KR101531344B1 - Method of recovering potassium compound from brine - Google Patents

Abstract

The present invention relates to a method for collecting a potassium compound from saline water, comprising the steps of preparing saline water; removing lithium, magnesium and calcium from the saline water, and obtaining mixed fuel salt; making slurry by mixing the mixed fuel salt with saturated saline water, and then mixing the same with a flotation reagent; injecting air bubbles into the slurry mixed with the mixed fuel salt, the saturated saline water and the flotation reagent, and selectively collecting a potassium compound; separating and screening potassium chloride and Na_2SO_4·3K_2SO_4 from the collected potassium compound; and extracting potassium sulfate from the separated Na_2SO_4·3K_2SO_4.

Description

METHOD OF RECOVERING POTASSIUM COMPOUND FROM BRINE BACKGROUND OF THE INVENTION [0001]

And recovering the potassium compound from the brine.

In general, potassium compounds such as potassium chloride (KCl) and potassium sulfate (K ₂ SO ₄ ), which are widely used for fertilizer, have been obtained from various raw materials.

One example of this is the recovery of potassium compounds from seawater or salt water.

However, since there are various monovalent or divalent metal ions in seawater or brine, it is very difficult to selectively recover only potassium compounds.

Also, considering the economical efficiency of the recovery process, a continuous process configuration is required and there is no corrosion due to high concentration of salt.

Thus, an economical and effective process for recovering potassium compounds is required.

Only potassium compounds (KCl, Na ₂ SO ₄ .3K ₂ SO ₄ ) were selectively collected and recovered from brine, and potassium chloride (KCl) and potassium sulfate (K ₂ SO ₄ ) were produced from the recovered potassium compound And the like.

In addition, it can provide a solution for corrosion of equipment due to continuous process composition and high concentration brine use for large commercialization.

In one embodiment of the present invention, there is provided a method of preparing a salt solution comprising: preparing a salt water; Removing lithium, magnesium, and calcium in the brine to obtain a mixed fuel salt; Mixing the mixed fuel salt and saturated brine to form a slurry, Selectively injecting bubbles into the slurry in which the mixed raw material salt, the saturated brine, and the sludge mixture are mixed to recover the potassium compound; Further comprising: from the recovered potassium screening to remove the potassium chloride and gras Celite _{(Na 2 SO 4 · 3K 2} SO 4); And extracting potassium sulfate from the separated gracellulose. The method for recovering potassium compounds from saline can be provided.

Mixing the mixed fuel salt and the saturated brine to prepare a slurry, and mixing the mixed salt with the pre-mixed agent, the mixed raw salt may be added at a weight ratio of 0.1 to 0.2 based on the saturated brine.

The pre-emulsifier may be sodium dodecyl sulfate.

Mixing the mixed fuel salt and the saturated brine to prepare a slurry, and mixing the pseudo-syringe with the pseudo-syringe, the pseudo-syringe may be added at a rate of 0.01 to 0.05 weight ratio to the slurry.

Separating and separating potassium chloride and gracellite (Na ₂ SO ₄ .3K ₂ SO ₄ ) from the recovered potassium compound, comprising: mixing a potassium compound and a non-mass liquid; And separating the potassium chloride and the saccharite using the difference in specific gravity of the potassium compound.

The specific weight of the specific weight may be 2.3 to 2.4.

In the step of mixing the potassium compound and the non-mass liquid, the potassium compound relative to the non-mass liquid may be 0.1 to 0.4 weight ratio.

The step of extracting potassium sulfate from the separated gracellulose comprises: mixing and stirring the separated gracellulose and a saturated aqueous potassium chloride solution; And extracting potassium sulfate from the sucralite.

Only potassium compounds (KCl, Na ₂ SO ₄ .3K ₂ SO ₄ ) were selectively collected and recovered from brine, and potassium chloride (KCl) and potassium sulfate (K ₂ SO ₄ ) were produced from the recovered potassium compound And the like.

