CN208667421U - A kind of high-salinity wastewater zero-emission processing unit based on nanofiltration membrane allotment - Google Patents
A kind of high-salinity wastewater zero-emission processing unit based on nanofiltration membrane allotment Download PDFInfo
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- CN208667421U CN208667421U CN201821122885.2U CN201821122885U CN208667421U CN 208667421 U CN208667421 U CN 208667421U CN 201821122885 U CN201821122885 U CN 201821122885U CN 208667421 U CN208667421 U CN 208667421U
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- 239000002351 wastewater Substances 0.000 title claims abstract description 80
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 79
- 239000012528 membrane Substances 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 119
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 116
- 239000013078 crystal Substances 0.000 claims abstract description 64
- 238000002425 crystallisation Methods 0.000 claims abstract description 55
- 239000011780 sodium chloride Substances 0.000 claims abstract description 55
- 150000003839 salts Chemical class 0.000 claims abstract description 51
- 230000008025 crystallization Effects 0.000 claims abstract description 49
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 75
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 63
- 238000001223 reverse osmosis Methods 0.000 claims description 50
- 239000007832 Na2SO4 Substances 0.000 claims description 40
- 238000007254 oxidation reaction Methods 0.000 claims description 33
- 238000000108 ultra-filtration Methods 0.000 claims description 33
- 230000003647 oxidation Effects 0.000 claims description 32
- 239000012452 mother liquor Substances 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 14
- 238000000909 electrodialysis Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000009287 sand filtration Methods 0.000 claims description 7
- 238000009298 carbon filtering Methods 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 abstract description 24
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 101
- 230000008569 process Effects 0.000 description 47
- 235000011152 sodium sulphate Nutrition 0.000 description 35
- 239000013505 freshwater Substances 0.000 description 25
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 18
- 239000012267 brine Substances 0.000 description 17
- 239000002699 waste material Substances 0.000 description 17
- 238000011084 recovery Methods 0.000 description 13
- 208000028659 discharge Diseases 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 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
- 238000005660 chlorination reaction Methods 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000010413 mother solution Substances 0.000 description 6
- 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 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
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- 241001529739 Prunella <angiosperm> Species 0.000 description 4
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- 229920002647 polyamide Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
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- 230000000087 stabilizing effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 230000004520 agglutination Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 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 description 1
- 239000002245 particle Substances 0.000 description 1
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- 238000007639 printing Methods 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The utility model relates to a kind of high-salinity wastewater zero-emission processing units based on nanofiltration membrane mixing system.It include: pretreatment system (1), for carrying out pretreatment removal of impurities to high-salt wastewater；Concentration systems (2) are connected to pretreatment system (1), and the waste water for obtaining to pretreatment system (1) carries out concentration；Melded system (3) is connected to concentration systems (2), for carrying out sofening treatment to the waste water after concentration；Nanofiltration membrane (4) is connected to melded system (3), for the separation for producing water and carrying out a divalent salts after sofening treatment；Sulfate crystal system (5) is connected to the dope side of nanofiltration membrane (4), for obtaining Na to nanofiltration dope crystallization treatment2SO4；Sodium chloride crystal system (6) is connected to the light liquid side of nanofiltration membrane (4), for obtaining NaCl to the light liquid crystallization treatment of nanofiltration.
Description
Technical field
The utility model relates to a kind of high-salinity wastewater zero-emission processing units based on nanofiltration membrane allotment, belong to water process skill
Art field.
Background technique
The waste water of the discharges such as paper industry, printing and dyeing industry, chemical engineering industry, pharmaceuticals industry contains certain density inorganic
Salt, the technique for all referring to how to separate inorganic salts from waste water in wastewater zero discharge treatment process.For brine waste zero
Discharge reduces COD and SS using advanced oxidation pretreatment, is concentrated on this basis using reverse osmosis membrane, with cycles of concentration
Rising, the hardness in waste water also gradually rises." two alkaline process " or " resin tenderizer " removing can be used in waste water after concentrated
Hardness in waste water.The waste water of hardness is removed after the techniques such as reverse osmosis or electrodialysis are further concentrated, is tied using evaporation
Brilliant technique obtains Nacl.The clear water that film concentration process generates is used for each production workshop section according to water quality difference.Such brine waste
Technique of zero discharge Chinese utility model patent (CN103508602A, CN104071808A) is it has been reported that but in these patents
It is not directed to how to realize that the separation problem of a divalent salts, obtained carnallite are difficult to resource utilization.
Brine waste zero emission technique is divided into circulation pretreatment, circulation minimizing and zero by Chinese patent CN105540972A
Three parts of exhaust unit.The separation of sal prunella is realized during evaporative crystallization technique.The technique is mainly in brine waste
Monovalent salt and the biggish system of divalent salts concentration difference, can be obtained by controlling the operating condition of crystallization processes technical grade monovalent salt and
Divalent salts, since industrial wastewater complicated component and monovalent salt and divalent salts concentration difference are difficult to meet the separation of sal prunella, this is specially
The restricted application of benefit.
Chinese patent CN104370405A carries out a point salt treatment to high concentration salt water using nanofiltration, by nanofiltration fresh water into
Regenerating softener is used for after row concentration.Nanofiltration concentrated water obtains solid content for evaporative crystallization, and the divalent salts that can get high-purity produce
Object, but the fresh water of nanofiltration does not do concentrate and obtains monovalence product salt, causes enrichment in the outlet or system of this part brine waste, it should
Patent addresses only the problem of part salt utilizes.
Utility model content
The technical problem to be solved by the utility model is to for the concentration ratio of sodium chloride and sodium sulphate in brine waste
Be not suitable for using method for crystallising separation the problem of, using nanofiltration technique in brine waste monovalent salt and divalent salinity carry out
It adjusts, waste water of the nanofiltration membrane after proportion adjustment is further concentrated using reverse osmosis or electrodialysis process, it is dense
The brine waste of contracting can obtain sodium chloride and sodium sulphate Nacl by corresponding crystallization processes respectively.
