JP5256509B2 - Method for producing N-acetylglucosamine and use thereof - Google Patents
Method for producing N-acetylglucosamine and use thereof Download PDFInfo
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- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 title claims description 95
- 229950006780 n-acetylglucosamine Drugs 0.000 title claims description 95
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 title claims description 90
- MBLBDJOUHNCFQT-LXGUWJNJSA-N N-acetylglucosamine Natural products CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 title claims description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 45
- 229920002101 Chitin Polymers 0.000 claims description 80
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 55
- 230000007062 hydrolysis Effects 0.000 claims description 24
- 238000006460 hydrolysis reaction Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 13
- 102000004190 Enzymes Human genes 0.000 claims description 12
- 108090000790 Enzymes Proteins 0.000 claims description 12
- 230000003544 deproteinization Effects 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 229920001542 oligosaccharide Polymers 0.000 description 33
- 150000002482 oligosaccharides Chemical class 0.000 description 22
- 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 21
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 21
- 229960002442 glucosamine Drugs 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 7
- 239000002778 food additive Substances 0.000 description 7
- 235000013373 food additive Nutrition 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- DUKURNFHYQXCJG-UHFFFAOYSA-N Lewis A pentasaccharide Natural products OC1C(O)C(O)C(C)OC1OC1C(OC2C(C(O)C(O)C(CO)O2)O)C(NC(C)=O)C(OC2C(C(OC3C(OC(O)C(O)C3O)CO)OC(CO)C2O)O)OC1CO DUKURNFHYQXCJG-UHFFFAOYSA-N 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000007071 enzymatic hydrolysis Effects 0.000 description 3
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- 241000238424 Crustacea Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000003599 food sweetener Nutrition 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003765 sweetening agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 241000223259 Trichoderma Species 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 235000013376 functional food Nutrition 0.000 description 1
- -1 glucosamine Chemical compound 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
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- Cosmetics (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Saccharide Compounds (AREA)
Description
この発明は、高純度のＮ−アセチルグルコサミンを容易に得ることのできる、Ｎ−アセチルグルコサミンの製造方法、並びにその用途に関する。 The present invention relates to a method for producing N-acetylglucosamine, which can easily obtain high-purity N-acetylglucosamine, and uses thereof.
従来、蟹等の甲殻類から抽出されるキチンを濃塩酸等で加水分解することにより得られるグルコサミンが、単体、若しくは、コラーゲン等と共に錠剤等に成形され、若しくは、食品等に添加され、生体防御、疾病予防、老化制御等を目的とする機能性食品に使用されている。これに対し、Ｎ‐アセチルグルコサミンは、グルコサミンと同じくキチンを濃塩酸によって加水分解して得られるが、当該グルコサミンの場合と比較して、これより低い温度で加水分解して得られる。また、食品添加物公定書によれば、食品添加物として使用されるＮ−アセチルグルコサミンは、キチンを塩酸、及び酵素による加水分解にて得られるＮ−アセチルグルコサミンと明記されており、この公定書に基づいた生産方法が重要である。そして、Ｎ−アセチルグルコサミンはその機能については多くのデータは示されていないが、甘味料として爽やかな甘味を持っており、グルコサミンとは別の用途が期待されている。 Conventionally, glucosamine obtained by hydrolyzing chitin extracted from crustaceans such as salmon with concentrated hydrochloric acid or the like is molded into tablets or the like alone or with collagen, etc., or added to foods, etc. It is used in functional foods for the purpose of disease prevention and aging control. On the other hand, N-acetylglucosamine is obtained by hydrolyzing chitin with concentrated hydrochloric acid like glucosamine, but is obtained by hydrolysis at a temperature lower than that of glucosamine. In addition, according to the Food Additives Official Statement, N-acetylglucosamine used as a food additive is specified as N-acetylglucosamine obtained by hydrolysis of chitin with hydrochloric acid and enzymes. The production method based on is important. N-acetylglucosamine does not show much data on its function, but has a refreshing sweetness as a sweetener and is expected to be used in a different manner from glucosamine.
そして、Ｎ−アセチルグルコサミンの製造方法としては、キチンを濃塩酸を用いて加水分解した後、水酸化ナトリウムを用いて中和し、活性炭等を用いて脱色した後、イオン交換樹脂を用いてグルコサミンやヘテロオリゴ糖等を除去する。さらに、逆浸透膜（以下、ＲＯ膜）を用いてＮ−アセチルグルコサミンと、残存しているキチンオリゴ糖とを分配し、凍結乾燥やスプレードライヤーを用いて該Ｎ−アセチルグルコサミンを粉末化する方法が考案されている（例えば、特許文献１）。 And as a manufacturing method of N-acetylglucosamine, after hydrolyzing chitin using concentrated hydrochloric acid, neutralizing using sodium hydroxide, decolorizing using activated carbon, etc., and then using glucosamine using ion exchange resin And heterooligosaccharides are removed. Furthermore, N-acetylglucosamine and the remaining chitin oligosaccharide are distributed using a reverse osmosis membrane (hereinafter referred to as RO membrane), and the N-acetylglucosamine is pulverized using lyophilization or a spray dryer. Has been devised (for example, Patent Document 1).
