JPS6317901A - Purification of chitosan - Google Patents

Purification of chitosan

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Publication number
JPS6317901A
JPS6317901A JP15979386A JP15979386A JPS6317901A JP S6317901 A JPS6317901 A JP S6317901A JP 15979386 A JP15979386 A JP 15979386A JP 15979386 A JP15979386 A JP 15979386A JP S6317901 A JPS6317901 A JP S6317901A
Authority
JP
Japan
Prior art keywords
chitosan
precipitate
acid
containing liquid
adjusted
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.)
Pending
Application number
JP15979386A
Other languages
Japanese (ja)
Inventor
Junichi Tamura
順一 田村
Kiyoshi Kadowaki
門脇 清
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.)
Higeta Shoyu Co Ltd
Original Assignee
Higeta Shoyu 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 Higeta Shoyu Co Ltd filed Critical Higeta Shoyu Co Ltd
Priority to JP15979386A priority Critical patent/JPS6317901A/en
Publication of JPS6317901A publication Critical patent/JPS6317901A/en
Pending legal-status Critical Current

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Abstract

PURPOSE:To easily purify large amount of chitosan useful as a flocculant for various dispersions and pharmaceuticals, etc., on an industrial scale, by adjusting a chitosan-containing liquid to a specific pH, thereby precipitating the chitosan from the liquid. CONSTITUTION:A chitosan-containing liquid (e.g. a process liquid obtained by deacetylation treatment and having high impurity content) is adjusted to >=6.0pH, preferably >=6.5pH to obtain a precipitate. The precipitate is, if necessary, washed, dissolved usually in an acid (acetic acid, hydrochloric acid, sulfuric acid, etc., having a concentration of 0.01-3mol) and adjusted to >=6.0pH, preferably >=6.5pH with an alkali such as KOH to again precipitate chitosan. The purity of chitosan can be improved by repeating the above steps of precipitation, washing and dissolution.

Description

【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] 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、陸産の
昆虫類の外殻成分、さらに、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。最も利用されている、エビ
、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複合素材で、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−
ア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質である。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。
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, is widely found in vertebrates, especially marine crustaceans such as shrimp and crabs, the outer shell components of terrestrial insects, the outer shell components of molluscs, and the cell walls of fungi. Although the annual biosynthesis amount is estimated to be several billion tons, it is one of the least utilized resources. The outer shell components of shrimp and crabs, which are most used, are a composite material consisting of chitin, protein, and calcium carbonate.To make chitin, the protein is removed with dilute alkali and the lime content is removed with dilute acid. Must-have. The chitin thus obtained is N-
It is a polymer substance with a molecular weight of several hundred thousand, consisting of acetylglucosamine linked 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できる。
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, their usefulness can be affected.

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、各種の
狭雑物があっても、pH6,0以上へのpH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 even if there were various impurities in the chitosan solution, chitosan could be purified by simply adjusting the pH to 6.0 or higher. I learned that precipitation occurs.

また、本発明においては、pH6,0以上のpH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、pH6,0以上へのpH
調整によりキトサンを析出させれば、著じるしく精製さ
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, chitosan precipitates resulting from pH adjustment to pH 6.0 or higher are separated and dissolved well in acid, so they are made into a chitosan solution again and adjusted to pH 6.0 or higher.
If chitosan is precipitated through adjustment, significantly purified chitosan can be obtained.

本発明は、キトサン含有液をpH6,0以上、好ましく
はpH6,5以上に調整し、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 chitosan purification method characterized by adjusting a chitosan-containing liquid to pH 6.0 or higher, preferably pH 6.5 or higher, and generating a precipitate.

また、本発明は、キトサン含有液をpH6.0以上、好
ましくはpH6.5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 the chitosan-containing liquid is adjusted to pH 6.0 or higher, preferably pH 6.5, the obtained precipitate is washed as necessary, and the precipitate is dissolved in an acid. This is a method for purifying chitosan.

また、本発明は、キトサン含有液をpH6,0以上、好
ましくはpH6,5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、pH6以上、好
ましくはpH6.5以上に調整し、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である。
In addition, the present invention adjusts the chitosan-containing liquid to pH 6.0 or higher, preferably pH 6.5, washes the obtained precipitate with water as needed, dissolves the precipitate in acid, and adjusts the chitosan-containing liquid to pH 6.0 or higher, preferably pH 6.5. is characterized by adjusting the pH to 6.5 or higher, washing the obtained precipitate as necessary, dissolving the precipitate in acid again, and repeating the above precipitation-washing-dissolution operation if necessary. This is a method for purifying chitosan.

