CN108285933A - Using shrimp and crab shells as the ammonia sugar preparation method of raw material - Google Patents

Using shrimp and crab shells as the ammonia sugar preparation method of raw material Download PDF

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Publication number
CN108285933A
CN108285933A CN201810225486.7A CN201810225486A CN108285933A CN 108285933 A CN108285933 A CN 108285933A CN 201810225486 A CN201810225486 A CN 201810225486A CN 108285933 A CN108285933 A CN 108285933A
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shrimp
chitin
crab shells
ammonia sugar
raw material
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CN108285933B (en
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平立凤
丁振中
柳志强
曾哲灵
冯小海
李恒
龚劲松
高小燕
徐俊山
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YANGZHOU RIXING BIO-TECH Co Ltd
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YANGZHOU RIXING BIO-TECH Co Ltd
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Priority to PCT/CN2018/116358 priority patent/WO2019179148A1/en
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    • C13SUGAR INDUSTRY
    • C13KSACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00Glucose; Glucose-containing syrups
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    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/00272-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23JPROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
    • A23J1/00Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites
    • A23J1/04Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites from fish or other sea animals
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23JPROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
    • A23J3/00Working-up of proteins for foodstuffs
    • A23J3/30Working-up of proteins for foodstuffs by hydrolysis
    • A23J3/32Working-up of proteins for foodstuffs by hydrolysis using chemical agents
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23JPROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
    • A23J3/00Working-up of proteins for foodstuffs
    • A23J3/30Working-up of proteins for foodstuffs by hydrolysis
    • A23J3/32Working-up of proteins for foodstuffs by hydrolysis using chemical agents
    • A23J3/34Working-up of proteins for foodstuffs by hydrolysis using chemical agents using enzymes
    • A23J3/341Working-up of proteins for foodstuffs by hydrolysis using chemical agents using enzymes of animal proteins
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/125Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives containing carbohydrate syrups; containing sugars; containing sugar alcohols; containing starch hydrolysates
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/17Amino acids, peptides or proteins
    • A23L33/18Peptides; Protein hydrolysates
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    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0003General processes for their isolation or fractionation, e.g. purification or extraction from biomass
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs

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Abstract

The present invention provides a kind of using shrimp and crab shells as the ammonia sugar preparation method of raw material:Include the following steps:The chitin extraction from shrimp and crab shells;With chitin described in hydroxypropylation agent modifier, then the secondary hydrolyzate of chitin is obtained through secondary water solution;Ammonia sugar is obtained after the secondary hydrolyzate of the chitin is concentrated successively, suction filtration and drying.It is of the present invention using shrimp and crab shells as the ammonia sugar preparation method of raw material, the chitin extraction from shrimp and crab shells, to carry out secondary water solution after chitin described in hydroxypropylation agent modifier, increase the water solubility of chitin, to which the macromolecular polysaccharide enhanced in chitin is converted into the percent hydrolysis of ammonia sugar, and then improve the yield for preparing final product ammonia sugar during ammonia sugar using shrimp and crab shells as raw material.

Description

Using shrimp and crab shells as the ammonia sugar preparation method of raw material
Technical field
The present invention relates to ammonia sugar preparing technical fields, and in particular to a kind of using shrimp and crab shells as the ammonia sugar preparation method of raw material.
Background technology
Glucosamine, full name are D- Glucosamines, and abbreviation ammonia sugar is before human body synthesis articular cartilage tissue is important Body.The Bones and joints of human body have one layer of cartilage coating in junction, are the neonychiums in joint, and buffer protection function is played to joint. If cartilage degradation, abrasion lose the protective effect to bone, osteoproliferation, osteoarthritis may result in.Ammonia sugar is joint The core substance of cartilage is considered as so far by medical field, only substance that can prevent, treat bone and joint diseases at all: Specific manifestation is as follows:
Supplement osteotrophy, strong bone, protection and repairing articular cartilage:Ammonia sugar can consumingly stimulate cartilage cell to synthesize people Collagen in body and hyaluronic acid repair the articular cartilage being worn, and can generate new articular cartilage and synovial membrane;
Lubricating joint:Ammonia sugar can promote the secretion of joint fluid, to continuous lubricating joint cartilage surface, reduce abrasion, make pass Save position nimbly and freely;
Arthritis is eliminated, arthralgia is slowed down:Ammonia sugar is " street cleaner " in articular cavity, can not only inhibit non-specific The inflammatory reaction of the factor blocks the development of arthritis, releases pain, and can eliminate and be harmful to enzyme in articular cavity, improves and closes The immunity of section and body.The raising that joint immunity is brought by supplementing ammonia sugar is the important prerequisite for eliminating arthritis.
