pumped at a pressure adequate in the passage of the device in which the flow pressure alternates in the designed mode, and therefore the cavitation characteristics are created in the mixture. Cavitation temporarily separates the high boiling point constituents of oil, trapped gases, water vapor and the vapors of the low boiling compounds that can be found in cavitation bubbles. The implosion of these bubbles makes a complete mixture of oil and water, increasing the area of the contact surface of the two immiscible liquids. Since GEA and GE are compounds with a high boiling point, they are likely to play a role as bubble-forming nuclei and thus are subjected to the full impact of implosions. The mixture loses the characteristics of cavitation in the final chamber of the cavitation equipment, and the purified oil and the layer enriched with impurities are separated by gravitational sedimentation, static decantation, centrifugation, filtration, distillation, freezing, absorption or other procedure or
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10/44 combination of both. In some cases, the purification of oils with hydrodynamic through-flow cavitation can be carried out by using water without any added agent or be followed by mechanical stirring to complete the enzymatic reactions.
[00021] The separated residue containing phytosterol varies in appearance and volume, depending on the temperature, the agent, the initial levels of GE and GEA in the oil, the water-oil ratio, the internal pressure of the cavitation equipment, the separation procedure and other conditions. With sodium hydroxide, separation by centrifugation can result in the formation of three layers. Diluted phosphoric, citric and other acids break the ether bond by releasing free sterols.
[00022] The hydrodynamic cavitation assisted purification of GE and GEA oil provides vigorous mixing and an extremely large water / oil interface, requires only a relatively small amount of agent and can be easily scaled to accommodate high throughput. Cavitation-assisted purification can be conducted at room temperature or below room temperature, which prevents unsaturated fatty acid from deteriorating and saves energy. In optimized cavitation conditions, no significant degradation or deactivation of phospholipases or LAT is observed, which guarantees the expected result of the enzymatic refining.
[00023] It is known that the content of lecithin oil produced by conventional methods is very high, reaching 35%. To release the TAG oil embedded in the gums and increase the oil yield, the isolated gums can be liquefied by dissolving in water, hexane or other solvents using
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11/44 use of increased temperature, suitable reagents and mechanical agitation and processed with the flow-through hydrodynamic cavitation device during the application of enzymes that act on the appropriate phosphatides or agents.
[00024] The present invention is directed to a process for removing impurities from oil containing triacylglycerol. The process begins with mixing the oil and a fluidic agent to form a fluid mixture having an oil phase and an aqueous phase. This fluid mixture is then pumped through a single-stage or multistage through-flow hydrodynamic cavitation equipment. In this equipment, hydrodynamic cavitation is created in the fluid mixture by pumping the fluid mixture at a predetermined pump inlet pressure. The hydrodynamic cavitation is maintained in the fluid mixture for a predetermined period of time. During hydrodynamic cavitation, impurities are moved from the oil phase to the water phase. Finally, the aqueous phase containing the impurities is separated from the oil phase.
[00025] In the present invention, the oil may include oil, tallow, fatty material or fat derived from a wild type, mutant or genetically altered from unicellular or multicellular algae, plants, animals, or mixtures thereof. The oil can be crude, refined, pressed, extracted, filtered or dewatered. In addition, the oil can be liquefied before the mixing step is carried out. The oil may also be a mixture of various phases of immiscible liquids, solutes, acids, bases, salts, or gases comprising a dispersion, an emulsion, a suspension, a molten solid, a gas under supercritical conditions or a mixture of those mentioned.
[00026] Hydrodynamic flow cavitation equipment
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Passing 12/44 preferably comprises a hydrodynamic through-flow cavitation equipment by high energy jet collision or a rotary-stator rotating through flow hydrodynamic cavitation equipment.
[00027] The fluid mixture within at least one region within the hydrodynamic cavitation equipment has a cavitation number less than or equal to 1. Such cavitation number is calculated using the equation: C _v = (P - P _v ) / 0 , 5 pV ² , where C _V is the cavitation number, P is the pressure downstream of a constriction, Pv is the vapor pressure of the fluid mixture, p is the density of the fluid mixture, and V is the speed of the fluid mixture in constriction.
[00028] The separation step can be carried out by absorption, centrifugation, decantation, distillation, extraction, filtration, freezing, decanting, sedimentation, or a combination thereof. The maintenance step may include the step of repeating the steps of repeating the pumping and creating steps one or more times on one or more hydrodynamic cavitation equipment.
[00029] The mixing step may include diluting the oil with an organic solvent. The process may also include cavitating the oil before the mixing step is carried out. The fluid mixture can be heated or cooled before performing the pumping step. Ammonia gas, nitrogen, carbon dioxide or a mixture of them can be introduced into the fluid mixture before or during the pumping, creation and / or maintenance of the stages. The oil is preferably degassed before pumping, creating and / or maintaining the stages.
[00030] Reagents, oxides, nitrides, ceramic materials,
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13/44 plastics, polytetrafluoroethylene, nanodiamonds, nanotubes, or combinations thereof, can be immobilized on the inside walls of the hydrodynamic cavitation equipment or for a removable insert configured for insertion into the hydrodynamic cavitation equipment. A selective membrane and / or whitening earth can be placed in a final chamber of the hydrodynamic cavitation equipment or in a chamber located downstream of the hydrodynamic cavitation equipment.
[00031] The fluid mixture can be subjected to acoustic cavitation during the inventive process. In addition, the fluid mixture can be subjected to an external electric and / or magnetic field to reinforce hydrodynamic-assisted purification.
[00032] In a particularly preferred embodiment, the impurities comprise phytosterols, sterol glycosides and / or sterol acylated glycosides. In this preferred embodiment, the fluidic agent is water which comprises 0.1-10% v / v of the fluid mixture. The water is preferably distilled, deionized, purified by reverse osmosis, soft water or otherwise conditioned. The fluidic agent may also comprise a solution of an alkali metal hydroxide which comprises sodium hydroxide or potassium hydroxide, an inorganic base, an organic base or a mixture of those mentioned. Alternatively, the fluidic agent may comprise a solution of phosphoric acid, citric acid, acetic acid or a mixture of those mentioned.
[00033] The separation step, as it is related to phytosterol impurities, can be carried out simultaneously with the maintenance step. The separation stage, as it is
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14/44 related to sterol glycosides, acylated sterol glycosides and / or concentrates enriched by derivatives thereof, can comprise the steps of: liquefaction of the separate sterol glycosides, acylated sterol glycosides and / or concentrates of these enriched by derivatives by pre -heating and / or treating them with solvents and / or liquefying agents, the addition of enzymes or chemical agents with the liquefied sterol glycosides, acylated sterol glycosides and / or concentrates enriched by derivatives; subjecting liquefied sterol glycosides, sterol glycosides and / or concentrates enriched by derivatives combined with enzymes or chemical agents to flow-through hydrodynamic cavitation; and release of the oil captured in the liquefied sterol glycosides, acylated and / or concentrated sterol glycosides enriched by derivatives.
[00034] In a second particularly preferred embodiment, the impurities comprise phosphatides and the fluidic agent comprises water and an enzyme. The enzyme can be 'kosher'. In this preferred embodiment, the enzyme can comprise a phospholipase, a lipid acyltransferase or a mixture of those mentioned. Phospholipase can be a wild type, mutant or recombinant phospholipase A, phospholipase A1, phospholipase A2, phospholipase B, lysophospholipase, phospholipase C, phospholipase D, phosphodiesterase, lipid acyltransferase, phosphodiesterase of bacterial origin, yeast, plant or animal or a mixture of these.
[00035] The oil can be mixed with water and the mixture is subjected to hydrodynamic cavitation followed by the addition of the enzyme comprising phospolipase, lipid acyltransferase or
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15/44 mixing them. The enzyme is preferably immobilized on a removable cartridge, grid, filter, insertion, internal surface, magnet, magnetic particles, metal parts, plastic particles, nanoparticles, nanotubes, nanodiamantes, carbonaceous nanoparticles, particles and / or vehicles placed in desired locations within of the hydrodynamic cavitation equipment. The fluid mixture is preferably heated or cooled to a temperature in the range of 40-60 ° C for optimal enzyme activity.
