JP4148563B2 - Method for decolorizing chitin or chitosan - Google Patents

Method for decolorizing chitin or chitosan Download PDF

Info

Publication number
JP4148563B2
JP4148563B2 JP18675498A JP18675498A JP4148563B2 JP 4148563 B2 JP4148563 B2 JP 4148563B2 JP 18675498 A JP18675498 A JP 18675498A JP 18675498 A JP18675498 A JP 18675498A JP 4148563 B2 JP4148563 B2 JP 4148563B2
Authority
JP
Japan
Prior art keywords
chitosan
chitin
decolorization
decolorizing
present
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
JP18675498A
Other languages
Japanese (ja)
Other versions
JP2000017001A (en
Inventor
博 亀山
祐二 前崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
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 Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to JP18675498A priority Critical patent/JP4148563B2/en
Publication of JP2000017001A publication Critical patent/JP2000017001A/en
Application granted granted Critical
Publication of JP4148563B2 publication Critical patent/JP4148563B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Landscapes

  • Polysaccharides And Polysaccharide Derivatives (AREA)

Description

【0001】
【発明の属する技術分野】
キチンはキトサン製造用及び関節炎治療剤として期待されているグルコサミン製造用等の原料として使用され、又、皮膚の損傷保護剤として使用される極めて重要な物質である。
キトサンは水質浄化用の凝集剤として使用され、近年では、難消化性により食物繊維の効果が期待され、中でも多くのアミノ基をもつことにより、消化管内で胆汁酸を吸着し、血清コレステロ−ル低下作用を示すことから、今後キトサンは降コレステロ−ル作用を活用した機能性食品への応用が期待されている。又、生分解性ポリマー、ダイエット補助食品等への開発が進められている。
本発明はキチン又はキトサンの脱色方法に関する。
【0002】
【従来の技術】
キチン又はキトサンの脱色は従来、カニ、エビ又はシャコ等の甲皮等又はイカの軟骨を脱蛋白処理、脱カルシウム処理した後のキチン又は脱アセチル化処理した後のキトサンを天日に曝す、又は、キチン又はキトサンに紫外線を照射する、又は、エチルアルコール、アセトン等の不溶性溶剤に浸す、又は、過酸化水素等の過酸化物質、亜塩素酸ナトリウム、次亜塩素酸ナトリウム等の酸化剤を添加する等の方法でキチン又はキトサンを脱色していた。
【0003】
【発明が解決しようとする課題】
しかし、天日に曝す方法は、砂、昆虫等の異物の混入が発生し、紫外線を照射する方法は、大がかりな設備が必要で実用的でない。不溶性溶剤に浸す方法は、乾燥による安全性の確保が必要でありかつ溶剤の完全除去が出来ず食品への使用が困難となり、過酸化水素等の過酸化物質、亜塩素酸ナトリウム、次亜塩素酸ナトリウム等の酸化剤を添加する方法は、残留が問題となり食品への使用が困難となる。
【0004】
このように、キチン又はキトサンの脱色には、膨大な製造設備と多大な製造時間が必要であり、脱色剤等を使用せず簡単で、安価で、安全性に富みしかも物性劣化の無い生産効率のよい脱色方法が望まれていた。
【0005】
【課題を解決するための手段】
そこで本発明者らは種々検討した結果、難脱色性のキチン又はキトサンを天日干しや薬剤処理なしでキチン又はキトサンに水を含ませ加温維持した後、乾燥することでキチン又はキトサンが脱色できる方法を見い出した。更に、この脱色方法はキチン又はキトサンの物性劣化が殆ど無いことを見い出した。
その結果、一般細菌や異物の混入が無く、脱色のための薬剤が不要となり、安価で安全で高品質の食品用には最も適した脱色方法となった。
本発明は上記知見に基づいて完成されたものである。
【0006】
即ち、本発明は、
(1)キチン又はキトサンに水を含ませ加温維持した後、乾燥することを特徴とするキチン又はキトサンの脱色方法
(2)キチン又はキトサンの含水率が50%以上である上記(1)記載の方法
(3)加温維持する温度が50℃以上である上記(1)又は(2)記載の方法
(4)加温維持する時間が2時間以上である上記(1)〜(3)のいずれかに記載の方法
(5)脱色による物性劣化を殆ど認めない上記(1)〜(4)のいずれかに記載の方法、に関する。
【0007】
本発明において用いるキチンは、どのような方法で得たものであってもかまわないが、通常、例えばカニ、エビ等の甲殻類の甲皮等を原料とし、それを希アルカリ又は酵素で脱蛋白し、さらに希酸で脱カルシウムして灰分を取り除き、反応終了後、数回水洗することによって得られる。
キトサンは、例えば、キチンを水酸化ナトリウム、水酸化カリウム等の強アルカリ剤中で脱アセチル化した後、数回水洗することによって得られる。
本発明の脱色における乾燥は、例えば乾燥機による乾燥が好ましい、使用する乾燥機は、如何なる乾燥機でも良いが、キチン又はキトサンの粒子同士が付着し合って団子状にならない様に撹拌装置の有るものが良く、ナウター乾燥機、コニカル乾燥機、スクリュウ式乾燥機が好ましい。
脱色前のキチン又はキトサンの粒子径は、粗粉砕されているものであれば如何なる粒子径でもよいが、小さい程脱色され易いので、好ましくは1cm以下であり、より好ましくは30〜200μmである。
本発明の脱色に使用するキチン又はキトサンに含まれる水の量は、キチン又はキトサン100重量部に対して100重量部以上であることが好ましく、より好ましくは150〜1000重量部であり、特に好ましくは200〜250重量部である。
本発明の脱色時の温度は、50℃以上に加温維持することが好ましく、より好ましくは70〜120℃であり、特に好ましくは80〜90℃である。
本発明の脱色時の加温維持時間は、加温維持する温度にもよるが2時間以上が好ましく、より好ましくは3〜24時間であり、特に好ましくは3〜8時間である。
脱色による物性劣化は、通常、天日曝露及び過酸化物質及び酸化剤の添加では、脱色前粘度の半分程度にまで低下する。本発明の脱色方法では、脱色前後の物性に殆ど変化が見られなかった。
【0008】
【発明の効果】
本発明は、薬剤や溶媒を全く使用せず、安全で安価で、高品質の脱色されたキチン又はキトサンが得られる極めて有効な製造方法である。
【0009】
以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
色調は、肉眼目視と色差計(日本電色(株)製)で観察した。
キチン粘度は、キチン10gに48%苛性ソーダ200mlを加え、95℃で3時間反応して得られたキトサンの粘度で表示した。
実施例1
2mのコニカル乾燥機に、乾燥粘度680mPa・s、平均粒子径300μmの赤褐色の粉末キチン500kg及び水道水1500kgを入れ、70℃で4時間撹拌した後、減圧下80℃で乾燥し微黄色キチン粉末495kgを得た。脱色前後の外観色調及び物性(粘度)を表1に示す。
【0010】
【表1】

