JPH03277601A - Utilization of crustacean as resources - Google Patents
Utilization of crustacean as resourcesInfo
- Publication number
- JPH03277601A JPH03277601A JP2077030A JP7703090A JPH03277601A JP H03277601 A JPH03277601 A JP H03277601A JP 2077030 A JP2077030 A JP 2077030A JP 7703090 A JP7703090 A JP 7703090A JP H03277601 A JPH03277601 A JP H03277601A
- Authority
- JP
- Japan
- Prior art keywords
- cuticle
- reaction
- chitosan
- crustacean
- deacetylation
- 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
- 241000238424 Crustacea Species 0.000 title claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 22
- 238000003381 deacetylation reaction Methods 0.000 claims description 21
- 238000004064 recycling Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005115 demineralization Methods 0.000 claims description 5
- 239000003929 acidic solution Substances 0.000 claims description 4
- 230000002328 demineralizing effect Effects 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 235000015170 shellfish Nutrition 0.000 claims 3
- 229920001661 Chitosan Polymers 0.000 abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 14
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000006196 deacetylation Effects 0.000 description 16
- 229920002101 Chitin Polymers 0.000 description 14
- 230000035484 reaction time Effects 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 241000238557 Decapoda Species 0.000 description 8
- 238000010335 hydrothermal treatment Methods 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003544 deproteinization Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical group CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- MSWZFWKMSRAUBD-QZABAPFNSA-N beta-D-glucosamine Chemical group N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-QZABAPFNSA-N 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000014616 translation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Jellies, Jams, And Syrups (AREA)
- Meat, Egg Or Seafood Products (AREA)
Abstract
Description
本発明は、例えばカニ、エビ、昆虫類等の甲殻類の資源
化方法に関するものである。
特に、本発明は、例えばカニ、エビ、昆虫類等の甲殻類
のクチクラから、クチクラに含有される炭酸カルシウム
等を成分とする無機塩、タンパク質、キチンを脱灰処理
及び脱タンパク質処理、さらには必要に応じて脱アセチ
ル化処理することによりキトサンを生成する方法に関す
るものである。The present invention relates to a method for recycling crustaceans such as crabs, shrimps, and insects. In particular, the present invention provides demineralization and deproteinization treatment of inorganic salts containing calcium carbonate, etc., protein, and chitin contained in the cuticle of crustaceans such as crabs, shrimp, and insects. The present invention relates to a method for producing chitosan by deacetylation treatment if necessary.
キチンは、Ｎ−アセチル−Ｄ−グルコサミン残基が多数
β−（１，４）結合した天然高分子であり、キトサンは
キチンの分子中のアセトアミド基（ＮＨＣＯＣＨ，）を
加水分解して脱アセチル化（脱ＣＨ３Ｃｏ○Ｈ）したも
ので、Ｄ−グルコサミン残基が多数β−（１，４）結合
した天然高分子である。
そして、キトサンは、例えば排水浄化凝集剤、化粧品素
材、食品素材、医薬品及び医療品素材として多方面の用
途が期待されているバイオマス資源であると言われてい
る。
現在、キチンやキトサンの原料は、食品加工場で廃棄さ
れているカニやエビの殻（クチクラ）であり、これらの
クチクラは、下記の表１に示す如く、主にキチン、タン
パク質及び炭酸カルシウムの３成分からなり、キチンの
含有量は１０〜３０％程度である。
表１（ｇ／１００ｇ）
ところで、クチクラからキチンを単離する現在の製法は
、第８図に示す如く、クチクラの粉末１に対して５０倍
量の希塩酸（２ＮのＨＣｊりを用い、室温下の条件で〜
４日時間かけて反応させることにより無機塩の除去を行
い、次いでこの脱灰物に３０倍量のカセイソーダ水溶１
ｆｆｌ（ＩＮ（７）ＮａＯＨ）を添加し、そして３６時
間もの長時間にわたって煮沸してタンパク質を除き、そ
のあと水、エタノール、エーテル等で順次洗浄して、キ
チンを単離生成している。
