CN102086218B - Preparating method for glucosamine hydrochloride from chitin - Google Patents
Preparating method for glucosamine hydrochloride from chitin Download PDFInfo
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- CN102086218B CN102086218B CN200910154761.1A CN200910154761A CN102086218B CN 102086218 B CN102086218 B CN 102086218B CN 200910154761 A CN200910154761 A CN 200910154761A CN 102086218 B CN102086218 B CN 102086218B
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Abstract
The invention belongs to the technology field of technology improved medical intermediate. A preparing method for glucosamine hydrochloride by chitin comprises the following steps: (1) crushing: crushing the chitin raw materials; (2) dissolving: adding 30% to 35% hydrochloric acid in a reaction vessel, heating to 50 to 65 DEG C, starting stirring, adding the chitin raw materials and dissolving; (3)hydrolysis: heating to 80 to 85 DEG C, keeping the temperature for 5 to 20 minutes, then starting to add hydrochloric acid at a concentration of 34% to 36%, keeping the concentration of the hydrochloric acid in the reaction system greater than 30%, continuing to keep the reaction system at a temperature of 80 to 85 DEG C, prolonging 5 to 30 minutes till the reaction ends, feeding after cooling, depositing below 40 DEG C and vacuum filtering to obtain crude material A; (4)extraction: extracting and drying crude material A to obtain a finished product. The technology of the invention can reduce carbonization rate by more than 10%, increase yield to 65% to 75%, reduce the consumption amount of the hydrochloric acid descends by more than 50%, reduce discharge capacity of waste mother liquor by more than 60% and reduce processing technology time by more than 60%.
Description
Technical field
The invention belongs to the technical field of the process modification of medical science intermediate, particularly relate to and preparing in glucosamine hydrochloride technological process a kind of method adopting new acid hydrolysis process with chitin.
Background technology
Glucosamine hydrochloride is called for short ammonia sugar, and being the intermediate in medical industries, is also end product.It has important physiological function to human body, participates in the removing toxic substances of liver kidney, plays anti-inflammatory, liver protection effect, and stimulating discrimination bacillus in enteron aisle to increase, have specific therapeutical, growth capable of inhibiting cell to treatment of arthritis and stomach ulcer, is the main raw material of synthesis cancer therapy drug.In food, makeup and fodder additives, purposes is also quite extensive simultaneously.The demand in the whole world is increasing, domestic export amount has reached more than tens0000 tons, twenties Nian Lai China are producing the acid hydrolysis process always followed conventional lines in ammonia sugar, productive rate is hovered between 45%-55%, often produce 1 ton of ammonia sugar need consume chitin 1.8-2.2 ton, consume hydrochloric acid (31%) 8-10 ton, often produce 1 ton of ammonia sugar process waste liquor (concentration of hydrochloric acid is at 23%-26%) 7-9 ton, after waste liquor dilution, discharge environmental issue is quite outstanding: sewage quantity 50-100 ton, COD > 10
5, PH < 1, colourity is grey black.
In recent years, have many about the patent by technological transformation, but the technical cost of complex process, input is huge, enterprise is difficult to digest (profit of ammonia sugar production is between 5%-10%).Therefore the technological transformation that use is simply reduced expenses improves the productive rate of ammonia sugar, reduces the usage quantity of hydrochloric acid and the emission treatment amount of waste liquor, the target that minimizing sewage discharge, energy efficient Deng Shiantang manufacturing enterprise are expected.
Summary of the invention
Low in order to solve productive rate in above-mentioned ammonia sugar production technique, with serious pollution technological deficiency, the object of the invention is to provide a kind of method that chitin prepares glucosamine hydrochloride, and the method improves ammonia sugar yield and save energy, minimizing sewage discharge.
