CN116835812A - Coking wastewater membrane filtration concentrated solution treatment system and method - Google Patents
Coking wastewater membrane filtration concentrated solution treatment system and method Download PDFInfo
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- CN116835812A CN116835812A CN202310951922.XA CN202310951922A CN116835812A CN 116835812 A CN116835812 A CN 116835812A CN 202310951922 A CN202310951922 A CN 202310951922A CN 116835812 A CN116835812 A CN 116835812A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 97
- 238000004939 coking Methods 0.000 title claims abstract description 51
- 238000011282 treatment Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000005374 membrane filtration Methods 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 548
- 239000012528 membrane Substances 0.000 claims abstract description 148
- 238000001179 sorption measurement Methods 0.000 claims abstract description 117
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 112
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 89
- 238000004821 distillation Methods 0.000 claims abstract description 78
- 238000004062 sedimentation Methods 0.000 claims abstract description 74
- 238000005189 flocculation Methods 0.000 claims abstract description 55
- 230000016615 flocculation Effects 0.000 claims abstract description 52
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 46
- 238000001728 nano-filtration Methods 0.000 claims abstract description 45
- 238000000909 electrodialysis Methods 0.000 claims abstract description 44
- 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 claims abstract description 42
- 239000011734 sodium Substances 0.000 claims abstract description 42
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 42
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 239000010802 sludge Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims description 99
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 90
- 238000006243 chemical reaction Methods 0.000 claims description 78
- 239000011347 resin Substances 0.000 claims description 49
- 229920005989 resin Polymers 0.000 claims description 49
- 239000002253 acid Substances 0.000 claims description 38
- 238000005273 aeration Methods 0.000 claims description 35
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 34
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 34
- 238000010521 absorption reaction Methods 0.000 claims description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 27
- 239000012452 mother liquor Substances 0.000 claims description 27
- 239000000945 filler Substances 0.000 claims description 25
- 239000012141 concentrate Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 22
- 238000000108 ultra-filtration Methods 0.000 claims description 21
- 238000005292 vacuum distillation Methods 0.000 claims description 21
- 229960004887 ferric hydroxide Drugs 0.000 claims description 16
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000002957 persistent organic pollutant Substances 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 239000007921 spray Substances 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 7
- 239000002918 waste heat Substances 0.000 claims description 7
- 239000008394 flocculating agent Substances 0.000 claims description 6
- 238000009388 chemical precipitation Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001447 ferric ion Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 239000013505 freshwater Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 22
- 238000004064 recycling Methods 0.000 abstract description 8
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 111
- 230000003647 oxidation Effects 0.000 description 32
- 238000007254 oxidation reaction Methods 0.000 description 32
- 150000003839 salts Chemical class 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 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 6
- 229910052742 iron Inorganic materials 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
- 239000003729 cation exchange resin Substances 0.000 description 5
- -1 hydrogen ions Chemical class 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005276 aerator Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003403 water pollutant 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a coking wastewater membrane filtration concentrated solution treatment system which comprises a first adsorption device, a micro-electrolysis device, a Fenton device, a neutralization tank, a flocculation sedimentation tank, an electro-oxidation device, a first hardness removal device, a nanofiltration device, a second vacuum membrane distillation device, a low-temperature crystallizer, a second adsorption device, a second hardness removal device, a bipolar membrane electrodialysis device, a first vacuum membrane distillation device, a water producing tank, a crystallizer and a sodium ferrate preparation device which are sequentially connected. The method comprises the steps of removing organic matters in the concentrated solution by adsorption, micro-electrolysis, fenton and electro-oxidation, recycling the concentrated solution by nanofiltration, vacuum membrane distillation and bipolar membrane electrodialysis, and simultaneously, preparing sodium ferrate solution by effectively utilizing waste gas generated in the electro-oxidation treatment process and sludge generated in the micro-electrolysis, fenton treatment, so that the high recycling rate of the coking wastewater is realized.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a coking wastewater membrane filtration concentrated solution treatment system and a coking wastewater membrane filtration concentrated solution treatment method.
Background
Coking wastewater is typical organic wastewater difficult to degrade, has high toxicity and poor biodegradability, and is one of wastewater difficult to treat in the steel industry. At present, the commonly adopted treatment method for iron and steel enterprises is a biochemical treatment, nanofiltration and reverse osmosis process, and a membrane process can generate concentrated solution in the treatment process.
At present, the recovery rate of the coking wastewater film treatment is generally about 70%, and the produced strong brine with the mass concentration of about 30% is mostly digested in enterprises, and is mainly used for coal blending, slag flushing, coke quenching and the like. In order to meet the requirements of energy conservation and emission reduction and water pollutant emission standards, related enterprises need to perfect the wastewater treatment process and adopt a reduction means.
When the coking wastewater is used as slag flushing water, toxic and harmful substances volatilize under the action of high temperature, and atmospheric pollution is generated. Efficient processing of concentrate is an integral part of the overall processing system and is one of the bottlenecks in current membrane processing technology.
In the steel manufacturing process flow, only 30% -50% of energy is effectively utilized, and a large amount of residual energy exists in a waste heat form, so that the recovery potential is huge. The efficient recycling of waste heat resources is realized, and the reduction of the energy cost of enterprises is a great problem to be considered in the research of iron and steel enterprises. For the treatment of high-salt wastewater, the traditional method is to firstly concentrate the wastewater in a reduced amount, then crystallize salt from the concentrated solution through an evaporation technology, and finally realize wastewater desalination and salt resource recovery. Currently, the large-scale industrialized concentration method mainly comprises a thermal method and a membrane separation method. The thermal method mainly evaporates the water in the high-salt wastewater in a heating mode to achieve the purposes of concentration and volume reduction, and the method generally uses water vapor as a heat source, so that the energy consumption is huge, and the operation cost is very high. The membrane distillation technology is a novel separation technology combining the traditional thermal evaporation process and the membrane separation technology, and the principle is that under the interception action of a hydrophobic microporous membrane, waste liquid is prevented from penetrating through a membrane hole in a liquid form, only volatile components penetrate through the membrane hole under the pushing of vapor pressure difference at two sides of the membrane, and non-volatile components are intercepted, so that the separation and purification of a mixture are finally realized, and the membrane distillation technology has the characteristics of high concentration multiple, low energy consumption and the like (using a low-grade heat source at 30-70 ℃).
A small amount of coking enterprises carry out evaporation crystallization on coking wastewater membrane filtration concentrated solution to obtain industrial water and mixed salt, 60-70% of sodium sulfate can be recovered by a thermal salt separation crystallization process, the comprehensive recovery rate of a crystalline salt product is 40-50%, about 90% of sodium sulfate can be recovered by membrane salt separation crystallization, and the comprehensive recovery rate of crystalline salt reaches about 80%. The existing salt separation crystallization process still has 15% of mixed salt to be treated, and the mixed salt contains organic matters and other impurities, so that the mixed salt belongs to hazardous wastes and has higher treatment cost. How to remove pollutants such as organic matters in the coking wastewater, and recycling salt matters in the coking wastewater, thereby having important significance in realizing the zero discharge technology of the coking wastewater.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a coking wastewater membrane filtration concentrated solution treatment system and a coking wastewater membrane filtration concentrated solution treatment method, which adopt adsorption, micro-electrolysis, fenton and electro-oxidation to remove organic matters in the concentrated solution, adopt nanofiltration, vacuum membrane distillation and bipolar membrane electrodialysis to carry out resource utilization on the concentrated solution, and simultaneously effectively utilize waste gas generated in the electro-oxidation treatment process and sludge generated in the micro-electrolysis and Fenton treatment to prepare sodium ferrate solution, thereby realizing zero emission of the coking wastewater.
In order to solve the problems, the invention provides the following scheme:
a coking wastewater membrane filtration concentrate treatment system comprises a first adsorption device, wherein the water outlet of the first adsorption device is connected with a micro-electrolysis water inlet pipe of a micro-electrolysis device, the water outlet of the micro-electrolysis device is connected with the water inlet of a Fenton device, the water outlet of the Fenton device is connected with the water inlet of a neutralization tank, the water outlet of the neutralization tank is connected with the water inlet of a flocculation sedimentation tank, the ferric hydroxide outlet of the flocculation sedimentation tank is connected with a sodium ferrate preparation device, the water outlet of the flocculation sedimentation tank is connected with the water inlet of an electric oxidation device, the sodium hypochlorite water outlet of the electric oxidation device is connected with the sodium ferrate preparation device, the water outlet of the electric oxidation device is connected with the water inlet of a first hard water removing device, the water outlet of the first hard water removing device is connected with the water inlet of a filter device, the nanofiltration water outlet of the nanofiltration device is connected with the water inlet of a first vacuum membrane distillation device, the concentrated water outlet of the first vacuum membrane distillation device is connected with a crystallizer, the mother liquor outlet of the crystallizer is respectively connected with the water inlet of the first vacuum membrane distillation device and the water inlet of a second adsorption device, the water outlet of the first vacuum membrane distillation device is connected with the bipolar distilled liquor of the second vacuum distillation device, the bipolar distilled water inlet of the bipolar distillation device is respectively connected with the water inlet of the second vacuum distillation device, the bipolar distilled water inlet of the bipolar distillation device is connected with the water inlet of the second vacuum distillation device, and the water outlet of the bipolar distillation device is connected with the water inlet of the water heater of the second vacuum distillation device, and the water heater is connected with the water inlet of the water heater, and the water outlet of the water heater is connected with the water tank and the water heater, the alkali liquor input port of the electro-oxidation device, the alkali liquor dosing pipe of the first hardness removal device and the sodium ferrate preparation device are connected, the acid liquor water outlet of the bipolar membrane electrodialysis device is connected with the acid dosing pipe of the micro-electrolysis device, and the fresh water outlet of the bipolar membrane electrodialysis device is connected with the water inlet of the nanofiltration device.
As described above, the first adsorption device comprises a first adsorption device water inlet tank, the water inlet of the first adsorption device water inlet tank is used as the water inlet of the first adsorption device, the first adsorption device water inlet tank is connected with the first water tank of the adsorption reaction tank through a water inlet pump, the bottom of the first water tank of the adsorption reaction tank and the bottom of the second water tank of the adsorption reaction tank are communicated through a flow passage, the bottoms of the first water tank and the second water tank of the adsorption reaction tank are both provided with aeration pipes, the inlet of the aeration pipes is connected with the first air blower, the second water tank of the adsorption reaction tank is connected with the water inlet of the filter device through the first lifting pump, the water outlet of the filter device (5) is connected with the first water tank of the adsorption reaction tank, the water outlet of the filter device is connected with the external sludge dehydrator, and the water outlet of the first water tank is the water outlet of the first adsorption device.
