CN112521427A - Preparation process of glucosamine hydrochloride - Google Patents
Preparation process of glucosamine hydrochloride Download PDFInfo
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- CN112521427A CN112521427A CN202011472886.1A CN202011472886A CN112521427A CN 112521427 A CN112521427 A CN 112521427A CN 202011472886 A CN202011472886 A CN 202011472886A CN 112521427 A CN112521427 A CN 112521427A
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- glucosamine hydrochloride
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- hydrolysate
- chitin
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- 229960001911 glucosamine hydrochloride Drugs 0.000 title claims abstract description 73
- CBOJBBMQJBVCMW-BTVCFUMJSA-N (2r,3r,4s,5r)-2-amino-3,4,5,6-tetrahydroxyhexanal;hydrochloride Chemical compound Cl.O=C[C@H](N)[C@@H](O)[C@H](O)[C@H](O)CO CBOJBBMQJBVCMW-BTVCFUMJSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 72
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 229920002101 Chitin Polymers 0.000 claims abstract description 52
- 239000000243 solution Substances 0.000 claims abstract description 52
- 239000000413 hydrolysate Substances 0.000 claims abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 37
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 31
- 229920001661 Chitosan Polymers 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 230000007935 neutral effect Effects 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 2
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 abstract description 9
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 abstract description 9
- 229960002442 glucosamine Drugs 0.000 abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 28
- 230000007062 hydrolysis Effects 0.000 description 19
- -1 ammonium ions Chemical class 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- 239000000843 powder Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 108010009736 Protein Hydrolysates Proteins 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 208000006820 Arthralgia Diseases 0.000 description 1
- 206010023232 Joint swelling Diseases 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 210000001188 articular cartilage Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 210000001179 synovial fluid Anatomy 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H5/00—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
- C07H5/04—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to nitrogen
- C07H5/06—Aminosugars
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to the technical field of glucosamine, in particular to a preparation process of glucosamine hydrochloride, which comprises the following steps: (1) placing the mixed solution of chitin or chitosan, ammonium chloride solution and volatile organic alcohol in a closed reaction container, and then heating the reaction container; after the reaction is finished, carrying out solid-liquid separation to obtain hydrolysate; (2) mixing the hydrolysate obtained in the step (1) with excessive sodium hydroxide, then reacting under a heating condition, and adjusting the pH of a reaction solution by using hydrochloric acid after the reaction is finished to obtain a glucosamine hydrochloride solution; (3) and (3) drying the glucosamine hydrochloride solution obtained in the step (2) to remove water in the glucosamine hydrochloride solution, thus obtaining the glucosamine hydrochloride. The invention abandons the method of adopting concentrated hydrochloric acid to carry out chitin or chitosan in the traditional process, and effectively relieves the problems of pollution and the like caused by the traditional process.
Description
Technical Field
The invention relates to the technical field of glucosamine preparation, in particular to a preparation process of glucosamine hydrochloride.
Background
Glucosamine (formula C)6H13NO5) Is natural glucosamine, and has effects in repairing articular cartilage, promoting secretion of joint fluid, and promoting joint growthThe synovial fluid has the functions of effectively reducing friction of joint surfaces, relieving joint pain and swelling, recovering joint gaps and the like. Currently, glucosamine is obtained by using chitin or chitosan as a raw material through the processes of hydrolysis, deacidification, decolorization, crystallization and the like. However, because the intramolecular and intermolecular hydrogen bonding of chitin or chitosan hardly dissolves these macromolecular organic substances in water, the existing method needs to hydrolyze chitin or chitosan by concentrated hydrochloric acid first when using chitin or chitosan to prepare glucosamine, but this method not only corrodes equipment seriously and makes treatment of a large amount of waste acid solution difficult, but also causes severe pollution to the production environment due to the strong volatility of concentrated hydrochloric acid, so it is necessary to research a cleaner and more green glucosamine preparation method.