The first aspect of the utility model:
A kind of high-salinity wastewater zero-emission method, includes the following steps:
Step 1 cleans the preprocessed system of brine waste；
Step 2 carries out concentration to the waste water that step 1 obtains；
Step 3 carries out sofening treatment to the waste water that step 2 obtains；
Step 4 is handled the waste water that step 3 obtains using nanofiltration membrane, adjusts the NaCl and Na in waste water2SO4Concentration
Ratio；
The concentrated water of step 5, nanofiltration membrane is sent into Na2SO4Crystal system obtains Na by Crystallization Separation2SO4Nacl and
First mother liquor；The fresh water of nanofiltration membrane is concentrated and then is sent into NaCl crystal system, obtains NaCl work by Crystallization Separation
Industry salt and the second mother liquor；
Step 6, the first mother liquor, which is sent into NaCl crystal system, carries out crystallization treatment, and the second mother liquor is sent into Na2SO4System of crystallization
System carries out crystallization treatment.
In one embodiment, pretreatment system is discharged COD between 10~200mg/L in step 1, SS 3~
50mg/L。
In one embodiment, the pretreatment in step 1 refers to pre-filtering, biofilter, precipitating, oxidation or ultrafiltration
One of or a variety of combinations.
In one embodiment, pre-filtering is one of sand filtration, multi-medium filtering or active carbon filtering or a variety of
Combination.
In one embodiment, oxidation is using one in ozonation technology, Fenton oxidation technology or microwave oxidation
Kind or a variety of combinations；Biofilter refers to activated carbon bio-filter.
In one embodiment, concentration makes in waste water TDS in 20~60g/L；Concentration process is dense using nanofiltration membrane
One of contracting, reverse osmosis concentration or electrodialysis concentration or kinds of processes combination.
In one embodiment, melded system goes out the water hardness between 20~200mg/L in step 3；Softening process can
Using one of film softening, medicament softening or ion exchange resin softening or kinds of processes combination.
In one embodiment, NaCl and Na in step 4, in nanofiltration membrane concentrated water2SO4The concentration mass ratio of concentration
0.01~0.07:1；Na in the concentrated water of nanofiltration membrane2SO4Mass concentration 8~15%.
In one embodiment, in step 5, the fresh water of nanofiltration membrane carry out concentration be using high pressure reverse osmosis membrane technique,
The combination of one or more of DTRO technique, electrodialysis process, MVR evaporation technology or multiple-effect evaporation technique；Nanofiltration membrane fresh water
NaCl mass concentration is between 10~20% after concentration.
In one embodiment, the first mother liquor is re-fed into NaCl crystal system after concentration and carries out at crystallization
Reason, the second mother liquor are re-fed into Na after crossing concentration2SO4Crystal system carries out crystallization treatment.
The second aspect of the utility model:
A kind of high-salinity wastewater zero-emission processing unit, comprising:
Pretreatment system, for carrying out pretreatment removal of impurities to high-salt wastewater；
Concentration systems are connected to pretreatment system, and the waste water for obtaining to pretreatment system carries out concentration；
Melded system is connected to concentration systems, for carrying out sofening treatment to the waste water after concentration；
Nanofiltration membrane is connected to melded system, for the separation for producing water and carrying out a divalent salts after sofening treatment；
Sulfate crystal system is connected to the dope side of nanofiltration membrane, for obtaining Na to nanofiltration dope crystallization treatment2SO4；
Sodium chloride crystal system is connected to the light liquid side of nanofiltration membrane, for obtaining NaCl to the light liquid crystallization treatment of nanofiltration.
In one embodiment, the mother liquor outlet of sulfate crystal system is connected to sodium chloride crystal system, sodium chloride
The mother liquor outlet of crystal system is connected to sulfate crystal system.
In one embodiment, the pretreatment system includes pre-filtrating equipment, biofilter, settler, oxygen
Makeup is set or one of ultrafiltration apparatus or a variety of combinations.
In one embodiment, pre-filtrating equipment is sand filtering device, multi-medium filtering device or active carbon filtering dress
It one of sets or a variety of combinations.
In one embodiment, bacteria filter device is activated carbon bio-filter device.
In one embodiment, oxidation unit is ozone-oxidizing device, Fenton oxidation device or microwave oxidation unit
One of or a variety of combinations.
In one embodiment, the concentration systems include nanofiltration film condensing device, reverse osmosis concentrated compression apparatus or
One of electrodialysis enrichment facility or a variety of combinations.
In one embodiment, the light liquid side of nanofiltration membrane is connect by enrichment facility with sodium chloride crystal system.
In one embodiment, enrichment facility is selected from high pressure reverse osmosis membrane apparatus, DTRO device, electrodialysis plant, MVR
The combination of one or more of vaporising device or multi-effect evaporating device.
Beneficial effect
The targeted brine waste wide adaptability of the utility model is adjusted by control nanofiltration cycles of concentration and rejection
The ratio for saving monovalent salt and divalent salts, meets subsequent NaCl and Na2SO4The requirement for crystallizing reuse technology respectively, realizes waste water zero-emission
It puts, and obtains the monovalent salt and divalent product salt of the technical grade of purity is high, have the advantages that energy-efficient emission reduction.
The main innovation point of the utility model is the monovalent salt being used for nanofiltration membrane in high-salt wastewater and divalent salts ratio
Example is adjusted, and meets NaCl and Na2SO4The requirement crystallized respectively recycles the mother liquor of crystallization process, reduces female
Liquid measure improves the efficiency that sal prunella joint process salt utilizes.High-purity is finally obtained while realizing brine waste zero emission
Monovalent salt and divalent salts realize the resource utilization of water and inorganic salts.
In addition, due in NaCl and Na2SO4During crystallizing respectively, the NaCl and Na in feed liquid are crystallized2SO4Concentration
It is bigger than differing, more it is conducive to the crystal salt that crystallization process forms high-purity.And since the salinity in high-salt wastewater can be sent out
Raw periodically fluctuation, is easy to cause the fluctuation for obtaining the generating period of the concentration in light liquid and dope in nanofiltration process, influences
To crystallization process.Therefore, by being returned again to later to upper level to the mother liquor after crystallization using the further concentrate of reverse osmosis membrane
Crystal system can effectively make NaCl and Na2SO4Concentration ratio fluctuation numerical value reduce, it is suppressed that the shakiness in crystallization process
Qualitatively occur.
