阅读说明：本技术 高钙盐类复合物及其制备方法 (High calcium salt compound and preparation method thereof ) 是由 刘豪 宗学醒 闫清泉 李志国 李玲玉 边燕飞 王彩霞 于 2019-09-11 设计创作，主要内容包括：本发明提出了高钙盐类复合物及其制备方法及含有其的食品或药品,所述高钙盐类复合物中含有钙、钾、钠、镁、磷酸根、氯离子、硫酸根和碳酸根,其中,基于所述高钙盐类复合物的总质量,所述钙、钾、钠、镁、磷酸根、氯离子、硫酸根和碳酸根的总含量为90～95质量％。本发明的高钙盐类复合物中富含多种营养物质,营养价值高,纯度好,安全性强,可用于食品或药品,具有广泛的应用前景。(The invention provides a high-calcium salt compound, a preparation method thereof and a food or a medicine containing the high-calcium salt compound, wherein the high-calcium salt compound contains calcium, potassium, sodium, magnesium, phosphate radical, chloride ion, sulfate radical and carbonate radical, and the total content of the calcium, potassium, sodium, magnesium, phosphate radical, chloride ion, sulfate radical and carbonate radical is 90-95 mass% based on the total mass of the high-calcium salt compound. The high calcium salt compound of the invention is rich in various nutrient substances, has high nutritive value, good purity and strong safety, can be used for food or medicine, and has wide application prospect.)

1. A high calcium salt compound is characterized in that the high calcium salt compound contains calcium, potassium, sodium, magnesium, phosphate radical, chloride ion, sulfate radical and carbonate radical,

wherein the total content of calcium, potassium, sodium, magnesium, phosphate, chloride, sulfate and carbonate is 90-95 mass% based on the total mass of the high-calcium salt compound.

2. The high calcium salt-based compound according to claim 1, wherein the raw material for preparing the high calcium salt-based compound comprises raw milk,

the ratio of the calcium content in the high-calcium salt compound to the calcium content in raw milk is 80-85 mass%;

the ratio of the potassium content in the high calcium salt compound to the potassium content in the raw milk is 55-60 mass%;

the ratio of the phosphate radical content in the high calcium salt compound to the phosphate radical content in raw cow milk is 55-60 mass%;

the ratio of the content of chloride ions in the high-calcium salt compound to the content of chloride ions in raw milk is 65-70 mass%.

3. A method for preparing a high calcium salt-based compound, comprising:

(1) curdling acidified raw milk by using rennin so as to obtain a clot, cutting, standing and stirring the clot;

(2) collecting the whey when the pH of the coagulum obtained after the stirring reaches a first predetermined pH, in order to remove casein;

(3) fermenting the whey, during which beta-lactoglobulin is removed;

simultaneously, piling the curd after discharging the whey liquid, collecting the whey liquid with the pH value of whey discharged from the curd reaching a second preset pH value from the beginning of piling, and mixing the whey liquid with the whey liquid after removing the beta-lactoglobulin;

(4) fermenting the mixed whey liquid obtained in the step (3), and sequentially removing bovine serum albumin and alpha-lactalbumin to obtain protein-removed liquid;

(5) and (3) filtering, sterilizing and drying the protein removing liquid by using a nanofiltration membrane so as to obtain the high calcium salt compound.

4. The method of claim 3, wherein the first predetermined pH is 6.1 to 6.2 and the second predetermined pH is 5.10 to 5.15;

optionally, in the step (3), when the whey liquid is fermented to a pH value of 5.3-5.4, filtering the whey liquid, and collecting filtrate so as to remove beta-lactoglobulin;

optionally, the filtration is performed with a 1-2 micron filter membrane.

5. The method of claim 3, wherein step (3) further comprises:

washing the curd with water when the pH of the curd-draining whey reaches a second predetermined pH and said mixing of the washed wash liquor, the collected whey and said beta-lactoglobulin-depleted whey;

optionally, the mixing temperature of the whey liquid and water is 25-30 ℃, and the mass ratio of the whey liquid to the water is 1: (1.8-2.3).