Disclosure of Invention
The invention mainly aims to provide a more environment-friendly preparation method of glucosamine hydrochloride, which overcomes a series of problems caused by strong acid hydrolysis of chitin or chitosan in the existing method. The invention abandons the method of adopting concentrated hydrochloric acid to carry out chitin or chitosan in the traditional process, and effectively relieves the problems of pollution and the like caused by the traditional process. In order to realize the purpose, the invention discloses the following technical scheme:
a preparation process of glucosamine hydrochloride comprises the following steps:
(1) placing the mixed solution of chitin or chitosan, ammonium chloride solution and volatile organic alcohol in a closed reaction container, and then heating the reaction container to make the hydrolysis reaction be carried out in a high-temperature high-pressure environment; and after the reaction is finished, carrying out solid-liquid separation to obtain hydrolysate.
(2) And (2) mixing the hydrolysate obtained in the step (1) with excessive sodium hydroxide, then reacting under a heating condition, and adjusting the pH of the reaction solution by using hydrochloric acid after the reaction is finished to obtain the glucosamine hydrochloride solution.
(3) And (3) drying the glucosamine hydrochloride solution obtained in the step (2) to remove water in the glucosamine hydrochloride solution, thus obtaining the glucosamine hydrochloride.
Preferably, in step (1), the volatile organic alcohol comprises at least one of methanol, ethanol, propanol, and the like. In the invention, the added volatile organic alcohol is heated to be in a gaseous state, so that the reaction environment is kept at a high pressure continuously, the hydrolysis of the chitin or the chitosan is accelerated, the volatile organic alcohol can be removed conveniently after the reaction is finished, and no additional impurity ions are introduced into the hydrolysate.
Preferably, in step (1), the volume ratio of the volatile organic alcohol to the ammonium salt solution is 0.25-0.40: 1.
Preferably, in the step (1), the mass concentration of the ammonium chloride solution is not less than 25%, and too low concentration is likely to cause insufficient hydrolysis of chitin or chitosan, thereby affecting the yield of glucosamine.
Preferably, in the step (1), the heating temperature is 105-.
Preferably, in the step (2), the addition amount of the sodium hydroxide is determined according to the pH value of the reaction solution after the reaction is finished being more than 7 and less than 8; the appropriate excess of sodium hydroxide is convenient for providing sodium ions for generating the glucosamine hydrochloride, and can also remove the incompletely reacted ammonium ions in the hydrolysate by heating after being converted into ammonia water, so that the obtained glucosamine hydrochloride is prevented from containing a large amount of ammonium ions.
Preferably, in the step (2), the hydrochloric acid is added in an amount to adjust the pH of the reaction solution to neutral. The dilute hydrochloric acid can effectively neutralize excessive sodium hydroxide, is convenient for generating glucosamine hydrochloride and avoids bringing extra impurity ions.
Preferably, in the step (2), the heating temperature is 60 to 75 ℃. Volatile substances such as ethanol, ammonia water and the like in the hydrolysate can be effectively removed through heating, and the purity of the glucosamine hydrochloride is ensured.
Preferably, in the step (3), the drying manner includes any one of vacuum drying, freeze drying, and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the traditional method for hydrolyzing chitin or chitosan by concentrated hydrochloric acid, the method adopts the ammonium chloride which is easy to hydrolyze and release hydrogen ions to hydrolyze the chitin or chitosan, namely the double hydrolysis process. On one hand, the hydrolysis of the ammonium chloride is a gradual process, so that the contact between a reaction container and a large amount of hydrogen ions is avoided, the serious corrosion to equipment is effectively relieved, and a large amount of waste acid liquor cannot be generated. On the other hand, ammonia water generated by ammonium chloride hydrolysis volatilizes from the reaction liquid at high temperature, so that the ammonium chloride hydrolysis is continuously carried out towards the direction of generating hydrogen ions, thereby continuously providing a required acidic environment for the hydrolysis of chitin or chitosan and enabling the whole reaction to be more controllable.
(2) In the double hydrolysis process, ammonia water generated by hydrolysis of ammonium chloride is volatilized into a closed container to provide a high-pressure environment for reaction, and the high-pressure and high-temperature reaction environment is helpful for accelerating the hydrolysis rate of chitin or chitosan, deepening the hydrolysis degree, improving the utilization rate of raw materials and increasing the yield of glucosamine hydrochloride.
