CN1247854A - Active calcium citrate and its synthesizing process and equipment - Google Patents

Active calcium citrate and its synthesizing process and equipment Download PDF

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CN1247854A
CN1247854A CN 99119538 CN99119538A CN1247854A CN 1247854 A CN1247854 A CN 1247854A CN 99119538 CN99119538 CN 99119538 CN 99119538 A CN99119538 A CN 99119538A CN 1247854 A CN1247854 A CN 1247854A
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calcium citrate
insulating container
calcium
transformer
electrode plates
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CN1085196C (en
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邹纪平
邹大纲
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Abstract

The present invention relates to, especically, the reinforced synthesis of calcium citrate molecule containing crystal water by means of high-energy physics measures. Calcium citrate is one kind of chelate essential for life. For sake of strengthening the activity of calcium citrate, very high alternate electric field is applied during the synthesis, which can modify the space configuration of molecule, weaken the bond of coordination compound with outer ions, increase the solubility and thus strengthen the activity of calcium citrate in organism.

Description

Active calcium citrate, synthesis method thereof and device for synthesis
The invention relates to a method and a device for synthesizing calcium citrate and calcium citrate obtained by the synthesis method. In particular to a method and a special device for strengthening calcium citrate molecules containing crystal water by using a high-energy physical means to synthesize the active form of the calcium citrate molecules.
The calcium citrate is an intermediate product for purifying citric acid in the process of preparing citric acid in fine chemical industry. Most factoriesat home and abroad adopt a calcium salt method to extract citric acid from citric acid fermentation liquor. For example, the calcium salt method is specifically described in the book "Fine chemical engineering" published by Song Qinhuang Master and chemical industry publishers, which generally employs high temperature neutralization, wherein citric acid filtrate is heated to 80 ℃, calcium carbonate is added, and lime milk may also be used. The pH value of the neutralization end point is 5.0-5.5, the residual acid is titrated to be 0.2%, the temperature is kept at 80 ℃ for 0.5 hour, and then the solution is placedWashing sugar in a vacuum suction filtration barrel, turning over and washing for many times by using hot water at 80 ℃, and then obtaining the citric acid by processes of acidolysis, decoloration, concentration, crystallization and the like. It has now been found that calcium citrate has the effect of chelating agents, calcium fortifiers, buffers, coagulants, etc. in food additives, making it an independent variety in the food industry, and the following processes are mostly used: the aqueous citric acid solution is neutralized with lime or calcium carbonate, and the resulting precipitate is filtered and washed and dried (see handbook of food additives, second edition, chemical industry Press, ed. in 1997). The preparation method is synthesized under natural conditions, the molecular weight is 570.50, and the molecular formula is as follows: ca3(C6H5O7)2·4H2O, the structural formula is shown as formula 1:the characteristics are as follows: white fine powder, odorless and slightly hygroscopic. Very slightly soluble in water (0.095g/100mL, 25)Almost insoluble in ethanol (0.0089g/100mL, 25 ℃), and the water of crystallization gradually lost when heated to 100 ℃ and completely lost at 120 ℃. The maximum dissolution of calcium citrate in 10mL of dilute HCl solution containing 10% HCl at room temperature (20 ℃) was 5000mg, and the dissociation equation was: (wherein Cit is an abbreviation for citric acid). Calcium citrate is an important substance in organisms, and can be used for supplementing calcium to human bodies. In order to increase the activity of calcium citrate in the body, it is desirable to increase the maximum amount of calcium citrate dissolved in dilute hydrochloric acid. However, this is difficult to achieve with calcium citrate synthesized under natural conditions.
The invention provides a method for strengthening the synthesis of active calcium citrate by calcium citrate molecules by using an extra-high voltage and alternating strong electric field and a special device for the method. The coordination position of the inner boundary of the chelate is adjusted through a high-energy field, so that the activity of the calcium citrate molecule is increased.
In another aspect of the invention, active calcium citrate is provided, obtainable by the above process.
The synthesis of the calcium citrate of the invention is carried out as follows: adding dry calcium citrate containing crystal water into an insulating container, or directly adding wet calcium citrate containing crystal water at a neutralization end point and at a temperature of 80 ℃ into the insulating container without drying, then placing the insulating container between two metal polar plates, introducing ultrahigh voltage, wherein the ultrahigh voltage can be 80-110KV, so that an alternating strong electric field with the frequency of 380-450Hz is formed, and strengthening is carried out in the high-energy physical field (the strengthening time is usually 60-90 minutes), thereby activating the citric acid molecules. Calcium citrate is a chelate in a coordination compound, and under the influence of an artificial high-energy change electric field, the spatial configuration (or called changed chelating branch) between the internal central ion of the complex and a ligand is changed, so that the coordination position of the external ion of the complex and the internal ion is influenced, and the combination of the external ion is relatively weakened.
The apparatus for the synthesis method of the present invention will be described in detail below with reference to the accompanying drawings.
Fig. 1 is a schematic front view of the device of the present invention.
Referring to fig. 1, the device for synthesizing calcium citrate of the present invention has the following structure: the device comprises two parallel metal electrode plates 1, an insulating container 3 arranged between the two electrode plates 1, and a step-up transformer 4 for supplying ultrahigh voltage to the electrode plates, wherein the transformer 4 is connected with a square wave pulse generator 5.
In the above-described device of the present invention, the metal electrode plate may be any conductive metal plate, such as a copper plate, an iron plate, a zinc plate, a silver plate, etc., but a copper plate having good conductivity and low price is generally used. The area of each metal plate is 1M2And the thickness is 5 mm. Flat between two platesL represented by the line distance 2 is equal to 10-20cm, preferably 15cm, and a change in the value thereof will affect the electric field strength between the electrodes, so that L represented by the distance 2 should not exceed the above range. 3 is a container for calcium citrate containing water of crystallization, which must be made of insulatingmaterial, for example, it may beMade of glass, ceramic, plastic, etc., although glass containers are preferred and the containers do not need to be sealed. The width of the container must be less than the width L of 2 and should be able to move freely between the two plates. The area parallel between the container 3 and the plate 1 is smaller than the plate area, i.e. within the electric field formed by the plates. And 4, a step-up transformer for applying an alternating voltage (ultrahigh voltage) of 80-110KV, preferably 100KV to the bipolar plate 1 to form an alternating strong electric field with a frequency of 380-450 Hz. And 5 is a square wave pulse generator, namely a switch type chopper is adopted, and the duty ratio is 0.5.
The calcium citrate molecules synthesized by the method are strengthened, the molecular formula is unchanged, the molecular weight is also unchanged, the dissolution in water is basically unchanged, but the dissolution in diluted hydrochloric acid is different from that before strengthening: the maximum dissolving amount of the active calcium citrate can reach 10000mg in 10mL of dilute hydrochloric acid solution containing 10% of hydrogen chloride at room temperature (20 ℃). It is considered that the molecular structure of the active calcium citrate obtained according to the method of the present invention is represented by the following formula (2):
Figure A9911953800051
therefore, the lemon is added under the condition of ensuring the original basic properties of the calcium citrate to be unchanged
The activity of calcium carbonate in vivo. Thus, the active calcium citrate of the present invention is particularly suitable for use as
Food additive, calcium supplement, etc.
The invention will now be further described with reference to the following examples, but it should be understood that these examples are intended to illustrate the invention
The examples are intended to illustrate the invention only and do not limit the scope of the invention.
Example 1
Calcium citrate (20g) containing water of crystallization [ this calcium citrate was prepared according to the method described in "Fine chemical engineering, proceedings of Soxhlet's edition, published by chemical industry Press, page 157 of the first book]Placing into an open glass insulating container at room temperature, placing the insulating container between two copper electrode plates, each having an area of 1M2The thickness of the copper plate is 5 mm. Between two polar platesIs 15 cm. The alternating voltage applied to the bipolar plate 1 is 100KV, the frequency is 400Hz, and the power is 8 KW. The square-wave pulse generator 5 has a duty cycle of 0.5, a frequency of 400Hz and a power of 10 KW. The calcium citrate described above was subjected to an intensive physical field for 70 minutes. The voltage was then turned off, the glass insulator removed, cooled to room temperature and dried, and the calcium citrate therein weighed, and it was found that the weight of calcium citrate did not change, indicating that the composition of calcium citrate did not change.
Example 2
At the end of neutralization, pH 5.0-5.5, 80 ℃ and a water of crystallization (20g, the weight is the dry weight after cooling the calcium citrate to room temperature) [ the calcium citrate is prepared according to the method described in page 157 of "Fine chemical engineering" published by Song Qinhuang Shu, chemical industry Press]Putting into an open glass insulating container, and placing the insulating container between two copper electrode plates, wherein the area of each copper electrode plate is 1M2The thickness of the copper plate is 5 mm. The distance L between the two plates is 15 cm. The alternating voltage applied to the bipolar plate 1 is 100KV, the frequency is 400Hz, and the power is 8 KW. The square-wave pulse generator 5 has a duty cycle of 0.5, a frequency of 400Hz and a power of 10 KW. The calcium citrate described above was subjected to an intensive physical field for 70 minutes. The voltage was then turned off, the glass insulator removed, cooled to room temperature and dried, and the calcium citrate therein weighed, and no change in weight of the calcium citrate was found.

