CN113045610B - Method for extracting glucosamine from N-acetylglucosamine fermentation liquor - Google Patents
Method for extracting glucosamine from N-acetylglucosamine fermentation liquor Download PDFInfo
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- 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 95
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229960002442 glucosamine Drugs 0.000 title claims abstract description 95
- 238000000855 fermentation Methods 0.000 title claims abstract description 61
- 230000004151 fermentation Effects 0.000 title claims abstract description 61
- 229950006780 n-acetylglucosamine Drugs 0.000 title claims abstract description 38
- 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 37
- 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 37
- 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 37
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 51
- 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 claims abstract description 49
- 229960001911 glucosamine hydrochloride Drugs 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
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- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 17
- 238000005189 flocculation Methods 0.000 claims description 13
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- 238000004042 decolorization Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000008213 purified water Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
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- 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 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
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- 150000004676 glycans Chemical class 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-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
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- 102000055008 Matrilin Proteins Human genes 0.000 description 1
- 108010072582 Matrilin Proteins Proteins 0.000 description 1
- 241001465754 Metazoa Species 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
- 206010028980 Neoplasm Diseases 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 206010041591 Spinal osteoarthritis Diseases 0.000 description 1
- 208000007107 Stomach Ulcer Diseases 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004263 amino monosaccharides Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 208000003455 anaphylaxis Diseases 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000003260 anti-sepsis Effects 0.000 description 1
- 210000001188 articular cartilage Anatomy 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
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- 235000012970 cakes Nutrition 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 208000036319 cervical spondylosis Diseases 0.000 description 1
- 230000004186 co-expression Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 238000001784 detoxification Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- CBMPTFJVXNIWHP-UHFFFAOYSA-L disodium;hydrogen phosphate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].OP([O-])([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O CBMPTFJVXNIWHP-UHFFFAOYSA-L 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- 201000005917 gastric ulcer Diseases 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 150000002301 glucosamine derivatives Chemical class 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007365 immunoregulation 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
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 201000008482 osteoarthritis Diseases 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
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- 239000000825 pharmaceutical preparation Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- 239000002351 wastewater 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
-
- 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)
- Saccharide Compounds (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a method for extracting glucosamine from N-acetylglucosamine fermentation liquor, which comprises the following process steps: acidifying and hydrolyzing the N-acetylglucosamine fermentation liquor by an acid ejector, then adding water for dilution, centrifugally separating, decompressing and concentrating to obtain a glucosamine concentrated solution, then flocculating and precipitating, standing and separating, filtering, decoloring by anion macroporous resin to obtain a glucosamine decoloring solution, extracting the glucosamine decoloring solution by cation macroporous resin, resolving by hydrochloric acid, crystallizing, and centrifugally separating to obtain a glucosamine hydrochloride crude product. The whole process operation is simpler and more convenient, the production progress is easy to guarantee, and the method is favorable for improving the product quality and the yield.
Description
Technical Field
The invention belongs to the technical field of biological fermentation and extraction, and particularly relates to a method for extracting glucosamine from N-acetylglucosamine fermentation liquor.
Background
Glucosamine is a natural amino monosaccharide, is a substance essential for synthesis of proteoglycan in human articular cartilage matrix, and has a molecular formula of C 6 H 13 O 5 N, the structural formula is as follows:
glucosamine is a compound in which one hydroxyl group of glucose is substituted by one amino group, commonly called glucosamine, and is easily soluble in water and hydrophilic solvents. They are usually present in polysaccharides of microbial, animal origin and in conjugated polysaccharides in the form of N-acetyl derivatives, such as chitin, or N-sulfates and N-acetyl-3-O-lactic acid ethers (muramic acid).
Glucosamine has the effects of immunoregulation, osteoarthritis treatment, antioxidation, anti-aging, antisepsis, antibiosis and the like, and is widely applied to medical treatment, food, cosmetics and agriculture.
In medical treatment, the glucosamine can slow down the pathological changes of joints and cartilage parts, relieve the joint pain and is beneficial to regenerating cartilage tissues; can also be used for treating gastric ulcer; if the antibiotics are taken while the glucosamine is taken, the absorption of blood to the antibiotics can be promoted, the curative effect is improved, and some side effects are reduced; in addition, the glucosamine has obvious curative effects on preventing cervical spondylosis, participating in liver and kidney detoxification, resisting cancer and the like.
