CN102351867B - Natural phyllo-iron calcium Salt And Preparation Method - Google Patents
Natural phyllo-iron calcium Salt And Preparation Method Download PDFInfo
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- CN102351867B CN102351867B CN201110270086.6A CN201110270086A CN102351867B CN 102351867 B CN102351867 B CN 102351867B CN 201110270086 A CN201110270086 A CN 201110270086A CN 102351867 B CN102351867 B CN 102351867B
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- chlorophyllin
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Abstract
The invention discloses a kind of preparation method of natural phyllo-iron calcium salt, and obtain natural phyllo-iron calcium salt (also claiming iron chlorophyllin calcium).The method is that directly replace, a step is made with sodium-iron-chlorophyllin and calcium salt for raw material.Sodium-iron-chlorophyllin and calcium salt are soluble in water respectively in mass ratio.Reacting liquid pH value is 8 ~ 9.Ca salt brine solution is slowly joined in sodium iron chlorophyllin salts solution, with about 1000r/min speed magnetic agitation, under room temperature, make its sufficient reacting.Ageing, be separated, 50 DEG C ~ 80 DEG C dryings, can obtain black (chocolate) chlorophyll iron calcium salt.The method prepares phyllins with the raw material natural phyllo-iron sodium salt that is easy to get---and chlorophyll iron (II) calcium salt, realizes giving the iron of people, calcium with mending and having no side effect.Preparation method is simple and direct, productive rate is high.Can be used as medicine and foodstuff additive, in food, medicine etc., have boundless application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of natural pigment salt, specifically a kind of preparation method of natural phyllo-iron calcium salt.Obtain natural phyllo-iron calcium salt, also claim iron chlorophyllin calcium.
Background technology
Chlorophyll needed for human survival belongs to magnesium porphyrin compound, is natural pigment.Phyllins product is obtained after being replaced with other metal ion by the magnesium ion at chlorophyll porphyrin ring center, as: Copper chlorophyllin a sodium salt, calcium CHLOROPHYLLINE sodium salt, sodium cobalt chlorophyllin salt, iron chlorophyllin sodium salt etc., there is excellent coloring effect, promote hematopoiesis, protect the liver, antimicrobial, the pharmacological function that promotes wound and the biological nature such as ulcer healing and anti-mutation and uniqueness, be easily absorbed by the body and have no side effect, be widely used in medicine, food, daily-use chemical industry and clinical.Chlorophyll structure is extremely similar to the structure of the protoheme in the mankind and most animals blood, is all tetrapyrrole metallic compound, and its key distinction is that the former central atom is magnesium and the latter is iron.If by chlorophyll iron (II) for de-magging, calcium ion salify is prepared into natural phyllo-iron calcium salt, iron can not only be mended and promote the regeneration of oxyphorase, there is certain anti-anemia action effect and antioxygenation, and give people and replenish the calcium simultaneously.
At present, calcium-supplementing preparation has inorganic calcium carbonate, secondary calcium phosphate, calcium chloride, calcium oxide etc., needs to consume hydrochloric acid in gastric juice after entering human body, and has hormesis to stomach and intestine; The calcium preparations such as organic calcium lactate, calcium acetate, calglucon, citrate of lime, l threonic acid.Natural phyllo-iron calcium salt provided by the invention adds a new kind in calcium-supplementing preparation field.
On carboxyl outside chlorophyll porphyrin ring, normally sodium replaces hydrogen salify.The situation that other metal ions replace hydrogen salify is rarely seen at present has two sections of reports (see the preparation method of 1. Liu refined duckweed ZL200710061547.2. natural phyllo-iron zinc salt, 2. to make pottery extra large roc. the preparation of Calcium pheophorbin. West China pharmacy will .2002,17 (2): 120).Through retrieval, natural phyllo-iron calcium salt and derive with sodium-iron-chlorophyllin the technical scheme turning to chlorophyll iron calcium salt and yet there are no report.
