Method for manufacturing functional fertilizer using shells
The method addresses the environmental and economic issues of existing shell waste conversion methods by using shells to produce functional fertilizers through organic acid mixing and microbial fermentation, resulting in reduced carbon emissions and enhanced plant growth promotion.
Patent Information
- Application Number
- PCT/KR2024/010129
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-09-26
- Filing Date
- 2024-07-15
- Publication Date
- 2025-04-03
AI Technical Summary
Existing methods for converting shell waste into fertilizers are energy-intensive and result in significant carbon dioxide emissions, posing environmental concerns and increased costs.
A method that utilizes shells to produce functional fertilizers by mixing organic acids with shells, capturing and converting carbon dioxide into a usable form through microbial fermentation, and then combining the resulting solutions to create a fertilizer with reduced carbon footprint.
The method significantly reduces carbon dioxide emissions, enhances the production yield of organic acids, and produces a functional fertilizer that promotes plant growth, seed germination, and root development, while also recycling all components of the shell waste.
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Figure KR2024010129_03042025_PF_FP_ABST
Abstract
Description
Method for manufacturing functional fertilizer using shells
[0001] The present invention relates to a method for manufacturing a functional fertilizer using shells, and more specifically, to a technology for recycling shells into a functional fertilizer that does not emit carbon dioxide.
[0002] Various shellfish wastes are generated during the shellfish farming process along South Korea's coasts. Over 300,000 tons of these shellfish and their byproducts are generated annually, and disposal costs alone are estimated at over 100,000 won per ton, resulting in over 30 billion won annually. However, small-scale fishermen are unable to afford these costs, so they are essentially dumped illegally on the coast, resulting in serious pollution of the marine ecosystem and the living environment.
[0003] Accordingly, various methods are being developed to recycle discarded shellfish as fertilizer. Existing methods for processing shellfish for use as agricultural fertilizer include heat treatment at high temperatures (450-800℃) to convert calcium carbonate (CaCO3) into calcium oxide (CaO), which supplies calcium to crops and neutralizes acidified soil. Alternatively, organic acids such as acetic acid are used to manufacture fertilizer in the form of calcium acetate.
[0004] However, the existing processing method is an energy-intensive industry that emits a huge amount of carbon by releasing carbon dioxide (CO2), which accounts for about 50% of the shell's components, into the atmosphere. If the 310,000 tons of shells produced annually in Korea were processed, at least 160,000 tons of carbon dioxide could be generated.
[0005] Meanwhile, the world is making various efforts to reduce carbon dioxide emissions to prevent global warming aggravated by the increase in carbon dioxide, and the need to effectively remove carbon dioxide generated during shell processing is emerging.
[0006] The present inventors have diligently researched and developed a method for manufacturing a functional fertilizer using all components of shells, including carbon dioxide generated during shell processing. As a result, a method for producing organic acids with excellent carbon capture / conversion efficiency and carbon reduction effect was established, and the carbon dioxide required for organic acid fermentation was obtained from the carbon dioxide generated during shell processing, thereby significantly reducing (or eliminating) the amount of carbon dioxide generated. Furthermore, the carbon dioxide generated by treating shells with organic acids was applied to microbial fermentation, significantly increasing the production volume (fermentation yield) of organic acids. Furthermore, in a subsequent step, the treated shell-organic acid and the fermented-organic acid were mixed to manufacture a fertilizer, and its functionality was confirmed, thereby completing the present invention.
[0007] Accordingly, the purpose of the present invention is to provide a method for manufacturing a functional fertilizer using shells.
[0008] Another object of the present invention is to provide a functional fertilizer manufactured by the above-described method.
[0009] The present inventors have conducted extensive research efforts to develop a method for manufacturing a functional fertilizer utilizing all components of shells, including carbon dioxide generated during shell processing. As a result, we established a method for producing organic acids with excellent carbon capture / conversion efficiency and carbon reduction effects. We also confirmed that the amount of carbon dioxide generated during organic acid fermentation is significantly reduced (or eliminated) by obtaining the carbon dioxide required for organic acid fermentation from the carbon dioxide generated during shell processing. Furthermore, by applying the carbon dioxide generated by treating shells with organic acids to microbial fermentation, the production of organic acids (fermentation yield) was significantly increased. Furthermore, in a subsequent step, the treated shell-organic acid and the fermented-organic acid were mixed to manufacture a fertilizer, and its functionality was confirmed.