Detailed description of the invention
Fig. 1 is method overall flow figure provided by the utility model.
Fig. 2 is device figure provided by the utility model.
Wherein, 1, pretreatment system；2, concentration systems；3, melded system；4, nanofiltration membrane；5, sulfate crystal system；6,
Sodium chloride crystal system.
Specific embodiment
The utility model is described in further detail below by specific embodiment.But those skilled in the art will
Understand, the following example is merely to illustrate the utility model, and should not be regarded as limiting the scope of the utility model.In embodiment not
Indicate particular technique or condition person, according to the literature in the art described technology or conditions or according to product description into
Row.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.
The value expressed using range format should be interpreted as not only including clearly enumerating as range in a flexible way
The numerical value of limit value, but also including covering all single numbers or subinterval in the range, like each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood as not only including clearly enumerating
4%) and subinterval (example the concentration of about 0.1% to about 5% further includes the single concentration in how (e.g., 1%, 2%, 3% and
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).
" one embodiment " for addressing in the present specification, " another embodiment ", " embodiment " etc., refer to
In conjunction with the specific features of embodiment description, structure or it is included at least one embodiment generally described herein.
It is not centainly to refer to the same embodiment that statement of the same race, which occur, in multiple places in the description.Furthermore, it is understood that in conjunction with any
When embodiment describes a specific features, structure or feature, what is advocated is that this spy is realized in conjunction with other embodiments
Sign, structure or feature are also fallen in the application scope of the claimed.
It should be understood that it can be direct with other elements when an element is mentioned with another element " connection "
It is connected or is indirectly connected with other elements, and inserted with element between them.Unless there are clearly opposite explanation, otherwise term
It includes listed element that " comprising " and " having ", which is interpreted as statement, and non-excluded any other elements.
Word "include", "comprise" used herein, " having " or its any other variant are intended to cover non-exclusionism
Including.E.g., including technique, method, article or the equipment for listing element are not necessarily limited by those elements, but may include
Other are not explicitly listed or belong to this technique, method, article or the intrinsic element of equipment.
The utility model relates to a kind of technique of high-salinity wastewater zero-emission, required high-salt wastewater to be processed is primarily referred to as containing
There are NaCl, Na2SO4, the substances such as COD waste water, wherein also containing some Ca2+、Mg2+Hardness etc..High-salt wastewater mainly may be used
With the middle water and tail water in paper-making process after treatment, it is also possible to coal chemical industrial waste water and passes through the middle water that processing obtains
With tail water etc..Some typical water quality situations are: COD in COD in 10~200mg/L, 50~1000 mg/L(of total hardness with
CaCO3Meter), TDS in 1000~20000 mg/L, total suspended matter SS in 3~50mg/L, NaCl concentration in 200~5000mg/L,
Na2SO4200~5000mg/L of concentration range.The method of the utility model is especially suitable for NaCl and Na2SO4Concentration proportion
The case where can not separating the two directly by way of evaporative crystallization；Such as NaCl and Na2SO4Mass concentration ratio 10:
This range of 1~1:10, is also possible to 5:1~1:5, is also possible to 2:1~1:2.
Main process flow is as follows:
Step 1: the preprocessed system of high-salt wastewater is cleaned, pretreatment system water outlet；
Step 2: entering salt upgrading system after removal of impurities, TDS is made in waste water to enter reuse in 20~60g/L, reverse osmosis freshwater
Water system；
Step 3, salt upgrading system concentrated water enter melded system, and melded system goes out the water hardness between 50~200mg/L；
Concentrated water after step 4, softening enters nanofiltration mixing system, deploys the concentration of a divalent salts, makes the one of nanofiltration concentrated water
The concentration ratio of divalent salts is between 0.01~0.1；
Step 5, nanofiltration mixing system concentrated water enter Na2SO4Crystal system acquisition meets Nacl requirement Na2SO4Nacl
And mother liquor；
Step 6, nanofiltration mixing system penetrating fluid enter NaCl crystal system after upgrading system again and obtain NaCl Nacl
And mother liquor；
Step 7, Na2SO4The condensed water of crystal system and NaCl crystal system enters reuse water system Na2SO4Crystal system
It discharges mother liquor to enter in NaCl crystal system after cleaning, NaCl crystal system discharges mother liquor and enters Na after cleaning2SO4Crystallization
In system, wastewater zero discharge is realized；
Step 8, each system purified water meet different reuse requirements after the allotment of reuse water system, realize quality classification water supply.
Further, pretreatment unit described in step 1 is mainly to carry out pre- removal of impurities processing using some pairs of conventional water quality
Process, main purpose is to get rid of the impurity that removal is easier in waste water, and mitigate subsequent membrane process, evaporation process etc.
