CN1107845A - Preparation method of calcium ascorbate - Google Patents
Preparation method of calcium ascorbate Download PDFInfo
- Publication number
- CN1107845A CN1107845A CN 94100392 CN94100392A CN1107845A CN 1107845 A CN1107845 A CN 1107845A CN 94100392 CN94100392 CN 94100392 CN 94100392 A CN94100392 A CN 94100392A CN 1107845 A CN1107845 A CN 1107845A
- Authority
- CN
- China
- Prior art keywords
- water
- calcium ascorbate
- reaction
- preparation
- crystallization
- 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
- BLORRZQTHNGFTI-ZZMNMWMASA-L calcium-L-ascorbate Chemical compound [Ca+2].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] BLORRZQTHNGFTI-ZZMNMWMASA-L 0.000 title claims abstract description 31
- 235000010376 calcium ascorbate Nutrition 0.000 title claims abstract description 30
- 229940047036 calcium ascorbate Drugs 0.000 title claims abstract description 30
- 239000011692 calcium ascorbate Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 230000008025 crystallization Effects 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 235000010323 ascorbic acid Nutrition 0.000 abstract 2
- 239000011668 ascorbic acid Substances 0.000 abstract 2
- 229960005070 ascorbic acid Drugs 0.000 abstract 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract 1
- 235000011941 Tilia x europaea Nutrition 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000004571 lime Substances 0.000 abstract 1
- 239000008267 milk Substances 0.000 abstract 1
- 210000004080 milk Anatomy 0.000 abstract 1
- 235000013336 milk Nutrition 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 6
- 235000013305 food Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 201000005569 Gout Diseases 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 206010039361 Sacroiliitis Diseases 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 208000007442 rickets Diseases 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
The process for preparing calcium ascorbate includes adding ascorbic acid into warm water, adding calcium carbonate to react, balancing, adding lime milk to make pH value of reaction liquid reach 4.5-7, vacuum filtering, vacuum concentrating mother liquid, crystallizing, adding edible alcohol until crystallization is complete, cooling, centrifugal separation, washing with alcohol to dewater and drying. The invention is fused with CaCO3Fahe Ca (OH)2The method has the advantages of integrating the advantages of purification and separation technologies such as reduced pressure concentration, natural crystallization, ethanol crystallization and the like, completely reacting the ascorbic acid, crystal seeds are crystal-clear and pure, the taste is comfortable, the yield reaches 94-98.5%, and the purity is more than or equal to 98.5%.
Description
The present invention relates to a kind of method with xitix and calcareous compound prepared in reaction calcium ascorbate.
Calcium ascorbate is a kind of compound with xitix and the dual physiological function of calcium, it both can be in order to have prevented and treated rickets, gout and the sacroiliitis that xitix for want of causes, also can be used as the antioxidant and the sanitas of food, stop in the food carcinogenic formation such as nitrosamine, prevent that food decay is rotten.
By xitix (V-C) preparation calcium ascorbate, traditional method is with V-C and calcium carbonate reaction, as RusRin at US2596103(date of publication 520513) and US2631155(date of publication 530310) method, and Scheur is at US4251449(date of publication 810217) method.The former is at room temperature, under a large amount of water medium existence conditions, gets the calcium ascorbate aqueous solution or adds a large amount of solvents (as acetone) crystallization with excessive V-C and calcium carbonate reaction, or evaporate pulpous state liquid, introduce seeded crystallization, tell crystal, washing, the dry calcium ascorbate that gets.The latter adopts excessive slightly CaCO
3, under 40-60 ℃, under less water medium existence condition, react, ascorbic acid calcium pulpous state liquid, nature or introduce seeded crystallization must contain the mixed crystallization product of calcium ascorbate 85 ± 2%.
Xin Mingqing is once to above-mentioned patent experiment (seeing " fermentation industry " 25281987), find that the former calcium ascorbate concentration of aqueous solution is too rare, need add a large amount of solvents again, and products therefrom only 70-80% adopt the latter, when then the mixture that reacts being chilled to-10 ℃, also still not having crystallization and separate out.
The people that waits of USSR (Union of Soviet Socialist Republics) adopts the rotary drum ball milled, uses solid phase Ca(OH)
2With the V-C reaction, preparation contains the calcium ascorbate of 2 crystal water.This method can only be used for the preparation of low amounts of product, as measures greatly, and not only quality can't guarantee, and needs to consume a large amount of unreacted V-C of ethanol flush away.