Chitin is also chitin, is being collectively referred to as chitin and chitosan.It is widely present insects, aquatic shell-fish, Without on spinal animal shell and on Mycophyta cell wall.It is unique existing cation in the nature found so far Type edible fibers, American-European medical field are set to isolating protein, fat, carbohydrate, vitamin, mineral in early 1990s " the 6th element of life " except matter.
Ammonia sugar can be obtained the study found that chitin is hydrolyzed in hydrochloric acid;It is existing in the prior art to utilize chitin system The process of standby ammonia sugar, but due to the intrinsic chemical property of chitin itself, cause chitin degree of hydrolysis in hydrochloric acid not high, from And greatly reduce the yield that ammonia sugar is prepared with chitin.
Invention content
In order to overcome the deficiencies of existing technologies, the present invention provide it is a kind of using shrimp and crab shells as the ammonia sugar preparation method of raw material, greatly The big yield for improving ammonia sugar.
In order to reach above-mentioned purpose, the technical solution adopted by the present invention is as follows:
Using shrimp and crab shells as the ammonia sugar preparation method of raw material, include the following steps:
S1 chitin extractions from shrimp and crab shells;
Then S2 obtains the secondary hydrolyzate of chitin with chitin described in hydroxypropylation agent modifier through secondary water solution;
S3:Ammonia sugar is obtained after the secondary hydrolyzate of the chitin is concentrated successively, suction filtration and drying.
Preferably, the step S1 includes:
S1-1 crushes clean shrimp and crab shells, obtains shrimp and crab shells crushed material;
S1-2 is under ultrasonic wave, by the shrimp and crab shells crushed material successively through acidolysis removing inorganic salts and enzymolysis deproteination matter Afterwards, catabolite is obtained;
The catabolite is carried out centrifugal treating by S1-3, and chitin is obtained after the drying precipitate centrifuged.
Preferably, described crush includes the high pressure crushing carried out successively and Ultrasonic Pulverization;
The high pressure crushes:Clean shrimp and crab shells are crushed into 1-5min in high pressure pulverizer at 1.6-2MPa;
The Ultrasonic Pulverization includes:By the shrimp and crab shells crushed through high pressure in distilled water under the ultrasonic wave of 350-400W into Row Ultrasonic Pulverization 5-8min;
Preferably, the acidolysis includes:Under the ultrasonic wave of 150-200W power, by the shrimp and crab shells crushed material in quality Filter liquor after 10-15min is impregnated in the citric acid solution that percentage concentration is 20-25%, and filter residue is washed with water to neutrality, is obtained To the shrimp and crab shells particle of removing inorganic salts;Preferably, the mass ratio of the shrimp and crab shells crushed material and citric acid solution is:1:1.2- 1.5。
Preferably, the enzymolysis includes:Under the ultrasonic wave of 250-300W power, the shrimp and crab shells particle of inorganic salts will be removed 15-25min is digested in papain under 33-38 degrees Celsius, enzymolysis product is washed with water to neutrality, deproteination is obtained The shrimp and crab shells particle of matter;The shrimp and crab shells particle of the removing inorganic salts and the mass ratio of papain are 90:1-2.
Preferably, in step S1-3, before the drying sediment, oxidative decoloration processing is carried out to it.
