KR20040065507A - watersoluble Calcium complex and manufacturing method thereof - Google Patents

Abstract

PURPOSE: A water-soluble composite calcium composition and its preparation method are provided, to obtain a highly pure powdered composite calcium composition whose calcium content is 18-40 %. CONSTITUTION: The water-soluble composite calcium composition comprises 5-60 wt% of a mixture comprising at three components selected from the group consisting of calcium carbonate, calcium hydroxide, calcium chloride, three kinds of calcium phosphate (I, II, III), calcium cyanate, calcium nitrate, calcium fluoride, magnesium oxide, magnesium sulfate, magnesium phosphate, magnesium hydroxide, potassium sulfate, potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide, ammonium phosphate, sulfuric acid and hydrochloric acid, wherein at least one is a calcium compound; 10-55 wt% of citric acid or sodium citrate; and 30-40 wt% of water.

Description

Water-soluble Calcium complex and manufacturing method

The present invention relates to a water-soluble complex calcium composition and a method for preparing the same, which are easily dissolved in water, and more specifically, to a calcium compound, a magnesium compound, a potassium compound, ammonium phosphate, sulfuric acid, hydrochloric acid and citric acid, or sodium citrate and water. The present invention relates to a powdery high purity water-soluble complex calcium composition having a pH in the range of 5.7 to 7.5 and having a main component calcium content of 18 to 40%, and a method for producing the same.

Water-soluble complex calcium is used as a fertilizer for dissolving the physiological disorders of vegetables and fruits by dissolving powdered calcium in water and spraying it on crops, etc., or for adsorbing, deodorizing and absorbing various mixed harmful gases. It is used in various ways. Calcium used for such various uses can obtain a desired effect as the main ingredient content is higher.

However, since calcium has a melting point that is almost insoluble in water, it is difficult to make it into an aqueous solution. As a method of manufacturing calcium, which is commonly used in the art, there is a method of extracting calcium after dissolving shellfish such as shellfish in acid. The prepared product was liquid in form and could not increase the main component content above a certain content.

As described above, since the current technology for producing water-soluble complex calcium has not been established, high purity water-soluble calcium containing 20% or more of calcium components could not be produced.

Therefore, conventional users had to use fertilizers with low concentration of calcium aqueous solution, and it was necessary to repeat the spraying on the crops several times so as to supply the calcium in a certain concentration so that the physiological disorders of the crops could be healed and sufficient nutrition was provided. Of course, there was a problem of deterioration of crop quality, and in order to improve it, the water-soluble complex calcium with high activity has a very high content of calcium as the main ingredient and contains a large number of active ingredients. Increases resistance to other obstacles.

The present invention has been researched and developed in order to effectively solve the above problems, an object of the present invention is to provide a powdery high purity water-soluble composite calcium composition in which the component content of the water-soluble composite calcium composition is increased by 18 to 40%.

Still another object of the present invention is to provide a method for producing a high purity water-soluble complex calcium having a high content of calcium.

In order to achieve the above object, the water-soluble composite calcium composition of the present invention is a calcium compound as calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (ⅠIIIII), calcium cyanide, calcium nitrate, calcium fluoride and magnesium oxide Magnesium sulphate, magnesium phosphate, magnesium hydroxide, potassium sulphate, potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide, ammonium phosphate, sulfuric acid, hydrochloric acid, a mixture of at least one of which is a calcium compound It consists of 5 to 60 weight%, 10 to 55 weight% of citric acid or sodium citrate, and 30 to 40 weight% of water.

In addition, the water-soluble composite calcium composition of the present invention is characterized in that the synthesized water-soluble composite calcium composition is in the range of pH 5.7 to 7.5 and the main component content is 18 to 40%.