しかし、食品等の工業用に使用されるＮ−アセチルグルコサミンを製造する際に、上述のようにＲＯ膜での分配工程を経ることは時間的に大きなロスであり、また、設備投資のための資金も必要である。しかし、ＲＯ膜を用いてＮ−アセチルグルコサミンと残存しているキチンオリゴ糖とを分配しないと、当該Ｎ−アセチルグルコサミンの純度が低下すると共に、これらの物質がＮ−アセチルグルコサミンの結晶化を阻害するという問題が生じる。 However, when producing N-acetylglucosamine used for industrial purposes such as food, passing through the RO membrane distribution process as described above is a significant loss in time, and for capital investment. Funds are also needed. However, if N-acetylglucosamine and the remaining chitin oligosaccharide are not distributed using the RO membrane, the purity of the N-acetylglucosamine decreases and these substances inhibit the crystallization of N-acetylglucosamine. Problem arises.
さらに、Ｎ−アセチルグルコサミンの製造に使用されるキチンの初期分子量が高い場合には、これらを加水分解した際に、速やかに加水分解される箇所と、そうでない箇所とで加水分解に時間差が生じる。そのため、初期に加水分解された箇所は、キチンのおよそ全てが加水分解された時点では、既にＮ−アセチルグルコサミンがさらにグルコサミンに変換され、加水分解後の溶液中に該グルコサミンが多く混在するという問題が生じる。また、グルコサミンの発生を抑制しようとして加水分解時間を短縮した場合には、逆にキチンからＮ−アセチルグルコサミンへの分解過程で生じるキチンオリゴ糖等が加水分解後の溶液中に多く混在するという問題が生じる。 Furthermore, when the initial molecular weight of chitin used for the production of N-acetylglucosamine is high, when these are hydrolyzed, there is a time difference in hydrolysis between the portion that is rapidly hydrolyzed and the portion that is not. . Therefore, at the point where almost all of chitin is hydrolyzed, the portion hydrolyzed in the early stage has already been converted into N-acetylglucosamine further to glucosamine, and a lot of the glucosamine is mixed in the solution after hydrolysis. Occurs. In addition, when the hydrolysis time is shortened in order to suppress the generation of glucosamine, conversely, a large amount of chitin oligosaccharides and the like produced in the decomposition process from chitin to N-acetylglucosamine are mixed in the solution after hydrolysis. Occurs.
このように、加水分解後の溶液中にＮ−アセチルグルコサミン以外に、グルコサミンやキチンオリゴ糖等の夾雑物が混在すると、この溶液を濃縮しＮ−アセチルグルコサミンの結晶を得る際に、結晶性の悪いこれらの夾雑物が該Ｎ−アセチルグルコサミンの結晶化を阻害するという問題が生じる。また、グルコサミンやヘテロオリゴ糖等の夾雑物は、Ｎ−アセチルグルコサミンの結晶を得る際の加水分解後の溶液の濃縮工程において、着色の原因となり、得られるＮ−アセチルグルコサミンの外観を損なうという問題や、該Ｎ−アセチルグルコサミンの純度や歩留りを低下させるという問題も生じている。 Thus, when impurities such as glucosamine and chitin oligosaccharide are mixed in the hydrolyzed solution in addition to N-acetylglucosamine, when the solution is concentrated to obtain N-acetylglucosamine crystals, The problem arises that these bad contaminants inhibit the crystallization of the N-acetylglucosamine. In addition, impurities such as glucosamine and hetero-oligosaccharides cause coloration in the concentration step of the solution after hydrolysis when obtaining crystals of N-acetylglucosamine, and the appearance of the obtained N-acetylglucosamine is impaired. There is also a problem that the purity and yield of the N-acetylglucosamine are lowered.
この発明は上記のような種々の課題を解決することを目的としてなされたものであって、ＲＯ膜を使用せずとも高純度のＮ−アセチルグルコサミンを製造することができ、さらに、加水分解後の溶液中のグルサミンやヘテロオリゴ糖等の量を減少させたＮ−アセチルグルコサミンの製造方法、並びにその用途に関する。 The present invention has been made for the purpose of solving the various problems as described above, and can produce high-purity N-acetylglucosamine without using an RO membrane. The present invention relates to a method for producing N-acetylglucosamine in which the amount of glucamine, hetero-oligosaccharide, etc. in the solution of 1 is reduced, and its use.
上記目的を達成するために、請求項１記載のＮ−アセチルグルコサミンの製造方法は、アルカリによる脱タンパク工程、及び塩酸による脱カルシウム工程を経て得られるキチンを濃塩酸で加水分解して得られるＮ−アセチルグルコサミンの製造方法であって、前記キチンの０.２ｗｔ％ジメチルアセトアミド溶液の粘度が２０〜２００ｍＰａ・Ｓであることを特徴としている。 In order to achieve the above object, the method for producing N-acetylglucosamine according to claim 1 is characterized in that N obtained by hydrolyzing chitin obtained through a deproteinization step with alkali and a decalcification step with hydrochloric acid with concentrated hydrochloric acid. A method for producing acetylglucosamine, characterized in that the viscosity of a 0.2 wt% dimethylacetamide solution of chitin is 20 to 200 mPa · S.
請求項２記載のＮ−アセチルグルコサミンの製造方法は、前記脱カルシウム工程の温度が５０〜７０℃であることを特徴としている。 The method for producing N-acetylglucosamine according to claim 2 is characterized in that a temperature of the decalcification step is 50 to 70 ° C.
