CN102732648A - Method for refining fructose as main raw material of carbohydrate and electrolyte injection - Google Patents
Method for refining fructose as main raw material of carbohydrate and electrolyte injection Download PDFInfo
- Publication number
- CN102732648A CN102732648A CN2012102364770A CN201210236477A CN102732648A CN 102732648 A CN102732648 A CN 102732648A CN 2012102364770 A CN2012102364770 A CN 2012102364770A CN 201210236477 A CN201210236477 A CN 201210236477A CN 102732648 A CN102732648 A CN 102732648A
- Authority
- CN
- China
- Prior art keywords
- fructose
- raw material
- main raw
- electrolyte injection
- purification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a method for refining fructose as main raw material of carbohydrate and electrolyte injection, comprising the following steps: (1) dissolving crude product fructose into hot aqueous solution of ethanol; (2) decreasing temperature, and adding an organic solvent, wherein the solvent is one or more of the acetonitrile, tetrahydrofuran, acetone, absolute ethanol and isopropanol; and (3) decreasing temperature for crystallization, filtering, and drying the obtained crystals under reduced pressure to obtain the fructose. The process for refining the fructose is simple and convenient to operate, low in cost and simple in crystallization condition, can ensure that the content of hydroxymethylfurfural (5-HMF) in the fructose as the main raw material of the carbohydrate and electrolyte injection is reduced effectively and the product is good in quality, high in yield and is suitable for industrial production.
Description
Technical field
The invention belongs to the pharmaceutical chemistry field, be specifically related to a kind of process for purification of mixing sugar electrolyte injection main raw material fructose.
Background technology
Fructose is the sweetest monose, contains 6 carbon atoms, is the isomers of glucose, and molecular structural formula is following:
Fructose widespread use in worldwide.Europe, U.S.A, daily listed pharmacopeia in, can be used as oral or injection.Fructose is oral slower than glucose absorption, but metabolism is faster than glucose in vivo after absorbing back or intravenously administrable, is prone to absorbed by body, and does not rely on Regular Insulin, and is little to blood sugar influence, is applicable to patient's supplementing energy of glucose metabolism and hepatic insufficiency.Therefore, fructose is specially adapted to glucose metabolism obstacle person (diabetics) as nutrition agent.Fructose can be accelerated the alcoholic acid metabolism, can be used for treating ethylism, and intravenous injection 500mL massfraction is the effect that 40% fructose soln can reach equivalent glucose stoste; Fructose can be made into injection liquid in pharmaceutical industries, is used for the treatment of cardiovascular diseases, mellitus, brainpan disease and liver etc. like the transfusion of national essential drugs Glycerin Fructose, fructose sodium chloride injection and making fructose Vc tablet etc.
Yet, all have a certain amount of impurity 5 hydroxymethyl furfural (5-HMF) in existing glucose and the fructose injection.5-HMF is the aldehyde compound that monose compound such as glucose dewaters under conditions such as high temperature or weak acid and produces, and this compound has infringement to human body voluntary muscle and internal organ.And 5-HMF stability is not good, be prone to further be decomposed into levulinic acid and formic acid, or polymerization reaction take place, the material of its generation is harmful.5-HMF itself is colourless, and its polymkeric substance is a coloring matter, can cause the injection liquid variable color, and the color and luster depth is directly proportional with the growing amount of 5-HMF, influences the quality of injection liquid.Therefore, along with being the continuous appearance of the various infusion solutions of carrier with glucose, fructose injection, the control of 5 hydroxymethyl furfural in glucose and the fructose injection (5-HMF) has caused concern.For glucose injection, the method that CHP (2010), EP (1998) and USP (24) standards of pharmacopoeia all adopt 284nm to measure optical density is controlled the content of 5-HMF in the product, and concentration is different, and the limit of optical density is different; The foreign enterprises standard has been carried out the limit handling of 5-HMF to the oral prepns of using monose such as glucose, and China's pharmacopeia is also carried out the strict limit handling of 5-HMF to honey, fructose raw material.The measuring method of stipulating in the Chinese Pharmacopoeia is a ultraviolet spectrophotometry, and its limit handling is that absorbancy is no more than 0.32.The content of 5-HMF for the mixing sugar electrolyte injection that contains fructose, is very important quality index.