[00036] The process can also include the steps of: reacting the phosphatides in the fluid mixture with the enzyme; stir the fluid mixture for a predetermined period of time to allow the completion of the phosphatide reaction; and stop the phosphatide reaction. The phosphatide reaction can be stopped by heating, changing the pH, applying an inhibitor, protease or chelating agent that forms a complex with the enzyme cofactor; perform the mixture in high shear; ultrasonic cavitation, and / or subject to hydrodynamic cavitation.
[00037] The separation step comprises the step of removing the reacted phosphatides. The reacted phosphatides can be removed by absorption, centrifugation, decantation, extraction, filtration, freezing, membrane filtration, or sedimentation. The separation step, which relates to the removal of phosphatides, can also comprise the steps of: liquefying the phosphatides removed by preheating the removed phosphatides, and / or adding solvents and liquefying agents to the removed phosphatides; subjecting liquefied phosphatides to hydrodynamic cavitation of passing fluid; and release the captured neutral oils and release the
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16/44 diacylglycerols and fatty acids in liquefied phosphatides. Alternatively, the separation step, which relates to the removed phosphatides, can also comprise the steps of: liquefying the phosphatides removed by preheating the removed phosphatides, and / or adding solvents and liquefying agents to the removed phosphatides; adding release agents and / or lipid-acetyltransferase, lipase, phospholipase or a mixture of those mentioned to liquefied phosphatides; release the oils captured in the liquefied phosphatides.
[00038] The present invention is also directed to a method of generating cavitation in a mixture of oil and agent flow that results in the production of refined oil from GEA, GE and phosphorus. This objective is achieved through the design of the cavitation equipment aimed at streamlining the purification followed by the separation of the waste enriched by impurities from the oil. According to the present invention, the method comprises feeding liquid oil and a solution of agent or a mixture thereof into the single-stage or multistage through-flow hydrodynamic cavitation equipment with a pump and controlling the cavitation by varying the inlet pressure pump, and continue to apply such treatment for a period of time sufficient to obtain the refined oil. The term oil includes, but is not limited to, oil containing homogeneous or heterogeneous triacylglycerol, tallow, fatty material and fats in a liquid phase before cavitation, produced by the mutated or genetically modified wild type of bacteria, yeast, algae, plants, animals, birds, fish and other prokaryotes or eukaryotes, a two-phase or multiphase system comprised of oil, water and / or other immiscible liquids,
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17/44 solution of salts, acids, bases, enzymes, gases and / or other solutes, dispersions, emulsions, suspensions, melted solids, gases in a supercritical state and mixtures thereof. The fluid
can be heated, cold, degassed or saturated with nitrogen, dioxide of carbon and other gases or mixtures From themselves.[00039] Therefore, in addition to of objectives and benefits gives
rapid oil purification described here, several objectives and advantages of the present invention are:
(1) provide a method for obtaining refined TAG oil suitable for human consumption and the production of turbidity-free biodiesel of ASTM quality;
(2) provide a method for removing GEA and GE from the oil in a drastically accelerated and simplified manner without the use of high temperature and pressure associated with conventional methods;
(3) provide a method to improve oil production by subjecting the oil and the phospholipase or lipid-acetyltransferase solution to hydrodynamic cavitation followed by submitting the residue separately (the swollen water-insoluble gels formed by hydrated phospholipids that precipitate from the oil ) to a subsequent cavitation treatment;
(4) providing a method, in which two or more cavitation equipment is used to provide high yield production.
[00040] The objectives of the present invention are achieved by feeding a mixture of oil and agent in a hydrodynamic cavitation equipment to carry out the conversion of impurities and the extraction of the corresponding products, with an aqueous phase. Cavitation
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18/44 hydrodynamics involves the formation of vapor bubbles of volatile compounds within the flow of the accelerated mixture with a pump to an appropriate speed. The phenomenon is called cavitation, because cavities form when the flow pressure is reduced to the vapor pressure of the volatile compound in the fluid. The bubbles expand and collapse, reaching a region of higher pressure. The implosion causes a localized increase in pressure and temperature and intense shear forces, resulting in a complete mixing and acceleration of reaction rates.
[00041] It is a cost decision that defines what type of hydrodynamic cavitation equipment to be employed since a number of configurations are viable, whether for large scale or small scale refining. One approach for the best result is to create an intense cavitation evenly distributing the flow, avoiding energy loss. Ideally, the energy applied should be optimized when the cavitation is still efficient and the energy expenditure is minimal. Other objectives and advantages of the present invention will be evident from the following detailed description, when viewed in conjunction with the accompanying drawings, which define the modalities of the present invention.
Brief Description of Drawings
[00042] The drawings what accompany illustrate the invention. We drawings:THE Figure 1 is a perspective view of a modality preferred of this device in cavitation multistage. THE Figure 2 is an cross section view taken at
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19/44 along line 2-2 of Figure 1.
The figure 3 is View in section transversal of disco of vortex taken to long of the line 3-3 of Figure 2. The figure 4 is View in section transversal of nozzle multijets outlet to long from lines 4-4 of Figure 2. The figure 5 is View in section transversal of body
cylindrical, taken along lines 5-5 of Figure 2.
Figure 6 is a side view of the cylindrical body.
The Figure is an enlarged view of the front interior of the working chamber and the toroidal vortex chamber illustrating the fluid flow.
Figure 8 is an enlarged view of the inner rear of the working chamber and the vortex toroidal chamber illustrating the fluid flow.
Figure 9 is a cross-sectional view of various shapes of the semi-spherical body.
Figure 10 is a cross-sectional view of another preferred embodiment of the multistage through-flow hydrodynamic cavitation device.
Figure 11 is a cross-sectional view taken along line 11-11 in Figure 10.
Detailed Description of Preferred Modalities [00043] With reference to the attached figures, a method for creating cavitation in an oil-water flow resulting in localized points of increased pressure, heat and vigorous mixing for oil refining is revealed. The method uses a flow-through hydrodynamic cavitation equipment to perform GEA, GE and / or the removal of phospholipids from the oil. The intense local heat released due to vapor compression and the formation of microjets, which accompany the bubble implosion,
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20/44 activate the molecules contained in the adjacent layers of the surrounding fluid and improve the mass transfer, thus promoting the targeted reactions and driving the modified impurities into the aqueous phase.
[00044] A preferred through-flow cavitation equipment should be made of inert material, for example, stainless steel. To improve its resistance to corrosive agents, the interior surface can be coated with oxides, nitrides, ceramic materials, plastics, polytetrafluoroethylene (PTFE), nanodiamonds, nanotubes, and other suitable compounds, composite materials, particles, nanoparticles and combinations of those mentioned. The equipment can be optimized through tempering, anodizing and other technologies. In another embodiment, the agents are immobilized over inserts and / or the internal surface of the device or are supported by magnets, magnetic materials or other particles attached to a desired location. The cavitation equipment can be equipped with a filter, membrane or selective absorber to allow an even better removal of impurities.
[00045] The through-flow cavitation device described in Figures 1 and 2 consists of a steel housing 22, which is connected to the inlet 24 and outlet 26 pipes for direct connection to an industrial pipe (not shown). The device 20 preferably has a mirrored symmetry such that from entry 24 to an intermediate point 27 it is repeated in reverse form from intermediate point 27 to an exit 26. The following description will follow the mirror symmetry and describe both entry 24 and outlet 26 towards intermediate point 27 simultaneously.
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21/44 [00046] Assuming the flow from left to right, front and rear multi-jet disc nozzles 28, 30 serve as the front and rear walls of the external working chambers 32, 34 and are located behind the inlet tube 24 and in in front of the outlet tube 26. The multi-jet nozzles 28, 30 are equipped with restriction and expansion channels 36, which are evenly distributed over the surfaces of the discs, which are the multi-jet nozzles 28, 30. The working chambers 32, 34 they are composed of radial cones 38, 44 and central guide cones 42, 43, which are connected to radial multi-jet nozzles 44, 46. Radial multi-jet nozzles 44, 46 have both restriction and expansion channels 48. Channels 48 are evenly distributed along the perimeter of the radial surface of the nozzles 44, 46, which direct the flow into the working chambers 50, 52.
[00047] Flow guides 54, 56, which direct the path from the perimeter to the center of the device 20, connect the chambers 50, 52. The cross section of the flow guides 54, 56 generally has an S-configuration. a semi-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 vortex disk 64, 66 (Figure 3), with curved guides 68 and central hole 69 is located behind the guides 54, 56 in the vortex chamber 70. The vortex chamber 70 is formed on the inner wall of the housing 22 and a cylindrical body placed in the center. The vortex chamber 70 directs the flow from hole 69 of the front disc 64. The holes 69 in the discs 64, 66 are coaxial. Their diameters are the same as those of the holes in the guides 54, 56. The intermediate point 27 is inside the vortex chamber 70.
[00048] Figure 3 is a diagram showing disks 64, 66
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22/44 with curved guides 68 and central holes 69. An inner side of the radial multi-jet nozzles 44, 46 is shown in Figure 4. Channels 48 lead into working chambers 50, 52 that house the semi-spherical body 58, 60 with the top niche 62. Figure 5 shows a cross-sectional view of the cylindrical body 72, which is provided with surface guides on the perimeter 74 that serve as channels for the flow of the fluid. Figure 6 is a drawing of a preferred embodiment for guides 74 of cylindrical body 72. Figures 7 and 8 illustrate the junction between working chambers 50, 52 and discs 64, 66 and illustrate the flow of fluid. At the junction between the guides 54, 56 and the discs 64, 66 are the toroidal vortex chambers 76 that are connected to the holes 69 and the working chambers 50, 52. Figure 9 is a simplified schematic illustration showing various modalities for the niche 62: a semi-sphere, a toroid and a parable.
[00049] The present through-flow cavitation device (Figure 2) operates as follows. The fluid, for example, a coarse dispersed emulsion is pumped into the inlet tube 24. The fluid moves to the multi-jet nozzle 28 and passes through its channels 36, which have both constraints and expansions. The flow through channels 36 induces the formation of vortices, individual flows and cavitation. The emulsion particles are subject to shear forces, and the quality of the emulsion improves. When the bubbles resulting from the cavitation reach the working chamber 32, they pulsate and collapse. The implosion of the bubbles results in an increase in pressure and temperature and in the formation of local jets that act on the particles of the emulsion, further improving the homogeneity of the emulsion. Then, the flow moves in a converging cone formed
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23/44 through the radial cone 38 and the central cone 42 which is mounted on the radial multi-jet nozzle 44. The flow is accelerated as it passes through the converging cone and then enters channels 48, which have both constrictions and expansions to generate vortices, individualized flows and cavitation in the fluid flow.
[00050] After passing through the radial multi-jet nozzle 44, the flow moves inside the working chamber 50, where the cavitation bubbles pulsate and implode. When the fluid flow moves downwards along the surface of the semi-spherical body 58 it falls from the edges of the top niche 62 generating toroidal vortices and a cavitation zone within the end of the working chamber 50. This cavitation field is characterized by a high intensity and a great
concentration in cavity. The final part of the guide in flow 54 is modeled how one mouthpiece constriction. Hole 69 at the disco 64 is molded how one mouthpiece expansion at the beginning and one resonator toroidal 76 is setted up at the site of constriction. [00051] When the fluid seeps along the zone gives Link gives
flow guide 54 to disk 64 it enters the ring grooves or toroidal resonator 76. The working principle of the toroidal resonator 76 is based on the high sensitivity of a symmetrical flow in relation to a lateral pressure. Changing the pressure at the point of origin of the jet will result in an angular change in the fluid flow. The fluid is forced out of the toroidal resonator 76 through discrete portions, which generate dynamic pulsations, vortexes and cavitation. The frequency of a toroidal resonator depends on its diameter (Agranat et al., 1987).
[00052] The flow moves out of the work chamber
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24/44
50, accelerating due to the passage through hole 69 in the front of the disc 64, and then enters channels located between the guides 68 located on the front disc 64 in the vortex chamber 70. To keep the fluid flow in a state of vortex and to prevent it from moving in a plane parallel to the central axis of the cavitator, the guides 74 are provided on the surface of the cylinder 72 to direct the flow into the channels 78 and sustain the spiral flow state (Figure 5 ). In the vortex chamber 70, cavitation bubbles are actuated by the action of centrifugal forces and Coriolis forces. As a result, the fluid pressure increases and the bubbles collapse.
[00053] The direction of the flow moving through the channels 78 formed by the guides 74 provided on the surface of the cylinder 72 is determined by the pitch angle with respect to the central axis of the cavitation device 20. In order to prevent the flow from flowing in line certain requirements must be met. The lines that are parallel to the main axis and advance by any point on the surface of a guide 74 must intersect the adjacent guide. In Figure 6, a straight line parallel to the central axis passes through a point on the guide 74 and intersects the adjacent guide 74 at point b. When more guides are intersected by a straight line (points c, a and b), the better the flow is swirled in the vortex chamber 70. The number of guides 74 that can be intersected by a line is limited due to the need for the total area of the guide channels 78 is equal to the area of the central hole 69 of discs 64, 66. The total area of the cross sections of channels 78 can be calculated by multiplying the number of channels by the height and width.
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25/44 [00054] After passing through channels 78 the fluid flow moves over the surface of vortex guides 68 and enters hole 69 at the rear of disc 66. This directs the flow along the central axis of the device 20. When the fluid flow exceeds the rear disk 66 and the rear guide 56, it enters the rear toroidal resonator 76, the operating principle of which is described above. The accelerated flow falls over the top niche 62 of the rear semi-spherical body 60, forming a pulsating toroidal vortex and cavitation zone (Dudzinskii and Nazarenko, 1996; Nazarenko, 1998). The frequency of pulsation and the shape of the cavitation zone depend on the properties of the fluid, flow rate and the shape of the niche. Preferred modalities for niche 62 are described above.
[00055] The fluid flow passes through the region of the toroidal resonator 76 and niche 62 and enters the working chamber 52 connected by the inner wall of the rear guide 56 and the rear semi-spherical body 60, which direct the flow from the center to the perimeter. The separate cavities of the toroidal flow region implode in the working chamber 52. After passing through the working chamber 52, the flow enters channels 48 of the radial multi-jet nozzle 46 provided with restrictions and expansions. This generates vortices, individualized jets of flow and cavitation. When the fluid flow moves in the working chamber 34, the flow speed is reduced, the pressure rises and the bubbles pulsate and implode. The flow then passes through the constrictions and expansions 36 of the rear multi-jet nozzle 30 followed by the generation of vortexes, individualized flow jets and cavitation. The emulsion particles that experience the
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26/44 cavitation process are reduced in size and their surfaces are modified. Cavitation bubbles pulsate and implode inside the working chamber 34, leading to the formation of shear forces and local jets. Then, the fluid flow leaves the cavitation device via the outlet tube 26.
[00056] This preferred embodiment of the device provides at least 11 cavitation zones: (1) the front multi-jet nozzle 28, (2) the front multi-jet nozzle 44, (3) top niche 62 in the front semi-spherical body 58, ( 4) front toroidal vortex chamber 76, (5) hole 69 and curved guides 68 of the front disc 64, (6) vortex chamber 70, (7) hole 69 and curved guides 68 of the rear disc 66, (8) toroidal vortex rear chamber 76, (9) top niche 62 in the rear semi-spherical body 60, (10) radial multi-jet rear nozzle 46, and (11), multi-jet end nozzle 30. The device design allows for two, four, six or even more cavitation regions of specular symmetry. The plane of specular symmetry crosses the intermediate point 27 of the vortex chamber 70 located between the disks 64, 66.
[00057] One of the many advantages of the preferred modality is its versatility with regard to fluid supply. The device 20 can be connected to a pump at either end and is especially suitable for technological applications with a demand to reverse the flow direction. The device 20 can be incorporated into a pipeline without any risk of confusing the inlet with the outlet. The main advantage of the present through-flow cavitation device 10 is the vortex interface and the cavitation generating zones with the working chambers with the highest pressure
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27/44 for the implosion of cavitation bubbles.
Figure 10 is a drawing showing an alternative embodiment of a through-flow multistage cavitation system 80 that provides as much as 10 zones 82 for the generation and collapse of cavitation bubbles and is comprised of 10 identical working chambers 84 and 10 nozzles multi-jets 86 that differ with respect to the cross-sectional areas created by their 88 channels.
When the fluid is introduced into the cavitation device 80 through a displacement pump or other means, the flow rate is the same within identical multi-jet nozzle channels 88 located sequentially. Thus, it is possible to reduce the flow of the fluid within the channels of the nearby multi-jet nozzles located downstream, while maintaining the cavitation at the same level. When the fluid flow passes through the front multi-jet nozzle 86 and the working chamber 84, the cavities implode and the fluid temperature rises. The increased temperature and the amplification of the nucleus facilitates the initiation of cavitation events in the cavitation zones located further on. Therefore, the same number of cavitations and the same concentration of the cavitation bubble can be achieved in the downstream areas with the lowest flow speed within the nozzle channels 88.
[00058] During the processing of the multistage fluid the hydraulic resistance is reduced by meeting the following condition: the cross section of the channel area (Sn) of each multi-jet nozzle is smaller than that of the next multi-jet nozzle (Sn + 1) following the path , according to the equation: 1.0 S _{n + i} / S _n 1.1, where n = 1, 2, 3, 4, 5, 6, 7, 8 or 9. This helps to save energy needed for the pumping a
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28/44 fluid flow through the multizone cavitation system. To reduce the scale of the parts of the cavitation device, for example, the multi-jet nozzle 86, it is necessary to place the channels 88 for the passage of the fluid, as close as possible. The number of channels 88 of the multi-jet channel 86 is limited by the ratio of the total area of the largest cross sections of the channel openings (Sd) to the surface area of the k multi-jet nozzle (SD): S _d / SD d 0.8, where SD = ΣS _t (k is the number 1 = 1
of channels nozzle multijets); Nd S ₁ = ₁ ^2/4, where di it's the bigger diameter of channels 1, and S nD = _D ^2/4, Where D is the diameter of the nozzle multijets. [00059] In one or another modality management in one fluid multi-component, the composition From vapors gives bubble of
cavitation is not uniform. The cavities are enriched with the vapors of the compound (s) which are more volatile under the given conditions. The bubble implosion releases energy that conducts chemical reactions and / or heats 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 treatment, the engineering design of the cavitation device and other conditions; such as the speed of a flow sustained by a pump. In practice, the pump pressure is increased until an adequate cavitation field strength is achieved. In addition to determining the size, concentration and composition of the bubbles, and as a consequence, the amount of energy released, the inlet pressure governs the result of chemical reactions. The faster the flow of movement, the less cavitation. A smaller cavitation number (especially when less than 1)
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29/44 implies a high degree of cavitation. The preferred embodiment of the present invention optimizes the cavitation to effect uniform change of fluids by applying the most suitable pump pressure. If too much energy is applied or the treatment time is too long, then the processing costs increase. Through the application of hydrodynamic cavitation at a pump pressure designed to generate cavitation and chemical conversion uniformly in the fluid, the change in physical and chemical properties occurs and the desired result is obtained.
[00060] The devices shown in Figures 1-11 are used to practice the method according to the present invention. According to the present invention, the fluid can be treated continuously or periodically, through the multistage devices 20, 80 consisting of vortices and zones of bubble production, as well as higher pressure working chambers. The systems can be placed anywhere around the production site, oil refining column or any other industrial facility. The device can be fixed in position or it can be mobile. The positioning of one device can be combined with the positioning of another device in series or in parallel. In practice, it is necessary to consider the cost of the device, the production and operating capacity and maintenance expenses. It should be noted that the operator of the cavitation device is not required to use high performance safety products for hearing protection; such as earmuffs or earplugs, as would be the case with high frequency acoustic cavitation.
[00061] The implosion of cavitation bubbles results in the formation of numerous microbubbles. Both the pressure and the
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The temperature of the steam contained within these bubbles is significant. If the fluid, which is enriched with these bubbles, moves to a lower pressure zone, the bubbles will play a core role and expand, increasing the intensity of the cavitation field (Zhang and Chai, 2001). The repeated multiplication, expansion and implosion of the cavities decrease the cavitation threshold. The bubbles grow from the nucleus, whose volume is greater than that of the nucleus originally present. This intensifies processing and allows for selective chemical reactions. This makes the present device unique and especially suitable for the treatment of multicomponent viscous fluids; such as petroleum, oils, rendered animal fat, cell extracts and other raw materials of high economic value.
[00062] With sonic and ultrasonic radiation, the results are mixed, unless the cavitation is uniform throughout the liquid. However, creating an even acoustic cavitation in large commercial tanks is a particular challenge. The present device achieves rapid fluid change through the use of multistage cavitation. The cavitation employed in accordance with the preferred embodiment of the present invention is achieved with a pump pressure selected in the range of approximately 3.45-344.74 bar (505,000 psi). The ideal pressure produces a sufficient number of cavities to achieve a high degree of treatment. However, the one usually versed in the technique can imagine that different fluids require different energies achieved through cavitation in order for changes to be achieved. Therefore, the range of 3.45-344.74 bar (50-5,000 psi) is in no way limited to use
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31/44 in the present invention. The energy released due to the bubble's implosion during the hydrodynamic pass-through cavitation activates molecules forcing them to react and form new compounds. The result is an improved product of high commercial value, whose components are easier to handle.
[00063] Purification of the oil by phosphorus-catalyzed lipid transferase can be coincident or conducted after the acid hydrolysis of GEs and GEAs to release sterile fatty acid esters. The bubbles generated during such a treatment are composed of the vapors of the compounds that are volatile under the established conditions, including those to be removed during the further downstream purification steps. The energy released due to the implosion of cavitation bubbles breaks the structure of the water and oil, mixing them significantly and improving mass transfer significantly, accelerating the targeted reactions. The ultrafine dispersions produced using a flow-through hydrodynamic cavitation device are relatively stable and do not coalesce quickly. They provide a very large water / oil contact surface that can be preserved through subsequent conventional mechanical agitation. Hydrodynamic cavitation equipment can be placed at the site of oil production, storage facilities or biodiesel facilities. There is yet another possibility, in which the equipment is mobile.
[00064] The size of the bubbles resulting from cavitation depends on the properties of the fluid mixture, the design of the cavitation device, the flow rate sustained by a pump, the temperature and other conditions. In practice, the pump pressure is increased until the level
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32/44 desired cavitation is achieved. The inlet pressure influences the size, concentration and composition of the bubbles and thus the composition of the processed oil. Preferably, cavitation is optimized to purify oil efficiently by applying the most suitable pressure. The desirable result is obtained through the generation of hydrodynamic cavitation with an ideal cavitation number and consistent density throughout the flow.
