CN1357549A - Practical prep. of L-ascorbic acid 2-monophosphate - Google Patents
Practical prep. of L-ascorbic acid 2-monophosphate Download PDFInfo
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- CN1357549A CN1357549A CN 00134517 CN00134517A CN1357549A CN 1357549 A CN1357549 A CN 1357549A CN 00134517 CN00134517 CN 00134517 CN 00134517 A CN00134517 A CN 00134517A CN 1357549 A CN1357549 A CN 1357549A
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Abstract
The practical preparation process of L-ascorbic acid 2-minophosphate is carried out in dilute solution with pH value of 9-11 and at normal temperature. The process uses L-ascorbic acid, sodium trimetaphophate and alkali earth metal hydroxide as material in proper molar ratio. The product of the process has L-ascorbic acid equivalent over 35%. L-ascorbic acid converting rate of 85%, calcium ion to sodium ion ratio of 0.5-0.75, high water insolubility and thus less application loss, and may be used as aquatic animal feed additive directly without need of coating.
Description
The present invention relates to a kind of preparation method's, particularly a kind of practicality of L-xitix phosphoric acid derivatives the preparation method of L-xitix 2-monophosphates, obtain by L-xitix, phosphorylation agent and alkaline earth metal hydroxides reaction.
As everyone knows, L-xitix (vitamins C) and salt thereof can be used as the additive of humans and animals food.But the L-vitamin c itself is a kind of also principle, be heated, in the presence of humidity and the metal ion, very easily oxidized, during particularly as additive, because of processing, being heated to decompose cause losing.L-xitix-2 monophosphates is a kind of phosphoric acid derivatives of L-xitix, and it has almost completely solved above-mentioned decomposition loss problem.For the problem of oxidation of L-xitix, L-ascorbic acid phosphoric acid esters salt-stable exceeds L-xitix 10-20 doubly, and its vitamin C bio utilization ratio is equivalent to the L-xitix.
So far, be phosphorylation agent with the metaphosphate, in the method for synthetic L-ascorbic acid phosphoric acid esters salt, it is important that two methods are arranged.A kind of is United States Patent (USP) 5,110, and 950 mention, and carry out phosphorylation with metaphosphate, for example: Trisodium trimetaphosphate, obtaining L-xitix 2-polyphosphate salt and L-xitix 2-monophosphates.This method adopts the L-xitix under alkaline condition, and be catalyzer with the divalent calcium ion, carry out phosphorylation reaction with Trisodium trimetaphosphate, wherein the mol ratio of L-xitix and Trisodium trimetaphosphate is 1: 1.3, and the mol ratio of calcium and phosphorus is 0.42 in the final reaction product.In order to obtain more the L-xitix 2-monophosphates of higher stability is being arranged aspect oxidation, the thermolysis, often in reaction process, to add a large amount of divalent calcium ion and alkali, for example: calcium chloride and calcium hydroxide, making the L-xitix 2-polyphosphate salt fractional hydrolysis of generation is L-xitix 2-monophosphates, generates the inorganic salt of phosphoric acid simultaneously.Because phosphorylation agent is excessive with respect to the L-xitix, the result causes the inorganic salt content of phosphoric acid in the reaction product to increase, have to adopt a large amount of solvents to carry out wash-out and purification, just can obtain the L-xitix 2-monophosphates of high level, bring many inconvenience to aftertreatment.The percentage composition maximum of L-xitix Equivalent is about 25% (weight) in the exsiccant product.
Find that after patent retrieval another kind of important method is the patent of invention that Switzerland Roche Holding Ag applied in China in September, 1998, its application number 98105706.3, publication number: 1193626A.This patent application is mentioned: in order to obtain more L-xitix 2-monophosphates, employing makes L-xitix 2-polyphosphate salt under the particular basic condition, reacting near in the saturated dense aqueous solution with the basic metal or the alkaline earth salt of L-xitix, because L-xitix 2-polyphosphate salt needs preparation in advance, make the technical process lengthening.When L-xitix 2-polyphosphate salt is the product of existing system, the preferred Trisodium trimetaphosphate of phosphorylation agent, the mol ratio of it and L-ascorbate salt is 0.3-0.5: 1.The alkaline earth metal hydroxides preferably calcium hydroxide, the mol ratio of it and L-ascorbate salt is 0.5-0.8: 1.Above phosphorylation agent and alkali as solid mixture, are added near in the saturated dense reaction soln according to special steps.Therefore this reacts and is inhomogeneous reaction.Must be at a high speed, carry out under the intensive mixing condition, and the solid mixture of phosphorylation agent and alkali has particular requirement on addition, interpolation step and interpolation opportunity.In addition, no matter L-xitix 2-polyphosphate salt is product existing system or that make in advance, needs holding temperature between 40-60 ℃ in the reaction mechanism that generates L-xitix 2-monophosphates.When the solid mixture interpolation speed of temperature factor and phosphorylation agent and alkali is inharmonious, will causes L-xitix 2-polyphosphate salt precipitation, thereby the viscosity of reaction liquid is raise rapidly, and then cause damage, the difficult control of its reaction process.
