CN116731088A - Preparation method of D-glucosamine sulfate - Google Patents
Preparation method of D-glucosamine sulfate Download PDFInfo
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- CN116731088A CN116731088A CN202310849704.5A CN202310849704A CN116731088A CN 116731088 A CN116731088 A CN 116731088A CN 202310849704 A CN202310849704 A CN 202310849704A CN 116731088 A CN116731088 A CN 116731088A
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- glucosamine sulfate
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- FGNPLIQZJCYWLE-BTVCFUMJSA-N (2r,3r,4s,5r)-2-amino-3,4,5,6-tetrahydroxyhexanal;sulfuric acid Chemical compound OS(O)(=O)=O.O=C[C@H](N)[C@@H](O)[C@H](O)[C@H](O)CO FGNPLIQZJCYWLE-BTVCFUMJSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000012265 solid product Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 32
- 239000012452 mother liquor Substances 0.000 claims description 31
- 238000006386 neutralization reaction Methods 0.000 claims description 19
- 238000001556 precipitation Methods 0.000 claims description 19
- 238000000855 fermentation Methods 0.000 claims description 18
- 230000004151 fermentation Effects 0.000 claims description 18
- 239000011780 sodium chloride Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 claims description 8
- OVRNDRQMDRJTHS-FMDGEEDCSA-N N-acetyl-beta-D-glucosamine Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O OVRNDRQMDRJTHS-FMDGEEDCSA-N 0.000 claims description 8
- MBLBDJOUHNCFQT-LXGUWJNJSA-N N-acetylglucosamine Natural products CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229950006780 n-acetylglucosamine Drugs 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000012869 ethanol precipitation Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 9
- 239000000243 solution Substances 0.000 abstract description 41
- 239000000047 product Substances 0.000 abstract description 14
- MTDHILKWIRSIHB-UHFFFAOYSA-N (5-azaniumyl-3,4,6-trihydroxyoxan-2-yl)methyl sulfate Chemical compound NC1C(O)OC(COS(O)(=O)=O)C(O)C1O MTDHILKWIRSIHB-UHFFFAOYSA-N 0.000 abstract description 10
- 229960002849 glucosamine sulfate Drugs 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 abstract 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract 2
- 235000010413 sodium alginate Nutrition 0.000 abstract 2
- 239000000661 sodium alginate Substances 0.000 abstract 2
- 229940005550 sodium alginate Drugs 0.000 abstract 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 abstract 1
- 229930003268 Vitamin C Natural products 0.000 abstract 1
- 239000001110 calcium chloride Substances 0.000 abstract 1
- 229910001628 calcium chloride Inorganic materials 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 239000012043 crude product Substances 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 230000003405 preventing effect Effects 0.000 abstract 1
- 235000019154 vitamin C Nutrition 0.000 abstract 1
- 239000011718 vitamin C Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 10
- 238000000605 extraction Methods 0.000 description 9
- 230000009471 action Effects 0.000 description 7
- 239000000413 hydrolysate Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 230000008569 process Effects 0.000 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 description 1
- MSFSPUZXLOGKHJ-PGYHGBPZSA-N 2-amino-3-O-[(R)-1-carboxyethyl]-2-deoxy-D-glucopyranose Chemical compound OC(=O)[C@@H](C)O[C@@H]1[C@@H](N)C(O)O[C@H](CO)[C@H]1O MSFSPUZXLOGKHJ-PGYHGBPZSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- MSFSPUZXLOGKHJ-UHFFFAOYSA-N Muraminsaeure Natural products OC(=O)C(C)OC1C(N)C(O)OC(CO)C1O MSFSPUZXLOGKHJ-UHFFFAOYSA-N 0.000 description 1
- 125000003047 N-acetyl group Chemical group 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 208000007107 Stomach Ulcer Diseases 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- MSWZFWKMSRAUBD-QZABAPFNSA-N beta-D-glucosamine Chemical compound N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-QZABAPFNSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 201000005917 gastric ulcer Diseases 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- 150000002301 glucosamine derivatives Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 201000003068 rheumatic fever Diseases 0.000 description 1
- 230000002194 synthesizing 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
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
-
- 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)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a preparation method of D-glucosamine sulfate, which comprises the following steps: (1) Dissolving the glucosamine sulfate crude product in water, deproteinizing, adding ethanol into the obtained purified solution, precipitating with ethanol again, separating solid product, drying to obtain glucosamine sulfate powder, and granulating. (2) And (3) applying the mixed solution of sodium alginate and vitamin C on the surface of the granular glucosamine sulfate, then continuously applying the ethanol solution of calcium chloride, then crosslinking the sodium alginate on the surface of the granular glucosamine sulfate into a film under the heating condition, washing the obtained product with water, drying, applying edible wax on the surface of the dried product, and solidifying to obtain the glucosamine sulfate product. The glucosamine sulfate prepared by the invention has good moisture absorption and deliquescence preventing effects, and is convenient for long-term storage of the glucosamine sulfate.