(3) According to the invention, volatile organic alcohol such as ethanol is added in the hydrolysis process of chitin or chitosan, although ammonia water generated in the hydrolysis process can provide a high-pressure environment for reaction after being volatilized, as the hydrolysis is a continuous process, the ammonia water generated in the early stage is not enough to provide a sufficient high-pressure environment, and after the volatile organic alcohol such as ethanol is added, a large amount of ammonia water can be volatilized at the initial stage of heating reaction to provide a sufficient high-pressure environment, and a gradual reinforcing effect can be provided for the existing high-pressure environment along with the gradual volatilization of ammonia gas, so that the problem of chitin or chitosan hydrolysis weakening caused by the gradual reduction of hydrogen ions released due to the consumption of ammonium salt can be solved.
(4) The ammonia gas generated by the hydrolysis of the volatile organic alcohol and the ammonium salt can not react, so that the ammonia gas can be easily removed from the hydrolysate of the chitin or the chitosan, and the introduction of extra impurity ions into the hydrolysate is avoided. Unreacted ammonium ions, acid radical ions generated by ammonium salts and the like can be conveniently removed through subsequent anion and cation exchange membranes, and the purity of the glucosamine is ensured.
(5) The process for preparing the glucosamine hydrochloride takes the specific substance ammonium chloride as a reaction raw material, not only meets the acid environment required by the hydrolysis of the chitin or the chitosan, but also can remove the residual ammonium ions by the heating of the specific alkaline substance sodium hydroxide, thereby avoiding bringing extra impurity ions and ensuring the purity of the obtained glucosamine hydrochloride.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. The invention will now be further illustrated by specific examples.
Example 1
A preparation process of glucosamine hydrochloride comprises the following steps:
(1) placing a mixed solution of chitin, an aqueous ammonium chloride solution and ethanol in a high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the mass concentration of the aqueous ammonium chloride solution is 35%, the volume ratio of the aqueous ammonium chloride solution to the ethanol is 1:0.35, and the mixed solution is completely submerged in the chitin. And then heating the reaction kettle to 115 ℃ to cook the chitin, so that the hydrolysis reaction is carried out in a high-temperature and high-pressure environment, and filtering and separating out the hydrolysate of the chitin for later use after the reaction is carried out for 3 hours.
(2) And (2) gradually adding sodium hydroxide into the hydrolysate obtained in the step (1), heating the hydrolysate to 60 ℃, detecting the pH of the hydrolysate by using a pH online tester in the heating process, stopping adding the sodium hydroxide when the pH is 7.5, continuously keeping the temperature at 60 ℃ for 20min to completely separate substances such as ethanol, ammonia water and the like in the hydrolysate, and then dropwise adding hydrochloric acid to adjust the pH of the hydrolysate to be neutral to obtain a glucosamine hydrochloride solution for later use.
(3) And (3) freeze-drying the glucosamine hydrochloride solution obtained in the step (2), and removing water in the solution to obtain glucosamine hydrochloride powder.
Example 2
A preparation process of glucosamine hydrochloride comprises the following steps:
(1) placing a mixed solution of chitin, an aqueous ammonium chloride solution and ethanol in a high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the mass concentration of the aqueous ammonium chloride solution is 30%, the volume ratio of the aqueous ammonium chloride solution to the ethanol is 1:0.25, and the mixed solution is completely submerged in the chitin. And then heating the reaction kettle to 105 ℃ to cook the chitin, so that the hydrolysis reaction is carried out in a high-temperature and high-pressure environment, and filtering and separating out the hydrolysate of the chitin for later use after the reaction is carried out for 3 hours.
(2) And (2) gradually adding sodium hydroxide into the hydrolysate obtained in the step (1), heating the hydrolysate to 65 ℃, detecting the pH of the hydrolysate by using a pH online tester in the heating process, stopping adding the sodium hydroxide when the pH is 7.2, continuously keeping the temperature at 65 ℃ for 20min to completely separate substances such as ethanol, ammonia water and the like in the hydrolysate, and then dropwise adding hydrochloric acid to adjust the pH of the hydrolysate to be neutral to obtain a glucosamine hydrochloride solution for later use.
(3) And (3) freeze-drying the glucosamine hydrochloride solution obtained in the step (2), and removing water in the solution to obtain glucosamine hydrochloride powder.
