KR100683023B1 - Manufacturing method of edible water-soluble calcium carbonate that eliminates the job evasion factor from eggshell - Google Patents

Abstract

The present invention relates to a method for producing an edible water-soluble organic acid calcium which eliminates the task of avoiding the egg from egg shell, and more specifically, dissolves egg shells of various algae such as chicken, duck egg, goose egg or quail egg in organic acid such as acetic acid or lactic acid. In order to prevent the organic acid from evaporating and becoming an environment in which the worker is hard to work, the organic acid vapor evaporated while distilling in the concentration step is collected, cooled, and used as an acetic acid solution, thereby preventing the organic acid vapor from spreading around the workplace. The present invention relates to a method for preparing an edible water-soluble organic calcium acid obtained by reconcentrating and drying a concentrated eggshell / organic acid solution.

The organic acid calcium produced in this way is not only able to obtain a large amount of organic calcium acid from raw materials of waste resources, but is also expected to be able to produce more value-added food by using water-soluble organic acid calcium in various food industries. It can be used to work and to prevent pollution in the surrounding environment.

Description

Method for manufacturing organic acid calcium from egg shells in solving a duty evasion factors}

The present invention relates to a method for producing an edible water-soluble organic acid calcium which eliminates the task of avoiding the egg from egg shell, and more specifically, dissolves egg shells of various algae such as chicken, duck egg, goose egg or quail egg in organic acid such as acetic acid or lactic acid. In order to prevent the organic acid from evaporating and becoming an environment in which the worker is hard to work, the organic acid vapor evaporated while distilling in the concentration step is collected, cooled, and used as an acetic acid solution, thereby preventing the organic acid vapor from spreading around the workplace. The present invention relates to a method for preparing an edible water-soluble organic calcium acid obtained by reconcentrating and drying a concentrated eggshell / organic acid solution.

The role of calcium in the human body forms the skeleton and teeth, coagulates blood, and as the concentration of intracellular calcium ions rises, neurotransmitters are released and nerve stimuli are delivered, and muscle contraction and relaxation functions. Calcium plays a very important role in the human body by assisting metabolic processes in cells by combining with several regulatory proteins.

Most egg shells are 94% inorganic salts, which gives a firm feeling. Inorganic salts contained in eggshell are calcium carbonate in large part, so they contain a large amount of calcium. There is also a small amount of magnesium carbonate and calcium magnesium phosphate. 4.5% organic matter and 1.5% moisture.

However, since the egg shell is poorly soluble in water, it is difficult to use calcium contained in the egg shell. Therefore, it is expected that the added value of the calcium carbonate contained in the eggshell is dissolved in the organic acid to make the edible organic calcium carbonate which is easy to use and used in the food industry.

On the other hand, the manufacturing process of dissolving calcium carbonate in the egg shell with organic acid can not only injure workers working around the workplace by the organic acid vapor which is volatilized during the concentration process, Since it pollutes the environment, it is very likely to be a workplace of job evasion factors.

It is an object of the present invention to provide a method for preparing poorly soluble calcium carbonate contained in eggshells with edible water-soluble organic calcium carbonate.

In addition, another object of the present invention is to provide a method for preparing edible water-soluble organic calcium acid which can eliminate the avoidance factors that can be generated by using an organic acid as a solvent.

In order to achieve the above object, the present invention comprises the steps of (a) crushing the eggshell to the size of 10 to 30 mesh with a grinder in the presence of water;

(b) drying the ground eggshell powder of (a);

(c) finely grinding the dried eggshell powder of (b) to a size of at least 80 mesh;

(d) adding the finely ground eggshell powder of (c) to 5-50% of an organic acid and allowing it to stand at a temperature of 70-100 ° C. to dissolve;

(e) filtering the eggshell / organic acid solution of (d) through a micro filter, and obtaining a filtrate thereof;

(f) distilling the filtrate under (e) under reduced pressure, and cooling and condensing the organic acid vapor which is evaporated, and collecting it as an organic acid and storing it separately, wherein the remaining filtrate is first concentrated to 40-50% of the volume of the initial filtrate.

(g) atmospheric distillation while stirring the primary concentrate of (f), and secondly concentrating the acetic acid vapor evaporated to a paste state having a water content of 20 to 30% while forcibly suctioning and discharging it to the outside; And

(h) drying the secondary concentrate of (f) at 70 to 80 ° C. to obtain a solid organic acid calcium having a water content of 8 to 12%. to provide.

Hereinafter, the present invention will be described in detail.

At this time, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art.

In addition, repeated description of the same technical configuration and operation as in the prior art will be omitted.