Description
Technical Field
The invention relates to the technical field of glucosamine sulfate, in particular to a preparation method of D-glucosamine sulfate.
Background
D-glucosamine (chemical formula C) 6 H 13 NO 5 ) Also known as glucosamine, etc., which is a compound in which one of the hydroxyl groups of glucose is replaced by one of the amino groups, is widely present in microorganisms, polysaccharides of animal origin and conjugated polysaccharides, generally in the form of N-acetyl derivatives such as chitin or in the form of N-sulfate and N-acetyl-3-O-lactic acid ether (muramic acid). D-glucosamine sulfate is one of the derivatives of glucosamine, which has important physiological functions for human body, such as being involved in detoxification of liver and kidney and playing an anti-inflammatory and liver-protecting role. In addition, the D-glucosamine sulfate has good curative effect on treating rheumatic arthritis and gastric ulcer, is a main raw material for synthesizing antibiotics and anticancer drugs, and can be also applied to foods, cosmetics and feed additives. At present, when D-glucosamine sulfate is prepared by a microbial fermentation method, the D-glucosamine sulfate needs to be extracted from hydrolysate by an alcohol precipitation mode, however, only part of the D-glucosamine sulfate can be extracted by the mode, and a considerable part of D-glucosamine sulfate still remains in the residual mother liquor, so that waste of target products is caused.
Disclosure of Invention
In view of the above problems, the invention provides a preparation method of D-glucosamine sulfate, which can effectively extract residual D-glucosamine sulfate in mother liquor, reduce waste of target products and improve extraction rate. In order to achieve the above purpose, the present invention discloses the following technical solutions.
A preparation method of D-glucosamine sulfate comprises the following steps:
(1) Adding sulfuric acid into the fermentation liquor to hydrolyze the N-acetylglucosamine, and adding alkaline substances into the obtained hydrolysis liquor to neutralize the redundant sulfuric acid after the hydrolysis is completed, so as to obtain the neutralization liquor containing D-glucosamine sulfate.
(2) Concentrating the neutralization solution to form a concentrated solution, adding ethanol, uniformly mixing, standing for alcohol precipitation, carrying out solid-liquid separation after the completion of the alcohol precipitation, respectively collecting a solid product and residual mother liquor, and drying the solid product to obtain the D-glucosamine sulfate for later use.
(3) Adding sodium chloride powder into the residual mother liquor, regulating the ethanol and water in the residual mother liquor to an azeotropic ratio, heating to an azeotropic temperature under an oxygen-isolation condition until the ethanol and water are volatilized, obtaining D-glucosamine sulfate, and combining the D-glucosamine sulfate with the D-glucosamine sulfate obtained in the step (2).
In a further scheme, in the step (1), the initial mass percentage of sulfuric acid in the fermentation broth is kept between 45 and 60 percent. Optionally, the hydrolysis is carried out for 3-5 hours at 70-85 ℃.
In a further embodiment, in the step (1), the alkaline substance includes any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium hydroxide, etc., so that D-glucosamine sulfate can be formed while neutralizing the excess sulfuric acid.
