JPH0717711A - Highly active calcium oxide and powdering agent - Google Patents

Abstract

(57) [Abstract] [Object] The present invention provides a highly active calcium oxide having a high activity that can be made into fine powder without impairing the dissolved component of a hydrous substance and without modifying the dissolved component of the hydrous substance. The purpose is to obtain. [Structure] Highly active calcium oxide obtained by firing egg shells at 900 ° C to 1500 ° C. A powdering agent comprising highly active calcium oxide obtained by firing egg shells at 900 ° C to 1500 ° C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to highly active calcium oxide obtained by treating egg shells at a high temperature. The present invention also relates to a powdering agent composed of highly active calcium oxide obtained by treating egg shells at a high temperature.

[0002]

2. Description of the Related Art Calcium oxide obtained by treating shells at a high temperature has been known. In the industrial production, it is customary to treat shells at 900 ° C to 1000 ° C for production.

[0003]

It has been known that calcium oxide obtained by subjecting the conventional shells to high temperature treatment has improved activity. What kind of activity improvement is conventionally known? It was unknown.

It is also known that when water is added to quicklime (calcium oxide), it becomes slaked lime (calcium hydroxide). If the amount of water added is large, it becomes muddy, and if it is small, it is uneven. It became a powder state and it was difficult to make the whole into a uniform powder.

[0005]

The first invention of the present application is a highly active calcium oxide obtained by baking egg shells at 900 ° C to 1500 ° C. The second invention is that the eggshell is 1200 ° C.
It is a highly active calcium oxide obtained by firing at ~ 1300 ° C. 3rd invention of this application WHEREIN: 900 degreeC-1500 degreeC of eggshell
It is a powdering agent composed of highly active calcium oxide obtained by firing at. Moreover, 4th invention WHEREIN: 1200 degreeC-13 degree
It is a powdering agent composed of highly active calcium oxide obtained by firing at 00 ° C.

The highly active calcium oxide obtained by these inventions of the present application, unlike conventionally known calcium oxide, reacts violently when mixed with a hydrous substance in substantially equal weight ratios, and a dissolved component of the hydrous substance. Without compromising
In addition, the dissolved component of the water-containing material could be made into fine powder without property modification.

Also, the powdering agent of the present invention composed of this highly active calcium oxide also reacts violently when mixed with the hydrous material in approximately equal weight ratios, without impairing the dissolved components of the hydrous material, and The dissolved component of the water-containing material can be made into fine powder without changing the properties.

In the above description, the water-containing material may be any solution containing water or water, and when it does not contain water, such as fats and oils, water may be suspended. Less than,
In the present specification, the term "water-containing material" includes not only water solutions and water-containing materials but also those that do not contain water and can be suspended in water.

[0009] In the above, when the firing temperature is lower than 900 ° C, due to lack of activity, when the obtained calcium is mixed with a water-containing material, the water-containing material becomes a mud and is not finely pulverized. Can not. When calcined at 900 ° C. or higher, the obtained highly active calcium oxide has the above-mentioned activity, and when mixed with a hydrous substance in approximately equal amounts by weight, it reacts violently to dissolve dissolved components of the hydrous substance. It is possible to make fine powder without damaging the dissolved component without modifying its properties. However, when the calcination treatment is performed at 1000 ° C. or lower, the reaction rate when the obtained highly active calcium oxide is mixed with a water-containing substance is slow,
When the baking treatment is performed at a temperature of ℃ or higher, the reaction rate becomes gradually higher than that at a baking temperature lower than this. Meanwhile, 1500 ° C
The reaction rate in the case of the baking treatment at 1 is almost the same as that in the case of the baking treatment at 1300 ° C. Therefore, the temperature for firing the egg shell to obtain the highly active calcium oxide of the present invention is preferably 900 ° C to 1500 ° C. However, the reaction rate when firing at 1500 ° C is
Since there is almost no difference from the case of firing at 1300 ° C, the most preferable upper limit of the firing temperature can be set to 1300 ° C from the viewpoint of efficiency and cost. On the other hand, as the firing temperature increases from 900 ° C,
The reaction rate of the obtained highly active calcium oxide gradually increases, but according to the experiments of the inventor, it is seen from the viewpoint of the reaction rate when the obtained highly active calcium oxide is mixed with a hydrate. Then, the lower limit of the most preferable range of the firing temperature was 1200 ° C.

