TWI815363B - Zymosis method of shell powder - Google Patents

Zymosis method of shell powder Download PDF

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TWI815363B
TWI815363B TW111110628A TW111110628A TWI815363B TW I815363 B TWI815363 B TW I815363B TW 111110628 A TW111110628 A TW 111110628A TW 111110628 A TW111110628 A TW 111110628A TW I815363 B TWI815363 B TW I815363B
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powder
enzymatic hydrolysis
carapace
raw material
chitosan
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TW202337915A (en
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吳孟昆
陳淑敏
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吳孟昆
陳淑敏
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Abstract

The present invention relates to a zymosis method of shell powder. The method includes: azymosis step, a drying step, and a film making step. The zymosis step includes adding a shell powder into a zymosis raw material, wherein the ratio of the zymosis raw material to the shell powder is between 1:500 and 1:2000 so that the shell powder and the zymosis raw material ferments at a working temperature between 65℃ and 95℃, thereby removing the protein and minerals from the shell powder and turning the shell powder into a chitosan powder. The drying step includes separating the chitosan powder from the zymosis raw material and then drying the chitosan powder. The film making step includes performing a film making process on the dried chitosan powder and thereby tuming the chitosan powder into a chitosan film.

Description

甲殼粉末的酶解方法 Enzymatic hydrolysis method of carapace powder

本發明係有關於一種甲殼粉末的酶解方法,特別是指一種將甲殼粉末進行酶解反應後獲得殼聚糖粉末的方法,及一種利用殼聚糖粉末製作的可生物分解薄膜的製造方法。 The present invention relates to an enzymatic hydrolysis method of carapace powder, and in particular, to a method of obtaining chitosan powder by subjecting carapace powder to an enzymatic hydrolysis reaction, and a method of manufacturing a biodegradable film made of chitosan powder.

中國專利公開號CN113372467A,揭露一種甲殼素液化製備殼聚糖的方法,其解決現有製備甲殼素需要高濃度酸、鹼處理而產生的廢液廢渣污染環境的問題。其經過以下步驟:1.甲殼素的降解;2.酶解;3.純化。 Chinese Patent Publication No. CN113372467A discloses a method for preparing chitosan by liquefying chitin, which solves the problem of environmental pollution caused by the waste liquid and residue produced by the existing high-concentration acid and alkali treatment required to prepare chitin. It goes through the following steps: 1. Chitin degradation; 2. Enzymatic hydrolysis; 3. Purification.

該發明以魷魚扇形骨為原料,通過雙氧水浸泡,利用雙氧水爆炸濃度,使用可控爆破技術,將魷魚扇形骨進行氧化降解,得降解的甲殼素,添加複合酶,將氧化降解甲殼素進一步分解,並通過二氧化碳超臨界流體除雜,即得殼聚糖,該發明工藝殼聚糖提取率為42%。 This invention uses squid fan-shaped bones as raw materials, soaks them in hydrogen peroxide, utilizes the explosion concentration of hydrogen peroxide, and uses controlled explosion technology to oxidatively degrade the squid fan-shaped bones to obtain degraded chitin, and then adds complex enzymes to further decompose the oxidatively degraded chitin. And impurities are removed through carbon dioxide supercritical fluid to obtain chitosan. The chitosan extraction rate of this invention process is 42%.

其採用雙氧水爆破聯合酶法,有鑑於甲殼素萃取透過去礦物質、脫蛋白、漂白、脫乙酰化之步驟,獲得殼聚的方法具有高污染、多廢液、生產過程時間長等多項缺點。 It uses hydrogen peroxide explosion combined with enzymatic method. In view of the steps of chitin extraction, demineralization, deproteinization, bleaching, and deacetylation, the method of obtaining chitopolymer has many shortcomings such as high pollution, excessive waste liquid, and long production process time.