In a further scheme, in the step (2), the neutralization solution is heated and concentrated to 40-55% of the initial volume to obtain a concentrated solution, so that the concentration of a target product in the neutralization solution is increased, the use amount of the ethanol is reduced, and the extraction rate of the target product is improved.
In a further scheme, in the step (2), the addition amount of the ethanol is 3-5 times of the volume of the concentrated solution, and the standing time is 30-40 min so as to crystallize and separate out the target product D-glucosamine sulfate in the concentrated solution.
In a further embodiment, in step (2), the drying mode includes any one of lyophilization, vacuum drying, and the like.
In a further scheme, in the step (3), the adding amount of sodium chloride in the residual mother liquor is 1-2.5 g/L. In the invention, the sodium chloride is not only beneficial to inducing the crystallization and precipitation of the target product dissolved in the residual mother solution after the ethanol is added, so that the extraction rate is improved, but also the hygroscopicity of the D-glucosamine sulfate is reduced, the stability is improved, and the D-glucosamine sulfate is easier to store.
In a further scheme, in the step (3), the mass percentage of the ethanol and the water in the residual mother liquor is adjusted to 95.6:4.4, said azeotropic temperature is 78.1 ℃ so that said residual mother liquor is co-evaporated at a lower azeotropic temperature.
In a further scheme, in the step (3), the oxygen isolation condition is an atmosphere environment formed by any one of nitrogen, argon and the like, so that oxygen in the air is isolated, and the oxidation of a target product at a high temperature is reduced.
In a further embodiment, the method further comprises a step of condensing and collecting the azeotrope volatilized by heating in the step (3); preferably, the ethanol solution obtained by condensation and collection is used for the ethanol precipitation procedure described in step (2).
Compared with the prior art, the invention has the following beneficial technical effects: when the D-glucosamine sulfate is prepared by a fermentation method, most of the D-glucosamine sulfate in the concentrated solution is extracted by adopting an alcohol precipitation mode. And then adjusting the ethanol and water added into the residual mother liquor to an azeotropic ratio, so that the ethanol added in the alcohol precipitation stage is exactly utilized to form an azeotrope with water, the azeotrope can be removed by evaporation at a lower temperature due to lower azeotropic temperature of the ethanol and the water, and the final residual product is the target product D-glucosamine sulfate which is remained in the residual mother liquor and is usually difficult to extract, so that the waste of the D-glucosamine sulfate is reduced, and the extraction rate of the D-glucosamine sulfate in the concentrated solution is effectively improved. The azeotrope is evaporated, condensed and collected to form high-concentration ethanol with concentration of 95 percent, and the high-concentration ethanol can be further used for the alcohol precipitation step of the subsequent process, thereby realizing the recycling of the ethanol. In addition, sodium chloride is added into the concentrated solution before alcohol precipitation, and the sodium chloride is separated out under the action of ethanol, so that the crystallization separation of a target product dissolved in the residual mother solution is induced, the extraction rate is improved, and meanwhile, the hygroscopicity of the D-glucosamine sulfate is reduced, the stability is improved, and the D-glucosamine sulfate is easier to store.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. The invention will now be further illustrated by means of a specific implementation.
Example 1
The preparation method of the D-glucosamine sulfate comprises the following steps:
(1) Sulfuric acid is added into the fermentation liquor to make the mass percent of the sulfuric acid be 55%, and then water bath heating is carried out to 80 ℃ for 4 hours, so that the N-acetylglucosamine in the fermentation liquor is hydrolyzed under the action of strong acid. And adding sodium hydroxide into the obtained hydrolysate to neutralize the excessive sulfuric acid after the completion of the hydrolysis, thereby obtaining the neutralization solution containing D-glucosamine sulfate.
(2) And heating the neutralization solution to 50% of the initial volume in a water bath to obtain a concentrated solution. Then adding 95% ethanol with the volume of 4.5 times of that of the concentrated solution, uniformly stirring, standing for 35min for alcohol precipitation, centrifuging (the speed is 12000 r/min, the time is 15 min) after the alcohol precipitation is finished, carrying out solid-liquid separation, respectively collecting a solid product and residual mother liquor, and carrying out vacuum drying on the solid product at 70 ℃ for 40min to obtain D-glucosamine sulfate powder for later use.