Preferably, the oxidative decoloration, which is handled, includes:The sediment is separated into suspension in deionized water, then Oxidant is added into the suspension and oxidation promoter carries out the decolorization;The oxidant is that mass percentage concentration is The hydrogenperoxide steam generator of 10-15%;The oxidation promoter includes that mass ratio is 0.5:The sodium metasilicate and manganese sulfate of 1-1.5;Press body Product ratio:The suspension:Oxidant:Oxidation promoter=1:0.3-0.5:0.1-0.15;
Preferably, the method for modifying of the chitin includes:
a:After the chitin is crushed, under subzero 5-10 degrees Celsius, in the hydrogen-oxygen that mass percentage concentration is 10-15% Change in sodium solution and impregnate 4-6h, then thaws under room temperature, be uniformly mixed to obtain chitin water soluble liquid;The sodium hydroxide is molten The mass ratio of liquid and chitin is 1-2:3-5.
b:Hydroxypropylation reagent will be added in the chitin water soluble liquid, 15-20h is stirred at room temperature, obtains reaction solution, institute State hydroxypropylation reagent include mass ratio be 1:The propylene oxide and bromopropyl alcohol of 1-2;The chitin water soluble liquid and hydroxypropylation The volume ratio of reagent is 2:0.1-0.3;
c:The reaction solution is adjusted into pH to 6-7, it is dry after dialysis removal of impurities, obtain hydroxypropyl modified chitin.
Preferably, the secondary water solution includes:With mass percentage concentration it is the salt acidleach of 20-25% the chitin Bubble is heated with stirring to 90~110 DEG C of heat preservation 1~10h of reflux, then adds activated carbon and is cooled to 65~80 DEG C of heat preservation 30- 50min;
The mass ratio of the chitin and the hydrochloric acid is 1:2-2.5;
The chitin and quality of activated carbon ratio are 80-100:1-5.
Preferably, the step S3 further comprises:
It is stirred in absolute ethyl alcohol injection addition activated carbon after the filtered filtrate concentration of the secondary hydrolyzate of the chitin It mixes mixing, stands after 8-10h successively through filtering and drying, obtain clear crystal powder, as ammonia sugar;
The mass ratio of the secondary hydrolyzate of the chitin, activated carbon and absolute ethyl alcohol is 1:0.1-0.3:2-2.5.
With immediate prior art ratio, technical scheme of the present invention has following advantageous effect:
Using shrimp and crab shells as the ammonia sugar preparation method of raw material, the chitin extraction from shrimp and crab shells is tried the present invention with hydroxypropylation Agent carries out secondary water solution after being modified the chitin, increases the water solubility of chitin, to enhance big point in chitin Sub- polysaccharide conversion is the percent hydrolysis of ammonia sugar, and then improves the final product ammonia sugar during preparing ammonia sugar using shrimp and crab shells as raw material Yield.
The present invention is using shrimp and crab shells as the ammonia sugar preparation method of raw material, from shrimp and crab shells during chitin extraction, first Shrimp and crab shells are carried out high pressure crushing and Ultrasonic Pulverization successively, compared to the prior art, are on the one hand shortened shrimp and crab shells acid subsequently Solution removing inorganic salts and the time for digesting deproteination matter, improve the production efficiency that ammonia sugar is prepared using shrimp and crab shells as raw material;It is another Aspect is using shrimp and crab shells in the ammonia sugar preparation process of raw material, to reduce the dosage of acid hydrolysis solution, enzymolysis liquid and washings, from life For production person's angle, production cost is reduced;For energy-saving and emission-reduction, the generation of technique waste water and waste liquid is reduced, environment is protected Shield contributes.
The present invention aoxidizes it before the drying sediment by the ammonia sugar preparation method of raw material of shrimp and crab shells On the other hand decolorization passes through on the one hand so that the indexs such as appearance luster of chitin of extraction meet the requirement of ammonia sugar preparation The chitin of peroxidating decolorization is easier to be modified with hydroxypropylation reagent, to further improve the ammonia sugar of ammonia sugar Yield.
