JPS62292802A - Purification of chitosan - Google Patents
Purification of chitosanInfo
- Publication number
- JPS62292802A JPS62292802A JP13479886A JP13479886A JPS62292802A JP S62292802 A JPS62292802 A JP S62292802A JP 13479886 A JP13479886 A JP 13479886A JP 13479886 A JP13479886 A JP 13479886A JP S62292802 A JPS62292802 A JP S62292802A
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- precipitate
- necessary
- salt
- acid
- 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.)
- Granted
Links
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 51
- 238000000746 purification Methods 0.000 title claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 18
- 239000012535 impurity Substances 0.000 abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005119 centrifugation Methods 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 abstract description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 3
- 230000009965 odorless effect Effects 0.000 abstract description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 2
- 239000001110 calcium chloride Substances 0.000 abstract description 2
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 2
- 235000011148 calcium chloride Nutrition 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000001103 potassium chloride Substances 0.000 abstract description 2
- 235000010344 sodium nitrate Nutrition 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 3
- 229910052925 anhydrite Inorganic materials 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 235000002639 sodium chloride Nutrition 0.000 description 20
- 229920002101 Chitin Polymers 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 241000238557 Decapoda Species 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 239000002195 soluble material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WTOIRKBUWMPVHG-VEIQOZLZSA-N (3R,4R,5S,6R)-3-amino-2-hexadecyl-6-(hydroxymethyl)oxane-2,4,5-triol Chemical compound CCCCCCCCCCCCCCCCC1(O)O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1N WTOIRKBUWMPVHG-VEIQOZLZSA-N 0.000 description 1
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 1
- 241000131500 Chionoecetes opilio Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- -1 acids Chemical class 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000850 deacetylating effect Effects 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Abstract
Description
【発明の詳細な説明】 ３、発明の詳細な説明 本発明はキトサンの精製法に関するものである。[Detailed description of the invention] 3. Detailed description of the invention The present invention relates to a method for purifying chitosan.
一般に、キトサン（ｃｈｉｔｏｓａｎ）はカニの甲羅な
どの主成分であるキチンを脱アセチルして得られる塩基
性多糖である。キトサンの原料となるキチンは無を椎動
物、特にエビやカニ等の水産の甲殻類をはじめ、Ｖ；！
ｉ！産の昆虫類の外殻成分、さらに。Generally, chitosan is a basic polysaccharide obtained by deacetylating chitin, which is a main component of crab shells and the like. Chitin, the raw material for chitosan, comes from vertebrates, especially marine crustaceans such as shrimp and crabs.
i! In addition, the outer shell components of insects produced in Japan.
軟体動物の外皮成分、菌類の細胞壁中などに広く存在し
ており、その年間の生合成量は、数十億トンとみられて
いるものの、殆ど利用されてない資源のひとつである。It is widely present in the outer skin components of molluscs and in the cell walls of fungi, and although its annual biosynthesis is estimated to be several billion tons, it is one of the resources that is hardly used.
最も利用されている。エビ。Most used. shrimp.
カニの外殻成分は、このキチンとタンパク質及び、炭酸
カルシウムから成る復合素材で、キチンにする為には、
希アルカリでタンパク質を、希酸で石灰分を除去しなく
てはならない。このようにして得られたキチンはＮ−７
セチルグルコサミンが直列にβ−１，４結合した分子量
数十万の高分子物ノαである。このキチンを４０〜５０
％の濃アルカリ存在下で加熱して、脱アセチル化すると
、キトサンが得られる。しかし、その性状は未だ甲羅の
名残を留め、カニ殻臭がかなり強く感じられ、かつ甲羅
由来の淡赤色の色素も残存しているものである。The crab's outer shell component is a composite material consisting of chitin, protein, and calcium carbonate, and in order to make chitin,
Proteins must be removed with dilute alkali and lime with dilute acid. The chitin thus obtained is N-7
It is a polymeric substance α with a molecular weight of several hundred thousand, in which cetylglucosamine is connected in series with β-1,4 bonds. This chitin is 40-50
Deacetylation by heating in the presence of % concentrated alkali yields chitosan. However, it still retains the remains of its shell, has a very strong crab shell odor, and also retains the pale red pigment derived from its shell.
