CN111170519A - Desulfurization wastewater treatment process and treatment system - Google Patents
Desulfurization wastewater treatment process and treatment system Download PDFInfo
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- CN111170519A CN111170519A CN201811341839.6A CN201811341839A CN111170519A CN 111170519 A CN111170519 A CN 111170519A CN 201811341839 A CN201811341839 A CN 201811341839A CN 111170519 A CN111170519 A CN 111170519A
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 74
- 230000023556 desulfurization Effects 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 66
- 230000008569 process Effects 0.000 title abstract description 30
- 238000004065 wastewater treatment Methods 0.000 title abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 265
- 238000001728 nano-filtration Methods 0.000 claims abstract description 211
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 162
- 239000012528 membrane Substances 0.000 claims abstract description 102
- 239000002351 wastewater Substances 0.000 claims abstract description 81
- 238000000926 separation method Methods 0.000 claims abstract description 62
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 56
- 150000003839 salts Chemical class 0.000 claims abstract description 52
- 238000002425 crystallisation Methods 0.000 claims abstract description 46
- 230000008025 crystallization Effects 0.000 claims abstract description 45
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 23
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 23
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001223 reverse osmosis Methods 0.000 claims description 110
- 238000000909 electrodialysis Methods 0.000 claims description 69
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 56
- 239000000047 product Substances 0.000 claims description 56
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 230000007935 neutral effect Effects 0.000 claims description 24
- 230000008878 coupling Effects 0.000 claims description 17
- 238000010168 coupling process Methods 0.000 claims description 17
- 238000005859 coupling reaction Methods 0.000 claims description 17
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910001424 calcium ion Inorganic materials 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000005352 clarification Methods 0.000 claims description 10
- 238000003672 processing method Methods 0.000 claims description 6
- 239000010802 sludge Substances 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 8
- 239000000920 calcium hydroxide Substances 0.000 abstract description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 5
- 239000012141 concentrate Substances 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 19
- 239000000460 chlorine Substances 0.000 description 19
- 229910052801 chlorine Inorganic materials 0.000 description 18
- 239000013505 freshwater Substances 0.000 description 16
- 239000002455 scale inhibitor Substances 0.000 description 16
- 239000000701 coagulant Substances 0.000 description 14
- 238000005265 energy consumption Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 13
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 12
- 229910001425 magnesium ion Inorganic materials 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 11
- 208000028659 discharge Diseases 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- 125000001741 organic sulfur group Chemical group 0.000 description 9
- 230000009467 reduction Effects 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000012267 brine Substances 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 238000000108 ultra-filtration Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010979 pH adjustment Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000001804 chlorine Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000009287 sand filtration Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000072 sodium resin Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Images
Classifications
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- 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
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—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
- C02F1/46109—Electrodes
-
- 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
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- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- 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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/05—Conductivity or salinity
- C02F2209/055—Hardness
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
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- Organic Chemistry (AREA)
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- Inorganic Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明涉及脱硫废水处理领域，公开了脱硫废水的处理方法和处理系统。该方法包括：(1)在氢氧化钠的存在下，将脱硫废水进行软化澄清处理，(2)向软化澄清出水中加入硫酸钠并进行常温结晶，得到常温结晶出水；(3)将所述常温结晶出水进行纳滤分离处理，得到纳滤产水和纳滤浓水；(4)将纳滤产水进行膜浓缩处理，得到膜浓缩产水和膜浓缩浓水；(5)将所述膜浓缩浓水进行隔膜电解，得到氯气和氢氧化钠。本发明的方法在膜浓缩后盐浓度可提高到180g/L以上，浓水流量减量至15％以下，隔膜电解得到的氢氧化钠返回到软化过程中循环使用，可以避免氢氧化钙的加入，同时减少硫酸钠的加药量，节省药剂和运行成本。
The invention relates to the field of desulfurization wastewater treatment, and discloses a desulfurization wastewater treatment method and a treatment system. The method comprises: (1) softening and clarifying desulfurization wastewater in the presence of sodium hydroxide, (2) adding sodium sulfate to the softened and clarifying effluent and performing crystallization at room temperature to obtain crystallization effluent at room temperature; The crystallization effluent at room temperature is subjected to nanofiltration separation treatment to obtain nanofiltration product water and nanofiltration concentrated water; (4) the nanofiltration product water is subjected to membrane concentration treatment to obtain membrane concentrated product water and membrane concentrated concentrated water; (5) the described The membrane concentrates the concentrated water for diaphragm electrolysis to obtain chlorine gas and sodium hydroxide. In the method of the invention, the salt concentration can be increased to more than 180 g/L after the membrane is concentrated, the flow rate of the concentrated water can be reduced to less than 15%, the sodium hydroxide obtained by the membrane electrolysis is returned to the softening process for recycling, and the addition of calcium hydroxide can be avoided. , while reducing the dosage of sodium sulfate, saving chemicals and operating costs.
Description
Technical Field
The invention relates to the field of desulfurization wastewater treatment, in particular to a desulfurization wastewater treatment method and a desulfurization wastewater treatment system.
Background
A plurality of flue gas desulfurization systems adopted at home and abroad are limestone-gypsum wet flue gas desulfurization processes, which are large-scale commercialized desulfurization methods in the world, and have the advantages of mature technology, relatively reliable operation, high desulfurization efficiency and good adaptability to coal types. In the desulfurization process, a certain amount of wastewater must be discharged regularly, so as to maintain the balance of the materials of a slurry circulating system of a desulfurization device, prevent the concentration of chlorine in flue gas from exceeding a specified value and ensure the quality of gypsum. The wastewater mainly comes from a flushing water system, gypsum dehydration and the like, and the desulfurization wastewater is generally acidic and has the characteristics of high salt content, high suspended matter content, heavy metal content and large water quality fluctuation. Such as direct discharge, will severely affect the surrounding environment.
The zero discharge of the waste water of the power plant is a water using mode with high water saving level of the power plant, and has good social and environmental benefits. With the rapid development of economy and electric power in China, in areas with more coal and less water in the north of China, the available amount of water resources is reduced day by day, and the water price and the pollution discharge cost are increased continuously, so that zero discharge of waste water of a power plant is necessary and inevitable.
CN205653287U discloses a device of desulfurization waste water zero release processing includes: a remove magnesium and remove the heavy pond group, the intercommunication remove magnesium and remove a calcium sedimentation pond group of heavy pond group, the intercommunication remove a nanofiltration system (it includes a sulfate dense water export and a chlorine salt fresh water export, the sulfate dense water export through a dense water return line with remove calcium sedimentation pond group intercommunication), with the chlorine salt fresh water export through the multistage reverse osmosis system of a concentrated conveying pipeline intercommunication, with an evaporative crystallizer of multistage reverse osmosis system's a dense water export intercommunication. The device can carry out the preliminary treatment to desulfurization waste water, makes desulfurization waste water accord with membrane separation technical requirement to reduce operation and treatment cost by a wide margin.