In addition, L-xitix 2-monophosphates is used for feeding additive aquatic animal more.The feeding additive aquatic animal characteristics are: heated time is generally long than the animal and fowl fodder time in the course of processing, and particulate material drops in the water, as the additive good water solubility, then feed before being eaten, soluble in water and lose.L-xitix 2-phosplate salt pair temperature variation is more stable, but water-soluble bigger with L-xitix 2-phosplate calcium salt or sodium salt proportionlity, promptly calcium ion is relevant with the sodium ion ratio in the product.The calcium salt content height of L-xitix 2-phosplate, product poorly water-soluble then, and the moisture resistance performance is good.The sodium salt content height of L-xitix 2-phosplate, product good water solubility then, moisture resistance poor performance.The sodium salt content height of L-xitix 2-phosplate in the patent 98105706.3 described methods, the ratio of its calcium ion and sodium ion is about 0.43: 1.In feed additive industry,, generally must increase the coating process of product, to overcome the moisture absorption in the product use in order to solve the product moisture absorption.
It is simple to the purpose of this invention is to provide a kind of technology, easy to operate, the preparation method of the L-xitix 2-monophosphates that yield is high; The product moisture resistance performance of utilizing this method to obtain is good.
For achieving the above object, the present invention takes following design:
Be that raw material is in dilute solution directly among the present invention with L-xitix, metaphosphate and alkaline earth metal hydroxides, under normal temperature condition, carry out, need not purification procedures, one-step synthesis moisture resistance performance good, need not coating handle, directly as the L-xitix 2-phosplate of commodity.Its concrete steps:
(1) preparation L-aqueous ascorbic acid, its concentration is the dilute solution of 1.4-1.43M;
(2) preparation alkaline earth metal hydroxides suspension liquid, the mol ratio of alkaline earth metal hydroxides and L-xitix is 1-1.2: 1;
(3) solution with (2) adds in (1), and adjusts the pH value between 9-11.
(4) once add phosphorylation agent in (3), the mol ratio of itself and L-xitix is 0.54-0.65: 1, and kept reaction 2-6 hour;
(5) regulate the pH value with the alkaline earth metal hydroxides suspension liquid, the pH value is controlled between the 9-11;
(6) temperature of reaction maintains between about 20-35 ℃.
Alkali preferably calcium hydroxide among the present invention preferably adopts the pH value that is equivalent to 1.1 normal calcium hydroxide suspension liquid conditioned reaction systems of L-xitix.Preferred Trisodium trimetaphosphate preferably adopts to be equivalent to 0.54 normal Trisodium trimetaphosphate of L-xitix as phosphorylation agent as phosphorylation agent.PH value of reaction system is preferably between 9-9.5.Temperature of reaction is preferably between 25-27 ℃.
Advantage:
The present invention is to provide a kind of preparation method of L-xitix 2-monophosphates of practicality, this method can obtain containing L-xitix Equivalent more than 35%, with respect to initial L-xitix transformation efficiency is 85%, reaction mixture need not purifying, the ratio of calcium ion and sodium ion is 0.5-0.75 in its finished product: 1, and it is water-soluble bad, and loss is few during application, can carry out coating and handle, directly be used for aquatic feeds as feeding additive aquatic animal.
The invention will be further described below in conjunction with embodiment.
Embodiment
In 500 liters of chuck stirred autoclaves, add 350 kg of water, open stirring.Add 88 kilograms of L-xitix (content is 99.9%), be stirred to whole dissolvings, this moment, the concentration of L-xitix was 1.428M.Take by weighing 44 kilograms in the calcium hydroxide (content is 93%) that is equivalent to 1.11 times in L-xitix, add the suspension liquid of water furnishing 30%.This calcium hydroxide suspension liquid is added in the above-mentioned L-ascorbic acid solution, and adjusting reaction mixture pH value is 9, and controlled temperature is between 25-30 ℃.88 kilograms of the Trisodium trimetaphosphates (content is 95.5%) that will be equivalent to 0.55 times in L-xitix.Add in the above-mentioned reaction system, and to regulate the pH value with the calcium hydroxide suspension liquid be 9, keep temperature of reaction between 25-30 ℃.The above-mentioned reaction mixture that makes is obtained 213.4 kilograms in light yellow solid powder after spray-dried.Wherein the L-TAA of phosphorylation is 35.18%, and L-xitix transformation efficiency is 85.3%.
