CN101210035A - Method for preparing aminoglucose hydrochloride - Google Patents
Method for preparing aminoglucose hydrochloride Download PDFInfo
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- CN101210035A CN101210035A CNA2007100330001A CN200710033000A CN101210035A CN 101210035 A CN101210035 A CN 101210035A CN A2007100330001 A CNA2007100330001 A CN A2007100330001A CN 200710033000 A CN200710033000 A CN 200710033000A CN 101210035 A CN101210035 A CN 101210035A
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Abstract
The invention provides a new method that prepares glucosamine hydrochloride by adopting chitosan, which comprises the steps of the hydrolysis of hydrochloric acid, the cooling crystallization of mother liquid, the concentration of filter liquid, the cooling crystallization of concentrated solution, decolorization, the crystallization of decolorized liquid, fining, etc. The preparation method of the invention adopts the cooling crystallization firstly after the hydrolysis and the concentration of filter liquid to cause the glucosamine hydrochloride to be separated from the liquid that contains relatively high impurity content and also cause grease and impurities to be separated and suspended at the top layer of crystalline solids, thus being beneficial for removing the grease and the impurities. The preparation method of the invention can obtain the glucosamine hydrochloride with high purity and high yield in the condition that hydrochloric acid concentration is 30-32 percent and reaction temperature is 85-88 DEG C and greatly reduces the dosage of activated carbon, thus greatly saving manufacturing cost.
Description
Technical field
The present invention relates to a kind of preparation method of glucosamine hydrochloride, relate in particular to the preparation method that a kind of chitin that extracts prepares the D-glucosamine hydrochloride from marine organisms such as shrimp, crab shell.
Background technology
Glucosamine hydrochloride (also being the D-glucosamine hydrochloride) is treatment bone and joint diseases medicine and microbiotic synergistic agent, be again sweeting agent, the antioxidant of food, also can make the nutrition accessory agent for the diabetic subject, but the also growth of anticancer simultaneously is the main raw material of synthesizing new anticarcinogen NSC-178248.Glucosamine hydrochloride and derivative thereof have a wide range of applications in fields such as medical science, light industry makeup.
Prepare the method for glucosamine hydrochloride with chitin, generally adopt the hydrochloric acid hydrolysis method, promptly in certain density hydrochloric acid, add chitin, through hydrolysis, concentrate, operations such as decolouring and crystallization, thereby obtain the glucosamine hydrochloride crystalline powder of white.In whole preparation process, hydrolysising condition is to influence the vital factor of product recovery rate, also is temperature of reaction, concentration of hydrochloric acid and reaction times.In order to obtain than high product yield, generally be to reach by concentration that improves hydrochloric acid or the temperature of reaction that improves hydrolysis, existing preparation technology, the concentration of hydrochloric acid is 36-38%, but glucosamine hydrochloride is under the acid solution and the situation of being heated of higher concentration, can cause complicated compound and decomposition reaction, not only make the color burn of crude product, and reduce the recovery rate of product purity and minimizing product; When concentration of hydrochloric acid reduced, temperature of reaction must improve, and generally was to bring up to 95 ℃ more than-100 ℃, but improved temperature of reaction simply, also can produce decomposition reaction, and easily produced sticking pot phenomenon, can influence the purity and the recovery rate of product on the contrary.In addition, existing preparation technology, it all is the method for filtered while hot after the employing hydrolysis, but since grease and impurity at high temperature solubleness is bigger, impurity is leached with mother liquor, not only influence the purity of product, and make the subsequent decolorization operation need consume a large amount of gacs, increase the cost of preparation.
Summary of the invention
For solving the problem of above existence, the invention provides a kind of novel method for preparing glucosamine hydrochloride, this method can be at low concentration of hydrochloric acid, than the glucosamine hydrochloride that obtains high purity and high yield under the low reaction temperatures.