In food, glucosamine is nontoxic to human body, has the effects of resisting aging, stimulating the growth of bifidobacteria in intestinal tracts of infants, regulating endocrine and the like, and can be used as a food ingredient. Some manufacturers, such as japan and the united states, add glucosamine to products such as cakes, breads, beverages, and the like.
Can be added into high-grade cosmetics, plant growth regulator, and feed additive in cosmetics and agriculture.
Glucosamine, which is a pharmaceutical product, is mostly present in the form of hydrochloride, sulfate or double salt because the glucosamine monomer is unstable and is very deliquescent in the air.
Currently, glucosamine is mainly produced by a biological extraction method and a microbial fermentation method, wherein
The biological extraction method is characterized in that chitin or chitosan is extracted from shrimp and crab shells, and then the chitin or chitosan is hydrolyzed by hydrochloric acid to form glucosamine hydrochloride.
The microbial fermentation process adopts transgenic engineering technology, co-expression of glucosamine synthase and glucosamine acetylase gene in colibacillus to obtain transgenic engineering bacteria, fermentation of glucose as fermenting material to obtain fermented liquid containing N-acetylglucosamine, adding 0.1 mol/L hydrochloric acid, boiling at 100 deg.c for 3 hr to convert over 90% of N-acetylglucosamine into glucosamine, extracting, purifying, concentrating, crystallizing, drying and other steps to produce serial glucosamine products. The product obtained by the microbial fermentation method has good quality, no fishy smell and no anaphylactic reaction, and is deeply welcomed by the market. Along with the improvement of fermentation technical level, the yield improvement space is larger, and the microbial fermentation method has the potential of industrial mass production and becomes the industry development direction.
In the process of preparing glucosamine from the N-acetylglucosamine fermentation liquor, the fermentation liquor is usually filtered, then extracted and purified by strong acid cation resin, and the N-acetylglucosamine is converted into glucosamine, or 0.1 mol/L hydrochloric acid is added, and the mixture is boiled at 100 ℃ for 3h, and the N-acetylglucosamine is converted into glucosamine, and then the glucosamine series products (hydrochloride and sulfate) are produced by the processes of concentration, crystallization and the like. The production process has the following problems:
the N-acetylglucosamine has the characteristics of insolubility in water, dilute acid, dilute alkali, concentrated alkali and organic solvent, so that the N-acetylglucosamine fermentation liquor is directly filtered without acid hydrolysis, the yield of glucosamine extracted is low, and the N-acetylglucosamine fermentation liquor is directly acidified and hydrolyzed by strong acid in an acidification tank, so that the hydrolysis efficiency is low and the equipment is easy to corrode.
The N-acetylglucosamine fermentation liquor contains glucosamine and a large amount of protein substances besides the N-acetylglucosamine, the protein is an amphoteric compound, when the N-acetylglucosamine is absorbed by cation exchange, part of the protein can be absorbed, the absorption yield of the cation resin is influenced, and the obtained glucosamine analysis liquor is directly crystallized without removing the protein, so that the quality is poor.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the method for extracting glucosamine from the N-acetylglucosamine fermentation broth, which effectively improves the product quality, improves the yield, is convenient and fast in process operation, generates less waste water and is beneficial to environmental protection treatment.
The technical scheme adopted for realizing the purpose is as follows:
a method for extracting glucosamine from N-acetylglucosamine fermentation liquor is characterized by comprising the following process steps: acidifying and hydrolyzing the N-acetylglucosamine fermentation liquor by an acid ejector, then adding water for dilution, centrifugally separating, decompressing and concentrating to obtain a glucosamine concentrated solution, then flocculating and precipitating, standing and separating, filtering, decoloring by anion macroporous resin to obtain a glucosamine decoloring solution, extracting the glucosamine decoloring solution by cation macroporous resin, resolving by hydrochloric acid, crystallizing, and centrifugally separating to obtain a glucosamine hydrochloride crude product.
During the acidification hydrolysis, the feeding ratio V is controlled Fermentation liquor ：V Sulfuric acid 0.15-0.18, hydrolysis temperature of 45-65 ℃, and ejector aperture phi of 2-5 mm.
When the water is added for dilution, the water adding amount is V Acidified hydrolysate : V Water (W) And (4) = 1.6-1.5.