Summary of the invention
The object of this invention is to provide a kind of is raw material with sodium-iron-chlorophyllin, and with single factor alternate method divalent calcium ions directly replaced the carboxyl sodium in sodium-iron-chlorophyllin, a step makes the high natural phyllo-iron calcium salt of purity, method is simple and direct, do not produce by product, environmental friendliness, productive rate is high.
In order to realize foregoing invention object, present invention employs following technical scheme:
A preparation method for natural phyllo-iron calcium salt, it is with sodium-iron-chlorophyllin and calcium acetate for raw material, and directly replace, a step is made.Also calcium acetate can be replaced to prepare with calcium chloride.
Particularly, chlorophyll iron calcium salt preparation method of the present invention, comprises the following steps:
1, sodium-iron-chlorophyllin and calcium acetate mass ratio are 1: 10.Soluble in water respectively;
2, be that 5.8 ~ 6.8Ca salt brine solution slowly adds in sodium iron chlorophyllin salts solution by pH value, note: calcium acetate aqueous solution matching while using;
3, reacting liquid pH value is 8 ~ 9;
4, to turn left right speed magnetic agitation with 1000r/min, under room temperature, make its sufficient reacting;
5, Aging Temperature 60 ~ 80 DEG C, digestion time 15 ~ 20min;
6, filtering separation, 50 DEG C ~ 80 DEG C dryings, can obtain black (or chocolate) chlorophyll iron calcium salt.Above-mentioned numerical range can arbitrary combination, does not have inevitable corresponding relation.
By complexometry assay products iron content, calcium amount, calculating productive rate is: 88% ~ 94%.By the generation of colour-change and precipitation in preparation and UV spectrogram and IR spectrogram qualitative, and illustrate that product is chlorophyll iron calcium salt through atlas analysis.
Remarkable advantage of the present invention is, 1. prepares phyllins with the raw material natural chlorophyll ferrisodium that is easy to get--chlorophyll iron (II) calcium salt, realizes giving the iron of people, calcium with mending and having no side effect; Chlorophyll iron calcium salt is black small-particle, has metalluster.Water insoluble be slightly soluble in acetone, ethanol, solution is yellow-green colour, dissolves in 1: 1 hydrochloric acid with in dilute hydrochloric acid, is comparatively soluble in pH and obtains yellow-green soln in more than 12 basic solutions.2. preparation method is simple and direct, cost is low, does not produce by product, environmental friendliness, and productive rate is high, does not produce chlorophyll iron (III) calcium salt; 3. be widely used, but medicine, may also be foodstuff additive.Boundless application prospect is had in food, medicine etc.
Accompanying drawing explanation
Fig. 1 is sodium iron chlorophyllin UV abosrption spectrogram
Fig. 2 is chlorophyll iron calcium UV abosrption spectrogram
Fig. 3 is the IR spectrogram of chlorophyll iron calcium.
Fig. 4 is the IR spectrogram that chlorophyll iron is received.
Embodiment
Below in conjunction with concrete accompanying drawing and by embodiment, the present invention will be further described.
The key instrument that the present invention uses: HH-S digital display thermostat water bath (Jintan); AEL-160 electronic balance; UV7652 spectrophotometer (Shanghai Precision Scientific Apparatus Co., Ltd); AVATAR360 Fourier transformation infrared spectrometer (Nicolet company of the U.S.).
The primary drug that the present invention uses:
Sodium-iron-chlorophyllin (Shandong Guang Tongbao Pharmaceuticals Ltd); Calcium acetate (AR, Shanghai stone flour factory); Calcium chloride (AR, Beijing).
Embodiment 1
Sodium-iron-chlorophyllin its strength of solution 13g/L water-soluble, pH value is 8.2.Calcium acetate its pH value of solution water-soluble is 5.8 (these solution matching while using).Ca salt brine solution is slowly joined in sodium iron chlorophyllin salts solution.To turn left right speed magnetic agitation with 1000r/min simultaneously, under room temperature, make its sufficient reacting.Aging Temperature 60 DEG C, digestion time 15min.Filtering separation, 80 DEG C of dryings, can obtain black (chocolate) chlorophyll iron calcium salt.Carry out each index determining.Wherein, by AVATAR360 type Fourier transformation infrared spectrometer and UV7652 spectrophotometric analysis, obtain sodium-iron-chlorophyllin and chlorophyll iron calcium salt spectrogram (see accompanying drawing 1 ~ 4), and analyse and compare, determine that product is chlorophyll iron calcium salt.
