CN1107845A - Preparation for calcium ascorbate - Google Patents
Preparation for calcium ascorbate Download PDFInfo
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- 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
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Abstract
The process for preparing calcium ascorbate includes such technological steps as reaction of ascorbic acid on calcium carbonate in hot water, addition of lime milk to make pH 4.5-7, vacuum filtering, reducing concentration, crystalline, addition of edible alcohol for complete crystallization, cooling, centrifugal separation, alcohol washing and dewatering, and features complete reaction of a scorbic acid, high yield rate up to 94-98.5% and high purity >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 for calcium ascorbate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94100392A CN1044706C (en) | 1994-01-13 | 1994-01-13 | Preparation for calcium ascorbate |
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| Publication Number | Publication Date |
|---|---|
| CN1107845A true CN1107845A (en) | 1995-09-06 |
| CN1044706C CN1044706C (en) | 1999-08-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94100392A Expired - Fee Related CN1044706C (en) | 1994-01-13 | 1994-01-13 | Preparation for calcium ascorbate |
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| 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 |
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| Publication number | Publication date |
|---|---|
| CN1044706C (en) | 1999-08-18 |
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