CN109956983A - The extracting method of trichloro-cane-6-ethyl ester - Google Patents
The extracting method of trichloro-cane-6-ethyl ester Download PDFInfo
- Publication number
- CN109956983A CN109956983A CN201711417933.0A CN201711417933A CN109956983A CN 109956983 A CN109956983 A CN 109956983A CN 201711417933 A CN201711417933 A CN 201711417933A CN 109956983 A CN109956983 A CN 109956983A
- Authority
- CN
- China
- Prior art keywords
- ethyl ester
- cane
- trichloro
- extracting method
- solvent
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
- C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
- C07H13/04—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
- C07H13/06—Fatty acids
Abstract
The extracting method of present invention offer trichloro-cane-6-ethyl ester, it include that " monoesters method " is prepared in the production process of Sucralose, after the chlorination workshop section for preparing trichloro-cane-6-ethyl ester by sucrose-6-ethyl ester chlorination, acid material obtained is neutralized with alkali, then nonpolarity or low polar solvent is added, it is stood after stirring, so that trichloro-cane-6-ethyl ester is formed solid and settles, then it is separated by solid-liquid separation, obtain trichloro-cane-6-ethyl ester solid crude product, optionally, it is recycled after being separated to liquid portion rectifying, and trichloro-cane-6-ethyl ester solid crude product is recrystallized.
Description
Technical field
The present invention relates to sweetener production fields, more particularly to the key in sweetening agent Sucralose preparation process
The extracting method of intermediate trichloro-cane-6-ethyl ester.
Background technique
Sucralose is current performance one of high sugariness sweetening agent the most excellent in the world, big with sugariness,
The features such as sweet taste characteristic is good and is not absorbed by the body.Solubility is larger in water for Sucralose, and does not generate bubble when dissolution, because
This is widely used in soda.Sucralose is the chemically treated natural semi-synthetic sweet tea using sucrose as primary raw material
Taste agent.
Current most of manufacturing enterprises all take " monoesters method " to produce Sucralose, it may be assumed that are esterified, obtain to sucrose first
Sucrose-6-ethyl ester, then chlorination generate trichloro-cane-6-ethyl ester, purify the trichloro-cane-6-ethyl ester of generation, then water again
Deacetylation is solved, Sucralose is generated.
During monoesters method prepares Sucralose, the preparation and extraction of intermediate trichloro-cane-6-ethyl ester are very
Crucial step.In chlorinating step, domestic enterprise is mostly to select thionyl chloride as chlorinating agent, trichloroethanes and N, N- bis-
Methylformamide (DMF) is used as solvent, prepares trichloro-cane-6-ethyl ester by sucrose-6-ethyl ester.It, will after chlorination reaction
Reaction mass is neutralized with alkaline matter, then distills material, to remove solvent trichloroethanes and DMF, remaining material
A certain amount of water is added, trichloro-cane-6-ethyl ester aqueous solution is made, then crystallized, filters, to extract Sucralose -6-
Ethyl ester solid.
CN1271077C discloses a kind of preparation method of trichloro-cane-6-ethyl ester, includes the following steps: sucrose -6-
Ethyl ester is added in the solvent containing DMF, uses thionyl chloride as chlorinating agent, and point three temperature stage chlorinations obtain Sucralose-
Reaction mixture is cooled to room temperature by 6- ethyl ester, adjusts pH to neutrality with lye, Sucralose -6- is then extracted with ethyl acetate
Ethyl ester, the organic phase obtained to extraction carry out that ethyl acetate is distilled off, and obtain the concentrate solution of trichloro-cane-6-ethyl ester, to
A small amount of ether solvent or water are added in the solution, obtains trichloro-cane-6-ethyl ester crystal.
In the method for the above-mentioned prior art, there is a very big difficult point to annoying each manufacturer, is exactly to trichlorine sugarcane
During the solution of sugar -6- ethyl ester carries out removing solvent, since the boiling point of solvent is relatively high, such as trichloroethanes boiling point 114
DEG C, 153 DEG C of DMF boiling point, 77 DEG C of ethyl acetate boiling point, and the quantity of solvent for needing to remove is big, usually requires heating distillation very
For a long time, such as 10 hours or more；And trichloro-cane-6-ethyl ester more than 70 DEG C at a temperature of be heated for a long time, be easy coking
Or it decomposes, therefore the process for removing solvent must use high vacuum low temperature distillation, cause technological operation at high cost.Nonetheless,
It also will cause 10% or more trichloro-cane-6-ethyl ester decomposition and DMF points of 20% or more during distillation removes solvent
Solution.
