CN110964004B - Refining method of thiothiamine, thiothiamine product obtained by refining method and vitamin B1 product - Google Patents
Refining method of thiothiamine, thiothiamine product obtained by refining method and vitamin B1 product Download PDFInfo
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Abstract
The invention provides a method for refining thiothiamine, a thiothiamine product and a vitamin B1 product, and relates to the technical field of compound purification. Firstly, carrying out alcohol washing and water washing on a thiamine crude product to obtain a crude product A; dissolving the crude product A in low-carbon alcohol to obtain a solution A, and decoloring to obtain a solution B; and precipitating the thiamine from the solution B, and drying to obtain the refined thiamine. The detection proves that the purity of the refined thiothiamine can be obviously improved compared with the thiothiamine synthesized by the prior art, and the preparation method provides guarantee for the subsequent preparation of vitamin B1 products.
Description
Technical Field
The invention relates to the technical field of compound purification, in particular to a method for refining thiothiamine, and a thiothiamine product and a vitamin B1 product obtained by the same.
Background
Thiamine is used as an intermediate for synthesizing vitamin B1, the content of the thiothiamine synthesized by the prior art can only reach 90-95%, and the thiothiamine containing 5-10% of impurities has great influence on the quality of later-stage preparation of vitamin B1, so that the detection indexes such as the chromatographic purity of vitamin B1 are easily unqualified, and the rework of a vitamin B1 product can even be caused in severe cases, so that the production cost of the vitamin B1 is increased.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for refining thiothiamine, wherein the method is used for purifying a crude thiothiamine product synthesized by the existing process, so that the purity of the purified thiothiamine can be obviously improved compared with the purity of the thiothiamine synthesized by the existing process, and guarantee is provided for the subsequent preparation of a vitamin B1 product.
The second purpose of the invention is to provide a thiothiamine product which is mainly prepared by the refining method.
The third purpose of the invention is to provide a vitamin B1 product, wherein the vitamin B1 product is mainly synthesized from the thiothiamine product.
The invention provides a refining method of thiothiamine, which comprises the following steps:
(a) sequentially carrying out alcohol washing and water washing on the thiothiamine crude product to obtain a crude product A;
(b) dissolving the crude product A in low-carbon alcohol to obtain a solution A, and then decoloring to obtain a solution B;
(c) and precipitating the thiothiamine from the solution B, and drying to obtain the refined thiothiamine.
Further, the alcohol washing in the step (a) is low-carbon alcohol washing;
preferably, the lower alcohol comprises methanol or ethanol;
preferably, the mass ratio of the crude thiamine disulfide product to the lower alcohol in the alcohol washing is 1: 2-5, preferably 1: 2;
preferably, the temperature of the alcohol washing is 15-25 ℃, and preferably 20 ℃.
Further, the mass ratio of the crude thiamine disulfide product in the water washing in the step (a) to the water is 1: 2-5, preferably 1: 2;
preferably, the temperature of the water washing is 15-25 ℃, and preferably 20 ℃.
Further, the refining method further comprises a step of performing first drying on a product obtained after the alcohol washing, before the water washing after the alcohol washing in step (a);
preferably, the temperature of the first drying is 40-50 ℃, and the drying time is 2-5 h;
preferably, the refining method further comprises a step of carrying out secondary drying on the product obtained after the step (a) of washing with water to obtain a crude product A;
preferably, the temperature of the second drying is 60-80 ℃, and the drying time is 5-8 h.
Further, the method for dissolving the crude product A in ethanol in the step (b) comprises the following steps: adding the crude product A into ethanol, heating to 70-80 ℃ to dissolve the crude product A into the ethanol;
preferably, the mass ratio of the crude product A to the ethanol is 1: 40-60, preferably 1: 50;
preferably, the temperature rise is reflux temperature rise.
Further, the decolorization in the step (b) is adsorbent decolorization, and the adsorbent is preferably activated carbon;
preferably, in the decoloring process by using activated carbon, the mass ratio of the solution A to the activated carbon is 1: 0.01 to 0.03, preferably 1: 0.01;
preferably, the time for decoloring the activated carbon is 15-20 min, preferably 15 min;
preferably, the activated carbon decolorization is carried out under the condition of stirring, and the stirring speed is 200-500 r/min.