6. The method according to claim 3, wherein in the step (4), when the whey is fermented to 5.1, the whey is filtered, the filtrate is collected to remove bovine serum albumin, and then when the filtrate is fermented to 4.4, the filtrate is filtered, the filtrate is collected to obtain the protein-removed liquid;

optionally, the filtration is performed with a 1-2 micron filter membrane.

7. The method according to claim 3, wherein the rennet is added in an amount of 30-35g/1000kg based on the mass of the acidified raw milk;

optionally, the temperature of the curd treatment is 37-39 ℃, and the time is 35-40 minutes;

optionally, the size of the cut of the clot is 2-3cm²。

8. The method according to claim 3, wherein in the step (5), the filtration is performed by adopting a nanofiltration mode, the aperture of the adopted nanofiltration membrane is 1-1.5nm, the permeation amount is 4-5L/min, and the temperature is 30-40 ℃;

optionally, the sterilization is carried out at 75-85 ℃ for 24-30 seconds;

optionally, the drying treatment is carried out in a spray drying mode, wherein the air exhaust temperature is 75-90 ℃, and the temperature of the sterilized filtrate is 40-60 ℃.

9. A high calcium salt-containing compound obtained by the method for producing a high calcium salt-containing compound according to any one of claims 3 to 8;

optionally, the high calcium salt compound contains calcium, potassium, sodium, magnesium, phosphate, chloride, sulfate and carbonate,

wherein the total content of calcium, potassium, sodium, magnesium, phosphate, chloride, sulfate and carbonate is 90-95 mass% based on the total mass of the high calcium salt compound;

optionally, the ratio of the calcium content in the high-calcium salt compound to the calcium content in raw milk is 80-85 mass%;

the ratio of the potassium content in the high calcium salt compound to the potassium content in the raw milk is 55-60 mass%;

the ratio of the phosphate radical content in the high calcium salt compound to the phosphate radical content in raw cow milk is 55-60 mass%;

the ratio of the content of chloride ions in the high-calcium salt compound to the content of chloride ions in raw milk is 65-70 mass%.

10. A food or pharmaceutical product comprising the high-calcium salt-based compound according to claim 1 or 2 or the high-calcium salt-based compound according to claim 9.

Technical Field

The invention relates to the field of food. In particular, the invention relates to a high calcium salt compound and a preparation method thereof.

Background

99% of calcium is found in bones of the human body, and since the human body cannot produce calcium by itself, it must be ingested from food. However, many people have unbalanced dietary habits and like to eat instant food, so that not only can enough calcium be absorbed, but also calcium in the body is easily lost; in addition, the bone loss speed is increased with age, and the bone crisis can be caused after a long time. Therefore, it has become a popular trend to meet the demand of calcium in human body by eating food with high calcium added. The studies published on the "lancets" of the international well-known journal show that: after the milk calcium is eaten, the increase of the bone density still exists after the milk calcium is stopped for several years, and the absorption effect is good. About 25% of calcium ions in fresh raw milk (pH of about 6.78) are on casein micelles, and how to increase calcium from insoluble to soluble calcium, i.e., a method for preparing calcium-rich salts from cow milk, is still under study.

Disclosure of Invention

The present invention aims to solve at least to some extent at least one of the technical problems of the prior art.

In one aspect of the invention, the invention provides a high calcium salt-based compound. According to the embodiment of the invention, the high-calcium salt compound contains calcium, potassium, sodium, magnesium, phosphate, chloride, sulfate and carbonate, wherein the total content of the calcium, potassium, sodium, magnesium, phosphate, chloride, sulfate and carbonate is 90-95 mass%, the content of the calcium is 36-38 mass%, the content of the potassium is 22-24 mass%, the content of the magnesium is 1-2 mass%, and the content of the sodium is 7-8 mass%, based on the total mass of the high-calcium salt compound. According to the embodiment of the invention, the high-calcium salt compound mainly comprises calcium, potassium, sodium, magnesium, phosphate, chloride ions, sulfate radicals and carbonate, the purity (content) of the compound is as high as 90-95 mass%, and the nutritive value of the compound is high. And the safety is high, the product can be used for food or medicine, and the application prospect is wide.

According to an embodiment of the present invention, the high calcium salt compound may further have the following additional technical features:

according to the embodiment of the invention, the raw material for preparing the high-calcium salt compound comprises raw milk, and the ratio of the calcium content in the high-calcium salt compound to the calcium content in the raw milk is 80-85 mass%; the ratio of the potassium content in the high calcium salt compound to the potassium content in the raw milk is 55-60 mass%; the ratio of the phosphate radical content in the high calcium salt compound to the phosphate radical content in raw cow milk is 55-60 mass%; the ratio of the content of chloride ions in the high-calcium salt compound to the content of chloride ions in raw milk is 65-70 mass%.

In another aspect of the invention, the invention provides a method for preparing high calcium salt complexes. According to an embodiment of the invention, the method comprises: (1) curdling acidified raw milk by using rennin so as to obtain a clot, cutting, standing and stirring the clot; (2) collecting the whey when the pH of the coagulum obtained after the stirring reaches a first predetermined pH, in order to remove casein; (3) fermenting the whey, during which beta-lactoglobulin is removed; simultaneously, piling the curd after discharging the whey liquid, collecting the whey liquid with the pH value of whey discharged from the curd reaching a second preset pH value from the beginning of piling, and mixing the whey liquid with the whey liquid after removing the beta-lactoglobulin; (4) fermenting the mixed whey liquid obtained in the step (3), and sequentially removing bovine serum albumin and alpha-lactalbumin to obtain protein-removed liquid; (5) and (3) filtering, sterilizing and drying the protein removing liquid by using a nanofiltration membrane so as to obtain the high calcium salt compound. Therefore, the high-calcium salt compound obtained by the method disclosed by the embodiment of the invention is high in purity, rich in calcium, magnesium, potassium, sodium, phosphate, chloride ions, sulfate and carbonate, simple and convenient to operate, high in safety and suitable for large-scale production.

According to the embodiment of the invention, the first predetermined pH value is 6.1-6.2, and the second predetermined pH value is 5.10-5.15.

According to an embodiment of the invention, in the step (3), when the whey is fermented to a pH value of 5.3-5.4, the whey is filtered, and the filtrate is collected so as to remove beta-lactoglobulin.

According to the embodiment of the invention, the filtration is carried out by using a 1-2 micron filter membrane.

According to an embodiment of the present invention, the step (3) further includes: when the pH of the curd-draining whey reaches a second predetermined pH, the curd is washed with water and the washed wash liquor, the collected whey and the beta-lactoglobulin-depleted whey are subjected to said mixing.

According to the embodiment of the invention, the mixing temperature of the whey liquid and water is 25-30 ℃, and the mass ratio of the whey liquid to the water is 1: (1.8-2.3).

According to the embodiment of the invention, in the step (4), when the whey is fermented to 5.1, the whey is filtered, the filtrate is collected so as to remove bovine serum albumin, and then when the filtrate is fermented to 4.4, the filtrate is filtered, and the filtrate is collected so as to obtain the protein removing liquid.

According to the embodiment of the invention, the filtration is carried out by using a 1-2 micron filter membrane.

According to the embodiment of the invention, the addition amount of the rennin is 30-35g/1000kg based on the mass of the acidified raw milk.

According to the embodiment of the invention, the temperature of the curd treatment is 37-39 ℃ and the time is 35-40 minutes.

According to the embodiment of the invention, the cutting size of the clot is 2-3cm²。

According to the embodiment of the invention, in the step (5), the filtration is performed in a nanofiltration mode, the aperture of the adopted nanofiltration membrane is 1-1.5nm, the permeation amount is 4-5L/min, and the temperature is 30-40 ℃.

According to the embodiment of the invention, the sterilization is carried out at 75-85 ℃ for 24-30 seconds.

According to the embodiment of the invention, the drying treatment is carried out in a spray drying mode, wherein the exhaust temperature is 75-90 ℃, and the temperature of the sterilized filtrate is 40-60 ℃.

In another aspect of the present invention, the present invention provides a high calcium salt compound. According to the embodiment of the present invention, the high calcium salt-based compound is obtained by the method for preparing the high calcium salt-based compound described above. Therefore, the high-calcium salt compound provided by the embodiment of the invention has high nutritive value and high safety, can be used for food or medicines, and has a wide application prospect.

According to the embodiment of the invention, the high-calcium salt compound contains calcium, potassium, sodium, magnesium, phosphate, chloride, sulfate and carbonate, wherein the total content of the calcium, potassium, sodium, magnesium, phosphate, chloride, sulfate and carbonate is 90-95 mass%, the content of the calcium is 36-38 mass%, the content of the potassium is 22-24 mass%, the content of the magnesium is 1-2 mass%, and the content of the sodium is 7-8 mass%, based on the total mass of the high-calcium salt compound.

According to the embodiment of the invention, the ratio of the calcium content in the high calcium salt compound to the calcium content in the raw milk is 80-85% by mass based on the mass of calcium in the raw milk; the ratio of the potassium content in the high calcium salt compound to the potassium content in the raw milk is 55-60 mass%; the ratio of the phosphate radical content in the high calcium salt compound to the phosphate radical content in raw cow milk is 55-60 mass%; the ratio of the content of chloride ions in the high-calcium salt compound to the content of chloride ions in raw milk is 65-70 mass%.

In yet another aspect of the invention, a food or pharmaceutical product is provided. According to an embodiment of the present invention, the food or pharmaceutical product contains the above-mentioned high calcium salt-based compound or the high calcium salt-based compound obtained by the above-mentioned method. As described above, the high calcium salt compound has high purity, is rich in calcium, magnesium, potassium, sodium, phosphate, chloride, sulfate and carbonate, has high nutritive value and high safety, and can be used as food or medicine.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Detailed Description

The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention.

The present invention provides a high calcium salt-based compound, a method for producing the same, food and pharmaceutical products, which will be described in detail below.

High calcium salt compound

In one aspect of the invention, the invention provides a high calcium salt-based compound. According to the embodiment of the invention, the high-calcium salt compound contains calcium, potassium, sodium, magnesium, phosphate, chloride, sulfate and carbonate, wherein the total content of the calcium, potassium, sodium, magnesium, phosphate, chloride, sulfate and carbonate is 90-95 mass%, the content of the calcium is 36-38 mass%, the content of the potassium is 22-24 mass%, the content of the magnesium is 1-2 mass%, and the content of the sodium is 7-8 mass%, based on the total mass of the high-calcium salt compound.

The high-calcium salt compound mainly comprises calcium, potassium, sodium, magnesium, phosphate radical, chloride ion, sulfate radical and carbonate radical, and the purity (content) of the high-calcium salt compound is as high as 90-95 mass%. In addition, the composition also contains small amount of other components such as zinc and selenium. Therefore, the high calcium salt compound provided by the embodiment of the invention has high nutritional value. And the safety is high, the product can be used for food or medicine, and the application prospect is wide.

According to the embodiment of the invention, the raw materials for preparing the high-calcium salt compound comprise raw milk, and the ratio of the calcium content in the high-calcium salt compound to the calcium content in the raw milk is 80-85 mass%; the ratio of the potassium content in the high-calcium salt compound to the potassium content in the raw milk is 55-60 mass%; the ratio of the phosphate radical content in the high-calcium salt compound to the phosphate radical content in raw milk is 55-60 mass%; the ratio of the content of chloride ions in the high-calcium salt compound to the content of chloride ions in raw milk is 65-70 mass%. Therefore, the extraction rate of calcium, potassium, phosphate radical and chloride ions in the high calcium salt compound is higher.

Method for preparing high calcium salt compound

In another aspect of the invention, the invention provides a method for preparing high calcium salt complexes.

At present, in order to enrich calcium in cow milk, a membrane filtration technology is mainly adopted. However, it has certain limitations, and the complex suspension system for processing milk has the following defects: A. the purity/content of the final concentrate is low; B. different substances need different membrane treatments, and the screening combination of a plurality of membranes is complex to use, so that the loss of nutrient substances is easily caused; C. high cost and difficult maintenance.

For this purpose, the inventor creatively adopts the natural cheese technology, under the action of pre-acidification and rennet, the casein is denatured and precipitated to form coagulum, thereby removing the casein. Then, the components in the discharged whey can be extracted by physical sieve pores and chemical actions such as anion-cation exchange adsorption, macroporous adsorption resin, ammonium salt precipitation, dialysis and the like. However, the treatment of whey in the above manner results in loss of nutrients on the one hand and some adsorbent filling materials on the other hand do not guarantee food safety. Further, the inventor utilizes the characteristic of whey protein isoelectric point aggregation and sedimentation, and precipitates and removes whey protein when the pH value is continuously reduced and the whey protein isoelectric point is reached in the process of stacking and brewing the clot. Lactose is changed into lactic acid in the fermentation process, and is filtered by a nanofiltration membrane (NF membrane for short) to finally obtain natural salt substances with high purity/content, wherein the natural salt substances are rich in calcium, potassium, sodium, magnesium, phosphate radical, chloride ion, sulfate radical and carbonate radical.

According to an embodiment of the present invention, a method of preparing a high calcium salt-based compound includes:

s100, curding the acidified raw milk by using rennin to obtain a curd, and cutting, standing and stirring the curd. Thus, the casein is removed by the natural cheese process to denature the casein for precipitation, forming a clot.

According to the embodiment of the invention, the addition amount of the rennin is 30-35g/1000kg based on the mass of the acidified raw milk. Thereby sufficiently denaturing and precipitating the casein to form a clot. In the traditional process, the addition of the chymosin is about 20g/1000kg probably, the chymosin addition of the application is higher, and most of casein enters the clot, so that the casein content in whey liquid is lower, and the subsequent protein removal process and difficulty are reduced. The action protein of chymosin is kappa-casein, if the addition amount is too high, non-specific enzyme digestion of the chymosin can be caused, some alpha-casein or beta-casein enters the whey liquid, the subsequent protein removal process and difficulty are increased, and the extraction rate of each ion and the purity of the product are low.

The source of chymosin in the present application is not limited, and it can be obtained by a method such as self-preparation, donation, or marketing, and can be selected flexibly according to actual conditions. According to a particular embodiment of the invention, the chymosin is selected from the group consisting of CHY-MAX from the company Kehansen^TM Power NB。

According to the embodiment of the invention, the temperature of the curd treatment is 37-39 ℃ and the time is 35-40 minutes. Thereby sufficiently denaturing and precipitating the casein to form a clot.

According to the embodiment of the invention, the cutting size is 2-3cm². Thereby facilitating the discharge of whey.

S200 when the pH of the coagulum obtained after stirring reaches a first predetermined pH, collecting the whey in order to remove casein.

According to an embodiment of the invention, the first predetermined pH value is 6.1-6.2. Insoluble calcium on casein micelles at this pH value can free from the micelles into the whey, forming soluble calcium.

S300, fermenting the whey liquid, and removing beta-lactoglobulin in the process; simultaneously, the curd after discharging the whey liquid is piled, the whey liquid with the pH value of whey discharged from the curd reaching a second preset pH value from the beginning of piling is collected, and the whey liquid is mixed with the whey liquid after removing the beta-lactoglobulin.

According to an embodiment of the invention, the second predetermined pH value is 5.10-5.15. When the pH value of the discharged whey reaches 5.10-5.15, almost all the bound calcium is converted into free calcium, and the free calcium is discharged from the whey.

According to the embodiment of the invention, in the step S300, when the whey liquid is fermented to the pH value of 5.3-5.4, the whey liquid is filtered, and the filtrate is collected so as to remove beta-lactoglobulin. When the pH value of the whey liquid is 5.3-5.4, the whey liquid reaches the isoelectric point of beta-lactoglobulin (the protein with the highest content in whey protein, the content is 50.77%), aggregation and sedimentation occur, and the whey liquid is removed by filtration.

According to the embodiment of the invention, the filtration is carried out by using a 1-2 micron filter membrane. Thereby, the beta-lactoglobulin is separated and removed.

According to an embodiment of the present invention, step S300 further includes: when the pH of the curd-draining whey reaches a second predetermined pH, the curd is washed with water and the washed wash liquor, the collected whey and the beta-lactoglobulin-depleted whey are mixed. As the pH is lowered, calcium ions bound to the casein gradually dissociate into free calcium, which is excreted with the whey. When the pH value of the discharged whey reaches 5.10-5.15, almost all the bound calcium is converted into free calcium, most of the free calcium is discharged along with whey, a small amount of the free calcium is adhered and remained on the surface of a clot, and water is mixed with the clot so as to wash out the residual calcium, thereby improving the yield of the calcium.