しかしながら、このような方法は、長時間かけての希塩
酸、熱希カセイソーダによる処理である為、キチン自体
に解重合、脱アセチル化などの変性を招来し、反応設備
も大型なものである等の問題がある。
尚、このキチンを原料として、４０〜６０％の濃カセイ
ソーダ溶液で３〜５時間加熱すると、脱アセチル化され
たキトサンが得られる。
又、キトサンの工業的製法を目的として、腐敗防止のた
め除タンパクを先に行ったり、原料の粉砕形状に種々の
考慮が払われたり、そして脱灰処理においては希塩酸の
代わりにＥＤＴＡを用いる方法が、又、徐タンパクにお
いては熱希アルカリの代わりにプロテアーゼ産生菌を用
いる方法が、さらに菌類の細胞壁に含まれるキチン及び
キトサンの存在に着目し、菌類の大量培養によってキト
サンを抽出する方法が試みられているが、実用化には至
っていない。
このようにクチクラからキトサンを生成するには、これ
までの方法では〜数日といったかなりの時間がかかり、
脱灰、脱タンパク賞、脱アセチル化の３工程を要し、そ
して反応工程がバッチ式である為、設備が大型化し、制
御性が悪く、生産性も低い。Chitin is a natural polymer with many β-(1,4) bonded N-acetyl-D-glucosamine residues, and chitosan is deacetylated by hydrolyzing the acetamido group (NHCOCH,) in the chitin molecule. (removed from CH3Co○H), and is a natural polymer in which many D-glucosamine residues are bonded with β-(1,4). Chitosan is said to be a biomass resource that is expected to be used in a wide variety of fields, such as as a wastewater purification flocculant, a cosmetic material, a food material, a drug, and a medical material. Currently, the raw material for chitin and chitosan is the shells (cuticles) of crabs and shrimps discarded at food processing plants, and these cuticles mainly contain chitin, protein, and calcium carbonate, as shown in Table 1 below. It consists of three components, and the chitin content is about 10 to 30%. Table 1 (g/100g) By the way, the current production method for isolating chitin from the cuticle is as shown in Figure 8, using 50 times the amount of dilute hydrochloric acid (2N HCJ) per 1 part cuticle powder at room temperature. Under the conditions of ~
The inorganic salts were removed by reacting for 4 days, and then 30 times the amount of caustic soda solution was added to the deashed product.
ffl (IN(7)NaOH) is added and boiled for as long as 36 hours to remove proteins, and then sequentially washed with water, ethanol, ether, etc. to isolate and produce chitin. However, since such a method involves long-time treatment with dilute hydrochloric acid and hot dilute caustic soda, chitin itself is subject to modifications such as depolymerization and deacetylation, and the reaction equipment is also large. There's a problem. If this chitin is used as a raw material and heated for 3 to 5 hours in a 40 to 60% concentrated caustic soda solution, deacetylated chitosan can be obtained. In addition, for the purpose of industrial production of chitosan, protein removal is performed first to prevent spoilage, various considerations are given to the shape of the pulverized raw material, and methods are used in which EDTA is used instead of dilute hydrochloric acid in the deashing process. However, for slow protein production, attempts have been made to use protease-producing bacteria instead of hot dilute alkali, and to focus on the presence of chitin and chitosan contained in fungal cell walls, attempts have been made to extract chitosan by mass culturing fungi. However, it has not been put into practical use. Generating chitosan from the cuticle in this way takes a considerable amount of time, up to several days, using conventional methods.
It requires three steps: deashing, deproteinization, and deacetylation, and the reaction process is a batch process, resulting in large equipment, poor controllability, and low productivity.
