CN101844992B - Preparation process of Beta lactamine - Google Patents
Preparation process of Beta lactamine Download PDFInfo
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- CN101844992B CN101844992B CN201010180188.4A CN201010180188A CN101844992B CN 101844992 B CN101844992 B CN 101844992B CN 201010180188 A CN201010180188 A CN 201010180188A CN 101844992 B CN101844992 B CN 101844992B
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Abstract
The invention discloses a preparation process of Beta lactamine, comprising the following steps of: A. feeding hydroquinone, acrylic acid and liquid ammonia into a reaction kettle; reacting the mixture for 10 hours to obtain a reaction solution; then adding methanol the weight of which is 10-20 times of that of the reaction solution into the reaction solution; filtering and carrying out pressure reduction and the distillation on filtrate; condensing the filtrate to be sticky and re-delivering the filtrate to a reaction kettle; centrifuging filter residue to obtain a Beta lactamine crude product; and B. feeding the crude product into the reaction kettle, adding 3-7 times of methanol; uniformly stirring and heating until the solution is boiled; and reducing the reaction solution to 10-15DEG C and centrifuging and drying a crystal to the refined Beta lactamine. The invention has the advantages of simple process, high product yield, high purity and the like. By the detection, the purity of the Beta lactamine prepared by the process is as high as 99 percent. Meanwhile, the reaction solution is circularly and mechanically used in the process and the product yield is greatly improved up to 73 percent.
Description
Technical field
The present invention relates to a kind of amino acid whose production technology, especially relate to a kind of preparation technology of Beta alanine.
Background technology
Calcium pantothenate (vitamin B5) is mainly used in medicine, food and feed additive.Being the composition of coenzyme A, participating in carbohydrate, fat and portein metabolism, is that human body and animal maintain the indispensable micro substance of normal physiological function.The important intermediate of preparation calcium pantothenate is Beta alanine (β-alanine, claims again Beta-alanine, 3-alanine).
The technique of producing now Beta alanine mainly contains propylene cyanogen method, olefin(e) acid method, succinimide method.Wherein vinyl cyanide route raw material is easy to get, and cost is lower, but has side reaction, and hydrolytic process generates a large amount of inorganic salt, and the more difficult purifying of product directly affects the quality of next step product.Although vinylformic acid route technique is simple, product yield is lower.The processing condition of succinimide route require harsh, and raw materials cost is higher and other side reaction easily occurs, and is not suitable for industrialization.
Summary of the invention
The present invention be mainly solve existing Beta alanine production technique existing raw materials cost higher, easily there is other side reaction, the technical problem such as product purity is low, product yield is lower.
The present invention is mainly solved the problems of the technologies described above by following technical proposals: preparation side's technique of this Beta alanine comprises the following steps:
A. by Resorcinol, Ursol D, vinylformic acid, liquefied ammonia drops in reactor successively, wherein the mol ratio of vinylformic acid and liquefied ammonia is 1: 7～9, Resorcinol, the addition of Ursol D is the 0.01-0.03 ‰ of vinylformic acid and liquefied ammonia gross weight, temperature of reaction is controlled to 145～150 ℃, pressure-controlling is at 2.0～2.5Mpa, isothermal reaction obtained reaction mother liquor after 10 hours, open the remaining ammonia of ammonia absorption pump absorption reaction, then to the methyl alcohol that adds 10～20 times of its weight in reaction mother liquor, after stirring, filter, gained filtrate adds gac in 80 ℃ of decolourings 0.5～1 hour, filtering gac again, filtrate decompression is distilled, be concentrated into thick being again delivered in reactor, the centrifugal Beta alanine crude product that obtains of filter residue,
B. Beta alanine crude product is dropped in reactor, add again the methyl alcohol of 3～7 times of Beta alanine weight, after mixing thoroughly, be heated to solution boiling, then reaction mother liquor temperature is down to 10～15 ℃, make the whole crystallizations of Beta alanine, xln is centrifugal, dry, obtains refining Beta alanine.
