CN106977509A - The multiple water law method for crystallising of thiamine hydrochloride - Google Patents
The multiple water law method for crystallising of thiamine hydrochloride Download PDFInfo
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- CN106977509A CN106977509A CN201710195515.5A CN201710195515A CN106977509A CN 106977509 A CN106977509 A CN 106977509A CN 201710195515 A CN201710195515 A CN 201710195515A CN 106977509 A CN106977509 A CN 106977509A
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- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
The present invention discloses a kind of multiple water crystallization technique of thiamine hydrochloride, comprises the following steps：By Temperature fall after thiamine hydrochloride crude product and purified water heating stirring to thiamine hydrochloride dissolving, then cooled with frozen water and be incubated crystallization and filtration, obtain filtrate I and filter residue I, filter residue I washs to obtain thiamine hydrochloride with ethanol；Filtrate I is concentrated, the Temperature fall of filtrate I is stirred, then is cooled with frozen water and is incubated crystallization and filtration, filter to get filtrate II and filter residue II, and filter residue II washs to obtain thiamine hydrochloride with ethanol；Temperature fall after filtrate II, stirring filtrate I is concentrated, then is cooled with frozen water and is incubated crystallization and filtration, filter to get filtrate III and filter residue III, and filter residue III washs to obtain thiamine hydrochloride with ethanol.The present invention replaces the crystallization of alcohol method using the crystallization of multiple water law, improves the yield of thiamine hydrochloride；It can also dramatically improve the natural deposited dry density of thiamine hydrochloride by the natural deposited dry density of thiamine hydrochloride from 0.20 lifting to 0.56g/mL simultaneously.
Description
Technical field
The invention belongs to the method for crystallising of thiamine hydrochloride, a kind of side of the multiple water law crystallization of thiamine hydrochloride is more particularly to
Method.
Background technology
Existing thiamine hydrochloride alcohol crystal need to consume a large amount of ethanol, and cost is higher；And the hydrochloric acid for passing through alcohol crystal
Thiamines, its natural deposited dry density is smaller, influences the quality of thiamine hydrochloride.
The content of the invention
It is an object of the invention to provide a kind of crystallization of the multiple water law for the thiamine hydrochloride that cost is relatively low and bulk density is higher
Method.
According to an aspect of the invention, there is provided a kind of multiple water crystallization technique of thiamine hydrochloride, it is characterised in that bag
Include following steps：
Thiamine hydrochloride crude product and purified water are stirred into the Temperature fall to thiamine hydrochloride dissolving at a temperature of 60 DEG C~70 DEG C
To 25 DEG C~27 DEG C, then it is cooled to frozen water 8 DEG C~12 DEG C, is incubated 15min~25min crystallization and filtrations, obtains filtrate I and filter residue
I, filter residue I washs to obtain thiamine hydrochloride with ethanol；
Filtrate I is concentrated, 20 DEG C~30 are naturally cooling to after I 15min of stirring filtrate~25min at a temperature of 45 DEG C~55 DEG C
DEG C, then be cooled to 8 DEG C~12 DEG C with frozen water and be incubated 15min~25min crystallization and filtrations, filter to get filtrate II and filter residue II,
Filter residue II washs to obtain thiamine hydrochloride with ethanol；
Concentrate filtrate II, be naturally cooling to after I 15min of stirring filtrate~25min at a temperature of 45 DEG C~55 DEG C 20 DEG C~
30 DEG C, then be cooled to 8 DEG C~12 DEG C with frozen water and be incubated 15min~25min crystallization and filtrations, filter to get filtrate III and filter residue
III, filter residue III washs to obtain thiamine hydrochloride with ethanol.
