CN101775079A - Method for pre-treating chitin raw material - Google Patents
Method for pre-treating chitin raw material Download PDFInfo
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- CN101775079A CN101775079A CN200910155130A CN200910155130A CN101775079A CN 101775079 A CN101775079 A CN 101775079A CN 200910155130 A CN200910155130 A CN 200910155130A CN 200910155130 A CN200910155130 A CN 200910155130A CN 101775079 A CN101775079 A CN 101775079A
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Abstract
The invention discloses a method for pre-treating a chitin raw material, which is characterized by comprising the following steps: 1), filling the chitin raw material in a gas explosion expansion tank and injecting a gas explosion expansion medium which may be vapor, water, aqueous ammonia or ethanol; and 2), relieving the pressure in the gas explosion expansion tank instantaneously and spraying the chitin raw material into a normal pressure container to obtain a chitin concentrate. Compared with the prior art, the method has the advantages of: 1), loosening the compact crystal structure of the chitin and increasing the exposure of active groups; 2), increasing the activity of chemical reaction to smoothly perform a main chemical reaction and increase the reaction speed; and 3), performing the main chemical reaction at a low temperature, inhibiting side reactions and improving product yield.
Description
Technical field
The present invention relates to a kind of pretreatment process of chitin raw material, particularly a kind of method of handling chitin raw material with the expanded method of gas explosion.
Background technology
Chitin has another name called chitin, chitin etc., and it is the polysaccharide that is formed by connecting with β-1,4 glycosidic link form by N-acetyl-2 amino-D-glucose, is a kind of natural chain macromolecule compound.Its chemical name is (1,4)-2-acetylaminohydroxyphenylarsonic acid 2-deoxidation-β-D-glucose.
Chitin is divided into α, β, three kinds of configurations of γ.With shrimp shell and crab shell be raw material produce in the chitin α type chitin occupy the majority, arrange with antiparallel manner between its molecular backbone chain, has hydrogen bond action power between the very strong molecule, the chitin of α, β, three kinds of configurations of γ is intertwined again in addition, and fine and close crystalline structure makes it be difficult for carrying out chemical modification.For example when with the chitin being feedstock production chitin derived product, will run into many troubles, as be difficult to make high deacetylized chitosan, D-glucosamine hydrochloric acid (sulfuric acid) salt, be difficult to obtain higher yield etc.
Present stage, the suitability for industrialized production chitin mainly was to be raw material with depleted shrimp shell and crab shell, and the chemical method that adopts HCl or NaOH to soak is removed lime carbonate and protein respectively and made.Chitin is that raw material can be produced a series of chitin derived product, as chitosan and derivative, oligose and derivative thereof, monose and derivative thereof etc.
Yet, before with the chitin being feedstock production chitin derived product, because fine and close structure own makes chitin be difficult for carrying out chemical modification.People expect naturally and will carry out pre-treatment to chitin raw material, as mechanical disintegration, ultrasonication, microwave treatment, and ultrasonication and microwave treatment still rest on laboratory stage at present, and being applied to industrial method up to now only is mechanical disintegration, but has little effect.
Summary of the invention
The objective of the invention is to propose a kind of pretreatment process of chitin raw material, particularly propose a kind of method of handling chitin raw material with the expanded method of gas explosion.
