METHOD FOR PRODUCING MICROPLATES FROM SHELLS, AND MATERIAL PRODUCED BY USING THE MICROPLATES

Abstract

The present invention relates to a method for producing microplates from shells. The production method of the present invention includes a step of treating pulverized shells with an alkaline solution, thereby separating microplates of shells, and a step of producing microplates in the form of precipitate from the solution.

Claims

1. A method for producing a microplate powder from a shell, comprising the steps of: (1) treating pulverized material of the shell with an alkaline solution to separate the microplates of the shell; and (2) producing a microplate in the form of a precipitate in the solution.

2. A method for producing a microplate powder from a shell, comprising the steps of: (1) separating calcium ions and carbon dioxide by treating the pulverized shell with an acidic solution, and collecting carbon dioxide; (2) treating the solution in which the calcium ions are separated with an alkaline solution to raise the pH; (3) recrystallizing the calcium carbonate by adding the collected carbon dioxide to the solution having the increased pH; and (4) separating the precipitate from the solution.

3. The method for producing a microplate powder from a shell according to claim 1, further comprising a pretreatment step for removing the ooze and the like adhering to the outside of the shell and for pulverizing the shell before the alkaline solution treatment or the acidic solution treatment.

4. The method for producing a microplate powder from a shell according to claim 1, wherein the step of the alkaline solution treatment or the acid solution treatment further uses one or more method among a method of using thermal expansion and contraction, a method of imparting vibration using ultrasonic waves, and a method of accelerating decomposition of an internal connecting protein by irradiating ultraviolet rays.

5. The method for producing a microplate powder from a shell according to claim 1, wherein the alkaline solution is an aqueous solution of sodium hydroxide.

6. The method for producing a microplate powder from a shell according to claim 2, wherein the acid solution is hydrochloric acid and the alkaline solution is an aqueous solution of sodium hydroxide.

7. The method for producing a microplate powder from a shell according to claim 2, wherein the step of separating calcium ions is performed at a pH of less than 2.

8. A calcium carbonate powder produced by the method of claim 1.

9. A method for producing a flat plate with shell microplate, comprising the steps of; (1) aligning microplates of the shell on a substrate; (2) fixing the aligned microplates to the substrate.

10. The method for producing a flat plate with shell microplate according to claim 9, wherein the surface of the substrate is made hydrophilized, hydrophobic, or electrified by imparting electric charge to the surface of the substrate or etched to impart irregularities to the surface, before the aligning step so that the microplates can be well aligned on the surface.

11. The method for producing a flat plate with shell microplate according to claim 9, wherein the aligning step utilizes one or more method among a method of aligning the microplate with the substrate according to a flow of fluid, a method of aligning using a 3D printing method, a brick cross-lamination method, and a continuous process by roll-to-roll sheet.

12. The method for producing a flat plate with shell microplate according to claim 9, wherein the fixing step utilizes one or more method among spreading or spraying an adhesive material to fix the microplate to the substrate, and a method of optically curing the microplate together with one side of the substrate.

13. A flat plate with shell microplate comprising: a substrate; and a microplate layer of the shells which is aligned and fixed on the substrate.

14. A method for finishing a surface of a target object with a shell microplate, comprising the steps of; (1) aligning the shell microplates on the surface of the object; and (2) fixing the aligned microplates to the surface of the object.

15. A method for producing a hard calcium carbonate powder with a shell microplate, comprising the steps of; (1) producing a calcium ion solution by dissolving a powder of a shell microplate in an acidic liquid; and (2) adding an alkaline liquid to the produced calcium ion solution, and injecting carbon dioxide into the solution to precipitate crystals of calcium carbonate.

16. A method for producing a calcium phosphate powder with a shell microplate, comprising the steps of; (1) putting a powder of a shell microplate into a phosphate ion solution to form a precipitate; and (2) washing and drying the precipitate to obtain calcium phosphate powder.

17. The method for producing a calcium phosphate powder with a shell microplate according to claim 16, wherein the phosphate ion solution in the step for forming a precipitate is a pyrophosphate solution.

18. The method for producing a microplate powder from a shell according to claim 2, further comprising a pretreatment step for removing the ooze and the like adhering to the outside of the shell and for pulverizing the shell before the alkaline solution treatment or the acidic solution treatment.

19. The method for producing a microplate powder from a shell according to claim 2, wherein the step of the alkaline solution treatment or the acid solution treatment further uses one or more method among a method of using thermal expansion and contraction, a method of imparting vibration using ultrasonic waves, and a method of accelerating decomposition of an internal connecting protein by irradiating ultraviolet rays.

