WO1994019282A1

WO1994019282A1 - High-activity calcium oxide, powder produced therefrom, process for producing the powder, and powdery preparation

Info

Publication number: WO1994019282A1
Application number: PCT/JP1994/000278
Authority: WO
Inventors: Masashi Shirane
Original assignee: Eisai Co., Ltd.; G & G Co., Ltd.
Priority date: 1993-02-24
Filing date: 1994-02-23
Publication date: 1994-09-01
Also published as: AU6114894A; AU701085B2; KR960700961A; NZ261904A

Abstract

High-activity calcium oxide produced by firing eggshells at 900-1,500 °C. A powdery preparation comprising high-activity calcium oxide produced by firing eggshells at 900-1,500 °C. A discharged animal blood powder produced by reacting discharged animal blood with high-activity calcium oxide produced by firing eggshells at 900-1,500 °C, and a process for producing the powder. A discharged animal blood powder produced by reacting discharged animal blood with high-activity calcium oxide produced by firing eggshells at 900-1,500 °C and an organic acid or a salt thereof, and a process for producing the powder. A fat or oil powder produced by reacting a liquid fat or oil with high-activity calcium oxide produced by firing eggshells at 900-1,500 °C and water or wood vinegar, and a process for producing the powder.

Description

Description Title of the Invention Highly active calcium oxide, powder using the same, method for producing the same, and powdering agent

The present invention relates to a highly active calcium oxide obtained by treating an eggshell at a high temperature. The present invention also relates to a powdering agent comprising a highly active calcium oxide obtained by subjecting an eggshell to a high temperature treatment. C Furthermore, the present invention relates to the use of the highly active calcium oxide to release a large amount of animal waste discharged at a slaughterhouse or the like. Animal blood excretion powder and a method for producing the same for the purpose of powdering blood without denaturing the active ingredient in the blood excretion, and a liquid oil and fat using the highly active calcium oxide The present invention relates to a fat and oil powder for pulverizing oils (animal fats, vegetable fats, mineral fats, etc.) and a method for producing the same. Background art

Conventionally, calcium oxide obtained by treating shells at high temperatures has been known. This was a common practice in industrial production where shells were processed at 900-1000 ° C. It has been known that calcium oxide obtained by high-temperature treatment of shells has improved activity, but it has not been known how much the activity is improved.

Also, when water is added to quick lime (calcium oxide), it becomes slaked lime (calcium hydroxide). It is a known force. When the amount of water is large, it becomes muddy. However, it was difficult to make the whole powder uniform.

Next, various treatment methods have been proposed for animal blood removal, and among these, adsorption drying and vacuum drying have been considered for powdering animal blood removal. According to the conventional technology for pulverizing animal blood, not only large and complicated devices are required but also large expenditures are required for any one of heat, cost, labor and time. It had been. In addition, if the animal blood was left untreated, there were a number of problems, such as spoilage and deterioration resulting in foul odors. Furthermore, although a large number of useful substances are contained during blood removal, the above-mentioned conventional processing method has a problem that this effective component is destroyed and cannot be used effectively.

Conventionally, in order to convert liquid fats and oils into powders, the fats and oils were usually absorbed into the powder.c According to this conventional method, the fats and oils were absorbed into the powder, so the properties as fats and oils remained unchanged. There was a problem in that it was retained and agglomerated during packaging, and the fat and oil powder itself was sticky, resulting in inconvenient SLh during use or I *. For example, if fats and oils in excess of 10% by weight of powder oxidizing powder are absorbed, it becomes a sticky powder and may be aggregated by packaging. In other words, liquid fats and oils alone do not cause a chemical reaction with powdered calcium oxide, and the liquid fats and oils are simply absorbed by the powdered calcium oxide. Is held. Further, there is a problem that it is often difficult to mix the liquid fat and oil uniformly with the powder. Disclosure of the invention

The first invention of the present application is a highly active oxidizing solution obtained by firing an eggshell at 900 ° (up to 150 ° C.). It is a highly active calcium oxide obtained by firing at 300 ° C. Further, a third invention of the present application is a highly active calcium oxide obtained by firing an eggshell at 900 ° C. to 150 ° C. The fourth invention of the present application is a powdering agent comprising a highly active calcium oxide obtained by subjecting an eggshell to a temperature of 1200 ° C. to 130 ° C. The highly active oxidizing solution obtained according to the invention of the present invention is different from the conventionally known calcium oxide in that the weight ratio is approximately equal to that of the hydrated product. When mixed together, they reacted violently, and could be pulverized without damaging the active ingredients of the hydrate and without modifying the properties of the active ingredients of the hydrate. Similarly, the powdering agent of the present invention composed of these highly active calcium oxides reacts violently when mixed with hydrated products in almost equal amounts by weight, without impairing the active ingredients of the hydrated products, and The active ingredient of the product can be pulverized without denaturing.

In the above description, the hydrate may be any one containing an aqueous solution or water, and if it does not contain water, it may be added with water in the case of oils and fats, for example. Hereinafter, in the present specification, the term “hydrated product” includes not only a solution containing an aqueous solution and water, but also a solution containing no water and a mixture of water.

In the above, when the calcination is less than 900, the resulting hydrate becomes muddy when the obtained calcium is mixed with the hydrate because of insufficient activity, and cannot be pulverized. . When calcined at 900 ° C. or higher, the obtained highly active calcium oxide has the above-mentioned activity, and reacts violently when mixed with a hydrated material in substantially equal amounts by weight. It can be pulverized without damaging the active ingredient of the product and without denaturing the active ingredient. However, when the calcination treatment was performed at 1000 ° C. or lower, the reaction rate when the obtained highly active oxidizing water was mixed with the hydrate was slow, and the calcination treatment was performed at 100 ° C. or more. In some cases, the reaction rate becomes progressively faster than at lower firing temperatures. On the other hand, the reaction rate in the case of baking at 1500 ° C. is almost the same as that in the case of baking at 130 ° C. Therefore, the temperature at which the eggshell is fired to obtain the highly active calcium oxide of the present invention is preferably 900 ° C. to 150 ° C. However, 150.000. The reaction rate in the case of baking at C is almost the same as that in the case of baking at 130 ° C., and from the viewpoint of efficiency and cost, the upper limit of the most preferable baking temperature is set to 130 Can be set to. On the other hand, as the firing temperature increases from 900 ° C., Although the reaction rate of the steam gradually increases, according to the experiments of the inventor, from the viewpoint of the reaction rate when the obtained highly active oxidizing water is mixed with a hydrate, the baking treatment is performed. The lower limit of the most preferable range of the temperature was 1200 ° C.