因此,本發明提供甲殼粉末的酶解方法,其步驟包含:一曝氣步驟,將一酶解原料進行曝氣,該酶解原料係包含一液態澱粉芽孢桿菌、一糖及一去離子水,曝氣時間介於120分鐘至180分鐘之間;一加熱步驟,將該酶解原料加熱至一工作溫度,該工作溫度係介於65℃至95℃之間;一酶解步驟,該酶 解步驟係將一甲殼粉末加入該酶解原料中,該液態澱粉芽孢桿菌與該甲殼粉末之添加比例係為1:500至1:2000之間,該甲殼粉末佔該去離子水總量的重量百分比的55%~86%之間,該糖佔該甲殼粉末的重量百分比的10%~25%之間,使該甲殼粉末與該酶解原料在該工作溫度下醱酵,藉此去除該甲殼粉末中的蛋白質及礦物質,使該甲殼粉末變為一殼聚糖粉末;一乾燥步驟,該乾燥步驟係將該殼聚糖粉末與該酶解原料分離,並將該殼聚糖粉末進行乾燥。 Therefore, the present invention provides an enzymatic hydrolysis method of carapace powder. The steps include: an aeration step to aerate an enzymatic hydrolysis raw material. The enzymatic hydrolysis raw material contains a liquid Bacillus amylolyticum, a sugar and a deionized water, The aeration time is between 120 minutes and 180 minutes; a heating step, the enzymatic hydrolysis raw material is heated to a working temperature, the working temperature is between 65°C and 95°C; an enzymatic hydrolysis step, the enzyme The hydrolysis step is to add a shell powder to the enzymatic hydrolysis raw material. The addition ratio of the liquid Bacillus amyloides and the shell powder is between 1:500 and 1:2000. The weight of the shell powder accounts for the total amount of deionized water. The sugar accounts for between 10% and 25% of the weight percentage of the carapace powder, so that the carapace powder and the enzymatic hydrolysis raw material are fermented at the working temperature, thereby removing the carapace The proteins and minerals in the powder turn the carapace powder into a chitosan powder; a drying step separates the chitosan powder from the enzymatic raw material and dries the chitosan powder .

進一步,包含一粉碎步驟,該粉碎步驟係在該酶解步驟前,將一甲殼粉碎成為該甲殼粉末。 Further, a pulverizing step is included. The pulverizing step is to pulverize a carapace into the carapace powder before the enzymatic hydrolysis step.

進一步,該甲殼係選自下列材料之一:蛹殼、黑水虻殼、獨角仙殼、蟑螂殼、瓢蟲殼、蒼蠅殼、魚鱗、蝦殼及蟹殼。 Further, the carapace is selected from one of the following materials: pupa shell, black soldier fly shell, unicorn shell, cockroach shell, ladybug shell, fly shell, fish scale, shrimp shell and crab shell.

本發明另提供一種殼聚糖膜的製造方法,其步驟包含:一製膜步驟,該製膜步驟係將乾燥的該殼聚糖粉末進行一製膜流程,使該殼聚糖粉末成為一殼聚糖膜。 The present invention also provides a method for manufacturing a chitosan film. The steps include: a film-making step, which involves subjecting the dried chitosan powder to a film-making process, so that the chitosan powder becomes a shell. polysaccharide film.

進一步,該製膜流程包含澆鑄成型、塗層成型、組裝成型或擠出成型。 Further, the film making process includes casting molding, coating molding, assembly molding or extrusion molding.

進一步,該製膜步驟中,該殼聚糖粉末係有包含一添加物,該添加物係選自下列材料之一或其組合:檸檬酸、明膠、甘油及澱粉。 Further, in the film-making step, the chitosan powder contains an additive, and the additive is selected from one of the following materials or a combination thereof: citric acid, gelatin, glycerol and starch.

本發明具有下列之優點: The present invention has the following advantages:

1.以液態澱粉芽孢桿菌混合去離子水作為酶解原料,降低酶解過程中對環境造成的汙染,同時提升酶解效率。 1. Use liquid Bacillus amyloides mixed with deionized water as the raw material for enzymatic hydrolysis to reduce environmental pollution during the enzymatic hydrolysis process and improve the enzymatic hydrolysis efficiency.