For achieving the above object, glucosamine hydrochloride preparation method of the present invention comprises the steps:
(1) hydrochloric acid hydrolysis: in the vacuum reaction still, ratio elder generation adding concentration in chitin and hydrochloric acid weight 1: 2-4 is the hydrochloric acid of 30-32%, after progressively add chitin, and begin to be warming up to 40-42 ℃, wait to feed intake and finish, when sealing is warming up to 85-88 ℃, be incubated 3-6 hour, the vacuum tightness in the control reactor is below 0.3MPa;
(2) mother liquor crystallisation by cooling: the aforesaid reaction vessel temperature is reduced to 38-40 ℃, and feed liquid changes the suction filtration groove over to and was cooled to room temperature 3-6 hour, and xln is separated out from mother liquor, filters, and removes the grease and the impurity on crystallizing layer surface, obtains crude product A;
(3) filtrate concentrates: change above-mentioned filtrate over to the vacuum concentration still, concentrate, and allow the hydrogen chloride gas that volatilizes reclaim through condensing works;
(4) concentrated solution crystallisation by cooling: the temperature of concentrated solution is reduced to 38-40 ℃, change the suction filtration groove over to and be cooled to room temperature 0.5-1 hour, xln is separated out from concentrated solution, filter, obtain crude product B;
(5) decolouring: change crude product A, B over to another reactor, add with respect to crude product A, the water of B weight 10-20 part and the gac of 0.015-0.02 part, heating, stirring, the feed liquid after the decolouring is put into suction filtration groove inner filtration;
(6) destainer condensing crystal: the filtrate in the step (5) is sucked the vacuum concentration still, concentrate,, be cooled to room temperature, change the suction filtration groove over to and filter, obtain crude product C to separating out crystal;
(7) refining: above-mentioned crude product C uses the ethanol with respect to crude product weight 3-4 part to clean, soak, the leaching crystallization, and oven dry obtains product.
Above-mentioned suction filtration groove is the double deck screen web frame, and the first layer is a 300-500 purpose filter cloth, and the second layer is a 500-600 purpose filter cloth.
Thickening temperature in the above-mentioned steps (3) is 80-82 ℃, and vacuum degree control is below 0.08MPa, and the time is 1-2 hour.
Granularity of activated carbon in the above-mentioned steps (5) is the 100-150 order, and temperature is controlled at 82-85 ℃, and the time is 1-1.5 hour.
Thickening temperature in the above-mentioned steps (6) is controlled at 60-65 ℃, and vacuum degree control is below 0.08MPa.
In order to reach better sterilization effect, after the ethanol cleaning for the first time of crude product C process, the immersion, change whizzer over to and dry in the above-mentioned steps (7), carry out the ethanol cleaning second time again, soak, soak time is 1-1.5 hour at every turn.
Preparation method of the present invention, concentrating the back with mother liquor behind hydrochloric acid hydrolysis adopts first crystallisation by cooling to separate out the method for crude product A, B, glucosamine hydrochloride is separated from the many solution of foreign matter content, and the xln top layer can be separated out and be suspended in to grease and impurity also from solution, can remove in this stage, this can not only fine raising product purity and recovery rate, and can significantly reduce the consumption of decolouring stage gac.Preparation method of the present invention can be at low concentration of hydrochloric acid, than the glucosamine hydrochloride that obtains high purity and high yield under the low reaction temperatures, and the reduction of activated carbon dosage can be saved cost greatly.In addition, adopt the lower hydrochloric acid of concentration, also can reduce cost and reduce the corrosion of acid mist equipment.
Description of drawings
Fig. 1 is that the present invention adopts chitin to prepare the process flow diagram of glucosamine hydrochloride.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, and following examples are explanation of the invention and the present invention is not limited to following examples.
Embodiment 1
Take by weighing the chitin of 600Kg and concentration and be 30% hydrochloric acid 1200Kg, be prepared in advance in the vacuum reaction still, in the hydrochloric acid sucting reaction still of getting ready, close feed valve, open and stir, open charging opening, begin to drop into chitin, open steam and be warming up to 40 ℃, stop steam, waiting to feed intake finishes, and sealing heats up, and the vacuum tightness in the control reactor is no more than 0.3MPa, begin to calculate soaking time during to 88 ℃, soaking time is 4.5 hours, opens water coolant turnover valve, allows its temperature in the kettle reduce to 40 ℃, open blow-off valve, change feed liquid over to double-layer vacuum suction filtration groove crystallisation by cooling 3.5 hours, double-layer vacuum suction filtration groove the first layer filter cloth is 300 orders, and second layer filter cloth is 500 orders; Open vacuum pump and open feed valve, mother liquor is sucked concentration kettle from the bottom, treat that suction filtration is done after, (grease that lifts and impurity may contain crystallisate to lift the grease that is deposited on the crystallizing layer surface and impurity with spades, can be according to circumstances go acidolysis again, to increase recovery rate), obtain crude product A; Temperature in the concentration kettle is controlled in 82 ℃, and vacuum tightness concentrates mother liquor below 0.08MPa, 1.5 hours time, and the hydrogen chloride gas that volatilizes is reclaimed through condensing works; The temperature of concentrated solution is reduced to 40 ℃, change double-layer vacuum suction filtration groove cooling 1 hour over to, xln is separated out from concentrated solution, filter, obtain crude product B; Get crude product A and B and mix into 550Kg, join in another reactor, add 8000 liters of deionized waters and 10Kg gac, open and stir, temperature in the kettle is transferred to 85 ℃, be incubated 1 hour; Change the feed liquid after the decolouring over to double-layer vacuum suction filtration groove suction filtration, filtrate goes to the vacuum concentration still again, and vacuum tightness is below 0.08MPa in the control still, temperature concentrates about 62 ℃, confirms that crystallization finishes, shutdown is cooled to room temperature, changes double-deck suction filtration groove over to and filters, and obtains crude product C; C puts soaking compartment into crude product, clean, soaked 1 hour with ethanol, in whizzer, dry, cleaning, soaking 1 hour with ethanol, centrifuge dripping goes in the drying machine, in temperature is 50 ℃, vacuum tightness below 0.08MPa dry 20-40 minute, glucosamine hydrochloride 295Kg, record its every quality index and see Table one.
