CN112174840B - Preparation method of beta-aminopropionic acid - Google Patents
Preparation method of beta-aminopropionic acid Download PDFInfo
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- CN112174840B CN112174840B CN202011033267.2A CN202011033267A CN112174840B CN 112174840 B CN112174840 B CN 112174840B CN 202011033267 A CN202011033267 A CN 202011033267A CN 112174840 B CN112174840 B CN 112174840B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
Abstract
The invention provides a preparation method of beta-aminopropionic acid, which comprises the following steps: mixing acrylic acid, ammonium bicarbonate and ammonia water for reaction to obtain mixed solution containing beta-aminopropionic acid; wherein the mass ratio of the acrylic acid to the ammonium bicarbonate to the ammonia water is 1 (0.01-0.1) to 5-30. The preparation method of the beta-aminopropionic acid provided by the invention has the advantages that the conversion efficiency of acrylic acid is high, and finally the obtained beta-aminopropionic acid has few impurities and higher purity; and the reaction time is short, the reaction efficiency is high, and the method is environment-friendly and safe.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a preparation method of beta-aminopropionic acid.
Background
Beta-aminopropionic acid, also called 3-aminopropionic acid, is an important organic synthesis intermediate, is mainly used for synthesizing pantothenic acid, calcium pantothenate, carnosine, pamidronate sodium, balsalazide and the like, and has very wide application in the fields of medicines, feeds, foods and the like.
The existing technology for producing beta-aminopropionic acid mainly comprises an acrylonitrile ammonification method, an acrylic acid (ester) ammonification method and a succinimide method. The succinimide method has high technological index requirements and high raw material cost; the ammonification method of acrylonitrile has long route, many side reactions, a large amount of salt generated in the process and high cost.
The patent reports a method for preparing beta-aminopropionic acid by reacting acrylic acid with ammonia water in an autoclave, but hydroquinone and p-phenylenediamine are required to be added as additives, the purification difficulty of the product is high, the final yield is only 73%, the reaction time is long, the cost is high, and the yield is low. It has also been reported that the reaction time is about 6-8 hours after adding acrylic acid to the autoclave and then adding ammonia and ammonium bicarbonate to mix; the process for preparing beta-aminopropionic acid is short in route, but the acrylic acid ammonification process is realized through an autoclave, the mass transfer and the heat transfer of a reaction system are slow, the back mixing of materials is serious, the reaction time is long, the impurities generated by side reaction are more, and on the other hand, the intermittent reaction also ensures that the space-time yield of the product is low, the energy consumption is increased, and the cost is increased. There are also technological studies of preparing beta-aminopropionic acid by ammonification of acrylic acid using a microchannel reactor, the reaction time is about 40-60 minutes, and although the reported conversion rate is very high, the impurity therein is slightly high, which leads to lower overall yield and lower purity in the subsequent treatment.
Therefore, it is desirable to provide a method for producing β -aminopropionic acid having high productivity and high purity of the product.
Disclosure of Invention
The invention aims to provide a preparation method of beta-aminopropionic acid, which has the advantages that the conversion efficiency of acrylic acid is high, and finally the obtained beta-aminopropionic acid has few impurities and higher purity; and the reaction time is short, the reaction efficiency is high, and the method is environment-friendly and safe.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a process for the preparation of β -aminopropionic acid, comprising the steps of: mixing acrylic acid, ammonium bicarbonate and ammonia water for reaction to obtain mixed solution containing beta-aminopropionic acid;
wherein the mass ratio of the acrylic acid to the ammonium bicarbonate to the ammonia water is 1 (0.01-0.1) to 5-30.
In the invention, the addition of ammonium bicarbonate can reduce the generation of side reaction, so that the purity of the final product can be improved, which is equivalent to indirectly improving the conversion rate of beta-aminopropionic acid.
The addition amount of the ammonium bicarbonate in the invention is required to be within the limit of the invention, and if the addition amount of the ammonium bicarbonate is too small, the side reaction cannot be reduced, and the purity of the product can be improved; if the amount of ammonium bicarbonate added is too large, the reaction tends to be severe, but the side reaction tends to occur more easily, and the purity of the product tends to be low.
In the present invention, the 0.01 to 0.1 may be 0.02, 0.04, 0.05, 0.06, 0.08, etc. The 5-30 may be 6, 8, 10, 15, 20, 25, etc.
In order to further improve the conversion rate of beta-aminopropionic acid, the mass ratio of the acrylic acid to the ammonium bicarbonate to the ammonia water is 1:0.03:15.
The concentration of the aqueous ammonia according to the present invention is 15 to 20%, for example, 16%, 17%, 18%, 19%, etc.