2.在殼聚糖膜的製膜過程中,將殼聚糖粉末加入不同的添加物,使製作完成的殼聚糖膜依照加入的添加物具有與添加物對應的特性。 2. During the film-making process of the chitosan film, different additives are added to the chitosan powder so that the completed chitosan film has characteristics corresponding to the additives.

S1:粉碎步驟 S1: crushing step

S2:曝氣步驟 S2: Aeration step

S3:加熱步驟 S3: Heating step

S4:酶解步驟 S4: Enzymatic hydrolysis step

S5:乾燥步驟 S5: Drying step

S6:製膜步驟 S6: Film making steps

1:甲殼粉末 1:Carapace powder

2:酶解原料 2: Enzymatic hydrolysis raw materials

3:殼聚糖粉末 3:Chitosan powder

4:殼聚糖膜 4: Chitosan film

A:基材 A:Substrate

B:容器 B: Container

[第一圖]係本發明實施例的流程圖。 [First Figure] is a flow chart of an embodiment of the present invention.

[第二圖]係本發明實施例的甲殼粉末的示意圖。 [The second figure] is a schematic diagram of the carapace powder according to the embodiment of the present invention.

[第三圖]係本發明實施例的酶解原料的示意圖。 [The third figure] is a schematic diagram of the enzymatic hydrolysis raw material according to the embodiment of the present invention.

[第四圖]係本發明實施例的殼聚糖粉末的示意圖。 [The fourth figure] is a schematic diagram of chitosan powder according to an embodiment of the present invention.

[第五圖]係本發明實施例的殼聚糖膜的示意圖。 [The fifth figure] is a schematic diagram of a chitosan film according to an embodiment of the present invention.

首先請參閱第一圖至第四圖,說明本發明甲殼粉末的酶解方法的實施例的流程,其步驟包含了粉碎步驟S1、曝氣步驟S2、加熱步驟S3、酶解步驟S4、乾燥步驟S5及成型步驟,粉碎步驟S1係將甲殼透過磨碎或是壓碎等方式進行粉碎,藉此將甲殼粉碎為甲殼粉末1,以提升後續酶解步驟S4的反應效率。 First, please refer to Figures 1 to 4 to illustrate the process of an embodiment of the enzymatic hydrolysis method of carapace powder of the present invention. The steps include a crushing step S1, an aeration step S2, a heating step S3, an enzymatic hydrolysis step S4, and a drying step. S5 and the forming step, the pulverizing step S1 is to pulverize the carapace by grinding or crushing, thereby pulverizing the carapace into shell powder 1 to improve the reaction efficiency of the subsequent enzymatic hydrolysis step S4.

曝氣步驟S2及加熱步驟S3則是對酶解原料2進行曝氣與加熱,在本實施例中,酶解原料2係為液態澱粉芽孢桿菌(Bacillus amyloliquefaciens)、糖與去離子水的混合液,其具有好氧性及耐高溫的性質,曝氣步驟S2是使酶解原料2在酶解步驟S4之前與空氣接觸120分鐘至180分鐘,藉此完成酶解原料2的曝氣步驟S2,而加熱步驟S3的順序同樣是在酶解步驟S4之前,是將酶解原料2加熱至工作溫度的流程,工作溫度是介於65℃至95℃之間,透過加熱步驟S3以使酶解原料2能在後續的酶解步驟S4中去除甲殼粉末1中的礦物質及蛋白質,藉此使甲殼粉末1轉化為純化的甲殼素,即殼聚糖粉末3。 The aeration step S2 and the heating step S3 are to aerate and heat the enzymatic hydrolysis raw material 2. In this embodiment, the enzymatic hydrolysis raw material 2 is a mixture of liquid Bacillus amyloliquefaciens, sugar and deionized water. , which has aerobic and high-temperature resistance properties. The aeration step S2 is to make the enzymatic hydrolysis raw material 2 contact the air for 120 minutes to 180 minutes before the enzymatic hydrolysis step S4, thereby completing the aeration step S2 of the enzymatic hydrolysis raw material 2. The sequence of the heating step S3 is also before the enzymatic hydrolysis step S4. It is a process of heating the enzymatic hydrolysis raw material 2 to the working temperature. The working temperature is between 65°C and 95°C. The heating step S3 enables the enzymatic hydrolysis of the raw material 2. 2 can remove minerals and proteins in the shell powder 1 in the subsequent enzymatic hydrolysis step S4, thereby converting the shell powder 1 into purified chitin, that is, chitosan powder 3.