A kind of multiple water crystallization technique of thiamine hydrochloride, comprises the following steps：
Thiamine hydrochloride crude product and purified water are stirred into the Temperature fall to thiamine hydrochloride dissolving at a temperature of 60 DEG C~70 DEG C
Filtered to 25 DEG C, then after being cooled to frozen water 10 DEG C, insulation 20min, obtain filtrate I and filter residue I, filter residue I washs to obtain salt with ethanol
Allithiamine；
Filtrate I is concentrated, 25 DEG C are naturally cooling to after stirring filtrate I 20min at a temperature of 50 DEG C, then 10 are cooled to frozen water
DEG C and be incubated 20min, filter to get filtrate II and filter residue II, and filter residue II washs to obtain thiamine hydrochloride with ethanol；
Filtrate II is concentrated, 25 DEG C are naturally cooling to after stirring filtrate I 20min at a temperature of 50 DEG C, then be cooled to frozen water
10 DEG C and 20min is incubated, filter to get filtrate III and filter residue III, and filter residue III washs to obtain thiamine hydrochloride with ethanol.
In some embodiments, the filtrate III is used to produce as subcrystalline raw material again, including：
Filtrate III and ammonium nitrate, ammoniacal liquor are reacted, reaction is cooled to 8 DEG C, filtering, the filter residue first obtained by filtering after terminating
Dry product I is dried to obtain after alcohol washing；
The dry product I and methanol, sour methanol are reacted, after reaction terminates, slow cooling is cooled to 25 DEG C, then with frozen water
15 DEG C, filtering, the filter residue obtained by filtering must be used for the raw material crystallized again with methanol washing and drying.
In some embodiments, concentration filtrate I to solid-liquid mass ratio is 100:74~76.
In some embodiments, concentration filtrate II to solid-liquid mass ratio is 100:74~76.
Its advantage is：The present invention replaces the crystallization of alcohol method using the crystallization of multiple water law, improves the yield of thiamine hydrochloride；
Filter residue is made to the raw material recrystallized, 20% cost is reduced on raw material；Crystallized by multiple water law, can also be by salt
The natural deposited dry density of allithiamine is from 0.20 lifting to 0.56g/mL, and the natural packing for dramatically improving thiamine hydrochloride is close
Degree.
Embodiment
Embodiment 1
200g thiamine hydrochlorides are added in three-necked flask, three-necked flask is put into 60 DEG C~70 DEG C of water by 152g purified waters
In bath, stirring is completely dissolved thiamine hydrochloride, closes the heater switch of water-bath, makes three-necked flask whole system with water-bath
Cool slowly together.When temperature drops to 25 DEG C or so, 10 DEG C are down to frozen water, and be incubated 20min.Filter to get filtrate I and filter
Slag I, filtrate I is stand-by, filter residue I dried after being washed with 30g ethanol weight be 72.43g thiamine hydrochloride, yield is 36.22%,
Quality analysis is qualified, and the bulk density of finished product is promoted to 0.5g/mL by the 0.2g/mL of raw material.
It is 100 that filtrate I is concentrated into solid-liquid mass ratio by Rotary Evaporators at 50 DEG C:76, then it is transferred to three mouthfuls
In flask, in the water-bath for inserting 50 DEG C, 20min is stirred, the heater switch of water-bath is closed, makes it with water-bath Temperature fall.
When temperature is reduced to 25 DEG C or so, 10 DEG C are cooled to frozen water, 20min is incubated.Filter to get filtrate II and filter residue II, filter residue II
Dried after being washed with 20g ethanol weight be 42.5g thiamine hydrochloride, yield is 21.25%, and quality analysis is qualified, finished product
Bulk density is promoted to 0.54g/mL by the 0.5g/mL of raw material.
It is 100 that filtrate II is concentrated into solid-liquid mass ratio by Rotary Evaporators at 50 DEG C:76, it is being transferred to three mouthfuls
In flask, in the water-bath for being placed in 50 DEG C, 20min is stirred, the heater switch of water-bath is closed, makes it with water-bath Temperature fall.
When temperature drops to 25 DEG C or so, 10 DEG C are down to frozen water, and be incubated 20min.Filtered to get filtrate III and filter residue III, and filter residue III is used
10g ethanol washing after dry weight be 20.84g thiamine hydrochloride, yield is 10.42%, and quality analysis is qualified, the heap of finished product
Product density is promoted to 0.56g/mL by the 0.54g/mL of raw material.