The present invention is to prepare an edible water-soluble organic calcium using eggshell and organic acids as a calcium source, a manufacturing method for avoiding the inconvenience that workers can avoid due to the use of organic acids, specifically chicken, duck eggs, goose eggs Or dissolve egg shells of various algae such as quail eggs in organic acids such as acetic acid or lactic acid, and organic acid vapors which are evaporated while distilling in the concentration step are collected and cooled in order to prevent the organic acids from evaporating and becoming an environment in which the worker is poor. The present invention relates to a method for preparing edible water-soluble organic calcium carbonate obtained by a process such as reconcentration and drying of a concentrated egg shell / organic acid solution while preventing the spread of organic acid vapor around the workplace by using it as an acetic acid solution.

And, the present invention, the step of grinding the eggshell in two steps, and the step of dissolving the crushed eggshell powder in an organic acid solution. Removing the insoluble material using a micro filter to obtain an eggshell / organic acid solution, concentrating the eggshell / organic acid solution in two steps, and drying the concentrate. The step of pulverizing the solid organic calcium acid obtained by the step of particles of 80 mesh or more.

At this time, the organic acid is preferably used acetic acid or lactic acid, more preferably using an organic acid having a concentration of 20 to 25%. This is because the solubility of the eggshell extracted within the above concentration range is the best.

Hereinafter, a method for preparing edible water-soluble organic acid calcium salt according to the present invention will be described in more detail. However, it is not limited thereto.

(1) eggshell washing process

This process is a process of washing using a washing apparatus in order to clean the white or yolk remaining in the discarded eggshell, it is preferable to use a blower type (blower type) washing apparatus.

(2) eggshell grinding process

When eggshell is dissolved in organic acid, it is ground to dissolve quickly and surely. When eggshell is crushed, dust is generated in large quantities, which not only contaminates the workplace but also causes workers' respiratory diseases. To facilitate grinding, a grinding step is carried out over two steps.

end. Crushing

This process is a pretreatment grinding process that is performed to facilitate the fine grinding while suppressing the generation of dust due to the remaining moisture by using the washed eggshell as it is, it is preferable to use a grinder having a compression force, The first grinding is performed by using a roll mill to the size of 10-30 mesh.

I. dry

Since the first crushed eggshell powder contains a lot of moisture and is agglomerated during fine grinding, it must go through a drying step, preferably hot air drying.

All. Pending

As a process for finely crushing the dried primary eggshell powder to a size of at least 80 mesh, it is preferable to use a grinder using a shear force or an impact force. Specifically, a pin mill is used.

At this time, the crushed eggshell powder is preferably passed through the sieve of the fine particles connected to the sealed reservoir, it is preferable to prevent the dust from entering the workplace.

(3) melting process

This process is performed by immersing and dissolving finely ground eggshell powder in an organic acid solution to obtain water-soluble calcium acetate in eggshells containing a large amount of insoluble calcium carbonate. It is desirable to. This is because carbon dioxide gas generated when the organic acid and the carbonate carbonate, which is the main component of the eggshell powder, forms a turbulent flow in the organic acid solvent in the dissolution tank, and thus is uniformly dissolved without a separate stirring device. However, in order to make reaction quicker, you may install the stirring apparatus further.

In this step, in order to sufficiently dissolve the egg shell meal, it is 1.5 to 2.5 hours, preferably about 2 hours in an organic acid solution of 5 to 50% concentration, preferably 20 to 25% organic acid solution at a temperature of 70 to 100 ℃ React and dissolve. This is because the dissolution efficiency of calcium is the best at the organic acid concentration in the above range.

At this time, in order to prevent the organic acid from volatilizing and polluting the workplace when the stationary dissolution tank is sealed, an inlet in which the eggshell powder and the organic acid are introduced is sealed, and a sealed inlet is used by connecting a duct for forced discharge to the outside. It is preferable.

In addition, when foaming is excessively generated upon dissolution and overflows into the reaction container, an antifoaming agent allowed for food may be used at 50 ppm or less.

(4) filtration process

The mining process is a process for removing an insoluble substance in a dissolved eggshell / organic acid solution to obtain high purity organic acid calcium, and it is preferable to use a filtrate obtained by filtration using a micro filter that can filter fine substances. Specifically, a membrane having a diameter of about 0.02 mm is used as a filter.

(5) concentration process

In this process, when the obtained filtrate is concentrated, the volatilized vapor contains a large amount of organic acid, which not only harms the worker but also pollutes the environment inside and outside the workplace. This is a process of performing a two-stage concentration step of vacuum distillation concentration that can collect and recycle most of the organic acid vapor and then back to atmospheric distillation concentration (open heat concentration).

end. Vacuum distillation

In order to prevent the volatilization of the organic acid vapor volatilized into and out of the workplace and to recycle it, the organic acid vapor volatilized by heating and concentrating primarily in a sealed heater at a level of 40 to 50% based on the volume of the filtrate obtained is passed through a cooler. Collect, condense and return to acetic acid.

This is because once the filtrate is fully concentrated it is difficult to discharge the concentrate out of the concentrator.

I. Atmospheric Distillation

The primary concentrate is concentrated in a paste state having a water content of about 20 to 30% while stirring in a heater that is opened and closed again.

At this time, the organic acid vapor generated by volatilization is to the worker (危害), avoiding work, it is preferable to perform the installation by installing the air conditioning on the ceiling so that the cutting and intake smoothly in the workplace.

(6) drying process

This step is to remove the organic acid solution remaining in the second concentrated eggshell / organic acid concentrate to obtain a solid organic acid calcium having a water content of about 10%, the temperature which does not deteriorate the quality of the obtained organic acid calcium It is preferable to perform hot air drying within the range. Specifically, it is dried for about 2 hours in a hot air of about 70 ℃.

(7) Calcium Organic Acid Grinding Process

This step is a step of pulverizing and producing a powder of a constant size in order to improve the availability and quality of the organic acid calcium dried in the step (6).

In the present invention, it is preferable to prepare calcium organic acid having a size of about 80 mesh.

(8) packing

This step is a step of standardizing and packaging the prepared calcium carbonate powder with a suitable packaging material, packaging unit, etc. to facilitate storage and handling.

Hereinafter, the present invention will be described in more detail with reference to specific examples and experimental examples. However, the present invention is not limited to the following examples, and it will be apparent to those skilled in the art that various changes or modifications can be made within the spirit and scope of the present invention.

Experimental Example 1

In this experiment, in order to determine the optimal organic acid concentration and the amount of use, the solubility of eggshell and the yield of calcium acetate obtained through various parameters were measured.

Ingredients: 10 kg of eggshells collected from bakery or restaurant

       Acetic Acid and Lactic Acid with 99.7% Purity

The egg shells were soaked in clean water for 30 minutes to remove foreign substances, washed, and dried. The dried egg shells were ground to about 100 mesh with a grinder.

1. Solubility of eggshell by concentration of organic acid

For solutions containing acetic acid and lactic acid at concentrations of 5, 10, 15, 20, 25, 30, 35, 40 45, and 50%, the values corresponding to the amount of acetic acid and lactic acid at 1 liter are 20, 10, 5, 1kg of eggshell 100 mesh powder was added to 8, 4 and 2 ℓ, and then immersed and dissolved for 2 hours, filtered through 120mesh sieve to remove insoluble materials, concentrated to 50%, sprayed and dried at 157 ℃ to obtain calcium acetate and calcium lactate. And solubility thereof were determined.

Type of mountain Acid concentration (%) 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 Acetic acid 86.8 86.9 87.3 87.5 85.0 80.3 77.5 67.5 59.1 Lactic acid 65.6 66.0 66.7 67.3 64.3 51.4 46.2 39.8 37.5

2. Solubility of eggshell by immersion time by type of organic acid

1 kg of eggshell powder was added to 4 l of a solution of 25% acetic acid and lactic acid, and the soaking and dissolution time were performed for 1 hour, 1 hour 30 minutes, 2 hours and 2 hours 30 minutes at a temperature of 90 ° C, respectively. After filtration and concentration, the solubility was determined by dipping time.

Kind of the mountain Immersion, melting time (hr) / 90 ℃ One 1.5 2.0 2.5 Acetic acid (%) 60.3 84.3 86.9 87.0 Lactic acid (%) 55.1 62.5 68.3 68.5

3. Eggshell and the content of calcium carbonate, calcium acetate and water-soluble calcium prepared in Experimental Example (2)

Calcium carbonate, calcium acetate and water-soluble calcium content of the product prepared using the egg shell and egg shell used in Experimental Example (2) were analyzed.

division CaCO ₃ Ca (CH ₃ COO) ₂ Water soluble calcium Egg shell (%) 94.0 0 0.01 Manufactured Products (%) 0 97.6 24.4

EXAMPLES Mass Production Method of Calcium Organic Acid According to the Present Invention

Preparation of Edible Water-Soluble Organic Calcium Acid Using Egg Shells

Ingredients: 10kg eggshells collected from bakery or restaurant

       Acetic Acid with 99.7% Purity

First, 10 kg of the egg shells collected are placed in a brower-type washer (3200L × 1700H, material: stainless steel), soaked for about 40 minutes while maintaining the temperature of water at 40 ° C, then stirred and washed with aeration, and washed twice by rinsing. The whites or yolks of the deteriorated eggs remaining in the shells were removed.

The washed egg shells were put into a roll mill (W600 × L680 × H1530, material: SUS 304), pulverized to about 10 mesh, and then dried in a hot air dryer at a temperature of 70 ° C. for about 2 hours. Then, the dried egg shells were put in a pin mill (W300 × L900 × H2000, material: stainless steel) and pulverized, and the pulverized particles were collected in an airtight box through a 180mesh sieve.

Then, in a stationary tank (Φ800 × H 1800, material: stainless steel) containing 25% of acetic acid solution, pulverized egg shell powder corresponding to 1/2 of the acetic acid solution is dissolved while heating at a temperature of 80 ° C. At this time, a large amount of foam was generated while dissolving, adding 0.17 g of antifoaming agent (30% of silicon resin, 7% of sorbitan fatty acid ester, 0.6% of carboxymethylcellulose) to 1kg of eggshell / acetic acid solution to suppress the overflowing of the fixed tank. .

The dissolved egg shell / acetic acid solution was filtered through a micro filter having a pore size of 0.02 mm to remove insoluble particles.

The acetic acid vapor generated by heating the filtrate at a temperature of 104 ° C. in a heating unit of a reduced pressure distillation condenser equipped with a heating unit, a middle stream unit, and a cooling unit is condensed by a cooler through a cooling tube to recover 15 kg of acetic acid per hour. And concentrated first until the filtrate reached 50% of its original volume.

The primary concentrate was put back into the open / close stirred heating concentrator and heated to secondary concentration until it became a paste at normal pressure. At this time, the opening and closing port was used by connecting a duct so that a small amount of acetic acid vapor can be discharged to the outside of the building.

The secondary concentrate was further dried for 2 hours in a hot air dryer at 70 ° C. to obtain calcium acetate having a water content of about 10%.

According to the present invention, by preparing edible water-soluble organic acid calcium using egg shells produced and discarded in various algae eggs as organic calcium source, not only a large amount of organic calcium acid can be obtained from raw materials of waste resources, It is expected that the food industry will be able to produce food with higher added value.

In addition, the present invention by developing a series of work avoidance environment improvement process that can reduce the environmental pollution and harm inside and outside the workplace due to the organic acid vapor generated by the use of organic acid, workers can work with confidence, and prevent environmental pollution It is to be done.

In addition, a range of modifications, changes, and substitutions may be made to the above disclosure, and in some cases only some of the features of the invention may be used. Accordingly, the appended claims should be construed broadly and in accordance with the spirit and scope of the invention.

Claims (6)

(A) a step of crushing the eggshell to the size of 10 to 30 mesh with a grinder in the presence of water; (b) drying the ground eggshell powder of (a); (c) finely pulverizing the dried eggshell powder of (b) to a size of at least 80 mesh in a sealed space; (d) adding the finely ground eggshell powder of (c) to 5-50% of an organic acid and allowing it to stand at a temperature of 70-100 ° C. to dissolve; (e) filtering the eggshell / organic acid solution of (d) through a micro filter, and obtaining a filtrate thereof; (f) The filtrate of (e) is distilled under reduced pressure, and the evaporated organic acid vapor is cooled and condensed, collected again as organic acid, stored separately and reused, and the remaining filtrate is first concentrated to 40-50% of the initial filtrate volume. step (g) atmospheric distillation while stirring the primary concentrate of (f), and secondly concentrating the acetic acid vapor evaporated to a paste state having a water content of 20 to 30% while forcibly suctioning and discharging it to the outside; And (h) drying the secondary concentrate of (f) in a hot-air drying chamber at 70-80 ° C. to obtain a solid organic calcium acid having a water content of 8-12%. Method for preparing calcium acid. delete The method of claim 1, The organic acid of the step (d) is a method for producing edible water-soluble organic calcium acid, characterized in that the organic acid of 20 to 25% concentration. The method according to claim 1 or 3, The organic acid is a manufacturing method of edible water-soluble organic calcium acid, characterized in that acetic acid or lactic acid. delete The method of claim 1, Eggshell is a method for producing edible water-soluble organic calcium acid, characterized in that the shell of at least one egg selected from the group consisting of eggs, goose eggs, duck eggs and quail eggs.