CN104788584B - Novel process for cleanly producing chitosan and carboxymethyl chitosan by using crustacean raw materials - Google Patents
Novel process for cleanly producing chitosan and carboxymethyl chitosan by using crustacean raw materials Download PDFInfo
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Abstract
The invention relates to a novel process for cleanly producing chitosan and carboxymethyl chitosan by using crustacean raw materials. After being crushed, the crustacean raw materials such as shrimp shells, crab shells and the like can directly react in an alcohol-alkali-water mixed system without decalcification and deproteinization, and can be washed and filtered to obtain a chitosan crude product containing calcium carbonate for direct use; or directly adding chloroacetic acid to perform carboxymethyl reaction of chitosan, washing the reacted solid, filtering, drying to obtain coarse carboxymethyl chitosan and calcium carbonate mixture, directly using the mixture or dissolving the mixture in water to obtain the product, using the separated calcium carbonate as filler, and using the solution directly or after concentration and drying as product or using alcohol to obtain pure carboxymethyl chitosan. The series crude products or pure products have wide application in the fields of papermaking, adhesives, coatings, slow and controlled release fertilizers and the like. The washed filtrate contains amino acid and small peptide, and can be used as animal amino acid feed raw materials, plant amino acid fertilizer or microorganism nitrogen source nourishment after concentrating and recovering the solvent.
Description
Technical Field
The invention relates to a novel process for cleanly producing chitosan and carboxymethyl chitosan by using a crustacean raw material, belonging to the technical field of biomass utilization and natural product modification.
Background
Chitin (chitin) is the second most renewable resource next to cellulose on earth, widely existing in cell walls of arthropod, mollusk, annelid, protozoan, and fungi and algae, wherein crustacean such as shrimp and crab is rich in chitin 15% -35%, and the biosynthesis amount of chitin is about 1000 hundred million tons per year. The basic unit of chitin is acetylglucosamine, which is a polymer formed by connecting 1000-3000 acetylglucosamine residues through beta- (1 → 4) -glycosidic bonds. Chitosan (chitosan) is a product of N-deacetylation of chitin, and is the only nitrogen-containing basic polysaccharide existing in large amount in nature. The chitin forms a secondary structure of macromolecules due to the existence of intramolecular and intermolecular hydrogen bonds, and simultaneously, the chitin molecules are easy to form crystals due to the regularity of the molecular structure, so that crustacean organisms have hard shells and are difficult to dissolve in water and organic solvents. By low-cost extraction and derivatization of the chitin, a new way can be added for the development of abundant chitin resources and the guarantee of raw materials in the post-petroleum era.
Carboxymethyl chitosan is an important water-soluble chitin derivative, has the functions of thickening, bonding, film forming, moisture absorption, emulsification and the like, and can be used in the fields of cosmetics, medicines, chemical industry, agriculture, paper making and the like. For example, the chitin derivative additive is added into the paper pulp, so that the effects of antibiosis, mould prevention, deodorization and moisture absorption can be achieved, and the functions of crease resistance, static resistance and strength improvement can be achieved; especially for treating the household paper, the paper has soft, plump and comfortable physical properties. However, as the carboxymethyl chitosan does not have an industrial application technology with economic and technical feasibility and product sales so far, the development of a process method for producing the carboxymethyl chitosan, which has high quality, low price, environmental protection, has a great value.
The prior method for preparing carboxymethyl chitosan mostly takes chitosan as a raw material, alkalinizes the chitosan in an organic solvent medium, and then performs carboxymethylation reaction, or takes chitin as a raw material, and deacetylates the chitin in a mixed solution of alkali liquor and an organic solvent and then performs carboxymethylation. The main disadvantages of these methods are:
1) the extraction cost of the raw material chitin is high, dilute acid decalcification is adopted for shrimp and crab shells, and then the shrimp and crab shells are subjected to a long-time boiling deproteinization process by 5-8% alkali liquor, so that the acid and alkali consumption is high, and serious environmental pollution is caused.