Summary of the invention
The present invention provides a kind of extracting method of trichloro-cane-6-ethyl ester, including in the production process of Sucralose,
After the chlorination workshop section for preparing trichloro-cane-6-ethyl ester by sucrose-6-ethyl ester chlorination, acid material obtained carried out with alkali
With nonpolarity or low polar solvent is then added, is stood after stirring, forms trichloro-cane-6-ethyl ester and solid and settles, then
It is separated by solid-liquid separation, obtains trichloro-cane-6-ethyl ester solid crude product, optionally, recycled after carrying out rectifying separation to liquid portion
It utilizes.
The extracting method of trichloro-cane-6-ethyl ester of the invention avoids the long-time heating after neutralization procedure and removes solvent
Caused by trichloro-cane-6-ethyl ester decomposition, reduce the decomposition of DMF, while the recycling of liquid portion reduces production
Cost.
Optionally, above method trichloro-cane-6-ethyl ester solid crude product obtained is recrystallized with water, obtains three
Chlorine sucrose-6-ethyl ester crystal.
Specific embodiment
Unless otherwise defined, all technical and scientific terms used herein have fields ordinary skill of the present invention
The identical meanings that personnel are generally understood.In the case where inconsistent, the definition in this specification shall prevail.
Unless otherwise stated, all percentage, number, ratio etc. be all by weight.
The extracting method of trichloro-cane-6-ethyl ester of the invention produces Sucralose using " monoesters method " suitable for all
No matter process which kind of chlorinating agent and solvent is used in the chlorinating step of sucrose-6-ethyl ester.
The present invention provides a kind of extracting method of trichloro-cane-6-ethyl ester, and this method is the production process in Sucralose
In, after preparing trichloro-cane-6-ethyl ester by sucrose-6-ethyl ester chlorination, trichloro-cane-6-ethyl ester reaction mixture is carried out with alkali
It neutralizes, the material after neutralization removes solvent without distillation, but nonpolarity or low polar solvent is added, and stands, makes after stirring
Trichloro-cane-6-ethyl ester forms solid and settles, and is then separated by solid-liquid separation, and trichloro-cane-6-ethyl ester solid crude product is obtained, and appoints
Selection of land, liquid portion recycle after being separated by rectifying.
In this application, described " nonpolarity or low polar solvent " is polar all lower than pentamethylene selected from solvent polarity
Solvent, more preferable polarity are the solvent of 0-0.2, particularly preferred petroleum ether, hexamethylene and white oil etc..
In a preferred embodiment of the present invention, wherein into the trichloro-cane-6-ethyl ester reaction mass after neutralization
Be added it is described nonpolarity or low polar solvent be 10-40 DEG C temperature carry out, preferably 15-35 DEG C, more preferably at room temperature into
Row.
In a preferred embodiment of the present invention, wherein based on the trichloro-cane-6-ethyl ester reaction mass after neutralization
Total weight, be added thereto it is described nonpolarity or low polar solvent weight be 30-150%, preferably 40-90%.
In this application, " separation of solid and liquid " includes any of mode for separating solid with liquid, such as
Filtering, pouring liquid, centrifuge separation etc..
It in a preferred embodiment of the present invention, further include to above method trichloro-cane-6-ethyl ester obtained
Water is added in solid crude product, is made into the aqueous solution of trichloro-cane-6-ethyl ester, concentration is 5-20 weight %, preferably 8-12 weight %,
It is warming up to 100 degree, sampling analysis trichloro-cane-6-ethyl ester aqueous solution, until being wherein free of trichloroethanes and other organic solvents,
Then 3-10 DEG C, preferably 5-8 DEG C are cooled to, stirs 3-15 hours, preferably 8-12 hours, recrystallizes trichloro-cane-6-ethyl ester
It is precipitated.Trichloro-cane-6-ethyl ester crystal is obtained by filtration.