Further, the method for precipitating thiamine from the solution B in the step (c) comprises the following steps: and cooling the solution B to 0-10 ℃ to recrystallize and separate out the thiamine.
Further, the drying temperature in the step (c) is 60-80 ℃, and the drying time is 5-8 hours.
The invention provides a thiothiamine product prepared by the refining method.
The invention provides a vitamin B1 product synthesized by adopting the thiothiamine product.
Compared with the prior art, the invention has the beneficial effects that:
the method for refining the thiamine takes a thiamine crude product which is synthesized by the prior art and has the content of 90-95 percent as a raw material. Firstly, carrying out alcohol washing and water washing on a thiamine crude product to obtain a crude product A; dissolving the crude product A in low-carbon alcohol to obtain a solution A, and decoloring to obtain a solution B; and precipitating the thiamine from the solution B, and drying to obtain the refined thiamine. The detection proves that the purity of the refined thiothiamine can be obviously improved compared with the thiothiamine synthesized by the prior art, and the preparation method provides guarantee for the subsequent preparation of vitamin B1 products.
The thiamine product is mainly prepared by the refining method, and the purity of the refined thiamine can be obviously improved by detection compared with the thiamine synthesized by the prior art.
The vitamin B1 product provided by the invention is a vitamin B1 product which is mainly synthesized from the thiothiamine product.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Note: the crude product of the thiamine refers to the thiamine with the content of 90-95% synthesized by using the prior art.
According to one aspect of the present invention, a method for refining thiothiamine, the method comprising the steps of:
(a) sequentially carrying out alcohol washing and water washing on the thiothiamine crude product to obtain a crude product A;
(b) dissolving the crude product A in low-carbon alcohol to obtain a solution A, and then decoloring to obtain a solution B;
(c) and precipitating the thiothiamine from the solution B, and drying to obtain the refined thiothiamine.
The method for refining the thiamine takes a thiamine crude product which is synthesized by the prior art and has the content of 90-95 percent as a raw material. Firstly, carrying out alcohol washing and water washing on a thiamine crude product to obtain a crude product A; dissolving the crude product A in low-carbon alcohol to obtain a solution A, and decoloring to obtain a solution B; and precipitating the thiamine from the solution B, and drying to obtain the refined thiamine. The detection proves that the purity of the refined thiothiamine can be obviously improved compared with the thiothiamine synthesized by the prior art, and the preparation method provides guarantee for the subsequent preparation of vitamin B1 products.
In a preferred embodiment of the present invention, the alcohol washing in the step (a) is a lower alcohol washing;
preferably, the lower alcohol comprises methanol or ethanol;
in the above preferred embodiment, the mass ratio of the crude thiamine disulfide to the lower alcohol in the alcohol washing is 1: 2-5, preferably 1: 2;
the mass ratio of thiothiamine to lower alcohol described above is typically, but not by way of limitation, a preferred embodiment: 1: 2. 1: 3. 1:4 and 1: 5.
in the preferred embodiment, the temperature of the alcohol washing is 15 to 25 ℃, preferably 20 ℃.
Typical but non-limiting preferred embodiments of the above-described alcohol wash temperature are: 15 deg.C, 16 deg.C, 17 deg.C, 18 deg.C, 19 deg.C, 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C and 25 deg.C.
In a preferred embodiment of the present invention, the mass ratio of thiamine disulfide to water in the water washing in the step (a) is 1: 2-5, preferably 1: 2;
in a preferred embodiment, the mass ratio of thiamine disulfide to water in the water washing is 1: 2-5, the larger the water consumption is, the more thorough the washing is, and the experiment shows that 2 times of water consumption can achieve better technical effect.
The above-described mass ratio of thiothiamine to water is typically, but not by way of limitation, a preferred embodiment: 1: 2. 1: 3. 1:4 and 1: 5.
in the preferred embodiment, the temperature of the water washing is 15 to 25 ℃, preferably 20 ℃.
