CN103265444A - Crystallization method of 5-aminolevulinic acid phosphate - Google Patents
Crystallization method of 5-aminolevulinic acid phosphate Download PDFInfo
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Abstract
The invention relates to a crystallization method of 5-aminolevulinic acid phosphate. The crystallization method comprises the following steps of carrying out ion-exchange of 5-aminolevulinate broth or other solutions containing 5-aminolevulinate to remove anions and a part of impurities, adding phosphoric acid into the treated solution according to a mole ratio of 1: 1 to 1.2: 1 to obtain a 5-aminolevulinic acid phosphate solution, carrying out decoloring and filtration of the 5-aminolevulinic acid phosphate solution, carrying out vacuum condensation of the 5-aminolevulinic acid phosphate solution to obtain 400 to 600g/l of the concentrated solution, gradually cooling the concentrated solution at a cooling rate of 10 to 15 DEG C/h with stirring at a stirring rate of 50 to 200rpm until crystal nucleuses are produced in the concentrated solution, carrying out constant-temperature crystal growing for 1 to 2h, sequentially carrying out stirring cooling until a temperature is in a range of -5 to 0 DEG C, carrying out filtration separation of the crystals, and drying at a temperature of 50 to 70 DEG C to obtain the 5-aminolevulinic acid phosphate crystals. The crystallization method does not adopt an organic solvent, avoids solvent residual and is conducive to use of 5-aminolevulinic acid phosphate in the medicine field.
Description
Technical field
The present invention relates to the phosphatic crystallization method of a kind of 5-amino-laevulic acid.
Background technology
(5-amino1evulinic acid is that the interior tetrapyrrole compounds of organism is (as protoheme, porphyrin and vitamins B ALA) to the 5-amino-laevulic acid
12Deng) common precursor, have the important physical activity.The 5-amino-laevulic acid can be used as photosynthesis promoter, adverse-resistant agent, defoliant and weedicide etc. in agricultural, and is of many uses, environmentally friendly.At medical field, the 5-amino-laevulic acid is having great using value as photodynamics medicine of new generation aspect the diagnosis of diseases such as brain tumor, skin carcinoma and the treatment.
The unstable chemcial property of 5-amino-laevulic acid, commercially available commercial form mostly is its hydrochloride, a kind of crystallization method of 5-aminolevulinic acid hydrochloride is disclosed among the CN 200910100980, because hydrochloric acid is volatility strong acid, the ALA hydrochloride is in preparation process and mixing, dispersion process, owing to the volatilization of hydrochloric acid equipment is produced corrosion, and produce irritating smell.
Differently with it be, phosphoric acid is non-volatile acid, and acid than hydrochloric acid be a little less than, in the phosphatic preparation process of ALA and mixing, dispersion process, no acidic gaseous volatilization also significantly reduces the corrosion of equipment.
Simultaneously, because the phosphatic solubleness of 5-amino-laevulic acid is starkly lower than hydrochloride, see accompanying drawing 1.Therefore, when preparing 5-amino-laevulic acid phosphoric acid salt from 5-amino-laevulic acid fermented liquid, can obtain higher crystallization yield.
Relate to the phosphatic crystallization method of ALA, that has reported is solvent-non-solvent precipitator method, be solvent precipitation as CN 200780000942 disclosed crystallization method, it uses methyl alcohol, ethanol, Virahol is as precipitation solvent, CN 200780022901 disclosed crystallization method are the poor solvent precipitator method, it uses methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetone, gamma-butyrolactone, 1, the 4-dioxan, methyl cellosolve, tetraethylene glycol dimethyl ether, triglyme is as poor solvent, because crystallisation process has used organic solvent, can bring problem of solvent residue inevitably, when product is used for field of medicaments, dissolvent residual just becomes the major issue that need keep a close eye on, especially for little poison such as 1,4-dioxan, there is the organic solvent of carinogenicity all the more so.
The present invention prepares highly purified ALA phosphate crystal under the situation of not using any organic solvent.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of 5-amino-laevulic acid phosphatic crystallization method, crystallization purity height of the present invention, good stability, cost is low and process is environmentally friendly.
The objective of the invention is to realize by following scheme: the phosphatic crystallization method of a kind of 5-amino-laevulic acid may further comprise the steps:
(1) preparation quality concentration is the phosphatic thick aqueous solution of 5-amino-laevulic acid of 400 ~ 600 g/L, and this step realizes by following substep:
(1.1) fermented liquid of 5-amino-laevulic acid is removed thalline through the ceramic membrane micro-filtration, obtain fermentation clear liquid; Be 0.1M with the dissolving of the salt of 5-amino-laevulic acid and the concentration that is diluted to the 5-amino-laevulic acid perhaps, obtain the dilute solution of 5-aminolevulinic acid.
(1.2) dilute solution of the fermentation clear liquid that step 1.1 is obtained or 5-aminolevulinic acid is by hydrogen type strong acid ion exchange resin, the 5-amino-laevulic acid is attracted on the resin, use the deionized water wash resin, remove impurity, use alkali lye desorb 5-amino-laevulic acid again, obtain stripping liquid.
(1.3) in the stripping liquid that obtains, add the phosphoric acid acidifying, make stripping liquid pH value reach 2.8 ~ 3.2.
(1.4) adding massfraction in stripping liquid is 1 ~ 5% Powdered Activated Carbon, and stirring at normal temperature decolouring 30 ~ 60min filters, and obtains the filtrate of achromaticity and clarification.
(1.5) filtrate is reached 400 ~ 600g/L at 65 ~ 70 ℃ of following vacuum concentration to 5-amino-laevulic acid phosphate concn, the phosphatic thick aqueous solution of 5-amino-laevulic acid that to obtain 65 ~ 70 ℃ of mass concentrations be 400 ~ 600 g/L.
(2) the phosphatic thick aqueous solution of the 5-amino-laevulic acid that step 1 is made is cooling gradually under agitation condition, mixing speed is 50 ~ 200 rpm, the rate of temperature fall control of crystallisation process is at 10 ~ 15 ℃/h, stir when 1-3h has nucleus to occur and stop to stir, constant temperature growing the grain 1 ~ 2 h continues stirring and is cooled to-5 ~ 0 ℃; With the gained crystal separation, solid obtains the phosphatic crystallization of 5-amino-laevulic acid at 2 ~ 6 h of vacuum-drying below 65 ℃.
(3) 1.2-1.5 and step 2 operation set by step of the liquid after will separating obtains the phosphatic secondary crystal of 5-amino-laevulic acid;
(4) the phosphatic secondary crystal of 5-amino-laevulic acid of the phosphatic crystallization of 5-amino-laevulic acid of combining step 2 acquisitions and step 3 acquisition obtains 5-amino-laevulic acid phosphoric acid salt.
The invention has the beneficial effects as follows that the present invention comes crystallization with the thick aqueous solution of the phosphatic high density of 5-amino-laevulic acid by cooling.Adopt aforesaid method, the purity of the 5-amino-laevulic acid phosphate crystal that obtains can reach more than 99 %, and the secondary crystallization total recovery reaches 91 %.The principal feature of this method is that 5-amino-laevulic acid phosphate crystal directly separates out from the aqueous solution.Compared with prior art, total recovery height of the present invention has been avoided the use of a large amount of organic solvent, has reduced and has realized the step that crystallization needs, and has saved production time and cost, and production process is environmentally friendly.
Description of drawings
Fig. 1 is ALA hydrochloride and phosphoric acid salt solubility curve figure under the differing temps.
Fig. 2 is 5-amino-laevulic acid phosphate crystal photo.
Embodiment
The phosphatic crystallization method of 5-amino-laevulic acid of the present invention may further comprise the steps:
1, preparation quality concentration is the phosphatic thick aqueous solution of 5-amino-laevulic acid of 400 ~ 600 g/L.
