WO2007020973A1 - Procédé de récupération de carnitine - Google Patents

Procédé de récupération de carnitine Download PDF

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Publication number
WO2007020973A1
WO2007020973A1 PCT/JP2006/316164 JP2006316164W WO2007020973A1 WO 2007020973 A1 WO2007020973 A1 WO 2007020973A1 JP 2006316164 W JP2006316164 W JP 2006316164W WO 2007020973 A1 WO2007020973 A1 WO 2007020973A1
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WO
WIPO (PCT)
Prior art keywords
carcin
column
solution
resin
permeate
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Application number
PCT/JP2006/316164
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English (en)
Japanese (ja)
Inventor
Shigeko Suido
Hiroshi Echizen
Original Assignee
Meiji Dairies Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Meiji Dairies Corporation filed Critical Meiji Dairies Corporation
Priority to JP2007531023A priority Critical patent/JP5405020B2/ja
Publication of WO2007020973A1 publication Critical patent/WO2007020973A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/38—Separation; Purification; Stabilisation; Use of additives
    • C07C227/40—Separation; Purification

Definitions

  • the present invention relates to an ultrafiltration permeate of milk or a dairy product or a method for recovering carcin in whey.
  • Carcin is biosynthesized from the essential amino acids lysine and methionine mainly in the liver and partially in the kidney. Its biosynthetic capacity is 0.16-0.48 mg / kg of body weight / day. In addition, since 95% of carcin is filtered and reabsorbed by the kidneys, it does not cause cartilin deficiency in healthy individuals. However, it is said that the ability of carcin to synthesize in newborns is lower than that of adults, and it is said to decrease with age. Carnitine plays an important role in fatty acid metabolism when fatty acids enter the mitochondria, and the functions of carnitine such as recovery from fatigue, improvement of exercise ability, and prevention of brain aging have recently been attracting attention.
  • Carcin is abundant in mutton, beef, etc., and extracts and synthetic products from these products, and recently, L-carcin preparations by microbial fermentation are sold.
  • the amount of carcin contained in milk is as low as around 40mg / 100g in terms of dry matter.
  • carcin is transferred to whey, a by-product of cheese and casein production, and to ultrafiltration (UF) permeate, a by-product of making WPC from whey. If whey or UF permeate can efficiently recover carcin, it can be used as a formula powder or functional health ingredient.
  • Carcin is a kind of amino acid having a dissociation constant of 3.8, and behaves as a cation in a solution having a pH of 3.8 or lower. Utilizing this property, a method for recovering UF permeate carcin using a column packed with cation exchange resin has been disclosed (see Patent Document 1). However, simply attaching the UF permeate to the cation exchange resin has the problem that ions such as calcium and sodium are also recovered along with the carcin.
  • Patent Document 1 JP-A 62-63553
  • an object of the present invention is to find a method for industrially advantageously recovering a carcin having a low ion content such as calcium from UF permeate of milk or dairy products or whey. is there.
  • the present inventor conducted intensive studies on adsorption and release of carcin and other ions in an ion exchange resin column. It is found that a large amount of carcin is adsorbed in the lower layer of about 1Z3 below the upper part, and if the eluate is supplied only to the lower part and the carcin is eluted, the content of other ions is small. The present invention was completed by finding that carcin can be efficiently recovered.
  • the present invention supplies ultrafiltration permeate or whey of milk or dairy products to the upper part of the column filled with cation exchange resin, and below about 1Z3 below the resin filler part of the column.
  • the present invention provides a method for recovering carcin, characterized in that carcin is adsorbed to a layer part, and then an eluate is supplied to the lower layer part to elute carcin.
  • carcin can be recovered from a UF permeate or whey of milk or dairy products with a low content of cations such as calcium.
  • FIG. 1 is a diagram showing an example of an apparatus used in the present invention.
  • FIG. 2 is a diagram showing the relationship between the length and absorption of scab.
  • FIG. 3 is a diagram showing the relationship between the length and absorption of scab.
  • FIG. 4 is a diagram showing the relationship between the length and absorption of scab.
  • FIG. 5 is a diagram showing the relationship between the length and absorption of scab.
  • FIG. 6 is a diagram showing a procedure for carcin elution.
  • FIG. 7 shows NaOH titration and pH change.
  • FIG. 8 is a diagram showing the relationship between KOH and recovery rate.
  • FIG. 9 is a diagram showing the relationship between KOH and recovery rate.
  • FIG. 10 is a diagram showing the relationship between KOH and recovery rate.
  • “Milk” as a starting material of the present invention refers to raw milk, milk, skim milk, partially skimmed milk, component-adjusted milk, etc.
  • “dairy product” refers to concentrated milk, whole milk powder, skim milk powder, whey, whey. Powder, condensed milk, milk protein concentrate (MPC), whey protein concentrate (WPC), whey protein isolate (WPI), etc.
  • Milk or dairy products are preferably subjected to UF (ultrafiltration) as follows.
  • the molecular weight cutoff of the UF membrane is not particularly limited, but is preferably about 1,000-50,000.
  • the membrane used in the UF device is not particularly limited, and a hollow type, a disk type, and the like can be used as appropriate.
  • any of the permeate obtained by UF treatment, the concentrate obtained by concentrating the permeate, and the liquid from which lactose precipitated during the concentration is removed can be used as a raw material.
  • cation exchange resin column Column packed with cation exchange resin (hereinafter referred to as "cation exchange resin column")
  • the cation exchange resin used in the present invention is not particularly limited, but is preferably strongly acidic.
  • the functional group is preferably sulfonic acid.
  • the total exchange capacity is preferably 1.6 to 2.2 eqZl, and particularly preferably 1.8 to 2 eqZl.
  • ion exchange resins include Amberlite IR120B (Rohm and Haas), Diaion ( R ) SKI ⁇ SKI 04 ⁇ S K110- SK112- SK116 -PK208 -PHK212-PK216 -PK220- PK228 -HPK25 etc. are mentioned.
  • the length of the packed cation exchange resin in the column should be at least 600 mm considering the position of the adsorption zone of carcin. Multiple columns are not necessary. You can connect them in series!
  • milk or dairy product UF permeate or whey (hereinafter referred to as “raw material”) is supplied from the top of the cation exchange resin column.
  • the supply line speed is preferably 1 to 12 mZh, particularly 3 to 8 mZh.
  • cations such as calcium are adsorbed on the resin, and hydrogen ions are released into the liquid phase, resulting in a low pH.
  • Carcin is then positively charged and is adsorbed by rosin.
  • the saturation point can be determined by the supply amount (volume or weight of the supply liquid) when the composition and concentration of the raw material are known.
  • the feed rate of the raw material is preferably 1.1 to 1.85 kg as the solid content of the raw material liquid per liter of fat. This corresponds to a total equivalent of calcium, magnesium, potassium and sodium of 1.5 to 2.4 eqZ 1—R (the nominal exchange capacity of the ion exchange resin is 1.9 eqZl—R).
  • a cartilage solution containing less calcium and the like can be obtained by supplying the eluate so that the entire column is washed from the upper part of the other column. .
  • ultrafiltration permeate of milk or dairy product or whey is supplied to the lower part of the column filled with cation exchange resin, and the upper layer of about 1Z3 above the resin-filled part of the column. It is also possible to adsorb the carcin to the part and then supply the eluate to the upper layer part to elute the carcin. In this case, if the upper layer of about 1Z3 above the resin-filled portion of the column is separated into a separate column, and the eluate is supplied after separation, the eluate does not go to the lower layer, and there is little contamination with calcium, etc. -U, which can get chin solution.
  • the eluate is preferably an alkaline solution, particularly a hydroxyl group.
  • a solution of potassium is preferred.
  • the concentration of the eluate is preferably 0.4 to 3N, and more preferably 0.5 to 2N. 1Z4 to 1 times is preferable, and 1Z3 to 1Z2 times is particularly preferable.
  • the operations of the present invention are all preferably carried out at 2 to 50 ° C, particularly 5 to 20 ° C.
  • the sample used was a whey UF permeate (hereinafter referred to as “UF permeate” t).
  • UF permeate t whey UF permeate
  • two types of UF permeate were prepared as follows.
  • the whey powder was dissolved in 27%, cooled to 10 ° C or lower, and separated by a hollow fiber type UF membrane with a molecular weight cut off of 10,000 to obtain a UF permeate.
  • this UF permeate has a lower calcium content than the UF permeate obtained by UF membrane separation without drying the liquid whey after cheese curd separation, salt calcium was added to adjust the calcium content.
  • Table 1 shows the composition of the sample. Calcium, magnesium, potassium and sodium, which are the main cations in the UF permeate, are summed in terms of equivalent amounts, and Dil. Liquid and Cone. Liquid contain 0.13eqZl and 0.32eqZl respectively. The ratio of monovalent ions and divalent ions is 80:20.
  • Figure 1 shows the experimental setup.
  • the height of the resin layer should be 600 mm or more considering the movement of the adsorption zone. Therefore, three glass columns with a diameter of 25 mm and a height of 500 mm were connected in series, and each column was filled with 160 ml of a strongly acidic styrene-based gel cation exchange resin “Amberlite IR-120BJ (Rohm & Haas), The total height of the resin layer was 980 mm.
  • backwashing was performed by flowing water at an upward flow of 8mZh for 12 minutes. Regeneration was performed with twice the normal amount of hydrochloric acid to stabilize the condition of the resin.
  • Carcin was measured according to Japanese Patent Application Laid-Open No. 2002-277452 (Method for measuring L-carcins in foods).
  • NPN Non-protein nitrogen
  • 12% trichloroacetic acid soluble nitrogen was determined by measuring 12% trichloroacetic acid soluble nitrogen by the Kjeldahl method and multiplying by a factor of 6.38.
  • the fraction soluble in 12% trichloroacetic acid was measured by “Urea Nitrogen B Test Sakai Koichi” (Wako Pure Chemical Industries). Minerals were measured by atomic absorption.
  • Dil. Liquid and Cone Liquid as solid content 1.2-1.6 kgZl—R (total equivalent of calcium, magnesium, potassium and sodium 1. 6, 1. 8, 2. 0, 2. 2eqZl—R) Then, the liquid remaining in the column was pushed out with 1.2 times the volume of the resin so that the sugar content (Brix) of the outlet liquid was 0.2 or less.
  • the supply line speeds were 8 mZh and 3.2 mZh for Dil. Liquid and Cone. Liquid, respectively.
  • the regenerated solution in the first column, Column I contains components adsorbed up to 330mm from the top layer of the resin.
  • the top layer force of the resin is 330 to 650m, 650 for the regenerated solution of the second column II and the third column III, respectively. It is adsorbed between ⁇ 980mm! Adsorbed up to 980 mm! / Min, the component is transferred to the desalting solution.
  • Figures 2 and 3 show the results of plotting the integrated ratio against the inlet liquid content of each component adsorbed up to the height on the horizontal axis on the horizontal axis and the vertical axis on the vertical axis.
  • Fig. 4 shows the adsorption distribution when 1.3 kg'TSZl-R is supplied.
  • Figure 5 shows the experimental results of using the Dil. Solution as a sample and reducing the supply line speed for the purpose of improving the separation of carnitine and other components. Although slowing the supply line speed tends to increase the amount of carcin adsorbed to column III, it has little effect on the adsorption distribution.
  • Carnitine is not adsorbed on the top of the column, and about 70% of carcin is just before the saccharite reaches adsorption saturation (approx. 1.3 kg. After feeding TSZl-R UF permeate). It was adsorbed on the lower 1Z3 resin.
  • the UF permeate was supplied in an amount equivalent to 1.3 kg / l-R (1.8 eq / l-R as the total equivalent of calcium, magnesium, potassium and sodium) as the solid content.
  • the supply rate of the UF permeate was the same as in Experiment 1-4.
  • the UF permeate in the column was pushed out with water of 1.2 times the volume of the resin and mixed with the desalted solution.
  • the following operation was performed to elute the carcin adsorbed on the resin.
  • salt-calcium, salt-potassium, and hydroxide-potassium which are soluble salt solutions having a higher adsorption selectivity for fat than sodium
  • hydrochloric acid used for regeneration was also used as a comparative control.
  • the concentration of the solution was 0.5 N, and 0.8 times (0.4 eqZl-R) of the volume of the resin was supplied so that the total equivalent of the UF permeate and the eluent was 2.2 eqZl-R.
  • the water of operation (2) was 0.2 times the volume of the resin so that the total volume of the water with the eluent was the same as the volume of the resin.
  • the eluent is potassium hydroxide and the supply amount of UF permeate and the supply amount of eluent are changed. Conducted experiments. Table 2 shows the experimental conditions.
  • the supply amount of UF permeate is 1.1 to 1.6 kgZl—R as solids (1.5 to 2.2 eqZl—R as the total equivalent of calcium, magnesium, potassium and sodium). did.
  • Test 3 since the desalinating solution supplied 1. lkg'TSZl-R from the start of feeding does not contain carcin to concentrate carcin, it was added as desalting solution (A). did. Sarasuko 1. Desalted solution supplied over lkg'TSZl-R was collected separately as desalted solution (B).
  • the weight of desalted solution and eluate was measured, and carnitine, NPN, urea, and mineral content were prayed.
  • the weight of each component of the supplied UF permeate, desalted solution, and eluate was calculated, and the recoveries in the desalted solution and eluate were determined.
  • the recovery rate of each cation the cations derived from the salt solution are used for elution.
  • Table 3 shows the recovery rate of each component in the eluate when salt-calcium, salt-potassium, hydroxide-potassium, and hydrochloric acid are used as the eluent. [0027] [Table 3] pH of recovery [%]
  • Figure 7 shows the change in pH when titrating 0.1 M sodium hydroxide to 10 ml of a 0.1 M solution of carcin and acetic acid.
  • Carnitine has a positively charged nitrogen atom group and a negatively charged carboxyl group, and a weak acid carboxyl group is not dissociated in an acidic solution, and carnitine is considered to be strongly positively charged in the acidic region.
  • the cartilage recovery rate to the eluate increases in proportion to the increase in the amount of potassium hydroxide solution supplied.
  • the Dil. And Cone. 79% and 61% carcin were recovered respectively (Figs. 9 and 10).
  • the carrot content in terms of dry matter of the liquid mixture is 0.1 to 0.2%.
  • carcin can be recovered from milk or dairy products in a state where the content of cations such as calcium is low.

Abstract

La présente invention concerne un procédé de récupération de carnitine dans un état à faible teneur en cations tels que le calcium, à partir du lait ou d'autres produits laitiers. Le procédé de récupération de carnitine comprend l'introduction d'un ultrafiltrat, ou petit-lait, de lait ou d'autres produits laitiers au sommet d'une colonne garnie d'une résine échangeuse de cations ; l'arrêt de l'introduction de l'ultrafiltrat lorsque la carnitine a été adsorbée dans la couche de base représentant environ le tiers inférieur de la partie garnie de résine de la colonne ; puis l'introduction d'un liquide d'élution uniquement dans la couche de base afin d'éluer la carnitine.
PCT/JP2006/316164 2005-08-18 2006-08-17 Procédé de récupération de carnitine WO2007020973A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007531023A JP5405020B2 (ja) 2005-08-18 2006-08-17 カルニチンの回収方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-237376 2005-08-18
JP2005237376 2005-08-18

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WO2007020973A1 true WO2007020973A1 (fr) 2007-02-22

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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016133036A1 (fr) * 2015-02-20 2016-08-25 株式会社明治 Agent d'amélioration de fatigue
JP2018064492A (ja) * 2016-10-18 2018-04-26 株式会社明治 たんぱく質効率向上用の組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6263553A (ja) * 1985-09-17 1987-03-20 Snow Brand Milk Prod Co Ltd Ｌ−カルニチンの調製方法
JP2000109453A (ja) * 1998-10-01 2000-04-18 Nippon Beet Sugar Mfg Co Ltd ベタイン及びアミノ酸の回収方法
JP2002320500A (ja) * 2001-02-23 2002-11-05 Meiji Milk Prod Co Ltd 乳由来の非タンパク態窒素化合物、ｌ−カルニチンの濃縮方法、ｌ−カルニチン濃縮物及びその利用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0267256A (ja) * 1988-09-02 1990-03-07 Bio-Le Kk カルニチンおよびカルニチンニトリルの単離精製法
JP4452341B2 (ja) * 1999-01-13 2010-04-21 雪印乳業株式会社 Ｌ−カルニチン剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6263553A (ja) * 1985-09-17 1987-03-20 Snow Brand Milk Prod Co Ltd Ｌ−カルニチンの調製方法
JP2000109453A (ja) * 1998-10-01 2000-04-18 Nippon Beet Sugar Mfg Co Ltd ベタイン及びアミノ酸の回収方法
JP2002320500A (ja) * 2001-02-23 2002-11-05 Meiji Milk Prod Co Ltd 乳由来の非タンパク態窒素化合物、ｌ−カルニチンの濃縮方法、ｌ−カルニチン濃縮物及びその利用

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JP5599446B2 (ja) 2014-10-01
JPWO2007020973A1 (ja) 2009-02-26
JP2013048631A (ja) 2013-03-14
JP5405020B2 (ja) 2014-02-05

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