[0010] The present invention relates to a method for manufacturing a functional fertilizer using shells and a functional fertilizer manufactured thereby.
[0011] Hereinafter, the present invention will be described in more detail.
[0012]
[0013] According to one aspect of the present invention, the present invention provides a method for producing a functional fertilizer using shells, comprising the following steps.
[0014] A reaction step of mixing organic acid into the shell;
[0015] A yielding step for obtaining the remaining solution excluding carbon dioxide (CO2) generated in the reaction step.
[0016] According to another aspect of the present invention, the present invention provides a method for producing a functional fertilizer using shells, comprising the following steps.
[0017] A reaction step of mixing organic acid into the shell;
[0018] A fermentation step in which carbon dioxide (CO2) generated during the reaction step is injected into a container containing anaerobic microorganisms;
[0019] A mixing step in which the fermentation step product is mixed with the remaining solution excluding the carbon dioxide generated among the reaction step products.
[0020] According to one embodiment of the present invention, the method for manufacturing a functional fertilizer using the shell may further include the following steps.
[0021] A drying step for drying the obtained or mixed solution.
[0022] Hereinafter, a method for manufacturing a functional fertilizer using the shell of the present invention will be described in detail.
[0023] [Reaction Stage]
[0024] This step involves placing the shells in a sealed container (reactor), injecting organic acid, and then reacting the shells with the organic acid to produce a carbon dioxide (CO2) and mineral (Mg, Ca, etc.)-organic acid solution.
[0025] As used herein, “shells” refers to the outer shells of mollusks that are hardened by the secretion of lime from the mantle, and may include, but are not limited to, oyster shells, clam shells, scallop shells, and by-products thereof.
[0026] According to one embodiment of the present invention, the shells used in this step can be used without preprocessing (grinding) into powder or the like. That is, the method for manufacturing a functional fertilizer using shells of the present invention uses the shells in their entirety, and thus has the advantage of not generating additional energy or carbon.
[0027] In this specification, “organic acid” refers to an acidic organic compound obtained from plants and animals, and may include, but is not limited to, succinic acid, formic acid, acetic acid, lactic acid, valeric acid, malic acid, and / or citric acid.
[0028] According to one embodiment of the present invention, the organic acid used in this step may further include an organic acid fermentation liquid, which is a product of the fermentation step described later.
[0029] The carbon dioxide generated in this step can have a purity of 90% or more and can be used as a carbon source in the fermentation step described later.
[0030] [Acquisition stage]
[0031] This step is the process of obtaining a shell mineral (Mg, Ca, etc.)-organic acid solution, which is the remaining solution excluding the carbon dioxide generated in the reaction step.
[0032] The shell mineral-organic acid solution of the present invention can be used independently as a functional fertilizer, and can also be used by mixing it with an organic acid fermentation solution, which is a product of the fermentation step described later.
[0033] [Fermentation stage]
[0034] This step involves using the carbon dioxide produced in the reactor as a carbon source to ferment organic acids, producing an organic acid fermentation solution. The carbon dioxide generated by treating shells with organic acids can be applied to microbial fermentation to increase organic acid production (fermentation yield).
[0035] Meanwhile, all existing fertilizer manufacturing methods using shells inevitably generate carbon dioxide, but the functional fertilizer manufacturing method using shells of the present invention is characterized by being a carbon reduction technology that does not emit carbon dioxide by using carbon dioxide generated during shell processing as a fermentation carbon source.
[0036] In the present invention, “fermentation” means a process in which microorganisms obtain energy by metabolizing organic nutrients (such as glucose) in an anaerobic environment.
[0037] At this stage, fermentation can be performed by microorganisms.
[0038] Specifically, fermentation at this stage can be performed by anaerobic microorganisms.
[0039] The fermentation step by the microorganism of the present invention is performed in a fermenter, and the microorganism and culture medium for performing organic acid fermentation are accommodated inside the fermenter.
[0040] The fermentation step by the microorganism of the present invention is suitable for producing various organic acids (fermentation liquid), and can produce an organic acid fermentation liquid selected from the group consisting of, but not limited to, succinic acid, formic acid, acetic acid, lactic acid, valeric acid, malic acid, citric acid and mixtures thereof.
[0041] Examples of fermentative (anaerobic) microorganisms used in the method according to the present invention include a single microorganism (Actinobacillus succinogenes) or a mixed microorganism that produces organic acids.