In order to realize above-mentioned object, chitin of the present invention prepares the method for glucosamine hydrochloride, and the method comprises the following steps:
1. pulverize: chitin raw material is pulverized;
2. dissolve: in the reactor that reflux is housed, add the hydrochloric acid of 30% ~ 35%, be warming up to 50 DEG C ~ 65 DEG C, start and stir, and the chitin raw material slowly adding pulverizing dissolves;
3. be hydrolyzed: after being warming up to 80 DEG C ~ 85 DEG C maintenance 5 ~ 20min, starting to drip concentration is 34% ~ 36% hydrochloric acid, the concentration of hydrochloric acid in reaction system is kept to be greater than 30%, dropping terminates rear continuation and keeps temperature 80 DEG C ~ 85 DEG C, prolong and terminate reaction after 5min ~ 30min, blowing after cooling, temperature < 40 DEG C precipitation, suction filtration obtains crude product A and expects;
4. extract: crude product A expects to dissolve, decolouring, concentrated, washing, recrystallization, drying become finished product.
As preferably, 1. chitin is crushed to 5 order ~ 10 orders by above-mentioned step, and shake sieved 20 mesh sieve holes, order ~ 40, sifts out fine sand.Chitin powder in sand reclaims chitin powder by salt solution hydrometer method, reduces the fine sand in shrimp, crab shell and the sand outside shell and to wear and tear under high-temperature strong acid the enamel surfaces of hydrolysis kettle.(in common process, want the application of slip every month once, in this technique, 10-12 month application of slip once).Adopt crushed material to make enhanced dissolution rate, be convenient to self-feeding simultaneously and controlling feeding time HCL gas leak.
As preferably, the concentration of above-mentioned step 2. hydrochloric acid is 32% ~ 35%, and the amount added of hydrochloric acid is hydrochloric acid: the weight ratio of chitin is 1.2 ~ 1.8: 1.As preferred again, above-mentioned step 2. time for adding is 15 ~ 30min, and the rotating speed of stirring is 40 ~ 50r/min.
As preferably, the amount hydrochloric acid added of above-mentioned step 3. hydrochloric acid: the weight ratio of chitin is 0.3 ~ 0.5: 1.As preferred again, the dropping flow velocity of above-mentioned step 3. hydrochloric acid is 8.0 ~ 10L/min.As preferred again, the dropping of above-mentioned step 3. hydrochloric acid adds in 60min, and the rotating speed of stirring is 15 ~ 20r/min.
As preferably, above-mentioned step 1. in 32% ~ 35% hydrochloric acid adopt the step waste liquor that 2. suction filtration obtains to add hydrochloric acid configuration to form.Waste liquor concentration of hydrochloric acid is generally at 24%-29%, and the amount of preparation 20%-40% of waste liquor, illustrates the acetic acid containing 2%-3% in waste liquor, do not affect hydrolysis reaction, have the polysaccharide hydrochloride of the different polymerization degree of 2%-5% simultaneously.Soak shrimp shell as adopted secondary waste liquor and prepare chitin, the product colourity caused is black, and chroma in waste water and viscosity greatly, are difficult to process.
As preferably, by the first time mother liquor concentrations after step 3. suction filtration, reclaim hydrochloric acid, the slag slurry after concentrated adds 34% ~ 36% hydrochloric acid, concentration of slurry is made to be 32% ~ 34%, be warming up to 80 DEG C ~ 85 DEG C, hydrolysis 1 ~ 2h, blowing after cooling, temperature < 40 DEG C, precipitation 4 ~ 8h, suction filtration obtains crude product B and expect, and crude product B expects that mixing crude product A expects to carry out to dissolve, decolours, concentrates, washs, recrystallization, drying become finished product.First time mother liquor concentrations is hydrolyzed again and can improves the productive rate of ammonia sugar further.As preferred again, adopt four ~ five slag slurries to be combined hydrolysis reaction again, and by produced second time mother liquor, can add in step hydrolysis reaction 3. in batches.The efficiency of production can be improved like this.