The micro-electrolysis device comprises a pipeline mixer, one inlet of the pipeline mixer is connected with an outlet of the micro-electrolysis water inlet pipe, the other inlet of the pipeline mixer is connected with an acid dosing pipe, the outlet of the pipeline mixer is connected with an inlet of the micro-electrolysis reactor water inlet pipe, the outlet of the micro-electrolysis reactor water inlet pipe extends to the lower part of the micro-electrolysis reactor, a plurality of filler supporting layers are arranged in the micro-electrolysis reactor, block fillers are arranged on the filler supporting layers, an aeration pipe of the micro-electrolysis reactor is arranged below each filler supporting layer, a first baffle is arranged at the bottom of the micro-electrolysis reactor and is positioned right below the outlet of the micro-electrolysis reactor water inlet pipe, a micro-electrolysis reactor access hole is formed in the side wall of the micro-electrolysis reactor and corresponds to each filler supporting layer, a first separator is arranged above the filler supporting layer of the uppermost layer, a first overflow weir is arranged at the upper part in the micro-electrolysis reactor and is connected with a water outlet pipe of the micro-electrolysis reactor, and a water outlet of the water outlet pipe of the micro-electrolysis reactor is used as a water outlet of the micro-electrolysis device.
As described above, the Fenton device comprises a Fenton reactor water inlet pipe, the Fenton reactor water inlet pipe water inlet is used as the water inlet of the Fenton reactor device to be connected with the water outlet of the micro-electrolysis reactor water outlet pipe, the Fenton reactor water inlet pipe water outlet extends to the lower part of the Fenton reactor, the bottom of the Fenton reactor is provided with an aerator pipe and a second baffle, the second baffle is positioned right below the Fenton reactor water inlet pipe water outlet, the second overflow weir is positioned on the upper part of the Fenton reactor, the second separator is positioned below the second overflow weir, the second overflow weir is connected with the Fenton reactor water outlet pipe inlet, the Fenton reactor water outlet pipe outlet is the water outlet of the Fenton device, and the bottom of the Fenton reactor is connected with a dosing pipeline of hydrogen peroxide solution.
The neutralization tank is connected with the outlet of the Fenton reactor water outlet pipe, the aeration pipe is arranged at the bottom of the neutralization tank, the aeration pipe of the neutralization tank is connected with the second blower, the bottom of the neutralization tank is connected with the bottom of the flocculation tank through a flow passage, and the flow passage is used as the water outlet of the neutralization tank and the water inlet of the flocculation sedimentation tank;
the flocculation sedimentation tank includes the flocculation tank, the flocculation tank is provided with the flocculation tank mixer, the overflow mouth and the sedimentation tank inlet tube entrance connection of flocculation tank upper portion are connected to the flocculation tank, the inlet tube export of sedimentation tank extends to the middle part of sedimentation tank, be provided with the sedimentation tank mud bucket in the bottom of sedimentation tank, the sedimentation tank mud bucket is located the below of the inlet tube export of sedimentation tank, the sedimentation tank mud bucket is connected with the inlet of dredge pump, the export of dredge pump is as the ferric hydroxide delivery outlet of flocculation sedimentation tank, the upper portion of sedimentation tank is provided with the sedimentation tank delivery port, the sedimentation tank delivery port is as the delivery port of flocculation sedimentation tank.
The electric oxidation device comprises an electric oxidation water inlet tank, a water inlet of the electric oxidation water inlet tank is used as a water inlet of the electric oxidation device, the top of the electric oxidation water inlet tank is sealed, an aeration pipe is arranged at the bottom of the electric oxidation water inlet tank, the aeration pipe of the electric oxidation water inlet tank is connected with a third air blower, an inlet of a second air suction fan is connected to a space above the liquid level in the electric oxidation water inlet tank, an outlet of the second air suction fan is connected with an air inlet of an absorption tower, an inlet of an electric oxidation water inlet pump is connected with a water outlet of the electric oxidation water inlet tank, an outlet of the electric oxidation water inlet pump is connected with an inlet of a filter, an air outlet of the filter is connected with the electric oxidation water inlet tank through an air outlet of the electrolytic tank, an air outlet of the electrolytic tank is positioned below the liquid level of the electric oxidation water inlet tank, a water outlet of the electrolytic tank is connected into the electric oxidation water producing tank, the top of the electric oxidation water producing tank is sealed, an inlet of the first air suction fan is connected with a space above the liquid level in the electric oxidation water producing tank, an outlet of the first air suction fan is connected with an air inlet of the absorption tower, the bottom of the absorption tower is connected with the water tank, alkali solution is provided with a plurality of groups, when the interior of the alkali liquor water tank is empty, the inlet of the alkali liquor water tank is used as an alkali liquor input port of the electro-oxidation device, when the alkali liquor water tank is filled with sodium hydroxide solution, the inlet of the alkali liquor water tank is disconnected with an alkali liquor output port of the bipolar membrane electrodialysis device, the outlet of the alkali liquor water tank is connected with the inlet of a spray pump, the outlet of the spray pump is connected with the upper water inlet of the absorption tower, the inlet of the alkali liquor water tank is connected with the water outlet of the absorption tower, when the concentration of the sodium hypochlorite solution in the alkali liquor water tank reaches a set value, the outlet of the alkali liquor water tank is a sodium hypochlorite water outlet of the electro-oxidation device, and the water outlet of the electro-oxidation water production tank is used as the water outlet of the electro-oxidation device.
The first hard removal device comprises a first reaction tank, the bottom of the first reaction tank is connected with the bottom of a second reaction tank through a through-flow channel, the upper part of the second reaction tank is connected with the upper part of a third reaction tank through an overflow channel, the first reaction tank is provided with a first stirrer, the second reaction tank is provided with a second stirrer, the third reaction tank is provided with a third stirrer, a water inlet of the first reaction tank is used as a water inlet of the first hard removal device, an alkali liquor dosing pipe is arranged in the first reaction tank, the alkali liquor dosing pipe of the first reaction tank is used as an alkali liquor dosing pipe of the first hard removal device, the second reaction tank is connected with a sodium carbonate dosing pipe, the third reaction tank is connected with an ultrafiltration membrane inlet through an ultrafiltration membrane concentrated water outlet which is connected with the third reaction tank, the ultrafiltration membrane water outlet is connected with a second water producing tank, the second water producing tank is connected with a first hard removal device resin tank through a second lift pump, strong acid cation exchange resin is filled in the first hard removal device resin tank, and an outlet of the first hard removal device resin tank is used as a water outlet of the first hard removal device.
A coking wastewater membrane filtration concentrate treatment method, which utilizes the coking wastewater membrane filtration concentrate treatment system, is characterized by comprising the following steps:
S1, removing most organic pollutants in coking wastewater membrane filtration concentrate in a first adsorption device through active carbon; the effluent of the first adsorption device enters a micro-electrolysis device, an acid solution is added to adjust the pH value of the inlet water of the micro-electrolysis device to 2-3, ferrous ions are generated while organic pollutants and chromaticity in the wastewater are further removed, the produced water of the micro-electrolysis device enters a Fenton device, and the Fenton device utilizes the ferrous ions and hydrogen peroxide to further oxidize and remove the organic pollutants and chromaticity in the wastewater, and ferric ions are generated;
s2, the effluent of the Fenton device enters a neutralization tank, the pH value in the neutralization tank is regulated to 7-8 by using alkali solution, a flocculating agent is added into a flocculation tank, then sedimentation is carried out in a sedimentation tank, the effluent of the sedimentation tank enters an electro-oxidation device, and ferric hydroxide sediment in the sedimentation tank enters a sodium ferrate preparation device;
s3, removing ammonia nitrogen, COD and chromaticity in the wastewater by using an electrooxidation device, generating a sodium hypochlorite solution by using an alkali solution, enabling the sodium hypochlorite solution to enter a sodium ferrate preparation device, and enabling electrooxidation produced water to enter a first hardness removal device; the first hardness removing device adopts chemical precipitation and resin softening to remove hardness in the wastewater, and the effluent after the hardness removal enters a nanofiltration device;
S4, the produced water of the first hardness removal device is subjected to nanofiltration to obtain nanofiltration produced water with sodium chloride as a main component, the nanofiltration produced water enters a first vacuum membrane distillation device, concentrated water of the first vacuum membrane distillation device enters a crystallizer to obtain sodium chloride crystals, a part of mother liquor output by the crystallizer flows back to the first vacuum membrane distillation device, the other part of mother liquor output by the crystallizer enters a second adsorption device, the produced water of the first vacuum membrane distillation device enters a produced water tank, the nanofiltration concentrated water enters a second vacuum membrane distillation device to be further concentrated, the concentrated water of the second vacuum membrane distillation device enters a low-temperature crystallizer to obtain sodium sulfate decahydrate crystals, the produced water of the second vacuum membrane distillation device enters a produced water tank, most of mother liquor of the low-temperature crystallizer flows back to the second vacuum membrane distillation device, and the rest part of mother liquor of the low-temperature crystallizer enters the second adsorption device;
s5, adsorbing and removing organic matters in the mother liquor output by the low-temperature crystallizer by using granular activated carbon and macroporous adsorption resin in a second adsorption device, enabling effluent of the second adsorption device to enter a second hardness removal device, softening by using resin to remove hardness in wastewater, and enabling effluent of the second hardness removal device to enter a bipolar membrane electrodialysis device;
S6, preparing mixed acid of hydrochloric acid and sulfuric acid and sodium hydroxide solution by the bipolar membrane electrodialysis device, wherein the mixed acid is reused for the micro-electrolysis device, one part of the sodium hydroxide solution is used for regulating the pH value by the neutralization tank, the other part of the sodium hydroxide solution is used for absorbing tail gas by an alkali liquor water tank of the electro-oxidation device, and the other part of the sodium hydroxide solution is used for preparing sodium ferrate solution by ferric hydroxide from a flocculation sedimentation tank and sodium hypochlorite from the electro-oxidation device in the sodium ferrate preparation device.
