CN106188168A - Utilize the method that the dreg producing glutamic acid prepares glucosamine hydrochloride - Google Patents
Utilize the method that the dreg producing glutamic acid prepares glucosamine hydrochloride Download PDFInfo
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- CN106188168A CN106188168A CN201610566219.7A CN201610566219A CN106188168A CN 106188168 A CN106188168 A CN 106188168A CN 201610566219 A CN201610566219 A CN 201610566219A CN 106188168 A CN106188168 A CN 106188168A
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- methanol
- supernatant
- glutamic acid
- glucosamine hydrochloride
- white precipitate
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- CBOJBBMQJBVCMW-BTVCFUMJSA-N (2r,3r,4s,5r)-2-amino-3,4,5,6-tetrahydroxyhexanal;hydrochloride Chemical compound Cl.O=C[C@H](N)[C@@H](O)[C@H](O)[C@H](O)CO CBOJBBMQJBVCMW-BTVCFUMJSA-N 0.000 title claims abstract description 53
- 229960001911 glucosamine hydrochloride Drugs 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 36
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 235000013922 glutamic acid Nutrition 0.000 title claims abstract description 30
- 239000004220 glutamic acid Substances 0.000 title claims abstract description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000006228 supernatant Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002244 precipitate Substances 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 241000894006 Bacteria Species 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- 239000012467 final product Substances 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 9
- 229960004756 ethanol Drugs 0.000 description 8
- 238000004809 thin layer chromatography Methods 0.000 description 6
- 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 5
- 230000000694 effects Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- UBDZFAGVPPMTIT-UHFFFAOYSA-N 2-aminoguanidine;hydron;chloride Chemical class [Cl-].NC(N)=N[NH3+] UBDZFAGVPPMTIT-UHFFFAOYSA-N 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 239000006227 byproduct Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000008121 dextrose Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229960002442 glucosamine Drugs 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 210000004185 liver Anatomy 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 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 description 1
- 206010018910 Haemolysis Diseases 0.000 description 1
- 208000007107 Stomach Ulcer Diseases 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 201000005917 gastric ulcer Diseases 0.000 description 1
- 229960002849 glucosamine sulfate Drugs 0.000 description 1
- 230000008588 hemolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 201000003068 rheumatic fever Diseases 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- -1 stand Substances 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- 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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a kind of method utilizing the dreg producing glutamic acid to prepare glucosamine hydrochloride, step is as follows: (1) takes glutamic acid wet bacteria slag, adds the ethanol solution of 23 times of volumes, reflux, extract, filters, obtain filtering residue；(2) in filtering residue, add water, supersound extraction, filter, obtain filtrate；(3) filtrate is evaporated, obtains dry, in dry, be sequentially added into water and hydrochloric acid, hydrolyze 35 hours under the conditions of 15 30 DEG C, after hydrolysis, add methanol, stand, pour out supernatant；(4) pH of regulation supernatant is 7 7.2, filters, obtains white precipitate；Adding methanol, stirring and dissolving in white precipitate, obtain methanol supernatant, residue white precipitate adds methanol and dissolves, and repeated several times merges methanol supernatant, is concentrated to dryness, to obtain final product.The present invention establishes a kind of method efficiently preparing glucosamine hydrochloride from the dreg producing glutamic acid first, and kind and the consumption of required reagent are few, reduce the preparation cost of glucosamine hydrochloride.
Description
Technical field
The present invention relates to a kind of method utilizing the dreg producing glutamic acid to prepare glucosamine hydrochloride, belong to food and change
Work field.
Background technology
Glucosamine hydrochloride is also known as glucosamine hydrochloride.Human body is had important physiological function, participates in liver, kidney solution
Poison, plays antiinflammatory liver protection effect.Treatment rheumatic arthritis and gastric ulcer there is good curative effect.It it is synthetic antibiotic and anticancer
The primary raw material of medicine, it is also possible in chemical industry, food, cosmetics and feed additive.The amino sold in the market
Sugar Capsules of health productions principle active component is glucosamine hydrochloride or glucosamine sulfate.
Glucosamine hydrochloride is as a kind of fine chemical product, and its product price is high, and the market demand is big, the most mostly by
Insecticide shell or carapace pyrohydrolysis prepare, and originate relatively limited.Glutamic acid dreg is the principal by product of monosodium glutamate industry, I
The glutamic acid dreg that state produces every year reaches million tons, for the recycling of glutamic acid dreg, the most how to make as feedstuff and fertilizer
With, produced value is relatively low.