Also, according to the experiments of the inventor, the highly active oxidizing power obtained at a firing temperature of 1200 ° C. to 130 ° C. is high active oxidizing power obtained by firing at another temperature range. Compared with calcium oxide, the activity of pulverizing hydrates is stable. That is, among the highly active calcium oxides obtained by the present invention, there is a highly active calcium oxide whose activity of making water-containing substances into fine powder becomes unstable as time elapses after generation. For example, hydrated materials can still be pulverized, but they are used after a certain amount of time has passed since their generation, rather than the time required for powdering if they are used shortly after generation. In some cases, the time required for pulverization becomes longer. However, 1 2 0 0. The highly active calcium oxide obtained at a calcination temperature of C to 130 has a stable activity of pulverizing hydrates even after a lapse of time after its generation, and has a high activity in other temperature ranges. The stability was the most excellent when compared with the high active oxidizing power calcium of the present invention obtained by firing.

As described above, the highly active calcium oxide obtained by the present invention and the powdering agent composed of the highly active oxidizing powder rapidly react and become fine powder due to the addition of water force. In this fine powder i-Dani, only water may be used, but a more abrupt reaction is seen when acid water (for example, wood vinegar) is added. The highly active calcium oxide obtained by the present invention and the powdering agent composed of the highly active oxidized calcium powder are particularly suitable for powders of viscous liquids such as blood and liquid fats (animal fats, vegetable fats, mineral fats, etc.). This is remarkably effective for the development. In addition, it is possible to pulverize the mixed water-containing active ingredient without damaging the active ingredient, and without changing the properties of the active ingredient of the mixed water-containing substance. Therefore, there is a great effect on powdering a liquid substance, which is difficult to finely powder, while retaining the active ingredient. This pulverization reaction only generates heat of reaction, No other operations need to be added.

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 oxidizing water and the hydrate is almost equal in weight ratio is that such ratio is powdered. This is because it is most suitable for accelerating the reaction, and according to such a ratio, the powder obtained by the pulverization reaction can contain the active ingredient such as a hydrate best. According to the experiment of the inventor of the present invention, about 0.3 to 3.3 parts by weight of a hydrate was contained with respect to 1 part by weight of the highly active calcium oxide of the present invention or 1 part by weight of the powdering agent comprising the highly active oxidizing medium. A powdering reaction occurred in the mixing ratio in the range. This also differs depending on the type of hydrated substance. For example, in the case of blood, the blood 0.6 to 3 parts by weight per 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 a mixing ratio of about 3 parts by weight. In the case of liquid fats and oils, about 0.3 to 1.7 parts by weight of liquid fats and oils per 1 part by weight of the highly active oxidizing solution of the present invention or 1 part by weight of a powdering agent comprising this highly active oxidizing solution. The powdering reaction occurred at a mixing ratio in the range of

The fifth and sixth inventions of the present application are animal blood discharge powders obtained by reacting animal blood discharge with highly active calcium oxide, and a method for producing the same. In the above, the animal bleeding powder is produced by putting animal bleeding and highly active calcium oxide into a reaction tank and stirring and reacting to obtain a powder. Here, animal blood loss and highly active calcium oxide are in a weight ratio of 1: 0.5 to 1.5, or 1: 0.7 to 1.2. Highly active calcium oxide is obtained by firing eggshell at 900 ° C. to 150 ° C. or at 1200 ° C. to 130 ° C.

The seventh and eighth inventions of the present application are directed to an animal blood discharge powder obtained by reacting animal blood discharge, highly active calcium oxide, and an organic acid or a salt thereof, and a method for producing the same. is there. In the above, the perfusion powder is prepared by charging perfusion, highly active calcium oxide, and an organic acid or a salt thereof into a reaction tank, and stirring and reacting to form a powder. It was made. Here, animal blood loss and highly active calcium oxide are in a weight ratio of 1: 0.3 to 1.5, or 1: 0.5 to 1.2. In addition, high active oxidizing power russium makes eggshell 900. It is obtained by firing at C to 1500 ° C or 1200 to 130 ° C. In the above, the organic acid is one of propionic acid, formic acid, malic acid, and lactic acid, and the salt of the organic acid is calcium propionate, sodium propionate, sodium sorbate, ammonium propionate. It is a kind of ammonium formate.

In the above, a sufficient reaction is carried out by mixing animal blood discharge with highly active calcium oxide, or animal blood discharge with highly active calcium oxide and an organic acid or a salt thereof, so that a reactant in a soft and scaly state is obtained. Generated. This product can be powdered by simply crushing, and a powder having a size of about 100 mesh can be obtained. In the above, highly active calcium oxide obtained by firing the eggshell at 900 to 150 or at 1200 to 130 ° C is used. Alternatively, it is possible to use shells and other materials obtained by baking high-temperature materials from which pure calcium can be easily collected. However, care must be taken since sufficient reaction may not occur unless firing at least at 900 ° C h.

In the above, the mixing ratio of animal blood discharge and highly active calcium oxide is such that when animal blood discharge is reacted only with high active oxidizing power calcium, the amount of highly active calcium oxide is 0 per part by weight of animal blood discharge. 5 to 1.5 parts by weight are preferred L, ₀ High active oxidizing power If the ratio of calcium is less than this, powdering reaction does not occur even after a long time after mixing, for example, 24 hours ^ High active oxidizing power If the proportion of calcium is larger than this, no difference is observed in the powdering reaction. Therefore, from the viewpoint of economy, the preferable upper limit of the mixing ratio is 1: 1.5 by weight. According to the experiment of the inventor, the reaction rate, the reaction time, and the product were obtained when 0.7 to 1.2 parts by weight of highly active calcium oxide was mixed and reacted with 1 dragon part of animal blood excretion. It was the best seen from the state. Therefore, judging from these points If the blood excretion of the animal and the highly active calcium oxide are mixed only when the animal exfoliation is reacted with the highly active oxidizing system only, the high active oxidizing system is equivalent to 1 part by weight of the animal bleeding. 0.7 to 1.2 parts by weight is most preferred.

Further, in the above, when the animal excretion is reacted with the highly active calcium oxide and an organic acid or a salt thereof, the mixing ratio between the animal excretion and the highly active calcium oxide is high with respect to 1 part by weight of the animal excretion. The amount of active calcium oxide is preferably from 0.3 to 1.5 parts by weight. If the proportion of the highly active calcium oxide is lower than this, the powdering reaction does not occur even after a long time after mixing, for example, 24 hours. If the proportion of highly active calcium oxide is higher than this, there is no difference in the pulverization reaction. Therefore, from the viewpoint of economy, the preferred upper limit of the mixing ratio is heavy ffit, 1: 1.5. Becomes Further, in order to complete powderization within a relatively short time after mixing, it is preferable that the high-active oxidizing water is 0.5 parts by weight or more per 1 part by weight of blood. As described above, from the viewpoint of the reaction rate, reaction time, and product state, it is most preferable that the ratio of highly active calcium oxide be 0.7 to 1.2 parts by weight with respect to 1 part by weight of animal blood excretion. preferable.

It is possible to lower the mixing ratio of highly active calcium oxide by allowing an organic acid or a salt thereof to participate in this reaction rather than by reacting animal blood with only highly active calcium oxide. This may be because highly active calcium oxide is alkaline, while organic acids or their salts are acidic.

The acid may be added as long as it is an acid. Particularly, an organic acid or a salt thereof is preferable. The organic acid or salt thereof to be added is not particularly limited. ^ Animal blood sample powder can be used for feed or fertilizers.For example, the type of organic acid or salt to be added may be determined in consideration of the use of such product animal blood sample powder. it can. For example, when the product animal blood bleeding powder is used for feed, the specified organic acids and salts thereof can be added to the feed additive. In this case, as the organic acid, propionic acid, formic acid, malic acid, lactic acid and the like can be added, and as the salt of the organic acid, Calcium propionate, sodium propionate, sodium sorbate, ammonium propionate, ammonium formate, etc. can be added.

The mixing ratio of the organic acid or its salt, yo if 0.1 part by weight or more relative to the total weight of the animal waste blood and highly active oxidation of calcium to be mixed L, ₀

In the above-mentioned production method, the stirring performed after being charged into the reaction vessel is not always essential, but it is preferable to perform slow stirring in order to uniformly mix the blood discharge and the highly active calcium oxide. .

In the above, when excretion and highly active calcium oxide are added and mixed, or when excretion and highly active calcium oxide and an organic acid or a salt thereof are added and mixed, an exothermic reaction starts rapidly after several minutes to several tens of minutes. After a few minutes to tens of minutes, a soft and scum-like reactant is formed. The resulting reactant can be ground very easily. Therefore, the powdered product is formed by simply pulverizing the reaction product without using any drying means, etc. be able to. However, the above-mentioned reaction speed time differs depending on ^ of the outside air, and a difference of several hours occurs particularly in summer and winter.

In the blood-discharge powder thus obtained, the active component of blood-discharge is held without any property modification.

Therefore, it is possible to easily process a large amount of blood bleeding which has been difficult to treat in the past, and the processed product contains various nutrients and can be made into powder or granules. , And fertilizer. In addition, according to the method of the present invention, a large amount of kinetic blood is easily and quickly pulverized, so that the blood removal process Si has a remarkable effect. In addition, there is no risk of secondary pollution (for example, generation of offensive odor) during processing, and since the product is a powder, there is no risk of deterioration even if it is kept as it is, and granulation and other processing are easy. There is also an effect.

According to the present invention, blood discharge that is hard to be powdered by ordinary heat dehydration, etc., is extremely tolerable. It can be manufactured easily and without using complicated equipment and heat. Also, during the production, only heat of reaction is generated, and no means such as heating is added, so that the active ingredient in the blood bleeding is retained almost as it is without undergoing property modification.

During blood removal, active ingredients such as calcium, iron, and various vitamins are contained. If this is treated according to the present invention before coagulation, the various active ingredients are retained as they are without undergoing property modification. Not only is it stabilized by powdering, it does not deteriorate under normal storage conditions. Therefore, it is effective to use the blood discharge powder obtained by the present invention for feed, fertilizer, and the like. Further, in the method of the present invention, 5 to 10% of an effective crude drug liquid or wood vinegar solution is added to and mixed with highly exfoliated animal blood before being reacted with calcium oxide, and this is mixed with highly active calcium oxide. By mixing and reacting with calcium oxide and pulverizing, the new feed L, which promotes the utilization of blood, can provide materials for fertilizer. In addition, it is easy to mix other active substances into the blood powder obtained by the present invention, so that the present invention provides a simple method of using animal blood removal. Also. For example, the produced animal blood drainage powder can be mixed with other medicinal materials (eg, wood vinegar powder) and used as a nutrient for humans and animals, or used as a plant activator.

The ninth and tenth inventions of the present application are a fat and oil powder comprising a reaction product of a liquid fat and oil, highly active calcium oxide and water or wood vinegar, and a method for producing the same. In the above, the fat and oil powder is produced by mixing a liquid fat and oil, highly active calcium oxide, and water or wood vinegar to form a powder. Here, 0.6 to 3.0 parts by weight of highly active calcium oxide and 0.1 to 1.0 parts by weight of water or wood vinegar are mixed with 1 part by weight of liquid fats and oils. . Highly active calcium oxide is obtained by calcining eggshell at 900 ° C. to 150 ° C. or at 1200 ° C. to 130 ° C. As the liquid fats, animal fats, vegetable fats, mineral fats and the like can be used. In the conventional technology, a chemical reaction occurs only with powdered calcium oxide and liquid fats and oils. Liquid oils and fats are not rubbed, they are simply absorbed by powdered calcium oxide, so the properties of the oils and fats are preserved as they are, so the force that retains adhesiveness Highly active calcium oxide of the present invention According to the above-mentioned method using, a powder of fats and oils without stickiness could be easily produced. According to the present invention, the oil and fats, the powdered highly active calcium oxide, and water or wood vinegar are chemically mixed to cause a chemical reaction, so that active processing (for example, mixing, adding Temperature, etc.) are not required. In the above, when the amount of water or wood vinegar is less than 10% by weight with respect to the fats and oils, the product becomes clay-like (sticky state) rather than powder. On the other hand, when the amount of water or wood vinegar exceeds 100% by weight of the fats and oils, the product is not in the form of powder but in the form of clay (having a sticky state), which is not preferable.

In the above, it was recognized that the highly active calcium oxide needed to be adjusted to 60% by weight with respect to fats and oils. If the amount is less than this, a favorable powdering reaction is difficult to occur, which is not preferable. According to experiments, even when the amount of highly active calcium oxide is larger than the sum of fats and oils and 10% by weight or more of water or wood vinegar, this amount of highly active calcium oxide corresponds to this amount. It was found that if there was enough water or wood vinegar, a sufficient reaction would take place, and oil and fat powder would be generated. Therefore, when the amount of the highly active calcium oxide and the amount of the water or wood vinegar are appropriate, for example, when the ratio is 1 to 1, the amount of the fats and oils is 10% by weight or less. Even then, there is no special restriction, the reaction takes place sufficiently, and a fat or oil powder is produced. However, if the amount of highly active calcium oxide increases and the amount of water or wood vinegar increases accordingly, the proportion of fats and oils will naturally decrease, and the proportion of fats and oils in the produced fat and oil powder will inevitably increase. Become smaller. If the proportion of the fats and oils in the produced fat and oil powders is below a certain level, there will be no demand, so the upper limit of the amount of highly active calcium oxide is determined economically (or as a commercial need). This upper limit is 300% by weight with respect to fats and oils.

In the above, either water or wood vinegar may be added.

0 Higher fatty acids and their ester compounds are more soluble in organic solvents or solutions containing organic substances (eg wood vinegar) than in water. Therefore, it was recognized that the reactivity of powdering was faster when wood vinegar was used than when water was used.

Here, as described in the invention of the highly active calcium oxide, the fine powder produced by using the highly active calcium oxide has the active ingredient of fats and oils as it is. . In addition, when a wood vinegar solution is used for the reaction, the wood fat component contains the wood vinegar liquid component almost as it is.

In the above, highly active calcium oxide obtained by baking eggshells at 900 ° C. to 150 ° C. or at 1200 ° C. to 130 ° C. is used. Alternatively, it is possible to use shells and other materials obtained by baking at a high temperature a material from which pure calcium can be easily collected. However, care must be taken since sufficient reaction may not occur unless firing at least at 900 ° CRi :. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, preferred embodiments of the present invention will be described.

Fiber example 1)

Washed white eggshell was naturally dried or Λ drying, the egg shell piece 4 OKG in an electric furnace, in air atmosphere of (8 0 cm ³ min), then baked 9 0 0 5 hours, then allowed to naturally cool . The baked white eggshell pieces thus obtained were finely pulverized into powder of one leg 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 eggshell pieces in an electric furnace at 900 ° C. In other words, the firing time is the time required for uniformly firing eggshell pieces in an electric furnace at a constant temperature, and is determined according to the amount of eggshell pieces, the firing temperature, and the like.

Also, the reason why the eggshell pieces after firing were finely pulverized into powders that are less The purpose is to make the product produced by the powdering reaction of calcium iodide into a uniform product, and to increase the reaction speed of the powdering.

In order to examine the activity of the generated highly active calcium oxide, the same amount (100 g, 100 ml) of wood vinegar was added to 100 g of the highly active calcium oxide, and the mixture was stirred for 30 seconds. , And left still. With the passage of time, the wood vinegar liquid floats on the surface of the muddy mixture, and after standing for 10 minutes, cracks are formed on the surface of the muddy mixture, the water evaporates, and the Ca bond of the fine powder Wood acetic acid powder was obtained.

When the components of the wood vinegar solution in the fine powder thus obtained were examined, they were found to be components of the wood vinegar solution combined with the added highly active calcium oxide.

(Example 2)

The washed white eggshell dried naturally or artificially dried, and fired the eggshell piece 4 0 kg ventilation棼囲vaporized in an electric furnace ^{(8 0 cm 3 Z min)} 5 hours 1 0 0 0 ° C in, then, natural Allow to cool. The fired white eggshell pieces thus obtained were finely pulverized into powder of one thigh 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 eggshell pieces in an electric furnace at 100 ° C.

The reason why the eggshell pieces after firing were pulverized into powders of one thigh or less was to make the product obtained by the powdering reaction of the obtained highly active calcium oxide into a uniform product. Yes, in order to increase the powdering reaction rate.

To examine the activity of the highly active calcium oxide produced, add the same amount (100 g, 100 ml) of wood vinegar to 100 g of highly active calcium oxide and stir for 30 seconds. , And left still. With the passage of time, the wood vinegar slightly floats on the surface of the muddy mixture, and after standing for about 7 minutes, cracks are formed on the surface of the muddy mixture, moisture evaporates, and instantaneous uniform fine powder A carbon-bonded acetic acid powder was formed.

When the components of the wood vinegar solution in the fine powder thus obtained were examined, the added highly active acid was added.

Two It was recognized as a component of the wood vinegar solution combined with calcium iodide.

(Example 3)

The washed white eggshell dried naturally or artificially dried, and fired the eggshell piece 4 O kg ventilation atmosphere of an electric furnace (8 0 cm ³ min) 5 hours 1 1 0 0 ° C in, then, naturally cooled I let it. The baked white eggshell pieces thus obtained were finely pulverized into powder of 1 liter or less to obtain about 20 kg of highly active calcium oxide.

In the above, the reason why the firing time is set to 5 hours is that it is necessary to uniformly fire the eggshell pieces in the electric furnace at 110 ° C.

The reason why the eggshell pieces after firing were pulverized into powders of 1 liter or less was to make the product obtained by the powdering reaction of the obtained highly active calcium oxide into a uniform product. This is for increasing the reaction speed of powdering.

In order to examine the activity of the generated highly active calcium oxide, the same amount (100 g, 100 ml) of wood vinegar was added to 100 g of the highly active calcium oxide, and the mixture was stirred for 30 seconds. And left still. With the passage of time, the wood vinegar slightly floats on the surface of the muddy mixture, and after standing for about 7 minutes, cracks are formed on the surface of the muddy mixture, moisture evaporates, and instantaneous uniform fine powder A carbon-bonded acetic acid powder was formed.

(Example 4)

It washed white eggshell was naturally dried or Λ dried, and fired the eggshell piece 4 0 kg ventilation atmosphere of an electric furnace ^{(8 0 cm 3 / min)} 5 hours 1 2 0 0 ° C in, then, naturally cooled I let it. The baked white eggshell pieces thus obtained were finely pulverized into powder of one leg or less to obtain about 20 kg of highly active calcium oxide.

In the above, the reason why the firing time is set to 5 hours is that it is necessary to uniformly fire eggshell pieces in an electric furnace at 1200.

Three The reason for crushing the eggshell pieces after baking into powder of not more than 1 band is to ensure that the product produced by the powdering reaction of the obtained highly active oxidizing powder becomes a uniform product. This is also to increase the reaction speed of the powder powder.

In order to examine the activity of the obtained highly active oxidizing solution, the same amount (100 g, 100 Oml) of narcotics was added to 100 g of the highly active oxidizing solution, and 30 The mixture was stirred for 2 seconds and allowed to stand. Wood vinegar slightly floats on the surface of the mud-like mixture with the passage of time, and after about 6 minutes after standing, cracks are formed on the surface of the mud-like mixture, moisture evaporates, and instantaneous uniform fine powder A carbon-bonded acetic acid powder was formed.

Examination of the components of the wood vinegar solution in the fine powder obtained in this way revealed that the components of the wood vinegar solution were combined with the added highly active calcium oxide.

Nada example 5)

Washed white eggshell was naturally dried or Λ dried and calcined for 4 hours at this eggshell pieces 4 0 kg 1 3 0 0 in air atmosphere of (8 0 cm ³ / min) in an electric furnace, then natural cooling I let it. The baked white eggshell pieces thus obtained were finely pulverized into powders of less than 1 liter to obtain about 20 kg of highly active calcium oxide.

In the above, the reason why the firing time is set to 4 hours is that it is necessary to uniformly fire the eggshell pieces in the electric furnace at 130 ° C.

The reason why the eggshell pieces after firing were pulverized into powders of one thigh or less was to make the product produced by the powdering reaction of the obtained highly active calcium oxide into a uniform product. Also, it is for increasing the reaction speed of the powdered sword.

In order to examine the activity of the generated highly active calcium oxide, the same amount (100 g, 100 ml) of wood vinegar was added to 100 g of the highly active calcium oxide, and the mixture was stirred for 30 seconds. , And left still. With the passage of time, the wood vinegar slightly floats on the surface of the muddy mixture, and after standing still for 6 minutes, cracks are formed on the surface of the muddy mixture, moisture evaporates, and fine powdered Ca-bonded wood Acetic acid powder was formed.

Four When the components of the wood vinegar solution in the fine powder thus obtained were examined, they were found to be components of the wood vinegar solution combined with the added highly active calcium oxide.

Next, only the firing temperature was changed to 150 ° C., and high-activity calcium oxide was produced in the same manner as in this example, and the activity was examined in the same manner as described above. Even in the case of firing at a high temperature of ° C, there was no difference in activity between the case of firing at a high temperature of 130 ° C and the reaction rate for adding the wood vinegar solution to make fine powder was almost the same. Therefore, the upper limit of the sintering temperature was set to 150 ° C for the sake of efficiency and economical efficiency.

(Comparative Example 1)

The washed white eggshell was air-dried, and the eggshell piece was fired in an electric furnace at 800 ° C. for 5 hours in a ventilated atmosphere (80 cm ³ / min), and then naturally cooled. The baked white eggshell pieces thus obtained were finely pulverized and powdered into one leg or less to obtain calcium. To examine the activity of the resulting calcium, the same weight of wood vinegar was added to calcium, stirred for 30 seconds, and allowed to stand. In this case, gas was generated, smelling, and foaming was observed. After 24 hours, the wood vinegar solution and calcium were still separated, and powder filing could not be performed.

According to Comparative Example 1, when the calcination temperature is 800, the resulting calcium cannot be finely powdered when the obtained calcium is mixed with the wood vinegar due to insufficient activity. There was found.

(Comparative Example 2)

Quicklime (calcium oxide manufactured by Adachi Lime Industry Co., Ltd.), which was obtained by calcining limestone at 900 ° C for 5 hours, was pulverized and poured into wood vinegar of the same weight. did. However, a heterogeneous mixture of the powdered and solidified parts was obtained. The solidified portion became a foam-like bonded solid, turned slightly brown, and could not be uniformly pulverized as a whole.

Therefore, the reaction between the highly active calcium oxide obtained according to the present invention and the wood vinegar solution

Five This is an unprecedented chemical modification that is completely different from the reaction of known quick lime (C a O) with wood vinegar, which allows the wood vinegar to be finely powdered without denaturing its components. This was evident from Control Example 2.

(Experimental example 1)

The highly active calcium oxide obtained according to the present invention and other calcium were examined for their electrical conductivity, color of calcium powder, and powdering reaction with wood vinegar. The following results were obtained.

/ 0

In this experiment, the books obtained at a firing temperature of 1300 ° C and 900 ° C were used. Oyster shell calcium and quicklime (made by Adachi Lime Industry Co., Ltd.) obtained at a firing temperature of 00 ° C were used.

① About conductivity

The conductivity means an index indicating the ease of current flow in a conductor. In this experiment, various kinds of calcium of 1Z1000 were respectively dissolved in purified water, and the conductivity based on ionic conduction was measured. The difference in the ionization rates of various calcium was determined based on the magnitude of the numerical value.

Current nutrition has shown that calcium cannot be absorbed unless it is ionized. Therefore, the ionization state of various calcium was determined by measuring the conductivity. According to experiments, 1 3 0 0. It was found that the highly active calcium oxide of the present invention obtained at the firing temperature of C had the highest conductivity, that is, the highest ionization rate.

Therefore, the highly active calcium oxide of the present invention obtained at a firing temperature of 130 ° C. is more in vivo (livestock) than oyster shell calcium and other calcium obtained at a firing temperature of 130 ° C. You can see that the body is easily absorbed and works well.

②About the color of calcium powder

The colors of various calcium powders were visually observed and compared.

6 The highly active oxidizing calcium of the present invention is white, but the calcium calcium is light L and has a cream color. In addition, quicklime also has a white color, and quicklime looks slightly darker than the highly active oxidizing solution of the present invention.

③ Powdering of wood vinegar

From the viewpoint of powdering, the highly active calcium oxide of the present invention was able to produce a uniform powder, but other calcium could not produce a uniform powder. The results of this experiment are shown in Table 1 below.

7 Calcium conductivity Calcium Type of calcium powder and wood vinegar (*) Color of powder State after powdering reaction

Highly active oxidation 0.664 ms / cm White Clean uniform fine powder

Calcium

(1300Ϊ)

Highly active oxidation 0.411 ms / cm White Clean uniform fine powder

Calcium

(900

Oyster grain calm 0.523 ms / cm Light cream color

(1300Ό

Oyster shell cal 0.427 ms / cm Light cream color

(Spirit)

Quicklime 0.30 ms / cm White color Foamed granular solids and non-granulated parts were present, making it impossible to obtain a uniform powder as a whole

(*: 1000-fold dilution with purified water)) (Experimental example 2)

Highly active calcium oxide of the present invention obtained at a firing temperature of 130 ° C., quicklime (made by Adachi Lime Industry Co., Ltd.) (Ca098%), oxidizing agent for reagents (made by Wako Pure Chemical Industries) (C a O

The anti-diarrheal effect on castor oil diarrhea model in rats was examined using 99.9%).

8 SLC _: 4 male SD rats (4 weeks old, body weight 100g-150g) were orally administered the above three types of CaO at 1 OmgZkg, 3 Omg / kg.10 Omg / kg as shown in the table below, In addition, physiological saline was orally administered as a control, lml of castor oil was orally administered 30 minutes later, and the antidiarrheal effect of each dose was determined based on the following formula.

Formula Onset time of diarrhea in sample Z Total fecal volume

-= Anti-diarrheal index

Time of onset of control diarrhea Z Total stool volume

(Note: The anti-diarrheal index of the control is 1.) The measured values and the anti-diarrheal index are shown in Table 2 below.

9 Table 2

As a result of this experiment shown in Table 2 above, anti-diarrheal effect was confirmed for all Ca0, but it was derived from eggshell organisms compared to mineral-derived quicklime and calcium oxide for reagents. The highly active oxidizing power of the present invention has the strongest anti-diarrheal effect, especially in the 100 mgZkg administration group, no diarrhea occurred within 2 hours.

(Example 6)

When 200 g of blood excretion from pigs obtained at the slaughterhouse and 200 g of highly active calcium oxide obtained by growing eggshell were put into a reaction tank and slowly stirred, 300 g React after ~ 40 minutes Was started, and the reaction was completed in 10 to 15 minutes thereafter. Since the reaction temperature was 80 ° C. to 100 ° C., evaporation of water was observed. This was left at room temperature, and a dark green (moss green) soft reactant was produced in 30 to 60 minutes. This product was easily crushed and powdered, and about 320 g of powder having a size of about 100 mesh was obtained.

When the obtained powder was analyzed, the results shown in Tables 3, 4 and 5 below were obtained.

Table 3 Blood meal analysis

Note 1. Nitrogen / protein conversion factor: 6.25

Note 2 · Measurement conditions: Temperature, 800 ^: ® »

Two Table 4 Amino acid analysis

Note 1. After performing formic acid oxidation, hydrolyze with hydrochloric acid and measure C Table 5 Inorganic analysis

In other words, according to the results of this analysis, it was found that the active ingredient contained in the bleeding of pigs was substantially contained in the powder without undergoing any property change.

The above-mentioned stirring in this example was performed using a normal vertical stirrer at 60 rotations for 1 minute, and it was confirmed that a sufficient mixing state was obtained within 10 minutes. In the case of visual observation, the stirring may be terminated in a state where the reaction is started uniformly in each part.

The highly active calcium oxide used in this example was produced as follows. The washed white eggshell dried naturally or artificially drying, the egg shell pieces 4 O kg was calcined electric furnace in air棼囲vaporization (8 O cm ³ min) 5 hours 9 0 0 ° C in, then allowed to naturally cool Was. The baked white eggshell pieces thus obtained were pulverized into powder of one thigh or less to obtain about 2 O kg of highly active calcium oxide. In the above, the baking time was set to 5 hours because it is necessary to uniformly bake the eggshell pieces in an electric furnace at 900 ° C. The reason for pulverization into powder is to make the product obtained by the pulverization reaction of the obtained highly active oxidizing agent into a homogeneous product, and to shorten the reaction time of the pulverization. (Example 1)

0.1 kg of wood vinegar solution and 10 kg of charcoal powder as a bulking agent were added to l kg of the blood discharge powder obtained in Example 6, and the mixture was mixed. 3 granules were obtained. By granulating in this way, the blood discharge powder can be mixed with the feed or the like at an accurate ratio. When this granular material is mixed into feed, for example, 0.1 to 1% by weight is added.

(Example 7)

When 200 g of blood excreted from pigs obtained at the slaughterhouse and 2000 g of oxidizing power lucidum obtained by baking shells (oyster shells) at high temperature were put into a reaction tank and slowly stirred. The reaction was started after 0 to 40 minutes, and was completed in about 15 minutes thereafter. When this was left at room temperature, a dark green (moss green) soft reactant was produced in 30 to 60 minutes. This ^^ product could be powdered as easily as crushed, and about 3200 g of powder with a size of 100 mesh ^ was obtained.

Analysis of the resulting powder showed that the active ingredient contained in the pig's bleeding was substantially retained in the powder without undergoing property modification.

The highly active oxidizing calcium used in this example was produced as follows. The washed shells are air-dried or 、 -dried, and 40 kg of the shell pieces are ventilated in an electric furnace and subjected to gasification (80 cm ³ Zmin) to 100 000. It was baked at C for 5 hours and then cooled naturally. The thus-obtained shell pieces after the calcination treatment were finely pulverized into powder of one thigh 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 shell pieces in an electric furnace at 100 ° C. The reason for crushing the shell pieces after firing into powders of one thigh or less is to make the ^^ products produced by the powdering reaction of highly active oxidizing calcium into uniform products. This is to make the reaction time of the powdering shorter.

From this example, powdering reaction also occurs in calcium oxide obtained by treating shells at high temperature. It was found that some of them had an activity of causing

(Experimental example 3)

Highly active calcium oxide of the present invention (obtained by baking eggshell at 125 ° C.) and rat blood (rat is SLC: SD male rat, 6 weeks old, body weight 250 g to 30 g 0 g) ¾r was used.

5 ml (approximately 5 g) of the blood of the rat and 5 g, 3.5 g, 2.5 g, 1.5 g, and 0.5 g of the highly active calcium oxide were mixed and stirred, and the reaction was started. Observation of the powder properties after and 24 hours gave the results shown in Table 6 below.

Table 6

Fiber: As a result of this experiment, it was found that the mixing ratio of animal blood and highly active calcium oxide should preferably be 0.5 parts by weight or more of high active calcium oxide per 1 part by weight of animal blood. did. In addition, in order to complete powdering in a relatively short time after the reaction, it was found that the content of the highly active calcium oxide was more preferably 0.7 part by weight or more.

(Experimental example 4)

Compounding and stirring under the same conditions as in Experimental Example 3 above, adding 0.1% by weight of calcium propionate to each sample, and observing the powder properties 4 hours and 24 hours after the start of the reaction. Was compared with the result. The results are shown in Table 7 below. Table 7

Result: By adding 0.1% by weight of calcium propionate, powdering was performed even when the mixing ratio of the highly active calcium oxide was smaller than in the case of Experimental Example 3. In addition, the time required for powdering has been shortened.

(Experimental example 5)

Compounded and stirred under the same conditions as in Experimental Example 3 above, added 0.5% by weight of sodium sorbate to each sample, and observed the powder properties 4 hours and 24 hours after the start of the reaction. Was compared with the result. The results are shown in Table 8 below. ¹

Table 8

Result: By adding 0.5% by weight of sodium sorbate, powder slurries were performed even when the mixing ratio of the highly active calcium oxide was smaller than in the case of Experimental Example 3. Also, the time required for powdering has been reduced.

m: Highly active calcium oxide is propionic acid because it has strong acidity If a small amount of an organic acid salt such as calcium or sodium sorbate or an organic acid is added, the amount of the highly active calcium oxide required for powdering can be reduced, and the time required for powdering can be shortened.

In other words, the mixing ratio of animal blood excretion to highly active calcium oxide is such that, with the addition of organic acid salts such as calcium propionate and sodium sorbate, the amount of highly active calcium oxide is 0.3 parts by weight or more is preferable, and from the viewpoint that powdering is completed within a relatively short period of time after the start of the reaction, 0.5 parts by weight J¾ ± is more preferable. found.

(Release 8)

To 100 g of squid liver oil, 20 g of wood vinegar solution and 120 g of the highly active oxidizing powder of the present invention obtained at a firing temperature of 130 ° C. were added, and allowed to stand after stirring. However, the reaction was completed in 10 minutes, and 230 g of squid liver oil fine powder was obtained.

An analysis of the components of the fine powder of coconut oil revealed that all of the following components were contained, and that the squid liver oil component was contained almost as is.

Ingredients contained in squid liver oil fine powder;

Myristic acid, pentadecanoic acid, panolemitic acid, hexadecanoic acid (n-11), hexadecanoic acid (n-5), palmitoleic acid, hexadecanoic acid (η-9), stearic acid, octadecanoic acid (n- 5), octadecanoic acid (n-7), oleic acid, linoleic acid, linolenic acid, octadecatetraenoic acid (n-3), eicosenoic acid (n-11), eicosenoic acid (n-7), Eicosenoic acid (n-9), eicosadinoic acid (n-6), dihomo-linolenic acid, eicosatetraenoic acid (n-3), arachidonic acid, eicosapentaenoic acid, docosenoic acid (n-11), dococene Acid (n-7), erucic acid, docosapentaenoic acid (n-3), docosahexaenoic acid (n-3), tetra: 3 senic acid (n-9) Conventionally, powdered calcium oxide and liquid fats and oils alone do not cause a chemical reaction, and liquid fats and oils are simply absorbed by powdered oxidized calcium, so the tackiness of the fats and oils is preserved as it is L, no fat or oil powder could be produced. However, using the highly active calcium oxide of the present invention as in this example, powders of fats and oils having no tackiness could be easily produced. In addition, since the powdering is a chemical reaction simply by mixing oils and fats with highly active calcium oxide and wood vinegar, active processing (eg, mixing, heating, other ) Was not needed.