請求項３記載のＮ−アセチルグルコサミンの製造方法は、請求項１又は２記載のＮ−アセチルグルコサミンの製造方法において、前記キチンを濃塩酸で加水分解した後に、さらに、酵素によって加水分解することを特徴としている。 The method for producing N-acetylglucosamine according to claim 3 is the method for producing N-acetylglucosamine according to claim 1 or 2, wherein the chitin is hydrolyzed with concentrated hydrochloric acid and then hydrolyzed by an enzyme. It is a feature.
請求項４記載のＮ−アセチルグルコサミンの製造方法は、請求項１乃至３記載のＮ−アセチルグルコサミンの製造方法において、前記濃塩酸による加水分解を３５〜５０℃で２〜５時間行うことを特徴としている。 The method for producing N-acetylglucosamine according to claim 4 is the method for producing N-acetylglucosamine according to claims 1 to 3, wherein the hydrolysis with concentrated hydrochloric acid is performed at 35 to 50 ° C for 2 to 5 hours. It is said.
請求項１記載のＮ−アセチルグルコサミンの製造方法によれば、アルカリによる脱タンパク工程、及び塩酸による脱カルシウム工程を経て得られるキチンを濃塩酸で加水分解して得られるＮ−アセチルグルコサミンの製造方法であって、前記キチンの０.２ｗｔ％ジメチルアセトアミド溶液の粘度が２０〜２００ｍＰａ・Ｓである。これにより、Ｎ−アセチルグルコサミンを製造する際に使用されるキチンの初期分子量を該キチンの脱カルシウム工程において予め低くしたので、加水分解に使用される濃塩酸等と接触するだけで該キチンが膨潤し速やかに均一状態となって、これらのキチンを一度に加水分解させＮ−アセチルグルコサミンを得ることができる。 According to the method for producing N-acetylglucosamine according to claim 1, a method for producing N-acetylglucosamine obtained by hydrolyzing chitin obtained by the deproteinization step with alkali and the decalcification step with hydrochloric acid with concentrated hydrochloric acid. The viscosity of the 0.2 wt% dimethylacetamide solution of chitin is 20 to 200 mPa · S. As a result, the initial molecular weight of chitin used in producing N-acetylglucosamine was previously reduced in the decalcification step of the chitin, so that the chitin swells only by contacting with concentrated hydrochloric acid used for hydrolysis. And it becomes a uniform state quickly and can hydrolyze these chitin at a time and can obtain N-acetylglucosamine.
これにより、加水分解後の水可溶部に含まれる加水分解後の溶液中のキチンオリゴ糖の発生を抑制することができる。従って、加水分解後の溶液中に極微量に存在するグルコサミンやヘテロオリゴ糖等をイオン交換樹脂で除去すれば、キチンオリゴ糖を除去するために逆浸透膜（ＲＯ膜）を使用する必要がなく、Ｎ−アセチルグルコサミンの製造工程を簡略化することができ、さらに高純度のＮ−アセチルグルコサミンを得ることができる。また、加水分解物中のキチンオリゴ糖の発生を抑制したので、Ｎ−アセチルグルコサミンの結晶化が阻害されることなく、該Ｎ−アセチルグルコサミンを容易に結晶化することができる。さらに、加水分解後の溶液中にはグルコサミンやヘテロオリゴ糖等の着色物質をほとんど含まないので、該溶液の濃縮工程においてほとんど着色することなく、ほぼ白色の高純度のＮ−アセチルグルコサミンの結晶を得ることができる。 Thereby, generation | occurrence | production of the chitin oligosaccharide in the solution after the hydrolysis contained in the water soluble part after hydrolysis can be suppressed. Therefore, if glucosamine, hetero-oligosaccharides, etc. that are present in trace amounts in the hydrolyzed solution are removed with an ion exchange resin, there is no need to use a reverse osmosis membrane (RO membrane) to remove chitin oligosaccharides, The production process of N-acetylglucosamine can be simplified, and high-purity N-acetylglucosamine can be obtained. Moreover, since generation | occurrence | production of the chitin oligosaccharide in a hydrolyzate was suppressed, this N-acetylglucosamine can be crystallized easily, without inhibiting crystallization of N-acetylglucosamine. Furthermore, since the solution after hydrolysis hardly contains coloring substances such as glucosamine and hetero-oligosaccharide, almost white high-purity N-acetylglucosamine crystals are obtained with little coloration in the concentration step of the solution. be able to.
請求項２記載のＮ−アセチルグルコサミンの製造方法によれば、前記脱カルシウム工程の温度が５０〜７０℃である。これにより、請求項１の効果に加えて、キチンの０.２ｗｔ％ジメチルアセトアミド溶液の粘度を容易に２０〜２００ｍＰａ・Ｓとして分子量を低下させることができる。 According to the method for producing N-acetylglucosamine according to claim 2, the temperature of the decalcification step is 50 to 70 ° C. Thereby, in addition to the effect of Claim 1, the viscosity of the 0.2 wt% dimethylacetamide solution of chitin can be easily set to 20 to 200 mPa · S to reduce the molecular weight.