Specific implementation mode
Technical scheme of the present invention is described further with reference to specific embodiment:
Embodiment 1
Using shrimp and crab shells as the ammonia sugar preparation method of raw material, include the following steps:
S1 chitin extractions from shrimp and crab shells;
S1-1 carries out high pressure crushing successively to clean shrimp and crab shells and Ultrasonic Pulverization crushes, and obtains shrimp and crab shells crushed material;
The high pressure crushes:Clean shrimp and crab shells are crushed into 1min in high pressure pulverizer at 1.6MPa;
The Ultrasonic Pulverization includes:The shrimp and crab shells crushed through high pressure are surpassed in distilled water under the ultrasonic wave of 350W Sound crushes 5min;
S1-2 is under ultrasonic wave, by the shrimp and crab shells crushed material successively through acidolysis removing inorganic salts and enzymolysis deproteination matter Afterwards, catabolite is obtained;
The acidolysis includes:Under the ultrasonic wave of 150W power, it is in mass percentage concentration by the shrimp and crab shells crushed material Filter liquor after immersion 10min in 20% citric acid solution, and filter residue is washed with water to neutrality, obtain the shrimp of removing inorganic salts Crab shell particle;Preferably, the mass ratio of the shrimp and crab shells crushed material and citric acid solution is:1:1.2;
The enzymolysis includes:Under the ultrasonic wave of 250W power, the shrimp and crab shells particle of inorganic salts will be removed in 33 degrees Celsius Under 15min is digested in papain, enzymolysis product is washed with water to neutrality, the shrimp and crab shells particle of deproteination matter is obtained; The shrimp and crab shells particle of the removing inorganic salts and the mass ratio of papain are 90:1;
The catabolite is carried out centrifugal treating by S1-3, and chitin is obtained after the drying precipitate centrifuged;
Then S2 obtains the secondary hydrolyzate of chitin with chitin described in hydroxypropylation agent modifier through secondary water solution;
The method of modifying of chitin described in S2-1 includes:
a:After the chitin is crushed, under subzero 10 degrees Celsius, the sodium hydroxide for being 10% in mass percentage concentration 4h is impregnated in solution, is then thawed under room temperature, and chitin water soluble liquid is uniformly mixed to obtain;The sodium hydroxide solution and first The mass ratio of shell element is 1:3;
b:Hydroxypropylation reagent will be added in the chitin water soluble liquid, 15h is stirred at room temperature, obtains reaction solution, it is described Hydroxypropylation reagent includes that mass ratio is 1:1 propylene oxide and bromopropyl alcohol;The chitin water soluble liquid and hydroxypropylation reagent Volume ratio be 2:0.1;
c:The reaction solution is adjusted into pH to 6, it is dry after dialysis removal of impurities, obtain hydroxypropyl modified chitin;
Secondary water solution described in S2-2 includes:The salt acid soak for being 20% with mass percentage concentration the chitin, stirring 90 DEG C of heat preservation reflux 1h are heated to, activated carbon is then added and is cooled to 65 DEG C of heat preservation 30min;
The mass ratio of the chitin and the hydrochloric acid is 1:2;
The chitin and quality of activated carbon ratio are 80:1;
S3 is concentrated successively the secondary hydrolyzate of the chitin, filters and obtained after dry ammonia sugar, specifically includes:
It is stirred in absolute ethyl alcohol injection addition activated carbon after the filtered filtrate concentration of the secondary hydrolyzate of the chitin It mixes mixing, stands after 8h successively through filtering and drying, obtain clear crystal powder, as ammonia sugar;
The mass ratio of the secondary hydrolyzate of the chitin, activated carbon and absolute ethyl alcohol is 1:0.1:2.
