CN105417820B - The separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater - Google Patents
The separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater Download PDFInfo
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- CN105417820B CN105417820B CN201510866873.5A CN201510866873A CN105417820B CN 105417820 B CN105417820 B CN 105417820B CN 201510866873 A CN201510866873 A CN 201510866873A CN 105417820 B CN105417820 B CN 105417820B
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- 239000011780 sodium chloride Substances 0.000 title claims abstract description 40
- 239000002351 wastewater Substances 0.000 title claims abstract description 31
- 238000000926 separation method Methods 0.000 title claims abstract description 28
- 239000000460 chlorine Substances 0.000 title claims abstract description 27
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000011084 recovery Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000001728 nano-filtration Methods 0.000 claims abstract description 48
- 238000000909 electrodialysis Methods 0.000 claims abstract description 42
- 238000001764 infiltration Methods 0.000 claims abstract description 27
- 238000007865 diluting Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims description 22
- 230000005712 crystallization Effects 0.000 claims description 22
- 238000007710 freezing Methods 0.000 claims description 22
- 238000001704 evaporation Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 238000000108 ultra-filtration Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 239000007832 Na2SO4 Substances 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 241000276438 Gadus morhua Species 0.000 description 3
- 235000019516 cod Nutrition 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 206010000234 Abortion spontaneous Diseases 0.000 description 1
- 210000002381 Plasma Anatomy 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009298 carbon filtering Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000001112 coagulant Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009434 installation 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
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005429 turbidity Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Abstract
The invention discloses the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater, the separation and recovery system includes pretreatment system, nanofiltration system, counter-infiltration system, electrodialysis system, the first after-treatment system and the second after-treatment system；High-salt wastewater enters pretreatment system and is pre-processed, enter nanofiltration system after pretreatment and carries out nanofiltration processing, the concentrated water flowed out from nanofiltration system enters counter-infiltration system and carries out reverse-osmosis treated, the concentrated water flowed out from counter-infiltration system is post-processed to obtain the product of containing sulfate radicals into the first after-treatment system, the enriched chamber that the production water flowed out from nanofiltration system enters electrodialysis system carries out electrodialysis process, the fresh water flowed out from the diluting compartment of electrodialysis system enters counter-infiltration system and carries out reverse-osmosis treated, the concentrated water flowed out from the enriched chamber of electrodialysis system is post-processed to obtain the product of the root containing chlorine into the second after-treatment system.Separation and recovery system provided by the present invention has preferable social and economic effects.
Description
Technical field
The invention belongs to Industrial Waste Water Treatments field, it is related to the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater
System.
Background technology
In short supply with water resource with the development of industry, production waste water caused by the industry of part contains higher salinity,
Such as Cl-、SO4 2-、Na+、Ca2+The trend risen is presented in plasma, pollution concentration and discharge capacity, therefore, to high-salt wastewater processing
Pure water reuse and inorganic salts recovery technology have become one of the hot spot of current wastewater treatment.
Currently, film combined treatment high salinity waste water realizes that zero-discharge technology is applied than wide, but integrated artistic is inadequate
System, the rate of recovery is not high, the inorganic purity salt of recycling is low, and system energy consumption is high.The high salinity industry that ZL201310311089.9 is introduced
Concentrate after filtering repeatedly is carried out electrodialysis process by process without drainage of waste water, and the material after electrodialysis concentrates carries out
Evaporation and crystallization, but the salt that this technique obtains does not have use value for carnallite.
Therefore, to make with high salt from clean manufacturing, watering balance, resource reclaim angle system analysis combination membrane process feature
Spending industrial wastewater integrated treatment has preferable social and economic effects.
Invention content
It is an object of the invention to for insufficient present on, provide point of chlorine root and sulfate radical in a kind of high-salt wastewater
From recovery system.
