CN111662396A - Method for recovering chitin from waste fish scale crab and shrimp shells - Google Patents
Method for recovering chitin from waste fish scale crab and shrimp shells Download PDFInfo
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- CN111662396A CN111662396A CN202010715017.0A CN202010715017A CN111662396A CN 111662396 A CN111662396 A CN 111662396A CN 202010715017 A CN202010715017 A CN 202010715017A CN 111662396 A CN111662396 A CN 111662396A
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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
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
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- C—CHEMISTRY; METALLURGY
- 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 method for recovering chitin from waste fish scale crab and shrimp shells, which comprises the following steps: (1) washing, airing and crushing fish scales, shrimp and crab shells, putting the fish scales, the shrimp and crab shells into a microwave reactor for microwave heating after adding a shell-crushing alkali solution and a soft soap, then transferring the fish scales and the shrimp and crab shells into an ultrasonic cleaning instrument for continuous ultrasonic treatment, standing and placing the fish scales and the shrimp and crab shells, and fishing out the fish scales and the shells to repeat the steps; (2) fishing out the shell soaked in the twice microwave ultrasonic reactions, filtering by using gauze, draining after washing to be neutral, adding a hydrochloric acid solution, continuously carrying out ultrasonic reaction in an ultrasonic cleaner for 15 minutes, fishing out the shell, continuously carrying out ultrasonic reaction in the hydrochloric acid solution ultrasonic cleaner for 10 minutes, filtering by using the gauze, washing to be neutral, and carrying out suction filtration to remove water; (3) adding 4 times of anhydrous ethanol into a target chitin crude product, heating and refluxing for 1 hour, filtering, rinsing a filter cake with clear water, adding 1 per mill of potassium permanganate solution, soaking for 1 hour, filtering, soaking the filter cake with 1% sodium bisulfite solution for 1 hour to obtain a milky semitransparent chitin wet product, and drying in the sun.
Description
Technical Field
The invention relates to the technical field of chitin recycling, in particular to a method for recycling chitin from waste fish scale crab and shrimp shells.
Background
Chitin is a new material in the 21 st century, and has a great effect on the development and progress of the human society. Has wide application in the fields of industry, agriculture, medicine, cosmetics, environmental protection, water treatment and the like. The mussel port area has extensive resources for extracting chitin, but for a long time, the chitin cannot be effectively utilized, and the environment is greatly polluted. The artificial extraction work of chitin is developed from the purposes of utilizing resources and reducing environmental pollution, so that the novel chitin resources in inland province are developed, waste is changed into valuable, and a stable raw material source is provided for the production of chitin derivatives. The subject group has strong interest in chitin and strong consciousness on environmental protection, and can change chitin into valuable, reduce resource waste and protect the environment.
The preparation and extraction of chitin generally have the advantages of high product quality of acid-base method, enzymolysis method, microbial fermentation method and ionic liquid method, but high cost, and are not suitable for industrial mass production at present; the intensified normal pressure plasma method needs to further examine the problems of energy consumption and chitin yield and quality; the EDTA method and the hot glycerol pretreatment method have simple steps, little pollution and better development prospect, and can even replace the position of the acid-base method in industrial production. The main operations for preparing chitin are as follows: decalcification and deproteinization. The traditional process for preparing chitin comprises the following steps: (1) the function of the acid is decalcification, namely that calcium carbonate and inorganic salt in the shrimp and crab shells are changed into water-soluble solution, carbon dioxide and the like when the shrimp and crab shells are soaked. (2) The action of the alkali is deproteinization, since the protein dissolves faster and more completely in the alkaline solution than in the acid solution. (3) The rest is chitin.
Disclosure of Invention
The invention aims to provide a method for recovering chitin from waste fish scale crab and shrimp shells, so as to solve the defects in the prior art.
The invention provides a method for recovering chitin from waste fish scale crab and shrimp shells, which comprises the following steps:
(1) washing, airing and crushing fish scales, shrimp and crab shells, putting the fish scales, the shrimp and crab shells into a microwave reactor for microwave heating after adding a shell-crushing alkali solution and a soft soap, then transferring the fish scales and the shrimp and crab shells into an ultrasonic cleaning instrument for continuous ultrasonic treatment, standing and placing the fish scales and the shrimp and crab shells, and fishing out the fish scales and the shells to repeat the steps;
(2) taking out the shell soaked by the microwave ultrasonic reaction twice, filtering by using gauze, washing by using water until the shell is neutral, draining, adding a hydrochloric acid solution, continuously carrying out ultrasonic reaction in an ultrasonic cleaner for 15 minutes, taking out the shell, continuously carrying out ultrasonic reaction in the hydrochloric acid solution ultrasonic cleaner for 10 minutes, filtering by using the gauze, washing by using water until the shell is neutral, carrying out suction filtration to remove water, and drying in the sun to obtain a target crude product;
(3) adding 4 times of anhydrous ethanol into a target chitin crude product, heating and refluxing for 1 hour, filtering, rinsing a filter cake with clear water, adding 1 per mill of potassium permanganate solution (1:2), soaking for 1 hour, filtering, soaking the filter cake with 1% sodium bisulfite solution (1:2) for 1 hour to obtain a milky white semitransparent chitin wet product, and drying in the sun to obtain an off-white chitin dried product.