This step can be realized by following dual mode:
First kind of mode: be the phosphatic thick aqueous solution of 5-amino-laevulic acid of 400 ~ 600 g/L by fermentation method preparation quality concentration.Comprise following substep:
1.1, the fermented liquid of the 5-amino-laevulic acid that obtained by the described methods of CN 200710068170.3, remove thalline through the ceramic membrane micro-filtration, obtain fermentation clear liquid.
1.2, with fermentation clear liquid by hydrogen type strong acid ion exchange resin, the 5-amino-laevulic acid is attracted on the resin, uses the deionized water wash resin, remove impurity such as the pigment that is not adsorbed, sugar, negatively charged ion, organic acid, use alkali lye desorb 5-amino-laevulic acid again, obtain stripping liquid.
1.3, in the stripping liquid that obtains, add the phosphoric acid acidifying, make stripping liquid pH value reach 2.8 ~ 3.2.
1.4, to add massfraction in stripping liquid be 1 ~ 5% Powdered Activated Carbon, stirring at normal temperature decolouring 30 ~ 60min filters, and obtains the filtrate of achromaticity and clarification.
1.5, filtrate is reached 400 ~ 600g/l at 65 ~ 70 ℃ of following vacuum concentration to 5-amino-laevulic acid phosphate concn, the phosphatic thick aqueous solution of 5-amino-laevulic acid that to obtain 65 ~ 70 ℃ of mass concentrations be 400 ~ 600 g/L.
The second way: salt (including but not limited to perchlorate, hydriodate, vitriol, hydrobromate, hydrochloride, nitrate, oxalate, sulphite, pyruvate salt, nitrite or their aqueous solution) the preparation quality concentration by the 5-amino-laevulic acid is the phosphatic thick aqueous solution of 5-amino-laevulic acid of 400 ~ 600 g/L.May further comprise the steps:
1.1, the salt (or their aqueous solution) of 5-amino-laevulic acid is dissolved and is diluted to 5-amino-laevulic acid concentration is 0.1 M, obtains the dilute solution of 5-aminolevulinic acid.
1.2, with the dilute solution of the 5-aminolevulinic acid that obtains by hydrogen type strong acid ion exchange resin, the 5-amino-laevulic acid is attracted on the resin, use the deionized water wash resin, remove the impurity such as negatively charged ion that are not adsorbed, use alkali lye desorb 5-amino-laevulic acid again, obtain stripping liquid.
1.3, in the stripping liquid that obtains, add the phosphoric acid acidifying, make stripping liquid pH value reach 2.8 ~ 3.2.
1.4, to add massfraction in stripping liquid be the Powdered Activated Carbon of 1 ~ 5 %, stirring at normal temperature decolouring 30 ~ 60 min filter, and obtain the filtrate of achromaticity and clarification.
1.5, filtrate is reached 400 ~ 600 g/L at 65 ~ 70 ℃ of following vacuum concentration to 5-amino-laevulic acid phosphate concn, the phosphatic thick aqueous solution of 5-amino-laevulic acid that to obtain 65 ~ 70 ℃ of mass concentrations be 400 ~ 600g/L.
2, the phosphatic thick aqueous solution of the 5-amino-laevulic acid that is 400 ~ 600 g/L with 65 ~ 70 ℃ of mass concentrations cooling gradually under agitation condition, mixing speed is 50 ~ 200 rpm, the rate of temperature fall control of crystallisation process is at 10 ~ 15 ℃/h, stir when 1-3h has nucleus to occur and stop to stir, constant temperature growing the grain 1 ~ 2 h continues stirring and is cooled to-5 ~ 0 ℃; With the gained crystal separation, solid obtains the phosphatic crystallization of 5-amino-laevulic acid at 2 ~ 6 h of vacuum-drying below 65 ℃.
3, the liquid after the separation is the phosphatic aqueous solution of 5-amino-laevulic acid, comprises impurity such as chlorion and sodium ion in addition.Liquid after the separation is 1.2-1.5 and step 2 operation set by step, obtains the phosphatic secondary crystal of 5-amino-laevulic acid, thereby improves utilization ratio of raw materials, reduces production costs.