CN104355473A discloses a method for carrying out desalination zero-emission treatment on power plant desulfurization wastewater by using an electrodialysis technology, wherein the power plant desulfurization wastewater is subjected to pretreatment such as neutralization, precipitation, coagulation, filtration and the like to remove COD (chemical oxygen demand), heavy metals, fluoride ions and the like in the wastewater; then, separating monovalent salt and divalent salt in the wastewater by using nanofiltration; and then desalting and concentrating nanofiltration produced water by utilizing multi-stage countercurrent reverse-flow electrodialysis, and evaporating and concentrating the electrodialysis concentrated water to obtain NaCl salt.
CN103979729A discloses a system and a method for recycling and zero discharge of desulfurization waste water, wherein the desulfurization waste water enters a nanofiltration system after being filtered, concentrated water of the nanofiltration system returns to a desulfurization tower, nanofiltration fresh water is concentrated by a brine concentration device and then is evaporated and crystallized, the obtained fresh water can be recycled, salt is separated out and dried into a crystal salt product, and therefore the zero discharge of the desulfurization waste water is realized, the quality of the recovered fresh water is high, and the whole process saves chemical reagents and operating cost.
CN104478141A discloses a power plant flue gas desulfurization wastewater treatment process, wherein desulfurization wastewater is firstly filtered by a plate-and-frame filter and is filtered by a micropore to obtain clear filtrate without suspended matters; secondly, concentrating the clear filtrate by using an electrodialysis membrane module with pH adjustment, and recycling the concentrated fresh water; and thirdly, performing microporous filtration on the mixture in the concentration chamber, recovering filter residues, and allowing filtrate to enter a calcium sulfate crystallization device for crystallization to separate out calcium sulfate crystals.
CN105174580A discloses a desulfurization waste water zero release processing system, and waste water gets into full-automatic softening filter, ultrafiltration, one-level RO and second grade RO system after neutralization equalizing basin, coagulating sedimentation tank in proper order, and the product water is as the clean water retrieval and utilization, and dense water gets into the salt manufacturing in the evaporation crystallizer. And the zero emission treatment of the desulfurization wastewater is realized through the combination of the membrane system.
CN105110538A discloses a desulfurization wastewater zero-discharge treatment method, wherein desulfurization wastewater is pretreated and then directly treated by an electrodialysis system, concentrated water is directly subjected to furnace-spraying incineration or evaporation, fresh water is treated by a reverse osmosis system, reverse osmosis produced water is directly recycled, and concentrated water is returned to the electrodialysis system for treatment. The invention adopts the 'pretreatment + membrane integration technology' to treat the desulfurization wastewater, so that most of water resources are recycled, and the environmental pollution is reduced.
CN105254104A discloses a low-cost power plant desulfurization wastewater zero-discharge treatment process, which mainly comprises a pretreatment process and an evaporative crystallization process. In the pretreatment process, lime and sodium sulfate are used for reaction in the first-stage reaction, sodium carbonate is used for complete softening in the second-stage reaction, the obtained wastewater enters a plate heat exchanger for temperature rise after pH adjustment, then enters an evaporator for evaporation and crystallization, and crystal slurry is subjected to crystallization and separation.
Aiming at the water quality characteristics of the desulfurization wastewater, the zero-emission treatment technology generally adopts two or more technologies of pretreatment, salt separation, membrane concentration, evaporative crystallization and the like to be integrated and combined, and the patent documents relate to the technologies. Through comparison, the subsequent treatment by utilizing the membrane technology is involved, the hardness in the wastewater is completely removed by adopting softening modes such as sodium carbonate, carbon dioxide flue gas or ion resin and the like in the pretreatment process, the running cost of sodium hydroxide, sodium carbonate, resin and the like used in the softening process is very high, and the development of the zero-emission technology is limited. The concentration degree and the reduction degree are different in the subsequent membrane treatment process, and the zero emission treatment is limited to be popularized.
The desulfurization wastewater not only has the characteristics of high suspended matters and heavy metals and is acidic, but also contains high-concentration chloride ions, calcium ions and sulfate ions. Therefore, after the conventional triple-box process is only utilized to adjust the pH value and remove suspended matters and heavy metals, the high-concentration salt-containing wastewater cannot meet the discharge requirement, and a zero-discharge process for recycling and reducing the wastewater is realized. As mentioned above, the recycling and reduction processes are mostly performed by using membrane technology, and in the using process of the membrane technology, the concentration and supersaturation of scaling factors such as calcium ions, magnesium ions and silicon which are easy to cause pollution to membrane elements are rapidly increased after membrane concentration, so that scaling is easily caused on the surface of a membrane concentration system to block the membrane elements, and further, the operation and maintenance costs of the process system are increased. Therefore, the removal of pollution factors such as calcium, magnesium, silicon and the like is important in the reduction and recycling process by using the membrane method. And the power plant desulfurization wastewater contains high-concentration calcium ions and magnesium ions, and scaling influence exists on a membrane system, a water path system and the like in the treatment process. In the conventional treatment process, calcium ions, magnesium ions, silicon and the like are mainly treated by the technologies of chemical precipitation, flue gas precipitation, electrochemical adsorption, resin softening and the like, so that the influence of the existence of the pollution factors on the system is reduced. However, the process flow is long, the operation is complicated, and the medicament cost is high in the operation process.
Therefore, the development of a low-cost and high-resource-recycling desulfurization wastewater treatment method and system has important practical significance and market application value.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method and a system for treating desulfurization wastewater.
According to a first aspect of the present invention, there is provided a method for treating desulfurization waste water, comprising:
(1) in the presence of sodium hydroxide, carrying out softening and clarifying treatment on the desulfurization wastewater to obtain softened and clarified effluent, and adding acid into the softened and clarified effluent to obtain neutral softened and clarified effluent;
(2) adding sodium sulfate into the neutral softened clarified effluent and crystallizing at normal temperature to obtain normal-temperature crystallized effluent and calcium sulfate product salt;
(3) carrying out nanofiltration separation treatment on the normal-temperature crystallized effluent to obtain nanofiltration product water and nanofiltration concentrated water, and returning the nanofiltration concentrated water to the step (2);
(4) carrying out membrane concentration treatment on the nanofiltration produced water to obtain membrane concentrated produced water and membrane concentrated water;
(5) and (3) carrying out diaphragm electrolysis on the membrane concentrated water to obtain chlorine and a sodium hydroxide aqueous solution, and returning the sodium hydroxide aqueous solution to the step (1).