Figure 0004148563
【0011】
実施例2
3mのナウター乾燥機に、乾燥粘度800mPa・s、脱アセチル化度93.0%、平均粒子径180μmの赤色の粉末キトサン300kg及び水道水600kgを入れ、80℃で6時間撹拌した後、減圧下90℃で乾燥し微黄色キトサン粉末299kgを得た。脱色前後の外観色調及び物性(粘度、脱アセチル化度)を表2に示す。
【0012】
【表2】
Figure 0004148563
【0013】
実施例3
3mのコニカル乾燥機に、乾燥粘度280mPa・s、脱アセチル化度96.0%、平均粒子径140μmの赤色の粉末キトサン400kg及び水道水700kgを入れ、85℃で4時間撹拌した後、減圧下85℃で乾燥し微黄色キトサン粉末397kgを得た。脱色前後の外観色調及び物性(粘度、脱アセチル化度)を表3に示す。
【0014】
【表3】
Figure 0004148563
[0001]
BACKGROUND OF THE INVENTION
Chitin is an extremely important substance that is used as a raw material for the production of chitosan and for the production of glucosamine, which is expected as an agent for treating arthritis.
Chitosan is used as a flocculant for water purification, and in recent years, it is expected to have an effect of dietary fiber due to indigestibility, and by having many amino groups, it absorbs bile acids in the digestive tract, and serum cholesterol Since it shows a lowering action, chitosan is expected to be applied to functional foods utilizing the cholesterol action. Development into biodegradable polymers, dietary supplements, and the like is underway.
The present invention relates to a method for decolorizing chitin or chitosan.
[0002]
[Prior art]
Decolorization of chitin or chitosan is conventionally exposed to the sun after chitin or deacetylation treatment after deproteinization, decalcification treatment of carcass of crabs, shrimp or shrimp, etc. or squid cartilage, or Irradiate chitin or chitosan with ultraviolet light, or immerse in an insoluble solvent such as ethyl alcohol or acetone, or add an oxidizing agent such as hydrogen peroxide or other peroxygen, sodium chlorite or sodium hypochlorite The chitin or chitosan was decolored by the method of doing.
[0003]
[Problems to be solved by the invention]
However, the sun exposure method involves the mixing of foreign substances such as sand and insects, and the method of irradiating with ultraviolet rays is not practical because it requires extensive equipment. The method of soaking in an insoluble solvent requires ensuring safety by drying, and the solvent cannot be completely removed, making it difficult to use in foods. Peroxides such as hydrogen peroxide, sodium chlorite, hypochlorite In the method of adding an oxidizing agent such as sodium acid, the residue becomes a problem and it is difficult to use it for food.
[0004]
In this way, decolorization of chitin or chitosan requires enormous production facilities and a great deal of production time, is simple and inexpensive without using a decolorizing agent, etc., is safe, and has no deterioration in physical properties. A good decolorization method was desired.
[0005]
[Means for Solving the Problems]
Therefore, as a result of various studies, the present inventors have found that chitin or chitosan can be decolored by drying the chitin or chitosan that is hardly decolorized by adding water to the chitin or chitosan without heating or chemical treatment, followed by heating. I found a way. Furthermore, it has been found that this decolorization method hardly causes deterioration of physical properties of chitin or chitosan.
As a result, there is no contamination with general bacteria and foreign substances, and no chemical for decolorization is required, and the decolorization method is most suitable for cheap, safe and high-quality foods.
The present invention has been completed based on the above findings.
[0006]
That is, the present invention
(1) A method for decolorizing chitin or chitosan, which comprises drying water after adding water to chitin or chitosan and maintaining the temperature. (2) The water content of chitin or chitosan is 50% or more. Method (3) The method of (1) or (2) above, wherein the temperature for maintaining the temperature is 50 ° C. or higher. (4) The time for maintaining the temperature is 2 hours or longer. The method according to any one of the above (1) to (4), wherein the method (5) according to any one of the methods does not substantially deteriorate physical properties due to decolorization.
[0007]