4, the phosphatic secondary crystal of 5-amino-laevulic acid of the phosphatic crystallization of 5-amino-laevulic acid of combining step 2 acquisitions and step 3 acquisition obtains 5-amino-laevulic acid phosphoric acid salt.
Method of the present invention is passed through the purifying of 5-aminolevulinic acid solution, the control of phosphoric acid consumption and the control of condensing crystal process, successfully realized the phosphatic aqueous solution crystallization of 5-amino-laevulic acid, avoided with an organic solvent, made the finished product stop dissolvent residual.
Further specify this invention below in conjunction with embodiment, it is more obvious that purpose of the present invention and effect will become.
Embodiment 1
Will be by 36 g 5-aminolevulinic acid hydrochloride crystallization deionized water dissolvings of CN 200910100980.1 described methods acquisitions, be diluted to 0.1 M, by hydrogen type strong acid ion exchange resin, use deionized water wash, remove chlorion, use the alkali lye desorb, collect stripping liquid 400 ml between the pH 3 to pH 7,5-amino-laevulic acid concentration is 0.43 M.In stripping liquid, add phosphoric acid and transfer to pH value of solution value to 2.8; Add 4 g Powdered Activated Carbons, 15 ℃ are stirred decolouring 30 minutes, filter, and obtain the destainer of achromaticity and clarification; Destainer is reached 430 g/l in 65 ℃ of vacuum concentration to 5-amino-laevulic acid phosphate concn; With concentrated solution cooling gradually under agitation condition, mixing speed is 60 rpm, and rate of temperature fall is controlled at 10 ℃/h, stops to stir when nucleus occurring in the solution, and constant temperature growing the grain 2 h continue stirring and are cooled to 0 ℃; The filtering separation crystal, 65 ℃ of dryings.Finally obtain 5-amino-laevulic acid phosphate crystal as shown in Figure 2, quality is 28.7 g, and purity is 99.3 %, and crystallization yield is 72.8 %.
Embodiment 2
Remove 5-amino-laevulic acid fermented liquid 18.6 L of thalline through micro-filtration, 5-amino-laevulic acid concentration is 25.1 mM, after the ion-exchange separation, stripping liquid between the pH 3 to pH 7 is transferred to pH 3.2 with 85% phosphoric acid solution, obtain the phosphatic thick aqueous solution of 5-amino-laevulic acid of 1850 ml, wherein 5-amino-laevulic acid phosphate concn is 46.8 g/L, with 37 g powder activity carbon decolorings, stir 30 min after-filtration, with small amount of deionized water detergent active charcoal filter cake, the filtrate that obtains reaches 570 g/l at 65 ℃ of following vacuum concentration to 5-amino-laevulic acid phosphate concn, with concentrated solution cooling gradually under agitation condition, mixing speed is 100 rpm, and rate of temperature fall is controlled at 15 ℃/h, stops to stir when nucleus occurring in the solution, constant temperature growing the grain 2 h, continue to stir and be cooled to 0 ℃, suction filtration isolation of crystalline, 65 ℃ of dryings.Finally obtain 5-amino-laevulic acid phosphate crystal 63.2 g, purity is 99.4 %, and the primary crystallization yield is 73.0 %.To suction filtration residue mother liquor decolour again, filtration, vacuum concentration post crystallization, separate obtaining 5-amino-laevulic acid phosphate crystal 16.4 g, purity is 99.2 %, two-stage crystallization total recovery is 91.9 %.
