CN116715705A - Process for preparing glucosamine by using N-acetylglucosamine fermentation broth - Google Patents
Process for preparing glucosamine by using N-acetylglucosamine fermentation broth Download PDFInfo
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- 238000000855 fermentation Methods 0.000 title claims abstract description 42
- 230000004151 fermentation Effects 0.000 title claims abstract description 42
- 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 title claims abstract description 35
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229960002442 glucosamine Drugs 0.000 title claims abstract description 35
- OVRNDRQMDRJTHS-UHFFFAOYSA-N N-acelyl-D-glucosamine Natural products CC(=O)NC1C(O)OC(CO)C(O)C1O OVRNDRQMDRJTHS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 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 title claims abstract description 31
- 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 title claims abstract description 31
- 229950006780 n-acetylglucosamine Drugs 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 53
- 239000003930 superacid Substances 0.000 claims abstract description 52
- 239000012265 solid product Substances 0.000 claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 23
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000413 hydrolysate Substances 0.000 claims abstract description 20
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 108010009736 Protein Hydrolysates Proteins 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 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 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 18
- 150000002337 glycosamines Chemical class 0.000 abstract description 16
- 239000002253 acid Substances 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 238000004042 decolorization Methods 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000238557 Decapoda Species 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000002301 glucosamine derivatives Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- 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 description 1
- CERZMXAJYMMUDR-QBTAGHCHSA-N 5-amino-3,5-dideoxy-D-glycero-D-galacto-non-2-ulopyranosonic acid Chemical compound N[C@@H]1[C@@H](O)CC(O)(C(O)=O)O[C@H]1[C@H](O)[C@H](O)CO CERZMXAJYMMUDR-QBTAGHCHSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229920000288 Keratan sulfate Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004263 amino monosaccharides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229960001911 glucosamine hydrochloride Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229920000669 heparin Polymers 0.000 description 1
- 229960002897 heparin Drugs 0.000 description 1
- 235000020256 human milk Nutrition 0.000 description 1
- 210000004251 human milk Anatomy 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- KXCLCNHUUKTANI-RBIYJLQWSA-N keratan Chemical compound CC(=O)N[C@@H]1[C@@H](O)C[C@@H](COS(O)(=O)=O)O[C@H]1O[C@@H]1[C@@H](O)[C@H](O[C@@H]2[C@H](O[C@@H](O[C@H]3[C@H]([C@@H](COS(O)(=O)=O)O[C@@H](O)[C@@H]3O)O)[C@H](NC(C)=O)[C@H]2O)COS(O)(=O)=O)O[C@H](COS(O)(=O)=O)[C@@H]1O KXCLCNHUUKTANI-RBIYJLQWSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- CERZMXAJYMMUDR-UHFFFAOYSA-N neuraminic acid Natural products NC1C(O)CC(O)(C(O)=O)OC1C(O)C(O)CO CERZMXAJYMMUDR-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a process for preparing glucosamine by using N-acetylglucosamine fermentation broth, which comprises the following steps: 1. ti is mixed with 4+ Source, fe 3+ Adding alkali liquor for precipitation after uniformly mixing the sources; then separating out a solid product, and washing and drying the solid product to obtain a precursor; impregnating the precursor by using ammonium persulfate solution, drying the obtained precursor, and calcining to obtain modified solid superacid; 2. adding modified solid superacid into fermentation liquor of N-acetylglucosamine, hydrolyzing under heating, irradiating a reaction system with light source after completion, and performing solid-liquid separation after completion to obtain hydrolysate; 3. concentrating the hydrolysate, and performing alcohol treatmentAnd (5) settling, separating out a solid product, and drying to obtain an amino sugar product. The process not only overcomes the problems caused by hydrolysis by adopting concentrated acid solution, but also can realize the decolorization of the hydrolysate by utilizing the solid super-strong acid, and improves the purity of the obtained amino sugar product.
Description
Technical Field
The invention relates to the technical field of glucosamine, in particular to a process for preparing glucosamine by utilizing N-acetylglucosamine fermentation broth.