[0042] The above Actinobacillus succinogenes strain (ATCC 55618) is characterized by including a 16s rRNA base sequence of sequence number 1.
[0043] Among the fermenters for producing the above organic acids, the fermenting microorganisms and the culture medium are mixed.
[0044] The above microorganisms can be added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the culture solution.
[0045] If the amount of the above microorganisms added is less than 0.1 parts by weight, the fermentation time becomes excessively long, and if the amount of the above microorganisms added exceeds 10 parts by weight, it is difficult to obtain a mature fermented product.
[0046] The culture solution of the present invention may include all states obtained by treating the culture solution or culture, such as the microorganism (strain) as an effective ingredient, a culture thereof, a culture containing the strain in addition to the isolated and / or purified strain, an extract of the strain, a culture supernatant, a concentrate, a concentrate, a dried product thereof, and also a dilution, a dilution, etc.
[0047] The culture medium used in the method according to the present invention may contain a carbon source, an alkaline base, and components essential for the growth of microorganisms (strains) (strain growth components).
[0048] In the present invention, the carbon source is a sugar, including a monosaccharide, a disaccharide, a polysaccharide, or a mixture thereof, and examples thereof include, but are not limited to, glucose, fructose, sucrose, galactose, mannose, xylose, arabinose, sugar cane, molasses, starch hydrolysate, etc.
[0049] In the present invention, the alkaline base is a weak base containing an alkali metal of Group 1 of the periodic table that maintains a pH suitable for the growth of microorganisms for fermentation of a carbon source, and examples thereof include, but are not limited to, KOH.
[0050] The ratio of carbon source and alkaline base in the culture medium supplied during fermentation can be arbitrarily adjusted by the user to suit fermentation characteristics, taking into account factors such as base solubility and organic acid production rate. This ratio can be arbitrarily adjusted during the fermentation process, provided that the supplied carbon source and alkaline base remain sterile.
[0051] In the present invention, essential components for the growth of the strain (strain growth components) include, but are not limited to, nitrogen sources, vitamins, inorganic salts, and / or carbon source decomposition enzymes such as invertase, in addition to carbon source substrates. Those skilled in the art can easily determine essential components for growth depending on the strain based on known techniques.
[0052] Specifically, in the present invention, the nitrogen source may include, but is not limited to, organic nitrogen sources such as yeast extract, corn steep liquor (CSL), peptone, meat juice, malt extract, and soybean meal; and inorganic nitrogen sources such as urea, ammonium sulfate, ammonium chloride, ammonium phosphate, ammonium carbonate, and ammonium nitrate; or combinations thereof.
[0053] The above method may further include a step of injecting carbonate.
[0054] In the present invention, the carbonate may include, but is not limited to, calcium carbonate (CaCO3), potassium carbonate (K2CO3), and sodium bicarbonate (NaHCO3).
[0055] In the present invention, a quantitative pump, a gas circulation pump, a batch culture incubator, or an airlift reactor is used to supply and stir carbon dioxide gas, and a separate stirring means (motor) is further provided to facilitate dissolution into the culture medium.
[0056] In the present invention, in order to facilitate the increase in carbon dioxide solubility in the fermenter, it is possible to increase the pressure of carbon dioxide inside the fermenter, continuously circulate carbon dioxide and supply it to a sparger in the reactor, or stir the mixed solution inside the fermenter. In this case, the stirring speed may be 200 to 500 rpm.
[0057] In the present invention, the pH of the mixed (fermentation) solution inside the fermenter can be maintained at 6.5 to 6.8.
[0058] According to one embodiment of the present invention, in order to improve the reaction with the shell in this step, the pH control may be stopped from 30 hours to 36 hours after completion of the culture, thereby lowering the acidity to pH 4.0 to 5.0.
[0059] At this time, if the pH of the shell-organic acid reaction solution is 4 or lower, the chemical reaction is slow, so a strong acid such as sulfuric acid, nitric acid, or hydrochloric acid can be added to maintain the pH of the mixed (fermented) solution at 4 or lower.
[0060] The above-described reaction time and / or pH can be arbitrarily adjusted by the user according to the fermentation characteristics, taking into account solubility, organic acid production rate, etc.
[0061] [Mixing stage]
[0062] This step is the process of mixing the shell mineral-organic acid solution produced in the reactor with the organic acid fermentation liquid fermented in the fermenter.