Jiang Xinying is hydrochloric acid ammonia during preparing 3-O-.alpha.-carboxyethyl-D-glucosamine. by the dreg producing glutamic acid it was confirmed in glutamic acid dreg
The existence of base glucose, but glucosamine hydrochloride is the by-product prepared as 3-O-.alpha.-carboxyethyl-D-glucosamine., and productivity is relatively low, and preparation technology
Complexity, required reagent type and consumption are too big, and preparation cost is the highest.
Summary of the invention
For above-mentioned prior art, it is an object of the invention to provide a kind of dreg utilizing production glutamic acid and prepare hydrochloric acid ammonia
The method of base glucose.
For achieving the above object, the present invention uses following technical proposals:
A kind of method utilizing the dreg producing glutamic acid to prepare glucosamine hydrochloride, step is as follows:
(1) take glutamic acid wet bacteria slag, add the ethanol solution of 2-3 times of volume (g/ml), reflux, extract, filter, obtain filtering residue；
(2) adding water in filtering residue, the addition of water is the 2-3 times of volume (g/ml) of glutamic acid wet bacteria slag, supersound extraction,
Filter, obtain filtrate；
(3) filtrate is evaporated, obtains dry, in dry, be sequentially added into water and hydrochloric acid, under the conditions of 15-30 DEG C, hydrolyze 3-
5 hours, after hydrolysis, add methanol, stand, liquid occurs crystallization, pours out supernatant；
(4) pH of regulation supernatant is 7-7.2, has a large amount of white precipitate to occur, filters, obtains white precipitate；Sink to white
Adding methanol, stirring and dissolving in shallow lake, obtain methanol supernatant, residue white precipitate adds methanol and dissolves, and repeated several times merges
Methanol supernatant, is concentrated to dryness, and obtains glucosamine hydrochloride.
In step (1), the water content of described glutamic acid wet bacteria slag is 45-55%；It is preferably 50%.
In step (1), the percentage by volume of described ethanol solution is 90-100%.Use ethanol solution to glutamic acid dreg
The purpose carrying out reflux, extract, is grease removal (the mainly two-layer fat of cell membrane), and this lipid material has certain water solublity, institute
Removing to select the percentage by volume ethanol solution as 90-100% to carry out backflow, with other solvent phase ratio, percentage by volume is
The grease removal effect of the ethanol solution of 90-100% is best.
In step (1), the time of described reflux, extract, is 1-2 hour, and reflow's cycle is 2-3 time.
In step (2), the condition of supersound extraction is: 20kHz, ultrasonic power 600～800W, ultrasonic 2 seconds gaps 2 seconds, super
Sound 4-6 time, each 0.5-1h.The purpose of supersound extraction is by broken wall treatment；The power of supersound extraction, extraction time and ultrasonic
Time is the principal element affecting broken wall treatment effect, and the present invention is by the optimization to ultrasonic process conditions so that it is ensureing relatively
On the premise of good shell-broken effect, reduce again energy consumption.
In step (3), the addition of water and hydrochloric acid is the 2-3 times of volume (g/ml) of dry (in i.e. every gram dry
It is separately added into water and the hydrochloric acid of 2-3 milliliter)；The addition of methanol is the 8-10 times of volume (g/ml) of dry.
In step (3), the concentration of described hydrochloric acid is 12mol/L.
In step (3), the time of standing is 1-1.5 hour.
In step (4), use the pH of sodium hydroxide regulation supernatant.Use the pH of sodium hydroxide regulation supernatant.This
Bright processed by regulation acidolysis after the pH value of supernatant, target product glucosamine hydrochloride is carried out point with sedimentary form
From, simplify the isolated and purified operation of glucosamine hydrochloride, be advantageously implemented industrialized production.
In step (4), the addition of methanol is that the 8-10 times of volume (g/ml) of white precipitate (adds in i.e. every gram white precipitate
Enter methanol 8-10 milliliter).
The glucosamine hydrochloride using the method for thin layer chromatography Scanning Detction to prepare the present invention detects, and takes 1.5
The glucosamine hydrochloride crystallized sample of milligram preparation is dissolved in 1 milliliter of water as sample liquid；Take 10.2 milligrams of aminoguanidine hydrochlorides
Dextrose standard sample is dissolved in 4 milliliters of water as titer.Take 1 μ l sample liquid and 0.25 μ l, 0.5 μ l, 1 μ l, 2 μ l, 3 μ l marks
Quasi-liquid point is on same GF254 High Performance Thin silica gel plate (10cm*10cm).Developing solvent is methanol-acetone-acetic acid-water-isopropyl
Alcohol (4:3:0.5:1:1.5).Panel is placed in expansion cylinder saturated about 20 minutes, then launches 8 centimetres in developing solvent.Take out
Dry.Plate is placed in the acetone soln of aniline-diphenylamines-trichloroacetic acid leaching plate, takes out and bake 10 minutes under 85 degree. sample liquid
Brown is dyed, the R of the two with the point of standard substance liquidfValue is 0.68.Sweep in the absorbing wavelength of 365nm with CAMAG3 thin-layer chromatogram scanner
Retouch to obtain integrating peak areas value, calculate integrating peak areas value and titer quality by the WINCATS1.4.1 software statistics of this instrument
Relation regression equation calculation, detects and calculates the amount of glucosamine hydrochloride.