Example 3
A preparation process of glucosamine hydrochloride comprises the following steps:
(1) placing a mixed solution of chitin, an ammonium chloride aqueous solution and methanol in a high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the mass concentration of the ammonium chloride aqueous solution is 25%, the volume ratio of the ammonium chloride aqueous solution to the methanol is 1:0.35, and the mixed solution is completely submerged in the chitin. And then heating the reaction kettle to 100 ℃ to cook the chitin, so that the hydrolysis reaction is carried out in a high-temperature and high-pressure environment, and filtering and separating out the hydrolysate of the chitin for later use after the reaction is carried out for 3 hours.
(2) And (2) gradually adding sodium hydroxide into the hydrolysate obtained in the step (1), heating the hydrolysate to 75 ℃, detecting the pH of the hydrolysate by using a pH online tester in the heating process, stopping adding the sodium hydroxide when the pH is 7.8, continuously keeping the temperature at 75 ℃ for 15min to completely separate out substances such as methanol, ammonia water and the like in the hydrolysate, and then dropwise adding hydrochloric acid to adjust the pH of the hydrolysate to be neutral to obtain a glucosamine hydrochloride solution for later use.
(3) And (3) drying the glucosamine hydrochloride solution obtained in the step (2) in vacuum, and removing water in the glucosamine hydrochloride solution to obtain glucosamine hydrochloride powder.
Example 4
A preparation process of glucosamine hydrochloride comprises the following steps:
(1) placing a mixed solution of chitin, an ammonium chloride aqueous solution and propanol in a high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the mass concentration of the ammonium chloride aqueous solution is 25%, the volume ratio of the ammonium chloride aqueous solution to the propanol is 1:0.4, and the mixed solution is completely submerged in the chitin. And then heating the reaction kettle to 120 ℃ to cook the chitin, so that the hydrolysis reaction is carried out in a high-temperature and high-pressure environment, and filtering and separating out the hydrolysate of the chitin for later use after the reaction is carried out for 3 hours.
(2) And (2) gradually adding sodium hydroxide into the hydrolysate obtained in the step (1), heating the hydrolysate to 70 ℃, detecting the pH of the hydrolysate by using a pH online tester in the heating process, stopping adding the sodium hydroxide when the pH is 7.9, continuously keeping the temperature at 70 ℃ for 20min to completely separate out propanol, ammonia water and other substances in the hydrolysate, dropwise adding hydrochloric acid to adjust the pH of the hydrolysate to be neutral, and obtaining the glucosamine hydrochloride solution for later use.
(3) And (3) drying the glucosamine hydrochloride solution obtained in the step (2) in vacuum, and removing water in the glucosamine hydrochloride solution to obtain glucosamine hydrochloride powder.
Example 5
A preparation process of glucosamine hydrochloride comprises the following steps:
(1) placing a mixed solution of chitosan, an ammonium chloride aqueous solution and methanol in a high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the mass concentration of the ammonium chloride aqueous solution is 35%, the volume ratio of the ammonium chloride aqueous solution to the methanol is 1:35, and the mixed solution is completely submerged in the chitosan. And then heating the reaction kettle to 120 ℃ to cook the chitosan, so that the hydrolysis reaction is carried out in a high-temperature and high-pressure environment, and filtering and separating out the hydrolysate of the chitosan for later use after the reaction is carried out for 3 hours.
(2) And (2) gradually adding sodium hydroxide into the hydrolysate obtained in the step (1), heating the hydrolysate to 65 ℃, detecting the pH of the hydrolysate by using a pH online tester in the heating process, stopping adding the sodium hydroxide when the pH is 7.3, continuously keeping the temperature at 65 ℃ for 20min to completely separate out substances such as methanol, ammonia water and the like in the hydrolysate, and then dropwise adding hydrochloric acid to adjust the pH of the hydrolysate to be neutral to obtain a glucosamine hydrochloride solution for later use.
(3) And (3) drying the glucosamine hydrochloride solution obtained in the step (2) in vacuum, and removing water in the glucosamine hydrochloride solution to obtain glucosamine hydrochloride powder.