續請參考第一圖至第三圖,說明本發明甲殼粉末的酶解方法的實施例中,將甲殼粉末1透過酶解成為殼聚糖粉末3的流程,將甲殼進行粉碎步驟S1後,獲得甲殼粉末1,甲殼的原料係選自蛹殼、黑水虻殼、獨角仙殼、蟑螂殼、瓢蟲殼、蒼蠅殼、魚鱗、蝦殼及蟹殼的其中之一。在流程中將甲殼粉末1倒於板型的基材A上,方便將甲殼粉末1倒入裝有酶解原料2的容器B中,進行後續的酶解步驟S4。 Please continue to refer to the first to third figures to illustrate the embodiment of the enzymatic hydrolysis method of carapace powder of the present invention. The process of enzymatic hydrolysis of carapace powder 1 into chitosan powder 3 is carried out. After the carapace is pulverized step S1, obtain Carapace powder 1, the raw material of the carapace is selected from one of pupa shells, black soldier fly shells, unicorn shells, cockroach shells, ladybug shells, fly shells, fish scales, shrimp shells and crab shells. In the process, the carapace powder 1 is poured onto the plate-shaped substrate A, so that the carapace powder 1 can be poured into the container B containing the enzymatic hydrolysis raw material 2 for subsequent enzymatic hydrolysis step S4.

酶解步驟S4係將甲殼粉末1倒入裝有酶解原料2的容器B中,甲殼粉末1約佔酶解原料2中的去離子水總量的重量百分比的55%~86%,而酶解原料2中的液態澱粉芽孢桿菌(Bacillus amyloliquefaciens)與甲殼粉末1之添加比例係為1:500至1:2000之間,酶解原料2中的糖約為甲殼粉末1的重量百分比的10%~25%,接著靜待甲殼粉末1與酶解原料2在工作溫度下醱酵,工作溫度係介於65℃至95℃,以去除甲殼粉末1中的蛋白質及礦物質。 Enzymatic hydrolysis step S4 is to pour the carapace powder 1 into the container B containing the enzymatic hydrolysis raw material 2. The carapace powder 1 accounts for about 55% to 86% of the total weight of the deionized water in the enzymatic hydrolysis raw material 2, and the enzyme The addition ratio of liquid Bacillus amyloliquefaciens and carapace powder 1 in the enzymatic hydrolysis raw material 2 is between 1:500 and 1:2000. The sugar in the enzymatic hydrolysis raw material 2 is about 10% of the weight percentage of the carapace powder 1. ~25%, and then wait for the carapace powder 1 and the enzymatic hydrolysis raw material 2 to ferment at the working temperature, which is between 65°C and 95°C, to remove the protein and minerals in the carapace powder 1.

續請參考第一圖至第四圖,說明本發明甲殼粉末的酶解方法的實施例中,將殼聚糖粉末3進行乾燥步驟S5的流程,承上所述,去除甲殼粉末1中的蛋白質及礦物質時,加入去離子水至酶解原料2中反覆沖洗,直至pH值的範圍介於6.5至7.5,甲殼粉末1會轉變為殼聚糖粉末3,將殼聚糖粉末3從酶解原料2中分離後放置於板型的基材A上待其乾燥,並通過分解過程將殼聚糖粉末3去乙醯化。 Please refer to Figures 1 to 4 to illustrate the embodiment of the enzymatic hydrolysis method of carapace powder of the present invention. The chitosan powder 3 is subjected to the drying step S5. Following the above, the protein in the carapace powder 1 is removed. When removing minerals, add deionized water to the enzymatic hydrolysis raw material 2 and rinse repeatedly until the pH value ranges between 6.5 and 7.5. The carapace powder 1 will be converted into chitosan powder 3, and the chitosan powder 3 will be enzymatically hydrolyzed from The raw material 2 is separated and placed on a plate-shaped substrate A to dry, and the chitosan powder 3 is deacetylated through a decomposition process.

