CN106115740B - 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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- CN106115740B CN106115740B CN201610420364.4A CN201610420364A CN106115740B CN 106115740 B CN106115740 B CN 106115740B CN 201610420364 A CN201610420364 A CN 201610420364A CN 106115740 B CN106115740 B CN 106115740B
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- 150000003839 salts Chemical class 0.000 title claims abstract description 210
- 238000000605 extraction Methods 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 574
- 238000002425 crystallisation Methods 0.000 claims abstract description 364
- 230000008025 crystallization Effects 0.000 claims abstract description 364
- 238000001728 nano-filtration Methods 0.000 claims abstract description 321
- 238000000926 separation method Methods 0.000 claims abstract description 256
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 195
- 238000005341 cation exchange Methods 0.000 claims abstract description 122
- 238000000034 method Methods 0.000 claims abstract description 100
- -1 anion salt Chemical class 0.000 claims abstract description 75
- 239000013078 crystal Substances 0.000 claims abstract description 37
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 86
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 76
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 69
- 239000012528 membrane Substances 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 57
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 45
- 235000011152 sodium sulphate Nutrition 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 39
- 238000001764 infiltration Methods 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 33
- 239000011780 sodium chloride Substances 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 24
- 239000011575 calcium Substances 0.000 claims description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 20
- 229910052791 calcium Inorganic materials 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 238000005342 ion exchange Methods 0.000 claims description 19
- 230000008595 infiltration Effects 0.000 claims description 15
- 239000010413 mother solution Substances 0.000 claims description 14
- 239000011833 salt mixture Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 8
- 230000002977 hyperthermial effect Effects 0.000 claims description 6
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 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
- 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
- 238000011084 recovery Methods 0.000 description 30
- 230000000694 effects Effects 0.000 description 22
- GJYLKIZKRHDRER-UHFFFAOYSA-N calcium;sulfuric acid Chemical compound [Ca].OS(O)(=O)=O GJYLKIZKRHDRER-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 241000370738 Chlorion Species 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 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 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 239000012267 brine Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 239000003729 cation exchange resin Substances 0.000 description 5
- 229940023913 cation exchange resins Drugs 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000036186 satiety Effects 0.000 description 1
- 235000019627 satiety Nutrition 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 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
- C01D3/14—Purification
-
- 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
- C01D5/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention relates to water treatment field, a kind of salt extraction process and salt making system are disclosed.The method includes：Brackish water is carried out into reverse-osmosis treated, reverse osmosis concentrated water and reverse osmosis produced water is obtained；Reverse osmosis concentrated water is carried out into the first Crystallization Separation treatment, the first crystal salt and the first crystallization concentrated water is obtained, the first crystallization concentrated water is divided into backflow crystallization water outlet and cation exchange water inlet；Cation exchange is carried out into cation exchange treatment, cation exchange water outlet is obtained；Cation exchange water outlet is carried out into nanofiltration separation treatment, nanofiltration is obtained and is produced water and nanofiltration concentrated water；The second Crystallization Separation treatment is carried out after nanofiltration concentrated water is cooled down, the second crystal salt and the second crystallization concentrated water is obtained；First nanofiltration product water is carried out into the treatment of the 3rd Crystallization Separation, rich univalent anion salt is obtained.The one-component salt of high-purity can be obtained using the method for the present invention and system, 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, water resource is not enough and environmental carrying capacity is limited etc., and contradiction is increasingly highlighted.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, improve water service efficiency, current brine waste generally use based on counter-infiltration embrane method treatment after reuse,
The service efficiency of water is improve to a certain extent.The occasion of zero liquid discharge is being required, reverse osmosis concentrated water is by further using steaming
Hair crystallization processes, obtain distilled water and solid carnallite.
Existing zero liquid discharge process generally existing film concentration and recovery rate is limited, solid carnallite is difficult to dispose etc., and protrusion is 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, obtained
One-component salt to higher degree is sold as byproduct, reduces carnallite cost of disposal and realizes 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
System, salt extraction process of the invention can be obtained the one-component salt of high-purity, 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, the method includes：
(1) brackish water containing dianion salt and univalent anion salt is carried out into the first reverse-osmosis treated, will be contained
Salt solution carries out initial concentration, obtains the first reverse osmosis concentrated water of rich salt and the first reverse osmosis produced water of poor salt；
(2) the first reverse osmosis concentrated water that step (1) is obtained is carried out into the first Crystallization Separation treatment, obtain the first crystal salt and
First crystallization concentrated water, two strands are divided into by the described first crystallization concentrated water, and step (1) is back to respectively as the first backflow crystallization water outlet
Carry out described the first reverse-osmosis treated and carry out follow-up cation exchange treatment as cation exchange；
(3) cation exchange for obtaining step (2) carries out cation exchange treatment, obtains rich monovalent cation salt
Cation exchange water outlet；
(4) the cation exchange water outlet for obtaining step (3) carries out the first nanofiltration separation treatment as the first nanofiltration,
To separate dianion salt and univalent anion salt, water and dianion are produced in the first nanofiltration for obtaining rich univalent anion salt
The first nanofiltration concentrated water that salt is concentrated；
(5) the second Crystallization Separation treatment is carried out after the first nanofiltration concentrated water cooling for obtaining step (4), the second crystallization is obtained
Salt and the second crystallization concentrated water；
(6) the first nanofiltration for obtaining step (4) is produced water and carries out the treatment of the 3rd Crystallization Separation, obtains rich univalent anion
Salt.
Second aspect, the invention provides a kind of salt making system, the salt making system includes the first reverse osmosis units, the first knot
Brilliant separative element, cation exchange unit, the first nanofiltration separation unit, the second Crystallization Separation unit and the 3rd Crystallization Separation list
Unit,
First reverse osmosis units are used to for the brackish water containing dianion salt and univalent anion salt to carry out the
One reverse-osmosis treated, obtains the first reverse osmosis concentrated water of rich salt and the first reverse osmosis produced water of poor salt；
The first Crystallization Separation unit is used to carry out the first reverse osmosis concentrated water from first reverse osmosis units
The treatment of first Crystallization Separation, obtains the first crystal salt and the first crystallization concentrated water, and the first Crystallization Separation unit and described the
One reverse osmosis units are connected, anti-at least part of first crystallization concentrate recirculation to first reverse osmosis units to be carried out into first
Infiltration is processed；
The cation exchange unit be used for by from the first Crystallization Separation unit not to be back to described first anti-
First crystallization concentrated water of permeation unit carries out cation exchange treatment as cation exchange, obtains rich monovalent cation salt
Cation exchange water outlet；
The first nanofiltration separation unit is used to that the cation exchange water outlet from the cation exchange unit will to be included
The first nanofiltration separation treatment is carried out as the first nanofiltration, water and divalence the moon are produced in the first nanofiltration for obtaining rich univalent anion salt
The first nanofiltration concentrated water that ion salt is concentrated；
The second Crystallization Separation unit is used for the first nanofiltration concentrated water from the first nanofiltration separation unit cold
But the second Crystallization Separation treatment is carried out under the conditions of, the second crystal salt and the second crystallization concentrated water is obtained；
The 3rd Crystallization Separation unit is used to include that water is produced in the first nanofiltration from the first nanofiltration separation unit
The 3rd Crystallization Separation is carried out as water inlet to process, obtain rich univalent anion salt.
Using the method for the present invention 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 the method can be greatly reduced energy consumption and throwing
Money cost.
One kind of the invention preferred embodiment, the second crystallization concentrated water that the treatment of the second Crystallization Separation is obtained is entered
The nanofiltration separation of row second treatment, it is possible to achieve the concentration again of one-component salt (sodium chloride), can realize comparing thoroughly single
The separation and crystallization of one component salt, effectively increase the rate of recovery of one-component salt, with preferable economic worth and use valency
Value.
One kind of the invention preferred embodiment, in the treatment of the second Crystallization Separation, is tied using by the second backflow
The circulate operation pattern that brilliant effluent recycling to the first nanofiltration separation is processed, it is possible to achieve the concentration again and circulation of one-component salt
Crystallization, can realize comparing the separation and crystallization of thoroughly one-component salt, effectively increase the rate of recovery of one-component salt, make
Obtain whole operation process and realize continuous operation, stable state produces salt, with preferable economic worth 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 another embodiment of the invention.
Fig. 3 is the schematic flow sheet of the salt extraction process of comparative example of the present invention 1.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope 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
One or more can be obtained with combination with one another between the endpoint value of individual scope and single point value, and individually between point value
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, the method includes：
(1) brackish water containing dianion salt and univalent anion salt is carried out into the first reverse-osmosis treated, will be contained
Salt solution carries out initial concentration, obtains the first reverse osmosis concentrated water of rich salt and the first reverse osmosis produced water of poor salt；
(2) the first reverse osmosis concentrated water that step (1) is obtained is carried out into the first Crystallization Separation treatment, obtain the first crystal salt and
First crystallization concentrated water, two strands are divided into by the described first crystallization concentrated water, and step (1) is back to respectively as the first backflow crystallization water outlet
Carry out described the first reverse-osmosis treated and carry out follow-up cation exchange treatment as cation exchange；
(3) cation exchange for obtaining step (2) carries out cation exchange treatment, obtains rich monovalent cation salt
Cation exchange water outlet；
(4) the cation exchange water outlet for obtaining step (3) carries out the first nanofiltration separation treatment as the first nanofiltration,
To separate dianion salt and univalent anion salt, water and dianion are produced in the first nanofiltration for obtaining rich univalent anion salt
The first nanofiltration concentrated water that salt is concentrated；
(5) the second Crystallization Separation treatment is carried out after the first nanofiltration concentrated water cooling for obtaining step (4), the second crystallization is obtained
Salt and the second crystallization concentrated water；
(6) the first nanofiltration for obtaining step (4) is produced water and carries out the treatment of the 3rd Crystallization Separation, obtains rich univalent anion
Salt.
In salt extraction process of the invention, in order to realize separation and the knot of more thorough one-component salt (mainly sodium chloride)
Crystalline substance, the more effective rate of recovery for improving one-component salt, under preferable case, the method also includes：Carrying out at the 3rd Crystallization Separation
Before reason, the second crystallization concentrated water that step (5) is obtained is carried out into the second nanofiltration separation treatment, obtain the of rich univalent anion salt
The second nanofiltration concentrated water that water and dianion salt are concentrated is produced in two nanofiltrations, and water is produced in the first nanofiltration for then obtaining step (4)
Water mixing is produced in the second nanofiltration obtained with the treatment of the second nanofiltration separation, and the mixing nanofiltration that will be obtained is produced water and carries out the 3rd crystallization point
From treatment, rich univalent anion salt is obtained.
It is more effective to improve in order to realize the separation and crystallization of more thorough one-component salt in salt extraction process of the invention
The rate of recovery of one-component salt, and cause that whole operation process realizes continuous operation, under preferable case, the method also includes：Will
The second crystallization concentrated water that step (5) is obtained is divided into two strands, is back to described in step (4) respectively as the second backflow crystallization water outlet
First nanofiltration separation is processed and post-processed as system concentrated water；
Wherein, in step (4), the first nanofiltration water inlet includes the cation exchange water outlet and described second that step (3) is obtained
Backflow crystallization water outlet；And in cation exchange water outlet dianion salt weight/mass percentage composition X%<When 5%, relational expression is met
R1<X/ (5-X), preferably meets R1<3X/ (50-3X), further preferably meets 4>R2>{ (R1+1) * X/5-R1 }, R1 is system
Concentrated water produces the volume flow ratio of water with the first nanofiltration, and R2 is the volume flow ratio that the first nanofiltration concentrated water produces water with the first nanofiltration.
