CN106632729A - Process for extracting chitin from shrimps and crabs - Google Patents
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- CN106632729A CN106632729A CN201611245131.1A CN201611245131A CN106632729A CN 106632729 A CN106632729 A CN 106632729A CN 201611245131 A CN201611245131 A CN 201611245131A CN 106632729 A CN106632729 A CN 106632729A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, 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
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, 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
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Abstract
The invention discloses a process for extracting chitin from shrimps and crabs, comprising the following steps: (1) cleaning: cleaning waste shrimps and crabs with clear water, removing silt and impurities from the surfaces of the shrimp and crab shells; (2) drying: drying and pulverizing the shrimp and crab shells obtained in the step (1) to obtain shrimp and crab shell coarse powder; (3) low-temperature pulverizing: sequentially carrying out low-temperature freezing and low-temperature sublimation drying on the shrimp and crab shell coarse powder obtained in the step (2), and with liquid nitrogen as a grinding medium, carrying out low-temperature pulverizing at -80 to -120 DEG C by using an ultralow-temperature pulverizer; (4) high-pressure homogenizing: adding purified water to the material obtained in the step (3), mixing evenly, then treating the mixture in a high-pressure homogenizer; and (5) acid treatment: adding the material obtained in the step (4) to dilute hydrochloric acid for soaking, washing with water for neutralizing, centrifuging and drying to obtain chitin. According to the process for extracting chitin from shrimps and crabs, black impurities cannot be produced in the middle procedure, and the obtained product is white in color.
Description
Technical field
The present invention relates in marine bioactivity extractive technique field, more particularly to a kind of crab from shrimp chitin extraction work
Skill.
Background technology
Chitin (Chitin), also referred to as chitin, are found, 1823 for 1811 by French scholar Bu Lakenuo (Braconno)
Nian Youou gills (0dier) are extracted from crustacean shell, and are named as CHITIN, and translated name is chitin.Chitin be
The second largest living resources of cellulose are only second in nature quantity, estimate that annual biosynthetic chitin is up to 10,000,000,000 tons,
It is one of organic matter most abundant on the earth, is the inexhaustible living resources of the mankind, is also not to be fully utilized in 20th century
One of natural resources, wherein marine organisms growing amount are up to 1,000,000,000 tons.Chitin has anticancer, suppresses cancer, oncocyte transfer, improves
Body immunity and liver detoxification are acted on.It is particularly suited for the diseases such as diabetes, liver-kidney diseases, hypertension, obesity, is conducive to pre- anti-cancer
Cytopathy and chemoradiation therapy treatment tumor disease.And torpescence on chitin chemistry, do not change with body fluid, with tissue
Do not play foreign body reaction, it is nontoxic, with antithrombotic, it is high temperature-resistant disinfected the features such as.
In nature, arthropod such as shrimp, crab etc. are up to 58-85% containing chitin, and chitin is only second to cellulose
Second largest renewable resource on the earth, shrimp shell, crab shell are the discarded objects in aquatic products processing industry, and yield is huge, and cost is relatively low, contains
Shitosan after having abundant chitin and its deacetylation.There are abundant shrimp, crab resource, the water of many shrimp crabs in Qinzhou Prefecture
The leftover bits and pieces such as shrimp shell, shrimp head, crab shell of the processing producer after processing shrimp crab are produced, it is difficult to process, because wherein containing abundant albumen
Matter, fat, after accumulation easily fermentation, it is spoiled, rise it is mould, affect environment.
