KR20150008349A - Resources recovery from waste-fertilizer solution of fdfo used for enrichment or desalination of seawater - Google Patents

Resources recovery from waste-fertilizer solution of fdfo used for enrichment or desalination of seawater Download PDF

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KR20150008349A
KR20150008349A KR20140088645A KR20140088645A KR20150008349A KR 20150008349 A KR20150008349 A KR 20150008349A KR 20140088645 A KR20140088645 A KR 20140088645A KR 20140088645 A KR20140088645 A KR 20140088645A KR 20150008349 A KR20150008349 A KR 20150008349A
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solution
fdfo
seawater
apatite
desalination
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KR20140088645A
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Korean (ko)
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KR101689200B1 (en
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곽성조
정남조
김동국
박종수
김찬수
최지연
김한기
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한국에너지기술연구원
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention relates to a system and a method for synthesizing apatite from an FDFO wastewater of a seawater concentration or seawater desalination system. The method comprises the steps of applying phosphoric acid or calcium to a dilute fetilzer solution discharged through FDFO, And the compound can be added to synthesize apatite. The system for synthesizing apatite from the FDFO wastewater of a seawater concentration or seawater desalination apparatus comprises a pretreatment device for removing impurities such as suspended matter and organic matter from the incoming seawater; A desalination device for concentrating the brine through the pretreatment device to separate the highly concentrated brine and fresh water; An FDFO device for introducing seawater and fertilizer solution from which impurities have been removed through a pretreatment device to dilute the concentration of the fertilizer solution by increasing the concentration of seawater through the osmotic pressure due to the difference in concentration of the two solutions; And apatite synthesizing means for synthesizing apatite by adding the additive solution to the fertilizer solution which is diluted through the FDFO apparatus and discharged to the waste solution. That is, the present invention can be applied to a dilute fetilzer solution which is discharged into waste solution through FDFO during a desalination process using FDFO or a desalination process of a seawater desalination system, in which a calcium compound, a magnesium compound and a phosphate solution To synthesize the apatite.

Description

Technical Field [0001] The present invention relates to a system and a method for synthesizing apatite from an FDFO wastewater of a seawater concentration or seawater desalination apparatus. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

TECHNICAL FIELD The present invention relates to a technology and a process for synthesizing new high-value-added substances from wastewater of fertilizer-derived forward osmosis (FDFO) applicable to a seawater concentration or seawater desalination system, and more particularly, And a method for synthesizing apatite from the FDFO wastewater of a seawater concentration or seawater desalination system utilizing a calcium component.

In general, the FDFO technique is a concept of adding a fertilizer solution to the FO technique. By supplying the fertilizer solution instead of the draw solution used in the FO system, the osmotic pressure is greatly increased and the seawater desalination and concentration phenomenon .

The fertilizer of the above-mentioned composition is gradually being developed from liquid fertilizer into fertilizer (fertilizer is mixed with water in a dropping watering apparatus). As the fertilizer, calcium nitrate, phosphoric acid, potassium chloride alone or a mixture thereof is generally used.

This technology is one of the most energy-consuming seawater desalination technologies currently in use. This technology produces concentrated water and diluted fertilizer solution, which can be concentrated at a high concentration, which can maximize the concentration rate. In addition, more than 80% of the diluted fertilizer solution is currently used only as agricultural water.

However, since the above-mentioned fertilizer solution contains calcium and phosphorus, which are essential ingredients of apatite, it can be easily used for synthesis of high value-added apatite material as well as agricultural water.

In fact, apatite can be synthesized in a variety of ways, including sol-gel, hydrothermal synthesis, and biomimetic formation. The basic materials used in this synthesis process are calcium compounds (calcium compounds: carlcium nitrite, calcium hydroxide etc.) Aqueous solution of phosphoric acid.

Therefore, if the diluted fertilizer freshwater solution discharged from the FDFO process contains phosphoric acid, apatite can be synthesized by adding a calcium compound. If the diluted fertilizer fresh water solution contains calcium nitrate, apatite can be synthesized by adding an aqueous phosphoric acid solution.

1. Korean Patent Publication No. 2010-0089311 (Released on Aug. 12, 2010) 2. Republic of Korea Patent Publication No. 2012-0015964 (2012.02.22)

The present invention has been devised to synthesize apatite by using a diluted fertilizer fresh water solution discharged from the FDFO process. It is a method of adding phosphoric acid or calcium to a dilute fetilzer solution discharged through FDFO, The present invention provides a method for synthesizing apatite from FDFO wastewater of a seawater concentration or seawater desalination system that can synthesize apatite by charging an ionic compound.

The present invention configured to achieve the above-described object is as follows. That is, the system for synthesizing apatite from the FDFO wastewater of the seawater concentrating or seawater desalination apparatus according to the present invention includes a pretreatment device for removing impurities such as suspended matter or organic matter from the incoming seawater; A desalination device for concentrating the brine through the pretreatment device to separate the highly concentrated brine and fresh water; A FDFO (Fertiliser Drawn Forward Osmosis) device for introducing seawater and fertilizer solution from which impurities have been removed through a pretreatment device to dilute the concentration of the fertilizer solution by increasing the concentration of seawater through osmotic pressure due to the difference in concentration of the two solutions; And apatite synthesizing means for synthesizing apatite by adding the additive solution to the fertilizer solution which is diluted through the FDFO apparatus and discharged to the waste solution.

In the constitution according to the present invention as described above, the additive solution to be injected into the fertilizer solution which is diluted through the FDFO apparatus in the apatite synthesizing means and discharged to the waste solution may be any one of a calcium compound, a magnesium compound and a phosphate solution .

According to another aspect of the present invention, there is provided a pretreatment apparatus comprising: a pretreatment device for removing impurities such as floating matters and organic matter from inflow seawater; A desalination device for concentrating the brine through the pretreatment device to separate the highly concentrated brine and fresh water; A FDFO (Fertiliser Drawn Forward Osmosis) device for introducing seawater and fertilizer solution from which impurities have been removed through a pretreatment device to dilute the concentration of the fertilizer solution by increasing the concentration of seawater through osmotic pressure due to the difference in concentration of the two solutions; And a multivalent ion synthesizing means for synthesizing apatite by injecting a multivalent ionic compound which is treated and discharged in a pretreatment device to a fertilizer solution which is diluted through an FDFO device and discharged into a waste solution.

In the composition according to the present invention as described above, the polyvalent ionic compound in the polyvalent ion synthesizing means may be calcium carbonate or magnesium carbonate.

A methodological feature of the present invention is to provide a dilute fetilzer solution which is discharged into the waste solution through the FDFO during the desalination process of the seawater desalination system using FDFO or a calcium compound, a magnesium compound and a phosphate solution solution is added to synthesize apatite.

In addition, another methodological feature of the present invention is that the dilute fetilzer solution discharged into the waste solution during the desalination process of the seawater desalination system using the FDFO is treated and discharged in the pretreatment process during the same seawater desalination process Ionic compound into a fertilizer solution to synthesize apatite.

In the above-described constitution, the polyvalent ionic compound may be composed of calcium carbonate or magnesium carbonate.

The present invention is a technology for obtaining a high-value-added apatite material from a pulp fertilizer solution of the FDFO process, which is one of the seawater desalination technologies, and maximizes utilization of the pulp fertilizer solution which has been used only for agriculture, It is meaningful to mass-produce apatite, which is a very important bioceramic material in applications. These inventions will open new possibilities for the utilization of marine resources.

FIG. 1 is a process for synthesizing apatite by artificially supplying an additive solution to a waste fertilizer solution of the FDFO process, which is one of the seawater desalination techniques according to the present invention, and then reacting.
FIG. 2 is a view showing a process of synthesizing apatite by supplying a multivalent ionic compound, which is a byproduct of waste treated in a pretreatment process for seawater desalination, to a waste fertilizer solution of an FDFO process, which is one of the seawater desalination technologies according to another embodiment of the present invention Degree.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings, It can be easily carried out. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail. Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a process diagram of synthesizing apatite by artificially supplying an additive solution to a waste fertilizer solution of the FDFO process, which is one of the seawater desalination techniques according to the present invention, FIG. 2 is a view This is a process for synthesizing apatite by supplying a multifunctional ionic compound, which is a byproduct of waste treated in the pretreatment process for seawater desalination, to the pulp fertilizer solution of the FDFO process, which is one of the technologies.

As shown in FIG. 1, the apatite composite system 100 according to the present invention includes a preprocessing unit 110 for removing impurities suspended in water from an incoming seawater, a pretreatment unit 110 for concentrating the saline water, The seawater concentration and the concentration of the fertilizer solution are increased by osmotic pressure due to the concentration difference between the two solutions by introducing the seawater and the fertilizer solution from which the impurities have been removed through the desalination device 120 and the pretreatment device 120 for separating the fresh water, And an apatite synthesizing unit 140 for synthesizing apatite by injecting the additive solution into the fertilizer solution diluted through the FDFO apparatus 130 and the FDFO apparatus 130 to be discharged into the waste solution .

In the technique according to the present invention constructed as described above, 3.5 wt.% Of seawater is separated into fresh water and salt water in a seawater desalination system after a pretreatment process. This seawater desalination system can be completed through conventional reverse osmosis (RO), electrodialysis (ED), membrane desalination (MD), heat pump crystallization (HP / Cr) and capacitive deionization (CDi).

On the other hand, the FDFO 130 technique described above is one of the seawater desalination techniques as described above. When the pretreated seawater and the fertilizer solution are respectively introduced into the system of the FDFO 130, osmotic pressure is formed due to the difference in the concentration of the two solutions in the intermediate membrane, and the concentration of the fertilizer solution is diluted. In this process, a large amount of calcium or phosphorus is present in the diluted fertilizer solution as described above.

The ingredients as described above are essential components of apatite. Therefore, as shown in FIG. 1, when the necessary ingredients are additionally supplied to the fertilizer solution through the apatite synthesizing means 140 for forming apatite, and utilizing various conventional synthesis methods (sol-gel, hydrothermal synthesis, biomimetic formation) Can be synthesized. At this time, any one of the calcium compound, the magnesium compound and the phosphate solution may be used as the additive solution which is diluted in the apatite synthesizer 140 through the FDFO device 130 and is introduced into the fertilizer solution discharged into the waste solution .

In the present invention, when the diluted fertilizer solution discharged from the FDFO 130 process contains only phosphoric acid component, a calcium compound is added. When calcium nitrate component is contained, a phosphoric acid aqueous solution is added to synthesize apatite. The existing process can be utilized to synthesize apatite.

In other words, the technique according to the present invention can be applied to a dilute fetilzer solution which is discharged to the waste solution through the FDFO 130 during the desalination process using the FDFO or the desalination process of the seawater desalination system. The calcium compound, the magnesium compound and the phosphate solution (phosphate solution) is added to synthesize apatite.

2, the apatite composite system 200 according to another embodiment of the present invention includes a pretreatment unit 210 for removing impurities such as suspended matter and organic matter from inflowing seawater, and a pretreatment unit 210 for concentrating The seawater concentration of the two solutions is increased by introducing seawater and fertilizer solution in which the impurities are removed through the desalination device 220 and the pretreatment device 210 for separating the highly concentrated brine and fresh water, Is diluted through the FDFO apparatus 230 and the FDFO apparatus 230 to dilute the concentration of the fertilizer solution, and the multifunctional ionic compound treated and discharged in the pretreatment apparatus 210 is introduced into the fertilizer solution discharged into the waste solution And a multivalent ion synthesizing means 240 for synthesizing apatite.

In the multivalent ion synthesizing means according to another embodiment of the present invention as described above, the multivalent ionic compound may be composed of calcium carbonate or magnesium carbonate.

Meanwhile, the embodiment of FIG. 1 is a method in which apatite is synthesized by injecting an additive solution into a fertilizer solution diluted through the FDFO device 130 and discharged into a waste solution, whereas the technique according to another embodiment of FIG. 230), and a polyvalent ionic compound, which is treated and discharged in the pretreatment unit 210, is added to the fertilizer solution discharged to the waste solution to synthesize the apatite.

In other words, the technology according to another embodiment of the present invention is applied to a dilute fetilzer solution discharged from the waste solution during the desalination process of the seawater desalination system using the FDFO in the pretreatment process during the same seawater desalination process And a polyvalent ionic compound to be discharged is put into a fertilizer solution to synthesize apatite.

If a large amount of phosphoric acid component is present in the above-mentioned fertilizer solution but the calcium or magnesium component is deficient, the necessary components may be separately supplied as shown in FIG. 1, but in the pretreatment step of the entire seawater desalination system Apatite can be synthesized by supplying a treated polyvalent ionic compound (calcium carbonate or magnesium carbonate).

100, 200. Apatite composite system
110, 210. Pretreatment device
120, 220. Desalination unit
130, 230. FDFO
140. Apatite composite means
240. The multivalent ion synthesizing means

Claims (7)

A pretreatment device for removing impurities such as suspended matter or organic matter from the incoming seawater;
A desalination device for concentrating the brine from the pretreatment device to separate the highly concentrated brine and fresh water;
An FDFO (Fertilizer Drawn Forward Osmosis) device for introducing seawater and fertilizer solution from which impurities have been removed through the pretreatment device to dilute the concentration of the fertilizer solution by increasing the concentration of seawater through osmotic pressure due to the difference in concentration of the two solutions; And
And an apatite synthesizing means for synthesizing apatite by injecting the additive solution into the fertilizer solution which is diluted through the FDFO apparatus and discharged into the waste solution, and synthesizes the apatite from the FDFO wastewater of the seawater desalination apparatus. The method according to claim 1, wherein the additive solution to be diluted through the FDFO apparatus in the apatite synthesis unit and discharged into the waste solution is one of a calcium compound, a magnesium compound, and a phosphate solution. A system for synthesizing apatite from the FDFO effluent of a seawater concentrate or seawater desalination plant. A pretreatment device for removing impurities such as suspended matter or organic matter from the incoming seawater;
A desalination device for concentrating the brine from the pretreatment device to separate the highly concentrated brine and fresh water;
An FDFO (Fertilizer Drawn Forward Osmosis) device for introducing seawater and fertilizer solution from which impurities have been removed through the pretreatment device to dilute the concentration of the fertilizer solution by increasing the concentration of seawater through osmotic pressure due to the difference in concentration of the two solutions; And
And a multivalent ion synthesizing means for synthesizing apatite by charging a multivalent ionic compound which is treated and discharged in the pretreatment device to a fertilizer solution which is diluted through the FDFO device and discharged into a waste solution, A system for synthesizing apatite from wastewater. The system for synthesizing apatite from the FDFO wastewater of a seawater desalination or seawater desalination apparatus according to claim 3, wherein the polyvalent ion compound in the multivalent ion synthesizing means is calcium carbonate or magnesium carbonate. A calcium compound, a magnesium compound, and a phosphate solution are injected into a dilute fetilzer solution discharged into the waste solution through the FDFO during the desalination process using the FDFO or the seawater desalination system, Wherein the method comprises the steps of: (a) combining the desulfurizing water with the fluoride water; A multifunctional ionic compound which is treated and discharged in a pretreatment process during the same seawater desalination process to a dilute fetilzer solution discharged into a waste solution during the desalination process of the seawater concentration using the FDFO or the seawater desalination system is inserted into the fertilizer solution, Wherein the method comprises the steps of: (a) combining the desulfurizing water with the fluoride water; The method according to claim 6, wherein the polyvalent ionic compound is calcium carbonate or magnesium carbonate. 8. The method according to claim 6, wherein the polyvalent ionic compound is calcium carbonate or magnesium carbonate.
KR1020140088645A 2013-07-12 2014-07-14 System for synthesizing apatite from waste-fertilizer solution of fdfo KR101689200B1 (en)

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RU2740289C2 (en) * 2019-04-15 2021-01-12 Федеральное государственное бюджетное образовательное учреждение высшего образования Новосибирский государственный архитектурно-строительный университет (Сибстрин) Method of afterpurification of waste liquid from phosphates

Citations (5)

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JP2000026187A (en) * 1998-07-03 2000-01-25 Fraunhofer G Zur Foerderung Der Angewanten Forschung Ev Utilization of liquid compost material
KR100751581B1 (en) * 2006-06-19 2007-08-22 (주)블루오션월드 Method for producing mineral water from deep ocean water with active control of mineral balances
KR100859594B1 (en) * 2007-05-15 2008-09-23 한국수자원공사 Advanced wastewater treatment method with the biosolids reduction and the recovery of rbdcod
KR20100089311A (en) 2009-02-03 2010-08-12 한국과학기술원 Hybrid type desalination device, desalinating method using the same and regenerating method thereof
KR20120015964A (en) 2010-08-13 2012-02-22 한국에너지기술연구원 Fluidized bed electrode system, mass flow energy storage system and water deionization method employing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000026187A (en) * 1998-07-03 2000-01-25 Fraunhofer G Zur Foerderung Der Angewanten Forschung Ev Utilization of liquid compost material
KR100751581B1 (en) * 2006-06-19 2007-08-22 (주)블루오션월드 Method for producing mineral water from deep ocean water with active control of mineral balances
KR100859594B1 (en) * 2007-05-15 2008-09-23 한국수자원공사 Advanced wastewater treatment method with the biosolids reduction and the recovery of rbdcod
KR20100089311A (en) 2009-02-03 2010-08-12 한국과학기술원 Hybrid type desalination device, desalinating method using the same and regenerating method thereof
KR20120015964A (en) 2010-08-13 2012-02-22 한국에너지기술연구원 Fluidized bed electrode system, mass flow energy storage system and water deionization method employing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A novel low energy fertilizer driven forward osmosis desalination for direct fertigation: evaluating the performance of fertilizer draw solutions. (2011)* *

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