A method for preparing high-density citric acid-malic acid chelates

Abstract

The application provides a preparation method of high-density citric malic chelate, and belongs to the technical field of dietary supplements, and comprises the following steps: mixing water, malic acid and citric acid to obtain an acid solution; mixing an alcohol reagent and a metal compound to obtain a slurry; mixing the acid solution and the slurry, and performing a crystallization reaction at 105-110 DEG C; and centrifuging the obtained reaction product to obtain a precipitate, which is the high-density citric malic chelate. The density of the citric malic chelate prepared by the method provided by the application is 0.54-0.65 g / ml.

Description

Technical Field

[0001] This invention belongs to the field of dietary supplement technology, and particularly relates to a method for preparing a high-density citric acid-malic acid chelate. Background Technology

[0002] In the field of dietary supplements both domestically and internationally, citric acid-malic acid chelated (calcium, magnesium, zinc, iron, copper) mineral salts have a wide range of applications. However, the existing production processes produce products with low bulk density, and low-density powder products cannot be directly used in tablets or capsules because of their large volume for the same weight. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to provide a method for preparing a high-density citric acid-malic acid chelate, which improves the density of the citric acid-malic acid chelate.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0005] This invention provides a method for preparing high-density citric acid-malic acid chelates, comprising the following steps:

[0006] 1) Mix water, malic acid, and citric acid to obtain an acidic solution;

[0007] 2) The alcohol reagent is mixed with the metal compound to obtain a slurry;

[0008] The metal compounds include one or more of calcium, magnesium, zinc, iron, and copper carbonates, hydroxides, and oxides;

[0009] 3) Mix the acid solution obtained in step 1) with the slurry obtained in step 2), and carry out a crystallization reaction at 105-110°C. Centrifuge the resulting reactants to obtain a high-density citric acid-malic acid chelate.

[0010] Steps 1) and 2) are not subject to any time order requirement.

[0011] Preferably, in step 1), the mass ratio of water to citric acid and malic acid is 439:48.5:51.

[0012] Preferably, the alcohol reagent includes one or more of propylene glycol, glycerol, and butanediol.

[0013] Preferably, the mass ratio of the alcohol reagent to the metal compound is 50–185:45–81.

[0014] Preferably, the mass ratio of water to alcohol reagent is 439:50 to 185.

[0015] Preferably, the crystallization reaction in step 3) takes 2 hours.

[0016] Preferably, the acid solution is mixed with the slurry, and the pH value is adjusted to 6.5-7.5 before the crystallization reaction is carried out.

[0017] Preferably, after the precipitate in step 3) is washed with water and dried, a high-density citric acid-malic acid chelate is obtained.

[0018] Preferably, the washing time is 15 minutes.

[0019] Preferably, the drying temperature is 150°C.

[0020] The principle of this invention to increase the density of citric acid-malic acid chelates is as follows: a mixed system is formed by a high-boiling-point alcohol reagent and water. The boiling point of this system is higher than that of water, thereby increasing the reaction temperature of citric acid-malic acid with metal compounds during chelation and crystallization, and thus increasing the bulk density of the final product.

[0021] The beneficial effects of the present invention are as follows: the density of the citric acid-malic acid chelate obtained by the method provided by the present invention is 0.54-0.65 g / ml. Detailed Implementation

[0022] This invention provides a method for preparing high-density citric acid-malic acid chelates, comprising the following steps:

[0023] 1) Mix water, malic acid, and citric acid to obtain an acidic solution;

[0024] 2) The alcohol reagent is mixed with the metal compound to obtain a slurry;

[0025] The metal compounds include one or more of the carbonates, hydroxides, and oxides of calcium, magnesium, zinc, iron, and copper;

[0026] 3) Mix the acid solution obtained in step 1) with the slurry obtained in step 2), and carry out a crystallization reaction at 105-110°C. Centrifuge the resulting reactants to obtain a high-density citric acid-malic acid chelate.

[0027] Steps 1) and 2) are not subject to any time order requirement.

[0028] This invention involves mixing water, malic acid, and citric acid to obtain an acidic solution. In this invention, the mass ratio of water to citric acid and malic acid is 439:48.5:51.

[0029] This invention involves mixing an alcohol reagent with a metal compound to obtain a slurry; the metal compound includes one or more of calcium carbonate, sodium hydroxide, zinc oxide, ferric oxide, and copper oxide. In this invention, the alcohol reagent preferably includes one or more of propylene glycol, glycerol, and butanediol. In this invention, the mass ratio of the alcohol reagent to the metal compound is preferably 50–185:45–81, more preferably 150:60–76. In this invention, the mass ratio of water to the alcohol reagent is preferably 439:50–185.