According to a second aspect of the present invention, there is provided a system for treating desulfurization waste water, comprising: softening and clarifying treatment unit, normal temperature crystallization unit, nanofiltration separation unit, membrane concentration unit and diaphragm electrolysis unit;
the softening and clarifying treatment unit is used for softening and clarifying the desulfurization wastewater to obtain softened and clarified effluent;
the normal-temperature crystallization unit is used for adding sodium sulfate into neutral softened and clarified effluent obtained after the softened and clarified effluent is subjected to acid pH adjustment and carrying out normal-temperature crystallization treatment to obtain normal-temperature crystallized effluent and calcium sulfate product salt;
the nanofiltration separation unit is used for carrying out nanofiltration separation treatment on the normal-temperature crystallized effluent to obtain nanofiltration product water and nanofiltration concentrated water, and returning the nanofiltration concentrated water to the normal-temperature crystallization unit;
the membrane concentration unit is used for carrying out membrane concentration treatment on the nanofiltration water to obtain membrane concentration water and membrane concentration water;
and the diaphragm electrolysis unit is used for diaphragm electrolysis of the membrane concentrated water to obtain chlorine and a sodium hydroxide aqueous solution, and returning the obtained sodium hydroxide aqueous solution to the softening and clarifying treatment unit.
The method combines normal temperature crystallization and nanofiltration technology, wastewater is not completely softened, and sodium sulfate is used for replacing expensive sodium carbonate to regulate and control hardness, so that the cost of the medicament is reduced; the concentrated water containing high-concentration sodium chloride can recover high-purity chlorine and sodium hydroxide aqueous solution through diaphragm electrolysis, the concentration of the sodium hydroxide aqueous solution is high, the sodium hydroxide aqueous solution returns to pretreatment for cyclic utilization, so that the addition of an additional alkaline medicament (such as calcium hydroxide) can be avoided, the self-sufficiency in the system is basically realized, the corresponding dosage of sodium sulfate in the normal-temperature crystallization process is greatly reduced, the effective coupling of the whole treatment process is realized, and the medicament cost is reduced. Moreover, the treatment method of the invention can simultaneously obtain byproducts (chlorine, calcium sulfate, magnesium hydroxide and the like) with high added values.
According to a preferred embodiment, when the membrane concentration treatment adopts electrodialysis-reverse osmosis coupling treatment, membrane concentration concentrated water with higher salt concentration can be obtained, and the concentrated water can be electrolyzed in diaphragm electrolysis to obtain a sodium hydroxide aqueous solution with higher concentration, and the energy consumption of the diaphragm electrolysis is reduced. According to a preferred embodiment, when the nanofiltration separation adopts two-stage nanofiltration separation, the hardness of nanofiltration produced water can be further reduced, so that the diaphragm electrolysis can obtain high-purity chlorine and high-concentration sodium hydroxide aqueous solution under the condition of lower current and/or voltage, and the electrolysis energy consumption is reduced.
Therefore, the wastewater removal treatment method can realize the reduction of the whole operation cost by effectively matching each treatment stage, ensure the stable operation of the system and obtain products with high added values.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a schematic diagram of one embodiment of a treatment process according to the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a method for treating desulfurization waste water, comprising:
(1) in the presence of sodium hydroxide, carrying out softening and clarifying treatment on the desulfurization wastewater to obtain softened and clarified effluent, and adding acid into the softened and clarified effluent to obtain neutral softened and clarified effluent;
(2) adding sodium sulfate into the neutral softened clarified effluent and crystallizing at normal temperature to obtain normal-temperature crystallized effluent and calcium sulfate product salt;
(3) carrying out nanofiltration separation treatment on the normal-temperature crystallized effluent to obtain nanofiltration product water and nanofiltration concentrated water, and returning the nanofiltration concentrated water to the step (2);
(4) carrying out membrane concentration treatment on the nanofiltration produced water to obtain membrane concentrated produced water and membrane concentrated water;
(5) and (3) carrying out diaphragm electrolysis on the membrane concentrated water to obtain chlorine and a sodium hydroxide aqueous solution, and returning the sodium hydroxide aqueous solution to the step (1).
The desulfurization waste water treated by the present invention is not particularly limited, and it is well known in the art that the desulfurization waste water may be waste water from a limestone-gypsum wet desulfurization system in which suspended substances, heavy metal ions, chloride ions, calcium ions, magnesium ions, sulfate ions, silicon, and other impurities are main components, and the waste water is acidic.
According to one embodiment, the desulfurization waste water has a pH of 4-6.5, a TDS value of 20000-40000mg/L, a conductivity of 20-35mS/cm, a calcium ion content of 400-6000mg/L, a magnesium ion content of 500-5000mg/L, a sodium ion content of 200-5000mg/L, a chloride ion content of 5000-20000mg/L, a sulfate ion content of 500-15000mg/L, a turbidity of 4000-15000NTU, a basicity of 0.2-50mg/L, and an ammonia nitrogen content of 10-200 mg/L.
In the treatment method of the present invention, preferably, in the step (1), the softening and clarifying treatment method includes: and adjusting the pH value of the desulfurization wastewater to 11-12 by using an aqueous solution of sodium hydroxide, reacting for 45-80min, and then settling for 80-150min to obtain the softened and clarified effluent.
In the step (1), the acid is preferably sulfuric acid, and the pH of the neutral softened clear effluent is 6-8, and more preferably 7-8. In the step, sulfuric acid is added into the softened and clarified effluent to adjust the pH value to be neutral, and the added sulfate ions react with calcium ions in water to generate a small amount of calcium sulfate crystals, so that the reaction in a subsequent normal-temperature crystallization reactor is facilitated.
In the treatment method of the present invention, the softening and clarifying treatment method further comprises: while adding sodium hydroxide to the desulfurized wastewater, an organic sulfur, a coagulant aid and optionally a flocculant are added thereto.
As will be understood by those skilled in the art, the invention can effectively remove suspended matters, heavy metal ions, magnesium ions, silicon and other pollutants which have influence on a subsequent membrane system through the softening and clarifying treatment of the step (1), and simultaneously obtain a magnesium hydroxide product, and can reduce the magnesium ion concentration to below 10mg/L through adjusting the pH of the wastewater to be 11-12.
The organic sulfur, the flocculant and the coagulant aid of the present invention are not particularly limited, and may be various organic sulfur, flocculant and coagulant aid, respectively, which are commonly used in the art. Preferably, the organic sulfur is at least one of TMT-15, TMT-55 and DTC; the flocculating agent is at least one of polyaluminium sulfate, polyferric chloride, ferric chloride and aluminium sulfate; the coagulant aid is polyacrylamide.
