KR101733071B1 - Method and Device for Producing Carbonate - Google Patents

Method and Device for Producing Carbonate Download PDF

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Publication number
KR101733071B1
KR101733071B1 KR1020150053354A KR20150053354A KR101733071B1 KR 101733071 B1 KR101733071 B1 KR 101733071B1 KR 1020150053354 A KR1020150053354 A KR 1020150053354A KR 20150053354 A KR20150053354 A KR 20150053354A KR 101733071 B1 KR101733071 B1 KR 101733071B1
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South Korea
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carbonated
solution
nozzle
carbonate
gas
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KR1020150053354A
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Korean (ko)
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KR20160123163A (en
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정우철
이상길
박광석
박성국
김기영
위진엽
이현우
박운경
이명규
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재단법인 포항산업과학연구원
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    • C01B31/24—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
    • B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/24—Magnesium carbonates

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Materials Engineering (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

The apparatus for producing carbonate according to an embodiment of the present invention includes a reactor in which a solution to be carbonated is reacted with a carbonated gas, a first nozzle located at one side of the reactor and discharging a solution to be carbonated into the reactor, A second nozzle for spraying a carbonic acid gas into the path through which the solution is discharged to form a mist composed of the solution to be carbonized and the carbonated gas and a recovery unit located at the lower end of the reactor for recovering the carbonate from the slurry formed in the reactor.
The method for producing carbonate according to an embodiment of the present invention includes the steps of discharging a solution to be carbonated from a first nozzle, spraying carbon dioxide gas from a second nozzle in a path through which the solution to be carbonated is discharged, Forming a slurry containing carbonate in the mist by reacting the cation of the solution to be carbonated with the carbonated gas, and recovering the carbonate from the slurry.

Description

METHOD AND DEVICE FOR PRODUCING CARBONATE

And more particularly, to a method and apparatus for producing carbonates.

The production process of lithium carbonate (Li 2 CO 3 ) using carbon dioxide (CO 2 ) gas uses a facility equipped with a reaction tank for the reaction of lithium hydroxide (LiOH) and carbon dioxide gas. The lithium hydroxide aqueous solution is a basic solution. The carbon dioxide gas is dissolved in the aqueous solution of lithium hydroxide to convert lithium hydroxide to lithium carbonate to produce lithium carbonate. This method should be controlled to maintain the base solution so that the carbonic acid gas is easily dissolved, and to prevent the carbonic acid gas from becoming excessively dissolved.

When the lithium hydroxide aqueous solution is in a strong base state, the carbonic acid gas dissolves very quickly, thereby causing a reaction with lithium carbonate. This reaction uses a method of bubbling carbonic acid gas into the lithium hydroxide aqueous solution in the tank. At this time, since the reaction with lithium carbonate is the fastest in the vicinity of the nozzle for bubbling carbon dioxide gas, the problem of nozzle clogging due to the reacted lithium carbonate occurs.

In order to solve such a problem, conventionally, a pressurized tank is prepared, a lithium hydroxide aqueous solution is filled therein, carbonic acid gas is injected under a pressurized state, and a lithium hydroxide aqueous solution is strongly mixed with a carbonic acid gas using a stirrer to cause a lithium carbonate reaction . This method has a problem that a large amount of carbon dioxide gas is used and a reaction time is long because a reaction vessel using high-pressure carbon dioxide gas is used.

As a conventional technique for solving such a problem, there is a carbonation apparatus in which a pressurized tank is prepared, and then a lithium hydroxide aqueous solution is dropped into a pressurized vessel in a droplet state to perform a reaction. However, even if a pressurized tank is used, this droplet jetting method requires carbon dioxide gas pressure maintaining equipment with very precise pressure means because it instantaneously causes negative pressure by consuming carbon dioxide gas in the tank immediately after jetting the droplet .

Further, since the process of reacting the injected lithium hydroxide aqueous solution with lithium carbonate is in a pressurized state, excessive carbon dioxide gas is dissolved. As a result, the pH of the aqueous solution of lithium hydroxide rapidly drops from neutral to neutral in the initial basic state due to excess unreacted carbon dioxide gas after the lithium carbonate reaction. excessive carbonic acid causes a carbonate reaction during the pH lowering process, resulting in a problem that the lithium carbonate produced is re-dissolving into aqueous lithium hydroxide solution.