20. A calcium carbonate powder produced by the method of claim 2.

Description

DESCRIPTION OF DRAWINGS

[0036] FIG. 1 illustrates a flow chart for producing a microplate from a shell according to an embodiment of the present invention and producing a flat plate, a hard calcium carbonate powder, and a calcium phosphate powder thereby.

[0037] FIG. 2 illustrates a structural diagram and crystal kinds of calcium carbonate.

[0038] FIG. 3 illustrates a process for producing a calcium carbonate powder by treating a shell with an alkaline solution in an embodiment of the present invention.

[0039] FIG. 4 illustrates a process of producing calcium carbonate powder with shells by collecting carbon dioxide and treating an alkaline solution after treating the shell with an acid solution in another embodiment of the present invention.

[0040] FIG. 5 is an EDX spectrum of the shell microplate calcium carbonate powder produced by an embodiment of the present invention and the comparative object powder prepared.

[0041] FIG. 6A to 6D are photographs of the particle size and shape of the shell microplate calcium carbonate powder produced in an embodiment of the present invention.

[0042] FIG. 7 is a graph comparing the absorbance (whiteness degree) of the shell microplate calcium carbonate powder produced in an embodiment of the present invention with the absorbance of the powder produced from limestone.

[0043] FIG. 8 illustrates a conceptual diagram of an apparatus for producing a large-area flat plate using a shell microplate calcium carbonate powder according to another embodiment of the present invention.

[0044] FIGS. 9A and 9B are photographs of the size and shape of the calcium phosphate powder produced in another embodiment of the present invention.

[0045] FIG. 10A is an EDX graph (A) of the calcium phosphate powder produced in another embodiment of the present invention, and FIG. 10B is a graph showing XRD analysis that the calcium phosphate powder produced in another embodiment of the present invention is of a Monetite crystal structure.

BEST MODE

[0046] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0047] In the present specification, the shell refers to the shell of the shellfish, and the shellfish is collectively referred to as molluscs belonging to the bivalves. Representative shellfish include oysters, clams, shells, and abalones. In this embodiment, it is possible to utilize the discarded waste shell on the coast.

[0048] FIG. 1 is a flow chart for preparing a microplate from a shell according to an embodiment of the present invention and producing a flat plate, a hard calcium carbonate powder, and a calcium phosphate powder.

[0049] This embodiment of the present invention (FIG. 1 (A), provides treating the abandoned shells treated with an alkaline solution to remove an organic material layer containing protein to produce a microplate constituting the shell as in type of powder (FIG. 1 (B)) and laminating it to be in a uniform alignment structure, and producing a large-area flat plate having excellent mechanical performance (FIG. 1 (E)). In addition, the present embodiment provides a method of finishing the surface of a target object with various colors by using the produced microplate (FIG. 1 (F)), a method of producing calcium carbonate (hard calcium carbonate) microplate powder using the produced microplate (FIG. 1 (C)), and a method of producing calcium phosphate powder (FIG. 1 (D)).

[0050] Limestone is a shell of billions of years old. Instead of pulverizing the limestone, there is a method of making a heavy calcium carbonate powder using a shell. To adopt this method, the first step is to produce microplate from the shell. According to the results of a study by many scholars, the shell is a structure in which micrometer-sized fine sections are stacked like a brick as shown in FIG. 1 (A). When such a microplate is produced with a shell, the microplate itself can be a calcium carbonate powder of uniform size and high purity (known as 98% or more). Since the microplates are bonded to each other by the internal connecting protein and the organic substance existing between the microplates like mortar between bricks, the remaining microplates can be prepared as they are by removing the protein or by applying energy above the binding force of the protein.

[0051] The calcium carbonate produced with the shell is eventually extracted in a crystalline form, and the crystal of calcium carbonate has a structure of calcite or aragonite as shown in FIG. 2.

[0052] In the conventional studies, a method of producing calcium carbonate powder from the shell goes through the process of i) crushing the shell or ii) preparing the calcium chloride or calcium hydroxide by treating the shell with an acidic solution and then injecting carbon dioxide at high temperature to precipitate calcium carbonate.

[0053] In this embodiment, the foreign material of the abandoned shell is first removed, and the shell is pulverized to an appropriate size (in centimeter unit or more) by applying an external force to the shell (coarse pulverization). The step of removing foreign material from the shells can be done by leaving them alone to let wind, light, animals, worms, and bacteria, and the like do the job. Or with the aid of solution containing an alkali the foreign material can be forcibly removed. Of these, one or a plurality of methods can be adopted. In the embodiment, the outside ooze is removed by natural standing for several days, and the soil is washed with water.