本発明の第１の目的は、甲殻類のクチクラからキトサン
を得るのに長時間を要さず、生産性が高い甲殻類の資源
化方法を提供することである。
本発明の第２の目的は、甲殻類のクチクラからキトサン
が高収率で得られ、生産性が高い甲殻類の資源化方法を
提供することである。
本発明の第３の目的は、甲殻類のクチクラから得られる
キトサンの純度が高い甲殻類の資源化方法を提供するこ
とである。
上記本発明の目的は、甲殻類のクチクラと酸性溶液とを
混合し、約１００〜１５０℃の温度条件下で反応させ、
クチクラの灰分を脱灰することを特徴とする甲殻類の資
源化方法によって達成される。
尚、この甲殻類の資源化方法において、反応脱灰後の溶
液を濾過し、残渣を水、アルコールで洗浄することが、
又、さらに反応脱灰物とアルカリ溶液とを混合し、約１
２０〜１８０℃の温度条件下で脱アセチル化反応を行う
ことが、又、脱アセチル化反応後の溶液を濾過し、水、
アルコールで洗浄することが好ましい。
又、上記甲殻類の資源化方法において、甲殻類のクチク
ラは粉末状に粉砕されていることが好ましく、そして粉
末状クチクラ１重量部対して酸性溶液、例えば２ＮのＨ
Ｃ１水溶液が約１０〜３０体積部用いられる。
又、反応脱灰物とアルカリ溶液との混合に際しては、脱
灰物１重量部対して１５ＮのＮａＯＨが約２０〜４０体
積部用いられる。
すなわち、本発明は、襄温高圧条件下で反応を行うこと
のできる水熱法をクチクラからキトサンを生成する脱灰
工程に取り入れることで反応時間の短縮化を図れ、又、
除タンパク工程や脱アセチル化の工程にも上記の手段を
取り入れることで、反応時間の短縮、生成工程の簡略化
が図れ、生産性良くキトサンが得られるのである。
そして、水熱条件下における約１時間以内の塩酸処理で
クチクラから無機塩除去がほぼ完全に行え、すなわち脱
灰率がほぼ１００％のものとなり、不純物のない高品質
のキトサンが得られる。
又、水熱条件下における約３時間以内のアルカリ処理で
、脱灰物から高い脱アセチル化度のキトサンを高収率で
得ることができ、そして反応温度、反応時間を調整する
ことにより、所望の脱アセチル化度で所望の分子量のキ
トサンが得られる。A first object of the present invention is to provide a method for recycling crustaceans that does not require a long time to obtain chitosan from the cuticle of crustaceans and is highly productive. A second object of the present invention is to provide a highly productive method for recycling crustaceans, in which chitosan can be obtained from the cuticle of crustaceans at a high yield. A third object of the present invention is to provide a method for recycling crustaceans in which chitosan obtained from the cuticle of the crustaceans has high purity. The object of the present invention is to mix the cuticle of a crustacean and an acidic solution and react at a temperature of about 100 to 150°C,
This is achieved by a method for recycling crustaceans, which is characterized by decalcifying the ash content of the cuticle. In addition, in this crustacean resource recycling method, filtering the solution after reaction deashing and washing the residue with water and alcohol,
Further, the reaction demineralized product and an alkaline solution are mixed, and about 1
It is also possible to carry out the deacetylation reaction under a temperature condition of 20 to 180°C, or to filter the solution after the deacetylation reaction and add water,
Cleaning with alcohol is preferred. Further, in the above-mentioned method for recycling crustaceans, the cuticle of the crustacean is preferably ground into powder, and 1 part by weight of the powdered cuticle is mixed with an acidic solution, for example, 2N H
About 10-30 parts by volume of C1 aqueous solution is used. Further, when mixing the reaction deashed product and the alkaline solution, about 20 to 40 parts by volume of 15N NaOH is used per 1 part by weight of the deashed product. That is, the present invention aims to shorten the reaction time by incorporating a hydrothermal method capable of carrying out the reaction under conditions of high temperature and high pressure into the demineralization process for producing chitosan from the cuticle.
By incorporating the above-mentioned means into the protein removal process and deacetylation process, the reaction time can be shortened, the production process can be simplified, and chitosan can be obtained with high productivity. Then, inorganic salts can be almost completely removed from the cuticle by hydrochloric acid treatment under hydrothermal conditions for about 1 hour, that is, the deashing rate is almost 100%, and high quality chitosan without impurities can be obtained. In addition, chitosan with a high degree of deacetylation can be obtained in high yield from the deashed product by alkali treatment within about 3 hours under hydrothermal conditions, and by adjusting the reaction temperature and reaction time, the desired amount of chitosan can be obtained. Chitosan of the desired molecular weight can be obtained with a degree of deacetylation of .