But prepare chitin using shrimp, crab shell and there is also some problems that can not be ignored, one is except some large-scale seas
Outside Product processing enterprise, shrimp, crab shell are difficult concentric acquisition, general eating at home or hotel it is edible after abandoned as rubbish and
It is difficult to reclaim；Two is that shrimp, crab shell are contained within the commensals such as substantial amounts of protein and fat, pre-processes cumbersome, is processed unnet
Or be not completely dried, matter of going mouldy easily is acted during preservation.Just because of such some reasons, it is subject to shrimp, making full use of for crab shell
Great restriction.Chinese patent CN103936884A, a kind of method of the chitin extraction from shrimp and crab shells, is the conjunction of applicant
Make the earlier application of partner, the method, although the chitin content for obtaining is high, but yield low (less than 20%), and
Color and luster is white or canescence, not ideal enough above color and luster.If can after treatment apply shrimp and crab shells, can realize giving up
The efficient utilization of gurry and maximum resource utilization is made, produce huge economic and social benefit.Resource circulation utilization and ecology
Energy environment protection is the target of China's Long-and Medium-term Development most important thing.
The content of the invention
The invention provides in a kind of crab from shrimp chitin extraction technique, high income, intermediate step is not in black
Impurity, the product color for obtaining is pure white.
The present invention is achieved through the following technical solutions：
The technique of chitin extraction, comprises the steps in a kind of crab from shrimp:
1) washing：Discarded shrimp and crab shells are cleaned with clear water, the silt and impurity on shrimp and crab shells surface is removed；
2) it is dried：By step 1) drying of the shrimp and crab shells that obtain, crush to obtain shrimp and crab shells meal；
3) low-temperature grinding：By step 2) the shrimp and crab shells meal that obtains, carry out cryogenic freezing successively and after low-temperature distillation is dried
With liquid nitrogen as abrasive media, low-temperature grinding is carried out with super-low temperature pulverizator at -80--120 DEG C；
4) it is high-pressure homogeneous：By step 3) material that obtains adds pure water to be well mixed, it is subsequently adding at high pressure homogenizer
Reason；
5) acid treatment：To step 4) material that obtains, watery hydrochloric acid immersion is added, neutrality is washed to, it is centrifuged, obtain after being dried
Chitin.
Step 1 of the present invention) described in crab shrimp shell, with arbitrary proportion mixing.
Step 2) described in crushing, preferably granularity is crushed in 80-100 mesh with ball mill.
Step 3) described in cryogenic freezing, preferable temperature 0--18 DEG C, more preferably -10--18 DEG C.
Step 4) described in it is high-pressure homogeneous, the pure water for being preferably added to 5-6 times of weight is well mixed, and is subsequently adding high pressure equal
The process of matter machine, 10000-15000psi, 5-10min.
Step 5) described in addition watery hydrochloric acid immersion, be preferably added to the watery hydrochloric acid of 1mol/L of 3-5 times of weight at room temperature
Immersion 0.5-1.0h；Described centrifugation, preferred 1500r/min, 10min.
Compared with prior art, advantages of the present invention：
1st, the chitin extraction from shrimp and crab shells, prior art is usually crushed to shrimp and crab shells after 20-60 mesh, directly adds
Hot extraction, ultrasonication, microwave treatment etc., are either separated or deproteination using enzymolysis, lactobacillus-fermented, but so
Place comprehend generation protein suspension and black impurity (protein suspension can adhering device inwall, affect production, it is and black
Colored foreign can affect finished product color and luster), then again with diluted alkaline deproteinising, degreasing, (acid-base neutralization can cause grease and alkali to occur
Saponification, makes liquid turns turbid), in order to color and luster is pure white, what is had can also be decolourized with liquor potassic permanganate, although color and luster is had
Improve, but have black impurity presence, and, whole operation needs multiple times of filtration, washing, causes production to waste.And this
Invention is by carrying out low-temperature grinding, high-pressure homogeneous process to shrimp and crab shells meal, it is to avoid more than loaded down with trivial details technique, directly destroy egg
White matter, fat, then with acid treatment, intermediate step is not in black impurity, and the product color for obtaining is pure white.