請求項３記載のＮ−アセチルグルコサミンの製造方法によれば、請求項１又は２記載のＮ−アセチルグルコサミンの製造方法において、前記キチンを濃塩酸で加水分解した後に、さらに、酵素によって加水分解している。ここで、加水分解後の溶液を濃縮した後、結晶とその母液とを分離するが、Ｎ−アセチルグルコサミンの製造の歩留りを向上するためには、該母液をさらに次バッチのＮ−アセチルグルコサミンの製造工程において再び使用することが好ましい。しかし、加水分解後の溶液に極微量に含まれ、結晶性の乏しいキチンオリゴ糖が母液の再利用の度に増加し、次バッチのＮ−アセチルグルコサミンの結晶化を阻害する可能性がある。 According to the method for producing N-acetylglucosamine according to claim 3, in the method for producing N-acetylglucosamine according to claim 1 or 2, the chitin is hydrolyzed with concentrated hydrochloric acid and further hydrolyzed with an enzyme. ing. Here, after concentrating the hydrolyzed solution, the crystal and its mother liquor are separated. In order to improve the production yield of N-acetylglucosamine, the mother liquor is further added to the next batch of N-acetylglucosamine. It is preferably used again in the manufacturing process. However, a very small amount of chitin oligosaccharide which is contained in a very small amount in the hydrolyzed solution increases every time the mother liquor is reused, and there is a possibility that the crystallization of N-acetylglucosamine in the next batch may be inhibited.
そのため、濃塩酸による加水分解後に、さらに、酵素による加水分解工程を経ることで、極微量のキチンオリゴ糖に至るまでＮ−アセチルグルコサミンに加水分解することができるので、該Ｎ−アセチルグルコサミンの結晶化をさらに容易にすることにより歩留りの向上に大きく貢献することができる。また、食品添加物公定書においては、キチンを加水分解してＮ−アセチルグルコサミンとする場合には、その工程中に酵素による加水分解工程を経ることが必須とされている。そのため、酵素による加水分解工程を経た本発明に係るＮ−アセチルグルコサミンは食品添加物として使用することができる。 Therefore, after hydrolysis with concentrated hydrochloric acid, it can be further hydrolyzed to N-acetylglucosamine by passing through an enzymatic hydrolysis step to reach a very small amount of chitin oligosaccharide. Making the process easier can contribute greatly to the improvement of the yield. In addition, in the food additive official document, when chitin is hydrolyzed to N-acetylglucosamine, it is essential to undergo an enzymatic hydrolysis step during that step. Therefore, the N-acetylglucosamine which concerns on this invention which passed through the hydrolysis process by an enzyme can be used as a food additive.
請求項４記載のＮ−アセチルグルコサミンの製造方法によれば、請求項１乃至３記載のＮ−アセチルグルコサミンの製造方法において、前記加水分解を３５〜５０℃で２〜５時間行うものである。これにより、予め低分子量化されたキチンを効率的に均一に加水分解することができ、キチンオリゴ糖、グルコサミン、ヘテロオリゴ糖等のＮ−アセチルグルコサミン以外の夾雑物の発生を抑制することができる。 According to the method for producing N-acetylglucosamine according to claim 4, in the method for producing N-acetylglucosamine according to claims 1 to 3, the hydrolysis is performed at 35 to 50 ° C for 2 to 5 hours. Thereby, chitin previously reduced in molecular weight can be efficiently and uniformly hydrolyzed, and generation of impurities other than N-acetylglucosamine, such as chitin oligosaccharide, glucosamine, and heterooligosaccharide, can be suppressed.
この発明におけるＮ−アセチルグルコサミンの製造方法の最良の実施形態について、以下に説明する。本発明に係るＮ−アセチルグルコサミンの製造方法は、キチンを濃塩酸で加水分解するものである。 The best embodiment of the method for producing N-acetylglucosamine in the present invention will be described below. The method for producing N-acetylglucosamine according to the present invention hydrolyzes chitin with concentrated hydrochloric acid.
前記キチンは、甲殻類の外骨格等に含まれるアミノ多糖類のことで、化学式は、アセチルグルコサミンが、繰り返して連結したポリ−Ｎ−アセチルグルコサミンからなり下記の構造式（Ｉ）に示される天然高分子である。 The chitin is an aminopolysaccharide contained in the crustacean exoskeleton and the like, and the chemical formula consists of poly-N-acetylglucosamine in which acetylglucosamine is linked repeatedly and is represented by the following structural formula (I) It is a polymer.
そして、キチンは一般的にエビ殻やカニ殻等が原料として使用されるが、カニ殻等はキチンの他に炭酸カルシウム、タンパク質等を含有しており、これらを除去する必要がある。そのため、カニ殻等からキチンを製造する際には、アルカリによる脱タンパク工程、及び酸による脱カルシウム工程を経て該キチンが得られる。 As chitin, shrimp shells and crab shells are generally used as raw materials. Crab shells and the like contain calcium carbonate, protein and the like in addition to chitin, and it is necessary to remove them. Therefore, when manufacturing chitin from a crab shell etc., this chitin is obtained through the deproteinization process by an alkali and the decalcification process by an acid.
また、本実施形態ではカニ殻を使用しているが、これを使用する場合には、カニ殻内に残存しているタンパク質の変性により該カニ殻が劣化しないように、入荷後速やかに該カニ殻をこれらの工程により、キチン、或いは、さらに処理を行ってキトサン等に変換することが好ましい。 In this embodiment, the crab shell is used. When this crab shell is used, the crab shell is promptly received after arrival so that the crab shell does not deteriorate due to the denaturation of the protein remaining in the crab shell. It is preferable that the shell is converted into chitosan or the like by carrying out further treatment by these steps.