[0030] In this invention, the obtained acid solution is mixed with the obtained slurry, and a crystallization reaction is carried out at 105-110°C. The resulting reactants are centrifuged, and the precipitate obtained is a high-density citric acid-malic acid chelate. Steps 1) and 2) are not limited by time order. In this invention, the crystallization reaction time is preferably 2 hours. In this invention, the acid solution and slurry are mixed, and the pH value is adjusted to 6.5-7.5 before the crystallization reaction. In this invention, the precipitate is preferably washed with water and dried to obtain the high-density citric acid-malic acid chelate. In this invention, the washing time is preferably 15 minutes. In this invention, the drying temperature is preferably 150°C.

[0031] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0032] Example 1

[0033] (1) Add 439 kg of water, 51 kg of malic acid and 48.5 kg of citric acid to a 1000 L jacketed and condenser No. 1 enamel reactor in sequence, stir until the solution is clear, pass steam through the jacket and heat the system to reflux state.

[0034] (2) Add 150kg of propylene glycol and 76kg of calcium carbonate to a 500L enamel reactor in sequence, and start stirring to make the system into a slurry.

[0035] (3) Use a diaphragm pump to slowly pump the calcium carbonate / propylene glycol slurry into the No. 1 enamel reactor, keeping the No. 1 reactor in a reflux state throughout the process, and gradually raising the reflux temperature to 105℃.

[0036] (4) Adjust the pH of the system to between 6.5 using calcium carbonate or citric acid, maintain the temperature at 105℃, and react for 2 hours;

[0037] (5) After the heat preservation reaction is completed, the reaction system is cooled to 20°C, the material is discharged and centrifuged. The centrifuge speed is 40Hz until no liquid is discharged from the outlet. The filter cake is washed with water for 15 minutes. After the gas phase detection shows no propylene glycol residue, the material is discharged.

[0038] (6) The filter cake after discharge is dried in a vacuum double cone dryer until the loss on drying is ≤10% (150℃, constant weight method);

[0039] (7) 120 kg of finished product calcium citrate malate was obtained from the collected materials. The bulk density of the finished product was 0.54 g / ml and the calcium content was 22.6% when tested with a powder tester.

[0040] Example 2

[0041] (1) Add 439 kg of water, 51 kg of malic acid and 48.5 kg of citric acid to a 1000 L jacketed and condenser No. 1 enamel reactor in sequence, stir until the solution is clear and the steam in the jacket is released, and heat the system to reflux.

[0042] (2) Add 185 kg of glycerol and 45 kg of magnesium hydroxide to a 500 L enamel-lined reactor in sequence, and start stirring to make the system into a slurry.

[0043] (3) The magnesium hydroxide / glycerol slurry was slowly pumped into the No. 1 enamel reactor using a diaphragm pump. The No. 1 reactor was kept in a reflux state throughout the process, and the reflux temperature was gradually increased to 110℃.

[0044] (4) Adjust the pH of the system to 7.5 using magnesium hydroxide or citric acid, maintain the temperature at 110℃, and react for 2 hours;

[0045] (5) After the heat preservation reaction is completed, the reaction system is cooled to 30°C, the material is discharged and centrifuged. The centrifuge speed is 40Hz until no liquid is discharged from the outlet. The filter cake is washed with water for 15 minutes. After the gas phase detection shows no glycerol residue, the material is discharged.

[0046] (6) The filter cake after discharge is dried in a vacuum double cone dryer until the loss on drying is ≤10% (150℃, constant weight method);

[0047] (7) 100 kg of magnesium citric acid malate was obtained from the collected materials. The bulk density of the finished product was 0.62 g / ml and the magnesium content was 11.4% when tested with a powder tester.

[0048] Example 3

[0049] (1) Add 439 kg of water, 51 kg of malic acid and 48.5 kg of citric acid to a 1000 L jacketed and condenser No. 1 enamel reactor in sequence, stir until the solution is clear and the steam in the jacket is released, and heat the system to reflux.

[0050] (2) Add 50 kg of butanediol and 62 kg of zinc oxide into a 500 L enamel-lined reactor in sequence, and start stirring to make the system into a slurry.

[0051] (3) The zinc oxide / butanediol slurry was slowly pumped into the No. 1 enamel reactor using a diaphragm pump. The No. 1 reactor was kept in a reflux state throughout the process, and the reflux temperature was gradually increased to 105℃.

[0052] (4) Adjust the pH of the system to 6.5 using zinc oxide or citric acid, maintain the temperature at 105℃, and react for 2 hours;

[0053] (5) After the heat preservation reaction is completed, the reaction system is cooled to 30°C, the material is discharged and centrifuged. The centrifuge speed is 40Hz until no liquid is discharged from the outlet. The filter cake is washed with water for 15 minutes. After the gas phase detection shows no butanediol residue, the material is discharged.

[0054] (6) The filter cake after discharge is dried in a vacuum double cone dryer until the loss on drying is ≤10% (150℃, constant weight method);

[0055] (7) 115 kg of zinc citrate malate was obtained from the collected materials. The bulk density of the finished product was 0.57 g / ml and the zinc content was 19.5% when tested with a powder tester.