Adding water with the weight 1.5-3 times of that of the centrifugal slag obtained after centrifugal separation into the centrifugal slag, stirring for 20-30 minutes, then carrying out centrifugal separation, and collecting the obtained centrifugal liquid into the previous centrifugal liquid for reduced pressure concentration.
The vacuum concentration ratio is preferably 3.0 to 5.0.
In the flocculation precipitation process, the used flocculating agent is polyacrylamide, the dosage of the flocculating agent is 0.6-0.9 percent of the mass of the glucosamine concentrated solution, the flocculation temperature is 35-45 ℃, the flocculation time is 15-20 minutes, and the flocculating agent is stirred once every 5 minutes in the flocculation precipitation process.
The standing separation time is 15-30 min.
When the anion macroporous resin is used for decoloring, the anion macroporous resin is a D900 column, and the decoloring feeding temperature is 40-45 ℃.
The extraction and hydrochloric acid resolution by using the cation macroporous resin means that the glucosamine decolorization solution is adjusted to 30-35 ℃, then the glucosamine decolorization solution is added into the cation macroporous resin, the feeding speed is controlled to be 1-2 BV/h, after the feed liquid is fed, the glucosamine decolorization solution is resolved by using 0.3-0.5 mol/L hydrochloric acid, and the resolution speed is 1-1.5 BV/h, wherein the cation macroporous resin is a D62 column.
The crystallization is to add 3-5 times of ethanol into the obtained analytic solution to separate out glucosamine hydrochloride.
Dissolving the obtained glucosamine hydrochloride crude product with purified water, adding activated carbon for decolorization, wherein the adding amount of the activated carbon is 0.6-0.8 percent of the mass of the crude product, the decolorizing temperature is 40-45 ℃, filtering with a plate frame, cooling the obtained filtrate to 10-15 ℃, adding ethanol with the volume of 3-5 times of the filtrate to separate out the glucosamine hydrochloride, centrifugally separating, and drying in vacuum to obtain the glucosamine hydrochloride finished product.
Compared with the traditional process for extracting glucosamine from fermentation liquor, the method has the technical advantages that:
the fermentation liquor of the 1N-acetylglucosamine is acidified and hydrolyzed by an acidification ejector to ensure that the N-acetylglucosamine is fully hydrolyzed to obtain the glucosamine, thereby avoiding the poor water solubility of the N-acetylglucosamine, entering the bacterial residue during filtration and separation to influence the yield of the glucosamine, leading the whole process operation to be simpler and more convenient, ensuring the production progress easily, and being beneficial to improving the product quality and the yield.
2 the invention adopts the anion flocculant and anion resin to remove protein and pigment, and then adopts the cation macroporous resin to extract the glucosamine, thereby improving the extraction yield and quality of the glucosamine.
Detailed Description
The invention is illustrated below by way of examples, which are to be understood as being illustrative and not limiting. The scope and spirit of the present invention are defined by the appended claims.
Taking 800L of N-acetylglucosamine fermentation liquor (fermentation titer is 78g/L, solid content is 0.22 w/w), and respectively carrying out the following experiments, wherein:
example 1
Taking 100L of N-acetylglucosamine fermentation liquor, heating to 45 ℃, adjusting the flow of the fermentation liquor and sulfuric acid to ensure that the fermentation liquor and the sulfuric acid are mixed according to a feeding ratio (fermentation liquor (V): sulfuric acid (V) = 0.15), atomizing sulfuric acid by an ejector (the aperture of the ejector is phi 2 mm), mixing the sulfuric acid with the fermentation liquor, adding water with the volume of 0.6 time of the acidified hydrolysis liquid into an acidification liquid tank, stirring for 15 minutes, carrying out centrifugal separation, respectively collecting filter residues and centrifugal liquid, adding water with the weight of 1.5 times of the weight of the centrifugal residues into a filter residue washing tank, stirring for 20 minutes, thoroughly washing the centrifugal residues with water, carrying out centrifugal separation, combining the two centrifugates, carrying out reduced-pressure concentration by using a thin-film evaporator, and concentrating the centrifugate by 3 times to obtain an glucosamine concentrated solution.
Heating the glucosamine concentrated solution to 35 ℃, adding 0.6% (w/v) polyacrylamide, flocculating and precipitating for 15 minutes, stirring once every 5 minutes during the flocculation and precipitation, stirring for 2min each time, standing for 15 minutes, filtering by a plate frame to obtain a filtrate, heating to 40 ℃, and filtering by anion decolorizing resin (D900 column) to obtain the glucosamine decolorizing solution.