2) The chitin is easily degraded in the acid treatment process, and precious biological calcium resources are wasted.
3) The chitosan is obtained by deacetylating chitin in 40-50% concentrated alkali liquor and separating and washing. And the carboxymethyl chitosan is prepared by low-temperature alkalization, so that the process is complex, and the alkali consumption, the energy consumption and the wastewater amount are large.
4) The existing production process of chitin and derivatives thereof can not realize the full utilization of crustacean resources such as shrimp and crab shells, and causes the waste of biological calcium and protein resources and serious environmental pollution, thus causing high production cost and high product price and restricting the development of rich crustacean resources.
Disclosure of Invention
The main components of the crustacean raw materials are calcium carbonate, protein and chitin, and the existing chitin extraction adopts the extraction mode of dissolving calcium carbonate by acid and removing protein by alkali, so that the consumption of acid and alkali is high, the protein and biological calcium are difficult to utilize, and the chitin can be degraded. Therefore, the method proposes that chitosan or carboxymethyl chitosan is prepared by performing derivatization on chitin in an alcohol-alkali-water system by a one-pot method, and simultaneously utilizes calcium carbonate and protein resources.
In order to achieve the purpose, the invention adopts the following technical scheme: pulverizing crustacean raw materials, deacetylating chitin into chitosan in an alcohol-alkali-water mixed system, degrading protein into amino acid and small peptide, washing the reacted solid with water, and filtering to obtain a mixture of chitosan and calcium carbonate; or directly adding chloroacetic acid to perform carboxymethylation on the chitosan after the reaction is finished to obtain the carboxymethyl chitosan. The scheme comprises the following steps:
1) and drying and crushing the shrimp and crab shells into powder of 30-300 meshes for later use.
2) Adding solid alkali into an alcohol-water mixed system, stirring to form white pasty liquid, weighing a certain amount of powder, adding into the mixed solution, heating and stirring to fully deacetylate chitin and fully hydrolyze protein, washing the solid after the reaction is finished, filtering to obtain a mixture of chitosan and calcium carbonate, and recovering amino acids, small peptides and other substances from the filtrate; the reaction can also be directly carried out to the next step.
3) After the chitin is fully deacetylated, monochloroacetic acid is added into the system for 3-7 times, and carboxymethylation reaction of chitosan is carried out under heating.
4) Washing the product with 70% ethanol solution for 3 times, recovering amino acids and small peptides from the filtrate, and recycling the solvent. The solid is dried to obtain the mixture of carboxymethyl chitosan and calcium carbonate for direct use, or the mixture can be dissolved by adding water to separate calcium carbonate precipitate, and the aqueous solution can be directly used or alcohol-separated to obtain the pure carboxymethyl chitosan.
The results of the process optimization show that: the alcohol is selected from isopropanol, ethanol, n-butanol, etc., and the alkali is selected from strong alkali such as sodium hydroxide, potassium hydroxide, etc. The deacetylation reaction temperature of the chitin is room temperature to boiling temperature, and the reaction time is 1-12 h; the carboxymethylation reaction temperature is between room temperature and 70 ℃, and the reaction time is 0.5 to 12 hours. The mass ratio of the alcohol to the raw material (containing 15% of chitin) is 1-5: 1, the mass ratio of the water to the raw material is 0.1-0.5: 1, and the mass ratio of the alkali to the raw material is 0.2-0.5: 1; in the carboxymethylation reaction, the mass ratio of monochloroacetic acid to the raw material is 0.1-0.5: 1.
