CN106082275B - A kind of salt extraction process and salt making system - Google Patents
A kind of salt extraction process and salt making system Download PDFInfo
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- CN106082275B CN106082275B CN201610412626.2A CN201610412626A CN106082275B CN 106082275 B CN106082275 B CN 106082275B CN 201610412626 A CN201610412626 A CN 201610412626A CN 106082275 B CN106082275 B CN 106082275B
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- reverse osmosis
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- 150000003839 salts Chemical class 0.000 title claims abstract description 146
- 238000000605 extraction Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 374
- 238000002425 crystallisation Methods 0.000 claims abstract description 354
- 230000008025 crystallization Effects 0.000 claims abstract description 337
- 238000000926 separation method Methods 0.000 claims abstract description 149
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 141
- 238000012545 processing Methods 0.000 claims abstract description 114
- 238000005341 cation exchange Methods 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 83
- 239000013078 crystal Substances 0.000 claims abstract description 45
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 68
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 62
- 238000001704 evaporation Methods 0.000 claims description 55
- 230000008020 evaporation Effects 0.000 claims description 55
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 54
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 34
- 235000011152 sodium sulphate Nutrition 0.000 claims description 34
- 239000011780 sodium chloride Substances 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 28
- -1 anion salt Chemical class 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 20
- 238000001764 infiltration Methods 0.000 claims description 17
- 238000005342 ion exchange Methods 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000010413 mother solution Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 230000002779 inactivation Effects 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 abstract description 5
- 235000011132 calcium sulphate Nutrition 0.000 description 24
- 238000011084 recovery Methods 0.000 description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000011833 salt mixture Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- GJYLKIZKRHDRER-UHFFFAOYSA-N calcium;sulfuric acid Chemical compound [Ca].OS(O)(=O)=O GJYLKIZKRHDRER-UHFFFAOYSA-N 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 229940023913 cation exchange resins Drugs 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000001175 calcium sulphate Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000001640 fractional crystallisation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- 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
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- 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
- C02F2301/04—Flow arrangements
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to water treatment field, discloses a kind of salt extraction process and salt making system.This method includes：Brackish water is subjected to reverse-osmosis treated, obtains reverse osmosis concentrated water and reverse osmosis produced water；Reverse osmosis concentrated water is subjected to the first Crystallization Separation processing, obtains the first crystal salt and the first crystallization concentrated water, the first crystallization concentrated water is divided into the first backflow crystallization water outlet and cation exchange is intake；Cation exchange is intake and carries out cation exchange treatment, obtains cation exchange water outlet；Cation exchange water outlet is subjected to the second Crystallization Separation processing, obtains the second crystal salt and the second crystallization concentrated water；Second crystallization concentrated water is subjected to the processing of the 3rd Crystallization Separation, obtains the 3rd crystal salt and the 3rd crystallization concentrated water.The one-component salt of high-purity can be made using the method and system of the present invention, Water Sproading rate is high, cation exchange load is low, and carnallite cost of disposal, cost of investment and operating cost can be greatly reduced.
Description
Technical field
The present invention relates to water treatment field, in particular it relates to a kind of salt extraction process and salt making system.
Background technology
With the continuous lifting of environmental requirement, the contradictions such as water resource deficiency and environmental carrying capacity are limited increasingly highlight.In stone
In the production processes such as oiling work, coal chemical industry, electric power, steel and desalinization, substantial amounts of brine waste can be produced.In order to reduce
Outer displacement, the service efficiency of water improving, brine waste typically uses reuse after the embrane method processing based on counter-infiltration at present,
The service efficiency of water is improved to a certain extent.The occasion of zero liquid discharge is being required, reverse osmosis concentrated water is by further using steaming
Crystallization processes are sent out, obtain distilled water and solid carnallite.
The protrusions such as existing zero liquid discharge process generally existing film concentration and recovery rate is limited, solid carnallite is difficult to dispose are asked
Topic.Therefore, it is necessary to be improved on the basis of existing zero liquid discharge process, the rate of recovery of film concentration process is improved, is obtained
To the one-component salt of higher degree to be sold as byproduct, reduce carnallite cost of disposal and realize the synthesis of zero liquid discharge
Cost.
The content of the invention
The invention aims to overcome drawbacks described above present in prior art, there is provided a kind of salt extraction process and salt manufacturing
The one-component salt of high-purity can be made in system, salt extraction process of the invention, and Water Sproading rate is high, cation exchange load is low,
And carnallite cost of disposal, cost of investment and operating cost can be greatly reduced.
To achieve these goals, in a first aspect, the invention provides a kind of salt extraction process, this method includes：
(1) reverse-osmosis treated will be carried out containing the brackish water of dianion salt and univalent anion salt, by brackish water
Initial concentration is carried out, obtains the reverse osmosis concentrated water of rich salt and the reverse osmosis produced water of poor salt；
(2) reverse osmosis concentrated water for obtaining step (1) carries out the first Crystallization Separation processing, obtains the first crystal salt and first
Concentrated water is crystallized, the described first crystallization concentrated water is divided into two strands, being back to step (1) respectively as the first backflow crystallization water outlet is carried out
Described reverse-osmosis treated and the cation exchange treatment follow-up as cation exchange water inlet progress；
(3) the cation exchange water inlet obtained step (2) carries out cation exchange treatment, obtains rich monovalent cation salt
Cation exchange water outlet；
(4) the cation exchange water outlet that step (3) obtains is intake as crystallization and carries out the second Crystallization Separation processing, obtained
Second crystal salt and the second crystallization concentrated water；
(5) the second crystallization concentrated water for obtaining step (4) carries out the processing of the 3rd Crystallization Separation, obtains the 3rd crystal salt and the
Three crystallization concentrated waters.
Second aspect, the invention provides a kind of salt making system, the salt making system includes reverse osmosis units, the first crystallization point
From unit, cation exchange unit, the second Crystallization Separation unit and the 3rd Crystallization Separation unit,
The reverse osmosis units are used to that counter-infiltration will to be carried out containing the brackish water of dianion salt and univalent anion salt
Processing, obtains the reverse osmosis concentrated water of rich salt and the reverse osmosis produced water of poor salt；
The first Crystallization Separation unit is used to the reverse osmosis concentrated water from the reverse osmosis units carrying out the first crystallization
Separating treatment, obtain the first crystal salt and the first crystallization concentrated water, and the first Crystallization Separation unit and the reverse osmosis units
It is connected, at least partly reverse-osmosis treated will to be carried out by the first crystallization concentrate recirculation to the reverse osmosis units；
The cation exchange unit is used to be back to the counter-infiltration from the first Crystallization Separation unit
First crystallization concentrated water of unit is intake as cation exchange carries out cation exchange treatment, obtains the sun of rich monovalent cation salt
Ion exchange water outlet；
The second Crystallization Separation unit be used for using from the cation exchange unit cation exchange water inlet as
Crystallization water inlet carries out the second Crystallization Separation processing, obtains the second crystal salt and the second crystallization concentrated water；
The 3rd Crystallization Separation unit is used to carry out the second crystallization concentrated water from the second Crystallization Separation unit
The processing of 3rd Crystallization Separation, obtain the 3rd crystal salt and the 3rd crystallization concentrated water.
Using the present invention method and system, can produce high-purity one-component salt (including sulfate crystal salt and
Sodium chloride crystal salt), the one-component salt rate of recovery, the Water Sproading rate of system and the calcium sulfate rate of recovery are significantly increased, while sulphur
The high efficiente callback of sour calcium also greatly reduces the load of follow-up cation exchange, and energy consumption and throwing can be greatly reduced in this method
Provide cost.
According to a kind of preferred embodiment of the present invention, the second Crystallization Separation before processing is being carried out, is first handing over cation
The water that swaps out is evaporated processing, then carries out second using the evaporation concentrated water close to saturation that evaporation process obtains as crystallization water inlet
Crystallization Separation processing, can be greatly reduced energy consumption and cost of investment.