In the present invention, the reaction is carried out in a microchannel reactor.
As a preferred embodiment of the present invention, the temperature of the microchannel reactor is 180-220 ℃, such as 185 ℃, 192 ℃, 195 ℃, 197 ℃, etc., preferably 190-200 ℃. The reaction is carried out at 180-220 ℃, so that the reaction time can be shortened, the occurrence of side reaction can be reduced, impurities can be reduced, and the purity of the product can be improved.
As a preferred embodiment of the present invention, the pressure of the microchannel reactor is 2.0-4.0MPa, for example 2.5MPa, 2.8MPa, 3.0MPa, 3.2MPa, 3.4MPa, 3.8MPa, etc., preferably 2.5-3.5MPa.
As a preferred embodiment of the present invention, the residence time of the reaction solution in the microchannel reactor is 5 to 25min, for example 8min, 10min, 15min, 18min, 20min, etc., preferably 10min.
The micro-channel reactor regulates the mass flow of the reaction raw materials through a metering pump, and controls the temperature of the constant-temperature reactor through an external heat exchanger.
In the present invention, the preparation method further comprises: and (3) sequentially decoloring, filtering, concentrating, crystallizing, dissolving, decoloring for the second time and drying the mixed solution containing the beta-aminopropionic acid to obtain the beta-aminopropionic acid.
The decolorization according to the invention is carried out with activated carbon for a time of 0.5-1h, for example 0.6h, 0.7h, 0.8h, 0.9h, etc.
As a preferred embodiment of the present invention, the concentration is performed by a blade concentrator, preferably a blade concentrator heated in a water bath.
The method for concentrating by utilizing the water bath heating is safer to produce, higher in purity of subsequent crystallization products and larger in dissolving amount of formaldehyde solvent, and further can reduce the using amount of the formaldehyde solvent.
The crystallization according to the present invention is performed using a 95% methanol solvent, preferably the mass of the methanol solvent is 2 to 5 times, for example 3 times, 4 times, etc., the mass of the acrylic acid.
The crystallization temperature of the present invention is 5-10deg.C, such as 6deg.C, 7deg.C, 8deg.C, 9deg.C, etc.
The drying according to the invention is selected from spray drying.
As a preferable technical scheme of the invention, the method further comprises the step of recovering the solvent from the crystallized mother liquor.
As a specific embodiment of the present invention, the preparation method comprises:
(1) Mixing acrylic acid, ammonium bicarbonate and ammonia water through a premixer of a micro-channel reactor, and then entering the reactor in the micro-channel reactor for reaction to obtain a mixed solution containing beta-aminopropionic acid;
(2) And (3) sequentially decoloring and filtering the mixed solution containing the beta-aminopropionic acid by using active carbon, concentrating by using a water bath scraping plate, crystallizing by using a 95% methanol solvent, recycling the crystallized mother solution to a premixer, dissolving the crystallized wet product, and then performing secondary decoloring, recycling the solvent and spray drying to obtain the beta-aminopropionic acid.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the beta-aminopropionic acid is simple, the conversion rate of the acrylic acid is extremely high, and the finally obtained product has higher yield and higher purity; and the reaction time is short, the reaction efficiency is high, and the method is environment-friendly and safe.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The preparation method of the beta-aminopropionic acid comprises the following steps:
(1) Preparing a mixed solution according to the proportion of 1100g of 18% ammonia water and 3.6g of ammonium bicarbonate, controlling the flow of acrylic acid to be 1.0mL/min, controlling the flow of the mixed solution of ammonium bicarbonate and ammonia water to be 8.6mL/min, simultaneously pumping the mixed solution of acrylic acid, ammonium bicarbonate and ammonia water into a mixer of a micro-channel reactor, enabling the mixed raw materials to enter the reactor to react at 180 ℃, enabling the reaction gauge pressure to be 3.0MPa, enabling the retention time of the reaction solution to be 10min, cooling to obtain the mixed solution containing beta-aminopropionic acid, and opening an ammonia absorption device to absorb residual ammonia;
(2) Adding active carbon into the mixed solution containing beta-aminopropionic acid, stirring for 0.5 hour, filtering the active carbon, concentrating the filtrate to syrup by a water bath scraping plate, adding 95% methanol of 2 times of the concentrated solution, slowly reducing the temperature to 10 ℃, crystallizing and separating out the beta-aminopropionic acid, filtering crystals to obtain a beta-aminopropionic acid wet product, dissolving the wet product beta-aminopropionic acid with 2 times of deionized water, decolorizing the wet product beta-aminopropionic acid with the 2 times of deionized water, feeding the wet product beta-aminopropionic acid into a rectifying tower to recover methanol, and spray drying the feed liquid after recovering the methanol to obtain the beta-aminopropionic acid.
