KR102298288B1 - Low power based nano calcium carbonate manufacturing device and nano calcium carbonate manufacturing method using same - Google Patents

Abstract

The nano calcium carbonate manufacturing apparatus and the nano calcium carbonate manufacturing method using the same disclosed herein utilize waste resources by using waste concrete based on low power, and can efficiently produce calcium carbonate and simultaneously remove carbon dioxide.

Description

Low-power-based nano calcium carbonate manufacturing device and nano calcium carbonate manufacturing method using the same

Disclosed herein are a low-power-based nano calcium carbonate manufacturing apparatus and a nano calcium carbonate manufacturing method using the same.

Carbon dioxide is the most important factor influencing global warming. The concentration of carbon dioxide in the atmosphere has steadily increased, reaching 405.5 ppm in 2017, an increase of about 46% compared to pre-industrial times (before 1750). Therefore, many scholars and researchers are looking for ways to reduce carbon dioxide emissions, and one promising option is mineral carbonation, that is, the storage and utilization of mineral carbonates and silica through carbonates of natural silicate minerals such as calcium and magnesium silicates. will do

Waste concrete is a construction waste, and it has the advantage of being easily supplied and supplied in large quantities during urban redevelopment, highway, bridge construction, and dismantling or new construction of buildings such as apartments. However, since the recycling rate is not high because of mixed discharge at the construction site, an efficient system has not been established. Fine-grained calcium carbonate, classified as nano calcium carbonate or precipitated calcium carbonate, is widely used in various fields such as building materials, paints, paper, medicine, cosmetics, and plastics. It is estimated to be about In order to preoccupy the market expansion according to the demand for high-end products in the future, it is necessary to secure price competitiveness by securing high-quality nano calcium carbonate production and process yield.

Microbubbles mean microbubbles with a bubble diameter of 50 μm or less. In water, the buoyancy is smaller than that of normal bubbles, so they are reduced and converted to nano-sized bubbles and then completely dissolved as they disappear. It can be generated in a variety of ways. Currently, it is widely used in various industries and environmental fields, and the application field is further expanding.

The principle of siphon refers to a tube or action and phenomenon that uses atmospheric pressure to move a liquid from a higher place to a lower place. This is because, according to Bernoulli's principle, the pressure of the liquid moving inside the tube is lower than the atmospheric pressure, so the effect of pressing the water surface of the barrel where the atmospheric pressure is high occurs. In real life, it is widely used in various fields such as the principle of the toilet, the principle of the gyeyeongbae drinking cup, petroleum bellows hose, drain trap, agricultural water irrigation, fabric softener inlet in washing machine, pressure gauge, and rain gauge.

In the case of KR10-0803706 B, which is a prior document, since the process of incineration of construction waste and waste wood is required, the limitation of installing a calcium carbonate device dependently on the incinerator and the reduction of carbon dioxide in the atmosphere is not helpful in reducing the concentration of carbon dioxide in the atmosphere limits arise. In addition, there is a limitation in that it is difficult to predict the quality due to the absence of quality information such as purity, particle size, and whiteness of calcium carbonate produced through the invention process.

Therefore, in the nano calcium carbonate manufacturing process, the commercialization of nano calcium carbonate production by carbon dioxide conversion from construction waste generated in large quantities is required.

Korean Registered Patent No. 10-0803706

In one aspect, an object of the present invention is to economically and efficiently produce calcium carbonate having a higher use value compared to general calcium carbonate by recycling waste concrete, which is a construction waste.