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いずれで
もよい。
The chitosan-containing liquid applicable to the purification method of the present invention includes:
Any treatment solution, such as a deacetylated treatment solution containing many impurities, may be used.

キトサン含有液をpH6以上、好ましくは、pH6,5
以上に調整することにより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る。
The chitosan-containing solution is adjusted to pH 6 or higher, preferably pH 6.5.
By making the above adjustments, chitosan is precipitated and separated from impurities. 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、pH
の調整だけでキトサンの析出が完全に起るということは
きわめて意外なことである。
Conventionally, chitosan was purified by gel filtration, etc., with extremely low yields.
It is extremely surprising that the precipitation of chitosan can occur completely just by adjusting the .

分離した析出物は夾雑物の一部を混在させているので、
これを水や溶媒で洗滌して酸に溶解する。
The separated precipitate contains some impurities, so
This is washed with water or a solvent and dissolved in acid.

酸としては酢酸などの有機酸、塩酸、硫酸などの無機酸
などいずれの酸でもよく、また、濃度としては0.01
〜3モル程度のものがよい。
The acid may be any acid such as an organic acid such as acetic acid or an inorganic acid such as hydrochloric acid or sulfuric acid, and the concentration is 0.01
It is preferable that the amount is about 3 mol.

析出物を酸に溶解した後は、pH6以上、好ましくはp
H6.5以上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、pH6
以上、好ましくはpH6,5以上にPH調整し、析出物
を得る。
After dissolving the precipitate in acid, the pH should be 6 or more, preferably p
Since it is easy to precipitate only by treatment at pH 6.5 or higher, add an alkali such as caustic soda and raise the pH to 6.5.
As described above, the pH is preferably adjusted to 6.5 or higher 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、
再び酸に溶解し、pH6以上、好ましくはpH6,5以
上の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 an acid again and adjusting the pH to 6 or higher, preferably 6.5 or higher.

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25gを0.25モルの塩酸5Qに溶解
し、溶解液を100n+ Qづつ11本用意し、第1図
のp)l調整を行い、析出物の量を測定した。得られた
結果は図1に示される。
Test Example 25 g of commercially available chitosan was dissolved in 0.25 mol of hydrochloric acid 5Q, 11 bottles of 100n+Q of the solution were prepared, p)l adjustment in Figure 1 was carried out, and the amount of precipitate was measured. The results obtained are shown in FIG.

第1図のキトサンの回収率は、溶解したキトサン100
mQ中のグルコサミン量(4N塩酸で加水分解後エルラ
ン−モルガン法で測定)に対する析出物の乾燥重量を百
分率で表示した。
The recovery rate of chitosan in Figure 1 is 100% of dissolved chitosan.
The dry weight of the precipitate was expressed as a percentage with respect to the amount of glucosamine in mQ (measured by the Erlan-Morgan method after hydrolysis with 4N hydrochloric acid).

その結果は第1図に示されるが、第1図からpH6を超
えるとキトサンの析出がはじまり、pH6,5以上とな
るとほとんど完全に析出するのがわかる。
The results are shown in FIG. 1, and it can be seen from FIG. 1 that chitosan begins to precipitate when the pH exceeds 6, and almost completely precipitates when the pH exceeds 6.5.

実施例1 市販のキトサン25gを0.5モルの塩酸5Qに溶解し
、不溶物を遠心分離(20,0OOG) して除いた。
Example 1 25 g of commercially available chitosan was dissolved in 0.5 mol of hydrochloric acid 5Q, and insoluble materials were removed by centrifugation (20.0 OOG).

得られた清澄液に40%カセイソーダを加え、pHを7
.0に調整した。生じた析出物をサラン製の布で濾過し
た後乾燥し、白色粉末状のキトサン22gを得た。精製
前後のキトサン中のグルコサミン量をそれぞれ、4N塩
酸で加水分解後エルラン−モルガン法で測定し、乾物に
対する含量で示すと、精製前92%であったのに対し、
精製後は96%であった。
Add 40% caustic soda to the resulting clear liquid to adjust the pH to 7.
.. Adjusted to 0. The resulting precipitate was filtered through Saran cloth and dried to obtain 22 g of white powdered chitosan. The amount of glucosamine in chitosan before and after purification was measured by the Erlan-Morgan method after hydrolysis with 4N hydrochloric acid, and when expressed as a content on dry matter, it was 92% before purification, whereas before purification, it was 92%.
After purification, it was 96%.