The invention is reacted in a mixed system of alcohol, alkali and water, and because alcohol molecules have a hydrophobic group with larger volume and only one active hydrogen, hydrogen bonds and pairs OH of the alcohol system-Much weaker solvation than water, OH-The alkalinity and the nucleophilicity of the chitosan complex are larger than those of a water system, the system realizes penetration and attack on a compact crust surface crystallization area, overcomes the shielding effect, enhances the nucleophilic ability to acyl, and realizes the degradation of protein into amino acid and small peptide in a short time and at a low alkali concentration and a low temperature and the reaction of chitosan preparation by chitosan through chitosan deacetylation. Meanwhile, chitosan can be fully swelled and alkalized in an organic system and a strong alkali body, conditions are created for the infiltration of monochloroacetic acid salt molecules and carboxymethylation reaction, the conversion rate of monochloroacetic acid can be improved, and the one-pot reaction is realized.
The protein hydrolysate obtained by filtration and separation is concentrated to recover amino acids and small peptides (see figure 2), and the solvent is recycled. The amino acid and the small peptide can be used for plant fertilizers, microbial nutrient sources, marine organism feed additives and the like, and precious protein resources in crustacean resources are utilized. The biological calcium carbonate can be widely applied as a product component or a raw material, and the crude product or the pure product of the chitosan or the carboxymethyl chitosan is applied to the fields of papermaking, adhesives, sustained and controlled release fertilizers and the like. The new process avoids the large consumption of acid and alkali and the generation of waste water, and realizes energy conservation, consumption reduction and clean production.
Detailed description of the preferred embodiment
1 analysis and preparation of raw materials
The shrimp shell of the prawn is crushed into 30-300 meshes for later use, and the contents of the basic components are as follows: 48% of calcium carbonate, 15% of chitin and 37% of lipid and protein. .
2 deacetylation of chitin
Adding a sodium hydroxide aqueous solution into isopropanol to prepare an isopropanol-alkali-water system, stirring to form a white pasty mixture, weighing a certain amount of powder, adding the powder into the mixed solution, and reacting for 3 hours under stirring to ensure that chitin is fully deacetylated and protein is fully degraded, wherein the experimental content of related process optimization is as follows:
a: different amounts of sodium hydroxide (m)(shrimp shell powder)：m(sodium hydroxide)Effect of = 4: 1, 3.5: 1, 3: 1, 2.5: 1) on deacetylation efficiency of chitin
B: influence of water content (5%, 10%, 15%, 20%) in the system on deacetylation effect of chitin
C: influence of different temperatures (50 ℃, 55 ℃, 60 ℃, 65 ℃) on deacetylation effect of chitin
Carboxymethylation of chitosan
After the reaction is finished, monochloroacetic acid is directly added into the system for 3-7 times to perform carboxymethylation reaction for 3 hours, and the related process experiment contents are as follows:
a: different dosage of monochloroacetic acid (m)(shrimp shell powder)：m(monochloroacetic acid)Effect of = 10: 1, 8: 1, 6: 1, 4: 1) on carboxymethylation effect of chitosan
B: effect of different temperatures (45 ℃, 50 ℃, 55 ℃, 60 ℃) on the carboxymethylation effect of chitosan
4 product analysis
See Table I for relevant inspection and analysis methods of the product
Table one: product analysis item and analysis method
Description of the drawings:
FIG. 1 shows FT-IR spectra of chitin, chitosan and carboxymethyl chitosan
FIG. 2 13C-NMR spectrum of carboxymethyl chitosan waste liquid substance
Detailed Description
The invention is further illustrated by the following examples. The following examples reflect the implementation effects of different conditions of sodium hydroxide, monochloroacetic acid, temperature and water content, the application implementation effects of the product in papermaking, and the like.
Example 1
Adding sodium hydroxide solid into an isopropanol-water mixed system, stirring for a period of time at 60 ℃ to form pasty liquid, weighing shrimp shell powder respectively, adding the shrimp shell powder into the mixed solution, stirring for 3 hours under electric action, fully deacetylating chitin, adding water into the solid, washing to obtain a chitosan-calcium carbonate mixture, dissolving chitosan and calcium carbonate with hydrochloric acid, precipitating with ethanol to obtain chitosan, and repeatedly washing with 70% alcohol-water solution to remove calcium chloride to obtain pure chitosan. The degree of deacetylation was determined by acid-base titration. Different m (shrimp shell meal): the relevant experimental results of m (sodium hydroxide), water content and temperature are shown in the second table, the third table and the fourth table.
