CN106830479A - Using flue gas and electrodialytic desulfurization wastewater zero-discharge treatment system and method - Google Patents
Using flue gas and electrodialytic desulfurization wastewater zero-discharge treatment system and method Download PDFInfo
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- CN106830479A CN106830479A CN201710021176.9A CN201710021176A CN106830479A CN 106830479 A CN106830479 A CN 106830479A CN 201710021176 A CN201710021176 A CN 201710021176A CN 106830479 A CN106830479 A CN 106830479A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 53
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 44
- 230000023556 desulfurization Effects 0.000 title claims abstract description 44
- 239000003546 flue gas Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000011282 treatment Methods 0.000 title claims abstract description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 208000028659 discharge Diseases 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000005189 flocculation Methods 0.000 claims abstract description 50
- 230000016615 flocculation Effects 0.000 claims abstract description 50
- 238000000909 electrodialysis Methods 0.000 claims abstract description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 21
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 20
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 19
- 238000009388 chemical precipitation Methods 0.000 claims abstract description 16
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 15
- 239000013505 freshwater Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 10
- 238000001764 infiltration Methods 0.000 claims abstract description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000005255 carburizing Methods 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 18
- 238000009993 causticizing Methods 0.000 claims description 17
- 238000000108 ultra-filtration Methods 0.000 claims description 17
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 16
- 238000006386 neutralization reaction Methods 0.000 claims description 14
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 13
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 11
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910001424 calcium ion Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 238000004062 sedimentation Methods 0.000 claims description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 125000001741 organic sulfur group Chemical group 0.000 claims description 7
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005352 clarification Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 241000628997 Flos Species 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052925 anhydrite Inorganic materials 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007832 Na2SO4 Substances 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000005370 electroosmosis Methods 0.000 claims description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 claims 1
- 229940079593 drug Drugs 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 235000017550 sodium carbonate Nutrition 0.000 abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 238000011369 optimal treatment Methods 0.000 abstract description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- 239000003643 water by type Substances 0.000 abstract 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 6
- 229910001425 magnesium ion Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MVZXTUSAYBWAAM-UHFFFAOYSA-N iron;sulfuric acid Chemical compound [Fe].OS(O)(=O)=O MVZXTUSAYBWAAM-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000013014 water-saving technology Methods 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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/08—Preparation by working up natural or industrial salt mixtures or siliceous minerals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
- C02F2201/007—Modular design
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
Using flue gas and electrodialytic desulfurization wastewater zero-discharge treatment system and method, the system includes chemical precipitation flocculation unit, lime-flue gas pliable cell, film upgrading unit and evaporative crystallization unit；Based on said system, desulfurization wastewater raw water is processed first with chemical precipitation flocculation unit, then using the CO in milk of lime and power plant flue gas2The hardness ionses such as the calcium and magnesium in efficient removal chemical precipitation flocculation unit water outlet, while realizing carbon dioxide discharge-reduction；Soften water outlet by carrying out efficient concentration into ion selectivity electrodialysis cell after hyperfiltration treatment, obtain NaCl concentrated waters, NaCl Nacls are further obtained by evaporative crystallization；, by low pressure coiled reverse osmosis membrane, acquisition can reuse fresh water for electrodialysis fresh water；Reverse osmosis concentrated water reenters electrodialysis cell；The present invention is using the CO in power plant flue gas2Instead of expensive soda ash, softening cost was both reduced, CO had been promoted again2Emission reduction；Introduce electroosmose process to be concentrated, electrodialysis and counter-infiltration is under optimal treatment condition, reduce energy consumption.
Description
Technical field
Technical field the present invention relates to process desulfurization wastewater using zero-discharge technology, and in particular to one kind utilizes flue gas
With electrodialytic desulfurization wastewater zero-discharge treatment system and method.