脱カルシウム工程、及び脱タンパク工程はどちらを先に行ってもよいが、これらの工程を行なう前に、カニ殻等の付着物を流水等で除去し乾燥させ、該カニ殻を粉砕する。そして、脱タンパク工程では、粉砕されたカニ殻に希アルカリを添加して脱タンパクを行う。この際には、希アルカリとして５％前後の水酸化ナトリウムを使用し、８０℃以上で３時間程度、脱タンパク工程を行う。 Either the decalcification process or the deproteinization process may be performed first, but before performing these processes, the deposits such as crab shells are removed with running water or the like and dried, and the crab shells are pulverized. In the deproteinization step, deproteinization is performed by adding a dilute alkali to the crushed crab shell. At this time, about 5% sodium hydroxide is used as a dilute alkali, and the deproteinization step is performed at 80 ° C. or more for about 3 hours.
そして、脱タンパク後のカニ殻に酸を添加し強攪拌して脱カルシウム工程を行う。この際には、酸として５〜１５％の希塩酸を使用し、Ｎ−アセチルグルコサミン生産用原料としてのキチンを得る場合は、５０〜７０℃で２〜４時間程度、好適には５５℃で３時間程度脱カルシウム工程を行うことが好ましく、これにより、予めキチンを低分子量化することができる。 Then, acid is added to the crab shell after deproteinization and the mixture is vigorously stirred to perform the decalcification step. In this case, when 5 to 15% dilute hydrochloric acid is used as the acid and chitin is obtained as a raw material for producing N-acetylglucosamine, it is 50 to 70 ° C. for about 2 to 4 hours, preferably 3 to 55 ° C. It is preferable to carry out a decalcification step for about an hour, whereby chitin can be reduced in molecular weight in advance.
また、脱カルシウム工程において、一般的なキチン生産方法に則って反応温度が５０度よりも低い室温等で処理した場合は、キチンの分子量は高いままキチン化される。これを濃塩酸で加水分解させた場合、反応が不均一に進行し、加水分解後の水可溶部にはＮ−アセチルグルコサミンの他にキチンオリゴ糖、ヘテロオリゴ糖、グルコサミン等を含む反応液が得られる。これらが夾雑物となってＮ−アセチルグルコサミンの結晶化が難しくなる。そして、脱カルシウムの温度が７０℃より高い場合は、歩留まりの低下、エネルギーコストの上昇等が考えられ、効率的な生産には不適である。 Further, in the decalcification step, when the reaction is performed at a room temperature or the like where the reaction temperature is lower than 50 degrees in accordance with a general chitin production method, the chitin is chitinated with a high molecular weight. When this is hydrolyzed with concentrated hydrochloric acid, the reaction proceeds non-uniformly, and a reaction solution containing chitin oligosaccharide, heterooligosaccharide, glucosamine, etc. in addition to N-acetylglucosamine is present in the water-soluble part after hydrolysis. can get. These become impurities and it is difficult to crystallize N-acetylglucosamine. And when the temperature of decalcification is higher than 70 degreeC, the fall of a yield, the raise of energy cost, etc. can be considered, and it is unsuitable for efficient production.
また、キチンは、一般的に使用されるテトラヒドロフランやクロロホルム等の有機溶媒に溶解しないことから、Gel Permeation Chromatography（ＧＰＣ）等で分子量の測定をすることが困難である。そのため、本実施形態では、キチンが可溶な塩化リチウムの８ｗｔ％ジメチルアセトアミド溶液を用いて、キチンの０.２ｗｔ％ジメチルアセトアミド溶液を作成し、これを例えば回転粘度計等を用いて恒温条件下で粘度測定を行い、測定された粘度から分子量の評価を行っている。 Moreover, since chitin does not dissolve in commonly used organic solvents such as tetrahydrofuran and chloroform, it is difficult to measure the molecular weight by Gel Permeation Chromatography (GPC) or the like. Therefore, in this embodiment, a 0.2 wt% dimethylacetamide solution of chitin is prepared using an 8 wt% dimethylacetamide solution of lithium chloride in which chitin is soluble, and this is subjected to isothermal conditions using, for example, a rotary viscometer or the like. Viscosity measurement is performed, and molecular weight is evaluated from the measured viscosity.
以上のように製造されるキチンの０.２ｗｔ％ジメチルアセトアミド溶液の粘度測定を行った結果、これらの粘度は２０〜１００ｍＰａ・Ｓであった。一方、上述の脱タンパク工程を常温下で行った場合は、同様にして粘度を測定したところ、１０００〜３０００ｍＰａ・Ｓであった。これらの結果より、キチン製造の際の脱カルシウム工程を常温で行うよりも、５０〜７０℃で行った方が、反応効率がよく、より分子鎖が切断され該キチンが低分子量化されていることがわかる。そして、予め低分子量化されたキチン使用することで該キチンを一度に加水分解することができ、グルコサミンやキチンオリゴ糖等の夾雑物をほとんど含有しない下記の構造式（II）に示されるＮ−アセチルグルコサミンを得ることができる。 As a result of measuring the viscosity of the 0.2 wt% dimethylacetamide solution of chitin produced as described above, these viscosities were 20 to 100 mPa · S. On the other hand, when the above-mentioned deproteinization step was performed at room temperature, the viscosity was measured in the same manner, and it was 1000 to 3000 mPa · S. From these results, the reaction efficiency is better when the decalcification step in the production of chitin is performed at room temperature than at normal temperature, and the molecular chain is cut and the chitin is reduced in molecular weight. I understand that. The chitin can be hydrolyzed at once by using chitin having a low molecular weight in advance, and N--shown in the following structural formula (II) containing almost no impurities such as glucosamine and chitin oligosaccharide. Acetylglucosamine can be obtained.