Test example 1
A preparation process of glucosamine hydrochloride comprises the following steps:
(1) placing a mixed solution of chitin and an ammonium chloride aqueous solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the mass concentration of the ammonium chloride aqueous solution is 35%, and the mixed solution is completely submerged in the chitin. And then heating the reaction kettle to 115 ℃ to cook the chitin, so that the hydrolysis reaction is carried out in a high-temperature environment, and filtering and separating out the hydrolysate of the chitin for later use after the reaction is carried out for 3 hours.
(2) And (2) gradually adding sodium hydroxide into the hydrolysate obtained in the step (1), heating the hydrolysate to 60 ℃, detecting the pH of the hydrolysate by using a pH online tester in the heating process, stopping adding the sodium hydroxide when the pH is 7.5, continuously keeping the temperature at 60 ℃ for 20min to completely separate ammonia water in the hydrolysate, and then dropwise adding hydrochloric acid to adjust the pH of the hydrolysate to be neutral to obtain a glucosamine hydrochloride solution for later use.
(3) And (3) freeze-drying the glucosamine hydrochloride solution obtained in the step (2), and removing water in the solution to obtain glucosamine hydrochloride powder.
Test example 2
A preparation process of glucosamine hydrochloride comprises the following steps:
(1) placing a mixed solution of chitin, a ferric chloride aqueous solution and ethanol in a high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the mass concentration of the ammonium chloride aqueous solution is 35%, the volume ratio of the ferric chloride aqueous solution to the ethanol is 1:0.35, and the mixed solution is completely submerged in the chitin. And then heating the reaction kettle to 115 ℃ to cook the chitin, so that the hydrolysis reaction is carried out in a high-temperature and high-pressure environment, and filtering and separating out the hydrolysate of the chitin for later use after the reaction is carried out for 3 hours.
(2) And (2) gradually adding sodium hydroxide into the hydrolysate obtained in the step (1), heating the hydrolysate to 60 ℃, detecting the pH of the hydrolysate by using a pH online tester in the heating process, stopping adding the sodium hydroxide when the pH is 7.5, continuously keeping the temperature at 60 ℃ for 20min to completely separate the ethanol in the hydrolysate, and then dropwise adding hydrochloric acid to adjust the pH of the hydrolysate to be neutral to obtain a glucosamine hydrochloride solution for later use.
(3) And (3) freeze-drying the glucosamine hydrochloride solution obtained in the step (2), and removing water in the solution to obtain glucosamine hydrochloride powder.
Test example 3
A preparation process of glucosamine hydrochloride comprises the following steps:
(1) placing a mixed solution of chitin, water and ethanol in a high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the mass concentration of an ammonium chloride aqueous solution is 35%, the volume ratio of water to ethanol is 1:0.35, and the mixed solution is completely submerged in the chitin. And then heating the reaction kettle to 115 ℃ to cook the chitin, carrying out the reaction at high temperature and high pressure, and filtering and separating out hydrolysate of the chitin for later use after reacting for 3 hours.
(2) And (2) gradually adding sodium hydroxide into the hydrolysate obtained in the step (1), heating the hydrolysate to 60 ℃, detecting the pH of the hydrolysate by using a pH online tester in the heating process, stopping adding the sodium hydroxide when the pH is 7.5, continuously keeping the temperature at 60 ℃ for 20min to completely separate the ethanol in the hydrolysate, and then dropwise adding hydrochloric acid to adjust the pH of the hydrolysate to be neutral to obtain a glucosamine hydrochloride solution for later use.
(3) And (3) freeze-drying the glucosamine hydrochloride solution obtained in the step (2), and removing water in the solution to obtain glucosamine hydrochloride powder.