According to a kind of preferred embodiment of the present invention, in the processing of the 3rd Crystallization Separation, by the obtain the 3rd crystallization
Concentrated water is divided into two strands, handles to the second Crystallization Separation respectively as the 3rd crystallization backflow mother liquor reflux and is carried out as system concentrated water
Post processing, it is possible to achieve the concentration again of one-component salt and fractional crystallization, can realize and compare thoroughly one-component salt
Separation and crystallization, effectively improving the rate of recovery of one-component salt so that whole operation process realizes continuous operation, and stable state produces salt,
With preferable economic value and use value.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the salt extraction process of one embodiment of the present invention.
Fig. 2 is the schematic flow sheet of the salt extraction process of comparative example 1 of the present invention.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
In a first aspect, the invention provides a kind of salt extraction process, this method includes：
(1) reverse-osmosis treated will be carried out containing the brackish water of dianion salt and univalent anion salt, by brackish water
Initial concentration is carried out, obtains the reverse osmosis concentrated water of rich salt and the reverse osmosis produced water of poor salt；
(2) reverse osmosis concentrated water for obtaining step (1) carries out the first Crystallization Separation processing, obtains the first crystal salt and first
Concentrated water is crystallized, the described first crystallization concentrated water is divided into two strands, being back to step (1) respectively as the first backflow crystallization water outlet is carried out
Described reverse-osmosis treated and the cation exchange treatment follow-up as cation exchange water inlet progress；
(3) the cation exchange water inlet obtained step (2) carries out cation exchange treatment, obtains rich monovalent cation salt
Cation exchange water outlet；
(4) the cation exchange water outlet that step (3) obtains is intake as crystallization and carries out the second Crystallization Separation processing, obtained
Second crystal salt and the second crystallization concentrated water；
(5) the second crystallization concentrated water for obtaining step (4) carries out the processing of the 3rd Crystallization Separation, obtains the 3rd crystal salt and the
Three crystallization concentrated waters.
In the salt extraction process of the present invention, in order to be greatly reduced energy consumption, under preferable case, this method also includes：Carrying out the
Before the processing of two Crystallization Separations, the cation exchange water outlet that step (3) obtains is evaporated processing, distilled water is obtained and approaches
The evaporation concentrated water of saturation, the evaporation concentrated water is then subjected to second Crystallization Separation as crystallization water inlet and handled.
Preferably, the condition of the evaporation process includes：Temperature is 50-135 DEG C, more preferably 90-120 DEG C.
Preferably, the saturation degree of sodium sulphate or sodium chloride is 50-99% in the evaporation concentrated water close to saturation, further
Preferably 70-95%, it is still more preferably 90-95%.Wherein, saturation degree can be by controlling suitable concentration rate come real
It is existing.
In the salt extraction process of the present invention, in order to realize more effectively concentration under normal temperature condition, the rate of recovery of water is improved, and
The load and energy consumption of subsequent evaporation crystallization process are reduced, under preferable case, in step (1), contains dianion salt and monovalence
The brackish water of anion salt contains raw water and the first backflow crystallization water outlet described in step (2)；And in raw water salt total matter
Measure percentage composition Y%<When 2.5%, meet relational expression R1<Y/ (2.5-Y), R1 are cation exchange water inlet and reverse osmosis produced water
Volume flow ratio.
In the salt extraction process of the present invention, under preferable case, in step (1), the condition of reverse-osmosis treated includes：Temperature is
10-40 DEG C, more preferably 15-30 DEG C；Pressure is 1-6MPa, more preferably 1.6-4MPa；The reverse osmosis concentrated water
Volume flow ratio with the reverse osmosis produced water is 0.2-2：1, more preferably 0.3-1：1.
In the salt extraction process of the present invention, under preferable case, this method also includes：In step (1), carried out instead by brackish water
Before infiltration processing, at least one antisludging agent is added into the brackish water；And in the first Crystallization Separation described in step (2)
In processing, control condition inactivates the antisludging agent, to carry out Crystallization Separation.
Preferably, relative to brackish water described in 1L, the dosage of antisludging agent is 2-15mg, more preferably 3-7mg.
Preferably, the antisludging agent be organic phosphine type antisludging agent, organic phospho acid salt form antisludging agent, polycarboxylic acid-based inhibitor and
At least one of composite scale agent.
In the salt extraction process of the present invention, under preferable case, mode makes the scale inhibition at least one of in the following ways
Agent inactivates：
Mode one：At least one solid matter that can act as normal temperature crystalline seed is added into the reverse osmosis concentrated water；
Mode two：At least one flocculant is added into the reverse osmosis concentrated water；
Mode three：Adjust the pH value of the reverse osmosis concentrated water.
Preferably, in mode one, the addition of solid matter make it that the mass concentration of crystal seed in reverse osmosis concentrated water is 2%-
12%, more preferably 4%-8%.
Preferably, in mode one, solid matter is identical with the species of the difficultly water soluble salts in reverse osmosis concentrated water, further excellent
Hydrate of the choosing selected from calcium sulfate and/or calcium sulfate.
Preferably, in mode two, relative to the reverse osmosis concentrated water described in 1L, the dosage of flocculant is 2-20mg, further
Preferably 5-15mg, the flocculant are preferably iron chloride and/or ferric sulfate；
Preferably, in mode three, the pH value of the reverse osmosis concentrated water is adjusted to 3-6, is further preferably adjusted to 3.5-
4.5。
In the salt extraction process of the present invention, under preferable case, in step (2), the condition of the first Crystallization Separation processing includes：Temperature
Spend for 10-40 DEG C, more preferably 15-30 DEG C；First backflow crystallization water outlet and the volume flow ratio of cation exchange water inlet
For 1-20：1, more preferably 3-9：1.
In the salt extraction process of the present invention, it can be realized to brackish water by reverse-osmosis treated and the processing of the first Crystallization Separation
Efficient concentration, and can substantially reduce the load of follow-up cation exchange.Wherein, the first Crystallization Separation processing is grasped at normal temperatures
Make, the spontaneous generation crystallization process mainly by solution supersaturation caused by reverse osmosis concentration, without expending big energy or chemistry
Medicament.Most low solubility divalent salts can be got rid of by being handled by the first Crystallization Separation, the first crystal salt obtained
It is under normal circumstances the higher calcium sulfate of purity, and the calcium sulfate degree of supersaturation of the first obtained crystallization concentrated water significantly reduces.
In the salt extraction process of the present invention, under preferable case, in step (3), the condition of cation exchange treatment includes：Temperature
For 10-40 DEG C, more preferably 15-30 DEG C；Residence time is 2-30 minutes, more preferably 5-15 minutes；Cation
The concentration for exchanging calcium ion in water outlet is 0.01-5mg/L, more preferably 0.05-1mg/L.
In the salt extraction process of the present invention, under preferable case, in step (4), the mode of the second Crystallization Separation processing is first
Evaporative crystallization processing or crystallisation by cooling processing.
Preferably, the condition of the first evaporative crystallization processing includes：Temperature is 50-120 DEG C；
Preferably, the condition of the crystallisation by cooling processing includes：Temperature is less than 5 DEG C and higher than the freezing point of the crystallization water inlet
Temperature, more preferably -2~2 DEG C.
In the salt extraction process of the present invention, under preferable case, in step (5), the mode of the 3rd Crystallization Separation processing is
The processing of second evaporative crystallization.
Preferably, the condition of the second evaporative crystallization processing includes：Temperature is 50-120 DEG C.
It is further preferred that when the mode of the second Crystallization Separation processing is handled for the first evaporative crystallization, described second
The temperature of evaporative crystallization processing is lower than the temperature that first evaporative crystallization is handled at least 20 DEG C；The second Crystallization Separation processing
Mode when being handled for crystallisation by cooling, the temperature of second evaporative crystallization processing is 50-80 DEG C.