以上のようにして低分子量化されたキチンを用いたＮ−アセチルグルコサミンの製造方法を以下に示す。 A method for producing N-acetylglucosamine using chitin reduced in molecular weight as described above is shown below.
〔実施例１〕
キチンの０.２ｗｔ％ジメチルアセトアミド溶液の粘度が２０〜２００ｍＰａ・Ｓであるキチン４００ｇに、該キチンに対して５倍量である２．０ｋｇの３５％の濃塩酸を加え、約４３℃で４時間加水分解を行った。反応液は速やかに均一となり、反応を停止するために水酸化ナトリウム溶液等の濃アルカリ溶液を投入し、ｐＨが５．０〜６．０程度に中和した。この際には、濃塩酸と水酸化ナトリウム溶液との中和反応熱によって、反応液の温度が６０℃以上にならないように適宜氷を反応液に投入する。
[Example 1]
To 400 g of chitin having a viscosity of 20 to 200 mPa · S of a 0.2 wt% dimethylacetamide solution of chitin, 2.0 kg of 35% concentrated hydrochloric acid, which is 5 times the amount of the chitin, is added, and 4% at 43 ° C. Time hydrolysis was performed. The reaction solution became uniform quickly, and a concentrated alkali solution such as sodium hydroxide solution was added to neutralize the reaction solution to a pH of about 5.0 to 6.0. At this time, ice is appropriately added to the reaction solution so that the temperature of the reaction solution does not exceed 60 ° C. due to the heat of neutralization reaction between concentrated hydrochloric acid and sodium hydroxide solution.
これにより、９０％以上の水溶化部を得ることができ、得られた加水分解後の溶液を活性炭を用いて脱色を行った後、電気透析装置によって脱塩処理を行う。そして、イオン交換樹脂によって、溶液中に残存する微量のグルコサミンやヘテロオリゴ糖等を除去し、再度活性炭による脱色を行った後、溶液を濃縮することによりＮ−アセチルグルコサミンの結晶を得た。こうして得られたＮ−アセチルグルコサミンの結晶は、ろ過によって結晶と母液とに分けられた後、乾燥され、純度が９８％以上のＮ−アセチルグルコサミンの結晶が得られた。また、母液は、Ｎ−アセチルグルコサミンの歩留り向上のために、次バッチのＮ−アセチルグルコサミン製造における、濃縮工程の溶液等に加えられ繰り返し使用される。 Thereby, 90% or more of the water-solubilized part can be obtained, and after the obtained hydrolyzed solution is decolorized using activated carbon, it is desalted by an electrodialyzer. Then, trace amounts of glucosamine, hetero-oligosaccharides and the like remaining in the solution were removed with an ion exchange resin, decolorization with activated carbon was performed again, and then the solution was concentrated to obtain N-acetylglucosamine crystals. The N-acetylglucosamine crystals thus obtained were separated into a crystal and a mother liquor by filtration and then dried to obtain N-acetylglucosamine crystals having a purity of 98% or more. Further, the mother liquor is repeatedly added to the solution in the concentration step in the production of the next batch of N-acetylglucosamine in order to improve the yield of N-acetylglucosamine.
そして、加水分解に使用される濃塩酸の量はキチンに対して３〜６倍量、好適には４〜５倍量が好ましく、３倍量よりも少ない場合には、キチンを十分に加水分解することができず水不溶部が多く残り、また、６倍量よりも多い場合には、キチンを十分に加水分解することができるものの、その後の中和や脱塩処理の工程に手間がかかる。そして、加水分解時間は２時間〜５時間程度、好適には３〜４時間が好ましく、２時間よりも短い場合には、キチンを十分に加水分解することができず水不溶部が多く残り、また、５時間よりも長い場合は生産効率が悪くなる。 The amount of concentrated hydrochloric acid used for hydrolysis is 3 to 6 times the amount of chitin, preferably 4 to 5 times the amount, and if less than 3 times the amount, the chitin is sufficiently hydrolyzed. If the amount of water-insoluble parts cannot be increased and more than 6 times the amount, chitin can be sufficiently hydrolyzed, but the subsequent neutralization and desalting processes are time-consuming. . And, the hydrolysis time is about 2 hours to 5 hours, preferably 3 to 4 hours, and when shorter than 2 hours, chitin cannot be sufficiently hydrolyzed, leaving many water-insoluble parts, Moreover, when it is longer than 5 hours, the production efficiency is deteriorated.