續請參考第一圖、第四圖及第五圖,說明本發明甲殼粉末的酶解方法的實施例中,將乾燥的殼聚糖粉末3製成殼聚糖膜4的製膜步驟S6的流程,乾燥的殼聚糖粉末3加入水混合後,可以透過澆鑄成型、塗層成型、組裝成型或擠出成型等方式在基材A的表面形成殼聚糖膜4。 Please refer to the first, fourth and fifth figures to illustrate the step S6 of making the dried chitosan powder 3 into a chitosan film 4 in an embodiment of the enzymatic hydrolysis method of carapace powder of the present invention. In the process, after the dry chitosan powder 3 is mixed with water, the chitosan film 4 can be formed on the surface of the substrate A through casting molding, coating molding, assembly molding or extrusion molding.

值得一提的是,殼聚糖粉末3可以透過加入水與添加物以改變殼聚糖膜4的性質,水溫係介於1℃至98℃,殼聚糖粉末3約占水的重量百分比的0.01%至15%,添加物係選自檸檬酸、明膠、甘油及澱粉其中之一或其組合。例如加入檸檬酸可以提升殼聚糖膜4的耐濕性、熱穩定性及抗氧化活性,檸檬酸約佔水的重量百分比的0.1%至5%;加入甘油可以提升殼聚糖膜4的柔韌性,甘油約佔水的重量百分比的0.2%至5%;也可以添加奈米銀增加殼聚糖膜4的抗菌活性,奈米銀約佔水的重量百分比的0.01%至15%;添加氧化鋅增加殼聚糖膜4 的拉伸強度,氧化鋅約佔水的重量百分比的0.01%至15%;添加單寧酸增加殼聚糖膜4的耐水性,單寧酸約佔水的重量百分比的0.01%至15%。 It is worth mentioning that the chitosan powder 3 can change the properties of the chitosan film 4 by adding water and additives. The water temperature ranges from 1°C to 98°C, and the chitosan powder 3 accounts for approximately the weight percentage of water. 0.01% to 15%, the additive system is selected from one or a combination of citric acid, gelatin, glycerin and starch. For example, adding citric acid can improve the moisture resistance, thermal stability and antioxidant activity of chitosan film 4. Citric acid accounts for about 0.1% to 5% of the weight of water; adding glycerin can improve the flexibility of chitosan film 4. properties, glycerol accounts for about 0.2% to 5% of the weight of water; nanosilver can also be added to increase the antibacterial activity of the chitosan film 4, nanosilver accounts for about 0.01% to 15% of the weight of water; adding oxidation Zinc increases chitosan film 4 The tensile strength of zinc oxide accounts for approximately 0.01% to 15% of the weight percent of water; adding tannic acid increases the water resistance of the chitosan film 4, and tannic acid accounts for approximately 0.01% to 15% of the weight percent of water.

綜合上述實施例之說明,當可充分瞭解本發明之操作、使用及本發明產生之功效,惟以上所述實施例僅係為本發明之較佳實施例,當不能以此限定本發明實施之範圍,即依本發明申請專利範圍及發明說明內容所作簡單的等效變化與修飾,皆屬本發明涵蓋之範圍內。 Based on the description of the above embodiments, the operation, use and effects of the present invention can be fully understood. However, the above embodiments are only preferred embodiments of the present invention and should not be used to limit the implementation of the present invention. The scope, that is, simple equivalent changes and modifications based on the patent scope of the present invention and the description of the invention, are all within the scope of the present invention.