Beneficial effects of the present invention:
(1) present invention establishes a kind of side efficiently preparing glucosamine hydrochloride from the dreg producing glutamic acid first
Method, the method only needs ethanol, hydrochloric acid and three kinds of organic reagents of methanol, and required reagent type is few, and process is simple, it is not necessary to de-
The step such as color, column chromatography for separation；When acidolysis processes, owing to first having carried out being evaporated process by the filtrate after supersound extraction, therefore institute
The amount of the hydrochloric acid added is few, and senior general reduces the preparation cost of glucosamine hydrochloride.
(2) using the method for the present invention to prepare glucosamine hydrochloride, the productivity of product is high, can prepare in dry dreg per ton
Obtain 2.4-2.7 kilogram of glucosamine hydrochloride, and the purity of the glucosamine hydrochloride prepared be high, up to 99.0% with
On.
(3) method utilizing the dreg producing glutamic acid to prepare glucosamine hydrochloride of the present invention, first selects volume
Percent is that the ethanol solution of 90-100% carries out grease removal process to the dreg producing glutamic acid, carries out ultrasonication after grease removal again
Process, first filtrate is evaporated after broken wall treatment, then acid adding carries out acidolysis, greatly reduces the consumption of acid hemolysis process acid solution, acidolysis
Afterwards by regulating the pH value of supernatant, target product glucosamine hydrochloride is separated with sedimentary form, simplifies
The isolated and purified operation of glucosamine hydrochloride.Above-mentioned each processing step is an organic whole, conditional, effectively simplifies
From the dreg producing glutamic acid, prepare the technological process of glucosamine hydrochloride, and improve glucosamine hydrochloride
Extraction ratio.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, it should explanation, following embodiment merely to
Explain the present invention, its content is not defined.
Embodiment 1: utilize the dreg producing glutamic acid to prepare glucosamine hydrochloride
Specifically comprise the following steps that
(1) glutamic acid wet bacteria slag 250g (water content is 50%, i.e. the dry weight of dreg is 125g) is taken, (the body that every time adds 95%
Long-pending percent) ethanol 600ml, refluxes 2 times, filters every time, finally obtain filtering residue after backflow 1h.
(2) 1000ml is added water to filtering residue, ultrasonic 0.5h under the conditions of 20kHz, power 700w, ultrasonic 2s interval 2s, mistake
Filter to obtain filtrate 400ml.Repeating above procedure ultrasonic 5 times altogether, 5 times filtrate merges, altogether 2000ml.
(3) filtrate rotary evaporation in vacuo at 65 DEG C is removed moisture, obtain dry 16g.
(4) in dry, add 32ml water, add the HCL of 32ml 12mol/L, after hydrolyzing 4h under room temperature (25 DEG C),
Adding 160ml methanol, stand 1h, there is crystallization in liquid, pours out supernatant.
(5) with NaOH, the supernatant poured out is adjusted PH=7, have a large amount of white precipitate.Filter to obtain white precipitate.Sink to white
Shallow lake adds 50ml methanol.Stirring, pours out supernatant.Adding 50ml methanol in residue precipitation again, stirring and dissolving obtains supernatant and (removes
Residue precipitation).Secondary supernatant is merged, is concentrated to dryness, obtains white precipitate powder, be weighed as 0.33g.
The glucosamine hydrochloride using the method for thin layer chromatography Scanning Detction to prepare the present embodiment detects, and takes
White precipitate powder prepared by 1.5 milligrams of the present embodiment is dissolved in 1 milliliter of water as sample liquid；Take 10.2 milligrams of aminoguanidine hydrochlorides
Dextrose standard sample is dissolved in 4 milliliters of water as titer.Take 1 μ l sample liquid and 0.25 μ l, 0.5 μ l, 1 μ l, 2 μ l, 3 μ l marks
Quasi-liquid point is on same GF254 High Performance Thin silica gel plate (10cm*10cm).Developing solvent is methanol-acetone-acetic acid-water-isopropyl
Alcohol (4:3:0.5:1:1.5).Panel is placed in expansion cylinder saturated about 20 minutes, then launches 8 centimetres in developing solvent.Take out
Dry.Plate is placed in the acetone soln of aniline-diphenylamines-trichloroacetic acid leaching plate, takes out and bake 10 minutes under 85 degree. sample liquid
Brown is dyed, the R of the two with the point of standard substance liquidfValue is 0.68, illustrates that white precipitate powder prepared by the present embodiment is salt
Acid glucosamine.