Wherein, the mode that the mode of the second Crystallization Separation processing is handled for the processing of the first evaporative crystallization, the 3rd Crystallization Separation
When being handled for the second evaporative crystallization, the second crystallization concentrated water that first can handle to obtain to the first evaporative crystallization carries out cooling processing,
Preferably, the cooling processing is carried out in spiral tube exchanger, tubular heat exchanger or double pipe heat exchanger, and described second
Crystallization concentrated water flows as tube side fluid in spiral tube exchanger, tubular heat exchanger or double pipe heat exchanger.This area skill
Art personnel can select the specific species of heat exchanger according to actual conditions, and this is well known to those skilled in the art, herein no longer
Repeat.Wherein, the second crystal salt is mainly sodium sulphate, and the 3rd crystal salt is mainly sodium chloride.
Wherein, the mode of the second Crystallization Separation processing be crystallisation by cooling processing, the mode of the 3rd Crystallization Separation processing be the
During the processing of two evaporative crystallizations, the evaporation concentrated water close to saturation that first can be obtained to evaporation process is carried out after cooling processing as knot
Crystalline substance water inlet carries out crystallisation by cooling processing, and the second crystallization concentrated water for then handling to obtain by crystallisation by cooling is carried out after carrying out heating treatment
The processing of second evaporative crystallization.
Preferably, the method for processing of cooling includes：It will be cooled close to the evaporation concentrated water of saturation by way of exchanging heat and handling
To crystallisation by cooling temperature, the crystallisation by cooling temperature is less than 5 DEG C and is higher than the freezing point temperature of the crystallization water inlet, further preferably
For -2~2 DEG C；And it is 1-20m/s, more preferably 2-5m/s to control flow velocity of the crystallization water inlet in heat exchange processing；
Preferably, the heat exchange processing is carried out in spiral tube exchanger, tubular heat exchanger or double pipe heat exchanger, and
The crystallization water inlet is flowed as tube side fluid in spiral tube exchanger, tubular heat exchanger or double pipe heat exchanger.Ability
Field technique personnel can select the specific species of heat exchanger according to actual conditions, and this is well known to those skilled in the art, herein
Repeat no more.Wherein, the second crystal salt is mainly sodium sulphate, and the 3rd crystal salt is mainly sodium chloride.
Preferably, the embodiment of the heating treatment is handled for heat exchange, and this is well known to those skilled in the art, herein
Repeat no more.
In the salt extraction process of the present invention, in order to further improve the rate of recovery of dianion salt, under preferable case, the party
Method also includes：The 3rd crystallization concentrated water that step (5) is obtained is divided into two strands, respectively as the 3rd crystallization backflow mother liquor reflux to step
Suddenly (4) carry out described the second Crystallization Separation processing and post-processed as system concentrated water.
Preferably, the 3rd crystallization backflow mother liquor and the volume flow ratio of the system concentrated water are 1-100：1, further
Preferably 3-50：1.
In the salt extraction process of the present invention, it is preferable that this method also includes the system concentrated water being evaporated crystallization treatment
To obtain the salt-mixture containing univalent anion salt and dianion salt.
In the salt extraction process of the present invention, under preferable case, the cation exchange water outlet contains dianion salt and one
Valency anion salt, and the weight/mass percentage composition of dianion salt is 0.2%-5% in the cation exchange water outlet；Further
Preferably, the dianion salt contains sodium sulphate, and the univalent anion salt contains sodium chloride；It is further preferred that
The dianion salt is sodium sulphate, and the univalent anion salt is sodium chloride.
Second aspect, as shown in figure 1, the invention provides a kind of salt making system, the salt making system include reverse osmosis units,
First Crystallization Separation unit, cation exchange unit, the second Crystallization Separation unit and the 3rd Crystallization Separation unit,
The reverse osmosis units are used to that counter-infiltration will to be carried out containing the brackish water of dianion salt and univalent anion salt
Processing, obtains the reverse osmosis concentrated water of rich salt and the reverse osmosis produced water of poor salt；
The first Crystallization Separation unit is used to the reverse osmosis concentrated water from the reverse osmosis units carrying out the first crystallization
Separating treatment, obtain the first crystal salt and the first crystallization concentrated water, and the first Crystallization Separation unit and the reverse osmosis units
It is connected, at least partly reverse-osmosis treated will to be carried out by the first crystallization concentrate recirculation to the reverse osmosis units；
The cation exchange unit is used to be back to the counter-infiltration from the first Crystallization Separation unit
First crystallization concentrated water of unit is intake as cation exchange carries out cation exchange treatment, obtains the sun of rich monovalent cation salt
Ion exchange water outlet；
The second Crystallization Separation unit be used for using from the cation exchange unit cation exchange water inlet as
Crystallization water inlet carries out the second Crystallization Separation processing, obtains the second crystal salt and the second crystallization concentrated water；
The 3rd Crystallization Separation unit is used to carry out the second crystallization concentrated water from the second Crystallization Separation unit
The processing of 3rd Crystallization Separation, obtain the 3rd crystal salt and the 3rd crystallization concentrated water.
In the salt making system of the present invention, under preferable case, the salt making system also includes evaporation element, and the evaporation element is used
In the cation exchange water outlet from the cation exchange unit is evaporated into processing, distilled water is obtained and close to saturation
Evaporate concentrated water；And the second Crystallization Separation unit be used for using the evaporation concentrated water from the evaporation element as crystallize into
Water carries out the second Crystallization Separation processing.
Preferably, the evaporation element includes evaporator.
In the salt making system of the present invention, under preferable case, reverse osmosis units include an at least reverse-osmosis membrane element, enter one
Preferably, reverse osmosis units include at least two reverse-osmosis membrane elements being used in series to step.
In the salt making system of the present invention, under preferable case, the first Crystallization Separation unit includes the first crystalline element and first
Solid-liquid separation unit,
First crystalline element is used to the reverse osmosis concentrated water from the reverse osmosis units carrying out the first crystallization treatment,
The first crystallization water outlet and the first crystallization solidliquid mixture used as the first crystallization concentrated water is obtained,
First solid-liquid separation unit is used to enter the first crystallization solidliquid mixture from first crystalline element
The processing of the separation of solid and liquid of row first, obtain the first crystal salt and the first crystalline mother solution used as the first crystallization concentrated water.
In the salt making system of the present invention, the mode of the second Crystallization Separation processing (is corresponded to according to a kind of preferred embodiment
Mode for crystallisation by cooling processing, the processing of the 3rd Crystallization Separation is the processing of the second evaporative crystallization), the salt making system also includes cooling
Unit and heating unit, the cooling unit are used to be cooled the evaporation concentrated water close to saturation from the evaporation element
Processing, cooling product is then subjected to crystallisation by cooling processing as crystallization water inlet supply to the second Crystallization Separation unit.The liter
Warm unit is used to carry out the handle to obtain through crystallisation by cooling second crystallization concentrated water from the second Crystallization Separation unit at heating
Supply to the 3rd Crystallization Separation unit carries out the second evaporative crystallization processing after reason.
Preferably, heating unit includes heat exchanger, it is further preferred that the heat exchanger is spiral tube exchanger, tubulation
Formula heat exchanger or double pipe heat exchanger.
In the salt making system of the present invention, the mode of the second Crystallization Separation processing (is corresponded to according to a kind of preferred embodiment
Mode for the processing of the first evaporative crystallization, the processing of the 3rd Crystallization Separation is the processing of the second evaporative crystallization), the salt making system also includes
Cooling unit, for will be supplied after the second crystallization concentrated water cooling from the second Crystallization Separation unit to the 3rd Crystallization Separation unit
Carry out the second evaporative crystallization processing.
Preferably, cooling unit includes heat exchanger, it is further preferred that the heat exchanger is spiral tube exchanger, tubulation
Formula heat exchanger or double pipe heat exchanger.Those skilled in the art can select the specific species of heat exchanger according to actual conditions, this
It is well known to those skilled in the art, will not be repeated here.
