CN106966536A - Strong brine zero-emission film concentration technology and equipment - Google Patents
Strong brine zero-emission film concentration technology and equipment Download PDFInfo
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- CN106966536A CN106966536A CN201610023871.4A CN201610023871A CN106966536A CN 106966536 A CN106966536 A CN 106966536A CN 201610023871 A CN201610023871 A CN 201610023871A CN 106966536 A CN106966536 A CN 106966536A
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- strong brine
- water
- hyperconcetration
- filtration
- reverse osmosis
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 96
- 239000012267 brine Substances 0.000 title claims abstract description 94
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000012528 membrane Substances 0.000 claims abstract description 78
- 238000001728 nano-filtration Methods 0.000 claims abstract description 50
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 49
- 238000001471 micro-filtration Methods 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 34
- 238000010612 desalination reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 19
- 230000008025 crystallization Effects 0.000 claims abstract description 19
- 239000002562 thickening agent Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims description 34
- 238000004140 cleaning Methods 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 22
- 239000012466 permeate Substances 0.000 claims description 11
- 239000010802 sludge Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- 239000004902 Softening Agent Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 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 claims description 4
- 239000002910 solid waste Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000000701 coagulant Substances 0.000 claims description 2
- 230000001112 coagulating effect Effects 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 claims description 2
- 230000016615 flocculation Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 238000001764 infiltration Methods 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000003814 drug Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 235000001055 magnesium Nutrition 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002455 scale inhibitor Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009292 forward osmosis Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- ARYKTOJCZLAFIS-UHFFFAOYSA-N hydrogen peroxide;ozone Chemical compound OO.[O-][O+]=O ARYKTOJCZLAFIS-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- XZPVPNZTYPUODG-UHFFFAOYSA-M sodium;chloride;dihydrate Chemical compound O.O.[Na+].[Cl-] XZPVPNZTYPUODG-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A kind of strong brine zero-emission film concentration technology and equipment, including：Soften micro-filtration, nanofiltration membrane separation device, strong brine desalination reverse osmosis membrane apparatus, hyperconcetration device, evaporated crystallization device.The reaction thickener delivery port for softening micro-filtration is connected with softening micro-filtration water inlet, soften and pH value governor motion is provided with before the delivery port of micro-filtration, softening micro-filtration is connected in series mutually with nanofiltration membrane separation device, strong brine desalination reverse osmosis membrane apparatus, hyperconcetration device, reuse water tank, the water inlet of each equipment and delivery port, and the super brine outlet of hyperconcetration device is connected with evaporated crystallization device.Present invention process includes pre-treatment step, film concentration step.It is an advantage of the invention that by the combination of a variety of concentration technologies, effectively improving the efficiency that equipment handles strong brine, realizing the target of minimizing, the zero-emission of strong brine, reduce the operating cost of strong brine processing equipment.
Description
Technical field
The present invention relates to a kind of water treatment technology and equipment, more particularly to a kind of strong brine zero-emission film concentration
Processes and apparatus.
Background technology
Wastewater zero discharge is the target that coal chemical industry requires to realize, realizes the important of sustainable stable development
Link, and in whole wastewater zero discharge processing links, the high cost of investment of evaporated crystallization device and operation
Cost is to restrict the big bottleneck that zero-emission is realized, therefore to entering the wastewater minimisation reuse before evaporative crystallization,
It is a crucial ring for effective reduction disposed of in its entirety cost.
The targeted strong brine of coal chemical industry Zero emission device is mainly coal chemical engineering equipment institute waste discharge difference
The strong brine for handling by wastewater biochemical, producing after advanced oxidation, Treated sewage reusing water dual membrane system, has
The features such as higher COD (COD), high salinity, high rigidity, high alkalinity, it is impossible to directly adopt
Reuse is further concentrated with conventional reverse osmosis, and because general water is larger, is directly entered evaporative crystallization and enters
The hot method condensing crystallizing of row, investment and operating cost are high.
Processing typically has for the decrement reuse method of such strong brine both at home and abroad now：Efficient oxidation, efficiently
Counter-infiltration, positive infiltration, electric desalination, membrane distillation etc..It is upper all in application although the method for processing is a lot
There is certain limitation, lack systemic flow, it is impossible to complete whole process processing, actual processing effect and warp
Ji property aspect has obvious shortcoming.