CN101638695 has described fructose liquid method of purification, fructose liquid is mixed the crystallization of in crystallizer, lowering the temperature with absolute ethyl alcohol or 95% ethanol; 50 ~ 60 ℃ of crystallization origin temps; PH value 3.3 ~ 4.5, degree of supersaturation 1.1 ~ 1.2, the alcohol add-on accounts for 0.5% of quantity of fructose; Crystallization time 32 ~ 36h, centrifugal, dry crystal diabetin.In this method, because fructose has very high solubleness (25 ℃ time 4.0g/g) in water, the fructose fluid viscosity is big; Cause crystal growth limited; The crystallization complicated condition, preparation cost is higher, and crystallization time is long; The content of objectionable impurities 5-HMF is not controlled, quality product can not satisfy the requirement of injection liquid.
At present, domestic refining to fructose for injection especially do not have ideal method to the control of objectionable impurities 5-HMF wherein as yet; And still have a lot of weak points in the existing fructose crystallization technique, the present invention provides a kind of process for purification, and this method is easy to operate; Cost is low, and crystallization condition is simple, can effectively reduce the content of 5-HMF in the fructose; Good product quality, yield is high, is fit to suitability for industrialized production.This method is specially adapted to the preparation of the fructose of mixing sugar electrolyte injection main raw material.
Summary of the invention
Goal of the invention:, the invention provides a kind of mixing sugar electrolyte injection main raw material fructose process for purification that can effectively reduce the content of 5-HMF in order to address the deficiencies of the prior art.
Technical scheme: the process for purification of fructose in a kind of mixing sugar electrolyte injection provided by the invention may further comprise the steps:
(1) the fructose bullion is dissolved in the aqueous ethanolic solution or absolute ethyl alcohol of heat, obtains the fructose ethanolic soln;
(2) cooling adds organic solvent, and said organic solvent is selected from one or more the mixture in acetonitrile, THF, acetone, absolute ethyl alcohol and the Virahol;
(3) the cooling crystallization filters, and gained crystal drying under reduced pressure promptly gets.
A kind of preferred as technical scheme of the present invention, in the step (1), said fructose bullion and consumption of ethanol are than being 1kg: (2 ~ 5) L most preferably is 1kg: (3 ~ 4) L; Solvent temperature is 60 ~ 70 ℃, most preferably is 60 ~ 65 ℃; Said aqueous ethanolic solution concentration expressed in percentage by volume is more than 70%, preferred 80-98%.
A kind of preferred as technical scheme of the present invention, in the step (2), the amount ratio of said organic solvent and fructose bullion be (0.5 ~ 1.5) L:1kg, lowers the temperature afterwards that temperature is 40 ~ 55 ℃, temperature fall time is 30 ~ 60min.
A kind of preferred as technical scheme of the present invention, in the step (3), said cooling crystallization step is: after reducing to 20 ~ 30 ℃ with the rate of temperature fall of 5 ~ 15 ℃/h, crystallization 2 ~ 4h reduces to-5 ~ 5 ℃ with the rate of temperature fall of 8 ~ 15 ℃/h, crystallization 10 ~ 20h again; Said drying temperature is 80 ~ 90 ℃.Through the control cooling rate, make in the fructose crystallization process 5-HMF not can with the fructose cocrystallization, further reduced the content of 5-HMF in the fructose crystals.
As a kind of improvement of technical scheme of the present invention, in the step (1), also comprise the activated carbon decolorizing step, promptly in the fructose ethanolic soln, add gac, heat up the insulated and stirred decolouring; Filtered while hot.Described amount of activated is 0.1 ‰ ~ 2.0 ‰ of a fructose bullion weight, most preferably is 1 ‰ ~ 2.0 ‰; The back temperature that heats up is 70 ~ 80 ℃; Bleaching time is 5 ~ 20min.Handle the fructose crude product solution through charcoal absorption, make that foreign matter content further reduces in the fructose, further improved the purity of fructose.
Beneficial effect: fructose process for purification technology provided by the invention is simple, easy to operate, and cost is low, and crystallization condition is simple, can effectively reduce the content of 5-HMF in the fructose, good product quality, and yield is high, is fit to suitability for industrialized production.