Adjusting the temperature of the glucosamine decolorant to 30 ℃, feeding into a cation macroporous resin (D62 column) at a feeding speed of 2BV/h, after the feed liquid is fed, resolving by using 0.3mol/L hydrochloric acid at a resolving speed of 1BV/h, and collecting the resolving liquid to obtain the glucosamine resolving liquid.
And (3) adding the glucosamine analytic solution into a crystallizer, slowly stirring, adding ethanol with the volume of 3 times to separate out glucosamine hydrochloride, and performing centrifugal separation to obtain a crude glucosamine hydrochloride product.
And adding purified water to dissolve the glucosamine hydrochloride crude product under stirring, heating to 40 ℃, adding activated carbon according to 0.6% (W/W) of the mass of the crude product for decoloring for 15 minutes, filtering by using a plate frame, collecting a decoloring solution, cooling to 10 ℃, slowly stirring, adding 3 times of ethanol by volume, separating out glucosamine hydrochloride, centrifugally separating, and drying in vacuum to obtain 5778g of glucosamine hydrochloride finished product. The total yield was 74.08%.
Example 2
Taking 100L of N-acetylglucosamine fermentation liquor, heating to 50 ℃, adjusting the flow of the fermentation liquor and sulfuric acid, mixing the fermentation liquor and the sulfuric acid according to a feeding ratio (fermentation liquor (V): sulfuric acid (V) = 1.16), atomizing the sulfuric acid by an ejector (the aperture of the ejector is phi 2 mm), adding the sulfuric acid into the fermentation liquor, adding 0.8 time of acidified hydrolysis liquid into an acidification tank, stirring for 15 minutes, carrying out centrifugal separation, respectively collecting filter residue and centrifugal liquid, diluting the filter residue and the centrifugal liquid by adding water in an amount which is 3 times of the weight of the centrifugal residue into a filter residue washing tank, stirring for 20 minutes, thoroughly washing the centrifugal residue with water, centrifuging, combining the two times of centrifugal liquid, carrying out reduced pressure concentration by using a film evaporator, and concentrating the centrifugal liquid by 4 times to obtain an glucosamine concentrated solution.
Heating the glucosamine concentrated solution to 40 ℃, adding 0.7% (w/v) polyacrylamide, flocculating and precipitating for 18 minutes, stirring once every 5 minutes during the flocculation and precipitation, stirring for 2min each time, standing for 15 minutes, filtering by a plate frame to obtain a filtrate, heating to 42 ℃, and filtering by anion decolorizing resin (D900 column) to obtain the glucosamine decolorizing solution.
Adjusting the temperature of the glucosamine decolorant liquid to 32 ℃, feeding into cation macroporous resin (D62 column) at a feeding speed of 1BV/h, after the feed liquid is fed completely, resolving with 0.5mol/L hydrochloric acid at a resolving speed of 1.2BV/h, and collecting the resolved liquid to obtain the glucosamine resolved liquid.
Adding the glucosamine analytic solution into a crystallizer, slowly stirring, adding 4 times volume of ethanol to separate out glucosamine hydrochloride, and centrifuging to obtain a glucosamine hydrochloride crude product.
And adding purified water to dissolve the glucosamine hydrochloride crude product under stirring, heating to 42 ℃, adding activated carbon to decolor according to 0.7% (W/W) of the weight of the crude product, decoloring for 15 minutes, filtering by using a plate frame, collecting a decolored solution, cooling to 12 ℃, slowly stirring, adding 4 times of ethanol by volume, separating out glucosamine hydrochloride, centrifuging to obtain a glucosamine hydrochloride pure product, and drying under vacuum to obtain 5775g of a glucosamine hydrochloride finished product. The total yield was 74.04%.
Example 3
Taking 100L of N-acetylglucosamine fermentation liquor, heating to 55 ℃, adjusting the flow of the fermentation liquor and sulfuric acid, mixing the fermentation liquor and the sulfuric acid according to a feeding ratio (fermentation liquor (V): sulfuric acid (V) = 0.16), atomizing the sulfuric acid by an ejector (the aperture of the ejector is phi 3 mm), adding the sulfuric acid into the fermentation liquor, adding 1 time of acidified hydrolysis liquid into an acidification tank, stirring for 15 minutes, performing centrifugal separation, collecting filter residues and centrifugate respectively, adding water in an amount which is 3.0 times of the weight of the centrifugate into a filter residue washing tank, stirring for 20 minutes, washing the centrifugate with water thoroughly, centrifuging, combining the centrifugates, performing reduced pressure concentration by using a film evaporator, and concentrating the centrifugate by 5 times to obtain an glucosamine concentrated solution.