2nd, freeze grinding technology, because the price of refrigerant is higher, is restricted, the now in actual industrial production
Succeeded using useless cold liquid nitrogen of producing during natural gas gasifying, liquid nitrogen prices, freeze grinding technology is just developed, but
The technology application shrimp and crab shells chitin extraction has no report.Ultralow temperature crushing technology is present invention employs, shrimp and crab shells are entered successively
Row cryogenic freezing, low-temperature distillation be dried after with liquid nitrogen as abrasive media, carry out with super-low temperature pulverizator at -80-120 DEG C low
Temperature is crushed, and using low temperature brittleness characteristic, can crush the material for being difficult to crush in thermal sensitivity or normal temperature, prevents rotten when crushing.
3rd, the present invention processes the shrimp and crab shells raw material for obtaining using high pressure homogenization method, not using adventitious solvent, by high pressure
Material can be directly crushed to the powerful shearing force and impulsive force that homogeneous method is produced cellular level, inorganic by what is contained in shrimp and crab shells
Matter and organic matter are crushed, and beneficial to the reaction with watery hydrochloric acid, the group of protein, fat, pigment can also be destroyed, beneficial to chitin
Dissolution.
Specific embodiment
Below with embodiment, the invention will be further described, but the invention is not limited in these embodiments.
Embodiment 1：
The technique of chitin extraction, comprises the steps in a kind of crab from shrimp:
1) washing：Discarded shrimp and crab shells are cleaned with clear water, the silt and impurity on shrimp and crab shells surface is removed；
2) it is dried：By step 1) the shrimp and crab shells 10kg that obtains drying, granularity is crushed to ball mill obtains shrimp and crab shells in 80 mesh
Meal；
3) low-temperature grinding：By step 2) the shrimp and crab shells meal that obtains, 0 DEG C of cryogenic freezing is carried out successively and low-temperature distillation is dried
Afterwards with liquid nitrogen as abrasive media, low-temperature grinding is carried out with super-low temperature pulverizator at -80 DEG C；
4) it is high-pressure homogeneous：By step 3) material that obtains adds the pure water of 5 times of weight to be well mixed, and is subsequently adding high pressure
Homogenizer process, 10000psi, 10min；
5) acid treatment：To step 4) material that obtains, the watery hydrochloric acid for adding the 1mol/L of 3 times of weight soaks at room temperature
1.0h, is washed to neutrality, centrifugation, and 1500r/min, 10min obtain chitin 2.53kg, purity 99.28% after being dried.
Embodiment 2：
The technique of chitin extraction, comprises the steps in a kind of crab from shrimp:
1) washing：Discarded shrimp and crab shells are cleaned with clear water, the silt and impurity on shrimp and crab shells surface is removed；
2) it is dried：By step 1) the shrimp and crab shells 10kg that obtains drying, granularity is crushed to ball mill obtains shrimp and crab shells in 100 mesh
Meal；
3) low-temperature grinding：By step 2) the shrimp and crab shells meal that obtains, -10 DEG C of cryogenic freezings are carried out successively and low-temperature distillation is dry
With liquid nitrogen as abrasive media after dry, low-temperature grinding is carried out with super-low temperature pulverizator at -100 DEG C；
4) it is high-pressure homogeneous：By step 3) material that obtains adds the pure water of 6 times of weight to be well mixed, and is subsequently adding high pressure
Homogenizer process, 15000psi, 5min；
5) acid treatment：To step 4) material that obtains, the watery hydrochloric acid for adding the 1mol/L of 4 times of weight soaks at room temperature
1.0h, is washed to neutrality, centrifugation, and 1500r/min, 10min obtain chitin 2.48kg, purity 99.21% after being dried.
Embodiment 3：
The technique of chitin extraction, comprises the steps in a kind of crab from shrimp:
1) washing：Discarded shrimp and crab shells are cleaned with clear water, the silt and impurity on shrimp and crab shells surface is removed；
2) it is dried：By step 1) the shrimp and crab shells 10kg that obtains drying, granularity is crushed to ball mill obtains shrimp and crab shells in 80 mesh
Meal；
3) low-temperature grinding：By step 2) the shrimp and crab shells meal that obtains, -18 DEG C of cryogenic freezings are carried out successively and low-temperature distillation is dry
With liquid nitrogen as abrasive media after dry, low-temperature grinding is carried out with super-low temperature pulverizator at -120 DEG C；
4) it is high-pressure homogeneous：By step 3) material that obtains adds the pure water of 5 times of weight to be well mixed, and is subsequently adding high pressure
Homogenizer process, 15000psi, 10min；
5) acid treatment：To step 4) material that obtains, the watery hydrochloric acid for adding the 1mol/L of 5 times of weight soaks at room temperature
1.0h, is washed to neutrality, centrifugation, and 1500r/min, 10min obtain chitin 2.63kg, purity 99.17% after being dried.