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts a kind of in water vapour, water, ammoniacal liquor, the ethanol;
When the expanded medium of gas explosion was water vapour, charged pressure was that 0.3～0.5MPa, temperature are 130～150 ℃ water vapour, keeps 5～15min;
When the expanded medium of gas explosion was water, the add-on of water was 10%～50% of a chitin raw material weight, was heated to 130～150 ℃, made jar interior corresponding pressure rise to 0.3～0.5MPa, kept 5～15min;
When the expanded medium of gas explosion was ammoniacal liquor, the add-on of ammoniacal liquor was 10%～50% of a chitin raw material weight, was heated to 100～150 ℃, made jar interior corresponding pressure rise to 0.3～0.8MPa, kept 5～15min;
When the expanded medium of gas explosion was ethanol, amount of alcohol added was 10%～50% of a chitin raw material weight, was heated to 100～150 ℃, made a jar interior relevant pressure rise to 0.3～0.8MPa, kept 5～15min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts a kind of in water vapour, water, ammoniacal liquor, the ethanol;
When the expanded medium of gas explosion was water vapour, charged pressure was that 0.3～0.5MPa, temperature are 130～150 ℃ water vapour, keeps 5～15min;
When the expanded medium of gas explosion was water, the add-on of water was 10%～50% of a chitin raw material weight, was heated to 130～150 ℃, made jar interior corresponding pressure rise to 0.3～0.5MPa, kept 5～15min;
When the expanded medium of gas explosion was ammoniacal liquor, the add-on of ammoniacal liquor was 10%～50% of a chitin raw material weight, was heated to 100～150 ℃, made jar interior corresponding pressure rise to 0.3～0.8MPa, kept 5～15min;
When the expanded medium of gas explosion was ethanol, amount of alcohol added was 10%～50% of a chitin raw material weight, was heated to 100～150 ℃, made a jar interior relevant pressure rise to 0.3～0.8MPa, kept 5～15min;
2) charge into N
2Perhaps CO
2, make pressure rise to 1.0～2.5MPa, keep 5～10min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Compared with prior art, the pretreatment process of chitin raw material of the present invention has the following advantages:
1) makes the crystalline structure of chitin densification become very loose, increase the exposed degree of active group on the chitin chain greatly; 2) increase the chitin chemistry reactive behavior, make the main chemical reaction of chitin hydrolysis and so on be very easy to carry out, and carry out thoroughly; 3) because the chitin chemistry reactive behavior increases, and main chemical reaction can carry out under lower conditions such as temperature, thereby has suppressed the carrying out of side reaction, raising product yield that therefore can be by a relatively large margin; 4) because main chemical reaction rate increases, and side reaction product reduces, and the reaction medium of hydrochloric acid and so on reclaims and becomes very simple, therefore not only can reduce the consumption of the reaction medium of hydrochloric acid and so on, and can reduce pollutant emission, realize cleaner production.
Embodiment
Embodiment 1:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts water vapour, and charged pressure is that 0.5MPa, temperature are 150 ℃ water vapour, keeps 5min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 2:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts water vapour, and charged pressure is that 0.4MPa, temperature are 140 ℃ water vapour, keeps 10min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 3:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts water vapour, and charged pressure is that 0.3MPa, temperature are 130 ℃ water vapour, keeps 15min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 4:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts water, and the add-on of water is 50% of a chitin raw material weight, is heated to 150 ℃, and corresponding pressure rises to 0.5MPa in making jar, keeps 5min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 5:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts water, and the add-on of water is 30% of a chitin raw material weight, is heated to 140 ℃, and corresponding pressure rises to 0.4MPa in making jar, keeps 10min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 6:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts water, and the add-on of water is 10% of a chitin raw material weight, is heated to 130 ℃, and corresponding pressure rises to 0.3MPa in making jar, keeps 15min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 7:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts ammoniacal liquor, and the add-on of ammoniacal liquor is 50% of a chitin raw material weight, is heated to 150 ℃, and corresponding pressure rises to 0.8MPa in making jar, keeps 5min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 8:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts ammoniacal