従来、キトサンは、その強い凝集力を利用して、各種分
散物の凝集剤として広く使用されて来た。Conventionally, chitosan has been widely used as a flocculant for various dispersions due to its strong cohesive force.
また、近年になって、キトサンに薬理効果が期待され、
医薬としての利用が研究されるようになって来た。その
為、不純物の存在、精製度の程度が問題となり、場合に
よっては、その有用性をも左右することがある。In addition, in recent years, chitosan has been expected to have pharmacological effects.
Research has begun on its use as a medicine. Therefore, the presence of impurities and the degree of purification become a problem, and in some cases may affect its usefulness.
しかしながら、キトサン自体凝集作用が非常に強く、精
製が困難で、純品を大量に得ることはできなかった。However, chitosan itself has a very strong aggregating effect, making purification difficult and making it impossible to obtain a pure product in large quantities.
本発明者らは、キトサンを工業的に大量に精製する方法
を求めて鋭意研究したところ、キトサン溶液に塩を存在
させれば、各種の夾雑物があっても、ρ１１調整だけで
キトサンだけの析出が起ることを知ったのである。The present inventors conducted extensive research in search of a method for industrially purifying chitosan in large quantities, and found that if salt is present in the chitosan solution, chitosan alone can be purified by simply adjusting ρ11, even if various impurities are present. I learned that precipitation occurs.
また、本発明においては、塩の存在下でρＩＩ調整によ
るキトサン析出物は、分離して酸に良好に溶解するので
、再びキトサン溶液にして塩を存在させて、ｐｌ＋調整
によりキトサンを析出させれば、著しるしく精製された
キトサンを得ることができるものである。In addition, in the present invention, the chitosan precipitate obtained by adjusting ρII in the presence of salt separates and dissolves well in acid, so it is necessary to make the chitosan solution again, make salt present, and precipitate chitosan by adjusting pl+. For example, significantly purified chitosan can be obtained.
本発明は、キトサン含有液に塩を添加し、必要によって
析出を生ずるｐＨに調整し、析出物を生成せしめること
を特徴とするキトサンの精製法である。The present invention is a method for purifying chitosan, which is characterized by adding a salt to a chitosan-containing liquid, adjusting the pH to a level that causes precipitation if necessary, and producing a precipitate.
また、本発明は、キトサン含有液に塩を添加し、必要に
よって析出を生ずるｐＨに調整し、得られた析出物を必
要に応じて洗滌し、該析出物を酸に溶解することを特徴
とするキトサンの精製法である。Further, the present invention is characterized in that a salt is added to the chitosan-containing liquid, the pH is adjusted as necessary to cause precipitation, the obtained precipitate is washed as necessary, and the precipitate is dissolved in an acid. This is a method for purifying chitosan.
また１本発明は、キトサン含有液に塩を添加し、必要に
よって析出を生ずるｐＨに調整し、得られた析出物を必
要に応じて水洗し、該析出物を酸に溶解し、析出を生ず
るｐＨに調整し、得られた析出物を必要に応じて洗滌し
、再び析出物を酸に溶解し。In addition, in the present invention, a salt is added to a chitosan-containing liquid, the pH is adjusted as necessary to cause precipitation, the obtained precipitate is washed with water as necessary, and the precipitate is dissolved in an acid to cause precipitation. The pH was adjusted, the resulting precipitate was washed as necessary, and the precipitate was dissolved in acid again.
必要があれば上記の析出−洗滌−溶解の操作をくり返す
ことを特徴とするキトサンの精製法である。This chitosan purification method is characterized by repeating the above-mentioned precipitation-washing-dissolution operations if necessary.
本発明の精製法に適用されるキトサン含有液としては、
夾雑物の多い脱アセチル化処理した処理液などに適用出
来る。The chitosan-containing liquid applicable to the purification method of the present invention includes:
It can be applied to deacetylated processing liquids that contain many impurities.
キトサン含有液に添加される塩としては、次の例示の塩
を含めて塩の１又は２以上である。The salt added to the chitosan-containing solution is one or more salts including the following salts.