Effect of the amount of Epihydroxide on the Deacetyl degree of chitin
Effect of the Water content of Table III on the degree of deacetylation of chitin
Influence of temperature on deacetylation degree of chitin
Example 2
Respectively adding 15g of sodium hydroxide solid into 100ml of isopropanol-water mixed system containing 10% of water, stirring for a period of time at 60 ℃ to form pasty liquid, then respectively weighing 45g of decalcified shrimp shell powder, adding into the mixed solution, and electrically stirring for 3h at 60 ℃ until the chitin is fully deacetylated. And adding monochloroacetic acid for 3-7 times respectively, and performing carboxymethylation on the chitosan for 3 hours. And washing the solid obtained by filtering and separating with 70% ethanol solution to obtain a mixture of carboxymethyl chitosan and calcium carbonate. Dissolving the mixture in water, centrifuging to obtain supernatant, adding 5 times volume of ethanol for precipitation, washing the precipitate with 80% ethanol for three times, drying to obtain pure carboxymethyl chitosan, and measuring carboxylation degree by potentiometric titration. Different m(shrimp shell powder)：m(-chloroacetic acid)And the relevant experimental results at the temperature are shown in the fifth table and the sixth table.
TABLE Effect of the amount of Pentachloroacetic acid on the degree of carboxylation of Chitosan
Influence of apparent six temperatures on Chitosan carboxylation degree
Example 3
Adding 30g of sodium hydroxide solid into 100ml of ethanol-water mixed system containing 10% of water, uniformly stirring, weighing 45g of decalcified shrimp shell powder, adding into the mixed solution, electrically stirring and refluxing for 3h at 80 ℃, and fully deacetylating the chitin. And adding monochloroacetic acid for 3-7 times to perform carboxymethylation on the chitosan for 3 hours. The product was washed with an aqueous alcohol solution and dried to give 28g of a mixture. Adding water to dissolve and precipitate 21g of calcium carbonate, and carrying out reverse precipitation on the solution by using ethanol to obtain 6.8 g of carboxymethyl chitosan. The degree of deacetylation of the carboxymethyl chitosan product was 0.72 and the degree of carboxylation was 0.69.
Example 4
Adding 15g of sodium hydroxide solid into 100ml of isopropanol-water mixed system containing 10% of water, stirring for a period of time at 60 ℃ to form pasty liquid, weighing 45g of decalcified shrimp shell powder, adding into the mixed solution, stirring electrically at 60 ℃ for 3h, and fully deacetylating chitin. And 7.5g of monochloroacetic acid is added for 3-7 times, and carboxymethylation is carried out on the chitosan for 3 hours. The product is washed three times by alcohol water solution and dried to obtain 28.5g of mixture of carboxymethyl chitosan and calcium carbonate, and the yield (calculated by the weight of the shrimp shell) is 63.3 percent. The filtrate was rotary evaporated to remove the alcohol aqueous solution, and the remaining solids containing amino acids, small peptides, etc. were vacuum dried to 33.2g, with a nitrogen content of 4% by elemental analysis. The mixture of calcium carbonate and carboxymethyl chitosan is dissolved in water to precipitate 21g of calcium carbonate, and the yield of calcium carbonate is 97%. The solution is subjected to ethanol reverse precipitation and dried to obtain 7.5g of carboxymethyl chitosan, and the yield is 115 percent (calculated according to the weight of the chitin).
Example 5
Carboxymethyl chitosan (degree of deacetylation 0.82, degree of carboxylation 0.89, 2% viscosity 453mpa.s) was added to the pulp and then papermaking was carried out, and the properties of the paper were measured, and the results are summarized in table seven.