(3) Adding sodium chloride powder into the residual mother liquor according to the proportion of 2g/L, stirring until the sodium chloride powder is dissolved, then continuously adding ethanol into the residual mother liquor, and adjusting the mass percent of the ethanol and the water to be 95.6:4.4, heating to 78.1 ℃ in a water bath in a nitrogen atmosphere until ethanol and water are volatilized, obtaining D-glucosamine sulfate, and combining the D-glucosamine sulfate with the D-glucosamine sulfate obtained in the step (2).
Example 2
The preparation method of the D-glucosamine sulfate comprises the following steps:
(1) Sulfuric acid is added into the fermentation liquor to make the mass percent of the sulfuric acid be 60%, and then water bath heating is carried out to 85 ℃ for 3 hours, so that the N-acetylglucosamine in the fermentation liquor is hydrolyzed under the action of strong acid. And adding sodium bicarbonate into the obtained hydrolysate to neutralize the excessive sulfuric acid, so as to obtain a neutralization solution containing D-glucosamine sulfate.
(2) Heating the neutralization solution in water bath to 40% of the initial volume to obtain a concentrated solution. Then adding 95% ethanol with the volume of 3 times of that of the concentrated solution, uniformly stirring, standing for 40min for alcohol precipitation, centrifuging (the speed is 12000 r/min, the time is 15 min) after the completion of the alcohol precipitation, carrying out solid-liquid separation, respectively collecting a solid product and the residual mother liquor, and carrying out vacuum drying on the solid product at 75 ℃ for 30min to obtain D-glucosamine sulfate powder for later use.
(3) Adding sodium chloride powder into the residual mother liquor according to the proportion of 1g/L, stirring until the sodium chloride powder is dissolved, then continuously adding ethanol into the residual mother liquor, and adjusting the mass percent of the ethanol and the water to be 95.6:4.4, heating to 78.1 ℃ in a water bath in a nitrogen atmosphere until ethanol and water are volatilized, obtaining D-glucosamine sulfate, and combining the D-glucosamine sulfate with the D-glucosamine sulfate obtained in the step (2).
Example 3
The preparation method of the D-glucosamine sulfate comprises the following steps:
(1) Sulfuric acid is added into the fermentation liquor to make the mass percentage of the sulfuric acid be 45%, and then water bath heating is carried out to 70 ℃ and the temperature is kept for 5 hours, so that the N-acetylglucosamine in the fermentation liquor is hydrolyzed under the action of strong acid. And adding sodium carbonate into the obtained hydrolysate to neutralize the excessive sulfuric acid, so as to obtain the neutralization solution containing D-glucosamine sulfate.
(2) And heating the neutralization solution to 55% of the initial volume in a water bath to obtain a concentrated solution. Then adding 95% ethanol with the volume of 5 times of that of the concentrated solution, uniformly stirring, standing for 30min for alcohol precipitation, centrifuging (the speed is 12000 r/min, the time is 15 min) after the completion of the alcohol precipitation, carrying out solid-liquid separation, respectively collecting a solid product and the residual mother liquor, and carrying out vacuum drying on the solid product at 70 ℃ for 45min to obtain D-glucosamine sulfate powder for later use.
(3) Adding sodium chloride powder into the residual mother liquor according to the proportion of 2.5g/L, stirring until the sodium chloride powder is dissolved, then continuously adding ethanol into the residual mother liquor, and adjusting the mass percent of the ethanol and the water to be 95.6:4.4, heating to 78.1 ℃ in a water bath in a nitrogen atmosphere until ethanol and water are volatilized, obtaining D-glucosamine sulfate, and combining the D-glucosamine sulfate with the D-glucosamine sulfate obtained in the step (2).