In addition, it can provide a solution for corrosion of equipment due to continuous process composition and high concentration brine use for large commercialization.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an overall process diagram of a potassium compound manufacturing apparatus according to an embodiment of the present invention. FIG.
FIG. 2 is a detailed process diagram of the continuous potassium compound collecting apparatus in FIG. 1.
FIG. 3 is a block diagram of a continuous potassium compound floating sorting apparatus in FIG. 2.
4 is a detailed process diagram of the continuous potassium compound separation and sorting apparatus in FIG.
FIG. 5 is a block diagram of a continuous potassium non-specific gravity sorter in FIG.
6 is a detailed process diagram of the continuous potassium sulfate converting apparatus in FIG.
FIG. 7 is a schematic view of the continuous potassium sulfate reactor in FIG.

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 potassium compounds according to one embodiment of the present invention may be an apparatus for producing a continuous, single-phase, non-corrosive potassium compound from brine.

More specifically, mixed raw materials (NaCl, KCl, Na ₂ SO ₄ .3K ₂ SO _4, etc.) obtained through selective natural evaporation after extracting lithium (Li), magnesium (Mg) A continuous type pretreatment apparatus such as crushing, crushing and granular separation for processing into granules having easy separation and sorting; A continuous potassium compound collecting device for continuously collecting and collecting only potassium compounds (KCl, Na ₂ SO ₄ .3K ₂ SO ₄ ) from the pretreated mixed raw salt continuously; The recovered potassium _{(KCl, Na 2 SO 4 ·} 3K 2 SO 4) potassium chloride (KCl) and gras Celite _{(Na 2 SO 4 · 3K 2} SO 4) the single continuous potassium compound daily continuous separation selected from A separation and sorting device; And a continuous potassium sulfate conversion apparatus for extracting potassium sulfate (K ₂ SO ₄ ) from the separated grachelite.

A continuous potassium compound collecting apparatus for continuously collecting and collecting only potassium compounds from the mixed raw material salt collectively includes a raw material salt, a saturated saline solution, and a pouring raw material, An automatic dispensing device; A conditioner for mixing the raw salt and the saturated brine to prepare a slurry and mixing the raw slurry with the saturated saline; A continuous potassium compound floating sorting apparatus for sorting a potassium compound by injecting bubbles into a slurry solution containing a raw material salt, a saturated salt water and a by-product; And a continuous solid-liquid separator for separating the selected potassium compound slurry and the remaining slurry into a salt cake and a filtrate (saturated brine) by solid-liquid separation, respectively.

When the slurry is prepared by mixing the raw salt and the saturated brine, the raw salt may be added to the slurry in a ratio of 0.1 to 0.2 by weight based on the saturated brine.

The saturated brine may be lithium, magnesium, and brine in a state in which calcium is removed.

On the other hand, sodium dodecyl sulfate may be used as a flotation agent for collectively selecting only the potassium compound from the mixed raw material salt. However, the present invention is not limited thereto.

At this time, the nascent agent may be added in a ratio of 0.01 to 0.05 weight ratio to the slurry solution. However, the present invention is not limited thereto.

The continuous potassium compound floating sorting apparatus includes a plurality of cells to be sorted; A diffuser installed in each of the cells and sucking outside air while rotating to form small bubbles in the slurry solution; A scraper for recovering the floated potassium compound; And a floating catcher that applies ultrasonic vibration at the bottom of the cell to improve separation efficiency and purity.

In this case, the separation cell can be further screened by transferring the slurry solution, which has not been completely sorted due to the connection of the channels, to the next cell. Further, the separated slurry solution is transferred to the next cell to improve the purity of the potassium compound .

Further, the diffuser can control the amount of bubbles by operating the air inflow control valve.

At this time, the rotational speed of the diffuser may be changed from 10 to 200 revolutions per minute.

On the other hand, the saturated brine obtained by subjecting the selected potassium compound slurry and the remaining slurry to solid-liquid separation can be sent to a saturated brine storage tank for recycling.

On the other hand, a continuous potassium compound separation and sorting apparatus for continuously separating and separating potassium chloride and gracellulose from the recovered potassium compound in a single phase comprises a raw material automatic injecting apparatus for continuously storing potassium compounds and a specific gravity solution, A mixer for mixing the charged potassium compound and the non-mass liquid to form a slurry; A continuous potassium sorbent non-sorbent screening device for continuously separating potassium chloride and grachelite using the specific gravity difference of the potassium compound; And a continuous solid-liquid separation device in which the selected potassium chloride slurry and the granular slurry are separated by solid-liquid separation and separated into potassium chloride and a mixture of a granular cake and a non-slurry liquid.