(3) The mother solution after crystallization is decompressed to recycle methanol, then water is added, and the mother solution is reused in batches under the microchannel reactor.
Examples 2 to 4
The difference from example 1 is that in this example, the reaction temperature in step (1) is 190 ℃ (example 2), 200 ℃ (example 3), 220 ℃ (example 4).
Example 5
The preparation method of the beta-aminopropionic acid comprises the following steps:
(1) Preparing a mixed solution according to the proportion of 1100g of 20% ammonia water and 4g of ammonium bicarbonate, controlling the flow of acrylic acid to be 1.0mL/min, controlling the flow of the mixed solution of ammonium bicarbonate and ammonia water to be 15mL/min, simultaneously pumping the mixed solution of acrylic acid, ammonium bicarbonate and ammonia water into a mixer of a microchannel reactor, enabling the mixed raw materials to enter the reactor to react at 200 ℃, controlling the reaction gauge pressure to be 3.2MPa, controlling the residence time of the reaction solution to be 10min, cooling to obtain the mixed solution containing beta-aminopropionic acid, and opening an ammonia absorption device to absorb residual ammonia;
(2) Adding active carbon into the mixed solution containing beta-aminopropionic acid, stirring for 1 hour, filtering the active carbon, concentrating the filtrate to syrup by a water bath scraping plate, adding 95% methanol of 2 times of the concentrated solution, then slowly reducing the temperature to 5 ℃, crystallizing and separating out the beta-aminopropionic acid, filtering crystals to obtain a wet beta-aminopropionic acid product, dissolving the wet beta-aminopropionic acid product with 2 times of deionized water, decolorizing the wet beta-aminopropionic acid product for the second time by the active carbon, feeding the wet beta-aminopropionic acid product into a rectifying tower for recovering methanol, and spray drying the feed liquid after recovering the methanol to obtain the beta-aminopropionic acid.
(3) The mother solution after crystallization is decompressed to recycle methanol, then water is added, and the mother solution is reused in batches under the microchannel reactor.
Example 6
The preparation method of the beta-aminopropionic acid comprises the following steps:
(1) Preparing a mixed solution according to the proportion of 1100g of 20% ammonia water and 3.5g of ammonium bicarbonate, controlling the flow of acrylic acid to be 1.0mL/min, controlling the flow of the mixed solution of ammonium bicarbonate and ammonia water to be 14.5mL/min, simultaneously pumping the mixed solution of acrylic acid, ammonium bicarbonate and ammonia water into a mixer of a micro-channel reactor, enabling the mixed raw materials to enter the reactor to react at 220 ℃, enabling the reaction gauge pressure to be 3.5MPa, enabling the retention time of the reaction solution to be 8min, cooling to obtain the mixed solution containing beta-aminopropionic acid, and opening an ammonia absorption device to absorb residual ammonia;
(2) Adding active carbon into the mixed solution containing beta-aminopropionic acid, stirring for 1 hour, filtering the active carbon, concentrating the filtrate to syrup by a water bath scraping plate, adding 95% methanol of 2 times of the concentrated solution, then slowly reducing the temperature to 6 ℃, crystallizing and separating out the beta-aminopropionic acid, filtering crystals to obtain a wet beta-aminopropionic acid product, dissolving the wet beta-aminopropionic acid product with 2 times of deionized water, decolorizing the wet beta-aminopropionic acid product for the second time by the active carbon, feeding the wet beta-aminopropionic acid product into a rectifying tower for recovering methanol, and spray drying the feed liquid after recovering the methanol to obtain the beta-aminopropionic acid.
(3) The mother solution after crystallization is decompressed to recycle methanol, then water is added, and the mother solution is reused in batches under the microchannel reactor.
Comparative examples 1 to 2
The difference from example 1 is that in this comparative example, the amount of ammonium bicarbonate added was 20g (comparative example 1) and 0.5g (comparative example 2).
Comparative example 3
The difference from example 1 is that in this comparative example, the reaction temperature of step (1) was 170 ℃.
Performance testing
The samples provided in examples 1-6 and comparative examples 1-3 were subjected to performance testing as follows:
(1) Acrylic acid conversion: detecting the content of acrylic acid in the mixed solution containing beta-aminopropionic acid obtained in the step (1) by utilizing a gas phase;
(2) Purity of beta-aminopropionic acid: detecting the purity of the beta-aminopropionic acid by utilizing a gas phase;
the test results are shown in Table 1:
TABLE 1
The embodiment and the performance test show that the preparation method of the beta-aminopropionic acid provided by the invention is simple, and the conversion rate of the acrylic acid is extremely high and is more than 99%; the purity of the finally obtained beta-aminopropionic acid is extremely high and is more than 99 percent.