Heating the glucosamine concentrated solution to 45 ℃, adding 0.8% (w/v) polyacrylamide, flocculating and precipitating for 15 minutes, stirring once every 5 minutes during the flocculation and precipitation, stirring for 2min each time, standing for 15 minutes, filtering by a plate frame to obtain a filtrate, heating to 44 ℃, and filtering by anion decolorizing resin (D900 column) to obtain the glucosamine decolorizing solution.
Adjusting the temperature of the glucosamine decolorant to 34 ℃, feeding into a cation macroporous resin (D62 column) at a feeding speed of 2BV/h, after the feed liquid is fed, resolving by using 0.5mol/L hydrochloric acid at a resolving speed of 1.5BV/h, and collecting the resolving liquid to obtain the glucosamine resolving liquid.
Adding the glucosamine analytic solution into a crystallizer, slowly stirring, adding 5 times volume of ethanol to separate out glucosamine hydrochloride, and centrifuging to obtain a crude glucosamine hydrochloride product.
Adding purified water to dissolve the glucosamine hydrochloride crude product under stirring, heating to 45 ℃, adding activated carbon to decolor according to 0.8% (W/W) of the weight of the crude product, decoloring for 15 minutes, filtering by using a plate frame, collecting a decolored solution, cooling to 15 ℃, slowly stirring, adding 5 times of ethanol by volume, separating out glucosamine hydrochloride, centrifugally separating to obtain a glucosamine hydrochloride pure product, and drying under vacuum to obtain a glucosamine hydrochloride finished product with the total yield of 5821g of 74.63%.
Example 4
Taking 100L of N-acetylglucosamine fermentation liquor, heating to 60 ℃, adjusting the flow of the fermentation liquor and sulfuric acid, mixing the fermentation liquor and the sulfuric acid according to a feeding ratio (fermentation liquor (V): sulfuric acid (V) = 0.18), atomizing the sulfuric acid by an ejector (the aperture of the ejector is phi 5 mm), adding the sulfuric acid into the fermentation liquor, adding 1.2 times of acidified hydrolysis liquid into an acidification tank, stirring for 15 minutes, carrying out centrifugal separation, respectively collecting filter residue and centrifugal liquid, adding water 2.0 times of the weight of the centrifugal residue into a filter residue washing tank, stirring for 20 minutes, thoroughly washing the centrifugal residue with water, centrifuging, combining the two centrifugates, carrying out reduced pressure concentration by using a film evaporator, and concentrating the centrifugate by 4 times to obtain an glucosamine concentrated solution.
Heating the glucosamine concentrated solution to 40 ℃, adding 0.63g of 0.9% (w/v) polyacrylamide, flocculating for 18 minutes, stirring once every 5 minutes during the flocculation, stirring for 2min each time, standing for 15 minutes, filtering by a plate frame to obtain a filtrate, heating to 45 ℃, and filtering by anion decolorizing resin (D900 column) to obtain the glucosamine decolorizing solution.
Adjusting the temperature of the glucosamine decolorant to 35 ℃, feeding into a cation macroporous resin (D62 column) at a feeding speed of 2BV/h, after the feed liquid is fed, resolving by using 0.4mol/L hydrochloric acid at a resolving speed of 1.2BV/h, and collecting the resolving liquid to obtain the glucosamine resolving liquid.
Adding the glucosamine analytic solution into a crystallizer, slowly stirring, adding 4 times of ethanol to separate out glucosamine hydrochloride, and performing centrifugal separation to obtain a glucosamine hydrochloride crude product;
adding purified water to dissolve the glucosamine hydrochloride crude product under stirring, heating to 42 ℃, adding activated carbon to decolor according to 0.7 percent (W/W) of the weight of the crude product, decoloring for 15 minutes, filtering by using a plate frame, collecting decolored liquid, cooling to 12 ℃, slowly stirring, adding 4 times of ethanol by volume, separating out glucosamine hydrochloride, centrifugally separating, and drying in vacuum to obtain 5856g glucosamine hydrochloride finished product. The total yield was 75.08%.