実施例2 市販のキトサン100gを0.5モルの酢酸25Ωに溶
解し、不溶物を遠心分離(20,0OOG) して除い
た。
Example 2 100 g of commercially available chitosan was dissolved in 0.5 mol of acetic acid 25Ω, and insoluble matter was removed by centrifugation (20.0 OOG).

得られた清澄液に40%カセイソーダを加え、pHを8
.5に合せた。静置後生じた析出物をサラン製の布上に
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を得た・精製前後のキトサンの性
状、分析値を表1に示した。
Add 40% caustic soda to the resulting clear liquid to adjust the pH to 8.
.. Adjusted to 5. After standing, the precipitate formed was collected on Saran cloth, thoroughly washed with water to remove soluble materials, and dried to obtain chitosan in the form of a white powder.Characteristics and analysis of chitosan before and after purification The values are shown in Table 1.

表中の色は日本重色工業社製の測色色差計で測定し、L
、a、bで示した。香はカニ殻臭の残存の程度を官能検
査によって示した。グルコサミンの含有量は精製前後の
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。
The colors in the table are measured with a colorimeter made by Nihon Heavy Industries Co., Ltd.
, a, b. The degree of residual crab shell odor was determined by a sensory test. The content of glucosamine was calculated by hydrolyzing chitosan before and after purification with 4N hydrochloric acid and then measured by the Erlan-Morgan method, and expressed as a percentage of the dry matter.

表1 表1より明らかなように色は明度(L)が大きくなり、
赤色(、)が減少し、黄色(b)も減少し、全体に色素
が除去され、白色になったことがわかる。
Table 1 As is clear from Table 1, the lightness (L) of colors increases,
It can be seen that the red color (,) has decreased and the yellow color (b) has also decreased, indicating that the pigment has been completely removed and the color becomes white.

香りについても臭気が除去されている。そして、グルコ
サミン含有量が上がり、不純物をほとんど含まないほぼ
純品に近いキトサンが得られた。
Regarding fragrance, odors are also removed. The glucosamine content increased, and almost pure chitosan containing almost no impurities was obtained.

実施例3 良く洗滌し、乾燥したズワイガニの殻3kgを公知の方
法(Makromol、 Chem、 vol、 17
73589(1976))に準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. 17).
73589 (1976)) to obtain about 800 g of crude dried chitosan.

この、粗キトサン50gを0.5N酢酸10Qに溶解し
、不溶解物を遠心分離して除去した。次に40%カセイ
ソーダを用いpHを7.5に調整した。生じた析出物を
遠心分離して集めた。次いでこの沈澱を水に分散させ、
水に可溶物を除いた。更に、この析出物を0.5モルの
酢酸に溶解し、40%カセイソーダでpHを7.5に合
わせた。生じた析出物をサラン製の布上に集め回収し、
大量の水で洗滌することにより可溶物を除いた。洗滌後
、析出物を乾燥して白色粉末状の無臭のキトサン42g
を得た。
50 g of this crude chitosan was dissolved in 10Q of 0.5N acetic acid, and undissolved matter was removed by centrifugation. Next, the pH was adjusted to 7.5 using 40% caustic soda. The resulting precipitate was collected by centrifugation. This precipitate is then dispersed in water,
Water-soluble materials were removed. Further, this precipitate was dissolved in 0.5 mol of acetic acid, and the pH was adjusted to 7.5 with 40% caustic soda. Collect and collect the resulting precipitate on a saran cloth,
Soluble materials were removed by washing with a large amount of water. After washing, dry the precipitate to obtain 42g of odorless chitosan in the form of white powder.
I got it.

粗精製物及び精製物の性状、分析値は表2に示す。The properties and analytical values of the crude and purified products are shown in Table 2.

表中の色は日本重色工業社製の測色色差計で測定し、L
、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。グ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。
The colors in the table are measured with a colorimeter made by Nihon Heavy Industries Co., Ltd.
, a, b. The degree of residual crab shell odor was determined by a sensory test. The glucosamine content was calculated by hydrolyzing each chitosan with 4N hydrochloric acid and then measuring by the Erlan-Morgan method, and expressed as % of dry matter.