As can be seen from a comparison of examples 1 and examples 2-4, the reaction temperature of the present invention is preferably 190-200℃and the final product has a higher purity; as can be seen from the comparison of example 1 and comparative examples 1-2, the addition amount of ammonium bicarbonate is required to be within the limit of the invention, so that impurities can be reduced, the purity of the product can be improved, and as can be seen from the comparison of example 1 and comparative example 3, the reaction temperature of the invention is required to be within the range of 180-220 ℃ so that the acrylic acid can be rapidly reacted in a short time, and the conversion rate is extremely high.
The applicant states that the present invention is illustrated by the above examples for the preparation of beta-aminopropionic acid according to the invention, but the invention is not limited to the above detailed methods, i.e. it is not meant that the invention must be carried out in dependence of the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (12)
1. A method for preparing beta-aminopropionic acid, comprising the steps of: mixing acrylic acid, ammonium bicarbonate and ammonia water for reaction to obtain mixed solution containing beta-aminopropionic acid;
wherein the mass ratio of the acrylic acid to the ammonium bicarbonate to the ammonia water is 1 (0.01-0.1) to 5-30;
the reaction is carried out in a microchannel reactor;
the temperature of the microchannel reactor is 190-200 ℃;
the pressure of the micro-channel reactor is 2.5-3.5MPa;
the residence time of the reaction solution in the microchannel reactor is 5-25min.
2. The preparation method according to claim 1, wherein the mass ratio of the acrylic acid, the ammonium bicarbonate and the ammonia water is 1:0.03:15.
3. The method according to claim 1, wherein the concentration of the aqueous ammonia is 15 to 20%.
4. The method according to claim 1, wherein the residence time of the reaction solution in the microchannel reactor is 10min.
5. The production method according to any one of claims 1 to 4, characterized in that the production method further comprises: and (3) sequentially decoloring, filtering, concentrating, crystallizing, dissolving, decoloring for the second time and drying the mixed solution containing the beta-aminopropionic acid to obtain the beta-aminopropionic acid.
6. The method according to claim 5, wherein the decoloring is performed with activated carbon for a period of 0.5 to 1 hour.
7. The method according to claim 5, wherein the concentration is performed by a blade concentrator.
8. The method of claim 5, wherein the scraper concentrator is heated in a water bath.
9. The method according to claim 5, wherein the crystallization is performed using a 95% methanol solvent;
and/or, the temperature of the crystallization is 5-10 ℃;
and/or the drying is selected from spray drying.
10. The production method according to claim 9, wherein the mass of the methanol solvent is 2 to 5 times the mass of the acrylic acid.
11. The method according to claim 9, further comprising subjecting the mother liquor after crystallization to a solvent recovery treatment.
12. The production method according to any one of claims 1 to 11, characterized in that the production method comprises:
(1) Mixing acrylic acid, ammonium bicarbonate and ammonia water through a premixer of a micro-channel reactor, and then entering the reactor in the micro-channel reactor for reaction to obtain a mixed solution containing beta-aminopropionic acid;
(2) And (3) sequentially decoloring and filtering the mixed solution containing the beta-aminopropionic acid by using active carbon, concentrating by using a water bath scraping plate, crystallizing by using a 95% methanol solvent, recycling the crystallized mother solution to a premixer, dissolving the crystallized wet product, and then performing secondary decoloring, recycling the solvent and spray drying to obtain the beta-aminopropionic acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068398A (en) * | 1988-12-24 | 1991-11-26 | Basf Aktiengesellschaft | Preparation of 6-aminocaproic esters |
| CN101701001A (en) * | 2009-07-22 | 2010-05-05 | 仙桃市高盛精细化工有限公司 | Method for preparing beta-lactamine |
| CN104531796A (en) * | 2014-12-11 | 2015-04-22 | 安徽华恒生物科技股份有限公司 | Synthetic method of beta-alanine |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068398A (en) * | 1988-12-24 | 1991-11-26 | Basf Aktiengesellschaft | Preparation of 6-aminocaproic esters |
| CN101701001A (en) * | 2009-07-22 | 2010-05-05 | 仙桃市高盛精细化工有限公司 | Method for preparing beta-lactamine |
| CN104531796A (en) * | 2014-12-11 | 2015-04-22 | 安徽华恒生物科技股份有限公司 | Synthetic method of beta-alanine |
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