Claims (2)
1, a kind of preparation method of L-xitix 2-monophosphates of practicality, it is characterized in that: it may further comprise the steps:
(1) preparation L-aqueous ascorbic acid, its concentration is the dilute solution of 1.4-1.43M;
(2) preparation alkaline earth metal hydroxides suspension liquid, the mol ratio of alkaline earth metal hydroxides and L-xitix is 1-1.2: 1;
(3) solution with (2) adds in (1), and the pH adjusted value is between 9-11.
(4) add phosphorylation agent in (3), its mol ratio with the L-xitix is 0.54-0.65: 1, and kept reaction 2-6 individual hour;
(5) regulate the pH value with the alkaline earth metal hydroxides suspension liquid, the pH value is controlled between the 9-11;
(6) temperature of reaction maintains between 20-35 ℃.
2, the preparation method of L-xitix 2-monophosphates according to claim 1, it is characterized in that: L-xitix starting point concentration is 1.428M, and phosphorylation agent is a Trisodium trimetaphosphate, and the mol ratio of itself and L-xitix is preferably 0.55; The alkaline-earth metal that adds is a calcium hydroxide, and the mol ratio of itself and L-xitix is 1.11: 1, and calcium ion is 0.5-0.75 with the ratio of sodium ion in the reaction product: 1, and the spray-dried product that obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB001345176A CN1159324C (en) | 2000-12-08 | 2000-12-08 | Practical prep. of L-ascorbic acid 2-monophosphate |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB001345176A CN1159324C (en) | 2000-12-08 | 2000-12-08 | Practical prep. of L-ascorbic acid 2-monophosphate |
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| CN1357549A true CN1357549A (en) | 2002-07-10 |
| CN1159324C CN1159324C (en) | 2004-07-28 |
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| CNB001345176A Expired - Lifetime CN1159324C (en) | 2000-12-08 | 2000-12-08 | Practical prep. of L-ascorbic acid 2-monophosphate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702264A (en) * | 2012-05-28 | 2012-10-03 | 石药集团维生药业（石家庄）有限公司 | Method for preparing feed grade L-ascorbate-2-phosphate |
| CN101665517B (en) * | 2008-09-03 | 2013-04-10 | 宜兴市江山生物科技有限公司 | Method for preparing L-ascorbic acid-2-phosphate |
| CN103113406A (en) * | 2012-11-14 | 2013-05-22 | 江苏江山制药有限公司 | Preparation method of phosphoric acid-2-ascorbic acid ester salt |
| CN103396442B (en) * | 2013-08-21 | 2015-09-09 | 安徽天寅生物技术有限公司 | Water soluble vitamin C sodium metaphosphate calcium and preparation method thereof |
| CN109081851A (en) * | 2018-08-17 | 2018-12-25 | 北京英惠尔生物技术有限公司 | The preparation method of feeding L-AA -2- tripolyphosphate |
| CN117105983A (en) * | 2023-08-24 | 2023-11-24 | 安徽天寅生物技术有限公司 | Synthesis method of L-ascorbic acid-2-monophosphate sodium salt |
-
2000
- 2000-12-08 CN CNB001345176A patent/CN1159324C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665517B (en) * | 2008-09-03 | 2013-04-10 | 宜兴市江山生物科技有限公司 | Method for preparing L-ascorbic acid-2-phosphate |
| CN102702264A (en) * | 2012-05-28 | 2012-10-03 | 石药集团维生药业（石家庄）有限公司 | Method for preparing feed grade L-ascorbate-2-phosphate |
| CN102702264B (en) * | 2012-05-28 | 2015-07-15 | 石药集团维生药业（石家庄）有限公司 | Method for preparing feed grade L-ascorbate-2-phosphate |
| CN103113406A (en) * | 2012-11-14 | 2013-05-22 | 江苏江山制药有限公司 | Preparation method of phosphoric acid-2-ascorbic acid ester salt |
| CN103396442B (en) * | 2013-08-21 | 2015-09-09 | 安徽天寅生物技术有限公司 | Water soluble vitamin C sodium metaphosphate calcium and preparation method thereof |
| CN109081851A (en) * | 2018-08-17 | 2018-12-25 | 北京英惠尔生物技术有限公司 | The preparation method of feeding L-AA -2- tripolyphosphate |
| CN117105983A (en) * | 2023-08-24 | 2023-11-24 | 安徽天寅生物技术有限公司 | Synthesis method of L-ascorbic acid-2-monophosphate sodium salt |
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| Publication number | Publication date |
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| CN1159324C (en) | 2004-07-28 |
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Effective date of registration: 20171116 Address after: Langfang City, Hebei province 065500 trench Guan county south of the village Patentee after: Guan universal Biochemical Technology Co., Ltd. Address before: 100054 Beijing you'anmen East Binhe Road, No. 2 Patentee before: Sangpu Biochemical Tech. Co., Ltd., Beijing |
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