また、反応温度は３５〜５０℃程度、好適には４０〜４５℃が好ましく、３５℃よりも低い場合にはキチンを十分に加水分解することができず水不溶部が多く残り、また、５０℃よりも高い場合には生産効率が悪くなる。そして、濃塩酸としては市販の２５〜３５％程度、好適には３５％の濃塩酸を適宜使用することができる。 The reaction temperature is preferably about 35 to 50 ° C., preferably 40 to 45 ° C. If it is lower than 35 ° C., chitin cannot be sufficiently hydrolyzed, leaving many water-insoluble parts, and 50 When it is higher than ° C, the production efficiency is deteriorated. As the concentrated hydrochloric acid, commercially available concentrated hydrochloric acid of about 25 to 35%, preferably 35% can be appropriately used.
また、実施例１のようにイオン交換樹脂を用いて脱グルコサミンや脱ヘテロオリゴ糖を行ったほうが、加水分解後の溶液を濃縮する工程において、溶液中に存在するグルコサミンやヘテロオリゴ糖等の着色物質が着色し、最終的に得られるＮ−アセチルグルコサミンが着色することがなく好ましい。しかし、予め低分子量化したキチンを使用し、該キチンを一度に低分子量化しているので、グルコサミンやヘテロオリゴ糖等が極めて生じにくいため、イオン交換樹脂でこれらを除去する工程を設けなくともほぼ白色のＮ−アセチルグルコサミンの結晶を得ることができる。 In addition, when deglucosamine or dehetero-oligosaccharide is performed using an ion exchange resin as in Example 1, in the step of concentrating the hydrolyzed solution, colored substances such as glucosamine and hetero-oligosaccharide present in the solution are present. N-acetylglucosamine which is colored and finally obtained is preferred without being colored. However, since chitin with a low molecular weight is used in advance and the chitin is reduced in molecular weight at a time, glucosamine, hetero-oligosaccharides, etc. are very unlikely to occur, so it is almost white without providing a process for removing these with an ion exchange resin. N-acetylglucosamine crystals can be obtained.
また、予め低分子量化したキチンを使用しているので、キチンオリゴ糖の発生も抑えることができ、該キチンオリゴ糖とＮ−アセチルグルコサミンとを逆浸透膜（ＲＯ膜）や液体クロマト分離等を用いてこれらを分配する必要がない。また、逆浸透膜を用いてキチンオリゴ糖とＮ−アセチルグルコサミンとを分配する工程を設けても該Ｎ−アセチルグルコサミンの結晶を得ることができるのは勿論である。 In addition, since chitin with a low molecular weight is used in advance, the generation of chitin oligosaccharides can be suppressed, and the chitin oligosaccharide and N-acetylglucosamine can be separated by reverse osmosis membrane (RO membrane) or liquid chromatography separation. There is no need to use them to distribute them. Of course, the N-acetylglucosamine crystals can be obtained even if a step of partitioning chitin oligosaccharides and N-acetylglucosamine using a reverse osmosis membrane is provided.
また、予め低分子量化されたキチンを使用することにより、濃塩酸による加水分解後の容器中にはキチンオリゴ糖が極微量しか含まれていないので、分解酵素を使用した加水分解工程を省略することも可能である。しかし、前述のように次バッチのＮ−アセチルグルコサミン製造の際に母液を再び使用する場合には、再利用ごとに該母液中の極微量のキチンオリゴ糖の割合が高くなり、Ｎ−アセチルグルコサミンの結晶化を阻害する原因となり得るので、実施例１において得られた濃縮前の濃塩酸による加水分解後の溶液中に分解酵素を加えて加水分解することが好ましい。また、加水分解に使用される分解酵素としては、Ｎ−アセチル−Ｄ−グルコサミニダーゼを含有した混合酵素や、菌体外粗酵素にＮ−アセチル−Ｄ−グルコサミニダーゼを含有するトリコデルマ菌等を好適に使用できる。そして、分解酵素を加えて約３７℃で２０時間程度加水分解することによって確実にキチンオリゴ糖をＮ−アセチルグルコサミンにすることができる。 In addition, by using chitin with a low molecular weight in advance, the container after hydrolysis with concentrated hydrochloric acid contains a very small amount of chitin oligosaccharide, so the hydrolysis step using a degrading enzyme is omitted. It is also possible. However, as described above, when the mother liquor is used again in the production of the next batch of N-acetylglucosamine, the amount of the extremely small amount of chitin oligosaccharide in the mother liquor increases with each reuse. Therefore, it is preferable to hydrolyze by adding a degrading enzyme to the solution after hydrolysis with concentrated hydrochloric acid before concentration obtained in Example 1. In addition, as a degrading enzyme used for hydrolysis, a mixed enzyme containing N-acetyl-D-glucosaminidase or Trichoderma bacterium containing N-acetyl-D-glucosaminidase as an extracellular crude enzyme is preferably used. it can. The chitin oligosaccharide can be reliably converted to N-acetylglucosamine by adding a degrading enzyme and hydrolyzing at about 37 ° C. for about 20 hours.