即ち、塩化カリ、塩化ナトリウム、塩化カルシウム、塩
化アンモニウムなどの塩酸塩、硝酸カリ、硝酸ナトリウ
ムなどの硝酸塩、酢酸ソーダなどの酢酸塩、硫酸２カリ
、硫安、硫酸カルシウム、硫酸銅などの硫酸塩、リン酸
２カリ、リン酸１カリ、リン酸２ソーダ、リン酸エソー
ダなどのリン酸塩などが例示される。Namely, hydrochlorides such as potassium chloride, sodium chloride, calcium chloride, ammonium chloride, nitrates such as potassium nitrate, sodium nitrate, acetates such as sodium acetate, sulfates such as dipotassium sulfate, ammonium sulfate, calcium sulfate, copper sulfate, Examples include phosphates such as dipotassium phosphate, monopotassium phosphate, disodic phosphate, and esodium phosphate.
添加する塩は溶解した状態であれば、どれだけでもよい
が、好ましいのはキトサン含有液に対し０．５〜５０％
、より好ましくは２〜４０％程度である。Any amount of salt may be added as long as it is dissolved, but it is preferably 0.5 to 50% based on the chitosan-containing liquid.
, more preferably about 2 to 40%.
添加する塩の種類によってはｐＨが７以上になるので、
この場合はｐＨの調整を行うことなく、キトサンが析出
するので、析出物を分離すればよい。Depending on the type of salt added, the pH will be higher than 7.
In this case, since chitosan precipitates without adjusting the pH, it is sufficient to separate the precipitate.
塩の添加によってｐＨが７より低くても差しつかえない
が好ましくはカセイソーダ等のアルカリを用いて、ｐｌ
＋を７〜９、更に好ましくは８．５附近にｐｌ＋調整を
行うのが好適である。Although it is acceptable to lower the pH to below 7 by adding salt, it is preferable to use an alkali such as caustic soda.
It is preferable to adjust pl+ to 7 to 9, more preferably around 8.5.
キトサン含有液に塩の添加とｐｌ＋７〜９の調整を行え
ば、夾雑物の妨害によって容易に沈澱乃至析出しなかっ
たキトサンが析出を起し、夾雑物とは分離して析出する
。この析出物は遠心分離又は濾布による濾過によって容
易に分離できろ。When salt is added to the chitosan-containing solution and PL+7 to 9 is adjusted, the chitosan that did not easily precipitate or precipitate due to the interference of impurities will precipitate, and will be separated from the impurities and precipitated. This precipitate can be easily separated by centrifugation or filtration with a filter cloth.
従来、キトサンの精製がゲル濾過等によってきわめて低
収率にしか行なわれていなかったことからみれば、塩の
添加だけでキトサンの析出が完全に起るということはき
わめ−で意外なことである。Considering that chitosan has traditionally been purified using gel filtration with extremely low yields, it is extremely surprising that chitosan can be completely precipitated just by adding salt. .
分離した析出物は多量の塩を含んでいるので、これを水
や溶媒で洗滌して脱塩し、酸に溶解する。Since the separated precipitate contains a large amount of salt, it is washed with water or a solvent to desalt it, and then dissolved in acid.
酸としては酢酸などの有機酸、塩酸、！酸などの無機酸
などいずれの酸でもよく、また、濃度と゛しては０．０
１〜３モル程度のものがよい。Acids include organic acids such as acetic acid, hydrochloric acid,! Any acid may be used, including inorganic acids such as acids, and the concentration is 0.0.
It is preferably about 1 to 3 moles.
析出物を酸に溶解した後は、２１１７〜９附近の処理の
みで容易に析出するようになっているので、カセイソー
ダ等のアルカリを添加し、２１１７〜９、好ましくはｐ
ｌ＋８．５にＰｉｔ調整し、析出物を得る。After dissolving the precipitate in acid, it is easy to precipitate by just treating around 2117-9, so add an alkali such as caustic soda and dissolve it in 2117-9, preferably p
Pit is adjusted to l+8.5 to obtain a precipitate.
更に、精製するためには、この析出物を水等で洗滌し、
再び酸に溶ｐし、ρ１１７〜９のｐＨ調整を行い、析出
物を得ることができる。Furthermore, in order to purify this precipitate, wash it with water etc.
A precipitate can be obtained by dissolving in acid again and adjusting the pH to ρ117 to 9.
この精製処理は何度でも行うことができ、はとんど純粋
なキトサンを得ることが可能となったのである。This purification process can be repeated any number of times, making it possible to obtain extremely pure chitosan.
次に本発明の試験例及び実施例を示す。Next, test examples and examples of the present invention will be shown.