It is simple that the present invention has technique, and product yield is high, purity advantages of higher.This technique is take vinylformic acid, liquefied ammonia as main raw material, cheap and easy to get, and adds dihydroxy-benzene and Ursol D, can suppress the generation of side reaction, and the process of accelerated reaction improves synthetic quality.After testing: adopt Beta alanine purity prepared by technique of the present invention more than 98.5%.In this technique, reaction mother liquor recycled, has improved product yield greatly simultaneously, and product yield reaches 73%.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1: by Resorcinol, Ursol D, vinylformic acid, liquefied ammonia drops in autoclave, wherein the mol ratio of vinylformic acid and liquefied ammonia is 1: 7, Resorcinol, the addition of Ursol D is 0.02 ‰ of vinylformic acid and liquefied ammonia gross weight, then cover kettle cover, temperature of reaction is controlled to 145 ℃, pressure-controlling is at 2.0Mpa, isothermal reaction obtained reaction mother liquor after 10 hours, open the remaining ammonia of ammonia absorption pump absorption reaction, then to the methyl alcohol that adds 10 times of its weight in reaction mother liquor, after stirring, filter, gained filtrate adds gac in 80 ℃ of decolourings 0.8 hour, filtering gac again, filtrate decompression is distilled, be concentrated into thick being again delivered in reactor, the centrifugal Beta alanine crude product that obtains of filter residue, then Beta alanine crude product is dropped in reactor, add again the methyl alcohol of 3 times of Beta alanine weight, after mixing thoroughly, be heated to solution boiling, then reaction mother liquor temperature is down to 10 ℃, make the whole crystallizations of Beta alanine, xln is centrifugal, dry, obtains refining Beta alanine.The yield of this Beta alanine is 73.0%, and outward appearance is white prismatic xln, 195～197 ℃ of fusing points, and purity is 98.7%.
Embodiment 2: by Resorcinol, Ursol D, vinylformic acid, liquefied ammonia drops in autoclave, wherein the mol ratio of vinylformic acid and liquefied ammonia is 1: 8, Resorcinol, the addition of Ursol D is 0.025 ‰ of vinylformic acid and liquefied ammonia gross weight, then cover kettle cover, temperature of reaction is controlled to 150 ℃, pressure-controlling is at 2.1Mpa, isothermal reaction obtained reaction mother liquor after 10 hours, open the remaining ammonia of ammonia absorption pump absorption reaction, then to the methyl alcohol that adds 15 times of its weight in reaction mother liquor, after stirring, filter, gained filtrate adds gac in 80 ℃ of decolourings 0.5 hour, filtering gac again, filtrate decompression is distilled, be concentrated into thick being again delivered in reactor, the centrifugal Beta alanine crude product that obtains of filter residue, then Beta alanine crude product is dropped in reactor, add again the methyl alcohol of 7 times of Beta alanine weight, after mixing thoroughly, be heated to solution boiling, then reaction mother liquor temperature is down to 10 ℃, make the whole crystallizations of Beta alanine, xln is centrifugal, dry, obtains refining Beta alanine.The yield of this Beta alanine is 73.8%, and outward appearance is white prismatic xln, 195～197 ℃ of fusing points, and purity is 99.1%.
Embodiment 3: by Resorcinol, Ursol D, vinylformic acid, liquefied ammonia drops in autoclave, wherein the mol ratio of vinylformic acid and liquefied ammonia is 1: 9, Resorcinol, the addition of Ursol D is 0.01 ‰ of vinylformic acid and liquefied ammonia gross weight, then cover kettle cover, temperature of reaction is controlled to 147 ℃, pressure-controlling is at 2.2Mpa, isothermal reaction obtained reaction mother liquor after 10 hours, open the remaining ammonia of ammonia absorption pump absorption reaction, then to the methyl alcohol that adds 12 times of its weight in reaction mother liquor, after stirring, filter, gained filtrate adds gac in 80 ℃ of decolourings 1 hour, filtering gac again, filtrate decompression is distilled, be concentrated into thick being again delivered in reactor, the centrifugal Beta alanine crude product that obtains of filter residue, then Beta alanine crude product is dropped in reactor, add again the methyl alcohol of 5 times of Beta alanine weight, after mixing thoroughly, be heated to solution boiling, then reaction mother liquor temperature is down to 13 ℃, make the whole crystallizations of Beta alanine, xln is centrifugal, dry, obtains refining Beta alanine.The yield of this Beta alanine is 73.1%, and outward appearance is white prismatic xln, 195～197 ℃ of fusing points, and purity is 99.2%.