第１図は、本発明に係る甲殻類の資源化方法のフローチ
ャートである。
先ず、第１図に示す如く、エビ、カニ等の甲殻類の甲殻
（クチクラ）を粉末状に粉砕した後、クチクラ粉末１に
対して２０倍量の塩酸水溶液（２ＮのＨＣｌ）を添加し
、オートクレーブ中で約１００〜１５０℃の水熱条件下
で約２時間以内、例えば１時間以内の脱灰反応を行わせ
る。
これにより、クチクラに３０〜７０％程度含有されてい
るＣａ５Ｍｇ、、Ｐを主成分とする無機塩（ＣａＣＯｘ
が多い）を熱水塩酸で反応させ、塩化物として塩酸可溶
分を溶解し、クチクラから脱灰される。
脱灰後、吸引濾過により分離し、この残渣を水及びエタ
ノールの洗浄液で洗浄、分離して脱灰物を得る。
次いで、脱灰物１に対して３０倍量の１５ＮのＮａＯＨ
水溶液を加え、掻き混ぜながらオートクレーブで約１２
０〜１８０℃の水熱条件下で５時間以内の除タンパク、
脱アセチル化反応を行わせ、反応後、吸引濾過し、そし
て水及びエタノールの洗浄液で洗浄するとキトサンが得
られる。
ところで、上記の工程（水熱脱灰反応）における反応温
度と脱灰率との関係を調べると、第２図に示す通りであ
り、反応温度を上げると脱灰率は向上し、例えば反応温
度１２０℃１反応時間１時間での脱灰率はほぼ１００％
となり、高品質の脱灰物（キトサンの中間原料）を得る
ことができる。
すなわち、約１００℃以上、より好ましくは約１１０℃
以上、さらに好ましくは約１２０〜１５０℃の温度で水
熱脱灰反応を行うと、高品質の脱灰物（キトサンの中間
原料）を得ることができる。
又、第３図に、クチクラ、クチクラの室温での脱灰処理
試料、クチクラの１２０℃での水熱処理試料、試薬キチ
ンの粉末Ｘ線回折図を示す。
このクチクラのＸ線回折図における２θ＝３０”付近に
あるピークは炭酸カルシウムであり、これに対して室温
処理及び水熱処理の試料では炭酸カルシウムのピークは
認められず、両者とも脱灰できていることが判る。
しかしながら、試薬キチンにみられる２θ＝１０°付近
のピークは、１２０℃での水熱処理を行った試料には明
確に認められ、結晶性が良いことを示しているのに対し
、室温処理を行った試料ではそのピークがブロードであ
り、室温処理を行った試料のものは結晶性が悪いことを
示している。
第４図に、水熱処理により生成したキトサンの脱アセチ
ル化度及び収率と反応温度（反応時間１時間）との関係
を示す。
これによれば、反応温度が高くなるにつれて脱アセチル
化度は高くなり、脱アセチル化度は反応温度１３０°（
４’は約８０％、１５０’Ｃでは約９０％であり、どち
らの温度でも収率はほぼ１００％であった。
尚、反応温度１８０℃では、脱アセチル化度は約９６％
であるが、収率が約８６％と低下した。
又、反応温度が約１３０℃〜１５０℃で得た生成キトサ
ンは白色であったのに対し、反応温度が約１８０℃で得
た生成キトサンは灰色を呈しており、高温での収率の低
下に対応して分子鎖の亀裂及び分解によってキトサンの
構造が一部変化するものと推察され、分解を起こさない
脱アセチル化のための反応温度は約１６０ ”Ｃ以下、
好ましくは約１５０℃以下であった。
第５図に、水熱処理時間（反応温度１５０℃）と脱アセ
チル化度及び収率との関係を示す。
これによれば、反応時間が長くなるにつれて脱アセチル
化度は上昇し、３時間で約１００％に達することが判る
。
一方、収率は反応時間が長くなるにつれてやや減少の傾
向を示し、３時間の反応で収率は約９８％、５時間で約
９２％であった。
それ故、高収率で、脱アセチル化度の高いキトサンを生
成する好適な条件は、反応温度が約１２０〜１８０℃２
より好ましくは約１３０〜１５０℃１反応時間は約５時
間以内、より好ましくは約３時間以内が望ましいことが
判る。
第６図に、アルカリ水熱処理における反応温度（反応時
間１時間）と生成キトサンの分子量並びに重合度の関係
を、第７図に、アルカリ水熱処理における反応時間（反
応温度１５０℃）と生成キトサンの分子量並びに重合度
の関係を示す。
これによれば、高分子量のキトサンを得る条件は、反応
温度が約１３０〜１５０℃、反応時間が約１時間以内で
あることが望ましい。
【効果１
本発明に係る甲殻類の資源化方法は、甲殻類のクチクラ
と酸性溶液とを混合し、約１００〜１５０℃の温度条件
下で反応させ、クチクラの灰分を脱灰するので、クチク
ラの脱灰処理が短時間で、かつ、効率よく行え、そして
純度が高く、さらには脱アセチル化度が高く、かつ分子
量の大きなキトサンを収率良く得られるようになり、又
、コンパクトな設備でキトサンを製造できるようになる
等の特長を有する。FIG. 1 is a flowchart of a method for recycling crustaceans according to the present invention. First, as shown in Fig. 1, the shells (cuticles) of crustaceans such as shrimp and crabs were ground into powder, and then an aqueous hydrochloric acid solution (2N HCl) was added in an amount of 20 times the amount of cuticle powder. The deashing reaction is carried out in an autoclave under hydrothermal conditions at about 100 to 150° C. within about 2 hours, for example within 1 hour. As a result, inorganic salts (CaCOx
is reacted with hot hydrochloric acid, the hydrochloric acid soluble content is dissolved as chloride, and the cuticle is demineralized. After deashing, it is separated by suction filtration, and the residue is washed with a washing solution of water and ethanol and separated to obtain a deashed product. Next, 30 times the amount of 15N NaOH per 1 part of the demineralized material
Add the aqueous solution and autoclave while stirring for about 12 hours.
