CN113185711A - Preparation method of acidic, neutral and alkaline stable dispersed nano chitin - Google Patents
Preparation method of acidic, neutral and alkaline stable dispersed nano chitin Download PDFInfo
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- CN113185711A CN113185711A CN202110563643.7A CN202110563643A CN113185711A CN 113185711 A CN113185711 A CN 113185711A CN 202110563643 A CN202110563643 A CN 202110563643A CN 113185711 A CN113185711 A CN 113185711A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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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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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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Abstract
The invention discloses a preparation method of acidic, neutral and alkaline stable dispersed nano chitin, which specifically comprises the following steps: step 1, pretreating a chitin raw material to obtain chitin slurry; step 2, treating the obtained chitin slurry with oxalic acid solution to obtain oxalic acid pretreated chitin slurry; step 3, the obtained chitin slurry pretreated by oxalic acid is mechanically treated in an aqueous solution to prepare nano chitin dispersion liquid, and the preparation of the nano chitin which can be stably dispersed under acidic, neutral and alkaline conditions is realized by adopting an oxalic acid hydrolysis method; and no toxic reagent is used in the preparation process, so that the safety of the nano chitin is ensured.
Description
Technical Field
The invention belongs to the technical field of preparation of chitin nano materials, and particularly relates to a preparation method of acidic, neutral and alkaline stable dispersed nano chitin.
Background
In the existing preparation methods of nano chitin, the most common pretreatment methods used include acid hydrolysis, partial deacetylation, TEMPO oxidation and the like, but the nano chitin prepared by the methods has generally single dispersion property and cannot realize stable dispersion under acidic, neutral and alkaline conditions, and the existing most widely used preparation method of carboxylated nano chitin, TEMPO oxidation, cannot avoid using a catalyst with toxicity in the treatment process, so that the application of the catalyst in the field of biological medicine is greatly limited.
Disclosure of Invention
The invention aims to provide a preparation method of acidic, neutral and alkaline stable dispersed nano chitin, so as to solve the technical problems.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of acidic, neutral and alkaline stable dispersed nano chitin specifically comprises the following steps:
step 2, treating the obtained chitin slurry with oxalic acid solution to obtain oxalic acid pretreated chitin slurry;
and 3, mechanically treating the obtained oxalic acid pretreated chitin slurry in an aqueous solution to obtain the nano chitin dispersion.
Preferably, in step 2: the mass concentration of the oxalic acid solution is 5-80%, the acid treatment temperature is 50-150 ℃, and the acid treatment time is 0.5-5 hours.
Preferably, in step 3: the pH of the aqueous solution is 2-11.
Preferably, the mechanical treatment mode includes but is not limited to ultrasonic treatment and high-pressure homogenization treatment.
Preferably, the chitin raw material includes, but is not limited to, shrimp shell, crab shell, squid parietal bone.
Preferably, the acidic medium in the acidic aqueous solution includes, but is not limited to, at least one of hydrochloric acid, sulfuric acid, formic acid, acetic acid, propionic acid, malonic acid, citric acid, oxalic acid; the alkaline medium in the alkaline aqueous solution includes, but is not limited to, at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and ammonia water.
Preferably, the alkaline medium in the alkaline aqueous solution includes, but is not limited to, at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and ammonia water.
Preferably, the step 1 pretreatment specifically comprises the following steps:
step 11, taking chitin raw materials, cleaning and cutting the chitin raw materials into pieces, and treating the cut chitin raw materials in sodium hydroxide and hydrochloric acid alternately for 12 hours and three cycles;
step 12, bleaching and removing pigments in chitin raw material fragments in a 0.5% sodium chlorite solution at 70 ℃ water bath;
step 13, washing the bleached chitin raw material to be neutral by using distilled water, sealing and placing in a 4 ℃ condition to balance moisture;
and step 14, crushing the chitin raw material fragments with balanced moisture into slurry to obtain chitin slurry.
The preparation method of the acidic, neutral and alkaline stable dispersed nano chitin has the following technical effects and advantages:
1. the preparation of the nano chitin which can be stably dispersed under acidic, neutral and alkaline conditions is realized by adopting an oxalic acid hydrolysis method;
2. no toxic reagent is used in the preparation process, so that the safety of the nano chitin is ensured;
3. realizes the cheap preparation of the carboxylated nano chitin.
Drawings
FIG. 1 is a photograph of a nano chitin dispersion stably dispersed at pH 3,4,6,8,10, 11;
FIG. 2 is a photograph showing the appearance of nano chitin dispersed under pH 3;
FIG. 3 is a photograph showing the appearance of nano chitin dispersed under pH 7;
fig. 4 is a photograph of the nano chitin dispersed under pH 10.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to fig. 1 to 4 in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The embodiment provides a preparation method of chitin slurry, which comprises the following steps:
step 11, cleaning and cutting the crab shell raw material into pieces, soaking the cut crab shell raw material in 1M sodium hydroxide for about 12 hours to remove protein components in the crab shell raw material, washing the crab shell raw material to be neutral by using distilled water, soaking the crab shell raw material in 1M hydrochloric acid for about 12 hours to remove mineral components in the crab shell raw material, repeating the treatment process for three times to remove calcium and protein components in the crab shell raw material as completely as possible, and finally washing the softened crab shell raw material to be neutral.