Preferably, the alkali solution in the step (1) is NaOH or KOH, and the concentration is 5 mol/L.
Preferably, 400ml of the alkali solution is used in the first treatment in step (1).
Preferably, the amount of the alkali solution used in the second treatment in step (1) is 300 ml.
Preferably, the two microwave heating temperatures in the step (1) are both 80 ℃, the first microwave heating time is 15min, and the second microwave heating time is 10 min.
Preferably, the standing time in step (1) is 30 min.
Preferably, the hydrochloric acid solution concentration in the step (2) is 2mol/L, the hydrochloric acid solution used for the first ultrasonic cleaning is 500ml, and the hydrochloric acid solution used for the second ultrasonic cleaning is 300 ml.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses sodium hydroxide solution to soak broken and cleaned fly maggot shells for deproteinization, uses potassium permanganate solution to soak for discoloring, uses oxalic acid or sodium bisulfite solution to soak for demanganization, uses superior pure hydrochloric acid solution to soak for purification, uses ultrapure water to wash until no chloride ion exists, and is dried to prepare the fly maggot shell detergent. The temperature of the whole process is kept between 30 and 90 ℃. The process is simple; the waste liquid is less, and the waste liquid can be recycled or regenerated. The purity of the prepared chitin is as high as 99-99.9%, the ash content is lower than 0.1%, the raw materials are convenient to collect, and the source is stable.
Drawings
Fig. 1 is an SEM image of chitin prepared by the method of the embodiment of the present invention;
FIG. 2 is an infrared spectrum of chitin prepared by the method of the embodiment of the invention;
FIG. 3 is an infrared spectrum of commercial chitin.
Detailed Description
The embodiments described below with reference to the drawings are illustrative only and should not be construed as limiting the invention.
A method for recovering chitin from waste fish scale crab and shrimp shells comprises the following steps:
(1) washing, airing and crushing fish scales, shrimp and crab shells, putting the fish scales, the shrimp and crab shells into a microwave reactor for microwave heating after adding a shell-crushing alkali solution and a soft soap, then transferring the fish scales and the shrimp and crab shells into an ultrasonic cleaning instrument for continuous ultrasonic treatment, standing and placing the fish scales and the shrimp and crab shells, and fishing out the fish scales and the shells to repeat the steps;
(2) taking out the shell soaked by the microwave ultrasonic reaction twice, filtering by using gauze, washing by using water until the shell is neutral, draining, adding a hydrochloric acid solution, continuously carrying out ultrasonic reaction in an ultrasonic cleaner for 15 minutes, taking out the shell, continuously carrying out ultrasonic reaction in the hydrochloric acid solution ultrasonic cleaner for 10 minutes, filtering by using the gauze, washing by using water until the shell is neutral, carrying out suction filtration to remove water, and drying in the sun to obtain a target crude product;
(3) adding 4 times of anhydrous ethanol into a target chitin crude product, heating and refluxing for 1 hour, filtering, rinsing a filter cake with clear water, adding 1 per mill of potassium permanganate solution (1:2), soaking for 1 hour, filtering, soaking the filter cake with 1% sodium bisulfite solution (1:2) for 1 hour to obtain a milky white semitransparent chitin wet product, and drying in the sun to obtain an off-white chitin dried product.
The alkali solution in the step (1) is NaOH or KOH, and the concentration is 5 mol/L.
400ml of alkaline solution is used in the first treatment in step (1).
The amount of the alkali solution used in the second treatment in step (1) was 300 ml.
In the step (1), the two microwave heating temperatures are both 80 ℃, the first microwave heating time is 15min, and the second microwave heating time is 10 min.
The standing time in the step (1) is 30 min.
In the step (2), the concentration of the hydrochloric acid solution is 2mol/L, the hydrochloric acid solution used for the first ultrasonic cleaning is 500ml, and the hydrochloric acid solution used for the second ultrasonic cleaning is 300 ml.