Protein removal within 5 hours under hydrothermal conditions of 0-180℃,
Chitosan is obtained by carrying out a deacetylation reaction, filtering with suction after the reaction, and washing with a washing solution of water and ethanol. By the way, when we examine the relationship between the reaction temperature and the deashing rate in the above process (hydrothermal deashing reaction), we find that as shown in Figure 2, the deashing rate improves as the reaction temperature increases. Deashing rate is almost 100% at 120℃ for 1 hour reaction time.
As a result, a high-quality deashed product (an intermediate raw material for chitosan) can be obtained. That is, about 100°C or more, more preferably about 110°C
If the hydrothermal deashing reaction is carried out at a temperature above, preferably about 120 to 150°C, a high quality deashed product (an intermediate raw material for chitosan) can be obtained. Further, FIG. 3 shows powder X-ray diffraction patterns of the cuticle, a sample of the cuticle decalcified at room temperature, a sample of the cuticle hydrothermally treated at 120° C., and the reagent chitin. The peak near 2θ=30'' in the X-ray diffraction diagram of the cuticle is calcium carbonate; on the other hand, no calcium carbonate peak was observed in the samples treated at room temperature and in the hydrothermal treatment, indicating that both were successfully demineralized. However, the peak around 2θ = 10° seen in the reagent chitin was clearly observed in the sample subjected to hydrothermal treatment at 120°C, indicating good crystallinity. The peak of the sample treated at room temperature is broad, indicating that the sample treated at room temperature has poor crystallinity. Figure 4 shows the degree of deacetylation and The relationship between yield and reaction temperature (reaction time: 1 hour) is shown. According to this, as the reaction temperature increases, the degree of deacetylation increases, and the degree of deacetylation increases at a reaction temperature of 130° (
4' was about 80%, and about 90% at 150'C, and the yield was almost 100% at both temperatures. At a reaction temperature of 180°C, the degree of deacetylation is approximately 96%.
However, the yield was reduced to about 86%. In addition, the produced chitosan obtained at a reaction temperature of about 130°C to 150°C was white, whereas the produced chitosan obtained at a reaction temperature of about 180°C was gray, indicating a decrease in yield at high temperatures. It is presumed that the structure of chitosan partially changes due to cracking and decomposition of the molecular chains in response to this, and the reaction temperature for deacetylation without decomposition is approximately 160 ''C or less.
Preferably it was about 150°C or less. FIG. 5 shows the relationship between the hydrothermal treatment time (reaction temperature: 150° C.), the degree of deacetylation, and the yield. According to this, it can be seen that the degree of deacetylation increases as the reaction time increases and reaches about 100% in 3 hours. On the other hand, the yield showed a tendency to decrease slightly as the reaction time increased, and the yield was about 98% after 3 hours of reaction and about 92% after 5 hours. Therefore, the preferred conditions for producing chitosan with a high yield and a high degree of deacetylation are a reaction temperature of about 120-180°C.
More preferably, the reaction time at about 130 to 150° C. is preferably within about 5 hours, more preferably within about 3 hours. Figure 6 shows the relationship between the reaction temperature (reaction time 1 hour) in the alkaline hydrothermal treatment and the molecular weight and degree of polymerization of the chitosan produced. The relationship between molecular weight and degree of polymerization is shown. According to this, the conditions for obtaining high molecular weight chitosan are preferably that the reaction temperature is about 130 to 150°C and the reaction time is about 1 hour or less. [Effect 1] The crustacean resource recycling method according to the present invention mixes the cuticle of the crustacean with an acidic solution and causes the mixture to react at a temperature of about 100 to 150°C to demineralize the ash content of the cuticle. The deashing process can be carried out in a short time and efficiently, and chitosan with high purity, high degree of deacetylation, and large molecular weight can be obtained in good yield, and it can be done with compact equipment. It has features such as being able to produce chitosan.
第１図は本発明に係る甲殻類の資源化方法のフローチャ
ートであり、第２図は水熱脱灰反応における反応温度と
脱灰率との関係を示すグラフ、第３図はクチクラ、クチ
クラの室温での脱灰処理試料、クチクラの１２０℃での
水熱処理試料、試薬キチンの粉末Ｘ線回折図、第４図は
水熱処理により生成したキトサンの脱アセチル化度及び
収率と反応温度（反応時間１時間）との関係をグラフ、
第５図は水熱処理時間（反応温度１５（１’ｃ）と脱ア
セチル化度及び収率との関係を示すグラフ１．第６圀は
アルカリ水熱処理における反応温度（反応時間１時間）
と生成キトサンの分子量並びに重合度との関係を示すグ
ラフ、第７図はアルカリ水熱処理における反応時間（反
応温度１５０℃）と生成キトサンの分子量並びに重合度
との関係を示すグラフであり、第８図は従来のクチクラ
からキトサンを得る工程を示すフローチャートである。Figure 1 is a flowchart of the method for recycling crustaceans according to the present invention, Figure 2 is a graph showing the relationship between reaction temperature and demineralization rate in a hydrothermal demineralization reaction, and Figure 3 is a graph showing the relationship between the cuticle and the cuticle. Powder X-ray diffractograms of a demineralized sample at room temperature, a sample of cuticle hydrothermally treated at 120°C, and the reagent chitin. Graph of the relationship between time (1 hour),
Figure 5 is a graph 1 showing the relationship between hydrothermal treatment time (reaction temperature 15 (1'c), degree of deacetylation, and yield). Figure 6 is the reaction temperature in alkaline hydrothermal treatment (reaction time 1 hour).
FIG. 7 is a graph showing the relationship between the molecular weight and degree of polymerization of chitosan produced, and FIG. The figure is a flowchart showing the conventional process of obtaining chitosan from cuticle.
Claims (4)
０〜１５０℃の温度条件下で反応させ、クチクラの灰分
を脱灰することを特徴とする甲殼類の資源化方法。(1) Mix the cuticle of the crustacean and an acidic solution, and
1. A method for recycling shellfish, which comprises reacting under a temperature condition of 0 to 150°C to demineralize the ash content of the cuticle.
において、反応脱灰後の溶液を濾過し、残渣を水、アル
コールで洗浄する方法。(2) In the method for recycling crustaceans according to claim 1, the solution after reaction demineralization is filtered, and the residue is washed with water and alcohol.
資源化方法において、反応脱灰物とアルカリ溶液とを混
合し、約１２０〜１８０℃の温度条件下で脱アセチル化
反応を行う方法。(3) In the method for recycling shellfish according to claim 1 or 2, the reaction deashing product and an alkaline solution are mixed, and a deacetylation reaction is carried out under a temperature condition of about 120 to 180°C. How to do it.
において、脱アセチル化反応後の溶液を濾過し、水、ア
ルコールで洗浄する方法。(4) In the method for recycling shellfish according to claim 3, the solution after the deacetylation reaction is filtered and washed with water and alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2077030A JPH0699486B2 (en) | 1990-03-28 | 1990-03-28 | How to treat crustaceans |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2077030A JPH0699486B2 (en) | 1990-03-28 | 1990-03-28 | How to treat crustaceans |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03277601A true JPH03277601A (en) | 1991-12-09 |
| JPH0699486B2 JPH0699486B2 (en) | 1994-12-07 |
Family
ID=13622354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2077030A Expired - Fee Related JPH0699486B2 (en) | 1990-03-28 | 1990-03-28 | How to treat crustaceans |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699486B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1247819A1 (en) * | 2001-04-04 | 2002-10-09 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Purified chitins and production process thereof |
| CN114014952A (en) * | 2021-09-24 | 2022-02-08 | 长春工业大学 | A kind of method for preparing chitosan by catalyzing hydrothermal treatment of shrimp and crab shells |
-
1990
- 1990-03-28 JP JP2077030A patent/JPH0699486B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1247819A1 (en) * | 2001-04-04 | 2002-10-09 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Purified chitins and production process thereof |
| CN114014952A (en) * | 2021-09-24 | 2022-02-08 | 长春工业大学 | A kind of method for preparing chitosan by catalyzing hydrothermal treatment of shrimp and crab shells |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0699486B2 (en) | 1994-12-07 |
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