試験例
市販のキトサン２５Ｋを０．５モルの酢酸 ５１２に溶
解し、溶解液を１００ｍ Ｑづつ２０本用意し、これに
表１の塩を添加し、表１のｐｌ＋調整を行い、沈澱物の
量を３１１定した。得られた結果は表１に示される。Test Example Commercially available chitosan 25K was dissolved in 0.5 mol of acetic acid 512, 20 bottles of 100 mQ each were prepared, the salts shown in Table 1 were added thereto, pl+ was adjusted as shown in Table 1, and the precipitate was dissolved. The amount was determined to be 311. The results obtained are shown in Table 1.
表 １
添加塩類 調整ρ１１ 添加量（％） 回収
キトサン（％）１無添加 ８．５
０ ０２ Ｋ２１１ＰＯ４８，５２０９８
３ＫＩＩ２ＰＯ４８，５２０９８
４Ｋ２ＳＯ４８，５５９６
５Ｎａ２５Ｏ＝ ８．５ ５
９８６ ＭｇＳＯ４８，５５９６
７ＣａＳＯ４８，５５６５
８（ＮＩ＋４）２Ｓ０４ ８．５ ５
８８９ （ＮＩ＋２）２＋１２ＳＯ４８，
５５９３１０ＮｌＩ４Ｃ１８，５５９５
１１ＫＣＩ ８．５ １０
８８添加塩類 調整ｐＨ添加量（％）
回収キトサン（幻１２ ＮａＣ１８，５１０６５
１３ＬｉＣ１８，５１０８１
１４ＣａＣ１８，５１０６５
１５ＫＮＯ３８，５４０５５
１６ＮａＮＯ３８，５２０６３
１７Ｃａ（ＮＯ３） ８．５ ２
０ ４７１８ ＣＨ３ＣＯＯＮａ
８．５ ４０ ９０１９ （Ｃ
ＩＩ２ＣＯＯ）２・２Ｎａ ８．５ ３
０ ８５２０ （ＣＨ２ＣＯＯＮａ）２・Ｃ
（Ｏｆｆ）ＣＯＯＮａ ８．５ ２５
７８実施例１
市販のキトサン５０ｇを０．５モルの酢Ｍ１ｉに溶解し
、不溶物を遠心分離（２０，０ＯＯＧ） ｌ、て除き
、１″）られた清澄液をＡ、Ｂ各５Ｑずつに分けた。Table 1 Added salts Adjustment ρ11 Amount added (%) Recovered chitosan (%) 1 No addition 8.5
0 02 K211PO48,52098 3KII2PO48,52098 4K2SO48,5596 5Na25O= 8.5 5
986 MgSO48,5596 7CaSO48,5565 8 (NI+4)2S04 8.5 5
889 (NI+2)2+12SO48,
559310NlI4C18,5595 11KCI 8.5 10
88 Added salts Adjusted pH addition amount (%)
Recovered chitosan (phantom 12 NaC18,51065 13LiC18,51081 14CaC18,51065 15KNO38,54055 16NaNO38,52063 17Ca(NO3) 8.5 2
0 4718 CH3COONa
8.5 40 9019 (C
II2COO)2・2Na 8.5 3
0 8520 (CH2COONa)2・C
(Off) COONa 8.5 25
78 Example 1 50 g of commercially available chitosan was dissolved in 0.5 mol of vinegar M1, and the insoluble matter was centrifuged (20,000 OOG) and the resulting clear liquid was divided into 5 Q each of A and B. divided.
Ａに酢酸ナトリウム１．５ｋｇを加え溶解した。生じた
析出物をサラン環の布上に集め、水で十分洗滌し可溶物
を除去した後、乾燥して白色粉末状のキトサン２０ｇを
得た。1.5 kg of sodium acetate was added to A and dissolved. The resulting precipitate was collected on a Saran ring cloth, thoroughly washed with water to remove soluble materials, and then dried to obtain 20 g of chitosan in the form of a white powder.
また、Ｂにも同様酢酸ナトリウム１．５Ｊを加え溶解し
た。次に４０％カセイソーダでＰＨを７．５に合せた。Similarly, 1.5 J of sodium acetate was added to B and dissolved therein. Next, the pH was adjusted to 7.5 with 40% caustic soda.