Comparative example 1：
20 mesh -1mol/L watery hydrochloric acid of washing-dry-be crushed to slough mineral matter-washing -2.5mol/L, and dilute caustic soda sloughs egg
White matter, degreasing-chitin crude product -0.7%KMnO4Bleaching-chitin.
10kg shrimp and crab shells obtain chitin 2.08kg, purity 98.11%.
Comparative example 2：
1) washing：Discarded shrimp and crab shells are cleaned with clear water, the silt and impurity on shrimp and crab shells surface is removed；
2) it is dried：By step 1) the shrimp and crab shells 10kg that obtains drying, granularity is crushed to ball mill obtains shrimp and crab shells in 80 mesh
Meal；
3) low-temperature grinding：By step 2) the shrimp and crab shells meal that obtains, -18 DEG C of cryogenic freezings are carried out successively and low-temperature distillation is dry
With liquid nitrogen as abrasive media after dry, low-temperature grinding is carried out with super-low temperature pulverizator at -120 DEG C；
4) acid treatment：To step 3) material that obtains, the watery hydrochloric acid for adding the 1mol/L of 5 times of weight soaks at room temperature
1.0h, is washed to neutrality, centrifugation, and 1500r/min, 10min obtain chitin 1.92kg, purity 91.33% after being dried.
Comparative example 3：
1) washing：Discarded shrimp and crab shells are cleaned with clear water, the silt and impurity on shrimp and crab shells surface is removed；
2) it is dried：By step 1) the shrimp and crab shells 10kg that obtains drying, granularity is crushed to ball mill obtains shrimp and crab shells in 80 mesh
Meal；
3) it is high-pressure homogeneous：By step 2) material that obtains adds the pure water of 5 times of weight to be well mixed, and is subsequently adding high pressure
Homogenizer process, 15000psi, 10min；
4) acid treatment：To step 3) material that obtains, the watery hydrochloric acid for adding the 1mol/L of 5 times of weight soaks at room temperature
1.0h, is washed to neutrality, centrifugation, and 1500r/min, 10min obtain chitin 1.96kg, purity 92.41% after being dried.
Comparative example 4：
1) Feedstock treating：Rub after 10kg shrimps head and crab shell are cleaned with pure water；
2) ultrasonication：The pure water of 15 times of weight, ultrasonication 15min, effect are added in raw material after rubbing
30 DEG C of temperature, power is 250W, after the completion of filter, collect filter residue；
3) HIGH PRESSURE TREATMENT：The filter residue that step b is obtained, adds pure water, and in 115 DEG C, 150MPa high pressure 30min is kept,
Filter, collect filter residue；
4) acid treatment：Obtain adding the 3.0mol/L hydrochloric acid solutions equivalent to 2 times of quality of filter residue in filter residue to step c, soak
Bubble 1h, is washed to neutrality, is centrifuged, and chitin 1.85kg, content 99.05% are obtained after freeze-drying.
Conclusion：The sample result of embodiment 3 is better than comparative example.