Background technology
Current China's major part coal-burning power plant carries out flue gas desulfurization using wet limestone-gypsum FGD technology (WFGD),
A certain amount of desulfurization wastewater of regular discharge is needed in sweetening process.Desulfurization waste water quality extreme difference, with salt content is high, solid suspension
Content is high, hardness is high, corrosivity is strong, water quality with time and big working conditions change the features such as.In addition, also containing micro in desulfurization wastewater
Heavy metal element, such as mercury, chromium, cadmium, lead, wherein being much the first kind pollution of the strict control of requirement in national environmental standard
Thing.Domestic power plant is generally processed desulfurization wastewater using chemical precipitation flocculence, can remove a most huge sum of money in waste water
The materials such as category ion, COD (COD), suspended solid (SS).However, by chemical precipitation flocculence process water outlet in
Still there is salt content very high.
As environmental protection problem becomes increasingly conspicuous, more and more closed using zero-discharge technology treatment desulfurization wastewater
Note.Promulgate within 2005《Chinese water-saving technology policy outline》It is distinctly claimed the reuse of enterprise development efflux wastewater and zero-emission skill
Art.The country for promulgating for 2015《Water prevention and cure of pollution action plan》(ten, water), encourages energy-saving and emission-reduction advanced enterprises, agglomeration of industry
Area's water-use efficiency, discharging intensity etc. reach higher standard.Therefore, research desulfurization wastewater technique of zero discharge is that thermal power plant is realized
The only way of sustainable development.
The domestic research to desulfurization wastewater technique of zero discharge at present is in the starting stage, and basic thought is to pass through desulfurization wastewater
Certain pretreatment is crossed, concentration, the steam condensation reuse of generation, concentrate knot are evaporated to desulfurization wastewater using steam heating
Brilliant product packaging outward transport.However, the investment operating cost of existing desulfurization wastewater technique of zero discharge is higher.This is primarily due to desulfurization
Calcium ions and magnesium ions in waste water easily cause the fouling and corrosion of evaporation and crystallization system, cause equipment depreciation expense to improve；And steam
Hair crystallization process energy consumption is higher, causes operating cost to increase.
In order to reduce equipment damage, it is necessary to carry out sofening treatment to desulfurization wastewater, the calcium ions and magnesium ions in removing water.Conventional
Softening process is lime-soda method, and medicament is costly.It is about 200mM by calcium ions and magnesium ions total amount in desulfurization wastewater to calculate, treatment
1 ton of waste water about needs to add carbonic acid 22kg, by the soda ash unit price accounting of 1500-2000 units/t, only the ton water medicament expense of soda ash just
Up to 40 yuan or so, significantly increase the cost of technique of zero discharge.
In order to reduce operation energy consumption, it is necessary to carry out decrement concentration to desulfurization wastewater.Hyperfiltration has process is simple, desalination
Rate advantage high, but, reverse osmosis process has that some intrinsic cannot be solved：Produce Water Sproading rate relatively low；To water quality requirement
It is high；The dirt of film is stifled more serious, and Membrane cleaning is difficult, and the life-span is relatively low；High salinity causes operating pressure big and energy consumption increases.At place
During the reason poor desulfurization wastewater of water quality, the operating pressure of hyperfiltration often reaches more than 6MPa, and investment and operating cost enter one
Step is improved.In order to reduce the process costs of desulfurization wastewater zero-emission, a kind of concentration work for being more suitable for desulfurization wastewater treatment is selected
Skill is very necessary.
The content of the invention
In order to solve the above problems, flue gas and electrodialytic desulfurization wastewater are utilized it is an object of the invention to provide one kind
Zero-discharge treatment system and method, by the coupling and optimization of each process procedure, reduce the operating cost of technique of zero discharge, realize
Resource recycling and environmental protection.