生じた析出物をサラン環の布上に集め水で十分洗滌し、
可溶物を除いた後、乾燥して白色粉末のキトサン２３ｇ
を得た。Collect the resulting precipitate on a Saran ring cloth and wash thoroughly with water.
After removing the soluble materials, dry and obtain 23g of chitosan as a white powder.
I got it.
実施例２
市販のキトサン１００ｇを０．５モルの酢酸１０Ｑに溶
解し、不溶解物を遠心分離（２０，０ＯＯＧ ）して除
去し、得られた清澄液に食塩３ｋｇを加えて溶解した。Example 2 100 g of commercially available chitosan was dissolved in 0.5 mol of acetic acid 10Q, undissolved substances were removed by centrifugation (20.0 OOG), and 3 kg of common salt was added and dissolved in the resulting clear liquid.
次いで４０％カセイソーダを用いｐ＋＋を８．５にした
。生じた析出物を遠心分離して回収し、さらにこれを透
枦した後、乾燥して白色粉末状のキトサン９４ｇを回収
した。Then, p++ was adjusted to 8.5 using 40% caustic soda. The resulting precipitate was collected by centrifugation, further filtered, and then dried to collect 94 g of chitosan in the form of a white powder.
実施例３
良く洗５條し乾燥したズワイガニの殻３ｋｇを公知の方
法（Ｍａｋｒｏｍｏｌ、 Ｃｈｅｍ、 ｖｏｌ、１７７
３５８９（１９７６）に傅じ処理することにより粗キト
サン乾燥物約８００Ｇを得た。Example 3 3 kg of well-washed and dried snow crab shells were prepared using a known method (Makromol, Chem, vol. 177).
Approximately 800 G of dried crude chitosan was obtained by the same treatment as in 3589 (1976).
この粗キトサン５０ｇを０．５モルの酢酸１０１２に溶
解し、不溶解物を遠心分離して除去した。得られた清澄
液に硫安５００已を加えて溶解した。次に４０％カセイ
ソーダを用いＰＨを８．５にした。生した析出物を遠心
分離して集めた。次いでこの沈殿を水に分散させて、硫
安を除いた。更に、脱塩した析出物を０．５モルの酢酸
に溶解し、４０％カセイソーダでｐＨを８．５に合せた
。生じた析出物をサラン環の布上に集め回収し、大量の
水で洗滌し可溶物を除いた。洗滌後、析出物を乾燥して
白色粉末状の無臭のキトサン４４．４ ｇを得た。50 g of this crude chitosan was dissolved in 0.5 mol of acetic acid 1012, and undissolved matter was removed by centrifugation. 500 μm of ammonium sulfate was added to the resulting clear liquid to dissolve it. Next, the pH was adjusted to 8.5 using 40% caustic soda. The resulting precipitate was collected by centrifugation. This precipitate was then dispersed in water to remove ammonium sulfate. Furthermore, the desalted precipitate was dissolved in 0.5 mol of acetic acid, and the pH was adjusted to 8.5 with 40% caustic soda. The resulting precipitate was collected on a Saran ring cloth and washed with a large amount of water to remove soluble materials. After washing, the precipitate was dried to obtain 44.4 g of odorless chitosan in the form of a white powder.
粗精製物及び精製物の性状、分析値を表２に示す。Table 2 shows the properties and analytical values of the crude and purified products.
表中の色は日本電色工業社製の測色色差計でａｌｌ定し
り、ａ、ｂで表示した。香はカニ殻臭の残存の程度を官
能検査によって示した。クルコサミンの含有量はそれぞ
れのキトサンを４Ｎ塩酸で加水分解した後エルラン−モ
ルガン法で測定し、算出し、乾物に対する％で表示した
。All colors in the table were determined using a colorimetric colorimeter manufactured by Nippon Denshoku Kogyo Co., Ltd., and expressed as a and b. The degree of residual crab shell odor was determined by a sensory test. The content of curcosamine was calculated by hydrolyzing each chitosan with 4N hydrochloric acid and then measuring by the Erlan-Morgan method, and expressed as % of dry matter.