Embodiment 2
Take by weighing the chitin of 300Kg and concentration and be 32% hydrochloric acid 800Kg, be prepared in advance in the vacuum reaction still, in the hydrochloric acid sucting reaction still of getting ready, close feed valve, open and stir, open charging opening, begin to drop into chitin, open steam and be warming up to 40 ℃, stop steam, waiting to feed intake finishes, and sealing heats up, and the vacuum tightness in the control reactor is no more than 0.3MPa, begin to calculate soaking time during to 85 ℃, soaking time is 3.5 hours, opens water coolant turnover valve, allows its temperature in the kettle reduce to below 40 ℃, open blow-off valve, change feed liquid over to double-layer vacuum suction filtration groove crystallisation by cooling 3.5 hours, double-layer vacuum suction filtration groove the first layer filter cloth is 300 orders, and second layer filter cloth is 500 orders; Open vacuum pump and open feed valve, mother liquor is sucked concentration kettle from the bottom, treat that suction filtration is done after, remove the grease and the impurity that are deposited on the crystallizing layer surface, obtain crude product A; Temperature in the concentration kettle is controlled in 82 ℃, and vacuum tightness concentrates mother liquor below 0.08 MPa, 2 hours time, and the hydrogen chloride gas that volatilizes is reclaimed through condensing works; The temperature of concentrated solution is reduced to below 40 ℃, change double-layer vacuum suction filtration groove cooling 1 hour over to, xln is separated out from concentrated solution, filter, obtain crude product B; Get crude product A and B and mix into 270Kg, join in another reactor, add 3000 liters of deionized waters and 4.5Kg gac, open and stir, temperature in the kettle is transferred to 85 ℃, be incubated 1 hour; Change the feed liquid after the decolouring over to double-layer vacuum suction filtration groove suction filtration, filtrate goes to the vacuum concentration still again, and vacuum tightness is below 0.08MPa in the control still, temperature concentrates about 62 ℃, confirms that crystallization finishes, shutdown is cooled to room temperature, changes the suction filtration groove over to and filters, and obtains crude product C; C puts soaking compartment into crude product, clean, soaked 1 hour with ethanol, in whizzer, dry, cleaning, soaking 1 hour with ethanol, centrifuge dripping goes in the drying machine, in temperature is 50 ℃, vacuum tightness below 0.08MPa dry 20-40 minute, glucosamine hydrochloride 150Kg, record its every quality index and see Table one.
Table one: glucosamine hydrochloride quality index
| Project | Embodiment 1 product | Embodiment 2 products |
| Proterties | White crystalline powder | White crystalline powder |
| Content | 99.8％ | 101.9％ |
| Ignition residue | ≤0.07％ | ≤0.07％ |
| Weight loss on drying | ≤0.5％ | ≤0.5％ |
| PH value (5%, 20 ℃) | 4.0 | 3.5 |
| Chlorion | ≤16.50％ | ≤16.50％ |
| Iron ion | ≤10ppm | ≤10ppm |
| Vitriol | ≤0.24％ | ≤0.23％ |
| Organic volatile impurity | Meet the requirements | Meet the requirements |
| Heavy metal | ≤10ppm | ≤10ppm |
| Specific optical rotation | +71.0° | +72.0° |
The product purity of existing prepared is generally 96-98%, as can be seen from the above table, adopts preparation method of the present invention, can hang down concentration of hydrochloric acid, reach glucosamine hydrochloride more than 99.5% than obtaining purity under the low reaction temperatures.The recovery rate of product and the quality of raw material have very big relation, and same raw material adopts preparation method of the present invention, and its recovery rate can improve 3-5%.