For conventional acid hydrolysis reaction, adopt technical hydrochloric acid, the concentration of acid is generally 31%, and add-on w hydrochloric acid: w chitin=3 ~ 6: 1, temperature is at 90 DEG C ~ 105 DEG C, and reaction times 5-8h, chitin is without pulverizing.Chitin is high molecular polymer (molecular weight 5 × 10
5-10
6) under concentrated hydrochloric acid high temperature, glycosidic link breaks to form multiple small molecules intasomies of unit molecule and 3-20, ethanoyl fracture simultaneously departs from, and adsorbs a salt acid molecule, forms monose hydrochloride and polysaccharide hydrochloride.The formation of glucosamine salt hydrochlorate is the process of progressively carrying out, when reacting the ammonia sugar and polysaccharide molecule also and then continuous carbonization (every gram of carbonization material consumes 3 grams of ammonia sugar) that have carried out under high temperature or strong acid, also carry out consuming the HCL in hydrochloric acid simultaneously, force concentration of hydrochloric acid to reduce gradually.In reaction process, HCL is due to high temperature loss through volatilization gradually, also impels concentration to reduce, and because concentration reduces, hydrolysis reaction just slowly, must improve the temperatures extend time, impel again carbonization to increase.Therefore, the carbonation rate of common process reaches 15% ~ 25%.
Because when hydrolysis, concentration of hydrochloric acid must be greater than 30%, temperature must be greater than 80 DEG C, could more fully be hydrolyzed, meanwhile, also containing moisture 10% in chitin.If the disposable hydrochloric acid that adds is hydrolyzed in employing prior art, concentration of hydrochloric acid is too high, and carbonation rate can be caused to rise, and concentration is too low, and the release carrying out moisture in consumption and chitin along with hydrolysis makes concentration of hydrochloric acid too low, and hydrolysis reaction just slowly.
The technical solution used in the present invention is hydrolyzed after chitin dissolves in 60 DEG C ~ 65 DEG C hydrochloric acid again.The process of dissolving makes the moisture in chitin fully be discharged, by keeping the constantly supplementary hydrochloric acid consumption of supplementary concentrated hydrochloric acid (34% ~ 36%) of the balance of concentration of hydrochloric acid and volatilization to make whole reaction process concentration of hydrochloric acid remain > 30% in hydrolytic process, impel hydrolysis thoroughly.So just can control temperature between 80 DEG C-85 DEG C, carbonation rate is made (to pass through test of many times at 5%-10%, 80 DEG C time, concentration of hydrochloric acid maintains 30% all the time, more thoroughly be hydrolyzed in reaction 2h, percent hydrolysis > 90%, carbonation rate < 4.88%).
The present invention is owing to have employed above-mentioned technical scheme, because carbonation rate reduces more than 10%, productive rate is made to bring up to 65% ~ 70%, hydrochloric acid usage quantity declines more than 50%, the quantity discharged of waste liquor reduces more than 60%, complete processing time decreased more than 60%, plant factor, labour productivity improve more than 50%, the corresponding minimizing more than 50% of maintenance cost of reactor etc.
Embodiment
Embodiment 1
Chitin prepares the method for glucosamine hydrochloride, and the method comprises the following steps:
(1) 30m is being housed
236% hydrochloric acid 1200kg is added in the 3000L enamel reaction still of straight pipe type reflux, add waste liquor 300kg, waste liquor concentration of hydrochloric acid 28%, heat to 60 DEG C, start whipping appts, rotating speed 45r/min, adds the chitin after pulverizing and sieving (ash content 8.4%, moisture 9.2%) 1000kg by the propeller of coating tetrafluoroethylene;
(2) be warming up to 82 DEG C, mixing speed 25r/min after dissolving, be incubated to 83 DEG C, after 15min, drip 36% hydrochloric acid, flow is 8.5L/min, and hydrochloric acid content is the follow-up continuation of insurance temperature 83 DEG C of 500L, 60min;
(3) after 30min with cooling water temperature to 40 DEG C, blowing, feed liquid precipitation 8h final vacuum suction filtration obtains crude product A and expects 977kg, obtains fine work 635kg, productive rate 63.5% through deionized water dissolving, decolouring, concentrated, recrystallization, vacuum-drying.
Embodiment 2
By the first time mother liquor concentrations after embodiment 1 suction filtration, reclaim hydrochloric acid, four ~ five slag slurries after concentrated are combined, and drip 36% hydrochloric acid, concentration of slurry is made to be 32% ~ 34%, be warming up to 82 DEG C, hydrolysis 1.5h, blowing after cooling, temperature < 40 DEG C, precipitation 8h, suction filtration obtains crude product B and expect, and crude product B expects that the obtained crude product A of mix embodiment 1 expects to carry out to dissolve, decolours, concentrates, washs, recrystallization, drying become finished product.
Secondary mother liquid 1725kg in above-mentioned technique, concentration and recovery hydrochloric acid 1380kg, reclaiming concentration of hydrochloric acid is 28.7%, and slag slurry repeats once by above-mentioned technique, and fine work yield 4.45%, overall yield is 68%.
The present invention's technique effect is compared with prior art as shown in the table
| Title | Common process | Present invention process | Remarks |
| Product yield | 45％-55％ | ＞65％ | Productive rate after secondary hydrolysis |
| Hydrochloric acid consumes | 7-9 ton | 2.5-3 ton | 36% hydrochloric acid unit price is 1.4-1.5 times of 31% hydrochloric acid |
| Waste liquor process is discharged | 6-8 ton | < 0.5 ton | |
| Steam consumption | 5-7 ton | 2-3 ton | Comprise mother liquor concentrations |
| Power consumption | 250 kilowatt-hours | 50 kilowatt-hours | The power consumption of power of agitator 7.5KW acid hydrolytic reaction |
| Power consumption | 0 | 100 kilowatt-hours | Pulverize after vibration sieve and conveyor power consumption |
| Hydrolysis time | 10-12h | 3-4h | Comprise add, the blowing time |
| Maintenance cost | 200 yuan/ton | 50 yuan/ton | Enamel hydrolysis kettle wards off expense again |
Claims (10)
1. chitin prepares the method for glucosamine hydrochloride, it is characterized in that the method comprises the following steps:
1. pulverize: chitin raw material is pulverized;
2. dissolve: in the reactor that reflux is housed, add the hydrochloric acid of 30% ~ 35%, be warming up to 50 DEG C ~ 65 DEG C, start and stir, and the chitin raw material slowly adding pulverizing dissolves;
3. be hydrolyzed: after being warming up to 80 DEG C ~ 85 DEG C maintenance 5 ~ 20min, starting to drip concentration is 34% ~ 36% hydrochloric acid, the concentration of hydrochloric acid in reaction system is kept to be greater than 30%, dropping terminates rear continuation and keeps temperature 80 DEG C ~ 85 DEG C, prolong and terminate reaction after 5min ~ 30min, blowing after cooling, temperature < 40 DEG C precipitation, suction filtration obtains crude product A and expects;
4. extract: crude product A expects to dissolve, decolouring, concentrated, washing, recrystallization, drying become finished product.
2. chitin according to claim 1 prepares the method for glucosamine hydrochloride, it is characterized in that: 1. chitin is crushed to 5 orders ~ 10 orders by step, and shake sieved 20 mesh sieve holes, order ~ 40, sifts out fine sand.
3. chitin according to claim 1 prepares the method for glucosamine hydrochloride, it is characterized in that: the concentration of step 2. hydrochloric acid is 32% ~ 35%, and the amount added of hydrochloric acid is hydrochloric acid: the weight ratio of chitin is 1.2 ~ 1.8:1.
4. chitin according to claim 3 prepares the method for glucosamine hydrochloride, it is characterized in that: the joining day of step 2. hydrochloric acid is 15 ~ 30min, and the rotating speed of stirring is 40 ~ 50r/min.