The redissolution problem of lithium carbonate can be prevented by precisely controlling the pH. However, it is not easy to control the reaction of the carbonic acid gas dissolved in the lithium hydroxide aqueous solution. If the additional reactant is added for the pH control, an unwanted reaction by-product is generated and an additional process for removing the reaction by- , It is very difficult to effectively regulate the redissolving reaction, resulting in a problem of lowering the production yield of lithium carbonate.

Provided are a method and apparatus for producing carbonates by spraying carbon dioxide gas into a discharge path of a solution to be carbonated to form a mist and immediately react the carbonated target solution and the carbonated gas in the mist.

There is provided a lithium carbonate powder produced from a lithium hydroxide droplet containing carbon dioxide gas.

The apparatus for producing carbonate according to an embodiment of the present invention includes a reactor in which a solution to be carbonated is reacted with a carbonated gas, a first nozzle located at one side of the reactor and discharging the solution to be carbonated into the reactor, A second nozzle for spraying a carbonic acid gas into the path through which the solution is discharged to form a mist composed of the solution to be carbonized and the carbonated gas and a recovery unit located at the lower end of the reactor for recovering the carbonate from the slurry formed in the reactor.

The recovery section may include a filtration section for filtering the carbonate from the slurry.

The collecting part may include a drying part for drying the filtered carbonate.

The recovery unit may include a plurality of filtration units, and the recovery unit may include a draw-out unit that connects the reactor and the plurality of filtration units, and a valve that is provided in the flow path that connects the draw-out units and the respective filtration units.

The recovery unit includes a control unit connected to the valve, and the control unit controls the valve to control the throughputs of the plurality of filtration units.

And a carbon dioxide gas recirculation unit for recycling the carbon dioxide gas injected from the second nozzle and recirculating the carbon dioxide gas to the second nozzle.

The carbonated target solution circulating unit may further include a carbonated target solution circulating unit that recovers the target carbonated solution from the slurry in which the carbonate is filtered and recycles the carbonated target solution to the first nozzle.

The second nozzle may be a plurality of nozzles.

The first nozzle and the second nozzle can form an angle of 10 [deg.] To 70 [deg.] In the flow vertical direction to the flow direction origin of the solution to be carbonated.

The first nozzle and the second nozzle can form an angle of 30 DEG to 50 DEG in the vertical direction of flow to the flow direction origin of the solution to be carbonated.

The first nozzle may be located on the upper side of the reactor, and the second nozzle may be installed below the first nozzle.

The second nozzle can inject carbon dioxide gas at a pressure of 1.5 bar to 2.5 bar.

The second nozzle may be installed so that carbon dioxide gas is injected in a direction away from the central portion of the carbonated target solution to be discharged on a plane perpendicular to the direction in which the solution to be carbonated is discharged.

According to an embodiment of the present invention, there is provided a method of producing carbonates, comprising: discharging a solution to be carbonated from a first nozzle (S10); injecting carbon dioxide gas from a second nozzle into a path through which a solution to be carbonated is discharged, A step S30 of forming a slurry containing a carbonate by reacting the cation of the solution to be carbonated with the carbonated gas in the mist, and a step S40 of recovering the carbonate from the slurry do.

The solution to be carbonated may be a cation, and may include calcium ion, magnesium ion or lithium ion.

The pH of the solution to be carbonated may be pH 10 or higher.

The discharge path of the carbonated object solution and the injection path of the carbonated gas can form an angle of 10 [deg.] To 70 [deg.] In the vertical direction of flow to the flow direction origin of the carbonated object solution.

The discharge path of the solution to be carbonated and the injection path of the carbon dioxide gas can form an angle of 30 ° to 50 ° in the vertical direction of flow to the flow direction origin of the carbonated target solution.

The carbonic acid gas may be injected in a direction away from the central portion of the carbonic acid solution to be discharged from a surface perpendicular to the direction in which the solution to be carbonated is discharged.

The droplet size of the solution to be carbonated in the mist may be 10 nm to 50 탆.

The carbon dioxide from the second nozzle can be injected at a pressure of 1.5 bar to 2 bar.

The step of recovering the produced carbonate may include a step of recovering the carbonate by filtering the solution to be carbonated containing the carbonate.

The step of recovering the carbonate produced may comprise drying the filtered carbonate.