The water-soluble composite calcium composition according to the present invention is calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (IIIIII), calcium cyanide, calcium nitrate, calcium fluoride and magnesium oxide in 30 to 40% by weight of water. Magnesium sulphate, magnesium phosphate, magnesium hydroxide, potassium sulphate, potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide, ammonium phosphate, sulfuric acid, hydrochloric acid, a mixture of at least one of which is a calcium compound Mixing 5 to 60% by weight with 10 to 55% by weight of citric acid or sodium citrate; stirring the mixture to maintain a temperature of 70 to 150 ° C. and rotating about 20 to 90 minutes at 100 to 150 rpm; Dehydration process that dehydrates the mixture by 50% or more by using filter press or vacuum dehydrator and 98% or more of the remaining moisture of the dehydrated mixture by electric or hot air dryer Completed through a drying process to remove.

The above manufacturing process will be described in more detail as follows.

First, as calcium compounds, calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (IIIIII), calcium cyanide, calcium nitrate and calcium fluoride were prepared, and magnesium compounds of magnesium oxide, magnesium sulfate, magnesium phosphate and magnesium hydroxide Prepare potassium sulfate, potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide potassium compound, ammonium phosphate, sulfuric acid, hydrochloric acid.

The calcium carbonate used as the main raw material of the present invention is a raw material having a purity of 98% or more, and calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (I, II, III), calcium cyanide, calcium nitrate, fluorinated Calcium, magnesium oxide, magnesium sulfate, magnesium phosphate, magnesium hydroxide, potassium sulfate, potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide, ammonium phosphate and sulfuric acid use raw materials with 95% purity. Preference is given to using phosphorus raw materials.

To prepare a raw material mixture by selecting from the above compounds, three or more compounds are selected and mixed so that the raw material mixture contains at least one calcium compound.

For example, a mixture can be made by selecting only calcium compounds such as calcium carbonate, calcium chloride, calcium hydroxide, three kinds of calcium phosphate (I, II, III), calcium sulfate, and calcium carbonate and calcium chloride as the calcium compound. Hydrochloric acid, potassium hydroxide, magnesium phosphate and magnesium hydroxide can be selected to form a mixture. Moreover, calcium fluoride can be selected as a calcium compound, and magnesium oxide, magnesium sulfate, potassium sulfate, ammonium phosphate, and potassium phosphate can also be selected and mixed.

According to the water-soluble composite calcium composition of the present invention, it is most preferable to select and mix calcium carbonate, calcium chloride, calcium hydroxide, calcium nitrate, three kinds of calcium phosphate, calcium cyanide, calcium fluoride and calcium sulfate as the raw material mixture.

A raw material mixture prepared by mixing the raw materials selected as described above in an appropriate amount is prepared. At this time, the raw materials to be mixed can adjust the amount of mutual mixing so that the pH of the finished water-soluble composite calcium composition is 5.7 to 7.5, calcium content 18 to 40%.

Also prepare citric acid or sodium citrate to be added to the mixture.

Citric acid (C ₆ H ₈ O ₇ ) is a hydroxyl-based polybasic carboxylic acid, also known as citric acid. It has good melting characteristics.

Sodium citrate is a granular powder of white crystals, easily soluble in water and used as a pH adjuster to precisely control pH in food production.

In addition, the citric acid or sodium citrate is preferably mixed in an amount of 10 to 55% by weight so as to adjust the pH range of the water-soluble composite calcium composition prepared.

30 to 40% by weight of water, 5 to 60% by weight of the mixed raw compound and 10 to 55% by weight of citric acid or sodium citrate are added to the stirrer and mixed. At this time, the mixing speed in the stirrer is adjusted to 100 ~ 150rpm and the reaction temperature is stirred for 20 to 90 minutes while maintaining at 70 ~ 150 ℃. The mixing speed, reaction temperature, and reaction time in the stirrer are set to solve the difficulty of mixing due to the weight difference between calcium and citric acid, and high purity water-soluble complex calcium when the mixing composition ratio and synthesis conditions of the raw materials do not match. It is desirable to meet the above conditions because the preparation of the composition is difficult and can not solve the pH problem of the side effect.