And step 12, bleaching and removing pigments in the crab shell raw material fragments in a 0.5% (w/w) sodium chlorite solution under the condition of water bath at 70 ℃ to obtain white chitin raw material fragments.
Step 13, washing the white chitin raw material fragments to be neutral by using distilled water, putting the white chitin raw material fragments into a sealing bag, sealing the sealing bag, and placing the sealing bag in a refrigerator at 4 ℃ for 2 days to balance the water content.
And step 14, crushing the chitin raw material fragments with balanced moisture into pulp by using a juicer to obtain chitin pulp.
Example two
The embodiment provides a preparation method of chitin slurry pretreated by oxalic acid, which comprises the following steps:
according to the solid-to-liquid ratio of the dry weight of the purified chitin slurry to the oxalic acid solution of 1: 50, preparing an oxalic acid solution with the mass ratio of about 5%, taking 4g of dry weight of the chitin slurry prepared in the first embodiment, adding the chitin slurry into the oxalic acid solution, fully stirring and uniformly mixing, placing in a constant-temperature water bath kettle at 90 ℃, stirring for 4 hours at 100 revolutions per minute, realizing chitin surface formylation modification and defibering of a fiber structure through oxalic acid, and finishing the reaction.
The reaction system is filtered by filter cloth to obtain sediment, and the sediment is washed by distilled water to be neutral, so that the chitin slurry pretreated by oxalic acid is obtained.
EXAMPLE III
The embodiment provides a preparation method of nano chitin stably dispersed in an acidic aqueous solution, which comprises the following steps:
further, the acidic medium in the acidic aqueous solution includes, but is not limited to, at least one of hydrochloric acid, sulfuric acid, formic acid, acetic acid, propionic acid, malonic acid, citric acid, and oxalic acid, and acetic acid is selected as the acidic medium in the acidic aqueous solution in this embodiment.
Fully stirring and mixing the oxalic acid pretreatment chitin slurry prepared in the second embodiment with 1% acetic acid solution in a solid-to-liquid ratio of 1:10, homogenizing and ultrasonically treating at 10000rpm for 3min, and finally centrifuging to obtain supernatant fluid to obtain the nano chitin stably dispersed in the acidic aqueous solution.
Example four
The embodiment provides a preparation method of nano chitin stably dispersed in a neutral aqueous solution, which comprises the following steps:
fully stirring and mixing the chitin slurry pretreated by the oxalic acid obtained in the second embodiment with distilled water according to the solid-to-liquid ratio of 1:20, homogenizing and ultrasonically treating at 10000rpm for 3min, and finally centrifuging to obtain the supernatant fluid to obtain the nano chitin stably dispersed in the neutral aqueous solution.
EXAMPLE five
The embodiment provides a preparation method of nano chitin stably dispersed in an alkaline aqueous solution, which comprises the following steps:
further, the alkaline medium in the alkaline aqueous solution includes, but is not limited to, at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and ammonia, and in this embodiment, sodium hydroxide is selected as the alkaline medium in the alkaline aqueous solution.
Fully stirring and mixing the oxalic acid pretreatment chitin slurry prepared in the second embodiment with 1% sodium hydroxide solution in a solid-to-liquid ratio of 1:10, homogenizing and ultrasonically treating at 10000rpm for 3min, and finally centrifuging to obtain supernatant fluid to obtain the nano chitin stably dispersed in the alkaline aqueous solution.
In the present invention:
specifically, the pH of the aqueous solution is 2-11, and the aqueous solution comprises acidic aqueous solution, neutral aqueous solution and alkaline aqueous solution.
Specifically, the mechanical treatment mode includes but is not limited to ultrasonic treatment and high-pressure homogenization treatment, wherein the ultrasonic treatment is 10000rpm homogenization treatment for 3min, so that the particle size of the chitin is further reduced; the high pressure homogenizing treatment is carried out for three times under the conditions of 100bar, 300bar and 500bar to further reduce the grain size of the chitin.
Specifically, the chitin raw material includes but is not limited to shrimp shell, crab shell, and squid parietal bone.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (8)
1. A preparation method of acidic, neutral and alkaline stable dispersed nano chitin is characterized by comprising the following steps:
step 1, pretreating a chitin raw material to obtain chitin slurry;
step 2, treating the obtained chitin slurry with oxalic acid solution to obtain oxalic acid pretreated chitin slurry;
and 3, mechanically treating the obtained oxalic acid pretreated chitin slurry in an aqueous solution to obtain the nano chitin dispersion.