Example 5
Taking 100L of N-acetylglucosamine fermentation liquor, heating to 65 ℃, adjusting the flow of the fermentation liquor and sulfuric acid to ensure that the fermentation liquor and the sulfuric acid are mixed according to a feeding ratio (fermentation liquor (V): sulfuric acid (V) = 0.17), atomizing sulfuric acid by an ejector (the aperture phi of the ejector is 5 mm), mixing the mixture with the fermentation liquor, adding 1.5 times of acidification hydrolysis liquid into an acidification liquid tank, adding water into the mixture, stirring for 15 minutes, carrying out centrifugal separation, respectively collecting filter residues and centrifugal liquid, adding water into the filter residues in an amount which is 1.5 times of the weight of the centrifugal residues in a filter residue washing tank, stirring for 15 minutes, thoroughly washing the centrifugal residues with water, carrying out centrifugal separation, combining the two times of centrifugal liquid, carrying out reduced pressure concentration by using a film evaporator, and concentrating the centrifugal liquid by 3 times to obtain an glucosamine concentrated solution.
Heating the glucosamine concentrated solution to 40 ℃, adding 0.8% (w/v) polyacrylamide, flocculating and precipitating for 20 minutes, stirring once every 5 minutes during the flocculation and precipitation, stirring for 2min each time, standing for 15 minutes, filtering by a plate frame to obtain a filtrate, heating to 42 ℃, and filtering by anion decolorizing resin (D900 column) to obtain the glucosamine decolorizing solution.
Adjusting the temperature of the glucosamine decolorant to 32 ℃, feeding into a cation macroporous resin (D62 column) at a feeding speed of 2BV/h, after the feed liquid is fed, resolving by using 0.4mol/L hydrochloric acid at a resolving speed of 1.2BV/h, and collecting the resolving liquid to obtain the glucosamine resolving liquid.
Adding the glucosamine analytic solution into a crystallizer, slowly stirring, adding 4 times volume of ethanol to separate out glucosamine hydrochloride, and centrifuging to obtain a glucosamine hydrochloride crude product.
Adding purified water into the glucosamine hydrochloride crude product under stirring for dissolving, heating to 42 ℃, adding activated carbon for decoloring for 15 minutes according to the weight of 0.7% (W/W) of the crude product, filtering by using a plate frame, collecting a decoloring solution, cooling to 12 ℃, slowly stirring, adding 4 times volume of ethanol, separating out glucosamine hydrochloride, performing centrifugal separation, and performing vacuum drying to obtain 5911g of glucosamine hydrochloride finished product. The total yield is 75.78%.
Comparative example 1
Taking 100L of N-acetylglucosamine fermentation liquor, adding 0.1 mol/L hydrochloric acid, decocting at 100 deg.C for 3h to obtain glucosamine hydrolysate, filtering with ceramic membrane to obtain glucosamine clear liquid, and concentrating under reduced pressure to obtain glucosamine concentrated solution.
Adding the glucosamine concentrated solution into a crystallizer, slowly stirring, adding ethanol with 4 times of volume, separating out crystals, and centrifuging to obtain a glucosamine hydrochloride crude product.
Adding purified water to dissolve the glucosamine hydrochloride crude product under stirring, heating to 42 ℃, adding activated carbon to decolor according to 0.7% (W/W) of the weight of the crude product, decoloring for 15 minutes, filtering by using a plate frame, collecting a decolored solution, cooling to 12 ℃, slowly stirring, adding 4 times of ethanol by volume, separating out glucosamine hydrochloride to obtain a glucosamine hydrochloride pure product, centrifuging to obtain a glucosamine hydrochloride finished product 5458g. The total yield is 69.97%.
Comparative example 2
Taking 100L of N-acetylglucosamine fermentation liquor, adding disodium hydrogen phosphate-citric acid buffer solution, adjusting pH to 2.2, controlling temperature to about 30 deg.C, introducing into strong acid cation exchange resin 001 × 8 to adsorb glucosamine, eluting with 0.7% ammonium sulfate solution to obtain glucosamine analysis solution, and concentrating under reduced pressure to obtain glucosamine concentrate.