In the treatment method of the present invention, preferably, the amount of the organic sulfur is 5 to 150mg/L, more preferably 5 to 80 mg/L; the dosage of the flocculating agent is 0-30mg/L, and the dosage of the coagulant aid is 3-10 mg/L.
In the treatment method, in the step (2), sodium sulfate is added into the softened and clarified effluent and the subsequently returned nanofiltration concentrated water, and the softened and clarified effluent and the subsequently returned nanofiltration concentrated water are subjected to normal-temperature crystallization treatment, the added sulfate radicals react with calcium ions to generate calcium sulfate, the solubility of the calcium sulfate in the wastewater is low, and the calcium sulfate can be crystallized and separated out under the normal-temperature condition to obtain calcium sulfate product salt. This step achieves regulation of wastewater hardness, rather than complete softening.
Preferably, the addition amount of the sodium sulfate is such that the concentration of calcium ions in the normal-temperature crystallization effluent water is below 20 mmol/L. The supersaturation degree of the calcium sulfate in the obtained normal temperature crystallization effluent water is generally 100-150%.
In the step (2), the normal temperature crystallization method further includes: the sodium sulfate is added simultaneously with the coagulant aid, which is preferably used in an amount of 1 to 10mg/L, as described above.
In the treatment method of the present invention, the nanofiltration membrane element used in the nanofiltration separation treatment is required to have a lower rejection rate of monovalent salt and a higher rejection rate of divalent salt so as to better realize the high-efficiency separation of monovalent salt and divalent salt and obtain a higher water recovery rate, preferably, the nanofiltration membrane element used in the nanofiltration separation treatment is a nanofiltration membrane element having a rejection rate of more than 98% for sulfate ions in the nanofiltration influent water and a rejection rate of more than 95% for calcium ions in the nanofiltration influent water, and may be, for example, a GE DL series nanofiltration membrane element, a GE SWSR series nanofiltration membrane, a GE DK series nanofiltration membrane element or a NE8040-40 nanofiltration membrane element of the korean TCK company.
In the step (3), the nanofiltration separation treatment can adopt one-stage nanofiltration or multi-stage nanofiltration treatment. In the invention, the step (2) of returning the nanofiltration concentrated water refers to mixing the nanofiltration concentrated water with neutral softened clarified effluent, adding sodium sulfate and crystallizing at normal temperature; or sodium sulfate is added into the two streams respectively to carry out normal temperature crystallization, and the former is preferably adopted.
In addition, when the multi-stage nanofiltration treatment is adopted, the nanofiltration concentrated water refers to nanofiltration concentrated water generated by the first-stage nanofiltration separation, and the nanofiltration water produced by the membrane concentration treatment refers to nanofiltration water produced by the last-stage separation.
According to one embodiment, the nanofiltration treatment adopts primary nanofiltration treatment, and the operating pressure of the nanofiltration separation treatment is 0.5-2 MPa; preferably, the flow of nanofiltration water production is controlled to be 40-60% of the nanofiltration water inlet flow.
According to another more preferred embodiment, the nanofiltration treatment employs a two-stage nanofiltration treatment comprising:
3-1: performing primary nanofiltration separation on the normal-temperature crystallized effluent to obtain primary nanofiltration concentrated water and primary nanofiltration produced water;
3-2: returning the primary nanofiltration concentrated water to the step (2), and performing secondary nanofiltration separation on the primary nanofiltration produced water to obtain secondary nanofiltration concentrated water and secondary nanofiltration produced water;
3-3: and returning the secondary nanofiltration concentrated water to perform primary nanofiltration separation, and performing membrane concentration treatment on the secondary nanofiltration produced water.
The preferred embodiment can further avoid the scaling problem during the membrane electrolysis process, reduce the operating current and/or voltage of the membrane electrolysis, and increase the concentration of the aqueous sodium hydroxide solution.
In the preferred embodiment, more preferably, the operating pressure of the first-stage nanofiltration is 0.5-2MPa, and the flow rate of the water produced by the first-stage nanofiltration is controlled to be 40-60 wt% of the inlet flow rate of nanofiltration.
In the preferred embodiment, more preferably, the operating pressure of the secondary nanofiltration is 0.4-1.2MPa, and the water yield of the secondary nanofiltration is controlled to be 70-90 wt% of the water yield of the primary nanofiltration.
In the step (3), preferably, the nanofiltration separation treatment is performed in the presence of a scale inhibitor. The type and amount of the scale inhibitor are not particularly limited, and can be selected by referring to the prior art. Preferably, the scale inhibitor is selected from an organic phosphine type scale inhibitor, an organic phosphonate type scale inhibitor, a polycarboxylic acid type scale inhibitor and a composite type scale inhibitor. The composite scale inhibitor is a scale inhibitor containing more than two effective components, for example, two or three of organic phosphine, organic phosphonate and polycarboxylic acid can be combined to be used as the scale inhibitor. In the composite scale inhibitor, the content of each effective component can be selected according to the type of the effective component, and is not particularly limited. The addition amount of the scale inhibitor can be 2-20mg/L, and preferably 3-10 mg/L.
In addition, in order to further remove suspended matters in the desulfurization wastewater, the method of the present invention may further include subjecting the hardness-controlled effluent to sand filtration and ultrafiltration before the nanofiltration separation, and the methods of sand filtration and ultrafiltration are well known in the art and will not be described herein again.
In the treatment method of the present invention, in the step (4), the membrane concentration treatment may be one-stage or multi-stage reverse osmosis concentration, one-stage or multi-stage electrodialysis concentration, or electrodialysis-reverse osmosis coupled concentration. In order to further improve the salt concentration of the diaphragm electrolysis and reduce the operation cost and energy consumption, the electrodialysis-reverse osmosis coupling concentration is preferably adopted in the membrane concentration treatment.
In the present invention, the electrodialysis-reverse osmosis coupled concentration includes:
4-1: carrying out reverse osmosis treatment on the nanofiltration produced water to obtain reverse osmosis produced water and reverse osmosis concentrated water;
4-2: and performing electrodialysis treatment on the obtained reverse osmosis concentrated water to obtain electrodialysis concentrated water and electrodialysis produced water, and returning the electrodialysis produced water to perform reverse osmosis treatment.
Preferably, the operating pressure of the reverse osmosis treatment is 2-5 MPa. Further preferably, the reverse osmosis treatment is carried out so that the recovery rate of the obtained reverse osmosis produced water is 50-75%, and the salt content of the obtained reverse osmosis concentrated water is 20-50 g/L.
Preferably, the current density of the electrodialysis treatment is 30-35mA/cm2The current is 120-150A, and the voltage is 100-120V.