In one aspect, in the present specification, as an apparatus for producing nano calcium carbonate, an extraction tank for supplying an acidic solution, eluting divalent or trivalent cations in waste concrete to produce an elution solution; a neutralization tank connected to the extraction tank at a position lower than the extraction tank and neutralizing the elution solution by supplying a basic solution; a precipitation tank connected to the neutralization tank at a lower position than the neutralization tank and recovering impurities precipitated in the neutralization process; a filtration tank connected to the settling tank at a lower position than the settling tank, and including one or more filtration membranes; a storage tank connected to the filtration tank and storing the supernatant that has passed through the filtration tank; one or more reactors connected to the storage tank and reacting the supernatant liquid supplied from the storage tank with carbon dioxide; and a microbubble device connected to the one or more reaction tanks and supplying carbon dioxide in the form of microbubbles to the one or more reaction tanks, wherein the solution is moved without power from the extraction tank to the storage tank. provide the device.

In another aspect, in the present specification, there is provided a method for producing calcium carbonate using the above-described nano calcium carbonate production apparatus, the method comprising: supplying an elution solution from an extraction tank to a neutralization tank; supplying the solution neutralized in the neutralization tank to the precipitation tank; supplying a solution from which the solids precipitated in the precipitation tank are removed to the filtration tank; supplying a supernatant that has passed through one or more filtration membranes in a filtration tank to a storage tank; supplying the reservoir solution to one or more reactors, and setting the one or more reactors to carbonation conditions; producing nano calcium carbonate by supplying carbon dioxide to the reactor using a microbubble device; and recovering the calcium carbonate produced in the reaction tank; it provides a method for producing nano calcium carbonate, including, wherein the solution is supplied without power from the extraction tank to the storage tank.

According to the present specification, it is possible to extract calcium from waste concrete containing various ions and selectively precipitate impurities in the form of hydroxide compounds to prepare nano calcium carbonate through carbon dioxide reaction.

In the method for manufacturing nano calcium carbonate disclosed herein, the use of a pump required in the extraction, neutralization, precipitation, filtration, and storage steps is replaced by an eco-friendly method without power consumption using the principle of siphon, which reduces the power consumption by about It can reduce production costs by 18%.

In addition, in the present specification, high-quality nano calcium carbonate is produced by reacting nano- and micro-sized carbon dioxide using a microbubble device. In this way, it is possible to secure competitiveness in the market.

In addition, the nano calcium carbonate produced according to the present specification can be used as a building material, paint, paper, medicine, cosmetic, plastic, etc. with high quality. This means that high concentrations of carbon dioxide and waste resources in the atmosphere are converted into usable resources through this method to produce added value.

In addition, in the case of the apparatus and manufacturing method according to the present specification, by designing a continuous automation program and establishing a low-power process, it is possible to preempt the market with features such as an economical production environment establishment and mass production of equal quality.

1 shows a conceptual diagram of the entire process of the inorganic carbonation production process using waste concrete.
2 is a conceptual diagram showing the movement of the solution from the extraction tank to the storage tank according to the principle of the siphon.
3 is a graph of the extraction amount of ^{Ca 2 +} ions in the waste concrete for each concentration of the hydrochloric acid solution.
4 is a graph showing the precipitation conditions of ions according to pH.
5 is a pH change according to the injection amount of NaOH of 1M concentration in the Ca ^{2 + extraction solution in the neutralization step.}

Term Definition

In the present specification, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

exemplary of embodiments Explanation

Hereinafter, the present invention will be described in detail.

Nano calcium carbonate manufacturing device

Hereinafter, it will be described in detail with reference to FIGS. 1 and 2 .

In the present specification, as a nano calcium carbonate manufacturing apparatus, by supplying an acidic solution, the extraction tank 101 for eluting divalent or trivalent cations in the waste concrete to produce an elution solution; a neutralization tank 102 connected to the extraction tank at a position lower than the extraction tank and neutralizing the elution solution by supplying a basic solution; a precipitation tank 103 connected to the neutralization tank at a lower position than the neutralization tank and recovering impurities precipitated in the neutralization process; a filtration tank 104 connected to the settling tank at a lower position than the settling tank, and including one or more filtration membranes; a storage tank 105 connected to the filtration tank and storing the supernatant that has passed through the filtration tank; one or more reaction tanks 106 connected to the storage tank and reacting the supernatant liquid supplied from the storage tank with carbon dioxide; and a microbubble device 107 connected to the one or more reaction tanks and supplying carbon dioxide in the form of microbubbles to the one or more reaction tanks, wherein the solution is moved without power from the extraction tank to the storage tank. A calcium carbonate manufacturing apparatus is provided.

The nano calcium carbonate manufacturing apparatus disclosed herein is characterized in that there is no consumption of power in the process of moving the solution, particularly from the extraction tank to the storage tank. This uses the difference in water level between the extraction tank, neutralization tank, sedimentation tank, filtration tank, and storage tank and the principle of siphon. can be maximized.

Specifically, the movement of the solution from the extraction tank, the neutralization tank, the settling tank, the filtration tank, to the storage tank moves through the principle of the siphon. Because it moves using the pressure difference and gravity, no power consumption occurs. However, because the pump is used only in the drainage process to remove impurities (sludge), the effect of reducing about 18% of the amount of power when using the existing flow pump causes

For example, the waste concrete contains ^{many elements such as Al 3 +} , Mg ^{2 +} , Fe ^{3 +} along with ^{calcium ions (Ca 2+} ). When the waste concrete is added to an acidic solution, the elements are can also be extracted together to produce an elution solution.

In the case of a moving pipe installed to connect the extraction tank - neutralization tank - sedimentation tank - filtration tank - storage tank, the movement starts from the moment when the solution level inside each process equipment exceeds the height of the tube. The diameter of the tube may preferably be 30 mm or less, since it shows a sufficient flow rate at 30 mm or less.

In one embodiment, the extraction tank may include one or more of a flow rate controller and a propeller for mixing the solution, and by using this, the reaction rate of the solution may be increased to shorten the process time.

For example, the acidic solution in the extraction tank may be at least one selected from the group consisting of hydrochloric acid, ammonium salt solution, ammonium acetate solution, and ammonium chloride solution, and if it is an acidic solution containing chloride ions capable of eluting calcium ions, it is limited thereto. doesn't happen

For example, in the extraction tank, a ratio of waste concrete and an acidic solution (eg, hydrochloric acid) may be maintained at 1:15, and hydrochloric acid having a concentration of 0.5M to 1.0M may be used. This is because the extraction efficiency of calcium in waste concrete is excellent.

For example, in the extraction tank, the reaction time of the waste concrete and the acidic solution may be maintained within 30 minutes, and the injection rate of the solution may be maintained at 1 to 5 L/min, preferably 3 L/min. After 30 minutes, the extraction efficiency does not rise any more, because the continuous process is made by maintaining the injection rate of about 3L/min.

Then, the number of the divalent or trivalent adding a basic solution to the eluted solution containing the cation in the neutralization tank, followed by the precipitation of elements other than the Ca ^{2 +} in the form of hydroxide compounds can be removed of impurities.

In one embodiment, the neutralization tank may include one or more selected from the group consisting of a flow controller, a propeller for solution mixing, and a pH meter, and increase the reaction rate of the solution by using the flow controller and the propeller for solution mixing to increase the process time can be shortened.

For example, in the neutralization tank, a basic solution (eg, sodium hydroxide) having a concentration of 0.5 to 2 M, preferably 1 M, may be injected to adjust the pH of the extraction solution to 11.5, which means that all ions except calcium are removed at pH 11.5. because it settles.

For example, the basic solution may be a sodium hydroxide solution.

In addition, in one embodiment, by installing a sludge pump in the extraction tank and the neutralization tank drain, it is possible to facilitate the discharge of waste concrete having a large particle size.

In this case, it is preferable to perform a process of filtering the impurities, and the filtering process is not limited thereto as long as it is a method capable of separating impurities other than calcium ions.

In one embodiment, the settling tank may include a propeller for removing sludge having a particle size of 300 μm or more. This is to form the sedimentation of the floats in a centralized type, and it is because it is possible to facilitate the discharge of the sediments and prevent the clogging of the drainage channels.