Background
Glucosamine is an amino monosaccharide in which the hydroxyl group on the 2-carbon of glucose is replaced by an amino group. The glucosamine is one of important monomers comprising polysaccharide hyaluronic acid, heparin, keratan sulfate and the like in organisms, is also a precursor substance for synthesizing breast milk oligosaccharide, neuraminic acid and chitosan oligosaccharide, and can maintain normal physiological functions of the organisms. In recent years, glucosamine derivatives (such as sulfate, hydrochloride and the like) are widely applied in the fields of foods, medicines and cosmetics, the demand of the glucosamine derivatives is increased year by year, and the glucosamine derivatives have wide market application prospects.
At present, the preparation process of the glucosamine mainly comprises a chemical extraction method and a microbial fermentation method, wherein the chemical extraction method takes shrimp and crab shells as raw materials, and the glucosamine is obtained by hydrochloric acid hydrolysis after chitin or chitosan is extracted from the shrimp and crab shells, but the glucosamine has fishy smell and is easy to cause allergy of people sensitive to marine products. In addition, because the heavy metals in the shrimp and crab shells are easy to exceed the standard, the glucosamine prepared by the chemical extraction method is easy to have the problem of exceeding the standard of the heavy metals. In contrast, glucosamine prepared by microbial fermentation does not have the above-described problems. The method firstly utilizes engineering bacteria to produce N-acetylglucosamine, and the N-acetylglucosamine is formed after the hydrolysis of concentrated acid, however, the use of the concentrated acid brings more pollution, a large amount of waste liquid is produced, and the concentrated acid has serious corrosion to equipment.
Disclosure of Invention
Aiming at the problems, the invention provides a process for preparing glucosamine by using N-acetylglucosamine fermentation broth, which adopts modified solid superacid to replace concentrated acid solution for hydrolysis, so that the problems brought by the concentrated acid solution are overcome, the solid superacid can be used for decoloring hydrolysate, and the purity of the obtained glucosamine product is improved. Specifically, the technical scheme of the invention is as follows.
A process for preparing glucosamine by using N-acetylglucosamine fermentation broth, comprising the steps of:
(1) Preparation of modified solid superacid: ti is mixed with 4+ Source, fe 3+ The sources are mixed uniformly, then alkali liquor is added while stirring, and the mixture is left to stand after the precipitation is completed. And separating out a solid product after the completion, and washing and drying the solid product to obtain a precursor. Impregnating the precursor with ammonium persulfate solution, drying the precursor, and calcining to obtain modified solid superacid (S) 2 O 8 2- /TiO 2 -Fe 2 O 3 ）。
(2) Adding modified solid super acid into fermentation liquor of N-acetylglucosamine, then carrying out hydrolysis reaction under the heating condition, irradiating a reaction system with light source after completion, and carrying out solid-liquid separation after completion to obtain hydrolysate.
(3) Concentrating the hydrolysate, precipitating with ethanol, separating solid product, and drying to obtain the final product.
Further, in the step (1), the Ti 4+ 、Fe 3+ The molar ratio of (3) to (5): 1-2. Optionally, the Ti is 4+ The source includes any one of titanium chloride, titanium nitrate, and the like. The Fe is 3+ Sources include any of ferric chloride, ferric nitrate, and the like.
Further, in the step (1), adding the alkali liquor until the pH of the reaction system is 9-11, and then standing for 20-24 hours. Optionally, the alkali liquor comprises any one of ammonia water, sodium hydroxide and the like.
Further, in the step (1), clean water is adopted to wash the solid product so as to remove residual soluble ions, and then the solid product is dried for 10-12 hours at the temperature of 95-110 ℃ to obtain the precursor.
Further, in the step (1), the concentration of the ammonium persulfate solution is 0.4-0.7 mol/L. The ammonium persulfate solution is used in an amount such that it can sufficiently impregnate the precursor.
Further, in the step (1), the dipping time is 10 to 14 hours, so that persulfate (S 2 O 8 2- ). And drying the obtained precursor for 1-2 hours at the temperature of 95-110 ℃.
Further, in the step (1), the calcination temperature is 470-550 ℃ and the calcination time is 2-3.5 hours, so as to form the modified solid super acid (S 2 O 8 2- /TiO 2 -Fe 2 O 3 ）。
Further, in the step (2), the mass ratio of the N-acetamido glucose in the fermentation liquid to the modified solid super acid is 10: 4-5.5.
Further, in the step (2), the heating temperature is 40-60 ℃, and the hydrolysis reaction time is 2-4 hours.
In the step (2), the power of the light source is 60-100W, and the irradiation time is 45-70 min.
Further, in the step (3), heating is performed to concentrate the hydrolysate to 40-55% of the initial volume. And then adding ethanol with the volume 3-5 times of the volume of the obtained concentrated solution for alcohol precipitation so as to crystallize and separate out the glucosamine in the concentrated solution.
Further, in the step (3), the drying mode includes freeze-drying, vacuum drying and the like.
Compared with the prior art, the invention has the following beneficial technical effects: the invention adopts modified solid super acid to replace concentrated hydrochloric acid to hydrolyze N-acetylglucosamine in the fermentation liquor, so that the N-acetylglucosamine is converted into glucosamine, thereby not only overcoming the concentrated acidThe solution brings the problems, and the solid superacid can be used for decoloring the hydrolysate, so that the purity of the obtained amino sugar product is improved. The reason for this is that: first, the modified solid superacid has a high-activity acid active center S 2 O 8 2- The method not only avoids the pollution problem caused by adopting concentrated hydrochloric acid under the catalysis of the method, but also removes residual concentrated hydrochloric acid without adding alkali liquor for neutralization because the modified solid superacid can be conveniently separated from the obtained hydrolysate by solid-liquid separation, thereby causing the obtained glucosamine to be actually glucosamine hydrochloride, and a large amount of chloride ions contained in the glucosamine can easily bring adverse effects. The modified solid superacid is adopted to hydrolyze the N-acetylglucosamine, so that chloride ions are not introduced, and the problems are well overcome. In addition, the modified solid super acid prepared by the invention uses TiO 2 Is a carrier and is doped with Fe 2 O 3 It not only serves as a promoter to further enhance the catalytic efficiency, but also improves the hydrolysis efficiency of the N-acetylglucosamine. And the Fe is 2 O 3 TiO is mixed with 2 The absorption side band of the modified solid super acid is extended to a visible light region, so that the modified solid super acid can be subjected to photocatalytic degradation and decoloration by utilizing visible light, and active oxygen generated by the modified solid super acid in the illumination process can degrade pigments in hydrolysate into water and carbon dioxide, so that the purity of an obtained amino sugar product is improved.
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 process for preparing glucosamine by using the N-acetylglucosamine fermentation broth comprises the following steps:
1. preparation of modified solid superacid:
TiCl is added to the mixture 4 Solution, feCl 3 According to Ti 4+ 、Fe 3+ The molar ratio of (2) is 4:1, and uniformly stirring the mixture. Concentrated aqueous ammonia was then added with rapid stirring to ph=10 of the reaction system, followed by standing for 24 hours. And (3) centrifuging to separate a solid product after completion, washing the solid product three times by adopting clear water, placing the solid product in an oven, and drying the solid product at 100 ℃ for 12 hours to obtain the precursor.
The precursor is immersed in 0.45mol/L ammonium persulfate solution for 12 hours, and after completion, the obtained precursor is placed in an oven and dried at 100 ℃ for 1.5 hours. And then placing the obtained precursor in a horse boiling furnace, and calcining for 3 hours at 500 ℃ to obtain the modified solid superacid.
2. According to the mass ratio of N-acetamido glucose in the fermentation liquid to modified solid super acid of 10:4.5, adding the modified solid super acid prepared in the embodiment into the fermentation broth. Then heated to 50℃in a water bath and incubated for 3 hours to carry out hydrolysis. And (3) irradiating the reaction system for 60min by using a 70W xenon lamp after completion, centrifuging to separate out the modified solid superacid after completion, and collecting a liquid phase to obtain the hydrolysate.
3. The hydrolysate was concentrated to 50% of the initial volume by heating in a water bath. And adding absolute ethyl alcohol with the volume 4 times of that of the obtained concentrated solution, uniformly stirring, and standing for 40min for alcohol precipitation. And after the completion, centrifugally separating a solid product, and drying the solid product in vacuum at 80 ℃ for 1 hour to obtain the amino sugar product. The purity of the amino sugar product described in this example was measured spectrophotometrically and found to be 92.33%.