Embodiment 2
Using shrimp and crab shells as the ammonia sugar preparation method of raw material, include the following steps:
S1 chitin extractions from shrimp and crab shells;
Clean shrimp and crab shells are carried out high pressure crushing and Ultrasonic Pulverization by S1-1 successively, obtain shrimp and crab shells crushed material;
The high pressure crushes:Clean shrimp and crab shells are crushed into 5min in high pressure pulverizer at 2MPa;
The Ultrasonic Pulverization includes:The shrimp and crab shells crushed through high pressure are surpassed in distilled water under the ultrasonic wave of 400W Sound crushes 8min;
S1-2 is under ultrasonic wave, by the shrimp and crab shells crushed material successively through acidolysis removing inorganic salts and enzymolysis deproteination matter Afterwards, catabolite is obtained;
The acidolysis includes:Under the ultrasonic wave of 200W power, it is in mass percentage concentration by the shrimp and crab shells crushed material Filter liquor after immersion 15min in 25% citric acid solution, and filter residue is washed with water to neutrality, obtain the shrimp of removing inorganic salts Crab shell particle;The mass ratio of the shrimp and crab shells crushed material and citric acid solution is:1:1.5;
The enzymolysis includes:Under the ultrasonic wave of 300W power, the shrimp and crab shells particle of inorganic salts will be removed in 38 degrees Celsius Under 25min is digested in papain, enzymolysis product is washed with water to neutrality, the shrimp and crab shells particle of deproteination matter is obtained; The shrimp and crab shells particle of the removing inorganic salts and the mass ratio of papain are 90:2;
The catabolite is carried out centrifugal treating by S1-3, and chitin is obtained after the drying precipitate centrifuged;
Then S2 obtains the secondary hydrolyzate of chitin with chitin described in hydroxypropylation agent modifier through secondary water solution;
The method of modifying of chitin described in S2-1 includes:
a:After the chitin is crushed, under subzero 5 degrees Celsius, the sodium hydroxide for being 15% in mass percentage concentration is molten 6h is impregnated in liquid, is then thawed under room temperature, and chitin water soluble liquid is uniformly mixed to obtain;The sodium hydroxide solution and crust The mass ratio of element is 2:3;
b:Hydroxypropylation reagent will be added in the chitin water soluble liquid, 20h is stirred at room temperature, obtains reaction solution, it is described Hydroxypropylation reagent includes that mass ratio is 1:2 propylene oxide and bromopropyl alcohol;The chitin water soluble liquid and hydroxypropylation reagent Volume ratio be 2:0.3;
c:The reaction solution is adjusted into pH to 7, it is dry after dialysis removal of impurities, obtain hydroxypropyl modified chitin;
Secondary water solution described in S2-2 includes:The salt acid soak for being 25% with mass percentage concentration the chitin, stirring 110 DEG C of heat preservation reflux 10h are heated to, activated carbon is then added and is cooled to 80 DEG C of heat preservation 50min;
The mass ratio of the chitin and the hydrochloric acid is 2-2.5;
The chitin and quality of activated carbon ratio are 100:5;
S3:Ammonia sugar is obtained after the secondary hydrolyzate of the chitin is concentrated successively, suction filtration and drying, is specifically included:
It is stirred in absolute ethyl alcohol injection addition activated carbon after the filtered filtrate concentration of the secondary hydrolyzate of the chitin It mixes mixing, stands after 10h successively through filtering and drying, obtain clear crystal powder, as ammonia sugar;
The mass ratio of the secondary hydrolyzate of the chitin, activated carbon and absolute ethyl alcohol is 1:0.3:2.5.
Embodiment 3
Using shrimp and crab shells as the ammonia sugar preparation method of raw material, include the following steps:
S1 chitin extractions from shrimp and crab shells;
Clean shrimp and crab shells are carried out high pressure crushing and Ultrasonic Pulverization by S1-1 successively, obtain shrimp and crab shells crushed material;
The high pressure crushes:Clean shrimp and crab shells are crushed into 3min in high pressure pulverizer at 1.8MPa;
The Ultrasonic Pulverization includes:The shrimp and crab shells crushed through high pressure are surpassed in distilled water under the ultrasonic wave of 380W Sound crushes 6min;
S1-2 is under ultrasonic wave, by the shrimp and crab shells crushed material successively through acidolysis removing inorganic salts and enzymolysis deproteination matter Afterwards, catabolite is obtained;
The acidolysis includes:Under the ultrasonic wave of 175W power, it is in mass percentage concentration by the shrimp and crab shells crushed material Filter liquor after immersion 13min in 22% citric acid solution, and filter residue is washed with water to neutrality, obtain the shrimp of removing inorganic salts Crab shell particle;The mass ratio of the shrimp and crab shells crushed material and citric acid solution is:1:1.3;
The enzymolysis includes:Under the ultrasonic wave of 280 power, the shrimp and crab shells particle of inorganic salts will be removed under 35 degrees Celsius 20min is digested in papain, enzymolysis product is washed with water to neutrality, obtains the shrimp and crab shells particle of deproteination matter;Institute The mass ratio of the shrimp and crab shells particle and papain of stating removing inorganic salts is 90:1.5;
The catabolite is carried out centrifugal treating by S1-3, and chitin is obtained after the drying precipitate centrifuged;
Then S2 obtains the secondary hydrolyzate of chitin with chitin described in hydroxypropylation agent modifier through secondary water solution;
The method of modifying of chitin described in S2-1 includes:
a:After the chitin is crushed, under subzero 7 degrees Celsius, the sodium hydroxide for being 12% in mass percentage concentration is molten 5h is impregnated in liquid, is then thawed under room temperature, and chitin water soluble liquid is uniformly mixed to obtain;The sodium hydroxide solution and crust The mass ratio of element is 1.5:4;
b:Hydroxypropylation reagent will be added in the chitin water soluble liquid, 18h is stirred at room temperature, obtains reaction solution, it is described Hydroxypropylation reagent includes that mass ratio is 1:1.5 propylene oxide and bromopropyl alcohol;The chitin water soluble liquid and hydroxypropylation examination The volume ratio of agent is 2:0.2;
c:The reaction solution is adjusted into pH to 6.5, it is dry after dialysis removal of impurities, obtain hydroxypropyl modified chitin;
Secondary water solution described in S2-2 includes:The salt acid soak for being 23% with mass percentage concentration the chitin, stirring 100 DEG C of heat preservation reflux 5h are heated to, activated carbon is then added and is cooled to 75 DEG C of heat preservation 40min;
The mass ratio of the chitin and the hydrochloric acid is 1.5-2.5;
The chitin and quality of activated carbon ratio are 90:3;
S3:Ammonia sugar is obtained after the secondary hydrolyzate of the chitin is concentrated successively, suction filtration and drying, is specifically included:
It is stirred in absolute ethyl alcohol injection addition activated carbon after the filtered filtrate concentration of the secondary hydrolyzate of the chitin It mixes mixing, stands after 9h successively through filtering and drying, obtain clear crystal powder, as ammonia sugar;
The mass ratio of the secondary hydrolyzate of the chitin, activated carbon and absolute ethyl alcohol is 1:0.2:2.3.
Embodiment 4
The present embodiment 4 is on the basis of embodiment 1-3, in step S1-3, before the drying sediment, to its into The processing of row oxidative decoloration;
The oxidative decoloration is handled:The sediment is separated into suspension in deionized water, then to described Oxidant is added in suspension and oxidation promoter carries out the decolorization;The oxidant is that mass percentage concentration is 10- 15% hydrogenperoxide steam generator;The oxidation promoter includes that mass ratio is 0.5:The sodium metasilicate and manganese sulfate of 1-1.5;By volume Than:The suspension:Oxidant:Oxidation promoter=1:0.3-0.5:0.1-0.15.
The ammonia sugar preparation method of embodiment 1-4 and the comparison of existing ammonia sugar preparation method technological parameter are as follows:
Table 1:
The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, although with reference to above-described embodiment pair The present invention is described in detail, those of ordinary skill in the art still can to the present invention specific implementation mode into Row modification either equivalent replacement these without departing from any modification of spirit and scope of the invention or equivalent replacement, applying Within the claims of the pending present invention.

Claims (10)

1. using shrimp and crab shells as the ammonia sugar preparation method of raw material, which is characterized in that include the following steps:
S1 chitin extractions from shrimp and crab shells;
Then S2 obtains the secondary hydrolyzate of chitin with chitin described in hydroxypropylation agent modifier through secondary water solution;
S3:Ammonia sugar is obtained after the secondary hydrolyzate of the chitin is concentrated successively, suction filtration and drying.
2. as described in claim 1 using shrimp and crab shells as the ammonia sugar preparation method of raw material, which is characterized in that the step S1 packets It includes:
S1-1 crushes clean shrimp and crab shells, obtains shrimp and crab shells crushed material;
S1-2, by the shrimp and crab shells crushed material successively through acidolysis removing inorganic salts and enzymolysis deproteination matter, is obtained under ultrasonic wave Catabolite;
The catabolite is carried out centrifugal treating by S1-3, and chitin is obtained after the drying precipitate centrifuged.