Adding the glucosamine concentrated solution into a crystallizer, slowly stirring, adding ethanol with 4 times of volume, separating out crystals, and centrifuging to obtain a glucosamine hydrochloride crude product.
And (2) adding purified water into the glucosamine hydrochloride crude product under stirring to dissolve, heating to 42 ℃, adding activated carbon for decoloring for 15 minutes according to the weight of 0.7% (W/W) of the crude product, filtering by using a plate frame, collecting a decoloring solution, cooling to 12 ℃, slowly stirring, adding 4 times of ethanol by volume, separating out glucosamine hydrochloride, centrifuging to obtain a glucosamine hydrochloride pure product, and drying in vacuum to obtain 5510g of a glucosamine hydrochloride finished product. The total yield is 70.64%.
Claims (7)
1. A method for extracting glucosamine from N-acetylglucosamine fermentation broth is characterized by comprising the following process steps: acidifying and hydrolyzing the N-acetylglucosamine fermentation liquor by an acid ejector, then adding water for dilution, centrifugally separating, decompressing and concentrating to obtain a glucosamine concentrated solution, then flocculating and precipitating, standing for separation, filtering, decoloring by anion macroporous resin to obtain a glucosamine decoloring solution, extracting the glucosamine decoloring solution by cation macroporous resin, resolving by hydrochloric acid, crystallizing, centrifugally separating to obtain a glucosamine hydrochloride crude product, wherein:
during the acidification hydrolysis, the feeding ratio V is controlled Fermentation liquor ：V Sulfuric acid =1: 0.15-0.18, hydrolysis temperature of 45-65 ℃, and ejector aperture phi of 2-5 mm;
in the flocculation precipitation process, the used flocculating agent is polyacrylamide, the dosage of the flocculating agent is 0.6-0.9 percent of the mass of the glucosamine concentrated solution, the flocculation temperature is 35-45 ℃, the flocculation time is 15-20 minutes, and the flocculating agent is stirred once every 5 minutes in the flocculation precipitation process;
when the anion macroporous resin is used for decoloring, the anion macroporous resin is a D900 column, and the decoloring feeding temperature is 40-45 ℃;
the extraction and hydrochloric acid resolution by using the cation macroporous resin means that the glucosamine decolorization solution is adjusted to 30-35 ℃, then the glucosamine decolorization solution is added into the cation macroporous resin, the feeding speed is controlled to be 1-2 BV/h, after the feed liquid is fed, the glucosamine decolorization solution is resolved by using 0.3-0.5 mol/L hydrochloric acid, and the resolution speed is 1-1.5 BV/h, wherein the cation macroporous resin is a D62 column.
2. The method for extracting glucosamine from an N-acetylglucosamine fermentation broth according to claim 1, wherein the amount of water added during the dilution with water is such that the hydrolysis solution is acidified according to V: v water =1:0.6 to 1.5.
3. The method for extracting glucosamine from N-acetylglucosamine fermentation broth according to claim 1, wherein water is added to the centrifuged residue after centrifugation in an amount of 1.5 to 3 times the weight of the centrifuged residue, the centrifuged residue is stirred for 20 to 30 minutes, and the resulting centrifugate is collected into the previous centrifugate and then concentrated under reduced pressure.
4. The process for extracting glucosamine from N-acetylglucosamine fermentation broth according to claim 1 or 3, wherein the concentration under reduced pressure is preferably 3.0 to 5.0.
5. The method for extracting glucosamine from N-acetylglucosamine fermentation broth according to claim 1, wherein the standing separation time is 15 to 30min.
6. The method for extracting glucosamine from N-acetylglucosamine fermentation broth according to claim 1, wherein the crystallization is performed by adding 3 to 5 times of ethanol to the resulting analysis solution to precipitate glucosamine hydrochloride.
7. The method for extracting glucosamine from N-acetylglucosamine fermentation broth according to claim 1, wherein the glucosamine hydrochloride crude product is dissolved in purified water, activated carbon is added for decolorization, the amount of activated carbon is 0.6-0.8% of the mass of the crude product, the decolorization temperature is 40-45 ℃, plate and frame filtration is performed, the obtained filtrate is cooled to 10-15 ℃, ethanol with the volume 3-5 times of the filtrate is added to separate glucosamine hydrochloride out, centrifugal separation is performed, and vacuum drying is performed to obtain the glucosamine hydrochloride finished product.
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