Claims (3)

1. A process for synthesizing calcium citrate features that the calcium citrate containing crystal water is put in an insulating container and then in an alternative strong electric field formed by two metal plates at 80-110V ultrahigh voltage and 380-450Hz frequency for strengthening.
2. Calcium citrate obtainable by the process according to claim 1.
3. A special device used in the method for synthesizing calcium citrate as claimed in claim 1, which comprises two parallel metal electrode plates 1, an insulating container 3, a step-up transformer 4, the transformer 4 is connected with a square wave pulse generator 5, characterized in that the insulating container 3 is placed between the two parallel metal electrode plates 1, and the overvoltage on the metal electrode plates is supplied by the step-up transformer 4.
CN99119538A 1999-09-02 1999-09-02 Active calcium citrate and its synthesizing process and equipment Expired - Fee Related CN1085196C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102060691A (en) * 2010-12-13 2011-05-18 日照鲁信金禾生化有限公司 Continuous acidolysis process for calcium hydrogen citrate

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1026488C (en) * 1992-06-25 1994-11-09 袁竞成 Preparation method of high purity medical calcium citrate using general calcium lime and edible citric acid

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102060691A (en) * 2010-12-13 2011-05-18 日照鲁信金禾生化有限公司 Continuous acidolysis process for calcium hydrogen citrate
CN102060691B (en) * 2010-12-13 2013-05-15 日照鲁信金禾生化有限公司 Continuous acidolysis process for calcium hydrogen citrate

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