The objective of the invention is to remain deficiency separately, be intended to design a kind of productive rate height, good product purity, be suitable for the preparation method of the calcium ascorbate of suitability for industrialized production at aforesaid method.
The objective of the invention is to realize in the following manner, the preparation method of calcium ascorbate adds xitix in the entry and calcium carbonate reaction.35.2 part xitix add in 35~70 parts of water, under room temperature-75 ℃, added 10-11 part calcium carbonate reaction 30-240 minute.After reaction reaches balance, add an amount of milk of lime again, make the reaction solution pH value reach 4.5-7.0, stirred 1-30 minute, excessive materials and water-insoluble are removed in vacuum filtration, and mother liquor is evaporated to content and is lower than 50% under 70 ℃.Stir crystallisation by cooling, the edible ethanol that slowly adds 20-100 part.Continue stirring and crystallizing, reduce to room temperature naturally, the small amount of ethanol washing dehydration is used in centrifugation, gets product in 50-60 ℃ of following vacuum-drying or constant pressure and dry.
Theoretically, the reaction of V-C and lime carbonate is along with the effusion reaction of carbonic acid gas is irreversible, and therefore, V-C and excessive calcium carbonate reaction can be converted into calcium ascorbate quantitatively.But ignored in the water at this and can dissolve a certain amount of CO
2, cause reaction when reaching balance, still have the about 5-10% of V-C(of a great deal of) and fail to be converted into calcium ascorbate.The residual quantity of V-C is directly proportional with the consumption of water, because of the consumption of water is big more, and dissolved CO
2Many more.Because the residual productive rate of product that causes of V-C is low.The present invention after reaction reaches balance, add again q.s, concentration is the milk of lime of 1-10%, best 1-5%, the CO in the water had both neutralized
2, again with residual V-C reaction.And this reaction is at CO soluble in water
2Protection under carry out, avoided adding merely Ca(OH)
2During reaction, alkaline medium has improved productive rate to the decomposition and the destruction of unsettled V-C and calcium ascorbate.Reaction mechanism of the present invention is:
The present invention adopts concentrating under reduced pressure, and the purifies and separates technology that natural crystallization and ethanol crystallization combine adds ethanol, and its amount can make calcium ascorbate fully isolate from reaction medium for 0.5~5 times of the water yield
, can make product have advantage sparkling and crystal-clear, pure, comfortable taste again.Adopt this preparation method, the yield of calcium ascorbate can be up to 94-98.5%.
Reaction medium water had both played solvent in reaction, in the crystallization process, provide crystal water again.Make reaction solution when filtering and impurity removing, calcium ascorbate is not separated out with insoluble impurities, and the consumption of water is particularly important.Because of the water yield is too little, will bring difficulty to the filtering separation of impurity; The water yield is too big, though reaction is not had influence, calcium ascorbate is further separated from solution bring difficulty.Through experiment, the present invention select the consumption of water be xitix weight 1-2 doubly.
Temperature of reaction of the present invention is a room temperature to 75 ℃, and the add-on of best 30-55 ℃ milk of lime should make pH value reach 4.5-7.0, best 5.0-6.0.
Fig. 1, Fig. 2, Fig. 3 be respectively the product of preparing with the inventive method IR spectrum,
13The CNMR collection of illustrative plates and
1The HNMR collection of illustrative plates.
Fig. 1, Fig. 2, Fig. 3 are provided by Institute of Analysis of Wuhan University. Among Fig. 1 3344,3360,3427,3592cm-1Etc. a series of bands of a spectrum, be hydroxyl absworption peak in hydroxyl in the Calcium Ascorbate molecule and the crystallization water molecule. 1727cm-1The peak is the absworption peak of free carboxylic carbonyl, because the effect of calcium ion moves to herein its 1750cm by V-C. The stretching vibration peak 1670cm of C=0 and C=C among the same V-C-1、1650cm
-1Move to 1615cm herein-1、1577cm
-1, these are consistent with the structure of reporting, also equate with the Calcium Ascorbate structural information. The result of Fig. 2 is the Calcium Ascorbate reported13The CNMR collection of illustrative plates consistent. Fig. 3 demonstrates four hydrogen-like families, and demonstrates 5 hydroxyls, and further showing has the crystallization water to exist in the molecule. The ratio of multiple hydrogen atom is 2: 1: 1: the numbers of hydrogen atoms of 5,2 multiples is 18, conforms to the structural information of Calcium Ascorbate, also conforms to number of hydrogen atoms in the molecule.