2. The method for preparing acidic, neutral and alkaline stable dispersed nano chitin according to claim 1, wherein in the step 2: the mass concentration of the oxalic acid solution is 5-80%, the acid treatment temperature is 50-150 ℃, and the acid treatment time is 0.5-5 hours.
3. The method for preparing acidic, neutral and alkaline stable dispersed nano chitin according to claim 1, wherein in step 3: the pH of the aqueous solution is 2-11.
4. The method for preparing acidic, neutral and alkaline stable dispersed nano chitin according to claim 1, wherein: the mechanical treatment mode includes but is not limited to ultrasonic treatment and high-pressure homogenization treatment.
5. The method for preparing acidic, neutral and alkaline stable dispersed nano chitin according to claim 1, wherein: the chitin raw material includes but is not limited to shrimp shell, crab shell, and squid parietal bone.
6. The method for preparing acidic, neutral and alkaline stable dispersed nano chitin according to claim 1, wherein: the acidic medium in the acidic aqueous solution includes, but is not limited to, at least one of hydrochloric acid, sulfuric acid, formic acid, acetic acid, propionic acid, malonic acid, citric acid, oxalic acid.
7. The method for preparing acidic, neutral and alkaline stable dispersed nano chitin according to claim 1, wherein: the alkaline medium in the alkaline aqueous solution includes, but is not limited to, at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and ammonia water.
8. The method for preparing acidic, neutral and alkaline stable dispersed nano chitin according to claim 1, wherein the pretreatment of step 1 specifically comprises the following steps:
step 11, taking chitin raw materials, cleaning and cutting the chitin raw materials into pieces, and treating the cut chitin raw materials in sodium hydroxide and hydrochloric acid alternately for 12 hours and three cycles;
step 12, bleaching and removing pigments in chitin raw material fragments in a 0.5% sodium chlorite solution at 70 ℃ water bath;
step 13, washing the bleached chitin raw material to be neutral by using distilled water, sealing and placing in a 4 ℃ condition to balance moisture;
and step 14, crushing the chitin raw material fragments with balanced moisture into slurry to obtain chitin slurry.
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| CN202110563643.7A CN113185711A (en) | 2021-05-24 | 2021-05-24 | Preparation method of acidic, neutral and alkaline stable dispersed nano chitin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2605187A (en) * | 2021-03-26 | 2022-09-28 | Futamura Chemical Uk Ltd | Dissolution method |
Citations (6)
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|---|---|---|---|---|
| KR950003318A (en) * | 1993-07-30 | 1995-02-16 | 전동원 | Method for preparing 0-carboxymethyl chitin |
| KR20040094491A (en) * | 2003-05-02 | 2004-11-10 | 주식회사 금호화성 | A method for producing highly purified chitin |
| CN102964394A (en) * | 2012-12-12 | 2013-03-13 | 石狮市华宝海洋生物化工有限公司 | Method for promoting production of glucosamine hydrochloride |
| CN105254903A (en) * | 2015-11-13 | 2016-01-20 | 南京林业大学 | Method for preparing oxidated chitin nanofiber dispersion liquid |
| CN105504093A (en) * | 2016-01-18 | 2016-04-20 | 南京林业大学 | Method for preparing membrane electrode from chitin nano fiber/carbon nanotube composite |
| CN108659135A (en) * | 2018-05-29 | 2018-10-16 | 南京林业大学 | A kind of cellulose nano-fibrous or chitin nanofiber dispersion liquid preparation method |
-
2021
- 2021-05-24 CN CN202110563643.7A patent/CN113185711A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR950003318A (en) * | 1993-07-30 | 1995-02-16 | 전동원 | Method for preparing 0-carboxymethyl chitin |
| KR20040094491A (en) * | 2003-05-02 | 2004-11-10 | 주식회사 금호화성 | A method for producing highly purified chitin |
| CN102964394A (en) * | 2012-12-12 | 2013-03-13 | 石狮市华宝海洋生物化工有限公司 | Method for promoting production of glucosamine hydrochloride |
| CN105254903A (en) * | 2015-11-13 | 2016-01-20 | 南京林业大学 | Method for preparing oxidated chitin nanofiber dispersion liquid |
| CN105504093A (en) * | 2016-01-18 | 2016-04-20 | 南京林业大学 | Method for preparing membrane electrode from chitin nano fiber/carbon nanotube composite |
| CN108659135A (en) * | 2018-05-29 | 2018-10-16 | 南京林业大学 | A kind of cellulose nano-fibrous or chitin nanofiber dispersion liquid preparation method |
Non-Patent Citations (1)
| Title |
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| 娄春华等: "《高分子科学导论》", 哈尔滨工业大学出版社, pages: 224 - 225 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2605187A (en) * | 2021-03-26 | 2022-09-28 | Futamura Chemical Uk Ltd | Dissolution method |
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