Example 2
The process for preparing glucosamine by using the N-acetylglucosamine fermentation broth comprises the following steps:
1. preparation of modified solid superacid:
TiCl is added to the mixture 4 Solution, feCl 3 According to Ti 4+ 、Fe 3+ The molar ratio of (3): 1, and uniformly stirring the mixture. Sodium hydroxide was then added to the reaction system with rapid stirring to ph=11, and then allowed to stand for 22 hours. Centrifuging to separate solid product, washing the solid product with clear water for three times, and standingAnd (3) drying in an oven at 95 ℃ for 11 hours to obtain the precursor.
The precursor is immersed in 0.4mol/L ammonium persulfate solution for 10 hours, and after completion, the obtained precursor is placed in an oven and dried at 95 ℃ for 2 hours. And then placing the obtained precursor in a horse boiling furnace, and calcining for 2 hours at 550 ℃ to obtain the modified solid superacid.
2. According to the mass ratio of N-acetamido glucose in the fermentation liquid to modified solid super acid of 10:5.5, adding the modified solid super acid prepared in the embodiment into the fermentation broth. Then heated to 60℃in a water bath and incubated for 2 hours to carry out hydrolysis. And (3) irradiating the reaction system for 70min by using a 60W xenon lamp after completion, centrifuging to separate out the modified solid superacid after completion, and collecting a liquid phase to obtain the hydrolysate.
3. The hydrolysate was concentrated to 55% of the initial volume by heating in a water bath. And adding absolute ethyl alcohol with the volume 5 times of that of the obtained concentrated solution, uniformly stirring, and standing for 45min for alcohol precipitation. And after the completion, centrifugally separating a solid product, and drying the solid product in vacuum at 80 ℃ for 1 hour to obtain the amino sugar product. The purity of the amino sugar product described in this example was measured spectrophotometrically and found to be 94.07%.
Example 3
The process for preparing glucosamine by using the N-acetylglucosamine fermentation broth comprises the following steps:
1. preparation of modified solid superacid:
ti (NO) 3 ) 4 Solution, fe (NO) 3 ) 3 According to Ti 4+ 、Fe 3+ The molar ratio of (2) is 5:2, and uniformly stirring the mixture after mixing the components in proportion. Then, concentrated aqueous ammonia was added to the reaction system with rapid stirring until ph=9, followed by standing for 20 hours. And (3) centrifuging to separate a solid product after completion, washing the solid product three times by adopting clear water, placing the solid product in an oven, and drying the solid product at 110 ℃ for 10 hours to obtain the precursor.
The precursor is immersed in 0.7mol/L ammonium persulfate solution for 14 hours, and after completion, the obtained precursor is placed in an oven and dried at 110 ℃ for 1 hour. And then placing the obtained precursor in a horse boiling furnace, and calcining at 470 ℃ for 3.5 hours to obtain the modified solid superacid.
2. According to the mass ratio of N-acetamido glucose in the fermentation liquid to modified solid super acid of 10:4, and adding the modified solid super acid prepared in the embodiment into the fermentation broth. Then heated to 40℃in a water bath and incubated for 4 hours to carry out the hydrolysis reaction. And (3) irradiating the reaction system for 45min by using a 100W xenon lamp after the completion of the reaction, centrifugally separating out the modified solid superacid after the completion of the reaction, and collecting a liquid phase to obtain the hydrolysate.
3. The hydrolysate was concentrated to 40% of the initial volume by heating in a water bath. And adding absolute ethyl alcohol with the volume 3 times of that of the obtained concentrated solution, uniformly stirring, and standing for 35min for alcohol precipitation. And centrifuging to separate a solid product after completion, and freeze-drying the solid product to obtain the amino sugar product. The purity of the amino sugar product described in this example was measured spectrophotometrically and found to be 94.67%.
Example 4
The process for preparing glucosamine by using the N-acetylglucosamine fermentation broth comprises the following steps:
1. preparation of modified solid superacid:
to TiCl under rapid stirring 4 Concentrated aqueous ammonia was added to the solution to ph=10 of the reaction system, followed by standing for 24 hours. And (3) centrifuging to separate a solid product after completion, washing the solid product three times by adopting clear water, placing the solid product in an oven, and drying the solid product at 100 ℃ for 12 hours to obtain the precursor.