Fructose process for purification of the present invention can effectively reduce the content of 5-HMF in the mixing sugar electrolyte injection main raw material fructose.This method with fructose bullion heating for dissolving in ethanol at the 5-HMF melting temperature more than 30 ~ 34 ℃; And add a kind of solvent to the fructose solubilizing poorly; Induce the fructose crystallization; This solvent is better to the 5-HMF solvability simultaneously, so that 5-HMF does not separate out with fructose simultaneously, has reduced the content of 5-HMF in the fructose crystals.In addition, through the control rate of temperature fall, make in the fructose crystallization process 5-HMF not can with the fructose cocrystallization, further reduced the content of 5-HMF in the fructose crystals.
Embodiment
According to following embodiment, can understand the present invention better.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, processing condition and result thereof only are used to explain the present invention, and the present invention that should also can not limit in claims to be described in detail.
Refining (amount changes industrialized amount into) of embodiment 1 fructose bullion
Add 98% ethanol 100L in the 500L reaction kettle, fructose bullion 50kg (the 5-HMF absorbancy is 0.280) is heated with stirring to 65 ℃, the fructose dissolving crude product; Filter, filtrating 60min is cooled to 40 ℃, adds acetonitrile 20L; Reduce to 20 ℃ of stirring and crystallizing 4h with the rate of temperature fall of 5 ℃/h, reduce to-5 ℃ of stirring and crystallizing 10h with the rate of temperature fall of 8 ℃/h again, filter; Absolute ethanol washing, 80 ℃ of drying under reduced pressure get fructose highly finished product 44.05kg; Yield 88.1%, purity (normalization method): 99.98%, 5-HMF absorbancy: 0.091.
Making with extra care of embodiment 2 fructose bullions
Add 70% ethanol 250L in the 500L reaction kettle, fructose bullion 50kg (the 5-HMF absorbancy is 0.280) is heated with stirring to 70 ℃, the fructose dissolving crude product; Filter, filtrating 50min is cooled to 50 ℃, adds Virahol 75L; Reduce to 30 ℃ of stirring and crystallizing 2h with the rate of temperature fall of 15 ℃/h, reduce to 5 ℃ of stirring and crystallizing 20h with the rate of temperature fall of 15 ℃/h again, filter; Absolute ethanol washing, 90 ℃ of drying under reduced pressure get fructose highly finished product 44.50kg; Yield 89.0%, purity (normalization method): 99.98%, 5-HMF absorbancy: 0.090.
Making with extra care of embodiment 3 fructose bullions
Add 80% ethanol 200L in the 500L reaction kettle, fructose bullion 50kg (the 5-HMF absorbancy is 0.280) is heated with stirring to 65 ℃, the fructose dissolving crude product; Filter, filtrating 30min is cooled to 45 ℃, adds THF 50mL; Reduce to 20 ℃ of stirring and crystallizing 2h with the rate of temperature fall of 15 ℃/h, reduce to-5 ℃ of stirring and crystallizing 10h with the rate of temperature fall of 10 ℃/h again, filter; Absolute ethanol washing, 80 ℃ of drying under reduced pressure get fructose highly finished product 43.95kg; Yield 87.9%, purity (normalization method): 99.98%, 5-HMF absorbancy: 0.092.
Embodiment 4: fructose bullion refining
Add 95% ethanol 200L in the 500L reaction kettle, fructose bullion 50kg (the 5-HMF absorbancy is 0.280) is heated with stirring to 60 ℃, the fructose dissolving crude product; The gac that adds fructose bullion quality 1.0 ‰ (w/v) stirs and is warming up to 80 ℃, and insulated and stirred 10min filters; Filtrating 40min is cooled to 55 ℃, adds absolute ethyl alcohol 50L, reduces to 25 ℃ of stirring and crystallizing 3h with the rate of temperature fall of 10 ℃/h, reduces to 0 ℃ of stirring and crystallizing 12h with the rate of temperature fall of 12 ℃/h again; Filter, absolute ethanol washing, 85 ℃ of drying under reduced pressure get fructose highly finished product 43.5kg; Yield 87%, purity (normalization method): 99.98%, 5-HMF absorbancy: 0.089.