ここで、Ｎ−アセチルグルコサミンを食品添加物として使用する場合には、食品添加物公定書によれば、キチンからＮ−アセチルグルコサミンを製造する過程において、酵素による加水分解工程を経る必要がある。そのため、前述のように分解酵素によって得られたＮ−アセチルグルコサミンは食品添加物としても菓子類や乳製品等の食品に甘味料等として好適に添加することができる。また、Ｎ−アセチルグルコサミンは経皮摂取による美肌効果を期待できることから、液体、クリーム状等の化粧料に好適に添加することもできる。さらに、Ｎ−アセチルグルコサミンは経口摂取による美肌効果を期待できることから、該Ｎ−アセチルグルコサミンをコラーゲン、ヒアルロン酸、各種ビタミン等と錠剤成形することで、美肌促進剤として使用することもできる。 Here, when N-acetylglucosamine is used as a food additive, according to the official standard for food additives, it is necessary to undergo an enzymatic hydrolysis step in the process of producing N-acetylglucosamine from chitin. Therefore, N-acetylglucosamine obtained by the degrading enzyme as described above can be suitably added as a sweetener or the like to foods such as confectionery and dairy products as food additives. Moreover, since N-acetylglucosamine can expect the skin beautifying effect by percutaneous ingestion, it can also be suitably added to cosmetics such as liquids and creams. Furthermore, since N-acetylglucosamine can be expected to have a skin beautifying effect when taken orally, it can also be used as a skin beautifying agent by tableting the N-acetylglucosamine with collagen, hyaluronic acid, various vitamins and the like.
〔比較例１〕
キチンの０.２ｗｔ％ジメチルアセトアミド溶液の粘度が１０００〜３０００ｍＰａ・Ｓであるキチンを用いて、実施例１と同様にＮ−アセチルグルコサミンの製造を行った。この場合には、加水分解後の溶液をイオン交換樹脂でグルコサミンやヘテロオリゴ糖等を除去し濃縮したが、該溶液にキチンオリゴ糖が多く含まれるためＮ−アセチルグルコサミンの結晶化が阻害され、該Ｎ−アセチルグルコサミンの結晶を得ることができなかった。そして、塩酸加水分解後の水溶部が残渣として多く２０％程度残り、キチンオリゴ糖も多く残った。
[Comparative Example 1]
N-acetylglucosamine was produced in the same manner as in Example 1 using chitin in which the viscosity of a 0.2 wt% dimethylacetamide solution of chitin was 1000 to 3000 mPa · S. In this case, the hydrolyzed solution was concentrated by removing glucosamine, hetero-oligosaccharides and the like with an ion exchange resin, but because the solution contains a large amount of chitin oligosaccharide, crystallization of N-acetylglucosamine was inhibited, N-acetylglucosamine crystals could not be obtained. And about 20% of the water-soluble part after hydrochloric acid hydrolysis remained as a residue, and a large amount of chitin oligosaccharide remained.
〔比較例２〕
濃塩酸の量をキチンの２倍量とし、反応時間を２．５時間とした以外は実施例１と同様にしてＮ−アセチルグルコサミンの製造を行った。この場合は、水可溶部が５５％程度であり、また、該水可溶部中のＮ−アセチルグルコサミンは５４％であり、その他はグルコサミン、ヘテロオリゴ糖、キチンオリゴ糖等であった。そのため、加水分解後の溶液をイオン交換樹脂でグルコサミンやヘテロオリゴ糖等を除去し濃縮したが、該溶液にキチンオリゴ糖が多く含まれるためＮ−アセチルグルコサミンの結晶化が阻害され、速やかに該Ｎ−アセチルグルコサミンの結晶を得ることができなかった。
[Comparative Example 2]
N-acetylglucosamine was produced in the same manner as in Example 1 except that the amount of concentrated hydrochloric acid was twice that of chitin and the reaction time was 2.5 hours. In this case, the water-soluble part was about 55%, N-acetylglucosamine in the water-soluble part was 54%, and the others were glucosamine, hetero-oligosaccharide, chitin oligosaccharide and the like. Therefore, the hydrolyzed solution was concentrated by removing glucosamine, hetero-oligosaccharides and the like with an ion exchange resin. However, since the solution contains a large amount of chitin oligosaccharide, crystallization of N-acetylglucosamine was inhibited, and the N -Crystals of acetylglucosamine could not be obtained.
本発明に係るＮ−アセチルグルコサミンの製造方法は、実験室レベルの小スケールから、プラント等の大型設備における大量生産まで幅広く適応することができる。 The method for producing N-acetylglucosamine according to the present invention can be widely applied from a small scale at a laboratory level to mass production in a large facility such as a plant.
Claims (4)
前記キチンの０.２ｗｔ％ジメチルアセトアミド溶液の粘度が２０〜２００ｍＰａ・Ｓであることを特徴とするＮ−アセチルグルコサミンの製造方法。 A method for producing N-acetylglucosamine obtained by hydrolyzing chitin obtained by deproteinization step with alkali and decalcification step with acid with concentrated hydrochloric acid,
A method for producing N-acetylglucosamine, wherein a viscosity of a 0.2 wt% dimethylacetamide solution of chitin is 20 to 200 mPa · S.
前記キチンを濃塩酸で加水分解した後に、さらに、酵素によって加水分解することを特徴とするＮ−アセチルグルコサミンの製造方法。 The method for producing N-acetylglucosamine according to claim 1 or 2,
A method for producing N-acetylglucosamine, wherein the chitin is hydrolyzed with concentrated hydrochloric acid and then hydrolyzed with an enzyme.
前記濃塩酸による加水分解を３５〜５０℃で２〜５時間行うことを特徴とするＮ−アセチルグルコサミンの製造方法。 In the manufacturing method of N-acetylglucosamine of Claims 1 thru | or 3,
A method for producing N-acetylglucosamine, wherein the hydrolysis with concentrated hydrochloric acid is performed at 35 to 50 ° C. for 2 to 5 hours.
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