The precursor is immersed in 0.45mol/L ammonium persulfate solution for 12 hours, and after completion, the obtained precursor is placed in an oven and dried at 100 ℃ for 1.5 hours. And then placing the obtained precursor in a horse boiling furnace, and calcining for 3 hours at 500 ℃ to obtain the modified solid superacid.
2. According to the mass ratio of N-acetamido glucose in the fermentation liquid to modified solid super acid of 10:4.5, adding the modified solid super acid prepared in the embodiment into the fermentation broth. Then heated to 50℃in a water bath and incubated for 3 hours to carry out hydrolysis. And (3) irradiating the reaction system for 60min by using a 70W xenon lamp after completion, centrifuging to separate out the modified solid superacid after completion, and collecting a liquid phase to obtain the hydrolysate.
3. The hydrolysate was concentrated to 50% of the initial volume by heating in a water bath. And adding absolute ethyl alcohol with the volume 4 times of that of the obtained concentrated solution, uniformly stirring, and standing for 40min for alcohol precipitation. And after the completion, centrifugally separating a solid product, and drying the solid product in vacuum at 80 ℃ for 1 hour to obtain the amino sugar product. The purity of the amino sugar product described in this example was measured spectrophotometrically and found to be 86.52%.
Example 5
The process for preparing glucosamine by using the N-acetylglucosamine fermentation broth comprises the following steps:
1. preparation of modified solid superacid:
TiCl is added to the mixture 4 Solution, feCl 3 According to Ti 4+ 、Fe 3+ The molar ratio of (3): 1, and uniformly stirring the mixture. Sodium hydroxide was then added to the reaction system with rapid stirring to ph=11, and then allowed to stand for 22 hours. And (3) centrifuging to separate a solid product after completion, washing the solid product three times by adopting clear water, placing the solid product in an oven, and drying the solid product at 95 ℃ for 11 hours to obtain the precursor.
The precursor was placed in an oven and dried at 95 ℃ for 2 hours. And then placing the obtained precursor in a horse boiling furnace, and calcining for 2 hours at 550 ℃ to obtain the modified solid superacid.
2. According to the mass ratio of N-acetamido glucose in the fermentation liquid to modified solid super acid of 10:5.5, adding the modified solid super acid prepared in the embodiment into the fermentation broth. Then heated to 60℃in a water bath and incubated for 2 hours to carry out hydrolysis. And (3) irradiating the reaction system for 70min by using a 60W xenon lamp after completion, centrifuging to separate out the modified solid superacid after completion, and collecting a liquid phase to obtain the hydrolysate.
3. The hydrolysate was concentrated to 55% of the initial volume by heating in a water bath. And adding absolute ethyl alcohol with the volume 5 times of that of the obtained concentrated solution, uniformly stirring, and standing for 45min for alcohol precipitation. And after the completion, centrifugally separating a solid product, and drying the solid product in vacuum at 80 ℃ for 1 hour to obtain the amino sugar product. The purity of the amino sugar product described in this example was measured spectrophotometrically and found to be 31.26%.
Example 6
The process for preparing glucosamine by using the N-acetylglucosamine fermentation broth comprises the following steps:
1. preparation of modified solid superacid:
to Fe (NO) with rapid stirring 3 ) 3 Concentrated aqueous ammonia was added to the solution to ph=9 of the reaction system, followed by standing for 20 hours. And (3) centrifuging to separate a solid product after completion, washing the solid product three times by adopting clear water, placing the solid product in an oven, and drying the solid product at 110 ℃ for 10 hours to obtain the precursor.
The precursor is immersed in 0.7mol/L ammonium persulfate solution for 14 hours, and after completion, the obtained precursor is placed in an oven and dried at 110 ℃ for 1 hour. And then placing the obtained precursor in a horse boiling furnace, and calcining at 470 ℃ for 3.5 hours to obtain the modified solid superacid.
2. According to the mass ratio of N-acetamido glucose in the fermentation liquid to modified solid super acid of 10:4, and adding the modified solid super acid prepared in the embodiment into the fermentation broth. Then heated to 40℃in a water bath and incubated for 4 hours to carry out the hydrolysis reaction. And (3) irradiating the reaction system for 45min by using a 100W xenon lamp after the completion of the reaction, centrifugally separating out the modified solid superacid after the completion of the reaction, and collecting a liquid phase to obtain the hydrolysate.