Calculating productive rate is 88%
See accompanying drawing 1,2 and following table.From UV spectrum analysis, the peak shape of sodium-iron-chlorophyllin has seen 400.5nm and 666.5nm typical case peak position.There is 401.0nm and 663..5nm at the absorption curve visible region place of chlorophyll iron calcium salt, both peak shapes are similar, but, calcium ion band two positive charges, its electronegativity is 1.00, the electronegativity of sodium ion is 0.93, therefore strong compared with sodium of its sucting electronic effect, thus make the wavelength of its main peaks by 666.5nm blue shift to 663.5nm.Viewed from absorbancy: sodium-iron-chlorophyllin is greater than chlorophyll iron calcium salt in 400.5nm absorbancy, and the value at 666.5nm place is less than its value.
Table iron chlorophyllin calcium and sodium iron chlorophyllin uv-spectrogram peak position, absorbancy
See accompanying drawing 3,4UV spectrogram, analysis draws: 1300cm
-1-C-O group stretching vibration peak due to Na
+, Ca
2+the inductive effect of two metal ion species causes peak position to be moved to high-selenium corn frequency displacement, therefore at 1400cm
-1occur, again because Ca
2+electronegativity is greater than Na
+, inductive effect is stronger, and therefore chlorophyll iron calcium salt is at 1411cm
-1.The vibration peak of carboxyl is at 1700cm
-1left and right, from accompanying drawing 3, does not find in 4, and carboxyl and Na are described
+, Ca
2+cause after salify.
From experimental phenomena change, after sodium iron chlorophyllin is water-soluble, solution colour is blackish green, adds Ca
2+during reagent salify, produce black precipitate immediately, illustrated that novel substance generates.
Salt-forming reaction equation:
In sum, can determine that product is chlorophyll iron calcium salt.
Embodiment 2
Sodium-iron-chlorophyllin its pH value of solution water-soluble is 9.0.Calcium acetate its pH value of solution water-soluble is 6.8 (these solution matching while using).Ca salt brine solution is slowly added in sodium-iron-chlorophyllin.To turn left right speed magnetic agitation with 1000r/min simultaneously, under room temperature, make its sufficient reacting.Aging Temperature 70 DEG C, digestion time 20min.Filtering separation, 60 DEG C of dryings, can obtain black (chocolate) chlorophyll iron calcium salt.
Calculating productive rate is 90%
Embodiment 3
Sodium-iron-chlorophyllin its pH value of solution water-soluble is 8.5.Calcium acetate its pH value of solution water-soluble is 6.5 (these solution matching while using).Ca salt brine solution is slowly added in sodium-iron-chlorophyllin.To turn left right speed magnetic agitation with 1000r/min simultaneously, under room temperature, make its sufficient reacting.Aging Temperature 80 DEG C, digestion time 15min.Filtering separation, 50 DEG C of dryings, can obtain black (chocolate) chlorophyll iron calcium salt.
Calculating productive rate is 94%
Iron chlorophyllin calcium salt proterties: black small-particle, has metalluster.Water insoluble be slightly soluble in acetone, ethanol, solution is yellow-green colour, dissolves in 1: 1 hydrochloric acid with in dilute hydrochloric acid, is comparatively soluble in pH and obtains yellow-green soln in more than 12 basic solutions.
Although give detailed description and explanation to the specific embodiment of the present invention above; but what should indicate is; we can carry out various equivalence according to conception of the present invention to above-mentioned embodiment and change and amendment; its function produced do not exceed that specification sheets contains yet spiritual time, all should within protection scope of the present invention.