Acid chlorization liquid material from chlorination workshop section is sent into and is neutralized by a preferred embodiment according to the present invention
In reactor, alkaline material (preferably ammonium hydroxide) is added and carries out neutralization reaction, makes material pH value 7-9, preferably 7-8, more preferable 7.
Reaction mass after the neutralization is transferred in sedimentation kettle, is added selected from the one or more non-of petroleum ether, hexamethylene, white oil etc.
Polar solvent is uniformly mixed, and settles time enough, the in the mixed solvent Sucralose -6- second until detecting liquid phase
When ester content is lower than 0.2%, it is separated by solid-liquid separation, liquid is sent to distillation system and separately recycles various solvents, will be consolidated
Body material is soluble in water, is recrystallized, and further purifies, obtains trichloro-cane-6-ethyl ester solid.
The direct distillation that the present invention saves in the prior art during extracting trichloro-cane-6-ethyl ester removes solvent
Step is instead added nonpolarity or low polar solvent, makes the sucrose derivatives such as trichloro-cane-6-ethyl ester in mild temperature strip
Solidify and settle under part, then be separated by solid-liquid separation, obtains trichloro-cane-6-ethyl ester solid, then recrystallized, obtain fine work.It keeps away
Exempt to cause product decomposition and solvolysis in a large amount of dissolving agent process of distillation removing, has significantly improved trichloro-cane-6-ethyl ester
Yield, such as yield improve 5% or more, and reduce the loss of solvent such as DMF, such as the loss of DMF reduces 20%
More than, greatly reduce production consumption and production cost.
Embodiment
Embodiment 1
It will be in the acid trichloro-cane-6-ethyl ester product mixture feeding of the chlorination workshop section from Sucralose preparation process
In reactor, ammonium hydroxide is added and carries out neutralization reaction, makes material pH value 7.1000 grams of solution after taking the chlorination to neutralize is (wherein
Containing 4 weight % of trichloro-cane-6-ethyl ester, trichloroethanes 80 weight %, DMF 5 weight %, 11 weight % of impurity), it is added to
In 2000 milliliters of band stirrings and electrically heated three-necked flask, 400 grams of hexamethylenes, i.e. hexamethylene and trichloroethanes are added at normal temperature
Weight ratio be 0.5:1, be sufficiently stirred 15 minutes, stand 30 minutes, there is trichloro-cane-6-ethyl ester solid to be deposited to flask bottom
Portion takes the 1 milliliter of progress chromatography of upper phase mixed solvent, measures the content of the in the mixed solvent trichloro-cane-6-ethyl ester
It is 0.18%, supernatant liquid is poured out 1200 grams into another 2000 milliliters of beakers at this time, what is left in three-necked flask is three
Chlorine sucrose-6-ethyl ester solid crude product and totally 200 grams of remaining mixed solvent.
350 grams of water are added into trichloro-cane-6-ethyl ester solid crude product mixture obtained, are then heated to 80 DEG C,
It is evacuated to 0.05 megapascal to be kept for 0.5 hour, it is total to steam part water and remaining a small amount of trichloroethanes, hexamethylene, DMF etc.
150 grams, the trichloro-cane-6-ethyl ester aqueous solution of remaining 400 grams of concentrations, sampling inspection results: the aqueous solution -6- containing Sucralose
Ethyl ester 9.46%, i.e. total amount containing trichloro-cane-6-ethyl ester are 37.84 grams, relative to trichlorine contained in 1000 grams of material solutions
Sucrose-6-ethyl ester, trichloro-cane-6-ethyl ester yield are 94.6%.
The trichloro-cane-6-ethyl ester aqueous solution of concentration obtained is cooled to 5-8 DEG C, stirs 8 hours, is recrystallized
Trichloro-cane-6-ethyl ester, dried after filtering, obtain 33.8 grams of fine work, yield 84.5%.
To the 1200 grams of mixed solvent sampling analyses poured out, contain trichloroethanes 64%, hexamethylene 32%, DMF 4%, warp
Rectifying column separation, obtains 768 grams of trichloroethanes, and 384 grams of hexamethylene, 48 grams of DMF, DMF recovery rate 96%.