The product of producing with the inventive method adopts the standard of american chemical pharmacopeia (Fcc) third edition to identify that quality is better than this standard through Hubei Province's epidemic prevention station, and concrete outcome is as follows:
Outward appearance: white is to light yellow crystalline powder
Physical property: odorless, soluble in water, be slightly soluble in ethanol, be insoluble to ether
10% aqueous ph value is 6.8-7.4
Optical activity: [2]25 D+95°~+97°
Quality standard:
Content 〉=98.5% arsenic<3ppm
Fluorochemical<10ppm heavy metal (pb)<10ppm
Oxalate test: feminine gender
CaCO has been merged in the present invention
3Method and Ca(OH)
2The advantage of method makes the entire reaction course can be at the CO that generates naturally
2Carry out under the gas shield, can make the V-C that adds in the reactor change into calcium ascorbate quantitatively again, overcome Ca(OH)
2The method alkaline medium is to the decomposition destruction of unsteady V-C and calcium ascorbate, and CaCO
3The method long reaction time, react incomplete deficiency.The present invention has also concentrated purifies and separates technology such as concentrating under reduced pressure, natural crystallization and ethanol crystallization, and calcium ascorbate is fully separated from reaction medium, can make product sparkling and crystal-clear, pure again, comfortable taste.Add to concentrate and reduced the water content in the slurries, alcohol consumption quantity is reduced, product yield is up to 94-98.5%, purity 〉=98.5%.
The specific embodiment of the invention sees the following form:
Comparing embodiment:
40 parts water is heated to 50~55 ℃, stirs down to add 35.2 parts of V-C, adds 10.5 parts of CaCO again
3, insulated and stirred 120 minutes, the filtering water-insoluble stirs and is lowered to 80 parts of ethanol, separates out solid, leaves standstill crystallization and filters fully, uses the small amount of ethanol washing dehydration, the anti-hematic acid calcium of exsiccant 19g, the calcium ascorbate 99.01% of 85.8%, 2 crystal water of productive rate.
Claims (4)
1, the preparation method of calcium ascorbate, calcium ascorbate added in the entry react with carbonic acid, the xitix that it is characterized in that 35.2 parts adds in 35~70 parts of water, under room temperature-75 ℃, added 10-11 part calcium carbonate reaction 30-240 minute, after reaction reaches balance, add an amount of milk of lime again, make the reaction solution pH value reach 4.5-7.0, stirred 1-30 minute, excessive materials and water-insoluble are removed in vacuum filtration, and mother liquor is evaporated to water content and is lower than 50% under 70 ℃, stir crystallisation by cooling, the edible ethanol that slowly adds 20-100 part continues stirring and crystallizing, reduces to room temperature naturally, centrifugation, with the washing with alcohol dehydration, get product in 50 ° of-60 ℃ of following vacuum-dryings or constant pressure and dry.
2, preparation method according to claim 1 is characterized in that water temperature is best for 30-55 ℃.
3, preparation method according to claim 1, the concentration that it is characterized in that milk of lime is 1-10%, best 1-5%.
4,, it is characterized in that the milk of lime add-on makes the best 5.0-6.0 of being of pH value of reaction solution according to claim 1,3 described methods.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN94100392A CN1044706C (en) | 1994-01-13 | 1994-01-13 | Preparation method of calcium ascorbate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN94100392A CN1044706C (en) | 1994-01-13 | 1994-01-13 | Preparation method of calcium ascorbate |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1107845A true CN1107845A (en) | 1995-09-06 |
CN1044706C CN1044706C (en) | 1999-08-18 |
Family
ID=5029614
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN94100392A Expired - Fee Related CN1044706C (en) | 1994-01-13 | 1994-01-13 | Preparation method of calcium ascorbate |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1044706C (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101899030A (en) * | 2010-07-09 | 2010-12-01 | 宜兴市江山生物科技有限公司 | Method for preparing vitamin C calcium salt |