In the electrodialysis-reverse osmosis coupling concentration treatment, the reverse osmosis is used for primarily concentrating the saline water (20-50g/L), then membrane concentrated water with the salt concentration of more than 190g/L can be obtained through electrodialysis, and the operation pressure and the energy consumption can be optimized through controlling the concentration degree. In addition, the reverse osmosis produced water can reach the standard of recycled water (the salt concentration is less than or equal to 1g/L), and is preferably returned to a factory for recycling. The water produced by nanofiltration is deeply concentrated by electrodialysis-reverse osmosis coupling, so that the problem of high energy consumption caused by separate electrodialysis or reverse osmosis deep concentration can be effectively solved.
In the step (5), the operation conditions of the membrane electrolysis include: the current density is 2-4kA/m2The voltage is 30-100V, preferably 30-50V.
It will be understood by those skilled in the art that the diaphragm electrolysis, in addition to producing chlorine and aqueous sodium hydroxide solution, will produce diaphragm electrolysis fresh water (i.e. sodium chloride solution, also called low concentration brine solution) after electrolysis, which is the solution after dechlorination in the anode region during diaphragm electrolysis, preferably with a salt content of 100-120 g/L. When the membrane concentration treatment employs the electrodialysis-reverse osmosis coupled concentration, the method of the present invention may further include: and returning the diaphragm electrolysis fresh water to continue the electrodialysis treatment.
According to a second aspect of the present invention, there is provided a system for treating desulfurization waste water, comprising: softening and clarifying treatment unit, normal temperature crystallization unit, nanofiltration separation unit, membrane concentration unit and diaphragm electrolysis unit.
The softening and clarifying treatment unit is used for softening and clarifying the desulfurization wastewater to obtain softened and clarified effluent;
the normal-temperature crystallization unit is used for adding sodium sulfate into neutral softened and clarified effluent obtained after the softened and clarified effluent is subjected to acid pH adjustment and carrying out normal-temperature crystallization treatment to obtain normal-temperature crystallized effluent and calcium sulfate product salt;
the nanofiltration separation unit is used for carrying out nanofiltration separation treatment on the normal-temperature crystallized effluent to obtain nanofiltration product water and nanofiltration concentrated water, and returning the nanofiltration concentrated water to the normal-temperature crystallization unit;
the membrane concentration unit is used for carrying out membrane concentration treatment on the nanofiltration water to obtain membrane concentration water and membrane concentration water;
and the diaphragm electrolysis unit is used for diaphragm electrolysis of the membrane concentrated water to obtain chlorine and a sodium hydroxide aqueous solution, and returning the obtained sodium hydroxide aqueous solution to the softening and clarifying treatment unit.
In the treatment system of the present invention, the softening and clarifying treatment unit may include a neutralization reaction tank and a clarifier. The neutralization reaction tank is used for adding sodium hydroxide into the desulfurization wastewater for reaction; and the clarification tank is used for settling the reaction product to obtain softened and clarified effluent and sludge.
In the treatment system, the nanofiltration separation unit comprises at least one nanofiltration membrane element, and the nanofiltration membrane element has a retention rate of more than 98% for sulfate ions in the hardness-regulated outlet water and a retention rate of more than 95% for calcium ions in the nanofiltration inlet water, and can be, for example, a GE DL series nanofiltration membrane element, a GE SWSR series nanofiltration membrane element, a GEDK series nanofiltration membrane element or a NE8040-40 nanofiltration membrane element of Korea TCK company.
The nanofiltration separation unit can be a one-stage nanofiltration system or a two-stage nanofiltration separation system.
According to a preferred embodiment, the nanofiltration separation unit adopts a two-stage nanofiltration system, the two-stage nanofiltration separation system is used for sequentially carrying out primary and secondary nanofiltration separation on the normal-temperature crystallized effluent, returning the primary nanofiltration concentrated water obtained by the primary separation to the normal-temperature crystallization unit, and returning the secondary nanofiltration concentrated water obtained by the secondary separation to carry out the primary nanofiltration separation.
In addition, in order to further remove suspended matters in the hardness-controlled effluent, the treatment systems of the present invention may further comprise a sand filtration-ultrafiltration treatment unit, respectively, through which the suspended matters in the hardness-controlled effluent are further removed and then enter the nanofiltration separation unit, and the arrangement of the sand filtration-ultrafiltration treatment unit is well known in the art and will not be described herein again.
The membrane concentration treatment unit can be selected from one or more stages of reverse osmosis concentration units, one or more stages of electrodialysis concentration units or electrodialysis-reverse osmosis coupling concentration units, and is preferably an electrodialysis-reverse osmosis coupling concentration unit. Wherein the electrodialysis-reverse osmosis coupling concentration unit comprises an electrodialysis unit and a reverse osmosis unit;
the reverse osmosis unit is used for performing reverse osmosis treatment on the nanofiltration produced water to obtain reverse osmosis produced water and reverse osmosis concentrated water which are used as membrane concentration produced water; and the electrodialysis unit is used for carrying out electrodialysis treatment on the obtained reverse osmosis concentrated water to obtain electrodialysis concentrated water and electrodialysis water production which are used as membrane concentrated water, and returning the obtained electrodialysis water production to the reverse osmosis unit.
The reverse osmosis unit and the electrodialysis unit are not particularly limited in the present invention, and may be selected from those commonly used in the art. Generally, the reverse osmosis unit may comprise at least one reverse osmosis membrane element, preferably at least two reverse osmosis membrane elements used in series, and the electrodialysis unit may be a stack comprising three hydraulic series electrodialysis membranes and corresponding auxiliary systems.
The diaphragm cell may be selected from diaphragm cells commonly used in the salt diaphragm electrolysis soda making technology, which generally comprise: a direct current stabilized voltage supply, a cation selective ion membrane, a chlorine gas recovery device and the like. Wherein the cation selective membrane can be cation selective ion membrane such as Asahi glass, Asahi chemical, and Home-made Dongye.
And electrolyzing to obtain a chlorine product at the anode of the diaphragm electrolysis unit and obtain a sodium hydroxide solution at the cathode.
The processing method of the first aspect of the invention may be implemented on a processing system of the invention.
The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited thereby.