Further, according to an experiment conducted by the inventor, 1200 ° C.
The highly active calcium oxide obtained at a calcination temperature of ˜1300 ° C. has a stable activity of making the hydrated substance into a fine powder when compared with the highly active calcium oxide obtained by calcination at other temperature ranges. . That is, among the highly active calcium oxides obtained in the present invention, there is one in which the activity of making the hydrated substance into a fine powder becomes unstable as time passes after generation. For example, although it is still possible to pulverize a water-containing material into fine powder, it was used after a certain amount of time had elapsed after the formation, rather than the time required for pulverization if it was used within a short time after the formation. In some cases, the time required for pulverization becomes longer. However, the highly active calcium oxide obtained at a calcination temperature of 1200 ° C to 1300 ° C has a stable activity of pulverizing the hydrous material even after a lapse of time after generation, and is calcined at other temperature ranges. When compared with the highly active calcium oxide of the present invention obtained in this way, this stability was the most excellent.

In the above, the reason why the mixing ratio of the highly active calcium oxide obtained by the present invention or the powdering agent composed of this highly active calcium oxide and the hydrate is approximately equal in weight ratio is the ratio. Is most suitable for accelerating the pulverization reaction, and at such a ratio, the powder obtained by the pulverization reaction can contain the active ingredient such as a hydrous substance most. According to the experiments conducted by the inventor of the present application, the highly active calcium oxide of the present invention or 1 part by weight of the powdering agent composed of this highly active calcium oxide is mixed in the range of about 0.3 to 3.3 parts by weight of the hydrate. A powdering reaction occurred in proportion. This differs depending on the kind of the hydrated substance. For example, in the case of blood, 0.6 to 3 parts of blood are added to 1 part by weight of the highly active calcium oxide of the present invention or a powdering agent composed of this highly active calcium oxide. The powdering reaction occurred at a mixing ratio of about 0.3 part by weight. Also,
In the case of liquid oils and fats, the mixing ratio of the liquid oils and fats in the range of 0.3 to 1.7 parts by weight to 1 part by weight of the highly active calcium oxide of the present invention or the powdering agent composed of this highly active calcium oxide. A powdering reaction occurred at.

[0012]

As described above, the highly active calcium oxide obtained in the present invention and the powdering agent composed of this highly active calcium oxide react rapidly when water is added,
Micronize. This pulverization may be water only,
A more rapid reaction can be seen by adding acidic water (such as wood vinegar). The highly active calcium oxide and the powdering agent composed of the highly active calcium oxide are remarkably effective for powdering viscous liquids such as blood, or liquid oils and fats such as animal oils, vegetable oils and mineral oils. . In addition, it is possible to make fine powder without damaging the dissolved components of the mixed hydrous material and without modifying the properties of the dissolved components of the hydrous material. Therefore, there is a great effect in pulverizing a liquid substance that is difficult to be pulverized while retaining the active ingredient. This pulverization reaction only generates heat of reaction and does not require drying or other operations.

[0013]

Example 1 A white egg shell washed with water was naturally or artificially dried, and 40 kg of this egg shell piece was fired in an electric furnace at 900 ° C. for 5 hours in a ventilated atmosphere (80 cm ³ / min), and then naturally cooled. It was The white egg shell pieces thus obtained after calcination were finely pulverized into powder of 1 mm or less to obtain about 20 kg of highly active calcium oxide.

In the above description, the reason for setting the firing time to 5 hours is that it is necessary to uniformly fire the eggshell pieces in the electric furnace at 900.degree. That is, the firing time is the time required to evenly fire the eggshell pieces in the electric furnace at a constant temperature, and is determined according to the amount of eggshell pieces, the firing temperature, and the like.

The reason why the egg shell pieces after firing were finely pulverized to a powder of 1 mm or less was to ensure that the product formed by the powdering reaction of the obtained highly active calcium oxide was a uniform product. This is also for increasing the reaction speed of powdering.

In order to examine the activity of the produced high-activity calcium oxide, the same amount (100 g, 100 ml) of wood vinegar solution was added to 100 g of high-activity calcium oxide, stirred for 30 seconds and allowed to stand. The wood vinegar slightly floated on the surface of the mud-like mixture with the passage of time, and after 10 minutes of standing, cracks were formed on the surface of the mud-like mixture, water vaporized, and fine powder of Ca was formed.
A combined wood acetic acid powder was created.

When the components of the wood vinegar solution in the fine powder thus obtained were examined, it was recognized as the components of the wood vinegar solution combined with the added highly active calcium oxide.

[0018]

Example 2 A white egg shell washed with water was naturally or artificially dried, and 40 kg of this egg shell piece was placed in a ventilated atmosphere in an electric furnace (8
It was calcined at 0 ° C. ³ / min) at 1000 ° C. for 5 hours and then naturally cooled. The white egg shell pieces thus obtained after calcination were finely pulverized into powder of 1 mm or less to obtain about 20 kg of highly active calcium oxide.

In the above, the reason for setting the firing time to 5 hours is that it is necessary to uniformly fire the eggshell pieces in the electric furnace at 1000.degree.

The reason why the egg shell pieces after firing were finely pulverized to a powder of 1 mm or less was to ensure that the product obtained by the pulverization reaction of the obtained highly active calcium oxide was a uniform product. This is also for increasing the reaction speed of powdering.

In order to examine the activity of the produced high-activity calcium oxide, the same amount (100 g, 100 ml) of wood vinegar solution was added to 100 g of high-activity calcium oxide, stirred for 30 seconds and allowed to stand. The wood vinegar solution floated a little on the surface of the mud-like mixture with the passage of time, and after standing for about 7 minutes, cracks were formed on the surface of the mud-like mixture, the water vaporized, and a momentarily uniform fine powder. A Ca-bonded wood acetic acid powder was prepared.

When the components of the wood vinegar solution in the fine powder thus obtained were examined, it was recognized as the components of the wood vinegar solution combined with the added highly active calcium oxide.

[0023]

Example 3 A white egg shell washed with water was naturally or artificially dried, and 40 kg of this egg shell piece was placed in a ventilated atmosphere in an electric furnace (8
It was calcined at 1100 ° C. for 5 hours at 0 cm ³ / min) and then naturally cooled. The white egg shell pieces thus obtained after calcination were finely pulverized into powder of 1 mm or less to obtain about 20 kg of highly active calcium oxide.

In the above, the reason for setting the baking time to 5 hours is that it is necessary for baking the eggshell pieces in the electric furnace uniformly at 1100.degree.

The reason why the egg shell pieces after firing were finely pulverized to a powder of 1 mm or less was to ensure that the product obtained by the powdering reaction of the obtained highly active calcium oxide was a uniform product. This is also for increasing the reaction speed of powdering.

In order to study the activity of the produced high-activity calcium oxide, the same amount (100 g, 100 ml) of wood vinegar was added to 100 g of high-activity calcium oxide, stirred for 30 seconds and allowed to stand. The wood vinegar solution floated a little on the surface of the mud-like mixture with the passage of time, and after standing for about 7 minutes, cracks were formed on the surface of the mud-like mixture, the water vaporized, and a momentarily uniform fine powder. A Ca-bonded wood acetic acid powder was prepared.

When the components of the wood vinegar solution in the fine powder thus obtained were examined, it was recognized as the components of the wood vinegar solution combined with the added highly active calcium oxide.

[0028]

Example 4 A white egg shell washed with water was naturally or artificially dried, and 40 kg of this egg shell piece was placed in a ventilated atmosphere in an electric furnace (8
It was baked at 1200 ° C. for 5 hours at 0 cm ³ / min) and then naturally cooled. The white egg shell pieces thus obtained after calcination were finely pulverized into powder of 1 mm or less to obtain about 20 kg of highly active calcium oxide.

In the above, the reason for setting the baking time to 5 hours is that it is necessary for baking the eggshell pieces in the electric furnace uniformly at 1200.degree.

The reason why the egg shell pieces after firing were finely pulverized to a powder of 1 mm or less was to ensure that the product obtained by the powdering reaction of the obtained highly active calcium oxide was a uniform product. This is also for increasing the reaction speed of powdering.

In order to examine the activity of the produced highly active calcium oxide, the same amount (100 g, 100 ml) of wood vinegar was added to 100 g of highly active calcium oxide, stirred for 30 seconds and allowed to stand. The wood vinegar solution floated a little on the surface of the mud-like mixture with the passage of time, and after standing for about 6 minutes, cracks were formed on the surface of the mud-like mixture, the water vaporized, and a momentarily uniform fine powder. A Ca-bonded wood acetic acid powder was prepared.

When the components of the wood vinegar solution in the fine powder thus obtained were examined, it was recognized as the components of the wood vinegar solution combined with the added highly active calcium oxide.

[0033]

[Embodiment 5] White eggshells washed with water are naturally dried or artificially dried, and 40 kg of the eggshell pieces are placed in a ventilated atmosphere in an electric furnace (8
It was baked at 1300 ° C. for 4 hours at 0 cm ³ / min) and then naturally cooled. The white egg shell pieces thus obtained after calcination were finely pulverized into powder of 1 mm or less to obtain about 20 kg of highly active calcium oxide.

In the above, the reason for setting the firing time to 4 hours is that it is necessary to uniformly fire the eggshell pieces in the electric furnace at 1300.degree.

The reason why the egg shell pieces after firing were finely pulverized to a powder of 1 mm or less was to ensure that the product obtained by the pulverization reaction of the obtained highly active calcium oxide was a uniform product. This is also for increasing the reaction speed of powdering.

In order to study the activity of the produced high-activity calcium oxide, the same amount (100 g, 100 ml) of wood vinegar was added to 100 g of high-activity calcium oxide, stirred for 30 seconds and allowed to stand. The wood vinegar slightly floated on the surface of the mud-like mixture with the passage of time, and after 6 minutes of standing, cracks were formed on the surface of the mud-like mixture, water evaporated, and fine powder of Ca-bonded wood acetic acid. A powder is formed.

When the components of the wood vinegar solution in the fine powder thus obtained were examined, it was recognized as the components of the wood vinegar solution combined with the added highly active calcium oxide.

Next, only the firing temperature was changed to 1500 ° C.,
Others produced highly active calcium oxide in the same manner as in this example and examined the activity in the same manner as described above.
Even in the case of the high temperature calcination at 0 ° C., there was no difference in the activity from the case of the high temperature calcination at 1300 ° C., and the reaction rates of adding wood vinegar and making it into fine powder were almost the same. Therefore, from the viewpoint of efficiency of generation and cost, the upper limit of the firing temperature is set to 1500 ° C.

[0039]

[Example 6] 100 g of squid liver oil, 20 g of wood vinegar solution and 1
120 g of the highly active calcium oxide powder of the present invention obtained at a firing temperature of 300 ° C. was added, and the mixture was left standing after stirring,
The reaction was completed in 10 minutes, and 230 g of squid liver oil fine powder was obtained.

When the components of this squid liver oil fine powder were analyzed, it was found that all of the following components were contained and that the squid liver oil component was contained almost as it was.

Components contained in squid liver oil fine powder: myristic acid, pentadecanoic acid, palmitic acid, hexadecanoic acid (n-11), hexadecanoic acid (n-5), palmitoleic acid, hexadecanoic acid (n-9), Stearic acid, octadecanoic acid (n-5), octadecanoic acid (n-
7), oleic acid, linoleic acid, linolenic acid, octadecatetraenoic acid (n-3), eicosenoic acid (n-1)
1), eicosenoic acid (n-7), eicosenoic acid (n-
9), eicosagenic acid (n-6), dihomo-γ-linolenic acid, eicosatetraenoic acid (n-3), arachidonic acid, eicosapentaenoic acid, docosenoic acid (n-11),
Docosenoic acid (n-7), erucic acid, docosapentaenoic acid (n-3), docosahexaenoic acid (n-3), tetracosenoic acid (n-9)

Conventionally, powdered calcium oxide and liquid oils and fats alone do not cause a chemical reaction, and liquid oils and fats are simply absorbed by powdered calcium oxides. No oily fat powder could be produced. However, as in this Example, the use of the highly active calcium oxide of the present invention made it possible to easily produce a powder of oils and fats having no stickiness. In addition, this powdering causes a chemical reaction by simply mixing oils and fats with highly active calcium oxide and wood vinegar, so that active processing (eg, mixing, heating, etc.), which is conventionally performed, is performed. Was not needed.

[0043]

Example 7: 120 g of highly active calcium oxide powder of the present invention obtained at a firing temperature of 1200 ° C. in 100 g of oil of heaven
Then, 20 g of water and 20 g of water were put in a container, stirred lightly, and left to stand, and 230 g of fine powder of top-grade oil was formed in 6 minutes.

[0044]

[Embodiment 8] 120 g of highly active calcium oxide powder of the present invention obtained at a firing temperature of 1200 ° C. in 100 g of plastic oil
Then, 20 g of wood vinegar was placed in a container, stirred lightly, and allowed to stand, and 230 g of fine powder of top-grade plastic oil was formed in 3 minutes.

As is clear from Examples 7 and 8, the oil and fat can be powdered by adding either water or wood vinegar to the reaction between the liquid oil and fat and the highly active calcium oxide of the present invention. The powdering reaction was faster with the addition of. This is because fatty acids with a large number of carbon atoms and their ester compounds generally dissolve better in an organic solvent or a solution containing an organic substance (for example, wood vinegar) than in water. Appears to have a faster powdering reaction than when water is used.

Further, from the above Examples 1 to 8, it was found that the highly active calcium oxide obtained in the present invention has an activity of finely pulverizing a water-containing substance and is useful as a powdering agent. did.

[0047]

[Comparative Example 1] White eggshells washed with water were naturally dried, and the eggshell pieces were fired in an electric furnace at 800 ° C for 5 hours in a ventilated atmosphere (80 cm ³ / min), and then naturally cooled. The thus-calcined white eggshell pieces were finely pulverized into powder of 1 mm or less to obtain calcium.

In order to examine the activity of the produced calcium, the same weight of wood vinegar solution was added to calcium, and the mixture was stirred for 30 seconds and allowed to stand. In this case, gas was generated, smelled, and bubbling was observed. Even after the lapse of 24 hours, the wood vinegar and calcium were still separated and could not be pulverized.

From Comparative Example 1, when the firing temperature is 800 ° C., the wood vinegar solution cannot be made into a fine powder when the obtained calcium is mixed with wood vinegar solution due to lack of activity. There was found.

[0050]

[Comparative Example 2] Quick lime (calcium oxide manufactured by Adachi lime Industry Co., Ltd.) obtained by firing limestone at 900 ° C for 5 hours was crushed and added to the same weight of wood vinegar solution, whereupon an exothermic reaction instantaneously occurred and the water content changed. Evaporated. However, it resulted in a heterogeneous mixture of powdered and solidified parts. The solidified portion became a bubble-like bonded solid and turned a little brown, and uniform fine powder could not be obtained as a whole.

Therefore, the reaction between the highly active calcium oxide obtained by the present invention and the wood vinegar solution is completely different from the reaction between known quick lime (CaO) and wood vinegar solution, and the properties of the wood vinegar solution are not modified. It was revealed from this control example 2 that it is an unprecedented chemical change that can be made into a fine powder.

[0052]

[Experimental Example 1] The high activity calcium oxide obtained in the present invention and other calcium were evaluated for their conductivity, color of calcium powder,
When the powdering reaction with wood vinegar was examined, the following results were obtained.

In this experiment, 1300 ° C. and 90
Highly active calcium oxide of the present invention obtained at a calcination temperature of 0 ° C, oyster shell calcium at 1300 ° C and oyster shell calcium obtained at a calcination temperature of 900 ° C, quicklime (manufactured by Adachi Lime Industry), calcium oxide for reagents (Wako Pure) (Medicinal product) was used.

Regarding Electric Conductivity The electric conductivity means an index showing the ease of current flow in the conductor. In this experiment, 1/10000 of each kind of calcium was dissolved in purified water, and the conductivity based on ionic conduction was measured. The difference in the ionization rate of each calcium was judged based on the magnitude of the numerical value. Current nutrition studies show that calcium must be ionized before it can be absorbed. Therefore, the ionization state of each calcium was determined by measuring the conductivity. Experiments revealed that the highly active calcium oxide of the present invention obtained at a firing temperature of 1300 ° C. has the highest conductivity, that is, the ionization rate. Therefore, the highly active calcium oxide of the present invention obtained at the calcination temperature of 1300 ° C. is absorbed in the living body (in the body of livestock etc.) as compared with the oyster shell calcium and other calcium obtained at the calcination temperature of 1300 ° C. It is easy to see that it is in a high working state.

Color of Calcium Powder The colors of various calcium powders were visually observed and compared. The highly active calcium oxide of the present invention is white, while the oyster shell calcium has a light cream color. In addition, quick lime and calcium oxide for reagents are also white, but quick lime looks slightly darker than the highly active calcium oxide and calcium oxide for reagents of the present invention.

Regarding pulverization of wood vinegar, from the viewpoint of pulverization, the highly active calcium oxide of the present invention and the reagent calcium oxide were able to produce a uniform powder, but other calcium gave a uniform powder. Could not be generated.

The results of this experiment are shown in the table below.

[0058]

[Table 1]

[0059]

[Experimental Example 2] Highly active calcium oxide of the present invention obtained at a calcination temperature of 1300 ° C. and quick lime (manufactured by Adachi lime industry) (C
aO 98%), calcium oxide for reagents (manufactured by Wako Pure Chemical Industries)
(CaO 99.9%) was used to investigate the anti-diarrheal effect on the castor oil diarrhea model in rats.

SLC: SD 4 male rats each (4
Weekly, body weight 100g to 150g)
O as shown in the table below: 10 mg / kg, 30 mg / kg, 1
Oral administration of 00 mg / kg, oral administration of physiological saline as a control, and 30 minutes later, oral administration of 1 ml of castor oil, and determination of each antidiarrheal effect at each dose based on the following formula did.

[0061]

[Equation 1]

The measured values and the anti-diarrhea index are shown in Table 2 below.

[0063]

[Table 2]

As a result of this experiment shown in the above table, the anti-diarrhea effect was confirmed for all CaO, but it was derived from the living body called egg shell as compared with quick lime derived from minerals and calcium oxide for reagents. The highly active calcium oxide of the present invention has the strongest antidiarrheal effect, and in the 100 mg / kg administration group, diarrhea did not occur at all within 2 hours.

[0065]

The highly active calcium oxide obtained in the present invention reacts rapidly when water is added,
Micronize. Further, since this highly active calcium oxide has a high activity of making a water-containing substance into a fine powder, it is useful as a powdering agent.

The above fine powder formation may be performed only with water,
A more rapid reaction can be seen by adding acidic water (such as wood vinegar). The highly active calcium oxide and the powdering agent composed of the highly active calcium oxide are remarkably effective for powdering viscous liquids such as blood, or liquid oils and fats such as animal oils, vegetable oils and mineral oils. . In addition, it is possible to make fine powder without damaging the dissolved components of the mixed hydrous material and without modifying the properties of the dissolved components of the hydrous material. Therefore, there is a great effect in pulverizing a liquid substance that is difficult to be pulverized while retaining the active ingredient. This pulverization reaction only generates heat of reaction and does not require drying or other operations.

Claims (4)

[Claims] 1. A highly active calcium oxide obtained by firing egg shells at 900 ° C to 1500 ° C. 2. Highly active calcium oxide obtained by firing egg shells at 1200 ° C. to 1300 ° C. 3. A powdering agent comprising highly active calcium oxide obtained by firing egg shells at 900 ° C. to 1500 ° C. 4. A powdering agent comprising highly active calcium oxide obtained by firing egg shells at 1200 ° C. to 1300 ° C.