(Example 9)

Tenbra oil to 100 g, 1 200 g. Place 120 g of the highly active calcium oxide powder of the present invention obtained at the calcination temperature of C and 20 g of water in a container, stir gently, and leave to stand. 230 g of powder were obtained.

(Example 10)

Put 100 g of Tenbra oil, 120 g of the highly active calcium oxide powder of the present invention obtained at a firing temperature of 1200 ° C., and 20 g of wood vinegar in a container, and gently stir. After that, the mixture was allowed to stand, and in 3 minutes, 230 g of fine powder of Tenbra oil was formed.

As is clear from Examples 9 and 10, the oils and fats can be powdered by adding either water or wood vinegar to the reaction between the liquid oil and the highly active calcium oxide of the present invention. The powdering reaction was faster with the addition. This is because fatty acids with a high number of carbon atoms and their ester compounds are more soluble in organic solvents or solutions containing organic substances (eg, wood vinegar) than in water. In this case, it seems that the reaction for powdering is faster than when water is used.

Further, from the above Examples 1 to 10 and Experimental Examples 1 and 3 to 5, the highly active calcium oxide obtained by the present invention does not impair the hydrated active ingredient and the active ingredient of the hydrated product. Has the activity of pulverizing without denaturing, It was found to be useful as a powdering agent.

(Comparative Example 3)

In 100 g of Tenbra oil, 110 g of powdered highly active oxidized calcium and 10 g of water were placed in a container, stirred, and allowed to stand.After 15 minutes, the reaction was terminated. The product was a viscous powder, as if it were clay.

This indicates that there is a boundary where the powdering reaction can occur when the weight ratio of oils and fats to water becomes 1: 0,1.

(Comparative Example 4)

In 100 g of Tenbra oil, 200 g of powdered highly active calcium oxide and 100 g of wood vinegar solution were placed in a container, stirred, and left to stand.The reaction was completed in 1 minute. 350 g of fine powder was obtained.

This indicates that where the weight ratio between the fats and oils and the wood vinegar liquid is in a 1: 1 relationship, a powdering reaction can occur.

Claims

The scope of the claims

1. Highly active calcium oxide obtained by baking eggshells at 900 ° C to 150 ° C.

2. One hundred two eggshells. C-1300. Highly active calcium oxide obtained by firing with C.

3. Powdering agent consisting of highly active calcium oxide obtained by baking eggshell at 900 ° C to 150 ° C.

4. Powdering agent consisting of highly active calcium oxide obtained by baking eggshell at 1200 ° C to 130 ° C.

5. An animal blood drainage powder obtained by reacting animal blood drainage with highly active calcium oxide.

6. The animal blood excretion powder according to claim 5, wherein the highly active calcium oxide is obtained by baking the eggshell at 900 ° C. to 150 ° C.

7. Animal blood sample powder obtained by reacting animal blood sample with highly active calcium oxide and an organic acid or a salt thereof.

8. The animal blood excretion powder according to claim 6, wherein the highly active calcium oxide is obtained by baking the eggshell at 900 ° C. to 150 ° C.

9. The blood perfusion powder according to claim 6, wherein the organic acid is one of propionic acid, formic acid, malic acid, and lactic acid.

10. The animal blood excretion according to claim 6, wherein the salt of the organic acid is one of calcium propionate, sodium propionate, sodium sorbate, ammonium propionate, and ammonium formate. Powder.

1 1. A method for producing animal blood excretion powder, which comprises introducing animal blood excretion and highly active calcium oxide into a reaction tank and stirring and reacting to produce a powder.

12. The method for producing animal blood-discharge powder according to claim 11, wherein the blood discharge of the animal and the highly active calcium oxide are in a weight ratio of 1: 0.5 to 1.5.

13. The method for producing a blood powder according to claim 11, wherein the highly active calcium oxide is obtained by baking the eggshell at 900 ° C. (up to 150 ° C.). .

1 4. A method for producing animal blood exudation powder, which comprises introducing animal blood excretion, highly active calcium oxide, and an organic acid or a salt thereof into a reaction tank, and stirring and reacting to produce powder.

15. The method for producing animal blood excretion powder according to claim 14, wherein the weight ratio between animal blood excretion and highly active calcium oxide is 1: 0.3 to 1.5.

16. The method for producing a blood powder according to claim 14, wherein the highly active calcium oxide is obtained by baking the eggshell at 900 ° C. to 150 ° C. .

17. The method according to claim 14, wherein the organic acid is one of propionic acid, formic acid, malic acid, and lactic acid.

18. The animal waste according to claim 14, wherein the salt of the organic acid is one of calcium propionate, sodium propionate, sodium sorbate, ammonium propionate, and ammonium formate. Method for producing blood powder.

1 9. Oil and fat powder consisting of the reaction product of liquid oil and fat with highly active calcium oxide and water or wood vinegar.

200. Highly active calcium oxide, 900 for eggshell. The fat and oil powder according to claim 19, obtained by calcining at C to 150 ° C.

2 1. A method for producing fats and oils, characterized by adding a highly active calcium oxide and water or wood vinegar to liquid fats and oils and stirring them to cause a chemical reaction.

2 2. It is characterized by using 0.6 to 3.0 parts by weight of powdered highly active calcium oxide and 0.1 to 1.0 part by weight of water or wood vinegar per 1 part by weight of liquid fats and oils. 21. The method for producing an oil and fat powder according to claim 21.

23. The method for producing an oil and fat powder according to claim 21, wherein the highly active calcium oxide is obtained by firing an eggshell at 900 to 150 ° C.

Three