In salt extraction process of the invention, the present inventor has found in surprise under study for action, system concentrated water and the first nanofiltration
Whether the volume flow ratio R1 of water is produced for that can realize that the purpose for continuously producing recovery dianion salt is most important, works as X<5
When, the selection of R1 is related to the weight/mass percentage composition X% of dianion salt in cation exchange water outlet, in order to realize continuous system
Fetch the purpose for receiving dianion salt, it is necessary to meet relational expression R1<X/(5-X)；And, inventor is also further under study for action
It was found that, meeting R1<In the case of X/ (5-X), R1 is further met<3X/ (50-3X), the rate of recovery of one-component salt is obvious
Higher (>70%).For example, the rate of recovery in order to further improve one-component salt, when in cation exchange water outlet divalence it is cloudy from
During the weight/mass percentage composition X%=3% of alite, the volume flow ratio R1 that system concentrated water produces water with the first nanofiltration meets R1<3*3/
(50-3*3), i.e. R1<0.22；And as the weight/mass percentage composition X%=1% of dianion salt in cation exchange water outlet,
The volume flow ratio R1 that system concentrated water produces water with the first nanofiltration meets R1<3*1/ (50-3*1), i.e. R1<0.064.
The present inventor has further been found that the first nanofiltration concentrated water produces the volume flow of water with the first nanofiltration under study for action
Amount is another vital parameter than R2, the weight/mass percentage composition X% of dianion salt in cation exchange water outlet<
When 5%, the selection of R2 is related with the volume flow ratio R1 that water is produced in the first nanofiltration with X% and system concentrated water, in order to preferably real
Now continuously produce and reclaim the purpose of dianion salt and the method is operated under suitable pressure condition, under preferable case,
Meet relational expression R2>{(R1+1)*X/5–R1}.For example, when the quality percentage of dianion salt in cation exchange water outlet contains
When amount X%=3%, system concentrated water produce the volume flow ratio R1=0.1 of water with the first nanofiltration, R2>(0.1+1) * 3/5-0.1, i.e.,
R2>0.56.Meanwhile, in order to avoid causing Crystallization Separation unit size, cost of investment and system because nanofiltration concentrated water flow is excessive
Energy consumption is excessive, and R2 typically requires to be less than 4, and preferred scope is R2<3, further preferred R2<1.5.
In salt extraction process of the invention, under preferable case, in step (1), contain dianion salt and univalent anion
The brackish water of salt contains raw water and the first backflow crystallization water outlet described in step (2)；And in raw water salt gross mass percentage
Content Y%<When 2.5%, relational expression R3 is met<Y/ (2.5-Y), R3 are the body of cation exchange water inlet and the first reverse osmosis produced water
Product flow-rate ratio.
In salt extraction process of the invention, under preferable case, in step (1), the condition of the first reverse-osmosis treated includes：Temperature
It is 10-40 DEG C, more preferably 15-30 DEG C；Pressure is 1-6MPa, more preferably 1.8-4MPa；First reverse osmosis
Saturating concentrated water is 0.2-2 with the volume flow ratio of first reverse osmosis produced water：1, more preferably 0.3-1：1.
In salt extraction process of the invention, under preferable case, the method also includes：In step (1), brackish water is being carried out
Before one reverse-osmosis treated, at least one antisludging agent of addition in the brackish water；And in the first crystallization described in step (2)
In separating treatment, control condition inactivates the antisludging agent, to carry out Crystallization Separation.
Preferably, relative to brackish water described in 1L, the consumption 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 in composite scale agent.
In salt extraction process of the invention, under preferable case, in the following ways at least one mode make the scale inhibition
Agent is inactivated：
Mode one：To adding at least one solids that can act as normal temperature crystalline seed in first reverse osmosis concentrated water
Matter；
Mode two：To at least one flocculant of addition in first reverse osmosis concentrated water；
Mode three：Adjust the pH value of first reverse osmosis concentrated water.
Preferably, in mode one, the addition of solid matter causes that the mass concentration of crystal seed in the first 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 the first reverse osmosis concentrated water, enters one
Step is preferably selected from the hydrate of calcium sulfate and/or calcium sulfate.
Preferably, in mode two, relative to the first reverse osmosis concentrated water described in 1L, the consumption of flocculant is 2-20mg, is entered
One step is preferably 5-15mg, and the flocculant is preferably iron chloride and/or ferric sulfate；
Preferably, in mode three, the pH value of first reverse osmosis concentrated water is adjusted to 3-6, is further preferably adjusted to
3.5-4.5。
In salt extraction process of the invention, under preferable case, in step (2), the condition of the first Crystallization Separation treatment includes：Temperature
It is 10-40 DEG C to spend, more preferably 15-30 DEG C；First backflow crystallization water outlet and the volume flow ratio of cation exchange water inlet
It is 1-20：1, more preferably 3-9：1.
In salt extraction process of the invention, being processed by the first reverse-osmosis treated and the first Crystallization Separation can realize to saliferous
The efficient concentration of water, and can substantially reduce the load of follow-up cation exchange.Wherein, the first Crystallization Separation is processed at normal temperatures
Operation, the solution supersaturation caused mainly by reverse osmosis concentration and spontaneous generation crystallization process, without expending big energy or change
Learn medicament.Being processed by the first Crystallization Separation can get rid of most low solubility divalent salts, the first crystallization for being obtained
Salt is under normal circumstances the calcium sulfate that purity is higher, and the calcium sulfate degree of supersaturation of the first crystallization concentrated water for obtaining is significantly reduced.
In salt extraction process of the invention, under preferable case, in step (3), the condition of cation exchange treatment includes：Temperature
It is 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 salt extraction process of the invention, in order to further improve the separating effect of dianion salt and univalent anion salt
And the rate of recovery, under preferable case, in step (4), the condition of the first nanofiltration separation treatment includes：Temperature is 10-40 DEG C, further
Preferably 15-30 DEG C；Pressure is 1-6MPa, more preferably 2-4MPa；The first nanofiltration concentrated water and first nanofiltration
The volume flow ratio for producing water is 0.05-2：1, more preferably 0.07-0.5：1.
In salt extraction process of the invention, have for the NF membrane component requirements that the treatment of the first nanofiltration separation is used relatively low
Univalent anion salt rejection rate, to improve the separating effect and the rate of recovery of dianion salt and univalent anion salt, preferably feelings
Under condition, in step (4), the nanofiltration membrane component that the treatment of the first nanofiltration separation is used is univalent anion salt in being intake to the first nanofiltration
Nanofiltration membrane component of the rejection less than 20%, for example can be GE DL series nanofiltration membrane component, GE SWSR series NF membranes
The NE8040-40 nanofiltration membrane components of element, DOW NF270 series nanofiltration membrane components or TCK companies of South Korea.
In salt extraction process of the invention, under preferable case, in step (5), the condition of the second Crystallization Separation treatment includes：Temperature
Degree is less than 5 DEG C and higher than the freezing point temperature of the first nanofiltration concentrated water, more preferably -2~2 DEG C.It is further preferred that will
The second crystallization concentrated water is evaporated crystallization treatment to obtain the salt-mixture containing univalent anion salt and dianion salt.
In salt extraction process of the invention, in order to further improve the rate of recovery of dianion salt and avoid dianion
Salt crystallizes precipitation in cooling procedure, and under preferable case, the method for cooling includes：By the first nanofiltration concentrated water by the treatment that exchanges heat
Mode is cooled to crystallization temperature, the crystallization temperature less than 5 DEG C and higher than the freezing point temperature of the first nanofiltration concentrated water, further
Preferably -2~2 DEG C；And it is 1-20m/s to control flow velocity of the first nanofiltration concentrated water in heat exchange treatment, more preferably
2-5m/s；
Preferably, the heat exchange treatment is carried out in spiral tube exchanger, tubular heat exchanger or double pipe heat exchanger, and
The first nanofiltration concentrated water flows as tube side fluid in spiral tube exchanger, tubular heat exchanger or double pipe heat exchanger.
Those skilled in the art can select the specific species of heat exchanger according to actual conditions, and this is well known to those skilled in the art,
Will not be repeated here.Wherein, the second crystal salt is mainly sodium sulphate.
In salt extraction process of the invention, in order to further improve the separating effect of dianion salt and univalent anion salt
And the rate of recovery, under preferable case, the condition of the second nanofiltration separation treatment includes：Temperature is 10-40 DEG C, more preferably 15-
30℃；Pressure is 1-6MPa, more preferably 2-4MPa；The second nanofiltration concentrated water produces the volume of water with second nanofiltration
Flow-rate ratio is 0.1-3：1, more preferably 0.5-2：1.
In salt extraction process of the invention, have for the NF membrane component requirements that the treatment of the second nanofiltration separation is used relatively low
Univalent anion salt rejection rate, to improve the separating effect and the rate of recovery of dianion salt and univalent anion salt, preferably feelings
Under condition, the nanofiltration membrane component that the treatment of the second nanofiltration separation is used is low to the rejection of univalent anion salt in the second crystallization concentrated water
In 20% nanofiltration membrane component, for example, can be GE DL series nanofiltrations membrane component, GE SWSR series nanofiltrations membrane component, DOW
NF270 series nanofiltration membrane components or the NE8040-40 nanofiltration membrane components of TCK companies of South Korea.
In salt extraction process of the invention, under preferable case, the method also includes：It is processed the second nanofiltration separation is carried out
Before, the second crystallization concentrated water is first carried out into hyperthermic treatment；It is further preferred that the implementation method of the hyperthermic treatment for heat exchange at
Reason.
In salt extraction process of the invention, under preferable case, the method for the 3rd Crystallization Separation treatment is evaporative crystallization treatment, institute
The condition for stating evaporative crystallization treatment includes：Temperature is 60-130 DEG C, more preferably 90-120 DEG C.
Preferably, before evaporative crystallization treatment, water and optional second are produced in the first nanofiltration that step (4) is obtained
Nanofiltration is produced water and carries out the second reverse-osmosis treated, obtains the second reverse osmosis concentrated water and the second reverse osmosis produced water, and by the second counter-infiltration
Concentrated water and the second reverse osmosis produced water are evaporated crystallization treatment and recycling treatment respectively.
In salt extraction process of the invention, under preferable case, the method also includes：Second nanofiltration concentrated water is carried out into the 4th crystallization
Separating treatment to obtain the salt-mixture containing univalent anion salt and dianion salt, the side of the 4th Crystallization Separation treatment
Method is evaporative crystallization treatment, and its treatment conditions includes：Temperature is 60-130 DEG C, more preferably 90-120 DEG C.
In salt extraction process of the invention, under preferable case, the cation exchange water outlet contains dianion salt and one
The weight/mass percentage composition of dianion salt is 0.2%-5% in valency anion salt, and 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 includes the first counter-infiltration
Unit, the first Crystallization Separation unit, cation exchange unit, the first nanofiltration separation unit, the second Crystallization Separation unit and the 3rd
Crystallization Separation unit,
First reverse osmosis units are used to for the brackish water containing dianion salt and univalent anion salt to carry out the
One reverse-osmosis treated, obtains the first reverse osmosis concentrated water of rich salt and the first reverse osmosis produced water of poor salt；
The first Crystallization Separation unit is used for the first reverse osmosis concentrated water from first reverse osmosis units (normal
Under temperature) the first Crystallization Separation treatment is carried out, obtain the first crystal salt and the first crystallization concentrated water, and the first Crystallization Separation unit
It is connected with first reverse osmosis units, at least part of first crystallization concentrate recirculation to first reverse osmosis units to be entered
The reverse-osmosis treated of row first；
The cation exchange unit be used for by from the first Crystallization Separation unit not to be back to described first anti-
First crystallization concentrated water of permeation unit carries out cation exchange treatment as cation exchange, obtains rich monovalent cation salt
Cation exchange water outlet；
The first nanofiltration separation unit is used to that the cation exchange water outlet from the cation exchange unit will to be included
The first nanofiltration separation treatment is carried out as the first nanofiltration, water and divalence the moon are produced in the first nanofiltration for obtaining rich univalent anion salt
The first nanofiltration concentrated water that ion salt is concentrated；
The second Crystallization Separation unit is used for the first nanofiltration concentrated water from the first nanofiltration separation unit cold
But the second Crystallization Separation treatment is carried out under the conditions of, the second crystal salt and the second crystallization concentrated water is obtained；
The 3rd Crystallization Separation unit is used to include that water is produced in the first nanofiltration from the first nanofiltration separation unit
The 3rd Crystallization Separation is carried out as water inlet to process, obtain rich univalent anion salt.
