WO2018101710A1 - Oil palm biomass solid phase extract containing high concentration of fat-soluble physiologically active substance produced from palm oil production by-products and method for producing same - Google Patents

Oil palm biomass solid phase extract containing high concentration of fat-soluble physiologically active substance produced from palm oil production by-products and method for producing same Download PDF

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WO2018101710A1
WO2018101710A1 PCT/KR2017/013717 KR2017013717W WO2018101710A1 WO 2018101710 A1 WO2018101710 A1 WO 2018101710A1 KR 2017013717 W KR2017013717 W KR 2017013717W WO 2018101710 A1 WO2018101710 A1 WO 2018101710A1
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biomass
palm
oil
extract
fat
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PCT/KR2017/013717
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French (fr)
Korean (ko)
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유주현
배재한
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한국화학연구원
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation

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  • the present invention is a method for extracting / recovering fat-soluble bioactive substances carotenoids, tocopherols and tocotrienols from the by-products or wastes left after the production of palm oil, and oil palm bio-containing high concentrations of fat-soluble bioactive substances such as carotenoids produced by the method. It relates to mass solid extract.
  • the fat-soluble physiological activity by solvent extraction including 10 to 30% by weight palm oil containing the fat-soluble bioactive substance, 15 to 40% by weight of solvent-insoluble oil palm biomass and 40 to 70% by weight of water
  • the present invention relates to an oil palm biomass solid extract and a method for preparing the same that can be used for industrial production of materials.
  • palm oil produced from oil palm fruit is composed of saturated fatty acid and unsaturated fatty acid in a ratio of 1: 1, so it shows semi-solid state at room temperature like animal oil or fat.
  • Unrefined palm oil is called crude palm oil (CPO), and 500 to 1,600 mg / kg carotenoids, 600 to 1,000 mg / kg tocopherol and tocotrienol, coenzyme Q10, It contains high value-added bioactive substances such as phytosterol and is red by beta-carotene.
  • EFB Empty fruit bunch of oil palm
  • Palm pressed fiber which is entangled like cobwebs in palm fruits containing palm oil and is released during the extraction process, accounts for 15% of palm fruits and contains a large amount of palm oil. Along with the room, it is used as boiler fuel for palm oil manufacturing plants.
  • This palm pulp fiber contains 5 to 7% by weight of palm oil, 4,000 to 6,000 mg / kg of carotenoids and 2,400 to 3,500 mg / kg of tocols, which are known to contain more bioactive substances than palm oil (Choo etc., JAOCS, 1996, 73, 599-602 .).
  • the palm fruit mill waste water (POME, palm oil mill) generated in the process of recovering palm oil by squeezing the nut and separating the liquid from the palm nut by steaming fresh fruit bunch of oil palm with high temperature steam.
  • effluent contains 95-96% by weight of water, 0.6-0.7% by weight of fat, and 4-5% by weight of solids. Protein, carbohydrates, fats and minerals are present in high concentrations. It can be used for the production of useful substances, but most of them are disposed of in wastewater treatment plants or used as raw materials for biogas production. It also contains a significant amount of palm oil, which contains a large amount of bioactive substances (about 1,500 mg / kg for carotenoids, Ahmad et al., Desalination Water Treat , 2009, 7, 251-256.).
  • palm oil production process by-products contain a significant amount of fat-soluble components, and these components also include high value-added bioactive substances such as beta carotene, alpha carotene, tocopherol and tocotrienol.
  • Beta-carotene has an antioxidant activity, has provitamin A activity, and has the characteristics of inhibiting the occurrence of various cancers such as pancreatic cancer, rectal cancer, prostate cancer, breast cancer, melanoma and skin cancer and preventing cataracts.
  • Alpha-carotene also has a cancer preventive effect and antioxidant activity and its activity is superior to beta-carotene, but provitamin A activity represents half of beta-carotene.
  • Tocopherol is an antioxidant that has vitamin E activity.
  • tocopherol When used in conjunction with other antioxidants, tocopherol prevents macular degeneration and prevents some cancers, cataracts, and Parkinson's disease. It is also used as a food preservative. Tocotrienols are more efficient antioxidants than tocopherols and have vitamin E activity, inhibit cancer formation and inhibit cholesterol formation.
  • bioactive materials are high value-added compounds present in a large amount in the by-products of palm oil production, but most of them are not recovered.
  • fat-soluble substances including such beta-carotene, alpha-carotene, tocopherol, tocotrienol are extracted from palm oil, but the amount is extremely limited.
  • beta-carotene is produced by chemical synthesis, which is less effective than natural substances, but the manufacturing cost is known to be 2,000 US dollars per kg.
  • these fat-soluble bioactive substances can be extracted inexpensively from palm oil manufacturing by-products, it is expected that their added value as natural bioactive substances will be more than synthetic materials.
  • the solvent-based extraction of fat-soluble physiologically active substances contained in such a large amount of biomass at low concentrations is 0.1 g / cm 3 for the bulk density of the biomass. Due to the excessive cost is inevitable, such as the use of an organic solvent and a large extraction equipment more than five times the weight of the biomass weight, more practical extraction methods are required.
  • the fat-soluble physiologically active substance contained in the palm oil by-product is dissolved in palm oil, and this palm oil has the characteristic of emulsifying and eluting in water when friction-pulverizing with water.
  • emulsion particles containing this fat-soluble physiologically active substance are attached to the biomass fine particles by coagulant, and if necessary, additional flocculant improves sedimentation by coarsening, thereby increasing dehydration efficiency.
  • the solid extract prepared in this way can be easily handled because it contains only a 1% of the volume of biomass while containing a high concentration of fat-soluble physiologically active substances of palm by-products.
  • the bioactive substance can be extracted at a high concentration even with a small amount of solvent, it is useful for the industrial production of high value-added bioactive substances contained in palm by-products.
  • the present invention was developed to solve the above problems, and aims to provide a simpler and more economical method for extracting a fat-soluble physiologically active substance containing a low concentration due to the small weight or excessive water content of palm oil production by-products. It is done.
  • oil palm biomass solid phase extract solidifying emulsion particles containing fat-soluble physiologically active substances that can be easily handled with only about 1% of the volume of biomass while containing a high concentration of fat-soluble physiologically active substances such as carotenoids, and a preparation method thereof.
  • the present invention provides solvent extraction including 10 to 30% by weight of palm oil containing fat-soluble physiologically active substance, 15 to 40% by weight of solvent-insoluble oil palm biomass and 40 to 70% by weight of water. It provides an oil palm biomass solid extract that can be used in the industrial production of fat-soluble physiologically active substances.
  • the biomass gruel manufacturing step of manufacturing a biomass gruel containing an emulsion by immersing the byproduct oil by-products in water and friction grinding; Liquid extract manufacturing step of preparing a liquid extract containing biomass fine particles and emulsion particles by solid-liquid separation of the biomass gruel obtained in the biomass gruel manufacturing step; Coagulant, flocculant or coagulant and flocculant are sequentially added to solidify palm oil emulsion particles containing fat-soluble bioactive substances in the liquid extract obtained from the liquid extract preparation step.
  • the oil palm biomass solid extract solidifying emulsion particles containing fat soluble bioactive substances according to the present invention can be easily handled because it contains only about 1% of the volume of biomass while containing a high concentration of fat soluble bioactive substances which palm by-products have. have.
  • the bioactive substance can be extracted at a high concentration even with a small amount of solvent, it is useful for the industrial production of high value-added bioactive substances contained in palm by-products.
  • the present invention enables to prepare a solid extract containing a high concentration of high value-added fat-soluble physiologically active substances such as beta-carotene from palm fruits, palm pulp fiber and palm oil plant wastewater, using as a raw material a small amount of organic solvent or supercritical extraction It is useful for industrially preparing fat-soluble physiologically active substances by utilizing various conventional extraction techniques and purification techniques such as chromatography.
  • 1 is a process chart showing the manufacturing step of the oil palm biomass solid extract according to an embodiment of the present invention.
  • lipophilic bioactive substance is a biochemical that is hardly soluble in water and soluble in organic solvents.
  • Carotenoids such as alpha carotene, beta carotene and gamma carotene, tocopherol and tocotrienol It refers to bioactive substances contained in palm fruits, palm pulp fiber and palm oil plant wastewater such as tocols.
  • carotenoid or “beta carotene” refers to a carotenoid and a beta form of the substance as a generic meaning containing various carotenes, respectively, but refers to other fat-soluble bioactive substances such as tocols. It is also used as a symbolic meaning.
  • biomass gruel refers to a biomass suspension prepared by adding water to biomass and friction grinding, and containing palm oil emulsion particles and biomass powder containing fat-soluble physiologically active substances. This biomass gruel is used as a raw material for primary solid-liquid separation, which separates palm oil emulsions and some fine biomass from most insoluble biomass.
  • liquid extract refers to a liquid substance in which most of the biomass is removed by solid-liquid separation of the biomass contaminants and palm oil emulsion particles and some biomass particles remaining in water.
  • Coagulant, flocculant or coagulant and flocculant is a target material to be aggregated by sequential addition.
  • coagulant refers to a substance used to adsorb / condense suspended particles to biomass particles in a liquid extract, and is a monomolecular inorganic coagulant, a high molecular weight inorganic coagulant, and a low molecular weight.
  • the organic polymer (molecular weight of 1 million or less) of the, the mono-molecular inorganic coagulant is aluminum sulfate (aluminum sulfate), ferrous sulfate (ferrous sulfate, ferric sulfate), ferric chloride (ferric chloride) and the like are representative, polymer type inorganic condensing agents include polyaluminum chloride (poly aluminum chloride: [Al 2 (OH) n Cl 6 -n] m), polyaluminum sulfate (poly aluminum sulfate: [Al 2 (OH) n (SO 4) 3 - n / 2 ] m ) and the like, and low molecular weight organic polymers include polydicyandiamide, polyamine, and polydiallydimethyldimethylammonium chl.
  • the coagulant according to the present invention may be in the form of a metal salt or any organic polymer, it is preferable to use an organic polymer in consideration of subsequent processes such as extraction of a fat-soluble physiologically active substance, and in particular, the organic polymer coagulant has a cationic property. It is preferable to use a polymer.
  • the coagulant according to the present invention serves to adsorb / condense the suspended particles to the biomass particles in the liquid extract.
  • floculant is a flocculant in order to more effectively perform the solidification of the adsorption / flocculation of the emulsion particles and biomass particles formed by the use of a coagulant in the solid-liquid separation step and solid extract form. It is a generic term for materials used to improve sedimentation and increase dehydration efficiency by coarsening, and is a polymer material having a molecular weight of 300 to 5 million or more, and is a nonionic polymer by homopolymerization mainly based on an acrylamide monomer. Anionic polymers prepared by copolymerization with phosphorus polyacrylamide, acrylate (acrylate) monomers or hydrolysis of acrylamide, etc.
  • the flocculant according to the present invention is very effective in coagulating adsorption / coagulum of emulsion particles and biomass particles to improve sedimentation and increase dehydration efficiency to solidify the solid extract form.
  • coagulant and "flocculant” are defined separately, but only coagulant or coagulant may be used, or more effective when both coagulant and flocculant are used.
  • the "solid extract” refers to palm oil, insoluble (solvent-insoluble) oil palm biomass, which is mostly produced when water is separated and solid-liquid separated by adding a polymer flocculant to the liquid extract. It means a solid material containing fine particles and a small amount of water.
  • Palm oil production by-products to extract the fat-soluble physiologically active substances in the present invention are palm fruit bunch (oil palm bunch), palm pressed fiber (palm pressed fiber) and palm oil mill effluent (palm oil mill effluent). Palm fruits contain both fresh fruit bunches at high temperature, dropping off palm fruits and then squeezed to recover the palm oil. do. These palm fruits and palm pulp fibers contain more physiologically active substances such as carotenoids, tocols and polyphenols, but are reduced rapidly as they decay due to the hot and humid environment of the mountain area, so it is desirable to dry them as soon as they are discharged from the factory. Do. Palm oil plant wastewater contains various water-soluble substances such as biomass, such as palm mesocarp in the form of fine particles, palm oil and protein in the emulsion state, and can be used for extraction of the bioactive substance as it is after being cooled to room temperature.
  • biomass such as palm mesocarp in the form of fine particles, palm oil and protein in the emulsion state
  • a coagulant or flocculant which serves to facilitate dehydration through filtration by adsorbing / coagulating / aggregating the palm oil in the oil state and the palm biomass in the particulate state is polydicyandiamide and polyacrylamide. It is preferable to use a cationic, anionic or nonionic polymer flocculant comprising a), and other coagulants or flocculants as described above may be added according to the type of biomass and the ratio of the emulsion, and are not limited thereto. Do not.
  • the solid extract containing a high concentration of a fat-soluble physiologically active substance prepared from the palm oil preparation by-product provided in the present invention is obtained as a solid after separation of the palm oil containing the fat-soluble physiologically active substance to biomass particles insoluble in water.
  • This solid extract consists of palm oil containing 40 to 70% water, 15 to 40% insoluble biomass and 15 to 30% bioactive material. It may also contain a small amount of coagulant or flocculant added during the preparation of the aggregate.
  • This solid extract contains bioactive substances such as alpha-carotene, beta-carotene, gamma-carotene, lycopene, tocopherol, tocotrienol and vegetable sterol, depending on the by-products of palm oil used, and the content of each bioactive substance depends on the type and composition of the raw materials. It is very different accordingly, and is not specifically limited. For example, when the fresh palm pulp fiber is used as a raw material, the concentration of the fat-soluble physiologically active substance of the solid extract is 2 to 5 times higher than that of the raw material, but the solid extract is 1/5 to 1 / by weight containing about 50% water. Decreases to 20 Among these solid extracts, insoluble in water is a biomass of cellulose main components derived from palm fruits, palm pulp or palm pulp.
  • the present invention is a.