[0054] Further, the microplate produced from the shell can be arranged on the surface of a tile or a wallpaper to obtain a decoration effect (see FIG. 1 (F)). By adjusting the arrangement of the microplate layer and the thickness of the laminate, the color of the reflected light can be selected, thereby obtaining various colors. The pearls are mainly milk-colored and black-colored. In this way, it is possible to make various colored pearls by coating on the surface of pearls in this way.

[0055] Further, a hard calcium carbonate powder can be produced from the shell (see FIG. 1 (C)). Instead of making reaction with the calcium oxide and water to obtain calcium hydroxide as in the conventional method for producing a hard calcium carbonate, the powder from the shell or the recrystallized powder can be used as a hard calcium carbonate powder.

[0056] FIG. 3 is a view illustrating a process for producing a calcium carbonate powder by treating a shell with an alkaline solution in an embodiment of the present invention.

[0057] As shown in Chemical Formula 1, the shell is treated with an aqueous solution of sodium hydroxide and subjected to ultrasonic treatment at 50 C. for 4 hours to obtain calcium carbonate in powder form. This reaction is reached by hydrolysis of the peptide bond of internal connecting protein by a hydroxyl ion, and this reaction can also inhibit the loss of carbonate into the form of carbon dioxide. In this solution, the calcium carbonate microplates are precipitated and microplates are produced when the solution containing contaminants and decomposed organic materials is removed. The more frequency and time of the ultrasonic treatment are increased, the smaller size of fine powder is produced. And the size of particles can be controlled by changing treatment conditions such as reaction time, temperature and ultrasonic.

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[0058] FIG. 4 illustrates a process for producing precipitated calcium carbonate (hard calcium carbonate) through recrystallization of calcium carbonate in another embodiment of the present invention.

[0059] The coarse pulverized material of the abandoned shells is put into water and the pH is adjusted to 2 or less by adding hydrochloric acid (4M concentration) as an acidic solution. As a result, calcium ions (Ca.sup.2+) are separated and carbon dioxide is separated into gas. When this gas is passed through a 6M sodium hydroxide solution, which is an alkaline solution, it is collected in an alkaline solution in carbonate form. The acid solution with calcium ions is treated with 6M sodium hydroxide solution to raise the pH again. Removal of the impurity solids results in calcium ions remaining in the solution layer, which are combined with carbonate ions captured in a 6M sodium hydroxide solution to form calcium carbonate crystals. When the unreacted solution is removed and filtered, a calcium carbonate powder is obtained. Through this process, hard calcium carbonate can be produced without a separate process of CO.sub.2 elimination from the shells and reinjection of CO.sub.2.

[0060] For aforementioned method of producing a fine powder and calcium carbonate recrystallization, one or a plurality of methods can be adopted from the following or other methods; a method of separating and reducing the adhesive force between the shell protein and the microplate using thermal expansion and contraction, a method of separating the microplate by vibration using ultrasonic waves, or a method of promoting the decomposition of the protein of the shells by irradiation of ultraviolet ray.

[0061] The EDX spectrum (See FIG. 5) of the calcium carbonate powder obtained as a result shows that the calcium carbonate powder of shell microplate designated by Hanbat A (microplate produced by treatment with an alkaline solution) and Hanbat B (calcium carbonate recrystallized by treatment of acidic solution) is well separated only into calcium, carbon, and oxygen. It can be seen that its level of purity is not lower than the reagent of Aldrich Sigma company by comparison, even has fewer impurities than a hard calcium carbonate (designated as OMYA PCC) and a heavy calcium carbonate (designated as OMYA GCC) originating from limestone by comparison.

[0062] Another embodiment for producing precipitated calcium carbonate (hard calcium carbonate) through calcium carbonate recrystallization is as follows. First, a calcium solution is produced by dissolving with an acidic ionized water liquid containing hydrogen cation. Carbon dioxide generated during this process is collected at the same time using collection equipment. Using carbon dioxide collection equipment, the generated carbon dioxide is not released to the atmosphere and is reused in a closed circuit manner in the powder producing system. An alkaline ionized water solution containing hydroxide ions and carbon dioxide collected in the previous step are injected/blown into the acid solution in which the calcium ions are dissolved from the shell, and crystals of calcium carbonate are precipitated at the bottom of the solution. The resulting crystals of calcium carbonate are washed and dried to finally produce a calcium carbonate powder. The particle size of the powder can be controlled by changing the concentration and temperature.

[0063] FIGS. 6A to 6D are photographs of the particle size and shape of the shell microplate calcium carbonate powder produced in the exemplary embodiment of the present invention. FIG. 6A is Omiya calcium carbonate (heavy calcium carbonate), and FIG. 6B is an enlarged view of FIG. 6A. FIG. 6C refers to calcium carbonate produced by this embodiment, and FIG. 6D is an enlarged view of FIG. 6C. As shown in FIGS. 6A to 6D, the particle size of the calcium carbonate powder obtained as a result of the producing process of this embodiment is better than the particle size of the product produced in the existing limestone with respect to crystalline property and even distribution.

[0064] FIG. 7 is a graph comparing the absorbance (whiteness degree) of the shell microplate calcium carbonate powder produced in the exemplary embodiment of the present invention with the absorbance of the powder produced from limestone.

[0065] It is confirmed that the whiteness (absorbance) of the calcium carbonate powder obtained as a result of the production of this embodiment is higher than that of the Omya powder, which is a powder originating from limestone.

[0066] FIG. 8 illustrates a conceptual diagram of an apparatus for producing a large-area flat plate using a shell microplate calcium carbonate powder according to another embodiment of the present invention. The large-area flat plate can be produced by applying the microplate horizontal alignment technique and the lamination technique using the shell microplate powder obtained through the aforementioned process.

[0067] First, a substrate which the produced microplate powder is to be aligned to is prepared. Next, the microplate powder is aligned on the prepared substrate and the aligned microplate powder is fixed to the substrate. Next, the microplate powder of the second layer is aligned on the previously aligned and fixed microplate powder layer, and the microplate powder of the second layer is fixed. And the above process may iterate to accomplish a desired property by laminating one or a plurality of layers.

[0068] The preparation of the substrate for aligning the microplate powder includes selecting the type of the substrate and pre-treating the surface of the substrate to facilitate alignment or fixation. At this time, pretreatment can be performed by making it hydrophilic or hydrophobic or giving charge with electrification. Also, the surface of the substrate may be preprocessed by a method in which irregularities are imparted to the surface of the substrate by etching or the like so that the microplates can be aligned well.

[0069] Aligning the microplate powder on the prepared substrate includes a method of aligning the microplate powder according to the flow of the fluid, a method of aligning using the 3D printing method, a brick cross-lamination technique, a continuous process by a roll to roll sheet, etc. One or more of these methods can be adopted.

[0070] For example of the alignment process, as illustrated in FIG. 8, a powder may be contained in a droplet to form a uniform layer by releasing on the surface of the substrate.

[0071] The fixation of the aligned microplate powder is performed by spreading or spraying an adhesive an adhesive material such as lacquer, natural adhesive or artificial adhesive, or by optically curing. One or more of these methods can be adopted.

[0072] In the structure where the microplates are stacked like bricks, the impact energy is absorbed as the progress of the fracture due to the external mechanical impact proceeds in a zigzag manner. A lightweight and high strength structure like a shell can be obtained by aligning the microplate powder produced from the shell evenly and laminating the flat surfaces.

[0073] An exemplary embodiment of producing calcium phosphate powder from shells is as follows. First, a microplate powder produced from shells or shells are put into a phosphate ion solution (of pH less than 2) to form a precipitate. In this process, the phosphoric acid ion of the phosphate ion solution and the calcium carbonate component of the shell react with each other to produce calcium phosphate, and the carbonic acid is gasified as carbon dioxide and removed. The precipitated calcium phosphate crystals are washed and dried to finally produce a calcium phosphate powder. In this process, a phosphoric acid or pyrophosphate solution can be used as the phosphate ion solution.

[0074] FIGS. 9A and 9B are photographs of the size and shape of the calcium phosphate powder produced in another embodiment of the present invention. FIG. 10A is an EDX graph of calcium phosphate powder produced in another embodiment of the present invention, and FIG. 10B is a graph (B) showing XRD analysis that the calcium phosphate powder produced in another embodiment of the present invention is of Monetite crystal structure.

[0075] As shown in FIG. 10A, the structure of the calcium phosphate powder is of a high purity. As illustrated in FIG. 10B, the peak is the same as the peak of the monetite crystal structure, so that the monetite crystal structure is the main structure.

[0076] The exemplary embodiments of the present invention have been described in detail above. It will be apparent to those skilled in the art that this specific description is merely a preferred embodiment and that the scope of the invention is not limited thereto. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.