In the salt making system of the present invention, under preferable case, the second Crystallization Separation unit includes the second crystalline element and second
Solid-liquid separation unit,
Second crystalline element is used to intake the crystallization from the cation exchange unit or the evaporation element
The second crystallization treatment is carried out, obtains the second crystallization water outlet and the second crystallization solidliquid mixture used as the second crystallization concentrated water,
Second solid-liquid separation unit is used to enter the second crystallization solidliquid mixture from second crystalline element
The processing of the separation of solid and liquid of row second, obtain the second crystal salt and the second crystalline mother solution used as the second crystallization concentrated water.
Preferably, second crystalline element includes crystallizing evaporator or cooler crystallizer.
The present invention salt making system in, under preferable case, the 3rd Crystallization Separation unit include the 3rd crystalline element and
3rd solid-liquid separation unit,
3rd crystalline element is used to the second crystallization concentrated water from second crystalline element carrying out the 3rd crystallization
Processing, the 3rd crystallization water outlet and the 3rd crystallization solidliquid mixture used as the 3rd crystallization concentrated water is obtained,
3rd solid-liquid separation unit is used to enter the 3rd crystallization solidliquid mixture from the 3rd crystalline element
The processing of the separation of solid and liquid of row the 3rd, obtain the 3rd crystal salt and the 3rd crystalline mother solution used as the 3rd crystallization concentrated water；
Preferably, the 3rd crystalline element includes crystallizing evaporator.
Preferably, the salt making system is also used for the system concentrated water from the 3rd Crystallization Separation unit including crystallizing evaporator
Crystallization treatment is evaporated to obtain the salt-mixture containing univalent anion salt and dianion salt.
Embodiment
The present invention will be described in detail by way of examples below, but and is not so limited the scope of the present invention.Below
In embodiment, unless otherwise instructed, used method is method commonly used in the art.
The each component and its content in water are determined using inductively coupled plasma (ICP) method and chromatography of ions (IC).
It is as shown in table 1 using synthesis brackish water analog raw material water, its component.
Table 1
| Project | Na+ | Ca2+ | Cl- | SO4 2- |
| Unit | mg/L | mg/L | mg/L | mg/L |
| Numerical value | 612.2 | 413.2 | 301.8 | 1859.3 |
Embodiment 1
With reference to Fig. 1, the present embodiment is used for the salt extraction process for illustrating the present invention.
The reverse osmosis units used in the present embodiment are to include 3 putaminas in parallel, every putamina built with 6 series connection
One section of counter-infiltration system of one-level of DOW BW30FR-400 reverse-osmosis membrane elements；First Crystallization Separation unit includes a total measurement (volume)
For 12.5m3Reaction depositing reservoir and centrifugal separating device；Cation exchange unit is that a volume is 0.15m3, filling DOWEX
The cation exchanger of MAC-3 Weak-acid cation exchange resins；Evaporation element is that a heat exchange area is 20m2Mechanical compress
Formula evaporator；Second Crystallization Separation unit is 1.0m including a heat exchange area2Forced-circulation evaporation crystallizer and centrifugation point
From device；3rd Crystallization Separation unit is 0.2m including a heat exchange area2Forced-circulation evaporation crystallizer and centrifugation
Device.The flow of inlet water of raw water is 11.0m3/ h, concrete technology flow process are as follows：
(1) it is 11.0m by flow3The synthesis brackish water shown in table 1 that/h, temperature are 25 DEG C is as raw water and flow
4.0m3After/h, the backflow crystallization water outlet mixing of first that temperature is 25 DEG C, 5.0mg/L antisludging agent (active ingredient is added thereto
For organic phosphonate, Ondeo Nalco Co., OSMOTREAT OSM1035) after, with 15.0m3/ h total flow, 25 DEG C of temperature are made
Water inlet supply is mixed into reverse osmosis units for counter-infiltration, and reverse-osmosis treated is carried out at 25 DEG C.Wherein, reverse osmosis units use
Part concentrated water circulate operation pattern, concentrated water internal circulating load are 15.0m3/ h, the intake pressure of reverse osmosis units is 1.6MPa.By anti-
After permeation unit processing, it is 10.0m to obtain flow3/ h, temperature are 25 DEG C of reverse osmosis produced water and flow is 5.0m3/ h, temperature are
25 DEG C of reverse osmosis concentrated water.The degree of supersaturation of calcium sulfate is 352.0% in reverse osmosis concentrated water.
(2) it is 5.0m to flow310.0mg/L chlorination ferric flocculant is added in/h, the reverse osmosis concentrated water that temperature is 25 DEG C
Afterwards, supply to the first Crystallization Separation unit and carry out the processing of normal temperature (25 DEG C) Crystallization Separation.Because the effect of flocculant causes part
Antisludging agent loses the effect for preventing crystallization, separates out part of sulfuric acid calcium crystalline solid in the oversaturated reverse osmosis concentrated water of calcium sulfate, obtains
Water outlet and the first crystallization solidliquid mixture are crystallized to the first of clarification, the first crystallization solidliquid mixture is entered with centrifugal separating device
Row centrifuging treatment, crystal of calcium sulfate salt (being 13.8kg/h after the deduction crystallization water) and the first crystalline mother solution are obtained, into split-phase
The first same crystallization water outlet is divided into two strands with the first crystalline mother solution as the first crystallization concentrated water, and one flow is 4.0m3/ h, temperature
It is 1.0m for 25 DEG C of the first backflow crystallization water outlet and another plume amount3/ h, the cation exchange that temperature is 25 DEG C are intake.By
One backflow crystallization water outlet supply to step (1) mix with raw water after into reverse osmosis units progress circular treatment.
(3) it is 1.0m by flow3/ h, the cation exchange that temperature is 25 DEG C water inlet are sent into cation exchange unit and carry out sun
Ion-exchange treatment, wherein, it is 9 minutes that cation exchange, which was intake in the residence time of cation exchange unit, and obtaining flow is
1.0m3The cation exchange water outlet that/h, temperature are 25 DEG C, calcium ion concentration is 0.05mg/l.
(4) it is 1.0m by flow3/ h, the cation exchange water outlet that temperature is 25 DEG C are supplied to evaporation element, at 105 DEG C
It is evaporated concentration.The concentration rate for controlling evaporation element is 16.7 times, and it is 0.94m to obtain flow3/ h condensation production water
It is 0.06m with flow3/ h, the evaporation element concentrated water (saturation degree 81.3% of sodium sulphate) close to saturation that temperature is 105 DEG C.
(5) it is 0.06m by flow3The evaporation element concentrated water and flow that/h, temperature are 105 DEG C are 0.14m3/ h, temperature 60
DEG C the 3rd crystallization backflow mother liquor mixing after as the second crystallized mixed water inlet supply to the second Crystallization Separation unit, at 100 DEG C
Under be evaporated Crystallization Separation processing.Because sodium sulphate prior to sodium chloride reaches saturation, part of sulfuric acid sodium separates out, using centrifugation point
After processing is centrifuged from device, sulfate crystal salt (being 13.3kg/h after the deduction crystallization water) is obtained.Meanwhile flowed
Measure as 0.047m3/ h distilled water and flow is 0.153m3/ h, the crystallization concentrated water of second that temperature is 100 DEG C.
(6) it is 0.153m by flow3/ h, the crystallization concentrated water of second that temperature is 100 DEG C are cooled to 60 through tubular heat exchanger
Supply is evaporated Crystallization Separation processing to the 3rd Crystallization Separation unit at 60 DEG C after DEG C.At this temperature, due to sodium chloride
Reach saturation prior to sodium sulphate, partial oxidation sodium separates out, and after processing is centrifuged using centrifugal separating device, obtains chlorination
Sodium crystal salt (being 3.7kg/h after the deduction crystallization water).Meanwhile it is 0.009m to obtain flow3/ h distilled water and flow is
0.144m3/ h, the crystallization concentrated water of the 3rd that temperature is 60 DEG C.3rd crystallization concentrated water is divided into two strands, will flow be wherein 0.140m3/
H one second Crystallization Separation unit circular treatment sent back to as the 3rd crystallization backflow mother liquor in step (5), it is by flow
0.004m3Another strand of/h supplies to crystallizing evaporator as system concentrated water and is evaporated crystallization treatment, obtains mainly including chlorine
Change the salt-mixture of sodium and sodium sulphate.