The purity and yield of glucosamine hydrochloride powders prepared in examples 1 to 5 and test examples 1 to 3 were measured, and the results are shown in tables 1 and 2, respectively.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Purity/wt.% of glucosamine hydrochloride | 98.16 | 98.57 | 97.84 | 99.06 | 98.22 |
| Glucosamine hydrochloride yield/wt. -%) | 77.46 | 78.11 | 75.92 | 74.43 | 76.69 |
TABLE 2
| Test example 1 | Test example 2 | Test example 3 | |
| Purity/wt.% of glucosamine hydrochloride | 97.88 | 84.71 | — |
| Glucosamine hydrochloride yield/wt. -%) | 56.19 | 47.37 | — |
As can be seen from the above table: in the experimental example 1, because ethanol is not added as a pressurizing agent, the hydrolysis rate of chitin is significantly influenced, so that the utilization rate of chitin is lower than that of the embodiment, and the final yield of glucosamine hydrochloride is obviously reduced compared with the embodiment. In the experimental example 2, because ferric chloride is adopted, firstly, gas cannot be released in the self-hydrolysis process to pressurize the reaction environment, so that the utilization rate of the chitin is lower than that of the embodiment, and secondly, impurity ion iron is brought in, and the impurity ion iron cannot be removed only through a simpler procedure of heating in the subsequent process, so that the purity of the obtained glucosamine hydrochloride is obviously lower than that of the embodiment. In contrast, in test example 3, water was used instead of ammonium chloride, so that chitin could not be significantly hydrolyzed, and almost no product was obtained at the end.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation process of glucosamine hydrochloride is characterized by comprising the following steps:
(1) placing the mixed solution of chitin or chitosan, ammonium chloride solution and volatile organic alcohol in a closed reaction container, and then heating the reaction container; after the reaction is finished, carrying out solid-liquid separation to obtain hydrolysate;
(2) mixing the hydrolysate obtained in the step (1) with excessive sodium hydroxide, then reacting under a heating condition, and adjusting the pH of a reaction solution by using hydrochloric acid after the reaction is finished to obtain a glucosamine hydrochloride solution;
(3) and (3) drying the glucosamine hydrochloride solution obtained in the step (2) to remove water in the glucosamine hydrochloride solution, thus obtaining the glucosamine hydrochloride.
2. The process for preparing glucosamine hydrochloride according to claim 1, wherein in step (1), the volatile organic alcohol comprises at least one of methanol, ethanol and propanol.
3. The process for preparing glucosamine hydrochloride according to claim 1, wherein the volume ratio of the volatile organic alcohol to the ammonium salt solution in step (1) is 0.25-0.40: 1.
4. The process for preparing glucosamine hydrochloride according to claim 1, wherein the mass concentration of the ammonium chloride solution in the step (1) is not less than 25%.
5. The process according to claim 1, wherein the heating temperature in step (1) is 105-120 ℃.
6. The process according to claim 1, wherein the sodium hydroxide is added in step (2) in such an amount that the pH of the reaction solution after the completion of the reaction is greater than 7 and less than 8.
7. The process according to claim 1, wherein the hydrochloric acid is added in an amount to adjust the pH of the reaction solution to neutral in step (2).
8. The process for the preparation of glucosamine hydrochloride according to any of claims 1-7, wherein the heating temperature in step (2) is 50-75 ℃.
9. The process for preparing glucosamine hydrochloride according to any one of claims 1-7, wherein the drying manner in step (3) comprises any one of vacuum drying and freeze drying.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314609A (en) * | 2008-06-20 | 2008-12-03 | 天津大学 | Process for preparing D-glucosamine hydrochlorate |
| CN107759546A (en) * | 2017-11-13 | 2018-03-06 | 天津工业大学 | A kind of method that catalyzed conversion chitin and monomer N acetylglucosamine prepares the acetyl furan of 3 acetylamino 5 |
| CN209957391U (en) * | 2018-11-27 | 2020-01-17 | 原初科技（北京）有限公司 | Preparation system for preparing hydrogen chloride and ammonia gas by utilizing ammonium chloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314609A (en) * | 2008-06-20 | 2008-12-03 | 天津大学 | Process for preparing D-glucosamine hydrochlorate |
| CN107759546A (en) * | 2017-11-13 | 2018-03-06 | 天津工业大学 | A kind of method that catalyzed conversion chitin and monomer N acetylglucosamine prepares the acetyl furan of 3 acetylamino 5 |
| CN209957391U (en) * | 2018-11-27 | 2020-01-17 | 原初科技（北京）有限公司 | Preparation system for preparing hydrogen chloride and ammonia gas by utilizing ammonium chloride |
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Denomination of invention: Preparation process of glucosamine hydrochloride Effective date of registration: 20231123 Granted publication date: 20211231 Pledgee: China Merchants Bank Co.,Ltd. Jinan Branch Pledgor: SHANDONG RUNDE BIOTECHNOLOGY Co.,Ltd. Registration number: Y2023980067276 |