The lithium carbonate powder according to an embodiment of the present invention is produced from a lithium hydroxide droplet containing carbon dioxide gas.

The size of the lithium carbonate powder may be 2 탆 to 20 탆.

The size of the lithium hydroxide droplet may be 10 nm to 50 탆.

The solution to be carbonated and the carbonated gas immediately react, and no additional reaction or side reaction occurs. Only water (H 2 O) is produced in addition to the carbonate in the reaction of the carbonation target solution with the carbonated gas, and side reactions other than the carbonate reaction do not occur.

The pH of the carbonation target solution before and after the carbonation target solution and the carbonation gas is reacted with each other is kept substantially constant so that the prepared carbonate solution does not redissolve into the reacted carbonation target solution.

This serves as a technical advantage in the actual process, which makes it possible to maintain the quality of the carbonate produced regardless of the flow of time, which makes the process management very easy and simple.

Further, even when the unreacted cations remaining in the filtrate are re-reacted, there is no change in the pH, so that the re-reaction can be repeated until a desired level of recovery is obtained several times.

In addition, the entire reaction process is performed at normal pressure and at room temperature, so that the reactor can be simply constructed.

The carbonated reaction takes place in the nozzle through which the solution to be carbonated is discharged or the mist sprayed with the carbonic acid gas, so that the nozzle is not blocked by the produced carbonate.

Continuous injection and reaction processes are possible, thus increasing the efficiency of production.

1 is a schematic view schematically showing an apparatus for producing carbonate according to an embodiment of the present invention.
2 is a schematic view showing a first nozzle and a second nozzle of a device for producing carbonate according to an embodiment of the present invention.
3 is a schematic top view of an apparatus for producing carbonate according to one embodiment of the present invention.
FIG. 4 is a schematic view schematically showing a state in which the solution to be carbonated is discharged in the apparatus for producing carbonate of FIG. 1;
FIG. 5 is a schematic view schematically showing a state in which carbon dioxide gas is injected into a mist state in the apparatus for producing carbonate of FIG. 1, and an enlarged view of collision of carbonated gas droplets and carbon dioxide gas.
FIG. 6 is a schematic flow chart of a method for producing carbonate according to an embodiment of the present invention.
FIG. 7 shows the XRD analysis results of the carbonate prepared by the production method of FIG.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention.

The singular forms as used herein include plural forms as long as the phrases do not expressly express the opposite meaning thereto. Means that a particular feature, region, integer, step, operation, element and / or component is specified, and that other specific features, regions, integers, steps, operations, elements, components, and / And the like.

Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

Commonly used predefined terms are further interpreted as having a meaning consistent with the relevant technical literature and the present disclosure, and are not to be construed as ideal or very formal meanings unless defined otherwise.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

The apparatus for producing carbonate comprises a reactor 50 in which a solution 60 to be carbonated and a carbonated gas 70 react with each other, a first nozzle (not shown) disposed at one side of the reactor 50 and discharging the solution 60 to be carbonated into the reactor 50 10, a mist generated by the carbonated target solution 60 and the carbonated gas 70 is formed by spraying the carbonated gas 70 in the path where the carbonated target solution 60 is discharged, positioned adjacent to the first nozzle 10 And a recovery unit 30 located at the lower end of the reactor 50 and for recovering the carbonate 80 from the slurry formed in the reactor 50. In addition, if necessary, the apparatus for producing carbonate may further include other constitutions.

1 schematically shows an apparatus for producing carbonate according to an embodiment of the present invention. The apparatus for producing a carbonate of FIG. 1 is merely for illustrating the present invention, and the present invention is not limited thereto. Therefore, the apparatus for producing carbonate can be variously modified.

Fig. 1 shows a schematic view of an apparatus for producing a whole carbonate, and Fig. 2 schematically shows a first nozzle and a second nozzle of a device for producing carbonate.

Referring to FIGS. 1 and 2, the carbonated target solution 60 and the carbonated gas 70 react in the reactor 50.

A nozzle unit 100 for discharging the carbonation target solution 60 and the carbonated gas 70 into the reactor 50 is disposed at one side of the reactor 50. The nozzle unit 100 includes a first nozzle 10 for discharging a solution 60 to be carbonated into the reactor 5 and a second nozzle 10 for supplying a carbonated gas 70 (Not shown).

A first nozzle (10) for discharging a solution to be carbonated into the reactor (50) is installed at one side of the reactor (50). A second nozzle (20) is provided at a position adjacent to the first nozzle (10). A carbonic acid gas 70 is sprayed from the second nozzle 20 to the path through which the carbonation target solution 60 is discharged from the first nozzle 10 to form a mist composed of the carbonation target solution 60 and the carbonated gas 70 And the carbonate solution 80 and the carbonated gas 70 react with each other in the mist.

At the lower end of the reactor 50, a recovery unit 30 for recovering the carbonate 80 from the slurry formed in the reactor 50 is provided.

The recovery section 30 includes filtration sections 31 and 32 for filtering the carbonate from the slurry and may include a drying section for drying the filtered carbonate. The recovery unit 30 may include a lead-out unit 34 connecting the reactor 50 and the filtration units 31 and 32.

The filtration units 31 and 32 may be composed of a plurality of filtration units 31 and 32. Although the two filtration units 31 and 32 are shown in FIG. 1 for the sake of convenience, . When a plurality of filtration units 31 and 32 are constructed, a valve 33 may be installed in the flow path connecting the extraction unit 34 and the respective filtration units 31 and 32.

The plurality of valves 33 provided in the respective flow paths are controlled by a controller (controller) 35 connected to the valves, so that the throughput of the plurality of filtration sections 31 and 32 can be controlled. The control unit controls the opening and locking of the plurality of valves 33 so that the slurry can be alternately filtered through the plurality of filtration units 31 and 32. For example, if the first filtration part 31 is filtrated with a certain amount of the carbonate 80 over the entire throughput, the filtration efficiency is lowered. Accordingly, the valve 33 installed in the flow path connected to the first filtration section 31 is closed through the control section and the valve 33 provided in the flow path connected to the second filtration section 32 is opened to supply the slurry to the second filtration section 32. [ Thereby controlling the throughputs of the first filtration unit and the second filtration unit.

The first filtration section 31 and the second filtration section 32 are repeatedly provided in such a manner that the filtration filter of the first filtration section 31 is replaced while the slurry containing the carbonate is filtered by the second filtration section 32 So that the filtration process can be continuously performed.

When the throughput of one of the plurality of the filtration units 31 and 32 reaches 80% or more of the total throughput of the filtration unit, the control unit locks the valve connected to the filtration unit, opens the valve connected to the other filtration unit, It is possible to control the valves so that the filtration units 31 and 32 can be alternately operated, thereby controlling the throughputs of the plurality of filtration units 31 and 32.

1, the apparatus for producing carbonate may further include a carbonated gas circulating unit 40. The carbonated gas circulating unit 40 recovers the carbonated gas 70 injected from the second nozzle 20, Dried through the filter, and circulated back to the second nozzle 20 together with the new carbonated gas 70. The carbonated gas 70 can be efficiently used by reusing the carbonated gas 70 through the carbonated gas circulation part 40. [

The apparatus for producing carbonate may further include a solution circulating unit 41 to be carbonated, and the solution circulating unit 41 to be carbonated may recover the solution 60 to be carbonated from the slurry in which the carbonate 80 is filtered, 10). ≪ / RTI > There is an advantage that the target carbonated solution 60 can be efficiently used by reusing the carbonated target solution 60 through the carbonated target solution circulating part 41 and almost no carbonated target solution 60 is discarded.

Hereinafter, the first nozzle 10 and the second nozzle 20 will be described in more detail with reference to FIG.

As shown in Fig. 2, a plurality of second nozzles 20 may be provided. In addition, the first nozzle 10 and the second nozzle 20 can form an angle? Of 10 ° to 70 ° in the flow vertical direction to the flow direction origin of the carbonation target solution 60. When the angle is less than 10 degrees, the carbonate 80 is produced at the inlet of the first nozzle 10 or the second nozzle 20, and the problem of clogging the inlet of the first nozzle 10 or the second nozzle 20 May occur. When the angle is 70 degrees or more, the area where the carbonated target solution 60 and the carbonated gas 70 collide with each other becomes narrow, so that the reaction between the carbonated target solution 60 and the carbonated gas 70 may not be smoothly performed have. More specifically, the first nozzle 10 and the second nozzle 20 preferably have an angle of 30 to 50 degrees in the flow vertical direction to the flow direction origin of the carbonation target solution 60. [