In other words, the settling propeller of the settling tank facilitates discharge by concentrating the sludge to the center where the drain pipe is located, and has a structure that can discharge the sludge with priority. When the sludge is exhausted, the sludge pump is stopped because the solution does not need to be discharged any more.

In one embodiment, while the sludge is moved from the settling tank to the sludge tank through the sludge pump, it is preferable to install a network capable of separating the sludge and the solution inside the sludge storage tank. This is because solid-liquid separation can facilitate the treatment of sludge and wastewater.

In one embodiment, the filtration tank includes one or more filtration membranes, and the position of the one or more filtration membranes may be lowered in a solution movement direction. This is because, depending on the direction of solution movement, if the filtration membrane is higher or the same, the filtration effect may be lost due to mixing with the initially injected solution.

In addition, as in the above principle, by placing the bottom of the storage tank at a lower place than the filtration tank, the solution can be moved to the storage tank by pressure, and even when moving from the storage tank to the reaction tank, the reaction tank is installed at a later position so that the water level difference can move

In one embodiment, the storage tank may be connected to the filtration tank at a position lower than the filtration tank, and the reaction tank may be connected to the storage tank at a position lower than the storage tank.

Thereafter, carbon dioxide is supplied to the elution solution from which the impurities are removed to produce calcium carbonate. As a mineral carbonation reaction, the carbon dioxide reacts with calcium ions contained in the elution solution to produce calcium carbonate.

For example, by using a plurality of reactors, the carbonation process and the injection of the solution immediately before carbonation may be alternately performed. This is because the time required for carbonation and the injection time of the solution are the same, so that a continuous process can be performed to maximize productivity. In addition, even when moving from the storage tank to the reaction tank, the reaction tank can be installed at a lower position to move by the water level difference.

In the reactor, a microbubble device is included therein, and carbon dioxide is supplied in the form of microbubbles to the elution solution from which impurities are removed. completely dissolved until As such, carbon dioxide in the form of microbubbles acts as a microreactor and reacts with calcium hydroxide to produce nano-sized calcium carbonate.

In one embodiment, the diameter of the microbubbles may be 50 μm or less.

In one embodiment, the one or more reaction tanks may include one or more selected from the group consisting of a flow controller, a gas controller, a pH meter, and a solenoid valve. The reason why the pH is installed inside the reaction tank is because it is possible to reliably control the completion of the reaction because the pH is decreased according to the injection of carbon dioxide. In addition, by installing a solenoid valve, the solution supplied from the microbubble device can be continuously operated.

In other words, the Ca(OH) ₂ solution and CO2 in the reactor may be injected into the microbubble device and mixed in the device. That is, the solution and CO ₂ are injected and discharged into the microbubble device, which can be controlled by a solenoid valve.

In one embodiment, the nano calcium carbonate manufacturing apparatus, connected to the at least one reaction tank, the recovery unit 108 for recovering the produced calcium carbonate using a centrifuge; may further include.

In one embodiment, the pH in the reaction tank may be 11.5.

In one embodiment, the microbubble device may be a microbubble pump or a pressure-dissolving microbubble device, and preferably, a pressure-dissolving microbubble device may be used. In addition, in the case of a microbubble pump, a method of mixing inside the device is used, because there is a limitation in setting design conditions according to the size and capacity of the pump.

In one embodiment, the calcium carbonate manufacturing apparatus, a control unit capable of controlling one or more selected from the group consisting of a propeller, a valve, a flow rate, a pump, and pH; may further include.