Typical but non-limiting preferred embodiments of the temperature of the water wash described above are: 15 deg.C, 16 deg.C, 17 deg.C, 18 deg.C, 19 deg.C, 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C and 25 deg.C.
In a preferred embodiment of the present invention, the purification method further comprises a step of subjecting the crude thiothiamine to a first drying step before the alcohol-washing step (a) with water;
in the preferred embodiment, the first drying temperature is 40-50 ℃, and the drying time is 2-5 h;
typical but non-limiting preferred embodiments of the temperature of the above-mentioned first drying are: 40 deg.C, 42 deg.C, 44 deg.C, 46 deg.C, 48 deg.C and 50 deg.C; typical but non-limiting preferred embodiments of the drying time of the above-mentioned first drying are: 2h, 3h, 4h and 5 h.
In a preferred embodiment of the present invention, the refining method further comprises a step of performing a second drying on the product obtained after the water washing in the step (a) to obtain a crude product a;
in the preferred embodiment, the second drying temperature is 60 to 80 ℃, and the drying time is 5 to 8 hours.
Typical but non-limiting preferred embodiments of the temperature of the above second drying are: 60 ℃, 65 ℃, 70 ℃, 73 ℃, 78 ℃ and 80 ℃; typical but non-limiting preferred embodiments of the drying time of the above-mentioned second drying are: 5h, 6h, 7h and 8 h.
In a preferred embodiment of the present invention, the method for dissolving crude product a in ethanol in step (b) comprises: adding the crude product A into ethanol, heating to 70-80 ℃ to dissolve the crude product A into the ethanol;
in the above preferred embodiment, the mass ratio of the crude product a to ethanol is 1: 40-60, preferably 1: 50;
typical but non-limiting preferred embodiments of the above mass ratio of crude a to ethanol are: 1: 40. 1: 45. 1: 50. 1:55 and 1: 60.
in the above preferred embodiment, the temperature rise is a reflux temperature rise, and the reflux temperature rise can achieve a technical effect of not losing the solvent ethanol.
In a preferred embodiment of the present invention, the decolorization in step (b) is adsorbent decolorization, preferably activated carbon;
in a preferred embodiment, the activated carbon decolorization can adsorb impurity substances of pigments in the solution, and the solution is clarified after the activated carbon decolorization.
In the above preferred embodiment, in the decoloring process using activated carbon, the mass ratio of the solution a to the activated carbon is 1: 0.01 to 0.03, preferably 1: 0.01;
the mass ratio of the solution A to the activated carbon is typically, but not limited to, the following preferred embodiments: 1: 0.01, 1: 0.02 and 1: 0.03.
in the preferred embodiment, the time for decolorizing the activated carbon is 15-20 min, preferably 15 min.
Typical but non-limiting preferred embodiments of the above stirring time are: 15min, 16min, 17min, 18min, 19min and 20 min.
In the above preferred embodiment, the activated carbon decolorization is performed under stirring conditions, and the stirring speed is preferably 200 to 500 r/min.
In a preferred embodiment of the present invention, the method for precipitating thiamine from solution B in step (c) comprises: and cooling the solution B to 0-10 ℃ to recrystallize and separate out the thiamine.
In a preferred embodiment, the solubility of thiothiamine in ethanol decreases with decreasing temperature, and therefore, the lower the deposition temperature of thiothiamine, the more thiothiamine crystals are deposited, the higher the yield.
In a preferred embodiment of the present invention, the drying temperature in the step (c) is 60 to 80 ℃, and the drying time is 5 to 8 hours.
Typical but non-limiting preferred embodiments of the temperature for drying in step (c) above are: 60 ℃, 65 ℃, 70 ℃, 73 ℃, 78 ℃ and 80 ℃; typical but non-limiting preferred embodiments of the drying time for drying in step (c) above are: 5h, 6h, 7h and 8 h.
According to one aspect of the invention, the thiothiamine product is prepared by the refining method.
The thiothiamine product provided by the invention is mainly prepared by the refining method.
According to one aspect of the invention, the vitamin B1 product is synthesized using the thiothiamine product described above.
