JPH0260303B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a calcium fortifying agent containing salts whose main component is calcium, which has a good calcium absorption rate from milk raw materials. It has been known that milk materials such as milk contain high-quality calcium, which is efficiently taken into the animal body and plays an important role in skeletal formation. This high-quality calcium is often discarded as waste such as whey in the milk processing process. For example, when producing fermented cheese, casein, etc., it is necessary to add a starter to milk or skim milk to make it acidic, or to add sulfuric acid to it. The coagulated proteins are acidified by adding acids such as hydrochloric acid or lactic acid, and the mother liquor is discarded as acidic whey. At this time, calcium, magnesium, phosphorus, etc. lose their bonds with colloidal proteins due to acidification. It migrates into the mother liquor and is disposed of. The reason for this is that when proteins are coagulated with rennet in an almost neutral state, calcium and other substances are transferred to the proteins, and the salt content in the mother liquor decreases, resulting in sweet whey that can be used as a raw material for confectionery. This is because some of them have a high salt content and give off an unpleasant taste, making them unusable.Currently, they are usually treated with wastewater treatment equipment and discharged into rivers. The present invention was made in view of the above-mentioned circumstances, and we conducted research to effectively utilize the acidic milk raw material processing solution that had been previously discarded.We focused on the high quality calcium salts in the milk raw material and acidified the milk raw material solution. The problem was solved by separating the coagulated proteins produced, adding an alkali to the mother liquor to precipitate and separate the salts containing calcium as the main component, and concentrating or drying the separated salts to obtain salts containing calcium as the main component. It is. The milk raw materials used in the present invention are milk such as whole milk, skim milk, partially skimmed milk, concentrated milk such as whole fat concentrated milk, partially skimmed concentrated milk, skim concentrated milk, or milk powder such as whole milk powder, skim milk powder. etc. In the case of regular milk, use it as is, or in the case of concentrated milk or powdered milk, add water to make an appropriate concentration and use it as a milk raw material solution. Acidification of milk raw materials can be achieved by directly adding inorganic acids such as hydrochloric acid, sulfuric acid, or nitric acid, or organic acids such as citric acid or lactic acid to the milk raw material solution, as in casein production, or by adding Streptococcus lactis (Str.
lactis), Streptococcus cremoris (Str.
cremoris), Str. thermophilus, Lactobacillus bulgaricus (L.bulgalrcus), etc., and carry out lactic acid fermentation, pH 3.0 to 5.5, preferably PH 4. .0 to 5.0. Proteins coagulate due to acidification, and the mother liquor becomes acidic whey containing a large amount of calcium and the like. To explain this relationship, Table 1 shows examples of the compositions of so-called sweet whey and acid whey after separating proteins before and after neutrality using rennet.

[Table] As can be seen from the table above, the ash content of acid whey is higher at 0.77% compared to 0.55% for regular sweet whey, and sweet whey contains almost no calcium at 0.05%, whereas acid whey contains almost no calcium at 0.05%. In whey, it is extremely high at 0.125%. Separation of salts from a solution such as acid whey is carried out by adding an alkali to neutralize the pH to 5.0 to 8.0, preferably 6.0 to 7.0, and insolubilize the salts. Examples of the alkali used include sodium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, etc., and sodium hydroxide is preferred. That is, when an alkali is added to a solution of acid whey or the like, calcium in the solution combines with the phosphorus component to produce insoluble salts. However, if they are added as they are, the insolubilized salt particles become extremely fine particles, which is inconvenient to separate. Therefore, it is preferable to heat a solution such as acid whey in advance and add an alkali to it to remove large particles that easily settle. can be easily separated. The relationship between heating temperature and sedimentation rate of insolubilized salts will now be explained with reference to FIG. In the experiment, the acid whey shown in Table 1 was heated to various temperatures, a sodium hydroxide solution was added to adjust the pH to 6.5, and the mixture was stirred at that temperature for 3 minutes. As is clear from FIG. 1, as the heating temperature increases, the sedimentation rate also increases. However, when heated below 60°C, the sedimentation rate is less than 2.5 x 10 ^-2 cm/sec, making it unsuitable for separation by sedimentation or centrifugation, and separation by filtration is preferable. Crystals grow well when heated above 60°C, and can be efficiently separated by centrifugation or sedimentation. Of course, raising the heating temperature further will result in crystals that are easy to separate, but heating to a high temperature of 130°C or higher will cause a browning phenomenon in solutions such as acid whey, and the insolubilized salts will also become colored, so it is better to avoid this. good. Heating may be achieved by indirect heating using a plate type, heating machine, jacket type heating machine, etc. In some cases, direct heating by steam blowing may be used. However, if this heating is performed after neutralization, crystals that easily settle will not be obtained, and proteins will adhere to the walls of the heating device, making the work difficult, so care must be taken. The neutralization involves dissolving the alkali to a concentration of 5 to 50% and directly adding it to the solution of acid whey after heating to adjust the pH.
is set to 5.0 to 8.0, preferably 6.0 to 7.0. This is PH
If the pH is below 5.0, almost no precipitate will be formed, and if the pH is above 8.0, a neutralized odor will be generated, especially if the pH is between 6.0 and 7.0.
The yield is good and the product is of excellent quality. Now, Fig. 2 shows an example in which acid whey having the composition shown in Table 1 is used and neutralized with a 20% sodium hydroxide solution. In the figure, the vertical axis shows the insolubilization rate of the salt, and the horizontal axis shows the pH. As can be seen from the figure, insolubilization is seen from PH5.0 and increases sharply when the pH is above 6.0. 60 of total calcium
% or more becomes insolubilized. However, beyond that, the rate of increase in yield gradually slows down. Therefore, PH6.0~7.0
is the practical range. Precipitated salts may be separated immediately after neutralization, but preferably 1 to 30 minutes after neutralization.
It is preferable to maintain the temperature for a minute to allow sufficient crystal precipitation. This maintenance may be carried out within the piping, or may be carried out in a holding tank provided, or furthermore, in the case where separation by a sedimentation method is employed, it may be carried out in a settling tank. Although the apparatus used for neutralization may be a batch type in the reaction bed, a continuous addition apparatus is preferable, and an example of such an addition apparatus is a static mixer. This mixer continuously adds and mixes an alkaline solution according to the flow rate of acid whey or the like in the piping, and has the advantage of being able to perform continuous operations. After neutralization, any conventional solid-liquid separation method can be used to separate the produced insolubilized salts, such as centrifugation, sedimentation, or filtration. In addition, the sedimentation method is especially convenient for separating the salts after neutralization by heating, and a device such as a hydrocyclone is used to continuously supply the neutralizing solution from the side, and continuously supply the supernatant from the top. If the precipitated insolubilized salts are taken out from the bottom intermittently, the operation can be made continuous using a simple device. By the above method, 50 to 60% of the amount of calcium in acid whey is usually extracted as insolubilized salts, but these insolubilized salts are in the form of mud. Table 2 shows an example of the composition of the insolubilized salts thus obtained and an example of the composition of the treated whey from which the insolubilized salts have been separated.

[Table] As is clear from Table 2, the insolubilized salts contain a large amount of ash and are mainly present as calcium salts of phosphoric acid, and detailed analysis values thereof are shown in Table 3.