Nano calcium carbonate manufacturing method

In the present specification, there is provided a method for producing calcium carbonate using the above-described nano calcium carbonate production apparatus, the method comprising: supplying an elution solution from an extraction tank to a neutralization tank; supplying the solution neutralized in the neutralization tank to the precipitation tank; supplying a solution from which the solids precipitated in the precipitation tank are removed to the filtration tank; supplying a supernatant that has passed through one or more filtration membranes in a filtration tank to a storage tank; supplying the reservoir solution to one or more reactors, and setting the one or more reactors to carbonation conditions; producing nano calcium carbonate by supplying carbon dioxide to the reactor using a microbubble device; and recovering the calcium carbonate produced in the reaction tank; it provides a method for producing nano calcium carbonate, including, wherein the solution is supplied without power from the extraction tank to the storage tank.

In one embodiment, when the pH of the solution in the neutralization tank reaches 11.5, the supply of the basic solution may be stopped.

In one embodiment, the composition of carbonation conditions in the reaction tank is performed by supplying a basic solution, and when the pH of the solution in the reaction tank reaches 12.5, the supply of the basic solution is stopped, and carbon dioxide can be injected have.

In one embodiment, when the pH of the solution in the reaction tank is 7 or less, the injection of carbon dioxide may be stopped.

In one embodiment, the flow rate of the carbon dioxide may be 5 L/min or more, preferably 6 L/min. When supplied in the above amount, the reaction of the reactor may be adjusted to 30 minutes or less.

In one embodiment, the step of generating nano calcium carbonate in the reactor may be performed within 30 minutes.

In one embodiment, the recovering may be recovered using a centrifuge.

Hereinafter, the present invention will be described in more detail through the following examples. However, the following examples are provided only for the purpose of illustration to help the understanding of the present invention, and the scope and scope of the present invention are not limited thereto.

Example

< from waste concrete Ca ^{2 +} Extraction of>

After pulverizing waste concrete using a boll-mill, particles of 150 μm or less were separated using a 100 mesh standard sieve. Then, 0.5M of HCl is injected for 30 minutes at a flow rate of 3L/min, CaCl ₂ It was extracted in the form of, and the chemical formula is as shown in the following formula (1).

CaO+2HCl→CaCl ₂ +H ₂ O Formula (1)

That is, the formula (1) through the waste concrete in the Ca ^{2 +} HCl in a 1: It can be seen that the reaction rate by two. ^{Many elements such as Al 3 +} , Mg ^{2 +} , Fe ^{3 +} are contained in the waste concrete, and the corresponding elements are also extracted according to the pH value. Thus by precipitating the element except Ca ^{2 +} in the form of hydroxide compound to remove the impurities.

<Removal of impurities through NaOH injection>

Injecting a NaOH concentration of 1M in order to remove the elements, except for Ca ^{2 +} in the extraction solution by M (OH) _x It was removed by precipitation in the form. At this time, in order to evaluate the conditions under which each element precipitates, the formation of precipitation of ions by pH was analyzed.

As a result, Fe ^{3 +} is above pH 3, Al ^{3 +} is pH 5.8, Mg ^{2 +} was fully precipitated at pH 11, Ca ^{2 +} is a case confirmed to exist in ionic form at pH 11.5 Injection of NaOH solution Conditions were set up to pH 11.5. The appropriate amount to achieve the pH 11.5 condition was derived to be 2/3 of the HCl content through the experiment.

Therefore, in this example, 1M NaOH solution was injected as much as 2/3 of the HCl content to achieve impurity removal conditions, and then the solution was moved.

<Separation of sediment>

When the solution mixed with impurities is injected into the settling tank, the impurities are aggregated to the center of the settling tank through the centralized propeller of the settling tank. was discharged with

The supernatant from which the sediment is separated from the settling tank is moved to the filtration tank, and three filtration membranes are installed inside the filtration tank. have.

<micro bubble injection of carbon dioxide in the form of >

Filtered Ca(OH) _{2 inside the reactor} The solution was injected, and sodium hydroxide was additionally injected until pH 12.5 was reached. Thereafter, carbon dioxide bubbles having a concentration of 99% of the micro size were mixed to produce calcium carbonate having a nano particle size. At this time, the completion of the reaction was set as a condition when pH 7 was reached.