The vitamin B1 product provided by the invention is a vitamin B1 product which is mainly synthesized from the thiothiamine product.
The technical solution of the present invention will be further described with reference to examples and comparative examples.
Note: the crude thiothiamine products in the following examples and comparative examples of the present invention are thiothiamine having a content of 90% to 95% synthesized using the existing process.
Example 1
A method of refinement of thiothiamine, said method comprising the steps of:
(1) firstly, washing a thiothiamine crude product with ethanol at 15 ℃, removing impurities dissolved in the ethanol in the thiothiamine crude product, and then filtering and drying to obtain an alcohol-washed thiothiamine crude product;
the ratio of the thiothiamine crude product to the ethanol is 1: 2.
The drying time after the alcohol washing is 2 hours, and the temperature is 40 ℃;
(2) washing the crude product of the thiamine after alcohol washing and drying with distilled water at 15 ℃ to remove impurities dissolved in water in the thiamine to obtain a crude product A;
the ratio of the crude thiothiamine to the distilled water is 1: 2.
The drying time after washing is 5 hours, and the temperature is 60 ℃;
(3) mixing the crude product A and ethanol according to the proportion of 1:40, and then refluxing and heating to 70 ℃ until the crude product A is completely dissolved to obtain a solution A;
(4) and mixing the activated carbon in a ratio of 0.01: 1, quickly stirring and decoloring for 16min, and filtering while hot to obtain a solution B;
(5) cooling the solution B to 0 ℃ to separate out thiothiamine, and then filtering and drying the separated thiothiamine to obtain refined thiothiamine;
the time for drying the precipitated thiothiamine is 5 hours, and the temperature is 60 ℃.
Example 2
A method of refinement of thiothiamine, said method comprising the steps of:
(1) firstly, washing a crude thiothiamine product with ethanol at 25 ℃, removing impurities dissolved in the ethanol in the crude thiothiamine product, and then filtering and drying to obtain an alcohol-washed crude thiothiamine product;
the ratio of the thiothiamine crude product to the ethanol is 1: 5.
The drying time after the alcohol washing is 5 hours, and the temperature is 50 ℃;
(2) washing the crude product of the thiamine after alcohol washing and drying with distilled water at 25 ℃ to remove impurities dissolved in water in the thiamine to obtain a crude product A;
the ratio of the crude thiothiamine to the distilled water is 1: 5.
The drying time after washing is 8 hours, and the temperature is 80 ℃;
(3) mixing the crude product A with ethanol according to the proportion of 1:60, and then refluxing and heating to 80 ℃ until the crude product A is completely dissolved to obtain a solution A;
(4) and mixing the activated carbon in a ratio of 0.03: 1, adding the mixture into the solution A, quickly stirring and decoloring for 20min, and filtering while the mixture is hot to obtain a solution B;
(5) cooling the solution B to 10 ℃ to separate out thiothiamine, and then filtering and drying the separated thiothiamine to obtain refined thiothiamine;
the time for drying the precipitated thiothiamine is 8 hours, and the temperature is 80 ℃.
Example 3
A method of refinement of thiothiamine, said method comprising the steps of:
(1) firstly, washing a thiothiamine crude product with ethanol at 18 ℃, removing impurities dissolved in the ethanol in the thiothiamine crude product, and then filtering and drying to obtain an alcohol-washed thiothiamine crude product;
the ratio of the thiothiamine crude product to the ethanol is 1: 3.
The drying time after the alcohol washing is 3 hours, and the temperature is 42 ℃;
(2) washing the crude product of the thiamine after alcohol washing and drying with distilled water at the temperature of 18 ℃ to remove impurities dissolved in water in the thiamine to obtain a crude product A;
the ratio of the crude thiothiamine to the distilled water is 1: 4.