Setting a plurality of groups of alkali liquor water tanks in the step S3, switching to the next group of alkali liquor water tanks to continue to run after the mass concentration of the sodium hypochlorite solution reaches 10%, and then conveying the alkali liquor water tanks to a sodium ferrate preparation device through a lifting pump; the first hard removing device resin tank is filled with strong acid cation exchange resin, and hydrogen ions are released to adjust the pH value of the wastewater; and (3) the mass concentration of the sodium hydroxide solution prepared by bipolar membrane electrodialysis in the step S6 is 8-10%, and the mixed acid is used for regulating the pH value of a micro-electrolysis device, regenerating the resin inside or outside the system and cleaning the membrane inside or outside the system.
And (2) heating the first vacuum membrane distillation device and the second vacuum membrane distillation device in the step S4 by using the waste heat of a steel mill to ensure that the operation temperature of the waste water is 50-70 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention utilizes the pretreatment process of adsorption, micro-electrolysis, fenton and electrooxidation, can effectively remove refractory organic matters and chromaticity in water, acid and alkali used in the treatment come from a bipolar membrane electrodialysis device in the system, and the combined application of micro-electrolysis and Fenton can omit the addition of ferrous sulfate, thereby reducing the addition of agents to increase the salt content in the wastewater and effectively improving the water quality of the subsequent salt separation crystallization process. Meanwhile, chemical precipitation is adopted to remove hardness and resin is adopted to remove hardness of calcium and magnesium in the concentrated solution effectively, impurities in the wastewater are reduced, and purity of a subsequent salt separation crystallization product is improved.
2. The concentration process adopted by the process combines nanofiltration, vacuum membrane distillation and crystallization processes, adopts nanofiltration to separate salt from wastewater, and utilizes the selective interception characteristic of the nanofiltration membrane on divalent salt to realize the separation of monovalent salt sodium chloride and divalent salt sodium sulfate in a liquid phase, wherein sodium chloride mainly enters nanofiltration produced water, sodium sulfate is concentrated in nanofiltration concentrated water, and the nanofiltration produced water and the nanofiltration concentrated water are respectively subjected to vacuum membrane distillation concentration and then are crystallized to obtain sodium chloride and sodium sulfate. The vacuum membrane distillation device adopts the waste heat of the steel mill as a heat source, so that the energy consumption can be effectively reduced, the heat energy utilization efficiency of the steel mill is improved, and the purposes of energy conservation and emission reduction are realized. High recovery rate, lower running cost, stable water quality of produced water, stable water quality of discharged water reaching the standard of reuse water and high comprehensive recovery rate of crystallized salt.
3. The mixed salt left after salt separation crystallization is used for preparing mixed acid and sodium hydroxide solution through adsorption, hardness removal and bipolar membrane electrodialysis, so that the recycling recovery rate of concentrated solution is further improved, the mixed acid and sodium hydroxide solution are used for the consumption of the inside of a treatment system, the chlorine and iron mud generated in the treatment process are continuously recycled, and the sodium ferrate solution obtained by synthesizing sodium ferrate at low temperature by utilizing ferric hydroxide, sodium hypochlorite and sodium hydroxide can be used for treating coking wastewater. The bipolar membrane electrodialysis technology is used for recycling mixed salt, and the ferric mud generated by the micro-electrolysis-Fenton technology and the sodium hypochlorite solution generated by electrooxidation are combined to prepare the sodium ferrate solution with obvious economic benefit, so that the recycling utilization rate of the concentrated solution is further improved, and zero discharge of the concentrated solution can be realized by adopting the technology.
Drawings
FIG. 1 is a process flow diagram of a coking wastewater membrane filtration concentrate treatment system.
Fig. 2 is a schematic structural view of the first adsorption apparatus.
FIG. 3 is a schematic diagram of the structure of a micro-electrolysis-Fenton reactor-neutralization tank-flocculation sedimentation tank device.
Fig. 4 is a schematic structural view of the electro-oxidation device.
FIG. 5 is a schematic diagram of the structure of the first hardness removing device.
In the figure: 1-a first adsorption device water inlet tank; 2-a water inlet pump; 3-a first blower; 4-an adsorption reaction tank; 5-a filtration device; 6-a first water producing tank; 7-a first lift pump; 10-a micro-electrolysis reactor; 11-a micro-electrolysis water inlet pipe; 12-acid dosing tube; 13-pipe mixer; 14-a water inlet pipe of the micro-electrolysis reactor; 15-a first separator; 16-a first weir; 17-a microelectrolysis reactor exhaust; 18-a micro-electrolysis reactor access port; 19-a micro-electrolysis reactor aerator pipe; 20-a first baffle; 21-a first air compressor; 22-a first air storage tank; 23-a filler support layer; 24-a water outlet pipe of the micro-electrolysis reactor; 25-Fenton reactor inlet pipe; a 26-Fenton reactor; 27-a second weir; 28-Fenton reactor access; 29-a second air compressor; 30-a second air storage tank; 31-a second baffle; 32-a second separator; a 33-Fenton reactor water outlet pipe; 34-a second blower; 35-a neutralization tank; 36-flocculation tank; 37-a sedimentation tank; 38-a sludge pump; 39-flocculation tank stirrer; 40-a water outlet of the sedimentation tank; 41-electro-oxidation water inlet tank; 42-a third blower; 43-electric oxidation water inlet pump; 44-a filter; 45-electrolytic cell; 46-a power supply; 47-an electrolyzer exhaust pipe; 48-electro-oxidation water producing tank; 49-a first air extraction fan; 50-a second air extraction fan; 51-an absorption column; 52-an alkali liquor tank; 53-a spray pump; 61-a first reaction tank; 62-a second reaction tank; 63-a third reaction tank; 64-ultrafiltering water inlet pump; 65-ultrafiltration membrane; 66-a first stirrer; 67-a second stirrer; 68-a third stirrer; 69-a second water production tank; 70-a second lift pump; 71-a first hardness removal device resin tank.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
In the specific implementation, the process flow of the coking wastewater membrane filtration concentrate treatment system is shown in fig. 1.
A coking wastewater membrane filtration concentrate treatment system comprises a first adsorption device, a micro-electrolysis device, a Fenton device, a neutralization tank 35, a flocculation sedimentation tank, an electro-oxidation device, a first hardness removal device, a nanofiltration device, a second vacuum membrane distillation device, a low-temperature crystallizer, a second adsorption device, a second hardness removal device, a bipolar membrane electrodialysis device, and further comprises a first vacuum membrane distillation device, a water production tank, a crystallizer and a sodium ferrate preparation device.
The concentrated solution of coking wastewater membrane filtration is input into a water inlet of a first adsorption device, a water outlet of the first adsorption device is connected with a micro-electrolysis water inlet pipe 11 of a micro-electrolysis device, a water outlet of the micro-electrolysis device is connected with a water inlet of a Fenton device, a water outlet of the Fenton device is connected with a water inlet of a neutralization tank 35, a water outlet of the neutralization tank 35 is connected with a water inlet of a flocculation sedimentation tank, an iron hydroxide output port of the flocculation sedimentation tank is connected with a sodium ferrate preparation device, a water outlet of the flocculation sedimentation tank is connected with a water inlet of an electro-oxidation device, a sodium hypochlorite water outlet of the electro-oxidation device is connected with the sodium ferrate preparation device, a water outlet of the electro-oxidation device is connected with a water inlet of a first hardness removal device, a water outlet of the first hardness removal device is connected with a water inlet of a receiving filter device, a nanofiltration water outlet of the nanofiltration device is connected with a water inlet of a first vacuum membrane distillation device, a concentrated water outlet of the first vacuum membrane distillation device is connected with a crystallizer, the mother liquor water outlet of the crystallizer is respectively connected with the water inlet of the first vacuum membrane distillation device and the water inlet of the second adsorption device, the water outlet of the first vacuum membrane distillation device is connected with the water producing pool, the concentrated water outlet of the nanofiltration device is connected with the water inlet of the second vacuum membrane distillation device, the water outlet of the second vacuum membrane distillation device is connected with the water producing pool, the concentrated water outlet of the second vacuum membrane distillation device is connected with the low-temperature crystallizer, the mother liquor water outlet of the low-temperature crystallizer is respectively connected with the water inlet of the second vacuum membrane distillation device and the water inlet of the second adsorption device, the water outlet of the second adsorption device is connected with the water inlet of the second hardness removing device, the water outlet of the second hardness removing device is connected with the water inlet of the bipolar membrane electrodialysis device, and the water outlet of the bipolar membrane electrodialysis device is respectively connected with the alkali liquor adding pipe of the neutralization pool 35, the alkali liquor input port of the electro-oxidation device, the alkali liquor dosing pipe of the first hardness removal device and the sodium ferrate preparation device are connected, the acid liquor water outlet of the bipolar membrane electrodialysis device is connected with the acid dosing pipe 12 of the micro-electrolysis device, and the fresh water outlet of the bipolar membrane electrodialysis device is connected with the water inlet of the nanofiltration device.