The chitin used in the present invention may be obtained by any method. Usually, for example, crustacean crusts such as crabs and shrimps are used as raw materials, which are deproteinized with a dilute alkali or enzyme. Further, it can be obtained by decalcifying with a dilute acid to remove ash, and washing with water several times after completion of the reaction.
Chitosan can be obtained, for example, by deacetylating chitin in a strong alkaline agent such as sodium hydroxide or potassium hydroxide and then washing with water several times.
The drying in the decolorization of the present invention is preferably, for example, drying with a dryer. The dryer used may be any dryer, but has a stirring device so that chitin or chitosan particles do not adhere to each other to form a dumpling. Things are good, and a Nauter dryer, a conical dryer and a screw dryer are preferred.
The particle size of chitin or chitosan before decolorization may be any particle size as long as it is coarsely pulverized, but the smaller the size, the easier it is to decolorize, so it is preferably 1 cm or less, more preferably 30 to 200 μm.
The amount of water contained in chitin or chitosan used for decolorization of the present invention is preferably 100 parts by weight or more, more preferably 150 to 1000 parts by weight, particularly preferably 100 parts by weight of chitin or chitosan. Is 200 to 250 parts by weight.
The temperature during decolorization of the present invention is preferably maintained at 50 ° C. or higher, more preferably 70 to 120 ° C., and particularly preferably 80 to 90 ° C.
The warming maintenance time at the time of decoloring of the present invention is preferably 2 hours or more, more preferably 3 to 24 hours, and particularly preferably 3 to 8 hours, although it depends on the temperature at which the warming is maintained.
Deterioration of physical properties due to decoloring usually decreases to about half of the viscosity before decolorization when exposed to the sun and the addition of peroxides and oxidizing agents. In the decolorization method of the present invention, there was almost no change in physical properties before and after decolorization.
[0008]
【The invention's effect】
The present invention is an extremely effective production method that can obtain high-quality decolorized chitin or chitosan without using any drug or solvent, and safe and inexpensive.
[0009]
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
The color tone was observed with the naked eye and a color difference meter (manufactured by Nippon Denshoku Co., Ltd.).
The chitin viscosity was expressed as the viscosity of chitosan obtained by adding 200 ml of 48% caustic soda to 10 g of chitin and reacting at 95 ° C. for 3 hours.
Example 1
In a 2 m 3 conical dryer, 500 kg of reddish brown powder chitin with a dry viscosity of 680 mPa · s and an average particle size of 300 μm and 1500 kg of tap water are stirred for 4 hours at 70 ° C., then dried at 80 ° C. under reduced pressure, and slightly yellow chitin 495 kg of powder was obtained. Table 1 shows the appearance color tone and physical properties (viscosity) before and after decolorization.
[0010]
[Table 1]
Figure 0004148563
[0011]
Example 2
A 3 m 3 Nauta dryer was charged with 300 kg of red powdered chitosan having a dry viscosity of 800 mPa · s, a degree of deacetylation of 93.0%, and an average particle size of 180 μm, and 600 kg of tap water. The resultant was dried at 90 ° C. to obtain 299 kg of slightly yellow chitosan powder. Table 2 shows the appearance color tone and physical properties (viscosity, degree of deacetylation) before and after decolorization.
[0012]
[Table 2]
Figure 0004148563
[0013]
Example 3
A 3 m 3 conical dryer was charged with 400 kg of red powdered chitosan having a dry viscosity of 280 mPa · s, a deacetylation degree of 96.0%, and an average particle diameter of 140 μm and 700 kg of tap water, and stirred at 85 ° C. for 4 hours, and then decompressed. The resultant was dried at 85 ° C. to obtain 397 kg of slightly yellow chitosan powder. Table 3 shows the appearance color tone and physical properties (viscosity, degree of deacetylation) before and after decolorization.
[0014]
[Table 3]
Figure 0004148563