The embodiment of the invention comprises the following steps:
a method for recovering chitin from waste fish scale crab and shrimp shells comprises the following steps:
(1) washing, airing and crushing fish scales, shrimp and crab shells, weighing 200g of crushed shells, adding 400ml of 5mol/L sodium hydroxide solution and 12g of soft soap, placing the mixture into a microwave reactor, heating at 80 ℃ for 15 minutes, transferring the mixture into an ultrasonic cleaner, carrying out ultrasonic treatment for 15 minutes, stopping ultrasonic treatment, and standing for 30 minutes;
(2) taking out the shell soaked by the two microwave ultrasonic reactions, filtering the shell by gauze, washing the shell to be neutral by water, slightly draining the shell, adding 500ml of 2mol/L hydrochloric acid solution, continuously carrying out ultrasonic reaction in an ultrasonic cleaning instrument for 15 minutes, taking out the shell, continuously carrying out ultrasonic reaction in the ultrasonic cleaning instrument for 10 minutes by using 300ml of 2mol/L hydrochloric acid solution, filtering the shell by gauze, washing the shell to be neutral by a large amount of water, carrying out suction filtration to remove water, and drying the shell in the sun to obtain the target crude product.
(3) Adding 4 times of anhydrous ethanol into a target chitin crude product, heating and refluxing for 1 hour, filtering, rinsing a filter cake with clear water, adding 1 per mill of potassium permanganate solution (1:2), soaking for 1 hour, filtering, soaking the filter cake with 1% sodium bisulfite solution (1:2) for 1 hour to obtain a milky white semitransparent chitin wet product, and drying in the sun to obtain an off-white chitin dried product.
The yield of the chitin target crude product prepared by the embodiment is calculated by coarse crushing and cleaning shells (dry products), and is 30 percent on average.
As shown in figure 1, it is easy to find from SEM scanning picture that the chitin is rapidly recovered and extracted from the waste fish scale crab and shrimp shells by microwave-ultrasonic assisted solvent method and is amplified by 20,000 times, the microstructure of the chitin is clear and visible, some reticular sheet structures exist, the length is concentrated on about 400nm, the chitin is not difficult to be found in comparison with the reported literature data, no black spot exists in the whole visual field, no impurity exists, and the chitin extracted by the method is high in quality.
And (3) product quality analysis: the molecular characteristics of fish scale, shrimp and crab shell extracts and complete deproteinization and desalination need to be considered.
Infrared absorption spectrum analysis: as shown in fig. 2 and fig. 3, the fish scale, the crab shell extract and the commercial chitin are taken, infrared absorption spectra are respectively drawn by using a KBr tabletting method, and the characteristic absorption is compared, so that the spectra of the fish scale, the crab shell extract and the commercial chitin are consistent, and the molecular group characteristics of the chitin extracted from the crab shell are proved to be consistent with those of a reference substance. The characteristic absorption peaks at 3268, 3106 and 1660cm-1 are more and more obvious, the absorption peak at 663cm-1 also disappears, and the chitin content in the insoluble substances is preliminarily proved to be gradually increased. And carrying out quantitative analysis on the obtained insoluble substances to determine the specific content of the chitin.
The chemical name of chitin is [ (1, 4) -2-acetamido-2-deoxy-beta-D-glucose ], the molecular formula is (C8H13NO5) n, monomers are connected by beta (1 → 4) glycosidic bond, the molecular weight is about 106 generally, and the theoretical nitrogen content is 6.9%. The molecular structure is characterized in that: the oxygen atom connects the sugar ring of each carbon atom to the next sugar ring, with the pendant groups "hanging" from these rings. The chitin has a molecular chemical structure very similar to that of cellulose widely existing in plants, except that hydroxyl (OH) on the second carbon atom of a glucose molecule, which is a single molecule constituting the cellulose, is replaced by acetamido (NHCOCH3), so that the cellulose becomes chitin, and the chitin can be said to be animal fiber in this sense.
Protein examination: 10g of the product is taken, added with 1mol/L sodium hydroxide solution, refluxed, boiled for 3 hours and centrifuged. Taking supernatant liquor and adding a biuret reagent, if the supernatant liquor does not show mauve color, the deproteinization of the process condition can be proved to meet the requirements.
Residue on ignition inspection: 2g of the product is taken and operated according to the item of 'residue on ignition' inspection in the appendix of Chinese pharmacopoeia, and if the residue left is less than 1.71 percent, the product meets the requirement of desalination (mainly calcium carbonate).