3. The hydrolysate was concentrated to 40% of the initial volume by heating in a water bath. And adding absolute ethyl alcohol with the volume 3 times of that of the obtained concentrated solution, uniformly stirring, and standing for 35min for alcohol precipitation. And centrifuging to separate a solid product after completion, and freeze-drying the solid product to obtain the amino sugar product. The purity of the amino sugar product described in this example was measured spectrophotometrically and found to be 89.84%.
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 process for preparing glucosamine by using N-acetylglucosamine fermentation broth is characterized in that: the method comprises the following steps:
(1) Preparation of modified solid superacid: ti is mixed with 4+ Source, fe 3+ Uniformly mixing the sources, adding alkali liquor while stirring, and standing after precipitation is completed; separating out a solid product after the completion, and washing and drying the solid product to obtain a precursor; impregnating the precursor by using ammonium persulfate solution, drying the obtained precursor after completion, and calcining to obtain modified solid superacid;
(2) Adding modified solid superacid into fermentation liquor of N-acetylglucosamine, then carrying out hydrolysis reaction under the heating condition, irradiating a reaction system with light source after completion, and carrying out solid-liquid separation after completion to obtain hydrolysate;
(3) Concentrating the hydrolysate, precipitating with ethanol, separating solid product, and drying to obtain the final product.
2. The process for preparing glucosamine by utilizing the N-acetylglucosamine fermentation broth of claim 1, wherein the process comprises the steps of: in step (1), the Ti is 4+ 、Fe 3+ The molar ratio of (3) to (5): 1-2;
optionally, the Ti is 4+ The source comprises any one of titanium chloride and titanium nitrate;
optionally, the Fe 3+ The source comprises any one of ferric chloride and ferric nitrate.
3. The process for preparing glucosamine by utilizing the N-acetylglucosamine fermentation broth of claim 1, wherein the process comprises the steps of: in the step (1), adding the alkali liquor until the pH of a reaction system is between 9 and 11, and then standing for 20 to 24 hours; optionally, the alkali liquor comprises any one of ammonia water and sodium hydroxide.
4. The process for preparing glucosamine by utilizing the N-acetylglucosamine fermentation broth of claim 1, wherein the process comprises the steps of: in the step (1), clean water is adopted to wash the solid product, and then the solid product is dried for 10-12 hours at the temperature of 95-110 ℃ to obtain the precursor.
5. The process for preparing glucosamine by utilizing the N-acetylglucosamine fermentation broth of claim 1, wherein the process comprises the steps of: in the step (1), the concentration of the ammonium persulfate solution is 0.4-0.7 mol/L;
optionally, in the step (1), the soaking time is 10-14 hours; and drying the obtained precursor for 1-2 hours at the temperature of 95-110 ℃.
6. The process for preparing glucosamine by utilizing the N-acetylglucosamine fermentation broth of claim 1, wherein the process comprises the steps of: in the step (1), the calcination temperature is 470-550 ℃ and the calcination time is 2-3.5 hours.
7. The process for preparing glucosamine by utilizing the N-acetylglucosamine fermentation broth of claim 1, wherein the process comprises the steps of: in the step (2), the mass ratio of the N-acetamido glucose in the fermentation liquid to the modified solid super acid is 10: 4-5.5;
optionally, in the step (2), the heating temperature is 40-60 ℃, and the hydrolysis reaction time is 2-4 hours.
8. The process for preparing glucosamine by utilizing the N-acetylglucosamine fermentation broth of claim 1, wherein the process comprises the steps of: in the step (2), the power of the light source is 60-100W, and the irradiation time is 45-70 min.
9. The process for preparing glucosamine by utilizing an N-acetylglucosamine fermentation broth according to any one of claims 1-8, wherein: in the step (3), heating to concentrate the hydrolysate to 40-55% of the initial volume; and then adding ethanol with the volume 3-5 times of that of the obtained concentrated solution for alcohol precipitation.
10. The process for preparing glucosamine by utilizing an N-acetylglucosamine fermentation broth according to any one of claims 1-8, wherein: in the step (3), the drying mode comprises freeze-drying or vacuum drying.
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