Claims (6)
1. the preparation method of a glucosamine hydrochloride comprises the steps:
(1) hydrochloric acid hydrolysis: in the vacuum reaction still, ratio elder generation adding concentration in chitin and hydrochloric acid weight 1: 2-4 is the hydrochloric acid of 30-32%, after progressively add chitin, and begin to be warming up to 40-42 ℃, wait to feed intake and finish, when sealing is warming up to 85-88 ℃, be incubated 3-6 hour, the vacuum tightness in the control reactor is below 0.3MPa;
(2) mother liquor crystallisation by cooling: the aforesaid reaction vessel temperature is reduced to 38-40 ℃, and feed liquid changes the suction filtration groove over to and was cooled to room temperature 3-4 hour, and xln is separated out from mother liquor, filters, and removes the grease and the impurity on crystallizing layer surface, obtains crude product A;
(3) filtrate concentrates: change above-mentioned filtrate over to the vacuum concentration still, concentrate, and allow the hydrogen chloride gas that volatilizes reclaim through condensing works;
(4) concentrated solution crystallisation by cooling: the temperature of above-mentioned concentrated solution is reduced to 38-40 ℃, change the suction filtration groove over to and be cooled to room temperature 0.5-1 hour, xln is separated out from concentrated solution, filter, obtain crude product B;
(5) decolouring: change crude product A, B over to another reactor, add with respect to crude product A, the water of B weight 10-20 part and the gac of 0.015-0.02 part,, heating, stirring, the feed liquid after the decolouring is put into suction filtration groove inner filtration;
(6) destainer condensing crystal: the filtrate in the step (5) is sucked the vacuum concentration still, concentrate,, be cooled to room temperature, change the suction filtration groove over to and filter, obtain crude product C to separating out crystal;
(7) refining: above-mentioned crude product C uses the ethanol with respect to crude product weight 3-4 part to clean, soak, the leaching crystallization, and oven dry obtains product.
2. glucosamine hydrochloride preparation method according to claim 1 is characterized in that: described suction filtration groove is the double deck screen web frame, and the first layer is a 300-500 purpose filter cloth, and the second layer is a 500-600 purpose filter cloth.
3. glucosamine hydrochloride preparation method according to claim 1 and 2 is characterized in that: the thickening temperature in the described step (3) is 80-82 ℃, and vacuum degree control is below 0.08MPa, and the time is 1-2 hour.
4. glucosamine hydrochloride preparation method according to claim 1 and 2 is characterized in that: the granularity of activated carbon in the described step (5) is the 100-150 order, and temperature is controlled at 82-85 ℃, and the time is 1-1.5 hour.
5. glucosamine hydrochloride preparation method according to claim 1 and 2 is characterized in that: the temperature in the described step (6) is controlled at 60-65 ℃, and vacuum degree control is below 0.08MPa.
6. glucosamine hydrochloride preparation method according to claim 1 and 2, it is characterized in that: crude product C is through after ethanol cleans, soaks for the first time in the described step (7), change whizzer over to doing, carry out the ethanol cleaning second time again, soak, each soak time is 1-1.5 hour
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| CN2007100330001A CN101210035B (en) | 2007-12-25 | 2007-12-25 | Method for preparing aminoglucose hydrochloride |
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| CN2007100330001A CN101210035B (en) | 2007-12-25 | 2007-12-25 | Method for preparing aminoglucose hydrochloride |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805379A (en) * | 2009-02-12 | 2010-08-18 | 林大昌 | Method for preparing D-glucosamine hydrochloride by chitin acid hydrolysis reaction |
| CN101429221B (en) * | 2008-12-19 | 2011-01-12 | 王纪杰 | Method for producing D-glucosamine hydrochlorate |