Embodiment 4: by Resorcinol, Ursol D, vinylformic acid, liquefied ammonia drops in autoclave, wherein the mol ratio of vinylformic acid and liquefied ammonia is 1: 8.5, Resorcinol, the addition of Ursol D is 0.02 ‰ of vinylformic acid and liquefied ammonia gross weight, then cover kettle cover, temperature of reaction is controlled to 146 ℃, pressure-controlling is at 2.3Mpa, isothermal reaction obtained reaction mother liquor after 10 hours, open the remaining ammonia of ammonia absorption pump absorption reaction, then to the methyl alcohol that adds 18 times of its weight in reaction mother liquor, after stirring, filter, gained filtrate adds gac in 80 ℃ of decolourings 0.6 hour, filtering gac again, filtrate decompression is distilled, be concentrated into thick being again delivered in reactor, the centrifugal Beta alanine crude product that obtains of filter residue, then Beta alanine crude product is dropped in reactor, add again the methyl alcohol of 4 times of Beta alanine weight, after mixing thoroughly, be heated to solution boiling, then reaction mother liquor temperature is down to 15 ℃, make the whole crystallizations of Beta alanine, xln is centrifugal, dry, obtains refining Beta alanine.The yield of this Beta alanine is 73.6%, and outward appearance is white prismatic xln, 195～197 ℃ of fusing points, and purity is 98.9%.
Embodiment 5: by Resorcinol, Ursol D, vinylformic acid, liquefied ammonia drops in autoclave, wherein the mol ratio of vinylformic acid and liquefied ammonia is 1: 7.7, Resorcinol, the addition of Ursol D is 0.022 ‰ of vinylformic acid and liquefied ammonia gross weight, then cover kettle cover, temperature of reaction is controlled to 148 ℃, pressure-controlling is at 2.5Mpa, isothermal reaction obtained reaction mother liquor after 10 hours, open the remaining ammonia of ammonia absorption pump absorption reaction, then to the methyl alcohol that adds 16 times of its weight in reaction mother liquor, after stirring, filter, gained filtrate adds gac in 80 ℃ of decolourings 0.5 hour, filtering gac again, filtrate decompression is distilled, be concentrated into thick being again delivered in reactor, the centrifugal Beta alanine crude product that obtains of filter residue, then Beta alanine crude product is dropped in reactor, add again the methyl alcohol of 6 times of Beta alanine weight, after mixing thoroughly, be heated to solution boiling, then reaction mother liquor temperature is down to 12 ℃, make the whole crystallizations of Beta alanine, xln is centrifugal, dry, obtains refining Beta alanine.The yield of this Beta alanine is 73.0%, and outward appearance is white prismatic xln, 195～197 ℃ of fusing points, and purity is 99.1%.
Comparative example 1: by Ursol D, vinylformic acid, liquefied ammonia drops in autoclave, wherein the mol ratio of vinylformic acid and liquefied ammonia is 1: 7.7, the addition of Ursol D is 0.022 ‰ of vinylformic acid and liquefied ammonia gross weight, then cover kettle cover, temperature of reaction is controlled to 148 ℃, pressure-controlling is at 2.5Mpa, isothermal reaction obtained reaction mother liquor after 10 hours, open after the remaining ammonia of ammonia absorption pump absorption reaction, reaction mother liquor adds gac in 70 ℃ of decolourings 0.5 hour, filtering gac again, filtrate decompression is concentrated into thick, treat that filtrate temperature is down to 60 ℃, to filtrate, adding weight is that its methyl alcohol of 3 times continues to stir 2 hours, in 10 ℃ of following placements, spend the night, crystallization obtains Beta alanine crude product, then Beta alanine crude product is dropped in reactor, add again the methyl alcohol of 6 times of Beta alanine weight, after mixing thoroughly, be heated to solution boiling, then reaction mother liquor temperature is down to 12 ℃, make the whole crystallizations of Beta alanine, xln is centrifugal, dry, obtains refining Beta alanine.The yield of this Beta alanine is 35.7%, and outward appearance is white prismatic xln, 195～197 ℃ of fusing points, and purity is 97.8%.