Load, and water quality can be improved, pretreatment here can be carried out according to conventional processing step, may include pre-filtering,
One of precipitating, oxidation technology are a variety of.Wherein pre-filtering is usually the centrifuge separation mode, expression separation side of can enumerating
Formula, filter type, floating separate mode, sedimentation separation mode.As centrifuge separation mode, horizontal continuous centrifugal point may be exemplified
It disembarks (processing of spiral decanter), separate board-like centrifugal separator, filter centrifugal, tall building Pu Lesi type UCF ultracentrifuge, make
For filter type, band filter, belt press, flypress, precoat filter, filter press may be exemplified, separate as floating
Mode may be exemplified continuous floating separator, as sedimentation separation mode, may be exemplified agglutination sedimentation separation machine, sinks rapidly
Seperator etc. is dropped, but is not particularly limited in above-mentioned any one.However it can be reduced by above-mentioned any one or combinations thereof
To the load of film when secondary filter film and/or ultrafiltration membrane treatment.It is particularly preferred that pretreating process can be using sand filtration, more Jie
One of matter filtering, active carbon filtering or multiple combinations.Here biofilter process refers to using with high-specific surface area
Adsorbent material as carrier in water macromolecular or other impurity be removed, carrier used herein above can be using normal
The organic or inorganic adsorbing material of rule, such as: the adsorbent materials such as macroporous absorbent resin, zeolite, active carbon；Bioactivity carbon filtration
Using lower to flow pattern formula, dissolved oxygen content of intaking can fully ensure that biodegrade to dissolved oxygen generally in 5~10mg/L or so in pond
Demand；Filter tank can use two-part air-water backwashing, i.e., be discharged first with air bump rinse operation, again with the sand filtration of non-chlorination anti-
Punching, backwashing period are 1~10 day；If generalling use iodine number and Asia when loading using active carbon as carrier in biofilter
First orchid adsorptive value carries out the standard of evaluation active carbon, can be respectively 300~2000 mg/g and 50~500mg/g with adsorbance, living
Property carbon build-up density can be 50~600g/L.Precipitating described here refers to by gravitational settling or in other external forces
Under sedimentation using the method that separates granule foreign with waste water, the method that can be used is sedimentation basin etc.；Oxidation is benefit
With pollutant in oxidizing Decomposition Wastewater, method to purify waste water, when being handled using advanced oxidation, mainly Fenton
Oxidizing process, ozone co-oxidation method, wet oxidation process, supercritical water oxidation method, photocatalytic oxidation and ultrasonic oxidation method etc. are several
Class particularly preferably using one of ozonation technology, Fenton technology, microwave oxidation or a variety of is combined processing.Using
When ozone oxidation, ozone concentration can be 10~500ppm, and oxidizing temperature can be 10~50 DEG C；When using Fenton oxidation, Fe2+
And H2O2Concentration can be respectively 10~50mg/L and 20~900mg/L, and system pH is 3~6, and reaction temperature is 10~60 DEG C,
Reaction time is 10~240min；When being aoxidized using microwave, 400~3000MHz of frequency, 10~60 DEG C of oxidizing temperature, processing
20~200min of time.Ultrafiltration used in pretreatment, which refers to, carried out the colloid in water, big molecular impurity by ultrafiltration membrane
The process of filter, " ultrafiltration membrane " in this specification refer to, the filter membrane and/or molecular cut off that aperture is 0.001~0.01 μm
For 1000~300000 or so filter membrane, the material of ultrafiltration membrane can use inoranic membrane and organic film, be further divided into thin
Aqueous and hydrophily.As hydrophobic organic film, it is not limited to this, polysulfones can be enumerated, polyether sulfone, polyethers, gathered partially
Difluoroethylene, polyethylene, polypropylene etc..As hydrophilic organic film, be not limited to this, can enumerate polyacrylonitrile,
Polyamide, polyimides, cellulose acetate etc..Its filter core shape includes that flat membrane, tubular film, spiral membrane, doughnut are (hollow
Silk) film etc..
Further, salt concentration systems described in step 2, cycles of concentration is between 2~20 times, according to water inlet salinity
Suitable cycles of concentration is selected, 10~40g/L of its salinity is for preferred salinity but according to salt component in water after concentration
Difference and water inlet salinity variation can appropriate adjustment, which is not the decision condition of process implementing.The salt concentrate of step 2
System is using one of nanofiltration membrane concentration, reverse osmosis concentration, electrodialysis concentration or kinds of processes combination.
The utility model involved in nanofiltration membrane, be defined as " preventing the pressure less than the particle of 2nm and the macromolecular of dissolution
It is sub- that cellulose acetate based polymer, polyamide, sulfonated polysulfone, polyacrylonitrile, polyester, polyamides can be used in the film of power drive film "
The high molecular materials such as amine and polyvinyl.Cellulose acetate Type of Collective can be used in reverse osmosis membrane in the utility model
The high molecular materials such as object, polyamide, polyester, polyimides, polyvinyl.The operating pressure of nanofiltration membrane can control
0.5~4.0MPa, the operating pressure of reverse osmosis membrane can control the range in 1.0MPa~10MPa.
Further, the purpose of the softening process of step 3 gets rid of the Ca in waste water2+、Mg2+It is soft that film can be used in ion
Change, medicament softening (such as be added NaOH and Na2CO3), ion exchange resin softening.
Further, the NaCl and Na in common middle water2SO4Concentration proportion be not able to satisfy respectively crystallization obtain NaCl
And Na2SO4Requirement when, the utility model by nanofiltration membrane be used for in high-salt wastewater monovalent salt and divalent salts ratio adjust
Section, meets NaCl and Na2SO4The requirement crystallized respectively recycles the mother liquor of crystallization process, reduces mother liquor amount, improves
The efficiency that sal prunella joint process salt utilizes.The monovalent salt and two of high-purity is finally obtained while realizing brine waste zero emission
Valence salt realizes the resource utilization of water and inorganic salts.NaCl and Na in the nanofiltration concentrated water of step 42SO4Mass concentration ratio
0.01~0.07 is selection process.
Further, the upgrading system again of step 6 uses high pressure reverse osmosis membrane technique, DTRO technique, electrodialysis process,
MVR evaporation technology or multiple-effect evaporation technique can be used.
Further, NaCl mass concentration is between 10~20% after the nanofiltration fresh water of step 4 is concentrated.
Further, Na after the nanofiltration concentrated water concentration of step 42SO4Mass concentration is between 8~15%.
Further, the 5th NaCl crystal system, Na described in step 6 step2SO4The evaporative crystallization that crystal system uses
Technique is one of multiple-effect evaporation or MVR evaporation.
Further, dedoping step described in step 7 step is using one in ozone oxidation, wet oxidation or light electrolysis oxidation
Kind or multiple combinations technique.
Further, reuse water system described in step 8 can realize quality classification water supply according to each system producing water water quality, be used for
One of boiler feedwater front end, industrial water, plant area's reclaimed water, recirculated water, landscape water are a variety of.
Further, Na2SO4Crystal system mother liquor is re-fed into NaCl crystal system after concentration and carries out at crystallization
Reason, NaCl crystal system mother liquor are re-fed into Na after crossing concentration2SO4Crystal system carries out crystallization treatment.Due to the monovalence in waste water
It can occur constantly to fluctuate with the concentration of divalent salts, and then influence whether the process of subsequent nanofiltration, crystallization, so that technological parameter
Need constantly to be adapted to the variation of salinity in water, therefore it is unstable, crystal salt pure to will lead to operating process
Degree cannot reach requirement.Meanwhile in NaCl and Na2SO4During crystallizing respectively, the NaCl and Na in feed liquid are crystallized2SO4's
Concentration is more conducive to the crystal salt that crystallization process forms high-purity than differing bigger.Such as: in the process crystallized to NaCl
In, NaCl and Na in crystal solution2SO4Concentration proportion be C1(NaCl)/C1(Na2SO4), when by Na2SO4It is obtained after crystallization
Mainly containing the mother liquor of NaCl, (concentration is calculated as C2And C (NaCl),2(NaCl)> C1(NaCl)) it is further added after concentration
During being crystallized to NaCl, it can increase the concentration on the molecule of ratio, improve concentration proportion；According to numerical value
Calculating could be aware that, as 10 < C1(NaCl)/C1(Na2SO4) < 100 when fluctuation, make molecular concentration increase can in ranges
The fluctuating range of whole ratio is obviously reduced, and plays the effect for stabilizing fluctuation.Similarly Na2SO4Crystallization process in, a divalent
The concentration proportion of salt is C1(Na2SO4)/C1(NaCl), what is obtained after crystallizing NaCl mainly contains Na2SO4Mother liquor concentrations
Afterwards, the C that will be obtained2(Na2SO4) concentrate is back to Na2SO4Crystallization process in after, due to C2(Na2SO4)> C1(Na2SO4),
Similarly play the role of stabilizing crystallization process fluctuation of concentration.Therefore, by using reverse osmosis membrane to the mother liquor after crystallization
It returns again to after further concentrate to the crystal system of upper level, can effectively make NaCl and Na2SO4Concentration ratio fluctuation
Numerical value reduces, it is suppressed that the instable generation in crystallization process.
Based on above method, processing unit provided by the utility model is as shown in Figure 2, comprising:
Pretreatment system 1, for carrying out pretreatment removal of impurities to high-salt wastewater；
Concentration systems 2 are connected to pretreatment system 1, and the waste water for obtaining to pretreatment system 1 carries out concentration；
Melded system 3 is connected to concentration systems 2, for carrying out sofening treatment to the waste water after concentration；
Nanofiltration membrane 4 is connected to melded system 3, for the separation for producing water and carrying out a divalent salts after sofening treatment；
Sulfate crystal system 5 is connected to the dope side of nanofiltration membrane 4, for obtaining to nanofiltration dope crystallization treatment
Na2SO4；
Sodium chloride crystal system 6 is connected to the light liquid side of nanofiltration membrane 4, for obtaining to the light liquid crystallization treatment of nanofiltration
NaCl。
In one embodiment, sulfate crystal system 5, mother liquor outlet be connected to sodium chloride crystal system 6, chlorination
The mother liquor outlet of sodium crystal system 6 is connected to sulfate crystal system 5.
In one embodiment, the pretreatment system 1 includes pre-filtrating equipment, biofilter, oxidation unit, sinks
One of shallow lake device, oxidation unit or ultrafiltration apparatus or a variety of combinations.
In one embodiment, pre-filtrating equipment is sand filtering device, multi-medium filtering device or active carbon filtering dress
It one of sets or a variety of combinations.
In one embodiment, oxidation unit is ozone-oxidizing device, Fenton oxidation device or microwave oxidation unit
One of or a variety of combination biofilters refer to activated carbon bio-filter device.
In one embodiment, the concentration systems 2 include nanofiltration film condensing device, reverse osmosis concentrated compression apparatus or
One of electrodialysis enrichment facility or a variety of combinations.
In one embodiment, the light liquid side of nanofiltration membrane 4 is connect by enrichment facility with sodium chloride crystal system.
In one embodiment, enrichment facility is selected from high pressure reverse osmosis membrane apparatus, DTRO device, electrodialysis plant, MVR
The combination of one or more of vaporising device or multi-effect evaporating device.
Embodiment 1
Wastewater zero discharge and Nacl recycling and reusing are realized using nanofiltration and crystallization joint production process for certain pulp-making waste-water.
Pulp-making waste-water raw water day output is 40000 tons.Main water quality parameter see the table below:
Pulp-making waste-water raw water after the homogeneous of homogeneous pond using sand filtration and ozone, activated carbon bio-filter technique to water into
Row pretreatment, ozone concentration 150ppm, ozone oxidation time 40min；Hydraulic detention time 15min；Activated carbon bio-filter charcoal
Bed height 2.0m, 25~30 DEG C for the treatment of temperature, air-land combat 20min；Waste water SS is down to 12~18mg/ after pretreatment
L, COD concentration are down to 45~53mg/L, and the pretreated water rate of recovery is greater than 97%.
Enter ultrafiltration system, the molecular cut off 100kDa of ultrafiltration membrane, ultrafiltration work pressure by pretreated brine waste
Power 0.3MPa, ultrafiltration operating flux 50L/(m2H), the ultrafiltration membrane cleaning frequency is more than 90 days, and water SDI is less than 2.5 for ultrafiltration production, turbid
Degree is lower than 0.2NTU, and the ultrafiltration system rate of recovery is greater than 93%.
Ultrafiltration produces water and enters primary reverse osmosis system, reverse osmosis operating pressure 1.5MPa, and 30 DEG C of temperature, the reverse osmosis rate of recovery
65%, 15 L/(m of average flux2H), it produces water TDS and is lower than 105mg/L.Water yield per day is 24500m3.First-stage reverse osmosis concentrated water into
Enter weak-acid ion exchange resin bed melded system, waste water hardness is down to 170 in 1200~1430mg/L after melded system
~187mg/L is down to 26mg/L by weak acid cation bed hardness, meets the reverse osmosis requirement of back segment.
Reverse osmosis concentrated water after softened enters two sections of counter-infiltration systems, reverse osmosis operating pressure 2.0MPa, and 30 DEG C of temperature,
Water inlet TDS is 10250~10560mg/L, and COD is 187~202mg/L, 3520~3640mg/L of sodium chloride concentration, and sodium sulphate is dense
Spend 6300~6550mg/L, day output 13500m3.The water rate of recovery is 75%, fresh water yield 10120m3/ d, concentrated water amount
3380m3/d.It producing water TDS and is lower than 210mg/L, concentrated water TDS is 40750~41300mg/L, sodium chloride concentration 13450 in concentrated water~
13920mg/L, 24700~25530mg/L of sodium sulfate concentration, 392~434mg/L of hardness.Concentrated water is soft again by weak acid cation bed
Hardness is reduced to 4~6mg/L after change.
Two-pass reverse osmosis concentrated water carries out the allotment of inorganic salts ratio by nanofiltration membrane, and operating pressure 54bar is handled through nanofiltration
Afterwards, fresh water amount is 2910m3/ d, 14700~15340mg/L of sodium chloride concentration, 260~285mg/L of fresh water sodium sulfate concentration.It receives
After filter fresh water is using high pressure is reverse osmosis and homogeneous membrane electrodialytic technique further be concentrated, concentration liquid measure is 245m3/ d, sodium chloride are dense
Spend 191100~203700mg/L, 5380~5500mg/L of sodium sulfate concentration.Nanofiltration concentrated water amount is 480m3/ d, sodium chloride concentration
11320~11890mg/L, 174200~17950mg/L of sodium sulfate concentration.
Nanofiltration fresh water is after reverse osmosis membrane is concentrated, NaCl concentration 31100~31880mg/L, NaCl and Na2SO4Quality it is dense
Degree meets the production requirement for entering NaCl crystallization processes section than being about 53:1.Sodium chloride crystal system uses triple effect evaporation, uses
Advection charging-is every to imitate out salt-mother liquor reflux mode of operation, crystallization temperature is controlled between 40~50 DEG C, in crystalline mother solution
Na2SO4Mass concentration 5380mg/L, send to sulfate crystal system reuse, day obtains 45.7 tons of sodium chloride.Nanofiltration concentrated water into
Enter sulfate crystal system, sulfate crystal system carries out Na using MVR technique2SO4Crystallization controls crystallization temperature 90~105
Between DEG C, Na2SO4Mass concentration ratio with NaCl is about 13:1, meets and enters Na2SO4The technique requirement of crystallization, crystalline mother solution
The mass concentration 58400mg/L of middle NaCl is sent to sodium chloride crystal system reuse, which produces 82.5 tons of anhydrous sodium sulfate daily.
The sodium chloride purity of two kinds of techniques reaches 98.3%, and sodium sulphate purity reaches 99.0%.
Using Nanofiltration-membrane technique in brine waste sodium chloride and sodium sulfate concentration be adjusted, fresh water and concentrated water chlorination
Sodium and sodium sulphate ratio meet the requirement for carrying out sodium sulphate or sodium chloride joint production process, finally the zero-emission of realization waste water, and from
The sodium chloride and sodium sulfate salt that can be recycled are obtained in waste water.
Embodiment 2
The existing Sewage Disposal of certain coal chemical industry enterprises one, wastewater discharge 2750m3/ h, waste water are able to satisfy row up to standard
Put requirement.It is as follows to discharge water water quality indicator:
Inorganic salts ingredients are mainly sodium chloride and sodium sulphate in waste water.Waste water is carried out using nanofiltration and crystallization joint production process
Zero discharge treatment.
Coal chemical industrial waste water is delivered to zero-emission raw water after the homogeneous of homogeneous pond using sand filtration and ozone, active carbon from plant area
Absorbing process pre-processes water, ozone concentration 200ppm, ozone oxidation time 50min；20 DEG C of activated carbon adsorption temperature,
Hydraulic detention time 12min；Waste water SS is down to 5~9mg/L after pretreatment, and COD concentration is down to 20~31mg/L, pretreatment
The water rate of recovery is greater than 98%.
Enter ultrafiltration system, the molecular cut off 50kDa of ultrafiltration membrane, ultrafiltration operating pressure by pretreated brine waste
0.4MPa, ultrafiltration operating flux 45L/(m2H), the ultrafiltration membrane cleaning frequency is more than 60 days, and ultrafiltration produces water SDI less than 2, and turbidity is low
In 0.3NTU, the ultrafiltration system rate of recovery is greater than 92%.
Ultrafiltration produces water and enters primary reverse osmosis system, reverse osmosis operating pressure 2.0MPa, and the reverse osmosis rate of recovery 60% is averaged
15 L/(m of flux2H), it produces water TDS and is lower than 50 mg/L, water yield 1625m3/h.First-stage reverse osmosis concentrated water enters faintly acid
Ion exchange resin bed melded system, waste water hardness drops 30~42mg/L, warp in 1050~1250mg/L after melded system
It crosses weak acid cation bed hardness and is down to 4mg/L hereinafter, meeting the reverse osmosis requirement of back segment.
Reverse osmosis concentrated water after softened enters two sections of counter-infiltration systems, reverse osmosis operating pressure 1.5MPa, and water inlet TDS is
4700~5230mg/L, COD are 38~47mg/L, 735~920mg/L of sodium chloride concentration, 3860~4340mg/ of sodium sulfate concentration
L, treating capacity 1150m3/h.The water rate of recovery is 75%, fresh water yield 860m3/ h, concentrated water amount 290m3/h.Water TDS is produced to be lower than
100mg/L, concentrated water TDS are 18500~20560mg/L, 2900~3130mg/L of sodium chloride concentration in concentrated water, sodium sulfate concentration
15460~17240mg/L, 76~85mg/L of hardness.
Two sections of reverse osmosis concentrated waters enter three sections of counter-infiltration systems, and water inlet TDS is 18500~19840mg/L, COD for 150~
167mg/L, 2900~3170mg/L of sodium chloride concentration, 15460~16710mg/L of sodium sulfate concentration, treating capacity 290m3/h。
The water rate of recovery is 60%, fresh water yield 175m3/ h, concentrated water amount 115m3/h.It produces water TDS and is lower than 400mg/L, concentrated water TDS is
46250~48220mg/L, 7050~7280mg/L of sodium chloride concentration, 38600~40530mg/L of sodium sulfate concentration in concentrated water, firmly
Spend 76~87mg/L.
Three-level reverse osmosis concentrated water carries out the allotment of inorganic salts ratio by nanofiltration membrane, and operating pressure 48bar is handled through nanofiltration
Afterwards, fresh water amount is 77m3/ h, 7120~7330mg/L of sodium chloride concentration, 390~419mg/L of fresh water sodium sulfate concentration.Nanofiltration is light
After water is using high pressure is reverse osmosis and homogeneous membrane electrodialytic technique further be concentrated, concentration liquid measure is 5.1m3/ h, sodium chloride concentration
106080~113500mg/L, 5840~6010mg/L of sodium sulfate concentration.Nanofiltration concentrated water amount is 38m3/ h, sodium chloride concentration 7035
~7230mg/L, 115800~123400mg/L of sodium sulfate concentration.
Nanofiltration fresh water is after reverse osmosis membrane is concentrated, NaCl and Na2SO4Mass concentration ratio be about 18:1, meet enter chlorination
The production requirement of sodium crystal system.Sodium chloride crystal system uses triple effect evaporation, imitates out salt-mother liquor using advection charging-is every
The mode of operation of reflux controls crystallization temperature between 40~50 DEG C, Na in crystalline mother solution2SO4Mass concentration 3070mg/L,
It send to sulfate crystal system reuse, day obtains 12.7 tons of sodium chloride.Nanofiltration concentrated water enters sulfate crystal system, sodium sulphate knot
Crystallographic system system uses MVR technique, controls crystallization temperature between 90~105 DEG C, Na2SO4Mass concentration ratio with NaCl is about 16:
1, meet the technique requirement for entering sodium chloride and sodium sulphate, the mass concentration 33120mg/L of NaCl, send to chlorination in crystalline mother solution
Sodium crystal system reuse, the technique produce 102.6 tons of anhydrous sodium sulfate daily.The sodium chloride purity of two kinds of techniques reaches 98.4%, sulfuric acid
Sodium purity reaches 99.3%.
Using Nanofiltration-membrane technique in coal chemical industrial waste water sodium chloride and sodium sulfate concentration be adjusted, fresh water and concentrated water chlorine
Change sodium and sodium sulphate ratio meets the requirement for carrying out sodium chloride and sulfate crystal technique, finally realizes the zero-emission of waste water, and
The sodium chloride and sodium sulfate salt of technical grade are obtained from waste water.
Embodiment 3
Wastewater zero discharge and Nacl recycling and reusing are realized using nanofiltration and crystallization joint production process for certain pulp-making waste-water.
Pulp-making waste-water raw water day output is 40000 tons.Main water quality parameter see the table below:
Pulp-making waste-water raw water after the homogeneous of homogeneous pond using sand filtration and ozone, activated carbon bio-filter technique to water into
Row pretreatment, ozone concentration 150ppm, ozone oxidation time 40min；Hydraulic detention time 15min；Activated carbon bio-filter charcoal
Bed height 2.0m, 25~30 DEG C for the treatment of temperature, air-land combat 20min；Waste water SS is down to 12~18mg/ after pretreatment
L, COD concentration are down to 45~53mg/L, and the pretreated water rate of recovery is greater than 97%.
Enter ultrafiltration system, the molecular cut off 100kDa of ultrafiltration membrane, ultrafiltration work pressure by pretreated brine waste
Power 0.3MPa, ultrafiltration operating flux 50L/(m2H), the ultrafiltration membrane cleaning frequency is more than 90 days, and water SDI is less than 2.5 for ultrafiltration production, turbid
Degree is lower than 0.2NTU, and the ultrafiltration system rate of recovery is greater than 93%.
Ultrafiltration produces water and enters primary reverse osmosis system, reverse osmosis operating pressure 1.5MPa, and 30 DEG C of temperature, the reverse osmosis rate of recovery
65%, 15 L/(m of average flux2H), it produces water TDS and is lower than 105mg/L.Water yield per day is 24500m3.First-stage reverse osmosis concentrated water into
Enter weak-acid ion exchange resin bed melded system, waste water hardness is down to 170 in 1200~1430mg/L after melded system
~187mg/L is down to 26mg/L by weak acid cation bed hardness, meets the reverse osmosis requirement of back segment.
Reverse osmosis concentrated water after softened enters two sections of counter-infiltration systems, reverse osmosis operating pressure 2.0MPa, and 30 DEG C of temperature,
Water inlet TDS is 10250~10560mg/L, and COD is 187~202mg/L, 3520~3640mg/L of sodium chloride concentration, and sodium sulphate is dense
Spend 6300~6550mg/L, day output 13500m3.The water rate of recovery is 75%, fresh water yield 10120m3/ d, concentrated water amount
3380m3/d.It producing water TDS and is lower than 210mg/L, concentrated water TDS is 40750~41300mg/L, sodium chloride concentration 13450 in concentrated water~
13920mg/L, 24700~25530mg/L of sodium sulfate concentration, 392~434mg/L of hardness.Concentrated water is soft again by weak acid cation bed
Hardness is reduced to 4~6mg/L after change.
Two-pass reverse osmosis concentrated water carries out the allotment of inorganic salts ratio by nanofiltration membrane, and operating pressure 54bar is handled through nanofiltration
Afterwards, fresh water amount is 2910m3/ d, 14700~15340mg/L of sodium chloride concentration, 260~285mg/L of fresh water sodium sulfate concentration.It receives
After filter fresh water is using high pressure is reverse osmosis and homogeneous membrane electrodialytic technique further be concentrated, concentration liquid measure is 245m3/ d, sodium chloride are dense
Spend 191100~203700mg/L, 5380~5500mg/L of sodium sulfate concentration.Nanofiltration concentrated water amount is 480m3/ d, sodium chloride concentration
11320~11890mg/L, 174200~17950mg/L of sodium sulfate concentration.