Making with extra care of embodiment 5 fructose bullions
Add 95% ethanol 100L in the 200L reaction kettle, fructose bullion 25kg (absorbancy is 0.280) is heated with stirring to 60 ℃, the fructose dissolving crude product; The gac that adds fructose bullion quality 1.0 ‰ (w/v) stirs and is warming up to 80 ℃, and insulated and stirred 10min filters; Filtrating 40min is cooled to 60 ℃, adds acetone 25L, reduces to 25 ℃ of stirring and crystallizing 3h with the rate of temperature fall of 10 ℃/h, reduces to 0 ℃ of stirring and crystallizing 12h with the rate of temperature fall of 12 ℃/h again; Filter, absolute ethanol washing, 85 ℃ of drying under reduced pressure get fructose highly finished product 21.56k g; Yield 86.24%, purity (normalization method): 99.99%, 5-HMF absorbancy: 0.085.
Making with extra care of embodiment 6 fructose bullions
Add 95% ethanol 150L in the 300L reaction kettle, fructose bullion 50kg (absorbancy is 0.280) is heated with stirring to 60 ℃, the fructose dissolving crude product; The gac that adds fructose bullion quality 1.0 ‰ (w/v) stirs and is warming up to 80 ℃, and insulated and stirred 10min filters; Filtrating 40min is cooled to 55 ℃, adds absolute ethyl alcohol 50L, reduces to 25 ℃ of stirring and crystallizing 3h with the rate of temperature fall of 10 ℃/h, reduces to 0 ℃ of stirring and crystallizing 12h with the rate of temperature fall of 12 ℃/h again; Filter, absolute ethanol washing, 85 ℃ of drying under reduced pressure get fructose highly finished product 43.21kg; Yield 86.42%, purity (normalization method): 99.99%, 5-HMF absorbancy: 0.083.
Making with extra care of embodiment 7 fructose bullions
Add 95% ethanol 60L in the 100L reaction kettle, fructose bullion 20kg (absorbancy is 0.280) is heated with stirring to 60 ℃, the fructose dissolving crude product; The gac that adds fructose bullion quality 1.0 ‰ (w/v) stirs and is warming up to 80 ℃, and insulated and stirred 10min filters; Filtrating 40min is cooled to 55 ℃, adds acetone 20L, reduces to 25 ℃ of stirring and crystallizing 3h with the rate of temperature fall of 10 ℃/h, reduces to 0 ℃ of stirring and crystallizing 12h with the rate of temperature fall of 12 ℃/h again; Filter, absolute ethanol washing, 85 ℃ of drying under reduced pressure get fructose highly finished product 17.6kg; Yield 88.02%, purity (normalization method): 99.99%, 5-HMF absorbancy: 0.088.
Making with extra care of embodiment 8 fructose bullions
The process for purification of present embodiment and parameter and embodiment 4 are basic identical, and difference only is: in the fructose crude product solution, add the gac of fructose bullion quality 0.5 ‰ (w/v), stir and be warming up to 70 ℃, insulated and stirred 15min.
Get fructose highly finished product 43.65kg, yield 87.3%, purity (normalization method): 99.98%, 5-HMF absorbancy: 0.084.
Making with extra care of embodiment 9 fructose bullions
Add 95% ethanol 200L in the 500L reaction kettle, fructose bullion 50kg (the 5-HMF absorbancy is 0.280) is heated with stirring to 60 ℃, the fructose dissolving crude product; The gac that adds fructose bullion quality 1.0 ‰ (w/v) stirs and is warming up to 80 ℃, and insulated and stirred 10min filters; Filtrating is cooled to 55 ℃, adds absolute ethyl alcohol 50L, is cooled to 0 ℃ of stirring and crystallizing 12h, filters; Absolute ethanol washing, 85 ℃ of drying under reduced pressure get fructose highly finished product 38.5kg; Yield 77%, purity (normalization method): 98.32%, 5-HMF absorbancy: 0.160.
Making with extra care of embodiment 10 fructose bullions
Add 95% ethanol 200L in the 500L reaction kettle, fructose bullion 50kg (the 5-HMF absorbancy is 0.280) is heated with stirring to 60 ℃, the fructose dissolving crude product; Filter, filtrating is cooled to 55 ℃, adds absolute ethyl alcohol 50L, is cooled to 0 ℃ of stirring and crystallizing 12h; Filter, absolute ethanol washing, 85 ℃ of drying under reduced pressure get fructose highly finished product 39.4kg; Yield 78.8%, purity (normalization method): 97.61%, 5-HMF absorbancy: 0.177.
Claims (10)
1. the process for purification of a mixing sugar electrolyte injection main raw material fructose is characterized in that: may further comprise the steps:
(1) the fructose bullion is dissolved in the aqueous ethanolic solution of heat, obtains the fructose ethanolic soln;
(2) cooling adds organic solvent, and said organic solvent is selected from one or more the mixture in acetonitrile, THF, acetone, absolute ethyl alcohol and the Virahol;
(3) the cooling crystallization filters, and gained crystal drying under reduced pressure promptly gets.
2. the process for purification of a kind of mixing sugar electrolyte injection main raw material fructose according to claim 1 is characterized in that: in the step (1), the amount ratio of said fructose bullion and aqueous ethanolic solution is 1kg: (2 ~ 5) L; Solution temperature is 60 ~ 70 ℃.
3. according to the process for purification of the said a kind of mixing sugar electrolyte injection main raw material fructose of claim 2, it is characterized in that: in the step (2), the amount ratio of said fructose bullion and aqueous ethanolic solution is 1kg: (3 ~ 4) L; Solution temperature is 60 ~ 65 ℃.
4. the process for purification of a kind of mixing sugar electrolyte injection main raw material fructose according to claim 1 is characterized in that: in the step (1), said aqueous ethanolic solution concentration expressed in percentage by volume is more than 70%.
5. the process for purification of a kind of mixing sugar electrolyte injection main raw material fructose according to claim 1 is characterized in that: in the step (2), the amount ratio of said organic solvent and fructose bullion is (0.5 ~ 1.5) L:1kg; Cooling back temperature is 40 ~ 55 ℃, and temperature fall time is 30 ~ 60min.
6. the process for purification of a kind of mixing sugar electrolyte injection main raw material fructose according to claim 1 is characterized in that: in the step (3), said cooling crystallization step is: reduce to 20 ~ 30 ℃ with the rate of temperature fall of 5 ~ 15 ℃/h, crystallization 2 ~ 4h; Reduce to-5 ~ 5 ℃ with the rate of temperature fall of 8 ~ 15 ℃/h again, crystallization 10 ~ 20h.
7. the process for purification of a kind of mixing sugar electrolyte injection main raw material fructose according to claim 1 is characterized in that: in the step (3), said drying temperature is 80 ~ 90 ℃.
8. the process for purification of a kind of mixing sugar electrolyte injection main raw material fructose according to claim 1 is characterized in that: in the step (1), also comprise the activated carbon decolorizing step, promptly in the fructose ethanolic soln, add gac, heat up, the insulated and stirred decolouring; Filtered while hot.
9. the process for purification of a kind of mixing sugar electrolyte injection main raw material fructose according to claim 8 is characterized in that: described quality of activated carbon is 0.1 ‰ ~ 2.0 ‰ of a fructose bullion quality; The back temperature that heats up is 70 ~ 80 ℃; Bleaching time is 5 ~ 20min.
10. the process for purification of a kind of mixing sugar electrolyte injection main raw material fructose according to claim 9 is characterized in that: described quality of activated carbon is 1 ‰ ~ 2.0 ‰ of a fructose bullion quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210236477 CN102732648B (en) | 2012-07-09 | 2012-07-09 | Method for refining fructose as main raw material of carbohydrate and electrolyte injection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210236477 CN102732648B (en) | 2012-07-09 | 2012-07-09 | Method for refining fructose as main raw material of carbohydrate and electrolyte injection |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102732648A true CN102732648A (en) | 2012-10-17 |
| CN102732648B CN102732648B (en) | 2013-07-24 |
Family
ID=46988943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210236477 Active CN102732648B (en) | 2012-07-09 | 2012-07-09 | Method for refining fructose as main raw material of carbohydrate and electrolyte injection |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102732648B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104382847A (en) * | 2014-11-06 | 2015-03-04 | 海南通用康力制药有限公司 | Preparation method of injection fructose |
| CN108085426A (en) * | 2017-12-26 | 2018-05-29 | 赵琪 | A kind of method that fructose is extracted in the crystalline mother solution from sodium gluconate |