| CN101775045B (en) * | 2009-12-07 | 2011-12-07 | 汪昔奇 | Method for preparing glucosamine hydrochloride |
| CN102391322A (en) * | 2011-12-15 | 2012-03-28 | 石狮市华宝海洋生物化工有限公司 | Method for recovering glucosamine hydrochloride from hydrolytic mother liquid of glucosamine hydrochloride |
| CN102492000A (en) * | 2011-12-15 | 2012-06-13 | 石狮市华宝海洋生物化工有限公司 | Method for preparing D-glucosamine hydrochloride |
| CN101671374B (en) * | 2009-09-18 | 2012-07-04 | 江苏澳新生物工程有限公司 | New technique for extracting D-glucosamine hydrochloride |
| CN103539825A (en) * | 2013-10-28 | 2014-01-29 | 扬州日兴生物科技股份有限公司 | Method for preparing BRC (British Retail Consortium) D-glucosamine by combining environmental-friendly and safe membrane spectrum |
| CN103910768A (en) * | 2012-12-29 | 2014-07-09 | 中国科学院烟台海岸带研究所 | 6-aminolactose, preparation and application thereof |
| CN102086218B (en) * | 2009-12-02 | 2015-01-21 | 林大昌 | Preparating method for glucosamine hydrochloride from chitin |
| CN104327129A (en) * | 2014-11-25 | 2015-02-04 | 广东侨丰实业股份有限公司 | Method for preparing glucosamine hydrochloride by taking crab shells as raw materials |
| CN108003200A (en) * | 2017-12-05 | 2018-05-08 | 中国科学院海洋研究所 | A kind of aminoglucose hydrochloride novel preparation method |
| CN111533769A (en) * | 2020-05-09 | 2020-08-14 | 马鞍山市天泰生物科技有限公司 | Preparation method of glucosamine hydrochloride granules |
| CN111606957A (en) * | 2020-07-01 | 2020-09-01 | 山东润德生物科技有限公司 | Process and device for producing and decoloring glucosamine hydrochloride |
| CN115340584A (en) * | 2021-05-12 | 2022-11-15 | 山东润德生物科技有限公司 | Cyclic preparation process of glucosamine salt |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161367C (en) * | 2001-08-24 | 2004-08-11 | 广东梅县梅雁蓝藻有限公司 | Prepn of aminoglucose hydrochloride |
-
2007
- 2007-12-25 CN CN2007100330001A patent/CN101210035B/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429221B (en) * | 2008-12-19 | 2011-01-12 | 王纪杰 | Method for producing D-glucosamine hydrochlorate |
| CN101805379A (en) * | 2009-02-12 | 2010-08-18 | 林大昌 | Method for preparing D-glucosamine hydrochloride by chitin acid hydrolysis reaction |
| CN101671374B (en) * | 2009-09-18 | 2012-07-04 | 江苏澳新生物工程有限公司 | New technique for extracting D-glucosamine hydrochloride |
| CN102086218B (en) * | 2009-12-02 | 2015-01-21 | 林大昌 | Preparating method for glucosamine hydrochloride from chitin |
| CN101775045B (en) * | 2009-12-07 | 2011-12-07 | 汪昔奇 | Method for preparing glucosamine hydrochloride |
| CN102492000A (en) * | 2011-12-15 | 2012-06-13 | 石狮市华宝海洋生物化工有限公司 | Method for preparing D-glucosamine hydrochloride |
| CN102391322A (en) * | 2011-12-15 | 2012-03-28 | 石狮市华宝海洋生物化工有限公司 | Method for recovering glucosamine hydrochloride from hydrolytic mother liquid of glucosamine hydrochloride |
| CN103910768A (en) * | 2012-12-29 | 2014-07-09 | 中国科学院烟台海岸带研究所 | 6-aminolactose, preparation and application thereof |
| CN103910768B (en) * | 2012-12-29 | 2016-03-02 | 中国科学院烟台海岸带研究所 | The amino lactose of a kind of 6-and Synthesis and applications thereof |
| CN103539825A (en) * | 2013-10-28 | 2014-01-29 | 扬州日兴生物科技股份有限公司 | Method for preparing BRC (British Retail Consortium) D-glucosamine by combining environmental-friendly and safe membrane spectrum |
| CN103539825B (en) * | 2013-10-28 | 2015-03-25 | 扬州日兴生物科技股份有限公司 | Method for preparing BRC (British Retail Consortium) D-glucosamine by combining environmental-friendly and safe membrane spectrum |
| CN104327129A (en) * | 2014-11-25 | 2015-02-04 | 广东侨丰实业股份有限公司 | Method for preparing glucosamine hydrochloride by taking crab shells as raw materials |
| CN108003200A (en) * | 2017-12-05 | 2018-05-08 | 中国科学院海洋研究所 | A kind of aminoglucose hydrochloride novel preparation method |
| CN111533769A (en) * | 2020-05-09 | 2020-08-14 | 马鞍山市天泰生物科技有限公司 | Preparation method of glucosamine hydrochloride granules |
| CN111606957A (en) * | 2020-07-01 | 2020-09-01 | 山东润德生物科技有限公司 | Process and device for producing and decoloring glucosamine hydrochloride |
| CN115340584A (en) * | 2021-05-12 | 2022-11-15 | 山东润德生物科技有限公司 | Cyclic preparation process of glucosamine salt |
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