The softening and clarifying unit comprises a volume of 20m3Has a neutralization reaction tank and a volume of 40m3The clarification tank of (1);
the nanofiltration separation unit comprises a first-stage two-stage nanofiltration system consisting of 7 membrane shells and provided with 4 GE DK 8040F30 nanofiltration membrane elements connected in series, and a second-stage two-stage nanofiltration system consisting of 6 membrane shells and provided with 4 GE DK 8040F30 nanofiltration membrane elements connected in series;
the normal temperature crystallization unit comprises a stirring device with a volume of 40m3The stainless steel container of (1);
the electrodialysis unit comprises a total membrane area of 1500m2The three-stage hydraulic series electrodialysis membrane stack and the corresponding auxiliary system;
the reverse osmosis unit is a first-stage two-stage reverse osmosis system consisting of 7 pressure containers and 4 series-connected seawater desalination reverse osmosis membrane elements assembled in the pressure containers;
the diaphragm electrolysis unit is a diaphragm electrolysis cell, wherein the cation selective ion membrane adopts an Asahi glass ion exchange membrane;
the flocculant is polyaluminium sulfate, which is purchased from Chengsheng water purification material factory in Chengsheng, Chengshen 05-11;
the coagulant aid is polyacrylamide, purchased from Nalcidae under the trademark 8103 PLUS;
the effective component of the scale inhibitor is organic phosphonate which is purchased from Nalco company and has the trade name of OSMOTREAT OSM 1035;
the power plant desulfurization wastewater comprises the following components: the pH value is 6.15, the TDS value is 27643mg/L, the conductivity is 29.6mS/cm, the calcium ion content is 1013.81mg/L, the magnesium ion content is 4722.03mg/L, the sodium ion content is 200.19mg/L, the chloride ion content is 6880.71mg/L, the sulfate ion content is 13093.41mg/L, the turbidity is 7269NTU, the alkalinity is 18mg/L, and the ammonia nitrogen content is 17.3 mg/L.
Example 1
This example will explain the method for treating desulfurization waste water of the present invention with reference to FIG. 1.
(1) Adding the sodium hydroxide aqueous solution obtained in the step (5) into the power plant desulfurization wastewater of 20t/h in a neutralization reaction tank for reaction, adjusting the pH value of the wastewater to 11.7, adding 10mg/L organic sulfur TMT-15 and 9mg/L coagulant aid, reacting for 60min, conveying the obtained reaction product into a clarification tank for standing for 120min for sedimentation to obtain softened and clarified effluent, wherein the concentration of magnesium ions is reduced to 6.9 mg/L;
adding sulfuric acid with the mass concentration of 5% into the softened and clarified effluent of 20t/h, and adjusting the pH to 7.3 to obtain neutral softened and clarified effluent;
(2) mixing 20t/h neutral softened clarified effluent with primary nanofiltration concentrated water, feeding the mixture into a normal-temperature crystallization reactor at a flow rate of 40t/h, adding a sodium sulfate solution with a mass concentration of 20%, adding a coagulant aid of 5mg/L, reacting for 60min under a stirring condition, feeding the obtained reaction product into a clarification tank, and settling for 90min to obtain normal-temperature crystallized effluent (the calcium ion concentration is 17.9mmol/L, and the supersaturation degree of calcium sulfate is 134%) and a calcium sulfate product;
(3) supplying 40t/h of normal-temperature crystallized effluent to a nanofiltration separation unit (a secondary two-stage nanofiltration system), and in the presence of 5mg/L of scale inhibitor, firstly performing primary nanofiltration separation treatment, wherein the operating pressure of primary nanofiltration is 1.8MPa, so as to obtain primary nanofiltration concentrated water (the supersaturation degree of calcium sulfate is 396%) and primary nanofiltration produced water, and the recovery rate of the produced water is 60%; returning the primary nanofiltration concentrated water and the neutral softened clear water to a normal-temperature crystallization reactor for reaction, continuously performing secondary nanofiltration separation treatment on the primary nanofiltration produced water, wherein the operating pressure of the secondary nanofiltration is 1.1MPa, so that secondary nanofiltration concentrated water and secondary nanofiltration produced water (the salt content is 11.3g/L) are obtained, the recovery rate of the produced water is 83%, and returning the secondary nanofiltration concentrated water to the primary nanofiltration for continuous treatment;
(4) performing reverse osmosis treatment on the secondary nanofiltration water product for 20t/h to obtain reverse osmosis water product and reverse osmosis concentrated water (the salt content is 45.7g/L), performing electrodialysis treatment on the obtained reverse osmosis concentrated water to obtain electrodialysis concentrated water (the salt content is 211g/L) and electrodialysis water product, and returning the obtained electrodialysis water product to reverse osmosis for continuous treatment;
wherein the reverse osmosis has the operation pressure of 3.9MPa and the water recovery rate of 70.6 percent;
the current density of the electrodialysis operation was 30mA/cm2Current 120A, voltage 110V;
the coupling treatment is carried out to obtain 1.2t/h electrodialysis concentrated water (the salt content is 211g/L) and 18.8t/h reverse osmosis produced water (the salt content is 0.5g/L), and the produced water is reused as recycled water;
(5) feeding the electrodialysis concentrated water at 1.2t/h into a diaphragm electrolytic cell, electrolyzing to obtain 109kg of chlorine (with the purity of 99.6%), 0.4t/h of sodium hydroxide aqueous solution (with the mass concentration of 31%) and 0.8t/h of diaphragm electrolysis fresh water (with the salt content of 100g/L), returning the sodium hydroxide aqueous solution to the step (1), and returning the diaphragm electrolysis fresh water to electrodialysis for concentration treatment;
wherein, the diaphragm electrolysis conditions are as follows: the current density is controlled at 3kA/m2And a voltage of 30V.
The results prove that the method of the embodiment realizes the reduction treatment of the desulfurization wastewater, and simultaneously recovers and obtains a calcium sulfate product, sodium hydroxide and a high-purity chlorine product; the electrodialysis concentrated water entering the diaphragm electrolysis unit accounts for 6% of the consumption of the desulfurization wastewater, and 94% of the reuse water is recovered. In addition, in the recycling of sodium hydroxide in this example, the dosage of calcium hydroxide added to each ton of water was reduced by 14.5kg, and the dosage of sodium sulfate added to each ton of water was further reduced by 14.8kg, compared with the case where the pH of the aqueous solution of calcium hydroxide was adjusted to the same pH. The nanofiltration produced water enters an electrodialysis-reverse osmosis coupling concentration unit for treatment, and the running energy consumption of the electrodialysis is 6.2 kWh/t; the energy consumption for membrane electrolysis was 3.1 kWh/t.
Example 2
This example will explain the method for treating desulfurization waste water of the present invention with reference to FIG. 1.