[00065] Hydrodynamic through-flow cavitation equipment is designed to express the purification of large volumes of oil. The equipment can be placed in sequence or mounted on sliding systems to increase capacity. The placement of one device can be combined with the placement of another device. The oil treatment aided by hydrodynamic cavitation can be repeated as many times as necessary to achieve the desired result. The implosion of the cavities results in the formation of deformed microbubbles, which become nuclei after passing into the zone of reduced pressure, increasing the field density and reducing the cavitation threshold. This makes multistage cavitation equipment especially suitable for refining high-quality oil. The equipment can be easily assembled and transported, making it suitable for field or remote locations. In practice, it is necessary to consider the cost of a device, its protein capacity and the energy required, maintenance and operating costs. An operator of hydrodynamic cavitation equipment is not required to wear hearing protection, as would be the case with acoustic cavitation equipment.
[00066] A practical approach to the best response from
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33/44 process is to adjust an inlet pressure that provides sufficient bubble implosion energy for the mixture of oil and agent and transfer the impurities to the aqueous phase. The amount of agent solution added to the oil depends on the level of contamination, but is preferably relatively small. Oil and agent can be cavitated at room temperature or can be preheated or cooled. Oil and agent are preferably cavitated in a 1.72 bar at 344, 74 bar (25-5000 psi). The oil can also be subjected to cavitation in the absence of the agent followed by purification aided by cavitation in the presence of a suitable agent. One usually skilled in the art will understand that different oils require different conditions to conduct an efficient purification and that a pump pressure of 1.72 bar to 344.74 bar (25-5000 psi) does not limit the application of this invention.
[00067] The application of flow-through hydrodynamic cavitation is not limited to the removal of phosphorus, GEAs and GEs from the oil to make it suitable for human consumption and biodiesel production. AGL, metals, sulfur compounds, carbohydrates, proteins, liposaccharides, aldehydes, ketones, terpenes, carotenes, chlorophyll and other impurities can also be removed. If necessary, phosphoric acid, citric acid or other agents can be added to modify GEA and GE and facilitate their removal.
[00068] The objectives of the present invention are achieved by feeding a mixture of liquid oil and an agent solution in a flow-through hydrodynamic cavitation equipment to perform chemical and enzymatic reactions that favor refining. Hydrodynamic cavitation involves
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34/44 formation of vapor bubbles in the accelerated oil-water flow with a pump. When the fluid pressure is reduced to the vapor pressure of water or the other volatile compounds contained in the fluid, bubbles form which expand and then collapse in a region of high pressure further downstream. The collapse produces sharp jumps in pressure and temperature, and shear forces, resulting in better mass transfer and higher reaction rates.
[00069] The following examples are given to illustrate the present invention and are not to be construed as limiting with respect to the scope or spirit of the invention.
Example 1 [00070] 10 Liters of RBD palm oil containing 430 ppm GEA, ppm GE and 0.045% AGL were mixed with 2.2% v / v of a 10% sodium hydroxide solution in water and subjected to a hydrodynamic cavitation of single-flow through-flow using three 11-stage equipment placed in series and operated at a pump inlet pressure of 58.6 bar (850 psi) at a temperature of 90 ° C. The cavitated mixture was stirred for 7 minutes, the oil and water phases were separated by centrifugation and the oil phase was analyzed as described here. (Verleyena et al., 2002). The cavitation-refined oil contained 61 ppm GEA, 14 ppm GE and 0.045% AGL. GEA is likely to be partially removed as GE after base-induced decomposition. There was no change in the AGL level. Therefore, it is concluded that palm oil can be efficiently refined through the rapid hydrodynamic cavitation method described here, which provides oil suitable for the production of turbidity-free biodiesel.
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Example 2 [00071] 10 Liters of RBD palm oil containing 430 ppm GEA, 11 ppm GE and 0.045% AGL were mixed with 2.2% v / v of a 10% sodium hydroxide solution in water and subjected to a hydrodynamic cavitation of single-pass through flow using three 11-stage equipment placed in series and operated at a pump inlet pressure of 58.6 bar (850 psi) at a temperature of 90 ° C. The cavitated mixture was stirred for 7 minutes, the oil and water phases were separated by centrifugation and the oil phase was analyzed as described here. (Verleyena et al., 2002). The cavitation-refined oil contained 17 ppm GEA, 6 ppm GE and 0.045% AGL.
Thus, it is concluded that the rapid method of hydrodynamic cavitation described achieves a significant reduction of both GEA and GE levels, providing a suitable oil for the production of turbidity-free biodiesel that meets the requirements of ASTM. It should be noted that no change in the AGL level was observed, similar to Example 1.
Example 3 [00072] To perform conventional enzymatic degumming, 2.16 g of 30% citric acid solution was added to 1 kg of crude soy oil containing 650.00 ppm P, 46.40 ppm Ca, 64, 70 ppm Mg and 0.80% AGL at 80-85 ° C. The mixture was subjected to high shear forces and then gently stirred for 15 minutes. Then, 1.45 g of 14% NaOH per 1 kg of oil was added and the mixture was vigorously stirred for 1 minute, cooled to 50-55 ° C and 100 ppm
phosphorylase A1 Lecitase Ultra by 2% of water was introduced. After another agitation a 300-350 rpm and 50-55 ° C, during an hour, The mixture was heated to 80-85 ° C followed in
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36/44 centrifugation. The oil refined by the conventional enzymatic degumming method contained 2.18 ppm P and 0.70% AGL. To perform an enzymatic degumming assisted by comparable hydrodynamic cavitation, with cavitated enzymes retaining full activity, 1.56% v / v of water was added to the soybean oil containing 650.00 ppm P, 46.40 ppm Ca, 64.70 ppm of Mg and 0.80% of AGL, followed by the hydrodynamic pass-through treatment of this mixture using three 11-stage equipment in series and operated at a pump inlet pressure of 55.16 bar (800 psi). The mixture was matured at 80 ° C for 20 minutes, cooled to 50-55 ° C and 100 ppm phosphorylase A1 Lecitase Ultra in 1% v / v water was added followed by a second hydrodynamic, single-pass through-flow cavitation treatment of the resulting mixture using three 11-stage equipment placed in series and operated at a pump inlet pressure of 55.16 bar (800 psi). The mixture was centrifuged after a rapid mechanical stirring at 50-55 ° C for 1 hour. The refined oil according to this method of enzymatic degumming assisted by hydrodynamic cavitation contained 2.99 ppm P, 1.49 ppm Ca, 0.76 ppm Mg and 1.06% AGL confirming the greater efficiency of the combined treatment, even with the steps of adding citric acid and NaOH being omitted. The refined oil that was subjected to cavitation after the addition of 100 ppm phospholipase contained 1.06% AGL, which is substantially higher when compared to 0.70% AGL obtained by conventional treatment with 100 ppm enzyme. It should be noted that neither citric acid nor NaOH was used in the last treatment. Hydrodynamic cavitation not only significantly increases oil yield, but eliminates the need for use
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37/44 of aggressive chemicals. The present invention provides a new method for removing LAT hydrolyzable and phospholipase hydrolyzable phosphatides from the oil and increases throughput without making major changes to conventional processing conditions.
Example 4 [00073] Crude soybean oil, containing 650.00 ppm P, 46.40 ppm Ca, 64.70 ppm Mg and 0.80% AGL was heated to 80-85 ° C and 10.56% v / v of water was added followed by high shear mixing for 20 minutes. The mixture was cooled to 50-55 ° C and 100 ppm of phosphorylase A1 Lecitase Ultra in 1% water v / v was introduced. After high shear mixing for 2 minutes and gentle stirring for 1 hour the mixture was heated to 80-85 ° C followed by centrifugation. The soybean oil refined by this method of enzymatic degumming in the absence of citric acid and NaOH contained 10.2 ppm P and 0.90% AGL. However, when 1.56% water v / v was added to the same crude soybean oil, containing 650.00 ppm P, 46.40 ppm Ca, 64.70 ppm Mg and 0.80% AGL followed by hydrodynamic through-flow cavitation treatment of this mixture using three 11-stage equipment placed in series and used for the pump inlet pressure of 55.16 bar (800 psi) and mixing under high shear at 80 ° C for 20 minutes , after which the mixture was cooled to 50-55 ° C and 100 ppm of phosphorylase A1 Lecitase Ultra in 1% v / v water was added and the mixture was vigorously stirred for 1 hour followed by centrifugation, the soy oil refined by this enzymatic degumming aided by hydrodynamic cavitation in the absence of citric acid and NaOH contained only 2.94 P ppm, 1.76 ppm Ca, 0.67 ppm Mg and 1.17% AGL. Thus, the
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38/44 hydrodynamic cavitation of oil and water before introducing phospholipase is highly beneficial, as it disrupts the structures of water and oil which allows for much greater interfacial area of oil / water by generating ultrafine dispersions. The combination of hydrodynamic oil and water cavitation with subsequent enzymatic degumming significantly reduces reagent costs and conserves energy while providing refined phosphorus and metal oil and provides the highest yield. In fact, the AGL level increased from 0.80 to 1.17%, suggesting a significantly higher oil yield.