The drying time after washing is 6 hours, and the temperature is 65 ℃;
(3) mixing the crude product A and ethanol according to the proportion of 1:55, and then refluxing and heating to 78 ℃ until the crude product A is completely dissolved to obtain a solution A;
(4) and mixing the activated carbon in a ratio of 0.02: 1, adding the mixture into the solution A, quickly stirring and decoloring for 18min, and filtering while the mixture is hot to obtain a solution B;
(5) cooling the solution B to 8 ℃ to separate out thiothiamine, and then filtering and drying the separated thiothiamine to obtain refined thiothiamine;
the time for drying the precipitated thiothiamine is 6 hours, and the temperature is 65 ℃.
Example 4
A method of refinement of thiothiamine, said method comprising the steps of:
(1) firstly, washing a crude thiothiamine product with ethanol at 22 ℃, removing impurities dissolved in the ethanol in the crude thiothiamine product, and then filtering and drying to obtain an alcohol-washed crude thiothiamine product;
the ratio of the thiothiamine crude product to the ethanol is 1: 4.
The drying time after the alcohol washing is 4 hours, and the temperature is 48 ℃;
(2) washing the crude product of the thiamine after alcohol washing and drying with distilled water at the temperature of 22 ℃ to remove impurities dissolved in water in the thiamine to obtain a crude product A;
the ratio of the thiothiamine crude product to the distilled water is 1: 3.
The drying time after washing is 7 hours, and the temperature is 75 ℃;
(3) mixing the crude product A and ethanol according to the proportion of 1:45, and then refluxing and heating to 72 ℃ until the crude product A is completely dissolved to obtain a solution A;
(4) and mixing the activated carbon in a ratio of 0.03: 1, adding the mixture into the solution A, quickly stirring and decoloring for 17min, and filtering while the mixture is hot to obtain a solution B;
(5) cooling the solution B to 2 ℃ to separate out thiothiamine, and then filtering and drying the separated thiothiamine to obtain refined thiothiamine;
the time for drying the precipitated thiothiamine is 7 hours, and the temperature is 75 ℃.
Example 5
A method of refinement of thiothiamine, said method comprising the steps of:
(1) firstly, washing a thiothiamine crude product with ethanol at the temperature of 20 ℃, removing impurities dissolved in the ethanol in the thiothiamine crude product, and then filtering and drying to obtain an alcohol-washed thiothiamine crude product;
the ratio of the thiothiamine crude product to the ethanol is 1: 2.
The drying time after the alcohol washing is 4 hours, and the temperature is 45 ℃;
(2) washing the crude product of the thiamine after alcohol washing and drying with distilled water at the temperature of 20 ℃, and removing impurities dissolved in water in the thiamine to obtain a crude product A;
the ratio of the crude thiothiamine to the distilled water is 1: 2.
The drying time after washing is 7 hours, and the temperature is 70 ℃;
(3) mixing the crude product A and ethanol according to a ratio of 1:50, and then refluxing and heating to 80 ℃ until the crude product A is completely dissolved to obtain a solution A;
(4) and mixing the activated carbon in a ratio of 0.01: 1, quickly stirring and decoloring for 15min, and filtering while hot to obtain a solution B;
(5) cooling the solution B to 4 ℃ to separate out thiothiamine, and then filtering and drying the separated thiothiamine to obtain refined thiothiamine;
the time for drying the precipitated thiothiamine is 7 hours, and the temperature is 70 ℃.
Comparative example 1
A method of refinement of thiothiamine, said method comprising the steps of:
(1) washing the crude product of the thiothiamine with distilled water at the temperature of 20 ℃, and removing impurities dissolved in water in the thiothiamine to obtain a crude product A;
the ratio of the crude thiothiamine to the distilled water is 1: 2.
The drying time after washing is 7 hours, and the temperature is 70 ℃;
(2) mixing the crude product A and ethanol according to a ratio of 1:50, and then refluxing and heating to 80 ℃ until the crude product A is completely dissolved to obtain a solution A;
(3) and mixing the activated carbon in a ratio of 0.01: 1, quickly stirring and decoloring for 15min, and filtering while hot to obtain a solution B;
(4) cooling the solution B to 4 ℃ to separate out thiothiamine, and then filtering and drying the separated thiothiamine to obtain refined thiothiamine;
the time for drying the precipitated thiothiamine is 7 hours, and the temperature is 70 ℃.