For this purpose, the present invention provides following solution：
The separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater, the separation and recovery system include that pretreatment is
System, nanofiltration system, counter-infiltration system, electrodialysis system, the first after-treatment system and the second after-treatment system；High-salt wastewater enters
Pretreatment system is pre-processed, and is entered nanofiltration system after pretreatment and is carried out nanofiltration processing, the concentrated water flowed out from nanofiltration system
Reverse-osmosis treated is carried out into counter-infiltration system, after the concentrated water flowed out from counter-infiltration system enters the progress of the first after-treatment system
Reason obtains the product of containing sulfate radicals, and the enriched chamber that the production water flowed out from nanofiltration system enters electrodialysis system carries out electrodialysis place
Reason, the fresh water flowed out from the diluting compartment of electrodialysis system enters counter-infiltration system and carries out reverse-osmosis treated, from electrodialysis system
The concentrated water of enriched chamber's outflow is post-processed to obtain the product of the root containing chlorine into the second after-treatment system.Nanofiltration system flows out dense
Sulfate ion is mainly contained in water, and chlorion, the nanofiltration of the nanofiltration system are mainly contained in the production water of nanofiltration system outflow
Film is used for through chlorion and retention sulfate ion.High-salt wastewater mentioned in context is that salt content is higher than 1.5% wt,
Dissolvability solid amount is higher than the high salinity industrial wastewater of 15000 mg/L.
Further, first after-treatment system includes freezing and crystallizing system and drying system, from counter-infiltration system stream
The concentrated water gone out enters freezing and crystallizing system and carries out freezing and crystallizing, the mother liquor reuse of the freezing and crystallizing system to electrodialysis system
Diluting compartment carries out electrodialysis process, and the crystallization of the freezing and crystallizing system is dried to obtain containing sulfate radicals into drying system
Product.
Further, setting ozone oxidation system between the concentrated water outlet and the entrance of freezing and crystallizing system of counter-infiltration system
System.
Further, second after-treatment system includes the second nanofiltration system and evaporation and crystallization system, from electrodialysis system
The concentrated water of system outflow enters the second nanofiltration system and carries out nanofiltration processing, and the concentrated water flowed out from the second nanofiltration system enters electrodialysis system
The diluting compartment of system carries out electrodialysis process, and the production water flowed out from the second nanofiltration system enters evaporation and crystallization system and is evaporated crystallization
Obtain the product of the root containing chlorine.
Further, the evaporation and crystallization system is MVR evaporation and crystallization systems, multiphase evaporation and crystallization system and membrane distillation system
One or more combinations in system.
Further, the pretreatment system is dosing melded system, ozone high grade oxidation system, activated carbon filtering system
One or more combinations in system, ultrafiltration system and resin melded system.
Further, the electrodialysis system detaches electrodialytic membranes using a divalent.
MVR is mechanical steam recompression technology（Mechanical Vapor Recompression）Abbreviation, be profit
The indirect steam and its energy generated with vapo(u)rization system itself promotes the heat content of indirect steam through vapour compression machine compressed action,
It leads into cooling tower, the cooling water circulation preheating material of cooling tower, so recycles to vapo(u)rization system and thermal energy is provided, it is external to reduce
One power-saving technology of the demand of boundary's energy.
The present invention provides the separation and recovery systems of chlorine root and sulfate radical in a kind of high-salt wastewater, and electricity is detached by a divalent
Dialysis UF membrane chlorine root and sulfate radical；The concentration that sulfate radical is improved by counter-infiltration system concentration, passes through freezing and crystallizing system
System improves the purity of sulfate radical；The concentration and purity of chlorine root are improved by the concentration and separation of the second nanofiltration system；It is provided
The cost of separation and recovery system is far below high-salinity wastewater zero-emission and comprehensive utilization cost and operating cost of the same trade, meanwhile, chlorine
Root is both greater than 92% with sulfate radical purity salt and meets industrial salt standard, therefore, chlorine root and sulfate radical in the high-salt wastewater provided
Separation and recovery system have preferable social and economic effects.
Description of the drawings
Fig. 1 is the schematic diagram of the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater provided by the present invention；
In figure：1- pretreatment systems；2- nanofiltration systems；3- counter-infiltration systems；4- electrodialysis systems；501- ozone oxidations system
System；502- freezing and crystallizing systems；503- drying systems；The second nanofiltration systems of 504-；505- evaporation and crystallization systems.
Specific implementation mode
The present invention is further described in detail with reference to the drawings and specific embodiments.
The separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater, the separation and recovery system include that pretreatment is
System 1, nanofiltration system 2, counter-infiltration system 3, electrodialysis system 4, the first after-treatment system and the second after-treatment system；High-salt wastewater
It is pre-processed into pretreatment system 1, enters nanofiltration system 2 after pretreatment and carry out nanofiltration processing, flowed out from nanofiltration system 2
Concentrated water enter counter-infiltration system 3 carry out reverse-osmosis treated, from counter-infiltration system 3 flow out concentrated water enter the first after-treatment system
It is post-processed to obtain the product of containing sulfate radicals, the enriched chamber that the production water flowed out from nanofiltration system 2 enters electrodialysis system 4 carries out
Electrodialysis process, the fresh water flowed out from the diluting compartment of electrodialysis system 4 enters counter-infiltration system 3 and carries out reverse-osmosis treated, from electricity
The concentrated water of enriched chamber's outflow of electrodialysis system is post-processed to obtain the product of the root containing chlorine into the second after-treatment system.
First after-treatment system includes freezing and crystallizing system 502 and drying system 503, is flowed out from counter-infiltration system 3
Concentrated water enter freezing and crystallizing system 502 and carry out freezing and crystallizing, the mother liquor reuse of the freezing and crystallizing system 502 to electrodialysis system
The diluting compartment of system 4 carries out electrodialysis process, and the crystallization of the freezing and crystallizing system 502 enters drying system 503 and is dried
To the product of containing sulfate radicals.
The concentrated water of counter-infiltration system 3 exports the setting ozone oxidation system 501 between the entrance of freezing and crystallizing system 502.
Second after-treatment system includes the second nanofiltration system 504 and evaporation and crystallization system 505, from electrodialysis system 4
The concentrated water of outflow enters the second nanofiltration system 504 and carries out nanofiltration processing, and the concentrated water flowed out from the second nanofiltration system 504 enters electric osmose
The diluting compartment of analysis system 4 carries out electrodialysis process, and the water gone out from the second nanofiltration system miscarriage 504 enters evaporation and crystallization system 505
It is evaporated crystallization and obtains the product of the root containing chlorine.
The evaporation and crystallization system 505 is in MVR evaporation and crystallization systems, multiphase evaporation and crystallization system and membrane distillation system
One or more combinations.
The pretreatment system 2 is dosing melded system, ozone high grade oxidation system, activated carbon filtration system, ultrafiltration system
One or more combinations in system and resin melded system.
The electrodialysis system 4 detaches electrodialytic membranes using a divalent.
Specifically, following technique may be used：
The design of each processing unit and installation and debugging with 360 tons per hour for the treatment of capacity to entire technique, finally carry out
Site test carries out certain high-salt wastewater the separation and recovery pilot plant test of sodium chloride and sodium sulphate：
The salt content 1%wt, COD of certain factory's high-salt wastewaterCr160 mg/L, suspended matter are less than 70 mg/L, Ca2+It is a concentration of
360 ppm, Mg2+A concentration of 35 ppm, a concentration of 50 ppm, Cl of silicon-A concentration of 1800 ppm, SO4 2-A concentration of 2540
ppm；
It is soft to be carried out the coagulatings such as addition alkali, soda ash, flocculant precipitation by pretreatment system for the high-salt wastewater of 360 m3/h
Change processing removal calcium ions and magnesium ions, is discharged Ca2+、Mg2+Concentration be below 50 ppm, the concentration of silicon is less than 5 ppm；Dosing softens
Waste water after clarification makes COD be less than 80 ppm through ozone high grade oxidation and activated carbon filter；It is less than again by ultrafiltration system turbidity
0.5NTU, and pass sequentially through cation bed, weak acid bed, degassing tower and ensure water outlet Ca2+、Mg2+、CO3 2-Less than 5 ppm；
By the high-salt wastewater that pretreatment system is handled, into nanofiltration system, the concentrated water of separation is 117 m3/h, is contained
NaCl concentration 0.3%wt, Na2SO4A concentration of 1.1%wt；The concentrated water of nanofiltration system is passed through counter-infiltration system separation concentration, reverse osmosis
The production water of permeable system carries out reuse, and the final concentrated water flow of counter-infiltration system is 15 m3/h, is 2.7% containing NaCl concentration
Wt, Na2SO4A concentration of 10%wt；Concentrated water, which is passed through ozone, reduces coloration, degradation COD；Enter drying after being passed through freezing and crystallizing system
System drying white crystal particle obtains Na2SO4Purity is more than 92%, the mother liquor of freezing and crystallizing system with NaCl concentration 2.9%wt,
Na2SO4A concentration of 4%wt is passed through the diluting compartment desalination of divalent separation electrodialysis system, and the fresh water of diluting compartment outflow is 12m3/h
1%wt containing NaCl concentration, Na2SO4A concentration of 4%wt is back to counter-infiltration system and is concentrated；
The production water of nanofiltration system is passed through the enriched chamber of divalent separation electrodialysis system, and the concentrated water of electrodialysis system enters the
Two nanofiltration systems carry out nanofiltration separation, obtained production water 15%wt containing NaCl concentration, SO4 2-Concentration is less than 0.15%wt, to recycle
High-purity chloro root；The concentrate recirculation of second nanofiltration system detaches the diluting compartment of electrodialysis system to a divalent.
Above-mentioned specific implementation mode is used for illustrating the present invention, is merely a preferred embodiment of the present invention, rather than
Limit the invention, in the protection domain of spirit and claims of the present invention, to the present invention make any modification,
Equivalent replacement, improvement etc., both fall within protection scope of the present invention.
Claims (6)
1. the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater, which is characterized in that the separation and recovery system packet
Include pretreatment system, nanofiltration system, counter-infiltration system, electrodialysis system, the first after-treatment system and the second after-treatment system；It is high
Salt waste water enters pretreatment system and is pre-processed, and enters nanofiltration system after pretreatment and carries out nanofiltration processing, from nanofiltration system
The concentrated water of outflow enters counter-infiltration system and carries out reverse-osmosis treated, and the concentrated water flowed out from counter-infiltration system enters the first post-processing and is
System is post-processed to obtain the product of containing sulfate radicals, and the enriched chamber that the production water flowed out from nanofiltration system enters electrodialysis system carries out
Electrodialysis process, the fresh water flowed out from the diluting compartment of electrodialysis system enters counter-infiltration system and carries out reverse-osmosis treated, from electric osmose
The concentrated water of enriched chamber's outflow of analysis system is post-processed to obtain the product of the root containing chlorine into the second after-treatment system；
The electrodialysis system detaches electrodialytic membranes using a divalent.
2. the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater according to claim 1, which is characterized in that
First after-treatment system includes freezing and crystallizing system and drying system, and the concentrated water flowed out from counter-infiltration system enters freezing knot
Crystallographic system system carries out freezing and crystallizing, and the diluting compartment of mother liquor reuse to the electrodialysis system of the freezing and crystallizing system carries out at electrodialysis
Reason, the crystallization of the freezing and crystallizing system are dried to obtain the product of containing sulfate radicals into drying system.
3. the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater according to claim 2, which is characterized in that
The concentrated water of counter-infiltration system is exported is arranged ozone oxidation system between the entrance of freezing and crystallizing system.
4. the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater according to claim 1, which is characterized in that
Second after-treatment system includes the second nanofiltration system and evaporation and crystallization system, and the concentrated water flowed out from electrodialysis system enters the
Two nanofiltration systems carry out nanofiltration processing, and the diluting compartment that the concentrated water flowed out from the second nanofiltration system enters electrodialysis system carries out electric osmose
Analysis handle, from the second nanofiltration system flow out production water enter evaporation and crystallization system be evaporated crystallize obtain the product of the root containing chlorine.
5. the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater according to claim 4, which is characterized in that
The evaporation and crystallization system is one or more in MVR evaporation and crystallization systems, multiphase evaporation and crystallization system and membrane distillation system
Combination.
6. the separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater according to claim 1, which is characterized in that
The pretreatment system is that dosing melded system, ozone high grade oxidation system, activated carbon filtration system, ultrafiltration system and resin are soft
One or more combinations in change system.
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| CN201510866873.5A CN105417820B (en) | 2015-12-01 | The separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510866873.5A CN105417820B (en) | 2015-12-01 | The separation and recovery system of chlorine root and sulfate radical in a kind of high-salt wastewater |
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| Publication Number | Publication Date |
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| CN105417820A CN105417820A (en) | 2016-03-23 |
| CN105417820B true CN105417820B (en) | 2018-08-31 |
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| CN205241414U (en) * | 2015-12-01 | 2016-05-18 | 杭州（火炬）西斗门膜工业有限公司 | Separation recovery system of chlorine root and sulfate radical in high salt waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN205241414U (en) * | 2015-12-01 | 2016-05-18 | 杭州（火炬）西斗门膜工业有限公司 | Separation recovery system of chlorine root and sulfate radical in high salt waste water |
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