The content of the invention
The purpose of the present invention is, for defect present in prior art, to provide a kind of strong brine zero-emission film
Concentration technology and equipment.The present invention effectively improves the cycles of concentration of strong brine by the combination of kinds of processes,
The minimizing of strong brine is realized, evaporated crystallization device scale is reduced to realize, overall operation cost is reduced.
The technology characteristics of the present invention comprise the following steps：
(1) high strong brine is delivered to pretreatment softening micro-filtration film device, removed for carrying out softening to high strong brine
Turbid pretreatment；
(2) the high strong brine after step (1) softens turbidity removal is delivered to nanofiltration membrane separation device, utilized
The stalling characteristic of NF membrane, by the COD (COD) in high strong brine, divalent salts and one
Valency salt separate, formed respectively based on COD (COD), the concentrate of divalent salts and
Based on monovalent salt, the permeate of microchemistry oxygen demand (COD)；
(3) permeate after step (2) nanofiltration separation is delivered to strong brine desalination reverse osmosis membrane apparatus,
Further the salts substances in removing nanofiltration permeate liquid, form the counter-infiltration for meeting reuse water quality requirement
Produce the reverse osmosis concentrated water of water and concentration monovalent salt；
(4) it will be formed after the concentrated water that step (3) strong brine desalinates reverse osmosis concentration is mixed with nanofiltration concentrated water
Compared with high chemical oxygen demand (COD), the high strong brine of high salinity, hyperconcetration film device is delivered to
Further decrement concentration, and set energy recycle device to reduce hyperconcetration plant running energy consumption, it is highly concentrated
Salt solution forms super strong brine after hyperconcetration device concentration decrement and goes successively to evaporative crystallization technique
Section, the hyperconcetration production water after desalination is mixed with by the reverse osmosis produced water of step (3) desalination,
Water quality meets reuse water quality requirement；
(5) the pretreatment softening sludge by step (1) formation is delivered to sludge dewatering unit, through overvoltage
After filter dehydration, filtrate return to step (1) softening micro-filtration film device improves overall Water Sproading rate,
The filter cake that press filtration is formed is disposed as common solid waste；
Rinsed in the step (1) (2) (3) (4), Chemical cleaning uses device self-produced with water
Water, the Chemical cleaning discharge water periodically produced is recycled to pretreatment unit, improves overall water use efficiency.
In the step (1), coagulating only adds softening agent, is not required to add coagulant and flocculation aid.
Nanofiltration membrane separation device selection in the step (2) is applied to carnallite and separates and be resistant to high COD
Nanofiltration membrane component, and pass through multi-stage series, improve nanofiltration membrane separation device the rate of recovery, design reclaim
Rate >=90%.
Strong brine desalination reverse osmosis membrane apparatus in the step (3), which is used, is applied to the dense of monovalent salt concentration
Saline-water reclamation membrane module, and by multi-stage series, the rate of recovery that strong brine desalinates reverse osmosis unit is improved,
Design the rate of recovery >=80%.
Hyperconcetration film device in the step (4) is used suitable for the super dense of high strong brine hyperconcetration technique
Contracting membrane module, tolerance high chemical oxygen demand (COD) pollution, high salinity concentration operating mode can be met simultaneously
It is required that, the rate of recovery >=45% is designed, hyperconcetration device concentrated water salt content reaches more than 10%, and uses energy
Rate of recovery device is measured, operation energy consumption is effectively reduced.
Present invention also offers a kind of strong brine zero-emission film concentrator, including:Softening micro-filtration,
Nanofiltration membrane separation device, strong brine desalination reverse osmosis membrane apparatus, hyperconcetration device, evaporated crystallization device,
Reuse water tank, it is characterised in that the softening micro-filtration front end is provided with a reaction thickener, reaction concentration
Provided with softening agent device is added in groove, the delivery port for reacting thickener is connected with softening micro-filtration water inlet,
The delivery port of softening micro-filtration is connected with the water inlet of nanofiltration membrane separation device, softens going out for micro-filtration
PH value governor motion is provided with before the mouth of a river, delivery port and the strong brine of nanofiltration membrane separation device desalinate counter-infiltration
The water inlet connection of film device, the strong brine desalination delivery port of reverse osmosis membrane apparatus and entering for hyperconcetration device
The mouth of a river is connected, and the delivery port of hyperconcetration device is connected with reuse water tank, and the super strong brine of hyperconcetration device goes out
Mouth is connected with evaporated crystallization device.