(1) Adding the sodium hydroxide aqueous solution obtained in the step (5) into the power plant desulfurization wastewater of 20t/h in a neutralization reaction tank for reaction, adjusting the pH value of the wastewater to 11.2, adding 10mg/L organic sulfur TMT-15 and 9mg/L coagulant aid, reacting for 60min, conveying the obtained reaction product into a clarification tank for standing for 120min for sedimentation to obtain softened and clarified effluent, wherein the concentration of magnesium ions is reduced to 8.9 mg/L;
adding sulfuric acid with the mass concentration of 5% into the softened and clarified effluent of 20t/h, and adjusting the pH to 7.8 to obtain neutral softened and clarified effluent;
(2) mixing 20t/h neutral softened clarified effluent with first-stage nanofiltration concentrated water, feeding the mixture into a normal-temperature crystallization reactor at a flow rate of 40t/h, adding a sodium sulfate solution with a mass concentration of 20%, adding a coagulant aid of 5mg/L, reacting for 60min under a stirring condition, feeding the obtained reaction product into a clarification tank, and settling for 90min to obtain normal-temperature crystallized effluent (the calcium ion concentration is 18.2mmol/L, and the supersaturation degree of calcium sulfate is 138%) and a calcium sulfate product;
(3) supplying 40t/h of normal-temperature crystallized effluent to a nanofiltration separation unit (a secondary two-stage nanofiltration system), and in the presence of 6mg/L of scale inhibitor, firstly performing primary nanofiltration separation treatment, wherein the operating pressure of primary nanofiltration is 1.85MPa, so as to obtain primary nanofiltration concentrated water (the supersaturation degree of calcium sulfate is 401%) and primary nanofiltration produced water, wherein the recovery rate of the produced water is 63%; the first-stage nanofiltration concentrated water returns to enter a normal-temperature crystallization reactor together with the neutral softened and clarified effluent to react, the first-stage nanofiltration produced water is continuously subjected to second-stage nanofiltration separation treatment, the operating pressure of the second-stage nanofiltration is 1.0MPa, so that second-stage nanofiltration concentrated water and second-stage nanofiltration produced water (the salt content is 11.6g/L) are obtained, the recovery rate of a second-stage nanofiltration system is 81%, and the second-stage nanofiltration concentrated water returns to the first-stage nanofiltration to be continuously treated;
(4) performing reverse osmosis treatment on the secondary nanofiltration water product for 20t/h to obtain reverse osmosis water product and reverse osmosis concentrated water (the salt content is 38.6g/L), performing electrodialysis treatment on the obtained reverse osmosis concentrated water to obtain electrodialysis concentrated water (the salt content is 192g/L) and electrodialysis water product, and returning the obtained electrodialysis water product to reverse osmosis for continuous treatment;
wherein the reverse osmosis operating pressure is 3.7MPa, and the water recovery rate is 68.1%;
the current density of the electrodialysis operation was 30mA/cm2Current 120A, voltage 115V;
the coupling treatment is carried out to obtain 1.5t/h electrodialysis concentrated water (the salt content is 192g/L) and 18.5t/h reverse osmosis produced water (the salt content is 0.5g/L), and the produced water is reused as recycled water;
(5) feeding the electrodialysis concentrated water at 1.5t/h into a diaphragm electrolytic cell, electrolyzing to obtain 106kg of chlorine (with the purity of 99.4%), 0.4t/h of sodium hydroxide aqueous solution (with the mass concentration of 32%) and 1.1t/h of low-concentration brine (with the salt content of 104g/L), returning the sodium hydroxide aqueous solution to the step (1), and returning the rest low-concentration brine to the electrodialysis for concentration treatment;
wherein, the diaphragm electrolysis conditions are as follows: the current density is controlled at 3kA/m2And a voltage of 36V.
The results prove that the method of the embodiment realizes the reduction treatment of the desulfurization wastewater, and simultaneously recovers and obtains a calcium sulfate product, sodium hydroxide and a high-purity chlorine product; the electrodialysis concentrated water entering the diaphragm electrolysis unit accounts for 7.5% of the consumption of the desulfurization wastewater, and 92.5% of the reuse water is recovered. In addition, the recycling of sodium hydroxide in this example can reduce the addition of 14.1 kg/ton of water to calcium hydroxide and further reduce the addition of 14.4 kg/ton of water to sodium sulfate, as compared with the adjustment of the pH of the calcium hydroxide aqueous solution to the same pH. The nanofiltration produced water enters an electrodialysis-reverse osmosis coupling concentration unit for concentration treatment, and the operation energy consumption of electrodialysis is 6.4 kWh/t; the energy consumption for membrane electrolysis was 3.7 kWh/t.
Example 3
(1) Adding the sodium hydroxide aqueous solution obtained in the step (5) into the power plant desulfurization wastewater of 20t/h in a neutralization reaction tank for reaction, adjusting the pH value of the wastewater to 11.4, adding 9mg/L organic sulfur TMT-15 and 7mg/L coagulant aid, reacting for 50min, conveying the obtained reaction product into a clarification tank, standing for 120min, and settling to obtain softened and clarified effluent, wherein the concentration of magnesium ions is reduced to 9.6 mg/L;
adding sulfuric acid with the mass concentration of 5% into the softened and clarified effluent of 20t/h, and adjusting the pH to 7.8 to obtain neutral softened and clarified effluent;
(2) mixing 20t/h neutral softened clarified effluent with nanofiltration concentrated water, feeding the mixture into a normal-temperature crystallization reactor at a flow rate of 40t/h, adding a sodium sulfate solution with a mass concentration of 20%, adding a coagulant aid of 5mg/L, reacting for 60min under a stirring condition, feeding the obtained reaction product into a clarification tank, and settling for 90min to obtain normal-temperature crystallized effluent (the calcium ion concentration is 17.6mmol/L, and the supersaturation degree of calcium sulfate is 131%) and a calcium sulfate product;
(3) supplying 40t/h of normal-temperature crystallized effluent to a nanofiltration separation unit (a first-stage two-stage nanofiltration system), performing nanofiltration separation treatment in the presence of 6mg/L of scale inhibitor, wherein the operating pressure is 1.9MPa, so as to obtain nanofiltration concentrated water (the supersaturation degree of calcium sulfate is 386%) and nanofiltration produced water (the salt content is 11.6g/L), and the recovery rate of the nanofiltration system is 50%; the nanofiltration concentrated water and the neutral softened clear effluent enter a normal-temperature crystallization reactor together for reaction;
(4) carrying out reverse osmosis treatment on nanofiltration produced water for 20t/h to obtain reverse osmosis produced water and reverse osmosis concentrated water (the salt content is 44.9g/L), carrying out electrodialysis treatment on the obtained reverse osmosis concentrated water to obtain electrodialysis concentrated water (the salt content is 197g/L) and electrodialysis produced water, and returning the obtained electrodialysis produced water to reverse osmosis for continuous treatment;
wherein the reverse osmosis operating pressure is 3.6MPa, and the water recovery rate is 67%;
the current density of the electrodialysis operation was 30mA/cm2Current 120A, voltage 117V;
the coupling treatment is carried out to obtain 1.4t/h electrodialysis concentrated water (the salt content is 197g/L) and 18.6t/h reverse osmosis produced water (the salt content is 0.5g/L), and the produced water is reused as recycled water;
(5) feeding the electrodialysis concentrated water at 1.4t/h into a diaphragm electrolytic cell, electrolyzing to obtain 99kg of chlorine (with the purity of 99.0%), 0.4t/h of sodium hydroxide aqueous solution (with the mass concentration of 29%) and 1.0t/h of diaphragm electrolysis fresh water (with the salt content of 114g/L), returning the sodium hydroxide aqueous solution to the step (1), and returning the diaphragm electrolysis fresh water to electrodialysis concentration treatment;
wherein, the diaphragm electrolysis conditions are as follows: the current density is controlled at 3kA/m2And a voltage of 42V.