  • biomass gruel manufacturing step of producing biomass grits containing emulsion by immersion by adding water to palm fruits or palm pulp, which is a by-product of palm oil, and by friction grinding;
  • Coagulant, flocculant or coagulant and flocculant are sequentially added to solidify palm oil emulsion particles containing fat-soluble bioactive substances in the liquid extract obtained from the liquid extract preparation step.
  • the fat-soluble physiologically active substance from palm oil manufacturing by-products includes a solid phase extracting step of preparing a solid extract including high concentrations of carotenoids and tocols through solid-liquid separation after the flocculation step but reducing the water content to about 40 to 70%. It provides a method for producing an oil palm biomass solid extract, characterized in that it contains a high concentration.
  • the friction grinding of the biomass grind production step may be to use the emulsification eluting principle of palm oil from the oil palm biomass.
  • the trituration of the biomass grind production step may use a twin screw extruder to extract the fat-soluble physiologically active material from the oil palm biomass.
  • the solid-liquid separation in the liquid extract manufacturing step may use a centrifugal separation method or a filtration method.
  • the step of producing the aggregates using at least one of a cationic, anionic or nonionic polymer flocculant including polydicyandiamide and polyacrylamide as a polymer flocculant It may be.
  • the solid-liquid separation in the solid phase extract manufacturing step may be to use a pressure filtration method including a filter press or a belt press.
  • the first step in the method for preparing a solid extract containing a high concentration of carotenoids and tocols from the palm oil production by-products according to the present invention is to add water to the palm oil production by-products and to prepare biomass grits through frictional grinding.
  • the palm bin or palm pulp fiber crushed is first subjected to 1 to 5 times more water than biomass drying and friction grinding.
  • the friction mill can be used is a twin screw extruder (disc mill) or disc mill (disc mill), in order to reduce the energy consumption and at the same time maximize the friction effect is preferably a twin screw extruder.
  • the palm biomass is crushed in water, and the palm oil contained in the biomass is eluted as emulsified particles by emulsification of glycolipids or phospholipids.
  • the efficiency of emulsifying and eluting palm oil may vary depending on the friction grinding conditions. When considering the properties of semi-solid palm oil at room temperature, the frictional grinding temperature is 20 o C or more and 100 o C or less, and the frictional grinding temperature is 20 to 50 o when additionally considering the carotenoid properties that may be altered at high temperature. C is preferred.
  • the operating conditions of the twin screw extruder or the disk mill are not limited to a specific range because they may vary depending on the type of equipment, the combination of screws or the type of the disk.
  • the second step of the present invention is the solid-liquid separation to prepare an emulsion containing the fat-soluble physiologically active component from the biomass gruel prepared in the first step and a liquid extract containing a small amount of biomass particles.
  • water is further added to the biomass gruel to contain 10 to 20 times more water than during drying to prepare a uniform gruel.
  • the solid-liquid separation of this gruel can be used a variety of methods commonly used in the art, and examples thereof include centrifugation, rotary dehydration, suction filtration and pressure filtration.
  • centrifugal separation using palm oil-containing emulsion particles having a specific gravity smaller than that of water is preferable. That is, some of the biomass particulates (eg, about 1% of the total biomass drying, etc.) are centrifuged at low speed so as to stay in the liquid phase (eg, 1 minute at 200 ⁇ g) and then fine biomass particles
  • the supernatant containing the emulsion can be separated from most of the biomass as a precipitate.
  • both filter press, belt press and centrifugal filtration can be used to separate and recover the emulsion and fine biomass from most biomass.
  • filter press or belt press with high energy recovery and high recovery of liquids can be used for solid-liquid separation.
  • the filter press having the highest recovery rate of the liquid is most preferred.
  • the third step of the present invention is to prepare a solid extract by adsorbing and dehydrating a small amount of biomass microparticles containing an emulsion containing a bioactive material.
  • the liquid extract obtained in the solid-liquid separation of the second step is treated with a polymer coagulant to coagulate the biomass fine particles and the emulsion particles, and thereafter, the coagulant is further treated to coagulate into particles that are hard enough to be filtered under pressure.
  • the polymer coagulant is made into a high concentration aqueous solution, and is added to the liquid phase and stirred while adsorbing to the suspended particles and the fine biomass.
  • the flocculant is then added and stirred and allowed to stand for at least several minutes so that aggregates can form.
  • the polymer coagulant and flocculant cationic, anionic and nonionic polymer coagulant including polydicyandiamide and polyacrylamide may be used, and solid phase extract may be prepared by solid-liquid separation.
  • the type and amount used are not limited as long as the aggregates are as hard as possible.
  • the pressurized filtration which is the lowest the water content of the solid extract obtained as a result of the solid-liquid separation is preferred, and it is more preferable to apply a filter press in terms of low energy consumption and low water content of the solid extract.
  • the solid extract containing high concentration of the bioactive substance prepared in this way is only 2 to 15% of the weight of the raw material biomass when compared to drying, and the water content is low to 40 to 70% by weight, so that a small amount of water-soluble organic solvent or supercritical water, Supercritical carbon dioxide can also extract economically soluble bioactive substances.
  • the present invention is 10 to 30% by weight of palm oil containing a fat-soluble bioactive substance such as carotenoids and tocol produced according to the above method; It provides an oil palm biomass solid phase extract that can be used for the industrial preparation of fat-soluble bioactive substances by solvent extraction, including 15 to 40% by weight of solvent-insoluble oil palm biomass and 40 to 70% by weight of water. .
  • the fat-soluble physiologically active substance may be a carotenoid or tocol, and at least one selected from the group consisting of alpha carotene, beta carotene, gamma carotene, lycopene, cotoperol and tocotrienol. Can be.
  • the oil palm biomass palm oil empty fruit bunch of oil palm
  • palm pressed fiber palm pressed fiber
  • palm oil plant generated as a by-product in the palm oil manufacturing process It may be at least one of palm oil mill effluent.
  • Solid extract containing a high concentration of the fat-soluble physiologically active substance of the present invention prepared as described above may then be used to extract carotenoids and tocol using a solvent. That is, the solvent was added at a ratio of 1: 1 (w / v) to 1:10 (w / v) with respect to the solid extract prepared by reducing the water content in step 3, followed by stirring to extract the bioactive material, followed by centrifugation or Filtration yields a solution containing carotenoids and tocols.
  • the solvent used to extract the fat-soluble physiologically active substance may include a water-soluble organic solvent, a poorly water-soluble organic solvent, supercritical water or supercritical carbon dioxide, and selected in consideration of the solubility and cost of the bioactive substance to be extracted.
  • Examples include water-soluble organic solvents such as alcohols such as ethanol, methanol and isopropyl alcohol, other organic solvents such as tetrahydrofuran, and poorly water-soluble organic solvents such as chloroform, dichloromethane, ethyl acetate, hexane, and other organic solvents.
  • water-soluble organic solvents such as alcohols such as ethanol, methanol and isopropyl alcohol
  • other organic solvents such as tetrahydrofuran
  • poorly water-soluble organic solvents such as chloroform, dichloromethane, ethyl acetate, hexane, and other organic solvents.
  • Supercritical water or supercritical carbon dioxide may be used in combination with the solvent, and all solvents and extraction methods available in the art may be used.
  • the small amount of solid extract containing high concentrations of carotenoids and tocol prepared from palm oil by-products according to the present invention enables economic production of industrial raw materials through solvent extraction and purification of physiologically active substances.
  • the solid extract was prepared by solid-liquid separation using a small filter press (Korea Institute of Chemical Research, Korea) attached to the 6 micron filter cloth. The solid extract was weighed, taken in small amounts and lyophilized to determine the moisture content. In addition, 2 g of this solid extract was taken in a 50 ml falcon tube, followed by ultrasonic extraction with 9 ml of ethanol, followed by centrifugation to prepare a supernatant. Carotenoids were quantified as indicators of fat-soluble bioactive substances by a spectrophotometer (Benchmark Plus microplate spectrophotometer, BIO RAD, USA, 450 nm).
  • the ethanol remaining in the falcon tube was decanted and blown with air to remove the ethanol by volatilization.
  • 50 ml of hexane (n-hexane) was added thereto, followed by ultrasonic extraction, centrifugation and supernatant removed. Air was blown to remove hexane, dried under reduced pressure for 24 hours, and weighed to calculate the weight of the solid extract from which the fat-soluble component was removed.
  • the composition and yield of the palm fruit fruit solid extract from the experimental values were calculated and shown in Table 1.
  • Polydicyandiamide (polydicyandiamide, DC-400, SNF Korea, Korea) was treated in a liquid extract at a concentration of 3,000 mg / L and stirred at a slow rate to cause the emulsion particles to coagulate in the fine biomass.
  • Cationic polyacrylamide (polyacrylamide C-211, SNF Korea, Korea) was added thereto at a concentration of 30 mg / L, and stirred for 60 minutes at room temperature to form an aggregate. After the aggregate was formed, the solid extract was prepared by solid-liquid separation using a small filter press (Korea Institute of Chemical Research, Korea) attached to the 6 micron filter cloth. The solid extract was weighed, taken in small amounts and lyophilized to determine the moisture content.
  • the solid extract was weighed, taken in small amounts and lyophilized to determine the moisture content.
  • 2 g of this solid extract was taken in a 50 ml falcon tube, followed by ultrasonic extraction with 9 ml of ethanol, followed by centrifugation to prepare a supernatant.
  • Carotenoids were quantified as indicators of fat-soluble bioactive substances by a spectrophotometer (Benchmark Plus microplate spectrophotometer, BIO RAD, USA, 450 nm). The ethanol remaining in the falcon tube was decanted and blown with air to remove the ethanol by volatilization.
  • the dried palm fruits and palm pulp fibers were cut and pulverized with a cutter mill (manufactured by Korea Powder Machinery, Korea) to prepare a powder of 20 mesh or less. Palm oil plant wastewater was lyophilized and ground to a powder of 20 mesh or less. 5 g (during drying) of these samples were taken and placed in a Soxhlet wobble, followed by Soxhlet extraction using ethanol as a solvent. The volume of the extract was measured and a portion was taken and centrifuged.
  • Beta carotene was quantified as an indicator of fat-soluble physiologically active substance, and the recovery rate of each example was calculated by comparing this value with the amount of carotenoid or beta carotene obtained in Examples, and the results are shown in Table 1.
  • Palm By-Products Composition (g) Example 1 (palm fruits and vegetables) Example 2 (palm pulp fiber) Example 3 (palm oil factory wastewater) Total amount 35.5 32.1 32.9 water 20.5 17.4 19.4 Insoluble Biomass 8.6 8.4 4.5 Fat-soluble ingredients 6.4 6.3 9.0 Beta-carotene or carotenoids (mg) in biomass (300g) 10.5 (carotenoids) 19.8 (beta carotene) 14.5beta carotene) Beta-carotene or carotenoids (mg) in solid extract 4.8 10.1 12.3 Carotene or carotenoid recovery rate (%) 45 51 85

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Abstract

The present invention relates to a solid phase extract containing, at a high concentration, a fat-soluble physiologically active substance, such as carotenoid and tocol, produced from by-products generated during a process of producing palm oil, and a method for producing the same. Since a fat-soluble physiologically active substance, which is contained in palm biomass at a low concentration and can only be extracted by using a large amount of solvent, is extracted by using only water and then adsorbed on a small amount of biomass to be solidified, the fat-soluble physiologically active substance subsequently can be extracted and recovered even after extraction with a small amount of solvent, whereby the present invention can produce raw materials useful for the industrial production of various physiologically active substances possessed by palm biomass. In addition, the present invention is a useful method to improve the economic feasibility of biorefinery by increasing the value added of palm oil production by-products.

Description

팜유 제조 부산물로부터 제조한 지용성 생리활성물질을 고농도로 포함하는 오일팜 바이오매스 고상추출물 및 그의 제조 방법Oil palm biomass solid extract containing high concentration of fat-soluble physiologically active substance prepared from palm oil manufacturing by-product and its manufacturing method
본 발명은 팜유 제조 후 남겨지는 부산물 혹은 폐기물로부터 지용성 생리활성물질인 카로티노이드, 토코페롤 및 토코트리에놀 등을 추출/회수하는 방법과 이 방법에 의해 제조된 카로티노이드 등 지용성 생리활성물질을 고농도로 함유하는 오일팜 바이오매스 고상추출물에 관한 것이다.The present invention is a method for extracting / recovering fat-soluble bioactive substances carotenoids, tocopherols and tocotrienols from the by-products or wastes left after the production of palm oil, and oil palm bio-containing high concentrations of fat-soluble bioactive substances such as carotenoids produced by the method. It relates to mass solid extract.
보다 구체적으로는 지용성 생리활성물질을 함유하는 팜유 10 내지 30 중량%, 불용성(solvent-insoluble) 오일팜 바이오매스 15 내지 40 중량% 및 물 40 내지 70 중량%를 포함하여 용매 추출에 의해 지용성 생리활성물질의 공업적 제조에 사용할 수 있는 오일팜 바이오매스 고상추출물 및 이의 제조방법에 대한 것이다.More specifically, the fat-soluble physiological activity by solvent extraction, including 10 to 30% by weight palm oil containing the fat-soluble bioactive substance, 15 to 40% by weight of solvent-insoluble oil palm biomass and 40 to 70% by weight of water The present invention relates to an oil palm biomass solid extract and a method for preparing the same that can be used for industrial production of materials.
본 출원은 2016년 12월 2일에 출원된 한국 특허출원 제10-2016-0163850호에 기초한 우선권을 주장하며, 해당 출원의 명세서 및 도면에 개시된 모든 내용은 본 출원에 원용된다.This application claims priority based on Korean Patent Application No. 10-2016-0163850, filed December 2, 2016, and all the contents disclosed in the specification and drawings of the application are incorporated in this application.
오일팜 열매로부터 생산되는 팜유는 다른 식물성 기름과는 다르게 포화지방산과 불포화지방산이 1:1의 비율로 구성되어 있어서 동물성 유지와 같이 상온에서 반고체의 상태를 나타낸다. 정제되지 않은 팜유는 CPO(crude palm oil)라 불리며, 500 내지 1,600 mg/kg의 카로티노이드(carotenoids), 600 내지 1,000 mg/kg의 토코페롤(tocopherol)과 토코트리에놀(tocotrienol), 코엔자임Q10(coenzyme Q10), 파이토스테롤(phytosterol)과 같은 고부가가치 생리활성물질을 함유하고 있고, 베타카로틴(β-carotene)에 의해 붉은색을 나타낸다. Unlike other vegetable oils, palm oil produced from oil palm fruit is composed of saturated fatty acid and unsaturated fatty acid in a ratio of 1: 1, so it shows semi-solid state at room temperature like animal oil or fat. Unrefined palm oil is called crude palm oil (CPO), and 500 to 1,600 mg / kg carotenoids, 600 to 1,000 mg / kg tocopherol and tocotrienol, coenzyme Q10, It contains high value-added bioactive substances such as phytosterol and is red by beta-carotene.
팜유 제조 과정에서 부산물로 배출되는 팜 공과방(EFB, empty fruit bunch of oil palm)은 팜 열매의 약 23 중량%를 차지하며, 일반적으로 수분 함량 약 40 중량%까지 건조된 것으로, 극히 일부분이 팜유 제조 공장의 보일러 연료로 사용되고, 이 후 남은 재와 대부분의 공과방은 비료와 퇴비로 사용되고 있다. 팜 열매를 고온에서 증자하여 과실을 탈락시키는 과정에서 팜유의 일부(예컨대 4.6 중량% 등)가 팜 공과방에 남게 되고, 이로 인하여 팜 공과방은 상기 여러 가지 생리활성물질도 함유하게 된다. Empty fruit bunch of oil palm (EFB), which is produced as a by-product of palm oil production, accounts for about 23% by weight of palm fruit, and is generally dried to about 40% by weight of moisture. It is used as boiler fuel in manufacturing plants, and the remaining ash and most of the process rooms are used for fertilizers and compost. Part of the palm oil (e.g., 4.6% by weight) is left in the palm fruits in the process of increasing the palm fruit at high temperature to remove the fruits, which causes the palm fruits to contain the various bioactive substances.
팜유를 머금고 있는 팜 열매 내에 거미줄처럼 얽혀 있다가 착즙 과정에서 유리되는 팜 과육섬유(palm pressed fiber, PPF)는 팜 열매의 15%를 차지하며, 많은 양의 팜유를 함유하므로 열량이 높아 팜 공과방과 함께 팜유 제조 공장의 보일러 연료로 사용된다. 이 팜 과육섬유는 팜유를 5 내지 7 중량% 함유하고 있으며, 카로티노이드를 4,000 내지 6,000 mg/kg, 토콜을 2,400 내지 3,500 mg/kg 함유하여 팜유보다 많은 생리활성물질을 함유하고 있는 것으로 알려져 있다(Choo 등, JAOCS, 1996, 73, 599-602.).Palm pressed fiber (PPF), which is entangled like cobwebs in palm fruits containing palm oil and is released during the extraction process, accounts for 15% of palm fruits and contains a large amount of palm oil. Along with the room, it is used as boiler fuel for palm oil manufacturing plants. This palm pulp fiber contains 5 to 7% by weight of palm oil, 4,000 to 6,000 mg / kg of carotenoids and 2,400 to 3,500 mg / kg of tocols, which are known to contain more bioactive substances than palm oil (Choo etc., JAOCS, 1996, 73, 599-602 .).
또한, 갓 따온 팜 열매(fresh fruit bunch of oil palm)를 고온의 증기로 쪄서 팜 너트를 탈락시킨 후 너트를 압착하고 고액분리하여 팜유를 회수하는 과정에서 발생하는 팜유 공장폐수(POME, palm oil mill effluent)는 95-96 중량%의 수분과 0.6-0.7 중량%의 지방, 그리고 4-5 중량%의 고형분을 포함하고 있으며, 단백질, 탄수화물, 지방, 미네랄 등이 높은 농도로 존재하여 미생물 발효에 의해 유용물질 생산에 이용될 수 있지만, 대부분은 폐수처리장에 버려지거나 바이오가스 제조용 원료로 이용된다. 여기에도 팜유가 상당량 함유되어 있으며, 이로 인하여 많은 양의 생리활성물질(카로티노이드의 경우 약 1,500 mg/kg, Ahmad 등, Desalination Water Treat, 2009, 7, 251-256.)을 포함한다. In addition, the palm fruit mill waste water (POME, palm oil mill) generated in the process of recovering palm oil by squeezing the nut and separating the liquid from the palm nut by steaming fresh fruit bunch of oil palm with high temperature steam. effluent) contains 95-96% by weight of water, 0.6-0.7% by weight of fat, and 4-5% by weight of solids. Protein, carbohydrates, fats and minerals are present in high concentrations. It can be used for the production of useful substances, but most of them are disposed of in wastewater treatment plants or used as raw materials for biogas production. It also contains a significant amount of palm oil, which contains a large amount of bioactive substances (about 1,500 mg / kg for carotenoids, Ahmad et al., Desalination Water Treat , 2009, 7, 251-256.).
상기와 같이 팜유 생산 공정 부산물들에는 상당량의 지용성 성분들이 포함되어 있고, 이러한 성분들에는 베타카로틴, 알파카로틴, 토코페롤, 토코트리에놀과 같은 고부가가치 생리활성물질도 포함된다. 베타카로틴은 항산화활성을 나타내며, 프로비타민 A 활성을 가지고 있고, 췌장암, 직장암, 전립선암, 유방암, 흑색종, 피부암과 같은 여러 가지 암 발생을 억제하는 효과와 백내장 예방 효과를 나타내는 특징이 있다. 알파카로틴도 역시 암 예방 효과를 나타내고 항산화 활성을 가지며 그 활성은 베타카로틴보다 우수하지만 프로비타민 A 활성은 베타카로틴의 절반을 나타낸다. 토코페롤은 항산화제로서 비타민 E 활성을 나타내며 다른 항산화제와 함께 사용하면 황반변성 예방 효과를 나타내고, 일부 암과 백내장, 파킨슨병의 예방효과가 있다. 또한, 식품의 방부제로 사용되기도 한다. 토코트리에놀은 토코페롤보다 더 효율적인 항산화제로서 비타민 E 활성을 나타내며, 암 형성 저해, 콜레스테롤 형성 억제 효과를 나타낸다. As mentioned above, palm oil production process by-products contain a significant amount of fat-soluble components, and these components also include high value-added bioactive substances such as beta carotene, alpha carotene, tocopherol and tocotrienol. Beta-carotene has an antioxidant activity, has provitamin A activity, and has the characteristics of inhibiting the occurrence of various cancers such as pancreatic cancer, rectal cancer, prostate cancer, breast cancer, melanoma and skin cancer and preventing cataracts. Alpha-carotene also has a cancer preventive effect and antioxidant activity and its activity is superior to beta-carotene, but provitamin A activity represents half of beta-carotene. Tocopherol is an antioxidant that has vitamin E activity. When used in conjunction with other antioxidants, tocopherol prevents macular degeneration and prevents some cancers, cataracts, and Parkinson's disease. It is also used as a food preservative. Tocotrienols are more efficient antioxidants than tocopherols and have vitamin E activity, inhibit cancer formation and inhibit cholesterol formation.
이러한 생리활성 물질들은 고부가가치 화합물로서 팜유 제조 부산물에 많은 양이 존재하나 대부분 회수되지 못하고 버려지는 실정이다. 현재 이러한 베타카로틴, 알파카로틴, 토코페롤, 토코트리에놀을 포함하는 지용성 물질들이 팜유로부터 추출되고 있지만, 그 양은 극히 제한적이다. 특히, 대부분의 베타카로틴은 화학적 합성으로 제조되어 천연물질보다 효능이 떨어지지만, 그 제조단가는 kg당 2,000 미국달러로 알려져 있다. 하지만, 이러한 지용성 생리활성물질들을 팜유 제조 부산물로부터 값싸게 추출할 수 있다면 천연 생리활성물질로서 그 부가가치는 합성물질 이상이 될 것으로 예상된다. These bioactive materials are high value-added compounds present in a large amount in the by-products of palm oil production, but most of them are not recovered. Currently, fat-soluble substances including such beta-carotene, alpha-carotene, tocopherol, tocotrienol are extracted from palm oil, but the amount is extremely limited. In particular, most beta-carotene is produced by chemical synthesis, which is less effective than natural substances, but the manufacturing cost is known to be 2,000 US dollars per kg. However, if these fat-soluble bioactive substances can be extracted inexpensively from palm oil manufacturing by-products, it is expected that their added value as natural bioactive substances will be more than synthetic materials.
이러한 이유로 최근까지 버려지는 팜유 제조 부산물로부터 생리활성 물질을 추출하는 연구가 꾸준히 이루어져 오고 있으나 아직 산업화되지는 못하였다. 특허 기술로는 팜 지방산 증류물로부터 토코페롤과 토코트리에놀을 추출한 것에 대해서만이 보고되어 있다(미국 등록특허공보 제5190618호, 대한민국 등록특허공보 제10-1481197호). 이들은 지용성 생리활성물질의 추출에 핵산 등 유기용매를 사용하였으며, 일부 추출 연구에 초임계수 혹은 초임계 이산화탄소 등을 사용하였다. For this reason, researches on extracting physiologically active substances from palm oil by-products discarded until recently have been steadily conducted, but they have not been industrialized yet. As a patented technology, only the extraction of tocopherol and tocotrienol from palm fatty acid distillate has been reported (US Patent No. 5190618, Korean Patent Publication No. 10-1481197). They used organic solvents such as nucleic acids for the extraction of fat-soluble bioactive substances and supercritical water or supercritical carbon dioxide for some extraction studies.
이렇게 대량의 바이오매스에 낮은 농도로 함유되어 있는 지용성 생리활성물질을 용매로 추출하는 데에는 바이오매스의 작은 가비중(bulk density, 팜 공과방은 0.1 g/cm3 내외)으로 인하여 바이오매스 무게의 5배 이상의 유기용매와 대형 추출장비를 사용해야 하는 등 과도한 비용 발생이 불가피하므로 보다 실용적인 추출 방법이 필요하다. The solvent-based extraction of fat-soluble physiologically active substances contained in such a large amount of biomass at low concentrations is 0.1 g / cm 3 for the bulk density of the biomass. Due to the excessive cost is inevitable, such as the use of an organic solvent and a large extraction equipment more than five times the weight of the biomass weight, more practical extraction methods are required.
본 발명자들은 팜 부산물이 함유하는 지용성 생리활성물질이 팜유에 녹아 있으며, 이 팜유는 물과 함께 있는 상태에서 마찰 분쇄할 때 수중에 유화 용출되는 특징이 있다는 것을 발견하였다. 또한, 이 지용성 생리활성물질을 함유하는 유탁입자는 응결제(coagulant)에 의해 바이오매스 미립자에 부착되고, 필요에 따라 추가적인 응집제(flocculant)의 사용에 의하여 조대화에 의한 침강성이 개선되므로 탈수효율을 증가시켜 고액분리를 통하여 고체화할 수 있었다. 이렇게 제조한 고상 추출물은 팜 부산물이 가지고 있는 지용성 생리활성물질을 고농도로 함유하면서 바이오매스 부피의 1% 정도에 불과하므로 간편하게 다룰 수 있다. 또한, 소량의 용매로도 생리활성물질을 고농도로 추출할 수 있으므로 팜 부산물이 함유하는 고부가가치 생리활성물질의 산업적 제조에 유용하다.The present inventors have found that the fat-soluble physiologically active substance contained in the palm oil by-product is dissolved in palm oil, and this palm oil has the characteristic of emulsifying and eluting in water when friction-pulverizing with water. In addition, emulsion particles containing this fat-soluble physiologically active substance are attached to the biomass fine particles by coagulant, and if necessary, additional flocculant improves sedimentation by coarsening, thereby increasing dehydration efficiency. To solidify through solid-liquid separation. The solid extract prepared in this way can be easily handled because it contains only a 1% of the volume of biomass while containing a high concentration of fat-soluble physiologically active substances of palm by-products. In addition, since the bioactive substance can be extracted at a high concentration even with a small amount of solvent, it is useful for the industrial production of high value-added bioactive substances contained in palm by-products.
본 발명은 상기 문제점들을 해결하기 위해 개발된 것으로, 팜유 제조 부산물의 작은 가비중 혹은 과도한 물 함량으로 인하여 낮은 농도로 함유하는 지용성 생리활성물질을 추출함에 있어서 보다 간편하고 경제적인 방법을 제공하는 것을 목적으로 한다.The present invention was developed to solve the above problems, and aims to provide a simpler and more economical method for extracting a fat-soluble physiologically active substance containing a low concentration due to the small weight or excessive water content of palm oil production by-products. It is done.
본 발명에서는 카로티노이드 등 지용성 생리활성물질을 고농도로 함유하면서 바이오매스 부피의 1% 정도에 불과하여 간편하게 다룰 수 있는 지용성 생리활성물질을 함유하는 유탁입자를 고체화한 오일팜 바이오매스 고상 추출물 및 이의 제조방법을 제공하고자 한다.In the present invention, oil palm biomass solid phase extract solidifying emulsion particles containing fat-soluble physiologically active substances that can be easily handled with only about 1% of the volume of biomass while containing a high concentration of fat-soluble physiologically active substances such as carotenoids, and a preparation method thereof. To provide.
본 발명에서는 상기 과제를 해결하기 위하여 지용성 생리활성물질을 함유하는 팜유 10 내지 30 중량%, 불용성(solvent-insoluble) 오일팜 바이오매스 15 내지 40 중량% 및 물 40 내지 70 중량%를 포함하여 용매 추출에 의해 지용성 생리활성물질의 공업적 제조에 사용할 수 있는 오일팜 바이오매스 고상추출물을 제공한다.In order to solve the above problems, the present invention provides solvent extraction including 10 to 30% by weight of palm oil containing fat-soluble physiologically active substance, 15 to 40% by weight of solvent-insoluble oil palm biomass and 40 to 70% by weight of water. It provides an oil palm biomass solid extract that can be used in the industrial production of fat-soluble physiologically active substances.
본원 발명에서는 팜유 제조 부산물을 물에 침지한 후 마찰 분쇄하여 유탁액을 함유하는 바이오매스 곤죽을 제조하는 바이오매스 곤죽 제조단계; 상기 바이오매스 곤죽 제조단계에서 얻은 바이오매스 곤죽을 고액분리하여 바이오매스 미립자 및 유탁입자를 함유하는 액상 추출물을 제조하는 액상 추출물 제조단계; 상기 액상 추출물 제조단계부터 얻은 액상 추출물 중 지용성 생리활성물질을 함유하는 팜유 유탁입자를 고체화하기 위해 응결제(coagulant), 응집제(flocculant) 또는 응결제(coagulant)와 응집제(flocculant)를 순차적으로 가하여 유탁입자를 바이오매스 미립자와 흡착/응결/응집시키는 응집물 제조단계; 및 상기 응집물 제조단계 이후 고액분리를 통하여 고상 추출물을 제조하는 고상 추출물 제조단계;를 포함하여 팜유 제조 부산물로부터 지용성 생리활성물질을 고농도로 함유하는 것을 특징으로 하는 오일팜 바이오매스 고상 추출물의 제조 방법을 제공한다.According to the present invention, the biomass gruel manufacturing step of manufacturing a biomass gruel containing an emulsion by immersing the byproduct oil by-products in water and friction grinding; Liquid extract manufacturing step of preparing a liquid extract containing biomass fine particles and emulsion particles by solid-liquid separation of the biomass gruel obtained in the biomass gruel manufacturing step; Coagulant, flocculant or coagulant and flocculant are sequentially added to solidify palm oil emulsion particles containing fat-soluble bioactive substances in the liquid extract obtained from the liquid extract preparation step. Preparing agglomerates to adsorb / coagulate / aggregate the biomass particles; And a solid extract preparation step of preparing a solid extract through solid-liquid separation after the agglomerate preparation step; and a process for producing an oil palm biomass solid phase extract, comprising a fat-soluble physiologically active substance from palm oil manufacturing by-products at a high concentration. to provide.
본 발명에 따른 지용성 생리활성물질을 함유하는 유탁입자를 고체화한 오일팜 바이오매스 고상 추출물은 팜 부산물이 가지고 있는 지용성 생리활성물질을 고농도로 함유하면서 바이오매스 부피의 1% 정도에 불과하므로 간편하게 다룰 수 있다. 또한, 소량의 용매로도 생리활성물질을 고농도로 추출할 수 있으므로 팜 부산물이 함유하는 고부가가치 생리활성물질의 산업적 제조에 유용하다. The oil palm biomass solid extract solidifying emulsion particles containing fat soluble bioactive substances according to the present invention can be easily handled because it contains only about 1% of the volume of biomass while containing a high concentration of fat soluble bioactive substances which palm by-products have. have. In addition, since the bioactive substance can be extracted at a high concentration even with a small amount of solvent, it is useful for the industrial production of high value-added bioactive substances contained in palm by-products.
본 발명은 팜 공과방, 팜 과육섬유 및 팜유 공장폐수로부터 베타카로틴 등 고부가가치 지용성 생리활성물질을 고농도로 함유하는 고상 추출물을 제조할 수 있게 됨으로써, 이를 원료로 하여 소량의 유기용매 혹은 초임계 추출 등 기존의 각종 추출기술과 크로마토그래피 등의 정제 기술을 활용하여 지용성 생리활성물질을 산업적으로 제조하는데 유용하다.The present invention enables to prepare a solid extract containing a high concentration of high value-added fat-soluble physiologically active substances such as beta-carotene from palm fruits, palm pulp fiber and palm oil plant wastewater, using as a raw material a small amount of organic solvent or supercritical extraction It is useful for industrially preparing fat-soluble physiologically active substances by utilizing various conventional extraction techniques and purification techniques such as chromatography.
도 1은 본원 발명의 일 구현예에 따른 오일팜 바이오매스 고상추출물의 제조단계를 나타낸 공정도이다.1 is a process chart showing the manufacturing step of the oil palm biomass solid extract according to an embodiment of the present invention.
이하, 본 발명에 대해 상세하게 설명하기로 한다. 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본원 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the present invention will be described in detail. The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
본 명세서의 전반에 걸쳐 사용되는 용어인 “지용성 생리활성물질”은 물에는 거의 녹지 않고 유기용매에 잘 녹는 생화학물질로, 알파카로틴, 베타카로틴 및 감마카로틴 등의 카로티노이드(carotenoid), 토코페롤과 토코트리에놀을 포함하는 토콜(tocols) 등 팜 공과방, 팜 과육섬유 및 팜유 공장 폐수 등이 함유하는 생리활성물질을 의미한다. As used throughout this specification, the term “lipophilic bioactive substance” is a biochemical that is hardly soluble in water and soluble in organic solvents. Carotenoids such as alpha carotene, beta carotene and gamma carotene, tocopherol and tocotrienol It refers to bioactive substances contained in palm fruits, palm pulp fiber and palm oil plant wastewater such as tocols.
본 발명에서 “카로티노이드” 혹은 “베타카로틴”이라 함은 여러 가지 카로틴을 함유하는 포괄적인 의미로서 카로티노이드와, 이 중 베타 형태의 물질을 지칭하는 물질을 각각 지칭하지만, 토콜 등 다른 지용성 생리활성물질을 상징하는 의미로도 사용된다. In the present invention, "carotenoid" or "beta carotene" refers to a carotenoid and a beta form of the substance as a generic meaning containing various carotenes, respectively, but refers to other fat-soluble bioactive substances such as tocols. It is also used as a symbolic meaning.
본 발명에서 “바이오매스 곤죽”은 바이오매스에 물을 가하고 마찰식 분쇄를 통하여 제조되고, 지용성 생리활성물질을 함유하는 팜유 유탁입자와 바이오매스 분쇄물이 함유되어 있는 바이오매스 현탁액을 의미한다. 이 바이오매스 곤죽은 팜유 유탁액과 일부 미세 바이오매스를 대부분의 불용성 바이오매스로부터 분리하는 1차 고액분리의 대상 원료로 사용한다. In the present invention, "biomass gruel" refers to a biomass suspension prepared by adding water to biomass and friction grinding, and containing palm oil emulsion particles and biomass powder containing fat-soluble physiologically active substances. This biomass gruel is used as a raw material for primary solid-liquid separation, which separates palm oil emulsions and some fine biomass from most insoluble biomass.
본 발명에서 “액상 추출물”은 상기 바이오매스 곤죽을 고액분리하여 대부분의 바이오매스는 제거되고 지용성 생리활성물질이 녹아있는 팜유 유탁입자와 일부 바이오매스 미립자가 물에 남아있는 액상물을 의미하며, 이후 응결제(coagulant), 응집제(flocculant) 또는 응결제(coagulant)와 응집제(flocculant)의 순차적인 첨가에 의하여 응집시킬 대상 물질이다.In the present invention, "liquid extract" refers to a liquid substance in which most of the biomass is removed by solid-liquid separation of the biomass contaminants and palm oil emulsion particles and some biomass particles remaining in water. Coagulant, flocculant or coagulant and flocculant is a target material to be aggregated by sequential addition.
본 발명에서 “응결제(coagulant)”는 액상 추출물에서 유탁입자를 바이오매스 미립자에 흡착/응결시키기 위하여 사용하는 물질을 총칭하는 것으로, 크게 금속염의 형태인 단분자 무기계 응결제, 고분자형 무기계 응결제 및 저분자량의 유기계 중합체(분자량 100만 이하)로 구분될 수 있고, 상기 단분자 무기계 응결제로는 황산 알루미늄(aluminum sulfate), 황산 철(ferrous sulfate, ferric sulfate), 염화철(ferric chloride) 등이 대표적이고, 상기 고분자형 무기계 응결제로는 폴리 알루미늄 클로라이드(poly aluminum chloride: [Al2(OH)nCl6 -n]m), 폴리 알루미늄 설페이트(poly aluminum sulfate: [Al2(OH)n(SO4)3 -n/ 2]m) 등이 대표적이며, 저분자량의 유기계 중합체로는 폴리디시안디아미드(polydicyandiamide), 폴리아민(polyamine), 폴리디아릴디메틸암모늄 클로라이드(Polydiallyldimethylammonium chloride: polyDADMAC 또는 polyDDA) 등이 대표적이다. 본 발명에 따른 응결제는 금속염의 형태 또는 유기계 중합체 어느것을 사용하여도 무방하지만 지용성 생리활성물질의 추출 등 후속 공정을 고려하면 유기계 중합체를 사용하는 것이 바람직하고, 특히, 유기계 중합체 응결제는 양이온성을 가지고 있는 고분자를 사용하는 것이 바람직하다. 본 발명에 따른 응결제는 액상 추출물에서 유탁입자를 바이오매스 미립자에 흡착/응결시키기는 역할을 하게 된다.In the present invention, "coagulant" refers to a substance used to adsorb / condense suspended particles to biomass particles in a liquid extract, and is a monomolecular inorganic coagulant, a high molecular weight inorganic coagulant, and a low molecular weight. The organic polymer (molecular weight of 1 million or less) of the, the mono-molecular inorganic coagulant is aluminum sulfate (aluminum sulfate), ferrous sulfate (ferrous sulfate, ferric sulfate), ferric chloride (ferric chloride) and the like are representative, polymer type inorganic condensing agents include polyaluminum chloride (poly aluminum chloride: [Al 2 (OH) n Cl 6 -n] m), polyaluminum sulfate (poly aluminum sulfate: [Al 2 (OH) n (SO 4) 3 - n / 2 ] m ) and the like, and low molecular weight organic polymers include polydicyandiamide, polyamine, and polydiallydimethyldimethylammonium chl. oride: polyDADMAC or polyDDA). Although the coagulant according to the present invention may be in the form of a metal salt or any organic polymer, it is preferable to use an organic polymer in consideration of subsequent processes such as extraction of a fat-soluble physiologically active substance, and in particular, the organic polymer coagulant has a cationic property. It is preferable to use a polymer. The coagulant according to the present invention serves to adsorb / condense the suspended particles to the biomass particles in the liquid extract.
본 발명에서 “응집제(flocculant)”는 응결제(coagulant)의 사용에 의하여 형성된 유탁입자와 바이오매스 미립자의 흡착/응결물을 이후 고액분리단계 및 고상 추출물 형태로 고체화하는 것을 더욱 효과적으로 수행하기 위하여 응결물을 조대화하여 침강성을 개선하고 탈수효율을 증가시키기 위하여 사용하는 물질을 총칭하는 것으로, 분자량이 300 내지 500만 이상인 고분자 물질로 주로 아크릴아미드(acrylamide) 단량체를 기반으로 하는 단독 중합에 의한 비이온성 고분자인 폴리아크릴아미드, 아크릴레이트(acrylate)계 단량체와 공중합 또는 아크릴아미드의 가수분해 등을 통하여 제조되는 음이온성 고분자 또는 양이온성 단량체와 공중합에 의한 양이온성 고분자 등을 사용할 수 있다. 본 발명에 따른 응집제는 유탁입자와 바이오매스 미립자의 흡착/응결물을 조대화하여 침강성을 개선하고 탈수효율을 증가시켜 고상 추출물 형태로 고체화하는데 매우 효과적이다.In the present invention, "flocculant" is a flocculant in order to more effectively perform the solidification of the adsorption / flocculation of the emulsion particles and biomass particles formed by the use of a coagulant in the solid-liquid separation step and solid extract form. It is a generic term for materials used to improve sedimentation and increase dehydration efficiency by coarsening, and is a polymer material having a molecular weight of 300 to 5 million or more, and is a nonionic polymer by homopolymerization mainly based on an acrylamide monomer. Anionic polymers prepared by copolymerization with phosphorus polyacrylamide, acrylate (acrylate) monomers or hydrolysis of acrylamide, etc. or cationic polymers by copolymerization with cationic monomers may be used. The flocculant according to the present invention is very effective in coagulating adsorption / coagulum of emulsion particles and biomass particles to improve sedimentation and increase dehydration efficiency to solidify the solid extract form.
본 발명에서는 “응결제(coagulant)”와 “응집제(flocculant)”의 역할을 구분하여 정의하였으나, 필요에 따라서 응결제만을 사용하거나 응집제만을 사용할 수도 있고, 응결제와 응집제 모두를 사용하는 경우에 보다 효과적이다.In the present invention, the roles of "coagulant" and "flocculant" are defined separately, but only coagulant or coagulant may be used, or more effective when both coagulant and flocculant are used.
본 발명에서 “고상 추출물”은 상기 액상 추출물에 고분자 응집제를 가하여 응집시킨 후 고액분리하였을 때 생성되는, 물이 대부분 제거되고 지용성 생리활성물질을 함유하는 팜유, 불용성(solvent-insoluble) 오일팜 바이오매스 미립자 및 소량의 물을 함유하는 고체상 물질을 의미한다. In the present invention, the "solid extract" refers to palm oil, insoluble (solvent-insoluble) oil palm biomass, which is mostly produced when water is separated and solid-liquid separated by adding a polymer flocculant to the liquid extract. It means a solid material containing fine particles and a small amount of water.
본 발명에서 지용성 생리활성물질을 추출하고자 하는 팜유 제조 부산물은 팜 공과방(empty fruit bunch of oil palm), 팜 과육섬유(palm pressed fiber) 및 팜유 공장폐수(palm oil mill effluent)이다. 팜 공과방은 신선한 팜 과실(fresh fruit bunch)을 고온에서 증자하여 팜 과일(palm fruit)을 탈락시킨 후 배출된 것, 혹은 여기에 묻어 있는 팜유를 회수하기 위해 압착한 후 배출되는 것 모두를 포함한다. 이 팜 공과방과 팜 과육섬유는 신선할수록 카로티노이드, 토콜 및 폴리페놀 등 생리활성물질을 더 많이 함유하지만, 산지의 덥고 습한 환경에 의해 부패하면서 급격하게 감소하므로 공장에서 배출되는 즉시 신속하게 건조된 것이 바람직하다. 팜유 공장폐수는 미립자 상태의 팜 과육(palm mesocarp) 등의 바이오매스, 유탁상태의 팜유 및 단백질 등 각종 수용성 물질을 함유하므로 상온까지 냉각시킨 후 그대로 상기 생리활성물질의 추출에 사용될 수 있다.Palm oil production by-products to extract the fat-soluble physiologically active substances in the present invention are palm fruit bunch (oil palm bunch), palm pressed fiber (palm pressed fiber) and palm oil mill effluent (palm oil mill effluent). Palm fruits contain both fresh fruit bunches at high temperature, dropping off palm fruits and then squeezed to recover the palm oil. do. These palm fruits and palm pulp fibers contain more physiologically active substances such as carotenoids, tocols and polyphenols, but are reduced rapidly as they decay due to the hot and humid environment of the mountain area, so it is desirable to dry them as soon as they are discharged from the factory. Do. Palm oil plant wastewater contains various water-soluble substances such as biomass, such as palm mesocarp in the form of fine particles, palm oil and protein in the emulsion state, and can be used for extraction of the bioactive substance as it is after being cooled to room temperature.
본 발명에서 유탁상태의 팜유와 미립자 상태의 팜 바이오매스를 서로 흡착/응결/응집시켜서 여과를 통한 탈수를 용이하게 하는 역할을 하는 응결제 혹은 응집제는 폴리디시안디아미드(polydicyandiamide)와 폴리아크릴아미드(polyacrylamide)를 포함하는 양이온성, 음이온성 혹은 비이온성의 고분자 응집제를 사용하는 것이 바람직하며, 바이오매스의 종류와 유탁액의 비율에 따라서 다른 앞서 기재한 다른 응결제 또는 응집제를 추가하여 사용할 수 있으므로 이에 제한되지 않는다.In the present invention, a coagulant or flocculant which serves to facilitate dehydration through filtration by adsorbing / coagulating / aggregating the palm oil in the oil state and the palm biomass in the particulate state is polydicyandiamide and polyacrylamide. It is preferable to use a cationic, anionic or nonionic polymer flocculant comprising a), and other coagulants or flocculants as described above may be added according to the type of biomass and the ratio of the emulsion, and are not limited thereto. Do not.
본 발명에서 제공하는 팜유 제조 부산물로부터 제조한 지용성 생리활성물질을 고농도로 함유하는 고상 추출물은 지용성 생리활성물질을 함유하는 팜유가 물에 불용성인 바이오매스 미립자에 흡착되어 고액분리 후에 고체로 얻어진다. 이 고상 추출물은 40 내지 70%의 물, 15 내지 40%의 불용성(solvent-insoluble) 바이오매스 및 15 내지 30%의 생리활성물질을 함유하는 팜유로 구성된다. 또한, 여기에는 응집물 제조과정에서 첨가된 소량의 응결제 또는 응집제가 함유되어 있을 수 있다. 이 고상 추출물은 사용한 팜유 제조 부산물에 따라 알파카로틴, 베타카로틴, 감마카로틴, 라이코펜, 토코페롤, 토코트리에놀 및 식물성 스테롤 등의 생리활성물질을 함유하며, 각 생리활성물질의 함량은 원료물질의 종류와 조성에 따라 매우 달라지므로 특별히 한정되지 않는다. 예컨대, 신선도가 높은 팜 과육섬유를 원료로 하였을 때 고상 추출물의 지용성 생리활성물질의 농도는 원료의 2 배 내지 5 배가 되지만, 고상 추출물은 수분을 50% 가량 함유하는 중량으로 1/5 내지 1/20으로 감소한다. 이 고상 추출물 중 물에 불용성인 성분은 팜 공과방, 팜 과육섬유 혹은 팜 과육에서 유래하는 셀룰로오스 주성분의 바이오매스이다. The solid extract containing a high concentration of a fat-soluble physiologically active substance prepared from the palm oil preparation by-product provided in the present invention is obtained as a solid after separation of the palm oil containing the fat-soluble physiologically active substance to biomass particles insoluble in water. This solid extract consists of palm oil containing 40 to 70% water, 15 to 40% insoluble biomass and 15 to 30% bioactive material. It may also contain a small amount of coagulant or flocculant added during the preparation of the aggregate. This solid extract contains bioactive substances such as alpha-carotene, beta-carotene, gamma-carotene, lycopene, tocopherol, tocotrienol and vegetable sterol, depending on the by-products of palm oil used, and the content of each bioactive substance depends on the type and composition of the raw materials. It is very different accordingly, and is not specifically limited. For example, when the fresh palm pulp fiber is used as a raw material, the concentration of the fat-soluble physiologically active substance of the solid extract is 2 to 5 times higher than that of the raw material, but the solid extract is 1/5 to 1 / by weight containing about 50% water. Decreases to 20 Among these solid extracts, insoluble in water is a biomass of cellulose main components derived from palm fruits, palm pulp or palm pulp.
본 발명은 The present invention
1) 팜유 제조 부산물인 팜 공과방 혹은 팜 과육섬유에 물을 가하여 침지한 후 마찰식 분쇄를 통하여 유탁액을 함유하는 바이오매스 곤죽을 제조하는 바이오매스 곤죽 제조단계;1) a biomass gruel manufacturing step of producing biomass grits containing emulsion by immersion by adding water to palm fruits or palm pulp, which is a by-product of palm oil, and by friction grinding;
2) 상기 바이오매스 곤죽 제조단계에서 얻은 바이오매스 곤죽을 고액분리하여 바이오매스 미립자 및 유탁입자를 함유하는 액상 추출물을 제조하는 액상 추출물 제조단계;2) a liquid extract manufacturing step of preparing a liquid extract containing biomass fine particles and emulsion particles by solid-liquid separation of the biomass gruel obtained in the biomass gruel manufacturing step;
3) 상기 액상 추출물 제조단계로부터 얻은 액상 추출물 중 지용성 생리활성물질을 함유하는 팜유 유탁입자를 고체화하기 위해 응결제(coagulant), 응집제(flocculant) 또는 응결제(coagulant)와 응집제(flocculant)를 순차적으로 가하여 유탁입자를 바이오매스 미립자와 흡착/응결/응집시키는 응집물 제조단계; 및3) Coagulant, flocculant or coagulant and flocculant are sequentially added to solidify palm oil emulsion particles containing fat-soluble bioactive substances in the liquid extract obtained from the liquid extract preparation step. Agglomerating step of adsorbing / aggregating / aggregating the particles with the biomass particles; And
4) 상기 응집물 제조단계 이후 고액분리를 통하여 카로티노이드와 토콜을 고농도로 포함하지만 수분함량이 40 내지 70% 내외로 줄어든 고상 추출물을 제조하는 고상 추출물 제조단계를 포함하여 팜유 제조 부산물로부터 지용성 생리활성물질을 고농도로 함유하는 것을 특징으로 하는 오일팜 바이오매스 고상 추출물의 제조 방법을 제공한다.4) The fat-soluble physiologically active substance from palm oil manufacturing by-products includes a solid phase extracting step of preparing a solid extract including high concentrations of carotenoids and tocols through solid-liquid separation after the flocculation step but reducing the water content to about 40 to 70%. It provides a method for producing an oil palm biomass solid extract, characterized in that it contains a high concentration.
본 발명에 따른 제조 방법에 있어서, 상기 바이오매스 곤죽 제조단계의 마찰식 분쇄는 오일팜 바이오매스로부터 팜유의 유화 용출 원리를 이용하는 것일 수 있다.In the production method according to the present invention, the friction grinding of the biomass grind production step may be to use the emulsification eluting principle of palm oil from the oil palm biomass.
본 발명에 따른 제조 방법에 있어서, 상기 바이오매스 곤죽 제조단계의 마찰식 분쇄는 오일팜 바이오매스로부터 지용성 생리활성물질을 추출하기 위해 이축 스크루 압출기(twin screw extruder)를 사용할 수 있다.In the manufacturing method according to the present invention, the trituration of the biomass grind production step may use a twin screw extruder to extract the fat-soluble physiologically active material from the oil palm biomass.
본 발명에 따른 제조 방법에 있어서, 상기 액상 추출물 제조단계에서 고액분리는 원심 분리법 또는 여과법을 이용할 수 있다.In the production method according to the present invention, the solid-liquid separation in the liquid extract manufacturing step may use a centrifugal separation method or a filtration method.
본 발명에 따른 제조 방법에 있어서, 상기 응집물 제조단계는 고분자 응집제로 폴리디시안디아미드(polydicyandiamide)와 폴리아크릴아미드(polyacrylamide)를 포함하는 양이온성, 음이온성 혹은 비이온성의 고분자 응집제 중 하나 이상을 사용하는 것일 수 있다.In the manufacturing method according to the present invention, the step of producing the aggregates using at least one of a cationic, anionic or nonionic polymer flocculant including polydicyandiamide and polyacrylamide as a polymer flocculant It may be.
본 발명에 따른 제조 방법에 있어서, 상기 고상 추출물 제조단계에서 고액분리는 필터프레스 혹은 벨트프레스를 포함하는 가압여과법을 사용하는 것일 수 있다.In the production method according to the present invention, the solid-liquid separation in the solid phase extract manufacturing step may be to use a pressure filtration method including a filter press or a belt press.
이하 본 발명에 따른 오일팜 바이오매스 고상 추출물의 제조 방법을 보다 상세하게 설명한다.Hereinafter, a method for preparing the oil palm biomass solid extract according to the present invention will be described in more detail.
본 발명에 따른 팜유 제조 부산물로부터 카로티노이드와 토콜을 고농도로 함유하는 고상 추출물을 제조하는 방법에서 첫 번째 단계는 팜유 제조 부산물에 물을 가하고 마찰식 분쇄를 통하여 바이오매스 곤죽을 제조하는 단계이다. 팜 공과방 혹은 팜 과육섬유 파쇄물에 먼저 바이오매스 건조중 대비 1 내지 5 배의 물을 가하고 마찰식 분쇄를 수행한다. 이때 사용될 수 있는 마찰식 분쇄기는 이축 스크루 압출기(twin screw extruder) 혹은 디스크 밀(disc mill)이며, 에너지 사용량을 줄이는 동시에 마찰 효과를 극대화하기 위해서는 이축 스크루 압출기가 바람직하다. 이 단계에서 팜 바이오매스는 물속에서 짓이겨지면서 바이오매스가 함유하는 팜유가 당지질(glycolipids) 혹은 인지질(phospholipids)의 유화작용에 의해 유탁입자로서 용출된다. 팜유가 유화 용출되는 효율은 마찰 분쇄 조건에 따라 달라질 수 있다. 상온에서 반고체인 팜유의 특성을 고려할 때 마찰식 분쇄의 온도는 20 oC 이상 100 oC 이하가 좋으며, 고온에서 변질될 수 있는 카로티노이드 특성을 추가로 고려할 때 마찰식 분쇄의 온도는 20 내지 50 oC가 바람직하다. 이축 스크루 압출기나 디스크 밀의 가동 조건은 기기의 종류, 스크루의 조합 혹은 디스크의 종류에 따라 달라질 수 있으므로 특정한 범위 내로 한정되지는 않는다. The first step in the method for preparing a solid extract containing a high concentration of carotenoids and tocols from the palm oil production by-products according to the present invention is to add water to the palm oil production by-products and to prepare biomass grits through frictional grinding. The palm bin or palm pulp fiber crushed is first subjected to 1 to 5 times more water than biomass drying and friction grinding. At this time, the friction mill can be used is a twin screw extruder (disc mill) or disc mill (disc mill), in order to reduce the energy consumption and at the same time maximize the friction effect is preferably a twin screw extruder. At this stage, the palm biomass is crushed in water, and the palm oil contained in the biomass is eluted as emulsified particles by emulsification of glycolipids or phospholipids. The efficiency of emulsifying and eluting palm oil may vary depending on the friction grinding conditions. When considering the properties of semi-solid palm oil at room temperature, the frictional grinding temperature is 20 o C or more and 100 o C or less, and the frictional grinding temperature is 20 to 50 o when additionally considering the carotenoid properties that may be altered at high temperature. C is preferred. The operating conditions of the twin screw extruder or the disk mill are not limited to a specific range because they may vary depending on the type of equipment, the combination of screws or the type of the disk.
본 발명의 두 번째 단계는 첫 단계에서 제조한 바이오매스 곤죽으로부터 지용성 생리활성 성분을 함유하는 유탁액과 소량의 바이오매스 미립자를 함유하는 액상 추출물을 제조하기 위한 고액 분리이다. 고액분리 전에 팜유 유탁액의 용출율과 회수율을 높이기 위해 먼저 바이오매스 곤죽에 바이오매스 건조중 대비 10 배 내지 20배의 물을 함유하도록 물을 더 첨가하고 교반하여 균일한 곤죽을 제조한다. 이 때 유탁입자의 생성을 촉진 혹은 생성된 유탁입자의 안정성을 증진하기 위해 상온 내지 50 oC 이하의 온수를 사용하거나 곤죽이 상온 내지 50 oC 이하가 되도록 가온할 수 있다. 이 곤죽의 고액분리에는 당업계에 통상적으로 사용되는 여러 가지 방법을 이용할 수 있으며, 그 예로 원심분리, 회전 탈수, 흡인 여과 및 가압여과 등을 들 수 있다. 생리활성물질이 함유된 유탁액을 높은 수율로 회수하는 데에는 팜유를 함유하는 유탁입자가 물보다 비중이 작은 특성을 이용하는 원심분리가 바람직하다. 즉, 바이오매스 미립자의 일부(예컨대 전체 바이오매스 건조중의 1% 내외 등)가 액상(liquid phase)에 머무르도록 저속으로 원심분리한 후(예컨대 200 ×g에서 1분) 미세한 바이오매스 입자와 유탁액을 함유하는 상징액을 회수함으로써 침전물인 대부분의 바이오매스와 분리할 수 있다. 하지만, 고액분리 후 회수되는 바이오매스의 수분함량이 커서 이후 추출성 성분이 제거된 바이오매스를 이용하는 목적으로는 부적합할 수도 있다. 바이오매스 곤죽으로부터 유탁액을 분리하기 위해 여과기술을 직접 적용할 수 있다. 이는 유탁입자의 크기가 수 미크론 이하로 대부분의 바이오매스보다는 작기 때문에 가능하다. 이때 바이오매스의 분쇄도를 고려하여 소량의 바이오매스 미립자와 유탁입자의 통과가 가능하도록 구멍크기가 2.5 미크론 내지 15 미크론의 여과포를 사용할 수 있다. 최종적으로 제조되는 고상 추출물 중 불용성 바이오매스의 비율이 고상 추출물 건조중의 15 내지 70 중량%가 되도록 미세 바이오매스가 통과할 수 있는 평균 구멍크기를 가지는 여과포를 선택하여 사용하는 것이 바람직하다. 이 단계에서 유탁액과 미세한 바이오매스를 대부분의 바이오매스로부터 분리 회수하기 위해 필터프레스, 벨트프레스 및 원심여과 모두 사용할 수 있지만, 고액분리에 에너지 사용량이 적고 액상물의 회수율이 높은 필터프레스 혹은 벨트프레스가 바람직하며, 액상물의 회수율이 가장 높은 필터프레스가 가장 바람직하다.The second step of the present invention is the solid-liquid separation to prepare an emulsion containing the fat-soluble physiologically active component from the biomass gruel prepared in the first step and a liquid extract containing a small amount of biomass particles. In order to increase the dissolution rate and recovery rate of the palm oil emulsion before solid-liquid separation, first, water is further added to the biomass gruel to contain 10 to 20 times more water than during drying to prepare a uniform gruel. At this time you can use a warm water of room temperature to 50 o C or less, or gonjuk can be allowed to warm to the room temperature to 50 o C or less in order to enhance the stability of the emulsion particles promote or generate the production of emulsion particles. The solid-liquid separation of this gruel can be used a variety of methods commonly used in the art, and examples thereof include centrifugation, rotary dehydration, suction filtration and pressure filtration. In order to recover the emulsion containing the physiologically active substance in high yield, centrifugal separation using palm oil-containing emulsion particles having a specific gravity smaller than that of water is preferable. That is, some of the biomass particulates (eg, about 1% of the total biomass drying, etc.) are centrifuged at low speed so as to stay in the liquid phase (eg, 1 minute at 200 × g) and then fine biomass particles By recovering the supernatant containing the emulsion can be separated from most of the biomass as a precipitate. However, since the moisture content of the biomass recovered after the solid-liquid separation is large, it may not be suitable for the purpose of using the biomass from which the extractable component is removed. Filtration techniques can be applied directly to separate the emulsion from biomass pellets. This is possible because the size of the emulsion particles is several microns or less, which is smaller than most biomass. At this time, in consideration of the pulverization degree of the biomass, a filter cloth having a pore size of 2.5 microns to 15 microns may be used to allow a small amount of biomass particles and emulsion particles to pass therethrough. It is preferable to select and use a filter cloth having an average pore size through which fine biomass can pass so that the ratio of insoluble biomass in the finally prepared solid extract is 15 to 70% by weight during solid extract extraction. At this stage, both filter press, belt press and centrifugal filtration can be used to separate and recover the emulsion and fine biomass from most biomass.However, filter press or belt press with high energy recovery and high recovery of liquids can be used for solid-liquid separation. Preferably, the filter press having the highest recovery rate of the liquid is most preferred.
본 발명의 세 번째 단계는 생리활성물질을 함유하는 유탁액을 공존하는 적은 양의 바이오매스 미립자에 흡착시키고 탈수하여 고상 추출물로 제조하는 단계이다. 이를 위해 상기 2단계의 고액분리에서 얻어진 액상추출물에 고분자 응결제를 처리하여 바이오매스 미립자와 유탁입자를 응결시키고 이후 응집제를 추가로 처리하여 가압여과할 수 있을 정도로 단단한 입자로 응집시킨다. 이를 위해 고분자 응결제를 고농도 수용액으로 만들어 상기 액상물에 첨가하면서 교반하여 유탁입자와 미세 바이오매스에 흡착시킨다. 이후 응집제를 첨가하고 교반한 후 응집물이 형성될 수 있도록 수 분 이상 정치한다. 이때 사용될 수 있는 고분자응결제와 응집제로는 폴리디시안디아미드(polydicyandiamide)와 폴리아크릴아미드(polyacrylamide)를 포함하는 양이온성, 음이온성, 비이온성의 고분자 응집제를 사용할 수 있으며, 고액분리로 고상 추출물을 제조할 수 있을 만큼 단단한 응집물이 형성되는 한 그 종류와 사용량이 제한되지 않는다. 응집물이 형성되면 이를 상기 단계 2에서 명시된 방법들을 사용하여 고액분리함으로써 수분함량이 낮은 고상 추출을 조제한다. 이때 고액분리 결과 얻어지는 고상 추출물의 수분함량이 가장 낮아지는 가압여과가 바람직하며, 적은 에너지 사용량과 고상 추출물의 낮은 수분함량 면에서 필터프레스를 적용하는 것이 더욱 바람직하다. 이렇게 제조한 생리활성물질 고농도 함유 고상 추출물은 건조중으로 비교할 때 원료 바이오매스 중량의 2 내지 15%에 불과하게 되며, 수분함량이 40 내지 70 중량%로 낮아서 이후 적은 양의 수용성 유기용매 혹은 초임계수, 초임계 이산화탄소로도 지용성 생리활성물질을 경제적으로 추출할 수 있게 된다.The third step of the present invention is to prepare a solid extract by adsorbing and dehydrating a small amount of biomass microparticles containing an emulsion containing a bioactive material. To this end, the liquid extract obtained in the solid-liquid separation of the second step is treated with a polymer coagulant to coagulate the biomass fine particles and the emulsion particles, and thereafter, the coagulant is further treated to coagulate into particles that are hard enough to be filtered under pressure. To this end, the polymer coagulant is made into a high concentration aqueous solution, and is added to the liquid phase and stirred while adsorbing to the suspended particles and the fine biomass. The flocculant is then added and stirred and allowed to stand for at least several minutes so that aggregates can form. At this time, as the polymer coagulant and flocculant, cationic, anionic and nonionic polymer coagulant including polydicyandiamide and polyacrylamide may be used, and solid phase extract may be prepared by solid-liquid separation. The type and amount used are not limited as long as the aggregates are as hard as possible. Once an aggregate is formed, it is subjected to solid-liquid separation using the methods described in Step 2 above to prepare a solid phase extraction having a low water content. At this time, the pressurized filtration which is the lowest the water content of the solid extract obtained as a result of the solid-liquid separation is preferred, and it is more preferable to apply a filter press in terms of low energy consumption and low water content of the solid extract. The solid extract containing high concentration of the bioactive substance prepared in this way is only 2 to 15% of the weight of the raw material biomass when compared to drying, and the water content is low to 40 to 70% by weight, so that a small amount of water-soluble organic solvent or supercritical water, Supercritical carbon dioxide can also extract economically soluble bioactive substances.
또한, 본 발명은 상기 방법에 따라 생산된 카로티노이드와 토콜 등 지용성 생리활성물질을 함유하는 팜유 10 내지 30 중량%; 불용성(solvent-insoluble) 오일팜 바이오매스 15 내지 40 중량% 및 물 40 내지 70 중량%를 포함하여 용매 추출에 의해 지용성 생리활성물질의 공업적 제조에 사용할 수 있는 오일팜 바이오매스 고상추출물을 제공한다.In addition, the present invention is 10 to 30% by weight of palm oil containing a fat-soluble bioactive substance such as carotenoids and tocol produced according to the above method; It provides an oil palm biomass solid phase extract that can be used for the industrial preparation of fat-soluble bioactive substances by solvent extraction, including 15 to 40% by weight of solvent-insoluble oil palm biomass and 40 to 70% by weight of water. .
본 발명에 따른 오일팜 바이오매스 고상추출물에 있어서, 상기 지용성 생리활성물질은 카로테노이드 또는 토콜일 수 있고, 알파카로틴, 베타카로틴, 감마카로틴, 라이코펜, 코토페롤 및 토코트리에놀로 이루어진 군에서 선택되는 어느 하나 이상일 수 있다.In the oil palm biomass solid extract according to the present invention, the fat-soluble physiologically active substance may be a carotenoid or tocol, and at least one selected from the group consisting of alpha carotene, beta carotene, gamma carotene, lycopene, cotoperol and tocotrienol. Can be.
본 발명에 따른 오일팜 바이오매스 고상추출물에 있어서, 상기 오일팜 바이오매스는 팜유 제조 과정에서 부산물로 발생하는 팜 공과방(empty fruit bunch of oil palm), 팜 과육섬유(palm pressed fiber) 및 팜유 공장폐수(palm oil mill effluent) 중 어느 하나 이상일 수 있다.In the oil palm biomass solid extract according to the present invention, the oil palm biomass palm oil (empty fruit bunch of oil palm), palm pressed fiber (palm pressed fiber) and palm oil plant generated as a by-product in the palm oil manufacturing process It may be at least one of palm oil mill effluent.
상기와 같이 제조한 본 발명의 지용성 생리활성물질을 고농도로 함유하는 고상 추출물은 이후 용매를 사용하여 카로티노이드와 토콜을 추출하는데 사용할 수 있다. 즉, 단계 3에서 수분 함량을 줄여 제조한 고상 추출물에 대해 1:1(w/v)에서 1:10 (w/v)의 비율로 용매를 가한 후 교반하여 생리활성물질을 추출한 후 원심분리 혹은 여과를 통하여 카로티노이드와 토콜을 포함하는 용액을 얻을 수 있다. 이 때 지용성 생리활성물질의 추출에 사용하는 용매는 수용성 유기용매, 수 난용성 유기용매, 초임계수 혹은 초임계 이산화탄소 등을 들 수 있으며, 추출하고자 하는 생리활성물질의 용해도와 소요비용을 고려하여 선정할 수 있다. 그 예로는 수용성 유기용매로서 에탄올, 메탄올, 이소프로필 알콜 등 알콜류, 테트라하이드로퓨란 등 기타 유기용매, 수 난용성 유기용매로는 클로로포름, 다이클로로메탄, 에틸아세테이트, 헥산(hexane), 그 외에 각종 유기용매와 혼합하여 사용할 수도 있는 초임계수 혹은 초임계 이산화탄소 등을 들 수 있으며, 당업계에서 사용 가능한 모든 용매와 추출 방법이 사용될 수 있다.Solid extract containing a high concentration of the fat-soluble physiologically active substance of the present invention prepared as described above may then be used to extract carotenoids and tocol using a solvent. That is, the solvent was added at a ratio of 1: 1 (w / v) to 1:10 (w / v) with respect to the solid extract prepared by reducing the water content in step 3, followed by stirring to extract the bioactive material, followed by centrifugation or Filtration yields a solution containing carotenoids and tocols. At this time, the solvent used to extract the fat-soluble physiologically active substance may include a water-soluble organic solvent, a poorly water-soluble organic solvent, supercritical water or supercritical carbon dioxide, and selected in consideration of the solubility and cost of the bioactive substance to be extracted. can do. Examples include water-soluble organic solvents such as alcohols such as ethanol, methanol and isopropyl alcohol, other organic solvents such as tetrahydrofuran, and poorly water-soluble organic solvents such as chloroform, dichloromethane, ethyl acetate, hexane, and other organic solvents. Supercritical water or supercritical carbon dioxide may be used in combination with the solvent, and all solvents and extraction methods available in the art may be used.
본 발명에 따른 팜유 부산물로부터 제조한 카로티노이드와 토콜을 고농도로 함유하는 소량의 고상 추출물은 이후 생리활성물질의 용매 추출과 정제를 통한 공업용 원료를 경제적으로 제조할 수 있게 한다. The small amount of solid extract containing high concentrations of carotenoids and tocol prepared from palm oil by-products according to the present invention enables economic production of industrial raw materials through solvent extraction and purification of physiologically active substances.
이하, 본원 발명의 바람직한 실시 예를 비교예와 함께 본원이 속하는 기술 분야에서 일반적인 지식을 가진 자가 쉽게 실시할 수 있도록 상세히 설명한다. 특히 이것에 의해 본 발명의 기술적 사상과 그 핵심 구성 및 작용이 제한을 받지 않는다. 또한, 본 발명의 내용은 여러 가지 다른 형태의 장비로 구현될 수 있으며, 여기에서 설명하는 구현 예 및 실시 예에 한정되지 않는다.Hereinafter, the preferred embodiment of the present invention will be described in detail with reference to the comparative example so that those skilled in the art can easily carry out. In particular, the technical spirit of the present invention and its core configuration and operation are not limited by this. In addition, the content of the present invention may be implemented in various other forms of equipment, and is not limited to the embodiments and embodiments described herein.