The mixture was subjected to the stirring process to dehydrate water by 50% or more using a filter press or a vacuum dehydrator, and then removes the remaining residual water by 98% or more using an electric furnace or a hot air dryer.

The reason for dehydrating more than 50% of the moisture in the filter press or vacuum dehydrator is to prevent the drying time in the electric furnace and the hot air dryer, which is the next process, and to remove 98% or more of the moisture in the electric furnace and the hot air dryer. The water-soluble complex calcium composition does not aggregate into agglomerates and is well powdered so that the quality of the product is excellent and it is for convenience when weighing to use it.

The water-soluble composite calcium composition of the present invention thus completed has a very high absorption power to the crop when used as a fertilizer because it is completely dissolved in water as high purity calcium having a main component content of 18 to 40%. Therefore, it is possible to strengthen the cell walls of crops through rapid nutrition, and to prevent and cure the occurrence of malnutrition and various physiological disorders and pests. Furthermore, the water-soluble complex calcium composition of the present invention may serve to reduce overuse of pesticides, which is one of the causes of environmental pollution, and to gradually convert the soil into neutral soil by preventing acidification of the soil.

Examples of the present invention and calcium compounds, magnesium compounds, potassium compounds, ammonium phosphate, sulfuric acid, hydrochloric acid and citric acid or sodium citrate to be used as the main raw material of the present invention will be shown an experimental example to find the optimum mixing ratio, but The protection scope of the invention is not limited thereto.

<Example 1>

35% by weight of the solvent, water, 30% by weight citric acid and calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (I, II, III), sulfuric acid, hydrochloric acid, potassium hydroxide, magnesium phosphate, magnesium hydroxide 35% by weight of the mixture was added.

The mixture was placed in a stirrer and stirred while rotating at a speed of 120 rpm for 60 minutes while maintaining the temperature of the stirrer at 100 ° C. The water used as solvent during the stirring process was somewhat removed.

The stirred mixture was put in a vacuum dehydrator to dehydrate more than 50% of water. In order to remove the water remaining even after the dehydration process, the mixture was passed through a belt through which a constant amount of hot air was continuously supplied by a hot air dryer to remove more than 98% of water.

The water-soluble composite calcium composition thus obtained is a powdery high purity product having a calcium content of 18 to 40%, which is completely soluble in water, and thus has very high absorption ability and rapid nutrition when used as a fertilizer for crops or soil. Through supply, it played a role of suppressing / minimizing the crop's nutrient deficiency and the occurrence of various pests as well as gradually converting the acidified soil into neutral soil.

Experimental Example 1

Calcium carbonate, calcium chloride, calcium hydroxide, calcium phosphate (I, II, III) and calcium sulfate and citric acid or sodium citrate were mixed in the following weight to prepare a water-soluble composite calcium composition.

NO. One 2 3 4 5 6 7 8 9 10 11 Calcium carbonate 40.2 35.6 35.6 32.9 21.4 24.0 18.6 24.6 27.5 27.8 27.9 Calcium chloride 15.7 13.9 13.9 16.5 21.4 19.2 18.6 19.7 18.3 16.6 16.7 Calcium hydroxide 2.8 2.5 2.5 5.5 5.3 4.8 4.7 4.9 4.6 5.6 5.6 Calcium phosphate - - 1.0 1.1 5.9 10.6 4.7 5.4 10.1 3.3 3.4 Calcium sulfate 1.1 1.0 - - 3.2 2.9 2.8 2.9 2.8 2.0 1.7 Citric Acid / Sodium Citrate 40.2 47.0 47.0 44.0 42.8 38.5 50.6 42.5 36.7 44.7 44.7 Gross weight (g) 100 100 100 100 100 100 100 100 100 100 100 pH 7.41 6.88 6.66 7.02 6.58 6.95 6.84 7.28 7.19 6.73 6.71 Dissolution state Good Good Good Good Good Good Good Good Good Good Good

This experiment was carried out to determine the pH and dissolution of calcium carbonate, calcium chloride, calcium hydroxide, calcium phosphate (I, II, III), and when dissolved in water by mixing the total amount of calcium sulfate and citric acid or sodium citrate to 100g. to be.

Good in the display of the dissolved state means that the calcium component in the aqueous solution is dissolved well when dissolved in the mixture is adjustable within 18 to 40% and the transparency is also high.

In Table 1, Test Nos. 1 to 4 are strains having a high main ingredient content, and Test Nos. 5 to 11 are strains having a low main ingredient content.

Experimental Example 2

Water-soluble complex calcium compositions were prepared by mixing calcium carbonate, calcium chloride, calcium hydroxide, calcium phosphate (I, II, III), calcium sulfate and calcium nitrate with citric acid or sodium citrate in the following weights.

NO. One 2 3 4 5 6 7 Calcium carbonate 27.4 27.4 27.4 27.4 27.4 27.4 27.4 Calcium chloride 4.5 4.5 4.5 4.5 13.6 9.1 4.5 Calcium hydroxide 18.2 13.6 9.1 4.5 - - - Calcium phosphate - 4.5 4.5 4.5 6.4 11.8 13.6 Calcium sulfate - - 4.5 3.6 2.7 1.8 2.7 Calcium nitrate - - - - - - 1.8 Citric Acid / Sodium Citrate 49.9 50.0 50.0 55.5 49.9 49.9 50.0 Gross weight (g) 100 100 100 100 100 100 100 pH 6.26 6.28 6.07 6.29 5.69 5.91 6.30 Dissolution state Good Good Good Good Good Good Good

In this experiment, the total mixing amount of calcium carbonate, calcium chloride, calcium hydroxide, calcium phosphate (I, II, III), calcium sulfate and calcium nitrate with 100 g of citric acid or sodium citrate was mixed to dissolve in water. This is the test I saw.

Good in the display of the dissolved state means that the calcium component in the aqueous solution is dissolved well when dissolved in the mixture is adjustable within 18 to 40% and the transparency is also high.

In Table 2, Test Nos. 1 to 7 indicate strains having a weak acidity between pH 5.7 and 6.3.

Experimental Example 3

Water-soluble complex calcium compositions were prepared by mixing calcium fluoride, magnesium oxide, magnesium sulfate, potassium sulfate, ammonium phosphate and potassium phosphate with citric acid or sodium citrate in the following weights.

No. Raw Material Name One 2 3 4 5 6 7 Calcium fluoride 27.4 27.4 27.4 27.4 27.4 27.4 27.4 Magnesium oxide 18.2 13.6 9.1 4.5 - - - Magnesium sulfate 4.5 4.5 4.5 4.5 13.6 9.1 4.5 Potassium sulfate - 4.5 4.5 4.5 6.4 11.8 13.6 Ammonium Phosphate - - 4.5 3.6 2.7 1.8 2.7 Potassium phosphate - - - - - - 1.8 Citric Acid / Sodium Citrate 49.9 50.0 50.0 55.5 49.9 49.9 50.0 Gross weight (g) 100 100 100 100 100 100 100 pH 6.01 6.11 5.84 6.08 6.11 6.08 6.35 Dissolution state Good Good Good Good Good Good Good

This experiment is to check the pH and dissolution of calcium fluoride, magnesium oxide, magnesium sulfate, potassium sulfate, ammonium phosphate, potassium phosphate, potassium phosphate and citric acid or sodium citrate in a total amount of 100g. .

Good in the display of the dissolved state means that the calcium component in the aqueous solution is dissolved well when dissolved in the mixture is adjustable within 18 to 40% and the transparency is also high.

In Table 3, Test No. 1-7 shows the system with high citric acid ratio.

Experimental Example 4

Water-soluble complex calcium compositions were prepared by mixing calcium carbonate, calcium chloride, calcium hydroxide, hydrochloric acid, magnesium phosphate, magnesium hydroxide and sulfuric acid with citric acid or sodium citrate in the following weights.

No. Raw Material Name One 2 3 4 5 6 7 8 Calcium carbonate 27.4 27.4 27.4 27.4 27.4 27.4 27.4 27.4 Calcium chloride 18.2 13.6 9.1 4.5 - - - 4.5 Calcium hydroxide 4.5 4.5 4.5 4.5 13.6 9.1 1.8 3.6 Hydrochloric acid - - - - - - - 4.5 Magnesium phosphate - 4.5 4.5 4.5 6.4 11.8 13.6 2.7 Magnesium hydroxide - - 4.5 3.6 2.7 1.8 2.7 2.7 Sulfuric acid - - - - - - 4.5 4.5 Citric Acid / Sodium Citrate 49.9 50.0 50.0 55.5 49.9 49.9 50.0 50.1 Gross weight (g) 100 100 100 100 100 100 100 100 pH 6.09 5.97 5.77 6.28 6.65 6.84 6.35 6.10 Dissolution state Good Good Good Good Good Good Good Good

This experiment is to check the pH and dissolution of calcium carbonate, calcium chloride, calcium hydroxide, hydrochloric acid, magnesium phosphate, magnesium hydroxide, sulfuric acid and citric acid or sodium citrate in a total mixing amount of 100g and dissolved in water.

Good in the display of the dissolved state means that the calcium component in the aqueous solution is dissolved well when dissolved in the mixture is adjustable within 18 to 40% and the transparency is also high.

In Table 4, Test Nos. 1 to 8 indicate strains having a pH between 5.7 and 6.8.

As described above, the water-soluble complex calcium composition of the present invention is a powder-soluble complex calcium composition having a high activity function, which can quickly supply nutrition to the crops, thereby making it possible to produce crops of high quality as well as reducing labor costs and working hours. By shortening the user's economic benefits and further reducing the overuse of pesticides, it is effective in improving the soil, which can serve as an environmental improvement agent.

In addition, the water-soluble composite calcium composition prepared according to the present invention is excellent in the effects of adsorption, deodorization, and moisture absorption of various types of mixed harmful gases and odors, and thus can be used in various applications.

Claims (3)

Calcium compounds include calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (IIIIII), calcium cyanide, calcium nitrate, calcium fluoride and magnesium oxide, magnesium sulfate, magnesium phosphate, magnesium hydroxide, potassium sulfate, potassium phosphate, Consists of at least three kinds of potassium carbonate, potassium chloride, potassium hydroxide, ammonium phosphate, sulfuric acid, and hydrochloric acid, 5 to 60% by weight of mixed raw material, at least one of which is a calcium compound, 10 to 55% by weight of citric acid or sodium citrate And 30 to 40 wt% of water. The water-soluble composite calcium composition according to claim 1, wherein the water-soluble composite calcium composition is in a range of pH 5.7 to 7.5 and maintains a calcium content of 18-40%. Calcium carbonate, calcium hydroxide, calcium chloride, calcium sulfate, three kinds of calcium phosphate (IIIIII), calcium cyanide, calcium nitrate, calcium fluoride and magnesium oxide, magnesium sulfate, magnesium phosphate, magnesium hydroxide in 30-40% by weight of water 5 to 60% by weight of a mixture of potassium sulfate, potassium phosphate, potassium carbonate, potassium chloride, potassium hydroxide, ammonium phosphate, sulfuric acid and hydrochloric acid so that at least one of them is a calcium compound and citric acid or citric acid Mixing 10 to 55% by weight of sodium; Stirring the mixture for about 20 to 90 minutes at 100 to 150 rpm while maintaining the temperature of 70 to 150 ° C; A dehydration step of dehydrating the stirred mixture by 50% or more of water using a filter press or a vacuum dehydrator; Method for producing a water-soluble composite calcium composition, characterized in that the drying step of removing the excess water of the dehydrated mixture of 98% or more by an electric furnace or a hot air dryer.