liquor, and the add-on of ammoniacal liquor is 30% of a chitin raw material weight, is heated to 130 ℃, and corresponding pressure rises to 0.5MPa in making jar, keeps 10min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 9:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts ammoniacal liquor, and the add-on of ammoniacal liquor is 10% of a chitin raw material weight, is heated to 100 ℃, and corresponding pressure rises to 0.3MPa in making jar, keeps 15min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 10:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts ethanol, and amount of alcohol added is 50% of a chitin raw material weight, is heated to 150 ℃, makes a jar interior relevant pressure rise to 0.8MPa, keeps 5min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 11:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts ethanol, and amount of alcohol added is 30% of a chitin raw material weight, is heated to 130 ℃, makes a jar interior relevant pressure rise to 0.5MPa, keeps 10min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 12:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts ethanol, and amount of alcohol added is 10% of a chitin raw material weight, is heated to 100 ℃, makes a jar interior relevant pressure rise to 0.3MPa, keeps 15min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 13:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts water vapour, and charged pressure is that 0.5MPa, temperature are 150 ℃ water vapour, keeps 5min;
2) charge into N
2Perhaps CO
2Make pressure rise to 1.0MPa, keep 10min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 14:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts water vapour, and charged pressure is that 0.4MPa, temperature are 140 ℃ water vapour, keeps 10min;
2) charge into N
2Perhaps CO
2Make pressure rise to 1.5MPa, keep 10min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 15:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts water vapour, and charged pressure is that 0.3MPa, temperature are 130 ℃ water vapour, keeps 15min;
2) charge into N
2Perhaps CO
2Make pressure rise to 2.5MPa, keep 5min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 16:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts water, and the add-on of water is 50% of a chitin raw material weight, is heated to 150 ℃, and corresponding pressure rises to 0.5MPa in making jar, keeps 5min;
2) charge into N
2Perhaps CO
2Make pressure rise to 1.0MPa, keep 10min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 17:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts water, and the add-on of water is 30% of a chitin raw material weight, is heated to 140 ℃, and corresponding pressure rises to 0.4MPa in making jar, keeps 10min;
2) charge into N
2Perhaps CO
2Make pressure rise to 1.5MPa, keep 10min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 18:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts water, and the add-on of water is 10% of a chitin raw material weight, is heated to 130 ℃, and corresponding pressure rises to 0.3MPa in making jar, keeps 15min;
2) charge into N
2Perhaps CO
2Make pressure rise to 2.5MPa, keep 5min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 19:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts ammoniacal liquor, and the add-on of ammoniacal liquor is 50% of a chitin raw material weight, is heated to 150 ℃, and corresponding pressure rises to 0.8MPa in making jar, keeps 5min;
2) charge into N
2Perhaps CO
2Make pressure rise to 1.0MPa, keep 10min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 20:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts ammoniacal liquor, and the add-on of ammoniacal liquor is 30% of a chitin raw material weight, is heated to 130 ℃, and corresponding pressure rises to 0.5MPa in making jar, keeps 10min;
2) charge into N
2Perhaps CO
2Make pressure rise to 1.5MPa, keep 10min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 21:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts ammoniacal liquor, and the add-on of ammoniacal liquor is 10% of a chitin raw material weight, is heated to 100 ℃, and corresponding pressure rises to 0.3MPa in making jar, keeps 15min;
2) charge into N
2Perhaps CO
2Make pressure rise to 2.5MPa, keep 5min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 22:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts ethanol, and amount of alcohol added is 50% of a chitin raw material weight, is heated to 150 ℃, makes a jar interior relevant pressure rise to 0.8MPa, keeps 5min;
2) charge into N
2Perhaps CO
2Make pressure rise to 1.0MPa, keep 10min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 23:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts ethanol, and amount of alcohol added is 30% of a chitin raw material weight, is heated to 130 ℃, makes a jar interior relevant pressure rise to 0.5MPa, keeps 10min;
2) charge into N
2Perhaps CO
2Make pressure rise to 1.5MPa, keep 10min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Embodiment 24:
A kind of pretreatment process of chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts ethanol, and amount of alcohol added is 10% of a chitin raw material weight, is heated to 100 ℃, makes a jar interior relevant pressure rise to 0.3MPa, keeps 15min;
2) charge into N
2Perhaps CO
2Make pressure rise to 2.5MPa, keep 5min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
Claims (2)
1. the pretreatment process of a chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts a kind of in water vapour, water, ammoniacal liquor, the ethanol;
When the expanded medium of gas explosion was water vapour, charged pressure was that 0.3～0.5MPa, temperature are 130～150 ℃ water vapour, keeps 5～15min;
When the expanded medium of gas explosion was water, the add-on of water was 10%～50% of a chitin raw material weight, was heated to 130～150 ℃, made jar interior corresponding pressure rise to 0.3～0.5MPa, kept 5～15min;
When the expanded medium of gas explosion was ammoniacal liquor, the add-on of ammoniacal liquor was 10%～50% of a chitin raw material weight, was heated to 100～150 ℃, made jar interior corresponding pressure rise to 0.3～0.8MPa, kept 5～15min;
When the expanded medium of gas explosion was ethanol, amount of alcohol added was 10%～50% of a chitin raw material weight, was heated to 100～150 ℃, made a jar interior relevant pressure rise to 0.3～0.8MPa, kept 5～15min;
2) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
2. the pretreatment process of a chitin raw material is characterized in that adopting following steps:
1) chitin raw material is packed in the gas explosion Bulking tank, inject the expanded medium of gas explosion, the expanded medium of gas explosion adopts a kind of in water vapour, water, ammoniacal liquor, the ethanol;
When the expanded medium of gas explosion was water vapour, charged pressure was that 0.3～0.5MPa, temperature are 130～150 ℃ water vapour, keeps 5～15min;
When the expanded medium of gas explosion was water, the add-on of water was 10%～50% of a chitin raw material weight, was heated to 130～150 ℃, made jar interior corresponding pressure rise to 0.3～0.5MPa, kept 5～15min;
When the expanded medium of gas explosion was ammoniacal liquor, the add-on of ammoniacal liquor was 10%～50% of a chitin raw material weight, was heated to 100～150 ℃, made jar interior corresponding pressure rise to 0.3～0.8MPa, kept 5～15min;
When the expanded medium of gas explosion was ethanol, amount of alcohol added was 10%～50% of a chitin raw material weight, was heated to 100～150 ℃, made a jar interior relevant pressure rise to 0.3～0.8MPa, kept 5～15min;
2) charge into N
2Perhaps CO
2Make pressure rise to 1.0～2.5MPa, keep 5～10min;
3) pressure in the moment venting gas explosion Bulking tank, and chitin raw material spurted in the non-pressure vessel, the chitin fine fodder obtained.
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| CN200910155130A CN101775079A (en) | 2009-12-07 | 2009-12-07 | Method for pre-treating chitin raw material |
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| CN102349668A (en) * | 2011-10-14 | 2012-02-15 | 浙江大学 | Preparation method of bio-active calcium jelly |
| CN102349601A (en) * | 2011-10-14 | 2012-02-15 | 浙江大学 | Preparation method of high-calcium jelly |
| CN102415517A (en) * | 2011-10-14 | 2012-04-18 | 浙江大学 | Method for preparing bioactive calcium jelly from shrimp shell |
| CN102423020A (en) * | 2011-10-14 | 2012-04-25 | 浙江大学 | Preparation method of jelly containing biological active calcium |
| CN102976802A (en) * | 2012-11-23 | 2013-03-20 | 山东嘉丰海洋生物科技有限公司 | Processing method of chitosan fluid fertilizer |
| CN103145873A (en) * | 2011-12-06 | 2013-06-12 | 蔡敏郎 | Deacetylation method for chitin |
| CN103936884A (en) * | 2014-04-18 | 2014-07-23 | 广西还珠海洋生物科技有限公司 | Method for extracting chitin from shrimp and crab shells |
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| CN102349668A (en) * | 2011-10-14 | 2012-02-15 | 浙江大学 | Preparation method of bio-active calcium jelly |
| CN102349601A (en) * | 2011-10-14 | 2012-02-15 | 浙江大学 | Preparation method of high-calcium jelly |
| CN102415517A (en) * | 2011-10-14 | 2012-04-18 | 浙江大学 | Method for preparing bioactive calcium jelly from shrimp shell |
| CN102423020A (en) * | 2011-10-14 | 2012-04-25 | 浙江大学 | Preparation method of jelly containing biological active calcium |
| CN102415517B (en) * | 2011-10-14 | 2012-11-07 | 浙江大学 | Method for preparing bioactive calcium jelly from shrimp shell |
| CN102423020B (en) * | 2011-10-14 | 2013-03-20 | 浙江大学 | Preparation method of jelly containing biological active calcium |
| CN103145873B (en) * | 2011-12-06 | 2015-12-09 | 蔡敏郎 | The method of chitin deacetylation |
| CN103145873A (en) * | 2011-12-06 | 2013-06-12 | 蔡敏郎 | Deacetylation method for chitin |
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