The present invention to achieve the above object, the technical scheme for being used for：
Using flue gas and electrodialytic desulfurization wastewater zero-discharge treatment system, including chemical precipitation flocculation unit 1, stone
Ash-flue gas pliable cell 2, film upgrading unit 3 and evaporative crystallization unit 4；
The chemical precipitation flocculation unit 1 is by being sequentially connected the neutralization pond for connecing, sedimentation basin, flocculation basin, clarification by pipeline
Pond and 1# clear water reserviors are constituted, and the water inlet of neutralization pond is connected with the floss hole of desulfurization wastewater；Lime is provided with the neutralization pond
Newborn chemicals dosing plant；Organic sulfur chemicals dosing plant is provided with the sedimentation basin；Flocculant and flocculation aid are provided with the flocculation basin
Chemicals dosing plant；Mud discharging mouth is arranged at the depositing reservoir bottom, and mud discharging mouth is connected by pipeline with device for dehydrating sladge waste；
The lime-flue gas pliable cell 2 by be sequentially connected by pipeline the causticizing reaction pond for connecing, carburizing reagent pond and
2# clear water reserviors are constituted, and causticizing reaction pond is connected with the 1# clear water reserviors in chemical precipitation flocculation unit 1 by pipeline；The causticization is anti-
Ying Chizhong is provided with milk of lime, sodium sulphate, flocculant and flocculation aid chemicals dosing plant, and there are mud discharging mouth, spoil disposal in causticizing reaction bottom of pond portion
Mouth is connected by pipeline with device for dehydrating sladge waste；The bottom in the carburizing reagent pond is disposed with gas distributor, gas distributor
It is connected with flue gas compression fan, flocculant, flocculation aid chemicals dosing plant is provided with carburizing reagent pond, carburizing reagent bottom of pond portion has
Mud discharging mouth, mud discharging mouth is connected by pipeline with device for dehydrating sladge waste；Watery hydrochloric acid chemicals dosing plant is provided with the 2# clear water reserviors；
The film upgrading unit 3 is by being sequentially connected the ultrafiltration apparatus for connecing, electrodialysis plant and reverse osmosis unit by pipeline
Composition；The water inlet of the ultrafiltration apparatus is connected with the delivery port of the 2# clear water reserviors of lime-flue gas pliable cell 2, ultrafiltration dress
The delivery port put is connected with the water inlet of electrodialysis plant, concentrated water water return outlet and the chemical precipitation flocculation unit 1 of ultrafiltration apparatus
Neutralization pond is connected；The concentrated water discharge of electrodialysis plant mouthful is connected with evaporative crystallization unit 4, fresh water floss hole and reverse osmosis unit
Water inlet is connected；The concentrated water discharge mouthful of the reverse osmosis unit counter-infiltration is connected with the water inlet of electrodialysis plant.
The electrodialysis plant is multi-stage countercurrent pole-reversing electroosmosis, employs monovalent ion selective membrane,
The reverse osmosis unit employs coiled reverse osmosis membrane.
The evaporative crystallization unit 4 employs mechanical recompression evaporator.
Using flue gas and electrodialytic zero emission treatment of desulfured waste water, the method is realized using the system
, methods described comprises the following steps：
(1) desulfurization wastewater raw water is passed through the neutralization pond of chemical precipitation flocculation unit 1, sedimentation basin, flocculation basin and clear successively
Clear pond is neutralized, is precipitated, being flocculated and clarifying treatment, and clarified solution finally enters 1# clear water reserviors；
(2) clarified solution in above-mentioned steps (1) is passed through the causticizing reaction pond in lime-flue gas pliable cell 2 successively
Causticization, carbonization treatment are carried out with carburizing reagent pond, clarified solution enters 2# clear water reserviors；
(3) clarified solution that above-mentioned steps (2) are obtained is passed through film upgrading unit 3, the clarified solution is carried out at ultrafiltration first
Reason, the product water of ultrafiltration is passed through electrodialysis plant carries out point salt and concentration；The fresh water that electrodialysis is produced is passed through reverse osmosis unit to be carried out
Purifying, while producing the concentrated water containing NaCl；The fresh water that counter-infiltration is produced is back to production, and the concentrated water of generation reenters electric osmose
Analysis apparatus are processed；
(4) concentrated water containing NaCl that above-mentioned steps (3) electrodialysis plant is produced is passed through evaporative crystallization unit 4, is obtained
To technical grade NaCl crystal salts and condensed water, recycling condensing water is in production；
In the step (1), milk of lime is added in neutralization pond, adds organic sulfur in sedimentation basin, milk of lime or organic sulfur with
Iron, lead, chromium, copper, the reaction of mercury heavy metal ion produce hydroxide or sulfide；
In the step (1), flocculant is added in flocculation basin, the suspension in waste water is produced precipitation, added in depositing reservoir
Enter flocculation aid, make the sediment of generation accelerate to separate；
In the step (2), milk of lime and sodium sulphate are added in causticizing reaction pond, following reactions occur：
Ca(OH)2+MgSO4→CaSO4+Mg(OH)2↓
Ca(OH)2+Na2SO4→CaSO4+2NaOH
Mg in removing waste water2+Ion simultaneously produces NaOH, then certain flocculant and helps solidifying to being added in system
Agent, fully flocculation clarification；
In the step (2), flue gas is passed through in carburizing reagent pond, following reactions occur：
2NaOH+CO2→Na2CO3+H2O
Na2CO3+Ca2+→CaCO3↓+2Na+
Ca in removing waste water2+Ion, then to certain flocculant and flocculation aid is added in system, fully flocculates clear
Clearly；
In the step (2), the addition of milk of lime and sodium sulphate should control to produce NaOH in causticizing reaction pond
Amount is between 0.05-0.2g/L；
In the step (2), the flue gas being passed through in carburizing reagent pond is the neat stress by denitration, dedusting and desulfurization,
It is slowly introducing at normal temperatures and pressures, the intake of flue gas should make the pH of system between 9-13；
In the step (3), the purpose of ultrafiltration is to remove the suspended solid (SS) in water, water outlet is met follow-up film process
With the requirement of evaporative crystallization treatment, the neutralization pond of ultrafiltration concentrate recirculation to chemical flocculation precipitation unit 1；
In the step (3), electrodialysis-ion exchange film uses monovalent ion selective membrane, makes the Cl in waste water-Dense
It is enriched with water, and SO4 2-Dilute side is stayed in, the purity of later crystallization is improved；
In the step (3), total dissolved solid (TDS) is full below 0.05% in the fresh water that reverse osmosis unit is produced
The requirement of sufficient industrial reuse water, film upgrading unit fresh-water recovery rate is not less than 90%.
In the step (1), the flocculant added in flocculation basin is poly-ferric sulfate chloride, aluminium polychloride, polymerised sulphur
One or more in sour iron；The flocculation aid added in depositing reservoir is the one kind in polyacrylamide, Sodium Polyacrylate, shitosan
Or it is several.
In the step (2), the flocculant added in causticizing reaction pond is poly-ferric sulfate chloride, aluminium polychloride, gathers
Close ferric sulfate in one or more；The flocculation aid added in causticizing reaction pond is polyacrylamide, Sodium Polyacrylate, shitosan
In one or more；
In the step (2), the flocculant added in carburizing reagent pond is poly-ferric sulfate chloride, aluminium polychloride, gathers
Close ferric sulfate in one or more；The flocculation aid added in carburizing reagent pond is polyacrylamide, Sodium Polyacrylate, shitosan
In one or more.
In the step (3), electrodialysis plant uses the operation of falling pole, it is to avoid the fouling of face.
Compared with prior art, the invention has the advantages that：
1) entered by the water outlet of the net flue gas to chemical precipitation flocculation unit of denitration, dedusting, desulfurization using coal-burning power plant
Row softens, and can either replace expensive soda ash, reduces and softens cost, reach softening efficiency higher, it is to avoid follow-up equipment
Fouling and corrosion, promote CO again2Emission reduction.Calculated by calcium ions and magnesium ions total amount 200mM in desulfurization wastewater, process desulfurization wastewater per ton
While can emission reduction about 8.8g carbon dioxide.
2) introduce electroosmose process and improve traditional film concentration technology, electrodialysis and counter-infiltration is in optimal treatment condition
Under, reducing energy consumption and processing cost；Electrodialysis-ion exchange film can use monovalent ion selective membrane, make the SO in waste water4 2-Stay
In dilute side, Cl-Ion is enriched with concentrated water, and then obtains technical grade NaCl crystal salts by evaporative crystallization.
Brief description of the drawings
Fig. 1 is present system and method flow diagram.
Specific embodiment
The present invention will be described in more detail with specific embodiment below in conjunction with the accompanying drawings.