The construction, features and functions of the present invention are described in detail in the embodiments illustrated in the drawings, which are only preferred embodiments of the present invention, but the present invention is not limited by the drawings, and all equivalent embodiments modified or changed according to the idea of the present invention should fall within the protection scope of the present invention without departing from the spirit of the present invention covered by the description and the drawings.
Claims (7)
1. A method for recovering chitin from waste fish scale crab and shrimp shells is characterized in that: the method comprises the following steps:
(1) washing, airing and crushing fish scales, shrimp and crab shells, putting the fish scales, the shrimp and crab shells into a microwave reactor for microwave heating after adding a shell-crushing alkali solution and a soft soap, then transferring the fish scales and the shrimp and crab shells into an ultrasonic cleaning instrument for continuous ultrasonic treatment, standing and placing the fish scales and the shrimp and crab shells, and fishing out the fish scales and the shells to repeat the steps;
(2) taking out the shell soaked by the microwave ultrasonic reaction twice, filtering by using gauze, washing by using water until the shell is neutral, draining, adding a hydrochloric acid solution, continuously carrying out ultrasonic reaction in an ultrasonic cleaner for 15 minutes, taking out the shell, continuously carrying out ultrasonic reaction in the hydrochloric acid solution ultrasonic cleaner for 10 minutes, filtering by using the gauze, washing by using water until the shell is neutral, carrying out suction filtration to remove water, and drying in the sun to obtain a target crude product;
(3) adding 4 times of anhydrous ethanol into a target chitin crude product, heating and refluxing for 1 hour, filtering, rinsing a filter cake with clear water, adding 1 per mill of potassium permanganate solution, soaking for 1 hour, filtering, soaking the filter cake with 1% sodium bisulfite solution for 1 hour to obtain a milky translucent chitin wet product, and drying in the sun to obtain an off-white chitin dried product.
2. The method for recovering the chitin from the waste fish scale crab and shrimp shells as claimed in claim 1, wherein: the alkali solution in the step (1) is NaOH or KOH, and the concentration is 5 mol/L.
3. The method for recovering the chitin from the waste fish scale crab and shrimp shells as claimed in claim 1, wherein: 400ml of alkaline solution is used in the first treatment in step (1).
4. The method for recovering the chitin from the waste fish scale crab and shrimp shells as claimed in claim 1, wherein: the amount of the alkali solution used in the second treatment in step (1) was 300 ml.
5. The method for recovering the chitin from the waste fish scale crab and shrimp shells as claimed in claim 1, wherein: in the step (1), the two microwave heating temperatures are both 80 ℃, the first microwave heating time is 15min, and the second microwave heating time is 10 min.
6. The method for recovering the chitin from the waste fish scale crab and shrimp shells as claimed in claim 1, wherein: the standing time in the step (1) is 30 min.
7. The method for recovering the chitin from the waste fish scale crab and shrimp shells as claimed in claim 1, wherein: in the step (2), the concentration of the hydrochloric acid solution is 2mol/L, the hydrochloric acid solution used for the first ultrasonic cleaning is 500ml, and the hydrochloric acid solution used for the second ultrasonic cleaning is 300 ml.
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| CN202010715017.0A CN111662396A (en) | 2020-07-23 | 2020-07-23 | Method for recovering chitin from waste fish scale crab and shrimp shells |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085564A (en) * | 1993-08-20 | 1994-04-20 | 连云港开发区金祥贸易有限公司 | A kind of preparation method of chitin |
| CN1302819A (en) * | 2000-11-08 | 2001-07-11 | 童文斌 | Process for preparing chitin |
| CN104231113A (en) * | 2014-08-26 | 2014-12-24 | 陕西盛迈石油有限公司 | Method for preparing chitin from lobster shells |
| CN105837706A (en) * | 2016-03-23 | 2016-08-10 | 卞毓平 | Extraction method of chitin and chitin product |
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2020
- 2020-07-23 CN CN202010715017.0A patent/CN111662396A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085564A (en) * | 1993-08-20 | 1994-04-20 | 连云港开发区金祥贸易有限公司 | A kind of preparation method of chitin |
| CN1302819A (en) * | 2000-11-08 | 2001-07-11 | 童文斌 | Process for preparing chitin |
| CN104231113A (en) * | 2014-08-26 | 2014-12-24 | 陕西盛迈石油有限公司 | Method for preparing chitin from lobster shells |
| CN105837706A (en) * | 2016-03-23 | 2016-08-10 | 卞毓平 | Extraction method of chitin and chitin product |
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Application publication date: 20200915 |