The chemical formula of nano calcium carbonate is shown in the following formula (2).

Ca(OH) ₂ +CO ₂ →CaCO ₃ +H ₂ O Formula (2)

That is, it can be seen that 44.01 g/mol of carbon dioxide reacts to produce 100.0869 g/mol of calcium carbonate, and through this, the amount of injected carbon dioxide can be calculated from the amount of calcium carbonate produced.

As a method applied to the process, it can be seen that the amount of dissolved gas increases in proportion to the pressure according to Bernoulli's Law PV=P'V' by installing a pressure-dissolving microbubble device at the bottom of the reactor. The pressure dissolution method uses these characteristics to dissolve carbon dioxide in an aqueous solution and then reduce pressure to create supersaturated conditions, and is designed to automatically shut off when pH 7 is reached through a pH meter.

The time to reach pH 8 may vary depending on the flow rate conditions, but in the process, it was set to 30 minutes so that a continuous process could be performed. In addition, it can be seen that the pressure dissolution method is inversely proportional to the pressure and flow rate based on the PV=nRT formula, and it is judged that it is not necessary to consider the bubble generation amount and the clogging problem by foreign substances in the process conditions.

3 is a graph of the extraction amount of ^{Ca 2 +} ions in the waste concrete for each concentration of the hydrochloric acid solution. In the graph, the efficiency compared to the HCl content of 0.5M and 0.75M HCl is indicated in red. When 0.5M HCl was used _{, 100% was extracted with CaCl 2} , and in the case of 0.75M, it was confirmed through analysis that the Ca extraction efficiency increased by 45% when the HCl concentration of 50% from 0.5M was increased, which is the HCl price. and CaCO _{3 It} is shown as a factor that can change conditions depending on the price.

4 is a graph showing the precipitation conditions of ions according to pH. Ions except Ca ions should be removed by precipitation. At this time, at pH 2.5-3, Fe ions are precipitated, in the pH 4.5-5 range, Al ions, and in the pH 10-10.5 range, Mg ions are precipitated. However, even at pH 11.5, it can be confirmed through the graph that Ca is not precipitated and exists in ionic form. Therefore, pH 11.5 was set as the neutralization condition.

5 is a pH change according to the injection amount of NaOH of 1M concentration in the Ca ^{2 + extraction solution in the neutralization step.} The pH change was measured by injecting 100 ml of 1M NaOH solution into 6L of the solution extracted with 0.5M HCl. Through the graph, it was confirmed that about 2 L of NaOH solution was injected to reach the neutralization condition, pH 11.5. Therefore, it can be indirectly confirmed that the neutralization condition can be reached by injecting a NaOH solution of about 2/3 of the HCl content.

Table 1 below shows the results regarding the difference according to the power consumption of the conventionally designed process and the low-power-based process. In the case of the existing process, a flow pump must be used to move the solution to each tank, such as extraction, neutralization, precipitation, filtration, and storage. % can be reduced.

Existing power consumption
(kW) division Low power based power consumption
(invention of the present invention)
(kW) 4.4 flow pump - 0.088 sludge pump 0.088 0.58 drain pump 0.58 0.3 pH meter 0.3 11 prop 11 8 microbubble 8 24.368 Sum 19.968

10: acid solution
20: basic solution
101: extraction tank
102: neutralization tank
103: sedimentation tank
104: filter tank
105: storage tank
106: reactor, 106a: reactor 1, 106b reactor 2
107: micro-bubble device, 107a: micro-bubble device 1, 107b: micro-bubble device 2
108: recovery unit

Claims (17)