This comparative example is the same as example 5 except that it does not include the alcohol wash step.
Comparative example 2
A method of refinement of thiothiamine, said method comprising the steps of:
(1) firstly, washing a thiothiamine crude product by using ethanol, removing impurities dissolved in the ethanol in the thiothiamine crude product, and then filtering and drying to obtain an alcohol-washed thiothiamine crude product;
the ratio of the thiothiamine crude product to the ethanol is 1: 2.
The drying time after the alcohol washing is 4 hours, and the temperature is 45 ℃;
(2) mixing the alcohol-washed crude thiamine with ethanol according to the proportion of 1:50, and then refluxing and heating to 80 ℃ until the mixture is completely dissolved to obtain a solution A;
(3) and mixing the activated carbon in a ratio of 0.01: 1, quickly stirring and decoloring for 15min, and filtering while hot to obtain a solution B;
(4) cooling the solution B to 4 ℃ to separate out thiothiamine, and then filtering and drying the separated thiothiamine to obtain refined thiothiamine;
the time for drying the precipitated thiothiamine is 7 hours, and the temperature is 70 ℃.
This comparative example is the same as example 5 except that it does not include a water washing step.
Comparative example 3
A method of refinement of thiothiamine, said method comprising the steps of:
(1) firstly, washing a thiothiamine crude product with ethanol at the temperature of 20 ℃, removing impurities dissolved in the ethanol in the thiothiamine crude product, and then filtering and drying to obtain an alcohol-washed thiothiamine crude product;
the ratio of the thiothiamine crude product to the ethanol is 1: 2.
The drying time after the alcohol washing is 4 hours, and the temperature is 45 ℃;
(2) washing the crude product of the thiamine after alcohol washing and drying with distilled water at the temperature of 20 ℃, and removing impurities dissolved in water in the thiamine to obtain a crude product A;
the ratio of the crude thiothiamine to the distilled water is 1: 2.
The drying time after washing is 7 hours, and the temperature is 70 ℃;
(3) mixing the crude product A and ethanol according to a ratio of 1:50, and then refluxing and heating to 80 ℃ until the crude product A is completely dissolved to obtain a solution A;
(4) cooling the solution A to 4 ℃ to separate out thiothiamine, and then filtering and drying the separated thiothiamine to obtain refined thiothiamine;
the time for drying the precipitated thiothiamine is 7 hours, and the temperature is 70 ℃.
This comparative example is identical to example 5 except that it does not include the step of decolorizing with activated carbon.
Comparative example 4
A method of refinement of thiothiamine, said method comprising the steps of:
(1) firstly, washing a crude thiothiamine product with methanol at the temperature of 20 ℃, removing impurities dissolved in the methanol in the crude thiothiamine product, and then filtering and drying to obtain an alcohol-washed crude thiothiamine product;
the ratio of the thiothiamine crude product to the ethanol is 1: 2.
The drying time after the alcohol washing is 4 hours, and the temperature is 45 ℃;
(2) washing the crude product of the thiamine after alcohol washing and drying with distilled water at the temperature of 20 ℃, and removing impurities dissolved in water in the thiamine to obtain a crude product A;
the ratio of the crude thiothiamine to the distilled water is 1: 2.
The drying time after washing is 7 hours, and the temperature is 70 ℃;
(3) mixing the crude product A and ethanol according to a ratio of 1:50, and then refluxing and heating to 80 ℃ until the crude product A is completely dissolved to obtain a solution A;
(4) and mixing the activated carbon in a ratio of 0.01: 1, quickly stirring and decoloring for 15min, and filtering while hot to obtain a solution B;
(5) cooling the solution B to 4 ℃ to separate out thiothiamine, and then filtering and drying the separated thiothiamine to obtain refined thiothiamine;
the time for drying the precipitated thiothiamine is 7 hours, and the temperature is 70 ℃.
This comparative example is the same as example 5 except that methanol is used to wash the crude thiothiamine in step (1).