Integrating peak areas value is scanned to obtain, with this instrument in the absorbing wavelength of 365nm with CAMAG3 thin-layer chromatogram scanner
WINCATS1.4.1 software statistics calculates integrating peak areas value and the relation regression equation calculation of titer quality, calculates hydrochloric acid
The amount of glucosamine, is computed, and the purity of glucosamine hydrochloride prepared by the present embodiment is 94.4%, gained aminoguanidine hydrochloride
Glucose is the 0.25% of dry dreg weight.
Embodiment 2: utilize the dreg producing glutamic acid to prepare glucosamine hydrochloride
Specifically comprise the following steps that
(1) take glutamic acid wet bacteria slag 150g (water content is 50%, and dry weight is 75g), add dehydrated alcohol 400ml every time, return
Flowing 2 times, filter after adding dehydrated alcohol 400ml backflow 1h every time, filtering residue repeats backflow 1 time, filters to obtain filtering residue.
(2) 600ml is added water to filtering residue, ultrasonic 0.5h under the conditions of 20kHz, power 600w, ultrasonic 2s interval 2s, filters
Obtaining filtrate 240ml, filtering residue adds water to 600ml, repeats ultrasonic totally 5 times by same method, and 5 times filtrates merge 1200ml altogether.
(3) filtrate rotary evaporation in vacuo at 65 DEG C is removed moisture, obtain dry 10g.
(4) in dry, add 20ml water, add 20ml 12mol/L HCL, after water at normal temperature solution 4h, add
100ml methanol, stands 1h, and crystallization occurs in liquid, pours out supernatant.
(5) with NaOH, the supernatant poured out is adjusted PH=7, have a large amount of white precipitate.Filter to obtain white precipitate.Sink to white
Shallow lake adds 25ml methanol.Stirring, pours out supernatant.Adding 25ml methanol in residue precipitation again, stirring and dissolving obtains supernatant and (removes
Residue precipitation).Secondary supernatant is merged, is concentrated to dryness, obtains white precipitate powder, be weighed as 0.22g.
The glucosamine hydrochloride using the method for thin layer chromatography Scanning Detction to prepare the present embodiment detects, result
Prove that white precipitate powder prepared by the present embodiment is glucosamine hydrochloride；The purity of the glucosamine hydrochloride of preparation is
93.2%, gained glucosamine hydrochloride is the 0.27% of dry dreg weight.
Embodiment 3: utilize the dreg producing glutamic acid to prepare glucosamine hydrochloride
Concentration of alcohol used for dreg backflow is adjusted to 90%, and ultrasonic power used is adjusted to 800w, and remaining operation is with real
Executing example 1, prepared dry is 17g, adds 34ml water, add 34ml 12mol/L HCL, room temperature in this dry
After lower hydrolysis 4h, adding 170ml methanol, stand 1h, there is crystallization in liquid, pours out supernatant.
With NaOH, the supernatant poured out is adjusted PH=7, have a large amount of white precipitate.Filter to obtain white precipitate.To white precipitate
Middle addition 50ml methanol.Stirring, pours out supernatant.Adding 50ml methanol in residue precipitation again, stirring and dissolving obtains supernatant, and it is heavy to remove
Form sediment.Secondary supernatant is merged, is concentrated to dryness, obtains white precipitate powder, be weighed as 0.35g.
The glucosamine hydrochloride using the method for thin layer chromatography Scanning Detction to prepare the present embodiment detects, result
Prove that white precipitate powder prepared by the present embodiment is glucosamine hydrochloride；The purity of the glucosamine hydrochloride of preparation is
93.8%, gained glucosamine hydrochloride is the 0.26% of dry dreg weight.
Comparative example 1:
Concentration of alcohol used for dreg backflow is adjusted to 70%, and ultrasonic power used is adjusted to 450w, and remaining operation is with real
Execute example 1, the glucosamine hydrochloride powder prepared, weigh.Gained glucosamine hydrochloride is 0.25g.
The glucosamine hydrochloride using the method for thin layer chromatography Scanning Detction to prepare the present embodiment detects, result
The purity showing glucosamine hydrochloride prepared by the present embodiment is 91.8%, and gained glucosamine hydrochloride is dry dreg weight
0.18%.