According to the embodiment of the invention, the mixing temperature of the whey liquid and water is 25-30 ℃, and the mass ratio of the whey liquid to the water is 1: (1.8-2.3). This can sufficiently wash off the salt-based complex remaining on the surface of the clot, thereby improving the calcium yield.

S400, fermenting the mixed whey liquid obtained in the step S300, and sequentially removing bovine serum albumin and alpha-lactalbumin to obtain a protein-removed liquid.

According to the embodiment of the present invention, in step S400, when the whey is fermented to 5.1, the whey is filtered, the filtrate is collected so as to remove bovine serum albumin, and then when the filtrate is fermented to 4.4, the filtrate is filtered, and the filtrate is collected so as to obtain the deproteinized liquid. The pH value is lowered with the fermentation of the whey liquid, and when the pH value reaches 5.1, the isoelectric point of BSA (whey protein content of about 6.21%) is reached, and the BSA is removed by using a 1-2 μm filter. And then, continuously reducing the pH value of the whey liquid, reaching the isoelectric point of the alpha-lactalbumin when the pH value reaches 4.4, and removing by adopting a filter membrane of 1-2 microns.

S500, filtering, sterilizing and drying the protein removing liquid by using a nanofiltration membrane so as to obtain the high calcium salt compound.

According to the embodiment of the invention, in the step S500, the filtration is performed by adopting a nanofiltration mode, the aperture of the adopted nanofiltration membrane is 1-1.5nm, the permeation quantity is 4-5L/min, and the temperature is 30-40 ℃. Therefore, the lactic acid can be effectively removed, and the loss of other nutrient substances is also avoided. If the temperature is too low, salts are likely to be precipitated. If the amount of the permeate is too large, the product tends to contain an excessive amount of the undesired substances.

According to the embodiment of the invention, sterilization is carried out at 75-85 ℃ for 24-30 seconds. According to another embodiment of the invention, the drying treatment is carried out by adopting a spray drying mode, wherein the exhaust temperature is 75-90 ℃, and the temperature of the sterilized filtrate is 40-60 ℃. Therefore, the aims of sterilization and drying are fulfilled, and the loss of other nutrient substances is avoided.

In another aspect of the present invention, the present invention provides a calcium salt-based compound obtained by the above-described method for preparing a high calcium salt-based compound. The high-calcium salt compound contains calcium, potassium, sodium, magnesium, phosphate radicals, chloride ions, sulfate radicals and carbonate radicals, wherein the total content of the calcium, the potassium, the sodium, the magnesium, the phosphate radicals, the chloride ions, the sulfate radicals and the carbonate radicals is 90-95 mass%, the content of the calcium is 36-38 mass%, the content of the potassium is 22-24 mass%, the content of the magnesium is 1-2 mass%, and the content of the sodium is 7-8 mass%, based on the total mass of the high-calcium salt compound. Therefore, the high calcium salt compound provided by the embodiment of the invention has high nutritional value. And the safety is high, the product can be used for food or medicine, and the application prospect is wide.

According to the embodiment of the invention, the raw materials for preparing the high-calcium salt compound comprise raw milk, and the ratio of the calcium content in the high-calcium salt compound to the calcium content in the raw milk is 80-85 mass%; the ratio of the potassium content in the high-calcium salt compound to the potassium content in the raw milk is 55-60 mass%; the ratio of the phosphate radical content in the high-calcium salt compound to the phosphate radical content in raw milk is 55-60 mass%; the ratio of the content of chloride ions in the high-calcium salt compound to the content of chloride ions in raw milk is 65-70 mass%. Therefore, the extraction rate of calcium, potassium, phosphate radical and chloride ions in the high calcium salt compound is higher.

Food or medicine

In yet another aspect of the invention, a food or pharmaceutical product is provided. According to an embodiment of the present invention, the food or pharmaceutical product contains the above-mentioned high calcium salt-based compound. As described above, the high calcium salt-based compound has high nutritional value and high safety, and can be widely used in foods or medicines.

The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.