In salt making system of the invention, under preferable case, the salt making system also includes the second nanofiltration separation unit, described the
Two nanofiltration separation units are used to be carried out at the second nanofiltration separation from the second of the second Crystallization Separation unit the crystallization concentrated water
The second nanofiltration concentrated water that water and dianion salt are concentrated is produced in reason, the second nanofiltration for obtaining rich univalent anion salt；And it is described
3rd Crystallization Separation unit is used to that water will to be produced from the first nanofiltration of the first nanofiltration separation unit and is received from described second
The the second nanofiltration product water for filtering separative element carries out the treatment of the 3rd Crystallization Separation as water inlet, obtains rich univalent anion salt.
In salt making system of the invention, under preferable case, the first reverse osmosis units include at least one reverse-osmosis membrane element,
It is further preferred that the first reverse osmosis units include at least two reverse-osmosis membrane elements being used in series.
In salt making system of the 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 for the first reverse osmosis concentrated water from first reverse osmosis units to carry out first
Crystallization treatment, obtains the first crystallization water outlet and the first crystallization solidliquid mixture used as the first crystallization concentrated water,
First solid-liquid separation unit is used to enter from the first of first crystalline element the crystallization solidliquid mixture
The treatment of the separation of solid and liquid of row first, obtains the first crystal salt and the first crystalline mother solution used as the first crystallization concentrated water.
In salt making system of the invention, there is relatively low monovalence for the NF membrane component requirements of the first nanofiltration separation unit
Anion salt rejection, to improve the separating effect and the rate of recovery of dianion salt and univalent anion salt, under preferable case,
First nanofiltration separation unit includes at least one nanofiltration membrane component, and the nanofiltration membrane component is one in being intake to first nanofiltration
Nanofiltration membrane component of the rejection of valency anion salt less than 20%, for example, can be GE DL series nanofiltrations membrane component, GE SWSR
The NE8040-40 nanofiltration membrane components of serial nanofiltration membrane component, DOW NF270 series nanofiltration membrane components or TCK companies of South Korea；Enter one
Preferably, the first nanofiltration separation unit includes at least two nanofiltration membrane components being used in series to step.
In salt making system of the invention, under preferable case, the salt making system also includes cooling unit, and the cooling unit is used
In the first nanofiltration concentrated water from the first nanofiltration separation unit is carried out cooling treatment to obtain cooling water outlet, the cooling
Unit includes heat exchanger, it is further preferred that the heat exchanger is spiral tube exchanger, tubular heat exchanger or casing type heat exchanging
Device.Those skilled in the art can select the specific species of heat exchanger according to actual conditions, and this is ripe for those skilled in the art
Know, will not be repeated here.
In salt making system of the 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 for the cooling water outlet from the cooling unit to carry out the second crystallization treatment, obtains
The the second crystallization water outlet used as the second crystallization concentrated water and the second crystallization solidliquid mixture,
Second solid-liquid separation unit is used to enter from the second of second crystalline element the crystallization solidliquid mixture
The treatment of the separation of solid and liquid of row second, obtains the second crystal salt and the second crystalline mother solution used as the second crystallization concentrated water.
Preferably, the salt making system also includes that crystallizing evaporator is used to be evaporated the described second crystallization concentrated water at crystallization
Manage to obtain the salt-mixture containing univalent anion salt and dianion salt.
In salt making system of the invention, there is relatively low monovalence for the NF membrane component requirements of the second nanofiltration separation unit
Anion salt rejection, to improve the separating effect and the rate of recovery of dianion salt and univalent anion salt, under preferable case,
Second nanofiltration separation unit includes at least one nanofiltration membrane component, and the nanofiltration membrane component is to one in the described second crystallization concentrated water
Nanofiltration membrane component of the rejection of valency anion salt less than 20%, for example, can be GE DL series nanofiltrations membrane component, GE SWSR
The NE8040-40 nanofiltration membrane components of serial nanofiltration membrane component, DOW NF270 series nanofiltration membrane components or TCK companies of South Korea；Enter one
Preferably, the second nanofiltration separation unit includes at least two nanofiltration membrane components being used in series to step.
In salt making system of the invention, under preferable case, the salt making system also includes intensification unit, and the intensification unit is used
Hyperthermic treatment is carried out in concentrated water will be crystallized from the second of the second Crystallization Separation unit.
Preferably, intensification 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 salt making system of the invention, under preferable case, the salt making system also includes the second reverse osmosis units, described second
Reverse osmosis units are used to that water will to be produced from the first nanofiltration of the first nanofiltration separation unit and alternatively from the second nanofiltration point
The second nanofiltration from unit is produced water and carries out the second reverse-osmosis treated, obtains the second reverse osmosis concentrated water and the second reverse osmosis produced water, and
Second reverse osmosis units are connected with the 3rd Crystallization Separation unit, for second reverse osmosis concentrated water to be supplied to institute
Stating the 3rd Crystallization Separation unit carries out the treatment of the 3rd Crystallization Separation.
In salt extraction process of the invention, under preferable case, the 3rd Crystallization Separation unit includes crystallizing evaporator with by steaming
Hair crystallization treatment obtains rich univalent anion salt.
In salt extraction process of the invention, under preferable case, the salt making system also includes the 4th Crystallization Separation unit, described the
Four Crystallization Separation units be used for by the second nanofiltration concentrated water from the second nanofiltration separation unit be evaporated crystallization treatment with
The salt-mixture containing univalent anion salt and dianion salt is obtained, the 4th Crystallization Separation unit includes evaporative crystallization
Device.
Embodiment
Below will by embodiment, the present invention will be described in detail, but and be not so limited the scope of the present invention.Below
In embodiment, unless otherwise instructed, the method for being used 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).
Using synthesis brackish water analog raw material water, its component is respectively as shown in table 1- tables 2.
Table 1
| Project | ||||
| Unit | mg/L | mg/L | mg/L | mg/L |
| Numerical value | 909.1 | 439.9 | 920.3 | 1705.7 |
Table 2
| Project | ||||
| Unit | mg/L | mg/L | mg/L | mg/L |
| Numerical value | 657.2 | 248.9 | 842.2 | 828.0 |
Embodiment 1
With reference to Fig. 1, the present embodiment is used to illustrate salt extraction process of the invention.
The first reverse osmosis units used in the present embodiment are to include 3 putaminas of parallel connection, every putamina built with 6 strings
One section of counter-infiltration system of one-level of the DOW BW30FR-400 reverse-osmosis membrane elements of connection；First Crystallization Separation unit includes one always
Volume is 12.5m3Reaction depositing reservoir and centrifugal separating device；Cation exchange unit is that a volume is 0.15m3, filling
The cation exchanger of DOWEX MAC-3 Weak-acid cation exchange resins；First nanofiltration separation unit is to include built-in 2 series connection
GE SWSR-400 nanofiltration membrane components monofilm shell one section of nanofiltration system of one-level；Second Crystallization Separation unit includes a band
The volume of heat-insulation layer is 0.3m3Rustless steel container and centrifugal separating device；Second nanofiltration separation unit is built-in 1 series connection
One section of nanofiltration system of monofilm shell one-level of GE DSL NF2540 nanofiltration membrane components.3rd crystalline element includes crystallizing evaporator.It is former
The flow of inlet water for expecting water is 11.0m3/ h, concrete technology flow process is as follows：
(1) it is 11.0m by flow3/ h, temperature are that the synthesis brackish water shown in 25 DEG C of table 1 is as raw water and flow
4.0m3/ h, temperature be 25 DEG C first backflow crystallization water outlet mixing after, the antisludging agent (active ingredient of 5.0mg/L is added thereto
It is organic phosphonate, Ondeo Nalco Co., OSMOTREAT OSM1035) after, with 15.0m3The total flow of/h, 25 DEG C of temperature are made
In for the first counter-infiltration mixing water inlet supply to the first reverse osmosis units, the first reverse-osmosis treated is carried out at 25 DEG C.Wherein,
One reverse osmosis units use part concentrated water circulate operation pattern, and concentrated water internal circulating load is 15.0m3/ h, first reverse osmosis units enter
Water pressure is 2.2MPa.By after the treatment of the first reverse osmosis units, obtaining flow for 10.0m3/ h, temperature are 25 DEG C first anti-
Water is produced in infiltration and flow is 5.0m3/ h, temperature are 25 DEG C of the first reverse osmosis concentrated water.The mistake of calcium sulfate in first reverse osmosis concentrated water
Saturation degree is 291.0%.
(2) it is 5.0m to flow3/ h, temperature are the iron chloride wadding that 10.0mg/L is added in 25 DEG C of the first reverse osmosis concentrated water
After solidifying agent, supply to the first Crystallization Separation unit carries out the treatment of normal temperature (25 DEG C) Crystallization Separation.Because the effect of flocculant is caused
Part antisludging agent loses the effect for preventing crystallization, and the crystallization of part of sulfuric acid calcium is separated out in oversaturated first reverse osmosis concentrated water of calcium sulfate
Solid, the first crystallization water outlet clarified and the first crystallization solidliquid mixture, by the first crystallization solidliquid mixture centrifugation point
Treatment is centrifuged from device, crystal of calcium sulfate salt (being 14.2kg/h after the deduction crystallization water) is obtained and the first crystallization is female
Liquid, the crystallization water outlet of composition identical first 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 are that 25 DEG C of the first backflow crystallizes water outlet and another plume amount for 1.0m3/ h, temperature are that 25 DEG C of cation is handed over
Swap-in water.First backflow crystallization water outlet is supplied to step (1) and is followed into the first reverse osmosis units after mixing with raw water
Ring treatment.
(3) it is 1.0m by flow3/ h, temperature are that 25 DEG C of cation exchange water inlet feeding cation exchange unit carries out sun
Ion-exchange treatment, wherein, it is 9 minutes that cation exchange 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, temperature are that 25 DEG C of cation exchange water outlet is supplied to the first nanofiltration separation unit,
The first nanofiltration separation treatment is carried out at 25 DEG C.Wherein, the first nanofiltration separation unit uses part concentrated water circulate operation pattern, dense
Water circulation amount is 7.0m3/ h, the intake pressure of the first nanofiltration separation unit is 3.9MPa.After the first nanofiltration separation is processed,
Flow is obtained for 0.88m3/ h, temperature are that 25 DEG C of the first nanofiltration produces water and flow for 0.12m3/ h, temperature are 25 DEG C and first receive
Filter concentrated water.Wherein, the weight/mass percentage composition of sodium sulphate is 9.81% in the first nanofiltration concentrated water.