Claims (2)
1. a preparation method for natural phyllo-iron calcium salt, is characterized in that: with sodium-iron-chlorophyllin and calcium acetate for raw material, by single factor alternate method, divalent calcium ions is directly replaced sodium ion, a step is made,
Specifically comprise the following steps:
1) sodium-iron-chlorophyllin and calcium acetate mass ratio are 1: 10, soluble in water respectively;
2) be that 5.8 ~ 6.8 calcium acetate aqueous solution slowly add in sodium-iron-chlorophyllin by pH value, described calcium acetate aqueous solution matching while using;
3) reaction solution pH is 8 ~ 9;
4) with 1000r/min rotary speed magnetic agitation, its sufficient reacting under room temperature, is made;
5) Aging Temperature 60 ~ 80 DEG C, digestion time 15 ~ 20min;
6) be separated, 50 DEG C ~ 80 DEG C dryings, black can be obtained or claim chocolate chlorophyll iron calcium salt;
By complexometry assay products iron content, calcium amount, calculating productive rate is: 88% ~ 94%.
2. method according to claim 1, is characterized in that, the concrete steps of described method are: sodium-iron-chlorophyllin its strength of solution 13g/L water-soluble, and pH value is 8.2; Calcium acetate its pH value of solution water-soluble is 5.8, the calcium acetate aqueous solution is slowly joined in sodium iron chlorophyllin salts solution, simultaneously with 1000r/min rotary speed magnetic agitation, its sufficient reacting is made, Aging Temperature 60 DEG C, digestion time 15min under room temperature, filtering separation, 80 DEG C of dryings, can obtain black chlorophyll iron calcium salt, and calculating productive rate is 88%.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102746311A (en) * | 2012-07-30 | 2012-10-24 | 河北联合大学 | Natural strontium ferrous chlorophyllin and preparation method thereof |
| CN102796108A (en) * | 2012-07-30 | 2012-11-28 | 河北联合大学 | Natural chlorophyll iron-manganese salt and preparation method thereof |
| CN102775416A (en) * | 2012-07-30 | 2012-11-14 | 河北联合大学 | Natural chlorophyll iron magnesium salt and method for preparing same |
| CN102757439A (en) * | 2012-07-30 | 2012-10-31 | 河北联合大学 | Natural cobalt iron chlorophyllin and preparation method thereof |
| CN102757438A (en) * | 2012-07-30 | 2012-10-31 | 河北联合大学 | Natural nickel ferrous chlorophyll salt and preparation method thereof |
| CN105037378A (en) * | 2015-07-30 | 2015-11-11 | 潍坊友容实业有限公司 | Method for preparing and extracting iron chlorophyll and prepared iron chlorophyll |
| CN105037377A (en) * | 2015-07-30 | 2015-11-11 | 潍坊友容实业有限公司 | Extraction preparation method for sodium ferrous chlorophyllin and sodium ferrous chlorophyllin prepared through extraction preparation method |
| CN110090211B (en) * | 2018-01-29 | 2021-09-28 | 武汉联合药业有限责任公司 | Use of chlorophyll derivatives for improving microcirculation disorders |
| CN109463491A (en) * | 2019-01-07 | 2019-03-15 | 刘安军 | A kind of instant green tea and preparation method thereof rich in chlorophillins |
Citations (2)
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|---|---|---|---|---|
| CN1105028A (en) * | 1993-12-11 | 1995-07-12 | 毕思彬 | Metal (copper, ferrons, zinc and germanium etc.) chlorophyllin basic salt and its preparing method |
| CN101045730A (en) * | 2007-02-15 | 2007-10-03 | 河北理工大学 | Preparation method of natural phyllo-iron zinc salt |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105028A (en) * | 1993-12-11 | 1995-07-12 | 毕思彬 | Metal (copper, ferrons, zinc and germanium etc.) chlorophyllin basic salt and its preparing method |
| CN101045730A (en) * | 2007-02-15 | 2007-10-03 | 河北理工大学 | Preparation method of natural phyllo-iron zinc salt |
Non-Patent Citations (1)
| Title |
|---|
| 脱镁叶绿酸钙的制备;陶海鹏等;《华西药学杂志》;20020430;第17卷(第2期);120 * |
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