| CN108998580A (en) * | 2018-09-10 | 2018-12-14 | 海南通用康力制药有限公司 | A kind of refining methd of fructose |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU407947A1 (en) * | 1972-05-31 | 1973-12-10 | Г. П. Федорченко , Н. В. Плеханова Шосткинский завод химических реактивов | METHOD FOR OBTAINING CRYSTALLINE pD-FRUCTOSES |
| EP0155803B1 (en) * | 1984-03-09 | 1988-08-03 | A.E. Staley Manufacturing Company | Crystalline fructose preparation |
| EP0293680A2 (en) * | 1987-06-03 | 1988-12-07 | Xyrofin Oy | A method for the crystallization of fructose |
| CN101638695A (en) * | 2009-08-24 | 2010-02-03 | 安徽丰原发酵技术工程研究有限公司 | Preparation method of crystalline fructose |
| CN101705312A (en) * | 2009-10-28 | 2010-05-12 | 陶灵刚 | New route fructose compound |
-
2012
- 2012-07-09 CN CN 201210236477 patent/CN102732648B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU407947A1 (en) * | 1972-05-31 | 1973-12-10 | Г. П. Федорченко , Н. В. Плеханова Шосткинский завод химических реактивов | METHOD FOR OBTAINING CRYSTALLINE pD-FRUCTOSES |
| EP0155803B1 (en) * | 1984-03-09 | 1988-08-03 | A.E. Staley Manufacturing Company | Crystalline fructose preparation |
| EP0293680A2 (en) * | 1987-06-03 | 1988-12-07 | Xyrofin Oy | A method for the crystallization of fructose |
| CN101638695A (en) * | 2009-08-24 | 2010-02-03 | 安徽丰原发酵技术工程研究有限公司 | Preparation method of crystalline fructose |
| CN101705312A (en) * | 2009-10-28 | 2010-05-12 | 陶灵刚 | New route fructose compound |
Non-Patent Citations (1)
| Title |
|---|
| 杨瑞金，潘允鸿，闻方: "蔗糖转化生产纯结晶果糖的工艺研究", 《食品与发酵工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104382847A (en) * | 2014-11-06 | 2015-03-04 | 海南通用康力制药有限公司 | Preparation method of injection fructose |
| CN108085426A (en) * | 2017-12-26 | 2018-05-29 | 赵琪 | A kind of method that fructose is extracted in the crystalline mother solution from sodium gluconate |
| CN108998580A (en) * | 2018-09-10 | 2018-12-14 | 海南通用康力制药有限公司 | A kind of refining methd of fructose |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102732648B (en) | 2013-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102732648B (en) | Method for refining fructose as main raw material of carbohydrate and electrolyte injection | |
| CN102367254B (en) | More stable doxofylline compound and pharmaceutical composite thereof | |
| CN104326984A (en) | Synthesis method of high-purity pharmaceutical injection-grade edaravone raw material | |
| CN102816085B (en) | Preparation method of iohexol impurity | |
| CN108084242A (en) | A kind of method for extracting moulting hormone | |
| CN101139280B (en) | Preparation method of sodium acetate anhydrous | |
| CN110721206A (en) | Deep eutectic solvent for extracting phellinus igniarius flavone and preparation method and extraction method thereof | |
| WO2021212535A1 (en) | Method for refining benzhexol hydrochloride | |
| CN102250110A (en) | Magnesium cantharidate and preparation method thereof | |
| CN102295648A (en) | Calcium cantharidinate and preparation method thereof | |
| CN101380329A (en) | Preparation method of arginine aspirin and powder and injection preparation thereof | |
| CN1374310A (en) | Prepn process of sodium cantharidinate | |
| CN110078667A (en) | A method of extracting huperzine | |
| CN101781215A (en) | Method for preparing propyl gallate bulk drug by chemical semi-synthesis | |
| CN105641001B (en) | Ganoderma lucidum amino acid extract and preparation method and application thereof | |
| CN108546278A (en) | The process for purification of Mecobalamin | |
| CN101633661B (en) | Process for preparing sodium cantharidinate | |
| CN100519514C (en) | Method of preparing D-p-hydroxyphenylglycine | |
| CN102372749A (en) | Method for preparing D-glucosamine hydrochloride by utilizing sleeve-fish sheathes | |
| CN103012069B (en) | Production process of medicinal phloroglucinol | |
| CN102085226A (en) | Japanese picris japonica extract and extracting method thereof | |
| CN101683320A (en) | Olprinone hydrochloric parenteral solution and method for preparing same | |
| CN102304027A (en) | Method for extracting magnolol from Magnolia officinalis tree leaves | |
| CN105968150A (en) | Preparation method for 7-O-ethylmorroniside | |
| CN103772256A (en) | Preparation method for high-purity sulpiride or optical isomers thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |