CN109824188A - It is a kind of to improve crystallization purity salt and resource rate divides salt system and method - Google Patents
It is a kind of to improve crystallization purity salt and resource rate divides salt system and method Download PDFInfo
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- CN109824188A CN109824188A CN201711182870.5A CN201711182870A CN109824188A CN 109824188 A CN109824188 A CN 109824188A CN 201711182870 A CN201711182870 A CN 201711182870A CN 109824188 A CN109824188 A CN 109824188A
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- 150000003839 salts Chemical class 0.000 title claims abstract description 243
- 238000002425 crystallisation Methods 0.000 title claims abstract description 143
- 230000008025 crystallization Effects 0.000 title claims abstract description 143
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000001728 nano-filtration Methods 0.000 claims abstract description 248
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 196
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 150
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 147
- 239000011780 sodium chloride Substances 0.000 claims abstract description 95
- 239000013078 crystal Substances 0.000 claims abstract description 78
- 239000005416 organic matter Substances 0.000 claims abstract description 73
- 230000015556 catabolic process Effects 0.000 claims abstract description 72
- 238000006731 degradation reaction Methods 0.000 claims abstract description 72
- 230000003750 conditioning effect Effects 0.000 claims abstract description 43
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 43
- 238000003672 processing method Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 129
- 238000001704 evaporation Methods 0.000 claims description 54
- 239000012452 mother liquor Substances 0.000 claims description 43
- 230000008020 evaporation Effects 0.000 claims description 34
- 238000004090 dissolution Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002440 industrial waste Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 18
- 239000002351 wastewater Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 208000028659 discharge Diseases 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000010850 salt effect Methods 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 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 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- -1 coal-to-olefin Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Crystallization purity salt is improved and resource rate divides salt system, including nanofiltration conditioning tank, nano-filtration unit, NaCl depth upgrading unit, NaCl evaporative crystallization unit, organic matter degradation unit, Na the invention discloses a kind of2SO4Depth upgrading unit, Na2SO4Evaporative crystallization unit and dissolving tank；Crystallization purity salt is improved and resource rate divides salt method the invention also discloses a kind of, according to c (Cl in high saliferous industrial wastewater‑): c (SO4 2‑), select the specific processing method of high saliferous industrial wastewater.The present invention divide salt system design rationally, can efficient process separate sources, heterogeneity, different impurities content high saliferous industrial wastewater.High saliferous industrial wastewater is handled using this system, divides that salt is more efficient, effect is good, divides salt system stability and capacity of resisting impact load stronger；Since the present invention handles different Industry Waste moisture situations with high salt, the crystal salt yield and purity of this method are higher.
Description
Technical field:
Crystallization purity salt is improved and resource rate divides salt system and method the present invention relates to a kind of, belongs to wastewater treatment neck
Domain.The high saliferous industrial wastewater especially generated in coal chemical industry enterprises production process improves high saliferous industrial wastewater sub-prime salt zero
The crystal salt yield of discharge process technique.
Background technique:
High saliferous industrial wastewater, especially coal chemical industry enterprises were waited in coal oil, ammonia from coal, coal-to-olefin, coal gas
The waste water generated in journey has the characteristics that salt content is high, hardness is high, COD content is high and biochemical is poor.
In numerous high saliferous industrial wastewater sub-prime salt Zero discharge treatment methods, two fraction salt that nanofiltration is coupled with thermal method
Method obtains the approval of insider and industry specialists, and nanofiltration divides salt, is by monovalent ion using Nanofiltration-membrane technique (with Cl-For
It is main) and divalent ion (with SO4 2-Based on) separate, the solution based on monovalent ion and the solution based on divalent ion are formed,
The two is evaporated respectively carries out a point salt；Thermal method divides salt, is to carry out a point salt using the changing rule of various salt solubilities.In actual motion
In the process, both crystallization purity salts for dividing salt method to separate substantially meet industrial salt requirement, but crystal salt yield is insufficient
55%, generate a large amount of carnallites.This part carnallite is named as hazardous waste and is disposed, and increases environmental protection of enterprise pressure and waste water
Processing cost.Therefore, crystal salt yield is improved, carnallite amount is reduced, becomes high saliferous industrial wastewater sub-prime salt zero discharge treatment work
The key of skill.
Summary of the invention:
The first purpose of this invention is to provide a kind of point salt system for improving crystallization purity salt and resource rate.
Second object of the present invention be to provide it is a kind of improve crystallization purity salt and resource rate divide salt method.
The first purpose of this invention is implemented by following technical solution: a kind of point improving crystallization purity salt and resource rate
Salt system comprising nanofiltration conditioning tank, nano-filtration unit, NaCl depth upgrading unit, NaCl evaporative crystallization unit, organic matter degradation
Unit, Na2SO4Depth upgrading unit, Na2SO4Evaporative crystallization unit and dissolving tank；
The nanofiltration conditioning tank respectively with the nano-filtration unit, the organic matter degradation unit, the Na2SO4Depth concentration
Unit is connected by pipeline, is equipped with the first shut-off valve on the pipeline for being connected to the nanofiltration conditioning tank and the nano-filtration unit,
The pipeline for being connected to the nanofiltration conditioning tank and the organic matter degradation unit is equipped with the second shut-off valve, is being connected to the nanofiltration tune
Save pond and the Na2SO4The pipeline of depth upgrading unit is equipped with third shut-off valve；
The nano-filtration unit is connect with the NaCl depth upgrading unit, the NaCl depth upgrading unit and the NaCl
Evaporative crystallization unit is connected by pipeline；
The organic matter degradation unit respectively with the Na2SO4Depth upgrading unit and the Na2SO4Evaporative crystallization unit
It is connected by pipeline, is being connected to the organic matter degradation unit and the Na2SO4The pipeline of depth upgrading unit is equipped with the 4th
Shut-off valve is being connected to the organic matter degradation unit and the Na2SO4The pipeline of evaporative crystallization unit is equipped with the 5th shut-off valve；
The Na2SO4Depth upgrading unit and the Na2SO4Evaporative crystallization unit is connected by pipeline, is being connected to the Na2SO4Depth
Upgrading unit and the Na2SO4Pipeline between evaporative crystallization unit is equipped with the 6th shut-off valve；The Na2SO4Evaporative crystallization
The mixed salt outlet of unit is connect with the dissolving tank, and the dissolving tank is logical with the nanofiltration conditioning tank and the nano-filtration unit respectively
Piping connection is equipped with the 7th shut-off valve on the pipeline for being connected to the dissolving tank and the nanofiltration conditioning tank, described in connection
Dissolving tank and the pipeline of the nano-filtration unit are equipped with the 8th shut-off valve；
The nano-filtration unit respectively with the organic matter degradation unit, the Na2SO4Depth upgrading unit is connected by pipeline
It connects, the 9th shut-off valve is equipped on the pipeline being connected between the nano-filtration unit and the organic matter degradation unit, in connection institute
State nano-filtration unit and the Na2SO4Pipeline between depth upgrading unit is equipped with the tenth shut-off valve.
Nano-filtration unit of the present invention, can be according to the height of intake total dissolved solid, chloride ion, sulfate radical isoconcentration
Determine the combining form of nano-filtration unit.It can be one or more levels nanofiltration, can be one or more snippets nanofiltration, be also possible to level-one
Multistage, one section of multistage or multistage multistage nanofiltration combination；
NaCl depth upgrading unit and Na of the present invention2SO4Depth upgrading unit can be high-pressure flat plate film
(DTRO), electrodialysis (ED), efficiently (high pressure) reverse osmosis, positive permeation unit etc., are also possible to the combination of above-mentioned a few persons.
Organic matter degradation unit of the present invention can be with catalytic ozonation technology, electro-catalytic oxidation technology, surpass
Technology of acoustic wave, plasma technology, light electrolysis-Fenton technology, supercritical oxidation, activated carbon adsorption, macroporous resin adsorption unit,
It can be the combination of above-mentioned a few persons.
NaCl evaporative crystallization unit and Na of the present invention2SO4It is single to can be single effect evaporation crystallization for evaporative crystallization unit
Member, multiple-effect evaporation crystalline element, MVR evaporative crystallization unit etc., are also possible to the combination of above-mentioned a few persons.
Second object of the present invention is implemented by following technical solution: a kind of point improving crystallization purity salt and resource rate
Salt method, high saliferous industrial wastewater after pretreatment are discharged into the quenched tune amount of nanofiltration conditioning tank, then according to described high containing salt worker
C (Cl in industry waste water-): c (SO4 2-), the specific processing method of high saliferous industrial wastewater is selected, is specifically included:
(1) as c (Cl in the high saliferous industrial wastewater-): c (SO4 2-) >=1:2, opens the first shut-off valve, and the height contains
Salt industrial waste water enters nano-filtration unit and carries out nanofiltration point salt treatment, obtains nanofiltration and produces water and nanofiltration concentrated water；The nanofiltration produce water according to
It is secondary to be evaporated crystallization into NaCl depth upgrading unit progress depth concentration, NaCl evaporative crystallization unit, obtain NaCl crystal；
According to the TDS content of the nanofiltration concentrated water, the specific processing method of the nanofiltration concentrated water is selected, is specifically included:
(1.1) as TDS >=100000mg/L of the nanofiltration concentrated water, the 9th shut-off valve, the 5th shut-off valve and the 7th are opened
Shut-off valve, the nanofiltration concentrated water sequentially enter organic matter degradation system and carry out organic matter degradation, Na2SO4Evaporative crystallization unit carries out
Evaporative crystallization obtains Na2SO4Crystal and Na2SO4Evaporate mother liquor, the Na2SO4Evaporation mother liquor continues evaporation and obtains mixed salt, described
Mixed salt is discharged into dissolving tank the quenched tune amount of the nanofiltration conditioning tank that enters after dissolution, after enter back into the nano-filtration unit and divide salt；
(1.2) it as TDS < 100000mg/L of the nanofiltration concentrated water, needs through Na2SO4At depth upgrading unit depth concentration
Na is entered back into after reason2SO4Evaporative crystallization unit is handled；Further according to the COD content of the nanofiltration concentrated water, described in selection
The specific processing method of nanofiltration concentrated water, specifically includes:
(1.2.1) as COD >=500mg/L of the nanofiltration concentrated water, the nanofiltration concentrated water need to be first through organic matter degradation unit
Degradation treatment enters back into Na after the COD being effectively reduced in the nanofiltration concentrated water2SO4Depth upgrading unit depth concentration, most
Enter Na afterwards2SO4Evaporative crystallization unit is evaporated crystallization, it may be assumed that open the 9th shut-off valve, the 4th shut-off valve, the 6th shut-off valve and
7th shut-off valve, the nanofiltration concentrated water sequentially enter organic matter degradation system and carry out organic matter degradation, Na2SO4Depth upgrading unit
Carry out depth concentration, Na2SO4Evaporative crystallization unit is evaporated crystallization, obtains Na2SO4Crystal and Na2SO4Mother liquor is evaporated, it is described
Na2SO4Evaporation mother liquor continues evaporation and obtains mixed salt, and the mixed salt, which is discharged into dissolving tank, enters the nanofiltration conditioning tank tune after dissolution
Matter tune amount, after enter back into the nano-filtration unit and divide salt；
(1.2.2) as COD < 500mg/L of the nanofiltration concentrated water, the nanofiltration concentrated water need to be first through Na2SO4Depth concentration is single
First depth concentration, salt and organic concentration increase, after enter back into organic matter degradation unit degradation treatment, finally enter
Na2SO4Evaporative crystallization unit is evaporated crystallization, it may be assumed that the tenth shut-off valve of opening, the 4th shut-off valve, the 5th shut-off valve and the 7th section
Only valve, the nanofiltration concentrated water sequentially enter Na2SO4Depth upgrading unit progress depth concentration, organic matter degradation system carry out organic
Object degradation, Na2SO4Evaporative crystallization unit is evaporated crystallization, obtains Na2SO4Crystal and Na2SO4Evaporate mother liquor, the Na2SO4
Evaporation mother liquor continues evaporation and obtains mixed salt, and the mixed salt, which is discharged into dissolving tank, enters the quenched tune of nanofiltration conditioning tank after dissolution
Amount, after enter back into the nano-filtration unit and divide salt；
(2) as c (Cl in the high saliferous industrial wastewater-): c (SO4 2-It, need to be according to the high saliferous Industry Waste when) < 1:2
TDS content in water, selects specific processing method, specifically includes:
(2.1) as TDS >=100000mg/L in the high saliferous industrial wastewater, the second shut-off valve and the 5th section are opened
Only valve, the high saliferous industrial wastewater sequentially enter organic matter degradation unit and carry out organic matter degradation, Na2SO4Evaporative crystallization unit
It is evaporated crystallization, obtains Na2SO4Crystal and Na2SO4Evaporate mother liquor, the Na2SO4Evaporation mother liquor continues evaporation and obtains mixed salt,
The mixed salt, which is discharged into dissolving tank after dissolution, enters nano-filtration unit progress nanofiltration point salt treatment, obtains nanofiltration and produces water and nanofiltration
Concentrated water；The nanofiltration production water sequentially enters NaCl depth upgrading unit progress depth concentration, NaCl evaporative crystallization unit is steamed
Hair crystallization, obtains NaCl crystal；The nanofiltration concentrated water returns to the nanofiltration conditioning tank, carries out circulation again and divides salt；
(2.2) it as TDS < 100000mg/L in the high saliferous industrial wastewater, needs through Na2SO4Depth upgrading unit is deep
Na is entered back into after degree concentration2SO4Evaporative crystallization unit is handled；Further according in the high saliferous industrial wastewater
COD content selects the specific processing method of the nanofiltration concentrated water, specifically includes:
(2.2.1) opens the second shut-off valve, the 4th shut-off valve as COD >=500mg/L in the high saliferous industrial wastewater
With the 6th shut-off valve, the high saliferous industrial wastewater sequentially enters the organic matter degradation unit and carries out organic matter degradation, Na2SO4
The concentration of depth upgrading unit depth, the Na2SO4Evaporative crystallization unit is evaporated crystallization, obtains Na2SO4Crystal and Na2SO4
Evaporate mother liquor, the Na2SO4Evaporation mother liquor continues evaporation and obtains mixed salt, after the mixed salt enters dissolving tank dissolution, opening the 8th
Shut-off valve and the first shut-off valve, the dissolved mixed salt enter nano-filtration unit progress nanofiltration and divide salt treatment, obtain nanofiltration
Produce water and nanofiltration concentrated water；The nanofiltration produces water and sequentially enters NaCl depth upgrading unit progress depth concentration, NaCl evaporative crystallization
Unit is evaporated crystallization, obtains NaCl crystal；The nanofiltration concentrated water returns to the nanofiltration conditioning tank, carries out circulation point again
Salt；
(2.2.2) opens third shut-off valve, the 4th shut-off valve as COD < 500mg/L in the high saliferous industrial wastewater
With the 5th shut-off valve, the high saliferous industrial wastewater sequentially enters the Na2SO4Depth upgrading unit depth is concentrated, is described organic
Object degradation unit carries out organic matter degradation, the Na2SO4Evaporative crystallization unit is evaporated crystallization, obtains Na2SO4Crystal and
Na2SO4Evaporate mother liquor, the Na2SO4Evaporation mother liquor, which continues to evaporate, obtains mixed salt, after the mixed salt enters dissolving tank dissolution, beats
The 8th shut-off valve and the first shut-off valve are opened, the dissolved mixed salt enters nano-filtration unit progress nanofiltration and divides salt treatment, obtains
Water and nanofiltration concentrated water are produced to nanofiltration；The nanofiltration produces water and sequentially enters NaCl depth upgrading unit progress depth concentration, NaCl steaming
Hair crystalline element is evaporated crystallization, obtains NaCl crystal；The nanofiltration concentrated water returns to the nanofiltration conditioning tank, carries out again
Circulation divides salt.
Advantages of the present invention: the present invention it is a kind of improve crystallization purity salt and resource rate divide salt system design rationally, can
The high saliferous industrial wastewater of efficient process separate sources, heterogeneity, different impurities content.
The present invention is a kind of to improve crystallization purity salt and resource rate is divided to the salt method to be in " two fraction of nanofiltration+evaporative crystallization
On the basis of salt ", by nanofiltration concentrated water through evaporative crystallization output Na2SO4Evaporation mother liquor later continues evaporative crystallization output mixed salt
(main component is NaCl and Na2SO4), nano-filtration unit front end is flowed back into after then dissolving mixed salt and repeats to divide salt, to enhance
Nano-filtration unit divides salt action.Compared with it will directly evaporate mother liquor reflux to nano-filtration unit front end, in the mixed salt that this method generates
The impurity contents such as organic matter, nitrate anion it is low, impact will not be generated because of reflux and to nano-filtration unit, and cause the impurity to be
Accumulation inside system and to dividing salt to bring adverse effect；Evaporation is continued through or compared with freezing and crystallizing divides salt with mother liquor will be evaporated,
This method can be resistant to very big impact load, will not reduce a point salt effect because of the biggish fluctuating range of influent quality.It should
Method also makes full use of nanofiltration membrane to the efficient rejection effect of organic matter, right by being used cooperatively with organic matter degradation system
Organic matter in nanofiltration concentrated water carries out concentration efficient process, significantly improves crystallization purity salt and crystal salt yield.
Organic matter degradation unit is placed on after nanofiltration divides salt by the present invention, greatly reduces treating capacity, save the cost；In nanofiltration
Divide after salt, most organic is trapped within nanofiltration concentrated water side, and since nanofiltration divides salt, dense discharge reduction causes organic
Object is concentrated at double, therefore organic matter degradation is high-efficient in the present invention, and removal effect is good.
In the present invention, after nanofiltration divides salt for the first time, will according to chlorine ion concentration and sulfate ion concentration in nanofiltration concentrated water,
Evaporation is divided salt to obtain the crystal salt of high-quality or evaporates the mixture of sodium chloride and sodium sulphate by selectivity, then by molten
Solution flows back into nanofiltration front end.The effect that nanofiltration divides salt is enhanced, ensure that a point salt effect, while greatly reducing evaporation and dividing salt
Difficulty and energy consumption.
In the present invention, for the concentration ratio of chloride ion and sulfate ion in salt concentrate to be divided, selective design
Divide concentration and evaporation after salt, or first concentration and evaporation to divide salt in nanofiltration for first nanofiltration, guarantees that nanofiltration divides salt in the case where most preferably dividing salt state, mention
High score salt efficiency and ability.
Detailed description of the invention:
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1, which is that embodiment 1 is a kind of, improves crystallization purity salt and resource rate divides salt system schematic diagram.
In figure: nanofiltration conditioning tank 1, nano-filtration unit 2, NaCl depth upgrading unit 3, NaCl evaporative crystallization unit 4, organic matter
Degradation unit 5, Na2SO4Depth upgrading unit 6, Na2SO4Evaporative crystallization unit 7, dissolving tank 8, the first shut-off valve 9, the second cut-off
Valve 10, third shut-off valve 11, the 4th shut-off valve 12, the 5th shut-off valve 13, the 6th shut-off valve 14, the 7th shut-off valve 15, the 8th section
Only valve 16, the 9th shut-off valve 17, the tenth shut-off valve 18.
Specific embodiment:
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1:
It is a kind of to improve crystallization purity salt and resource rate divides salt system comprising nanofiltration conditioning tank 1, nano-filtration unit 2,
NaCl depth upgrading unit 3, NaCl evaporative crystallization unit 4, organic matter degradation unit 5, Na2SO4Depth upgrading unit 6, Na2SO4
Evaporative crystallization unit 7 and dissolving tank 8；
Nanofiltration conditioning tank 1 respectively with nano-filtration unit 2, organic matter degradation unit 5, Na2SO4Depth upgrading unit 6 passes through pipeline
Connection, connection nanofiltration conditioning tank 1 and nano-filtration unit 2 pipeline on be equipped with the first shut-off valve 9, connection nanofiltration conditioning tank 1 with
The pipeline of organic matter degradation unit 5 is equipped with the second shut-off valve 10, in connection nanofiltration conditioning tank 1 and Na2SO4Depth upgrading unit 6
Pipeline be equipped with third shut-off valve 11；
Nano-filtration unit 2 is connect with NaCl depth upgrading unit 3 by pipeline, and NaCl depth upgrading unit 3 and NaCl evaporate
Crystalline element 4 is connected by pipeline；
Organic matter degradation unit 5 respectively with Na2SO4Depth upgrading unit 6 and Na2SO4Evaporative crystallization unit 7 passes through pipeline
Connection, in connection organic matter degradation unit 5 and Na2SO4The pipeline of depth upgrading unit 6 is equipped with the 4th shut-off valve 12, is being connected to
Organic matter degradation unit 5 and Na2SO4The pipeline of evaporative crystallization unit 7 is equipped with the 5th shut-off valve 13；Na2SO4Depth concentration is single
6 and Na of member2SO4Evaporative crystallization unit 7 is connected by pipeline, in connection Na2SO4Depth upgrading unit 6 and Na2SO4Evaporative crystallization
Pipeline between unit 7 is equipped with the 6th shut-off valve 14；Na2SO4The mixed salt outlet of evaporative crystallization unit 7 is connect with dissolving tank 8,
Dissolving tank 8 is connect with nanofiltration conditioning tank 1 and nano-filtration unit 2 by pipeline respectively, in connecting dissolution slot 8 and nanofiltration conditioning tank 1
Pipeline is equipped with the 7th shut-off valve 15, and the 8th shut-off valve 16 is equipped on connecting dissolution slot 8 and the pipeline of nano-filtration unit 2；
Nano-filtration unit 2 respectively with organic matter degradation unit 5, Na2SO4Depth upgrading unit 6 is connected by pipeline, is being connected to
Pipeline between nano-filtration unit 2 and organic matter degradation unit 5 is equipped with the 9th shut-off valve 17, in connection nano-filtration unit 2 and Na2SO4
Pipeline between depth upgrading unit 6 is equipped with the tenth shut-off valve 18.
As a kind of specific embodiment, nano-filtration unit 2 uses the combining form of two-stage nanofiltration.
As a kind of specific embodiment, NaCl depth upgrading unit 3 and Na2SO4Depth upgrading unit 6 is all made of can be with
It is high-pressure flat plate film (DTRO).
As a kind of specific embodiment, organic matter degradation unit 5 is three-dimensional integrated using ozone, ultrasonic wave, ultraviolet light
The combination of advanced oxidation unit.
As a kind of specific embodiment, NaCl evaporative crystallization unit 4 and Na2SO4Evaporative crystallization unit 7 is all made of evaporation
Crystalline element 7.
Embodiment 2:
Certain coal-to-olefin item is handled using a kind of point salt system for improving crystallization purity salt and resource rate described in embodiment 1
Purpose waste water,
Waste water water Q:10m3/ h, COD:60mg/L, TDS:15503mg/L, Cl-: 4695mg/L, SO4 2-: 5300mg/
L, total hardness: 2101mg/L, silica: 35mg/L, turbidity: 4NTU.
After front end pretreatment and preliminary film concentration, ion exchange resin, into the high saliferous Industry Waste of nanofiltration conditioning tank 1
Water water quality indicator are as follows: TDS=75011mg/L, Cl-=22990mg/L, SO4 2-=25020mg/L, total hardness 0.5mg/L,
COD=315mg/L, pH 7.5, flow Q=2.0m3/h。
The first shut-off valve 9 is opened, high saliferous industrial wastewater enters nano-filtration unit 2 and carries out nanofiltration processing, obtains nanofiltration and produces water
With nanofiltration concentrated water；
Wherein, nanofiltration produces water TDS=43015mg/L, total hardness 0mg/L, Cl-=26052mg/L, SO4 2-=82mg/
L, COD=120mg/L, nanofiltration produce water flow Q=1.36m3/h；Nanofiltration concentrated water TDS=115011mg/L, total hardness 2.5mg/L,
SO4 2-=66001mg/L, Cl-=12500mg/L, COD=685mg/L, nanofiltration concentrated water flow 0.64m3/h。
Nanofiltration production water sequentially enters the progress of NaCl depth upgrading unit 3 depth concentration, NaCl evaporative crystallization unit 4 is steamed
Hair crystallization produces to obtain NaCl crystal salt, and NaCl depth upgrading unit 3 uses DTRO system, and NaCl evaporative crystallization unit 4 uses MVR
Evaporative crystallization unit, the NaCl crystallization purity salt produced is 99.7%, meets " Nacl " (GB/T 5462-2015) " purification work
Industry salt level-one " standard.
The 9th shut-off valve 17 and the 5th shut-off valve 13 are opened, nanofiltration concentrated water enters organic matter degradation unit 5 and carries out organic matter
Degradation, the organic matter degradation unit three-dimensional integrated using ozone, ultrasonic wave, ultraviolet light of organic matter degradation unit 5；It is discharged TDS=
115011mg/L, COD=101mg/L then enter Na2SO4Evaporative crystallization unit 7 is evaporated crystallization, at a temperature of 105 DEG C
Obtain Na2SO4Crystal and Na2SO4Evaporate mother liquor, Na2SO4Evaporative crystallization system is crystallized using triple effect evaporation；The sodium sulphate knot produced
Brilliant purity salt is 98.8%, meets " industrial anhydrous sodium sulfate " (GB/T 6009-2014) " II class Grade A " standard；
Na2SO4Evaporation mother liquor continues evaporation to obtain main component to be Na2SO4With the mixed salt of NaCl, mixed salt is discharged into dissolving tank 8
It is interior to enter the quenched tune amount of nanofiltration conditioning tank 1 after the dissolution of system total yield water, it is again introduced into this system circulation and divides salt；
By 72 hours continuous operations, 720 tons of water are handled, obtains 5.3 tons of NaCl crystal salt, Na2SO4Crystal salt 4.5
Ton, crystal salt relative productivity (crystal salt relative productivity=NaCl crystal salt and Na2SO4Crystal salt product volume/salinity of always intaking) be
90.7%.
Embodiment 3:
Certain coal-to-olefin item is handled using a kind of point salt system for improving crystallization purity salt and resource rate described in embodiment 1
Purpose waste water,
Waste water water Q:10m3/ h, COD:65mg/L, TDS:10180mg/L, Cl:3065mg/L, SO4 2-: 3802mg/
L, total hardness: 2489mg/L, silica: 47mg/L, turbidity: 3NTU, through front end pretreatment and preliminary film concentration, ion exchange
After resin, into the high saliferous industrial wastewater water quality indicator of nanofiltration conditioning tank 1 are as follows: TDS=55220mg/L, Cl-=16621mg/
L, SO4 2-=18519mg/L, total hardness 0.5mg/L, COD=335mg/L, pH=7.5, flow Q=1.2m3/h。
The first shut-off valve 9 is opened, high saliferous industrial wastewater enters nano-filtration unit 2 and carries out nanofiltration processing, obtains nanofiltration and produces water
With nanofiltration concentrated water；
Wherein, nanofiltration produces water TDS=30560mg/L, total hardness 0mg/L, Cl-=19775mg/L, SO4 2-=52mg/
L, COD=125mg/L, nanofiltration produce water flow Q=0.815m3/h；Nanofiltration concentrated water TDS=80700mg/L, total hardness 2.55mg/
L, SO4 2-=54022.9mg/L, Cl-=9945mg/L, COD=795mg/L, nanofiltration concentrated water flow 0.385m3/h。
Nanofiltration production water sequentially enters the progress of NaCl depth upgrading unit 3 depth concentration, NaCl evaporative crystallization unit 4 is steamed
Hair crystallization produces to obtain NaCl crystal salt, and NaCl depth upgrading unit 3 uses DTRO system, and NaCl evaporative crystallization unit 4 uses MVR
Evaporative crystallization unit, the NaCl crystallization purity salt produced is 99.7%, meets " Nacl " (GB/T 5462-2015) " purification work
Industry salt level-one " standard.
Meanwhile it is dense to open the 9th shut-off valve 17, the 4th shut-off valve 12, the 6th shut-off valve 14 and the 7th shut-off valve 15, nanofiltration
Water enters organic matter degradation unit 5 and carries out organic matter degradation, and organic matter degradation unit 5 is three-dimensional using ozone, ultrasonic wave, ultraviolet light
The organic matter degradation unit of one；It is discharged TDS=80500mg/L, COD=105mg/L, then enters Na2SO4Depth concentration is single
Member 6 carries out depth concentration, Na2SO4Depth upgrading unit 6 uses DTRO system, is discharged TDS=181350mg/L, COD=
225mg/L finally enters Na2SO4Evaporative crystallization unit 7 is evaporated crystallization, obtains Na at a temperature of 105 DEG C2SO4Crystal and
Na2SO4Evaporate mother liquor, Na2SO4Evaporative crystallization system is crystallized using triple effect evaporation；The sulfate crystal purity salt produced is
98.7%, meet " industrial anhydrous sodium sulfate " (GB/T 6009-2014) " II class Grade A " standard；
Na2SO4Evaporation mother liquor continues evaporation to obtain main component to be Na2SO4With the mixed salt of NaCl, mixed salt is discharged into dissolving tank 8
It is interior to enter the quenched tune amount of nanofiltration conditioning tank 1 after the dissolution of system total yield water, it is again introduced into this system circulation and divides salt；
By 72 hours continuous operations, 720 tons of water are handled, obtains 3.1 tons of NaCl crystal salt, Na2SO4Crystal salt 3.4
Ton, crystal salt relative productivity (crystal salt relative productivity=NaCl crystal salt and Na2SO4Crystal salt product volume/salinity of always intaking) be
89%.
Embodiment 4:
Certain coal-to-olefin item is handled using a kind of point salt system for improving crystallization purity salt and resource rate described in embodiment 1
Purpose waste water,
Waste water water Q:20m3/ h, COD:35mg/L, TDS:101850mg/L, Cl-: 3055mg/L, SO4 2-: 3800mg/
L, total hardness: 2545mg/L, silica: 42mg/L, turbidity: 2.5NTU.It is handed over through front end pretreatment and preliminary film concentration, ion
After changing resin, into the high saliferous industrial wastewater water quality indicator of nanofiltration conditioning tank 1 are as follows: TDS=54980mg/L, Cl-=
16211mg/L, SO4 2-=18513mg/L, total hardness 0.5mg/L, COD=179mg/L, pH=7.5, flow Q=
2.4m3/h。
Open the first shut-off valve 9, high saliferous industrial wastewater enters nano-filtration unit and carries out nanofiltration processing, obtain nanofiltration produce water and
Nanofiltration concentrated water；
Wherein, nanofiltration produces water TDS=30490mg/L, total hardness 0mg/L, Cl-=19735mg/L, SO4 2-=
51.5mg/L, COD=63mg/L, nanofiltration produce water flow Q=1.63m3/h；Nanofiltration concentrated water TDS=80505mg/L, total hardness
2.5mg/L, SO4 2-=54012.5mg/L, Cl-=8751mg/L, COD=441mg/L, nanofiltration concentrated water flow 0.77m3/h。
Nanofiltration production water sequentially enters the progress of NaCl depth upgrading unit 3 depth concentration, NaCl evaporative crystallization unit 4 is steamed
Hair crystallization produces to obtain NaCl crystal salt, and NaCl depth upgrading unit 3 uses DTRO system, and NaCl evaporative crystallization unit 4 uses MVR
Evaporative crystallization unit, the NaCl crystallization purity salt produced is 99.8%, meets " Nacl " (GB/T 5462-2015) " purification work
Industry salt level-one " standard.
The tenth shut-off valve 18, the 4th shut-off valve 12, the 5th shut-off valve 13 and the 7th shut-off valve 15 are opened, nanofiltration concentrated water enters
Na2SO4Depth upgrading unit 6 carries out depth concentration, Na2SO4Depth upgrading unit 6 uses DTRO system, is discharged TDS=
181350mg/L, COD=789mg/L then enter organic matter degradation unit 5 and carry out organic matter degradation, organic matter degradation unit 5
Using the three-dimensional integrated organic matter degradation unit of ozone, ultrasonic wave, ultraviolet light；It is discharged TDS=181350mg/L, COD=
103mg/L finally enters Na2SO4Evaporative crystallization unit 7 is evaporated crystallization, obtains Na at a temperature of 105 DEG C2SO4Crystal and
Na2SO4Evaporate mother liquor, Na2SO4Evaporative crystallization system is crystallized using triple effect evaporation；The sulfate crystal purity salt produced is
98.9%, meet " industrial anhydrous sodium sulfate " (GB/T 6009-2014) " II class Grade A " standard；
Na2SO4Evaporation mother liquor continues evaporation to obtain main component to be Na2SO4With the mixed salt of NaCl, mixed salt is discharged into dissolving tank 8
It is interior to enter the quenched tune amount of nanofiltration conditioning tank 1 after the dissolution of system total yield water, it is again introduced into this system circulation and divides salt；
By 36 hours continuous operations, 720 tons of water are handled, obtains 3.1 tons of NaCl crystal salt, Na2SO4Crystal salt 3.5
Ton, crystal salt relative productivity (crystal salt relative productivity=NaCl crystal salt and Na2SO4Crystal salt product volume/salinity of always intaking) be
90.3%.
Embodiment 5:
Certain coal to olefin project is handled using a kind of point salt system for improving crystallization purity salt and resource rate of embodiment 1
Waste water,
Waste water water Q:6m3/ h, COD:605mg/L, TDS:110150mg/L, Cl-: 18055mg/L, SO4 2-:
52005mg/L, total hardness: 3009mg/L, silica: 49mg/L, turbidity: 3.5NTU.
After front end pretreatment and preliminary film concentration, ion exchange resin, the height into nanofiltration conditioning tank 11 contains salt industrial
Waste water quality index are as follows: TDS=103220mg/L, Cl-=18031mg/L, SO4 2-=52009mg/L, total hardness 0.5mg/
L, COD=585mg/L, pH=7.5, flow Q=6m3/h。
The second shut-off valve 10 and the 5th shut-off valve 13 are opened, high saliferous industrial wastewater enters the progress of organic matter degradation unit 5
Organic matter degradation, the organic matter degradation unit three-dimensional integrated using ozone, ultrasonic wave, ultraviolet light of organic matter degradation unit 5, water outlet
TDS=103220mg/L, Cl-=18031mg/L, SO4 2-=52009mg/L, total hardness 0.5mg/L, COD=85mg/L, and
Enter Na afterwards2SO4Evaporative crystallization unit 7 is evaporated crystallization, obtains Na at a temperature of 105 DEG C2SO4Crystal and Na2SO4Evaporation is female
Liquid；Na2SO4Evaporation mother liquor continues evaporation and obtains mixed salt, and mixed salt enters nano-filtration unit 2 after the dissolution of system total yield water and carries out nanofiltration
Divide salt, solution TDS=75005mg/L, Cl after mixed salt dissolution-=34031mg/L, SO4 2-=14009mg/L, pH 7.3, flow
For Q=3.2m3/h。
The nanofiltration obtained after nanofiltration divides salt produces water and nanofiltration concentrated water, and nanofiltration produces water TDS=61560mg/L, and total hardness is
0mg/L, Cl-=37725mg/L, SO4 2-=95mg/L, COD=25mg/L, nanofiltration produce water flow 2.4m3/h.Nanofiltration concentrated water TDS
=110701mg/L, total hardness 2.5mg/L, SO4 2-=56305mg/L, Cl-=16545mg/L, COD=415mg/L, nanofiltration are dense
Water flow 0.8m3/ h, nanofiltration concentrated water return to nanofiltration conditioning tank 1 and carry out quenched tune amount, and then circulation divides salt；Nanofiltration produce water successively into
Enter NaCl depth upgrading unit 3 and carry out depth concentration, NaCl evaporative crystallization unit 4 to be evaporated crystallization, produces to obtain NaCl crystal salt,
NaCl depth upgrading unit 3 uses DTRO system, and NaCl evaporative crystallization unit 4 uses MVR evaporative crystallization unit, the NaCl produced
Crystallizing purity salt is 99.3%, meets " Nacl " (GB/T 5462-2015) " refining industrial salt level-one " standard；The sulphur produced
Sour sodium crystallization purity salt is 99.1%, meets " industrial anhydrous sodium sulfate " (GB/T 6009-2014) " II class Grade A " standard.
By 72 hours continuous operations, 432 tons of water are handled, obtains 9.8 tons of NaCl crystal salt, Na2SO4Crystal salt 30.2
Ton, crystal salt relative productivity (crystal salt relative productivity=NaCl crystal salt and Na2SO4Crystal salt product volume/salinity of always intaking) be
89.4%.
Embodiment 6:
Certain coal to olefin project is handled using a kind of point salt system for improving crystallization purity salt and resource rate of embodiment 1
Waste water,
Waste water water Q:10m3/ h, COD:605mg/L, TDS:31750mg/L, Cl-: 6058mg/L, SO4 2-:
15802mg/L, total hardness: 608mg/L, silica: 30mg/L, turbidity: 3.5NTU.
After front end pretreatment and preliminary film concentration, ion exchange resin, the height into nanofiltration conditioning tank 11 contains salt industrial
Waste water quality index are as follows: TDS:30850mg/L, Cl-: 6163mg/L, SO4 2-: 15407mg/L, total hardness 0.5mg/L, COD
=575mg/L, pH 7.1, flow Q=10m3/h。
The second shut-off valve 10, the 4th shut-off valve 12 and the 6th shut-off valve 14 are opened, high saliferous industrial wastewater has initially entered
Machine object unit 5 of degrading carries out organic matter degradation, organic matter degradation unit 5 using ozone, ultrasonic wave, ultraviolet light is three-dimensional integrated has
Machine object degradation unit, is discharged TDS=30850mg/L, COD=85mg/L, then enters Na2SO4Depth upgrading unit 6 carries out depth
Degree concentration, Na2SO4Depth upgrading unit 6 uses DTRO system, is discharged TDS=165345mg/L, COD=415mg/L, most laggard
Enter Na2SO4Evaporative crystallization unit 7 is evaporated crystallization, obtains Na at a temperature of 105 DEG C2SO4Crystal and Na2SO4Mother liquor is evaporated,
Na2SO4Evaporative crystallization system is crystallized using triple effect evaporation；The sulfate crystal purity salt produced is 98.9%, is met " industrial anhydrous
Sodium sulphate " (GB/T 6009-2014) " II class Grade A " standard；
Na2SO4Evaporation mother liquor continues evaporation and obtains mixed salt, Na2SO4Evaporation mother liquor continues evaporation and obtains main component and be
Na2SO4With the mixed salt of NaCl, mixed salt, which is discharged into dissolving tank 8, divides salt into the progress nanofiltration of nano-filtration unit 2 through the dissolution of system total yield water,
Solution TDS=45005mg/L, Cl after mixed salt dissolution-=20842mg/L, SO4 2-=8109mg/L, pH=7.3, flow Q=
2.6m3/h。
The nanofiltration obtained after nanofiltration divides salt produces water and nanofiltration concentrated water, and nanofiltration produces water TDS=33960mg/L, and total hardness is
0mg/L, Cl-=21718mg/L, SO4 2-=85mg/L, COD=165mg/L, nanofiltration produce water flow Q=2.1m3/h.Nanofiltration concentrated water
TDS=95705mg/L, total hardness 2.5mg/L, SO4 2-=46605mg/L, Cl-=17045mg/L, COD=615mg/L, nanofiltration
Concentrated water flow Q=0.45m3/ h, nanofiltration concentrated water return to nanofiltration conditioning tank 1 and carry out quenched tune amount, and then circulation divides salt；Nanofiltration produces water
It sequentially enters NaCl depth upgrading unit 3 and carries out depth concentration, NaCl evaporative crystallization unit 4 and be evaporated crystallization, produce to obtain NaCl
Crystal salt, NaCl depth upgrading unit 3 use DTRO system, and NaCl evaporative crystallization unit 4 uses MVR evaporative crystallization unit, produce
The NaCl crystallization purity salt obtained is 99.7%, meets " Nacl " (GB/T 5462-2015) " refining industrial salt level-one " standard.
By 72 hours continuous operations, 720 tons of water are handled, obtains 6.1 tons of NaCl crystal salt, Na2SO4Crystal salt 14.4
Ton, crystal salt relative productivity (crystal salt relative productivity=NaCl crystal salt and Na2SO4Crystal salt product volume/salinity of always intaking) be
92.0%.
Embodiment 7:
Certain coal to olefin project is handled using a kind of point salt system for improving crystallization purity salt and resource rate of embodiment 1
Waste water,
Waste water water Q:10m3/ h, COD:125mg/L, TDS:31305mg/L, Cl-: 6102mg/L, SO4 2-:
14975mg/L, total hardness: 605mg/L, silica: 33mg/L, turbidity: 3.5NTU.
After front end pretreatment and preliminary film concentration, ion exchange resin, the height into nanofiltration conditioning tank 11 contains salt industrial
Waste water quality index are as follows: TDS:31215mg/L, Cl-: 6165mg/L, SO4 2-: 14807mg/L, total hardness 0.5mg/L, COD
=125mg/L, pH 7.4, flow Q=10m3/h。
Third shut-off valve 11, the 4th shut-off valve 12 and the 5th shut-off valve 13, high saliferous industrial wastewater is opened to initially enter
Na2SO4Depth upgrading unit 6 carries out depth concentration, Na2SO4Depth upgrading unit 6 uses DTRO system, is discharged TDS=
175035mg/L, COD=635mg/L；Then enter organic matter degradation unit 5 and carries out organic matter degradation, organic matter degradation unit 5
Using the three-dimensional integrated organic matter degradation unit of ozone, ultrasonic wave, ultraviolet light, it is discharged TDS=175035mg/L, COD=89mg/
L；Finally enter Na2SO4Evaporative crystallization unit 7 is evaporated crystallization, obtains Na at a temperature of 105 DEG C2SO4Crystal and Na2SO4It steams
Send out mother liquor, Na2SO4Evaporative crystallization system is crystallized using triple effect evaporation；The sulfate crystal purity salt produced is 98.7%, meets " work
Industry anhydrous sodium sulfate " (GB/T 6009-2014) " II class Grade A " standard；
Na2SO4Evaporation mother liquor continues evaporation and obtains mixed salt, Na2SO4Evaporation mother liquor continues evaporation and obtains main component and be
Na2SO4With the mixed salt of NaCl, mixed salt, which is discharged into dissolving tank 8, divides salt into the progress nanofiltration of nano-filtration unit 2 through the dissolution of system total yield water,
Solution TDS=46105mg/L, Cl after mixed salt dissolution-=21335mg/L, SO4 2-=8205mg/L, pH 7.2, flow Q=
2.6m3/h。
The nanofiltration obtained after nanofiltration divides salt produces water and nanofiltration concentrated water, and nanofiltration produces water TDS=34135mg/L, and total hardness is
0mg/L, Cl-=21833mg/L, SO4 2-=87mg/L, COD=45mg/L, nanofiltration produce water flow Q=2.1m3/h；Nanofiltration concentrated water
TDS=93908mg/L, total hardness 2.5mg/L, SO4 2-=46816mg/L, Cl-=17352mg/L, COD=315mg/L, nanofiltration
Concentrated water flow Q=0.45m3/h；Nanofiltration concentrated water returns to nanofiltration conditioning tank 1 and carries out quenched tune amount, and then circulation divides salt；Nanofiltration produces water
It sequentially enters NaCl depth upgrading unit 3 and carries out depth concentration, NaCl evaporative crystallization unit 4 and be evaporated crystallization, produce to obtain NaCl
Crystal salt, NaCl depth upgrading unit 3 use DTRO system, and NaCl evaporative crystallization unit 4 uses MVR evaporative crystallization unit, produce
The NaCl crystallization purity salt obtained is 99.7%, meets " Nacl " (GB/T 5462-2015) " refining industrial salt level-one " standard.
By 72 hours continuous operations, 720 tons of water are handled, obtains 6.1 tons of NaCl crystal salt, Na2SO4Crystal salt 14.2
Ton, crystal salt relative productivity (crystal salt relative productivity=NaCl crystal salt and Na2SO4Crystal salt product volume/salinity of always intaking) be
93.4%.
The present invention is a kind of to improve crystallization purity salt and resource rate is divided to the salt method to be in " two fraction of nanofiltration+evaporative crystallization
On the basis of salt ", by nanofiltration concentrated water through evaporative crystallization output Na2SO4Evaporation mother liquor later continues evaporative crystallization output mixed salt
(main component is NaCl and Na2SO4), nano-filtration unit front end is flowed back into after then dissolving mixed salt and repeats to divide salt, to enhance
Nano-filtration unit divides salt action.Compared with it will directly evaporate mother liquor reflux to nano-filtration unit front end, in the mixed salt that this method generates
The impurity contents such as organic matter, nitrate anion it is low, impact will not be generated because of reflux and to nano-filtration unit, and cause the impurity to be
Accumulation inside system and to dividing salt to bring adverse effect；Evaporation is continued through or compared with freezing and crystallizing divides salt with mother liquor will be evaporated,
This method can be resistant to very big impact load, will not reduce a point salt effect because of the biggish fluctuating range of influent quality.It should
Method also makes full use of nanofiltration membrane to the efficient rejection effect of organic matter, right by being used cooperatively with organic matter degradation system
Organic matter in nanofiltration concentrated water carries out concentration efficient process, it is found that crystallization purity salt produced by the invention and production from embodiment
Rate is higher.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (2)
- Crystallization purity salt is improved and resource rate divides salt system 1. a kind of, which is characterized in that it includes nanofiltration conditioning tank, nanofiltration Unit, NaCl depth upgrading unit, NaCl evaporative crystallization unit, organic matter degradation unit, Na2SO4Depth upgrading unit, Na2SO4Evaporative crystallization unit and dissolving tank；The nanofiltration conditioning tank respectively with the nano-filtration unit, the organic matter degradation unit, the Na2SO4Depth upgrading unit Connection；The nanofiltration of the nano-filtration unit produces water side and connect with the NaCl depth upgrading unit, the NaCl depth upgrading unit and The NaCl evaporative crystallization unit connection；The organic matter degradation unit respectively with the Na2SO4Depth upgrading unit and the Na2SO4The connection of evaporative crystallization unit； The Na2SO4Depth upgrading unit and the Na2SO4The connection of evaporative crystallization unit；The Na2SO4The mixed salt of evaporative crystallization unit Outlet is connect with the dissolving tank, and the dissolving tank is connect with the nanofiltration conditioning tank and the nano-filtration unit respectively；The nanofiltration concentrated water side of the nano-filtration unit respectively with the organic matter degradation unit, the Na2SO4Depth upgrading unit connects It connects.
- 2. the method for crystallizing point salt system of purity salt and resource rate and carrying out point salt is improved using a kind of described in claim 1, It is characterized in that, high saliferous industrial wastewater after pretreatment is discharged into the quenched tune amount of nanofiltration conditioning tank, then contained according to the height C (Cl in salt industrial waste water-): c (SO4 2-), the specific processing method of high saliferous industrial wastewater is selected, is specifically included:(1) as c (Cl in the high saliferous industrial wastewater-): c (SO4 2-) >=1:2, the high saliferous industrial wastewater is by nanofiltration Reason obtains nanofiltration and produces water and nanofiltration concentrated water；The nanofiltration produces water and successively passes through depth concentration, evaporative crystallization, obtains NaCl crystal；Then according to the TDS content of the nanofiltration concentrated water, the specific processing method of the nanofiltration concentrated water is selected, is specifically included:(1.1) as TDS >=100000mg/L of the nanofiltration concentrated water, the nanofiltration concentrated water successively passes through organic matter degradation and evaporation Crystallization, obtains Na2SO4Crystal and Na2SO4Evaporate mother liquor, the Na2SO4Evaporation mother liquor continues evaporation and obtains mixed salt, the mixed salt The nanofiltration conditioning tank is flowed back into after dissolving, after enter back into the nano-filtration unit and divide salt；(1.2) as TDS < 100000mg/L of the nanofiltration concentrated water, further according to the COD content of the nanofiltration concentrated water, selection The specific processing method of the nanofiltration concentrated water, specifically includes:(1.2.1) as COD >=500mg/L of the nanofiltration concentrated water, it is dense that the nanofiltration concentrated water successively passes through organic matter degradation, depth Contracting and evaporative crystallization, obtain Na2SO4Crystal and Na2SO4Evaporate mother liquor, the Na2SO4Evaporation mother liquor continues evaporation and obtains mixed salt, Flow back into the nanofiltration conditioning tank after mixed salt dissolution, after enter back into the nano-filtration unit and divide salt；(1.2.2) as COD < 500mg/L of the nanofiltration concentrated water, the nanofiltration concentrated water successively passes through depth concentration, organic matter drops Solution and evaporative crystallization, obtain Na2SO4Crystal and Na2SO4Evaporate mother liquor, the Na2SO4Evaporation mother liquor continues evaporation and obtains mixed salt, Flow back into the nanofiltration conditioning tank after mixed salt dissolution, after enter back into the nano-filtration unit and divide salt；(2) as c (Cl in the high saliferous industrial wastewater-): c (SO4 2-It, need to be according in the high saliferous industrial wastewater when) < 1:2 TDS content selects specific processing method, specifically includes:(2.1) as TDS >=100000mg/L in the high saliferous industrial wastewater, the high saliferous industrial wastewater successively passes through Organic matter degradation and evaporative crystallization, obtain Na2SO4Crystal and Na2SO4Evaporate mother liquor, the Na2SO4Evaporation mother liquor continues to evaporate Mixed salt is obtained, the mixed salt enters nano-filtration unit progress nanofiltration and divides salt treatment, obtains nanofiltration and produce water and nanofiltration concentrated water；It is described Nanofiltration produces water and successively passes through depth concentration and evaporative crystallization, obtains NaCl crystal；The nanofiltration concentrated water returns to the nanofiltration tune Pond is saved, circulation is carried out and divides salt；(2.2) as TDS < 100000mg/L in the high saliferous industrial wastewater, further according to the high saliferous industrial wastewater In COD content, select the specific processing method of the nanofiltration concentrated water, specifically include:(2.2.1) as COD >=500mg/L in the high saliferous industrial wastewater, the high saliferous industrial wastewater is successively by having The degradation of machine object, depth concentration and evaporative crystallization, obtain Na2SO4Crystal and Na2SO4Evaporate mother liquor, the Na2SO4Evaporate mother liquor after Continuous evaporation obtains mixed salt, and the mixed salt enters nano-filtration unit progress nanofiltration and divides salt treatment, obtains nanofiltration production water and nanofiltration is dense Water；The nanofiltration produces water and successively passes through depth concentration and evaporative crystallization, obtains NaCl crystal；The nanofiltration concentrated water is described in Nanofiltration conditioning tank carries out circulation and divides salt；(2.2.2) successively passes through depth when COD < 500mg/L in the high saliferous industrial wastewater, the high saliferous industrial wastewater Concentration, organic matter degradation and evaporative crystallization, obtain Na2SO4Crystal and Na2SO4Evaporate mother liquor, the Na2SO4Mother liquor is evaporated to continue Evaporation obtains mixed salt, and the mixed salt enters nano-filtration unit progress nanofiltration and divides salt treatment, obtains nanofiltration and produce water and nanofiltration concentrated water； The nanofiltration produces water and successively passes through depth concentration and evaporative crystallization, obtains NaCl crystal；The nanofiltration concentrated water is received back to described Conditioning tank is filtered, circulation is carried out and divides salt.
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| CN112591973A (en) * | 2020-12-25 | 2021-04-02 | 淄博格瑞水处理工程有限公司 | Reclaimed water recycling zero-emission system |
| CN112624505A (en) * | 2020-12-17 | 2021-04-09 | 内蒙古久科康瑞环保科技有限公司 | Treatment method and system for evaporation mother liquor of high-salt-content wastewater |
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