[0056] Example 4

[0057] (1) Add 439 kg of water, 51 kg of malic acid and 48.5 kg of citric acid to a 1000 L jacketed and condenser No. 1 enamel reactor in sequence, stir until the solution is clear and the steam in the jacket is released, and heat the system to reflux.

[0058] (2) Add 185kg of glycerol and 81kg of ferric oxide into a 500L enamel reactor in sequence, and start stirring to make the system into a slurry.

[0059] (3) Use a diaphragm pump to slowly pump the ferric oxide / glycerol slurry into the No. 1 enamel reactor, keeping the No. 1 reactor in a reflux state throughout the process, and gradually raising the reflux temperature to 105℃.

[0060] (4) Adjust the pH of the system to 6.5 using ferric oxide or citric acid, maintain the temperature at 105℃, and react for 2 hours;

[0061] (5) After the heat preservation reaction is completed, the reaction system is cooled to 20°C, the material is discharged and centrifuged. The centrifuge speed is 40Hz until no liquid is discharged from the outlet. The filter cake is washed with water for 15 minutes. After the gas phase detection shows no glycerol residue, the material is discharged.

[0062] (6) The filter cake after discharge is dried in a vacuum double cone dryer until the loss on drying is ≤10% (150℃, constant weight method);

[0063] (7) 130 kg of citric acid malate finished product was obtained from the collected materials. The bulk density of the finished product was 0.65 g / ml and the iron content was 21.8% when tested with a powder tester.

[0064] Example 5

[0065] (1) Add 439 kg of water, 51 kg of malic acid and 48.5 kg of citric acid to a 1000 L jacketed and condenser No. 1 enamel reactor in sequence, stir until the solution is clear and the steam in the jacket is released, and heat the system to reflux.

[0066] (2) Add 150kg of propylene glycol and 60kg of copper oxide into a 500L enamel-lined reactor in sequence, and start stirring to make the system into a slurry.

[0067] (3) The copper oxide / propylene glycol slurry was slowly pumped into the No. 1 enamel reactor using a diaphragm pump. The No. 1 reactor was kept in a reflux state throughout the process, and the reflux temperature was gradually increased to 105℃.

[0068] (4) Adjust the pH of the system to 7.5 using copper oxide or citric acid, maintain the temperature at 105℃, and react for 2 hours;

[0069] (5) After the heat preservation reaction is completed, the reaction system is cooled to 30°C, the material is discharged and centrifuged. The centrifuge speed is 40Hz until no liquid is discharged from the outlet. The filter cake is washed with water for 15 minutes. After the gas phase detection shows no propylene glycol residue, the material is discharged.

[0070] (6) The filter cake after discharge is dried in a vacuum double cone dryer until the loss on drying is ≤10% (150℃, constant weight method);

[0071] (7) 110 kg of copper citric acid malate finished product was obtained from the collected materials. The bulk density of the finished product was 0.58 g / ml and the copper content was 18.9% when tested with a powder tester.

[0072] Comparative Example 1

[0073] Compared with Example 1, Comparative Example 1 used water as the reaction system, the reaction temperature was 100°C, and the other parameters remained unchanged. The results showed that the bulk density of the finished product was 0.35 g / ml when measured by a powder analyzer.

[0074] Comparative Example 2

[0075] Compared with Example 2, the pH value of Comparative Example 2 was adjusted to 6.0, while the other parameters remained unchanged. No crystals were precipitated after the reaction was completed.

[0076] Comparative Example 3

[0077] Compared with Example 3, the pH value of Comparative Example 3 was adjusted to 7.6, while the other parameters remained unchanged. The bulk density of the finished product was measured to be 0.45 g / ml using a powder analyzer.

[0078] As can be seen from the above examples, the bulk density of the citric acid-malic acid chelate prepared by the method provided by the present invention is 0.54-0.65 g / ml, which is much higher than that of the citric acid-malic acid chelate prepared by the comparative example, and its application effect in tablet and capsule formulations is greatly improved.

[0079] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A process for the preparation of a high density citric malic chelate, characterized in that, The steps are: 1) mixing water, malic acid and citric acid to obtain an acid solution; 2) mixing glycerol reagent with ferric trioxide to obtain a slurry; 3) mixing the acid solution obtained in step 1) with the slurry obtained in step 2) to perform a crystallization reaction at 105℃, and centrifuging the obtained reaction product to obtain a high-density citric acid-malic acid chelate as a precipitate; The steps 1) and 2) are not limited in time sequence; The mass ratio of water to citric acid and malic acid in step 1) is 439:48.5:51; The mass ratio of glycerol to ferric trioxide is 185:81; The mass ratio of water to alcohol reagent is 439:185; The crystallization reaction in step 3) is performed for 2h; The acid solution is mixed with the slurry, and the pH value is adjusted to 6.5 before the crystallization reaction is performed; The precipitate in step 3) is washed with water and dried to obtain a high-density citric acid-malic acid chelate; The washing time is 15min; The drying temperature is 150℃.