Comparative example 1
1000 grams of solution (the wherein 4 weight % containing trichloro-cane-6-ethyl ester, trichlorine after taking sucrose-6-ethyl ester chlorination to neutralize
Ethane 80 weight %, DMF 5 weight %, 11 weight % of impurity), it is put into 2000 milliliters of there-necked flasks with stirring and electric heater
In, it is heated to 80 DEG C under stirring, opens vacuum to 0.09 megapascal, holding 10 hours steams 810 grams of trichloroethanes and DMF mixed liquor,
Wherein DMF 1.25%, trichloroethanes 98.75%, into remaining 190 grams of concentrates plus 200 grams of water are distilled again, in Gao Zhen
Empty 0.09 megapascal at a temperature of 80 DEG C, steams 200 grams of mixing liquids, wherein DMF content 11%, water 89%, remaining raffinate adds again
It 400 grams of water, detects in 590 grams of liquid, contains trichloro-cane-6-ethyl ester 5.93%, i.e. 35 grams of trichloro-cane-6-ethyl ester total amount,
Yield 87.5% has 12.5% trichloro-cane-6-ethyl ester to decompose in evaporation process.
Above-mentioned 590 grams of liquid is transferred in 1000 milliliters of there-necked flasks, cools to 0-5 degree under stiring, stirs 20 hours, obtains
Trichloro-cane-6-ethyl ester crystal obtains 31 grams of trichloro-cane-6-ethyl ester fine work, yield 77.5%, than the present invention through filtering drying
New method low 7%.
In the 810 grams of trichloroethanes and DMF mixed liquor steamed for the first time, contain DMF1.25%, extract rectifying again through water,
DMF9.5 grams of recycling.In second of 200 grams of mixed liquor for adding water to steam, 22 grams of DMF total amount, 31.5 grams of DMF are recycled altogether,
Contain 50 grams of DMF in former 1000 milliliters of chlorination neutralizers, actual recovery 63% there are 18.5 grams of DMF to decompose in distillation twice.
Claims (9)
1. the extracting method of trichloro-cane-6-ethyl ester, including in the production process of Sucralose, by sucrose-6-ethyl ester chlorine
After change prepares the chlorination workshop section of trichloro-cane-6-ethyl ester, acid material obtained is neutralized with alkali, non-pole is then added
Property or low polar solvent, stood after stirring, form trichloro-cane-6-ethyl ester and solid and settle, be then separated by solid-liquid separation, obtained
Trichloro-cane-6-ethyl ester solid crude product is obtained, optionally, is recycled after being separated to liquid portion rectifying.
2. the extracting method of trichloro-cane-6-ethyl ester according to claim 1, wherein the nonpolar or low polarity is molten
Agent is selected from the polar organic solvent that solvent polarity is lower than pentamethylene, and more preferable polarity is the solvent of 0-0.2, particularly preferred petroleum
Ether, hexamethylene and white oil.
3. the extracting method of trichloro-cane-6-ethyl ester according to claim 1 or 2, wherein the nonpolarity or low polarity
Solvent is the temperature at 10-40 DEG C, preferably 15-35 DEG C, is more preferably added in room temperature.
4. the extracting method of trichloro-cane-6-ethyl ester according to claim 1 or 2, wherein based on the trichlorine sugarcane after neutralization
The total weight of sugar -6- ethyl ester product solution, the weight of the nonpolarity or low polar solvent that are added thereto are 30-150%,
It is preferred that 40-90%.
5. the extracting method of trichloro-cane-6-ethyl ester according to claim 1 or 2 further includes to trichlorine obtained
Water is added in sucrose-6-ethyl ester solid crude product, is made into the aqueous solution of trichloro-cane-6-ethyl ester, then cools down and stir, so that three
Chlorine sucrose-6-ethyl ester recrystallization is precipitated, and trichloro-cane-6-ethyl ester crystal is obtained by filtration.
6. the extracting method of trichloro-cane-6-ethyl ester according to claim 5, wherein the trichloro-cane-6-ethyl ester being made into
The concentration of aqueous solution is 5-20 weight %, preferably 8-12 weight %.