S1:粉碎步驟 S1: crushing step

S2:曝氣步驟 S2: Aeration step

S3:加熱步驟 S3: Heating step

S4:酶解步驟 S4: Enzymatic hydrolysis step

S5:乾燥步驟 S5: Drying step

S6:製膜步驟 S6: Film making steps

Claims (3)

一種甲殼粉末的酶解方法,其步驟包含:一曝氣步驟,將一酶解原料進行曝氣,該酶解原料係包含一液態澱粉芽孢桿菌、一糖及一去離子水,曝氣時間介於120分鐘至180分鐘之間;一加熱步驟,將該酶解原料加熱至一工作溫度,該工作溫度係介於65℃至95℃之間;一酶解步驟,該酶解步驟係將一甲殼粉末加入該酶解原料中,該液態澱粉芽孢桿菌與該甲殼粉末之添加比例係為1:500至1:2000之間,該甲殼粉末佔該去離子水總量的重量百分比的55%~86%之間,該糖佔該甲殼粉末的重量百分比的10%~25%之間,使該甲殼粉末與該酶解原料在該工作溫度下醱酵,藉此去除該甲殼粉末中的蛋白質及礦物質,使該甲殼粉末變為一殼聚糖粉末;一乾燥步驟,該乾燥步驟係將該殼聚糖粉末與該酶解原料分離,並將該殼聚糖粉末進行乾燥。 An enzymatic hydrolysis method of carapace powder, the steps include: an aeration step, aerating an enzymatic raw material, the enzymatic raw material contains a liquid Bacillus amylolyticus, a sugar and a deionized water, the aeration time is between Between 120 minutes and 180 minutes; a heating step, heating the enzymatic hydrolysis raw material to a working temperature, the working temperature is between 65°C and 95°C; an enzymatic hydrolysis step, the enzymatic hydrolysis step is to The carapace powder is added to the enzymatic hydrolysis raw material. The addition ratio of the liquid Bacillus amyloides and the carapace powder is between 1:500 and 1:2000. The carapace powder accounts for 55% of the total weight of the deionized water. Between 86% and 10% to 25% of the weight of the carapace powder, the sugar is allowed to ferment the carapace powder and the enzymatic raw material at the working temperature, thereby removing the protein and Minerals are used to turn the carapace powder into chitosan powder; a drying step is to separate the chitosan powder from the enzymatic hydrolysis raw material and dry the chitosan powder. 如請求項1所述之甲殼粉末的酶解方法,其中包含一粉碎步驟,該粉碎步驟係在該酶解步驟前,將一甲殼粉碎成為該甲殼粉末。 The enzymatic hydrolysis method of carapace powder as described in claim 1, which includes a crushing step. The crushing step is to crush a carapace into the carapace powder before the enzymatic hydrolysis step. 如請求項2所述之甲殼粉末的酶解方法,其中該甲殼係選自下列材料之一:蛹殼、黑水虻殼、獨角仙殼、蟑螂殼、瓢蟲殼、蒼蠅殼、魚鱗、蝦殼及蟹殼。 The enzymatic hydrolysis method of carapace powder as described in claim 2, wherein the carapace is selected from one of the following materials: pupa shell, black soldier fly shell, unicorn shell, cockroach shell, ladybug shell, fly shell, fish scale, Shrimp and crab shells.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103205024A (en) * 2013-04-17 2013-07-17 湖北工程学院 Edible food packaging film with Chinese chestnut and chitosan as matrixes and preparation method of edible food packaging film
CN107428849A (en) * 2014-12-31 2017-12-01 昆虫公司 Chitin, hydrolysate and the mode by means of enzymatic hydrolysis are used for the method that one or more desired products are produced from insect

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103205024A (en) * 2013-04-17 2013-07-17 湖北工程学院 Edible food packaging film with Chinese chestnut and chitosan as matrixes and preparation method of edible food packaging film
CN107428849A (en) * 2014-12-31 2017-12-01 昆虫公司 Chitin, hydrolysate and the mode by means of enzymatic hydrolysis are used for the method that one or more desired products are produced from insect

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