Embodiment 3
In embodiment 1 and embodiment 2, the suction filtration residue mother liquor that the Crystallization Separation step obtains mixes, being diluted to 5-amino-laevulic acid concentration with deionized water is 0.1 M, liquor capacity is 5.49 L, remove negatively charged ion in the solution by ion-exchange, use the alkali lye desorb, collect stripping liquid 1050 ml between the pH 3 to pH 7,5-amino-laevulic acid concentration is 0.42 M, phosphoric acid 35.6 ml that add 85 % in stripping liquid transfer to pH 3.2, add 40 g Powdered Activated Carbons in the stripping liquid, and 15 ℃ are stirred decolouring 50 minutes, filter, obtain the destainer of achromaticity and clarification.Destainer is reached 580 g/l in 70 ℃ of following vacuum concentration to 5-amino-laevulic acid phosphate concn, with concentrated solution cooling gradually under agitation condition, mixing speed is 200 rpm, rate of temperature fall control is at 10 ℃/h, stop to stir when nucleus occurring in the solution, constant temperature growing the grain 1 h continues stirring and is cooled to 0 ℃, isolation of crystalline, 65 ℃ of vacuum-dryings.Finally obtain 5-amino-laevulic acid phosphate crystal 78.1 g, purity is 99.6 %, and crystallization yield is 77.3 %.
Above-described embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (2)
1. the phosphatic crystallization method of 5-amino-laevulic acid is characterized in that, may further comprise the steps:
(1) preparation quality concentration is the phosphatic thick aqueous solution of 5-amino-laevulic acid of 400 ~ 600 g/L, and this step realizes by following substep:
(1.1) fermented liquid of 5-amino-laevulic acid is removed thalline through the ceramic membrane micro-filtration, obtain fermentation clear liquid; Be 0.1M with the dissolving of the salt of 5-amino-laevulic acid and the concentration that is diluted to the 5-amino-laevulic acid perhaps, obtain the dilute solution of 5-aminolevulinic acid;
(1.2) dilute solution of the fermentation clear liquid that step 1.1 is obtained or 5-aminolevulinic acid is by hydrogen type strong acid ion exchange resin, the 5-amino-laevulic acid is attracted on the resin, use the deionized water wash resin, remove impurity, use alkali lye desorb 5-amino-laevulic acid again, obtain stripping liquid;
(1.3) in the stripping liquid that obtains, add the phosphoric acid acidifying, make stripping liquid pH value reach 2.8 ~ 3.2;
(1.4) adding massfraction in stripping liquid is 1 ~ 5% Powdered Activated Carbon, and stirring at normal temperature decolouring 30 ~ 60min filters, and obtains the filtrate of achromaticity and clarification;
(1.5) filtrate is reached 400 ~ 600g/L at 65 ~ 70 ℃ of following vacuum concentration to 5-amino-laevulic acid phosphate concn, the phosphatic thick aqueous solution of 5-amino-laevulic acid that to obtain 65 ~ 70 ℃ of mass concentrations be 400 ~ 600 g/L;
(2) the phosphatic thick aqueous solution of the 5-amino-laevulic acid that step 1 is made is cooling gradually under agitation condition, mixing speed is 50 ~ 200 rpm, the rate of temperature fall control of crystallisation process is at 10 ~ 15 ℃/h, stir when 1-3h has nucleus to occur and stop to stir, constant temperature growing the grain 1 ~ 2 h continues stirring and is cooled to-5 ~ 0 ℃; With the gained crystal separation, solid obtains the phosphatic crystallization of 5-amino-laevulic acid at 2 ~ 6 h of vacuum-drying below 65 ℃;
(3) 1.2-1.5 and step 2 operation set by step of the liquid after will separating obtains the phosphatic secondary crystal of 5-amino-laevulic acid;
(4) the phosphatic secondary crystal of 5-amino-laevulic acid of the phosphatic crystallization of 5-amino-laevulic acid of combining step 2 acquisitions and step 3 acquisition obtains 5-amino-laevulic acid phosphoric acid salt.