7. the extracting method of trichloro-cane-6-ethyl ester according to claim 5, wherein the recrystallization is at 3-10 DEG C, it is excellent
Select and stir 3-15 hours at 5-8 DEG C, preferably 8-12 hours and carry out.
8. the extracting method of trichloro-cane-6-ethyl ester according to claim 1 or 2, wherein by the acid from chlorination workshop section
Property chlorizate solution be sent into neutralization reactor in, be added alkaline material carry out neutralization reaction, make material pH value 7-9, preferably
7-8, more preferable 7.
9. the extracting method of trichloro-cane-6-ethyl ester according to claim 8, wherein the alkaline material is selected from ammonia
Water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711417933.0A CN109956983B (en) | 2017-12-25 | 2017-12-25 | Method for extracting sucralose-6-ethyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711417933.0A CN109956983B (en) | 2017-12-25 | 2017-12-25 | Method for extracting sucralose-6-ethyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109956983A true CN109956983A (en) | 2019-07-02 |
| CN109956983B CN109956983B (en) | 2022-11-01 |
Family
ID=67020474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711417933.0A Active CN109956983B (en) | 2017-12-25 | 2017-12-25 | Method for extracting sucralose-6-ethyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109956983B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563777A (en) * | 2019-08-30 | 2019-12-13 | 山东新和成精化科技有限公司 | method for post-treating sucralose chlorination liquid |
| CN112125938A (en) * | 2020-09-26 | 2020-12-25 | 安徽金禾实业股份有限公司 | Method for extracting sucralose-6-ethyl ester from sugar residues |
| CN112457356A (en) * | 2020-11-30 | 2021-03-09 | 安徽金禾实业股份有限公司 | Method for removing ethyl ester from secondary esterified crude product in sucralose production |
| CN112638924A (en) * | 2020-11-27 | 2021-04-09 | 安徽金禾实业股份有限公司 | Purification method of sucralose-6-ethyl ester |
| CN113767109A (en) * | 2021-08-04 | 2021-12-07 | 安徽金禾实业股份有限公司 | Preparation method of sucralose |
| WO2022056840A1 (en) * | 2020-09-18 | 2022-03-24 | 安徽金禾实业股份有限公司 | Post-treatment method of sucrose-6-carboxylic ester chlorination reaction liquid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619083A (en) * | 2009-06-19 | 2010-01-06 | 盐城捷康三氯蔗糖制造有限公司 | Chlorination method for industrial production of sucralose-6-acetic ester |
| WO2010013157A2 (en) * | 2008-07-29 | 2010-02-04 | Alembic Limited | Cost efficient process for preparation of sucralose |
| CN102164938A (en) * | 2008-07-23 | 2011-08-24 | 玛特科国际有限公司 | Methods for extracting and purifying sucralose intermediate |
| CN102391320A (en) * | 2011-12-23 | 2012-03-28 | 盐城捷康三氯蔗糖制造有限公司 | Method for purifying sucralose by solvent thermal refluxing |
| CN105111246A (en) * | 2015-08-22 | 2015-12-02 | 安徽金禾实业股份有限公司 | Method for recycling organic tin in sucralose production |
| CN106957345A (en) * | 2017-04-10 | 2017-07-18 | 王满堂 | Improve the production method of the ethyl ester yield of Sucralose 6 |
-
2017
- 2017-12-25 CN CN201711417933.0A patent/CN109956983B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102164938A (en) * | 2008-07-23 | 2011-08-24 | 玛特科国际有限公司 | Methods for extracting and purifying sucralose intermediate |
| WO2010013157A2 (en) * | 2008-07-29 | 2010-02-04 | Alembic Limited | Cost efficient process for preparation of sucralose |
| CN101619083A (en) * | 2009-06-19 | 2010-01-06 | 盐城捷康三氯蔗糖制造有限公司 | Chlorination method for industrial production of sucralose-6-acetic ester |
| CN102391320A (en) * | 2011-12-23 | 2012-03-28 | 盐城捷康三氯蔗糖制造有限公司 | Method for purifying sucralose by solvent thermal refluxing |
| CN105111246A (en) * | 2015-08-22 | 2015-12-02 | 安徽金禾实业股份有限公司 | Method for recycling organic tin in sucralose production |