Example 5 [00074] To perform cavitation-assisted enzymatic degumming, a 50% citric acid solution was added to the crude soybean oil to create a 0.03325% v / v percentage solution. The crude soybean oil contained 650.00 ppm P, 46.40 ppm Ca, 64.70 ppm Mg and 0.80% AGL. This mixture was treated with the hydrodynamic flow-through cavitation process of the present invention by means of 3 11-stage equipment placed in series and operated at a pump pressure of 55.16 bar (800 psi), and smooth mixing at 80 ° C for 30 minutes. The mixture was subjected to high shear and then gently stirred for 15 minutes. Then, 1.56% v / v water was added and the mixture was cavitated again, maintained at 80 ° C for 20 minutes, cooled to 5055 ° C and 100 ppm phosphorylase A1 Lecitase Ultra in 1% water v / v was added. After stirring at 50-55 ° C for one hour, the mixture was centrifuged. The oil refined by this method contained 0.20 ppm P, 3.30 ppm Ca, 0.11 ppm Mg and 0.89% AGL. When the previous treatment was repeated with 50 ppm of phosphorylase, the refined oil contained 0.81 ppm P, 0.18 ppm
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Ca, 0.07 ppm Mg and 0.83% AGL. Based on the comparison of these data, it can be concluded that hydrodynamic cavitation allows to significantly increase the oil yield while reducing the use of phospholipase by at least 50%.
Example 6 [00075] For comparison purposes, assisted cavitation assisted degumming was performed in the absence of enzymes using a 50% citric acid solution added to the crude soybean oil to create a 0.03325% v /% solution v. The crude soybean oil contained 650.00 ppm P, 46.40 ppm Ca, 64.70 ppm Mg and 0.80% AGL. The mixture was stirred gently at 80 ° C for 30 minutes followed by the addition of 10.56% v / v water. The mixture was subjected to treatment by a hydrodynamic single-pass through-flow cavitation process of the present invention, using 3 11-stage equipment placed in series and operated at a pump pressure of 55.16 bar (800 psi ), and centrifuged after maturation at 80 ° C for 20 minutes. The oil refined by this method contained 3.15 ppm P, 0.38 ppm Ca, 0.26 ppm Mg and only 0.51% AGL.
[00076] In a similar experiment, a 50% citric acid solution was added to the soybean oil to create a 0.03325% v / v percentage solution. The soybean oil contained 650.00 ppm P, 46.40 ppm Ca, 64.70 ppm Mg and 0.80% AGL and the mixture was subjected to a treatment by a through-flow hydrodynamic cavitation process of the present invention, using 3 11-stage equipment placed in series and operated at a pump pressure of 55.16 bar (800 psi), followed by stirring at 80 ° C for 30 minutes and adding 10.56 % v / v of water. Then the
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The mixture was again subjected to a hydrodynamic single-pass through-flow cavitation process of the present invention using 3 11-stage equipment placed in series and operated at a pump pressure of 55.16 bar (800 psi ) and centrifuged after maturing 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% AGL. Thus, no increase in yield was observed and phosphorus concentrations were higher than those obtained with the combined treatment of cavitation and enzyme.
[00077] The preferred modality of the cavitation system that is especially suitable for the removal of GEAs and GEs from oil containing triacylglycerol using the process described here is three 11-stage devices that are placed in series and operated at a pressure of 55.16-82, 74 bar (800-1200 psi) pump inlet. In this preferred embodiment, the temperature of the oil and agent solution is in the range of 10-90 ° C and the fluidic agent comprises a solution in a percentage of 0.1-5%.
[00078] The preferred modality of the cavitation system which is especially suitable for the enzymatic removal of phosphatides from oil containing triacylglycerol using the process described here is 3 11-stage devices that are placed in series and operated at a pump inlet pressure 55.16-82.74 bar (800-1200 psi). In the preferred embodiment, the temperature of the oil and enzyme solution is in the range of 40-60 ° C and the aqueous phase containing the enzyme comprises a 0.1 -5% v / v percentage solution.
[00079] The purified oil and the residues or enriched gums of GEA and / or GE are separated by centrifugation at temperature
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41/44 environment or at other temperatures; for example, 10 ° C. Often, neutralization is not necessary before the transesterification of the purified phytosterol oil by means of hydrodynamic cavitation. With the low amount of water added during cavitation-assisted purification, the moisture content of the resulting purified oil is low and drying is not necessary.
[00080] Although the above descriptions contain many specificities, they should not be interpreted as limiting the scope of the invention, but merely to provide illustrations of some of the preferred embodiments of the present invention, which offers many potential uses. The localized heat released due to the compression of gas and microjets that accompanies the bubble implosion mixes oil and water, thus increasing mass transfer, reactions and modification and extraction of impurities, as well as other processes. Many other embodiments of the present invention are possible, which would be evident to those usually skilled in the art. For example, there are many techniques for creating cavitation in fluid mixture streams other than those described here. Therefore, the scope of the invention should be determined only by the appended claims and their legal equivalents, rather than by the examples given.
[00081] The present invention uses the energy released during the implosion of the cavitation bubbles to purify the oil. Hydrodynamic cavitation is the formation of bubbles filled with vapor in the fluid flow, followed by the collapse of these bubbles in a high pressure zone. In practice, the process is carried out as follows: the fluid is introduced into the inlet passage of the cavitation equipment with a pump. In areas
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42/44 located, the flow velocity increases, inducing pressure to fall according to Bernoulli's Law. This pressure drop causes the formation of bubbles filled with the vapors of compounds that boil under the given conditions; that is, the fluid pressure drops below the vapor pressure. When the pressure in the flow increases, the bubbles collapse, exposing the vapors contained in them and the surrounding medium layer, to high pressure and temperature, shear forces, shock waves, acoustic vibration and electromagnetic radiation. These factors result in changes in the fluid components and reactions take place inside the collapsing bubbles and / or in the adjacent layers of the fluid.
[00082] According to the present invention, the intensity of the cavitation field is controlled by means of a properly designed device, inlet pressure, temperature and composition of the fluid medium. For example, the high viscosity of the oil can be lowered by adding solvents or surfactants or mixtures thereof, by heating, applying external electric or magnetic fields or any of those mentioned.
[00083] The present invention creates beneficial conditions that cannot be duplicated. The efficiency of the method can be further improved through consecutive applications of high pressure, high heat, turbulence and vigorous mixing, applied in a through-flow mode within a short period. The preferred embodiments of the present invention apply optimized levels of both pressure and heat through controlled hydrodynamic cavitation. The process is independent of external conditions and provides a highly effective method of purifying the oil by removing
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43/44 compounds containing phosphorus, GEA and GE.
[00084] Important economic benefits can be experienced through the implementation of this invention. The optimized use of flow-through hydrodynamic cavitation allows a reduction in equipment, maintenance and energy costs, as it produces oil suitable for the production of biodiesel without turbidity of ASTM quality. Cavitation-assisted purification poses no environmental threats and is economically viable. The combination of technological simplicity and economic viability makes this method attractive to small and large producers of biodiesel and oil refineries.
[00085] The detailed embodiments of the present invention are disclosed herein. However, it should be understood that the embodiments disclosed are merely exemplary of the present invention, which can be accomplished in several ways. Therefore, the details disclosed herein are not to be construed as limiting, but merely as a basis for the claims and guidance of the one usually skilled in the art as to how to use the invention. The beneficial effects obtained through the present invention cannot be achieved through acoustic cavitation, in which the bubbles attenuate the sound waves, limiting the effective distance of the sound wave generator. In addition, ultrasonic irradiation modifies a medium in specific locations, depending on the frequency and interference patterns. The present invention overcomes these limitations by uniformly purifying oil. Although the preferred embodiments have been described, it will be understood that there is no intention to limit the invention by such disclosure, but instead, it is intended to cover the
Petition 870190002650, of 01/09/2019, p. 47/98
44/44 modifications that fit the spirit and scope of the present invention. Various modifications can be made without departing from the scope and spirit of the invention. Consequently, the invention is not to be limited, except for the appended claims.

权利要求:
Claims (5)
[1]
1. PROCESS FOR REMOVING IMPURITIES FROM OIL CONTAINING TRIACYLGLYCEROL, comprising the steps of:
mixing the oil and a fluidic agent to form a fluid mixture that has an oil phase and an aqueous phase;
create hydrodynamic cavitation in the fluid mixture by pumping the fluid mixture with a predetermined pump inlet pressure;
maintaining hydrodynamic cavitation in the fluid mixture for a predetermined period of time;
moving impurities from the oil phase to the aqueous phase; and separate the aqueous phase from the oil phase, characterized by:
the fluidic agent is added to the oil in an amount so as to form between 0.1% and 5.0% v / v of the fluid mixture;
heat or cool down mixture fluid to an temperature in the range 10-90 ° C; and The mixture fluid be pumped through three equipment hydrodynamic cavitation (20, 80) of eleven
stages placed in series and operated at a pump inlet pressure in the range of 5500 - 8300 kPa (800 - 1,200 psi).
[2]
2/5 of a constriction, P _v is the vapor pressure of the fluid mixture, p is the density of the fluid mixture, and V is the velocity of the fluid mixture in the constriction.
2. Process according to claim 1, characterized in that the fluid mixture within at least one region within the hydrodynamic cavitation equipment has a cavitation number less than or equal to one, when calculated using the equation: Cv = (P - Pv) / 0.5 pV ² , where C _V is the cavitation number, P is the downstream pressure
Petition 870190002650, of 01/09/2019, p. 49/98
[3]
3/5 mix of those mentioned; or a solution of phosphoric acid, citric acid, acetic acid or a mixture of those mentioned.
Process according to claim 6, characterized in that the separation step, with regard to phytosterol impurities, is carried out simultaneously with the maintenance step.
Process according to claim 6, characterized in that the separation step, with regard to sterol glycosides, acylated and / or concentrated sterol glycosides enriched by derivatives thereof, additionally comprises the steps of:
liquefy the separate sterol glycosides, acylated and / or concentrated sterol glycosides enriched by their derivatives by preheating and / or treating them with solvents and / or liquefying agents;
adding enzymes or chemical agents to liquefied sterol glycosides, acylated sterol glycosides and / or concentrates enriched by derivatives;
subjecting the liquefied sterol glycosides, acylated sterol glycosides and / or concentrates enriched by derivatives combined with enzymes or chemical agents to flow-through hydrodynamic cavitation; and releasing the oil trapped in the liquefied sterol glycosides, acylated sterol glycosides and / or concentrates enriched by derivatives.
Process according to claim 1, characterized in that the impurities comprise phosphatides and the fluidic agent comprises water and an enzyme comprising a phospholipase, a lipid acyltransferase or a mixture
Petition 870190002650, of 01/09/2019, p. 51/98
Process according to claim 1, characterized in that it additionally comprises the step of introducing ammonia gas, nitrogen, carbon dioxide or a mixture of those mentioned in the fluid mixture, before or during the pumping, creating and / or maintaining stages .
[4]
4/5 of those mentioned; the additionally comprising the step of the fluid mixture being heated or cooled to a temperature in the range of 40-60 ° C for optimal enzymatic activity.
Process according to claim 9, characterized in that the oil is mixed with water and the mixture is subjected to hydrodynamic cavitation, followed by the addition of the enzyme.
Process according to claim 9, characterized in that it additionally comprises the steps of:
react the phosphatides in the fluid mixture with the enzyme; stir the fluid mixture for a predetermined period of time to allow the phosphatide reaction to end; and stop the phosphatide reaction.
Process according to claim 11, characterized in that the separation step comprises the step of removing the reacted phosphatides.
13. Process according to claim 12, characterized in that the separation step, in relation to the phosphatides removed, additionally comprises the steps of:
liquefy the removed phosphatides by preheating the removed phosphatides, and / or adding solvents and liquefying agents to the removed phosphatides;
subject the liquefied phosphatides to hydrodynamic cavitation with passing flow; and release the trapped neutral oils and release the diacylglycerols and fatty acids in the liquefied phosphatides.
14. Process according to claim 12, characterized in that the separation step, in relation to the removed phosphatides, additionally comprises the
Petition 870190002650, of 01/09/2019, p. 52/98
4. Process according to claim 1, characterized in that it additionally comprises the step of immobilization reagents, oxides, nitrides, ceramic materials, plastics, polytetrafluoroethylene, nanodiamonds, nanotubes, or combinations of those mentioned, over the internal walls of the equipment hydrodynamic cavitation (20, 80) or over a removable insert (28, 30, 38, 40, 42, 43, 44, 46, 54, 56, 58, 60, 64, 66, 72, 86) configured for insertion into the hydrodynamic cavitation equipment.
5. Process according to claim 1, characterized in that it additionally comprises the step of placing a selective membrane and / or whitening earth, in a final chamber (26) of the hydrodynamic cavitation equipment (20, 80) or in a chamber located downstream of the hydrodynamic cavitation equipment.
Process according to claim 1, characterized in that impurities comprise phytosterols, sterol glucosides and / or acylated sterol glucosides, and the fluidic agent is: water; an alkali metal hydroxide solution comprising sodium hydroxide or potassium hydroxide, an inorganic base, an organic base or a
Petition 870190002650, of 01/09/2019, p. 50/98
[5]
5/5 steps of:
liquefy the removed phosphatides by preheating the removed phosphatides, and / or adding solvents and liquefying agents to the removed phosphatides;
adding release agents and / or lipidoacetyltransferase, lipase, phospholipase or a mixture of these to liquefied phosphatides; and release the neutral oils trapped in the phosphatides
liquefied.15. Process, according with the claim 9, featured per additionally understand the step in immobilize the enzyme per about a cartridge removable, grid,
filter, insertion, internal surface, magnet, magnetic particles, metallic particles, plastic particles, nanoparticles, nanotubes, nanodiamonds, carbonaceous nanoparticles, particles and / or carriers positioned in desired positions within the hydrodynamic cavitation equipment (20, 80).