[0063] At this stage, the shell mineral-organic acid solution can be mixed with the organic acid fermented solution produced by carbon dioxide fermentation to increase the mineral content (magnesium, calcium, etc.) within the solution. The organic acid can then act as a catalyst, enabling plants to absorb these minerals (trace elements).
[0064] When mixing, a mineral-organic acid solution can be used, or the mineral-organic acid solution can be added in dried solid (powder) form. When using a mineral-organic acid solution, it can be produced as a shell (liquid) fertilizer, and when using a dried solid (powder) form, it can be produced as a shell (solid) fertilizer.
[0065] According to one embodiment of the present invention, the shell mineral-organic acid solution and the organic acid fermentation liquid may be included in a ratio of 1:8 to 12, preferably 1:10, but is not limited thereto.
[0066] At this stage, since calcium may react with phosphorus in the fermentation medium and precipitate when a large amount of calcium is added, it is desirable to add less than 5% of the shell mineral-organic acid solution and maintain the pH at 6.0 or lower.
[0067] [Drying stage]
[0068] This step is the process of drying the shell mineral-organic acid solution produced in the reactor.
[0069] The shell mineral-organic acid solution can be dried and used in solid (powder) form.
[0070]
[0071] According to another aspect of the present invention, the present invention provides a functional fertilizer manufactured by the above-described manufacturing method.
[0072] The functional fertilizer may include at least one organic acid selected from the group consisting of succinic acid, formic acid, acetic acid, lactic acid, valeric acid, malic acid, and citric acid.
[0073] The above organic acid may be produced by fermentation of Actinobacillus succinogenes (ATCC 55618).
[0074] The functional fertilizer of the present invention may further include trace elements generally related to plant growth and fruit production, such as potassium, calcium, magnesium, sulfur, and boric acid, as needed.
[0075] Furthermore, the functional fertilizer of the present invention can be used in combination with humic acid, fulvic acid, seaweed extract, and / or conventional chemical fertilizers related to plant growth and fruit production.
[0076] Since each plant / fruit has different nutritional requirements, a person skilled in the art can easily determine the ingredients related to plant growth and fruit production according to the requirements based on known technology.
[0077] The functional fertilizer of the present invention has the effects of suppressing cold damage, promoting root growth, and promoting germination.
[0078] The present invention relates to a method for manufacturing a functional fertilizer using shells, and the manufacturing method of the present invention has an excellent carbon reduction effect by utilizing carbon dioxide, which is a main component of shells. In addition, the functional fertilizer manufactured by the manufacturing method of the present invention has the effect of promoting plant growth, seed germination, and root growth by utilizing the mineral components (Ca, Mg, Zn, etc.) of shells, and has the effect of recycling all components of shells by utilizing the carbon dioxide generated during shell processing. Furthermore, while the existing shell processing method takes more than 6 months, the present manufacturing method has the effect of processing shells within a few days without any unpleasant odor or energy consumption.
[0079] Figure 1 is a schematic diagram showing a method for manufacturing a functional fertilizer according to one embodiment of the present invention.
[0080] Figures 2a and 2b show the results of confirming the plant growth promotion effect of a functional fertilizer manufactured according to one embodiment of the present invention.
[0081] Figures 3a to 3c show the results of confirming the seed germination and leaf size change of plants by a functional fertilizer manufactured according to one embodiment of the present invention.
[0082] Figures 4a to 4c are results confirming the effect of promoting plant root growth by a functional fertilizer manufactured according to one embodiment of the present invention.
[0083] Hereinafter, the present invention will be described in more detail through examples. These examples are intended solely to illustrate the present invention more specifically, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.
[0084]
[0085] Example. Manufacturing of functional fertilizer
[0086] After washing 1 kg of shells with water, they were placed in a sealed 20 L reactor and organic acid (20% diluted acetic acid) was slowly added using a metering pump to generate carbon dioxide. The amount of organic acid (diluted acetic acid) added was adjusted according to the progress of fermentation, and the amount of carbon dioxide emitted was confirmed by immersing the organic acid fermentation tank vent (gas outlet) line in water. No mixing or temperature control was performed when adding organic acid.
[0087] Carbon dioxide (CO2) generated through the reaction was injected into the fermenter (180-600 mL / h) and fermented at 37°C for 36 hours with stirring at a speed of 200 rpm. At this time, the 5-L reactor contained 3 L of microbial culture. From 30 to 36 hours after completion of cultivation, pH control was stopped to lower the acidity to pH 4.0 to 5.0.
[0088] A shell (liquid) fertilizer was prepared by mixing 1 L of the fermented organic acid fermentation liquid and 0.1 L of the shell mineral-organic acid solution previously produced in the reactor.
[0089]
[0090] Experimental Example 1. Organic Acid Analysis
[0091] For the organic acids produced in the above examples, the concentration (production amount) of organic acids was measured at 210 nm using HPLC (Algilent, USA), an Aminex HPX-87H column (Bio-Rad, USA), and a UV meter (Algilent). 0.005 N sulfuric acid was used as the HPLC mobile phase, and the mobile phase speed was set to 0.6 ml / min. The measurement results are shown in Table 1 below.
[0092] Carbon dioxide capture and organic acid production (36 hours) Analyte g / L Carbon dioxide (CO2) capture and conversion 5.2 Succinic acid production 15.2 Lactic acid production 9.4 Acetic acid production 7.1
[0093] Experimental Example 2. Confirmation of Fertilizer Functionality 2-1. Confirmation of Growth Promotion Effect
[0094] The growth promotion effect of air purifying plants was confirmed.
[0095] As a result, as can be seen in FIGS. 2a and 2b, it was found that when the functional fertilizer of the present invention was used, the number of leaves of both the Bengal rubber tree (FIG. 2a) and the ginseng Benjamin (FIG. 2b) increased compared to the group without fertilizer addition.
[0096]
[0097] 2-2. Checking seed germination and leaf size changes
[0098] The effects of promoting root growth and growth of plants were confirmed.
[0099] As a result, as can be seen in FIGS. 3a and 3b, when the functional fertilizer of the present invention was used, germination of radish (FIG. 3a) seeds was promoted compared to the group without fertilizer addition, and the size of basil (FIG. 3b) and strawberry (FIG. 3c) leaves increased and the leaf stems became thicker.
[0100]
[0101] 2-3. Confirmation of root growth promotion effect
[0102] The effects of promoting root growth and growth of plants were confirmed.
[0103] As a result, as can be seen in FIGS. 4a to 4c, it was found that when the functional fertilizer of the present invention was used, root growth was promoted in all of the rubber tree (FIG. 4a), rose herb (FIG. 4b), kale (FIG. 4c left), and basil (FIG. 4c right) compared to the group without fertilizer addition.
[0104] The present invention relates to a method for manufacturing a functional fertilizer using shells, and more specifically, to a technology for recycling shells into a functional fertilizer that does not emit carbon dioxide.
Claims
1. A method for manufacturing a functional fertilizer using shells comprising the following steps: A reaction step of mixing organic acid into the shell; A yielding step for obtaining the remaining solution excluding carbon dioxide (CO2) generated in the reaction step.
2. A method for manufacturing a functional fertilizer using shells comprising the following steps: A reaction step of mixing organic acid into the shell; A fermentation step in which carbon dioxide generated in the reaction step is injected into a container containing anaerobic microorganisms; A mixing step in which the fermentation step product is mixed with the remaining solution excluding the carbon dioxide generated among the reaction step products.
3. A method for manufacturing a functional fertilizer using shells according to claim 1 or 2, further comprising the following steps: A drying step for drying the obtained or mixed solution.
4. A method for manufacturing a functional fertilizer using shells, wherein in the first or second paragraph, the reaction step further includes mixing an organic acid fermentation liquid, which is a product of the fermentation step of the second paragraph.
5. A method for manufacturing a functional fertilizer using shells, wherein in paragraph 1 or 2, the organic acid is at least one selected from the group consisting of succinic acid, formic acid, acetic acid, lactic acid, valeric acid, malic acid, and citric acid.
6. A method for manufacturing a functional fertilizer using shells, wherein the carbon dioxide generated in the reaction step in paragraph 1 or 2 has a purity of 90% or higher.
7. A method for manufacturing a functional fertilizer using shells, wherein in the second paragraph, the anaerobic microorganism is Actinobacillus succinogenes (ATCC 55618).
8. Functional fertilizer manufactured by the manufacturing method of paragraph 1 or 2.
9. In paragraph 8, the functional fertilizer has the effect of promoting plant growth, seed germination, and root growth.
10. In paragraph 8, the functional fertilizer is a functional fertilizer used in combination with humic acid, fulvic acid, seaweed extract, and / or conventional chemical fertilizer.
Citation Information
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