실시예 1. 팜 공과방으로부터 지용성 생리활성물질을 고농도로 함유하는 고상 추출물의 제조 Example 1. Preparation of solid extract containing high concentration of fat-soluble bioactive substance from palm fruit
팜 공과방(empty fruit bunch of oil palm, 인도네시아 산) 300 g(건조중, 에탄올 추출성 성분 4.6%)을 바이오매스와 물의 비율이 1:5가 되도록 침지하였다. 트윈 스크루 압출기(TEK 40 MHS, 에스엠플라텍, 한국)에 니딩 블록과 믹싱 스크루를 혼합하여 장착하고, 50 oC에서 분당 20 회전의 속도로 운전하면서 물에 침지한 팜 공과방을 주입하여 마찰식 분쇄를 실시하였다. 마찰식 분쇄를 통하여 제조된 바이오매스 곤죽은 물과의 최종 비율이 1:20(바이오매스:물)이 되도록 물을 가하고 교반한 후 6 미크론 여과포가 부착된 소형 필터프레스(한국화학연구원 제작, 한국)에 주입하여 유탁액과 바이오매스 미립자가 포함된 액상 추출물과 대량의 바이오매스로 각각 분리 회수하였다(A). 이 액상 추출물에 폴리디시안디아미드(polydicyandiamide, DC-400, SNF Korea, 한국)를 3,000 mg/L의 농도로 처리하고 느린 속도로 교반하여 유탁입자를 바이오매스 미립자에 흡착 응결되게 하였다. 여기에 양이온성 폴리아크릴아마이드(cationic polyacrylamide, C-211, SNF Korea, 한국) 수용액을 20 mg/L의 농도로 첨가하고 교반한 후 응집물이 형성되도록 상온에서 60 분간 정치하였다. 응집물이 형성된 후 상기 6 미크론 여과포가 부착된 소형 필터프레스(한국화학연구원 제작, 한국)를 이용하여 고액분리함으로써 고상 추출물을 제조하였다. 이 고상 추출물의 무게를 측정하고, 소량 취하여 동결건조하여 수분함량을 측정하였다. 또한, 이 고상 추출물 2 g을 50 ml용 팔콘 튜브에 취하고 에탄올 9 ml를 가하여 초음파 추출한 후 원심분리하여 상징액을 조제하였다. 분광광도계(Benchmark Plus microplate spectrophotometer, BIO RAD, 미국, 450 nm)로 지용성 생리활성물질의 지표로서 카로티노이드를 정량하였다. 팔콘 튜브에 남아 있는 에탄올을 따라내고 공기를 불어넣어 에탄올을 휘발시켜 제거하였다. 여기에 헥산(n-hexane)을 50 ml 가하고 초음파 추출한 후 원심분리하고 상징액을 제거하였다. 공기를 불어넣어 헥산을 제거한 후 24시간 동안 감압건조하고 무게를 측정함으로써 지용성 성분이 제거된 고상 추출물의 무게를 산출하였다. 상기 실험치로부터 팜 공과방 고상 추출물의 조성과 수율을 산출하여 표 1에 표시하였다.300 g (empty fruit bunch of oil palm, Indonesia) immersed so that the ratio of biomass to water is 1: 5 during drying. The twin screw extruder (TEK 40 MHS, SM PLATEC, Korea) is equipped with a kneading block and a mixing screw, and is operated at a speed of 20 revolutions per minute at 50 o C while injecting palm-based fruits immersed in water. Grinding was carried out. Biomass grits prepared by friction grinding were added with water to a final ratio of 1:20 (biomass: water) and stirred, followed by a small filter press with 6 micron filter cloth (manufactured by Korea Research Institute of Chemical Technology, Korea). ) Was separated and recovered as a liquid extract containing an emulsion and biomass particles and a large amount of biomass, respectively (A). Polydicyandiamide (polydicyandiamide, DC-400, SNF Korea, Korea) was treated to this liquid extract at a concentration of 3,000 mg / L and stirred at a slow rate to allow the adsorbed particles to adsorb to the biomass particles. Cationic polyacrylamide (C-211, SNF Korea, Korea) aqueous solution was added thereto at a concentration of 20 mg / L, and stirred for 60 minutes at room temperature to form aggregates. After the aggregate was formed, the solid extract was prepared by solid-liquid separation using a small filter press (Korea Institute of Chemical Research, Korea) attached to the 6 micron filter cloth. The solid extract was weighed, taken in small amounts and lyophilized to determine the moisture content. In addition, 2 g of this solid extract was taken in a 50 ml falcon tube, followed by ultrasonic extraction with 9 ml of ethanol, followed by centrifugation to prepare a supernatant. Carotenoids were quantified as indicators of fat-soluble bioactive substances by a spectrophotometer (Benchmark Plus microplate spectrophotometer, BIO RAD, USA, 450 nm). The ethanol remaining in the falcon tube was decanted and blown with air to remove the ethanol by volatilization. 50 ml of hexane (n-hexane) was added thereto, followed by ultrasonic extraction, centrifugation and supernatant removed. Air was blown to remove hexane, dried under reduced pressure for 24 hours, and weighed to calculate the weight of the solid extract from which the fat-soluble component was removed. The composition and yield of the palm fruit fruit solid extract from the experimental values were calculated and shown in Table 1.
실시예 2. 팜 과육섬유로부터 지용성 생리활성물질을 고농도로 함유하는 고상 추출물의 제조 Example 2. Preparation of solid extract containing high concentration of fat soluble bioactive substance from palm pulp fiber
팜 과육섬유(palm pressed fiber, 인도네시아 산) 300 g(건조중, 에탄올 추출성 성분 6.4%)을 바이오매스와 물의 비율이 1:5가 되도록 침지하였다. 트윈 스크루 압출기(TEK 40 MHS, 에스엠플라텍, 한국)에 니딩 블록과 믹싱 스크루를 혼합하여 장착하고, 50 oC에서 분당 20 회전의 속도로 운전하면서 물을 흡수한 팜 공과방을 주입하여 마찰식 분쇄를 실시하였다. 마찰식 분쇄를 통하여 제조된 바이오매스 곤죽은 물과의 최종 비율이 1:20(바이오매스:물)이 되도록 물을 가하고 교반함으로써 혼합한 후 6 미크론 여과포가 부착된 소형 필터프레스(한국화학연구원 제작, 한국)를 이용하여 유탁액과 바이오매스 미립자가 포함된 액상 추출물과 대량의 바이오매스로 각각 분리 회수하였다(A). 액상 추출물에 폴리디시안디아미드(polydicyandiamide, DC-400, SNF Korea, 한국)를 3,000 mg/L의 농도로 처리하고 느린 속도로 교반하여 유탁입자를 미세 바이오매스에 응결되게 하였다. 여기에 양이온성 폴리아크릴아마이드(polyacrylamide C-211, SNF Korea, 한국) 수용액을 30 mg/L의 농도로 첨가하고 교반한 후 응집물이 형성되도록 상온에서 60 분간 정치하였다. 응집물이 형성된 후 상기 6 미크론 여과포가 부착된 소형 필터프레스(한국화학연구원 제작, 한국)를 이용하여 고액분리함으로써 고상 추출물을 제조하였다. 이 고상 추출물의 무게를 측정하고, 소량 취하여 동결건조하여 수분함량을 측정하였다. 또한, 이 고상 추출물 2 g을 50 ml용 팔콘 튜브에 취하고 에탄올 9 ml를 가하여 초음파 추출한 후 원심분리하여 상징액을 조제하였다. 흡광검출기(absorbance detecter)가 부착된 고속액체크로마토그래프(high performance liquid chromatography, Waters, 미국)로 지용성 생리활성물질의 지표로서 베타카로틴을 정량하였다. 팔콘 튜브에 남아 있는 에탄올을 따라내고 공기를 불어넣어 에탄올을 휘발시켜 제거하였다. 여기에 헥산(n-hexane)을 50 ml 가하고 초음파 추출한 후 원심분리하고 상징액을 제거하였다. 공기를 불어넣어 헥산을 제거한 후 24시간 동안 감압건조하고 무게를 측정함으로써 지용성 성분이 제거된 고상 추출물의 무게를 산출하였다. 상기 실험치로부터 팜 과육섬유 고상 추출물의 조성과 수율을 산출하여 표 1에 표시하였다.300 g of palm pressed fiber (from Indonesia) (during drying, 6.4% ethanol extractable ingredient) was immersed so that the ratio of biomass and water was 1: 5. A twin screw extruder (TEK 40 MHS, SM PLATEC, Korea) is equipped with a kneading block and mixing screw, and is operated at a rate of 20 revolutions per minute at 50 o C. Grinding was carried out. Biomass grits prepared by friction grinding are mixed by adding water and stirring to make a final ratio of 1:20 (biomass: water) with water (small chemical press with 6 micron filter cloth) , Korea) were separated and recovered as a liquid extract containing the emulsion and biomass particles and a large amount of biomass (A). Polydicyandiamide (polydicyandiamide, DC-400, SNF Korea, Korea) was treated in a liquid extract at a concentration of 3,000 mg / L and stirred at a slow rate to cause the emulsion particles to coagulate in the fine biomass. Cationic polyacrylamide (polyacrylamide C-211, SNF Korea, Korea) was added thereto at a concentration of 30 mg / L, and stirred for 60 minutes at room temperature to form an aggregate. After the aggregate was formed, the solid extract was prepared by solid-liquid separation using a small filter press (Korea Institute of Chemical Research, Korea) attached to the 6 micron filter cloth. The solid extract was weighed, taken in small amounts and lyophilized to determine the moisture content. In addition, 2 g of this solid extract was taken in a 50 ml falcon tube, followed by ultrasonic extraction with 9 ml of ethanol, followed by centrifugation to prepare a supernatant. Beta-carotene was quantified as an indicator of fat-soluble bioactive substance by high performance liquid chromatography (Waters, USA) with an absorbance detector. The ethanol remaining in the falcon tube was decanted and blown with air to remove the ethanol by volatilization. 50 ml of hexane (n-hexane) was added thereto, followed by ultrasonic extraction, centrifugation and supernatant removed. Air was blown to remove hexane, dried under reduced pressure for 24 hours, and weighed to calculate the weight of the solid extract from which the fat-soluble component was removed. The composition and yield of palm pulp fiber solid extract were calculated from the experimental values, and are shown in Table 1.
실시예 3. 팜유 공장폐수로부터 지용성 생리활성물질을 고농도로 함유하는 고상 추출물의 제조 Example 3. Preparation of solid extract containing high concentration of fat-soluble bioactive substance from palm oil factory wastewater
팜유 공장폐수(palm oil mill effluent, 팜 과육 포함, 인도네시아 산) 1,000 g에 폴리디시안디아미드(polydicyandiamide, DC-400, SNF Korea, 한국)를 3,000 mg/L의 농도로 처리하고 느린 속도로 교반하여 유탁입자를 미세 바이오매스에 응결되게 하였다. 여기에 양이온성 폴리아크릴아마이드(polyacrylamide C-211, SNF Korea, 한국) 수용액을 40 mg/L의 농도로 첨가하고 교반한 후 응집물이 형성되도록 상온에서 60 분간 정치하였다. 응집물이 형성된 후 상기 6 미크론 여과포가 부착된 소형 필터프레스(한국화학연구원 제작, 한국)를 이용하여 고액분리함으로써 고상 추출물을 제조하였다. 이 고상 추출물의 무게를 측정하고, 소량 취하여 동결건조하여 수분함량을 측정하였다. 또한, 이 고상 추출물 2 g을 50 ml용 팔콘 튜브에 취하고 에탄올 9 ml를 가하여 초음파 추출한 후 원심분리하여 상징액을 조제하였다. 분광광도계(Benchmark Plus microplate spectrophotometer, BIO RAD, 미국, 450 nm)로 지용성 생리활성물질의 지표로서 카로티노이드를 정량하였다. 팔콘 튜브에 남아 있는 에탄올을 따라내고 공기를 불어넣어 에탄올을 휘발시켜 제거하였다. 여기에 헥산(n-hexane)을 50 ml 가하고 초음파 추출한 후 원심분리하고 상징액을 제거하였다. 공기를 불어넣어 헥산을 제거한 후 24시간 동안 감압건조하고 무게를 측정함으로써 지용성 성분이 제거된 고상 추출물의 무게를 산출하였다. 상기 실험치로부터 팜유 공장폐수 고상 추출물의 조성과 수율을 산출하여 표 1에 표시하였다.1,000 g of palm oil mill effluent (including palm pulp, Indonesia) was treated with polydicyandiamide (polydicyandiamide, DC-400, SNF Korea, Korea) at a concentration of 3,000 mg / L and stirred at a slow rate. The emulsion particles were allowed to coagulate in the fine biomass. Cationic polyacrylamide (polyacrylamide C-211, SNF Korea, Korea) was added thereto at a concentration of 40 mg / L, and stirred for 60 minutes at room temperature to form an aggregate. After the aggregate was formed, the solid extract was prepared by solid-liquid separation using a small filter press (Korea Institute of Chemical Research, Korea) attached to the 6 micron filter cloth. The solid extract was weighed, taken in small amounts and lyophilized to determine the moisture content. In addition, 2 g of this solid extract was taken in a 50 ml falcon tube, followed by ultrasonic extraction with 9 ml of ethanol, followed by centrifugation to prepare a supernatant. Carotenoids were quantified as indicators of fat-soluble bioactive substances by a spectrophotometer (Benchmark Plus microplate spectrophotometer, BIO RAD, USA, 450 nm). The ethanol remaining in the falcon tube was decanted and blown with air to remove the ethanol by volatilization. 50 ml of hexane (n-hexane) was added thereto, followed by ultrasonic extraction, centrifugation and supernatant removed. Air was blown to remove hexane, dried under reduced pressure for 24 hours, and weighed to calculate the weight of the solid extract from which the fat-soluble component was removed. The composition and yield of the palm oil plant wastewater solid extract were calculated from the experimental values and are shown in Table 1.