Claims (2)

キチン又はキトサンに水を含ませ70〜90℃で3〜24時間加温維持した後、乾燥することを特徴とする物性劣化を殆ど認めないキチン又はキトサンの脱色方法。A method for decolorizing chitin or chitosan with little deterioration in physical properties , characterized in that water is contained in chitin or chitosan and maintained at 70 to 90 ° C. for 3 to 24 hours and then dried. キチン又はキトサンの含水率が50%以上である請求項1記載の方法。  The method according to claim 1, wherein the water content of chitin or chitosan is 50% or more.
JP18675498A 1998-07-02 1998-07-02 Method for decolorizing chitin or chitosan Expired - Lifetime JP4148563B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP18675498A JP4148563B2 (en) 1998-07-02 1998-07-02 Method for decolorizing chitin or chitosan

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP18675498A JP4148563B2 (en) 1998-07-02 1998-07-02 Method for decolorizing chitin or chitosan

Publications (2)

Publication Number Publication Date
JP2000017001A JP2000017001A (en) 2000-01-18
JP4148563B2 true JP4148563B2 (en) 2008-09-10

Family

ID=16194064

Family Applications (1)

Application Number Title Priority Date Filing Date
JP18675498A Expired - Lifetime JP4148563B2 (en) 1998-07-02 1998-07-02 Method for decolorizing chitin or chitosan

Country Status (1)

Country Link
JP (1) JP4148563B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111138563B (en) * 2020-03-13 2022-04-22 山东美佳集团有限公司 Method for preparing chitosan from snow crab shells

Also Published As

Publication number Publication date
JP2000017001A (en) 2000-01-18

Similar Documents

Publication Publication Date Title
US8993015B2 (en) Method for manufacturing pure guar flour
Barikani et al. Preparation and application of chitin and its derivatives: a review
Raj et al. Grafting modification of okra mucilage: Recent findings, applications, and future directions
EP2188315B1 (en) Method of preparing fibre-containing pectin product and pectin products hereof
JPH0730123B2 (en) Method for producing high-purity chitin and chitosan
DK165276B (en) ANIMAL PRODUCTS
Simpson et al. Bioprocessing of chitin and chitosan
Oyatogun et al. Chitin, chitosan, marine to market
US20040215005A1 (en) Chitosan preparation
CN107511135A (en) A kind of ferric trichloride hydrotalcite chitosan polymer and preparation method thereof
Adekanmi et al. Different processing sequential protocols for extraction, quantification and characterization of chitosan from cray fish
Yang et al. Effects of UV/H2O2 degradation on Moringa oleifera Lam. leaves polysaccharides: Composition, in vitro fermentation and prebiotic properties on gut microorganisms
JP4148563B2 (en) Method for decolorizing chitin or chitosan
JP2901176B2 (en) Low viscosity chitosan and method for producing the same
JP4119482B2 (en) Chitin derivative having carboxyl lower alkyl group and hydrophobic substituent as hydrophilic substituents, polymeric micelle type carrier comprising the chitin derivative and micelle-like aqueous composition thereof
JP4140741B2 (en) Method for producing dry chitin powder or dry chitosan powder
CN107641159B (en) Production process of low-viscosity whitening carrageenan
CA2514952A1 (en) Chitosan foodstuff
WO2014102332A1 (en) Depolymerisation of alginic acid
Montilla et al. Biological effects and extraction processes used to obtain marine chitosan
EP1142987A1 (en) Composition of powdered aureobacidium culture solution, manufacturing method thereof and powder mixture with the composition
TWI718844B (en) Method for extracting chitosan
JPH01185301A (en) Manufacture of low-molecular chitosan
JP3359739B2 (en) Marine health food
Chatterjee et al. Preparation and characterization of lobster shell chitosan: Modification of

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20040721

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20080415

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20080603

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20080624

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20080624

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110704

Year of fee payment: 3

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110704

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20140704

Year of fee payment: 6

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

EXPY Cancellation because of completion of term