Claims (5)
1. in a kind of crab from shrimp chitin extraction technique, it is characterised in that comprise the steps：
1) washing：Discarded shrimp and crab shells are cleaned with clear water, the silt and impurity on shrimp and crab shells surface is removed；
2) it is dried：By step 1) drying of the shrimp and crab shells that obtain, crush to obtain shrimp and crab shells meal；
3) low-temperature grinding：By step 2) the shrimp and crab shells meal that obtains, carry out cryogenic freezing successively and after low-temperature distillation is dried with liquid
Nitrogen is abrasive media, and low-temperature grinding is carried out with super-low temperature pulverizator at -80--120 DEG C；
4) it is high-pressure homogeneous：By step 3) material that obtains adds pure water to be well mixed, and is subsequently adding high pressure homogenizer process；
5) acid treatment：To step 4) material that obtains, watery hydrochloric acid immersion is added, neutrality is washed to, it is centrifuged, obtain crust after being dried
Element.
2. in a kind of crab from shrimp according to claim 1 chitin extraction technique, it is characterised in that：Step 2) described in
Crush, be that granularity is crushed in 80-100 mesh with ball mill.
3. in a kind of crab from shrimp according to claim 1 chitin extraction technique, it is characterised in that：Step 3) described in
Cryogenic freezing, temperature is 0--18 DEG C.
4. in a kind of crab from shrimp according to claim 1 chitin extraction technique, it is characterised in that：Step 4) described in
It is high-pressure homogeneous, it is that the pure water for adding 5-6 times of weight is well mixed, it is subsequently adding high pressure homogenizer process, 10000-
15000psi、5-10min。
5. in a kind of crab from shrimp according to claim 1 chitin extraction technique, it is characterised in that：Step 5) described in
Add watery hydrochloric acid immersion, be that the watery hydrochloric acid of the 1mol/L for adding 3-5 times of weight soaks at room temperature 0.5-1.0h, it is described from
The heart, 1500r/min, 10min.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107500943A (en) * | 2017-10-17 | 2017-12-22 | 薛炜 | A kind of nutrient solution for increasing growing tomatoes soil fertility |
| CN107573128A (en) * | 2017-10-17 | 2018-01-12 | 薛炜 | Increase the nutrient solution of growing tomatoes soil fertility |
| CN109160958A (en) * | 2018-08-07 | 2019-01-08 | 东山县吉兴水产加工有限公司 | A kind of technique of the chitin extraction from shrimp crab |
| CN113088045A (en) * | 2021-03-16 | 2021-07-09 | 晋江市新迪新材料科技有限公司 | Shrimp shell-based powder modified fully-degradable composite material |
| CN116478311A (en) * | 2022-11-25 | 2023-07-25 | 湖北工业大学 | Method for extracting chitin by using shrimp and crab shells as raw materials |
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| 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 |
| CN104725530A (en) * | 2014-09-11 | 2015-06-24 | 迪沙药业集团有限公司 | Preparation method of O-carboxylated chitin |
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2016
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| JPH08208709A (en) * | 1995-02-04 | 1996-08-13 | Nippon Kichin Kitosan Kk | Method for eliminating bitter taste from chitosan |
| 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 |
| CN104725530A (en) * | 2014-09-11 | 2015-06-24 | 迪沙药业集团有限公司 | Preparation method of O-carboxylated chitin |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107500943A (en) * | 2017-10-17 | 2017-12-22 | 薛炜 | A kind of nutrient solution for increasing growing tomatoes soil fertility |
| CN107573128A (en) * | 2017-10-17 | 2018-01-12 | 薛炜 | Increase the nutrient solution of growing tomatoes soil fertility |
| CN109160958A (en) * | 2018-08-07 | 2019-01-08 | 东山县吉兴水产加工有限公司 | A kind of technique of the chitin extraction from shrimp crab |
| CN113088045A (en) * | 2021-03-16 | 2021-07-09 | 晋江市新迪新材料科技有限公司 | Shrimp shell-based powder modified fully-degradable composite material |
| CN113088045B (en) * | 2021-03-16 | 2023-03-10 | 晋江市新迪新材料科技有限公司 | Shrimp shell-based powder modified fully-degradable composite material |
| CN116478311A (en) * | 2022-11-25 | 2023-07-25 | 湖北工业大学 | Method for extracting chitin by using shrimp and crab shells as raw materials |
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Application publication date: 20170510 |