KR101451078B1 - Decreasing Methods of Fluoride Content in Antarctic Krill by Different Physicochemical Treatment - Google Patents
Decreasing Methods of Fluoride Content in Antarctic Krill by Different Physicochemical Treatment Download PDFInfo
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- 241000239366 Euphausiacea Species 0.000 title claims abstract description 84
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 36
- 238000011282 treatment Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000003247 decreasing effect Effects 0.000 title 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 44
- 239000011737 fluorine Substances 0.000 claims abstract description 44
- 241000238557 Decapoda Species 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 230000001603 reducing effect Effects 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 12
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- 229960003403 betaine hydrochloride Drugs 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- MEJYXFHCRXAUIL-UHFFFAOYSA-N 2-[carbamimidoyl(methyl)amino]acetic acid;hydrate Chemical compound O.NC(=N)N(C)CC(O)=O MEJYXFHCRXAUIL-UHFFFAOYSA-N 0.000 claims description 7
- UBDZFAGVPPMTIT-UHFFFAOYSA-N 2-aminoguanidine;hydron;chloride Chemical compound [Cl-].NC(N)=N[NH3+] UBDZFAGVPPMTIT-UHFFFAOYSA-N 0.000 claims description 7
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004475 Arginine Substances 0.000 claims description 6
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- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 6
- 239000004472 Lysine Substances 0.000 claims description 6
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 6
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- -1 hydrate Chemical compound 0.000 claims description 2
- JXXCENBLGFBQJM-FYZOBXCZSA-N [(2r)-3-carboxy-2-hydroxypropyl]-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)C[C@H](O)CC(O)=O JXXCENBLGFBQJM-FYZOBXCZSA-N 0.000 claims 2
- 235000013372 meat Nutrition 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 12
- 235000013305 food Nutrition 0.000 abstract description 10
- 150000001413 amino acids Chemical class 0.000 abstract description 4
- 206010001497 Agitation Diseases 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- PHIQHXFUZVPYII-ZCFIWIBFSA-N (R)-carnitine Chemical compound C[N+](C)(C)C[C@H](O)CC([O-])=O PHIQHXFUZVPYII-ZCFIWIBFSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 241000238154 Carcinus maenas Species 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 229940024606 amino acid Drugs 0.000 description 2
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 229960004203 carnitine Drugs 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000125205 Anethum Species 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 102000008934 Muscle Proteins Human genes 0.000 description 1
- 108010074084 Muscle Proteins Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 208000004042 dental fluorosis Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 108010084072 krill protein extract Proteins 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000008935 nutritious Nutrition 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000010257 thawing Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L17/00—Food-from-the-sea products; Fish products; Fish meal; Fish-egg substitutes; Preparation or treatment thereof
- A23L17/40—Shell-fish
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
- A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/30—Physical treatment, e.g. electrical or magnetic means, wave energy or irradiation
- A23L5/32—Physical treatment, e.g. electrical or magnetic means, wave energy or irradiation using phonon wave energy, e.g. sound or ultrasonic waves
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2300/00—Processes
- A23V2300/48—Ultrasonic treatment
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Abstract
본 발명은 높은 불소 함량에 의해 식용으로 이용하기 어려운 크릴새우의 이용도를 높이고자 남극크릴새우에 물리화학적 처리를 하여 불소 함량을 저감화 시키는 방법에 관한 것으로, 이를 더욱 상세하게 설명하면, 남극크릴새우 전어체 및 육에 물리화학적인 처리를 한 후, 남아있는 불소함량을 측정함으로써 처리 전과 처리 후의 불소 저감화 정도를 나타내었으며, 그 결과는 남극크릴새우의 부위별 불소함량을 측정에서, 단위 중량당 불소함량은 꼬리 부분이 가장 높았고, 육 부분이 가장 낮았다.
또한, 동결 생크릴새우는 물리화학적 처리를 한 후, 불소 함량을 측정하였을 때 무처리 동결 생크릴새우와 비교하여 불소 저감화 효과가 없었으나, 동결 생크릴새우에서 분리한 크릴새우육을 용매처리 한 결과는 크릴새우육의 손실은 발생하지만 무처리 크릴육과 비교하여 확실한 불소 저감화 효과가 있었고 그 중에서도 아미노산용매처리에서 저감화 효과가 크게 나타난 것을 특징으로 하는 물리화학적 처리에 의한 남극크릴새우의 불소 저감화 방법에 관한 것이다.The present invention relates to a method for reducing the fluorine content by physicochemical treatment of an Antarctic krill with a high fluorine content in order to improve the utilization of the krill shrimp which is difficult to use for food. More specifically, The results showed that fluorine content of the Antarctic krill was measured by measuring fluorine content per unit weight of fluoride, The content was highest at the tail and lowest at the meat.
In addition, when frozen raw krill was measured by fluorine content after physico-chemical treatment, there was no effect of reducing fluoride as compared with untreated frozen raw krill, but the krill shrimp isolated from frozen raw krill was treated with solvent The results showed that although loss of krill shrimp occurred, there was a definite effect of fluorine abatement compared with untreated krill meat, among which the effect of reduction in amino acid solvent treatment was remarkably enhanced, and a method of reducing fluoride of Antarctic krill shrimp by physicochemical treatment .
Description
본 발명은 남극크릴새우에 다량 함유되어 있는 불소 저감화에 관한 것으로, 물리적, 화학적인 방법을 통하여 각 조건에서 불소 저감화 경향을 파악하고 가장 좋은 효과를 보이는 방법을 제공하고자 하였다.
The present invention relates to fluorine abatement contained in a large amount in an Antarctic krill shrimp, and aims to provide a method of grasping fluorine abatement tendency under the respective physical and chemical methods and showing the best effect.
불소는 강력한 반응성의 할로겐 원소로 자연계에 화합물의 형태로 널리 존재한다. 세계보건기구(WHO)의 먹는 물 수질관리 지침서에 의하면 적정량의 불소가 포함되어 있는 물을 섭취하는 경우 충치예방에 효과가 있어 인위적으로 먹는 물에 첨가되기도 한다.
Fluorine is a strongly reactive halogen element and exists widely in the form of compounds in nature. According to the World Health Organization (WHO) Guideline on the Management of Drinking Water Quality, water containing fluoride in proper amounts is effective in preventing tooth decay and may be added to artificially ingested water.
그러나 고농도의 양(1.5mg/L 이상)을 장기적으로 섭취하는 경우 치아 및 뼈에 불소 침착증 등을 일으키고 독성을 남기는 것으로 보고되어 있다.
However, long-term ingestion of high concentrations (over 1.5 mg / L) has been reported to cause fluorosis and other toxic effects on teeth and bones.
이에 남극크릴새우는 영양학적으로 우수한 식품소재이나 외골격(exoskeleton)에 다량의 불소가 포함되어 있어 이를 제거하는 기술이 요구되고 있다 (J A. Camargo., 2003. Fluoride toxicity to aquatic organisms: a review. Chemosphere 50, 251-264).Antarctic krill is a nutritionally good food material, and it requires a technology to remove it because it contains a large amount of fluorine in the exoskeleton (J A. Camargo., 2003. Fluoride toxicity to aquatic organisms: a review. Chemosphere 50, 251-264).
미국FDA에서는 불소에 대하여 식품 중의 최대 잔존량을 법적으로 규제하고 있으며 100ppm 이하로 규정하고 있다.
The US Food and Drug Administration (FDA) regulates the maximum amount of residual fluoride in food and regulates it to be less than 100ppm.
불소의 감량에 대한 연구에서 Park 등은 크릴 단백질 추출용액에 처리하는 용매의 pH와 이온의 종류 및 이온강도가 크릴 근육단백질에 결합된 불소함량에 미치는 영향에 대하여 조사하였으며, 그 결과 NaCl의 이온강도 0.05M, pH11일 때 불소감량 효과가 좋은 것으로 나타났다 (HJ Park, KS Ham, DM Kim & KH Kim, 1988. Korean J. Food sci. technol. 20(1) 19-22).
In a study of fluoride reduction, Park et al. Examined the effect of pH, ionic strength and ionic strength of solvent on the krill protein extract solution on the fluoride content of krill muscle protein. As a result, the ionic strength of NaCl 0.05M and pH 11, respectively. (HJ Park, KS Ham, DM Kim & KH Kim, 1988. Korean J. Food Sci. Technol. 20 (1) 19-22).
kim 등의 연구에서는 불소를 알루미늄전극에 결합, 침전시키는 방법을 이용하여 크릴에 과량 함유된 불소를 제거함과 동시에 총 불소농도, 이온상태의 불소농도 및 결합상태의 불소농도의 감량변화를 측정하여 크릴체내에서의 불소이동기작에 대한 기초자료를 제시하고 있다(KH Kim, DM Kim & YH Kim, 1990. Korean J. Food sci. Technol. 22(2) 172-176).
In Kim et al., fluorine contained in an excess amount of krill was removed and fluorine concentration in an ionic state and change in weight loss of a fluorine concentration in a bonded state were measured using a method of binding fluorine to an aluminum electrode and precipitating the fluorine, (Kim, YH Kim, 1990. Korean J. Food Sci. Technol. 22 (2) 172-176).
상기 종래의 남극크릴새우는 양식 사료로 이용되고 있으며, 사료 내 크릴새우의 함량에 따라 양식어류의 성장에 저해 작용이 있다는 연구가 보고 되었으며, 이는 크릴새우사료를 먹은 어류의 체내 불소 함량을 보면 뼈에 다량의 불소가 축적되는 문제점을 가지고 있었다.
The above-mentioned conventional Antarctic krill was used as a feed for the study, and research on the effect of the content of the krill shrimp on the growth of the aquaculture fish was reported, A large amount of fluorine is accumulated in the water.
미국 FDA에서는 불소에 대하여 식품 중의 최대 잔존량을 법적으로 규제하고 있어 크릴새우의 체내에 축적된 불소함량이 큰 문제가 되고 있다.
The US Food and Drug Administration (FDA) regulates the maximum amount of residual fluoride in food, and the fluoride content accumulated in the body of krill shrimp becomes a big problem.
따라서, 본 발명은 상기와 같은 점들을 감안하여 완성한 것으로, 본 발명에서는 남극크릴새우를 식품소재로 활용하는데 문제가 되고 있는 불소의 함량을 저감화하여 고영양, 청정 식품소재로 개발하기 위한 방법으로, 남극크릴새우를 어획 후 동결보관하기 전에 크릴 전어체나 탈각크릴에 대하여 용매에 침지, 교반 하거나 추가로 가열과정을 진행한 후 동결 보관하는 방법이다. 동결 보관한 크릴새우을 식품소재나 사료원료로 이용하기 위하여 가공과정에서 용매에 침지, 교반 하거나 가열하는 방법을 포함한다.
SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to provide a method for developing a nutritious and clean food material by reducing fluorine content, which is a problem in using Antarctic krill shrimp as a food material, After the Antarctic krill is caught, it is immersed in a solvent for the krill body or the krill krill before it is frozen, or it is stirred, or the krill is further frozen after being heated. In order to use the frozen krill shrimp as a food material or a feed material, it includes a method of immersing, stirring or heating in a solvent during processing.
상기에서 말한 용매의 종류로는 증류수, 에탄올과 염으로는 아황산나트륨(Sodium sulfate), 염화나트륨(Sodium chloride)을 사용하였으며, 라이신 (Lysine), 알기닌 (Arginine), 카르니틴 하이드로클로라이드 (Carnitine hydrochloride), 베타인 하이드로클로라이드 (Betaine hydrochloride) 크레아틴 하이드레이트 (Creatine hydrate), 아미노구아니딘 하이드로클로라이드 (Aminoguanidine hydrochloride) 용액에 가열 및 교반 처리하여 불소의 감소율을 제시하고 각 용매별 크릴새우의 수율을 함께 고려하여 불소 저감화의 최적 방법을 제공하고자함을 그 목적으로 한다.
Sodium sulfate and sodium chloride were used as the solvents and distilled water, ethanol and salts, and lysine, arginine, carnitine hydrochloride, beta- Betaine hydrochloride Creatine hydrate and Aminoguanidine hydrochloride solution were heated and stirred to show the reduction rate of fluorine and the yield of krill shrimp was determined by considering the yield of each solvent. The present invention is directed to provide a method for providing a service to a user.
이상의 설명에서와 같이, 본 발명에 따른 남극크릴새우에서 불소를 저감화 시키기 위하여 용매별 교반, 가열하였을 때 크릴 전어체 보다는 탈각크릴에서 효과가 있었고, 가열과 비가열 교반에 따른 차이는 용매 종류에 따라 달랐으나 전반적으로 가열교반보다는 교반에서 효과가 있었으며, 수율에서도 교반 처리한 것이 높은 수율을 나타내었다. As described above, in the Antarctic krill shrimp according to the present invention, when the solvent was stirred and heated to reduce fluorine, the effect was more pronounced in the off-angle krill than in the krill body, and the difference between the heating and the non- But, overall, it was effective in agitation rather than heating agitation, and agitation treatment showed high yield even in yield.
용매에 따른 차이는 아미노산에서 효과가 좋았으며, 그 중에서도 카르니틴 하이드로크로라이드(Carnitine hydrochloride), 베타인 하이드로크로라이드(Betaine hydrochloride)에서 효과가 뛰어났다. The differences between the solvents were good for amino acids, especially for carnitine hydrochloride and betaine hydrochloride.
이러한 결과로 보았을 때 탈각크릴에 대하여 불소 저감 효과가 좋은 것으로 나타났으며 탈각크릴에 위와 같은 용매처리를 하여 식품소재 및 사료소재 산업에서 매우 유용하게 사용할 수 있는 뛰어난 효과가 있다.
As a result, it was found that the fluoride reducing effect was excellent for the breakout krill, and the solvent treatment was applied to the breakout krill, which is very useful in the food material and feed materials industry.
도 1은 크릴새우의 몸체 부위별 불소 함량도
도 2는 동결 생크릴새우와 동결 자숙크릴새우의 해동에 따른 불소함량 비교도
도 3은 동결 생크릴새우와 동결 자숙크릴새우의 부위별 상대적인 불소 분포도
도 4는 가열교반 및 비가열 교반 처리한 시료의 불소 함량을 측정하고 초기 무게와 나중 무게로 수율을 구한 결과도
도 5는 껍질을 제거한 크릴육에 염, 알코올, 물, 초음파 세척에서의 불소 함량 변화와 수율을 나타낸 그림
도 6은 껍질을 제거한 크릴육에 아미노산, 카르니틴, 베타인, 크리아틴, 아미노구아니딘 용매처리에 대한 불소 함량 변화와 수율을 나타낸 그림1 is a graph showing the fluorine content
FIG. 2 is a graph comparing the fluoride content of frozen fresh krill and frozen fresh krill
Fig. 3 shows the relative distribution of fluoride in frozen fresh krill and frozen fresh krill
FIG. 4 is a graph showing the results obtained by measuring the fluorine content of a sample subjected to heating agitation and non-heat agitation, and calculating the initial and final yields
FIG. 5 is a graph showing changes in fluorine content and yields of salt, alcohol, water, and ultrasonic washing on krill meat,
Fig. 6 is a graph showing changes in fluoride content and yield of krill meat treated with the amino acid, carnitine, betaine, cryatin and aminoguanidine solvents in the peeled krill meat
본 발명은 물리·화학적 처리에 의한 남극크릴새우의 불소 저감화 방법에 관한 것으로, 더욱 상세하게 설명하면, 남극크릴새우를 식품소재로 활용하는데 문제가 되고 있는 불소의 함량을 저감화하여 고영양, 청정 식품소재로 개발하기 위한 방법으로, 남극크릴새우의 불소를 저감화 하기 위해 크릴새우를 염, 알코올, 물, 아미노산, 카르니틴, 베타인, 크리아틴, 아미노구아니딘 용액에 가열 및 교반 처리하여 불소의 감소율을 제시하고 각 용매별 크릴새우의 수율을 함께 고려하여 불소 저감화의 최적 방법을 제공하고자함을 그 목적으로 한다.
The present invention relates to a method for reducing fluoride in Antarctic krill shrimp by physical and chemical treatments and more specifically to a method for reducing fluorine content which is a problem in using Antarctic krill shrimp as a food material, In order to reduce the fluoride content of the Antarctic krill, the krill shrimp was treated with a salt, alcohol, water, amino acid, carnitine, betaine, cryatin and aminoguanidine solution by heating and stirring to show the reduction rate of fluoride And to provide an optimal method of reducing fluoride by considering the yield of krill shrimp for each solvent.
하기 실시예 및 실험예는 본 발명을 구체적으로 설명하기 위한 것으로, 본 발명의 범주가 이들 실시예 및 실험예에 국한되는 것은 아니다.
The following Examples and Experimental Examples are intended to illustrate the present invention specifically, and the scope of the present invention is not limited to these Examples and Experimental Examples.
본 발명의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되어 지는 것이다.
The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.
[실시예 1] 크릴새우의 부위별 중량비율 비교
[Example 1] Comparison of weight ratio of krill by shrimp
본 발명에 사용될 동결된 남극크릴새우를 머리(Head), 몸체껍질(Body Shell), 육(Meat), 다리(Leg), 꼬리(Tail)로 분리하여 상압건조 한 후, 무게를 측정하여 몸체에서 차지하는 비율을 나타내었다. The frozen Antarctic krill shrimp to be used in the present invention is separated into a head, a body shell, a meat, a leg, and a tail, dried at atmospheric pressure, Respectively.
상기 표 1에 나타낸바와 같이, 남극크릴새우에서 머리가 36.98%로 가장 큰 비율을 차지하고 있으며, 그 다음으로는 육, 껍질, 다리, 꼬리 순으로 비율을 차지한다.
As shown in Table 1, the largest proportion of the head in Antarctic krill was 36.98%, followed by meat, shell, leg, and tail.
도 1은 크릴새우의 몸체 부위별 불소 함량을 나타낸 것으로, 그 결과를 살펴보면, 단위 중량에 대한 불소 함량(ppm)은 껍질(1,243.18±10.48 ppm)이 가장 높았고, 다음으로 꼬리(1108.72±4.35 ppm), 다리(936.38±18.15 ppm), 머리(739.69±10.66 ppm), 육(130.22±3.09 ppm) 순서로 나타났다(도 1의 막대그래프).
FIG. 1 shows the fluoride content of the krill shrimp according to the body part. As a result, the fluorine content (ppm) of the unit weight was highest in shell (1,243.18 ± 10.48 ppm), followed by tail (1108.72 ± 4.35 ppm) , Legs (936.38 ± 18.15 ppm), head (739.69 ± 10.66 ppm) and meat (130.22 ± 3.09 ppm), respectively.
상기 표 1의 몸체 비율에 따라 남극크릴새우에 분포되어 있는 불소 함량(%)을 계산해 보면, 전체 불소 함량(100%)에서 불소를 가장 많이 포함하고 있는 부위는 머리(41.35%)이고, 그 다음이 껍질(37.59%), 다리(18.15%), 육(6.54%), 꼬리(4.33%) 순서로 나타났다(도 1의 사선그래프).
Calculating the fluorine content (%) distributed in the Antarctic krill according to the body ratio in the above Table 1, the region containing the greatest amount of fluorine in the total fluorine content (100%) is the head (41.35%), (37.59%), legs (18.15%), meat (6.54%), and tail (4.33%).
[실시예 2] 동결 생크릴새우와 동결 자숙크릴새우의 해동에 따른 불소 함량
[Example 2] Fluorine content due to thawing of frozen raw krill and frozen krill
상기 동결된 남극크릴새우를 이용하여, 동결 생크릴새우와 동결 자숙크릴새우를 실온에서 해동하여 육, 껍질(머리+몸체껍질+다리+꼬리) 그리고 드립(drip)으로 분리한 후, 동결 건조하여 건조물 기준의 불소함량을 측정하였다.Using the frozen Antarctic krill shrimp, the frozen raw krill and the frozen dill krill were separated at the room temperature into meat, shell (head + body skin + leg + tail) and drip, followed by lyophilization The fluorine content on a dry basis was measured.
도 2는 동결 생크릴새우와 동결 자숙크릴새우의 해동에 따른 불소함량을 나타낸 것으로, 남극크릴새우는 자숙과정(Boiled) 중에 불소가 788.266 ppm에서 424.53 ppm으로 약 50% 제거되는 것을 알 수 있었다.
FIG. 2 shows the fluoride content of frozen green crab shrimp and frozen tender krill shrimp, and it was found that about 50% of fluoride was removed from 788.266 ppm to 424.53 ppm during the boiling time of the Antarctic krill shrimp.
그리고, 도 3은 동결 생크릴새우와 동결 자숙크릴새우의 전체 불소 함량에서 부위별 상대적인 불소 분포를 나타낸 것으로, 이를 비교해 보면 동결 생크릴새우와 동결 자숙크릴새우 모두의 껍질(Shell)부위에 전체 불소의 약 90%가 함유되어 있고 육(Meat)에는 약 10%, 드립에는 5% 미만의 비슷한 분포 경향을 보였다.
Fig. 3 shows the relative fluoride distribution in the whole fluorine content of frozen green crab shrimp and freeze-cooked krill shrimp. In comparison, when the total fluoride content of the frozen green crab shrimp and the freeze- , About 90%, and about 10% for Meat and less than 5% for drip.
[실시예 3] 용매처리에 따른 동결 생크릴새우의 불소 함량 및 수율 측정
[Example 3] Measurement of fluorine content and yield of frozen raw krill shrimp by solvent treatment
남극크릴새우에 물리적 또는 화학적 처리를 통하여 크릴새우의 불소 저감화 방법으로는, As a method for reducing fluoride in krill shrimp by physical or chemical treatment of an antarctic krill,
먼저, 물리적 처리를 통하여 남극크릴새우의 불소를 저감시키는 방법으로, 상기 동결 생크릴새우 중량의 1~10배 양의 화학적 용매에 넣고 10~30분 간 비가열 교반 또는 80~100℃ 에서 5~10분 간 가열교반 또는 초음파처리에 의해 크릴새우의 불소를 저감시키는 것과,
First, in order to reduce the fluoride content of the Antarctic krill shrimp through physical treatment, it is added to a chemical solvent in an amount of 1 to 10 times the weight of the frozen raw krill shrimp, and the mixture is heated for 10 to 30 minutes, Reducing fluoride in the krill shrimp by heating agitation or ultrasonic treatment for 10 minutes,
화학적 처리를 통하여 남극크릴새우의 불소를 저감시키는 방법으로, 화학적 처리에 사용된 화학적 용매의 농도는, 0.05~1N 아황산나트륨, 1~5% 염화나트륨, 2~15% 에탄올과 라이신(Lysine), 아르기닌(Arginine), 카르니틴 하이드로클로라이드(Carnitine hydrochloride), 베타인 하이드로클로라이드(Betaine hydrochloride), 크레아틴 하이드라이트(Creatine hydrate), 아미노구아니딘 하이드로클로라이(Aminoguanidine hydrochloride) 는 0.05~1N 농도의 용액 처리에 의해 크릴새우의 불소(F)가 저감화 되어진다.
The concentration of the chemical solvent used for the chemical treatment is 0.05 to 1 N sodium sulfite, 1 to 5% sodium chloride, 2 to 15% ethanol and lysine, arginine Carinitine hydrochloride, Betaine hydrochloride, Creatine hydrate and Aminoguanidine hydrochloride were treated with a solution of 0.05 to 1 N concentration of krill shrimp The fluorine (F) of the fluorine-containing polymer is reduced.
본 실험에서는 동결 생크릴새우 1~100 g에 화학적 용매로 0.1N 아황산나트륨(Sodium sulfate) 용액과 바닷물과 비슷한 농도인 3.2%염화나트륨(Sodium chloride), 10% 에탄올(Ethanol), 증류수(Distilled water)를 각각 크릴 중량의 3배로 넣고 90~100℃에서 5~10분 동안 가열교반(HSFFK : Heat stirred fresh frozen krill) 하였다.
In this experiment, 1 ~ 100 g of frozen raw krill shrimp was treated with 0.1 N sodium sulfate solution and 3.2% sodium chloride, 10% ethanol, distilled water, Was added to the mixture at three times the weight of the krill, and the mixture was heated and stirred at 90 to 100 ° C for 5 to 10 minutes (heat-stirred fresh frozen krill).
그리고 동일한 방법으로 실온에서 20분간 비가열 교반(NHSFFK : Non-Heat stirred fresh frozen krill) 한 다음 30 메쉬(mesh)의 체로 크릴새우를 걸러 용매를 제거한 후, 동결건조 하였다.
The same procedure was followed by non-heat stirring fresh frozen krill (NHSFFK) at room temperature for 20 min. Then, the krill shrimp was sieved with a 30 mesh sieve to remove the solvent, followed by lyophilization.
또한, 증류수를 가해준 동결 생크릴새우를 초음파를 이용하여 분쇄하는 소니케이트(Sonicater)를 이용하여 80℃에서 10분 가열하고, 실온에서 20분간 비가열 초음파처리 하여 각각 30 메쉬(mesh)의 체로 걸러 물을 제거한 후 동결건조 하였다.
In addition, the frozen raw krill shrimp to which distilled water was added was heated at 80 DEG C for 10 minutes using Sonicater, which was pulverized using ultrasonic waves, and subjected to a non-heat ultrasonic treatment for 20 minutes at room temperature to obtain a sieve of 30 mesh The water was removed by filtration and then lyophilized.
상기 가열교반(HSFFK : Heat stirred fresh frozen krill) 또는 비가열 교반(NHSFFK : Non-Heat stirred fresh frozen krill) 처리한 시료에 대하여 불소 함량을 측정하고 초기 무게와 나중 무게로 수율을 구한 결과는 도 4에 나타내었으며, 그 결과에서 대조군(control)은 용매처리를 하지 않은 동결 생크릴새우에 대한 건조물 기준 불소함량을 나타낸 것이다.
The fluorine content of the sample treated with the heat stirring fresh frozen krill (HSFFK) or the non-heat stirred fresh frozen krill (NHSFFK) was measured and the yield was calculated from the initial weight and the latter weight. , And the control (control) shows the fluoride content on the basis of the dried material for the frozen raw krill without the solvent treatment.
전반적으로 수율이 적게는 20%에서 많게는 60%까지 떨어지고, 그로 인하여 불소 함량은 대조군(control) 보다 높게 나타났다. 이는 용매 처리 과정에서 불소함량이 낮은 크릴육의 유실이 발생하면서 상대적으로 껍질의 비율이 늘어났기 때문이다.
Overall yield was reduced from less than 20% to as much as 60%, resulting in a higher fluoride content than the control (control). This is due to the fact that the proportion of shells was relatively increased due to the loss of krill meat with low fluoride content during the solvent treatment.
가열교반(HSFFK)과 비가열교반(NHSFFK)을 비교해 보면, 가열교반보다는 비가열교반에서 크릴육의 유실 정도가 약하고 불소 함량도 낮게 나타났다. 동결 생크릴새우 자체에 여러 종류의 용매를 첨가하여 가열이나 교반하는 방법은 불소 저감화 효과가 없는 것으로 나타났다.
Comparing the heat agitation (HSFFK) and the non-heat agitation (NHSFFK), the degree of loss of krill meat was weaker and the fluorine content was lower than that of heating agitation. The method of adding various kinds of solvents to the frozen raw krill itself and heating or stirring showed no effect of reducing fluoride.
[실시예 4] 용매처리에 따른 크릴육의 불소 함량 및 수율 측정[Example 4] Measurement of fluorine content and yield of krill meat by solvent treatment
상기 [실시예 3]의 결과에서, 동결 생크릴새우에서 껍질을 제거하지 않고 화학적 용매처리를 하였을 때 무처리 동결 생크릴새우인 대조군(control)과 비교하여 불소제거 효과가 없는 것으로 나타난 결과로 인하여,
As a result of [Example 3] above, when the chemical solvent treatment was performed without removing the bark from the frozen raw krill shrimp, it was found that there was no fluorine removal effect as compared with the control without freeze-thawed krill shrimp control ,
[실시예 4]에서는, 껍질을 제거한 크릴육에 [실시예 3]과 동일한 방법으로 가열교반(HSFKM) 또는 비가열 교반(NHSFKM) 처리한 시료에 대하여 불소 함량을 측정하고 초기 무게와 나중 무게로 수율을 구하였으며, 그 결과는 도 5와 도 6에 나타낸바와 같았다.
In Example 4, the fluorine content was measured for a sample in which peeled krill meat was treated with heating stirring (HSFKM) or non-heating stirring (NHSFKM) in the same manner as in [Example 3] The yield was determined, and the results were as shown in Fig. 5 and Fig.
그리고, 상기 [실시예 3]의 동결 생크릴새우에서 실시하지 않은 화학적 처리로, By the chemical treatment not carried out in the frozen green crab shrimp of [Example 3]
라이신(Lysine), 알기닌(Arginine), 카르니틴 하이드로클로라이드(Carnitine hydrochloride), 베타인 하이드로클로라이드(Betaine hydrochloride), 크레아틴 하이드레이트(Creatine hydrate), 아미노구아니딘 하이드로클로라이드(Aminoguanidine hydrochloride) 용매처리를 추가로 실시하였다.
Lysine, Arginine, Carnitine hydrochloride, Betaine hydrochloride, Creatine hydrate and Aminoguanidine hydrochloride were further treated with a solvent.
도 5는 껍질을 제거한 크릴육에 염, 알코올, 물 그리고 초음파 세척에서의 불소 함량 변화와 수율을 나타낸 것으로, 그 결과를 살펴보면, 전체적으로 무처리한 대조군(control)과 비교하여 염, 에탄올, 증류수 그리고 초음파 세척에서의 불소 저감 효과가 나타났으며, 10%에탄올 용액을 제외하고는 가열교반(HSFFK)처리에서 불소 저감 효과가 더 크게 나타났다.
FIG. 5 shows changes and yields of fluoride in salt, alcohol, water, and ultrasonic washing of krill meat with the skin removed. As a result, it was found that salt, ethanol, distilled water, The effect of fluorine abatement in ultrasonic cleaning was shown. The effect of fluoride abatement was higher in HSFFK treatment except 10% ethanol solution.
특히, 가열교반(HSFFK) 처리에서 아황산나트륨(Sodium sulfate) 처리와 초음파(Sonicate) 처리에서 불소 저감 효과가 크나, 수율(Yield)이 58%와 50%로 낮은 것을 확인 할 수 있었다.
In particular, in the HSFFK treatment, the sodium sulfate treatment and the sonicate treatment showed a high fluorine abatement effect, but yields were as low as 58% and 50%, respectively.
도 6은 껍질을 제거한 크릴육에 화학적 처리로 라이신(Lysine), 알기닌(Arginine), 카르니틴 하이드로클로라이드(Carnitine hydrochloride), 베타인 하이드로클로라이드(Betaine hydrochloride), 크레아틴 하이드레이트(Creatine hydrate), 아미노구아니딘 하이드로클로라이드(Aminoguanidine hydrochloride) 용매처리에 대한 결과를 나타낸 것으로, 도 5의 염, 알코올, 물 그리고 초음파 처리와 비교하였을 때, 도 6에 나타난 결과에서, 수율(Yield)이 높게 나타났으며, 불소 함량도 상당히 저감화 된 것을 확인 할 수 있었다.
FIG. 6 is a graph showing the results of chemical treatment of krill meat, which has been peeled off, by chemical treatment such as lysine, arginine, carnitine hydrochloride, betaine hydrochloride, creatine hydrate, aminoguanidine hydrochloride (Aminoguanidine hydrochloride) solvent treatment. When compared with the salt, alcohol, water and ultrasonic treatment of FIG. 5, yield was high in the result shown in FIG. 6, and the fluorine content was also considerably high It can be confirmed that it is reduced.
비가열교반(NHSFKM) 처리에서는 수율이 약 80%로 전반적으로 안정적이며 불소 함량도 100 ppm 전후로 낮게 나타났다.
In the non-heat agitation (NHSFKM) treatment, the overall yield was about 80%, and the fluorine content was low around 100 ppm.
특히, 카르니틴 하이드로클로라이드(Carnitine hydrochloride), 베타인 하이드로클로라이드(Betaine hydrochloride)의 비가열교반(NHSFKM) 처리 결과에서, 불소함량이 각 38ppm과 30ppm으로 산, 알칼리, 염, 알코올, 물, 초음파 처리 결과와 비교하여도 가장 낮은 결과를 보였다.
In particular, in the results of non-heat agitation (NHSFKM) treatment of carnitine hydrochloride and betaine hydrochloride, the fluorine content was 38 ppm and 30 ppm in terms of acid, alkali, salt, alcohol, water, The results are also the lowest.
Claims (7)
크릴새우 중량의 1~10배 양의 아황산나트륨, 염화나트륨, 에탄올, 증류수, 라이신(Lysine), 아르기닌(Arginine), 카르니틴 하이드로클로라이드 (Carnitine hydrochloride), 베타인 하이드로클로라이드(Betaine hydrochloride), 크레아틴 하이드레이트(Creatine hydrate), 아미노구아니딘 하이드로클로라이드 (Aminoguanidine hydrochloride) 중 선택된 하나 또는 하나 이상의 화학적 용매를 넣고 10~30분 간 비가열 교반 또는 80~100℃에서 5~10분 간 가열교반 또는 초음파처리에 의해 크릴새우의 불소를 저감시키는 것을 특징으로 하는 크릴새우의 불소 저감화 방법
In reducing the fluoride of krill shrimp through physical or chemical treatment of Antarctic krill,
Lysine, Arginine, Carnitine hydrochloride, Betaine hydrochloride, Creatine hydrate, Creatine hydrate, Sodium sulfite, Sodium chloride, Ethanol, Distilled water, hydrate, and aminoguanidine hydrochloride, followed by agitation for 10 to 30 minutes or heating at 80 to 100 ° C for 5 to 10 minutes, followed by stirring or ultrasonic treatment. A method for reducing fluoride in krill shrimp characterized by reducing fluorine
화학적 용매의 농도는, 0.05~1N 아황산나트륨, 1~5% 염화나트륨, 2~15% 에탄올과 라이신(Lysine), 아르기닌(Arginine), 카르니틴 하이드로클로라이드(Carnitine hydrochloride), 베타인 하이드로클로라이드(Betaine hydrochloride), 크레아틴 하이드라이트(Creatine hydrate), 아미노구아니딘 하이드로클로라이드(Aminoguanidine hydrochloride)는 0.05~1N 농도의 용액처리에 의해 크릴새우의 불소를 저감시키는 것을 특징으로 하는 크릴새우의 불소 저감화 방법
The method according to claim 1,
The concentration of the chemical solvent should be 0.05 to 1 N sodium sulfite, 1 to 5% sodium chloride, 2 to 15% ethanol and lysine, arginine, carnitine hydrochloride, betaine hydrochloride, , Creatine hydrate and aminoguanidine hydrochloride are used to reduce the fluoride content of krill shrimp by a solution treatment with a concentration of 0.05 to 1N.
초음파처리는 80℃에서 10분 가열 또는 실온에서 20분간 비가열 초음파처리하여 짐을 특징으로 하는 크릴새우의 불소 저감화 방법
The method according to claim 1,
The ultrasonic treatment is carried out by heating at 80 DEG C for 10 minutes or by non-heat ultrasonic treatment at room temperature for 20 minutes.
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| KR20110084878A (en) * | 2008-09-12 | 2011-07-26 | 에머랄드 피셔리스 에이에스 | Process for reducing the fluoride content when producing proteinaceous concentrates from krill |
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| KR910015233A (en) * | 1990-02-13 | 1991-09-30 | 권태완 | Fluorine Reduction Method of Antarctic Shrimp Using Electroconcentration Method |
| KR20110084878A (en) * | 2008-09-12 | 2011-07-26 | 에머랄드 피셔리스 에이에스 | Process for reducing the fluoride content when producing proteinaceous concentrates from krill |
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