Comparative example 2: by 42mL vinyl cyanide, 355mL ammoniacal liquor, 688mL water, 0.5g pentanoic drops in autoclave, cover kettle cover, slowly be warming up to 175 ℃, react 4 hours, after reaction finishes, remove by filter insolubles, filtrate adds gac in 70 ℃ of decolourings 0.5 hour, filtering gac again, then concentrate filtrate to thick, use again 50mL methyl alcohol heating for dissolving, in 10 ℃ of following placements, spend the night, crystallization, filter, use methanol wash filter cake, after dry, obtaining outward appearance is white prismatic Beta alanine xln 19.6g, yield is 37.1%, 192～193 ℃ of fusing points, purity is 97.3%.
From finding out for example above, various embodiments of the present invention and comparative example are contrasted and shown, no matter, in product yield or product purity index, technique of the present invention is all obviously better than comparative example 1 and comparative example 2.
Claims (1)
1. a preparation technology for Beta alanine, is characterized in that this technique comprises the following steps:
A. by Resorcinol, Ursol D, vinylformic acid, liquefied ammonia drops in reactor successively, wherein the mol ratio of vinylformic acid and liquefied ammonia is 1: 7～9, Resorcinol, the addition of Ursol D is the 0.01-0.03 ‰ of vinylformic acid and liquefied ammonia gross weight, temperature of reaction is controlled to 145～150 ℃, pressure-controlling is at 2.0～2.5Mpa, isothermal reaction obtained reaction mother liquor after 10 hours, open the remaining ammonia of ammonia absorption pump absorption reaction, then to the methyl alcohol that adds 10～20 times of its weight in reaction mother liquor, after stirring, filter, gained filtrate adds gac in 80 ℃ of decolourings 0.5～1 hour, filtering gac again, filtrate decompression is distilled, be concentrated into thick being again delivered in reactor, the centrifugal Beta alanine crude product that obtains of filter residue,
B. Beta alanine crude product is dropped in reactor, add again the methyl alcohol of 3～7 times of Beta alanine weight, after mixing thoroughly, be heated to solution boiling, then reaction mother liquor temperature is down to 10～15 ℃, make the whole crystallizations of Beta alanine, xln is centrifugal, dry, obtains refining Beta alanine.
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| CN105037182B (en) * | 2015-08-10 | 2016-09-28 | 湖北荆洪生物科技股份有限公司 | A kind of preparation method of Beta-alanine |
| CN108892621B (en) * | 2018-07-25 | 2020-11-17 | 浙江新和成股份有限公司 | Method for preparing beta-aminopropionic acid by adopting microchannel reactor |
| CN111470993A (en) * | 2020-05-22 | 2020-07-31 | 安徽安力肽生物科技有限公司 | Preparation method of non-caking Beta-alanine |
| CN113603602B (en) * | 2021-07-09 | 2022-07-12 | 万华化学集团股份有限公司 | Method for preparing beta-aminopropionic acid with high selectivity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1379268A (en) * | 1972-06-30 | 1975-01-02 | Tokyo Fine Chemical Co Ltd | Process for production of beta-alanine |
| CN1240205A (en) * | 1998-06-11 | 2000-01-05 | 住友化学工业株式会社 | Preparation of prepenoic acid and its polymerization inhibition |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1379268A (en) * | 1972-06-30 | 1975-01-02 | Tokyo Fine Chemical Co Ltd | Process for production of beta-alanine |
| CN1240205A (en) * | 1998-06-11 | 2000-01-05 | 住友化学工业株式会社 | Preparation of prepenoic acid and its polymerization inhibition |
Non-Patent Citations (5)
| Title |
|---|
| β-氨基丙酸的合成与应用;罗积杏;《氨基酸和生物资源》;20051231;第27卷(第1期);52-55 * |
| β-氨基丙酸的合成工艺;任怡;《辽宁化工》;20060430;第35卷(第4期);187-188 * |
| 任怡.β-氨基丙酸的合成工艺.《辽宁化工》.2006,第35卷(第4期),187-188. |
| 罗积杏.β-氨基丙酸的合成与应用.《氨基酸和生物资源》.2005,第27卷(第1期),52-55. |
| 陆乃宸，等.丙烯酸氨化生产β-氨基丙酸的反应动力学和工艺过程的模拟.《化学反应工程与工艺》.1996,第12卷(第2期),144-150. * |
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