The joint yield of three step water crystallizations is 67.89%.
By filtrate III and ammonium nitrate, ammoniacal liquor reaction, after reaction terminates, 8 DEG C are cooled to, the filter residue IV obtained by filtering uses 30g
Dried after methanol washing, obtain 55.23g dry products I.
55.23g dry products and methanol, sour methanol are reacted, after reaction terminates, when slow cooling is to 25 DEG C or so, then ice is used
Water is cooled to 15 DEG C.The dry product II for the 55.78g that filter residue obtained by filtering is washed and dried with 30g methanol, quality analysis is qualified.
Dry product II is as the raw material of water crystallization, and repeat the above steps carries out three step water crystallization methods it is crystallized again,
The comprehensive utilization ratio of raw material is 95.8%.
Embodiment 2
200g thiamine hydrochlorides are added in three-necked flask, three-necked flask is put into 60 DEG C~70 DEG C of water by 152g purified waters
In bath, stirring is completely dissolved thiamine hydrochloride, closes the heater switch of water-bath, makes three-necked flask whole system with water-bath
Cool slowly together.When temperature drops to 27 DEG C or so, 12 DEG C are down to frozen water, and be incubated 25min.Filter to get filtrate I and filter
Slag I, filtrate I is stand-by, filter residue I dried after being washed with 30g ethanol weight be 73.56g thiamine hydrochloride, yield is 36.78%,
Quality analysis is qualified, and the bulk density of finished product is promoted to 0.5g/mL by the 0.2g/mL of raw material.
It is 100 that filtrate I is concentrated into solid-liquid mass ratio by Rotary Evaporators at 50 DEG C:74, then it is transferred to three mouthfuls
In flask, in the water-bath for inserting 50 DEG C, 15min is stirred, the heater switch of water-bath is closed, makes it with water-bath Temperature fall.
When temperature is reduced to 25 DEG C or so, 8 DEG C are cooled to frozen water, 15min is incubated.Filter to get filtrate II and filter residue II, filter residue II
Dried after being washed with 20g ethanol weight be 42.8g thiamine hydrochloride, yield is 21.4%, and quality analysis is qualified, the heap of finished product
Product density is promoted to 0.52g/mL by the 0.5g/mL of raw material.
It is 100 that filtrate II is concentrated into solid-liquid mass ratio by Rotary Evaporators at 50 DEG C:78, it is being transferred to three mouthfuls
In flask, in the water-bath for being placed in 50 DEG C, 25min is stirred, the heater switch of water-bath is closed, makes it with water-bath Temperature fall.
When temperature drops to 30 DEG C or so, 12 DEG C are down to frozen water, and be incubated 25min.Filtered to get filtrate III and filter residue III, and filter residue III is used
10g ethanol washing after dry weight be 22.04g thiamine hydrochloride, yield is 11.02%, and quality analysis is qualified, the heap of finished product
Product density is promoted to 0.56g/mL by the 0.52g/mL of raw material.
The joint yield of three step water crystallizations is 69.2%.
By filtrate III and ammonium nitrate, ammoniacal liquor reaction, after reaction terminates, 8 DEG C are cooled to, the filter residue IV obtained by filtering uses 30g
Dried after methanol washing, obtain 56.04g dry products I.
56.04g dry products and methanol, sour methanol are reacted, after reaction terminates, when slow cooling is to 25 DEG C or so, then ice is used
Water is cooled to 15 DEG C.The dry product II for the 55.18g that filter residue obtained by filtering is washed and dried with 30g methanol, quality analysis is qualified.
Dry product II is as the raw material of water crystallization, and repeat the above steps carries out three step water crystallization methods it is crystallized again,
The comprehensive utilization ratio of raw material is 96.5%.
Embodiment 1
200g thiamine hydrochlorides are added in three-necked flask, three-necked flask is put into 60 DEG C~70 DEG C of water by 152g purified waters
In bath, stirring is completely dissolved thiamine hydrochloride, closes the heater switch of water-bath, makes three-necked flask whole system with water-bath
Cool slowly together.When temperature drops to 27 DEG C or so, 12 DEG C are down to frozen water, and be incubated 25min.Filter to get filtrate I and filter
Slag I, filtrate I is stand-by, filter residue I dried after being washed with 30g ethanol weight be 72.02g thiamine hydrochloride, yield is 36.01%,
Quality analysis is qualified, and the bulk density of finished product is promoted to 0.5g/mL by the 0.2g/mL of raw material.
It is 100 that filtrate I is concentrated into solid-liquid mass ratio by Rotary Evaporators at 50 DEG C:74, then it is transferred to three mouthfuls
In flask, in the water-bath for inserting 45 DEG C, 15min is stirred, the heater switch of water-bath is closed, makes it with water-bath Temperature fall.
When temperature is reduced to 20 DEG C or so, 8 DEG C are cooled to frozen water, 15min is incubated.Filter to get filtrate II and filter residue II, filter residue II
Dried after being washed with 20g ethanol weight be 43.6g thiamine hydrochloride, yield is 21.8%, and quality analysis is qualified, the heap of finished product
Product density is promoted to 0.53g/mL by the 0.5g/mL of raw material.
It is 100 that filtrate II is concentrated into solid-liquid mass ratio by Rotary Evaporators at 50 DEG C:78, it is being transferred to three mouthfuls
In flask, in the water-bath for being placed in 45 DEG C, 15min is stirred, the heater switch of water-bath is closed, makes it with water-bath Temperature fall.
When temperature drops to 25 DEG C or so, 11 DEG C are down to frozen water, and be incubated 20min.Filtered to get filtrate III and filter residue III, and filter residue III is used
10g ethanol washing after dry weight be 21.24g thiamine hydrochloride, yield is 10.62%, and quality analysis is qualified, the heap of finished product
Product density is promoted to 0.56g/mL by the 0.53g/mL of raw material.
The joint yield of three step water crystallizations is 68.43%.
By filtrate III and ammonium nitrate, ammoniacal liquor reaction, after reaction terminates, 8 DEG C are cooled to, the filter residue IV obtained by filtering uses 30g
Dried after methanol washing, obtain 55.43g dry products I.
55.43g dry products and methanol, sour methanol are reacted, after reaction terminates, when slow cooling is to 25 DEG C or so, then ice is used
Water is cooled to 15 DEG C.The dry product II for the 56.87g that filter residue obtained by filtering is washed and dried with 30g methanol, quality analysis is qualified.
Dry product II is as the raw material of water crystallization, and repeat the above steps carries out three step water crystallization methods it is crystallized again,
The comprehensive utilization ratio of raw material is 96.7%.
Above-described is only some embodiments of the present invention.For those of ordinary skill in the art, do not taking off
On the premise of the invention design, various modifications and improvements can be made, these belong to protection scope of the present invention.
Claims (5)
1. the multiple water crystallization technique of thiamine hydrochloride, it is characterised in that comprise the following steps：
Thiamine hydrochloride crude product and purified water are stirred at a temperature of 60 DEG C~70 DEG C and are naturally cooling to 25 to thiamine hydrochloride dissolving
DEG C~27 DEG C, then it is cooled to frozen water 8 DEG C~12 DEG C, insulation 15mi n~25mi n crystallization and filtrations obtain filtrate I and filter residue I,
Filter residue I washs to obtain thiamine hydrochloride with ethanol；
Filtrate I is concentrated, 20 DEG C~30 are naturally cooling to after stirring filtrate I 15mi n~25mi n at a temperature of 45 DEG C~55 DEG C
DEG C, then be cooled to 8 DEG C~12 DEG C with frozen water and be incubated 15mi n~25mi n crystallization and filtrations, filter to get filtrate II and filter residue
II, filter residue II washs to obtain thiamine hydrochloride with ethanol；
Filtrate II is concentrated, 20 DEG C~30 are naturally cooling to after stirring filtrate I 15mi n~25mi n at a temperature of 45 DEG C~55 DEG C
DEG C, then be cooled to 8 DEG C~12 DEG C with frozen water and be incubated 15mi n~25mi n crystallization and filtrations, filter to get filtrate III and filter residue
III, filter residue III washs to obtain thiamine hydrochloride with ethanol.
2. the multiple water crystallization technique of thiamine hydrochloride according to claim 1, it is characterised in that comprise the following steps：
Thiamine hydrochloride crude product and purified water are stirred at a temperature of 60 DEG C~70 DEG C and are naturally cooling to 25 to thiamine hydrochloride dissolving
DEG C, then filter after being cooled to frozen water 10 DEG C, insulation 20mi n, filtrate I and filter residue I are obtained, filter residue I washs to obtain hydrochloric acid sulphur with ethanol
Amine；
Filtrate I is concentrated, 25 DEG C are naturally cooling to after stirring filtrate I 20mi n at a temperature of 50 DEG C, then is cooled to frozen water 10 DEG C
And 20mi n are incubated, filter to get filtrate II and filter residue II, and filter residue II washs to obtain thiamine hydrochloride with ethanol；
Filtrate II is concentrated, 25 DEG C are naturally cooling to after stirring filtrate I 20mi n at a temperature of 50 DEG C, then is cooled to frozen water 10 DEG C
And 20mi n are incubated, filter to get filtrate III and filter residue III, and filter residue III washs to obtain thiamine hydrochloride with ethanol.
3. the multiple water crystallization technique of thiamine hydrochloride according to claim 1, it is characterised in that the filtrate III is used to make
It is taken as subcrystalline raw material again, including：
Filtrate III and ammonium nitrate, ammoniacal liquor are reacted, reaction is cooled to 8 DEG C after terminating, filtering, the filter residue obtained by filtering is washed with methanol
Dry product I is dried to obtain after washing；
The dry product I and methanol, sour methanol are reacted, after reaction terminates, slow cooling is cooled to 15 to 25 DEG C, then with frozen water
DEG C, filtering, the filter residue obtained by filtering must be used for the raw material crystallized again with methanol washing and drying.
4. the multiple water crystallization technique of thiamine hydrochloride according to claim 1, it is characterised in that concentration filtrate I to solid-liquid
Mass ratio is 100:74~78.
5. the multiple water crystallization technique of thiamine hydrochloride according to claim 1, it is characterised in that concentration filtrate II to solid-liquid
Mass ratio is 100:74~78.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087393A (en) * | 2019-12-30 | 2020-05-01 | 江苏兄弟维生素有限公司 | Thiamine hydrochloride, drying method and application thereof, and vitamin B1 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952126A (en) * | 2012-12-03 | 2013-03-06 | 华中药业股份有限公司 | Novel method for synthesizing vitamin B1 hydrochloride |
| CN104817551A (en) * | 2015-05-07 | 2015-08-05 | 常州大学 | New method of preparing vitamin B1 hydrochloride |
| CN105315272A (en) * | 2015-10-19 | 2016-02-10 | 天津大学 | Method for preparing thiamine hydrochloride crystal product |
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2017
- 2017-03-29 CN CN201710195515.5A patent/CN106977509B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952126A (en) * | 2012-12-03 | 2013-03-06 | 华中药业股份有限公司 | Novel method for synthesizing vitamin B1 hydrochloride |
| CN104817551A (en) * | 2015-05-07 | 2015-08-05 | 常州大学 | New method of preparing vitamin B1 hydrochloride |
| CN105315272A (en) * | 2015-10-19 | 2016-02-10 | 天津大学 | Method for preparing thiamine hydrochloride crystal product |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087393A (en) * | 2019-12-30 | 2020-05-01 | 江苏兄弟维生素有限公司 | Thiamine hydrochloride, drying method and application thereof, and vitamin B1 |
| CN111087393B (en) * | 2019-12-30 | 2021-11-23 | 江苏兄弟维生素有限公司 | Thiamine hydrochloride, drying method and application thereof, and vitamin B1 |
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