表２
表より明らかなように色は明度（Ｌ）が大きくなり赤色
（ａ）が減少し、黄色（ｂ）も減少し、全体に白色にな
ったことがわかる。香りについても無臭になった。そし
てグルコサミン含有量も上がり、不純物をほとんど含ま
ないほぼ純品のキトサンが得られた。Table 2 As is clear from the table, the lightness (L) increased, red color (a) decreased, yellow color (b) decreased, and the overall color became white. The fragrance has also become odorless. The glucosamine content also increased, and almost pure chitosan containing almost no impurities was obtained.
代理人 弁理士 戸 １）親 男 手続補正書 昭和６１年１０月２２日Agent Patent Attorney 1) Parent Male Procedural amendment October 22, 1985
Claims (3)
を生ずるｐＨに調整し、析出物を生成せしめることを特
徴とするキトサンの精製法。(1) A method for purifying chitosan, which is characterized by adding a salt to a chitosan-containing liquid and adjusting the pH to a level that causes precipitation, if necessary, to generate a precipitate.
を生ずるｐＨに調整し、得られた析出物を必要に応じて
洗滌し、該析出物を酸に溶解することを特徴とするキト
サンの精製法。(2) Adding a salt to a chitosan-containing solution, adjusting the pH to a level that causes precipitation if necessary, washing the obtained precipitate as necessary, and dissolving the precipitate in an acid. Purification method.
を生ずるｐＨに調整し、得られた析出物を必要に応じて
水洗し、該析出物を酸に溶解し、析出を生ずるｐＨに調
整し、得られた析出物を必要に応じて洗滌し、再び析出
物を酸に溶解し、必要があれば上記の析出−洗滌−溶解
の操作をくり返すことを特徴とするキトサンの精製法。(3) Add salt to the chitosan-containing solution, adjust the pH to a level that causes precipitation if necessary, wash the obtained precipitate with water as necessary, dissolve the precipitate in acid, and adjust the pH to a level that causes precipitation. A method for purifying chitosan, which comprises washing the obtained precipitate as necessary, dissolving the precipitate again in acid, and repeating the above precipitation-washing-dissolution operation if necessary.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13479886A JPS62292802A (en) | 1986-06-12 | 1986-06-12 | Purification of chitosan |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13479886A JPS62292802A (en) | 1986-06-12 | 1986-06-12 | Purification of chitosan |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62292802A true JPS62292802A (en) | 1987-12-19 |
| JPH0133482B2 JPH0133482B2 (en) | 1989-07-13 |
Family
ID=15136777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13479886A Granted JPS62292802A (en) | 1986-06-12 | 1986-06-12 | Purification of chitosan |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62292802A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998017693A1 (en) * | 1996-10-23 | 1998-04-30 | Transgene S.A. | Composition containing chitosan |
| WO2003066682A1 (en) * | 2002-02-07 | 2003-08-14 | Abbott Laboratories De Costa Rica Ltd | Method for deproteinization of chitosan |
| EP1701980A1 (en) * | 2004-01-06 | 2006-09-20 | Université de Sherbrooke | A simplified method to retrieve chitosan from acidic solutions thereof |
| JP2008094989A (en) * | 2006-10-13 | 2008-04-24 | Hyogo Prefecture | Method for dissolution of chitosan to water and resulting composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6176504A (en) * | 1984-09-21 | 1986-04-19 | Fuji Boseki Kk | Production of porous granular chitosan |
-
1986
- 1986-06-12 JP JP13479886A patent/JPS62292802A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6176504A (en) * | 1984-09-21 | 1986-04-19 | Fuji Boseki Kk | Production of porous granular chitosan |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998017693A1 (en) * | 1996-10-23 | 1998-04-30 | Transgene S.A. | Composition containing chitosan |
| WO2003066682A1 (en) * | 2002-02-07 | 2003-08-14 | Abbott Laboratories De Costa Rica Ltd | Method for deproteinization of chitosan |
| EP1701980A1 (en) * | 2004-01-06 | 2006-09-20 | Université de Sherbrooke | A simplified method to retrieve chitosan from acidic solutions thereof |
| EP1701980A4 (en) * | 2004-01-06 | 2011-07-06 | Commercialisation Des Produits De La Rech Appliquee Socpra Sciences Sante Et Humaines S F C Soc D | A simplified method to retrieve chitosan from acidic solutions thereof |
| JP2008094989A (en) * | 2006-10-13 | 2008-04-24 | Hyogo Prefecture | Method for dissolution of chitosan to water and resulting composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0133482B2 (en) | 1989-07-13 |
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