Desulfurization wastewater raw water main component is as follows：TDS 20000‐60000mg/L；SS 5000‐10000mg/L；SO4 2‐
2000‐6000mg/L；Ca2+1500‐5000mg/L；Mg2+3000‐6000mg/L.As shown in figure 1, by being passed through of desulfurization wastewater
Precipitation flocculation unit 1 is neutralized, precipitated, being flocculated, clarifying treatment, by adding milk of lime, organic sulfur, polyaluminium sulfuric acid
Iron and polyacrylamide carry out precipitation flocculation reaction, are met《Thermal power plant's Limestone-gypsum Wet Flue Gas Desulfurization Process waste water quality control
Index》The clarified solution of the water quality requirement of (DL/T 997-2006)；The clarified solution of acquisition is passed through lime-flue gas pliable cell 2
Causticization, carbonization and clarifying treatment are carried out, by adding milk of lime and sodium sulphate, makes the Mg in system2+Settle down, while sulfuric acid
Sodium and milk of lime reaction generation calcium sulfate precipitation and NaOH；To addition poly-ferric sulfate chloride and polyacrylamide in system
Amine, fully flocculation clarification.Gained clarified solution is passed through carbonization pond, carbonization will be passed through by the neat stress of denitration, dedusting and desulfurization
Chi Zhong, the carbon dioxide in flue gas is absorbed by the NaOH in system and produces carbonate, and carbonate forms carbon with calcium ion
Sour calcium precipitate.In the lime-flue gas pliable cell 2, the accumulation of causticizing reaction NaOH is 0.1g/L, and flue gas is passed through
System pH is changed into 10 afterwards.To bodied ferric sulfate and Sodium Polyacrylate is added in system, fully flocculation is clarified.Lime-flue gas is soft
The water outlet calcium ions and magnesium ions total amount for changing unit 2 is no more than 20mg/L.The clarified solution that lime-flue gas pliable cell 2 is obtained is carried out
Hyperfiltration treatment, ultrafiltration producing water ratio is 95%, concentrate recirculation to chemical precipitation flocculation unit again coagulating sedimentation；It is light that ultrafiltration is produced
SS is less than 0.2mg/L in water, is passed through electrodialysis plant and is concentrated.Electrodialysis plant is operated using frequently pole-reversing, prevents fouling；
Amberplex makes the Cl in waste water from monovalent ion selectivity exchange membrane‐And SO4 2‐Separate, make sodium chloride in electric osmose
It is enriched with analysis concentrated water, improves the purity of later crystallization.Electrodialysis produces the concentrated water that TDS is 15% using 5 and 2 string connected modes,
By obtaining technical grade NaCl crystal salts after the evaporative crystallization of evaporative crystallization unit 4.Electrodialysis fresh water TDS is 0.5%, by resistant
Dye coiled reverse osmosis membrane is further purified, and reverse osmosis freshwater TDS, can be used as industrial reuse water below 0.05%.It is reverse osmosis concentrated
Water TDS is 2%, and 6% is concentrated into by one-level electrodialysis, by obtaining technical grade Na after evaporative crystallization2SO4Crystal salt, electrodialysis
Fresh water is back at feed water by reverse osmosis.It is 80% that film upgrading unit produces Water Sproading rate.Desulfurization wastewater zero-emission proposed by the present invention
Method, is capable of achieving changing waste into resources and utilizes, and waste water and solid waste pollution is eliminated, with good economy and environmental benefit.
Claims (9)
1. flue gas and electrodialytic desulfurization wastewater zero-discharge treatment system are utilized, it is characterised in that：The system includes chemistry
Precipitation flocculation unit (1), lime-flue gas pliable cell (2), film upgrading unit (3) and evaporative crystallization unit (4)；
The chemical precipitation flocculation unit (1) is by being sequentially connected the neutralization pond for connecing, sedimentation basin, flocculation basin, depositing reservoir by pipeline
Constituted with 1# clear water reserviors, the water inlet of neutralization pond is connected with the floss hole of desulfurization wastewater；Milk of lime is provided with the neutralization pond
Chemicals dosing plant；Organic sulfur chemicals dosing plant is provided with the sedimentation basin；Flocculant is provided with the flocculation basin and flocculation aid adds
Medicine device；Mud discharging mouth is arranged at the depositing reservoir bottom, and mud discharging mouth is connected by pipeline with device for dehydrating sladge waste；
The lime-flue gas pliable cell (2) is by being sequentially connected the causticizing reaction pond for connecing, carburizing reagent pond and 2# by pipeline
Clear water reserviors are constituted, and causticizing reaction pond is connected with the 1# clear water reserviors in chemical precipitation flocculation unit (1) by pipeline；The causticization is anti-
Ying Chizhong is provided with milk of lime, sodium sulphate, flocculant and flocculation aid chemicals dosing plant, and there are mud discharging mouth, spoil disposal in causticizing reaction bottom of pond portion
Mouth is connected by pipeline with device for dehydrating sladge waste；The bottom in the carburizing reagent pond is disposed with gas distributor, gas distributor
It is connected with flue gas compression fan, flocculant, flocculation aid chemicals dosing plant is provided with carburizing reagent pond, carburizing reagent bottom of pond portion has
Mud discharging mouth, mud discharging mouth is connected by pipeline with device for dehydrating sladge waste；Watery hydrochloric acid chemicals dosing plant is provided with the 2# clear water reserviors；
The film upgrading unit (3) is by being sequentially connected the ultrafiltration apparatus for connecing, electrodialysis plant and reverse osmosis unit group by pipeline
Into；The water inlet of the ultrafiltration apparatus is connected with the delivery port of the 2# clear water reserviors of lime-flue gas pliable cell (2), ultrafiltration dress
The delivery port put is connected with the water inlet of electrodialysis plant, concentrated water water return outlet and the chemical precipitation flocculation unit (1) of ultrafiltration apparatus
Neutralization pond be connected；The concentrated water discharge mouthful of electrodialysis plant is connected with evaporative crystallization unit (4), and fresh water floss hole is filled with counter-infiltration
The water inlet put is connected；The concentrated water discharge mouthful of the reverse osmosis unit counter-infiltration is connected with the water inlet of electrodialysis plant.
2. utilization flue gas according to claim 1 and electrodialytic desulfurization wastewater zero-discharge treatment system, its feature exist
In：The electrodialysis plant is multi-stage countercurrent pole-reversing electroosmosis, employs monovalent ion selective membrane.
3. utilization flue gas according to claim 1 and electrodialytic desulfurization wastewater zero-discharge treatment system, its feature exist
In：The reverse osmosis unit employs coiled reverse osmosis membrane.
4. utilization flue gas according to claim 1 and electrodialytic desulfurization wastewater zero-discharge treatment system, its feature exist
In：The evaporative crystallization unit (4) employs mechanical recompression evaporator.
5. flue gas and electrodialytic zero emission treatment of desulfured waste water are utilized, it is characterised in that：The method is to utilize right
It is required that what system described in 1 to 4 any one was realized, methods described comprises the following steps：
(1) desulfurization wastewater raw water is passed through neutralization pond, sedimentation basin, flocculation basin and the clarification of chemical precipitation flocculation unit (1) successively
Pond is neutralized, is precipitated, being flocculated and clarifying treatment, and clarified solution finally enters 1# clear water reserviors；
(2) by the clarified solution in above-mentioned steps (1) be passed through successively causticizing reaction pond in lime-flue gas pliable cell (2) and
Carburizing reagent pond carries out causticization, carbonization treatment, and clarified solution enters 2# clear water reserviors；
(3) clarified solution that above-mentioned steps (2) are obtained is passed through film upgrading unit (3), hyperfiltration treatment is carried out to the clarified solution first,
The product water of ultrafiltration is passed through electrodialysis plant and carries out point salt and concentration；Electrodialysis produce fresh water be passed through reverse osmosis unit carry out it is pure
Change, while producing the concentrated water containing NaCl；The fresh water that counter-infiltration is produced is back to production, and the concentrated water of generation reenters electrodialysis
Device is processed；
(4) concentrated water containing NaCl that above-mentioned steps (3) electrodialysis plant is produced is passed through evaporative crystallization unit (4), is acquired
Technical grade NaCl crystal salts and condensed water, recycling condensing water is in production；
In the step (1), milk of lime is added in neutralization pond, add organic sulfur in sedimentation basin, milk of lime or organic sulfur and iron,
Lead, chromium, copper, the reaction of mercury heavy metal ion produce hydroxide or sulfide；
In the step (1), flocculant is added in flocculation basin, the suspension in waste water is produced precipitation, added in depositing reservoir and helped
Solidifying agent, makes the sediment of generation accelerate to separate；
In the step (2), milk of lime and sodium sulphate are added in causticizing reaction pond, following reactions occur：
Ca(OH)2+MgSO4→CaSO4+Mg(OH)2↓
Ca(OH)2+Na2SO4→CaSO4+2NaOH
Mg in removing waste water2+Ion simultaneously produces NaOH, then to certain flocculant and flocculation aid is added in system, fills
Divide flocculation clarification；
In the step (2), flue gas is passed through in carburizing reagent pond, following reactions occur：
2NaOH+CO2→Na2CO3+H2O
Na2CO3+Ca2+→CaCO3↓+2Na+
Ca in removing waste water2+Ion, then to certain flocculant and flocculation aid is added in system, fully flocculation clarification；
In the step (2), the addition of milk of lime and sodium sulphate should control to produce the amount of NaOH to exist in causticizing reaction pond
Between 0.05-0.2g/L；
In the step (2), the flue gas being passed through in carburizing reagent pond is the neat stress by denitration, dedusting and desulfurization, normal
It is slowly introducing under normal temperature and pressure, the intake of flue gas should make the pH of system between 9-13；
In the step (3), the purpose of ultrafiltration is to remove the suspended solid (SS) in water, water outlet is met follow-up film process and steaming
Send out the requirement of crystallization treatment, the neutralization pond of ultrafiltration concentrate recirculation to chemical flocculation precipitation unit (1)；
In the step (3), electrodialysis-ion exchange film uses monovalent ion selective membrane, makes the Cl- in waste water in concentrated water
Enrichment, and SO4 2-Dilute side is stayed in, the purity of later crystallization is improved；
In the step (3), total dissolved solid TDS meets industry below 0.05% in the fresh water that reverse osmosis unit is produced
The requirement of recycle-water, film upgrading unit fresh-water recovery rate is not less than 90%.
6. method according to claim 5, it is characterised in that：In the step (1), the flocculant added in flocculation basin is
One or more in poly-ferric sulfate chloride, aluminium polychloride, bodied ferric sulfate；The flocculation aid added in depositing reservoir is poly- third
One or more in acrylamide, Sodium Polyacrylate, shitosan.
7. method according to claim 5, it is characterised in that：In the step (2), the flocculation added in causticizing reaction pond
Agent is one or more in poly-ferric sulfate chloride, aluminium polychloride, bodied ferric sulfate；What is added in causticizing reaction pond helps solidifying
Agent is one or more in polyacrylamide, Sodium Polyacrylate, shitosan.
8. method according to claim 5, it is characterised in that：In the step (2), the flocculation added in carburizing reagent pond
Agent is one or more in poly-ferric sulfate chloride, aluminium polychloride, bodied ferric sulfate；What is added in carburizing reagent pond helps solidifying
Agent is one or more in polyacrylamide, Sodium Polyacrylate, shitosan.
9. method according to claim 5, it is characterised in that：In the step (3), electrodialysis plant uses the behaviour of falling pole
Make, it is to avoid the fouling of face.
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| CN112897730A (en) * | 2021-01-07 | 2021-06-04 | 易门铜业有限公司 | System and method for treating and recycling high-arsenic high-fluorine waste acid |
| CN113292188A (en) * | 2021-03-17 | 2021-08-24 | 华电水务工程有限公司 | Non-softening concentrated high-salinity wastewater treatment process based on precipitated salt recovery |
| CN115490387A (en) * | 2021-06-18 | 2022-12-20 | 新特能源股份有限公司 | Comprehensive treatment method and device for various tail gas treatment recovery liquids |
| CN114735874A (en) * | 2022-04-08 | 2022-07-12 | 中国石油化工股份有限公司 | Method and device for continuously treating high-salinity desulfurization wastewater |
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Application publication date: 20170613 |