The first nozzle 10 may be installed on the upper side of the reactor 50 and the first nozzle 10 may be installed on the upper side of the second nozzle 20. Specifically, it is preferable that the second nozzle 20 is installed at a position 3 mm to 20 mm below the first nozzle 10. The distance between the first nozzle 10 and the second nozzle 20 can be determined in proportion to the amount of the solution to be carbonated 60 discharged from the first nozzle 10. For example, the amount of the carbonated target solution 60 discharged from the first nozzle 10 may be from 100 ml / min to 5000 ml / min, and the amount of the carbonated target solution 60 discharged from the first nozzle 10 and the second nozzle 20 The distance can be adjusted in the range of 3 mm to 20 mm. When the amount of the carbonation target solution 60 discharged from the first nozzle 10 exceeds 5000 ml / min, the second nozzle 20 can be additionally provided.

The carbon dioxide gas 70 is injected from the second nozzle 20 into the path 11 through which the carbonated target solution 60 is discharged so that the carbonated gas 70 immediately reacts with the carbonated target solution 60, (60) is pulverized into a mist state.

The pressure of the carbonated gas 70 injected from the second nozzle 20 may be 1.5 bar to 2.5 bar.

3, the second nozzle 20 is carbonated in a direction away from the center portion c of the carbonated target solution 60 to be discharged on a plane perpendicular to the direction in which the carbonated target solution 60 is discharged Gas may be injected. When a plurality of the second nozzles 20 are provided, the plurality of second nozzles 20 are arranged in a direction away from the center portion of the carbonated target solution 60 to be discharged from the right side (or left side) The carbonated target solution 60 is crushed and twisted in the counterclockwise (or clockwise) direction, so that the mist can be formed. In FIG. 3, two second nozzles 20 are provided so as to inject carbon dioxide gas to the right from the center of the carbonation target solution 60, thereby showing an example in which the target carbonated solution 60 is misted in the counterclockwise direction while being rotated do.

Fig. 4 schematically shows the shape of the solution 60 to be carbonated discharged from the first nozzle 10. Fig.

The discharged carbonated target solution 60 can flow out from the first nozzle 10 with a constant flow. Specifically, the solution to be carbonated 60 leaving the first nozzle 10 can be configured to have a flow similar to the free flow in the gravitational field.

5 schematically shows a state in which carbonic acid gas 70 is injected from the second nozzle 20 and the carbonation target solution 60 is in a mist state and the collision of the droplets of the carbonation target solution 60 with the carbonated gas 70 The enlarged view is shown.

The droplet size of the liquid to be carbonated 60 in the mist state can be 10 nm to 50 占 퐉. If the droplet size is too small, the surface area of the droplet becomes large and the carbonated gas 70 may be over-soluble in the carbonation target solution 60. If the droplet size is too large, the surface area of the droplet becomes small, 70 may not be sufficiently dissolved in the carbonization target solution 60. [

The injected carbonated gas 70 is instantaneously dissolved in the solution 60 to be carbonated in a strong base and reacts with cations in the carbonation target solution 60 to be converted into carbonate 80. [ For example, when the solution 60 to be carbonated is an aqueous lithium hydroxide solution and the carbonated gas 70 is carbon dioxide gas, the reaction formula can be expressed as follows.

2Li + + 2OH - + CO 2 (aq) + H 2 O → 2Li + + 2OH - + H 2 CO 3 (aq) →

2Li + + 2OH - + H + + HCO 3 - → 2Li + + OH - + HCO 3 - + H 2 O →

2Li + + CO 3 2- + 2H 2 O → Li 2 CO 3 ↓ + 2H 2 O

As shown in the above reaction formula, only water (H 2 O) is generated in addition to the carbonate (80) in the reaction of the carbonation target solution (60) and the carbonated gas (70), and side reactions other than the carbonate reaction do not occur.

As a result, the pH of the carbonation target solution 60 before / after the carbonation target solution 60 and the carbonated gas 70 are reacted with each other is kept substantially constant, so that the prepared carbonate 80 is reused as a reaction target carbonated solution The sun will not rise. This serves as a technical advantage in the actual process, and it is possible to maintain the quality of the carbonate 80 produced regardless of the flow of time, so that the process control becomes very easy and simple. Further, even when the unreacted cations remaining in the filtrate are re-reacted, there is no change in the pH, so that the re-reaction can be repeated until a desired level of recovery is obtained several times. Also, the entire reaction process is performed at normal pressure and at room temperature, and thus the reactor 50 can be simply constructed.

Figure 6 schematically shows a flow chart of a process for producing carbonates according to one embodiment of the present invention. The flowchart of the method for producing carbonate of FIG. 6 is merely for illustrating the present invention, and the present invention is not limited thereto. Therefore, the method of manufacturing the carbonate can be variously modified.

As shown in FIG. 6, in the method for producing carbonates, carbonic acid gas is injected from a second nozzle into a path for discharging a solution to be carbonated from a first nozzle (S10) A step S30 of forming a slurry containing a carbonate by reacting the cation of the solution to be carbonated with the carbonated gas in the mist, and a step S40 of recovering the carbonate from the slurry do. In addition, the carbonate manufacturing method may further include other steps as needed.

First, in step S10, the carbonic acid production method discharges a solution to be carbonated from the first nozzle. The solution to be carbonated can be used without particular limitation as long as it is a substance that reacts with carbonated gas to cause carbonation. Specifically, the solution to be carbonated may include a calcium ion, a magnesium ion, or a lithium ion as a cation. More specifically, the solution to be carbonated may be an aqueous solution of lithium hydroxide.

The pH of the solution to be carbonated may be above pH 10. If the pH of the solution to be carbonated is too low, there is a possibility that the produced carbonate is redissolved in the solution to be carbonated.

The discharged carbonated target solution can be flowed out from the first nozzle with a constant flow. Specifically, the solution to be carbonated which leaves the first nozzle can be configured to have a flow similar to the free flow in the gravitational field.

Fig. 2 schematically shows the shape of the solution to be carbonated discharged from the first nozzle.

In step S20, carbon dioxide gas is injected from the second nozzle into the path through which the solution to be carbonated is discharged to form a mist composed of the carbonation target solution and the carbonated gas.

The discharge route of the carbonated object solution and the injection route of the carbonated gas can form an angle of 10 ° to 70 ° in the vertical direction of flow to the flow direction origin of the carbonated object solution. If the angle is too small, carbonate may be produced at the inlet of the first nozzle or the second nozzle, thereby blocking the inlet of the first nozzle or the second nozzle. If the angle is too large, the area of collision between the carbonated target solution and the carbonated gas becomes narrow, so that the reaction between the carbonated target solution and the carbonated gas may not be smoothly performed. More specifically, the discharge path of the solution to be carbonated and the injection path of the carbon dioxide gas can form an angle of 30 ° to 50 ° in the flow vertical direction to the flow direction starting point of the carbonation target solution.

The carbon dioxide gas is sprayed from the second nozzle to the path through which the solution to be carbonated is discharged, thereby pulverizing the carbonation target solution to form a mist composed of the carbonation target solution and the carbonated gas.

As shown in FIG. 3, the carbon dioxide gas can be injected in a direction away from the central portion (c) of the carbonated target solution to be discharged on a plane perpendicular to the direction in which the carbonated target solution is discharged. In the case where there are a plurality of second nozzles through which carbon dioxide gas is discharged, carbon dioxide gas is injected in a direction away from the center portion of the carbonated target solution to be discharged from the right side (or left side) of the carbonated gas based on the injection direction, Crushed, and twisted in a counterclockwise (or clockwise) direction to form a mist. In FIG. 3, two second nozzles are provided so as to inject carbon dioxide gas to the right from the center of the solution to be carbonated, thereby showing an example of making the object to be carbonized while rotating the carbonation target solution counterclockwise.

At this time, the size of the droplet of the solution to be carbonated in the mist state may be 10 nm to 50 占 퐉. If the droplet size is too small, the surface area of the droplet becomes large and the carbonated gas becomes over-soluble in the carbonated target solution. If the droplet size is too large, the surface area of the droplet becomes small, A problem that can not be solved can occur.

The pressure of the carbon dioxide gas to be injected can be adjusted from 1.5 bar to 2.5 bar to make the droplet size of the solution to be carbonated.