3. as claimed in claim 2 using shrimp and crab shells as the ammonia sugar preparation method of raw material, which is characterized in that it is described crushing include according to The high pressure of secondary progress crushes and Ultrasonic Pulverization;
The high pressure crushes:Clean shrimp and crab shells are crushed into 1-5min in high pressure pulverizer at 1.6-2MPa;
The Ultrasonic Pulverization includes:The shrimp and crab shells crushed through high pressure are surpassed in distilled water under the ultrasonic wave of 350-400W Sound crushes 5-8min.
4. as claimed in claim 2 using shrimp and crab shells as the ammonia sugar preparation method of raw material, which is characterized in that the acidolysis includes: It is under the ultrasonic wave of 150-200W power, the shrimp and crab shells crushed material is molten in the citric acid that mass percentage concentration is 20-25% Filter liquor after immersion 10-15min in liquid, and filter residue is washed till neutrality, obtain the shrimp and crab shells particle of removing inorganic salts.
5. as claimed in claim 4 using shrimp and crab shells as the ammonia sugar preparation method of raw material, which is characterized in that the enzymolysis includes: Under the ultrasonic wave of 250-300W power, the shrimp and crab shells particles of inorganic salts will be removed under 33-38 degrees Celsius in papain Middle enzymolysis 15-25min, neutrality is washed till by enzymolysis product, obtains the shrimp and crab shells particle of deproteination matter.
6. as claimed in claim 2 using shrimp and crab shells as the ammonia sugar preparation method of raw material, which is characterized in that in step S1-3, Before the dry sediment, oxidative decoloration processing is carried out to it.
7. as claimed in claim 6 using shrimp and crab shells as the ammonia sugar preparation method of raw material, which is characterized in that at the oxidative decoloration Reason includes:The sediment is separated into suspension in deionized water, oxidant and oxygen are then added into the suspension Change auxiliary agent and carries out the decolorization;The oxidant is the hydrogenperoxide steam generator that mass percentage concentration is 10-15%;The oxygen Change auxiliary agent includes that mass ratio is 0.5:The sodium metasilicate and manganese sulfate of 1-1.5.
8. as described in claim 2 or 6 using shrimp and crab shells as the ammonia sugar preparation method of raw material, which is characterized in that the chitin Method of modifying include:
a:After the chitin is crushed, under subzero 5-10 degrees Celsius, in the sodium hydroxide that mass percentage concentration is 10-15% 4-6h is impregnated in solution, is then thawed under room temperature, and chitin water soluble liquid is uniformly mixed to obtain;
b:Hydroxypropylation reagent will be added in the chitin water soluble liquid, 15-20h is stirred at room temperature, obtains reaction solution;
c:The reaction solution is adjusted into pH to 6-7, it is dry after dialysis removal of impurities, obtain hydroxypropyl modified chitin.
9. as claimed in claim 8 using shrimp and crab shells as the ammonia sugar preparation method of raw material, which is characterized in that the secondary water unpacks It includes:With mass percentage concentration it is the salt acid soak of 20-25% the chitin, is heated with stirring to 90~110 DEG C of heat preservation reflux 1 Then~10h adds activated carbon and is cooled to 65~80 DEG C of heat preservation 30-50min;
The mass ratio of the chitin and the hydrochloric acid is 1:2-2.5;
The chitin and quality of activated carbon ratio are 80-100:1-5.
10. as claimed in claim 9 using shrimp and crab shells as the ammonia sugar preparation method of raw material, which is characterized in that the step S3 into One step includes:
It is stirred in absolute ethyl alcohol injection addition activated carbon after the filtered filtrate concentration of the secondary hydrolyzate of the chitin mixed It is even, after standing 8-10h clear crystal powder, as ammonia sugar are obtained through filtering and drying successively.
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WO2019179148A1 (en) * 2018-03-19 2019-09-26 扬州日兴生物科技股份有限公司 Method for preparing glucosamine by using shrimp and crab shells as raw materials
CN111227026A (en) * 2020-03-09 2020-06-05 中国海洋大学 Method for preparing meat preservative film by using shrimp and crab shells

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