The specific gravity of potassium chloride in the raw material is 1.99 and the specific gravity of the grcellite is 2.70. The specific gravity liquid used for separating the two materials using the specific gravity difference is tetrabromoethane (specific gravity 2.96) and carbon Tetrachloride (specific gravity: 1.58) may be mixed at a certain ratio so that the total specific gravity becomes 2.3 to 2.4.

At this time, when the slurry is prepared by mixing the potassium compound and the non-slurry, the potassium compound may be added at a weight ratio of 0.1 to 0.4 relative to the non-slurry. However, the present invention is not limited thereto.

In addition, a certain amount of the slurry in which the potassium compound and the non-mass liquid are mixed is continuously fed to the potassium compound specific gravity sorter by gravity, at which time the input can be controlled by the proportional control automatic valve.

The potassium compound slurry continuously flows into the middle portion of the side of the potassium compound specific gravity sorter, potassium chloride which is light in specific weight floats and is drawn out through the potassium chloride outlet at the upper part of the specific gravity separator, And can be taken out through the Gracellite outlet of the lower part of the specific gravity sorting device.

The separated potassium chloride slurry and the granular slurry separated and drawn out are continuously solid-liquid separated continuously using a continuous-type solid-liquid separator, and the recovered non-selected liquid can be sent to the non-liquid storage tank and recycled.

On the other hand, the continuous potassium sulfate converting apparatus for extracting potassium sulfate from the separated grachelite includes: a raw material automatic charging device for continuously supplying the amount of the aqueous solution of sucralite and saturated potassium chloride; A continuous potassium sulfate reactor for continuously producing potassium sulfate from the gracellulose; And a continuous solid-liquid separator for recovering the potassium sulfate cake by solid-liquid separation of the potassium sulfate slurry after completion of the reaction.

The continuous potassium sulfate reactor comprises a reaction tank composed of two reaction vessels (A) and (B); And a continuous reaction mixer which is located at the bottom of the two reactors and mixes the slurry to induce the reaction through high-speed stirring.

In the case of the reaction tank, the slurry is drawn into the upper part of the A reaction tank, the outlet exists in the lower part of the partition wall between the A reaction tank and the B reaction tank, and the slurry flows from the A reaction tank to the B reaction tank. There is an outlet at the upper part of the partition wall opposite the partition wall so that the slurry flowing from the A reaction tank flows out to the outside.

The continuous reaction mixer may be configured to introduce a portion of the slurry flowing from the A reactor into the B reactor from the bottom of the B reactor to induce the reaction through high-speed agitation and then return to the upper portion of the A reactor.

Therefore, the slurry flow in the continuous potassium sulfate reactor flows into the upper portion of the reactor A, flows into the reactor B through the passage located at the lower portion of the reactor vessel, flows to the outside through the outlet of the reactor B, And may be returned to the reactor A by a continuous reaction mixer.

The continuous reaction mix may control the amount of the slurry returned from the B reactor to the A reactor by controlling the amount of the slurry drawn in and drawn out through the rotation speed control, .

The continuous potassium sulfate reactor may be a structure capable of increasing the treatment efficiency by connecting a plurality of reactors in series.

The potassium sulfate slurry produced through the continuous potassium sulfate reactor is subjected to continuous solid-liquid separation continuously using a continuous type solid-liquid separation apparatus, and the recovered aqueous solution of saturated potassium chloride is sent to the storage tank and can be recycled.

In addition, all facilities in contact with the brine can be made of PVC, PE, FRP, etc. to prevent corrosion.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The operation of the apparatus for producing a non-corrosive continuous single potassium compound from brine having the above-described structure will be described as follows.

First, a lithium (Li), magnesium (Mg), calcium (Ca) is the the removed brine when natural evaporation (such as _{NaCl, KCl, Na 2 SO 4} · 3K 2 SO 4) mixing the raw material salt precipitation, and the precipitation mixture The raw material salt is recovered, dried and pulverized to prepare a raw material. Also, a saturated aqueous solution of sodium chloride (NaCl) and potassium chloride (KCl) is prepared to prevent the raw material salt from being dissolved by the water added for the preparation of the raw salt slurry. Prepare Sodium Dodecyl Sulfate as a barge.

The raw salt powder, the saturated salt water and the pre-pellet are respectively put into a storage tank and continuously fed into a conditioner by a predetermined amount through an automatic feeding device, and then mixed thoroughly by high-speed agitation so that the flotation liquid is coated well on the surface of raw salt particles.

When the raw material salt, the saturated salt water and the preheating agent are sufficiently mixed in the conditioner, the side line agent is coated only on the surface of the potassium (K) compound particle by the surface charge of the raw salt particle, and the particle coated with the side line agent becomes hydrophobic.

The raw salt slurry thus pretreated by the pretreatment is continuously supplied to the primary cell of the potassium compound flotation screening apparatus by using a slurry pump.

The continuous potassium compound floating sorting apparatus is composed of at least two cells, and each cell is equipped with a diffuser which induces a vacuum through rotation in the solution to introduce air and bubbles with the introduced air. The diffuser is capable of regulating the amount of air inflow through the air inflow control valve, and is capable of controlling the amount of air inflow and bubble generation by changing the rotation speed from 10 to 200 rpm.

The bottom of the cell is equipped with a float assist to improve the recovery rate and purity of potassium compounds by allowing rapid separation of potassium (K) compound particles and sodium chloride (NaCl) particles in solution through ultrasonic vibration.

When bubbles are generated by the diffuser under the raw salt slurry supplied to the primary cell of the continuous potassium compound floating sorting apparatus, the bubbles float to the upper part of the slurry solution and the potassium (K) compound particles which become hydrophobic by the pre- It comes to rise together.

The floating potassium (K) compound is recovered by a scraper, and the remaining slurry is passed to the secondary cell through a flow path formed on the side of the cell. The potassium compound, which has not been recovered in the primary cell, It is once again recovered by the same operation. In the same way, more than 90% of the potassium compounds are recovered in the slurry passing through the tertiary cell and the fourth cell, and the number of cells may be further added to increase the recovery rate.

On the other hand, the recovered potassium compound enters the cell for washing, and the purity can be improved by performing the same treatment as in the separation sorting cell once again.

The recovered potassium compound slurry is recovered from the potassium compound cake through a continuous solid-liquid separator, and the remaining saturated brine filtrate is recycled to the process.

Meanwhile, the remaining slurry after the recovery of the potassium compound is separated into sodium chloride (NaCl) cake and saturated brine by the same continuous liquid-solid separator, and the saturated brine is recycled during the process.

The recovered potassium compound cake is passed to a continuous potassium compound separation screening device for separation and recovery into a single phase of potassium chloride and sucrose.

The potassium compound cake recovered by the continuous potassium compound collecting device is continuously fed into the mixer of the continuous potassium compound separation and sorting device at a predetermined feed rate together with the previously prepared specific gravity solution and mixed uniformly by the stirrer in the mixer.

In order to maximize the separation efficiency between potassium chloride (specific gravity 1.99) and gracellite (specific gravity 2.70), the specific gravity solution used in this case is made to have a median value of 2.3 to 2.4 in the specific gravity of the two materials. Tetrabromoethane (specific gravity: 2.96) and Carbon Tetrachloride (specific gravity: 1.58) can be mixed at a certain ratio to obtain a desired specific gravity.

The potassium compound slurry uniformly mixed in the mixer is fed to the continuous potassium compound non-sorbent separator at a constant rate using the gravity of the equipment.

At this time, the slurry input speed control for establishing the separation condition can be adjusted by operating a proportional control automatic valve mounted at the bottom of the mixer.

The potassium compound slurry injected into the continuous potassium compound nonaqueous separator at a constant rate causes the potassium chloride particles to rise to the top due to the specific gravity difference, and the floated potassium chloride slurry is drawn to the top outlet.

In addition, the gracellite particles having a high specific gravity are lowered to the bottom, and the gracellite slurry descending to the bottom is drawn out to the lower outlet.

The potassium chloride slurry drawn out from the upper and lower outlets of the continuous potassium-based non-specific gravity separator and the slurry of the granite were respectively introduced into the continuous type solid-liquid separator to recover the potassium chloride and the sucralite in a cake state, Enter the liquid storage tank for recycling.

The recovered potassium chloride cake is finally commercialized, and the recovered sucralite cake is passed to a continuous potassium sulfate converter to extract a single phase of potassium sulfate.

The Gracellite cake is triturated in a storage tank with a previously prepared saturated aqueous solution of potassium chloride to form a slurry, and this slurry is continuously introduced into the top of the A reactor of the continuous potassium sulfate reactor at a constant rate.

The charged granular slurry moves to the bottom of the partition wall between the B reactor and the B reactor through the outlet.

Part of the slurry moved to the reaction tank B is passed to the next reaction tank through the outlet located at the upper part of the opposite partition wall to the partition wall with respect to the reaction tank A and the other slurry is introduced into the continuous reaction mixer through the inlet located below the reaction tank B do.

The slurry introduced into the continuous reaction mixer induces the potassium sulfate extraction reaction through the high-speed agitation and is returned to the A reactor through the inlet located at the top of the A reactor.

The continuous potassium sulfate reactor can control the overall slurry movement speed by moving a part of the slurry moved to the next reaction tank to the previous reaction vessel as described above, thereby securing a reaction time for potassium sulfate extraction.

This slurry movement speed control can be achieved by controlling the number of revolutions of the continuous reaction mixer and controlling the amount of slurry returned to the previous reaction vessel.

As described above, a plurality of continuous potassium sulfate reactors composed of the A reactor, the B reactor, and the continuous reaction mixer may be connected in series to constitute the entire reactor.

The slurry withdrawn through the final reaction tank of the continuous potassium sulfate reactor obtains a potassium sulfate cake through a continuous solid-liquid separator and finally commercializes it.

In addition, a saturated aqueous solution of potassium chloride can be sent to a storage tank for recycling.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

3-1: Continuous potassium compound collecting device selection cell
3-2: Diffuser
3-3: Scraper
3-4: Floating Agent
5-1: Mixer
5-2: Stirrer
5-3: Proportional control automatic valve
5-4: Continuous potassium compound specific gravity sorter
5-5: Slurry outlet of potassium chloride
5-6: Glucelite slurry outlet
7-1: Reaction tank A
7-2: Reactor B
7-3: A reactor outlet
7-4: B reactor outlet
7-5: Continuous Reaction Mixer

Claims (8)

Preparing salt water;
Removing lithium, magnesium, and calcium in the brine to obtain a mixed fuel salt;
Mixing the mixed fuel salt and saturated brine to form a slurry,
Selectively injecting bubbles into the slurry in which the mixed raw material salt, the saturated brine, and the sludge mixture are mixed to recover the potassium compound;
Further comprising: from the recovered potassium screening to remove the potassium chloride and gras Celite _{(Na 2 SO 4 · 3K 2} SO 4); And
Extracting potassium sulfate from the separated gracellulose;
And recovering the potassium compound from the brine.
The method according to claim 1,
Mixing the mixed fuel salt and the saturated brine to prepare a slurry,
Wherein the mixed raw material salt is added at a ratio of 0.1 to 0.2 by weight relative to the saturated brine, and the potassium compound is recovered from the brine.
The method according to claim 1,
Wherein the osmotic agent is sodium dodecyl sulfate. ≪ RTI ID = 0.0 > 25. < / RTI >
The method according to claim 1,
Mixing the mixed fuel salt and the saturated brine to prepare a slurry,
Wherein the osmotic agent is added at a rate of 0.01 to 0.05 weight ratio to the slurry.
The method according to claim 1,
Separating and separating potassium chloride and gracellite (Na ₂ SO ₄ .3K ₂ SO ₄ ) from the recovered potassium compound,
Mixing the potassium compound and the non-diluted liquid; And
Separating potassium chloride and grachelite using the specific gravity difference of the potassium compound;
And recovering the potassium compound from the brine.
6. The method of claim 5,
Wherein the specific gravity of the specific gravity solution is 2.3 to 2.4.
6. The method of claim 5,
Mixing the potassium compound and the non-diluted liquid,
Wherein the potassium compound is 0.1 to 0.4 weight ratio relative to the non-specific weight.
The method according to claim 1,
Extracting potassium sulfate from the separated gracellulose,
Mixing and stirring the separated gracellulose and a saturated aqueous potassium chloride solution; And
Extracting potassium sulfate from the sucralite;
And recovering the potassium compound from the brine.

Images