表より明らかなように色は明度(L)が大きくなり赤色
(、)が減少し、黄色(b)も減少し、色素が除去され
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。
As is clear from the table, the lightness (L) increases, the red color (,) decreases, and the yellow color (b) decreases, indicating that the pigment was removed 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.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図は試験例において、各poにおけるキ1〜サンの
析出物の乾燥重量の百分率を示す図である。
FIG. 1 is a diagram showing the percentage of the dry weight of the precipitates of Ki1-San in each po in the test example.

Claims (3)

【特許請求の範囲】[Claims] (1)キトサン含有液をpH6.0以上、好ましくはp
H6.5以上に調整し、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) Adjust the chitosan-containing liquid to pH 6.0 or higher, preferably p
A method for purifying chitosan, which comprises adjusting H to 6.5 or higher and producing a precipitate.
(2)キトサン含有液をpH6.0以上、好ましくはp
H6.5以上に調整し、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) Adjust the chitosan-containing liquid to pH 6.0 or higher, preferably p
A method for purifying chitosan, which comprises adjusting H to 6.5 or higher, washing the obtained precipitate as necessary, and dissolving the precipitate in an acid.
(3)キトサン含有液をpH6.0以上、好ましくはp
H6.5以上に調整し、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、pH6.0以上、好ま
しくはpH6.5以上に調整し、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−溶解をくり返すことを特徴とする
キトサンの精製法。
(3) Adjust the chitosan-containing liquid to a pH of 6.0 or higher, preferably p
Adjust the pH to 6.5 or higher, wash the resulting precipitate with water as necessary, dissolve the precipitate in acid, adjust the pH to 6.0 or higher, preferably pH 6.5 or higher, and then the resulting precipitate A method for purifying chitosan, which comprises washing the precipitate as necessary, dissolving the precipitate in acid again, and repeating the above precipitation-washing-dissolution process as necessary.
JP15979386A 1986-07-09 1986-07-09 Purification of chitosan Pending JPS6317901A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP15979386A JPS6317901A (en) 1986-07-09 1986-07-09 Purification of chitosan

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP15979386A JPS6317901A (en) 1986-07-09 1986-07-09 Purification of chitosan

Publications (1)

Publication Number Publication Date
JPS6317901A true JPS6317901A (en) 1988-01-25

Family

ID=15701389

Family Applications (1)

Application Number Title Priority Date Filing Date
JP15979386A Pending JPS6317901A (en) 1986-07-09 1986-07-09 Purification of chitosan

Country Status (1)

Country Link
JP (1) JPS6317901A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02174654A (en) * 1988-12-26 1990-07-06 Nakano Vinegar Co Ltd Decoloring of liquid food
WO2001004207A1 (en) * 1999-07-12 2001-01-18 Cognis Deutschland Gmbh Preparations containing no cross-linking agents
WO2001004187A1 (en) * 1999-07-12 2001-01-18 Cognis Deutschland Gmbh Preparations that are devoid of cross-linking agents
WO2003066682A1 (en) * 2002-02-07 2003-08-14 Abbott Laboratories De Costa Rica Ltd Method for deproteinization of chitosan

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5857401A (en) * 1981-09-30 1983-04-05 Agency Of Ind Science & Technol Production of particulate porous chitosan
JPS61133143A (en) * 1984-11-30 1986-06-20 Fuji Boseki Kk Heavy metal adsorbent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5857401A (en) * 1981-09-30 1983-04-05 Agency Of Ind Science & Technol Production of particulate porous chitosan
JPS61133143A (en) * 1984-11-30 1986-06-20 Fuji Boseki Kk Heavy metal adsorbent

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02174654A (en) * 1988-12-26 1990-07-06 Nakano Vinegar Co Ltd Decoloring of liquid food
JP2762087B2 (en) * 1988-12-26 1998-06-04 株式会社中埜酢店 Decolorization method for liquid food
WO2001004207A1 (en) * 1999-07-12 2001-01-18 Cognis Deutschland Gmbh Preparations containing no cross-linking agents
WO2001004187A1 (en) * 1999-07-12 2001-01-18 Cognis Deutschland Gmbh Preparations that are devoid of cross-linking agents
WO2003066682A1 (en) * 2002-02-07 2003-08-14 Abbott Laboratories De Costa Rica Ltd Method for deproteinization of chitosan

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