The injected carbon dioxide gas is instantaneously dissolved in the solution to be carbonated in a strong base, and reacts with lithium hydroxide in the solution to be carbonated to be converted into carbonate. For example, when the solution to be carbonated is a lithium hydroxide aqueous solution and the carbonated gas is carbon dioxide gas, the reaction formula can be expressed as follows.

2Li + + 2OH - + CO 2 (aq) + H 2 O → 2Li + + 2OH - + H 2 CO 3 (aq) →

2Li + + 2OH - + H + + HCO 3 - → 2Li + + OH - + HCO 3 - + H 2 O →

2Li + + CO 3 2- + 2H 2 O → Li 2 CO 3 ↓ + 2H 2 O

As shown in the above reaction formula, in addition to the carbonate, only water (H 2 O) is produced in the reaction of the carbonated target solution and the carbonated gas, and side reactions other than the carbonate reaction do not occur.

As a result, the pH of the solution to be carbonated before and after the reaction of the carbonation target solution with the carbonated gas is kept substantially constant, so that the produced carbonate does not redissolve into the reacted carbonated target solution. This is a very important technological advantage in the actual process, and the quality of the carbonate produced can be maintained regardless of the flow of time, which makes the process management very easy and simple. In addition, even when the unreacted Li ions remaining in the filtrate are re-reacted, there is no change in pH, so that the re-reaction can be repeated until a desired level of recovery is obtained several times. In addition, the entire reaction process is performed at normal pressure and at room temperature, so that the reactor can be simply constructed.

FIG. 2 schematically shows a state in which a carbonic acid gas is injected from a second nozzle to convert a liquid to be carbonated to a mist state, and a contact state of a carbonic acid gas with a droplet of a carbonated object solution is shown in an enlarged scale in a mist state.

In step S30, the cation of the solution to be carbonated reacts with the carbonated gas in the mist to form a slurry containing carbonate. The carbonate produced is contained in the slurry in a solid state.

In step S40, the carbonate is recovered from the slurry. The carbonate can be recovered by filtering the slurry. The filtered carbonate is dried to obtain a high-purity carbonate powder.

The lithium carbonate according to one embodiment of the present invention is produced from lithium hydroxide droplets containing carbon dioxide gas.

The prepared lithium carbonate is in the form of powder and may have a size of 2 탆 to 20 탆. More specifically, the powder size of lithium carbonate may be 4 탆 to 8 탆, and the size of the lithium droplets may be 10 nm to 50 탆.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited to the following examples.

Example

As the solution to be carbonated, a lithium hydroxide aqueous solution was used, and carbon dioxide gas was used as carbon dioxide gas. The lithium hydroxide aqueous solution was discharged into the reactor through the first nozzle and the carbon dioxide gas was injected from the second nozzle to react the aqueous solution of lithium hydroxide with the carbon dioxide gas. The angle between the discharge path of the first nozzle and the spray path formed by the second nozzle was adjusted to be 50 degrees in the vertical direction of flow to the flow direction origin of the solution to be carbonated and the pressure of the carbon gas injected from the second nozzle was adjusted to 2 bar Respectively. The reactor was maintained at normal pressure and room temperature.

The aqueous solution of lithium hydroxide reacted with carbon gas was filtered to obtain lithium carbonate, which was dried to finally obtain lithium carbonate in powder form. XRD analysis thereof is shown in FIG.

The lithium hydroxide aqueous solution was recovered in the lithium carbonate-filtered slurry and the same procedure was repeated.

The concentration of lithium in the aqueous solution of lithium hydroxide before the reaction, the concentration of lithium in the aqueous solution of lithium hydroxide after the first reaction, and the concentration of lithium in the aqueous solution of lithium hydroxide after the second reaction are summarized in Table 1 below.

Before reaction After one reaction After 2 reactions Lithium hydroxide concentration (mg / L) 30520 (100 wt%) 7642 (25.03 wt%)
74.96 wt% reaction 4748 (15.55 wt%)
84.44 wt% reaction

As shown in Table 1, it was confirmed that lithium carbonate could be obtained at a high yield of 84 wt% or more through two successive reactions.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

10: First nozzle 11: Carbonation target solution discharge path
20: second nozzle 21: carbon dioxide gas injection path
30: recovery unit 31, 32: filtration unit
33: valve 34:
35: control section 40: carbon dioxide gas circulation section
41: solution circulating part to be carbonated 50: reactor
60: solution to be carbonated 70: carbonated gas
80: Carbonate 100: Nozzle part

Claims (26)

A reactor in which carbonic acid gas reacts with a solution to be carbonated;
A first nozzle positioned at one side of the reactor for discharging the target carbonated solution into the reactor,
A second nozzle positioned adjacent to the first nozzle and spraying carbon dioxide gas to a path through which the carbonated target solution is discharged to form a mist composed of the solution to be carbonated and the carbonated gas,
And a recovery unit located at the lower end of the reactor for recovering carbonate from the slurry formed in the reactor,
Wherein the second nozzle is provided so that carbon dioxide gas is injected in a direction away from a central portion of the carbonated target solution to be discharged on a plane perpendicular to a direction in which the solution to be carbonated is discharged,
Apparatus for the production of carbonates. The method according to claim 1,
And the recovering portion includes a filtration portion for filtering the carbonate from the slurry. 3. The method of claim 2,
Wherein the recovery unit comprises a drying unit for drying the filtered carbonate. 3. The method of claim 2,
Wherein the recovery unit includes a plurality of filtration units,
Wherein the recovery unit includes a draw-out unit connecting the reactor and the plurality of filtration units, and a valve provided in a flow path connecting the draw-out unit and each of the filtration units. 5. The method of claim 4,
Wherein the recovery unit includes a control unit connected to the valve,
Wherein the control unit controls the valve to control the throughput of the plurality of filtration units. The method according to claim 1,
And a carbon dioxide gas recirculation unit for recycling the carbon dioxide gas injected from the second nozzle and recirculating the carbon dioxide gas to the second nozzle. The method according to claim 1,
Further comprising a carbonylation target solution circulating unit for collecting the carbonylation target solution from the slurry filtered with the carbonate and recirculating the carbonylation target solution to the first nozzle. The method according to claim 1,
Wherein the second nozzle comprises a plurality of carbonates. The method according to claim 1,
Wherein the first nozzle and the second nozzle form an angle of 10 DEG to 70 DEG in the vertical direction of flow to the flow direction origin of the solution to be carbonated. 10. The method of claim 9,
Wherein the first nozzle and the second nozzle form an angle of 30 ° to 50 ° in the vertical direction of flow to the flow direction origin of the solution to be carbonated. The method according to claim 1,
Wherein the first nozzle is located on the upper side of the reactor and the second nozzle is installed below the first nozzle. The method according to claim 1,
Wherein the second nozzle injects carbon dioxide gas at a pressure of 1.5 bar to 2.5 bar. delete Discharging a solution to be carbonated from the first nozzle;
Spraying a carbon dioxide gas from the second nozzle onto a path through which the carbonated target solution is discharged to form a mist composed of the carbonated target solution and the carbonated gas;
Forming a slurry containing a carbonate by reacting a cation of the solution to be carbonated with a carbonated gas in the mist; And
Recovering the carbonate from the slurry,
Wherein the carbonated gas is injected in a direction away from a central portion of the carbonated target solution to be discharged from a surface perpendicular to a direction in which the carbonated target solution is discharged,
≪ / RTI > 15. The method of claim 14,
Wherein the solution to be carbonated includes a calcium ion, a magnesium ion or a lithium ion as a cation. 15. The method of claim 14,
Wherein the pH of the solution to be carbonated is pH 10 or more. 15. The method of claim 14,
Wherein the discharge path of the carbonated object solution and the injection path of the carbonated gas form an angle of 10 ° to 70 ° in the vertical direction of flow to the flow direction origin of the carbonated target solution. 18. The method of claim 17,
Wherein the discharge route of the carbonated object solution and the injection route of the carbonated gas form an angle of 30 to 50 degrees in the vertical direction of the flow to the flow direction origin of the carbonation target solution. delete 15. The method of claim 14,
Wherein the droplet size of the solution to be carbonated in the mist is 10 nm to 50 占 퐉. 15. The method of claim 14,
And spraying the carbon dioxide gas from the second nozzle at a pressure of 1.5 bar to 2 bar. 15. The method of claim 14,
Wherein the step of recovering the carbonate comprises filtering the solution to be carbonated containing the carbonate to recover the carbonate. 23. The method of claim 22,
Wherein the step of recovering the carbonate salt comprises drying the filtered carbonate salt.

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