2. according to the phosphatic crystallization method of the described 5-amino-laevulic acid of claim 1, it is characterized in that, in the described step 1.1, the salt of described 5-amino-laevulic acid is made up of one or more of perchlorate, hydriodate, vitriol, hydrobromate, hydrochloride, nitrate, oxalate, sulphite, pyruvate salt and the nitrite of 5-amino-laevulic acid.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106187793A (en) * | 2016-01-26 | 2016-12-07 | 赵鸣 | 5 aminolevulinic acids and the salt compound of derivant thereof and application |
| CN111517973A (en) * | 2019-02-02 | 2020-08-11 | 中国科学院天津工业生物技术研究所 | Production process for preparing 5-aminolevulinic acid hydrochloride from fermentation liquor and application thereof |
| CN111838421A (en) * | 2020-07-27 | 2020-10-30 | 中国科学院天津工业生物技术研究所 | Method for preparing 5-aminolevulinic acid from fermentation liquor and application thereof |
| CN113862179A (en) * | 2021-09-15 | 2021-12-31 | 上海农乐生物制品股份有限公司 | Rhodopseudomonas palustris, application and method for preparing 5-ALA by using rhodopseudomonas palustris |
| CN113912508A (en) * | 2021-08-31 | 2022-01-11 | 新泰市佳禾生物科技有限公司 | Method for separating and purifying 5-aminolevulinic acid from fermentation liquor |
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| CN101472879A (en) * | 2006-08-15 | 2009-07-01 | 克斯莫石油株式会社 | Novel crystal of 5-aminolevulinic acid phosphate and process for production thereof |
| CN101624350A (en) * | 2009-08-06 | 2010-01-13 | 浙江大学 | Crystallization method of 5-aminolevulinic propionic hydrochloride |
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| CN1942430A (en) * | 2004-03-30 | 2007-04-04 | 克斯莫石油株式会社 | 5-aminolevulinic acid phosphate, method for producing the same and use thereof |
| CN101472879A (en) * | 2006-08-15 | 2009-07-01 | 克斯莫石油株式会社 | Novel crystal of 5-aminolevulinic acid phosphate and process for production thereof |
| CN101624350A (en) * | 2009-08-06 | 2010-01-13 | 浙江大学 | Crystallization method of 5-aminolevulinic propionic hydrochloride |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187793A (en) * | 2016-01-26 | 2016-12-07 | 赵鸣 | 5 aminolevulinic acids and the salt compound of derivant thereof and application |
| US10653653B2 (en) | 2016-01-26 | 2020-05-19 | Ming Zhao | Salts of 5-aminolevulinic acid and derivatives |
| CN111517973A (en) * | 2019-02-02 | 2020-08-11 | 中国科学院天津工业生物技术研究所 | Production process for preparing 5-aminolevulinic acid hydrochloride from fermentation liquor and application thereof |
| CN111517973B (en) * | 2019-02-02 | 2023-08-04 | 中国科学院天津工业生物技术研究所 | Production process for preparing 5-aminolevulinic acid hydrochloride from fermentation broth and application of production process |
| CN111838421A (en) * | 2020-07-27 | 2020-10-30 | 中国科学院天津工业生物技术研究所 | Method for preparing 5-aminolevulinic acid from fermentation liquor and application thereof |
| CN111838421B (en) * | 2020-07-27 | 2023-04-21 | 中国科学院天津工业生物技术研究所 | Method for preparing 5-aminolevulinic acid from fermentation broth and application thereof |
| CN113912508A (en) * | 2021-08-31 | 2022-01-11 | 新泰市佳禾生物科技有限公司 | Method for separating and purifying 5-aminolevulinic acid from fermentation liquor |
| CN113862179A (en) * | 2021-09-15 | 2021-12-31 | 上海农乐生物制品股份有限公司 | Rhodopseudomonas palustris, application and method for preparing 5-ALA by using rhodopseudomonas palustris |
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Application publication date: 20130828 Assignee: Jiangsu Good Harvest-Weien Agrochemical Co., Ltd. Assignor: Zhejiang University Contract record no.: 2015990000776 Denomination of invention: Crystallization method of 5-aminolevulinic acid phosphate Granted publication date: 20141105 License type: Common License Record date: 20150906 |
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