The NF membrane of the nanofiltration membrane separation device is that receiving for high COD is separated and be resistant to suitable for carnallite
Filter membrane component, is multi-stage series structure.
The strong brine desalination reverse osmosis membrane apparatus is that the strong brine concentrated suitable for monovalent salt desalinates film group
Part, and pass through multi-stage series.
The softening micro-filtration film device uses organic tube type filter membrance, 0.1 micron of filtering accuracy ＜.
It is an advantage of the invention that by the combination of a variety of concentration technologies, effectively improving equipment processing strong brine
Efficiency, realizes the target of minimizing, the zero-emission of strong brine, reduce the operation of strong brine processing equipment into
This.
Brief description of the drawings
Fig. 1 strong brine zero-emission film concentration technology FB(flow block)s；
The structural representation of Fig. 2 present invention.
In figure：1 reaction thickener, 2 softening micro-filtrations, 3 nanofiltration membrane separation devices, the desalination of 4 strong brines are anti-
Permeable membrane device, 5 hyperconcetration devices, 6 evaporated crystallization devices, 7 reuse water tanks；
Pre-process workshop section：It is 101 storage regulating reservoirs, 102 advanced oxidation devices, 103 reaction thickeners, 104 soft
Change micro-filtration, it is 105 intermediate pools, 106 sludge dewatering units, 107 regulating reservoir elevator pumps, 108 micro-
Filter membrane suction pump, 110 strong oxidizer throwing devices, 111 softening medicament addition devices；
Film concentration section：201 cartridge filters, 202 nanofiltration membrane separation devices, 203 nanofiltration effluent troughs,
204 cartridge filters, 205 strong brines desalination reverse osmosis unit, 206 reverse osmosis concentrated tanks, 207 films are soft
Makeup put, 208 hyperconcetration intake chambers, 209 hyperconcetration devices, 210 reuse tanks, 211 ultrafiltration water inlet
Pump, 212 feed water by reverse osmosis pumps, 213 reverse osmosis high-pressure pumps, 214 films softening feed pump, 215 hyperconcetration
Feed pump, 216 hyperconcetration high-pressure pumps, 217 ultrafiltration apparatus cleaning pumps, 219 air compressor machines, 220 chemistry are clear
Cleaning device, 221 sodium hypochlorite throwing devices, 222 softening agent throwing devices, 223 scale inhibitor feeding devices,
224 citric acid throwing devices；230 evaporated crystallization devices.
Embodiment
Embodiments of the invention are further illustrated below in conjunction with the accompanying drawings：
Embodiment one：
Strong brine enters the reaction thickener 1 of the softening micro-filtration film device 2 of pre-treatment step, (referring to Fig. 1)
Enter softening micro-filtration after abundant coagulation softening reaction after the softening agents such as feeding lime in reaction thickener 1
Film device 2 carried out filtering out hard turbidity removal, removes most calcium and magnesiums in strong brine, hardness, basicity and hangs
Float impurity；Soften the inorganic sludge of the cycle emissions of micro-filtration film device 2 after filter-press dehydration, filtrate returns anti-
Answer thickener 1, dehydrated sludge cake formation common sludge solid waste outward transport disposal, the water outlet pH of softening micro-filtration film device 2
Enter NF membrane separator 3 after readjustment；Strong brine separates concentration by nanofiltration membrane separation device 3, is formed
The nanofiltration concentrated water of main sulfur acid sodium and overwhelming majority COD with it is main contain sodium nitrate, it is sodium chloride, micro
COD nanofiltration production water；Nanofiltration production water enters strong brine and desalinates the further desalination and concentration of reverse osmosis unit 4, enters
Reverse osmosis produced water after one step desalination, which is met, enters recycle-water case 7 after reuse requirement, reverse osmosis concentration formation
High strong brine is mixed into the further desalination and concentration of hyperconcetration device 5 with nanofiltration concentrated water, after further desalination
The water that hyperconcetration film is produced, which is met, enters recycle-water case 7 after reuse requirement, for plant area's circulating cooling make-up water, surpass
The super strong brine that concentration is formed enters follow-up evaporated crystallization device 6.Solid-liquid is completed by evaporated crystallization device 6
Separation.
Micro-filtration, nanofiltration, counter-infiltration, the cycle of hyperconcetration film make up a prescription, cleaned etc. in device is used with water
The self-produced water of device, cleaning discharge water returns to the reaction thickener 1 of softening micro-filtration film device 2.
The technique of the present embodiment comprises the following steps：
(1) high strong brine is delivered to pretreatment softening micro-filtration film device, removed for carrying out softening to high strong brine
Turbid pretreatment；
(2) the high strong brine after step (1) softens turbidity removal is delivered to nanofiltration membrane separation device, utilized
The stalling characteristic of NF membrane, the COD in high strong brine, divalent salts are separated with monovalent salt, respectively
Formed based on COD, the concentrate of divalent salts with based on monovalent salt, trace amounts of CO D
Permeate；
(3) permeate after step (2) nanofiltration separation is delivered to strong brine desalination reverse osmosis membrane apparatus,
Further the salts substances in removing nanofiltration permeate liquid, form the counter-infiltration for meeting reuse water quality requirement
Produce the reverse osmosis concentrated water of water and concentration monovalent salt；
(4) it will be formed after the concentrated water that step (3) strong brine desalinates reverse osmosis concentration is mixed with nanofiltration concentrated water
Higher COD, high salinity high strong brine, are delivered to the further decrement concentration of hyperconcetration film device,
And setting energy recycle device to reduce hyperconcetration plant running energy consumption, high strong brine is filled by hyperconcetration
Put the super strong brine of formation after concentration decrement and go successively to evaporative crystallization technique section, it is super after desalination
Concentration production water is mixed with by the reverse osmosis produced water of step (3) desalination, and water quality meets reuse water quality
It is required that；
(5) the pretreatment softening sludge by step (1) formation is delivered to sludge dewatering unit, through overvoltage
After filter dehydration, filtrate return to step (1) softening micro-filtration film device improves overall Water Sproading rate,
The filter cake that press filtration is formed is disposed as common solid waste；
Rinsed in above-mentioned steps (1) (2) (3) (4), Chemical cleaning uses device certainly with water
Water is produced, the Chemical cleaning discharge water periodically produced is recycled to pretreatment unit, improves overall water conservancy and uses
Rate.
Strong brine after the separation of step (2) solid-liquid centrifugation is transported to nano filter membrance device, utilizes NF membrane
Component is to COD tolerance far above the characteristic of common counter-infiltration and to monovalent salt, divalent salts in water body
Selection pass through characteristic, using nanofiltration to by pretreatment strong brine carry out pre-concentration separation, formed with
COD, divalent salts are the concentrate and the permeate based on monovalent salt, trace amounts of CO D of main body.
The permeate produced by step (3) nanofiltration separation mainly contains monovalent salt and micro-filtration COD, therefore
Reuse can be concentrated again using strong brine desalination film device, desalination producing water water quality reaches country《City is dirty
Water reuse (treatment utilizes industry water standard》It is used as open type on recycled water in (GB/T 19923-2005)
Recirculated cooling water supplements the water standard of water, and concentration side formation salt content reaches 5% or so high strong brine.
After high strong brine mixing by step (3) (4) formation, COD reaches 1000mg/L or so,
Salt content reaches 6% or so, and concentration can not be continued using conventional reverse osmosis membrane module, therefore use can be simultaneously
The hyperconcetration membrane module for meeting the high COD of tolerance and high salinity operating mode carries out hyperconcetration, by step (3)
(4) the high strong brine formed further concentrates decrement, strong brine salt content is reached more than 10%, COD
Reach more than 2000mg/L.Due to desalinating to overcome high osmotic pressure, it is necessary to be higher than conventional strong brine
The operating pressure of counter-infiltration, operation energy consumption is higher, and this hyperconcetration dress is effectively reduced using energy recycle device
The operation energy consumption put.Hyperconcetration device produces water after water is mixed with leading portion strong brine desalination reverse osmosis unit production water
Matter reaches country《Urban sewage reutilization industry water standard》Closed in (GB/T 19923-2005)
It is used as the water standard that open type recirculated cooling water supplements water in recycled water.
By taking the typical pending strong brine of coal chemical industry Zero emission device as an example, amount of inlet water 60m3/ h, saliferous
1.7%, COD300mg/L, total hardness 1000mg/L, total alkalinity 2000mg/L are measured, work is concentrated by this film
After skill decrement reuse, super strong brine water ＜ 10m are ultimately formed37 yuan/m of/h, overall operation cost ＜3。
In pretreatment section, strong brine is stored in storage regulating reservoir 101 and carries out water quality and quantity regulation, stores regulating reservoir
Delivery port is connected by pipeline and regulating reservoir elevator pump 107 with the water inlet of advanced oxidation device 102；It is high
Level oxidation unit 102 is provided with strong oxidizer throwing device 110, adds strong oxidizer and is aoxidized；It is senior
The delivery port of oxidation unit 102 is connected to reaction thickener 103 by pipeline, and reaction thickener 103 is provided with soft
Change medicament addition device 111, add softening agent, the calcium and magnesium plasma in water is produced sediment follow-up
Removed in process；The reaction delivery port of thickener 103 is connected by pipeline with softening micro-filtration 104；Carbon
The metal such as sour calcium, magnesium hydroxide flco is removed in softening micro-filtration 104 by micro-filtrate membrane filtration；
Soften the water outlet of micro-filtration 104 and intermediate pool 105 is entered by pipeline and microfiltration membranes suction pump 108, in
Between the delivery port of pond 105 film concentration section is connected to by pipeline.Soften the sediment in micro-filtration 104
Handled by mud mouth through pumping to sludge treating block 106.
In film concentration section, by pipeline and nanofiltration intake pump 211 by the intermediate pool 106 of pretreatment section
Delivery port is connected to cartridge filter 201, and scale inhibitor feeding device 223 is provided with before cartridge filter 201,
For adding antisludging agent；The delivery port of cartridge filter 201 is connected to nanofiltration membrane separation device 202 by pipeline
Water inlet, waste water is after nanofiltration UF membrane, and suspension, divalent ion in waste water etc. are removed,
Delivery port is connected to nanofiltration effluent trough 203 by pipeline；Nanofiltration membrane separation device 202 is filled provided with Chemical cleaning
220 are put, when film is contaminated serious, for cleaning milipore filter, cleaning decoction is back to Chemical cleaning dress
Put 220 reusable, rows outside the cleaning fluid of failure；One delivery port of nanofiltration effluent trough 203 passes through
Pipeline and feed water by reverse osmosis pump 212 are connected with the water inlet of cartridge filter 204, and another delivery port leads to
Piping and nanofiltration membrane separation device cleaning pump 217 are connected with the Butterworth Hatch of nanofiltration membrane separation device 202,
Its pipeline can enter provided with sodium hypochlorite throwing device 221 and citric acid throwing device 224 to NF membrane
The daily cleaning of row, the concentrated water that nanofiltration membrane separation device 202 is produced enters reverse osmosis concentrated tank 206；Security personnel
The outlet of filter 204 reverse osmosis unit 205 is desalinated with strong brine by pipeline and reverse osmosis high-pressure pump 213
Water inlet connection, the salt in waste water can be concentrated in concentrated water by water after reverse osmosis membrane separation, dense
Saline-water reclamation reverse osmosis unit is provided with scale inhibitor feeding device 223, can add antisludging agent and slow down film fouling；
Reverse osmosis produced water is demineralized water, and the clean water outlet for desalinating reverse osmosis unit 205 by strong brine is connect by pipeline
To reuse tank 210, concentrated water is then connected to reverse osmosis concentrated tank 206 by pipeline；Strong brine desalinates counter-infiltration
The cleaning of device 205 is imported and exported to be connected by export and import of the pipeline respectively with chemically-cleaning device 220,
After reverse osmosis membrane is contaminated, Chemical cleaning can be carried out.Reverse osmosis concentrated tank 206 is added provided with softening agent
Device 222, can add softening medicament, by the calcium and magnesium plasma formation sediment in concentrated water；It is reverse osmosis concentrated
The water outlet of tank 206 softens feed pump 214 by pipeline and film and enters film softening plant 207, soft in film
During makeup is put, the sediment such as calcium and magnesium, which is separated, to be removed.The delivery port of film softening plant 207 is entered by pipeline
Enter hyperconcetration intake chamber 208, the delivery port of hyperconcetration intake chamber 208 passes through pipeline and hyperconcetration feed pump
215 are connected with cartridge filter 204, and the delivery port of cartridge filter 204 passes through pipeline and hyperconcetration high pressure
Pump 216 is connected with the water inlet of hyperconcetration device 209, and hyperconcetration device 209 is high pressure counter-infiltration rolling
Film, in hyperconcetration device, by UF membrane, the salinity in concentrated water is further concentrated；Hyperconcetration device
209 fresh water produced enter reuse tank 210, hyperconcetration dress by the clean water outlet of hyperconcetration device by pipeline
The dope for putting 209 generations is connected to evaporated crystallization device 230 by pipeline.Hyperconcetration device 209 it is clear
Wash provided with chemically-cleaning device 220, Chemical cleaning can be carried out after film is contaminated.
During aforesaid operations, the following parameter of control should be noted：
Pre-process workshop section：Store the residence time of regulating tank 101, the dosing of Strong oxdiative throwing device 110
Soften the dosage and pH, concentration of suspension of medicament in amount and pH, reaction thickener 103, soften micro-
Filter the membrane flux, membrane area and the turbidity of water outlet, SDI and hardness of device 104.
Film concentration section：The membrane flux of nanofiltration membrane separation device 202, strong brine desalination reverse osmosis unit 205
Membrane flux, the membrane flux of film softening plant 207, the throwing of the softening medicament in reverse osmosis concentrated tank 206
Dosage, the membrane flux of hyperconcetration device 209, the membrane flux of above-mentioned various films will with different raw water qualities
There are different values.The electrical conductivity of each section of film water outlet is also controlled, in addition the kind of various film chemical cleaning medicaments
Class and consumption, cleaning frequency etc. also change with the change of raw water.The evaporation capacity of evaporated crystallization device 230,
Operating temperature and pressure.
Embodiment two：
The present embodiment is identical with embodiment one, except that advanced oxidation can be ozone oxidation (or
Catalytic ozonation, ozone hydrogen peroxide oxidation).Hyperconcetration device 209 can be vibrating membrane, high pressure
Film or forward osmosis membrane.Softening micro-filtration film device 104 can be precipitation+submergence decline it is (super) filter, or
Micro- (super) filter membrane of precipitation+tubular type or traditional medicament softening process, i.e. dosing reaction+precipitation+
Filtering+ultrafiltration.Crystallizing evaporator 230 can be that multiple-effect evaporation concentration or mechanical compress are concentrated by evaporation.Receive
Filter membrane separator 202 can make Weak-acid cation exchange, the supporting auxiliary equipment one of nanofiltration system into
Rise and make the corollary system of ion exchange into, while the film softening plant 207 of film process section and its with being arranged
It is standby to save.
Embodiment three：
The present embodiment is identical with embodiment one, except that when hardness is relatively low in raw water, film process
Film softening plant 207 in process can save.
Claims (10)
1. a kind of strong brine zero-emission film concentration technology, its technology characteristics comprise the following steps：
(1) high strong brine is delivered to pretreatment softening micro-filtration film device, removed with carrying out softening to high strong brine
Turbid pretreatment；
(2) nanofiltration UF membrane dress will be delivered to by step (1) the softening pretreated high strong brine of turbidity removal
Put, using the stalling characteristic of NF membrane, by the COD in high strong brine, divalent salts with
Monovalent salt is separated, and is formed respectively based on COD, the concentrate of divalent salts and with one
Valency salt, microchemistry oxygen demand are the permeate of main body；
(3) permeate after step (2) nanofiltration separation is delivered to strong brine desalination reverse osmosis membrane dress
Put, further the salts substances in removing nanofiltration permeate liquid, formation meets reuse water quality requirement
The reverse osmosis concentrated water of reverse osmosis produced water and concentration monovalent salt；
(4) will by step (3) strong brine desalinate reverse osmosis concentration concentrated water mixed with nanofiltration concentrated water after shape
Into the high strong brine compared with high chemical oxygen demand, high salinity, it is delivered to hyperconcetration film device and enters one
Decrement concentration is walked, high strong brine forms super strong brine after hyperconcetration device concentration decrement and continued
Into evaporative crystallization technique section, the hyperconcetration production water after desalination by step (3) with removing
The reverse osmosis produced water mixing of salt, water quality meets reuse water quality requirement；
(5) the pretreatment softening sludge by step (1) formation is delivered to sludge dewatering unit, passed through
After filter-press dehydration, filtrate return to step (1) softening micro-filtration film device improves overall Water Sproading
Rate, the filter cake that press filtration is formed is disposed as common solid waste.
2. strong brine zero-emission film concentration technology according to claim 1, it is characterised in that the step
(1) rinsed in (2) (3) (4), Chemical cleaning uses the self-produced water of device, cycle with water
Property produce Chemical cleaning discharge water be recycled to pretreatment unit.
3. strong brine zero-emission film concentration technology according to claim 1, it is characterised in that the step
Suddenly in (1), coagulating only adds softening agent, is added without coagulant and flocculation aid.
4. strong brine zero-emission film concentration technology according to claim 1, it is characterised in that the step
Suddenly the nanofiltration membrane separation device selection in (2) is applied to carnallite separation and is resistant to high chemical oxygen demand
Nanofiltration membrane component, and by multi-stage series, improve the rate of recovery of nanofiltration membrane separation device, if
Count the rate of recovery >=90%.
5. strong brine zero-emission film concentration technology according to claim 1, it is characterised in that the step
Suddenly the strong brine desalination reverse osmosis membrane apparatus in (3), which is used, is applied to the strong brine that monovalent salt is concentrated
Desalinate membrane module, and by multi-stage series, improve the rate of recovery that strong brine desalinates reverse osmosis unit,
Design the rate of recovery >=80%.
6. strong brine zero-emission film concentration technology according to claim 1, it is characterised in that the step
(4) the hyperconcetration film device in uses the hyperconcetration film group suitable for high strong brine hyperconcetration technique
Part, the high COD pollutions of tolerance, high salinity concentration working condition requirement can be met simultaneously, the rate of recovery is designed
>=45%, hyperconcetration device concentrated water salt content reaches more than 10%.
7. a kind of strong brine zero-emission film concentrator, including：Soften micro-filtration, nanofiltration membrane separation device,
Strong brine desalination reverse osmosis membrane apparatus, hyperconcetration device, evaporated crystallization device, reuse water tank, its
It is characterised by that the softening micro-filtration front end, provided with a reaction thickener, is reacted and is provided with thickener
Softening agent device is added, the delivery port for reacting thickener is connected with softening micro-filtration water inlet, soft
The delivery port for changing micro-filtration is connected with the water inlet of nanofiltration membrane separation device, softening micro-filtration
PH value governor motion is provided with before delivery port, the delivery port of nanofiltration membrane separation device and strong brine desalination are anti-
The water inlet connection of permeable membrane device, the delivery port of strong brine desalination reverse osmosis membrane apparatus and hyperconcetration
The water inlet connection of device, the delivery port of hyperconcetration device is connected with reuse water tank, hyperconcetration device
Super brine outlet be connected with evaporated crystallization device.
8. strong brine zero-emission film concentrator according to claim 7, it is characterised in that the softening
Micro-filtration film device uses organic tube type filter membrance, 0.1 micron of filtering accuracy ＜.
9. strong brine zero-emission film concentrator according to claim 7, it is characterised in that the nanofiltration
The NF membrane of membrane separation device is the NF membrane that high chemical oxygen demand is separated and be resistant to suitable for carnallite
Component, is multi-stage series structure.
10. strong brine zero-emission film concentrator according to claim 7, it is characterised in that the dense salt
Water desalination reverse osmosis membrane apparatus is that the strong brine concentrated suitable for monovalent salt desalinates membrane module, and is passed through
Multi-stage series.
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| CN108423903A (en) * | 2018-02-27 | 2018-08-21 | 四川美富特水务有限责任公司 | Dyeing waste water zero-discharge treatment system |
| CN108726741A (en) * | 2018-06-14 | 2018-11-02 | 天津市尚拓环保科技有限公司 | Mature landfill leachate processing system and processing method |
| CN109179826A (en) * | 2018-08-16 | 2019-01-11 | 江苏华晖环保科技有限公司 | A kind of strong brine processing technology of achievable zero-emission |
| WO2020181866A1 (en) * | 2019-03-12 | 2020-09-17 | 扬州佳境环境科技股份有限公司 | Device and process for processing wastewater generated in fastener surface treatment |
| CN112358011A (en) * | 2020-11-16 | 2021-02-12 | 淄博格瑞水处理工程有限公司 | Energy-saving seawater desalination device |
| CN112919715A (en) * | 2021-02-05 | 2021-06-08 | 深圳市长隆科技有限公司 | Zero-discharge treatment process for recycling textile printing and dyeing wastewater |
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