The results prove that the method can realize the reduction treatment of the desulfurization wastewater through the hardness regulation treatment and the electrodialysis-reverse osmosis coupling concentration treatment, and can recover calcium sulfate products, sodium hydroxide and high-purity chlorine products; in addition, the electrodialysis concentrated water entering the diaphragm electrolysis unit accounts for 7% of the consumption of the desulfurization wastewater, and 93% of the reuse water is recovered.
In addition, in this example, the sodium hydroxide was recycled by adding 14.1 kg/ton of water to calcium hydroxide and 14.4 kg/ton of water to sodium sulfate, compared with the case where the pH of the aqueous solution of calcium hydroxide was adjusted to the same value. And (3) the nanofiltration produced water enters an electrodialysis-reverse osmosis coupling concentration unit for concentration treatment, the operation energy consumption of electrodialysis is 6.2kWh/t, and the energy consumption of diaphragm electrolysis is 6.4 kWh/t.
Example 4
Treating the desulfurization wastewater according to the steps (1) to (4) of the embodiment 1 to obtain secondary nanofiltration concentrated water and secondary nanofiltration produced water, and returning the secondary nanofiltration concentrated water to the primary nanofiltration for continuous treatment;
(5) performing primary reverse osmosis treatment on the secondary nanofiltration produced water for 20t/h to obtain primary reverse osmosis produced water and primary reverse osmosis concentrated water (the salt content is 40.7g/L), performing high-pressure reverse osmosis treatment on the primary reverse osmosis concentrated water to obtain high-pressure reverse osmosis concentrated water and high-pressure reverse osmosis produced water, and returning the high-pressure reverse osmosis produced water to continue the primary reverse osmosis treatment; the treatment can obtain 3.4t/h high-pressure reverse osmosis concentrated water (the salt content is 98.7g/L) and 16.6t/h first-stage reverse osmosis produced water (the salt content is 0.5 g/L);
wherein, the operating pressure of the first-stage reverse osmosis is 3.7MPa, and the water recovery rate is 68.1 percent;
the operating pressure of the high-pressure reverse osmosis is 9.0MPa, and the water recovery rate is 70.2%;
(6) 3.4t/h of the obtained high-pressure reverse osmosis concentrated water is sent into a diaphragm electrolytic cell, 102kg of chlorine (with the purity of 99.6 percent), 0.7t/h of sodium hydroxide aqueous solution (with the mass concentration of 16.5 percent) and 2.7t/h of diaphragm electrolytic fresh water (with the salt content of 62.3g/L) are obtained through electrolysis.
Wherein, the diaphragm electrolysis conditions are as follows: the current density is controlled at 3kA/m2And a voltage of 60V.
The results prove that the method can realize the reduction treatment of the desulfurization wastewater, and simultaneously can recover and obtain calcium sulfate products, sodium hydroxide and high-purity chlorine products; in addition, the electrodialysis concentrated water entering the diaphragm electrolysis unit accounts for 17% of the consumption of the desulfurization wastewater, and 83% of reuse water is recovered. Compared with the embodiment 1, in order to obtain high-concentration brine for electrolysis, high-pressure reverse osmosis treatment is required, on one hand, the operating pressure of the high-pressure reverse osmosis is too high, and the requirement on equipment is higher; on the other hand, the concentration of sodium hydroxide is low in the diaphragm electrolysis operation process, the operation cost is high, and the energy consumption of diaphragm electrolysis is 9.5 kWh/t.
Comparative example 1
(1) Adding the sodium hydroxide aqueous solution obtained in the step (3) into the power plant desulfurization wastewater of 20t/h in a neutralization reaction tank for reaction, adjusting the pH value of the wastewater to 11.7, adding 10mg/L organic sulfur TMT-15 and 9mg/L coagulant aid, reacting for 60min, sending the obtained reaction product into a clarification tank for standing for 120min for sedimentation to obtain softened and clarified effluent, wherein the concentration of magnesium ions is reduced to 6.8 mg/L;
adding sulfuric acid with the mass concentration of 5% into the softened and clarified effluent of 20t/h, and adjusting the pH to 7.4 to obtain neutral softened and clarified effluent;
(2) performing reverse osmosis treatment on the neutral softened clear effluent at 20t/h to obtain reverse osmosis produced water and reverse osmosis concentrated water (the salt content is 57.9g/L), and reusing the reverse osmosis produced water as reuse water;
the reverse osmosis operating pressure is 4.2MPa, and the water recovery rate is 74 percent;
(3) 5t/h of the reverse osmosis concentrated water is sent into a diaphragm electrolytic cell, 109kg of chlorine (with the purity of 99.6%), 2.0t/h of sodium hydroxide aqueous solution (with the mass concentration of 10%) and 3.0t/h of diaphragm electrolytic fresh water (with the salt content of 15g/L) are obtained through electrolysis, the sodium hydroxide aqueous solution returns to the step (1), and the diaphragm electrolytic fresh water returns to the reverse osmosis to continue to be concentrated;
wherein, the diaphragm electrolysis conditions are as follows: the current density is 4kA/m2And a voltage of 75V.
The results prove that the comparative example causes the over-high hardness in the reverse osmosis operation process, and the chemical scaling in the diaphragm electrolysis process causes the unstable operation of the system and needs to be stopped and cleaned frequently; the concentration of sodium hydroxide in the cathode chamber of the diaphragm electrolysis is low, and the energy consumption is 16.2 kWh/t.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
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| CN114933384A (en) * | 2022-05-25 | 2022-08-23 | 上海电站辅机厂有限公司 | Selective electrodialysis concentration salt separation recycling system and method for power plant desulfurization wastewater treatment |
| CN115477431A (en) * | 2022-08-03 | 2022-12-16 | 易钛珑(浙江)水务有限公司 | A low-cost high-salt wastewater reduction and resource utilization method |
| CN115490355A (en) * | 2022-08-22 | 2022-12-20 | 安徽普朗膜技术有限公司 | Coal fired power plant desulfurization effluent treatment plant |
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