5. chitin according to claim 3 prepares the method for glucosamine hydrochloride, it is characterized in that: the amount hydrochloric acid added of step 3. hydrochloric acid: the weight ratio of chitin is 0.3 ~ 0.5:1.
6. chitin prepares the method for glucosamine hydrochloride according to claim 1 or 5, it is characterized in that: the dropping flow velocity of step 3. hydrochloric acid is 8.0 ~ 10L/min.
7. chitin according to claim 5 prepares the method for glucosamine hydrochloride, it is characterized in that: the dropping of step 3. hydrochloric acid adds in 60min, and the rotating speed of stirring is 15 ~ 20r/min.
8. the chitin according to claim 1,2,3,5 or 7 prepares the method for glucosamine hydrochloride, it is characterized in that: above-mentioned step 2. in 30% ~ 35% hydrochloric acid adopt the step waste liquor that 3. suction filtration obtains to add hydrochloric acid configuration to form.
9. the chitin according to claim 1,2,3,5 or 7 prepares the method for glucosamine hydrochloride, it is characterized in that: by the first time mother liquor concentrations after step 3. suction filtration, reclaim hydrochloric acid, slag slurry after concentrated adds 34% ~ 36% hydrochloric acid, concentration of slurry is made to be 32% ~ 34%, be warming up to 80 DEG C ~ 85 DEG C, hydrolysis 1 ~ 2h, blowing after cooling, temperature < 40 DEG C, precipitation 4 ~ 8h, suction filtration obtains crude product B and expect, and crude product B expects that mixing crude product A expects to carry out to dissolve, decolours, concentrates, washs, recrystallization, drying become finished product.
10. chitin according to claim 9 prepares the method for glucosamine hydrochloride, it is characterized in that: adopt four ~ five slag slurries to be combined hydrolysis reaction again, and by produced second time mother liquor, can add in step hydrolysis reaction 3. in batches.
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| CN200910154761.1A CN102086218B (en) | 2009-12-02 | 2009-12-02 | Preparating method for glucosamine hydrochloride from chitin |
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| CN102086218B true CN102086218B (en) | 2015-01-21 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103360432A (en) * | 2013-07-10 | 2013-10-23 | 东台市天元化工有限公司 | Production method for glucosamine hydrochloride |
| CN103694280B (en) * | 2013-11-29 | 2015-11-25 | 安徽丰原发酵技术工程研究有限公司 | From containing the method extracting glucosamine hydrochloride glucosamine hydrochloride mother liquid |
| CN110734465B (en) * | 2019-11-08 | 2021-05-28 | 山东润德生物科技有限公司 | Preparation method of glucosamine potassium sulfate salt |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210035A (en) * | 2007-12-25 | 2008-07-02 | 谢锐权 | Method for preparing aminoglucose hydrochloride |
| CN101314609A (en) * | 2008-06-20 | 2008-12-03 | 天津大学 | Process for preparing D-glucosamine hydrochlorate |
| CN101671374A (en) * | 2009-09-18 | 2010-03-17 | 连云港澳兴生物科技有限公司 | Novel process for extracting D-glucosamine hydrochloride |
| CN101475611B (en) * | 2008-11-20 | 2011-05-11 | 浙江海力生制药有限公司 | Method for preparing high-purity aminoglucose hydrochloride |
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2009
- 2009-12-02 CN CN200910154761.1A patent/CN102086218B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210035A (en) * | 2007-12-25 | 2008-07-02 | 谢锐权 | Method for preparing aminoglucose hydrochloride |
| CN101314609A (en) * | 2008-06-20 | 2008-12-03 | 天津大学 | Process for preparing D-glucosamine hydrochlorate |
| CN101475611B (en) * | 2008-11-20 | 2011-05-11 | 浙江海力生制药有限公司 | Method for preparing high-purity aminoglucose hydrochloride |
| CN101671374A (en) * | 2009-09-18 | 2010-03-17 | 连云港澳兴生物科技有限公司 | Novel process for extracting D-glucosamine hydrochloride |
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