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CA2809236A1|2012-03-22|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

JPS636600B2|1978-11-30|1988-02-10|Showa Sangyo Co|

---

SK284128B6|1996-05-10|2004-09-08|Unilever Nv|Composition containing organogel|

---

RU2164629C1|1999-10-04|2001-03-27|Иванников Владимир Иванович|Method and device for cavitation of liquid flow|

---

US20090188157A1|1999-10-26|2009-07-30|Holloway Jr William D|Device and method for combining oils with other fluids and mixtures generated therefrom|

---

US20040251566A1|2003-06-13|2004-12-16|Kozyuk Oleg V.|Device and method for generating microbubbles in a liquid using hydrodynamic cavitation|

---

DK1791933T3|2004-07-16|2011-09-05|Danisco|Process for enzymatic boiling of oil|

---

RU2333942C1|2007-03-07|2008-09-20|Государственное научное учреждение "Всероссийский научно-исследовательский институт жиров" Российской академии сельскохозяйственных наук |Method of extraction of phosphatides from vegetable oils|

---

US7935157B2|2007-08-08|2011-05-03|Arisdyne Systems, Inc.|Method for reducing free fatty acid content of biodiesel feedstock|

---

US8911808B2|2008-06-23|2014-12-16|Cavitation Technologies, Inc.|Method for cavitation-assisted refining, degumming and dewaxing of oil and fat|

---

US7762715B2|2008-10-27|2010-07-27|Cavitation Technologies, Inc.|Cavitation generator|CN101909730B|2008-01-10|2013-07-10|株式会社盛长|Static fluid mixer|

---

US8042989B2|2009-05-12|2011-10-25|Cavitation Technologies, Inc.|Multi-stage cavitation device|

---

DE102009034977B4|2009-07-28|2011-07-21|Technische Universität München, 80333|Cavitation reactor and a method for the hydrodynamic generation of homogeneous, oscillating cavitation bubbles in a fluid, a method for disinfecting a fluid and a method for emulsifying or suspending or for the reaction favoring at least two substances|

---

GB201007655D0|2010-05-07|2010-06-23|Isis Innovation|Localised energy concentration|

---

US8940347B2|2011-04-08|2015-01-27|H R D Corporation|High shear application in processing oils|

---

US9126176B2|2012-05-11|2015-09-08|Caisson Technology Group LLC|Bubble implosion reactor cavitation device, subassembly, and methods for utilizing the same|

---

GB201208939D0|2012-05-21|2012-07-04|Isis Innovation|Localised energy concentration|

---

RU2544696C2|2012-11-02|2015-03-20|Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тамбовский государственный технический университет" ФГБОУ ВПО ТГТУ|Method of removing water-soluble admixtures from suspensions of organic products|

---

CN103223311B|2013-05-15|2014-03-26|陕西师范大学|Turbulence energy-reinforced hydraulic transient cavitated venturi tube|

---

US20150045543A1|2013-08-12|2015-02-12|Melvin Mitchell|Isolation method for water insoluble components of a biomass and products provided therefrom|

---

US9421477B2|2013-08-12|2016-08-23|Green Extraction Technologies|Biomass fractionation and extraction apparatus|

---

US20150044306A1|2013-08-12|2015-02-12|Melvin Mitchell|Process for fractionation and extraction of herbal plant material to isolate extractives for pharmaceuticals and nutraceuticals|

---

WO2015100063A1|2013-12-26|2015-07-02|Exxonmobil Research And Engineering Company|Methods of inhibiting precipitation of biodiesel fuel components|

---

US9321983B2|2014-07-03|2016-04-26|Arisdyne Systems, Inc.|Methods for degumming oils|

---

CN104263523A|2014-09-17|2015-01-07|江苏大学|Cavitator for preparing biodiesel|

---

US9453180B2|2014-10-15|2016-09-27|Arisdyne Systems, Inc.|Process for degumming oils|

---

US9290717B1|2014-12-15|2016-03-22|Arisdyne Systems, Inc.|Reactor for degumming|

---

WO2016099440A1|2014-12-15|2016-06-23|Arisdyne Systems, Inc.|Reactor for degumming|

---

US9340749B1|2015-05-06|2016-05-17|Arisdyne Systems, Inc.|Method for degumming triglyceride oils|

---

MX2017013955A|2015-05-06|2018-04-11|Arisdyne Systems Inc|Method for degumming triglyceride oils.|

---

EP3362540B8|2015-10-14|2020-06-17|Archer-Daniels-Midland Company|Method for reducing neutral oil losses during neutralization step|

---

WO2017127240A1|2016-01-19|2017-07-27|Arisdyne Systems, Inc.|Method for degumming vegetable oil|

---

JP6129390B1|2016-07-28|2017-05-17|株式会社カクイチ製作所|Nanobubble generating nozzle and nanobubble generating apparatus|

---

CN106512619B|2016-11-21|2018-08-21|江苏建筑职业技术学院|A kind of equipment and its minimizing technology of high speed rotation inhalation removal industrial dust|

---

CN106804694B|2017-03-16|2021-03-30|许昌学院|Ultrasonic supercritical-low-temperature vacuum frying and drying process for mushrooms|

---

US10344246B2|2017-05-24|2019-07-09|Arisyne Systems, Inc.|Oil degumming systems|

---

CN207124204U|2017-08-16|2018-03-20|君泰创新（北京）科技有限公司|Device for uniform circulation making herbs into wool cleaning decoction|

---

CN107881010A|2017-11-25|2018-04-06|防城港市润禾农林科技有限公司|A kind of pressing device refined for balsamic essential oil|

---

WO2019182737A1|2018-03-21|2019-09-26|Arisdyne Systems, Inc.|Methods for reducing soap formation during vegetable oil refining|

---

CN108514805B|2018-05-03|2021-12-28|闫家义|High-speed vortex flow gas separation device|

---

CN112204118A|2018-05-30|2021-01-08|道达尔研究技术弗吕公司|Process for hydrotreating a feed of diesel fuel and of a naturally occurring oil, hydrotreating unit for implementing the process and corresponding hydrorefining unit|

---

GB201817692D0|2018-10-30|2018-12-19|Ge Healthcare|Mixing device|

---

CA3122441A1|2019-01-03|2020-07-09|Vitalis Extraction Technology Inc.|Induced cavitation mixing apparatus|

---

US10808202B2|2019-01-25|2020-10-20|N.V. Desmet Ballestra Engineering S.A.|In line degumming and neutralization of oils and fats using hydrodynamic flow-through cavitation reactors|

---

CN110027238B|2019-05-17|2020-08-04|福建福迩金生物科技有限公司|A raw materials preprocessing device for phytosterol draws|

---

EP3799954A1|2019-10-04|2021-04-07|SQW Sauerländer Quality Water GmbH & Co. KG|Device, system and method for reducing a surface tension and / or a viscosity of a fluid|

---

CH717232A1|2020-03-16|2021-09-30|Shcheblanov Aleksandr|Generator for generating rig-shaped and spatial eddies in a liquid.|

---

GB2594546A|2020-03-16|2021-11-03|Vozyakov Igor|Method and apparatus for water processing|

---

GB2593980A|2020-03-16|2021-10-13|Vozyakov Igor|Method and apparatus for water processing|

---

CN111561452B|2020-04-27|2021-04-09|江苏博利源机械有限公司|Floating pump|

---

CN111632420B|2020-06-04|2021-08-03|湖南银城湘味食品有限公司|Device and process for purifying waste oil of fried food based on continuous uninterrupted mode|

---

WO2021262468A1|2020-06-24|2021-12-30|Cargill, Incorporated|Oil processing|

---

WO2021262466A1|2020-06-24|2021-12-30|Cargill, Incorporated|Oil processing|

法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2018-12-18| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

---

2019-07-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US12/883,328|US8945644B2|2009-06-15|2010-09-16|Process to remove impurities from triacylglycerol oil|

---

US12/883,328|2010-09-16|

---

PCT/US2010/049284|WO2012036695A1|2010-09-16|2010-09-17|Process to remove impurities from triacylglycerol oil|

---