As a nano calcium carbonate manufacturing apparatus,
an extraction tank for producing an elution solution by supplying an acidic solution and eluting divalent or trivalent cations in the waste concrete;
a neutralization tank connected to the extraction tank at a position lower than the extraction tank and neutralizing the elution solution by supplying a basic solution;
a precipitation tank connected to the neutralization tank at a lower position than the neutralization tank and recovering impurities precipitated in the neutralization process;
a filtration tank connected to the settling tank at a lower position than the settling tank, and including one or more filtration membranes;
a storage tank connected to the filtration tank and storing the supernatant that has passed through the filtration tank;
one or more reactors connected to the storage tank and reacting the supernatant liquid supplied from the storage tank with carbon dioxide; and
a microbubble device connected to the one or more reaction tanks and supplying carbon dioxide in the form of microbubbles to the one or more reaction tanks;
The solution is moved without power from the extraction tank to the storage tank, and the solution is moved using a water level difference, nano calcium carbonate manufacturing apparatus. According to claim 1,
The extraction tank will include at least one of a flow controller and a propeller for solution mixing, nano calcium carbonate manufacturing apparatus. According to claim 1,
The neutralization tank will include at least one selected from the group consisting of a flow control meter, a propeller for solution mixing, and a pH meter. According to claim 1,
The settling tank is a nano calcium carbonate manufacturing apparatus comprising a propeller for removing sludge having a particle size of 300 μm or more. According to claim 1,
The filtration tank comprises one or more filtration membranes,
The position of the one or more filtration membranes is that the height is lowered in the solution movement direction, nano calcium carbonate manufacturing apparatus. According to claim 1,
The one or more reaction tanks will include one or more selected from the group consisting of a flow controller, a gas controller, a pH meter, and a solenoid valve, nano calcium carbonate production apparatus. According to claim 1,
The nano calcium carbonate manufacturing apparatus,
It is connected to the one or more reaction tanks, and a recovery unit for recovering the calcium carbonate produced by using a centrifuge; will further include, the nano calcium carbonate manufacturing apparatus. According to claim 1,
The pH in the reaction tank is 11.5, nano calcium carbonate manufacturing apparatus. According to claim 1,
The microbubble device is a microbubble pump or a pressure dissolution type microbubble device. According to claim 1,
The calcium carbonate production apparatus,
A control unit capable of controlling one or more selected from the group consisting of a propeller, a valve, a flow rate, a pump, and pH; Will further comprising a, nano calcium carbonate manufacturing apparatus. As a nano calcium carbonate manufacturing method using the nano calcium carbonate manufacturing apparatus according to any one of claims 1 to 10,
supplying the elution solution from the extraction tank to the neutralization tank;
supplying the solution neutralized in the neutralization tank to the precipitation tank;
supplying a solution from which the solids precipitated in the precipitation tank are removed to the filtration tank;
supplying a supernatant that has passed through one or more filtration membranes in a filtration tank to a storage tank;
supplying the reservoir solution to one or more reactors, and setting the one or more reactors to carbonation conditions;
generating nano calcium carbonate by supplying carbon dioxide to the reactor using a microbubble device; and
Including; recovering the calcium carbonate produced in the reaction tank;
The solution is supplied without power from the extraction tank to the storage tank, and the solution is moved using a water level difference, nano calcium carbonate manufacturing method. 12. The method of claim 11,
The recovering step is to be recovered using a centrifuge, nano calcium carbonate production method. 12. The method of claim 11,
When the pH of the solution in the neutralization tank reaches 11.5, the supply of the basic solution is stopped, nano calcium carbonate manufacturing method. 12. The method of claim 11,
To create carbonation conditions in the reaction tank,
carried out by supplying a basic solution,
When the pH of the solution in the reaction tank reaches 12.5, the supply of the basic solution is stopped, and carbon dioxide is injected. 15. The method of claim 14,
When the pH of the solution in the reaction tank is 7 or less, the carbon dioxide injection is stopped, nano calcium carbonate manufacturing method. 12. The method of claim 11,
The flow rate of the carbon dioxide is 5 L / min or more, nano calcium carbonate manufacturing method. 12. The method of claim 11,
The step of generating the nano calcium carbonate in the reaction tank will be performed within 30 minutes, nano calcium carbonate manufacturing method.

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