As shown in fig. 2, the first adsorption device comprises a first adsorption device water inlet tank 1, a water inlet pump 2, an adsorption reaction tank 4, a first lift pump 7, a filtering device 5 and a first water production tank 6 which are sequentially connected. The water inlet of the water inlet tank 1 of the first adsorption device is used as the water inlet of the first adsorption device, the water inlet of the water inlet pump 2 is connected with the water inlet tank 1 of the first adsorption device, the water outlet of the water inlet pump 2 is connected with the adsorption reaction tank 4, the adsorption reaction tank 4 is divided into a first tank and a second tank by a partition plate, an overflow channel is reserved between the lower part of the partition plate and the bottom of the adsorption reaction tank 4, the bottom of the first tank and the bottom of the second tank of the adsorption reaction tank 4 are communicated through the overflow channel, the adsorption reaction tank 4 is changed into a partial plug flow type from a general complete mixing type, a certain removal efficiency can be improved, the water outlet of the water inlet pump 2 is connected with the first tank of the adsorption reaction tank 4, aeration pipes are arranged at the bottoms of the first tank and the second tank of the adsorption reaction tank 4, and the first tankThe inlets of the aeration pipes of the water tank and the second water tank are connected with the first blower 3, and the aeration amount is 3-5L/(m) according to the area of the liquid level 2 S), the inlet of the first lifting pump 7 is connected with the second water tank of the adsorption reaction tank 4, the outlet of the first lifting pump 7 is connected with the water inlet of the filtering device 5, the concentrated water port of the filtering device 5 is connected with the first water tank of the adsorption reaction tank 4, and the water outlet of the filtering device 5 is connected with the first water tank 6; the filtering device 5 adopts a rotary disc type filtering machine, the filtering precision of the rotary disc filtering material is 5 mu m, the running pressure is 0.1-0.4 Mpa, the rotating speed of the rotary disc is 60-300 r/min, a water outlet of the filtering device 5 is connected with an external sludge dehydrator, a part of water which is provided with activated carbon (sludge) and needs to be discharged during cleaning and maintenance after the filtering device 5 runs for a period of time is discharged through the water outlet, the water discharged from the water outlet enters the sludge dehydrator, the sludge dehydrator adopts a plate-and-frame filter press, the water after filter pressing flows back to the first water producing tank 6, the waste water in the first water producing tank 6 is lifted to the micro-electrolysis device through a water pump, a water outlet of the first water producing tank 6 is a water outlet of the first adsorption device, and a water outlet of the first water producing tank 6 is connected with an inlet of the micro-electrolysis water inlet pipe 11. Most of organic pollutants in the coking wastewater membrane filtration concentrated solution are removed by activated carbon in an adsorption reaction tank 4 of the first adsorption device.
As shown in fig. 3, the micro-electrolysis apparatus includes a micro-electrolysis reactor 10, a micro-electrolysis water inlet pipe 11, an acid dosing pipe 12, a pipe mixer 13, a micro-electrolysis reactor water inlet pipe 14, a micro-electrolysis reactor air outlet 17, a first separator 15, a first overflow weir 16, a micro-electrolysis reactor access opening 18, a micro-electrolysis reactor aeration pipe 19, a first baffle 20, a first air compressor 21, a first air tank 22, a filler support layer 23, and a micro-electrolysis reactor water outlet pipe 24. One inlet of the pipeline mixer 13 is connected with the outlet of the micro-electrolysis water inlet pipe 11, the other inlet of the pipeline mixer 13 is connected with the acid dosing pipe 12, the outlet of the pipeline mixer 13 is connected with the inlet of the micro-electrolysis reactor water inlet pipe 14, the outlet of the micro-electrolysis reactor water inlet pipe 14 extends to the lower part of the micro-electrolysis reactor 10, a plurality of filler supporting layers 23 are arranged in the micro-electrolysis reactor 10 from top to bottom, a filler is arranged on each filler supporting layer 23, a micro-electrolysis reactor aeration pipe 19 is arranged below each filler supporting layer 23, the bottom of the micro-electrolysis reactor 10 is provided with a first baffle 20, the first baffle 20 is positioned right below the outlet of the bottom of the micro-electrolysis reactor water inlet pipe 14, the first baffle 20 can form a rotational flow with the effluent of the micro-electrolysis reactor water inlet pipe 14, a micro-electrolysis reactor overhaul port 18 is arranged on the side wall of the micro-electrolysis reactor 10 corresponding to each filler supporting layer 23, each micro-electrolysis reactor aeration pipe 19 is connected with the outlet of a first air storage tank 22, the inlet of the first air storage tank 22 is connected with a first air reservoir 21, the upper supporting layer 23 is provided with a first weir 15, a first overflow weir 16 is arranged on the micro-electrolysis reactor 16, and a water outlet pipe 16 is connected with a first overflow device; the micro-electrolysis reactor 10 uses high-temperature sintered iron carbon filler, the filler arranged on a filler supporting layer 23 is in a block shape, the diameter is 3-5 cm, the filler is added from a micro-electrolysis reactor maintenance hole 18, compressed air aeration provided by a first air compressor 21 and a first air storage tank 22 is utilized to wash the surface of the filler, so that the filler is stirred, the mass transfer effect is improved, and the pressure of the compressed air is 0.4-0.7 Mpa; the separator 15 at the top adopts a two-layer triangle, the top of the triangle is provided with exhaust pipes, each exhaust pipe is integrated into a first exhaust manifold, the first exhaust manifold extends to the position above the liquid level, and the first exhaust manifold is connected to the exhaust port 17 of the micro-electrolysis reactor; the hydraulic retention time of the micro-electrolysis reactor 10 is 2 to 4 hours. Organic contaminants and chromaticity in the wastewater are further removed in the micro-electrolysis reactor 10 while a large amount of ferrous ions are generated, and then the produced water of the micro-electrolysis reactor 10 enters the Fenton device.
The Fenton device comprises a Fenton reactor water inlet pipe 25, a Fenton reactor 26, a second overflow weir 27, a Fenton reactor access hole 28, a second air compressor 29, a second air storage tank 30, a second baffle 31, a second separator 32 and a Fenton reactor water outlet pipe 33. The water inlet at the top of the Fenton reactor water inlet pipe 25 is used as the water inlet of the Fenton reactor device and is connected with the water outlet of the micro-electrolysis reactor water outlet pipe 24 through a water pipeline, and the water outlet at the bottom of the Fenton reactor water inlet pipe 25 extends to the lower part of the Fenton reactor 26The bottom of the reactor 26 is provided with an aeration pipe and a second baffle 31, the second baffle 31 is positioned under the water outlet at the bottom end of the Fenton reactor water inlet pipe 25, the aeration pipe of the Fenton reactor 26 is connected with the outlet of a second air storage tank 30, the inlet of the second air storage tank 30 is connected with a second air compressor 29, a second overflow weir 27 is positioned at the upper part of the Fenton reactor 26, a second separator 32 is positioned under the second overflow weir 27, the second overflow weir 27 is connected with the inlet of a Fenton reactor water outlet pipe 33, and the outlet of the Fenton reactor water outlet pipe 33 is the water outlet of a Fenton device; the separator 32 is formed by two layers of triangular plates, the top of each triangular plate is provided with an exhaust pipe, and each exhaust pipe is integrated into a second exhaust manifold which is communicated above the liquid level and is communicated with a Fenton reactor air outlet arranged at the top of the Fenton reactor 26; the lower part of the side wall of the Fenton reactor 26 is provided with a Fenton reactor overhaul port 28 for overhauling the inside of the Fenton reactor 26; the bottom of the Fenton reactor 26 is connected with a dosing pipeline, the dosing pipeline is used for adding hydrogen peroxide solution, the aeration amount of the Fenton reactor 26 is calculated according to the liquid level area, and the value range is 0.6-3L/(m) 2 S), the aeration pressure is 0.3-0.4 Mpa; the hydraulic retention time of the Fenton reactor 26 is 1-2 hours;
the neutralization tank 35 is connected with the outlet of the Fenton reactor water outlet pipe 33, the neutralization tank 35 is provided with an alkali liquor dosing pipe, the alkali liquor dosing pipe of the neutralization tank 35 is connected with an alkali liquor output port of bipolar membrane electrodialysis, the bottom of the neutralization tank 35 is provided with an aeration pipe, and the aeration amount of the neutralization tank 35 is calculated to be 3-5L/(m) according to the liquid level area 2 S) the aeration pipe of the neutralization tank 35 is connected with the second blower 34, the bottom of the neutralization tank 35 and the bottom of the flocculation tank 36 are connected through a flow passage, and the flow passage is used as the water outlet of the neutralization tank 35 and the water inlet of the flocculation tank 36 (namely the water inlet of the flocculation sedimentation tank).