Table 2 gives the flow and component of each material flow in embodiment 1.
Table 2
From table 2 it can be seen that temperature is to contain higher calcium, sodium, chlorion and sulfate radical simultaneously in 25 DEG C of raw water,
With temperature is 25 DEG C obtain after the first backflow crystallization water outlet mixes temperature be 25 DEG C, calcium sulfate degree of supersaturation be 99.0% it is anti-
Infiltration mixing water inlet, after reverse-osmosis treated, the calcium sulfate degree of supersaturation of obtained reverse osmosis concentrated water is 352.0%, due to
The effect of antisludging agent, now reverse osmosis concentrated water is still stable.Reverse osmosis concentrated water loses resistance by flocculant antisludging agent
After the effect only crystallized, calcium sulphate solid, the calcium sulfate mistake of the first backflow crystallization water outlet are separated out in normal temperature Crystallizing process
Saturation degree declines to a great extent to 116.6%, close to saturation state (calcium sulfate degree of supersaturation 100%), reaches a kind of new stabilization
State, reverse osmosis units are back to afterwards and carry out circular treatment.This circular treatment also causes the Water Sproading rate and sulfuric acid of system
The calcium rate of recovery increases considerably, in the present embodiment, the combined system that is made up of reverse osmosis units and the first Crystallization Separation unit
Water Sproading rate be 90.9%, and the rate of recovery (in terms of calcium) of crystal of calcium sulfate salt then be 89.5%.The efficient crystallization of calcium sulfate
Recovery also greatly reduces the load of follow-up cation exchange.In the present embodiment, for raw water, cation exchange
The ion exchange load that unit is intake for cation exchange is only 10.5%, greatly reduces the investment and operation of ion exchange
Cost.
On the other hand, using the difference of the solubility with temperature of sodium sulphate and sodium chloride change (in 60 DEG C of -100 DEG C of scopes
It is interior, sodium sulphate in water solubility with temperature rise and reduce, the rise of the solubility with temperature of sodium chloride and raise), adopt
It is combined with the second Crystallization Separation (100 DEG C) with the 3rd Crystallization Separation (60 DEG C), furthermore achieved that sodium sulphate and sodium chloride
Separation.In the present embodiment, the rate of recovery (in terms of sulfate radical in ion exchange water outlet) of sodium sulphate is 91.4%, and sodium chloride returns
Yield (with chloride ion in ion exchange water outlet) is 74.6%, realizes the higher rate of recovery.
Embodiment 2
With reference to Fig. 1, the present embodiment is used for the salt extraction process for illustrating the present invention.
The reverse osmosis units used in the present embodiment are to include 3 putaminas in parallel, every putamina built with 6 series connection
One section of counter-infiltration system of one-level of DOW BW30FR-400 reverse-osmosis membrane elements；First Crystallization Separation unit includes a total measurement (volume)
For 12.5m3Reaction depositing reservoir and centrifugal separating device；Cation exchange unit is that a volume is 0.15m3, filling DOWEX
The cation exchanger of MAC-3 Weak-acid cation exchange resins；Evaporation element is that a heat exchange area is 20m2Mechanical compress
Formula evaporator；Second Crystallization Separation unit is 0.15m including a volume with heat-insulation layer3Rustless steel container and centrifugation
Device；3rd Crystallization Separation unit is 1.0m including a heat exchange area2Forced-circulation evaporation crystallizer and centrifuge fill
Put.The flow of inlet water of raw water is 11.0m3/ h, concrete technology flow process are as follows：
(1) it is 11.0m by flow3The synthesis brackish water shown in table 1 that/h, temperature are 25 DEG C is as raw water and flow
4.0m3After/h, the backflow crystallization water outlet mixing of first that temperature is 25 DEG C, 5.0mg/L antisludging agent (active ingredient is added thereto
For organic phosphonate, Ondeo Nalco Co., OSMOTREAT OSM1035) after, with 15.0m3/ h total flow, 25 DEG C of temperature are made
Water inlet supply is mixed into reverse osmosis units for counter-infiltration, and reverse-osmosis treated is carried out at 25 DEG C.Wherein, reverse osmosis units use
Part concentrated water circulate operation pattern, concentrated water internal circulating load are 15.0m3/ h, the intake pressure of reverse osmosis units is 1.6MPa.By anti-
After permeation unit processing, it is 10.0m to obtain flow3/ h, temperature are 25 DEG C of reverse osmosis produced water and flow is 5.0m3/ h, temperature are
25 DEG C of reverse osmosis concentrated water.The degree of supersaturation of calcium sulfate is 352.0% in reverse osmosis concentrated water.
(2) it is 5.0m to flow310.0mg/L chlorination ferric flocculant is added in/h, the reverse osmosis concentrated water that temperature is 25 DEG C
Afterwards, supply to the first Crystallization Separation unit and carry out the processing of normal temperature (25 DEG C) Crystallization Separation.Because the effect of flocculant causes part
Antisludging agent loses the effect for preventing crystallization, separates out part of sulfuric acid calcium crystalline solid in the oversaturated reverse osmosis concentrated water of calcium sulfate, obtains
Water outlet and the first crystallization solidliquid mixture are crystallized to the first of clarification, the first crystallization solidliquid mixture is entered with centrifugal separating device
Row centrifuging treatment, crystal of calcium sulfate salt (being 13.8kg/h after the deduction crystallization water) and the first crystalline mother solution are obtained, into split-phase
The first same crystallization water outlet is divided into two strands with the first crystalline mother solution as the first crystallization concentrated water, and one flow is 4.0m3/ h, temperature
It is 1.0m for 25 DEG C of the first backflow crystallization water outlet and another plume amount3/ h, the cation exchange that temperature is 25 DEG C are intake.By
One backflow crystallization water outlet supply to step (1) mix with raw water after into reverse osmosis units progress circular treatment.
(3) it is 1.0m by flow3/ h, the cation exchange that temperature is 25 DEG C water inlet are sent into cation exchange unit and carry out sun
Ion-exchange treatment, wherein, it is 9 minutes that cation exchange, which was intake in the residence time of cation exchange unit, and obtaining flow is
1.0m3The cation exchange water outlet that/h, temperature are 25 DEG C, calcium ion concentration is 0.05mg/l.
(4) it is 1.0m by flow3/ h, the cation exchange water outlet that temperature is 25 DEG C are supplied to evaporation element, at 105 DEG C
It is evaporated concentration.Controlling the concentration rate of evaporation element, it is 0.94m to obtain flow to 16.7 times3/ h condensation production water
It is 0.06m with flow3/ h, the evaporation element concentrated water (saturation degree 81.3% of sodium sulphate) close to saturation that temperature is 105 DEG C.
(5) it is 0.06m by flow3The evaporation element concentrated water and flow that/h, temperature are 105 DEG C are 0.01m3/ h, temperature 60
DEG C the 3rd crystallization backflow mother liquor mixing, be cooled to by spiral tube exchanger after 0 DEG C be used as the second crystallized mixed water inlet supply
To the second Crystallization Separation unit, crystallisation by cooling separating treatment is carried out at 0 DEG C.Due to sodium sulphate solubility at low temperature drastically
Decline (solubility of the sodium sulphate in water is about 4.9 grams at 0 DEG C), part of sulfuric acid sodium separates out, and is carried out using centrifugal separating device
After centrifuging treatment, sulfate crystal salt (being 14.0kg/h after the deduction crystallization water) is obtained.Meanwhile obtain flow and be
0.07m3/ h, the crystallization concentrated water of second that temperature is 0 DEG C.
(6) it is 0.07m by flow3/ h, the crystallization concentrated water of second that temperature is 0 DEG C are after tubular heat exchanger is warming up to 60 DEG C
Supply is evaporated Crystallization Separation processing to the 3rd Crystallization Separation unit at 60 DEG C.At this temperature, due to sodium chloride prior to
Sodium sulphate reaches saturation, and partial oxidation sodium separates out, and after processing is centrifuged using centrifugal separating device, obtains sodium chloride knot
Brilliant salt (being 4.4kg/h after the deduction crystallization water).Meanwhile it is 0.058m to obtain flow3/ h distilled water and flow is 0.012m3/h、
The 3rd crystallization concentrated water that temperature is 60 DEG C.3rd crystallization concentrated water is divided into two strands, will flow be wherein 0.010m3/ h one work
The the second Crystallization Separation unit circular treatment sent back to for the 3rd crystallization backflow mother liquor in step (5), is 0.002m by flow3/ h's
Another burst of conduct system concentrated water supplies to crystallizing evaporator and is evaporated crystallization treatment, obtains mainly including sodium chloride and sodium sulphate
Salt-mixture.
Table 3 gives the flow and component of each material flow in embodiment 2.
Table 3
From table 3 it can be seen that temperature is to contain higher calcium, sodium, chlorion and sulfate radical simultaneously in 25 DEG C of raw water,
With temperature is 25 DEG C obtain after the first backflow crystallization water outlet mixes temperature be 25 DEG C, calcium sulfate degree of supersaturation be 99.0% it is anti-
Infiltration mixing water inlet, after reverse-osmosis treated, the calcium sulfate degree of supersaturation of obtained reverse osmosis concentrated water is 352.0%, due to
The effect of antisludging agent, now reverse osmosis concentrated water is still stable.Reverse osmosis concentrated water loses resistance by flocculant antisludging agent
After the effect only crystallized, calcium sulphate solid, the calcium sulfate mistake of the first backflow crystallization water outlet are separated out in normal temperature Crystallizing process
Saturation degree declines to a great extent to 116.6%, close to saturation state (calcium sulfate degree of supersaturation 100%), reaches a kind of new stabilization
State, reverse osmosis units are back to afterwards and carry out circular treatment.This circular treatment also causes the Water Sproading rate and sulfuric acid of system
The calcium rate of recovery increases considerably, in the present embodiment, the combined system that is made up of reverse osmosis units and the first Crystallization Separation unit
Water Sproading rate be 90.9%, and the rate of recovery (in terms of calcium) of crystal of calcium sulfate salt then be 89.5%.The efficient crystallization of calcium sulfate
Recovery also greatly reduces the load of follow-up cation exchange.In the present embodiment, for raw water, cation exchange
The ion exchange load that unit is intake for cation exchange is only 10.5%, greatly reduces the investment and operation of ion exchange
Cost.
On the other hand, varied with temperature using the solubility of sodium sulphate and sodium chloride in low-temperature region significant difference (from
40 DEG C to 0 DEG C, solubility of the sodium sulphate in water is drastically reduced to about 4.9 grams from about 49 grams, and the solubility of sodium chloride only from
36.6 grams faint to be reduced to 35.7 grams), it is combined using the second Crystallization Separation (0 DEG C) with the 3rd Crystallization Separation (60 DEG C), enters one
Step realizes the separation of sodium sulphate and sodium chloride.In the present embodiment, the rate of recovery of sodium sulphate is (with the sulfuric acid in ion exchange water outlet
Root meter) it is 96.1%, the rate of recovery (with chloride ion in ion exchange water outlet) of sodium chloride is 89.1%, is realized higher
The rate of recovery.
Embodiment 3
According to the method for embodiment 2, the difference is that, in step (6), using the 3rd crystallization concentrated water of whole as system concentrated water
Supply is evaporated crystallization treatment to crystallizing evaporator, and specifically, step (5) and step (6) are：
(5) it is 0.06m by flow3/ h, the evaporation element concentrated water that temperature is 105 DEG C are cooled to 0 by spiral tube exchanger
Crystallisation by cooling separating treatment is carried out at 0 DEG C to the second Crystallization Separation unit as the second crystallization water inlet supply after DEG C.Due to sulphur
The solubility of sour sodium drastically declines at low temperature, and part of sulfuric acid sodium separates out, and processing is centrifuged using centrifugal separating device
Afterwards, sulfate crystal salt (being 11.6kg/h after the deduction crystallization water) is obtained.Meanwhile it is 0.06m to obtain flow3/ h, temperature are 0 DEG C
Second crystallization concentrated water.
(6) it is 0.06m by flow3/ h, the crystallization concentrated water of second that temperature is 0 DEG C are after tubular heat exchanger is warming up to 60 DEG C
Supply is evaporated Crystallization Separation processing to the 3rd Crystallization Separation unit at 60 DEG C.At this temperature, due to sodium chloride prior to
Sodium sulphate reaches saturation, and partial oxidation sodium separates out, and after processing is centrifuged using centrifugal separating device, obtains sodium chloride knot
Brilliant salt (being 2.3kg/h after the deduction crystallization water).Meanwhile it is 0.05m to obtain flow3/ h distilled water and flow is 0.01m3/ h, temperature
Spend the 3rd crystallization concentrated water for 60 DEG C.Using the 3rd crystallization concentrated water as system concentrated water, all supply to crystallizing evaporator is evaporated
Crystallization treatment, obtain the main salt-mixture comprising sodium chloride and sodium sulphate.
Table 4 gives the flow and component of each material flow in embodiment 3.
Table 4
In the present embodiment, the rate of recovery (in terms of sulfate radical in ion exchange water outlet) of sodium sulphate is 79.8%, sodium chloride
The rate of recovery (with chloride ion in ion exchange water outlet) be 45.3, respectively significantly lower than embodiment 2 sodium sulphate recovery
The rate of recovery (89.1%) of rate (96.1%) and sodium chloride.Show to crystallize concentrated water as the 3rd crystallization backflow using at least partly the 3rd
Mother liquor reflux to the second Crystallization Separation is handled, it is possible to achieve the concentration again of one-component salt and fractional crystallization, can realize ratio
The separation and crystallization of one-component salt more thoroughly, effectively improve the rate of recovery of one-component salt.
Comparative example 1
This comparative example uses flow shown in Fig. 2, the advance for the salt extraction process of the comparative illustration present invention.
The reverse osmosis units used in this comparative example are to include 3 putaminas in parallel, every putamina built with 6 series connection
One section of counter-infiltration system of one-level of DOW BW30FR-400 reverse-osmosis membrane elements；Cation exchange unit is that a volume is
0.80m3, filling DOWEX MAC-3 Weak-acid cation exchange resins cation exchanger；Evaporation element is a heat exchange area
For 60m2Mechanical compression type evaporator；Crystallization Separation unit is 3.0m including a heat exchange area2Forced-circulation evaporation crystallization
Device and centrifugal separating device.The flow of inlet water of raw water is 11.0m3/ h, concrete technology flow process are as follows：
(1) it is 11.0m by flow3/ h, temperature are synthesis brackish water shown in 25 DEG C of table 1 as raw water, thereto
After the antisludging agent (active ingredient is organic phosphonate, Ondeo Nalco Co., OSMOTREAT OSM1035) for adding 5.0mg/L, supply
Into reverse osmosis units, reverse-osmosis treated is carried out at 25 DEG C.Wherein, reverse osmosis units use part concentrated water circulate operation mould
Formula, concentrated water internal circulating load are 19.0m3/ h, the intake pressure of reverse osmosis units is 0.9MPa.After reverse osmosis units are handled, obtain
It is 7.72m to flow3/ h, temperature are 25 DEG C of reverse osmosis produced water and flow is 3.28m3/ h, temperature are 25 DEG C reverse osmosis concentrated
Water.Now, the degree of supersaturation of calcium sulfate is the degree of supersaturation of reverse osmosis concentrated water in 353.0%, with embodiment 1 in reverse osmosis concentrated water
Quite.
(2) it is 3.28m by flow3/ h, the reverse osmosis concentrated water that temperature is 25 DEG C be sent into cation exchange unit carry out sun from
Sub- exchange processing, wherein, it is 15 minutes that cation exchange, which was intake in the residence time of cation exchange unit, and obtaining flow is
3.28m3The cation exchange water outlet that/h, temperature are 25 DEG C, calcium ion concentration is 0.1mg/l.