[Table] The above insolubilized salts contain a large amount of water and will rot if left as is, so they must be concentrated or dried. Concentration is conveniently carried out by using a dehydrator in a conventional manner, and usually the solid content is 50% or more. Drying is carried out after dehydration by methods such as sun drying, surface drying, hot air drying, and vacuum drying, and drying is usually carried out until the moisture content is 10% or less. The preparations obtained as above are mainly powders,
Although it is used as a tablet, it may be mixed with a substance such as lactose that helps absorption of calcium and also has a shaping effect. Moreover, since the above-mentioned preparation contains high-quality calcium as its main component, when used as a food additive, feed additive, or soil conditioner, it has an extremely large effect on the growth of animals and plants.
Now, an experiment was conducted in which the same amounts of calcium carbonate a, beef bone meal b, oyster shell meal c, calcined beef bone meal d, eggshell meal e, and the formulation f of the present invention were added as calcium to the basic feed, and a feeding test was conducted on rats. explain. The test involved feeding rats with diets containing different calcium sources.
The animals were kept for 24 days and 30 days, and the calcium absorption rate and bone breaking force after slaughter were tested.
As shown in Figures (24th) and Figure 4 (31st). In the figure, the bar graph shows the bone breaking force, and the line graph shows the corresponding calcium absorption rate. As is clear from the figure, the calcium absorption rate and the bone breaking force differ depending on the calcium source, and the present invention formulation f shows excellent results in both cases. The salts containing calcium as a main component of the present invention can be used alone or in combination with lactose, etc., and added as a calcium fortifier to soups, baby foods, candy, and other sweets and foods, or added to feed for livestock and pets. When sprayed on fields as a soil conditioner, it promotes the growth of plants and animals, and is highly effective.
In addition, treated whey from which salts containing calcium as a main component have been removed has a reduced salt content, so it can be used as a raw material for confectionery after being concentrated and dried in the same way as conventional sweet whey. Therefore, when the present invention is applied to acid whey, the acid whey that was conventionally discarded can be fully utilized, making it an extremely useful invention industrially. This will be explained below using examples. Example 1 1250 kg of skim milk was heat sterilized at 95°C for 5 minutes, and after cooling, Str. lactis
and Streptococcus cremoris (Str.
cremoris) mixed starter and heated at 22℃.
Fermented for 16 hours to a pH of 4.5. Next, the curd was crushed, heat sterilized at 62℃ for 2 minutes, and 250 kg of quark and 1000 kg of quark whey (acid whey) were separated using a whey separator, the quark separator (manufactured in West Germany).
I got it. The above quark whey is produced using a plate heat exchanger at 95%
℃, 20% sodium hydroxide solution was added and mixed using a static mixer installed in the piping, and the pH was adjusted to 6.5. After neutralization, the average residence time in the pipe was approximately 2 minutes, and this was sent to 150 hydrocyclones. The average residence time of this liquid cyclone is approximately 6 minutes, and 983 kg of processed whey and insolubilized salt water are processed.
Obtained 17.3Kg. Its composition is as shown in Tables 2 and 3 above. The above-mentioned insolubilized salts were further dehydrated under pressure to form a cake, dried with hot air and pulverized to obtain 2.2 kg of a product containing calcium as the main component and having a moisture content of 2.7%. This product was suitable as a calcium fortifier for baking and confectionery.

[Brief explanation of drawings]

Figure 1 shows the relationship between sedimentation rate of insolubilized salts and heating temperature, Figure 2 shows the insolubilization rate of acid whey PH and salt (mainly composed of calcium), and Figure 3
Figure 4 shows bone breaking force (bar graph) and calcium absorption in rats using calcium carbonate a, beef bone powder b, oyster shell powder c, calcined beef bone powder d, eggshell powder e, and preparation f of the present invention as calcium sources, respectively. It is a figure showing a rate (line graph).

Claims (1)

[Claims] 1. A process of acidifying the milk raw material solution and removing the generated coagulates, and PHing with alkali after removing the coagulates.
Contains salts whose main component is calcium from milk raw materials, which are obtained from the steps of neutralizing to a pH of over 6.0 and below 8.0 and precipitating and separating the salts, and concentrating or drying the separated salts. Calcium fortifier. 2 Acidification is done by adding acid or by lactic acid fermentation.
3.0 to 5.5. A calcium fortifying agent containing salts containing calcium as a main component from a milk raw material according to claim 1.