Example 4
The preparation method of the D-glucosamine sulfate comprises the following steps:
(1) Sulfuric acid is added into the fermentation liquor to make the mass percent of the sulfuric acid be 55%, and then water bath heating is carried out to 80 ℃ for 4 hours, so that the N-acetylglucosamine in the fermentation liquor is hydrolyzed under the action of strong acid. And adding sodium hydroxide into the obtained hydrolysate to neutralize the excessive sulfuric acid after the completion of the hydrolysis, thereby obtaining the neutralization solution containing D-glucosamine sulfate.
(2) And heating the neutralization solution to 50% of the initial volume in a water bath to obtain a concentrated solution. And adding 95% ethanol with the volume of 4.5 times of that of the concentrated solution, uniformly stirring, standing for 35min for alcohol precipitation, centrifuging (the speed is 12000 r/min and the time is 15 min) after the alcohol precipitation is finished, carrying out solid-liquid separation, respectively collecting a solid product and residual mother liquor, and carrying out vacuum drying on the solid product at 70 ℃ for 40min to obtain the D-glucosamine sulfate powder.
Example 5
The preparation method of the D-glucosamine sulfate comprises the following steps:
(1) Sulfuric acid is added into the fermentation liquor to make the mass percent of the sulfuric acid be 60%, and then water bath heating is carried out to 85 ℃ for 3 hours, so that the N-acetylglucosamine in the fermentation liquor is hydrolyzed under the action of strong acid. And adding sodium bicarbonate into the obtained hydrolysate to neutralize the excessive sulfuric acid, so as to obtain a neutralization solution containing D-glucosamine sulfate.
(2) Heating the neutralization solution in water bath to 40% of the initial volume to obtain a concentrated solution. Then adding 95% ethanol with the volume of 3 times of that of the concentrated solution, uniformly stirring, standing for 40min for alcohol precipitation, centrifuging (the speed is 12000 r/min, the time is 15 min) after the completion of the alcohol precipitation, carrying out solid-liquid separation, respectively collecting a solid product and the residual mother liquor, and carrying out vacuum drying on the solid product at 75 ℃ for 30min to obtain D-glucosamine sulfate powder for later use.
(3) Continuously adding ethanol into the residual mother liquor, and adjusting the mass percent of the ethanol and the water to be 95.6:4.4, heating to 78.1 ℃ in a water bath in a nitrogen atmosphere until ethanol and water are volatilized, obtaining D-glucosamine sulfate, and combining the D-glucosamine sulfate with the D-glucosamine sulfate obtained in the step (2).
Example 6
The preparation method of the D-glucosamine sulfate comprises the following steps:
(1) Sulfuric acid is added into the fermentation liquor to make the mass percent of the sulfuric acid be 55%, then water bath heating is carried out to 75 ℃ and the temperature is kept for 3.5 hours, so that the N-acetylglucosamine in the fermentation liquor is hydrolyzed under the action of strong acid. And adding potassium hydroxide into the obtained hydrolysate to neutralize the excessive sulfuric acid, so as to obtain the neutralization solution containing D-glucosamine sulfate.
(2) And heating the neutralization solution to 45% of the initial volume in a water bath to obtain a concentrated solution. Then adding 4 times of ethanol (the ethanol is an ethanol solution formed by condensing the collected volatile ethanol and water azeotrope in the step (3) of the embodiment 3) into the concentrated solution, uniformly stirring, standing for 35min for ethanol precipitation, centrifuging (speed 12000 r/min and time 15 min) after the completion of the ethanol precipitation, performing solid-liquid separation, respectively collecting a solid product and residual mother liquor, and vacuum drying the solid product at 70 ℃ for 45min to obtain D-glucosamine sulfate powder for later use.
(3) Adding sodium chloride powder into the residual mother liquor according to the proportion of 1.5g/L, stirring until the sodium chloride powder is dissolved, then continuously adding ethanol into the residual mother liquor, and adjusting the mass percent of the ethanol and the water to be 95.6:4.4, heating to 78.1 ℃ in a water bath in a nitrogen atmosphere until ethanol and water are volatilized, obtaining D-glucosamine sulfate, and combining the D-glucosamine sulfate with the D-glucosamine sulfate obtained in the step (2).