CN102219767A (en) * | 2011-04-27 | 2011-10-19 | 中国水产科学研究院南海水产研究所 | Method for preparing calcium ascorbate by utilizing shrimp shells |
CN102584753A (en) * | 2011-11-01 | 2012-07-18 | 江苏江山制药有限公司 | Processing method of low-turbidity vitamin C calcium |
CN106866592A (en) * | 2016-12-28 | 2017-06-20 | 安徽泰格生物技术股份有限公司 | A kind of preparation method of L Calcium Ascorbates |
CN114369074A (en) * | 2021-12-14 | 2022-04-19 | 安徽泰格生物技术股份有限公司 | Method for preparing L-calcium ascorbate and byproduct L-ascorbic acid-2-phosphate |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4251449A (en) * | 1975-07-11 | 1981-02-17 | Clarence Schreur | Method of making a solid crystalline composition consisting essentially of calcium ascorbate |
CN1006077B (en) * | 1984-10-26 | 1989-12-13 | 乔治费希尔股份公司 | Process for producing worm-shape graphitic cast iron |
CH667627A5 (en) * | 1985-09-03 | 1988-10-31 | Sulzer Ag | SHIP DRIVE. |
-
1994
- 1994-01-13 CN CN94100392A patent/CN1044706C/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101899030A (en) * | 2010-07-09 | 2010-12-01 | 宜兴市江山生物科技有限公司 | Method for preparing vitamin C calcium salt |
CN102219767A (en) * | 2011-04-27 | 2011-10-19 | 中国水产科学研究院南海水产研究所 | Method for preparing calcium ascorbate by utilizing shrimp shells |
CN102219767B (en) * | 2011-04-27 | 2013-06-26 | 中国水产科学研究院南海水产研究所 | Method for preparing calcium ascorbate by utilizing shrimp shells |
CN102584753A (en) * | 2011-11-01 | 2012-07-18 | 江苏江山制药有限公司 | Processing method of low-turbidity vitamin C calcium |
CN106866592A (en) * | 2016-12-28 | 2017-06-20 | 安徽泰格生物技术股份有限公司 | A kind of preparation method of L Calcium Ascorbates |
CN114369074A (en) * | 2021-12-14 | 2022-04-19 | 安徽泰格生物技术股份有限公司 | Method for preparing L-calcium ascorbate and byproduct L-ascorbic acid-2-phosphate |
CN114369074B (en) * | 2021-12-14 | 2023-12-05 | 安徽泰格生物技术股份有限公司 | Method for preparing L-calcium ascorbate byproduct L-ascorbic acid-2-phosphate |
Also Published As
Publication number | Publication date |
---|---|
CN1044706C (en) | 1999-08-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN100357307C (en) | Crystallization method of abamectin Bla | |
DE19653225A1 (en) | New creatine pyruvate derivatives from crystallisation in polar solvents | |
US4393200A (en) | 18 α-Glycyrrhizinic acid and salt thereof | |
CN1044706C (en) | Preparation method of calcium ascorbate | |
CN102557970A (en) | Preparation method of anhydrous betaine | |
CN101307075B (en) | Method for preparing L-ascorbate-2-phosplate magnesium | |
US5231193A (en) | Process for producing ellagic acid | |
US6326513B1 (en) | Process for producing creatine or creatine-monohydrate | |
CN114292203B (en) | Preparation method of DL-panthenol | |
US5304251A (en) | Crystalline lactulose trihydrate and a method for its manufacture | |
KR20070024490A (en) | Process for the manufacture of lysergic acid | |
CN112375007B (en) | Treatment process of leftovers generated in preparation process of glycine ethyl ester hydrochloride | |
CN1070843C (en) | Process for crystallization from water of (S)-N,N'-bis[2-hydroxy-1-(hydroxymethyl) ethyl]-5-[(2-hydroxy-1-oxopropyl)amino]-2,4,6-triiodo-1,3-benzendicarboxamide | |
WO2008053437A2 (en) | A method for preparing ascorbic acid or a salt thereof from plant matrices | |
US4072695A (en) | 3α,7α-Dihydroxy-cholanic acid derivatives | |
Grün et al. | INVESTIGATION OF THE ESSENTIAL CONSTITUENT OF TURKEY-RED OIL AND ITS DERIVATIVES. | |
US4228081A (en) | Separation of isomers | |
US4162255A (en) | Process for extracting aristolochic acids | |
US2763681A (en) | Chlortetracycline, purification and alkaline earth salts | |
CN103172532B (en) | A kind of preparation method of ethylenediaminetetraacidic acidic calcium disodium salt | |
CN110143864B (en) | Method for preparing high-purity dihydroartemisinic acid by removing oil in dihydroartemisinic acid crude product | |
SU1747385A1 (en) | Method of calcium fluoride preparation | |
CN1117068C (en) | Method for preparation of hypotensor-laminine | |
MX2008012948A (en) | Narcotine purification process. | |
US4014908A (en) | Chemical process |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |