A preparation process of nano calcium nutrient

Abstract

The invention discloses a preparation process of nano calcium nutrient, and relates to the technical field of nutrients. The preparation process consists of the following steps: S1, filling 2 cationic resin columns, denoted as column 1 and column 2, column 1 and column 2 are soaked with saturated calcium chloride solution, then rinsed with saturated calcium chloride solution to pH value 5-6, and rinsed with purified water to neutrality for standby use; S2, adding homemade milk hydrolysis mixed amino acid sodium salt aqueous solution to the cationic resin column column 1 prepared in step S1 at room temperature, slowly eluting and exchanging, and the effluent is circulated and exchanged 3-5 times to obtain effluent 1; S3, passing the effluent 1 obtained in step S2 through the cationic resin column 2, slowly eluting and exchanging, and obtaining effluent 2; S4, vacuum decompression and concentration of the effluent 2 obtained in step S3, the concentrated solution is sprayed and enters the high-speed airflow chamber, and the atomized liquid enters the freezing chamber after further cutting by the high-speed airflow, and freeze-dried. The nano mixed amino acid chelated calcium provided by the present invention has small toxic and side effects and good safety.

Description

Technical Field

[0001] The invention belongs to the field of nutrients, and specifically relates to a preparation process of nano calcium nutrients. Background Art

[0002] Calcium is the most abundant mineral element in the human body. In addition to being a component of the body, bones, and teeth, it also participates in various physiological activities. People call the calcium element absorbed by the human body in ionic form active calcium. The initial research on active calcium mainly focused on inorganic active calcium, and the compound was mainly glucose calcium.

[0003] Inorganic calcium, represented by fresh animal bones, shells, calcium carbonate ore, etc., contains high calcium content, but is insoluble in water. After entering the stomach, it must be neutralized by gastric acid and dissociated into Ca2+, so it is highly irritating to the stomach. In addition, since most of it is not neutralized and is excreted in the form of insoluble salts, the absorption rate is low, and it is easy to stay in the kidneys, which can easily cause kidney stones.

[0004] Traditional organic calcium is represented by calcium lactate, calcium acetate, calcium gluconate, etc. Organic calcium has a higher molecular weight and relatively low calcium content, but a higher absorption rate. Its effect is better than inorganic calcium preparations with high calcium content but low absorption rate. However, organic calcium also has the disadvantage of having different degrees of toxic side effects. Summary of the invention

[0005] The purpose of the present invention is to provide a preparation process of nano calcium nutrients.

[0006] Technical solution: A preparation process of nano calcium nutrient, which consists of the following steps:

[0007] S1, packing two cationic resin columns, denoted as column 1 and column 2, soaking column 1 and column 2 in saturated calcium chloride solution, then washing with saturated calcium chloride solution to pH 5-6, and washing with purified water to neutrality for standby use;

[0008] S2, adding the homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution to the cationic resin column 1 prepared in step S1 at room temperature, slowly eluting and exchanging, and cyclically exchanging the effluent 3-5 times to obtain the effluent 1;

[0009] S3, passing the effluent 1 obtained in step S2 through a cationic resin column 2, and slowly eluting and exchanging to obtain an effluent 2;

[0010] S4, the effluent 2 obtained in step S3 is concentrated under vacuum, the concentrated liquid is sprayed and then enters the high-speed airflow chamber, the atomized liquid is further cut by the high-speed airflow and then enters the freezing chamber, and freeze-dried to obtain the product.

[0011] Preferably, in step S1, columns 1 and 2 are soaked in saturated calcium chloride solution for 4 hours, the filling volume of column 1 is twice the filling volume of column 2, the diameter of column 1 is twice the diameter of column 2, and the aqueous solution is ensured to exceed the cation exchange resin by 10 cm during soaking.

[0012] Preferably, in step S2, the preparation method of the homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution is: after pasteurization of fresh milk, add cyclohexane with a volume of 0.5 times the volume of fresh milk, heat to 50°C for extraction for 2h, separate the liquids, discard the cyclohexane layer, add papain with a mass of 0.5% of the mass of fresh milk and alkaline protease with a mass of 0.2% of the mass of fresh milk to the remaining water layer, heat to 60°C for hydrolysis for 6h under stirring, add 2 mol / L sodium hydroxide dropwise to adjust the pH to 8, and filter to obtain.

[0013] Preferably, in step S2, the filling volume of the cationic resin column 1 is 1 times the volume of the homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution, and the elution flow rate is 1 column volume / hour.

[0014] Preferably, in step S3, the elution flow rate is 1.5-2 times column volume / hour.

[0015] Preferably, in step S4, the vacuum decompression concentration temperature is 60° C., the residual volume of the concentrate is twice the volume of the homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution, the spray volume is 5 kg / h, and the high-speed airflow ejection speed is 50 m / s.

[0016] The beneficial effects of the present invention are:

[0017] 1. The nano-mixed amino acid chelated calcium provided by the present invention has little toxicity and side effects, good safety, and is easy to absorb.

[0018] 2. The amino acid chelated calcium preparation process provided by the present invention adopts ion exchange resin, and the obtained product has better purity, high chelation rate and simpler operation.

[0019] 3. The preparation process of amino acid chelated calcium provided by the present invention adopts air flow cutting after spraying and then freeze drying. During the air flow cutting, part of the solution will volatilize, the solution temperature will decrease, and the amino acid chelated calcium will form crystal nuclei. Freeze drying will increase the crystal nuclei and grow to the nanometer scale, and the prepared nanoparticles will be more uniform. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the infrared spectrum of the amino acid chelated calcium of the present invention.

[0021] Figure 2 The schematic diagram of the structure of amino acid chelated calcium of the present invention is shown in FIG. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Embodiment 1:

[0024] Preparation of homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution: 5L fresh milk was pasteurized, added with 2.5L cyclohexane, heated to 50℃ with stirring for 2h, allowed to stand for 10min, separated, the cyclohexane layer discarded, and 25.8g papain and 10.3g alkaline protease were added to the remaining water layer with stirring, heated to 60℃ with stirring for hydrolysis for 6h, 2mol / L sodium hydroxide was added dropwise to adjust the pH to 8, 5L purified water was added, and the solution was filtered through a precision filter with a pore size of 0.45μm.

[0025] Prepare the cationic resin column:

[0026] Column 1: Fill 5L D001 cation exchange resin in a φ10cm resin column, add saturated calcium chloride solution, initially open the bottom valve, slowly let 5L of aqueous solution flow out, then close the bottom valve and let it soak for 4h. During soaking, ensure that the aqueous solution exceeds the cation exchange resin by 10cm. After 4h, open the bottom valve, wash with saturated calcium chloride to pH 5-6, rinse with purified water to neutrality, and set aside.

[0027] Column 2: Fill 2.5L D001 cation exchange resin in a φ5cm resin column, add saturated calcium chloride solution, initially open the bottom valve, slowly let 2.5L aqueous solution flow out, then close the bottom valve and let it soak for 4h. During soaking, ensure that the aqueous solution exceeds the cation exchange resin by 10cm. After 4h, open the bottom valve, wash with saturated calcium chloride to pH 5-6, rinse with purified water to neutrality, and set aside.

[0028] The homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution was added to the prepared cationic resin column 1 at room temperature, and the flow rate was controlled to be about 5L / h for slow elution and exchange. The effluent was circulated and exchanged 4 times to obtain effluent 1, and then column 1 was rinsed with 10L purified water, and the flow rate was controlled to be about 10L / h for rinsing to obtain rinsing solution 1; the effluent 1 was added to the prepared cationic resin column 2 at room temperature, and the flow rate was controlled to be about 3.75L / h for slow elution and exchange to obtain eluent 2, and the rinsing solution 1 was added to resin column 2, and the flow rate was controlled to be about 7.5L / h for rinsing until the end to obtain rinsing solution 2, and the eluent 2 and the rinsing solution 2 were combined, and the concentrated solution was concentrated under reduced pressure at 60℃ to a residual volume of 10L, and the concentrated solution was sprayed and atomized at a spray rate of 5kg / h and then entered the high-speed airflow chamber, and the high-speed airflow spraying speed was 50m / s. The atomized solution was further cut by the high-speed airflow and entered the freezing chamber, and freeze-dried to obtain it.

[0029] Embodiment 2:

[0030] Preparation of homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution: 5L fresh milk was pasteurized, added with 2.5L cyclohexane, heated to 50℃ with stirring for 2h, allowed to stand for 10min, separated, the cyclohexane layer discarded, and 25.8g papain and 10.3g alkaline protease were added to the remaining water layer with stirring, heated to 60℃ with stirring for hydrolysis for 6h, 2mol / L sodium hydroxide was added dropwise to adjust the pH to 8, 5L purified water was added, and the solution was filtered through a precision filter with a pore size of 0.45μm.

[0031] Prepare the cationic resin column:

[0032] Column 1: Fill 5L D001 cation exchange resin in a φ10cm resin column, add saturated calcium chloride solution, initially open the bottom valve, slowly let 5L of aqueous solution flow out, then close the bottom valve and let it soak for 4h. During soaking, ensure that the aqueous solution exceeds the cation exchange resin by 10cm. After 4h, open the bottom valve, wash with saturated calcium chloride to pH 5-6, rinse with purified water to neutrality, and set aside.

[0033] Column 2: Fill 2.5L D001 cation exchange resin in a φ5cm resin column, add saturated calcium chloride solution, initially open the bottom valve, slowly let 2.5L aqueous solution flow out, then close the bottom valve and let it soak for 4h. During soaking, ensure that the aqueous solution exceeds the cation exchange resin by 10cm. After 4h, open the bottom valve, wash with saturated calcium chloride to pH 5-6, rinse with purified water to neutrality, and set aside.

[0034] The homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution was added to the prepared cationic resin column 1 at room temperature, and the flow rate was controlled to be about 5L / h for slow elution and exchange. The effluent was circulated and exchanged 5 times to obtain effluent 1. The column 1 was then rinsed with 10L of purified water, and the flow rate was controlled to be about 10L / h for rinsing to obtain rinsing solution 1; the effluent 1 was added to the prepared cationic resin column 2 at room temperature, and the flow rate was controlled to be about 4.25L / h for slow elution and exchange to obtain eluent 2. The rinsing solution 1 was added to the resin column 2, and the flow rate was controlled to be about 7.5L / h for rinsing until the end to obtain rinsing solution 2. The eluent 2 and the rinsing solution 2 were combined, and the concentrated solution was concentrated under reduced pressure at 60°C to a residual volume of 10L. The concentrated solution was sprayed and atomized at a spray rate of 5kg / h and then entered the high-speed airflow chamber. The high-speed airflow spraying speed was 50m / s. The atomized solution was further cut by the high-speed airflow and entered the freezing chamber, and freeze-dried to obtain it.

[0035] Embodiment 3:

[0036] Preparation of homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution: 5L fresh milk was pasteurized, added with 2.5L cyclohexane, heated to 50℃ with stirring for 2h, allowed to stand for 10min, separated, the cyclohexane layer discarded, and 25.8g papain and 10.3g alkaline protease were added to the remaining water layer with stirring, heated to 60℃ with stirring for hydrolysis for 6h, 2mol / L sodium hydroxide was added dropwise to adjust the pH to 8, 5L purified water was added, and the solution was filtered through a precision filter with a pore size of 0.45μm.

[0037] Prepare the cationic resin column:

[0038] Column 1: Fill 5L D001 cation exchange resin in a φ10cm resin column, add saturated calcium chloride solution, initially open the bottom valve, slowly let 5L of aqueous solution flow out, then close the bottom valve and let it soak for 4h. During soaking, ensure that the aqueous solution exceeds the cation exchange resin by 10cm. After 4h, open the bottom valve, wash with saturated calcium chloride to pH 5-6, rinse with purified water to neutrality, and set aside.

[0039] Column 2: Fill 2.5L D001 cation exchange resin in a φ5cm resin column, add saturated calcium chloride solution, initially open the bottom valve, slowly let 2.5L aqueous solution flow out, then close the bottom valve and let it soak for 4h. During soaking, ensure that the aqueous solution exceeds the cation exchange resin by 10cm. After 4h, open the bottom valve, wash with saturated calcium chloride to pH 5-6, rinse with purified water to neutrality, and set aside.

[0040] The homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution was added to the prepared cationic resin column 1 at room temperature, and the flow rate was controlled to be about 5L / h for slow elution and exchange. The effluent was circulated and exchanged 6 times to obtain effluent 1. Column 1 was then rinsed with 10L of purified water, and the flow rate was controlled to be about 10L / h for rinsing to obtain rinsing solution 1; effluent 1 was added to the prepared cationic resin column 2 at room temperature, and the flow rate was controlled to be about 5L / h for slow elution and exchange to obtain eluent 2. The rinsing solution 1 was added to resin column 2, and the flow rate was controlled to be about 7.5L / h for rinsing until the end to obtain rinsing solution 2. The eluent 2 and the rinsing solution 2 were combined, and the concentrated solution was concentrated under reduced pressure at 60°C to a residual volume of 10L. The concentrated solution was sprayed and atomized at a spray rate of 5kg / h and then entered the high-speed airflow chamber. The high-speed airflow spraying speed was 50m / s. The atomized solution was further cut by the high-speed airflow and entered the freezing chamber, and freeze-dried to obtain the product.

[0041] Comparative Example 1:

[0042] Preparation of homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution: 5L fresh milk was pasteurized, added with 2.5L cyclohexane, heated to 50℃ with stirring for 2h, allowed to stand for 10min, separated, the cyclohexane layer discarded, and 25.8g papain and 10.3g alkaline protease were added to the remaining water layer with stirring, heated to 60℃ with stirring for hydrolysis for 6h, 2mol / L sodium hydroxide was added dropwise to adjust the pH to 8, 5L purified water was added, and the solution was filtered through a precision filter with a pore size of 0.45μm.

[0043] Prepare the cationic resin column:

[0044] Column 1: Fill 5L D001 cation exchange resin in a φ10cm resin column, add saturated calcium chloride solution, initially open the bottom valve, slowly let 5L of aqueous solution flow out, then close the bottom valve and let it soak for 4h. During soaking, ensure that the aqueous solution exceeds the cation exchange resin by 10cm. After 4h, open the bottom valve, wash with saturated calcium chloride to pH 5-6, rinse with purified water to neutrality, and set aside.

[0045] Column 2: Fill 2.5L D001 cation exchange resin in a φ5cm resin column, add saturated calcium chloride solution, initially open the bottom valve, slowly let 2.5L aqueous solution flow out, then close the bottom valve and let it soak for 4h. During soaking, ensure that the aqueous solution exceeds the cation exchange resin by 10cm. After 4h, open the bottom valve, wash with saturated calcium chloride to pH 5-6, rinse with purified water to neutrality, and set aside.

[0046] The homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution was added to the prepared cationic resin column 1 at room temperature, and the flow rate was controlled to be about 5L / h for slow elution and exchange. The effluent was circulated and exchanged 3 times to obtain effluent 1. The column 1 was then rinsed with 10L of purified water, and the flow rate was controlled to be about 10L / h for rinsing to obtain rinsing solution 1; the effluent 1 was added to the prepared cationic resin column 2 at room temperature, and the flow rate was controlled to be about 3.75L / h for slow elution and exchange to obtain eluent 2. The rinsing solution 1 was added to the resin column 2, and the flow rate was controlled to be about 7.5L / h for rinsing until the end to obtain rinsing solution 2. The eluent 2 and the rinsing solution 2 were combined, and the concentrated solution was concentrated under reduced pressure at 60°C to a residual volume of 10L. The concentrated solution was sprayed and atomized at a spray rate of 5kg / h and then entered the high-speed airflow chamber. The high-speed airflow spraying speed was 50m / s. The atomized solution was further cut by the high-speed airflow and entered the freezing chamber, and freeze-dried to obtain the product.

[0047] Comparative Example 2:

[0048] Preparation of homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution: 5L fresh milk was pasteurized, added with 2.5L cyclohexane, heated to 50℃ with stirring for 2h, allowed to stand for 10min, separated, the cyclohexane layer discarded, and 25.8g papain and 10.3g alkaline protease were added to the remaining water layer with stirring, heated to 60℃ with stirring for hydrolysis for 6h, 2mol / L sodium hydroxide was added dropwise to adjust the pH to 8, 5L purified water was added, and the solution was filtered through a precision filter with a pore size of 0.45μm.

[0049] Prepare the cationic resin column:

[0050] Column 1: Fill 5L D001 cation exchange resin in a φ10cm resin column, add saturated calcium chloride solution, initially open the bottom valve, slowly let 5L of aqueous solution flow out, then close the bottom valve and let it soak for 4h. During soaking, ensure that the aqueous solution exceeds the cation exchange resin by 10cm. After 4h, open the bottom valve, wash with saturated calcium chloride to pH 5-6, rinse with purified water to neutrality, and set aside.

[0051] Column 2: Fill 2.5L D001 cation exchange resin in a φ5cm resin column, add saturated calcium chloride solution, initially open the bottom valve, slowly let 2.5L aqueous solution flow out, then close the bottom valve and let it soak for 4h. During soaking, ensure that the aqueous solution exceeds the cation exchange resin by 10cm. After 4h, open the bottom valve, wash with saturated calcium chloride to pH 5-6, rinse with purified water to neutrality, and set aside.

[0052] The homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution was added to the prepared cationic resin column 1 at room temperature, and the flow rate was controlled to be about 10L / h for slow elution and exchange. The effluent was circulated and exchanged 4 times to obtain effluent 1, and then column 1 was rinsed with 10L purified water, and the flow rate was controlled to be about 10L / h for rinsing to obtain rinsing solution 1; the effluent 1 was added to the prepared cationic resin column 2 at room temperature, and the flow rate was controlled to be about 3.75L / h for slow elution and exchange to obtain eluent 2, and the rinsing solution 1 was added to resin column 2, and the flow rate was controlled to be about 7.5L / h for rinsing until the end to obtain rinsing solution 2, and the eluent 2 and the rinsing solution 2 were combined, and the concentrated solution was concentrated under reduced pressure at 60℃ to a residual volume of 10L, and the concentrated solution was sprayed and atomized at a spray rate of 5kg / h and then entered the high-speed airflow chamber, and the high-speed airflow spraying speed was 50m / s. The atomized solution was further cut by the high-speed airflow and entered the freezing chamber, and freeze-dried to obtain it.

[0053] The test results are shown in the following table:

[0054] Table 1 Chelation rate and average particle size of comparative examples and examples

[0055] sample Column 1 exchange bottom valve flow rate (L / h) Column 1 effluent circulation exchange (times) Calcium chelation rate (%) Average particle size D90 (nm) Example 1 5 4 97.0 116 Example 2 5 5 97.1 117 Example 3 5 6 97.1 115 Comparative Example 1 5 3 88.5 117 Comparative Example 2 10 4 87.4 116

[0056] Forty SPF Wistar rats weaned 20 days after birth, half of which were female and weighed 55±5g, were randomly divided into four groups, A, B, C, and D, with 10 rats in each group. After 5 days of adaptive feeding, group A was fed with a low-calcium feed, group B was fed with a low-calcium feed + the nano-amino acid chelated calcium of the present invention, group C was fed with a low-calcium feed + a commercially available calcium gluconate preparation, and group D was fed with a low-calcium feed + a commercially available calcium carbonate preparation. The rats drank deionized water and ate freely. After 4 weeks of feeding, the daily calcium intake of rats in groups B, C, and D was 20 mg of elemental calcium by gavage, and group A was given an equal volume of deionized water. After each group was fed with a low-calcium feed for 4 weeks, the rats in each group were transferred to a stainless steel metabolic cage for calcium metabolism measurement. The results are shown in Table 2.

[0057] Table 2 Calcium metabolism results of rats in animal feeding experiment (χ±S, n=8)

[0058] Group Blood calcium mmol / L Fecal calcium content mg / d / head Urine calcium content Mg / d / head Total calcium daily intake including feed mg Apparent absorption rate % Retention rate% Group A 1.59 9.68 2.05 31.3 69.07 62.52 Group B 2.93 5.75 2.28 49.9 88.48 83.91 Group C 1.95 8.76 9.6 50.1 82.51 63.35 Group D 2.21 7.27 10.49 50.2 85.51 64.62

[0059] Test results: It is known from Examples 1-3 and Comparative Examples 1-2 that when passing through column 1, the flow rate of the bottom valve is too fast or the number of effluent circulation exchanges when passing through column 1 is insufficient, which will lead to incomplete exchange and a slightly low chelation rate; the chelation rate of the amino acid chelated calcium of the present invention can reach more than 97%, and the average particle size is relatively stable, and the apparent absorption rate and the in vivo retention rate both show good test results.

[0060] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A preparation process of nano calcium nutrient, characterized in that: The preparation process consists of the following steps: S1, pack two cationic resin columns, record as column 1 and column 2, soak column 1 and column 2 in saturated calcium chloride solution for 4 hours, then rinse with saturated calcium chloride solution to pH 5-6, rinse with purified water to neutrality, and set aside; S2, adding the homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution to the cationic resin column 1 prepared in step S1 at room temperature, slowly eluting and exchanging at an elution flow rate of 1 column volume / hour, and cyclically exchanging the effluent 4-6 times to obtain effluent 1; then washing column 1 with 10L of purified water, controlling the flow rate to 10L / h, to obtain flushing solution 1; The preparation method of the homemade milk hydrolyzed mixed amino acid sodium salt aqueous solution is as follows: 5L fresh milk is pasteurized, then 2.5L cyclohexane is added, stirred and heated to 50°C for 2h, allowed to stand for 10min, separated, the cyclohexane layer is discarded, 25.8g papain and 10.3g alkaline protease are added to the remaining water layer under stirring, heated to 60°C for hydrolysis for 6h under stirring, 2mol / L sodium hydroxide is added dropwise to adjust the pH to 8, 5L purified water is added, and the solution is filtered through a precision filter with a pore size of 0.45μm. S3, passing the effluent 1 obtained in step S2 through a cationic resin column 2, slowly eluting and exchanging at an elution flow rate of 1.5-2 times the column volume / hour to obtain an effluent 2; adding the flushing liquid 1 to the resin column 2, controlling the flow rate to 7.5 L / h to flush until the end to obtain the flushing liquid 2; combining the effluent 2 and the flushing liquid 2 to obtain a combined liquid; S4, the combined liquid obtained in step S3 is concentrated under vacuum and reduced pressure, the concentrated liquid is sprayed and then enters the high-speed airflow chamber, the atomized liquid is further cut by the high-speed airflow with a spraying speed of 50m / s and then enters the freezing chamber, and freeze-dried.

2. The preparation process of nano calcium nutrient according to claim 1, characterized in that: In step S1, the filling volume of column 1 is twice that of column 2, and the diameter of column 1 is twice that of column 2. During immersion, ensure that the aqueous solution exceeds the cation exchange resin by 10 cm.

3. The preparation process of nano calcium nutrient according to claim 1, characterized in that: In step S4, the spraying amount is 5 kg / h.

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