Nanofiltration fresh water is after reverse osmosis membrane is concentrated, NaCl concentration 31100~31880mg/L, NaCl and Na2SO4Quality it is dense
Degree meets the production requirement for entering NaCl crystallization processes section than being about 53:1.Sodium chloride crystal system uses triple effect evaporation, uses
Advection charging-is every to imitate out salt-mother liquor reflux mode of operation, controls crystallization temperature between 40~50 DEG C, crystalline mother solution warp
Na after high pressure reverse osmosis concentration2SO4Mass concentration 217710mg/L, send to sulfate crystal system reuse, day obtains sodium chloride
48.6 tons.Nanofiltration concentrated water enters sulfate crystal system, and sulfate crystal system carries out Na using MVR technique2SO4Crystallization, control
Crystallization temperature is between 90~105 DEG C, Na2SO4Mass concentration ratio with NaCl is about 13:1, meets and enters Na2SO4Crystallization
Technique requirement, the mass concentration 63320mg/L of crystalline mother solution middle NaCl after high pressure reverse osmosis concentration are sent to sodium chloride system of crystallization
System reuse, the technique produce 84.7 tons of anhydrous sodium sulfate daily.The sodium chloride purity of two kinds of techniques reaches 99.0%, and sodium sulphate purity reaches
To 99.4%.
Using Nanofiltration-membrane technique in brine waste sodium chloride and sodium sulfate concentration be adjusted, fresh water and concentrated water chlorination
Sodium and sodium sulphate ratio meet the requirement for carrying out sodium sulphate or sodium chloride joint production process, finally the zero-emission of realization waste water, and from
The sodium chloride and sodium sulfate salt that can be recycled are obtained in waste water.
Claims (8)
1. a kind of high-salinity wastewater zero-emission processing unit characterized by comprising
Pretreatment system (1), for carrying out pretreatment removal of impurities to high-salt wastewater；
Concentration systems (2) are connected to pretreatment system (1), and the waste water for obtaining to pretreatment system (1) carries out concentration；
Melded system (3) is connected to concentration systems (2), for carrying out sofening treatment to the waste water after concentration；
Nanofiltration membrane (4) is connected to melded system (3), for the separation for producing water and carrying out a divalent salts after sofening treatment；
Sulfate crystal system (5) is connected to the dope side of nanofiltration membrane (4), for obtaining to nanofiltration dope crystallization treatment
Na2SO4；
Sodium chloride crystal system (6) is connected to the light liquid side of nanofiltration membrane (4), for obtaining NaCl to the light liquid crystallization treatment of nanofiltration.
2. high-salinity wastewater zero-emission processing unit according to claim 1, which is characterized in that sulfate crystal system (5)
Mother liquor outlet be connected to sodium chloride crystal system (6), the mother liquor outlet of sodium chloride crystal system (6) is connected to sulfate crystal
System (5).
3. high-salinity wastewater zero-emission processing unit according to claim 1, which is characterized in that the pretreatment system
It (1) include one of pre-filtrating equipment, biofilter, oxidation unit, settler, oxidation unit or ultrafiltration apparatus or more
The combination of kind.
4. high-salinity wastewater zero-emission processing unit according to claim 3, which is characterized in that pre-filtrating equipment is sand filtration dress
It sets, one of multi-medium filtering device or active carbon filtering device or a variety of combinations.
5. high-salinity wastewater zero-emission processing unit according to claim 3, which is characterized in that oxidation unit is ozone oxidation
One of device, Fenton oxidation device or microwave oxidation unit or a variety of combination biofilters refer to active carbon biological filter
Pool device.
6. high-salinity wastewater zero-emission processing unit according to claim 1, which is characterized in that the concentration systems (2)
Including one of nanofiltration film condensing device, reverse osmosis concentrated compression apparatus or electrodialysis enrichment facility or a variety of combinations.
7. high-salinity wastewater zero-emission processing unit according to claim 1, which is characterized in that the light liquid side of nanofiltration membrane (4)
It is connect by enrichment facility with sodium chloride crystal system.
8. high-salinity wastewater zero-emission processing unit according to claim 7, which is characterized in that it is anti-that enrichment facility is selected from high pressure
The combination of one or more of permeable membrane device, DTRO device, electrodialysis plant, MVR vaporising device or multi-effect evaporating device.
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| CN108623104A (en) * | 2018-07-16 | 2018-10-09 | 南京工业大学 | A kind of high-salinity wastewater zero-emission processing method and processing device based on NF membrane allotment |
| CN110217927A (en) * | 2019-04-25 | 2019-09-10 | 天津市环境保护科学研究院 | The processing method of sodium chloride and sodium sulphate rejection in a kind of control high-salt wastewater |
| CN110217928A (en) * | 2019-04-25 | 2019-09-10 | 天津市环境保护科学研究院 | A kind of sub-prime method of the strand industry with sodium chloride in high-salt wastewater and sodium sulphate |
| CN111233233A (en) * | 2019-11-21 | 2020-06-05 | 江苏久吾高科技股份有限公司 | Resource utilization method and device for RO concentrated solution |
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| CN108623104A (en) * | 2018-07-16 | 2018-10-09 | 南京工业大学 | A kind of high-salinity wastewater zero-emission processing method and processing device based on NF membrane allotment |
| CN108623104B (en) * | 2018-07-16 | 2023-08-22 | 南京工业大学 | High-salinity wastewater zero-emission treatment method and device based on nanofiltration membrane allocation |
| CN110217927A (en) * | 2019-04-25 | 2019-09-10 | 天津市环境保护科学研究院 | The processing method of sodium chloride and sodium sulphate rejection in a kind of control high-salt wastewater |
| CN110217928A (en) * | 2019-04-25 | 2019-09-10 | 天津市环境保护科学研究院 | A kind of sub-prime method of the strand industry with sodium chloride in high-salt wastewater and sodium sulphate |
| CN111233233A (en) * | 2019-11-21 | 2020-06-05 | 江苏久吾高科技股份有限公司 | Resource utilization method and device for RO concentrated solution |
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