Espacenet — Bibliographic data
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` Espacenet
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`Bibliographic data: JP4057853 (A) 7— 1992-02-25
`
`METHOD FOR EXTRACTING AND SEPARATING COLORING MATTER FROM KRILL
`
`'"V8"t°r(s)‘
`Applicant(s):
`.
`.
`.
`Classrficatlon:
`
`TOKUMORI TSUNEO; SUMIDA YOKO; TSUYAMA KOICHI;
`KUNISHIRO lYOKO; OKADA HARUO; TANl TOSHlFUMl _+_
`CHLORINE ENG CORP LTD; ITANO RElTOU KK i
`- international:
`009361/00;(lP01-7): COQBGi/OO
`
`- European:
`
`Application
`number:
`
`JP19900170549 19900628
`
`EST” "umber
`25° pUb'iShEd
`
`JP19900170549 19900628
`JP2963152 (B2)
`
`Abstract of JP4057853 (A)
`
`PURPOSErTo prepare a reddish orange
`coloring matter having a high safety in a
`high concn. by extracting, with 002 in a
`supercritical state, krill shells of which the
`protein has been decomposed by a
`protease. CONSTITUTIONzKrill shells are
`treated with a protease to decompose the
`protein in the shells and the treatment
`product is filtered. The residue of filtration is
`dried to give treated shells having a water
`content of 6-894) and a mean particle size of
`200 mum or lower. The treated shells are
`put into an extraction vessel 5. An
`extractant comprising a liq.; CO2 in an amt.
`of 30-40 pts.wt. based on one ptwt. treated
`shells having a coloring matter concn. of 30
`mg/100 g is supplied through a
`supercooling apparatus 2 to a pump 3,
`pressurized at the pump 3 to 100-250
`kg/cm<2>, heated with a heat exchanger 4
`to 35-40 deg.C to bring it into a supercritical
`
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`state. and transferred to the extraction
`vessel 5 to extract an oil in the treated
`shells. After the pressure of the oil-contg.
`002 in the supercritical state is reduced to 40-60 kg/cm<2> with a pressure reducing
`valve 6, the 002 is delivered through a selector valve 11 to the first separating vessel 7
`to separate the oil, and recycled through a selector valve 13, a pressure reducing valve
`9, a condense 10, a water separator 15, and a storage vessel 1 to the extraction vessel
`5.; Then, selector valves 11 and 13 are closed while selector valves 12 and 14 are
`opened, and the 002 contg. the coloring matter is transferred to the second separating
`
`8/05/2012
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`Espacenet — Bibliographic data
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`Page 2 of 2
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`vessel 8. where the 002 is evaporated to give a coloring matter with a concn. of 2000—
`10000 mg/100g.
`
`Last Updated: 14332012 Woneride Database
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`5.7.38: 93;)
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`(19) Japan Patent Office (JP)
`(12) Unexamined Patent Application Publication (A)
`
`(11) Unexamined Patent
`Application Publication No.
`H4-5785 3
`
`(51) Intl. Classifications:
`C 09 B 61/00
`
`ID Code:
`A
`
`Internal File No.2
`75 37-4H
`
`(43) Publication Date: February 25, 1992
`
`Examination Requested: No Number of Claims: 5
`
`(7 Pages Total)
`
`(54) Title of Invention: METHOD FOR EXTRACTING AND SEPARATING PIGMENT FROM KRILL
`
`(21) Patent Application No.: H2-170549
`(22) Filing Date: June 28, 1990
`
`N
`
`(72) Inventor:
`
`Tsuneo TOKUMORI
`201 Koporasusan, 2097—3 Chayamachi, Kurashiki City, Okayama Prefecture
`\ (2) Inventor: Yoko SUMIDA
`1-6-29 Gakunancho, Okayama City, Okayama Prefecture
`(72) Inventor: Koichi TSUYAMA
`202 Sejuru Shinbo-Kita, 1135-10 Shinbo, Okayama City, Okayama Prefecture
`Iyoko KUNISHIRO
`706-1 Shinbo, Okayama City, Okayama Prefecture
`(72) Inventor: Hamo OKADA
`1068 Ushijima, Kamajimacho, Oe-gun, Tokushima Prefecture _
`Toshifumi TANI
`26—4 Higashiboji, Kitanadacho Awata, Naruto City, Tokushima Prefecture
`(71) Applicant: Chlorine Engineers Corp. Ltd.
`Shosen Mitsu Bldg, 2-1—1 Toranomon, Minato-ku, Tokyo
`Itano Reitou K.K.
`33-2 Nikkenya, Setocho Myoj in, Naruto City, Tokushima Prefecture
`Akira YONEZAWA, Patent Agent, and seven others
`
`(72) Inventor:
`
`(72) Inventor:
`
`(71) Applicant:
`
`(74) Agent:
`
`Specification
`
`1. Title of Invention
`
`Method for extracting and separating pigment
`from krill
`
`2. Claims
`(1) A method for extracting and separating
`pigment from krill, wherein, using as a starting
`material krill shells that are the residue after krill
`has been decomposed by a protease and the protein
`removed, pigment is extracted and separated with
`supercritical carbon dioxide as an extraction agent.
`(2) The method for extracting and separating
`pigment from krill according to claim 1, wherein
`extraction and separation are characterized in that
`
`the extract from the krill shells is fractionated while
`varying the pressure of supercritical carbon dioxide
`in two stages.
`(3) The method for extracting and separating
`pigment from krill according to claim 1, wherein
`extraction and separation are characterized in that
`the extract from the krill shells is fractionated by
`separation over time without varying the pressure of
`supercritical carbon dioxide.
`(4) The method for extracting and separating
`pigment from krill according to claim 1, wherein
`extraction and separation are characterized in that
`components extracted in an extraction tank are
`fractionated by a plurality of separation tanks of
`different conditions.
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`(5) The method for extracting and separating
`pigment from krill according to any one of claims 1
`through 4, characterized in that the moisture content
`ratio ofkrill shells is from 10% to 30%.
`
`3. Detailed Description of the Invention
`(Industrial Field of Use)
`The present invention relates to a method for
`obtaining high-concentration pigment by separating
`the reddish-orange pigment having a primary
`component of astaxanthin contained in krill, and in
`particular, it relates to a method of extraction and
`separation using supercritical carbon dioxide.
`(Prior Art)
`The reddish-orange pigment having a primary
`component of astaxanthin contained in krill has
`generally been extracted from krill organisms using
`an organic solvent. This extract contains various
`components, starting with the lipids that are
`contained in krill. In particular, concentration and
`separation of only the pigment contained in the
`pigment extract is necessary because oxidative
`decomposition products such as unsaturated fatty
`acids and glycerol esters thereof bonded to or
`coexisting with the pigment give off an unpleasant
`odor, or reaction products in the course of oxidative
`decomposition such as unsaturated fatty acids cause
`fading of the pigment.
`As methods for concentrating and separating
`pigment from krill pigment extract liquid, Japanese
`Unexamined Patent Application Publication No.
`860-4558 and Japanese Examined Patent
`Application Publication No. 861-52183 propose a
`method in which the pH of krill pigment extract
`liquid extracted by an organic solvent such as n-
`hexane or acetone is neutralized and lipids are then
`decomposed by a lipase, and a method in which
`pigment liquid is separated from a liquid in which
`an alkali has been added to decompose lipids or
`other impurities, and then this pigment liquid is
`extracted and separated by molecular distillation or
`by a fluid in the supercritical state.
`(Problems the Invention is to Solve)
`In the proposed krill pigment concentration and
`separation methods of prior art, numerous steps are
`required, including a step of extracting krill pigment
`liquid from krill organisms by an organic solvent, a
`neutralization step, a step of decomposing lipids and
`impurities by lipase or alkali, a step of decomposing
`the decomposition products of impurities and krill
`
`pigment, and an extraction step by molecular
`distillation or a fluid in the supercritical state.
`Furtherrnore, it has been reported that the reddish—
`orange pigment contained in krill has astaxanthin as
`a primary component and has 100 to 1000 times the
`antioxidant action of vitamin E, and is anticipated to
`be used as a drug starting substance in the future. If
`used as a drug starting substance, however, steps
`such as solvent removal will be required in order to
`completely eliminate residue of the organic solvent
`used in the krill pigment liquid extraction step.
`A method has also been considered wherein lqill
`
`
`
`4%
`
`i
`
`7
`
`are extracted directly by supercritical carbon
`dioxide without going through treatment steps, but
`it is difficult to extract and separate only the
`pigment because the large amount of moisture and
`various useful components contained in krill are
`simultaneously extracted.
`(Means for Solving Problems)
`The present inventors arrived at the present
`invention as a result of diligent research to solve the
`above problems.
`Since krill contains a large amount of useful
`components such as proteins, it has been used in
`applications such as starting materials for processed
`foods. Among these applications, the proteins
`contained in krill have been separated and used in
`the starting materials of amino acids, rather than
`krill being used as is. However, the krill shells from
`which such proteins used in starting materials of
`amino acids have been removed were discarded or
`only used as feed for cultivated fish in the past.
`The present inventors discovered that krill
`pigment is produced without going through special
`pretreatment steps by employing a simple method
`wherein krill pigment liquid is extracted from krill
`using a supercritical fluid, by using the shells
`remaining after components such as proteins from
`krill have been removed as the starting material of
`pigment production.
`That is to say, pigment is extracted by a
`supercritical fluid using as a starting material krill
`shells that are the residue obtained by methods such
`as filtration after the useful components such as
`proteins in the krill have been decomposed by
`enzymes.
`
`The supercritical fluid in the present invention is a
`fluid in a state beyond the critical temperature and
`critical pressure. In the case of carbon dioxide, it is
`the state at 31°C or above, 75.3 Kg/cm2 or above;
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`for propane, 967°C or above, 43.4 Kg/cm2 or
`above; for ethane, 99°C or above, 52.2 Kg/cm2 or
`above. These fluids are characterized by having
`density close to that of a liquid and a large
`expansion coefficient close to that of a gas, and can
`be used in extraction and separation of various
`organic matter. In the method of the present
`invention, carbon dioxide in particular is used as the
`supercritical fluid. When carbon dioxide gas is used,
`not only are the steps required in extraction and
`separation of pigment simplified, but there is
`absolutely no danger even if the carbon dioxide
`used as the extraction agent remains in the extracted
`pigment, for example, and the obtained pigment can
`7 be used without a problem in many fields starting
`ith pharmaceuticals.
`Additionally, supercritical carbon dioxide used as
`an extraction agent has no risk of explosion or
`combustion in air like hydrocarbons do.
`Furthermore, since the critical temperature and
`critical pressure of carbon dioxide are relatively low,
`dissolution characteristics can be easily varied by
`varying the temperature and pressure, and it is
`possible to perform extraction with an extraction
`agent having dissolution characteristics suited to
`pigment extraction and separation.
`The method of the present invention is to extract
`pigment with supercritical carbon dioxide using
`krill shells as a starting material. The method of the
`present invention was achieved by studying the
`extraction conditions such as extraction pressure,
`temperature and fractionation method for
`-“~erforming efficient extraction and separation of
`gment, and by studying the water content ratio of
`the starting material krill.
`The present invention will be described below in
`reference to the drawings.
`FIG. 1 is a flowchart of equipment having a
`means for switching among a plurality of separation
`tanks for implementing the method of the present
`invention.
`
`The extraction agent carbon dioxide passes from a
`liquid carbon dioxide storage tank 1 to a
`supercooler 2, after which it is pressurized to a
`prescribed pressure by a pump 3, and then heated to
`a prescribed temperature by a heat exchanger 4, and
`supplied as supercritical carbon dioxide to an
`extraction tank 5 filled with krill shells.
`The starting material krill shells primarily contain
`chitin, proteins, triglyceride esters, triglyceride
`
`esters, monoglyceride esters (oil components) and
`pigment (astaxanthin). The residue obtained when
`frozen krill is thawed and then the extract portion in
`which the proteins decomposed by a protease have
`been filtered out is a powder with an average
`particle size of 200 um, and normally has a water
`content ratio of 6% to 8% after it is dried.
`Since supercritical carbon dioxide has the
`characteristic that it decomposes the oil components
`and pigment of krill shells, only two components
`are extracted from the krill shells, but in order to
`separate these two components, the extraction
`operation is divided into two stages.
`Namely, in the first extraction, the oil components
`contained in the krill shells are extracted by passing
`through 30 parts by weight to 40 parts by weight of
`supercritical carbon dioxide having a temperature of
`30°C to 50°C and a relatively low pressure of 100
`Kg/cm2 to 250 Kg/cm2 for every 1 part by weight of
`krill shells having a pigment concentration of 30
`mg/ 100 g, which is equivalent to the concentration
`of contained astaxanthin.
`The supercritical carbon dioxide that contains oil
`components is reduced in pressure to 40 Kg/cm2 to
`60 Kg/cm2 by a pressure reducing valve 6, and led
`into a first separation tank 7 via a switching valve
`11.
`In the first separation tank 7, carbon dioxide in the
`gas state which has separated the oil components is
`further reduced in pressure and adiabatically
`expanded by a switching valve 13 and a pressure
`reducing valve 9, and after being liquefied by a
`condenser 10, it passes through a water separator 15
`and returns to the liquid carbon dioxide storage tank
`1 where it is recirculated.
`Then, supercritical carbon dioxide is supplied to
`the extraction tank 5 at a pressure higher than the
`pressure during the first extraction stage. That is, 30
`parts by weight to 40 parts by weight of
`supercritical carbon dioxide having a temperature of
`30°C to 50°C and a pressure of 300 Kg/cm2 to 500
`Kg/cm2 is supplied to the extraction tank for every 1
`part by weight of krill shells, and by closing the
`switching valves 11 and 13 and opening switching
`valves 12 and 14, carbon dioxide containing extract
`with a pressure of 40 Kg/cm2 to 60 Kg/cm2 is led to
`a second separation tank 8 by the pressure reducing
`valve 6.
`In the second separation tank 8, carbon dioxide in
`the gas state is returned to the liquid carbon dioxide
`
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`storage tank 1 in the same way as in the first
`extraction step. From the second separation tank,
`pigment with an extremely high concentration of
`2000 mg/100 g to 10,000 mg/100 g can be obtained.
`High-concentration pigment is obtained by
`successive two-stage high-pressure extraction as
`described above, but it is possible to efficiently
`collect it by providing a plurality of separation tanks
`and switching among them.
`Furthermore, even if the two-stage extraction is
`not performed while varying the pressure as
`described above, it is possible to similarly perform
`extraction and separation at the same pressure.
`That is, extraction and separation of high-
`concentration pigment is also possible by the
`extraction operation illustrated in FIG. 2. To
`describe the operation in reference to FIG. 2, carbon
`dioxide is fed from the liquid carbon dioxide
`storage tank 1 through the supercooler 2 to the
`pump 3, and pressured to a prescribed pressure.
`Then, it is heated to a prescribed temperature by the
`heat exchanger 4 to make a supercritical fluid,
`which is supplied to the extraction tank 5 filled with
`krill shells.
`
`30 parts by weight to 50 parts by weight of
`supercritical carbon dioxide at a temperature of
`35°C to 50°C and a pressure of 300 Kg/cm2 to 500
`Kg/cm2 is passed through for every 1 part by weight
`of krill shells (pigment concentration 30 mg/ 100 g).
`In the extraction tank, oil components are extracted
`initially, and then high-concentration pigment is
`extracted, and the supercritical carbon dioxide gas
`containing the extract is reduced in pressure to 40
`Kg/cm2 to 60 Kg/cm2 by the pressure reducing
`valve 6 and led to the first separation tank 7.
`The carbon dioxide that comes out from the first
`separation tank is further reduced in pressure by the
`pressure reducing valve 9, and after being liquefied
`by the condenser 10, it passes through the water
`separator 15 and returns to the liquid carbon dioxide
`storage tank 1.
`In this extraction method, because supercritical
`carbon dioxide of relatively high pressure is used
`from the start of extraction, pigment is also
`extracted together with the oil components,
`resulting in loss of pigment. Therefore, after
`extraction is performed by supplying 15 parts by
`weight to 25 parts by weight of supercritical carbon
`dioxide for every 1 part of krill shells, the extract,
`which is primarily made up of oil components, is
`
`separated from a feed out valve 16 provided on the
`bottom of the first separation tank 7. Then, by
`supplying 15 parts by weight to 25 parts by weight
`of supercritical carbon dioxide for every 1 part of
`krill shells, pigment concentrate is obtained in the
`first separation tank.
`The pigment concentration in the oil components
`obtained by this method was from 10 mg/ 100 g to
`30 mg/ 100 g, and the pigment concentration in the
`pigment concentrate was from 2000 mg/ 100 g to
`10,000 mg/100 g.
`In this method, because supercritical carbon
`dioxide of relatively high pressure is used from the
`start of extraction, a slight amount of pigment is
`contained in the oil components that constitute the
`initial extract, but this method has the advantage
`that extraction time can be shortened compared to
`the aforementioned method that uses supercritical
`carbon dioxide in two stages of low pressure and
`high pressure.
`Furthermore, FIG. 3 illustrates a method in which
`a plurality of tanks are provided in succession, and
`pigment is efficiently recovered while varying the
`separation conditions by varying the set pressure
`and temperature of each separation tank.
`The method will be described below in reference
`to FIG. 3.
`
`
`
`Carbon dioxide is fed from the liquid carbon
`dioxide storage tank 1 through the supercooler 2 to
`the pump 3, and pressurized to a prescribed pressure.
`After that, it is heated to a prescribed temperature
`by the heat exchanger 4 and supplied as
`supercritical carbon dioxide to the extraction tank 5 5%
`filled with krill shells.
`
`Here, the supercritical carbon dioxide supplied to
`the extraction tank 5 has a temperature of 35°C to
`50°C and a pressure of 300 Kg/cm2 to 500 Kg/cmz.
`Oil components and pigment are extracted from
`the krill shells in the extraction tank, and the
`supercritical carbon dioxide that contains these oil
`components and pigment is reduced in pressure by
`the pressure reducing valve 6, and led to a high-
`pressure separation tank 17.
`The high-pressure separation tank 17 is held in the
`supercritical state at a pressure lower than inside the
`extraction tank at a temperature of 35°C to 50°C
`and a pressure of 100 Kg/cm2 to 300 Kg/cmz.
`Pigment concentrate is collected in the tank, and the
`supercritical carbon dioxide that contains oil
`components is reduced in pressure by a pressure
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`reducing valve 18 and led to a low-pressure
`separation tank 19.
`While the low--pressure separation tank 17 is held
`in a gas state at a temperature of 20°C to 30°C and a
`pressure of 40 Kg/cm2 to 60 Kg/cmz, the carbon
`dioxide13 again reduced1n pressure by the pressure
`reducing valve 9, and after being liquefied by the
`condenser 10, the moisture it contains is removed
`by the water separator 15, and the carbon dioxide is
`returned to the liquid carbon dioxide storage tank 1.
`When this method is used, by passing through 30
`parts by weight to 40 parts by weight of
`supercritical carbon dioxide of a relatively high
`pressure of 300 Kg/cm2 to 500 Kg/cm2 for every 1
`, part by weight of krill shells (pigment concentration
`'1 mg/ 100 g), pigment with an extremely high
`Jncentration of 2000 mg/ 100 g to 10,000 mg/ 100 g
`can be obtained in the high-pressure separation tank,
`and oil components having a low pigment
`concentration can be obtained as an extract in the
`
`'
`
`low—pressure separation tank.
`In the method in which the supercritical carbon
`dioxide supplied to the extraction tank15 initially at
`a relatively low pressure below 300 Kg/cm2 and
`then supercritical carbon dioxide at a relatively high
`pressure is supplied, the yielded quantity of pigment
`is high because almost no pigment is extracted in
`the initial extract, but extraction takes a long time.
`On the other hand, in the method in which the initial
`extraction extracts oil components are extracted in
`the initial extraction step using supercritical carbon
`dioxide at a relatively high pressure of 300 Kg/cm2
`'1 500 Kg/cm2 and then the extract of pigment
`1ncentrate is separated over time, the equipment
`configuration is simple and extraction time is short,
`but since some pigment is contained in the oil
`components obtained as the initial extract, there is
`the problem that the yielded quantity of pigment is
`reduced. However, the method illustrated in FIG. 3,
`in which a plurality of separation tanks having
`different set pressures and temperatures is provided
`and extracts of components are obtained in
`succession under different extraction conditions, is
`superior to the aforementioned two methods.
`Furthermore, in the present invention, by
`performing extraction alter increasing the moisture
`content of the krill shells (pigment concentration 30
`mg/ 100 g) used as the starting material to 10 wt% to
`30 wt%, it is possible to speed up extraction speed,
`particularly the initial extraction speed, and as a
`
`result, it is possible to reduce the amount of pigment
`contained in the extract of oil components initially
`obtained1n extraction when supercritical carbon
`dioxide at a relatively high pressure of 300 Kg/cm2
`to 500 Kg/cm2 is used, and therefore, a reduction of
`the amount of pigment contained in the oil
`components and lost can be prevented.
`Because water has been added, water is extracted
`together with pigment, but since water and pigment
`can be easily separated into two layers, adding
`water does not hinder extraction and separation of
`
`pigment in any way.
`However, if the water content ratio exceeds 30%,
`a reductionin extraction speedin the initial
`extraction is seen, and therefore it is undesirable if
`the amount of water exceeds 30%.
`It is preferred that the water content ratio of the
`krill shells be adjusted by controlling the dry state
`in the krill treatment step, but in cases where krill
`shells of relatively low moisture content in the dry
`state are used, it is necessary to disperse water in
`the krill shells and sufficiently mix before the
`
`extraction step
`[Operation]
`The present invention is a method for producing
`pigment made up of astaxanthin contained1n krill1n
`which it is extracted using as a production starting
`material krill shells that are the residue after krill
`has been decomposed by a protease and the protein
`and so forth removed, and using supercritical
`carbon dioxide as an extraction agent. The method
`of the present invention can produce krill pigment
`without going through a special pretreatment step
`using an organic solvent.
`(Examples)
`The present invention will be described1n further
`detail below by giving examples of the present
`invention.
`
`Example 1
`Using a protease as a protein decomposition
`enzyme, frozen krill after thawing were made to
`undergo a proteolysis reaction for 2 hours at 47 °C
`to 48°C, and then the liquid was filtered and the
`separated residue was dried to obtain krill shells
`containing 6% water. An extraction tank having a
`volume of 25 liters was packed with 6 Kg of these
`krill shells (pigment concentration 30 mg/ 100 g).
`While holding the tank temperature at 40°C,
`supercritical carbon dioxide having a temperature of
`40°C and pressure of 200 Kg/cm2 was supplied for
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`4 hours at a supply rate of 60 Kg per hour. In a
`separation tank set to a pressure of 50 Kg/cm2 and
`temperature of 30°C, carbon dioxide and liquid
`were separated, and 1398 g of extract with a
`pigment concentration of 7.1 mg/ 100 g was
`obtained from a feed out valve on the bottom of the
`separation tank.
`Additionally, in the extraction tank, supercritical
`carbon dioxide at a temperature of 40°C and
`pressure of 400 Kg/cm2 was supplied for 4 hours at
`a supply rate of 60 Kg per hour, and in the
`separation tank set to a pressure of 50 Kg/cm2 and
`temperature of 30°C, 13.4 g of high-concentration
`extract having a pigment concentration of 8331
`mg/ 100 g was obtained from the residue of the
`previous extract.
`Example 2
`An extraction tank having a volume of 25 liters
`was packed with 6 Kg of krill shells (pigment
`concentration 30 mg/ 100 g) having the same
`components as those used as a starting material in
`example 1. While holding the tank temperature at
`40°C, supercritical carbon dioxide having a
`temperature of 40°C and pressure of 400 Kg/cm2
`was supplied for 2 hours at a supply rate of 60 Kg
`per hour. 1703 g of extract with a pigment
`concentration of 42.8 mg/ 100 g was obtained from a
`feed out valve on the bottom of a separation tank set
`to a pressure of 50 Kg/cm2 and temperature of 30°C.
`Additionally, in the extraction tank, supercritical
`carbon dioxide at a temperature of 40°C and
`pressure of 400 Kg/cm2 was supplied for 5 hours at
`a supply rate of 60 Kg per hour, and in the
`separation tank set to a pressure of 50 Kg/cm2 and
`temperature of 30°C, 10 g of high-concentration
`pigment having a pigment concentration of 5874
`mg/ 100 g was obtained.
`Example 3
`An extraction tank having a volume of 1 liter was
`packed with 250 g of krill shells (pigment
`concentration 30 mg/ 100 g) having the same
`components as those used as a starting material in
`example 1. While holding the tank temperature at
`40°C, supercritical carbon dioxide having a
`
`temperature of 40°C and pressure of 400 Kg/cm2
`was supplied for 2.5 hours at a supply rate of 2.5 Kg
`per hour. The supercritical carbon dioxide
`containing the extract obtained in the extraction
`tank was supplied to a high-pressure separation tank
`held in the supercritical state.
`While holding the high-pressure separation tank at
`a temperature of 40°C and pressure of 250 Kg/cmz,
`the extract in the low-pressure separation tank was
`supplied Via a pressure reducing valve to a low-
`pressure separation tank held at 20°C and 60
`Kg/cmz.
`As a result, 0.44 g of pigment with a pigment
`concentration of 7072 mg/ 100 g was obtained from
`the high-pressure separation tank, and 70.57 g of
`pigment with a pigment concentration of 6.2
`mg/ 100 g was obtained from the low—pressure
`separation tank.
`
`
`
`Example 4
`Water was dispersed and sufficiently mixed with
`6 Kg of krill shells having the same components as
`those used as a starting material in example 1, and
`extraction and separation of pigment were
`performed while varying the water content ratio of
`the starting material.
`An extraction tank having a volume of 25 liters
`was packed with the krill shells of different water
`content ratios, and while holding the extraction tank
`temperature at 40°C, supercritical carbon dioxide
`having a temperature of 40°C and pressure of 400
`Kg/cm2 was supplied, and it was separated in a
`separation tank set to a pressure of 50 Kg/cm2 and
`temperature of 30°C. The amount of oil component %
`fraction obtained from the start of extraction and thel~
`amount of pigment obtained after fractionation of
`the oil components ended are shown in Table 1
`together with extraction time.
`
`(intentionally blank)
`
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`

`
`
`Table l
`
`Pigment concentrate
`Oil components
`
`Extraction time
`Extracted quantity (g)
`Extraction time
`Water content ratio
`Extracted quantity (g)
`(%)
`(hours)
`Pigment concentration
`(hours)
`Pigment concentration
`(mg/ 100 g)
`(mg/ 100 g)
`
`3
`2
`1649
`3
`18.7
`12.3
`1660
`
`7
`2
`1703
`3
`6.8
`42.8
`7832
`
`14
`1
`1546
`2
`1 1.9
`28.3
`6084
`
`
`
`(5
`
`(Advantageous Effect of the Invention)
`The present invention is a method that extracts
`‘ :ldish-orange pigment containing astaxanthin from
`mill shells using supercritical carbon dioxide, which
`makes effective use of krill shells as starting
`materials, which were treated as waste in the past,
`by extracting the useful components from krill.
`Moreover, since it does not use organic solvents and
`so forth, the process is simple and does not require
`organic solvent separation steps, and it can extract
`and separate pigment by a method that is highly
`safe even in the fields of foods and pharmaceuticals.
`
`4. Brief Description of the Drawings
`FIG. 1 is a flowchart of extraction equipment that
`switches among multiple separation tanks used for
`implementing the method of the present invention.
`FIG. 2 is a flowchart of equipment used when
`fractionating two components at the same pressure
`‘rr implementing the method of the present
`,vention. FIG. 3 is a flowchart of equipment
`having separation tanks at different pressures used
`for implementing the method of the present
`invention.
`
`Liquid carbon dioxide storage tank
`Supercooler
`2
`Pump
`3
`Heat exchanger
`Extraction tank
`
`4
`5
`
`1
`
`7
`
`6
`
`8
`9
`
`Pressure reducing valve
`First separation tank
`Second separation tank
`Pressure reducing valve
`Condenser
`10
`Switching valves... 11, 12, 13, 14
`Water separator 15
`Feed out valve
`l6
`High-pressure separation tank
`Pressure reducing valve
`18
`Low-pressure separation tank
`
`17
`
`19
`
`Patent Applicant: Chlorine Engineers Corp. Ltd.
`(and one other)
`Agent: Akira YONEZAWA, Patent Agent (and
`seven others)
`
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`