(3) it is 3.28m by flow3/ h, the cation exchange water outlet that temperature is 25 DEG C supply evaporation element, at 105 DEG C
It is evaporated concentration.The concentration rate for controlling evaporation element is 25 times, and it is 3.15m to obtain flow3/ h condensation production water and
Flow is 0.13m3/ h, temperature are 105 DEG C close to saturation evaporation element concentrated water (saturation degree 75.8% of sodium sulphate).
(4) it is 0.13m by flow3/ h, the evaporation element concentrated water that temperature is 105 DEG C are supplied to Crystallization Separation unit and steamed
Crystallization treatment is sent out, obtains the salt-mixture comprising sodium chloride and sodium sulphate.
Table 5 gives the flow and component of each material flow in comparative example 1.
Table 5
As can be seen from Table 5, temperature is to contain higher calcium, sodium, chlorion and sulfate radical simultaneously in 25 DEG C of raw water,
Calcium sulfate degree of supersaturation is 80.7%, in undersaturated condition, after reverse-osmosis treated, the sulfuric acid of obtained reverse osmosis concentrated water
Calcium degree of supersaturation is 353.0%, suitable with the fouling risk of embodiment 1.Due to no the first crystallization being introduced into embodiment 1-2
Unit (normal temperature crystallization), calcium sulfate is all gathered in reverse osmosis concentrated water, and the Water Sproading rate for limiting reverse osmosis units (is only
70.2%, far below in embodiment 1 90.9%).Suffer from this, in this comparative example, the load (3.15m of evaporation element3/h)
Load (the 0.94m of evaporation element about in embodiment 13/ h) 3.4 times, evaporation energy consumption accordingly increases.
Part of sulfuric acid calcium is removed because no normal temperature crystallizes, the load that this comparative example cationic exchanges is (in terms of Ca)
4.48kg/h, it is 10 times of the load (0.42kg/h is calculated as with Ca) of cation exchange in embodiment 1, the investment of ion exchange
Dramatically increased with regenerative agent expense.
Combination crystalline element (the second crystalline element and the controlled respectively due to no introducing operation temperature and condensing crystallizing
Three crystalline elements), evaporation element concentrated water after single evaporative crystallization cell processing by can only obtain comprising sodium sulphate and sodium chloride
Salt-mixture, the weight/mass percentage composition of sodium sulphate and sodium chloride is about under the condition of water quality that this comparative example uses, in the salt-mixture
Respectively 85.0% and 15.0%.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (54)
1. a kind of salt extraction process, it is characterised in that this method includes：
(1) reverse-osmosis treated will be carried out containing the brackish water of dianion salt and univalent anion salt, brackish water is carried out
Initial concentration, obtain the reverse osmosis concentrated water of rich salt and the reverse osmosis produced water of poor salt；
(2) reverse osmosis concentrated water for obtaining step (1) carries out the first Crystallization Separation processing, obtains the first crystal salt and the first crystallization
Concentrated water, the described first crystallization concentrated water is divided into two strands, be back to respectively as the first backflow crystallization water outlet described in step (1) progress
Reverse-osmosis treated and carry out follow-up cation exchange treatment as cation exchange water inlet；
(3) the cation exchange water inlet obtained step (2) carries out cation exchange treatment, obtains the sun of rich monovalent cation salt
Ion exchange water outlet；
(4) the cation exchange water outlet that step (3) obtains is intake as crystallization and carries out the second Crystallization Separation processing, obtain second
Crystal salt and the second crystallization concentrated water；
(5) the second crystallization concentrated water for obtaining step (4) carries out the processing of the 3rd Crystallization Separation, obtains the 3rd crystal salt and the 3rd knot
Brilliant concentrated water.
2. according to the method for claim 1, wherein, this method also includes：, will before the second Crystallization Separation processing is carried out
The cation exchange water outlet that step (3) obtains is evaporated processing, obtains distilled water and the evaporation concentrated water close to saturation, then will
The evaporation concentrated water carries out the second Crystallization Separation processing as crystallization water inlet.
3. according to the method for claim 2, wherein, the condition of the evaporation process includes：Temperature is 50-135 DEG C.
4. according to the method for claim 3, wherein, the temperature of the evaporation process is 90-120 DEG C.
5. according to the method for claim 2, wherein, sodium sulphate or sodium chloride satisfies in the evaporation concentrated water close to saturation
It is 50-99% with degree.
6. according to the method for claim 5, wherein, sodium sulphate or sodium chloride satisfies in the evaporation concentrated water close to saturation
It is 70-95% with degree.
7. according to the method for claim 6, wherein, sodium sulphate or sodium chloride satisfies in the evaporation concentrated water close to saturation
It is 90-95% with degree.
8. according to the method described in any one in claim 1-7, wherein, it is described to contain dianion salt in step (1)
Contain the first backflow crystallization water outlet described in raw water and step (2) with the brackish water of univalent anion salt；And salt in raw water
Gross mass percentage composition Y%<When 2.5%, meet relational expression R1<Y/ (2.5-Y), R1 are cation exchange water inlet and counter-infiltration
Produce the volume flow ratio of water.
9. according to the method described in any one in claim 1-7, wherein, in step (1), the condition bag of reverse-osmosis treated
Include：Temperature is 10-40 DEG C, pressure 1-6MPa；The volume flow ratio of the reverse osmosis concentrated water and the reverse osmosis produced water is
0.2-2：1.
10. according to the method for claim 9, wherein, in step (1), the temperature of reverse-osmosis treated is 15-30 DEG C.
11. according to the method for claim 9, wherein, in step (1), the pressure of reverse-osmosis treated is 1.6-4MPa.
12. the method according to claim 11, wherein, in step (1), the reverse osmosis concentrated water and the reverse osmosis produced water
Volume flow ratio be 0.3-1：1.
13. according to the method described in any one in claim 1-7, wherein, this method also includes：In step (1), it will contain
Before salt solution carries out reverse-osmosis treated, at least one antisludging agent is added into the brackish water；And in described in step (2)
In the processing of one Crystallization Separation, control condition inactivates the antisludging agent, to carry out Crystallization Separation.
14. according to the method for claim 13, wherein, relative to brackish water described in 1L, the dosage of the antisludging agent is 2-
15mg。
15. according to the method for claim 14, wherein, relative to brackish water described in 1L, the dosage of the antisludging agent is 3-
7mg。
16. according to the method for claim 13, wherein, the antisludging agent is organic phosphine type antisludging agent, organic phospho acid salt form
At least one of antisludging agent, polycarboxylic acid-based inhibitor and composite scale agent.
17. according to the method for claim 13, wherein, mode makes the antisludging agent at least one of in the following ways
Inactivation：
Mode one：At least one solid matter that can act as normal temperature crystalline seed is added into the reverse osmosis concentrated water；
Mode two：At least one flocculant is added into the reverse osmosis concentrated water；
Mode three：Adjust the pH value of the reverse osmosis concentrated water.
18. according to the method for claim 17, wherein, in mode one, the addition of the solid matter causes counter-infiltration
The mass concentration of crystal seed is 2%-12% in concentrated water.
19. according to the method for claim 18, wherein, in mode one, the addition of the solid matter causes counter-infiltration
The mass concentration of crystal seed is 4%-8% in concentrated water.
20. the method according to claim 11, wherein, in mode one, the solid matter and the water in reverse osmosis concentrated water
The species of indissoluble salt is identical.
21. according to the method for claim 20, wherein, in mode one, the solid matter is selected from calcium sulfate and/or sulfuric acid
The hydrate of calcium.
22. the method according to claim 11, wherein, in mode two, relative to the reverse osmosis concentrated water described in 1L, the wadding
The dosage of solidifying agent is 2-20mg.
23. the method according to claim 11, wherein, in mode two, relative to the reverse osmosis concentrated water described in 1L, the wadding
The dosage of solidifying agent is 5-15mg.
24. according to the method for claim 17, wherein, in mode two, the flocculant is iron chloride and/or ferric sulfate.
25. according to the method for claim 17, wherein, in mode three, the pH value of the reverse osmosis concentrated water is adjusted to 3-
6。
26. according to the method for claim 25, wherein, in mode three, the pH value of the reverse osmosis concentrated water is adjusted to
3.5-4.5。
27. according to the method described in any one in claim 1-7, wherein, in step (2), at first Crystallization Separation
The condition of reason includes：Temperature is 10-40 DEG C；The volume flow ratio of first backflow crystallization water outlet and cation exchange water inlet is 1-
20：1.
28. according to the method for claim 27, wherein, in step (2), the temperature of the first Crystallization Separation processing is
15-30℃。
29. according to the method for claim 27, wherein, in step (2), the first backflow crystallization water outlet and cation exchange are entered
The volume flow ratio of water is 3-9：1.
30. according to the method described in any one in claim 1-7, wherein, in step (3), the cation exchange treatment
Condition include：Temperature is 10-40 DEG C, and the residence time is 2-30 minutes；The concentration of calcium ion is in cation exchange water outlet
0.01-5mg/L。
31. according to the method for claim 30, wherein, in step (3), the temperature of the cation exchange treatment is 15-
30℃。
32. according to the method for claim 30, wherein, in step (3), the residence time of the cation exchange treatment is
5-15 minutes.
33. according to the method for claim 30, wherein, in step (3), the concentration of calcium ion is in cation exchange water outlet
0.05-1mg/L。
34. according to the method described in any one in claim 1-7, wherein, in step (4), at second Crystallization Separation
The mode of reason is that the first evaporative crystallization is handled or crystallisation by cooling is handled.
35. according to the method for claim 34, wherein, the condition of the first evaporative crystallization processing includes：Temperature is 50-
120℃。
36. according to the method for claim 34, wherein, the condition of the crystallisation by cooling processing includes：Temperature less than 5 DEG C and
Higher than the freezing point temperature of the crystallization water inlet.
37. according to the method for claim 36, wherein, the temperature of the crystallisation by cooling processing is -2~2 DEG C.
38. according to the method for claim 34, wherein, in step (5), the mode of the 3rd Crystallization Separation processing is the
The processing of two evaporative crystallizations.
39. according to the method for claim 38, wherein, the condition of the second evaporative crystallization processing includes：Temperature is 50-
120℃。
40. according to the method for claim 39, wherein, the mode of the second Crystallization Separation processing is the first evaporative crystallization
During processing, the temperature of the second evaporative crystallization processing is lower than the temperature that first evaporative crystallization is handled at least 20 DEG C；It is described
When the mode of second Crystallization Separation processing is handled for crystallisation by cooling, the temperature of the second evaporative crystallization processing is 50-80 DEG C.
41. according to the method described in any one in claim 1-7, wherein, this method also includes：Step (5) is obtained
3rd crystallization concentrated water is divided into two strands, and the second described crystallization is carried out respectively as the 3rd crystallization backflow mother liquor reflux to step (4)
Separating treatment and conduct system concentrated water are post-processed.
42. according to the method for claim 41, wherein, the described 3rd crystallizes backflow mother liquor and the volume of the system concentrated water
Flow-rate ratio is 1-100：1.
43. according to the method for claim 42, wherein, the described 3rd crystallizes backflow mother liquor and the volume of the system concentrated water
Flow-rate ratio is 3-50：1.
44. according to the method described in any one in claim 1-7, wherein, the cation exchange water outlet contains divalence the moon
Ion salt and univalent anion salt, and the weight/mass percentage composition of dianion salt is 0.2%- in the cation exchange water outlet
5%.
45. according to the method for claim 44, wherein, the dianion salt is sodium sulphate, the univalent anion
Salt is sodium chloride.
A kind of 46. salt making system, it is characterised in that the salt making system include reverse osmosis units, the first Crystallization Separation unit, sun from
Sub- crosspoint, the second Crystallization Separation unit and the 3rd Crystallization Separation unit,
The reverse osmosis units are used to that reverse-osmosis treated will to be carried out containing the brackish water of dianion salt and univalent anion salt,
Obtain the reverse osmosis concentrated water of rich salt and the reverse osmosis produced water of poor salt；
The first Crystallization Separation unit is used to the reverse osmosis concentrated water from the reverse osmosis units carrying out the first Crystallization Separation
Processing, the first crystal salt and the first crystallization concentrated water are obtained, and the first Crystallization Separation unit is connected with the reverse osmosis units,
For at least partly reverse-osmosis treated will to be carried out by the first crystallization concentrate recirculation to the reverse osmosis units；
The cation exchange unit is used to be back to the reverse osmosis units from the first Crystallization Separation unit
First crystallization concentrated water as cation exchange water inlet progress cation exchange treatment, obtain the cation of rich monovalent cation salt
Exchange water outlet；
The second Crystallization Separation unit is used for using the cation exchange water inlet from the cation exchange unit as crystallization
Water inlet carries out the second Crystallization Separation processing, obtains the second crystal salt and the second crystallization concentrated water；
The 3rd Crystallization Separation unit is used to the second crystallization concentrated water from the second Crystallization Separation unit carrying out the 3rd
Crystallization Separation processing, obtain the 3rd crystal salt and the 3rd crystallization concentrated water.
47. salt making system according to claim 46, wherein, the salt making system also includes evaporation element, and the evaporation is single
Member is used to the cation exchange water outlet from the cation exchange unit being evaporated processing, obtains distilled water and approaches full
The evaporation concentrated water of sum；And the second Crystallization Separation unit is used for using the evaporation concentrated water from the evaporation element as knot
Crystalline substance water inlet carries out the second Crystallization Separation processing.
48. the salt making system according to claim 46 or 47, wherein, the reverse osmosis units include an at least counter-infiltration
Membrane component.
49. salt making system according to claim 48, wherein, what the reverse osmosis units were used in series including at least two
Reverse-osmosis membrane element.
50. the salt making system according to claim 46 or 47, wherein, the first Crystallization Separation unit includes the first crystallization
Unit and the first solid-liquid separation unit,
First crystalline element is used to the reverse osmosis concentrated water from the reverse osmosis units carrying out the first crystallization treatment, obtains
The the first crystallization water outlet used as the first crystallization concentrated water and the first crystallization solidliquid mixture,
First solid-liquid separation unit is used to the first crystallization solidliquid mixture from first crystalline element carrying out the
The processing of one separation of solid and liquid, obtain the first crystal salt and the first crystalline mother solution used as the first crystallization concentrated water.
51. the salt making system according to claim 46 or 47, wherein, the second Crystallization Separation unit includes the second crystallization
Unit and the second solid-liquid separation unit,
Second crystalline element, which is used to intake the crystallization from the cation exchange unit or the evaporation element, to be carried out
Second crystallization treatment, the second crystallization water outlet and the second crystallization solidliquid mixture used as the second crystallization concentrated water is obtained,
Second solid-liquid separation unit is used to the second crystallization solidliquid mixture from second crystalline element carrying out the
The processing of two separation of solid and liquid, obtain the second crystal salt and the second crystalline mother solution used as the second crystallization concentrated water.
52. salt making system according to claim 51, wherein, second crystalline element includes crystallizing evaporator or cooling
Crystallizer.
53. the salt making system according to claim 46 or 47, wherein, the 3rd Crystallization Separation unit includes the 3rd crystallization
Unit and the 3rd solid-liquid separation unit,
3rd crystalline element is used to the second crystallization concentrated water from second crystalline element carrying out the 3rd crystallization treatment,
The 3rd crystallization water outlet and the 3rd crystallization solidliquid mixture used as the 3rd crystallization concentrated water is obtained,
3rd solid-liquid separation unit is used to the 3rd crystallization solidliquid mixture from the 3rd crystalline element carrying out the
The processing of three separation of solid and liquid, obtain the 3rd crystal salt and the 3rd crystalline mother solution used as the 3rd crystallization concentrated water.
54. salt making system according to claim 53, wherein, the 3rd crystalline element includes crystallizing evaporator.
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