| CN106957345A (en) * | 2017-04-10 | 2017-07-18 | 王满堂 | Improve the production method of the ethyl ester yield of Sucralose 6 |
Non-Patent Citations (2)
| Title |
|---|
| 吴妤萱 等: "三氯蔗糖工业生产中氯代反应后处理的工艺改进", 《山西化工》 * |
| 游华彬 等: "三氯蔗糖-6-乙酯的制备工艺", 《武汉工程大学学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563777A (en) * | 2019-08-30 | 2019-12-13 | 山东新和成精化科技有限公司 | method for post-treating sucralose chlorination liquid |
| CN110563777B (en) * | 2019-08-30 | 2020-07-24 | 山东新和成精化科技有限公司 | Method for post-treating sucralose chlorination liquid |
| WO2022056840A1 (en) * | 2020-09-18 | 2022-03-24 | 安徽金禾实业股份有限公司 | Post-treatment method of sucrose-6-carboxylic ester chlorination reaction liquid |
| CN112125938A (en) * | 2020-09-26 | 2020-12-25 | 安徽金禾实业股份有限公司 | Method for extracting sucralose-6-ethyl ester from sugar residues |
| CN112638924A (en) * | 2020-11-27 | 2021-04-09 | 安徽金禾实业股份有限公司 | Purification method of sucralose-6-ethyl ester |
| WO2022110017A1 (en) * | 2020-11-27 | 2022-06-02 | 安徽金禾实业股份有限公司 | Method for purifying sucralose-6-ethyl ester |
| CN112457356A (en) * | 2020-11-30 | 2021-03-09 | 安徽金禾实业股份有限公司 | Method for removing ethyl ester from secondary esterified crude product in sucralose production |
| CN113767109A (en) * | 2021-08-04 | 2021-12-07 | 安徽金禾实业股份有限公司 | Preparation method of sucralose |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109956983B (en) | 2022-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109956983A (en) | The extracting method of trichloro-cane-6-ethyl ester | |
| KR101650694B1 (en) | Lactic acid extraction | |
| CN111171103B (en) | Method for extracting oryzanol by multiple solvents | |
| CN104649300B (en) | The method of recovery and refining sodium bromide from dipropyl cyanoacetate mixture | |
| CN106957345B (en) | Improve the production method of trichloro-cane-6-ethyl ester yield | |
| WO2005090376A1 (en) | An improved process for producing chlorinated sucrose | |
| JPH04228084A (en) | Recovery of citric acid | |
| CN111039777A (en) | Refining and purifying method of dodecyl dicarboxylic acid with high yield and low cost | |
| CN104693081B (en) | Method for refining bisphenol S by using mixed solvent | |
| CN112300071B (en) | Synthetic method of high-purity chloroquine phosphate | |
| CN109956982A (en) | A kind of preparation method of Sucralose | |
| CN107540715A (en) | DMF liquid-liquid extraction | |
| CN107522614A (en) | A kind of low-carbon halogenated alkane is used for the method for glutaric acid in Separation ＆ Purification mixed dibasic acid | |
| US2508545A (en) | Process of recovering caffein | |
| CN100595193C (en) | Industrial method for producing natural capsicine | |
| CN106883227B (en) | The method for preparing ergometrine by ergot fermentation waste | |
| CN113366006B (en) | Method for purifying sucralose-6-ethyl ester | |
| CN108191927A (en) | The removal methods of inorganic salts and organic impurities in a kind of Sucralose chloro liquid | |
| WO2016189200A1 (en) | Production of sterols | |
| CN106220520B (en) | A kind of processing method of beet alkali hydrochlorate calcium method production technology waste liquor | |
| CN220656435U (en) | Device for recycling pyridine or pyridine derivative in hexachlorocyclo-triphosphazene synthetic waste residues | |
| CN108892619A (en) | A kind of separation method of nitro neighbour acetophenone admixture of isomeric compound | |
| CN115572296B (en) | Method for reducing absorbance index of caffeine product | |
| CN106366038A (en) | Method of recycling dextromethorphan from crystallization mother liquid | |
| CN105198858B (en) | The purification process of Zaltoprofen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |