CN108002490A - A kind of method that crude salt is extracted from concentrated seawater - Google Patents
A kind of method that crude salt is extracted from concentrated seawater Download PDFInfo
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- CN108002490A CN108002490A CN201710601857.2A CN201710601857A CN108002490A CN 108002490 A CN108002490 A CN 108002490A CN 201710601857 A CN201710601857 A CN 201710601857A CN 108002490 A CN108002490 A CN 108002490A
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- electrodialysis
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000013535 sea water Substances 0.000 title claims abstract description 35
- 150000003839 salts Chemical class 0.000 title claims abstract description 27
- 239000012528 membrane Substances 0.000 claims abstract description 66
- 238000000909 electrodialysis Methods 0.000 claims abstract description 56
- 239000012141 concentrate Substances 0.000 claims abstract description 34
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 238000012545 processing Methods 0.000 claims abstract description 13
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 25
- 238000011033 desalting Methods 0.000 claims description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- 229910001424 calcium ion Inorganic materials 0.000 claims description 13
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 10
- 238000005341 cation exchange Methods 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 238000005349 anion exchange Methods 0.000 claims description 5
- 238000009388 chemical precipitation Methods 0.000 claims description 5
- 238000010612 desalination reaction Methods 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229940006460 bromide ion Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims 1
- 229910001414 potassium ion Inorganic materials 0.000 claims 1
- 230000008020 evaporation Effects 0.000 abstract description 10
- 239000011780 sodium chloride Substances 0.000 abstract description 6
- 239000012267 brine Substances 0.000 abstract description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000012530 fluid Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- AYNDKKQQUZPETC-NXVVXOECSA-N (z)-2,3-bis(2,4,5-trimethylthiophen-3-yl)but-2-enedinitrile Chemical compound CC1=C(C)SC(C)=C1\C(C#N)=C(\C#N)C1=C(C)SC(C)=C1C AYNDKKQQUZPETC-NXVVXOECSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000000262 chemical ionisation mass spectrometry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/58—Multistep processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/05—Conductivity or salinity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Urology & Nephrology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
A kind of method that crude salt is extracted from concentrated seawater, the method are：(1) electrodialysis process, including three-level operation are carried out to the concentrated seawater from desalinator：First order operation is to use the first order electrodialysis membrane stack equipped with Monovalent selectivity amberplex to be handled, and obtains desalinization liquor I and concentrate I；Second level operation is to use the second level electrodialysis membrane stack equipped with conventional ion exchange membrane to obtain desalinization liquor II and concentrate II to concentrate I processing；Third level operation is to use the second level electrodialysis membrane stack equipped with conventional ion exchange membrane to obtain desalinization liquor III and concentrate III to concentrate II processing；(2) crude salt is made through evaporating in concentrate III.The present invention can efficiently separate the multivalent ion in concentrated seawater, improve crude salt purity, and can achieve the purpose that to concentrate sodium chloride brine, mitigate subsequent evaporation pressure, so as to produce the refined salt of higher degree by evaporation process；In addition the overall Water Sproading rate of system can be significantly increased.
Description
Technical field
The present invention relates to it is a kind of from concentrated seawater extract crude salt method, more particularly to a kind of electrodialysis system of design from
The method that crude salt is extracted in concentrated seawater.
Background technology
With the quick increase of world population, shortage of water resources problem becomes to become increasingly conspicuous.Seawater desalination is as a kind of raw
The effective means of production fresh water can alleviate water shortage crisis.At present, it is reverse osmosis to be used as a kind of best-of-breed technology for seawater desalination technology
It is widely used in all over the world.However, also being limited in its application by some factors, most important one limiting factor is reverse osmosis
The processing of concentrated seawater.Traditionally, concentrated seawater is in line into ocean or passes through evaporation process.The former can make marine ecosystems
Into potential hazard；The latter's cost is high, because evaporation process expends the wide variety of conventional energy.
Electrodialysis is widely used in water treatment procedure as a kind of ripe technology, because it is significant excellent with some
Gesture, such as expends less, is easy to operate, environmental-friendly.Electrodialysis membrane stack is the electrode plate that anions and canons exchange membrane is placed in membrane stack
In the middle, it is alternately arranged and is composed.Electrodialysis basic functional principle is：Passed through using selection of the amberplex to zwitterion
Performance, under DC electric field effect, makes zwitterion occur directional migration, separation so as to fulfill pending feed liquid, purification and
The purpose of concentration.And the electrodialysis membrane stack equipped with Monovalent selectivity yin, yang film utilizes Monovalent selectivity film to the saturating of monovalent ion
Cross and the retention property of multivalent ion, the multivalent ion in concentrated seawater can be efficiently separated, so as to achieve the purpose that to produce crude salt.
The content of the invention
The present invention is based on the deficiencies in the prior art, there is provided a kind of method that crude salt is extracted from concentrated seawater, the party
Method can efficiently separate the multivalent ion in concentrated seawater, improve crude salt purity, and can reach the mesh of concentration sodium chloride brine
, mitigate subsequent evaporation pressure, so as to produce the refined salt of higher degree by evaporation process；Additionally it has been significantly increased and has been
The overall Water Sproading rate of system.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of method that crude salt is extracted from concentrated seawater, the method are：
(1) electrodialysis process is carried out to the concentrated seawater from desalinator, the electrodialysis process includes three-level
Operation：
First order operation is to use the first order electrodialysis membrane stack equipped with Monovalent selectivity amberplex to be handled, will
Concentrated seawater and deionized water are separately added into the desalting chamber and enriched chamber of first order electrodialysis membrane stack, and it is molten to add sodium sulphate in the liquid chamber of pole
Liquid, is the terminal of first order operation when the electrical conductivity of processing to desalinization liquor is less than 20ms/cm, first order operation at this time is tied
Beam, obtains desalinization liquor I and concentrate I, wherein desalinization liquor I is after chemical precipitation removes calcium and magnesium ion, back to sea water desalination
Factory's preparing fresh again；And concentrate I is operated into the second level；
The second level operation be use equipped with conventional ion exchange membrane second level electrodialysis membrane stack to concentrate I at
Reason, adds concentrate I, pole liquid chamber adds metabisulfite solution, works as place toward the enriched chamber of second level electrodialysis membrane stack and desalting chamber
Reason to desalinization liquor electrical conductivity less than 5ms/cm when, be the second level operation terminal, the second level operation terminates, obtain desalinization liquor II
Operated with concentrate II, wherein concentrate II into the third level, desalinization liquor II, which can be back in first order membrane stack, (adds concentration
Room)；
The third level operation be use equipped with conventional ion exchange membrane second level electrodialysis membrane stack to concentrate II at
Reason, adds concentrate II, pole liquid chamber adds metabisulfite solution, works as place toward the enriched chamber of third level electrodialysis membrane stack and desalting chamber
Reason to desalinization liquor electrical conductivity less than 5ms/cm when, be the third level operation terminal, the third level operation terminates, obtain desalinization liquor
III and concentrate III, wherein desalinization liquor III can be back in first order membrane stack and (add enriched chamber)；
(2) crude salt is made through evaporating in concentrate III.
Further, the mass fraction for the metabisulfite solution that pole liquid chamber adds is preferably 3-5% in three-level operation, is most preferably
3%.
Further, in first order operation, desalinization liquor I can remove calcium and magnesium ion by following chemical precipitation method：Toward desalination
Sodium hydroxide and sodium carbonate are added in liquid, precipitates calcium and magnesium ion, so as to remove a large amount of calcium and magnesium ions.
In the method for the invention, the amount that feed liquid adds in each compartment is determined according to the size of film size, and usual each compartment adds
The volume entered is identical.
First order electrodialysis membrane stack of the present invention is alternately arranged by Monovalent selectivity anion and cation exchange membrane to be formed, and
Membrane stack is respectively put into a pole film adjacent to electrode plate both sides, for protecting Monovalent selectivity film so that formed pole liquid chamber, enriched chamber and
Desalting chamber；The second level, third level electrodialysis membrane stack are alternately arranged composition by common anion and cation exchange membrane, respectively shape
Poling liquid chamber, enriched chamber and desalting chamber.
Further, (i.e. an anode membrane adds number of repeat unit in the first order, the second level, third level electrodialysis membrane stack
One cavity block adds an anode membrane again) respectively preferably 5 (i.e. 6 anode membranes and 5 cavity blocks altogether).
Further, in the first order electrodialysis membrane stack, Monovalent selectivity anion and cation exchange membrane is Japanese Asahi Chemical Industry
Monovalent selectivity anode membrane, Japanese Asahi Chemical Industry Monovalent selectivity cavity block, and pole film is Japan AGC pole film.
Further, in the second level, third level electrodialysis membrane stack, common anion and cation exchange membrane is Japanese Asahi Chemical Industry
Anode membrane, Japanese Asahi Chemical Industry cavity block.
Further, in the electrodialysis system, electrode plate used is by titanium plating ruthenium processing.
Further, in the first order electrodialysis membrane stack, partition plate is provided between adjacent two films, it is by polypropylene system
Into.
Further, in the second level, third level electrodialysis membrane stack, partition plate is provided between negative and positive film, it is by poly- third
Made of alkene.
Further, in first order operation, preferred operations current density is 4mA/cm2, each compartment flow is 40L/h.
Further, in the second level and third level operation, preferred operations current density is 10mA/cm2, each compartment flow is equal
For 40L/h.
In the present invention, the electrodialysis process can be necessary to determine whether to need according to the composition and processing of concentrated seawater into
One step increases electrodialysis operation.
In the present invention, the concentrated seawater electrical conductivity from desalinator is 55-75ms/cm, and calcium and magnesium ion concentration is distinguished
For 600-700mg/L, 1400-1600mg/L, Na ion concentration 14000-16000mg/L, chlorine ion concentration 21000-
24000mg/L, sulfate ion concentration 2800-3200mg/L, potassium concentration 300-500mg/L, bromide ion concentration are
80-90mg/L.For above-mentioned concentrated seawater, preferably described electrodialysis process is operated by the first order, the second level operates and third level behaviour
Form.
The present invention has the advantages that compared with prior art:
(1) electrodialysis system that the present invention designs can efficiently separate the multivalent ion in concentrated seawater, can improve crude salt
Purity, and can achieve the purpose that concentrate sodium chloride brine, mitigate subsequent evaporation pressure so that by evaporation process produce compared with
The refined salt of high-purity.In addition, can after the first order desalinization liquor produced through system removes substantial amounts of calcium and magnesium ion by chemical precipitation
Back to desalinator again preparing fresh, and the second level and third level desalinization liquor can also be back to first order operation, from
And the overall Water Sproading rate of system is significantly increased.
(2) the more traditional concentrated seawater treatment technology of electrodialysis system that designs of the present invention, have expend less, easy to operate, ring
The advantages that border is friendly；Marine environmental pollution problem caused by avoiding concentrated seawater discharge at the same time, realizes the sustainable profit of resource
With.
Brief description of the drawings
Fig. 1 is the process flow chart for the electrodialysis system that the present invention designs, and is also especially given in figure equipped with unit price selection
The decomposition diagram of the electrodialysis membrane stack of property film；Wherein 1. it is the first order electrodialytic membranes equipped with Monovalent selectivity amberplex
Heap, is respectively 2., 3. the second level equipped with conventional ion exchange membrane, third level electrodialysis membrane stack.
Embodiment
With reference to specific embodiment, the invention will be further described, but protection scope of the present invention not limited to this.
Embodiment is as follows：
Embodiment 1
This example is using the electrodialysis system shown in Fig. 1.Specifically include：One is equipped with Monovalent selectivity amberplex
Electrodialysis membrane stack and two electrodialysis membrane stacks that common amberplex is housed.In addition, also a vaporising device is used to steam
The final concentrate rich in sodium chloride of hair.The specification of three electrodialysis membrane stacks is just the same.The repetition of each membrane stack
Unit number is 5.The area of every film is 11cm × 27cm.By the electrodialytic membranes equipped with Monovalent selectivity amberplex
The first order of system is stacked in, Monovalent selectivity amberplex used is respectively Japanese Asahi Chemical Industry Monovalent selectivity anode membrane
(NEOSEPTA CIMS), Japanese Asahi Chemical Industry's Monovalent selectivity cavity block (NEOSEPTA ACS), and membrane stack is each adjacent to electrode plate both sides
A Japan AGC pole film (SELEMION CMTE) is put into, for protecting Monovalent selectivity film.And two equipped with it is common from
The second level of the electrodialysis membrane stack of proton exchange respectively as system, the third level, conventional ion exchange membrane used is respectively day
This Asahi Chemical Industry anode membrane (NEOSEPTA CMX), Japanese Asahi Chemical Industry's cavity block (NEOSEPTA AMX).Electrode plate used passes through titanium
Plate ruthenium processing；The baffle dimensions being placed between two films are also 11cm × 27cm, are made up of polypropylene.
As shown in Figure 1, by 1L concentrated seawaters, (the concentrated seawater electrical conductivity is 60ms/cm, and calcium and magnesium ion concentration is respectively
665mg/L, 1546mg/L, Na ion concentration 15117mg/L, chlorine ion concentration 23525mg/L, sulfate ion concentration are
3041mg/L, potassium concentration 392mg/L, bromide ion concentration 89mg/L) and 1L deionized waters be separately added into first order film
The desalting chamber and enriched chamber of heap, it is 3% metabisulfite solution that pole liquid chamber, which adds 1L mass fractions,.Operation electric current density is 4mA/cm2,
Each compartment flow is 40L/h.When the electrical conductivity of desalting chamber's solution is less than 20ms/cm (i.e. salt rejection rate is higher than 70%), the
Level-one operation terminates.Then the feed liquid in enriched chamber is put into fluid reservoir, and first order desalinization liquor removes greatly by chemical precipitation
After the calcium and magnesium ion of amount, back to desalinator again preparing fresh.Several batch experiments are repeated, are made in fluid reservoir
Feed liquid reaches the demand of second level operation.Found by detection, enriched chamber's feed liquid electrical conductivity is left in 50ms/cm in each batch
The right side, wherein calcium and magnesium ion concentration drop to 175mg/L, 200mg/L or so respectively.Show to operate by the first order, can be significantly
Separate the multivalent ion in concentrated seawater.Then second level enriched chamber is pumped into first order concentrate 1L with desalting chamber；The third level is dense
Contracting room is pumped into second level concentrate 1L with desalting chamber, and it is 3% metabisulfite solution that pole liquid chamber, which adds 1L mass fractions,；Operation electricity
Current density is 10mA/cm2, each compartment flow is 40L/h, and it is equal to work as desalinization liquor electrical conductivity in the second level, third level membrane stack
Less than 5ms/cm, operation terminates.And the second level, third level desalinization liquor can be back in first order membrane stack.Finally obtain at this time
Concentrate electrical conductivity rich in sodium chloride close to 110ms/cm, wherein calcium and magnesium ion concentration be respectively 976mg/L, 1432mg/
L or so.Finally crude salt is produced by evaporation process again.By repeat experiment find, the crude salt purity stabilization of extraction 85%, and
Concentrated seawater is only 56% without the crude salt purity that system is handled.
Embodiment 2
Electrodialysis system used is the same as embodiment 1.The difference is that the area of every film is 200cm × 400cm.Phase
Ying Di, it is also 200cm × 400cm to be placed on the baffle dimensions between two films.
In addition, the operating procedures at different levels of system are the same as embodiment 1.The difference is that by the 10L concentrated seawaters (concentrated seawater
Electrical conductivity is 60ms/cm, and calcium and magnesium ion concentration is respectively 665mg/L, 1546mg/L, Na ion concentration 15117mg/L, chlorine
Ion concentration is 23525mg/L, sulfate ion concentration 3041mg/L, potassium concentration 392mg/L, and bromide ion concentration is
The desalting chamber and enriched chamber of the first order membrane stack 89mg/L) are separately added into 10L deionized waters, second level enriched chamber and desalting chamber are equal
First order concentrate 10L is pumped into, third level enriched chamber and desalting chamber are pumped into second level concentrate 10L, and pole liquid chamber adds 10L
Mass fraction is 3% metabisulfite solution.The concentrate electrical conductivity rich in sodium chloride finally obtained at this time is close to 130ms/cm.
Finally crude salt is produced by evaporation process again.By repeat experiment find, the crude salt purity stabilization of extraction 85%~87%, and
Concentrated seawater is only 56% without the crude salt purity that system is handled.
Results showed that the electrodialysis system of design can effectively improve the purity of crude salt.It is so of the invention from concentrated seawater
Middle extraction crude salt is effective, and the economized for realizing resource utilizes.
Claims (10)
1. a kind of method that crude salt is extracted from concentrated seawater, the method are：
(1) electrodialysis process is carried out to the concentrated seawater from desalinator, the electrodialysis process is operated including three-level：
First order operation is to use the first order electrodialysis membrane stack equipped with Monovalent selectivity amberplex to be handled, by dense sea
Water and deionized water are separately added into the desalting chamber and enriched chamber of first order electrodialysis membrane stack, and metabisulfite solution is added in the liquid chamber of pole,
It is the terminal of first order operation when the electrical conductivity of processing to desalinization liquor is less than 20ms/cm, first order operation at this time terminates,
Desalinization liquor I and concentrate I are obtained, wherein desalinization liquor I is after chemical precipitation removes calcium and magnesium ion, back to sea water desalination work
Factory's preparing fresh again；And concentrate I is operated into the second level；
Second level operation is to use the second level electrodialysis membrane stack equipped with conventional ion exchange membrane to concentrate I processing, past
The enriched chamber of second level electrodialysis membrane stack adds concentrate I with desalting chamber, and pole liquid chamber adds metabisulfite solution, when processing is to de-
It is the terminal of the second level operation when saline solution electrical conductivity is less than 5ms/cm, second level operation terminates, and obtains desalinization liquor II and concentration
Liquid II, wherein concentrate II are operated into the third level, and desalinization liquor II can be back in first order membrane stack；
Third level operation is to use the second level electrodialysis membrane stack equipped with conventional ion exchange membrane to concentrate II processing, past
The enriched chamber of third level electrodialysis membrane stack adds concentrate II with desalting chamber, and pole liquid chamber adds metabisulfite solution, when processing extremely
When desalinization liquor electrical conductivity is less than 5ms/cm, be the third level operation terminal, the third level operation terminates, obtain desalinization liquor III and
Concentrate III, wherein desalinization liquor III can be back in first order membrane stack；
(2) crude salt is made through evaporating in concentrate III.
2. the method as described in claim 1, it is characterised in that：Concentrated seawater electrical conductivity from desalinator is 55-
75ms/cm, calcium and magnesium ion concentration are respectively 600-700mg/L, 1400-1600mg/L, Na ion concentration 14000-
16000mg/L, chlorine ion concentration 21000-24000mg/L, sulfate ion concentration 2800-3200mg/L, potassium ion are dense
Spend for 300-500mg/L, bromide ion concentration 80-90mg/L.
3. method as claimed in claim 2, it is characterised in that：The electrodialysis process is operated by the first order, the second level operates
Operate and form with the third level.
4. the method as described in one of claims 1 to 3, it is characterised in that：The sodium sulphate that pole liquid chamber adds in three-level operation is molten
The mass fraction of liquid is 3-5%.
5. method as claimed in claim 4, it is characterised in that：The quality for the metabisulfite solution that pole liquid chamber adds in three-level operation
Fraction is 3%.
6. the method as described in one of claims 1 to 3, it is characterised in that：First order electrodialysis membrane stack is cloudy by Monovalent selectivity
Cation-exchange membrane is alternately arranged composition, and membrane stack is respectively put into a pole film adjacent to electrode plate both sides, for protecting monovalent selection
Property film, so as to form pole liquid chamber, enriched chamber and desalting chamber；The second level, third level electrodialysis membrane stack are by common negative and positive
Amberplex is alternately arranged composition, forms pole liquid chamber, enriched chamber and desalting chamber respectively.
7. method as claimed in claim 6, it is characterised in that：In the first order electrodialysis membrane stack, Monovalent selectivity is cloudy
Cation-exchange membrane is Japanese Asahi Chemical Industry Monovalent selectivity anode membrane, Japanese Asahi Chemical Industry Monovalent selectivity cavity block, and pole film is Japan
Asahi Glass pole film；In the second level, third level electrodialysis membrane stack, common anion and cation exchange membrane is Japanese Asahi Chemical Industry's sun
Film, Japanese Asahi Chemical Industry cavity block.
8. the method for claim 7, it is characterised in that：In the first order, the second level, third level electrodialysis membrane stack
Number of repeat unit is respectively 5.
9. the method as described in one of claims 1 to 3, it is characterised in that：In the electrodialysis system, electrode plate used is equal
By titanium plating ruthenium processing；In the first order, the second level, third level electrodialysis membrane stack, it is both provided between adjacent two films
Partition plate, what it was made up of polypropylene.
10. the method as described in one of claims 1 to 3, it is characterised in that：In first order operation, operation electric current density is
4mA/cm2, each compartment flow is 40L/h；In the second level and third level operation, operation electric current density is 10mA/cm2, respectively
Compartment flow is 40L/h.
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