Comparative example 5
A method of refinement of thiothiamine, said method comprising the steps of:
(1) firstly, washing a thiothiamine crude product with ethanol at the temperature of 20 ℃, removing impurities dissolved in the ethanol in the thiothiamine crude product, and then filtering and drying to obtain an alcohol-washed thiothiamine crude product;
the ratio of the thiothiamine crude product to the ethanol is 1: 2.
The drying time after the alcohol washing is 4 hours, and the temperature is 45 ℃;
(2) washing the crude product of the thiamine after alcohol washing and drying with distilled water at the temperature of 20 ℃, and removing impurities dissolved in water in the thiamine to obtain a crude product A;
the ratio of the crude thiothiamine to the distilled water is 1: 2.
The drying time after washing is 7 hours, and the temperature is 70 ℃;
(3) mixing the crude product A and methanol according to the proportion of 1:50, and then refluxing and heating to 80 ℃ until the crude product A is completely dissolved to obtain a solution A;
(4) and mixing the activated carbon in a ratio of 0.01: 1, quickly stirring and decoloring for 15min, and filtering while hot to obtain a solution B;
(5) cooling the solution B to 4 ℃ to separate out thiothiamine, and then filtering and drying the separated thiothiamine to obtain refined thiothiamine;
the time for drying the precipitated thiothiamine is 7 hours, and the temperature is 70 ℃.
This comparative example is the same as example 5 except that in step (3), methanol is used to dissolve crude product A.
Effect example 1
The thiothiamine obtained through purification has high purity which can reach 98-99%, and guarantee can be provided for subsequent preparation of a vitamin B1 product. Now, the purity of the thiamine refined in examples 1 to 5 and comparative examples 1 to 3 is detected by a liquid chromatography detection method, which specifically comprises the following steps:
the peak information of the detection map is as follows:
| group of | Peak area | Peak width | Retention time |
| Example 1 | 98.332％ | 0.1932 | 8.432 |
| Example 2 | 98.563％ | 0.1936 | 8.435 |
| Example 3 | 98.623％ | 0.1938 | 8.442 |
| Example 4 | 98.654％ | 0.1943 | 8.430 |
| Example 5 | 98.265％ | 0.1921 | 8.451 |
| Comparative example 1 | 96.867％ | 0.1886 | 8.442 |
| Comparative example 2 | 97.236％ | 0.1864 | 8.463 |
| Comparative example 3 | 96.261％ | 0.1855 | 8.436 |
From the peak information, the purity of the thiothiamine obtained in examples 1 to 5 and comparative examples 1 to 3 of the present application is:
in conclusion, the refining method of thiamine is simple and efficient, the content of purified thiamine can reach 98% -99%, and the vast majority of impurities are removed, so that the synthesis quality of vitamin B1 is guaranteed.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (1)
1. A method for refining thiothiamine, comprising the steps of:
(a1) firstly, washing a thiothiamine crude product with ethanol at 15-25 ℃, removing impurities dissolved in the ethanol in the thiothiamine crude product, and then filtering and drying to obtain an alcohol-washed thiothiamine crude product;
the mass ratio of the thiothiamine crude product to the ethanol is 1: 2-5;
drying the alcohol washed product for 2-5 hours at the temperature of 40-50 ℃;
(a2) washing the crude product of the thiamine after alcohol washing and drying with distilled water at 15-25 ℃, and removing impurities dissolved in water in the thiamine to obtain a crude product A;
the mass ratio of the thiothiamine crude product to the distilled water is 1: 2-5;
the drying time after washing is 5-8 h, and the temperature is 60-80 ℃;
(b1) mixing the crude product A and ethanol according to the mass ratio of 1: 40-60, and then refluxing and heating to 70-80 ℃ until the crude product A is completely dissolved to obtain a solution A;
(b2) and mixing the activated carbon in a hot state in a ratio of 0.01-0.03: 1, quickly stirring and decoloring for 15-20 min at a stirring speed of 200-500 r/min, and filtering while hot to obtain a solution B;
(c) cooling the solution B to 0-10 ℃ to separate out thiothiamine, and then filtering and drying the separated thiothiamine to obtain refined thiothiamine;
the time for drying the precipitated thiothiamine is 5-8 hours, and the temperature is 60-80 ℃.
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