Influence of the addition amount of heptacarboxymethyl chitosan on various properties of paper
Claims (6)
1. A method for cleanly producing chitosan or carboxymethyl chitosan by using crustacean raw materials mainly comprises the following steps: crushing a crustacean raw material into 30-300 meshes, deacetylating chitin into chitosan in an alcohol-alkali-water mixed system, degrading protein into amino acid and small peptide, washing the reacted solid with water, and filtering to obtain a mixture of chitosan and calcium carbonate; or after the reaction is finished, monochloroacetic acid is directly added to carry out carboxymethylation on the chitosan in the solution, and the solid after the reaction is washed and filtered to obtain the mixture of carboxymethyl chitosan and calcium carbonate.
2. The method of claim 1, wherein: the crustacean material is shrimp and crab shell, the alcohol is isopropanol, ethanol or n-butanol, and the alkali is sodium hydroxide or potassium hydroxide.
3. The method of claim 1, wherein the deacetylation reaction temperature of chitin is room temperature to boiling temperature, and the reaction time is 1-12 h in an alcohol-alkali-water system; the carboxymethylation reaction temperature is between room temperature and 70 ℃, and the reaction time is 0.5 to 12 hours.
4. The method according to claim 1, wherein the mass ratio of the alcohol to the raw material is 1-5: 1, the mass ratio of the water to the raw material is 0.1-0.5: 1, and the mass ratio of the alkali to the raw material is 0.2-0.5: 1; in the carboxymethylation reaction, the mass ratio of monochloroacetic acid to the raw materials is 0.1-0.5: 1, and the monochloroacetic acid is added in batches.
5. The method of claim 1, wherein: dissolving the mixture of carboxymethyl chitosan and calcium carbonate in water to separate out calcium carbonate precipitate, and directly using the water solution or precipitating with alcohol.
6. The method as claimed in claim 1, wherein the protein hydrolysate is obtained by filtration and separation, and the amino acids and small peptides are recovered by concentration while the solvent is recycled.
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| CN106581039B (en) * | 2016-11-02 | 2020-01-14 | 上海陶盛生物技术有限公司 | Application of carboxymethyl chitosan in preparing antiallergic product |
| CN107096508B (en) * | 2017-06-28 | 2019-12-06 | 江西省农业科学院土壤肥料与资源环境研究所 | Modified biological crusta heavy metal adsorbent and preparation method and application thereof |
| CN107722138A (en) * | 2017-07-31 | 2018-02-23 | 山东人文置业有限公司 | A kind of chitin prepares the new method of water-soluble carboxymethyl chitosan |
| CN107892371B (en) * | 2017-10-12 | 2020-11-13 | 广州振清环保技术有限公司 | Polysilicate metal and modified chitosan composite coagulant and preparation method thereof |
| CN108940373B (en) * | 2018-07-16 | 2021-07-09 | 广东石油化工学院 | Organic reaction catalyst based on shrimp and crab wastes and preparation method and application thereof |
| CN109796542B (en) * | 2018-12-25 | 2020-09-18 | 华中科技大学 | System and method for recycling crustacean solid waste |
| CN109966505B (en) * | 2019-03-29 | 2021-03-19 | 厦门大学 | Nano-pore natural sustained and controlled release carrier material and preparation method thereof |
| CN110054912B (en) * | 2019-04-10 | 2020-08-18 | 华中科技大学 | Method for preparing rubber filler based on shrimp and crab-based shell pyrolysis and product |
| CN110563860A (en) * | 2019-10-25 | 2019-12-13 | 石家庄亿生堂医用品有限公司 | preparation method of carboxymethyl chitosan |
| CN112375159A (en) * | 2020-11-13 | 2021-02-19 | 浙江万里学院 | Method for preparing chitosan by comprehensively treating shrimp and crab shells |
| CN112891369A (en) * | 2021-04-09 | 2021-06-04 | 厦门大学 | Potassium chloride sustained-release tablet prepared by taking crab shell powder and derivative product thereof as auxiliary materials and preparation method |
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