1. The above examples 1 to 6 were tested for the extraction rate of D-glucosamine sulfate in the concentrated solution, which is the percentage of the extracted D-glucosamine sulfate to all D-glucosamine sulfate in the concentrated solution, and the results are shown in Table 1 below.
2. The hygroscopicity of the D-glucosamine sulfate obtained in examples 1 to 6 was measured by the following method: a 20g sample of the glucosamine sulfate was taken and allowed to stand in a ventilated natural environment for one week, after which the weight of the sample was tested and its change relative to the initial sample weight was calculated and the results are shown in table 1 below.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Extraction yield/% | 99.67 | 99.84 | 99.56 | 88.13 | 97.06 | 99.61 |
| Moisture absorption rate/% | 2.66 | 2.72 | 3.02 | 6.29 | 6.43 | 2.79 |
From the above test results, it can be seen that the process of example 4 and example 5 showed a decrease in the extraction capacity of D-glucosamine sulfate in the concentrate, especially example 4, which did not further extract the mother liquor, resulting in a waste of the target product due to the fact that a large amount of D-glucosamine sulfate remained therein was not extracted, and the extraction yield was significantly decreased. In addition, it can be seen that the glucosamine sulfate prepared in example 4 and example 5 has a significantly increased moisture absorption rate due to the absence of sodium chloride, and thus has a lower stability.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of D-glucosamine sulfate is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding sulfuric acid into the fermentation liquor to hydrolyze N-acetylglucosamine, and adding alkaline substances into the obtained hydrolysis liquor to neutralize the redundant sulfuric acid after the hydrolysis is completed, so as to obtain a neutralization liquor containing D-glucosamine sulfate;
(2) Concentrating the neutralization solution to form a concentrated solution, adding ethanol, uniformly mixing, standing for alcohol precipitation, carrying out solid-liquid separation after completion, respectively collecting a solid product and residual mother liquor, and drying the solid product to obtain D-glucosamine sulfate for later use;
(3) Adding sodium chloride powder into the residual mother liquor, regulating the ethanol and water in the residual mother liquor to an azeotropic ratio, heating to an azeotropic temperature under an oxygen-isolation condition until the ethanol and water are volatilized, obtaining D-glucosamine sulfate, and combining the D-glucosamine sulfate with the D-glucosamine sulfate obtained in the step (2).
2. The method for producing D-glucosamine sulfate according to claim 1, wherein: in the step (1), the initial mass percentage of sulfuric acid in the fermentation broth is kept between 45 and 60 percent.
3. The method for producing D-glucosamine sulfate according to claim 1, wherein: the hydrolysis is carried out for 3-5 hours at 70-85 ℃.
4. The method for producing D-glucosamine sulfate according to claim 1, wherein: in the step (1), the alkaline substance comprises any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium hydroxide.
5. The method for producing D-glucosamine sulfate according to claim 1, wherein: in the step (2), heating and concentrating the neutralization solution to 40-55% of the initial volume to obtain a concentrated solution.
6. The method for producing D-glucosamine sulfate according to claim 1, wherein: in the step (2), the addition amount of the ethanol is 3-5 times of the volume of the concentrated solution.
7. The method for producing D-glucosamine sulfate according to claim 1, wherein: in the step (3), the adding amount of sodium chloride in the residual mother liquor is 1-2.5 g/L.
8. The method for producing D-glucosamine sulfate according to claim 1, wherein: in the step (3), the mass percentage of the ethanol and the water in the residual mother liquor is adjusted to 95.6:4.4, wherein the azeotropic temperature is 78.1 ℃; optionally, the oxygen-barrier condition is an atmosphere environment formed by any one of nitrogen and argon.
9. The method for producing D-glucosamine sulfate according to any one of claims 1-8, wherein: the method also comprises the step of condensing and collecting the azeotrope which is heated and volatilized in the step (3); preferably, the ethanol solution obtained by condensation and collection is used for the ethanol precipitation procedure described in step (2).
10. The method for producing D-glucosamine sulfate according to any one of claims 1-8, wherein: in the step (2), the drying mode comprises any one of freeze-drying and vacuum drying.
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