The flocculation sedimentation tank comprises a flocculation tank 36 and a sedimentation tank 37, wherein the flocculation tank 36 is provided with a flocculation tank stirrer 39, the flocculation tank 36 is connected with a flocculant dosing pipe, an overflow port at the upper part of the flocculation tank 36 is connected with a water inlet pipe inlet of the sedimentation tank 37, a water inlet pipe outlet of the sedimentation tank 37 extends to the middle part of the sedimentation tank 37, a sedimentation tank mud bucket is arranged at the bottom of the sedimentation tank 37 and is positioned below a water inlet pipe outlet of the sedimentation tank 37, an inlet of a mud pump 38 is connected with the sedimentation tank mud bucket, an outlet of the mud pump 38 is used as a ferric hydroxide output port of the flocculation sedimentation tank to be connected with a sodium ferrate preparation device, a sedimentation tank water outlet 40 is positioned at the upper part of the sedimentation tank 37, and the sedimentation tank water outlet 40 is used as a water outlet of the flocculation sedimentation tank to be connected with a water inlet of an electro-oxidation device; specifically, the hydraulic retention time of the neutralization tank 35 is 15-30 min, the hydraulic retention time of the flocculation tank 36 is 5-10 min, and the hydraulic retention time of the sedimentation tank 37 is 2 hours;
As shown in fig. 4, the electro-oxidation device comprises an electro-oxidation water inlet tank 41, a third blower 42, an electro-oxidation water inlet pump 43, a filter 44, an electrolytic cell 45, a power supply 46, an electrolytic cell exhaust pipe 47, an electro-oxidation water producing tank 48, a first air suction fan 49, a second air suction fan 50, an absorption tower 51, an alkali liquor tank 52 and a spray pump 53. The water inlet of the electric oxidation water inlet tank 41 is used as the water inlet of the electric oxidation device, the top of the electric oxidation water inlet tank 41 is closed, an aeration pipe is arranged at the bottom of the electric oxidation water inlet tank 41, the aeration pipe of the electric oxidation water inlet tank 41 is connected with a third blower 42, the inlet of the second air suction blower 50 is connected with the space above the liquid level in the electric oxidation water inlet tank 41 through a gas transmission pipeline, the outlet of the second air suction blower 50 is connected with the air inlet of the absorption tower 51, the inlet of the electric oxidation water inlet pump 43 is connected with the water outlet of the electric oxidation water inlet tank 41, the outlet of the electric oxidation water inlet pump 43 is connected with the inlet of the filter 44, the outlet of the filter 44 is connected with the inlet of the electrolytic tank 45, the air outlet of the electrolytic tank 45 is connected with the electric oxidation water inlet tank 41 through an electrolytic tank air outlet 47, and the air outlet of the electrolytic tank air outlet 47 is positioned below the liquid level of the electric oxidation water inlet tank 41, the water outlet of the electrolytic tank 45 is connected with the inside of the electro-oxidation water producing tank 48, the top of the electro-oxidation water producing tank 48 is closed, each electrolytic tank 45 is powered by a power supply 46, the inlet of a first air suction fan 49 is connected with the space above the liquid level in the electro-oxidation water producing tank 48 through a gas pipeline, the outlet of the first air suction fan 49 is connected with the air inlet of an absorption tower 51, the bottom of the absorption tower 51 is connected with an alkali liquor water tank 52, the alkali liquor water tanks 52 are provided with a plurality of groups, when the inside of the alkali liquor water tank 52 is the space-time inlet of the alkali liquor water tank 52 serving as the alkali liquor inlet of the electro-oxidation device and the alkali liquor outlet of the bipolar membrane electrodialysis device, and the inlet of the alkali liquor water tank 52 is disconnected with the alkali liquor outlet of the bipolar membrane electrodialysis device after sodium hydroxide solution is to be filled in The inlet of the outlet spray pump 53 of the alkali liquor water tank 52 is connected to absorb chlorine, the outlet of the spray pump 53 is connected to the upper water inlet of the absorption tower 51, and at this time, the inlet of the alkali liquor water tank 52 is connected to the lower water outlet of the absorption tower 51 to collect the generated sodium hypochlorite solution; when the sodium hypochlorite solution generated by the absorption of the chlorine by the alkali liquor water tank 52 reaches the set concentration, the water outlet of the alkali liquor water tank 52 filled with the sodium hypochlorite solution with the set concentration is the sodium hypochlorite water outlet of the electro-oxidation device, at the moment, the next alkali liquor water tank 52 assembled with the sodium hydroxide solution is switched to be connected with the inlet of the spray pump 53 to continue to operate the absorption tower 51, and the alkali liquor water tank 52 containing the sodium hypochlorite solution is connected with an external lifting pump to send the sodium hypochlorite solution to the sodium ferrate preparation device; the water outlet of the electrooxidation water producing tank 48 serves as the water outlet of the electrooxidation device. The electro-oxidation water inlet tank 41 and the electro-oxidation water producing tank 48 are stirred by adopting microporous aeration, and the chlorine generated in the electro-oxidation water inlet tank 41 and the electro-oxidation water producing tank 48 is respectively sucked by a second suction fan 50 and a first suction fan 49 and is conveyed to an absorption tower 51, and the absorption tower 51 absorbs the chlorine by alkali liquor to obtain sodium hypochlorite solution; the electrode plate of the electrolytic tank 45 adopts a porous electrode plate, the aperture is 20-50 mu m, the thickness of the electrode plate is 3-5 mm, the water flow direction in the electrolytic tank 45 is vertical to the electrode plate, the waste water sequentially penetrates through each electrode plate, the anode plate and the cathode plate are sequentially and alternately arranged, the electrode plate distance is 1-2 cm, and the current density of the electrolytic tank 45 is 600-800A/m 2 。
As shown in fig. 5, the first hardness removing device includes a first reaction tank 61, a second reaction tank 62, a third reaction tank 63, an ultrafiltration water inlet pump 64, an ultrafiltration membrane 65, a second water production tank 69, a second lift pump 70, and a first hardness removing device resin tank 71, which are sequentially connected. The bottom of the first reaction tank 61 is connected with the bottom of the second reaction tank 62 through a flow passage, the upper part of the second reaction tank 62 is connected with the upper part of the third reaction tank 63 through an overflow passage, the first reaction tank 61 is provided with a first stirrer 66, the second reaction tank 62 is provided with a second stirrer 67, the third reaction tank 63 is provided with a third stirrer 68, the water outlet of the electro-oxidation water producing tank 48 is connected with the water inlet of the first reaction tank 61, the water inlet of the first reaction tank 61 is used as the water inlet of the first hard removing device, the first reaction tank 61 is provided with an alkali liquor adding pipe, the alkali liquor adding pipe of the first reaction tank 61 is used as the alkali liquor adding pipe of the first hard removing device and is connected with the alkali liquor output port of the bipolar membrane electrodialysis device, the second reaction tank 62 is connected with a sodium carbonate adding pipe, the inlet of the ultrafiltration water inlet pump 64 is connected with the inlet of the ultrafiltration membrane 65, the ultrafiltration water outlet of the ultrafiltration water inlet pump 64 is connected with the third reaction tank 63, the water outlet of the ultrafiltration membrane 65 is connected with the water producing tank 69, the inlet of the second hard lifting pump 70 is connected with the water outlet of the second lifting tank 69, the second lifting pump 70 is connected with the water outlet of the first hard removing device 71; the ultrafiltration membrane 65 of the first hardness removal device was a tubular ultrafiltration membrane having a filtration accuracy of 50nm, and the resin tank 71 of the first hardness removal device was a strongly acidic cation exchange resin; during the operation of the ultrafiltration membrane 65, a part of concentrated water needs to be discharged, the discharged concentrated water enters an external sludge dehydrator, the sludge dehydrator adopts a plate-and-frame filter press, and the discharged water after being filtered by the plate-and-frame filter press flows back to the second water producing tank 69; when the resin in the first hardness removal device resin tank 71 needs to be regenerated during use, the mixed acid produced by the bipolar membrane electrodialysis device is used for regeneration.
After the hardness is removed by the first hardness removal device, the concentration of calcium and magnesium is lower, but after the concentration treatment of the wastewater by the second vacuum membrane distillation device, the concentration of calcium and magnesium is increased, so that the concentration of calcium and magnesium is required to be reduced by using the resin of the second hardness removal device, and the water quality of the inlet water of bipolar membrane electrodialysis is ensured.
Example 2
In specific implementation, the process flow of the coking wastewater membrane filtration concentrated solution treatment method is shown in figure 1.
A coking wastewater membrane filtration concentrate treatment method, which utilizes the coking wastewater membrane filtration concentrate treatment system described in the embodiment 1, comprises the following steps:
s1, removing organic pollutants and chromaticity in the coking wastewater membrane filtration concentrated solution. Removing most organic pollutants in coking wastewater membrane filtration concentrated solution in a first adsorption device through active carbon; the effluent of the first adsorption device enters a micro-electrolysis device, the pH value of the water entering the micro-electrolysis device is adjusted to be 2-3 by adding the mixed acid solution from bipolar membrane electrodialysis, the organic pollutants and chromaticity in the wastewater are further removed, meanwhile, ferrous ions are generated, the produced water of the micro-electrolysis device enters a Fenton device, and the Fenton device utilizes the ferrous ions and hydrogen peroxide to further oxidize and remove the organic pollutants and chromaticity in the wastewater, and meanwhile, ferric ions are generated. The specific process is as follows:
The coking wastewater membrane filtration concentrated solution is firstly stored in a concentrated solution pond, then is sent to a first adsorption device water inlet tank 1 through a lifting pump, is then sent to an adsorption reaction tank 4 through a water inlet pump 2, is added with a powdery active carbon solution with the mass concentration of 5-10%, the powdery active carbon is used for removing most organic pollutants in wastewater, the wastewater of the adsorption reaction tank 4 is sent to a filtering device 5 through a first lifting pump 7, the separation of the powdery active carbon is realized by filtering in the filtering device 5, part of separated concentrated water flows back to the adsorption reaction tank 4, part of separated concentrated water is discharged to an external powdery active carbon dehydration device (such as a plate-and-frame filter press in the embodiment) during maintenance and cleaning, the dehydrated clear liquid flows to a first water production tank 6, and the wastewater in the first water production tank 6 is lifted to a micro-electrolysis device through a water pump;
the wastewater in the first water production tank 6 enters the pipeline mixer 13 from the micro-electrolysis water inlet pipe 11, and meanwhile, an acid solution is added into the pipeline mixer 13 from the acid adding pipe 12, wherein the acid solution is mixed acid solution (HCl solution and H 2 SO 4 Solution) output port, the micro-electrolysis reactor 10 is provided with a pH meter, the pH of the inlet water of the micro-electrolysis reactor 10 is controlled to be 2-3, the micro-electrolysis reactor 10 is filled with iron-carbon filler, the iron-carbon micro-electrolysis reaction is utilized to further remove organic pollutants and chromaticity in the wastewater, a large amount of ferrous ions are generated, and the produced water of the micro-electrolysis reactor 10 enters the Fenton reactor 26;
The Fenton reactor 26 further oxidizes and removes organic pollutants and chromaticity in the wastewater by utilizing ferrous ions and hydrogen peroxide solution added in a dosing pipeline at the bottom of the Fenton reactor 26, and simultaneously generates a large amount of ferric ions;
the micro-electrolysis reactor 10 and the Fenton reactor 26 are both stirred by adopting an air compressor for aeration, the air inlet pressure of the micro-electrolysis reactor 10 is 0.4-0.7 Mpa, and the aeration pressure of the Fenton reactor 26 is 0.3-0.4 Mpa;
s2, removing iron ions. The effluent of the Fenton device enters a neutralization tank 35, the pH value in the neutralization tank 35 is regulated to 7-8 by utilizing an alkali solution from a bipolar membrane electrodialysis device, a flocculating agent is added into a flocculation tank 36, then precipitation is carried out in a precipitation tank 37, the effluent of the precipitation tank 37 enters an electro-oxidation device, and ferric hydroxide precipitate in the precipitation tank 37 enters a sodium ferrate preparation device:
the effluent of the Fenton device enters a neutralization tank 35 from a water outlet pipe 33 of the Fenton reactor, an alkali solution is added into the neutralization tank 35, the alkali solution is taken from an alkali solution outlet of bipolar membrane electrodialysis, the pH value of wastewater in the neutralization tank 35 is regulated to 7-8, a second blower 34 is utilized for aeration stirring in the neutralization tank 35, the divalent iron which is not oxidized is continuously oxidized into trivalent iron, and then the effluent of the neutralization tank 35 is regulated to overflow to a flocculation tank 36;
Adding a flocculating agent (the flocculating agent is anionic polyacrylamide PAM with the mass concentration of 0.1-0.2%) into a flocculation tank 36, stirring by a flocculation tank stirrer 39, then, entering a sedimentation tank 37 from a sedimentation tank water inlet pipe, precipitating wastewater in the sedimentation tank 37, then, entering an electro-oxidation device from the water outlet of the sedimentation tank 37, and conveying ferric hydroxide sediment in a mud bucket of the sedimentation tank 37 to a sodium ferrate preparation device by a mud pump 38;
s3, removing ammonia nitrogen, COD, chromaticity and hardness in the wastewater to generate sodium hypochlorite solution. The electro-oxidation device removes ammonia nitrogen, COD and chromaticity in the wastewater, and simultaneously utilizes an alkali solution from the bipolar membrane electrodialysis device to generate sodium hypochlorite solution, wherein the sodium hypochlorite solution enters a sodium ferrate preparation device, and electro-oxidation produced water enters a first hardness removal device; the first hardness removal device adopts chemical precipitation and resin softening to remove hardness in wastewater, and effluent after hardness removal enters a nanofiltration device:
the effluent of the sedimentation tank 37 is firstly stored in an electrooxidation water inlet tank 41, lifted into an electrolytic tank 45 by an electrooxidation water inlet pump 43, a porous electrode plate is arranged in the electrolytic tank 45, the thickness of the electrode plate is 3-5 mm, the anode plate and the cathode plate are alternately arranged, the distance between the electrode plates is 1-2 cm, The electrolytic tank 45 is connected with a power supply 46, and the current density of the electrolytic tank 45 is 600-800A/m 2 The waste water is oxidized to remove ammonia nitrogen, COD and chromaticity when passing through the porous electrode plate, tail gas (mainly comprising air, chlorine and a small amount of hydrogen) generated in the oxidation process firstly enters an electro-oxidation water inlet tank 41 to be absorbed by a solution, unabsorbed tail gas is sent into an absorption tower 51 by a second air suction fan 50, meanwhile, produced water of an electro-oxidation device firstly enters an electro-oxidation water producing tank 48 and then is sent to a first hardness removing device, the electro-oxidation water inlet tank 41 and the electro-oxidation water producing tank 48 are both blown off and stirred by using a third air blower 42, the tail gas in the electro-oxidation water producing tank 48 is sent into the absorption tower 51 by using a first air suction fan 49, the absorption tower 51 adopts alkali liquor to spray, sodium hypochlorite solution is generated after absorbing the chlorine, alkali liquor in an alkali liquor water tank 52 is from an alkali solution of a bipolar membrane electrodialysis device, and the alkali liquor is sent into the absorption tower 51 by using a spray pump 53. The alkali liquor water tanks 52 are provided with a plurality of groups, firstly the empty alkali liquor water tanks 52 are connected with an alkali liquor output port of the bipolar membrane electrodialysis device, and sodium hydroxide solution is collected; then an alkali liquor water tank 52 filled with sodium hydroxide solution is connected to the inlet of a spray pump 53 to absorb chlorine; when a group of alkali liquor water tanks 52 absorb sodium hypochlorite solution generated by chlorine to reach the mass concentration of 10%, the next alkali liquor water tank 52 assembled with sodium hydroxide solution is switched to be connected with the inlet of a spray pump 53 to continuously operate an absorption tower 51, the alkali liquor water tank 52 containing sodium hypochlorite solution is connected with an external lifting pump so as to send the sodium hypochlorite solution to a sodium ferrate preparation device, besides the alkali liquor by utilizing bipolar membrane electrodialysis, sodium hydroxide solids can be added into the alkali liquor water tank 52 to increase the concentration of the alkali liquor, so that the efficiency of chlorine absorption is improved, the electrooxidation produced water enters a first reaction tank 61 of a first hardness removal device, tail gas after the absorption tower 51 absorbs the chlorine is mainly air and a small amount of hydrogen, and the tail gas is discharged from an exhaust port of the absorption tower 51 to the outside of the system;
Adding alkali solution into the first reaction tank 61, wherein the alkali solution is from an alkali solution output port of a bipolar membrane electrodialysis device, adding sodium carbonate solution into the second reaction tank 62, delivering the wastewater in the third reaction tank 63 into an ultrafiltration membrane 65 through an ultrafiltration water inlet pump 64 for filtration separation, refluxing a part of concentrated water generated by the ultrafiltration membrane 65 to the third reaction tank 63, discharging a part of concentrated water to a sludge dehydrator for dehydration treatment, delivering the dehydrated clear solution to a second water production tank 69, delivering the water produced by the ultrafiltration membrane 65 into the second water production tank 69, delivering the wastewater in the second water production tank 69 into a first hard removal device resin tank 71 by a second lifting pump 70, filling strong acid cation exchange resin into the first hard removal device resin tank 71, and regulating the pH of the wastewater by releasing hydrogen ions after calcium and magnesium ions in the wastewater by using the resin, wherein the water produced by the first hard removal device resin tank 71 enters a water inlet tank of a nanofiltration device;
s4, obtaining sodium chloride crystals and sodium sulfate decahydrate crystals. The method comprises the steps that nanofiltration water with the main component of sodium chloride is obtained after the water produced by a first hardness removal device passes through a nanofiltration device, the nanofiltration water enters a first vacuum membrane distillation device, concentrated water of the first vacuum membrane distillation device enters a crystallizer to obtain sodium chloride crystals, a part of mother liquor output by the crystallizer flows back to the first vacuum membrane distillation device, the other part of mother liquor output by the crystallizer enters a second adsorption device, the water produced by the first vacuum membrane distillation device enters a water producing tank, after the nanofiltration concentrated water enters the second vacuum membrane distillation device to be further concentrated, the concentrated water of the second vacuum membrane distillation device enters a low-temperature crystallizer to obtain sodium sulfate decahydrate crystals, the water produced by the second vacuum membrane distillation device enters a water producing tank, most of mother liquor of the low-temperature crystallizer flows back to the second vacuum membrane distillation device, and the rest of mother liquor of the low-temperature crystallizer enters the second adsorption device:
The method comprises the steps that produced water of a first hardness removal device enters a nanofiltration device, the nanofiltration device separates monovalent salt and divalent salt in wastewater to obtain produced water and concentrated water, the main components of the nanofiltration produced water are sodium chloride, the nanofiltration produced water enters a first vacuum membrane distillation device, the first vacuum membrane distillation device utilizes waste heat of a steel plant to heat the inlet water of the first vacuum membrane distillation device so that the inlet water temperature of the first vacuum membrane distillation device is controlled to be 50-70 ℃, the heated inlet water of the first vacuum membrane distillation device is separated in the first vacuum membrane distillation device to obtain concentrated water and vapor, the vapor of the first vacuum membrane distillation device is condensed to obtain produced water, the concentrated water of the first vacuum membrane distillation device enters a crystallizer to obtain sodium chloride crystals, one part of mother liquor output by the crystallizer flows back to the first vacuum membrane distillation device to be continuously concentrated, the other part of the mother liquor output by the crystallizer enters a second adsorption device, the produced water output by the nanofiltration device enters a second vacuum membrane distillation device, the waste heat of the second vacuum membrane distillation device is also used to heat the second vacuum membrane distillation device so that the temperature of the second vacuum membrane distillation device is controlled to be 50 ℃ and the second vacuum membrane distillation device is further subjected to obtain concentrated solution, and the residual concentrated solution enters the second vacuum distillation device after the second vacuum distillation device is subjected to be subjected to the second vacuum distillation device to be subjected to the low temperature of the second vacuum distillation device to be subjected to the second vacuum distillation to be output to the concentrated to be subjected to the mother liquor of the second vacuum distillation to be subjected to the concentrated to the second vacuum distillation of the mother liquor;
S5, sequentially removing organic matters and hardness. In the second adsorption device, granular activated carbon and macroporous adsorption resin are adopted to adsorb and remove organic matters in mother liquor output by the low-temperature crystallizer; the effluent of the second adsorption device enters a second hardness removal device and the hardness in the effluent of the second adsorption device is removed by softening resin, and the effluent of the second hardness removal device enters a bipolar membrane electrodialysis device:
the second adsorption device comprises a water inlet tank, a lifting pump, an adsorption tank and a resin tank, wherein the second adsorption device adopts granular active carbon and resin for adsorption, mother liquor output by the low-temperature crystallizer firstly enters the water inlet tank of the second adsorption device and is conveyed into the adsorption tank by the lifting pump, the granular active carbon is filled in the adsorption tank, water discharged from the adsorption tank enters the resin tank, the resin tank is filled with macroporous adsorption resin which is medium polarity macroporous adsorption resin and is adsorption resin containing ester groups, the surface of the adsorption resin is provided with two parts of hydrophobic and hydrophilic, the organic matters in the mother liquor are removed by the granular active carbon and the resin adsorption of the second adsorption device, the resin tank structure of the second adsorption device is the same as that of the first hard removing device resin tank 71, but the types of the filled resins are different (the first hard removing device resin tank 71 is filled with ion exchange resin, the second adsorption device is filled with macroporous adsorption resin), the resin adsorption is added to strengthen the removal effect, the two-stage adsorption (activated carbon adsorption and resin adsorption) is adopted to improve the removal effect of organic matters, the bipolar membrane electrodialysis device has higher requirement on the quality of the water of the inlet water, the concentration of the organic matters is lower after the treatment in the step S1, but the concentration of the organic matters is increased after the treatment in the step S5 is still needed to be further reduced after the concentration of the organic matters is concentrated through the second vacuum membrane distillation device and the low-temperature crystallizer.
The effluent of the second adsorption device enters the second hardness removal device, strong acid cation exchange resin is filled in a resin tank of the second hardness removal device, the hardness in the effluent of the second adsorption device is removed by using the resin of the second hardness removal device, and the effluent of the second hardness removal device enters the bipolar membrane electrodialysis device;
s6, preparing mixed acid of hydrochloric acid and sulfuric acid and sodium hydroxide solution by the bipolar membrane electrodialysis device. The mixed acid is recycled to the micro-electrolysis device, a part of the sodium hydroxide solution is used for regulating the pH of the neutralization tank 35, a part of the sodium hydroxide solution is used for absorbing tail gas by the alkali liquor water tank 52 of the electro-oxidation device, and the rest of the sodium hydroxide solution is used for preparing sodium ferrate solution in the sodium ferrate preparation device together with ferric hydroxide from the flocculation precipitation tank and sodium hypochlorite from the electro-oxidation device:
in the bipolar membrane electrodialysis device, sodium ions, sulfate ions and chloride ions in the wastewater are separated by an ion exchange membrane to obtain mixed acid of hydrochloric acid and sulfuric acid and sodium hydroxide solution, wherein the mass concentration of the sodium hydroxide solution is 8-10%, the mixed acid is recycled in the processes of acid regulation of the micro-electrolysis device, regeneration of resin inside or outside the system and membrane cleaning inside or outside the system, and a part of alkali solution is used for regulating the pH value of a neutralization tank 35 and absorbing tail gas by an alkali solution water tank 52 of the electro-oxidation device; and the other part of the sodium ferrate solution is used for preparing sodium ferrate solution by washing and filtering ferric hydroxide, and then utilizing sodium hydroxide solution, washed ferric hydroxide and sodium hypochlorite solution at low temperature, and the obtained sodium ferrate solution is used for treating coking wastewater or other wastewater and can be used as a strong oxidant and a flocculant. Sodium chloride impurities contained in the sodium ferrate solution can be removed by a recrystallization method, thereby purifying the sodium ferrate solution.
Fe 3+ +3OH - →Fe(OH) 3
2Fe(OH) 3 +3NaClO+4NaOH→2Na 2 FeO 4 +3NaCl+5H 2 O
Example 3
The treatment object of the present invention was selected from the concentrated solution of membrane filtration of coking wastewater from a steel mill in Hubei province, and example 2 was carried out as described above, wherein the water quality of the concentrated solution of membrane filtration of coking wastewater was: pH is 7.0-8.5, SS concentration is 20-70 mg/L, conductivity is 15500-18000 mu s/cm, COD (chemical oxygen demand) concentration is 480-650 mg/L, TDS (total dissolved solid matter) concentration is 12800-15500 mg/L, ammonia nitrogen concentration is 35-60 mg/L, sulfate concentration is 5000-7000 mg/L, chloride ion concentration is 3500-5000 mg/L, ca 2+ The concentration is 260-280 Mg/L, mg 2+ The concentration is 80-100 mg/L.
In step S1: after the coking wastewater membrane filtration concentrated solution is treated by a first adsorption device, the COD of effluent is 150-170 mg/L, and the produced water of the first adsorption device enters a micro-electrolysis reactor 10 and a Fenton reactor 26 for treatment;
in step S2: the COD of the effluent of the sedimentation tank 37 is 100-120 mg/L, after the effluent of the sedimentation tank 37 is treated by an electro-oxidation device, the COD of the effluent is less than 30mg/L, and the ammonia nitrogen is less than 0.2mg/L;
in step S3: the hardness of the effluent of the electro-oxidation device is removed by a chemical precipitation method in a first hardness removal device, the hardness of the effluent of an ultrafiltration membrane 65 in the first hardness removal device is less than 20mg/L, the hardness of the effluent of a resin tank 71 of the first hardness removal device is less than 5mg/L,
In step S4: the effluent of the first hardness removal device is treated by a nanofiltration device, nanofiltration produced water is subjected to first vacuum membrane distillation concentration treatment, the first vacuum membrane distillation concentrated water is crystallized by a crystallizer to obtain sodium chloride, and the first vacuum membrane distillation produced water enters a produced water tank for storage, wherein the produced water in the produced water tank reaches the reuse water standard; after the nanofiltration concentrated water is treated by a second vacuum membrane distillation device, sodium sulfate decahydrate is obtained by crystallization by a low-temperature crystallizer,
in step S5: a part of mother liquor discharged from the low-temperature crystallizer flows back to the second vacuum membrane distillation device, and the other part of mother liquor enters the second adsorption device, the COD of water discharged from the second adsorption device is less than 10mg/L, the water discharged from the second adsorption device enters the second hardness removal device, and the hardness of water discharged from the second hardness removal device is less than 5mg/L;
in step S6: the effluent of the second hardness removing device enters a bipolar membrane electrodialysis device to finally prepare mixed acid of sulfuric acid solution and hydrochloric acid solution and sodium hydroxide solution with mass concentration of 8-10%; the sodium ferrate preparation device utilizes ferric hydroxide, sodium hydroxide and sodium hypochlorite generated by the system to prepare sodium ferrate solution at low temperature, and the sodium ferrate solution is used for pretreatment of coking wastewater.
By the process method, the recycling utilization rate of the coking wastewater membrane filtration concentrated solution reaches more than 95%, the running cost of a treatment system is reduced, and the zero discharge of the concentrated solution is basically realized.
It should be noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (10)
1. A coking wastewater membrane filtration concentrate treatment system comprises a first adsorption device, and is characterized in that the water outlet of the first adsorption device is connected with a micro-electrolysis water inlet pipe (11) of the micro-electrolysis device, the water outlet of the micro-electrolysis device is connected with the water inlet of a Fenton device, the water outlet of the Fenton device is connected with the water inlet of a neutralization pond (35), the water outlet of the neutralization pond (35) is connected with the water inlet of a flocculation sedimentation pond, the ferric hydroxide outlet of the flocculation sedimentation pond is connected with a sodium ferrate preparation device, the water outlet of the flocculation sedimentation pond is connected with the water inlet of an electro-oxidation device, the sodium hypochlorite water outlet of the electro-oxidation device is connected with the sodium ferrate preparation device, the water outlet of the electro-oxidation device is connected with the water inlet of a first hard removing device, the water outlet of the first hard removing device is connected with the water inlet of a filter device, the concentrated water outlet of the nanofiltration device is connected with the water inlet of a first vacuum membrane distillation device, the concentrated water outlet of the first vacuum membrane distillation device is connected with a crystallizer, the mother liquor water outlet of the crystallizer is respectively connected with the water inlet of the first vacuum distillation device and the water inlet of a second vacuum distillation device, the water inlet of the second vacuum distillation device is connected with the second vacuum distillation device, the low-concentration water outlet of the low vacuum distillation device is connected with the second vacuum distillation device is connected with the water inlet of the second vacuum distillation device, the low-distillation device is connected with the water inlet of the second vacuum distillation device of the low-vacuum distillation device is connected with the water inlet of the second vacuum distillation device, the alkali liquor water outlet of the bipolar membrane electrodialysis device is respectively connected with an alkali liquor dosing pipe of the neutralization tank (35), an alkali liquor input port of the electro-oxidation device, an alkali liquor dosing pipe of the first hardness removal device and a sodium ferrate preparation device, the acid liquor water outlet of the bipolar membrane electrodialysis device is connected with an acid dosing pipe (12) of the micro-electrolysis device, and the fresh water outlet of the bipolar membrane electrodialysis device is connected with a water inlet of the nanofiltration device.
2. The coking wastewater membrane filtration concentrate treatment system according to claim 1, wherein the first adsorption device comprises a first adsorption device water inlet tank (1), a water inlet of the first adsorption device water inlet tank (1) is used as a water inlet of the first adsorption device, the first adsorption device water inlet tank (1) is connected with a first water tank of an adsorption reaction tank (4) through a water inlet pump (2), the bottom of the first water tank of the adsorption reaction tank (4) and the bottom of a second water tank of the adsorption reaction tank (4) are communicated through a flow passage, aeration pipes are arranged at the bottoms of the first water tank and the second water tank of the adsorption reaction tank (4), an inlet of the aeration pipes is connected with a first air blower (3), a second water tank of the adsorption reaction tank (4) is connected with a water inlet of a filter device (5) through a first lifting pump (7), a water outlet of the filter device (5) is connected with a first water tank of the adsorption reaction tank (4), a water outlet of the filter device (5) is connected with a first water production tank (6), and a water outlet of the filter device (5) is connected with an external sludge dewatering machine.
3. The coking wastewater membrane filtration concentrate treatment system according to claim 2, wherein the micro-electrolysis device comprises a pipeline mixer (13), one inlet of the pipeline mixer (13) is connected with an outlet of a micro-electrolysis water inlet pipe (11), the other inlet of the pipeline mixer (13) is connected with an acid dosing pipe (12), the outlet of the pipeline mixer (13) is connected with an inlet of a micro-electrolysis reactor water inlet pipe (14), the outlet of the micro-electrolysis reactor water inlet pipe (14) extends to the lower part of the micro-electrolysis reactor (10), a plurality of filler supporting layers (23) are arranged in the micro-electrolysis reactor (10), a block filler is arranged on the filler supporting layers (23), a micro-electrolysis reactor aeration pipe (19) is arranged below each filler supporting layer (23), a first baffle plate (20) is arranged at the bottom of the micro-electrolysis reactor (10), the first baffle plate (20) is positioned right below the outlet of the micro-electrolysis reactor water inlet pipe (14), a micro-electrolysis reactor port (18) is arranged on the side wall of the micro-electrolysis reactor (10) corresponding to the inlet of each filler supporting layer (23), a first overflow weir (16) is arranged above the first overflow weir (15), a first overflow separator (16) is arranged above the first overflow weir (16), the first overflow weir (16) is connected with a water outlet pipe (24) of the micro-electrolysis reactor, and a water outlet of the water outlet pipe (24) of the micro-electrolysis reactor is used as a water outlet of the micro-electrolysis device.
4. A coking wastewater membrane filtration concentrate treatment system according to claim 3, wherein the Fenton device comprises a Fenton reactor water inlet pipe (25), a water inlet of the Fenton reactor water inlet pipe (25) is used as a water inlet of the Fenton reactor device to be connected with a water outlet of a micro-electrolysis reactor water outlet pipe (24), a water outlet of the Fenton reactor water inlet pipe (25) extends to the lower part of a Fenton reactor (26), an aeration pipe and a second baffle (31) are arranged at the bottom of the Fenton reactor (26), the second baffle (31) is positioned under the water outlet of the Fenton reactor water inlet pipe (25), the second overflow weir (27) is positioned at the upper part of the Fenton reactor (26), the second separator (32) is positioned under the second overflow weir (27), the second overflow weir (27) is connected with a water outlet pipe (33) of the Fenton reactor, the outlet pipe (33) is the water outlet of the Fenton reactor, and the bottom of the Fenton reactor (26) is connected with a dosing pipeline of hydrogen peroxide solution.
5. The coking wastewater membrane filtration concentrate treatment system according to claim 4, wherein the neutralization tank (35) is connected with an outlet of a Fenton reactor water outlet pipe (33), an aeration pipe is arranged at the bottom of the neutralization tank (35), the aeration pipe of the neutralization tank (35) is connected with a second blower (34), the bottom of the neutralization tank (35) and the bottom of the flocculation tank (36) are connected through a flow passage, and the flow passage is used as a water outlet of the neutralization tank (35) and a water inlet of the flocculation sedimentation tank;
The flocculation sedimentation tank includes flocculation tank (36), flocculation tank (36) are provided with flocculation tank mixer (39), flocculation tank (36) are connected the flocculating agent and are added the pencil, overflow mouth and sedimentation tank (37) inlet tube inlet connection on flocculation tank (36) upper portion, the inlet tube export of sedimentation tank (37) extends to the middle part of sedimentation tank (37), be provided with sedimentation tank mud bucket in the bottom of sedimentation tank (37), sedimentation tank mud bucket is located the below of the inlet tube export of sedimentation tank (37), the inlet connection of sedimentation tank mud bucket and dredge pump (38), the export of dredge pump (38) is as the ferric hydroxide delivery port of flocculation sedimentation tank, the upper portion of sedimentation tank (37) is provided with sedimentation tank delivery port (40), sedimentation tank delivery port (40) are as the delivery port of flocculation sedimentation tank.
6. The coking wastewater membrane filtration concentrate treatment system according to claim 5, wherein the electro-oxidation device comprises an electro-oxidation water inlet tank (41), a water inlet of the electro-oxidation water inlet tank (41) is used as a water inlet of the electro-oxidation device, the top of the electro-oxidation water inlet tank (41) is closed, an aeration pipe is arranged at the bottom of the electro-oxidation water inlet tank (41), an aeration pipe of the electro-oxidation water inlet tank (41) is connected with a third blower (42), an inlet of a second air suction fan (50) is connected to a space above the liquid level in the electro-oxidation water inlet tank (41), an outlet of the second air suction fan (50) is connected with an air inlet of an absorption tower (51), an inlet of an electro-oxidation water inlet pump (43) is connected with an water outlet of the electro-oxidation water inlet tank (41), an outlet of the electro-oxidation water inlet pump (43) is connected with an inlet of a filter (44), an outlet of the filter (44) is connected with an inlet of an electrolytic tank (45), an air outlet of the electrolytic tank (45) is connected with the electro-oxidation water inlet tank (41) through an electrolytic tank air outlet pipe (47) and an air outlet of the electrolytic tank (47) is positioned below the liquid level of the electro-oxidation water inlet tank (41), an outlet of the electrolytic tank (45) is connected with the water outlet of the electro-oxidation water pump (48) to the electro-oxidation water pump (48) in the water tank (48) to be connected with the top of the electro-oxidation water tank (48), the outlet of the first air extraction fan (49) is connected with the air inlet of the absorption tower (51), the bottom of the absorption tower (51) is connected with the alkali liquor water tanks (52), the alkali liquor water tanks (52) are provided with a plurality of groups, when the inside of the alkali liquor water tanks (52) is hollow, the inlet of the alkali liquor water tanks (52) is used as an alkali liquor input port of the electro-oxidation device, when the alkali liquor water tanks (52) are filled with sodium hydroxide solution, the inlet of the alkali liquor water tanks (52) is disconnected with an alkali liquor output port of the bipolar membrane electrodialysis device, the outlet of the alkali liquor water tanks (52) is connected with an inlet of the spray pump (53), the outlet of the spray pump (53) is connected with an upper water inlet of the absorption tower (51), the inlet of the alkali liquor water tanks (52) is connected with a water outlet of the absorption tower (51), when the concentration of sodium hypochlorite solution in the alkali liquor water tanks (52) reaches a set value, the outlet of the sodium hypochlorite of the electro-oxidation device, and the water outlet of the electro-oxidation water production tank (48) is used as a water outlet of the electro-oxidation device.
7. The coking wastewater membrane filtration concentrate treatment system according to claim 6, wherein the first hard removal device comprises a first reaction tank (61) connected in sequence, the bottom of the first reaction tank (61) is connected with the bottom of a second reaction tank (62) through a flow passage, the upper part of the second reaction tank (62) is connected with the upper part of a third reaction tank (63) through an overflow passage, the first reaction tank (61) is provided with a first stirrer (66), the second reaction tank (62) is provided with a second stirrer (67) and the third reaction tank (63) is provided with a third stirrer (68), the water inlet of the first reaction tank (61) is used as the water inlet of the first hard removal device, the first reaction tank (61) is provided with an alkali liquor adding pipe and the alkali liquor adding pipe of the first hard removal device is used as the alkali liquor adding pipe of the first hard removal device, the second reaction tank (62) is connected with a sodium carbonate adding pipe, the third reaction tank (63) is connected with the inlet of an ultrafiltration membrane (65) through an ultrafiltration water inlet pump (64), the outlet of the second reaction tank (65) is connected with a third hard filtration membrane (69) is connected with a second hard filtration membrane (69), the second hard filtration membrane (69) is connected with a third hard filtration resin lifting tank (71) is filled with a second hard filtration resin lifting tank (71), the outlet of the resin tank (71) of the first hardness removing device is used as the water outlet of the first hardness removing device.
8. A method for treating coking wastewater membrane filtration concentrate, which utilizes the coking wastewater membrane filtration concentrate treatment system of claim 7, and is characterized by comprising the following steps:
s1, removing most organic pollutants in coking wastewater membrane filtration concentrate in a first adsorption device through active carbon; the effluent of the first adsorption device enters a micro-electrolysis device, an acid solution is added to adjust the pH value of the inlet water of the micro-electrolysis device to 2-3, ferrous ions are generated while organic pollutants and chromaticity in the wastewater are further removed, the produced water of the micro-electrolysis device enters a Fenton device, and the Fenton device utilizes the ferrous ions and hydrogen peroxide to further oxidize and remove the organic pollutants and chromaticity in the wastewater, and ferric ions are generated;
s2, the effluent of the Fenton device enters a neutralization tank (35), the pH value in the neutralization tank (35) is regulated to 7-8 by utilizing alkali solution, a flocculating agent is added into a flocculation tank (36) and then is precipitated in a precipitation tank (37), the effluent of the precipitation tank (37) enters an electro-oxidation device, and ferric hydroxide precipitate in the precipitation tank (37) enters a sodium ferrate preparation device;
s3, removing ammonia nitrogen, COD and chromaticity in the wastewater by using an electrooxidation device, generating a sodium hypochlorite solution by using an alkali solution, enabling the sodium hypochlorite solution to enter a sodium ferrate preparation device, and enabling electrooxidation produced water to enter a first hardness removal device; the first hardness removing device adopts chemical precipitation and resin softening to remove hardness in the wastewater, and the effluent after the hardness removal enters a nanofiltration device;
S4, the produced water of the first hardness removal device is subjected to nanofiltration to obtain nanofiltration produced water with sodium chloride as a main component, the nanofiltration produced water enters a first vacuum membrane distillation device, concentrated water of the first vacuum membrane distillation device enters a crystallizer to obtain sodium chloride crystals, a part of mother liquor output by the crystallizer flows back to the first vacuum membrane distillation device, the other part of mother liquor output by the crystallizer enters a second adsorption device, the produced water of the first vacuum membrane distillation device enters a produced water tank, the nanofiltration concentrated water enters a second vacuum membrane distillation device to be further concentrated, the concentrated water of the second vacuum membrane distillation device enters a low-temperature crystallizer to obtain sodium sulfate decahydrate crystals, the produced water of the second vacuum membrane distillation device enters a produced water tank, most of mother liquor of the low-temperature crystallizer flows back to the second vacuum membrane distillation device, and the rest part of mother liquor of the low-temperature crystallizer enters the second adsorption device;
s5, adsorbing and removing organic matters in the mother liquor output by the low-temperature crystallizer by using granular activated carbon and macroporous adsorption resin in a second adsorption device, enabling effluent of the second adsorption device to enter a second hardness removal device, softening by using resin to remove hardness in wastewater, and enabling effluent of the second hardness removal device to enter a bipolar membrane electrodialysis device;
S6, preparing mixed acid of hydrochloric acid and sulfuric acid and sodium hydroxide solution by the bipolar membrane electrodialysis device, wherein the mixed acid is reused for the micro-electrolysis device, one part of the sodium hydroxide solution is used for regulating the pH value by a neutralization tank (35), one part of the sodium hydroxide solution is used for absorbing tail gas by an alkali liquor water tank (52) of the electro-oxidation device, and the other part of the sodium hydroxide solution is used for preparing sodium ferrate solution by the sodium ferrate preparation device, ferric hydroxide from a flocculation sedimentation tank and sodium hypochlorite from the electro-oxidation device.
9. The coking wastewater membrane filtration concentrate treatment method according to claim 7, wherein: the alkali liquor water tanks (52) in the step S3 are provided with a plurality of groups, when the mass concentration of the sodium hypochlorite solution reaches the set concentration, the alkali liquor water tanks (52) in the next group are switched to be conveyed to a sodium ferrate preparation device through a lifting pump; and (3) the mass concentration of the sodium hydroxide solution prepared by bipolar membrane electrodialysis in the step S6 is 8-10%, and the mixed acid is used for regulating the pH value of a micro-electrolysis device, regenerating the resin inside or outside the system and cleaning the membrane inside or outside the system.
10. The coking wastewater membrane filtration concentrate treatment method according to claim 7, wherein: and in the step S4, the heat sources of the first vacuum membrane distillation device and the second vacuum membrane distillation device adopt the waste heat of a steel mill, so that the operation temperature of the waste water is 50-70 ℃.
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| CN117486433A (en) * | 2023-12-29 | 2024-02-02 | 北京启元汇通水务科技股份有限公司 | Coking wastewater deep purification equipment and application method thereof |
| CN118026393A (en) * | 2024-04-09 | 2024-05-14 | 广州大学 | Wastewater utilization system of anaerobic membrane distillation bioreactor based on no-salinity accumulation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117486433A (en) * | 2023-12-29 | 2024-02-02 | 北京启元汇通水务科技股份有限公司 | Coking wastewater deep purification equipment and application method thereof |
| CN117486433B (en) * | 2023-12-29 | 2024-03-12 | 北京启元汇通水务科技股份有限公司 | Coking wastewater deep purification equipment and application method thereof |
| CN118026393A (en) * | 2024-04-09 | 2024-05-14 | 广州大学 | Wastewater utilization system of anaerobic membrane distillation bioreactor based on no-salinity accumulation |
| CN118026393B (en) * | 2024-04-09 | 2024-06-07 | 广州大学 | Method for treating wastewater by using wastewater utilization system based on anaerobic membrane distillation bioreactor without salt accumulation |
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