비교예 1. 팜 공과방 , 팜 과육섬유 및 팜유 공장폐수에 함유된 지용성 생리활성물질의 총량 추정 Comparative Example 1. The estimated total amount of the fat-soluble physiologically active substance contained in the palm ball rooms, and pulp fiber palm and palm oil Waste Water
건조된 팜 공과방과 팜 과육섬유를 커터밀(cutter mill, 한국분체기계 제품, 한국)로 커팅 분쇄하여 20 메쉬 이하 분말로 조제하였다. 팜유 공장폐수는 동결건조하고 분쇄하여 20 메쉬 이하 분말로 조제하였다. 이 시료들을 5 g(건조중) 취하여 속시렛용 띰블에 넣고 에탄올을 용매로 하여 속시렛 추출하였다. 추출액의 부피를 측정하고 일부를 취하여 원심분리하였다. 상징액을 취하여 450 nm에서 흡광도를 측정하여 카로티노이드를 정량(팜 공과방과 팜유공장폐수의 경우)하거나 흡광검출기(absorbance detecter, 검출파장 450nm)가 부착된 고속액체크로마토그래프(high performance liquid chromatography, Waters, 미국)로 지용성 생리활성물질의 지표로서 베타카로틴을 정량한 다음 이 값을 실시예에서 얻은 카로티노이드 혹은 베타카로틴의 양과 비교하여 각 실시예의 회수율을 산출하고 그 결과를 표 1에 나타내었다.The dried palm fruits and palm pulp fibers were cut and pulverized with a cutter mill (manufactured by Korea Powder Machinery, Korea) to prepare a powder of 20 mesh or less. Palm oil plant wastewater was lyophilized and ground to a powder of 20 mesh or less. 5 g (during drying) of these samples were taken and placed in a Soxhlet wobble, followed by Soxhlet extraction using ethanol as a solvent. The volume of the extract was measured and a portion was taken and centrifuged. Take supernatant and measure absorbance at 450 nm to quantify carotenoids (for palm fruits and palm oil plant wastewater) or high performance liquid chromatography (absorption detector 450 nm) with high performance liquid chromatography, Waters, USA Beta carotene was quantified as an indicator of fat-soluble physiologically active substance, and the recovery rate of each example was calculated by comparing this value with the amount of carotenoid or beta carotene obtained in Examples, and the results are shown in Table 1.
팜 부산물Palm By-Products 조성(g)Composition (g)
실시예 1(팜 공과방)Example 1 (palm fruits and vegetables) 실시예 2(팜 과육섬유)Example 2 (palm pulp fiber) 실시예 3(팜유 공장폐수)Example 3 (palm oil factory wastewater)
총량Total amount 35.535.5 32.132.1 32.932.9
물water 20.520.5 17.417.4 19.419.4
불용성 바이오매스Insoluble Biomass 8.68.6 8.48.4 4.54.5
지용성 성분Fat-soluble ingredients 6.46.4 6.36.3 9.09.0
바이오매스(300g) 중 베타카로틴 혹은 카로티노이드(mg)Beta-carotene or carotenoids (mg) in biomass (300g) 10.5(카로티노이드)10.5 (carotenoids) 19.8(베타카로틴)19.8 (beta carotene) 14.5베타카로틴)14.5beta carotene)
고상 추출물 중 베타카로틴 혹은 카로티노이드(mg)Beta-carotene or carotenoids (mg) in solid extract 4.84.8 10.110.1 12.312.3
카로틴 혹은 카로티노이드회수율(%)Carotene or carotenoid recovery rate (%) 4545 5151 8585
상기 표 1에서 보는 바와 같이, 건조중 300 g의 팜 공과방과 팜 과육섬유를 본 발명의 기술을 사용하여 고상 추출물로 제조한 결과 원료 바이오매스 중량의 10%로 무게를 줄인 고상 추출물로도 원료 바이오매스가 함유하는 지용성 생리활성물질의 30% 이상을 회수할 수 있다. 또한, 팜유 공장폐수 중량의 4% 이하 중량으로 제조한 고상 추출물로 폐수에 함유되어 있던 지용성 생리활성물질의 85%를 회수할 수 있다. 이는 원료 바이오매스의 제조 후 오랜 시간이 지나 지용성 생리활성물질의 함량이 극히 낮아진 시료를 사용한 결과이다. 따라서 문헌에서 볼 수 있는 것처럼 지용성 생리활성성분의 함유율이 높은 산지의 신선한 재료를 사용할 경우 본 발명의 기술은 지용성 생리활성물질을 보다 더 높은 수율로 회수할 수 있을 것이다.As shown in Table 1 above, 300 g of the palm oatmeal and palm pulp fiber during drying were prepared as a solid extract using the technique of the present invention, and the raw material biomass was reduced to 10% of the weight of the raw biomass. More than 30% of the fat-soluble bioactive substance contained in the mass can be recovered. In addition, it is possible to recover 85% of the fat-soluble physiologically active substance contained in the wastewater as a solid extract prepared at 4% or less by weight of the palm oil factory wastewater. This is a result of using a sample in which the content of fat-soluble physiologically active substance is extremely low after a long time after the preparation of the raw biomass. Thus, as can be seen in the literature, the technique of the present invention will be able to recover the fat-soluble physiologically active material in a higher yield when using a fresh material from a mountain region having a high content of fat-soluble physiologically active ingredients.

Claims (10)

  1. 지용성 생리활성물질을 함유하는 팜유 10 내지 30 중량%;10 to 30% by weight of palm oil containing fat-soluble bioactive substance;
    불용성(solvent-insoluble) 오일팜 바이오매스 15 내지 40 중량%; 및15 to 40% by weight of solvent-insoluble oil palm biomass; And
    물 40 내지 70 중량%를 포함하여 용매 추출에 의해 지용성 생리활성물질의 공업적 제조에 사용할 수 있는 오일팜 바이오매스 고상추출물.Oil palm biomass solid phase extract that can be used in the industrial production of fat-soluble bioactive substances by solvent extraction, including 40 to 70% by weight of water.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 지용성 생리활성물질은 카로티노이드 또는 토콜인 것을 특징으로 하는 오일팜 바이오매스 고상추출물.The fat-soluble physiologically active substance is an oil palm biomass solid extract, characterized in that the carotenoid or tocol.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 지용성 생리활성물질은 알파카로틴, 베타카로틴, 감마카로틴, 라이코펜, 코토페롤 및 토코트리에놀로 이루어진 군에서 선택되는 어느 하나 이상인 것을 특징으로 하는 오일팜 바이오매스 고상추출물.The fat-soluble bioactive substance is oil palm biomass solid extract, characterized in that any one or more selected from the group consisting of alpha carotene, beta carotene, gamma carotene, lycopene, cotoperol and tocotrienols.
  4. 청구항 1에 있어서,The method according to claim 1,
    상기 오일팜 바이오매스는 팜유 제조 과정에서 부산물로 발생하는 팜 공과방(empty fruit bunch of oil palm), 팜 과육섬유(palm pressed fiber) 및 팜유 공장폐수(palm oil mill effluent) 중 어느 하나 이상인 것을 특징으로 하는 오일팜 바이오매스 고상추출물.The oil palm biomass may be any one or more of an empty fruit bunch of oil palm, palm pressed fiber, and palm oil mill effluent generated as a by-product during the production of palm oil. Oil palm biomass solid extract.
  5. 팜유 제조 부산물을 물에 침지한 후 마찰식 분쇄를 통하여 유탁액을 함유하는 바이오매스 곤죽을 제조하는 바이오매스 곤죽 제조단계;Biomass gruel manufacturing step of preparing biomass gruel containing an emulsion by immersing palm oil by-products in water and then by friction grinding;
    상기 바이오매스 곤죽 제조단계에서 얻은 바이오매스 곤죽을 고액분리하여 바이오매스 미립자 및 유탁입자를 함유하는 액상 추출물을 제조하는 액상 추출물 제조단계;Liquid extract manufacturing step of preparing a liquid extract containing biomass fine particles and emulsion particles by solid-liquid separation of the biomass gruel obtained in the biomass gruel manufacturing step;
    상기 액상 추출물 제조단계부터 얻은 액상 추출물 중 지용성 생리활성물질을 함유하는 팜유 유탁입자를 고체화하기 위해 응결제(coagulant), 응집제(flocculant) 또는 응결제(coagulant)와 응집제(flocculant)를 순차적으로 가하여 유탁입자를 바이오매스 미립자와 흡착/응결/응집시키는 응집물 제조단계; 및Coagulant, flocculant or coagulant and flocculant are sequentially added to solidify palm oil emulsion particles containing fat-soluble physiologically active substances in the liquid extract obtained from the liquid extract preparation step. Preparing agglomerates to adsorb / coagulate / aggregate the biomass particles; And
    상기 응집물 제조단계 이후 고액분리를 통하여 고상 추출물을 제조하는 고상 추출물 제조단계를 포함하여 팜유 제조 부산물로부터 지용성 생리활성물질을 고농도로 함유하는 것을 특징으로 하는 오일팜 바이오매스 고상 추출물의 제조 방법.The method of producing an oil palm biomass solid phase extract, characterized in that it contains a fat-soluble physiologically active substance from palm oil production by-products, including a solid phase extracting step of preparing a solid extract through solid-liquid separation after the flocculation step.
  6. 청구항 5에 있어서,The method according to claim 5,
    상기 바이오매스 곤죽 제조단계의 마찰식 분쇄는 오일팜 바이오매스로부터 팜유의 유화 용출 원리를 이용하는 것을 특징으로 하는 오일팜 바이오매스 고상 추출물의 제조 방법.Friction pulverization of the biomass porridge production step is a method for producing an oil palm biomass solid phase extract, characterized in that using the palm oil emulsification eluting principle from the oil palm biomass.
  7. 청구항 5에 있어서,The method according to claim 5,
    상기 바이오매스 곤죽 제조단계의 마찰식 분쇄는 오일팜 바이오매스로부터 지용성 생리활성물질을 추출하기 위해 이축 스크루 압출기(twin screw extruder)를 사용하는 것을 특징으로 하는 오일팜 바이오매스 고상 추출물의 제조 방법.Friction pulverization of the biomass gruel manufacturing step is a method for producing an oil palm biomass solid phase extract, characterized in that to use a twin screw extruder (twin screw extruder) to extract the fat-soluble bioactive material from the oil palm biomass.
  8. 청구항 5에 있어서,The method according to claim 5,
    상기 액상 추출물 제조단계에서 고액분리는 원심 분리법 또는 여과법을 이용하는 것을 특징으로 하는 오일팜 바이오매스 고상 추출물의 제조 방법.Solid-liquid separation in the liquid extract manufacturing step is a method for producing an oil palm biomass solid extract, characterized in that using centrifugal separation or filtration.
  9. 청구항 5에 있어서,The method according to claim 5,
    상기 응집물 제조단계는 고분자 응집제로 폴리디시안디아미드(polydicyandiamide)와 폴리아크릴아미드(polyacrylamide)를 포함하는 양이온성, 음이온성 혹은 비이온성의 고분자 중 하나 이상을 사용하는 것을 특징으로 하는 오일팜 바이오매스 고상 추출물의 제조 방법.The agglomerate preparation step is an oil palm biomass solid phase, characterized in that using at least one of a cationic, anionic or nonionic polymer including polydicyandiamide and polyacrylamide as a polymer flocculant. Method of Preparation of Extracts.
  10. 청구항 5에 있어서,The method according to claim 5,
    상기 고상 추출물 제조단계에서 고액분리는 필터프레스 혹은 벨트프레스를 포함하는 가압여과법을 사용하는 것을 특징으로 하는 오일팜 바이오매스 고상 추출물의 제조 방법.Solid-liquid separation in the solid phase extract manufacturing step is a method for producing an oil palm biomass solid phase extract, characterized in that using a pressure filtration method including a filter press or belt press.
PCT/KR2017/013717 2016-12-02 2017-11-28 Oil palm biomass solid phase extract containing high concentration of fat-soluble physiologically active substance produced from palm oil production by-products and method for producing same WO2018101710A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5190618A (en) * 1988-03-16 1993-03-02 Bioindustry Development Centre (Bidec) Production of high concentration tocopherols and tocotrienols from palm-oil by-products
KR101029879B1 (en) * 2011-02-09 2011-04-15 주식회사 덕분 Method of manufacturing environment-friendly biobunker c oil containing low content of sulfur using palm oil byproduct
US8048652B2 (en) * 2005-05-12 2011-11-01 Martek Biosciences Corporation Biomass hydrolysate and uses and production thereof
KR20130115577A (en) * 2012-04-12 2013-10-22 주식회사 창해에탄올 Device for prducing fermentable sugar having high concentration, method of producing fermentable sugar having high concentration using the same, and bio fuel and bio chemical material produced using the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8673967B2 (en) 2007-05-24 2014-03-18 Loders Croklaan B.V. Process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5190618A (en) * 1988-03-16 1993-03-02 Bioindustry Development Centre (Bidec) Production of high concentration tocopherols and tocotrienols from palm-oil by-products
US8048652B2 (en) * 2005-05-12 2011-11-01 Martek Biosciences Corporation Biomass hydrolysate and uses and production thereof
KR101029879B1 (en) * 2011-02-09 2011-04-15 주식회사 덕분 Method of manufacturing environment-friendly biobunker c oil containing low content of sulfur using palm oil byproduct
KR20130115577A (en) * 2012-04-12 2013-10-22 주식회사 창해에탄올 Device for prducing fermentable sugar having high concentration, method of producing fermentable sugar having high concentration using the same, and bio fuel and bio chemical material produced using the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KURNIN, NOR AZRIN AHMAD: "Recovery of palm oil and valuable material from oil palm empty fruit bunch by sub-critical water", JOURNAL OF OLEO SCIENCE, vol. 65, no. 4, April 2016 (2016-04-01), pages 283 - 289, XP055606983 *

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