(5) it is 0.12m by flow3/ h, temperature are that 25 DEG C of the first nanofiltration concentrated water passes through -10 DEG C using spiral tube exchanger
Chilled brine carries out cooling heat transferring treatment, wherein, the first nanofiltration concentrated water is walked in helix tube, and the flow velocity in spiral tube exchanger is
3.0m/s.By after cooling heat transferring treatment, obtaining the first nanofiltration concentrated water that temperature is 0 DEG C and being supplied to the second Crystallization Separation
Unit, carries out Crystallization Separation treatment at 0 DEG C.Because solubility of the sodium sulphate at 0 DEG C is relatively low, part of sulfuric acid sodium is in supersaturation
Solid sodium sulfate crystallization is separated out under the promotion of degree.After being processed through low temperature crystallization, the second crystallization water outlet and the second knot clarified
Brilliant solidliquid mixture, treatment is centrifuged by the second crystallization solidliquid mixture centrifugal separating device, obtains sodium sulphate knot
Brilliant salt (being 5.76kg/h after the deduction crystallization water) and the second crystalline mother solution, the crystallization water outlet of composition identical second and the second crystallization mother
Flow is obtained after liquid mixing for 0.12m3/ h, temperature are 0 DEG C of the second crystallization concentrated water.
(6) it is 0.12m by flow3/ h, temperature are 0 DEG C of the second crystallization concentrated water through tubular heat exchanger heating heat exchange to 25
Supplied after DEG C to the second nanofiltration separation unit, the second nanofiltration separation treatment is carried out at 25 DEG C.Wherein, the second nanofiltration separation unit
Using part concentrated water circulate operation pattern, concentrated water internal circulating load is 0.5m3/ h, the intake pressure of the second nanofiltration separation unit is
3.9MPa.By after the treatment of the second nanofiltration separation, obtaining flow for 0.05m3/ h, temperature are that water and stream are produced in 25 DEG C of the second nanofiltration
It is 0.07m to measure3/ h, temperature are 25 DEG C of the second nanofiltration concentrated water.After second nanofiltration product water and the first nanofiltration product water are mixed, obtain
Flow is 0.93m3/ h, temperature are that water is produced in 25 DEG C of mixing nanofiltration.Will mixing nanofiltration produce water supply to the second reverse osmosis units and
3rd Crystallization Separation unit carries out the second reverse-osmosis treated and evaporative crystallization treatment successively, obtains solid sodium chloride salt.By second
Nanofiltration concentrated water is supplied to crystallizing evaporator and is evaporated crystallization treatment, obtains the main salt-mixture comprising sodium chloride and sodium sulphate.
Table 3 gives the flow and component of each material stream in embodiment 1.
Table 3
From table 3 it can be seen that temperature is simultaneously containing calcium higher, sodium, chlorion and sulfate radical in 25 DEG C of raw water,
Obtained after the first backflow crystallization water outlet mixes with temperature is 25 DEG C temperature be 25 DEG C, that calcium sulfate degree of supersaturation is 81.9%
One counter-infiltration mixing water inlet, in undersaturated condition, the sulphur of the first reverse osmosis concentrated water by after the first reverse-osmosis treated, obtaining
Sour calcium degree of supersaturation is 291.0%, and due to the effect of antisludging agent, now the first reverse osmosis concentrated water is still stabilization.First is anti-
Infiltration concentrated water separates out sulfuric acid after flocculant causes that antisludging agent loses the effect for preventing crystallization in normal temperature Crystallizing process
Calcium solid, the calcium sulfate degree of supersaturation of the first backflow crystallization water outlet declines to a great extent to 118.6%, close to saturation state (sulfuric acid
Calcium degree of supersaturation 100%), a kind of new steady s tate is reached, the first reverse osmosis units are back to afterwards is circulated treatment.This
Plant circular treatment and also cause that the Water Sproading rate and the calcium sulfate rate of recovery of system are increased considerably, it is anti-by first in the present embodiment
Permeation unit and the first Crystallization Separation unit composition combined system Water Sproading rate be 90.9%, and crystal of calcium sulfate salt return
Yield (in terms of calcium) is then 86.3%.The efficient crystallization of calcium sulfate is reclaimed and also greatly reduces the negative of follow-up cation exchange
Lotus.In the present embodiment, for raw water, cation exchange unit is for ion exchange load that cation exchange is intake
Only 13.7%, greatly reduce investment and the operating cost of ion exchange.
On the other hand, due to the greatest differences (sodium sulphate at 25 DEG C and 0 DEG C changed using the solubility with temperature of sodium sulphate
Solubility in water respectively may be about 30 grams and 5 grams), using the first nanofiltration separation (25 DEG C) and the second Crystallization Separation (0 DEG C) phase
With reference to furthermore achieved that sodium sulphate is separated with sodium chloride.In the present embodiment, the quality hundred of sodium chloride in water is produced in mixing nanofiltration
Content is divided to be 1.502%, sodium sulphate is only 0.023%, by after the second counter-infiltration and evaporative crystallization treatment, gained crystal salt is consolidated
The purity of sodium chloride is 98.5% in body, and the rate of recovery (as chloride ion) of sodium chloride is 83.8%, and at the second Crystallization Separation
The purity of the sodium sulphate that reason is obtained is 99.1%, and the rate of recovery (in terms of sulfate radical in ion exchange water outlet) is 48.1%.
Embodiment 2
With reference to Fig. 1, the present embodiment is used to illustrate salt extraction process of the invention.
The first reverse osmosis units used in the present embodiment are to include 3 putaminas of parallel connection, every putamina built with 6 strings
One section of counter-infiltration system of one-level of the DOW BW30FR-400 reverse-osmosis membrane elements of connection；First Crystallization Separation unit includes one always
Volume is 9.0m3Reaction depositing reservoir and centrifugal separating device；Cation exchange unit is that a volume is 0.25m3, filling
The cation exchanger of DOWEX MAC-3 Weak-acid cation exchange resins；First nanofiltration separation unit is to include built-in 2 series connection
GE SWSR-400 nanofiltration membrane components monofilm shell one section of nanofiltration system of one-level；Second Crystallization Separation unit includes a band
The volume of heat-insulation layer is 0.3m3Rustless steel container and centrifugal separating device；Second nanofiltration separation unit is built-in 1 series connection
One section of nanofiltration system of monofilm shell one-level of GE DSL NF2540 nanofiltration membrane components.3rd crystalline element includes crystallizing evaporator.It is former
The flow of inlet water for expecting water is 11.0m3/ h, concrete technology flow process is as follows：
(1) it is 11.0m by flow3/ h, temperature are that the synthesis brackish water shown in 15 DEG C of table 2 is as raw water and flow
2.3m3/ h, temperature be 15 DEG C first backflow crystallization water outlet mixing after, the antisludging agent (active ingredient of 3.0mg/L is added thereto
It is organic phosphonate, Ondeo Nalco Co., OSMOTREAT OSM1035) after, with 13.3m3The total flow of/h, 15 DEG C of temperature are made
In for the first counter-infiltration mixing water inlet supply to the first reverse osmosis units, the first reverse-osmosis treated is carried out at 15 DEG C.Wherein,
One reverse osmosis units use part concentrated water circulate operation pattern, and concentrated water internal circulating load is 16.7m3/ h, first reverse osmosis units enter
Water pressure is 1.9MPa.By after the treatment of the first reverse osmosis units, obtaining flow for 10.0m3/ h, temperature are 15 DEG C first anti-
Water is produced in infiltration and flow is 3.3m3/ h, temperature are 15 DEG C of the first reverse osmosis concentrated water.The mistake of calcium sulfate in first reverse osmosis concentrated water
Saturation degree is 209.3%.
(2) it is 3.3m to flow3/ h, temperature are the iron chloride wadding that 5.0mg/L is added in 15 DEG C of the first reverse osmosis concentrated water
After solidifying agent, supply to the first Crystallization Separation unit carries out the treatment of normal temperature (15 DEG C) Crystallization Separation.Because the effect of flocculant is caused
Part antisludging agent loses the effect for preventing crystallization, and the crystallization of part of sulfuric acid calcium is separated out in oversaturated first reverse osmosis concentrated water of calcium sulfate
Solid, the first crystallization water outlet clarified and the first crystallization solidliquid mixture, by the first crystallization solidliquid mixture centrifugation point
Treatment is centrifuged from device, crystal of calcium sulfate salt (being 6.2kg/h after the deduction crystallization water) and the first crystalline mother solution is obtained,
Composition identical first crystallizes water outlet and is divided into two strands as the first crystallization concentrated water with the first crystalline mother solution, and one flow is 2.3m3/
H, temperature are that 15 DEG C of the first backflow crystallizes water outlet and another plume amount for 1.0m3/ h, temperature are that 15 DEG C of cation exchange is entered
Water.First backflow crystallization water outlet is supplied to step (1) and be circulated place into the first reverse osmosis units after mixing with raw water
Reason.
(3) it is 1.0m by flow3/ h, temperature are that 15 DEG C of cation exchange water inlet feeding cation exchange unit carries out sun
Ion-exchange treatment, wherein, it is 15 minutes that cation exchange was intake in the residence time of cation exchange unit, and obtaining flow is
1.0m3The cation exchange water outlet that/h, temperature are 15 DEG C, calcium ion concentration is 0.11mg/l.
(4) it is 1.0m by flow3/ h, temperature are that 15 DEG C of cation exchange water outlet is supplied to the first nanofiltration separation unit,
The first nanofiltration separation treatment is carried out at 15 DEG C.Wherein, the first nanofiltration separation unit uses part concentrated water circulate operation pattern, dense
Water circulation amount is 7.0m3/ h, the intake pressure of the first nanofiltration separation unit is 3.6MPa.After the first nanofiltration separation is processed,
Flow is obtained for 0.93m3/ h, temperature are that 15 DEG C of the first nanofiltration produces water and flow for 0.07m3/ h, temperature are 15 DEG C and first receive
Filter concentrated water.Wherein, the weight/mass percentage composition of sodium sulphate is 9.05% in the first nanofiltration concentrated water.
(5) it is 0.07m by flow3/ h, temperature are that 15 DEG C of the first nanofiltration concentrated water passes through -10 DEG C using spiral tube exchanger
Chilled brine carries out cooling heat transferring treatment, wherein, the first nanofiltration concentrated water is walked in helix tube, and the flow velocity in spiral tube exchanger is
5.0m/s.By after cooling heat transferring treatment, obtaining the first nanofiltration concentrated water that temperature is -2 DEG C and being supplied to the second crystallization point
From unit, Crystallization Separation treatment is carried out at -2 DEG C.Because solubility of the sodium sulphate at -2 DEG C is relatively low, part of sulfuric acid sodium is in mistake
Solid sodium sulfate crystallization is separated out under the promotion of saturation degree.After being processed through low temperature crystallization, the second crystallization water outlet clarified and the
Two crystallization solidliquid mixtures, treatment is centrifuged by the second crystallization solidliquid mixture centrifugal separating device, obtains sulfuric acid
Sodium crystal salt (being 2.82kg/h after the deduction crystallization water) and the second crystalline mother solution, the crystallization water outlet of composition identical second and the second knot
Flow is obtained for 0.07m after brilliant mother liquor mixing3/ h, temperature are -2 DEG C of the second crystallization concentrated water.
(6) it is 0.07m by flow3/ h, temperature are that -2 DEG C of the second crystallization concentrated water exchanges heat extremely through tubular heat exchanger heating
Supplied after 15 DEG C to the second nanofiltration separation unit, the second nanofiltration separation treatment is carried out at 15 DEG C.Wherein, the second nanofiltration separation list
Unit uses part concentrated water circulate operation pattern, and concentrated water internal circulating load is 0.4m3/ h, the intake pressure of the second nanofiltration separation unit is
3.8MPa.By after the treatment of the second nanofiltration separation, obtaining flow for 0.03m3/ h, temperature are that water and stream are produced in 15 DEG C of the second nanofiltration
It is 0.04m to measure3/ h, temperature are 15 DEG C of the second nanofiltration concentrated water.After second nanofiltration product water and the first nanofiltration product water are mixed, obtain
Flow is 0.96m3/ h, temperature are that water is produced in 15 DEG C of mixing nanofiltration.Will mixing nanofiltration produce water supply to the second reverse osmosis units and
3rd Crystallization Separation unit carries out the second reverse-osmosis treated and evaporative crystallization treatment successively, obtains solid sodium chloride salt.By second
Nanofiltration concentrated water is supplied to crystallizing evaporator and is evaporated crystallization treatment, obtains the main salt-mixture comprising sodium chloride and sodium sulphate.
Table 4 gives the flow and component of each material stream in embodiment 2.
Table 4
From table 4, it can be seen that temperature is simultaneously containing calcium higher, sodium, chlorion and sulfate radical in 15 DEG C of raw water,
Obtained after the first backflow crystallization water outlet mixes with temperature is 15 DEG C temperature be 15 DEG C, that calcium sulfate degree of supersaturation is 41.5%
One counter-infiltration mixing water inlet, in undersaturated condition, the sulphur of the first reverse osmosis concentrated water by after the first reverse-osmosis treated, obtaining
Sour calcium degree of supersaturation is 209.3%, and due to the effect of antisludging agent, now the first reverse osmosis concentrated water is still stabilization.First is anti-
Infiltration concentrated water separates out sulfuric acid after flocculant causes that antisludging agent loses the effect for preventing crystallization in normal temperature Crystallizing process
Calcium solid, the calcium sulfate degree of supersaturation of the first backflow crystallization water outlet declines to a great extent to 109.3%, close to saturation state (sulfuric acid
Calcium degree of supersaturation 100%), a kind of new steady s tate is reached, the first reverse osmosis units are back to afterwards is circulated treatment.This
Plant circular treatment and also cause that the Water Sproading rate and the calcium sulfate rate of recovery of system are increased considerably, it is anti-by first in the present embodiment
Permeation unit and the first Crystallization Separation unit composition combined system Water Sproading rate be 90.9%, and crystal of calcium sulfate salt return
Yield (in terms of calcium) is then 68.1%.The load for also greatly reducing follow-up cation exchange is reclaimed in the crystallization of calcium sulfate.This
In embodiment, for raw water, cation exchange unit is only for the ion exchange load that cation exchange is intake
31.9%, greatly reduce investment and the operating cost of ion exchange.
On the other hand, due to the greatest differences changed using the solubility with temperature of sodium sulphate, using the first nanofiltration separation
(15 DEG C) are combined with the second Crystallization Separation (- 2 DEG C), furthermore achieved that sodium sulphate is separated with sodium chloride.In the present embodiment,
The weight/mass percentage composition that sodium chloride in water is produced in mixing nanofiltration is 1.358%, and sodium sulphate is only 0.020%, by the second counter-infiltration
After evaporative crystallization treatment, the purity of sodium chloride is 98.5% in gained crystal salt solid, and the rate of recovery of sodium chloride is (with chlorion
Meter) it is 85.5%, and the purity of the sodium sulphate that the treatment of the second Crystallization Separation is obtained is 99.2%, the rate of recovery (is gone out with ion exchange
Sulfate radical meter in water) it is 44.5%.
Embodiment 3
With reference to Fig. 2, the present embodiment is used to illustrate salt extraction process of the invention.
The first reverse osmosis units used in the present embodiment are to include 3 putaminas of parallel connection, every putamina built with 6 strings
One section of counter-infiltration system of one-level of the DOW BW30FR-400 reverse-osmosis membrane elements of connection；First Crystallization Separation unit includes one always
Volume is 12.5m3Reaction depositing reservoir and centrifugal separating device；Cation exchange unit is that a volume is 0.15m3, filling
The cation exchanger of DOWEX MAC-3 Weak-acid cation exchange resins；First nanofiltration separation unit is to include built-in 2 series connection
GE SWSR-400 nanofiltration membrane components monofilm shell one section of nanofiltration system of one-level；Second Crystallization Separation unit includes a band
The volume of heat-insulation layer is 0.3m3Rustless steel container and centrifugal separating device；3rd crystalline element includes crystallizing evaporator.Raw material
The flow of inlet water of water is 11.0m3/ h, concrete technology flow process is as follows：
(1) it is 11.0m by flow3/ h, temperature are that the synthesis brackish water shown in 25 DEG C of table 1 is as raw water and flow
4.0m3/ h, temperature be 25 DEG C first backflow crystallization water outlet mixing after, the antisludging agent (active ingredient of 5.0mg/L is added thereto
It is organic phosphonate, Ondeo Nalco Co., OSMOTREAT OSM1035) after, with 15.0m3The total flow of/h, 25 DEG C of temperature are made
In for the first counter-infiltration mixing water inlet supply to the first reverse osmosis units, the first reverse-osmosis treated is carried out at 25 DEG C.Wherein,
One reverse osmosis units use part concentrated water circulate operation pattern, and concentrated water internal circulating load is 15.0m3/ h, first reverse osmosis units enter
Water pressure is 2.2MPa.By after the treatment of the first reverse osmosis units, obtaining flow for 10.0m3/ h, temperature are 25 DEG C first anti-
Water is produced in infiltration and flow is 5.0m3/ h, temperature are 25 DEG C of the first reverse osmosis concentrated water.The mistake of calcium sulfate in first reverse osmosis concentrated water
Saturation degree is 291.0%.
(2) it is 5.0m to flow3/ h, temperature are the iron chloride wadding that 10.0mg/L is added in 25 DEG C of the first reverse osmosis concentrated water
After solidifying agent, supply to the first Crystallization Separation unit carries out the treatment of normal temperature (25 DEG C) Crystallization Separation.Because the effect of flocculant is caused
Part antisludging agent loses the effect for preventing crystallization, and the crystallization of part of sulfuric acid calcium is separated out in oversaturated first reverse osmosis concentrated water of calcium sulfate
Solid, the first crystallization water outlet clarified and the first crystallization solidliquid mixture, by the first crystallization solidliquid mixture centrifugation point
Treatment is centrifuged from device, crystal of calcium sulfate salt (being 14.2kg/h after the deduction crystallization water) is obtained and the first crystallization is female
Liquid, the crystallization water outlet of composition identical first 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 are that 25 DEG C of the first backflow crystallizes water outlet and another plume amount for 1.0m3/ h, temperature are that 25 DEG C of cation is handed over
Swap-in water.First backflow normal temperature crystallization water outlet is supplied to step (1) and is entered into the first reverse osmosis units after mixing with raw water
Row circular treatment.
(3) it is 1.0m by flow3/ h, temperature are that 25 DEG C of cation exchange water inlet feeding cation exchange unit carries out sun
Ion-exchange treatment, wherein, it is 9 minutes that cation exchange 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, temperature are 25 DEG C of cation exchange water outlet, are 0.24m with flow3/ h, it is heated to
Temperature be 25 DEG C second backflow crystallization water outlet mixing after, with 1.24m3The total flow of/h is supplied to the first nanofiltration separation unit,
The first nanofiltration separation treatment is carried out at 25 DEG C.Wherein, the first nanofiltration separation unit uses part concentrated water circulate operation pattern, dense
Water circulation amount is 5.0m3/ h, the intake pressure of the first nanofiltration separation unit is 2.7MPa.After the first nanofiltration separation is processed,
Flow is obtained for 0.93m3/ h, temperature are that 25 DEG C of the first nanofiltration produces water and flow for 0.31m3/ h, temperature are 25 DEG C and first receive
Filter concentrated water.Wherein, the weight/mass percentage composition of sodium sulphate is 7.69% in the first nanofiltration concentrated water.
(5) it is 0.31m by flow3/ h, temperature are that 25 DEG C of the first nanofiltration concentrated water passes through -10 DEG C using spiral tube exchanger
Chilled brine carries out cooling heat transferring treatment, wherein, the first nanofiltration concentrated water is walked in helix tube, and the flow velocity in spiral tube exchanger is
3.0m/s.By after cooling heat transferring treatment, obtaining the first nanofiltration concentrated water that temperature is 0 DEG C and being supplied to the second Crystallization Separation
Unit, carries out Crystallization Separation treatment at 0 DEG C.Because solubility of the sodium sulphate at 0 DEG C is relatively low, part of sulfuric acid sodium is in supersaturation
Solid sodium sulfate crystallization is separated out under the promotion of degree.After being processed through low temperature crystallization, the second crystallization water outlet and the second knot clarified
Brilliant solidliquid mixture, treatment is centrifuged by the second crystallization solidliquid mixture centrifugal separating device, obtains sodium sulphate knot
Brilliant salt (being 8.33kg/h after the deduction crystallization water) and the second crystalline mother solution, the crystallization water outlet of composition identical second and the second crystallization mother
Flow is obtained after liquid mixing for 0.31m3/ h, temperature are that 0 DEG C of the second crystallization concentrated water is divided into two strands, and one flow is 0.24m3/h、
Temperature is that 0 DEG C of the second backflow crystallizes water outlet and another plume amount for 0.07m3/ h, temperature are 0 DEG C of system concentrated water.By second
Backflow crystallization water outlet is through tubular heat exchanger heating heat exchange to after supplying to step (4) after 25 DEG C and mix with cation exchange water outlet
Treatment is circulated into the first nano-filtration unit.
(6) the first nanofiltration product water supplies to the second reverse osmosis units and the 3rd Crystallization Separation unit to carry out second successively anti-
Infiltration treatment and evaporative crystallization treatment, obtain solid sodium chloride salt.System concentrated water is supplied to crystallizing evaporator and is evaporated knot
Crystalline substance treatment, obtains the main salt-mixture comprising sodium chloride and sodium sulphate.
Table 5 gives the flow and component of each material stream in embodiment 3.
Table 5
As can be seen from Table 5, temperature be in 25 DEG C of raw water simultaneously containing calcium higher, sodium, chlorion and sulfate radical,
Obtained after the first backflow crystallization water outlet mixes with temperature is 25 DEG C temperature be 25 DEG C, that calcium sulfate degree of supersaturation is 81.9%
One counter-infiltration mixing water inlet, in undersaturated condition, the sulphur of the first reverse osmosis concentrated water by after the first reverse-osmosis treated, obtaining
Sour calcium degree of supersaturation is 291.0%, and due to the effect of antisludging agent, now the first reverse osmosis concentrated water is still stabilization.First is anti-
Infiltration concentrated water separates out sulfuric acid after flocculant causes that antisludging agent loses the effect for preventing crystallization in normal temperature Crystallizing process
Calcium solid, the calcium sulfate degree of supersaturation of the first backflow crystallization water outlet declines to a great extent to 118.6%, close to saturation state (sulfuric acid
Calcium degree of supersaturation 100%), a kind of new steady s tate is reached, the first reverse osmosis units are back to afterwards is circulated treatment.This
Plant circular treatment and also cause that the Water Sproading rate and the calcium sulfate rate of recovery of system are increased considerably, it is anti-by first in the present embodiment
Permeation unit and the first Crystallization Separation unit composition combined system Water Sproading rate be 90.9%, and crystal of calcium sulfate salt return
Yield (in terms of calcium) is then 86.3%.The efficient crystallization of calcium sulfate is reclaimed and also greatly reduces the negative of follow-up cation exchange
Lotus.In the present embodiment, for raw water, cation exchange unit is for ion exchange load that cation exchange is intake
Only 13.7%, greatly reduce investment and the operating cost of ion exchange.
On the other hand, due to the greatest differences changed using the solubility with temperature of sodium sulphate, using the first nanofiltration separation
(25 DEG C) are combined with the second Crystallization Separation (0 DEG C), furthermore achieved that sodium sulphate is separated with sodium chloride.In the present embodiment,
The weight/mass percentage composition that sodium chloride in water is produced in first nanofiltration is 1.499%, and sodium sulphate is only 0.015%, by the second counter-infiltration
After evaporative crystallization treatment, the purity of sodium chloride is 99.0% in gained crystal salt solid, and the rate of recovery of sodium chloride is (with chlorion
Meter) it is 83.6%, and the purity of the sodium sulphate that the treatment of the second Crystallization Separation is obtained is 99.3%, the rate of recovery (is gone out with ion exchange
Sulfate radical meter in water) it is 70.4%.
Embodiment 4
With reference to Fig. 2, the present embodiment is used to illustrate salt extraction process of the invention.
The first reverse osmosis units used in the present embodiment are to include 3 putaminas of parallel connection, every putamina built with 6 strings
One section of counter-infiltration system of one-level of the DOW BW30FR-400 reverse-osmosis membrane elements of connection；First Crystallization Separation unit includes one always
Volume is 9.0m3Reaction depositing reservoir and centrifugal separating device；Cation exchange unit is that a volume is 0.25m3, filling
The cation exchanger of DOWEX MAC-3 Weak-acid cation exchange resins；First nanofiltration separation unit is to include built-in 2 series connection
GE SWSR-400 nanofiltration membrane components monofilm shell one section of nanofiltration system of one-level；Second Crystallization Separation unit includes a band
The volume of heat-insulation layer is 0.3m3Rustless steel container and centrifugal separating device；3rd crystalline element includes crystallizing evaporator.Raw material
The flow of inlet water of water is 11.0m3/ h, concrete technology flow process is as follows：
(1) it is 11.0m by flow3/ h, temperature are that the synthesis brackish water shown in 15 DEG C of table 2 is as raw water and flow
2.3m3/ h, temperature be 15 DEG C first backflow crystallization water outlet mixing after, the antisludging agent (active ingredient of 3.0mg/L is added thereto
It is organic phosphonate, Ondeo Nalco Co., OSMOTREAT OSM1035) after, with 13.3m3The total flow of/h, 15 DEG C of temperature are made
In for the first counter-infiltration mixing water inlet supply to the first reverse osmosis units, the first reverse-osmosis treated is carried out at 15 DEG C.Wherein,
One reverse osmosis units use part concentrated water circulate operation pattern, and concentrated water internal circulating load is 16.7m3/ h, first reverse osmosis units enter
Water pressure is 1.9MPa.By after the treatment of the first reverse osmosis units, obtaining flow for 10.0m3/ h, temperature are 15 DEG C first anti-
Water is produced in infiltration and flow is 3.3m3/ h, temperature are 15 DEG C of the first reverse osmosis concentrated water.The mistake of calcium sulfate in first reverse osmosis concentrated water
Saturation degree is 209.3%.
(2) it is 3.3m to flow3/ h, temperature are the iron chloride wadding that 5.0mg/L is added in 15 DEG C of the first reverse osmosis concentrated water
After solidifying agent, supply to the first Crystallization Separation unit carries out the treatment of normal temperature (15 DEG C) Crystallization Separation.Because the effect of flocculant is caused
Part antisludging agent loses the effect for preventing crystallization, and the crystallization of part of sulfuric acid calcium is separated out in oversaturated first reverse osmosis concentrated water of calcium sulfate
Solid, the first crystallization water outlet clarified and the first crystallization solidliquid mixture, by the first crystallization solidliquid mixture centrifugation point
Treatment is centrifuged from device, crystal of calcium sulfate salt (being 6.2kg/h after the deduction crystallization water) and the first crystalline mother solution is obtained,
Composition identical first crystallizes water outlet and is divided into two strands as the first crystallization concentrated water with the first crystalline mother solution, and one flow is 2.3m3/
H, temperature are that 15 DEG C of the first backflow crystallizes water outlet and another plume amount for 1.0m3/ h, temperature are that 15 DEG C of cation exchange is entered
Water.First backflow normal temperature crystallization water outlet is supplied to step (1) and is followed into the first reverse osmosis units after mixing with raw water
Ring treatment.
(3) it is 1.0m by flow3/ h, temperature are that 15 DEG C of cation exchange water inlet feeding cation exchange unit carries out sun
Ion-exchange treatment, wherein, it is 15 minutes that cation exchange was intake in the residence time of cation exchange unit, and obtaining flow is
1.0m3The cation exchange water outlet that/h, temperature are 15 DEG C, calcium ion concentration is 0.11mg/l.
(4) it is 1.0m by flow3/ h, temperature are 15 DEG C of cation exchange water outlet, are 0.42m with flow3/ h, it is heated to
Temperature be 15 DEG C second backflow crystallization water outlet mixing after, with 1.42m3The total flow of/h is supplied to the first nanofiltration separation unit,
The first nanofiltration separation treatment is carried out at 15 DEG C.Wherein, the first nanofiltration separation unit uses part concentrated water circulate operation pattern, dense
Water circulation amount is 5.0m3/ h, the intake pressure of the first nanofiltration separation unit is 2.5MPa.After the first nanofiltration separation is processed,
Flow is obtained for 0.95m3/ h, temperature are that 15 DEG C of the first nanofiltration produces water and flow for 0.47m3/ h, temperature are 15 DEG C and first receive
Filter concentrated water.Wherein, the weight/mass percentage composition of sodium sulphate is 6.00% in the first nanofiltration concentrated water.
(5) it is 0.47m by flow3/ h, temperature are that 15 DEG C of the first nanofiltration concentrated water passes through -10 DEG C using spiral tube exchanger
Chilled brine carries out cooling heat transferring treatment, wherein, the first nanofiltration concentrated water is walked in helix tube, and the flow velocity in spiral tube exchanger is
5.0m/s.By after cooling heat transferring treatment, obtaining the first nanofiltration concentrated water that temperature is -2 DEG C and being supplied to the second crystallization point
From unit, Crystallization Separation treatment is carried out at -2 DEG C.Because solubility of the sodium sulphate at -2 DEG C is relatively low, part of sulfuric acid sodium is in mistake
Solid sodium sulfate crystallization is separated out under the promotion of saturation degree.After being processed through low temperature crystallization, the second crystallization water outlet clarified and the
Two crystallization solidliquid mixtures, treatment is centrifuged by the second crystallization solidliquid mixture centrifugal separating device, obtains sulfuric acid
Sodium crystal salt (being 3.80kg/h after the deduction crystallization water) and the second crystalline mother solution, the crystallization water outlet of composition identical second and the second knot
Flow is obtained for 0.47m after brilliant mother liquor mixing3/ h, temperature are that -2 DEG C of the second crystallization concentrated water is divided into two strands, and one flow is
0.42m3/ h, temperature are that -2 DEG C of the second backflow crystallizes water outlet and another plume amount for 0.05m3/ h, temperature are that -2 DEG C of system is dense
Water.Second backflow is crystallized into water outlet through tubular heat exchanger heating heat exchange to supplying to step (4) and cation exchange after 15 DEG C
After water outlet mixing treatment is circulated into the first nano-filtration unit.
(6) the first nanofiltration product water supplies to the second reverse osmosis units and the 3rd Crystallization Separation unit to carry out second successively anti-
Infiltration treatment and evaporative crystallization treatment, obtain solid sodium chloride salt.System concentrated water is supplied to crystallizing evaporator and is evaporated knot
Crystalline substance treatment, obtains the main salt-mixture comprising sodium chloride and sodium sulphate.
Table 6 gives the flow and component of each material stream in embodiment 4.
Table 6
As can be seen from Table 6, temperature be in 15 DEG C of raw water simultaneously containing calcium higher, sodium, chlorion and sulfate radical,
Obtained after the first backflow crystallization water outlet mixes with temperature is 15 DEG C temperature be 15 DEG C, that calcium sulfate degree of supersaturation is 41.5%
One counter-infiltration mixing water inlet, in undersaturated condition, the sulphur of the first reverse osmosis concentrated water by after the first reverse-osmosis treated, obtaining
Sour calcium degree of supersaturation is 209.3%, and due to the effect of antisludging agent, now the first reverse osmosis concentrated water is still stabilization.First is anti-
Infiltration concentrated water separates out sulfuric acid after flocculant causes that antisludging agent loses the effect for preventing crystallization in normal temperature Crystallizing process
Calcium solid, the calcium sulfate degree of supersaturation of the first backflow crystallization water outlet declines to a great extent to 109.3%, close to saturation state (sulfuric acid
Calcium degree of supersaturation 100%), a kind of new steady s tate is reached, the first reverse osmosis units are back to afterwards is circulated treatment.This
Plant circular treatment and also cause that the Water Sproading rate and the calcium sulfate rate of recovery of system are increased considerably, it is anti-by first in the present embodiment
Permeation unit and the first Crystallization Separation unit composition combined system Water Sproading rate be 90.9%, and crystal of calcium sulfate salt return
Yield (in terms of calcium) is then 68.1%.The load for also greatly reducing follow-up cation exchange is reclaimed in the crystallization of calcium sulfate.This
In embodiment, for raw water, cation exchange unit is only for the ion exchange load that cation exchange is intake
31.9%, greatly reduce investment and the operating cost of ion exchange.
On the other hand, due to the greatest differences changed using the solubility with temperature of sodium sulphate, using the first nanofiltration separation
(15 DEG C) are combined with the second Crystallization Separation (- 2 DEG C), furthermore achieved that sodium sulphate is separated with sodium chloride.In the present embodiment,
The weight/mass percentage composition that sodium chloride in water is produced in first nanofiltration is 1.356%, and sodium sulphate is only 0.012%, by the second counter-infiltration
After evaporative crystallization treatment, the purity of sodium chloride is 99.1% in gained crystal salt solid, and the rate of recovery of sodium chloride is (with chlorion
Meter) it is 84.4%, and the purity of the sodium sulphate that the treatment of the second Crystallization Separation is obtained is 99.2%, the rate of recovery (is gone out with ion exchange
Sulfate radical meter in water) it is 59.4%.
Comparative example 1
This comparative example uses flow shown in Fig. 3, for the advance of comparative illustration salt extraction process of the invention.
The reverse osmosis units used in this comparative example are to include 3 putaminas of parallel connection, 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 for a volume
0.50m3, filling DOWEX MAC-3 Weak-acid cation exchange resins cation exchanger；Nanofiltration separation unit be include it is built-in
6 one section of nanofiltration systems of one-level of the monofilm shell of the GE SWSR-400 nanofiltration membrane components of series connection.The flow of inlet water of raw water is
11.0m3/ h, concrete technology flow process is 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 adding the antisludging agent (active ingredient is organic phosphonate, Ondeo Nalco Co., OSMOTREAT OSM1035) of 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 is 19.0m3/ h, the intake pressure of reverse osmosis units is 1.1MPa.By after reverse osmosis units treatment, obtaining
It is 7.61m to flow3/ h, temperature are 25 DEG C of reverse osmosis produced water and flow is 3.39m3/ h, temperature are 25 DEG C reverse osmosis concentrated
Water.Now, the degree of supersaturation of calcium sulfate is the satiety of the first reverse osmosis concentrated water in 291.5%, with embodiment 1 in reverse osmosis concentrated water
It is suitable with degree.
(2) it is 3.39m by flow3/ h, temperature be 25 DEG C reverse osmosis concentrated water feeding cation exchange unit carry out sun from
Sub- exchange treatment, wherein, it is 9 minutes that cation exchange was intake in the residence time of cation exchange unit, and obtaining flow is
3.39m3The cation exchange water outlet that/h, temperature are 25 DEG C, calcium ion concentration is 0.05mg/l.
(3) it is 3.39m by flow3/ h, temperature are that 25 DEG C of cation exchange water outlet is supplied to nanofiltration separation unit, 25
Nanofiltration separation treatment is carried out at DEG C.Wherein, using part concentrated water circulate operation pattern, concentrated water internal circulating load is nanofiltration separation unit
6.6m3/ h, the intake pressure of nanofiltration separation unit is 3.7MPa.By after nanofiltration separation treatment, obtaining flow for 3.12m3/h、
Temperature is that 25 DEG C of nanofiltration produces water and flow for 0.27m3/ h, temperature are 25 DEG C of nanofiltration concentrated water.
(4) it is 3.12m by flow3/ h, temperature are that 25 DEG C of nanofiltration product water is supplied to the second reverse osmosis units and evaporation knot
Brilliant unit carries out the second reverse-osmosis treated and evaporative crystallization treatment successively, obtains solid sodium chloride salt.It is 0.27m by flow3/h、
Temperature is that 25 DEG C of nanofiltration concentrated water is supplied to the second evaporative crystallization unit and is evaporated crystallization treatment, is obtained comprising sodium chloride and sulphur
The salt-mixture of sour sodium.
Table 7 gives the flow and component of each material stream in comparative example 1.
Table 7
As can be seen from Table 7, temperature be in 25 DEG C of raw water simultaneously containing calcium higher, sodium, chlorion and sulfate radical,
Calcium sulfate degree of supersaturation is 70.7%, in undersaturated condition, the sulfuric acid of the reverse osmosis concentrated water by after reverse-osmosis treated, obtaining
Calcium degree of supersaturation is 291.5%, and the fouling risk with embodiment 1 is suitable.Due to without the first crystallization being introduced into embodiment 1-4
Unit (normal temperature crystallization), calcium sulfate is all gathered in reverse osmosis concentrated water, limits the Water Sproading rate of reverse osmosis units (only
69.2%, far below embodiment 1 in 90.9%).
Due to no normal temperature crystallization removal part of sulfuric acid calcium, the load (in terms of Ca) that this comparative example cationic is exchanged is
4.79kg/h, is 5.6 times of the load (being calculated as 0.85kg/h with Ca) of cation exchange in embodiment 1, the throwing of ion exchange
Money and regenerative agent expense are dramatically increased.
As a result of nanofiltration, this comparative example still partly realizes the separation of sodium chloride and sodium sulphate.Wherein, nanofiltration is produced
The weight/mass percentage composition of sodium chloride is 0.473% in water, and sodium sulphate is 0.018%, at the second counter-infiltration and evaporative crystallization
After reason, the purity of sodium chloride is 96.3% in gained crystal salt solid, not as good as the sodium chloride purity (98.5%) in embodiment 1.
The percentage composition of sodium sulphate is 9.855% in nanofiltration concentrated water, and sodium chloride is 0.478%, after evaporative crystallization is processed, gained knot
The purity of sodium sulphate is 95.4% in brilliant salt solid, not as good as the purity (99.1%) of the sodium sulphate in embodiment 1.
Further, since not introducing the second crystalline element (low temperature crystallization), sodium sulphate is all gathered in nanofiltration concentrated water, limit
Nanofiltration concentrated water is made and has further concentrated decrement, the part has needed the water of evaporation to also have 0.27m3/ h, second is received in embodiment 1
Filter concentrated water (0.07m3/ h) nearly 4 times, its energy consumption is also corresponding much higher.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various 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 specific 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 is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, 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 (64)
1. a kind of salt extraction process, it is characterised in that the method includes：
(1) brackish water containing dianion salt and univalent anion salt is carried out into the first reverse-osmosis treated, by brackish water
Initial concentration is carried out, the first reverse osmosis concentrated water of rich salt and the first reverse osmosis produced water of poor salt is obtained；
(2) the first reverse osmosis concentrated water that step (1) is obtained is carried out into the first Crystallization Separation treatment, obtains the first crystal salt and first
Crystallization concentrated water, two strands are divided into by the described first crystallization concentrated water, and being back to step (1) respectively as the first backflow crystallization water outlet is carried out
Described the first reverse-osmosis treated and carry out follow-up cation exchange treatment as cation exchange；First crystallization
Salt includes calcium sulfate；
(3) cation exchange for obtaining 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 for obtaining step (3) carries out the first nanofiltration separation treatment as the first nanofiltration, to divide
From dianion salt and univalent anion salt, water and dianion salt quilt are produced in the first nanofiltration for obtaining rich univalent anion salt
First nanofiltration concentrated water of concentration；
(5) step (4) is obtained the first nanofiltration concentrated water cooling after carry out the second Crystallization Separation treatment, obtain the second crystal salt and
Second crystallization concentrated water；
(6) the first nanofiltration for obtaining step (4) is produced water and carries out the treatment of the 3rd Crystallization Separation, obtains rich univalent anion salt.
2. method according to claim 1, wherein, the method also includes：Before the treatment of the 3rd Crystallization Separation is carried out, will
The second crystallization concentrated water that step (5) is obtained carries out the second nanofiltration separation treatment, and the second nanofiltration for obtaining rich univalent anion salt is produced
The second nanofiltration concentrated water that water and dianion salt are concentrated, the first nanofiltration for then obtaining step (4) is produced water and second and is received
Water mixing is produced in the second nanofiltration that filter separating treatment is obtained, and the mixing nanofiltration that will be obtained is produced water and carries out the treatment of the 3rd Crystallization Separation,
Obtain rich univalent anion salt.
3. method according to claim 1, wherein, the method also includes：The second crystallization concentrated water point that step (5) is obtained
It it is two strands, the first nanofiltration separation being back to described in step (4) respectively as the second backflow crystallization water outlet is processed and as system
Concentrated water is post-processed；
Wherein, in step (4), the first nanofiltration water inlet includes the cation exchange water outlet and second backflow that step (3) is obtained
Crystallization water outlet；And in cation exchange water outlet dianion salt weight/mass percentage composition X%<When 5%, relational expression R1 is met<
X/ (5-X), R1 are the volume flow ratio that system concentrated water produces water with the first nanofiltration, and R2 is that the first nanofiltration concentrated water produces water with the first nanofiltration
Volume flow ratio.
4. method according to claim 3, wherein, the weight/mass percentage composition of dianion salt in cation exchange water outlet
X%<When 5%, R1 is met<3X/(50-3X).
5. method according to claim 4, wherein, the weight/mass percentage composition of dianion salt in cation exchange water outlet
X%<When 5%, 4 are met>R2>{(R1+1)*X/5–R1}.
6. the method according to any one in claim 1-5, 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%, relational expression R3 is met<Y/ (2.5-Y), R3 are that cation exchange water inlet is anti-with first
The volume flow ratio of water is produced in infiltration.
7. the method according to any one in claim 1-5, wherein, in step (1), the condition of the first reverse-osmosis treated
Including：Temperature is 10-40 DEG C, and pressure is 1-6MPa, the volume of first reverse osmosis concentrated water and first reverse osmosis produced water
Flow-rate ratio is 0.2-2：1.
8. method according to claim 7, wherein, in step (1), the condition of the first reverse-osmosis treated includes：Temperature is
15-30 DEG C, pressure is 1.8-4MPa, and first reverse osmosis concentrated water is with the volume flow ratio of first reverse osmosis produced water
0.3-1：1.
9. the method according to any one in claim 1-5, wherein, the method also includes：In step (1), will contain
Before salt solution carries out the first reverse-osmosis treated, at least one antisludging agent of addition in the brackish water；And it is described in step (2)
The treatment of the first Crystallization Separation in, control condition inactivates the antisludging agent, to carry out Crystallization Separation.
10. method according to claim 9, wherein, relative to brackish water described in 1L, the consumption of the antisludging agent is 2-
15mg。
11. methods according to claim 10, wherein, relative to brackish water described in 1L, the consumption of the antisludging agent is 3-
7mg。
12. methods according to claim 9, wherein, the antisludging agent is organic phosphine type antisludging agent, the resistance of organic phospho acid salt form
At least one in dirty agent, polycarboxylic acid-based inhibitor and composite scale agent.
13. methods according to claim 9, wherein, in the following ways at least one mode make the antisludging agent
Inactivation：
Mode one：To adding at least one solid matter that can act as normal temperature crystalline seed in first reverse osmosis concentrated water；
Mode two：To at least one flocculant of addition in first reverse osmosis concentrated water；
Mode three：Adjust the pH value of first reverse osmosis concentrated water.
14. methods according to claim 13, wherein, in mode one, the addition of the solid matter causes that first is anti-
The mass concentration of crystal seed is 2%-12% in infiltration concentrated water.
15. methods according to claim 14, wherein, in mode one, the addition of the solid matter causes that first is anti-
The mass concentration of crystal seed is 4%-8% in infiltration concentrated water.
16. methods according to claim 13, wherein, in mode one, in the solid matter and the first reverse osmosis concentrated water
Difficultly water soluble salts species it is identical.
17. methods according to claim 16, wherein, in mode one, the solid matter is selected from calcium sulfate and/or sulfuric acid
The hydrate of calcium.
18. methods according to claim 13, wherein, in mode two, relative to the first reverse osmosis concentrated water described in 1L, institute
The consumption of flocculant is stated for 2-20mg, the flocculant is iron chloride and/or ferric sulfate.
19. methods according to claim 18, wherein, in mode two, relative to the first reverse osmosis concentrated water described in 1L, institute
The consumption for stating flocculant is 5-15mg.
20. methods according to claim 13, wherein, in mode three, the pH value of first reverse osmosis concentrated water is adjusted
It is 3-6.
21. methods according to claim 20, wherein, in mode three, the pH value of first reverse osmosis concentrated water is adjusted
It is 3.5-4.5.
22. method according to any one in claim 1-5, wherein, in step (2), at first Crystallization Separation
The condition of reason includes：Temperature is 10-40 DEG C, and the volume flow ratio of the first backflow crystallization water outlet and cation exchange water inlet is 1-
20：1.
23. methods according to claim 22, wherein, in step (2), the condition bag of the first Crystallization Separation treatment
Include：Temperature is 15-30 DEG C, and the volume flow ratio of the first backflow crystallization water outlet and cation exchange water inlet is 3-9：1.
24. method according to any one in claim 1-5, wherein, in step (3), the cation exchange treatment
Condition include：Temperature is 10-40 DEG C, and the residence time is 2-30 minutes, and the concentration of calcium ion is in cation exchange water outlet
0.01-5mg/L。
25. methods according to claim 24, wherein, in step (3), the condition of the cation exchange treatment includes：
Temperature is 15-30 DEG C, and the residence time is 5-15 minutes, and the concentration of calcium ion is 0.05-1mg/L in cation exchange water outlet.
26. method according to any one in claim 1-5, wherein, in step (4), at first nanofiltration separation
The condition of reason includes：Temperature is 10-40 DEG C, and pressure is 1-6MPa, and the first nanofiltration concentrated water produces water with first nanofiltration
Volume flow ratio is 0.05-2：1.
27. methods according to claim 26, wherein, in step (4), the condition bag of the first nanofiltration separation treatment
Include：Temperature is 15-30 DEG C, and pressure is 2-4MPa, and the first nanofiltration concentrated water produces the volume flow ratio of water with first nanofiltration
It is 0.07-0.5：1.
28. method according to any one in claim 1-5, wherein, in step (4), at first nanofiltration separation
The nanofiltration membrane component that reason is used is the NF membrane of the rejection less than 20% of univalent anion salt in being intake to first nanofiltration
Element.
29. method according to any one in claim 1-5, wherein, in step (5), at second Crystallization Separation
The condition of reason includes：Temperature is less than 5 DEG C and higher than the freezing point temperature of the first nanofiltration concentrated water.
30. methods according to claim 29, wherein, in step (5), the condition bag of the second Crystallization Separation treatment
Include：Temperature is -2~2 DEG C.
31. methods according to claim 29, wherein, in step (5), the described second crystallization concentrated water is evaporated crystallization
Process to obtain the salt-mixture containing univalent anion salt and dianion salt.
32. method according to any one in claim 1-5, wherein, the method for the cooling includes：By the first nanofiltration
Concentrated water is cooled to crystallization temperature by way of the treatment that exchanges heat, and the crystallization temperature is less than 5 DEG C and dense higher than first nanofiltration
The freezing point temperature of water, and it is 1-20m/s to control flow velocity of the first nanofiltration concentrated water in heat exchange treatment.
33. methods according to claim 32, wherein, the crystallization temperature is -2~2 DEG C.
34. methods according to claim 32, wherein, control the first nanofiltration concentrated water heat exchange treatment in flow velocity be
2-5m/s。
35. methods according to claim 32, wherein, the heat exchange treatment is in spiral tube exchanger, tubular heat exchanger
Or carried out in double pipe heat exchanger, and the first nanofiltration concentrated water exchanges heat as tube side fluid in spiral tube exchanger, shell and tube
Flowed in device or double pipe heat exchanger.
36. methods according to claim 2, wherein, the condition of the second nanofiltration separation treatment includes：Temperature is 10-
40 DEG C, pressure is 1-6MPa, and the volume flow ratio that the second nanofiltration concentrated water produces water with second nanofiltration is 0.1-3：1.
37. methods according to claim 36, wherein, the condition of the second nanofiltration separation treatment includes：Temperature is 15-
30 DEG C, pressure is 2-4MPa, and the volume flow ratio that the second nanofiltration concentrated water produces water with second nanofiltration is 0.5-2：1.
38. methods according to claim 2, wherein, the nanofiltration membrane component that the second nanofiltration separation treatment is used is right
The nanofiltration membrane component of the rejection less than 20% of univalent anion salt in the second crystallization concentrated water.
39. methods according to claim 2, wherein, the method also includes：Before the second nanofiltration separation treatment is carried out,
The second crystallization concentrated water is first carried out into hyperthermic treatment.
40. method according to claim 39, wherein, the implementation method of the hyperthermic treatment is heat exchange treatment.
41. method according to any one in claim 1-5, wherein, the method for the 3rd Crystallization Separation treatment is
Evaporative crystallization treatment, the condition of the evaporative crystallization treatment includes：Temperature is 60-130 DEG C.
42. methods according to claim 41, wherein, the condition of the evaporative crystallization treatment includes：Temperature is 90-120
℃。
43. methods according to claim 41, wherein, before evaporative crystallization treatment, that step (4) is obtained
Water is produced in one nanofiltration and optional second nanofiltration is produced water and carries out the second reverse-osmosis treated, obtains the second reverse osmosis concentrated water and the second reverse osmosis
Water is produced thoroughly, and the second reverse osmosis concentrated water and the second reverse osmosis produced water are evaporated crystallization treatment and recycling treatment respectively.
44. methods according to claim 2, wherein, the method also includes：Second nanofiltration concentrated water is carried out into the 4th crystallization point
From treatment to obtain the salt-mixture containing univalent anion salt and dianion salt, the method for the 4th Crystallization Separation treatment
It is evaporative crystallization treatment, its treatment conditions includes：Temperature is 60-130 DEG C.
45. methods according to claim 44, wherein, its treatment conditions includes：Temperature is 90-120 DEG C.
46. method according to any one in claim 1-5, wherein, it is cloudy that the cation exchange water outlet contains divalence
The weight/mass percentage composition of dianion salt is 0.2%- in ion salt and univalent anion salt, and the cation exchange water outlet
5%.
47. methods according to claim 46, wherein, the dianion salt is sodium sulphate, the univalent anion
Salt is sodium chloride.
A kind of 48. salt making systems, it is characterised in that the salt making system include the first reverse osmosis units, the first Crystallization Separation unit,
Cation exchange unit, the first nanofiltration separation unit, the second Crystallization Separation unit and the 3rd Crystallization Separation unit,
First reverse osmosis units are anti-for the brackish water containing dianion salt and univalent anion salt to be carried out into first
Infiltration is processed, and obtains the first reverse osmosis concentrated water of rich salt and the first reverse osmosis produced water of poor salt；
The first Crystallization Separation unit is used to for the first reverse osmosis concentrated water from first reverse osmosis units to carry out first
Crystallization Separation treatment, obtains the first crystal salt and the first crystallization concentrated water, and the first Crystallization Separation unit is anti-with described first
Permeation unit is connected, at least part of first crystallization concentrate recirculation to first reverse osmosis units to be carried out into the first counter-infiltration
Treatment；
The cation exchange unit is used to that first counter-infiltration will not to be back to from the first Crystallization Separation unit
First crystallization concentrated water of unit carries out cation exchange treatment as cation exchange, obtains the sun of rich monovalent cation salt
Ion exchange water outlet；
The first nanofiltration separation unit be used for will include the cation exchange water outlet from the cation exchange unit as
First nanofiltration carries out the first nanofiltration separation treatment, and water and dianion are produced in the first nanofiltration for obtaining rich univalent anion salt
The first nanofiltration concentrated water that salt is concentrated；
The second Crystallization Separation unit is used for the first nanofiltration concentrated water from the first nanofiltration separation unit in cooling bar
The second Crystallization Separation treatment is carried out under part, the second crystal salt and the second crystallization concentrated water is obtained；
The 3rd Crystallization Separation unit be used to including the first nanofiltration from the first nanofiltration separation unit produce water as
The treatment of the 3rd Crystallization Separation is carried out, rich univalent anion salt is obtained.
49. salt making systems according to claim 48, wherein, the salt making system also includes the second nanofiltration separation unit, institute
The second nanofiltration separation unit is stated for the second nanofiltration point will to be carried out from the second of the second Crystallization Separation unit the crystallization concentrated water
From treatment, the second nanofiltration concentrated water that water and dianion salt are concentrated is produced in the second nanofiltration for obtaining rich univalent anion salt；And
The 3rd Crystallization Separation unit is used to that water will to be produced and from described the from the first nanofiltration of the first nanofiltration separation unit
Second nanofiltration of two nanofiltration separation units is produced water and carries out the treatment of the 3rd Crystallization Separation as water inlet, obtains rich univalent anion salt.
50. salt making system according to claim 48 or 49, wherein, first reverse osmosis units include at least one instead
Permeable membrane device.
51. salt making systems according to claim 50, wherein, first reverse osmosis units make including at least two series connection
Reverse-osmosis membrane element.
52. salt making system according to claim 48 or 49, wherein, the first Crystallization Separation unit includes the first crystallization
Unit and the first solid-liquid separation unit,
First crystalline element is used to for the first reverse osmosis concentrated water from first reverse osmosis units to carry out the first crystallization
Treatment, obtains the first crystallization water outlet and the first crystallization solidliquid mixture used as the first crystallization concentrated water,
First solid-liquid separation unit is used to that the will to be carried out from the first of first crystalline element the crystallization solidliquid mixture
The treatment of one separation of solid and liquid, obtains the first crystal salt and the first crystalline mother solution used as the first crystallization concentrated water.
53. salt making system according to claim 48 or 49, wherein, the first nanofiltration separation unit includes at least one
Nanofiltration membrane component, the nanofiltration membrane component is that the rejection of univalent anion salt in being intake to first nanofiltration is less than 20%
Nanofiltration membrane component.
54. salt making system according to claim 48 or 49, wherein, the salt making system also includes cooling unit, described cold
But unit is used to for the first nanofiltration concentrated water from the first nanofiltration separation unit to carry out cooling treatment to obtain cooling water outlet,
The cooling unit includes heat exchanger.
55. salt making systems according to claim 54, wherein, the heat exchanger is spiral tube exchanger, shell and tube heat exchange
Device or double pipe heat exchanger.
56. salt making systems according to claim 54, wherein, the second Crystallization Separation unit includes the second crystalline element
With the second solid-liquid separation unit,
Second crystalline element is used to for the cooling water outlet from the cooling unit to carry out the second crystallization treatment, obtains conduct
The second crystallization water outlet and the second crystallization solidliquid mixture that second crystallization concentrated water is used,
Second solid-liquid separation unit is used to that the will to be carried out from the second of second crystalline element the crystallization solidliquid mixture
The treatment of two separation of solid and liquid, obtains the second crystal salt and the second crystalline mother solution used as the second crystallization concentrated water.
57. salt making systems according to claim 56, wherein, the salt making system also includes that crystallizing evaporator is used for by described in
Second crystallization concentrated water is evaporated crystallization treatment to obtain the salt-mixture containing univalent anion salt and dianion salt.
58. salt making system according to claim 48 or 49, wherein, the second nanofiltration separation unit includes at least one
Nanofiltration membrane component, the nanofiltration membrane component is to be less than 20% to the rejection of univalent anion salt in the described second crystallization concentrated water
Nanofiltration membrane component.
59. salt making system according to claim 48 or 49, wherein, the salt making system also includes intensification unit, the liter
Warm unit is used to that hyperthermic treatment will to be carried out from the second of the second Crystallization Separation unit the crystallization concentrated water.
60. salt making systems according to claim 59, wherein, the intensification unit includes heat exchanger.
61. salt making systems according to claim 60, wherein, the heat exchanger is spiral tube exchanger, shell and tube heat exchange
Device or double pipe heat exchanger.
62. salt making system according to claim 48 or 49, wherein, the salt making system also includes the second reverse osmosis units,
Second reverse osmosis units are used to that water will to be produced from the first nanofiltration of the first nanofiltration separation unit and alternatively come from the
Second nanofiltration of two nanofiltration separation units is produced water and carries out the second reverse-osmosis treated, obtains the second reverse osmosis concentrated water and the second counter-infiltration
Water is produced, and second reverse osmosis units are connected with the 3rd Crystallization Separation unit, for by second reverse osmosis concentrated water
Supply to the 3rd Crystallization Separation unit carries out the treatment of the 3rd Crystallization Separation.
63. salt making system according to claim 48 or 49, wherein, the 3rd Crystallization Separation unit includes evaporative crystallization
Device obtains rich univalent anion salt to be processed by evaporative crystallization.
64. salt making system according to claim 48 or 49, wherein, the salt making system also includes the 4th Crystallization Separation list
Unit, the 4th Crystallization Separation unit is used to for the second nanofiltration concentrated water from the second nanofiltration separation unit to be evaporated knot
To obtain the salt-mixture containing univalent anion salt and dianion salt, the 4th Crystallization Separation unit includes steaming for crystalline substance treatment
Hair crystallizer.
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| CN109956578B (en) * | 2017-12-22 | 2022-10-11 | 国家能源投资集团有限责任公司 | Pretreatment method and system for high-salinity desulfurization wastewater of coal-fired power plant |
| CN110386639B (en) * | 2018-04-18 | 2022-01-21 | 国家能源投资集团有限责任公司 | Method and system for treating brine containing divalent anion salt and monovalent anion salt |
| CN111807471B (en) * | 2019-04-10 | 2022-06-14 | 国家能源投资集团有限责任公司 | Treatment method and treatment system for salt-containing water |
| CN112777815B (en) * | 2019-11-11 | 2022-11-29 | 国家能源投资集团有限责任公司 | Treatment method and treatment system for salt-containing water |
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