Comparative example 2:
The pH value of supernatant in embodiment 1 step (5) is adjusted to 8.5, and remaining operation, with embodiment 1, prepares
Glucosamine hydrochloride powder, weighs.Gained glucosamine hydrochloride is 0.29g.
The glucosamine hydrochloride using the method for thin layer chromatography Scanning Detction to prepare the present embodiment detects, result
The purity showing glucosamine hydrochloride prepared by the present embodiment is 81.6%, and gained glucosamine hydrochloride is dry dreg weight
0.19%.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. one kind utilizes the method that the dreg producing glutamic acid prepares glucosamine hydrochloride, it is characterised in that step is as follows:
(1) take glutamic acid wet bacteria slag, add the ethanol solution of 2-3 times of volume (g/ml), reflux, extract, filter, obtain filtering residue；
(2) adding water in filtering residue, the addition of water is the 2-3 times of volume (g/ml) of glutamic acid wet bacteria slag, supersound extraction, mistake
Filter, obtains filtrate；
(3) filtrate is evaporated, obtains dry, in dry, be sequentially added into water and hydrochloric acid, hydrolyze 3-5 under the conditions of 15-30 DEG C little
Time, add methanol after hydrolysis, stand, liquid occurs crystallization, pours out supernatant；
(4) pH of regulation supernatant is 7-7.2, filters, obtains white precipitate；In white precipitate, add methanol, stirring and dissolving, obtain
Methanol supernatant, residue white precipitate adds methanol and dissolves, and repeated several times merges methanol supernatant, is concentrated to dryness, to obtain final product
Glucosamine hydrochloride.
2. the method for claim 1, it is characterised in that in step (1), the water content of described glutamic acid wet bacteria slag is
45-55%；It is preferably 50%.
3. the method for claim 1, it is characterised in that in step (1), the percentage by volume of described ethanol solution is
90-100%.
4. the method for claim 1, it is characterised in that in step (1), the time of described reflux, extract, is 1-2 hour,
Reflow's cycle is 2-3 time.
5. the method for claim 1, it is characterised in that in step (2), the condition of supersound extraction is: 20kHz, ultrasonic
Power 600～800W, ultrasonic 2 seconds gaps 2 seconds, ultrasonic 4-6 time, each 0.5-1h.
6. detection method as claimed in claim 1, it is characterised in that in step (3), the addition of water and hydrochloric acid is dry
The 2-3 times of volume (g/ml) of matter；The addition of methanol is the 8-10 times of volume (g/ml) of dry.
7. method as claimed in claim 6, it is characterised in that in step (3), the concentration of described hydrochloric acid is 12mol/L.
8. the method for claim 1, it is characterised in that in step (3), the time of standing is 1-1.5 hour.
9. the method described in claim 1, it is characterised in that in step (4), uses the pH of sodium hydroxide regulation supernatant.
10. the method described in claim 1, it is characterised in that in step (4), the addition of methanol is the 8-10 of white precipitate
Times volume (g/ml).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610566219.7A CN106188168B (en) | 2016-07-18 | 2016-07-18 | The method for preparing aminoglucose hydrochloride using the bacteria residue of production glutamic acid |
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| CN113981026A (en) * | 2021-11-19 | 2022-01-28 | 青岛海辰生物技术有限公司 | High-purity glucosamine hydrochloride and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2004071496A1 (en) * | 2003-02-12 | 2004-08-26 | Degussa Ag | Oral administration form containing liponic acid for colon-specific release of active substances |
| CN103954726A (en) * | 2014-05-06 | 2014-07-30 | 山东师范大学 | Method for extracting muramic acid from corynebacterium glutamicum dregs and detection method |
| US20150050410A1 (en) * | 2013-03-14 | 2015-02-19 | Chromocell Corporation | Compounds, compositions, and methods for modulating sweet taste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2004071496A1 (en) * | 2003-02-12 | 2004-08-26 | Degussa Ag | Oral administration form containing liponic acid for colon-specific release of active substances |
| US20150050410A1 (en) * | 2013-03-14 | 2015-02-19 | Chromocell Corporation | Compounds, compositions, and methods for modulating sweet taste |
| CN103954726A (en) * | 2014-05-06 | 2014-07-30 | 山东师范大学 | Method for extracting muramic acid from corynebacterium glutamicum dregs and detection method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113981026A (en) * | 2021-11-19 | 2022-01-28 | 青岛海辰生物技术有限公司 | High-purity glucosamine hydrochloride and preparation method thereof |
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